original_index
int64
2
1.77M
extracted_from_file
stringclasses
489 values
date_of_experiment
timestamp[ns]date
grant_date
timestamp[ns]date
1976-01-01 00:01:00
2016-01-01 00:09:00
is_mapped
bool
1 class
rxn_str
stringlengths
87
6.12k
reactant_000
stringlengths
1
902
reactant_001
stringlengths
1
902
reactant_002
null
agent_000
stringlengths
1
540
agent_001
stringlengths
1
852
agent_002
stringlengths
1
247
agent_003
null
agent_004
null
agent_005
null
agent_006
null
agent_007
null
agent_008
null
agent_009
null
agent_010
null
agent_011
null
agent_012
null
agent_013
null
agent_014
null
agent_015
null
agent_016
null
solvent_000
stringclasses
446 values
solvent_001
stringclasses
405 values
solvent_002
null
solvent_003
null
solvent_004
null
solvent_005
null
solvent_006
null
solvent_007
null
solvent_008
null
solvent_009
null
solvent_010
null
temperature
float64
-230
30.1k
rxn_time
float64
0
2.16k
procedure_details
stringlengths
8
24.5k
product_000
stringlengths
1
484
product_001
null
yield_000
float64
0
90,205,156,600B
yield_001
float64
0
100M
37,306
ord_dataset-3e699bae9dce4a0f996c34a7c5a4b79a
null
1978-01-01T00:02:00
true
Cl.[CH2:2]1[CH:11]2[N:6]([CH2:7][CH2:8][C:9]3[CH:15]=[CH:14][CH:13]=[CH:12][C:10]=32)[CH2:5][CH2:4][CH:3]1[NH:16][C:17]([NH:19]C(=O)C1C=CC=CC=1)=[O:18]>[OH-].[Na+]>[CH2:2]1[CH:11]2[N:6]([CH2:7][CH2:8][C:9]3[CH:15]=[CH:14][CH:13]=[CH:12][C:10]=32)[CH2:5][CH2:4][CH:3]1[NH:16][C:17]([NH2:19])=[O:18]
O=C(NC(=O)c1ccccc1)NC1CCN2CCc3ccccc3C2C1
null
null
Cl
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1-(1,3,4,6,7,11b-Hexahydro-2H-benzo[a]quinolizin-2-yl)-3-benzoylurea hydrochloride (0.98 g) was refluxed in 2N sodium hydroxide solution (50 ml) for 4 hours. The solution was filtered and the residue washed with water, then ethanol, and finally ether before drying to give the title compound (0.46 g) melting point 235° C. C14H19N3O requires: C, 68.54%; H, 7.81%; N, 17.13%. Found: C, 68.53%; H, 7.79%; N, 17.33%.
NC(=O)NC1CCN2CCc3ccccc3C2C1
null
73.8
null
1,770,938
ord_dataset-0b32b90cc77b4a3db47ad263e0bbc1a8
null
2016-01-01T00:09:00
true
[CH:1]1([CH2:7][O:8][C:9]2[C:10]3[N:11]([C:15]([C:19]([NH:21][CH:22]4[CH2:27][CH2:26][N:25](C(OC(C)(C)C)=O)[CH2:24][CH2:23]4)=[O:20])=[C:16]([CH3:18])[N:17]=3)[CH:12]=[CH:13][CH:14]=2)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[ClH:35].C(OCC)(=O)C>C(OCC)(=O)C>[ClH:35].[ClH:35].[CH:1]1([CH2:7][O:8][C:9]2[C:10]3[N:11]([C:15]([C:19]([NH:21][CH:22]4[CH2:23][CH2:24][NH:25][CH2:26][CH2:27]4)=[O:20])=[C:16]([CH3:18])[N:17]=3)[CH:12]=[CH:13][CH:14]=2)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1
Cc1nc2c(OCC3CCCCC3)cccn2c1C(=O)NC1CCN(C(=O)OC(C)(C)C)CC1
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOC(C)=O
null
null
null
null
null
null
null
null
null
null
null
24
To a solution of 1.44 g of tert-butyl 4-({[8-(cyclohexylmethoxy)-2-methylimidazo[1,2-a]pyridin-3-yl]carbonyl}amino)piperidine-1-carboxylate in 15 ml of ethyl acetate was added 3.8 ml of a 4 M hydrogen chloride/ethyl acetate solution, followed by stirring for 1 day. The reaction mixture was concentrated under reduced pressure, and to the obtained residue were added ethyl acetate and ethanol. The resulting solid was collected by filtration and dried to obtain 1.29 g of 8-(cyclohexylmethoxy)-2-methyl-N-(piperidin-4-yl)imidazo[1,2-a]pyridine-3-carboxamide dihydrochloride.
Cc1nc2c(OCC3CCCCC3)cccn2c1C(=O)NC1CCNCC1
null
null
null
1,694,634
ord_dataset-c1e70ad912eb438f8d34b1dc681f809a
null
2016-01-01T00:02:00
true
[Br:1][C:2]1[C:11]([F:12])=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([CH3:13])[CH:3]=1.[Br:14]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl.C(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[Br:1][C:2]1[C:11]([F:12])=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([CH2:13][Br:14])[CH:3]=1
O=C1CCC(=O)N1Br
COC(=O)c1cc(F)c(Br)cc1C
null
O=C(OOC(=O)c1ccccc1)c1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)(Cl)Cl
ClCCl
null
null
null
null
null
null
null
null
null
null
null
A mixture of methyl 4-bromo-5-fluoro-2-methylbenzoate (1.0 g, 4.0 mmol) (Ellanoval Laboratories Cat. No. 38-0304), N-bromosuccinimide (900. mg, 5.06 mmol) and benzoyl peroxide (50 mg, 0.2 mmol) in carbon tetrachloride (50 mL) was refluxed under a nitrogen atmosphere for 4 h. After cooling the mixture was diluted with methylene chloride. The organic solution was washed with brine, then dried over Na2SO4. After filtration the filtrate was concentrated under reduced pressure. The residue was purified by flash chromatography on a silica gel column with ethyl acetate in hexanes (0-50%) to afford the desired product (1.2 g).
COC(=O)c1cc(F)c(Br)cc1CBr
null
92
null
180,600
ord_dataset-ed5a3d1f8dc744759e7fa1c320a44e59
null
1988-01-01T00:11:00
true
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[C:12]3=[N:19][N:20]=[C:21](S(C)=O)[N:11]3[N:10]=2)=[CH:5][CH:4]=1.[NH:25]1[CH2:29][CH2:28][CH2:27][CH2:26]1>>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[C:12]3=[N:19][N:20]=[C:21]([N:25]4[CH2:29][CH2:28][CH2:27][CH2:26]4)[N:11]3[N:10]=2)=[CH:5][CH:4]=1
COc1ccc(-c2nn3c(S(C)=O)nnc3c3ccccc23)cc1
C1CCNC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
A mixture of 6-(4-methoxyphenyl)-3-(methylsulfinyl)-1,2,4-triazolo[3,4-a]phthalazine (3.5 g) and pyrrolidine (30 ml) is heated to 120°/140° C. in a steel bomb for 16 hours. The mixture is then cooled, and the excess of the amine is evaporated off yielding a residue which is washed carefully with a small amount of water and crystallized from 70% ethanol. Yield: 45%. M.p. 196°-98° C.
COc1ccc(-c2nn3c(N4CCCC4)nnc3c3ccccc23)cc1
null
45
null
1,042,806
ord_dataset-3af92aec23dc4810b92eb0d8c60023ee
null
2011-01-01T00:03:00
true
C([Li])CCC.CC1(C)CCCC(C)(C)N1.[C:16]([O:20][C:21]([NH:23][C:24]1[CH:29]=[N:28][CH:27]=[CH:26][N:25]=1)=[O:22])([CH3:19])([CH3:18])[CH3:17].CN([CH:33]=[O:34])C>O1CCCC1>[C:16]([O:20][C:21]([NH:23][C:24]1[C:29]([CH:33]=[O:34])=[N:28][CH:27]=[CH:26][N:25]=1)=[O:22])([CH3:19])([CH3:17])[CH3:18]
CC(C)(C)OC(=O)Nc1cnccn1
CN(C)C=O
null
CC1(C)CCCC(C)(C)N1
[Li]CCCC
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
-70
0.5
After adding 4 ml of n-butyllithium (2.46 M, n-hexane solution) to a solution of 1.384 g of 2,2,6,6-tetramethylpiperidine in tetrahydrofuran (15 ml) at −20° C. under a nitrogen atmosphere, the mixture was stirred for 30 minutes while cooling on ice. The reaction mixture was cooled to −70° C., and then a solution of 800 mg of 2-(tert-butoxycarbonylamino)pyrazine in tetrahydrofuran (3 ml) was added dropwise, the mixture was stirred for 1 hour, 3 ml of N,N-dimethylformaldehyde was added, and stirring was continued for 30 minutes. After removing the cooling bath and stirring for 30 minutes, water was added and extraction was performed with ethyl acetate. The extract was dried and concentrated and then purified by silica gel column chromatography (solvent: ethyl acetate/n-hexane) to obtain 72 mg of crude 2-(tert-butoxycarbonylamino)pyrazine-3-carboxaldehyde.
CC(C)(C)OC(=O)Nc1nccnc1C=O
null
null
null
693,729
ord_dataset-35824232b132464aa99e71aba765981d
null
2005-01-01T00:12:00
true
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C@@H:9]([NH:29][C:30]([C@@H:32]2[CH2:41][C:40]3[C:35](=[CH:36][CH:37]=[CH:38][CH:39]=3)[CH2:34][N:33]2C(OC(C)(C)C)=O)=[O:31])[C:10]([N:12]2[CH2:17][CH2:16][CH:15]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=3[NH:24][CH2:25][CH:26]3[CH2:28][CH2:27]3)[CH2:14][CH2:13]2)=[O:11])=[CH:4][CH:3]=1.C(O)(C(F)(F)F)=O>C(Cl)Cl>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C@@H:9]([NH:29][C:30]([C@@H:32]2[CH2:41][C:40]3[C:35](=[CH:36][CH:37]=[CH:38][CH:39]=3)[CH2:34][NH:33]2)=[O:31])[C:10]([N:12]2[CH2:17][CH2:16][CH:15]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=3[NH:24][CH2:25][CH:26]3[CH2:28][CH2:27]3)[CH2:14][CH2:13]2)=[O:11])=[CH:4][CH:3]=1
CC(C)(C)OC(=O)N1Cc2ccccc2C[C@H]1C(=O)N[C@H](Cc1ccc(Cl)cc1)C(=O)N1CCC(c2ccccc2NCC2CC2)CC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O=C(O)C(F)(F)F
ClCCl
null
null
null
null
null
null
null
null
null
null
0.5
The title compound was prepared according to the procedure described in Example 3 (Step b) using tert-butyl 3-{N-[(1R)-1-[(4-chlorophenyl)methyl]-2-(4-(2-[(cyclopropylmethyl)-amino]phenyl}piperidyl)-2-oxoethyl]carbamoyl}(3S)-1,2,3,4-tetrahydroisoquinoline-2-carboxylate (Step a) (431 mg, 0.64 mmol) and 50% TFA in CH2Cl2 (20 mL). Purification by reverse phase preparative HPLC [Phenomenex; 5 μm 250×21.2 mm, 5% to 95% CH3CN (0.1% TFA) in H2O (0.1% TFA) over 30 min, then 100% CH3CN (0.1% TFA) for 2 min] provided the title compound (TFA salt) as a white foam (207 mg). MS (ESI, pos. ion) m/z: 571 (M+1); (ESI, neg. ion) m/z: 569 (M−1). Calc'd for C34H39ClN4O2: 570.28. Anal. Calcd for C34H39ClN4O2-2.4C2HF3O2: C, 55.16; H, 4.94; N, 6.63. Found: C, 55.18; H, 5.13; N, 6.61.
O=C(N[C@H](Cc1ccc(Cl)cc1)C(=O)N1CCC(c2ccccc2NCC2CC2)CC1)[C@@H]1Cc2ccccc2CN1
null
null
null
229,086
ord_dataset-9adbd9cd2fd941f7af27fb31c9bf3bac
null
1991-01-01T00:06:00
true
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([N:9]2[CH2:14][CH2:13][N:12]([C:15]3[CH:16]=[CH:17][C:18]([N+:21]([O-])=O)=[N:19][CH:20]=3)[CH2:11][CH2:10]2)=[CH:5][CH:4]=1>C(OCC)(=O)C.[Pt]>[NH2:21][C:18]1[CH:17]=[CH:16][C:15]([N:12]2[CH2:13][CH2:14][N:9]([C:6]3[CH:7]=[CH:8][C:3]([O:2][CH3:1])=[CH:4][CH:5]=3)[CH2:10][CH2:11]2)=[CH:20][N:19]=1
COc1ccc(N2CCN(c3ccc([N+](=O)[O-])nc3)CC2)cc1
null
null
[Pt]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOC(C)=O
null
null
null
null
null
null
null
null
null
null
null
12
A suspension of the product of part (i) (0.65 g, 2.0 mmole) in ethyl acetate (30 ml) was hydrogenated over 5% platinum on carbon (25 mg) at 45 p.s.i. (310 kPa) and at 50° for 12 hours, followed by 45 hours at room temperature. The resulting mixture was filtered to remove the catalyst, concentrated under reduced pressure and the residue triturated with ether to yield the desired product, m.p. 182°-188° (0.28 g, 50%), which was used without further purification.
COc1ccc(N2CCN(c3ccc(N)nc3)CC2)cc1
null
null
null
1,599,000
ord_dataset-e8c6a25568b64529b960953990e6921f
null
2015-01-01T00:06:00
true
[N:1]1[CH:6]=[CH:5][C:4]([CH2:7][CH:8](C(C(OCC)=O)C(OCC)=O)[CH3:9])=[CH:3][CH:2]=1.[C:21](=[O:24])(O)[O-:22].[Na+]>Cl>[N:1]1[CH:6]=[CH:5][C:4]([CH2:7][CH:8]([CH3:9])[C:21]([OH:22])=[O:24])=[CH:3][CH:2]=1
O=C([O-])O
CCOC(=O)C(C(=O)OCC)C(C)Cc1ccncc1
null
Cl
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Compound diethyl 2-(1-(pyridin-4-yl)propan-2-yl)malonate (2.50 g, 9.43 mmol) was refluxed in cone. HCl (30 ml) for 16 h. The pH of the reaction mixture was adjusted to 6 by adding solid sodium bicarbonate and extracted with ethyl acetate. The combined ethyl acetate layer was washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated in vacuum to afford 1.20 g (76.9%) of 2-((pyridin-4-yl)methyl)propanoic acid as an off-white solid.
CC(Cc1ccncc1)C(=O)O
null
76.9
null
919,205
ord_dataset-8e59bd24817446f7b1c68e805b8e5f1d
null
2009-01-01T00:11:00
true
Cl[C:2]1[CH:7]=[CH:6][N:5]=[C:4]([NH:8][CH:9]2[CH2:14][C:13]([CH3:16])([CH3:15])[NH:12][C:11]([CH3:18])([CH3:17])[CH2:10]2)[N:3]=1.CC1(C)C(C)(C)OB([C:27]2[CH:32]=[CH:31][C:30]([CH2:33][C:34](=[O:36])[CH3:35])=[CH:29][CH:28]=2)O1>>[CH3:15][C:13]1([CH3:16])[CH2:14][CH:9]([NH:8][C:4]2[N:3]=[C:2]([C:27]3[CH:32]=[CH:31][C:30]([CH2:33][C:34](=[O:36])[CH3:35])=[CH:29][CH:28]=3)[CH:7]=[CH:6][N:5]=2)[CH2:10][C:11]([CH3:18])([CH3:17])[NH:12]1
CC(=O)Cc1ccc(B2OC(C)(C)C(C)(C)O2)cc1
CC1(C)CC(Nc2nccc(Cl)n2)CC(C)(C)N1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared from (4-chloro-pyrimidin-2-yl)(2,2,6,6-tetramethyl-piperidin-4-yl)-amine and 1-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-propan-2-one according to Method C (Example 178). Yield: 160 mg (78%).
CC(=O)Cc1ccc(-c2ccnc(NC3CC(C)(C)NC(C)(C)C3)n2)cc1
null
null
null
293,842
ord_dataset-b90b48a6c23149a1aa2d91b92b1a31e4
null
1994-01-01T00:07:00
true
[O:1]=[C:2]([N:5]1[C@H:9]([CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH2:8][O:7][C:6]1=[O:17])[CH2:3][CH3:4].[CH3:18][C@@H:19]([CH2:22][O:23][Si:24]([C:27]([CH3:30])([CH3:29])[CH3:28])([CH3:26])[CH3:25])[CH:20]=[O:21]>>[O:1]=[C:2]([N:5]1[C@H:9]([CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH2:8][O:7][C:6]1=[O:17])[C@H:3]([CH3:4])[C@H:20]([OH:21])[C@@H:19]([CH3:18])[CH2:22][O:23][Si:24]([C:27]([CH3:29])([CH3:28])[CH3:30])([CH3:25])[CH3:26]
CCC(=O)N1C(=O)OC[C@H]1Cc1ccccc1
C[C@H](C=O)CO[Si](C)(C)C(C)(C)C
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
This material is prepared from (R)-3-(1-oxopropyl)-4-(phenylmethyl)-2-oxazolidinone and 2-(S)-methyl-3-t-butyldimethylsiloxypropanal following the method of Evans and Gage, as described in Org. Syn., Vol. 68, 19xx, p. 83.
C[C@@H](CO[Si](C)(C)C(C)(C)C)[C@@H](O)[C@@H](C)C(=O)N1C(=O)OC[C@H]1Cc1ccccc1
null
null
null
863,412
ord_dataset-b8b98725045d45bdbd73512048f4b47e
null
2009-01-01T00:02:00
true
[CH3:1][O:2][C:3]1[C:17]([O:18][CH3:19])=[CH:16][CH:15]=[CH:14][C:4]=1[CH2:5][NH:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH3:13].[CH2:20]([O:22][C@H:23]([C:36]([O:38][CH2:39][CH3:40])=[O:37])[CH2:24][C:25]1[CH:35]=[CH:34][C:28]([O:29][CH2:30][C:31](O)=[O:32])=[CH:27][CH:26]=1)[CH3:21].C(N(CC)C(C)C)(C)C.F[B-](F)(F)F.N1(OC(N(C)C)=[N+](C)C)C2C=CC=CC=2N=N1>C(Cl)Cl>[CH3:1][O:2][C:3]1[C:17]([O:18][CH3:19])=[CH:16][CH:15]=[CH:14][C:4]=1[CH2:5][N:6]([CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH3:13])[C:31](=[O:32])[CH2:30][O:29][C:28]1[CH:27]=[CH:26][C:25]([CH2:24][C@H:23]([O:22][CH2:20][CH3:21])[C:36]([O:38][CH2:39][CH3:40])=[O:37])=[CH:35][CH:34]=1
CCOC(=O)[C@H](Cc1ccc(OCC(=O)O)cc1)OCC
CCCCCCCNCc1cccc(OC)c1OC
null
CN(C)C(On1nnc2ccccc21)=[N+](C)C
F[B-](F)(F)F
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(C(C)C)C(C)C
ClCCl
null
null
null
null
null
null
null
null
null
25
8
To a solution of N-(2,3-dimethoxybenzyl)-N-heptylamine (1.46 g, 5.5 mmol) and {4-[(2S)-2,3-diethoxy-3-oxopropyl]phenoxy}acetic acid (1.48 g, 5.0 mmol) in methylene chloride (50 mL) at 0° C. were added N,N-diisopropylethylamine (2.0 mL, 11.5 mmol) and O-(benzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium tetrafluoroborate (1.93 g, 6.0 mmol) and the reaction mixture was stirred at room temperature overnight and then concentrated in vacuo. The residue was taken up in ethyl acetate (200 mL) and the organic phase was washed with saturated aqueous NaHCO3 (3×100 mL), 5% HCl (3×100 mL), and brine (100 mL), dried over Na2SO4, and concentrated in vacuo. Purification on silica gel (100 g) with methanol (0-2% gradient) in methylene chloride as the eluent and collection of pure fractions yielded 1.57 g (58%) of a pale yellow oil.
CCCCCCCN(Cc1cccc(OC)c1OC)C(=O)COc1ccc(C[C@H](OCC)C(=O)OCC)cc1
null
57.8
null
893,221
ord_dataset-11068b1e475b4c5b82e56726ab0dddb7
null
2009-01-01T00:07:00
true
[NH:1]1[CH2:5][CH2:4][N:3]=[C:2]1[C:6]([NH2:26])([C:17]1[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[C:19]([CH3:25])[CH:18]=1)[C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([O:13][CH2:14][CH2:15][CH3:16])[CH:8]=1.[N:27]#[C:28]Br>C(Cl)(Cl)Cl>[CH3:24][O:23][C:20]1[CH:21]=[CH:22][C:17]([C:6]2([C:7]3[CH:12]=[CH:11][CH:10]=[C:9]([O:13][CH2:14][CH2:15][CH3:16])[CH:8]=3)[C:2]3=[N:1][CH2:5][CH2:4][N:3]3[C:28]([NH2:27])=[N:26]2)=[CH:18][C:19]=1[CH3:25]
N#CBr
CCCOc1cccc(C(N)(C2=NCCN2)c2ccc(OC)c(C)c2)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)Cl
null
null
null
null
null
null
null
null
null
null
60
null
A solution of [4,5-dihydro-1H-imidazol-2-yl(4-methoxy-3-methylphenyl)(3-propoxyphenyl)methyl]amine (0.6 g) in chloroform is treated with cyanogen bromide (0.581 g), heated at 60° C. for 5 days and filtered through a pad of silica. The silica pad was eluted with ethyl acetate, followed by elution with (40:5:5) ethyl acetate: methanol: ammonium hydroxide. The eluents were combined and concentrated in vacuo to give a thick yellow oil, which was purified by Gilson preparative reverse phase HPLC system YMC Pro C18, 20 mm×50 mm ID, 5 uM column; 2 mL injection; Solvent A: 0.02% NH4OH/water; Solvent B:0.02% NH4OH/acetonitrile; Gradient: Time O: 95% A; 2 min: 95% A; 14 min: 10% A, 15 min: 10% A, 16 min: 95% A; Flow rate 22.5 mL/min; Detection: 254 nm DAD to afford the title compound was as an off-white, amphorous solid (0.131 g), characterized by LCMS analysis. LCMS Conditions: HP 1100 HPLC system; Waters Xterra MS C18, 2 mm (i.d.)×50 mm (length), 3.5 um column, set at 50° C.; Flow rate 1.0 mL/min; Solvent A: 0.02% NH4OH in water; Solvent B 0.02% NH4OH in ACN; Gradient: Time O: 10% B; 2.5 min 90% B; 3 min 90% B; Sample concentration: ˜2.0 mM; Injection volume: 5 uL; Detection: 220 nm, 254 nm DAD; retention time: 2.34 min, [M−H] 377, [M+H] 379.
CCCOc1cccc(C2(c3ccc(OC)c(C)c3)N=C(N)N3CCN=C32)c1
null
null
null
1,290,896
ord_dataset-de51ecc8d4434bacaa8bc32d7d73484c
null
2013-01-01T00:05:00
true
[Cl:1][C:2]1[N:7]=[C:6]([NH:8][CH2:9][C:10]([CH3:14])([CH3:13])[CH2:11][NH2:12])[CH:5]=[C:4]([C:15]2[C:23]3[C:18](=[N:19][CH:20]=[CH:21][CH:22]=3)[NH:17][CH:16]=2)[CH:3]=1.C(N(CC)CC)C.[N:31]1[CH:36]=[CH:35][CH:34]=[C:33]([S:37](Cl)(=[O:39])=[O:38])[CH:32]=1>CN(C=O)C>[Cl:1][C:2]1[N:7]=[C:6]([NH:8][CH2:9][C:10]([CH3:14])([CH3:13])[CH2:11][NH:12][S:37]([C:33]2[CH:32]=[N:31][CH:36]=[CH:35][CH:34]=2)(=[O:39])=[O:38])[CH:5]=[C:4]([C:15]2[C:23]3[C:18](=[N:19][CH:20]=[CH:21][CH:22]=3)[NH:17][CH:16]=2)[CH:3]=1
O=S(=O)(Cl)c1cccnc1
CC(C)(CN)CNc1cc(-c2c[nH]c3ncccc23)cc(Cl)n1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(CC)CC
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
4
To a solution of Example 74 (55.0 mg, 0.167 mmol) in DMF (1 mL) was added triethylamine (0.070 mL, 0.50 mmol) and pyridine-3-sulfonyl chloride (35.5 mg, 0.200 mmol). After 4 hours, the reaction was quenched with 20% brine and extracted with EtOAc (2×). The organic layers were combined, concentrated, and purified by reverse-phase HPLC as described in Example 56 to give the title compound (28.5 mg) as trifluoroacetic acid salts. 1H NMR (500 MHz, DMSO-d6) ppm 0.89 (s, 6H), 2.68 (d, J=7.02 Hz, 2H), 3.13 (s, 2H), 6.80 (s, brd, 1H), 6.89 (d, J=1.22 Hz, 1H), 6.94 (s, 1H), 7.22 (dd, J=8.09, 4.73 Hz, 1H), 7.60 (dd, J=7.63, 4.58 Hz, 1H), 7.77 (t, J=6.87 Hz, 1H), 8.12-8.18 (m, 2H), 8.28-8.35 (m, 2H), 8.77 (d, J=6.41 Hz, 1H), 8.94 (d, J=2.14 Hz, 1H), 12.19 (s, 1H). MS (APCI+) m/z 471.2 (M+H)+.
