USOO6239324B1 (12) United States Patent (10) Patent No.: US 6,239,324 B1 Fujiwhara et al. (45) Date of Patent: May 29, 2001

(54) DIENE COMPOUND AND PROCESS FOR * cited by examiner PRODUCING THE SAME Primary Examiner Johann Richter (75) Inventors: Mitsuhiko Fujiwhara; Takenobu ASSistant Examiner Brian J. Davis Nishikawa; Yoji Hori; Toshimitsu (74) Attorney, Agent, or Firm-Sughrue, Mion, Zinn, Hagiwara; Hisao Iwai; Takashi Macpeak & Seas, PLLC Miura, all of Kanagawa (JP) (57) ABSTRACT The invention provides a chain diene compound with desir (73) Assignee: Takasago International Corporation, able regioSelectivity, in the presence of a specific ruthenium Tokyo (JP) compound. This chain diene compound is a promising raw (*) Notice: Subject to any disclaimer, the term of this material for terpene. It has a Structure represented by the patent is extended or adjusted under 35 general formula (IX): U.S.C. 154(b) by 0 days. (IX) (21) Appl. No.: 09/383,920 R1 (22) Filed: Aug. 26, 1999 N-N-N- (30) Foreign Application Priority Data Aug. 26, 1998 (JP) ...... 10-240413 wherein R' represents H, a C-C alkyl group which may be Substituted or a C-C alkenyl group which may be Nov. 12, 1998 (JP). ... 10-321700 Feb. 3, 1999 (JP). ... 11-025781 Substituted, Rf represents a phenyl group which may Jul. 8, 1999 (JP) ...... 11-1941.85 have a C-C alkyl group or a C-C acyloxy group which may have a phenyl group or a naphthyl group, or (51) Int. Cl." ...... C07C2/02; CO7C 2/40; a benzyl group or R is a hydroxy group which revers C07C 2/72; CO7C 5/41; CO7C 15/46 ibly forms an aldehyde group through shifting of the (52) U.S. Cl...... 585/422; 585/429; 585/434; position of the double bond adjacent to said hydroxy 585/438: 560/243; 560/244; 568/450 group. The chain diene compound is produced by (58) Field of Search ...... 556/136; 502/152; reacting 2-substituted-1,3-butadienes with terminal 514/1; 560/1, 243, 244; 568/1, 450; 585/422, olefins in the presence of a ruthenium compound in a 429, 434, 438 hydrophilic solvent. Further, the above method pro vides an inexpensive proceSS for preparing a mild (56) References Cited fragrant component and a perfume composition, Such U.S. PATENT DOCUMENTS as 4-methyl-5-hexen-1-al and 4-vinyl-8-methyl-7- nonenal. 4,692,548 9/1987 Drent ...... 560/202 5,113,033 * 5/1992 Myers et al...... 585/506 14 Claims, No Drawings US 6,239,324 B1 1 2 DIENE COMPOUND AND PROCESS FOR Moreover, these methods are Susceptible to forming ring PRODUCING THE SAME products, which is a handicap for the Synthesis of chain terpene. BACKGROUND OF THE INVENTION Meanwhile, organometallic reagents have been widely used in reactions for Synthesizing carbon-carbon bonds, So 1. Field of the Invention as to form desirable skeletons Selectively (Japanese Patent The present invention relates to diene compounds, in Application Laid-Open (JP-A) No. H3-148228). However, particular, co-dimer diene compounds. These compounds these reactions not only involve use of a cumberSome are prepared through the reactions of conjugated diene organometal in a Stoichiometric amount but also requires the compounds with Vinyl esters in the presence of a ruthenium So-called "elimination group', namely, a functional group Salt. The invention especially relates to a chain co-dimer which does not participate in the Structure of the resultant diene compound which is a promising raw material for product. This is a disadvantage from the industrial and preparing terpenes. Chain co-dimer diene compounds are environmental points of View, and the reactions become obtained by reacting a 2-substituted-1,3-butadiene (a con costlier. It is therefore desirable to develop a novel route for jugated diene part) with a compound having a double bond 15 Synthesizing a carbon-carbon bond. This novel route should at its terminal (a vinyl ester part). The invention also relates involve the reaction which does not require any elimination to a method of producing these co-dimer diene compounds. group, and may proceed on a catalytic basis. Typical conjugated dienes used in the invention include isoprene and myrcene. The isoprene is reacted with a vinyl SUMMARY OF THE INVENTION ester to prepare 4-methyl-5-hexen-1-al, which is a useful An object of the present invention is to provide a com perfume material and can be used in a perfume composition. pound having a mild fragrance without emanating irritant The invention relates also to this aspect. odor. Another object of the invention is to provide a method Likewise, myrcene gives rise to 4-Vinyl-8-methyl-7- of preparing Such a compound, the method involving nonenal which is also a useful perfume material. The inven reduced proceSS Steps. The compound can thus be produced tion relates therefore to 4-vinyl-8-methyl-7-nonenal, a 25 at lower costs. A further object of the invention is to provide method of production thereof and a perfume composition a perfume composition comprising Such a compound. prepared therefrom. The 4-vinyl-8-methyl-7-nonenal has a In view of the above, there has been conceived a novel Strong, aliphatic aldehyde-like fragrance, emanating a method of forming a carbon-carbon bond in a regioSelective citrus-as well as rose-like Scent, and can be used as manner through a catalytic reaction. This method allows perfumes or in perfume compositions. preparing new diene compounds which provide promising 2. Description of Related Art raw materials for the production of terpene. Generally, a Small difference in chemical Structures After extensive Studies, the present inventors found that a among compounds gives rise to a considerable difference in novel co-dimer diene compound having a desirable regiose fragrances of the compounds and the other related lectivity can be obtained by reacting 2-Substituted-1,3- properties, e.g. retentivity and volatility. The Search for new 35 butadienes with an olefin compound having a double bond perfumes involves therefore an important workload in Such at its terminal position (hereinafter referred to as "terminal fields as Synthesis of various compounds and tests of their olefins') in a hydrophilic Solvent, in the presence of a fragrance. Among these compounds, aliphatic aldehydes are ruthenium catalyst, and thus completed the present inven known as a useful Source for perfume essence materials. 40 tion. From this viewpoint, many aldehydes have been produced A first aspect of the invention concerns a process for and put to actual use (Motoichi INDO, “Synthetic Perfume", producing diene compounds from 2-substituted-1,3- Chemistry and Product Information, 1996, published by butadienes and terminal olefins. This object required the Kagaku Kogyo Nippoh). For instance, melonal, citral and discovery of a novel carbon-carbon bond-creating reaction citronellal emanate a green melon-like, lemon-like and 45 which proceeds on a catalytic basis. The process provides a hawthorn-like fragrance, respectively, and give a specific novel compound useful as a perfume component. Scent to perfume compositions. They are therefore widely A Second aspect of the invention relates to a diene used as a blending essence for a perfume. compound represented by the following general formula AS for 4-methyl-5-hexen-1-al, a method of its production (IX): from citronellal is reported in J. Org. Chem., Vol. 42, pp. 50 3622, 1977. This method has the disadvantage of involving many StepS and incurring high production costs. Moreover, (IX) there has been no description on the fragrant characteristics R1 of 4-methyl-5-hexen-1-al, nor on its use as perfume com N-N-N- positions. Cis-3-hexenal, a compound Similar to 4-methyl 55 5-hexen-1-al, is very expensive, and trans-2-hexenal, another Similar compound, has a strongly irritant odor. wherein R' represents a hydrogen atom, a C-C alkyl In order to form a carbon-carbon bond with butadiene or group which may have a Substituent or a C-C an Substituted butadienes efficiently, methods involving a alkenyl group which may have a Substituent and R' Diels-Alder reaction (B. M. Trost et al., Angew. Chem. Int. 60 represents a phenyl group which may have a C-C, Ed. Engl, Vol.34, pp. 259 (1995)) and reactions with a triple lower alkyl group or a C-C acyloxy group which bond (T. Mitsudo et al., J. Org. Chem., Vol. 50, pp. 565 may have a phenyl group, a naphthyl group or a benzyl (1985)) have been well-known. group or R is a hydroxy group which reversibly forms All these methods, however, have the disadvantages that an aldehyde group through shifting of the position of the conjugated double bond of butadienes or its counter part 65 the double bond adjacent Said hydroxy group. compound must be activated and the regioSelectivity cannot A third aspect of the invention is concerned with be controlled. 