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
337,676
ord_dataset-4706e7a7f3cd421bb42b7f877cff8af9
null
1996-01-01T00:09:00
true
[Li]CCCC.[CH3:6][N:7]1[CH:11]=[CH:10][S:9][CH2:8]1.CN(P(N(C)C)(N(C)C)=O)C.[CH3:23][N:24]1[N:28]=[N:27][C:26]([C:29]2[CH:39]=[C:38]([CH3:40])[C:32]([O:33][CH2:34][CH2:35][CH2:36]Br)=[C:31]([CH3:41])[CH:30]=2)=[N:25]1.[Cl-].[NH4+]>C1COCC1>[CH3:6][N:7]1[CH:11]=[C:10]([CH2:36][CH2:35][CH2:34][O:33][C:32]2[C:31]([CH3:41])=[CH:30][C:29]([C:26]3[N:27]=[N:28][N:24]([CH3:23])[N:25]=3)=[CH:39][C:38]=2[CH3:40])[S:9][CH2:8]1
Cc1cc(-c2nnn(C)n2)cc(C)c1OCCCBr
CN1C=CSC1
null
[Cl-]
[Li]CCCC
[NH4+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)P(=O)(N(C)C)N(C)C
C1CCOC1
null
null
null
null
null
null
null
null
null
-78
0.25
n-BuLi (2.5M, 1.33 ml, 3.33 mmol) was added slowly at -78° C. to a solution of 3-methyl-thiazole (300 mg, 3.03 mmol) in 8 ml of THF under nitrogen. After stirring at -78° C. for 15 min, HMPA (1.08 g, 6.06 mmol) was added and the resulting mixture was stirred for 10 min. To the above mixture was added at -78° C. 3-[4-(2-methyl-tetrazol-5-yl)-2,6-dimethylphenoxy]-propylbromide (985 mg, 3.03 mmol) in 5 ml of THF. The mixture was allowed to warm to 20° C. and stirred for 3 h. Saturated ammonium chloride solution was added and the aqueous layer was extracted with ether (3×), and the organic layer was dried over sodium sulfate and concentrated in vacuo. The residue was purified by silica column chromatography (15 cm column, ethyl acetate/hexane, 1/8-3/1) to afford 290 mg (28%) of 3-methyl-5-[3-[4-(2-methyl-tetrazol-5-yl)-2,6-dimethylphenoxy]-propyl]thiazole.
Cc1cc(-c2nnn(C)n2)cc(C)c1OCCCC1=CN(C)CS1
null
27.7
null
305,053
ord_dataset-180e296d6d6245638d4d22a59120ea01
null
1995-01-01T00:02:00
true
Cl.Cl.[NH2:3][CH2:4][CH2:5][CH2:6][S:7][C:8]1[CH:13]=[CH:12][N:11]=[CH:10][CH:9]=1.C(N(CC)CC)C.[C:21](Cl)(=[O:25])[CH2:22][CH2:23][CH3:24]>C(Cl)Cl>[C:21]([NH:3][CH2:4][CH2:5][CH2:6][S:7][C:8]1[CH:13]=[CH:12][N:11]=[CH:10][CH:9]=1)(=[O:25])[CH2:22][CH2:23][CH3:24]
NCCCSc1ccncc1
CCCC(=O)Cl
null
Cl
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
To a solution of 700 mg (2.90 mmol) of 4-(3-aminopropylthio)pyridine dihydrochloride and 1.62 ml (11.6 mmol) of triethylamine in 30 ml of methylene chloride was added 0.36 ml (3.48 mmol) of butyryl chloride under ice-cooling with stirring and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was washed with an aqueous saturated sodium bicarbonate solution and water and dried. The solvent was distilled off. The residue was purified by column chromatography (eluent: methanol/ethyl acetate=1:1) to obtain 630 mg of the desired compound (91.1%, pale yellow oil).
CCCC(=O)NCCCSc1ccncc1
null
91.1
null
589,785
ord_dataset-7a74d48eeefd45aba53e7258f3ae067a
null
2003-01-01T00:04:00
true
[C:1]([O:5][C:6](=[O:25])[NH:7][C:8]1[CH:13]=[C:12]([N:14]([CH2:16][CH:17]([CH3:19])[CH3:18])[CH3:15])[C:11]([C:20]([F:23])([F:22])[F:21])=[CH:10][C:9]=1[NH2:24])([CH3:4])([CH3:3])[CH3:2].C([O:30][C:31](=O)[CH2:32][C:33]([C:35]1[CH:40]=[CH:39][CH:38]=[C:37]([C:41]2[O:45][N:44]=[C:43]([CH3:46])[CH:42]=2)[CH:36]=1)=[O:34])(C)(C)C>>[C:1]([O:5][C:6](=[O:25])[NH:7][C:8]1[CH:13]=[C:12]([N:14]([CH2:16][CH:17]([CH3:19])[CH3:18])[CH3:15])[C:11]([C:20]([F:23])([F:22])[F:21])=[CH:10][C:9]=1[NH:24][C:31](=[O:30])[CH2:32][C:33]([C:35]1[CH:40]=[CH:39][CH:38]=[C:37]([C:41]2[O:45][N:44]=[C:43]([CH3:46])[CH:42]=2)[CH:36]=1)=[O:34])([CH3:3])([CH3:4])[CH3:2]
CC(C)CN(C)c1cc(NC(=O)OC(C)(C)C)c(N)cc1C(F)(F)F
Cc1cc(-c2cccc(C(=O)CC(=O)OC(C)(C)C)c2)on1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared from [2-amino-5-(isobutyl-methyl-amino)-4-trifluoromethyl-phenyl]-carbamic acid tert-butyl ester (Example J36) (360 mg, 1.0 mmol) and 3-[3-(3-methyl-isoxazol-5-yl)-phenyl]-3-oxo-propionic acid tert-butyl ester (Example K4) (302 mg, 1.0 mmol) according to the general procedure M. Obtained as a light brown foam (430 mg, 73%).
Cc1cc(-c2cccc(C(=O)CC(=O)Nc3cc(C(F)(F)F)c(N(C)CC(C)C)cc3NC(=O)OC(C)(C)C)c2)on1
null
null
null
62,824
ord_dataset-9240b22758dd4f9e981f9ad2d5394155
null
1980-01-01T00:02:00
true
[C:1]([O:5][CH2:6][CH3:7])(=[O:4])[C:2]#[CH:3].[NH:8]1[CH2:12][CH2:11][CH2:10][CH2:9]1>C1C=CC=CC=1>[N:8]1([CH:3]=[CH:2][C:1]([O:5][CH2:6][CH3:7])=[O:4])[CH2:12][CH2:11][CH2:10][CH2:9]1
C#CC(=O)OCC
C1CCNC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
c1ccccc1
null
null
null
null
null
null
null
null
null
null
null
8
A solution of 29.43 g of ethyl propiolate (0.30 mol) in 200 ml of benzene was held at 25° in a water bath with magnetic stirring. A solution of 21.34 g of pyrrolidine in 50 ml of benzene was added dropwise over a period of 45 minutes, during which time the temperature rose to 35°. The clear brown solution was stirred overnight and the solvent removed under reduced pressure at 55°. The residue was distilled under reduced pressure to give 35.05 g of yellow oil, boiling point 110° (0.4 torr), which crystallized upon standing. The yellow solid was recrystallized from petroleum ether to give 31.36 (62%) of yellowish platelets, m.p. 37.5°-39.5°.
CCOC(=O)C=CN1CCCC1
null
69
null
432,658
ord_dataset-8cbb58558c904b2b85fa7a1b084a0de9
null
1999-01-01T00:06:00
true
[C:1]([C:3]1[C:4]([C:25]([F:28])([F:27])[F:26])=[N:5][N:6]([C:13]2[C:18]([Cl:19])=[CH:17][C:16]([C:20]([F:23])([F:22])[F:21])=[CH:15][C:14]=2[Cl:24])[C:7]=1[N:8]=[CH:9]OCC)#[N:2].[BH4-].[Na+]>CO>[C:1]([C:3]1[C:4]([C:25]([F:27])([F:28])[F:26])=[N:5][N:6]([C:13]2[C:14]([Cl:24])=[CH:15][C:16]([C:20]([F:22])([F:21])[F:23])=[CH:17][C:18]=2[Cl:19])[C:7]=1[NH:8][CH3:9])#[N:2]
CCOC=Nc1c(C#N)c(C(F)(F)F)nn1-c1c(Cl)cc(C(F)(F)F)cc1Cl
null
null
[BH4-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
25
null
To a suspension of 4-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-ethoxymethyleneamino-3-trifluoromethylpyrazole (1.0 g) in methanol (10 ml) stirred at room temperature was added sodium borohydride (0.17 g). After 2 hours an additional 0.17 g of sodium borohydride was added, and another 0.34 g added after 1 hours. One hour later the mixture was poured onto water (80 ml). The combined extracts were dried over anhydrous magnesium sulphate, filtered, and evaporated in vacuo. The white solid thus obtained was purified by chromatography on silica (Merck, 230-400 mesh, 0.7 kg cm-2) with dichloromethane as eluent, to furnish 4-cyano-5-methylamino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-trifluoromethylpyrazole as a white solid )0.6 g), m.p. 200-202° C.
CNc1c(C#N)c(C(F)(F)F)nn1-c1c(Cl)cc(C(F)(F)F)cc1Cl
null
null
null
43,060
ord_dataset-4c8627b52d564809adb9b494879c07c0
null
1978-01-01T00:07:00
true
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([N:16]=[C:17]([O:20][CH2:21][CH3:22])[CH2:18]Br)=[C:6]([CH:15]=1)[C:7]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=O.[NH3:23]>C(Cl)Cl>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[N:16]=[C:17]([O:20][CH2:21][CH3:22])[CH2:18][N:23]=[C:7]([C:9]3[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=3)[C:6]=2[CH:15]=1
CCOC(CBr)=Nc1ccc(Cl)cc1C(=O)c1ccccc1
N
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
25
1
A mixture of a solution of 0.38 part of 5-chloro-2-(2-bromo-1-ethoxyethylideneamino)benzophenone in 8 parts by volume of methylenechloride and 2 parts by volume of liquid ammonia is stirred in a sealed vessel at room temperature for 1 hour, followed by evaporation at room temperature to remove the ammonia. The resultant is shaken well with a mixture of 10 parts by volume of methylenechloride and 5 parts by volume of water. The methylene chloride layer is washed with water and dried over sodium sulfate, followed by evaporation of the solvent gives 7-chloro-2-ethoxy-5-phenyl-3H-1,4-benzodiazepine as an oily substance.
CCOC1=Nc2ccc(Cl)cc2C(c2ccccc2)=NC1
null
null
null
1,294,962
ord_dataset-de51ecc8d4434bacaa8bc32d7d73484c
null
2013-01-01T00:05:00
true
C(N(CC)CC)C.[NH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[NH:15][C:16]([C:18]1[S:19][C:20]2[CH2:21][NH:22][CH2:23][CH2:24][C:25]=2[N:26]=1)=[O:17].[CH3:27][C:28]1[CH:33]=[CH:32][C:31]([S:34](Cl)(=[O:36])=[O:35])=[CH:30][CH:29]=1>C1COCC1>[NH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[NH:15][C:16]([C:18]1[S:19][C:20]2[CH2:21][N:22]([S:34]([C:31]3[CH:32]=[CH:33][C:28]([CH3:27])=[CH:29][CH:30]=3)(=[O:36])=[O:35])[CH2:23][CH2:24][C:25]=2[N:26]=1)=[O:17]
Cc1ccc(S(=O)(=O)Cl)cc1
Nc1ccccc1NC(=O)c1nc2c(s1)CNCC2
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
0
2
Triethyl amine (1.0 eq) was added to solution of N-(2-aminophenyl)-4,5,6,7-tetrahydro[1,3]thiazolo[5,4-c]pyridine-2-carboxamide obtained in step VIII of example I (1.0 mmol) in 10 mL THF. The solution was cooled to 0° C. 4-Methyl-benzenesulfonyl chloride (1.0 mmol) was added slowly with continuous stirring. Reaction mixture was brought to room temperature and stirred for 2 h Reaction mixture was concentrated, diluted with water, extracted dichloromethane, washed with brine solution, and dried over anhydrous Na2SO4. Concentrated and purified by column chromatography to yield the title compound.
Cc1ccc(S(=O)(=O)N2CCc3nc(C(=O)Nc4ccccc4N)sc3C2)cc1
null
null
null
1,199,035
ord_dataset-fb72428f30234761b4216139dc228d0c
null
2012-01-01T00:09:00
true
[H-].[Na+].[CH3:3][O:4][C:5]1[CH:6]=[C:7]2[C:11](=[CH:12][CH:13]=1)[NH:10][C:9]([CH3:14])=[CH:8]2.C[N:16](C=O)C>>[CH3:3][O:4][C:5]1[CH:6]=[C:7]2[C:11](=[CH:12][CH:13]=1)[N:10]([NH2:16])[C:9]([CH3:14])=[CH:8]2
CN(C)C=O
COc1ccc2[nH]c(C)cc2c1
null
[H-]
[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
0.5
A suspension of NaH (1.25 g, 51 mmol, 60% in mineral oil) in DMF (47 mL) at 0° C. is treated with 5-methoxy-2-methylindole (500 mg, 3.1 mmol) and stirred at 0° C. for 0.5 h. The mixture is treated with HOSA (1.92 g, 17.0 mmol) portion wise and warmed to rt over 2 h. The mixture is then poured over ice, and extracted with EtOAc (3×50 mL). The combined organic layer is dried (Na2SO4), filtered and concentrated in vacuo to afford 5-methoxy-2-methyl-indol-1-ylamine, which is used in the next step without further purification.
COc1ccc2c(c1)cc(C)n2N
null
null
null
270,478
ord_dataset-a20aed058d7b40bc81fdf50bc5b03f97
null
1993-01-01T00:06:00
true
[NH:1]=[C:2]1[NH:6][C:5]([C:11]([F:14])([F:13])[F:12])([C:7]([F:10])([F:9])[F:8])[C:4](=[C:15]([F:20])[C:16]([F:19])([F:18])[F:17])[S:3]1.C(N(CC)CC)C.[N+:28]([C:31]1[CH:32]=[C:33]([CH:37]=[CH:38][CH:39]=1)[C:34](Cl)=[O:35])([O-:30])=[O:29]>C1(C)C=CC=CC=1>[N+:28]([C:31]1[CH:32]=[C:33]([CH:37]=[CH:38][CH:39]=1)[C:34]([NH:1][C:2]1[S:3][C:4](=[C:15]([F:20])[C:16]([F:17])([F:18])[F:19])[C:5]([C:7]([F:10])([F:9])[F:8])([C:11]([F:12])([F:13])[F:14])[N:6]=1)=[O:35])([O-:30])=[O:29]
N=C1NC(C(F)(F)F)(C(F)(F)F)C(=C(F)C(F)(F)F)S1
O=C(Cl)c1cccc([N+](=O)[O-])c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
CCN(CC)CC
null
null
null
null
null
null
null
null
null
103
3
In toluene (40 ml) were dissolved 2-imino-4,4-bis(trifluoromethyl)-5-(tetrafluoroethylidene)-1,3-thiazolidine (2.0 g) and triethylamine (1.0 ml), and a solution of 3-nitrobenzoyl chloride (1.3 g) dissolved in toluene (10 ml) was gradually added thereto under cooling and the mixture was stirred at 103° C. for 3 hours.
O=C(NC1=NC(C(F)(F)F)(C(F)(F)F)C(=C(F)C(F)(F)F)S1)c1cccc([N+](=O)[O-])c1
null
null
null
762,555
ord_dataset-2e58cb8db2bf482bbea23283b7e04488
null
2007-01-01T00:03:00
true
[CH:1]1([N:6]2[C:11]3=[N:12][C:13](S(C)=O)=[N:14][CH:15]=[C:10]3[CH2:9][N:8]([C:19]3[CH:24]=[C:23]([O:25][CH3:26])[CH:22]=[C:21]([O:27][CH3:28])[C:20]=3[F:29])[C:7]2=[O:30])[CH2:5][CH2:4][CH2:3][CH2:2]1.[NH2:31][CH2:32][C@H:33]([OH:38])[C@@H:34]([OH:37])[CH2:35][OH:36]>>[CH:1]1([N:6]2[C:11]3=[N:12][C:13]([NH:31][CH2:32][C@H:33]([OH:38])[C@@H:34]([OH:37])[CH2:35][OH:36])=[N:14][CH:15]=[C:10]3[CH2:9][N:8]([C:19]3[CH:24]=[C:23]([O:25][CH3:26])[CH:22]=[C:21]([O:27][CH3:28])[C:20]=3[F:29])[C:7]2=[O:30])[CH2:5][CH2:4][CH2:3][CH2:2]1
NC[C@H](O)[C@@H](O)CO
COc1cc(OC)c(F)c(N2Cc3cnc(S(C)=O)nc3N(C3CCCC3)C2=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
1-Cyclopentyl-3-(2-fluoro-3,5-dimethoxy-phenyl)-7-([S,S]-2,3,4-trihydroxy-butylamino)-3,4-dihydro-1H-pyrimido[4,5-d]pyrimidin-2-one was prepared as in Example 2 using 0.40 g (0.92 mmol) 1-cyclopentyl-3-(2-fluoro-3,5-dimethoxy-phenyl)-7-methanesulfinyl-3,4-dihydro-1H-pyrimido[4,5-d]pyrimidin-2-one and 0.33 g (2.76 mmol) (S,S)-4-amino-1,2,3-butanetriol. The final product was purified by column chromatography (20:1 dichloromethane/methanol) to get 0.05 g (11%) as a white solid: mp 86° C.–88° C.; MS (APCI) m/z 492.2, 493.2.
COc1cc(OC)c(F)c(N2Cc3cnc(NC[C@H](O)[C@@H](O)CO)nc3N(C3CCCC3)C2=O)c1
null
null
null
858,528
ord_dataset-93908aaae836460ebd48d733eccad483
null
2009-01-01T00:01:00
true
C(OC(=O)NC1C=CC(N2C=[C:20]([S:22][CH3:23])[N:19]=N2)=C(F)C=1)C1C=CC=CC=1.[Li+].C[Si]([N-][Si](C)(C)C)(C)C.[F:36][C:37]1[CH:38]=[C:39]([N:49]2[CH2:53][C@H:52]([CH2:54][OH:55])[O:51][C:50]2=[O:56])[CH:40]=[CH:41][C:42]=1[N:43]1[CH:47]=NC(C)=[N:44]1>>[F:36][C:37]1[CH:38]=[C:39]([N:49]2[CH2:53][C@H:52]([CH2:54][OH:55])[O:51][C:50]2=[O:56])[CH:40]=[CH:41][C:42]=1[N:43]1[CH:47]=[C:20]([S:22][CH3:23])[N:19]=[N:44]1
Cc1ncn(-c2ccc(N3C[C@H](CO)OC3=O)cc2F)n1
CSc1cn(-c2ccc(NC(=O)OCc3ccccc3)cc2F)nn1
null
C[Si](C)(C)[N-][Si](C)(C)C
[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
[3-Fluoro-4-[4-(methylthio)-1H-1,2,3-triazol-1-yl]phenyl] carbamic acid benzyl ester (Intermediate 49) (27.4 g, 76.5 mmol), LiHMDS (1M in THF, 91 ml) and R-(−)-glycidyl butyrate (11.5 g, 79.7 mmol) were reacted following the procedure for Intermediate 25 to give the crude title compound (19.4 g), which was used without further purification.
CSc1cn(-c2ccc(N3C[C@H](CO)OC3=O)cc2F)nn1
null
null
null
1,028,134
ord_dataset-83acb82dc5ba4f7aba439b9875aaac43
null
2011-01-01T00:02:00
true
[O:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[C:6]1[N:7]=[C:8]([NH:18][C:19]([C:21]2[CH:26]=[CH:25][N:24]=[CH:23][CH:22]=2)=[O:20])[S:9][C:10]=1[C:11]([C:13]1[CH:17]=[CH:16][NH:15][CH:14]=1)=[O:12].[H-].[Na+].[CH3:29]I.O>CN(C=O)C>[O:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[C:6]1[N:7]=[C:8]([NH:18][C:19]([C:21]2[CH:22]=[CH:23][N:24]=[CH:25][CH:26]=2)=[O:20])[S:9][C:10]=1[C:11]([C:13]1[CH:17]=[CH:16][N:15]([CH3:29])[CH:14]=1)=[O:12]
O=C(Nc1nc(-c2ccco2)c(C(=O)c2cc[nH]c2)s1)c1ccncc1
CI
null
[H-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
O
null
null
null
null
null
null
null
null
null
25
2
Compound 353 (105 mg, 0.288 mmol) was dissolved in DMF (1.4 mL), and 55% sodium hydride (25.3 mg, 0.576 mmol) and methyl iodide (0.0179 mL, 0.288 mmol) were added thereto, followed by stirring at room temperature for 2 hours. The reaction mixture was poured into water, followed by extraction with ethyl acetate. The organic layer was washed with a saturated aqueous solution of sodium chloride and dried over anhydrous magnesium sulfate, and then the solvent was distilled away under reduced pressure. The resulting residue was purified through silica gel column chromatography (hexane:ethyl acetate=1:1) to afford the entitled Compound 354 (97.0 mg, 89%).
Cn1ccc(C(=O)c2sc(NC(=O)c3ccncc3)nc2-c2ccco2)c1
null
89
null
1,201,285
ord_dataset-fb72428f30234761b4216139dc228d0c
null
2012-01-01T00:09:00
true
[OH:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH:5]=[CH:4][C:3]=1[C:12]([OH:14])=O.[F:15][C:16]([F:29])([F:28])[C:17]1[CH:18]=[C:19]([CH:21]=[C:22]([C:24]([F:27])([F:26])[F:25])[CH:23]=1)[NH2:20]>>[F:15][C:16]([F:28])([F:29])[C:17]1[CH:18]=[C:19]([NH:20][C:12]([C:3]2[CH:4]=[CH:5][C:6]3[C:11](=[CH:10][CH:9]=[CH:8][CH:7]=3)[C:2]=2[OH:1])=[O:14])[CH:21]=[C:22]([C:24]([F:25])([F:27])[F:26])[CH:23]=1
Nc1cc(C(F)(F)F)cc(C(F)(F)F)c1
O=C(O)c1ccc2ccccc2c1O
null
null
null
null
null
null
null
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 1-hydroxynaphthalene-2-carboxylic acid and 3,5-bis(trifluoromethyl)aniline as the raw materials, the same operation as the example 16 gave the title compound.
