Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 4, pp. 695−699.
Pleiades Publishing, Ltd., 2010.
Original Russian Text
D.A. Ponomarev, E.V. Vishnyakova, N.V. Rudometova, 2010, published in Zhurnal Prikladnoi Khimii, 2010, Vol. 83, No. 4, pp. 642−646.
AND INDUSTRIAL ORGANIC CHEMISTRY
Preparation of Fragrant Substances from Bornyl Chloride
D. A. Ponomarev, E. V. Vishnyakova, and N. V. Rudometova
St. Petersburg State Academy of Forestry Engineering, St. Petersburg, Russia
All-Russia Research Institute of Food Aromas, Acids, and Dyes, State Institution,
Russian Academy of Agricultural Sciences, St. Petersburg, Russia
Received June 24, 2009
Abstract—Organocuprate reagents were used for introducing bornane (1,7,7-trimethylbicyclo[2.2.1]heptane)
moiety into the carbon skeleton of α,β-unsaturated carbonyl compounds. Prospects for use of the products obtained
as fragrant substances were assessed.
Monoterpenes and their derivatives (alcohols,
aldehydes, esters), as a rule, have pleasant odor and are
components of various essential oils released by plants.
Individual terpene compounds are mainly used today
not as ﬁ nished products but as raw materials for organic
synthesis [1, 2]. Because of growing consumption of
fragrant substances by industrial enterprises producing
various household chemicals (synthetic detergents,
soaps, shampoos, etc.), it becomes necessary to set up
production of cheap synthetic fragrances.
One of raw materials for producing synthetic fragrant
substances is turpentine. Its main components are α-
and β-pinenes, 3-carene, and limonene . Because the
α-pinene content of Russian turpentines is about 70%,
the majority of fragrant substances are produced from
α-pinene and its isomerization products.
Long-term studies in the ﬁ eld of chemistry of
fragrant substances [4, 5], including those prepared from
monoterpenes, led to empirical elucidation of structural
elements responsible for the odor and of the inﬂ uence
exerted on the odor strength and character by their
mutual position in molecules of fragrant substances. It
could be expected that carbonyl compounds containing
the bornane (1,7,7-trimethylbicyclo[2.2.1]heptane)
moiety would have a pleasant odor.
To examine the possibility of synthetic use of
halogenated monoterpenes, we performed syntheses
of fragrant substances from bornyl chloride. The
synthetic route was chosen so as to meet the following
requirements : the products should contain a carbonyl
group; the monoterpene substituent should be located no
closer than the β-position relative to the carbonyl group.
The synthesis procedure that we suggest is based on
preparation of an intermediate organolithium compound
from bornyl chloride, its conversion into a lithium
dialkylcuprate complex, and reaction of the latter with
α,β-unsaturated carbonyl compounds. Addition of
organocopper compounds to α,β-unsaturated carbonyl
compounds is regiospeciﬁ c, which allows introduction
of the alkyl substituent into the β-position relative to the
carbonyl group [7, 8].
Despite wide use of cuprate reagents in modern
organic synthesis [9–11], their preparation from
cycloalkyl and bicycloalkyl chlorides has not been
described in the literature. We were able to prepare
and use in conjugated addition lithium dialkylcuprate
reagents derived from bornyllithium. Bornyllithium
was prepared following the procedure described in 
As substrates for addition we used the following