Chloroacetaldehyde → HCID 20188836, compound

HRID 1789194Notes

Reaction equation

HRID 1789194 reaction equation
O.[NH:2]1[C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][C:5]=2[N:4]=[C:3]1[S:11][CH2:12][C:13]1[C:14]([NH2:19])=[N:15][CH:16]=[CH:17][CH:18]=1.N1[C:24]2C=CC=C[C:23]=2N=C1SCC1C(N)=NC=CC=1.ClCC=O.C(=O)(O)[O-].[Na+]>C(O)C>[N:19]1[CH:23]=[CH:24][N:15]2[CH:16]=[CH:17][CH:18]=[C:13]([CH2:12][S:11][C:3]3[NH:4][C:5]4[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=4[N:2]=3)[C:14]=12

Participants

5

Reactant 3

HCID 33ChloroacetaldehydeHCID 516892Sodium BicarbonateHCID 69793526HCID 69793526, compound

Product 1

HCID 20188836HCID 20188836, compoundYield 71.3%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of 9.6 g (63 mmole) of 2-mercaptobenzimidazole and 7.7 g (62 mmole) of 3-hydroxymethyl-2-pyridinamine was dissolved in 60 ml of 48% aqueous hydrobromic acid and 60 ml of acetic acid and heated to reflux. After being cooled to room temperature, the mixture was poured into water and make alkaline with potassium carbonate. The oil that separated solidified upon addition of diethyl ether to the aqueous mixture. The solid was collected by filtration, washed with portions of diethyl ether and water, and air dried to yield 12.4 g of analytically pure 3-[(1H-benzimidazol-2-ylthio)methyl]-2-pyridinamine hemihydrate, as confirmed by the nmr and infrared spectra and by elemental analysis. [Calcd. for C13H12N4S.1/2H2O: C, 58.84; H, 4.93; N, 21.11; S, 12.08. Found: C, 59.06; H, 4.48; N, 20.82; S, 12.16.]A mixture of 4.0 g (15 mmole) of 3-[(1H-benzimidazol-2-ylthio)methyl]-2-pyridinamine hemihydrate, 1.9 ml (ca. 18 mmole) of 50% aqueous chloroacetaldehyde, and 1.5 g (18 mmole) of sodium bicarbonate in 25 ml of ethanol was stirred at room temperature. After three days the mixture was filtered and the filtrate was concentrated in vacuo. Trituration of the residue from the filtrate with a mixture of water and dichloromethane induced crystallization. The solid was collected, washed sequentially with water and dichloromethane, and air dried to yield 3.0 g of the title compound. Structure assignment was supported by the nmr and infrared spectra and by elemental analysis.

Workup

  1. filtrationAfter three days the mixture was filtered
  2. concentrationthe filtrate was concentrated in vacuo
  3. additionTrituration of the residue from the filtrate with a mixture of water and dichloromethane
  4. customcrystallization
  5. customThe solid was collected
  6. washwashed sequentially with water and dichloromethane, and air
  7. customdried

Sources & evidence

ORD record
ord-0be0315eef2a4e0bbe52f53f5fca31f4
Source dataset
uspto-grants-1987_08
Patent number
US04687775

Reaction notes

Loading…