Abstract: Methods for preparing self-aldol condensation products of prenyl aldehyde (3-methyl-2-butenal) by use of an amine catalyst under weakly acidic conditions at temperatures of 10° C. or higher are disclosed. Methods are disclosed for the selective formation of ?-1,2-adducts and ?-1,2-adducts of prenyl aldehyde, and for the formation of specialty compositions useful in the flavor and fragrance industries.

Abstract: Methods for preparing self-aldol condensation products of prenyl aldehyde (3-methyl-2-butenal) by use of an amine catalyst under weakly acidic conditions at temperatures of 10° C. or higher are disclosed. Methods are disclosed for the selective formation of ?-1,2-adducts and ?-1,2-adducts of prenyl aldehyde, and for the formation of specialty compositions useful in the flavor and fragrance industries.

Abstract: Methods for preparing ester derivatives of 3-methyl-2-buten-1-ol (prenyl alcohol) from 2-methyl-1,3-butadiene (isoprene) and alkanoic acids in the presence of an inorganic acid catalyst are disclosed. The resultant prenyl ester (e.g., prenyl acetate) can be converted to prenyl alcohol by reaction with water in the presence of either a suitable enzyme or a base.

Abstract: A method for preparation of a dicarbonyl compound of the following formula ##STR1## by reacting a conjugated alkadiene compound of the formula ##STR2## with a 1,3-dicarbonyl compound of the formula ##STR3## in the presence of an acid catalyst. The products of the method are useful in the preparation of compounds such as vitamins A and E, various carotenoids, Retin A, dehydrolinalool, pseudoionone, citral, and linalool.

Abstract: The present invention describes novel phosphonate reagent compositions of the formula: ##STR1## wherein R and R'=C.sub.1 -C.sub.4 alkyl groups, or R, R'=(CH.sub.2).sub.n (n=2 or 3) or [CH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 ].The invention also describes allylic C-15 phosphonate compounds of the formula: ##STR2## wherein R and R'=C.sub.1 -C.sub.4 alkyl groups. The invention also describes methods of preparing phosphonate reagent compositions (4), allylic phosphonate compounds (5), and lycopene.

Abstract: The present invention describes novel C-15 allenic phosphonate reagent compositions of the formula: ##STR1## The invention also describes novel C-15 allylic phosphonate reagent compositions of the formula: ##STR2## The invention also describes methods of preparing canthaxanthin, the phosphonate reagent compositions, and a tertiary propargylic alcohol of the formula: ##STR3##

Abstract: Methods for preparing 3-methyl-2-buten-1-ol (prenyl alcohol) from 2-methyl-1,3-butadiene (isoprene) and carboxylic acids are disclosed. Carboxylic acids which can be used in the process have a K.sub.a (relative to water) greater than 10.sup.-4 ; dichloroacetic acid is especially preferred. The process involves the slow (e.g., dropwise) addition of isoprene to the carboxylic acid to form a prenyl ester. The ester-formation reaction proceeds at room temperature in most cases; use of an organic base catalyst, preferably a sodium or potassium salt of the reactant carboxylic acid, improves the yield. The resultant prenyl ester can be converted to prenyl alcohol by reaction with a base. Prenyl alcohol can be readily converted to citral, a chemical intermediate in the synthesis of vitamins A and E, and several widely-used carotenoids.

Abstract: Allenic phosphonate reagent compositions are described which have the formula: ##STR1## wherein R and R'=C.sub.1 -C.sub.4 alkyl groups, or R, R'=(CH.sub.2).sub.n (n=2 or 3) or ?CH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 !.Also described are methods for forming such allenic phosphonates from ethynyl-.beta.-ionol, and for converting these allenic compounds to allylic phosphonate compounds which can be used in the synthesis of a variety of biologically-active materials.

Abstract: A procedure for forming methylmalonaldehyde from propionaldehyde, an alkyl formate and a sodium alkoxide, utilizing a crossed-Claisen condensation is disclosed. The procedure avoids the formation of aldol condensation products. Also disclosed are processes for preparing 3-alkoxy-2-methylpropenals such as 2-methyl-3-(2-methyl-2-propenoxy)propenal from methylmalonaldehyde. The latter products are useful in the synthesis of carotenoids.

Abstract: Processes for synthesizing tertiary alkynols by reacting carbonyl-group-containing compounds with alkynes in the presence of a basic catalyst are disclosed. Preferred products are 6,10,14-trimethyl-4-pentadecyn-6-ol compounds having the structure: ##STR1## A preferred, novel compound, 6,10,14-trimethyl-4-pentadecyne-2,6-diol, can be used in the synthesis of Vitamin E or Vitamin K.sub.1.

Abstract: Processes for synthesizing tertiary alkynols by reacting carbonyl-group-containing compounds with alkynes in the presence of a basic catalyst are disclosed. Preferred products are 6,10,14-trimethyl-4-pentadecyn-6-ol compounds having the structure: ##STR1## A preferred, novel compound, 6,10,14-trimethyl-4-pentadecyne-2,6-diol, can be used in the synthesis of Vitamin E or Vitamin K.sub.1.

