Cyanamide → HCID 131710994, compound

HRID 462258Notes

Reaction equation

HRID 462258 reaction equation
[ClH:1].[C:2]1([CH:8]2[CH:12]3[CH2:13][NH:14][CH2:15][C:16](=[CH:17][C:18]4[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=4)[C:11]3=[N:10][N:9]2[CH2:24][C:25]([F:28])([F:27])[F:26])[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N:29]#[C:30][NH2:31]>C(O)C>[ClH:1].[C:2]1([CH:8]2[CH:12]3[CH2:13][N:14]([C:30](=[NH:29])[NH2:31])[CH2:15][C:16](=[CH:17][C:18]4[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=4)[C:11]3=[N:10][N:9]2[CH2:24][C:25]([F:27])([F:26])[F:28])[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 9864CyanamideHCID 1317109933,3a,4,5,6,7-hexahydro-3-phenyl-7-(phenylmethylene)-2-(2,2,2-trifluoroethyl)-2H-pyrazolo[4,3-c]-pyridine, monohydrochloride

Product 1

HCID 131710994HCID 131710994, compoundYield 48%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Ten grams of 3,3a,4,5,6,7-hexahydro-3-phenyl-7-(phenylmethylene)-2-(2,2,2-trifluoroethyl)-2H-pyrazolo[4,3-c]-pyridine, monohydrochloride (see Example 2) is reacted with 8.2 g of cyanamide in 350 ml of ethanol at reflux temperature for 24 hours. The bulk of ethanol is removed on a rotary evaporator and the residue (which does not crystallize) is converted to 10.8 g of the free base (using sodium hydroxide and chloroform extractions); melting point 155°-157° C (foaming), sintering at 120° C. The base is dissolved in 400 ml of dichloromethane, treated with 5 ml of 6.1 N alcoholic hydrogen chloride, and the solvents removed on a rotary evaporator. The foamy residue (11.7 g) is stirred with 50 ml of water and 150 ml of ether. The material becomes gummy, then slowly crystallizes on cooling in ice-water, continued stirring, and rubbing. After standing in the cold for about 16 hours, the product is filtered, washed with ether, and air-dried, yielding 5.3 g of material; melting point 222°-225° C, sintering at 210° C. Crystallization from acetonitrile (dissolved in 200 ml of boiling solvent, then concentrated to approximately 100 ml; crystallization proceeeds very slowly while standing in the cold for several days) yields 3.0 g of product; melting point 230°-232° C, sintering at 223° C.

Workup

  1. temperatureat reflux temperature for 24 hours
  2. customThe bulk of ethanol is removed on a rotary evaporator
  3. customthe residue (which does not crystallize)
  4. customsintering at 120° C
  5. dissolutionThe base is dissolved in 400 ml of dichloromethane
  6. additiontreated with 5 ml of 6.1 N alcoholic hydrogen chloride
  7. customthe solvents removed on a rotary evaporator
  8. customslowly crystallizes
  9. temperatureon cooling in ice-water
  10. stirringcontinued stirring
  11. customcold for about 16 hours
  12. filtrationthe product is filtered
  13. washwashed with ether
  14. customair-dried

Sources & evidence

ORD record
ord-fb1cf4db587d41b1bf88074ee6b2df16
Source dataset
uspto-grants-1977_12
Patent number
US04065617

Reaction notes

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