Diethyl-geranyl

Geraniol/Nerol N,N-Diethyl-o-geranyl (neryl)-hydroxylamine University of New Castle... 

Some examples of naturally occurring esters and amides are shown here. Isoamyl acetate gives ripe bananas their characteristic odor, and geranyl acetate is found in the oil of roses, geraniums, and many other flowers. N,N-Diethyl- i / -toluamide (DEBT ) is one of the best insect repellents known, and penicillin G is one of the antibiotics that revolutionized modem medicine. 

Ambergris Ambrettolide Asafetida (Ferula foetida) extract Balsam copaiba (Copaifera officinalis) Balsam Peru (Myroxylon pereirae) Benzyl cinnamate Benzylsalicylate L-Borneol 6-t-Butyl-m-cresol C12-15 alkyl benzoate Cinnamyl acetate Cinnamyl alcohol Civet Dibutyl phthalate Diethyl phthalate Dimethyl isophthalate 1,4-Dioxacyclohexadecane-5,16-dione Ethylene glycol diacetate Geranyl phenylacetate Hexyl benzoate... 

Heptanal diethyl acetal 211-708-6 Blemmer EMMA 2-Ethyl hexyl methacrylate Mhoromer BM 713 211-711-2 Geranyl acetone f 211-712-8 Methyl sorbate 211-734-8... 

Figure 8 Thin-layer chromatography of prenylquinones and prenols. Adsorption chromatography on (A) silica gel plates, solvent light petroleum-diethyl ether (9 1), and (B) on silica gel plates impregnated with AgN03, solvent light petroleum-chloroform-acetone (50 10 17) Ki, phylloquinone, vitamin Ki MKa, menaquinone-4 PQ-9, plastoquinone-9 Q-9 and Q-10, ubiquinone-9 and -10 a-T, a-tocopherol a-Ts, a-tocotrienol 3-C, P-carotene GG, geranyl-geraniol (Source From Ref. 18, with permission of the copyright owner).

Prins reaction of P-pinene with formaldehyde gives the alcohol nopol (39) and its acetate [35836-72-7] (40) is used as a fragrance ingredient. Base-catalyzed addition of dieth-ylamine to myrcene gives geranyl diethyl amine (41), which is converted to menthol (42) as described below. 

The synthesis starts with myrcene (32), which can be obtained from 3-pinene as described above. Addition of the diethylamide anion gives geranyl diethyl amine (41). Isomerization using ruthenium (S)-BINAP gives the A,A-diethylenamine of enantiomeric excess (ee) of >96% and the catalyst turn over number is 400,000, which makes the process very efficient. The remainder of the synthesis follows that of the standard synthesis of /-menthol from citronellal. The zinc-catalyzed ene reaction converts /-citronellal to /-isopulegol [89-79-2] (172) and this is hydrogenated to /-menthol (42). More detail on this chemistry is given below. 

Geranyl diethyl phosphate allowed to react 0.5 hr. with 4 equivalents tert-h xXy -thio)dimethylaluminum prepared in situ by treatment of t rt-butanethiol at 0° with trimethylaluminum in hexane -> product. Y 97%. F. e. and reactions s. Y. Kitagawa et al., Am. Soc. 98, 5030 (1976). 

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