Methyl iodide → methyl N-[[2'-(t-butoxycarbonyl)biphenyl-4-yl]methyl]dithiocarbamate

HRID 36171Notes

Reaction equation

HRID 36171 reaction equation
[NH2:1][CH2:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=2[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])=[CH:5][CH:4]=1.C(N(CC)CC)C.[C:29](=[S:31])=[S:30].[CH3:32]I>CO>[C:18]([O:17][C:15]([C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=1[C:6]1[CH:7]=[CH:8][C:3]([CH2:2][NH:1][C:29](=[S:31])[S:30][CH3:32])=[CH:4][CH:5]=1)=[O:16])([CH3:21])([CH3:20])[CH3:19]

Participants

6

Reactant 4

HCID 6328Methyl iodideHCID 6348Carbon DisulfideHCID 8471TriethylamineHCID 99710734'-(Aminomethyl)-biphenyl-2-carboxylic acid 1,1-dimethylethyl ester

Product 1

HCID 10339332methyl N-[[2'-(t-butoxycarbonyl)biphenyl-4-yl]methyl]dithiocarbamate

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent3×

Procedure

A solution of 1.415 g (5 mmole) of 4-aminomethyl-2'-(t-butoxycarbonyl)biphenyl and 751 μl (545 mg, 5.4 mmole) of triethylamine in 5 ml of methanol was stirred under N2 at room temperature as a solution of 342 μl (434 mg, 5.7 mmole) of carbon disulfide in 2 ml of methanol was added dropwise over about 10 minutes. After 2.5 hours the solution was cooled in an ice-methanol bath, and a solution of 311 μl (710 mg, 5 mmole) of methyl iodide in 2 ml of methanol was added dropwise over about 10 minutes. The cooling bath was removed, and the solution was allowed to warm to room temperature. After 2 hours the solution was concentrated at 25° C. The residue was partitioned between 50 ml of ether plus 10 ml of CH2Cl2 and 50 ml of 0.2N HCl. The organic phase was washed with 25 ml of saturated NaCl solution (aqueous), dried over MgSO4, filtered, and concentrated. Crystallization of the residual oil from ether yielded 1.57 g (84%) of nearly colorless crystals, mp 127.5°-128.5° C., satisfactory purity by TLC in 4:1 hexane-EtOAc; mass spectrum (FAB) m/e 374 (M+1)+.

Workup

  1. additionwas added dropwise over about 10 minutes
  2. temperatureAfter 2.5 hours the solution was cooled in an ice-methanol bath
  3. customThe cooling bath was removed
  4. concentrationAfter 2 hours the solution was concentrated at 25° C
  5. customThe residue was partitioned between 50 ml of ether plus 10 ml of CH2Cl2 and 50 ml of 0.2N HCl
  6. washThe organic phase was washed with 25 ml of saturated NaCl solution (aqueous)
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customCrystallization of the residual oil from ether
  11. customyielded 1.57 g (84%) of nearly colorless crystals, mp 127.5°-128.5° C., satisfactory purity by TLC in 4:1 hexane-EtOAc

Sources & evidence

ORD record
ord-10c8e392db614eeb9a93a7df3321f01b
Source dataset
uspto-grants-1995_05
Patent number
US05411980

Reaction notes

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