Synthesis of civetone from palm oil products

Abstract

Metathesis of ethyl oleate, catalyzed by WCI6 and SnMe4, provided diethyl 9-octadecenedioate (the desired starting material for the synthesis of civetone) in 99% yield. Dieckmann condensation of diethyl 9-octadecenedioate gave 2-ethoxycarbonyl-9-cycloheptadecenone (63% yield), the hydrolysis-decarboxylation reaction of which yielded civetone (93%). Identification of all products was by 1H nuclear magnetic resonance, infrared and mass spectroscopic data. This is the first report of the synthesis of civetone from palm oil-derived products.KEY WORDS : Civet, civetone, diethyl 9-oetadecenedioate, 2~ethoxycarbonyl-9-cyeloheptadecenone, ethyl oleate, metathesis, palm oil.Civetone (9-cis-cycloheptadecenone), commonly known as

Transformação de triglicerídeos em combustíveis, materiais poliméricos e insumos químicos: algumas aplicações da catálise na oleoquímica

“…Por ex., a metátese do oleato de etila resulta na formação do 9-octadeceno-1,18-diato de dietila, conforme ilustrado na Figura 7, que é empregado como matéria-prima na obtenção de perfumes 79,80 . A partir de oleatos e linoleatos pode-se obter ésteres dicarboxílicos insaturados, que são matérias-primas para a síntese de poliésteres, poliamidas etc, constituindo um exemplo a metátese cruzada do oleato de metila com eteno, que leva à formação de 9-decenoato de metila.…”

Applications of Olefin Metathesis in the Oleochemistry

“…For instance, the diester obtained by metathesis of ethyl oleate has been subjected to a two-step reaction sequence, i.e. a Dieckmann condensation followed by hydrolysis-decarboxylation to give the unsaturated macrocyclic ketone 9-cycloheptadecen-I-one, whose cis form, civetone, is an attractive perfume component [4,5]; equation (2). Moreover, unsaturated dicarboxylic esters and acids are interesting starting materials for the manufacture of polyesters and polyamides [6].…”

Metathesis in Oleochemistry

“…For ins tan ce, the di es ter ob ta i ned by me tathe sis of ethyl ole a te has been sub jec ted to a two-step re ac ti on se quen ce, i.e. a Di eck mann con den sa ti on fol lo wed by hydroly sis-decarboxylation to give 9-cycloheptadecen-1-one, who se cis form, ci ve to ne , is an im por tant base ma te ri al in the per fu me in dustry 4,5 , re ac ti on (4). Mo re o ver, un sa tu ra ted di car boxy lic es ters and acids are in te res ting star ting ma te ri als for the ma nu fac tu re of pol yesters and pol ya mi des 6 .On the ot her hand, the pro duct oc tadec-9-ene can be di me ri zed and hydro ge na ted to 10,11-dioctyleicosane, a lu be-oil ran ge hydro car bon in terme di a te 7 .…”

“…On the ot her hand, two-component ca talyst systems, mainly WOCl 4 and WCl 6 with a su i ta ble co ca talyst (an alk ylating agent such as Me 4Sn), have been wi dely em plo yed on a la bo ra tory sca le. The se are che a per and ea si er to hand le than the alk yli de ne com ple xes.…”

“…The ac ti vity of Re 2 O 7 /Al 2 O 3 ca talysts can be ex pla i ned on the ba sis of the ac ti vity of the sur fa ce ReO 4 groups which have re ac ted with Le wis acid si tes and with the dif fe rent alu mi nium-bonded OH groups du ring the pre pa ra ti on of the catalyst 41 . The most ac ti ve si tes ari se from the re ac ti on bet ween ReO 4 -ions and the most aci dic OH groups on the alu mi na sur fa ce to form Al-bonded ReO 4 spe ci es. Such re ac ti ons are fa vou red only af ter the ba sic and ne u tral OH groups have reac ted to some ex tent.…”