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
523,761
ord_dataset-293186f5c9b441cab57f03cd3a18ac26
null
2001-01-01T00:11:00
true
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([N:9]2[CH2:14][CH2:13][N:12]([C:15]3[CH:20]=[CH:19][N:18]=[CH:17][CH:16]=3)[CH2:11][CH2:10]2)=[CH:5][CH:4]=1)#[N:2].N>C(O)C.[Ni]>[NH2:2][CH2:1][C:3]1[CH:4]=[CH:5][C:6]([N:9]2[CH2:10][CH2:11][N:12]([C:15]3[CH:20]=[CH:19][N:18]=[CH:17][CH:16]=3)[CH2:13][CH2:14]2)=[CH:7][CH:8]=1
N#Cc1ccc(N2CCN(c3ccncc3)CC2)cc1
null
null
[Ni]
N
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
null
null
A solution of 1-(4-cyanophenyl)-4-(4-pyridyl)piperazine (1.8 g) in ethanol saturated with ammonia gas (150 ml) was hydrogenated at 150 atmospheres and 100° C. (using Raney Nickel as catalyst) in a high pressure hydrogenation apparatus for 18 hours. The solution was filtered through diatomaceous earth and the filtrate evaporated to give a solid which was purified by flash chromatography on alumina (ICN Alumina N 32-63) using a mixture of 95:5 dichloromethane:methanol as eluant. The residue was recrystallised from tetrahydrofuran/isohexane to give 1-(4-aminomethylphenyl)-4-(4-pyridyl)piperazine (1.3 g) m.p.168-170° C.; microanalysis, found: C,71.5; H,7.6; N,20.5%; C16H20N4 requires: C,71.6; H,7.5; N,20.9%; NMR: 3.2-3.4(m,4H), 3.4-3.6(m,4H), 3.65(s,2H), 6.8-6.9(d,2H), 6.9-7.0(d,2H), 7.15-7.25(d,2H), 8.15-8.25(d,2H); MS: m/z 269 (MH)+.
NCc1ccc(N2CCN(c3ccncc3)CC2)cc1
null
71.1
null
1,211,058
ord_dataset-dc3bb1b1ac4e4229a3fc28fb559a9777
null
2012-01-01T00:10:00
true
[CH3:1][N:2]([CH3:8])[CH2:3][CH2:4][CH2:5][NH:6][CH3:7].CCN(C(C)C)C(C)C.[N:18]([C:21]([CH3:27])([CH3:26])[CH2:22][C:23](Cl)=[O:24])=[N+:19]=[N-:20].[OH-].[Na+]>ClCCCl>[N:18]([C:21]([CH3:27])([CH3:26])[CH2:22][C:23]([N:6]([CH2:5][CH2:4][CH2:3][N:2]([CH3:8])[CH3:1])[CH3:7])=[O:24])=[N+:19]=[N-:20]
CC(C)(CC(=O)Cl)N=[N+]=[N-]
CNCCCN(C)C
null
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(C(C)C)C(C)C
ClCCCl
null
null
null
null
null
null
null
null
null
0
1
To a stirred ice cold solution of N1,N1,N3-trimethylpropane-1,3-diamine (5.0 g, 1 equiv, 43.0 mmol) and DIEA (11.2 mL, 1.5 equiv, 64.5 mmol) in anhydrous DCE (200 mL) was added 3-azido-3-methylbutanoyl chloride (6.95 g, 43.0 mmol) in small portions. The reaction was stirred and left at 0° C. for 1 h. Aqueous NaOH (5N, 4 equiv, 34.5 mmol) was added to the reaction mixture. The solvent and DIEA was removed via rotovap to give an oily aqueous mixture. The contents of the flask was poured into a separatory funnel and extracted with DCM (2×100 mL). The organic layer was dried over anhydrous MgSO4, filtered, concentrated and dried under high vacuum to give a crude oil (8.71 g, 84.0%). This material was used without further purification. 1H NMR (D2O, 400 MHz): δ 1.34 (t, J=7.2, 3H), 1.43 (s, 6H), 2.11-2.15 (m, 2H), 3.09 (s, 3 H), 3.35 (s, 2H), 3.41 (dt, J=7.2, 4H). LRMS (ESI+) for C11H23N5O (241.2); Found: 241 (M+).
CN(C)CCCN(C)C(=O)CC(C)(C)N=[N+]=[N-]
null
83.9
null
533,606
ord_dataset-b1a34bc8c1204d51a772ed27396c794e
null
2002-01-01T00:02:00
true
[C:1]([C:5]1[CH:6]=[C:7]([C:16]([CH3:19])([CH3:18])[CH3:17])[C:8]2[O:12][C:11](=[O:13])[CH:10](O)[C:9]=2[CH:15]=1)([CH3:4])([CH3:3])[CH3:2].[CH3:20][C:21]1[CH:22]=[CH:23][C:24]([CH3:27])=[CH:25][CH:26]=1>O>[C:1]([C:5]1[CH:6]=[C:7]([C:16]([CH3:19])([CH3:17])[CH3:18])[C:8]2[O:12][C:11](=[O:13])[CH:10]([C:26]3[CH:25]=[C:24]([CH3:27])[CH:23]=[CH:22][C:21]=3[CH3:20])[C:9]=2[CH:15]=1)([CH3:4])([CH3:3])[CH3:2]
Cc1ccc(C)cc1
CC(C)(C)c1cc2c(c(C(C)(C)C)c1)OC(=O)C2O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
null
null
null
null
null
null
null
null
null
null
null
null
To a solution of 262.3 g (1.00 mol) of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (compound (201), Table 2, Example 1a) in 500 ml (4.05 mol) of p-xylene are added 40 g of Fulcat 22B and the mixture is refluxed for 15 hours on a water separator. The Fulcat 22B catalyst is then removed by filtration and excess p-xylene is removed by distillation on a vacuum rotaray evaporator. Crystallisation of the residue from 400 ml of methanol yields 280.6 g (80%) of 5,7-di-tert-butyl-3-(2,5-dimethylphenyl)-3H-benzofuran-2-one, m.p. 93-97° C. (compound (101), Table 1).
Cc1ccc(C)c(C2C(=O)Oc3c2cc(C(C)(C)C)cc3C(C)(C)C)c1
null
80.1
null
857,443
ord_dataset-faa0236be76c4501841c954527cd1b6c
null
2008-01-01T00:12:00
true
[C:1]([O:5][C:6]([NH:8][CH:9]1[CH2:14][CH2:13][CH2:12][N:11]([C:15]2[N:19]([CH2:20][C:21]#[C:22][CH3:23])[C:18]([C:24]([O:26]CC)=[O:25])=[CH:17][N:16]=2)[CH2:10]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].Cl>[OH-].[K+].O1CCCC1>[C:1]([O:5][C:6]([NH:8][CH:9]1[CH2:14][CH2:13][CH2:12][N:11]([C:15]2[N:19]([CH2:20][C:21]#[C:22][CH3:23])[C:18]([C:24]([OH:26])=[O:25])=[CH:17][N:16]=2)[CH2:10]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]
CC#CCn1c(C(=O)OCC)cnc1N1CCCC(NC(=O)OC(C)(C)C)C1
null
null
Cl
[K+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
null
A solution of 4.40 g ethyl 2-(3-tert-butoxycarbonylamino-piperidin-1-yl)-3-(but-2-ynyl)-3H-imidazole-4-carboxylate in 28 ml 4 M potassium hydroxide solution and 20 ml of tetrahydrofuran is stirred for 14 h at 100° C. Then the solution is neutralized with 2 M hydrochloric acid and extracted with dichloromethane. The combined organic extracts are dried over sodium sulphate and evaporated to dryness.
CC#CCn1c(C(=O)O)cnc1N1CCCC(NC(=O)OC(C)(C)C)C1
null
null
null
429,523
ord_dataset-8cce6f317d644b348a7978a2dce3ea01
null
1999-01-01T00:03:00
true
[FH:1].C(N(C(C)C)CC)(C)C.O.[F:12][C:13]([F:23])([F:22])[CH:14]([O:19][CH2:20]Cl)[C:15]([F:18])([F:17])[F:16]>>[CH2:20]([F:1])[O:19][CH:14]([C:15]([F:18])([F:17])[F:16])[C:13]([F:23])([F:22])[F:12]
F
FC(F)(F)C(OCCl)C(F)(F)F
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CCN(C(C)C)C(C)C
null
null
null
null
null
null
null
null
null
10
null
In an efficient fume hood, liquid hydrogen fluoride (85.1 g, 4.25 mol) was transferred into a 1 liter Teflon® reaction vessel chilled in a dry ice/acetone cold bath. The vessel was fitted with a dry ice condenser, thermocouple, and addition funnel and a portion of chloromethyl 2,2,2-trifluoro-1-(trifluoromethyl)ethyl ether (80.1 g) was added. A solution of diisopropylethylamine (249.0 g, 1.93 mol) in chloromethyl 2,2,2-trifluoro-1-(trifluoromethyl)ethyl ether (271.0 g) was slowly added while maintaining the internal temperature in the range of -5°to 10° C. After completing the addition, the mixture was transferred to a 2 liter glass boiling flask and the Teflon® vessel was rinsed out with a solution of diisopropylethylamine (307.0 g, 2.38 mol) in chloromethyl 2,2,2-trifluoro-1-(trifluoromethyl)ethyl ether (180.0 g) which was also transferred to the glass flask. An additional 850 g of chloromethyl 2,2,2-trifluoro-1-(trifluoromethyl)ethyl ether was added to the reaction flask to bring the total to 1381.1 g (6.38 mol). This mixture was heated at reflux for 16 hours. After cooling to ambient temperature, water (700 mL) was added to the reaction mixture and, after vigorous shaking, the resultant layers were separated. The lower organic layer was further washed with 700 mL of dilute hydrochloric acid (35 mL of 12 N HCl in 665 mL of water). The organic layer (1259.7 g) was analyzed by NMR and gas chromatography and was shown to consist of 63.6% fluoromethyl 2,2,2-trifluoro-1-(trifluoromethyl)ethyl ether (sevoflurane) and 35.4% recovered chloromethyl 2,2,2-trifluoro-1-(trifluoromethyl)ethyl ether, giving a 95% yield of sevoflurane based on starting material consumed.
FCOC(C(F)(F)F)C(F)(F)F
null
95
null
1,224,879
ord_dataset-cde802cdb7434a5f82a22981ccaefc4e
null
2012-01-01T00:11:00
true
[CH:1]1([CH:7]([C:18]2[CH:22]=[C:21]([C:23]3[CH2:24][CH2:25][S:26][CH2:27][CH:28]=3)[S:20][C:19]=2[CH2:29][CH3:30])[O:8][C:9]2[CH:17]=[CH:16][C:12]([C:13](O)=[O:14])=[CH:11][CH:10]=2)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[CH3:31][NH:32][CH2:33][CH2:34][C:35]([O:37]CC)=[O:36]>>[CH:1]1([CH:7]([C:18]2[CH:22]=[C:21]([C:23]3[CH2:24][CH2:25][S:26][CH2:27][CH:28]=3)[S:20][C:19]=2[CH2:29][CH3:30])[O:8][C:9]2[CH:10]=[CH:11][C:12]([C:13]([N:32]([CH3:31])[CH2:33][CH2:34][C:35]([OH:37])=[O:36])=[O:14])=[CH:16][CH:17]=2)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1
CCOC(=O)CCNC
CCc1sc(C2=CCSCC2)cc1C(Oc1ccc(C(=O)O)cc1)C1CCCCC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
An operation similar to that in Example 69 (9) was performed using 4-{cyclohexyl[5-(3,6-dihydro-2H-thiopyran-4-yl)-2-ethylthiophen-3-yl]methoxy}benzoic acid (234 mg) synthesized in Example 85 (4) and ethyl 3-(methylamino)propanoate (79.8 mg) to give the title compound (89.2 mg, 33%).
CCc1sc(C2=CCSCC2)cc1C(Oc1ccc(C(=O)N(C)CCC(=O)O)cc1)C1CCCCC1
null
32
null
193,723
ord_dataset-11b3c3b41eda49e196ec983a65d3b2c0
null
1989-01-01T00:07:00
true
[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[NH:9][C:10]1[N:23]=[C:22]([O:24][CH3:25])[C:21]([F:26])=[CH:20][C:11]=1[C:12]([CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16])=[O:13].[CH3:27]OC(OC)N(C)C.C(OCC)C>C1C=CC=CC=1>[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[N:9]1[C:10]2[C:11](=[CH:20][C:21]([F:26])=[C:22]([O:24][CH3:25])[N:23]=2)[C:12](=[O:13])[C:14]([C:15]([O:17][CH2:18][CH3:19])=[O:16])=[CH:27]1
COC(OC)N(C)C
CCOC(=O)CC(=O)c1cc(F)c(OC)nc1Nc1ccc(F)cc1F
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
c1ccccc1
CCOCC
null
null
null
null
null
null
null
null
null
null
null
In 4 ml of benzene was suspended 200 mg of ethyl 2-[2-(2,4-difluorophenylamino)-5-fluoro-6-methoxynicotinoyl]acetate, and 71 mg of N,N-dimethylformamide dimethylacetal was added thereto, after which the resulting mixture was subjected to reaction under reflux for 9 hours. The solvent was removed by distillation under reduced pressure, and to the residue thus obtained was added 2 ml of diethyl ether, after which the crystals thus deposited were collected by filtration to obtain 130 mg (yield 63.3%) of ethyl 1-(2,4-difluorophenyl)-6-fluoro-1,4-dihydro-7-methoxy-4-oxo-1,8-naphthyridine-3-carboxylate having a melting point of 190°-192° C.
CCOC(=O)c1cn(-c2ccc(F)cc2F)c2nc(OC)c(F)cc2c1=O
null
63.3
null
189,923
ord_dataset-be83cbc722064f3696975001242f9f1a
null
1989-01-01T00:05:00
true
[CH3:1][C:2]1[C:7]([N+:8]([O-])=O)=[CH:6][CH:5]=[CH:4][C:3]=1[C:11]([F:14])([F:13])[F:12].[H][H]>CO.[Pd]>[NH2:8][C:7]1[C:2]([CH3:1])=[C:3]([C:11]([F:12])([F:13])[F:14])[CH:4]=[CH:5][CH:6]=1
Cc1c([N+](=O)[O-])cccc1C(F)(F)F
[H][H]
null
[Pd]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
25
null
A solution of 2-methyl-3-nitrobenzotrifluoride (41.0 g, 0.2 m) in methanol (100 ml) was stirred under an atmosphere of dry nitrogen at room temperature and palladium on charcoal catalyst (10% w/w, 1.0 g) was added. The stirred mixture was warmed to 40°-45° and then hydrogen was passed into the solution at atmospheric pressure until the reduction, as observed by thin-layer chromatography, was complete (4-5 hours). The solution was cooled to room temperature and the catalyst removed by filtration. Distillation of the solvent at atmospheric pressure followed by steam distillation of the crude product gave 3-amino-2-methylbenzotrifluoride (32.2 g, 92% yield), as a pale-brown oil which slowly crystallized.
Cc1c(N)cccc1C(F)(F)F
null
92
null
311,986
ord_dataset-04982f13ed08448d93df6794846500f3
null
1995-01-01T00:06:00
true
[C:1]([OH:7])(=[O:6])[CH2:2][C:3]([OH:5])=[O:4].[N+:8]([O-])([O:10]C(=O)C)=[O:9]>C(O)(=O)C.C(OC(=O)C)(=O)C>[N+:8]([CH:2]([C:1]([OH:7])=[O:6])[C:3]([OH:5])=[O:4])([O-:10])=[O:9]
CC(=O)O[N+](=O)[O-]
O=C(O)CC(=O)O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(=O)OC(C)=O
CC(=O)O
null
null
null
null
null
null
null
null
null
null
null
Nitration of malonic acid with acetyl nitrate in acetic acid/acetic anhydride was conducted to obtain nitromalonic acid. To the nitromalonic acid is added urea to obtain a condensation reaction mixture which is refluxed to form dilituric acid in situ. Various salts are separately prepared from the dilituric acid in situ using as cation sources potassium chloride, ammonia, and guanidinium chloride. The potassium diliturate salt, ammonium diliturate, guanidinium diliturate salts are each recovered and isolated by filtration.
O=C(O)C(C(=O)O)[N+](=O)[O-]
null
null
null
200,679
ord_dataset-31f00a039ca0424788e5e1970d25a8fd
null
1989-01-01T00:12:00
true
[CH3:1][C:2]1[CH:3]=[C:4]2[C:11](=[CH:12][CH:13]=1)[C:7]([CH2:8][CH2:9][NH2:10])=[CH:6][NH:5]2.Cl[CH2:15][C:16]#[N:17]>O1CCCC1.C(Cl)Cl>[CH3:1][C:2]1[CH:3]=[C:4]2[C:11]([C:7]([CH2:8][CH2:9][NH:10][CH2:15][C:16]#[N:17])=[CH:6][NH:5]2)=[CH:12][CH:13]=1
Cc1ccc2c(CCN)c[nH]c2c1
N#CCCl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
ClCCl
null
null
null
null
null
null
null
null
null
null
15
17 g of 6-methyltryptamine were dissolved at 40° C. under inert atmosphere in 500 ml of tetrahydrofuran, and the solution was allowed to return to ambient temperature. 14.6 ml of 1,5-diaza[5,4,0]undec-5-ene were added followed by 6.2 ml of chloroacetonitrile and stirring for 15 hours. The solvent was eliminated under reduced pressure and the residue was taken up in 250 ml of methylene chloride, washed with water, dried and concentrated to dryness. The 25 g of crude product was purified by chromatography on silica (eluent: methylene chloride-ethyl acetate 3-7) to obtain 13.2 g of the expected product melting at 92° C.
Cc1ccc2c(CCNCC#N)c[nH]c2c1
null
null
null
1,221,527
ord_dataset-cde802cdb7434a5f82a22981ccaefc4e
null
2012-01-01T00:11:00
true
[BH4-].[Na+].[C:3]1([C@@H:9]([N:11]=[C:12]2[C:33]3[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=3)[C:15]3([CH2:20][CH2:19][N:18]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[CH2:17][CH2:16]3)[CH2:14][CH2:13]2)[CH3:10])[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.C([O-])(O)=O.[Na+]>CO>[C:3]1([C@@H:9]([NH:11][C@@H:12]2[C:33]3[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=3)[C:15]3([CH2:16][CH2:17][N:18]([C:21]([O:23][C:24]([CH3:26])([CH3:27])[CH3:25])=[O:22])[CH2:19][CH2:20]3)[CH2:14][CH2:13]2)[CH3:10])[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1
C[C@H](N=C1CCC2(CCN(C(=O)OC(C)(C)C)CC2)c2ccccc21)c1ccccc1
null
null
O=C([O-])O
[BH4-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
0
null
At −78° C., NaBH4 (760 mg, 20 mmol) was added to a solution of the imine (B1) (7.82 g, 20 mmol) in methanol (100 ml). The reaction mixture was allowed to warm to 0° C. over 2-3 hours then treated with saturated NaHCO3 (ca. 100 ml), concentrated under reduced pressure at <30° C. to remove the solvent. The residue was extracted with ethyl acetate. The organic phase was washed with water, dried over Na2SO4 and concentrated to give (S)-tert-butyl 4-((S)-1-phenylethylamino)-3,4-dihydro-2H-spiro[naphthalene-1,4′-piperidine]-1′-carboxylate (B2) as a solid. LC-MS: m/e=421.32 (M+H). Rt=2.20 min.
C[C@H](N[C@H]1CCC2(CCN(C(=O)OC(C)(C)C)CC2)c2ccccc21)c1ccccc1
null
null
null
926,450
ord_dataset-cc0899cd744f4f7f8e7f2463560faad1
null
2009-01-01T00:12:00
true
Cl[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][N:7]1[C:13](=[O:14])[CH2:12][CH2:11][N:10]([C:15](=[O:26])/[CH:16]=[CH:17]/[C:18]2[CH:23]=[CH:22][C:21]([Cl:24])=[C:20]([Cl:25])[CH:19]=2)[CH2:9][CH2:8]1.[I-:27].[Na+]>>[Cl:25][C:20]1[CH:19]=[C:18](/[CH:17]=[CH:16]/[C:15]([N:10]2[CH2:11][CH2:12][C:13](=[O:14])[N:7]([CH2:6][CH2:5][CH2:4][CH2:3][CH2:2][I:27])[CH2:8][CH2:9]2)=[O:26])[CH:23]=[CH:22][C:21]=1[Cl:24]
O=C(/C=C/c1ccc(Cl)c(Cl)c1)N1CCC(=O)N(CCCCCCl)CC1
[I-]
null
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
90
20
In analogy to the procedure described in example 6D, 4-(5-chloro-pentyl)-1-[(E)-3-(3,4-dichloro-phenyl)-acryloyl]-[1,4]diazepan-5-one and sodium iodide were stirred at 90° C. for 20 h to give the title compound as orange oil. MS: 509.2 (MH+, 2Cl).
O=C(/C=C/c1ccc(Cl)c(Cl)c1)N1CCC(=O)N(CCCCCI)CC1
null
null
null
903,815
ord_dataset-46d216f2c4374ef5b9df90427e2a4cd4
null
2009-01-01T00:09:00
true
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][N:11]([C:14]2[CH:22]=[CH:21][CH:20]=[C:19]3[C:15]=2[C:16](=[O:32])[C:17](=[O:31])[N:18]3[CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[C:26]([F:30])[CH:25]=2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH3:33][Li]>C1COCC1>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][N:11]([C:14]2[CH:22]=[CH:21][CH:20]=[C:19]3[C:15]=2[C:16]([OH:32])([CH3:33])[C:17](=[O:31])[N:18]3[CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[C:26]([F:30])[CH:25]=2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]
CC(C)(C)OC(=O)N1CCN(c2cccc3c2C(=O)C(=O)N3Cc2cccc(F)c2)CC1
[Li]C
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
-78
null
4-[1-(3-Fluoro-benzyl)-2,3-dioxo-2,3-dihydro-1H-indol-4-yl]-piperazine-1-carboxylic acid tert-butyl ester (330 mg) was dissolved in 4 mL of THF and cooled to −78° C. before adding 1.6 M methyl lithium in hexaness (800 uL). The solution was stirred and warmed to room temperature, then stirred for an hour at room temperature. The reaction was quenched by addition of water and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate and evaporated under reduced pressure. The residue was purified by column chromatography afforded 315 mg of 4-[1-(3-fluoro-benzyl)-3-hydroxy-3-methyl-2-oxo-2,3-dihydro-1H-indol-4-yl]-piperazine-1-carboxylic acid tert-butyl ester. MS: 356 (M−Boc+H)+.
