Ethyl chloroformate → HCID 20334482, compound

HRID 437176Notes

Reaction equation

HRID 437176 reaction equation
[C:1]([CH2:4][CH2:5][C:6]1([C:13]2[CH:18]=[CH:17][CH:16]=[C:15]([O:19][CH3:20])[CH:14]=2)[CH2:11][CH2:10][CH2:9][CH2:8][C:7]1=[O:12])(O)=[O:2].S([O-])([O-])(=O)=O.[Na+].[Na+].ClC(OCC)=O.[N-:34]=[N+:35]=[N-:36].[Na+]>O.CCOCC.C(N(CC)CC)C>[N:34]([C:1]([CH2:4][CH2:5][C:6]1([C:13]2[CH:18]=[CH:17][CH:16]=[C:15]([O:19][CH3:20])[CH:14]=2)[CH2:11][CH2:10][CH2:9][CH2:8][C:7]1=[O:12])=[O:2])=[N+:35]=[N-:36]

Participants

8

Reactant 4

HCID 10928Ethyl chloroformateHCID 24436Sodium SulfateHCID 33557Sodium AzideHCID 20334481HCID 20334481, compound

Product 1

HCID 20334482HCID 20334482, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
0 °C

Procedure

About 225 g. of 2-(β-carboxyethyl)-2-(m-methoxyphenyl)cyclohexanone were mixed with 125 g. of triethylamine and about 20 g. of sodium sulfate. A solution of 99 g. of ethyl chloroformate in 3250 ml. of anhydrous ether was added in dropwise fashion, thus converting the carboxyethyl group to an acid chloride. The reaction mixture was stirred for about 1 hour at about 0° C. at which point 89 g. of sodium azide in 350 ml. of water were added in dropwise fashion. After the addition had been completed, the reaction mixture was stirred for an additional 2 hours at 0° C. The organic layer was separated. 2-(β-Azidoformylethyl)-2-(m-methoxyphenyl)cyclohexanone formed in the above reaction was isolated as an oil by evaporation of the ether in vacuo. The residual oil was dissolved in 3.5 l. of benzene, and the solution heated at refluxing temperature for about 1.5 hours. The benzene was removed by evaporation in vacuo. By this procedure the azidoformyl group was rearranged under Curtius conditions to yield the corresponding isocyanate. The benzene was removed by evaporation in vacuo. The residual isocyanate was next hydrolyzed to the cyclic imine by heating overnight in a mixture containing 1200 ml. of water, 1200 ml. of glacial acetic acid and 1200 ml. of 12N aqueous hydrochloric acid. The hydrolysis mixture was cooled and then made strongly basic with 50 percent aqueous sodium hydroxide. 3a-(m-methoxyphenyl)-2,3,3a,4,5,6,7-heptahydroindole thus produced was extracted into ether, and the ether layer separated, washed with water and dried. Evaporation of the ether layer to dryness yielded 153.2 g. of 3a-(-m-methoxyphenyl)-2,3,3a,4,5,6,7-heptahydroindole, distilling at about 140° C. at 0.07 mm/g. (For comparison, see Langlois et al., Tetrahedron, 27, 5641 (1971) compound 10 and page 5647, table 4, compound 42).

Workup

  1. additionAfter the addition
  2. stirringthe reaction mixture was stirred for an additional 2 hours at 0° C
  3. customThe organic layer was separated

Sources & evidence

ORD record
ord-f85cd6f4c5d14abb9a798146fe12e20c
Source dataset
uspto-grants-1977_06
Patent number
US04029796

Reaction notes

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