Diethyl Ether → 1-Methoxy-4-(4-carboxymethyl phenyl)-1-butene

HRID 36771Notes

Reaction equation

HRID 36771 reaction equation
[Cl-].[CH3:2][O:3][CH2:4][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CC(C)([O-])C.[K+].[C:30]([CH2:33][C:34]1[CH:39]=[CH:38][C:37]([CH2:40][CH2:41][CH:42]=O)=[CH:36][CH:35]=1)([OH:32])=[O:31].C(OCC)C>C1(C)C=CC=CC=1.O1CCCC1>[CH3:2][O:3][CH:4]=[CH:42][CH2:41][CH2:40][C:37]1[CH:36]=[CH:35][C:34]([CH2:33][C:30]([OH:32])=[O:31])=[CH:39][CH:38]=1

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 15284223(4-(Carboxymethyl)phenyl)propanalHCID 23665647Potassium tert-butoxide

Product 1

HCID 544918961-Methoxy-4-(4-carboxymethyl phenyl)-1-buteneYield 78.1%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

To 3.77 g (11 mmol) of methoxymethyltriphenyl phosphonium chloride in 10 ml of toluene at 0° C. under nitrogen was added 11 ml (11 mmol) of 1M potassium t-butoxide in tetrahydrofuran over 20 minutes. The resulting solution was stirred for 10 minutes, then 1.92 g (10 mmol) of 3-(4-carboxymethylphenyl)-propanal in 10 ml of toluene was added over 15 minutes. After stirring the mixture for 20 minutes 40 ml of ethyl ether were added. The resulting precipitate was filtered with diatomaceous earth, collected, washed with 20 ml of water, 20 ml of saturated sodium chloride and dried with a 9:1 sodium sulfate:saturated sodium chloride mixture. Vacuum concentration of the filtered solution and trituration of the residue with hexane gave 1.72 g of 1-methoxy-4-(4-carboxymethyl phenyl)-1-butene. Chromatography of the above product (silica gel, 8:2 hexane:ethyl acetate) gave 1.0 g of a mixture of geometric isomers (Z/E-6:4) of the above product in a combined yield of 45 percent. b.p. 140° C. @0.07 torr. 1H NMR (CDCl3) δ2.23 (dq, J=1.0, 8.1 Hz), 2.40 (dq, J=1.3, 8.0 Hz) total 2H, 2.70 (t, J=8.1 Hz), 2.71 (t, J=8.0 Hz), total 2H, 3.48 (s), 3.55 (s), total 3H, 3.89 (s), 3.90 (s), total 3H, 4.32 (q, J=6.2 Hz), 4.71 (dr, J=7.3, 12.6 Hz), total 1H, 5.87 (dr, J=1.3, 6.2 Hz), 6.28 (dt, J=1.0, 12.6 Hz) , total 1H, 7.23 (d, J=8.2 Hz), 7.27 (d, J=8.2 Hz), total 1H, 7.94 (d, J=8.2 Hz), 7.95 (d, J=8.2 Hz), total 2H; 13C NMR (CDCl3) δ8 25.2, 29.3, 36.0, 37.4, 51.9, 56.0, 59.5, 101.8, 101.9, 105.5, 127.9, 28.0, 128.5, 128.6, 129.6, 129.7, 146.9, 147.5, 147.9, 48.0, 167.1, 167.2; IR (CHCl3) 3025, 2954, 1716, 1656, 1610, 1437, 1284, 1112 cm-1 ; MS(FD) m/z 220 (M+).

Workup

  1. additionwere added
  2. filtrationThe resulting precipitate was filtered with diatomaceous earth
  3. customcollected
  4. washwashed with 20 ml of water, 20 ml of saturated sodium chloride
  5. dry with materialdried with a 9:1 sodium sulfate

Sources & evidence

ORD record
ord-be4213c9e8f445ef97d0071410b158f6
Source dataset
uspto-grants-1995_05
Patent number
US05416211

Reaction notes

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