Diisopropylcarbodiimide → HCID 178454160、化合物

HRID 34687

反応式

HRID 34687 の反応式
[CH:1]1[CH:6]=[CH:5][C:4](/[C:7](/[C:10]2[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[CH:12][CH:11]=2)=[N:8]/[OH:9])=[CH:3][CH:2]=1.[C:19]([NH:26][C@H:27]([C:35]([OH:37])=[O:36])[CH2:28][C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20].C(N=C=NC(C)C)(C)C>C(Cl)Cl>[NH:26]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[C@H:27]([C:35]([OH:37])=[O:36])[CH2:28][C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1.[CH:1]1[CH:2]=[CH:3][C:4](/[C:7](/[C:10]2[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[CH:12][CH:11]=2)=[N:8]/[OH:9])=[CH:5][CH:6]=1

参加物

5

反応物 3

HCID 12734DiisopropylcarbodiimideHCID 77857L-Phenylalanine, N-[(1,1-dimethylethoxy)carbonyl]-HCID 6506582Benzophenone, 4-nitro-, oxime

生成物 1

HCID 178454160HCID 178454160、化合物収率 398%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

A suspension of 8.6 g (5 mmol) of oxime resin (described in W. F. DeGrado and E. T. Kaiser, J. Org. Chem., 47, 3258 (1982)), 2.652 g of BOC-L-phenylalanine and 5.0 ml of 2.0M diisopropylcarbodiimide (DIC) in 96 ml of CH2Cl2 was shaken gently for 3days. The resulting resin was filtered off and washed successively with 5×100 ml of 2:1 CH2Cl2 /C2H5OH, 3×100 ml CH3OH and dried. Unreacted sites were blocked by shaking for 15 ml with 6.05 ml of C6H5COCl and 9.05 ml of diisopropylethylamine (DIEA) in 100 ml of CH2Cl2. The solid was filtered off and vacuum dried to give 10.1 g of BOC-L-Phe-oxime resin. A 4.69 g portion (1.37 mmol) of the resin was coupled successively with 2.6 mmoles of the symmetric anhydrides of BOC-L-proline (3 h) and BOC-L-tyrosine (t-butyl ether) (17 h) using a Beckman 990B synthesizer and the program of Nakagawa and Kaiser, described in J. Org. Chem., 48, 678 (1983). The symmetric anhydride was prepared by treating 7.2 mmoles of the corresponding BOC-amino acid (Bachem, Switzerland) in 38 ml of CH2Cl2 and 10 ml of dimethylformamide (DMF) with 3.6 ml of 1M DIC in CH2Cl2 at 0°. Note that there is no neutralization step in this program; after the addition of 3.6 mmole of the preformed BOC symmetric anhydride, 4.6 ml of 10% DIEA in CH2Cl2 was added. The resulting BOC-Tyr(tBu)-Pro-Phe-resin was washed with ethanol and after vacuum drying weighed 5.17 g. (Amino acid analysis found: Tyr, 0.301; Pro, 0.272; Phe. 0.292 mmol/g).

後処理

  1. filtrationThe resulting resin was filtered off
  2. washwashed successively with 5×100 ml of 2:1 CH2Cl2 /C2H5OH, 3×100 ml CH3OH
  3. customdried
  4. stirringby shaking for 15 ml with 6.05 ml of C6H5COCl and 9.05 ml of diisopropylethylamine (DIEA) in 100 ml of CH2Cl2
  5. filtrationThe solid was filtered off
  6. customvacuum dried

出典と根拠

ORDレコード
ord-7d0b5e9cd1864395a5c3503192d5ae1f
出典データセット
uspto-grants-1988_08
特許番号
US04762881

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