Benzyl Bromide → 6-[p-(Benzyloxy)phenyl]-3,4-dihydro-1-methylpyrrolo[1,2-a]pyrazine fumarate

HRID 486571

反応式

HRID 486571 の反応式
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:12]3[CH2:13][CH2:14][N:15]=[C:16]([CH3:17])[C:11]3=[CH:10][CH:9]=2)=[CH:4][CH:3]=1.[CH2:18](Br)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.[OH-].[Na+].[C:28]([OH:35])(=[O:34])/[CH:29]=[CH:30]/[C:31]([OH:33])=[O:32]>[Br-].C([N+](CCCC)(CCCC)CCCC)C1C=CC=CC=1.O.C(O)C.C(Cl)Cl>[C:28]([OH:35])(=[O:34])/[CH:29]=[CH:30]/[C:31]([OH:33])=[O:32].[CH2:18]([O:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[N:12]3[CH2:13][CH2:14][N:15]=[C:16]([CH3:17])[C:11]3=[CH:10][CH:9]=2)=[CH:6][CH:7]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

参加物

9

反応物 4

HCID 7498Benzyl BromideHCID 14798Sodium HydroxideHCID 444972Fumaric AcidHCID 1357369333,4-Dihydro-6-(4-hydroxyphenyl)-1-methylpyrrolo[1,2-a]pyrazine

生成物 1

HCID 190954396-[p-(Benzyloxy)phenyl]-3,4-dihydro-1-methylpyrrolo[1,2-a]pyrazine fumarate収率 19%

試薬・触媒・溶媒 4

HCID 2724282Benzenemethanaminium, N,N,N-tributyl-, bromide触媒HCID 702Ethanol溶媒HCID 962Water溶媒2 回HCID 6344Dichloromethane溶媒2 回

実験手順

3,4-Dihydro-6-(4-hydroxyphenyl)-1-methylpyrrolo[1,2-a]pyrazine (5.0 g), 100 ml of methylene chloride, 5.3 ml of benzyl bromide and 0.8 g of benzyltributylammonium bromide was added in succession to a solution of 1.8 g of sodium hydroxide in 100 ml of water under argon. The mixture was boiled under reflux overnight and stirred and subsequently cooled. After the addition of 100 ml of methylene chloride and 100 ml of water the phases were separated and the aqueous phase was extracted twice with 100 ml of methylene chloride each time. The organic phases were combined, dried with MgSO4 and freed from solvent. The residue, 10.3 g of brown oil, was chromatographed on 500 g of silica gel with methylene chloride/methanol mixtures (99:1 to 9:1) as the eluent. The crude product, 4.9 g of brown, amorphous material, was dissolved in a 10-fold amount of hot ethanol and treated with 1.1 equivalents of a saturated solution of fumaric acid in ethanol. The product, 2.2 g of yellow crystals, was recrystallized from a 20-fold amount of ethanol. There were obtained 1.8 g (19%) of 6-[p-(benzyloxy)phenyl]-3,4-dihydro-1-methylpyrrolo[1,2-a]pyrazine fumarate (1:1); m.pt.: 165°-168° C. (dec.).

後処理

  1. temperatureunder reflux overnight
  2. temperaturesubsequently cooled
  3. customwere separated
  4. extractionthe aqueous phase was extracted twice with 100 ml of methylene chloride each time
  5. dry with materialdried with MgSO4
  6. customThe residue, 10.3 g of brown oil, was chromatographed on 500 g of silica gel with methylene chloride/methanol mixtures (99:1 to 9:1) as the eluent
  7. dissolutionThe crude product, 4.9 g of brown, amorphous material, was dissolved in a 10-fold amount of hot ethanol
  8. customThe product, 2.2 g of yellow crystals, was recrystallized from a 20-fold amount of ethanol

出典と根拠

ORDレコード
ord-1d37091acaeb42c99925bb1b37d2d860
出典データセット
uspto-grants-1994_03
特許番号
US05292732

関連ノート

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