4-Chlorobenzaldehyde → Benzene, 1-chloro-4-ethynyl-

HRID 65225

反応式

HRID 65225 の反応式
[Br-].Br[CH2:3][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CC(C)([O-])C.[K+].[Cl:29][C:30]1[CH:37]=[CH:36][C:33]([CH:34]=O)=[CH:32][CH:31]=1.[Cl-].[NH4+]>C1COCC1.O>[Cl:29][C:30]1[CH:37]=[CH:36][C:33]([C:34]#[CH:3])=[CH:32][CH:31]=1

参加物

7

反応物 4

HCID 77264-ChlorobenzaldehydeHCID 25517Ammonium ChlorideHCID 2733422Phosphonium, (bromomethyl)triphenyl-, bromide (1:1)HCID 23665647Potassium tert-butoxide2 回

生成物 1

HCID 70118Benzene, 1-chloro-4-ethynyl-

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

Dissolve 276.5 g (0.634 mole) of bromomethyltriphenylphosphonium bromide in 1800 ml THF and cool to -78° C. Add 67.6 g (0.062 mole) potassium tert.-butoxide and stir at -78° C. for 2 hours. Add 89.12 g p-chlorobenzaldehyde in 200 ml THF to cold reaction mixture and stir for 30 minutes. Add 142.3 g potassium tert.-butoxide and then allow to warm to room temperature. After 18 hours, add 500 ml saturated aqueous ammonium chloride solution and 500 ml H2O and extract with 500 ml diethyl ether. Wash organic layer with 2×400 ml saturated aqueous sodium chloride solution, dry over magnesium sulfate, filter and evaporate solvent to dryness. Wash residue with 200 ml hexane and filter off precipitate. Evaporate hexane and dissolve material in 150 ml hexane methylene chloride (66:33) solution and elute through column containing 300 g silica gel (Merck 60-230 mesh) with hexane: methylene chloride (66:33) solution. Monitor column chromatography using thin-layer chromatography on silica gel (hexane: methylene chloride, 66:33). Collect desired fraction and evaporate solvent. Distill residue in vacuo and collect fraction boiling at 65° C. (8.5 mmHg) to obtain the title compound.

後処理

  1. customto cold reaction mixture
  2. stirringstir for 30 minutes
  3. temperatureto warm to room temperature
  4. waitAfter 18 hours
  5. extractionextract with 500 ml diethyl ether
  6. dry with materialWash organic layer with 2×400 ml saturated aqueous sodium chloride solution, dry over magnesium sulfate
  7. filtrationfilter
  8. customevaporate solvent to dryness
  9. filtrationWash residue with 200 ml hexane and filter off precipitate
  10. dissolutionEvaporate hexane and dissolve material in 150 ml hexane methylene chloride (66:33) solution
  11. washelute through column
  12. additioncontaining 300 g silica gel (Merck 60-230 mesh) with hexane: methylene chloride (66:33) solution
  13. customCollect desired fraction
  14. customevaporate solvent
  15. distillationDistill residue in vacuo and collect fraction boiling at 65° C. (8.5 mmHg)

出典と根拠

ORDレコード
ord-f49c603bd83546558a5b9c53d1ab9bc8
出典データセット
uspto-grants-1986_09
特許番号
US04613609

関連ノート

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