Carbon Dioxide → HCID 53755068, 화합물

HRID 376123

반응식

HRID 376123 반응식
[CH2:1]([O:3][C:4](=[O:30])[CH:5]([NH:27][CH:28]=[O:29])[CH:6](O)[C:7](=[CH2:25])[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][NH:14][C:15]([O:17][CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:16])[CH3:2].C=CCCC=C.S(Br)(Br)=O.[P:41]([O:50]C(C)C)([O:46][CH:47]([CH3:49])[CH3:48])[O:42][CH:43]([CH3:45])[CH3:44].C(OC(=O)C(NC=O)C=C(CBr)CCCCCCNC(OCC1C=CC=CC=1)=O)C.C(Br)(C)C.C(=O)=O>O1CCCC1>[CH2:1]([O:3][C:4](=[O:30])[CH:5]([NH:27][CH:28]=[O:29])[CH:6]=[C:7]([CH2:25][P:41]([O:46][CH:47]([CH3:49])[CH3:48])([O:42][CH:43]([CH3:45])[CH3:44])=[O:50])[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][NH:14][C:15]([O:17][CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:16])[CH3:2]

참가 물질

9

반응물 7

HCID 280Carbon DioxideHCID 63582-BromopropaneHCID 8304Triisopropyl phosphiteHCID 115981,5-HexadieneHCID 68176Thionyl bromideHCID 14966609HCID 14966609, 화합물HCID 53891339HCID 53891339, 화합물

생성물 1

HCID 53755068HCID 53755068, 화합물수율 47.1%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

To 13.70 g (32.60 mmol) of crude 10-(N-benzyloxycarbonylamino)-2-formylamino-3-hydroxy-4-methylene-decanoic acid ethyl ester in 137 ml of tetrahydrofuran there are added, under argon, 18.5 ml (156.4 mmol) of hexa-1,5-diene and then, dropwise at 10° within a period of 15 minutes, 6.1 ml (78.2 mmol) of thionyl bromide. The mixture is stirred for one hour at 10° and for 2 hours at room temperature and is then poured into 200 ml of ice-cold saturated sodium hydrogen carbonate solution; the organic phase is separated off and re-extracted once with dichloromethane. The organic phases are washed with ice-cold 0.5-normal sodium hydrogen carbonate solution and then with saturated sodium chloride solution, dried over sodium sulfate and concentrated to dryness by evaporation in vacuo at 40°. 64 ml (260 mmol) of triisopropyl phosphite (96%) are added immediately to the resulting crude 10-(N-benzyloxycarbonylamino)-4-bromomethyl-2-formylamino-dec-3-enoic acid ethyl ester (27 g, yellow honey), and the mixture is stirred for 17 hours at 80° under a pressure of approximately 100 mbar, the isopropyl bromide that forms being captured in a cold trap (CO2). The excess triisopropyl phosphite is then distilled off under reduced pressure and the evaporation residue (23 g) is purified by chromatography on a column filled with 650 mg of silica gel (0.04-0.063 mm) with ethyl acetate/methanol (95:5). 8.73 g of 10-(N-benzyloxycarbonylamino)-4-diisopropylphosphonomethyl-2-formylaminodec-3-enoic acid ethyl ester are obtained in the form of a yellowish honey.

후처리

  1. customthe organic phase is separated off
  2. extractionre-extracted once with dichloromethane
  3. washThe organic phases are washed with ice-cold 0.5-normal sodium hydrogen carbonate solution
  4. dry with materialwith saturated sodium chloride solution, dried over sodium sulfate
  5. concentrationconcentrated to dryness by evaporation in vacuo at 40°
  6. stirringthe mixture is stirred for 17 hours at 80° under a pressure of approximately 100 mbar
  7. distillationThe excess triisopropyl phosphite is then distilled off under reduced pressure
  8. customthe evaporation residue (23 g) is purified by chromatography on a column
  9. additionfilled with 650 mg of silica gel (0.04-0.063 mm) with ethyl acetate/methanol (95:5)

출처 및 근거

ORD 기록
ord-a6aac26bf5ce469ead695ca8d8741c5f
출처 데이터셋
uspto-grants-1996_01
특허 번호
US05488140

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