Sodium Carbonate → 4-[4-Amino-3-(4,4-dimethyl-cyclohex-1-enyl)-phenyl]-1,1-dioxo-hexahydro-1lambda6-thiopyran-4-carbonitrile

HRID 1054291ノート

反応式

HRID 1054291 の反応式
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2([C:16]#[N:17])[CH2:13][CH2:12][S:11](=[O:15])(=[O:14])[CH2:10][CH2:9]2)=[CH:4][C:3]=1Br.[CH3:19][C:20]1([CH3:35])[CH2:25][CH2:24][C:23](B2OC(C)(C)C(C)(C)O2)=[CH:22][CH2:21]1.C([O-])([O-])=O.[Na+].[Na+]>CN(C=O)C.CCOC(C)=O.O.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:16]#[N:17])[CH2:13][CH2:12][S:11](=[O:15])(=[O:14])[CH2:10][CH2:9]2)=[CH:4][C:3]=1[C:23]1[CH2:24][CH2:25][C:20]([CH3:35])([CH3:19])[CH2:21][CH:22]=1

参加物

8

反応物 3

HCID 10340Sodium CarbonateHCID 231420132-(4,4-Dimethylcyclohex-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 589950244-(4-Amino-3-bromo-phenyl)-1,1-dioxo-hexahydro-1lambda6-thiopyran-4-carbonitrile

生成物 1

HCID 589950684-[4-Amino-3-(4,4-dimethyl-cyclohex-1-enyl)-phenyl]-1,1-dioxo-hexahydro-1lambda6-thiopyran-4-carbonitrile収率 100%

試薬・触媒・溶媒 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
60 °C

実験手順

A solution of 4-(4-amino-3-bromo-phenyl)-1,1-dioxo-hexahydro-1λ6-thiopyran-4-carbonitrile (109 mg, 0.332 mmol, as prepared in the previous step) in DMF (4 mL) was treated with 2-(4,4-dimethyl-cyclohex-1-enyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (94.1 mg, 0.398 mmol) and aq Na2CO3 (1.32 mL, 2.66 mmol, 2.0 M). The mixture was degassed via sonication, placed under Ar, treated with Pd(dppf)Cl2 (24.3 mg, 0.034 mmol), and heated to 60° C. for 24 h. The cooled mixture was diluted with EtOAc and water. The aqueous layer was extracted with EtOAc (4×). The combined organic layers were dried over MgSO4 and concentrated in vacuo. Purification of the residue by silica gel chromatography on a 10-g Isolute SPE column (FlashMaster system) with 25% EtOAc-hexane afforded the title compound (119 mg, 100%) as a white solid. Mass spectrum (ESI, m/z): Calcd. for C20H26N2O2S, 359.2 (M+H). found 359.3.

後処理

  1. customThe mixture was degassed via sonication
  2. extractionThe aqueous layer was extracted with EtOAc (4×)
  3. dry with materialThe combined organic layers were dried over MgSO4
  4. concentrationconcentrated in vacuo
  5. customPurification of the residue by silica gel chromatography on a 10-g Isolute SPE column (FlashMaster system) with 25% EtOAc-hexane

出典と根拠

ORDレコード
ord-bd07f93c31db46a38755928708c50cd6
出典データセット
uspto-grants-2016_07
特許番号
US09394289B2

反応ノート

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