CC(C)(C)OC(=O)N1CCN(c2cccc3c2C(C)(O)C(=O)N3Cc2cccc(F)c2)CC1
null
null
null
516,111
ord_dataset-a495451286334c5c9bbcbd48a00c1350
null
2001-01-01T00:09:00
true
[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[CH2:12][CH2:11][CH2:10][NH:9]2)=[CH:4][CH:3]=1.[Cl:13][C:14]1[CH:15]=[C:16]([S:21](Cl)(=[O:23])=[O:22])[CH:17]=[CH:18][C:19]=1[CH3:20]>>[Cl:13][C:14]1[CH:15]=[C:16]([S:21]([N:9]2[CH2:10][CH2:11][CH2:12][CH:8]2[C:5]2[CH:4]=[CH:3][C:2]([F:1])=[CH:7][CH:6]=2)(=[O:23])=[O:22])[CH:17]=[CH:18][C:19]=1[CH3:20]
Fc1ccc(C2CCCN2)cc1
Cc1ccc(S(=O)(=O)Cl)cc1Cl
null
null
null
null
null
null
null
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, off-white solid, m.p. 134° C. and MS: m/e=353 (M+) was prepared in accordance with the general method of example 1e from (RS)-2-(4-fluoro-phenyl)-pyrrolidine and 3-chloro-4-methyl-benzenesulfonyl chloride.
Cc1ccc(S(=O)(=O)N2CCCC2c2ccc(F)cc2)cc1Cl
null
null
null
392,112
ord_dataset-4bc8addcf9cf4845817557760d62d5b5
null
1998-01-01T00:02:00
true
[CH2:1]([O:3][C:4]([CH:6]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH2:7][CH2:8][C:9]1[CH:15]=[C:14]([CH2:16][NH:17][C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH:13]=[CH:12][C:10]=1[NH2:11])=[O:5])[CH3:2].[Br:30][C:31]1[CH:32]=[C:33]2[CH2:45][CH2:44][C@@H:43]([CH2:46][C:47](O)=[O:48])[N:35]3[C:36](=[O:42])[C:37](=[O:41])[NH:38][C:39]([CH:40]=1)=[C:34]23>C(O)(=O)C.C(OCC)(=O)C>[Br:30][C:31]1[CH:32]=[C:33]2[CH2:45][CH2:44][C@@H:43]([CH2:46][C:47](=[O:48])[NH:11][C:10]3[CH:12]=[CH:13][C:14]([CH2:16][NH:17][C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])=[CH:15][C:9]=3[CH2:8][CH2:7][CH:6]([C:4]([O:3][CH2:1][CH3:2])=[O:5])[C:25]([O:27][CH2:28][CH3:29])=[O:26])[N:35]3[C:36](=[O:42])[C:37](=[O:41])[NH:38][C:39]([CH:40]=1)=[C:34]23
O=C(O)C[C@@H]1CCc2cc(Br)cc3[nH]c(=O)c(=O)n1c23
CCOC(=O)C(CCc1cc(CNC(=O)OC(C)(C)C)ccc1N)C(=O)OCC
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(=O)O
CCOC(C)=O
null
null
null
null
null
null
null
null
null
null
null
A procedure similar to that described in Example 18-6) was performed with 2-(3,3-diethoxycarbonylpropyl)-4-tert-butoxycarbonylaminomethylaniline (1.5 g, 3.67 mmol) and (S)-9-bromo-5-carboxymethyl-6,7-dihydro-1H, 5H-pyrido[1,2,3-de]quinoxaline-2,3-dione (1.37 g, 4.04 mmol) to give 1.60 g of the title compound after silica gel column chromatography with 0.3% acetic acid/ethyl acetate (60%).
CCOC(=O)C(CCc1cc(CNC(=O)OC(C)(C)C)ccc1NC(=O)C[C@@H]1CCc2cc(Br)cc3[nH]c(=O)c(=O)n1c23)C(=O)OCC
null
59.8
null
611,038
ord_dataset-73916d628db147c89020b3baac642d48
null
2003-01-01T00:09:00
true
[CH2:1]([N:8]([C:33](=[O:39])[C:34]([O:36]CC)=[O:35])[CH2:9][CH:10]([CH:27]1[CH2:32][CH2:31][CH2:30][CH2:29][CH2:28]1)[C:11]1[CH:16]=[CH:15][C:14]([C:17]2[C:26]3[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=3)[CH:20]=[CH:19][CH:18]=2)=[CH:13][CH:12]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH-].[Na+].Cl>C(O)C>[CH2:1]([N:8]([C:33](=[O:39])[C:34]([OH:36])=[O:35])[CH2:9][CH:10]([CH:27]1[CH2:32][CH2:31][CH2:30][CH2:29][CH2:28]1)[C:11]1[CH:12]=[CH:13][C:14]([C:17]2[C:26]3[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=3)[CH:20]=[CH:19][CH:18]=2)=[CH:15][CH:16]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
CCOC(=O)C(=O)N(Cc1ccccc1)CC(c1ccc(-c2cccc3ccccc23)cc1)C1CCCCC1
null
null
Cl
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
null
2
A solution of Example 16C (50.0 mg, 0.096 mmol) in ethanol (2 mL) at room temperature was treated with 2M NaOH (0.2 mL), stirred for 2 hours, adjusted to pH 1 with 1M HCl, and extracted with ethyl acetate. The extract was dried (Na2SO4), filtered, and concentrated to provide the desired product. MS (ESI(+)) m/z 492 (M+H)+; 1H NMR (300 MHz, DMSO-d6) δ8.04-7.83 (m, 2H), 7.67-7.00 (m, 14H), 4.54-4.33 (m, 1H), 3.93-3.62 (m, 1H), 3.00-2.70 (m, 1H), 1.83-0.67 (m, 11H).
O=C(O)C(=O)N(Cc1ccccc1)CC(c1ccc(-c2cccc3ccccc23)cc1)C1CCCCC1
null
null
null
1,486,632
ord_dataset-c3c1091f873b4f40827973a6f1f9b685
null
2014-01-01T00:09:00
true
Br[C:2]1[CH:3]=[C:4]([N:8]2[CH2:16][CH:15]3[CH2:17][N:11]4[CH2:12][CH:13]([CH2:18][CH:9]2[CH2:10]4)[CH2:14]3)[CH:5]=[N:6][CH:7]=1.[C:19]([NH:22][C:23]1[CH:24]=[C:25](B(O)O)[CH:26]=[CH:27][CH:28]=1)(=[O:21])[CH3:20]>>[N:11]12[CH2:17][CH:15]3[CH2:14][CH:13]([CH2:18][CH:9]([N:8]([C:4]4[CH:3]=[C:2]([C:27]5[CH:28]=[C:23]([NH:22][C:19](=[O:21])[CH3:20])[CH:24]=[CH:25][CH:26]=5)[CH:7]=[N:6][CH:5]=4)[CH2:16]3)[CH2:10]1)[CH2:12]2
CC(=O)Nc1cccc(B(O)O)c1
Brc1cncc(N2CC3CC4CC2CN(C4)C3)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 from the product of Example 65A and 3-acetamidophenylboronic acid according to General Method B: LC-MS Method D (ESI+) m/z 363.0 (M+H)+, retention time 1.21 minutes.
CC(=O)Nc1cccc(-c2cncc(N3CC4CC5CC3CN(C5)C4)c2)c1
null
null
null
1,724,455
ord_dataset-36057d699ac5449e9c37eb99abf78b03
null
2016-01-01T00:05:00
true
[Br:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[CH:9]1[C:14]([C:15]([O:17][CH2:18][CH3:19])=[O:16])=[C:13]([CH3:20])[NH:12][C:11]([C:21]2[N:25]=[CH:24][N:23]([CH3:26])[N:22]=2)=[N:10]1.C1C(=O)N([Br:34])C(=O)C1>C(Cl)(Cl)Cl>[Br:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[CH:9]1[C:14]([C:15]([O:17][CH2:18][CH3:19])=[O:16])=[C:13]([CH2:20][Br:34])[NH:12][C:11]([C:21]2[N:25]=[CH:24][N:23]([CH3:26])[N:22]=2)=[N:10]1
O=C1CCC(=O)N1Br
CCOC(=O)C1=C(C)NC(c2ncn(C)n2)=NC1c1ccc(F)cc1Br
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)Cl
null
null
null
null
null
null
null
null
null
null
null
null
Ethyl 4-(2-bromo-4-fluorophenyl)-6-methyl-2-(1-methyl-1H-1,2,4-triazol-3-yl)-1,4-dihydropyrimidine-5-carboxylate (5 g, 12 mmol) was reacted with NBS (2.1 g, 12 mmol) in chloroform (150 mL) according to the procedure as described in Example 1, Step B to give the title compound as a yellow solid (2.4 g, 40%). The compound was characterized by the following spectroscopic data:
CCOC(=O)C1=C(CBr)NC(c2ncn(C)n2)=NC1c1ccc(F)cc1Br
null
39.9
null
1,697,352
ord_dataset-54347fcace774f89850681d6dec8009f
null
2016-01-01T00:03:00
true
[F:1][C:2]1[CH:10]=[CH:9][C:8]([CH2:11][C:12]2[C:21]3[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=3)[C:15](=[O:22])[NH:14][N:13]=2)=[CH:7][C:3]=1[C:4](O)=[O:5].ON1C2C=CC=CC=2N=N1.[F:33][C:34]([F:47])([F:46])[C:35]1[N:39]2[CH2:40][CH2:41][NH:42][CH2:43][C:38]2=[C:37]([CH2:44][OH:45])[N:36]=1.C(N(CC)CC)C>CN(C)C=O>[F:1][C:2]1[CH:10]=[CH:9][C:8]([CH2:11][C:12]2[C:21]3[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=3)[C:15](=[O:22])[NH:14][N:13]=2)=[CH:7][C:3]=1[C:4]([N:42]1[CH2:41][CH2:40][N:39]2[C:35]([C:34]([F:47])([F:33])[F:46])=[N:36][C:37]([CH2:44][OH:45])=[C:38]2[CH2:43]1)=[O:5]
OCc1nc(C(F)(F)F)n2c1CNCC2
O=C(O)c1cc(Cc2n[nH]c(=O)c3ccccc23)ccc1F
null
On1nnc2ccccc21
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
12
2-Fluoro-5-[(4-oxo-3H-phthalazin-1-yl)methyl]benzoic acid 1a (372 mg, 1.25 mmol) was dissolved in 5 mL of N,N-dimethylformamide, followed by addition of N-hydroxybenzotriazole (85 mg, 0.63 mmol), [3-(trifluoromethyl)-5,6,7,8-tetrahydro imidazo[1,5-a]pyrazin-1-yl]methanol 6a (277 mg, 1.25 mmol), 1-ethyl-(3-dimethyl-aminopropyl) carbodiimide hydrochloride (359 mg, 1.88 mmol) and triethylamine (0.3 mL, 2.5 mmol). After stirring for 12 hours, the reaction mixture was concentrated under reduced pressure and the resulting residue was purified by thin layer chromatography with elution system A to obtain 4-[[4-fluoro-3-[1-(hydroxymethyl)-3-(trifluoromethyl)-6,8-dihydro-5H-imidazo[1,5-a]pyrazine-7-carbonyl]phenyl]methyl]-2H-phthalazin-1-one 6 (400 mg, yield 64.0%) as a white solid.
O=C(c1cc(Cc2n[nH]c(=O)c3ccccc23)ccc1F)N1CCn2c(C(F)(F)F)nc(CO)c2C1
null
63.8
null
1,310,745
ord_dataset-2d6edb8ffd434003bb508360153bd9bb
null
2013-01-01T00:07:00
true
[OH:1][CH:2]([CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)[C:3]#[N:4].Cl.[CH3:18][OH:19]>>[OH:1][CH:2]([CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1)[C:3](=[NH:4])[O:19][CH3:18]
CO
N#CC(O)CCCCCCc1ccccc1
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
15
A solution of 2-hydroxy-8-phenyloctanenitrile (5 g) in methanol (50 mL) was cooled to −78° C. and a stream of HCl (g) was introduced for 4 min. The mixture was stored at −10° C. for 15 h, then concentrated to yield methyl 2-hydroxy-8-phenyloctanimidate. (MH+=286).
COC(=N)C(O)CCCCCCc1ccccc1
null
null
null
1,712,217
ord_dataset-3f2a531ffbae4b9eb1048afcd7953beb
null
2016-01-01T00:04:00
true
[N:1]([C:4]1[C:9]([F:10])=[CH:8][N:7]=[CH:6][C:5]=1[CH:11]=O)=[N+:2]=[N-:3].[Br:13][C:14]1[CH:19]=[C:18]([Cl:20])[C:17]([NH2:21])=[C:16]([Cl:22])[CH:15]=1.C(N(CC)CC)C>C(Cl)Cl.[Ti](Cl)(Cl)(Cl)Cl>[N:1]([C:4]1[C:9]([F:10])=[CH:8][N:7]=[CH:6][C:5]=1/[CH:11]=[N:21]/[C:17]1[C:18]([Cl:20])=[CH:19][C:14]([Br:13])=[CH:15][C:16]=1[Cl:22])=[N+:2]=[N-:3]
Nc1c(Cl)cc(Br)cc1Cl
[N-]=[N+]=Nc1c(F)cncc1C=O
null
Cl[Ti](Cl)(Cl)Cl
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
0
8
A solution of 4-azido-5-fluoropyridine-3-carbaldehyde (10.0 g, 60.0 mmol) and 4-bromo-2,6-dichlorophenylamine (14.4 g, 60.0 mmol) in DCM (200 mL) was cooled to 0° C., under an atmosphere of nitrogen. Triethylamine (25 mL, 180 mmol) was added, followed by dropwise addition of titanium (IV) chloride solution (1 N in DCM, 36 mL, 36 mmol). The reaction mixture was stirred at 0° C. then allowed to reach room temperature overnight. The resultant mixture was concentrated under reduced pressure and the residue was suspended in toluene and filtered through a pad of Celite®. The filtrate was concentrated under reduced pressure to afford the title compound (quantitative yield). This was used in the next step without further purification.
[N-]=[N+]=Nc1c(F)cncc1/C=N/c1c(Cl)cc(Br)cc1Cl
null
null
null
1,241,440
ord_dataset-c544c0c663f54dbea4ddb52ddde7934e
null
2013-01-01T00:01:00
true
C([O:8][C:9]1[CH:10]=[C:11]([N:15]2[CH:19]=[N:18][CH:17]=[N:16]2)[CH:12]=[CH:13][CH:14]=1)C1C=CC=CC=1>CO.[Pd]>[N:15]1([C:11]2[CH:10]=[C:9]([OH:8])[CH:14]=[CH:13][CH:12]=2)[CH:19]=[N:18][CH:17]=[N:16]1
c1ccc(COc2cccc(-n3cncn3)c2)cc1
null
null
[Pd]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
25
null
1-[3-(benzyloxy)phenyl]-1H-1,2,4-triazole (250 mg, 0.995 mmol) was dissolved in 5 mL methanol. The solution was degassed and backfilled with nitrogen. Palladium on carbon (10% w/w, 106 mg, 0.1 mmol) was then added. The reaction vessel was degassed and backfilled with hydrogen 3 times and stirred under a hydrogen balloon at room temperature. The reaction was stirred overnight. It was then diluted with 5 mL acetone and filtered through a plug of silica gel (5 g), which was washed thoroughly with acetone. Concentration afforded the product as white solid. LRMS calc: 161.1; obs: 162.2 (M+1).
Oc1cccc(-n2cncn2)c1
null
null
null
97,214
ord_dataset-0bf72e95d80743729fdbb8b57a4bc0c6
null
1982-01-01T00:08:00
true
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH2:9][C:10]2[C:18]3[C:13](=[CH:14][CH:15]=[C:16]([OH:19])[CH:17]=3)[NH:12][C:11]=2[CH3:20])=[CH:4][CH:3]=1.[CH2:21]([O:23][C:24](=[O:29])[C:25](Br)([CH3:27])[CH3:26])[CH3:22]>>[CH2:21]([O:23][C:24](=[O:29])[C:25]([O:19][C:16]1[CH:17]=[C:18]2[C:13](=[CH:14][CH:15]=1)[NH:12][C:11]([CH3:20])=[C:10]2[CH2:9][CH2:8][C:5]1[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][CH:4]=1)([CH3:27])[CH3:26])[CH3:22]
Cc1[nH]c2ccc(O)cc2c1CCc1ccc(Cl)cc1
CCOC(=O)C(C)(C)Br
null
null
null
null
null
null
null
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 above compound was prepared from 3-[2-(4-chloro-phenyl)-ethyl]-2-methyl-1H-indole-5-ol and 2-bromo-2-methyl-propanoic acid ethylester using a procedure analogous to that of Example 10.
CCOC(=O)C(C)(C)Oc1ccc2[nH]c(C)c(CCc3ccc(Cl)cc3)c2c1
null
null
null
731,908
ord_dataset-eb4226b4f7644a01a737e7547b70014a
null
2006-01-01T00:09:00
true
[N:1]1[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[C:7]1[N:8]=[CH:9][N:10](C(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[CH:11]=1.Cl>O1CCCC1>[N:1]1[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[C:7]1[N:8]=[CH:9][NH:10][CH:11]=1
c1ccc(C(c2ccccc2)(c2ccccc2)n2cnc(-c3ccccn3)c2)cc1
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
null
A solution of the crude 4-(2-pyridyl)-1-trityl-1H-imidazole (0.69 g) in tetrahydrofuran (14 mL) was treated with 2 N hydrochloric acid (7.2 mL) and heated at reflux for 45 minutes. After cooling the reaction mixture was concentrated in vacuo and the residue was dissolved in dichloromethane (20 mL). The organic solution was successively washed with aqueous 1N sodium hydroxide (10 mL), water (20 mL) and brine (20 mL). The organic solution was then dried over anhydrous sodium sulfate, filtered, and concentrated in-vacuo to afford 0.12 g of crude 4-(2-pyridyl)imidazole, as a sticky white solid.
c1ccc(-c2c[nH]cn2)nc1
null
46.4
null
1,119,264
ord_dataset-4226e9b4f9f845db967ed997270dcafc
null
2011-01-01T00:12:00
true
C([O:8][C:9]1[CH:14]=[C:13]([C:15]#[C:16][CH2:17][CH:18]2[CH2:22][CH2:21][CH2:20][S:19]2(=[O:24])=[O:23])[CH:12]=[CH:11][C:10]=1[N:25]1[S:29](=[O:31])(=[O:30])[NH:28][C:27](=[O:32])[CH2:26]1)C1C=CC=CC=1.B(Br)(Br)Br>C(Cl)Cl>[O:24]=[S:19]1(=[O:23])[CH2:20][CH2:21][CH2:22][CH:18]1[CH2:17][C:16]#[C:15][C:13]1[CH:12]=[CH:11][C:10]([N:25]2[S:29](=[O:31])(=[O:30])[NH:28][C:27](=[O:32])[CH2:26]2)=[C:9]([OH:8])[CH:14]=1
O=C1CN(c2ccc(C#CCC3CCCS3(=O)=O)cc2OCc2ccccc2)S(=O)(=O)N1
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
25
18
To a solution of 5-{2-benzyloxy-4-[3-(1,1-dioxotetrahydrothiophen-2-yl)-prop-1-ynyl]-phenyl}-1,1-dioxo-1,2,5-thiadiazolidin-3-one in methylene chloride (5 mL) is added BBr3 (0.35 mL of 1.0 M in methylene chloride) and the mixture is stirred at RT for 18 h. The solvent is removed under reduced pressure and the residue purified by preparative HPLC followed by lyophilization to give the title compound: (M−1)−=383; HPLC retention time=0.72 min. (Method A)
O=C1CN(c2ccc(C#CCC3CCCS3(=O)=O)cc2O)S(=O)(=O)N1
null
null
null
1,354,074
ord_dataset-6034127657614f02860ed057b62b882e
null
2013-01-01T00:10:00
true
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C@:8]2([CH2:32][CH2:33][CH2:34][OH:35])[O:13][C:12](=[O:14])[N:11]([C@H:15]([C:17]3[CH:22]=[CH:21][C:20](B4OC(C)(C)C(C)(C)O4)=[CH:19][CH:18]=3)[CH3:16])[CH2:10][CH2:9]2)=[CH:4][CH:3]=1.Cl[C:37]1[CH:42]=[CH:41][N:40]=[CH:39][N:38]=1>>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C@:8]2([CH2:32][CH2:33][CH2:34][OH:35])[O:13][C:12](=[O:14])[N:11]([C@H:15]([C:17]3[CH:18]=[CH:19][C:20]([C:37]4[CH:42]=[CH:41][N:40]=[CH:39][N:38]=4)=[CH:21][CH:22]=3)[CH3:16])[CH2:10][CH2:9]2)=[CH:4][CH:3]=1
C[C@@H](c1ccc(B2OC(C)(C)C(C)(C)O2)cc1)N1CC[C@](CCCO)(c2ccc(F)cc2)OC1=O
Clc1ccncn1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared from (R)-6-(4-fluorophenyl)-6-(3-hydroxypropyl)-3-((S)-1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)ethyl)-1,3-oxazinan-2-one and 4-chloropyrimidine following a procedure analogous to that described in Example 1 Step 2. LC-MS Method 2 tR=1.172, m/z=392.1; 1H NMR (CDCl3) 1.28-1.40 (m, 1H), 1.52 (m, 3H), 1.64 (m, 2H), 1.81-1.99 (m, 2H), 2.09-2.37 (m, 3H), 2.90 (m, 1H), 3.51 (t, 2H), 5.68 (m, 1H), 6.88-7.07 (m, 3H), 7.16-7.28 (m, 3H), 7.58 (m, 1H), 7.79 (d, 2H), 8.61-8.80 (d, 1H), 9.18 (s, 1H).
C[C@@H](c1ccc(-c2ccncn2)cc1)N1CC[C@](CCCO)(c2ccc(F)cc2)OC1=O
null
null
null
707,525
ord_dataset-c8069773c1a148aca8ab417108daacc5
null
2006-01-01T00:05:00
true
[C:1]([C:3]1[CH:4]=[C:5]([NH:9][C:10](=S)[C:11]2[CH:16]=[C:15]([N+:17]([O-:19])=[O:18])[CH:14]=[CH:13][C:12]=2F)[CH:6]=[CH:7][CH:8]=1)#[N:2].O.[NH2:23][NH2:24]>C(O)CCC>[N+:17]([C:15]1[CH:16]=[C:11]2[C:12](=[CH:13][CH:14]=1)[NH:24][N:23]=[C:10]2[NH:9][C:5]1[CH:4]=[C:3]([CH:8]=[CH:7][CH:6]=1)[C:1]#[N:2])([O-:19])=[O:18]
NN
N#Cc1cccc(NC(=S)c2cc([N+](=O)[O-])ccc2F)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CCCCO
null
null
null
null
null
null
null
null
null
null
null
To a solution of N-(3-Cyano-phenyl)-2-fluoro-5-nitro-thiobenzamide (8.56 g; 0.028 mol) in n-butanol (300 mL) was added hydrazine hydrate (2.54 mL; 0.053 mol) and the solution refluxed for 3 hours. The reaction mixture was concentrated in vacuo and triturated with hot ethanol to afford the title compound as a red solid (4.93 g; 62%). 1H NMR (400 MHz, DMSO-d6) δH 7.30 (1H, d), 7.45–7.60 (2H, m), 7.90 (1H, d), 8.20 (1H, d), 8.25 (1H, s), 9.20 (1H, s), 9.85 (1H, s). Mass Spectrum (ES−) m/e=278.28.
