original_index
int64
2
1.77M
agent_000
stringlengths
1
540
agent_001
stringlengths
1
852
agent_002
stringlengths
1
247
date_of_experiment
timestamp[ns]date
extracted_from_file
stringclasses
489 values
grant_date
timestamp[ns]date
1976-01-01 00:01:00
2016-01-01 00:09:00
is_mapped
bool
1 class
procedure_details
stringlengths
8
24.5k
product_000
stringlengths
1
484
product_001
stringlengths
1
208
reactant_000
stringlengths
1
902
reactant_001
stringlengths
1
902
reactant_002
stringlengths
1
285
rxn_str
stringlengths
87
6.12k
rxn_time
float64
0
2.16k
solvent_000
stringclasses
446 values
solvent_001
stringclasses
405 values
solvent_002
stringclasses
330 values
temperature
float64
-230
30.1k
yield_000
float64
0
90,205,156,600B
yield_001
float64
0
100M
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_003
null
solvent_004
null
solvent_005
null
solvent_006
null
solvent_007
null
solvent_008
null
solvent_009
null
solvent_010
null
1,704,561
O=C[O-]
[NH4+]
null
null
ord_dataset-54347fcace774f89850681d6dec8009f
2016-01-01T00:03:00
true
A mixture of benzyl ((3R,4R)-4-fluoro-1-(9-isopropyl-6-((1-methyl-1H-pyrazol-4-yl)amino)-9H-purin-2-yl)pyrrolidin-3-yl)carbamate (390 mg, 0.8 mmol), ammonium formate (514 mg, 8 mmol) in ethanol (20 mL) was degassed for 3 min and 10%-Pd/C (50 mg) was then added. The reaction was stirred and heated to gentle reflux for 45 min. The catalyst was removed by filtration and washed well with ethanol (40 mL). The combined liquors were concentrated to give a residue, which was taken into water (5 mL) and extracted with DCM-isopropanol (9:1, 2×70 mL). The combined organic extracts were washed with saturated NaHCO3 (5 mL), dried over Na2SO4 and evaporated to give the title compound as a light yellow solid (272 mg, 96% yield). 1H NMR (400 MHz, DMSO-d6) δ ppm 9.58 (s, 1 H) 8.00 (s, 2 H) 7.90 (s, 2 H) 7.73 (s, 1 H) 4.89-5.08 (m, 1 H) 4.56-4.66 (m, 1 H) 3.86-4.00 (m, 1 H) 3.81-3.85 (m, 3 H) 3.58-3.80 (m, 3 H) 3.53 (d, J=11.13 Hz, 1 H) 1.51 (d, J=6.72 Hz, 6 H). 19F NMR (376 MHz, DMSO-d6) δ ppm −177.42 (s, 1F). m/z (APCI+) for C16H22FN9 360.2 (M+H)+. Chiral purity was determined as below (using racemic sample to compare):
CC(C)n1cnc2c(Nc3cnn(C)c3)nc(N3C[C@@H](N)[C@H](F)C3)nc21
null
CC(C)n1cnc2c(Nc3cnn(C)c3)nc(N3C[C@@H](F)[C@H](NC(=O)OCc4ccccc4)C3)nc21
null
null
[F:1][C@@H:2]1[CH2:6][N:5]([C:7]2[N:15]=[C:14]3[C:10]([N:11]=[CH:12][N:13]3[CH:16]([CH3:18])[CH3:17])=[C:9]([NH:19][C:20]3[CH:21]=[N:22][N:23]([CH3:25])[CH:24]=3)[N:8]=2)[CH2:4][C@H:3]1[NH:26]C(=O)OCC1C=CC=CC=1.C([O-])=O.[NH4+].O>C(O)C>[NH2:26][C@H:3]1[C@H:2]([F:1])[CH2:6][N:5]([C:7]2[N:15]=[C:14]3[C:10]([N:11]=[CH:12][N:13]3[CH:16]([CH3:18])[CH3:17])=[C:9]([NH:19][C:20]3[CH:21]=[N:22][N:23]([CH3:25])[CH:24]=3)[N:8]=2)[CH2:4]1
null
CCO
O
null
null
null
94.6
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,488,457
[Pd]
[NH4+]
[OH-]
null
ord_dataset-c3c1091f873b4f40827973a6f1f9b685
2014-01-01T00:09:00
true
A solution of 1-(4-chloro-pyrrolo[2,3-d]pyrimidin-7-yl)-cyclopropanecarboxylic acid methyl ester (Preparation 245, 920 mg, 3.65 mmol) in ethanol (20 mL) was degassed with argon for 15 min. Ammonium hydroxide (4 mL) and 10% palladium on charcoal were added and the reaction mixture was stirred at room temperature under hydrogen (balloon pressure) for 5 hours. The reaction mixture was filtered on a celite bed, washed with ethanol (2×10 mL) and the filtrate was evaporated in vacuo. The crude material was purified by column chromatography on silica gel (gradient of DCM:methanol 100:0 to 98:2) to afford the title compound as a gum in 59% yield, 470 mg.
COC(=O)C1(n2ccc3cncnc32)CC1
null
COC(=O)C1(n2ccc3c(Cl)ncnc32)CC1
null
null
[CH3:1][O:2][C:3]([C:5]1([N:8]2[C:12]3[N:13]=[CH:14][N:15]=[C:16](Cl)[C:11]=3[CH:10]=[CH:9]2)[CH2:7][CH2:6]1)=[O:4].[OH-].[NH4+]>C(O)C.[Pd]>[CH3:1][O:2][C:3]([C:5]1([N:8]2[C:12]3[N:13]=[CH:14][N:15]=[CH:16][C:11]=3[CH:10]=[CH:9]2)[CH2:6][CH2:7]1)=[O:4]
5
CCO
null
null
25
59
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
786,033
O=C([O-])[O-]
[Br-]
[Cs+]
null
ord_dataset-4ad5db8537994579bef51f16dd8bf0bd
2007-01-01T00:08:00
true
Phenol (0.518 g, 5.5 mmol) is combined with anhydrous acetonitrile (20 mL) and cesium carbonate (2.3 g, 10 mmol) and allowed to stir at room temperature under nitrogen. To the reaction is added 4-bromomethyl-2-(4-trifluoromethyl-phenyl)-thiazole-5-carboxylic acid ethyl ester (1.97 g, 5.00 mmol). The reaction is monitored by TLC until all of the bromide is consumed. The reaction is diluted with ethyl ether (100 mL), then o.1N NaOH (50 mL) is added. The two phases are separated, then the organic layer is washed with water (50 mL) and brine (50 mL). The organic layer is dried over anhydrous sodium sulfate, then concentrated. The material is further purified using flash chromatography to yield 1.75 g or 86% yield of the product.
CCOC(=O)c1sc(-c2ccc(C(F)(F)F)cc2)nc1COc1ccccc1
null
CCOC(=O)c1sc(-c2ccc(C(F)(F)F)cc2)nc1CBr
Oc1ccccc1
null
[C:1]1([OH:7])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[CH2:14]([O:16][C:17]([C:19]1[S:23][C:22]([C:24]2[CH:29]=[CH:28][C:27]([C:30]([F:33])([F:32])[F:31])=[CH:26][CH:25]=2)=[N:21][C:20]=1[CH2:34]Br)=[O:18])[CH3:15].[Br-]>C(#N)C>[CH2:14]([O:16][C:17]([C:19]1[S:23][C:22]([C:24]2[CH:29]=[CH:28][C:27]([C:30]([F:32])([F:33])[F:31])=[CH:26][CH:25]=2)=[N:21][C:20]=1[CH2:34][O:7][C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)=[O:18])[CH3:15]
null
CC#N
null
null
25
null
86
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
753,699
O=C([O-])[O-]
[Cs+]
null
null
ord_dataset-844a22e1fcab44a5b59c5e2922b2855a
2007-01-01T00:01:00
true
Stir at 50° C. for 10 min. a mixture of 3-(4-pyridinylamino)-1H-indole-2-carboxylic acid (1.27 g, 5 mmol) in DMF (25 mL), and add Cs2CO3 (1.63 g, 5 mmol). After 10 min. add bromomethyl acetate (0.95 g, 6.21 mmol) and one minute thereafter quench into aqueous NH4Cl solution. Extract with EtOAc and wash the extract with aqueous NaHCO3 solution. Dry the extract (MgSO4), filter and concentrate under vacuum to give a solid. Triturate the solid with EtOAc and obtain the title compound as a solid: MS 326(M+H).
CC(=O)OCOC(=O)c1[nH]c2ccccc2c1Nc1ccncc1
null
CC(=O)OCBr
O=C(O)c1[nH]c2ccccc2c1Nc1ccncc1
null
[N:1]1[CH:6]=[CH:5][C:4]([NH:7][C:8]2[C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[NH:10][C:9]=2[C:17]([OH:19])=[O:18])=[CH:3][CH:2]=1.C([O-])([O-])=O.[Cs+].[Cs+].[C:26]([O:29][CH2:30]Br)(=[O:28])[CH3:27]>CN(C=O)C>[C:26]([O:29][CH2:30][O:18][C:17]([C:9]1[NH:10][C:11]2[C:16]([C:8]=1[NH:7][C:4]1[CH:5]=[CH:6][N:1]=[CH:2][CH:3]=1)=[CH:15][CH:14]=[CH:13][CH:12]=2)=[O:19])(=[O:28])[CH3:27]
0.17
CN(C)C=O
null
null
50
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
588,681
[Pt]
null
null
null
ord_dataset-7a74d48eeefd45aba53e7258f3ae067a
2003-01-01T00:04:00
true
N-(4-Chloro-3-methyl-5-isothiazolyl)-4-hydroxy-3-nitrophenylacetamide (374 g, 0.114 mol) was hydrogenated at 15 bar over a 3% w/w platinum on carbon catalyst (15 g) in N,N-dimethylformamide (180 ml). Once the reduction was complete, the catalyst was removed by filtration and the filtrate was evaporated in vacuo to give N-(4-chloro-3-methyl-5-isothiazolyl)-3-amino-4-hydroxyphenylacetamide (26.8 g) as a pale brown solid, which used without further purification in the next step.
Cc1nsc(NC(=O)Cc2ccc(O)c(N)c2)c1Cl
null
Cc1nsc(NC(=O)Cc2ccc(O)c([N+](=O)[O-])c2)c1Cl
null
null
[Cl:1][C:2]1[C:3]([CH3:21])=[N:4][S:5][C:6]=1[NH:7][C:8](=[O:20])[CH2:9][C:10]1[CH:15]=[CH:14][C:13]([OH:16])=[C:12]([N+:17]([O-])=O)[CH:11]=1>[Pt].CN(C)C=O>[Cl:1][C:2]1[C:3]([CH3:21])=[N:4][S:5][C:6]=1[NH:7][C:8](=[O:20])[CH2:9][C:10]1[CH:15]=[CH:14][C:13]([OH:16])=[C:12]([NH2:17])[CH:11]=1
null
CN(C)C=O
null
null
null
null
79
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
979,306
O=[Os](=O)(=O)=O
[Na+]
null
null
ord_dataset-f886e51ba1484c76a94bce1482f1eab9
2010-01-01T00:07:00
true
A commercial 4% w/w solution of osmium tetraoxide (10 mL, 0.82 mmol, 0.005 eq) was added to a stirred mixture of 4-allyloxy-7a-methyl-hexahydro-indene-1,5-dione (36.4 g, 164 mmol), 2,6-lutidine (57.2 mL, 246 mmol, 1.5 eq) and sodium periodate (210.6 g, 492 mmol, 3 eq) in dioxane (900 mL) and water (300 mL) at 0° C. The reaction mixture was then allowed to warm slowly to room temperature, and stirred for 24 h. The reaction mixture was cooled to 0° C., and then filtered through a fritted funnel. DCM (1 L) was used to wash to salt cake, and the filtrate was used to extract the separated aqueous solution (4×250 mL). The combined organic layer was dried with magnesium sulfate. The resulting mixture was filtered, condensed and the resulting residue purified by flash chromatography using 20-90% ethyl acetate in hexane yield the title compound as a light yellow foam.
CC12CCC(=O)C(OCC=O)C1CCC2=O
null
[O-][I+3]([O-])([O-])[O-]
C=CCOC1C(=O)CCC2(C)C(=O)CCC12
null
[CH2:1]([O:4][CH:5]1[C:13](=[O:14])[CH2:12][CH2:11][C:10]2([CH3:15])[CH:6]1[CH2:7][CH2:8][C:9]2=[O:16])[CH:2]=C.N1C(C)=CC=CC=1C.I([O-])(=O)(=O)=[O:26].[Na+]>O1CCOCC1.O.[Os](=O)(=O)(=O)=O>[CH3:15][C:10]12[C:9](=[O:16])[CH2:8][CH2:7][CH:6]1[CH:5]([O:4][CH2:1][CH:2]=[O:26])[C:13](=[O:14])[CH2:12][CH2:11]2
24
C1COCCO1
Cc1cccc(C)n1
O
25
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
910,920
Br
null
null
null
ord_dataset-c663259b80f947e2a8923796fb0e9a6b
2009-01-01T00:10:00
true
To N-[6-(4-fluorobenzyl)-4-methoxy-2-methyl-3,5-dioxo-2,3,5,6,7,8-hexahydro-2,6-naphthyridin-1-yl]-N-methylacetamide (0.070 g, 0.181 mmol) was dissolved in 1 mL glacial acetic acid and 0.75 mL 30% by weight HBr in acetic acid solution was added. The reaction was stirred for 1.5 hours, water was added and the reaction evaporated to dryness under vacuum. The residue was purified on reverse phase and the fractions collected and evaporated. The residue was dissolved in dioxane, from which crystals formed and were collected. The crystals were dried under vacuum with heat to give the product.
CC(=O)N(C)c1c2c(c(O)c(=O)n1C)C(=O)N(Cc1ccc(F)cc1)CC2
null
COc1c2c(c(N(C)C(C)=O)n(C)c1=O)CCN(Cc1ccc(F)cc1)C2=O
null
null
[F:1][C:2]1[CH:28]=[CH:27][C:5]([CH2:6][N:7]2[CH2:16][CH2:15][C:14]3[C:9](=[C:10]([O:24]C)[C:11](=[O:23])[N:12]([CH3:22])[C:13]=3[N:17]([CH3:21])[C:18](=[O:20])[CH3:19])[C:8]2=[O:26])=[CH:4][CH:3]=1.Br.O>C(O)(=O)C>[F:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:6][N:7]2[CH2:16][CH2:15][C:14]3[C:9](=[C:10]([OH:24])[C:11](=[O:23])[N:12]([CH3:22])[C:13]=3[N:17]([CH3:21])[C:18](=[O:20])[CH3:19])[C:8]2=[O:26])=[CH:27][CH:28]=1
1.5
O
CC(=O)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
608,384
O=C([O-])Cl
[K+]
null
null
ord_dataset-73916d628db147c89020b3baac642d48
2003-01-01T00:09:00
true
The preparation was carried out as in Example 2 but using 250 g of ethylene carbonate, 90 g (1.55 mol) of potassium fluoride and 162.6 g (1.0 mol) of cyclohexyl chloroformate. After addition of the chloroformate, stirring of the mixture was continued for 45 minutes at 45° C. Evaporation under vacuum was carried out as above. By distillation under reduced pressure, 122.7 g (84% yield) of cyclohexyl fluoroformate with a boiling point of 55-56° C. at 22 mm Hg were obtained.
O=C(F)OC1CCCCC1
null
O=C(Cl)OC1CCCCC1
[F-]
null
C1(=O)OCCO1.[F-:7].[K+].Cl[C:10]([O:12][CH:13]1[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1)=[O:11].ClC([O-])=O>>[F:7][C:10]([O:12][CH:13]1[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1)=[O:11]
0.75
O=C1OCCO1
null
null
null
null
83.9
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,113,509
CN(C)C(On1nnc2ccccc21)=[N+](C)C
F[P-](F)(F)(F)(F)F
null
null
ord_dataset-375a420ee9b042918ddca20f02df37d3
2011-01-01T00:11:00
true
A mixture of 3-[({[1,6-diethyl-4-(tetrahydro-2H-pyran-4-ylamino)-1H-pyrazolo[3,4-b]pyridin-5-yl]methyl}amino)carbonyl]benzoic acid (69 mg), 1,1-dimethylethyl (2S)-4-{[3′-(aminomethyl)-3-biphenylyl]methyl}-2-methyl-1-piperazinecarboxylate (60 mg), HBTU (68 mg) and diisopropyl ethyl amine (112.5 μL) in DCM (5 mL) and THF (1 mL) were stirred at room temperature overnight. It was concentrated. Separation via CombiFlash then afforded the desired product (33 mg).
CCc1nc2c(cnn2CC)c(NC2CCOCC2)c1CNC(=O)c1cccc(C(=O)NCc2cccc(-c3cccc(CN4CCN(C(=O)OC(C)(C)C)[C@@H](C)C4)c3)c2)c1
null
C[C@H]1CN(Cc2cccc(-c3cccc(CN)c3)c2)CCN1C(=O)OC(C)(C)C
CCc1nc2c(cnn2CC)c(NC2CCOCC2)c1CNC(=O)c1cccc(C(=O)O)c1
null
[CH2:1]([N:3]1[C:7]2=[N:8][C:9]([CH2:32][CH3:33])=[C:10]([CH2:19][NH:20][C:21]([C:23]3[CH:24]=[C:25]([CH:29]=[CH:30][CH:31]=3)[C:26](O)=[O:27])=[O:22])[C:11]([NH:12][CH:13]3[CH2:18][CH2:17][O:16][CH2:15][CH2:14]3)=[C:6]2[CH:5]=[N:4]1)[CH3:2].[NH2:34][CH2:35][C:36]1[CH:37]=[C:38]([C:42]2[CH:47]=[CH:46][CH:45]=[C:44]([CH2:48][N:49]3[CH2:54][CH2:53][N:52]([C:55]([O:57][C:58]([CH3:61])([CH3:60])[CH3:59])=[O:56])[C@@H:51]([CH3:62])[CH2:50]3)[CH:43]=2)[CH:39]=[CH:40][CH:41]=1.CN(C(ON1N=NC2C=CC=CC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F.C(N(C(C)C)CC)(C)C>C(Cl)Cl.C1COCC1>[CH2:1]([N:3]1[C:7]2=[N:8][C:9]([CH2:32][CH3:33])=[C:10]([CH2:19][NH:20][C:21]([C:23]3[CH:24]=[C:25]([C:26]([NH:34][CH2:35][C:36]4[CH:37]=[C:38]([C:42]5[CH:47]=[CH:46][CH:45]=[C:44]([CH2:48][N:49]6[CH2:54][CH2:53][N:52]([C:55]([O:57][C:58]([CH3:61])([CH3:60])[CH3:59])=[O:56])[C@@H:51]([CH3:62])[CH2:50]6)[CH:43]=5)[CH:39]=[CH:40][CH:41]=4)=[O:27])[CH:29]=[CH:30][CH:31]=3)=[O:22])[C:11]([NH:12][CH:13]3[CH2:18][CH2:17][O:16][CH2:15][CH2:14]3)=[C:6]2[CH:5]=[N:4]1)[CH3:2]
8
C1CCOC1
CCN(C(C)C)C(C)C
ClCCl
25
26.2
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,576,890
[N-]=O
[NH-]O
null
null
ord_dataset-9741bb5fd93044078df2a45f45733054
2015-01-01T00:04:00
true
Coupling of (S)-1-benzyl-5-oxopyrrolidine-2-carboxylic acid with 3-amino-2-hydroxy-4-phenylbutanamide was followed by oxidation of the resulting hydroxyamide intermediate to the corresponding ketoamide.
NC(=O)C(=O)C(Cc1ccccc1)NC(=O)[C@@H]1CCC(=O)N1Cc1ccccc1
null
NC(=O)C(O)C(N)Cc1ccccc1
O=C(O)[C@@H]1CCC(=O)N1Cc1ccccc1
null
[CH2:1]([N:8]1[C:12](=[O:13])[CH2:11][CH2:10][C@H:9]1[C:14]([OH:16])=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH2:17][CH:18]([CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[CH:19]([OH:23])[C:20]([NH2:22])=[O:21].O[NH-].O=[N-]>>[NH2:22][C:20](=[O:21])[C:19](=[O:23])[CH:18]([NH:17][C:14]([C@@H:9]1[CH2:10][CH2:11][C:12](=[O:13])[N:8]1[CH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)=[O:16])[CH2:24][C:25]1[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1
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
839,737
Cl
[Li+]
[OH-]
null
ord_dataset-074f86301ec5441ab3b52d902ac06949
2008-01-01T00:09:00
true
To a solution of 5-tert-Butoxycarbonylamino-2-tert-butoxycarbonylmethyl-2H-pyrazole-3-carboxylic acid methyl ester (0.5 gm) dissolved in 25 ml of tetrahydrofuran was added 5 ml of 1M lithium hydroxide. After stirring the reaction mixture at 60 C for 2 hours, 1N hydrochloric acid was added and the product extracted with dichloromethane. The extract was dried over magnesium sulfate, filtered and evaporated to obtain 0.49 gm of title product. ESI M+1=286.
CC(C)(C)OC(=O)Nc1cc(C(=O)O)n(CC(=O)O)n1
null
COC(=O)c1cc(NC(=O)OC(C)(C)C)nn1CC(=O)OC(C)(C)C
null
null
C[O:2][C:3]([C:5]1[N:6]([CH2:18][C:19]([O:21]C(C)(C)C)=[O:20])[N:7]=[C:8]([NH:10][C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH:9]=1)=[O:4].[OH-].[Li+].Cl>O1CCCC1>[C:14]([O:13][C:11]([NH:10][C:8]1[CH:9]=[C:5]([C:3]([OH:4])=[O:2])[N:6]([CH2:18][C:19]([OH:21])=[O:20])[N:7]=1)=[O:12])([CH3:17])([CH3:15])[CH3:16]
2
C1CCOC1
null
null
null
null
122.1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,682,523
null
null
null
null
ord_dataset-3953983e052a4076aa7cc0880b79cb8b
2016-01-01T00:01:00
true
A stirred solution of 2-(2-(2-(2,5-Dichloropyrimidin-4-yl)ethyl)phenyl)propanamide (A30) (0.120 g, 0.370 mmol), tert-butyl 4-(4-amino-1H-pyrazol-1-yl)piperidine-1-carboxylate (0.177 g, 0.666 mmol) in n-butanol (3 mL) and glacial acetic acid (0.004 mL, 0.074 mmol) was stirred at 150° C. in the microwave for 30 minutes. After cooling, the solvent was removed to afford a crude purple oil which was purified by silica gel column chromatography (Combiflash Rf, 0-30% MeOH in DCM) to give the title compound A32 as a red oil (0.090 g, 44% yield). LCMS-C: rt 5.44 min; m/z 554 [M+H]+.
CC(C(N)=O)c1ccccc1CCc1nc(Nc2cnn(C3CCN(C(=O)OC(C)(C)C)CC3)c2)ncc1Cl
null
CC(C)(C)OC(=O)N1CCC(n2cc(N)cn2)CC1
CC(C(N)=O)c1ccccc1CCc1nc(Cl)ncc1Cl
null
Cl[C:2]1[N:7]=[C:6]([CH2:8][CH2:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[CH:16]([CH3:20])[C:17]([NH2:19])=[O:18])[C:5]([Cl:21])=[CH:4][N:3]=1.[NH2:22][C:23]1[CH:24]=[N:25][N:26]([CH:28]2[CH2:33][CH2:32][N:31]([C:34]([O:36][C:37]([CH3:40])([CH3:39])[CH3:38])=[O:35])[CH2:30][CH2:29]2)[CH:27]=1.C(O)(=O)C>C(O)CCC>[NH2:19][C:17](=[O:18])[CH:16]([C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][C:10]=1[CH2:9][CH2:8][C:6]1[C:5]([Cl:21])=[CH:4][N:3]=[C:2]([NH:22][C:23]2[CH:24]=[N:25][N:26]([CH:28]3[CH2:29][CH2:30][N:31]([C:34]([O:36][C:37]([CH3:40])([CH3:39])[CH3:38])=[O:35])[CH2:32][CH2:33]3)[CH:27]=2)[N:7]=1)[CH3:20]
null
CCCCO
CC(=O)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
391,988
null
null
null
null
ord_dataset-4bc8addcf9cf4845817557760d62d5b5
1998-01-01T00:02:00
true
Water (9 ml) and N,N'-dimethylethylenediamine (0.8 ml, 7.7 mmol) were added to 6-amino-4,5-dichloro-2-methyl-3(2H)-pyridazinone (500 mg, 2.6 mmol) as described in Chemical Pharmaceutical Bulletin, 30, 832 (1982), and the mixture was refluxed under heating for 3 hours. The reaction mixture was concentrated, added with chloroform, washed with water and brine and dried over anhydrous sodium sulfate. The solvent was distilled away and the residue obtained was subjected to silica gel column chromatography (chloroform:methanol=40:1) to give 448 mg of 8-amino-1,2,3,4-tetrahydro-1,4,6-trimethylpyrazino[2,3-d]pyridazin-5(6H)-one.
