1,2-Dichloroethane → 3-nitro-4-bromomethyl-benzoic acid N'-(4-chloro-benzoyl)-hydrazide

HRID 1360802Notes

Reaction equation

HRID 1360802 reaction equation
[Cl:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([NH:8][NH2:9])=[O:7])=[CH:4][CH:3]=1.[Br:12][CH2:13][C:14]1[CH:22]=[CH:21][C:17]([C:18](O)=[O:19])=[CH:16][C:15]=1[N+:23]([O-:25])=[O:24].C(Cl)CCl>C(Cl)Cl>[Cl:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([NH:8][NH:9][C:18](=[O:19])[C:17]2[CH:21]=[CH:22][C:14]([CH2:13][Br:12])=[C:15]([N+:23]([O-:25])=[O:24])[CH:16]=2)=[O:7])=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 111,2-DichloroethaneHCID 108164-ChlorobenzohydrazideHCID 1323864-Bromomethyl-3-nitrobenzoic acid

Product 1

HCID 669668063-nitro-4-bromomethyl-benzoic acid N'-(4-chloro-benzoyl)-hydrazide

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a 100 mL round-bottom flask was added 2.1 g (12.3 mmol) of 4-chlorobenzoic acid hydrazide, 3.20 g (12.3 mmol) of 4-bromomethyl-3-nitro benzoic acid, 3.54 g (18.5 mmol) of EDC, and 200 mL of DCM. Allowed to stir at room temperature for 18 h. Removed ⅔ of DCM, added water and filtered off white solid and washed with Et2O to give 3-nitro-4-bromomethyl-benzoic acid N′-(4-chloro-benzoyl)-hydrazide as white solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 4.99 (s, 1H) 5.12 (s, 1H) 7.59-7.64 (m, 2H) 7.91-7.95 (m, 2H) 7.96 (d, J=8.21 Hz, 1H) 8.22-8.29 (m, 1H) 8.57 (dd, J=6.57, 1.77 Hz, 1H) 10.76 (s, 1H) 10.94 (dd, J=5.18, 0.88 Hz, 1H). MS (m/z) 413.9 M (+1), tR=1.28, Meth 10. To a 500 mL round-bottom flask was added 4.95 g (12.0 mmol) of 3-nitro-4-bromomethyl-benzoic acid N′-(4-chloro-benzoyl)-hydrazide, 6.09 g (36.0 mmol) DMC, and 100 mL of DCE. To this pale yellow solution was added 6.70 mL (48.0 mmol) of Et3N, slowly over 5 min. The dark green solution was allowed to stir at 40° C. for 30 min. then cooled to room temperature stirred for 18 h. Removed solvent and purified over a silica plug 10-30% EtOAc/Hep to give the title compound as yellow solid. MS (m/z) 350.0 M (+1), retention time=1.51, Method 10.

Workup

  1. customRemoved ⅔ of DCM
  2. additionadded water
  3. filtrationfiltered off white solid
  4. washwashed with Et2O

Sources & evidence

ORD record
ord-94506e084ae3494788012ace72032413
Source dataset
uspto-grants-2011_02
Patent number
US07879850B2

Reaction notes

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