Thionyl Chloride → (S)-[2-[[2-(2-Chlorobenzoyl)-4-nitrophenyl]amino]-1-methyl-2-oxoethyl]-carbamic Acid Phenylmethyl Ester

HRID 1632167Notes

Reaction equation

HRID 1632167 reaction equation
[C:1]([NH:11][C@H:12]([C:14]([OH:16])=O)[CH3:13])([O:3][CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:2].S(Cl)(Cl)=O.[NH2:21][C:22]1[CH:36]=[CH:35][C:34]([N+:37]([O-:39])=[O:38])=[CH:33][C:23]=1[C:24]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=1[Cl:32])=[O:25]>O1CCCC1>[CH2:4]([O:3][C:1](=[O:2])[NH:11][C@H:12]([C:14](=[O:16])[NH:21][C:22]1[CH:36]=[CH:35][C:34]([N+:37]([O-:39])=[O:38])=[CH:33][C:23]=1[C:24](=[O:25])[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=1[Cl:32])[CH3:13])[C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=1

Participants

5

Reactant 3

HCID 24386Thionyl ChlorideHCID 748302-Amino-5-nitro-2'-chlorobenzophenoneHCID 736104N-carbobenzyloxyalanine

Product 1

HCID 131713833(S)-[2-[[2-(2-Chlorobenzoyl)-4-nitrophenyl]amino]-1-methyl-2-oxoethyl]-carbamic Acid Phenylmethyl Ester

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

53.6 g of carbobenzoxy-L-alanine are dissolved in 400 ml of dry tetrahydrofuran, the solution is treated dropwise with 30 g of thionyl chloride while cooling with ice and the mixture is stirred for 1 hour in the cold. A solution of 54 g (0.2 mol) of 2-amino-5-nitro-2'-chlorobenzophenone in 150 ml of dry tetrahydrofuran is subsequently added dropwise thereto rapidly, whereupon the mixture is stirred at room temperature for 24 hours. The solution obtained is concentrated, the residue is treated with ice and 10 percent sodium bicarbonate solution and extracted with methylene chloride. The organic solution is dried over sodium sulphate and evaporated. The residue is treated with dry ether, left to crystallize for 1 hour and then filtered while rinsing with ether/petroleum ether (1:1). After drying, there is obtained (S)-benzyl-[1-[[2-(o-chlorobenzoyl)-4-nitrophenyl]carbamoyl]ethyl]carbamate of melting point 143°-145°; [α]25 D =18° (1 percent solution in methylene chloride).

Workup

  1. temperaturewhile cooling with ice
  2. stirringrapidly, whereupon the mixture is stirred at room temperature for 24 hours
  3. customThe solution obtained
  4. concentrationis concentrated
  5. additionthe residue is treated with ice and 10 percent sodium bicarbonate solution
  6. extractionextracted with methylene chloride
  7. dry with materialThe organic solution is dried over sodium sulphate
  8. customevaporated
  9. additionThe residue is treated with dry ether
  10. waitleft
  11. customto crystallize for 1 hour
  12. filtrationfiltered
  13. washwhile rinsing with ether/petroleum ether (1:1)
  14. customAfter drying

Sources & evidence

ORD record
ord-651b8ff5012c4842ba876c94a322e15a
Source dataset
uspto-grants-1984_10
Patent number
US04474777

Reaction notes

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