Hexane → Methyl 2-(1-Decenyl)benzoate

HRID 365040Notes

Reaction equation

HRID 365040 reaction equation
[C:1](=[O:3])=[O:2].[CH3:4][C:5]([CH3:7])=O.[Br-].[CH2:9]([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16]C.[Li][CH2:38]CCC.[CH3:42][CH2:43][CH2:44][CH2:45][CH2:46]C.CN(P(N(C)C)(N(C)C)=O)C>C1COCC1.CCOC(C)=O.O>[CH:5]([C:7]1[CH:46]=[CH:45][CH:44]=[CH:43][C:42]=1[C:1]([O:3][CH3:38])=[O:2])=[CH:4][CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH3:9]

Participants

9

Reactant 5

HCID 8058HexaneHCID 12679HexamethylphosphoramideHCID 2724864Phosphonium, nonyltriphenyl-, bromide (1:1)HCID 18522661Acetone cardiceHCID 178418339Butyllithium

Product 1

HCID 54112223Methyl 2-(1-Decenyl)benzoate

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred, cooled (-78° C., dry ice/acetone) solution of nonyltriphenylphosphonium bromide (prepared as described in Example 1 Part A) (12.09 g, 22 mM, 1.2 eq.) in dry THF (125 ml) was added dropwise under argon a 2.5M solution of n-BuLi in hexane (7.32 ml, 18.3 mM, 1 eq.). Twenty minutes after completed addition HMPA (19 ml, 110 mM, 6 eq.) was added followed by dropwise addition of the title A aldehyde (3.0 g, 183 mM) in 25 ml of THF over a 1.5 hour period. The mixture was warmed to 0° C. (ice bath) over a 30 minute period, then added to 200 ml of H2O and extracted (2×) with ethyl acetate. The organic phase was washed with saturated NH4Cl, dried over anhydrous Na2SO4 and evaporated to a thick brown oil. Crude oil was flash chromatographed on LPS-1 silica gel eluting with (8:2) Hex-CH2Cl2. Product containing fractions were evaporated to give 1.65 g (33%) of the desired title Wittig product (mixture of cis and trans isomers obtained) as a clear oil with consistent NMR (CDCl3, 60 MHz) spectral data. TLC (1:1) EtOAc-Hex, Rf product=0.80, UV and PMA, single spot.

Workup

  1. customprepared
  2. customTwenty minutes
  3. additionwas added
  4. extractionextracted (2×) with ethyl acetate
  5. washThe organic phase was washed with saturated NH4Cl
  6. dry with materialdried over anhydrous Na2SO4
  7. customevaporated to a thick brown oil
  8. customchromatographed on LPS-1 silica gel eluting with (8:2) Hex-CH2Cl2
  9. additionProduct containing fractions
  10. customwere evaporated
  11. customto give 1.65 g (33%) of the desired title
  12. additionWittig product (mixture of cis and trans isomers obtained) as a clear oil with consistent NMR (CDCl3, 60 MHz) spectral data

Sources & evidence

ORD record
ord-f8f3f362619a444c96fb2f95ae1f6bb8
Source dataset
uspto-grants-1986_08
Patent number
US04607053

Reaction notes

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