4-methyl-5-hexen-1-all represented by the formula (X): US 6,239,324 B1 4 In the above process, the ruthenium compound may (X) comprise a ruthenium catalyst represented by the following general formula (III): N-- (III) This product can be obtained easily at low costs by hydrolyzing a compound represented by the formula (IX): 1O (DX) R1 N-S-N- R2 wherein R, R, R, R7 and R, which may be the same or 15 different, respectively represent a hydrogen atom or a C-C lower alkyl group, though two adjacent groups in which R" is a methyl group, and R represents a C-C, among R', R. R. R7 and R may be bonded to each acyloxy group which may have a phenyl group, a other so as to form a five- or six-membered ring; W naphthyl group or a benzyl group or R is a hydroxy represents 1,3-butadiene, isoprene, myrcene, 1,5- group which reversibly forms an aldehyde group cyclooctadiene, norbornadiene, 2,3-dimethyl-1,3- through shifting of the position of the double bond butadiene or a halogen atom; and X' represents a adjacent Said hydroxy group; the wavy line shows halogen atom. cis-isomer, trans-isomer,or a mixture thereof. Alternatively, the ruthenium compound may comprise a 4-Methyl-5-hexen-1-all has a high level of fragrance ruthenium catalyst formed by mixing a ruthenium com which is easily diffusible, and contains a strongly fresh and 25 green fruit-like Scent. This aldehyde compound is milder, pound represented by the following general formula (IV): less irritating and more fruity in comparison with Similar perfume compounds Such as cis-3-hexenal and trans-2- (IV) hexenal. | R15 A fourth aspect of the invention relates to 4-vinyl-8- R10 R"14 N. methyl-7-nonenal (XI) and a method of preparing this A compound from myrcene (VIII), one type of 2-substituted RuX R16 V 1,3-butadienes. 4-Vinyl-8-methyl-7-nonenal (XI) gives a R11 R13 N ln Strong, aliphatic aldehyde-like fragrance, emanating a / citrus-as well as rose-like Scent, and thus provides a useful 35 R12 OS V 17 perfume essence material. The product (XI) is also Suitable R for use as a perfume composition. To the above-mentioned end, there is first provided a proceSS for producing a diene compound at least comprising wherein R,R,R,R,R' and R', which may be the the Step of reacting 2-Substituted-1,3-butadienes represented 40 Same or different, respectively represent a hydrogen by the following general formula (I): atom or a C-C lower alkyl group, though two adja cent groups among R, R', R', R', RandR'' may bond to each other So as to form a five- or six (I) membered ring; X' represents a halogen atom; R' and R1 R" respectively represent a hydrogen atom, a C-C, 45 lower alkyl group, a C-C-7 cycloalkyl group, or a N-N phenyl, naphthyl or benzyl group, each of which may be substituted with a C-C lower alkyl group or with wherein R represents a hydrogen atom, a C-C alkyl a halogen atom, or RandR'' are combined with each group which may have a Substituent or a C-C alkenyl 50 other to form a C-C alkylene group; R7 represents a group which may have a Substituent; hydrogen atom, a C-C lower alkyl group, a C-C, with terminal olefins represented by the following general cycloalkyl group, a lower alkyl halide, or a phenyl, formula (II): naphthyl or benzyl group, each of which may be Substituted with a C-C lower alkyl group or with a (II) 55 halogen atom; and n denotes 0 or 1; with Salts repre R2 sented by the following general formula (V): M(X), (V) wherein M represents a mono-, di-, or tri-cation Such as wherein R represents a phenyl group which may have a 60 an alkaline metal, an alkaline earth metal, C-C lower alkyl group, or a C-C acyloxy group ammonium, Silver, aluminum, lanthanum or which may have a phenyl group, a naphthyl group or a Samarium; X represents an anion Such as CIO, benzyl group; in a hydrophilic Solvent in the presence BF, PF, BPhi(where Ph represents a phenyl of a ruthenium compound. group), CFSOO, CHSOO, CHSOO, Preferably, R in the formula (II) is a C-C, acyloxy 65 4-CHCHSOO, 4CICH ISO-O or CFSOO; group which may have a phenyl group, a naphthyl group or a denotes 1 when M is a mono-cation, 2 when M is a benzyl group. a di-cation or 3 when M is a tri-cation. US 6,239,324 B1 S 6 Alternatively, the ruthenium compound may comprise a with salts represented by the following general formula (V): ruthenium catalyst formed by mixing a ruthenium com pound represented by the following general formula (VI): MCX), (V) (VI) 5 R9 wherein M, X and a are the same as defined above; R10 R14 So that the activity of Said ruthenium catalyst can be con trolled. Oux, In the above process, the hydrophilic Solvent may com R11 R13 prise at least one Solvent Selected from the group consisting R12 of methanol, ethanol, water, or mixtures thereof. Preferably, in the above process, 2-substituted-1,3- wherein R, R', R'', R', R', R'' and X’ are the same 15 butadienes are at least one compound Selected from the as defined above; group consisting of with salts represented by the following general formula (V): a) isoprene M(X), (V) b) butadiene; and c) myrcene represented by the formula (VIII): wherein M, X and a are the same as defined above. Preferably, a nitrogen bidentate ligand represented by the following general formula (VII): (VIII)

(VII) 25

S1S

Further, there is provided a diene compound obtainable by the process at least comprising the Step of reacting 2-substituted-1,3-butadienes represented by the following 35 wherein R and R', which may be the same or different, general formula (I): respectively represent an aryl group which may have a C-C lower alkyl group, a C-C lower alkyl group, (I) an aralkyl group or a C-C lower alkenyl group; R. R1 and R', which may be the same or different, respec 40 tively represent an aryl group which may have a C-C, N-N lower alkyl group, a C-C lower alkyloxy group which may have a substituent or a hydrogen atom; R' and R or R' and R' may form a ring which may wherein R represents a hydrogen atom, a C-C alkyl include an oxygen atom, r, S, t and u respectively 45 group which may have a Substituent or a C-C alkenyl denote 0 or 1; and R to R", which may be the same group which may have a Substituent; or different, respectively represent a hydrogen atom, a with terminal olefins represented by the following general C-C lower alkyl group or a C-C lower alkenyl group, though any two groups among R to R' may formula (II): be bonded to each other so as to form a five-or 50 Six-membered ring which may have Substituents, (II) is added to the ruthenium catalyst formed by mixing a R2 ruthenium compound represented by the following general formula (VI): 55 (VI) wherein R represents a phenyl group which may have a R9 C-C lower alkyl group, or a C-C acyloxy group which may have a phenyl group, a naphthyl group or a R10 R14 benzyl group; or R is a hydroxy group which revers 60 ibly forms an aldehyde group through shifting of the Oux, position of the double bond adjacent Said hydroxy R11 R13 grOup, R12 in a hydrophilic Solvent in the presence of a ruthenium 65 compound. wherein R, R', R'', R', R', R'' and X’ are the same The diene compound of the invention may have a struc as defined above; ture represented by the following general formula (IX): US 6,239,324 B1

