Thiophosgene → HCID 86675384, compound

HRID 1523110Notes

Reaction equation

HRID 1523110 reaction equation
[C:1]([CH2:4][N:5]1[CH2:18][CH2:17][CH2:16][NH:15][CH2:14][CH2:13][N:12]([CH2:19][C:20]([OH:22])=[O:21])[CH2:11][CH2:10][CH2:9][N:8]([CH2:23][CH2:24][C:25]2[CH:30]=[CH:29][C:28]([NH2:31])=[CH:27][CH:26]=2)[CH2:7][CH2:6]1)([OH:3])=[O:2].[C:32](Cl)(Cl)=[S:33]>Cl.C(Cl)(Cl)Cl>[C:1]([CH2:4][N:5]1[CH2:18][CH2:17][CH2:16][NH:15][CH2:14][CH2:13][N:12]([CH2:19][C:20]([OH:22])=[O:21])[CH2:11][CH2:10][CH2:9][N:8]([CH2:23][CH2:24][C:25]2[CH:26]=[CH:27][C:28]([N:31]=[C:32]=[S:33])=[CH:29][CH:30]=2)[CH2:7][CH2:6]1)([OH:3])=[O:2]

Participants

5

Reactant 2

HCID 10040ThiophosgeneHCID 86675383HCID 86675383, compound

Product 1

HCID 86675384HCID 86675384, compoundYield 98.3%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 6212ChloroformSolvent

Procedure

To a solution of compound (12) (0.79 g, 1.81 mmol) in 0.5 M HCl (10 ml) was carefully added thiophosgene (CSCl2) (4.17 ml, 6.26 g, 54.4 mmol) in CHCl3 (10 ml). The reaction mixture was stirred at an ambient temperature for 5 hours to separate the layers. After removing the aqueous layer, the organic CHCl3 layer was washed with water (2×50 ml). The combined aqueous layer was washed with CHCl3 (3×50 ml) to remove the unreacted thiophosgene. Finally, the aqueous layer was lyophilized to obtain a white solid of compound (14) (0.85 g, 98% yield). 1H NMR (500 MHz, D2O): δ 7.67-7.65 (dd, 2H), 7.50-7.48 (dd, 2H), 3.923 (s, 4H), 3.48-2.52 (m, 20H), 1.98 (brs, 2H), 1.88 (brs, 2H); 13C NMR (125 MHz, D2O): δ 187.9, 174.4, 173.2, 145.7, 137.5, 136.8, 135.1, 129.1, 128.6, 125.5, 122.6, 121.6, 60.4, 59.7, 57.8, 57.2, 56.9, 56.1, 54.5, 48.5, 35.5, 29.7, 23.3, 20.7; HRMS (FAB) calculated for C23H36N5O4S: 478.2488 [(M+H)+], measured value: 478.2484 [(M+H)+].

Workup

  1. customto separate the layers
  2. customAfter removing the aqueous layer
  3. washthe organic CHCl3 layer was washed with water (2×50 ml)
  4. washThe combined aqueous layer was washed with CHCl3 (3×50 ml)
  5. customto remove the unreacted thiophosgene

Sources & evidence

ORD record
ord-db48dd952fda4a40b32587a0671b2b69
Source dataset
uspto-grants-2015_07
Patent number
US09079867B2

Reaction notes

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