Diphenylmethylidenehydrazine → 4-(N'-benzhydrylidenehydrazino)-2-methyl-N-(2-morpholin-4-yl-ethyl)benzene sulfonamide

HRID 221873Notes

Reaction equation

HRID 221873 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([S:8]([NH:11][CH2:12][CH2:13][N:14]2[CH2:19][CH2:18][O:17][CH2:16][CH2:15]2)(=[O:10])=[O:9])=[C:4]([CH3:20])[CH:3]=1.[C:21](=[N:34][NH2:35])([C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CC1(C)C2C=CC=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=2OC2C1=CC=CC=2P(C1C=CC=CC=1)C1C=CC=CC=1>[C:21](=[N:34][NH:35][C:2]1[CH:7]=[CH:6][C:5]([S:8]([NH:11][CH2:12][CH2:13][N:14]2[CH2:19][CH2:18][O:17][CH2:16][CH2:15]2)(=[O:10])=[O:9])=[C:4]([CH3:20])[CH:3]=1)([C:28]1[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1

Participants

7

Reactant 3

HCID 79304DiphenylmethylidenehydrazineHCID 23676156Sodium t-butoxideHCID 595579324-bromo-2-methyl-N-(2-morpholin-4-yl-ethyl)benzene-sulfonamide

Product 1

HCID 536301814-(N'-benzhydrylidenehydrazino)-2-methyl-N-(2-morpholin-4-yl-ethyl)benzene sulfonamideYield 81%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 1140TolueneSolvent

Conditions

Temperature
85 °C

Procedure

To a degassed solution of 4-bromo-2-methyl-N-(2-morpholin-4-yl-ethyl)benzene-sulfonamide (939 mg, 2.58 mmol), benzophenone hydrazone (558 mg, 2.84 mmol, 1.1 eq), and 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (75 mg, 0.13 mmol, 0.05 eq) in anhydrous toluene (13 mL, 0.2M) was added sodium tert-butoxide (596 mg, 6.20 mmol, 2.4 eq) followed by palladium(II) acetate (29 mg, 0.13 mmol, 0.05 eq), and the reaction mixture was stirred at 85° C. under nitrogen for 17 h. The reaction mixture was cooled to room temperature and was partitioned between EtOAc and water. The organic layer was washed with water and brine, dried over Na2SO4, and concentrated at reduced pressure. Purification by MPLC (75% EtOAc/hexane) afforded the title compound (1.00 g, 80%) as a white solid. 1H-NMR (DMSO-d6) δ 9.25 (s, 1H), 7.64 to 7.52 (m, 4H), 7.44 to 7.41 (m, 2H), 7.35 to 7.26 (m, 5H), 7.16 to 7.13 (m, 3H), 3.45 (t, J=4.8 Hz, 4H), 2.79 (q, J=6.3 Hz, 2H), 2.47 (s, 3H), 2.21 to 2.15 (m, 6H); MS LC-MS [M+H]+=479, RT=3.15 min.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. customwas partitioned between EtOAc and water
  3. washThe organic layer was washed with water and brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated at reduced pressure
  6. customPurification by MPLC (75% EtOAc/hexane)

Sources & evidence

ORD record
ord-fbeeb5d6fadb4240b52012b65a54ad6e
Source dataset
uspto-grants-2012_06
Patent number
US08207166B2

Reaction notes

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