Oxalyl chloride → (+)-N-[2-[[(2,3-Dihydro-1,4-benzodioxin-2-yl)methyl]amino]ethyl]-7,7-dimethyl-2-oxobicyclo[2,2,1]heptane-1-carboxamide

HRID 893728노트

반응식

HRID 893728 반응식
[CH3:1][C:2]1([CH3:15])[C:6]2([CH2:10]S(Cl)(=O)=O)[C:7]([CH2:9][CH:3]1[CH2:4][CH2:5]2)=[O:8].C(Cl)(=O)C(Cl)=[O:18].[NH2:22][CH2:23][CH2:24][NH:25][CH2:26][CH:27]1[O:32][C:31]2[CH:33]=[CH:34][CH:35]=[CH:36][C:30]=2[O:29][CH2:28]1.C(N(C(C)C)CC)(C)C>C(Cl)Cl>[O:32]1[C:31]2[CH:33]=[CH:34][CH:35]=[CH:36][C:30]=2[O:29][CH2:28][CH:27]1[CH2:26][NH:25][CH2:24][CH2:23][NH:22][C:10]([C:6]12[C:2]([CH3:15])([CH3:1])[CH:3]([CH2:4][CH2:5]1)[CH2:9][C:7]2=[O:8])=[O:18]

참가 물질

6

반응물 4

HCID 65578Oxalyl chlorideHCID 81531DiisopropylethylamineHCID 26579910-Camphorsulfonyl chlorideHCID 146529492-[N-(2-aminoethyl)]aminomethyl-2,3-dihydrobenzodioxin

생성물 1

HCID 19891064(+)-N-[2-[[(2,3-Dihydro-1,4-benzodioxin-2-yl)methyl]amino]ethyl]-7,7-dimethyl-2-oxobicyclo[2,2,1]heptane-1-carboxamide

시약·촉매·용매 1

HCID 6344Dichloromethane용매2회

실험 절차

(+)-Ketopinic acid (900 mg, 5.0 mmole), prepared from (+)-10-camphorsulfonyl chloride by the procedure of Bartlett and Knox, Org. Syn., 45, p. 55, was converted to the acid chloride by treatment of a solution of the compound in 50 ml of methylene chloride with 1.0 ml (11.5 mmole) of oxalyl chloride. After stirring for 2 hours at room temperature, the mixture was concentrated in vacuum. It was then redissolved in 50 ml of methylenechloride and added at 0° C. to a solution of 1.04 g (10 mmole) of 2-[N-(2-aminoethyl)]aminomethyl-2,3-dihydrobenzodioxin and 1.3 g (10 mmole) of diisopropylethylamine in 50 ml of dichloromethane. After stirring overnight at room temperature, the mixture was washed with saturated sodium bicarbonate solution, with saturated sodium chloride, dried over sodium sulfate, filtered and concentrated in vacuum. The residue was column chromatographed on 75 g of silica gel with chloroform as eluant and the title compound crystallized from isopropanol with the addition of 4 N HCl/isopropyl alcohol and 3 volumes of diethyl ether. This procedure gave 835 mg of title compound as the monohydrochloride, m.p. 172°-173° C., with an [α]D25 =+32.7 (MeOH).

후처리

  1. concentrationthe mixture was concentrated in vacuum
  2. dissolutionIt was then redissolved in 50 ml of methylenechloride
  3. stirringAfter stirring overnight at room temperature
  4. washthe mixture was washed with saturated sodium bicarbonate solution, with saturated sodium chloride
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuum
  8. customchromatographed on 75 g of silica gel with chloroform as eluant
  9. customthe title compound crystallized from isopropanol with the addition of 4 N HCl/isopropyl alcohol and 3 volumes of diethyl ether

출처 및 근거

ORD 기록
ord-4af8689d729349fe90129fcd35a816be
출처 데이터셋
uspto-grants-1992_06
특허 번호
US05126367

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