O=C(Nc1cc(C(F)(F)F)cc(C(F)(F)F)c1)c1ccc2ccccc2c1O
null
65.5
null
539,984
ord_dataset-49124ff635234889bd8dcfe87f4f9013
null
2002-01-01T00:04:00
true
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[NH:9][C:10]3[CH:16]=[CH:15][C:14]([NH2:17])=[CH:13][C:11]=3[N:12]=2)=[CH:4][CH:3]=1.[CH:18]1([C:24](Cl)=[O:25])[CH2:23][CH2:22][CH2:21][CH2:20][CH2:19]1>>[CH:18]1([C:24]([NH:1][C:2]2[CH:3]=[CH:4][C:5]([C:8]3[NH:9][C:10]4[CH:16]=[CH:15][C:14]([NH:17][C:24]([CH:18]5[CH2:23][CH2:22][CH2:21][CH2:20][CH2:19]5)=[O:25])=[CH:13][C:11]=4[N:12]=3)=[CH:6][CH:7]=2)=[O:25])[CH2:23][CH2:22][CH2:21][CH2:20][CH2:19]1
O=C(Cl)C1CCCCC1
Nc1ccc(-c2nc3cc(N)ccc3[nH]2)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
2-(N-Cyclohexylcarbanoyl-4′-aminophenyl)-6-(cyclohexylcarbanoylamino)-benzimidazole was prepared by Method A from 2-(4-aminophenyl)-6-aminobenzimidazole (0.195 g, 0.87 mmole) and cyclohexylcarbonyl chloride (0.291 ml, 0.319 g, 2.175 mmole). The resulting solid (76.7 mg) was purified by preparative HPLC.
O=C(Nc1ccc(-c2nc3cc(NC(=O)C4CCCCC4)ccc3[nH]2)cc1)C1CCCCC1
null
null
null
1,054,680
ord_dataset-373415d3e0e54004837cf4831e67666f
null
2011-01-01T00:05:00
true
[CH2:1]([N:8]1[C:12](=[O:13])[N:11]([C:14]2[CH:15]=[N:16][N:17]([CH2:19][C:20]3[C:21]([CH3:26])=[N:22][O:23][C:24]=3[CH3:25])[CH:18]=2)[C:10](=[O:27])[NH:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br[CH2:29][CH2:30][CH3:31]>>[CH2:1]([N:8]1[C:12](=[O:13])[N:11]([C:14]2[CH:15]=[N:16][N:17]([CH2:19][C:20]3[C:21]([CH3:26])=[N:22][O:23][C:24]=3[CH3:25])[CH:18]=2)[C:10](=[O:27])[N:9]1[CH2:29][CH2:30][CH3:31])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
CCCBr
Cc1noc(C)c1Cn1cc(-n2c(=O)[nH]n(Cc3ccccc3)c2=O)cn1
null
null
null
null
null
null
null
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 as in example 10-91 from 1-benzyl-4-(1-((3,5-dimethylisoxazol-4-yl)methyl)-1H-pyrazol-4-yl)-1,2,4-triazolidine-3,5-dione (example 10-9a) and 1-bromopropane. Yield: 38%. MS M+H calculated 409.19; found 409.2. The title compound was shown to inhibit hT2R08 bitter receptor and had an IC50 of 0.06 μM.
CCCn1c(=O)n(-c2cnn(Cc3c(C)noc3C)c2)c(=O)n1Cc1ccccc1
null
38
null
495,681
ord_dataset-9df8b3ec9c8742b3802e0efaac6f6ef3
null
2001-01-01T00:03:00
true
[Cl:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([O:8][C:9]2[CH:14]=[CH:13][C:12]([C:15]([F:18])([F:17])[F:16])=[CH:11][C:10]=2[NH2:19])[CH:7]=1.[F:20][C:21]([F:33])([F:32])[C:22]1[CH:27]=[CH:26][C:25]([S:28](Cl)(=[O:30])=[O:29])=[CH:24][CH:23]=1>CCOCC>[Cl:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([O:8][C:9]2[CH:14]=[CH:13][C:12]([C:15]([F:17])([F:16])[F:18])=[CH:11][C:10]=2[NH:19][S:28]([C:25]2[CH:24]=[CH:23][C:22]([C:21]([F:20])([F:32])[F:33])=[CH:27][CH:26]=2)(=[O:30])=[O:29])[CH:7]=1
Nc1cc(C(F)(F)F)ccc1Oc1cncc(Cl)c1
O=S(=O)(Cl)c1ccc(C(F)(F)F)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOCC
null
null
null
null
null
null
null
null
null
null
null
null
Using the method of Example 17.4, 4-(3-chloro-5-pyridyloxy)-3-aminobenzotrifluoride (0.4 g) and 4-trifluoromethylbenzenesulfonyl chloride ((0.339 g ) were combined to provide, after trituration with ether, the title sulfonamide (0.198 g) which was obtained as a crystalline solid. mp 169-171° C.
O=S(=O)(Nc1cc(C(F)(F)F)ccc1Oc1cncc(Cl)c1)c1ccc(C(F)(F)F)cc1
null
null
null
1,350,609
ord_dataset-6034127657614f02860ed057b62b882e
null
2013-01-01T00:10:00
true
F[C:2]1[CH:7]=[CH:6][C:5]([C:8]([F:11])([F:10])[F:9])=[CH:4][C:3]=1[N+:12]([O-:14])=[O:13].[NH:15]1[CH2:20][CH2:19][S:18][CH2:17][CH2:16]1.C(=O)(O)[O-].[Na+]>C1COCC1>[N+:12]([C:3]1[CH:4]=[C:5]([C:8]([F:11])([F:10])[F:9])[CH:6]=[CH:7][C:2]=1[N:15]1[CH2:20][CH2:19][S:18][CH2:17][CH2:16]1)([O-:14])=[O:13]
C1CSCCN1
O=[N+]([O-])c1cc(C(F)(F)F)ccc1F
null
O=C([O-])O
[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
48
To a solution of 1-fluoro-2-nitro-4-(trifluoromethyl)benzene (7.00 g, 33.48 mmol) in THF (250 ml) at room temperature was added thiomorpholine (3.45 g, 33.48 mmol) and sodium bicarbonate (3.66 g, 43.52 mmol). The vessel was purged with nitrogen and stirred at room temperature for 48 hours. After removal of solvent under reduced pressure, the mixture was taken up in ethyl acetate and filtered. The organics were washed with water, then brine and dried with magnesium sulfate. Filtration and concentration provided the title compound as a bright orange solid. MS m/z: 293.1 (M+H+); calc MW=292.28.
O=[N+]([O-])c1cc(C(F)(F)F)ccc1N1CCSCC1
null
null
null
72,906
ord_dataset-10f2568b472a4cabb35c3f313a159005
null
1980-01-01T00:11:00
true
[C:1]1([OH:7])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[OH:8][C:9]1[CH:17]=[CH:16][C:12]([C:13]([OH:15])=O)=[CH:11][CH:10]=1.F>O>[C:9]([O:7][C:1]1[CH:6]=[CH:5][C:4]([C:13]([C:12]2[CH:11]=[CH:10][C:9]([O:8][C:13](=[O:15])[CH3:12])=[CH:17][CH:16]=2)=[O:15])=[CH:3][CH:2]=1)(=[O:8])[CH3:10]
O=C(O)c1ccc(O)cc1
Oc1ccccc1
null
F
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
45.5 g (0.52 mole) of phenol, 69.0 g (0.50 mole) of 4-hydroxybenzoic acid, and 500 mL of hydrogen fluoride were heated together for 6 hr under autogenous pressure in an autoclave. Then the contents were mixed in excess water to precipitate a pink solid. Yield was 99 g (92.5%). The crude product was acetylated directly, without purification, by refluxing 2 hr in 3 times its volume of acetic anhydride and about 8 drops of sulfuric acid. Precipitation in excess water yielded 113 g of 4,4'-diacetoxybenzophenone of such high purity that no recrystallization was required (melting point 150-152° C. ).
CC(=O)Oc1ccc(C(=O)c2ccc(OC(C)=O)cc2)cc1
null
151.5
null
1,121,852
ord_dataset-285df12e34cd46e993e3c8ebc3a8962a
null
2012-01-01T00:01:00
true
O.O.O.[F-].C([N+](CCCC)(CCCC)CCCC)CCC.O.[Cl:23][C:24]1[CH:25]=[C:26]([C:49]2[CH:54]=[CH:53][C:52]([C:55]([N:57]3[CH2:62][CH2:61][CH:60]([C:63]([F:66])([F:65])[F:64])[CH2:59][CH2:58]3)=[O:56])=[CH:51][CH:50]=2)[CH:27]=[C:28]([Cl:48])[C:29]=1[CH2:30][C@@H:31]1[CH2:35][CH2:34][N:33]([C@H:36]2[CH2:41][CH2:40][C@H:39](OS(C)(=O)=O)[CH2:38][CH2:37]2)[C:32]1=[O:47]>C(#N)C>[CH:36]1([N:33]2[CH2:34][CH2:35][C@@H:31]([CH2:30][C:29]3[C:24]([Cl:23])=[CH:25][C:26]([C:49]4[CH:50]=[CH:51][C:52]([C:55]([N:57]5[CH2:58][CH2:59][CH:60]([C:63]([F:66])([F:65])[F:64])[CH2:61][CH2:62]5)=[O:56])=[CH:53][CH:54]=4)=[CH:27][C:28]=3[Cl:48])[C:32]2=[O:47])[CH2:41][CH2:40][CH:39]=[CH:38][CH2:37]1
CS(=O)(=O)O[C@H]1CC[C@H](N2CC[C@@H](Cc3c(Cl)cc(-c4ccc(C(=O)N5CCC(C(F)(F)F)CC5)cc4)cc3Cl)C2=O)CC1
null
null
CCCC[N+](CCCC)(CCCC)CCCC
[F-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC#N
O
null
null
null
null
null
null
null
null
null
80
12
Dissolve tetrabutylammonium fluoride trihydrate (0.436 g, 1.36 mmol) in 5 ml of acetonitrile. Add water (0.05 ml. 2.72 mmol) and stir for 10 minutes. Add trans-methanesulfonic acid 4-{(R)-3-[3,5-dichloro-4′-(4-trifluoromethyl-piperidine-1-carbonyl)-biphenyl-4-ylmethyl]-2-oxo-pyrrolidin-1-yl}-cyclohexyl ester (0.458 g, 0.68 mmol). Stir at 80° C. for 12 hours. Quench with saturated aqueous sodium bicarbonate and extract with ethyl acetate. Wash the extract with brine. Dry the organic layer over magnesium sulfate, filter, and concentrate under vacuum. Purify by silica gel chromatography recover 0.036 g (9%) of the title compound: MS (m/z): 579 (M+).
O=C(c1ccc(-c2cc(Cl)c(C[C@@H]3CCN(C4CC=CCC4)C3=O)c(Cl)c2)cc1)N1CCC(C(F)(F)F)CC1
null
null
null
851,659
ord_dataset-171b840ae6e84e45bab43b987d09f5c7
null
2008-01-01T00:11:00
true
Br[CH2:2][C:3]1[CH:8]=[CH:7][C:6]([Cl:9])=[CH:5][C:4]=1[O:10][CH3:11].[C:12]1(B(O)O)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C([O-])([O-])=O.[K+].[K+]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:2]([C:3]1[CH:8]=[CH:7][C:6]([Cl:9])=[CH:5][C:4]=1[O:10][CH3:11])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1
OB(O)c1ccccc1
COc1cc(Cl)ccc1CBr
null
c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1COCCO1
null
null
null
null
null
null
null
null
null
null
null
null
1-Bromomethyl-4-chloro-2-methoxy-benzene (50 mg, 0.21 mmol), phenyl boronic acid (28 mg, 0.23 mmol), Pd(PPh3)4 (24 mg, 0.021 mmol) and K2CO3 (87 mg, 0.63 mmol) were combined in dioxane, purged with N2, and heated to reflux for 16 hours. The mixture was then partitioned between ethyl acetate and water. The organic layer was washed with brine, dried (MgSO4), filtered, and concentrated under vacuum. The residue was purified by flash column chromatography on silica gel eluting with 4:1 hexanes/ethyl acetate to provide 9 mg (18%) of the title compound. MS (ESI) m/e 233 (M+H)+.
COc1cc(Cl)ccc1Cc1ccccc1
null
18.4
null
49,233
ord_dataset-0bb2e99daa66408fb8dbd6a0781d241c
null
1978-01-01T00:12:00
true
[CH3:1][O:2][C:3](=[O:42])[C@H:4]([CH2:38][CH:39]([CH3:41])[CH3:40])[NH:5][C:6](=[O:37])[CH2:7][NH:8][C:9](=[O:36])[C@H:10]([CH2:28][C:29]1[CH:34]=[CH:33][C:32]([OH:35])=[CH:31][CH:30]=1)[NH:11][C:12](=[O:27])[C@H:13]([CH2:25][OH:26])[NH:14]C(OCC1C=CC=CC=1)=O.[ClH:43]>CO.[Pd]>[ClH:43].[CH3:1][O:2][C:3](=[O:42])[C@H:4]([CH2:38][CH:39]([CH3:40])[CH3:41])[NH:5][C:6](=[O:37])[CH2:7][NH:8][C:9](=[O:36])[C@H:10]([CH2:28][C:29]1[CH:34]=[CH:33][C:32]([OH:35])=[CH:31][CH:30]=1)[NH:11][C:12](=[O:27])[C@H:13]([CH2:25][OH:26])[NH2:14]
COC(=O)[C@H](CC(C)C)NC(=O)CNC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@H](CO)NC(=O)OCc1ccccc1
null
null
[Pd]
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
null
null
A mixture consisting of 2.4 g. of N-benzyloxycarbonyl-L-seryl-L-tyrosylglycyl-L-leucine methyl ester, 60 ml. of methanol, 240 mg. of 5% palladium-on-carbon, and 5.4 ml. of 1.26 N hydrogen chloride in methanol is hydrogenated at one atmosphere and 25° C. for one hour. The mixture is then filtered to remove the catalyst, and the filtrate is evaporated to dryness under reduced pressure to give an amorphous solid residue of L-seryl-L-tyrosylglycyl-L-leucine methyl ester hydrochloride; [α]D25 -12.9° (2% in methanol); λmax 278, E11 33.6 (methanol).
COC(=O)[C@H](CC(C)C)NC(=O)CNC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](N)CO
null
null
null
73,665
ord_dataset-10f2568b472a4cabb35c3f313a159005
null
1980-01-01T00:11:00
true
C[N:2]([CH3:17])[CH:3]=[CH:4][C:5]([C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([C:13]([F:16])([F:15])[F:14])[CH:8]=1)=O.N[C:19]1[C:23]([C:24]#[N:25])=C[NH:21][N:20]=1>C(O)(=O)C>[F:16][C:13]([F:14])([F:15])[C:9]1[CH:10]=[CH:11][CH:12]=[C:7]([C:5]2[N:21]3[N:20]=[CH:19][C:23]([C:24]#[N:25])=[C:17]3[N:2]=[CH:3][CH:4]=2)[CH:8]=1
CN(C)C=CC(=O)c1cccc(C(F)(F)F)c1
N#Cc1c[nH]nc1N
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(=O)O
null
null
null
null
null
null
null
null
null
null
null
null
A mixture of 3.15 g. of 3-dimethylamino-3'-(trifluoromethyl)acrylophenone and 1.40 g. of 3-aminopyrazole-4-carbonitrile in 25 ml. of glacial acetic acid is refluxed for 6 hours. The mixture is evaporated and the residue is treated as described in Example 1, giving the desired product, m.p. 144°-145° C.
N#Cc1cnn2c(-c3cccc(C(F)(F)F)c3)ccnc12
null
null
null
674,933
ord_dataset-632f0d9054ce41aba87d4970966c34a6
null
2005-01-01T00:06:00
true
[CH2:1]([CH:5]([C:9](O)=O)[C:6]([OH:8])=[O:7])[CH2:2][CH2:3][CH3:4].N1CCCCC1.C=O>C(O)C>[CH2:1]([C:5](=[CH2:9])[C:6]([OH:8])=[O:7])[CH2:2][CH2:3][CH3:4]
CCCCC(C(=O)O)C(=O)O
null
null
C=O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCNCC1
CCO
null
null
null
null
null
null
null
null
null
80
8
To a solution of n-butylmalonic acid (17.2 g, 107 mmol) in ethanol (200 ml) was added piperidine (12.76 ml, 129 mmol) and 37% aq. formaldehyde (40.3 ml, 538 mmol). The solution was heated to 80° C. during which time a precipitate appeared and gradually redissolved over 1 hour. The reaction mixture was stirred at 80° C. overnight then cooled to room temperature. The solvents were removed under reduced pressure and the residue was dissolved in ethyl acetate (200 ml), washed successively with 1 M hydrochloric acid and brine, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated to give the title compound as a clear oil (13.37 g, 97%). 1H-NMR; δ (CDCl3), 6.29 (1H, s), 5.65 (1H, s), 2.34-2.28 (2H, m), 1.54-1.26 (4H, m), 0.94 (3H, t, J=7.1 Hz).
C=C(CCCC)C(=O)O
null
97.5
null
1,697,090
ord_dataset-54347fcace774f89850681d6dec8009f
null
2016-01-01T00:03:00
true
[C:1]([NH:4][CH2:5][CH2:6][N:7]1[CH2:16][CH:15]2[CH:10]([CH2:11][CH2:12][CH2:13][CH2:14]2)[N:9]2[C:17](=[O:46])[C:18]3[N:19]([CH:21]=[C:22]([C:34]([NH:36][CH2:37][C:38]4[CH:43]=[CH:42][C:41]([F:44])=[CH:40][C:39]=4[F:45])=[O:35])[C:23](=[O:33])[C:24]=3[O:25]CC3C=CC=CC=3)[CH2:20][CH:8]12)(=[O:3])[CH3:2]>[Pd]>[C:1]([NH:4][CH2:5][CH2:6][N:7]1[CH2:16][CH:15]2[CH:10]([CH2:11][CH2:12][CH2:13][CH2:14]2)[N:9]2[C:17](=[O:46])[C:18]3[N:19]([CH:21]=[C:22]([C:34]([NH:36][CH2:37][C:38]4[CH:43]=[CH:42][C:41]([F:44])=[CH:40][C:39]=4[F:45])=[O:35])[C:23](=[O:33])[C:24]=3[OH:25])[CH2:20][CH:8]12)(=[O:3])[CH3:2]
CC(=O)NCCN1CC2CCCCC2N2C(=O)c3c(OCc4ccccc4)c(=O)c(C(=O)NCc4ccc(F)cc4F)cn3CC12
null
null
[Pd]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
racemic-4aS,6aS,14aS)-6-[2-(Acetylamino)ethyl]-N-[(2,4-difluorophenyl)methyl]-12-hydroxy-11,13-dioxo-1,2,3,4,4a,5,6,6a,7,11,13,14a-dodecahydropyrido[1′,2′:4,5]pyrazino[1,2-a]quinazoline-10-carboxamide. In a manner similar to that described in example Z-35, from racemic-N-[2-({[(1S,2S)-2-aminocyclohexyl]methyl}amino)ethyl]acetamide hydrochloride (82 mg, 0.849 mmol) and 16a (50 mg, 0.106 mmol) was prepared the title compound (24 mg, 86%). This material was deprotected in a second step similar to the procedure described in example Z-37. Thus, from racemic (4aS,6aS,14aS)-6-[2-(acetylamino)ethyl]-N-[(2,4-difluorophenyl)methyl]-11,13-dioxo-12-[(phenylmethyl)oxy]-1,2,3,4,4a,5,6,6a,7,11,13,14a-dodecahydropyrido[1′,2′:4,5]pyrazino[1,2-a]quinazoline-10-carboxamide (24 mg, 0.0379 mmol) and 10% Pd/C (1 mg) was prepared the title compound as a white solid after purification by HPLC. 1H NMR (CDCl3) 12.50 (s, 1H), 10.44 (s, 1H), 8.35 (s, 1H), 7.32 (m, 1H), 6.79 (m, 2H), 5.86 (s, 1H), 4.78 (m, 1H), 4.61-4.50 (m, 3H), 4.30 (m, 1H), 8.35 (m, 1H), 3.18 (m, 1H), 2.96 (m, 1H), 2.76 (m, 2H), 2.48 (m, 1H), 2.19 (m, 1H), 1.89-1.28 (m, 12H): ES+MS: 544 (M+1).
CC(=O)NCCN1CC2CCCCC2N2C(=O)c3c(O)c(=O)c(C(=O)NCc4ccc(F)cc4F)cn3CC12
null
null
null
804,245
ord_dataset-ed846b4b229e4bb09ad9dba95ad7ebeb
null
2008-01-01T00:01:00
true
[CH3:1][C:2]1([CH3:20])[C:10]2[C:5](=[CH:6][CH:7]=[C:8](OS(C(F)(F)F)(=O)=O)[CH:9]=2)[C:4](=[O:19])[CH2:3]1.[CH3:21][O:22][C:23]1[CH:28]=[CH:27][C:26](B(O)O)=[CH:25][CH:24]=1>>[CH3:21][O:22][C:23]1[CH:28]=[CH:27][C:26]([C:8]2[CH:9]=[C:10]3[C:5](=[CH:6][CH:7]=2)[C:4](=[O:19])[CH2:3][C:2]3([CH3:20])[CH3:1])=[CH:25][CH:24]=1
COc1ccc(B(O)O)cc1
CC1(C)CC(=O)c2ccc(OS(=O)(=O)C(F)(F)F)cc21
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared from trifluoro-methanesulfonic acid 3,3-dimethyl-1-oxo-indan-5-yl ester and 4-methoxyphenyl boronic acid according to the procedure described in example 21. MS (ES) m/z 267.1. HRMS: calcd for C18H18O2+H+, 267.13796; found (ESI, [M+H]+), 267.1373.
COc1ccc(-c2ccc3c(c2)C(C)(C)CC3=O)cc1
null
null
null
673,703
ord_dataset-632f0d9054ce41aba87d4970966c34a6
null
2005-01-01T00:06:00
true
[F:1][C:2]1[CH:20]=[CH:19][C:5]([CH2:6][O:7][C:8]2[CH:9]=[C:10]3[C:14](=[CH:15][CH:16]=2)[C:13](=[O:17])[NH:12][C:11]3=[O:18])=[CH:4][CH:3]=1.[H-].[Na+].Br[CH2:24][C:25]([NH2:27])=[O:26].O>O1CCCC1>[F:1][C:2]1[CH:20]=[CH:19][C:5]([CH2:6][O:7][C:8]2[CH:9]=[C:10]3[C:14](=[CH:15][CH:16]=2)[C:13](=[O:17])[N:12]([CH2:24][C:25]([NH2:27])=[O:26])[C:11]3=[O:18])=[CH:4][CH:3]=1
O=C1NC(=O)c2cc(OCc3ccc(F)cc3)ccc21
NC(=O)CBr
null
[H-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
C1CCOC1
null
null
null
null
null
null
null
null
null
25
3
A mixture of 5-(4-fluoro-benzyloxy)-isoindole-1,3-dione (100 mg, 0.37 mmol), sodium hydride (55% in mineral oil, 18 mg, 0.42 mmol) and 2-bromoacetamide (61 mg, 0.44 mmol) in dry tetrahydrofuran (5 mL) at 0° C. was stirred at room temperature for 3 h and then heated at 50° C. for 1 h. After cooling to 0° C., water (2 mL) was added and the product extracted with ethyl acetate. The organic extracts were then washed with brine and dried over sodium sulfate. Filtration and evaporation gave a residue which was purified by chromatography (SiO2, heptane-CH2Cl2 2:3 then CH2Cl2— 2N NH3-MeOH 99:1: to 4:1) to afford the title compound (78 mg, 65%) as a white solid.