CN1CCN(C)c2c1c(N)nn(C)c2=O
null
Cn1nc(N)c(Cl)c(Cl)c1=O
CNCCNC
null
O.[CH3:2][NH:3][CH2:4][CH2:5][NH:6][CH3:7].[NH2:8][C:9]1[C:10](Cl)=[C:11](Cl)[C:12](=[O:16])[N:13]([CH3:15])[N:14]=1.C(Cl)(Cl)Cl>CO>[NH2:8][C:9]1[C:10]2[N:3]([CH3:2])[CH2:4][CH2:5][N:6]([CH3:7])[C:11]=2[C:12](=[O:16])[N:13]([CH3:15])[N:14]=1
null
CO
ClC(Cl)Cl
O
null
null
82.3
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,203,456
null
null
null
null
ord_dataset-fb72428f30234761b4216139dc228d0c
2012-01-01T00:09:00
true
Intermediate 111 was coupled with 2-(3,5-difluoro-phenyl)-ethylamine following procedure F. The resulting product was deprotected following procedure G2. LC-MS showed the product had the expected M+H+ of 425. 1H NMR (Varian 300 MHz, CD3OD, shifts relative to the solvent peak at 3.3 ppm) δ 8.72 (s, 1H), 8.36 (t, 2H), 7.97 (d, 1H), 7.73 (d, 1H), 7.69 (d, 1H), 7.01 (d, 2H), 6.72 (s, 1H), 4.43 (d, 1H), 4.05 (m, 3H), 3.55 (m, 6H), 3.39 (m, 1H), 3.06 (t, 2H), 1.77 (d, 3H).
C[C@@H]1CNCCN1Cc1cccc(-c2ccnc(NCCc3cc(F)cc(F)c3)n2)c1
null
CC1CN(C(=O)OC(C)(C)C)CCN1Cc1cccc(-c2ccnc(Cl)n2)c1
NCCc1cc(F)cc(F)c1
null
C(OC([N:8]1[CH2:13][CH2:12][N:11]([CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[C:17]([C:21]3[CH:26]=[CH:25][N:24]=[C:23](Cl)[N:22]=3)[CH:16]=2)[CH:10]([CH3:28])[CH2:9]1)=O)(C)(C)C.[F:29][C:30]1[CH:31]=[C:32]([CH2:37][CH2:38][NH2:39])[CH:33]=[C:34]([F:36])[CH:35]=1>>[F:29][C:30]1[CH:31]=[C:32]([CH2:37][CH2:38][NH:39][C:23]2[N:22]=[C:21]([C:17]3[CH:18]=[CH:19][CH:20]=[C:15]([CH2:14][N:11]4[CH2:12][CH2:13][NH:8][CH2:9][C@H:10]4[CH3:28])[CH:16]=3)[CH:26]=[CH:25][N:24]=2)[CH:33]=[C:34]([F:36])[CH:35]=1
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
274,081
c1ccc(P(c2ccccc2)c2ccccc2)cc1
null
null
null
ord_dataset-ee287d49cb8642e59ae9c3951f746312
1993-01-01T00:08:00
true
A flask was charged with (S)-1-[(tert-Butyldiphenylsilyl)oxy]-3-butyn-2-ol (1) (1.30 g, 4 mmol), triphenylphosphine (2.52 g, 9.60 mmol), THF (30 mL), pyridine (360 mg, 4.56 mmol). To this mixture was added carbon tetrabromide (1.53 g, 4.60 mmol) in THF (10 ml) over a 5 minute period. The resulting reaction mixture was stirred for 45 minutes. Hexanes (50 mL) was added, and the mixture was filtered and concentrated in vacuo. The residue was taken up into hexanes (50 mL), washed with 1 M HCl (40 mL), saturated NaCl (40 mL). The organic extracts were dried (MgSO4) and concentrated by rotary evaporation to yield a yellow oil. Purification by flash silica gel chromatography (98:02 hexane/EtOAc) afforded (R)-2-bromo-1-[tert-butyldiphenylsilyloxy]-3-butyne (4) (1.50 g, 97%) as a colorless oil (Note: this material is unstable and should be used immediately): Rf 0.74 (90:10 hexane/EtOAc); IR (neat) 3308, 1437, 1112, 701 cm-1 ; 1H NMR (CDCl3) δ 7.70 (m, 4 H), 7.42 (m, 6 H), 4.46 (dt, J1 =6.66 Hz, J2 =2.36 Hz, 1 H), 3.91 (ddd, J1 =10.7 Hz, J2 =6.32, Hz, J3 =3.78 Hz, 2H), 2.59 (d, J=2.4 Hz, 2 H), 1.08 (m, 9H); 13C NMR (CDCl3); δ 135.8, 132.8, 129.6, 127.6, 80.3, 75.6, 67.5, 36.2, 26.8, 19.3. ##STR19##
C#C[C@@H](Br)CO[Si](c1ccccc1)(c1ccccc1)C(C)(C)C
null
C#C[C@H](O)CO[Si](c1ccccc1)(c1ccccc1)C(C)(C)C
BrC(Br)(Br)Br
null
[Si:1]([O:18][CH2:19][C@@H:20](O)[C:21]#[CH:22])([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N1C=CC=CC=1.C(Br)(Br)(Br)[Br:50]>C1COCC1>[Br:50][C@H:20]([C:21]#[CH:22])[CH2:19][O:18][Si:1]([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
0.75
C1CCOC1
c1ccncc1
null
null
null
96.8
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,348,892
null
null
null
null
ord_dataset-6034127657614f02860ed057b62b882e
2013-01-01T00:10:00
true
In an analogous procedure to Example 651, part c, 7-Amino-5,5-dimethyl-1,3,4,5-tetrahydro-benzo[b]azepin-2-one and 3-(2,5-Dichloro-pyrimidin-4-ylamino)-N-methyl-benzamide were combined to yield 3-[5-Chloro-2-(5,5-dimethyl-2-oxo-2,3,4,5-tetrahydro-1H-benzo[b]azepin-7-ylamino)-pyrimidin-4-ylamino]-N-methyl-benzamide (19.47 mg, 19% yield) as a white amorphous solid. 1H-NMR (CDCl3) δ 8.10 (s, 1H), 8.01 (s, 1H), 7.75 (d, J=7.8 Hz, 1H), 7.58 (d, J=8.60 Hz, 1H), 7.48 (m, 1H), 7.38 (m, 1H), 7.38 (m, 1H), 7.32 (s, 1H), 7.17 (d, J=14.9 Hz, 1H), 7.07 (s, 1H), 6.81 (d, J=7.8 Hz, 1H), 6.06 (br s, 1H), 2.97 (s, 3H), 2.37 (m, 2H), 2.07 (m, 2H), 1.33 (s, 6H). LC/MS (ESI+)=465 (M+H). MP=184.5° C.
CNC(=O)c1cccc(Nc2nc(Nc3ccc4c(c3)C(C)(C)CCC(=O)N4)ncc2Cl)c1
null
CNC(=O)c1cccc(Nc2nc(Cl)ncc2Cl)c1
CC1(C)CCC(=O)Nc2ccc(N)cc21
null
[NH2:1][C:2]1[CH:15]=[CH:14][C:5]2[NH:6][C:7](=[O:13])[CH2:8][CH2:9][C:10]([CH3:12])([CH3:11])[C:4]=2[CH:3]=1.Cl[C:17]1[N:22]=[C:21]([NH:23][C:24]2[CH:25]=[C:26]([CH:31]=[CH:32][CH:33]=2)[C:27]([NH:29][CH3:30])=[O:28])[C:20]([Cl:34])=[CH:19][N:18]=1>>[Cl:34][C:20]1[C:21]([NH:23][C:24]2[CH:25]=[C:26]([CH:31]=[CH:32][CH:33]=2)[C:27]([NH:29][CH3:30])=[O:28])=[N:22][C:17]([NH:1][C:2]2[CH:15]=[CH:14][C:5]3[NH:6][C:7](=[O:13])[CH2:8][CH2:9][C:10]([CH3:12])([CH3:11])[C:4]=3[CH:3]=2)=[N:18][CH:19]=1
null
null
null
null
null
19
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
173,940
[K+]
[OH-]
null
null
ord_dataset-3844acbccc714c04ab757ec4fca10bd0
1988-01-01T00:06:00
true
To a stirred warm solution of 58.0 g (0.88 mol) of potassium hydroxide (85%) in 500 ml of methanol was added portionwise 81.7 g (0.21 mol) of 1,3,4,5-tetrahydro-3-(methoxycarbonyl)-4-(methoxyphenyl)-6-(trifluoromethyl)-2H-1-benzazepin-2-one - most of the solid dissolved. The mixture was diluted with 100 ml of dioxane and the resulting solution was refluxed for 6 hours. After standing overnight at room temperature, about 50% of the solvent was removed on a rotary evaporator and the residue was diluted with 4 liters of cold water. The insoluble material was filtered and dried (10 g) and the filtrate was cooled and treated portionwise with 270 ml of acetic acid to give a colorless granular solid. The latter was filtered, washed with cold water and dried in a desicator; yield 69.0 g, melting point 179°-181° C. (s. 128° C.).
COc1ccccc1C1Cc2c(cccc2C(F)(F)F)NC(=O)C1C(=O)O
null
COC(=O)C1C(=O)Nc2cccc(C(F)(F)F)c2CC1c1ccccc1OC
null
null
[OH-].[K+].C[O:4][C:5]([CH:7]1[CH:13]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[O:20][CH3:21])[CH2:12][C:11]2[C:22]([C:26]([F:29])([F:28])[F:27])=[CH:23][CH:24]=[CH:25][C:10]=2[NH:9][C:8]1=[O:30])=[O:6]>CO.O1CCOCC1>[C:5]([CH:7]1[CH:13]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[O:20][CH3:21])[CH2:12][C:11]2[C:22]([C:26]([F:28])([F:29])[F:27])=[CH:23][CH:24]=[CH:25][C:10]=2[NH:9][C:8]1=[O:30])([OH:6])=[O:4]
8
CO
C1COCCO1
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
830,492
null
null
null
null
ord_dataset-47bd90bf5ec74fcd99ce250a56e18c8f
2008-01-01T00:07:00
true
4-{3-Hydroxy-1-[(methylamino)methyl]propyl}benzonitrile (0.55 g, 2.69 mmol) and DIPEA (0.77 g, 5.9 mmol) were dissolved in CH2Cl2 (5 mL). 3-Cyano-1-naphthoyl chloride (sse Method 11; 0.58 g, 2.69 mmol) was added in portions with stirring and cooling (external ice-bath). The mixture was stirred for 2 h with cooling and then diluted with CH2Cl2 (10 mL). The solution was washed twice with water, twice with a saturated aqueous KHSO4 solution and then with brine. The solvent was removed by evaporation and the residue flash chromatographed on silica gel (CH2Cl2-MeOH, 9:1). There was obtained 0.70 g (67%) of 3-cyano-N-[2-(4-cyanophenyl)-4-hydroxybutyl]-N-methyl-1-naphthamide as a white solid. 1H NMR (400 MHz, CDCl3): 1.4-2.5 (cm, 2H), 2.6 (s, 3H), 3.1-4.6 (cm, 6H), 6.4-7.8 (cm, 8H), 7.9 (d, 1H), 8.2 (s, 1H); LCMS: m/z 384 (M+1)+.
CN(CC(CCO)c1ccc(C#N)cc1)C(=O)c1cc(C#N)cc2ccccc12
null
N#Cc1cc(C(=O)Cl)c2ccccc2c1
CNCC(CCO)c1ccc(C#N)cc1
null
[OH:1][CH2:2][CH2:3][CH:4]([C:8]1[CH:15]=[CH:14][C:11]([C:12]#[N:13])=[CH:10][CH:9]=1)[CH2:5][NH:6][CH3:7].CCN(C(C)C)C(C)C.[C:25]([C:27]1[CH:28]=[C:29]([C:37](Cl)=[O:38])[C:30]2[C:35]([CH:36]=1)=[CH:34][CH:33]=[CH:32][CH:31]=2)#[N:26]>C(Cl)Cl>[C:25]([C:27]1[CH:28]=[C:29]([C:37]([N:6]([CH2:5][CH:4]([C:8]2[CH:15]=[CH:14][C:11]([C:12]#[N:13])=[CH:10][CH:9]=2)[CH2:3][CH2:2][OH:1])[CH3:7])=[O:38])[C:30]2[C:35]([CH:36]=1)=[CH:34][CH:33]=[CH:32][CH:31]=2)#[N:26]
null
ClCCl
CCN(C(C)C)C(C)C
null
null
null
67.9
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,703,575
O=c1[nH]nc(CCc2ccccc2)cc1O
null
null
null
ord_dataset-54347fcace774f89850681d6dec8009f
2016-01-01T00:03:00
true
Prepared as described for 4-hydroxy-6-(2-phenylethyl)pyridazin-3(2H)-one (Example 1) from 3,4-bis(benzyloxy)-6-[(E)-2-[2,4-bis(trifluoromethyl)phenyl]-ethenyl]pyridazine (Intermediate 72) in 31% yield.
O=c1[nH]nc(CCc2ccc(C(F)(F)F)cc2C(F)(F)F)cc1O
null
FC(F)(F)c1ccc(/C=C/c2cc(OCc3ccccc3)c(OCc3ccccc3)nn2)c(C(F)(F)F)c1
null
null
OC1C(=O)NN=C(CCC2C=CC=CC=2)C=1.C([O:24][C:25]1[N:26]=[N:27][C:28](/[CH:39]=[CH:40]/[C:41]2[CH:46]=[CH:45][C:44]([C:47]([F:50])([F:49])[F:48])=[CH:43][C:42]=2[C:51]([F:54])([F:53])[F:52])=[CH:29][C:30]=1[O:31]CC1C=CC=CC=1)C1C=CC=CC=1>>[F:54][C:51]([F:52])([F:53])[C:42]1[CH:43]=[C:44]([C:47]([F:48])([F:50])[F:49])[CH:45]=[CH:46][C:41]=1[CH2:40][CH2:39][C:28]1[CH:29]=[C:30]([OH:31])[C:25](=[O:24])[NH:26][N:27]=1
null
null
null
null
null
null
31
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
526,007
null
null
null
null
ord_dataset-293186f5c9b441cab57f03cd3a18ac26
2001-01-01T00:11:00
true
A mixture of 4-(2,3-diaminobenzoyl)amino-3-methoxy-N-methyl-N-[4-methyl-2-[5-(4-methylpiperazin-1-yl)carbonylpent-1-yloxy]phenyl]benzamide (150 mg) and diphenyl N-sulfamoylcarbonimidate (85 mg) in dichloromethane (8 ml) was refluxed for 24 hours under nitrogen. The reaction mixture was poured into water and extracted with chloroform. The organic layer was washed with water, driver over magnesium sulfate and evaporated in vacuo. The residue was purified by preparative thin-layer chromatography (chloroform:methanol=10:1/chloroform:methanol=6:1) to give 3-methoxy-N-methyl-N-[4-methyl-2-[5-(4-methylpiperazin-1-yl)carbonylpent-1-yloxy]phenyl]-4-(2-sulfamoylamino-1H-benzimidazol-4-yl)carbonylaminobenzamide (38 mg).
COc1cc(C(=O)N(C)c2ccc(C)cc2OCCCCCC(=O)N2CCN(C)CC2)ccc1NC(=O)c1cccc2[nH]c(NS(N)(=O)=O)nc12
null
NS(=O)(=O)N=C(Oc1ccccc1)Oc1ccccc1
COc1cc(C(=O)N(C)c2ccc(C)cc2OCCCCCC(=O)N2CCN(C)CC2)ccc1NC(=O)c1cccc(N)c1N
null
[NH2:1][C:2]1[C:44]([NH2:45])=[CH:43][CH:42]=[CH:41][C:3]=1[C:4]([NH:6][C:7]1[CH:38]=[CH:37][C:10]([C:11]([N:13]([CH3:36])[C:14]2[CH:19]=[CH:18][C:17]([CH3:20])=[CH:16][C:15]=2[O:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][C:27]([N:29]2[CH2:34][CH2:33][N:32]([CH3:35])[CH2:31][CH2:30]2)=[O:28])=[O:12])=[CH:9][C:8]=1[O:39][CH3:40])=[O:5].[S:46]([N:50]=[C:51](OC1C=CC=CC=1)OC1C=CC=CC=1)(=[O:49])(=[O:48])[NH2:47].O>ClCCl>[CH3:40][O:39][C:8]1[CH:9]=[C:10]([CH:37]=[CH:38][C:7]=1[NH:6][C:4]([C:3]1[C:2]2[N:1]=[C:51]([NH:50][S:46](=[O:49])(=[O:48])[NH2:47])[NH:45][C:44]=2[CH:43]=[CH:42][CH:41]=1)=[O:5])[C:11]([N:13]([CH3:36])[C:14]1[CH:19]=[CH:18][C:17]([CH3:20])=[CH:16][C:15]=1[O:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][C:27]([N:29]1[CH2:34][CH2:33][N:32]([CH3:35])[CH2:31][CH2:30]1)=[O:28])=[O:12]
null
ClCCl
O
null
null
null
21.7
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
882,795
null
null
null
null
ord_dataset-3592bd645cd143ee8274cd0d834ae581
2009-01-01T00:05:00
true
To a solution of Example 139 (40 mg, 0.078 mmol) in dioxane (3 mL) was added a solution of 6N aqueous hydrochloric acid (3 mL). The mixture was heated at 65 C for 3 hours, and the solvent removed in vacuo. The resultant residue was purified by reverse phase preparative HPLC on a Waters Symmetry C8 column (25 mm×100 mm, 7 μm particle size) using a gradient of 10% to 100% acetonitrile/0.1% trifluoroacetic acid in water over 8 minutes (10 minutes run time) at a flow rate of 40 mL/min to provide the title (4 mg, 9%). MS (ESI) m/z=550 (M−H)+. 1H NMR (300 MHz, DMSO-d6): δ 0.96 (m, 1H), 1.24 (m, 1H), 1.40 (s, 3H), 1.42 (s, 3H), 1.60 (s, 3H), 2.29 (m, 1H), 2.42 (m, 1H), 3.08 (s, 3H), 7.56 (m, 3H), 7.73 (m, 3H), 8.16 (d, J=7.4 Hz, 1H), 10.24 (s, 1H), 13.81 (s, 1H).
CC(C)(Cl)CCC1(C)C(=O)C(C2=NS(=O)(=O)c3cc(NS(C)(=O)=O)ccc3N2)=C(O)c2ccccc21
null
CC(C)=CCC1(C)C(=O)C(C2=NS(=O)(=O)c3cc(NS(C)(=O)=O)ccc3N2)=C(O)c2ccccc21
Cl
null
[OH:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([CH3:17])([CH2:12][CH:13]=[C:14]([CH3:16])[CH3:15])[C:4](=[O:18])[C:3]=1[C:19]1[NH:24][C:23]2[CH:25]=[CH:26][C:27]([NH:29][S:30]([CH3:33])(=[O:32])=[O:31])=[CH:28][C:22]=2[S:21](=[O:35])(=[O:34])[N:20]=1.[ClH:36]>O1CCOCC1>[Cl:36][C:14]([CH3:15])([CH3:16])[CH2:13][CH2:12][C:5]1([CH3:17])[C:6]2[C:11](=[CH:10][CH:9]=[CH:8][CH:7]=2)[C:2]([OH:1])=[C:3]([C:19]2[NH:24][C:23]3[CH:25]=[CH:26][C:27]([NH:29][S:30]([CH3:33])(=[O:32])=[O:31])=[CH:28][C:22]=3[S:21](=[O:35])(=[O:34])[N:20]=2)[C:4]1=[O:18]
null
C1COCCO1
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
563,936
[Pd]
null
null
null
ord_dataset-7c28974b7fcf4c9c86d5f2a42ba328a2
2002-01-01T00:09:00
true
To a solution of ethyl 4-nitromesitylenate (7.7 g) in ethyl acetate (300 ml) was added 10% palladium-carbon (3 g) and the mixture was stirred for 3.5 hr under a hydrogen atmosphere. The catalyst was filtered off from the reaction mixture and the filtrate was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated to give the title compound (6.6 g) as pale-brown crystals.
CCOC(=O)c1cc(C)c(N)c(C)c1
null
CCOC(=O)c1cc(C)c([N+](=O)[O-])c(C)c1
null
null
[N+:1]([C:4]1[C:9]([CH3:10])=[CH:8][C:7]([C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:6][C:5]=1[CH3:16])([O-])=O>C(OCC)(=O)C.[C].[Pd]>[NH2:1][C:4]1[C:9]([CH3:10])=[CH:8][C:7]([C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:6][C:5]=1[CH3:16]
3.5
CCOC(C)=O
null
null
null
null
99
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,283,230
O=C([O-])O
[Na+]
null
null
ord_dataset-d5c54236ecd94d61aaa071461bcfc426
2013-01-01T00:04:00
true
A solution of 1-[(1-methylcyclopropyl)sulfonyl]-3-[(triethylsilyl)oxy]azetidine (0.125 g, 0.41 mmol) in tetrahydrofuran (3 mL), water (1 mL) and acetic acid (1 mL) was stirred at room temperature for four hours. The mixture was neutralized by pouring into a solution of sodium bicarbonate. The product was extracted with ethyl acetate, the extracts were washed with brine, dried over sodium sulfate, decanted and concentrated to afford product, used without further purification (64 mg, 82%).
CC1(S(=O)(=O)N2CC(O)C2)CC1
null
CC[Si](CC)(CC)OC1CN(S(=O)(=O)C2(C)CC2)C1
null
null
[CH3:1][C:2]1([S:5]([N:8]2[CH2:11][CH:10]([O:12][Si](CC)(CC)CC)[CH2:9]2)(=[O:7])=[O:6])[CH2:4][CH2:3]1.C(=O)(O)[O-].[Na+]>O1CCCC1.O.C(O)(=O)C>[CH3:1][C:2]1([S:5]([N:8]2[CH2:9][CH:10]([OH:12])[CH2:11]2)(=[O:7])=[O:6])[CH2:4][CH2:3]1
null
CC(=O)O
C1CCOC1
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
57,321
Cl
[K+]
[OH-]
null
ord_dataset-56a7c92b497c48c59951f153285b4adc
1979-01-01T00:07:00
true
2-Hydroxy-3,6-dichlorobenzoic acid (44.4 g) is dissolved in a solution of potassium hydroxide (11.2 g, 0.2 mole) and water (100 ml). The solution is heated to reflux (about 100° C.) and stirred vigorously while dimethyl sulfate (63.1 g, 0.5 mole) is added dropwise. The reaction mixture is then treated with a solution of potassium hydroxide (14.0 g, 0.25 mole) in 25.0 ml of water and refluxed for an additional 2 hours. The reaction mixture is then cooled and acidified to Congo red with hydrochloric acid to precipitate the desired 2-methoxy-3,6-dichlorobenzoic acid.
COc1c(Cl)ccc(Cl)c1C(=O)O
null
COS(=O)(=O)OC
O=C(O)c1c(Cl)ccc(Cl)c1O
null
[OH:1][C:2]1[C:10]([Cl:11])=[CH:9][CH:8]=[C:7]([Cl:12])[C:3]=1[C:4]([OH:6])=[O:5].[OH-].[K+].S(OC)(O[CH3:19])(=O)=O.Cl>O>[CH3:19][O:1][C:2]1[C:10]([Cl:11])=[CH:9][CH:8]=[C:7]([Cl:12])[C:3]=1[C:4]([OH:6])=[O:5]
null
O
null
null
100
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,495,752
[Cs+]
null
null
null
ord_dataset-366bdd9ee72d474cbe6f3f9e54dd96d2
2014-01-01T00:10:00
true
1-Bromopropane (192 mg, 1.57 mmol) was added to a solution of 2-chloro-5H-pyrrolo[3,2-d]pyrimidine (200 mg, 1.31 mmol) in DMF (15 mL) followed by cesium carbonate (0.855 g, 2.63 mmol), and the mixture was stirred at 70° C. for 0.5 h. Insoluble solids were filtered off, filtrate was concentrated and partitioned between ethyl acetate and water. Organic layer was separated, washed with brine, dried over sodium sulphate and filtered. The filtrate was concentrated in vacuo to afford title compound (0.22 g, 86%) as an oil. 1H NMR (300 MHz, CDCl3): δ 7.59 (d, J=8.7 Hz, 1H), 7.34 (d, J=3.3 Hz, 1H), 7.10 (d, J=8.4 Hz, 1H), 6.62 (d, J=3.6 Hz, 1H), 4.07 (t, J=6.9 Hz, 2H), 1.86 (m, 2H), 0.91 (t, J=7.5 Hz, 3H).
