original_index
int64
2
1.77M
extracted_from_file
stringclasses
489 values
date_of_experiment
timestamp[ns]date
grant_date
timestamp[ns]date
1976-01-01 00:01:00
2016-01-01 00:09:00
is_mapped
bool
1 class
rxn_str
stringlengths
87
6.12k
reactant_000
stringlengths
1
902
reactant_001
stringlengths
1
902
reactant_002
null
agent_000
stringlengths
1
540
agent_001
stringlengths
1
852
agent_002
stringlengths
1
247
agent_003
null
agent_004
null
agent_005
null
agent_006
null
agent_007
null
agent_008
null
agent_009
null
agent_010
null
agent_011
null
agent_012
null
agent_013
null
agent_014
null
agent_015
null
agent_016
null
solvent_000
stringclasses
446 values
solvent_001
stringclasses
405 values
solvent_002
null
solvent_003
null
solvent_004
null
solvent_005
null
solvent_006
null
solvent_007
null
solvent_008
null
solvent_009
null
solvent_010
null
temperature
float64
-230
30.1k
rxn_time
float64
0
2.16k
procedure_details
stringlengths
8
24.5k
product_000
stringlengths
1
484
product_001
null
yield_000
float64
0
90,205,156,600B
yield_001
float64
0
100M
15,735
ord_dataset-b971427c0b944c56b63bb2356fa8ca69
null
1976-01-01T00:11:00
true
[CH2:1]([CH:5]1[C:10](=O)[CH2:9][CH2:8][N:7]([CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH2:6]1)[C:2]([CH3:4])=O.[CH2:19]([NH2:26])[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>>[CH2:19]([N:26]1[C:10]2[CH2:9][CH2:8][N:7]([CH2:12][C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[CH2:6][C:5]=2[CH:1]=[C:2]1[CH3:4])[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1
CC(=O)CC1CN(Cc2ccccc2)CCC1=O
NCc1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Using a procedure analogous to Example 3, 3-acetonyl-1-benzyl-4-piperidone may be reacted with benzylamine to give the title compound.
Cc1cc2c(n1Cc1ccccc1)CCN(Cc1ccccc1)C2
null
null
null
1,747,422
ord_dataset-60a3e71da3174666a50a61dcfa611a9f
null
2016-01-01T00:07:00
true
[S:1]1[CH:5]=[CH:4][C:3]([C:6]2[CH:13]=[CH:12][C:9]([CH:10]=[O:11])=[CH:8][N:7]=2)=[CH:2]1.[CH3:14][Mg]Br>>[S:1]1[CH:5]=[CH:4][C:3]([C:6]2[N:7]=[CH:8][C:9]([CH:10]([OH:11])[CH3:14])=[CH:12][CH:13]=2)=[CH:2]1
C[Mg]Br
O=Cc1ccc(-c2ccsc2)nc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Synthesized using compound 56b (260 mg, 1.37 mmol) and methylmagnesium bromide (2.74 mL, 2.74 mmol, 1 M in THF) according to Method D. Crude product was purified by flash chromatography on silica-gel using a mixture of hexane/ethyl acetate (1:1) as eluent. Yellow solid. Yield: 240 mg, 85%. 1H NMR (CDCl3, 500 MHz): δH (ppm)=1.50 (d, J=6.6 Hz, 3H), 4.90 (q, J=6.3 Hz, 1H), 7.38 (dd, J=5.0, 2.8 Hz, 1H), 7.55 (d, J=8.2 Hz, 1H), 7.61 (dd, J=5.0, 1.3 Hz, 1H), 7.70 (dd, J=8.2, 2.2 Hz, 1H), 7.85 (dd, J=2.8, 1.3 Hz, 1H), 8.48 (d, J=2.2 Hz, 1H); 13C NMR (CDCl3, 125 MHz): δC (ppm)=25.2, 68.0, 120.4, 123.6, 126.4, 126.5, 134.3, 139.5, 142.0, 147.4, 152.9; (ESI): m/z=206.29 [M+H]+.
CC(O)c1ccc(-c2ccsc2)nc1
null
null
null
1,205,034
ord_dataset-fb72428f30234761b4216139dc228d0c
null
2012-01-01T00:09:00
true
[Cl:1][C:2]1[CH:3]=[C:4]([NH2:19])[CH:5]=[N:6][C:7]=1[O:8][C:9]1[CH:10]=[N:11][C:12]2[C:17]([CH:18]=1)=[CH:16][CH:15]=[CH:14][CH:13]=2.[CH3:20][O:21][C:22]1[CH:23]=[C:24]([S:30](Cl)(=[O:32])=[O:31])[CH:25]=[CH:26][C:27]=1[O:28][CH3:29]>>[Cl:1][C:2]1[CH:3]=[C:4]([NH:19][S:30]([C:24]2[CH:25]=[CH:26][C:27]([O:28][CH3:29])=[C:22]([O:21][CH3:20])[CH:23]=2)(=[O:32])=[O:31])[CH:5]=[N:6][C:7]=1[O:8][C:9]1[CH:10]=[N:11][C:12]2[C:17]([CH:18]=1)=[CH:16][CH:15]=[CH:14][CH:13]=2
Nc1cnc(Oc2cnc3ccccc3c2)c(Cl)c1
COc1ccc(S(=O)(=O)Cl)cc1OC
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared by reacting 5-chloro-6-(quinolin-3-yloxy)pyridin-3-amine (obtained as per procedure described in preparation 1) and 3,4-dimethoxybenzene-1-sulfonyl chloride.
COc1ccc(S(=O)(=O)Nc2cnc(Oc3cnc4ccccc4c3)c(Cl)c2)cc1OC
null
null
null
1,750,665
ord_dataset-97eb2ab57fec4160922caae33b54d956
null
2016-01-01T00:08:00
true
Cl.[F:2][C:3]1[CH:8]=[CH:7][C:6]([F:9])=[CH:5][C:4]=1[C@H:10]1[CH2:14][C@H:13]([F:15])[CH2:12][NH:11]1.Br[C:17]1[CH:22]=[CH:21][N:20]2[N:23]=[CH:24][C:25]([C:26]([O:28][CH2:29][CH3:30])=[O:27])=[C:19]2[CH:18]=1>>[F:2][C:3]1[CH:8]=[CH:7][C:6]([F:9])=[CH:5][C:4]=1[C@H:10]1[CH2:14][C@H:13]([F:15])[CH2:12][N:11]1[C:17]1[CH:22]=[CH:21][N:20]2[N:23]=[CH:24][C:25]([C:26]([O:28][CH2:29][CH3:30])=[O:27])=[C:19]2[CH:18]=1
CCOC(=O)c1cnn2ccc(Br)cc12
Fc1ccc(F)c([C@H]2C[C@H](F)CN2)c1
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound (Int-67) was prepared by the method similar to that for Int-84 using (2R,4S)-2-(2,5-difluorophenyl)-4-fluoropyrrolidine hydrochloride (Int-47) and Ethyl 5-bromopyrazolo[1,5-a]pyridine-3-carboxylate to afford as yellow solid. LCMS (ESI): m/z 390.8 (M+H).
CCOC(=O)c1cnn2ccc(N3C[C@@H](F)C[C@@H]3c3cc(F)ccc3F)cc12
null
null
null
718,645
ord_dataset-c3a75813d0b24864aa4f7cd526efd6aa
null
2006-01-01T00:07:00
true
[Cl:1][C:2]1[CH:3]=[C:4]([C:8]2[N:12]=[C:11]([CH:13]3[CH2:18][O:17][CH2:16][CH2:15][NH:14]3)[O:10][N:9]=2)[CH:5]=[CH:6][CH:7]=1.[S:19]1[CH:23]=[CH:22][N:21]=[C:20]1[CH:24]=O.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>>[Cl:1][C:2]1[CH:3]=[C:4]([C:8]2[N:12]=[C:11]([CH:13]3[CH2:18][O:17][CH2:16][CH2:15][N:14]3[CH2:24][C:20]3[S:19][CH:23]=[CH:22][N:21]=3)[O:10][N:9]=2)[CH:5]=[CH:6][CH:7]=1
Clc1cccc(-c2noc(C3COCCN3)n2)c1
O=Cc1nccs1
null
CC(=O)O[BH-](OC(C)=O)OC(C)=O
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
3-[3-(3-Chloro-phenyl)-[1,2,4]oxadiazol-5-yl]-4-pyridin-2-ylmethyl-morpholine was obtained as described in Example 43 from (48 mg, 44%) 3-[3-(3-Chloro-phenyl)-[1,2,4]oxadiazol-5-yl]-morpholine (80 mg, 0.30 mmol) with 2-thiazolecarboxaldehyde (68 mg, 0.60) and sodium triacetoxyborohydride (89 mg, 0.42 mmol). The product was purified by SPE chromatography on silica gel using 20–60% ethyl acetate in hexanes. 1H NMR (CDCl3), δ(ppm): 8.13 (s, 1H), 8.01 (d, 1H), 7.75 (d, 1H), 7.47 (m, 2H), 7.33 (d, 1H), 4.29 (m, 1H), 4.15 (m, 4H), 3.88 (m, 2H), 3.30 (m, 1H), 2.70 (m, 1H).
Clc1cccc(-c2noc(C3COCCN3Cc3nccs3)n2)c1
null
null
null
870,900
ord_dataset-c31cb9b44c404c10ba3aa533aa079e2b
null
2009-01-01T00:03:00
true
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:10]2[N:11]([CH3:25])[C:12]([S:15][CH2:16][CH2:17][CH2:18][N:19]3[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20]3)=[N:13][CH:14]=2)=[O:9])=[CH:4][CH:3]=1>O=[Mn]=O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([C:10]2[N:11]([CH3:25])[C:12]([S:15][CH2:16][CH2:17][CH2:18][N:19]3[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20]3)=[N:13][CH:14]=2)[OH:9])=[CH:4][CH:3]=1
Cn1c(C(=O)c2ccc(Br)cc2)cnc1SCCCN1CCCCC1
null
null
O=[Mn]=O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The product of Example III, Step B (0.11 g) in acetone (5 mL) and DMF (5 mL) was treated with piperidine (0.22 g) and K2CO3 (1.8 g). The reaction mixture was allowed to stir for 16 h and then partitioned between EtOAc (75 mL) and aqueous (aq.) saturated (satd.) NaHCO3 (50 mL). The organic portion was washed with brine (50 mL), dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel using 2-5% MeOH/CH2Cl2 as the eluent to provide the title compound (0.27 g, 55%). M calc=423; M+H found=424. Step D: (4-Bromophenyl)-[3-methyl-2-(3-piperidin-1-yl-propylsulfanyl)-3H-imidazol-4-yl]-methanone. The product from Example III, Step C (0.05 g) was subjected to the same conditions described in Example I, Step C (MnO2, 0.05g) to provide the title compound (0.01 g, 20%). M calc=421; M+H found=422. 1H NMR (400 MHz, CDCl3): δ 7.65 (dd, J=8.6, 2.0 Hz, 2H), 7.55 (dd, J=8.6, 2.0 Hz, 2H), 7.46 (s, 1H), 3.86 (s, 3H), 3.28 (t, J=7.1 Hz, 2H), 2.36 (tm, J=7.0 Hz, 6H), 1.91 (m, 2H), 1.55 (m, 4H), 1.40 (br m, 2H). The compound demonstrated useful biological activity when assessed with a [3H]—N-methylhistamine binding assay (see Table in Example XXV). Step E: Additional compounds prepared following Scheme I, and Example III, Steps A, B, C, and D. The following compounds of formula (I) were prepared following Scheme I and Example III, Steps A, B, C, and D; and substituting reagents, and adjusting reaction conditions as needed. The compounds were found to have useful biological activity based on the Ki (nM) value from a [3H]-N-methylhistamine binding assay.
Cn1c(C(O)c2ccc(Br)cc2)cnc1SCCCN1CCCCC1
null
20
null
1,310,993
ord_dataset-2d6edb8ffd434003bb508360153bd9bb
null
2013-01-01T00:07:00
true
Br[C:2]1[CH:11]=[CH:10][C:9]2[N:8]=[CH:7][C:6]3[N:12]([CH3:23])[C:13](=[O:22])[N:14]([C:15]4[C:16]([CH3:21])=[N:17][N:18]([CH3:20])[CH:19]=4)[C:5]=3[C:4]=2[CH:3]=1.[CH:24]([O:27][C:28]1[CH:29]=[C:30](B(O)O)[CH:31]=[CH:32][CH:33]=1)([CH3:26])[CH3:25]>>[CH3:20][N:18]1[CH:19]=[C:15]([N:14]2[C:5]3[C:4]4[CH:3]=[C:2]([C:32]5[CH:31]=[CH:30][CH:29]=[C:28]([O:27][CH:24]([CH3:26])[CH3:25])[CH:33]=5)[CH:11]=[CH:10][C:9]=4[N:8]=[CH:7][C:6]=3[N:12]([CH3:23])[C:13]2=[O:22])[C:16]([CH3:21])=[N:17]1
Cc1nn(C)cc1-n1c(=O)n(C)c2cnc3ccc(Br)cc3c21
CC(C)Oc1cccc(B(O)O)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was synthesized in a similar manner as described for Example 1.1 using 8-bromo-1-(1,3-dimethyl-1H-pyrazol-4-yl)-3-methyl-1,3-dihydro-imidazo[4,5-c]quinolin-2-one (Intermediate A) and 3-isopropoxyphenylboronic acid (Aldrich, Buchs, Switzerland) to give the title compound as a white solid. (HPLC: tR 2.95 min (Method A); M+H=428 MS-ES; 1H-NMR (d6-DMSO, 400 MHz) 8.96 (s, 1H), 8.19-8.16 (m, 1H), 8.09-8.05 (m, 1H), 7.94-7.89 (m, 1H), 7.57-7.54 (m, 1H), 7.39-7.33 (m, 1H), 7.10-7.06 (m, 1H), 6.94-9-6.90 (m, 2H), 4.68 (hp, 1H), 3.92 (s, 3H), 3.57 (s, 3H), 1.95 (s, 3H), 1.30 (t, 6H))
Cc1nn(C)cc1-n1c(=O)n(C)c2cnc3ccc(-c4cccc(OC(C)C)c4)cc3c21
null
null
null
1,147,659
ord_dataset-b195433d5c354ddfb6cde0d53c41910f
null
2012-01-01T00:04:00
true
[Cl:1][C:2]1[N:7]=[CH:6][C:5]([OH:8])=[CH:4][C:3]=1[F:9].CN(C)C=O.C(=O)([O-])[O-].[K+].[K+].[CH2:21](Br)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1>O>[Cl:1][C:2]1[C:3]([F:9])=[CH:4][C:5]([O:8][CH2:21][C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[CH:6][N:7]=1
BrCc1ccccc1
Oc1cnc(Cl)c(F)c1
null
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CN(C)C=O
null
null
null
null
null
null
null
null
null
80
null
0.5 g (3.38 mM) of 6-chloro-5-fluoro-3-pyridinol, 10 ml of dimethyl-formamide and 0.843 g (6.08 mM) of potassium carbonate are mixed. 0.8 ml (6.76 mM) of benzyl bromide is added and the mixture is heated at 80° C. for one hour. After hydrolysis in 100 ml of water, the mixture is extracted with ethyl acetate and the organic phases are washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The crude product is purified by chromatography on silica gel (eluent: pure toluene) to give the expected product in the form of a white solid with a quantitative yield.
Fc1cc(OCc2ccccc2)cnc1Cl
null
null
null
1,113,348
ord_dataset-375a420ee9b042918ddca20f02df37d3
null
2011-01-01T00:11:00
true
[O:1]=[C:2]([NH:19][C:20]1[CH:25]=[CH:24][CH:23]=[C:22]([C:26]([F:29])([F:28])[F:27])[CH:21]=1)[CH2:3][NH:4][C:5]([C@@H:7]1[CH2:11][CH2:10][N:9](C(OC(C)(C)C)=O)[CH2:8]1)=[O:6].[ClH:30].O1CCOCC1>O1CCOCC1>[ClH:30].[O:1]=[C:2]([NH:19][C:20]1[CH:25]=[CH:24][CH:23]=[C:22]([C:26]([F:29])([F:27])[F:28])[CH:21]=1)[CH2:3][NH:4][C:5]([C@@H:7]1[CH2:11][CH2:10][NH:9][CH2:8]1)=[O:6]
CC(C)(C)OC(=O)N1CC[C@@H](C(=O)NCC(=O)Nc2cccc(C(F)(F)F)c2)C1
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1COCCO1
null
null
null
null
null
null
null
null
null
null
25
2
To a solution of tert-butyl (3R)-3-{[(2-oxo-2-{[3-(trifluoromethyl)phenyl]amino}ethyl)amino]carbonyl}pyrrolidine-1-carboxylate (0.170 g, 0.41 mmol) in dioxane (0.5 ml), was added 4M HCl/dioxane (2 mL). The mixture was stirred at RT for 2 h. The mixture was concentrated, and (3R)—N-(2-oxo-2-{[3-(trifluoromethyl)phenyl]amino}ethyl)pyrrolidine-3-carboxamide hydrochloride was obtained as a white solid and was used in the next step without further purification.
O=C(CNC(=O)[C@@H]1CCNC1)Nc1cccc(C(F)(F)F)c1
null
null
null
910,255
ord_dataset-46d216f2c4374ef5b9df90427e2a4cd4
null
2009-01-01T00:09:00
true
[C:1]1([C:7]2[C:11]3[CH:12]=[N:13][CH:14]=[CH:15][C:10]=3[NH:9][CH:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[F:16][C:17]1[CH:36]=[CH:35][C:20]([CH2:21][NH:22][C:23]([C:25]2[CH:30]=[CH:29][C:28]([S:31](Cl)(=[O:33])=[O:32])=[CH:27][CH:26]=2)=[O:24])=[CH:19][CH:18]=1>C1COCC1>[F:16][C:17]1[CH:18]=[CH:19][C:20]([CH2:21][NH:22][C:23](=[O:24])[C:25]2[CH:30]=[CH:29][C:28]([S:31]([N:9]3[C:10]4[CH:15]=[CH:14][N:13]=[CH:12][C:11]=4[C:7]([C:1]4[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=4)=[CH:8]3)(=[O:32])=[O:33])=[CH:27][CH:26]=2)=[CH:35][CH:36]=1
c1ccc(-c2c[nH]c3ccncc23)cc1
O=C(NCc1ccc(F)cc1)c1ccc(S(=O)(=O)Cl)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
null
Add a 5 ml THF solution of 3-Phenyl-1H-pyrrolo[3,2-c]pyridine (500 mg, 2.57 mmol, 1 eq) to a 4 ml THF solution of KotBu (303 mg, 2.70 mmol, 1.05 eq) under N2 atmosphere. Stir reaction for 10 minutes and then add a 5 ml THF solution of 4-(4-Fluoro-benzylcarbamoyl)-benzenesulfonyl chloride (844 mg, 2.57 mmol, 1 eq). Stir reaction for 16 hours, remove solvent on rotovap, and purify by silica gel chromatography to give N-(4-Fluoro-benzyl)-4-(3-phenyl-pyrrolo[3,2-c]pyridine-1-sulfonyl)-benzamide (982 mg, 79% yield). Mass Spectrum (m/e): 485.96 (MH+).
O=C(NCc1ccc(F)cc1)c1ccc(S(=O)(=O)n2cc(-c3ccccc3)c3cnccc32)cc1
null
78.7
null
63,418
ord_dataset-9240b22758dd4f9e981f9ad2d5394155
null
1980-01-01T00:02:00
true
[CH:1]#[C:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].CC(N=NC(C#N)(C)C)(C#N)C.[CH2:21]([SnH:25]([CH2:30][CH2:31][CH2:32][CH3:33])[CH2:26][CH2:27][CH2:28][CH3:29])[CH2:22][CH2:23][CH3:24]>C1(C)C=CC=CC=1>[CH2:30]([Sn:25]([CH2:21][CH2:22][CH2:23][CH3:24])([CH2:26][CH2:27][CH2:28][CH3:29])/[CH:1]=[CH:2]/[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8])[CH2:31][CH2:32][CH3:33]
CCCC[SnH](CCCC)CCCC
C#CCCCCCC
null
CC(C)(C#N)N=NC(C)(C)C#N
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
null
null
null
null
null
null
null
null
null
null
25
null
A solution of 10.0 g (0.0908 mol) of 1-octyne, 60 ml of anhydrous toluene, 230 mg of azobisisobutylonitrile (AIBN), and 25 (0.0943 mol) of tri-n-butyltin hydride is refluxed under an argon atomosphere for 3 hours. The reaction mixture is cooled to ambient temperature and concentrated in vacuo. The resulting yellow liquid is distilled (bulb to bulb) to give 36.29 (99%) of the stannyl octene as a pale yellow liquid.
CCCCCC/C=C/[Sn](CCCC)(CCCC)CCCC
null
null
null
813,600
ord_dataset-892acf7477db4d3a8a8559f004a7c0a2
null
2008-01-01T00:03:00
true
[CH3:1][N:2]([CH3:16])[C:3]1([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH2:8][CH2:7][CH:6]([NH2:9])[CH2:5][CH2:4]1.[Cl-].COC1N=C(OC)N=C([N+]2(C)CCOCC2)N=1.[NH:35]1[C:43]2[C:38](=[CH:39][CH:40]=[CH:41][CH:42]=2)[C:37]([CH2:44][C:45]([NH:47][C@H:48]([C:53](O)=[O:54])[CH2:49][CH:50]([CH3:52])[CH3:51])=[O:46])=[CH:36]1>CO>[CH3:1][N:2]([CH3:16])[C:3]1([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH2:8][CH2:7][CH:6]([NH:9][C:53](=[O:54])[CH:48]([NH:47][C:45](=[O:46])[CH2:44][C:37]2[C:38]3[C:43](=[CH:42][CH:41]=[CH:40][CH:39]=3)[NH:35][CH:36]=2)[CH2:49][CH:50]([CH3:52])[CH3:51])[CH2:5][CH2:4]1
CC(C)C[C@H](NC(=O)Cc1c[nH]c2ccccc12)C(=O)O
CN(C)C1(c2ccccc2)CCC(N)CC1
null
COc1nc(OC)nc([N+]2(C)CCOCC2)n1
[Cl-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
25
24
The more polar diastereomer of (4-dimethylamino-4-phenyl-cyclohexyl)amine (143 mg, 0.66 mmole) and 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (272 mg, 0.98 mmole) were added to a solution of N-(3-indolylacetyl)-L-leucine (189 mg, 0.66 mmole) in MeOH and stirred for 24 h at room temperature. Working up was performed by removing MeOH by distillation. The residue was re-dissolved with water, adjusted to pH 11 with 5M NaOH and extracted with ethyl acetate. The organic phase was dried with Na2SO4 and then evaporated. The product was obtained as a colorless oil in a yield of 320 mg (100%).
CC(C)CC(NC(=O)Cc1c[nH]c2ccccc12)C(=O)NC1CCC(c2ccccc2)(N(C)C)CC1
null
null
null
1,615,689
ord_dataset-35c51552812941cda45194a013d34bb9
null
2015-01-01T00:08:00
true
[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[CH:7][C:8](Cl)=[N:9]2)=[N:4][CH:3]=1.[NH:13]1[CH2:18][CH2:17][O:16][CH2:15][CH2:14]1>C(OCC)(=O)C>[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[CH:7][C:8]([N:13]3[CH2:18][CH2:17][O:16][CH2:15][CH2:14]3)=[N:9]2)=[N:4][CH:3]=1
Clc1ccc2ncc(Br)cc2n1
C1COCCN1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOC(C)=O
null
null
null
null
null
null
null
null
null
null
140
8
A mixture of 7-bromo-2-chloro-1,5-naphthyridine (F-31) (200 mg, 0.82 mmol, 1.0 eq) and morpholine (10 mL) was stirred in a sealed-tube at 140° C. overnight. The reaction mixture was cooled to RT, diluted with ethyl acetate (150 mL) and then washed with brine, dried over Na2SO4 and filtered. The filtrate was concentrated in vacuo to afford the desired product 7-bromo-2-morpholino-1,5-naphthyridine (F-32) (180 mg, 74.7% yield). ESI-MS m/z: 294.01 [M+H]+.