NC(=O)CN1C(=O)c2ccc(OCc3ccc(F)cc3)cc2C1=O
null
64.2
null
669,419
ord_dataset-e90cd41afe844e49875435eb99903799
null
2005-01-01T00:05:00
true
[F:1]/[C:2](=[C:13](/[C:15]1[CH:16]=[C:17]2[C:22](=[CH:23][C:24]=1[O:25][CH2:26][CH2:27][CH3:28])[O:21][C:20]([CH3:30])([CH3:29])[CH:19]=[C:18]2[CH:31]([CH3:33])[CH3:32])\[CH3:14])/[CH:3]=[CH:4]/[C:5](/[CH3:12])=[CH:6]/[C:7]([O:9]CC)=[O:8].[OH-].[Na+]>C(O)C.C1COCC1>[F:1]/[C:2](=[C:13](/[C:15]1[CH:16]=[C:17]2[C:22](=[CH:23][C:24]=1[O:25][CH2:26][CH2:27][CH3:28])[O:21][C:20]([CH3:30])([CH3:29])[CH:19]=[C:18]2[CH:31]([CH3:32])[CH3:33])\[CH3:14])/[CH:3]=[CH:4]/[C:5](/[CH3:12])=[CH:6]/[C:7]([OH:9])=[O:8]
CCCOc1cc2c(cc1/C(C)=C(F)\C=C\C(C)=C\C(=O)OCC)C(C(C)C)=CC(C)(C)O2
null
null
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
Following General Procedure G, a solution of ethyl (2E,4E,6E)-6-fluoro-7-(4-isopropyl-2,2-dimethyl-7-propoxy-2H-chromen-6-yl)-3-methyl-octa-2,4,6-trienoate (Compound 112, 73 mg, 0.16 mmo) in ethanol and THF was hydrolyzed with NaOH to yield the title compound as a yellow solid after recrystallized from acetonitrile.
CCCOc1cc2c(cc1/C(C)=C(F)\C=C\C(C)=C\C(=O)O)C(C(C)C)=CC(C)(C)O2
null
null
null
203,223
ord_dataset-19e5fc80c1554f4f8641c835e055f02b
null
1990-01-01T00:01:00
true
[C:1]([O:7][CH2:8][CH3:9])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].[H-].[Na+].[Li]CCCC.[F:17][C:18]1[CH:23]=[CH:22][C:21]([C:24]([C:36]2[CH:41]=[CH:40][C:39]([F:42])=[C:38]([CH3:43])[CH:37]=2)=[C:25]([C:30]2[N:34]([CH3:35])[N:33]=[N:32][N:31]=2)[CH:26]=[CH:27][CH:28]=[O:29])=[CH:20][C:19]=1[CH3:44]>O1CCCC1.CCCCCC>[F:17][C:18]1[CH:23]=[CH:22][C:21]([C:24]([C:36]2[CH:41]=[CH:40][C:39]([F:42])=[C:38]([CH3:43])[CH:37]=2)=[C:25]([C:30]2[N:34]([CH3:35])[N:33]=[N:32][N:31]=2)[CH:26]=[CH:27][CH:28]([OH:29])[CH2:5][C:3](=[O:4])[CH2:2][C:1]([O:7][CH2:8][CH3:9])=[O:6])=[CH:20][C:19]=1[CH3:44]
Cc1cc(C(=C(C=CC=O)c2nnnn2C)c2ccc(F)c(C)c2)ccc1F
CCOC(=O)CC(C)=O
null
[H-]
[Li]CCCC
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
CCCCCC
null
null
null
null
null
null
null
null
null
-78
0.25
A solution of the dianion of ethyl acetoacetate (1.42 mL, 11.1 mmoles) in dry tetrahydrofuran (15 mL) was generated as described in Example 10 using 450 mg (11.3 mmoles) of NaH (60% in mineral oil) and 4.5 mL (11.1 mmoles) of 2.5M n-BuLi in hexane at 0° C. under argon. The orange dianion solution, after being chilled to -78° C., was transferred via a cannula into a tetrahydrofuran (15 mL) solution containing 5,5-bis(4-fluoro-3-methylphenyl)-4-(1-methyl-1H-tetrazol-5-yl)-2,4-pentadienal (2.12 g, 5.6 mmoles) at -78° C. The reaction mixture was stirred at -78° C. for 15 minutes. Analytical TLC eluted once with 50% (v/v) ethyl acetate in hexanes showed a major product at Rf =0.16. The reaction mixture was diluted with 20 mL of 1N HCl and the organic residues were extracted with ethyl acetate (30 mL×2). The organic layers were combined, dried over MgSO4 and concentrated under reduced pressure to give a pale syrup. The crude product was chromatographed on a silica gel column eluted with 35% (v/v) ethyl acetate in hexanes to give 1.39 g (48.7%) of the title compound. MS (CI): m/e=511 for (M+H)+ ;
CCOC(=O)CC(=O)CC(O)C=CC(=C(c1ccc(F)c(C)c1)c1ccc(F)c(C)c1)c1nnnn1C
null
48.6
null
8,688
ord_dataset-ad879e603f9440f6bfb7fbd18e5e8761
null
1976-01-01T00:06:00
true
[N+:1]([C:4]1[CH:5]=[C:6]([CH:10]=[CH:11][CH:12]=1)[C:7]([OH:9])=[O:8])([O-:3])=[O:2].[CH3:13]N(N=O)C(N)=O.[OH-].[K+]>COCCOC.O>[N+:1]([C:4]1[CH:5]=[C:6]([CH:10]=[CH:11][CH:12]=1)[C:7]([O:9][CH3:13])=[O:8])([O-:3])=[O:2]
O=C(O)c1cccc([N+](=O)[O-])c1
CN(N=O)C(N)=O
null
[K+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
COCCOC
O
null
null
null
null
null
null
null
null
null
null
null
1.00 grams (6 millimoles) of m-nitrobenzoic acid and 2.4 grams (2.4 millimoles) of N-methyl,N-nitrosourea were dissolved in 25 milliliters of a 5:1 mixture of 1,2-dimethoxyethane and water. 40 milliliters of 0.6 N potassium hydroxide was added in a dropwise manner while the mixture was held at 0°C. in an ice bath. The solution was extracted with ether (4×50 milliliters) and the water layer (pH 10) was saved. The ether layer was dried (MgSO4) and workup gave 0.65 grams of methyl m-nitrobenzoate, melting point 71°-72°C. The water layer gave 0.25 grams of unreacted acid. Yield, based on consumed acid, was approximately 85 percent.
COC(=O)c1cccc([N+](=O)[O-])c1
null
149.5
null
416,591
ord_dataset-1cb9d78632144c5f8acfc3e9ff388678
null
1998-01-01T00:11:00
true
[Cl:1][C:2]1[CH:3]=[C:4]([CH:9]([CH:15]2[CH2:17][O:16]2)[CH2:10][C:11]([O:13]C)=O)[CH:5]=[CH:6][C:7]=1[Cl:8].[CH3:18][NH:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>FC(F)(F)CO>[Cl:1][C:2]1[CH:3]=[C:4]([CH:9]2[CH:15]([CH2:17][N:19]([CH3:18])[C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[O:16][C:11](=[O:13])[CH2:10]2)[CH:5]=[CH:6][C:7]=1[Cl:8]
COC(=O)CC(c1ccc(Cl)c(Cl)c1)C1CO1
CNc1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
OCC(F)(F)F
null
null
null
null
null
null
null
null
null
null
23
6
Treat a solution of the product of step 2 (368 mg, 1.34 mmol) in 2,2,2 trifluoroethanol (1 mL) with N-methyl aniline (217 μL, 2.01 mmol, 1.5 eq) and stir for 6 h at 23° C. followed by 6 h at 80° C. Cool to 23° C., concentrate in vacuo and purify by silica gel chromatography (column: 3.5×12 cm; eluant: hexane:EtOAc (4:1)) to provide 446 mg (1.3 mmol, 97%) of 4-(3,4-dichlorophenyl)-dihydro-5-[(methylphenylamino)methyl]-2(3H)-furanone as a white solid.
CN(CC1OC(=O)CC1c1ccc(Cl)c(Cl)c1)c1ccccc1
null
97
null
903,409
ord_dataset-46d216f2c4374ef5b9df90427e2a4cd4
null
2009-01-01T00:09:00
true
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[C:16]([O:20][CH3:21])[C:15]=2[CH3:22])=[C:6]([CH2:8][C:9](O)=O)[CH:7]=1.O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.[OH-:37].[Na+]>C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[CH2:12][CH2:13][C:14]3[C:15]([CH3:22])=[C:16]([O:20][CH3:21])[CH:17]=[CH:18][C:19]=3[C:9](=[O:37])[CH2:8][C:6]=2[CH:7]=1
[OH-]
COc1cccc(CCc2ccc(Br)cc2CC(=O)O)c1C
null
O=P12OP3(=O)OP(=O)(O1)OP(=O)(O2)O3
[Na+]
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
90
null
To a stirred suspension of 5-bromo-2-[2-(3-methoxy-2-methyl-phenyl)-ethyl]-phenylacetic acid (11) (4.38 g; 12.06 mmol) in toluene (20 mL), was added phosphorous pentoxide (6.0 g; 42.2 mmol). The mixture was heated at 90° C. for 16 hours. The mixture was cooled, treated with 1.0 N solution of sodium hydroxide and extracted with chloroform. The extracts were combined, dried over Na2SO4, and evaporated. The resultant residue was chromatograped on silica gel using hexane and ethyl acetate (4:1) to give compound 12 as colorless crystals, 2.40 g; 55% yield.
COc1ccc2c(c1C)CCc1ccc(Br)cc1CC2=O
null
55
null
838,245
ord_dataset-074f86301ec5441ab3b52d902ac06949
null
2008-01-01T00:09:00
true
[CH3:1][C:2]1[CH:3]=[C:4]([C:9]2[C:18]3[C:13](=[CH:14][C:15]([O:19][CH3:20])=[CH:16][CH:17]=3)[C:12](=O)[NH:11][N:10]=2)[CH:5]=[CH:6][C:7]=1[CH3:8].P(Cl)(Cl)([Cl:24])=O>>[Cl:24][C:12]1[C:13]2[C:18](=[CH:17][CH:16]=[C:15]([O:19][CH3:20])[CH:14]=2)[C:9]([C:4]2[CH:5]=[CH:6][C:7]([CH3:8])=[C:2]([CH3:1])[CH:3]=2)=[N:10][N:11]=1
COc1ccc2c(-c3ccc(C)c(C)c3)n[nH]c(=O)c2c1
O=P(Cl)(Cl)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
null
null
This compound is obtained according to the procedure described in 1.3. by reacting 4-(3,4-dimethylphenyl)-7-methoxy-2H-phthalazin-1-one with phosphoryl chloride.
COc1ccc2c(-c3ccc(C)c(C)c3)nnc(Cl)c2c1
null
null
null
382,204
ord_dataset-f367d8d2baac490b9204609a79420961
null
1997-01-01T00:11:00
true
[C:1]([O:5][C:6]([NH:8][C@H:9]([C:14]([OH:16])=O)[C@H:10]([CH2:12][CH3:13])[CH3:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(N1CCOCC1)C.ClC(OCC(C)C)=O.[CH2:33]([NH2:40])[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1>C1COCC1>[CH2:33]([NH:40][C:14](=[O:16])[C@H:9]([C@H:10]([CH2:12][CH3:13])[CH3:11])[NH:8][C:6]([O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:7])[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1
CC[C@H](C)[C@H](NC(=O)OC(C)(C)C)C(=O)O
NCc1ccccc1
null
CC(C)COC(=O)Cl
CCN1CCOCC1
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
-5
null
Into a 500 mL round bottomed flask equipped with a magnetic stirrer was added N-(tert-butoxycarbonyl)-L-isoleucine (22.53 g, 97.39 mmol, 1.0 eq) and THF (300 mL). The solution was stirred until homogeneous, cooled to -5° C., and treated with N-ethylmorpholine (14.23 mL, 12.88 g, 112.0 mmol, 1.15 eq). The solution was stirred at -5° C. for 20 min, and isobutyl chloroformate (13.24 mL, 13.90 g, 102 mmol, 1.05 eq) was added dropwise over 10 min. After stirring at -5° C. for 30 min, benzylamine (12.24 mL, 12.0 g, 112.0 mmol, 1.15 eq) was added dropwise over 10 min. After the addition was complete, the flask was removed from the cold bath and the solution was stirred at 22° C. for 2.5 hrs. The solution was concentrated to a residue, and partitioned between ethyl acetate (200 mL) and water (100 mL). The aqueous layer was extracted with ethyl ether (2×100 mL) and discarded. The organic extracts were combined, washed with 1N HCl (5×50 mL), 1N NaOH (3×50 mL), satd. aq NaCl (50 mL), and dried (MgSO4). The solution was concentrated in vacuo to provide 29.93 g (96%) of N-(tert-butoxycarbonyl)-L-Isoleucine benzylamide as a white solid.
CC[C@H](C)[C@H](NC(=O)OC(C)(C)C)C(=O)NCc1ccccc1
null
95.9
null
589,752
ord_dataset-7a74d48eeefd45aba53e7258f3ae067a
null
2003-01-01T00:04:00
true
[C:1]([O:5][C:6](=[O:22])[NH:7][C:8]1[CH:13]=[C:12]([N:14]([CH3:16])[CH3:15])[C:11]([C:17]([F:20])([F:19])[F:18])=[CH:10][C:9]=1[NH2:21])([CH3:4])([CH3:3])[CH3:2].[N:23]1([C:28]2[CH:29]=[C:30]([C:34]3[O:39]C(C)(C)[O:37][C:36](=O)[CH:35]=3)[CH:31]=[CH:32][CH:33]=2)[CH:27]=[CH:26][N:25]=[CH:24]1>>[C:1]([O:5][C:6](=[O:22])[NH:7][C:8]1[CH:13]=[C:12]([N:14]([CH3:16])[CH3:15])[C:11]([C:17]([F:20])([F:19])[F:18])=[CH:10][C:9]=1[NH:21][C:36](=[O:37])[CH2:35][C:34]([C:30]1[CH:31]=[CH:32][CH:33]=[C:28]([N:23]2[CH:27]=[CH:26][N:25]=[CH:24]2)[CH:29]=1)=[O:39])([CH3:4])([CH3:2])[CH3:3]
CN(C)c1cc(NC(=O)OC(C)(C)C)c(N)cc1C(F)(F)F
CC1(C)OC(=O)C=C(c2cccc(-n3ccnc3)c2)O1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared from (2-amino-5-dimethylamino-4-trifluoromethyl-phenyl)-carbamic acid tert.-butyl ester (Example J6) and 6-(3-imidazol-1-yl-phenyl)-2,2-dimethyl-[1,3]dioxin-4-one (Example L3) according to the general procedure M. Obtained as an orange oil (238 mg).
CN(C)c1cc(NC(=O)OC(C)(C)C)c(NC(=O)CC(=O)c2cccc(-n3ccnc3)c2)cc1C(F)(F)F
null
null
null
279,017
ord_dataset-140fb5527ff24f97bcf0094c5d100120
null
1993-01-01T00:11:00
true
I[C:2](=[CH2:16])[CH2:3][CH:4]([C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:9]=[CH:8][CH:7]=1)[OH:5].[OH-].[Na+].Cl>CN(C)C=O>[C:6]1([CH:4]([CH2:3][C:2]#[CH:16])[OH:5])[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:9]=[CH:8][CH:7]=1
C=C(I)CC(O)c1cccc2ccccc12
null
null
Cl
[Na+]
[OH-]
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
6
5.00 Grams of 2-iodoallyl-α-naphthylcarbinol were disolved in 50 g of dimethylformamide, and 1.23 g of sodium hydroxide in a flake form were added. The mixture was stirred at room temperature for 6 hours. After the reaction was completed the reaction mixture was neutralized with concentrated hydrochloric acid, insolubles were filtered off, and the filtrate was concentrated under reduced pressure. The concentration residue was subjected to extraction with toluene and washed with a 7% sodium carbonate aqueous solution, and then the toluene was distilled off under reduced pressure to give 2.78 g of α-naphthylpropargylcarbinol; nD25 =1.549, FI-MS m/e 196(M+).
C#CCC(O)c1cccc2ccccc12
null
null
null
1,337,681
ord_dataset-08852243bba44cb28769a5833f1515fe
null
2013-01-01T00:09:00
true
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[S:9][C:10]([CH:13]([OH:15])C)=[CH:11][N:12]=2)=[CH:4][CH:3]=1.[H-].[Na+].Cl[C:19]1[CH:27]2[CH:22]([C:23]3([CH3:29])[O:28][CH:26]2[CH2:25][CH2:24]3)[C:21](=[O:30])[CH:20]=1>O1CCCC1>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[S:9][C:10]([CH2:13][O:15][C:19]3[CH:27]4[CH:22]([C:23]5([CH3:29])[O:28][CH:26]4[CH2:25][CH2:24]5)[C:21](=[O:30])[CH:20]=3)=[CH:11][N:12]=2)=[CH:6][CH:7]=1
CC(O)c1cnc(-c2ccc(Cl)cc2)s1
CC12CCC(O1)C1C(Cl)=CC(=O)C12
null
[H-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
25
0.08
To a solution of 1-[2-(4-chloro-phenyl)-thiazol-5-yl]ethanol (264 mg, 1.1 mmol) in tetrahydrofuran (5 ml) is added in one portion the sodium hydride (60% dispersion in mineral oil, 44 mg, 1.1 mmol). The reaction mixture is stirred for five minutes at room temperature and 5-Chloro-1-methyl-10-oxa-tricyclo[5.2.1.0*2,6*]dec-4-en-3-one (219 mg, 1.1 mmol) is added in one-portion. The reaction mixture is stirred at room temperature overnight. Silica gel is added to the crude reaction mixture, the solvent is evaporated under reduced pressure and the residue is purified by flash chromatography on silica gel to give 5-[2-(4-chloro-phenyl)-thiazol-5-ylmethoxy]-1-methyl-10-oxa-tricyclo[5.2.1.0*2,6*]dec-4-en-3-one (410 mg).
CC12CCC(O1)C1C(OCc3cnc(-c4ccc(Cl)cc4)s3)=CC(=O)C12
null
96.1
null
1,112,623
ord_dataset-375a420ee9b042918ddca20f02df37d3
null
2011-01-01T00:11:00
true
[CH2:1]([O:3][C:4](=[O:26])[CH2:5][C:6]1[CH:7]=[C:8]([C:14]2[CH:19]=[CH:18][C:17]([C:20]([F:23])([F:22])[F:21])=[CH:16][C:15]=2[CH2:24][NH2:25])[C:9]([O:12][CH3:13])=[CH:10][CH:11]=1)[CH3:2].[CH2:27]([N:34]=[C:35]=[O:36])[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1>>[CH2:1]([O:3][C:4](=[O:26])[CH2:5][C:6]1[CH:7]=[C:8]([C:14]2[CH:19]=[CH:18][C:17]([C:20]([F:23])([F:21])[F:22])=[CH:16][C:15]=2[CH2:24][NH:25][C:35]([NH:34][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)=[O:36])[C:9]([O:12][CH3:13])=[CH:10][CH:11]=1)[CH3:2]
O=C=NCc1ccccc1
CCOC(=O)Cc1ccc(OC)c(-c2ccc(C(F)(F)F)cc2CN)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 according to the procedure described in Example 95, Step 1, using the following starting materials: (2′-aminomethyl-6-methoxy-4′-trifluoromethyl-biphenyl-3-yl)-acetic acid ethyl ester and benzyl isocyanate.
CCOC(=O)Cc1ccc(OC)c(-c2ccc(C(F)(F)F)cc2CNC(=O)NCc2ccccc2)c1
null
null
null
479,141
ord_dataset-21c1b1c06c7e4e09a38b5b1c71a32e52
null
2000-01-01T00:10:00
true
[CH2:1]1[O:12][C:11]2[CH:10]=[CH:9][C:5]([CH2:6][CH2:7][NH2:8])=[CH:4][C:3]=2[O:2]1.[Cl:13][C:14]1[N:15]=[C:16](Cl)[C:17]2[CH:22]=[C:21]([C:23]([F:26])([F:25])[F:24])[S:20][C:18]=2[N:19]=1>>[Cl:13][C:14]1[N:15]=[C:16]([NH:8][CH2:7][CH2:6][C:5]2[CH:9]=[CH:10][C:11]3[O:12][CH2:1][O:2][C:3]=3[CH:4]=2)[C:17]2[CH:22]=[C:21]([C:23]([F:25])([F:26])[F:24])[S:20][C:18]=2[N:19]=1
NCCc1ccc2c(c1)OCO2
FC(F)(F)c1cc2c(Cl)nc(Cl)nc2s1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Following the procedure of Example 1, the reaction of 3,4-methylenedioxyphenethylamine with 2,4-dichloro-6-trifluoromethyl-thieno-[2,3-d]-pyrimidine yields 2-chloro-6-trifluoromethyl-4-(3,4-methylenedioxyphenethylamino)-thieno-[2,3-d]-pyrimidine.
FC(F)(F)c1cc2c(NCCc3ccc4c(c3)OCO4)nc(Cl)nc2s1
null
null
null
1,000,735
ord_dataset-70899a0178cc441482746c093624afa0
null
2010-01-01T00:10:00
true
[CH3:1][O:2][C:3]1[C:4]([CH2:12][N:13]([CH3:15])[CH3:14])=[C:5]2[C:9](=[CH:10][CH:11]=1)[NH:8][CH:7]=[CH:6]2.CN(C=O)C.[C:21]([C:23]1[CH:24]=[C:25]([S:29](Cl)(=[O:31])=[O:30])[CH:26]=[CH:27][CH:28]=1)#[N:22]>>[CH3:15][N:13]([CH2:12][C:4]1[C:3]([O:2][CH3:1])=[CH:11][CH:10]=[C:9]2[C:5]=1[CH:6]=[CH:7][N:8]2[S:29]([C:25]1[CH:24]=[C:23]([CH:28]=[CH:27][CH:26]=1)[C:21]#[N:22])(=[O:31])=[O:30])[CH3:14]
N#Cc1cccc(S(=O)(=O)Cl)c1
COc1ccc2[nH]ccc2c1CN(C)C
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
25
0.25
To a solution of 1-(5-methoxy-1H-indol-4-yl)-N,N-dimethylmethanamine (15 mg, 0.07 mmol; Intermediate 97) in DMF (1 mL) NaH (4 mg, 0.15 mmol) was added at rt. The reaction mixture was stirred at rt for 15 min and 3-cyanobenzenesulphonyl chloride (22 mg, 0.11 mmol) was added. The reaction mixture was allowed to stir at rt over night. The reaction was quenched by addition of water. Purification by preparative HPLC/UV (System B) afforded the title product (4 mg, 13%) as a white solid. MS (ESI+) for C19H19N3O3S m/z 370 (M+H)+.
