Phosphorus oxychloride → Chloro-N,N-dimethylformiminium chloride

HRID 648416노트

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HRID 648416 반응식
P(Cl)(Cl)([Cl:3])=O.[C:6]([O:25][N:26]=[C:27]([C:31]1[N:32]=[C:33]([NH:36][C:37]([C:50]2[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=2)([C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)[C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[S:34][CH:35]=1)[C:28]([OH:30])=O)([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)([C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[NH2:56][CH:57]1[C:78](=[O:79])[N:59]2[C:60]([C:75]([OH:77])=[O:76])=[C:61]([CH2:64][S:65][C:66]3[N:70]([CH2:71][C:72]([OH:74])=[O:73])[N:69]=[N:68][N:67]=3)[CH2:62][S:63][C@H:58]12.C[Si](CC(N)=O)(C)C.C[Si](C([Si](C)(C)C)C(N)=O)(C)C>O.C(OCC)(=O)C.C(Cl)Cl.CN(C)C=O>[CH3:58][N+:59]([CH3:78])=[CH:60][Cl:3].[Cl-:3].[C:6]([O:25][N:26]=[C:27]([C:31]1[N:32]=[C:33]([NH:36][C:37]([C:50]2[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=2)([C:38]2[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=2)[C:44]2[CH:45]=[CH:46][CH:47]=[CH:48][CH:49]=2)[S:34][CH:35]=1)[C:28]([NH:56][CH:57]1[C:78](=[O:79])[N:59]2[C:60]([C:75]([OH:77])=[O:76])=[C:61]([CH2:64][S:65][C:66]3[N:70]([CH2:71][C:72]([OH:74])=[O:73])[N:69]=[N:68][N:67]=3)[CH2:62][S:63][C@H:58]12)=[O:30])([C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

참가 물질

11

반응물 5

HCID 24813Phosphorus oxychlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 11708267BistrimethylsilylacetamidHCID 127691497-amino-3-(1-carboxymethyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acidHCID 53447342HCID 53447342, 화합물

생성물 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 1317124087-[2-trityloxyimino-2-(2-tritylamino-1,3-thiazol-4-yl)acetamido]-3-(1-carboxymethyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid

시약·촉매·용매 4

HCID 962Water용매HCID 6228Dimethylformamide용매HCID 6344Dichloromethane용매HCID 8857Ethyl Acetate용매2회

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온도
-3 °C

실험 절차

The Vilsmeier reagent was prepared from dry dimethylformamide (0.26 ml), phosphorus oxychloride (0.31 ml) and dry ethyl acetate (1 ml) according to a conventional method. Dry methylene chloride (40 ml) and 2-trityloxyimino-2-(2-tritylamino-1,3-thiazol-4-yl)acetic acid (syn isomer) (2.1 g) were added thereto at -3° C., and the resulting mixture was stirred for 30 minuts at the same temperature. The resulting solution was added at -10° C. to a suspension, which was prepared by stirring and warming at 40° C. a mixture of 7-amino-3-(1-carboxymethyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid (1.0 g), dry ethyl acetate (40 ml), trimethylsilylacetamide (2.9 g) and bis(trimethylsilyl)acetamide (1.7 g), and the resulting mixture was stirred for 2 hours at -10° to -5° C. Water (30 ml) was added to the reaction mixture and the mixture was filtered. To the filtrate was added methylene chloride (20 ml) and the organic layer was separated. To the organic layer was added water (30 ml) and the mixture was adjusted to pH 7.0 with sodium bicarbonate. The aqueous layer was separated, washed with ethyl acetate and, after addition of ethyl acetate (100 ml), adjusted to pH 3.0 under stirring with conc. hydrochloric acid. The ethyl acetate layer was separated, washed with water, dried over magnesium sulfate and concentrated to dryness to give 7-[2-trityloxyimino-2-(2-tritylamino-1,3-thiazol-4-yl)acetamido]-3-(1-carboxymethyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid (syn isomer) (0.48 g).

후처리

  1. additionThe resulting solution was added at -10° C. to a suspension, which
  2. customwas prepared
  3. stirringby stirring
  4. temperaturewarming at 40° C.
  5. stirringthe resulting mixture was stirred for 2 hours at -10° to -5° C
  6. filtrationthe mixture was filtered
  7. additionTo the filtrate was added methylene chloride (20 ml)
  8. customthe organic layer was separated
  9. additionTo the organic layer was added water (30 ml)
  10. customThe aqueous layer was separated
  11. washwashed with ethyl acetate
  12. additionafter addition of ethyl acetate (100 ml)
  13. stirringunder stirring with conc. hydrochloric acid
  14. customThe ethyl acetate layer was separated
  15. washwashed with water
  16. dry with materialdried over magnesium sulfate
  17. concentrationconcentrated to dryness

출처 및 근거

ORD 기록
ord-85481b81f12441759be3cc2a6b1d7688
출처 데이터셋
uspto-grants-1983_10
특허 번호
US04411898

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