CC(C)(CNc1cc(-c2c[nH]c3ncccc23)cc(Cl)n1)CNS(=O)(=O)c1cccnc1
null
36.2
null
693,742
ord_dataset-35824232b132464aa99e71aba765981d
null
2005-01-01T00:12:00
true
Cl.[Br:2][C:3]1[CH:11]=[C:10]2[C:6]([C:7]([CH2:16][C:17]#[N:18])=[CH:8][N:9]2[S:12]([CH3:15])(=[O:14])=[O:13])=[CH:5][C:4]=1[F:19].[CH2:20](N)[CH2:21][NH2:22]>C(O)C>[Br:2][C:3]1[CH:11]=[C:10]2[C:6]([C:7]([CH2:16][C:17]3[NH:22][CH2:21][CH2:20][N:18]=3)=[CH:8][N:9]2[S:12]([CH3:15])(=[O:14])=[O:13])=[CH:5][C:4]=1[F:19]
NCCN
CS(=O)(=O)n1cc(CC#N)c2cc(F)c(Br)cc21
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
null
72
Hydrogen chloride gas was bubbled through a cold (0° C.) suspension of (6-Bromo-5-fluoro-1-methanesulfonyl-1H-indol-3-yl)-acetonitrile (0.215 g, 0.65 mmol) in anhydrous ethanol (20 ml) for 15 minutes. The reaction mixture was refrigerated for 72 hours and the solvent was removed under reduced pressure. The solid residue was re-dissolved in anhydrous methanol (10 ml), and ethylene diamine (0.05 ml, 0.77 mmol) was added. The reaction mixture was heated to reflux for 24 hours and the solvent was removed under reduced pressure. The resulting residue was purified by flash column chromatography over silica gel eluting with 7% methanol in dichloromethane with 0.1% concentrated ammonium hydroxide to give 6-Bromo-3-(4,5-dihydro-1H-imidazol-2-ylmethyl)-5-fluoro-1-methanesulfonyl-1H-indole, which was recrystallized from methanol and ether (0.133 g, 55%). 1H NMR (DMSO) d: 3.56 (s, 3H), 3.82(s, 4H), 4.07 (s, 2H), 7.84 (s, 1H), 7.90 (d, 1H, J=9.1 Hz), 8.10 (d, 1H, J=5.8 Hz), 10.23 (bs, 1H). M+H: 374.
CS(=O)(=O)n1cc(CC2=NCCN2)c2cc(F)c(Br)cc21
null
null
null
1,049,369
ord_dataset-dd320ded4b3f4764af39de99491533f7
null
2011-01-01T00:04:00
true
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([CH3:9])=[CH:5][C:4]=1[NH:10][C:11](=O)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[O:18][CH3:19])#[N:2].[OH-:21].[Na+].OO>C(O)C>[CH3:19][O:18][C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][C:12]=1[C:11]1[NH:2][C:1](=[O:21])[C:3]2[C:4](=[CH:5][C:6]([CH3:9])=[CH:7][CH:8]=2)[N:10]=1
[OH-]
COc1ccccc1C(=O)Nc1cc(C)ccc1C#N
null
OO
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
80
null
To a mechanically stirred suspension of N-(2-cyano-5-methylphenyl)-2-methoxybenzamide (180 g, 0.67 mol) in 1.8 L ethanol under an N2 atmosphere was added 6 N sodium hydroxide solution (310 g in 1.25 L water). To the above mixture, 30% hydrogen peroxide (350 mL, 3.64 mol) was slowly added. The solution was then slowly heated to 80° C. and maintained at this temperature for 4 h. The reaction mixture was concentrated under reduced pressure to remove ethanol, giving a suspension, which was quenched with ice-cold water (1.8 L) and acidified with acetic acid to pH 5-6 to give a solid residue. The solid was filtered and washed with water, then dissolved in 5.5 L CH2Cl2 and washed with water (2×18 L). The organic layer was dried over sodium sulfate, and the solvent was removed under reduced pressure to give a light yellow solid (100 g, 54%). mp 165-170° C.
COc1ccccc1-c1nc2cc(C)ccc2c(=O)[nH]1
null
56
null
171,005
ord_dataset-41558b7e18dd41999311b1762e0e13a3
null
1988-01-01T00:04:00
true
[S:1]1[CH2:6][CH2:5][N:4]([CH2:7][N:8]2[C:13](=[O:14])[CH2:12][N:11]([CH2:15][CH:16]([N:18]3[CH2:23][C:22](=[O:24])[N:21](CN4CCSCC4)[C:20](=[O:32])[CH2:19]3)[CH3:17])[CH2:10][C:9]2=[O:33])[CH2:3][CH2:2]1>O>[S:1]1[CH2:6][CH2:5][N:4]([CH2:7][N:8]2[C:13](=[O:14])[CH2:12][N:11]([CH2:15][CH:16]([N:18]3[CH2:19][C:20](=[O:32])[NH:21][C:22](=[O:24])[CH2:23]3)[CH3:17])[CH2:10][C:9]2=[O:33])[CH2:3][CH2:2]1
CC(CN1CC(=O)N(CN2CCSCC2)C(=O)C1)N1CC(=O)N(CN2CCSCC2)C(=O)C1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
null
null
null
null
null
null
null
null
null
null
25
5
Water (30 ml) was added to dl-1,2-bis(4-thiomorpholinomethyl-3,5-dioxopiperazin-1-yl)-propane (0.6 g) and the suspension thus obtained was stirred at room temperature for 5 hours. Then, the precipitates thus obtained were collected and were dried under a reduced pressure. Chloroform (10 ml) was added to the dried precipitates and the whole was stirred at room temperature for 20 minutes, then was filtered. The filtration residue was dried under a reduced pressure to give the titled compound (0.2 g; yield 43%).
CC(CN1CC(=O)N(CN2CCSCC2)C(=O)C1)N1CC(=O)NC(=O)C1
null
43.3
null
181,197
ord_dataset-ed5a3d1f8dc744759e7fa1c320a44e59
null
1988-01-01T00:11:00
true
C[O:2][C:3](=[O:21])/[CH:4]=[CH:5]/[CH:6]=[C:7](/[C:13]1[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[CH:15][CH:14]=1)\[CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].[OH-].[Na+]>CO>[CH3:20][O:19][C:16]1[CH:15]=[CH:14][C:13](/[C:7](/[CH2:8][CH2:9][CH2:10][CH2:11][CH3:12])=[CH:6]/[CH:5]=[CH:4]/[C:3]([OH:21])=[O:2])=[CH:18][CH:17]=1
CCCCC/C(=C\C=C\C(=O)OC)c1ccc(OC)cc1
null
null
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
null
0.75
As described in Example 99, (E,E)-5-(4-methoxyphenyl)-2,4-decadienoic acid methyl ester 6.1 g) was saponified in a refluxing mixture of methanol (25 mL) and 2N NaOH (25 mL). After 45 minutes the reaction was worked up in the usual way and the crude acid crystallized from 2-propanol to give 4.7 g of (E,E)-5-(4-methoxyphenyl)-2,4-decadienoic acid, mp 126°-127.5° C.
CCCCC/C(=C\C=C\C(=O)O)c1ccc(OC)cc1
null
81
null
293,478
ord_dataset-b90b48a6c23149a1aa2d91b92b1a31e4
null
1994-01-01T00:07:00
true
C[O:2][C:3](=[O:30])[C@:4]([C:20]1[CH:29]=[CH:28][C:27]2[C:22](=[CH:23][CH:24]=[CH:25][CH:26]=2)[N:21]=1)([CH3:19])[NH:5][C:6]([O:8][CH:9]1[CH:16]2[CH2:17][CH:12]3[CH2:13][CH:14]([CH2:18][CH:10]1[CH2:11]3)[CH2:15]2)=[O:7]>CCCCC>[CH:10]12[CH2:18][CH:14]3[CH2:13][CH:12]([CH2:17][CH:16]([CH2:15]3)[CH:9]1[O:8][C:6]([NH:5][C@:4]([C:20]1[CH:29]=[CH:28][C:27]3[C:22](=[CH:23][CH:24]=[CH:25][CH:26]=3)[N:21]=1)([C:3]([OH:30])=[O:2])[CH3:19])=[O:7])[CH2:11]2
COC(=O)[C@](C)(NC(=O)OC1C2CC3CC(C2)CC1C3)c1ccc2ccccc2n1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCCCC
null
null
null
null
null
null
null
null
null
null
null
null
Method was as described for Example 30, Step 5, but using N-(2-adamantyloxy-carbonyl)-2-(quinolin-yl)-alanine methyl ester (3.5 g, 8.3 mmol) to obtain N-(2-adamantyloxy-carbonyl)-2-(quinolin-yl)-alanine (2.0 g, 59.0%) as a beige solid from n-pentane.
C[C@](NC(=O)OC1C2CC3CC(C2)CC1C3)(C(=O)O)c1ccc2ccccc2n1
null
61.1
null
94,333
ord_dataset-62e11cab5a6e47d89878616c244e20ef
null
1982-01-01T00:05:00
true
[C:1]([O:4][C@@H:5]1[CH2:10][C@H:9]2[C@H:11]3[C@H:21]([CH2:22][CH2:23][C@:7]2([CH3:8])[C@H:6]1[N:25]([CH3:32])[C:26](=[O:31])[C:27]([F:30])([F:29])[F:28])[C@:19]1([CH3:20])[C:14](=[CH:15][C:16](=[O:24])[CH2:17][CH2:18]1)[CH2:13][CH2:12]3)(=[O:3])[CH3:2].C1(C)C=CC=CC=1>ClC1C=CC=CC=1>[C:1]([O:4][C@@H:5]1[CH2:10][C@H:9]2[C@H:11]3[C@H:21]([CH2:22][CH2:23][C@:7]2([CH3:8])[C@H:6]1[N:25]([CH3:32])[C:26](=[O:31])[C:27]([F:29])([F:28])[F:30])[C@:19]1([CH3:20])[C:14](=[CH:15][C:16](=[O:24])[CH:17]=[CH:18]1)[CH2:13][CH2:12]3)(=[O:3])[CH3:2]
CC(=O)O[C@@H]1C[C@H]2[C@@H]3CCC4=CC(=O)CC[C@]4(C)[C@H]3CC[C@]2(C)[C@H]1N(C)C(=O)C(F)(F)F
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Clc1ccccc1
Cc1ccccc1
null
null
null
null
null
null
null
null
null
null
null
A solution of 16α-acetyloxy-17β-(N-trifluoroacetyl-methylamino)-androst-4-en-3-one (1.88 g) and diphenylselenic anhydride (1.7 g) in chlorobenzene (39 ml) was heated under reflux for 1 h. The solution was cooled, toluene was added and the solution was filtered through a column (7.5 cm×2.5 cm) of silica gel (0.063-0.2 mm). Elution with toluene removed diphenylselenide. Elution with ether yielded a fraction which was evaporated to dryness to give 16α-acetyloxy-17β-(N-trifluoroacetyl-methylamino)-androsta-1,4-dien-3-one as a yellow gum (1.52 g). A solution of the product in ethanol (40 ml) and aqueous sodium hydroxide solution (3 ml; 4 N) was heated under reflux for 1.5 h.; the solution was concentrated and cooled, then water was added to precipitate an off-white solid, which was filtered off, washed with water and dried in vacuo to give 16α-hydroxy-17β-methylamino-androsta-1,4-dien-3-one (1 g). The product was dissolved in ethanol (20 ml), a solution of maleic acid (0.37 g) in ethanol (10 ml) was added and the resulting solution was treated with charcoal, filtered and evaporated to give a pale yellow gum (1.44 g). Crystallisation from acetone gave 16α-hydroxy-17β-methylamino-androsta-1,4-dien-3-one (Z)-2-butenedioate (1:1) (salt) as colourless prisms (0.88 g), m.p. 184°-191° C. (decomp.), [α]D +14.2° (c 0.88 in ETOH).
CC(=O)O[C@@H]1C[C@H]2[C@@H]3CCC4=CC(=O)C=C[C@]4(C)[C@H]3CC[C@]2(C)[C@H]1N(C)C(=O)C(F)(F)F
null
81.2
null
1,333,632
ord_dataset-cfad8b3f00044bcda60a96b019f09872
null
2013-01-01T00:08:00
true
[F:1][C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[N:9]1[CH:13]=[C:12](I)[N:11]=[CH:10]1.C([Mg]Cl)(C)C.[CH2:20]([Sn:24](Cl)([CH2:29][CH2:30][CH2:31][CH3:32])[CH2:25][CH2:26][CH2:27][CH3:28])[CH2:21][CH2:22][CH3:23].[NH4+].[Cl-]>O1CCCC1>[F:1][C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[N:9]1[CH:13]=[C:12]([Sn:24]([CH2:25][CH2:26][CH2:27][CH3:28])([CH2:29][CH2:30][CH2:31][CH3:32])[CH2:20][CH2:21][CH2:22][CH3:23])[N:11]=[CH:10]1
Fc1ccc(F)c(-n2cnc(I)c2)c1
CCCC[Sn](Cl)(CCCC)CCCC
null
CC(C)[Mg]Cl
[Cl-]
[NH4+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
1.5
A solution of 1-(2,5-difluorophenyl)-4-iodo-1H-imidazole (0.115 g, 0.38 mmol) in 2 mL of tetrahydrofuran was chilled in an ice/water bath 5 min. Isopropylmagnesium chloride solution (2.0 M in tetrahydrofuran, 0.190 mL, 0.38 mmol) was added all at once. The bath was removed, and the pale yellow solution stirred 1.5 h. Tributyltin chloride (0.105 mL, 0.39 mmol) was added all at once, and the pale yellow solution was stirred 1.5 h. A sat. aq. NH4Cl solution (10 mL) was added, and the mixture was extracted with two 10 mL portions of ethyl acetate. The combined organic layers were washed with 20 mL of a sat. aq. NaCl solution, dried over Na2SO4, filtered and concentrated to provide 0.198 g of 1-(2,5-difluoro-phenyl)-4-tributylstannanyl-1H-imidazole as a yellow oil which was used without further purification. MS: (M+H)+=471.
CCCC[Sn](CCCC)(CCCC)c1cn(-c2cc(F)ccc2F)cn1
null
111.1
null
845,790
ord_dataset-e2b35e721c2741999b0005d12691f9fe
null
2008-01-01T00:10:00
true
C(OC(=O)[NH:10][CH2:11][C:12]1[NH:13][C:14]2[C:19]([CH:20]=1)=[CH:18][CH:17]=[C:16]([OH:21])[CH:15]=2)C1C=CC=CC=1.C([O-])([O-])=O.[Cs+].[Cs+].Cl[CH:30]([C:36]([O:38][CH2:39][CH3:40])=[O:37])[C:31]([O:33][CH2:34][CH3:35])=[O:32]>CC(C)=O.C(OCC)(=O)C>[CH2:34]([O:33][C:31](=[O:32])[CH:30]([O:21][C:16]1[CH:15]=[C:14]2[C:19]([CH:20]=[C:12]([CH2:11][NH2:10])[NH:13]2)=[CH:18][CH:17]=1)[C:36]([O:38][CH2:39][CH3:40])=[O:37])[CH3:35]
O=C(NCc1cc2ccc(O)cc2[nH]1)OCc1ccccc1
CCOC(=O)C(Cl)C(=O)OCC
null
O=C([O-])[O-]
[Cs+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(C)=O
CCOC(C)=O
null
null
null
null
null
null
null
null
null
null
8
(6-Hydroxy-1H-indol-2-ylmethyl)-carbamic acid benzyl ester was dissolved in 10 ml acetone, Cs2CO3 and diethyl chloromalonate were added. The reaction is stirred overnight. HPLC and TLC indicated the reaction is done. The mixture was diluted with ethyl acetate and filtered through silica gel plug. The filtrate is concentrated and redissolved in ethanol, hydrogenated for 3 hours at 40 psi of hydrogen. The mixture is filtered, washed with ethyl acetate. The filtrate is concentrated to give 2-(2-Aminomethyl-1H-indol-6-yloxy)-malonic acid diethyl ester.
CCOC(=O)C(Oc1ccc2cc(CN)[nH]c2c1)C(=O)OCC
null
null
null
868,815
ord_dataset-c31cb9b44c404c10ba3aa533aa079e2b
null
2009-01-01T00:03:00
true
[C:1]([C:3]([C:24]#[N:25])=[C:4]([N:11]1[CH2:16][CH2:15][N:14](C(OC(C)(C)C)=O)[CH2:13][CH2:12]1)[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)#[N:2]>C(O)(C(F)(F)F)=O.C(Cl)Cl>[C:5]1([C:4]([N:11]2[CH2:16][CH2:15][NH:14][CH2:13][CH2:12]2)=[C:3]([C:1]#[N:2])[C:24]#[N:25])[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1
CC(C)(C)OC(=O)N1CCN(C(=C(C#N)C#N)c2ccccc2)CC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
O=C(O)C(F)(F)F
null
null
null
null
null
null
null
null
null
null
16
tert-Butyl 4-(2,2-dicyano-1-phenylvinyl)piperazine-1-carboxylate (2 g) was dissolved in a 33.3% solution of TFA in methylene chloride (20 ml). After 16 hour at room temperature, solvents were removed under vacuum to offer a residue which was purified using silica gel chromatography to give 2-(phenyl(piperazin-1-yl)methylene)malononitrile (1 g). 1H NMR (500 MHz, CD3OD) □7.62 (m, 5H), 3.70 (b, 4H), 3.47 (b, 4H); 13C NMR (125 MHz, CD3OD) □172.9, 132.7, 132.5, 129.6, 116.6, 116.0, 55.2, 43.4. MS m/z: (M+H)+ calcd for C14H15N4 239.13, found 239.13. Retention time 0.56 min (column A).
N#CC(C#N)=C(c1ccccc1)N1CCNCC1
null
71
null
1,752,496
ord_dataset-97eb2ab57fec4160922caae33b54d956
null
2016-01-01T00:08:00
true
[NH2:1][CH2:2][C@H:3]1[CH2:8][CH2:7][CH2:6][N:5]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:4]1.Br[C:17]1[C:18]([NH2:24])=[N:19][CH:20]=[C:21]([Br:23])[N:22]=1.CCN(CC)CC>CS(C)=O>[NH2:24][C:18]1[C:17]([NH:1][CH2:2][C@H:3]2[CH2:8][CH2:7][CH2:6][N:5]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:4]2)=[N:22][C:21]([Br:23])=[CH:20][N:19]=1
Nc1ncc(Br)nc1Br
CC(C)(C)OC(=O)N1CCC[C@H](CN)C1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CS(C)=O
CCN(CC)CC
null
null
null
null
null
null
null
null
null
130
8
(R)-tert-butyl 3-(aminomethyl)piperidine-1-carboxylate (4.97 g, 22.40 mmol) was dissolved in DMSO (80 ml), and then 3,5-dibromopyrazine-2-amine (8.5 g, 33.60 mmol) and Et3N (6.3 ml) were added, followed by stirring at 130° C. overnight. After the completion of the reaction, the reaction mixture was extracted with H2O, EA, and brine, followed by drying (Na2SO4), filtration, and concentration under reduced pressure, and the residue was purified by column chromatography (EA:Hex=1:1), to give (R)-tert-butyl 3-(((3-amino-6-bromopyrazine-2-yl)amino)methyl)piperidine-1-carboxylate (2.19 g, two steps: 26%).
CC(C)(C)OC(=O)N1CCC[C@H](CNc2nc(Br)cnc2N)C1
null
25.3
null
196,391
ord_dataset-a58d1baeeea441fb9918c10f18f2cdb9
null
1989-01-01T00:09:00
true
C(C1[CH:13]=[CH:12][C:6]([NH:7][S:8]([CH3:11])(=[O:10])=[O:9])=[C:5]([O:14][C:15]2[CH:20]=[CH:19][C:18]([F:21])=[CH:17][C:16]=2[F:22])[CH:4]=1)#N.Cl.[C:24]([OH:27])(=[O:26])[CH3:25]>>[F:22][C:16]1[CH:17]=[C:18]([F:21])[CH:19]=[CH:20][C:15]=1[O:14][C:5]1[CH:4]=[C:25]([CH:13]=[CH:12][C:6]=1[NH:7][S:8]([CH3:11])(=[O:9])=[O:10])[C:24]([OH:27])=[O:26]
CC(=O)O
CS(=O)(=O)Nc1ccc(C#N)cc1Oc1ccc(F)cc1F
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
A mixture of 4'-cyano-2'-(2,4-difluorophenoxy)methanesulfonanilide (1.3 g) and concentrated hydrochloric acid (13 ml) in acetic acid (8 ml) was refluxed for 8 hours. The precipitates were filtered, washed with water, dried, and recrystallized from a mixture of ethyl acetate and hexane to give crystals of 3-(2,4-difluorophenoxy)-4-(methanesulfonamido)benzoic acid (0.72 g).
CS(=O)(=O)Nc1ccc(C(=O)O)cc1Oc1ccc(F)cc1F
null
null
null
780,214
ord_dataset-8034115bd2ec4d3e95bd3ff7cfde0bde
null
2007-01-01T00:07:00
true
[OH:1][CH:2]1[CH:7]2[CH2:8][CH2:9][N:4]([CH2:5][CH2:6]2)[CH2:3]1.I[C:11]1[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][CH:12]=1>>[N+:17]([C:14]1[CH:15]=[CH:16][C:11]([O:1][CH:2]2[CH:7]3[CH2:8][CH2:9][N:4]([CH2:5][CH2:6]3)[CH2:3]2)=[CH:12][CH:13]=1)([O-:19])=[O:18]
O=[N+]([O-])c1ccc(I)cc1
OC1CN2CCC1CC2
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
3-Hydroxy quinuclidine (Aldrich, 2.54 g, 10 mmol) was treated with 1-iodo-4-nitro-benzene (5 g, 20 mmol) according to the procedure of Example 14A. The title compound was purified by chromatography (SiO2, CH2Cl2:MeOH:NH3.H2O, 90:10:1, Rf. 0.20) (1.02 g, yield, 21%). 1H NMR (MeOH-d4, 300 MHz) δ 1.40–1.56 (m, 1H), 1.65–1.90 (m, 2H), 1.90–2.08 (m, 1H), 2.15–2.25 (m, 1H), 2.75–3.00 (m, 5H), 3.34–3.40 (m, 1H), 4.69 (m, 1H), 7.07 (d, J=9.5 Hz, 2H), 8.21 (d, J=9.2, Hz, 2H) ppm. MS (DCl/NH3) m/z 249 (M+H)+.
O=[N+]([O-])c1ccc(OC2CN3CCC2CC3)cc1
null
null
null
129,860
ord_dataset-2f37329a4b254471a74f2eb0981f11ec
null
1985-01-01T00:05:00
true
Cl.[C:2]([O:5][CH:6]1[CH2:14][CH2:13][CH:12]2[CH:7]1[CH2:8][CH:9]=[C:10]([O:15]C)[CH2:11]2)(=[O:4])[CH3:3]>CO>[C:2]([O:5][CH:6]1[CH2:14][CH2:13][CH:12]2[CH:7]1[CH2:8][CH2:9][C:10](=[O:15])[CH2:11]2)(=[O:4])[CH3:3]
COC1=CCC2C(CCC2OC(C)=O)C1
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
25
0.08
Concentrated hydrochloric acid (3.5 ml) was added to a solution of 7-acetoxy-3-methoxybicyclo[4,3,0]non-3-ene (58.9 g; prepared as described in Reference Example 3) in methanol (500 ml), and the mixture was stirred at the ambient temperature for 5 minutes. It was then concentrated under reduced pressure, to give 7-acetoxybicyclo[4,3,0]nonan-3-one (54.7 g).