COc1ccc2c(ccn2S(=O)(=O)c2cccc(C#N)c2)c1CN(C)C
null
15.5
null
1,533,027
ord_dataset-8d5c200bca27407ab9febe7598e16458
null
2015-01-01T00:01:00
true
[Cl:1][C:2]1[N:3]=[C:4]([C:9]([OH:11])=O)[NH:5][C:6]=1[CH2:7][CH3:8].S(Cl)(Cl)=O.[NH2:16][C:17]1[CH:22]=[CH:21][C:20]([C:23]2[O:24][CH:25]=[C:26]([C:28]([O:30][CH3:31])=[O:29])[N:27]=2)=[CH:19][C:18]=1[CH3:32]>N1C=CC=CC=1>[Cl:1][C:2]1[N:3]=[C:4]([C:9]([NH:16][C:17]2[CH:22]=[CH:21][C:20]([C:23]3[O:24][CH:25]=[C:26]([C:28]([O:30][CH3:31])=[O:29])[N:27]=3)=[CH:19][C:18]=2[CH3:32])=[O:11])[NH:5][C:6]=1[CH2:7][CH3:8]
COC(=O)c1coc(-c2ccc(N)c(C)c2)n1
CCc1[nH]c(C(=O)O)nc1Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
c1ccncc1
O=S(Cl)Cl
null
null
null
null
null
null
null
null
null
null
null
The same operation as in Example (91c) was performed using 4-chloro-5-ethyl-1H-imidazole-2-carboxylic acid (0.12 g, 0.69 mmol), thionyl chloride (4 mL), methyl 4-amino-3-methylphenyl)-1,3-oxazole-4-carboxylate obtained in Example (109e) (0.23 g, 0.95 mmol) and pyridine (5 mL), to obtain 135 mg of the title compound as a light brown solid (50%).
CCc1[nH]c(C(=O)Nc2ccc(-c3nc(C(=O)OC)co3)cc2C)nc1Cl
null
50.3
null
1,733,808
ord_dataset-eacfee6d16d8455a93348409f1b37be4
null
2016-01-01T00:06:00
true
[Cl:1][C:2]1[N:3]=[C:4]([C:7]2[C:15]3[N:11]([C:12]([C:24]4[CH:28]=[CH:27][N:26]([CH3:29])[N:25]=4)=[C:13]4[C:19](=[O:20])[N:18]([CH3:21])[C:17](=[O:22])[N:16]([CH3:23])[C:14]4=3)[CH2:10][CH2:9][CH:8]=2)[S:5][CH:6]=1>[Pt].C(O)C.C1COCC1>[Cl:1][C:2]1[N:3]=[C:4]([CH:7]2[C:15]3[N:11]([C:12]([C:24]4[CH:28]=[CH:27][N:26]([CH3:29])[N:25]=4)=[C:13]4[C:19](=[O:20])[N:18]([CH3:21])[C:17](=[O:22])[N:16]([CH3:23])[C:14]4=3)[CH2:10][CH2:9][CH2:8]2)[S:5][CH:6]=1
Cn1ccc(-c2c3c(=O)n(C)c(=O)n(C)c3c3n2CCC=C3c2nc(Cl)cs2)n1
null
null
[Pt]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
C1CCOC1
null
null
null
null
null
null
null
null
null
null
168
A suspension of 10-(4-chlorothiazol-2-yl)-1,3-dimethyl-5-(1-methyl-1H-pyrazol-3-yl)-7,8-dihydropyrimido[4,5-a]indolizine-2,4(1H,3H)-dione (25 mg, 0.058 mmol) and 10% platinum on carbon (12 mg, 6.15 μmol) in ethanol (2.2 ml) and THF (6.6 ml) was stirred under an atmosphere of hydrogen for 7 days. The mixture was filtered and the residue rinsed thoroughly with ethanol and the combined filtrates evaporated under vacuum. Purification by chromatography on silica, eluting with 80% EtOAc/hexane afforded a crude material which was triturated with diethyl ether to afford the title compound.
Cn1ccc(-c2c3c(=O)n(C)c(=O)n(C)c3c3n2CCCC3c2nc(Cl)cs2)n1
null
null
null
1,767,115
ord_dataset-0b32b90cc77b4a3db47ad263e0bbc1a8
null
2016-01-01T00:09:00
true
[CH3:1][N:2]1[CH2:6][CH2:5][CH2:4][C@H:3]1[C:7]1[N:11]2[CH:12]=[C:13]([O:16][C@H:17]3[C:26]4[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=4)[C@@H:20]([NH2:27])[CH2:19][CH2:18]3)[CH:14]=[CH:15][C:10]2=[N:9][N:8]=1.ClC(Cl)(Cl)C[O:31][C:32](=O)[NH:33][C:34]1[N:35]([C:43]2[CH:48]=[CH:47][C:46]([Cl:49])=[C:45]([O:50][Si](C(C)C)(C(C)C)C(C)C)[CH:44]=2)[N:36]=[C:37]([C:39]([CH3:42])([CH3:41])[CH3:40])[CH:38]=1>>[C:39]([C:37]1[CH:38]=[C:34]([NH:33][C:32]([NH:27][C@@H:20]2[C:21]3[C:26](=[CH:25][CH:24]=[CH:23][CH:22]=3)[C@H:17]([O:16][C:13]3[CH:14]=[CH:15][C:10]4[N:11]([C:7]([C@@H:3]5[CH2:4][CH2:5][CH2:6][N:2]5[CH3:1])=[N:8][N:9]=4)[CH:12]=3)[CH2:18][CH2:19]2)=[O:31])[N:35]([C:43]2[CH:48]=[CH:47][C:46]([Cl:49])=[C:45]([OH:50])[CH:44]=2)[N:36]=1)([CH3:42])([CH3:40])[CH3:41]
CC(C)[Si](Oc1cc(-n2nc(C(C)(C)C)cc2NC(=O)OCC(Cl)(Cl)Cl)ccc1Cl)(C(C)C)C(C)C
CN1CCC[C@H]1c1nnc2ccc(O[C@@H]3CC[C@H](N)c4ccccc43)cn12
null
null
null
null
null
null
null
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 (193 mg, 76%) was prepared starting from Intermediate E (155 mg, 0.427 mmol) and [5-tert-butyl-2-(4-chloro-3-triisopropylsilanyloxy-phenyl)-2H-pyrazol-3-yl]-carbamic acid 2,2,2-trichloro-ethyl ester (WO2011/154734A1, which is incorporated herein by reference, 260 mg, 0.436 mmol), using analogous procedures to those described in Example 50. LCMS (Method 5): Rt 3.54 min, m/z 655.2 [MH+]. 1H NMR (400 MHz, d6-DMSO): 1.27 (9H, s), 1.82-2.26 (11H, m), 2.31-2.39 (1H, m), 3.10-3.17 (1H, m), 3.99 (1H, d, J=8.1 Hz), 4.78-4.86 (1H, m), 5.37-5.42 (1H, m), 6.33 (1H, s), 6.89-6.95 (1H, br d), 7.07-7.12 (2H, m), 7.24-7.38 (5H, m), 7.42 (1H, d, J=8.4 Hz), 7.75 (1H, dd, J=9.8 Hz), 8.12 (1H, s), 8.25 (1H, br d), 10.64 (1H, v br).
CN1CCC[C@H]1c1nnc2ccc(O[C@@H]3CC[C@H](NC(=O)Nc4cc(C(C)(C)C)nn4-c4ccc(Cl)c(O)c4)c4ccccc43)cn12
null
76
null
439,494
ord_dataset-3e8f24b5bc8e4d8bb9b6e7e89a956e12
null
1999-01-01T00:09:00
true
[CH2:1]([O:3][C:4](=[O:32])[C@@H:5]([NH:22][S:23]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)(=[O:25])=[O:24])[CH2:6][NH:7][C:8](=[O:21])[CH2:9][NH:10]C(OCC1C=CC=CC=1)=O)[CH3:2]>CCO.[Pd]>[CH2:1]([O:3][C:4](=[O:32])[C@@H:5]([NH:22][S:23]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)(=[O:24])=[O:25])[CH2:6][NH:7][C:8](=[O:21])[CH2:9][NH2:10])[CH3:2]
CCOC(=O)[C@H](CNC(=O)CNC(=O)OCc1ccccc1)NS(=O)(=O)c1ccccc1
null
null
[Pd]
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
4
Protected amine 3-5 (0.47 g, 1.01 mmol) was dissolved in 10 mL EtOH, 10% Pd/C (94 mg) was added, and the reaction was stirred under an H2 balloon. After 4 h, additional 10% Pd/C was added (94 mg), and the reaction was continued for 3 d. The mixture was filtered through Celite, concentrated, and azeotroped with CHCl3, providing amine 3-6 as a gum.
CCOC(=O)[C@H](CNC(=O)CN)NS(=O)(=O)c1ccccc1
null
null
null
211,350
ord_dataset-e0a818f9350b46cdb184d2ac404ede9f
null
1990-01-01T00:06:00
true
Br[CH2:2][CH2:3][CH2:4][O:5][CH2:6][CH2:7][O:8][CH2:9][CH2:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.[CH2:18]([NH2:25])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>C(OCC)(=O)C>[C:12]1([CH2:11][CH2:10][CH2:9][O:8][CH2:7][CH2:6][O:5][CH2:4][CH2:3][CH2:2][NH:25][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1
NCc1ccccc1
BrCCCOCCOCCCc1ccccc1
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
null
4.5
[3-[2-(3-Bromopropoxy)ethoxy]propyl]benzene (3.01 g) was added dropwise over 5 min to benzylamine (5.35 g) at 120° under nitrogen. The solution was stirred at 130° for 4.5 h, cooled, diluted with ethyl acetate (200 ml) and washed with 2N hydrochloric acid (150 ml). The aqueous phase was re-extracted with ethyl acetate (2×100 ml) and the combined organic phases washed with 8% sodium bicarbonate solution (200 ml), dried and evaporated in vacuo to give the title compound (2.58 g) as an oil. T.l.c. (System E 40:10:1) Rf 0.49
c1ccc(CCCOCCOCCCNCc2ccccc2)cc1
null
78.8
null
671,042
ord_dataset-e90cd41afe844e49875435eb99903799
null
2005-01-01T00:05:00
true
[NH2:1][C:2]1[C:7](Br)=[N:6][C:5]([Br:9])=[CH:4][N:3]=1.[C:10]([O:14][C:15]([N:17]1[CH2:22][CH2:21][NH:20][CH2:19][CH2:18]1)=[O:16])([CH3:13])([CH3:12])[CH3:11]>CCOC(C)=O>[C:10]([O:14][C:15]([N:17]1[CH2:22][CH2:21][N:20]([C:7]2[C:2]([NH2:1])=[N:3][CH:4]=[C:5]([Br:9])[N:6]=2)[CH2:19][CH2:18]1)=[O:16])([CH3:13])([CH3:11])[CH3:12]
CC(C)(C)OC(=O)N1CCNCC1
Nc1ncc(Br)nc1Br
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
120
null
2-Amino-3,5-dibromopyrazine (1.26 g, 5.0 mmol) and piperazine-1-carboxylic acid tert-butyl ester (4.64 g, 25 mmol) were placed in a dry RBF and heated with stirring to 120° C. under dry nitrogen. Molten mixture was stirred at this temperature for 6 h and cooled to room temperature. The resulting slurry was diluted with EtOAc (20 mL) and stirred for 20 min. Amine salts were removed by filtration and washed with EtOAc (3×5 mL). Filtrate was washed with pH 4 buffer (35 mL) and brine (35 mL), dried over Na2SO4 (anhydrous), filtered, and concentrated in vacuo. The residue was purified by flash chromatography (hexanes/EtOAc 7:3) gives the title compound I-3r as an off white solid (1.64 g, 92% yield).
CC(C)(C)OC(=O)N1CCN(c2nc(Br)cnc2N)CC1
null
null
null
1,753,723
ord_dataset-97eb2ab57fec4160922caae33b54d956
null
2016-01-01T00:08:00
true
Cl[C:2]1[CH:7]=[C:6]([C:8]#[N:9])[CH:5]=[C:4]([N:10]2[CH2:14][CH2:13][CH2:12][CH2:11]2)[N:3]=1.[F:15][C:16]([F:28])([F:27])[O:17][C:18]1[CH:23]=[CH:22][C:21](B(O)O)=[CH:20][CH:19]=1.C([O-])(O)=O.[Na+]>COCCOC.O>[N:10]1([C:4]2[CH:5]=[C:6]([C:8]#[N:9])[CH:7]=[C:2]([C:21]3[CH:20]=[CH:19][C:18]([O:17][C:16]([F:15])([F:27])[F:28])=[CH:23][CH:22]=3)[N:3]=2)[CH2:14][CH2:13][CH2:12][CH2:11]1
OB(O)c1ccc(OC(F)(F)F)cc1
N#Cc1cc(Cl)nc(N2CCCC2)c1
null
O=C([O-])O
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
COCCOC
O
null
null
null
null
null
null
null
null
null
100
12
A solution of nitrile 25A (2.58 g, 12.5 mmol) in DME (90 mL) was added with 4-trifluoromethoxy phenyl boronic acid (2.64 g, 1.0 mol eq,) and NaHCO3 (3.15 g, 3 mol eq,) suspended in water (45 mL). The mixture was degassed under vacuum, then Palladium Tetrakis was added (catalytic amount) and the reaction was stirred at 100° C. under inert atmosphere for 12 h. The solvent was removed under reduced pressure and water was added to the residue (80 mL). The aqueous phase was extracted with EtOAc (3×60 mL) and the combined organic layer was washed with brine (80 mL) and dried over Na2SO4. The solvent was evaporated under vacuum to afford 26C as deliquescent yellow solid (3.2 g, 9.6 mmol, 77% Yield). 1HNMR (DMSO, 400 MHz) δ 1.85 (m, 4H), 3.42 (m, 4H), 6.38 (s, 1H), 7.08 (s, 1H), 7.38 (d, 2H, J=8), 8.05 (d, 2H, J=8).
N#Cc1cc(-c2ccc(OC(F)(F)F)cc2)nc(N2CCCC2)c1
null
76.8
null
1,275,645
ord_dataset-d5c54236ecd94d61aaa071461bcfc426
null
2013-01-01T00:04:00
true
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[CH:13]=[C:12]([C:14]([F:17])([F:16])[F:15])[CH:11]=[CH:10][N:9]=1.C1C=C([Cl:24])C=C(C(OO)=O)C=1>CCOC(C)=O>[Cl:24][C:10]1[CH:11]=[C:12]([C:14]([F:17])([F:15])[F:16])[CH:13]=[C:8]([C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=2[Cl:1])[N:9]=1
O=C(OO)c1cccc(Cl)c1
FC(F)(F)c1ccnc(-c2ccccc2Cl)c1
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
null
null
To a solution of 2-(2-chlorophenyl)-4-(trifluoromethyl)pyridine (5.40 g, 21.0 mmol) in EtOAc (100 mL) was added mCPBA (7.25 g, 42.0 mmol) in EtOAc (100 mL) over 30 min and then the mixture was heated at reflux (caution: use shield) for 3 h. The reaction mixture was cooled and then washed twice with sat. aq. NaHCO3 and concentrated.
FC(F)(F)c1cc(Cl)nc(-c2ccccc2Cl)c1
null
null
null
187,994
ord_dataset-3ec273742a0345ea916ad5fd071167f2
null
1989-01-01T00:04:00
true
[BH4-].[Na+].C[O:4][C:5]([C@H:7]1[N:10]([CH2:11][C:12]2[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[CH:14][C:13]=2[O:20][CH3:21])[C:9](=[O:22])[C@H:8]1[NH:23][C:24](=[O:32])[CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)=O>O1CCCC1>[CH3:21][O:20][C:13]1[CH:14]=[C:15]([O:18][CH3:19])[CH:16]=[CH:17][C:12]=1[CH2:11][N:10]1[C@H:7]([CH2:5][OH:4])[C@H:8]([NH:23][C:24](=[O:32])[CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C:9]1=[O:22]
COC(=O)[C@@H]1[C@H](NC(=O)Cc2ccccc2)C(=O)N1Cc1ccc(OC)cc1OC
null
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
null
1.5
Under ice-cooling and stirring, 12 ml of an aqueous solution containing 570 mg of sodium borohydride is added to a solution of 2.06 g of cis-1-(2,4-dimethoxybenzyl)-3-phenylacetamido-2-oxoazetidine-4-carboxylic acid methyl ester in 24 ml of tetrahydrofuran. The reaction mixture is stirred for 30 minutes under ice-cooling and then for 1.5 hours at room temperature. The tetrahydrofuran is distilled off in vacuo and an aqueous sodium chloride solution and ethyl acetate are added to the residue. The resulting ethyl acetate layer is separated and washed successively with an aqueous sodium hydrogen carbonate and an aqueous sodium chloride. It is then dried over magnesium sulfate and the solvent is distilled off in vacuo. Ether is added to the residue and the precipitated crystals are collected by filtration to give 1.75 g (91%) of cis-1-(2,4-dimethoxybenzyl)-4-hydroxymethyl-3-phenylacetamido-2-oxoazetidine, m.p. 152°-154° C.
COc1ccc(CN2C(=O)[C@@H](NC(=O)Cc3ccccc3)[C@H]2CO)c(OC)c1
null
91.1
null
847,635
ord_dataset-171b840ae6e84e45bab43b987d09f5c7
null
2008-01-01T00:11:00
true
[ClH:1].[CH:2]1([N:6]2[CH2:11][CH2:10][CH:9]([O:12][C:13]3[CH:21]=[CH:20][C:16]([C:17](O)=[O:18])=[CH:15][CH:14]=3)[CH2:8][CH2:7]2)[CH2:5][CH2:4][CH2:3]1>S(Cl)(Cl)=O>[ClH:1].[CH:2]1([N:6]2[CH2:11][CH2:10][CH:9]([O:12][C:13]3[CH:21]=[CH:20][C:16]([C:17]([Cl:1])=[O:18])=[CH:15][CH:14]=3)[CH2:8][CH2:7]2)[CH2:5][CH2:4][CH2:3]1
O=C(O)c1ccc(OC2CCN(C3CCC3)CC2)cc1
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O=S(Cl)Cl
null
null
null
null
null
null
null
null
null
null
null
null
4-[(1-Cyclobutyl-4-piperidinyl)oxy]benzoic acid hydrochloride (D24) (0.20 g) was dissolved in thionyl chloride (10 ml) and heated under reflux for 1.5 h. The thionyl chloride was removed by evaporation and the residue evaporated from DCM (3×10 ml) to give the title compound (D25) (0.21 g).
O=C(Cl)c1ccc(OC2CCN(C3CCC3)CC2)cc1
null
198.3
null
937,419
ord_dataset-90b0aa1f83334a02919b2be3a1c04542
null
2010-01-01T00:02:00
true
[Cl:1][C:2]1[CH:3]=[C:4]([CH:26]=[CH:27][C:28]=1[F:29])[NH:5][C:6]1[C:15]2[C:10](=[CH:11][C:12]([O:24][CH3:25])=[CH:13][C:14]=2[O:16][CH2:17][C@@H:18]2[NH:22][CH2:21][C@@H:20]([OH:23])[CH2:19]2)[N:9]=[CH:8][N:7]=1.[CH3:30][O:31][CH2:32][C:33](O)=[O:34]>>[Cl:1][C:2]1[CH:3]=[C:4]([CH:26]=[CH:27][C:28]=1[F:29])[NH:5][C:6]1[C:15]2[C:10](=[CH:11][C:12]([O:24][CH3:25])=[CH:13][C:14]=2[O:16][CH2:17][C@@H:18]2[N:22]([C:33](=[O:34])[CH2:32][O:31][CH3:30])[CH2:21][C@@H:20]([OH:23])[CH2:19]2)[N:9]=[CH:8][N:7]=1
COc1cc(OC[C@H]2C[C@H](O)CN2)c2c(Nc3ccc(F)c(Cl)c3)ncnc2c1
COCC(=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
null
null
null
The procedure described in Example 20 was repeated using (3S,5R)-5-[({4-[3-chloro-4-fluoroanilino]-7-methoxyquinazolin-5-yl}oxy)methyl]pyrrolidin-3-ol (120 mg) with methoxyacetic acid (24 μl) to give the title compound as a white solid in 60% yield; NMR spectrum (DMSO-d6) 9.96 (s, 1H), 8.45 (s, 1H), 8.17-8.14 (m, 1H), 7.76-7.72 (m, 1H), 7.45 (t, 1H), 6.83 (s, 2H), 5.10 (m, 1H), 4.73-4.69 (m, 1H), 4.47-4.38 (m, 2H), 4.25 (dd, 1H), 4.10-3.98 (m, 2H), 3.94 (s, 3H), 3.51 (dd, 1H), 3.40 (s, 1H), 3.29 (s, 3H), 2.05-2.02 (m, 2H); Mass spectrum MH+ 491.
COCC(=O)N1C[C@@H](O)C[C@@H]1COc1cc(OC)cc2ncnc(Nc3ccc(F)c(Cl)c3)c12
null
60
null
1,709,475
ord_dataset-3f2a531ffbae4b9eb1048afcd7953beb
null
2016-01-01T00:04:00
true
[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]2[N:10]=[CH:9][N:8]([CH2:11][CH2:12]O)[C:7]=2[CH:14]=1.C(Br)(Br)(Br)[Br:16].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>C(Cl)Cl>[Br:16][CH2:12][CH2:11][N:8]1[C:7]2[CH:14]=[C:3]([O:2][CH3:1])[CH:4]=[CH:5][C:6]=2[N:10]=[CH:9]1
BrC(Br)(Br)Br
COc1ccc2ncn(CCO)c2c1
null
c1ccc(P(c2ccccc2)c2ccccc2)cc1
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
2
To a solution of 2-(6-methoxy-1H-benzo[d]imidazol-1-yl)ethanol (200 mg, 1.04 mmol) in DCM (6.0 mL), CBr4 (397 mg, 1.20 mmol) was added, then the reaction mixture was cooled to 0° C. and PPh3 (314 mg, 1.20 mmol) was added. After stirring at rt for 2 h the solvent was removed under reduced pressure to yield the title compound as a brown oil, which was used us such in the next step. LC-MS conditions B: tR=0.42 min, [M(79Br)+H]+=255.08.
COc1ccc2ncn(CCBr)c2c1
null
null
null
128,765
ord_dataset-d6b60b593b1c4668bc6843cd65a5d232
null
1985-01-01T00:04:00
true
[NH2:1][C:2]1[C:3](=[O:16])[NH:4][C:5]2[CH2:6][CH2:7][C:8]3[CH:15]=[CH:14][CH:13]=[CH:12][C:9]=3[C:10]=2[CH:11]=1.N1C=CC=CC=1.[C:23](Cl)(=[O:25])[CH3:24]>C(Cl)(Cl)Cl>[C:23]([NH:1][C:2]1[C:3](=[O:16])[NH:4][C:5]2[CH2:6][CH2:7][C:8]3[CH:15]=[CH:14][CH:13]=[CH:12][C:9]=3[C:10]=2[CH:11]=1)(=[O:25])[CH3:24]
Nc1cc2c([nH]c1=O)CCc1ccccc1-2
CC(=O)Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)Cl
c1ccncc1
null
null
null
null
null
null
null
null
null
null
null
To 2.0 gm of 2-amino-5,6-dihydrobenzo[f]quinolin-3(4H)-one, in 100 ml of chloroform containing 1 ml of pyridine add 0.80 gm of acetyl chloride. Stir the reaction at room temperature for 5 hours. Filter and wash the solution with water. Remove the solvent by stripping to give the title compound.