(DX) (II) R2 N-N-N- 5 =/ wherein R represents a C-C, acyloxy group which wherein R' represents a hydrogen atom, a C-C alkyl may have a phenyl group, a naphthyl group or a group which may have a substituent O C-C, alkenyl benzyl group; in a hydrophilic Solvent in the pres group which may have a Substituent; R represents a ence of a ruthenium compound, to obtain a corre phenyl group which may have a C-C lower alkyl sponding diene compound; and group or a C-C acyloxy group which may have a phenyl group, a naphthyl group or a benzyl group; or b) hydrolyzing said diene compound. R’ is a hydroxy group which reversibly forms an 15 Further yet, there is provided a perfume composition at aldehyde group through shifting of the position of the least comprising 4-methyl-5-hexen-1-all represented by the double bond adjacent Said hydroxy group; and the following general formula (X): wavy line shows cis-isomer, trans-isomer,or a mixture thereof. (X) In the above structure, R is preferably a C-C2 acyloxy 2O group which may have a phenyl group, a naphthyl group or N-- a benzyl group. S. CHO There is further provided a process for producing 4-methyl-5-hexen-1-all represented by the general formula 25 (X): The diene compound of the invention may be 4-vinyl-8- methyl-7-nonenal represented by the formula (XI): (X)

3O S CHO

Said process comprising the Steps of: 35 a) preparing a diene compound represented by the for mula (IX): N CHO (DX) R1 40 There is also provided a perfume composition N-N-N- comprising, as an essential component, 4-Vinyl-8-methyl-7- N S nonenal represented by the formula (XI):

wherein R represents a methyl group; R represents a 45 (XI) C-C acyloxy group which may have a phenyl, naphthyl or benzyl group; and the wavy line shows N cis-isomer, trans-isomer, or a mixture thereof; by reacting 2-Substituted-1,3-butadienes represented by 50 the following general formula (I): (I) S. CHO R1 N-N 55 The invention relates also to a proceSS for producing 4-vinyl-8-methyl-7-nonenal represented by the formula (XI): wherein R' represents a methyl group; with terminal olefins represented by the following general formula (II): US 6,239,324 B1

(XI) (III) R4 R8 R5 O-Ruwx R7 R6 N CHO 1O wherein R, R, R, R7 and R, which may be the same or different, respectively represent a hydrogen atom or a Said process comprising the Steps of: C-C lower alkyl group, though two adjacent groups among R', R. R. R7 and R may be bonded to each a) reacting myrcene represented by the formula (VIII): 15 other so as to form a five- or six-membered ring; W represents 1,3-butadiene, isoprene, myrcene, 1,5- (VIII) cyclooctadiene, norbornadiene,2,3-dimethyl-1,3- butadiene or a halogen atom; and X' represents a halogen atom. Alternatively, the ruthenium compound may comprise a ruthenium catalyst formed by mixing a ruthenium com pound represented by the following general formula (IV):

(IV) S1S 25 f R15 R10 R"14 N. with a vinyl acylate represented by the following M RuX R16 general formula (XII): V R11 R13 N. ln (XII) / R12 os R17

35 wherein R,R,R,R,R' and R', which may be the Same or different, respectively represent a hydrogen wherein R represents a hydrogen atom, a C-C lower atom or a C-C lower alkyl group, though two adja alkyl group or a phenyl, naphthyl or benzyl group, cent groups among R, R', R', R', RandR'' may each of which may have a C-C lower alkyl group; be bonded to each other so as to form a five- or in a hydrophilic Solvent in the presence of a ruthenium 40 six-membered ring; X' represents a halogen atom; R' compound, So as to form 4-vinyl-8-methyl-1,7- and R' respectively represent a hydrogen atom, a nonadienyl acylate represented by the following gen C-C lower alkyl group, a C-C, cycloalkyl group, or eral formula (XIII): a phenyl, naphthyl or benzyl group, each of which may be substituted with a C-C lower alkyl group or with 45 a halogen atom, or RandR'' are combined with each (XIII) other so as to form a C-C alkylene group; R' represents a hydrogen atom, a C-C lower alkyl group, a C-C7 cycloalkyl group, a lower alkyl halide group, or a phenyl, naphthyl or benzyl group, each of 50 which may be substituted with a C-C lower alkyl group or with a halogen atom; and n denotes 0 or 1; with salts represented by the following general formula (V): M(X), (V) 55 wherein M represents a mono-, di- or tri-cation Such as an alkaline metal, an alkaline earth metal, ammonium, wherein R represents a hydrogen atom, a C-C lower silver, aluminum, lanthanum or Samarium; X repre alkyl group or a phenyl, naphthyl or benzyl group, sents a anion such as CIO, BF, PF, B.Ph. 60 (where Ph represents a phenyl group), CFSO-O", each of which may have a C-C lower alkyl group; CHSOO, CH, SOO, CHSO, O, and 4-CHCHSO-O or 4-CICHSOO'; a denotes 1 b) hydrolyzing said 4-vinyl-8-methyl-1,7-nonadienyl acy when M is a mono-cation, 2 when M is a di-cation or late. 3 when M is a tri-cation. In the process for producing 4-vinyl-8-methyl-7-nonenal 65 Alternatively yet, the ruthenium compound may comprise (XI), the ruthenium compound may comprise a ruthenium a ruthenium catalyst formed by mixing a ruthenium com catalyst represented by the following general formula (III): pound represented by the following general formula (VI): US 6,239,324 B1 12 M(X), (V) (VI) wherein M, X and a are the same as defined above; so R9 that the activity of Said ruthenium catalyst can be R10 R14 controlled. DETAILED DESCRIPTION OF THE Oux, PREFERRED EMBODIMENTS R11 R13 The above and other objects, features and advantages of R12 the present invention will be made apparent from the fol 1O lowing description of the preferred embodiments, given as non-limiting examples. wherein R, R 9, R'', R'', R, R'' and X are the same Typical examples of the C-C alkyl group, represented as defined above; by R' in the diene compound (IX) of the present invention, with salts represented by the following general formula (V): include a methyl group, ethyl group, propyl group, isopropyl 15 group, butyl group, isobutyl group, Sec-butyl group, tert M(X), (V) butyl group, pentyl group and hexyl group. Examples of the Substituent for these groupS may include C-C lower alkyl wherein M, X and a are the same as defined above. groupS Such as a methyl group, ethyl group, propyl group, In the proceSS for producing 4-vinyl-8-methyl-7-nonenal, isopropyl group, butyl group, isobutyl group, Sec-butyl a nitrogen bidentate ligand represented by the following group and tert-butyl group; C-C lower alkoxy groupS. Such general formula (VII): as a methoxy group, ethoxy group, propoxy group, isopro poxy group, butoxy group and tert-butoxy group; C1-C (VII) acyloxy groups, which may have a phenyl group, a naphthyl group or a benzyl group, Such as a formyloxy group, acetoxy 25 group, propanoyloxy group, butanoyloxy group, pivaloy loxy group, pentanoyloxy group, phenylacetoxy group, acetoactoxy group, benzoyloxy group and naphthoyloxy group, and C-C alkoxycarboxy groups which may have a phenyl group or a naphthyl group, Such as a methoxycar boxy group, ethoxycarboxy group and phenoxycarboxy grOup. Typical examples of the C-C alkenyl group represented by R' include a vinyl group, propenyl group, butenyl group, wherein R and R', which may be the same or different, pentenyl group, hexenyl group and 4-methyl-3-pentenyl respectively represent an aryl group which may have a 35 group. Further, examples of the Substituent for the alkenyl C-C lower alkyl group, a C-C lower alkyl group, group include C-C lower alkyl groupS. Such as a methyl an aralkyl group or a C-C lower alkenyl group; R. group, ethyl group, propyl group, isopropyl group, butyl and R', which may be the same or different, respec group, isobutyl group, Sec-butyl group and tert-butyl group; tively represent an aryl group which may have a C-C, C-C lower alkoxy groupS. Such as a methoxy group, lower alkyl group, a C-C lower alkyloxy group 40 ethoxy group, propoxy group, isopropoxy group, butoxy which may have a substituent or a hydrogen atom; R' group and tert-butoxy group; C1-C acyloxy groups, which and R or R' and R' may form a ring which may may have a phenyl group, a naphthyl group or a benzyl include an oxygen atom, r, S, t and u respectively group, Such as a formyloxy group, acetoxy group, propanoy denote 0 or 1; and R to R' which may be the same loxy group, butanoyloxy group, pivaloyloxy group, pen or different, respectively represent a hydrogen atom, a 45 tanoyloxy group, phenylacetoxy group, acetoactoxy group, C-C lower alkyl group or a C-C lower alkenyl benzoyloxy group and naphthoyloxy group; and C-C2 group, though any two groups among R33 to R0 may alkoxycarboxy groups, which may have a phenyl, naphthyl be bonded to each other so as to form a five-or or benzyl group, Such as a methoxycarboxy group, ethoxy Six-membered ring which may have Substituents, 50 carboxy group and phenoxycarboxy group. may be added to the ruthenium catalyst formed by mixing a Preferably, the group represented by R' in the diene ruthenium compound represented by the following general compound (IX) include a hydrogen atom, methyl group, formula (VI): ethyl group, 4-methylpentyl group, 4-methyl-3-pentenyl group and 4-acetoxy-4-methylpentyl group. (VI) 55 AS Substituents of the phenyl group represented by R in R9 the diene compound (IX), C-C lower alkyl groups may include a methyl group, ethyl group, propyl group, isopropyl R10 R14 group, butyl group, isobutyl group, Sec-butyl group, and tert-butyl group. 