Thionyl Chloride → 2-(3-Methoxy-4-methyl-phenyl)vinylisocyanate

HRID 394600ノート

反応式

HRID 394600 の反応式
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:10]=[CH:11]C(O)=O)[CH:6]=[CH:7][C:8]=1[CH3:9].S(Cl)(Cl)=O.[N-:19]=[N+]=[N-].[Na+].O.[O:24]1[CH2:29]COCC1>C1C=CC=CC=1>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][N:19]=[C:29]=[O:24])[CH:6]=[CH:7][C:8]=1[CH3:9]

参加物

6

反応物 4

HCID 24386Thionyl ChlorideHCID 33557Sodium AzideHCID 218864351,4-Dioxane--water (1/1)HCID 534017143-Methoxy-4-methylcinnamic acid

生成物 1

HCID 538573922-(3-Methoxy-4-methyl-phenyl)vinylisocyanate

試薬・触媒・溶媒 1

HCID 241Benzene溶媒

実験手順

3-(3-Methoxy-4-methylphenyl)propenoic acid (5.33 g, 27.7 mmol) (prepared according to the procedure described in J. Med. Chem. 1991, 34, 1662-1668) is suspended in benzene (30 mL) and treated dropwise with thionyl chloride (2.22 mL, 30.5 mmol) at 0° C. The reaction is heated to reflux and it is maintained for 1 hour. The volatiles are removed in vacuo and the resulting solid is dissolved in dioxane and added dropwise to a mixture of sodium azide (3.6 g, 55.4 mmol) in water/dioxane (30 mL, 1:5) at 0° C. After stirring 1 hours, the solution is poured over ice-water, the precipitate is collected and washed with water. The solid is dried under vacuum over P2O5(24 hours), dissolved in benzene (30 mL) and heated to reflux slowly over about 4 hours. The benzene is removed to give 2-(3-methoxy-4-methyl-phenyl)vinylisocyanate as a brown oil. The oil is taken tip in o-dichlorobenzene, treated with iodine and heated to reflux for 3.5 hours. The volatiles are removed and the residue is mixed with 2.5% MeOH/CH2Cl2 (10 mL), then allowed to stand overnight at room temperature. The resulting solid is collected washed with hexane and ether, and dried to give the title compound (2.67 g, 14.1 mmol).

後処理

  1. temperatureThe reaction is heated
  2. temperatureto reflux
  3. temperatureit is maintained for 1 hour
  4. customThe volatiles are removed in vacuo
  5. dissolutionthe resulting solid is dissolved in dioxane
  6. customthe precipitate is collected
  7. washwashed with water
  8. dry with materialThe solid is dried under vacuum over P2O5(24 hours)
  9. dissolutiondissolved in benzene (30 mL)
  10. temperatureheated
  11. temperatureto reflux slowly over about 4 hours
  12. customThe benzene is removed

出典と根拠

ORDレコード
ord-eec3adaac62846cd99c1b97b83b552c7
出典データセット
uspto-grants-2003_08
特許番号
US06602864B1

反応ノート

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