CC(=O)Nc1cc2c([nH]c1=O)CCc1ccccc1-2
null
null
null
804,404
ord_dataset-ed846b4b229e4bb09ad9dba95ad7ebeb
null
2008-01-01T00:01:00
true
[NH2:1][CH:2]1[CH:7]([CH:8]=O)[CH:6]=[N:5][C:4]([S:10][CH2:11][CH2:12][CH2:13][CH3:14])=[N:3]1.[CH2:15]([O:17][CH2:18][C:19](OCC)=[O:20])[CH3:16].CC(C)([O-])C.[K+]>C1(C)C=CC=CC=1>[CH2:11]([S:10][C:4]1[N:5]=[CH:6][CH:7]2[CH:8]=[C:18]([O:17][CH2:15][CH3:16])[C:19](=[O:20])[NH:1][CH:2]2[N:3]=1)[CH2:12][CH2:13][CH3:14]
CCCCSC1=NC(N)C(C=O)C=N1
CCOCC(=O)OCC
null
CC(C)(C)[O-]
[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
25
48
4-Amino-2-butylsulfanyl-4,5-dihydro-pyrimidine-5-carbaldehyde (3 g, 14.2 mmol, funished by scaleup) and ethyl ethoxyacetate (2.34 g, 2.4 ml, 17.75 mmol) were stirred in 80 ml toluene at 0°-5° C. under nitrogen. Potassium t-butoxide (1.75 g, 15.6 mmol) was added gradually. The mixture was stirred to ambient temperature, and then to 65° C. for 48 hours. An additional 20 ml of toluene and 2.4 ml ethyl ethoxyacetate were added and the reaction was maintained at 65° C. over the weekend. The reaction mixture was concentrated in vacuo and triturated with EtOAc to remove the remaining starting aldehyde. The remaining solid was further triturated with chloroform to remove additional impurities. 3.66 g of 2-Butylsulfanyl-6-ethoxy-8,8a-dihydro-4aHpyrido[2,3-d]pyrimidin-7-one (1A) of a purity greater than 80% as judged by MS/HPLC and NMR was collected.
CCCCSC1=NC2NC(=O)C(OCC)=CC2C=N1
null
null
null
488,170
ord_dataset-37b0416f244344a08cf357e851eedf2a
null
2001-01-01T00:01:00
true
C[O:2][C:3]1[N:10]=[C:9]([O:11][CH3:12])[CH:8]=[CH:7][C:4]=1[CH:5]=[O:6].B(Cl)(Cl)Cl>C(Cl)Cl>[OH:2][C:3]1[N:10]=[C:9]([O:11][CH3:12])[CH:8]=[CH:7][C:4]=1[CH:5]=[O:6]
COc1ccc(C=O)c(OC)n1
null
null
ClB(Cl)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
20
8.4 g (0.05 mol) 2,6-dimethoxy-nicotinaldehyde was solved in 75 ml methylene chloride. At 0° C. (0.2 mol) BCl3 as 1 molar solution in methylene chloride 200 ml was added and stirred at room temperature for 20 h. The mixture was poured on ice/water, neutralized and extracted with CH2Cl2. Evaporation of the solvent affords 5.7 g (75%) of the title compound.
COc1ccc(C=O)c(O)n1
null
74.4
null
882,744
ord_dataset-3592bd645cd143ee8274cd0d834ae581
null
2009-01-01T00:05:00
true
Cl.[NH2:2][C:3]1[CH:33]=[CH:32][C:6]2[NH:7][C:8]([C:13]3[C:14](=[O:31])[C:15]([CH3:30])([CH2:24][CH2:25][C@@H:26]([CH3:29])[CH2:27][CH3:28])[C:16]4[C:21]([C:22]=3[OH:23])=[CH:20][CH:19]=[CH:18][CH:17]=4)=[N:9][S:10](=[O:12])(=[O:11])[C:5]=2[CH:4]=1.[S:34](Cl)([CH3:37])(=[O:36])=[O:35].N1C=CC=CC=1>CC(C)=O>[OH:23][C:22]1[C:21]2[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=2)[C:15]([CH3:30])([CH2:24][CH2:25][C@@H:26]([CH3:29])[CH2:27][CH3:28])[C:14](=[O:31])[C:13]=1[C:8]1[NH:7][C:6]2[CH:32]=[CH:33][C:3]([NH:2][S:34]([CH3:37])(=[O:36])=[O:35])=[CH:4][C:5]=2[S:10](=[O:12])(=[O:11])[N:9]=1
CC[C@H](C)CCC1(C)C(=O)C(C2=NS(=O)(=O)c3cc(N)ccc3N2)=C(O)c2ccccc21
CS(=O)(=O)Cl
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(C)=O
c1ccncc1
null
null
null
null
null
null
null
null
null
null
null
A solution of Example 43F (0.119 g, 0.240 mmol), mesyl chloride (0.075 mL, 0.970 mmol), and pyridine (0.157 mL, 1.94 mmol) in acetone (3 mL) was stirred at 25° C. for 18 hours. The solution was partitioned between ethyl acetate and dilute citric acid and the layers were separated. The ethyl acetate layer was dried with sodium sulfate, filtered, and concentrated in vacuo. The residue was chromatographed on silica gel eluting with methylene chloride and 2.5% methanol in methylene chloride to give a yellow solid.
CC[C@H](C)CCC1(C)C(=O)C(C2=NS(=O)(=O)c3cc(NS(C)(=O)=O)ccc3N2)=C(O)c2ccccc21
null
null
null
1,567,568
ord_dataset-4e54080057a44c3887653391e24c90b6
null
2015-01-01T00:03:00
true
[C:1]([CH2:4][CH2:5][CH2:6][N:7]([CH3:66])[C@H:8]([C:12]([NH:14][C@H:15]([C:19]([N:21]([C@@H:23]([C@@H:62]([CH3:65])[CH2:63][CH3:64])[C@H:24]([O:60][CH3:61])[CH2:25][C:26]([N:28]1[CH2:32][CH2:31][CH2:30][C@H:29]1[C@H:33]([O:58][CH3:59])[C@@H:34]([CH3:57])[C:35]([NH:37][C@@H:38]([CH2:50][C:51]1[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=1)[CH2:39][S:40]([CH2:43][C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1)(=[O:42])=[O:41])=[O:36])=[O:27])[CH3:22])=[O:20])[CH:16]([CH3:18])[CH3:17])=[O:13])[CH:9]([CH3:11])[CH3:10])([OH:3])=O.Cl.[O:68]=[C:69]1[CH:73]=[CH:72][C:71](=[O:74])[N:70]1[CH2:75][CH2:76][CH2:77][CH2:78][CH2:79][C:80]([NH:82][NH2:83])=[O:81]>>[O:74]=[C:71]1[CH:72]=[CH:73][C:69](=[O:68])[N:70]1[CH2:75][CH2:76][CH2:77][CH2:78][CH2:79][C:80]([NH:82][NH:83][C:1](=[O:3])[CH2:4][CH2:5][CH2:6][N:7]([CH3:66])[C@H:8]([C:12]([NH:14][C@H:15]([C:19]([N:21]([C@@H:23]([C@@H:62]([CH3:65])[CH2:63][CH3:64])[C@H:24]([O:60][CH3:61])[CH2:25][C:26]([N:28]1[CH2:32][CH2:31][CH2:30][C@H:29]1[C@H:33]([O:58][CH3:59])[C@@H:34]([CH3:57])[C:35]([NH:37][C@@H:38]([CH2:50][C:51]1[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=1)[CH2:39][S:40]([CH2:43][C:44]1[CH:45]=[CH:46][CH:47]=[CH:48][CH:49]=1)(=[O:42])=[O:41])=[O:36])=[O:27])[CH3:22])=[O:20])[CH:16]([CH3:17])[CH3:18])=[O:13])[CH:9]([CH3:10])[CH3:11])=[O:81]
CC[C@H](C)[C@@H]([C@@H](CC(=O)N1CCC[C@H]1[C@H](OC)[C@@H](C)C(=O)N[C@@H](Cc1ccccc1)CS(=O)(=O)Cc1ccccc1)OC)N(C)C(=O)[C@@H](NC(=O)[C@H](C(C)C)N(C)CCCC(=O)O)C(C)C
NNC(=O)CCCCCN1C(=O)C=CC1=O
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
7.4 mg (7.9 mmol) of N-(3-carboxypropyl)-N-methyl-L-valyl-N-[(3R,4S,5S)-1-{(2S)-2-[(1R,2R)-3-{[(2S)-1-(benzylsulphonyl)-3-phenylpropan-2-yl]amino}-1-methoxy-2-methyl-3-oxopropyl]pyrrolidin-1-yl}-3-methoxy-5-methyl-1-oxoheptan-4-yl]-N-methyl-L-valinamide and 6.2 mg (23.5 mmol) of 6-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)hexanehydrazide hydrochloride were coupled and worked up in analogy to Intermediate 157. 6.9 mg (74% of theory) of the title compound were obtained as a solid.
CC[C@H](C)[C@@H]([C@@H](CC(=O)N1CCC[C@H]1[C@H](OC)[C@@H](C)C(=O)N[C@@H](Cc1ccccc1)CS(=O)(=O)Cc1ccccc1)OC)N(C)C(=O)[C@@H](NC(=O)[C@H](C(C)C)N(C)CCCC(=O)NNC(=O)CCCCCN1C(=O)C=CC1=O)C(C)C
null
null
null
1,331,765
ord_dataset-cfad8b3f00044bcda60a96b019f09872
null
2013-01-01T00:08:00
true
Cl[C:2]1[O:3][C:4]2[CH:10]=[CH:9][C:8]([N+:11]([O-:13])=[O:12])=[CH:7][C:5]=2[N:6]=1.C([Sn](CCCC)(CCCC)[C:19]1[S:20][CH:21]=[CH:22][CH:23]=1)CCC.C(OCC)(=O)C>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[N+:11]([C:8]1[CH:9]=[CH:10][C:4]2[O:3][C:2]([C:19]3[S:20][CH:21]=[CH:22][CH:23]=3)=[N:6][C:5]=2[CH:7]=1)([O-:13])=[O:12]
O=[N+]([O-])c1ccc2oc(Cl)nc2c1
CCCC[Sn](CCCC)(CCCC)c1cccs1
null
c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOC(C)=O
C1COCCO1
null
null
null
null
null
null
null
null
null
100
null
A mixture of 2-chloro-5-nitrobenzo[d]oxazole (404 mg, 2.04 mmol), 2-(tributylstannyl)-thiophene (648 μL, 2.04 mmol) and tetrakis(triphenylphosphine)palladium (0) (40.8 mg) in dioxane (12.2 mL) was heated at 100° C. for 16 h under nitrogen. Ethyl acetate was added, the organic layer was washed with water, dried over anhydrous MgSO4 and evaporated. The resulting solid was purified by column chromatography eluting with ethyl acetate/hexanes 10:90 v/v, and then purified by reverse phase HPLC to afford 3 mg (2%) of the title product (LCMS RT=6.95 min)
O=[N+]([O-])c1ccc2oc(-c3cccs3)nc2c1
null
0.6
null
1,564,450
ord_dataset-4e54080057a44c3887653391e24c90b6
null
2015-01-01T00:03:00
true
[Br:1][C:2]1[CH:3]=[C:4]2[C:10](I)=[CH:9][N:8]([CH3:12])[C:5]2=[N:6][CH:7]=1.[CH3:13][N:14]1[CH2:19][CH2:18][NH:17][CH2:16][CH2:15]1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].C(O)CO>C(O)(C)C.[Cu]I>[Br:1][C:2]1[CH:3]=[C:4]2[C:10]([N:17]3[CH2:18][CH2:19][N:14]([CH3:13])[CH2:15][CH2:16]3)=[CH:9][N:8]([CH3:12])[C:5]2=[N:6][CH:7]=1
Cn1cc(I)c2cc(Br)cnc21
CN1CCNCC1
null
[Cu]I
O=P([O-])([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(C)O
OCCO
null
null
null
null
null
null
null
null
null
25
null
A solution of 5-bromo-3-iodo-1-methyl-1H-pyrrolo[2,3-b]pyridine (150 mg, 0.445 mmol), 1-methylpiperazine (356.7 mg, 3.56 mmol), copper(I) iodide (84.8 mg, 0.445 mmol), K3PO4 (378 mg, 1.78 mmol), 1,2-ethanediol (138 mg, 2.225 mmol) in isopropyl alcohol (5 mL) in a sealed tubes was heated at 70° C. for 2 days. After cooling to room temperature, the reaction mixture was filtered through celite. The filtrate was concentrated in vacuo. The residue was taken up in EtOAc and the solution was washed with saturated NaHCO3, dried and concentrated. Purification by flash chromatography afforded the title compound. LCMS-ESI+: calc'd for C13H17BrN4 309.1 (M+H+); Found: 309.1 (M+H+).
CN1CCN(c2cn(C)c3ncc(Br)cc23)CC1
null
null
null
1,751,514
ord_dataset-97eb2ab57fec4160922caae33b54d956
null
2016-01-01T00:08:00
true
[H-].[Na+].[F:3][C:4]([F:8])([F:7])[CH2:5][OH:6].Br[C:10]1[S:11][C:12]([C:15]([O:17][CH3:18])=[O:16])=[CH:13][N:14]=1.[OH-].[Na+]>C(OCC)(=O)C.O1CCCC1>[F:3][C:4]([F:8])([F:7])[CH2:5][O:6][C:10]1[S:11][C:12]([C:15]([O:17][CH3:18])=[O:16])=[CH:13][N:14]=1
COC(=O)c1cnc(Br)s1
OCC(F)(F)F
null
[H-]
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
CCOC(C)=O
null
null
null
null
null
null
null
null
null
null
null
To a tetrahydrofuran solution (5.0 mL) of sodium hydride (465 mg, 11.6 mmol) and 2,2,2-trifluoroethanol (1.70 mL, 23.3 mmol), methyl 2-bromothiazole-5-carboxylate (517 mg, 2.33 mmol) was added and the resultant mixture was stirred at room temperature for 2 hours. After completion of the reaction, 1 M sodium hydroxide aqueous solution was added to the reaction solution and extraction from the resultant mixture with ethyl acetate was performed. The organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product of the title compound (444 mg).
COC(=O)c1cnc(OCC(F)(F)F)s1
null
79
null
750,813
ord_dataset-844a22e1fcab44a5b59c5e2922b2855a
null
2007-01-01T00:01:00
true
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4](F)[CH:3]=1.[OH:12][C:13]1[CH:14]=[C:15]([C@@H:19]([NH:21][C:22](=[O:28])[O:23][C:24]([CH3:27])([CH3:26])[CH3:25])[CH3:20])[CH:16]=[CH:17][CH:18]=1.C(=O)([O-])[O-].[K+].[K+].CN(C)C=O>O>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]([CH:3]=1)[O:12][C:13]1[CH:14]=[C:15]([C@@H:19]([NH:21][C:22](=[O:28])[O:23][C:24]([CH3:27])([CH3:26])[CH3:25])[CH3:20])[CH:16]=[CH:17][CH:18]=1
O=[N+]([O-])c1ccc(Cl)cc1F
C[C@H](NC(=O)OC(C)(C)C)c1cccc(O)c1
null
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
O
null
null
null
null
null
null
null
null
null
100
1
A mixture of 4-chloro-2-fluoronitrobenzene (10.4 g, 59.2 mmols), tert-butyl(1S)-1-(3-hydroxyphenyl)ethylcarbamate (13.4 g, 56.5 mmols), potassium carbonate (9.4 g, 68 mmols) and N,N-dimethylformamide (150 ml) was stirred at 100° C. for 1 hour. The reaction mixture was cooled, poured into water, and extracted with ethyl acetate. The extract was washed with water and brine, and then dried with anhydrous magnesium sulfate, and the solvent was evaporated away. The residue was purified through silica gel column chromatography, and the resulting crystal was re-crystallized from hexane/ethyl acetate to give a crystal of tert-butyl(1S)-(-)-1-[3-(5-chloro-2-nitrophenoxy)phenyl]ethylcarbamate (15.7 g, 71%).
C[C@H](NC(=O)OC(C)(C)C)c1cccc(Oc2cc(Cl)ccc2[N+](=O)[O-])c1
null
70.7
null
751,324
ord_dataset-844a22e1fcab44a5b59c5e2922b2855a
null
2007-01-01T00:01:00
true
[CH2:1]([O:4][C:5]1[CH:10]=[CH:9][C:8]([Br:11])=[CH:7][C:6]=1[N+:12]([O-])=O)[CH:2]=[CH2:3].[NH4+].[Cl-].C(O)C>[Fe].O>[CH2:1]([O:4][C:5]1[CH:10]=[CH:9][C:8]([Br:11])=[CH:7][C:6]=1[NH2:12])[CH:2]=[CH2:3]
C=CCOc1ccc(Br)cc1[N+](=O)[O-]
null
null
[Fe]
[Cl-]
[NH4+]
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
null
null
A mixture of Example 66A (5.06 g, 19.69 mmol), iron powder (11.02 g, 196.9 mmol), NH4Cl (0.53 g, 9.85 mmol), ethanol (160 mL), and water (40 mL) were heated at 80° C. for 6 hours. The solution was filtered, concentrated with silica gel powder (18 g), and purified by flash chromatography eluting with 10% ethyl acetate in hexanes (1 L) to give the title compound (4.53 g, 97%). MS (DCI) m/z 227.91 (M+H)+; 1H NMR (300 MHz, CDCl3) δ ppm 4.54 (d, J=5.43 Hz, 2 H) 5.29 (dd, J=10.51, 1.36 Hz, 1 H) 5.40 (dd, J=17.46, 1.53 Hz, 1 H) 6.09 (m, 1 H) 6.65 (d, J=8.48 Hz, 1 H) 6.84 (m, 1 H) 6.91 (d, J=2.37 Hz, 1 H).
C=CCOc1ccc(Br)cc1N
null
100.9
null
1,388,111
ord_dataset-31641fb65b34430fa7435229b949b604
null
2014-01-01T00:01:00
true
[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6](SC)=[N:7][C:8]([C:12]([F:21])([F:20])[C:13]3[CH:18]=[CH:17][C:16]([F:19])=[CH:15][N:14]=3)=[N:9]2)=[CH:4][CH:3]=1.ClC1C=C(C=CC=1)C(OO)=O.[CH3:35][C:36]1[NH:40][N:39]=[C:38]([NH2:41])[CH:37]=1>C(Cl)Cl.C1COCC1>[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6]([NH:41][C:38]3[CH:37]=[C:36]([CH3:35])[NH:40][N:39]=3)=[N:7][C:8]([C:12]([F:21])([F:20])[C:13]3[CH:18]=[CH:17][C:16]([F:19])=[CH:15][N:14]=3)=[N:9]2)=[CH:4][CH:3]=1
Cc1cc(N)n[nH]1
CSc1nc(C(F)(F)c2ccc(F)cn2)nc2cc(Br)ccc12
null
O=C(OO)c1cccc(Cl)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
ClCCl
null
null
null
null
null
null
null
null
null
0
1.33
To 7-bromo-2-(difluoro(5-fluoropyridin-2-yl)methyl)-4-(methylthio)quinazoline (100 mg, 0.25 mmol) in DCM (3 mL) at 0° C. was added 70% meta-chloroperoxybenzoic acid (74 mg, 0.30 mmol) and the mixture was stirred at 0° C. for 80 min. Then additional 70% meta-chloroperoxybenzoic acid (70%, 15 mg, 0.086 mmol) was added and the mixture was stirred at 0° C. for 10 min. The mixture was diluted with DCM (10 mL), washed with saturated aq NaHCO3 (20 mL) and saturated aq sodium thiosulfate (20 mL), dried over Na2SO4 and concentrated under reduced pressure. To the residue (133 mg) at rt was added 5-methyl-1H-pyrazol-3-amine (92 mg, 0.96 mmol) in THF (3 mL). The mixture was stirred for 40 min and then concentrated under reduced pressure. The residue was purified by preparative HPLC (Phenomenex C-18 reverse phase column, eluted with gradient of solvent B=0.05% AcOH/ACN and solvent A=5% ACN/0.05% AcOH/H2O) to afford 7-bromo-2-(difluoro(5-fluoropyridin-2-yl)methyl)-N-(5-methyl-1H-pyrazol-3-yl)quinazolin-4-amine (4.42 mg, 3.1%). 1H NMR (300 MHz, DMSO-d6) δ 12.09-12.33 (m, 1H), 10.73-10.99 (m, 1H), 8.66 (s, 2H), 8.00 (d, J=5.5 Hz, 3H), 7.74-7.87 (m, 1H), 5.95 (br s, 1H), 2.16 (s, 3H); LC-MS (ESI) m/z 449/451 (M+H)+.
Cc1cc(Nc2nc(C(F)(F)c3ccc(F)cn3)nc3cc(Br)ccc23)n[nH]1
null
3.9
null
965,776
ord_dataset-03ba810b7f464a06b5d8787af2e8b64e
null
2010-01-01T00:06:00
true
C(Cl)(Cl)Cl.[N+:5]([C:8]1[CH:15]=[CH:14][C:11]([CH:12]=[O:13])=[C:10]([F:16])[CH:9]=1)([O-:7])=[O:6].[CH2:17]([Si](C)(C)C)[CH:18]=[CH2:19]>C(OCC)(=O)C.[Ti](Cl)(Cl)(Cl)Cl>[F:16][C:10]1[CH:9]=[C:8]([N+:5]([O-:7])=[O:6])[CH:15]=[CH:14][C:11]=1[CH:12]([OH:13])[CH2:19][CH:18]=[CH2:17]
C=CC[Si](C)(C)C
O=Cc1ccc([N+](=O)[O-])cc1F
null
Cl[Ti](Cl)(Cl)Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)Cl
CCOC(C)=O
null
null
null
null
null
null
null
null
null
25
0.17
0.65 ml of titanium tetrachloride was added to a chloroform (12 ml) solution of 2.00 g of 4-nitro-2-fluoro-benzaldehyde produced according to the method described in U.S. Pat. No. 6,239,152, and the reaction liquid was stirred at room temperature for 10 minutes, and then 2.4 ml of allyl-trimethyl-silane was added to it, and the reaction liquid was stirred at room temperature for 20 minutes. The reaction liquid was diluted with ethyl acetate, washed with water and saturated saline, and dried with anhydrous sodium sulfate. The solvent was evaporated away under reduced pressure, and the residue was purified through silica gel column chromatography (developing solvent: hexane/ethyl acetate=3/1) to obtain the entitled compound as an orange solid.