CC(=O)OC1CCC2CC(=O)CCC21
null
99.5
null
1,254,228
ord_dataset-c544c0c663f54dbea4ddb52ddde7934e
null
2013-01-01T00:01:00
true
[CH3:1][C:2]1[C:7]([N+:8]([O-])=O)=[CH:6][CH:5]=[C:4]([C:11]([S:14]([CH3:17])(=[O:16])=[O:15])([CH3:13])[CH3:12])[N:3]=1>C(O)(=O)C.[Zn]>[CH3:1][C:2]1[C:7]([NH2:8])=[CH:6][CH:5]=[C:4]([C:11]([S:14]([CH3:17])(=[O:16])=[O:15])([CH3:13])[CH3:12])[N:3]=1
Cc1nc(C(C)(C)S(C)(=O)=O)ccc1[N+](=O)[O-]
null
null
[Zn]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(=O)O
null
null
null
null
null
null
null
null
null
null
25
1
To a solution of 2-methyl-6-(2-(methylsulfonyl)propan-2-yl)-3-nitropyridine (1.27 g, 4.92 mmol) in 50 mL acetic acid, zinc dust (1.6 g, 24.5 mmol) was added in small portions under ice-cooling. After 1 h, more zinc dust (ca. 2 g, 31 mmol) was added in small portions and mixture was stirred at room temperature for another hour. Solids were filtered off, washed with CH3CN, and filtrate was concentrated. Residue was purified by CC(CH2Cl2/MeOH 20:1+1% NEt3). Fractions containing product were concentrated and re-purified by HPLC. Fractions containing product were partly concentrated and residue was extracted with 1M NaHCO3 and CH2Cl2. Organic phases were dried over MgSO4, filtered and concentrated to give 2-methyl-6-(2-(methylsulfonyl)propan-2-yl)pyridin-3-amine (0.664 g, 59% yield) as a white solid. 1HNMR (CDCl3, 400 MHz) δ 1.84 (s, 6H), 2.39 (s, 3H), 2.76 (s, 3H), 3.68 (s, 2H), 6.92-6.94 (d, J=8.3 Hz, 1H), 7.29-7.31 (d, J=8.3 Hz, 1H). Exact mass calculated for C10H16N2O2S 228.09 found 229.2 (MH+).
Cc1nc(C(C)(C)S(C)(=O)=O)ccc1N
null
59.1
null
609,719
ord_dataset-73916d628db147c89020b3baac642d48
null
2003-01-01T00:09:00
true
C([O:5][C@@H:6]1[C@@H:10]([O:11]C(=O)CC)[C@@H:9]([C@@H:16]([CH2:22][O:23]C(=O)CC)[O:17]C(=O)CC)[O:8][C@H:7]1[N:28]1[CH:35]=[CH:34][C:32](=[O:33])[NH:31][C:29]1=[O:30])(=O)CC>CO.N>[C@@H:7]1([N:28]2[CH:35]=[CH:34][C:32](=[O:33])[NH:31][C:29]2=[O:30])[O:8][C@H:9]([C@@H:16]([CH2:22][OH:23])[OH:17])[C@H:10]([OH:11])[C@H:6]1[OH:5]
CCC(=O)OC[C@@H](OC(=O)CC)[C@H]1O[C@@H](n2ccc(=O)[nH]c2=O)[C@H](OC(=O)CC)[C@H]1OC(=O)CC
null
null
N
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
null
8
1-(2,3,5,6-Tetra-O-propanoyl-β-D-glucofuranosyl)uracil was dissolved in methanol saturated with ammonia (15 mL) and left at room temperature overnight. After concentrating in vacuo, the resulting residue was purified by flash silica chromatography, eluting with CHCl3/CH3OH/NH3 aq. (84:15:1), to give 1-βD-glucofuranosyluracil as a colourless solid (680 mg, 75%). A sample was recrystallised from EtOH to give the product as colourless needles, mp 175-176.5° C. (from EtOH), [α]D21=+9.91 (c 1.1 in H2O), (Found: C, 44.0; H, 5.0; N, 10.35. C10H14N2O7 requires C, 43.8; H, 5.15; N, 10.2%); δH (D2O) 7.82 (1H, d, J 8.1, 6-H), 5.79 (1H, d, J 8.1, 5-H), 5.75 (1H, s, 1′-H), 4.27-4.25 (2H, m, 2′- and 3′-H), 4.23 (1H, dd, J 8.6 and 2.7, 4′-H), 4.12 (1H, ddd, J 8.6, 5.4 and 2.7, 5′-H), 3.86 (1H, dd, J 12.1 and 2.7, 6′a-H), 3.37 (1H, dd, J 12.1 and 5.4, 6′b-H); δC (D2O) 166.8 (3-C), 151.9 (2-C), 142.6 (6-C), 101.5 (5-C), 92.4 (1′-C), 82.8 (4′-C), 80.7, 74.7 (2′- and 3′-C), 68.9 (5′-C), 63.8 (6′-C); m/z (FAB) 275.088448 (MH+, C10H15N2O7 requires 275.087926).
O=c1ccn([C@@H]2O[C@H]([C@H](O)CO)[C@H](O)[C@H]2O)c(=O)[nH]1
null
75
null
366,594
ord_dataset-b18df02d6e9345faa0f2dae281a0870a
null
1997-01-01T00:06:00
true
[C:1]([C:3]1[CH:4]=[CH:5][C:6]2[O:10][C:9]([C:11]([NH:13][C:14]3[CH:28]=[CH:27][C:17]([O:18][CH2:19][C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])=[CH:16][CH:15]=3)=[O:12])=[CH:8][C:7]=2[CH:29]=1)#[N:2].[SH2:30]>N1C=CC=CC=1.C(N(CC)CC)C>[C:1]([C:3]1[CH:4]=[CH:5][C:6]2[O:10][C:9]([C:11]([NH:13][C:14]3[CH:28]=[CH:27][C:17]([O:18][CH2:19][C:20]([O:22][C:23]([CH3:24])([CH3:25])[CH3:26])=[O:21])=[CH:16][CH:15]=3)=[O:12])=[CH:8][C:7]=2[CH:29]=1)(=[S:30])[NH2:2]
S
CC(C)(C)OC(=O)COc1ccc(NC(=O)c2cc3cc(C#N)ccc3o2)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
c1ccncc1
CCN(CC)CC
null
null
null
null
null
null
null
null
null
null
18
t-Butyl 4-[(5-cyano-2-benzofuranyl)carbonylamino]phenoxyacetate (430 mg, 1.10 mmol) was dissolved in a mixed solution of pyridine (30 ml) and triethylamine (7 ml), and hydrogen sulfide gas was blown in for 10 minutes at room temperature, which was followed by stirring for 18 hours. Low boiling matters were distilled away from the reaction mixture under reduced pressure and the residue was dissolved in ethyl acetate. The mixture was washed with a 2N aqueous potassium hydrogensulfate solution, water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration, low boiling matters were distilled away from the filtrate under reduced pressure to give t-butyl 4-[(5-thiocarbamoyl-2-benzofuranyl)carbonylamino]phenoxyacetate as a yellow solid. The solid was dissolved in acetone (50 ml) and methyl iodide (2 ml) was added. The mixture was refluxed under heating for 40 minutes. Low boiling matters were distilled away from the reaction mixture under reduced pressure to give t-butyl 4-[[5-[(1-methylthio)iminomethyl]-2-benzofuranyl)carbonylamino]phenoxyacetate as a yellow solid. Thereto were added methanol (30 ml) and ammonium acetate (280 mg, 3.64 mmol), and the mixture was refluxed under heating for 3 hours. Low boiling matters were distilled away from the reaction mixture under reduced pressure and the residue was purified by silica gel column chromatography (chloroform/methanol=100/3-3/1) to give 596 mg of hydriodide of compound (8) as a yellow solid (quantitatively in 3 steps).
CC(C)(C)OC(=O)COc1ccc(NC(=O)c2cc3cc(C(N)=S)ccc3o2)cc1
null
null
null
1,389,915
ord_dataset-31641fb65b34430fa7435229b949b604
null
2014-01-01T00:01:00
true
[F:1][C:2]1[CH:38]=[CH:37][C:5]([CH2:6][O:7][C:8]2[CH:13]=[CH:12][N:11]([C:14]3[CH:15]=[CH:16][C:17]4[C:18]5[CH2:28][CH2:27][N:26](C(OC(C)(C)C)=O)[CH2:25][CH2:24][C:19]=5[N:20]([CH3:23])[C:21]=4[CH:22]=3)[C:10](=[O:36])[CH:9]=2)=[CH:4][CH:3]=1.[ClH:39]>ClCCl>[ClH:39].[F:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:6][O:7][C:8]2[CH:13]=[CH:12][N:11]([C:14]3[CH:15]=[CH:16][C:17]4[C:18]5[CH2:28][CH2:27][NH:26][CH2:25][CH2:24][C:19]=5[N:20]([CH3:23])[C:21]=4[CH:22]=3)[C:10](=[O:36])[CH:9]=2)=[CH:37][CH:38]=1
Cn1c2c(c3ccc(-n4ccc(OCc5ccc(F)cc5)cc4=O)cc31)CCN(C(=O)OC(C)(C)C)CC2
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
25
8
To a solution of tert-butyl 8-(4-(4-fluorobenzyloxy)-2-oxopyridin-1(2H)-yl)-6-methyl-1,2,4,5-tetrahydroazepino[4,5-b]indole-3(6H)-carboxylate (120 mg, 0.23 mmol) in dichloromethane (1.0 mL) was added HCl (2M in diethyl ether, 5.0 mL). The resulting slurry was stirred at room temperature overnight and concentrated under reduced pressure to afford the title compound (85 mg, 82%) as a yellow solid: 1H NMR (500 MHz, CD3OD) δ 7.59 (d, J=8.5 Hz, 2H), 7.50 (dd, J=8.0, 5.5 Hz, 2H), 7.40 (s, 1H), 7.15 (t, J=8.5 Hz, 2H), 7.01 (d, J=8.5 Hz, 1H), 6.30 (t, J=6.5 Hz, 1H), 6.14 (br s, 1H), 5.16 (s, 2H), 3.74 (s, 3H), 3.54 (t, J=5.5 Hz, 2H), 3.48 (t, J=5.5 Hz, 2H), 3.34 (t, J=5.5 Hz, 2H), 3.24 (t, J=5.5 Hz, 2H); ESI MS m/z 418 [M+H]+.
Cn1c2c(c3ccc(-n4ccc(OCc5ccc(F)cc5)cc4=O)cc31)CCNCC2
null
82
null
488,537
ord_dataset-37b0416f244344a08cf357e851eedf2a
null
2001-01-01T00:01:00
true
[CH:1]1([CH:4]([O:6][CH2:7][C:8]([OH:10])=[O:9])[CH3:5])[CH2:3][CH2:2]1.O[C:12]([CH3:27])([CH2:25][CH3:26])[C:13]([C:15]1[CH:20]=[CH:19][C:18]([S:21]([CH3:24])(=[O:23])=[O:22])=[CH:17][CH:16]=1)=[O:14]>>[CH3:27][C@@:12]([O:9][C:8](=[O:10])[CH2:7][O:6][CH:4]([CH:1]1[CH2:3][CH2:2]1)[CH3:5])([CH2:25][CH3:26])[C:13]([C:15]1[CH:20]=[CH:19][C:18]([S:21]([CH3:24])(=[O:23])=[O:22])=[CH:17][CH:16]=1)=[O:14]
CCC(C)(O)C(=O)c1ccc(S(C)(=O)=O)cc1
CC(OCC(=O)O)C1CC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared as described in Example 134 Step 2 using (1-cyclopropylethoxy)acetic acid and 2(R) 2-hydroxy-2-methyl-1-(4-(methylsulfonyl)phenyl)butan-1-one from Example 117, Step 3.
CC[C@@](C)(OC(=O)COC(C)C1CC1)C(=O)c1ccc(S(C)(=O)=O)cc1
null
null
null
443,485
ord_dataset-ba7561dae3884c07a8beddd0b9f1222e
null
1999-01-01T00:10:00
true
[CH:1]([C:3]1[CH:17]=[CH:16][CH:15]=[CH:14][C:4]=1[CH:5]([C:8]1[S:12][CH2:11][N:10]([CH3:13])[CH:9]=1)[O:6][CH3:7])=O.[F:18][C:19]([F:31])([F:30])[C:20]1[CH:25]=[CH:24][C:23]([C:26](=[N:28][NH2:29])[CH3:27])=[CH:22][CH:21]=1>CO>[CH3:7][O:6][CH:5]([C:8]1[S:12][CH2:11][N:10]([CH3:13])[CH:9]=1)[C:4]1[CH:14]=[CH:15][CH:16]=[CH:17][C:3]=1[CH:1]=[N:29][N:28]=[C:26]([C:23]1[CH:24]=[CH:25][C:20]([C:19]([F:18])([F:31])[F:30])=[CH:21][CH:22]=1)[CH3:27]
COC(C1=CN(C)CS1)c1ccccc1C=O
CC(=NN)c1ccc(C(F)(F)F)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
25
3
To 0.23 g (1 mmol) of 5-(2-formyl-α-methoxybenzyl)-3-methylthiazole in 2 ml of methanol was added 0.22 g (1.1 mmol) of 4'-(trifluoromethyl)acetophenone hydrazone and stirred at room temperature for 3 hours. After completion of the reaction, methanol was concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (ethyl acetate/n-hexane) to give 5-[α-methoxy-2-{4-(4-trifluoromethylphenyl)-2,3-diaza-1,3-pentadienyl}benzyl]-3-methylthiazole (0.23 g, 55.4%) as oil.
COC(C1=CN(C)CS1)c1ccccc1C=NN=C(C)c1ccc(C(F)(F)F)cc1
null
53.1
null
791,544
ord_dataset-744b04e8228742eb9aa4bde36f5dedf1
null
2007-01-01T00:10:00
true
[OH:1][C@@H:2]([CH2:6][CH:7]([CH3:9])[CH3:8])[C:3]([OH:5])=[O:4].[H-].[Na+].I[CH2:13][CH2:14][CH2:15][CH2:16][CH3:17].O>CN(C=O)C>[CH3:8][CH:7]([CH3:9])[CH2:6][C@H:2]([O:1][CH2:3][CH2:2][CH2:6][CH2:7][CH3:8])[C:3]([O:5][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])=[O:4]
CC(C)C[C@H](O)C(=O)O
CCCCCI
null
[H-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
0.33
To a solution of (2S)-2-hydroxy-4-methylpentanoic acid 8 (1 g, 7.6 mmol) in 50 mL DMF at 0° C. was added NaH (0.6 g, 15.2 mmol) and stirred for 20 min, followed by the addition of iodopentane (1.5 g, 7.6 mmol). The reaction mixture was stirred at rt for additional 16 h. The solution was poured into water and the layers separated. The aqueous layer was extracted with methylene chloride and the combined extracts were washed with sat'd NaHCO3, dried over magnesium sulfate, and concentrated to a crude product. Upon further purification, compound 9 was obtained as an oil (80 mg, 4%). MS [M+H]+ 273. Step 2: Preparation of (2S)-4-methyl-2-pentyloxypentanoic acid 10. To a solution of (2S)-pentyl 4-methyl-2-pentyloxypentanoate 9 (80 mg, 0.3 mmol) in 20 mL of THF cooled to 0° C. was added dropwise a solution of lithium hydroxide monohydrate (25 mg, 0.6 mmol) in 5 mL of water. The reaction mixture was stirred at rt for 16 h. THF was removed under reduced pressure to give an yellow oil which was diluted with 10 mL of 1 N HCl. The aqueous phase was extracted with CH2Cl2 (8×15 mL), and the extracts were combined, dried over Na2SO4, and concentrated to afford compound 10 (45 mg, 74%). MS [M+H]+ 203. Step 3: Preparation of (7S)-[(2S)-1-oxo-2-pentyloxy-(4-methylpentyl)]amino-5-methyl-5H,7H-dibenzo[b,d]azepin-6-one, 12. To a solution of (2S)-4-methyl-2-pentyloxypentanoic acid 10 (45 mg, 0.22 mmol) in CH2Cl2/DMF (5:1, 15 mL) at 0° C. was added HOBT (40 mg, 0.26 mmol) and EDC (50 mg, 0.26 mmol). The mixture was stirred for 10 min then the amine 11 (52 mg, 0.22 mmol) was added and stirring was continued for 1 h. The solution was poured into water and the layers separated. The aqueous layer was extracted with methylene chloride and the combined extracts were washed with water, 1 N HCl, sat'd NaHCO3, dried over magnesium sulfate, and concentrated to a glassy solid compound 12 (80 mg, 86%). MS [M+H]+ 423.
CCCCCOC(=O)[C@H](CC(C)C)OCCCCC
null
null
null
786,187
ord_dataset-4ad5db8537994579bef51f16dd8bf0bd
null
2007-01-01T00:08:00
true
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:9]2[O:10][C:11]([CH3:30])=[C:12]([CH2:14][O:15][C@@H:16]3[CH2:21][CH2:20][CH2:19][C@H:18]([CH2:22][CH:23]=[CH:24][C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH2:17]3)[N:13]=2)[CH:6]=[CH:7][CH:8]=1>CO.[Pd]>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:9]2[O:10][C:11]([CH3:30])=[C:12]([CH2:14][O:15][C@@H:16]3[CH2:21][CH2:20][CH2:19][C@H:18]([CH2:22][CH2:23][CH2:24][C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH2:17]3)[N:13]=2)[CH:6]=[CH:7][CH:8]=1
CCOC(=O)C=CC[C@H]1CCC[C@@H](OCc2nc(-c3cccc(OC)c3)oc2C)C1
null
null
[Pd]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
25
7
190 mg of ethyl 4-{cis-3-[2-(3-methoxyphenyl)-5-methyloxazol-4-yl-methoxy]cyclohexyl}but-2-enoate are dissolved in 25 ml of methanol, and 20 mg of Pd (10% on activated carbon) are added. The mixture is stirred at room temperature and under an atmosphere of hydrogen for 7 hours. The catalyst is filtered off through Celite and the filtrate is concentrated under reduced pressure. This gives 110 mg of ethyl 4-{cis-3-[2-(3-methoxyphenyl)-5-methyloxazol-4-ylmethoxy]cyclohexyl}butyrate as an oil. C24H33NO5 (415.53), MS(ESI): 416 (M+H+).
CCOC(=O)CCC[C@H]1CCC[C@@H](OCc2nc(-c3cccc(OC)c3)oc2C)C1
null
null
null
1,254,328
ord_dataset-c544c0c663f54dbea4ddb52ddde7934e
null
2013-01-01T00:01:00
true
Cl.[CH3:2][O:3][C:4](=[O:46])[NH:5][C@H:6]([C:10]([N:12]1[CH2:16][CH2:15][CH2:14][C@H:13]1[C:17]1[NH:18][CH:19]=[C:20]([C:22]2[CH:27]=[CH:26][C:25]([C:28]3[C:29]4[S:35][CH:34]=[C:33]([C:36]5[NH:37][C:38]([C@@H:41]6[CH2:45][CH2:44][CH2:43][NH:42]6)=[N:39][CH:40]=5)[C:30]=4[S:31][CH:32]=3)=[CH:24][CH:23]=2)[N:21]=1)=[O:11])[CH:7]([CH3:9])[CH3:8].[C:47]([O:51][C:52]([NH:54][C@H:55]([C:66]1[CH:71]=[CH:70][CH:69]=[CH:68][CH:67]=1)[C:56](N1CCC[C@H]1C(O)=O)=[O:57])=[O:53])(C)(C)C.CN(C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F.CCN(CC)CC>CN(C)C=O>[CH3:2][O:3][C:4](=[O:46])[NH:5][C@H:6]([C:10]([N:12]1[CH2:16][CH2:15][CH2:14][C@H:13]1[C:17]1[NH:18][CH:19]=[C:20]([C:22]2[CH:27]=[CH:26][C:25]([C:28]3[C:29]4[S:35][CH:34]=[C:33]([C:36]5[NH:37][C:38]([C@@H:41]6[CH2:45][CH2:44][CH2:43][N:42]6[C:56](=[O:57])[C@H:55]([NH:54][C:52]([O:51][CH3:47])=[O:53])[C:66]6[CH:71]=[CH:70][CH:69]=[CH:68][CH:67]=6)=[N:39][CH:40]=5)[C:30]=4[S:31][CH:32]=3)=[CH:24][CH:23]=2)[N:21]=1)=[O:11])[CH:7]([CH3:9])[CH3:8]
COC(=O)N[C@H](C(=O)N1CCC[C@H]1c1nc(-c2ccc(-c3csc4c(-c5cnc([C@@H]6CCCN6)[nH]5)csc34)cc2)c[nH]1)C(C)C
CC(C)(C)OC(=O)N[C@@H](C(=O)N1CCC[C@H]1C(=O)O)c1ccccc1
null
CN(C)C(On1nnc2cccnc21)=[N+](C)C
Cl
F[P-](F)(F)(F)(F)F
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
CCN(CC)CC
null
null
null
null
null
null
null
null
null
25
12
To a mixture of compound 71 (0.078 mmol), compound 33 (0.085 mmol), and HATU (0.085 mmol) in dimethylformamide (1 mL) was added Et3N (0.465 mmol) dropwise. The reaction mixture was stirred at room temperature during 12 hrs. The solvent was removed under reduced pressure and the residue was dissolved in methanol. This mixture was eluted through a SCX-2 column. The filtrate was concentrated and the residue was purified by semi-preparative HPLC to give compound A200 as a white solid in 25% yield. 1H NMR (DMSO-d6, 400 MHz) δ (ppm) 0.85 (d, J=6.46 Hz, 3H), 0.91 (d, J=6.64 Hz, 3H), 1.84-2.20 (m, 8H), 3.11-3.22 (m, 1H), 3.35-3.38 (m, 1H), 3.51-3.54 (m, 6H), 3.77-3.92 (m, 2H), 4.04-4.09 (m, 1H), 5.06-5.11 (m, 2H), 5.48-5.52 (m, 1H), 6.88-8.40 (m, 13H), 11.80-11.87 (m, 1H); MS (ESI, EI+) m/z=835.4 (MH+).
COC(=O)N[C@H](C(=O)N1CCC[C@H]1c1nc(-c2ccc(-c3csc4c(-c5cnc([C@@H]6CCCN6C(=O)[C@H](NC(=O)OC)c6ccccc6)[nH]5)csc34)cc2)c[nH]1)C(C)C
null
25
null
1,750,491
ord_dataset-60a3e71da3174666a50a61dcfa611a9f
null
2016-01-01T00:07:00
true
[C:1]([BH3-])#N.[Na+].Cl.[S:6]1[C:14]2[CH2:13][CH2:12][NH:11][CH2:10][C:9]=2[CH:8]=[CH:7]1.C=O>ClCCl>[CH3:1][N:11]1[CH2:12][CH2:13][C:14]2[S:6][CH:7]=[CH:8][C:9]=2[CH2:10]1
[BH3-]C#N
c1cc2c(s1)CCNC2
null
C=O
Cl
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
25
16
Sodium cyanoborohydride (10 g, 160 mmol) was slowly added to a mixture of 4,5,6,7-tetrahydrothieno[3,2-c]pyridine hydrochloride (7.0 g, 40.0 mmol) and formaldehyde (35% in water, 10 mL) in dichloromethane (100 mL) at room temperature. The resulting mixture was stirred at room temperature for 16 h. Work-up: the reaction mixture was partitioned between ethyl acetate (300 mL) and water (200 mL). The organic layer was separated, washed with brine (100 mL), dried over Na2SO4, and concentrated in vacuo. The residue was purified by column chromatography on silica gel (EtOAc/petroleum ether=1:5˜1:1) to afford the title compound as a white solids (2.0 g, 33%). 1H NMR (DMSO-d6, 400 MHz): δ 7.26 (d, 1H), 6.77 (d, 1H), 3.37 (s, 2H), 2.80-2.77 (m, 2H), 2.64-2.60 (m, 2H), 2.34 (s, 3H).
CN1CCc2sccc2C1
null
32.6
null
898,627
ord_dataset-de6bce51790e4004a27e1a8f2bcc7ded
null
2009-01-01T00:08:00
true
[CH3:1][C:2]1[S:3][C:4]2[C:10](=[O:11])[CH:9]([CH:12]=O)[CH2:8][CH2:7][C:5]=2[N:6]=1.[NH:14]1[CH2:19][CH2:18][O:17][CH2:16][CH2:15]1>C1(C)C=CC=CC=1>[CH3:1][C:2]1[S:3][C:4]2[C:10](=[O:11])[C:9](=[CH:12][N:14]3[CH2:19][CH2:18][O:17][CH2:16][CH2:15]3)[CH2:8][CH2:7][C:5]=2[N:6]=1
C1COCCN1
Cc1nc2c(s1)C(=O)C(C=O)CC2
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
To a solution of 2-methyl-7-oxo-4,5,6,7-tetrahydro-benzothiazole-6-carbaldehyde (2.0 g, 10.2 mmol) in dry toluene (8.1 mL), morpholine (1.0 mL, 1.0 g, 11.3 mmol) was added. The reaction mixture was heated under reflux for 2 h. On cooling a brown precipitate formed. The solvent was removed under vacuum and the brown solid residue was fractionated by flash column chromatography (20% EtOAc:hexane) to leave a yellow solid that was purified further by crystallisation from EtOH to afford the pure title product as yellow crystals (2.4 g, 87%): mp 186-187° C. Anal. RP-HPLC: tR 12.7 min (0-60% MeCN, purity 100%). 1H-NMR (CDCl3): δ 7.50 (s, 1H, CH), 3.80 (t, 4H, J 4.6), 3.55 (t, 4H, J 4.6), 3.00 (m, 4H, CH2—CH2), 2.80 (s, 3H, CH3). 13C-NMR (CDCl3): δ 182.0, 171.6, 162.3, 147.9, 133.2, 103.3, 67.0, 51.4, 26.7, 24.9, 20.2. MS (ESI+): m/z 287.05 (M+Na)+, 265.07 (M+H)+. Anal. (C13H16N2O2S)C, H, N.
