Tri-o-tolylphosphine → HCID 178471560, 화합물

HRID 1639243

반응식

HRID 1639243 반응식
[C:1]([NH:7][C:8]1[N:9]=[C:10]([OH:28])[C:11]2[CH:17]=[C:16]([CH:18]=[CH:19][CH2:20][O:21][CH:22]3[CH2:27][CH2:26][CH2:25][CH2:24][O:23]3)[CH:15]=[N:14][C:12]=2[N:13]=1)(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].I[C:30]1[CH:51]=[CH:50][C:33]([C:34]([NH:36][C@H:37]([C:45]([O:47][CH2:48][CH3:49])=[O:46])[CH2:38][CH2:39][C:40]([O:42][CH2:43][CH3:44])=[O:41])=[O:35])=[CH:32][CH:31]=1.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>C(N(CC)CC)C.C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[O:23]1[CH2:24][CH2:25][CH2:26][CH2:27][CH:22]1[O:21][CH2:20][C:19]([C:30]1[CH:51]=[CH:50][C:33]([C:34]([NH:36][C@H:37]([C:45]([O:47][CH2:48][CH3:49])=[O:46])[CH2:38][CH2:39][C:40]([O:42][CH2:43][CH3:44])=[O:41])=[O:35])=[CH:32][CH:31]=1)=[CH:18][C:16]1[CH:15]=[N:14][C:12]2[N:13]=[C:8]([NH:7][C:1](=[O:6])[C:2]([CH3:4])([CH3:5])[CH3:3])[N:9]=[C:10]([OH:28])[C:11]=2[CH:17]=1

참가 물질

7

반응물 3

HCID 80271Tri-o-tolylphosphineHCID 1885228diethyl (2S)-2-[(4-iodobenzoyl)amino]pentanedioate2회HCID 178447254HCID 178447254, 화합물

생성물 1

HCID 178471560HCID 178471560, 화합물

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 6342Acetonitrile용매HCID 8471Triethylamine용매

실험 절차

A mixture containing 3.48 g (9 mm) of 2-pivaloylamino-4-hydroxy-6-(3-tetrahydropyr-2-yloxyprop-1-en-1-yl)-pyrido[2,3-d]pyrimidine, 3.12 g, (1.2 equiv.) of diethyl N-(4-iodobenzoyl)glutamate, 546 mg (20%) of tris(2-methylphenyl)phosphine, 201 mg (10%) of palladium acetate and 85.5 mg (5%) of cuprous iodide in 15 ml of triethylamine and 240 ml of acetonitrile was heated at reflux under nitrogen. After 12 hours., 1.17 g of diethyl N-(4-iodobenzoyl)glutamate was added and the reaction mixture was heated at reflux under nitrogen for an additional 12 hours. The reaction mixture then was concentrated under reduced pressure and the residue was chromatographed on silica gel, eluting with 20:1 ethyl acetate:hexane. (Recovered starting material can be recycled through the foregoing procedure.) The concentrated material was dissolved in 1:5 ethyl acetate:ether and this solution was refrigerated for 15 hours. The solid which formed was collected by filtration, washed with cold ethyl acetate and dried to yield diethyl N-[4-{1-(tetrahydropyr-2-yloxy)-3-(2-pivaloylamino-4-hydroxypyrido[2,3-d]pyrimidin-6-yl)prop-2-en-2-yl}benzoyl]glutamate. mp. 273°-275° C. Analysis calculated for C36H45N4O9 ; C, 62.50; H, 6.56; N, 10.12. Found: C, 62.21; H, 6.34; N, 9.83. NMR (CDCL3), delta, 1.24 (t, 3H, J=7 Hz), 1.32 (t 3H, J=7 Hz), 1.32 (s, 9H), 1.53-1.87 (m, 6H), 2.11-2.22 (m, 1H), 2.29-2.41 (m 1H), 2.42-2.58 (m, 2H), 3.53-3.59 (m, 1H), 3.80-3.88 (m, 1H), 4.13 (q, 2H, J=7 Hz), 4.25 (q, 2H, J=7 Hz), 4.33 (d, 1H, J=14 Hz), 4.62 (d, 1H, J=14 Hz), 4.75-4.83 (m, 2H), 6.84 (s, 1H), 7.12 (brs, 1H, NH, J =7 Hz), 7.31 (d, 2H, J=8.1 Hz), 7.79 (d, 2H, J=8.1 Hz), 8.13 (d, 1H, J=1.6 Hz), 8.34 (brs, NH), 8.42 (d, 1H, J=1.6 Hz), 11.99 (brs, NH).

후처리

  1. temperaturewas heated
  2. temperatureat reflux under nitrogen
  3. temperaturethe reaction mixture was heated
  4. temperatureat reflux under nitrogen for an additional 12 hours
  5. concentrationThe reaction mixture then was concentrated under reduced pressure
  6. customthe residue was chromatographed on silica gel
  7. washeluting with 20:1 ethyl acetate
  8. custom(Recovered
  9. dissolution) The concentrated material was dissolved in 1:5 ethyl acetate
  10. waitether and this solution was refrigerated for 15 hours
  11. customThe solid which formed
  12. filtrationwas collected by filtration
  13. washwashed with cold ethyl acetate
  14. customdried

출처 및 근거

ORD 기록
ord-001076e4e5e546a8a007a4d5eb067dff
출처 데이터셋
uspto-grants-1989_11
특허 번호
US04883799

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