Brc1cnc2ccc(N3CCOCC3)nc2c1
null
74.7
null
1,567,131
ord_dataset-4e54080057a44c3887653391e24c90b6
null
2015-01-01T00:03:00
true
[CH3:1][C:2]1[N:3]=[C:4]([C:7]2[C:15]3[C:14]([C:16]4[CH:21]=[CH:20][CH:19]=[C:18]([N+:22]([O-])=O)[CH:17]=4)=[N:13][CH:12]=[N:11][C:10]=3[N:9]([CH2:25][O:26][CH2:27][CH2:28][Si:29]([CH3:32])([CH3:31])[CH3:30])[CH:8]=2)[O:5][CH:6]=1>CO.[OH-].[OH-].[Pd+2]>[CH3:1][C:2]1[N:3]=[C:4]([C:7]2[C:15]3[C:14]([C:16]4[CH:17]=[C:18]([CH:19]=[CH:20][CH:21]=4)[NH2:22])=[N:13][CH:12]=[N:11][C:10]=3[N:9]([CH2:25][O:26][CH2:27][CH2:28][Si:29]([CH3:30])([CH3:32])[CH3:31])[CH:8]=2)[O:5][CH:6]=1
Cc1coc(-c2cn(COCC[Si](C)(C)C)c3ncnc(-c4cccc([N+](=O)[O-])c4)c23)n1
null
null
[Pd+2]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
25
4
To a solution of 4-methyl-2-(4-(3-nitrophenyl)-7-((2-(trimethylsilyl)ethoxy)methyl)-7H-pyrrolo[2,3-d]pyrimidin-5-yl)oxazole (0.30 g, 0.66 mmol) in methanol (20 mL), was added Pd(OH)2 on carbon (300 mg, 10 wt. %). The flask was purged with hydrogen and was stirred for 4 hours at room temperature under hydrogen atmosphere (1 atm). The reaction was filtered, and concentrated in vacuo to afford crude 3-(5-(4-methyloxazol-2-yl)-7-((2-(trimethylsilyl)ethoxy)methyl)-7H-pyrrolo[2,3-d]pyrimidin-4-yl)aniline as a colorless oil. LRMS (ESI) calc'd for C22H28N5O2Si [M+H]+: 422, found 422.
Cc1coc(-c2cn(COCC[Si](C)(C)C)c3ncnc(-c4cccc(N)c4)c23)n1
null
null
null
1,390,519
ord_dataset-31641fb65b34430fa7435229b949b604
null
2014-01-01T00:01:00
true
[CH2:1]([O:3][C:4]1[CH:5]=[C:6]([CH:10]=[CH:11][C:12]=1[O:13][CH2:14][CH3:15])[C:7]([NH2:9])=[O:8])[CH3:2].Br[CH2:17][C:18](=O)[CH2:19][CH2:20][C:21]([O:23][CH3:24])=[O:22]>CN(C)C=O>[CH2:1]([O:3][C:4]1[CH:5]=[C:6]([C:7]2[O:8][CH:17]=[C:18]([CH2:19][CH2:20][C:21]([O:23][CH3:24])=[O:22])[N:9]=2)[CH:10]=[CH:11][C:12]=1[O:13][CH2:14][CH3:15])[CH3:2]
CCOc1ccc(C(N)=O)cc1OCC
COC(=O)CCC(=O)CBr
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
130
16
A 40 g quantity of 3,4-diethoxybenzamide and 80 g of methyl 5-bromo-4-oxopentanoate (containing about 35% of methyl 3-bromo-4-oxopentanoate) were added to 400 ml of dimethylformamide, and the mixture was stirred at 130° C. for 16 hours. The reaction mixture was concentrated under reduced pressure and diluted with ethyl acetate. Ethyl acetate (500 ml) and saturated sodium bicarbonate solution (500 ml) were gradually added with stirring, and stirring was continued. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:n-hexane=1:8 to 1:4) to give 18 g of white powdery methyl 3-[2-(3,4-diethoxyphenyl)oxazol-4-yl]propionate.
CCOc1ccc(-c2nc(CCC(=O)OC)co2)cc1OCC
null
null
null
1,216,060
ord_dataset-dc3bb1b1ac4e4229a3fc28fb559a9777
null
2012-01-01T00:10:00
true
[N+:1]([C:4]1[CH:56]=[CH:55][C:7]([O:8][C:9]2[CH:14]=[CH:13][C:12]([C:15]3[C:16]4[NH:20][C:19]([CH:21]=[C:22]5[N:54]=[C:25]([C:26]([C:38]6[CH:43]=[CH:42][C:41]([O:44][C:45]7[CH:50]=[CH:49][C:48]([N+:51]([O-])=O)=[CH:47][CH:46]=7)=[CH:40][CH:39]=6)=[C:27]6[NH:37][C:30](=[CH:31][C:32]7[CH:33]=[CH:34][C:35]=3[N:36]=7)[CH:29]=[CH:28]6)[CH:24]=[CH:23]5)=[CH:18][CH:17]=4)=[CH:11][CH:10]=2)=[CH:6][CH:5]=1)([O-])=O.Cl.O.O.Cl[Sn]Cl.N>C(Cl)(Cl)Cl.O>[NH2:1][C:4]1[CH:56]=[CH:55][C:7]([O:8][C:9]2[CH:14]=[CH:13][C:12]([C:15]3[C:16]4[NH:20][C:19]([CH:21]=[C:22]5[N:54]=[C:25]([C:26]([C:38]6[CH:43]=[CH:42][C:41]([O:44][C:45]7[CH:50]=[CH:49][C:48]([NH2:51])=[CH:47][CH:46]=7)=[CH:40][CH:39]=6)=[C:27]6[NH:37][C:30](=[CH:31][C:32]7[CH:33]=[CH:34][C:35]=3[N:36]=7)[CH:29]=[CH:28]6)[CH:24]=[CH:23]5)=[CH:18][CH:17]=4)=[CH:11][CH:10]=2)=[CH:6][CH:5]=1
O=[N+]([O-])c1ccc(Oc2ccc(-c3c4nc(cc5ccc([nH]5)c(-c5ccc(Oc6ccc([N+](=O)[O-])cc6)cc5)c5nc(cc6ccc3[nH]6)C=C5)C=C4)cc2)cc1
null
null
Cl
Cl[Sn]Cl
N
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)Cl
O
null
null
null
null
null
null
null
null
null
null
24
To a solution of 5,15-bis-[4-(4-nitrophenoxy)phenyl]porphyrin (70 mg, 0.095 mmol) in CHCl3 (10 ml), saturated with concentrated HCl, SnCl2.2H2O (105 mg, 0.475 mmol) was added and the mixture was kept under magnetic stirring, at room temperature for 24 h, then cold water was added, the mixture was neutralized with a solution 15% of ammonia, and the organic phase was extracted, dried on Na2SO4, then the solvent was removed by evaporation. The crude product was purified by chromatography on silica gel (THF to THF/DMF 9/1), to give 43 mg of title product (yield 67%).
Nc1ccc(Oc2ccc(-c3c4nc(cc5ccc([nH]5)c(-c5ccc(Oc6ccc(N)cc6)cc5)c5nc(cc6ccc3[nH]6)C=C5)C=C4)cc2)cc1
null
66.9
null
461,823
ord_dataset-5ca9db262dd24c5a9315cdc8ef055b7e
null
2000-01-01T00:04:00
true
[CH3:1][CH:2]([C:4](=[O:16])[CH2:5][CH2:6][C:7]1[CH:12]=[CH:11][C:10]([N+:13]([O-])=O)=[CH:9][CH:8]=1)[CH3:3].[H][H]>[Ni].C1COCC1>[NH2:13][C:10]1[CH:9]=[CH:8][C:7]([CH2:6][CH2:5][C:4](=[O:16])[CH:2]([CH3:1])[CH3:3])=[CH:12][CH:11]=1
CC(C)C(=O)CCc1ccc([N+](=O)[O-])cc1
[H][H]
null
[Ni]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
null
A mixture of 13.6 g (62 mmol) of 2-methyl-5-(4-nitro-phenyl)-pentan-3-one (Y. Huang, L. Shi, S. Li, Synthesis, 1988, 975-977), 400 mL of THF, and 2.6 g of Raney Nickel was shaken in a hydrogen atmosphere (24 p.s.i.) at 25° C. for 56 hours. The catalyst was filtered, and the filtrate was concentrated to give the title compound. 1H NMR (CDCl3) δ 1.01 (d, 6 H), 2.46-2.55 (m, 1 H), 2.65-2.83 (m, 4 H), 3.55 (br s , 2 H), 6.56 (d, 2 H), 6.92 (d, 2 H).
CC(C)C(=O)CCc1ccc(N)cc1
null
null
null
204,193
ord_dataset-76a008eb2d3f48d891cad325041f3d1e
null
1990-01-01T00:02:00
true
[CH3:1]/[CH:2]=[C:3](/[C:5]([O:7][C@@H:8]1[C@:16]23[C@H:20]([C@@:21]([C@:25]45[O:30][C@@:29]4([CH3:31])[C@H:28]4[C@:32]6([OH:38])[C@H:36]([O:37][C@@H:26]5[CH2:27]4)[O:35][CH:34]=[CH:33]6)([CH3:24])[C@H:22]([OH:23])[C@H:14]4[C@H:15]2[C@:11]([C:44]([O:46][CH3:47])=[O:45])([CH2:12][O:13]4)[C@H:10]([O:48][C:49]([CH3:51])=[O:50])[CH2:9]1)[C@@:19]([OH:43])([C:39]([O:41][CH3:42])=[O:40])[O:18][CH2:17]3)=[O:6])\[CH3:4].[H][H]>O.O.[Pt](=O)=O.C(OCC)(=O)C>[CH3:1]/[CH:2]=[C:3](/[C:5]([O:7][C@@H:8]1[C@:16]23[C@H:20]([C@@:21]([C@:25]45[O:30][C@@:29]4([CH3:31])[C@@H:28]4[C@:32]6([OH:38])[C@@H:36]([O:37][C@H:26]5[CH2:27]4)[O:35][CH2:34][CH2:33]6)([CH3:24])[C@H:22]([OH:23])[C@H:14]4[C@H:15]2[C@:11]([C:44]([O:46][CH3:47])=[O:45])([CH2:12][O:13]4)[C@H:10]([O:48][C:49]([CH3:51])=[O:50])[CH2:9]1)[C@@:19]([OH:43])([C:39]([O:41][CH3:42])=[O:40])[O:18][CH2:17]3)=[O:6])\[CH3:4]
[H][H]
C/C=C(\C)C(=O)O[C@H]1C[C@@H](OC(C)=O)[C@@]2(C(=O)OC)CO[C@H]3[C@@H](O)[C@@](C)([C@]45O[C@@]4(C)[C@@H]4C[C@H]5O[C@@H]5OC=C[C@@]54O)[C@H]4[C@]1(CO[C@]4(O)C(=O)OC)[C@@H]32
null
O=[Pt]=O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOC(C)=O
O
null
null
null
null
null
null
null
null
null
null
1.25
40.8 mg. azadirachtin A (5.67×1031 5 mole) were dissolved in 4 ml. ethyl acetate and 20 mg. platinum dioxide dihydrate were added thereto. The mixture was stirred and hydrogen passed therethrough for 75 minutes, the course of the reaction being monitored by HPLC. After the disappearance of the azadirachtin A peak, the reaction was discontinued and the reaction mixture centrifuged. The supernatant solution was evaporated and purified on silicon dioxide thin layer chromatography plates using the elution agent chloroform/acetone (7:3 v/v); Rf 0.33. Yield: 28.2 mg. (69% of theory).
C/C=C(\C)C(=O)O[C@H]1C[C@@H](OC(C)=O)[C@@]2(C(=O)OC)CO[C@H]3[C@@H](O)[C@@](C)([C@]45O[C@@]4(C)[C@H]4C[C@@H]5O[C@H]5OCC[C@@]54O)[C@H]4[C@]1(CO[C@]4(O)C(=O)OC)[C@@H]32
null
null
null
1,749,000
ord_dataset-60a3e71da3174666a50a61dcfa611a9f
null
2016-01-01T00:07:00
true
CO[C:3]([C:5]1[CH:10]=[N:9][CH:8]=[CH:7][N:6]=1)=[O:4].[C:11](#[N:13])[CH3:12].[H-].[Na+:15].C(OC)(C)(C)C>C1COCC1>[C:11]([CH:12]=[C:3]([C:5]1[CH:10]=[N:9][CH:8]=[CH:7][N:6]=1)[O-:4])#[N:13].[Na+:15]
CC#N
COC(=O)c1cnccn1
null
[H-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
COC(C)(C)C
null
null
null
null
null
null
null
null
null
null
0.5
A solution of 1.5 g (10.9 mmol) of methylpyrazine-2-carboxylate and 446 mg (10.9 mmol) of acetonitrile in 16.5 ml of THF was added dropwise to a suspension, heated under reflux, of 434 mg of sodium hydride (60% strength suspension in mineral oil) in 10 ml of THF. The reaction mixture was heated under reflux for 20 h. After cooling, 50 ml of methyl tert-butyl ether were added and the mixture was stirred for 30 minutes. The precipitate formed was filtered off with suction over a frit and dried under oil pump vacuum. This gave 1.77 g (96% of theory) of the title compound which was used without further characterization for the next step.
N#CC=C([O-])c1cnccn1
null
null
null
1,733,217
ord_dataset-eacfee6d16d8455a93348409f1b37be4
null
2016-01-01T00:06:00
true
[Si]([O:8][CH2:9][CH:10]([O:44][CH3:45])[CH2:11][N:12]1[C:20](=[O:21])[C:19]2[N:18]([CH2:22][C:23]3[CH:28]=[CH:27][C:26]([Cl:29])=[CH:25][CH:24]=3)[C:17]([O:30][C:31]3[CH:36]=[CH:35][CH:34]=[C:33]([O:37][C:38]([F:41])([F:40])[F:39])[CH:32]=3)=[N:16][C:15]=2[N:14]([CH3:42])[C:13]1=[O:43])(C(C)(C)C)(C)C.Cl>C(O)C>[Cl:29][C:26]1[CH:25]=[CH:24][C:23]([CH2:22][N:18]2[C:19]3[C:20](=[O:21])[N:12]([CH2:11][CH:10]([O:44][CH3:45])[CH2:9][OH:8])[C:13](=[O:43])[N:14]([CH3:42])[C:15]=3[N:16]=[C:17]2[O:30][C:31]2[CH:36]=[CH:35][CH:34]=[C:33]([O:37][C:38]([F:41])([F:39])[F:40])[CH:32]=2)=[CH:28][CH:27]=1
COC(CO[Si](C)(C)C(C)(C)C)Cn1c(=O)c2c(nc(Oc3cccc(OC(F)(F)F)c3)n2Cc2ccc(Cl)cc2)n(C)c1=O
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
null
0.17
To a solution of 1-(3-(tert-butyldimethylsilyloxy)-2-methoxypropyl)-7-(4-chlorobenzyl)-3-methyl-8-(3-(trifluoromethoxy)phenoxy)-1H-purine-2,6(3H,7H)-dione (150 mg, 0.22 mmol) in ethyl alcohol (5 mL) was added concentrated HCl (0.1 mL). The reaction was stirred for 10 minutes. Then it was concentrated and purified by preparative HPLC to give 7-(4-chlorobenzyl)-1-(3-hydroxy-2-methoxypropyl)-3-methyl-8-(3-(trifluoromethoxy)phenoxy)-1H-purine-2,6(3H,7H)-dione (18 mg, 16.2% yield) as white solid. 1H-NMR (DMSO-d6) δ 7.63-7.59(t, 1H), 7.50(s, 1H), 7.45-7.43(m, 5H), 7.34-7.32(d, 1H), 5.44(s, 2H), 4.65-4.62(t, 1H), 4.12-4.08(q, 1H), 3.84-3.79(q, 1H), 3.53-3.41(m, 2H), 3.29-3.28(d, 6H). LCMS retention time 3.089 min; LCMS MH+ 555.
COC(CO)Cn1c(=O)c2c(nc(Oc3cccc(OC(F)(F)F)c3)n2Cc2ccc(Cl)cc2)n(C)c1=O
null
14.7
null
1,053,862
ord_dataset-373415d3e0e54004837cf4831e67666f
null
2011-01-01T00:05:00
true
[C:1]1([C:6]2[CH:30]=[CH:29][C:9]([C:10]([NH:12][CH2:13][C:14]3[C:15]([CH2:20][NH:21]C(=O)OC(C)(C)C)=[N:16][CH:17]=[CH:18][CH:19]=3)=[O:11])=[C:8]([NH:31][CH2:32][CH2:33][C:34]3[CH:39]=[CH:38][CH:37]=[C:36]([F:40])[CH:35]=3)[N:7]=2)[CH2:5][CH2:4][CH2:3][CH:2]=1.Cl.O1CCOCC1>CO>[NH2:21][CH2:20][C:15]1[C:14]([CH2:13][NH:12][C:10](=[O:11])[C:9]2[CH:29]=[CH:30][C:6]([C:1]3[CH2:5][CH2:4][CH2:3][CH:2]=3)=[N:7][C:8]=2[NH:31][CH2:32][CH2:33][C:34]2[CH:39]=[CH:38][CH:37]=[C:36]([F:40])[CH:35]=2)=[CH:19][CH:18]=[CH:17][N:16]=1
CC(C)(C)OC(=O)NCc1ncccc1CNC(=O)c1ccc(C2=CCCC2)nc1NCCc1cccc(F)c1
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
C1COCCO1
null
null
null
null
null
null
null
null
null
25
null
tert-butyl (3-((6-cyclopentenyl-2-(3-fluorophenethylamino)nicotinamido)methyl)pyridin-2-yl)methylcarbamate was dissolved in MeOH (1 mL) and allowed to stir at room temperature. HCl/dioxane (4M, 2 mL) was added dropwise and stirred until complete. The reaction mixture was concentrated, diluted with EtOAc, washed with saturated sodium bicarbonate, brine and dried (Na2SO4). The organics were concentrated and purified by RP-HPLC with a mixture of acetonitrile and H2O to give N-((2-(aminomethyl)pyridin-3-yl)methyl)-6-cyclopentenyl-2-(3-fluorophenethylamino)nicotinamide as a solid (0.026 g, 25%). LC/MS (M+H+) m/z 446.2.
NCc1ncccc1CNC(=O)c1ccc(C2=CCCC2)nc1NCCc1cccc(F)c1
null
25
null
1,137,467
ord_dataset-aaeaab5f3720492494c1cbbdd0ed2820
null
2012-01-01T00:02:00
true
[Br:1][C:2]1[CH:10]=[C:9]([F:11])[C:8]([F:12])=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].S(=O)(=O)(O)O.[CH3:18]O>>[CH3:18][O:5][C:4](=[O:6])[C:3]1[CH:7]=[C:8]([F:12])[C:9]([F:11])=[CH:10][C:2]=1[Br:1]
CO
O=C(O)c1cc(F)c(F)cc1Br
null
O=S(=O)(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
80
null
To a solution of 2-bromo-4,5-difluoro-benzoic acid (5 g, 21.10 mmol) in methanol (100 mL) was added concentrated sulfuric acid (0.21 mL, 2.11 mmol) at 0° C. The reaction mixture was then heated at 80° C. for 4 hours. After cooling to room temperature, the mixture was poured into ice water, and extracted with ethyl acetate. The organic layer was washed with saturated sodium bicarbonate, then brine, dried over sodium sulfate, filtered, and concentrated to afford the crude product 2-bromo-4,5-difluoro-benzoic acid methyl ester (1.48 g, 28%) as a clear oil, which was used in the next step without further purification.
COC(=O)c1cc(F)c(F)cc1Br
null
28
null
84,120
ord_dataset-7bed824f566d4af0b51d74d386b14bd6
null
1981-01-01T00:07:00
true
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[C:14]2[CH:15]=[C:16]([NH:19][C:20]([N:22]3[CH2:24][CH2:23]3)=[O:21])[CH:17]=[CH:18][C:13]=2[N:12]([CH3:25])[C:11](=[O:26])[CH2:10][N:9]=1.S(=O)(=O)(O)O.C(=O)(O)[O-].[Na+].[C:37]([OH:41])([CH3:40])([CH3:39])[CH3:38]>>[C:37]([O:41][CH2:24][CH2:23][NH:22][C:20]([NH:19][C:16]1[CH:17]=[CH:18][C:13]2[N:12]([CH3:25])[C:11](=[O:26])[CH2:10][N:9]=[C:8]([C:3]3[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=3[F:1])[C:14]=2[CH:15]=1)=[O:21])([CH3:40])([CH3:39])[CH3:38]
CC(C)(C)O
CN1C(=O)CN=C(c2ccccc2F)c2cc(NC(=O)N3CC3)ccc21
null
O=C([O-])O
O=S(=O)(O)O
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
0.33
2 g (0.0057 M) of N-[5-(o-fluorophenyl)-2,3-dihydro-1-methyl-2-oxo-1H-1,4-benzodiazepin-7-yl]-1-aziridinecarboxamide in 50 ml of tert.butanol are treated with 3 ml of 25% sulphuric acid. After 20 minutes, the mixture is made alkaline with 10% sodium bicarbonate solution and extracted several times with methylene chloride. The methylene chloride solution is dried over sodium sulphate, filtered and concentrated. The residue is purified on a 80 g silica gel column using ethyl acetate as the eluting agent and recrystallised from ethyl acetate. There is obtained 1-(2-tert.butoxyethyl)-3-[5-(o-fluorophenyl)-2,3-dihydro-1-methyl-2-oxo-1H-1,4-benzodiazepin-7-yl]urea which melts at 177° C.
CN1C(=O)CN=C(c2ccccc2F)c2cc(NC(=O)NCCOC(C)(C)C)ccc21
null
null
null
1,247,551
ord_dataset-c544c0c663f54dbea4ddb52ddde7934e
null
2013-01-01T00:01:00
true
[CH3:1][N:2](C=O)C.C1COCC1.CN(C)[CH2:13][C:14]1[C:22]2[C:17](=[CH:18][C:19]([N+:23]([O-:25])=[O:24])=[CH:20][CH:21]=2)[NH:16][CH:15]=1.[C-]#N.[K+]>O>[N+:23]([C:19]1[CH:18]=[C:17]2[C:22]([C:14]([CH2:13][C:1]#[N:2])=[CH:15][NH:16]2)=[CH:21][CH:20]=1)([O-:25])=[O:24]
CN(C)Cc1c[nH]c2cc([N+](=O)[O-])ccc12
CN(C)C=O
null
[C-]#N
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
O
null
null
null
null
null
null
null
null
null
25
null
To a mixture of DMF (35 mL) and Mel (74.6 g, 0.53 mol) in water (35 mL) and THF (400 mL) was added dimethyl-(6-nitro-1H-indol-3-ylmethyl)-amine (23 g, 0.105 mol). After the reaction mixture was refluxed for 10 min, potassium cyanide (54.6 g, 0.84 mol) was added and the mixture was kept refluxing overnight. The mixture was then cooled to room temperature and filtered. The filtrate was washed with brine (300 mL×3), dried over Na2SO4, filtered and concentrated. The residue was purified by column chromatography to give (6-nitro-1H-indol-3-yl)-acetonitrile (B-9-a) (7.5 g, 36%).