60 Also in R, examples of the C-C2 acyloxy group which R11 Oux,R13 may have a phenyl group, a naphthyl group or a benzyl group may include a formyloxy group, acetoxy group, R12 propanoyloxy group, butanoyloxy group, pivaloyloxy group, pentanoyloxy group, phenylacetoxy group, acetoac wherein R, R', R'', R', R', R'' and X’ are the same 65 toxy group, benzoyloxy group and naphthoyloxy group. as defined above; Preferable examples among the diene compounds (IX) of with salts represented by the following general formula (V): the invention include a compound (IX) represented by the US 6,239,324 B1 13 14 following general formula: parts, preferably 0.8 to 3 parts, relative to one part of 2-substituted-1,3-butadienes (I). (DX) Preferred examples of 2-substituted-1,3-butadiens (I), which are one of the Starting materials for diene compound R1 (IX), include butadiene, 2-methylbutadiene (isoprene), 7-methyl-3-methylene-1-octene,2-methyl-6-methylene-7- N-N-N- octen-2-yl acetate (myrcenyl acetate), 2-methyl-6- methylene-7-octen-2-yl methyl carbonate and 7-methyl-3- methylene-1,6-Octadiene (myrcene) wherein R' is the same as defined above and R represents Preferred examples of the terminal olefins (II), which are a C-C acyloxy group which may have a phenyl the counter-part Starting material, are Styrene, Vinyl acetate, group, a naphthyl group or a benzyl group or R is a vinylbutyrate, vinyl pivalate and vinyl benzoate. In order to hydroxy group which reversibly forms an aldehyde obtain more preferable compounds (IX) among the diene group through shifting of the position of the double compounds (IX) of the invention, terminal olefins repre bond adjacent to Said hydroxy group. Sented by the general formula (II) may be used in place of The compound (IX) gives a higher yield in a vinyl ester 15 reaction, compared with the compounds in which the group the terminal olefins represented by the general formula (II). R is a phenyl group which may have a C-C lower alkyl Preferred examples of the ruthenium compound used for grOup. the production of diene compound (IX) comprise the ruthe In the diene compounds (IX), the double bond may give nium catalysts represented by the general formula (III). rise to either trans-isomers, cis-isomers or a mixture thereof, Another preferred type of ruthenium catalysts are pre and all types can be used. However, the preferred type is pared by mixing a ruthenium compound represented by the cis-isomers. following general formula (IV), or a ruthenium compound The diene compound (IX) of the invention is produced by represented by the general formula (VI), with Salts repre reacting 2-substituted-1,3-butadienes (I) with terminal ole sented by the general formula (V). fins (II) in the presence of a ruthenium compound in a The ruthenium catalyst (III) used in the above reaction hydrophilic Solvent according to the following chemical 25 includes ligands. One of them has the following general formula: formula (XIV): (XIV)

He (II) Ru compound

N-N-N- 35 (IX) wherein R, R, R, R7 and R are the same as defined above. wherein R' and R are the same as defined supra. Specific examples of R, R, R, R7 and R of the In the preparation of diene compound (IX), the terminal 40 compound include a hydrogen atom or C-C lower alkyl olefins (II) may generally be reacted in an amount of about groupS Such as a methyl group, ethyl group, propyl group, 0.05 to 50 equivalents, preferably about 0.1 to 10 isopropyl group, butyl group, isobutyl group, Sec-butyl equivalents, relative to one equivalent of 2-Substituted-1,3- group, and tert-butyl group. butadienes (I). Preferred examples of the ligand (III), include The amount of ruthenium compound used in the reaction 45 cyclopentadienyl, tetramethylcyclopentadienyl, pentameth generally ranges from about 0.001 to 50 mol %, preferably ylcyclopentadienyl and indenyl. from about 0.08 to 10 mol %, based on 2-substituted-1,3- Examples of the group W in the general formula (III) butadiens (I). include 1,3-butadiene, isoprene, myrcene, 1,5- The above reaction is generally carried out at about 0 to cyclooctadiene, norbornadiene, 2,3-dimethyl-1,3-butadiene, 200° C., preferably about 70 to 120° C., generally for about 50 and a halogen atom which comprises a fluorine atom, 1 to 72 hours, preferably about 5 to 24 hours. These chlorine atom, bromine atom and iodine atom. conditions may be appropriately modified depending on Specific examples of the ruthenium compound of the materials Subjected to the reaction and amount of the ruthe formula (III) include the compounds below, in which “m" nium compound. Although the reaction is usually conducted indicates the number of coordinate electrons, m being their in an atmosphere of inert gas Such as nitrogen gas or argon 55 number (for instance, “m” means that the number of coor gas, it may also be conducted in an atmosphere of gasified dinate electrons is 6): Starting material. The reaction may be carried out in a batch or continuous process. (m-cyclopentadienyl)ruthenium (III) dichloride; The hydrophilic solvents to be used in the reaction include (m-cyclopentadienyl)ruthenium (III) dibromide; any inert Solvent as far as it does not participate in the 60 (m-cyclopentadienyl) (m"-1,3-butadiene)ruthenium (II) reaction. Preferably used are water, lower alcohols Such as chloride; methanol, ethanol, propanol, isopropanol and butanol or (m-cyclopentadienyl) (m"-isoprene)ruthenium (II) chloride; amides Such as dimethylformamide, dimethylacetamide, (m-cyclopentadienyl) (m-myrcene)ruthenium (II) chloride; dimethylimidazolidinone and N-methylpyrrollidone or a (m-cyclopentadienyl) (m'-1,5-cyclooctadiene)ruthenium mixture thereof. Among these Solvents, methanol, ethanol, 65 (II) chloride; aqueous ethanol and the like are more preferred. The hydro (m-cyclopentadienyl) (m"-norbornadiene)ruthenium (II) philic Solvent is generally used in a weight ratio of 0.1 to 25 chloride; US 6,239,324 B1 15 16 (m-cyclopentadienyl) (m"-2,3-dimethyl-1,3-butadiene) formula (XVI): ruthenium (II) chloride; (m-pentamethylcyclopentadienyl)ruthenium (III) dichlo (XVI) ride; (m-pentamethylcyclopentadienyl)ruthenium (III) dibro mide, (m-pentamethylcyclopentadienyl) (m"-1,3-butadiene) R16 (m-pentamethylcyclopentadienyl)ruthenium (II) chloride; (m"-isoprene)ruthenium (II) chloride; (m-pentamethylcyclopentadienyl) (n'-myrcene)ruthenium 1O (m-pentamethylcyclopentadienyl)(II) chloride; (m'-1,5-cyclooctadiene) ruthenium (II) chloride; wherein R', R'R'' and n are the same as defined (m-pentamethylcyclopentadienyl) (m"-norbornadiene) above. ruthenium (II) chloride; and 15 Specific examples of the group R' or R' include a (m-pentamethylcyclopentadienyl) (n'-2,3-dimethyl-1,3- hydrogen atom, C-C lower alkyl groups Such as a methyl butadiene)ruthenium (II) chloride. group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, Sec-butyl group and tert-butyl group; The ruthenium compound represented by the general Cs-C, cycloalkyl groups Such as a cyclopentyl group, formula (III) may be prepared according to a method cyclohexyl group and cycloheptyl group; phenyl groups described by K. Masuda et al. in Organometallics, Vol. 12, which may be Substituted with a C-C lower alkyl group or pp. 2221, 1993, a method disclosed in “Jikken Kagaku a halogen atom, (where examples of the C-C lower alkyl Kouza, Fourth Edition' Vol. 18, Organometallic Complex, groups include a methyl group, ethyl group, propyl group, pp. 269, 1991, edited by Japan Society of Chemical Engi isopropyl group, butyl group, isobutyl group, Sec-butyl neers and published by Maruzen, or by other similar meth 25 group and tert-butyl group and examples of the halogen ods. atoms include a fluorine