Iopanoic Acid → Methyl 2-cyanomethyl-2-phenylmethylbutanoate

HRID 1108366

반응식

HRID 1108366 반응식
[C:1]1([CH2:7][CH:8]([CH2:13][CH3:14])[C:9]([O:11][CH3:12])=[O:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[CH2:16][C:17]#[N:18].C([N-]C(C)C)(C)C.[Li+].CN(P(N(C)C)(N(C)C)=O)C.CCC(C(O)=O)CC1C(I)=CC(I)=C(N)C=1I>C1COCC1>[C:1]1([CH2:7][CH:8]([CH2:13][CH3:14])[C:9]([O:11][CH3:12])=[O:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:17]([CH2:16][C:8]([CH2:7][C:1]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1)([CH2:13][CH3:14])[C:9]([O:11][CH3:12])=[O:10])#[N:18]

참가 물질

8

반응물 5

HCID 3735Iopanoic AcidHCID 11534BromoacetonitrileHCID 12679HexamethylphosphoramideHCID 2724682Lithium diisopropylamideHCID 12647073Methyl 2-phenylmethylbutyrate

생성물 2

HCID 10609559Methyl 2-cyanomethyl-2-phenylmethylbutanoate수율 103.4%HCID 12647073Methyl 2-phenylmethylbutyrate

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

Methyl 2-phenylmethylbutyrate (9.60 g, 50 mmol) was reacted with bromoacetonitrile (7.20 g, 60 mmol) in the presence of lithium diisopropylamide in THF (150 mL) and HMPA (4.3 mL, 25 mmol), as described above in the preparation of Example 4, to give 12.08 g of the crude product as a dark colored liquid. Methyl 2-phenylmethylbutyrate was prepared as in Colombo M, De Amici M, De Micheli C, Pitre D, Carrea G, Riva S (1991) "Chemoenzymatic synthesis of the enantiomers of iopanic acid" Tetrahedron:Asymmetry, 2, 1021-1030. Column chromatography over silica gel (hexanes-CH2Cl2, 3:2) afforded 5.98 g (52%) of the nitrile as a colorless viscous liquid. Analytical sample was prepared by bulb-to-bulb distillation (pot temp. 105° C. (0.5 mmHg)). Lithium diisopropylamide was prepared by treating diisopropylamine (5.56 g, 55 mmol) with butyllithium in hexanes (2.5 M, 22 mL, 55 mmol).

후처리

  1. customas described above in the preparation of Example 4
  2. customto give 12.08 g of the crude product as a dark colored liquid

출처 및 근거

ORD 기록
ord-9b11bd59a46b4a20a4f6931baf252a2c
출처 데이터셋
uspto-grants-2000_05
특허 번호
US06066666

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