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
603,317
ord_dataset-82e842e611ef4a05b6e7f9ea0a46d52d
null
2003-01-01T00:07:00
true
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Cl:8])[C:3]=1[CH2:9][S:10]([C:13]1[CH:14]=[C:15]2[C:19](=[CH:20][CH:21]=1)[NH:18][C:17](=[O:22])[CH2:16]2)(=[O:12])=[O:11].[OH:23][C@@H:24]1[CH2:28][CH2:27][N:26]([CH2:29][C:30]2[C:31]([CH3:38])=[C:32]([CH:36]=O)[NH:33][C:34]=2[CH3:35])[CH2:25]1>C(O)C.N1CCCCC1>[Cl:8][C:4]1[CH:5]=[CH:6][CH:7]=[C:2]([Cl:1])[C:3]=1[CH2:9][S:10]([C:13]1[CH:14]=[C:15]2[C:19](=[CH:20][CH:21]=1)[NH:18][C:17](=[O:22])/[C:16]/2=[CH:36]\[C:32]1[NH:33][C:34]([CH3:35])=[C:30]([CH2:29][N:26]2[CH2:27][CH2:28][C@@H:24]([OH:23])[CH2:25]2)[C:31]=1[CH3:38])(=[O:12])=[O:11]
Cc1[nH]c(C=O)c(C)c1CN1CC[C@@H](O)C1
O=C1Cc2cc(S(=O)(=O)Cc3c(Cl)cccc3Cl)ccc2N1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
C1CCNCC1
null
null
null
null
null
null
null
null
null
null
null
5-(2,6-Dichloro-phenylmethanesulfonyl)-1,3-dihydro-indol-2-one was condensed with 4-((R)-3-hydroxy-pyrrolidin-1-ylmethyl)-3,5-dimethyl-1H-pyrrole-2-carbaldehyde in ethanol and piperidine to give the titled compound as a yellow solid.
Cc1[nH]c(/C=C2\C(=O)Nc3ccc(S(=O)(=O)Cc4c(Cl)cccc4Cl)cc32)c(C)c1CN1CC[C@@H](O)C1
null
null
null
891,804
ord_dataset-11068b1e475b4c5b82e56726ab0dddb7
null
2009-01-01T00:07:00
true
[CH2:1]([O:8][C:9]([N:11]([CH2:32][C:33]([N:35]1[CH2:39][C@@H:38]([F:40])[CH2:37][C@H:36]1[C:41]#[N:42])=[O:34])[C:12]12[CH2:19][CH2:18][C:15]([C:20](ON3C4C=CC=CC=4N=N3)=[O:21])([CH2:16][CH2:17]1)[CH2:14][CH2:13]2)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH:43]1([NH2:46])[CH2:45][CH2:44]1>>[CH2:1]([O:8][C:9]([N:11]([CH2:32][C:33]([N:35]1[CH2:39][C@@H:38]([F:40])[CH2:37][C@H:36]1[C:41]#[N:42])=[O:34])[C:12]12[CH2:17][CH2:16][C:15]([C:20]([NH:46][CH:43]3[CH2:45][CH2:44]3)=[O:21])([CH2:18][CH2:19]1)[CH2:14][CH2:13]2)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
N#C[C@@H]1C[C@H](F)CN1C(=O)CN(C(=O)OCc1ccccc1)C12CCC(C(=O)On3nnc4ccccc43)(CC1)CC2
NC1CC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
In a similar manner to Example 4, (2S,4S)-1-[[N-benzyloxycarbonyl-N-[4-(benzotriazol-1-yl)oxycarbonylbicyclo[2.2.2]oct-1-yl]amino]acetyl]-4-fluoropyrrolidine-2-carbonitrile (50.0 mg) and cyclopropylamine (8.0 μL) were used to obtain (2S,4S)-1-[[N-benzyloxycarbonyl-N-[4-(N-cyclopropylamino)carbonylbicyclo[2.2.2]oct-1-yl]amino]acetyl]-4-fluoropyrrolidine-2-carbonitrile (31.6 mg).
N#C[C@@H]1C[C@H](F)CN1C(=O)CN(C(=O)OCc1ccccc1)C12CCC(C(=O)NC3CC3)(CC1)CC2
null
null
null
330,575
ord_dataset-2c460e2ef9934444aaf26fec1f75741f
null
1996-01-01T00:05:00
true
N[C:2]1[C:7]([C:8]#[N:9])=[N:6][C:5]([C:10]2[CH:15]=[C:14]([C:16]([F:19])([F:18])[F:17])[CH:13]=[C:12]([C:20]([F:23])([F:22])[F:21])[CH:11]=2)=[CH:4][N:3]=1.C(=O)(O)O.[NH2:28][C:29]([NH2:31])=[NH:30].O>CN(C)C(=O)C>[NH2:30][C:29]1[N:31]=[C:8]([NH2:9])[C:7]2[C:2](=[N:3][CH:4]=[C:5]([C:10]3[CH:15]=[C:14]([C:16]([F:19])([F:18])[F:17])[CH:13]=[C:12]([C:20]([F:22])([F:21])[F:23])[CH:11]=3)[N:6]=2)[N:28]=1
N=C(N)N
N#Cc1nc(-c2cc(C(F)(F)F)cc(C(F)(F)F)c2)cnc1N
null
O=C(O)O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CC(=O)N(C)C
null
null
null
null
null
null
null
null
null
null
null
Under a nitrogen atmosphere, a stirred solution of 1.0 gram (0.003 mole) of 2-amino-3-cyano-5-[3,5-di(trifluoromethyl)phenyl]pyrazine and 1.3 grams (0.007 mole) of guanidine carbonate in 10 mL of N,N-dimethylacetamide is heated at about 150° C. for 40 hours. After this time, the reaction mixture is poured into 50 mL of water. The resultant solid is collected by filtration and is then slurried in 25 mL of diethyl ether. The solid is again collected by filtration and is then recrystallized from ethanol, yielding 2,4-diamino-6-[3,5-di(trifluoromethyl)phenyl]pteridine.
Nc1nc(N)c2nc(-c3cc(C(F)(F)F)cc(C(F)(F)F)c3)cnc2n1
null
null
null
706,426
ord_dataset-c8069773c1a148aca8ab417108daacc5
null
2006-01-01T00:05:00
true
[CH2:1]([O:3][CH2:4][CH2:5][CH2:6][NH:7][C:8](=[O:23])[CH:9]([NH:14][C:15]1[CH:20]=[C:19]([Cl:21])[N:18]=[C:17](Cl)[N:16]=1)[CH2:10][CH:11]([CH3:13])[CH3:12])[CH3:2].[F:24][C:25]([F:39])([F:38])[O:26][C:27]1[CH:28]=[C:29]([C:33]2[N:34]=[CH:35][NH:36][CH:37]=2)[CH:30]=[CH:31][CH:32]=1.C([O-])([O-])=O.[K+].[K+].[F-].[K+]>CS(C)=O.O>[CH2:1]([O:3][CH2:4][CH2:5][CH2:6][NH:7][C:8](=[O:23])[CH:9]([NH:14][C:15]1[CH:20]=[C:19]([Cl:21])[N:18]=[C:17]([N:36]2[CH:37]=[C:33]([C:29]3[CH:30]=[CH:31][CH:32]=[C:27]([O:26][C:25]([F:24])([F:38])[F:39])[CH:28]=3)[N:34]=[CH:35]2)[N:16]=1)[CH2:10][CH:11]([CH3:13])[CH3:12])[CH3:2]
CCOCCCNC(=O)C(CC(C)C)Nc1cc(Cl)nc(Cl)n1
FC(F)(F)Oc1cccc(-c2c[nH]cn2)c1
null
O=C([O-])[O-]
[F-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CS(C)=O
null
null
null
null
null
null
null
null
null
25
null
A solution of 2-(2,6-dichloro-pyrimidin-4-ylamino)-4-methylpentanoic acid (3-ethoxypropyl)amide (1.5 gram), 4-(3-trifluoromethoxyphenyl)-1H-imidazole (0.99 gram), K2CO3 (1.7 gram) and KF (0.24 gram) in dimethylsulfoxide (40 ml) was heated to 100° C. for 17 hours. The solution was cooled to room temperature, taken up in water, and extracted three times with ethyl acetate. The etyl acetate layers were combined, washed with brine, dried over magnesium sulfate, filtered, and the solvents were removed in vacuo. Silica gel chromatography (toluene/acetone 4/1) provided 2.8 g of 4-methyl-2-{6-chloro-2-[4-(3-trifluoromethoxyphenyl)-imidazol-1-yl]-pyrimidin-4-ylamino}-pentanoic acid (3-ethoxypropyl)amide as an orange oil.
CCOCCCNC(=O)C(CC(C)C)Nc1cc(Cl)nc(-n2cnc(-c3cccc(OC(F)(F)F)c3)c2)n1
null
122.2
null
817,266
ord_dataset-50f99930fc41474db226bc80774b38df
null
2008-01-01T00:04:00
true
[Cl:1][C:2]1[CH:28]=[CH:27][C:5]([C:6]([NH:8][C:9]2[S:10][CH:11]=[C:12]([CH2:14][C:15]([N:17]3[CH2:22][CH2:21][N:20]([CH2:23][C:24](O)=[O:25])[CH2:19][CH2:18]3)=[O:16])[N:13]=2)=[O:7])=[CH:4][CH:3]=1.[CH3:29][N:30]1[CH2:35][CH2:34][NH:33][CH2:32][CH2:31]1>>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:6]([NH:8][C:9]2[S:10][CH:11]=[C:12]([CH2:14][C:15]([N:17]3[CH2:22][CH2:21][N:20]([CH2:23][C:24]([N:33]4[CH2:34][CH2:35][N:30]([CH3:29])[CH2:31][CH2:32]4)=[O:25])[CH2:19][CH2:18]3)=[O:16])[N:13]=2)=[O:7])=[CH:27][CH:28]=1
O=C(O)CN1CCN(C(=O)Cc2csc(NC(=O)c3ccc(Cl)cc3)n2)CC1
CN1CCNCC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
22.3 Using general procedure A, (4-{2-[2-(4-chloro-benzoylamino)-thiazol-4-yl]-acetyl}-piperazin-1-yl)-acetic acid was coupled with 1-methyl piperazine to give 4-chloro-N-[4-(2-{4-[2-(4-methyl-piperazin-1-yl)-2-oxo-ethyl]-piperazin-1-yl}-2-oxo-ethyl)-thiazol-2-yl]-benzamide. White solid. MS 505.3 ([M+H]+)
CN1CCN(C(=O)CN2CCN(C(=O)Cc3csc(NC(=O)c4ccc(Cl)cc4)n3)CC2)CC1
null
null
null
609,845
ord_dataset-73916d628db147c89020b3baac642d48
null
2003-01-01T00:09:00
true
[CH:1]1([NH:5][C:6](=[O:27])[C:7]2[CH:12]=[C:11]([O:13][C:14]3[C:19]([Cl:20])=[CH:18][C:17]([CH2:21][O:22][CH3:23])=[CH:16][C:15]=3[Cl:24])[CH:10]=[CH:9][C:8]=2[O:25][CH3:26])[CH2:4][CH2:3][CH2:2]1.[H-].[Na+].[CH3:30]I>CN(C)C=O.Cl>[CH:1]1([N:5]([CH3:30])[C:6](=[O:27])[C:7]2[CH:12]=[C:11]([O:13][C:14]3[C:19]([Cl:20])=[CH:18][C:17]([CH2:21][O:22][CH3:23])=[CH:16][C:15]=3[Cl:24])[CH:10]=[CH:9][C:8]=2[O:25][CH3:26])[CH2:4][CH2:3][CH2:2]1
COCc1cc(Cl)c(Oc2ccc(OC)c(C(=O)NC3CCC3)c2)c(Cl)c1
CI
null
Cl
[H-]
[Na+]
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
0
0.5
To a solution of the title compound of Step E (170 mg, 0.41 mmol) in dimethylformamide (4 ml) at 0° C. under nitrogen was added sodium hydride (60% dispersion in mineral oil, 41 mg, 1 mmol). The resulting slurry mixture was stirred at 0° C. for about 30 minutes and gradually became a brownish-yellow solution. To this solution at 0° C. was added methyl iodide (0.13 ml, 2 mmol). The resulting solution was warmed to room temperature and stirred for about 19 hours. The solution was diluted with 1N HCl (30 ml) and extracted with ethyl acetate (3×15 ml). The combined organic extracts were washed with 1N HCl (3×50 ml), brine, dried, filtered, and concentrated. The residue was purified by preparative TLC (50% ethyl acetate in hexanes) to afford the title compound (155 mg). MS (APCl+) Calc: 423.1, found: 424.0 (M+1).
COCc1cc(Cl)c(Oc2ccc(OC)c(C(=O)N(C)C3CCC3)c2)c(Cl)c1
null
89.1
null
261,440
ord_dataset-ddb1b60bec5c45e9a2938b6dac04376c
null
1993-01-01T00:02:00
true
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[NH:8][C:9]1[CH2:14][CH2:13][NH:12][C:11](=[O:15])[CH:10]=1>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[F:1][C:2]1[C:3]2[NH:8][C:9]3[CH2:14][CH2:13][NH:12][C:11](=[O:15])[C:10]=3[C:4]=2[CH:5]=[CH:6][CH:7]=1
O=C1C=C(Nc2ccccc2F)CCN1
null
null
[Pd+2]
CC(=O)[O-]
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
null
null
Cupric acetate (2.71 g) was added to a stirred solution of 4-[(2-fluorophenyl)amino]-5,6-dihydro-2(1H)-pyridinone (1.4 g) and palladium (II) acetate (280 mg) in dry DMF (28 ml) under nitrogen. The mixture was heated at 130° for 1.5 h and the solvent was removed in vacuo. The residue was treated with hot methanol (50 ml) and the suspension was filtered and washed with hot methanol (3×50 ml). The combined filtrates were evaporated to give a gum (2.16 g) which was purified by FCC eluting with System A (200:10:1) to give the title compound (490 mg), m.p. 255°-257°.
O=C1NCCc2[nH]c3c(F)cccc3c21
null
155.8
null
1,373,042
ord_dataset-d23f2f15886d4c22b7d7ba5f0e203e81
null
2013-01-01T00:12:00
true
[Br:1][C:2]1[C:10]2[C:9](Cl)=[N:8][CH:7]=[N:6][C:5]=2[N:4]([CH3:12])[CH:3]=1.[OH-].[NH4+:14]>>[Br:1][C:2]1[C:10]2[C:9]([NH2:14])=[N:8][CH:7]=[N:6][C:5]=2[N:4]([CH3:12])[CH:3]=1
Cn1cc(Br)c2c(Cl)ncnc21
[NH4+]
null
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
100
48
A suspension of 5-bromo-4-chloro-7-methyl-7H-pyrrolo[2,3-d]pyrimidine (17 g, 69.0 mmol) in ammonium hydroxide (150 mL, 3852 mmol) was stirred for 2 days at 100° C. in a sealed vessel. The reaction was allowed to cool to room temperature and filtered. The collected solid was washed with Et2O to afford the product 5-bromo-7-methyl-7H-pyrrolo[2,3-d]pyrimidin-4-amine (12.5 g) as a white solid.
Cn1cc(Br)c2c(N)ncnc21
null
79.8
null
852,466
ord_dataset-faa0236be76c4501841c954527cd1b6c
null
2008-01-01T00:12:00
true
[C:1]([OH:6])(=[O:5])[C:2]#[C:3][CH3:4].[CH:7]1[C:19]2[CH:18]([CH2:20]O)[C:17]3[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=3)[C:11]=2[CH:10]=[CH:9][CH:8]=1.C1(C)C=CC(S(O)(=O)=O)=CC=1.CN(C1C=CC=CN=1)C.C1(N=C=NC2CCCCC2)CCCCC1>ClCCl>[C:1]([O:6][CH2:20][CH:18]1[C:19]2[CH:7]=[CH:8][CH:9]=[CH:10][C:11]=2[C:12]2[C:17]1=[CH:16][CH:15]=[CH:14][CH:13]=2)(=[O:5])[C:2]#[C:3][CH3:4]
CC#CC(=O)O
OCC1c2ccccc2-c2ccccc21
null
C(=NC1CCCCC1)=NC1CCCCC1
CN(C)c1ccccn1
Cc1ccc(S(=O)(=O)O)cc1
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
0.25
First, 9-fluorenylmethyl 2-butynoate was prepared. A mixture of 2-butynoic acid (11.6 g, 138 mmol), 9-fluorenemethanol (35.2 g, 179 mmol), dimethylamino-pyridine-p-toluenesulfonic acid salt (16.3 g, 55 mmol), and anhydrous dichloromethane (210 mL) was cooled to 0° C. under nitrogen, and 1,3-dicyclohexylcarbodiimide (34.2 g, 166 mmol) was added. After 15 min, the reaction mixture was warmed to ambient and stirred for 12 h. The urea by product was filtered, and the filtrate was washed successively with 10% aqueous HCl, 10% aqueous NaHCO3, water, and brine. The solution was dried (Na2SO4) and concentrated to deposit a yellow oil. The product was purified by column chromatography to provide 20.0 g (54% of theory) of 9-fluorenylmethyl 2-butynoate as a yellow-green solid. 1H NMR (CDCl3): δ 1.98 (s, 3H), 4.20 (m, 1H), 4.45 (d, 2H), 7.32 (m, 4H), 7.60 (d, 2H), 7.70 (d, 2H).
CC#CC(=O)OCC1c2ccccc2-c2ccccc21
null
55.3
null
146,068
ord_dataset-4731a430f0af464b83e8b5b145cd2c77
null
1986-01-01T00:07:00
true
[F:1][C:2]1[CH:14]=[C:12]2[C:13]3[N:8]([CH:9]=[C:10]([C:16]([OH:18])=[O:17])[C:11]2=[O:15])[CH:7]([CH3:19])[CH2:6][CH2:5][C:4]=3[C:3]=1[N:20]1[CH2:25][CH2:24][NH:23][CH2:22][CH2:21]1.Cl.[N+:27]([C:30]1[CH:37]=[CH:36][C:33]([CH2:34]Br)=[CH:32][CH:31]=1)([O-:29])=[O:28].C(N(CC)CC)C>CN(C)C=O>[N+:27]([C:30]1[CH:37]=[CH:36][C:33]([CH2:34][N:23]2[CH2:22][CH2:21][N:20]([C:3]3[C:4]4=[C:13]5[N:8]([CH:7]([CH3:19])[CH2:6][CH2:5]4)[CH:9]=[C:10]([C:16]([OH:18])=[O:17])[C:11](=[O:15])[C:12]5=[CH:14][C:2]=3[F:1])[CH2:25][CH2:24]2)=[CH:32][CH:31]=1)([O-:29])=[O:28]
O=[N+]([O-])c1ccc(CBr)cc1
CC1CCc2c(N3CCNCC3)c(F)cc3c(=O)c(C(=O)O)cn1c23
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(CC)CC
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
10
A mixture of 9-fluoro-6,7-dihydro-5-methyl-8-(1-piperazinyl)-1-oxo-1H,5H-benzo[ij]quinolizine-2-carboxylic acid (Compound [III]), hydrochloride (1.1 g), p-nitrobenzyl bromide (Compound [IV]) (1.87 g) and triethylamine (1.46 g) in N,N-dimethylformamide (50 ml) was heated with stirring at 80°-90° C. for 10 hr. After evaporation of the solvent, water was added to the residue, and the aqueous mixture was extracted with chloroform. The chloroform layer was dried over anhydrous sodium sulfate and evaporated to dryness. The residue was recrystallized from a mixture of N,N-dimethylformamide and ethanol (2:1) to give 0.83 g (yield: 60%) of 8-[4-(4-nitrobenzyl)-1-piperazinyl]-9-fluoro-6,7-dihydro-5-methyl-1-oxo-1H, 5H-benzo[ij]quinolizine-2-carboxylic acid (Compound [II]) as pale yellow needles, m.p. 230°-233° C. (decompd.).
CC1CCc2c(N3CCN(Cc4ccc([N+](=O)[O-])cc4)CC3)c(F)cc3c(=O)c(C(=O)O)cn1c23
null
60
null
792,159
ord_dataset-744b04e8228742eb9aa4bde36f5dedf1
null
2007-01-01T00:10:00
true
[CH3:1][O:2][C:3]1[C:11]2[O:10][CH:9]=[C:8]([CH2:12][C:13]([CH3:15])=O)[C:7]=2[CH:6]=[CH:5][CH:4]=1.[CH3:16][C:17]1[CH:18]=[C:19]2[C:24](=[C:25]([N:27]3[CH2:32][CH2:31][NH:30][CH2:29][CH2:28]3)[CH:26]=1)[N:23]=[CH:22][CH:21]=[CH:20]2.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCCl.C(O)(=O)C>[CH3:16][C:17]1[CH:18]=[C:19]2[C:24](=[C:25]([N:27]3[CH2:28][CH2:29][N:30]([CH:13]([CH3:15])[CH2:12][C:8]4[C:7]5[CH:6]=[CH:5][CH:4]=[C:3]([O:2][CH3:1])[C:11]=5[O:10][CH:9]=4)[CH2:31][CH2:32]3)[CH:26]=1)[N:23]=[CH:22][CH:21]=[CH:20]2
COc1cccc2c(CC(C)=O)coc12
Cc1cc(N2CCNCC2)c2ncccc2c1
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
ClCCCl
CC(=O)O
null
null
null
null
null
null
null
null
null
null
null
6-methyl-8-{4-[2-(7-methoxy-1-benzofuran-3-yl)-1-methylethyl)piperazin-1-yl]quinoline was prepared by generally following the procedure outlined in example 35, step 2, starting from the 1-(7-methoxy-1-benzofuran-3-yl)acetone (204 mg, 1 mmol) and 6-methyl-8-piperazino quinoline (227.0 mg, 1 mmol) in 1,2-dichloroethane (100 ml) and acetic acid (1 ml), sodium triacetoxyborohydride (422 mg, 2 mmol). The product was purified by silica-gel column chromatography by eluting it initially with 80% ethyl acetate:hexane and then with 5% methanol:ethyl acetate, yielding a yellow oil. Yield: 40 mg (9%); (M+H): 416; 1HNMR (400 MHz, CDCl3): δ 8.86˜8.79 (dd, J1=1.8 Hz, J2=1.8 Hz, 1H), 8.02˜7.56 (dd, J1=1.8 Hz, J2=1.8 Hz, 1H), 7.56˜6.80 (m, 7 H), 3.89 (s, 3H), 3.50˜2.60 (m, 11H); 2.50 (s, 3H) 1.12˜114 (d, J=7.0 Hz, 3H).