N#Cc1cccc(Nc2n[nH]c3ccc([N+](=O)[O-])cc23)c1
null
63.1
null
433,040
ord_dataset-386da077ab2340638cada986e2ef0770
null
1999-01-01T00:07:00
true
CS([O:5][CH:6]1[CH2:11][CH2:10][N:9]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH2:8][CH2:7]1)(=O)=O.O[C:18]1[CH:25]=[CH:24][C:21]([CH:22]=[O:23])=[CH:20][CH:19]=1.C([O-])([O-])=O.[K+].[K+].O>CN(C=O)C>[CH2:15]([O:14][C:12]([N:9]1[CH2:10][CH2:11][CH:6]([O:5][C:18]2[CH:25]=[CH:24][C:21]([CH:22]=[O:23])=[CH:20][CH:19]=2)[CH2:7][CH2:8]1)=[O:13])[CH3:16]
CCOC(=O)N1CCC(OS(C)(=O)=O)CC1
O=Cc1ccc(O)cc1
null
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
O
null
null
null
null
null
null
null
null
null
80
12
To a mixture of 1-(ethoxycarbonyl)piperidin-4-yl methanesulfonate (10 g) and 4-hydroxy benzaldehyde (5.8 g) in dry DMF (75 ml), K2CO3 (11 g) was added and the mixture was stirred at 80° C. for 12 h. At the end of this time, the reaction mixture was cooled, added water and extracted with EtOAc. The EtOAc extract was washed with 5% aqueous Na2CO3 solution followed by brine and dried over anhydrous sodium sulphate. The solvent was then removed by distillation under reduced pressure to give 7 g (63.6%) of the title compound as a semi solid.
CCOC(=O)N1CCC(Oc2ccc(C=O)cc2)CC1
null
63.4
null
669,991
ord_dataset-e90cd41afe844e49875435eb99903799
null
2005-01-01T00:05:00
true
CC1(C)[O:6][C:5](=[CH:7][C:8]([N:10]([CH2:13][C:14]2[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=2)[O:11][CH3:12])=[O:9])[C:4](=[O:21])O1.[CH3:23][C:24]1[C:28]([S:29]([NH2:32])(=[O:31])=[O:30])=[C:27]([CH3:33])[O:26][N:25]=1>>[F:20][C:17]1[CH:16]=[CH:15][C:14]([CH2:13][N:10]([O:11][CH3:12])[C:8](=[O:9])[CH:7]=[C:5]([OH:6])[C:4]([NH:32][S:29]([C:28]2[C:24]([CH3:23])=[N:25][O:26][C:27]=2[CH3:33])(=[O:30])=[O:31])=[O:21])=[CH:19][CH:18]=1
CON(Cc1ccc(F)cc1)C(=O)C=C1OC(C)(C)OC1=O
Cc1noc(C)c1S(N)(=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
2-(2,2-Dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-N-(4-fluoro-benzyl)-N-methoxy-acetamide was treated with 3,5-dimethyl-isoxazole-4-sulfonic acid amide as described in the preparation of compound 1 to yield the title compound. LCMS (M+H) calcd for C17H19FN3O7S: 428.1; found: 428.0. 1H NMR (500 MHz, CDCl3) δ: 2.44 (s, 3), 2.75 (s, 3), 3.65 (s, 3), 4.77 (s, 2), 6.45 (s, 1), 7.01 (m, 2), 7.26 (m, 2). 13C NMR (125 MHz, CDCl3) δ:10.83, 13.24, 48.33, 63.23, 92.57, 114.23, 115.71, 115.89, 130.19, 130.29, 130.96, 157.85, 158.89, 159.44, 161.71, 163.68, 170.81, 177.09.
CON(Cc1ccc(F)cc1)C(=O)C=C(O)C(=O)NS(=O)(=O)c1c(C)noc1C
null
null
null
1,282,275
ord_dataset-d5c54236ecd94d61aaa071461bcfc426
null
2013-01-01T00:04:00
true
C(OC([N:8]1[CH2:12][CH:11]([O:13][C:14]2[CH:19]=[CH:18][C:17]([F:20])=[C:16]([F:21])[CH:15]=2)[CH:10]2[N:22]([C:25](=[O:48])[CH:26]([NH:31][C:32](=[O:47])[CH:33]([N:35]([C:37]([O:39][CH2:40][C:41]3[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=3)=[O:38])[CH3:36])[CH3:34])[C:27]([CH3:30])([CH3:29])[CH3:28])[CH2:23][CH2:24][CH:9]12)=O)(C)(C)C.C(O)(C(F)(F)F)=O>C(Cl)Cl>[CH2:40]([O:39][C:37](=[O:38])[N:35]([CH:33]([C:32](=[O:47])[NH:31][CH:26]([C:25]([N:22]1[CH2:23][CH2:24][CH:9]2[NH:8][CH2:12][CH:11]([O:13][C:14]3[CH:19]=[CH:18][C:17]([F:20])=[C:16]([F:21])[CH:15]=3)[CH:10]12)=[O:48])[C:27]([CH3:28])([CH3:30])[CH3:29])[CH3:34])[CH3:36])[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1
CC(C(=O)NC(C(=O)N1CCC2C1C(Oc1ccc(F)c(F)c1)CN2C(=O)OC(C)(C)C)C(C)(C)C)N(C)C(=O)OCc1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
O=C(O)C(F)(F)F
null
null
null
null
null
null
null
null
null
0
2
The Boc-containing compound 34 (2.0 g, 3.0 mmol) was dissolved in DCM (30 mL) and cooled to 0° C. TFA (10 mL) was added and the reaction mixture was slowly warmed to ambient temperature. After 2 h, the reaction mixture was concentrated in vacuo and the crude residue was dissolved in EtOAc and washed successively with saturated aqueous NaHCO3 and brine. The organic extract was dried over anhydrous Na2SO4, filtered, and concentrated to afford 1.75 g of compound 35 as a white solid. Mass spectrum, m/z [573.1] (M+H)+.
CC(C(=O)NC(C(=O)N1CCC2NCC(Oc3ccc(F)c(F)c3)C21)C(C)(C)C)N(C)C(=O)OCc1ccccc1
null
101.9
null
377,235
ord_dataset-846d411edee44814931e062174d7ef12
null
1997-01-01T00:09:00
true
C([NH:8][CH2:9][C:10]1[O:14][N:13]=[C:12]([C:15]2[N:16]=[CH:17][N:18]3[C:24]4[CH:25]=[CH:26][CH:27]=[C:28]([C:29]([F:32])([F:31])[F:30])[C:23]=4[C:22](=[O:33])[N:21]4[CH2:34][CH2:35][C@H:20]4[C:19]=23)[N:11]=1)(OC(C)(C)C)=O>FC(F)(F)C(O)=O>[NH2:8][CH2:9][C:10]1[O:14][N:13]=[C:12]([C:15]2[N:16]=[CH:17][N:18]3[C:24]4[CH:25]=[CH:26][CH:27]=[C:28]([C:29]([F:32])([F:31])[F:30])[C:23]=4[C:22](=[O:33])[N:21]4[CH2:34][CH2:35][C@H:20]4[C:19]=23)[N:11]=1
CC(C)(C)OC(=O)NCc1nc(-c2ncn3c2[C@@H]2CCN2C(=O)c2c-3cccc2C(F)(F)F)no1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O=C(O)C(F)(F)F
null
null
null
null
null
null
null
null
null
null
null
null
7.8 g (15.9 mmol) of crude (S)-1-[5-(N-BOC-aminomethyl)-1,2,4-oxadiazol-3-yl]-8-trifluoromethyl-12,12a-dihydro-9H,11H-azeto[2,1-c]imidazo[1,5-a][1,4]benzodiazepin-9-one and 30 ml of trifluoroacetic acid were stirred at room temperature for 1hour. The solution was evaporated. The residue was dissolved in water and washed three times with methylene chloride. The aqueous phase was made alkaline with conc. ammonia and extracted nine times with ethyl acetate (a total of about 1 I). By evaporating the organic phases, combined and dried over magnesium sulfate, there were obtained 4.57 g (73%) of (S)-1-(5-aminomethyl-1,2,4-oxadiazol-3-yl)-8-trifluoromethyl-12,12a-dihydro-9H,11H-azeto[2,1-c]imidazo[1,5-a][1,4]benzodiazepin-9-one, which was used without further purification as the starting material for the Example described hereinafter.
NCc1nc(-c2ncn3c2[C@@H]2CCN2C(=O)c2c-3cccc2C(F)(F)F)no1
null
73.6
null
170,242
ord_dataset-37d3220f708c49ad839bab296b722248
null
1988-01-01T00:03:00
true
[Cl:1][C:2]1[CH:3]=[C:4]([CH:18]=[CH:19][C:20]=1[Cl:21])[CH2:5][N:6]1[C:15](=[O:16])[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[NH:8][C:7]1=[O:17].[H-].[Na+].Br[CH2:25][C:26]([O:28][CH2:29][CH3:30])=[O:27].Cl>CN(C)C=O>[Cl:1][C:2]1[CH:3]=[C:4]([CH:18]=[CH:19][C:20]=1[Cl:21])[CH2:5][N:6]1[C:15](=[O:16])[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[N:8]([CH2:25][C:26]([O:28][CH2:29][CH3:30])=[O:27])[C:7]1=[O:17]
O=c1[nH]c2ccccc2c(=O)n1Cc1ccc(Cl)c(Cl)c1
CCOC(=O)CBr
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
null
To a suspension of 3-(3,4-dichlorobenzyl)-1,2,3,4-tetrahydro-2,4-dioxoquinazoline (1 g) in N,N-dimethylformamide (15 ml) was added sodium hydride (60% in mineral oil, 0.17 g) with stirring at 0° C. and the mixture was stirred for 15 minutes at the same temperature. To this mixture was added ethyl bromoacetate (0.45 ml) and the mixture was stirred for 1 hour at room temperature. The reaction mixture was poured into diluted hydrochloric acid and extracted with ethyl acetate. The extract was washed with brine, dried and evaporated to give a residue. Thus obtained product was purified by recrystallization from isopropyl ether to give ethyl 2-[3-(3,4-dichlorobenzyl)-1,2,3,4-tetrahydro-2,4-dioxoquinazolin-1-yl]acetate (1.21 g).
CCOC(=O)Cn1c(=O)n(Cc2ccc(Cl)c(Cl)c2)c(=O)c2ccccc21
null
null
null
195,381
ord_dataset-b83b16f2fb1a4f8782f3d82c1766cc6b
null
1989-01-01T00:08:00
true
[F:1][C:2]1[CH:13]=[CH:12][C:5]([O:6][CH2:7][C@H:8]([OH:11])[CH2:9][OH:10])=[CH:4][CH:3]=1.N1C=CC=CC=1.CC1C=CC(S(Cl)(=O)=O)=CC=1>ClC(Cl)Cl>[F:1][C:2]1[CH:3]=[CH:4][C:5]([O:6][CH2:7][C@@H:8]([OH:11])[CH2:9][OH:10])=[CH:12][CH:13]=1
OC[C@@H](O)COc1ccc(F)cc1
null
null
Cc1ccc(S(=O)(=O)Cl)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
c1ccncc1
ClC(Cl)Cl
null
null
null
null
null
null
null
null
null
25
8
To a stirred mixture of 11 parts of (-)-(R)-3-(4-fluorophenoxy)-1,2-propanediol, 23.3 parts of pyridine and 240 parts of trichloromethane were added 12.3 parts of 4-methylbenzenesulfonyl chloride. The whole was stirred overnight at room temperature. It was washed successively with acid water, a sodium carbonate solution and water, dried, filtered and evaporated. The residue was purified by column chromatography over silica gel using a mixture of trichloromethane and methanol (98:2 by volume) as eluent. The pure fractions were collected and the eluent was evaporated, yielding 13.5 parts (67.2%) of (+)-(S)-3-(4-fluorophenoxy)-1,2-propanediol, O1 -4-methylbenzenesulfonate; [α]D =+11.11° (c=0.5% in trichloromethane) (147).
OC[C@H](O)COc1ccc(F)cc1
null
67.2
null
829,329
ord_dataset-47bd90bf5ec74fcd99ce250a56e18c8f
null
2008-01-01T00:07:00
true
[C:1]([C:3]1[N:8]=[C:7]([CH2:9][NH:10][C:11](=[O:17])[O:12][C:13]([CH3:16])([CH3:15])[CH3:14])[CH:6]=[CH:5][CH:4]=1)#[N:2].[C:18](OC)(=[O:26])[C:19]1[C:20](=[CH:22][CH:23]=[CH:24][CH:25]=1)[SH:21].C(N(CC)CC)C>C1(C)C=CC=CC=1>[O:26]=[C:18]1[C:19]2[CH:25]=[CH:24][CH:23]=[CH:22][C:20]=2[S:21][C:1]([C:3]2[N:8]=[C:7]([CH2:9][NH:10][C:11](=[O:17])[O:12][C:13]([CH3:14])([CH3:16])[CH3:15])[CH:6]=[CH:5][CH:4]=2)=[N:2]1
COC(=O)c1ccccc1S
CC(C)(C)OC(=O)NCc1cccc(C#N)n1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
CCN(CC)CC
null
null
null
null
null
null
null
null
null
null
null
tert-Butyl (6-cyano-2-pyridyl)methylcarbamate (1.6 g, 6.8 mmol) and methyl thiosalicylate (1.8 g, 10.9 mmol) were dissolved in toluene (6 ml), and triethylamine (3.0 ml, 21.5 mmol) was added thereto. The mixture was refluxed for 20 hrs. After cooling, the precipitates were collected by filtration and dissolved in chloroform. The solution was subjected to a silica gel column chromatography. The fractions eluted with chloroform-methanol (20:1, v/v) were collected, concentrated and recrystallized from hexane-chloroform to give the titled compound (1.8 g, 72%) as pale yellow crystals.
CC(C)(C)OC(=O)NCc1cccc(-c2nc(=O)c3ccccc3s2)n1
null
71.7
null
1,079,131
ord_dataset-afd812677c134591a99f46ce28de2524
null
2011-01-01T00:08:00
true
[CH2:1]([C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[N:9]=[CH:8][C:7]([N+:13]([O-:15])=[O:14])=[C:6]2O)[CH3:2].O=P(Cl)(Cl)[Cl:19]>>[Cl:19][C:6]1[C:5]2[C:10](=[CH:11][CH:12]=[C:3]([CH2:1][CH3:2])[CH:4]=2)[N:9]=[CH:8][C:7]=1[N+:13]([O-:15])=[O:14]
O=P(Cl)(Cl)Cl
CCc1ccc2ncc([N+](=O)[O-])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
The title compound is prepared in analogy to Example 19c starting from 3.6 g (16.49 mmol) 6-ethyl-3-nitro-quinolin-4-ol (Example 49d) and 24 ml POCl3. mp: 290-295° C.; MS: 237 (M++1); HPLC: tret=13.72 min (Grad 1).
CCc1ccc2ncc([N+](=O)[O-])c(Cl)c2c1
null
null
null
1,466,640
ord_dataset-fd1fa959d6264608b0b7fcda16741bfd
null
2014-01-01T00:08:00
true
[N+:1]([C:4]1[CH:12]=[C:11]2[C:7]([CH:8]=[CH:9][NH:10]2)=[CH:6][CH:5]=1)([O-:3])=[O:2].[C:13]([O-])([O-])=O.[K+].[K+].O>CN(C=O)C>[CH3:13][N:10]1[C:11]2[C:7](=[CH:6][CH:5]=[C:4]([N+:1]([O-:3])=[O:2])[CH:12]=2)[CH:8]=[CH:9]1
O=C([O-])[O-]
O=[N+]([O-])c1ccc2cc[nH]c2c1
null
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CN(C)C=O
null
null
null
null
null
null
null
null
null
25
8
To a solution of 6-nitroindole (4.05 g 25 mmol) in DMF (50 mL) was added K2CO3 (8.63 g, 62.5 mmol) and Me (5.33 g, 37.5 mmol). After stirring at room temperature overnight, the mixture was poured into water and extracted with ethyl acetate. The combined organic layers were dried over Na2SO4 and concentrated under vacuum to give the product 1-methyl-6-nitro-1H-indole (4.3 g, 98%).
Cn1ccc2ccc([N+](=O)[O-])cc21
null
97.6
null
1,205,469
ord_dataset-fb72428f30234761b4216139dc228d0c
null
2012-01-01T00:09:00
true
N1C=CN=C1.[CH3:6][C:7]([Si:10](Cl)([CH3:12])[CH3:11])([CH3:9])[CH3:8].[Cl:14][C:15]1[C:16]([CH3:41])=[C:17]([NH:23][C@H:24]([CH2:39][OH:40])[C:25]([NH:27][NH:28][C:29](=[O:38])[C:30]2[CH:35]=[CH:34][C:33]([C:36]#[N:37])=[CH:32][CH:31]=2)=[O:26])[CH:18]=[CH:19][C:20]=1[C:21]#[N:22].O>CN(C=O)C>[Si:10]([O:40][CH2:39][C@@H:24]([NH:23][C:17]1[CH:18]=[CH:19][C:20]([C:21]#[N:22])=[C:15]([Cl:14])[C:16]=1[CH3:41])[C:25]([NH:27][NH:28][C:29](=[O:38])[C:30]1[CH:35]=[CH:34][C:33]([C:36]#[N:37])=[CH:32][CH:31]=1)=[O:26])([C:7]([CH3:9])([CH3:8])[CH3:6])([CH3:12])[CH3:11]
Cc1c(N[C@H](CO)C(=O)NNC(=O)c2ccc(C#N)cc2)ccc(C#N)c1Cl
CC(C)(C)[Si](C)(C)Cl
null
c1c[nH]cn1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CN(C)C=O
null
null
null
null
null
null
null
null
null
25
20
Imidazole (1.3 g, 19.1 mol) and TBDMS-Cl (1.73 g, 11.46 mmol) were added sequentially to a pre-cooled (0° C.) solution of (R)—N′-(2-(3-chloro-4-cyano-2-methylphenylamino)-3-hydroxypropanoyl)-4-cyanobenzohydrazide (1.52 g, 3.82 mmol) in DMF (145 mL). The reaction mixture was allowed to warm to room temperature and stirred for 20 h, whereupon the solution was poured into H2O (200 mL). The white precipitate was filtered, washed with H2O (35 mL) and taken up in CH2Cl2 (300 mL). This organic layer was washed with brine (1×160 mL), dried (Na2SO4), filtered and concentrated to provide the title compound (1.52 g, 78%). 1H NMR (400 MHz, acetone-d6, δ in ppm) 9.6 (br s, 1H), 7.97 (d, J=8.0 Hz, 2H), 7.80 (d, J=9 Hz, 2H), 7.41 (d, J=8 Hz, 1H), 6.63 (d, J=8 Hz, 3H), 5.45 (d, J=8 Hz, 1H), 4.29-4.23 (m, 1H), 4.05-4.02 (m, 2H), 2.21 (s, 3H), 0.79 (s, 9H), 0.01 (s, 6H).
Cc1c(N[C@H](CO[Si](C)(C)C(C)(C)C)C(=O)NNC(=O)c2ccc(C#N)cc2)ccc(C#N)c1Cl
null
77.7
null
103,328
ord_dataset-bdb961f26fac426eaa2de8f54a284acf
null
1983-01-01T00:02:00
true
[N+]([C:4]1[CH:13]=[CH:12][CH:11]=[C:6]([C:7]([O:9]C)=[O:8])[C:5]=1[C:14]([O:16][CH3:17])=[O:15])([O-])=O.[CH3:18][O-:19].[Na+]>CN(C)P(=O)(N(C)C)N(C)C.O>[C:14]([C:5]1[C:4]([O:19][CH3:18])=[CH:13][CH:12]=[CH:11][C:6]=1[C:7]([OH:9])=[O:8])([O:16][CH3:17])=[O:15]
C[O-]
COC(=O)c1cccc([N+](=O)[O-])c1C(=O)OC
null
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)P(=O)(N(C)C)N(C)C
O
null
null
null
null
null
null
null
null
null
null
44
Dimethyl 3-nitrophthalate (4.8 g, 20 mmol) was added to a cold solution of sodium methoxide (2.61 g, 48.3 mmol) in dry hexamethylphosphoric triamide (75 ml). The resulting dark solution was gradually brought to room temperature and the reaction mixture was stirred for 44 hrs. It was then diluted with water (125 ml) and extracted with benzene. (This extract contained a variable quantity of dimethyl 3-methoxyphthalate. The aqueous layer was acidified with hydrochloric acid and extracted with benzene. The combined organic layers were washed with water (5×30 ml) and then brine (1×15 ml), dried over sodium sulfate, filtered and evaporated to give 3.25 g (75%) of 2-carbomethoxy-3-methoxybenzoic acid, mp 140°-141° C. (benzene). Identity was confirmed by mixture mp, co-chromatography and spectroscopic comparison with an authentic sample. 1H NMR (CDCl3) δ 3.86 (3H, s, ArCO2CH3), 3.93 (3H, s, ArOCH3), 7.13 (1H, dd, J=8,2 Hz, ArH4), 7.43 (1H, t, J=8 Hz, ArH5), 7.68 (1H, dd, J=8,2 Hz, ArH6, 10.50 (1H, broad s, ArCO2H); IR (KBr) 3200 (br), 2960, 1740, 1690, 1585, 1475, 1310, 1050 cm-1 , etc.; mass spectrum m/e (rel. intensity) 211 (m+ +1,5%), 210 M+, 30%), 193 (M+ -OH, 2%), 180 (M+ -2CH3, 100%), 179 (M+ -OCH3, 10%), etc.