CCCn1ccc2nc(Cl)ccc21
null
Clc1ncc2[nH]ccc2n1
O=C([O-])[O-]
CCCBr
Br[CH2:2][CH2:3][CH3:4].[Cl:5][C:6]1N=[CH:8][C:9]2[NH:14][CH:13]=[CH:12][C:10]=2[N:11]=1.[C:15](=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C>[Cl:5][C:6]1[N:11]=[C:10]2[CH:12]=[CH:13][N:14]([CH2:2][CH2:3][CH3:4])[C:9]2=[CH:8][CH:15]=1
0.5
CN(C)C=O
null
null
70
null
86.3
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,549,652
null
null
null
null
ord_dataset-cac8df8aff894288876df4e093c9877f
2015-01-01T00:02:00
true
4.6 g of methyl 6-chloronicotinate and 40.5 ml of N-benzylethylenediamine are heated at 135° C. for 6 hours in a round-bottomed flask. The resulting product is poured into water and extraction is carried out with ethyl acetate. The resulting product is dried and evaporated under vacuum; the crude product thus obtained is purified by flash chromatography.
COC(=O)c1ccc(NCCNCc2ccccc2)nc1
null
NCCNCc1ccccc1
COC(=O)c1ccc(Cl)nc1
null
Cl[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][N:3]=1.[CH2:12]([NH:19][CH2:20][CH2:21][NH2:22])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.O>C(OCC)(=O)C>[CH3:9][O:8][C:6](=[O:7])[C:5]1[CH:10]=[CH:11][C:2]([NH:22][CH2:21][CH2:20][NH:19][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[N:3][CH:4]=1
null
CCOC(C)=O
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
1,649,591
null
null
null
null
ord_dataset-bcc0b01d4f58457a8733b10a099f43ba
2015-01-01T00:10:00
true
To a solution of (S)-tert-butyl pyrrolidin-3-ylcarbamate (0.50 g, 2.7 mmol, 1 eq) and diisopropylamine (0.66 mL, 3.8 mmol, 1.4 eq) in 0.2 mL of NMP was added 4-chloropyrazolo[1,5-a]pyrazine (0.47 mL, 3.1 mmol, 1.1 eq). After stirring for 1 h at room temperature, the mixture was concentrated and purified by silica gel column chromatography (100% EtOAc) to afford (S)-tert-butyl (1-(pyrazolo[1,5-a]pyrazin-4-yl)pyrrolidin-3-yl)carbamate (0.740 g, 2.4 mmol, 91%).
CC(C)(C)OC(=O)N[C@H]1CCN(c2nccn3nccc23)C1
null
CC(C)(C)OC(=O)N[C@H]1CCNC1
Clc1nccn2nccc12
null
[NH:1]1[CH2:5][CH2:4][C@H:3]([NH:6][C:7](=[O:13])[O:8][C:9]([CH3:12])([CH3:11])[CH3:10])[CH2:2]1.C(NC(C)C)(C)C.Cl[C:22]1[C:23]2[N:24]([N:28]=[CH:29][CH:30]=2)[CH:25]=[CH:26][N:27]=1>CN1C(=O)CCC1>[N:28]1[N:24]2[CH:25]=[CH:26][N:27]=[C:22]([N:1]3[CH2:5][CH2:4][C@H:3]([NH:6][C:7](=[O:13])[O:8][C:9]([CH3:10])([CH3:12])[CH3:11])[CH2:2]3)[C:23]2=[CH:30][CH:29]=1
1
CC(C)NC(C)C
CN1CCCC1=O
null
25
null
88.9
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,174,947
[BH3-]C#N
[Na+]
null
null
ord_dataset-0f9d2dbe929a45c3892ae75e81e99443
2012-01-01T00:06:00
true
A solution of 1-methyl-2-formylbenzimidazole (1 g) in methanol (27 mL) and acetic acid (0.54 mL) was treated with aminoacetaldehyde diethylacetal (0.9 g, 1 equivalent) and NaCNBH3 (0.85 g, 2 equivalents) at 25° C., stirred for 1 hour. The mixture was partitioned between water and ethyl acetate. The organic layer was separated, washed sequentially with saturated NaHCO3 and brine, and concentrated. The residue was chromatographed on silica gel, eluting with 8% methanol/dichloromethane to give 1.2 g (64%) of the title compound.
COC(CNCc1nc2ccccc2n1C)OC
null
Cn1c(C=O)nc2ccccc21
CCOC(CN)OCC
null
[CH3:1][N:2]1[C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][C:5]=2[N:4]=[C:3]1[CH:11]=O.[CH2:13]([O:15][CH:16]([O:19][CH2:20]C)[CH2:17][NH2:18])C.[BH3-]C#N.[Na+]>CO.C(O)(=O)C>[CH3:13][O:15][CH:16]([O:19][CH3:20])[CH2:17][NH:18][CH2:11][C:3]1[N:2]([CH3:1])[C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][C:5]=2[N:4]=1
1
CC(=O)O
CO
null
null
null
77.1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
144,326
null
null
null
null
ord_dataset-d6cdba90760a47779a36ece5962905eb
1986-01-01T00:06:00
true
6-Amino-3,4-dihydrocarbostyril (1 g) is suspended in benzene (20 ml), and thereto is added dropwise a solution of N,N-dimethylcarbamoyl chloride (0.86 ml) in benzene (10 ml) at room temperature. The mixture is reacted at 50° C. for 3 hours, and thereto is added triethylamine (0.86 ml), and the mixture is further reacted at 50° to 60° C. for 5 hours. After the reaction, benzene is distilled off under reduced pressure, and water is added to the residue. The resulting precipitate is separated by filtration and washed with water. The crystal thus obtained is purified by silica gel column chromatography (solvent; chloroform:methanol=100:1) and then recrystallized from methanol-diethyl ether to give 6-(3,3-dimethylureido)-3,4-dihydrocarbostyril (0.6 g), as colorless prisms, m.p. 181°-183° C.
CN(C)C(=O)Nc1ccc2c(c1)CCC(=O)N2
null
CN(C)C(=O)Cl
Nc1ccc2c(c1)CCC(=O)N2
null
[NH2:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[NH:8][C:7](=[O:12])[CH2:6][CH2:5]2.[CH3:13][N:14]([CH3:18])[C:15](Cl)=[O:16].C(N(CC)CC)C>C1C=CC=CC=1>[CH3:13][N:14]([CH3:18])[C:15](=[O:16])[NH:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[NH:8][C:7](=[O:12])[CH2:6][CH2:5]2
null
CCN(CC)CC
c1ccccc1
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
1,045,453
null
null
null
null
ord_dataset-dd320ded4b3f4764af39de99491533f7
2011-01-01T00:04:00
true
The above mentioned tert-butyl (S)-1-(5-(3-fluoro-4-nitrophenyl)-1,3,4-thiadiazol-2-yl-boc-amino)-3-(4-(trifluoromethyl)phenyl)propan-2-ylcarbamate was dissolved in 20 mL 2M THF solution of methanamine (20 mL, 40 mmol) in a microwave heating tube. The tube was heated at 120° C. for 10 minutes. The THF solution was mixed with 200 mL EtOAc. The organic phase was washed with water, twice with saturated aqueous ammonium sulfate twice, and dried over sodium sulfate. After removing the solvent, the product was used directly in the next step.
CNc1cc(-c2nnc(N(C[C@H](Cc3ccc(C(F)(F)F)cc3)NC(=O)OC(C)(C)C)C(=O)OC(C)(C)C)s2)ccc1[N+](=O)[O-]
null
CN
CC(C)(C)OC(=O)N[C@@H](Cc1ccc(C(F)(F)F)cc1)CN(C(=O)OC(C)(C)C)c1nnc(-c2ccc([N+](=O)[O-])c(F)c2)s1
null
F[C:2]1[CH:3]=[C:4]([C:11]2[S:15][C:14]([N:16]([C:38]([O:40][C:41]([CH3:44])([CH3:43])[CH3:42])=[O:39])[CH2:17][C@@H:18]([NH:30][C:31](=[O:37])[O:32][C:33]([CH3:36])([CH3:35])[CH3:34])[CH2:19][C:20]3[CH:25]=[CH:24][C:23]([C:26]([F:29])([F:28])[F:27])=[CH:22][CH:21]=3)=[N:13][N:12]=2)[CH:5]=[CH:6][C:7]=1[N+:8]([O-:10])=[O:9].[CH3:45][NH2:46].CCOC(C)=O>C1COCC1>[CH3:45][NH:46][C:2]1[CH:3]=[C:4]([C:11]2[S:15][C:14]([N:16]([C:38]([O:40][C:41]([CH3:44])([CH3:42])[CH3:43])=[O:39])[CH2:17][C@@H:18]([NH:30][C:31](=[O:37])[O:32][C:33]([CH3:36])([CH3:34])[CH3:35])[CH2:19][C:20]3[CH:21]=[CH:22][C:23]([C:26]([F:29])([F:27])[F:28])=[CH:24][CH:25]=3)=[N:13][N:12]=2)[CH:5]=[CH:6][C:7]=1[N+:8]([O-:10])=[O:9]
null
CCOC(C)=O
C1CCOC1
null
120
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
880,434
O=C(C(F)(F)F)C(F)(F)F
[F-]
[K+]
null
ord_dataset-3592bd645cd143ee8274cd0d834ae581
2009-01-01T00:05:00
true
CH2═C(CF3)CF2OSO2F (10 g, 0.041 mole) is added at 20° C. to (CF3)2CFOK, prepared from freshly dried potassium fluoride (KF) (2.4 g, 0.041 mole), hexafluoroacetone (HFA) (9.3 g, 0.056 mole) and dry diglyme (10 ml). The reaction mixture is agitated for 2 hours and then poured into water, the organic layer separating. The organic layer is washed with dilute hydrochloric acid, then sodium bicarbonate solution, then water, after which it is dried over magnesium sulfate (MgSO4). Distillation of the reaction mixture gives CH2═C(CF3)CF2OCF(CF3)2 (10.2 g, 75% yield, b.pt. 87-88° C.).
C=C(C(F)(F)F)C(F)(F)OC(F)(C(F)(F)F)C(F)(F)F
null
C=C(C(F)(F)F)C(F)(F)OS(=O)(=O)F
FC(F)(F)C(F)(O[K])C(F)(F)F
null
[CH2:1]=[C:2]([C:7]([O:10]S(F)(=O)=O)([F:9])[F:8])[C:3]([F:6])([F:5])[F:4].[C:15](O[K])([C:21]([F:24])([F:23])[F:22])([C:17]([F:20])([F:19])[F:18])[F:16].[F-].[K+].FC(F)(F)C(C(F)(F)F)=O>O.COCCOCCOC>[CH2:1]=[C:2]([C:7]([O:10][C:15]([C:21]([F:24])([F:23])[F:22])([C:17]([F:20])([F:19])[F:18])[F:16])([F:9])[F:8])[C:3]([F:6])([F:5])[F:4]
2
O
COCCOCCOC
null
null
75
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,070,361
Cl
null
null
null
ord_dataset-5df93261afc143c3ae919a57ff4fc1d4
2011-01-01T00:07:00
true
To a suspension of trans-2-aminocyclohexylmethanol hydrochloride (214 mg, 1.30 mmol) and triethylamine (0.538 mL, 3.9 mmol) in 5 mL dichloromethane at 0° C. was added a solution of 5-chlorothiophene-2-sulfonyl chloride (0.267 mL, 1.23 mmol) in 1 mL dichloromethane. The reaction was stirred at 0° C. for 30 min and at room temperature for 30 min. The crude reaction mixture was purified by flash chromatography on silica gel using a gradient of 0 to 100% ethyl acetate in hexane to give 5-chloro-N-(trans-2-(hydroxymethyl)cyclohexyl)thiophene-2-sulfonamide (330 mg, 84%). 1H NMR (400 MHz, CDCl3) δ ppm 7.40 (d, J=4.03 Hz, 1H), 6.91 (d, J=4.03 Hz, 1H), 5.24 (d, J=7.30 Hz, 1H), 3.86 (d, J=11.33 Hz, 1H), 3.32-3.48 (m, 1H), 3.05 (d, J=6.55 Hz, 1H), 2.32 (br. s., 1H), 1.72-1.83 (m, 1H), 1.58-1.73 (m, 3H), 1.11-1.36 (m, 5H). MS [M+H]+=310; [M+Na]+=332.
O=S(=O)(N[C@@H]1CCCC[C@H]1CO)c1ccc(Cl)s1
null
N[C@@H]1CCCC[C@H]1CO
O=S(=O)(Cl)c1ccc(Cl)s1
null
Cl.[NH2:2][C@@H:3]1[CH2:8][CH2:7][CH2:6][CH2:5][C@H:4]1[CH2:9][OH:10].C(N(CC)CC)C.[Cl:18][C:19]1[S:23][C:22]([S:24](Cl)(=[O:26])=[O:25])=[CH:21][CH:20]=1>ClCCl>[Cl:18][C:19]1[S:23][C:22]([S:24]([NH:2][C@@H:3]2[CH2:8][CH2:7][CH2:6][CH2:5][C@H:4]2[CH2:9][OH:10])(=[O:26])=[O:25])=[CH:21][CH:20]=1
0.5
CCN(CC)CC
ClCCl
null
0
null
86.6
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
318,313
[H-]
[Na+]
null
null
ord_dataset-eb32c2b9cbdf4fc39ce6c9fe0fa11430
1995-01-01T00:10:00
true
To a solution of 3-(pyridin-3-yl)-7-(6-phenylmethoxyindol-3-yl)carbonyl-1H,3H-pyrrolo[1,2-c]thiazole (200 mg, 0.443 mmol), prepared as in Example 4, in DMF (12 mL) was added NaH (60% oil dispersion, 19 mg, 0.465 mmol) and the reaction mixture was stirred for 7 min at ambient temperature. 4-nitrophenyl chloroformate (94 mg, 0.45 mmol) was added and the amber solution was stirred for two hours at ambient temperature. The reaction mixture was partitioned between H2O and ethyl acetate. The organic phase was dried over MgSO4, filtered,and concentrated. The title compound (98 mg), was purified by flash chromatography on silica gel (60 g, 1:1 ethyl acetate, hexanes).
O=C(c1ccn2c1CSC2c1cccnc1)c1cn(C(=O)Oc2ccc([N+](=O)[O-])cc2)c2cc(OCc3ccccc3)ccc12
null
O=C(c1ccn2c1CSC2c1cccnc1)c1c[nH]c2cc(OCc3ccccc3)ccc12
O=C(Cl)Oc1ccc([N+](=O)[O-])cc1
null
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([CH:7]2[N:11]3[CH:12]=[CH:13][C:14]([C:15]([C:17]4[C:25]5[C:20](=[CH:21][C:22]([O:26][CH2:27][C:28]6[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=6)=[CH:23][CH:24]=5)[NH:19][CH:18]=4)=[O:16])=[C:10]3[CH2:9][S:8]2)[CH:2]=1.[H-].[Na+].Cl[C:37]([O:39][C:40]1[CH:45]=[CH:44][C:43]([N+:46]([O-:48])=[O:47])=[CH:42][CH:41]=1)=[O:38]>CN(C=O)C>[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([CH:7]2[N:11]3[CH:12]=[CH:13][C:14]([C:15]([C:17]4[C:25]5[C:20](=[CH:21][C:22]([O:26][CH2:27][C:28]6[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=6)=[CH:23][CH:24]=5)[N:19]([C:37]([O:39][C:40]5[CH:41]=[CH:42][C:43]([N+:46]([O-:48])=[O:47])=[CH:44][CH:45]=5)=[O:38])[CH:18]=4)=[O:16])=[C:10]3[CH2:9][S:8]2)[CH:2]=1
0.12
CN(C)C=O
null
null
25
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,607,743
null
null
null
null
ord_dataset-9cecb3a8d3b9494191b28dcefea66af2
2015-01-01T00:07:00
true
To a solution of the compound (0.10 g) obtained in Example 33, step 1 in THF (3 mL)/diethyl ether (3 mL) was added tert-butyl isocyanate (41 μL), and the mixture was stirred at room temperature for 16 hr. The solvent was evaporated under reduced pressure, and the obtained solid was washed with diethyl ether/hexane to give tert-butyl 8-{4-[(tert-butylamino)carbonyl]piperazin-1-yl}-2,3-dihydropyrido[3,2-f][1,4]oxazepine-4(5H)-carboxylate (0.11 g, 85%) as a white powder.
CC(C)(C)NC(=O)N1CCN(c2ccc3c(n2)OCCN(C(=O)OC(C)(C)C)C3)CC1
null
CC(C)(C)N=C=O
CC(C)(C)OC(=O)N1CCOc2nc(N3CCNCC3)ccc2C1
null
[N:1]1([C:7]2[CH:8]=[CH:9][C:10]3[CH2:11][N:12]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:13][CH2:14][O:15][C:16]=3[N:17]=2)[CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1.C(OCC)C.[C:30]([N:34]=[C:35]=[O:36])([CH3:33])([CH3:32])[CH3:31]>C1COCC1>[C:30]([NH:34][C:35]([N:4]1[CH2:5][CH2:6][N:1]([C:7]2[CH:8]=[CH:9][C:10]3[CH2:11][N:12]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:13][CH2:14][O:15][C:16]=3[N:17]=2)[CH2:2][CH2:3]1)=[O:36])([CH3:33])([CH3:32])[CH3:31]
16
C1CCOC1
CCOCC
null
25
null
85
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,035,997
null
null
null
null
ord_dataset-3af92aec23dc4810b92eb0d8c60023ee
2011-01-01T00:03:00
true
Isobutylamine (15.6 mL, 157 mmol) was added dropwise to a 5° C. solution of 4-chloro-3-nitro[1,5]naphthyridine (15.0 g, 71.6 mmol) in dichloromethane (300 mL). The reaction was allowed to stir at room temperature for 4 hours, then was concentrated under reduced pressure to afford a residue that was treated with water (300 mL). The mixture was stirred for 30 minutes, then a solid was isolated by filtration, rinsed with water (100 mL), and dried in a vacuum oven at 50° C. overnight to afford 17.25 g of N-(2-methylpropyl)-3-nitro[1,5]naphthyridin-4-amine as a yellow solid.
CC(C)CNc1c([N+](=O)[O-])cnc2cccnc12
null
O=[N+]([O-])c1cnc2cccnc2c1Cl
CC(C)CN
null
[CH2:1]([NH2:5])[CH:2]([CH3:4])[CH3:3].Cl[C:7]1[C:16]2[C:11](=[CH:12][CH:13]=[CH:14][N:15]=2)[N:10]=[CH:9][C:8]=1[N+:17]([O-:19])=[O:18].O>ClCCl>[CH3:3][CH:2]([CH3:4])[CH2:1][NH:5][C:7]1[C:16]2[C:11](=[CH:12][CH:13]=[CH:14][N:15]=2)[N:10]=[CH:9][C:8]=1[N+:17]([O-:19])=[O:18]
4
O
ClCCl
null
25
97.8
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,437,344
C=C[Mg]Br
null
null
null
ord_dataset-275a3da8f45f4536ad29727f0ef9ba66
2014-01-01T00:06:00
true
In a flame dried roundbottomflask (E)-but-2-enoic acid methoxy-methyl-amide (Einhorn et al., Synth. Commun. 20 (8), 1105-1112 (1990)) (8.0 g, 61.9 mmol) was dissolved in 150 ml of THF. A 1M solution of vinylmagnesium bromide in Et2O (68.1 ml, 68.1 mmol) was added at 0° C. and then the mixture was stirred for 1 h at rt. (S)-(−)-alpha-methylbenzylamin (15.8 ml, 124 mmol) was added at rt, followed by water (15 ml). The reaction was stirred at rt for 1 h. THF was evaporated and 150 ml of water was added. Then the mixture was extracted three times with CH2Cl2 The organic layer was washed with brine, dried over Na2 SO4 and evaporated. The crude product was purified by flash chromatography (silica gel, 20% EtOAc/cyclohexane) which furnished the (S,S) product as the first fraction (confirmed by x-ray).
C[C@H]1CC(=O)CCN1[C@@H](C)c1ccccc1
null
CCc1nn2c(C)cc(C)nc2c1Cc1ccc(O)cc1
C[C@H](N)c1ccccc1
null
C(C1C(C[C:15]2[CH:20]=[CH:19][C:18]([OH:21])=[CH:17][CH:16]=2)=C2N=C(C)C=C(C)N2N=1)C.C([Mg]Br)=C.CCOCC.[CH3:31][C@H:32]([NH2:39])[C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1>C1COCC1.O>[CH3:15][C@H:16]1[CH2:17][C:18](=[O:21])[CH2:19][CH2:20][N:39]1[C@H:32]([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[CH3:31]
1
O
C1CCOC1
CCOCC
25
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,707,554
[Na]
null
null
null
ord_dataset-54347fcace774f89850681d6dec8009f
2016-01-01T00:03:00
true
Sodium metal (12 mg, 0.52 mmol) was added to anhydrous ethanol (3 mL) at room temperature and the mixture was stirred for 15 min. 1-(1H-pyrazol-1-yl)cyclopropanecarbonitrile (0.1 g, 0.75 mmol) dissolved in ethanol (2 mL) was added and the reaction mixture was heated to 70° C. for 90 min. The resulting solution was used without further purification.
CCOC(=N)C1(n2cccn2)CC1
null
N#CC1(n2cccn2)CC1
CCO
null
[Na].[N:2]1([C:7]2([C:10]#[N:11])[CH2:9][CH2:8]2)[CH:6]=[CH:5][CH:4]=[N:3]1.[CH2:12]([OH:14])[CH3:13]>>[N:2]1([C:7]2([C:10](=[NH:11])[O:14][CH2:12][CH3:13])[CH2:9][CH2:8]2)[CH:6]=[CH:5][CH:4]=[N:3]1
0.25
null
null
null
70
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
848,765
[BH4-]
[Na+]
null
null
ord_dataset-171b840ae6e84e45bab43b987d09f5c7
2008-01-01T00:11:00
true
To a solution of 2-(tetrahydropyran-4-ylamino)-6-(2-fluorobenzoyl)thieno[2,3-d]pyrimidine (300 mg) in ethanol (30 mL) was added sodium borohydride (0.4 g) at room temperature and stirred overnight. Ethyl acetate (50 mL) was added to the reaction mixture. The organic layer was separated, washed with brine, dried, and evaporated. Purification by preparative TLC (silica gel, 50% EtOAc/hexanes) gave 140 mg of the alcohol. MS: 360.2 (M+H).
OC(c1cc2cnc(NC3CCOCC3)nc2s1)c1ccccc1F
null
O=C(c1cc2cnc(NC3CCOCC3)nc2s1)c1ccccc1F
null
null
[O:1]1[CH2:6][CH2:5][CH:4]([NH:7][C:8]2[N:9]=[CH:10][C:11]3[CH:16]=[C:15]([C:17](=[O:25])[C:18]4[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=4[F:24])[S:14][C:12]=3[N:13]=2)[CH2:3][CH2:2]1.[BH4-].[Na+].C(OCC)(=O)C>C(O)C>[O:1]1[CH2:2][CH2:3][CH:4]([NH:7][C:8]2[N:9]=[CH:10][C:11]3[CH:16]=[C:15]([CH:17]([C:18]4[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=4[F:24])[OH:25])[S:14][C:12]=3[N:13]=2)[CH2:5][CH2:6]1
8
CCO
CCOC(C)=O
null
null
46.4
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
26,446
O=C([O-])[O-]
[Na+]
null
null
ord_dataset-2ada3fda46fc44719ba0c8001f53c1b3
1977-01-01T00:06:00
true
A mixture of 7.3 parts of N-(2-bromoethyl)-4-fluoro-2-nitrobenzamide, 6.2 parts of 5-chloro-1,3-dihydro-1-(4-piperidinyl)-2H-benzimidazol-2-one, 5.2 parts of sodium carbonate and 80 parts of 4-methyl-2-pentanone is stirred and refluxed overnight. The reaction mixture is cooled, water is added and the layers are separated. The aqueous phase is extracted with 4-methyl-2-pentanone. The combined organic phases are washed with water, dried, filtered and evaporated. The residue is purified by column-chromatography over silica gel using a mixture of trichloromethane and methanol (90:10 by volume) as eluent. The pure fractions are collected and the eluent is evaporated. The oily residue is crystallized from 2-propanone. The product is filtered off and dried, yielding 1 part of N-{2-[4-(5-chloro-2,3-dihydro-2-oxo-1H-benzimidazol-1-yl)-1-piperidinyl]-ethyl}-4-fluoro-2-nitrobenzamide.