COc1cccc2c(CC(C)N3CCN(c4cc(C)cc5cccnc45)CC3)coc12
null
null
null
465,011
ord_dataset-6c36eb0f817d4144988b8963c5d58879
null
2000-01-01T00:05:00
true
[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH2:9][C:10]([C:12]2[NH:16][C:15]([CH3:17])=[C:14]([CH3:18])[CH:13]=2)=[O:11])=[CH:4][CH:3]=1.[CH:19]1([CH2:22]Br)[CH2:21][CH2:20]1>>[CH:19]1([CH2:22][N:16]2[C:12]([C:10](=[O:11])[CH2:9][CH2:8][C:5]3[CH:4]=[CH:3][C:2]([F:1])=[CH:7][CH:6]=3)=[CH:13][C:14]([CH3:18])=[C:15]2[CH3:17])[CH2:21][CH2:20]1
Cc1cc(C(=O)CCc2ccc(F)cc2)[nH]c1C
BrCC1CC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared as a pale yellow oil in 64.8% yield in a similar procedure to that described in Referential Example 97 by using 5-[3-(4-fluorophenyl)propionyl]-2,3-dimethylpyrrole and cyclopropylmethyl bromide.
Cc1cc(C(=O)CCc2ccc(F)cc2)n(CC2CC2)c1C
null
64.8
null
163,757
ord_dataset-f5dc3e448c204058b116bf1970695bef
null
1987-01-01T00:09:00
true
[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([NH2:11])=[C:7]([NH2:12])[CH:6]=1)=[O:4].[CH3:13][O:14][C:15]1[CH:23]=[C:22]([NH:24][S:25]([CH3:28])(=[O:27])=[O:26])[CH:21]=[CH:20][C:16]=1[C:17](O)=O>>[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]2[N:11]=[C:17]([C:16]3[CH:20]=[CH:21][C:22]([NH:24][S:25]([CH3:28])(=[O:27])=[O:26])=[CH:23][C:15]=3[O:14][CH3:13])[NH:12][C:7]=2[CH:6]=1)=[O:4]
COC(=O)c1ccc(N)c(N)c1
COc1cc(NS(C)(=O)=O)ccc1C(=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
Prepared analogously to Example 14 from 4-methoxycarbonyl-1,2-phenylenediamine and 2-methoxy-4-methanesulfonylamino-benzoic acid.
COC(=O)c1ccc2nc(-c3ccc(NS(C)(=O)=O)cc3OC)[nH]c2c1
null
null
null
1,011,650
ord_dataset-7448b89163bf426c9d9777809ce24cec
null
2010-01-01T00:11:00
true
[OH:1][CH:2]1[CH:7]([C:8]2[CH:13]=[CH:12][C:11]([OH:14])=[CH:10][CH:9]=2)[CH2:6][CH2:5][N:4]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:3]1.Br[CH2:23][CH2:24][CH2:25][O:26][C:27]1[CH:32]=[CH:31][CH:30]=[C:29]([F:33])[CH:28]=1>>[F:33][C:29]1[CH:28]=[C:27]([CH:32]=[CH:31][CH:30]=1)[O:26][CH2:25][CH2:24][CH2:23][O:14][C:11]1[CH:10]=[CH:9][C:8]([CH:7]2[CH2:6][CH2:5][N:4]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:3][CH:2]2[OH:1])=[CH:13][CH:12]=1
Fc1cccc(OCCCBr)c1
CC(C)(C)OC(=O)N1CCC(c2ccc(O)cc2)C(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
Analogously to Method I, 0.750 g of tert-butyl 3-hydroxy-4-(4-hydroxyphenyl)piperidine-1-carboxylate and 0.723 g of 1-(3-bromopropoxy)-3-fluorobenzene are reacted. The title compound is obtained as a slightly yellowish oil. Rf=0.30 (1:2 EtOAc-heptane); Rt=5.29.
CC(C)(C)OC(=O)N1CCC(c2ccc(OCCCOc3cccc(F)c3)cc2)C(O)C1
null
null
null
1,670,583
ord_dataset-9cc455db05a444779921f786a45b21a6
null
2015-01-01T00:12:00
true
Cl[C:2]1[CH:11]=[CH:10][C:9]2[C:4](=[CH:5][C:6]([CH3:12])=[CH:7][CH:8]=2)[N:3]=1.[C:13]([NH2:16])(=[O:15])[CH3:14].C([O-])([O-])=O.[K+].[K+]>O>[C:13]([NH:16][C:2]1[CH:11]=[CH:10][C:9]2[C:4](=[CH:5][C:6]([CH3:12])=[CH:7][CH:8]=2)[N:3]=1)(=[O:15])[CH3:14]
Cc1ccc2ccc(Cl)nc2c1
CC(N)=O
null
O=C([O-])[O-]
[K+]
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
230
null
Chloride 19a (0.300 g, 1.69 mmol) was diluted with molten anhydrous acetamide (8 g, 135 mmol) and K2CO3 (1.17 g, 8.45 mmol) was added. The mixture was heated in a sand bath, at reflux (˜230° C.) for 17 h. The mixture was cooled, poured into H2O (120 mL) and extracted with EtOAc (4×30 mL). The organic layers were washed with H2O (3×100 mL) and sat. aq. NaCl (50 mL), dried over anhydrous sodium sulfate, and concentrated. Purification of the residue by flash column chromatography (SiO2, 15% EtOAc in CH2Cl2) afforded the desired compound as a white solid (0.265 g, 78%). 1H-NMR chemical shifts for this compound are consistent with those reported in the literature for the 7-isomer. H-NMR (500 MHz; CDCl3): δ 9.89-9.88 (br s, 1 H), 8.40 (d, J=8.9 Hz, 1 H), 8.15 (d, J=9.0 Hz, 1 H), 7.67 (d, J=8.3 Hz, 1 H), 7.58 (d, J=0.6 Hz, 1 H), 7.29 (dd, J=8.3, 1.4 Hz, 1 H), 2.54 (s, 3 H), 2.27 (s, 3 H).
CC(=O)Nc1ccc2ccc(C)cc2n1
null
78.3
null
1,461,725
ord_dataset-a86112d52cd54525a5e36d41f18aced2
null
2014-01-01T00:07:00
true
[CH3:1][N:2]1[C:7](=[O:8])[CH:6]=[C:5]([N:9]2[CH2:14][CH2:13][O:12][CH2:11][CH2:10]2)[N:4]=[C:3]1[CH2:15][C:16]([O-:18])=O.[Na+].[NH:20]1[C:28]2[C:23](=[CH:24][CH:25]=[CH:26][CH:27]=2)[CH2:22][CH2:21]1.Cl.CN(C)CCCN=C=NCC>N1C=CC=CC=1.CN(C)C=O>[N:20]1([C:16](=[O:18])[CH2:15][C:3]2[N:2]([CH3:1])[C:7](=[O:8])[CH:6]=[C:5]([N:9]3[CH2:10][CH2:11][O:12][CH2:13][CH2:14]3)[N:4]=2)[C:28]2[C:23](=[CH:24][CH:25]=[CH:26][CH:27]=2)[CH2:22][CH2:21]1
c1ccc2c(c1)CCN2
Cn1c(CC(=O)[O-])nc(N2CCOCC2)cc1=O
null
CCN=C=NCCCN(C)C
Cl
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
c1ccncc1
null
null
null
null
null
null
null
null
null
80
null
The product is prepared according to the procedure described in example 5, using 200 mg of sodium [1-methyl-4-(morpholin-4-yl)-6-oxo-1,6-dihydropyrimidin-2-yl]acetate prepared in stage 1 of example 68, 174 mg of 2,3-dihydro-1H-indole, and 185 mg of N-[3-(dimethylamino)propyl]-N′-ethylcarbodiimide hydrochloride in a mixture of 0.12 ml of pyridine and 3 ml of N,N-dimethylformamide. After silica column purification, eluent: 93/07 CH2Cl2/MeOH, the solid is taken up with 4 ml of methanol and a few drops of acetone. The suspension is heated at a temperature of 80° C., filtered while hot, and then recrystallized at a temperature of 20° C. and then of 0° C. The solid is filtered off, rinsed with diethyl ether, and then dried under a vacuum bell jar. 52 mg of 2-[2-(2,3-dihydro-1H-indol-1-yl)-2-oxoethyl]-3-methyl-6-(morpholin-4-yl)pyrimidin-4(3H)-one are obtained in the form of white crystals, the characteristics of which are the following:
Cn1c(CC(=O)N2CCc3ccccc32)nc(N2CCOCC2)cc1=O
null
20.2
null
1,750,352
ord_dataset-60a3e71da3174666a50a61dcfa611a9f
null
2016-01-01T00:07:00
true
[NH:1]1[CH2:4][CH2:3][CH2:2]1.Cl[C:6]1[N:11]=[C:10]([NH:12][C:13]2[CH:14]=[C:15]([CH:18]=[CH:19][N:20]=2)[C:16]#[N:17])[CH:9]=[C:8]([C:21]2([C:27]#[N:28])[CH2:26][CH2:25][O:24][CH2:23][CH2:22]2)[CH:7]=1>>[N:1]1([C:6]2[N:11]=[C:10]([NH:12][C:13]3[CH:14]=[C:15]([CH:18]=[CH:19][N:20]=3)[C:16]#[N:17])[CH:9]=[C:8]([C:21]3([C:27]#[N:28])[CH2:26][CH2:25][O:24][CH2:23][CH2:22]3)[CH:7]=2)[CH2:4][CH2:3][CH2:2]1
C1CNC1
N#Cc1ccnc(Nc2cc(C3(C#N)CCOCC3)cc(Cl)n2)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
Reaction of azetidine with 2-((6-chloro-4-(4-cyanotetrahydro-2H-pyran-4-yl)pyridin-2-yl)amino)isonicotinonitrile (50.0 mg, 0.147 mmol) following procedure of Method A afforded the target compound as a colorless solid (8.9 mg, 17%); 1H NMR (400 MHz, DMSO) δ 9.95 (br s, 1H), 8.48 (s, 1H), 8.42 (d, J=5.0 Hz, 1H), 7.23 (dd, J=5.0, 1.4 Hz, 1H), 6.89 (d, J=1.2 Hz, 1H), 5.99 (d, J=1.2 Hz, 1H), 4.06-3.98 (m, 6H), 3.70-3.59 (m, 2H), 2.41-2.28 (m, 2H), 2.08-1.96 (m, 4H); ESI-LRMS m/z [M+1]+=361.
N#Cc1ccnc(Nc2cc(C3(C#N)CCOCC3)cc(N3CCC3)n2)c1
null
17
null
890,992
ord_dataset-11068b1e475b4c5b82e56726ab0dddb7
null
2009-01-01T00:07:00
true
[O:1]1[C:6]2[CH:7]=[CH:8][C:9]([C:11]([C:13]3[C:22](=[O:23])[C:21]4[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=4)[NH:15][CH:14]=3)=[O:12])=[CH:10][C:5]=2[O:4][CH2:3][CH2:2]1.Br[CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[C:28]([C:32]([F:35])([F:34])[F:33])[CH:27]=1>>[O:1]1[C:6]2[CH:7]=[CH:8][C:9]([C:11]([C:13]3[C:22](=[O:23])[C:21]4[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=4)[N:15]([CH2:25][C:26]4[CH:31]=[CH:30][CH:29]=[C:28]([C:32]([F:33])([F:34])[F:35])[CH:27]=4)[CH:14]=3)=[O:12])=[CH:10][C:5]=2[O:4][CH2:3][CH2:2]1
O=C(c1ccc2c(c1)OCCO2)c1c[nH]c2ccccc2c1=O
FC(F)(F)c1cccc(CBr)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
Experimental conditions analogous to those described for Step 3 of Example 1, from 3-(2,3-Dihydro-benzo[1,4]dioxine-6-carbonyl)-1H-quinolin-4-one 70.7 mg (0.296 mmol) and 71.1 mg (0.296 mmol) of 1-Bromomethyl-3-trifluoromethyl-benzene, to give 21 mg of desired compound. LCMS (M+H)+: 466.
O=C(c1ccc2c(c1)OCCO2)c1cn(Cc2cccc(C(F)(F)F)c2)c2ccccc2c1=O
null
15.2
null
1,712,061
ord_dataset-3f2a531ffbae4b9eb1048afcd7953beb
null
2016-01-01T00:04:00
true
[C:1]([O:5][C:6]([NH:8][C@H:9]([CH2:26][C:27]1[CH:32]=[CH:31][C:30]([NH:33]C(OCC2C3C=CC=CC=3C3C2=CC=CC=3)=O)=[CH:29][CH:28]=1)[C:10]([NH:12][C@@H:13]([CH:23]([CH3:25])[CH3:24])[CH2:14][O:15][CH2:16][CH2:17][C:18]([O:20]CC)=[O:19])=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].[Li+].[OH-].Cl>C1COCC1.CO>[NH2:33][C:30]1[CH:31]=[CH:32][C:27]([CH2:26][C@@H:9]([NH:8][C:6]([O:5][C:1]([CH3:3])([CH3:2])[CH3:4])=[O:7])[C:10]([NH:12][C@@H:13]([CH:23]([CH3:25])[CH3:24])[CH2:14][O:15][CH2:16][CH2:17][C:18]([OH:20])=[O:19])=[O:11])=[CH:28][CH:29]=1
CCOC(=O)CCOC[C@@H](NC(=O)[C@@H](Cc1ccc(NC(=O)OCC2c3ccccc3-c3ccccc32)cc1)NC(=O)OC(C)(C)C)C(C)C
null
null
Cl
[Li+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
C1CCOC1
null
null
null
null
null
null
null
null
null
null
1
355.0 mg (0.52 mmol) of ethyl 3-((S)-2-{(R)-2-tert-butoxycarbonylamino-3-[4-(9H-fluoren-9-ylmethoxycarbonylamino)phenyl]propionylamino}-3-methylbutoxy)propionate were dissolved in a mixture of 9 ml of THF and 3 ml of MeOH. 1.29 ml (1.29 mmol) of an aqueous 1M LiOH solution were added, and the resulting reaction mixture was stirred at room temp. for 1 h. After the reaction was complete, the mixture was neutralized by adding a little aqueous 1N HCl solution, concentrated under reduced pressure and codistilled with toluene. The product obtained in this way (225.0 mg) was employed crude in the next reaction.
CC(C)[C@@H](COCCC(=O)O)NC(=O)[C@@H](Cc1ccc(N)cc1)NC(=O)OC(C)(C)C
null
null
null
1,770,688
ord_dataset-0b32b90cc77b4a3db47ad263e0bbc1a8
null
2016-01-01T00:09:00
true
[CH3:1][N:2]1[C:6]([C:7]2[CH:16]=[CH:15][CH:14]=[CH:13][C:8]=2[C:9]([O:11]C)=[O:10])=[C:5]([CH3:17])[CH:4]=[N:3]1.[Li+].[OH-]>CO>[CH3:1][N:2]1[C:6]([C:7]2[CH:16]=[CH:15][CH:14]=[CH:13][C:8]=2[C:9]([OH:11])=[O:10])=[C:5]([CH3:17])[CH:4]=[N:3]1
COC(=O)c1ccccc1-c1c(C)cnn1C
null
null
[Li+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
50
null
To a solution of the title compound of Step A (680 mg, 2.95 mmol) in MeOH (15 mL) was added 4 M LiOH (4 mL). The mixture was heated at 50° C. overnight. MeOH was removed and HCl added until pH=2. White solids precipitated from the reaction mixture and the precipitate was filtered, washed with EtOAc and collected to give intermediate A-31, which was used without further purification in subsequent steps. MS (ESI) mass calcd. for C12H12N2O2, 216.1. m/z found 217.1 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ 12.87 (s, 1H), 7.95 (dd, J=7.8, 1.5 Hz, 1H), 7.67 (td, J=7.5, 1.5 Hz, 1H), 7.59 (td, J=7.6, 1.4 Hz, 1H), 7.33 (dd, J=7.6, 1.4 Hz, 1H), 7.25 (s, 1H), 3.48 (s, 3H), 1.77 (s, 3H).
Cc1cnn(C)c1-c1ccccc1C(=O)O
null
null
null
1,219,088
ord_dataset-dc3bb1b1ac4e4229a3fc28fb559a9777
null
2012-01-01T00:10:00
true
[H-].[Na+].[CH2:3]([O:10][CH2:11][C:12]([CH3:18])([CH3:17])[C:13]([O:15]C)=O)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[C:19](#[N:21])[CH3:20].Cl>C1(C)C=CC=CC=1>[CH2:3]([O:10][CH2:11][C:12]([CH3:18])([CH3:17])[C:13](=[O:15])[CH2:20][C:19]#[N:21])[C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][CH:9]=1
CC#N
COC(=O)C(C)(C)COCc1ccccc1
null
Cl
[H-]
[Na+]
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
1
To a suspension of sodium hydride (1.62 g of a 60% w/w dispersion in mineral oil, 40.5 mmol) in toluene (20 mL) at reflux was added a solution of methyl 3-(benzyloxy)-2,2-dimethylpropanoate [Eur. J. Org. Chem., 2007 (6) 934-942] (6.00 g, 27.0 mmol) and acetonitrile (2.12 ml, 40.5 mmol) in toluene, dropwise over 1 hr. The reaction mixture was heated for a further 5 hr at reflux then cooled to RT. The mixture was acidified to pH 4 with aqueous hydrochloric acid (1M) and extracted with EtOAc. The organic extract was washed with water and with brine then dried (MgSO4) and evaporated in vacuo to afford 5-(benzyloxy)-4,4-dimethyl-3-oxopentanenitrile as a yellow oil (7.50 g, 96%): m/z 232 (M+H)+ (ES+), which was used without purification in the next step.
CC(C)(COCc1ccccc1)C(=O)CC#N
null
120.1
null
1,648,483
ord_dataset-bcc0b01d4f58457a8733b10a099f43ba
null
2015-01-01T00:10:00
true
[CH2:1]([C:3]1[N:12]([CH2:13][CH2:14][N:15]2[CH2:20][CH2:19][N:18]([C:21]3[CH:26]=[CH:25][CH:24]=[C:23](C(F)(F)F)[CH:22]=3)[CH2:17][CH2:16]2)[C:11](=[O:31])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[N:4]=1)[CH3:2].[CH3:32][O:33]C1C=CC=CC=1N1CCNCC1>>[CH2:1]([C:3]1[N:12]([CH2:13][CH2:14][N:15]2[CH2:20][CH2:19][N:18]([C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][C:22]=3[O:33][CH3:32])[CH2:17][CH2:16]2)[C:11](=[O:31])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[N:4]=1)[CH3:2]
COc1ccccc1N1CCNCC1
CCc1nc2ccccc2c(=O)n1CCN1CCN(c2cccc(C(F)(F)F)c2)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
This compound was prepared in compliance with the procedure described in 7d, using 1-(2-methoxyphenyl)piperazine instead of 1-(3-(trifluoromethyl)phenyl)piperazine.
CCc1nc2ccccc2c(=O)n1CCN1CCN(c2ccccc2OC)CC1
null
null
null
155,426
ord_dataset-d1c545e3afc447099315419421478aab
null
1987-01-01T00:03:00
true
[Cl:1][C:2]1[C:7]([Cl:8])=[CH:6][CH:5]=[CH:4][C:3]=1[CH:9]1[C:14]([C:15]([O:17][CH3:18])=[O:16])=[C:13]([CH3:19])[NH:12][C:11]([CH2:20][O:21][CH2:22][C:23](O)=[O:24])=[C:10]1[C:26]([O:28][CH2:29][CH3:30])=[O:27].B>>[Cl:1][C:2]1[C:7]([Cl:8])=[CH:6][CH:5]=[CH:4][C:3]=1[CH:9]1[C:14]([C:15]([O:17][CH3:18])=[O:16])=[C:13]([CH3:19])[NH:12][C:11]([CH2:20][O:21][CH2:22][CH2:23][OH:24])=[C:10]1[C:26]([O:28][CH2:29][CH3:30])=[O:27]
CCOC(=O)C1=C(COCC(=O)O)NC(C)=C(C(=O)OC)C1c1cccc(Cl)c1Cl
null
null
B
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
was prepared by the method described in Example 1 using 2-{[4-(2,3-dichlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-1,4-dihydropyrid-2-yl]methoxy}acetic acid (see Preparation 5 of European patent application publication No. 0100189) and borane as the starting materials.
CCOC(=O)C1=C(COCCO)NC(C)=C(C(=O)OC)C1c1cccc(Cl)c1Cl
null
null
null
472,993
ord_dataset-cd531114850e4f239b2a3661044ae672
null
2000-01-01T00:08:00
true
C(OC(=O)[NH:7][C@@H:8]([C:16](=[O:19])[NH:17][CH3:18])[CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)(C)(C)C.[ClH:21].O1CCOCC1>>[ClH:21].[NH2:7][C@H:8]([CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[C:16]([NH:17][CH3:18])=[O:19]
CNC(=O)[C@@H](Cc1ccccc1)NC(=O)OC(C)(C)C
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1COCCO1
null
null
null
null
null
null
null
null
null
null
25
1
(R)-(1-Methylcarbamoyl-2-phenyl-ethyl)-carbamic acid tert-butyl ester (722 mg, 2.6 mmol) was dissolved in 4M HCl-dioxane (10 mL) at 0° C. The mixture was stirred for 1 hour at 25° C., concentrated and the residue triturated with ether. Yield, 517 mg, 93%.
CNC(=O)[C@H](N)Cc1ccccc1
null
null
null
517,121
ord_dataset-a495451286334c5c9bbcbd48a00c1350
null
2001-01-01T00:09:00
true
Cl[C:2]1[C:11]2[C:6](=[CH:7][C:8]([O:15][CH2:16][CH3:17])=[C:9]([O:12][CH2:13][CH3:14])[CH:10]=2)[N:5]=[CH:4][C:3]=1[C:18]#[N:19].[NH2:20][C:21]1[CH:30]=[C:29]2[C:24]([C:25]([CH3:32])=[CH:26][C:27](=[O:31])[O:28]2)=[CH:23][CH:22]=1.C(=O)([O-])[O-].[Na+].[Na+]>COCCO>[CH2:13]([O:12][C:9]1[CH:10]=[C:11]2[C:6](=[CH:7][C:8]=1[O:15][CH2:16][CH3:17])[N:5]=[CH:4][C:3]([C:18]#[N:19])=[C:2]2[NH:20][C:21]1[CH:30]=[C:29]2[C:24]([C:25]([CH3:32])=[CH:26][C:27](=[O:31])[O:28]2)=[CH:23][CH:22]=1)[CH3:14]
Cc1cc(=O)oc2cc(N)ccc12
CCOc1cc2ncc(C#N)c(Cl)c2cc1OCC
null
O=C([O-])[O-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
COCCO
null
null
null
null
null
null
null
null
null
null
100
null
A solution of 400 mg (1.44 mM) of 4-chloro-6,7-diethoxy-quinoline-3-carbonitrile and 330 mg (1.88 mM) of 7-Amino-4-methyl-coumarin in 15 ml of 2-methoxyethanol was refluxed for 3 hours. To the warm solution was added 1 ml of 1M sodium carbonate and the sample was heated for 5 minutes at 100° C., then poured into 300 ml of ice water. The solid was collected, washed with water followed by ether and dried under vacuum at 80° C. to yield 431 mg of 6,7-Diethoxy-4-(4-methyl-2-oxo-2H-chromen-7-ylamino)-quinoline-3-carbonitrile as a tan solid: mass spectrum (electrospray, m/e): M+H 416.0, mp=282-284° C.
