Cinnamyl acetate

Unusual cyclocarbonylation of allylic acetates proceeds in the presence of acetic anhydride and an amine to afford acetates of phenol derivatives. The cinnamyl acetate derivative 408 undergoes carbonylation and Friedel-Crafts-type cyclization to form the a-naphthyl acetate 410 under severe condi-tions[263,264]. The reaction proceeds at 140-170 under 50-70 atm of CO in the presence of acetic anhydride and Et N. Addition of acetic anhydride is essential for the cyclization. The key step seems to be the Friedel-Crafts-type cyclization of an acylpalladium complex as shown by 409. When MeOH is added instead of acetic anhydride, /3,7-unsaturated esters such as 388 are... 

Health and Safety. Cinnamyl alcohol has been evaluated by FEMA and given GRAS status (FEMA No. 2294). Two of its esters, cinnamyl cinnamate (FEMA No. 2298) and cinnamyl acetate (FEMA No. 2293), ate also used extensively in flavor and fragrance compositions. Cinnamyl alcohol has also been tested by RIFM (48) and found to be safe for use. There have been reported cases of irritation and several manufacturers market a desensitized alcohol for use in fragrance appHcations. 

Uses. Cinnamyl alcohol and its esters, especially cinnamyl acetate, are widely employed in perfumery because of their excellent sensory and fixative properties. They are frequently used in blossom compositions such as lilac, jasmine, lily of the valley, hyacinth, and gardenia to impart balsamic and oriental notes to the fragrance. In addition, they ate utilized as modifiers in berry, nut, and spice flavor systems. The value of cinnamyl alcohol has also been mentioned in a variety of appHcations which include the production of photosensitive polymers (49), the creation of inks for multicolor printing (50), the formulation of animal repellent compositions (51), and the development of effective insect attractants (52). 

The monoanions of primary nitroalkanes, phenylnitromethane, and a-nitro esters are all preferentially C-alkylated by cinnamyl acetate and 2-butenyl acetate in 50-89% yield in the presence of Pd catalyst (Eq. 5.51).75 The a-nitro ester gives the C-alkylate in 89% yield, but 2-nitropropane gives the C-alkylate in only 29% yield. The main product is cinnamaldehyde, which is derived from 0-alkylation.75a... 

The first enantioselective, iridium-catalyzed allylic substitution was reported by Helmchen and coworkers soon after the initial report by Takeuchi. Helmchen studied catalysts generated from phosphinooxazoline (PHOX) ligands and [Ir(COD)Cl]2 for the reactions of sodium dimethylmalonate with cinnamyl acetates (Scheme 2) [50]. The alkylation products were isolated in nearly quantitative yield and were formed with ratios of branched-to-Unear products up to 99 1 and with enantioselectivities up to 95% ee. In this and subsequent studies with PHOX ligands [51,52], Helmchen et al. demonstrated that the highest yields and selectivities were obtained with a PHOX ligand containing electron-withdrawing substituents and... 

This tethered ferrocenyl-based Pd complex on MCM-41 (17) was then used for the catalytic amination reaction between cinnamyl acetate and benzylamine (40 °C, THF) [59]. In this case, confinement of the catalyst results in profound changes in regio- and enantioselectivity. When the homogeneous equivalent is used to catalyze the reaction, the straight chained derivative is the sole product. Similar results (only 2% of the branched product) were obtained when the catalyst was tethered to the surface of the non-porous silica Cabosil. When tethered inside the pores of MCM-41 a major change occurred in that now the branched product accounts for about 50% and a change in e.e. from 49% e.e. when anchored to the Cabosil support to +99% when anchored inside the MCM-41 pore could be observed. If the catalyst s chirality was reversed in the MCM-41 immobihzed case, so was the chirality of the product (measured at 93% e.e.) [60]. 

Cinnamaldehyde diacetate was reduced by heating at 100° with iron in 50% acetic acid to cinnamyl acetate in 60.7% yield [800]. 