Cc1nc2c(s1)C(=O)C(=CN1CCOCC1)CC2
null
89
null
166,352
ord_dataset-5c25f386f4664070a72d578feacedf86
null
1987-01-01T00:12:00
true
[C:1]1([CH3:11])[CH:6]=[CH:5][C:4]([S:7]([O-:10])(=[O:9])=[O:8])=[CH:3][CH:2]=1.[F:12][C:13]([F:27])([F:26])[C:14]1[CH:15]=[CH:16][C:17]2[S:21][C:20]([CH3:22])=[N+:19]([CH2:23][CH3:24])[C:18]=2[CH:25]=1.CC(C)=O.[C:32]([O:35][CH2:36][CH3:37])(=O)[CH3:33]>>[C:1]1([CH3:11])[CH:2]=[CH:3][C:4]([S:7]([O-:10])(=[O:8])=[O:9])=[CH:5][CH:6]=1.[F:27][C:13]([F:12])([F:26])[C:14]1[CH:15]=[CH:16][C:17]2[S:21][C:20]([CH:22]=[C:36]3[CH:37]=[C:5]([CH3:4])[C:6]4[C:32](=[CH:33][CH:3]=[CH:2][CH:1]=4)[O:35]3)=[N+:19]([CH2:23][CH3:24])[C:18]=2[CH:25]=1
CCOC(C)=O
CC[n+]1c(C)sc2ccc(C(F)(F)F)cc21
null
Cc1ccc(S(=O)(=O)[O-])cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(C)=O
null
null
null
null
null
null
null
null
null
null
150
0.67
2.37 g of 5-trifluoromethyl-3-ethyl-2-methylbenzothiazolium p-toluenesulfonate and 1.0 g of 4-methylcoumarin-2-thione were reacted under heat at 150° C. for 20 hours, and then 10 ml of metrhanol, 10 ml of acetone, and 20 ml of ethyl acetate were added to the reaction mixture in the order listed to obtain a uniform solution. After cooling to room temperature, crystals precipitated out therefrom. The crystals formed were separated by filtration and washed with a small amount of acetone, and thereafter the crystlas were placed in a mixed solvent comprising 10 ml of methanol, 10 ml of acetone, and 20 ml of ethyl acetate at room temperature, and stirred for 40 minutes. Then, the crystals were again taken out by filtration and washed with acetone, at last to obtain 1.47 g of the desired p-toluenesulfonate product. Yield: 46%. Appearance: brown crystal. M.P.: 272°-273° C. (decomposition).
CC[n+]1c(C=C2C=C(C)c3ccccc3O2)sc2ccc(C(F)(F)F)cc21
null
46
null
171,891
ord_dataset-7860c6f563014da8948ede63b7110bde
null
1988-01-01T00:05:00
true
Cl.[NH2:2][C:3]1[S:4][CH:5]=[C:6]([CH2:8][Cl:9])[N:7]=1.N1C=CC=CC=1.[CH3:16][C:17]([CH3:23])([CH3:22])[CH2:18][C:19](Cl)=[O:20]>CN(C)C=O>[CH3:16][C:17]([CH3:23])([CH3:22])[CH2:18][C:19]([NH:2][C:3]1[S:4][CH:5]=[C:6]([CH2:8][Cl:9])[N:7]=1)=[O:20]
CC(C)(C)CC(=O)Cl
Nc1nc(CCl)cs1
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
c1ccncc1
CN(C)C=O
null
null
null
null
null
null
null
null
null
0
null
To a mixture of 2-amino-4-chloromethylthiazole hydrochloride (5 g), anhydrous pyridine (5 ml) and anhydrous N,N-dimethylformamide (25 ml) was slowly added 3,3-dimethylbutyryl chloride (4.4 g) with stirring at 0° to 3° C. After an hour of stirring, the reaction mixture was poured into ice water. The resulting precipitate was collected, washed with water and dried to give 2-(3,3-dimethylbutyrylamino)-4-chloromethylthiazole (6.62 g).
CC(C)(C)CC(=O)Nc1nc(CCl)cs1
null
99.3
null
820,366
ord_dataset-ec58fad8331a42c5a67ad75aac6713b4
null
2008-01-01T00:05:00
true
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH2:23][OH:24])[CH:6]=[CH:7][C:8]=1[O:9][CH2:10][C:11]1[N:12]=[C:13]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[S:14][C:15]=1[CH3:16].O[C:26]1[C:30]([CH:31]=[O:32])=[CH:29][N:28]([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[N:27]=1.C(P(CCCC)CCCC)CCC.N(C(N1CCCCC1)=O)=NC(N1CCCCC1)=O>O1CCCC1>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:6]=[CH:7][C:8]=1[O:9][CH2:10][C:11]1[N:12]=[C:13]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[S:14][C:15]=1[CH3:16])[CH2:23][O:24][C:26]1[C:30]([CH:31]=[O:32])=[CH:29][N:28]([C:33]2[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=2)[N:27]=1
COc1cc(CO)ccc1OCc1nc(-c2ccccc2)sc1C
O=Cc1cn(-c2ccccc2)nc1O
null
CCCCP(CCCC)CCCC
O=C(N=NC(=O)N1CCCCC1)N1CCCCC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
15
To a mixture of {3-methoxy-4-[(5-methyl-2-phenyl-1,3-thiazol-4-yl)methoxy]phenyl}methanol (0.95 g), 3-hydroxy-1-phenyl-1H-pyrazole-4-carbaldehyde (0.58 g), tributylphosphine (0.85 g) and tetrahydrofuran (100 mL) was added 1,1′-(azodicarbonyl)dipiperidine (1.06 g) at room temperature, and the mixture was stirred for 15 hrs. The precipitated crystals were removed by filtration and the filtrate was concentrated. The residue was subjected to silica gel column chromatography to give 3-({3-methoxy-4-[(5-methyl-2-phenyl-1,3-thiazol-4-yl)methoxy]benzyl}oxy)-1-phenyl-1H-pyrazole-4-carbaldehyde as colorless crystals (0.83 g, yield 58%) from a fraction eluted with ethyl acetate-hexane (2:1, v/v). Recrystallization from ethyl acetate-hexane gave colorless prism crystals. melting point: 164-165° C.
COc1cc(COc2nn(-c3ccccc3)cc2C=O)ccc1OCc1nc(-c2ccccc2)sc1C
null
58.3
null
605,235
ord_dataset-273fda773e864aaf9b71a30a2d9f2162
null
2003-01-01T00:08:00
true
[CH2:1]([NH:5][C:6]([C:8]1[N:9]([CH2:27][CH2:28][CH2:29][C:30]#[N:31])[C:10]2[C:15]([CH:16]=1)=[CH:14][C:13]([O:17][CH2:18][C:19]1[C:24]([Cl:25])=[CH:23][CH:22]=[CH:21][C:20]=1[Cl:26])=[CH:12][CH:11]=2)=[O:7])[CH:2]([CH3:4])[CH3:3].[N:32]([Si](C)(C)C)=[N+:33]=[N-:34].C([Sn](=O)CCCC)CCC>C1(C)C=CC=CC=1>[CH2:1]([NH:5][C:6]([C:8]1[N:9]([CH2:27][CH2:28][CH2:29][C:30]2[NH:34][N:33]=[N:32][N:31]=2)[C:10]2[C:15]([CH:16]=1)=[CH:14][C:13]([O:17][CH2:18][C:19]1[C:24]([Cl:25])=[CH:23][CH:22]=[CH:21][C:20]=1[Cl:26])=[CH:12][CH:11]=2)=[O:7])[CH:2]([CH3:4])[CH3:3]
C[Si](C)(C)N=[N+]=[N-]
CC(C)CNC(=O)c1cc2cc(OCc3c(Cl)cccc3Cl)ccc2n1CCCC#N
null
CCCC[Sn](=O)CCCC
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
To a solution of 1-(3-cyanopropyl)-5-(2,6-dichlorobenzyloxy)-1H-indole-2-carboxylic acid isobutyl amide (0.076 g, 0.17 mmol) in toluene (10 mL) was added azidotrimethylsilane (0.066 mL, 0.50 mmol) and dibutyltin oxide (0.012 g, 0.050 mmol). The reaction mixture was heated to reflux and stirred under argon at reflux temperature for 40 h. The solution was then cooled and the toluene removed under reduced pressure. Methanol was added and removed under reduced pressure. Ethyl acetate was added and the reaction mixture was washed with water and brine. The organic layer was dried over MgSO4, filtered, and the solvent removed under reduced pressure. Purification by flash chromatography (silica gel, 10% methanol/dichloromethane) yielded a white solid (0.032 g, 38%). MS(ES) m/e 501.2 [M +H]+.
CC(C)CNC(=O)c1cc2cc(OCc3c(Cl)cccc3Cl)ccc2n1CCCc1nnn[nH]1
null
37.5
null
1,247,454
ord_dataset-c544c0c663f54dbea4ddb52ddde7934e
null
2013-01-01T00:01:00
true
[CH3:1][O:2][C:3]1[C:8]([CH2:9][CH2:10][O:11][C:12]2[CH:20]=[CH:19][CH:18]=[C:17]3[C:13]=2[CH:14]=[C:15]([C:21]([OH:23])=O)[NH:16]3)=[CH:7][CH:6]=[CH:5][N:4]=1.[NH2:24][CH:25]1[CH2:30][CH2:29][C:28]([CH2:32][CH2:33][N:34]2[CH2:39][CH2:38][C@H:37]([OH:40])[C@@H:36]([CH3:41])[CH2:35]2)([OH:31])[CH2:27][CH2:26]1>>[OH:31][C:28]1([CH2:32][CH2:33][N:34]2[CH2:39][CH2:38][C@H:37]([OH:40])[C@@H:36]([CH3:41])[CH2:35]2)[CH2:29][CH2:30][CH:25]([NH:24][C:21]([C:15]2[NH:16][C:17]3[C:13]([CH:14]=2)=[C:12]([O:11][CH2:10][CH2:9][C:8]2[C:3]([O:2][CH3:1])=[N:4][CH:5]=[CH:6][CH:7]=2)[CH:20]=[CH:19][CH:18]=3)=[O:23])[CH2:26][CH2:27]1
C[C@H]1CN(CCC2(O)CCC(N)CC2)CC[C@@H]1O
COc1ncccc1CCOc1cccc2[nH]c(C(=O)O)cc12
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
This compound is synthesized analogously to example 1 from 4-[2-(2-methoxy-pyridin-3-yl)-ethoxy]-1H-indole-2-carboxylic acid 16m and amine 14.
COc1ncccc1CCOc1cccc2[nH]c(C(=O)NC3CCC(O)(CCN4CC[C@H](O)[C@@H](C)C4)CC3)cc12
null
null
null
1,676,149
ord_dataset-9cc455db05a444779921f786a45b21a6
null
2015-01-01T00:12:00
true
Cl[C:2]1[C:3]2[CH2:17][CH2:16][CH2:15][C:4]=2[N:5]=[C:6]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([Cl:14])[CH:9]=2)[N:7]=1.CN1C(=O)CCC1.[CH3:25][C:26]1[CH:34]=[CH:33][C:29]([CH2:30][Mg]Cl)=[CH:28][CH:27]=1.[Cl-]>C1COCC1>[Cl:14][C:10]1[CH:9]=[C:8]([C:6]2[N:7]=[C:2]([CH2:25][C:26]3[CH:34]=[CH:33][C:29]([CH3:30])=[CH:28][CH:27]=3)[C:3]3[CH2:17][CH2:16][CH2:15][C:4]=3[N:5]=2)[CH:13]=[CH:12][CH:11]=1
Clc1cccc(-c2nc(Cl)c3c(n2)CCC3)c1
Cc1ccc(C[Mg]Cl)cc1
null
[Cl-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN1CCCC1=O
C1CCOC1
null
null
null
null
null
null
null
null
null
0
null
A 25-mL round bottom flask, with stirrer bar, was charged with 4-chloro-2-(3-chlorophenyl)-6,7-dihydro-5H-cyclopenta[d]pyrimidine (318 mg, 1.20 mol, 1.0 eq.) and Fe(acac)3 (6.6 mg, 19 mol, 0.05 eq.), NMP (0.4 mL) and THF (4.0 mL). The mixture was cooled to 0° C. under nitrogen. A solution of 4-methylbenzylmagnesium chloride (0.83 mL, 0.5M in THF, 0.41 mmol, 1.1 eq.) was added dropwise over 2 minutes. The resulting mixture was stirred 0° C. for 1.5 hr until the starting chloride was consumed. The reaction was quenched with a 9:1 sat. NH4Cl/conc. NH4OH solution (10 mL) then diluted with ethyl acetate (75 mL). The organic layer was washed with sat. sodium chloride (3×5 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue (175 mg) was purified by chromatography on silica gel using dichloromethane as the eluent, to afford 2-(3-chlorophenyl)-4-(4-methylbenzyl)-6,7-dihydro-5H-cyclopenta[d]pyrimidine (65 mg, 52% yield) as a white solid. MW=334.84. 1H NMR (DMSO-d6, 500 MHz) δ 8.35-8.30 (m, 2H), 7.58-7.51 (m, 2H), 7.20 (d, J=8.0 Hz, 2H), 7.11 (d, J=8.0 Hz, 2H), 4.07 (s, 2H), 2.97 (t, J=7.5 Hz, 2H), 2.88 (t, J=7.5 Hz, 2H), 2.25 (s, 3H), 2.06 (quintet, J=7.5 Hz, 2H).
Cc1ccc(Cc2nc(-c3cccc(Cl)c3)nc3c2CCC3)cc1
null
47.3
null
1,096,106
ord_dataset-af85e6f81c2d49f08086afd6d9e6959c
null
2011-01-01T00:10:00
true
[CH2:1]([O:8][C:9]([NH:11][CH2:12][CH2:13][CH2:14][C@@H:15]([C:29]([NH:31][C@H:32]1[CH2:36][CH2:35][CH2:34][C@H:33]1[C:37]([O:39]C(C)(C)C)=[O:38])=[O:30])[NH:16][C:17]([C:19]1[N:20]([CH3:28])[C:21]2[C:26]([CH:27]=1)=[CH:25][CH:24]=[CH:23][CH:22]=2)=[O:18])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl.C(OCC)(=O)C>C(Cl)(Cl)Cl>[CH2:1]([O:8][C:9]([NH:11][CH2:12][CH2:13][CH2:14][C@@H:15]([C:29]([NH:31][C@H:32]1[CH2:36][CH2:35][CH2:34][C@H:33]1[C:37]([OH:39])=[O:38])=[O:30])[NH:16][C:17]([C:19]1[N:20]([CH3:28])[C:21]2[C:26]([CH:27]=1)=[CH:25][CH:24]=[CH:23][CH:22]=2)=[O:18])=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
Cn1c(C(=O)N[C@@H](CCCNC(=O)OCc2ccccc2)C(=O)N[C@H]2CCC[C@H]2C(=O)OC(C)(C)C)cc2ccccc21
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)Cl
CCOC(C)=O
null
null
null
null
null
null
null
null
null
25
3
To a mixture of tert-butyl (1R,2S)-2-({N5-[(benzyloxy)carbonyl]-N2-[(1-methyl-1H-indol-2-yl)carbonyl]-L-ornithyl}amino)cyclopentanecarboxylate (0.40 g) and chloroform (10 ml) was added a 4 M hydrogen chloride/ethyl acetate solution (20 ml) under ice-cooling, followed by stirring at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure, and to the residue were added ethyl acetate and water. The aqueous layer was separated, and the organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The organic layer was concentrated under reduced pressure, and diethyl ether was added to the residue for solidification, followed by washing with diethyl ether and a 50% aqueous methanol solution. Further, it was purified by silica gel column chromatography (0→2% MeOH/chloroform), and the obtained solid was washed with a 50% aqueous methanol solution to obtain (1R,2S)-2-({N5-[(benzyloxy)carbonyl]-N2-[(1-methyl-1H-indol-2-yl)carbonyl]-L-ornithyl}amino)cyclopentanecarboxylic acid (0.25 g).
Cn1c(C(=O)N[C@@H](CCCNC(=O)OCc2ccccc2)C(=O)N[C@H]2CCC[C@H]2C(=O)O)cc2ccccc21
null
69.1
null
589,827
ord_dataset-7a74d48eeefd45aba53e7258f3ae067a
null
2003-01-01T00:04:00
true
C(OC(=O)[NH:7][C:8]1[CH:13]=[C:12]([N:14]([CH3:16])[CH3:15])[C:11]([Cl:17])=[CH:10][C:9]=1[NH:18][C:19](=[O:38])[CH2:20][C:21]([C:23]1[CH:28]=[CH:27][CH:26]=[C:25]([N:29]2[C:33]([CH2:34][N:35]([CH3:37])[CH3:36])=[CH:32][N:31]=[N:30]2)[CH:24]=1)=O)(C)(C)C.C(O)(C(F)(F)F)=O>C(Cl)Cl>[Cl:17][C:11]1[C:12]([N:14]([CH3:16])[CH3:15])=[CH:13][C:8]2[N:7]=[C:21]([C:23]3[CH:28]=[CH:27][CH:26]=[C:25]([N:29]4[C:33]([CH2:34][N:35]([CH3:37])[CH3:36])=[CH:32][N:31]=[N:30]4)[CH:24]=3)[CH2:20][C:19](=[O:38])[NH:18][C:9]=2[CH:10]=1
CN(C)Cc1cnnn1-c1cccc(C(=O)CC(=O)Nc2cc(Cl)c(N(C)C)cc2NC(=O)OC(C)(C)C)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O=C(O)C(F)(F)F
ClCCl
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared from (4-chloro-5-dimethylamino-2-{3-[3-(5-dimethylaminomethyl-[1,2,3]triazol-1-yl)-phenyl]-3-oxo-propionylamino}-phenyl)-carbamic acid tert.-butyl ester (Example M19) by treatment with TFA in CH2Cl2 according to the general procedure N. Obtained as a beige solid (34 mg).
CN(C)Cc1cnnn1-c1cccc(C2=Nc3cc(N(C)C)c(Cl)cc3NC(=O)C2)c1
null
null
null
1,532,321
ord_dataset-8d5c200bca27407ab9febe7598e16458
null
2015-01-01T00:01:00
true
[NH2:1][CH:2]([C:6]1[CH:11]=[CH:10][C:9]([F:12])=[CH:8][CH:7]=1)[C:3]([OH:5])=[O:4].Cl[C:14](Cl)([O:16]C(=O)OC(Cl)(Cl)Cl)Cl>C1COCC1>[F:12][C:9]1[CH:10]=[CH:11][C:6]([CH:2]2[C:3](=[O:5])[O:4][C:14](=[O:16])[NH:1]2)=[CH:7][CH:8]=1
NC(C(=O)O)c1ccc(F)cc1
O=C(OC(Cl)(Cl)Cl)OC(Cl)(Cl)Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
-20
3
To a solution of 2-amino-2-(4-fluorophenyl)acetic acid (5 g, 29.5 mmol) in THF (50 mL) at 50° C. was added triphosgene (8.77 g, 29.5 mmol), then heating was continued for 3 h. The reaction mixture was then filtered and evaporated to a volume of about 10 mL, followed by addition of 150 mL of hexanes. The mixture was heated slightly, and then cooled to −20° C. for 1 h. The crude slurry was filtered to give 4-(4-fluorophenyl)oxazolidine-2,5-dione (5.03 g, 87%) which was used without further purification.
O=C1NC(c2ccc(F)cc2)C(=O)O1
null
87.4
null
1,138,682
ord_dataset-68715347640045adb1b09e6a04722b0e
null
2012-01-01T00:03:00
true
[OH-].[Na+].Br[CH2:4][C@H:5]([C:7]1[CH:12]=[CH:11][C:10]([Br:13])=[CH:9][CH:8]=1)[OH:6]>C(OCC)C>[Br:13][C:10]1[CH:11]=[CH:12][C:7]([C@H:5]2[CH2:4][O:6]2)=[CH:8][CH:9]=1
O[C@H](CBr)c1ccc(Br)cc1
null
null
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOCC
null
null
null
null
null
null
null
null
null
null
25
5
Aqueous sodium hydroxide (1M, 400 ml) was added to 2-bromo-(1S)-1-(4-bromophenyl)ethanol (77.0 g) in diethyl ether (400 ml) and stirred at room temperature for 5 hours. The organic layer was separated and aqueous layer was extracted with ether. The combined organic layer was washed with brine and dried over anhydrous sodium sulfate. Removal of the solvent yielded (2S)-2-(4-bromophenyl) oxirane (55.0 g) as a pale brown oil.
Brc1ccc([C@H]2CO2)cc1
null
100.5
null
496,423
ord_dataset-9df8b3ec9c8742b3802e0efaac6f6ef3
null
2001-01-01T00:03:00
true
C[O:2][C:3](=O)[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][S:15][CH2:16][CH2:17][S:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][C:30](O)=[O:31].[H-].[Al+3].[Li+].[H-].[H-].[H-].[H][H]>C1COCC1>[CH2:17]([S:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][OH:31])[CH2:16][S:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][OH:2]
[H][H]
COC(=O)CCCCCCCCCCCSCCSCCCCCCCCCCCC(=O)O
null
[Al+3]
[H-]
[Li+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
30
4
Ethylenedithio-bislauryl alcohol was prepared as the final intermediate as ethylenedithio-bislauric acid methyl ester (8 g) was dissolved in dry THF at 0° C. (ice bath). Lithium aluminum hydride (1.16 g) was added to the flask slowly. Hydrogen was generated, and the reaction temperature was gradually raised to 30° C. After stirring for 4 hours, the reaction was quenched by pouring the solution thus formed into ice water. The aqueous solution was neutralized by adding concentrated HCl, and the crude product was then extracted with ethyl acetate three times. After evaporating the solvents, the compound (7.0 gm) was dried under vacuum and analyzed by NMR. NMR data agrees with the expected structure of the final product as set forth in the reaction summary below.
OCCCCCCCCCCCCSCCSCCCCCCCCCCCCO
null
null
null
592,948
ord_dataset-278fb6af8a994ac69e4d95e6e6eff756
null
2003-01-01T00:05:00
true
[C:1](Cl)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:10]([NH2:18])[CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1>C(Cl)Cl>[CH2:10]([NH:18][C:1](=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1
NCCc1ccccc1
O=C(Cl)c1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
25
3
To a solution of benzoyl chloride (0.123 moles) (Aldrich) in 600 mL of CH2Cl2 was added 2.0 eq. of phenethylamine (Aldrich) dropwise. The reaction mixture was stirred at room temperature for 3 hours and then poured into a separatory and extracted with CH2Cl2. The organic extracts were washed with water and 1N HCl, and then dried over Na2SO4, filtered and concentrated to give N-phenethyl benzamide.
O=C(NCCc1ccccc1)c1ccccc1
null
null
null
1,501,423
ord_dataset-366bdd9ee72d474cbe6f3f9e54dd96d2
null
2014-01-01T00:10:00
true
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([CH:9]2[CH2:14][CH2:13][N:12]([C:15]([C:17]3[C:18]([CH2:30][CH3:31])=[CH:19][C:20]([CH:27]4[CH2:29][CH2:28]4)=[C:21]([CH:26]=3)[C:22](OC)=[O:23])=[O:16])[CH2:11][CH2:10]2)=[CH:5][CH:4]=1)#[N:2].[NH2:32][NH2:33]>C(O)C>[C:1]([C:3]1[CH:8]=[CH:7][C:6]([CH:9]2[CH2:10][CH2:11][N:12]([C:15]([C:17]3[C:18]([CH2:30][CH3:31])=[CH:19][C:20]([CH:27]4[CH2:29][CH2:28]4)=[C:21]([CH:26]=3)[C:22]([NH:32][NH2:33])=[O:23])=[O:16])[CH2:13][CH2:14]2)=[CH:5][CH:4]=1)#[N:2]
NN
CCc1cc(C2CC2)c(C(=O)OC)cc1C(=O)N1CCC(c2ccc(C#N)cc2)CC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
100
15
To a round-bottom flask was added a solution of methyl 5-(4-(4-cyanophenyl)piperidine-1-carbonyl)-2-cyclopropyl-4-ethylbenzoate (compound 228.1, 830 mg, 1.99 mmol, 1.00 equiv) in ethanol (15 mL). Hydrazine (5 mL, 100 equiv) was added to the reaction. The resulting solution was stirred for 15 h at 100° C., then concentrated in vacuo. The residue was extracted with 100 mL of dichloromethane and the combined organic layers were washed with 1×30 mL of brine, dried over anhydrous sodium sulfate and concentrated in vacuo. This resulted in 0.800 g (96%) of 5-(4-(4-cyanophenyl)piperidine-1-carbonyl)-2-cyclopropyl-4-ethylbenzohydrazide as a white solid.
