Ammonia → HCID 70076920, compound

HRID 1490120Notes

Reaction equation

HRID 1490120 reaction equation
C(OC(Cl)=O)C.[C:7]([C:10]12[CH2:17][CH2:16][C:13]([C:18]#[N:19])([CH2:14][CH2:15]1)[CH2:12][CH2:11]2)(O)=[O:8].C([N:22](CC)CC)C.N>C(Cl)(Cl)Cl>[NH2:22][C:7]([C:10]12[CH2:17][CH2:16][C:13]([C:18]#[N:19])([CH2:14][CH2:15]1)[CH2:12][CH2:11]2)=[O:8]

Participants

6

Reactant 4

HCID 222AmmoniaHCID 8471TriethylamineHCID 10928Ethyl chloroformateHCID 3600093Bicyclo[2.2.2]octane-1-carboxylic acid, 4-cyano-

Product 1

HCID 70076920HCID 70076920, compoundYield 86%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

2.6 ml of ethylchloroformate are rapidly added, dropwise, to a solution of 4.9 g of 1-carboxy-4-cyano-bicyclo[2.2.2]-octane and 3.8 ml of triethylamine in 130 ml of chloroform at -10° C. After 15 minutes of stirring, ammonia gas is introduced to the mixture for 10 minutes. The mixture is stirred for 10 minutes at 0° C., warmed to ambient temperature and after an hour, evaporated to dryness. The residue is stirred with water under heating, cooled, suction filtered, washed with water and dried. The 1-aminocarbonyl-4-cyano-bicyclo[2.2.2]octane [4.2 g (86% of theory); Rf value: 0.78 (Silica gel; methylene chloride/methanol/conc. aqueous ammonia=4:1:0.2)] obtained is suspended in 100 ml of acetonitrile/water (1:1), combined with 15.0 g of bis(trifluoroacetoxy) iodobenzene and stirred for 18 hours at ambient temperature. The reaction mixture is evaporated down to half its volume, shaken twice with ethyl acetate and the aqueous phase is adjusted to a pH of 12 to 13. The aqueous phase is extracted 3 times with ethyl acetate and the combined organic phases are washed with saturated saline solution and dried. The residue is dissolved in ethyl acetate acid and a little acetone and ethereal hydrochloric acid are added. The mixture is cooled in an ice-bath, suction filtered and the product is washed with ethyl acetate.

Workup

  1. customat -10° C
  2. stirringThe mixture is stirred for 10 minutes at 0° C.
  3. customevaporated to dryness
  4. stirringThe residue is stirred with water
  5. temperatureunder heating
  6. temperaturecooled
  7. filtrationsuction filtered
  8. washwashed with water
  9. customdried

Sources & evidence

ORD record
ord-ffd138b767db412495c900aea445c3e9
Source dataset
uspto-grants-1997_10
Patent number
US05681841

Reaction notes

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