Potassium borohydride → HCID 23458684, compound

HRID 1679951Notes

Reaction equation

HRID 1679951 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([NH:8][C:9](=[S:22])[S:10][CH2:11][CH2:12][C:13]([C:15]2[CH:20]=[CH:19][C:18]([F:21])=[CH:17][CH:16]=2)=[O:14])=[N:6][CH:7]=1.[BH4-].[K+]>C(#N)C.O.C(Cl)(Cl)Cl.C(OCC)(=O)C>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([NH:8][C:9](=[S:22])[S:10][CH2:11][CH2:12][CH:13]([C:15]2[CH:16]=[CH:17][C:18]([F:21])=[CH:19][CH:20]=2)[OH:14])=[N:6][CH:7]=1

Participants

7

Reactant 2

HCID 4192641Potassium borohydrideHCID 23458673HCID 23458673, compound

Product 1

HCID 23458684HCID 23458684, compoundYield 48.1%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6212ChloroformSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
2 °C

Procedure

The procedure of Example 1 is followed, but a suspension of 3-(4-fluorophenyl)-3-oxopropyl 5-chloropyrid-2-yldithiocarbamate (25.0 g) in acetonitrile (225 cc) and a solution of potassium borohydride (5.6 g) in distilled water (56 cc) are used as the starting materials at a maximum of 25° C. The reaction is allowed to proceed for 1 hour at between 20° and 25° C. The residual oil thus obtained (20.2 g) is dissolved in a mixture (100 cc) of chloroform (80 cc) and ethyl acetate (20 cc) and the solution is chromatographed on a column of diameter 4 cm, containing silica (0.063-0.2 mm, 450 g). Elution is carried out first with a mixture of chloroform (800 cc) and ethyl acetate (200 cc), this eluate being discarded, and then with a mixture (2,500 cc) of chloroform (2,000 cc) and ethyl acetate (500 cc), this eluate being evaporated under reduced pressure (20 mm Hg) at 50° C. The resulting product (16.5 g) is recrystallised from boiling isopropyl ether (80 cc). After filtering the boiling solution and then cooling for 2 hours at 2° C., the crystals which have appeared are filtered off, washed 4 times with ice-cooled isopropyl ether (20 cc in total), and dried under reduced pressure (0.1 mm Hg) at 45° C. 3-(4-Fluorophenyl)-3-hydroxypropyl 5-chloropyrid-2-yldithiocarbamate (12.1 g), which melts at 86° C., is thus obtained.

Workup

  1. customare used as the starting materials at a maximum of 25° C
  2. customThe residual oil thus obtained (20.2 g)
  3. customthe solution is chromatographed on a column of diameter 4 cm
  4. additioncontaining silica (0.063-0.2 mm, 450 g)
  5. washElution
  6. additionis carried out first with a mixture of chloroform (800 cc) and ethyl acetate (200 cc)
  7. customwith a mixture (2,500 cc) of chloroform (2,000 cc) and ethyl acetate (500 cc), this eluate being evaporated under reduced pressure (20 mm Hg) at 50° C
  8. customThe resulting product (16.5 g) is recrystallised
  9. filtrationAfter filtering the boiling solution
  10. filtrationthe crystals which have appeared are filtered off
  11. washwashed 4 times with ice-
  12. temperaturecooled isopropyl ether (20 cc in total)
  13. customdried under reduced pressure (0.1 mm Hg) at 45° C

Sources & evidence

ORD record
ord-30cecba0bbfe470abc66d8de9d6ff2ca
Source dataset
uspto-grants-1981_06
Patent number
US04271167

Reaction notes

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