CCc1cc(C2CC2)c(C(=O)NN)cc1C(=O)N1CCC(c2ccc(C#N)cc2)CC1
null
null
null
768,886
ord_dataset-8214eb8444a44dc2900ccb42dbeff15e
null
2007-01-01T00:05:00
true
Br[C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[C:8]([C:11]([NH2:13])=[O:12])[CH:9]=2)[N:4]([CH:14]2[CH2:19][CH2:18][CH2:17][CH2:16][O:15]2)[N:3]=1.[S:20]1[C:24](B(O)O)=[CH:23][C:22]2[CH:28]=[CH:29][CH:30]=[CH:31][C:21]1=2.ClCCl.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>COCCOC>[S:20]1[C:24]([C:2]2[C:10]3[C:5](=[CH:6][CH:7]=[C:8]([C:11]([NH2:13])=[O:12])[CH:9]=3)[N:4]([CH:14]3[CH2:19][CH2:18][CH2:17][CH2:16][O:15]3)[N:3]=2)=[CH:23][C:22]2[CH:28]=[CH:29][CH:30]=[CH:31][C:21]1=2
OB(O)c1cc2ccccc2s1
NC(=O)c1ccc2c(c1)c(Br)nn2C1CCCCO1
null
O=P([O-])([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
COCCOC
null
null
null
null
null
null
null
null
null
null
null
A mixture of 3-bromo-1-perhydro-2H-pyran-2-yl-1H-indazole-5-carboxamide (425 mg, 1.31 mmol), benzo[b]thiophene-2-boronic acid (348 mg, 1.95 mmol, 1.49 equiv.), [1,1′-bis(diphenylphosphino)-ferrocene} dichloropalladium (II) complex with dichloromethane (107 mg, 0.131 mmol, 0.10 equiv.), potassium phosphate (K3PO4, 1.38 g, 6.50 mmol, 4.96 equiv.) and 6.5 mL of DME were refluxed for 18 h and concentrated. Purification by silica gel chromatography using 0–5% MeOH in EtOAc as eluent afforded the title compound (126 mg, 26% yield): ES-MS (m/z) 378 [M+1]+.
NC(=O)c1ccc2c(c1)c(-c1cc3ccccc3s1)nn2C1CCCCO1
null
25.5
null
1,153,990
ord_dataset-b195433d5c354ddfb6cde0d53c41910f
null
2012-01-01T00:04:00
true
[C:1]([O:5][C:6](=[O:33])[N:7]([C@@H:21]([C:23]1[C:32]2[C:27](=[CH:28][CH:29]=[CH:30][CH:31]=2)[CH:26]=[CH:25][CH:24]=1)[CH3:22])[CH2:8][CH:9]1[CH2:14][CH2:13][NH:12][CH2:11][CH:10]1[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)([CH3:4])([CH3:3])[CH3:2].Br[C:35]1[S:36][CH:37]=[C:38]([C:40]([O:42][CH3:43])=[O:41])[N:39]=1.C(=O)([O-])[O-].[K+].[K+].CS(C)=O>O>[C:1]([O:5][C:6]([N:7]([CH2:8][CH:9]1[CH2:14][CH2:13][N:12]([C:35]2[S:36][CH:37]=[C:38]([C:40]([O:42][CH3:43])=[O:41])[N:39]=2)[CH2:11][CH:10]1[C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1)[C@@H:21]([C:23]1[C:32]2[C:27](=[CH:28][CH:29]=[CH:30][CH:31]=2)[CH:26]=[CH:25][CH:24]=1)[CH3:22])=[O:33])([CH3:2])([CH3:3])[CH3:4]
C[C@H](c1cccc2ccccc12)N(CC1CCNCC1c1ccccc1)C(=O)OC(C)(C)C
COC(=O)c1csc(Br)n1
null
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CS(C)=O
null
null
null
null
null
null
null
null
null
25
8
To a mixture of 136 mg of the crude tert-butyl[(1R)-1-(1-naphthyl)ethyl][(3-phenylpiperidin-4-yl)methyl]carbamate, 64 mg of methyl 2-bromo-1,3-thiazole-4-carboxylate, and 38 mg of potassium carbonate was added 1.5 mL of DMSO at room temperature, and the mixed solution was stirred at room temperature overnight. To the reaction mixture was added water, followed by extraction with ethyl acetate, and the organic layer was then washed with water and saturated brine in this order, and then dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (hexane-ethyl acetate) to obtain 113 mg of methyl 2-[4-({(tert-butoxycarbonyl)[(1R)-1-(1-naphthyl)ethyl]amino}methyl)-3-phenylpiperidin-1-yl]-1,3-thiazole-4-carboxylate as a colorless foamy substance. ESI+: 586
COC(=O)c1csc(N2CCC(CN(C(=O)OC(C)(C)C)[C@H](C)c3cccc4ccccc34)C(c3ccccc3)C2)n1
null
66.9
null
1,064,886
ord_dataset-ffbef48837674f39816de887b5dc8bae
null
2011-01-01T00:06:00
true
[C:1]([C:5]1[CH:10]=[CH:9][C:8]([C:11]2[N:12]([C:30](Cl)=[O:31])[C@H:13]([C:23]3[CH:28]=[CH:27][C:26]([Cl:29])=[CH:25][CH:24]=3)[C@H:14]([C:16]3[CH:21]=[CH:20][C:19]([Cl:22])=[CH:18][CH:17]=3)[N:15]=2)=[C:7]([O:33][CH2:34][CH3:35])[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].Cl.[N:37]1([CH2:43][CH2:44][NH:45][C:46](=[O:48])[CH3:47])[CH2:42][CH2:41][NH:40][CH2:39][CH2:38]1>>[ClH:22].[C:1]([C:5]1[CH:10]=[CH:9][C:8]([C:11]2[N:12]([C:30]([N:40]3[CH2:41][CH2:42][N:37]([CH2:43][CH2:44][NH:45][C:46](=[O:48])[CH3:47])[CH2:38][CH2:39]3)=[O:31])[C@H:13]([C:23]3[CH:24]=[CH:25][C:26]([Cl:29])=[CH:27][CH:28]=3)[C@H:14]([C:16]3[CH:17]=[CH:18][C:19]([Cl:22])=[CH:20][CH:21]=3)[N:15]=2)=[C:7]([O:33][CH2:34][CH3:35])[CH:6]=1)([CH3:4])([CH3:2])[CH3:3]
CCOc1cc(C(C)(C)C)ccc1C1=N[C@@H](c2ccc(Cl)cc2)[C@@H](c2ccc(Cl)cc2)N1C(=O)Cl
CC(=O)NCCN1CCNCC1
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
N-(2-{4-[(4S,5R)-2-(4-tert-Butyl-2-ethoxy-phenyl)-4,5-bis-(4-chloro-phenyl)-4,5-dihydro-imidazole-1-carbonyl]-piperazin-1-yl}-ethyl)-acetamide hydrochloride was prepared from (4S,5R)-2-(4-tert-butyl-2-ethoxy-phenyl)-4,5-bis-(4-chloro-phenyl)-4,5-dihydro-imidazole-1-carbonyl chloride (example 11) and N-(2-piperazin-1-yl-ethyl)-acetamide hydrochloride (example 23) in an analogous manner as described in example 25. LR-MS: 664.5 [(M+H)+]
CCOc1cc(C(C)(C)C)ccc1C1=N[C@@H](c2ccc(Cl)cc2)[C@@H](c2ccc(Cl)cc2)N1C(=O)N1CCN(CCNC(C)=O)CC1
null
null
null
1,460,355
ord_dataset-a86112d52cd54525a5e36d41f18aced2
null
2014-01-01T00:07:00
true
[CH2:1]([O:8][CH2:9][C@@H:10]([C:12]1[NH:16][C:15]2[CH:17]=[CH:18][C:19]([O:21][C:22]3[CH:27]=[CH:26][C:25]([F:28])=[CH:24][CH:23]=3)=[CH:20][C:14]=2[N:13]=1)[NH2:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl.[NH:30]1[CH:34]=[C:33]([CH2:35][C:36](O)=[O:37])[N:32]=[CH:31]1>>[CH2:1]([O:8][CH2:9][C@H:10]([NH:11][C:36](=[O:37])[CH2:35][C:33]1[N:32]=[CH:31][NH:30][CH:34]=1)[C:12]1[NH:16][C:15]2[CH:17]=[CH:18][C:19]([O:21][C:22]3[CH:23]=[CH:24][C:25]([F:28])=[CH:26][CH:27]=3)=[CH:20][C:14]=2[N:13]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
N[C@@H](COCc1ccccc1)c1nc2cc(Oc3ccc(F)cc3)ccc2[nH]1
O=C(O)Cc1c[nH]cn1
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Proceeding as in Example 1, but substituting (R)-2-(benzyloxy)-1-(5-(4-fluorophenoxy)-1H-benzo[d]imidazol-2-yl)ethanamine and 4-imidazoleacetic acid hydrochloride gave Compound 59, (R)—N-(2-(benzyloxy)-1-(5-(4-fluorophenoxy)-1H-benzo[d]imidazol-2-yl)ethyl)-2-(1H-imidazol-4-yl)acetamide (75 mg, 39%). 1H NMR (400 MHz, DMSO-d6) δ 8.75 (d, J=8.0 Hz, 1H), 7.77 (s, 1H), 7.56 (d, J=9.2 Hz, 1H), 7.33-7.25 (m, 5H), 7.20-7.16 (m, 3H), 7.00-6.96 (m, 3H), 6.89 (dd, J=8.8, 2.0 Hz, 1H), 5.35-5.30 (m, 1H), 4.52 (s, 2H), 3.95-3.84 (m, 2H), 3.56-3.46 (m, 2H); ESI MS: m/z 486.2 (M+1).
O=C(Cc1c[nH]cn1)N[C@@H](COCc1ccccc1)c1nc2cc(Oc3ccc(F)cc3)ccc2[nH]1
null
39
null
181,213
ord_dataset-ed5a3d1f8dc744759e7fa1c320a44e59
null
1988-01-01T00:11:00
true
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1/[C:9](/[C:16]1[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=1)=[CH:10]/[CH:11]=[CH:12]/[C:13]([OH:15])=[O:14].[N+:24]([C:27]1[CH:32]=[CH:31][C:30](O)=[CH:29][CH:28]=1)([O-:26])=[O:25].C1(N=C=NC2CCCCC2)CCCCC1>ClCCl>[N+:24]([C:27]1[CH:32]=[CH:31][C:30]([O:14][C:13](=[O:15])/[CH:12]=[CH:11]/[CH:10]=[C:9](/[C:4]2[CH:5]=[CH:6][CH:7]=[CH:8][C:3]=2[O:2][CH3:1])\[C:16]2[CH:17]=[CH:18][C:19]([O:22][CH3:23])=[CH:20][CH:21]=2)=[CH:29][CH:28]=1)([O-:26])=[O:25]
O=[N+]([O-])c1ccc(O)cc1
COc1ccc(/C(=C\C=C\C(=O)O)c2ccccc2OC)cc1
null
C(=NC1CCCCC1)=NC1CCCCC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
25
2
As in Example 115, (E,E)-5-(2-methoxyphenyl)-5-(4-methoxyphenyl)-2,4-pentadienoic acid (3.4 g) and 4-nitrophenol (1.8 g) in 25 mL of dichloromethane was treated with 1,3-dicyclohexylcarbodiimide (2.27 g). The mixture was stirred at room temperature for 2 hours. After the usual work up, the ester was crystallized from 2-propanol to yield 3.0 g of (E,E)-5-(2-methoxyphenyl)-5-(4-methoxyphenyl)-2,4-pentadienoic acid 4-nitrophenyl ester, mp 149°-150° C.
COc1ccc(/C(=C\C=C\C(=O)Oc2ccc([N+](=O)[O-])cc2)c2ccccc2OC)cc1
null
63.5
null
474,044
ord_dataset-cd531114850e4f239b2a3661044ae672
null
2000-01-01T00:08:00
true
Br[CH2:2][C:3]([O:5][CH3:6])=[O:4].[Br:7][C:8]1[CH:13]=[C:12]([C:14]2[C:23]3[C:24]4[CH:30]=[CH:29][CH:28]=[CH:27][C:25]=4[O:26][C:22]=3[C:21]([Br:31])=[C:20]3[C:15]=2[CH:16]=[CH:17][CH:18]=[CH:19]3)[CH:11]=[C:10]([Br:32])[C:9]=1[OH:33].C(=O)([O-])[O-].[K+].[K+].CN(C)C=O>O>[CH3:6][O:5][C:3](=[O:4])[CH2:2][O:33][C:9]1[C:8]([Br:7])=[CH:13][C:12]([C:14]2[C:23]3[C:24]4[CH:30]=[CH:29][CH:28]=[CH:27][C:25]=4[O:26][C:22]=3[C:21]([Br:31])=[C:20]3[C:15]=2[CH:16]=[CH:17][CH:18]=[CH:19]3)=[CH:11][C:10]=1[Br:32]
Oc1c(Br)cc(-c2c3ccccc3c(Br)c3oc4ccccc4c23)cc1Br
COC(=O)CBr
null
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
21
Methyl bromoacetate (0.554 mL, 5.8 mmol) was added to a stirred, room temperature suspension of 2, 6-dibromo-4-(6-bromo-benzo[b]naphtho[2,3-d]furan-11yl)-phenol (1.6 g, 2.92 mmol), potassium carbonate (0.81 g, 5.8 mmol) and dimethylformamide (7 mL). After 21 h, the reaction mixture was added to water and filtered. The solid was taken up in THF and silica gel was added. The solvent was removed. The adsorbate was flash chromatographed (9:1 petroleum ether:ethyl acetate as eluent) to provide the title compound as a white solid (0.987 g, 55%): mp 188-189° C.: NMR (DMSO-d6); δ8.37 (d, J=8 Hz, 1 H), 7.91 (s, 2 H), 7.84 (d, J=8 Hz, 1 H), 7.80 (ddd, J=8, 7, 1 Hz, 1 H), 7.70 (d, J=8 Hz, 1 H), 7.64-7.58 (m, 2 H), 7.31 (t, J=8 Hz, 1 H), 6.92 (d, J=8, 1 H), 4.88 (s, 2 H), 3.80 (s, 3 H); MS (EI): [M+], 3 bromine isotope pattern, 616 (30%), 618 (100%) 620 (100%) 622 (30%); Anal. Calc. for C25H15Br3O4: C, 48.50, H, 2.44, N, 0.00. Found: C, 48.53, H, 2.29, N, 0.00.
COC(=O)COc1c(Br)cc(-c2c3ccccc3c(Br)c3oc4ccccc4c23)cc1Br
null
54.6
null
256,208
ord_dataset-30ad5cf6083a45a387b45bebad1a4d65
null
1992-01-01T00:10:00
true
[C:1]([C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=1[C:11]1[CH:16]=[CH:15][C:14]([CH2:17][N:18]2[C:22]([CH2:23][OH:24])=[C:21]([Cl:25])[N:20]=[C:19]2[CH2:26][CH2:27][CH2:28][CH3:29])=[CH:13][CH:12]=1)([O:3]C)=[O:2].C(O)(=[O:32])C>O.[O-2].[O-2].[O-2].[Cr+6]>[C:1]([C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=1[C:11]1[CH:12]=[CH:13][C:14]([CH2:17][N:18]2[C:22]([C:23]([OH:24])=[O:32])=[C:21]([Cl:25])[N:20]=[C:19]2[CH2:26][CH2:27][CH2:28][CH3:29])=[CH:15][CH:16]=1)([OH:3])=[O:2]
CC(=O)O
CCCCc1nc(Cl)c(CO)n1Cc1ccc(-c2ccccc2C(=O)OC)cc1
null
[Cr+6]
[O-2]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
null
null
null
null
null
null
null
null
null
null
null
0.25
To a solution of 1.03 g of 1-[(2'-carbomethoxybiphenyl-4-yl)methyl]-2-butyl-4-chloro-5-hydroxymethylimidazole in 10 mL of anhydrous acetic acid at 25° was added a solution of 0.62 g of chromium trioxide in 10 mL of water. The mixture was stirred at 25° for 15 minutes and then poured into water. The precipitated solids were recovered by filtration and then dissolved in 50 mL of 1.0N aqueous sodium hydroxide solution. The alkaline solution was allowed to stand at 25° overnight and then was acidified to pH 3 with 10% aqueous hydrochloric acid. The precipitated solid was recovered by filtration and recrystallized from ethyl acetate to afford 0.10 g of 1-[(2'-carboxybiphenyl-4-yl)methyl]-2-butyl-4-chloroimidazole-5-carboxylic acid (m.p. 186°-187° (decomp.)). NMR (DMSO-d6) δ 12.97 (br s, 2H); 7.68 (d, 1H); 7.53 (t, 1H); 7.41 (t, 1H); 7.34 (d, 1H); 7.28 (d, 2H); 7.02 (d, 2H); 5.61 (s, 2H); 2.60 (t, 2H); 1.53 (quint., 2H); 1.27 (sext., 2H); 0.81 (t, 3H).
CCCCc1nc(Cl)c(C(=O)O)n1Cc1ccc(-c2ccccc2C(=O)O)cc1
null
null
null
1,207,037
ord_dataset-fb72428f30234761b4216139dc228d0c
null
2012-01-01T00:09:00
true
[F:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH2:8][N:7]([CH2:12][CH2:13][NH2:14])[CH:6]([CH2:15][C:16]1[CH:21]=[CH:20][C:19]([F:22])=[CH:18][CH:17]=1)[CH2:5]2.[CH2:23]([C:25]1[CH:30]=[C:29]([CH2:31]OS(C)(=O)=O)[CH:28]=[CH:27][N:26]=1)[CH3:24].C(=O)([O-])[O-].[K+].[K+]>C(#N)C>[CH2:23]([C:25]1[CH:30]=[C:29]([CH2:31][NH:14][CH2:13][CH2:12][N:7]2[CH:6]([CH2:15][C:16]3[CH:17]=[CH:18][C:19]([F:22])=[CH:20][CH:21]=3)[CH2:5][C:4]3[C:9](=[CH:10][CH:11]=[C:2]([F:1])[CH:3]=3)[CH2:8]2)[CH:28]=[CH:27][N:26]=1)[CH3:24]
NCCN1Cc2ccc(F)cc2CC1Cc1ccc(F)cc1
CCc1cc(COS(C)(=O)=O)ccn1
null
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC#N
null
null
null
null
null
null
null
null
null
null
60
2
67 mg of 2-[6-fluoro-3-(4-fluorobenzyl)-3,4-dihydroisoquinolin-2(1H)-yl]ethanamine obtained in Example 180-b), 47 mg of 2-ethyl-4-[(methyl sulfonyl oxy)methyl]pyridine, and 30 mg of potassium carbonate were added to acetonitrile (2 ml), followed by stirring at 60° C. for 2 hours. After concentration, it was purified by PLC (chloroform:methanol=10:1) to obtain 26 mg (yield 28%) of a title compound as a yellow oily substance.
CCc1cc(CNCCN2Cc3ccc(F)cc3CC2Cc2ccc(F)cc2)ccn1
null
28.3
null
465,489
ord_dataset-6c36eb0f817d4144988b8963c5d58879
null
2000-01-01T00:05:00
true
[H-].[Na+].[CH:3]1([CH:6]([C:8]2[O:9][C:10]3[C:16]([O:17][CH3:18])=[CH:15][CH:14]=[CH:13][C:11]=3[CH:12]=2)[OH:7])[CH2:5][CH2:4]1.I[CH3:20]>O1CCCC1>[CH:3]1([CH:6]([O:7][CH3:20])[C:8]2[O:9][C:10]3[C:16]([O:17][CH3:18])=[CH:15][CH:14]=[CH:13][C:11]=3[CH:12]=2)[CH2:4][CH2:5]1
CI
COc1cccc2cc(C(O)C3CC3)oc12
null
[H-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
0.08
To a stirred suspension of sodium hydride (60% dispersion in mineral oil, 0.52 g) in tetrahydrofuran (60 ml) under an atmosphere of nitrogen was added slowly a solution of cyclopropyl-(7-methoxybenzofuran-2-yl)-methanol (1.88 g) in tetrahydrofuran (15 ml). After stirring for 5 minutes, iodomethane (1.6 ml) was added and the mixture concentrated in vacuo. The residue was partitioned between ethyl acetate (100 ml) and water (100 ml), the organic layer washed with water (100 ml), separated, dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by flash chromatography on silica eluting with dichloromethane afforded the title compound as a yellow gum (1.62 g).
COc1cccc2cc(C(OC)C3CC3)oc12
null
null
null
834,098
ord_dataset-ec576c604a9d47258c87c732a043ec71
null
2008-01-01T00:08:00
true
[Br:1][C:2]1[CH:3]=[C:4]2[N:10]=[C:9]([C:11]3[CH:16]=[CH:15][C:14]([N+:17]([O-])=O)=[CH:13][CH:12]=3)[NH:8][C:5]2=[N:6][CH:7]=1.CO>>[Br:1][C:2]1[CH:3]=[C:4]2[N:10]=[C:9]([C:11]3[CH:16]=[CH:15][C:14]([NH2:17])=[CH:13][CH:12]=3)[NH:8][C:5]2=[N:6][CH:7]=1
O=[N+]([O-])c1ccc(-c2nc3cc(Br)cnc3[nH]2)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
25
0.5
To a stirred solution of 6-bromo-2-(4-nitrophenyl)-3H-imidazo[4,5-b]pyridine (1.6 g, 5 mmol) in methanol (45 ml) ammonium sulfide (8.5 ml, 25 mmol, 20% solution in water) was added slowly. The mixture was stirred at room temperature for 30 minutes and then heated and refluxed for 5 h. The reaction mixture was concentrated and cooled to 0° C. The precipitate was filtered off, washed with cold methanol and dried to give the title compound.
Nc1ccc(-c2nc3cc(Br)cnc3[nH]2)cc1
null
null
null
549,710
ord_dataset-e967d076b4894c2c854795f019ed3c39
null
2002-01-01T00:06:00
true
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([CH2:7]O)[CH:2]=1.[BrH:9]>CCOC(C)=O>[BrH:9].[Br:9][CH2:7][C:3]1[CH:2]=[N:1][CH:6]=[CH:5][CH:4]=1
OCc1cccnc1
null
null
Br
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOC(C)=O
null
null
null
null
null
null
null
null
null
null
null
null
To 3-pyridylcarbinol (2 g, 18.3 mmol) was added 47-49% hydrobromic acid (2 mL, 13.7 mmol). The solution was refluxed for 3 hours. The solution was diluted with EtOAc and extracted thrice with EtOAc. The organic layer was dried over MgSO4, filtered and concentrated under reduced pressure to give a solid. The solid was recrystallized in ethanol to afford the title compound as a white solid (2.13 g, 45.8%). ES (+) MS m/e=173 (M+H).
BrCc1cccnc1
null
122.9
null
330,334
ord_dataset-2c460e2ef9934444aaf26fec1f75741f
null
1996-01-01T00:05:00
true
[Cl:1][C:2]1[C:3]([CH2:12][C:13]([CH3:15])=[CH2:14])=[C:4]([OH:11])[C:5]([N+:8]([O-:10])=[O:9])=[CH:6][CH:7]=1.C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C(C)=CC=CC=1>[Cl:1][C:2]1[C:3]2[CH2:12][C:13]([CH3:15])([CH3:14])[O:11][C:4]=2[C:5]([N+:8]([O-:10])=[O:9])=[CH:6][CH:7]=1
C=C(C)Cc1c(Cl)ccc([N+](=O)[O-])c1O
null
null
Cc1ccc(S(=O)(=O)O)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1C
null
null
null
null
null
null
null
null
null
null
null
null
A mixture of 20.0 g (0.088 mole) of 3-chloro-2-(2-methyl-2-propen-1-yl)-6-nitrophenol and 0.35 g (0.002 mole) of p-toluenesulfonic acid in 100 mL of xylene was heated at reflux for approximately 16 hours. The solvent was evaporated under reduced pressure, leaving a residue which was passed through a column of silica gel, eluting with methylene chloride. The product-containing fractions were combined, washed with an aqueous solution of sodium hydroxide, dried over anhydrous magnesium sulfate, and the solvent evaporated under reduced pressure, yielding 16.85 g of 4-chloro-2,3-dihydro-2,2-dimethyl-7-nitrobenzofuran as an oil.
