Methanol → HCID 11646965, compound

HRID 2245750Notes

Reaction equation

HRID 2245750 reaction equation
[CH3:1]/[C:2](/[CH2:8][CH2:9]/[CH:10]=[C:11](\[CH3:18])/[CH2:12][CH2:13][CH:14]=[C:15]([CH3:17])[CH3:16])=[CH:3]\[CH2:4][C:5]([OH:7])=[O:6].[CH3:19][O:20][C:21](=[O:30])[C@@H:22]([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)O.CO.C1(N=C=NC2CCCCC2)CCCCC1>C(OC)(C)(C)C.CN(C)C1C=CN=CC=1>[CH3:19][O:20][C:21]([C@H:22]([O:6][C:5](=[O:7])[CH2:4]/[CH:3]=[C:2](\[CH3:1])/[CH2:8][CH2:9]/[CH:10]=[C:11](\[CH3:18])/[CH2:12][CH2:13][CH:14]=[C:15]([CH3:17])[CH3:16])[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)=[O:30]

Participants

7

Reactant 4

HCID 887MethanolHCID 10868DicyclohexylcarbodiimideHCID 2724623(R)-(-)-Methyl mandelateHCID 10422241462-66-8

Product 1

HCID 11646965HCID 11646965, compoundYield 97.9%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
28 °C

Procedure

To a solution of 12.5 g (50 mmol) (E,E)-4,8,12-trimethyl-trideca-3,7,11-trienoic acid (isomeric purity of 95%) [K. Ishihara et al., J. Am. Chem. Soc. 2002, 124, 3647-3655] in 100 ml methyl tert-butyl ether (MTBE) were added at r.t. 8.35 g (50 mmol) (R)-(−)-mandelic acid methyl ester, [α]D=−147.3 (c=1.0, MeOH), and 1.5 g 4-dimethylaminopyridine (DMAP). After stirring for 15 min at 28° C., 10.5 g (51 mmol) N,N′-dicyclohexylcarbodiimide (DCC) were added, during which the temperature raised to 35° C. The reaction mixture was stirred for 1.5 h at 38-40° C., cooled to r.t. and filtered. The resulting solution was concentrated in vacuo. The residue (23.1 g) was purified over 100 g silicagel, elution of the product with hexane/MTBE 1:1. Concentration of the combined fractions in vacuo and drying of the product in high vacuo (50° C./0.08 Torr) afforded 19.5 g (97%) of (E,E)-4,8,12-trimethyl-trideca-3,7,11-trienoic acid (R)-methoxycarbonyl-phenyl-methyl ester (1) in form of a colorless oil.

Workup

  1. temperatureraised to 35° C
  2. stirringThe reaction mixture was stirred for 1.5 h at 38-40° C.
  3. temperaturecooled to r.t.
  4. filtrationfiltered
  5. concentrationThe resulting solution was concentrated in vacuo
  6. customThe residue (23.1 g) was purified over 100 g silicagel, elution of the product with hexane/MTBE 1:1
  7. customConcentration of the combined fractions in vacuo and drying of the product in high vacuo (50° C./0.08 Torr)

Sources & evidence

ORD record
ord-4862d78613d9406f8f21eab24abda5a4
Source dataset
uspto-grants-2010_03
Patent number
US07683190B2

Reaction notes

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