O=C(NCCN1CCC(n2c(=O)[nH]c3cc(Cl)ccc32)CC1)c1ccc(F)cc1[N+](=O)[O-]
null
O=c1[nH]c2cc(Cl)ccc2n1C1CCNCC1
O=C(NCCBr)c1ccc(F)cc1[N+](=O)[O-]
null
Br[CH2:2][CH2:3][NH:4][C:5](=[O:16])[C:6]1[CH:11]=[CH:10][C:9]([F:12])=[CH:8][C:7]=1[N+:13]([O-:15])=[O:14].[Cl:17][C:18]1[CH:33]=[CH:32][C:21]2[N:22]([CH:26]3[CH2:31][CH2:30][NH:29][CH2:28][CH2:27]3)[C:23](=[O:25])[NH:24][C:20]=2[CH:19]=1.C(=O)([O-])[O-].[Na+].[Na+].CC(C)CC(=O)C>O>[Cl:17][C:18]1[CH:33]=[CH:32][C:21]2[N:22]([CH:26]3[CH2:27][CH2:28][N:29]([CH2:2][CH2:3][NH:4][C:5](=[O:16])[C:6]4[CH:11]=[CH:10][C:9]([F:12])=[CH:8][C:7]=4[N+:13]([O-:15])=[O:14])[CH2:30][CH2:31]3)[C:23](=[O:25])[NH:24][C:20]=2[CH:19]=1
null
O
CC(=O)CC(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
11,646
null
null
null
null
ord_dataset-7c810806c4564bada4a9550135bbb06f
1976-01-01T00:08:00
true
The reaction of ethyl 2-hydroxyimino-2-cyanoacetate (8.5 g) with ethyl chloroformate (6.0 g) is carried out as in Example 3 to give ethyl 2-ethoxycarbonyloxyimino-2-cyanoacetate (8.8 g) as an oil.
CCOC(=O)ON=C(C#N)C(=O)OCC
null
CCOC(=O)C(C#N)=NO
CCOC(=O)Cl
null
[OH:1][N:2]=[C:3]([C:9]#[N:10])[C:4]([O:6][CH2:7][CH3:8])=[O:5].Cl[C:12]([O:14][CH2:15][CH3:16])=[O:13]>>[CH2:15]([O:14][C:12]([O:1][N:2]=[C:3]([C:9]#[N:10])[C:4]([O:6][CH2:7][CH3:8])=[O:5])=[O:13])[CH3:16]
null
null
null
null
null
null
74.3
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
516,276
BrB(Br)Br
null
null
null
ord_dataset-a495451286334c5c9bbcbd48a00c1350
2001-01-01T00:09:00
true
To a solution of {2-[3-ethyl-3-(3-methoxy-phenyl)-2-oxo-azepan-1-yl]-ethyl}-urea (as described above in Step B) (0.14 g, 0.421 mmol) in CH2Cl2 (10 mL) at −78° C. was added BBr3 (1M, 0.842 mL, 0.842 rnmol). After stirring for 1 hr at 25° C. the reaction was quenched with H2O and partitioned with EtOAc and 10% HCl. The organic layer was washed with brine and dried (MgSO4), and the solvent removed in vacuo to obtain the title compound.
CCC1(c2cccc(O)c2)CCCCN(CCNC(N)=O)C1=O
null
CCC1(c2cccc(OC)c2)CCCCN(CCNC(N)=O)C1=O
null
null
[CH2:1]([C:3]1([C:17]2[CH:22]=[CH:21][CH:20]=[C:19]([O:23]C)[CH:18]=2)[CH2:9][CH2:8][CH2:7][CH2:6][N:5]([CH2:10][CH2:11][NH:12][C:13]([NH2:15])=[O:14])[C:4]1=[O:16])[CH3:2].B(Br)(Br)Br>C(Cl)Cl>[CH2:1]([C:3]1([C:17]2[CH:22]=[CH:21][CH:20]=[C:19]([OH:23])[CH:18]=2)[CH2:9][CH2:8][CH2:7][CH2:6][N:5]([CH2:10][CH2:11][NH:12][C:13]([NH2:15])=[O:14])[C:4]1=[O:16])[CH3:2]
1
ClCCl
null
null
25
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
853,503
[K+]
null
null
null
ord_dataset-faa0236be76c4501841c954527cd1b6c
2008-01-01T00:12:00
true
A mixture of 2-bromopyridine (3.4 mmol), 3-pyrazolecarboxaldehyde (3.2 mmol), and potassium carbonate (3.4 mmol) in anhydrous DMF (6 mL) was heated to 120° C. for 24 h. The reaction was cooled to RT, diluted with water, and extracted with EtOAc (3 x). The organic layers were combined and dried (Na2SO4), filtered, and concentrated. The title compound was obtained upon purification (SGC using EtOAc:hexanes gradient eluant from 0% to 100% EtOAc).
O=Cc1cnn(-c2ccccn2)c1
null
O=C([O-])[O-]
O=Cc1cc[nH]n1
Brc1ccccn1
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1.[NH:8]1[CH:12]=[CH:11][C:10](C=O)=[N:9]1.[C:15](=O)([O-])[O-:16].[K+].[K+]>CN(C=O)C.O>[N:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[N:9]1[CH:10]=[C:11]([CH:15]=[O:16])[CH:12]=[N:8]1
null
O
CN(C)C=O
null
120
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,395,874
[Pd]
CC1(C)c2cccc(P(c3ccccc3)c3ccccc3)c2Oc2c(P(c3ccccc3)c3ccccc3)cccc21
O=C(/C=C/c1ccccc1)/C=C/c1ccccc1
null
ord_dataset-12dc3bd21bcf44d09e5b4249afe15161
2014-01-01T00:02:00
true
A mixture of 2-(5-bromo-2-neopentyl-1H-benzo[d]imidazol-1-yl)-N,N-dimethylethanamine (prepared in STEP A of Example 1, 1.41 g, 4.15 mmol), tert-butyl 4-(mercaptomethyl)piperidine-1-carboxylate (prepared in STEP B of Example 5, 1.20 g, 5.19 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (120 mg, 0.208 mmol), tris(dibenzylideneacetone)dipalladium(0) (95.2 mg, 0.104 mmol) and N,N-diisopropylethylamine (1.09 mL, 6.23 mmol) in 1,4-dioxane (8.5 mL) was stirred at 130° C. for 18 h. The mixture was filtered through a celite and the filtrate was concentrated in vacuo. The residue (2.40 g) was used for the next step without purification.
CN(C)CCn1c(CC(C)(C)C)nc2cc(SCC3CCN(C(=O)OC(C)(C)C)CC3)ccc21
null
CN(C)CCn1c(CC(C)(C)C)nc2cc(Br)ccc21
CC(C)(C)OC(=O)N1CCC(CS)CC1
null
Br[C:2]1[CH:20]=[CH:19][C:5]2[N:6]([CH2:14][CH2:15][N:16]([CH3:18])[CH3:17])[C:7]([CH2:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[N:8][C:4]=2[CH:3]=1.[SH:21][CH2:22][CH:23]1[CH2:28][CH2:27][N:26]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[CH2:25][CH2:24]1.C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.C(N(CC)C(C)C)(C)C>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:17][N:16]([CH3:18])[CH2:15][CH2:14][N:6]1[C:5]2[CH:19]=[CH:20][C:2]([S:21][CH2:22][CH:23]3[CH2:28][CH2:27][N:26]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[CH2:25][CH2:24]3)=[CH:3][C:4]=2[N:8]=[C:7]1[CH2:9][C:10]([CH3:13])([CH3:12])[CH3:11]
18
CCN(C(C)C)C(C)C
C1COCCO1
null
130
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
966,514
[Li+]
[OH-]
null
null
ord_dataset-03ba810b7f464a06b5d8787af2e8b64e
2010-01-01T00:06:00
true
Methyl 3-[(dipropylamino)carbonyl]-5-(1,3-thiazol-2-yl)benzoate (4.4 g, 12.8 mmol) is dissolved in 1:1:1 tetrahydrofuran/methanol/water (60 mL), and lithium hydroxide monohydrate is added (1.1 g, 25.6 mmol). The reaction is stirred 15 min and is concentrated under reduced pressure. The residue is diluted in chloroform and washed with water, brine, dried (magnesium sulfate), filtered, and concentrated under reduced pressure to give the title compound. ESI MS m/z 333.1 [M+H]+.
CCCN(CCC)C(=O)c1cc(C(=O)O)cc(-c2nccs2)c1
null
CCCN(CCC)C(=O)c1cc(C(=O)OC)cc(-c2nccs2)c1
null
null
[CH2:1]([N:4]([CH2:22][CH2:23][CH3:24])[C:5]([C:7]1[CH:8]=[C:9]([CH:14]=[C:15]([C:17]2[S:18][CH:19]=[CH:20][N:21]=2)[CH:16]=1)[C:10]([O:12]C)=[O:11])=[O:6])[CH2:2][CH3:3]>O1CCCC1.CO.O.O.[OH-].[Li+]>[CH2:22]([N:4]([CH2:1][CH2:2][CH3:3])[C:5]([C:7]1[CH:8]=[C:9]([CH:14]=[C:15]([C:17]2[S:18][CH:19]=[CH:20][N:21]=2)[CH:16]=1)[C:10]([OH:12])=[O:11])=[O:6])[CH2:23][CH3:24]
0.25
CO
C1CCOC1
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
516,053
CN(C)C(On1nnc2ccccc21)=[N+](C)C
Cl
F[B-](F)(F)F
null
ord_dataset-a495451286334c5c9bbcbd48a00c1350
2001-01-01T00:09:00
true
To a solution of 3-amino-1-(4-methoxybenzyl)-4-methyl-2-pyridone (5.03 g, 20.6 mmol), DIEA (3.76 mL, 21.6 mmol) and N-Boc-p-nitrophenylalanine (6.71 g, 21.6 mmol) in acetonitrile (100 mL) cooled on ice was added TBTU (7.94 g, 24.7 mmol). The mixture was stirred at rt overnight. Additional DIEA (3.76 mL, 21,6 mmol) was added, and the slurry was stirred for another 6 hours. 1N HCl (50 mL) was added, and the acetonitrile was removed under reduced pressure. Ethyl acetate (300 mL) was added, and the organic suspension was separated and washed with 1N HCl, 2.5N NaOH and brine. Ethyl acetate (50 mL) and THF (100 mL) were added to the suspension to dissolve all solids, and the organic phase was washed with brine, and dried (MgSO4/silica gel/charcoal). Evaporation of the solvent gave 3-2′-(S)-tbutoxycarbonylamino-3′-(4″-nitro)benzene]propanoylamino-1-(4-methoxybenzyl)-4-methyl-2-pyridone as a brown solid (9.73 g, 88%).
CCC(=O)Nc1c(C)ccn(Cc2ccc(OC)cc2)c1=O
null
COc1ccc(Cn2ccc(C)c(N)c2=O)cc1
CC(C)(C)OC(=O)N[C@@H](Cc1ccc([N+](=O)[O-])cc1)C(=O)O
null
[NH2:1][C:2]1[C:3](=[O:18])[N:4]([CH2:9][C:10]2[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][CH:11]=2)[CH:5]=[CH:6][C:7]=1[CH3:8].CCN(C(C)C)C(C)C.C(N[C@H:36]([C:47](O)=[O:48])[CH2:37]C1C=CC([N+]([O-])=O)=CC=1)(OC(C)(C)C)=O.CN(C(ON1N=NC2C=CC=CC1=2)=[N+](C)C)C.[B-](F)(F)(F)F.Cl>C(#N)C>[C:47]([NH:1][C:2]1[C:3](=[O:18])[N:4]([CH2:9][C:10]2[CH:11]=[CH:12][C:13]([O:16][CH3:17])=[CH:14][CH:15]=2)[CH:5]=[CH:6][C:7]=1[CH3:8])(=[O:48])[CH2:36][CH3:37]
8
CC#N
CCN(C(C)C)C(C)C
null
25
157.3
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,184,177
Cc1ccc(S(=O)(=O)O)cc1
null
null
null
ord_dataset-9cd817a75dfc4fe7ad19d4232772d5ff
2012-01-01T00:07:00
true
To a solution of 4-bromo-benzene-1,2-diamine (3.0 g, 16.1 mmol) in anhydrous toluene (50 ml) was added a solution of 3-cyclohexyl-acryloyl chloride (as prepared in STEP B above, 32.5 mmol) in toluene (5 ml). The resulting solution was stirred at 40° C. for 6 h. To the resulting solution was added p-toluenesulfonic acid (3.0 g, 16 mmol) and heated to reflux for 18 h. The resulting solution was concentrated. The residue obtained was partitioned between ethyl acetate and a saturated solution of sodium bicarbonate. The layers were separated. The organic layer was washed successively with saturated sodium bicarbonate, water, brine, then dried over sodium sulfate, filtered and concentrated. The residue was chromatographed using a silica gel to yield 5-bromo-2-(2-cyclohexyl-vinyl)-1H-benzoimidazole.
Brc1ccc2[nH]c(C=CC3CCCCC3)nc2c1
null
Nc1ccc(Br)cc1N
O=C(Cl)C=CC1CCCCC1
null
[Br:1][C:2]1[CH:3]=[C:4]([NH2:9])[C:5]([NH2:8])=[CH:6][CH:7]=1.[CH:10]1([CH:16]=[CH:17][C:18](Cl)=O)[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]1.C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]2[NH:8][C:18]([CH:17]=[CH:16][CH:10]3[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]3)=[N:9][C:4]=2[CH:3]=1
6
Cc1ccccc1
null
null
40
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
530,906
[BH4-]
[Na+]
null
null
ord_dataset-7774db17e619477ea20ee621abe71257
2002-01-01T00:01:00
true
7-Chloro-5-[(4-methyl-1-piperazinyl)carbonylmethyl]-1-{4-[2-(2-methylphenyl)acetyl]benzoyl}-2,3,4,5-tetrahydro-1H-benzazepine (2.06 g) is dissolved in a mixture of methylene chloride (20 ml) and methanol (20 ml), and thereto ia added with stirring sodium borohydride (0.28 g) under cooling over an ice-bath. The mixture is stirred for two hours over an ice-bath, and the mixture is evaporated to remove almost of the solvent. To the residue is added water, and the mixture is extracted with methylene chloride. The organic layer is washed with a saturated aqueous sodium chloride solution, dried over magnesium sulfate, and concentrated. The residue is purified by silica gel column chromatography (solvent; methylene chloride:methanol=20˜10:1) to give 7-chloro-5-[(4-methyl-1-piperazinyl)carbonylmethyl]-1-{4-[2-(2-methylphenyl)-1-hydroxyethyl]benzoyl}-2,3,4,5-tetrahydro-1H-benzazepine (2.08 g) as colorless amorphous.
Cc1ccccc1CC(O)c1ccc(C(=O)N2CCCC(CC(=O)N3CCN(C)CC3)c3cc(Cl)ccc32)cc1
null
Cc1ccccc1CC(=O)c1ccc(C(=O)N2CCCC(CC(=O)N3CCN(C)CC3)c3cc(Cl)ccc32)cc1
null
null
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[N:11]([C:12](=[O:29])[C:13]3[CH:18]=[CH:17][C:16]([C:19](=[O:28])[CH2:20][C:21]4[CH:26]=[CH:25][CH:24]=[CH:23][C:22]=4[CH3:27])=[CH:15][CH:14]=3)[CH2:10][CH2:9][CH2:8][CH:7]([CH2:30][C:31]([N:33]3[CH2:38][CH2:37][N:36]([CH3:39])[CH2:35][CH2:34]3)=[O:32])[C:6]=2[CH:40]=1.[BH4-].[Na+]>C(Cl)Cl.CO>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[N:11]([C:12](=[O:29])[C:13]3[CH:18]=[CH:17][C:16]([CH:19]([OH:28])[CH2:20][C:21]4[CH:26]=[CH:25][CH:24]=[CH:23][C:22]=4[CH3:27])=[CH:15][CH:14]=3)[CH2:10][CH2:9][CH2:8][CH:7]([CH2:30][C:31]([N:33]3[CH2:38][CH2:37][N:36]([CH3:39])[CH2:35][CH2:34]3)=[O:32])[C:6]=2[CH:40]=1
2
CO
ClCCl
null
null
100.6
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,541,479
null
null
null
null
ord_dataset-cac8df8aff894288876df4e093c9877f
2015-01-01T00:02:00
true
The crude product N-hydroxy-1-[2-(trimethylsilyl)ethoxy]methyl-1H-pyrrolo[2,3-b]pyridine-4-carboximidamide (0.06 gm, 0.0002 mol) was dissolved in pyridine (1.0 mL, 0.012 mol) and then 3-cyanobenzoyl chloride (0.040 g, 0.00024 mol) was added at rt. This mixture was stirred for 1 h and heated to 80° C. in an oil bath. After heating for 18 h the reaction was allowed to cool to rt and then diluted with ACN and concentrated in vacuo to give 3-[3-(1-[2-(trimethylsilyl)ethoxy]methyl-1H-pyrrolo[2,3-b]pyridin-4-yl)-1,2,4-oxadiazol-5-yl]benzonitrile 0.08 gm as an off white residue, LC/MS (M+H)+ 418.
C[Si](C)(C)CCOCn1ccc2c(-c3noc(-c4cccc(C#N)c4)n3)ccnc21
null
N#Cc1cccc(C(=O)Cl)c1
C[Si](C)(C)CCOCn1ccc2c(C(=N)NO)ccnc21
null
[OH:1][NH:2][C:3]([C:5]1[C:6]2[CH:13]=[CH:12][N:11]([CH2:14][O:15][CH2:16][CH2:17][Si:18]([CH3:21])([CH3:20])[CH3:19])[C:7]=2[N:8]=[CH:9][CH:10]=1)=[NH:4].N1C=CC=CC=1.[C:28]([C:30]1[CH:31]=[C:32]([CH:36]=[CH:37][CH:38]=1)[C:33](Cl)=O)#[N:29]>C(#N)C>[CH3:19][Si:18]([CH3:21])([CH3:20])[CH2:17][CH2:16][O:15][CH2:14][N:11]1[C:7]2=[N:8][CH:9]=[CH:10][C:5]([C:3]3[N:4]=[C:33]([C:32]4[CH:31]=[C:30]([CH:38]=[CH:37][CH:36]=4)[C:28]#[N:29])[O:1][N:2]=3)=[C:6]2[CH:13]=[CH:12]1
1
c1ccncc1
CC#N
null
80
null
95.8
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
843,364
null
null
null
null
ord_dataset-e2b35e721c2741999b0005d12691f9fe
2008-01-01T00:10:00
true
The pyrazole acid, prepared as described in Procedure 8, was coupled with (R)—N,N-dimethyl-4-phenyl-1,2-butanediamine (prepared as shown in Procedure 2) using the method of Procedure 3.
CN(C)C[C@@H](CCc1ccccc1)NC(=O)c1n[nH]c(NC(=O)c2ccccc2Cl)c1Br
null
CC(CNC(=O)c1n[nH]c(NC(=O)c2ccccc2Cl)c1Br)N1CCCC1
c1cn[nH]c1
null
N1[CH:5]=[CH:4][CH:3]=N1.[N:6]1([CH:11](C)[CH2:12][NH:13][C:14]([C:16]2[C:20]([Br:21])=[C:19]([NH:22][C:23](=[O:31])[C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][C:25]=3[Cl:30])[NH:18][N:17]=2)=[O:15])[CH2:10]CC[CH2:7]1>>[CH3:10][N:6]([CH2:11][C@H:12]([NH:13][C:14]([C:16]1[C:20]([Br:21])=[C:19]([NH:22][C:23](=[O:31])[C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][C:25]=2[Cl:30])[NH:18][N:17]=1)=[O:15])[CH2:3][CH2:4][C:5]1[CH:28]=[CH:29][CH:24]=[CH:25][CH:26]=1)[CH3:7]
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
786,142
CC(=NO)C(=O)C1CCCCC1
Cc1ccc(C=O)cc1
null
null
ord_dataset-4ad5db8537994579bef51f16dd8bf0bd
2007-01-01T00:08:00
true
Analogously to the building block synthesis of 4-iodomethyl-5-phenyl-2-p-tolyloxazole, 1-cyclohexyl-1,2-propanedione-2-oxime and p-tolu-aldehyde gave 4-iodomethyl-5-cyclohexyl-2-p-tolyloxazole.
Cc1ccc(-c2nc(CI)c(C3CCCCC3)o2)cc1
null
Cc1ccc(-c2nc(CI)c(-c3ccccc3)o2)cc1
null
null
[I:1][CH2:2][C:3]1[N:4]=[C:5]([C:14]2[CH:19]=[CH:18][C:17]([CH3:20])=[CH:16][CH:15]=2)[O:6][C:7]=1[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.C1(C(=O)C(=NO)C)CCCCC1.C1(C)C=CC(C=O)=CC=1>>[I:1][CH2:2][C:3]1[N:4]=[C:5]([C:14]2[CH:15]=[CH:16][C:17]([CH3:20])=[CH:18][CH:19]=2)[O:6][C:7]=1[CH:8]1[CH2:9][CH2:10][CH2:11][CH2:12][CH2:13]1
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
1,133,628
null
null
null
null
ord_dataset-aaeaab5f3720492494c1cbbdd0ed2820
2012-01-01T00:02:00
true
The title compound was prepared from (S)-6-(2-hydroxy-2-methylpropyl)-6-phenyl-3-[(S)-1-(4-(4,4,5,5-tetra methyl-1,3,2-d ioxaborolan-2-yl)phenyl)ethyl]-1,3-oxazinan-2-one and 4-bromo-1-(2-methoxy-2-methyl-propyl)-1H-pyridin-2-one following a procedure analogous to that described in Example 75 Method 1. Mass spectrum (ESI+): m/z=533 [M+H]+.
COC(C)(C)Cn1ccc(-c2ccc(C(C)N3CC[C@](CC(C)(C)O)(c4ccccc4)OC3=O)cc2)cc1=O
null
COC(C)(C)Cn1ccc(Br)cc1=O
C[C@@H](c1ccc(B2OC(C)(C)C(C)(C)O2)cc1)N1CC[C@](CC(C)(C)O)(c2ccccc2)OC1=O
null
[OH:1][C:2]([CH3:35])([CH3:34])[CH2:3][C@@:4]1([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[O:9][C:8](=[O:10])[N:7]([C@H:11]([C:13]2[CH:18]=[CH:17][C:16](B3OC(C)(C)C(C)(C)O3)=[CH:15][CH:14]=2)[CH3:12])[CH2:6][CH2:5]1.Br[C:37]1[CH:42]=[CH:41][N:40]([CH2:43][C:44]([O:47][CH3:48])([CH3:46])[CH3:45])[C:39](=[O:49])[CH:38]=1>>[OH:1][C:2]([CH3:35])([CH3:34])[CH2:3][C@@:4]1([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[O:9][C:8](=[O:10])[N:7]([CH:11]([C:13]2[CH:14]=[CH:15][C:16]([C:37]3[CH:42]=[CH:41][N:40]([CH2:43][C:44]([O:47][CH3:48])([CH3:46])[CH3:45])[C:39](=[O:49])[CH:38]=3)=[CH:17][CH:18]=2)[CH3:12])[CH2:6][CH2:5]1
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
302,561
null
null
null
null
ord_dataset-bfcf5a01f1a04ec585ba3f28cb93c8c9
1995-01-01T00:01:00
true
Gaseous methylamine was introduced into a solution of 1.33 g (3.76 mmole) of (3S, 5S)-5-[(1S)-1-(t-butoxycarbonyl)amino-2-cyclohexylethyl]-3-isopropyldihydrofuran-2(3H)-one (prepared as described in Preparation 1) in 10 ml of methanol to ensure saturation, whilst ice-cooling. The reaction vessel was then stoppered tightly and allowed to stand overnight. At the end of this time, the solvent was removed by distillation under reduced pressure and the residue was recrystallized from hexane to afford 1.32 g (yield 91%) of the title compound as white crystals, melting at 154°-157° C.
