Phosgene → HCID 54312346, compound

HRID 1632872Notes

Reaction equation

HRID 1632872 reaction equation
C(N[CH2:5][CH2:6][S:7]C(=O)C)(=O)C.C[N:12]1[CH2:17]CO[CH2:14][CH2:13]1.[C:18](Cl)(Cl)=[O:19].[N-:22]=[N+:23]=[N-:24].CN(C)C(=[NH2+])N(C)C>ClCCl>[C:6]([O:19][CH2:18][CH2:17][N:12]1[C:13]([CH3:14])=[N:24][N:23]=[N:22]1)(=[S:7])[CH3:5]

Participants

6

Reactant 4

HCID 6371PhosgeneHCID 79724-MethylmorpholineHCID 14997N,S-DiacetylcysteamineHCID 178484365HCID 178484365, compound

Product 1

HCID 54312346HCID 54312346, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

N,S-Diacetyl β-mercaptoethylamine, (805 mg) in dichloromethane (16 ml) was treated with N-methylmorpholine (3.3 ml). The reaction mixture was cooled to -40° and treated with phosgene (8.7 ml, 12.5% solution in toluene, d. 0.91; 990 mg COCl2). After warming to room temperature tetramethylguanidinium azide (1.0 g) in dichloromethane (10 ml) was added. After stirring for 15 min. the reaction mixture was washed with water (2×20 ml), dried (MgSO4) and evaporated in vacuo. Toluene was added to the residue and evaporated in vacuo to remove residual N-methylmorpholine. The crude product was chromatographed on silica gel (230-400 mesh ASTM, 2.5×12 cm column) eluting with ethyl acetate to give 2-(5-methyltetrazol-1-yl)ethyl thioacetate (767 mg), λmax. (CH2Cl2) 1 795, 1 530, 1 410, 1 360, 1 135, 1 110, 1 080 and 940 cm-1., δ(CDCl3) 2.30 (3H,s), 2.68 (3H,s), 3.40 (2H, t, J ca 7.5 Hz), 4.54 (2H, t, J ca 7.5 Hz). 2-(5-methyltetrazol-1-yl)ethyl thioacetate (100 mg) was suspended in 0.1M aqueous NaOH (11 ml) and the mixture was stirred vigourously under argon at room temperature. After ca 15 min. the oil seemed to have dissolved. After 30 min. the solution was neutralised to pH 7 by addition of dilute HCl. The solution was then extracted with ethyl acetate (2×20 ml) and the extract dried (MgSO4) and evaporated in vacuo. Toluene (20 ml) was added and evaporated in vacuo. The residue was taken up in dichloromethane (20 ml). Evaporation in vacuo left the thiol as an oil (31 mg), νmax. (CH2Cl2) 3 050, 2 950, 2 850 (broad), 1 530, 1 410, 1 320, 1 110, 1 085 cm-1., δ(CDCl3) 1.51 (1H, broad s), 2.65 (3H,s), 3.12 (2H, broad t, J ca 6 Hz), 4.51 (2H, t, J 6.5 Hz) ppm. Found M+ m/e 144.046 7; C4H8N4S requires m/e 144.046 9.

Workup

  1. temperatureThe reaction mixture was cooled to -40°
  2. additionwas added
  3. washwas washed with water (2×20 ml)
  4. dry with materialdried (MgSO4)
  5. customevaporated in vacuo
  6. additionToluene was added to the residue
  7. customevaporated in vacuo
  8. customto remove residual N-methylmorpholine
  9. customThe crude product was chromatographed on silica gel (230-400 mesh ASTM, 2.5×12 cm column)
  10. washeluting with ethyl acetate

Sources & evidence

ORD record
ord-6800efc2100e4382a9031b8b229d667b
Source dataset
uspto-grants-1984_10
Patent number
US04477662

Reaction notes

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