N#CCc1c[nH]c2cc([N+](=O)[O-])ccc12
null
36
null
799,690
ord_dataset-56a22bc0c3b14f87b9aa3f2fc6488ee7
null
2007-01-01T00:12:00
true
Cl[C:2]([O:4][CH3:5])=[O:3].[CH2:6]([NH:9][C:10]1[CH:15]=[CH:14][C:13]([C:16]2([C:19]([O:21]C(C)(C)C)=[O:20])[CH2:18][CH2:17]2)=[CH:12][CH:11]=1)[CH:7]=[CH2:8].C(N(CC)CC)C.C(#N)C>>[CH2:6]([N:9]([C:2]([O:4][CH3:5])=[O:3])[C:10]1[CH:15]=[CH:14][C:13]([C:16]2([C:19]([OH:21])=[O:20])[CH2:17][CH2:18]2)=[CH:12][CH:11]=1)[CH:7]=[CH2:8]
COC(=O)Cl
C=CCNc1ccc(C2(C(=O)OC(C)(C)C)CC2)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC#N
CCN(CC)CC
null
null
null
null
null
null
null
null
null
25
0.5
Methyl chloroformate (34 μL, 0.00044 mol) was added to a mixture of tert-butyl 1-[4-(allylamino)phenyl]cyclopropanecarboxylate (6.0×10−1 mg, 0.00022 mol) and triethylamine (92 μL, 0.00066 mol) in acetonitrile (1.0 mL, 0.019 mol) at rt. The reaction mixture was stirred at rt for 30 minutes, then was washed with water, and then extracted with EtOAc (3×). The organic layers were combined and concentrated. To the residue was added 4.0M HCl in dioxane and the reaction was stirred at rt for 2 h. The solvent was removed in-vacuo and used in the following step. LC/MS: 276.2 (M+H+).
C=CCN(C(=O)OC)c1ccc(C2(C(=O)O)CC2)cc1
null
null
null
1,741,378
ord_dataset-eacfee6d16d8455a93348409f1b37be4
null
2016-01-01T00:06:00
true
[CH2:1]([N:3]([CH:26]1[CH2:31][CH2:30][O:29][CH2:28][CH2:27]1)[C:4]1[CH:5]=[C:6]([CH:15]2[CH2:18][N:17]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:16]2)[CH:7]=[C:8]([C:11]([O:13]C)=[O:12])[C:9]=1[CH3:10])[CH3:2].[OH-].[Na+]>C1COCC1.CO>[C:22]([O:21][C:19]([N:17]1[CH2:18][CH:15]([C:6]2[CH:5]=[C:4]([N:3]([CH2:1][CH3:2])[CH:26]3[CH2:27][CH2:28][O:29][CH2:30][CH2:31]3)[C:9]([CH3:10])=[C:8]([CH:7]=2)[C:11]([OH:13])=[O:12])[CH2:16]1)=[O:20])([CH3:24])([CH3:25])[CH3:23]
CCN(c1cc(C2CN(C(=O)OC(C)(C)C)C2)cc(C(=O)OC)c1C)C1CCOCC1
null
null
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
CO
null
null
null
null
null
null
null
null
null
25
16
To a stirred solution of tert-butyl 3-{3-[ethyl(oxan-4-yl)amino]-5-(methoxycarbonyl)-4-methylphenyl}azetidine-1-carboxylate (78 mg, 0.18 mmol) in THF (2 ml) and MeOH (0.1 ml) was added 2M NaOH solution (0.9 ml, 1.8 mmol) and the reaction was stirred at room temperature for 16 h followed by heating at 50° C. for 22 h. The reaction was cooled to room temperature and the solvent removed in vacuo after which the aqueous solution was adjusted to pH5 using 1M HCl. The product was extracted into DCM (2×50 ml), dried with Na2SO4 and filtered to afford the title compound as a colourless oil (54 mg, 72%). LC-MS 100%, 1.70 min (3.5 minute LC-MS method), m/z=419.2, 1H NMR (500 MHz, MeOD) δ 7.77 (s, 1H), 7.55 (s, 1H), 4.36 (t, J=8.2 Hz, 2H), 3.90 (d, J=27.0 Hz, 5H), 3.71 (t, J=6.5 Hz, 1H), 3.36 (t, J=11.3 Hz, 3H), 2.55 (s, 3H), 1.92-1.81 (m, 1H), 1.64 (d, J=55.8 Hz, 3H), 1.49-1.42 (m, 10H), 0.93 (s, 3H).
CCN(c1cc(C2CN(C(=O)OC(C)(C)C)C2)cc(C(=O)O)c1C)C1CCOCC1
null
71.7
null
124,162
ord_dataset-d6752864fa634eb3b05f7440b4fb9a70
null
1984-01-01T00:11:00
true
[C:1]1([O:7][CH3:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.FC(F)(F)C1C=C([C:17]23[CH2:26][CH:21]([O:22][C:23]2([CH3:25])[CH3:24])[N:20]([CH3:27])[CH2:19][CH2:18]3)C=CC=1>CC(C)=O>[CH3:8][O:7][C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[C:17]1([C:23]([CH3:25])([CH3:24])[OH:22])[CH2:26][CH2:21][N:20]([CH3:27])[CH2:19][CH2:18]1
CN1CCC2(c3cccc(C(F)(F)F)c3)CC1OC2(C)C
COc1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(C)=O
null
null
null
null
null
null
null
null
null
null
null
null
4-(2'-Methoxyphenyl)-α,α,1-trimethyl-4-piperidinemethanol was prepared from anisole by the procedure described in Example 3 except that acetone was used in place of cyclopentanone in the preparation of III; m.p. 110°-111°; NMR (in CDCl3): τ2.6-3.1 (m, 4H); 6.2 (s, 3H); 6.7-8.5 (m, 9H); 7.9 (s, 3H) and 8.9 (broad s, 6H). Anal. Calcd. for C16H25NO2 : C, 72.96; H, 9.57; N, 5.32. Found: C, 73.02; H, 9.56; N, 5.41.
COc1ccccc1C1(C(C)(C)O)CCN(C)CC1
null
null
null
1,421,922
ord_dataset-f8e6e6a2d2bf4135b9e346456c81700f
null
2014-01-01T00:04:00
true
[F:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]=[CH:7][C:6](B1OC(C)(C)C(C)(C)O1)=[CH:5]2.[O-]P([O-])([O-])=O.[K+].[K+].[K+].[Cl:29][C:30]1[CH:35]=[C:34]([N:36]([CH2:45][O:46][CH2:47][CH2:48][Si:49]([CH3:52])([CH3:51])[CH3:50])[CH2:37][O:38][CH2:39][CH2:40][Si:41]([CH3:44])([CH3:43])[CH3:42])[N:33]2[N:53]=[CH:54][C:55](I)=[C:32]2[N:31]=1>O1CCOCC1.O>[Cl:29][C:30]1[CH:35]=[C:34]([N:36]([CH2:45][O:46][CH2:47][CH2:48][Si:49]([CH3:52])([CH3:51])[CH3:50])[CH2:37][O:38][CH2:39][CH2:40][Si:41]([CH3:44])([CH3:42])[CH3:43])[N:33]2[N:53]=[CH:54][C:55]([C:6]3[CH:7]=[N:8][C:9]4[C:4]([CH:5]=3)=[CH:3][C:2]([F:1])=[CH:11][CH:10]=4)=[C:32]2[N:31]=1
C[Si](C)(C)CCOCN(COCC[Si](C)(C)C)c1cc(Cl)nc2c(I)cnn12
CC1(C)OB(c2cnc3ccc(F)cc3c2)OC1(C)C
null
O=P([O-])([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
C1COCCO1
null
null
null
null
null
null
null
null
null
80
8
6-fluoro-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quinoline (3.65 mmol, 996.4 mg), K3PO4 (9.12 mmol, 1933.6 mg), and PdCl2(dppf)CH2Cl2 (0.30 mmol, 248 mg) was added to a solution of 5-chloro-3-iodo-N,N-bis((2-(trimethylsilyl)ethoxy)methyl)pyrazolo[1,5-a]pyrimidin-7-amine (3.04 mmol, 1684.3 mg) in dioxane (18 mL) and H2O (3 mL). The resulting solution was stirred at 80° C. under argon overnight. The mixture was diluted with H2O and then extracted with ethyl acetate (×2). The combined organic layers were washed with brine and dried with Na2SO4. Evaporation and purification by column chromatography afforded 5-chloro-3-(6-fluoroquinolin-3-yl)-N,N-bis((2-(trimethylsilyl)ethoxy)methyl)pyrazolo[1,5-a]pyrimidin-7-amine: LCMS tR=3.36 Min (5 min run, UV254nm). Mass calculated for, M+ 581.2, observed LC/MS m/z 582.2 (M+H).
C[Si](C)(C)CCOCN(COCC[Si](C)(C)C)c1cc(Cl)nc2c(-c3cnc4ccc(F)cc4c3)cnn12
null
null
null
379,125
ord_dataset-846d411edee44814931e062174d7ef12
null
1997-01-01T00:09:00
true
[C:1]1([NH:7][C:8](=[O:17])[C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=2[S:15][CH3:16])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C(=O)(O)[O-:19].[K+].BrBr>C1(C)C=CC=CC=1>[C:1]1([NH:7][C:8](=[O:17])[C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=2[S:15]([CH3:16])=[O:19])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
O=C([O-])O
CSc1ccccc1C(=O)Nc1ccccc1
null
BrBr
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
To a 1000 ml four-necked flask equipped with a stirrer, a thermometer, and a condenser, 48.6 g (0.2 mol) of N-phenyl-2-(methylthio)benzamide obtained in Example 1, 300 g of toluene, and 200 g of a 10% by weight aqueous solution of potassium bicarbonate are placed. To the above mixture in the flask, 32.0 g (0.2 mol) of bromine is added dropwise while stirring at a temperature of from 10° to 15° C. to be allowed to react with each other for about 10 minutes. After completion of the reaction, the produced white crystals are filtered and then recrystallized from a mixture of water and ethanol (1:9) to give 48.7 g of N-phenyl-2-(methylsulfinyl)benzamide (melting point: 194° to 195° C.). The yield of the product against N-phenyl-2-(methylthio)benzamide is 94%.
CS(=O)c1ccccc1C(=O)Nc1ccccc1
null
null
null
639,767
ord_dataset-1c0bae7388cf460091d56129e95b3145
null
2004-01-01T00:06:00
true
[CH3:1][CH:2]1[NH:7][CH2:6][C:5]2[S:8][C:9]([C:11]([O-:13])=O)=[N:10][C:4]=2[CH2:3]1.[Li+].[Cl:15][C:16]1[CH:17]=[C:18]2[C:23](=[CH:24][CH:25]=1)[CH:22]=[C:21]([S:26]([N:29]1[CH2:34][CH2:33][NH:32][CH:31]([CH2:35][C:36]([O:38][CH3:39])=[O:37])[CH2:30]1)(=[O:28])=[O:27])[CH:20]=[CH:19]2>>[Cl:15][C:16]1[CH:17]=[C:18]2[C:23](=[CH:24][CH:25]=1)[CH:22]=[C:21]([S:26]([N:29]1[CH2:34][CH2:33][N:32]([C:11]([C:9]3[S:8][C:5]4[CH2:6][NH:7][CH:2]([CH3:1])[CH2:3][C:4]=4[N:10]=3)=[O:13])[CH:31]([CH2:35][C:36]([O:38][CH3:39])=[O:37])[CH2:30]1)(=[O:27])=[O:28])[CH:20]=[CH:19]2
COC(=O)CC1CN(S(=O)(=O)c2ccc3cc(Cl)ccc3c2)CCN1
CC1Cc2nc(C(=O)[O-])sc2CN1
null
[Li+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Starting materials: lithium 6-methyl-4,5,6,7-tetrahydrothiazolo[5,4-c]pyridine-2-carboxylate, 1-[(6-chloronaphthalen-2-yl)sulfonyl]-3-[methoxycarbonylmethyl]piperazine
COC(=O)CC1CN(S(=O)(=O)c2ccc3cc(Cl)ccc3c2)CCN1C(=O)c1nc2c(s1)CNC(C)C2
null
null
null
333,309
ord_dataset-ba1248d90e3e465693710bbc45866f37
null
1996-01-01T00:07:00
true
Cl[P:2]1[N:5]([C:6]2[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=2)[P:4](Cl)[N:3]1[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[CH:19]([C:22]1[CH:27]=[CH:26][CH:25]=[C:24]([CH:28]([CH3:30])[CH3:29])[C:23]=1[OH:31])([CH3:21])[CH3:20]>C(N(CC)CC)C>[CH:28]([C:24]1[CH:25]=[CH:26][CH:27]=[C:22]([CH:19]([CH3:21])[CH3:20])[C:23]=1[O:31][P:2]1[N:5]([C:6]2[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=2)[P:4]([O:31][C:23]2[C:24]([CH:28]([CH3:29])[CH3:30])=[CH:25][CH:26]=[CH:27][C:22]=2[CH:19]([CH3:21])[CH3:20])[N:3]1[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)([CH3:30])[CH3:29]
ClP1N(c2ccccc2)P(Cl)N1c1ccccc1
CC(C)c1cccc(C(C)C)c1O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(CC)CC
null
null
null
null
null
null
null
null
null
null
null
null
The procedure of Example 1 is repeated using 2,4-dichloro-1,3-diphenyl-1,3,2,4-diazadiphosphetidine, 2,6-diisopropylphenol and triethylamine to give the title compound.
CC(C)c1cccc(C(C)C)c1OP1N(c2ccccc2)P(Oc2c(C(C)C)cccc2C(C)C)N1c1ccccc1
null
null
null
1,516,487
ord_dataset-8c74302143c04eb9983e4b3a7ead2d72
null
2014-01-01T00:12:00
true
[Cl:1][C:2]1[C:10]2[N:9]=[C:8]3[N:11]([C:15]4[CH:20]=[CH:19][C:18]([Cl:21])=[CH:17][C:16]=4[Cl:22])[CH2:12][CH2:13][CH2:14][N:7]3[C:6]=2[C:5]([CH:23]([CH2:30][CH3:31])[CH:24]([OH:29])[C:25]([F:28])([F:27])[F:26])=[CH:4][CH:3]=1.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>C(#N)C>[Cl:1][C:2]1[C:10]2[N:9]=[C:8]3[N:11]([C:15]4[CH:20]=[CH:19][C:18]([Cl:21])=[CH:17][C:16]=4[Cl:22])[CH2:12][CH2:13][CH2:14][N:7]3[C:6]=2[C:5]([CH:23]([CH2:30][CH3:31])[C:24](=[O:29])[C:25]([F:26])([F:27])[F:28])=[CH:4][CH:3]=1
CCC(c1ccc(Cl)c2nc3n(c12)CCCN3c1ccc(Cl)cc1Cl)C(O)C(F)(F)F
null
null
CC(=O)OI1(OC(C)=O)(OC(C)=O)OC(=O)c2ccccc21
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC#N
null
null
null
null
null
null
null
null
null
null
null
1
To a stirred solution of 3-[9-chloro-1-(2,4-dichlorophenyl)-1,2,3,4-tetrahydropyrimido[1,2-a]benzimidazol-6-yl]-1,1,1-trifluoropentan-2-ol (47.4 mg, 0.0961 mmol) in acetonitrile (0.6 mL) was added Dess-Martin reagent (48.9 mg, 0.115 mmol) at room temperature. After 1 h, the reaction mixture was concentrated in vacuo and purified by flash column chromatography on NH silica gel eluting with a 0-10% methanol/ethyl acetate gradient mixture to give the title compound as a colorless amorphous (33.3 mg, 0.0678 mmol, 71%).
CCC(C(=O)C(F)(F)F)c1ccc(Cl)c2nc3n(c12)CCCN3c1ccc(Cl)cc1Cl
null
null
null
967,622
ord_dataset-03ba810b7f464a06b5d8787af2e8b64e
null
2010-01-01T00:06:00
true
[CH3:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[CH:4][C:3]=1[SH:9].[Br:10][C:11]1[CH:16]=[C:15]([C:17]([F:20])([F:19])[F:18])[CH:14]=[CH:13][C:12]=1I>>[Br:10][C:11]1[CH:16]=[C:15]([C:17]([F:18])([F:19])[F:20])[CH:14]=[CH:13][C:12]=1[S:9][C:3]1[CH:4]=[CH:5][C:6]([CH3:8])=[CH:7][C:2]=1[CH3:1]
FC(F)(F)c1ccc(I)c(Br)c1
Cc1ccc(S)c(C)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Prepared from 2,4-dimethyl-benzenethiol and 2-bromo-1-iodo-4-trifluoromethyl-benzene.
Cc1ccc(Sc2ccc(C(F)(F)F)cc2Br)c(C)c1
null
null
null
699,755
ord_dataset-bbd7e53f000345838ad4920a07a169ff
null
2006-01-01T00:03:00
true
[C:1]1([CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13]O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C(Br)(Br)(Br)[Br:16].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(C)=O>C(Cl)Cl>[Br:16][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
BrC(Br)(Br)Br
OCCCCCCCc1ccccc1
null
c1ccc(P(c2ccccc2)c2ccccc2)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOC(C)=O
ClCCl
null
null
null
null
null
null
null
null
null
null
0.01
To a solution of 7-phenyl-1-heptanol (29.1 g, 151.3 mmol) in 800 mL CH2Cl2 at room temperature was added CBr4 (60.2 g, 181.6 mmol) then triphenylphosphine (47.6 g, 181.6 mmol). After 30 s, the reaction had turned a light green color. TLC indicated that the reaction was complete at this point. The solvent was removed in vacuo to give a greenish-white semisolid. To this material was added 10% EtOAc: 90% Hexanes and the resulting suspension was filtered through a pad of silica gel washing well with the same solvent system. There yielded 57 g of a colorless oil as the desired bromide and triphenylphosphine oxide. This oil was then flash chromatographed (Hexanes) to yield 38.6 g, 100% of the bromide as a colorless oil. 1H NMR (CDCl3) δ 1.30–1.49 (m, 6H); 1.60 (quintet, J=8.18 Hz, 2H); 2.60 (t, J=8.18 Hz, 2H); 3.39 (t, J=8.18 Hz, 2H); 7.13–7.20 (m, 3H); 7.21–7.31 (m, 2H).
BrCCCCCCCc1ccccc1
null
147.6
null
725,318
ord_dataset-0387783899c642a8b7eb4ba379bcdf5d
null
2006-01-01T00:08:00
true
[NH2:1][CH2:2][CH:3]([C:9]1([CH3:14])[O:13][CH2:12][CH2:11][O:10]1)[C:4]([O:6][CH2:7][CH3:8])=[O:5].[F:15][C:16]1[CH:26]=[CH:25][C:24]([F:27])=[C:18]2[C:19]([O:21][C:22](=O)[C:17]=12)=[O:20]>>[F:15][C:16]1[CH:26]=[CH:25][C:24]([F:27])=[C:18]2[C:17]=1[C:22](=[O:21])[N:1]([CH2:2][CH:3]([C:9]1([CH3:14])[O:10][CH2:11][CH2:12][O:13]1)[C:4]([O:6][CH2:7][CH3:8])=[O:5])[C:19]2=[O:20]
O=C1OC(=O)c2c(F)ccc(F)c21
CCOC(=O)C(CN)C1(C)OCCO1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Ethyl 3-(4,7-difluoro-1,3-dioxo-1,3-dihydro-isoindol-2-yl)-2-(2-methyl-[1,3]dioxolan-2-yl)propionate was prepared in the same manner as described in the above example 5 (20) from ethyl 3-amino-2-(2-methyl-[1,3]dioxolan-2-yl)propionate (0.80 g, 3.94 mmol) and 3,6-difluorophthalic anhydride (0.94 g, 4.33 mmol), and the obtained product was identified with the following NMR data.
CCOC(=O)C(CN1C(=O)c2c(F)ccc(F)c2C1=O)C1(C)OCCO1
null
null
null
626,850
ord_dataset-e44331dc51de453ca14b7032593c1958
null
2004-01-01T00:02:00
true
[F:1]C1C=CC(OC)=C(C2C(C(O)=O)=CC([N+]([O-])=O)=CC=2)C=1.C[C:23]1[CH:28]=[CH:27][C:26]([O:29][CH3:30])=[CH:25][C:24]=1[C:31]1[C:32]([C:41]([O:43]C)=[O:42])=[CH:33][C:34]([N+:38]([O-:40])=[O:39])=[CH:35][C:36]=1C>>[F:1][C:23]1[CH:28]=[CH:27][C:26]([O:29][CH3:30])=[CH:25][C:24]=1[C:31]1[C:32]([C:41]([OH:43])=[O:42])=[CH:33][C:34]([N+:38]([O-:40])=[O:39])=[CH:35][CH:36]=1
COc1ccc(F)cc1-c1ccc([N+](=O)[O-])cc1C(=O)O
COC(=O)c1cc([N+](=O)[O-])cc(C)c1-c1cc(OC)ccc1C
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
This compound was prepared in a manner similar to that of 5′-fluoro-2′-methoxy-4-nitro-2-biphenylcarboxylic acid (EXAMPLE 107) from methyl 2′-methyl-5′-methoxy-6-methyl-4-nitro-2-biphenylcarboxylate (0.77 g) to afford 0.73 g (99%) of 2′-fluoro-5′-methoxy-4-nitro-2-biphenylcarboxylic acid as a white solid, which was used in the next step without further purification.
COc1ccc(F)c(-c2ccc([N+](=O)[O-])cc2C(=O)O)c1
null
99
null
1,081,716
ord_dataset-afd812677c134591a99f46ce28de2524
null
2011-01-01T00:08:00
true
[N:1]1([C:7]2[CH:8]=[CH:9][C:10]3[N:11]([C:13]([C:16]([F:19])([F:18])[F:17])=[N:14][N:15]=3)[N:12]=2)[CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1.[CH:20]([C:22]1[CH:31]=[CH:30][C:25]([O:26][CH2:27][C:28]#[N:29])=[CH:24][CH:23]=1)=O>>[F:19][C:16]([F:17])([F:18])[C:13]1[N:11]2[N:12]=[C:7]([N:1]3[CH2:2][CH2:3][N:4]([CH2:20][C:22]4[CH:31]=[CH:30][C:25]([O:26][CH2:27][C:28]#[N:29])=[CH:24][CH:23]=4)[CH2:5][CH2:6]3)[CH:8]=[CH:9][C:10]2=[N:15][N:14]=1
N#CCOc1ccc(C=O)cc1
FC(F)(F)c1nnc2ccc(N3CCNCC3)nn12
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Reductive amination of 6-(piperazin-1-yl)-3-(trifluoromethyl)-[1,2,4]triazolo[4,3-b]pyridazine with 2-(4-formylphenoxy)acetonitrile was carried out according to General Synthetic Method 7. The crude product was purified by hplc using a Waters XBridge Prep C18 OBD column, 5μ silica, 30 mm diameter, 100 mm length eluted with decreasingly polar mixtures of water (containing 0.1% aqueous ammonia) and acetonitrile as eluents to give 2-[4-[[4-[3-(trifluoromethyl)-[1,2,4]triazolo[4,3-b]pyridazin-6-yl]piperazin-1-yl]methyl]phenoxy]acetonitrile.
N#CCOc1ccc(CN2CCN(c3ccc4nnc(C(F)(F)F)n4n3)CC2)cc1
null
null
null
471,482
ord_dataset-cd531114850e4f239b2a3661044ae672
null
2000-01-01T00:08:00
true
O1[CH:5]=[CH:4][CH:3]=[C:2]1[C:6](=[O:15])[CH:7]=[CH:8][C:9]1[CH:14]=[CH:13][N:12]=[CH:11][CH:10]=1.[C:16](C1CCCCC1)(=O)[CH3:17]>>[CH:2]1([C:6](=[O:15])[CH:7]=[CH:8][C:9]2[CH:14]=[CH:13][N:12]=[CH:11][CH:10]=2)[CH2:17][CH2:16][CH2:5][CH2:4][CH2:3]1
CC(=O)C1CCCCC1
O=C(C=Cc1ccncc1)c1ccco1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
1-(2-Furyl-3-(4-pyridyl)-2-propene-1-one: MS (m/z): 200.0 (M+H)+ ; C12H9NO2 requir. 199.2. 1-Cyclohexyl-3-(4-pyridyl)-2-propene-1-one was prepared in the same way using acetylcyclohexane: MS (m/z): 216.2 (M+H)+ ; C14H17NO requir. 215.3.
