Sulfuryl chloride → HCID 13188207, compound

HRID 485764Notes

Reaction equation

HRID 485764 reaction equation
[Cl:1][CH2:2][C:3]1[N:4]=[C:5]2[S:12][CH:11]=[N:10][N:6]2[C:7](=[O:9])[CH:8]=1.S(Cl)([Cl:16])(=O)=O>ClC(Cl)C>[Cl:16][C:8]1[C:7](=[O:9])[N:6]2[N:10]=[CH:11][S:12][C:5]2=[N:4][C:3]=1[CH2:2][Cl:1]

Participants

4

Reactant 2

HCID 24648Sulfuryl chlorideHCID 71307877-(chloromethyl)-5H-[1,3,4]thiadiazolo[3,2-a]pyrimidin-5-one(SALTDATA: FREE)

Product 1

HCID 13188207HCID 13188207, compound

Reagents, catalysts & solvents 1

HCID 63651,1-DichloroethaneSolvent

Conditions

Temperature
60 °C

Procedure

7-chloromethyl-5H-1,3,4-thiadiazolo[3,2-a]pyrimidine-5-one (10 g), prepared according to Example 1, was reacted with sulfuryl chloride (7.5 g) in dichloroethane (150 ml) under stirring at 60° C. for 2 hours. After cooling the precipitate was filtered then was suspended in water (500 ml) and neutralized by treatment with 35% NaOH. Filtration and washings with water gave 6-chloro-7-chloromethyl-5H-1,3,4-thiadiazolo[3,2-a]pyrimidine-5-one, m.p. 193°-195° C. (7.5 g), which was reacted with triphenylphosphine (9.1 g) in acetonitrile (125 ml) under stirring at reflux temperature for 20 hours. After cooling the precipitate was filtered and washed with ethyl acetate to give (6-chloro-5-oxo-5H-1,3,4-thiadiazolo[3,2-a]pyrimidine-7-yl)-methyl-triphenylphosphonium chloride (16 g), which was suspended in dimethylsulphoxide (60 ml) and treated dropwise with potassium terbutoxide (3.6 g) dissolved in dimethylsulphoxide (30 ml) at a temperature of about 20° C. The solution of the ylide so obtained was then reacted with benzaldehyde (6 g) at 80° C. for 8 hours. After cooling the solution was diluted with ice water and the precipitate was filtered and washed with water. Crystallization from chloroform-ethanol gave 3.4 g of 6-chloro-7-trans-(2-phenyl-ethenyl)-5H-1,3,4-thiadiazolo[3,2-a]pyrimidine-5-one, m.p. 265°-270° C. dec., N.M.R. (CF3COOD) δ p.p.m.: 7.45 (m) (3H, C-3, C-4 and C-5 phenyl protons), 7.53 (d) (1H, β-ethenyl proton), 7.66 (dd) (2H, C-2 and C-6 phenyl protons), 8.05 (d), (1H, α-ethenyl proton), 9.02 (s) (1H, C-2 proton); JHα↑Hβ =16 Hz.

Workup

  1. temperatureAfter cooling the precipitate
  2. filtrationwas filtered
  3. filtrationFiltration and washings with water

Sources & evidence

ORD record
ord-d55a6d6b244a466ab2f4402f4e4efaaf
Source dataset
uspto-grants-1985_08
Patent number
US04537962

Reaction notes

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