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Hydrochloric Acid → 7-Chloro-2,2-difluorobenzo[d][1,3]dioxole-4-carboxylic Acid

HRID 1586344
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HRID 1586344 반응식
[F:1][C:2]1([F:14])[O:6][C:5]2[CH:7]=[CH:8][CH:9]=[C:10]([C:11]([OH:13])=[O:12])[C:4]=2[O:3]1.C([Li])CCC.[Cl:20]C(Cl)(Cl)C(Cl)(Cl)Cl.Cl>O1CCCC1.CCCCCC>[Cl:20][C:7]1[C:5]2[O:6][C:2]([F:1])([F:14])[O:3][C:4]=2[C:10]([C:11]([OH:13])=[O:12])=[CH:9][CH:8]=1
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참가 물질

7

반응물 4

HCID 313Hydrochloric AcidHCID 6214HexachloroethaneHCID 27740672,2-Difluoro-1,3-dioxaindane-4-carboxylic acidHCID 178418339Butyllithium

생성물 1

HCID 103768457-Chloro-2,2-difluorobenzo[d][1,3]dioxole-4-carboxylic Acid수율 42.1%

시약·촉매·용매 2

HCID 8028
Tetrahydrofuran
용매
2회
HCID 8058Hexane용매

실험 절차

7.5 g (0.038 mol) of 2,2-difluoro-1,3-benzodioxole-4-carboxylic acid, prepared according to the process described in European Application 0,333,658, are dissolved, with stirring and under an argon atmosphere, in 75 ml of dry tetrahydrofuran (THF). ml (0.081 mol) of n-butyllithium in solution in hexane are run in dropwise at -70° C. After stirring for 1 hour, 8.9 g (0.038 mol) of hexachloroethane in solution in 50 ml of dry tetrahydrofuran (THF) are run in. After 2 hours at -70° C., the temperature is allowed to return to 10° C. The reaction mixture is hydrolysed with 150 ml of ice-cold water and brought to a pH of approximately 1 by addition of 1N hydrochloric acid. The aqueous phase is extracted with ether, dried over magnesium sulphate and concentrated under vacuum. The solid is washed with heptane to give 3.7 g (0.016 mol) of 7-chloro-2,2-difluoro-1,3-benzodioxole-4-carboxylic acid (yield: 42%; melting point: 185° C.).

후처리

  1. dissolutionare dissolved
  2. customdropwise at -70° C
  3. waitAfter 2 hours at -70° C.
  4. customto return to 10° C
  5. extractionThe aqueous phase is extracted with ether
  6. dry with materialdried over magnesium sulphate
  7. concentrationconcentrated under vacuum
  8. washThe solid is washed with heptane

출처 및 근거

ORD 기록
ord-17233b19b9334af382f9e6a9fb6aa25e
출처 데이터셋
uspto-grants-1999_08
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US05945382

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