Methyl Methacrylate → cis,cis-9,12-Octadecadienyl methacrylate

HRID 847762Notes

Reaction equation

HRID 847762 reaction equation
[CH2:1]([OH:19])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8]/[CH:9]=[CH:10]\[CH2:11]/[CH:12]=[CH:13]\[CH2:14][CH2:15][CH2:16][CH2:17][CH3:18].[C:20](OC)(=[O:24])[C:21]([CH3:23])=[CH2:22]>CC([O-])C.CC([O-])C.CC([O-])C.CC([O-])C.[Ti+4].C1C2NC3C(=CC=CC=3)SC=2C=CC=1>[C:20]([O:19][CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8]/[CH:9]=[CH:10]\[CH2:11]/[CH:12]=[CH:13]\[CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])(=[O:24])[C:21]([CH3:23])=[CH2:22]

Participants

5

Reactant 2

HCID 6658Methyl MethacrylateHCID 5365682Linoleyl alcohol

Product 1

HCID 86733419cis,cis-9,12-Octadecadienyl methacrylateYield 1,032.5%

Reagents, catalysts & solvents 2

HCID 7108PhenothiazineCatalystHCID 11026Titanium isopropoxideCatalyst

Procedure

The method of Example 1 was substantially repeated with cis,cis-9,12-octadecadien-1-ol (25.0 g, 9.38 mmol), methyl methacrylate (40 mL, 38 mmol), phenothiazine (0.1 g), and tetraisopropyl titanate (1 mL). When the head temperature rose to 99° C. (pot 112° C.), the reaction mixture was cooled. The material was filtered through activity grade I alumina (30 g, Woelm), and the column was rinsed with ethyl acetate. The combined filtrates were concentrated on a rotary evaporator, finally down to 0.5 mm, to give 32.4 g of light-yellow cis,cis-9,12-octadecadienyl methacrylate. Analysis by HPLC (dichloromethane:ethyl acetate:isopropyl alcohol, 90:10:1, silica gel column) showed that no unreacted octadecadienol was present. 90 MHz 1H NMR: δ 6.03 (1H, broad s, methacrylate vinyl), 5.47 (1H, m, methacrylate vinyl), 5.30 (4H, m, vinyl), 4.09 (2H, t, J=7, OCH2), 2.75 (2H, broad t, J~6, doubly allylic CH2), 2.2-1.1 (27H, m), and 0.89 (3H, t, J~6, --CH2CH3). The NMR spectrum indicated the presence of about 10 mole % methyl methacrylate.

Workup

  1. customrose to 99° C.
  2. custom(pot 112° C.)
  3. temperaturethe reaction mixture was cooled
  4. filtrationThe material was filtered through activity grade I alumina (30 g, Woelm)
  5. washthe column was rinsed with ethyl acetate
  6. concentrationThe combined filtrates were concentrated on a rotary evaporator, finally down to 0.5 mm

Sources & evidence

ORD record
ord-4e6d58e6f9524c9db10f92a1fb137ce3
Source dataset
uspto-grants-1981_10
Patent number
US04293674

Reaction notes

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