atom, chlorine atom, bromine atom For instance, (mi-pentamethylcyclopentadienyl) (m"- and iodine atom), naphthyl groups which may be Substituted isoprene) ruthenium (II) chloride can be synthesized by the with a C-C lower alkyl group or a halogen atom, where following method: examples of the C-C lower alkyl groups or the halogen Pentamethylcyclopentadienyl ruthenium (II) dichloride atoms are the same as above, and benzyl groups which may dimer and one equivalent of Zinc powder are Suspended in be Substituted with a C-C lower alkyl group or a halogen methanol (100 times the amount of the ruthenium complex) atom, where examples of the C-C lower alkyl groups or at 0° C. Then, 30 equivalents of isoprene are added to the the halogen atoms are the same as above. Alternatively, R' Suspension. After the mixture is reacted for 15 minutes, a and R' may be combined with each other to form an Solid portion is separated by filtration. The resulting Solution 35 alkylene group having 3-6 carbon atoms, where examples of is concentrated to obtain a crude product. The crude product the alkylene group having 3-6 carbon atoms include 1,3- is recrystallized from ethanol to yield (m-pentamethyl propylene, 1,4-butylene, 1,5-pentylene and 1,6-hexelene. cyclopentadienyl) (m"-isoprene) ruthenium (II) chloride. Specific examples of the group R' in the ligand (XVI) The above method may be utilized to prepare ruthenium include a hydrogen atom and C-C lower alkyl groups Such compounds represented by the general formula (III), other 40 as a methyl group, ethyl group, propyl group, isopropyl than for (m-pentamethylcyclopentadienyl) (m"-isoprene) group, butyl group, isobutyl group, Sec-butyl group and ruthenium (II) chloride. tert-butyl group; Cs-C7 cycloalkyl groupS Such as a cyclo The ruthenium compound represented by the general pentyl group, cyclohexyl group and cycloheptyl group; formula (IV) or (VI) used in the inventive reaction includes lower alkyl halides Such as a trifluoromethyl group and a plurality of ligands. One of them has a structure repre 45 trichloromethyl group; phenyl, naphthyl and benzyl groups, sented by the following general formula (XV): each of which may be substituted with a C-C lower alkyl group or a halogen atom, where examples of the C-C, (XV) lower alkyl groups include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, 50 Sec-butyl group and tert-butyl group and examples of the halogen atoms include a fluorine atom, chlorine atom, bromine atom and iodine atom. Preferred examples of the ligand (XVI) include N-2- aminoethyl-methane Sulfonamide, N-2-aminoethyl 55 ben Zene Sulfonamide, N-2-amino ethyl-p- R12 tolue ne sulfonamide, N-2-aminoethyl-trifluoro me thane Sulfonamide, N-2-amino ethyl wherein R, R', R'', R', R and R'' are the same as trichloromethaneSulfonamide, N-3-aminopropyl-methane defined above. sulfonamide, N-3-aminopropyl-benzenesulfonamide,N-3- Specific examples of R,R,R,R,R or R' include 60 aminopropyl-p-toluenesulfonamide, N-3-aminopropyl a hydrogen atom and lower alkyl groupS. Such as a methyl trifluorome thane Sulfonamide, N-3-aminopropyl group, ethyl group, propyl group, isopropyl group, butyl trichlorome thane Sulfonamide, N-2-amino-1,2- group, isobutyl group, Sec-butyl group and tert-butyl group. dimethylethyl-methanesulfonamide, N-2-amino-1,2- Preferred examples of the ligand (XV) include benzene, dimethylethyl-benzenesulfonamide, N-2-amino-1,2- p-cymene, mesitylene and hexamethylbenzene. 65 dimethylethyl-p-toluenesulfonamide, N-2-amino-1,2- One of the ligands in the ruthenium compound of the dimethylethyl-trifluoromethanesulfonamide, N-2-amino-1, general formula (IV) is represented by the following general 2-dimethylethyl-trichloromethane sulfonamide, N-2-amino US 6,239,324 B1 17 18 1,2-diphenylethyl-methaneSulfonamide, N-2-amino-1,2- mono-, di- or tri-cation Such as alkaline metals, alkaline diphenylethyl-benzene Sulfonamide, N-2-amino-1,2- earth metals, ammonium, Silver, aluminum, lanthanum or diphenylethyl-p-toluenesulfonamide, N-2-amino-1,2- Samarium. Specific examples of these cations include Li", diphenylethyl-trifluoromethanesulfonamide, N-2-amino-1, Na', K", Mg, Ca, NH', Ag", Al", La" and Smt. 2-diphenylethyl-trichlorome thane Sulfonamide, Specific examples of X which represents anions may 2-methaneSulfonylamino-cyclohexylamine, 2-benzene include Co., BF, PF, B.Ph., (where Ph represents a Sulfonyl amino - cyclohe Xyla mine, 2-p- phenyl group), CFSOO, CHSOO, CHSOO, toluene Sulfonylamino-cyclohexylamine,2-trifluoro 4-CHCHSOO and 4-CICHSOO. me thane Sulfonylamino - cyclohe Xylamine and The ruthenium catalyst is formed by mixing the ruthe 2-trichloromethaneSulfonylamino-cyclohexylamine. nium compound of the general formula (IV) or (VI) with the X" in the compound (IV) or (VI) is a halogen atom. Salts of the general formula (V) in an appropriate reaction Specific examples of the halogen atom may include a System. fluorine atom, chlorine atom, bromine atom and iodine Preferably, to the ruthenium catalyst system formed from atOm. the ruthenium compound of the formula (IV) or (VI) and the Specific examples of the ruthenium compound repre 15 Salts of the formula (V) is added a nitrogen bidentate ligand Sented by the general formula (IV) include the compounds represented by the general formula (VII). below, in which “m"' indicates the number of coordinate The addition of this nitrogen bidentate ligand further electrons, m being their number: improves the activity of the ruthenium catalyst, and the objective product can be obtained more economically than (N-2-aminoethyl-p-toluenesulfonamide) (m-benzene) when the foregoing ruthenium catalyst is used. ruthenium (II) chloride; In the nitrogen bidentate ligand (VII), Specific examples (N-2-aminoethyl-p-toluenesulfonamide) (m-p-cymene) of the groups R to R' include C-C lower alkyl groups ruthenium (II) chloride; Such as a methyl group and ethyl group, aryl groupS. Such as (N-2-aminoethyl-p-toluenesulfonamide) (m-mesitylene) a phenyl group and tolyl group and alkoxy groupS. Such as a ruthenium (II) chloride; 25 methoxy group and ethoxy group. R and R or R'' and (N-2-aminoethyl-p-toluenesulfonamide) (m-benzene) R' may be bonded to each other to form, a pyridine ring, an ruthenium (II) bromide; Oxazoline ring or the like. Moreover, any two groups among (N-2-aminoethyl-p-toluenesulfonamide) (m-p-cymene) R to R' may be bonded to each other, whereby the moiety ruthenium (II) bromide; and linking imine groups may form a ring Such as a phenyl, (N-2-aminoethyl-p-toluenesulfonamide) (m-mesitylene) naphthyl or benzyl group. ruthenium (II) bromide. More specific examples of the nitrogen bidentate ligand (VII) include 2.2-piperidine, 2,2'-bis(4-benzyl-2-oxazoline), The ruthenium compound represented by the general 2,2'-bis(2-oxazolinyl)naphthyl and 2,2'-methylenebis(4- formula (IV) may be produced according to a well-known phenyl-2-oxazoline). method (for instance, the method described in WO97/ 35 In the preparation process of the diene compound (IX), 20789) or the methods Supra. previously prepared ruthenium compound may be used as a For instance, (N-2-aminoethyl-p-toluene Sulfonamide) catalyst. Alternatively, the Starting materials of ruthenium (aryl)ruthenium (II) chloride may be synthesized by the compound may be added Separately to the reaction System. following method: In the Second aspect of the invention, 4-methyl-5-hexen (m-Benzene))ruthenium (II) dichloride and one equiva 40 1-all of the formula (X) can be easily obtained at low costs lent of N-2-aminoethyl-p-toluene sulfonamide are heated by hydrolyzing a compound of the formula (IX). 4-Methyl and stirred at 80 C., together with isopropyl alcohol. The 5-hexen-1-all has a fragrance that is easily diffusible and resulting mixture is then concentrated and washed to obtain gives a highly fresh and green fruit-like Scent. This fragrance (N-2-aminoethyl-p-toluenesulfonamide) (m-benzene) is milder, less irritating and more fruity than Similar perfume ruthenium (II) dichloride. 