Propylene Oxide → t-Butyl 3-acetoxymethyl-7beta-(pyrid-4-ylacetamido)ceph-3-em-4-carboxylate

HRID 258651노트

반응식

HRID 258651 반응식
Cl.[N:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9](Cl)=[O:10])=[CH:4][CH:3]=1.C1OC1C.[C:16]([O:19][CH2:20][C:21]1[CH2:22][S:23][C@@H:24]2[C@H:35]([NH2:36])[C:34](=[O:37])[N:25]2[C:26]=1[C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])(=[O:18])[CH3:17]>C(OCC)(=O)C>[C:30]([O:29][C:27]([C:26]1[N:25]2[C:34](=[O:37])[C@@H:35]([NH:36][C:9](=[O:10])[CH2:8][C:5]3[CH:6]=[CH:7][N:2]=[CH:3][CH:4]=3)[C@H:24]2[S:23][CH2:22][C:21]=1[CH2:20][O:19][C:16](=[O:18])[CH3:17])=[O:28])([CH3:33])([CH3:31])[CH3:32]

참가 물질

5

반응물 3

HCID 6378Propylene OxideHCID 15573427tert-butyl (6R,7R)-3-[(acetyloxy)methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylateHCID 232920204-Pyridineacetyl chloride hydrochloride

생성물 1

HCID 131710773t-Butyl 3-acetoxymethyl-7beta-(pyrid-4-ylacetamido)ceph-3-em-4-carboxylate

시약·촉매·용매 1

HCID 8857Ethyl Acetate용매2회

실험 절차

A suspension of pyrid-4-ylacetyl chloride hydrochloride (6.0 g.) in ethyl acetate (50 ml) containing propylene oxide (12 ml.) was stirred, cooled in ice and treated dropwise with a solution of t-butyl 3-acetoxymethyl-7β-aminoceph-3-em-4-carboxylate (5.0 g.) in ethyl acetate (50 ml.). The mixture was stirred at 20° for 20 hours and then washed with saturated sodium bicarbonate solution and extracted with 2 N hydrochloric acid. The aqueous extract was washed with ethyl acetate, neutralised with saturated sodium bicarbonate solution and extracted with ethyl acetate. The extract was washed with water, dried over magnesium sulphate and evaporated to small bulk whereupon crystallisation began. The crystalline solid was washed well with petroleum spirit (bp. 40°-60°) and dried to give the title ester as a buff coloured powder (5.4 g., 80% based on amine). A portion (250 mg.) was recrystallised from ethyl acetate as white needles (170 mg.), [α]D +94° (c 0.9, DMSO) λmax. (EtOH) 256.5 nm (ε 9,900), νmax. (CHBr3) 3412 (NH), 1784 (β-lactam), 1736 (OAc), 1722 (CO2R), 1690 and 1512 cm.-1 (CONH), τ (d6 -DMSO) 0.81 (d, J 8 Hz; NH), 1.47 and 2.68 (2d, J 5 Hz; aromatic protons), 4.27 (q, J 8 and 5 Hz; C-7H), 4.85 (d, J 5 Hz; C-6 H), 5.01 and 5.36 (2d, J 13 Hz; C-3CH2), 6.38 (s; CH2CONH), 6.39 (s; C-2H2), 7.96 (s; OCOCH3), and 8.50 (s; C(CH3)3).

후처리

  1. temperaturecooled in ice
  2. stirringThe mixture was stirred at 20° for 20 hours
  3. washwashed with saturated sodium bicarbonate solution
  4. extractionextracted with 2 N hydrochloric acid
  5. extractionThe aqueous extract
  6. washwas washed with ethyl acetate
  7. extractionextracted with ethyl acetate
  8. washThe extract was washed with water
  9. dry with materialdried over magnesium sulphate
  10. customevaporated to small bulk whereupon crystallisation
  11. washThe crystalline solid was washed well with petroleum spirit (bp. 40°-60°)
  12. customdried

출처 및 근거

ORD 기록
ord-08b6ed9c33d54ffe867cfd76cd7c8c4f
출처 데이터셋
uspto-grants-1977_07
특허 번호
US04033950

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