4,5-Dibromothiophene-2-carbaldehyde → cis-3-(4,5-Dibromo-thiophen-2-yl)-acrylic acid tert-butyl ester

HRID 30245

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HRID 30245 반응식
[C:1]([O:5][C:6](=[O:24])[CH2:7]P(OC1C=CC=CC=1)(OC1C=CC=CC=1)=O)([CH3:4])([CH3:3])[CH3:2].[Br:25][C:26]1[CH:27]=[C:28]([CH:32]=O)[S:29][C:30]=1[Br:31]>C1COCC1.CO>[C:1]([O:5][C:6](=[O:24])/[CH:7]=[CH:32]\[C:28]1[S:29][C:30]([Br:31])=[C:26]([Br:25])[CH:27]=1)([CH3:2])([CH3:3])[CH3:4]

참가 물질

5

반응물 2

HCID 8131644,5-Dibromothiophene-2-carbaldehydeHCID 10689048Tert-butyl (diphenoxyphosphoryl)acetate

생성물 1

HCID 67205492cis-3-(4,5-Dibromo-thiophen-2-yl)-acrylic acid tert-butyl ester

시약·촉매·용매 2

HCID 887Methanol용매HCID 8028Tetrahydrofuran용매2회

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온도
-78 °C

실험 절차

(Diphenoxy-phosphoryl)-acetic acid tert-butyl ester (8.49 g, 24.4 mmol) was dissolved in THF (519 ml) and cooled to −78° C. followed by the addition of triton B (13.3 ml, 40% by wt. in MeOH). After 15 minutes a solution of 4,5-Dibromo-thiophene-2-carbaldehyde (7.0 g, 25.9 mmol) in THF (20 ml) was added and the reaction was stirred for 1 hour. Next, the reaction mixture was quenched with sat. NH4Cl (250 ml), diluted with H2O (500 ml), and extracted with EtOAc (2×300 ml). The organic layers were washed with water (2×200 ml), brine (100 ml), and dried (MgSO4). The crude was passed through a plug of silica gel with EtOAc providing the desired product 9.2 g (96%) as a 4:1 mixture of cis:trans. MS calculated for C10H12BrNS−H 367, observed M-tBu 309, 311, 313.

후처리

  1. customNext, the reaction mixture was quenched with sat. NH4Cl (250 ml)
  2. additiondiluted with H2O (500 ml)
  3. extractionextracted with EtOAc (2×300 ml)
  4. washThe organic layers were washed with water (2×200 ml), brine (100 ml)
  5. dry with materialdried (MgSO4)
  6. additionas a 4:1 mixture of cis

출처 및 근거

ORD 기록
ord-295c8f725dc14dd58e85687443b962aa
출처 데이터셋
uspto-grants-2008_09
특허 번호
US07423056B2

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