Phosgene → HCID 18957141, compound

HRID 2379469Notes

Reaction equation

HRID 2379469 reaction equation
[CH:1]1([NH:7][C:8]2[N:9]=[N:10][N:11]([CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])[N:12]=2)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.C(N(C(C)C)CC)(C)C.[C:34](Cl)(Cl)=[O:35].[F:38][C:39]1[CH:45]=[C:44]([F:46])[CH:43]=[CH:42][C:40]=1[NH2:41]>C1(C)C=CC=CC=1>[CH:1]1([N:7]([C:8]2[N:9]=[N:10][N:11]([CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])[N:12]=2)[C:34]([NH:41][C:40]2[CH:42]=[CH:43][C:44]([F:46])=[CH:45][C:39]=2[F:38])=[O:35])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6]1

Participants

6

Reactant 4

HCID 6371PhosgeneHCID 97092,4-DifluoroanilineHCID 81531Diisopropylethylamine2×HCID 18957138HCID 18957138, compound

Product 1

HCID 18957141HCID 18957141, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
45 °C

Procedure

To a stirred mixture of N-cyclohexyl-2-dodecyl-2H-tetrazol-5-amine (0.3349 g, 0.0009981 mol) and diisopropylethylamine (1.7 mL, 0. 0098 mol) at room temperature under nitrogen atmosphere was added a 12.5 wt/wt % solution of phosgene in toluene (8 mL). The mixture was heated at 45° C. for 22 hours and allowed to cool. Excess phosgene was removed, and the mixture was rotoevaporated to a sludge. The residue was suspended in anhydrous tetrahydrofuran (25 mL), additional diisopropylethylamine (0.35 mL, 0. 0020 mol) and 2,4-difluoroaniline (0.11 mL, 0.0011 mol) were added, and the mixture was refluxed for 6 days. The mixture was partitioned between diethyl ether and 1M hydrochloric acid. The organic layer was washed with saturated sodium chloride, dried (Na2SO4), and rotoevaporated to an oil. The oil was chromatographed twice on silica gel: (80 g, 230-400 mesh) using PET ether-acetone (7:1) and (68 g, 230-400 mesh) using PET ether-acetone (40:1) to give the title compound as a yellow oil, yield 0.2995 g (61%). 1H NMR (CDCl3): δ 9.9 (s, 1H) , 8.2 (m, 1H) , 6.9 (m, 2H), 4.6 (m, 3H), 2.1 (m, 4H), 1.8 (m, 4H), 1.6 (m, 2H), 1.3 (m, 20H), 0.9 (t, 3H).

Workup

  1. temperatureto cool
  2. customExcess phosgene was removed
  3. temperaturethe mixture was refluxed for 6 days
  4. customThe mixture was partitioned between diethyl ether and 1M hydrochloric acid
  5. washThe organic layer was washed with saturated sodium chloride
  6. dry with materialdried (Na2SO4)
  7. customThe oil was chromatographed twice on silica gel

Sources & evidence

ORD record
ord-c7f73e89e1a44850be98b51a1b27dd5a
Source dataset
uspto-grants-1994_11
Patent number
US05362744

Reaction notes

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