N-Methylbutylamine → HCID 54079109, compound

HRID 275530Notes

Reaction equation

HRID 275530 reaction equation
[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.[CH2:46]([N:50](CC(C)C)CC(C)C)C(C)C.C(OC(Cl)=O)C(C)C.CNCCCC>CC(C)=O.O.C(Cl)Cl.C(O)(C)C>[CH3:46][NH:50][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]

Participants

10

Reactant 5

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

Product 1

HCID 54079109HCID 54079109, compoundYield 75.6%

Reagents, catalysts & solvents 4

HCID 180AcetoneSolventHCID 962WaterSolventHCID 3776IsopropanolSolventHCID 6344DichloromethaneSolvent

Procedure

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 12,13-Bis (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 (3X), dried on magnesium sulfate and evaporated to dryness. The residue was purified by "Flash chromatography" on silica gel (Kieselgel 60, Merck, unter 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 λmax (log ε)=230 (4.39) nm; 1H-NMR (δ, CDCl3), 0.85-0.98 (6H, m, 2--CH2CH3), 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+).

Workup

  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 12,13-Bis (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 (3X)
  10. customdried on magnesium sulfate
  11. customevaporated to dryness
  12. customThe residue was purified by "Flash chromatography" on silica gel (Kieselgel 60, Merck, unter 0.063 mm, 50 g)
  13. washElution
  14. additionwith a mixture of hexane-ethyl acetate (4:1 v/v)

Sources & evidence

ORD record
ord-ed54096612e749e7bc502c6cb216b869
Source dataset
uspto-grants-1995_02
Patent number
US05393785

Reaction notes

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