Iopanoic Acid → Methyl 2-cyanomethyl-2-phenylmethylbutanoate

HRID 1108366

反応式

HRID 1108366 の反応式
[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]

参加物

8

反応物 5

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

生成物 2

HCID 10609559Methyl 2-cyanomethyl-2-phenylmethylbutanoate収率 103.4%HCID 12647073Methyl 2-phenylmethylbutyrate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-9b11bd59a46b4a20a4f6931baf252a2c
出典データセット
uspto-grants-2000_05
特許番号
US06066666

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