CNC(=O)[C@@H](C[C@H](O)[C@H](CC1CCCCC1)NC(=O)OC(C)(C)C)C(C)C
null
CN
CC(C)[C@@H]1C[C@@H]([C@H](CC2CCCCC2)NC(=O)OC(C)(C)C)OC1=O
null
[CH3:1][NH2:2].[C:3]([O:7][C:8]([NH:10][C@H:11]([C@H:19]1[O:23][C:22](=[O:24])[C@H:21]([CH:25]([CH3:27])[CH3:26])[CH2:20]1)[CH2:12][CH:13]1[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1)=[O:9])([CH3:6])([CH3:5])[CH3:4]>CO>[C:3]([O:7][C:8]([NH:10][C@@H:11]([CH2:12][CH:13]1[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1)[C@@H:19]([OH:23])[CH2:20][C@@H:21]([CH:25]([CH3:27])[CH3:26])[C:22]([NH:2][CH3:1])=[O:24])=[O:9])([CH3:6])([CH3:5])[CH3:4]
8
CO
null
null
null
null
91
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
302,915
[Mn+4]
[O-2]
null
null
ord_dataset-bfcf5a01f1a04ec585ba3f28cb93c8c9
1995-01-01T00:01:00
true
1.0 g (0.0038 mole) of 2-cyano-1-[4-(hydroxymethyl)phenyl]indole was dissolved in 150 ml tetrahydrofuran, 10.0 g of activated manganese dioxide was added, and the mixture stirred at room temperature for 16 hours. The reaction was filtered and the filtrate evaporated to an oil, which was crystallized from a mixture of methyl-t-butyl ether and hexane 1:1 to give 0.63 g (0.0026 mole) of 1-(4-formylphenyl)-2-cyanoindole as an oil.
N#Cc1cc2ccccc2n1-c1ccc(C=O)cc1
null
N#Cc1cc2ccccc2n1-c1ccc(CO)cc1
null
null
[C:1]([C:3]1[N:4]([C:12]2[CH:17]=[CH:16][C:15]([CH2:18][OH:19])=[CH:14][CH:13]=2)[C:5]2[C:10]([CH:11]=1)=[CH:9][CH:8]=[CH:7][CH:6]=2)#[N:2]>O1CCCC1.[O-2].[O-2].[Mn+4]>[CH:18]([C:15]1[CH:16]=[CH:17][C:12]([N:4]2[C:5]3[C:10](=[CH:9][CH:8]=[CH:7][CH:6]=3)[CH:11]=[C:3]2[C:1]#[N:2])=[CH:13][CH:14]=1)=[O:19]
16
C1CCOC1
null
null
25
68.4
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
247,387
null
null
null
null
ord_dataset-75ca79f43dad4cc8a934fe6487fa8eb1
1992-01-01T00:05:00
true
First 1.96 g (12.5 mmol) of piperidine-3-carboxylic acid ethyl ester and then 2.58 g (20 mmol) of N-ethyl-N,N-diisopropylamine are added to a solution of 3.34 g 10 mmol) of 2-[2-(p-toluenesulphonyloxy)ethyl]-benzo-1,4-dioxan in 50 ml of absolute dimethylformamide. The mixture is stirred for 16 hours at 60° and, after cooling, is concentrated by evaporation under a high vacuum. Water is added to the oily residue and extraction is carried out with diethyl ether. The combined organic phases are washed with water and extracted with 2N hydrochloric acid. The combined hydrochloric acid extracts are rendered alkaline, while cold, with sodium hydroxide solution (30% strength) and extracted with dichloromethane. The combined dichloromethane phases are dried over sodium sulphate and concentrated by evaporation in vacuo. 3.82 g (100%) of crude product are obtained which are filtered over 190 g of silica gel (0.040-0.063 mm) using ethyl acetate as the eluant. 3.70 g (96.6%) of 1-[2-(benzo-1,4-dioxan-2-yl)ethyl]-piperidine-3-carboxylic acid ethyl ester are then obtained in the form of a pale yellow oil. The 1-[2-(benzo-1,4-dioxan-2-yl)ethyl]-piperidine-3-carboxylic acid ethyl ester hydrochloride produced therefrom using hydrochloric acid in diethyl ether crystallises from ethanol/diethyl ether and melts at 162°-165°.
CCOC(=O)C1CCCN(CCC2COc3ccccc3O2)C1
null
CCOC(=O)C1CCCNC1
Cc1ccc(S(=O)(=O)OCCC2COc3ccccc3O2)cc1
null
[CH2:1]([O:3][C:4]([CH:6]1[CH2:11][CH2:10][CH2:9][NH:8][CH2:7]1)=[O:5])[CH3:2].C(N(C(C)C)C(C)C)C.C1(C)C=CC(S(O[CH2:31][CH2:32][CH:33]2[O:38][C:37]3[CH:39]=[CH:40][CH:41]=[CH:42][C:36]=3[O:35][CH2:34]2)(=O)=O)=CC=1>CN(C)C=O>[CH2:1]([O:3][C:4]([CH:6]1[CH2:11][CH2:10][CH2:9][N:8]([CH2:31][CH2:32][CH:33]2[O:38][C:37]3[CH:39]=[CH:40][CH:41]=[CH:42][C:36]=3[O:35][CH2:34]2)[CH2:7]1)=[O:5])[CH3:2]
16
CCN(C(C)C)C(C)C
CN(C)C=O
null
null
null
96.6
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,018,770
null
null
null
null
ord_dataset-f024e9664ab64906a71a2ff6004cb3d0
2010-01-01T00:12:00
true
To a solution of (R)-tert-butyl 2-((S)-(6-fluoro-3′-methylbiphenyl-2-yl)(2-hydroxyethoxy)methyl)morpholine-4-carboxylate (498 mg, 1.12 mmol) in dry CH2Cl2 (15 mL) was added Et3N (472 mg, 4.68 mmol) at ˜0 to −5° C. A solution of MsCl (267 mg, 2.34 mmol) in dry CH2Cl2 (10 mL) was added dropwise at the same temperature. The mixture was allowed to warm to rt gradually. Tlc showed the stating material had disappeared. Water (10 mL) was added and the aqueous layer was extracted with CH2Cl2 (3×20 mL). The combined organic layers were washed with 10% aq citric acid, satd aq NaHCO3 and brine, dried over Na2SO4, filtered and concentrated to afford crude (R)-tert-butyl 2-((S)-(6-fluoro-3′-methylbiphenyl-2-yl)(2-(methylsulfonyloxy)ethoxy)methyl)morpholine-4-carboxylate (554 mg, 95%). which was used in the next step without further purification. MS (E/Z): 524 (M+H+)
Cc1cccc(-c2c(F)cccc2[C@H](OCCOS(C)(=O)=O)[C@H]2CN(C(=O)OC(C)(C)C)CCO2)c1
null
CS(=O)(=O)Cl
Cc1cccc(-c2c(F)cccc2[C@H](OCCO)[C@H]2CN(C(=O)OC(C)(C)C)CCO2)c1
null
[F:1][C:2]1[C:7]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([CH3:14])[CH:9]=2)=[C:6]([C@H:15]([O:29][CH2:30][CH2:31][OH:32])[C@@H:16]2[O:21][CH2:20][CH2:19][N:18]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:17]2)[CH:5]=[CH:4][CH:3]=1.CCN(CC)CC.[CH3:40][S:41](Cl)(=[O:43])=[O:42].O>C(Cl)Cl>[F:1][C:2]1[C:7]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([CH3:14])[CH:9]=2)=[C:6]([C@H:15]([O:29][CH2:30][CH2:31][O:32][S:41]([CH3:40])(=[O:43])=[O:42])[C@@H:16]2[O:21][CH2:20][CH2:19][N:18]([C:22]([O:24][C:25]([CH3:26])([CH3:27])[CH3:28])=[O:23])[CH2:17]2)[CH:5]=[CH:4][CH:3]=1
null
CCN(CC)CC
ClCCl
O
25
null
94.5
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
672,557
null
null
null
null
ord_dataset-e90cd41afe844e49875435eb99903799
2005-01-01T00:05:00
true
A mixture of 2-bromo-1-(5-fluorobenzo[b]thiophen-2-yl)propan-1-one (0.2 g), 2-imidazolidinethione (0.08 g) and ethanol (6 ml) was heated under reflux for 10 minutes. Acetic acid (3 ml) was added, the mixture was heated under reflux for 24 hours, then the solvents were removed in vacuo. Ethanol (10 ml) was added then removed in vacuo, and the residue was dried in vacuo at 60° C. to give 3-(5-fluorobenzo[b]thiophen-2-yl)-3-methyl-5,6-dihydroimidazo[2,1-b]thiazole hydrobromide (0.2 g) as an off-white solid, 1H-nmr (DMSO-d6): δH 2.43 (3H, s, —CH3), 4.22-4.51 (4H, m, —CH2CH2—), 7.36-7.44 (1H, m, ArH), 7.79 (1H, s, ArH), 7.81 (1H, dd, J 9.6 Hz, 2.5 Hz, ArH), 8.13-8.19 (1H, m ArH), 9.3-9.9 (1H, br, H+).
Br
CC1(c2cc3cc(F)ccc3s2)CSC2=NCCN21
CCO
CC(Br)C(=O)c1cc2cc(F)ccc2s1
S=C1NCCN1
[Br:1][CH:2](C)[C:3]([C:5]1[S:9][C:8]2[CH:10]=[CH:11][C:12]([F:14])=[CH:13][C:7]=2[CH:6]=1)=O.[NH:16]1[CH2:20][CH2:19][NH:18][C:17]1=[S:21].[CH2:22](O)C>C(O)(=O)C>[BrH:1].[F:14][C:12]1[CH:11]=[CH:10][C:8]2[S:9][C:5]([C:3]3([CH3:2])[CH2:22][S:21][C:17]4=[N:18][CH2:19][CH2:20][N:16]34)=[CH:6][C:7]=2[CH:13]=1
null
CC(=O)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
1,586,963
CN(C)C(On1nnc2cccnc21)=[N+](C)C
Cl
F[P-](F)(F)(F)(F)F
null
ord_dataset-380e279f82154dba9e08ab51b3bdd08a
2015-01-01T00:05:00
true
To a solution of 4-{[2-(benzyloxy)-4,6-dimethylpyridin-3-yl]methyl}-6-methyl-5-oxo-2,3,4,5-tetrahydro-1,4-benzoxazepine-7-carboxylic acid (130f, 0.17 g, 0.38 mmol), dimethylamine hydrochloride (47 mg, 0.57 mmol) and DIPEA (0.25 g, 1.90 mmol) in DMF (10 mL) was added HATU (0.29 g, 0.76 mmol). The mixture was stirred at room temperature under N2 for 5 hours. To the reaction mixture was added H2O (30 mL). The mixture was extracted with EtOAc (2×20 mL). The combined organic layers were washed with brine (4×30 mL), dried over Na2SO4, and concentrated under vacuum. The residue was purified by column chromatography (petroleum ether/EtOAc, 1/1) to give 4-{[2-(benzyloxy)-4,6-dimethylpyridin-3-yl]methyl}-N,6-dimethyl-5-oxo-2,3,4,5-tetrahydro-1,4-benzoxazepine-7-carboxamide (130 g, 0.17 g, 94.6%) as a white solid.
CNC(=O)c1ccc2c(c1C)C(=O)N(Cc1c(C)cc(C)nc1OCc1ccccc1)CCO2
null
Cc1cc(C)c(CN2CCOc3ccc(C(=O)O)c(C)c3C2=O)c(OCc2ccccc2)n1
CNC
null
[CH2:1]([O:8][C:9]1[C:14]([CH2:15][N:16]2[C:22](=[O:23])[C:21]3[C:24]([CH3:31])=[C:25]([C:28](O)=[O:29])[CH:26]=[CH:27][C:20]=3[O:19][CH2:18][CH2:17]2)=[C:13]([CH3:32])[CH:12]=[C:11]([CH3:33])[N:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl.[CH3:35][NH:36]C.CCN(C(C)C)C(C)C.CN(C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F>CN(C=O)C.O>[CH2:1]([O:8][C:9]1[C:14]([CH2:15][N:16]2[C:22](=[O:23])[C:21]3[C:24]([CH3:31])=[C:25]([C:28]([NH:36][CH3:35])=[O:29])[CH:26]=[CH:27][C:20]=3[O:19][CH2:18][CH2:17]2)=[C:13]([CH3:32])[CH:12]=[C:11]([CH3:33])[N:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
5
O
CCN(C(C)C)C(C)C
CN(C)C=O
25
null
74,445.7
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,518,592
O=C([O-])[O-]
[K+]
null
null
ord_dataset-8c74302143c04eb9983e4b3a7ead2d72
2014-01-01T00:12:00
true
A mixture of the 7-chloro-2-iodothieno[3,2-b]pyridine (23) (Ragan J. A. et al, Organic Process Research and Development 2003, 7, 676-683) (7.0 g, 23.7 mmol), 2-fluoro-4-nitrophenol (3) (11.15 g, 71.1 mmol), K2CO3 (13.08 g, 94.8 mmol) in Ph2O (30 ml) was heated at 200° C. for 3 h. The reaction mixture was cooled to room temperature, diluted with DCM and filtered; the filtrate was collected and then concentrated. The resultant solid was triturated with diethyl ether, to afford intermediate 24 (7.3 g, 74% yield), which was used directly in the next step with no additional purification. MS (m/z): 417.0 (M+H).
O=[N+]([O-])c1ccc(Oc2ccnc3cc(I)sc23)c(F)c1
null
Clc1ccnc2cc(I)sc12
O=[N+]([O-])c1ccc(O)c(F)c1
null
Cl[C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[CH:8]=[C:9]([I:11])[S:10][C:3]=12.[N+:12]([C:15]1[CH:20]=[CH:19][C:18]([OH:21])=[C:17]([F:22])[CH:16]=1)([O-:14])=[O:13].C([O-])([O-])=O.[K+].[K+]>O(C1C=CC=CC=1)C1C=CC=CC=1.C(Cl)Cl>[F:22][C:17]1[CH:16]=[C:15]([N+:12]([O-:14])=[O:13])[CH:20]=[CH:19][C:18]=1[O:21][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[CH:8]=[C:9]([I:11])[S:10][C:3]=12
null
ClCCl
c1ccc(Oc2ccccc2)cc1
null
25
74
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
15,773
null
null
null
null
ord_dataset-b971427c0b944c56b63bb2356fa8ca69
1976-01-01T00:11:00
true
4-Hydroxy-2-methyl-N-(3-methyl-5-isothiazolyl)-2H-naphtho[2,1-e]-1,2-thiazine-3-carboxamide-1,1-dioxide was prepared analogous to Example 22 from 4-hydroxy-2-methyl-2H-naphtho[2,1-e]-1,2-thiazine-3-carboxylic acid methylester-1,1-dioxide and 5-amino-3-methyl-isothiazole. Yield: 44% of theory; m.p. 268° C (decomp.; from ethylene chloride).
Cc1cc(NC(=O)C2=C(O)c3ccc4ccccc4c3S(=O)(=O)N2C)sn1
null
COC(=O)C1=C(O)c2ccc3ccccc3c2S(=O)(=O)N1C
Cc1cc(N)sn1
null
CO[C:3]([C:5]1[N:6]([CH3:22])[S:7](=[O:21])(=[O:20])[C:8]2[C:19]3[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=3)[CH:13]=[CH:12][C:9]=2[C:10]=1[OH:11])=[O:4].[NH2:23][C:24]1[S:28][N:27]=[C:26]([CH3:29])[CH:25]=1>C(Cl)CCl>[OH:11][C:10]1[C:9]2[CH:12]=[CH:13][C:14]3[C:19]([C:8]=2[S:7](=[O:20])(=[O:21])[N:6]([CH3:22])[C:5]=1[C:3]([NH:23][C:24]1[S:28][N:27]=[C:26]([CH3:29])[CH:25]=1)=[O:4])=[CH:18][CH:17]=[CH:16][CH:15]=3
null
ClCCCl
null
null
null
44
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
740,834
null
null
null
null
ord_dataset-437aa6654d5044ddaef3346dc4c6e08a
2006-01-01T00:11:00
true
4-[(6,7-Dimethoxy-4-quinolyl)oxy]aniline (78 mg) was added to toluene/triethylamine=10/1 (8 ml), and the mixture was heated under reflux to prepare a solution. A solution of triphosgene (120 mg) in methylene chloride was then added to the solution, and the mixture was heated under reflux for 15 min. Subsequently, 3-dimethylamino-α-methylbenzyl alcohol (65 mg) was added thereto, and the mixture was further stirred with heating under reflux for 2 hr. After the completion of the reaction, the reaction solution was allowed to cool to room temperature before distilled water was added thereto. The mixture was subjected to separatory extraction with chloroform, followed by washing with a 1 N aqueous hydrochloric acid solution and saturated brine. The washed solution was dried over sodium sulfate and was concentrated. The residue was purified on a column using chloroform/methanol to give the title compound (61 mg, yield 44%).
COc1cc2nccc(Oc3ccc(NC(=O)OC(C)c4cccc(N(C)C)c4)cc3)c2cc1OC
null
COc1cc2nccc(Oc3ccc(N)cc3)c2cc1OC
O=C(OC(Cl)(Cl)Cl)OC(Cl)(Cl)Cl
CC(O)c1cccc(N(C)C)c1
[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][C:12]=1[O:13][CH3:14])[N:9]=[CH:8][CH:7]=[C:6]2[O:15][C:16]1[CH:22]=[CH:21][C:19]([NH2:20])=[CH:18][CH:17]=1.C1(C)C=CC=CC=1.C(N(CC)CC)C.Cl[C:38](Cl)([O:40]C(=O)OC(Cl)(Cl)Cl)Cl.[CH3:49][N:50]([CH3:60])[C:51]1[CH:52]=[C:53]([CH:57]=[CH:58][CH:59]=1)[CH:54]([OH:56])[CH3:55]>C(Cl)Cl>[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][C:12]=1[O:13][CH3:14])[N:9]=[CH:8][CH:7]=[C:6]2[O:15][C:16]1[CH:22]=[CH:21][C:19]([NH:20][C:38](=[O:40])[O:56][CH:54]([C:53]2[CH:57]=[CH:58][CH:59]=[C:51]([N:50]([CH3:49])[CH3:60])[CH:52]=2)[CH3:55])=[CH:18][CH:17]=1
null
CCN(CC)CC
ClCCl
Cc1ccccc1
25
47.5
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
806,169
CCOc1ccc(Br)cc1F
[BH4-]
[Na+]
null
ord_dataset-da49b0378abf41bf92ab8ecdd3feb28b
2008-01-01T00:02:00
true
2.00 g (5.24 mmol) of 3-benzyloxy-8-ethoxy-4,7-difluoro-6H-benzo[c]chromen-6-one, the compound of Example 841, were dissolved in 12 ml of THF, and 2.37 ml (23.0 mmol) of boron trifluoride/THF complex were added with ice-cooling. 24 ml of ethylene glycol dimethyl ether and then in portions 530 mg of sodium borohydride were subsequently added. The mixture was subsequently stirred at room temperature for 18 hours and then transferred onto ice. The mixture was subjected to conventional purification, giving 1.5 g (78% of theory) of 3-benzyloxy-8-ethoxy-4,7-difluoro-6H-benzo[c]chromene as colourless crystals. These were dissolved in THF, hydrogenated at a pressure of 1 bar in the presence of 0.6 g of Pd/C (5%), filtered and evaporated, giving 1.2 g (99% of theory) of 8-ethoxy-4,7-difluoro-3-hydroxy-6H-benzo[c]chromene as colourless crystals.
CCOc1ccc2c(c1F)COc1c-2ccc(OCc2ccccc2)c1F
null
CCOc1ccc2c(c1F)c(=O)oc1c(F)c(OCc3ccccc3)ccc12
null
null
[CH2:1]([O:8][C:9]1[C:18]([F:19])=[C:17]2[C:12]([C:13]3[CH:24]=[CH:23][C:22]([O:25][CH2:26][CH3:27])=[C:21]([F:28])[C:14]=3[C:15](=O)[O:16]2)=[CH:11][CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.BrC1C=CC(OCC)=C(F)C=1.COCCOC.[BH4-].[Na+]>C1COCC1>[CH2:1]([O:8][C:9]1[C:18]([F:19])=[C:17]2[C:12]([C:13]3[CH:24]=[CH:23][C:22]([O:25][CH2:26][CH3:27])=[C:21]([F:28])[C:14]=3[CH2:15][O:16]2)=[CH:11][CH:10]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
18
C1CCOC1
COCCOC
null
25
null
77.7
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,347,214
[K+]
null
null
null
ord_dataset-6034127657614f02860ed057b62b882e
2013-01-01T00:10:00
true
N-[2-(2-Mercapto-7,8-dihydro-6H-indeno[5,4-d][1,3]oxazol-8-yl)ethyl]acetamide (108 mg, 0.391 mmol) was dissolved in N,N-dimethylformamide (4 mL), iodomethane (48.6 μL, 0.782 mmol) and potassium carbonate (59.4 mg, 0.430 mmol) were added, and the mixture was stirred at room temperature for 15 min. The reaction solution was diluted with diethyl ether, washed with saturated aqueous sodium hydrogencarbonate solution and saturated brine and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate/hexane=50/50→100/0) to give the title compound (81.2 mg, yield 72%).
CSc1nc2ccc3c(c2o1)C(CCNC(C)=O)CC3
null
CC(=O)NCCC1CCc2ccc3nc(S)oc3c21
O=C([O-])[O-]
null
[SH:1][C:2]1[O:3][C:4]2[C:13]3[CH:12]([CH2:14][CH2:15][NH:16][C:17](=[O:19])[CH3:18])[CH2:11][CH2:10][C:9]=3[CH:8]=[CH:7][C:5]=2[N:6]=1.IC.[C:22](=O)([O-])[O-].[K+].[K+]>CN(C)C=O.C(OCC)C>[CH3:22][S:1][C:2]1[O:3][C:4]2[C:13]3[CH:12]([CH2:14][CH2:15][NH:16][C:17](=[O:19])[CH3:18])[CH2:11][CH2:10][C:9]=3[CH:8]=[CH:7][C:5]=2[N:6]=1
0.25
CI
CN(C)C=O
CCOCC
25
null
71.5
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
186,616
O=C1C=CC(=O)O1
null
null
null
ord_dataset-754e10d30fb249229e130865010ab25b
1989-01-01T00:03:00
true
In 200 ml of methyl ethyl ketone were dissolved 18.14 g of maleic anhydride and 21.86 g of α-methylstyrene, and to the solution was added 1.82 g of azobisisobutylnitrile (AIBN). The resulting mixture was heated at 60° C. for 7 hours under nitrogen atmosphere for performing polymerization. The reaction solution was then dropwise added to 500 ml of ethyl ether under stirring to precipitate a polymer. Thus precipitated polymer was collected by filtration and purified by repeating twice the THF dissolution-ethyl ether precipitation procedure described in Example 1. Thus purified polymer was dried under vacuum at 100° C. for 24 hours to give 17.0 g of a maleic anhydride-styrene copolymer. It was confiremed by elementary analysis that the copolymerization ratio was approximately 1:1. Mn was 11,730.
C=Cc1ccccc1
null
C=C(C)c1ccccc1
null
null
[C:1]1(=[O:7])[O:6][C:4](=[O:5])[CH:3]=[CH:2]1.[CH3:8][C:9]([C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)=C.C(OCC)C>C(C(C)=O)C>[CH2:8]=[CH:9][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[CH:2]1[C:1](=[O:7])[O:6][C:4](=[O:5])[CH:3]=1
null
CCOCC
CCC(C)=O
null
60
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
603,290
CCN=C=NCCCN(C)C
Cl
On1nnc2ccccc21
null
ord_dataset-82e842e611ef4a05b6e7f9ea0a46d52d
2003-01-01T00:07:00
true
5-[5-(2,6-Dimethyl-phenylmethanesulfonyl)-2-oxo-1,2-dihydro-indol-(3Z)-ylidenemethyl]-2,4-dimethyl-1H-pyrrole-3-carboxylic acid (120 mg, 0.26 mmol) was coupled with (S)-2-pyrrolidin-1-ylmethyl-pyrrolidine (50 mg, 1.2 eq.), HOBt (42 mg, 1.2 eq.), EDAC.HCl (60 mg, 1.2 eq.) and TEA (3 eq.) in acetonitrile: DMF (3:1) to give the titled compound.
