Hexamethylenetetramine → HCID 69778877, compound

HRID 1279895Notes

Reaction equation

HRID 1279895 reaction equation
C1N2CN3CN(C2)CN1C3.CCCCCCC=CCCC.[CH3:22][C:23]([CH3:43])([CH3:42])[CH2:24][C:25](=[O:41])[CH2:26][C@H:27]([C:31]1[O:32][CH2:33][C@@H:34]([C:36]([O:38][CH2:39][CH3:40])=[O:37])[N:35]=1)[CH2:28][CH:29]=[CH2:30]>ClCCl.[Cu](Br)Br>[CH3:42][C:23]([CH3:22])([CH3:43])[CH2:24][C:25](=[O:41])[CH2:26][C@H:27]([C:31]1[O:32][CH:33]=[C:34]([C:36]([O:38][CH2:39][CH3:40])=[O:37])[N:35]=1)[CH2:28][CH:29]=[CH2:30]

Participants

6

Reactant 3

HCID 4101HexamethylenetetramineHCID 136496Undec-4-eneHCID 86583709HCID 86583709, compound

Product 1

HCID 69778877HCID 69778877, compoundYield 66.3%

Reagents, catalysts & solvents 2

HCID 24611Copper bromide (CuBr2)CatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

A suspension of copper (II) bromide (50.6 g, 226.6 mmol) and hexamethylenetetramine (31.6 g, 225.5 mmol) in dichloromethane (250 ml), under a nitrogen atmosphere, was treated with 1,8-diazabicyco[5.4.0]undec-7-ene (33 ml, 220.7 mmol). The mixture was cooled to 0° C. and treated with a solution of ethyl (4S)-2-[(1R)-1-(4,4-dimethyl-2-oxopentyl)-3-butenyl]4,5-dihydro-1,3-oxazole-4-carboxylate (Preparation 114) (17.6 g, 56.4 mmol) in dichloromethane (250 ml) via a cannula. The reaction mixture was allowed to warm to room temperature and stirred for 18 hours. The solvent was removed under reduced pressure and the residue was azeotroped with ethyl acetate. The residue was dissolved in ethyl acetate and washed with a 1:1 mixture of 0.880 ammonia solution: saturated aqueous ammonium chloride solution (×2), water, hydrochloric acid (2M) (×3), saturated aqueous sodium hydrogen carbonate solution and brine. The solvent was removed under reduced pressure. The oil was purified by column chromatography on silica gel eluting with a solvent gradient of 95:5 (hexane:diethylether) gradually changing to 50:50 (hexane:diethylether) to afford the title compound as a colourless oil (11.5 g).

Workup

  1. temperatureto warm to room temperature
  2. customThe solvent was removed under reduced pressure
  3. customthe residue was azeotroped with ethyl acetate
  4. dissolutionThe residue was dissolved in ethyl acetate
  5. washwashed with a 1:1 mixture of 0.880 ammonia solution
  6. customThe solvent was removed under reduced pressure
  7. customThe oil was purified by column chromatography on silica gel eluting with a solvent gradient of 95:5 (hexane:diethylether)

Sources & evidence

ORD record
ord-3013147e453d4ea68d4465462de7a961
Source dataset
uspto-grants-2002_09
Patent number
US06448278B2

Reaction notes

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