Chloroacetone → HCID 59324083, compound

HRID 602579Notes

Reaction equation

HRID 602579 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[NH2:9].CCN(CC)CC.[C:17](=[S:20])([S-:19])N.Cl[CH2:22][C:23](=O)[CH3:24]>C(=S)=S.CC#N>[NH2:9][C:3]1[CH:4]=[C:5]([F:8])[CH:6]=[CH:7][C:2]=1[N:1]1[C:23]([CH3:24])=[CH:22][S:19][C:17]1=[S:20]

Participants

7

Reactant 4

HCID 6571ChloroacetoneHCID 8471TriethylamineHCID 1645844-Fluorobenzene-1,2-diamineHCID 3037131Carbamodithioate

Product 1

HCID 59324083HCID 59324083, compound

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 6348Carbon DisulfideSolvent

Procedure

10 g (79 mmol) of commercially available 1,2-diamino-4-fluorobenzene 1b were suspended in CS2 (500 mL), then NEt3 (2 eq, 22 ml) were added dropwise and the mixture stirred at r.t. for 2 h. The resulting dithiocarbamate salt was then filtered off, washed with Et2O and used without further purifications (24 g, yellow powder, 99%). 24 g (79 mmol) of dithiocarbamate salt were suspended in MeCN (500 mL), then commercially available chloroacetone (1.1 eq, 7.14 mL) was added dropwise and the mixture stirred at r.t. for 12 h. The solvent was then removed and HCl 37% (21 mL) was added under vigorous stirring. After 15 min, water (150 mL) was added and the mixture extracted 3×150 mL of CH2Cl2. The organic layer was washed 3×400 mL of water, dried with MgSO4 and evaporated under reduced pressure. 3-(2-Amino-4-fluorophenyl)-4-methyl-1,3-thiazole-2(3H)-thione 2b was obtained by crystallisation from CH2Cl2 as yellow crystals (12.1 g, 68%). Mp=138° C.; 1H NMR (300 MHz, CDCl3) δ=1.95 (3H, d, J=1.2, CH3), 3.80 (2H, brs, NH2), 6.37 (1H, q, J=1.2, H5), 6.57-6.99 (3H, m, Ar); 13C NMR (75 MHz, CDCl3) δ=15.44, 103.9 (d, J=26), 106.4 (d, J=24), 106.6, 119.3 (d, J=3), 130.0 (d, J=11), 144.6 (d, J=12), 163.8 (d, J=248), 189.2; HRMS m/z C10H10N2FS2 [M+H]+ calcd: 241.0264, found: 241.0262. The structure of 3-(2-amino-4-fluorophenyl)-4-methyl-1,3-thiazole-2(3H)-thione was fully established by X-ray single crystal analysis.

Workup

  1. filtrationThe resulting dithiocarbamate salt was then filtered off
  2. washwashed with Et2O
  3. stirringthe mixture stirred at r.t. for 12 h
  4. customThe solvent was then removed
  5. additionHCl 37% (21 mL) was added under vigorous stirring
  6. waitAfter 15 min
  7. additionwater (150 mL) was added
  8. extractionthe mixture extracted 3×150 mL of CH2Cl2
  9. washThe organic layer was washed 3×400 mL of water
  10. dry with materialdried with MgSO4
  11. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-f9f91ffed70148b88193781dd4f238ed
Source dataset
uspto-grants-2011_03
Patent number
US07906541B2

Reaction notes

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