CC1(C)Cc2c(Cl)ccc([N+](=O)[O-])c2O1
null
84.1
null
1,227,093
ord_dataset-cde802cdb7434a5f82a22981ccaefc4e
null
2012-01-01T00:11:00
true
C([O:3][C:4]([C:6]1[S:10][C:9]([C:11]2[CH:15]=[C:14]([CH3:16])[N:13]([CH2:17][CH2:18][C:19]3[CH:24]=[CH:23][C:22]([F:25])=[CH:21][CH:20]=3)[N:12]=2)=[N:8][C:7]=1[CH3:26])=[O:5])C.[OH-].[Na+]>O1CCCC1.O>[F:25][C:22]1[CH:23]=[CH:24][C:19]([CH2:18][CH2:17][N:13]2[C:14]([CH3:16])=[CH:15][C:11]([C:9]3[S:10][C:6]([C:4]([OH:5])=[O:3])=[C:7]([CH3:26])[N:8]=3)=[N:12]2)=[CH:20][CH:21]=1
CCOC(=O)c1sc(-c2cc(C)n(CCc3ccc(F)cc3)n2)nc1C
null
null
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
A mixture of 2-{1-[2-(4-fluoro-phenyl)-ethyl]-5-methyl-1H-pyrazol-3-yl}-4-methyl-thiazole-5-carboxylic acid ethyl ester (0.32 g, 0.86 mmol), NaOH (0.17 g, 4.29 mmol) in tetrahydrofuran (5 mL) and water (5 mL) was heated to reflux for 16 hr. The solvent was removed in vacuo and the residue was neutralized with 5% HCl to pH 5-6. The resulting solid was filtered and dried to provide 2-{1-[2-(4-fluoro-phenyl)-ethyl]-5-methyl-1H-pyrazol-3-yl}-4-methyl-thiazole-5-carboxylic acid as a white solid (0.21 g, 70% yield). This material was used without further purification.
Cc1nc(-c2cc(C)n(CCc3ccc(F)cc3)n2)sc1C(=O)O
null
70.7
null
785,964
ord_dataset-4ad5db8537994579bef51f16dd8bf0bd
null
2007-01-01T00:08:00
true
Br[C:2]1[N:3]=[C:4]([NH:11][CH2:12][C:13]2[CH:18]=[CH:17][N:16]=[CH:15][CH:14]=2)[C:5]2[N:6]([CH:8]=[CH:9][N:10]=2)[CH:7]=1.[NH2:19][C:20]1[CH:21]=[C:22](B(O)O)[CH:23]=[CH:24][CH:25]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].O1CCOCC1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[NH2:19][C:20]1[CH:25]=[C:24]([C:2]2[N:3]=[C:4]([NH:11][CH2:12][C:13]3[CH:18]=[CH:17][N:16]=[CH:15][CH:14]=3)[C:5]3[N:6]([CH:8]=[CH:9][N:10]=3)[CH:7]=2)[CH:23]=[CH:22][CH:21]=1
Nc1cccc(B(O)O)c1
Brc1cn2ccnc2c(NCc2ccncc2)n1
null
c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
O=P([O-])([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1COCCO1
O
null
null
null
null
null
null
null
null
null
25
null
A mixture of (6-Bromo-imidazo[1,2-a]pyrazin-8-yl)-pyridin-4-ylmethyl-amine 4 (1.0 equiv.), 3-aminophenyl boronic acid (1.1 equiv.), Pd (PPh3)4 (0.10 equiv.), and K3PO4 (2.20 equiv.) in 4:1 1,4-dioxane:water is heated to 90° C. for 24 hr. The mixture is cooled to RT and partitioned between EtOAc and sat. NaHCO3. The aqueous phase is extracted with EtOAc and combined extracts are dried over Na2SO4. The solvent is removed under reduced pressure and the resulting residue is purified by flash chromatography (EtOAc) to yield [6-(3-Amino-phenyl)-imidazo[1,2-a]pyrazin-8-yl]-pyridin-4-ylmethyl-amine 5.
Nc1cccc(-c2cn3ccnc3c(NCc3ccncc3)n2)c1
null
null
null
834,094
ord_dataset-ec576c604a9d47258c87c732a043ec71
null
2008-01-01T00:08:00
true
[Br:1][C:2]1[CH:3]=[C:4]2[N:10]=[C:9]([C:11]3[CH:16]=[CH:15][C:14]([O:17][CH2:18][CH:19]4[CH2:21][O:20]4)=[CH:13][CH:12]=3)[NH:8][C:5]2=[N:6][CH:7]=1.[NH:22]1[CH2:27][CH2:26][O:25][CH2:24][CH2:23]1>>[Br:1][C:2]1[CH:3]=[C:4]2[N:10]=[C:9]([C:11]3[CH:16]=[CH:15][C:14]([O:17][CH2:18][CH:19]([OH:20])[CH2:21][N:22]4[CH2:27][CH2:26][O:25][CH2:24][CH2:23]4)=[CH:13][CH:12]=3)[NH:8][C:5]2=[N:6][CH:7]=1
Brc1cnc2[nH]c(-c3ccc(OCC4CO4)cc3)nc2c1
C1COCCN1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared from 6-bromo-2-[4-(oxiran-2-ylmethoxy)phenyl]-3H-imidazo[4,5-b]pyridine and morpholine.
OC(COc1ccc(-c2nc3cc(Br)cnc3[nH]2)cc1)CN1CCOCC1
null
null
null
1,013,674
ord_dataset-f024e9664ab64906a71a2ff6004cb3d0
null
2010-01-01T00:12:00
true
[CH3:1][NH:2][C:3]1[C:8]([CH:9]=[O:10])=[CH:7][N:6]=[C:5]2[NH:11][CH:12]=[CH:13][C:4]=12.C([O-])([O-])=O.[Na+].[Na+].[CH2:20](Br)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>CN(C=O)C>[CH2:20]([N:6]1[CH:7]=[C:8]([CH:9]=[O:10])[C:3]([NH:2][CH3:1])=[C:4]2[CH:13]=[CH:12][N:11]=[C:5]12)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1
BrCc1ccccc1
CNc1c(C=O)cnc2[nH]ccc12
null
O=C([O-])[O-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
25
12
To solution of 4-methylamino-1H-pyrrolo[2,3-b]pyridine-5-carbaldehyde (0.5 g, 2.86 mmol) in DMF is added Na2CO3 (900 mg, 8.6 mmol) and benzyl bromide (0.5 ml, 4.3 mmol). The reaction is stirred at room temperature for 12 hours. The reaction mixture is partitioned in 100 ml water and 100 ml ethyl acetate, extracted with ethyl acetate three times. The organic phase is combined and washed with brine, dried over Na2SO4. The crude product is purified by silica gel flash chromatography, eluted with 5% methanol in ethyl acetate to give the title compound as yellow solid. 1H NMR 400 MHz (DMSO-d6) δ 9.70 (s, 1H), 9.20 (q, 1H, J=5.2 Hz), 8.59 (s, 1H), 7.46 (m, 2H), 7.35 (m, 3H), 7.28 (d, 1H, J=2.8 Hz), 7.22 (d, 1H, J=2.4 Hz), 5.65 (s, 2H), 3.31 (d, 2H, J=2.4 Hz). MS m/z 266.2 (M+1).
CNc1c(C=O)cn(Cc2ccccc2)c2nccc1-2
null
null
null
538,093
ord_dataset-1884c7bf3d544afdb8d17b5d41b90a27
null
2002-01-01T00:03:00
true
O1CCCCC1[O:7][C@@H:8]1[CH2:12][C@H:11]([O:13]C2CCCCO2)[C@H:10]([CH2:20]/[CH:21]=[CH:22]\[CH2:23][CH2:24][C:25](=[O:31])[CH2:26][O:27][C:28](=[O:30])[CH3:29])[C@H:9]1/[CH:32]=[CH:33]/[C@@H:34]([O:40]C1CCCCO1)[CH2:35][CH2:36][CH2:37][CH2:38][CH3:39]>CO>[OH:7][C@@H:8]1[CH2:12][C@H:11]([OH:13])[C@H:10]([CH2:20]/[CH:21]=[CH:22]\[CH2:23][CH2:24][C:25](=[O:31])[CH2:26][O:27][C:28](=[O:30])[CH3:29])[C@H:9]1/[CH:32]=[CH:33]/[C@@H:34]([OH:40])[CH2:35][CH2:36][CH2:37][CH2:38][CH3:39]
CCCCC[C@@H](/C=C/[C@@H]1[C@@H](C/C=C\CCC(=O)COC(C)=O)[C@@H](OC2CCCCO2)C[C@H]1OC1CCCCO1)OC1CCCCO1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
25
null
A solution of the acetate of Example 25 (36 mg, 0.055 mmol) and PPTs (2 mg) in MeOH (1.0 mL) was stirred at 45° C. for 4 h. The reaction was cooled to room temperature and the solvent was removed in vacuo. The residue was diluted with EtOAc and washed with 1N HCl, saturated aqueous NaHCO3 and brine. The organic portion was dried (MgSO4), filtered and concentrated in vacuo. FCC (silica gel, 50%-100% EtOAc/hex) afforded 18 mg of the named compound.
CCCCC[C@H](O)/C=C/[C@@H]1[C@@H](C/C=C\CCC(=O)COC(C)=O)[C@@H](O)C[C@H]1O
null
82.5
null
559,014
ord_dataset-f483e698250b4da0a84f425c7bfa965a
null
2002-01-01T00:08:00
true
[C:1]([C:9]1[CH:10]=[C:11]([O:16][CH2:17][C@@H:18]2[CH2:21][CH2:20][N:19]2C(OC(C)(C)C)=O)[CH:12]=[N:13][C:14]=1[Cl:15])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(O)(C(F)(F)F)=O>C(Cl)Cl>[C:1]([C:9]1[CH:10]=[C:11]([O:16][CH2:17][C@@H:18]2[CH2:21][CH2:20][NH:19]2)[CH:12]=[N:13][C:14]=1[Cl:15])(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
CC(C)(C)OC(=O)N1CC[C@H]1COc1cnc(Cl)c(C(=O)c2ccccc2)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O=C(O)C(F)(F)F
ClCCl
null
null
null
null
null
null
null
null
null
0
0.75
5-benzoyl-6-chloro-3-(1-BOC-2-(S)-azetidinylmethoxy)pyridine from step 107a is dissolved in CH2Cl2 (10 mL). The mixture is cooled to 0° C., TFA (10 mL) is added and the reaction is stirred for 45 minutes as it warms to room temperature. The mixture is concentrated in vacuo and taken up in a minimum amount of H2O. The aqueous mixture is basified with 15% NaOH and extracted with CH2Cl2 (200 mL), which is dried (MgSO4) and concentrated. The residue is chromatographed (silica gel) to afford the free amine. The isolated free amine is taken up in a minimum amount of Et2O, cooled to 0° C., and treated with HCl in EtOH to afford the hydrochloride salt.
O=C(c1ccccc1)c1cc(OC[C@@H]2CCN2)cnc1Cl
null
null
null
175,229
ord_dataset-4937da99a6a247eb90fa70f0d2eac3db
null
1988-01-01T00:07:00
true
C([NH:3][C@H:4]([C:9]([NH:11][C@H:12]([C:20]([OH:22])=[O:21])[CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)=[O:10])[CH2:5][C:6](=[O:8])[OH:7])=O.Cl.O.[CH3:25]O>>[CH3:25][O:22][C:20](=[O:21])[C@H:12]([CH2:13][C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1)[NH:11][C:9](=[O:10])[C@H:4]([CH2:5][C:6](=[O:8])[OH:7])[NH2:3]
O=CN[C@@H](CC(=O)O)C(=O)N[C@@H](Cc1ccccc1)C(=O)O
CO
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
null
null
null
null
null
null
null
null
null
null
null
null
deformylating formyl-α-L-aspartyl-L-phenylalanine in the presence of hydrogen chloride, methanol and water. Then, adding methanol and hydrogen chloride directly to the resulting solution to obtain the chloride salt of α-L-aspartyl-L-phenylalanine methyl ester.
COC(=O)[C@H](Cc1ccccc1)NC(=O)[C@@H](N)CC(=O)O
null
null
null
767,601
ord_dataset-7a8649d55889427e85b208ae89475895
null
2007-01-01T00:04:00
true
[CH3:1][N:2]([CH3:52])[CH2:3][C:4]([NH:6][C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([C:13]2[C:21]3[C:16](=[CH:17][CH:18]=[C:19]([C:22]4[N:26]=[CH:25][N:24](C(C5C=CC=CC=5)(C5C=CC=CC=5)C5C=CC=CC=5)[N:23]=4)[CH:20]=3)[N:15](C3CCCCO3)[N:14]=2)[CH:8]=1)=[O:5]>Cl.O1CCOCC1>[NH:24]1[CH:25]=[N:26][C:22]([C:19]2[CH:20]=[C:21]3[C:16](=[CH:17][CH:18]=2)[NH:15][N:14]=[C:13]3[C:9]2[CH:8]=[C:7]([NH:6][C:4](=[O:5])[CH2:3][N:2]([CH3:1])[CH3:52])[CH:12]=[CH:11][CH:10]=2)=[N:23]1
CN(C)CC(=O)Nc1cccc(-c2nn(C3CCCCO3)c3ccc(-c4ncn(C(c5ccccc5)(c5ccccc5)c5ccccc5)n4)cc23)c1
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1COCCO1
null
null
null
null
null
null
null
null
null
null
25
3
2-(Dimethylamino)-N-(3-{1-perhydro-2H-pyran-2-yl-5-[1-(triphenylmethyl)(1,2,4-triazol-3-yl)](1H-indazol-3-yl)}phenyl)acetamide was dissolved in 4 mL of 4.0 N HCl in 1,4-dioxane and the reaction was stirred at room temperature for 3 hours. After neutralization with aqueous NaHCO3, the reaction mixture was evaporated to dryness and purified by preparatory HPLC. (0.023 g, 13% yield over 2 steps): 1H NMR (CD3OD) δ 8.7 (d, 1H), 8.32 (br s, 1H), 8.17 (t, 1H), 8.05 (dd, 1H), 7.7 (t, 2H), 7.6 (dd, 1H), 7.4 (t, 1H), 3.18 (s, 2H), 2.38 (s, 6H); ES-MS (m/z) 362 [M+H]+.
CN(C)CC(=O)Nc1cccc(-c2n[nH]c3ccc(-c4nc[nH]n4)cc23)c1
null
13
null
1,285,664
ord_dataset-d5c54236ecd94d61aaa071461bcfc426
null
2013-01-01T00:04:00
true
[C:1]([O:5][C:6]([N:8]1[CH2:12][CH:11]([CH2:13][OH:14])[CH:10]2[O:15][CH2:16][C:17]([O:20][CH3:21])([O:18][CH3:19])[CH:9]12)=[O:7])([CH3:4])([CH3:3])[CH3:2].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>C(Cl)Cl>[C:1]([O:5][C:6]([N:8]1[CH2:12][CH:11]([CH:13]=[O:14])[CH:10]2[O:15][CH2:16][C:17]([O:20][CH3:21])([O:18][CH3:19])[CH:9]12)=[O:7])([CH3:4])([CH3:3])[CH3:2]
COC1(OC)COC2C(CO)CN(C(=O)OC(C)(C)C)C21
null
null
CC(=O)OI1(OC(C)=O)(OC(C)=O)OC(=O)c2ccccc21
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
null
0.67
To a solution of the alcohol 1g (370 mg, 1.22 mmol) dissolved in dry DCM (10 mL) was added Dess Martin periodinane (673 mg, 1.59 mmol). The reaction was stirred for 40 minutes and then quenched by addition of 10 mL of 10% Na2S2O3: NaHCO3(sat) 1:1. The solution was diluted with DCM (50 mL) and extracted with a 1:1 mixture of 10% Na2S2O3: NaHCO3(sat) (50 mL). The organic phase was dried with Na2SO4, filtered and evaporated. The crude product was purified by flash chromatography (heptane: ethyl acetate (2:1) which gave the title compound (290 mg, 79%).
COC1(OC)COC2C(C=O)CN(C(=O)OC(C)(C)C)C21
null
78.9
null
1,063,735
ord_dataset-ffbef48837674f39816de887b5dc8bae
null
2011-01-01T00:06:00
true
[Cl:1][C:2]1[CH:10]=[CH:9][C:8]([Cl:11])=[CH:7][C:3]=1[C:4]([OH:6])=O.[CH:12]1([CH2:15][CH2:16][NH:17][C:18]([C:20]2[N:21]=[N:22][C:23]([N:26]3[CH2:31][CH2:30][NH:29][CH2:28][CH2:27]3)=[CH:24][CH:25]=2)=[O:19])[CH2:14][CH2:13]1>>[CH:12]1([CH2:15][CH2:16][NH:17][C:18]([C:20]2[N:21]=[N:22][C:23]([N:26]3[CH2:31][CH2:30][N:29]([C:4](=[O:6])[C:3]4[CH:7]=[C:8]([Cl:11])[CH:9]=[CH:10][C:2]=4[Cl:1])[CH2:28][CH2:27]3)=[CH:24][CH:25]=2)=[O:19])[CH2:14][CH2:13]1
O=C(NCCC1CC1)c1ccc(N2CCNCC2)nn1
O=C(O)c1cc(Cl)ccc1Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Following the procedure of Example 9, making variations only as required to use 2,5-dichlorobenzoic acid in place of 2,5-dichlorobenzoic acid to react with 6-piperazin-1-yl-pyridazine-3-carboxylic acid (2-cyclopropylethyl)amide, the title compound was obtained as a white solid (56% yield). 1H NMR (300 MHz, CDCl3) δ 8.05, 7.96, 7.38-7.30, 6.97, 4.12-3.23, 1.50, 0.80-0.67, 0.51-0.38, 0.16-0.06. MS (ES+) m/z 448.2 (M+1).
O=C(NCCC1CC1)c1ccc(N2CCN(C(=O)c3cc(Cl)ccc3Cl)CC2)nn1
null
null
null
1,749,467
ord_dataset-60a3e71da3174666a50a61dcfa611a9f
null
2016-01-01T00:07:00
true
[S:1]([N:11]1[CH:15]=[CH:14][C:13]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])=[CH:12]1)([C:4]1[CH:10]=[CH:9][C:7]([CH3:8])=[CH:6][CH:5]=1)(=[O:3])=[O:2].[CH:23](=[N:25]/[S@:26]([C:28]([CH3:31])([CH3:30])[CH3:29])=[O:27])\[CH3:24]>C1COCC1>[CH3:29][C:28]([CH3:31])([S@@:26]([NH:25][C@@H:23]([C:12]1[N:11]([S:1]([C:4]2[CH:5]=[CH:6][C:7]([CH3:8])=[CH:9][CH:10]=2)(=[O:2])=[O:3])[CH:15]=[CH:14][C:13]=1[C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH3:24])=[O:27])[CH3:30]
C/C=N/[S@@](=O)C(C)(C)C
Cc1ccc(S(=O)(=O)n2ccc(C(=O)OC(C)(C)C)c2)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
0.75
To a solution of tert-butyl 1-tosyl-1H-pyrrole-3-carboxylate (,287a 1.67 g, 5.20 mmol) in 40 mL of THF at −78° C. was added LDA(Aldrich) (1.7 M solution in heptane/THF/ethylbenzene, 3.67 mL, 6.24 mmol) slowly dropwise. After 45 min, a solution of (S,E)-N-ethylidene-2-methylpropane-2-sulfinamide (Prepared according to PCT Int. Appl., WO2005103020; 0.765 g, 5.20 mmol) in THF was added slowly dropwise via syringe over several min. After 15 min, the acetone/dry ice bath was removed and the reaction was quenched by dropwise addition of saturated aq. NH4Cl and Et2O. The organic layer was washed with saturated aq. NH4Cl once, saturated aq. NaCl once and the organics were dried over anhydrous MgSO4, filtered, and concentrated in vacuo. The material was treated with DCM and purified by silica gel chromatography (80 g ISCO redisep gold column) using 0-50% EtOAc/hexanes. The product-containing fractions were concentrated to afford tert-butyl 2-((R)-1-((S)-1,1-dimethylethylsulfinamido)ethyl)-1-tosyl-1H-pyrrole-3-carboxylate (287b; 1.05 g, 2.24 mmol, 43% yield) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 7.73 (2H, d, J=8.2 Hz), 7.28-7.34 (3H, m), 6.58 (1H, d, J=3.3 Hz), 5.95 (1H, d, J=9.2 Hz), 5.14 (1H, br. s.), 2.43 (3H, s), 1.50-1.54 (12H, m), 0.96 (9H, s). m/z (ESI, +ve) 469.1 (MA-1)11.
Cc1ccc(S(=O)(=O)n2ccc(C(=O)OC(C)(C)C)c2[C@@H](C)N[S@@](=O)C(C)(C)C)cc1
null
43.1
null
1,070,270
ord_dataset-5df93261afc143c3ae919a57ff4fc1d4
null
2011-01-01T00:07:00
true
[CH2:1]([O:8][C:9]1[CH:18]=[CH:17][CH:16]=[C:15]2[C:10]=1[CH:11]=[C:12]([C:19]([O:21]CC)=[O:20])[CH:13]=[N:14]2)C1C=CC=CC=1.[Li+].[OH-]>C1COCC1.O>[CH3:1][O:8][C:9]1[CH:18]=[CH:17][CH:16]=[C:15]2[C:10]=1[CH:11]=[C:12]([C:19]([OH:21])=[O:20])[CH:13]=[N:14]2
CCOC(=O)c1cnc2cccc(OCc3ccccc3)c2c1
null
null
[Li+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
O
null
null
null
null
null
null
null
null
null
null
null
A solution of ethyl 5-methoxyquinoline-3-carboxylate (2.31 g, 10 mmol) prepared in stage B of example 2 and LiOH (0.4 g, 20 mmol) in THF (20 mL) and water (0.5 mL) was refluxed for 2 hours. After cooling, the solvents were evaporated under vacuum. The solid residue was used in the next step without further purification.
COc1cccc2ncc(C(=O)O)cc12
null
null
null
880,191
ord_dataset-3592bd645cd143ee8274cd0d834ae581
null
2009-01-01T00:05:00
true
[CH3:1][C:2]1([OH:8])[CH2:7][CH2:6][NH:5][CH2:4][CH2:3]1.Br[CH2:10][CH2:11][Cl:12]>>[Cl:12][CH2:11][CH2:10][N:5]1[CH2:6][CH2:7][C:2]([CH3:1])([OH:8])[CH2:3][CH2:4]1
ClCCBr
CC1(O)CCNCC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
4-methylpiperidin-4-ol (made via literature methods) and 1-bromo-2-chloroethane are reacted using the procedure for Example OO to afford 1-(2-chloroethyl)-4-methylpiperidin-4-ol.
CC1(O)CCN(CCCl)CC1
null
null
null
1,676,691
ord_dataset-9cc455db05a444779921f786a45b21a6
null
2015-01-01T00:12:00
true
[NH2:1][C:2]1([C:6]2[CH:11]=[CH:10][C:9]([C:12]3[C:13]([C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)=[CH:14][C:15]4[N:20]([CH2:21][CH2:22][C:23]#N)[C:19](=[O:25])[CH2:18][O:17][C:16]=4[N:26]=3)=[CH:8][CH:7]=2)[CH2:5][CH2:4][CH2:3]1.[C:33](OC(=O)NC1(C2C=CC(C3C(C4C=CC=CC=4)=CC4N(CCC)C(=O)COC=4N=3)=CC=2)CCC1)(C)(C)C>>[NH2:1][C:2]1([C:6]2[CH:7]=[CH:8][C:9]([C:12]3[C:13]([C:27]4[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=4)=[CH:14][C:15]4[N:20]([CH2:21][CH:22]([CH3:33])[CH3:23])[C:19](=[O:25])[CH2:18][O:17][C:16]=4[N:26]=3)=[CH:10][CH:11]=2)[CH2:5][CH2:4][CH2:3]1
CCCN1C(=O)COc2nc(-c3ccc(C4(NC(=O)OC(C)(C)C)CCC4)cc3)c(-c3ccccc3)cc21
N#CCCN1C(=O)COc2nc(-c3ccc(C4(N)CCC4)cc3)c(-c3ccccc3)cc21
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Following the procedure for 3-(6-(4-(1-aminocyclobutyl)phenyl)-2-oxo-7-phenyl-2,3-dihydro-1H-pyrido[2,3-b][1,4]oxazin-1-yl)propanenitrile, tert-butyl(1-(4-(2-oxo-7-phenyl-1-propyl-2,3-dihydro-1H-pyrido[2,3-b][1,4]oxazin-6-yl)phenyl)cyclobutyl)carbamate (50 mg, 0.078 mmol) was reacted to afford the title compound (34.5 mg). 1H NMR (500 MHz, CH3OD) 7.57 (1H, s), 7.38-7.42 (4H, m), 7.30-32 (3H, m), 7.21-7.2 (2H, m), 4.97 (2H, s), 3.92 (2H, d), 2.73-2.79 (2H, m), 2.54-2.60 (2H, m), 2.22-2.25 (1H, m), 2.13-2.16 (1H, m), 1.95-1.99 (1H, m), 1.0 (6H, d). LCMS (method D) RT: 0.93, M+H+=428.2.