CCOc1cc2ncc(C#N)c(Nc3ccc4c(C)cc(=O)oc4c3)c2cc1OCC
null
71.8
null
1,315,218
ord_dataset-2d6edb8ffd434003bb508360153bd9bb
null
2013-01-01T00:07:00
true
[NH2:1][C:2]1[CH:7]=[C:6]([NH:8][C:9](=[O:18])[C:10]2[C:15]([Cl:16])=[CH:14][CH:13]=[CH:12][C:11]=2[Cl:17])[CH:5]=[CH:4][N:3]=1.[S:19]1[CH:23]=[CH:22][CH:21]=[C:20]1[C:24](Cl)=[O:25].O>N1C=CC=CC=1>[Cl:16][C:15]1[CH:14]=[CH:13][CH:12]=[C:11]([Cl:17])[C:10]=1[C:9]([NH:8][C:6]1[CH:5]=[CH:4][N:3]=[C:2]([NH:1][C:24]([C:20]2[S:19][CH:23]=[CH:22][CH:21]=2)=[O:25])[CH:7]=1)=[O:18]
Nc1cc(NC(=O)c2c(Cl)cccc2Cl)ccn1
O=C(Cl)c1cccs1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
c1ccncc1
O
null
null
null
null
null
null
null
null
null
0
0.33
N-(2-aminopyridin-4-yl)-2,6-dichlorobenzamide (240 mg, 0.86 mmol) was dissolved in pyridine (10 mL). The mixture was stirred at 0° C. for 20 min. and then thiophene-2-carbonyl chloride (113 mg, 0.77 mmol) was added dropwise. The mixture was warmed to 23° C. and stirred under nitrogen overnight. The next day, water (1 mL) was added and the mixture was stirred for 5 min. The reaction was concentrated under reduced pressure and the residue was purified by reverse-phase HPLC (Gemini, 200 mm×25 mm, gradient: CH3CN/0.05% NH3.H2O, 50-80, 10 min) to afford the desired product (72.6 mg, yield: 22%). 1HNMR: (DMSO-d6, 400 MHz): δ 11.38 (s, 1H), 10.92 (s, 1H), 8.47 (s, 1H), 8.33 (d, J=5.6 Hz, 1H), 8.26 (d, J=2.8 Hz, 1H), 7.90 (d, J=5.2 Hz, 1H), 7.62-7.51 (m, 4H), 7.22 (t, J=4.4 Hz, 1H). LCMS (ESI) (m/z): 414.3 [M+Na+].
O=C(Nc1cc(NC(=O)c2c(Cl)cccc2Cl)ccn1)c1cccs1
null
24
null
1,625,544
ord_dataset-35c51552812941cda45194a013d34bb9
null
2015-01-01T00:08:00
true
[C:1]([C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[C:9]1[CH:14]=[CH:13][C:12]([CH2:15][CH:16]([C:22](=O)[CH2:23][CH2:24][CH3:25])[C:17](OCC)=[O:18])=[C:11]([F:27])[CH:10]=1)#[N:2].[CH3:28][O:29][CH2:30][CH:31]([NH:33][C:34]1[NH:38][C:37]([CH3:39])=[N:36][N:35]=1)[CH3:32]>>[F:27][C:11]1[CH:10]=[C:9]([C:4]2[C:3]([C:1]#[N:2])=[CH:8][CH:7]=[CH:6][CH:5]=2)[CH:14]=[CH:13][C:12]=1[CH2:15][C:16]1[C:17](=[O:18])[N:33]([CH:31]([CH3:32])[CH2:30][O:29][CH3:28])[C:34]2[N:35]([N:36]=[C:37]([CH3:39])[N:38]=2)[C:22]=1[CH2:23][CH2:24][CH3:25]
COCC(C)Nc1nnc(C)[nH]1
CCCC(=O)C(Cc1ccc(-c2ccccc2C#N)cc1F)C(=O)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
250
0.33
A mixture of ethyl 2-[(2′-cyano-3-fluorobiphenyl-4-yl)methyl]-3-oxohexanoate (1 g) and N-(2-methoxy-1-methylethyl)-5-methyl-4H-1,2,4-triazol-3-amine (0.25 g) was stirred at 250° C. for 20 min under microwave irradiation. The obtained reaction mixture was purified by silica gel column chromatography to give the title compound as a colorless solid (0.28 g, 40%).
CCCc1c(Cc2ccc(-c3ccccc3C#N)cc2F)c(=O)n(C(C)COC)c2nc(C)nn12
null
40.3
null
1,414,098
ord_dataset-f8e6e6a2d2bf4135b9e346456c81700f
null
2014-01-01T00:04:00
true
[Br:1][C:2]1[C:7]([CH:8]=[O:9])=[C:6]([OH:10])[C:5]([O:11][CH3:12])=[CH:4][CH:3]=1.[OH:13][CH2:14][C:15]([CH3:19])([CH2:17]O)[CH3:16].C(OCC)(OCC)OCC>CC1C=CC(S(O)(=O)=O)=CC=1>[Br:1][C:2]1[C:7]([CH:8]2[O:13][CH2:14][C:15]([CH3:19])([CH3:17])[CH2:16][O:9]2)=[C:6]([OH:10])[C:5]([O:11][CH3:12])=[CH:4][CH:3]=1
CC(C)(CO)CO
COc1ccc(Br)c(C=O)c1O
null
Cc1ccc(S(=O)(=O)O)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOC(OCC)OCC
null
null
null
null
null
null
null
null
null
null
110
null
A mixture of 6-bromo-2-hydroxy-3-methoxy-benzaldehyde (2.31 g, 10.0 mmol), neopentyl glycol (1.14 g, 11.0 mmol), TsOH (9.5 mg) and triethyl orthoformate (1.93 g, 13.0 mmol) were heated at 110° C. for 30 min and then partitioned between NaHCO3 (300 mL) solution and EtOAc (200 mL). The aqueous layer was extracted with EtOAc (3×30 mL) and the combined extracts were washed with brine and dried through Na2SO4. Evaporation of solvent afforded the title compound (3.17 g, 100%). 1H NMR (CDCl3) δ 0.85 (s, 3H), 1.27 (s, 3H), 3.70 (s, 2H), 3.82 (s, 2H), 3.85 (s, 3H), 5.90 (s, 1H), 6.72 (d, J=8 Hz, 1H), 7.02 (d, J=8 Hz, 1H).
COc1ccc(Br)c(C2OCC(C)(C)CO2)c1O
null
99.9
null
679,369
ord_dataset-3947f3e1be17462c8f7c7e6ea6e57d0a
null
2005-01-01T00:08:00
true
[CH3:1][S:2]([C:5]1[CH:6]=[C:7]([N:13]2[CH2:18][CH2:17][NH:16][CH2:15][CH2:14]2)[CH:8]=[CH:9][C:10]=1[O:11][CH3:12])(=[O:4])=[O:3].[CH2:19](Br)[CH:20]=[CH2:21]>>[CH2:21]([N:16]1[CH2:15][CH2:14][N:13]([C:7]2[CH:8]=[CH:9][C:10]([O:11][CH3:12])=[C:5]([S:2]([CH3:1])(=[O:3])=[O:4])[CH:6]=2)[CH2:18][CH2:17]1)[CH:20]=[CH2:19]
COc1ccc(N2CCNCC2)cc1S(C)(=O)=O
C=CCBr
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Beginning with 1-(3-Methanesulfonyl-4-methoxy-phenyl)-piperazine and allylbromide, the title compound was recovered by the procedure described in Example 2: MS m/z (rel. intensity, 70 eV)) 310 (M+, 91), 214 (73), 96 (86), 69 (80), 56 (bp).
C=CCN1CCN(c2ccc(OC)c(S(C)(=O)=O)c2)CC1
null
null
null
1,502,088
ord_dataset-366bdd9ee72d474cbe6f3f9e54dd96d2
null
2014-01-01T00:10:00
true
[F:1][C:2]([F:7])([F:6])[C:3]([OH:5])=[O:4].F[C:9](F)(F)[C:10](O)=[O:11].[Cl:15][C:16]1[CH:17]=[N:18][C:19]2[NH:20][C:21]3[CH:22]=[CH:23][CH:24]=[C:25]([CH:47]=3)[CH2:26][CH2:27][C:28]3[CH:36]=[C:32]([NH:33][C:34]=1[N:35]=2)[CH:31]=[CH:30][C:29]=3[NH:37][C:38](=[O:46])[CH2:39][C@@H:40]1[CH2:45][CH2:44][CH2:43][NH:42][CH2:41]1.C(Cl)(=O)C>>[F:1][C:2]([F:7])([F:6])[C:3]([OH:5])=[O:4].[C:10]([N:42]1[CH2:43][CH2:44][CH2:45][C@@H:40]([CH2:39][C:38]([NH:37][C:29]2[CH:30]=[CH:31][C:32]3[NH:33][C:34]4[N:35]=[C:19]([NH:20][C:21]5[CH:22]=[CH:23][CH:24]=[C:25]([CH:47]=5)[CH2:26][CH2:27][C:28]=2[CH:36]=3)[N:18]=[CH:17][C:16]=4[Cl:15])=[O:46])[CH2:41]1)(=[O:11])[CH3:9]
O=C(C[C@@H]1CCCNC1)Nc1ccc2cc1CCc1cccc(c1)Nc1ncc(Cl)c(n1)N2
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(=O)Cl
O=C(O)C(F)(F)F
null
null
null
null
null
null
null
null
null
null
null
The desired compound was prepared according to the procedure of Example D94 using N-[6-chloro-2,4,8,22-tetraazatetracyclo[14.3.1.1(3,7).1(9,13)]docosa-1(20),3(22),4,6,9(21),10,12,16,18-nonaen-12-yl]-2-[(3S)-piperidin-3-yl]acetamide bis(trifluoroacetate) and acetyl chloride as the starting materials in 67% yield. LCMS for C27H30ClN6O2 (M+H)+: m/z=505.1.
CC(=O)N1CCC[C@@H](CC(=O)Nc2ccc3cc2CCc2cccc(c2)Nc2ncc(Cl)c(n2)N3)C1
null
67
null
1,601,848
ord_dataset-e8c6a25568b64529b960953990e6921f
null
2015-01-01T00:06:00
true
[CH3:1][C:2]1([CH3:23])[C@@H:5]([C:6]([O:8]C(C)(C)C)=[O:7])[CH2:4][C@H:3]1[C:13]([O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)=[O:14].Cl.O1CCOCC1>C(OCC)(=O)C>[CH2:16]([O:15][C:13]([C@@H:3]1[CH2:4][C@H:5]([C:6]([OH:8])=[O:7])[C:2]1([CH3:23])[CH3:1])=[O:14])[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1
CC(C)(C)OC(=O)[C@H]1C[C@@H](C(=O)OCc2ccccc2)C1(C)C
null
null
Cl
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
25
12
To a solution of (1R,3S)-1-benzyl 3-tert-butyl 2,2-dimethylcyclobutane-1,3-dicarboxylate (step 3, 1.0 g) dioxane-HCl (10 ml) was added at about 0° C. under nitrogen atmosphere. The reaction mixture was stirred for about 12 hours at room temperature. After completion of the reaction (monitored by TLC), the reaction mixture was diluted with ethyl acetate and washed with water. The organic layer was washed with brine, dried over Na2SO4 and concentrated under reduced pressure to give crude product, which upon column chromatography to afford the title compound (800 mg, 97.2% Yield). 1H NMR (300 MHz, CDCl3): δ 7.35 (5H, s), 5.12 (2H, d, J=2.7 Hz), 2.84 (2H, m), 2.63 (1H, m), 2.0 (1H, m), 1.35 (3H, s), 0.99 (3H, s); Mass: [M+H]+ 263.1 (20%), 285.1 [M+Na]+.
CC1(C)[C@@H](C(=O)O)C[C@H]1C(=O)OCc1ccccc1
null
97.1
null
755,960
ord_dataset-1b0cd79134f0450eaac8396a4f956c30
null
2007-01-01T00:02:00
true
[NH2:1][CH:2]1[CH2:6][CH2:5][S:4](=[O:8])(=[O:7])[CH2:3]1.CCN(C(C)C)C(C)C.[F:18][C:19]1[CH:24]=[CH:23][C:22]([NH:25][C:26]([C:28]2[C:29](Cl)=[N:30][C:31]([S:34][CH3:35])=[N:32][CH:33]=2)=[O:27])=[CH:21][CH:20]=1>CO>[F:18][C:19]1[CH:24]=[CH:23][C:22]([NH:25][C:26]([C:28]2[C:29]([NH:1][CH:2]3[CH2:6][CH2:5][S:4](=[O:8])(=[O:7])[CH2:3]3)=[N:30][C:31]([S:34][CH3:35])=[N:32][CH:33]=2)=[O:27])=[CH:21][CH:20]=1
CSc1ncc(C(=O)Nc2ccc(F)cc2)c(Cl)n1
NC1CCS(=O)(=O)C1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(C(C)C)C(C)C
CO
null
null
null
null
null
null
null
null
null
0
16
To a suspension of 3-amino-1,1-dioxotetrahydrothiophene (345 mg, 2.01 mmol) in methanol (5 mL) was added DIPEA (350 μL) followed by 4-chloro-2-methylsulfanylpyrimidine-5-carboxylic acid (4-fluorophenyl)amide (200 mg, 0.67 mmol). The mixture was allowed to stir for 16 h. The resulting mixture was poured into ice-water and the resulting solids were collected by filtration. The solids were washed with ethyl acetate and hexanes and were dried. This afforded 147 mg (0.37 mmol, 55% yield) of the titled product as a solid. 1H NMR (300 MHz, DMSO-d6) δ 10.25 (s, 1H), 8.78 (d, 1H), 8.65 (s, 1H), 7.65 (m, 2H), 7.18 (m, 2H), 4.87 (m, 1H), 3.52 (m, 1H), 3.35–3.04 (m, 3H), 2.50, M, 1H), 2.22 (m, 1H); MS (EI) m/z 395.05 (M−H)−.
CSc1ncc(C(=O)Nc2ccc(F)cc2)c(NC2CCS(=O)(=O)C2)n1
null
55.2
null
191,182
ord_dataset-d1bd8c96676b4d21aad27b173c6b4eff
null
1989-01-01T00:06:00
true
[C:1]1([CH:8]=[CH:7][CH:6]=[C:4]([OH:5])[CH:3]=1)[OH:2].CO[CH:11]([CH3:15])[C:12](=O)[CH3:13]>C1(C)C=CC=CC=1>[CH3:15][C:11]1[O:2][C:1]2[CH:3]=[C:4]([OH:5])[CH:6]=[CH:7][C:8]=2[C:12]=1[CH3:13]
Oc1cccc(O)c1
COC(C)C(C)=O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
null
null
null
null
null
null
null
null
null
null
90
10
A mixture of 1.9 g of resorcinol, 1.8 g of 3-methoxy-2-butanone, 0.2 g of Amberlyst-15 and 2 ml of toluene was stirred at 90° C. for 10 hours. After cooling, the catalyst was separated, and the filtrate was concentrated. The residue was purified by column chromatography to give 1.7 g of 2,3-dimethyl-6-hydroxybenzofuran as pale yellow crystals. The crystals were dissolved in 20 ml of acetic acid, and 0.2 g of 5% palladium-carbon was added. The mixture was stirred at room temperature for 12 hours in an atmosphere of hydrogen. The crude product was purified by column chromatography to give 1.5 g (yield 54%) of the desired product as a brown liquid.
Cc1oc2cc(O)ccc2c1C
null
60.7
null
1,460,433
ord_dataset-a86112d52cd54525a5e36d41f18aced2
null
2014-01-01T00:07:00
true
Cl[C:2]1[N:7]=[C:6]([NH:8][CH3:9])[C:5]([C:10]([F:13])([F:12])[F:11])=[CH:4][N:3]=1.[CH3:14][O:15][C:16]1[CH:22]=[C:21]([N:23]2[CH:27]=[N:26][CH:25]=[N:24]2)[CH:20]=[CH:19][C:17]=1[NH2:18].C1(C)C=CC(S(O)(=O)=O)=CC=1>O1CCOCC1>[CH3:14][O:15][C:16]1[CH:22]=[C:21]([N:23]2[CH:27]=[N:26][CH:25]=[N:24]2)[CH:20]=[CH:19][C:17]=1[NH:18][C:2]1[N:7]=[C:6]([NH:8][CH3:9])[C:5]([C:10]([F:13])([F:12])[F:11])=[CH:4][N:3]=1
COc1cc(-n2cncn2)ccc1N
CNc1nc(Cl)ncc1C(F)(F)F
null
Cc1ccc(S(=O)(=O)O)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1COCCO1
null
null
null
null
null
null
null
null
null
null
100
null
A mixture of 2-chloro-N-methyl-5-(trifluoromethyl)pyrimidin-4-amine (80 mg, 0.38 mmol), 2-methoxy-4-(1H-1,2,4-triazol-1-yl)aniline (72 mg, 0.38 mmol) and p-toluene sulphonic acid (72 mg, 0.38 mmol) in dioxane (2 mL) was heated at 100° C. for 1 h. The mixture was cooled and filtered. The solid was partitioned between dichloromethane (10 mL) and saturated aqueous NaHCO3 (10 mL) and the product was extracted into dichloromethane (3×10 mL). The combined organics were passed through a phase separation cartridge and the solvent removed under reduced pressure. Purification of the residue via silica gel column chromatography (0-100% ethyl acetate/isohexane) afforded a residue that was triturated with methanol/diethyl ether yielding N2-(2-methoxy-4-(1H-1,2,4-triazol-1-yl)phenyl)-N4-methyl-5-(trifluoromethyl)pyrimidine-2,4-diamine as a white solid (34.5 mg, 25%). LCMS (10 cm_ESCI_Formic_MeCN): [MH+]=366 at 3.13 min. 1H NMR (400 MHz, DMSO): δ 9.29 (s, 1H); 8.33 (d, J=8.7, 1H); 8.24-8.15 (m, 3H); 7.53 (d, J=2.4, 1H); 7.45 (dd, J=8.7, 2.4, 1H); 7.23 (d, J=5.2, 1H); 3.97 (s, 3H); 2.92 (d, J=4.4, 3H).
CNc1nc(Nc2ccc(-n3cncn3)cc2OC)ncc1C(F)(F)F
null
24.9
null
1,655,471
ord_dataset-42cd9bc5aae3485f9a58f1527bd3abf0
null
2015-01-01T00:11:00
true
[C:1]([C:3]1[CH:4]=[C:5]2[C:9](=[CH:10][CH:11]=1)[CH2:8][N:7]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:6]2)#[N:2].Cl.[NH2:20][OH:21].CCN(C(C)C)C(C)C>CCO>[OH:21][NH:20][C:1]([C:3]1[CH:4]=[C:5]2[C:9](=[CH:10][CH:11]=1)[CH2:8][N:7]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:6]2)=[NH:2]
NO
CC(C)(C)OC(=O)N1Cc2ccc(C#N)cc2C1
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(C(C)C)C(C)C
CCO
null
null
null
null
null
null
null
null
null
null
null
A product of Step C (0.22 g; 0.904 mmol), HCl×NH2OH (0.16 g; 2.3 mmol) and DIPEA (0.48 ml; 5 mmol) in anhydrous EtOH (3.5 ml) was refluxed for 2 h under N2. The solvents were removed under reduced pressure and the residue was diluted to 30 ml with EtOAc, washed with H2O (2×5 ml), brine, dried over anhydrous MgSO4, filtered and the filtrate evaporated to dryness to give the title compound (0.25 g; 100%) as colourless foam, which was used in next step without further purification.
CC(C)(C)OC(=O)N1Cc2ccc(C(=N)NO)cc2C1
null
99.7
null
1,047,715
ord_dataset-dd320ded4b3f4764af39de99491533f7
null
2011-01-01T00:04:00
true
Cl[C:2]1[N:7]=[C:6]([C:8]2[CH:20]=[CH:19][C:11]3[N:12]=[C:13]([NH:15][C:16](=[O:18])[CH3:17])[S:14][C:10]=3[CH:9]=2)[CH:5]=[CH:4][N:3]=1.[N:21]1(N)[CH2:26][CH2:25][CH2:24][CH2:23][CH2:22]1>CS(C)=O>[N:21]1([C:2]2[N:7]=[C:6]([C:8]3[CH:20]=[CH:19][C:11]4[N:12]=[C:13]([NH:15][C:16](=[O:18])[CH3:17])[S:14][C:10]=4[CH:9]=3)[CH:5]=[CH:4][N:3]=2)[CH2:26][CH2:25][CH2:24][CH2:23][CH2:22]1
NN1CCCCC1
CC(=O)Nc1nc2ccc(-c3ccnc(Cl)n3)cc2s1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CS(C)=O
null
null
null
null
null
null
null
null
null
null
80
0.33
A mixture of N-(6-(2-chloropyrimidin-4-yl)benzo[d]thiazol-2-yl)acetamide (0.100 g, 0.3 mmol) and piperidin-1-amine (0.03 g, 0.3 mmol) in DMSO (0.03 g, 0.3 mmol) was heated under microwave (CEM) at 80° C. and 130 W (Powermax® off) for 20 min. Then, the mixture was diluted with 1 ml of DMSO and purified by HPLC (5-50% CH3CN in water) to give a light yellow solid (20 mg) as a TFA salt. MS (ESI pos. ion) Found m/z: 354, (M+H)+.
CC(=O)Nc1nc2ccc(-c3ccnc(N4CCCCC4)n3)cc2s1
null
18.9
null
1,754,713
ord_dataset-97eb2ab57fec4160922caae33b54d956
null
2016-01-01T00:08:00
true
[CH3:1][O:2][C:3]1[N:8]=[C:7]([N:9]2[CH2:14][CH2:13][O:12][CH2:11][CH2:10]2)[CH:6]=[CH:5][C:4]=1[N+:15]([O-])=O.[H][H]>CCOC(C)=O.CCO.[Pd]>[CH3:1][O:2][C:3]1[C:4]([NH2:15])=[CH:5][CH:6]=[C:7]([N:9]2[CH2:14][CH2:13][O:12][CH2:11][CH2:10]2)[N:8]=1
[H][H]
COc1nc(N2CCOCC2)ccc1[N+](=O)[O-]
null
[Pd]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
CCOC(C)=O
null
null
null
null
null
null
null
null
null
25
2
To a solution of 4-(6-methoxy-5-nitropyridin-2-yl)morpholine (Preparation 81, 280 mg, 1.170 mmol) in EtOAc/EtOH (1:1, 10 ml) was added palladium on charcoal (10%, 100 mg). The flask was charged with hydrogen and the reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was filtered through Celite® and concentrated in vacuo to give the title compound (245 mg, 99%).
