Hydrochloric Acid → 6-chloro-4',5'-dihydrospiro[benzo[b]thiophene-2(3H),3'(2'H)-furan]-3,2'-dione

HRID 1902242ノート

反応式

HRID 1902242 の反応式
[Cl:1][C:2]1[CH:3]=[C:4]([SH:11])[C:5](=[CH:9][CH:10]=1)[C:6]([OH:8])=O.C(=O)([O-])[O-].[Na+].[Na+].Br[CH:19]1[CH2:24][CH2:23][O:22][C:20]1=[O:21].Cl>O.C(OC(=O)C)(=O)C.C(N(CC)CC)C>[Cl:1][C:2]1[CH:10]=[CH:9][C:5]2[C:6](=[O:8])[C:19]3([CH2:24][CH2:23][O:22][C:20]3=[O:21])[S:11][C:4]=2[CH:3]=1

参加物

8

反応物 4

HCID 313Hydrochloric AcidHCID 10340Sodium CarbonateHCID 954632(3H)-Furanone, 3-bromodihydro-HCID 204569744-Chloro-2-sulfanylbenzoic acid

生成物 1

HCID 127679226-chloro-4',5'-dihydrospiro[benzo[b]thiophene-2(3H),3'(2'H)-furan]-3,2'-dione収率 8.3%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 7918Acetic Anhydride溶媒HCID 8471Triethylamine溶媒

実験手順

In 200 ml of water were dissolved 14.2 g of 4-chlorothiosalicylic acid and 20 g of sodium carbonate, and 19.1 g of α-bromo-γ-butyrolactone was added dropwise to the solution under ice-cooling. After stirring the solution at room temperature for 6 hours, 35 ml of concentrated hydrochloric acid was added to the reaction solution at room temperature to acidify. After stirring at room temperature for 3 hours, the precipitate was collected, washed with water and dried, resulting in crude α-[(2-carboxy-5-chlorophenyl)thio]-γ-butyrolactone. The crude product was dissolved in 150 ml of acetic anhydride and 30 ml of triethylamine, and heated under a stream of nitrogen at 130° C. for 10 minutes. The reaction solution was evaporated to dryness under reduced pressure, and the resulting residue was chromatographed on a column of activated carbon and silica gel. Recrystallization from ethanol of the resultant crude crystals yielded 1.60 g of 6-chloro-4',5'-dihydrospiro[benzo[b]thiophene-2(3H),3'(2'H)-furan]-3,2'-dione as colorless needles. Melting point: 157°-158° C.

後処理

  1. additionwas added dropwise to the solution under ice-
  2. temperaturecooling
  3. stirringAfter stirring at room temperature for 3 hours
  4. customthe precipitate was collected
  5. washwashed with water
  6. customdried
  7. customresulting in crude α-[(2-carboxy-5-chlorophenyl)thio]-γ-butyrolactone
  8. customThe reaction solution was evaporated to dryness under reduced pressure
  9. customthe resulting residue was chromatographed on a column of activated carbon and silica gel
  10. customRecrystallization from ethanol of the resultant crude crystals

出典と根拠

ORDレコード
ord-8e5a66bb914a45868ede14f402161416
出典データセット
uspto-grants-1982_12
特許番号
US04362740

反応ノート

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