Mixed ( )-cinnamyl acetals 460 undergo the enantioselective carbolithiation readily in the presence of stoichiometric or catalytic amounts, as low as 1 mol%, of (—)-sparteine (11) (equation 126) °. When quenching the reaction mixture of 461, 462 below —50°C with MeOH/HCl, the alcohols 463 are obtained with good yields and excellent ee values. However, upon warming to 20 °C, a 1,3-cycloelimination from conformation 462 gives rise to the formation of optically active trani-cyclopropanes 464 °. 

Fio. 37. Van t Hoff plots for various compounds. Eluites (1) cinnamyl aldehyde, (2) es-tragole, (3) cinnamyl alcohol, (4) cinnamyl acetate. (5) methyleugenol, and (6) s role. The data were obtained on pyrocarbon, 400 x 2.17 mm i.d., with acetonitrile as mobile phase. Reprinted with permission from Colin ei al. (142). 

Chlorophyll, 295 Chlorotil s, 135, 140 m-Chlorotoluene, 182,183 Chloitoluron, 292 Chlorzoxoneacetaminophen, 264 4 -Cholettenone, 74 Cholestanyl silica, 158 Cholesterol, 283, 295 Cholinesterase, 293 Chromatographic enzyme reactor, 291 Chrysene, 69, 105, 107 Cinnamic acid, 293 Cinnamyl acetate, 198 Cinnamyl alcohol, 198 Cinnamyl aldehyde, 198 dausius-Mosotti fimction, 208 Qindamycin, 297 Clonazqmm, 195 Clusters of hetaeron, 250 Coating of polar adsoibent by polar solvent, 86... 

Allylic arylations of substituted cinnamyl acetates can be carried out with Ar3Bi under Pd catalysis. The couplings afforded 1,3-diarylpropenes in good yields in short reaction times (Scheme 52) [66],... 

Cinnamomum aromaticum Nees. C. cassia Presl. Gui Zhi (Cinnamon) (twig, bark) Cinnamic aldehyde, cinnamyl acetate, cinnamic acid, eugenol, phellandrene, phenylpropyl alcohol, coumarin, cinnamic aldehyde, orthomethylcoumaric aldehyde.33-49-254-435-510 Antibacterial, vasodilatation, aromatic stomachic, astringent, tonic, analgesic, stimulate human lymphocytes to proliferate. 

Flowery Anisyl alcohol Benzyl acetate, phenylaceiate Cinnamic acid Cinnamyl acetate Citronellyl formate Crcsyl acetate Decanal Dimethyl benzyl carbinol Dimethyl benzyl carbinyl acetate Ethyl anthranilate Geranyl acetate Hydroxycitronellal dimethyl acetate Linalool Linalyl acetate Methyl benzoate Pcnethyl acetate 2-Phcnylpropionaldehyde 3-Phenylpropionaldehvde. 

Pineapple Allyl capruale, cyclohexylacetaie. cyclohexylbutyrate, cyclohexylptopionate. 2-nonylenate, phenoxyacetate Benzyl formate Bomyl acetate n-Bulyl acetate Butyl isobutyrate Cinnamyl acetate Decanal dimethyl acetal Ethyl butyrate, hexadienoate. phenoxyacetate Hexyl butyrate 2-Methylallyl capruale Methyl heia-methy Ipropionaie Methyl undecylate Propyl isobutyrate. 

Cinnamaldehyde (75-90%), cinnamyl acetate, hydrocarbons Cedarwood or gurjun oil, mineral Oil, colophony, fatty oils may contain traces of Pb... 

An exciting development has come from work with an iridium catalyst. The use of the complex derived from phosphinoaryloxazoline ligand 149 leads to an efficient alkylation of E-cinnamyl acetate (Eq. 8E.32) [217], It is of note that electron-withdrawing substituents on the phosphorus atom, which are known to be required to give a good regioselectivity in general [218], also increased the enantioselectivity dramatically. 

Chiral disubstituted cyclopropanes have been formed by enantioselective carbolithia-tion of cinnamyl acetals.99... 

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