COc1nc(N2CCOCC2)ccc1N
null
100.1
null
100,844
ord_dataset-d06b137b66b3478fb6a0d41a5efd32f8
null
1982-01-01T00:12:00
true
[C:1]([C:4]1[CH:9]=[C:8]([CH2:10][CH3:11])[CH:7]=[CH:6][C:5]=1[S:12][CH:13]1[CH2:18][CH2:17][O:16][C:14]1=[O:15])([OH:3])=O.N#N>C(OC(=O)C)(=O)C.C(N(CC)CC)C>[CH2:10]([C:8]1[CH:7]=[CH:6][C:5]2[S:12][C:13]3([C:1](=[O:3])[C:4]=2[CH:9]=1)[CH2:18][CH2:17][O:16][C:14]3=[O:15])[CH3:11]
CCc1ccc(SC2CCOC2=O)c(C(=O)O)c1
null
null
N#N
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(CC)CC
CC(=O)OC(C)=O
null
null
null
null
null
null
null
null
null
null
null
A mixture of α-[(2-carboxy-4-ethylphenyl)thio]-γ-butyrolactone (1.0 g) in acetic anhydride (30 ml) and triethylamine (6 ml) was heated at 130° C. for 30 minutes under a stream of N2 gas with stirring. The mixture was evaporated in vacuo. The resulting residue was submitted to column chromatography on silica gel (20 g) and charcoal (5 g) eluting with CHCl3 to give 5-ethyl-4',5'-dihydrospiro[benzo[b]thiophene-2(3H),3'(2'H)-furan]-3,2'-dione as colorless oil. Anal. Calcd. for C13H12O3S: C, 62.88; H, 4.87. Found: C, 62.83; H, 4.83.
CCc1ccc2c(c1)C(=O)C1(CCOC1=O)S2
null
null
null
934,038
ord_dataset-d8a5dc784dde4465894ec7c69d2e3ba6
null
2010-01-01T00:01:00
true
[N:1]1([C:7]2[N:12]=[CH:11][NH:10][C:9](=[O:13])[CH:8]=2)[CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1.[Cl:14][C:15]1[CH:22]=[C:19]([CH:20]=O)[C:18]([OH:23])=[CH:17][CH:16]=1>>[Cl:14][C:15]1[CH:16]=[CH:17][C:18]([OH:23])=[C:19]([CH:22]=1)[CH2:20][N:4]1[CH2:5][CH2:6][N:1]([C:7]2[N:12]=[CH:11][NH:10][C:9](=[O:13])[CH:8]=2)[CH2:2][CH2:3]1
O=c1cc(N2CCNCC2)nc[nH]1
O=Cc1cc(Cl)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
6-[4-(5-Chloro-2-hydroxy-benzyl)-piperazin-1-yl]-3H -pyrimidin-4-one was prepared using Procedure B from 6-piperazin-1-yl-3H-pyrimidin-4-one (Intermediate 4) and 5-chlorosalicylaldehyde (available from Aldrich). 1H NMR (400 MHz, CDCl3) δ 2.60-2.64 (m, 4H), 3.58-3.65 (m, 4H), 3.70 (s, 2H), 5.40 (s, 1H), 6.76-6.78 (m, 1H), 6.96-6.99 (m, 1H), 7.13-7.15 (m, 1H), 7.85 (s, 1H), 10.60 (br s, 1H), 12.65 (br s, 1H). Mass spectrum (ES) MH+=321.
O=c1cc(N2CCN(Cc3cc(Cl)ccc3O)CC2)nc[nH]1
null
null
null
1,759,630
ord_dataset-97eb2ab57fec4160922caae33b54d956
null
2016-01-01T00:08:00
true
[C:1]([N:4]1[C:13]2[C:8](=[CH:9][C:10]([C:14]3[CH:15]=[N:16][N:17]([CH:19]4[CH2:22][O:21][CH2:20]4)[CH:18]=3)=[CH:11][CH:12]=2)[N:7]([C:23](Cl)=[O:24])[CH2:6][C@@H:5]1[CH3:26])(=[O:3])[CH3:2].[N:27]1[CH:32]=[CH:31][CH:30]=[C:29]([OH:33])[CH:28]=1.N1C=CC=CC=1>ClCCCl>[C:1]([N:4]1[C:13]2[C:8](=[CH:9][C:10]([C:14]3[CH:15]=[N:16][N:17]([CH:19]4[CH2:22][O:21][CH2:20]4)[CH:18]=3)=[CH:11][CH:12]=2)[N:7]([C:23]([O:33][C:29]2[CH:28]=[N:27][CH:32]=[CH:31][CH:30]=2)=[O:24])[CH2:6][C@@H:5]1[CH3:26])(=[O:3])[CH3:2]
Oc1cccnc1
CC(=O)N1c2ccc(-c3cnn(C4COC4)c3)cc2N(C(=O)Cl)C[C@@H]1C
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCCl
c1ccncc1
null
null
null
null
null
null
null
null
null
50
6
A solution of (S)-4-acetyl-3-methyl-7-(1-(oxetan-3-yl)-1H-pyrazol-4-yl)-3,4-dihydroquinoxaline-1(2H)-carbonyl chloride (0.050 g, 0.13 mmol) in 1,2-dichloroethane (1 mL) was added dropwise to a 50° C. solution of pyridine-3-ol (0.053 g, 0.26 mmol) and pyridine (1 mL) in 1,2-dichloroethane (20 mL). The resulting solution was stirred for 6 h at 50° C. and then concentrated under vacuum. The residue was purified by preparative thin layer chromatography (eluting with 1-20% methanol-dichloromethane) and then by preparative-HPLC (conditions: Column, SunFire™Prep C18OBD™, 19×150 nm; Mobile phase, A: 0.05% ammonium carbonate, B: acetonitrile; Detector, 220 and 254 nm) to afford (S)-pyridin-3-yl 4-acetyl-3-methyl-7-(1-(oxetan-3-yl)-1H-pyrazol-4-yl)-3,4-dihydroquinoxaline-1(2H)-carboxylate (0.026 mg, 46%) as a white solid. 1H NMR (300 MHz, CD3OD) 1.17 (d, J=6.60 Hz, 3H), 2.27 (s, 3H), 3.50-3.79 (m, 1H), 4.35-4.45 (m, 1H), 5.02-5.25 (m, 5H), 5.55-5.65 (m, 1H), 7.39-7.49 (m, 2H), 7.51-7.57 (m, 1H), 7.78-7.83 (m, 1H), 7.97 (s, 1H), 8.10-8.19 (m, 2H), 8.47-8.50 (m, 1H), 8.52-8.56 (m, 1H). MS (ESI, pos. ion) m/z 434 [M+H]+.
CC(=O)N1c2ccc(-c3cnn(C4COC4)c3)cc2N(C(=O)Oc2cccnc2)C[C@@H]1C
null
0
null
1,299,856
ord_dataset-de51ecc8d4434bacaa8bc32d7d73484c
null
2013-01-01T00:05:00
true
Br[C:2]1[C:10]2[S:9][CH:8]=[N:7][C:6]=2[CH:5]=[CH:4][CH:3]=1.[C:11]([OH:17])([C:13](F)(F)F)=[O:12]>>[S:9]1[C:10]2[C:2]([CH2:13][C:11]([OH:17])=[O:12])=[CH:3][CH:4]=[CH:5][C:6]=2[N:7]=[CH:8]1
O=C(O)C(F)(F)F
Brc1cccc2ncsc12
null
null
null
null
null
null
null
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 (20 mg) was prepared from 7-bromobenzo[d]thiazole according to protocol P. LCMS (0.05% TFA): [M+1]+ 194.1. 1H-NMR (CDCl3, 400 MHz): δ9.05 (s, 1H), 8.10 (d, 1H, J=6.8 Hz), 7.53 (m, 1H), 7.39 (d, 1H, J=6.8 Hz), 3.96 (s, 2H).
O=C(O)Cc1cccc2ncsc12
null
null
null
1,730,265
ord_dataset-36057d699ac5449e9c37eb99abf78b03
null
2016-01-01T00:05:00
true
[NH2:1][C@@H:2]([C:6]([OH:8])=[O:7])[C@H:3]([CH3:5])[OH:4].C([O-])(O)=O.[Na+].[CH:14]1([O:20][C:21](N2C=CC=CC2=O)=[O:22])[CH2:19][CH2:18][CH2:17][CH2:16][CH2:15]1>O.C1COCC1>[CH:14]1([O:20][C:21]([NH:1][C@H:2]([C@@H:3]([OH:4])[CH3:5])[C:6]([OH:8])=[O:7])=[O:22])[CH2:19][CH2:18][CH2:17][CH2:16][CH2:15]1
O=C(OC1CCCCC1)n1ccccc1=O
C[C@H](O)[C@@H](N)C(=O)O
null
O=C([O-])O
[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
null
null
To a stirred mixture of D-threonine (0.150 g, 1.25 mmol) and NaHCO3 (0.158 g, 1.89 mmol) in H2O (3.5 mL), the crude mixture containing cyclohexyl-2-pyridyl-carbonate and cyclohexyl-2-oxopyridine 1-carboxylate (0.418 g, 1.89 mmol) in THF (3.5 mL) was added. After 15 h at rt the crude mixture was rotary evaporated to remove the organics and subsequently extracted with Et2O (3×5 mL). The aqueous phase was acidified with 2M HCl solution to pH 2-3 and subsequently extracted with AcOEt (3×10 mL). The organic fraction was dried over Na2SO4, filtered and concentrated to dryness to afford the title compound (0.3 g, 97%) as transparent oil, which was used in the next step without further purification. MS (ESI) m/z: 246 [M−H]+; (ESI) m/z: 244 [M−H]−. 1H NMR (DMSO-d6): δ 1.09 (d, J=6.2 Hz, 3H), 1.16-1.43 (m, 5H), 1.49 (s, 1H), 1.69 (s, 2H), 1.80 (s, 2H), 3.93 (dd, J=2.9, 8.8 Hz, 1H), 3.99-4.12 (m, 1H), 4.44-4.61 (m, 1H), 6.59 (d, J=8.9 Hz, 1H), 12.32 (br s, 1H).
C[C@H](O)[C@@H](NC(=O)OC1CCCCC1)C(=O)O
null
97.9
null
427,830
ord_dataset-8cce6f317d644b348a7978a2dce3ea01
null
1999-01-01T00:03:00
true
C[O:2][C:3]1[CH:20]=[CH:19][C:18]2[C@@H:17]3[C@H:8]([C@H:9]4[C@@:13]([CH2:15][CH2:16]3)([CH3:14])[C@@H:12]([NH:21][C:22](=[O:30])[CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH3:29])[CH2:11][CH2:10]4)[CH2:7][CH2:6][C:5]=2[CH:4]=1.B(Br)(Br)Br>C(Cl)Cl>[OH:2][C:3]1[CH:20]=[CH:19][C:18]2[C@@H:17]3[C@H:8]([C@H:9]4[C@@:13]([CH2:15][CH2:16]3)([CH3:14])[C@@H:12]([NH:21][C:22](=[O:30])[CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH3:29])[CH2:11][CH2:10]4)[CH2:7][CH2:6][C:5]=2[CH:4]=1
CCCCCCCC(=O)N[C@H]1CC[C@H]2[C@@H]3CCc4cc(OC)ccc4[C@H]3CC[C@]12C
null
null
BrB(Br)Br
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
2.5
To a solution comprising about 1.3 g of compound 9a (m=6) in 50 ml of CH2Cl2 was added 7.0 ml of boron tribromide (BBr3, 1M solution in CH2Cl2) at 0° C. under nitrogen atmosphere. The reaction mixture was stirred at 0° C. for 2.5 h and quenched by adding about 30 ml of 1N HCl. The organic layer was separated and the aqueous layer was extracted with CH2Cl2 (2×30 ml). The combined organic layer was dried with Na2SO4 and concentrated in vacuo. The residue was purified by silica gel chromatography (petroleum ether: EtOAc, 1:1) affording the phenol 10a (1.1 g, 88%).
CCCCCCCC(=O)N[C@H]1CC[C@H]2[C@@H]3CCc4cc(O)ccc4[C@H]3CC[C@]12C
null
87.6
null
1,213,559
ord_dataset-dc3bb1b1ac4e4229a3fc28fb559a9777
null
2012-01-01T00:10:00
true
[F:1][C:2]([F:15])([F:14])[C:3]1[NH:12][C:11](=O)[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[N:4]=1.P(Cl)(Cl)([Cl:18])=O>CN(C=O)C>[Cl:18][C:11]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[N:4]=[C:3]([C:2]([F:15])([F:14])[F:1])[N:12]=1
O=P(Cl)(Cl)Cl
O=c1[nH]c(C(F)(F)F)nc2ccccc12
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
null
null
To a mixture of 2-(trifluoromethyl)quinazolin-4(3H)-one (12 g) and phosphorous oxychloride (100 ml) was added DMF (0.5 ml) and the mixture was refluxed under nitrogen for 16 h. The excess phosphorous oxychloride was distilled off and the residue was diluted with ethyl acetate (200 ml). The ethyl acetate layer was washed with 10% solution of sodium bicarbonate, water and brine. The solvent was dried and evaporated. The residue was purified by chromatography (silica gel: 60-120 mesh) eluting with pet ether/ethyl acetate (9/1) to afford 8 g (61%) of the titled compound as a pale yellow solid.
FC(F)(F)c1nc(Cl)c2ccccc2n1
null
61
null
1,390,098
ord_dataset-31641fb65b34430fa7435229b949b604
null
2014-01-01T00:01:00
true
[CH3:1][C:2]1[CH:3]=[C:4]([C:17]#[N:18])[C:5]2[CH:6]=[N:7][N:8]([CH:11]3[CH2:16][CH2:15][CH2:14][CH2:13][O:12]3)[C:9]=2[CH:10]=1>[Ni].N.CO>[CH3:1][C:2]1[CH:10]=[C:9]2[C:5]([CH:6]=[N:7][N:8]2[CH:11]2[CH2:16][CH2:15][CH2:14][CH2:13][O:12]2)=[C:4]([CH2:17][NH2:18])[CH:3]=1
Cc1cc(C#N)c2cnn(C3CCCCO3)c2c1
null
null
[Ni]
N
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
2
To a solution of 6-methyl-1-(tetrahydro-2H-pyran-2-yl)-1H-indazole-4-carbonitrile (120 mg, 0.5 mmol) in a solution of NH3/MeOH (7 N, 10 mL) was added Raney nickel (50 mg). The mixture was stirred under hydrogen at RT for 2 hours. It was filtered with Celite, and the filtrate was concentrated in vacuo to afford (6-methyl-1-(tetrahydro-2H-pyran-2-yl)-1H-indazol-4-yl)methanamine (113) as brown solid (120 mg, ˜100%). MS (ESI): m/z=246.3 [M+1]+.
Cc1cc(CN)c2cnn(C3CCCCO3)c2c1
null
97.8
null
94,712
ord_dataset-6f715747ea754945a2f0af4a8482c7d2
null
1982-01-01T00:06:00
true
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([OH:10])=[CH:6][CH:5]=1)([O-:3])=[O:2].[Cl:11][C:12]1[N:17]=[CH:16][C:15]([CH2:18]Br)=[CH:14][CH:13]=1>>[Cl:11][C:12]1[CH:13]=[CH:14][C:15]([CH2:18][O:10][C:7]2[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=2)=[CH:16][N:17]=1
O=[N+]([O-])c1ccc(O)cc1
Clc1ccc(CBr)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
The substituted aniline compounds of formula (I) wherein W is oxygen can be prepared by the reaction of nitrophenol with a substituted pyridylalkyl halide to obtain the corresponding substituted nitrobenzene which is reduced to the desired substituted aniline of formula (I). For example, the reaction of 4-nitrophenol and 6-chloro-3-pyridylmethyl bromide gives 4-(2-chloro-5-pyridylmethyloxy)nitrobenzene which is then reduced to 4-(2-chloro-5-pyridylmethyloxy)aniline of formula I. Alternatively, the compounds of formula I can be prepared by the reaction of a halo-nitrobenzene with a substituted pyridylalkyl alcohol or substituted pyridylalkyl thiol followed by reduction of the nitro group. For example, the reaction of 4-fluoronitrobenzene and 5-bromo-2-pyridine methanol gives 4-(5-bromo-2-pyridylmethyloxy)nitrobenzene which is then reduced using, for example, iron powder to give 4-(5-bromo-2-pyridylmethyloxy)aniline.
O=[N+]([O-])c1ccc(OCc2ccc(Cl)nc2)cc1
null
null
null
651,607
ord_dataset-271c0b74f4794a06992957029b3151ba
null
2004-01-01T00:10:00
true
C[O:2][C:3](=O)[CH2:4][N:5]([S:11]([C:14]1[CH:19]=[CH:18][C:17]([N:20]2[C:24]([C:25]3[CH:30]=[CH:29][C:28]([CH3:31])=[CH:27][CH:26]=3)=[CH:23][C:22]([C:32]([F:35])([F:34])[F:33])=[N:21]2)=[CH:16][CH:15]=1)(=[O:13])=[O:12])[CH2:6][C:7](OC)=[O:8].[BH4-].[Na+]>CO>[OH:8][CH2:7][CH2:6][N:5]([CH2:4][CH2:3][OH:2])[S:11]([C:14]1[CH:19]=[CH:18][C:17]([N:20]2[C:24]([C:25]3[CH:30]=[CH:29][C:28]([CH3:31])=[CH:27][CH:26]=3)=[CH:23][C:22]([C:32]([F:33])([F:35])[F:34])=[N:21]2)=[CH:16][CH:15]=1)(=[O:13])=[O:12]
COC(=O)CN(CC(=O)OC)S(=O)(=O)c1ccc(-n2nc(C(F)(F)F)cc2-c2ccc(C)cc2)cc1
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
null
2
To a solution of methyl N-(2-methoxy-2-oxoethyl)-N-({4-[5-(4-methylphenyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl]phenyl}sulfonyl)glycinate prepared as in example 2.A. (0.330 g, 0.628 mmol) in anhydrous methanol (50 mL), was added NaBH4 (0.4 g, 10.6 mmol) and the mixture was allowed to stand at room temperature for 2 hours. Additional NaBH4 (0.4 g, 10.6 mmol) was then added and after 1 hour, the solvent was removed in vacuo. The residue was dissolved in water (100 mL), saturated with NaCl and the pH was adjusted to 2 with 1N HCl. The solution was extracted with ethyl acetate (200 mL). The organic solution was washed with sat. NaCl (50 mL), dried over MgSO4, filtered and concentrated under vacuum to afford 0.285 g (97% yield) of the product as a white powder: mp, 79.1° C.; 1H NMR (dmso-d6/300 MHz) δ 7.87 (d, 2H, J=8.7 Hz), 7.54 (d, 2H, J=8.7 Hz), 7.23-7.16 (m, 5H), 4.81 (exchangeable with D2O, t, 2H, J=5.4 Hz), 3.52-3.46 (m, 4H), 3.20 (t, 4H, J=6.0 Hz), 2.30 (s, 3H); HRMS (M+H)+ calcd. for C21H23F3N3O4S: 470.1361; found 470.1330.
Cc1ccc(-c2cc(C(F)(F)F)nn2-c2ccc(S(=O)(=O)N(CCO)CCO)cc2)cc1
null
97
null
688,580
ord_dataset-56747de2718a4ac5bf061651d1cc9e3e
null
2005-01-01T00:10:00
true
[NH2:1][C:2]1[S:3][C:4]2[C:9]([NH:10][C@H:11]([CH3:14])[CH2:12][OH:13])=[N:8][C:7]([SH:15])=[N:6][C:5]=2[N:16]=1.Cl[CH2:18][C:19]1[N:20]=[C:21]([NH:24][C:25](=[O:27])[CH3:26])[S:22][CH:23]=1>>[NH2:1][C:2]1[S:3][C:4]2[C:9]([NH:10][C@H:11]([CH3:14])[CH2:12][OH:13])=[N:8][C:7]([S:15][CH2:18][C:19]3[N:20]=[C:21]([NH:24][C:25](=[O:27])[CH3:26])[S:22][CH:23]=3)=[N:6][C:5]=2[N:16]=1
C[C@H](CO)Nc1nc(S)nc2nc(N)sc12
CC(=O)Nc1nc(CCl)cs1
null
null
null
null
null
null
null
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 titled compound was prepared from the product of example 4, step (b), and N-[4-(chloromethyl)-2-thiazolyl]-acetamide, using the method of example 4, step (c)
CC(=O)Nc1nc(CSc2nc(N[C@H](C)CO)c3sc(N)nc3n2)cs1
null
null
null
110,937
ord_dataset-ac04cf1ba5724e9b93d39b77e9740b21
null
1983-01-01T00:11:00
true
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C@H:8]2[CH2:12][C@H:11]([CH2:13]OS(C3C=CC(C)=CC=3)(=O)=O)[CH2:10][O:9]2)=[CH:4][CH:3]=1.[I-:25].[Na+]>CC(C)=O>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C@H:8]2[CH2:12][C@H:11]([CH2:13][I:25])[CH2:10][O:9]2)=[CH:4][CH:3]=1
Cc1ccc(S(=O)(=O)OC[C@@H]2CO[C@@H](c3ccc(F)cc3)C2)cc1
[I-]
null
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(C)=O
null
null
null
null
null
null
null
null
null
null
null
null
A mixture of 9.2 g of trans-2-(4-fluorophenyl)-4-(tosyloxymethyl)tetrahydrofuran and 12.6 g of sodium iodide in 130 ml of acetone is heated under reflux for 6 hours. The solvent is then distilled off under reduced pressure, and the residue is extracted with ether. The extract is washed with water and dried over magnesium sulfate, and the solvent is distilled off to give a quantitative yield of trans-2-(4-fluorophenyl)-4-(iodomethyl)tetrahydrofuran as colorless oil, nD27 1.5675.
