Hydrochloric Acid → 6-(2-Chloroethyl)-1,3,3-trimethylbicyclo[2.2.2]octan-2-one

HRID 1390648Notes

Reaction equation

HRID 1390648 reaction equation
[CH3:1][C:2]12[CH2:12][CH2:11][CH:5]([CH2:6][CH:7]1[CH2:8][CH2:9]O)[C:4]([CH3:14])([CH3:13])[C:3]2=[O:15].S(Cl)([Cl:18])=O.Cl>C1C=CC=CC=1>[CH3:1][C:2]12[CH2:12][CH2:11][CH:5]([CH2:6][CH:7]1[CH2:8][CH2:9][Cl:18])[C:4]([CH3:14])([CH3:13])[C:3]2=[O:15]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 24386Thionyl Chloride3×HCID 21419393HCID 21419393, compound

Product 1

HCID 213335696-(2-Chloroethyl)-1,3,3-trimethylbicyclo[2.2.2]octan-2-one

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Conditions

Temperature
90 °C

Procedure

To a 100 ml microflask equipped with thermometer, reflux condenser, dropping funnel and magnetic stirrer is charged 12.3 g of 1,3,3-trimethyl-6-(2-hydroxyethyl) bicyclo(2.2.2)-octan-2-one prepared according to the process of Example XVII, and 20 ml benzene. The dropping funnel is charged with 12 g thionyl chloride. The thionyl chloride is added to the reaction mass from the dropping funnel, slowly, over a period of five minutes as the temperature of the reaction mass rises to 35° C. The reaction mass is then refluxed for a period of 10 hours at 90° C. The flask is then vented to the atmosphere and heated on a steam bath in order to volatilize the unreacted thionyl chloride and any hydrogen chloride reaction product remaining. The reaction mass is then cooled and hydrolyzed with 50 g ice. The organic layer is separated, and the aqueous phase is extracted with four 20 ml portions of anhydrous diethyl ether. The organic layers are bulked and washed with (i) three 20 ml portions of saturated sodium bicarbonate solution and (ii) one 20 ml portion of water. The organic phase is then dried over anhydrous magnesium sulfate and stripped of the diethyl ether. The reaction product is then distilled at 105°-115° C. at a pressure of 0.2 mm Hg. Its structure, confirmed by NMR and mass spectral analyses is as follows: ##STR32## NMR Analysis: δ, 0.92 (s, 3H), 1.08 (s, 3H), 1.15 (s, 3H), 1.44-2.17 (m, 10H), 3.55 (m, 2H) ppm

Workup

  1. customTo a 100 ml microflask equipped with thermometer
  2. temperaturereflux condenser
  3. customprepared
  4. temperatureheated on a steam bath in order
  5. customThe organic layer is separated
  6. extractionthe aqueous phase is extracted with four 20 ml portions of anhydrous diethyl ether
  7. washwashed with (i) three 20 ml portions of saturated sodium bicarbonate solution and (ii) one 20 ml portion of water
  8. dry with materialThe organic phase is then dried over anhydrous magnesium sulfate
  9. distillationThe reaction product is then distilled at 105°-115° C. at a pressure of 0.2 mm Hg

Sources & evidence

ORD record
ord-e9e039ebb7544ca2bc369ec431a1f18d
Source dataset
uspto-grants-1979_02
Patent number
US04139650

Reaction notes

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