Borane → HCID 23320956、化合物

HRID 280660ノート

反応式

HRID 280660 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([S:8][C:9]2[C:17]([Cl:18])=[CH:16][C:12]([C:13]([NH2:15])=O)=[CH:11][C:10]=2[Cl:19])=[CH:4][CH:3]=1.B>O1CCCC1>[ClH:1].[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([S:8][C:9]2[C:17]([Cl:18])=[CH:16][C:12]([CH2:13][NH2:15])=[CH:11][C:10]=2[Cl:19])=[CH:6][CH:7]=1

参加物

4

反応物 2

HCID 6331BoraneHCID 13649684HCID 13649684、化合物

生成物 1

HCID 23320956HCID 23320956、化合物収率 162.5%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

A solution of 4-(4-chlorophenylthio)-3,5-dichlorobenzamide (25.7 g, 77.3 mmol) in tetrahydrofuran (155 ml) was added dropwise over 25 minutes to a stirred 1.0M solution of borane in tetrahydrofuran (232 ml) at ambient temperature under nitrogen atmosphere. The mixture was refluxed for 16 hours, cooled to 0° C., and quenched by addition of 2.0N hydrochloric acid. Solvent was evaporated under vacuum and the residue treated with water (400 ml) and diethyl ether. The mixture was basified with 2.5N aqueous sodium hydroxide, the phases were separated, and the aqueous phase extracted twice with diethyl ether. The combined extracts were washed with water (2X) and brine, dried over anhydrous magnesium sulfate, and evaporated under vacuum. The residual oil was dissolved in methanol (500 ml), treated with concentrated hydrochloric acid, and evaporated to dryness at 50° C. under vacuum. The residue was azeotroped twice with methanol, stirred 30 minutes with diethyl ether (300.ml), filtered, washed with diethyl ether (4X), and dried at 40° C. under vacuum to provide 22.3 g (81%) of 4-(4-chlorophenylthio)-3,5-dichlorobenzylamine hydrochloride, m.p. 217°-219° C. The free base was liberated by suspending the salt (4.0 g) in water, basifying with dilute aqueous sodium hydroxide, and extracting with diethyl ether (3X). The combined extracts were washed with water (2X) and brine, dried over anhydrous magnesium sulfate, and evaporated under vacuum to provide 3.59 g (100%) of oily free base.

後処理

  1. temperatureThe mixture was refluxed for 16 hours
  2. customquenched by addition of 2.0N hydrochloric acid
  3. customSolvent was evaporated under vacuum
  4. additionthe residue treated with water (400 ml) and diethyl ether
  5. customthe phases were separated
  6. extractionthe aqueous phase extracted twice with diethyl ether
  7. washThe combined extracts were washed with water (2X) and brine
  8. dry with materialdried over anhydrous magnesium sulfate
  9. customevaporated under vacuum
  10. dissolutionThe residual oil was dissolved in methanol (500 ml)
  11. additiontreated with concentrated hydrochloric acid
  12. customevaporated to dryness at 50° C. under vacuum
  13. customThe residue was azeotroped twice with methanol
  14. filtrationfiltered
  15. washwashed with diethyl ether (4X)
  16. customdried at 40° C. under vacuum

出典と根拠

ORDレコード
ord-798aa1218e774315b93b16f4decb35cb
出典データセット
uspto-grants-1986_05
特許番号
US04590201

反応ノート

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