Fc1ccc([C@H]2C[C@H](CI)CO2)cc1
null
null
null
1,325,913
ord_dataset-cfad8b3f00044bcda60a96b019f09872
null
2013-01-01T00:08:00
true
Br[C:2]1[CH:7]=[C:6]([Br:8])[CH:5]=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[CH3:12][NH2:13].O>C(O)C>[Br:8][C:6]1[CH:5]=[CH:4][C:3]([N+:9]([O-:11])=[O:10])=[C:2]([NH:13][CH3:12])[CH:7]=1
CN
O=[N+]([O-])c1ccc(Br)cc1Br
null
null
null
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
80
3
To a solution of 2,4-dibromo-1-nitro-benzene (2.0 g, 7.14 mmol) in ethanol (50 mL) was added a 40% aqueous solution of methylamine (50 mL). The reaction mixture was stirred at 80° C. in a closed vessel for 3 h, then cooled to 0° C. Water was added and the precipitate was filtered, washed with water, and dried in vacuo to give 1.26 g of (5-bromo-2-nitro-phenyl)-methyl-amine as an orange solid (76% yield): 1H NMR (CDCl3) δ 3.04 (s, 3H), 6.79 (dd, 1H), 7.03 (d, 1H), 8.05 (d, 1H), 8.0-8.1 (broad s, 1H); MS (m/z) 231, 233 [M+H+]+.
CNc1cc(Br)ccc1[N+](=O)[O-]
null
76
null
486,846
ord_dataset-7b02d32cc502407f94aea8e5caf405a2
null
2000-01-01T00:12:00
true
[Cl:1][C:2]1[C:3]([C:12]2[CH:17]=[CH:16][C:15](F)=[C:14]([N+:19]([O-:21])=[O:20])[CH:13]=2)=[N:4][CH:5]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:7]=1>C(N)(C)C>[Cl:1][C:2]1[C:3]([C:12]2[CH:17]=[CH:16][C:15]([NH:4][CH:3]([CH3:12])[CH3:2])=[C:14]([N+:19]([O-:21])=[O:20])[CH:13]=2)=[N:4][CH:5]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:7]=1
O=[N+]([O-])c1cc(-c2ncc(C(F)(F)F)cc2Cl)ccc1F
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(C)N
null
null
null
null
null
null
null
null
null
null
null
null
44.0 g of 3-chloro-2-(4-fluoro-3-nitrophenyl)-5-trifluoromethylpyridine in 250 ml of isopropylamine were stirred at 23° C. for six hours. The reaction mixture was then concentrated. The residue was stirred with 100 ml of water, after which the residual solid portion was separated off, washed with water and dried in a vacuum drying oven. Yield: 48.2 g (98%) of colorless crystals; m.p.: 107-109° C.
CC(C)Nc1ccc(-c2ncc(C(F)(F)F)cc2Cl)cc1[N+](=O)[O-]
null
null
null
468,221
ord_dataset-f1b9e9741a6a4cc68e7070df811f86bb
null
2000-01-01T00:07:00
true
[CH2:1]1[O:9][C:8]2[CH:7]=[CH:6][C:5]([CH2:10][C:11](=[O:13])[CH3:12])=[CH:4][C:3]=2[O:2]1.[H-].[Na+].[CH2:16]([O:18][CH:19]([O:22][CH2:23][CH3:24])[CH2:20]I)[CH3:17]>CN(C)C=O>[CH2:16]([O:18][CH:19]([O:22][CH2:23][CH3:24])[CH2:20][CH:10]([C:5]1[CH:6]=[CH:7][C:8]2[O:9][CH2:1][O:2][C:3]=2[CH:4]=1)[C:11](=[O:13])[CH3:12])[CH3:17]
CCOC(CI)OCC
CC(=O)Cc1ccc2c(c1)OCO2
null
[H-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
null
null
To 11.7 g of 3,4-methylenedioxyphenylacetone in 100 ml of dimethylformamide, 2.76 g of 60% oily sodium hydride was added under cooling with ice with stirring, and after stirring at the same temperature for 30 minutes, 20.9 g of iodoacetaldehyde diethyl acetal in 20 ml of dimethylformamide was added. The reaction solution was stirred at room temperature for 2 hours and partitioned between water and ethyl ether. The organic layer was washed with saturated aqueous sodium chloride and then dried over anhydrous magnesium sulfate. The desiccant was filtered off, and the solvent was evaporated in vacuo. The residue was purified by silica gel column chromatography [hexane/ethyl acetate=15/1→10/1] to give 18.3 g of the title compound.
CCOC(CC(C(C)=O)c1ccc2c(c1)OCO2)OCC
null
94.7
null
261,527
ord_dataset-ddb1b60bec5c45e9a2938b6dac04376c
null
1993-01-01T00:02:00
true
[CH2:1]([C:5]1[N:9]([CH2:10][C:11]2[CH:16]=[CH:15][C:14]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=3[C:23]#[N:24])=[CH:13][CH:12]=2)[N:8]=[C:7]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH:6]=1)[CH2:2][CH2:3][CH3:4].[N-:30]=[N+:31]=[N-:32].[Na+].[Cl-].[NH4+]>CN(C)C=O>[CH2:1]([C:5]1[N:9]([CH2:10][C:11]2[CH:16]=[CH:15][C:14]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=3[C:23]3[NH:32][N:31]=[N:30][N:24]=3)=[CH:13][CH:12]=2)[N:8]=[C:7]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH:6]=1)[CH2:2][CH2:3][CH3:4]
CCCCc1cc(C(=O)OCC)nn1Cc1ccc(-c2ccccc2C#N)cc1
[N-]=[N+]=[N-]
null
[Cl-]
[NH4+]
[Na+]
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
null
72
To a solution of ethyl 5-butyl-1-[(2'-cyanobiphenyl-4-yl)methyl]pyrazole-3-carboxylate (730 mg) in dimethylformamide (10 ml) were added sodium azide (1.3 g) and ammonium chloride (1.07 g) and the mixture was stirred at 110°-115° C. for 72 hours. Insoluble materials were filtered off, and the filtrate was concentrated to dryness. To the residue were added 0.5 N-hydrochloric acid (40 ml) and ether (100 ml) for partitioning, and the organic layer was washed with water, dried, and concentrated to dryness. The residue was purified by column chromatography on silica gel to give the desired product as a colorless powder (470 mg, 58%).
CCCCc1cc(C(=O)OCC)nn1Cc1ccc(-c2ccccc2-c2nnn[nH]2)cc1
null
57.9
null
1,676,726
ord_dataset-9cc455db05a444779921f786a45b21a6
null
2015-01-01T00:12:00
true
[C:1]([O:5][C:6](=[O:35])[NH:7][C:8]1([C:12]2[CH:17]=[CH:16][C:15]([C:18]3[C:19]([C:29]4[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=4)=[CH:20][C:21]4[NH:26][C:25](=S)[CH2:24][O:23][C:22]=4[N:28]=3)=[CH:14][CH:13]=2)[CH2:11][CH2:10][CH2:9]1)([CH3:4])([CH3:3])[CH3:2].[CH3:36][O:37][CH2:38][CH2:39][C:40]([NH:42][NH2:43])=O>CC1C=CC(C)=CC=1>[CH3:36][O:37][CH2:38][CH2:39][C:40]1[N:26]2[C:21]3[CH:20]=[C:19]([C:29]4[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=4)[C:18]([C:15]4[CH:16]=[CH:17][C:12]([C:8]5([NH:7][C:6](=[O:35])[O:5][C:1]([CH3:4])([CH3:3])[CH3:2])[CH2:11][CH2:10][CH2:9]5)=[CH:13][CH:14]=4)=[N:28][C:22]=3[O:23][CH2:24][C:25]2=[N:43][N:42]=1
CC(C)(C)OC(=O)NC1(c2ccc(-c3nc4c(cc3-c3ccccc3)NC(=S)CO4)cc2)CCC1
COCCC(=O)NN
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccc(C)cc1
null
null
null
null
null
null
null
null
null
null
150
null
A suspension of tert-butyl(1-(4-(7-phenyl-2-thioxo-2,3-dihydro-1H-pyrido[2,3-b][1,4]oxazin-6-yl)phenyl)cyclobutyl)carbamate (100 mg, 0.205 mmol) and 3-methoxypropanehydrazide (48 mg, 0.410 mmol) in p-xylene (2 ml) was heated to 150° C. for 15 minutes under microwave irradiation. The resulting reaction mixture was concentrated to dryness under reduced pressure and purified by Biotage silica gel chromatography (gradient 0% to 20% ethyl acetate in cyclohexane) to give the title compound (33 mg, 30%). LCMS (Method D): RT=1.414 min, M+1=554. 1H NMR (500 MHz, CDCl3) δ 8.16 (1H, s), 7.27-7.36 (7H, m), 7.23-7.18 (2H, m), 5.60 (2H, s), 3.99 (2H, t), 3.43 (3H, s), 3.38 (2H, t), 2.57-2.40 (4H, m), 2.12-2.01 (1H, m), 1.87-1.77 (1H, m), 1.49-1.27 (9H, bs).
COCCc1nnc2n1-c1cc(-c3ccccc3)c(-c3ccc(C4(NC(=O)OC(C)(C)C)CCC4)cc3)nc1OC2
null
29.1
null
1,628,021
ord_dataset-f0794d5ded7a4d3fab45cc3d7a89ee3d
null
2015-01-01T00:09:00
true
C1([O:7][C:8](=O)[NH:9][C:10]2[CH:15]=[CH:14][C:13]([C:16]3[C:26]4[C:25](=[O:27])[N:24]([CH:28]5[CH2:33][CH2:32][O:31][CH2:30][CH2:29]5)[CH2:23][C:22]([CH3:35])([CH3:34])[O:21][C:20]=4[N:19]=[C:18]([N:36]4[CH2:42][CH:41]5[O:43][CH:38]([CH2:39][CH2:40]5)[CH2:37]4)[N:17]=3)=[CH:12][CH:11]=2)C=CC=CC=1.[CH3:45][N:46]1[CH:50]=[CH:49][C:48]([NH2:51])=[N:47]1.CN(C=O)C>C1COCC1>[CH3:35][C:22]1([CH3:34])[O:21][C:20]2[N:19]=[C:18]([N:36]3[CH2:37][CH:38]4[O:43][CH:41]([CH2:40][CH2:39]4)[CH2:42]3)[N:17]=[C:16]([C:13]3[CH:12]=[CH:11][C:10]([NH:9][C:8]([NH:51][C:48]4[CH:49]=[CH:50][N:46]([CH3:45])[N:47]=4)=[O:7])=[CH:15][CH:14]=3)[C:26]=2[C:25](=[O:27])[N:24]([CH:28]2[CH2:33][CH2:32][O:31][CH2:30][CH2:29]2)[CH2:23]1
CC1(C)CN(C2CCOCC2)C(=O)c2c(nc(N3CC4CCC(C3)O4)nc2-c2ccc(NC(=O)Oc3ccccc3)cc2)O1
Cn1ccc(N)n1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
CN(C)C=O
null
null
null
null
null
null
null
null
null
100
null
50 mg (83.4 μmol) of {4-[8,8-dimethyl-2-(8-oxa-3-azabicyclo[3.2.1]oct-3-yl)-5-oxo-6-(tetrahydropyran-4-yl)-5,6,7,8-tetrahydro-9-oxa-1,3,6-triazabenzocyclohepten-4-yl]phenyl}carbamic acid phenyl ester are placed in a microwave reactor and 25 mg (26 μmol) of 1-methyl-1H-pyrazol-3-ylamine are added. 1 ml of DMF and 2 ml of THF are added. The reactor is heated in a Biotage microwave machine for 30 minutes at 100° C. 100 mg (100 μmol) of 1-methyl-1H-pyrazol-3-ylamine are added and the mixture is heated for 2 hours at 110° C. The solvents are evaporated off. The residue is chromatographed on silica gel, eluting with an MeOH/DCM mixture from (0/100 v/v) up to (5/95 v/v) to give a solid, which is then washed with water and dried. 23 mg of 1-{4-[8,8-dimethyl-2-(8-oxa-3-azabicyclo[3.2.1]oct-3-yl)-5-oxo-6-(tetrahydropyran-4-yl)-5,6,7,8-tetrahydro-9-oxa-1,3,6-triazabenzocyclohepten-4-yl]phenyl}-3-(1-methyl-1H-pyrazol-3-yl)urea are recovered.
Cn1ccc(NC(=O)Nc2ccc(-c3nc(N4CC5CCC(C4)O5)nc4c3C(=O)N(C3CCOCC3)CC(C)(C)O4)cc2)n1
null
null
null
977,691
ord_dataset-f886e51ba1484c76a94bce1482f1eab9
null
2010-01-01T00:07:00
true
[CH3:1][C:2]1([CH3:21])[C:6](=[O:7])[N:5]([C:8]2[CH:15]=[CH:14][C:11]([C:12]#[N:13])=[C:10]([C:16]([F:19])([F:18])[F:17])[CH:9]=2)[C:4](=[O:20])[NH:3]1.[Br:22][C:23]1[C:30]([Cl:31])=[CH:29][C:28]([Cl:32])=[CH:27][C:24]=1[CH2:25]Br>>[Br:22][C:23]1[C:30]([Cl:31])=[CH:29][C:28]([Cl:32])=[CH:27][C:24]=1[CH2:25][N:3]1[C:2]([CH3:21])([CH3:1])[C:6](=[O:7])[N:5]([C:8]2[CH:15]=[CH:14][C:11]([C:12]#[N:13])=[C:10]([C:16]([F:19])([F:17])[F:18])[CH:9]=2)[C:4]1=[O:20]
Clc1cc(Cl)c(Br)c(CBr)c1
CC1(C)NC(=O)N(c2ccc(C#N)c(C(F)(F)F)c2)C1=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
Compound 38.2 was prepared as described for example 6.2, by reacting compound 1.1 with 2-bromo-3,5-dichlorobenzyl bromide. 4-[3-(2-Bromo-3,5-dichlorobenzyl)-4,4-dimethyl-2,5-dioxoimidazolidin-1-yl]-2-trifluoromethylbenzonitrile was obtained in a yield of 55%. 1H NMR: 8.35, d, 1H, 8.25, s, 1H, 8.1, d, 1H, 7.7, s, 1H, 7.65, s, 1H; 4.65, s, 2H, 1.45, s, 6H.
CC1(C)C(=O)N(c2ccc(C#N)c(C(F)(F)F)c2)C(=O)N1Cc1cc(Cl)cc(Cl)c1Br
null
55
null
1,247,046
ord_dataset-c544c0c663f54dbea4ddb52ddde7934e
null
2013-01-01T00:01:00
true
C(OC([N:8]1[CH2:13][CH2:12][N:11]([C:14]2[CH:19]=[CH:18][C:17]([CH3:20])=[CH:16][C:15]=2[CH3:21])[C:10](=[O:22])[CH2:9]1)=O)(C)(C)C.[ClH:23].C(OCC)(=O)C>C(Cl)(Cl)Cl>[ClH:23].[CH3:21][C:15]1[CH:16]=[C:17]([CH3:20])[CH:18]=[CH:19][C:14]=1[N:11]1[CH2:12][CH2:13][NH:8][CH2:9][C:10]1=[O:22]
Cc1ccc(N2CCN(C(=O)OC(C)(C)C)CC2=O)c(C)c1
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)Cl
CCOC(C)=O
null
null
null
null
null
null
null
null
null
25
3
To a mixture of 3-oxopiperazine-1-carboxylic acid tert-butyl ester (5 g), 1-bromo-2,4-dimethylbenzene (3.4 mL), potassium carbonate (10.6 g) and copper (I) iodide (952 mg) were added toluene (25 mL) and N,N′-dimethylethylenediamine (1.1 mL), and the mixture was refluxed for 8 hr. After cooling, water was added to the reaction mixture, and the mixture was extracted with chloroform. The organic layer was washed with saturated brine, and the solvent was evaporated. The residue was purified by column chromatography (chloroform:methanol) to give 4-(2,4-dimethylphenyl)-3-oxopiperazine-1-carboxylic acid tert-butyl ester. The obtained 4-(2,4-dimethylphenyl)-3-oxopiperazine-1-carboxylic acid tert-butyl ester was dissolved in chloroform (10 mL), 4N hydrogen chloride/ethyl acetate (10 mL) was added, and the mixture was stirred at room temperature for 3 hr. The precipitate was collected by filtration to give 1-(2,4-dimethylphenyl)piperazin-2-one hydrochloride (3 g).
Cc1ccc(N2CCNCC2=O)c(C)c1
null
null
null
838,211
ord_dataset-074f86301ec5441ab3b52d902ac06949
null
2008-01-01T00:09:00
true
[CH:1]1([CH2:4][C:5]2[C:14]3[C:9](=[CH:10][C:11]([O:15][CH3:16])=[CH:12][CH:13]=3)[C:8](=O)[NH:7][N:6]=2)[CH2:3][CH2:2]1.P(Cl)(Cl)([Cl:20])=O>>[Cl:20][C:8]1[C:9]2[C:14](=[CH:13][CH:12]=[C:11]([O:15][CH3:16])[CH:10]=2)[C:5]([CH2:4][CH:1]2[CH2:3][CH2:2]2)=[N:6][N:7]=1
O=P(Cl)(Cl)Cl
COc1ccc2c(CC3CC3)n[nH]c(=O)c2c1
null
null
null
null
null
null
null
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-cyclopropylmethyl-7-methoxy-2H-phthalazin-1-one with phosphoryl chloride.
COc1ccc2c(CC3CC3)nnc(Cl)c2c1
null
null
null
440,717
ord_dataset-3e8f24b5bc8e4d8bb9b6e7e89a956e12
null
1999-01-01T00:09:00
true
[Cl:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([O:13][CH3:14])[C:10]=1[O:11][CH3:12])C(O)=O.[N+:15]([O-])([OH:17])=[O:16]>C(O)(=O)C>[Cl:1][C:2]1[CH:3]=[C:4]([N+:15]([O-:17])=[O:16])[CH:8]=[C:9]([O:13][CH3:14])[C:10]=1[O:11][CH3:12]
COc1cc(C(=O)O)cc(Cl)c1OC
O=[N+]([O-])O
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
from 2-chloro-N-(3-methoxyphenyl)-4-pyrimidineamine (0.50 g, 2.13 mmol) [see Example 92] and 3-chloro-4,5-dimethoxyaniline (0.40 g, 2.13 mmol) to give the title compound (0.55 g) as a white soid m.p. 204-205°. δH (d6DMSO) 11.19 (1H, br s),10.85 (1H, brs), 8.00 (1H, d, J 7.1 Hz), 7.23 (4H, m), 7.12 (1H, d, J 4.4 Hz), 6.75 (1H, m), 6.59 (1H, d, J 7.1 Hz), 3.74 (3H, s), 3.69 (3H, s) and 3.65 (3H, s). MS m/z 387 (M+H)+. The aniline starting material was prepared in a similar manner to the analogous aniline of Example 113, from 1-chloro-2,3-dimethoxy-5-nitrobenzene (1.08 g, 5.82 mmol), to give the desired product (0.85 g) as a white solid m.p. 66-68°. MS m/z 188 (M+H)+. The 1-chloro-2,3-dimethoxy-5-nitrobenzene was prepared by heating a solution of 3-chloro-4,5-dimethoxybenzoic acid (3.50 g, 16.2 mmol) in glacial acetic acid (15 ml) and 70% nitric acid (15 ml) at 600 for 1 h. The reaction was poured onto ice-water and the white precipitate which formed was filtered off, washed with water and dried in vacuo and washed thoroughly with hexane. The hexane washings were evaporated and the residue subjected to column chromatography [silica 20% ethyl acetate-hexane] to give the desired product (1.03 g) as a white solid m.p. 104-105°. MS m/z 217 (M+H)+. The acid used as starting material was prepared according to the method of Y. Ohtani et al. Acta. Chem. Scand., Ser B. B36, 613 (1982).
COc1cc([N+](=O)[O-])cc(Cl)c1OC
null
null
null
1,411,939
ord_dataset-f8e6e6a2d2bf4135b9e346456c81700f
null
2014-01-01T00:04:00
true
[CH2:1]([O:3][C:4](=[O:31])/[C:5](/[C:17]([CH:19]1[CH2:24][CH2:23][CH:22]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[CH2:21][CH2:20]1)=[O:18])=[CH:6]\[C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([C:13]([F:16])([F:15])[F:14])[CH:8]=1)[CH3:2]>C(O)C.[Pd]>[CH2:1]([O:3][C:4](=[O:31])[CH:5]([CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([C:13]([F:15])([F:16])[F:14])[CH:8]=1)[C:17](=[O:18])[CH:19]1[CH2:24][CH2:23][CH:22]([C:25]2[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=2)[CH2:21][CH2:20]1)[CH3:2]
CCOC(=O)/C(=C\c1cccc(C(F)(F)F)c1)C(=O)C1CCC(c2ccccc2)CC1
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
2
A mixture of (Z)-2-(4-phenylcyclohexanecarbonyl)-3-(3-trifluoromethylphenyl)-acrylic acid ethyl ester (10) (12.3 g, 28.6 mmol) and 10% Pd on carbon (2.5 g, 20% by weight) in denatured ethanol (250 mL) was stirred under a hydrogen atmosphere for 2 hr. The solids were removed by filtration through celite and washed with ethanol. The filtrate was evaporated under vacuum to yield a clear oil. The residue was purified by column chromatography on silica gel (gradient: 0 to 10% tert-butyl methyl ether in cyclohexane) to afford 8.6 g (70%) of 3-oxo-3-(4-phenylcyclohexyl)-2-(3-trifluoromethylbenzyl)-propionic acid ethyl ester (22). 1H NMR (400 MHz, 192227). LCMS (method A), Rt=4.76 min, (M+H)+=433.2 (94%); Rt=5.22 min, (M+H)+=262.9 (6.5%).
CCOC(=O)C(Cc1cccc(C(F)(F)F)c1)C(=O)C1CCC(c2ccccc2)CC1
null
69.5
null
1,570,594
ord_dataset-9741bb5fd93044078df2a45f45733054
null
2015-01-01T00:04:00
true
P(Cl)(Cl)(Cl)=[O:2].[CH3:6][N:7]1[C:12]2[C:13]([CH3:16])=[CH:14][NH:15][C:11]=2[C:10](=[O:17])[N:9]([CH3:18])[C:8]1=[O:19]>CN(C)C=O>[CH3:6][N:7]1[C:12]2[C:13]([CH:16]=[O:2])=[CH:14][NH:15][C:11]=2[C:10](=[O:17])[N:9]([CH3:18])[C:8]1=[O:19]
O=P(Cl)(Cl)Cl
Cc1c[nH]c2c(=O)n(C)c(=O)n(C)c12
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
null
2
At a temperature of 5-10° C., phosphorous oxychloride (1.84 ml, 20.087 mmol) was mixed with N,N-dimethylformamide (2 mL). Then a solution of Intermediate 1 (600 mg, 3.348 mmol) in N,N-dimethylformamide (3 mL) was added while stirring. The reaction mixture was held for 2 h at 95° C., cooled and poured onto ice (10 g). The precipitate formed was filtered off and recrystallised from water to give 300 mg of the product as an off-white solid; 1H NMR (δ ppm, 300 MHz, DMSO-d6) 3.25 (s, 3H), 3.75 (s, 3H), 8.06 (s, 1H), 9.79 (s, 1H), 13.15 (br s, 1H); APCI-MS (m/z) 208.20 (M+H)+.
