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

HRID 536972노트

반응식

HRID 536972 반응식
[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

참가 물질

8

반응물 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

생성물 1

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

시약·촉매·용매 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)촉매HCID 962Water용매HCID 6228Dimethylformamide용매HCID 8857Ethyl Acetate용매

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온도
60 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-47fc93bd29fd46cdac74c717e851105a
출처 데이터셋
uspto-grants-2014_10
특허 번호
US08859602B2

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