COC(=O)c1c(OC)cccc1C(=O)O
null
77.3
null
729,787
ord_dataset-eb4226b4f7644a01a737e7547b70014a
null
2006-01-01T00:09:00
true
[C:1]1([CH:7]([O:14][C:15]([C:17]2[N:18]3[CH:21]([CH2:22][CH2:23][C:24]=2[SH:25])[C@@H:20]([NH:26][C:27](=[O:57])/[C:28](/[C:50]2[N:51]=[C:52]([NH2:56])[S:53][C:54]=2[Cl:55])=[N:29]\[O:30][C:31]([C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[C:19]3=[O:58])=[O:16])[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:59]([O:63][C:64]([NH:66][CH2:67][CH2:68][S:69][CH2:70][C:71]1[CH:72]=[N:73][CH:74]=[CH:75][C:76]=1Cl)=[O:65])([CH3:62])([CH3:61])[CH3:60].O>CN(C)C=O>[C:1]1([CH:7]([O:14][C:15]([C:17]2[N:18]3[CH:21]([CH2:22][CH2:23][C:24]=2[S:25][C:76]2[CH:75]=[CH:74][N:73]=[CH:72][C:71]=2[CH2:70][S:69][CH2:68][CH2:67][NH:66][C:64]([O:63][C:59]([CH3:62])([CH3:61])[CH3:60])=[O:65])[C@@H:20]([NH:26][C:27](=[O:57])/[C:28](/[C:50]2[N:51]=[C:52]([NH2:56])[S:53][C:54]=2[Cl:55])=[N:29]\[O:30][C:31]([C:38]2[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=2)([C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[C:44]2[CH:45]=[CH:46][CH:47]=[CH:48][CH:49]=2)[C:19]3=[O:58])=[O:16])[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
CC(C)(C)OC(=O)NCCSCc1cnccc1Cl
Nc1nc(/C(=N/OC(c2ccccc2)(c2ccccc2)c2ccccc2)C(=O)N[C@H]2C(=O)N3C(C(=O)OC(c4ccccc4)c4ccccc4)=C(S)CCC23)c(Cl)s1
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
null
8
To a solution of (7R)-7-[(Z)-2-(2-amino-5-chlorothiazol-4-yl)-2-(triphenylmethoxyimino]-acetamido]-3-mercapto-8-oxo-1-aza-bicyclo[4.2.0]oct-2-ene-2-carboxylate diphenylmethyl ester (3.0 g, 0.0036 mol) in dimethylformamide (30 mL) was added 3-(N-tert-butoxycarbonylaminoethylthiomethyl)-4-chloropyridine (1.3 g, 0.0043 mol) at room temperature. After stirring overnight, the reaction mixture was treated with water (200 mL), and the solid that formed was filtered and dried to afford the crude title compound (2.9 g).
CC(C)(C)OC(=O)NCCSCc1cnccc1SC1=C(C(=O)OC(c2ccccc2)c2ccccc2)N2C(=O)[C@H](NC(=O)/C(=N\OC(c3ccccc3)(c3ccccc3)c3ccccc3)c3nc(N)sc3Cl)C2CC1
null
73.7
null
1,097,806
ord_dataset-af85e6f81c2d49f08086afd6d9e6959c
null
2011-01-01T00:10:00
true
[N:1]1[CH:2]=[CH:3][N:4]2[C:9]=1[CH:8]=[CH:7][C:6]([O:10][C:11]1[CH:12]=[C:13]([CH:15]=[CH:16][CH:17]=1)[NH2:14])=[N:5]2.C(N(CC)CC)C.[C:25]1([N:31]=[C:32]=[O:33])[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1>O1CCCC1>[N:1]1[CH:2]=[CH:3][N:4]2[C:9]=1[CH:8]=[CH:7][C:6]([O:10][C:11]1[CH:12]=[C:13]([NH:14][C:32]([NH:31][C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)=[O:33])[CH:15]=[CH:16][CH:17]=1)=[N:5]2
O=C=Nc1ccccc1
Nc1cccc(Oc2ccc3nccn3n2)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(CC)CC
C1CCOC1
null
null
null
null
null
null
null
null
null
25
18
To a solution of 3-(imidazo[1,2-b]pyridazin-6-yloxy)aniline (181 mg, 0.80 mmol) and triethylamine (0.011 mL, 0.08 mmol) in tetrahydrofuran (10 mL) was added phenyl isocyanate (0.104 mL, 0.96 mmol), and the mixture was stirred at room temperature for 18 hr. The reaction mixture was concentrated under reduced pressure, and the residue was purified by NH silica gel column chromatography (ethyl acetate/methanol=100/0→90/10) and precipitated from ethyl acetate to give the title compound (196 mg, 71%) as a white powder.
O=C(Nc1ccccc1)Nc1cccc(Oc2ccc3nccn3n2)c1
null
70.9
null
1,493,798
ord_dataset-366bdd9ee72d474cbe6f3f9e54dd96d2
null
2014-01-01T00:10:00
true
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([S:8](Cl)(=[O:10])=[O:9])=[CH:4][CH:3]=1.[Cl:12][C:13]1[CH:25]=[N:24][C:16]2[NH:17][C:18]3[CH2:23][CH2:22][NH:21][CH2:20][C:19]=3[C:15]=2[CH:14]=1.O>N1C=CC=CC=1>[Cl:12][C:13]1[CH:25]=[N:24][C:16]2[NH:17][C:18]3[CH2:23][CH2:22][N:21]([S:8]([C:5]4[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][CH:4]=4)(=[O:10])=[O:9])[CH2:20][C:19]=3[C:15]=2[CH:14]=1
Clc1cnc2[nH]c3c(c2c1)CNCC3
O=S(=O)(Cl)c1ccc(Cl)cc1
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
8
4-Chlorobenzenesulfonyl chloride (56 mg, 0.26 mmol) was added to a solution of 3-chloro-6,7,8,9-tetrahydro-5H-dipyrido[2,3-b;3′,4′-d]pyrrole (50 mg, 0.24 mmol) in pyridine (2 mL), and the reaction was stirred overnight at room temperature. The reaction mixture was added to water (20 mL), and the resulting precipitate was filtered and dried under vacuum to provide 33 (92 mg, 99% yield) as a yellow solid. LC-MS (M+H=382, obsd.=382).
O=S(=O)(c1ccc(Cl)cc1)N1CCc2[nH]c3ncc(Cl)cc3c2C1
null
100.3
null
1,476,559
ord_dataset-c3c1091f873b4f40827973a6f1f9b685
null
2014-01-01T00:09:00
true
[NH2:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[SH:9].Br[CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C([O-])([O-])=O.[K+].[K+]>CN(C=O)C>[CH2:11]([S:9][C:3]1[CH:4]=[CH:5][C:6]([Cl:8])=[CH:7][C:2]=1[NH2:1])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1
Nc1cc(Cl)ccc1S
BrCc1ccccc1
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
Following General Procedure A, the title compound (819 mg, 100%) was prepared from 2-amino-4-chlorobenzenethiol (700 mg, 4.39 mmol), (bromomethyl)benzene (560 mg, 2.92 mmol), K2CO3 (2.0 g, 14.62 mmol) in DMF (20 ml).
Nc1cc(Cl)ccc1SCc1ccccc1
null
112.3
null
1,264,903
ord_dataset-d3580a12b15e46cc91aa73f4f1a4a8cc
null
2013-01-01T00:03:00
true
[Cl:1][C:2]1[CH:3]=[C:4]([C:12]2[S:16][N:15]=[C:14]([C:17]3[C:18]([CH2:26][CH3:27])=[C:19]([CH2:23][CH:24]=O)[CH:20]=[CH:21][CH:22]=3)[N:13]=2)[CH:5]=[N:6][C:7]=1[O:8][CH:9]([CH3:11])[CH3:10].[NH:28]1[CH2:33][CH2:32][CH:31]([C:34]([O:36][CH2:37][CH3:38])=[O:35])[CH2:30][CH2:29]1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCl>[Cl:1][C:2]1[CH:3]=[C:4]([C:12]2[S:16][N:15]=[C:14]([C:17]3[C:18]([CH2:26][CH3:27])=[C:19]([CH2:23][CH2:24][N:28]4[CH2:33][CH2:32][CH:31]([C:34]([O:36][CH2:37][CH3:38])=[O:35])[CH2:30][CH2:29]4)[CH:20]=[CH:21][CH:22]=3)[N:13]=2)[CH:5]=[N:6][C:7]=1[O:8][CH:9]([CH3:11])[CH3:10]
CCc1c(CC=O)cccc1-c1nsc(-c2cnc(OC(C)C)c(Cl)c2)n1
CCOC(=O)C1CCNCC1
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
ClCCl
null
null
null
null
null
null
null
null
null
null
null
8
To a solution of [3-(5-{5-chloro-6-[(1-methylethyl)oxy]-3-pyridinyl}-1,2,4-thiadiazol-3-yl)-2-ethylphenyl]acetaldehyde (D111) (2 g, 2.488 mmol) in Dichloromethane (DCM) (10 mL) was added ethyl 4-piperidinecarboxylate (0.430 g, 2.74 mmol). The reaction solution was stirred for 5 min before sodium triacetoxyborohydride (0.791 g, 3.73 mmol) was added. The reaction solution was stirred overnight. The reaction solution was washed with water, dried, concentrated and purified by ISCO column chromatography to afford the crude product ethyl 1-{2-[3-(5-{5-chloro-6-[(1-methylethyl)oxy]-3-pyridinyl}-1,2,4-thiadiazol-3-yl)-2-ethylphenyl]ethyl}-4-piperidinecarboxylate (D112) (450 mg). MS (ES): C28H35ClN4O3S requires 542.2. found 543.2 (M+H+).
CCOC(=O)C1CCN(CCc2cccc(-c3nsc(-c4cnc(OC(C)C)c(Cl)c4)n3)c2CC)CC1
null
33.3
null
620,781
ord_dataset-c9f990dde2dc45d0948ecbe037a0d819
null
2004-01-01T00:01:00
true
[O:1]([C:8]1[CH:9]=[C:10]([C:14]2[CH2:18][CH:17]([CH2:19][CH2:20][CH:21]=O)[O:16][N:15]=2)[CH:11]=[CH:12][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:23]1([CH:29]([C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[N:30]2[CH2:35][CH2:34][NH:33][CH2:32][CH2:31]2)[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+]>C(Cl)Cl>[CH:29]([N:30]1[CH2:35][CH2:34][N:33]([CH2:21][CH2:20][CH2:19][CH:17]2[O:16][N:15]=[C:14]([C:10]3[CH:11]=[CH:12][CH:13]=[C:8]([O:1][C:2]4[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=4)[CH:9]=3)[CH2:18]2)[CH2:32][CH2:31]1)([C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1
O=CCCC1CC(c2cccc(Oc3ccccc3)c2)=NO1
c1ccc(C(c2ccccc2)N2CCNCC2)cc1
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
ClCCl
null
null
null
null
null
null
null
null
null
null
null
null
3-[3-(3-Phenoxyphenyl)-4,5-dihydroisoxazol-5-yl]propanal (27.1 mg, 0.087 mmol), 1-(diphenylmethyl)piperazine (20.0 mg, 0.078 mmol), molecular sieve (5 beads) and NaBH(OAc)3 (50.0 mg, 0.237 mmol) were reacted in 3 mL of methylene chloride for about 12 hr. With the following processes the same as in Example 1, 20.2 mg (53.3%) of the target compound was obtained.
c1ccc(Oc2cccc(C3=NOC(CCCN4CCN(C(c5ccccc5)c5ccccc5)CC4)C3)c2)cc1
null
48.7
null
202,033
ord_dataset-19e5fc80c1554f4f8641c835e055f02b
null
1990-01-01T00:01:00
true
[OH:1][C:2]1[CH:18]=[CH:17][C:5]([O:6][CH2:7][CH2:8][CH2:9][CH2:10][C:11]([CH3:16])([CH3:15])[C:12]([NH2:14])=[O:13])=[CH:4][CH:3]=1.C(=O)([O-])[O-].[K+].[K+].[Br:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30]Br>C(O)C>[Br:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][O:1][C:2]1[CH:3]=[CH:4][C:5]([O:6][CH2:7][CH2:8][CH2:9][CH2:10][C:11]([CH3:15])([CH3:16])[C:12]([NH2:14])=[O:13])=[CH:17][CH:18]=1
CC(C)(CCCCOc1ccc(O)cc1)C(N)=O
BrCCCCCBr
null
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
null
null
A mixture of 3.0 g 6-(4-hydroxyphenoxy)-2,2-dimethylhexanamide, 50 ml ethanol, 2.5 g potassium carbonate and 3.6 g 1,5-dibromopentane was heated under reflux overnight with stirring. The solvent was distilled off under reduced pressure, the residue was extracted with chloroform, the extract was washed with water and worked up as usual. The crude product thus obtained was purified by silica gel column chromatography, affording 2.90 g of 6-[p-(5-bromopentyloxy)phenoxy]-2,2-dimethylhexanamide.
CC(C)(CCCCOc1ccc(OCCCCCBr)cc1)C(N)=O
null
60.7
null
1,621,651
ord_dataset-35c51552812941cda45194a013d34bb9
null
2015-01-01T00:08:00
true
[CH3:1]CN(CC)CC.[CH2:8]([O:15][N:16]1[C:22](=[O:23])[N:21]2[CH2:24][C@H:17]1[CH2:18][CH2:19][C@H:20]2[C:25]1[O:26][C:27]([N:30]2[CH2:35][CH2:34][NH:33][CH2:32][CH2:31]2)=[N:28][N:29]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.CI>CN(C=O)C>[CH2:8]([O:15][N:16]1[C:22](=[O:23])[N:21]2[CH2:24][C@H:17]1[CH2:18][CH2:19][C@H:20]2[C:25]1[O:26][C:27]([N:30]2[CH2:35][CH2:34][N:33]([CH3:1])[CH2:32][CH2:31]2)=[N:28][N:29]=1)[C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1
O=C1N2C[C@@H](CC[C@H]2c2nnc(N3CCNCC3)o2)N1OCc1ccccc1
CCN(CC)CC
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CI
CN(C)C=O
null
null
null
null
null
null
null
null
null
25
6
Et3N (631 μL, 4.5 mmol) was added to a solution of crude (2S,5R)-6-(benzyloxy)-2-(5-(piperazin-1-yl)-1,3,4-oxadiazol-2-yl)-1,6-diaza-bicyclo[3.2.1]octan-7-one (997 mg) in DMF (15 mL). Then, MeI (106 μL, 1.6 mmol) was slowly added at 0° C. The mixture was stirred at rt for 6 hrs then, the mixture was concentrated and purified by reverse phase column chromatography (gradient elution, 0 to 80% of acetonitrile in water) to give (2S,5R)-6-(benzyloxy)-2-(5-(4-methylpiperazin-1-yl)-1,3,4-oxadiazol-2-yl)-1,6-diaza-bicyclo[3.2.1]octan-7-one (202 mg, 34% for two steps) as a yellow solid. ESI-MS (EI+, m/z): 399.3 [M+H]+.
CN1CCN(c2nnc([C@@H]3CC[C@@H]4CN3C(=O)N4OCc3ccccc3)o2)CC1
null
19.5
null
1,607,308
ord_dataset-9cecb3a8d3b9494191b28dcefea66af2
null
2015-01-01T00:07:00
true
Cl[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[CH:10][C:11]([NH2:14])=[N:12][CH:13]=2)=[C:4]([F:15])[CH:3]=1.CC1(C)C(C)(C)[O:20][B:19](B2OC(C)(C)C(C)(C)O2)[O:18]1.CC([O-])=O.[K+].Cl>CCOC(C)=O.O1CCOCC1>[NH2:14][C:11]1[N:12]=[CH:13][C:8]([C:5]2[CH:6]=[CH:7][C:2]([B:19]([OH:20])[OH:18])=[CH:3][C:4]=2[F:15])=[CH:9][CH:10]=1
Nc1ccc(-c2ccc(Cl)cc2F)cn1
CC1(C)OB(B2OC(C)(C)C(C)(C)O2)OC1(C)C
null
CC(=O)[O-]
Cl
[K+]
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
80
0.33
5-(4-Chloro-2-fluorophenyl)pyridin-2-amine (2.0 g, 9.0 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (2.9 g, 11.0 mmol), chloro(2-dicyclohexyl-phosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II) (0.14 g, 0.18 mmol), and KOAc (2.7 g, 27 mmol) were combined in a sealable reaction vessel under nitrogen, and then treated with anhydrous 1,4-dioxane (100 mL, sparged with nitrogen). The vessel was sealed and then heated at 80° Celsius for 16 hours. The mixture was cooled to rt, HCl (1 m, 50 mL) was added and the mixture stirred for 20 min. The mixture was then diluted with EtOAc (200 mL) and the aqueous phase was collected. The organic phase was extracted with 1 M HCl (2×75 mL). The combined aqueous phases were cooled in an icebath and the pH was adjusted to ca. 7 using solid sodium bicarbonate. The resulting precipitate was collected by filtration, washed well with water, and dried to provide the title compound (2.1 g, 98%). MS (CI): mass calcd. for C11H10BFN2O2, 232.08; m/z found, 233.1 [M+H]+. 1H NMR (500 MHz, DMSO-d6) δ 8.29-8.20 (s, 2H), 8.18-8.13 (s, 1H), 7.80-7.72 (m, 1H), 7.69-7.63 (m, 1H), 7.63-7.57 (m, 1H), 7.51-7.44 (m, 1H), 6.84-6.57 (m, 3H).
Nc1ccc(-c2ccc(B(O)O)cc2F)cn1
null
100.6
null
349,308
ord_dataset-66f304805e5d47fc8d3c722b1bd8dfa2
null
1996-01-01T00:12:00
true
[F:1][C:2]1[C:3]([CH3:27])=[C:4]2[C:9](=[CH:10][C:11]=1F)[N:8]([C:13]1[CH:18]=[CH:17][C:16]([F:19])=[CH:15][C:14]=1[F:20])[CH:7]=[C:6]([C:21]([O:23]CC)=[O:22])[C:5]2=[O:26].[NH:28]1[CH2:33][CH2:32][NH:31][CH2:30][CH2:29]1>C(#N)C>[F:1][C:2]1[C:3]([CH3:27])=[C:4]2[C:9](=[CH:10][C:11]=1[N:28]1[CH2:33][CH2:32][NH:31][CH2:30][CH2:29]1)[N:8]([C:13]1[CH:18]=[CH:17][C:16]([F:19])=[CH:15][C:14]=1[F:20])[CH:7]=[C:6]([C:21]([OH:23])=[O:22])[C:5]2=[O:26]
CCOC(=O)c1cn(-c2ccc(F)cc2F)c2cc(F)c(F)c(C)c2c1=O
C1CNCCN1
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
A solution of 0.76 g (2.00 mmol) of ethyl 6,7-difluoro-1-(2,4-difluorophenyl)-1,4-dihydro-5-methyl-4-oxo-3-quinolinecarboxylate, 0.69 g (8.00 mmol) of anhydrous piperazine, and 30 mL of acetonitrile was refluxed for 18 hours, cooled, and concentrated. The residue was dissolved in 20 mL 6N hydrochloric acid and refluxed for 3 hours. The suspension was cooled, concentrated by half and filtered, and the solids were washed with water. The crude product was suspended in water which was made basic (pH 12), and the resulting solution was filtered and neutralized to pH 6.8. The precipitate which formed was filtered, washed with water, and dried to give 0.58 g of the title compound, mp 198°-200° C.
Cc1c(F)c(N2CCNCC2)cc2c1c(=O)c(C(=O)O)cn2-c1ccc(F)cc1F
null
69.5
null
1,184,865
ord_dataset-9cd817a75dfc4fe7ad19d4232772d5ff
null
2012-01-01T00:07:00
true
CCN=C=NCCCN(C)C.C1C=CC2N(O)N=NC=2C=1.[C:22]([C:24]1[CH:25]=[C:26]([CH:30]=[CH:31][C:32]=1[O:33][CH:34]([CH3:36])[CH3:35])[C:27]([OH:29])=O)#[N:23].O[NH:38][C:39]([C:41]1[CH:42]=[C:43]2[C:47](=[CH:48][CH:49]=1)[NH:46][C:45]([CH2:50][OH:51])=[CH:44]2)=[NH:40]>CN(C=O)C.CCOC(C)=O>[OH:51][CH2:50][C:45]1[NH:46][C:47]2[C:43]([CH:44]=1)=[CH:42][C:41]([C:39]1[N:40]=[C:27]([C:26]3[CH:30]=[CH:31][C:32]([O:33][CH:34]([CH3:36])[CH3:35])=[C:24]([CH:25]=3)[C:22]#[N:23])[O:29][N:38]=1)=[CH:49][CH:48]=2
N=C(NO)c1ccc2[nH]c(CO)cc2c1
CC(C)Oc1ccc(C(=O)O)cc1C#N
null
CCN=C=NCCCN(C)C
On1nnc2ccccc21
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
CCOC(C)=O
null
null
null
null
null
null
null
null
null
80
0.25
EDCI (144 mg) and HOBT (104 mg) were added to a solution of 3-cyano-4-[(1-methylethyl)oxy]benzoic acid (can be prepared as described on WO2005/58848, 144 mg) in DMF (5 mL) at RT. The resulting solution was stirred for 15 min. N-Hydroxy-2-(hydroxymethyl)-1H-indole-5-carboximidamide (D25) (144 mg) was added and the reaction mixture was stirred at RT for 1 hour. The reaction mixture was heated to 80° C. and stirred at that temperature for 4 hours. EtOAc (50 mL) was added and the organic solution was washed with water (50 mL), saturated aqueous sodium bicarbonate solution (50 mL) and water (50 mL). The organic fraction was dried over anhydrous magnesium sulfate. The dried solution was concentrated. The residue was recrystallized from EtOAc/ether to afford 5-{3-[2-(hydroxymethyl)-1H-indol-5-yl]-1,2,4-oxadiazol-5-yl}-2-[(1-methylethyl)oxy]benzonitrile (E12) (70 mg) as a light brown solid. δH (DMSO-d6, 400 MHz): 1.39 (6H, d), 4.65 (2H, d), 4.99 (1H, m), 5.36 (1H, t), 6.46 (1H, s), 7.49 (1H, d), 7.56 (1H, d), 7.79 (1H, dd), 8.28 (1H, dd), 8.42 (1H, d), 8.52 (1H, d), 11.43 (1H, s). MS (ES): C21H18N4O3 requires 374; found 375.0 (M+H+).
