Diisopropylaniline → HCID 9807094, compound

HRID 2379465Notes

Reaction equation

HRID 2379465 reaction equation
[CH2:1]([N:13]1[N:17]=[N:16][C:15]([NH:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[N:14]1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].C([Li])CCC.ClC(Cl)(O[C:34](=[O:40])OC(Cl)(Cl)Cl)Cl.C(N(C(C)C)CC)(C)C.[CH3:51][CH:52]([C:54]1[CH:60]=[CH:59][CH:58]=[C:57]([CH:61]([CH3:63])[CH3:62])[C:55]=1[NH2:56])[CH3:53]>O1CCCC1>[CH3:63][CH:61]([C:57]1[CH:58]=[CH:59][CH:60]=[C:54]([CH:52]([CH3:53])[CH3:51])[C:55]=1[NH:56][C:34](=[O:40])[N:18]([C:15]1[N:16]=[N:17][N:13]([CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12])[N:14]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[CH3:62]

Participants

7

Reactant 5

HCID 32484DiisopropylanilineHCID 81531DiisopropylethylamineHCID 94429TriphosgeneHCID 10806269HCID 10806269, compoundHCID 178418339Butyllithium

Product 1

HCID 9807094HCID 9807094, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred, cold (-78° C.) solution of 2-dodecyl-N-phenyl-2H-tetrazol-5-amine (2.2 g, 0.0067 mol) in anhydrous tetrahydrofuran (30 mL) under nitrogen atmosphere was added dropwise a 2.5 M solution of n-butyl lithium in hexanes (2.7 mL, 0.0068 mol), and the mixture was stirred for 25 minutes. To the mixture was added triphosgene (0.6385 g, 0.002152 mol) in one portion. The mixture was stirred for 1.5 hours and then allowed to warm to room temperature. The resulting orange solution was stirred for 3 days. To the mixture was added diisopropylethylamine (1.3 mL, 0.0069 mol) and 2,6-bis(1-methylethyl)aniline (1.3 mL, 0.0069 mol), and the mixture was refluxed for 3 days. The reaction mixture was allowed to cool and then rotoevaporated. The residue was partitioned between diethyl ether and saturated sodium bicarbonate. The organic layer was washed with additional saturated sodium bicarbonate, 1M hydrochloric acid, saturated sodium chloride, and was dried over magnesium sulfate. The organics were rotoevaporated to an oil. The oil was dissolved in PET ether and chromatographed on silica gel (360 g, 230-400 mesh) using PET ether-ethyl acetate (15:1, 3×300 mL; 11:1, 20×350 mL) as eluent. Fractions containing product were rotoevaporated from dichloromethane and dried in vacuo (50° C.), yield 2.798 g (78%) of the title compound. 1H NMR (CDCl3): δ 9.3 (s, 1H), 7.5 (m, 6H), 7.2 (d, 2H), 4.5 (t, 2H), 3.2 (septet, 2H), 1.9 (m, 2H), 1.2 (m, 18H), 0.9 (t, 3H).

Workup

  1. stirringThe mixture was stirred for 1.5 hours
  2. stirringThe resulting orange solution was stirred for 3 days
  3. temperaturethe mixture was refluxed for 3 days
  4. temperatureto cool
  5. customThe residue was partitioned between diethyl ether and saturated sodium bicarbonate
  6. washThe organic layer was washed with additional saturated sodium bicarbonate, 1M hydrochloric acid, saturated sodium chloride
  7. dry with materialwas dried over magnesium sulfate
  8. dissolutionThe oil was dissolved in PET ether
  9. customchromatographed on silica gel (360 g, 230-400 mesh)
  10. additionFractions containing product
  11. dry with materialdried in vacuo (50° C.), yield 2.798 g (78%) of the title compound

Sources & evidence

ORD record
ord-9ecd84f7e2a641e09a791003d82e4039
Source dataset
uspto-grants-1994_11
Patent number
US05362744

Reaction notes

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