This invention provides efficient and scalable enantioselective methods that yield 2-alkyl-2-allylcycloalkyanone compounds with quaternary stereogenic centers. Methods include the method for the preparation of a compound of formula (I):

##STR00001##

comprising treating a compound of formula (II) or (III):

##STR00002##

with a palladium (II) catalyst under alkylation conditions.

This invention provides efficient and scalable enantioselective methods that yield 2-alkyl-2-allylcycloalkyanone compounds with quaternary stereogenic centers. Methods include the method for the preparation of a compound of formula (I): ##STR00001##
comprising treating a compound of formula (II) or (III): ##STR00002##
with a palladium (II) catalyst under alkylation conditions.

This invention provides efficient and scalable enantioselective methods that yield 2-alkyl-2-allylcycloalkyanone compounds with quaternary stereogenic centers. Methods include the method for the preparation of a compound of formula (I): ##STR00001##
comprising treating a compound of formula (II) or (III): ##STR00002##
with a palladium (II) catalyst under alkylation conditions.

The present invention relates to novel compounds of general formulae (la), (lb) and (Ic) and to the stereoisomers thereof. The compounds are useful as a fragrance or as flavor as they have a sandalwood like scent. The invention also relates to a method for imparting or modifying a scent or a flavor to a composition by including said compounds into such composition, to a fragrance containing composition and/or a fragrance material containing said compound and to a process for preparing these compounds. X is C(R.sup.4)OH or CO; R.sup.1 is selected from the group consisting of hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl and C.sub.3-C.sub.4-cycloalkyl, R.sup.2 is selected from the group consisting of hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl and C.sub.3-C.sub.4-cycloalkyl, R.sup.3 is C.sub.1-C.sub.4-alkyl, R.sup.3a is selected from the group consisting of hydrogen and C.sub.1-C.sub.4-alkyl, R.sup.3b is hydrogen or together with R.sup.3a is CH.sub.2; R.sup.4 is selected from the group consisting of hydrogen and C.sub.1-C.sub.4-alkyl.

##STR00001##

The present invention relates to novel compounds of general formulae (la), (lb) and (Ic) and to the stereoisomers thereof. The compounds are useful as a fragrance or as flavor as they have a sandalwood like scent. The invention also relates to a method for imparting or modifying a scent or a flavor to a composition by including said compounds into such composition, to a fragrance containing composition and/or a fragrance material containing said compound and to a process for preparing these compounds. X is C(R.sup.4)OH or CO; R.sup.1 is selected from the group consisting of hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl and C.sub.3-C.sub.4-cycloalkyl, R.sup.2 is selected from the group consisting of hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl and C.sub.3-C.sub.4-cycloalkyl, R.sup.3 is C.sub.1-C.sub.4-alkyl, R.sup.3a is selected from the group consisting of hydrogen and C.sub.1-C.sub.4-alkyl, R.sup.3b is hydrogen or together with R.sup.3a is CH.sub.2; R.sup.4 is selected from the group consisting of hydrogen and C.sub.1-C.sub.4-alkyl.

##STR00001##

Control and repellency of biting flies, house flies, ticks, ants, fleas, biting midges, cockroaches, spiders and stink bugs is obtained by contact of the insects with at least one of the compounds of the structure (I)

##STR00001##

wherein
R is OH, O, OC(O)R.sub.4, OR.sub.6, or (OR.sub.6).sub.2, wherein each R.sub.6 is independently an alkyl group containing from 1 to 4 carbon atoms and R.sub.4 is a branched or straight chain, saturated or unsaturated, hydrocarbyl group with zero to two double bonds and from 1 to 15 carbon atoms;
X is O or CH.sub.2, with the proviso that when X is O R can only be O:
each Z is independently (CH) or (CH.sub.2);
y is a numeral selected from 1 and 2;
R.sub.1 is H or a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to two double bonds and from 1 to 15 carbon atoms;
R.sub.2 is H and a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms;
R.sub.3 is H, a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms, (CH.sub.2).sub.nOH, C(O)OR.sub.5, CH.sub.2C(O)OR.sub.7, CH.sub.2C(O)R.sub.8, C(O)NR.sub.9R.sub.10,
or CH.sub.2C(O)NR.sub.11R.sub.12 where each of R.sub.5, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11 and R.sub.12 is independently H or a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms, and n is n integer of from 1 to 12;
the bond between the 2 and 3 positions in the ring structure may be a single or a double bond; and
wherein the compounds of structure (I) contain from 11 to 20 carbon atoms except where R is O, XCH.sub.2 and y is 1 the compounds of structure (I) contain from 13 to 20 carbon atoms, with the proviso that when R.sub.3 is CH.sub.2C(O)OR.sub.7 R.sub.1 and R.sub.2 must be H or a saturated hydrocarbyl group with zero double bonds. The invention also includes optical isomers, diastereomers and enantiomers of the compounds of structure (I).

Control and repellency of biting flies, house flies, ticks, ants, fleas, biting midges, cockroaches, spiders and stink bugs is obtained by contact of the insects with at least one of the compounds of the structure (I)

##STR00001##

wherein
R is OH, O, OC(O)R.sub.4, OR.sub.6, or (OR.sub.6).sub.2, wherein each R.sub.6 is independently an alkyl group containing from 1 to 4 carbon atoms and R.sub.4 is a branched or straight chain, saturated or unsaturated, hydrocarbyl group with zero to two double bonds and from 1 to 15 carbon atoms;
X is O or CH.sub.2, with the proviso that when X is O R can only be O:
each Z is independently (CH) or (CH.sub.2);
y is a numeral selected from 1 and 2;
R.sub.1 is H or a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to two double bonds and from 1 to 15 carbon atoms;
R.sub.2 is H and a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms;
R.sub.3 is H, a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms, (CH.sub.2).sub.nOH, C(O)OR.sub.5, CH.sub.2C(O)OR.sub.7, CH.sub.2C(O)R.sub.8, C(O)NR.sub.9R.sub.10,
or CH.sub.2C(O)NR.sub.11R.sub.12 where each of R.sub.5, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11 and R.sub.12 is independently H or a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms, and n is n integer of from 1 to 12;
the bond between the 2 and 3 positions in the ring structure may be a single or a double bond; and
wherein the compounds of structure (I) contain from 11 to 20 carbon atoms except where R is O, XCH.sub.2 and y is 1 the compounds of structure (I) contain from 13 to 20 carbon atoms, with the proviso that when R.sub.3 is CH.sub.2C(O)OR.sub.7 R.sub.1 and R.sub.2 must be H or a saturated hydrocarbyl group with zero double bonds. The invention also includes optical isomers, diastereomers and enantiomers of the compounds of structure (I).

Cyclohexenone and cyclohexenol compounds are provided having specific fragrances and remanence properties, along with methods for synthesizing these compounds, including obtaining the compound by condensing a ketone on an ?-methylene-aldehyde in order to obtain, by means of a domino reaction, compounds of formula (II) as follows: ##STR00001##

Cyclohexenone and cyclohexenol compounds are provided having specific fragrances and remanence properties, along with methods for synthesizing these compounds, including obtaining the compound by condensing a ketone on an ?-methylene-aldehyde in order to obtain, by means of a domino reaction, compounds of formula (II) as follows: ##STR00001##

Control and repellency of biting flies, house flies, ticks, ants, fleas, biting midges, cockroaches, spiders and stink bugs is obtained by contact of the insects with at least one of the compounds of the structure (I). ##STR00001##