Dimethyl Sulfoxide → (Rac)-4-(1-methoxycarbonyl-3-oxo-propyl)-5-oxo-[1,4]diazepane-1-carboxylic acid benzyl ester

HRID 655505Notes

Reaction equation

HRID 655505 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[CH2:11]([O:18][C:19]([N:21]1[CH2:27][CH2:26][C:25](=[O:28])[N:24]([CH:29]([C:33]([O:35][CH3:36])=[O:34])[CH2:30][CH2:31][OH:32])[CH2:23][CH2:22]1)=[O:20])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(N(CC)CC)C.P([O-])(O)(O)=O.[K+]>ClCCl>[CH2:11]([O:18][C:19]([N:21]1[CH2:27][CH2:26][C:25](=[O:28])[N:24]([CH:29]([C:33]([O:35][CH3:36])=[O:34])[CH2:30][CH:31]=[O:32])[CH2:23][CH2:22]1)=[O:20])[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

7

Reactant 5

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 516951Monobasic potassium phosphateHCID 67080666(Rac)-4-(3-hydroxy-1-methoxycarbonyl-propyl)-5-oxo-[1,4]diazepane-1-carboxylic acid benzyl ester

Product 1

HCID 87260904(Rac)-4-(1-methoxycarbonyl-3-oxo-propyl)-5-oxo-[1,4]diazepane-1-carboxylic acid benzyl ester

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
0 °C

Procedure

To a solution of 0.31 ml (3.60 mmol) of oxalyl chloride in 7.7 ml dichloromethane at −50 to −60° C. was added a solution of 0.53 ml (7.51 mmol) dimethylsulfoxide in 1.6 ml of dichloromethane within 10 min. The solution was stirred for 5 min and a solution of 1.14 (3.13 mmol) (rac)-4-(3-hydroxy-1-methoxycarbonyl-propyl)-5-oxo-[1,4]diazepane-1-carboxylic acid benzyl ester in 6.8 ml dichloromethane was added within 10 min. The mixture was stirred for 15 min and 2.18 ml (15.64 mmol) of triethylamine were added within 20 min. The suspension was stirred for 1¼ h and slowly warmed to 0° C. The reaction was neutralized with cold 10% aq. potassium dihydrogenphosphate solution (adjusted with 10% aq. potassium hydrogensulfate solution to pH 4-5) and extracted with diethyl ether (3×). The organic phases were washed with 10% aq. potassium dihydrogenphosphate solution, sat. aq. sodium hydrogencarbonate solution, 10% aq. sodium chloride solution, dried over Na2SO4 evaporated to yield 1.25 g (quantitative) of the title compound as yellow oil. MS: 363.2 (MH+).

Workup

  1. stirringThe mixture was stirred for 15 min
  2. stirringThe suspension was stirred for 1¼ h
  3. extractionextracted with diethyl ether (3×)
  4. washThe organic phases were washed with 10% aq. potassium dihydrogenphosphate solution, sat. aq. sodium hydrogencarbonate solution, 10% aq. sodium chloride solution
  5. dry with materialdried over Na2SO4
  6. customevaporated

Sources & evidence

ORD record
ord-1f9138b1369d44a0b51bf12058ad2c41
Source dataset
uspto-grants-2011_12
Patent number
US08071586B2

Reaction notes

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