Cc1cccc(C)c1CS(=O)(=O)c1ccc2c(c1)/C(=C/c1[nH]c(C)c(C(=O)N3CCC[C@H]3CN3CCCC3)c1C)C(=O)N2
null
Cc1cccc(C)c1CS(=O)(=O)c1ccc2c(c1)/C(=C/c1[nH]c(C)c(C(=O)O)c1C)C(=O)N2
C1CN[C@H](CN2CCCC2)C1
null
[CH3:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH3:8])[C:3]=1[CH2:9][S:10]([C:13]1[CH:14]=[C:15]2[C:19](=[CH:20][CH:21]=1)[NH:18][C:17](=[O:22])/[C:16]/2=[CH:23]\[C:24]1[NH:28][C:27]([CH3:29])=[C:26]([C:30](O)=[O:31])[C:25]=1[CH3:33])(=[O:12])=[O:11].[N:34]1([CH2:39][C@@H:40]2[CH2:44][CH2:43][CH2:42][NH:41]2)[CH2:38][CH2:37][CH2:36][CH2:35]1.C1C=CC2N(O)N=NC=2C=1.CCN=C=NCCCN(C)C.Cl>C(#N)C.CN(C=O)C>[CH3:8][C:4]1[CH:5]=[CH:6][CH:7]=[C:2]([CH3:1])[C:3]=1[CH2:9][S:10]([C:13]1[CH:14]=[C:15]2[C:19](=[CH:20][CH:21]=1)[NH:18][C:17](=[O:22])/[C:16]/2=[CH:23]\[C:24]1[NH:28][C:27]([CH3:29])=[C:26]([C:30]([N:41]2[CH2:42][CH2:43][CH2:44][C@H:40]2[CH2:39][N:34]2[CH2:38][CH2:37][CH2:36][CH2:35]2)=[O:31])[C:25]=1[CH3:33])(=[O:11])=[O:12]
null
CC#N
CN(C)C=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
1,505,053
On1nnc2ccccc21
null
null
null
ord_dataset-1a1aa5d1c3224edca0aec6e3398da985
2014-01-01T00:11:00
true
(4-acetyl-phenylazo)-(3,3-dimethyl-3,4-dihydro-2H-isoquinoline-1-ylidene)-acetic acid, dimethylamine, HOBt (Advanced ChemTech Corp., USA) and triethylamine are dissolved in DMF, a dichloromethane solution of HETU (Advanced ChemTech Corp., USA) is added, and then the mixture is stirred at room temperature. The stirred and blended solvent is washed with a saturated aqueous sodium chloride solution and a 5% aqueous sodium hydrogen carbonate solution. The reaction product is dried with anhydrous sodium sulfate and filtered and, then, the solvent is removed by reducing the pressure. The residue containing the reaction product is purified by column chromatography to obtain the title compound.
CC(=O)c1ccc(N=NC(C(=O)N(C)C)=C2NC(C)(C)Cc3ccccc32)cc1
null
CNC
CC(=O)c1ccc(N=NC(C(=O)O)=C2NC(C)(C)Cc3ccccc32)cc1
null
[C:1]([C:4]1[CH:9]=[CH:8][C:7]([N:10]=[N:11][C:12](=[C:16]2[C:25]3[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=3)[CH2:19][C:18]([CH3:27])([CH3:26])[NH:17]2)[C:13](O)=[O:14])=[CH:6][CH:5]=1)(=[O:3])[CH3:2].[CH3:28][NH:29][CH3:30].C1C=CC2N(O)N=NC=2C=1.C(N(CC)CC)C>CN(C=O)C.ClCCl>[C:1]([C:4]1[CH:9]=[CH:8][C:7]([N:10]=[N:11][C:12](=[C:16]2[C:25]3[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=3)[CH2:19][C:18]([CH3:26])([CH3:27])[NH:17]2)[C:13]([N:29]([CH3:30])[CH3:28])=[O:14])=[CH:6][CH:5]=1)(=[O:3])[CH3:2]
null
CN(C)C=O
ClCCl
CCN(CC)CC
25
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,477,142
null
null
null
null
ord_dataset-c3c1091f873b4f40827973a6f1f9b685
2014-01-01T00:09:00
true
Using a procedure similar to that described in Example 1, except using 2-amino-3-(4-bromo-5,7-dichloro-2H-benzotriazol-2-yl)-2-methylpropionitrile and 4-trifluoromethylthiobenzoyl chloride, the title compound was isolated as a white solid (110 mg, described in Example 55). MS (ES): M/Z [M+H]=552. NMR: (400 MHz, DMSO-d6): 1.75 (s, 3H), 5.44 (d, J=13.3 Hz, 1H), 5.60 (d, J=13.7 Hz, 1H), 7.75-8.04 (m, 5H) and 8.91 (s, 1H). 19F NMR (376 MHz, DMSO-d6): −42.0 (s, 3F).
CC(C#N)(Cn1nc2c(Cl)cc(Cl)c(Br)c2n1)NC(=S)c1ccc(C(F)(F)F)cc1
null
FC(F)(F)c1ccc(C(=S)Cl)cc1
CC(N)(C#N)Cn1nc2c(Cl)cc(Cl)c(Br)c2n1
null
[NH2:1][C:2]([CH3:18])([CH2:5][N:6]1[N:10]=[C:9]2[C:11]([Cl:17])=[CH:12][C:13]([Cl:16])=[C:14]([Br:15])[C:8]2=[N:7]1)[C:3]#[N:4].[F:19][C:20]([F:31])([F:30])[C:21]1[CH:29]=[CH:28][C:24]([C:25](Cl)=[S:26])=[CH:23][CH:22]=1>>[Br:15][C:14]1[C:8]2[C:9](=[N:10][N:6]([CH2:5][C:2]([NH:1][C:25](=[S:26])[C:24]3[CH:23]=[CH:22][C:21]([C:20]([F:19])([F:30])[F:31])=[CH:29][CH:28]=3)([C:3]#[N:4])[CH3:18])[N:7]=2)[C:11]([Cl:17])=[CH:12][C:13]=1[Cl:16]
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
161,729
COS(=O)(=O)[O-]
null
null
null
ord_dataset-c34472859da14a81bfe0f74e60f15c43
1987-01-01T00:08:00
true
A mixture of 2-methyl-3-trimethylammoniomethylimidazo[2,1-a]isoquinoline methylsulfate (3 g) and 2-methylimidazole (1.6 g) in ethanol (50 ml) was refluxed with stirring for 4 hours and evaporated in vacuo. To the residue was added water and the resulting precipitates were collected by filtration, dried and recrystallized from ethyl acetate to give 2-methyl-3-(2-methyl-1-imidazolylmethyl)imidazo[2,1-a]isoquinoline (0.85 g).
Cc1nc2c3ccccc3ccn2c1CC1(C)N=CC=N1
null
Cc1ncc[nH]1
Cc1nc2c3ccccc3ccn2c1C[N+](C)(C)C
null
COS([O-])(=O)=O.[CH3:7][C:8]1[N:9]=[C:10]2[C:19]3[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=3)[CH:13]=[CH:12][N:11]2[C:20]=1[CH2:21][N+](C)(C)C.[CH3:26][C:27]1[NH:28][CH:29]=[CH:30][N:31]=1>C(O)C>[CH3:7][C:8]1[N:9]=[C:10]2[C:19]3[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=3)[CH:13]=[CH:12][N:11]2[C:20]=1[CH2:21][C:27]1([CH3:26])[N:31]=[CH:30][CH:29]=[N:28]1
4
CCO
null
null
null
37.5
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
693,606
CCN=C=N
Cl
On1nnc2ccccc21
null
ord_dataset-35824232b132464aa99e71aba765981d
2005-01-01T00:12:00
true
10-(4-Cyclohex-1-en-1-yl-3-methyl-benzoyl)-10,11-dihydro-5H-pyrrolo[2,1-c][1,4]benzodiazepine-3-carboxylic acid (0.300 g, 0.703 mmol) of Example 5 Step E, D-serine methyl ester hydrochloride (0.131 g, 0.844 mmol), 1-hydroxy benzotriazole (0.104 g, 0.773 mmol) and 1-[3-dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (0.148 g, 0.773 mmol) were combined in amine-free N,N-dimethylformamide (2.8 mL), followed by the addition of N,N-diisopropylethylamine (0.307 mL, 1.76 mmol). The reaction was stirred at room temperature for 12 hours, then diluted with ethyl acetate and washed with water, 1 N hydrochloric acid, 1 N sodium hydroxide and brine. The combined aqueous washings were saturated with sodium chloride, and extracted with ethyl acetate. The organic phases were combined, dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by flash column chromatography on silica gel eluting with 10% methanol in chloroform, to afford 0.320 g of the title compound as a pale yellow solid.
COC(=O)[C@@H](CO)NC(=O)c1ccc2n1Cc1ccccc1N(C(=O)c1ccc(C3=CCCCC3)c(C)c1)C2
null
COC(=O)[C@H](N)CO
Cc1cc(C(=O)N2Cc3ccc(C(=O)O)n3Cc3ccccc32)ccc1C1=CCCCC1
null
[C:1]1([C:7]2[CH:31]=[CH:30][C:10]([C:11]([N:13]3[C:19]4[CH:20]=[CH:21][CH:22]=[CH:23][C:18]=4[CH2:17][N:16]4[C:24]([C:27](O)=[O:28])=[CH:25][CH:26]=[C:15]4[CH2:14]3)=[O:12])=[CH:9][C:8]=2[CH3:32])[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]=1.Cl.[CH3:34][O:35][C:36](=[O:41])[C@@H:37]([CH2:39][OH:40])[NH2:38].ON1C2C=CC=CC=2N=N1.Cl.C(N=C=N)C.C(N(CC)C(C)C)(C)C>C(OCC)(=O)C>[CH3:34][O:35][C:36](=[O:41])[C@H:37]([NH:38][C:27]([C:24]1[N:16]2[C:15]([CH2:14][N:13]([C:11](=[O:12])[C:10]3[CH:30]=[CH:31][C:7]([C:1]4[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]=4)=[C:8]([CH3:32])[CH:9]=3)[C:19]3[CH:18]=[CH:23][CH:22]=[CH:21][C:20]=3[CH2:17]2)=[CH:26][CH:25]=1)=[O:28])[CH2:39][OH:40]
12
CCN(C(C)C)C(C)C
CCOC(C)=O
null
25
null
86.3
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,261,873
null
null
null
null
ord_dataset-266f60b4555945d6afb2d2bdf5fa04e0
2013-01-01T00:02:00
true
To a stirred solution of 1-Boc-piperazine (0.50 g, 2.7 mmol) and diisopropylethylamine (1.75 g, 13.5 mmol) in dichloromethane at 0° C. was added a solution of 2-trifluoromethylbenzoyl chloride (0.626 g, 3.0 mmol). The resulting mixture was stirred at room temperature for 20 h and then quenched with water (25 mL). The organic phase was washed with water, dried over anhydrous Na2SO4, filtered and concentrated in vacuo to yield 4-(2-trifluoromethylbenzoyl)piperazine-1-carboxylic acid tent-butyl ester as a pale brown oil (0.948 g, 98% yield). 1H NMR (300 MHz, CDCl3) δ 7.69, 7.54, 7.30, 3.77, 3.51, 3.33, 3.14, 1.45.
O=C(O)N1CCN(C(=O)c2ccccc2C(F)(F)F)CC1
null
O=C(Cl)c1ccccc1C(F)(F)F
CC(C)(C)OC(=O)N1CCNCC1
null
[C:1]([N:8]1[CH2:13][CH2:12][NH:11][CH2:10][CH2:9]1)([O:3]C(C)(C)C)=[O:2].C(N(C(C)C)CC)(C)C.[F:23][C:24]([F:35])([F:34])[C:25]1[CH:33]=[CH:32][CH:31]=[CH:30][C:26]=1[C:27](Cl)=[O:28]>ClCCl>[F:23][C:24]([F:34])([F:35])[C:25]1[CH:33]=[CH:32][CH:31]=[CH:30][C:26]=1[C:27]([N:11]1[CH2:10][CH2:9][N:8]([C:1]([OH:3])=[O:2])[CH2:13][CH2:12]1)=[O:28]
20
ClCCl
CCN(C(C)C)C(C)C
null
25
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,589,305
[H-]
[Na+]
null
null
ord_dataset-e8c6a25568b64529b960953990e6921f
2015-01-01T00:06:00
true
To a solution of NaH (60% dispersed in oil, 32 mg, 0.81 mmo) in THF (4 mL) at 0° C. was added alcohol 1 (180 mg, 0.62 mmol) in THF (1 mL) and the reaction mixture was stirred for 30 min at this temperature. Then 3-pyridyl isothiocyanate (169 mg, 124 mmol) in THF (1 mL) was added and stirred at rt. After stirring for 12 h, the reaction mixture was quenched water and extracted with EtOAc (3×). The organic layer was dried and concentrated to get a residue, which was purified by column chromatography (Hexane/EtOAc) to yield thiocarbamate 38a as a viscous liquid (179 mg, 70%). TLC Rf: 0.23 (20% EtOAc/hexanes); 1H NMR (300 MHz, CDCl3): δ 8.55 (d, 1H), 8.40 (d, 1H), 7.95 (m, 1H), 7.30 (m, 2H), 5.49 (t, 1H), 5.11 (m, 3H), 4.70 (d, 2H), 2.16-1.19 (m, 12H), 1.76 (s, 3H), 1.68 (s, 3H), 1.60 (s, 9H); LCMS: MS (m/z): 427 (M+H).
CC(C)=CCC/C(C)=C/CC/C(C)=C/CC/C(C)=C/COC(=S)Nc1cccnc1
null
S=C=Nc1cccnc1
CC(C)=CCC/C(C)=C/CC/C(C)=C/CC/C(C)=C/CO
null
[H-].[Na+].[CH2:3]([CH2:13]/[C:14](/[CH3:23])=[CH:15]/[CH2:16][CH2:17]/[C:18](/[CH3:22])=[CH:19]/[CH2:20][OH:21])/[CH:4]=[C:5](/[CH2:7][CH2:8][CH:9]=[C:10]([CH3:12])[CH3:11])\[CH3:6].[N:24]1[CH:29]=[CH:28][CH:27]=[C:26]([N:30]=[C:31]=[S:32])[CH:25]=1>C1COCC1>[N:24]1[CH:29]=[CH:28][CH:27]=[C:26]([NH:30][C:31](=[S:32])[O:21][CH2:20]/[CH:19]=[C:18](\[CH3:22])/[CH2:17][CH2:16]/[CH:15]=[C:14](\[CH3:23])/[CH2:13][CH2:3]/[CH:4]=[C:5](\[CH3:6])/[CH2:7][CH2:8][CH:9]=[C:10]([CH3:12])[CH3:11])[CH:25]=1
0.5
C1CCOC1
null
null
null
67.7
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,117,117
null
null
null
null
ord_dataset-4226e9b4f9f845db967ed997270dcafc
2011-01-01T00:12:00
true
Using general procedure 2 with [(R)-2-(2-fluoro-phenyl)-1-(methoxy-methyl-carbamoyl)-ethyl]-carbamic acid tert-butyl ester (1.5 g, 4.6 mmol) and N-tert-butyl-2-chloro-6-methyl-benzamide (1.5 g, 4.6 mmol), followed by purification by silica gel flash column chromatography gives the title compound.
CC(C)(C)NC(=O)c1c(Cl)cccc1CC(=O)[C@@H](Cc1ccccc1F)NC(=O)OC(C)(C)C
null
Cc1cccc(Cl)c1C(=O)NC(C)(C)C
CON(C)C(=O)[C@@H](Cc1ccccc1F)NC(=O)OC(C)(C)C
null
[C:1]([O:5][C:6](=[O:23])[NH:7][C@@H:8]([C:17](=[O:22])N(OC)C)[CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[F:16])([CH3:4])([CH3:3])[CH3:2].[C:24]([NH:28][C:29](=[O:38])[C:30]1[C:35]([CH3:36])=[CH:34][CH:33]=[CH:32][C:31]=1[Cl:37])([CH3:27])([CH3:26])[CH3:25]>>[C:1]([O:5][C:6](=[O:23])[NH:7][C@H:8]([CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[F:16])[C:17](=[O:22])[CH2:36][C:35]1[CH:34]=[CH:33][CH:32]=[C:31]([Cl:37])[C:30]=1[C:29](=[O:38])[NH:28][C:24]([CH3:26])([CH3:25])[CH3:27])([CH3:2])([CH3:3])[CH3:4]
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
1,361,615
null
null
null
null
ord_dataset-d932d1d683704a8bad3d064bcb197acc
2013-01-01T00:11:00
true
A solution of 2-butyl-1-[4-(4-chloro-phenoxy)-phenyl]-4-[4-((S)-1-oxiranylmethoxy)-phenyl]-1H-imidazole (from intermediate A3) in 3 mL of dimethylamine in THF (2M) was stirred at 76° C. for 1 h in a microwave reactor. Upon completion (determined by LC/MS), the reaction was evaporated in vacuo and purified by silica gel flash column chromatography using a gradient of EtOAc to 96% EtOAc/(2M NH3/MeOH) as an eluent to afford (S)-1-(4-{2-butyl-1-[4-(4-chloro-phenoxy)-phenyl]-1H-imidazol-4-yl}-phenoxy)-3-dimethylamino-propan-2-ol.
CCCCc1nc(-c2ccc(OC[C@@H](O)CN(C)C)cc2)cn1-c1ccc(Oc2ccc(Cl)cc2)cc1
null
CCCCc1nc(-c2ccc(OC[C@@H]3CO3)cc2)cn1-c1ccc(Oc2ccc(Cl)cc2)cc1
CNC
null
[CH2:1]([C:5]1[N:6]([C:21]2[CH:26]=[CH:25][C:24]([O:27][C:28]3[CH:33]=[CH:32][C:31]([Cl:34])=[CH:30][CH:29]=3)=[CH:23][CH:22]=2)[CH:7]=[C:8]([C:10]2[CH:15]=[CH:14][C:13]([O:16][CH2:17][C@@H:18]3[CH2:20][O:19]3)=[CH:12][CH:11]=2)[N:9]=1)[CH2:2][CH2:3][CH3:4].[CH3:35][NH:36][CH3:37]>C1COCC1>[CH2:1]([C:5]1[N:6]([C:21]2[CH:22]=[CH:23][C:24]([O:27][C:28]3[CH:33]=[CH:32][C:31]([Cl:34])=[CH:30][CH:29]=3)=[CH:25][CH:26]=2)[CH:7]=[C:8]([C:10]2[CH:11]=[CH:12][C:13]([O:16][CH2:17][C@@H:18]([OH:19])[CH2:20][N:36]([CH3:37])[CH3:35])=[CH:14][CH:15]=2)[N:9]=1)[CH2:2][CH2:3][CH3:4]
null
C1CCOC1
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
1,071,431
null
null
null
null
ord_dataset-5df93261afc143c3ae919a57ff4fc1d4
2011-01-01T00:07:00
true
0.63 g of 6-(2H-tetrazol-5-yl)-2,2′-bipyridine was dissolved in 10 ml of dehydrated pyridine, and 0.29 g of isophthaloyl dichloride was gradually added. Temperature was elevated to 115° C., and stirring was conducted for 6 hours under reflux. After cooling to room temperature, the reaction solution was poured into water, and a precipitated white solid was taken out by suction filtration, and washed with water. The solid obtained was vacuum dried at 80° C. for 20 hours, and purified with column chromatography (carrier: silica gel, eluting solution: chloroform/methanol=20/1) to obtain 0.62 g (yield 81%) of BpyOXDm. The product was identified with NMR analysis. The result of NMR analysis (CDCl3) was as follows. 9.071 ppm (1H), 8.639-8.714 ppm (6H), 8.325-8.477 ppm (4H), 8.037 ppm (2H), 7.756-7.854 ppm (3H), 7.330 ppm (2H).
c1ccc(-c2cccc(-c3nnc(-c4cccc(-c5nnc(-c6cccc(-c7ccccn7)n6)o5)c4)o3)n2)nc1
null
c1ccc(-c2cccc(-c3nn[nH]n3)n2)nc1
O=C(Cl)c1cccc(C(=O)Cl)c1
null
N1N[N:3]=[N:4][C:5]=1[C:6]1[N:11]=[C:10]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][N:13]=2)[CH:9]=[CH:8][CH:7]=1.[C:18](Cl)(=[O:28])[C:19]1[CH:27]=[CH:26][CH:25]=[C:21]([C:22](Cl)=[O:23])[CH:20]=1.O>N1C=CC=CC=1>[N:11]1[C:6]([C:5]2[O:28][C:18]([C:19]3[CH:27]=[CH:26][CH:25]=[C:21]([C:22]4[O:23][C:5]([C:6]5[N:11]=[C:10]([C:12]6[CH:17]=[CH:16][CH:15]=[CH:14][N:13]=6)[CH:9]=[CH:8][CH:7]=5)=[N:4][N:3]=4)[CH:20]=3)=[N:3][N:4]=2)=[CH:7][CH:8]=[CH:9][C:10]=1[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][N:13]=1
6
O
c1ccncc1
null
25
null
81
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
517,739
Cl
null
null
null
ord_dataset-a495451286334c5c9bbcbd48a00c1350
2001-01-01T00:09:00
true
A mixture of N-[(3RS)-1-(3-azabicyclo[3.2.2]non-3-yl)carbonylmethyl-2,3-dihydro-9-methyl-5-(2-fluorophenyl)-2-oxo-1H-1,4-benzodiazepin-3-yl]-N′-(3-acetylphenyl)urea (217 mg) and hydroxylamine-hydrochloride (124 mg), triethylamine (180 mg) in tetrahydrofuran (4 ml) was stirred at room temperature overnight. Ethyl acetate and 1N aqueous hydrochloric acid solution were added the reaction mixture. The separated organic layer was washed with 1N aqueous hydrochloric acid twice, saturated aqueous sodium bicarbonate and brine successively and then dried over magnesium sulfate. The solvent was evaporated in vacuo to afford N-[(3RS)-1-(3-azabicyclo[3.2.2]non-3-yl)carbonylmethyl-2,3-dihydro-9-methyl-5-(2-fluorophenyl)-2-oxo-1H-1,4-benzodiazepin-3-yl]-N′-[3-(1-hydroxyiminoethyl)phenyl]urea (235.0 mg) as a crystalline powder.
CC(=NO)c1cccc(NC(=O)NC2N=C(c3ccccc3F)c3cccc(C)c3N(CC(=O)N3CC4CCC(CC4)C3)C2=O)c1
null
NO
CC(=O)c1cccc(NC(=O)NC2N=C(c3ccccc3F)c3cccc(C)c3N(CC(=O)N3CC4CCC(CC4)C3)C2=O)c1
null
[CH:1]12[CH2:9][CH2:8][CH:5]([CH2:6][CH2:7]1)[CH2:4][N:3]([C:10]([CH2:12][N:13]1[C:19]3[C:20]([CH3:24])=[CH:21][CH:22]=[CH:23][C:18]=3[C:17]([C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=3[F:31])=[N:16][CH:15]([NH:32][C:33]([NH:35][C:36]3[CH:41]=[CH:40][CH:39]=[C:38]([C:42](=O)[CH3:43])[CH:37]=3)=[O:34])[C:14]1=[O:45])=[O:11])[CH2:2]2.Cl.[NH2:47][OH:48].C(N(CC)CC)C.Cl>O1CCCC1.C(OCC)(=O)C>[CH:5]12[CH2:6][CH2:7][CH:1]([CH2:9][CH2:8]1)[CH2:2][N:3]([C:10]([CH2:12][N:13]1[C:19]3[C:20]([CH3:24])=[CH:21][CH:22]=[CH:23][C:18]=3[C:17]([C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=3[F:31])=[N:16][CH:15]([NH:32][C:33]([NH:35][C:36]3[CH:41]=[CH:40][CH:39]=[C:38]([C:42](=[N:47][OH:48])[CH3:43])[CH:37]=3)=[O:34])[C:14]1=[O:45])=[O:11])[CH2:4]2
8
CCOC(C)=O
CCN(CC)CC
C1CCOC1
25
105.7
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
964,465
null
null
null
null
ord_dataset-03ba810b7f464a06b5d8787af2e8b64e
2010-01-01T00:06:00
true
The bromination of 2-isobutyl-2-methyl-cyclohexanone takes place in a manner similar to that described above for the preparation of 2-bromo-4-isopropyl-cyclohexanone. The title compound is reacted as a crude product without further characterization.
