Nitrogen → 5-Cyano-2-{[(2-nitro-benzenesulfonyl)-(5,6,7,8-tetrahydro-quinolin-8-yl)-amino}-methyl}-benzoic acid methyl ester

HRID 1592683Notes

Reaction equation

HRID 1592683 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[S:10]([NH:13][CH:14]1[C:23]2[N:22]=[CH:21][CH:20]=[CH:19][C:18]=2[CH2:17][CH2:16][CH2:15]1)(=[O:12])=[O:11])([O-:3])=[O:2].[CH3:24][O:25][C:26](=[O:37])[C:27]1[CH:32]=[C:31]([C:33]#[N:34])[CH:30]=[CH:29][C:28]=1[CH2:35]Br.C([O-])([O-])=O.[K+].[K+].N#N>CC#N>[CH3:24][O:25][C:26](=[O:37])[C:27]1[CH:32]=[C:31]([C:33]#[N:34])[CH:30]=[CH:29][C:28]=1[CH2:35][N:13]([S:10]([C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=1[N+:1]([O-:3])=[O:2])(=[O:11])=[O:12])[CH:14]1[C:23]2[N:22]=[CH:21][CH:20]=[CH:19][C:18]=2[CH2:17][CH2:16][CH2:15]1

Participants

6

Reactant 4

HCID 947NitrogenHCID 11430Potassium CarbonateHCID 17965928Methyl 2-(bromomethyl)-5-cyanobenzoateHCID 226013948-(2-Nitrobenzenesulfonyl)amino-5,6,7,8-tetrahydroquinoline

Product 1

HCID 672716105-Cyano-2-{[(2-nitro-benzenesulfonyl)-(5,6,7,8-tetrahydro-quinolin-8-yl)-amino}-methyl}-benzoic acid methyl esterYield 52%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of 2-nitro-N-(5,6,7,8-tetrahydro-quinolin-8-yl)-benzenesulfonamide (3.72 g, 11.0 mmol) dissolved in CH3CN (120 mL) was added 2-bromomethyl-5-cyano-benzoic acid methyl ester (2.79 g, 11.0 mmol) and K2CO3 (4.56 g, 33.0 mmol). The mixture was stirred for 18 hours at 80° C. under a positive pressure of N2. The mixture was concentrated in vacuo and redissolved in CH2Cl2 (150 mL). Brine (150 mL) was added and the mixture was extracted with CH2Cl2 (2×150 mL). The combined organic extracts were dried (Na2SO4), filtered, and concentrated in vacuo to afford a black oil. Purification via column chromatography on silica gel (hexanes:EtOAc, 2:1, v/v) afforded 5-cyano-2-{[(2-nitro-benzenesulfonyl)-(5,6,7,8-tetrahydro-quinolin-8-yl)-amino}-methyl}-benzoic acid methyl ester as a yellow solid (2.89 g, 52%). 1H NMR (CDCl3) δ 1.55 (m, 1H), 1.89 (m, 2H), 2.34 (m, 1H), 2.66 (m, 2H), 4.44 (d, 1H, J=18.9 Hz), 5.18 (d, 1H, J=18.9 Hz), 5.38 (m, 1H), 6.98 (dd, 1H, J=7.5, 4.8 Hz), 7.31 (d, 1H, J=7.5 Hz), 7.75 (m, 4H), 7.91 (d, 1H, J=4.4 Hz), 8.12 (m, 3H).

Workup

  1. concentrationThe mixture was concentrated in vacuo
  2. dissolutionredissolved in CH2Cl2 (150 mL)
  3. additionBrine (150 mL) was added
  4. extractionthe mixture was extracted with CH2Cl2 (2×150 mL)
  5. dry with materialThe combined organic extracts were dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto afford a black oil
  9. customPurification via column chromatography on silica gel (hexanes

Sources & evidence

ORD record
ord-489e03d0e9d44b08ad55cdea359fc6b4
Source dataset
uspto-grants-2007_11
Patent number
US07291631B2

Reaction notes

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