O=C(C=Cc1ccncc1)C1CCCCC1
null
null
null
1,254,775
ord_dataset-c544c0c663f54dbea4ddb52ddde7934e
null
2013-01-01T00:01:00
true
COC1C=CC(C[N:8](CC2C=CC(OC)=CC=2)[C:9]2[N:14]=[C:13]([CH3:15])[N:12]=[C:11]([C:16]3[C:17]([NH:24][C:25]4[CH:26]=[N:27][C:28]([O:31][CH3:32])=[CH:29][CH:30]=4)=[N:18][CH:19]=[C:20]([CH:23]=3)[CH:21]=O)[N:10]=2)=CC=1.[N:44]1[CH:45]=[N:46][N:47]2[CH2:52][CH2:51][NH:50][CH2:49][C:48]=12>>[N:44]1[CH:45]=[N:46][N:47]2[CH2:52][CH2:51][N:50]([CH2:21][C:20]3[CH:23]=[C:16]([C:11]4[N:12]=[C:13]([CH3:15])[N:14]=[C:9]([NH2:8])[N:10]=4)[C:17]([NH:24][C:25]4[CH:26]=[N:27][C:28]([O:31][CH3:32])=[CH:29][CH:30]=4)=[N:18][CH:19]=3)[CH2:49][C:48]=12
c1nc2n(n1)CCNC2
COc1ccc(CN(Cc2ccc(OC)cc2)c2nc(C)nc(-c3cc(C=O)cnc3Nc3ccc(OC)nc3)n2)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was synthesized following an analogous procedure to Example 220 using 5-(4-(bis(4-methoxybenzyl)amino)-6-methyl-1,3,5-triazin-2-yl)-6-(6-methoxypyridin-3-ylamino)nicotinaldehyde (178 mg, 0.308 mmol) and 5,6,7,8-tetrahydro-[1,2,4]triazolo[1,5-a]pyrazine (GeneTech, Indianapolis, Ind.) (57.4 mg, 0.462 mmol). 1H NMR (400 MHz, CDCl3) δ 11.70 (s, 1H); 8.78 (d, J=2.54 Hz, 1H); 8.36 (d, J=2.74 Hz, 1H); 8.25 (d, J=2.35 Hz, 1H); 8.10 (dd, J=8.80, 2.74 Hz, 1H); 7.87 (s, 1H); 6.78 (d, J=8.61 Hz, 1H); 5.59 (s, 2H); 4.20 (t, J=5.38 Hz, 2H); 3.94 (s, 3H); 3.84 (s, 2H); 3.73 (s, 2H); 3.00 (t, J=5.48 Hz, 2H); 2.56 (s, 3H). m/z (ESI, +ve ion) 445.9 (M+H)+.
COc1ccc(Nc2ncc(CN3CCn4ncnc4C3)cc2-c2nc(C)nc(N)n2)cn1
null
null
null
1,462,825
ord_dataset-fd1fa959d6264608b0b7fcda16741bfd
null
2014-01-01T00:08:00
true
[Cl:1][C:2]1[CH:30]=[CH:29][C:5]([CH2:6][N:7]2[C:15]3[C:10](=[CH:11][C:12](/[CH:16]=[C:17]4/[C:18](=[O:28])[N:19]([C@H:23]5[CH2:27][CH2:26][NH:25][CH2:24]5)[C:20](=[O:22])[S:21]/4)=[CH:13][CH:14]=3)[CH:9]=[N:8]2)=[C:4]([C:31]([F:34])([F:33])[F:32])[CH:3]=1.[CH2:35](I)[CH3:36]>>[Cl:1][C:2]1[CH:30]=[CH:29][C:5]([CH2:6][N:7]2[C:15]3[C:10](=[CH:11][C:12](/[CH:16]=[C:17]4/[C:18](=[O:28])[N:19]([C@H:23]5[CH2:27][CH2:26][N:25]([CH2:35][CH3:36])[CH2:24]5)[C:20](=[O:22])[S:21]/4)=[CH:13][CH:14]=3)[CH:9]=[N:8]2)=[C:4]([C:31]([F:34])([F:33])[F:32])[CH:3]=1
O=C1S/C(=C\c2ccc3c(cnn3Cc3ccc(Cl)cc3C(F)(F)F)c2)C(=O)N1[C@H]1CCNC1
CCI
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
(5Z)-5-({1-[4-Chloro-2-(trifluoromethyl)benzyl]-1H-indazol-5-yl}methylidene)-3-[(3S)-1-ethylpyrrolidin-3-yl]-1,3-thiazolidine-2,4-dione was prepared from (5Z)-5-({1-[4-chloro-2-(trifluoromethyl)benzyl]-1H-indazol-5-yl}methylidene)-3-[(3S)-pyrrolidin-3-yl]-1,3-thiazolidine-2,4-dione (Example 114) and ethyl iodide at rt following General Procedure S.
CCN1CC[C@H](N2C(=O)S/C(=C\c3ccc4c(cnn4Cc4ccc(Cl)cc4C(F)(F)F)c3)C2=O)C1
null
null
null
1,478,577
ord_dataset-c3c1091f873b4f40827973a6f1f9b685
null
2014-01-01T00:09:00
true
[C:1]([C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][CH:4]=1)#[N:2].[CH2:13]([Mg]Br)[CH3:14].B(F)(F)F.CCOCC.Cl>C(OCC)C.[Ti+4]>[NH2:2][C:1]1([C:3]2[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][CH:4]=2)[CH2:14][CH2:13]1
CC[Mg]Br
COC(=O)c1ccc(C#N)cc1
null
[Ti+4]
Cl
FB(F)F
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOCC
null
null
null
null
null
null
null
null
null
null
null
1
To the solution of methyl 4-cyanobenzoate (100 g, 620 mmol) in diethyl ether (3 L) was added titanium (IV) isospropoxide (194 g, 682 mmol), followed by dropwise addition of ethylmagnesium bromide 3M solution in diethylether (450 ml, 1.36 mol) at −70° C. The mixture was stirred for 1 h, and then boron trifluoride etherate (157 ml, 1.24 mol) was added at once. After 2 hours, aqueous HCl (5%) was added until the pH showed acidy, then the mixture was filtered. The solid was washed with ethylacetate. The aqueous phase was separated and the organic layer was washed with water. All aqueous layers were collected together, basified with 1M NaOH and extracted with ethylacetate. The organic layer was dried (Na2SO4) and concentrated to afford the title compound (D6) (32.0 g).
COC(=O)c1ccc(C2(N)CC2)cc1
null
null
null
825,378
ord_dataset-0ca5627a13c049a99463095023b09fe5
null
2008-01-01T00:06:00
true
[NH2:1][CH2:2][C:3]1[N:4]=[C:5]([NH:8][C:9]([NH:11][C:12]2[CH:17]=[CH:16][C:15]([CH3:18])=[CH:14][C:13]=2[C:19]([CH:21]2[CH2:25][CH2:24][CH2:23][CH2:22]2)=[O:20])=[O:10])[S:6][CH:7]=1.[CH3:26][N:27]([CH3:32])[S:28](Cl)(=[O:30])=[O:29]>>[CH:21]1([C:19]([C:13]2[CH:14]=[C:15]([CH3:18])[CH:16]=[CH:17][C:12]=2[NH:11][C:9](=[O:10])[NH:8][C:5]2[S:6][CH:7]=[C:3]([CH2:2][NH:1][S:28]([N:27]([CH3:32])[CH3:26])(=[O:30])=[O:29])[N:4]=2)=[O:20])[CH2:25][CH2:24][CH2:23][CH2:22]1
CN(C)S(=O)(=O)Cl
Cc1ccc(NC(=O)Nc2nc(CN)cs2)c(C(=O)C2CCCC2)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
N-{2-[3-(2-Cyclopentanecarbonyl-4-methyl-phenyl)-ureido]-thiazol-4-ylmethyl)-N′,N′-dimethylsulfamide (104 mg, 89%) was prepared from 1-(4-aminomethyl-thiazol-2-yl)-3-(2-cyclopentanecarbonyl-4-methyl-phenyl)-urea (90 mg, 0.25 mmol) and dimethylsulfamoyl chloride (0.06 mL, 0.5 mmol) following the general procedure T.
Cc1ccc(NC(=O)Nc2nc(CNS(=O)(=O)N(C)C)cs2)c(C(=O)C2CCCC2)c1
null
89.3
null
172,217
ord_dataset-7860c6f563014da8948ede63b7110bde
null
1988-01-01T00:05:00
true
[CH3:1][C:2]1[NH:6][C:5]([C:7]2[CH:12]=[CH:11][C:10]([CH3:13])=[CH:9][CH:8]=2)=[N:4][C:3]=1[C:14]([O:16]CC)=O.[NH2:19][NH2:20]>O>[CH3:1][C:2]1[NH:6][C:5]([C:7]2[CH:8]=[CH:9][C:10]([CH3:13])=[CH:11][CH:12]=2)=[N:4][C:3]=1[C:14]([NH:19][NH2:20])=[O:16]
CCOC(=O)c1nc(-c2ccc(C)cc2)[nH]c1C
NN
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
null
null
null
null
null
null
null
null
null
null
null
null
A mixture of 4.9 g of the above ester and 15 ml of anhydrous hydrazine was stirred and refluxed overnight. Water was added, the mixture was evaporated and the residue recrystallized from ethanol, giving 3.45 g of 5-methyl-2-(4-methylphenyl)-1H-imidazole-4-carboxylic acid, hydrazide.
Cc1ccc(-c2nc(C(=O)NN)c(C)[nH]2)cc1
null
null
null
1,523,564
ord_dataset-8c74302143c04eb9983e4b3a7ead2d72
null
2014-01-01T00:12:00
true
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH:10]=O)=[N:6][C:7]=1[O:8][CH3:9].[NH2:12][CH3:13].[BH4-].[Na+]>C1COCC1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:10][NH:12][CH3:13])=[N:6][C:7]=1[O:8][CH3:9]
CN
COc1nc(C=O)ccc1Br
null
[BH4-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
25
0.75
5-Bromo-6-methoxypicolinaldehyde of preparation 78 (69 mg, 0.32 mmol) in a solution of NH2CH3 in THF (2M, 3 mL) was stirred under nitrogen at room temperature for 45 mins, and LCMS showed a mass of 230 which indicated the presence of the iminium ion. Sodium borohydride (36.2 mg, 0.957 mmol) was added, and the reaction was stirred at room temperature overnight. The desired product was detected by LCMS, and the reaction was quenched with MeOH (0.5 mL) and water (10 ml), then partitioned with EtOAc (10 mL). The organic layer was dried over sodium sulfate, filtered and evaporated to give the title compound as a yellow oil (47 mg), which was taken into the next step without further purification.
CNCc1ccc(Br)c(OC)n1
null
null
null
395,439
ord_dataset-018fd0e1351f4fd09b20fcddd97b4c7a
null
1998-01-01T00:03:00
true
[I:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][C:10]=1[CH3:11])[C:5](O)=[O:6].S(Cl)(C1C=CC(C)=CC=1)(=O)=O.Cl.[CH3:24][NH2:25]>>[CH3:24][NH:25][C:5]([C:4]1[CH:8]=[CH:9][C:10]([CH3:11])=[C:2]([I:1])[CH:3]=1)=[O:6]
CN
Cc1ccc(C(=O)O)cc1I
null
Cc1ccc(S(=O)(=O)Cl)cc1
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
5
A solution of 1.0 mmol of 3-iodo-4-methylbenzoic acid, 1.2 mmol of TsCl, and 25 mmol of Py was stirred for 3 h and then 5 mmol of methylamine hydrochloride was added and stirring continued for 5 h. Chromatography provided N-methyl-(3-iodo-4-methylphenyl)carboxamide.
CNC(=O)c1ccc(C)c(I)c1
null
null
null
1,663,953
ord_dataset-42cd9bc5aae3485f9a58f1527bd3abf0
null
2015-01-01T00:11:00
true
[CH2:1]([NH:8][C:9]([NH:11][N:12]([CH2:14][C:15]([OH:17])=O)[CH3:13])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH2:18][C@H:19]([C:28]([N:30]([C@@H:42]([CH3:50])[CH:43]([O:47][CH2:48][CH3:49])[O:44][CH2:45][CH3:46])[CH2:31][C:32]1[C:41]2[C:36](=[CH:37][CH:38]=[CH:39][CH:40]=2)[CH:35]=[CH:34][CH:33]=1)=[O:29])[CH2:20][C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22]>>[CH2:1]([NH:8][C:9]([NH:11][N:12]([CH2:14][C:15]([NH:18][C@H:19]([C:28]([N:30]([C@@H:42]([CH3:50])[CH:43]([O:47][CH2:48][CH3:49])[O:44][CH2:45][CH3:46])[CH2:31][C:32]1[C:41]2[C:36](=[CH:37][CH:38]=[CH:39][CH:40]=2)[CH:35]=[CH:34][CH:33]=1)=[O:29])[CH2:20][C:21]([O:23][C:24]([CH3:27])([CH3:25])[CH3:26])=[O:22])=[O:17])[CH3:13])=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
CCOC(OCC)[C@H](C)N(Cc1cccc2ccccc12)C(=O)[C@@H](N)CC(=O)OC(C)(C)C
CN(CC(=O)O)NC(=O)NCc1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
According to the procedure described in the synthesis method of Compound II-15, 2-(2-(benzylcarbamoyl)-1-methylhydrazinyl)acetic acid (Compound VI-3) 78 mg (0.33 mmol) was coupled with (S)-tert-butyl 3-amino-4-(((S)-1,1-diethoxypropan-2-yl)-(naphthalen-1-ylmethyl)amino)-4-oxobutanoate (Compound IV-16) 100 mg (0.22 mmol) to obtain the title compound.
CCOC(OCC)[C@H](C)N(Cc1cccc2ccccc12)C(=O)[C@H](CC(=O)OC(C)(C)C)NC(=O)CN(C)NC(=O)NCc1ccccc1
null
null
null
56,284
ord_dataset-159c363342e44b539e7a5975c873e30d
null
1979-01-01T00:05:00
true
[Cl:1][CH2:2][CH2:3][N:4]([N:17]=[O:18])[C:5](=O)[O:6]C1C=CC=CC=1[N+]([O-])=O.[NH2:19][C@@H:20]1[O:28][C@H:27]([CH2:29][OH:30])[C@@H:25]([OH:26])[C@H:23]([OH:24])[C@H:21]1[OH:22]>CN(C)C=O.C(O)C>[C@@H:20]1([NH:19][C:5](=[O:6])[N:4]([CH2:3][CH2:2][Cl:1])[N:17]=[O:18])[O:28][C@H:27]([CH2:29][OH:30])[C@@H:25]([OH:26])[C@H:23]([OH:24])[C@H:21]1[OH:22]
N[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O
O=NN(CCCl)C(=O)Oc1ccccc1[N+](=O)[O-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
CCO
null
null
null
null
null
null
null
null
null
null
0.17
3.28 g (12 mmol) of o-nitrophenyl N-(2-chloroethyl)-N-nitrosocarbamate is dissolved in a mixture of 10 ml anhydrous dimethylformamide and 10 ml anhydrous ethanol, and to this solution is added little by little 1.79 g (10 mmol) of 1-amino-1-deoxy-β-D-glucopyranose powder, while stirring, at 5°-10° C. over 10 minutes. The resultant mixture is, after adding 5 ml of anhydrous dimethylformamide thereto, stirred further at 10° C. for 5 hours, and the thus reacted solution is concentrated at 40° C. and below, under reduced pressure. The crystalline residue obtained is washed with anhydrous ethyl ether and then with acetone, dried under reduced pressure, and recrystallized from anhydrous ethanol-ethyl ether (1:5) to give 2.47 g of 3-(β-D-glucopyranosyl)-1-(2-chloroethyl)-1-nitrosourea. Yield 78.7%. mp 77°-78° C. (decomp.). [α]D25 -10.3° (C 1.0, water). Analysis for C9H16N3O7Cl (MW 313.69):
O=NN(CCCl)C(=O)N[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O
null
78.7
null
176,514
ord_dataset-07db50a3ce6941919df30a9e2898988f
null
1988-01-01T00:08:00
true
[Cl:1][CH2:2][O:3][C:4](F)(F)[CH:5]([C:10]([F:13])([F:12])[F:11])[C:6]([F:9])([F:8])[F:7].[Si](=O)=[O:17].S(=O)(=O)(O)O>>[F:7][C:6]([F:9])([F:8])[CH:5]([C:10]([F:13])([F:12])[F:11])[C:4]([O:3][CH2:2][Cl:1])=[O:17]
FC(F)(F)C(C(F)(F)F)C(F)(F)OCCl
O=[Si]=O
null
O=S(=O)(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
null
21
In a four necked 1 liter flask equipped with a thermometer, a condenser and a stirrer, 1-chloromethoxy-1,1-difluoro-2-trifluoromethyl-3,3,3-trifluoropropane (276.6 g, 1.04 mol) and silicon dioxide (50.8 g, 0.85 mol) were charged, and concentrated sulfuric acid (60 g, 0.61 mol) was dropwise added thereto while stirring. The reaction was continued at 110° C. for 21 hours. Then, the reaction mixture was distilled to give monochloromethyl 2-trifluoromethyl-3,3,3-trifluoropropanoate (192.9 g).
O=C(OCCl)C(C(F)(F)F)C(F)(F)F
null
92.8
null
1,241,171
ord_dataset-c544c0c663f54dbea4ddb52ddde7934e
null
2013-01-01T00:01:00
true
C(OC([N:8]1[CH2:13][CH2:12][N:11]([CH2:14][C:15]2[CH:20]=[CH:19][C:18]([C:21]3[CH:22]=[C:23]([C:27]4[CH:32]=[C:31]([NH2:33])[N:30]=[C:29]([C:34]5[CH:39]=[CH:38][CH:37]=[CH:36][N:35]=5)[CH:28]=4)[CH:24]=[N:25][CH:26]=3)=[CH:17][CH:16]=2)[CH2:10][CH2:9]1)=O)(C)(C)C.C(O)(C(F)(F)F)=O>C(Cl)Cl>[N:11]1([CH2:14][C:15]2[CH:20]=[CH:19][C:18]([C:21]3[CH:22]=[C:23]([C:27]4[CH:32]=[C:31]([NH2:33])[N:30]=[C:29]([C:34]5[CH:39]=[CH:38][CH:37]=[CH:36][N:35]=5)[CH:28]=4)[CH:24]=[N:25][CH:26]=3)=[CH:17][CH:16]=2)[CH2:10][CH2:9][NH:8][CH2:13][CH2:12]1
CC(C)(C)OC(=O)N1CCN(Cc2ccc(-c3cncc(-c4cc(N)nc(-c5ccccn5)c4)c3)cc2)CC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O=C(O)C(F)(F)F
ClCCl
null
null
null
null
null
null
null
null
null
25
0.5
To a solution of 4-[4-(6′-Amino-[2,2′;4′,3″]terpyridin-5″-yl)-benzyl]-piperazine-1-carboxylic acid tert-butyl ester (1.0 eq, 0.105 mmol, 55.1 mg) in DCM (1.0 ml) is added TFA (24.0 eq, 2.60 mmol, 0.2 ml). The reaction mixture is allowed to stir at room temperature for 30 minutes. The organic solvent is reduced in vacuo. The residue is purified by reverse phase chromatography (Isolute™ C18, 0-20% acetonitrile in water—0.1% TFA). The appropriate fractions by HPLC are combined and concentrated in vacuo. The resulting residue is dissolved in MeOH and loaded onto a SCX-2 cartridge eluting with MeOH and 2M NH3 in MeOH. The methanolic ammonia fractions are combined, concentrated in vacuo and dried under vacuum to afford the title compound; [M+H]+ 423.
Nc1cc(-c2cncc(-c3ccc(CN4CCNCC4)cc3)c2)cc(-c2ccccn2)n1
null
null
null
528,580
ord_dataset-f027aa93238e424fbbf9bad1c7699adc
null
2001-01-01T00:12:00
true
[CH3:1][C:2]1[O:6][C:5]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)=[N:4][C:3]=1[CH2:13][CH2:14][C@@H:15]([C:18]1[CH:23]=[CH:22][C:21]([CH:24]=[C:25]2[S:29][C:28](=[O:30])[NH:27][C:26]2=[O:31])=[CH:20][CH:19]=1)[O:16][CH3:17].[S]>C1COCC1>[CH3:1][C:2]1[O:6][C:5]([C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=2)=[N:4][C:3]=1[CH2:13][CH2:14][CH:15]([C:18]1[CH:23]=[CH:22][C:21]([CH2:24][C@@H:25]2[S:29][C:28](=[O:30])[NH:27][C:26]2=[O:31])=[CH:20][CH:19]=1)[O:16][CH3:17]
CO[C@@H](CCc1nc(-c2ccccc2)oc1C)c1ccc(C=C2SC(=O)NC2=O)cc1
null
null
[S]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
null
The title compound of Example 17 (640 mg, 1.5 mmol) was dissolved in THF (50 mL) and hydrogenated in the presence of sulfur-resistant 10% palladium on carbon (640 mg) on a Parr Shaker at 50 PSI for 20 hours. The catalyst was removed via filtration through diatomaceous earth and the filtrate was concentrated in vacuo. The residue was purified on silica gel, eluting with hexane/ethyl acetate (3/1) plus 5% acetic acid, to afford crude material which was further purified by (dissolving the residue in 50 mL of ethyl acetate, washing with water (25 mL), saturated aqueous sodium bicarbonate (25 mL), brine (25 mL) and drying (MgSO4), to afford a colorless gum (229 mg, 35%). 1HNMR (300 MHz, CDCl3): δ2.0 (m, 2H), 2.3 (s, 3H), 2.5 (t, 2H), 3.1 (dd, 1H), 3.2 (s, 3H), 3.5 (dd, 1H), 4.1 (dd, 1H), 4.4 (dd, 1H), 7.2 (m, 4H), 7.4 (m, 3H), 7.9 (m, 2H), 8.1 (bs, 1H, NH).
COC(CCc1nc(-c2ccccc2)oc1C)c1ccc(C[C@@H]2SC(=O)NC2=O)cc1
null
35
null
1,240,850
ord_dataset-c544c0c663f54dbea4ddb52ddde7934e
null
2013-01-01T00:01:00
true
C([O:3][C:4](=[O:24])[CH2:5][C@H:6]1[O:10][B:9]([OH:11])[C:8]2[CH:12]=[C:13]([O:17][C:18]3[CH:23]=[N:22][CH:21]=[CH:20][N:19]=3)[CH:14]=[C:15]([CH3:16])[C:7]1=2)C.[Li+].[OH-].Cl>CO.O>[OH:11][B:9]1[C:8]2[CH:12]=[C:13]([O:17][C:18]3[CH:23]=[N:22][CH:21]=[CH:20][N:19]=3)[CH:14]=[C:15]([CH3:16])[C:7]=2[C@@H:6]([CH2:5][C:4]([OH:24])=[O:3])[O:10]1
CCOC(=O)C[C@H]1OB(O)c2cc(Oc3cnccn3)cc(C)c21
null
null
Cl
[Li+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
O
null
null
null
null
null
null
null
null
null
25
3
To a solution of (3R)-[1-hydroxy-4-methyl-6-(pyrazin-2-yloxy)-1,3-dihydro-benzo[c][1,2]-oxaborol-3-yl]-acetic acid ethyl ester (0.90 g, 2.74 mmol, 1st peak) in methanol (15 mL) was added a solution of LiOH (0.328 g, 13.7 mmol) in water (12 mL) at 0° C. The resulting mixture was stirred at room temperature for 3 hours then acidified to pH=2 with dilute hydrochloric acid and extracted with EtOAc (2×30 mL). The organic extracts were washed with brine, dried over sodium sulfate and concentrated in vacuo. The residue was purified by silica gel flash column chromatography (DCM/MeOH/AcOH=20:1:trace) to give pure product as a white powder after lyophilization (0.681 g, 82.8%). 1HNMR (400 MHz, DMSO-d δ 9.20 (s, 1H), 8.53 (d, J=1.17 Hz, 1H), 8.35 (d, J=2.64 Hz, 1H), 8.19 (dd, J=2.63, 1.46 Hz, 1H), 7.25 (d, J=2.05 Hz, 1H), 7.10 (d, J=1.46 Hz, 1H), 5.51 (dd, J=9.51, 2.20 Hz, 1H), 3.07 (dd, J=15.52, 2.63 Hz, 1H), 2.28 (s, 3H), 2.13 (dd, 1H). MS (ESI) m/z=301 [M+H]+.