Abstract: Methods of forming unsaturated C-18 ketones which can be used in the synthesis of Vitamins E and K.sub.1 are disclosed. One procedure involves coupling a C-9 primary allylic halide to a carbonyl-group-containing C-9 terminal alkyne. A second, two-step procedure employs a C-4 bis allylic halide (molar excess) and a carbonyl-group-containing C-9 terminal alkyne to form a C-13 primary allylic halide. The C-13 primary allylic halide can then be converted to the desired C-18 ketone by reaction with 2-methyl-3-butyn-2-ol. Novel C-18 ketones (e.g., 14-hydroxy-6,14-dimethyl-10-methylene-5-pentadecen-7,12-diyn-2-one), C-13 allylic halides (e.g., 10-chloromethyl-6-methyl-5,10-undecadien-7-yn-2-one) and C-9 allylic halides (e.g., 6-chloromethyl-2-methyl-6-hepten-3-yn-2-ol) are formed in the process.

Abstract: This invention provides glyoxal derivatives and a method for making these derivatives. A particularly useful derivative, 1-chloro-1,2,2-trialkoxyethane, and a facile method for making these alpha-halo ethers are provided. The alpha-halo ethers are valuable intermediates in the manufacture of a variety of commercial compounds.

Abstract: The present invention is an improved method to prepare 2,7-dimethyl-2,4,6-octatrienedial and related derivative compounds. This method of making 2,7-dimethyl-2,4,6-octatrienedial and derivatives thereof includes reacting 2-butenyl-bisphosphonic acid tetraalkyl ester and at least two equivalents of protected pyruvic aldehyde derivative in a nonpolar organic solvent in the presence of an alkali metal hydroxide. Compounds prepared by this invention are useful intermediates in the preparation of carotenoids.

Abstract: Processes for synthesizing novel phosphonate diester compounds of the general formula ##STR1## are disclosed and claimed. The claimed process includes forming a reaction mixture of a C-14 aldehyde and a methylene-bis-phosphonic acid ester, separating a pentadienyl phosphonic acid dialkyl ester intermediate from the reaction mixture, optionally isomerizing the intermediate in the presence of a basic catalyst, and isolating the desired pentadienylphosphonic acid dialkyl ester compound. The isolated phosphonate compounds made according to the processes of the present invention may be employed in synthesizing retinoids such as retinoic acid or carotenoids such as beta-carotene.

Abstract: Novel phosphonate compounds of the formula ##STR1## are disclosed and claimed, as well as methods for manufacturing the phosphonates from C-14 through C-16 aldehydes. The phosphonate compounds of the present invention can be employed to form 13-cis retinoic acid, retin-A and beta-carotene.

Abstract: Cyclopropanoid cyanoesters of the formula: ##STR1## where R' is --CH.sub.3 or --CH.sub.2 CH.sub.3, and A is (a) --H, or(b) A, B represents an aliphatic group joined to a carbon atom on the cyclopropanoid ring, thereby forming a spiro group, A, B being selected from structures having the formula:(i) --(CH.sub.2).sub.n --, wherein n=3, 4, or 5, and(ii) --(CH.sub.2).sub.2 --Y--(CH.sub.2).sub.2 --, wherein Y is NCH.sub.3, O, or S); and,when A is --H, B is selected from the group consisting of: ##STR2## are disclosed. These compositions are useful in the synthesis of pyrethroids. A process for synthesis of cyclopropanoid cyanoesters by reacting 2-nitropropane with cyanoesters of the general formula: ##STR3## is also disclosed and claimed.

Abstract: Monoesters of symmetrical dicarboxylic acids and symmetrical diols are prepared in high yield by reacting a diacid or a diol with a monohydric alcohol or monocarboxylic acid, respectively, in an aqueous solution. The resultant monoester is removed from the aqueous solution immediately after its formation by continuous extraction with a nonpolar solvent.

Abstract: E-4-acetoxy-2-methyl-2-butenal is prepared by: (1) preparation of an intermediate allylic halide from isoprene; and (2) reaction of the allylic halide with dimethyl sulfoxide in the presence of a non-nucleophilic base to form the desired product.

Abstract: The present invention is concerned with a method for preparing grandisol, the major component of the boll weevil sex pheromone. This method involves the conversion of 4-chloro-2-butanone to 5-chloro-3-methyl-1-penten-3-ol, acid-catalyzed isomerization of the latter compound to E- and Z-5-chloro-3-methyl-2-penten-1-ol, followed by conversion to ethyl 3-[2-chloroethyl]-3-methyl-4-pentenoate by treatment with triethyl orthoacetate, cyclization of ethyl 3-[2-chloroethyl]-3-methyl-4-pentenoate to ethyl Z- and E-2-vinyl-2-methylcyclobutanecarboxylate by reaction with base, conversion of ethyl Z- and E-2-vinyl-2-methylcyclobutanecarboxylate to Z- and E-2-[2-methyl-2-vinylcyclobutyl]-2-propanol by reaction with methyllithium, and the conversion of the latter compound to grandisol by reaction with diborane and basic hydrogen peroxide followed by dehydration.