Potassium hydride → 5-cinnamyloxymethyl-3-cyclopropylmethyl-9-methoxy-1,2,5,6,7,7a-hexahydro-4a,7-ethanobenzofuro[3,2-e]isoquinolin-4(3H)-one

HRID 35528

反応式

HRID 35528 の反応式
[H-].[K+].[CH:3]1([CH2:6][N:7]2[CH2:16][CH2:15][C:14]34[C:17]5[CH:23]=[CH:22][CH:21]=[C:20]([O:24][CH3:25])[C:18]=5[O:19][CH:13]3[CH:12]3[CH2:26][CH2:27][C:9]4([CH:10]([CH2:28][OH:29])[CH2:11]3)[C:8]2=[O:30])[CH2:5][CH2:4]1.C1(CN2[CH2:44][CH2:43][C:42]34C5C=CC=C(OC)C=5OC3[CH:40]3[CH2:54][CH2:55][C:37]4([CH:38](C(OC)=O)[CH2:39]3)C2=O)CC1.C(Br)C=CC1C=CC=CC=1>O1CCCC1.C(Cl)Cl.O.CCCCCC>[CH2:44]([O:29][CH2:28][CH:10]1[C:9]23[CH2:27][CH2:26][CH:12]([CH:13]4[O:19][C:18]5[C:20]([O:24][CH3:25])=[CH:21][CH:22]=[CH:23][C:17]=5[C:14]42[CH2:15][CH2:16][N:7]([CH2:6][CH:3]2[CH2:5][CH2:4]2)[C:8]3=[O:30])[CH2:11]1)[CH:43]=[CH:42][C:37]1[CH:55]=[CH:54][CH:40]=[CH:39][CH:38]=1

参加物

9

反応物 4

HCID 82127Potassium hydrideHCID 98116BromomethylstyreneHCID 212944573-cyclopropylmethyl-9-methoxy-5-methoxycarbonyl-1,2,5,6,7,7a-hexahydro-4a,7-ethanobenzofuro[3,2-e]isoquinolin-4(3H)-oneHCID 212944613-cyclopropylmethyl-5-hydroxymethyl-9-methoxy-1,2,5,6,7,7a-hexahydro-4a,7-ethanobenzofuro[3,2-e]isoquinolin-4(3H)-one

生成物 1

HCID 704165665-cinnamyloxymethyl-3-cyclopropylmethyl-9-methoxy-1,2,5,6,7,7a-hexahydro-4a,7-ethanobenzofuro[3,2-e]isoquinolin-4(3H)-one

試薬・触媒・溶媒 4

HCID 962Water溶媒HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒HCID 8058Hexane溶媒

実験手順

To a solution of 2.06 g of 35% potassium hydride in oil, prewashed with hexane, in 15 mL of tetrahydrofuran was added 0.70 g of 3-cyclopropylmethyl-5-hydroxymethyl-9-methoxy-1,2,5,6,7,7a-hexahydro-4a,7-ethanobenzofuro[3,2-e]isoquinolin-4(3H)-one (synthesized by following the procedures of Example 1, Method A, using 3-cyclopropylmethyl-9-methoxy-5-methoxycarbonyl-1,2,5,6,7,7a-hexahydro-4a,7-ethanobenzofuro[3,2-e]isoquinolin-4(3H)-one, U.S. Pat. No. 4,477,456, as the starting material) and the mixture was heated under reflux for 30 min. Cinnamyl bromide (2 mL) was added to the cooled mixture which was then heated under reflux for 20 minutes. Water and methylene chloride were added, and the aqueous layer was extracted with methylene chloride. Removal of the solvent from the dried organic phases gave 0.84 of 5-cinnamyloxymethyl-3-cyclopropylmethyl-9-methoxy-1,2,5,6,7,7a-hexahydro-4a,7-ethanobenzofuro[3,2-e]isoquinolin-4(3H)-one. NMR spectrum (δ in CDCl3): 7.1-7.4 (m, 5H); 6.8 (m, 2H); 6.7 (m, 1H); 6.6 (d, J=15 Hz, 1H); 6.3 (d/t, J=15/7 Hz, 1H), 4.4 (s, 1H); 5.8 (m, 2H); 3.9 (s, 3H); 0.5 (m, 2H); and 0.2 (m, 2H), among others.

後処理

  1. customsynthesized
  2. temperature4,477,456, as the starting material) and the mixture was heated
  3. temperatureunder reflux for 30 min
  4. temperaturewas then heated
  5. temperatureunder reflux for 20 minutes
  6. extractionthe aqueous layer was extracted with methylene chloride
  7. customRemoval of the solvent from the dried organic phases

出典と根拠

ORDレコード
ord-7ed96d5c211b4ecca6f4426ef547f4ce
出典データセット
uspto-grants-1988_08
特許番号
US04767764

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