Cc1cc(Oc2cnccn2)cc2c1[C@@H](CC(=O)O)OB2O
null
null
null
852,590
ord_dataset-faa0236be76c4501841c954527cd1b6c
null
2008-01-01T00:12:00
true
[Br:1][C:2]1[CH:3]=[C:4]([C:8]2[C:13]([CH:14]=[N:15]O)=[C:12]([CH3:17])[N:11]=[C:10]3[N:18]([CH2:21][CH3:22])[N:19]=[CH:20][C:9]=23)[CH:5]=[N:6][CH:7]=1.C(OC(=O)C)(=O)C>O>[Br:1][C:2]1[CH:3]=[C:4]([C:8]2[C:13]([C:14]#[N:15])=[C:12]([CH3:17])[N:11]=[C:10]3[N:18]([CH2:21][CH3:22])[N:19]=[CH:20][C:9]=23)[CH:5]=[N:6][CH:7]=1
CCn1ncc2c(-c3cncc(Br)c3)c(C=NO)c(C)nc21
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CC(=O)OC(C)=O
null
null
null
null
null
null
null
null
null
150
2
A mixture of 4-(5-bromo-3-pyridyl)-1-ethyl-6-methyl-1H-pyrazolo[3,4-b]pyridine-5-carbaldehyde oxime (34 mg) and acetic anhydride (1 ml) was stirred at 90° C. for 2 hours and 150° C. for 2 hours. The reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with water, brine, dried over anhydrous MgSO4 and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel eluting with a mixture of EtOAc and n-hexane (1:2). The crystalline residue was recrystallized from EtOAc and n-hexane to give 4-(5-bromo-3-pyridyl)-1-ethyl-6-methyl-1H-pyrazolo[3,4-b]pyridine-5-carbonitrile (15.5 mg) as a colorless crystal.
CCn1ncc2c(-c3cncc(Br)c3)c(C#N)c(C)nc21
null
48
null
1,358,804
ord_dataset-d932d1d683704a8bad3d064bcb197acc
null
2013-01-01T00:11:00
true
[Br:1][C:2]1[CH:3]=[C:4]([C@@H:8]([N:10]2[CH2:15][CH2:14][C@@:13]([C:20]3[CH:25]=[CH:24][C:23]([F:26])=[CH:22][CH:21]=3)([CH2:16][C:17](=[O:19])[CH3:18])[O:12][C:11]2=[O:27])[CH3:9])[CH:5]=[CH:6][CH:7]=1.[CH3:28][Mg+].[Br-]>C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:3]=[C:4]([C@@H:8]([N:10]2[CH2:15][CH2:14][C@@:13]([C:20]3[CH:21]=[CH:22][C:23]([F:26])=[CH:24][CH:25]=3)([CH2:16][C:17]([OH:19])([CH3:28])[CH3:18])[O:12][C:11]2=[O:27])[CH3:9])[CH:5]=[CH:6][CH:7]=1
CC(=O)C[C@]1(c2ccc(F)cc2)CCN([C@@H](C)c2cccc(Br)c2)C(=O)O1
C[Mg+]
null
[Br-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
null
null
null
null
null
null
null
null
null
null
25
0.25
A solution of (S)-3-((S)-1-(3-bromophenyl)ethyl)-6-(4-fluorophenyl)-6-(2-oxopropyl)-1,3-oxazinan-2-one (18.5 mg, 0.043 mmol) in dry toluene (3 mL) was cooled to 0° C. A solution of MeMgBr (3.0M in THF, 45 μL, 3 equiv) was added. After 15 min, the mixture was warmed to rt slowly and stirred 2 h. LC-MS found reaction completed. The reaction was quenched by satd aq NH4Cl solution (2 mL), diluted with EtOAc (10 mL), washed with 1% aq HCl (3 mL), brine (3 mL), and dried over Na2SO4. After filtration and concentration, the residue was purified by preparative HPLC to afford (S)-3-((S)-1-(3-bromophenyl)ethyl)-6-(4-fluorophenyl)-6-(2-hydroxy-2-methylpropyl)-1,3-oxazinan-2-one (8.0 mg, 42%). LC-MS (3 min) tR=1.75 min, m/z=472, 474 (M+Na); 1H NMR (CDCl3) 7.32-7.21 (m, 3H), 7.12-6.98 (m, 4H), 6.89 (m, 1H), 5.65 (q, 1H), 2.89 (m, 1H), 1.50 (d, 3H), 1.15 (d, 6H).
C[C@@H](c1cccc(Br)c1)N1CC[C@](CC(C)(C)O)(c2ccc(F)cc2)OC1=O
null
42
null
1,712,993
ord_dataset-3f2a531ffbae4b9eb1048afcd7953beb
null
2016-01-01T00:04:00
true
[CH3:1][C:2]([O:5][C:6]([NH:8][C@H:9]([C:13]([OH:15])=O)[CH2:10][C:11]#[CH:12])=[O:7])([CH3:4])[CH3:3].CCN=C=NCCCN(C)C.C1C=CC2N(O)N=NC=2C=1.[NH2:37][C@H:38]([C:43]([O:45][CH3:46])=[O:44])[CH2:39][CH:40]([CH3:42])[CH3:41].Cl.C(N(C(C)C)CC)(C)C>CN(C=O)C>[C:2]([O:5][C:6]([NH:8][CH:9]([CH2:10][C:11]#[CH:12])[C:13]([NH:37][CH:38]([CH2:39][CH:40]([CH3:42])[CH3:41])[C:43]([O:45][CH3:46])=[O:44])=[O:15])=[O:7])([CH3:1])([CH3:3])[CH3:4]
C#CC[C@H](NC(=O)OC(C)(C)C)C(=O)O
COC(=O)[C@@H](N)CC(C)C
null
CCN=C=NCCCN(C)C
Cl
On1nnc2ccccc21
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
CCN(C(C)C)C(C)C
null
null
null
null
null
null
null
null
null
25
8
To a solution of Boc-L-propargylglycine (26.65 g; 125 mmol) in dry DMF (170 mL) was added EDCI (29.23 g; 152.5 mmol) and HOBt (23.5 g; 122.5 mmol), and the reaction mixture was stirred at room temperature for 40 min (solution A). In a separate RB flask, (L) Leu-OMe hydrochloride (22.72 g; 125 mmol) in dry DMF (82 mL) kept at 0° C. was treated with diisopropyl ethyl amine (DIEA) (64.62 g; 500 mmol) and the solution was stirred for 25 min (solution B). Solution B was added to solution A and the reaction mixture was stirred overnight at room temperature. The solvent was removed on the rotary evaporator and the residue was taken up in dichloromethane (DCM) (600 mL) and washed sequentially with saturated sodium bicarbonate (2×200 mL), 5% HCl (2×200 mL) and brine (200 mL). The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated, leaving a crude product which was purified using flash chromatography (silica gel; hexane/ethyl acetate 75:25) to give 1 as a white solid (38.12 g; 89% yield); 1H NMR (CDCl3) δ 8.2 (s, 1H), 7.0 (s, 1H), 4.3 (m, 1H), 4.1 (m, 1H), 3.6 (s, 3H), 2.8 (s, 1H), 2.4 (m, 2H), 2.3 (m, 1H), 1.6 (m, 2H), 1.5 (m, 1H), 1.38 (s, 9H), 0.87 (d, 6H).
C#CCC(NC(=O)OC(C)(C)C)C(=O)NC(CC(C)C)C(=O)OC
null
89.6
null
432,417
ord_dataset-8cbb58558c904b2b85fa7a1b084a0de9
null
1999-01-01T00:06:00
true
[C:1]1(=[O:7])[O:6][C:4](=[O:5])[CH:3]=[CH:2]1.[CH3:8][OH:9]>>[CH3:8][O:9][C:4](=[O:5])/[CH:3]=[CH:2]\[C:1]([OH:6])=[O:7]
O=C1C=CC(=O)O1
CO
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
3
The same procedure as that of process (I) of Example 1 was conducted to obtain a 50% by weight methanol solution of (A1). In the same manner, to a 1 liter flask were added 24.00 g of maleic anhydride and 39.68 g of methanol, and the resulting mixture was stirred under reflux in a water bath kept at 90° C. Thirty minutes after initiation of the stirring, solid components disappeared, 3 hours after, the temperature was lowered to room temperature to obtain a 50% by weight methanol solution of maleic monomethyl ester.
COC(=O)/C=C\C(=O)O
null
null
null
317,703
ord_dataset-eb32c2b9cbdf4fc39ce6c9fe0fa11430
null
1995-01-01T00:10:00
true
[Cl:1][C:2]1[C:3](F)=[CH:4][CH:5]=[C:6]2[C:11]=1[N:10]([CH:12]1[CH2:14][CH2:13]1)[CH:9]=[C:8]([C:15]([OH:17])=[O:16])[C:7]2=[O:18].[CH:20]12[CH2:27][NH:26][CH2:25][CH:24]1[CH2:23][CH2:22][NH:21]2>CS(C)=O>[CH:20]12[CH2:27][N:26]([C:3]3[C:2]([Cl:1])=[C:11]4[C:6]([C:7](=[O:18])[C:8]([C:15]([OH:17])=[O:16])=[CH:9][N:10]4[CH:12]4[CH2:14][CH2:13]4)=[CH:5][CH:4]=3)[CH2:25][CH:24]1[CH2:23][CH2:22][NH:21]2
O=C(O)c1cn(C2CC2)c2c(Cl)c(F)ccc2c1=O
C1CC2CNCC2N1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CS(C)=O
null
null
null
null
null
null
null
null
null
null
null
null
650 mg (2.3 mmol) of 8-chloro-l-cyclopropyl-7-fluoro-1,4 -dihydro-4 -oxo-3 -quinolinecarboxylic acid together with 315 mg (2.8 retool) of 2,7-diazabicyclo[3.3.0]octane and 510 mg (4.6 mmol) of 1,4-diazabicyclo[2.2.21]octane are heated for six hours at 120° C. in 23 ml of dimethyl sulphoxide. All volatile components are removed under a high vacuum, and the residue is stirred thoroughly with acetonitrile and dried at approximately 100° C.
O=C(O)c1cn(C2CC2)c2c(Cl)c(N3CC4CCNC4C3)ccc2c1=O
null
null
null
583,122
ord_dataset-60f3171f0342452f8814e7f294e2be8b
null
2003-01-01T00:02:00
true
C(N(CC)CC)C.[CH3:8][O:9][C:10]1[CH:11]=[C:12]2[C:16](=[CH:17][C:18]=1[O:19][CH3:20])[C:15](=[O:21])[O:14][CH:13]2[PH2](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[N:41]1[CH:46]=[CH:45][C:44]([CH:47]=O)=[CH:43][CH:42]=1>C(Cl)Cl>[CH3:8][O:9][C:10]1[CH:11]=[C:12]2[C:16](=[CH:17][C:18]=1[O:19][CH3:20])[C:15](=[O:21])[O:14][C:13]2=[CH:47][C:44]1[CH:45]=[CH:46][N:41]=[CH:42][CH:43]=1
O=Cc1ccncc1
COc1cc2c(cc1OC)C([PH2](c1ccccc1)(c1ccccc1)c1ccccc1)OC2=O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(CC)CC
ClCCl
null
null
null
null
null
null
null
null
null
null
null
Triethylamine (20 ml, 145 mmoles) was dropwise added to a suspension of 5,6-dimethoxy-3-(triphenyl-λ6-phosphanyl)-3H-isobenzofuran-1-one (78 g, 145 mmoles), obtained as described in example 3, and 4-pyridincarboxaldehyde (13 ml, 145 mmoles) in CH2Cl2 (1 l), at room temperature under stirring. After 1.5 hours the mixture was filtered and evaporated and the residue was treated with ethanol under reflux, cooled and filtered. The mother liquors were chromatographed (eluent: 100% CH2Cl2, then with 1% CH3OH) and the residue was brought to dryness and joined to the above filtrate to give 25 g of the title compound.
COc1cc2c(cc1OC)C(=Cc1ccncc1)OC2=O
null
60.9
null
1,326,464
ord_dataset-cfad8b3f00044bcda60a96b019f09872
null
2013-01-01T00:08:00
true
Cl.[NH2:2][C@@H:3]1[C:11]2[C:6](=[C:7]([C:12]3[S:16][C:15]([C:17]4[CH:18]=[CH:19][C:20]([O:25][CH:26]([CH3:28])[CH3:27])=[C:21]([CH:24]=4)[C:22]#[N:23])=[N:14][N:13]=3)[CH:8]=[CH:9][CH:10]=2)[CH2:5][CH2:4]1.Cl[C:30]([O:32][CH3:33])=[O:31]>C(Cl)Cl>[CH3:33][O:32][C:30](=[O:31])[NH:2][C@@H:3]1[C:11]2[C:6](=[C:7]([C:12]3[S:16][C:15]([C:17]4[CH:18]=[CH:19][C:20]([O:25][CH:26]([CH3:28])[CH3:27])=[C:21]([C:22]#[N:23])[CH:24]=4)=[N:14][N:13]=3)[CH:8]=[CH:9][CH:10]=2)[CH2:5][CH2:4]1
COC(=O)Cl
CC(C)Oc1ccc(-c2nnc(-c3cccc4c3CC[C@@H]4N)s2)cc1C#N
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
25
16
Prepared using General Procedure 8. To a stirred solution of (S)-5-(5-(1-amino-2,3-dihydro-1H-inden-4-yl)-1,3,4-thiadiazol-2-yl)-2-isopropoxybenzonitrile hydrochloride 4 (15 mg, 0.03 mmol) and TEA (11 mg, 0.1 mmol) in DCM (1 mL) was added methyl chloroformate (10 mg, 0.1). The reaction mixture was stirred at room temperature for 16 h. The solvent was evaporated and water (2 mL) was added. The resulting solid was filtered, washed with water, and dried under high vacuum to afford 12 mg (92%) of (S)-methyl(4-(5-(3-cyano-4-isopropoxyphenyl)-1,3,4-thiadiazol-2-yl)-2,3-dihydro-1H-inden-1-yl)carbamate 16 as white solid. LCMS-ESI (m/z) calculated for C23H22N4O3S: 434.1; found 435.3 [M+H]+, tR=3.69 min.
COC(=O)N[C@H]1CCc2c(-c3nnc(-c4ccc(OC(C)C)c(C#N)c4)s3)cccc21
null
92.1
null
1,246,936
ord_dataset-c544c0c663f54dbea4ddb52ddde7934e
null
2013-01-01T00:01:00
true
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]([N:10]2[CH2:15][CH2:14][N:13]([C:16]3[C:21]([CH3:22])=[CH:20][C:19]([CH:23]4[CH2:25][CH2:24]4)=[CH:18][N:17]=3)[CH2:12][CH2:11]2)=[O:9])=[C:4]([CH3:26])[CH:3]=1.[O:27]=[C:28]1[NH:32][C@H:31]([CH2:33][O:34]C(=O)C2C=CC=CC=2)[CH2:30][O:29]1>>[CH:23]1([C:19]2[CH:20]=[C:21]([CH3:22])[C:16]([N:13]3[CH2:14][CH2:15][N:10]([C:8]([C:5]4[CH:6]=[CH:7][C:2]([N:32]5[C@H:31]([CH2:33][OH:34])[CH2:30][O:29][C:28]5=[O:27])=[CH:3][C:4]=4[CH3:26])=[O:9])[CH2:11][CH2:12]3)=[N:17][CH:18]=2)[CH2:25][CH2:24]1
Cc1cc(Br)ccc1C(=O)N1CCN(c2ncc(C3CC3)cc2C)CC1
O=C1N[C@H](COC(=O)c2ccccc2)CO1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
By reaction and treatment in the same manner as in Example 19 and using (4-bromo-2-methylphenyl)[4-(5-cyclopropyl-3-methylpyridin-2-yl)piperazin-1-yl]methanone (347 mg) described in Preparation Example 130 and benzoic acid (R)-2-oxooxazolidin-4-ylmethyl ester (278 mg), the title compound (270 mg) was obtained.
Cc1cc(N2C(=O)OC[C@H]2CO)ccc1C(=O)N1CCN(c2ncc(C3CC3)cc2C)CC1
null
71.6
null
1,588,360
ord_dataset-380e279f82154dba9e08ab51b3bdd08a
null
2015-01-01T00:05:00
true
C(O)(C(F)(F)F)=O.[C:8]([C:10]1[CH:15]=[CH:14][C:13]([C:16]2[CH:17]=[N:18][N:19]([C:22]3[CH:30]=[CH:29][C:25]([C:26](O)=[O:27])=[CH:24][N:23]=3)[C:20]=2[OH:21])=[C:12]([CH3:31])[CH:11]=1)#[N:9].[CH3:32][N:33]1[CH2:37][CH2:36][CH2:35][CH:34]1[CH2:38][CH2:39][NH2:40]>>[C:8]([C:10]1[CH:15]=[CH:14][C:13]([C:16]2[CH:17]=[N:18][N:19]([C:22]3[CH:30]=[CH:29][C:25]([C:26]([NH:40][CH2:39][CH2:38][CH:34]4[CH2:35][CH2:36][CH2:37][N:33]4[CH3:32])=[O:27])=[CH:24][N:23]=3)[C:20]=2[OH:21])=[C:12]([CH3:31])[CH:11]=1)#[N:9]
Cc1cc(C#N)ccc1-c1cnn(-c2ccc(C(=O)O)cn2)c1O
CN1CCCC1CCN
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O=C(O)C(F)(F)F
null
null
null
null
null
null
null
null
null
null
null
null
The title compound, as a TFA salt, was prepared in a manner similar to Example 74 using 6-(4-(4-cyano-2-methylphenyl)-5-hydroxy-1H-pyrazol-1-yl)nicotinic acid and 2-(1-methylpyrrolidin-2-yl)ethanamine 1H NMR (400 MHz, DMSO-d6) δ ppm 1.60-1.83 (m, 2H) 1.83-2.08 (m, 2 H) 2.18 (dd, J=12.88, 4.29 Hz, 1 H) 2.27-2.41 (m, 1 H) 2.44 (s, 3 H) 2.84 (d, J=3.54 Hz, 3 H) 3.08 (br. s., 1 H) 3.29 (br. s., 1 H) 3.40 (q, J=6.57 Hz, 2 H) 3.58 (d, J=4.29 Hz, 1 H) 7.67 (d, J=7.58 Hz, 1 H) 7.70-7.89 (m, 2 H) 8.20 (br. s., 1 H) 8.42 (br. s., 1H) 8.50-8.71 (m, 1 H) 8.84 (br. s., 1 H) 8.89-8.95 (m, 1 H) 9.53 (br. s., 1 H) 12.81-13.56 (m, 1 H). MS m/z [M+H]+ 431.2.
Cc1cc(C#N)ccc1-c1cnn(-c2ccc(C(=O)NCCC3CCCN3C)cn2)c1O
null
null
null
1,187,792
ord_dataset-9cd817a75dfc4fe7ad19d4232772d5ff
null
2012-01-01T00:07:00
true
[CH:1]1([CH:6]=[C:7]([C:17]2[CH:22]=[CH:21][C:20]([C:23]([OH:28])([CH2:26][CH3:27])[CH2:24][CH3:25])=[CH:19][CH:18]=2)[C:8]2[NH:16][C:11]3=[N:12][CH:13]=[CH:14][CH:15]=[C:10]3[CH:9]=2)[CH2:5][CH2:4][CH2:3][CH2:2]1>[Pd].CO>[CH:1]1([CH2:6][CH:7]([C:17]2[CH:18]=[CH:19][C:20]([C:23]([OH:28])([CH2:26][CH3:27])[CH2:24][CH3:25])=[CH:21][CH:22]=2)[C:8]2[NH:16][C:11]3=[N:12][CH:13]=[CH:14][CH:15]=[C:10]3[CH:9]=2)[CH2:5][CH2:4][CH2:3][CH2:2]1
CCC(O)(CC)c1ccc(C(=CC2CCCC2)c2cc3cccnc3[nH]2)cc1
null
null
[Pd]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
50
null
A mixture of 3-{4-[2-cyclopentyl-1-(1H-pyrrolo[2,3-b]pyridin-2-yl)-vinyl]-phenyl}-pentan-3-ol (120 mg, 0.32 mmol) and 10% palladium on activated carbon (36 mg) in methanol (250 mL) was heated at 50° C. under hydrogen (50 psi) for 16 h. The mixture was cooled to 25° C., the solids filtered off, washed with ethyl acetate and concentrated in vacuo. Purification using a Waters automated flash system (column: Xterra 30 mm×100 mm, sample manager 2767, pump 2525, detector: ZQ mass and UV 2487, solvent system: acetonitrile and 0.1% ammonium hydroxide in water) afforded 3-{4-[2-cyclopentyl-1-(1H-pyrrolo[2,3-b]pyridin-2-yl)-ethyl]-phenyl}-pentan-3-ol (68 mg, 60%): LC/MS m/e calcd for C25H32N2O [M+H]+ 377.55, observed 377.3; 1H NMR (400 MHz, CD3OD) δ ppm 8.04 (d, J=3.8 Hz, 1H), 7.87 (dd, J=7.7, 1.1 Hz, 1H), 7.25-7.34 (m, 4H), 7.02 (dd, J=7.7, 4.9 Hz, 1H), 6.31 (s, 1H), 4.15 (t, J=7.8 Hz, 1H), 2.21 (dt, J=13.7, 7.2 Hz, 1H), 2.03-2.11 (m, 1H), 1.58-1.85 (m, 9H), 1.42-1.54 (m, 2H), 1.14-1.28 (m, 2H), 0.72 (td, J=7.4, 2.1 Hz, 6H).
CCC(O)(CC)c1ccc(C(CC2CCCC2)c2cc3cccnc3[nH]2)cc1
null
56.4
null
665,003
ord_dataset-5a3d853c53674888a5691dce2e398792
null
2005-01-01T00:03:00
true
[C:1]([N:4]1[C:13]2[C:12]3=[N:14][C:15]([CH3:17])=[CH:16][N:11]3[CH:10]=[CH:9][C:8]=2[C@@H:7]([O:18][CH2:19][CH2:20][O:21][CH3:22])[C@H:6]([O:23][C:24](=[O:29])[C:25]([CH3:28])([CH3:27])[CH3:26])[C@H:5]1[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1)(=[O:3])[CH3:2].C1C(=O)N([Cl:43])C(=O)C1>C(O)C>[C:1]([N:4]1[C:13]2[C:12]3=[N:14][C:15]([CH3:17])=[C:16]([Cl:43])[N:11]3[CH:10]=[CH:9][C:8]=2[C@@H:7]([O:18][CH2:19][CH2:20][O:21][CH3:22])[C@H:6]([O:23][C:24](=[O:29])[C:25]([CH3:26])([CH3:27])[CH3:28])[C@H:5]1[C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1)(=[O:3])[CH3:2]
O=C1CCC(=O)N1Cl
COCCO[C@@H]1c2ccn3cc(C)nc3c2N(C(C)=O)[C@H](c2ccccc2)[C@H]1OC(=O)C(C)(C)C
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
null
2
To a of 0° C. cooled solution of 1.00 g (2.10 mmol) (7R,8R,9R)-10-acetyl-7-(2-methoxyethoxy)-2-methyl-9-phenyl-8-pivaloyloxy-7,8,9,10-tetrahydroimidazo[1,2-h][1,7]naphthyridine in ethanol (20 ml) is added 0.28 g (2.10 mmol) NCS and the mixture is stirred for 2 h. Afterwards the reaction is quenched by adding of saturated aqueous sodium hydrogen carbonate solution and is extracted twice with dichloromethane. The combined organic layers are washed with brine, dried over sodium sulphate and evaporated in vacuo. The crude product is purified by column chromatography (ethyl acetate/cylohexane: 1/1) to provide 0.89 g (1.73 mmol/82%) of the title compound as a colourless solid with a melting point of 167-170° C. (cyclohexane).
