Zwitterion ligand metal complexes and methods of aerobic oxidation using a zwitterion ligand metal complex are provided. The zwitterion ligand metal complexes can include a transition metal salt and a zwitterion ligand, which can comprise a non-conjugated amide anion-phosphonium cation, an amide anion-ammonium cation, or an iminium cation. The methods of aerobic oxidation can include combining the zwitterion ligand metal complex with an oxidizable compound and molecular oxygen to allow the isolation of an oxidized compound from the oxidizable compound.

The present invention relates to a process for the preparation of enantiomerically and diastereomerically enriched cyclobutane amines and amides by reacting (a) cyclopropylcarbonitrile to a cyclopropylcarbaldehyde, (b) further reacting to a cyclobutanone, or (d) further reacting to an enamide, 5 (c) further reacting to enantiomerically and diastereomerically enriched cyclobutane amines, or (d) further reacting to an enamide and (e) to an enantiomerically and diastereomerically enriched cyclobutylamide to obtain (f) an enantiomerically and diastereomerically enriched cyclobutane amine, and (g) further reacting to an enantiomerically and diastereomerically enriched cyclobutane amide.

The invention provides efficient cyclization processes of hydroxyalkenoic acids and products produced therefrom. The following reactions are claimed: Formula (I), (II), (V) and (VI). ##STR00001##

The invention provides efficient cyclization processes of hydroxyalkenoic acids and products produced therefrom. The following reactions are claimed: Formula (I), (II), (V) and (VI). ##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).

A process for purifying a crude composition includes a monoterpene compound selected from the group consisting of monocyclic monoterpene alcohols, monocyclic monoterpene ketones, bicyclic epoxy monoterpenes and mixtures of two or more of the aforementioned compounds, such as preferably a monocyclic monoterpene alcohol. The process comprises performing a layer crystallization with a melt of the crude composition, and the melt of the crude composition subjected to the layer crystallization includes oxygen-containing solvent in a concentration of 20 ppm to 2% by weight. The oxygen-containing solvent is selected from the group consisting of water, C1-6-alcohols, C1-6-carboxylic acids, C1-6-ketones, C1-6-aldehydes, C1-12-ethers, C1-12-esters and mixtures of two or more of the aforementioned solvents.

A process for purifying a crude composition includes a monoterpene compound selected from the group consisting of monocyclic monoterpene alcohols, monocyclic monoterpene ketones, bicyclic epoxy monoterpenes and mixtures of two or more of the aforementioned compounds, such as preferably a monocyclic monoterpene alcohol. The process comprises performing a layer crystallization with a melt of the crude composition, and the melt of the crude composition subjected to the layer crystallization includes oxygen-containing solvent in a concentration of 20 ppm to 2% by weight. The oxygen-containing solvent is selected from the group consisting of water, C1-6-alcohols, C1-6-carboxylic acids, C1-6-ketones, C1-6-aldehydes, C1-12-ethers, C1-12-esters and mixtures of two or more of the aforementioned solvents.

A process for purifying a crude composition includes a monoterpene compound selected from the group consisting of monocyclic monoterpene alcohols, monocyclic monoterpene ketones, bicyclic epoxy monoterpenes and mixtures of two or more of the aforementioned compounds, such as preferably a monocyclic monoterpene alcohol. The process comprises performing a layer crystallization with a melt of the crude composition, and the melt of the crude composition subjected to the layer crystallization includes oxygen-containing solvent in a concentration of 20 ppm to 2% by weight. The oxygen-containing solvent is selected from the group consisting of water, C1-6-alcohols, C1-6-carboxylic acids, C1-6-ketones, C1-6-aidehydes, C1-12-ethers, C1-12-esters and mixtures of two or more of the aforementioned solvents.

A process for purifying a crude composition includes a monoterpene compound selected from the group consisting of monocyclic monoterpene alcohols, monocyclic monoterpene ketones, bicyclic epoxy monoterpenes and mixtures of two or more of the aforementioned compounds, such as preferably a monocyclic monoterpene alcohol. The process comprises performing a layer crystallization with a melt of the crude composition, and the melt of the crude composition subjected to the layer crystallization includes oxygen-containing solvent in a concentration of 20 ppm to 2% by weight. The oxygen-containing solvent is selected from the group consisting of water, C1-6-alcohols, C1-6-carboxylic acids, C1-6-ketones, C1-6-aidehydes, C1-12-ethers, C1-12-esters and mixtures of two or more of the aforementioned solvents.