Hydrochloric Acid → HCID 23458680, compound

HRID 1679945Notes

Reaction equation

HRID 1679945 reaction equation
[BH4-].[K+].[Cl:3][C:4]1[CH:5]=[CH:6][C:7]([N:10]2[CH:14]([OH:15])[CH2:13][S:12][C:11]2=[S:16])=[N:8][CH:9]=1.Cl>O.C(#N)C>[Cl:3][C:4]1[CH:5]=[CH:6][C:7]([NH:10][C:11](=[S:16])[S:12][CH2:13][CH2:14][OH:15])=[N:8][CH:9]=1

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 4192641Potassium borohydrideHCID 23458655HCID 23458655, compound

Product 1

HCID 23458680HCID 23458680, compoundYield 48.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

A solution of potassium borohydride (8.35 g) in distilled water (95 cc) is added, at a maximum of 30° C., to a suspension of 3-(5-chloropyrid-2-yl)-4-hydroxythiazolidine-2-thione (38.0 g) in acetonitrile (380 cc). The reaction is allowed to proceed for 30 minutes at between 25° and 30° C. A 3 N aqueous solution of hydrochloric acid (51 cc) is added at a maximum of 20° C. The acetonitrile is evaporated off under reduced pressure (20 mm Hg) at 45° C. The resulting crystals are filtered off, washed with acetonitrile (B 15 cc) and isopropyl ether (25 cc) and then 4 times with distilled water (250 cc in total) and dried in air at 20° C. The resulting product (23.7 g; m.p.=100° C.) is suspended in chloroform (480 cc). The suspension is chromatographed on silica (0.2-0.5 mm) (240 g) contained in a column of diameter 3.8 cm. Elution is carried out with chloroform (400 cc) and then with a mixture of chloroform (1,380 cc) and methanol (35 cc), this eluate being discarded. Elution is continued with a mixture of chloroform (720 cc) and methanol (80 cc), this eluate being collected and evaporated to dryness under reduced pressure (20 mm Hg) at 45° C. The resulting crystals are washed with isopropyl ether (60 cc) and then with ice-cooled acetonitrile (10 cc) and dried under reduced pressure (0.2 mm Hg) at 45° C. 2-Hydroxyethyl 5-chloropyrid-2-yldithiocarbamate (18.5 g), which melts at 108° C., is thus obtained.

Workup

  1. customThe acetonitrile is evaporated off under reduced pressure (20 mm Hg) at 45° C
  2. filtrationThe resulting crystals are filtered off
  3. washwashed with acetonitrile (B 15 cc) and isopropyl ether (25 cc)
  4. dry with material4 times with distilled water (250 cc in total) and dried in air at 20° C
  5. customThe suspension is chromatographed on silica (0.2-0.5 mm) (240 g)
  6. washElution
  7. additionwith a mixture of chloroform (1,380 cc) and methanol (35 cc)
  8. washElution
  9. additionis continued with a mixture of chloroform (720 cc) and methanol (80 cc)
  10. customthis eluate being collected
  11. customevaporated to dryness under reduced pressure (20 mm Hg) at 45° C
  12. washThe resulting crystals are washed with isopropyl ether (60 cc)
  13. temperaturewith ice-cooled acetonitrile (10 cc)
  14. customdried under reduced pressure (0.2 mm Hg) at 45° C

Sources & evidence

ORD record
ord-2cc64a3e53d046f4b7973a60b4e2aa88
Source dataset
uspto-grants-1981_06
Patent number
US04271167

Reaction notes

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