45 compounds Such as cis-3-hexenal and trans-2-hexenal. The above method may be utilized to obtain the ruthe nium compounds represented by the general formula (IV), The invention also relates to a proceSS for producing other than for (N-2-aminoethyl-p-toluenesulfonamide) 4-methyl-5-hexen-1-all of the general formula (X). (aryl)ruthenium (II) chloride. The process comprises hydrolyzing a diene compound of AS Specific examples of the ruthenium compound of the 50 the formula (IX). general formula (VI), the following compounds may be given. (IX) R1 Ruthenium m-benzene dichloride Ruthenium m-p-cymene dichloride 55 N-N-N- R2 Ruthenium m-mesitylene dichloride R1 R1 Ruthenium m-benzene dibromide Ruthenium m-p-cymene dibromide N-N-N-" stationicle N-N- Ruthenium m-mesitylene dibromide (IX)-1 (X) Ruthenium m-benzene diiodide 60 Ruthenium m-p-cymene diiodide Ruthenium m-mesitylene diiodide Further, there is provided a perfume composition com prising 4-methyl-5-hexen-1-all of the formula (X). On the other hand, the Salts represented by the general The diene compound of the formula (IX) can be synthe formula (V) form the ruthenium catalyst in combination 65 sized from isoprene (I) and a vinyl acylate compound (II) in with the ruthenium compound represented by the general the presence of a ruthenium catalyst as shown in the reaction formula (IV) or (VI). In the formula (V), M represents a below: US 6,239,324 B1 19 20 be appropriately modified, depending upon the materials R1 Subjected to the reaction and the content of the ruthenium R2 compound. / Ru catalsyt Although the reaction is usually conducted in an atmo N-N -- He Sphere of inert gas Such as nitrogen gas or argon gas, it may (I) (II) also be conducted in an atmosphere of gasified Starting material. In the diene compound (IX) thus obtained, the double N-N-N- bond is preferably cis-type, though it may be any one of (IX) trans-type, cis-type and a mixture of both. 4-Methyl-5-hexen-1-all (X) used in the present invention In the vinyl acylate compound of the formula (II), R is can be obtained with ease by hydrolyzing the diene com a C-C acyloxy group which may have a phenyl, naphthyl pound (IX). According to a specific hydrolyzing method, the or benzyl group or R is a hydroxy group which reversibly diene compound (IX) is heated and stirred in an aqueous forms an aldehyde group through shifting of the position of 15 Sulfuric acid Solution, aqueous hydrochloric acid and/or the double bond adjacent to Said hydroxy group. aqueous acetic acid Solution. Alternatively, it can be heated, Examples of the C-C acyloxy group (which may have depending on the necessity, in an aqueous Solution of an a phenyl, naphthyl or benzyl group) may include a formy alkali Such as Sodium hydroxide. loxy group, acetoxy group, propanoyloxy group, butanoy 4-Methyl-5-hexen-1-all represented by the formula (X), as loxy group, pivaloyloxy group, pentanoyloxy group, phenyl described in test examples infra, has high diffusibility, a acetoxy group, acetoacetoxy group, benzoyloxy group or Strongly fresh green fruit-like fragrance, and emanates a leSS naphthoyloxy group. irritating odor. It is fruitier and milder than Similar perfume Preferred examples of the vinyl acylate compound include compounds Such as cis-3-hexenal and trans-2-hexenal. It can Vinyl acetate, Vinyl butylate, Vinyl pivalate and Vinyl ben therefore be used in general-purpose applications Such as ZOate. 25 fruity type or floral green type perfumes, as well as additive In the diene compound (IX) which is the starting material materials for a green apple, kiwi, or apple flavor. It may also of the present invention, R is a C-C acyloxy group which be used as adjuvant for fruit fragrances. may have a phenyl, naphthyl or benzyl group. The perfume composition according to the present Examples of the C-C acyloxy group (which may have embodiment can provide aromatics, various cosmetics and a phenyl, naphthyl or benzyl group) may include a formy Sanitary materials. For instance, 4-methyl-5-hexen-1-all (X) loxy group, acetoxy group, propanoyloxy group, butanoy is added to aromatics Such as deodorants and interior aro loxy group, pivaloyloxy group, pentanoyloxy group, phenyl matics, various cosmetics including cleaning cosmetics Such acetoxy group, acetoacetoxy group, benzoyloxy group or as Soaps, Shampoos and rinses, hair cosmetics Such as hair naphthoyloxy group. dyes and hair tonics, fundamental cosmetics Such as creams, Preferred examples of the diene compound (IX) are 35 face lotions, colognes and packs, make-up cosmetics Such as 4-methyl-1,5-hexadien-1-yl acetate, 4-methyl-1,5-hexadien powders, foundations and rouges, fragrant cosmetics Such as 1-yl butanoate, 4-methyl-1,5-hexadien-1-yl pivalate and Scents, Sunburn or Sunscreen cosmetics, lip cosmetics Such 4-methyl-1,5-hexadien-1-yl benzoate. as lipstickS and lip creams, oral cosmetics Such as dental The ruthenium compound represented by the general creams and mouth washes and bath cosmetics, Sanitary formula (IV) may be produced according to a well-known 40 materials. Such as disinfectants and insecticides, bleaches, method, e.g. method described in WO97/20789, or a method SoftenerS or tableware detergents. Supra. 4-Methyl-5-hexen-1-al(X) is added to the above products The Solvent used in the co-dimerization reaction of iso in an amount Sufficient to confer fragrance to them and prene (I) with the vinyl acylate compound (II) may include heighten the product value. any inert Solvent as far as it does not participate in the 45 The content of 4-methyl-5-hexen-1-all (X) to be added in reaction. Hydrophilic Solvents including water, lower alco the perfume composition may be determined depending on hols Such as methanol, ethanol, propanol, isopropanol and the object. It is preferably 10 ppm to 10% by weight in the butanol or amides Such as dimethylformamide, total amount, although no particular limitation is imposed on dimethylacetamide, dimethyl-imidazolidinone and the content. The perfume composition according to the N-methylpyrrolidone or a mixture of these solvents may 50 present embodiment may be Supplemented with various preferably be used. Among them, methanol, ethanol, aque blending perfume elements or base agents for designing ous methanol and aqueous ethanol and the like are the fragrances. preferred Solvents. The present invention thus enables the production of The hydrophilic Solvent is generally used in a ratio of 4-methyl-5-hexen-1-all (X) with high purity in a simple about 0.1 to 25 parts by volume, preferably 0.8 to 3 parts by 55 process at a lower cost. This compound is highly diffusible, Volume, relative to one part by weight of isoprene. and has a strong and fresh green fruit-like fragrance. In the co-dimerization reaction, the content of the vinyl Moreover, the inventive compound has a less irritating odor acylate compound (II) is generally 0.05 to 50 equivalents, and is fruitier and milder than the Similar perfume com preferably 0.1 to 10 equivalents, relative to one equivalent of pounds Such as cis-3-hexenal and trans-2-hexenal. It can isoprene. 60 therefore be used for general-purpose applications Such as In the co-dimerization reaction, the content of the ruthe fruity type or floral green type perfumes, as well as raw nium compound to be used is about 0.001 to 50 equivalents, blending agents for green apples, kiwis, apples or the like. preferably about 0.08 to 10 equivalents, relative to one Also it can be used to enhance the fragrances of fruits. equivalent of isoprene. Therefore, the perfume composition comprising the inven The above reaction is generally carried out at about 0 to 65 tive compound can be utilized in a wide range of application 200° C., preferably about 70 to 120° C. for about 1 to 72 fields Such as aromatics, various cosmetics or Sanitary hours, preferably about 5 to 24 hours. These conditions may materials. US 6,239,324 B1 21 22 In a fourth aspect of the invention, there is provided R in the vinyl acylate compound (XII) is a hydrogen atom, 4-vinyl-8-methyl-7-nonenal. This product is a novel com a C-C lower alkyl group or a phenyl, naphthyl or benzyl pound which has a high diffusibility and a strong aliphatic group which may have a C-C lower alkyl group. Among aldehyde-like fragrance, emanating Simultaneously a citrus these groups, specific examples of the C-C lower alkyl and rose-like fragrance. This product can therefore be used 5 group include a methyl group, ethyl group, propyl group, for conferring Scents to perfume compositions. These char