Carbon Tetrachloride → HCID 12939897, compound

HRID 1632348Notes

Reaction equation

HRID 1632348 reaction equation
[C:1]([Cl:5])(Cl)(Cl)Cl.CN(C)P(N(C)C)N(C)C.O=C1[CH2:21][C@@H:20]([C@H:22]([N:39]2[C:43](=[O:44])[C:42]3=[CH:45][CH:46]=[CH:47][CH:48]=[C:41]3[C:40]2=[O:49])[C:23]([O:25][CH:26]([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)=[O:24])[O:19][NH:18]1.[Cl-].[Cl-].CN(C)P(N(C)C)N(C)C>O1CCCC1.C(OCC)(=O)C>[Cl:5][C:1]1[CH2:21][C@@H:20]([C@H:22]([N:39]2[C:40](=[O:49])[C:41]3=[CH:48][CH:47]=[CH:46][CH:45]=[C:42]3[C:43]2=[O:44])[C:23]([O:25][CH:26]([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)=[O:24])[O:19][N:18]=1

Participants

7

Reactant 4

HCID 5943Carbon TetrachlorideHCID 15355Hexamethylphosphorous triamideHCID 12939895HCID 12939895, compoundHCID 13953172HCID 13953172, compound

Product 1

HCID 12939897HCID 12939897, compoundYield 42%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8857Ethyl AcetateSolvent

Procedure

To 192 μl (2 mmole) of carbon tetrachloride in 25 ml of dry tetrahydrofuran under N2 at room temperature is added 310 μl (1.9 mmole) of hexamethylphosphorous triamide dropwise over one minute. Within two minutes 590 mg. (1.3 mmole) of (αS,5S)-oxo-α-phthalimido-5-isoxazolidine acetic acid, benzhydryl ester acid in approximately 5 ml of dry THF is added rapidly. The heterogeneous solution in stirred at 45° for 48 hours. Alternatively, to 590 mg. (1.3 mmole) of (αS,5S)-oxo-α-phthalimido-5-isoxolidine in 20 ml. of dry tetrahydrofuran under N2 at room temperature is added 610 mg. (2.6 mmole) of hexamethylphosphorous triamide dichloride (prepared by hexachloroethane in acetonitrile with hexamethylphosphorous triamide according to R. Appel and H. Scholer, Chem. Ber., 110, 2382 (1977)). The solution is refluxed for 48 hours. The reaction is taken up in 150 ml of ethyl acetate and washed with 50 ml of 0.1N hydrochloric acid followed by brine and then dried over sodium sulfate. After concentrating in vacuo the residue is chromatographed on 50 g of silica gel with 30% ethyl acetate hexane (200 ml elution) which yields 200 mg of crude product (33% yield), 245 mg of starting material (42%). The crude product yielded (α5,5S) 3-chloro-4,5-dihydro-α-phthalimido-5-isoxazole acetic acid as needles, m.p. 178°-9° upon recrystallization from methanol.

Workup

  1. temperatureThe solution is refluxed for 48 hours
  2. washwashed with 50 ml of 0.1N hydrochloric acid
  3. dry with materialdried over sodium sulfate
  4. concentrationAfter concentrating in vacuo the residue
  5. customis chromatographed on 50 g of silica gel with 30% ethyl acetate hexane (200 ml elution) which

Sources & evidence

ORD record
ord-8f47912707f646d2a4f91d6cf5245d17
Source dataset
uspto-grants-1984_10
Patent number
US04474968

Reaction notes

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