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

HRID 132074ノート

反応式

HRID 132074 の反応式
[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]

参加物

6

反応物 4

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

生成物 1

HCID 738521524-Bromo-5-nitro-thiophene-2-carbaldehyde oxime収率 97.5%

試薬・触媒・溶媒 1

HCID 21899848Ethylacetate heptane溶媒

反応条件

温度
80 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-999775abc284420c80748a857f21ae39
出典データセット
uspto-grants-2008_06
特許番号
US07385066B2

反応ノート

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