CC(C)CC1(C)CCCC(Br)C1=O
null
CC(C)CC1(C)CCCCC1=O
CC(C)C1CCC(=O)C(Br)C1
null
[CH2:1]([C:5]1([CH3:12])[CH2:10][CH2:9][CH2:8][CH2:7][C:6]1=[O:11])[CH:2]([CH3:4])[CH3:3].[Br:13]C1CC(C(C)C)CCC1=O>>[Br:13][CH:7]1[C:6](=[O:11])[C:5]([CH2:1][CH:2]([CH3:4])[CH3:3])([CH3:12])[CH2:10][CH2:9][CH2:8]1
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
1,685,231
[Ni]
N
null
null
ord_dataset-3953983e052a4076aa7cc0880b79cb8b
2016-01-01T00:01:00
true
To a solution of 2,6-dimethyl-2H-indazole-7-carbonitrile (1 equiv.) in methanol and aq. ammonia solution (9:1), catalytic amount of Raney Nickel was added. Reaction mass was stirred at room temperature under hydrogen pressure (balloon pressure) for 2-5 h. On completion of reaction, it was filtered through celite bed and filtrate was concentrated under reduce pressure to afford the title compound (quant. yield).
Cc1ccc2cn(C)nc2c1CN
null
Cc1ccc2cn(C)nc2c1C#N
null
null
[CH3:1][N:2]1[CH:10]=[C:9]2[C:4]([C:5]([C:12]#[N:13])=[C:6]([CH3:11])[CH:7]=[CH:8]2)=[N:3]1>CO.N.[Ni]>[CH3:1][N:2]1[CH:10]=[C:9]2[C:4]([C:5]([CH2:12][NH2:13])=[C:6]([CH3:11])[CH:7]=[CH:8]2)=[N:3]1
3.5
CO
null
null
25
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,167,218
null
null
null
null
ord_dataset-d24cc23b3db94284bb83a2ccdd9eb880
2012-01-01T00:05:00
true
cis-cis-1,12-Dibromo-dodeca-5,7-diene was added to a solution of 3-picoline (3 mmol) in acetonitrile and the solution refluxed for 24 hours. The acetonitrile was removed in vacuum and the resulting residue was partitioned between ether and water. The aqueous layer was washed extensively with ether until no picoline left in the aqueous layer. The resulting aqueous solution of the product was lyophilized to yield the pure product. (76%). 1HNMR (300 MHz, D2O, ppm) 8.50 (s, 2H), 8.44 (d, J=6.3, 2H), 8.16 (d, J=7.8, 2H), 7.74 (dd, J=7.8, J=6.3, 2H), 6.15-6.18 (m, 2H), 5.38-5.38 (m, 2H), 4.38 (t, J=5.7, 4H), 2.35 (s, 6H), 2.06 (q, J=7.5, 4H), 1.83 (p, J=7.5, 4H), 1.25 (p, J=7.5, 4H). 13CNMR, 145.99, 143.71, 141.30, 139.95, 132.19, 127.46, 124.06, 61.69, 30.27, 26.35, 25.44, 17.93.
Cc1ccc[n+](CCCC/C=C\C=C/CCCC[n+]2cccc(C)c2)c1
[Br-]
Cc1cccnc1
BrCCCC/C=C\C=C/CCCCBr
null
[Br:1][CH2:2][CH2:3][CH2:4][CH2:5]/[CH:6]=[CH:7]\[CH:8]=[CH:9]/[CH2:10][CH2:11][CH2:12][CH2:13]Br.[N:15]1[CH:20]=[CH:19][CH:18]=[C:17]([CH3:21])[CH:16]=1>C(#N)C>[Br-:1].[Br-:1].[CH2:2]([N+:15]1[CH:20]=[CH:19][CH:18]=[C:17]([CH3:21])[CH:16]=1)[CH2:3][CH2:4][CH2:5]/[CH:6]=[CH:7]\[CH:8]=[CH:9]/[CH2:10][CH2:11][CH2:12][CH2:13][N+:15]1[CH:20]=[CH:19][CH:18]=[C:17]([CH3:21])[CH:16]=1
null
CC#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
776,665
null
null
null
null
ord_dataset-bf316bf78f4f45d4b275959c08104b7c
2007-01-01T00:06:00
true
A solution of 2-[[bis(allyloxy)phosphoryl]oxymethyl]-3-methylbenzoic acid (880 mg, 2.70 mmol) obtained from Example 22-(5) in dichloromethane (15 ml) was cooled to 0° C., and then N,N-dimethylformamide (15 μl) and oxalyl chloride (1.71 g, 13.5 mmol) were added thereto. After the mixture was stirred at room temperature for 30 minutes, crude 2-[[bis(allyloxy)phosphoryl]oxymethyl]-3-methylbenzoyl chloride was obtained according to a similar procedure to that described in Example 1-(12).
C=CCOP(=O)(OCC=C)OCc1c(C)cccc1C(=O)Cl
null
C=CCOP(=O)(OCC=C)OCc1c(C)cccc1C(=O)O
O=C(Cl)C(=O)Cl
null
[CH2:1]([O:4][P:5]([O:11][CH2:12][C:13]1[C:21]([CH3:22])=[CH:20][CH:19]=[CH:18][C:14]=1[C:15](O)=[O:16])([O:7][CH2:8][CH:9]=[CH2:10])=[O:6])[CH:2]=[CH2:3].CN(C)C=O.C(Cl)(=O)C([Cl:31])=O>ClCCl>[CH2:1]([O:4][P:5]([O:11][CH2:12][C:13]1[C:21]([CH3:22])=[CH:20][CH:19]=[CH:18][C:14]=1[C:15]([Cl:31])=[O:16])([O:7][CH2:8][CH:9]=[CH2:10])=[O:6])[CH:2]=[CH2:3]
0.5
CN(C)C=O
ClCCl
null
25
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
65,115
null
null
null
null
ord_dataset-d986d6c6630b41ee8d401fd85be47701
1980-01-01T00:04:00
true
A mixture of 2-methyleneglutaric acid [Ber. 34, 427 (1901)] (40 g.) and acetyl chloride (80 ml.) is heated on the steam bath for 1.5 hours. The excess acetyl chloride is removed in vacuo (75°) and the residue is evaporated from toluene twice. Finally, the residue is dissolved in ethanol and heated on the steam bath for one hour. The reaction mixture is concentrated to dryness to yield 2-methylene-4-(ethoxycarbonyl)butyric acid.
C=C(CCC(=O)OCC)C(=O)O
null
C=C(CCC(=O)O)C(=O)O
CC(=O)Cl
null
[CH2:1]=[C:2]([CH2:6][CH2:7][C:8]([OH:10])=[O:9])[C:3]([OH:5])=[O:4].[C:11](Cl)(=O)[CH3:12]>>[CH2:1]=[C:2]([CH2:6][CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:3]([OH:5])=[O:4]
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
700,867
[Na+]
[OH-]
null
null
ord_dataset-bbd7e53f000345838ad4920a07a169ff
2006-01-01T00:03:00
true
Ethyl N-(3-cyano-4-neopentyloxyphenyl)-N-[1-(3-trifluoromethylphenyl)-3-methylpyrazol-4-ylcarbonyl]glycine (1.5 g) was added to ethanol (15 ml). 10% Aqueous sodium hydroxide solution (10 ml) was added and the mixture was stirred at a refluxing temperature for 30 min. The solvent was evaporated under reduced pressure. Dilute hydrochloric acid was added to the residue and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate, after which the solvent was evaporated under reduced pressure. A mixed solvent of chloroform-n-hexane was added to the residue to allow crystallization. The crystals were recrystallized from hydrous acetic acid to give the title compound (0.9 g), melting point: 110–112° C.
Cc1nn(-c2cccc(C(F)(F)F)c2)cc1C(=O)N(CC(=O)O)c1ccc(OCC(C)(C)C)c(C#N)c1
null
CCC(C(=O)O)N(C(=O)c1cn(-c2cccc(C(F)(F)F)c2)nc1C)c1ccc(OCC(C)(C)C)c(C#N)c1
null
null
C([CH:3]([C:37]([OH:39])=[O:38])[N:4]([C:23]1[CH:28]=[CH:27][C:26]([O:29][CH2:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[C:25]([C:35]#[N:36])[CH:24]=1)[C:5]([C:7]1[C:8]([CH3:22])=[N:9][N:10]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([C:18]([F:21])([F:20])[F:19])[CH:13]=2)[CH:11]=1)=[O:6])C.[OH-].[Na+]>C(O)C>[C:35]([C:25]1[CH:24]=[C:23]([N:4]([C:5]([C:7]2[C:8]([CH3:22])=[N:9][N:10]([C:12]3[CH:17]=[CH:16][CH:15]=[C:14]([C:18]([F:20])([F:21])[F:19])[CH:13]=3)[CH:11]=2)=[O:6])[CH2:3][C:37]([OH:39])=[O:38])[CH:28]=[CH:27][C:26]=1[O:29][CH2:30][C:31]([CH3:34])([CH3:33])[CH3:32])#[N:36]
0.5
CCO
null
null
null
null
63.3
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,393,050
Br[P+](N1CCCC1)(N1CCCC1)N1CCCC1
F[P-](F)(F)(F)(F)F
null
null
ord_dataset-12dc3bd21bcf44d09e5b4249afe15161
2014-01-01T00:02:00
true
To a solution of (R)-1-(3-fluoro-5-(1,1,2,2-tetrafluoroethoxy)phenyl)-1-(4-fluorophenyl)-2-phenylethanamine (31 mg, 0.07 mmol), prepared as described in Procedure 3, 4, 5 and 6, in DCM (1 mL) was added (9H-fluoren-9-yl)methyl 1-amino-4,4,4-trifluoro-1-oxobutan-2-ylcarbamate (31 mg, 0.08 mmol), followed by PyBrOP and iPr2NEt. The reaction mixture was stirred at rt for 72 h and concentrated. The residue was purified by preparative HPLC (Axia column, 30×100 mm, 60-100% MeOH/H2O with 0.1% TFA over 12 min, flow rate 40 mL/min, monitoring at 220 nm) to yield (9H-fluoren-9-yl)methyl 4,4,4-trifluoro-1-((R)-1-(3-fluoro-5-(1,1,2,2-tetrafluoroethoxy)phenyl)-1-(4-fluorophenyl)-2-phenylethylamino)-1-oxobutan-2-ylcarbamate as white solid (20 mg, 38% yield). LCMS: RT=4.5 min [M+H] 787.3 (Phenomenex Luna C18 column, 4.6×50 mm eluting with 10-90% MeOH/H2O over 4 minutes containing 0.1% TFA; 4 mL/min, monitoring at 220 nm). This diastereomer mixture was separated by Chiralpak AD column eluting with 10% MeOH/EtOH (1:1)/90% heptane with flow rate 20 mL/min. (9H-fluoren-9-yl)methyl (S)-4,4,4-trifluoro-1-((R)-1-(3-fluoro-5-(1,1,2,2-tetrafluoroethoxy)phenyl)-1-(4-fluorophenyl)-2-phenylethylamino)-1-oxobutan-2-ylcarbamate was eluted at a retention time of 8.26 min and isolated as a white solid (10 mg). (9H-fluoren-9-yl)methyl (R)-4,4,4-trifluoro-1-((R)-1-(3-fluoro-5-(1,1,2,2-tetrafluoroethoxy)phenyl)-1-(4-fluorophenyl)-2-phenylethylamino)-1-oxobutan-2-ylcarbamate was eluted at a retention time of 12.97 min and isolated as a white solid (10 mg). The stereochemistry of (9H-fluoren-9-yl)methyl (S)-4,4,4-trifluoro-1-((R)-1-(3-fluoro-5-(1,1,2,2-tetrafluoroethoxy)phenyl)-1-(4-fluorophenyl)-2-phenylethylamino)-1-oxobutan-2-ylcarbamate and (9H-fluoren-9-yl)methyl (R)-4,4,4-trifluoro-1-((R)-1-(3-fluoro-5-(1,1,2,2-tetrafluoroethoxy)phenyl)-1-(4-fluorophenyl)-2-phenylethylamino)-1-oxobutan-2-ylcarbamate was assigned arbitrarily.
O=C(NC(CC(F)(F)F)C(=O)N[C@](Cc1ccccc1)(c1ccc(F)cc1)c1cc(F)cc(OC(F)(F)C(F)F)c1)OCC1c2ccccc2-c2ccccc21
null
N[C@](Cc1ccccc1)(c1ccc(F)cc1)c1cc(F)cc(OC(F)(F)C(F)F)c1
NC(=O)C(CC(F)(F)F)NC(=O)OCC1c2ccccc2-c2ccccc21
null
[F:1][C:2]1[CH:3]=[C:4]([C@@:15]([C:24]2[CH:29]=[CH:28][C:27]([F:30])=[CH:26][CH:25]=2)([NH2:23])[CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:5]=[C:6]([O:8][C:9]([F:14])([F:13])[CH:10]([F:12])[F:11])[CH:7]=1.N[C:32](=[O:57])[CH:33]([NH:39][C:40](=[O:56])[O:41][CH2:42][CH:43]1[C:55]2[CH:54]=[CH:53][CH:52]=[CH:51][C:50]=2[C:49]2[C:44]1=[CH:45][CH:46]=[CH:47][CH:48]=2)[CH2:34][C:35]([F:38])([F:37])[F:36].C1CN([P+](Br)(N2CCCC2)N2CCCC2)CC1.F[P-](F)(F)(F)(F)F.CCN(C(C)C)C(C)C>C(Cl)Cl>[F:36][C:35]([F:37])([F:38])[CH2:34][CH:33]([NH:39][C:40](=[O:56])[O:41][CH2:42][CH:43]1[C:44]2[CH:45]=[CH:46][CH:47]=[CH:48][C:49]=2[C:50]2[C:55]1=[CH:54][CH:53]=[CH:52][CH:51]=2)[C:32]([NH:23][C@@:15]([C:4]1[CH:5]=[C:6]([O:8][C:9]([F:14])([F:13])[CH:10]([F:12])[F:11])[CH:7]=[C:2]([F:1])[CH:3]=1)([C:24]1[CH:29]=[CH:28][C:27]([F:30])=[CH:26][CH:25]=1)[CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)=[O:57]
72
ClCCl
CCN(C(C)C)C(C)C
null
25
36.3
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,221,038
null
null
null
null
ord_dataset-dc3bb1b1ac4e4229a3fc28fb559a9777
2012-01-01T00:10:00
true
To a stirring solution of 1.00 g (6.77 mmol) of benzofuran-2-ylmethanol in 10 mL of toluene at r.t. was added 1.7 mL (7.89 mmol) of DPPA. The solution was cooled to 0° C. and 1.2 ml (8.02 mmol) of DBU was added. The ice bath was removed, and the mixture was stirred with warming to r.t. After 12.5 h, 1N HCl was added to a pH=4, and the aqueous layer was extracted with EtOAc. The pH of the aqueous layer was then adjusted to pH=6 with saturated NaHCO3 solution, and the aqueous layer was extracted with EtOAc. The combined extracts were washed with brine, dried over Na2SO4, filtered, and concentrated. Purification by flash silica gel chromatography (5% EtOAc/hexanes) provided 2-(azidomethyl)benzofuran as a pale yellow oil in quantitative yield.
[N-]=[N+]=NCc1cc2ccccc2o1
null
[N-]=[N+]=NP(=O)(c1ccccc1)c1ccccc1
OCc1cc2ccccc2o1
null
[O:1]1[C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[CH:3]=[C:2]1[CH2:10]O.C1C=CC(P([N:26]=[N+:27]=[N-:28])(C2C=CC=CC=2)=O)=CC=1.C1CCN2C(=NCCC2)CC1>C1(C)C=CC=CC=1>[N:26]([CH2:10][C:2]1[O:1][C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[CH:3]=1)=[N+:27]=[N-:28]
12.5
Cc1ccccc1
C1CCC2=NCCCN2CC1
null
0
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
926,051
null
null
null
null
ord_dataset-cc0899cd744f4f7f8e7f2463560faad1
2009-01-01T00:12:00
true
To a mixture of 1-(2,6-difluorophenyl)-4-hydroxy-6-methylpyridin-2(1H)-one (0.30 g, 1.26 mmol) in dichloromethane (5 mL) was added NCS (2.52 g, 1.90 mmol). The reaction mixture stirred at room temperature under nitrogen for 4.5 hours. The suspension was cooled in ice bath, filtered, and the solid was rinsed with fresh dichloromethane to afford the desired product (0.271 g, 79%) as a white solid. 1H-NMR (CD3OD, 400 MHz) δ 7.58 (m, 1H), 7.22 (m, 2H), 6.20 (s 1H), 2.00 (s, 3H); ES-HRMS m/z 272.0287 (M+H calculated for C12H9NO2F2Cl requires 272.0290).
Cc1cc(O)c(Cl)c(=O)n1-c1c(F)cccc1F
null
Cc1cc(O)cc(=O)n1-c1c(F)cccc1F
O=C1CCC(=O)N1Cl
null
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([F:8])[C:3]=1[N:9]1[C:14]([CH3:15])=[CH:13][C:12]([OH:16])=[CH:11][C:10]1=[O:17].C1C(=O)N([Cl:25])C(=O)C1>ClCCl>[Cl:25][C:11]1[C:10](=[O:17])[N:9]([C:3]2[C:4]([F:8])=[CH:5][CH:6]=[CH:7][C:2]=2[F:1])[C:14]([CH3:15])=[CH:13][C:12]=1[OH:16]
4.5
ClCCl
null
null
25
null
79.2
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,568,172
[H-]
[Na+]
null
null
ord_dataset-9741bb5fd93044078df2a45f45733054
2015-01-01T00:04:00
true
A mixture of compound 2,3,4,5-tetrahydro-2,8-dimethyl-1H-pyrido[4,3-b]indole (2.6 g, 13.1 mmol, 1 equiv.) and NaH (55%, 750 mg, 17.2 mmol, 1.3 equiv.) in 60 ml of THF was heated to 120 deg C. for 1 h. It was then cooled to RT and compound 2-(4-fluorophenyl)-2-methyloxirane (4 g, 26 mmol, 2 equiv.) in 25 ml of DMF was added dropwise for 5 mins at RT followed by heating at 120 deg C. for 2 h. It was cooled to RT and 10 ml of water was added followed by dilution with 800 ml of ethyl acetate, which was first washed with water (150 ml×3) and then brine, dried over sodium sulphate and concentrated under vacuum. Column purified over 230-400 Silica gel (flash) using 15% methanol in ethyl acetate as eluent, Yield: 3 g (66%).
Cc1ccc2c(c1)c1c(n2C(c2ccc(F)cc2)C(C)O)CCN(C)C1
null
CC1(c2ccc(F)cc2)CO1
Cc1ccc2[nH]c3c(c2c1)CN(C)CC3
C1CCOC1
[CH3:1][N:2]1[CH2:15][CH2:14][C:5]2[NH:6][C:7]3[CH:8]=[CH:9][C:10]([CH3:13])=[CH:11][C:12]=3[C:4]=2[CH2:3]1.[H-].[Na+].[F:18][C:19]1[CH:24]=[CH:23][C:22]([C:25]2(C)[CH2:27][O:26]2)=[CH:21][CH:20]=1.O.[CH2:30]1COCC1>CN(C=O)C.C(OCC)(=O)C>[F:18][C:19]1[CH:20]=[CH:21][C:22]([CH:25]([N:6]2[C:7]3[CH:8]=[CH:9][C:10]([CH3:13])=[CH:11][C:12]=3[C:4]3[CH2:3][N:2]([CH3:1])[CH2:15][CH2:14][C:5]2=3)[CH:27]([OH:26])[CH3:30])=[CH:23][CH:24]=1
1
O
CCOC(C)=O
CN(C)C=O
25
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,349,741
null
null
null
null
ord_dataset-6034127657614f02860ed057b62b882e
2013-01-01T00:10:00
true
To a stirred solution of 6.16 g (30.2 mmol) 2c and 110 ml dichloromethane were added 50.0 g (302 mmol) methyltriflate (Aldrich) drop wisely. The reaction mixture was stirred over night and diethylether was added. After evaporation of one third of the solvent volume the desired compound precipitates and the rest of the solvent was decanted. The solid was washed extensively (ten times) with large amounts of diethylether. The solid was dried by use of oil pump vacuum and purified by (C-18) RP-column chromatography (acetonitril/water-gradient 1:99 to 80:20). The desired compound 2d was obtained in 69% yield (20.8 mmol, 7.68 g).
COC(=O)c1ccc([N+](C)(C)C)c(C#N)c1
O=S(=O)([O-])C(F)(F)F
ClCCl
COS(=O)(=O)C(F)(F)F
COC(=O)c1ccc(N(C)C)c(C#N)c1
[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[CH:8][C:7]([N:10]([CH3:12])[CH3:11])=[C:6]([C:13]#[N:14])[CH:5]=1.Cl[CH2:17]Cl.C[O:20][S:21]([C:24]([F:27])([F:26])[F:25])(=[O:23])=[O:22]>C(OCC)C>[F:25][C:24]([F:27])([F:26])[S:21]([O-:23])(=[O:22])=[O:20].[C:13]([C:6]1[CH:5]=[C:4]([C:3]([O:2][CH3:1])=[O:15])[CH:9]=[CH:8][C:7]=1[N+:10]([CH3:17])([CH3:11])[CH3:12])#[N:14]
null
CCOCC
null
null
null
null
69
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,246,842
Cl
null
null
null
ord_dataset-c544c0c663f54dbea4ddb52ddde7934e
2013-01-01T00:01:00
true
By reaction and treatment in the same manner as in Example 49 and using (S)-4-(4-isopropyl-2-oxooxazolidin-3-yl)benzoic acid (496 mg) described in Preparation Example 80 and 1-(3,5-dimethylpyridin-2-yl)piperazine hydrochloride (455 mg) described in Preparation Example 64, the title compound (583 mg) was obtained.
Cc1cnc(N2CCN(C(=O)c3ccc(N4C(=O)OC[C@@H]4C(C)C)cc3)CC2)c(C)c1
null
CC(C)[C@H]1COC(=O)N1c1ccc(C(=O)O)cc1
Cc1cnc(N2CCNCC2)c(C)c1
null
[CH:1]([C@H:4]1[CH2:8][O:7][C:6](=[O:9])[N:5]1[C:10]1[CH:18]=[CH:17][C:13]([C:14]([OH:16])=O)=[CH:12][CH:11]=1)([CH3:3])[CH3:2].Cl.[CH3:20][C:21]1[C:22]([N:28]2[CH2:33][CH2:32][NH:31][CH2:30][CH2:29]2)=[N:23][CH:24]=[C:25]([CH3:27])[CH:26]=1>>[CH3:20][C:21]1[C:22]([N:28]2[CH2:29][CH2:30][N:31]([C:14]([C:13]3[CH:12]=[CH:11][C:10]([N:5]4[C@@H:4]([CH:1]([CH3:2])[CH3:3])[CH2:8][O:7][C:6]4=[O:9])=[CH:18][CH:17]=3)=[O:16])[CH2:32][CH2:33]2)=[N:23][CH:24]=[C:25]([CH3:27])[CH:26]=1
null
null
null
null
null
null
69.3
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,458,914
CC(=O)OI1(OC(C)=O)(OC(C)=O)OC(=O)c2ccccc21
null
null
null
ord_dataset-a86112d52cd54525a5e36d41f18aced2
2014-01-01T00:07:00
true
To a solution of [9-chloro-1-(6-methoxy-2-methylpyridin-3-yl)-1,2,3,4-tetrahydropyrimido[1,2-a]benzimidazol-6-yl]methanol (4.00 g, 11.15 mmol) in dimethylsulfoxide (70.0 mL) was added Dess-Martin reagent (5.20 g, 12.26 mmol). The mixture was stirred at room temperature for 3 hrs. The mixture was quenched with aqueous saturated sodium hydrogen carbonate and aqueous saturated sodium thiosulfate and extracted with ethyl acetate (×3). The combined organic layer was washed with water (×2) and brine (×1), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The resulting solid was washed with ethyl acetate/diisopropyl ether to give the title compound as a pale yellow solid (3.69 g, 10.34 mmol, 93%).
