Ethyl Bromide → (2,4Dichlorophenyl)-2-buten-1,4-diol

HRID 322842

반응식

HRID 322842 반응식
[Mg].C(Br)C.[Cl:5][C:6]1[CH:11]=[CH:10][C:9](I)=[C:8]([Cl:13])[CH:7]=1.C[Mg]Cl.[CH2:17]([OH:22])[C:18]#[C:19][CH2:20][OH:21].[NH4+].[Cl-]>C(OCC)C.C1COCC1>[Cl:13][C:8]1[CH:7]=[C:6]([Cl:5])[CH:11]=[CH:10][C:9]=1[CH:17]([OH:22])[CH:18]=[CH:19][CH2:20][OH:21]

참가 물질

9

반응물 6

HCID 6332Ethyl Bromide2회HCID 80662-Butyne-1,4-diolHCID 25517Ammonium ChlorideHCID 968642,4-Dichloro-1-iodobenzeneHCID 5462224MagnesiumHCID 178418332HCID 178418332, 화합물

생성물 1

HCID 53770236(2,4Dichlorophenyl)-2-buten-1,4-diol수율 7%

시약·촉매·용매 2

HCID 3283Diethyl Ether용매2회HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
0 °C

실험 절차

A suspension under nitrogen of magnesium (0.8 g; 32.7 mmoles) in ethyl ether (17 ml) kept at 20° C. under stirring, was added with ethyl bromide (25 mg). After 15 minutes a solution of 1,3-dichloro4-iodobenzene (5.95 g; 21.8 mmoles) and ethyl bromide (25 mg) in dry ether (13 ml) was dropwise added (about 1 hour) keeping the temperature at 15-20° C. At the end of the dropping the suspension was kept at 15-20° C. for 2 hours more. The magnesium in excess was removed and the obtained solution was dropped, keeping the temperature at 0-5° C., in a second flask containing a suspension formerly prepared. Such suspension was obtained by adding, at 0-5° C., a THF solution of 3M methyl magnesium chloride (9.6 ml; 29 mmoles) to a solution of 2-butin-1,4-diol (1.25 g; 14.5 mmoles) in THF (30 ml). At the end of the addition the suspension was refluxed and stirred at mild reflux for 24 hours. After cooling to 0° C., an aqueous solution of saturated NH4Cl was added, the phases were divided and the aqueous one extracted in ether (30 ml). The joined organic phases were washed with water (30 ml), anhydrified over dry Na2SO4, dried. The product was purified by flash chromatography (SiO2; petrolatum/ethyl acetate 60/40) to give 0.24 g of (E) (2,4dichlorophenyl)-2-buten-1,4-diol (yield 7,3%). The 1H-NMR effected on the product is practically the same of the one reported in example 4.

후처리

  1. customkept at 20° C.
  2. customat 15-20° C
  3. customThe magnesium in excess was removed
  4. additionthe obtained solution was dropped
  5. customat 0-5° C.
  6. additionin a second flask containing a suspension
  7. customformerly prepared
  8. customSuch suspension was obtained
  9. additionby adding, at 0-5° C.
  10. additionAt the end of the addition the suspension
  11. temperaturewas refluxed
  12. stirringstirred
  13. temperatureat mild reflux for 24 hours
  14. extractionthe aqueous one extracted in ether (30 ml)
  15. washThe joined organic phases were washed with water (30 ml)
  16. dry with materialover dry Na2SO4, dried
  17. customThe product was purified by flash chromatography (SiO2; petrolatum/ethyl acetate 60/40)

출처 및 근거

ORD 기록
ord-43e2bcdba08e429fa4a6111cd76f8875
출처 데이터셋
uspto-grants-2001_04
특허 번호
US06211387B1

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