Formaldehyde → HCID 131712278, compound

HRID 1680865Notes

Reaction equation

HRID 1680865 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[C:7]([CH2:9][NH:10][CH2:11][CH2:12][CH2:13][NH:14][CH2:15][CH2:16][CH2:17][CH2:18][NH:19][CH2:20][CH2:21][CH2:22][NH2:23])[CH:6]=[CH:5][C:4]=1[OH:24].Cl.Cl.N[N:28]1[C:36]2[CH2:35][CH2:34][CH2:33][CH2:32][C:31]=2[CH:30]=[N:29]1.[C:37]1([NH2:48])[C:42](F)=[C:41](F)[C:40](F)=[C:39](N)[C:38]=1F.Cl.Cl.C([O-])(=O)C.[Na+].C([BH3-])#N.[Na+].C=O>C(O)C>[CH3:1][O:2][C:3]1[CH:8]=[C:7]([CH2:9][NH:10][CH2:11][CH2:12][CH2:13][NH:14][CH2:15][CH2:16][CH2:17][CH2:18][NH:19][CH2:20][CH2:21][CH2:22][NH2:23])[CH:6]=[CH:5][C:4]=1[OH:24].[CH3:13][N:14]([N:48]1[C:37]2[CH2:38][CH2:39][CH2:40][CH2:41][C:42]=2[CH:36]=[N:28]1)[CH3:15].[CH3:1][O:2][C:3]1[CH:8]=[C:7]([CH2:9][NH:10][CH2:11][CH2:12][CH2:13][NH:14][CH2:15][CH2:16][CH2:17][CH2:18][NH:19][CH2:20][CH2:21][CH2:22][NH2:23])[CH:6]=[CH:5][C:4]=1[OH:24].[CH3:9][N:10]([N:29]1[CH:30]=[C:31]2[C:36]([CH2:35][CH2:34][CH2:33][CH2:32]2)=[N:28]1)[CH3:11]

Participants

8

Reactant 5

HCID 712FormaldehydeHCID 149026Tetrafluoro-m-phenylenediamine dihydrochlorideHCID 517045Sodium AcetateHCID 5003444Sodium cyanoborohydrideHCID 131712274HCID 131712274, compound

Product 2

HCID 131712278HCID 131712278, compoundHCID 131712280HCID 131712280, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A reaction mixture was prepared containing 630 mg. of dl-5-amino-4,5,6,7-tetrahydro-1H-indazole dihydrochloride and its 2H tautomer dihydrochloride 410 mg. of sodium acetate, and 75 ml. of ethanol. To this mixture was added 380 mg. of sodium cyanoborohydride followed by 1 ml. of 37% aqueous formalin. The resulting mixture was stirred at ambient temperature for about 17 hours, after which time it was poured into an ice-1N aqueous hydrochloric acid mixture. The aqueous layer was extracted with chloroform and the chloroform extract discarded. The aqueous layer was then made basic with 14N aqueous ammonium hydroxide and the resulting alkaline solution extracted several times with a chloroform-isopropanol solvent mixture. The extracts were combined and the combined extracts washed with saturated aqueous sodium chloride and then dried. Evaporation of the solvent yielded 0.43 g. of a residue comprising dl-5-dimethylamino-4,5,6,7-tetrahydro-1H-indazole and dl-5-dimethylamino-4,5,6,7-tetrahydro-2H-indazole formed in the above reaction. NMR of the tautomeric mixture gave characteristic peaks at 142 cps (singlet-aminomethyl) 432 and 440 cps (broad singlet C--3H) using CDCl3. The compounds were further purified by dissolving the residue in 10 ml. of 1N aqueous hydrochloric acid and diluting this mixture with anhydrous ethanol. This solution was evaporated to dryness in vacuo and the resulting residue crystallized from a methanol/ether solvent mixture. dl-5-Dimethylamino-4,5,6,7-tetrahydro-1H-indazole dihydrochloride and dl-5-dimethylamino-4,5,6,7-tetrahydro-2H-indazole dihydrochloride thus prepared melted at 230°-38° with foaming; yield=430 mg.

Workup

  1. customA reaction mixture was prepared
  2. additioncontaining 630 mg
  3. additionTo this mixture was added 380 mg
  4. extractionThe aqueous layer was extracted with chloroform
  5. extractionthe chloroform extract
  6. extractionthe resulting alkaline solution extracted several times with a chloroform-isopropanol solvent mixture
  7. washthe combined extracts washed with saturated aqueous sodium chloride
  8. customdried
  9. customEvaporation of the solvent
  10. customyielded 0.43 g

Sources & evidence

ORD record
ord-df668dc6ef4d415b8733e5468fd5b987
Source dataset
uspto-grants-1981_06
Patent number
US04276300

Reaction notes

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