Cn1c(=O)c2[nH]cc(C=O)c2n(C)c1=O
null
43.2
null
1,563,441
ord_dataset-4e54080057a44c3887653391e24c90b6
null
2015-01-01T00:03:00
true
[NH:1]([C:3]1[CH:8]=[C:7]([C:9]#[N:10])[CH:6]=[CH:5][N:4]=1)[NH2:2].[Cl:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[C:18](=O)[CH2:19][C:20](OCC)=[O:21]>>[Cl:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[C:18]1[CH:19]=[C:20]([OH:21])[N:1]([C:3]2[CH:8]=[C:7]([C:9]#[N:10])[CH:6]=[CH:5][N:4]=2)[N:2]=1
CCOC(=O)CC(=O)c1ccccc1Cl
N#Cc1ccnc(NN)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared in 75% yield from 2-hydrazinylpyridine-4-carbonitrile (PREPARATION 2) and ethyl 3-(2-chlorophenyl)-3-oxopropanoate according to the procedure for the preparation of Example 3, part A. [M+H] Calc'd for C15H9ClN4O 297; Found, 297.
N#Cc1ccnc(-n2nc(-c3ccccc3Cl)cc2O)c1
null
75
null
1,591,930
ord_dataset-e8c6a25568b64529b960953990e6921f
null
2015-01-01T00:06:00
true
[Cl:1][C:2]1[CH:3]=[C:4]([CH3:31])[C:5]2[N:10]=[C:9]([C:11]3[N:15]([C:16]4[C:21]([Cl:22])=[CH:20][CH:19]=[CH:18][N:17]=4)[N:14]=[C:13]([O:23][CH2:24][C:25]([F:28])([F:27])[F:26])[CH:12]=3)[O:8][C:7](=[O:29])[C:6]=2[CH:30]=1.[CH3:32][NH2:33].C(OCC)C>O1CCCC1>[Cl:1][C:2]1[CH:30]=[C:6]([C:7]([NH:33][CH3:32])=[O:29])[C:5]([NH:10][C:9]([C:11]2[N:15]([C:16]3[C:21]([Cl:22])=[CH:20][CH:19]=[CH:18][N:17]=3)[N:14]=[C:13]([O:23][CH2:24][C:25]([F:28])([F:27])[F:26])[CH:12]=2)=[O:8])=[C:4]([CH3:31])[CH:3]=1
CN
Cc1cc(Cl)cc2c(=O)oc(-c3cc(OCC(F)(F)F)nn3-c3ncccc3Cl)nc12
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
CCOCC
null
null
null
null
null
null
null
null
null
25
0.75
To a suspension of the 6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-(2,2,2-trifluoroethoxy)-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazin-4-one (i.e. precipitate product of Step E) (3.53 g, 7.5 mmol) in tetrahydrofuran (15 mL), methylamine (2.0 M solution in THF, 11 mL, 22 mmol) was added dropwise, and the resulting solution was stirred at room temperature for 45 minutes. Thin layer chromatography then showed the reaction to be complete. Ethyl ether (100 mL) was added, and the reaction mixture was stirred for 2 hours while a precipitate formed. The precipitate was collected by filtration and then recrystallized from acetonitrile to yield a white solid (0.82 g). A second crop of white solid (0.35 g) precipitated from the acetonitrile mother liquor and was collected by filtration. The initial ether/tetrahydrofuran mother liquor was concentrated to dryness, and the residual solid was recrystallized from acetonitrile to yield a third crop of white solid (0.95 g). The three crops were combined, totaling 2.12 g (after drying) of the title compound, isolated as a white solid, melting at 207-208° C.
CNC(=O)c1cc(Cl)cc(C)c1NC(=O)c1cc(OCC(F)(F)F)nn1-c1ncccc1Cl
null
21.8
null
240,956
ord_dataset-685186618e9f4e7aaa72ac40c16ef354
null
1992-01-01T00:01:00
true
C1(C[N:8]2[CH2:13][CH2:12][CH:11]([NH:14][C:15](=[O:21])[O:16][CH2:17][CH2:18][O:19][CH3:20])[CH2:10][CH2:9]2)C=CC=CC=1>C(OCC)(=O)C.[OH-].[Pd+2].[OH-]>[CH3:20][O:19][CH2:18][CH2:17][O:16][C:15](=[O:21])[NH:14][CH:11]1[CH2:12][CH2:13][NH:8][CH2:9][CH2:10]1
COCCOC(=O)NC1CCN(Cc2ccccc2)CC1
null
null
[Pd+2]
[OH-]
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
6
2-Methoxyethyl (1-phenylmethyl-4-piperidyl)carbamate (9.6 g), prepared according to Preparation 3, was dissolved in ethyl acetate (100 mL). Palladium hydroxide (10% on carbon, 1 g) was added, and the mixture was stirred under hydrogen (1 bar) for 6 hours. The catalyst was removed by filtration, and the solvent evaporated to give 6.5 g of 2-methoxyethyl-4-piperidylcarbamate as an oil, which was used without further purification.
COCCOC(=O)NC1CCNCC1
null
97.9
null
1,267,895
ord_dataset-d3580a12b15e46cc91aa73f4f1a4a8cc
null
2013-01-01T00:03:00
true
[Cl:1][C:2]1[N:10]=[C:9]2[C:5]([N:6]=[C:7]([CH:17]=O)[N:8]2[CH:11]2[CH2:16][CH2:15][CH2:14][CH2:13][O:12]2)=[C:4]([N:19]2[CH2:24][CH2:23][O:22][CH2:21][CH2:20]2)[N:3]=1.[NH:25]1[CH2:28][CH:27]([N:29]2[CH2:34][CH2:33][NH:32][C:31](=[O:35])[CH2:30]2)[CH2:26]1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCCl.CN(C=O)C>[Cl:1][C:2]1[N:10]=[C:9]2[C:5]([N:6]=[C:7]([CH2:17][N:25]3[CH2:26][CH:27]([N:29]4[CH2:34][CH2:33][NH:32][C:31](=[O:35])[CH2:30]4)[CH2:28]3)[N:8]2[CH:11]2[CH2:16][CH2:15][CH2:14][CH2:13][O:12]2)=[C:4]([N:19]2[CH2:20][CH2:21][O:22][CH2:23][CH2:24]2)[N:3]=1
O=C1CN(C2CNC2)CCN1
O=Cc1nc2c(N3CCOCC3)nc(Cl)nc2n1C1CCCCO1
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
CN(C)C=O
ClCCCl
null
null
null
null
null
null
null
null
null
25
0.17
A mixture of 2-chloro-6-morpholin-4-yl-9-(tetrahydropyran-2-yl)-9H-purine-8-carbaldehyde (1.06 g, 3.01 mmol) and 4-azetidin-3-ylpiperazin-2-one (560 mg, 3.61 mmol) in DCE (60 mL) and DMF (20 mL) was allowed to stir at r.t. for 10 min before the addition of 4 Å powdered molecular sieves (3.0 g) followed by sodium triacetoxyborohydride (1.28 g, 6.04 mmol). The resulting mixture was allowed to stir for 64 h then filtered through Celite® which was washed with DCM. The filtrate was concentrated in vacuo and the resulting residue dissolved in EtOAc and washed with NaHCO3, H2O and brine. The organic phase was dried (Na2SO4) and concentrated in vacuo affording the title compound as a yellow gum (997 mg, 67%). LCMS (method A): RT 2.19 and 2.11 min [M−C5H9O+H]+407.3
O=C1CN(C2CN(Cc3nc4c(N5CCOCC5)nc(Cl)nc4n3C3CCCCO3)C2)CCN1
null
67.5
null
1,153,968
ord_dataset-b195433d5c354ddfb6cde0d53c41910f
null
2012-01-01T00:04:00
true
C(OC([N:8]([CH2:21][CH:22]1[CH2:27][CH2:26][N:25]([C:28]([O:30][C:31]2[CH:32]=[C:33]([CH:37]=[CH:38][CH:39]=2)[C:34]([OH:36])=[O:35])=[O:29])[CH2:24][CH:23]1[C:40]1[CH:45]=[CH:44][CH:43]=[C:42]([F:46])[CH:41]=1)[C@@H:9]([C:11]1[C:20]2[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=2)[CH:14]=[CH:13][CH:12]=1)[CH3:10])=O)(C)(C)C.[ClH:47].C(OCC)(=O)C>C(OCC)(=O)C>[ClH:47].[F:46][C:42]1[CH:41]=[C:40]([CH:23]2[CH:22]([CH2:21][NH:8][C@@H:9]([C:11]3[C:20]4[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=4)[CH:14]=[CH:13][CH:12]=3)[CH3:10])[CH2:27][CH2:26][N:25]([C:28]([O:30][C:31]3[CH:32]=[C:33]([CH:37]=[CH:38][CH:39]=3)[C:34]([OH:36])=[O:35])=[O:29])[CH2:24]2)[CH:45]=[CH:44][CH:43]=1
C[C@H](c1cccc2ccccc12)N(CC1CCN(C(=O)Oc2cccc(C(=O)O)c2)CC1c1cccc(F)c1)C(=O)OC(C)(C)C
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOC(C)=O
null
null
null
null
null
null
null
null
null
null
null
2
To a solution of 88 mg of 3-({[4-({(tert-butoxycarbonyl)[(1R)-1-(1-naphthyl)ethyl]amino}methyl)-3-(3-fluorophenyl)piperidin-1-yl]carbonyl}oxy)benzoic acid in 2.0 mL of ethyl acetate was added 1.00 mL of a 4 M hydrogen chloride/ethyl acetate solution at room temperature, followed by stirring for 2 hours. The resulting precipitate was collected by filtration, and dried under reduced pressure to obtain 22 mg of 3-({[3-(3-fluorophenyl)-4-({[(1R)-1-(1-naphthyl)ethyl]amino}methyl)piperidin-1-yl]carbonyl}oxy)benzoic acid hydrochloride as a white solid.
C[C@@H](NCC1CCN(C(=O)Oc2cccc(C(=O)O)c2)CC1c1cccc(F)c1)c1cccc2ccccc12
null
null
null
418,759
ord_dataset-94e21e9990034c729ea727e7d2ab0eb0
null
1998-01-01T00:12:00
true
[I-:1].[Na+].I.Cl[C:5]1[CH:13]=[CH:12][C:8]([C:9]([OH:11])=[O:10])=[CH:7][N:6]=1>CC(C)=O>[I:1][C:5]1[CH:13]=[CH:12][C:8]([C:9]([OH:11])=[O:10])=[CH:7][N:6]=1
O=C(O)c1ccc(Cl)nc1
[I-]
null
I
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(C)=O
null
null
null
null
null
null
null
null
null
null
25
0.08
To 27.97 g (186.6 mmol) of sodium iodide cooled to -78° C. was added 121.77 g (71.6 ml, 952.0 mmol) of hydriodic acid (in 57 wt % aqueous solution). The reaction mixture was allowed to warm slightly with stirring for 5 minutes and then 30.00 g (190.4 mmol) of 6-chloronicotinic acid was added. The resulting mixture was allowed to warm to room temperature with stirring and then heated at 120°-125° C. in an oil bath for 42 hours. A dark brown layer formed above the yellow solid material. The reaction mixture was allowed to cool to room temperature and then poured into acetone (chilled to 0° C.). The resultant yellow solid was collected by filtration, washed with 200 ml of 1N aqueous NaHSO3 solution, and dried in vacuum (3 mm Hg) to give the title compound as a pale yellow solid. PMR (DMSO-d6): d 7.90 (1H, dd, J=8.1, 2 Hz), 7.99 (1H, d, J=8.1 Hz), 8.80 (1H, d, J=2 Hz).
O=C(O)c1ccc(I)nc1
null
null
null
1,486,902
ord_dataset-c3c1091f873b4f40827973a6f1f9b685
null
2014-01-01T00:09:00
true
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:9]=[C:10]3[CH:15]=[CH:14][C:13]([N:16]4[CH2:21][CH2:20][N:19]([CH3:22])[CH2:18][CH2:17]4)=[N:12][N:11]3[C:23]=2[C:24]2[CH:29]=[CH:28][N:27]=[C:26](F)[CH:25]=2)=[CH:4][CH:3]=1.[CH3:31][NH:32][CH3:33]>O>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:9]=[C:10]3[CH:15]=[CH:14][C:13]([N:16]4[CH2:17][CH2:18][N:19]([CH3:22])[CH2:20][CH2:21]4)=[N:12][N:11]3[C:23]=2[C:24]2[CH:29]=[CH:28][N:27]=[C:26]([N:32]([CH3:33])[CH3:31])[CH:25]=2)=[CH:4][CH:3]=1
CN1CCN(c2ccc3nc(-c4ccc(F)cc4)c(-c4ccnc(F)c4)n3n2)CC1
CNC
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
null
null
null
null
null
null
null
null
null
null
150
null
0.10 g (0.25 mmol) of 2-(4-fluorophenyl)-3-(2-fluoropyrid-4-yl)-6-(4-methylpiperazin-1-yl)imidazo[1,2-b]pyridazine and 10 mL of dimethylamine are introduced into an autoclave. The mixture is heated at 150° C. overnight and then cooled and poured into water. The product is extracted with chloroform, and the organic phase is dried over sodium sulfate and then concentrated under reduced pressure to give a solid. This solid is crystallized and recrystallized from acetonitrile to give 0.028 g of a white powder after cooling, filtering off and drying.
CN1CCN(c2ccc3nc(-c4ccc(F)cc4)c(-c4ccnc(N(C)C)c4)n3n2)CC1
null
null
null
728,788
ord_dataset-eb4226b4f7644a01a737e7547b70014a
null
2006-01-01T00:09:00
true
O[C:2]1[C:7]([C:8]#[N:9])=[CH:6][N:5]=[C:4]2[C:10]3[CH:16]=[CH:15][CH:14]=[CH:13][C:11]=3[O:12][C:3]=12.CCCCCC.P(Cl)(Cl)([Cl:25])=O>>[Cl:25][C:2]1[C:7]([C:8]#[N:9])=[CH:6][N:5]=[C:4]2[C:10]3[CH:16]=[CH:15][CH:14]=[CH:13][C:11]=3[O:12][C:3]=12
O=P(Cl)(Cl)Cl
N#Cc1cnc2c(oc3ccccc32)c1O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCCCCC
null
null
null
null
null
null
null
null
null
null
25
null
A mixture of 2.10 g (11.0 mmol) of 4-hydroxybenzo[4,5]furo[3,2-b]pyridine-3-carbonitrile in 15 mL of phosphorous oxychloride is heated at reflux temperature for 1.5 hours, then cooled to room temperature. Hexane is added and the solid is collected by filtration, dissolved in ethyl acetate and washed with cold 1 N NaOH. The organic layer is dried over sodium sulfate, filtered through a pad of diatomaceous earth and concentrated in vacuo to give 1.55 g (65%) of a red solid, mp 229–231° C.
N#Cc1cnc2c(oc3ccccc32)c1Cl
null
65
null
777,806
ord_dataset-bf316bf78f4f45d4b275959c08104b7c
null
2007-01-01T00:06:00
true
CS([Cl:5])(=O)=O.[CH2:6]([O:9][C:10]1[CH:15]=[CH:14][C:13]([CH2:16]O)=[CH:12][CH:11]=1)[CH:7]=[CH2:8].C(N(CC)CC)C>ClCCl>[CH2:6]([O:9][C:10]1[CH:15]=[CH:14][C:13]([CH2:16][Cl:5])=[CH:12][CH:11]=1)[CH:7]=[CH2:8]
CS(=O)(=O)Cl
C=CCOc1ccc(CO)cc1
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
25
8
7.67 g (67.0 mmol) methanesulfonyl chloride were given at 0° C. to a solution of 10.0 g (60.9 mmol) (4-allyloxy-phenyl)-methanol and 9.34 ml (67.0 mmol) triethylamine in 35 ml dichloromethane and stirred at r.t. overnight. The mixture was poured in ice water, extracted with dichloromethane and the organic phase dried over Na2SO4. After removal of solvents the residue was purified by chromatography on silica gel (ethyl acetate/n-heptane 1:5) to yield 3.12 g (28%) pale yellow oil.
C=CCOc1ccc(CCl)cc1
null
null
null
822,131
ord_dataset-ec58fad8331a42c5a67ad75aac6713b4
null
2008-01-01T00:05:00
true
[C:1]([O:5][C:6]([NH:8][C:9]([CH3:14])([CH3:13])[C:10]([OH:12])=O)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH2:15]([O:22][C:23]([N:25]1[CH2:30][CH2:29][NH:28][CH2:27][CH2:26]1)=[O:24])[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.ON1C2C=CC=CC=2N=N1.Cl.C(N=C=NCCCN(C)C)C>O1CCCC1.O>[CH2:15]([O:22][C:23]([N:25]1[CH2:30][CH2:29][N:28]([C:10](=[O:12])[C:9]([NH:8][C:6]([O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:7])([CH3:14])[CH3:13])[CH2:27][CH2:26]1)=[O:24])[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1
O=C(OCc1ccccc1)N1CCNCC1
CC(C)(C)OC(=O)NC(C)(C)C(=O)O
null
CCN=C=NCCCN(C)C
Cl
On1nnc2ccccc21
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
8
To a solution of 2-(tert-butoxycarbonylamino)-2-methylpropionic acid (10 g) in tetrahydrofuran (20 mL) were added 1-(benzyloxycarbonyl)piperazine (16.3 g), 1-hydroxybenzotriazole (8.02 g) and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (11.4 g), and the mixture was stirred at room temperature overnight. The reaction mixture was poured into water, and the resulting mixture was extracted with ethyl acetate. The extract was washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure. The residue was dissolved in a mixed solvent of n-hexane and ethyl acetate (1/1) (40 mL) at 60° C. with heating, and the solution was stirred at room temperature overnight. To the mixture was added the same solvent (30 mL), and the mixture was further stirred overnight. The precipitated crystals were collected by filtration, and washed with the same solvent and dried under reduced pressure to give 4-benzyloxycarbonyl-1-[2-(tert-butoxycarbonylamino)-2-methylpropionyl]piperazine (13.5 g). To a solution of the obtained 4-benzyloxycarbonyl-1-[2-(tert-butoxycarbonylamino)-2-methylpropionyl]piperazine (5 g) in tetrahydrofuran (30 mL) was added hydrochloric acid (4 mol/L 1,4-dioxane solution, 40 mL), and the mixture was stirred at room temperature overnight. The precipitated crystals were collected by filtration. The obtained crystals were dissolved in ethyl acetate and a saturated aqueous sodium hydrogen carbonate solution. The organic layer was separated, and the organic layer was washed with brine and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to give the title compound (3.65 g).
CC(C)(C)OC(=O)NC(C)(C)C(=O)N1CCN(C(=O)OCc2ccccc2)CC1
null
67.7
null
70,187
ord_dataset-06d4002fc4d34860a0688cba690e12dc
null
1980-01-01T00:09:00
true
[H-].[Al+3].[Li+].[H-].[H-].[H-].[Cl:7][C:8]1[CH:22]=[CH:21][C:11]([CH2:12][CH:13]2[NH:19][C:18](=O)[CH2:17][CH2:16][CH2:15][CH2:14]2)=[CH:10][CH:9]=1>O1CCCC1>[Cl:7][C:8]1[CH:22]=[CH:21][C:11]([CH2:12][CH:13]2[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][NH:19]2)=[CH:10][CH:9]=1
O=C1CCCCC(Cc2ccc(Cl)cc2)N1
null
null
[Al+3]
[H-]
[Li+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
0
null
Add 0.5 g of lithium aluminum hydride to a solution of 2.8 g 7-(4-chlorobenzyl)-perhydroazepin -2-one in 30 ml of tetrahydrofurane. Boil the mixture under reflux for 16 hours, cool it and then carefully treat it with ice-water. After extraction with diethyl ether, dry the extract over sodium sulfate concentrate the oily residue and distill in a vacuum to obtain 1.8 g of the title compound with a BP of 90° to 92° at 0.05 mm Hg.
Clc1ccc(CC2CCCCCN2)cc1
null
68.3
null
750,590
ord_dataset-844a22e1fcab44a5b59c5e2922b2855a
null
2007-01-01T00:01:00
true
[CH2:1]([N:4]1[C:9](=[O:10])[C:8]([C:11]2[CH:16]=[CH:15][C:14](=[O:17])[NH:13][CH:12]=2)=[C:7]([C:18]2[CH:23]=[CH:22][CH:21]=[C:20]([F:24])[CH:19]=2)[N:6]=[C:5]1[NH2:25])[CH:2]=[CH2:3].[C:26](=O)([O-])[O-].[K+].[K+].IC>CS(C)=O>[CH2:1]([N:4]1[C:9](=[O:10])[C:8]([C:11]2[CH:16]=[CH:15][C:14](=[O:17])[N:13]([CH3:26])[CH:12]=2)=[C:7]([C:18]2[CH:23]=[CH:22][CH:21]=[C:20]([F:24])[CH:19]=2)[N:6]=[C:5]1[NH2:25])[CH:2]=[CH2:3]
O=C([O-])[O-]
C=CCn1c(N)nc(-c2cccc(F)c2)c(-c2ccc(=O)[nH]c2)c1=O
null
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CI
CS(C)=O
null
null
null
null
null
null
null
null
null
50
16
To a solution of 3-allyl-2-amino-6-(3-fluorophenyl)-5-(6-oxo-1,6-dihydro-3-pyridinyl)-3,4-dihydro-4-pyrimidinone in dimethyl sulfoxide were added potassium carbonate (2 equivalents) and iodomethane (4 equivalents), followed by stirring at 50° C. for 16 hours. After filtering off the insoluble matters, the filtrate was purified by HPLC, to give the title compound.
C=CCn1c(N)nc(-c2cccc(F)c2)c(-c2ccc(=O)n(C)c2)c1=O
null
null
null
1,421,191
ord_dataset-f8e6e6a2d2bf4135b9e346456c81700f
null
2014-01-01T00:04:00
true
[CH3:1][NH:2][CH2:3][CH2:4][OH:5].CO[C:8]([C:10]1[C:14]([NH:15][C:16]([C:18]2[C:23]([NH:24][C:25]3[CH:26]=[N:27][CH:28]=[N:29][CH:30]=3)=[CH:22][CH:21]=[C:20]([CH:31]3[CH2:33][CH2:32]3)[N:19]=2)=[O:17])=[CH:13][N:12]([CH3:34])[N:11]=1)=[O:9]>>[OH:5][CH2:4][CH2:3][N:2]([CH3:1])[C:8]([C:10]1[C:14]([NH:15][C:16]([C:18]2[C:23]([NH:24][C:25]3[CH:26]=[N:27][CH:28]=[N:29][CH:30]=3)=[CH:22][CH:21]=[C:20]([CH:31]3[CH2:32][CH2:33]3)[N:19]=2)=[O:17])=[CH:13][N:12]([CH3:34])[N:11]=1)=[O:9]
COC(=O)c1nn(C)cc1NC(=O)c1nc(C2CC2)ccc1Nc1cncnc1
CNCCO
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
According to the general method described in step 5 of example 27, reaction of 2-methylamino-ethanol with 4-{[6-cyclopropyl-3-(pyrimidin-5-ylamino)-pyridine-2-carbonyl]-amino}-1-methyl-1H-pyrazole-3-carboxylic acid methyl ester provided the title compound (13%) as amorphous yellow solid.