C=CCC(O)c1ccc([N+](=O)[O-])cc1F
null
null
null
606,631
ord_dataset-273fda773e864aaf9b71a30a2d9f2162
null
2003-01-01T00:08:00
true
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([CH:9]([C:20]2[CH:25]=[CH:24][C:23]([O:26][CH2:27][CH:28]3[O:30][CH2:29]3)=[C:22]([CH3:31])[CH:21]=2)[CH:10]2[C:19]3[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=3)[CH2:13][CH2:12][CH2:11]2)=[CH:5][CH:4]=1.[CH2:32]([NH2:36])[CH2:33][CH2:34][CH3:35]>C(O)C>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([CH:9]([C:20]2[CH:25]=[CH:24][C:23]([O:26][CH2:27][CH:28]([OH:30])[CH2:29][NH:36][CH2:32][CH2:33][CH2:34][CH3:35])=[C:22]([CH3:31])[CH:21]=2)[CH:10]2[C:19]3[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=3)[CH2:13][CH2:12][CH2:11]2)=[CH:5][CH:4]=1
COc1ccc(C(c2ccc(OCC3CO3)c(C)c2)C2CCCc3ccccc32)cc1
CCCCN
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
null
A mixture of (4-methoxyphenyl)-(3-methyl-4-(2,3-epoxypropyloxy)phenyl)-1,2,3,4-tetrahydronaphth-1-yl-methane (300 mg, 0.001 mol), n-butyl amine (1.0 m, 0.01 mol) and ethanol (15 ml) was refluxed for 8 hrs. Ethanol was distilled off and the residue was passed through a basic alumina column using hexane:ethyl acetate as the eluent. Solvent was distilled off to give the title compound. Yield 212 mg, (60.05%).
CCCCNCC(O)COc1ccc(C(c2ccc(OC)cc2)C2CCCc3ccccc32)cc1C
null
null
null
380,891
ord_dataset-993feac5ecf54388aa6326a220e46db3
null
1997-01-01T00:10:00
true
[CH:1]([C:3]1[CH:4]=[C:5]([S:14]([OH:17])(=[O:16])=[O:15])[C:6]2[CH:7]=[CH:8][CH:9]=[N:10][C:11]=2[C:12]=1[OH:13])=[O:2].C(=O)([O-])[O-:19].[Na+].[Na+].[K]>>[C:1]([C:3]1[CH:4]=[C:5]([S:14]([OH:17])(=[O:16])=[O:15])[C:6]2[CH:7]=[CH:8][CH:9]=[N:10][C:11]=2[C:12]=1[OH:13])([OH:19])=[O:2]
O=Cc1cc(S(=O)(=O)O)c2cccnc2c1O
O=C([O-])[O-]
null
[K]
[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
52
0.92
The 7-formyl-8-hydroxyquinoline-5-sulfonic acid (15 mmol, 3.80 g) was dissolved in sodium carbonate solution (34.5 mmol, 3.66 g in 200 mL of H2O). The solution was stirred and heated at 52° C. (oil bath). Then to the hot solution potassium permaganate (37.5 mmol, 5.94 g) was added. The temperature was increased to 68° C. The stirring and heating (60°-65° C.) was continued for 55 minutes. After that time the reaction mixture was filtered, and the solid was washed with sodium carbonate solution followed by water. The filtrate was concentrated under reduced pressure, acidified with 50% sulfuric acid (pH 3) and left for crystallization. The precipitate was filtered off, washed with a small amount of water and dried to give 1.96 g of 7-carboxy-8-hydroxyquinoline-5-sulfonic acid (48.5%).
O=C(O)c1cc(S(=O)(=O)O)c2cccnc2c1O
null
48.5
null
418,927
ord_dataset-94e21e9990034c729ea727e7d2ab0eb0
null
1998-01-01T00:12:00
true
C1(N=C=NC2CCCCC2)CCCCC1.[C:16]([NH:20][S:21]([C:24]1[CH:33]=[C:32]([NH:34][NH2:35])[CH:31]=[CH:30][C:25]=1[C:26]([O:28][CH3:29])=[O:27])(=[O:23])=[O:22])([CH3:19])([CH3:18])[CH3:17].[C:36]1([CH2:42][C:43](O)=[O:44])[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1>CN(C)C1C=CN=CC=1.C(Cl)Cl>[C:16]([NH:20][S:21]([C:24]1[CH:33]=[C:32]([NH:34][NH:35][C:43](=[O:44])[CH2:42][C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[CH:31]=[CH:30][C:25]=1[C:26]([O:28][CH3:29])=[O:27])(=[O:23])=[O:22])([CH3:19])([CH3:17])[CH3:18]
O=C(O)Cc1ccccc1
COC(=O)c1ccc(NN)cc1S(=O)(=O)NC(C)(C)C
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
25
15
1.5 g (7.3 mmol) of dicyclohexylcarbodiimide (DCC) are added to a solution of 2.0 g (6.6 mmol) of methyl 2-(N-tert-butylsulfamoyl)-4-hydrazinobenzoate, 0.9 g (6.6 mmol) of phenylacetic acid and 0.03 g of 4-dimethylaminopyridine (DMAP) in 20 ml of CH2Cl2 at 0° C. The mixture is stirred at 25° C. for 15 hours, the solid is filtered off with suction and the organic phase is washed successively with water, 1N HCl and NaHCO3 solution, dried and evaporated. This gives 1.6 g (58% of theory) of methyl 2-(N-tert-butylsulfamoyl)-4-(2-phenylacetyl-hydrazino)benzoate with the following nuclear magnetic resonance data:
COC(=O)c1ccc(NNC(=O)Cc2ccccc2)cc1S(=O)(=O)NC(C)(C)C
null
null
null
178,376
ord_dataset-4d84abdf99524e0fb6c42ab2a3300790
null
1988-01-01T00:10:00
true
C[Li].[N+:3]([C:6]1[CH:49]=[CH:48][CH:47]=[CH:46][C:7]=1[CH2:8][O:9][C:10]([CH:12]([PH:27]([C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1)([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)[N:13]1[CH:16]([CH2:17][C:18]([C:20]2C=CC=CC=2)=S)[CH2:15][C:14]1=[O:26])=[O:11])([O-:5])=[O:4].[NH4+].[Cl-].CC[O:54]CC>C1COCC1.C(Cl)Cl>[N+:3]([C:6]1[CH:49]=[CH:48][CH:47]=[CH:46][C:7]=1[CH2:8][O:9][C:10]([CH:12]([PH:27]([C:34]1[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=1)([C:28]1[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1)[C:40]1[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=1)[N:13]1[CH:16]([CH2:17][C:18]([CH3:20])=[O:54])[CH2:15][C:14]1=[O:26])=[O:11])([O-:5])=[O:4]
CCOCC
O=C(OCc1ccccc1[N+](=O)[O-])C(N1C(=O)CC1CC(=S)c1ccccc1)[PH](c1ccccc1)(c1ccccc1)c1ccccc1
null
[Cl-]
[Li]C
[NH4+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
C1CCOC1
null
null
null
null
null
null
null
null
null
null
0.08
Cuprous iodide (0.380 g) is suspended in 10 ml anhydrous ether under N2, in a dry flask and cooled to 0°. Methyl lithium (3.0 ml, 1.3 Molar) is added dropwise and the mixture is stirred at 0° for 5 min to give a yellow suspension. The mixture is then cooled to -50°. 1-(o-nitrobenzyloxycarbonyl-triphenylphosphoranylmethyl)-4-(phenylthiocarbonylmethyl)-2-azetidinone (0.674 g) in 10 ml THF is added dropwise over 5 min. The mixture is stirred at -50° for 5 min and allowed to come to -20° over 20 min and stirred at -20° for 5 min. Saturated NH4Cl solution 5 ml is added and the mixture is diluted with CH2Cl2. Stirred at r.t. for 5 min. The organic phase is separated, dried and evaporated. The residue is chromatographed on silica gel using EtOAc as eluant to give 0.162 g of the product 0.112 g of recovered thio ester.
CC(=O)CC1CC(=O)N1C(C(=O)OCc1ccccc1[N+](=O)[O-])[PH](c1ccccc1)(c1ccccc1)c1ccccc1
null
null
null
220,755
ord_dataset-42629b4cf1094978a5e5f29f22639ee7
null
1991-01-01T00:01:00
true
[CH3:1][O-:2].[Na+].[SH:4][CH2:5][CH2:6][CH2:7][Si:8]([O:13][CH3:14])([O:11][CH3:12])[O:9][CH3:10].II>CO>[CH3:12][O:11][Si:8]([O:13][CH3:14])([O:9][CH3:10])[CH2:7][CH2:6][CH2:5][S:4][S:4][CH2:5][CH2:6][CH2:7][Si:8]([O:11][CH3:12])([O:9][CH3:10])[O:2][CH3:1]
C[O-]
CO[Si](CCCS)(OC)OC
null
II
[Na+]
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
0
0.5
A 28% solution of sodium methylate in methanol (97.6 g. 0.51 mole) is diluted with methanol (100 ml), and thereto is added γ-mercaptopropyltrimethoxysilane (100 g, 0.51 mole). The temperature of the mixture raises in a certain degree owing to the mixing heat but return to room temperature after about 30 minutes. To the mixture is added in portions iodine (64.6 g. 0.51 mole) with stirring. In view of exothermic reaction, the reaction vessel is cooled with ice water. After completion of the addition of iodine, the brown mixture is allowed to stand at room temperature for 3 hours to give a clean liquid having pale yellow color. The reaction mixture is moved to a flask, and the methanol solvent is distilled off under reduced pressure with a rotary evaporator. The residue containing white crystals and pale yellow liquid is filtered to separate the oily liquid (86.4 g). This liquid is subjected to analyses of IR, H-NMR and UV spectra, and thereby, it is confirmed that the liquid product is bis[γ-(trimethoxysilyl)propyl ]disulfide of the formula:
CO[Si](CCCSSCCC[Si](OC)(OC)OC)(OC)OC
null
null
null
1,588,262
ord_dataset-380e279f82154dba9e08ab51b3bdd08a
null
2015-01-01T00:05:00
true
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[C:5]([CH3:9])=[CH:4][N:3]=1.[Br:10]N1C(=O)CCC1=O>ClC1C=CC=CC=1.N(C(C)(C)C#N)=NC(C)(C)C#N>[Br:10][CH2:9][C:5]1[C:6]([Cl:8])=[CH:7][C:2]([Cl:1])=[N:3][CH:4]=1
Cc1cnc(Cl)cc1Cl
O=C1CCC(=O)N1Br
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
Clc1ccccc1
null
null
null
null
null
null
null
null
null
null
132
16
2,4-dichloro-5-methylpyridine (13.64 g, 82.50 mmol), N-bromosuccinimide (15.42 g, 86.63 mmol) were dissolved in chlorobenzene (300 mL). 2,2′-azobis(isobutyronitrile) (1.355 g, 8.250 mmol) in chlorobenzene (160 mL) was added slowly in two times: first approximately a third of the total amount at room temperature, then the rest dropwise (over 40 min) at 132° C. The reaction mixture was stirred at 132° C. for 16 h. The reaction mixture was washed with a saturated sodium sulfite solution (organic layer at the top), then with a saturated sodium bicarbonate solution (organic layer at the bottom). The organic phase was dried with sodium sulfate, then filtered and concentrated. A crude material was obtained as a yellow oil (24.9 g). It was purified by flash chromatography (Heptanes/AcOEt gradient from 0 to 10% AcOEt) to yield pale yellow crystals (13.84 g).
Clc1cc(Cl)c(CBr)cn1
null
125.3
null
1,435,245
ord_dataset-275a3da8f45f4536ad29727f0ef9ba66
null
2014-01-01T00:06:00
true
[C:1]([C:5]1[CH:13]=[CH:12][C:11]([N+:14]([O-])=O)=[CH:10][C:6]=1[C:7]([O-:9])=[O:8])([CH3:4])([CH3:3])[CH3:2].[CH:17]([O-])=O.[K+]>CCO.O.[Pd]>[C:1]([C:5]1[CH:13]=[CH:12][C:11]([NH2:14])=[CH:10][C:6]=1[C:7]([O:9][CH3:17])=[O:8])([CH3:4])([CH3:3])[CH3:2]
O=C[O-]
CC(C)(C)c1ccc([N+](=O)[O-])cc1C(=O)[O-]
null
[Pd]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CCO
null
null
null
null
null
null
null
null
null
25
null
To a refluxing solution of 2-tert-butyl-5-nitrobenzoate (90 mg, 0.38 mmol) in EtOH (2.0 mL) was added potassium formate (400 mg, 4.76 mmol) in water (1 mL), followed by the addition of 20 mg of 10% Pd—C. The reaction mixture was refluxed for additional 40 min, cooled to room temperature and filtered through Celite. The filtrate was concentrated to give methyl 2-tert-butyl-5-aminobenzoate (E-6) (76 mg, 95%), which was used without further purification. 1H NMR (400 MHz, CDCl3) δ 7.24 (d, J=8.6 Hz, 1H), 6.67 (dd, J=8.6, 2.7 Hz, 1H), 6.60 (d, J=2.7 Hz, 1H), 3.86 (s, 3H), 1.34 (s, 9H); HPLC ret. time 2.19 min, 10-99% CH3CN, 5 min run; ESI-MS 208.2 m/z (MH+).
COC(=O)c1cc(N)ccc1C(C)(C)C
null
96.5
null
1,610,872
ord_dataset-9cecb3a8d3b9494191b28dcefea66af2
null
2015-01-01T00:07:00
true
Cl[C:2]1[C:7]([F:8])=[C:6]([CH:9]=[N:10]O)[CH:5]=[CH:4][N:3]=1>C(O)(=O)C.[Zn]>[F:8][C:7]1[CH:2]=[N:3][CH:4]=[CH:5][C:6]=1[CH2:9][NH2:10]
ON=Cc1ccnc(Cl)c1F
null
null
[Zn]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(=O)O
null
null
null
null
null
null
null
null
null
null
25
2
Zinc dust (2.52 g, 38.6 mmol) was added at RT to a solution of 2-chloro-3-fluoro-pyridine-4-carbaldehyde oxime (1.34 g, 6.29 mmol) in acetic acid (30 mL). The reaction mixture was stirred at RT for 2 h, then concentrated in vacuo. The colored oily residue was partitioned between CH2Cl2 and 1N HCl. The layers were separated and the aqueous phase was extracted twice with CH2Cl2. The pH of the aqueous layer was then adjusted to pH=9 with 1N NaOH, and the resulting white suspension was extracted repeatedly with CH2Cl2. The combined organics were dried (phase separator) and concentrated in vacuo to afford the title compound as a yellow oil. MS (LC/MS): 127.0 [M+H]+; tR (HPLC conditions c): 0.50 min.
NCc1ccncc1F
null
null
null
1,166,627
ord_dataset-d24cc23b3db94284bb83a2ccdd9eb880
null
2012-01-01T00:05:00
true
C[O:2][C:3](=[O:13])[C:4]1[CH:9]=[C:8]([O:10][CH3:11])[C:7]([Cl:12])=[N:6][CH:5]=1.[OH-].[Na+].Cl>CO>[Cl:12][C:7]1[C:8]([O:10][CH3:11])=[CH:9][C:4]([C:3]([OH:13])=[O:2])=[CH:5][N:6]=1
COC(=O)c1cnc(Cl)c(OC)c1
null
null
Cl
[Na+]
[OH-]
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
24
To a solution of 6-chloro-5-methoxynicotinic acid methyl ester (1.3 g, 6.4 mmol) in MeOH (4 mL) at 25° C. was added 10% NaOH aqueous solution (19.3 mmol). The reaction was stirred for 24 h, then placed into an ice water bath and acidified with 2M HCl until pH=2 was achieved. The flask was then placed into a refrigerator for 3 h. The white precipitate was filtered off and rinsed with cold H2O. The solid was dissolved in acetone, dried over MgSO4 and concentrated to furnish the product 6-chloro-5-methoxynicotinic acid as a yellow solid (0.895 g, 74%); 1H NMR (400 MHz, CDCl3) δ 8.45 (d, 1H), 7.66 (d, 1H), 3.83 (s, 3H).
COc1cc(C(=O)O)cnc1Cl
null
74.6
null
913,228
ord_dataset-c663259b80f947e2a8923796fb0e9a6b
null
2009-01-01T00:10:00
true
[CH2:1]([N:8]1[C:13](=[O:14])[C:12]([CH3:16])([CH3:15])[CH2:11][C:10]([C:17]2[C:25]3[C:20](=[CH:21][CH:22]=[C:23]([Cl:26])[CH:24]=3)[NH:19][C:18]=2[CH3:27])=[N:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([O-])([O-])=O.[K+].[K+].Br[CH2:35][C:36]([O:38]C(C)(C)C)=[O:37]>CN(C=O)C.CCOC(C)=O>[CH2:1]([N:8]1[C:13](=[O:14])[C:12]([CH3:16])([CH3:15])[CH2:11][C:10]([C:17]2[C:25]3[C:20](=[CH:21][CH:22]=[C:23]([Cl:26])[CH:24]=3)[N:19]([CH2:35][C:36]([OH:38])=[O:37])[C:18]=2[CH3:27])=[N:9]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
CC(C)(C)OC(=O)CBr
Cc1[nH]c2ccc(Cl)cc2c1C1=NN(Cc2ccccc2)C(=O)C(C)(C)C1
null
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOC(C)=O
CN(C)C=O
null
null
null
null
null
null
null
null
null
80
null
The product of step b) (˜0.3 mmol) was dissolved in 5 mL DMF and treated with K2CO3 (1 mmol, 138 mg) and t-butyl bromoacetate (1 mmol, 195 mg). After heating to 80° C. for ½ h, the reaction was cooled, diluted with EtOAc and washed 5× water. The reaction was concentrated, dissolved in EtOH (5 mL) and treated with 1.4 mL of 1M NaOH. After heating to 80° C. for ½ h, the reaction was acidified with 3 M HCl and extracted into DCM (3×).
Cc1c(C2=NN(Cc3ccccc3)C(=O)C(C)(C)C2)c2cc(Cl)ccc2n1CC(=O)O
null
null
null
396,197
ord_dataset-018fd0e1351f4fd09b20fcddd97b4c7a
null
1998-01-01T00:03:00
true
[C:1](Cl)(=[O:19])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[S:8][S:9][C:10]1[CH:18]=[CH:17][CH:16]=[CH:15][C:11]=1[C:12](Cl)=[O:13].[NH2:21][C:22]1[CH:29]=[CH:28][C:25]([C:26]#[N:27])=[CH:24][CH:23]=1>ClCCl.N1C=CC=CC=1>[C:26]([C:25]1[CH:28]=[CH:29][C:22]([NH:21][C:1](=[O:19])[C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=2[S:8][S:9][C:10]2[CH:18]=[CH:17][CH:16]=[CH:15][C:11]=2[C:12]([NH:21][C:22]2[CH:29]=[CH:28][C:25]([C:26]#[N:27])=[CH:24][CH:23]=2)=[O:13])=[CH:23][CH:24]=1)#[N:27]
O=C(Cl)c1ccccc1SSc1ccccc1C(=O)Cl
N#Cc1ccc(N)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
c1ccncc1
null
null
null
null
null
null
null
null
null
null
null
This compound was prepared according to the general method of Example 77 using 2,2'-dithiobisbenzoyl chloride (2.00 g, 5.83 mmol) in 50 mL of dichloromethane and 4-aminobenzonitrile (1.38 g, 11.7 mmol) in 11 mL of pyridine. The crude product was triturated with a hot mixture of ethyl acetate and ethanol (1:1), filtered, and recrystallized from ethanol-DMF-water to yield 0.37 g of the title compound, mp 239°-241° C.
N#Cc1ccc(NC(=O)c2ccccc2SSc2ccccc2C(=O)Nc2ccc(C#N)cc2)cc1
null
12.5
null
367,615
ord_dataset-b18df02d6e9345faa0f2dae281a0870a
null
1997-01-01T00:06:00
true
[C:1]1([P:7](=[O:17])([O-:16])[O:8][CH2:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Cl.Cl[CH2:20][CH2:21][N:22]1[CH2:27][CH2:26][O:25][CH2:24][CH2:23]1.C(=O)([O-])[O-].[K+].[K+].C(OCC)(=O)C>CN(C=O)C>[C:1]1([P:7](=[O:16])([O:17][CH2:20][CH2:21][N:22]2[CH2:27][CH2:26][O:25][CH2:24][CH2:23]2)[O:8][CH2:9][C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
O=P([O-])(OCc1ccccc1)c1ccccc1
ClCCN1CCOCC1
null
Cl
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
CCOC(C)=O
null
null
null
null
null
null
null
null
null
65
22
A mixture of monobenzyl phenylphosphonate (115 mg, 0.46 mmol), N-(2-chloroethyl)morpholine hydrochloride (95 mg, 0.51 mmol) and potassium carbonate (140 mg, 1.0 mmol) in anhydrous DMF was stirred at 65° C. for 22 hours. Following dilution with ethyl acetate (40 ml), the mixture was washed with water four times and finally brine before being dried over magnesium sulfate, filtered and concentrated to leave 124 mg (74%) of the title compound as a pale yellow oil which was used without further purification. MS: 362 m/z (M+H)+.
O=P(OCCN1CCOCC1)(OCc1ccccc1)c1ccccc1
null
74.6
null
1,719,767
ord_dataset-3f2a531ffbae4b9eb1048afcd7953beb
null
2016-01-01T00:04:00
true
Br[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5](=[O:12])[O:4][C:3]=1[CH:13]([OH:15])[CH3:14].[C:16]1(B(O)O)[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.C([O-])([O-])=O.[Cs+].[Cs+]>CN(C=O)C.CCOC(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[OH:15][CH:13]([C:3]1[O:4][C:5](=[O:12])[C:6]2[C:11]([C:2]=1[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)=[CH:10][CH:9]=[CH:8][CH:7]=2)[CH3:14]
OB(O)c1ccccc1
CC(O)c1oc(=O)c2ccccc2c1Br
null
c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
O=C([O-])[O-]
[Cs+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOC(C)=O
CN(C)C=O
null
null
null
null
null
null
null
null
null
120
null
4-Bromo-3-(1-hydroxyethyl)-1H-isochromen-1-one (Intermediate A2, 0.77 g, 2.88 mmol), phenylboronic acid (0.63 g, 5.18 mmol), Pd(PPh3)4 (0.199 g, 0.173 mmol) and Cs2CO3 (1.49 g, 4.6 mmol) were dissolved in DMF (10.7 ml) and heated under microwave irradiation at 120° C. for 20 min. The reaction mixture was then diluted with AcOEt (100 mL) and filtrate. The organic phase was washed twice with 0.5 M HClaqueous, twice with water, sat NaHCO3 and once with sat NaClaqueous. The resulting organic phase was dried over Na2SO4, filtered and concentrated. The crude was finally purified on Biotage Si 50 g Ultra with a gradient of Hexane and EtOAc. The title compound was recovered as dark pink solid (0.53 g, 1.99 mmol, 69.3%) as a dark pink solid.
