Methanol → HCID 86619079, compound

HRID 2245751Notes

Reaction equation

HRID 2245751 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.C1CCC(N=C=NC2CCCCC2)CC1>CC(OC)(C)C.CN(C1C=CN=CC=1)C>[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 643570methyl (2S)-2-hydroxy-2-phenylacetateHCID 10422241462-66-8

Product 1

HCID 86619079HCID 86619079, compoundYield 99.4%

Reagents, catalysts & solvents 2

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

Conditions

Temperature
35 °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 MTBE were added at r.t. 8.4 g (50 mmol) (S)-(+)-mandelic acid methyl ester [α]D=+144.9 (c=1.04, MeOH) and 1.5 g DMAP. After stirring for 15 min, 10.5 g (51 mmol) DCC is added, during which the temperature raised to 35° C. The reaction mixture was stirred for 4 h at 35° C., cooled to room temperature and filtered. The resulting solution was concentrated in vacuo to a volume of ca. 50 ml and filtered over 100 g of silicagel. The product was eluted with ca. 600 ml 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 19.8 g (98%) of (E,E)-4,8,12-Trimethyl-trideca-3,7,11-trienoic acid (S)-methoxycarbonyl-phenyl-methyl ester (2) in form of a colorless oil.

Workup

  1. stirringThe reaction mixture was stirred for 4 h at 35° C.
  2. temperaturecooled to room temperature
  3. filtrationfiltered
  4. concentrationThe resulting solution was concentrated in vacuo to a volume of ca. 50 ml
  5. filtrationfiltered over 100 g of silicagel
  6. washThe product was eluted with ca. 600 ml 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-fbe77c50787d4e76a9a70acf14177e2b
Source dataset
uspto-grants-2010_03
Patent number
US07683190B2

Reaction notes

Loading…