1,1'-Thiocarbonyldiimidazole → Ethyl N-methyl-N-(4-isothiocyanatophenyl)glycinate

HRID 1005271Notes

Reaction equation

HRID 1005271 reaction equation
[CH3:1][N:2]([C:9]1[CH:14]=[CH:13][C:12]([N:15]=O)=[CH:11][CH:10]=1)[CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5].[C:17](N1C=CN=C1)(N1C=CN=C1)=[S:18]>C(OCC)(=O)C.C(Cl)Cl.[Pd]>[CH3:1][N:2]([C:9]1[CH:14]=[CH:13][C:12]([N:15]=[C:17]=[S:18])=[CH:11][CH:10]=1)[CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5]

Participants

6

Reactant 2

HCID 802641,1'-ThiocarbonyldiimidazoleHCID 12038854Ethyl N-methyl-N-(4-nitrosophenyl)glycinate

Product 1

HCID 12038855Ethyl N-methyl-N-(4-isothiocyanatophenyl)glycinate

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A solution of 14.7 g (66 mmol) of ethyl N-methyl-N-(4-nitrosophenyl)glycinate in 200 mL of ethyl acetate was reduced (10% Pd/C, 50 psi H2) until uptake was complete, dried 1 hr (Na2SO4), filtered, concentrated, and dissolved in a solution of 12.5 g (70 mmol) of thiocarbonyldimidazole in 100 mL CH2Cl2 /300 ml toluene. When tlc showed only product (2 hr,Rf 0.6, CH2Cl2), the solution was washed with 2×100 mL of water, passed throug a silica plug to remove color, and recrystallized from hexane (300 mL) to give 13.6g (54 mmol, 82%) mp 90-91°. Anal. C12H14N2O2S (250): Calcd.: C,57.58; H,5.64; N,11.19; S,12.81. Found: C,57.63; H,5.59; N,11.17; S,12.49. MS(FD) m/z250. 1H NMR(CDCl3)δ: 7.10,d,2H,ArH; 6.58,d,2H,ArH; 4.18,q,2H,CH2 --O; 4.05,s,2H,CH2 --N; 3.07,s,3H,CH3 --N; 1.25,s,3H,CH3 --C.

Workup

  1. dry with materialdried 1 hr (Na2SO4)
  2. filtrationfiltered
  3. concentrationconcentrated
  4. washthe solution was washed with 2×100 mL of water
  5. customto remove color
  6. customrecrystallized from hexane (300 mL)
  7. customto give 13.6g (54 mmol, 82%) mp 90-91°

Sources & evidence

ORD record
ord-30efff228fb2432da51a0e31d4079a58
Source dataset
uspto-grants-2000_04
Patent number
US06054260

Reaction notes

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