CN(CCO)C(=O)c1nn(C)cc1NC(=O)c1nc(C2CC2)ccc1Nc1cncnc1
null
13
null
1,632,110
ord_dataset-f0794d5ded7a4d3fab45cc3d7a89ee3d
null
2015-01-01T00:09:00
true
[Cl:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][N:5]=[C:4]([OH:11])[CH:3]=1.O[CH2:13][C@@H:14]([NH:16][C:17](=[O:23])[O:18][C:19]([CH3:22])([CH3:21])[CH3:20])[CH3:15].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(C)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>C1COCC1>[Cl:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][N:5]=[C:4]([O:11][CH2:15][C@@H:14]([NH:16][C:17](=[O:23])[O:18][C:19]([CH3:20])([CH3:22])[CH3:21])[CH3:13])[CH:3]=1
C[C@@H](CO)NC(=O)OC(C)(C)C
O=[N+]([O-])c1cnc(O)cc1Cl
null
CC(C)OC(=O)N=NC(=O)OC(C)C
c1ccc(P(c2ccccc2)c2ccccc2)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
C1CCOC1
null
null
null
null
null
null
null
null
null
25
0.5
To a solution of 4-chloro-5-nitropyridin-2-ol (1.00 g), tert-butyl ((2S)-1-hydroxypropan-2-yl)carbamate (1.51 g) and triphenylphosphine (2.25 g) in THF (10 mL) was added dropwise diisopropyl azodicarboxylate toluene solution (1.9 M, 4.52 mL), and the mixture was stirred at room temperature for 30 min. The reaction mixture was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (NH, hexane/ethyl acetate) to give the title compound (860 mg).
C[C@@H](COc1cc(Cl)c([N+](=O)[O-])cn1)NC(=O)OC(C)(C)C
null
45.2
null
422,939
ord_dataset-1a231de00bfe4443b547e1f03885ed41
null
1999-01-01T00:01:00
true
F[CH2:2][C:3]([C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=O.[NH2:11][NH2:12].C(Cl)Cl>C(O)CO>[CH3:2][C:3]1[C:5]2[C:10](=[CH:9][CH:8]=[CH:7][CH:6]=2)[NH:12][N:11]=1
NN
O=C(CF)c1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
OCCO
null
null
null
null
null
null
null
null
null
25
2
To a stirring solution of 36.2 g (0.26 mol) of 2-Fluoroacetophenone in 120 mL of ethylene glycol is added 8.6 mL (0.27 mol, 1.05 equiv.) of hydrazine. The resulting solution is stirred 2 h at RT and then heated at 165° C. for 40 h. The solution is cooled to RT, poured into CH2Cl2 (200 mL) and extracted with H2O (2×200 mL). The organic layers were combined, dried (MgSO4), and the solvent removed in vacuo. Purification of the crude material by recrystallization form hexane/CHCl3 afforded 26 g of 3-Methylindazole as a light tan solid: 1H NMR (CDCl3, 300 MHz) δ7.73 (d, 1H, J=8.1), 7.44 (m, 2H), 7.19 (dd, 1H, J=7.0,7.0), 2.67 (s, 3H).
Cc1n[nH]c2ccccc12
null
75.7
null
1,294,340
ord_dataset-de51ecc8d4434bacaa8bc32d7d73484c
null
2013-01-01T00:05:00
true
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C@H:8]([O:10][C:11](=[O:26])[NH:12][C:13]1[C:14]([CH3:25])=[N:15][O:16][C:17]=1[C:18]1[CH:23]=[CH:22][C:21](Br)=[CH:20][CH:19]=1)[CH3:9].[CH2:27]([O:29][C:30](=[O:49])[C:31]([CH3:48])([C:33]1[CH:38]=[CH:37][C:36](B2OC(C)(C)C(C)(C)O2)=[CH:35][CH:34]=1)[CH3:32])[CH3:28]>>[CH2:27]([O:29][C:30](=[O:49])[C:31]([C:33]1[CH:38]=[CH:37][C:36]([C:21]2[CH:22]=[CH:23][C:18]([C:17]3[O:16][N:15]=[C:14]([CH3:25])[C:13]=3[NH:12][C:11]([O:10][C@@H:8]([C:3]3[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=3[F:1])[CH3:9])=[O:26])=[CH:19][CH:20]=2)=[CH:35][CH:34]=1)([CH3:48])[CH3:32])[CH3:28]
CCOC(=O)C(C)(C)c1ccc(B2OC(C)(C)C(C)(C)O2)cc1
Cc1noc(-c2ccc(Br)cc2)c1NC(=O)O[C@H](C)c1ccccc1F
null
null
null
null
null
null
null
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 described in Example 36, Step 6, [5-(4-bromo-phenyl)-3-methyl-isoxazol-4-yl]-carbamic acid (R)-1-(2-fluoro-phenyl)-ethyl ester and 2-methyl-2-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-propionic acid ethyl ester were reacted to provide 2-(4′-{4-[(R)-1-(2-Fluoro-phenyl)-ethoxycarbonylamino]-3-methyl-isoxazol-5-yl}-biphenyl-4-yl)-2-methyl-propionic acid ethyl ester, which was hydrolyzed to the acid as described in Example 17, Step 3.
CCOC(=O)C(C)(C)c1ccc(-c2ccc(-c3onc(C)c3NC(=O)O[C@H](C)c3ccccc3F)cc2)cc1
null
null
null
790,641
ord_dataset-530502f8e61e455784f93c5faa45c94b
null
2007-01-01T00:09:00
true
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9]1[C:18]([C:19]2[CH:24]=[CH:23][C:22]([Cl:25])=[CH:21][CH:20]=2)=[CH:17][C:12]([C:13]([O:15][CH3:16])=[O:14])=[C:11](Cl)[N:10]=1.[Cl:27][C:28]1[CH:29]=[N:30][CH:31]=[C:32]([OH:34])[CH:33]=1>>[Cl:25][C:22]1[CH:23]=[CH:24][C:19]([C:18]2[C:9]([C:3]3[CH:4]=[CH:5][C:6]([Cl:8])=[CH:7][C:2]=3[Cl:1])=[N:10][C:11]([O:34][C:32]3[CH:31]=[N:30][CH:29]=[C:28]([Cl:27])[CH:33]=3)=[C:12]([CH:17]=2)[C:13]([O:15][CH3:16])=[O:14])=[CH:20][CH:21]=1
Oc1cncc(Cl)c1
COC(=O)c1cc(-c2ccc(Cl)cc2)c(-c2ccc(Cl)cc2Cl)nc1Cl
null
null
null
null
null
null
null
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 the procedure described in Example 84, methyl 6-(2,4-dichlorophenyl)-5-(4-chlorophenyl)-2-chloro-nicotinate Example 83 was reacted with 3-chloro-5-hydroxypyridine to afford the title compound: m/e=521 (M+3); Rt=4.65 min
COC(=O)c1cc(-c2ccc(Cl)cc2)c(-c2ccc(Cl)cc2Cl)nc1Oc1cncc(Cl)c1
null
null
null
138,903
ord_dataset-3fa0a6b7d51b4fc6a5380aa0d03ac884
null
1985-01-01T00:12:00
true
[Cl:1][CH:2]=[C:3]1[C:7]([CH2:9][CH3:10])([CH3:8])[CH2:6][CH2:5][O:4]1.[ClH:11]>>[Cl:1][CH2:2][C:3](=[O:4])[C:7]([CH2:9][CH3:10])([CH3:8])[CH2:6][CH2:5][Cl:11]
CCC1(C)CCOC1=CCl
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
2
64 g (0.4 mole) of 2-chloromethylene-3-ethyl-3-methyl-tetrahydrofuran are saturated with hydrogen chloride gas at 10° to 20° C., while cooling with ice. After the mixture has been left to stand at room temperature for 2 hours, excess hydrogen chloride is stripped off and the residue is distilled. 60 g (81% of theory) of 1,5-dichloro-3-ethyl-3-methyl-2-pentanone of boiling point 92°-101° C./0.05 mbar are obtained. ##STR102##
CCC(C)(CCCl)C(=O)CCl
null
81
null
389,881
ord_dataset-44d518e567bd4c039d77233023f78bb2
null
1998-01-01T00:01:00
true
S(=O)(=O)(O)O.[CH3:6]O.[C:8]([OH:17])(=[O:16])[CH2:9][CH2:10][CH2:11][CH2:12][CH:13]([CH3:15])[CH3:14]>C1(C)C=CC=CC=1>[CH3:6][O:16][C:8](=[O:17])[CH2:9][CH2:10][CH2:11][CH2:12][CH:13]([CH3:15])[CH3:14]
CO
CC(C)CCCCC(=O)O
null
O=S(=O)(O)O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
2 g concentrated sulfuric acid were added to a solution of 32 g (1 mol) methanol and 144 g (1 mol) "isooctanoic acid" (isomeric mixture from Ruhrchemie A. G. Oberhausen) in 200 ml toluene and heated to boiling with hater separation until the equimolar amount of water separates (about 2 hours). After cooling it was washed with water and then with 10% sodium bicarbonate solution. The solvent was distilled off under reduced pressure. The remaining end-product after distillation over a 15 cm Vigreux column gave 150 g (95%) isooctanoic acid methylester as an easily mobile liquid with a fruity smell.
COC(=O)CCCCC(C)C
null
95
null
1,626,462
ord_dataset-f0794d5ded7a4d3fab45cc3d7a89ee3d
null
2015-01-01T00:09:00
true
C1C=CC(C2C=CC=CC=2)=CC=1.C1C=CC(OC2C=CC=CC=2)=CC=1.[Br:26][C:27]1[CH:32]=[CH:31][C:30]([NH:33][CH:34]=[C:35]([S:41]([CH3:44])(=[O:43])=[O:42])[C:36]([O:38]CC)=O)=[CH:29][CH:28]=1>>[Br:26][C:27]1[CH:28]=[C:29]2[C:30](=[CH:31][CH:32]=1)[N:33]=[CH:34][C:35]([S:41]([CH3:44])(=[O:42])=[O:43])=[C:36]2[OH:38]
CCOC(=O)C(=CNc1ccc(Br)cc1)S(C)(=O)=O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
c1ccc(Oc2ccccc2)cc1
c1ccc(-c2ccccc2)cc1
null
null
null
null
null
null
null
null
null
25
2
To Dowtherm at 250° C. was added ethyl 3-(4-bromophenylamino)-2-(methylsulfonyl)acrylate (1.08 g, 3.10 mmol) portionwise and the reaction mixture was stirred for 2 h. The reaction mixture was cooled to room temperature, diluted with hexanes and the resulting precipitate was filtered to afford the desired product (573 mg, 61%) as a tan solid: ESI MS m/z 302 [C10H8BrNO3S+H]+.
CS(=O)(=O)c1cnc2ccc(Br)cc2c1O
null
61.2
null
391,607
ord_dataset-4bc8addcf9cf4845817557760d62d5b5
null
1998-01-01T00:02:00
true
[C:1]([O:5]/[N:6]=[C:7](\[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][N:17]=1)/[C:8]1[CH:13]=[C:12](Br)[CH:11]=[CH:10][C:9]=1[OH:15])([CH3:4])([CH3:3])[CH3:2].C(N)[CH2:23][NH2:24]>CN(C=O)C.O>[C:1]([O:5]/[N:6]=[C:7](\[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][N:17]=1)/[C:8]1[CH:13]=[C:12]([C:23]#[N:24])[CH:11]=[CH:10][C:9]=1[OH:15])([CH3:4])([CH3:3])[CH3:2]
CC(C)(C)O/N=C(\c1ccccn1)c1cc(Br)ccc1O
NCCN
null
null
null
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
0.5
(Z)-2-(5-bromo-2-hydroxybenzoyl)pyridine O-t-butyloxime (12.7 g) was dissolved in DMF (100 ml). To the solution was added cuprous cyanide (4.64 g), and the mixture was heated, under argon atmosphere, for 3 hours under reflux. To the reaction mixture was added a solution of ethylenediamine (30 ml) in water (20 ml). The mixture was stirred for 30 minutes at room temperature, followed by extraction with ethyl acetate. The organic layer was dried (anhydrous magnesium sulfate), then the solvent was distilled off. The residue was purified by means of a silica gel column chromatography, eluting with ethyl acetate/hexane, to give (Z)-2-(5-cyano-2-hydroxybenzoyl)pyridine O-t-butyloxime (4.31 g) (Compound 76).
CC(C)(C)O/N=C(\c1ccccn1)c1cc(C#N)ccc1O
null
null
null
525,035
ord_dataset-293186f5c9b441cab57f03cd3a18ac26
null
2001-01-01T00:11:00
true
[C:1]([C:3]1[CH:4]=[N:5][CH:6]=[CH:7][CH:8]=1)#[CH:2].Br[C:10]1[C:18]([N+:19]([O-:21])=[O:20])=[CH:17][CH:16]=[C:15]2[C:11]=1/[C:12](=[CH:23]/[C:24]1[NH:25][CH:26]=[CH:27][C:28]=1[O:29][CH3:30])/[C:13](=[O:22])[NH:14]2>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.[Cu]I.CN(C=O)C.CCN(CC)CC>[CH3:30][O:29][C:28]1[CH:27]=[CH:26][NH:25][C:24]=1/[CH:23]=[C:12]1\[C:13](=[O:22])[NH:14][C:15]2[C:11]\1=[C:10]([C:2]#[C:1][C:3]1[CH:4]=[N:5][CH:6]=[CH:7][CH:8]=1)[C:18]([N+:19]([O-:21])=[O:20])=[CH:17][CH:16]=2
COc1cc[nH]c1/C=C1\C(=O)Nc2ccc([N+](=O)[O-])c(Br)c21
C#Cc1cccnc1
null
[Cu]I
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
CCN(CC)CC
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
null
Using Method D above, 3-ethynyl pyridine (0.14 g, 1.38 mmol) (see Example 64) was coupled with (Z)-4-bromo-1,3-dihydro-3-[(3-methoxy-1H-pyrrol-2-yl)methylene]-5-nitro-2H-indol-2-one (0.2 g, 0.55 mmol) (Starting Material 3) using (Ph3P)4Pd (31.8 mg) (Aldrich) and CuI (5.3 mg) (Aldrich) as catalyst in DMF (6 mL) and Et3N (6 mL) as solvent and at 85° C. for 18 h, yielding (Z)-1,3-dihydro-3-[(3-methoxy-1H-pyrrol-2-yl)methylene]-5-nitro-4-[(3-pyridinyl)ethynyl]-2H-indol-2-one. (Yield 0.16 g, 71%).
COc1cc[nH]c1/C=C1\C(=O)Nc2ccc([N+](=O)[O-])c(C#Cc3cccnc3)c21
null
null
null
1,142,483
ord_dataset-68715347640045adb1b09e6a04722b0e
null
2012-01-01T00:03:00
true
[Cl:1][C:2]1[CH:9]=[C:6]([CH:7]=[O:8])[C:5]([OH:10])=[CH:4][CH:3]=1.[CH3:11][C:12]1([CH3:25])[CH2:17][CH:16](OS(C)(=O)=O)[CH2:15][C:14]([CH3:24])([CH3:23])[O:13]1.C([O-])([O-])=O.[K+].[K+]>CN(C)C=O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([O:10][CH:16]2[CH2:15][C:14]([CH3:24])([CH3:23])[O:13][C:12]([CH3:25])([CH3:11])[CH2:17]2)=[C:6]([CH:9]=1)[CH:7]=[O:8]
CC1(C)CC(OS(C)(=O)=O)CC(C)(C)O1
O=Cc1cc(Cl)ccc1O
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
null
null
null
null
null
null
null
null
null
null
null
null
In a manner similar to the method described in example 4a, 5-chlorosalicylaldehyde (4.6 g, 30 mmol) (Aldrich) reacted with methanesulfonic acid 2,2,6,6-tetramethyl-tetrahydro-pyran-4-yl ester (8 g, 34 mmol) and K2CO3 in N,N-dimethylformamide to give 5-chloro-2-(2,2,6,6-tetramethyl-tetrahydro-pyran-4-yloxy)-benzaldehyde as a off white solid (Yield 0.94 g, 10%).
CC1(C)CC(Oc2ccc(Cl)cc2C=O)CC(C)(C)O1
null
null
null
1,272,094
ord_dataset-d3580a12b15e46cc91aa73f4f1a4a8cc
null
2013-01-01T00:03:00
true
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[NH:8][C:9]([C:12]1[S:25][C:15]2[C:16]3[CH:24]=[N:23][CH:22]=[CH:21][C:17]=3[O:18][CH2:19][CH2:20][C:14]=2[CH:13]=1)=[N:10][NH2:11].[CH2:26](OC(OCC)OCC)C>>[S:25]1[C:15]2[C:16]3[CH:24]=[N:23][CH:22]=[CH:21][C:17]=3[O:18][CH2:19][CH2:20][C:14]=2[CH:13]=[C:12]1[C:9]1[N:8]([C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=2[Cl:1])[CH:26]=[N:11][N:10]=1
NN=C(Nc1ccccc1Cl)c1cc2c(s1)-c1cnccc1OCC2
CCOC(OCC)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
85
null
A mixture of N-(2-chlorophenyl)-4,5-dihydropyrido[4,3-b]thieno[2,3-d]oxepine-2-carbohydrazonamide (44 mg, 0.12 mmol) and 3 ml of triethylorthoformate was heated at 85° C. for 4 hours. The mixture was concentrated in vacuum and triturated with diethylether. The precipitate was collected, washed with diethylether and purified by flash chromatography eluting with 60% of ethyl acetate in hexane to give 320 (17 mg, 38%). MS: (ESI+) 381.1
Clc1ccccc1-n1cnnc1-c1cc2c(s1)-c1cnccc1OCC2
null
38
null
359,342
ord_dataset-58ec5adfcd8648dc9e26ee757d289517
null
1997-01-01T00:03:00
true
[O:1]1[CH2:3][C@H:2]1[CH2:4][O:5][C:6]1[CH:14]=[CH:13][CH:12]=[C:11]2[C:7]=1[CH:8]=[CH:9][NH:10]2.[Cl:15][C:16]1[CH:17]=[C:18]2[C:22](=[CH:23][CH:24]=1)[NH:21][CH:20]=[C:19]2[CH:25]1[CH2:30][CH2:29][NH:28][CH2:27][CH2:26]1.C(O)C>CS(C)=O>[Cl:15][C:16]1[CH:17]=[C:18]2[C:22](=[CH:23][CH:24]=1)[NH:21][CH:20]=[C:19]2[CH:25]1[CH2:30][CH2:29][N:28]([CH2:3][C@H:2]([OH:1])[CH2:4][O:5][C:6]2[CH:14]=[CH:13][CH:12]=[C:11]3[C:7]=2[CH:8]=[CH:9][NH:10]3)[CH2:27][CH2:26]1
c1cc(OC[C@@H]2CO2)c2cc[nH]c2c1
Clc1ccc2[nH]cc(C3CCNCC3)c2c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
CS(C)=O
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared in a fashion similar to that described in Example 1 using (S)-(+)-4-(oxiranylmethoxy)-1H-indole and 5-chloro-3-(piperidin-4-yl)-1H-indole using ethanol as the reaction solvent. Yield 0.380 g (42%) as a yellowish foam. mp 109°-114° C. (dec) FDMS m/e=423 (M+ of free base). α[D]589 =+6.5 (c=1.04, dimethylsulfoxide).
O[C@H](COc1cccc2[nH]ccc12)CN1CCC(c2c[nH]c3ccc(Cl)cc23)CC1
null
null
null
409,358
ord_dataset-324fb6fdc2414cb79e436bf5d04d4bd2
null
1998-01-01T00:08:00
true
[CH3:1][N:2]([O:7][CH3:8])[C:3](=[O:6])[CH2:4]Br.[C:9]([NH:12][C:13]1[CH:18]=[CH:17][C:16]([OH:19])=[CH:15][CH:14]=1)(=[O:11])[CH3:10].C(=O)([O-])[O-].[Cs+].[Cs+]>C(#N)C>[CH3:1][N:2]([O:7][CH3:8])[C:3](=[O:6])[CH2:4][O:19][C:16]1[CH:15]=[CH:14][C:13]([NH:12][C:9](=[O:11])[CH3:10])=[CH:18][CH:17]=1
CON(C)C(=O)CBr
CC(=O)Nc1ccc(O)cc1
null
O=C([O-])[O-]
[Cs+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC#N
null
null
null
null
null
null
null
null
null
null
null
null
This bromoacetamide was dissolved in acetonitrile and to the solution were added 10.75 gm (71.15 mMol) 4-acetamidophenol followed by 23.10 gm (71.1 mMol) cesium carbonate. The reaction mixture was heated at reflux for 3 hours and then concentrated under reduced pressure. The residue was partitioned between dichloromethane and 1N aqueous sodium hydroxide. The organic phase was separated, washed sequentially with water and saturated aqueous sodium chloride, dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel chromatography, eluting with ethyl acetate. Fractions containing product were combined and concentrated under reduced pressure to provide 10.34 gm (74%) of the desired compound.