CC(C)CN1C(=O)COc2nc(-c3ccc(C4(N)CCC4)cc3)c(-c3ccccc3)cc21
null
null
null
1,225,380
ord_dataset-cde802cdb7434a5f82a22981ccaefc4e
null
2012-01-01T00:11:00
true
C(=O)([O-])[O-].[K+].[K+].[NH2:7][CH:8]1[CH2:13][C:12]([CH3:15])([CH3:14])[N:11]([CH3:16])[C:10]([CH3:18])([CH3:17])[CH2:9]1.[C:19]([C:21]1[N:26]=[CH:25][C:24]([C:27]2[C:39]3[C:38]4[C:33](=[CH:34][CH:35]=[CH:36][CH:37]=4)[N:32]([C:40]4[CH:52]=[CH:51][C:43]([C:44]([O:46][C:47]([CH3:50])([CH3:49])[CH3:48])=[O:45])=[C:42](F)[CH:41]=4)[C:31]=3[CH:30]=[CH:29][CH:28]=2)=[CH:23][CH:22]=1)#[N:20]>CS(C)=O.O>[C:19]([C:21]1[N:26]=[CH:25][C:24]([C:27]2[C:39]3[C:38]4[C:33](=[CH:34][CH:35]=[CH:36][CH:37]=4)[N:32]([C:40]4[CH:41]=[CH:42][C:43]([C:44]([O:46][C:47]([CH3:48])([CH3:49])[CH3:50])=[O:45])=[C:51]([NH:7][CH:8]5[CH2:9][C:10]([CH3:18])([CH3:17])[N:11]([CH3:16])[C:12]([CH3:14])([CH3:15])[CH2:13]5)[CH:52]=4)[C:31]=3[CH:30]=[CH:29][CH:28]=2)=[CH:23][CH:22]=1)#[N:20]
CN1C(C)(C)CC(N)CC1(C)C
CC(C)(C)OC(=O)c1ccc(-n2c3ccccc3c3c(-c4ccc(C#N)nc4)cccc32)cc1F
null
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CS(C)=O
null
null
null
null
null
null
null
null
null
90
null
0.95 g of potassium carbonate and 7.8 ml of 4-amino-1,2,2,6,6-pentamethylpiperidine are successively added to a solution of 1.06 g of 2-methylpropan-2-yl 4-[4-(6-cyanopyridin-3-yl)-9H-carbazol-9-yl]-2-fluorobenzoate, obtained in stage 1 of Example 49, in 8 ml of dimethyl sulphoxide. The reaction mixture is heated at 90° C. for 2 hours and 15 minutes in a microwave, and then diluted with distilled water. The aqueous phase is extracted twice with ethyl acetate and the combined organic phases are washed with water and a saturated solution of sodium chloride and dried over magnesium sulphate. The residue is purified by silica gel chromatography, elution being carried out with a mixture of dichloromethane and methanol (97/3 by volume), so as to give 0.8 g of 2-methylpropan-2-yl 4-[4-(6-cyanopyridin-3-yl)-9H-carbazol-9-yl]-2-[(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]benzoate in the form of a yellow oil, the characteristics of which are the following:
CN1C(C)(C)CC(Nc2cc(-n3c4ccccc4c4c(-c5ccc(C#N)nc5)cccc43)ccc2C(=O)OC(C)(C)C)CC1(C)C
null
null
null
1,655,460
ord_dataset-42cd9bc5aae3485f9a58f1527bd3abf0
null
2015-01-01T00:11:00
true
[C:1]12([C:11]3[CH:16]=[CH:15][C:14]([CH2:17][OH:18])=[CH:13][C:12]=3[O:19][CH:20]([CH3:22])[CH3:21])[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2>O1CCOCC1.O=[Mn]=O>[C:1]12([C:11]3[CH:16]=[CH:15][C:14]([CH:17]=[O:18])=[CH:13][C:12]=3[O:19][CH:20]([CH3:22])[CH3:21])[CH2:8][CH:7]3[CH2:9][CH:3]([CH2:4][CH:5]([CH2:6]3)[CH2:10]1)[CH2:2]2
CC(C)Oc1cc(CO)ccc1C12CC3CC(CC(C3)C1)C2
null
null
O=[Mn]=O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1COCCO1
null
null
null
null
null
null
null
null
null
null
null
6
A mixture of the product of Step B (0.7 g) and MnO2 (1.5 g) in dioxane (20 ml) was stirred for 6 h at reflux. The mixture was filtered through Celite pad and the filtrate was evaporated to dryness to give the title compound (0.51 g, 73.4%) as creamy solid. 1H-NMR (CDCl3) 1.4 (d, 6H, J=6 Hz); 1.76 (s, 6H); 2.07 (s, 3H); 2.11 (s, 6H); 4.7-4.78 (m, 1H); 7.32-7.42 (m, 3H); 9.91 (s, 1H).
CC(C)Oc1cc(C=O)ccc1C12CC3CC(CC(C3)C1)C2
null
73.3
null
587,551
ord_dataset-7a74d48eeefd45aba53e7258f3ae067a
null
2003-01-01T00:04:00
true
[Br:1][C:2]1[C:7](=[O:8])[NH:6][C:5]2[N:9]([C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)[N:10]=[CH:11][C:4]=2[CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].Cl.Cl[CH2:26][C:27]1[N:28]([CH3:32])[N:29]=[CH:30][N:31]=1>CN(C=O)C>[Br:1][C:2]1[CH:3]=[C:4]2[CH:11]=[N:10][N:9]([C:12]3[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=3)[C:5]2=[N:6][C:7]=1[O:8][CH2:26][C:27]1[N:28]([CH3:32])[N:29]=[CH:30][N:31]=1
O=c1[nH]c2c(cnn2-c2ccccc2)cc1Br
Cn1ncnc1CCl
null
Cl
O=C([O-])[O-]
[Cs+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
60
null
To a solution of 5-bromo-1,7-dihydro-1-phenylpyrazolo[3,4-b]pyridin-6-one (0.29 g, 1.0 mmol) in DMF (4 ml) under nitrogen was added cesium carbonate (0.98 g, 3.0 mmol) followed by 3-chloromethyl-2-methyl-2H-[1,2,4]triazole hydrochloride (0.25 g, 1.5 mmol). The resulting suspension was heated at 60° C. for 17 h. The mixture was partitioned between ammonium chloride solution (saturated aqueous) and ethyl acetate. The layers were separated and the aqueous phase extracted a second time with ethyl acetate. The combined organic extracts were washed with brine, dried (MgSO4) and concentrated in vacuo to give 5-bromo-6-(2-methyl-2H-[1,2,4]triazol-3-ylmethoxy)-1-phenyl-1H-pyrazolo[3,4-b]pyridine (0.40 g) of adequate purity. δH (400 MHz; CDCl3) 4.04 (3H, s), 5.70 (2H, s), 7.33-7.37 (1H, m), 7.52-7.56 (2H, m), 7.90 (1H, s), 8.06 (1H, s), 8.16-8.19 (2H, m), 8.27 (1H, s); m/z (ES+) 387 (M+H+), 385 (M+H+).
Cn1ncnc1COc1nc2c(cnn2-c2ccccc2)cc1Br
null
103.8
null
531,494
ord_dataset-7774db17e619477ea20ee621abe71257
null
2002-01-01T00:01:00
true
[CH2:1]([NH:4][C:5]1[C:14]2[C:9](=[CH:10][CH:11]=[C:12]([N+:15]([O-:17])=[O:16])[CH:13]=2)[N:8]=[C:7](Cl)[N:6]=1)[CH:2]=[CH2:3].[C:19]([NH2:23])([CH3:22])([CH3:21])[CH3:20]>O>[CH2:1]([NH:4][C:5]1[C:14]2[C:9](=[CH:10][CH:11]=[C:12]([N+:15]([O-:17])=[O:16])[CH:13]=2)[N:8]=[C:7]([NH:23][C:19]([CH3:22])([CH3:21])[CH3:20])[N:6]=1)[CH:2]=[CH2:3]
CC(C)(C)N
C=CCNc1nc(Cl)nc2ccc([N+](=O)[O-])cc12
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
null
null
null
null
null
null
null
null
null
null
null
null
At 80° C. were stirred 225 mg (0.85 mmol) of 4-allylamino-2-chloro-6-nitroquinazoline and 696 mg (9.52 mmol) of t-butylamine overnight. Water was added to the reaction mixture, followed by extraction with ethyl acetate, washing with brine and drying over anhydrous sodium sulfate. After the solvent was distilled off, the residue was purified by a silica gel column to give 240 mg (yield: 93.7%) of the title compound.
C=CCNc1nc(NC(C)(C)C)nc2ccc([N+](=O)[O-])cc12
null
93.7
null
1,457,620
ord_dataset-a86112d52cd54525a5e36d41f18aced2
null
2014-01-01T00:07:00
true
[C:1]1([C:7]2[CH:8]=[C:9]([OH:33])[C:10]([NH:13]C(C3C=CC=CC=3)(C3C=CC=CC=3)C3C=CC=CC=3)=[N:11][CH:12]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([O-])([O-])=O.[Cs+].[Cs+].[CH3:40][O:41][C:42]1[CH:43]=[C:44]([CH:47]=[CH:48][CH:49]=1)[CH2:45]Br>C1COCC1.ClCCl>[CH3:40][O:41][C:42]1[CH:43]=[C:44]([CH:47]=[CH:48][CH:49]=1)[CH2:45][O:33][C:9]1[C:10]([NH2:13])=[N:11][CH:12]=[C:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[CH:8]=1
Oc1cc(-c2ccccc2)cnc1NC(c1ccccc1)(c1ccccc1)c1ccccc1
COc1cccc(CBr)c1
null
O=C([O-])[O-]
[Cs+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
ClCCl
null
null
null
null
null
null
null
null
null
25
0.33
To a solution of 5-phenyl-2-(trityl-amino)-pyridin-3-ol (100 mg, 0.24 mmol) in THF (3 mL) was added Cs2CO3 (79 mg, 0.24 mmol). The mixture was stirred at room temperature for 20 minutes, and then 3-methoxybenzylbromide (0.037 mL, 0.26 mmol) was added. The reaction was stirred at room temperature overnight, diluted with dichloromethane (5 mL), and filtered to remove the salts. The solvents were evaporated, and the residue was dissolved in 10% trifluoroacetic acid in dichloromethane (2 mL). The reaction was stirred for 2 hr, and evaporated. The residue was dissolved in dichloromethane, washed by sat. NaHCO3, and dried over Na2SO4. After filtration and concentration, the crude product was purified on a silica gel column eluting with methanol-dichloromethane (from 3% to 15% gradient) to provide 3-(3-methoxy-benzyloxy)-5-phenyl-pyridin-2-ylamine as a white solid (43.5 mg, 60% yield).
COc1cccc(COc2cc(-c3ccccc3)cnc2N)c1
null
59.2
null
1,449,877
ord_dataset-a86112d52cd54525a5e36d41f18aced2
null
2014-01-01T00:07:00
true
[F:1][CH:2]([F:39])[C:3]1[N:7]([C:8]2[N:13]=[C:12]([N:14]3[CH2:19][CH2:18][O:17][CH2:16][CH2:15]3)[N:11]=[C:10]([C:20]3[CH2:21][CH2:22][N:23]([C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[CH2:24][CH:25]=3)[N:9]=2)[C:6]2[CH:33]=[CH:34][CH:35]=[C:36]([O:37][CH3:38])[C:5]=2[N:4]=1>CO.C1COCC1.[Pd]>[F:39][CH:2]([F:1])[C:3]1[N:7]([C:8]2[N:13]=[C:12]([N:14]3[CH2:15][CH2:16][O:17][CH2:18][CH2:19]3)[N:11]=[C:10]([CH:20]3[CH2:25][CH2:24][N:23]([C:26]([O:28][C:29]([CH3:31])([CH3:32])[CH3:30])=[O:27])[CH2:22][CH2:21]3)[N:9]=2)[C:6]2[CH:33]=[CH:34][CH:35]=[C:36]([O:37][CH3:38])[C:5]=2[N:4]=1
COc1cccc2c1nc(C(F)F)n2-c1nc(C2=CCN(C(=O)OC(C)(C)C)CC2)nc(N2CCOCC2)n1
null
null
[Pd]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
A solution of tert-butyl 4-[4-[2-(difluoromethyl)-4-methoxy-1H-benzimidazol-1-yl]-6-(4-morpholinyl)-1,3,5-triazin-2-yl]-3,6-dihydro-1(2H)-pyridinecarboxylate (1.79 g, 3.29 mmol) in a mixture of MeOH (80 mL) and THF (80 mL) was hydrogenated over 10% Pd on carbon (100 mg). After removal of the hydrogen, the mixture was refluxed in air for additional 2 hrs. The catalyst Pd/C was removed by filtration through celite, and the solvents were removed under vacuum. Recrystallization of the residue from methanol gave tert-butyl 4-[4-[2-(difluoromethyl)-4-methoxy-1H-benzimidazol-1-yl]-6-(4-morpholinyl)-1,3,5-triazin-2-yl]-1-piperidine-carboxylate: mp (MeOH) 177-179° C.; 1H NMR (CDCl3) δ 8.01 (dd, J=8.4, 0.7 Hz, 1H), 7.58 (t, JHF=53.6 Hz, 1H), 7.38 (t, J=8.2 Hz, 1H), 6.84 (d, J=7.8 Hz, 1H), 4.22 (m, 2H), 4.05 (s, 3H), 3.99 (m, 2H), 3.94 (m, 2H), 3.81 (m, 4H), 2.94-2.78 (m, 3H), 2.05 (dd, J=13.0, 1.9 Hz, 2H), 1.81 (qd, J=12.7, 4.4 Hz, 2H), 1.49 (s, 9H); Anal. Calcd. for C26H33F2N7O4: C, 57.2; H, 6.1; N, 18.0. Found: C, 57.4; H, 6.15; N, 18.1%.
COc1cccc2c1nc(C(F)F)n2-c1nc(C2CCN(C(=O)OC(C)(C)C)CC2)nc(N2CCOCC2)n1
null
null
null
519,404
ord_dataset-262b40ea420c471da9b9244fe9b8f645
null
2001-01-01T00:10:00
true
[O:1]([C:8]1[CH:9]=[C:10]([NH:14][NH2:15])[CH:11]=[CH:12][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(OCC)(=O)C.Cl[C:23]([O:25][CH:26]([CH2:28][CH3:29])[CH3:27])=[O:24]>N1C=CC=CC=1>[O:1]([C:8]1[CH:9]=[C:10]([NH:14][NH:15][C:23]([O:25][CH:26]([CH3:27])[CH2:28][CH3:29])=[O:24])[CH:11]=[CH:12][CH:13]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
NNc1cccc(Oc2ccccc2)c1
CCC(C)OC(=O)Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOC(C)=O
c1ccncc1
null
null
null
null
null
null
null
null
null
25
1
To 3.0 g of 3-phenoxyphenyl hydrazine, 100 ml of ethyl acetate and 2.5 ml of pyridine were added and the resultant solution was then stirred at room temperature for 30 minutes. Then, 2.5 ml of sec-butyl chloro-formate was added dropwise to the solution and stirred for 1 hour at room temperature. The solution was then washed twice, each time with 100 ml of water. After each wash, the aqueous fraction was removed from the organic (ethyl acetate) fraction. The resulting ethyl acetate fraction was then dried over anhydrous sodium sulfate, evaporated under reduced pressure, and then purified by column chromatography on silica gel, to produce 1.5 g of 1-methylpropyl 2-(3-phenoxyphenyl)hydrazine carboxylate as an oil.
CCC(C)OC(=O)NNc1cccc(Oc2ccccc2)c1
null
null
null
1,763,221
ord_dataset-0b32b90cc77b4a3db47ad263e0bbc1a8
null
2016-01-01T00:09:00
true
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:25]#[N:26])=[C:6]([C:8]2[C:13]([O:14][CH3:15])=[CH:12][N:11]([CH:16]([CH2:20][CH:21]3[CH2:23][CH2:22]3)[C:17](O)=[O:18])[C:10](=[O:24])[CH:9]=2)[CH:7]=1.[NH2:27][C:28]1[CH:40]=[CH:39][C:31]([C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33])=[CH:30][CH:29]=1>>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:25]#[N:26])=[C:6]([C:8]2[C:13]([O:14][CH3:15])=[CH:12][N:11]([CH:16]([CH2:20][CH:21]3[CH2:22][CH2:23]3)[C:17]([NH:27][C:28]3[CH:40]=[CH:39][C:31]([C:32]([O:34][C:35]([CH3:36])([CH3:37])[CH3:38])=[O:33])=[CH:30][CH:29]=3)=[O:18])[C:10](=[O:24])[CH:9]=2)[CH:7]=1
CC(C)(C)OC(=O)c1ccc(N)cc1
COc1cn(C(CC2CC2)C(=O)O)c(=O)cc1-c1cc(Cl)ccc1C#N
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
420 mg (purity 92%, 1.04 mmol) of 2-[4-(5-chloro-2-cyanophenyl)-5-methoxy-2-oxopyridin-1(2H)-yl]-3-cyclopropylpropanoic acid (racemate) and 1.2 eq. of tert-butyl 4-aminobenzoate were reacted according to General Method 5A. Yield: 348 mg (61% of theory)
COc1cn(C(CC2CC2)C(=O)Nc2ccc(C(=O)OC(C)(C)C)cc2)c(=O)cc1-c1cc(Cl)ccc1C#N
null
null
null
596,881
ord_dataset-843ef38b45484f72826f5f39d8a29c4d
null
2003-01-01T00:06:00
true
[NH2:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([NH:8][CH2:9][CH2:10][CH2:11][O:12][C:13]2[CH:14]=[CH:15][C:16]3[CH2:22][C@@H:21]([CH2:23][C:24]([O:26]CC)=[O:25])[C:20]4[CH:29]=[CH:30][CH:31]=[CH:32][C:19]=4[CH2:18][C:17]=3[CH:33]=2)[CH:3]=1.O[Li].O.C1COCC1>O>[NH2:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([NH:8][CH2:9][CH2:10][CH2:11][O:12][C:13]2[CH:14]=[CH:15][C:16]3[CH2:22][C@@H:21]([CH2:23][C:24]([OH:26])=[O:25])[C:20]4[CH:29]=[CH:30][CH:31]=[CH:32][C:19]=4[CH2:18][C:17]=3[CH:33]=2)[CH:3]=1
CCOC(=O)C[C@@H]1Cc2ccc(OCCCNc3cc(N)ccn3)cc2Cc2ccccc21
null
null
[Li]O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
C1CCOC1
null
null
null
null
null
null
null
null
null
25
48
A mixture of ethyl (S)-10,11-dihydro-3-[3-(4-aminopyridin-2-ylamino)-1-propyloxy]-5H-dibenzo[a,d]cycloheptene-10-acetate (2.4 g, 5 mmole), LiOH.H2O (0.3 g, 7 mmole), THF (30 mL), and H2O (10 mL) was stirred at RT for 48 hr, then was concentrated. The residue was diluted with H2O and extracted with Et2O. The Et2O layers were discarded. The aqueous layer was stirred with gentle warming under vacuum to remove residual organic solvents, then was filtered. The resulting aqueous solution was stirred at RT while the pH was slowly and carefully adjusted to 5.5-6.0 with 1.0 N HCl The mixture was stirred for 0.5 hr, then the solid was collected by suction filtration and washed with plenty of H2O. Drying in high vacuum at 60° C. gave the title compound (1.0 g, 42%) as a glassy solid: MS (ES) m/e 417.7 (M+H)+. Anal. Calcd for C25H27N3O3 1.4 HCl (468.554): C, 64.08; H, 6.11; N, 8.97. Found: C, 64.16; H, 6.20; N, 8.71.
Nc1ccnc(NCCCOc2ccc3c(c2)Cc2ccccc2[C@H](CC(=O)O)C3)c1
null
47.9
null
1,010,093
ord_dataset-7448b89163bf426c9d9777809ce24cec
null
2010-01-01T00:11:00
true
C(OC(=O)[NH:7][CH2:8][C:9](=[O:44])[NH:10][CH2:11][C:12]1[CH:17]=[CH:16][C:15]([N:18]2[C:22]([NH:23][C:24]([NH:26][C:27]3[CH:32]=[CH:31][C:30]([O:33][C:34]4[CH:39]=[CH:38][N:37]=[CH:36][CH:35]=4)=[CH:29][CH:28]=3)=[O:25])=[CH:21][C:20]([C:40]([CH3:43])([CH3:42])[CH3:41])=[N:19]2)=[CH:14][CH:13]=1)(C)(C)C.C(O)(C(F)(F)F)=O>C1COCC1>[NH2:7][CH2:8][C:9]([NH:10][CH2:11][C:12]1[CH:17]=[CH:16][C:15]([N:18]2[C:22]([NH:23][C:24]([NH:26][C:27]3[CH:32]=[CH:31][C:30]([O:33][C:34]4[CH:35]=[CH:36][N:37]=[CH:38][CH:39]=4)=[CH:29][CH:28]=3)=[O:25])=[CH:21][C:20]([C:40]([CH3:43])([CH3:42])[CH3:41])=[N:19]2)=[CH:14][CH:13]=1)=[O:44]
CC(C)(C)OC(=O)NCC(=O)NCc1ccc(-n2nc(C(C)(C)C)cc2NC(=O)Nc2ccc(Oc3ccncc3)cc2)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
O=C(O)C(F)(F)F
null
null
null
null
null
null
null
null
null
25
18
To a solution of {[4-(3-tert-butyl-5-{3-[4-(pyridin-4-yloxy)-phenyl]-ureido}-pyrazol-1-yl)-benzylcarbamoyl]-methyl}-carbamic acid tert-butyl ester (60 mg, 0.10 mmol) in THF (5 mL) was added TFA (3 mL), and the resulting mixture was stirred at room temperature for 18 h. The reaction mixture was partitioned between EtOAc (20 mL) and saturated NaHCO3 aqueous solution (20 mL), and the organic layer was removed and washed with brine, dried over Na2SO4, and concentrated at reduced pressure. The residue was purified by preparative TLC (90:10 CH2Cl2/MeOH) to give 10 mg (20%) of the desired product. 1H-NMR (DMSO-d6) δ 8.72 (s, 1H), 8.32 (d, J=5.7 Hz, 2H), 8.02 (s, 1H), 7.53 to 7.30 (m, 6H), 6.96 (d, J=6.6 Hz, 2H), 6.73 (d, J=6.3 Hz, 2H), 6.32 (s, 1H), 4.36 (s, 2H), 3.70 (S, 2H), 1.18 (s, 9H); MS LC-MS [M+H]+=513, RT=2.01 min.
CC(C)(C)c1cc(NC(=O)Nc2ccc(Oc3ccncc3)cc2)n(-c2ccc(CNC(=O)CN)cc2)n1
null
19.5
null
1,588,816
ord_dataset-380e279f82154dba9e08ab51b3bdd08a
null
2015-01-01T00:05:00
true
[CH3:1][N:2]1[CH2:7][CH2:6][CH:5]([NH2:8])[CH2:4][CH2:3]1.C(N(CC)CC)C.[Br:16][C:17]1[S:18][C:19]([C:23](O)=[O:24])=[C:20]([CH3:22])[N:21]=1.Cl.CN(C)CCCN=C=NCC.ON1C2C=CC=CC=2N=N1>O1CCCC1>[CH3:1][N:2]1[CH2:7][CH2:6][CH:5]([NH:8][C:23]([C:19]2[S:18][C:17]([Br:16])=[N:21][C:20]=2[CH3:22])=[O:24])[CH2:4][CH2:3]1
Cc1nc(Br)sc1C(=O)O
CN1CCC(N)CC1
null
CCN=C=NCCCN(C)C
Cl
On1nnc2ccccc21
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
CCN(CC)CC
null
null
null
null
null
null
null
null
null
25
22
To a stirred mixture of 1-methyl-4-aminopiperidine (125 μL, 114 mg, 1 mmol) and triethylamine (570 μL, 414 mg, 4.1 mmol) in anhydrous tetrahydrofuran (1.0 mL), 2-bromo-4-methyl-thiazole-5-carboxylic acid (266 mg, 1.2 mmol), (3-dimethylaminopropyl)-ethyl-carbodiimide hydrochloride (232 mg, 1.2 mmol) and 1-hydroxy-benzotriazole (164 mg, 1.2 mmol) were sequentially and the mixture was stirred at room temperature for 22 h. After dilution with dichloromethane (20 mL), the mixture was washed with water (3×10 mL), dried over MgSO4 and concentrated. In this manner the title compound (277 mg, 0.87 mmol, 87%) was obtained as a yellow solid.