CC(O)c1oc(=O)c2ccccc2c1-c1ccccc1
null
null
null
169,464
ord_dataset-37d3220f708c49ad839bab296b722248
null
1988-01-01T00:03:00
true
Cl.[CH2:2]([O:4][C:5]([C:7]1[C:19]2[C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[NH:12][C:11]=2[CH:10]=[N:9][CH:8]=1)=[O:6])[CH3:3].[CH2:20](O)CC>>[CH2:2]([O:4][C:5]([C:7]1[C:19]2[C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[NH:12][C:11]=2[CH:10]=[N:9][CH:8]=1)=[O:6])[CH2:3][CH3:20]
CCCO
CCOC(=O)c1cncc2[nH]c3ccccc3c12
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 compound is produced by transesterification of the β-carboline-4-carboxylic acid-ethyl ester-hydrochloride with n-propanol.
CCCOC(=O)c1cncc2[nH]c3ccccc3c12
null
null
null
462,064
ord_dataset-5ca9db262dd24c5a9315cdc8ef055b7e
null
2000-01-01T00:04:00
true
O[C:2]1[CH:7]=[CH:6][C:5](/[CH:8]=[CH:9]/[CH2:10][N:11]2[CH2:16][CH2:15][CH:14]([C:17]3[CH:22]=[CH:21][C:20]([O:23][C:24]4[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=4)=[CH:19][CH:18]=3)[CH2:13][CH2:12]2)=[CH:4][C:3]=1OC.[F:32]C1C=CC(C=CCBr)=CC=1>>[F:32][C:2]1[CH:7]=[CH:6][C:5](/[CH:8]=[CH:9]/[CH2:10][N:11]2[CH2:16][CH2:15][CH:14]([C:17]3[CH:22]=[CH:21][C:20]([O:23][C:24]4[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=4)=[CH:19][CH:18]=3)[CH2:13][CH2:12]2)=[CH:4][CH:3]=1
Fc1ccc(C=CCBr)cc1
COc1cc(/C=C/CN2CCC(c3ccc(Oc4ccccc4)cc3)CC2)ccc1O
null
null
null
null
null
null
null
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 same procedure was followed as in Example 11 using the compound (9) synthesized in Example 2 and 4-fluorocinnamyl bromide to produce the above.
Fc1ccc(/C=C/CN2CCC(c3ccc(Oc4ccccc4)cc3)CC2)cc1
null
null
null
1,275,190
ord_dataset-d5c54236ecd94d61aaa071461bcfc426
null
2013-01-01T00:04:00
true
[H-].[Na+].[Br:3][C:4]1[C:5](Cl)=[N:6][CH:7]=[C:8]([N+:10]([O-:12])=[O:11])[CH:9]=1.[CH2:14]([OH:19])[C:15]([F:18])([F:17])[F:16]>>[Br:3][C:4]1[C:5]([O:19][CH2:14][C:15]([F:18])([F:17])[F:16])=[N:6][CH:7]=[C:8]([N+:10]([O-:12])=[O:11])[CH:9]=1
OCC(F)(F)F
O=[N+]([O-])c1cnc(Cl)c(Br)c1
null
[H-]
[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
25
0.5
Sodium hydride (3.2 g, 80.02 mmol) was added carefully in small portions to 2,2,2-trifluroethanol (CAS Registry No. 75-89-8) (60 ml) at 0° C. under nitrogen atmosphere and stirred at 25° C. for 30 minutes. Then 3-bromo-2-chloro-5-nitropyridine (CAS Registry No. 5470-17-7) (2 g, 8.42 mmol) in trifluoroethanol was added, and the reaction mixture was refluxed for 16h. The solvent was evaporated in vacuo, and the residue was taken up in water and extracted with ethyl acetate (3×120 ml). The combined organic layers were washed with water and brine, dried over Na2SO4 and concentrated to get the crude residue (3 g). The crude was purified by column chromatography (3% ethyl acetate/hexane) to give the desired product (2.4 g, 95%) as yellow liquid. MS (LC/MS): not responding, NMR is in agreement with the structure: 1H-NMR (400 MHz, CDCl3): δ 4.90 (m, 2H), 8.68 (d, 1H), 8.98 (d, 1H).
O=[N+]([O-])c1cnc(OCC(F)(F)F)c(Br)c1
null
95
null
1,083,085
ord_dataset-afd812677c134591a99f46ce28de2524
null
2011-01-01T00:08:00
true
[F:1][C:2]1[CH:3]=[C:4]([NH2:31])[CH:5]=[CH:6][C:7]=1[O:8][C:9]1[CH:14]=[CH:13][N:12]=[C:11]2[CH:15]=[C:16]([C:18]3[O:19][C:20]([CH2:23][N:24]4[CH2:29][CH2:28][N:27]([CH3:30])[CH2:26][CH2:25]4)=[CH:21][CH:22]=3)[S:17][C:10]=12.C1(C)C=CC=CC=1.C(O)C.[C:42]1([CH2:48][C:49]([N:51]=[C:52]=[S:53])=[O:50])[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=1>C1(C)C=CC=CC=1>[F:1][C:2]1[CH:3]=[C:4]([NH:31][C:52]([NH:51][C:49](=[O:50])[CH2:48][C:42]2[CH:43]=[CH:44][CH:45]=[CH:46][CH:47]=2)=[S:53])[CH:5]=[CH:6][C:7]=1[O:8][C:9]1[CH:14]=[CH:13][N:12]=[C:11]2[CH:15]=[C:16]([C:18]3[O:19][C:20]([CH2:23][N:24]4[CH2:25][CH2:26][N:27]([CH3:30])[CH2:28][CH2:29]4)=[CH:21][CH:22]=3)[S:17][C:10]=12
CN1CCN(Cc2ccc(-c3cc4nccc(Oc5ccc(N)cc5F)c4s3)o2)CC1
O=C(Cc1ccccc1)N=C=S
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
Cc1ccccc1
null
null
null
null
null
null
null
null
null
25
0.5
To a 5 mL round bottom flask was added 3-fluoro-4-(2-(5-((4-methylpiperazin-1-yl)methyl)furan-2-yl)thieno[3,2-b]pyridin-7-yloxy)benzenamine (32 mg, 0.0713 mmol) and 1:1 toluene/ethanol (1 mL). 2-Phenylethanoyl isothiocyanate (25.3 mg, 0.143 mmol; prepared according to the procedure described by J. Org. Chem. 1964, 29, 1115-1119) was added as a solution in toluene (0.5 mL). After stirring for 30 minutes at room temperature, the crude was concentrated in vacuo. The crude was dissolved in MeOH and purified by preparative TLC, eluting with 9:1 CH2Cl2/MeOH. The product was collected at Rf 0.4 just above the unreacted starting material at Rf 0.3 to provide the product (5 mg, 10%) as a white solid. LRMS (APCI+) m/e 626 (M+1) detected; 1H NMR (CDCl3, 400 MHz) δ 9.98 (s, 1H), 8.45 (d, J=5.5 Hz, 1H), 8.22 (s, 1H), 7.75 (d, J=13.7 Hz, 1H), 7.62 (s, 1H), 7.45 (m, 2H), 7.24 (m, 2H), 7.07 (t, J=8.6 Hz, 2H), 6.71 (s, 1H), 6.35 (s, 1H), 3.66 (s, 2H), 2.58 (m, 8H), 2.29 (s, 3H), 1.79 (m, 4H).
CN1CCN(Cc2ccc(-c3cc4nccc(Oc5ccc(NC(=S)NC(=O)Cc6ccccc6)cc5F)c4s3)o2)CC1
null
10
null
1,570,647
ord_dataset-9741bb5fd93044078df2a45f45733054
null
2015-01-01T00:04:00
true
[CH:1]1([N:4]([CH:18]2[CH2:23][CH2:22][NH:21][CH2:20][CH2:19]2)[S:5]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([C:14]([F:17])([F:16])[F:15])[CH:9]=2)(=[O:7])=[O:6])[CH2:3][CH2:2]1.[N:24]1[CH:29]=[CH:28][CH:27]=[C:26]([CH:30]=O)[CH:25]=1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClC(Cl)C>[CH:1]1([N:4]([CH:18]2[CH2:23][CH2:22][N:21]([CH2:30][C:26]3[CH:25]=[N:24][CH:29]=[CH:28][CH:27]=3)[CH2:20][CH2:19]2)[S:5]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([C:14]([F:17])([F:15])[F:16])[CH:9]=2)(=[O:6])=[O:7])[CH2:3][CH2:2]1
O=Cc1cccnc1
O=S(=O)(c1cccc(C(F)(F)F)c1)N(C1CCNCC1)C1CC1
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
CC(Cl)Cl
null
null
null
null
null
null
null
null
null
null
25
12
To a solution of N-cyclopropyl-N-piperidin-4-yl-3-trifluoromethyl-benzenesulfonamide (150 mg, 0.43 mmol) and pyridine-3-carboxaldehyde (46 mg, 0.43 mmol) in dichloroethane was added sodium triacetoxyborohydride (128 mg, 0.60 mmol, 1.4 eq.). The reaction mixture was stirred at room temperature for 12 hours. After this period, the solution was decanted and purified by flash chromatography to give the title compound 19 as a yellow oil. 1H NMR (CDCl3): δ 8.55-8.48 (m, 2H), 8.15-8.11 (m, 1H), 8.08-8.02 (m, 1H), 7.87-7.81 (m, 1H), 7.71-7.59 (m, 1H), 7.25-7.20 (m, 1H), 3.92-3.81 (m, 1H), 3.48 (s, 2H), 2.91-2.81 (m, 2H), 2.10-1.87 (m, 5H), 1.56-1.45 (m, 2H), 1.01-0.94 (m, m, 2H), 0.82-0.74 (m, 2H). LC: 100%. MS (EI): m/z 440 (M+H+).
O=S(=O)(c1cccc(C(F)(F)F)c1)N(C1CC1)C1CCN(Cc2cccnc2)CC1
null
null
null
911,768
ord_dataset-c663259b80f947e2a8923796fb0e9a6b
null
2009-01-01T00:10:00
true
[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6]([NH:15][CH2:16][CH2:17][CH2:18][CH2:19][Cl:20])=[C:7]([N+:12]([O-])=O)[CH:8]=[N:9]2)=[CH:4][CH:3]=1.S(S([O-])=O)([O-])=O.[Na+].[Na+]>CO.O>[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6]([NH:15][CH2:16][CH2:17][CH2:18][CH2:19][Cl:20])=[C:7]([NH2:12])[CH:8]=[N:9]2)=[CH:4][CH:3]=1
O=[N+]([O-])c1cnc2cc(Br)ccc2c1NCCCCCl
null
null
O=S([O-])S(=O)[O-]
[Na+]
null
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
0
2
A suspension of (7-bromo-3-nitroquinolin-4-yl)-(4-chlorobutyl)amine (8.05 g, 22.5 mmol) in methanol (250 mL) was cooled to 0° C.; a solution of sodium hydrosulfite (19.5 g, 112 mmol) in water (80 mL) was added dropwise over a period of 30 minutes. The reaction was stirred at ambient temperature for two hours and then concentrated under reduced pressure. The residue was partitioned between dichloromethane (300 mL) and aqueous sodium bicarbonate (150 mL of 50%). The aqueous layer was separated and extracted with dichloromethane (2×50 mL). The combined organic fractions were dried over magnesium sulfate, filtered, and concentrated under reduced pressure to provide 7.25 g of crude 7-bromo-N4-(4-chlorobutyl)quinoline-3,4-diamine as a light brown semi-solid.
Nc1cnc2cc(Br)ccc2c1NCCCCCl
null
98
null
584,370
ord_dataset-cb5dd7a8b94e4f19a9148a1904b0dcb6
null
2003-01-01T00:03:00
true
[NH2:1][C:2]1[CH:3]=[C:4]([CH:16]=[CH:17][C:18]=1[O:19][CH3:20])[C:5]([NH:7][C:8]1[CH:13]=[CH:12][C:11]([CH3:14])=[C:10]([Cl:15])[CH:9]=1)=[O:6].[Cl:21][C:22]1[CH:23]=[C:24]([N:29]=[C:30]=[S:31])[CH:25]=[C:26]([Cl:28])[CH:27]=1>ClCCl.CN(C=O)C>[Cl:15][C:10]1[CH:9]=[C:8]([NH:7][C:5](=[O:6])[C:4]2[CH:16]=[CH:17][C:18]([O:19][CH3:20])=[C:2]([NH:1][C:30]([NH:29][C:24]3[CH:25]=[C:26]([Cl:28])[CH:27]=[C:22]([Cl:21])[CH:23]=3)=[S:31])[CH:3]=2)[CH:13]=[CH:12][C:11]=1[CH3:14]
COc1ccc(C(=O)Nc2ccc(C)c(Cl)c2)cc1N
S=C=Nc1cc(Cl)cc(Cl)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
16
A solution of 3-amino-N-(3-chloro-4-methylphenyl)-4-methoxy-benzamide from Example 12 (0.581 g, 2.00 mmol) and 3,5-dichlorophenyl isothiocyanate (0.409 g, 2.00 mmol) in dichloromethane (40 mL) and DMF (3 mL) was allowed to stand at room temperature. After 16 hours, filtration afforded the product (0.57 g); m.p. 195-196° C.
COc1ccc(C(=O)Nc2ccc(C)c(Cl)c2)cc1NC(=S)Nc1cc(Cl)cc(Cl)c1
null
57.6
null
476,334
ord_dataset-d56f0a7ec215495c92e641d9fa932d28
null
2000-01-01T00:09:00
true
[F:1][C:2]1[CH:11]=[C:10]2[C:5]([CH2:6][CH2:7][CH2:8][C:9]2=O)=[CH:4][CH:3]=1.C(OP([CH2:21][C:22](=[O:27])[NH:23][CH:24]1[CH2:26][CH2:25]1)(=O)OCC)C>>[CH:24]1([NH:23][C:22](=[O:27])/[CH:21]=[C:9]2\[CH2:8][CH2:7][CH2:6][C:5]3[C:10]\2=[CH:11][C:2]([F:1])=[CH:3][CH:4]=3)[CH2:26][CH2:25]1
O=C1CCCc2ccc(F)cc21
CCOP(=O)(CC(=O)NC1CC1)OCC
null
null
null
null
null
null
null
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 an analogous manner to Example 12f with the replacement of 5-fluoro 1-tetralone and diethyl (cyclopropylcarbamoyl)methyl phosphonate with 7-fluoro-1-tetralone (7.76 g, 0.05 mol) and diethyl(cyclopropylcarbamoyl)methylphosphonate (11.1 g, 0.05 mol). Chromatography on Silca gel using ethyl acetate:hexanes (1:2) as eluent gave 4.38 g (37%) of (E-N-Cyclopropyl-2-(7-fluoro-1,2,3,4-tetrahydro-1-naphthylidene)acetamide. m.p., 122.8-123.3° C.; NMR (DMSO-d6): d 8.00 (d, J=4.0 Hz, 1H), 7.32 (dd J=11.0 Hz, 1H), 7.04-7.23 (m, 2H), 6.33 (s, 1H), 3.06 (m, 2H), 2.69 (m, 3H), 1.70 (m, 2H), 0.66 (m, 2H), 0.40 (m, 2H); steady-state nOe: irradiation at 6.39 d, observed significant nOe at 7.32 d.
O=C(/C=C1\CCCc2ccc(F)cc21)NC1CC1
null
null
null
409,658
ord_dataset-324fb6fdc2414cb79e436bf5d04d4bd2
null
1998-01-01T00:08:00
true
[F:1][C:2]([F:28])([F:27])[C:3]1[CH:8]=[CH:7][C:6]([C:9]([C:17]2[CH:22]=[CH:21][C:20]([C:23]([F:26])([F:25])[F:24])=[CH:19][CH:18]=2)([OH:16])[CH:10]2[CH2:15][CH2:14][NH:13][CH2:12][CH2:11]2)=[CH:5][CH:4]=1.[CH:29]1([CH2:32][O:33][C:34]2[CH:39]=[CH:38][C:37]([CH2:40]Cl)=[CH:36][CH:35]=2)[CH2:31][CH2:30]1.CCN(C(C)C)C(C)C.C(=O)(O)[O-].[Na+]>CS(C)=O>[CH:29]1([CH2:32][O:33][C:34]2[CH:35]=[CH:36][C:37]([CH2:40][N:13]3[CH2:12][CH2:11][CH:10]([C:9]([C:6]4[CH:5]=[CH:4][C:3]([C:2]([F:1])([F:27])[F:28])=[CH:8][CH:7]=4)([C:17]4[CH:22]=[CH:21][C:20]([C:23]([F:26])([F:24])[F:25])=[CH:19][CH:18]=4)[OH:16])[CH2:15][CH2:14]3)=[CH:38][CH:39]=2)[CH2:30][CH2:31]1
ClCc1ccc(OCC2CC2)cc1
OC(c1ccc(C(F)(F)F)cc1)(c1ccc(C(F)(F)F)cc1)C1CCNCC1
null
O=C([O-])O
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(C(C)C)C(C)C
CS(C)=O
null
null
null
null
null
null
null
null
null
null
null
A solution of 20.5 grams (0.051 mole) of 4-[bis(4-trifluoromethylphenyl)hydroxymethyl]piperidine, 10.0 grams (0.051 mole) of 4-(cyclopropylmeth-oxy)phenylmethyl chloride (prepared as in Step A of Example 1), and 35.4 mL (0.203 mole) of N,N'-diisopropylethylamine in 200 mL of dimethyl sulfoxide was stirred at ambient temperature for about 18 hours. The reaction mixture was then poured into an aqueous solution saturated with sodium bicarbonate. The mixture was extracted with two portions of ethyl acetate, and the extracts combined. The combination was dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to a residue, which was subjected to column chromatography on silica gel with 50% heptane in methylene chloride to 50% acetone in methylene chloride. The product-containing fractions were combined and concentrated under reduced pressure, yielding 22.0 grams of N-[4-(cyclopropylmethoxy)phenylmethyl]-4-[bis(4-trifluoromethylphenyl)hydroxymethyl]piperidine. The NMR spectrum was consistent with the proposed structure.
OC(c1ccc(C(F)(F)F)cc1)(c1ccc(C(F)(F)F)cc1)C1CCN(Cc2ccc(OCC3CC3)cc2)CC1
null
76.5
null
1,017,316
ord_dataset-f024e9664ab64906a71a2ff6004cb3d0
null
2010-01-01T00:12:00
true
[CH2:1]([NH2:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:9](Br)[CH:10]=[CH2:11].C(=O)(O)[O-].[Na+]>CS(C)=O.[I-].[Na+]>[C:2]1([CH2:1][NH:8][CH2:11][CH:10]=[CH2:9])[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
NCc1ccccc1
C=CCBr
null
O=C([O-])O
[I-]
[Na+]
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
25
3
To a solution of benzylamine (5.7 ml, 52.2 mmol) and sodium iodide (38 mg, 0.25 mmol) in DMSO (30 ml) was added dropwise allyl bromide (2.2 ml, 25.4 mmol) at 0° C. under argon. After stirring for 3 h at room temperature the reaction was complete as shown by TLC (cyclohexanes:ethyl acetate 1:1). Then saturated aqueous sodium bicarbonate solution was added, the product was extracted with diethyl ether (100 ml) and the organic layer was washed with brine. The crude product was purified via flash chromatography to give the title compound (2.1 g, 57%) as a clear oil. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.4-7.2 (m, 5H), 6.0-5.9 (m, 1H), 5.3-5.1 (m, 2H), 3.8 (s, 2H), 3.3 (d, 2H), 1.5 (bs, 1H).
C=CCNCc1ccccc1
null
56.2
null
1,240,011
ord_dataset-e96f5a2842f14e5380461c234100f05a
null
2012-01-01T00:12:00
true
Cl[C:2]1[CH:11]=[CH:10][N:9]=[C:8]2[C:3]=1[CH:4]=[CH:5][C:6]([CH3:12])=[N:7]2.[NH2:13][C:14]1[CH:19]=[C:18]([CH2:20][O:21][C:22]2[CH:27]=[CH:26][C:25]([Br:28])=[CH:24][CH:23]=2)[CH:17]=[CH:16][C:15]=1[S:29][C:30]1[CH:35]=[CH:34][C:33]([OH:36])=[CH:32][CH:31]=1>>[Br:28][C:25]1[CH:26]=[CH:27][C:22]([O:21][CH2:20][C:18]2[CH:17]=[CH:16][C:15]([S:29][C:30]3[CH:35]=[CH:34][C:33]([OH:36])=[CH:32][CH:31]=3)=[C:14]([NH:13][C:2]3[C:3]4[C:8](=[N:7][C:6]([CH3:12])=[CH:5][CH:4]=4)[N:9]=[CH:10][CH:11]=3)[CH:19]=2)=[CH:23][CH:24]=1
Nc1cc(COc2ccc(Br)cc2)ccc1Sc1ccc(O)cc1
Cc1ccc2c(Cl)ccnc2n1
null
null
null
null
null
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
The product from Example 1d (0.03 g, 0.167 mmol) was reacted with the product from Example 223c (0.060 g, 0.15 mmol) for 17.5 h following the procedure from Example 1g. Consumption of starting material required a second addition of the product from Example 1d (0.016 g, 0.09 mmol) and continued heating at 80° C. (18 h). The crude title compound was purified by HPLC with TFA providing the product as a trifluoroacetic acid salt (0.056 g, 55%). 1H NMR (300 MHz, DMSO-d6) δ ppm: 2.77 (s, 3H) 5.12 (s, 2H) 6.30 (d, J=6.99 Hz, 1H) 6.79 (d, J=8.82 Hz, 2H) 6.92-7.08 (m, 3H) 7.25 (d, J=8.82 Hz, 2H) 7.42-7.54 (m, 4H) 7.81 (d, J=8.82 Hz, 1H) 8.47 (d, J=6.99 Hz, 1H) 9.01 (d, J=8.46 Hz, 1H) 9.98 (s, 1H); MS (ESI+) m/z 546.0 (M+H)+.
Cc1ccc2c(Nc3cc(COc4ccc(Br)cc4)ccc3Sc3ccc(O)cc3)ccnc2n1
null
null
null
37,525
ord_dataset-b0ddd49dad024fc7a23ae6f474f9c52f
null
1978-01-01T00:03:00
true
Cl[C:2]1[C:3]2[N:4]([N:13]=[CH:14][C:15]=2[C:16]([O:18][CH2:19][CH3:20])=[O:17])[C:5]2[N:10]([CH3:11])[N:9]=[C:8]([CH3:12])[C:6]=2[N:7]=1.[SH-:21].[Na+]>C(O)CC>[CH3:11][N:10]1[C:5]2[N:4]3[N:13]=[CH:14][C:15]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[C:3]3[C:2]([SH:21])=[N:7][C:6]=2[C:8]([CH3:12])=[N:9]1
CCOC(=O)c1cnn2c1c(Cl)nc1c(C)nn(C)c12
[SH-]
null
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCCO
null
null
null
null
null
null
null
null
null
null
null
null
5.86 gms. of 5-chloro-1,3-dimethyl-1H-dipyrazolo[1,5-a:4',3'-e]pyrazine-6-carboxylic acid, ethyl ester, are refluxed with 2 gms. of sodium bisulfide and 50 ml. of n-propanol for 3 hours. On cooling, the product, 1,3-dimethyl-5-mercapto-1H-dipyrazolo[1,5-a:4',3'-e]pyrazine-6-carboxylic acid, ethyl ester, crystallizes in the form of yellow filamentous needles which are recrystallized from n-propanol, yield 4.76 gms., m.p. 189°-191°.