COc1ccc(N2CCCn3c2nc2c(Cl)ccc(C=O)c23)c(C)n1
null
COc1ccc(N2CCCn3c2nc2c(Cl)ccc(CO)c23)c(C)n1
null
null
[Cl:1][C:2]1[C:10]2[N:9]=[C:8]3[N:11]([C:15]4[C:16]([CH3:23])=[N:17][C:18]([O:21][CH3:22])=[CH:19][CH:20]=4)[CH2:12][CH2:13][CH2:14][N:7]3[C:6]=2[C:5]([CH2:24][OH:25])=[CH:4][CH:3]=1.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>CS(C)=O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH:24]=[O:25])=[C:6]2[C:10]=1[N:9]=[C:8]1[N:11]([C:15]3[C:16]([CH3:23])=[N:17][C:18]([O:21][CH3:22])=[CH:19][CH:20]=3)[CH2:12][CH2:13][CH2:14][N:7]21
3
CS(C)=O
null
null
25
null
92.7
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,334,315
CCOC(=O)N=NC(=O)OCC
c1ccc(P(c2ccccc2)c2ccccc2)cc1
null
null
ord_dataset-08852243bba44cb28769a5833f1515fe
2013-01-01T00:09:00
true
To a mixture of 0.81 g of 4-hydroxy-3-[3-(3-methylphenyl)-1-oxo-2-propenyl]-6-methyl-2H-pyran-2-one, 10 ml of tetrahydrofuran, 0.25 ml of 2-methoxyethanol, and 0.87 g of triphenylphosphine was added dropwise a solution of 0.57 g of diethyl azodicarboxylate in 6 ml of tetrahydrofuran, and this was stirred at room temperature overnight. The solvent was distilled off under reduced pressure, and the resulting residue was subjected to silica gel column chromatography to obtain 389 mg of 4-(2-methoxyethoxy)-3-[3-(3-methylphenyl)-1-oxo-2-propenyl]-6-methyl-2H-pyran-2-one [Compound No. (2a-24)] as a yellow oil.
COCCOc1cc(C)oc(=O)c1C(=O)C=Cc1cccc(C)c1
null
COCCO
Cc1cccc(C=CC(=O)c2c(O)cc(C)oc2=O)c1
null
[OH:1][C:2]1[CH:7]=[C:6]([CH3:8])[O:5][C:4](=[O:9])[C:3]=1[C:10](=[O:20])[CH:11]=[CH:12][C:13]1[CH:18]=[CH:17][CH:16]=[C:15]([CH3:19])[CH:14]=1.[CH3:21][O:22][CH2:23][CH2:24]O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[CH3:21][O:22][CH2:23][CH2:24][O:1][C:2]1[CH:7]=[C:6]([CH3:8])[O:5][C:4](=[O:9])[C:3]=1[C:10](=[O:20])[CH:11]=[CH:12][C:13]1[CH:18]=[CH:17][CH:16]=[C:15]([CH3:19])[CH:14]=1
8
C1CCOC1
null
null
25
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,761,688
Cl
null
null
null
ord_dataset-97eb2ab57fec4160922caae33b54d956
2016-01-01T00:08:00
true
4 M HCl in 1,4-dioxane (6 mL, 24 mmol) was added to a solution of 1-benzyl 4-tert-butyl 2-(2-(pyridin-3-yl)ethyl)piperazine-1,4-dicarboxylate (130.2 mg, 0.306 mmol) in MeOH (1 mL). After 1 h, the reaction mixture was concentrated under reduced pressure and purified by HPLC (5 to 50% MeCN/0.1% TFA in H2O/0.1% TFA gradient). The fractions containing the desired product were concentrated under reduced pressure. The material was dissolved in MeOH (1 mL) and 4 M HCl in 1,4-dioxane (0.015 mL) was added. The mixture was concentrated under reduced pressure to give 71.0 mg (58%) of the desired product. LC-MS: RT=3.50 min, [M+H]+=326.2.
O=C(OCc1ccccc1)N1CCNCC1CCc1cccnc1
null
CC(C)(C)OC(=O)N1CCN(C(=O)OCc2ccccc2)C(CCc2cccnc2)C1
null
null
[ClH:1].O1CCOCC1.[N:8]1[CH:13]=[CH:12][CH:11]=[C:10]([CH2:14][CH2:15][CH:16]2[CH2:21][N:20](C(OC(C)(C)C)=O)[CH2:19][CH2:18][N:17]2[C:29]([O:31][CH2:32][C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)=[O:30])[CH:9]=1>CO>[ClH:1].[ClH:1].[N:8]1[CH:13]=[CH:12][CH:11]=[C:10]([CH2:14][CH2:15][CH:16]2[CH2:21][NH:20][CH2:19][CH2:18][N:17]2[C:29]([O:31][CH2:32][C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)=[O:30])[CH:9]=1
1
CO
C1COCCO1
null
null
58
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,703,551
[Pd]
null
null
null
ord_dataset-54347fcace774f89850681d6dec8009f
2016-01-01T00:03:00
true
A suspension of 5,6-bis(benzyloxy)-N-(cyclopropylmethyl)-N-methylpyridazin-3-amine (Intermediate 46; 2.44 mmol) and palladium on carbon (10% wt loading, dry basis; 0.259 g, 0.244 mmol) in ethyl acetate (10 ml) was stirred under a hydrogen atmosphere for 2 hours. The reaction mixture was filtered through a diatomaceous earth cartridge commercially sold under the trade mark ‘Celite’, eluting with ethyl acetate, tetrahydrofuran and methanol. The filtrate was concentrated in vacuo to afford a brown solid, which was triturated from ethyl acetate to give the title compound as a pale brown solid (27.9 mg, 38%).
CN(CC1CC1)c1cc(O)c(=O)[nH]n1
null
CN(CC1CC1)c1cc(OCc2ccccc2)c(OCc2ccccc2)nn1
null
null
C([O:8][C:9]1[CH:10]=[C:11]([N:23]([CH2:25][CH:26]2[CH2:28][CH2:27]2)[CH3:24])[N:12]=[N:13][C:14]=1[O:15]CC1C=CC=CC=1)C1C=CC=CC=1>[Pd].C(OCC)(=O)C>[CH:26]1([CH2:25][N:23]([CH3:24])[C:11]2[CH:10]=[C:9]([OH:8])[C:14](=[O:15])[NH:13][N:12]=2)[CH2:27][CH2:28]1
2
CCOC(C)=O
null
null
null
null
5.9
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,642,822
Cl
[Na+]
[OH-]
null
ord_dataset-bcc0b01d4f58457a8733b10a099f43ba
2015-01-01T00:10:00
true
Water (2 ml) and 4N aqueous solution of sodium hydroxide (2 ml) were added to a solution of 1-(3-chloro-5-cyclopropylpyridin-2-yl)-5-methyl-1H-pyrazole-4-carboxylic acid ethyl ester (240 mg) in ethanol (4 ml) at room temperature, and stirred at 90° C. for six hours. After completion of the reaction, the reaction solution was cooled to 0° C. and 1N hydrochloric acid aqueous solution (9 ml) was added. The precipitated solid was collected by filtration to give the titled compound (157 mg) as a light brown solid.
Cc1c(C(=O)O)cnn1-c1ncc(C2CC2)cc1Cl
null
CCOC(=O)c1cnn(-c2ncc(C3CC3)cc2Cl)c1C
null
null
O.[OH-].[Na+].C([O:6][C:7]([C:9]1[CH:10]=[N:11][N:12]([C:15]2[C:20]([Cl:21])=[CH:19][C:18]([CH:22]3[CH2:24][CH2:23]3)=[CH:17][N:16]=2)[C:13]=1[CH3:14])=[O:8])C.Cl>C(O)C>[Cl:21][C:20]1[C:15]([N:12]2[C:13]([CH3:14])=[C:9]([C:7]([OH:8])=[O:6])[CH:10]=[N:11]2)=[N:16][CH:17]=[C:18]([CH:22]2[CH2:23][CH2:24]2)[CH:19]=1
6
CCO
O
null
90
null
72
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,540,923
Cl
null
null
null
ord_dataset-cac8df8aff894288876df4e093c9877f
2015-01-01T00:02:00
true
In 4 mL of dioxane, tert-butyl (1-(3,5-difluorophenyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl)methylcarbamate (214 mg, 0.567 mmol, 1 equiv.) was dissolved and hydrogen chloride in dioxane (0.923 mL, c=4 mol/L, 3.69 mmo, 6.5 equiv.) was added. The reaction mixture was stirred overnight at room temperature, the precipitate was filtered out, washed with dioxane (2×15 mL) and dried to give (1-(3,5-difluorophenyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl)methanamine hydrochloride (139 mg, 78%).
NCc1cc(C(F)(F)F)nn1-c1cc(F)cc(F)c1
null
CC(C)(C)OC(=O)NCc1cc(C(F)(F)F)nn1-c1cc(F)cc(F)c1
null
null
[F:1][C:2]1[CH:3]=[C:4]([N:9]2[C:13]([CH2:14][NH:15]C(=O)OC(C)(C)C)=[CH:12][C:11]([C:23]([F:26])([F:25])[F:24])=[N:10]2)[CH:5]=[C:6]([F:8])[CH:7]=1.[ClH:27]>O1CCOCC1>[ClH:27].[F:1][C:2]1[CH:3]=[C:4]([N:9]2[C:13]([CH2:14][NH2:15])=[CH:12][C:11]([C:23]([F:25])([F:24])[F:26])=[N:10]2)[CH:5]=[C:6]([F:8])[CH:7]=1
8
C1COCCO1
null
null
25
78
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
925,357
C[O-]
[Na+]
null
null
ord_dataset-cc0899cd744f4f7f8e7f2463560faad1
2009-01-01T00:12:00
true
A mixture of 113 mg of 4-hydroxy-7-phenylsulfanyl-isoquinoline-3-carboxylic acid butyl ester (0.32 mmol), 244 mg of glycine (3.2 mmol), and 6.4 ml of a 0.5 N solution of sodium methoxide in methanol (3.2 mmol) was refluxed for 24 h with stirring. Then the solvent was evaporated in vacuo, the residue dissolved in 25 ml of water and the resulting solution was washed twice with 50 ml of ethyl acetate. The pH of the solution was subsequently adjusted to about 3 by addition of concentrated hydrochloric acid and the resulting slurry was extracted twice with 25 ml of ethyl acetate. The combined extracts were dried over MgSO4 and evaporated in vacuo. 103 mg of the title compound were obtained; 1H NMR (DMSO-d6): δ=9.32 (t, 1H), 8.74 (s, 1H), 8.19 (d, 1H), 7.94 (d, 1H), 7.45 to 7.65 (m, 6H), 4.02 (d, 2H).
O=C(O)CNC(=O)c1ncc2cc(Sc3ccccc3)ccc2c1O
null
NCC(=O)O
CCCCOC(=O)c1ncc2cc(Sc3ccccc3)ccc2c1O
null
C(O[C:6]([C:8]1[N:9]=[CH:10][C:11]2[C:16]([C:17]=1[OH:18])=[CH:15][CH:14]=[C:13]([S:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[CH:12]=2)=[O:7])CCC.[NH2:26][CH2:27][C:28]([OH:30])=[O:29].C[O-].[Na+].CO>>[OH:18][C:17]1[C:16]2[C:11](=[CH:12][C:13]([S:19][C:20]3[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=3)=[CH:14][CH:15]=2)[CH:10]=[N:9][C:8]=1[C:6]([NH:26][CH2:27][C:28]([OH:30])=[O:29])=[O:7]
null
CO
null
null
null
null
90.8
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,651,192
null
null
null
null
ord_dataset-42cd9bc5aae3485f9a58f1527bd3abf0
2015-01-01T00:11:00
true
The title compound was synthesized from 1-bromo-4-hydroxy-6-(2,4,6-trimethyl-phenoxy)-isoquinoline-3-carboxylic acid butyl ester and CuCN in analogy to example 3a; MS-(−)-ion: M−1=403.4.
CCCCOC(=O)c1nc(C#N)c2ccc(Oc3c(C)cc(C)cc3C)cc2c1O
null
N#C[Cu]
CCCCOC(=O)c1nc(Br)c2ccc(Oc3c(C)cc(C)cc3C)cc2c1O
null
[CH2:1]([O:5][C:6]([C:8]1[N:9]=[C:10](Br)[C:11]2[C:16]([C:17]=1[OH:18])=[CH:15][C:14]([O:19][C:20]1[C:25]([CH3:26])=[CH:24][C:23]([CH3:27])=[CH:22][C:21]=1[CH3:28])=[CH:13][CH:12]=2)=[O:7])[CH2:2][CH2:3][CH3:4].[C:30]([Cu])#[N:31]>>[CH2:1]([O:5][C:6]([C:8]1[N:9]=[C:10]([C:30]#[N:31])[C:11]2[C:16]([C:17]=1[OH:18])=[CH:15][C:14]([O:19][C:20]1[C:25]([CH3:26])=[CH:24][C:23]([CH3:27])=[CH:22][C:21]=1[CH3:28])=[CH:13][CH:12]=2)=[O:7])[CH2:2][CH2:3][CH3:4]
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
1,480,741
Cl
null
null
null
ord_dataset-c3c1091f873b4f40827973a6f1f9b685
2014-01-01T00:09:00
true
15.5 g (43.9 mmol) 1-benzyl-4-(2-chloro-quinolin-3-yl)-piperidin-4-ol were refluxed for 8 h in 150 mL of a 6M aqueous hydrochloric acid solution. 100 mL water were added dropwise to the reaction mixture and the precipitated solid was suction filtered, dried and then stirred into 150 mL of a 15%, aqueous potassium carbonate solution. After the precipitate had been suction filtered the product was obtained as a free base and dried.
Oc1nc2ccccc2cc1C1=CCN(Cc2ccccc2)CC1
null
OC1(c2cc3ccccc3nc2Cl)CCN(Cc2ccccc2)CC1
O
null
[CH2:1]([N:8]1[CH2:13][CH2:12][C:11]([C:15]2[C:16](Cl)=[N:17][C:18]3[C:23]([CH:24]=2)=[CH:22][CH:21]=[CH:20][CH:19]=3)(O)[CH2:10][CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl.[OH2:27]>>[CH2:1]([N:8]1[CH2:13][CH:12]=[C:11]([C:15]2[C:16]([OH:27])=[N:17][C:18]3[C:23]([CH:24]=2)=[CH:22][CH:21]=[CH:20][CH:19]=3)[CH2:10][CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
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
550,148
null
null
null
null
ord_dataset-e967d076b4894c2c854795f019ed3c39
2002-01-01T00:06:00
true
To a mixture of 1-[(1R,2R)-2-(2,4-difluorophenyl)-2-hydroxy-1-methyl-3-(1H-1,2,4-triazol-1-yl)propyl]-3-[4-(1H-tetrazol-1-yl)phenyl]-2-imidazolidinone (0.80 g) and chloromethyl propanate (4.07 g) was added acetonitrile (1.6 ml), and the mixture was stirred for 10 hours at 100° C. under an argon atmosphere. The reaction mixture was concentrated under reduced pressure, and to the residue was added diisopropyl ether (8 ml). The resulting powder was collected by filtration. The powder was subjected to silica gel flush chromatography (eluent: ethyl acetate→acetone→acetone/ethanol=9/1→5/1), and the fraction containing the desired compound was concentrated under reduced pressure. The residue was subjected to ODS column chromatography (eluent: methanol/water=3/2). The eluate was concentrated in vacuo, and the residue was dissolved in water (10 ml). The solution was lyophilized to give 1-[(2R,3R)-2-(2,4-difluorophenyl)-2-hydroxy-3-[2-oxo-3-[4-(1H-tetrazol-1-yl)phenyl]-1-imidazolidinyl]butyl]-4-propanoyloxymethyl-1H-1,2,4-triazolium chloride (Compound 14, 0.04 g) as a white powder.
CCC(=O)OCN1C=N[NH+](C[C@](O)(c2ccc(F)cc2F)[C@@H](C)N2CCN(c3ccc(-n4cnnn4)cc3)C2=O)C1
[Cl-]
C[C@@H](N1CCN(c2ccc(-n3cnnn3)cc2)C1=O)[C@](O)(Cn1cncn1)c1ccc(F)cc1F
CCC(=O)OCCl
null
[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[C@@:9]([OH:35])([CH2:29][N:30]1[CH:34]=[N:33][CH:32]=[N:31]1)[C@H:10]([N:12]1[CH2:16][CH2:15][N:14]([C:17]2[CH:22]=[CH:21][C:20]([N:23]3[CH:27]=[N:26][N:25]=[N:24]3)=[CH:19][CH:18]=2)[C:13]1=[O:28])[CH3:11].[C:36]([O:40][CH2:41][Cl:42])(=[O:39])[CH2:37][CH3:38]>C(#N)C>[Cl-:42].[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[C@:9]([OH:35])([C@H:10]([N:12]1[CH2:16][CH2:15][N:14]([C:17]2[CH:22]=[CH:21][C:20]([N:23]3[CH:27]=[N:26][N:25]=[N:24]3)=[CH:19][CH:18]=2)[C:13]1=[O:28])[CH3:11])[CH2:29][NH+:30]1[CH2:34][N:33]([CH2:41][O:40][C:36](=[O:39])[CH2:37][CH3:38])[CH:32]=[N:31]1
10
CC#N
null
null
100
null
4
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,411,409
null
null
null
null
ord_dataset-7456bda2326f4bebaa874a5474d4cc0d
2014-01-01T00:03:00
true
Triethylamine (5 ml, 35.9 mmol) is added, dropwise, to a solution of 4-(4-benzyloxy-2,6-dimethylphenyl)-10-oxatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione (5.0 g, 13.4 mmol) and trimethylacetyl chloride (5 ml, 40.6 mmol) in dry dichloromethane (75 ml). The mixture is stirred for 2 hours at room temperature, then silica gel is added and the solvent is evaporated under reduced pressure. The residue is purified by column chromatography on silica gel to give rac-(1R,2S,6R,7S)-4-(4-benzyloxy-2,6-dimethylphenyl)-5-oxo-10-oxatricyclo[5.2.1.02,6]deca-3,8-dien-3-yl 2,2-dimethylpropionate.
Cc1cc(OCc2ccccc2)cc(C)c1C1=C(OC(=O)C(C)(C)C)C2C3C=CC(O3)C2C1=O
null
Cc1cc(OCc2ccccc2)cc(C)c1C1C(=O)C2C3C=CC(O3)C2C1=O
CC(C)(C)C(=O)Cl
null
C(N(CC)CC)C.[CH2:8]([O:15][C:16]1[CH:21]=[C:20]([CH3:22])[C:19]([CH:23]2[C:31](=[O:32])[CH:30]3[CH:25]([CH:26]4[O:33][CH:29]3[CH:28]=[CH:27]4)[C:24]2=[O:34])=[C:18]([CH3:35])[CH:17]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[CH3:36][C:37]([CH3:42])([CH3:41])[C:38](Cl)=[O:39]>ClCCl>[CH3:36][C:37]([CH3:42])([CH3:41])[C:38]([O:32][C:31]1[CH:30]2[CH:25]([C:24](=[O:34])[C:23]=1[C:19]1[C:18]([CH3:35])=[CH:17][C:16]([O:15][CH2:8][C:9]3[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=3)=[CH:21][C:20]=1[CH3:22])[CH:26]1[O:33][CH:29]2[CH:28]=[CH:27]1)=[O:39]
2
ClCCl
CCN(CC)CC
null
25
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1,051,845
O=C([O-])C(F)(F)F
null
null
null
ord_dataset-373415d3e0e54004837cf4831e67666f
2011-01-01T00:05:00
true
The title compound was prepared from 3-(1-benzyl-1H-[1,2,4]triazol-3-yl)-2-[cyclopropyl-(4-trifluoromethoxy-benzoyl)-amino]-3-oxo-propionic acid ethyl ester in direct analogy to intermediate 8B, by reaction with ammonium trifluoroacetate. MS: 498.2 (MH+).
CCOC(=O)c1c(-c2ncn(Cc3ccccc3)n2)nc(-c2ccc(OC(F)(F)F)cc2)n1C1CC1
null
[NH4+]
CCOC(=O)C(C(=O)c1ncn(Cc2ccccc2)n1)N(C(=O)c1ccc(OC(F)(F)F)cc1)C1CC1
null
[CH2:1]([O:3][C:4](=[O:37])[CH:5]([N:20]([CH:34]1[CH2:36][CH2:35]1)[C:21](=O)[C:22]1[CH:27]=[CH:26][C:25]([O:28][C:29]([F:32])([F:31])[F:30])=[CH:24][CH:23]=1)[C:6]([C:8]1[N:12]=[CH:11][N:10]([CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[N:9]=1)=O)[CH3:2].FC(F)(F)C([O-])=O.[NH4+:45]>>[CH2:1]([O:3][C:4]([C:5]1[N:20]([CH:34]2[CH2:35][CH2:36]2)[C:21]([C:22]2[CH:27]=[CH:26][C:25]([O:28][C:29]([F:31])([F:32])[F:30])=[CH:24][CH:23]=2)=[N:45][C:6]=1[C:8]1[N:12]=[CH:11][N:10]([CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[N:9]=1)=[O:37])[CH3:2]
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
941,601
null
null
null
null
ord_dataset-ed680843f6d14f5c9901869b2a06b4a4
2010-01-01T00:03:00
true
To a solution of Example 17D (32 mg, 0.1 mmol) in anhydrous THF (5 mL) was added N,N-diisopropylethylamine (0.035 mL, 0.2 mmol), followed by phenyl chloroformate (17.22 mg, 0.11 mmol). The mixture was stirred for 8 hours at room temperature and concentrated under reduced pressure. The residue was taken up in anhydrous dichloromethane (3 mL) and trifluoracetic acid (0.075 mL) in dichloromethane (0.075 mL) were added. The mixture was stirred for 5 hours at room temperature, concentrated under reduced pressure and purified using RP-HPLC to provide the titled compound. MS (ESI) m/e 336 (M+H)+; 1H NMR (400 MHz, CD3OD) δ ppm 1.77 (m, 1 H) 2.69 (m, 2 H) 3.07 (m, 1 H) 3.17 (m, 2 H) 3.25 (m, 1 H) 3.52 (m, 2 H) 3.75 (m, 1 H) 3.88 (m, 1 H) 4.52 (m, 1 H) 4.66 (m, 2 H) 7.10 (d, 2 H) 7.21 (t, 1 H) 7.37 (t, 2 H).
O=C(NC[C@@H]1CN[C@H](C(=O)N2CCSC2)C1)Oc1ccccc1
null
CC(C)(C)OC(=O)N1C[C@@H](CN)C[C@H]1C(=O)N1CCSC1
O=C(Cl)Oc1ccccc1
null
C(OC([N:8]1[CH2:12][C@@H:11]([CH2:13][NH2:14])[CH2:10][C@H:9]1[C:15]([N:17]1[CH2:21][CH2:20][S:19][CH2:18]1)=[O:16])=O)(C)(C)C.C(N(CC)C(C)C)(C)C.Cl[C:32]([O:34][C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)=[O:33]>C1COCC1>[C:35]1([O:34][C:32](=[O:33])[NH:14][CH2:13][C@H:11]2[CH2:10][C@@H:9]([C:15]([N:17]3[CH2:21][CH2:20][S:19][CH2:18]3)=[O:16])[NH:8][CH2:12]2)[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1
8
CCN(C(C)C)C(C)C
C1CCOC1
null
25
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
249,634
null
null
null
null
ord_dataset-4f3b2ca6df1d41ef8b5008f1f39da0e2
1992-01-01T00:06:00
true
Mon-ethyl methoxy(methyl)malonate (14.52 grams, 0.08 mole) was reacted with thionyl chloride (19.61 grams, 0.16 mole) at 50° C. for a 13-hour reaction period with an additional holding period of approximately 32 hours at room temperature. Vacuum evaporation of the excess thionyl chloride gave 15.2 grams (0.08 mole) of ethyl 2-(chlorocarbonyl)-2-methoxypropionate. NMR analysis of the product indicated the following:
CCOC(=O)C(C)(OC)C(=O)Cl
null
CCOC(=O)C(C)(OC)C(=O)[O-]
O=S(Cl)Cl
null
[CH3:1][O:2][C:3]([CH3:12])([C:9]([O-])=[O:10])[C:4]([O:6][CH2:7][CH3:8])=[O:5].S(Cl)([Cl:15])=O>>[Cl:15][C:9]([C:3]([O:2][CH3:1])([CH3:12])[C:4]([O:6][CH2:7][CH3:8])=[O:5])=[O:10]
null
null
null
null
null
null
100
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null