Dimethylformamide → HCID 178459256, 화합물

HRID 2272664노트

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HRID 2272664 반응식
[CH3:1][O:2][C:3]([C@H:5]1[CH2:10][CH2:9][C@H:8]([C:11]([OH:13])=O)[CH2:7][CH2:6]1)=[O:4].CN(C=O)C.[C:19](Cl)(=O)[C:20](Cl)=O.C([Zn]CC)C.[Cl-].[NH4+]>C(OCC)C.Cl[Pd]Cl.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].O1CCCC1.ClCCl>[C:11]([C@H:8]1[CH2:7][CH2:6][C@H:5]([C:3]([O:2][CH3:1])=[O:4])[CH2:10][CH2:9]1)(=[O:13])[CH2:19][CH3:20]

참가 물질

10

반응물 5

HCID 6228DimethylformamideHCID 25517Ammonium ChlorideHCID 65578Oxalyl chlorideHCID 178418750HCID 178418750, 화합물HCID 178501163HCID 178501163, 화합물

생성물 1

HCID 178459256HCID 178459256, 화합물

시약·촉매·용매 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)촉매HCID 3283Diethyl Ether용매HCID 6344Dichloromethane용매HCID 8028Tetrahydrofuran용매2회

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온도
0 °C

실험 절차

A dry round bottom flask was charged with trans-4-(methoxycarbonyl)cyclohexanecarboxylic acid (2.00 g, 10.74 mmol) and the reaction vessel was placed under an atmosphere of argon (3× vacuum/argon cycle). Dichloromethane (11 mL) was added followed by DMF (0.01 mL, 0.129 mmol). The reaction was cooled to 0° C. in an ice bath, then oxalyl chloride (1.00 mL, 11.42 mmoles) was added drop-wise. The ice bath was removed after 1 hour and the reaction was stirred at ambient temperature for 14 hours as gradual gas evolution occurred. [1,1′-Bis(diphenylphosphino)ferrocene]-dichloropalladium(II) (236.0 mg, 0.322 mmol) was then added to the reaction flask followed by tetrahydrofuran (11 mL) then a solution of diethylzinc in tetrahydrofuran (1.0 M, 12.9 mL, 12.9 mmol). The reaction was stirred at ambient temperature for two hours and was then poured into cold saturated aqueous ammonium chloride (100 mL). The resulting biphasic solution was diluted with diethyl ether (100 mL). The organic phase was separated and dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (0-100% ethyl acetate/hexanes) to afford methyl trans-4-propanoylcyclohexanecarboxylate as a clear oil. 1H NMR (500 MHz, CDCl3) δ 3.67 (s, 3H), 2.47 (q, J=7.3 Hz, 2H), 2.40-2.21 (m, 2H), 2.12-2.00 (m, 2H), 1.94 (d, J=13.9 Hz, 2H), 1.53-1.20 (m, 4H), 1.03 (t, J=7.3 Hz, 3H).

후처리

  1. customThe ice bath was removed after 1 hour
  2. stirringThe reaction was stirred at ambient temperature for two hours
  3. customThe organic phase was separated
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by silica gel chromatography (0-100% ethyl acetate/hexanes)

출처 및 근거

ORD 기록
ord-427b14d11b0845ecab3f97c435d24b90
출처 데이터셋
uspto-grants-2015_09
특허 번호
US09120785B2

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