CC(C)Oc1ccc(-c2nc(-c3ccc4[nH]c(CO)cc4c3)no2)cc1C#N
null
26.6
null
1,246,519
ord_dataset-c544c0c663f54dbea4ddb52ddde7934e
null
2013-01-01T00:01:00
true
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:9]=[C:10]3[C:15]([CH3:16])=[C:14]([CH3:17])[C:13]([N:18]4[CH2:23][CH2:22][N:21](C(OC(C)(C)C)=O)[CH2:20][CH2:19]4)=[N:12][N:11]3[C:31]=2[C:32]2[CH:37]=[CH:36][N:35]=[CH:34][CH:33]=2)=[CH:4][CH:3]=1.FC(F)(F)C(O)=O>ClCCl>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:9]=[C:10]3[C:15]([CH3:16])=[C:14]([CH3:17])[C:13]([N:18]4[CH2:23][CH2:22][NH:21][CH2:20][CH2:19]4)=[N:12][N:11]3[C:31]=2[C:32]2[CH:33]=[CH:34][N:35]=[CH:36][CH:37]=2)=[CH:4][CH:3]=1
Cc1c(N2CCN(C(=O)OC(C)(C)C)CC2)nn2c(-c3ccncc3)c(-c3ccc(F)cc3)nc2c1C
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O=C(O)C(F)(F)F
ClCCl
null
null
null
null
null
null
null
null
null
25
4
To a solution of 0.43 g (0.86 mmol) of tert-butyl 4-[2-(4-fluorophenyl)-7,8-dimethyl-3-pyrid-4-ylimidazo[1,2-b]pyridazin-6-yl]piperazine-1-carboxylate in 5 mL of dichloromethane at 0° C. is added dropwise 0.64 mL (8.6 mmol) of trifluoroacetic acid. After stirring for 4 hours at room temperature, a further 0.64 mL (8.6 mmol) of trifluoroacetic acid is added and the reaction mixture is left for 18 hours. The solvent is then removed under reduced pressure and the residue is taken up in water. The resulting aqueous phase is washed with ether and then basified by addition of aqueous sodium hydrogen carbonate solution. The product is extracted with dichloromethane, the organic phase is dried over sodium sulfate and filtered, and the solvent is evaporated off to give 0.285 g of a white powder.
Cc1c(N2CCNCC2)nn2c(-c3ccncc3)c(-c3ccc(F)cc3)nc2c1C
null
82.3
null
1,399,550
ord_dataset-12dc3bd21bcf44d09e5b4249afe15161
null
2014-01-01T00:02:00
true
[C:1](O)(=[O:3])[CH3:2].[NH2:5][CH2:6][C@@H:7]1[O:11][C:10](=[O:12])[N:9]([C:13]2[CH:18]=[CH:17][C:16]([N:19]3[CH2:24][CH2:23][O:22][CH2:21][CH2:20]3)=[C:15]([F:25])[CH:14]=2)[CH2:8]1.C(OC(=O)C)(=O)C>O>[CH3:2][C:1]([NH:5][CH2:6][C@@H:7]1[O:11][C:10](=[O:12])[N:9]([C:13]2[CH:18]=[CH:17][C:16]([N:19]3[CH2:20][CH2:21][O:22][CH2:23][CH2:24]3)=[C:15]([F:25])[CH:14]=2)[CH2:8]1)=[O:3]
NC[C@H]1CN(c2ccc(N3CCOCC3)c(F)c2)C(=O)O1
CC(=O)O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CC(=O)OC(C)=O
null
null
null
null
null
null
null
null
null
50
2
(S)-5-(aminomethyl)-3-(3-fluoro-4-morpholinophenyl)oxazolidin-2-one acetate (3.5 g, 10 mmol) was dissolved in 20 mL of water. The solution was heated to 50° C. and then acetic anhydride (0.72 g, 12 mmol) was added dropwise and stirred at 50° C. for 2 hours. The mixture was cooled down to 0° C. to crystallize, filtered, washed with water, dried and recrystallized with ethyl acetate to provide 3.0 g of Linezolid in 88% yield.
CC(=O)NC[C@H]1CN(c2ccc(N3CCOCC3)c(F)c2)C(=O)O1
null
88.9
null
801,704
ord_dataset-56a22bc0c3b14f87b9aa3f2fc6488ee7
null
2007-01-01T00:12:00
true
[OH:1][N:2]1[C:6](=[O:7])[C:5]2=[CH:8][CH:9]=[CH:10][CH:11]=[C:4]2[C:3]1=[O:12].[C:13]1(B(O)O)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.N1C=CC=CC=1>[Cu]Cl.ClCCCl>[O:1]([N:2]1[C:3](=[O:12])[C:4]2=[CH:11][CH:10]=[CH:9][CH:8]=[C:5]2[C:6]1=[O:7])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1
OB(O)c1ccccc1
O=C1c2ccccc2C(=O)N1O
null
Cl[Cu]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
c1ccncc1
ClCCCl
null
null
null
null
null
null
null
null
null
25
null
A 20 mL scintillation vial was charged with N-hydroxyphthalimide (163 mg, 1.0 mmol), copper (I) chloride (99 mg, 1.0 mmol), freshly activated 4 Å molecular sieves (˜250 mg), and phenylboronic acid (244 mg, 2.0 mmol). 1,2-Dichloroethane (5 mL) was added followed by pyridine (90 μL, 1.1 mmol), resulting in a light brown suspension. The cap was loosely applied such that the reaction suspension was open to air and stirred at room temperature until completion as detected by analytical RP-HPLC (mixture color turned from brown to emerald green as the reaction proceeded). Upon completion (˜48 h), the mixture was adsorbed onto silica gel and concentrated to a powder. Flash chromatographic purification over silica (25% EtOAc in hexanes) afforded N-phenoxyphthalimide 9 as a white solid (216 mg, 90%); see below for characterization data.
O=C1c2ccccc2C(=O)N1Oc1ccccc1
null
90.3
null
263,197
ord_dataset-a7bd0db0684c464bb02ff6a36065fee3
null
1993-01-01T00:03:00
true
[CH2:1]([C:8]([C:21]#[N:22])([CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:9]([O:11]CC)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH-].[K+]>O.C(O)C.O>[CH2:14]([C:8]([C:21]#[N:22])([CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[C:9]([OH:11])=[O:10])[C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1
CCOC(=O)C(C#N)(Cc1ccccc1)Cc1ccccc1
null
null
[K+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
O
null
null
null
null
null
null
null
null
null
null
null
Ethyl 2-benzyl-2-cyano-3-phenylpropionate (3.20 g, 11 mmol) was saponified at room temperature overnight with potassium hydroxide (6.17 g, 0.11 mol) in 10% water/ethanol. The mixture was diluted with water (200 mL) and extracted with hexane (2×50 mL). The aqueous layer was acidified with 1M phosphoric acid and extracted with methylene chloride (4×100 mL). The combined organic extracts were dried over magnesium sulfate and freed of solvent to afford 2-benzyl-2-cyano-3-phenylpropionic acid (2.94 g, 11 mmol) as a colorless solid: 1H NMR (CDCl3, 300 MHz) δ 7.34 (br s, 10 H), 3.24 (dd, J=13.5, 57 Hz); mass spectrum m/e 283 (M+NH4+).
N#CC(Cc1ccccc1)(Cc1ccccc1)C(=O)O
null
100
null
1,049,954
ord_dataset-dd320ded4b3f4764af39de99491533f7
null
2011-01-01T00:04:00
true
C(OC([O:8][NH:9][C:10]([C:12]1[CH:13]=[N:14][C:15]([N:18]2[CH2:23][CH:22]3[CH:20]([CH:21]3[CH2:24][NH:25][CH2:26][C:27]3[CH:36]=[CH:35][C:34]4[C:29](=[CH:30][CH:31]=[CH:32][CH:33]=4)[CH:28]=3)[CH2:19]2)=[N:16][CH:17]=1)=[O:11])C)C(C)C.Cl.O1CCOCC1>C(Cl)Cl>[OH:8][NH:9][C:10]([C:12]1[CH:13]=[N:14][C:15]([N:18]2[CH2:23][CH:22]3[CH:20]([CH:21]3[CH2:24][NH:25][CH2:26][C:27]3[CH:36]=[CH:35][C:34]4[C:29](=[CH:30][CH:31]=[CH:32][CH:33]=4)[CH:28]=3)[CH2:19]2)=[N:16][CH:17]=1)=[O:11]
CC(C)COC(C)ONC(=O)c1cnc(N2CC3C(CNCc4ccc5ccccc5c4)C3C2)nc1
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
C1COCCO1
null
null
null
null
null
null
null
null
null
null
0.17
N-(1-Isobutoxyethoxy) 2-(6-{[(naphthalen-2-ylmethyl)amino]methyl}-3-azabicyclo[3.1.0]hex-3-yl)pyrimidine-5-carboxamide (43 mg, 0.09 mmol) was stirred in DCM (2 ml) at r.t. under N2 and 4M HCl in dioxane (45 μl, 0.18 mmol) was added. This immediately caused a solid to precipitate. The reaction was allowed to stir for 10 min and then the solvent was removed in vacuo to give the title compound as a white solid (16 mg, 50%). LCMS purity 98%, m/z 390 [M+H]+, 1H NMR (300 MHz, d6-DMSO) δ: 1.91 (2H, m), 2.50 (1H, m), 2.99 (2H, m), 3.55 (2H, m), 3.88 (2H, d, J=11.7 Hz), 4.34 (2H, m), 7.58 (2H, m), 7.68 (1H, m), 7.95 (2H, m), 8.03 (2H, m), 8.66 (2H, s), 9.11 (2H, br s), 11.07 (1H, br s).
O=C(NO)c1cnc(N2CC3C(CNCc4ccc5ccccc5c4)C3C2)nc1
null
45.6
null
979,751
ord_dataset-f886e51ba1484c76a94bce1482f1eab9
null
2010-01-01T00:07:00
true
Cl[C:2]1[C:11]2[C:6](=[N:7][CH:8]=[CH:9][CH:10]=2)[N:5]=[CH:4][CH:3]=1.[NH2:12][C:13]1[CH:18]=[C:17]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][C:24]([Cl:27])=[CH:23][CH:22]=2)[CH:16]=[CH:15][C:14]=1[S:28][C:29]1[CH:34]=[CH:33][C:32]([OH:35])=[CH:31][CH:30]=1>>[Cl:27][C:24]1[CH:25]=[CH:26][C:21]([CH2:20][O:19][C:17]2[CH:16]=[CH:15][C:14]([S:28][C:29]3[CH:34]=[CH:33][C:32]([OH:35])=[CH:31][CH:30]=3)=[C:13]([NH:12][C:2]3[C:11]4[C:6](=[N:7][CH:8]=[CH:9][CH:10]=4)[N:5]=[CH:4][CH:3]=3)[CH:18]=2)=[CH:22][CH:23]=1
Nc1cc(OCc2ccc(Cl)cc2)ccc1Sc1ccc(O)cc1
Clc1ccnc2ncccc12
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The product from Example 16c (50 mg, 0.30 mmol) was reacted with the product from Example 143a (107 mg, 0.30 mmol) for 24 h following the procedure from Example 1g giving the crude title compound which was purified by HPLC with TFA providing the product as a trifluoroacetic acid (50 mg, 27%). 1H NMR (300 MHz, DMSO-d6) δ ppm: 5.14 (s, 2 H) 6.31 (d, J=7.36 Hz, 1 H) 6.64 (d, J=8.82 Hz, 2 H) 7.05-7.40 (m, J=8.46 Hz, 4 H) 7.46 (m, J=5.52 Hz, 3 H) 7.93 (m, J=4.41 Hz, 1 H) 8.48 (d, J=6.98 Hz, 1 H) 9.17 (m, J=1.47 Hz, J=5.88 Hz, 3 H) 9.79 (s,1 H) 11.15 (br s, 1 H) 14.54 (br s, 1 H); MS (ESI+) m/z,486 (M+H−TFA)+; (ESI−) m/z,484 (M−H−TFA)−.
Oc1ccc(Sc2ccc(OCc3ccc(Cl)cc3)cc2Nc2ccnc3ncccc23)cc1
null
null
null
1,347,066
ord_dataset-6034127657614f02860ed057b62b882e
null
2013-01-01T00:10:00
true
[OH-].[Na+].C([O:5][C:6](=[O:26])[CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][N:13]1[CH:17]=[CH:16][C:15]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=2[O:24][CH3:25])=[N:14]1)C>CO>[CH3:25][O:24][C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][C:18]=1[C:15]1[CH:16]=[CH:17][N:13]([CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][C:6]([OH:26])=[O:5])[N:14]=1
CCOC(=O)CCCCCCn1ccc(-c2ccccc2OC)n1
null
null
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
null
8
Add 2 N sodium hydroxide (20 mL) to a solution of 7-[3-(2-Methoxyphenyl)pyrazol-1-yl]heptanoic acid ethyl ester (3.75 g, 11.4 mmol) in methanol (40 mL) at room temperature under nitrogen and stir the mixture for 8 hours. Remove the solvent under reduced pressure, dilute the residue with water (100 mL), acidify to pH 3 with 1 N HCl, extract with ethyl acetate (200 mL), and dry over sodium sulfate. Remove the solvent under reduced pressure to provide 7-[3-(2-methoxyphenyl)pyrazol-1-yl]heptanoic acid (3.06 g, 89%). APCI mass spectrum m/z 303 [C17H22N2O3+H]+.
COc1ccccc1-c1ccn(CCCCCCC(=O)O)n1
null
88.8
null
642,430
ord_dataset-ce71a906ea9c4399a2014cbaaff88c8f
null
2004-01-01T00:07:00
true
C([N:4]1[C:12]2[C:7](=[CH:8][CH:9]=[C:10]([C:13]([O:15][CH3:16])=[O:14])[CH:11]=2)[C:6](=[C:17](OCC)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:5]1=[O:27])(=O)C.[CH3:28][N:29]([CH3:44])[CH2:30][CH2:31][N:32]([C:37]1[CH:43]=[CH:42][C:40]([NH2:41])=[CH:39][CH:38]=1)[C:33](=[O:36])[CH2:34][CH3:35]>>[CH3:44][N:29]([CH3:28])[CH2:30][CH2:31][N:32]([C:37]1[CH:38]=[CH:39][C:40]([NH:41]/[C:17](=[C:6]2\[C:5](=[O:27])[NH:4][C:12]3[C:7]\2=[CH:8][CH:9]=[C:10]([C:13]([O:15][CH3:16])=[O:14])[CH:11]=3)/[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[CH:42][CH:43]=1)[C:33](=[O:36])[CH2:34][CH3:35]
CCC(=O)N(CCN(C)C)c1ccc(N)cc1
CCOC(=C1C(=O)N(C(C)=O)c2cc(C(=O)OC)ccc21)c1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Prepared from 1-acetyl-3-(1-ethoxy-1-phenylmethylene)-6-methoxycarbonyl-2-indolinone and 4-(N-(2-dimethylamino-ethyl)-N-propionyl-amino)-aniline Rf value: 0.5 (silica gel, methylene chloride/methanol=9:1) C30H32N4O4
CCC(=O)N(CCN(C)C)c1ccc(N/C(=C2\C(=O)Nc3cc(C(=O)OC)ccc32)c2ccccc2)cc1
null
null
null
1,322,932
ord_dataset-cfad8b3f00044bcda60a96b019f09872
null
2013-01-01T00:08:00
true
Cl.[NH2:2][CH2:3][C:4]1[C:13](=[O:14])[C:12]2[C:7](=[N:8][C:9]([C:15]([F:18])([F:17])[F:16])=[CH:10][CH:11]=2)[N:6]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:5]=1[C:25]([O:27][CH3:28])=[O:26].[Cl:29][C:30]1[CH:31]=[C:32]([CH:36]=[CH:37][C:38]=1[Cl:39])[C:33](O)=[O:34]>>[CH3:28][O:27][C:25]([C:5]1[N:6]([C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)[C:7]2[C:12]([C:13](=[O:14])[C:4]=1[CH2:3][NH:2][C:33](=[O:34])[C:32]1[CH:36]=[CH:37][C:38]([Cl:39])=[C:30]([Cl:29])[CH:31]=1)=[CH:11][CH:10]=[C:9]([C:15]([F:16])([F:17])[F:18])[N:8]=2)=[O:26]
O=C(O)c1ccc(Cl)c(Cl)c1
COC(=O)c1c(CN)c(=O)c2ccc(C(F)(F)F)nc2n1-c1ccccc1
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
3-[(3,4-Dichloro-benzoylamino)-methyl]-4-oxo-1-phenyl-7-trifluoromethyl-1,4-dihydro-[1,8]-naphthyridine-2-carboxylic acid methyl ester was prepared starting from intermediate J and 3,4-dichlorobenzoic acid. 1H NMR (400 MHz, DMSO-d6) δ ppm 8.90 (d, J=8.06 Hz, 1H) 8.80 (t, J=4.63 Hz, 1H) 8.04 (d, J=1.81 Hz, 1H) 7.97 (d, J=8.06 Hz, 1H) 7.67-7.83 (m, 2H) 7.51-7.60 (m, 3H) 7.35-7.47 (m, 2H) 4.44 (d, J=4.83 Hz, 2H) 3.39 (s, 3H). MS calcd. for C25H16Cl2F3N3O4 [(M+H)+] 549.0, obsd. 549.9.
COC(=O)c1c(CNC(=O)c2ccc(Cl)c(Cl)c2)c(=O)c2ccc(C(F)(F)F)nc2n1-c1ccccc1
null
null
null
1,730,273
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+].[C:14]1([CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][O:26][C:27](N2C=CC=CC2=O)=[O:28])[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>O.C1COCC1>[OH:4][C@@H:3]([CH3:5])[C@@H:2]([NH:1][C:27]([O:26][CH2:25][CH2:24][CH2:23][CH2:22][CH2:21][CH2:20][C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1)=[O:28])[C:6]([OH:8])=[O:7]
C[C@H](O)[C@@H](N)C(=O)O
O=C(OCCCCCCc1ccccc1)n1ccccc1=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
15
To a stirred mixture of D-threonine (0.12 g, 1.0 mmol) and NaHCO3 (0.13 g, 1.5 mmol) in H2O (3.5 mL), the crude mixture containing 6-phenylhexyl-2-pyridyl-carbonate and 6-phenylhexyl-2-oxopyridine 1-carboxylate (0.45 g, 1.5 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 (0.25 g, 78%) as transparent oil, which was used in the next step without further purification. MS (ESI) m/z: 324 [M−H]+; (ESI) m/z: 322 [M−H]−. 1H NMR (DMSO-d6): δ 1.08 (d, J=6.4 Hz, 3H), 1.24-1.40 (m, 4H), 1.46-1.63 (m, 4H), 2.56 (t, J=7.6 Hz, 2H), 3.88-3.99 (m, 3H), 4.00-4.12 (m, 1H), 6.67 (d, J=9.0 Hz, 1H), 7.13-7.21 (m, 3H), 7.22-7.31 (m, 2H), 12.40 (br s, 1H).
C[C@H](O)[C@@H](NC(=O)OCCCCCCc1ccccc1)C(=O)O
null
77.3
null
712,203
ord_dataset-c8a367b56b4f406b878f51867b157d19
null
2006-01-01T00:06:00
true
[CH:1]1([NH2:7])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[Cl:8][C:9]1[CH:14]=[C:13]([Cl:15])[CH:12]=[CH:11][C:10]=1[C:16]1[N:17]=[C:18]([C:30](OCC)=[O:31])[N:19]([CH3:29])[C:20]=1[C:21]1[CH:26]=[CH:25][C:24]([Cl:27])=[CH:23][C:22]=1[Cl:28]>>[CH:1]1([NH:7][C:30]([C:18]2[N:19]([CH3:29])[C:20]([C:21]3[CH:26]=[CH:25][C:24]([Cl:27])=[CH:23][C:22]=3[Cl:28])=[C:16]([C:10]3[CH:11]=[CH:12][C:13]([Cl:15])=[CH:14][C:9]=3[Cl:8])[N:17]=2)=[O:31])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1
CCOC(=O)c1nc(-c2ccc(Cl)cc2Cl)c(-c2ccc(Cl)cc2Cl)n1C
NC1CCCCC1
null
null
null
null
null
null
null
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 essentially the same procedure as Example 30, Step E, but using cyclohexylamine (1 mL), ethyl 4,5-di-(2,4-dichlorophenyl)-1-methylimidazole-2-carboxylate (10 mg, 0.022 mmol) from Example 30, Step D was converted to the title compound. HPLC/MS: 496 (M+1), 498 (100%, M+3), 500 (M+5); Rt=5.04 min.
Cn1c(C(=O)NC2CCCCC2)nc(-c2ccc(Cl)cc2Cl)c1-c1ccc(Cl)cc1Cl
null
null
null
302,279
ord_dataset-bfcf5a01f1a04ec585ba3f28cb93c8c9
null
1995-01-01T00:01:00
true
[C:1]1([N:7]=[C:8]=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[F:10][C:11]1[CH:29]=[CH:28][C:14]2[C:15]([CH:18]3[CH2:23][CH2:22][N:21]([CH2:24][CH2:25][CH2:26][OH:27])[CH2:20][CH2:19]3)=[N:16][O:17][C:13]=2[CH:12]=1.[ClH:30]>C1(C)C=CC=CC=1.CCOCC>[ClH:30].[F:10][C:11]1[CH:29]=[CH:28][C:14]2[C:15]([CH:18]3[CH2:23][CH2:22][N:21]([CH2:24][CH2:25][CH2:26][O:27][C:8](=[O:9])[NH:7][C:1]4[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=4)[CH2:20][CH2:19]3)=[N:16][O:17][C:13]=2[CH:12]=1
O=C=Nc1ccccc1
OCCCN1CCC(c2noc3cc(F)ccc23)CC1
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
CCOCC
null
null
null
null
null
null
null
null
null
25
null
Phenylisocyanate (0.36 g, 3 mmol) and 3-[4-(6-fluoro-1,2-benzisoxazol-3-yl)piperidino]propanol (0.3 g, 1.1 mmol) was refluxed in toluene (25 ml) for 6 h. The mixture was cooled to room temperature and hydrochloric acid in ether was added. The resulting precipitate was recrystallized from ethanol/ether and isopropanol/ether to give 180 mg of the title compound as white crystals. M.p. 204.5°-205.5° C. MS (70 eV): m/z 397 (39%, M+), 278 (4), 259 (26), 233 (50), 178 (28), 96 (100).
O=C(Nc1ccccc1)OCCCN1CCC(c2noc3cc(F)ccc23)CC1
null
null
null
949,386
ord_dataset-3feb2a95f66e4706a4a50c977ccd9bf8
null
2010-01-01T00:04:00
true
[O:1]=[C:2]1[CH2:10][C:9]2[C:4](=[CH:5][C:6]([C:11]([C:13]3[CH:14]=[C:15]([NH:19][C:20](=[O:22])[CH3:21])[CH:16]=[CH:17][CH:18]=3)=[O:12])=[CH:7][CH:8]=2)[NH:3]1.[CH:23](OCC)=[O:24].[O-]CC.[Na+].Cl>C(O)C>[OH:24][CH:23]=[C:10]1[C:9]2[C:4](=[CH:5][C:6]([C:11]([C:13]3[CH:14]=[C:15]([NH:19][C:20](=[O:22])[CH3:21])[CH:16]=[CH:17][CH:18]=3)=[O:12])=[CH:7][CH:8]=2)[NH:3][C:2]1=[O:1]
CC(=O)Nc1cccc(C(=O)c2ccc3c(c2)NC(=O)C3)c1
CCOC=O
null
CC[O-]
Cl
[Na+]
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
78
null
N-[3-(2-Oxo-2,3-dihydro-1H-indole-6-carbonyl)-phenyl]-acetamide (0.957 g, 3.25 mmol) and ethyl formate (0.781 mL, 9.75 mmol) were dissolved in anhydrous ethanol (6.50 mL). The resulting solution was treated in dropwise fashion with a 21 wt % solution of sodium ethoxide in ethanol (6.07 mL, 16.26 mmol). This reaction mixture was heated at 78° C. for 1 h, producing a black oil. Subsequently, the reaction mixture was cooled to room temperature, and then the reaction pH was adjusted to pH 1 with dropwise addition of 1M HCl(aq) causing the formation of a pale orange precipitate. The suspension was filtered yielding an orange solid as the pure N-[3-(3-Hydroxymethylene-2-oxo-2,3-dihydro-1H-indole-6-carbonyl)-phenyl]-acetamide (0.752 g, 2.33 mmol, 71%).