Cc1nc(Br)sc1C(=O)NC1CCN(C)CC1
null
87
null
1,008,191
ord_dataset-7448b89163bf426c9d9777809ce24cec
null
2010-01-01T00:11:00
true
FC(F)(F)COP([CH2:13][C:14]([O:16][CH3:17])=[O:15])(OCC(F)(F)F)=O.C1OCCOCCOCCOCCOCCOC1.C[Si]([N-][Si](C)(C)C)(C)C.[K+].[Cl:48][C:49]1[CH:50]=[C:51]([C:59]2[N:63]=[C:62]([C:64]3[CH:71]=[CH:70][C:67]([CH:68]=O)=[CH:66][CH:65]=3)[O:61][N:60]=2)[CH:52]=[CH:53][C:54]=1[O:55][CH:56]([CH3:58])[CH3:57]>C1COCC1>[Cl:48][C:49]1[CH:50]=[C:51]([C:59]2[N:63]=[C:62]([C:64]3[CH:65]=[CH:66][C:67](/[CH:68]=[CH:13]\[C:14]([O:16][CH3:17])=[O:15])=[CH:70][CH:71]=3)[O:61][N:60]=2)[CH:52]=[CH:53][C:54]=1[O:55][CH:56]([CH3:57])[CH3:58]
COC(=O)CP(=O)(OCC(F)(F)F)OCC(F)(F)F
CC(C)Oc1ccc(-c2noc(-c3ccc(C=O)cc3)n2)cc1Cl
null
C1COCCOCCOCCOCCOCCO1
C[Si](C)(C)[N-][Si](C)(C)C
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
-78
null
A two-neck round bottom flask was charged with methyl 2-(bis(2,2,2-trifluoroethoxy)phosphoryl)acetate (0.235 ml, 1.109 mmol), 18-crown-6 (1465 mg, 5.54 mmol) and THF (15 ml). The mixture was then cooled to −78° C. under an atmosphere of nitrogen. Potassium bis(trimethylsilyl)amide (221 mg, 1.109 mmol) was added and the mixture stirred for a few minutes. 4-(3-(3-chloro-4-isopropoxyphenyl)-1,2,4-oxadiazol-5-yl)benzaldehyde (380 mg, 1.109 mmol) was added and the mixture stirred at −78° C. for 90 minutes and then left to warm to room temperature overnight. Reaction was quenched by the addition of saturated NH4Cl (aqueous). The mixture was separated and the aqueous layer was extracted with ether (3×10 mL). The combined organics were dried over MgSO4 and concentrated to give an off-white solid. The solid was triturated with MeOH and collected by vacuum filtration and washed with MeOH (3×10 mL). Collected solid was dried overnight in a vacuum oven to give (Z)-methyl 3-(4-(3-(3-chloro-4-isopropoxyphenyl)-1,2,4-oxadiazol-5-yl)phenyl)acrylate (325 mg, 73.5%).
COC(=O)/C=C\c1ccc(-c2nc(-c3ccc(OC(C)C)c(Cl)c3)no2)cc1
null
73.5
null
1,055,994
ord_dataset-373415d3e0e54004837cf4831e67666f
null
2011-01-01T00:05:00
true
CCCC[N+](CCCC)(CCCC)CCCC.[F-].[Si]([O:26][C:27]([CH3:60])([CH3:59])[CH2:28][C:29]1[CH:30]=[CH:31][C:32]2[C:45]3[N:44]=[C:43]([C:46]4[C:51]([Br:52])=[CH:50][CH:49]=[CH:48][C:47]=4[Br:53])[NH:42][C:41]=3[C:40]3[C:35](=[CH:36][C:37]([O:54][CH2:55][CH:56]4[CH2:58][CH2:57]4)=[CH:38][CH:39]=3)[C:33]=2[CH:34]=1)(C(C)(C)C)(C)C>O>[CH:56]1([CH2:55][O:54][C:37]2[CH:36]=[C:35]3[C:40](=[CH:39][CH:38]=2)[C:41]2[NH:42][C:43]([C:46]4[C:47]([Br:53])=[CH:48][CH:49]=[CH:50][C:51]=4[Br:52])=[N:44][C:45]=2[C:32]2[CH:31]=[CH:30][C:29]([CH2:28][C:27]([CH3:60])([OH:26])[CH3:59])=[CH:34][C:33]3=2)[CH2:57][CH2:58]1
CC(C)(Cc1ccc2c(c1)c1cc(OCC3CC3)ccc1c1[nH]c(-c3c(Br)cccc3Br)nc21)O[Si](C)(C)C(C)(C)C
null
null
CCCC[N+](CCCC)(CCCC)CCCC
[F-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
null
null
null
null
null
null
null
null
null
null
null
null
TBAF (1 M in THF, 10 mL) was added to a flask containing 6-(2-{[tert-butyl(dimethyl)silyl]oxy}-2-methylpropyl)-9-(cyclopropylmethoxy)-2-(2,6-dibromophenyl)-1H-phenanthro[9,10-d]imidazole (0.223 g, 0.31 mmol) from Step 7 above, at room temperature. The resulting solution was heated at reflux for 36 h, after which water was added to the reaction mixture. The aqueous layer was extracted with ethyl acetate, the organic layer dried over MgSO4, filtered and concentrated. The crude product was used directly in the next reaction (Step 9 below).
CC(C)(O)Cc1ccc2c(c1)c1cc(OCC3CC3)ccc1c1[nH]c(-c3c(Br)cccc3Br)nc21
null
null
null
1,759,689
ord_dataset-97eb2ab57fec4160922caae33b54d956
null
2016-01-01T00:08:00
true
[C:1]([N:4]1[C:13]2[C:8](=[CH:9][C:10]([C:15]3[CH:16]=[N:17][N:18]([CH:20]4[CH2:22][CH2:21]4)[CH:19]=3)=[C:11](N)[CH:12]=2)[N:7]([C:23]([O:25][CH:26]([CH3:28])[CH3:27])=[O:24])[CH2:6][C@@H:5]1[CH3:29])(=[O:3])[CH3:2].C(N1C2C(=CC(C3C=CC(S(C)(=O)=O)=CC=3)=C([Br:43])C=2)N(C(OC(C)C)=O)C[C@@H]1C)(=O)C>>[C:1]([N:4]1[C:13]2[C:8](=[CH:9][C:10]([C:15]3[CH:16]=[N:17][N:18]([CH:20]4[CH2:22][CH2:21]4)[CH:19]=3)=[C:11]([Br:43])[CH:12]=2)[N:7]([C:23]([O:25][CH:26]([CH3:28])[CH3:27])=[O:24])[CH2:6][C@@H:5]1[CH3:29])(=[O:3])[CH3:2]
CC(=O)N1c2cc(N)c(-c3cnn(C4CC4)c3)cc2N(C(=O)OC(C)C)C[C@@H]1C
CC(=O)N1c2cc(Br)c(-c3ccc(S(C)(=O)=O)cc3)cc2N(C(=O)OC(C)C)C[C@@H]1C
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Isopropyl (S)-4-acetyl-6-bromo-7-(1-cyclopropyl-1H-pyrazol-4-yl)-3-methyl-3,4-dihydroquinoxaline-1(2H)-carboxylate was synthesized from isopropyl (S)-4-acetyl-6-amino-7-(1-cyclopropyl-1H-pyrazol-4-yl)-3-methyl-3,4-dihydroquinoxaline-1(2H)-carboxylate according to the procedure described above for isopropyl (S)-4-acetyl-6-bromo-3-methyl-7-(4-(methylsulfonyl)phenyl)-3,4-dihydroquinoxaline-1(2H)-carboxylate (Example 238). MS (ESI, pos. ion) m/z 461, 463 [M+H]+.
CC(=O)N1c2cc(Br)c(-c3cnn(C4CC4)c3)cc2N(C(=O)OC(C)C)C[C@@H]1C
null
null
null
1,172,210
ord_dataset-d24cc23b3db94284bb83a2ccdd9eb880
null
2012-01-01T00:05:00
true
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:19](=[O:20])[N:18]([CH3:21])[C:11]3[N:12]=[C:13](SC)[N:14]=[CH:15][C:10]=3[CH:9]=2)=[CH:4][C:3]=1[NH:22][C:23]([NH:25][C:26]1[CH:31]=[CH:30][CH:29]=[C:28]([C:32]([F:35])([F:34])[F:33])[CH:27]=1)=[O:24].[CH3:36][NH2:37].C1COCC1>>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:19](=[O:20])[N:18]([CH3:21])[C:11]3[N:12]=[C:13]([NH:37][CH3:36])[N:14]=[CH:15][C:10]=3[CH:9]=2)=[CH:4][C:3]=1[NH:22][C:23]([NH:25][C:26]1[CH:31]=[CH:30][CH:29]=[C:28]([C:32]([F:35])([F:34])[F:33])[CH:27]=1)=[O:24]
CN
CSc1ncc2cc(-c3ccc(F)c(NC(=O)Nc4cccc(C(F)(F)F)c4)c3)c(=O)n(C)c2n1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
null
Using a procedure analogous to Example A1, 1-(2-fluoro-5-(8-methyl-2-(methylthio)-7-oxo-7,8-dihydropyrido[2,3-d]pyrimidin-6-yl)phenyl)-3-(3-(trifluoromethyl)phenyl)urea (436 mg, 0.866 mmol) and 2.00N methylamine in THF (1.93 mL, 3.85 mmol) were combined to provide 1-(2-fluoro-5-(8-methyl-2-(methylamino)-7-oxo-7,8-dihydropyrido[2,3-d]pyrimidin-6-yl)phenyl)-3-(3-(trifluoromethyl)phenyl)urea (141 mg, 75% yield). 1H NMR (300 MHz, DMSO-d6): δ 2.89 (s, 3 H), 3.53-3.61 (m, 3 H), 7.24-7.31 (m, 3 H), 7.49-7.51 (m, 2 H), 7.65-7.75 (br. m, 1 H), 7.79 (m, 1 H), 8.03 (s, 1 H), 8.37-8.39 (m, 1 H), 8.65-8.73 (m, 2 H), 9.40 (s, 1H); MS (ESI) m/z: 487.0 (M+H+).
CNc1ncc2cc(-c3ccc(F)c(NC(=O)Nc4cccc(C(F)(F)F)c4)c3)c(=O)n(C)c2n1
null
75
null
1,410,745
ord_dataset-7456bda2326f4bebaa874a5474d4cc0d
null
2014-01-01T00:03:00
true
Cl[C:2]1[C:3]2[CH2:10][C:9](=[O:11])[NH:8][C:4]=2[N:5]=[CH:6][N:7]=1.[C:12]([N:19]1[CH2:24][CH2:23][NH:22][CH2:21][CH2:20]1)([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13].CCN(C(C)C)C(C)C>CC(O)C>[C:12]([N:19]1[CH2:20][CH2:21][N:22]([C:6]2[N:7]=[CH:2][C:3]3[CH2:10][C:9](=[O:11])[NH:8][C:4]=3[N:5]=2)[CH2:23][CH2:24]1)([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13]
CC(C)(C)OC(=O)N1CCNCC1
O=C1Cc2c(Cl)ncnc2N1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(C(C)C)C(C)C
CC(C)O
null
null
null
null
null
null
null
null
null
null
14
A solution of 4-chloro-5,7-dihydropyrrolo[2,3-d]pyrimidin-6-one (prepared according to the literature: Li Sun et al. Bioorg. and Med. Chem. Lett. 2002, 12, 2153-2157; 690 mg, 3.7 mmol), Boc-piperazine (630 mg, 3.7 mmol), and DIEA (0.96 mL, 5.5 mmol) in 20 mL IPA was heated to reflux and stirred 14 hours, after which the reaction mixture was concentrated. The crude was purified on silica gel (1:2 DCM:EtOAc to 1:4 DCM:EtOAc gradient) to give 4-Boc-piperazin-1-yl-5,7-dihydropyrrolo[2,3-d]pyrimidin-6-one, which was used in the next step.
CC(C)(C)OC(=O)N1CCN(c2ncc3c(n2)NC(=O)C3)CC1
null
null
null
939,828
ord_dataset-90b0aa1f83334a02919b2be3a1c04542
null
2010-01-01T00:02:00
true
[CH2:1]([N:7]([CH3:51])[C:8]([CH:10]1[CH:14]([C:15](=[O:32])[NH:16][C:17]2([C:22]([NH:24][S:25]([C:28]3([CH3:31])[CH2:30][CH2:29]3)(=[O:27])=[O:26])=[O:23])[CH2:19][CH:18]2C=C)[CH2:13][CH:12]([O:33][C:34](=[O:50])[NH:35][C:36]2[CH:41]=[C:40]([CH3:42])[CH:39]=[CH:38][C:37]=2[C:43]2[S:44][C:45](CC)=[CH:46][N:47]=2)[CH2:11]1)=[O:9])[CH2:2][CH2:3][CH2:4][CH:5]=[CH2:6].[CH:52]1(S(O)(=O)=O)C[CH2:53]1>>[CH3:51][N:7]1[C:8](=[O:9])[CH:10]2[CH:14]([CH2:13][CH:12]([O:33][C:34](=[O:50])[NH:35][C:36]3[CH:41]=[C:40]([CH3:42])[CH:39]=[CH:38][C:37]=3[C:43]3[S:44][CH:45]=[C:46]([CH2:52][CH3:53])[N:47]=3)[CH2:11]2)[C:15](=[O:32])[NH:16][C:17]2([C:22]([NH:24][S:25]([C:28]3([CH3:31])[CH2:30][CH2:29]3)(=[O:26])=[O:27])=[O:23])[CH:19]([CH2:18]2)[CH:6]=[CH:5][CH2:4][CH2:3][CH2:2][CH2:1]1
O=S(=O)(O)C1CC1
C=CCCCCN(C)C(=O)C1CC(OC(=O)Nc2cc(C)ccc2-c2ncc(CC)s2)CC1C(=O)NC1(C(=O)NS(=O)(=O)C2(C)CC2)CC1C=C
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The procedure described in Example 18-10 was followed, but using the compound prepared in Example 22 (112) (22 mg, 30 μmol) instead of the corresponding cyclopropanesulphonic acid derivative, which gave the title compound (2.1 mg, 10%). LC/MS (Method I): tr=2.41 min, >95%, m/z (ESI+)=712 (MH+).
CCc1csc(-c2ccc(C)cc2NC(=O)OC2CC3C(=O)NC4(C(=O)NS(=O)(=O)C5(C)CC5)CC4C=CCCCCN(C)C(=O)C3C2)n1
null
10
null
714,502
ord_dataset-c8a367b56b4f406b878f51867b157d19
null
2006-01-01T00:06:00
true
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([CH:10]=1)[C:7]([NH2:9])=[O:8].[Cu](C#N)[C:12]#[N:13].N>CN(C=O)C>[C:12]([C:2]1[CH:3]=[N:4][CH:5]=[C:6]([CH:10]=1)[C:7]([NH2:9])=[O:8])#[N:13]
N#C[Cu]C#N
NC(=O)c1cncc(Br)c1
null
N
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
140
24
5-Bromonicotinamide (905 mg) and copper cyanide (630 mg) were suspended in DMF (15 ml) and the mixture was stirred at 140° C. for 24 hrs. Aqueous ammonia was added to the reaction mixture at room temperature and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography (eluent, methanol:ethyl acetate=1:10) for purification to give the title compound (110 mg) as a colorless powder.
N#Cc1cncc(C(N)=O)c1
null
16.6
null
172,564
ord_dataset-7860c6f563014da8948ede63b7110bde
null
1988-01-01T00:05:00
true
[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([C:20]([O:22]C)=[O:21])[C:12](=[C:17]([CH3:19])[CH:18]=1)[C:13]([O:15][CH3:16])=[O:14])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>[OH-].[Na+].COCCOC>[C:13]([C:12]1[C:17]([CH3:19])=[CH:18][C:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)=[CH:10][C:11]=1[C:20]([OH:22])=[O:21])([O:15][CH3:16])=[O:14]
COC(=O)c1cc(OCc2ccccc2)cc(C)c1C(=O)OC
null
null
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
COCCOC
null
null
null
null
null
null
null
null
null
null
null
null
A solution of dimethyl 4-benzyloxy-6-methyl-phthalate (1.5 gm) in sodium hydroxide (2% solution, 12 ml) and 1,2-dimethoxyethane (12 ml) was stirred at room temperature for 4 hours. The solvent was removed under reduced pressure. The aqueous solution was washed with ethyl acetate (3×125 ml). The organic extract was dried over magnesium sulphate and evaporated to give a solid. This solid was recrystallized from ethyl acetate: pet. ether 30-60 to yield 2-carbomethoxy-3-methyl-5-benzyloxy-benzoic acid (750 mg), m.p. 132°-133° C., IR (KBr): 2500-3200, 1725, 1685, 1600 cm-1. Anal. calcd. for C17H16O5 : C, 67.99, H, 5.37. Found: C, 68.01, H, 5.42.
COC(=O)c1c(C)cc(OCc2ccccc2)cc1C(=O)O
null
52.3
null
1,607,667
ord_dataset-9cecb3a8d3b9494191b28dcefea66af2
null
2015-01-01T00:07:00
true
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([N:9]2[CH2:13][CH2:12][C@H:11]([O:14][C:15]3[CH:16]=[C:17]([CH:21]=[CH:22][CH:23]=3)[C:18]([OH:20])=O)[CH2:10]2)=[CH:5][CH:4]=1)#[N:2].C(Cl)CCl.C1C=CC2N(O)N=NC=2C=1.[CH3:38][N:39]1[CH2:44][CH2:43][C:42]2[N:45]=[C:46]([NH2:48])[S:47][C:41]=2[CH2:40]1>CN(C=O)C>[C:1]([C:3]1[CH:8]=[CH:7][C:6]([N:9]2[CH2:13][CH2:12][C@H:11]([O:14][C:15]3[CH:16]=[C:17]([CH:21]=[CH:22][CH:23]=3)[C:18]([NH:48][C:46]3[S:47][C:41]4[CH2:40][N:39]([CH3:38])[CH2:44][CH2:43][C:42]=4[N:45]=3)=[O:20])[CH2:10]2)=[CH:5][CH:4]=1)#[N:2]
N#Cc1ccc(N2CC[C@H](Oc3cccc(C(=O)O)c3)C2)cc1
CN1CCc2nc(N)sc2C1
null
On1nnc2ccccc21
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCCl
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
1
Dissolve 3-[(S)-1-(4-cyano-phenyl)-pyrrolidin-3-yloxy]-benzoic acid (80.2 mg, 0.26 mmol), EDC (99.2 mg, 0.52 mmol) and HOBT (79.6 mg, 0.52 mmol) into 2 mL of DMF. The mixture is stirred for 1 h. Add 5-methyl-4,5,6,7-tetrahydro-thiazolo[5,4-c]pyridin-2-ylamine (46.5 mg, 0.28 mmol) to the mixture and place in a 60° C. bath with an Ar stream blowing over it. Stir mixture for 14 h resulting in a concentrated residue. LC-MS analysis indicates the desired product. Dissolve into 5 mL of DMF and purify via the Gilson Prep HPLC system (5%-80% CH3CN/H2O) to give 59.4 mg of the title compound, MS, electrospray 560.58 (M+H), rt 6.01 min.
CN1CCc2nc(NC(=O)c3cccc(O[C@H]4CCN(c5ccc(C#N)cc5)C4)c3)sc2C1
null
null
null
1,188,857
ord_dataset-9cd817a75dfc4fe7ad19d4232772d5ff
null
2012-01-01T00:07:00
true
[C:1]1([CH3:29])[CH:6]=[C:5]([CH3:7])[CH:4]=[C:3]([CH3:8])[C:2]=1[O:9][C:10]1[C:11]2[N:27]([CH3:28])[CH:26]=[CH:25][C:12]=2[N:13]=[C:14]([NH:16][C:17]2[CH:24]=[CH:23][C:20]([C:21]#[N:22])=[CH:19][CH:18]=2)[N:15]=1.C1C(=O)N([Cl:37])C(=O)C1>C(Cl)Cl>[Cl:37][C:25]1[C:12]2[N:13]=[C:14]([NH:16][C:17]3[CH:24]=[CH:23][C:20]([C:21]#[N:22])=[CH:19][CH:18]=3)[N:15]=[C:10]([O:9][C:2]3[C:1]([CH3:29])=[CH:6][C:5]([CH3:7])=[CH:4][C:3]=3[CH3:8])[C:11]=2[N:27]([CH3:28])[CH:26]=1
Cc1cc(C)c(Oc2nc(Nc3ccc(C#N)cc3)nc3ccn(C)c23)c(C)c1
O=C1CCC(=O)N1Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
null
null
To a solution of 4-(4-(mesityloxy)-5-methyl-5H-pyrrolo[3,2-d]pyrimidin-2-ylamino)benzonitrile (17.3 mg, 0.05 mmol) in CH2Cl2 (5 mL) was added NCS (6.03 mg, 0.05 mmol) and the resultant mixture was refluxed for 16 h. After completion of the reaction, the solvent was concentrated and purified by preparative TLC, eluting with hexanes:ethyl acetate (3:1), to give the product as an off-white solid (3.4 mg, 6%).
Cc1cc(C)c(Oc2nc(Nc3ccc(C#N)cc3)nc3c(Cl)cn(C)c23)c(C)c1
null
16.3
null
1,769,180
ord_dataset-0b32b90cc77b4a3db47ad263e0bbc1a8
null
2016-01-01T00:09:00
true
[NH2:1][C:2](=[O:25])[C:3]([NH:5][C:6]1[CH:11]=[C:10]([C:12]2[S:13][CH:14]=[CH:15][CH:16]=2)[CH:9]=[CH:8][C:7]=1[NH:17]C(=O)OC(C)(C)C)=[O:4].C(O)(C(F)(F)F)=O>C(Cl)Cl>[NH2:17][C:7]1[CH:8]=[CH:9][C:10]([C:12]2[S:13][CH:14]=[CH:15][CH:16]=2)=[CH:11][C:6]=1[NH:5][C:3](=[O:4])[C:2]([NH2:1])=[O:25]
CC(C)(C)OC(=O)Nc1ccc(-c2cccs2)cc1NC(=O)C(N)=O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O=C(O)C(F)(F)F
ClCCl
null
null
null
null
null
null
null
null
null
25
2
To a solution of tert-butyl (2-(2-amino-2-oxoacetamido)-4-(thiophen-2-yl)phenyl)carbamate (0.1 g, 0.28 mmol) in DCM (3 mL) was added TFA (1 mL, 13 mmol) at 0° C. The reaction was warmed to room temperature and stirred for 2 h. The reaction was then concentrated under reduced pressure. The residue was basified with a saturated aqueous solution of Na2CO3. The obtained solid was filtered, washed with water and ether then dried to afford N1-(2-amino-5-(thiophen-2-yl)phenyl)oxalamide (40 mg, 55% yield). ESI+ MS: m/z 262 ([M+H]+), 1H NMR (500 MHz, d6-DMSO): δ 9.89 (s, 1H), 8.24 (s, 1H), 7.94 (s, 1H), 7.59 (d, J=2.0 Hz, 1H), 7.6 (d, J=5 Hz, 1H), 7.29-7.26 (m, 1H), 7.23 (d, J=4.0 Hz, 1H), 7.05 (t, J=4.0 Hz, 1H), 6.80 (d, J=9.0 Hz, 1H), 5.16 (s, 2H).
NC(=O)C(=O)Nc1cc(-c2cccs2)ccc1N
null
54.7
null
491,942
ord_dataset-3f9174c7efcb4f31becbd3516cde9572
null
2001-01-01T00:02:00
true
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([N:9]2[CH2:14][CH2:13][CH:12]([NH:15][C:16](=O)[CH2:17][CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[CH2:11][CH2:10]2)=[CH:5][CH:4]=1.[H-].[H-].[H-].[H-].[Li+].[Al+3]>>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]([N:9]2[CH2:10][CH2:11][CH:12]([NH:15][CH2:16][CH2:17][CH2:18][C:19]3[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=3)[CH2:13][CH2:14]2)=[CH:7][CH:8]=1
COc1ccc(N2CCC(NC(=O)CCc3ccccc3)CC2)cc1
null
null
[Al+3]
[H-]
[Li+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Following the general procedure of example 40b, N-[1-(4-methoxy-phenyl)-piperidin-4-yl]-3-phenyl-propionamide (1.87 g, 5.53 mmol) was reduced with LiAlH4 to give [1-(4-methoxy-phenyl)-piperidin-4-yl]-(3-phenyl-propyl)-amine (1.64 g, 91%, MS: m/e=325.4 (M+H+)) as a white solid.
COc1ccc(N2CCC(NCCCc3ccccc3)CC2)cc1
null
91.4
null
1,207,827
ord_dataset-fb72428f30234761b4216139dc228d0c
null
2012-01-01T00:09:00
true
[Br:1][C:2]1[C:3]([O:10][CH3:11])=[N+:4]([O-])[C:5]([CH3:8])=[CH:6][CH:7]=1.[C:12]([O:15][C:16](=O)C)(=[O:14])C>>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:12]([O:15][CH3:16])=[O:14])=[N:4][C:3]=1[O:10][CH3:11]
CC(=O)OC(C)=O
COc1c(Br)ccc(C)[n+]1[O-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
step c—A solution of 357b (0.47 g) and acetic anhydride (4.0 mL) was heated at 120° C. for 2 h, The reaction mixture was concentrated in vacuo and purified on a SiO2 column eluting with 5% EtOAc/hexane to afford methyl 5-bromo-6-methoxy-pyridin-2-yl-acetate (357c).
COC(=O)Cc1ccc(Br)c(OC)n1
null
null
null