COCCO[C@@H]1c2ccn3c(Cl)c(C)nc3c2N(C(C)=O)[C@H](c2ccccc2)[C@H]1OC(=O)C(C)(C)C
null
null
null
1,684,757
ord_dataset-3953983e052a4076aa7cc0880b79cb8b
null
2016-01-01T00:01:00
true
[NH2:1][CH:2]([C:11]1[C:16]([O:17][CH3:18])=[CH:15][N:14]=[CH:13][C:12]=1[O:19][CH3:20])[CH2:3][CH2:4][CH2:5][CH2:6][C:7]([O:9]C)=O.[C:21]1([C:27]2[S:28][CH:29]=[C:30]([CH:32]=O)[N:31]=2)[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>>[CH3:20][O:19][C:12]1[CH:13]=[N:14][CH:15]=[C:16]([O:17][CH3:18])[C:11]=1[CH:2]1[N:1]([CH2:32][C:30]2[N:31]=[C:27]([C:21]3[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=3)[S:28][CH:29]=2)[C:7](=[O:9])[CH2:6][CH2:5][CH2:4][CH2:3]1
COC(=O)CCCCC(N)c1c(OC)cncc1OC
O=Cc1csc(-c2ccccc2)n1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Prepared according to the described general procedure 1 (GP1) by reaction of methyl 6-amino-6-(3,5-dimethoxypyridin-4-yl)hexanoate with commercially available 2-phenylthiazole-4-carbaldehyde. Subsequent purification by preparative HPLC afforded the target compound. LC-MS (conditions A): tR=0.61 min.; [M+H]+: 423.86 g/mol.
COc1cncc(OC)c1C1CCCCC(=O)N1Cc1csc(-c2ccccc2)n1
null
null
null
234,844
ord_dataset-45d20d09e4d64f45bdd419044025b4d3
null
1991-01-01T00:09:00
true
O.[OH-].[Li+].[NH2:4][CH2:5][CH2:6][CH2:7][P:8]([CH:13]([O:18][CH2:19][CH2:20][CH3:21])[O:14][CH2:15][CH2:16][CH3:17])(=[O:12])[O:9]CC>O.C(O)C>[NH2:4][CH2:5][CH2:6][CH2:7][P:8]([CH:13]([O:18][CH2:19][CH2:20][CH3:21])[O:14][CH2:15][CH2:16][CH3:17])(=[O:9])[OH:12]
CCCOC(OCCC)P(=O)(CCCN)OCC
null
null
[Li+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
O
null
null
null
null
null
null
null
null
null
25
120
To a stirred solution of 0.05 g of lithium hydroxide monohydrate in 7.7 ml of water, is added a solution of 4.37 g of ethyl 3-aminopropyl(di-n-propyloxymethyl)phosphinate in 16.2 ml of ethanol. A slight exothermic reaction ensues and the reaction mixture becomes cloudy.A further 2 ml of water are added and the clear solution stirred at room temperature for 5 days. After: this time the mixture is concentrated in vacuo at 55° and the residue redissolved in water and extracted with 3×10 ml of dichloromethane. The aqueous layer is again evaporated to dryness and the residue dissolved in 20 ml of water and treated with 0.51 ml of 85% phosphoric acid. After stirring overnight, thesolid is removed by filtration. Evaporation of the filtrate and crystallisation of the residue from ethanol/ether affords 3-aminopropyl(di-n-propyloxymethyl) phosphinic acid, m.p. 223°-225°, as a white solid.
CCCOC(OCCC)P(=O)(O)CCCN
null
null
null
1,159,820
ord_dataset-b195433d5c354ddfb6cde0d53c41910f
null
2012-01-01T00:04:00
true
C[O:2][C:3]([C@@H:5]1[CH2:9][C@@H:8]([S:10]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)(=[O:12])=[O:11])[CH2:7][N:6]1[C:19]1[N:20]([C:25]2[CH:30]=[CH:29][C:28]([C:31]([F:34])([F:33])[F:32])=[CH:27][CH:26]=2)[N:21]=[C:22]([CH3:24])[CH:23]=1)=[O:4].[OH-].[Li+]>>[C:13]1([S:10]([C@H:8]2[CH2:7][N:6]([C:19]3[N:20]([C:25]4[CH:30]=[CH:29][C:28]([C:31]([F:33])([F:34])[F:32])=[CH:27][CH:26]=4)[N:21]=[C:22]([CH3:24])[CH:23]=3)[C@H:5]([C:3]([OH:4])=[O:2])[CH2:9]2)(=[O:12])=[O:11])[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1
COC(=O)[C@@H]1C[C@@H](S(=O)(=O)c2ccccc2)CN1c1cc(C)nn1-c1ccc(C(F)(F)F)cc1
null
null
[Li+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
In analogy to the procedure described in example 253e, (2S,4R)-4-benzenesulfonyl-1-[5-methyl-2-(4-trifluoromethyl-phenyl)-2H-pyrazol-3-yl]-pyrrolidine-2-carboxylic acid methyl ester was saponified in the presence of lithium hydroxide to give the title compound as yellow solid. MS (ESI): m/z=480.1 [M+H]+.
Cc1cc(N2C[C@H](S(=O)(=O)c3ccccc3)C[C@H]2C(=O)O)n(-c2ccc(C(F)(F)F)cc2)n1
null
null
null
639,650
ord_dataset-1c0bae7388cf460091d56129e95b3145
null
2004-01-01T00:06:00
true
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][OH:9])=[C:4]([O:10][CH3:11])[CH:3]=1.CN1CCOCC1>C(Cl)Cl.[Ru]([O-])(=O)(=O)=O.C([N+](CCC)(CCC)CCC)CC>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]=[O:9])=[C:4]([O:10][CH3:11])[CH:3]=1
COc1cc(Cl)ccc1CO
null
null
O=[Ru](=O)(=O)[O-]
CCC[N+](CCC)(CCC)CCC
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN1CCOCC1
ClCCl
null
null
null
null
null
null
null
null
null
25
2.5
In methylene chloride (80 ml) was dissolved (4-chloro-2-methoxyphenyl)methanol (3.69 g). Under ice cooling, molecular sieve 4A (4.57 g), N-methylmorpholine (2.81 g) and tetra-n-propylammonium perruthenate (420 mg) were added to the resulting solution, followed by stirring at room temperature for 2.5 hours. The reaction mixture was distilled under reduced pressure. The residue was subjected to chromatography on a silica gel column (hexane:ethyl acetate=9:1), whereby the title compound (3.07 g) was obtained as pale yellow oil.
COc1cc(Cl)ccc1C=O
null
null
null
331,375
ord_dataset-1558660634294cc8ad7e01746e9083fd
null
1996-01-01T00:06:00
true
[CH3:1][O:2][C:3]1[C:4]([N+:20]([O-])=O)=[C:5]([C:9]2[O:10][C:11]3[CH:19]=[CH:18][CH:17]=[CH:16][C:12]=3[C:13](=[O:15])[CH:14]=2)[CH:6]=[CH:7][CH:8]=1>CO.C1COCC1.[Ni]>[NH2:20][C:4]1[C:3]([O:2][CH3:1])=[CH:8][CH:7]=[CH:6][C:5]=1[C:9]1[O:10][C:11]2[CH:19]=[CH:18][CH:17]=[CH:16][C:12]=2[C:13](=[O:15])[CH:14]=1
COc1cccc(-c2cc(=O)c3ccccc3o2)c1[N+](=O)[O-]
null
null
[Ni]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
2-(3-Methoxy-2-nitrophenyl)-4-oxo-4H-[1]benzopyran (1.73 g, 5.8 mmol) in methanol (50 mL) and THF (50 mL) is hydrogenated under pressure with RaNi (0.5 g). The solution is concentrated under reduced pressure and recrystallized from toluene to yield 2-(2-amino-3-methoxyphenyl)-4-oxo-4H-[1]benzopyran (900 mg, 58%) as a solid. 1H NMR (DMSO): δ8.07 (1H, d, J=8.0 Hz), 7.83 (1H, t, J=6.9 Hz), 7.70 (1H, d, J=7.7 Hz), 7.51 (1H, t, J=7.0 Hz), 7.09 (1H, d, J=8.0 Hz), 7.00 (1H, d, J=7.0 Hz), 6.71 (1H, t, J=8.0 Hz), 6.56 (1H, s), 5.30 (2H, s), 3.85 (3H, s).
COc1cccc(-c2cc(=O)c3ccccc3o2)c1N
null
58.1
null
818,214
ord_dataset-50f99930fc41474db226bc80774b38df
null
2008-01-01T00:04:00
true
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([N:11]([CH2:13][C:14]2[S:15][CH:16]=[C:17]([C:19]([O:21]CC)=[O:20])[N:18]=2)[CH3:12])(=[O:10])=[O:9])=[CH:4][CH:3]=1.[OH-].[Li+]>O1CCOCC1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([N:11]([CH2:13][C:14]2[S:15][CH:16]=[C:17]([C:19]([OH:21])=[O:20])[N:18]=2)[CH3:12])(=[O:10])=[O:9])=[CH:4][CH:3]=1
CCOC(=O)c1csc(CN(C)S(=O)(=O)c2ccc(Br)cc2)n1
null
null
[Li+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1COCCO1
null
null
null
null
null
null
null
null
null
null
50
72
Ethyl 2-(N-(4-bromobenzenesulphonyl)-N-methylaminomethyl)thiazole-4-carboxylate (2.19, 5.2 mmol) was added to mixture of 1N lithium hydroxide solution (10 ml, 10 mmol) and dioxan (20 ml) and heated to 50° C. until a solution was obtained. The mixture was stirred at room temperature for a further 3 days. The mixture was evaporated, taken up in EtOAc and acidified with 1N potassium hydrogen sulphate solution. The phases were separated and the organic phase washed with water and brine, dried and reduced to afford 2-(N-(4-bromobenzenesulphonyl)-N-methylaminomethyl)thiazole-4-carboxylic acid (1.86 g, 95%) as a white solid.
CN(Cc1nc(C(=O)O)cs1)S(=O)(=O)c1ccc(Br)cc1
null
91.4
null
1,713,585
ord_dataset-3f2a531ffbae4b9eb1048afcd7953beb
null
2016-01-01T00:04:00
true
O[C@@:2]([CH3:54])([C:5](=[O:53])[C@@H:6]([NH:11][C:12](=[O:52])[C@@H:13]([NH:21][C:22](=[O:51])[C@@H:23]([N:28](C)[C:29](=[O:49])[C@@H:30]([NH:39][C:40](=[O:48])[CH2:41][N:42]1[CH2:47][CH2:46][O:45][CH2:44][CH2:43]1)[CH2:31][CH2:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[CH2:24][CH:25]([CH3:27])[CH3:26])[CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[CH2:7][CH:8]([CH3:10])[CH3:9])[CH2:3][I:4].[CH3:55][O:56][C:57]1[CH:71]=[CH:70][C:60]([CH2:61][O:62][C:63](=[O:69])[CH2:64][CH2:65][C:66]([OH:68])=[O:67])=[CH:59][CH:58]=1.C1CCC(N=C=NC2CCCCC2)CC1>C(Cl)Cl.CN(C1C=CN=CC=1)C>[C:66]([O:68][C@:2]([CH3:54])([CH2:3][I:4])[C:5](=[O:53])[C@H:6]([CH2:7][CH:8]([CH3:9])[CH3:10])[NH:11][C:12](=[O:52])[C@H:13]([CH2:14][C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1)[NH:21][C:22](=[O:51])[C@H:23]([CH2:24][CH:25]([CH3:27])[CH3:26])[NH:28][C:29](=[O:49])[C@H:30]([CH2:31][CH2:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[NH:39][C:40](=[O:48])[CH2:41][N:42]1[CH2:43][CH2:44][O:45][CH2:46][CH2:47]1)(=[O:67])[CH2:65][CH2:64][C:63]([O:62][CH2:61][C:60]1[CH:59]=[CH:58][C:57]([O:56][CH3:55])=[CH:71][CH:70]=1)=[O:69]
COc1ccc(COC(=O)CCC(=O)O)cc1
CC(C)C[C@H](NC(=O)[C@H](Cc1ccccc1)NC(=O)[C@H](CC(C)C)N(C)C(=O)[C@H](CCc1ccccc1)NC(=O)CN1CCOCC1)C(=O)[C@](C)(O)CI
null
C(=NC1CCCCC1)=NC1CCCCC1
CN(C)c1ccncc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
30
3
Referring to FIG. 43, to a solution of compound (S)—N—((S)-1-(((2S,4S)-2-hydroxy-1-iodo-2,6-dimethyl-3-oxoheptan-4-yl)amino)-1-oxo-3-phenylpropan-2-yl)-4-methyl-2-((S)—N-methyl-2-(2-morpholinoacetamido)-4-phenylbutanamido)pentanamide (20, 1.5 g, 1.77 mmol) in DCM (10 mL) were added 4-((4-methoxybenzyl)oxy)-4-oxobutanoic acid (2.1 g, 8.81 mmol), DCC (1.82 g, 8.82 mmol) and DMAP (1.08 g, 8.84 mmol). The reaction mixture was stirred for 3 h at 30° C. (TLC analysis showed very little of 19 was left). The mixture was diluted with DCM (100 mL) and then filtered. The filtrate was washed with saturated citric acid solution (50 mL×2) and saturated NaHCO3 solution (50 mL×3), dried over anhydrous Na2SO4 and concentrated. The residue was purified by flash column chromatography (EtOAc/DCM=1:15 to 2:1) to give product (1.7 g, 90% yield) as a yellow powder.
COc1ccc(COC(=O)CCC(=O)O[C@](C)(CI)C(=O)[C@H](CC(C)C)NC(=O)[C@H](Cc2ccccc2)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CCc2ccccc2)NC(=O)CN2CCOCC2)cc1
null
89.9
null
81,375
ord_dataset-f196f0a87dd74fcd82ca019f8ff5cf9c
null
1981-01-01T00:05:00
true
[OH:1][C:2]1[CH:3]=[CH:4][C:5]([N+:10]([O-:12])=[O:11])=[C:6]([CH:9]=1)[CH:7]=[O:8].[C:13](OC(=O)C)(=[O:15])[CH3:14]>O>[C:13]([O:1][C:2]1[CH:3]=[CH:4][C:5]([N+:10]([O-:12])=[O:11])=[C:6]([CH:9]=1)[CH2:7][OH:8])(=[O:15])[CH3:14]
O=Cc1cc(O)ccc1[N+](=O)[O-]
CC(=O)OC(C)=O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
null
null
null
null
null
null
null
null
null
null
null
null
A mixture of 5-hydroxy-2-nitrobenzaldehyde (4 g.) and acetic anhydride (10 ml.) was heated on a steam bath for 1 hour, then poured into water (100 ml.) and extracted with diethyl ether (3×50 ml.). The extracts were combined and dried, and the solvent was evaporated. The residue of 5-acetoxy-2-nitrobenzaldehyde was dissolved in absolute ethanol (100 ml.), and stirred and ice-cooled while sodium borohydride (1.5 g.) was added in portions. The reaction mixture was stirred at room temperature for 1 hour, then water (100 ml.) was added, and the mixture was extracted with ether (3×70 ml.). The extracts were combined and dried, and the solvent was evaporated to give 5-acetoxy-2-nitrobenzyl alcohol, which was hydrogenated by the general process described in the latter part of Example 13(a) to give the required starting material.
CC(=O)Oc1ccc([N+](=O)[O-])c(CO)c1
null
null
null
992,866
ord_dataset-b6d8835b0c934476a36e6149e7597487
null
2010-01-01T00:09:00
true
[Br:1][C:2]1[NH:3][C:4]2[C:9]([C:10]=1[CH:11]1[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]1)=[CH:8][CH:7]=[C:6]([C:17]([O:19][CH3:20])=[O:18])[CH:5]=2.[H-].[Na+].[CH3:23][O:24][CH:25]([O:28][CH3:29])[CH2:26]Br>CN(C=O)C>[Br:1][C:2]1[N:3]([CH2:26][CH:25]([O:28][CH3:29])[O:24][CH3:23])[C:4]2[C:9]([C:10]=1[CH:11]1[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]1)=[CH:8][CH:7]=[C:6]([C:17]([O:19][CH3:20])=[O:18])[CH:5]=2
COC(=O)c1ccc2c(C3CCCCC3)c(Br)[nH]c2c1
COC(CBr)OC
null
[H-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
80
1
To a stirred solution of methyl 2-bromo-3-cyclohexyl-1H-indole-6-carboxylate (prepared as described in published International patent application WO2004/087714) (0.2 M, 1 eq.) in DMF at RT was added NaH (60% dispersion in mineral oil, 1.75 eq). After 1 h, KI (8 mol %) and bromoacetaldehyde dimethyl acetal (2.5 eq) were added and the reaction heated at 80° C. for 17 h. After cooling to RT, the reaction was quenched by addition of aqueous HCl (1N) and extracted into EtOAc (×3). The combined organics were washed with HCl (1N), H2O and brine before being dried (Na2SO4), filtered and concentrated in vacuo. Purification by flash column chromatography (Biotage, 5-10% EtOAc/PE gradient) gave the title compound as a white solid (79%); MS (ES+) m/z 446 (M+H)+, 448 (M+H)+.
COC(=O)c1ccc2c(C3CCCCC3)c(Br)n(CC(OC)OC)c2c1
null
79
null
1,362,738
ord_dataset-d932d1d683704a8bad3d064bcb197acc
null
2013-01-01T00:11:00
true
[C:1]([C:4]1[CH:11]=[CH:10][C:7]([C:8]#[N:9])=[CH:6][CH:5]=1)(=[O:3])[CH3:2].[CH2:12]([Mg]Cl)[C:13]([CH3:16])([CH3:15])[CH3:14].C(OCC)C>C(OCC)C.C1COCC1>[OH:3][C:1]([C:4]1[CH:11]=[CH:10][C:7]([C:8]#[N:9])=[CH:6][CH:5]=1)([CH3:2])[CH2:12][C:13]([CH3:16])([CH3:15])[CH3:14]
CC(=O)c1ccc(C#N)cc1
CC(C)(C)C[Mg]Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOCC
C1CCOC1
null
null
null
null
null
null
null
null
null
0
8
Dissolve 4-acetylbenzonitrile (1 g, 6.88 mmol) in diethyl ether/THF (1:1, 60 mL) and cool the solution to 0° C. Add 1 M neopentylmagnesium chloride in diethyl ether (8.3 mL, 8.3 mmol) under nitrogen and stir the mixture at room temperature overnight. Add saturated aqueous NH4Cl and extract the mixture twice with EtOAc. Dry the combined organic extracts over MgSO4, filter and concentrate in vacuo. Purify the crude mixture by chromatography on silica gel eluting with hexane and hexane/EtOAc (19:1, 9:1) to give the desired intermediate (364 mg, 24%).
CC(C)(C)CC(C)(O)c1ccc(C#N)cc1
null
24
null
157,121
ord_dataset-58ec6779628e43e2b3f0972725f262e6
null
1987-01-01T00:05:00
true
[CH2:1]([N:8]1[C:13](=[O:14])[C:12](=[C:15]2[S:19][CH:18]=[CH:17][S:16]2)[C:11](=[O:20])[CH:10](C(OCC)=O)[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH-].[Na+].Cl>C(O)C>[CH2:1]([N:8]1[CH2:9][CH2:10][C:11](=[O:20])[C:12](=[C:15]2[S:16][CH:17]=[CH:18][S:19]2)[C:13]1=[O:14])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
CCOC(=O)C1CN(Cc2ccccc2)C(=O)C(=C2SC=CS2)C1=O
null
null
Cl
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
null
null
Ethyl 1-benzyl-5-(1,3-dithiol-2-ylidene)-4,6-dioxopiperidine-3-carboxylate (2.0 g) is dissolved in ethanol (160 ml), and a 10% aqueous sodium hydroxide solution (8.0 ml) is added thereto. The mixture is refluxed for 2 hours. The mixture is cooled, neutralized with 10% hydrochloric acid, and then evaporated under reduced pressure to remove the solvent. The residue is dissolved in ethyl acetate, and the solution is washed with water, dried and then evaporated to remove the solvent. The residue thus obtained is recrystallized from isopropanol, whereby 1-benzyl-3-(1,3-dithiol-2-ylidene)-2,4-dioxopiperidine (1.26 g) is obtained as pale yellow needles. Yield: 78%.
O=C1CCN(Cc2ccccc2)C(=O)C1=C1SC=CS1
null
78
null
1,473,097
ord_dataset-fd1fa959d6264608b0b7fcda16741bfd
null
2014-01-01T00:08:00
true
Cl.[NH2:2][C@@H:3]1[CH2:8][CH2:7][C@H:6]([NH:9][C:10]([C:12]2[C:16]3=[N:17][CH:18]=[CH:19][C:20]([C:21]4[CH:26]=[CH:25][C:24]([O:27][CH3:28])=[CH:23][C:22]=4[O:29][CH2:30][CH:31]4[CH2:33][CH2:32]4)=[C:15]3[NH:14][C:13]=2[CH3:34])=[O:11])[CH2:5][CH2:4]1.C([O:38][C@@H:39]([CH3:43])[C:40](Cl)=[O:41])(=O)C>>[CH:31]1([CH2:30][O:29][C:22]2[CH:23]=[C:24]([O:27][CH3:28])[CH:25]=[CH:26][C:21]=2[C:20]2[CH:19]=[CH:18][N:17]=[C:16]3[C:12]([C:10]([NH:9][C@H:6]4[CH2:7][CH2:8][C@@H:3]([NH:2][C:40](=[O:41])[C@@H:39]([OH:38])[CH3:43])[CH2:4][CH2:5]4)=[O:11])=[C:13]([CH3:34])[NH:14][C:15]=23)[CH2:32][CH2:33]1
CC(=O)O[C@@H](C)C(=O)Cl
COc1ccc(-c2ccnc3c(C(=O)N[C@H]4CC[C@@H](N)CC4)c(C)[nH]c23)c(OCC2CC2)c1
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Starting from N-(cis-4-aminocyclohexyl)-7-[2-(cyclopropylmethoxy)-4-methoxyphenyl]-2-methyl-1H-pyrrolo[3,2-b]pyridine-3-carboxamide hydrochloride (example D.f13) and commercially available (2S)-1-chloro-1-oxopropan-2-yl acetate the title compound is obtained as colorless solid.