CC(=O)Nc1cccc(C(=O)c2ccc3c(c2)NC(=O)C3=CO)c1
null
71.7
null
363,867
ord_dataset-c2ad1656a3ca4d08888ffb6e3f3a2742
null
1997-01-01T00:05:00
true
C[O:2][C:3](=[O:24])[C@@H:4]1[CH2:8][CH2:7][CH2:6][N:5]1[CH:9]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[C@@H:10]1[C@@H:14]([CH2:15][CH3:16])[CH2:13][CH2:12][NH:11]1.[OH-].[Na+].Cl>CO>[C:20]([O:19][C:17]([CH:9]([C@@H:10]1[C@@H:14]([CH2:15][CH3:16])[CH2:13][CH2:12][NH:11]1)[N:5]1[CH2:6][CH2:7][CH2:8][C@H:4]1[C:3]([OH:24])=[O:2])=[O:18])([CH3:23])([CH3:22])[CH3:21]
CC[C@H]1CCN[C@@H]1C(C(=O)OC(C)(C)C)N1CCC[C@H]1C(=O)OC
null
null
Cl
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
0
3
N-[(tert-Butyloxy)carbonyl-3(S)-ethylpyrrolidin-2(S)-ylmethyl]-proline methyl ester 0.081 g, 0.238 mmol) was dissolved in CH3OH (2 mL), cooled to 0° C. and treated with 1N NaOH solution (0.952 mL, 0.952 mmol). After stirring at 23° C. for 3 h, the solution was neutralized with 1N HCl (0.952 mL, 0.952 mmol), concentrated to remove the CH3OH, then lyophilized and the residue used as is.
CC[C@H]1CCN[C@@H]1C(C(=O)OC(C)(C)C)N1CCC[C@H]1C(=O)O
null
null
null
702,529
ord_dataset-c408dfed796e4354b61e312e67f7143f
null
2006-01-01T00:04:00
true
C(=O)([O-])[O-].[K+].[K+].[C:7]([O:11][C:12]([N:14]1[CH2:19][CH2:18][N:17]([C:20]([O:22][CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[C:26]([OH:30])[CH:25]=2)=[O:21])[CH2:16][CH2:15]1)=[O:13])([CH3:10])([CH3:9])[CH3:8].Br[CH2:32][CH2:33][C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1>CC(C)=O>[C:7]([O:11][C:12]([N:14]1[CH2:19][CH2:18][N:17]([C:20]([O:22][CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[C:26]([O:30][CH2:32][CH2:33][C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=3)[CH:25]=2)=[O:21])[CH2:16][CH2:15]1)=[O:13])([CH3:10])([CH3:8])[CH3:9]
CC(C)(C)OC(=O)N1CCN(C(=O)OCc2cccc(O)c2)CC1
BrCCc1ccccc1
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
25
null
potassium carbonate (0.072 g, 0.52 mmol) was added to a solution of piperazine-1,4-dicarboxylic acid (3-hydroxy)benzyl ester tert-butyl ester (0.16 g, 0.48 mmol) in acetone (5 mL) at 0° C. and the reaction mixture was stirred at 0° C. for 30 min. (2-Bromoethyl)-benzene (0.097 g, 0.52 mmol) was added and the reaction mixture was allowed to warm to room temperature and then heated under reflux for 24 h. After cooling, the reaction mixture was concentrated in vacuo and the residue was partitioned between water (20 mL) and ethyl acetate (20 mL). The organic phase was separated, washed with saturated brine (25 mL), dried (MgSO4) and concentrated in vacuo to give an oil which was purified by column chromatography [SiO2; heptane-ethyl acetate (3:1)] to yield the title compound (0.10 g, 48%) as a colourless oil. 1H-NMR (400 MHz, CDCl3): 1.46 (9H, s), 3.10 (2H, t, J=7.0 Hz), 3.40 (4H, m), 3.46 (4H, m), 4.18 (2H, t, J=7.0 Hz), 5.09 (2H, s), 6.84 (1H, m), 6.88 (1H, m), 6.91 (1H, m) and 7.22–7.34 (6H, m).
CC(C)(C)OC(=O)N1CCN(C(=O)OCc2cccc(OCCc3ccccc3)c2)CC1
null
47.3
null
277,447
ord_dataset-ad17798fcea64e26ba91604fca520090
null
1993-01-01T00:10:00
true
[C:1]([Si:5]([CH2:8]Cl)([CH3:7])[CH3:6])([CH3:4])([CH3:3])[CH3:2].[I-:10].[Na+]>CC(C)=O>[C:1]([Si:5]([CH2:8][I:10])([CH3:7])[CH3:6])([CH3:4])([CH3:3])[CH3:2]
[I-]
CC(C)(C)[Si](C)(C)CCl
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
24
t-Butyl(chloromethyl)dimethylsilane [Makoto Kumada, Mitsuo Ishikawa, Sajiro Meada and Katsuyata Ikura, J. Organometal. Chem. 2, 146, (1964)] (16.4 g, 0.1 mmol) and sodium iodide (60 g, 0.4 mmol) in acetone (500 ml) are refluxed with stirring during 24 hours. The reaction mixture is cooled, filtered and the solvent is evaporated under reduced pressure. The residue is dissolved in ether and washed with water. The organic layer is dried over sodium sulfate, filtered and concentrated under reduced pressure to afford t-butyl(iodomethyl)dimethylsilane (20.9 g, 80%) as a slightly yellow oil.
CC(C)(C)[Si](C)(C)CI
null
81,576.9
null
1,452,030
ord_dataset-a86112d52cd54525a5e36d41f18aced2
null
2014-01-01T00:07:00
true
Cl[C:2]1[N:7]=[C:6]([CH3:8])[N:5]=[C:4]([NH2:9])[N:3]=1.[Cl:10][C:11]1[CH:12]=[C:13](B(O)O)[C:14]([F:17])=[N:15][CH:16]=1.C([O-])(=O)C.[K+]>CCO.O>[Cl:10][C:11]1[CH:12]=[C:13]([C:2]2[N:7]=[C:6]([CH3:8])[N:5]=[C:4]([NH2:9])[N:3]=2)[C:14]([F:17])=[N:15][CH:16]=1
OB(O)c1cc(Cl)cnc1F
Cc1nc(N)nc(Cl)n1
null
CC(=O)[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
O
null
null
null
null
null
null
null
null
null
100
null
To a 20 mL microwave reaction tube was added 4-chloro-6-methyl-1,3,5-triazin-2-amine (Example 9, 1.00 g, 6.94 mmol), 5-chloro-2-fluoropyridin-3-ylboronic acid (Combi-Blocks, 1.62 g, 9.22 mmol), potassium acetate (Aldrich, 2.07 g, 21.1 mmol) and Am-Phos (Aldrich, 0.247 g, 0.349 mmol) in EtOH (12 mL) and water (1.2 mL). The mixture was degassed by bubbling argon through for 5 min. The tube was heated in an microwave reactor (Biotage) at 100° C. for 20 min. The reaction mixture was partitioned between water (100 mL) and 25% IPA in chloroform with 1% NH4OH (60 mL). The aqueous phase was extracted with 25% IPA in chloroform with 1% NH4OH (2×50 mL). The combined organic phases were washed with saturated aqueous sodium chloride (40 mL). The organic phase was dried over sodium sulfate, filtered and concentrated in vacuo. Adding DCM to the residue resulted in precipitate formation. The solid was collected via filtration and washed with MeOH to afford 4-(5-chloro-2-fluoropyridin-3-yl)-6-methyl-1,3,5-triazin-2-amine (0.937 g) as a light yellow powder. The filtrate and the wash were combined and concentrated, then purified by column chromatography (eluent: iPrOH (w/10% NH4OH) in CHCl3 0.25% to 6.25%) followed by washing with MeOH to afford additional product (0.149 g) as a white solid. The total yield is 1.08 g (65%). 1H NMR (400 MHz, DMSO-d6) δ ppm 8.54 (dd, J=8.02, 2.74 Hz, 1H) 8.46-8.51 (m, 1H) 7.73 (s, 2H) 2.37 (s, 3H). m/z (ESI, positive ion) m/z: 240.1 (M+H)+.
Cc1nc(N)nc(-c2cc(Cl)cnc2F)n1
null
56.3
null
1,363,750
ord_dataset-d932d1d683704a8bad3d064bcb197acc
null
2013-01-01T00:11:00
true
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[CH2:10][CH:11]([CH3:16])[C:12](=[O:15])[NH:13][N:14]=2)=[CH:5][CH:4]=1.CI.[C:19]([O-])([O-])=O.[Cs+].[Cs+]>>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[CH:10]=[C:11]([CH3:16])[C:12](=[O:15])[N:13]([CH3:19])[N:14]=2)=[CH:5][CH:4]=1
O=C([O-])[O-]
COc1ccc(C2=NNC(=O)C(C)C2)cc1
null
[Cs+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CI
null
null
null
null
null
null
null
null
null
null
null
null
The product of step 2 (6-(4-methoxy-phenyl)-2,4-dimethyl-2H-pyridazin-3-one) was prepared as described for example 22 step 2 using 6-(4-methoxy-phenyl)-4-methyl-4,5-dihydro-2H-pyridazin-3-one, MeI and Cs2CO3.
COc1ccc(-c2cc(C)c(=O)n(C)n2)cc1
null
null
null
1,403,102
ord_dataset-7456bda2326f4bebaa874a5474d4cc0d
null
2014-01-01T00:03:00
true
[CH:1]([O:4][C:5]([N:7]1[CH2:12][CH2:11][CH:10]([CH:13]2[CH2:17][C:16]3[CH:18]=[C:19](B4OC(C)(C)C(C)(C)O4)[CH:20]=[CH:21][C:15]=3[O:14]2)[CH2:9][CH2:8]1)=[O:6])([CH3:3])[CH3:2].Br[C:32]1[CH:37]=[CH:36][C:35]([S:38]([CH3:41])(=[O:40])=[O:39])=[CH:34][N:33]=1>>[CH:1]([O:4][C:5]([N:7]1[CH2:12][CH2:11][CH:10]([CH:13]2[CH2:17][C:16]3[CH:18]=[C:19]([C:32]4[CH:37]=[CH:36][C:35]([S:38]([CH3:41])(=[O:40])=[O:39])=[CH:34][N:33]=4)[CH:20]=[CH:21][C:15]=3[O:14]2)[CH2:9][CH2:8]1)=[O:6])([CH3:3])[CH3:2]
CC(C)OC(=O)N1CCC(C2Cc3cc(B4OC(C)(C)C(C)(C)O4)ccc3O2)CC1
CS(=O)(=O)c1ccc(Br)nc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound is prepared from 4-[5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-2,3-dihydro-benzofuran-2-yl]-piperidine-1-carboxylic acid isopropyl ester and 2-bromo-5-methanesulfonyl-pyridine following a procedure analogous to that described in Example 1.
CC(C)OC(=O)N1CCC(C2Cc3cc(-c4ccc(S(C)(=O)=O)cn4)ccc3O2)CC1
null
58
null
1,113,520
ord_dataset-375a420ee9b042918ddca20f02df37d3
null
2011-01-01T00:11:00
true
[CH2:1]([N:3]1[C:7]2=[N:8][C:9]([CH2:48][CH3:49])=[C:10]([CH2:19][NH:20][C:21]([C:23]3[CH:28]=[CH:27][CH:26]=[C:25]([C:29]([NH:31][CH2:32][C:33]4[CH:34]=[C:35]([C:40]5[CH:45]=[CH:44][CH:43]=[C:42]([CH2:46][OH:47])[CH:41]=5)[C:36]([F:39])=[CH:37][CH:38]=4)=[O:30])[CH:24]=3)=[O:22])[C:11]([NH:12][CH:13]3[CH2:18][CH2:17][O:16][CH2:15][CH2:14]3)=[C:6]2[CH:5]=[N:4]1)[CH3:2]>C1COCC1.O=[Mn]=O>[CH2:1]([N:3]1[C:7]2=[N:8][C:9]([CH2:48][CH3:49])=[C:10]([CH2:19][NH:20][C:21]([C:23]3[CH:28]=[CH:27][CH:26]=[C:25]([C:29]([NH:31][CH2:32][C:33]4[CH:34]=[C:35]([C:40]5[CH:45]=[CH:44][CH:43]=[C:42]([CH:46]=[O:47])[CH:41]=5)[C:36]([F:39])=[CH:37][CH:38]=4)=[O:30])[CH:24]=3)=[O:22])[C:11]([NH:12][CH:13]3[CH2:18][CH2:17][O:16][CH2:15][CH2:14]3)=[C:6]2[CH:5]=[N:4]1)[CH3:2]
CCc1nc2c(cnn2CC)c(NC2CCOCC2)c1CNC(=O)c1cccc(C(=O)NCc2ccc(F)c(-c3cccc(CO)c3)c2)c1
null
null
O=[Mn]=O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
25
16
To N-{[1,6-diethyl-4-(tetrahydro-2H-pyran-4-ylamino)-1H-pyrazolo[3,4-b]pyridin-5-yl]methyl}-N′-{[6-fluoro-3′-(hydroxymethyl)-3-biphenylyl]methyl}-1,3-benzenedicarboxamide (0.665 g, 1 mmol) in THF (20 mL) was added MnO2 (0.869 g, 10.00 mmol) and the mixture was stirred at room temperature for 16 h. More MnO2 (10 eq) was added and stirred at room temperature for 4 h and then again for 22 h and then more MnO2 (10 eq) was added. This mixture was stirred at room temperature for 21 h and 94 h then filtered and concentrated to afford the title compound (0.6472 g, 98%). LC-MS m/z 663 (M+H)+.
CCc1nc2c(cnn2CC)c(NC2CCOCC2)c1CNC(=O)c1cccc(C(=O)NCc2ccc(F)c(-c3cccc(C=O)c3)c2)c1
null
97.7
null
117,853
ord_dataset-3708161f4ba04e959b9a7a8d59fd86e1
null
1984-01-01T00:05:00
true
[C:1]([NH:3][C:4](=[N:7][CH2:8][CH2:9][S:10][CH2:11][C:12]1[NH:16][CH:15]=[N:14][C:13]=1[CH3:17])SC)#[N:2].[CH2:18]([NH2:23])[CH2:19][CH2:20][C:21]#[CH:22]>C(#N)C>[C:1]([NH:3][C:4]([NH:7][CH2:8][CH2:9][S:10][CH2:11][C:12]1[NH:16][CH:15]=[N:14][C:13]=1[CH3:17])=[N:23][CH2:18][CH2:19][CH2:20][C:21]#[CH:22])#[N:2]
CSC(=NCCSCc1[nH]cnc1C)NC#N
C#CCCCN
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
96
A mixture of N-cyano-N'-{2-[(4-methyl-5-imidazolyl)methylthio]ethyl}-S-methylisothiourea (3.00 g., 0.0111 mole) and 4-pentyn-1-amine (3.69 g., 0.0445 mole) in 60 ml. of acetonitrile was stirred at reflux for 24 hours, and then allowed to stand at room temperature for 96 hours. The solvent and excess amine were removed under reduced pressure and the residual yellow gum was purified by chromatography on 50 g. of 100-200 mesh silica gel, using gradient elution with methylene chloride/methanol (99:1-96:4). The middle fractions indicated by TLC to be pure were combined and evaporated to give 1.91 g. of yellow gum which was crystallized at -15° C. from 18 ml. of ethyl acetate. The resulting white solid (1.25 g.) was recrystallized at -15° C. from 10 ml. of acetonitrile to give 1.063 g. of product; m.p. 99°-103° C.
C#CCCCN=C(NC#N)NCCSCc1[nH]cnc1C
null
null
null
1,401,261
ord_dataset-7456bda2326f4bebaa874a5474d4cc0d
null
2014-01-01T00:03:00
true
C(OC([N:8]1[CH2:12][CH2:11][C@H:10]([O:13][NH2:14])[CH2:9]1)=O)(C)(C)C.[ClH:15]>CCOC(C)=O>[ClH:15].[ClH:15].[NH:8]1[CH2:12][CH2:11][C@H:10]([O:13][NH2:14])[CH2:9]1
CC(C)(C)OC(=O)N1CC[C@H](ON)C1
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
null
(S)-1-tert-Butoxycarbonyl-3-pyrrolidinyloxyamine (1.67 g) was dissolved in a 5M HCl solution in EtOAc (20 ml). After 1 h the solvent was removed under reduced pressure to give (S)-3-pyrrolidinyloxyamine dihydrochloride (1.04 g, 73%) as an off-white solid.
NO[C@H]1CCNC1
null
73
null
332,062
ord_dataset-1558660634294cc8ad7e01746e9083fd
null
1996-01-01T00:06:00
true
[CH2:1]([C:3]1[CH:4]=[C:5]([OH:20])[CH:6]=[CH:7][C:8]=1[O:9][C:10]1[CH:15]=[CH:14][C:13]([O:16][CH:17]([CH3:19])[CH3:18])=[CH:12][CH:11]=1)[CH3:2].C(=O)([O-])[O-].[K+].[K+].[Br:27][C:28]([Br:32])=[CH:29][CH2:30]Br>CN(C)C=O>[CH2:1]([C:3]1[CH:4]=[C:5]([O:20][CH2:30][CH:29]=[C:28]([Br:32])[Br:27])[CH:6]=[CH:7][C:8]=1[O:9][C:10]1[CH:15]=[CH:14][C:13]([O:16][CH:17]([CH3:19])[CH3:18])=[CH:12][CH:11]=1)[CH3:2]
BrCC=C(Br)Br
CCc1cc(O)ccc1Oc1ccc(OC(C)C)cc1
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
0
null
To a mixture of 0.65 g of 3-ethyl-4-(4-isopropoxyphenoxy)phenol, 0.35 g of potassium carbonate and 10 ml of N,N-dimethylformamide, a solution prepared by dissolving 0.73 g of 1,1,3-tribromo-1-propene in 5 ml of N,N-dimethylformamide was added dropwise at room temperature with stirring. After stirring at room temperature for 12 hours, the reaction solution was poured into ice-water, and extracted twice with 50 ml, of diethyl ether. Then, the ether layers were combined, washed with water, dried over anhydrous magnesium sulfate and then concentrated to give a crude product. This crude product was subjected to silica gel chromatography to give 0.80 g of 3-ethyl-4-(4-isopropoxyphenoxy)-1-(3,3-dibromo-2-propenyloxy)benzene, yield 71%; nD23.0 1.5761.
CCc1cc(OCC=C(Br)Br)ccc1Oc1ccc(OC(C)C)cc1
null
71.3
null
425,210
ord_dataset-1ecf96d88f254270bff816ee7eeffef6
null
1999-01-01T00:02:00
true
N(C(OCC)=O)=NC(OCC)=O.O[C@H:14]1[CH2:18][N:17]([C:19]([O:21][CH2:22][C:23]2[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[CH:25][CH:24]=2)=[O:20])[C@H:16]([C:32]([N:34]2[CH2:39][CH2:38][N:37]([CH2:40][CH2:41][O:42][C:43]([O:45][CH2:46][C:47]3[CH:52]=[CH:51][C:50]([N+:53]([O-:55])=[O:54])=[CH:49][CH:48]=3)=[O:44])[CH2:36][CH2:35]2)=[O:33])[CH2:15]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[SH:75]CC(O)=O>O1CCCC1>[SH:75][C@@H:14]1[CH2:18][N:17]([C:19]([O:21][CH2:22][C:23]2[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[CH:25][CH:24]=2)=[O:20])[C@H:16]([C:32]([N:34]2[CH2:39][CH2:38][N:37]([CH2:40][CH2:41][O:42][C:43]([O:45][CH2:46][C:47]3[CH:52]=[CH:51][C:50]([N+:53]([O-:55])=[O:54])=[CH:49][CH:48]=3)=[O:44])[CH2:36][CH2:35]2)=[O:33])[CH2:15]1
O=C(O)CS
O=C(OCCN1CCN(C(=O)[C@@H]2C[C@@H](O)CN2C(=O)OCc2ccc([N+](=O)[O-])cc2)CC1)OCc1ccc([N+](=O)[O-])cc1
null
CCOC(=O)N=NC(=O)OCC
c1ccc(P(c2ccccc2)c2ccccc2)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
0.17
A solution of 36.5 g of diethyl azodicarboxylate in 100 ml of tetrahydrofuran was added dropwise, whilst ice-cooling, to a solution of 105 g of (2S,4R)-4-hydroxy-2-{4-[2-(4-nitrobenzyloxycarbonyl)oxyethyl]-1-piperazinylcarbonyl}-1-(4-nitrobenzyloxycarbonyl)pyrrolidine [prepared as described in steps 90(b)(i), 90(b)(i') and 90(b)(i") above] and 55 g of triphenylphosphine in 700 ml of tetrahydrofuran, and the resulting mixture was stirred at the same temperature for 10 minutes. A solution of 15.9 g of mercaptoacetic acid in 100 ml of tetrahydrofuran was then added dropwise to the mixture, and the mixture was stirred at room temperature for 1 hour. At the end of this time, the reaction mixture was concentrated by evaporation under reduced pressure, and the concentrate was dissolved in 1.5 liters of ethyl acetate. The resulting solution was then washed with water and with an aqueous solution of sodium chloride, in that order, after which it was dried over anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure, and then the residue was mixed with 400 ml of diisopropyl ether. The diisopropyl ether-soluble materials were extracted and discarded. The same extraction operations were repeated four times, and then the resulting residue was purified by column chromatography through 3 kg of silica gel, using a gradient elution method, with mixtures of ethyl acetate and methanol ranging from 1:0 to 20:1 by volume as the eluent, to give 88.4 g of the title compound, as a colorless powder.
