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

HRID 991997

反応式

HRID 991997 の反応式
[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

参加物

7

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 634876Binap, (A+-)-触媒HCID 1140Toluene溶媒2 回

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-bed432e978144fa7a87409aaa2215474
出典データセット
uspto-grants-2002_10
特許番号
US06465693B2

関連ノート

読み込み中…