N,N,N',N'-Tetramethylethylenediamine → 1-[2,5-Dimethoxy-3,6-bis(methoxymethoxy)phenyl]-5-[2,5-dimethoxy-3,6-bis(methoxymethoxy)-4-bromophenyl]pentane

HRID 1588167ノート

反応式

HRID 1588167 の反応式
[CH3:1][O:2][C:3]1[C:8]([O:9][CH2:10][O:11][CH3:12])=[CH:7][C:6]([O:13][CH3:14])=[C:5]([O:15][CH2:16][O:17][CH3:18])[C:4]=1[CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][C:24]1[C:29]([O:30][CH2:31][O:32][CH3:33])=[C:28]([O:34][CH3:35])[CH:27]=[C:26]([O:36][CH2:37][O:38][CH3:39])[C:25]=1[O:40][CH3:41].CN(C)CCN(C)C.C([Li])CCC.[Br:55]N1C(=O)CCC1=O>O1CCCC1.CN(C)P(=O)(N(C)C)N(C)C>[CH3:41][O:40][C:25]1[C:26]([O:36][CH2:37][O:38][CH3:39])=[CH:27][C:28]([O:34][CH3:35])=[C:29]([O:30][CH2:31][O:32][CH3:33])[C:24]=1[CH2:23][CH2:22][CH2:21][CH2:20][CH2:19][C:4]1[C:5]([O:15][CH2:16][O:17][CH3:18])=[C:6]([O:13][CH3:14])[C:7]([Br:55])=[C:8]([O:9][CH2:10][O:11][CH3:12])[C:3]=1[O:2][CH3:1]

参加物

7

反応物 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 67184N-bromobutanimideHCID 136460702,2'-Pentamethylene-bis[1,4-dimethoxy-3,6-bis(methoxymethoxy)benzene]HCID 178418339Butyllithium

生成物 1

HCID 139226831-[2,5-Dimethoxy-3,6-bis(methoxymethoxy)phenyl]-5-[2,5-dimethoxy-3,6-bis(methoxymethoxy)-4-bromophenyl]pentane

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 12679Hexamethylphosphoramide溶媒

反応条件

温度
-78 °C

実験手順

998 Milligrams of 2,2'-pentamethylenebis[1,4-dimethoxy-3,6-bis(methoxymethoxy)benzene] was dissolved in a mixed solvent of 30 ml of tetrahydrofuran with 3 ml of hexamethylphosphoric triamide, to this solution was added 1.03 ml of N,N,N',N'-tetramethylethylenediamine, was cooled to -78° C. on a dry ice-acetone mixture bath. 4.56 Milliliters of n-butyllithium (1.6 M, n-hexane solution) was added dropwise to the reaction mixture and stirred for 30 minutes. Next, 15 ml of tetrahydrofuran solution containing 1.22 g of N-bromosuccinimide was added dropwise and the reaction mixture was stirred overnight. The solvent was removed under reduced pressure, and the residue obtained was extracted twice with 50 ml of diethyl ether, and the diethyl ether layer was washed twice with 50 ml of water, and washed twice with 50 ml of a saturated sodium chloride aqueous solution, then dried over anhydrous magnesium sulfate. The diethyl ether solution was concentrated under reduced pressure, the residue obtained was purified by means of a preparative thin layer chromatography (thickness: 2 mm, adsorbent: Merck 5717 silica gel, developing solvent: 40% ethyl acetate-n-hexane). There were obtained 155 mg of 1-[2,5-dimethoxy-3,6-bis(methoxymethoxy)phenyl]-5-[2,5-dimethoxy- 3,6-bis(methoxymethoxy)-4-bromophenyl]pentane, as well as 22 mg of 2,2'-pentamethylenebis[1,4-dimethoxy-3,6-bis(methoxymethoxy)-5-bromobenzene].

後処理

  1. additionwas added dropwise
  2. stirringthe reaction mixture was stirred overnight
  3. customThe solvent was removed under reduced pressure
  4. customthe residue obtained
  5. extractionwas extracted twice with 50 ml of diethyl ether
  6. washthe diethyl ether layer was washed twice with 50 ml of water
  7. washwashed twice with 50 ml of a saturated sodium chloride aqueous solution
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationThe diethyl ether solution was concentrated under reduced pressure
  10. customthe residue obtained
  11. customwas purified by means of a preparative thin layer chromatography (thickness: 2 mm, adsorbent: Merck 5717 silica gel, developing solvent: 40% ethyl acetate-n-hexane)

出典と根拠

ORDレコード
ord-3615392963374954aacf7bf437e2d50c
出典データセット
uspto-grants-1993_06
特許番号
US05220042

反応ノート

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