O=C(OCCN1CCN(C(=O)[C@@H]2C[C@H](S)CN2C(=O)OCc2ccc([N+](=O)[O-])cc2)CC1)OCc1ccc([N+](=O)[O-])cc1
null
82.9
null
1,173,111
ord_dataset-d24cc23b3db94284bb83a2ccdd9eb880
null
2012-01-01T00:05:00
true
Br[C:2]1[C:10]2[C:5](=[N:6][CH:7]=[CH:8][CH:9]=2)[N:4]([S:11]([C:14]2[CH:19]=[CH:18][C:17]([CH3:20])=[CH:16][CH:15]=2)(=[O:13])=[O:12])[CH:3]=1.[Cl:21][C:22]1[CH:27]=[C:26](B(O)O)[CH:25]=[CH:24][N:23]=1.C(=O)([O-])[O-].[Na+].[Na+]>COCCOC.C(OCC)(=O)C.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>[Cl:21][C:22]1[CH:27]=[C:26]([C:2]2[C:10]3[C:5](=[N:6][CH:7]=[CH:8][CH:9]=3)[N:4]([S:11]([C:14]3[CH:19]=[CH:18][C:17]([CH3:20])=[CH:16][CH:15]=3)(=[O:13])=[O:12])[CH:3]=2)[CH:25]=[CH:24][N:23]=1
Cc1ccc(S(=O)(=O)n2cc(Br)c3cccnc32)cc1
OB(O)c1ccnc(Cl)c1
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
COCCOC
CCOC(C)=O
null
null
null
null
null
null
null
null
null
null
null
A mixture of azaindole 3 (80 mg, 0.23 mmol), 2-chloropyridine-4-boronic acid (41 mg, 0.27 mmol), Pd(Ph3P)4 (20 mg, 0.11 mmol) and 2 M sodium carbonate (0.34 mL, 0.68 mmol) in 2 mL of DME was microwaved on high at 160° C. for under nitrogen for 15 minutes. Diluted with ethyl acetate and the organic phase washed with water and brine then dried (Na2SO4) and concentrated in vacuo. The residue was subjected to flash chromatography (40% EtOAc/60% hexanes) to give 60 mg (68%) of the desired product 14. 1H NMR CDCl3 8.6 (d, 2H), 8.1 (m, 4H), 7.25 (m, 5H), 2.5 (s, 3H). The 2-chloropyridine could be displaced, for example, with benzylamine in a microwave reaction at 250° C. for 30 min followed by deprotection to give compound 15.
Cc1ccc(S(=O)(=O)n2cc(-c3ccnc(Cl)c3)c3cccnc32)cc1
null
68
null
1,183,857
ord_dataset-9cd817a75dfc4fe7ad19d4232772d5ff
null
2012-01-01T00:07:00
true
[NH2:1][C@:2]1([C:14]([O:16][CH3:17])=[O:15])[CH2:6][CH2:5][C@@H:4]([C:7]2[CH:12]=[CH:11][C:10]([Br:13])=[CH:9][CH:8]=2)[CH2:3]1.[CH2:18]([O:25][C:26](ON1C(=O)CCC1=O)=[O:27])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.C(=O)([O-])[O-].[K+].[K+]>C(#N)C.O>[CH2:18]([O:25][C:26]([NH:1][C@:2]1([C:14]([O:16][CH3:17])=[O:15])[CH2:6][CH2:5][C@@H:4]([C:7]2[CH:12]=[CH:11][C:10]([Br:13])=[CH:9][CH:8]=2)[CH2:3]1)=[O:27])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1
COC(=O)[C@@]1(N)CC[C@@H](c2ccc(Br)cc2)C1
O=C(OCc1ccccc1)ON1C(=O)CCC1=O
null
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CC#N
null
null
null
null
null
null
null
null
null
25
1
To (1R,3R)-methyl 1-amino-3-(4-bromophenyl)cyclopentanecarboxylate (1.5 g, 5.03 mmol) in acetonitrile (7.2 ml) and water (1.800 ml) was added N-(Benzyloxycarbonyloxy)succinimide (1.254 g, 5.03 mmol) followed by potassium carbonate (0.695 g, 5.03 mmol). The reaction mixture was stirred for 1 hour at room temperature. The solvent was removed and the remaining aqueous slurry was taken up in water and ethyl acetate. The organic layer was removed and washed with brine, dried over MgSO4 and concentrated in vacuo. The crude was purified by flash chromatography to yield (1R,3R)-methyl 1-(benzyloxycarbonylamino)-3-(4-bromophenyl)cyclopentanecarboxylate (1.4 g, 3.24 mmol, 64.4% yield) as an off white gum.
COC(=O)[C@@]1(NC(=O)OCc2ccccc2)CC[C@@H](c2ccc(Br)cc2)C1
null
64.4
null
195,473
ord_dataset-b83b16f2fb1a4f8782f3d82c1766cc6b
null
1989-01-01T00:08:00
true
Cl[CH2:2][CH2:3][CH2:4][CH2:5][O:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1/[CH:13]=[CH:14]/[C:15]1[S:16][C:17]2[CH:23]=[CH:22][CH:21]=[CH:20][C:18]=2[N:19]=1.[NH:24]1[CH:28]=[CH:27][N:26]=[CH:25]1.Cl>>[N:24]1([CH2:2][CH2:3][CH2:4][CH2:5][O:6][C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=2/[CH:13]=[CH:14]/[C:15]2[S:16][C:17]3[CH:23]=[CH:22][CH:21]=[CH:20][C:18]=3[N:19]=2)[CH:28]=[CH:27][N:26]=[CH:25]1
c1c[nH]cn1
ClCCCCOc1ccccc1/C=C/c1nc2ccccc2s1
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The named compound was prepared as described in Example 38 starting with (H) of Example 38 (3.0 g, 8.7 mmol) and using imidazole in place of dipropylamine to produce 1.5 g (46% yield) of the named compound as the HCl salt, mp 214°-217° C. IR(KBr): 3400, 1595 cm-1. MS: 376(MH+). 1H NMR (CD3OD): δ 9.01 (s, 1H), 7.88-6.91 (m, 12H), 4.21 (t, J=5.2 Hz, 2H), 3.34 (t, J=5.2 Hz, 2H), 2.25 (m, 4H).
C(=C/c1ccccc1OCCCCn1ccnc1)\c1nc2ccccc2s1
null
46
null
179,188
ord_dataset-4d84abdf99524e0fb6c42ab2a3300790
null
1988-01-01T00:10:00
true
[F:1][C:2]1[CH:3]=[C:4]([C:10]([F:13])([F:12])[F:11])[CH:5]=[CH:6][C:7]=1[O:8]C.S(=O)(=O)(O)O.[N+:19]([O-])([O-:21])=[O:20].[K+]>ClCCCl>[F:1][C:2]1[CH:3]=[C:4]([C:10]([F:13])([F:12])[F:11])[CH:5]=[C:6]([N+:19]([O-:21])=[O:20])[C:7]=1[OH:8]
O=[N+]([O-])[O-]
COc1ccc(C(F)(F)F)cc1F
null
O=S(=O)(O)O
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCCl
null
null
null
null
null
null
null
null
null
null
0
null
The product from (c) (4.1 g) in 1,2-dichloro-ethane (25 ml) was chilled to -10° C. and concentrated sulphuric acid (25 ml) added. The mixture was stirred and kept at -5° to -10° C. while potassium nitrate (2.3 g) was added in portions over a period of 30 minutes. The mixture was stirred for a further 30 minutes at below 0° C. and then poured on to ice (150 ml). The mixture was extracted with chloroform (150 ml) and the extracts washed with water (100 ml), dried (MgSO4) and evaporated to give 3-fluoro-4-hydroxy-5-nitrobenzotrifluoride as a pale yellow liquid (4.1 g).
O=[N+]([O-])c1cc(C(F)(F)F)cc(F)c1O
null
86.2
null
453,439
ord_dataset-3bcdb559226a40d89406474c02d082d1
null
1999-01-01T00:12:00
true
[Cl:1][C:2]1[CH:3]=[C:4]([C:9]2[O:13][N:12]=[C:11]([OH:14])[CH:10]=2)[CH:5]=[CH:6][C:7]=1[Cl:8].[C:15]([O:19][C:20]([NH:22][CH2:23][CH2:24]O)=[O:21])([CH3:18])([CH3:17])[CH3:16]>>[C:15]([O:19][C:20]([NH:22][CH2:23][CH2:24][O:14][C:11]1[CH:10]=[C:9]([C:4]2[CH:5]=[CH:6][C:7]([Cl:8])=[C:2]([Cl:1])[CH:3]=2)[O:13][N:12]=1)=[O:21])([CH3:18])([CH3:17])[CH3:16]
CC(C)(C)OC(=O)NCCO
Oc1cc(-c2ccc(Cl)c(Cl)c2)on1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
5-(3,4-Dichlorophenyl)-3-hydroxyisoxazole (0.3 g) and 2-(N-tert-butoxycarbonylamino)ethanol (0.23 g) were subjected to reaction and post-treatment in a similar manner to that described in Example 9(a) to obtain the title compound (0.41 g, 85%) as a colorless powder.
CC(C)(C)OC(=O)NCCOc1cc(-c2ccc(Cl)c(Cl)c2)on1
null
84.2
null
790,138
ord_dataset-530502f8e61e455784f93c5faa45c94b
null
2007-01-01T00:09:00
true
[C:1]([N:4]1[CH2:9][CH2:8][NH:7][CH2:6][CH2:5]1)(=[O:3])[CH3:2].Br[CH2:11][CH2:12][OH:13].C(=O)([O-])[O-].[K+].[K+]>C(#N)C>[C:1]([N:4]1[CH2:9][CH2:8][N:7]([CH2:11][CH2:12][OH:13])[CH2:6][CH2:5]1)(=[O:3])[CH3:2]
CC(=O)N1CCNCC1
OCCBr
null
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC#N
null
null
null
null
null
null
null
null
null
null
null
null
A mixture of 1-acetylpiperazine (2.5 g, 19.5 mmol), 2-bromoethanol (1.38 ml, 19.5 mmol) and potassium carbonate (6.7 g, 48.8 mmol) in acetonitrile (30 ml) was heated at reflux for 3 hours. The mixture was cooled, filtered and concentrated under reduced pressure. The residue was purified by column chromatography eluting with methylene chloride/methanol (9/1) to give 2-(4-acetylpiperazin-1-yl)ethanol (1.89 g, 56%) as a colourless oil.
CC(=O)N1CCN(CCO)CC1
null
56.3
null
1,581,517
ord_dataset-380e279f82154dba9e08ab51b3bdd08a
null
2015-01-01T00:05:00
true
[NH2:1][C:2]1[C:7]([C:8]([F:11])([F:10])[F:9])=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:12][OH:13]>C(Cl)Cl.[O-2].[O-2].[Mn+4]>[NH2:1][C:2]1[C:7]([C:8]([F:9])([F:10])[F:11])=[CH:6][CH:5]=[CH:4][C:3]=1[CH:12]=[O:13]
Nc1c(CO)cccc1C(F)(F)F
null
null
[Mn+4]
[O-2]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
25
18
Manganese dioxide (27 g, 0.32 mol) was added to a solution of [2-amino-3-(trifluoromethyl)phenyl]methanol (12.0 g, 0.063 mol) in DCM (150 mL) and the mixture was stirred for 18 h at room temperature. After this time, more manganese dioxide (27 g, 0.32 mol) was added, and the reaction mixture was left for a further 18 h. The reaction mixture was filtered through Celite, then the solvent was removed in vacuo to afford the title compound (9.5 g, 80%) as an orange oil. δH (DMSO-d6) 9.93 (s, 1H), 7.68 (m, 2H), 6.82 (m, 3H).
Nc1c(C=O)cccc1C(F)(F)F
null
79.7
null
474,579
ord_dataset-d56f0a7ec215495c92e641d9fa932d28
null
2000-01-01T00:09:00
true
[SH:1][C:2]1[NH:3][C:4]2[CH:10]=[CH:9][CH:8]=[CH:7][C:5]=2[N:6]=1.[CH2:11]([N:15]=[C:16]=[O:17])[CH2:12][CH2:13][CH3:14]>>[CH2:11]([NH:15][C:16]([N:3]1[C:4]2[CH:10]=[CH:9][CH:8]=[CH:7][C:5]=2[NH:6][C:2]1=[S:1])=[O:17])[CH2:12][CH2:13][CH3:14]
CCCCN=C=O
Sc1nc2ccccc2[nH]1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
135
null
The mixture of 2-mercaptobenzimidazole (29.30 g, 0.195 mole) and butyl isocyanate (48.3 mL, 0.33 mole) in a 500 ml of round-bottom flask equipped with a condenser was heated to 130-140° C. in an oil bath for 45 min. After the reaction mixture was cooled to room temperature, the solid was filtered, washed with hexane, and dried under vacuum to give 43.48 g (89%) of 1-(butylcarbamoyl)-1,3-dihydrobenz-imidazole-2-thione as white crystals: mp 179-180° C.
CCCCNC(=O)n1c(=S)[nH]c2ccccc21
null
89.4
null
1,023,845
ord_dataset-136cfada6ce247b4919085a57363459e
null
2011-01-01T00:01:00
true
[C:1]([Si:5]([CH3:38])([CH3:37])[O:6][C:7]1[CH:8]=[C:9]([C:13]2[N:14]=[C:15]([N:31]3[CH2:36][CH2:35][O:34][CH2:33][CH2:32]3)[C:16]3[S:21][C:20]([CH2:22][N:23]4[CH2:28][C@H:27]([CH3:29])[NH:26][C@H:25]([CH3:30])[CH2:24]4)=[CH:19][C:17]=3[N:18]=2)[CH:10]=[CH:11][CH:12]=1)([CH3:4])([CH3:3])[CH3:2].C(N(CC)CC)C.[C:46](Cl)(=[O:48])[CH3:47]>ClCCl>[C:1]([Si:5]([CH3:38])([CH3:37])[O:6][C:7]1[CH:8]=[C:9]([C:13]2[N:14]=[C:15]([N:31]3[CH2:32][CH2:33][O:34][CH2:35][CH2:36]3)[C:16]3[S:21][C:20]([CH2:22][N:23]4[CH2:24][C@H:25]([CH3:30])[N:26]([C:46](=[O:48])[CH3:47])[C@H:27]([CH3:29])[CH2:28]4)=[CH:19][C:17]=3[N:18]=2)[CH:10]=[CH:11][CH:12]=1)([CH3:4])([CH3:2])[CH3:3]
CC(=O)Cl
C[C@@H]1CN(Cc2cc3nc(-c4cccc(O[Si](C)(C)C(C)(C)C)c4)nc(N4CCOCC4)c3s2)C[C@H](C)N1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
CCN(CC)CC
null
null
null
null
null
null
null
null
null
null
8
To a solution of 2-[3-(tert-butyl-dimethyl-silanyloxy)-phenyl]-6-((3R,5S)-3,5-dimethyl-piperazin-1-ylmethyl)-4-morpholin-4-yl-thieno[3,2-d]pyrimidine (80 mg, 0.14 mmol) in dichloromethane (5 mL) was added triethylamine (40 μL, 2.0 equivalents) followed by acetyl chloride (15 μL, 1.5 eq.). After stirring overnight, the reaction mixture was diluted with dichloromethane, washed with aqueous sodium carbonate solution, dried (MgSO4) and the solvent removed in vacuo to yield 1-((2R,6S)-4-{2-[3-(tert-butyl-dimethyl-silanyloxy)-phenyl]-4-morpholin-4-yl-thieno[3,2-d]pyrimidin-6-ylmethyl}-2,6-dimethyl-piperazin-1-yl)-ethanone (80 mg) as a white solid. Removal of the tert-butyldimethylsilyl protecting group was performed as described above to yield the title compound.
CC(=O)N1[C@H](C)CN(Cc2cc3nc(-c4cccc(O[Si](C)(C)C(C)(C)C)c4)nc(N4CCOCC4)c3s2)C[C@@H]1C
null
null
null
909,492
ord_dataset-46d216f2c4374ef5b9df90427e2a4cd4
null
2009-01-01T00:09:00
true
N[C:2]1[C:6]([C:7]#[N:8])=[C:5]([S:9][CH3:10])[S:4][C:3]=1[C:11]([O:13][CH2:14][CH3:15])=[O:12].N(OCCC(C)C)=O>CN(C)C=O>[C:7]([C:6]1[CH:2]=[C:3]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[S:4][C:5]=1[S:9][CH3:10])#[N:8]
CCOC(=O)c1sc(SC)c(C#N)c1N
null
null
CC(C)CCON=O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
25
null
A solution of 50 g (0.21 mol) of ethyl 3-amino-4-cyano-5-methylsulfanylthiophene-2-carboxylate in 500 mL of dimethylformamide under an argon atmosphere is heated to a temperature in the region of 60° C., and a solution of 71.1 mL (0.45 mol) of isopentyl nitrite in 100 mL of dimethylformamide is then introduced with stirring, while maintaining the temperature between 65 and 70° C. The reaction mixture is then stirred at a temperature in the region of 60° C. for 2.5 hours, and then cooled to a temperature in the region of 25° C. and stirred for one hour. The mixture is then treated with 1 L of ice-cold water and then stirred at a temperature in the region of 0° C. for one hour. The precipitate obtained is filtered off and then washed successively three times with 200 mL of water and three times with 200 mL of petroleum ether. 40.5 g (86%) of ethyl 4-cyano-5-methylsulfanylthiophene-2-carboxylate are thus obtained, after drying under reduced pressure, in the form of a yellow crystalline powder melting at 100° C. MS-CI (NH3): 245(+)=(M+NH4)(+).
CCOC(=O)c1cc(C#N)c(SC)s1
null
84.8
null
275,326
ord_dataset-02ee2261663048188cf6d85d2cc96e3f
null
1993-01-01T00:09:00
true
[CH2:1]([OH:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:9][OH:10]>>[C:1]1([C:2]2[C:7](=[CH:6][CH:5]=[CH:4][CH:3]=2)[CH2:9][O:10]1)=[O:8]
CO
OCc1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The procedure described in method F is repeated, except that the methanol is replaced by 50 ml of benzyl alcohol, affording a phthalide compound of the formula ##STR19## melting point 183°-184° C.
O=C1OCc2ccccc21
null
null
null
1,519,142
ord_dataset-8c74302143c04eb9983e4b3a7ead2d72
null
2014-01-01T00:12:00
true
[CH3:1][C:2]1([CH3:22])[CH2:11][CH2:10][C:9]([CH3:13])([CH3:12])[C:8]2[CH:7]=[C:6]([C:14]3[N:15]=[C:16]([CH2:19][CH2:20][NH2:21])[S:17][CH:18]=3)[CH:5]=[CH:4][C:3]1=2.[C:23]([O:27][C:28]([NH:30][C@@H:31]([CH2:35][OH:36])[C:32](O)=[O:33])=[O:29])([CH3:26])([CH3:25])[CH3:24]>>[C:23]([O:27][C:28](=[O:29])[NH:30][C@H:31]([C:32](=[O:33])[NH:21][CH2:20][CH2:19][C:16]1[S:17][CH:18]=[C:14]([C:6]2[CH:5]=[CH:4][C:3]3[C:2]([CH3:22])([CH3:1])[CH2:11][CH2:10][C:9]([CH3:12])([CH3:13])[C:8]=3[CH:7]=2)[N:15]=1)[CH2:35][OH:36])([CH3:26])([CH3:24])[CH3:25]
CC(C)(C)OC(=O)N[C@@H](CO)C(=O)O
CC1(C)CCC(C)(C)c2cc(-c3csc(CCN)n3)ccc21
null
null
null
null
null
null
null
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 preparation is carried out as already described starting from 186 mg (0.59 mmol) of 2-[4-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)thiazol-2-yl]ethylamine from step b and 133 mg (0.65 mmol) of (S)-2-tert-butoxycarbonylamino-3-hydroxypropionic acid.
CC(C)(C)OC(=O)N[C@@H](CO)C(=O)NCCc1nc(-c2ccc3c(c2)C(C)(C)CCC3(C)C)cs1
null
null
null
836,807
ord_dataset-074f86301ec5441ab3b52d902ac06949
null
2008-01-01T00:09:00
true
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:16])=[C:6]([C:8]2[CH:13]=[C:12](Cl)[N:11]=[C:10]([NH2:15])[N:9]=2)[CH:7]=1.[NH2:17][C:18]1[CH:25]=[CH:24][C:21]([C:22]#[N:23])=[CH:20][CH:19]=1>>[NH2:15][C:10]1[N:11]=[C:12]([NH:17][C:18]2[CH:25]=[CH:24][C:21]([C:22]#[N:23])=[CH:20][CH:19]=2)[CH:13]=[C:8]([C:6]2[CH:7]=[C:2]([Br:1])[CH:3]=[CH:4][C:5]=2[CH3:16])[N:9]=1
Cc1ccc(Br)cc1-c1cc(Cl)nc(N)n1
N#Cc1ccc(N)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
Following the method described in Example 26, 4-(5-bromo-2-methyl-phenyl)-6-chloro-pyrimidin-2-ylamine and 4-amino-benzonitrile provided the title compound (72% yield). 1H NMR (CD3OD) δ 2.40 (s, 3H, CH3), 6.38 (s, 1H, Ar), 7.39 (d, 1H, J=8.9 Hz, Ar), 7.68-7.69 (m, 2H, Ar), 7.78-7.80 (m, 2H, Ar), 8.07 (d, 2H, J=7.6 Hz, Ar).
Cc1ccc(Br)cc1-c1cc(Nc2ccc(C#N)cc2)nc(N)n1
null
72
null
1,558,184
ord_dataset-4e54080057a44c3887653391e24c90b6
null
2015-01-01T00:03:00
true
[H-].[Na+].[Br:3][C:4]1[CH:5]=[C:6]([CH2:21][OH:22])[CH:7]=[N:8][C:9]=1[O:10][C:11]1[CH:16]=[CH:15][CH:14]=[C:13]([C:17]([F:20])([F:19])[F:18])[CH:12]=1.Cl[C:24]1[CH:25]=[C:26]2[N:33]([CH3:34])[CH2:32][CH2:31][N:27]2[C:28](=[O:30])[N:29]=1>C1COCC1>[Br:3][C:4]1[CH:5]=[C:6]([CH2:21][O:22][C:24]2[CH:25]=[C:26]3[N:33]([CH3:34])[CH2:32][CH2:31][N:27]3[C:28](=[O:30])[N:29]=2)[CH:7]=[N:8][C:9]=1[O:10][C:11]1[CH:16]=[CH:15][CH:14]=[C:13]([C:17]([F:18])([F:19])[F:20])[CH:12]=1
OCc1cnc(Oc2cccc(C(F)(F)F)c2)c(Br)c1
CN1CCn2c1cc(Cl)nc2=O
null
[H-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
null
Prepared in a manner similar to that described for E1 using NaH (6.89 mg, 0.172 mmol), (5-bromo-6-(3-(trifluoromethyl)phenoxy)pyridin-3-yl)methanol (60 mg, 0.17 mmol) in THF (8 mL) and 7-chloro-1-methyl-2,3-dihydroimidazo[1,2-c]pyrimidin-5(1H)-one (32.0 mg, 0.172 mmol).