COc1ccc(-c2ccnc3c(C(=O)N[C@H]4CC[C@@H](NC(=O)[C@H](C)O)CC4)c(C)[nH]c23)c(OCC2CC2)c1
null
null
null
275,975
ord_dataset-02ee2261663048188cf6d85d2cc96e3f
null
1993-01-01T00:09:00
true
[CH3:1][C:2]([Si:5]([CH3:23])([CH3:22])[O:6][CH2:7][C@H:8]1[C@H:12]([CH2:13][O:14][Si:15]([C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:17])[CH3:16])[C:9]21[O:11][CH2:10]2)([CH3:4])[CH3:3].[I-].[Li+]>C(Cl)Cl>[CH3:4][C:2]([Si:5]([CH3:22])([CH3:23])[O:6][CH2:7][C@H:8]1[C@H:12]([CH2:13][O:14][Si:15]([C:18]([CH3:20])([CH3:19])[CH3:21])([CH3:16])[CH3:17])[CH2:10][C:9]1=[O:11])([CH3:3])[CH3:1]
CC(C)(C)[Si](C)(C)OC[C@H]1[C@H](CO[Si](C)(C)C(C)(C)C)C12CO2
null
null
[I-]
[Li+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
0
1
A solution of 12.752 g (35.6 mmol) of [4R,5R]-4,5-bis(((1,1-dimethylethyl)-dimethylsilyl)oxymethyl)-1-oxaspiro[2,2]pentane, from Step D, in 50 mL of methylene chloride was added to a solution of 3.814 g (28.5 mmol) of lithium iodide in 200 mL of methylene chloride which had been cooled in an ice bath. After stirring the reaction mixture for 1 h at 0° C., the ice bath was removed and the reaction mixture was stirred for 20 minutes at ambient temperature. The reaction mixture was then washed with 5% aqueous sodium bicarbonate solution, 5% sodium bisulfite solution and brine, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure to give 12.317 g (96.6% crude yield) of the title compound which was taken on to the next step without purifiaction; MS DCI-NH3M/Z: 376 (M+NH4)+.
CC(C)(C)[Si](C)(C)OC[C@@H]1CC(=O)[C@H]1CO[Si](C)(C)C(C)(C)C
null
null
null
528,577
ord_dataset-f027aa93238e424fbbf9bad1c7699adc
null
2001-01-01T00:12:00
true
[CH3:1][C:2]1[O:6][C:5]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)=[N:4][C:3]=1[CH2:13][CH2:14][C:15]([C:17]1[CH:22]=[CH:21][C:20]([Br:23])=[CH:19][CH:18]=1)=[O:16].[BH4-].[Na+]>C1COCC1.C(O)C>[CH3:1][C:2]1[O:6][C:5]([C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=2)=[N:4][C:3]=1[CH2:13][CH2:14][CH:15]([C:17]1[CH:22]=[CH:21][C:20]([Br:23])=[CH:19][CH:18]=1)[OH:16]
Cc1oc(-c2ccccc2)nc1CCC(=O)c1ccc(Br)cc1
null
null
[BH4-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
CCO
null
null
null
null
null
null
null
null
null
0
3
The title compound of Example 2 (5.0 g, 13 mmol) was dissolved in THF (75 mL) and added dropwise over 20 minutes to a suspension of sodium borohydride (513 mg, 13 mmol) in 75 mL of ethanol at 0° C. and the reaction mixture was stirred for 3 hours at 0° C. The reaction mixture was poured onto ice-water (500 mL) and extracted twice with diethyl ether (700 mL). The organic extracts were combined and washed with water (250 mL), brine (250 mL) and dried (MgSO4). The solvent was removed in vacuo and the residue was recrystallized from hexane to afford 4.4 g (92%) of the racemic title compound. mp 82-83° C. 1HNMR (60 MHz, CDCl3): δ2.0 (m, 2H), 2.2 (s, 3H), 2.5 (t, J=6 Hz, 2H), 4.6 (m, 1H), 4.7 (broad s, 1H, hydroxyl proton), 7.1-7.5 (m, 7H), 7.8-8.0 (m, 2H).
Cc1oc(-c2ccccc2)nc1CCC(O)c1ccc(Br)cc1
null
90.9
null
1,101,975
ord_dataset-af85e6f81c2d49f08086afd6d9e6959c
null
2011-01-01T00:10:00
true
[NH2:1][C:2]1[CH:3]=[C:4]([CH:19]=[CH:20][CH:21]=1)[O:5][C:6]1[CH:7]=[CH:8][C:9]2[N:10]([CH:12]=[C:13]([C:15]([NH:17][CH3:18])=[O:16])[N:14]=2)[N:11]=1.[CH3:22][N:23]1[C:27]([C:28](Cl)=[O:29])=[CH:26][C:25]([CH3:31])=[N:24]1.O>CN(C)C(=O)C>[CH3:22][N:23]1[C:27]([C:28]([NH:1][C:2]2[CH:3]=[C:4]([CH:19]=[CH:20][CH:21]=2)[O:5][C:6]2[CH:7]=[CH:8][C:9]3[N:10]([CH:12]=[C:13]([C:15]([NH:17][CH3:18])=[O:16])[N:14]=3)[N:11]=2)=[O:29])=[CH:26][C:25]([CH3:31])=[N:24]1
CNC(=O)c1cn2nc(Oc3cccc(N)c3)ccc2n1
Cc1cc(C(=O)Cl)n(C)n1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(=O)N(C)C
O
null
null
null
null
null
null
null
null
null
25
1
To a solution of 6-(3-aminophenoxy)-N-methylimidazo[1,2-b]pyridazine-2-carboxamide (250 mg, 0.88 mmol) in N,N-dimethylacetamide (2.5 mL) was added 1,3-dimethyl-1H-pyrazole-5-carbonyl chloride (253 mg, 1.59 mmol). After stirring at room temperature for 1 hr, water was added to the reaction mixture, and the precipitate was collected by filtration. The obtained residue was washed with water, acetonitrile and diethyl ether to give the title compound (262 mg, 73%) as a white powder.
CNC(=O)c1cn2nc(Oc3cccc(NC(=O)c4cc(C)nn4C)c3)ccc2n1
null
73.4
null
1,288,375
ord_dataset-d5c54236ecd94d61aaa071461bcfc426
null
2013-01-01T00:04:00
true
[OH-].[K+].[N:3]1[CH:8]=[CH:7][C:6]([CH:9]=[O:10])=[CH:5][CH:4]=1.[N+:11]([CH2:13][C:14]([N:16]1[CH2:21][CH2:20][N:19]([CH3:22])[CH2:18][CH2:17]1)=[O:15])#[C-:12]>CO>[N:3]1[CH:8]=[CH:7][C:6]([C@@H:9]2[O:10][CH:12]=[N:11][C@H:13]2[C:14]([N:16]2[CH2:17][CH2:18][N:19]([CH3:22])[CH2:20][CH2:21]2)=[O:15])=[CH:5][CH:4]=1
O=Cc1ccncc1
[C-]#[N+]CC(=O)N1CCN(C)CC1
null
[K+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
null
null
To a stirred and cooled (0° C.) solution of KOH (0.335 g, 5.98 mmol) in 7 mL MeOH were added successively pyridine-4-carbaldehyde (0.705 g, 6.58 mmol) and 2-isocyano-1-(4-methyl-piperazin-1-yl)-ethanone VIB 01128 (1.00 g, 6.58 mmol). The mixture was stirred at 0° C. until precipitation and concentrated. The mixture was partitioned between EtOAc (20 mL) and H2O (10 mL). The aqueous layer was extracted twice with EtOAc (60 mL). The EtOAc fractions were combined, washed twice with brine (2×10 mL), dried over MgSO4 and filtered. After evaporation and drying trans-(4,5-dihydro-5-(pyridin-4-yl)oxazol-4-yl)(4-methylpiperazin-1-yl)methanone VIB 01130 was obtained (1.282 g, 78% yield) as a yellow oil.
CN1CCN(C(=O)[C@@H]2N=CO[C@H]2c2ccncc2)CC1
null
78
null
537,584
ord_dataset-1884c7bf3d544afdb8d17b5d41b90a27
null
2002-01-01T00:03:00
true
[NH2:1][C:2]1[C:10]([N+:11]([O-])=O)=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].[H][H]>CO.[Pd]>[NH2:1][C:2]1[C:10]([NH2:11])=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5]
Nc1c(C(=O)O)cccc1[N+](=O)[O-]
[H][H]
null
[Pd]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
null
4
14 g (76.9 mmol) of 2-amino-3-nitrobenzoic acid (1b) were dissolved in 500 ml of methanol, treated with Pd/C, and hydrogenated with hydrogen. After 4 h, the catalyst was filtered off with suction and concentrated. A dark-brown solid was obtained. Yield: 11.67 g (99%).
Nc1cccc(C(=O)O)c1N
null
null
null
1,209,087
ord_dataset-fb72428f30234761b4216139dc228d0c
null
2012-01-01T00:09:00
true
Br[C:2]1[CH:3]=[N:4][N:5]([CH3:18])[C:6]=1[C:7]1[CH:8]=[C:9]([C:14]([O:16][CH3:17])=[O:15])[S:10][C:11]=1[CH2:12][CH3:13].C(=O)([O-])[O-].[K+].[K+].O1CCO[CH2:27][CH2:26]1>O.CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[CH:26]([C:2]1[CH:3]=[N:4][N:5]([CH3:18])[C:6]=1[C:7]1[CH:8]=[C:9]([C:14]([O:16][CH3:17])=[O:15])[S:10][C:11]=1[CH2:12][CH3:13])=[CH2:27]
CCc1sc(C(=O)OC)cc1-c1c(Br)cnn1C
C1COCCO1
null
CC(C)(C)[P]([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)(C(C)(C)C)C(C)(C)C
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
null
null
null
null
null
null
null
null
null
null
null
null
A solution of methyl 4-(4-bromo-1-methyl-1H-pyrazol-5-yl)-5-ethyl-2-thiophenecarboxylate (300 mg, 0.91 mmol), potassium carbonate (630 mg, 4.56 mmol), bis(tri-t-butylphosphine)palladium(0) (23 mg, 0.05 mmol) and 2,4,6-trivinylcycloboroxane-pyridine complex (110 mg, 0.46 mmol) in 1,4-dioxane (5 ml) and water (1 ml) was stirred at 80° C. in a sealed tube for 2 h. The reaction contents were partitioned between H2O-DCM and the aqueous phase was washed several times with DCM. The combined organic fractions were dried over Na2SO4, concentrated and purified via column chromatography (10-50% EtOAc in hexanes) affording methyl 4-(4-ethenyl-1-methyl-1H-pyrazol-5-yl)-5-ethyl-2-thiophenecarboxylate (187 mg, 0.66 mmol, 73% yield) as a clear oil: LCMS (ES) m/z=277 (M+H)+.
C=Cc1cnn(C)c1-c1cc(C(=O)OC)sc1CC
null
73
null
1,302,638
ord_dataset-78c3f723155a4347a902b53bcee1524d
null
2013-01-01T00:06:00
true
Cl[CH2:2][C:3]1[N:4]=[C:5]([NH:18][C:19](=[O:28])[C:20]2[C:25]([F:26])=[CH:24][CH:23]=[CH:22][C:21]=2[F:27])[S:6][C:7]=1[C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([C:14]([F:17])([F:16])[F:15])[CH:9]=1.[NH:29]([CH3:31])[CH3:30].CCN(CC)CC>C1COCC1>[CH3:30][N:29]([CH2:2][C:3]1[N:4]=[C:5]([NH:18][C:19](=[O:28])[C:20]2[C:25]([F:26])=[CH:24][CH:23]=[CH:22][C:21]=2[F:27])[S:6][C:7]=1[C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([C:14]([F:17])([F:16])[F:15])[CH:9]=1)[CH3:31]
CNC
O=C(Nc1nc(CCl)c(-c2cccc(C(F)(F)F)c2)s1)c1c(F)cccc1F
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(CC)CC
C1CCOC1
null
null
null
null
null
null
null
null
null
25
1
Into a solution of Compound 70 (50 mg, 0.12 mmol) in 5 mL of THF was added NH(Me)2 (40% solution in water, 0.1 mL) and NEt3 (0.1 ml) at room temperature. The solution was stirred at room temperature for 1 hour. The solution was washed with 5 mL of water and dried (Na2SO4), filtered and concentrated. The residue was purified on silica (eluted with 5-100% ethyl acetate in hexane) to give Compound 71 (44 mg, 84%) as a white solid.
CN(C)Cc1nc(NC(=O)c2c(F)cccc2F)sc1-c1cccc(C(F)(F)F)c1
null
84
null
303,877
ord_dataset-bfcf5a01f1a04ec585ba3f28cb93c8c9
null
1995-01-01T00:01:00
true
Cl.[CH2:2]([CH:10]1[CH2:18][C:17]2[C:12](=[CH:13][CH:14]=[C:15]([C:19](=[NH:21])[NH2:20])[CH:16]=2)[CH2:11]1)[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH3:9].C[O-].[Na+]>CO>[CH2:2]([CH:10]1[CH2:18][C:17]2[C:12](=[CH:13][CH:14]=[C:15]([C:19]3[N:20]=[CH:13][C:12]([CH2:11][CH2:10][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH3:9])=[CH:17][N:21]=3)[CH:16]=2)[CH2:11]1)[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH3:9]
CCCCCCCCC1Cc2ccc(C(=N)N)cc2C1
null
null
C[O-]
Cl
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
null
48
1.00 g (3.24 mM) of 2-octyl-5-amidinoindan hydrochloride, 0.40 g (7.40 mM) of sodium methylate, 0.82 g (3.43 mM) of α-octyloxy-β-dimethylaminoacrolein and 15 ml of methanol were placed in a 30 ml-round bottomed flask, followed by refluxing for 10.5 hours under stirring. After the reaction, the reaction mixture was left standing in a refrigerator for 2 days to precipitate a crystal. The crystal was recovered by filtration and dissolved in toluene, followed by drying with anhydrous sodium sulfate and filtration. The filtrate was evaporated to obtain a residue. The residue was purified by silica gel column chromatography (eluent: toluene/ethyl acetate=100/1) and recrystallized from a mixture solvent (toluene/methanol) to obtain 0.79 g of 2-octyl-5-(5-decylpyrimidine-2-yl)indan (Yield: 54.4%). ##STR151##
CCCCCCCCCCc1cnc(-c2ccc3c(c2)CC(CCCCCCCC)C3)nc1
null
108.8
null
137,638
ord_dataset-3fa0a6b7d51b4fc6a5380aa0d03ac884
null
1985-01-01T00:12:00
true
[NH:1]([C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=1[CH2:11][C:12]([OH:14])=O)[C:2]([NH2:4])=[O:3].FC(F)(F)C(OC(=O)C(F)(F)F)=O>FC(F)(F)C(O)=O>[N:1]1([C:2]([NH2:4])=[O:3])[C:5]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH2:11][C:12]1=[O:14]
NC(=O)Nc1ccccc1CC(=O)O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O=C(O)C(F)(F)F
O=C(OC(=O)C(F)(F)F)C(F)(F)F
null
null
null
null
null
null
null
null
null
null
null
To a solution of 194 mg (1.0 mmole) of 2-(2-ureidophenyl)acetic acid in 4 ml of trifluoroacetic acid was added 630 mg (3.0 mmole) of trifluoroacetic anhydride, and the mixture was then heated under reflux for ca. 1 hour. The reaction mixture was cooled and the solvent was removed by evaporation in vacuo. The residue was triturated under 5-8 ml of saturated sodium bicarbonate solution, and the material which remained out of solution was collected by filtration. The solid thus obtained was recrystallized from ethanol to give 61 mg of the title compound as colorless needles, m.p. 179°-180° C. (slight decomposition).
NC(=O)N1C(=O)Cc2ccccc21
null
34.6
null
1,400,742
ord_dataset-12dc3bd21bcf44d09e5b4249afe15161
null
2014-01-01T00:02:00
true
[C:1]([NH:5][C:6]([C:8]1[C:16]2[C:11](=[N:12][CH:13]=[C:14]([C:17]3[C:25]4[C:20](=[CH:21][C:22]([F:26])=[CH:23][CH:24]=4)[N:19]([CH2:27][CH:28]4[CH2:31][N:30](C(OC(C)(C)C)=O)[CH2:29]4)[N:18]=3)[N:15]=2)[N:10](COCC[Si](C)(C)C)[CH:9]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[F:47][C:48]([F:53])([F:52])[C:49]([OH:51])=[O:50]>ClCCl>[F:47][C:48]([F:53])([F:52])[C:49]([OH:51])=[O:50].[C:1]([NH:5][C:6]([C:8]1[C:16]2[C:11](=[N:12][CH:13]=[C:14]([C:17]3[C:25]4[C:20](=[CH:21][C:22]([F:26])=[CH:23][CH:24]=4)[N:19]([CH2:27][CH:28]4[CH2:29][NH:30][CH2:31]4)[N:18]=3)[N:15]=2)[NH:10][CH:9]=1)=[O:7])([CH3:4])([CH3:2])[CH3:3]
CC(C)(C)NC(=O)c1cn(COCC[Si](C)(C)C)c2ncc(-c3nn(CC4CN(C(=O)OC(C)(C)C)C4)c4cc(F)ccc34)nc12
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O=C(O)C(F)(F)F
ClCCl
null
null
null
null
null
null
null
null
null
null
null
To a stirred solution of tert-butyl 3-((3-(7-(tert-butylcarbamoyl)-5-((2-(trimethylsilyl)ethoxy)methyl)-5H-pyrrolo[2,3-b]pyrazin-2-yl)-6-fluoro-1H-indazol-1-yl)methyl)azetidine-1-carboxylate (70 mg, 107 μmol) in dichloromethane (5 mL) was added trifluoroacetic acid (1 mL). After 15 h the mixture was concentrated in vacuo and the residue dissolved in 25 mL of a Jan. 10, 1960 mixture of ammonium hydroxide/methanol/dichloromethane. After 1 h the mixture was concentrated in vacuo. Purification by chromatography (silica, 24 g Analogix column, 0-6% methanol containing 10% ammonium hydroxide in dichloromethane) followed by SFC chromatography (eluent contained TFA) gave 2-(1-azetidin-3-ylmethyl-6-fluoro-1H-indazol-3-yl)-5H-pyrrolo[2,3-b]pyrazine-7-carboxylic acid tert-butyl amide trifluoroacetate (10 mg, 17%). MS (M+H)+=422; 1H NMR (DMSO-d6) δ: 9.09 (s, 1H), 8.49 (dd, J=8.9, 5.4 Hz, 1H), 8.40 (s, 1H), 7.92 (s, 1H), 7.77 (dd, J=9.8, 1.9 Hz, 1H), 7.20 (d, J=2.1 Hz, 1H), 4.77 (d, J=7.0 Hz, 2H), 3.87-4.18 (m, 4H), 1.52 (s, 9H), 1.24 (d, J=4.5 Hz, 1H).
CC(C)(C)NC(=O)c1c[nH]c2ncc(-c3nn(CC4CNC4)c4cc(F)ccc34)nc12
null
17
null
738,143
ord_dataset-76dd1b78ee414d2da0ed30700ef026f7
null
2006-01-01T00:10:00
true
[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([CH:10]([O:14][CH3:15])[C:11]([OH:13])=O)=[CH:9][C:4]=2[O:3][CH2:2]1.[NH2:16][CH2:17][C:18]1[CH:25]=[CH:24][C:21]([C:22]#[N:23])=[CH:20][CH:19]=1>>[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([CH:10]([O:14][CH3:15])[C:11]([NH:23][CH2:22][C:21]3[CH:24]=[CH:25][C:18]([C:17]#[N:16])=[CH:19][CH:20]=3)=[O:13])=[CH:9][C:4]=2[O:3][CH2:2]1
COC(C(=O)O)c1ccc2c(c1)OCO2
N#Cc1ccc(CN)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
(RS)-Benzo[1,3]dioxol-5-yl-methoxy-acetic acid was coupled with 4-aminomethyl benzonitrile according to general procedure C to give (RS)-2-benzo[1,3]dioxol-5-yl-N-(4-cyano-benzyl)-2-methoxy-acetamide. Light yellow solid.
COC(C(=O)NCc1ccc(C#N)cc1)c1ccc2c(c1)OCO2
null
null
null
362,906
ord_dataset-0b24d1f58a024ed7bc2bda95b2430c72
null
1997-01-01T00:04:00
true
[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][N:7]=[C:6]2[N:15]1[CH2:20][CH2:19][CH:18]([N:21]2[C:30](=[O:31])[C:29]3[C:24](=[CH:25][CH:26]=[C:27]([N+:32]([O-:34])=[O:33])[CH:28]=3)[NH:23][C:22]2=[O:35])[CH2:17][CH2:16]1.[CH:36]1([CH2:39]Br)[CH2:38][CH2:37]1>>[CH:36]1([CH2:39][N:23]2[C:24]3[C:29](=[CH:28][C:27]([N+:32]([O-:34])=[O:33])=[CH:26][CH:25]=3)[C:30](=[O:31])[N:21]([CH:18]3[CH2:19][CH2:20][N:15]([C:6]4[C:5]5[C:10](=[CH:11][C:12]([O:13][CH3:14])=[C:3]([O:2][CH3:1])[CH:4]=5)[N:9]=[CH:8][N:7]=4)[CH2:16][CH2:17]3)[C:22]2=[O:35])[CH2:38][CH2:37]1
COc1cc2ncnc(N3CCC(n4c(=O)[nH]c5ccc([N+](=O)[O-])cc5c4=O)CC3)c2cc1OC
BrCC1CC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The procedure similar to that described in Example 1 was repeated, except that 300 mg (0.63 mmol) of Compound 24 was used and cyclopropylmethyl bromide was used in place of methyl iodide. As a result, 89 mg (yield: 27%) of Compound 26 was obtained as pale yellow crystals.
COc1cc2ncnc(N3CCC(n4c(=O)c5cc([N+](=O)[O-])ccc5n(CC5CC5)c4=O)CC3)c2cc1OC
null
27
null
1,346,975
ord_dataset-6034127657614f02860ed057b62b882e
null
2013-01-01T00:10:00
true
CC(N=NC(C#N)(C)C)([C:4]#[N:5])C.C1C(=O)N(Br)C(=O)C1.[CH3:21][C:22]1[CH:31]=[C:30]([N+:32]([O-:34])=[O:33])[CH:29]=[CH:28][C:23]=1[C:24](OC)=[O:25]>C(Cl)(Cl)(Cl)Cl>[CH3:4][N:5]1[CH2:21][C:22]2[C:23](=[CH:28][CH:29]=[C:30]([N+:32]([O-:34])=[O:33])[CH:31]=2)[C:24]1=[O:25]
CC(C)(C#N)N=NC(C)(C)C#N
COC(=O)c1ccc([N+](=O)[O-])cc1C
null
O=C1CCC(=O)N1Br
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)(Cl)Cl
null
null
null
null
null
null
null
null
null
null
79
2
AIBN (84 mg, 0.51), NBS (1.1 gram, 6.4 mmol), and the methyl 2-methyl-4-nitrobenzoate (1 g, 5.1 mmol, as prepared in Step 1, Example 44) were suspended in CCl4 (12.8 ml), the vessel evacuated and backfilled with N2 (2×) and the mixture heated under N2 at 79° C. overnight. The solution was filtered, and concentrated in vacuum. One third of the crude material was dissolved in 2 N methylamine in methanol (18 ml), 2N methylamine in THF added (18 ml) and the solution stirred for 2 hours at RT. The volatiles were removed in vacuum and the product was purified by chromatography on SiO2 eluting with 10% acetone:DCM to give the titled compound.
