Цитронелал

Химические свойства

(?)-Citronellal occurs in Java citronella oil at a concentration of 35%. Racemic citronellal is the main constituent of E. citriodora oil with a content of up to 85%.
Pure citronellal is a colorless liquid with a refreshing odor, reminiscent of lemon balm. Upon catalytic hydrogenation, citronellal yields dihydrocitronellal, citronellol, or dihydrocitronellol, depending on the reaction conditions. Protection of the aldehyde group, followed by addition of water to the double bond in the presence of mineral acids or ion-exchange resins results in the formation of 3,7-dimethyl-7-hydroxy-octan-l-al (hydroxydihydrocitronellal). Acid-catalyzed cyclization to isopulegol is an important step in the synthesis of (?)-menthol.

Вхождение

The d-form of citronellal has been reported in the oil of citronella (Ceylon, Jammus, Kaschmis), in the oil from leaves of Barosma pulchella, in the oil from roots of Phebalium nudum and in the oils of Eucalyptus citriodora, Leptospermum citratum and Baeckea citriodora. The /-form is present in the oils of Backhousia citriodora var. A, E. citriodora, Litsea cubeba (fruits) and lemongrass. Citronellal is generally present also in the oils of lemon, mandarin, Lavandula delphinensis, Ocimum canum f. citrata and many others (Fenarolis Handbook of Flavor Ingredients, 1971).

Использование

rac-Citronellal is a monoterpenoid and the major isolate in citronella oil. Citronella oil is an essential oil bearing insecticidal properties. rac-Citronellal is also often used as a fragrance ingred ient.

Подготовка

Citronellal is still isolated from essential oils in considerable quantities; it is also produced synthetically.
1) Isolation from essential oils:(+)-Citronellal is obtained from citronella oils by fractional distillation. Racemic citronellal is isolated from E. citriodora oil; when necessary, it is purified by using an addition compound, for example, the bisulfite derivative.
2) Synthesis from geraniol or nerol: Racemic citronellal can be obtained by vaporphase rearrangement of geraniol or nerol in the presence of, for example, a barium-containing copper–chromium oxide catalyst.
3) Synthesis from citronellol: Racemic citronellal can also be obtained by dehydrogenation of citronellol under reduced pressure with a copper chromite catalyst.
4) Synthesis from citral: Selective hydrogenation of citral to citronellal can be accomplished in the presence of a palladium catalyst in an alkaline alcoholic reaction medium. A continuously operating process for the hydrogenation on a palladium catalyst in the presence of trimethylamine has been developed.
5) Synthesis from myrcene: (+)- and (?)-Citronellal are available from myrcene via geranyldiethylamine, which is enantioselectively isomerized to (+)- or (?)-citronellalenamine. Hydrolysis yields pure (+)- or (?)-citronellal; see monograph menthol.

Определение

ChEBI: A monoterpenoid, the main component of citronella oil which gives it its distinctive lemon aroma.

Cостав эфирных масел

Citronella oil contains a number of fragrant fractions of which citronellal, geraniol and citronellol are the major components. Ceylon citronella oil contains 55 to 65% total acetylizable alcohols (calculated as citronellol) and 7 to 15% total aldehyde (calculated as citronellal). The main constituents are geraniol (18 to 20%), citronellol (6.4 to 8.4%), citronellal (5 to 15%), geranyl acetate (2%); limonene (9 to 11%) and methyl isoeugenol (7.2 to 11.3%). Other constituents are camphene, caryophyllene, linalool, citral (neral and geranial), methylheapenone, methyleugenol, l-borneol, nerol, eugenol and farnesol.* Java citronella oil contains not less than 35% alcohols (calculated as citronellol) and not less than 35% aldehydes (calculated as citronellal). The Java type appears to have higher concentrations of citronellol (35%) and geraniol (21%) than does the Ceylon type (citronellol 10% and geraniol 18%).

Общее описание

(±)-Citronellal was studied for its fumigant antifungal activity against Pyricularia (Magnaporthe) grisea.

Метаболизм

Feeding 50 g citronellal to rabbits was followed by the isolation of 13 g of a crystalline glucuronide, which proved to be p-menthane-3.8-diol-D-glucuronide. The citronellal appeared to have been cyclized and the glucuronide obtained was identical with that obtained on feeding p-menthane-3,8-diol (menthoglycol) (Kühn & Low, 1938). However, evidence was produced to show that the cyclization was not, strictly speaking, a biological reaction, but a chemical one which took place in the stomach under the influence of the gastric hydrochloric acid. The conjugation of the menthoglycol with glucuronic acid was, of course, a purely biological reaction. It was found that on shaking 20 g citronellal with 200 ml 0-5% HCl for 48 hr at 37 C, 12 g menthoglycol was formed (Kühn & Low, 1938).