CN1CCn2c1cc(OCc1cnc(Oc3cccc(C(F)(F)F)c3)c(Br)c1)nc2=O
null
null
null
1,231,064
ord_dataset-e96f5a2842f14e5380461c234100f05a
null
2012-01-01T00:12:00
true
[C:1]([O:5][C:6](=[O:31])[CH2:7][O:8][C@H:9]1[CH2:14][CH2:13][CH2:12][C@@H:11]([O:15][C:16]2[C:17]3[C:24]([C:25]4[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=4)=[CH:23][O:22][C:18]=3[N:19]=[CH:20][N:21]=2)[CH2:10]1)([CH3:4])([CH3:3])[CH3:2].C1C(=O)N([Br:39])C(=O)C1>ClC(Cl)(Cl)Cl>[C:1]([O:5][C:6](=[O:31])[CH2:7][O:8][C@H:9]1[CH2:14][CH2:13][CH2:12][C@@H:11]([O:15][C:16]2[C:17]3[C:24]([C:25]4[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=4)=[C:23]([Br:39])[O:22][C:18]=3[N:19]=[CH:20][N:21]=2)[CH2:10]1)([CH3:4])([CH3:2])[CH3:3]
O=C1CCC(=O)N1Br
CC(C)(C)OC(=O)CO[C@H]1CCC[C@@H](Oc2ncnc3occ(-c4ccccc4)c23)C1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)(Cl)Cl
null
null
null
null
null
null
null
null
null
null
60
2
Suspend 100 mg (0.236 mmol) of (+/−)-cis-({3-[(5-phenylfuro[2,3-d]pyrimidin-4-yl)oxy]cyclohexyl}oxy)acetic acid tert-butyl ester in 0.2 ml of tetrachloromethane and add 46.1 mg (0.259 mmol) of NBS. Stir the reaction mixture at 60° C. for a total of 2 h, and add a further 23 mg of NBS after 1 h. After cooling, remove the tetrachloromethane under reduced pressure and purify the residue by preparative RP-HPLC (eluent: acetonitrile/water). 43.6 mg (36.8% of theory) of the target product are obtained.
CC(C)(C)OC(=O)CO[C@H]1CCC[C@@H](Oc2ncnc3oc(Br)c(-c4ccccc4)c23)C1
null
null
null
1,336,078
ord_dataset-08852243bba44cb28769a5833f1515fe
null
2013-01-01T00:09:00
true
[CH2:1]([O:3][C:4]([C:6]1[CH:14]=[C:13]2[C:9]([C:10]([CH:25]=[O:26])=[C:11]([CH:22]([CH3:24])[CH3:23])[N:12]2[CH2:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][N:17]=2)=[CH:8][CH:7]=1)=[O:5])[CH3:2].[O-:27]Cl=O.[Na+]>CC(O)(C)C.CC(=CC)C.O>[CH2:1]([O:3][C:4]([C:6]1[CH:14]=[C:13]2[C:9]([C:10]([C:25]([OH:27])=[O:26])=[C:11]([CH:22]([CH3:23])[CH3:24])[N:12]2[CH2:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][N:17]=2)=[CH:8][CH:7]=1)=[O:5])[CH3:2]
[O-][Cl+][O-]
CCOC(=O)c1ccc2c(C=O)c(C(C)C)n(Cc3ccccn3)c2c1
null
CC=C(C)C
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CC(C)(C)O
null
null
null
null
null
null
null
null
null
25
12
Following General Procedure D, ethyl3-formyl-2-isopropyl-1-(pyridin-2-ylmethyl)-1H-indole-6-carboxylate (Compound 36, 287 mg, 0.82 mmol) in t-BuOH (6 ml), 2-methyl-2-butene (2.29 ml) was added a solution of NaH2PO4 (1.97 g, 16.4mmol) and NaClO2 (80%, 1.48 g, 16.4 mmol) in H2O (6 ml). The mixture was stirred at room temperature for 12 h. The reaction mixture was extracted with EtOAc (×3) and the combined organic layer was washed with brine, dried over Na2SO4, and concentrated in vacuo. The residue was purified by chromatography on silica gel (0→50% EtOAc-hexanes) to yield the title compound as a light yellow solid.
CCOC(=O)c1ccc2c(C(=O)O)c(C(C)C)n(Cc3ccccn3)c2c1
null
null
null
992,143
ord_dataset-b6d8835b0c934476a36e6149e7597487
null
2010-01-01T00:09:00
true
[SH:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[C:5]#[N:6].C(=O)([O-])[O-].[K+].[K+].Br[CH2:23][CH2:24][CH2:25][O:26][Si:27]([C:30]([CH3:33])([CH3:32])[CH3:31])([CH3:29])[CH3:28]>CN(C)C=O>[Si:27]([O:26][CH2:25][CH2:24][CH2:23][S:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1)[C:5]#[N:6])([C:30]([CH3:31])([CH3:32])[CH3:33])([CH3:29])[CH3:28]
CC(C)(C)[Si](C)(C)OCCCBr
N#Cc1ccc(-c2ccccc2)c(S)c1
null
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
25
16
To a solution of 3-mercapto-4-phenylbenzonitrile (0.44 g) in N,N-dimethylformamide (5.0 mL) was added potassium carbonate (0.43 g). Then (3-bromopropoxy)-tert-butyldimethylsilane (0.72 mL) was added, and the resulting mixture was stirred at room temperature for 16 hours. The reaction mixture was partitioned between diethyl ether (55 mL) and water (10 mL). The organic layer was washed with water (10 mL×2) and brine (10 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: hexane/ethylacetate=3/2) to give the title compound (0.8 g).
CC(C)(C)[Si](C)(C)OCCCSc1cc(C#N)ccc1-c1ccccc1
null
null
null
1,337,046
ord_dataset-08852243bba44cb28769a5833f1515fe
null
2013-01-01T00:09:00
true
Br[CH2:2][CH2:3][N:4]1[C:28](=[O:29])[N:7]2[CH:8]([C:21]3[CH:26]=[CH:25][CH:24]=[C:23]([OH:27])[CH:22]=3)[C:9]3[NH:10][C:11]4[C:16]([C:17]=3[CH2:18][C:6]2([CH3:30])[C:5]1=[O:31])=[CH:15][C:14]([O:19][CH3:20])=[CH:13][CH:12]=4.[CH2:32]([NH2:34])[CH3:33]>CO>[CH2:32]([NH:34][CH2:2][CH2:3][N:4]1[C:28](=[O:29])[N:7]2[CH:8]([C:21]3[CH:26]=[CH:25][CH:24]=[C:23]([OH:27])[CH:22]=3)[C:9]3[NH:10][C:11]4[C:16]([C:17]=3[CH2:18][C:6]2([CH3:30])[C:5]1=[O:31])=[CH:15][C:14]([O:19][CH3:20])=[CH:13][CH:12]=4)[CH3:33]
CCN
COc1ccc2[nH]c3c(c2c1)CC1(C)C(=O)N(CCBr)C(=O)N1C3c1cccc(O)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
null
null
The title compound is prepared similarly as described for example 30 using (3aSR,10RS)-2-(2-Bromoethyl)-10-(3-hydroxy-phenyl)-6-methoxy-3a-methyl-3a,4,9,10-tetrahydro-2,9,10a-triaza-cyclopenta[b]-fluorene-1,3-dione (example 24) and a 2 M solution of ethyl amine in methanol as starting materials.
CCNCCN1C(=O)N2C(c3cccc(O)c3)c3[nH]c4ccc(OC)cc4c3CC2(C)C1=O
null
null
null
98,560
ord_dataset-b37811c5ed724c3b844cc4d2b5640398
null
1982-01-01T00:09:00
true
[CH2:1]([NH:17][C:18]1[CH:30]=[CH:29][C:21]([CH2:22][CH2:23][C:24](OCC)=[O:25])=[CH:20][CH:19]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16].[H-].[Al+3].[Li+].[H-].[H-].[H-]>>[CH2:1]([NH:17][C:18]1[CH:30]=[CH:29][C:21]([CH2:22][CH2:23][CH2:24][OH:25])=[CH:20][CH:19]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16]
CCCCCCCCCCCCCCCCNc1ccc(CCC(=O)OCC)cc1
null
null
[Al+3]
[H-]
[Li+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
By a method analogous to that described in Example 16, ethyl 4-hexadecylaminohydrocinnamate is reduced with lithium aluminum hydride to provide the title compound.
CCCCCCCCCCCCCCCCNc1ccc(CCCO)cc1
null
null
null
1,610,583
ord_dataset-9cecb3a8d3b9494191b28dcefea66af2
null
2015-01-01T00:07:00
true
[F:1]C1C=C2C(=CC=1)NC=C2C=O.C(O[C:17]1[CH:18]=[C:19]2[C:23](=[CH:24][CH:25]=1)[N:22]([C:26]([NH2:28])=[O:27])[CH:21]=[C:20]2[N:29]=[C:30]=[O:31])C=C>>[F:1][C:17]1[CH:18]=[C:19]2[C:23](=[CH:24][CH:25]=1)[N:22]([C:26]([NH2:28])=[O:27])[CH:21]=[C:20]2[N:29]=[C:30]=[O:31]
O=Cc1c[nH]c2ccc(F)cc12
C=CCOc1ccc2c(c1)c(N=C=O)cn2C(N)=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
was prepared from 5-fluoro-1H-indole-3-carbaldehyde using the protocol described for steps C, D and E in scheme A4 for the preparation of 5-allyloxy-3-isocyanato-indole-1-carboxylic acid amide.
NC(=O)n1cc(N=C=O)c2cc(F)ccc21
null
null
null
995,685
ord_dataset-b6d8835b0c934476a36e6149e7597487
null
2010-01-01T00:09:00
true
[CH3:1][N:2]1[C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][C:5]=2[N:4]=[C:3]1[CH2:11][C:12]1[CH:21]=[CH:20][C:15]([C:16]([O:18]C)=[O:17])=[CH:14][CH:13]=1.[OH-].[Na+]>CO>[CH3:1][N:2]1[C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][C:5]=2[N:4]=[C:3]1[CH2:11][C:12]1[CH:21]=[CH:20][C:15]([C:16]([OH:18])=[O:17])=[CH:14][CH:13]=1
COC(=O)c1ccc(Cc2nc3ccccc3n2C)cc1
null
null
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
25
null
A solution of methyl 4-[(1-methyl-1H-benzimidazol-2-yl)methyl]benzoate (7.0 g, 25 mmol) in methanol was treated with 2.5 N sodium hydroxide, heated at reflux temperature for 2 h, cooled to room temperature and concentrated in vacuo. The residue was dissolved in water and acidified with 6N HCl solution and filtered. The filtercake was air dried to afford 4-[(1-methyl-1H-benzoimidazol-2-yl)methyl]benzoic acid in 81% yield; 1H NMR (400 MHz, DMSO-d6): 7.90 (d, J=8 Hz, 2H), 7.57 (d, J=8 Hz, 1H), 7.49 (d, J=8 Hz, 1H), 7.40 (d, J=8 Hz, 2H), 7.17-7.20 (m, 2H), 4.39 (s, 2H), 3.70 (s, 3H). LCMS (ESI+) 276 (MH+).
Cn1c(Cc2ccc(C(=O)O)cc2)nc2ccccc21
null
81
null
605,595
ord_dataset-273fda773e864aaf9b71a30a2d9f2162
null
2003-01-01T00:08:00
true
[Cl:1][C:2]1[CH:13]=[CH:12][C:5](/[CH:6]=[CH:7]/[C:8]([O:10][CH3:11])=[O:9])=[C:4]([NH:14]S(C2C=CC=CC=2)(=O)=O)[CH:3]=1.[CH:24]1([C:28]([CH2:30]Br)=[O:29])[CH2:27][CH2:26][CH2:25]1>>[CH3:11][O:10][C:8](=[O:9])[CH2:7][C:6]1[C:5]2[C:4](=[CH:3][C:2]([Cl:1])=[CH:13][CH:12]=2)[NH:14][C:30]=1[C:28]([CH:24]1[CH2:27][CH2:26][CH2:25]1)=[O:29]
COC(=O)/C=C/c1ccc(Cl)cc1NS(=O)(=O)c1ccccc1
O=C(CBr)C1CCC1
null
null
null
null
null
null
null
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 according to the procedure described in Example 57 from methyl trans-4-chloro-2-(phenylsulfonylamino)cinnamate (step 1 of Example 8, Method A) and bromomethyl cyclobutyl ketone*.
COC(=O)Cc1c(C(=O)C2CCC2)[nH]c2cc(Cl)ccc12
null
null
null
1,710,904
ord_dataset-3f2a531ffbae4b9eb1048afcd7953beb
null
2016-01-01T00:04:00
true
[C:1]([N:8]1[CH2:16][CH2:15][CH2:14][C@H:10]([C:11]([OH:13])=O)[CH2:9]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[CH3:17][NH:18][CH2:19][CH2:20][O:21][CH2:22][CH2:23][O:24][CH2:25][CH2:26][O:27][CH2:28][CH2:29][O:30][CH2:31][CH2:32][O:33][CH2:34][CH2:35][O:36][CH2:37][CH2:38][O:39][CH3:40].CCN(C(C)C)C(C)C.CN(C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F>CN(C=O)C>[CH3:40][O:39][CH2:38][CH2:37][O:36][CH2:35][CH2:34][O:33][CH2:32][CH2:31][O:30][CH2:29][CH2:28][O:27][CH2:26][CH2:25][O:24][CH2:23][CH2:22][O:21][CH2:20][CH2:19][N:18]([CH3:17])[C:11]([C@H:10]1[CH2:14][CH2:15][CH2:16][N:8]([C:1]([O:3][C:4]([CH3:5])([CH3:6])[CH3:7])=[O:2])[CH2:9]1)=[O:13]
CC(C)(C)OC(=O)N1CCC[C@H](C(=O)O)C1
CNCCOCCOCCOCCOCCOCCOCCOC
null
CN(C)C(On1nnc2cccnc21)=[N+](C)C
F[P-](F)(F)(F)(F)F
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
CCN(C(C)C)C(C)C
null
null
null
null
null
null
null
null
null
null
1
To a solution of Boc-(S)-nipecotic acid (137 mg, 0.60 mmol), N-methyl-2,5,8,11,14,17,20-heptaoxadocosan-22-amine 135c.1 (310 mg, 0.88 mmol) and DIPEA (335 mg, 2.6 mmol) in DMF (3 mL) was added HATU (285 mg, 0.75 mmol). The reaction was stirred for 1 hour and then the DMF was removed under vacuum. The residue was added to saturated aqueous NaHCO3 (10 mL) and extracted with DCM (3×20 mL). The combined organic layers were dried (Na2SO4) and concentrated to give (S)-tert-butyl 3-(2,5,8,11,14,17,20-heptaoxadocosan-22-yl(methyl)carbamoyl)piperidine-1-carboxylate (720 mg).
COCCOCCOCCOCCOCCOCCOCCN(C)C(=O)[C@H]1CCCN(C(=O)OC(C)(C)C)C1
null
212.5
null
133,767
ord_dataset-34cf5f1378de4e34844aea93a2f9a9d3
null
1985-01-01T00:08:00
true
[Na].[O-]CC.[Na+].[S:6]1[CH:10]=[CH:9][CH:8]=[C:7]1[CH:11]([OH:16])[C:12]([O:14]C)=O.[F:17][C:18]([F:29])([F:28])[C:19]1[CH:20]=[C:21]([CH2:25][C:26]#[N:27])[CH:22]=[CH:23][CH:24]=1>C(O)C.O>[S:6]1[CH:10]=[CH:9][CH:8]=[C:7]1[CH:11]1[C:12](=[O:14])[C:25]([C:21]2[CH:22]=[CH:23][CH:24]=[C:19]([C:18]([F:28])([F:17])[F:29])[CH:20]=2)=[C:26]([NH2:27])[O:16]1
COC(=O)C(O)c1cccs1
N#CCc1cccc(C(F)(F)F)c1
null
CC[O-]
[Na+]
[Na]
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
null
null
A dry, 250-ml, three-neck, round-bottom flask equipped with a mechanical stirrer, addition funnel and a reflux condenser bearing a nitrogen inlet tube was charged with 4.2 g of sodium and 100 ml of absolute ethanol. To the resulting sodium ethoxide solution was added dropwise a mixture of 21.1 g of methyl thien-2-yl-hydroxyacetate and 22.7 g of m-trifluoromethylphenyl-acetonitrile in 20 ml of ethanol. The resulting mixture was heated at reflux for 4-5 hours after which time it was added to 300-400 ml of water and extracted with petroleum ether. The aqueous phase was acidified with aqueous 10 weight percent hydrochloric acid and extracted two times with diethyl ether. The ether extracts were washed twice with saturated aqueous sodium bicarbonate, dried over magnesium sulfate and concentrated in vacuo to yield a thick dark oil. This oil was triturated with 20-30% ether/petroleum ether which afforded 4.9 g of the title compound as a tan powder.
NC1=C(c2cccc(C(F)(F)F)c2)C(=O)C(c2cccs2)O1
null
12.3
null
1,205,264
ord_dataset-fb72428f30234761b4216139dc228d0c
null
2012-01-01T00:09:00
true
O1[C:5]2([CH2:10][CH2:9][C:8]([C:11]3[C:12]([O:17][CH3:18])=[N:13][CH:14]=[CH:15][CH:16]=3)=[CH:7][CH2:6]2)[O:4]CC1.Cl>C(#N)C>[CH3:18][O:17][C:12]1[C:11]([C:8]2[CH2:9][CH2:10][C:5](=[O:4])[CH2:6][CH:7]=2)=[CH:16][CH:15]=[CH:14][N:13]=1
COc1ncccc1C1=CCC2(CC1)OCCO2
null
null
Cl
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
25
null
To a mixture of 3-(1,4-Dioxa-spiro[4.5]dec-7-en-8-yl)-2-methoxy-pyridine (as prepared in the previous step, 211 mg, 0.854 mmol) in acetonitrile was added aqueous HCl (5 mL, 5 mmol, 1M). The mixture was stirred at room temperature until HPLC indicated consumption of starting material. The reaction mixture was poured onto saturated sodium bicarbonate solution and extracted with ethyl acetate. The organic layer washed with brine, dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was purified by flash chromatography (SiO2, 0-10% MeOH/CH2Cl2) to afford 4-(2-methoxy-pyridin-3-yl)-cyclohex-3-enone.
COc1ncccc1C1=CCC(=O)CC1
null
null
null
1,174,393
ord_dataset-0f9d2dbe929a45c3892ae75e81e99443
null
2012-01-01T00:06:00
true
[C:1]([O:9][CH2:10][C@@:11]1([C:26]#[CH:27])[O:15][C@@H:14]([N:16]2[CH:24]=[C:22]([CH3:23])[C:20](=[O:21])[NH:19][C:17]2=[O:18])[CH2:13][C@H:12]1[OH:25])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CCN(CC)CC.[Si]([O:39][S:40]([C:43](F)(F)F)(=O)=[O:41])(C)(C)C.O=O>CC([O-])=O.CC([O-])=O.[Pd+2]>[C:1]([O:9][CH2:10][C@@:11]1([C:26]#[CH:27])[O:15][C@@H:14]([N:16]2[CH:24]=[C:22]([CH3:23])[C:20](=[O:21])[NH:19][C:17]2=[O:18])[CH2:13][C@H:12]1[O:25][S:40]([CH3:43])(=[O:41])=[O:39])(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
C[Si](C)(C)OS(=O)(=O)C(F)(F)F
C#C[C@]1(COC(=O)c2ccccc2)O[C@@H](n2cc(C)c(=O)[nH]c2=O)C[C@H]1O
null
[Pd+2]
CC(=O)[O-]
O=O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(CC)CC
null
null
null
null
null
null
null
null
null
null
null
0.5
To a stirring mixture of 4 (3.58 g, 8.72 mmol) and Et3N (6.1 ml, 43.6 mmol) was added Me3SiOSO2CF3 (2.56 mL, 13.0 mmol) at 0° C. under positive pressure of dry Ar. The mixture was stirred for 30 min at the same temperature, and then partitioned between CH2Cl2 and sat. aqueous NaHCO3. The organic layer was dried (Na2SO4) and evaporated. The residue was dissolved in DMSO (12 mL). To this solution was added Pd(OAc)2 (98 mg, 0.44 mmol), and the mixture was stirred for 36 h under positive pressure of O2. The mixture was partitioned between EtOAc and brine. The organic layer was dried (Na2SO4), evaporated, and chromatographed on a silica gel column (hexane/EtOAc=5/1) to give 5 (3.13 g, 88%) as a white solid.
C#C[C@]1(COC(=O)c2ccccc2)O[C@@H](n2cc(C)c(=O)[nH]c2=O)C[C@H]1OS(C)(=O)=O
null
80
null
579,316
ord_dataset-a9ba4801408c4b01922886164c10a391
null
2003-01-01T00:01:00
true
F[B-](F)(F)F.[CH3:6][C:7]1[CH:12]=[C:11]([CH3:13])[C:10]([CH3:14])=[CH:9][C:8]=1[C:15]1[CH:20]=[C:19]([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH:18]=[C:17]([C:27]2[CH:32]=[C:31]([CH3:33])[C:30]([CH3:34])=[CH:29][C:28]=2[CH3:35])[O+]=1.[PH3:36]>C(O)CCC>[CH3:6][C:7]1[CH:12]=[C:11]([CH3:13])[C:10]([CH3:14])=[CH:9][C:8]=1[C:15]1[CH:20]=[C:19]([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH:18]=[C:17]([C:27]2[CH:32]=[C:31]([CH3:33])[C:30]([CH3:34])=[CH:29][C:28]=2[CH3:35])[P:36]=1
Cc1cc(C)c(-c2cc(-c3ccccc3)cc(-c3cc(C)c(C)cc3C)[o+]2)cc1C
P
null
F[B-](F)(F)F
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCCCO
null
null
null
null
null
null
null
null
null
null
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2.1 g (4.4 mmol) of 2,6-bis(2,4,5-trimethylphenyl)-4-phenylpyrylium tetrafluoroborate in 150 ml of n-butanol were used as starting material. The autoclave product obtained after the reaction with PH3 was evaporated to about 50 ml under reduced pressure at about 80° C. The solid which precipitated was filtered off with suction, washed with n-pentane and subsequently dissolved in toluene. The toluene solution was then washed with water until the aqueous phase was neutral. After removing the solvent and washing with a little n-pentane, the residue was dissolved in dichloromethane. The resulting solution was diluted with methanol and then evaporated under reduced pressure at 30° C. until a solid precipitated. The solid was filtered off with suction, washed with a little n-pentane and subsequently dried in a high vacuum. Yield: 0.8 g (45%) of light-yellow solid.
Cc1cc(C)c(-c2cc(-c3ccccc3)cc(-c3cc(C)c(C)cc3C)p2)cc1C
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