p-Bromochlorobenzene → N-Benzhydrylidene-N'-(4-chlorophenyl)hydrazine

HRID 1978276

Reaction equation

HRID 1978276 reaction equation
[C:1](=[N:14][NH2:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Cl:16][C:17]1[CH:22]=[CH:21][C:20](Br)=[CH:19][CH:18]=1.CC([O-])(C)C.[Na+]>CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.C1(C)C=CC=CC=1>[Cl:16][C:17]1[CH:22]=[CH:21][C:20]([NH:15][N:14]=[C:1]([C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[CH:19][CH:18]=1

Participants

7

Reactant 3

HCID 7806p-BromochlorobenzeneHCID 79304DiphenylmethylidenehydrazineHCID 23676156Sodium t-butoxide

Product 1

HCID 9948495N-Benzhydrylidene-N'-(4-chlorophenyl)hydrazineYield 64%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 634876Binap, (A+-)-CatalystHCID 1140TolueneSolvent2×

Procedure

Benzophenone hydrazone (1 equiv., 10 mmol, 2.04 g), 4-chlorobromobenzene (1.0 equiv., 10 mmol, 1.915 g), Pd(OAc)2 (0.01 equiv., 0.1 mmol, 23 mg), BINAP (0.01 equiv., 0.1 mmol, 63 mg), and toluene (5 mL) were added to an oven dried Schlenk flask and stirred at room temperature for 2 minutes, NaOtBu (1.4 equiv., 14 mmol, 1.345 g) and an additional 5 mL of toluene were then added. The flask was capped with a septum and purged briefly with argon (˜1 min.) and heated to 80° C. under argon for 13 hours. The reaction mixture was then cooled to room temperature, diluted with Et2O (10 mL), and concentrated under vacuum to give the crude product as a brown solid. Recrystallization of the crude product from hot isopropanol (100 mL) gave the desired product as a yellow solid (1.971 g, 6.4 mmol, 64% yield). The mother liquor was concentrated under vacuum and purified by column chromatography (5% EtOAc/Hex) to give an additional 550 mg of the desired product (1.79 mmol, 18% yield), to give an 82% overall yield of the title product.

Workup

  1. customdried Schlenk flask
  2. customThe flask was capped with a septum
  3. custompurged briefly with argon (˜1 min.)
  4. temperatureheated to 80° C. under argon for 13 hours
  5. temperatureThe reaction mixture was then cooled to room temperature
  6. additiondiluted with Et2O (10 mL)
  7. concentrationconcentrated under vacuum
  8. customto give the crude product as a brown solid
  9. customRecrystallization of the crude product from hot isopropanol (100 mL)

Sources & evidence

ORD record
ord-78c86af2905349f298b2174eeca2cbed
Source dataset
uspto-grants-2001_05
Patent number
US06235936B1

Linked notes

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