Sodium Carbonate → 1-[4-Amino-3-(4,4-dimethyl-cyclohex-1-enyl)-phenyl]-cyclohexanecarbonitrile

HRID 2408506ノート

反応式

HRID 2408506 の反応式
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2([C:14]#[N:15])[CH2:13][CH2:12][CH2:11][CH2:10][CH2:9]2)=[CH:4][C:3]=1Br.[CH3:17][C:18]1([CH3:27])[CH2:23][CH2:22][C:21](B(O)O)=[CH:20][CH2:19]1.C([O-])([O-])=O.[Na+].[Na+]>CN(C=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2([C:14]#[N:15])[CH2:13][CH2:12][CH2:11][CH2:10][CH2:9]2)=[CH:4][C:3]=1[C:21]1[CH2:22][CH2:23][C:18]([CH3:27])([CH3:17])[CH2:19][CH:20]=1

参加物

6

反応物 3

HCID 10340Sodium CarbonateHCID 441195554,4-Dimethylcyclohexen-1-ylboronic acidHCID 589937601-(4-Amino-3-bromo-phenyl)-cyclohexane carbonitrile

生成物 1

HCID 589937171-[4-Amino-3-(4,4-dimethyl-cyclohex-1-enyl)-phenyl]-cyclohexanecarbonitrile収率 30%

試薬・触媒・溶媒 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
80 °C

実験手順

A solution of 1-(4-amino-3-bromo-phenyl)-cyclohexane carbonitrile (136 mg, 0.487 mmol, as prepared in the previous step) in DMF (10 mL) was treated with 4,4-dimethyl-cyclohex-1-enylboronic acid (90.0 mg, 0.585 mmol) and Na2CO3 (1.95 mL, 3.90 mmol, 2 M aq). The mixture was degassed via sonication, placed under Ar, treated with Pd(dppf)Cl2 (35.6 mg, 0.0487 mmol), and heated to 80° C. overnight. The cooled mixture was partitioned between EtOAc (50 mL) and water (50 mL). The aqueous layer was extracted with EtOAc (2×50 mL). The combined organic layers was dried over MgSO4 and concentrated in vacuo. Silica gel chromatography of the residue on a 20-g Isolute SPE column with 10-15% EtOAc-hexane afforded the title compound (45.9 mg, 30%) as a colorless glassy solid. Mass spectrum (ESI, m/z): Calcd. for C21H28N2, 309.2 (M+H), found 309.2.

後処理

  1. customThe mixture was degassed via sonication
  2. customThe cooled mixture was partitioned between EtOAc (50 mL) and water (50 mL)
  3. extractionThe aqueous layer was extracted with EtOAc (2×50 mL)
  4. dry with materialThe combined organic layers was dried over MgSO4
  5. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-ea923c6529fb4d848a9090ff965baf7f
出典データセット
uspto-grants-2014_08
特許番号
US08815867B2

反応ノート

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