Phosgene → 8-Chloro-6-(2-chlorophenyl)-1,2-dihydro-1-oxo-4H-imidazo[1,5-a][1,4]benzodiazepine-3-carboxylic acid methyl ester

HRID 261694ノート

反応式

HRID 261694 の反応式
N[CH2:2][O:3][C:4]([CH:6]=[C:7]1[CH2:13][N:12]=[C:11]([C:14]2C=[CH:18][CH:17]=[CH:16][C:15]=2Cl)[C:10]2[CH:21]=[C:22]([Cl:25])[CH:23]=[CH:24][C:9]=2[NH:8]1)=[O:5].O1C(C[O:30][C:31]2C=CC=CC=2)C1.[C:37]([Cl:40])(Cl)=O.[OH-].[NH4+:42].[K+].[Br-]>C(Cl)Cl.C1C=CC=CC=1>[CH3:2][O:3][C:4]([C:6]1[NH:42][C:31](=[O:30])[N:8]2[C:9]3[CH:24]=[CH:23][C:22]([Cl:25])=[CH:21][C:10]=3[C:11]([C:14]3[CH:15]=[CH:16][CH:17]=[CH:18][C:37]=3[Cl:40])=[N:12][CH2:13][C:7]=12)=[O:5]

参加物

8

反応物 5

HCID 6371PhosgeneHCID 14923Ammonium HydroxideHCID 31217Phenyl glycidyl etherHCID 253877Potassium BromideHCID 700515042-[(amino)methoxycarbonylmethylene]-7-chloro-5-(2-chlorophenyl)-1,3-dihydro-2H-1,4-benzodiazepine

生成物 1

HCID 127034758-Chloro-6-(2-chlorophenyl)-1,2-dihydro-1-oxo-4H-imidazo[1,5-a][1,4]benzodiazepine-3-carboxylic acid methyl ester

試薬・触媒・溶媒 2

HCID 241Benzene溶媒HCID 6344Dichloromethane溶媒

実験手順

A stirred solution of 15 g (0.04 mole) of 2-[(amino)methoxycarbonylmethylene]-7-chloro-5-(2-chlorophenyl)-1,3-dihydro-2H-1,4-benzodiazepine and 12 g (0.08 mole) of 1,2-epoxy-3-phenoxypropane in 150 ml of methylene chloride was cooled in an ice-salt bath and treated with 47 g (0.06 mole) of a 12.5% solution of phosgene in benzene at a moderate rate. Stirring in the cold under a drying tube was continued for 2 hours. A cold solution of 3 N ammonium hydroxide (50 ml) was added and stirring was continued for 10 min. The organic phase was separated, dried over sodium sulfate and evaporated under reduced pressure. Stirring the oily residue with anhydrous ether gave off-white crystals. The crystals were filtered, washed with ether and air dried on the funnel to yield the end product. Recrystallization from ethanol methylene chloride gave white needles with mp 273°-276° (dec). Uv λ max 223 mμ (ε=43800) 276 (21100) infl 348 (1100) ir (KBr) 3150 (NH) 1720 (COOMe, CO) nmr (CDCl3) δ 3.80 ppm (s, 3, OCH3) 4.11 (broad d, 1) and 5.58 (broad d, 1) (AB-system, J=12 Hz, C4 --H) 6.95 (d, 1, J=2.5 Hz, C7 --H) 7.3-7.8 (m, 5, aromatic H) 7.96 (d, 1, J=8 Hz, C10 --H) 11.19 (broad s, 1, NH).

後処理

  1. stirringstirring
  2. waitwas continued for 10 min
  3. customThe organic phase was separated
  4. dry with materialdried over sodium sulfate
  5. customevaporated under reduced pressure
  6. stirringStirring the oily residue with anhydrous ether
  7. customgave off-white crystals
  8. filtrationThe crystals were filtered
  9. washwashed with ether and air
  10. customdried on the funnel
  11. customto yield the end product
  12. customRecrystallization from ethanol methylene chloride
  13. customgave white needles with mp 273°-276° (dec)

出典と根拠

ORDレコード
ord-5e12860fb47c43a38970039545d48bb1
出典データセット
uspto-grants-1979_08
特許番号
US04166185

反応ノート

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