Ethanol → 4-Bromo-5-nitro-thiophene-2-carbaldehyde oxime

HRID 132074

반응식

HRID 132074 반응식
[Br:1][C:2]1[CH:3]=[C:4]([CH:10]=O)[S:5][C:6]=1[N+:7]([O-:9])=[O:8].C(O)C.N1C=CC=CC=1.Cl.[NH2:22][OH:23]>CCCCCCC.CCOC(C)=O>[Br:1][C:2]1[CH:3]=[C:4]([CH:10]=[N:22][OH:23])[S:5][C:6]=1[N+:7]([O-:9])=[O:8]

참가 물질

6

반응물 4

HCID 702EthanolHCID 1049PyridineHCID 443297Hydroxyamine hydrochlorideHCID 218862814-Bromo-5-nitrothiophene-2-carbaldehyde

생성물 1

HCID 738521524-Bromo-5-nitro-thiophene-2-carbaldehyde oxime수율 97.5%

시약·촉매·용매 1

HCID 21899848Ethylacetate heptane용매

반응 조건

온도
80 °C

실험 절차

A 12-L three neck, round bottom flask equipped with mechanical stirring, a temperature probe and a reflux condenser was charged with 4-Bromo-5-nitro-thiophene-2-carbaldehyde (Example 25: step b, 426.0 g, 1.805 mol), absolute ethanol (4L) and pyridine (189.9 mL, 2.35 mol). Hydroxylamine hydrochloride (163.3 g, 2.35 mol) was added in one portion and the mixture was heated. The mixture became a slurry at 27° C., turned clear at 50° C. and was refluxed at 80° C. for 1.5 hour. TLC analysis showed reaction completion (2:1 heptane/EtOAc). The cooled reaction mixture was concentrated in vaccuo then dried azeotrophically using toluene (1L). The resulting moist solids were transferred to a 10-L glass carboy and stirred with H2O (3L). After 1 hour, the solids were isolated by filtration, rinsed with H2O (3L) and heptane (3L), then dried in vacuum oven to give the desired title compound as a brown powder (441.65 g, 97%). 1H-NMR (DMSO): δ 13.0 (1H, br s), 8.1 (1H, s), 7.8 (1H, s).

후처리

  1. temperaturethe mixture was heated
  2. customat 27° C.
  3. customturned clear at 50° C.
  4. customThe cooled reaction mixture
  5. concentrationwas concentrated in vaccuo
  6. dry with materialthen dried azeotrophically using toluene (1L)
  7. customthe solids were isolated by filtration
  8. washrinsed with H2O (3L) and heptane (3L)
  9. customdried in vacuum oven

출처 및 근거

ORD 기록
ord-999775abc284420c80748a857f21ae39
출처 데이터셋
uspto-grants-2008_06
특허 번호
US07385066B2

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