CON(C)C(=O)COc1ccc(NC(C)=O)cc1
null
74
null
166,688
ord_dataset-5c25f386f4664070a72d578feacedf86
null
1987-01-01T00:12:00
true
[F:1][CH2:2][C:3]([CH3:13])([CH3:12])[C:4](=[O:11])[CH2:5][N:6]1[CH:10]=[N:9][CH:8]=[N:7]1.[OH-].[K+].[CH3:16]I.[ClH:18]>CS(C)=O.O>[ClH:18].[F:1][CH2:2][C:3]([CH3:13])([CH3:12])[C:4](=[O:11])[CH:5]([N:6]1[CH:10]=[N:9][CH:8]=[N:7]1)[CH3:16]
CI
CC(C)(CF)C(=O)Cn1cncn1
null
Cl
[K+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CS(C)=O
null
null
null
null
null
null
null
null
null
25
24
37.2 g (0.2 mol) of 1-fluoro-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-butan-3-one were dissolved in 200 ml of dimethylsulphoxide, 11.2 g (0.2 mol) of potassium hydroxide, dissolved in 24 ml of water, were added and 28.4 g (0.2 mol) of methyl iodide were added dropwise at 20° C., whilst cooling. The reaction mixture was subsequently stirred at room temperature for 24 hours and poured onto 1,000 ml of water, the mixture was extracted twice with 200 ml of methylene chloride each time, the combined organic phases were washed five times with 100 ml of water each time and dried over sodium sulphate, the solvent was distilled off, the residue was taken up in 100 ml of acetone, the mixture was filtered and the solvent was distilled off from the mother liquor. The residue was taken up in 150 ml of ethyl acetate, and 14.4 g (0.2 mol) of hydrogen chloride were passed in. Thereafter, the mixture was allowed to crystallise out. 33.8 g (72% of theory) of 1-fluoro-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-pentan-3-one hydrochloride of melting point 142° C. were obtained. ##STR62##
CC(C(=O)C(C)(C)CF)n1cncn1
null
71.7
null
496,927
ord_dataset-9df8b3ec9c8742b3802e0efaac6f6ef3
null
2001-01-01T00:03:00
true
[C:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[CH2:10][CH:11]([CH:19]([CH:21]1[CH2:26][CH2:25][CH2:24][CH2:23][CH2:22]1)[OH:20])[C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])([OH:3])=[O:2].[CH2:27](Br)[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1.C(=O)([O-])[O-].[K+].[K+]>CN(C)C=O>[CH2:27]([O:2][C:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[CH2:10][CH:11]([CH:19]([CH:21]1[CH2:22][CH2:23][CH2:24][CH2:25][CH2:26]1)[OH:20])[C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])=[O:3])[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1
BrCc1ccccc1
CC(C)(C)OC(=O)C(Cc1ccccc1C(=O)O)C(O)C1CCCCC1
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
null
null
null
null
null
null
null
null
null
null
null
0.5
To a solution of t-butyl 2-(2-carboxyphenylmethyl)-3-cyclohexyl-3-hydroxypropionate (200 mg) in dimethylformamide (2 ml) were added benzyl bromide (100 mg) and potassium carbonate (270 mg) successively. After being stirred for 30 minutes the mixture was filtered and the filtrate was evaporated under reduced pressure. The residue was purified by preparative thin layer chromatography [silica gel, ethyl acetate - n-hexane (1:1)] to afford t-butyl 2-(2-benzyloxycarbonylphenylmethyl)-3-cyclohexyl-3-hydroxypropionate (108 mg).
CC(C)(C)OC(=O)C(Cc1ccccc1C(=O)OCc1ccccc1)C(O)C1CCCCC1
null
43.2
null
274,978
ord_dataset-02ee2261663048188cf6d85d2cc96e3f
null
1993-01-01T00:09:00
true
Br[CH2:2][CH2:3][CH2:4][CH2:5][N:6]1[C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=2[N:8]=[CH:7]1.[N:15]1([C:21]2[CH:30]=[CH:29][C:24]3[O:25][CH2:26][CH2:27][O:28][C:23]=3[CH:22]=2)[CH2:20][CH2:19][NH:18][CH2:17][CH2:16]1>C(#N)C>[N:6]1([CH2:5][CH2:4][CH2:3][CH2:2][N:18]2[CH2:19][CH2:20][N:15]([C:21]3[CH:30]=[CH:29][C:24]4[O:25][CH2:26][CH2:27][O:28][C:23]=4[CH:22]=3)[CH2:16][CH2:17]2)[C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=2[N:8]=[CH:7]1
c1cc2c(cc1N1CCNCC1)OCCO2
BrCCCCn1cnc2ccccc21
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC#N
null
null
null
null
null
null
null
null
null
null
null
null
Analogously to Example 1, reaction of 1-(4-bromobutyl)benzimidazole with 6-piperazino-1,4-benzodioxane ("A") in 200 ml of acetonitrile gives 6-[4-(4-(benzimidazol-1-yl)butyl)piperazino]-1,4-benzodioxane, m.p. 247-248°.
c1ccc2c(c1)ncn2CCCCN1CCN(c2ccc3c(c2)OCCO3)CC1
null
null
null
557,759
ord_dataset-f483e698250b4da0a84f425c7bfa965a
null
2002-01-01T00:08:00
true
[C:1]([C:5]1[CH:6]=[C:7]([CH:28]=[CH:29][C:30]=1[OH:31])[O:8][C:9]1[CH:10]=[CH:11][C:12]([N+:25]([O-])=O)=[C:13]([N:15]([CH2:23]C)[C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19])[CH:14]=1)([CH3:4])([CH3:3])[CH3:2]>[Pd].CO>[NH2:25][C:12]1[CH:11]=[CH:10][C:9]([O:8][C:7]2[CH:28]=[CH:29][C:30]([OH:31])=[C:5]([C:1]([CH3:4])([CH3:2])[CH3:3])[CH:6]=2)=[CH:14][C:13]=1[N:15]([CH3:23])[C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19]
CCN(C(=O)OC(C)(C)C)c1cc(Oc2ccc(O)c(C(C)(C)C)c2)ccc1[N+](=O)[O-]
null
null
[Pd]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
null
null
In a similar manner to that described in Reference Example 7, a reaction was carried out using t-butyl N-[5-(3-t-butyl-4-hydroxyphenoxy)-2-nitrophenyl]-N-ethylcarbamate (1.29 g), palladium on carbon (10%, 0.16 g) and methanol (40 ml) and the reaction mixture was purified to give the title compound (1.11 g).
CN(C(=O)OC(C)(C)C)c1cc(Oc2ccc(O)c(C(C)(C)C)c2)ccc1N
null
95.8
null
1,067,321
ord_dataset-ffbef48837674f39816de887b5dc8bae
null
2011-01-01T00:06:00
true
[C:1]([SiH2:5][O:6][C:7]([CH3:19])([CH3:18])[C:8]1[CH:9]=[C:10]([CH2:15][CH2:16][OH:17])[CH:11]=[CH:12][C:13]=1[Cl:14])([CH3:4])([CH3:3])[CH3:2].CCN(CC)CC.[CH3:27][S:28](Cl)(=[O:30])=[O:29]>C(Cl)Cl>[C:1]([SiH2:5][O:6][C:7]([CH3:19])([CH3:18])[C:8]1[CH:9]=[C:10]([CH2:15][CH2:16][O:17][S:28]([CH3:27])(=[O:30])=[O:29])[CH:11]=[CH:12][C:13]=1[Cl:14])([CH3:4])([CH3:3])[CH3:2]
CS(=O)(=O)Cl
CC(C)(C)[SiH2]OC(C)(C)c1cc(CCO)ccc1Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(CC)CC
ClCCl
null
null
null
null
null
null
null
null
null
0
1
To a sol. of 2-[3-(tert-butyl-dimethyl-silanyloxymethyl)-4-chloro-phenyl]-ethanol (2.00 g, 6.65 mmol) in CH2Cl2 (66 mL) at 0° C. were added dropwise Et3N (1.02 mL, 7.31 mmol) and methanesulfonyl chloride (0.57 mL, 7.3 mmol). The reaction was stirred at 0° C. for 1 h, and was diluted with CH2Cl2 (40 mL). The resulting mixture was washed with aq. sat. NH4Cl (2×). The org. layer was dried over MgSO4, filtered, and the solvents were removed under reduced pressure to yield the crude title compound (2.55 g, quantitative yield) that was used further without purification. LC-MS: tR=1.13 min; ES+: 379.29.
CC(C)(C)[SiH2]OC(C)(C)c1cc(CCOS(C)(=O)=O)ccc1Cl
null
101.2
null
464,331
ord_dataset-6c36eb0f817d4144988b8963c5d58879
null
2000-01-01T00:05:00
true
[C:1]1([CH2:7][CH:8]=[CH:9][C:10]([OH:12])=[O:11])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH3:13][O:14][C:15]1[CH:16]=[C:17]([SH:23])[CH:18]=[CH:19][C:20]=1[O:21][CH3:22].N1CCCCC1>>[CH3:13][O:14][C:15]1[CH:16]=[C:17]([S:23][CH:8]([CH2:7][C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH2:9][C:10]([OH:12])=[O:11])[CH:18]=[CH:19][C:20]=1[O:21][CH3:22]
COc1ccc(S)cc1OC
O=C(O)C=CCc1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCNCC1
null
null
null
null
null
null
null
null
null
null
110
null
A mixture of 4-phenylbut-2-enoic acid (2 g, 12.33 mmol) prepared as in Example 6, Step B, 3,4-dimethoxybenzenethiol (2.1 mL, 14.79 mmol, 1.2 eq), and piperidine (0.4 mL (3.7 mmol, 0.3 eq) is heated at 110° C. in a bomb for 18 hours. The reaction is partitioned between ethyl ether and 1 N HCl. The organic layer is dried over anhydrous MgSO4 and concentrated in vacuo. The product is purified by flash silica gel chromatography to afford 3-(3,4-dimethoxyphenylsulfanyl)-4-phenylbutanoic acid as a yellow oil. (4.1 g, 100%): 1H-NMR (300 MHz, CDCl3) δ (TMS) 2.54(d, 0.5×2H), 2.56(d, 0.5×2H), 2.83(d, 0.5×2H), 2.98(d, 0.5×2H), 3.56(m, 1H), 3.85(s, 3H), 3.88(s, 3H), 6.8(d, 1H), 6.97(d, 1H), 7.05(d, 0.5×1H), 7.09(d, 0.5×1H), 7.15-7.32(m, 5H).
COc1ccc(SC(CC(=O)O)Cc2ccccc2)cc1OC
null
null
null
1,610,657
ord_dataset-9cecb3a8d3b9494191b28dcefea66af2
null
2015-01-01T00:07:00
true
[Al+3].[Cl-].[Cl-].[Cl-].[CH3:5][O:6][C:7]1[N:15]=[C:14]2[C:10]([CH:11]=[CH:12][NH:13]2)=[CH:9][CH:8]=1.[C:16](Cl)(=[O:18])[CH3:17].CO>C(Cl)Cl>[CH3:5][O:6][C:7]1[N:15]=[C:14]2[NH:13][CH:12]=[C:11]([C:16](=[O:18])[CH3:17])[C:10]2=[CH:9][CH:8]=1
COc1ccc2cc[nH]c2n1
CC(=O)Cl
null
[Al+3]
[Cl-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
CO
null
null
null
null
null
null
null
null
null
25
0.5
To a suspension of AlCl3 (1.37 g, 10.3 mmol) in CH2Cl2 (40 mL) was added 6-methoxy-7-azaindole (315 mg, 2.07 mmol) and the mixture was stirred at RT for 30 min under nitrogen. Acetyl chloride (736 μL, 10.3 mmol) was added dropwise and the resulting mixture stirred at RT overnight. MeOH (8 mL) was added cautiously to quench the reaction and the solvents were removed under vacuum. The residue was purified by flash column chromatography on silica gel (CH2Cl2 to CH2Cl2/MeOH 93-7) and by preparative HPLC (Waters Sunfire C18-ODB, 5 μm, 30×100 mm, 5% to 100% CH3CN in H2O in 25 min, CH3CN and H2O containing 0.1% TFA, flow: 40 mL/min) to give after neutralization (aqueous saturated NaHCO3) and extraction (CH2Cl2) of the purified fractions the desired compound TLC, Rf (CH2Cl2/MeOH 9:1)=0.55; MS (UPLC/MS): 191.2 [M+H]+, 189.1 [M−H]−, 379.2 [2M−H]−; tR (HPLC conditions f): 1.45 min. 1H-NMR (400 MHz, DMSO): δ (ppm): 8.35 (d, 1H), 8.29 (s, 1H), 6.75 (d, 1H), 5.04 (s, 2H), 3.89 (s, 3H), 2.44 (s, 3H).
COc1ccc2c(C(C)=O)c[nH]c2n1
null
null
null
1,034,101
ord_dataset-83acb82dc5ba4f7aba439b9875aaac43
null
2011-01-01T00:02:00
true
[Br:1][CH2:2][C:3]([C:5]1[CH:6]=[CH:7][C:8]2[O:13][C:12]([CH3:15])([CH3:14])OC[C:9]=2[CH:16]=1)=[O:4].B.C1C[O:21][CH2:20]C1>C1COCC1>[Br:1][CH2:2][C@@H:3]([C:5]1[CH:6]=[CH:7][C:8]2[O:13][C:12]([CH3:14])([CH3:15])[CH2:20][O:21][C:9]=2[CH:16]=1)[OH:4]
C1CCOC1
CC1(C)OCc2cc(C(=O)CBr)ccc2O1
null
B
null
null
null
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
To the product of step (c) (10 g, 35.1 mmol) in 100 mL of THF was added the solid catalyst of Preparation 13, step (c)(1) (0.97 g, 3.5 mmol). The solution was cooled to between −20° C. and −10° C. and BH3-THF (35 mL, 35 mmol) diluted with 50 mL THF was added dropwise via a dropping funnel. After the addition was complete, the reaction mixture was allowed to warm to ambient temperature. After 30 minutes, the reaction mixture was quenched by slow addition of 50 mL of methanol and then concentrated to a thick oil. The oil was purified by silica gel chromatography eluted with 1:2 ethyl acetate/hexanes. The fractions were combined and concentrated to give the title compound as an off-white solid.
CC1(C)COc2cc([C@@H](O)CBr)ccc2O1
null
null
null
1,275,233
ord_dataset-d5c54236ecd94d61aaa071461bcfc426
null
2013-01-01T00:04:00
true
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[C:10]([NH2:20])[CH:11]=[N:12][C:13]=2[O:14][CH2:15][C:16]([F:19])([F:18])[F:17])=[CH:4][CH:3]=1.[CH3:21][C:22]1[O:26][CH:25]=[N:24][C:23]=1[C:27](O)=[O:28]>>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[CH:9]=[C:10]([NH:20][C:27]([C:23]3[N:24]=[CH:25][O:26][C:22]=3[CH3:21])=[O:28])[CH:11]=[N:12][C:13]=2[O:14][CH2:15][C:16]([F:17])([F:18])[F:19])=[CH:6][CH:7]=1
Nc1cnc(OCC(F)(F)F)c(-c2ccc(Cl)cc2)c1
Cc1ocnc1C(=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 title compound was synthesized in analogy to Example 1, using 5-(4-chloro-phenyl)-6-(2,2, 2-trifluoro-ethoxy)-pyridin-3-ylamine and 5-methyl-4-oxazolecarboxylic acid as starting materials, MS (LC/MS): 412.2 (M+H).
Cc1ocnc1C(=O)Nc1cnc(OCC(F)(F)F)c(-c2ccc(Cl)cc2)c1
null
null
null
988,749
ord_dataset-35b56288528641309a040cc2b6710b61
null
2010-01-01T00:08:00
true
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:10])[CH3:9])=[CH:4][CH:3]=1.Br[CH2:12][CH2:13][Cl:14].C([O-])([O-])=O.[K+].[K+]>CC(C)=O>[Cl:14][CH2:13][CH2:12][O:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:10])[CH3:9])=[CH:4][CH:3]=1
ClCCBr
CC(=O)c1ccc(O)cc1
null
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(C)=O
null
null
null
null
null
null
null
null
null
null
null
null
To a solution of 4′-hydroxyacetophenone (101 g, 0.74 mole) in acetone (800 mL) was added 1-bromo-2-chloroethane (638 g, 4.45 mole) followed by K2CO3 (307 g, 2.22 mole). The reaction was heated to reflux for 48 h then filtered. The K2CO3 was washed with acetone (1 L) and the filtrate was evaporated. The residue was then partitioned between EtOAc (800 mL) and 1 N NaOH (250 mL). The organic layer was washed with 1N NaOH (250 mL) then dried and evaporated to yield 146 g of the desired product (99% yield).
CC(=O)c1ccc(OCCCl)cc1
null
99.3
null
1,077,205
ord_dataset-afd812677c134591a99f46ce28de2524
null
2011-01-01T00:08:00
true
[C:1]([C:4]1[CH:5]=[C:6]2[C:11](=[CH:12][C:13]=1[O:14][CH3:15])[N:10]=[CH:9][CH:8]=[C:7]2[O:16][C:17]1[CH:22]=[CH:21][C:20]([NH:23][C:24](=O)[O:25]C2C=CC=CC=2)=[C:19]([Cl:33])[CH:18]=1)(=[O:3])[NH2:2].[CH:34]1([NH2:37])[CH2:36][CH2:35]1.O>CN(C)C=O>[Cl:33][C:19]1[CH:18]=[C:17]([CH:22]=[CH:21][C:20]=1[NH:23][C:24]([NH:37][CH:34]1[CH2:36][CH2:35]1)=[O:25])[O:16][C:7]1[C:6]2[C:11](=[CH:12][C:13]([O:14][CH3:15])=[C:4]([C:1]([NH2:2])=[O:3])[CH:5]=2)[N:10]=[CH:9][CH:8]=1
COc1cc2nccc(Oc3ccc(NC(=O)Oc4ccccc4)c(Cl)c3)c2cc1C(N)=O
NC1CC1
null
null
null
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
8
To a solution of phenyl N-(4-(6-carbamoyl-7-methoxy-4-quinolyl)oxy-2-chlorophenyl)carbamate (described in WO02/32872; 17.5 g, 37.7 mmol) dissolved in N,N-dimethylformamide (350 mL), was added cyclopropylamine (6.53 mL, 94.25 mmol) under nitrogen atmosphere, and the mixture were stirred at room temperature overnight. The mixture was poured into water (1.75 L), and stirred. Precipitated crude crystals were filtered off, washed with water, and dried at 70° C. for 50 minutes. Ethanol (300 mL) was added to the crude crystals, the mixture was heated to reflux for about 30 minutes to dissolve the crystals, and gradually cooled to room temperature overnight while stirring. Precipitated crystals were filtered off, dried in vacuo, and dried at 70° C. for 8 hours to give crystals of the title compound (12.91 g, yield 80.2 %).
COc1cc2nccc(Oc3ccc(NC(=O)NC4CC4)c(Cl)c3)c2cc1C(N)=O
null
80.2
null
1,518,261
ord_dataset-8c74302143c04eb9983e4b3a7ead2d72
null
2014-01-01T00:12:00
true
[OH:1][C:2]1([C:17]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)=[O:18])[CH2:7][CH2:6][C:5](B2OC(C)(C)C(C)(C)O2)=[CH:4][CH2:3]1.FC(F)(F)S(O[C:33]1[C:34]([CH3:62])([CH3:61])[C@H:35]2[C@:48]([CH3:51])([CH2:49][CH:50]=1)[C@@H:47]1[C@:38]([CH3:60])([C@@:39]3([CH3:59])[C@H:44]([CH2:45][CH2:46]1)[C@H:43]1[C@H:52]([C:55]([CH3:57])=[CH2:56])[CH2:53][CH2:54][C@:42]1([NH2:58])[CH2:41][CH2:40]3)[CH2:37][CH2:36]2)(=O)=O.O.C(=O)([O-])[O-].[Na+].[Na+]>O1CCOCC1.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>[NH2:58][C@:42]12[CH2:54][CH2:53][C@@H:52]([C:55]([CH3:57])=[CH2:56])[C@@H:43]1[C@@H:44]1[C@@:39]([CH3:59])([CH2:40][CH2:41]2)[C@@:38]2([CH3:60])[C@@H:47]([C@:48]3([CH3:51])[C@@H:35]([CH2:36][CH2:37]2)[C:34]([CH3:61])([CH3:62])[C:33]([C:5]2[CH2:6][CH2:7][C:2]([OH:1])([C:17]([O:19][CH2:20][C:21]4[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=4)=[O:18])[CH2:3][CH:4]=2)=[CH:50][CH2:49]3)[CH2:46][CH2:45]1
CC1(C)OB(C2=CCC(O)(C(=O)OCc3ccccc3)CC2)OC1(C)C
C=C(C)[C@@H]1CC[C@]2(N)CC[C@]3(C)[C@H](CC[C@@H]4[C@@]5(C)CC=C(OS(=O)(=O)C(F)(F)F)C(C)(C)[C@@H]5CC[C@]43C)[C@@H]12
null
c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
O=C([O-])[O-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
C1COCCO1
null
null
null
null
null
null
null
null
null
85
null
A flask containing benzyl 1-hydroxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohex-3-enecarboxylate (0.113 g, 0.221 mmol) and (1R,3aS,5aR,5bR,7aR,11aR,11bR,13 aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl trifluoromethanesulfonate (0.082 g, 0.147 mmol) was diluted with 1,4-dioxane (1 mL) and water (0.25 mL). To the mixture was added sodium carbonate hydrate (0.075 g, 0.605 mmol) and the mixture was degassed with nitrogen for five minutes. To the mixture was added palladium tetrakis (5.10 mg, 4.41 mmol) then the flask was purged then refilled with nitrogen three times. The mixture was heated to 85° C. for 4 h then was cooled to rt and was purified by flash chromatography using a 20-80% ethyl acetate in hexanes gradient and a 25 g silica gel column. The fractions containing the expected product were combined and concentrated under reduced pressure to give benzyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)-1-hydroxycyclohex-3-enecarboxylate (0.053 g, 0.083 mmol, 56.3% yield) as an off-white foam. LCMS: m/e 640.6 (M+H)+, 1.91 min (method 1).
C=C(C)[C@@H]1CC[C@]2(N)CC[C@]3(C)[C@H](CC[C@@H]4[C@@]5(C)CC=C(C6=CCC(O)(C(=O)OCc7ccccc7)CC6)C(C)(C)[C@@H]5CC[C@]43C)[C@@H]12
null
56.5
null
735,345
ord_dataset-76dd1b78ee414d2da0ed30700ef026f7
null
2006-01-01T00:10:00
true
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl[C:9](=[O:15])[C:10]([O:12][CH2:13][CH3:14])=[O:11]>N1C=CC=CC=1.O>[CH2:13]([O:12][C:10](=[O:11])[C:9]([NH:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)=[O:15])[CH3:14]
Nc1ccccc1
CCOC(=O)C(=O)Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
c1ccncc1
O
null
null
null
null
null
null
null
null
null
25
48
Aniline (3.4 g, 37 mmol) was dissolved in pyridine (50 mL), then ethyl chloroxoacetate (5.0 g, 37 mmol) was added to the resulting solution dropwise. The resulting mixture was stirred at room temperature for 48 hours, then diluted with water and extracted twice with EtOAc. The combined organic extracts were washed with 1N HCl, water, brine, then dried (Na2SO4) and concentrated to provide 5.8 g (81%) of an oil that crystallized on standing. 1H-NMR (DMSO-d6) δ: 1.3 (t, J=7 Hz, 3H), 4.3 (q, J=7 Hz, 2H), 7.1–7.8 (m, 5H), 10.7 (s, 1H); MS ES+m/e 194.2 (p+1), ES−m/e 192.3 (p−1).
CCOC(=O)C(=O)Nc1ccccc1
null
81.1
null