Benzoyl chloride → N-[1-[(3-Buten-1-yl)methylphenylsilyl]-3-methyl-1-butyl]benzamide

HRID 2306516Notes

Reaction equation

HRID 2306516 reaction equation
[N:1]([CH:4]([Si:9]([CH2:17][CH2:18][CH:19]=[CH2:20])([CH3:16])[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[CH2:5][CH:6]([CH3:8])[CH3:7])=[N+]=[N-].[H-].[Al+3].[Li+].[H-].[H-].[H-].[C:27](Cl)(=[O:34])[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1>C(OCC)C.C(Cl)Cl.CCN(CC)CC>[CH2:17]([Si:9]([CH3:16])([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[CH:4]([NH:1][C:27](=[O:34])[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)[CH2:5][CH:6]([CH3:8])[CH3:7])[CH2:18][CH:19]=[CH2:20]

Participants

7

Reactant 3

HCID 7412Benzoyl chlorideHCID 21226445Aluminium lithium hydrideHCID 22967160(1-Azido-3-methyl-1-butyl)(3 buten-1-yl)methylphenylsilane

Product 1

HCID 22967188N-[1-[(3-Buten-1-yl)methylphenylsilyl]-3-methyl-1-butyl]benzamide

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolvent2×HCID 6344DichloromethaneSolventHCID 8471TriethylamineSolvent

Procedure

To a solution of azide 47 (2.75 g, 9.57 mmol) in ethyl ether (100 mL) at 0° C. was added dropwise over 5 min lithium aluminum hydride (1 M in ether, 47.8 mmol), and the mixture was allowed to warm to rt over 10 min. After stirring for 30 min under argon; the mixture was cooled to 0° C. and diluted with ether (100 mL). This mixture was quenched with saturated aqueous Na2SO4 solution until evolution of hydrogen had ceased. The mixture was dried with solid Na2SO4 and filtered. The residue was extracted with ether (50 mL) and the organic extracts combined. Concentration gave crude amine 48 as a colorless oil. This amine was dissolved in CH2Cl2 (60 mL) and Et3N (5 mL), and the solution was cooled to 0° C. To this solution was added dropwise over min benzoyl chloride (1.34 g, 9.57 mmol), and the mixture was allowed to warm to rt. After stirring overnight under argon, the reaction mixture was quenched with saturated aqueous NaHCO3 (20 mL). The organic layer was isolated and the aqueous layer extracted twice with 50-mL portions of CH2Cl2. The combined organic extracts were washed with saturated aqueous NaCl, dried over Na2SO4, and concentrated. Flash chromatography over silica gel (1/9 EtOAc:hexane) gave a sticky colorless solid of 49 as a mixture of diastereomers (2.6 g, 74%): Rf=0.20 (1/9 EtOAc:hexane); 1H NMR (300 MHz, CDCl3) δ 7.69-7.60 (m, 2H), 7.56-7.54 (m, 2H), 7.48-7.37 (m, 6H), 5.95-5.80 (m, 1H), 5.57 (d, J=9.9 Hz, 1H), 5.0 (d, J=17.0 Hz, 1H), 4.90 (d, J=8.6 Hz, 1H), 4.24-4.13 (m, 1H), 2.17-2.07 (m, 2H), 1.68-1.55 (m, 1H), 1.44-1.24 (m, 2H), 1.07-0.99 (m, 2H), 0.93 (d, J=6.4 Hz, 3H), 0.85 and 0.84 (two doublets due to diastereomers, J=6.6 Hz, 3H), 0.40 and 0.39 (two singlets due to diastereomers, 3H); 13C NMR (75 MHz, CDCl3) δ 166.7, 140.9, 135.0, 134.7, 134.5, 134.34, 134.31, 131.1, 131.0, 130.5, 129.64, 129.61, 128.8, 128.54, 1128.0, 126.6, 113.3, 113.2, 40.5, 40.4, 37.2, 36.9, 27.5, 25.1, 23.6, 21.2, 11.3, 10.7, −6.7, −7.4; IR (neat) 3279 (m, br), 3064 (m), 2954 (s), 2919 (m), 2867 (m), 1787 (w), 1727 (w), 1628 (s), 1577 (m), 1536 (s), 1487 (m), 1427 (m), 1323 (m), 1252 (m), 1110 (m), 994 (m), 902 (m), 791 (m), 699 (s) cm−1; MS (FAB) m/e (rel. intensity) 366 (MH+, 11), 365 (9), 364 (5), 350 (6), 322 (11), 311 (11), 310 (34), 290 (10), 289 (26), 288 (100), 253 (8); HRMS (FAB) calcd for C23H31NOSi: 365.2175 (MH+−1), found: 365.2172. Anal. Calcd for C23H31NOSi: C, 75.56; H, 8.55; N; 3.83. Found: C, 75.18; H, 8.41; N, 3.72.

Workup

  1. temperaturethe mixture was cooled to 0° C.
  2. customThis mixture was quenched with saturated aqueous Na2SO4 solution until evolution of hydrogen
  3. dry with materialThe mixture was dried with solid Na2SO4
  4. filtrationfiltered
  5. extractionThe residue was extracted with ether (50 mL)
  6. concentrationConcentration
  7. customgave crude amine 48 as a colorless oil
  8. temperatureto warm to rt
  9. stirringAfter stirring overnight under argon
  10. customthe reaction mixture was quenched with saturated aqueous NaHCO3 (20 mL)
  11. customThe organic layer was isolated
  12. extractionthe aqueous layer extracted twice with 50-mL portions of CH2Cl2
  13. washThe combined organic extracts were washed with saturated aqueous NaCl
  14. dry with materialdried over Na2SO4
  15. concentrationconcentrated

Sources & evidence

ORD record
ord-40f1519b3f8f4a06a5e279ac8685df77
Source dataset
uspto-grants-2002_08
Patent number
US06441212B1

Reaction notes

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