Thionyl Chloride → (S)-benzyl-{1-[[2-(o-fluorobenzoyl)-4-nitrophenyl]carbamoyl]ethyl}carbamate

HRID 848126

Reaction equation

HRID 848126 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[F: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[F:32])[CH3:13])[C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=1

Participants

5

Reactant 3

HCID 24386Thionyl ChlorideHCID 676572-Amino-2'-fluoro-5-nitrobenzophenoneHCID 736104N-carbobenzyloxyalanine

Product 1

HCID 131712080(S)-benzyl-{1-[[2-(o-fluorobenzoyl)-4-nitrophenyl]carbamoyl]ethyl}carbamate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

120 g of carbobenzoxy-L-alanine are dissolved in 800 ml of absolute tetrahydrofuran, treated dropwise while cooling with ice with 70 g of thionyl chloride and stirred for 40 minutes while cooling with ice. There is then rapidly added dropwise thereto a suspension of 100 g (0.38 M) of 2-amino-5-nitro-2'-fluorobenzophenone in 400 ml of absolute tetrahydrofuran and the mixture is stirred at room temperature for 24 hours. The solution obtained is concentrated and the residue is treated with ice and 10% sodium bicarbonate solution and extracted with methylene chloride. The organic solution is dried over sodium sulphate, filtered and concentrated. The residue is dissolved in a small amount of methylene chloride and treated with ether. There is obtained (S)-benzyl-{1-[[2-(o-fluorobenzoyl)-4-nitrophenyl]carbamoyl]ethyl}carbamate. A further recrystallisation from methylene chloride/ether yields a product which melts at 158°-160° C. and shows a rotation of [α]25D =-23.4° (in methylene chloride; 1%). The mother liquors are purified on a 600 g in silica gel column using methylene chloride as the eluting agent, an additional amount of the aforementioned product being obtained.

Workup

  1. additiontreated dropwise
  2. temperaturewhile cooling with ice
  3. additionThere is then rapidly added dropwise
  4. stirringthe mixture is stirred at room temperature for 24 hours
  5. customThe solution obtained
  6. concentrationis concentrated
  7. additionthe residue is treated with ice and 10% sodium bicarbonate solution
  8. extractionextracted with methylene chloride
  9. dry with materialThe organic solution is dried over sodium sulphate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. dissolutionThe residue is dissolved in a small amount of methylene chloride
  13. additiontreated with ether

Sources & evidence

ORD record
ord-87921082936540e4968c6966adcb46a0
Source dataset
uspto-grants-1981_10
Patent number
US04294758

Linked notes

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