butyl group, isobutyl group, Sec-butyl group and tert-butyl group. Examples of the C-C lower alkyl group in the acteristics of 4-vinyl-8-methyl-7-nonenal (XI) have been phenyl, naphthyl or benzyl group which may have the C-C, hitherto unknown. lower alkyl group include a methyl group, ethyl group, The product (XI) can be obtained in the reactions illus propyl group, butyl group, isobutyl group, Sec-butyl group trated below: myrcene (VIII) is reacted with a vinyl acylate and tert-butyl group. compound (XII) under a low polymerization reaction Preferred Specific examples of the Vinyl acylate com process, i.e., a co-dimerization reaction process, thereby pound represented by the general formula (XII) are vinyl obtaining 4-vinyl-8-methyl-1,7-nonadienyl acylate (XIII). acetate, Vinyl butyrate, Vinyl pivalate and Vinyl benzoate. Then, the latter is hydrolyzed to give 4-vinyl-8-methyl-7- In 4-vinyl-8-methyl-1,7-nonadienyl acylate (XIII) which nonenal (XI): 15 is obtained as the intermediate for the present invention, R is a hydrogen atom, C-C lower alkyl group or phenyl, naphthyl or benzyl group which may have a C-C alkyl grOup. N Preferred specific examples of 4-vinyl-8-methyl-1,7- nonadienyl acylate represented by the general formula (XIII) include 4-vinyl-8-methyl-1,7-nonadienyl acetate, 4-vinyl-8- N- R Ru catalysis methyl-1,7-nonadienyl propionate, 4-Vinyl-8-methyl-1,7- nonadienylbutyrate, 4-Vinyl-8-methyl-1,7-nonadienyl piv S N O alate and 4-Vinyl-8-methyl-1,7-nonadienyl benzoate. (VIII) (XII) 25 In the production of 4-vinyl-8-methyl-1,7-nonadienyl acylate (XIII), the vinyl acylate compound (XII) may be reacted generally in an amount of about 0.05 to 50 N equivalents, preferably 0.1 to 10 equivalents, relative to one equivalent of myrcene (VIII). The content of the ruthenium compound used in this reaction ranges from about 0.001 to 50 mol %, preferably from about 0.8 to 10 mol %, based on one mol of myrcene S. S. s R (VIII). The above reaction is carried out generally at about 0 to O 35 200° C., preferably about 70 to 120° C., for about 1 to 72 (XIII) hours, preferably about 5 to 24 hours. These conditions may be appropriately modified depending upon the materials Subjected to the reaction and the amount of ruthenium N compound. Although the reaction is usually conducted in an 40 atmosphere of inert gas Such as nitrogen gas or argon gas, it may also be conducted in an atmosphere of gasified Starting material. Further, the reaction may be conducted in a batch or continuous process. N S “ R Hydrolysis The hydrophilic solvent used in the above reaction may 45 O include any inert Solvent, as far as it does not participate in (XIII) the reaction. Preferably used hydrophilic solvents include water, lower alcohols Such as methanol, ethanol, propanol, isopropanol and butanol or amide S Such as dimethylformamide, dimethylacetamide, dimethylimidazo S(R) 50 lidinone and N-methylpyrrolidone or a mixture of these Solvents. Among them, methanol, ethanol, aqueous ethanol and the like are more preferably used. The hydrophilic (R2) Solvent is used in a ratio ranging generally from 0.1 to 25 S S OH parts by volume, preferably from 0.8 to 3 parts by volume, 55 relative to one part by weight of myrcene (VIII). After the reaction is completed, the resultant reaction mixture is treated in a usual way. Then, the resulting mixture S(R) N is distilled to extract 4-vinyl-8-methyl-1,7-nonadienyl acy late (XIII) as an intermediate. 60 To prepare 4-vinyl-8-methyl-1,7-nonadienyl acylate (R2) (XIII), a ruthenium compound can be used. Preferred N S OH N CHO examples of the ruthenium compound include ruthenium (XI) catalyst represented by the following general formula (III) Supra. 65 Another preferred ruthenium catalyst is prepared by mix The codimerization reaction is conducted in a hydrophilic ing a ruthenium compound having the formula (IV) and a Solvent, in the presence of a ruthenium catalyst. Salt having the formula (V) Supra. US 6,239,324 B1 23 24 R in the vinyl acylate compound (XII) is a hydrogen atom, The above hydrolysis is generally carried out at about 20 a C-C lower alkyl group or a phenyl, naphthyl or benzyl to 120° C., preferably about 30 to 100° C. for about 1 to 72 group which may have a C-C lower alkyl group. Among hours, preferably about 5 to 24 hours. These conditions may these groups, specific examples of the C-C lower alkyl be appropriately modified depending upon the materials group include a methyl group, ethyl group, propyl group, Subjected to the reaction and the content of the aqueous acid butyl group, isobutyl group, Sec-butyl group and tert-butyl or alkali Solution. Although the reaction is usually conducted group. Examples of the C-C lower alkyl group in the in an atmosphere of inert gas Such as nitrogen gas or argon phenyl, naphthyl or benzyl group which may have the C-C, lower alkyl group include a methyl group, ethyl group, gas, it may also be conducted in an atmosphere of gasified propyl group, butyl group, isobutyl group, Sec-butyl group Starting material. The reaction may be conducted either in a and tert-butyl group. batch process or in a continuous process. Preferred Specific examples of the vinyl acylate com Any inert Solvent may be used in the above reaction, as far pound (XII) include vinyl acetate, vinyl butyrate, vinyl as it does not participate in the reaction. Commonly used pivalate and Vinyl benzoate. Solvents include water, lower alcohols Such as methanol, In 4-vinyl-8-methyl-1,7-nonadienyl acylate (XIII) ethanol, propanol, isopropanol and butanol or amides Such obtained as the intermediate, R is a hydrogen atom, C-C, 15 as tetrahydrofuran, dimethylformamide, dimethylacetamide, lower alkyl group or a phenyl, naphthyl or benzyl group dimethylimidazolidinone and N-methylpyrrollidone or a which may have a C-C alkyl group. mixture of these Solvents. Among them, methanol, ethanol, Preferred specific examples of 4-vinyl-8-methyl-1,7- tetrahydrofuran and the like may be preferably used. The nonadienyl acylate (XIII) include 4-vinyl-8-methyl-1,7- hydrophilic Solvent is generally used in a ratio ranging from nonadienyl acetate, 4-Vinyl-8-methyl-1,7-nonadienyl about 0.1 to 25 parts by volume, preferably from 0.8 to 3 propionate, 4-Vinyl-8-methyl-1,7-nonadienyl butyrate, parts by Volume, relative to one part by weight of 4-vinyl 4-vinyl-8-methyl-1,7-nonadienyl pivalate and 4-vinyl-8- 8-methyl-1,7-nonadienyl acylate (XIII). methyl-1,7-nonadienylbenzoate. After the reaction is completed, the resulting reaction Specific examples of the salts (V) include silver triflate mixture is treated in a usual way. The mixture is then (CFSOOAg), potassium nonaflate (CFSOOK), lantha 25 distilled to extract the objective 4-vinyl-8-methyl-7-nonenal num triflate (CFSOO)-La, Samarium triflate (CFSOO) (XI). Sm and ammonium triflate (CFSOONH). Commer 4-Vinyl-8-methyl-7-nonenal (XI) according to the present cially available products may be used as it is. invention has a high diffusibility and a Strong aliphatic To form a ruthenium catalyst from the ruthenium com aldehyde-like fragrance, emanating Simultaneously a citrus pound (IV) and the salts (V), the compounds (IV) and (V) and rose-like fragrance. When it is diluted, it exudes a Sweet may be mixed in an appropriate reaction System. The and milky fragrance like 1-citronellol. Therefore, it can be amount of Salts (V) used in the reaction generally ranges used in general-purpose applications Such as citrus type or from 0.5 to 10 equivalents, preferably from 1.0 to 3.0 floral green type perfumes, as Well as raw blending essences equivalents, relative to one equivalent of the ruthenium for melons, cucumbers or the like. According to the present compound. 35 invention, a perfume composition containing 4-vinyl-8- In the preparation of the 4-vinyl-8-methyl-1,7-nonadienyl methyl-7-nonenal, alone or with other common perfume acylate (XIII), previously prepared ruthenium compounds essences, may be used as the fragrance component. may be used as reaction catalysts. Alternatively, the Starting The other perfume essences include Such widespread materials of ruthenium compound may be separately added perfume components as those described by S. Arctander in to the reaction System, So as to catalyze the reaction. 