N-Methylbutylamine → HCID 54103883、化合物

HRID 357324ノート

反応式

HRID 357324 の反応式
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]([CH:22]([C:25]2[CH:30]=[CH:29][C:28]([O:31][CH3:32])=[CH:27][CH:26]=2)[CH2:23][CH3:24])=[CH:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][OH:21])=[CH:5][CH:4]=1.CC(C)=O.OS(O)(=O)=O.O=[Cr](=O)=O.C(N(CC(C)C)CC(C)C)C(C)C.C(OC(Cl)=O)C(C)C.[CH3:67][NH:68][CH2:69][CH2:70][CH2:71][CH3:72]>CC(C)=O.O.C(Cl)Cl.C(O)(C)C>[CH2:69]([N:68]([CH3:67])[C:20](=[O:21])[CH2:19][CH2:18][CH2:17][CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH:10]=[C:9]([C:6]1[CH:5]=[CH:4][C:3]([O:2][CH3:1])=[CH:8][CH:7]=1)[CH:22]([C:25]1[CH:26]=[CH:27][C:28]([O:31][CH3:32])=[CH:29][CH:30]=1)[CH2:23][CH3:24])[CH2:70][CH2:71][CH3:72]

参加物

10

反応物 5

HCID 8068N-MethylbutylamineHCID 14222TriisobutylamineHCID 62365Isobutyl chloroformateHCID 5423478012,13-Bis(4-methoxyphenyl)-11-pentadecenolHCID 131709961Jones' reagent

生成物 1

HCID 54103883HCID 54103883、化合物収率 68%

試薬・触媒・溶媒 4

HCID 180Acetone溶媒HCID 962Water溶媒HCID 3776Isopropanol溶媒HCID 6344Dichloromethane溶媒

実験手順

To a cooled solution of alcohol 3 (710 mg, 1.56 mmol) in acetone (17 ml) was added Jones' reagent (8N-chromic acid solution, 0.77 ml). After 30 minutes, isopropanol (5 ml) was added and the mixture was poured in water and extracted three times with ethyl acetate. The organic layer was washed twice with brine, dried over magnesium sulfate and evaporated to dryness. The crude 12,13Bis(4-methoxyphenyl)-11-pantadecenoic acid was used in the next step without purification. To its solution in anhydrous methylene chloride (4 ml) at -10° C. was added, under stirring, triisobutylamine (470 μl , 1.96 mmol) and isobutylchloroformate (280 μl, 2.1 mmol). After 40 minutes, N-methylbutylamine (1.5 ml) was added and the mixture was stirred at room temperature during 1 hour. Methylene chloride (50 ml) was added. The organic solution was washed with 1N HCl, saturated sodium bicarbonate solution and water (3×), dried on magnesium sulfate and evaporated to dryness. The residue was purified by "Flash chromatography" on silica gel (Kieselgel 60, Merck, under 0.063 mm, 50 g). Elution with a mixture of hexane-ethyl acetate (4:1 v/v) gave N-butyl,N-methyl-12,13-Bis(4-methoxyphenyl)-11-pentadecenoic amide (4) (549 mg, 68%) colorless oil; IR νmax (neat), 1640, 1600 cm-1 ; UV γmax (log ε)=230, (4.39) nm; 1H-NMR (δ, CDCl3), 0.85-0.98 (6H, m, 2CH2CH3), 2.27 (2H, t, J=7.1 Hz, CH2CON), 2.91 and 2.96 (3H, 2s, --NCH3), 3.25-3.36 (3H, m, --NCH2 and CH3CH2CH--), 3.77 and 3.78 (6H, 2s, OCH3), 5.50 (1H, J=7.1 Hz, --C=CH--) and 6.69-7.01 (8H, m, H--Ar) ppm; MS m/e=521 (M+).

後処理

  1. extractionextracted three times with ethyl acetate
  2. washThe organic layer was washed twice with brine
  3. dry with materialdried over magnesium sulfate
  4. customevaporated to dryness
  5. customThe crude 12,13Bis(4-methoxyphenyl)-11-pantadecenoic acid was used in the next step without purification
  6. additionTo its solution in anhydrous methylene chloride (4 ml) at -10° C. was added
  7. waitAfter 40 minutes
  8. stirringthe mixture was stirred at room temperature during 1 hour
  9. washThe organic solution was washed with 1N HCl, saturated sodium bicarbonate solution and water (3×)
  10. customdried on magnesium sulfate
  11. customevaporated to dryness
  12. customThe residue was purified by "Flash chromatography" on silica gel (Kieselgel 60, Merck, under 0.063 mm, 50 g)
  13. washElution
  14. additionwith a mixture of hexane-ethyl acetate (4:1 v/v)

出典と根拠

ORDレコード
ord-1bded450925a4946a21c883479861307
出典データセット
uspto-grants-1998_11
特許番号
US05840735

反応ノート

読み込み中…