HCID 20312027, compound → HCID 131711206, compound

HRID 2420570Notes

Reaction equation

HRID 2420570 reaction equation
O.[C:2]([O:6][CH2:7][C:8]([Cl:11])([Cl:10])[Cl:9])(=[O:5])[CH:3]=O.C1(P(=[CH:31][C:32]2[CH2:33][S:34][C@@H:35]3[C@H:55]([NH:56][C:57](=[O:64])[CH2:58][C:59]4[S:60][CH:61]=[CH:62][CH:63]=4)[C:54](=[O:65])[N:36]3[C:37]=2[C:38]([O:40][CH:41]([C:48]2[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=2)[C:42]2[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=2)=[O:39])(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(Cl)Cl>[Cl:11][C:8]([Cl:9])([Cl:10])[CH2:7][O:6][C:2]([CH:3]=[CH:31][C:32]1[CH2:33][S:34][C@@H:35]2[C@H:55]([NH:56][C:57](=[O:64])[CH2:58][C:59]3[S:60][CH:61]=[CH:62][CH:63]=3)[C:54](=[O:65])[N:36]2[C:37]=1[C:38]([O:40][CH:41]([C:48]1[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=1)[C:42]1[CH:43]=[CH:44][CH:45]=[CH:46][CH:47]=1)=[O:39])=[O:5]

Participants

4

Reactant 2

HCID 20312027HCID 20312027, compoundHCID 53998408HCID 53998408, compound

Product 1

HCID 131711206HCID 131711206, compoundYield 47%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A suspension of 2,2,2-trichloroethyl glyoxylate monohydrate (435 mg., 1.86 mmole) in dry methylene chloride (25 ml.) was stirred at 23° and treated, over 10 minutes, with diphenylmethyl 3-(triphenylphosphoranylidenemethyl)-7β-(2-thienylacetamido)ceph-3-em-4-carboxylate (765 mg., 1 mmole). After stirring for 45 minutes, the solvent was removed in vacuo and the residue was extracted with ethyl acetate (50 ml.); the insoluble material was filtered off and the filtrate was washed well with water (2 × 50 ml.) and brine (50 ml.), dried, and evaporated to an oil (1.07 g.). This material was purified by chromatography on 0.05-0.2mm. Kieselgel, with benzene; ethyl acetate = 10:1 as eluent. Combination of similar fractions (as judged by t.l.c.) gave the title compound (325 mg., 47%), as an amorphous white solid, m.p. 70° to 81° (decomp.), [α] - 72.2° (CHCl3), λmax. 313 nm (ε 9,300) with an inflexion at 237 nm. (ε 14,900), νmax. (CHBr3) 3415 (NH), 1789 (β-lactam), 1728 (--CO2R), and 1682 and 1510 cm.-1 (CONH); the p.m.r. spectrum (CDCl3) indicated that this compound was mainly the cis-isomer, with signals at τ 3.50 (NH, d, J 9 Hz.); 4.08 and ca. 2.60 (CH=CH, two d, JAB 12 Hz.); 4.09 (C(7) -H, dd, J 5, 9 Hz.); 4.93 (C(6) -H, d, J 5 Hz.); 5.33 (--CH2CCl3, s); 6.16 (--CH2CONH--, s); and 6.29 and 6.61 (C(2) --CH2, AB-q J 18 Hz.), together with the trans-isomer (10 to 15%) with signals at τ 3.88 and 1.96 (CH=CH, two d, J 16 Hz.) [Found: C, 53.4; H, 3.6; N, 3.8; S, 9.1; Cl, 15.25; C31H25Cl3N2O6S2 (692.0) requires C, 53.8; H, 3.6; N, 4.05; S, 9.3; Cl, 15.4%]. Rf 0.54 (Merck GF254 + 266 plates, with benzene: ethyl acetate = 5:1 for development).

Workup

  1. stirringAfter stirring for 45 minutes
  2. customthe solvent was removed in vacuo
  3. extractionthe residue was extracted with ethyl acetate (50 ml.)
  4. filtrationthe insoluble material was filtered off
  5. washthe filtrate was washed well with water (2 × 50 ml.) and brine (50 ml.)
  6. customdried
  7. customevaporated to an oil (1.07 g.)
  8. customThis material was purified by chromatography on 0.05-0.2mm

Sources & evidence

ORD record
ord-fb7809e632c44511b2bb3fe20901baeb
Source dataset
uspto-grants-1978_08
Patent number
US04110534

Reaction notes

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