Carbonic acid, 1-chloroethyl ethyl ester → HCID 178473648, compound

HRID 1979961Notes

Reaction equation

HRID 1979961 reaction equation
C(OC([NH:8][CH2:9][C@H:10]1[CH2:15][CH2:14][C@H:13]([C:16]([OH:18])=[O:17])[CH2:12][CH2:11]1)=O)(C)(C)C.[C:19](=[O:27])([O:23][CH:24]([Cl:26])[CH3:25])[O:20][CH2:21][CH3:22]>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.[OH-].[Na+].C(Cl)(Cl)Cl.ClC=C(Cl)Cl.C(O)(C)C>[ClH:26].[NH2:8][CH2:9][C@H:10]1[CH2:11][CH2:12][C@H:13]([C:16]([O:18][CH:21]([O:20][C:19]([O:23][CH2:24][CH3:25])=[O:27])[CH3:22])=[O:17])[CH2:14][CH2:15]1

Participants

8

Reactant 2

HCID 162095Carbonic acid, 1-chloroethyl ethyl esterHCID 178453624HCID 178453624, compound

Product 1

HCID 178473648HCID 178473648, compound

Reagents, catalysts & solvents 5

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 3776IsopropanolSolventHCID 6212ChloroformSolventHCID 6575TrichloroethyleneSolventHCID 14798Sodium HydroxideSolvent

Conditions

Temperature
0 °C

Procedure

A solution of trans-4-(tert.-butoxycarbonylaminomethyl) cyclohexanecarboxylic acid (25.7 g; 0.1 mol) and tetrabutylammonium hydrogen sulfate (34 g; 0.1 mol) in 2N sodium hydroxide (100 ml) was extracted with ethanolfree chloroform. The chloroform solution was dried and evaporated to give 50 g. This was dissolved in trichloroethylene (200 ml) and ethyl (1-chloroethyl) carbonate (16.8 g; 0.11 mol) was added. After refluxing for 3 h the solution was washed with dilute sulphuric acid, sodium bicarbonate solution and water. After evaporation of chloroform the residue was dissolved in ethyl acetate cooled to 0° C. To this solution a cold solution of hydrochloric acid in ethyl acetate was added. After 3 h at ice bath temperature the solvent was evaporated to give 23 g. This was dissolved in isopropyl alcohol and precipitated with diisopropyl ether. Yield 15 g (49%), m.p. 139° C.

Workup

  1. dry with materialThe chloroform solution was dried
  2. customevaporated
  3. customto give 50 g
  4. temperatureAfter refluxing for 3 h the solution
  5. washwas washed with dilute sulphuric acid, sodium bicarbonate solution and water
  6. customAfter evaporation of chloroform the residue
  7. dissolutionwas dissolved in ethyl acetate
  8. additionTo this solution a cold solution of hydrochloric acid in ethyl acetate was added
  9. customAfter 3 h at ice bath temperature the solvent was evaporated
  10. customto give 23 g
  11. customprecipitated with diisopropyl ether

Sources & evidence

ORD record
ord-704c5fef3e7b4fdb942173af5f36b61c
Source dataset
uspto-grants-1984_11
Patent number
US04483867

Reaction notes

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