CCOC(=O)c1cnn2c1c(S)nc1c(C)nn(C)c12
null
null
null
1,564,805
ord_dataset-4e54080057a44c3887653391e24c90b6
null
2015-01-01T00:03:00
true
C[O:2][C:3](=[O:53])[C@@H:4]([NH:20][C:21]([C@@H:23]1[CH2:32][C:31]2[CH:30]=[C:29]3[O:33][CH2:34][C@H:35]([C:37]4[CH:42]=[CH:41][C:40]([O:43][CH2:44][C:45]5[CH:50]=[CH:49][C:48]([Cl:51])=[C:47]([Cl:52])[CH:46]=5)=[CH:39][CH:38]=4)[O:36][C:28]3=[CH:27][C:26]=2[CH2:25][NH:24]1)=[O:22])[CH2:5][C:6]1[CH:11]=[CH:10][C:9]([C:12]2[CH:17]=[CH:16][N:15]=[C:14]([CH3:18])[C:13]=2[CH3:19])=[CH:8][CH:7]=1.[N:54]([C:57]([CH3:61])([CH2:59][CH3:60])[CH3:58])=[C:55]=[O:56].[N-]=C=O>>[Cl:52][C:47]1[CH:46]=[C:45]([CH:50]=[CH:49][C:48]=1[Cl:51])[CH2:44][O:43][C:40]1[CH:39]=[CH:38][C:37]([C@H:35]2[CH2:34][O:33][C:29]3=[CH:30][C:31]4[CH2:32][C@@H:23]([C:21]([NH:20][C@@H:4]([CH2:5][C:6]5[CH:11]=[CH:10][C:9]([C:12]6[CH:17]=[CH:16][N:15]=[C:14]([CH3:18])[C:13]=6[CH3:19])=[CH:8][CH:7]=5)[C:3]([OH:53])=[O:2])=[O:22])[N:24]([C:55](=[O:56])[NH:54][C:57]([CH3:61])([CH3:58])[CH2:59][CH3:60])[CH2:25][C:26]=4[CH:27]=[C:28]3[O:36]2)=[CH:42][CH:41]=1
CCC(C)(C)N=C=O
COC(=O)[C@H](Cc1ccc(-c2ccnc(C)c2C)cc1)NC(=O)[C@@H]1Cc2cc3c(cc2CN1)O[C@@H](c1ccc(OCc2ccc(Cl)c(Cl)c2)cc1)CO3
null
[N-]=C=O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
(S)-2-({(3S,8S)-3-[4-(3,4-Dichloro-benzyloxy)-phenyl]-2,3,6,7,8,9-hexahydro-[1,4]dioxino[2,3-g]isoquinoline-8-carbonyl}-amino)-3-[4-(2,3-dimethyl-pyridin-4-yl)-phenyl]-propionic acid methyl ester (20 mg) was reacted with 2-isocyanato-2-methyl-butane (prepared according to General Procedure AD) according to General Procedure I (with excess of isocyanate). The resulting compound was hydrolyzed according to General Procedure B to give the title compound (7 mg). LCMS (m/z): 852.
CCC(C)(C)NC(=O)N1Cc2cc3c(cc2C[C@H]1C(=O)N[C@@H](Cc1ccc(-c2ccnc(C)c2C)cc1)C(=O)O)OC[C@H](c1ccc(OCc2ccc(Cl)c(Cl)c2)cc1)O3
null
null
null
139,376
ord_dataset-7d359d96b3a64882921ebdc6c850e22e
null
1986-01-01T00:01:00
true
C([NH:3][C:4]1[S:5][CH:6]=[C:7]([C:9](=[N:27][O:28][CH2:29][C:30]#[CH:31])[C:10]([NH:12][CH:13]2[C:25](=[O:26])[N:15]3[C:16]([C:22]([OH:24])=[O:23])=[C:17]([O:20][CH3:21])[CH2:18][S:19][C@H:14]23)=[O:11])[N:8]=1)=O.Cl>CO>[NH2:3][C:4]1[S:5][CH:6]=[C:7]([C:9](=[N:27][O:28][CH2:29][C:30]#[CH:31])[C:10]([NH:12][CH:13]2[C:25](=[O:26])[N:15]3[C:16]([C:22]([OH:24])=[O:23])=[C:17]([O:20][CH3:21])[CH2:18][S:19][C@H:14]23)=[O:11])[N:8]=1
C#CCON=C(C(=O)NC1C(=O)N2C(C(=O)O)=C(OC)CS[C@H]12)c1csc(NC=O)n1
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
25
4
A mixture of 7-[2-(2-formamidothiazol-4-yl)-2-propargyloxyiminoacetamido]-3-methoxy-3-cephem-4-carboxylic acid (syn isomer, 0.9 g.), conc. hydrochloric acid (0.9 ml.) and methanol (13.5 ml.) was stirred at room temperature for 4 hours. After concentrating the resultant solution in vacuo at 35° C., the residue was dissolved in water and washed with ethyl acetate. The aqueous solution was adjusted to pH 7.0 with sodium bicarbonate and washed with ethyl acetate and diethyl ether. After removing the organic solvent by bubbling nitrogen gas, the solution was adjusted to pH 3.0 with 10% hydrochloric acid and stirred under ice cooling. The precipitates were collected by filtration, washed with water and dried to give 7-[2-(2-aminothiazol-4-yl)-2-propargyloxyiminoacetamido]-3-methoxy-3-cephem-4-carboxylic acid (syn isomer, 0.25 g.), whitish yellow powder.
C#CCON=C(C(=O)NC1C(=O)N2C(C(=O)O)=C(OC)CS[C@H]12)c1csc(N)n1
null
29.6
null
898,778
ord_dataset-de6bce51790e4004a27e1a8f2bcc7ded
null
2009-01-01T00:08:00
true
[Cl:1][C:2]1[CH:11]=[C:10]([C:12]#[C:13][CH:14]2[CH2:16][CH2:15]2)[CH:9]=[CH:8][C:3]=1[C:4]([O:6]C)=[O:5].[OH-].[Na+].C1COCC1>CO>[Cl:1][C:2]1[CH:11]=[C:10]([C:12]#[C:13][CH:14]2[CH2:16][CH2:15]2)[CH:9]=[CH:8][C:3]=1[C:4]([OH:6])=[O:5]
COC(=O)c1ccc(C#CC2CC2)cc1Cl
null
null
[Na+]
[OH-]
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
25
5
A mixture of methyl 2-chloro-4-(2-cyclopropylethynyl)benzoate (310 mg, 0.0013 mol), 2N aq. NaOH (3.0 mL), THF (5 mL), and MeOH (5 mL) was stirred at rt for 5 h. The mixture was concentrated under vacuum and the residue was treated with water and acidified with 1N HCl to pH 2-3, and extracted with EtOAc. The organic layer was washed with brine, dried (Na2SO4), filtered and concentrated under vacuum to give the product (270 mg, 93%) as a yellow solid. LC-MS: 3.18 min, 218.9 & 220.9 (M−1).
O=C(O)c1ccc(C#CC2CC2)cc1Cl
null
94.1
null
82,813
ord_dataset-b1023e5ccd7142de9d250aa2e3e124db
null
1981-01-01T00:06:00
true
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[O:9][C:10]3[CH:22]=[CH:21][CH:20]=[CH:19][C:11]=3[C:12]=2[N:13]2[CH2:18][CH2:17][NH:16][CH2:15][CH2:14]2)=[CH:4][CH:3]=1.[C:23](Cl)(=[O:32])[CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31]>C(N(CC)CC)C.C(Cl)Cl>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[O:9][C:10]3[CH:22]=[CH:21][CH:20]=[CH:19][C:11]=3[C:12]=2[N:13]2[CH2:18][CH2:17][N:16]([C:23](=[O:32])[CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])[CH2:15][CH2:14]2)=[CH:6][CH:7]=1
Clc1ccc(-c2oc3ccccc3c2N2CCNCC2)cc1
CCCCCCCCC(=O)Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
CCN(CC)CC
null
null
null
null
null
null
null
null
null
null
0.5
To the solution of 56 g of 1-(2-p-chlorophenyl-3-benzofuryl)piperazine in 25.2 g of triethylamine and 500 ml of methylene chloride, 31.7 g of pelargonic acid chloride in 300 ml of methylene chloride are added while stirring at 0° for 1/2 hour and stirring is continued for 15 hours. The mixture is washed successively with 1 N-hydrochloric acid, 2 N-aqueous sodium hydroxide and saturated aqueous sodium chloride, dried and evaporated to yield the 1-(2-p-chlorophenyl-3-benzofuryl)-4-pelargonylpiperazine as an oil showing in the 1R-spectrum characteristic bands at 1640 and 812 cm-1.
CCCCCCCCC(=O)N1CCN(c2c(-c3ccc(Cl)cc3)oc3ccccc23)CC1
null
null
null
577,320
ord_dataset-a9ba4801408c4b01922886164c10a391
null
2003-01-01T00:01:00
true
[O:1]=[C:2]1[CH2:11][CH2:10][CH2:9][C:8]2[C:7]([NH:12][S:13]([CH3:16])(=[O:15])=[O:14])=[CH:6][CH:5]=[CH:4][C:3]1=2.[H-].[Na+].[CH3:19][O:20][CH2:21]Cl.O>CN(C=O)C>[CH3:19][O:20][CH2:21][N:12]([C:7]1[C:8]2[CH2:9][CH2:10][CH2:11][C:2](=[O:1])[C:3]=2[CH:4]=[CH:5][CH:6]=1)[S:13]([CH3:16])(=[O:15])=[O:14]
COCCl
CS(=O)(=O)Nc1cccc2c1CCCC2=O
null
[H-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CN(C)C=O
null
null
null
null
null
null
null
null
null
0
0.75
A solution of Example 15A (4.0 g, 17 mmol) in anhydrous DMF (40 mL) under a nitrogen atmosphere was treated with a 60% dispersion of sodium hydride (0.74 g, 18 mmol) in portions over 5 minutes, stirred for 45 minutes, cooled to 0° C., treated dropwise with chloromethyl methyl ether (1.3 mL, 18 mmol), stirred at ambient temperature for 2 hours, treated with cold water (250 mL) and extracted with diethyl ether (3×). The combined diethyl ether extracts were washed with water, washed with brine, dried (MgSO4), filtered and concentrated. Purification of the residue on silica gel with 1:1 hexanes:ethyl acetate provided the desired product.
COCN(c1cccc2c1CCCC2=O)S(C)(=O)=O
null
null
null
122,637
ord_dataset-a9b95e50436441ff8f3f12dd60d1e1b2
null
1984-01-01T00:10:00
true
[NH:1]([C:5]1[CH:10]=[CH:9][C:8]([C:11](=[O:15])[CH2:12][CH2:13][CH3:14])=[CH:7][CH:6]=1)C(C)=O.[OH-].[Na+]>Cl>[NH2:1][C:5]1[CH:6]=[CH:7][C:8]([C:11](=[O:15])[CH2:12][CH2:13][CH3:14])=[CH:9][CH:10]=1
CCCC(=O)c1ccc(NC(C)=O)cc1
null
null
Cl
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
0
null
20 g of p-acetaminobutyrophenone are suspended in 40 ml of semi-concentrated hydrochloric acid and the suspension is heated under reflux for 25 minutes and poured into a mixture of 100 ml of ice and 30 ml of concentrated sodium hydroxide solution. The mixture is filtered with suction, then the residue is washed twice with ice-cold water, dried in the atmosphere and recrystallised from methanol/water (20 ml+100 ml). p-Aminobutyrophenone having a melting point of 93°-94° is obtained.
CCCC(=O)c1ccc(N)cc1
null
null
null
1,509,290
ord_dataset-1a1aa5d1c3224edca0aec6e3398da985
null
2014-01-01T00:11:00
true
[CH2:1]([O:8][C@@H:9]1[CH2:13][C@H:12]([O:14][C:15]2[C:20]([F:21])=[CH:19][C:18]([S:22]([N:25](CC3C=CC(OC)=CC=3OC)[C:26]3[CH:31]=[CH:30][N:29]=[CH:28][N:27]=3)(=[O:24])=[O:23])=[C:17]([F:43])[CH:16]=2)[C@@H:11]([C:44]2[N:48]([CH3:49])[N:47]=[CH:46][CH:45]=2)[CH2:10]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([SiH](CC)CC)C.FC(F)(F)C(O)=O>ClCCl>[CH2:1]([O:8][C@@H:9]1[CH2:13][C@H:12]([O:14][C:15]2[C:20]([F:21])=[CH:19][C:18]([S:22]([NH:25][C:26]3[CH:31]=[CH:30][N:29]=[CH:28][N:27]=3)(=[O:23])=[O:24])=[C:17]([F:43])[CH:16]=2)[C@@H:11]([C:44]2[N:48]([CH3:49])[N:47]=[CH:46][CH:45]=2)[CH2:10]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
COc1ccc(CN(c2ccncn2)S(=O)(=O)c2cc(F)c(O[C@H]3C[C@@H](OCc4ccccc4)C[C@@H]3c3ccnn3C)cc2F)c(OC)c1
null
null
CC[SiH](CC)CC
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
O=C(O)C(F)(F)F
null
null
null
null
null
null
null
null
null
null
null
The reaction and aftertreatment were conducted in the same manner as in Example 1b by using the 4-{[(1S*,2R*,4S*)-4-(benzyloxy)-2-(1-methyl-1H-pyrazol-5-yl)cyclopentyl]oxy}-N-(2,4-dimethoxybenzyl)-2,5-difluoro-N-(pyrimidin-4-yl)benzenesulfonamide (143 mg, 0.207 mmol) prepared in Example 98b, triethylsilane (0.20 mL), trifluoroacetic acid (2.0 mL) and dichloromethane (2.0 mL), to yield the title compound (91 mg, 81%) as a colorless solid.
Cn1nccc1[C@H]1C[C@H](OCc2ccccc2)C[C@@H]1Oc1cc(F)c(S(=O)(=O)Nc2ccncn2)cc1F
null
81.2
null
1,740,336
ord_dataset-eacfee6d16d8455a93348409f1b37be4
null
2016-01-01T00:06:00
true
[F:1][C:2]1[CH:31]=[CH:30][C:5]([C:6]([NH:8][C:9](=[S:29])[NH:10][C:11]2[S:21][C:14]3[CH2:15][O:16][C:17]([CH3:20])([CH3:19])[CH2:18][C:13]=3[C:12]=2[C:22]([O:24]C(C)(C)C)=[O:23])=[O:7])=[CH:4][CH:3]=1>C(O)(C(F)(F)F)=O.C(Cl)Cl>[F:1][C:2]1[CH:3]=[CH:4][C:5]([C:6]([NH:8][C:9](=[S:29])[NH:10][C:11]2[S:21][C:14]3[CH2:15][O:16][C:17]([CH3:20])([CH3:19])[CH2:18][C:13]=3[C:12]=2[C:22]([OH:24])=[O:23])=[O:7])=[CH:30][CH:31]=1
CC(C)(C)OC(=O)c1c(NC(=S)NC(=O)c2ccc(F)cc2)sc2c1CC(C)(C)OC2
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
1
A solution of 40% v/v TFA/DCM (20 mL) was added to tert-butyl 2-(3-(4-fluorobenzoyl)thioureido)-5,5-dimethyl-5,7-dihydro-4H-thieno[2,3-c]pyran-3-carboxylate (0.33 g, 0.71 mmol) and the mixture was stirred at RT for 1 hour. The volatiles were removed at 30° C. and the material was purified by reverse-phase chromatography (10-100% MeCN/water). 2-(3-(4-Fluorobenzoyl)thioureido)-5,5-dimethyl-5,7-dihydro-4H-thieno[2,3-c]pyran-3-carboxylic acid (0.21 g, 0.51 mmol, 72% yield) was isolated as a pale, yellow solid. 1H NMR (400 MHz, DMSO) δ 14.81 (s, 1H), 13.36 (s, 1H), 11.83 (s, 1H), 8.11-8.00 (m, 2H), 7.38 (apparent t, J=8.9 Hz, 2H), 4.66 (s, 2H), 2.74 (s, 2H), 1.23 (s, 6H). 13C NMR (101 MHz, DMSO) δ 174.33, 166.13, 165.72, 165.35, 163.63, 146.76, 131.80, 131.70, 129.08, 128.60, 128.57, 124.06, 116.48, 115.54, 115.32, 70.12, 58.80, 37.25, 26.16. LCMS retention time: 3.206 min; LCMS purity at 214 nm=98%. HRMS m/z calculated for C18H18FN2O4S2 [M++1]: 409.0687. found 409.0687. Melting point 205.3° C., decomposition.
CC1(C)Cc2c(sc(NC(=S)NC(=O)c3ccc(F)cc3)c2C(=O)O)CO1
null
71.8
null
6,520
ord_dataset-653be8036d754ce7b8a1c4cd419eaf55
null
1976-01-01T00:05:00
true
[CH3:1][S:2]([C:4]1[CH:12]=[CH:11][C:7]([C:8](Cl)=[O:9])=[CH:6][CH:5]=1)=[O:3].[F:13][C:14]1[CH:19]=[CH:18][C:17]([CH3:20])=[CH:16][CH:15]=1>FC(F)(F)S(O)(=O)=O>[F:13][C:14]1[CH:15]=[CH:16][C:17]([CH3:20])=[C:18]([CH:19]=1)[C:8]([C:7]1[CH:11]=[CH:12][C:4]([S:2]([CH3:1])=[O:3])=[CH:5][CH:6]=1)=[O:9]
Cc1ccc(F)cc1
CS(=O)c1ccc(C(=O)Cl)cc1
null
O=S(=O)(O)C(F)(F)F
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
p-Methylsulfinylbenzoyl chloride (0.2 mole) and p-fluorotoluene (0.2 mole) are refluxed together in trifluoromethanesulfonic acid for 6 hours according to the procedure of Chodroff and Klein, J.A.C.S. 70, 7209 (1948).
Cc1ccc(F)cc1C(=O)c1ccc(S(C)=O)cc1
null
null
null
695,599
ord_dataset-a7baa616c65d42559e25ca0ba61e0744
null
2006-01-01T00:01:00
true
[CH:1]([C:4]1[C:5](=[O:21])[NH:6][C:7](=[O:20])[NH:8][C:9]=1[C:10](=[O:19])[C:11]1[CH:16]=[C:15]([CH3:17])[CH:14]=[C:13]([CH3:18])[CH:12]=1)([CH3:3])[CH3:2].Cl[CH2:23][C:24]1[C:25]2[C:30]([CH:31]=[C:32]3[C:37]=1[CH:36]=[CH:35][CH:34]=[CH:33]3)=[CH:29][CH:28]=[CH:27][CH:26]=2>>[CH:26]1[C:25]2[C:30](=[CH:31][C:32]3[C:37]([C:24]=2[CH2:23][N:8]2[C:9]([C:10](=[O:19])[C:11]4[CH:12]=[C:13]([CH3:18])[CH:14]=[C:15]([CH3:17])[CH:16]=4)=[C:4]([CH:1]([CH3:3])[CH3:2])[C:5](=[O:21])[NH:6][C:7]2=[O:20])=[CH:36][CH:35]=[CH:34][CH:33]=3)[CH:29]=[CH:28][CH:27]=1
ClCc1c2ccccc2cc2ccccc12
Cc1cc(C)cc(C(=O)c2[nH]c(=O)[nH]c(=O)c2C(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
5-Isopropyl-6-(3,5-dimethylbenzoyl)-2,4-pyrimidinedione and 9-chloromethyl anthracene were reacted by the same way with the example 1 to obtain the titled compound (192 mg, yield: 40.3%).
Cc1cc(C)cc(C(=O)c2c(C(C)C)c(=O)[nH]c(=O)n2Cc2c3ccccc3cc3ccccc23)c1
null
40.3
null
578,478
ord_dataset-a9ba4801408c4b01922886164c10a391
null
2003-01-01T00:01:00
true
[CH3:1][O:2][C:3]1[CH:4]=[C:5](B(O)O)[CH:6]=[C:7]([O:11][CH3:12])[C:8]=1[O:9][CH3:10].Cl[C:17]1[CH:18]=[C:19]([CH:25]=[CH:26][N:27]=1)[C:20]([O:22][CH2:23][CH3:24])=[O:21]>>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:17]2[CH:18]=[C:19]([CH:25]=[CH:26][N:27]=2)[C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH:6]=[C:7]([O:11][CH3:12])[C:8]=1[O:9][CH3:10]
COc1cc(B(O)O)cc(OC)c1OC
CCOC(=O)c1ccnc(Cl)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
3,4,5-Trimethoxyphenylboronic acid (15.29 g) and ethyl 2-chloroisonicotinate (13.39 g) were reacted in the same manner as in Preparation Example 1 to obtain the title compound.
CCOC(=O)c1ccnc(-c2cc(OC)c(OC)c(OC)c2)c1
null
null
null
1,641,909
ord_dataset-bcc0b01d4f58457a8733b10a099f43ba
null
2015-01-01T00:10:00
true
[OH:1][C:2]([CH3:29])([CH3:28])[CH:3]([C:22]1[CH:23]=[N:24][CH:25]=[CH:26][CH:27]=1)[O:4][C:5]1[C:6]([NH:15][S:16]([CH2:19][CH2:20][CH3:21])(=[O:18])=[O:17])=[N:7][C:8]2[C:13]([N:14]=1)=[CH:12][CH:11]=[CH:10][CH:9]=2.ClC1C=CC=C(C(OO)=[O:38])C=1>ClCCl>[OH:1][C:2]([CH3:28])([CH3:29])[CH:3]([C:22]1[CH:23]=[N+:24]([O-:38])[CH:25]=[CH:26][CH:27]=1)[O:4][C:5]1[C:6]([NH:15][S:16]([CH2:19][CH2:20][CH3:21])(=[O:18])=[O:17])=[N:7][C:8]2[C:13](=[CH:12][CH:11]=[CH:10][CH:9]=2)[N:14]=1
O=C(OO)c1cccc(Cl)c1
CCCS(=O)(=O)Nc1nc2ccccc2nc1OC(c1cccnc1)C(C)(C)O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
25
2
Compound 1 (89.6 mg, 0.215 mmol) obtained in Example 1 was dissolved in dichloromethane (5.0 mL). To the solution was added 65% meta-chloroperbenzoic acid (85.7 mg, 0.323 mmol) and the mixture was stirred at room temperature for 2 hours. The solvent was evaporated under reduced pressure. The residue was purified by preparative thin-layer chromatography (chloroform/methanol=9/1) to give Compound 2 (47.7 mg, 51% yield).
CCCS(=O)(=O)Nc1nc2ccccc2nc1OC(c1ccc[n+]([O-])c1)C(C)(C)O
null
51.3
null