CN1Cc2cc([N+](=O)[O-])ccc2C1=O
null
null
null
1,158,611
ord_dataset-b195433d5c354ddfb6cde0d53c41910f
null
2012-01-01T00:04:00
true
[NH2:1][C:2]1[CH:10]=[CH:9][CH:8]=[C:7]2[C:3]=1[CH:4]([CH2:17][C:18]([O:20]C)=O)[CH2:5][N:6]2[CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C=CC=CC=1>[O:20]=[C:18]1[CH2:17][CH:4]2[CH2:5][N:6]([CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:7]3[C:3]2=[C:2]([CH:10]=[CH:9][CH:8]=3)[NH:1]1
CCOC(=O)CN1CC(CC(=O)OC)c2c(N)cccc21
null
null
Cc1ccc(S(=O)(=O)O)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
O
null
null
null
null
null
null
null
null
null
25
null
To a solution of (±)-ethyl methyl 2,2′-(4-amino-2,3-dihydro-1H-indole-1,3-diyl)diacetate from Step D (490 mg, 1.70 mmol) in toluene (35 mL) was added p-toluenesulfonic acid monohydrate (5 mg, 0.026 mmol) and the mixture was heated at reflux for 48 h. The mixture was cooled to ambient temperature and was partitioned between saturated aqueous NaHCO3 (5 mL) and EtOAc (40 mL). The organic layer was dried over Na2SO4, filtered, and concentrated in vacuo. The crude product was purified by silica gel chromatography, eluting with a gradient of CHCl3:EtOAc—90:10 to 40:60, to give the racemic product. The enantiomers were resolved by HPLC, utilizing a Chiralpak AS column and eluting with MeOH. The first major peak to elute was ethyl (4-oxo-2a,3,4,5-tetrahydropyrrolo[4,3,2-de]quinolin-1(2H)-yl)acetate, enantiomer A, and the second major peak to elute was ethyl (4-oxo-2a,3,4,5-tetrahydropyrrolo[4,3,2-de]quinolin-1(2H)-yl)acetate, enantiomer B, the title compound. MS: m/z=261 (M+1).
CCOC(=O)CN1CC2CC(=O)Nc3cccc1c32
null
null
null
1,544,440
ord_dataset-cac8df8aff894288876df4e093c9877f
null
2015-01-01T00:02:00
true
[NH2:1][C:2]1[C:7]([N+:8]([O-])=O)=[CH:6][C:5]([OH:11])=[CH:4][C:3]=1[CH3:12]>CO.[Pd]>[NH2:8][C:7]1[CH:6]=[C:5]([OH:11])[CH:4]=[C:3]([CH3:12])[C:2]=1[NH2:1]
Cc1cc(O)cc([N+](=O)[O-])c1N
null
null
[Pd]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
null
null
6.00 g (35.7 mmol) 4-amino-3-methyl-5-nitro-phenol in 200 mL MeOH was combined with 0.600 g palladium on charcoal (Pd/C 10%) and hydrogenated for 4 h under a hydrogen atmosphere of 60 psi at 50° C. The catalyst was removed by suction filtering, the filtrate was evaporated down and the residue was dried under HV.
Cc1cc(O)cc(N)c1N
null
null
null
1,077,523
ord_dataset-afd812677c134591a99f46ce28de2524
null
2011-01-01T00:08:00
true
[Br:1][C:2]1[CH:3]=[C:4]([CH:23]2[C:32]3[C:31](=[O:33])[CH2:30][CH:29]([CH2:34][CH2:35][CH3:36])[CH2:28][C:27]=3[NH:26][C:25]([CH3:37])=[C:24]2[C:38]#[N:39])[CH:5]=[C:6]([O:20][CH2:21][CH3:22])[C:7]=1[O:8][CH2:9][C:10]1[CH:15]=[C:14]([F:16])[CH:13]=[CH:12][C:11]=1[N+:17]([O-])=O.C(O)(=O)C>C1COCC1.[Zn]>[NH2:17][C:11]1[CH:12]=[CH:13][C:14]([F:16])=[CH:15][C:10]=1[CH2:9][O:8][C:7]1[C:6]([O:20][CH2:21][CH3:22])=[CH:5][C:4]([CH:23]2[C:32]3[C:31](=[O:33])[CH2:30][CH:29]([CH2:34][CH2:35][CH3:36])[CH2:28][C:27]=3[NH:26][C:25]([CH3:37])=[C:24]2[C:38]#[N:39])=[CH:3][C:2]=1[Br:1]
CCCC1CC(=O)C2=C(C1)NC(C)=C(C#N)C2c1cc(Br)c(OCc2cc(F)ccc2[N+](=O)[O-])c(OCC)c1
null
null
[Zn]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(=O)O
C1CCOC1
null
null
null
null
null
null
null
null
null
50
null
To a solution of the product of step b (3.8 g) in THF (110 ml) were added acetic acid (3.6 ml) and zinc dust (8.2 g). The suspension was heated for 1 h at 50° C. The reaction mixture was filtered and concentrated. The residue was dissolved in ethyl acetate and washed with sat. NalCO3 and brine. The organic layer was separated, dried (Na2SO4) and concentrated. The remaining solid was stirred with a small amount of ethyl acetate to give the title compound as a pale yellow solid after filtration.
CCCC1CC(=O)C2=C(C1)NC(C)=C(C#N)C2c1cc(Br)c(OCc2cc(F)ccc2N)c(OCC)c1
null
null
null
1,676,474
ord_dataset-9cc455db05a444779921f786a45b21a6
null
2015-01-01T00:12:00
true
[CH:1]1([C:6]2[N:7]=[C:8](O)[C:9]3[S:15](=[O:17])(=[O:16])[CH2:14][CH2:13][CH2:12][C:10]=3[N:11]=2)[CH2:5][CH2:4][CH2:3][CH2:2]1.P(Cl)(Cl)[Cl:20]>ClC(Cl)C>[Cl:20][C:8]1[C:9]2[S:15](=[O:17])(=[O:16])[CH2:14][CH2:13][CH2:12][C:10]=2[N:11]=[C:6]([CH:1]2[CH2:5][CH2:4][CH2:3][CH2:2]2)[N:7]=1
O=S1(=O)CCCc2nc(C3CCCC3)nc(O)c21
ClP(Cl)Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(Cl)Cl
null
null
null
null
null
null
null
null
null
null
65
24
To mixture of 2-cyclopentyl-4-hydroxy-7,8-dihydro-6H-thiopyrano[3,2-d]pyrimidine 5,5-dioxide (0.650 g, 2.42 mmol) in dichloroethane (10 mL) was added phosphorous trichloride (1.35 mL, 14.5 mmol). The mixture was stirred at 65° C. for 24 h. The reaction was quenched into a mixture of methylene chloride and a saturated solution of NaHCO3 and extracted with methylene chloride. The organic layers were dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. The residue was purified by column chromatography (silica, hexanes/ethyl acetate) to afford the title compound (0.150 g, 22%) as a tan solid. MW=286.78. 1H NMR (CDCl3, 500 MHz) δ 3.49-3.42 (m, 2H), 3.31 (p, J=8.0 Hz, 1H), 3.11 (t, J=6.2 Hz, 2H), 2.53-2.45 (m, 2H), 2.13-2.04 (m, 2H), 1.94-1.78 (m, 4H), 1.75-1.65 (m, 2H); APCI MS m/z 287 [M+H]+.
O=S1(=O)CCCc2nc(C3CCCC3)nc(Cl)c21
null
21.6
null
989,656
ord_dataset-b6d8835b0c934476a36e6149e7597487
null
2010-01-01T00:09:00
true
CI.[C:3](=O)([O-])[O-].[K+].[K+].[NH2:9][C:10]1[C:15]([OH:16])=[CH:14][CH:13]=[CH:12][C:11]=1[C:17](=[O:19])[CH3:18]>CN(C=O)C>[NH2:9][C:10]1[C:15]([O:16][CH3:3])=[CH:14][CH:13]=[CH:12][C:11]=1[C:17](=[O:19])[CH3:18]
O=C([O-])[O-]
CC(=O)c1cccc(O)c1N
null
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CI
CN(C)C=O
null
null
null
null
null
null
null
null
null
25
1
Under an atmosphere of nitrogen, methyl iodide (1.35 g, 10 mmol) and potassium carbonate (4.39 g, 320 mmol) were added to a solution of 2′-amino-3′-hydroxyacetophenone (960 mg, 6 mmol, TCI Europe) in DMF (6 ml). The reaction mixture was stirred for 1 h at r.t., during which time the color of the mixture changed from light brown to dark green. The mixture was then worked up by extraction with H2O/ethyl acetate, drying of the organic phase (Na2SO4), and evaporation of solvent. The title compound (960 mg, 92%) was isolated from the residue by column chromatography (silica gel, heptan/ethyl acetate=100/0-70/30).
COc1cccc(C(C)=O)c1N
null
96.9
null
1,560,074
ord_dataset-4e54080057a44c3887653391e24c90b6
null
2015-01-01T00:03:00
true
CN([CH:4]=[C:5]1[C:10](=O)[C:9]([O:12][CH2:13][CH3:14])=[CH:8][CH2:7][CH2:6]1)C.[CH2:15]([S:22][C:23](=[NH:25])[NH2:24])[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>CN(C)C=O>[CH2:15]([S:22][C:23]1[N:24]=[CH:4][C:5]2[CH2:6][CH2:7][CH:8]=[C:9]([O:12][CH2:13][CH3:14])[C:10]=2[N:25]=1)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1
N=C(N)SCc1ccccc1
CCOC1=CCCC(=CN(C)C)C1=O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
95
4
To a solution of 2.0 g (0.01 mol) of 6-[(dimethylamino)methylene]-2-ethoxycyclohex-2-en-1-one in 20 mL of dimethylformamide 2.6 g of S-benzylisothiourea (2 eq. mol.) were added. The reaction mixture was stirred at 95° C. for 4 hours. The solvent was then evaporated under reduced pressure and the crude purified by chromatography on a silica gel column (eluant dichloromethane/methanol 9/1) leading 1.5 g (50% yield) of the title compound.
CCOC1=CCCc2cnc(SCc3ccccc3)nc21
null
50
null
1,129,320
ord_dataset-285df12e34cd46e993e3c8ebc3a8962a
null
2012-01-01T00:01:00
true
[CH3:1][CH:2]([CH3:16])[CH2:3][NH:4][C:5]([C:7]1[CH:12]=[CH:11][C:10](B(O)O)=[CH:9][CH:8]=1)=[O:6].Br[C:18]1[CH:23]=[CH:22][C:21]([O:24][CH2:25][CH:26]2[CH2:31][CH2:30][N:29]([C:32]([O:34][CH:35]([CH3:37])[CH3:36])=[O:33])[CH2:28][CH2:27]2)=[CH:20][CH:19]=1>>[CH3:1][CH:2]([CH3:16])[CH2:3][NH:4][C:5]([C:7]1[CH:12]=[CH:11][C:10]([C:18]2[CH:19]=[CH:20][C:21]([O:24][CH2:25][CH:26]3[CH2:27][CH2:28][N:29]([C:32]([O:34][CH:35]([CH3:37])[CH3:36])=[O:33])[CH2:30][CH2:31]3)=[CH:22][CH:23]=2)=[CH:9][CH:8]=1)=[O:6]
CC(C)CNC(=O)c1ccc(B(O)O)cc1
CC(C)OC(=O)N1CCC(COc2ccc(Br)cc2)CC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound (21 mg, 19%) was prepared from (4-{[(2-methylpropyl)amino]carbonyl}phenyl)boronic acid (44 mg, 0.2 mmol) and 1-methylethyl 4-{[(4-bromophenyl)oxy]methyl}-1-piperidinecarboxylate (prepared as in Example 9, Step 2, 71 mg, 0.2 mmol) in a manner similar to Example 21, Step 3 and worked up in a manner similar to Example 9, Step 3. 1H NMR (400 MHz, CDCl3): δ 7.80 (d, 2H, J=8.6 Hz), 7.60 (d, 2H, J=8.6 Hz), 7.54 (d, 2H, J=8.8 Hz), 6.96 (d, 2H, J=8.9 Hz), 6.17 (t, 1H, J=5.8 Hz), 4.97-4.84 (m, 1H), 4.21 (bs, 2H), 3.85 (d, 2H, J=6.4 Hz), 3.34-3.27 (m, 2H), 2.83-2.73 (m, 2H), 2.05-1.95 (m, 1H), 1.95-1.89 (m, 1H), 1.90-1.80 (m, 2H), 1.35-1.26 (m, 2H), 1.24 (d, 6H, J=6.2 Hz), 0.99 (d, 6H, J=6.7 Hz); LRMS (ESI), m/z 453 (M+H).
CC(C)CNC(=O)c1ccc(-c2ccc(OCC3CCN(C(=O)OC(C)C)CC3)cc2)cc1
null
23.2
null
1,009,194
ord_dataset-7448b89163bf426c9d9777809ce24cec
null
2010-01-01T00:11:00
true
[O:1]=[C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[C:4](=[O:11])[N:3]1[CH2:12][C:13]1[CH:14]=[C:15]2[C:20](=[CH:21][CH:22]=1)[N:19]=[C:18]([CH:23]=[CH:24][C:25]#[N:26])[CH:17]=[CH:16]2>C(O)C.C(Cl)(Cl)Cl.[OH-].[Pd+2].[OH-].[C]>[O:11]=[C:4]1[C:5]2[C:10](=[CH:9][CH:8]=[CH:7][CH:6]=2)[C:2](=[O:1])[N:3]1[CH2:12][C:13]1[CH:14]=[C:15]2[C:20](=[CH:21][CH:22]=1)[N:19]=[C:18]([CH2:23][CH2:24][C:25]#[N:26])[CH:17]=[CH:16]2
N#CC=Cc1ccc2cc(CN3C(=O)c4ccccc4C3=O)ccc2n1
null
null
[Pd+2]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)Cl
CCO
null
null
null
null
null
null
null
null
null
25
16
The compound (574.4 mg) obtained in Example 119-6 was dissolved in ethanol (20 ml) and chloroform (10 ml). Then, the solution was added with 20% palladium hydroxide-carbon (172.3 mg) and then stirred at room temperature for 16 hours under a hydrogen atmosphere. After the reaction, the solution was filtrated through Celite and the solvent was then distilled off under reduced pressure. The residue was purified through silica gel column chromatography (hexane/ethyl acetate), thereby obtaining the subject compound (101.9 mg) as a yellow solid.
N#CCCc1ccc2cc(CN3C(=O)c4ccccc4C3=O)ccc2n1
null
17.6
null
1,341,276
ord_dataset-08852243bba44cb28769a5833f1515fe
null
2013-01-01T00:09:00
true
Cl[C:2]1[N:7]=[CH:6][C:5]([S:8]([N:11]([CH2:18][CH:19]2[CH2:23][O:22][C:21]([CH3:25])([CH3:24])[O:20]2)[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)(=[O:10])=[O:9])=[CH:4][CH:3]=1.O.[NH2:27][NH2:28]>>[CH3:24][C:21]1([CH3:25])[O:20][CH:19]([CH2:18][N:11]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[S:8]([C:5]2[CH:6]=[N:7][C:2]([NH:27][NH2:28])=[CH:3][CH:4]=2)(=[O:10])=[O:9])[CH2:23][O:22]1
CC1(C)OCC(CN(c2ccccc2)S(=O)(=O)c2ccc(Cl)nc2)O1
NN
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
null
null
null
null
null
null
null
null
null
null
null
null
According to process 5.2, starting with 0.54 g of 6-chloro-N-[(2,2-dimethyl-1,3-dioxolan-4-yl)methyl]-N-phenylpyridine-3-sulfonamide and 30 μL of hydrazine hydrate, 0.53 g of N-[(2,2-dimethyl-1,3-dioxolan-4-yl)methyl]-6-hydrazinyl-N-phenylpyridine-3-sulfonamide is obtained in the form of a white solid.
CC1(C)OCC(CN(c2ccccc2)S(=O)(=O)c2ccc(NN)nc2)O1
null
99
null
1,569,507
ord_dataset-9741bb5fd93044078df2a45f45733054
null
2015-01-01T00:04:00
true
[CH3:1][O:2][C:3]1[CH:8]=[C:7]([CH2:9]/[CH:10]=[C:11](\[CH3:23])/[CH2:12][CH2:13]/[CH:14]=[C:15](\[CH3:22])/[CH2:16][CH2:17][CH:18]=[C:19]([CH3:21])[CH3:20])[CH:6]=[C:5]([CH3:24])[CH:4]=1.C1C=C(Cl)C=C(C(OO)=[O:33])C=1>C(Cl)Cl>[CH3:1][O:2][C:3]1[CH:8]=[C:7]([CH2:9]/[CH:10]=[C:11](\[CH3:23])/[CH2:12][CH2:13]/[CH:14]=[C:15](\[CH3:22])/[CH2:16][CH2:17][CH:18]2[O:33][C:19]2([CH3:20])[CH3:21])[CH:6]=[C:5]([CH3:24])[CH:4]=1
O=C(OO)c1cccc(Cl)c1
COc1cc(C)cc(C/C=C(\C)CC/C=C(\C)CCC=C(C)C)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
0
1
To a solution of 24 (488.2 mg, 1.5 mmol) in 12 mL of dry CH2Cl2 at 0° C. was added a solution of MCPBA (403.4 mg, 1.80 mmol in 4 mL of CH2Cl2), the reaction mixture was stirred at 0° C. for 1 hr and then quenched with saturated aqueous NaHCO3 (50 mL). Et2O (3×50 mL) was then added, and the organic layer was washed with saturated aqueous NaHCO3, water, and brine, and dried with MgSO4 and concentrated to give a crude product. The crude product was passed through a silica gel column (hexanes/EtOAc 80:1, 40:1, 20:1) to give the pure epoxide 25 (104 mg: yield 20%) as a colorless oil.
COc1cc(C)cc(C/C=C(\C)CC/C=C(\C)CCC2OC2(C)C)c1
null
20.2
null
557,788
ord_dataset-f483e698250b4da0a84f425c7bfa965a
null
2002-01-01T00:08:00
true
[H-].[Na+].[C:3]([O:7][C:8]([NH:10][C:11]1[CH:31]=[CH:30][C:14]([O:15][C:16]2[CH:17]=[CH:18][C:19]([N+:27]([O-:29])=[O:28])=[C:20]([N:22]([CH3:26])[C:23](=[O:25])[O-:24])[CH:21]=2)=[CH:13][CH:12]=1)=[O:9])([CH3:6])([CH3:5])[CH3:4].[CH2:32](Br)[CH2:33][CH2:34][CH2:35][CH2:36][CH3:37]>CN(C)C=O>[C:3]([O:7][C:8]([N:10]([CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH3:37])[C:11]1[CH:31]=[CH:30][C:14]([O:15][C:16]2[CH:17]=[CH:18][C:19]([N+:27]([O-:29])=[O:28])=[C:20]([N:22]([CH3:26])[C:23](=[O:24])[O:25][C:3]([CH3:6])([CH3:5])[CH3:4])[CH:21]=2)=[CH:13][CH:12]=1)=[O:9])([CH3:6])([CH3:4])[CH3:5]
CCCCCCBr
CN(C(=O)[O-])c1cc(Oc2ccc(NC(=O)OC(C)(C)C)cc2)ccc1[N+](=O)[O-]
null
[H-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
25
1
To a suspension of sodium hydride (55 wt. %, 1.26 g) in anhydrous N,N-dimethylformamide (100 ml) was added N-[5-(4-t-butoxycarbonylaminophenoxy)-2-nitrophenyl]-N-methylcarbamate (12.1 g). The mixture was stirred at ambient temperature for several minutes. To the mixture was added hexyl bromide (6.5 g) under ice cooling and the mixture was stirred at the same temperature for 30 minutes and then at room temperature for 1.0 hour. The reaction mixture was concentrated and the residue was partitioned between ethyl acetate and water. The ethyl acetate layer was dried over anhydrous sodium sulfate and concentrated. The residue was purified by chromatography on a silica gel column using toluene/diisopropyl ether=100/7 as the eluant to give the title compound (13.8 g).
CCCCCCN(C(=O)OC(C)(C)C)c1ccc(Oc2ccc([N+](=O)[O-])c(N(C)C(=O)OC(C)(C)C)c2)cc1
null
168.8
null
144,219
ord_dataset-1895fe091c3f47afa1ee96a41a250de4
null
1986-01-01T00:05:00
true
[CH2:1]([O:3][C:4]([C@@H:6]([NH:26][C@@H:27]1[C:33](=[O:34])[N:32]([CH2:35][C:36]([O:38][C:39]([CH3:42])([CH3:41])[CH3:40])=[O:37])[C:31]2[CH:43]=[CH:44][CH:45]=[CH:46][C:30]=2[O:29][CH2:28]1)[CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][N:15]1[C:19](=[O:20])C2=CC=CC=C2C1=O)=[O:5])[CH3:2].[OH2:47].NN>C(O)C>[C:39]([O:20][C:19]([NH:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][C@H:6]([NH:26][C@@H:27]1[C:33](=[O:34])[N:32]([CH2:35][C:36]([O:38][C:39]([CH3:41])([CH3:42])[CH3:40])=[O:37])[C:31]2[CH:43]=[CH:44][CH:45]=[CH:46][C:30]=2[O:29][CH2:28]1)[C:4]([O:3][CH2:1][CH3:2])=[O:5])=[O:47])([CH3:42])([CH3:41])[CH3:40]
CCOC(=O)[C@H](CCCCCCCCN1C(=O)c2ccccc2C1=O)N[C@H]1COc2ccccc2N(CC(=O)OC(C)(C)C)C1=O
O
null
NN
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
null
8
A mixture of tert-butyl 3(S)-[1(S)-ethoxycarbonyl-9-phthalimidononyl]amino-4-oxo-2,3,4,5-tetrahydro-1,5-benzoxazepine-5-acetate (0.46 g), hydrazine hydrate (0.18 g) and ethanol (10 ml) is allowed to stand overnight at room temperature. The mixture is concentrated under reduced pressure, diluted with water (50 ml) and extracted with ethyl acetate (50 ml×4). Water (50 ml) and sodium bicarbonate (0.5 g) are added to the organic extract, and to the resulting mixture is added dropwise di-tert-butyl dicarbonate (0.24 g) with stirring. After stirring for 30 minutes at room temperature, the ethyl acetate layer is dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue is purified by silica gel column chromatography using hexane-ethyl acetate (2:1) as an eluent to yield tert-butyl 3(S)-[9-tert-butoxycarbonylamino-1(S)-ethoxycarbonylnonyl]amino-4-oxo-2,3,4,5-tetrahydro-1,5-benzoxazepine-5-acetate (0.35 g) as a colorless oil.
CCOC(=O)[C@H](CCCCCCCCNC(=O)OC(C)(C)C)N[C@H]1COc2ccccc2N(CC(=O)OC(C)(C)C)C1=O
null
159.7
null
1,121,130
ord_dataset-285df12e34cd46e993e3c8ebc3a8962a
null
2012-01-01T00:01:00
true
O[C:2]1[C:11]([NH:12][C:13](=[O:26])[C:14]2[CH:19]=[CH:18][CH:17]=[C:16]([C:20]3[CH:21]=[N:22][CH:23]=[CH:24][CH:25]=3)[CH:15]=2)=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].O.CC1C=CC(S(O)(=O)=O)=CC=1>C1(C)C=CC=CC=1>[N:22]1[CH:23]=[CH:24][CH:25]=[C:20]([C:16]2[CH:15]=[C:14]([C:13]3[O:26][C:2]4[C:3]([C:4]([O:6][CH3:7])=[O:5])=[CH:8][CH:9]=[CH:10][C:11]=4[N:12]=3)[CH:19]=[CH:18][CH:17]=2)[CH:21]=1
COC(=O)c1cccc(NC(=O)c2cccc(-c3cccnc3)c2)c1O
null
null
Cc1ccc(S(=O)(=O)O)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
O
null
null
null
null
null
null
null
null
null
null
null
Methyl 2-hydroxy-3-(3-(pyridin-3-yl)benzamido)benzoate (0.9 g, 2.5 mmol) and 4-methylbenzenesulfonic acid monohydrate (1 g, 5 mmol) were added to toluene (20 mL) and the mixture was stirred under reflux for 2 days. The resulting mixture was extracted with ethyl acetate (100 mL×4) and concentrated. The crude product was purified by column chromatography (silica gel, petroleum ether/ethyl acetate=20:1 to 10:1). 130 mg of methyl 2-(3-(pyridin-3-yl)phenyl)benzo[d]oxazole-7-carboxylate as a solid was obtained. Yield: 15%. LC-MS (ESI) m/z: 331 (M+1)+.
COC(=O)c1cccc2nc(-c3cccc(-c4cccnc4)c3)oc12
null
15.7
null