Hydrochloric Acid → Tert-butyl 2-fluoro-cyclopropane-1-carboxylate

HRID 130612

反応式

HRID 130612 の反応式
[BH4-].[Na+].Cl[C:4]1([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:6][CH:5]1[F:7].O.Cl>CN1C(=O)CCC1.O.O.O.O.O.O.[Co](Cl)Cl.C1(C)C=CC=CC=1>[F:7][CH:5]1[CH2:6][CH:4]1[C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9]

参加物

8

反応物 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 4311764Sodium borohydrideHCID 11858685Tert-butyl 1-chloro-2-fluoro-cyclopropane-1-carboxylate

生成物 1

HCID 11819326Tert-butyl 2-fluoro-cyclopropane-1-carboxylate収率 98%

試薬・触媒・溶媒 3

HCID 517166Dichlorocobalt hexahydrate触媒HCID 1140Toluene溶媒HCID 13387N-methyl-2-pyrrolidone溶媒3 回

実験手順

Sodium borohydride (8.75 g, 231.21 mmol) was dissolved in NMP (95 mL) under stirring with a stirring blade at room temperature. Subsequently, to the resultant solution was added an NMP solution (20 mL) of tert-butyl 1-chloro-2-fluoro-cyclopropane-1-carboxylate (cis/trans=62/38) (hereinafter the compound will be referred to as “compound (1a)”) (30 g, 154.14 mmol). An NMP solution (35 mL) of cobalt chloride hexahydrate (1.1 g, 4.62 mmol) was gradually added to the resultant reaction mixture under ice cooling. After completion of dropwise addition, the resultant mixture was stirred with a stirring blade at room temperature for 30 minutes, and at 40° C. for three hours. After completion of reaction, water (120 mL) was added to the resultant reaction mixture at the same temperature, followed by addition of 5 N hydrochloric acid (30 mL). Subsequently, toluene was added to the reaction mixture for extraction. The resultant toluene layer was washed with water, and then dried over sodium sulfate, to thereby yield a toluene solution containing 24.3 g (yield: 98%) of the title compound. Yield was determined by means of high performance liquid chromatography (HPLC) (the same shall apply hereinafter).

後処理

  1. customreaction mixture under ice cooling
  2. additionAfter completion of dropwise addition
  3. additionwas added to the resultant
  4. customreaction mixture at the same temperature
  5. washThe resultant toluene layer was washed with water
  6. dry with materialdried over sodium sulfate
  7. customto thereby yield a toluene solution

出典と根拠

ORDレコード
ord-31dde147dee64b16bd0a80d7ce46349c
出典データセット
uspto-grants-2008_06
特許番号
US07381833B2

関連ノート

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