40 “Perfume and Flavor Chemicals”, published in 1969, In 4-vinyl-8-methyl-1,7-nonadienyl acylate (XIII) thus Montclair, N.J., U.S.A. Typical examples of the perfume are obtained, the double bond may form any one of trans-type, C-pinene, limonene, cis-3-hexenol, phenylethyl alcohol, cis-type and a mixture of the both. However, preferred form Styraryl acetate, eugenol, rose oxide, linalool and benzalde is cis-type. hyde. The inventive 4-vinyl-8-methyl-7-nonenal (XI) can be 45 The proportion of 4-vinyl-8-methyl-7-nonenal (XI) to be obtained easily by hydrolyzing 4-vinyl-8-methyl-1,7- included in the perfume composition may be determined nonadienyl acylate (XIII). according to the type and purpose of perfume preparation. According to a specific hydrolyzing method, 4-Vinyl-8- Preferably it is in the range of between 10 ppm and 10% by methyl-1,7-nonadienyl acylate (XIII) is heated and stirred in weight, based on the total amount of the perfume an aqueous acid Solution Such as acqueous Sulfuric acid, 50 composition, though no particular limitation is imposed on aqueous hydrochloric acid and/or aqueous acetic acid. it. Various blending perfumes and fragrance-controlling Alternatively, it can be heated, where necessary, in an agents may be appropriately added, depending on the pur aqueous alkali Solution Such as Sodium hydroxide. pOSe. Examples of the acid used in the production of 4-Vinyl The present invention enables the production of 4-vinyl 8-methyl-7-nonenal (XI) include mineral acids Such as Sul 55 8-methyl-7-nonenal (XI) with high purity in a simple furic acid and hydrochloric acid, and organic acids Such as method at a low cost. This compound is a novel perfume acetic acid. These acids may be used either alone or in an which has a high diffusibility and a strong aliphatic appropriate mixture thereof. aldehyde-like fragrance, emanating Simultaneously a Examples of the alkali Sodium include Sodium hydroxide, Slightly citrus- and rose-like fragrance. The inventive com potassium hydroxide and barium hydroxide. These alkalis 60 pound can therefore be used for general-purpose applica may be used either alone or in an appropriate mixture tions Such as citrus type or floral green type perfumes, as thereof. The concentration of the aqueous acid or alkali well as raw blending agents for melons, cucumbers or the Solutions may be adjusted depending upon the reaction like. Also it can be used to enhance a citrus-like fragrance. condition. In a mineral acid, an organic acid and an alkali, The perfume composition of the present invention compris the preferred concentration ranges from 1 to 30% by 65 ing the inventive compound can be used in a wide range of equivalent, 1 to 5% by equivalent and 1 to 5% by equivalent, application fields Such as aromatics, various cosmetics, respectively. Sanitary materials. US 6,239,324 B1 25 26 The diene compound of the present invention is a very mixture was heated to 70° C. and stirred for one hour. After important compound as an intermediate for Synthesizing the temperature of the reaction mixture was returned to room compounds, particularly, terpenes, which are useful for temperature, the reaction mixture was concentrated under intermediates for Synthesizing medicines. reduced pressure and passed through an alumina column to According to the present invention, a low molecular 5 purify. A yellow band was collected, followed by distilling weight diene compound of high purity which is Superior in the solvent to obtain a yellowish orange solid. This solid was regioSelectivity can be produced in a simple method at a low recrystallized from chloroform/diethyl ether to obtain 0.256 price. g(yield: 77%) of (m-pentamethylcyclopentadienyl) (m- norbornadiene) ruthenium (II) chloride. EXAMPLE The various spectrum data of the product accorded with The present invention will be hereinafter described in the value of the literature. more detail by way of examples, reference examples and comparative examples, which are not intended to limit the Reference Example 3 present invention. It is needless to Say that the present 15 Synthesis of (N-2-aminoethyl-p- invention can be changed variously without departing from toluenesulfonamide) (m-benzene) ruthenium (II) the technological idea of the invention. chloride In the examples described below, the product is measured for its chemical purity and identified according to the 2.5 g (10 mmol) of (m-benzene)ruthenium(II) dichloride following methods. dimer and 2.14 g (10 mmol) of N-2-aminoethyl-p- (Measurement of chemical purity) toluenesulfonamide were heated with Stirring together with The chemical purity is measured by a gas chromato 80 ml of isopropyl alcohol at 80 C. for 4 hours. The reaction graphic method (GLC). The conditions for the measurement mixture was concentrated and washed to obtain 4 g (yield: are as follows: 93%) of (N-2-aminoethyl-p-toluenesulfonamide) (m- 25 benzene) ruthenium (II) chloride. Applied analytical instrument: HP5890 Series II Gas The various spectrum data of the product accorded with chromatograph manufactured by Hewlett Packard the value of the literature. Column: Neutrabond-1 (NB-1:0.25 mmx30 m) Detector: FID Example 1 "H-Nuclear magnetic resonance spectrum (H-NMR) Synthesis of 4-methylhexa-1,5-dien-1-yl acetate Instrument: GEMINI2000 (1H,200 MHz), (manufactured by Varian) 6.5 mg (0.020 mmol) of (m- Infrared absorption spectrum (IR) pentamethylcyclopentadienyl) (m"-isoprene) ruthenium (II) Instrument: FTIR-8200 PC model (manufactured by Nip chloride obtained in the Reference Example 1, 5 ml(50 pon Bunko Kogyo Kabushiki Kaisha) 35 mmol) of isoprene, 5 ml (54 mmol) of vinyl acetate and 5 ml of methanol were heated with stirring at 80° C. for 15 hours Measuring method: Film in an argon atmosphere. The reaction mixture was distilled (Identification of products) to obtain non-reacted isoprene and Vinyl acetate and, in The identification of the product was made using a Succession, 1.07 g (yield: 14% based on isoprene) of a "H-NMR spectrum by comparing with data described in 40 co-dimer (4-methylhexa-1,5-dien-1-yl acetate). No distilla known literature. tion residue, Such as polymers, was observed and the reac tion proceeded selectively (purity: 91%, regioisomer: 4%, Reference Example 1 cyclic dimer of dienes: 5%). Boiling point: 80-100° C./10 mmHg Synthesis of (m-pentamethylcyclopentadienyl) (m- 45 isoprene) ruthenium (II) chloride H-NMR (200 MHz, CDC1): 200 mg (0.65 mmol as a monomer) of a (m- 81.01(3H, d, J=6.6 Hz), 2.14(3H, s), 2.0–2.4(3H, m), pentamethylcyclopentadienyl) ruthenium (III) dichloride 4.8–5.1(3H, m), 5.74(1H, ddd, J=6.8, 10.2, 17.2 Hz), 7.08 dimer and 42 mg of a Zinc powder were Suspended in 20 ml (1H, dm, J=6.6 Hz) of methanol and the Suspension was cooled in an argon 50 Gas chromatography analysis: atmosphere in an ice-cooled bath. To the mixture was added Column: NB-1 (produced by G. L. Science) 2 ml of isoprene and further 42 mg of zinc. The reaction Measurement temperature: 60-250° C. (temperature was mixture was stirred for one hour while it is ice-cooled, raised at a rate of 10° C./minute) followed by filtration and concentration, to obtain 75 mg Retention time=7.29 minutes (product), 7.84 minutes (yield: 34%) of (mi-pentamethylcyclopentadienyl) (m- 55 (isomer), 7.53 minutes (dimer) isoprene) ruthenium (II) chloride. The various spectrum data of the product accorded with Example 2 the value of the literature. Synthesis of 4-methylhexa-1,5-dien-1-yl acetate 60 Reference Example 2 16.5 mg (0.038 mmol) of (N-2-aminoethyl-p- Synthesis of (m-pentamethylcyclopentadienyl)(m- toluenesulfonamide) (m-benzene) ruthenium (II) chloride obtained in the Reference Example 3 and 9 mg (0.035 norbornadiene) ruthenium (II) chloride mmol) of silver triflate were prepared together with 2.5 ml 270 mg of a (m-pentamethylcyclopentadienyl)ruthenium 65 (20 mmol) of methanol, 2.5 ml of isoprene and 2 ml (22 (II) dichloride dimer was suspended in 10 ml of methanol, mmol) of vinyl acetate and the mixture was heated with to which was added 3 ml (24.5 mmol) of norbornadiene. The stirring at 100° C. for 13 hours in an argon atmosphere. The US 6,239,324 B1 27 28 reaction mixture was poured into water and the Separated erence Example 1, 10 ml (100 mmol) of isoprene, 10 ml (87 organic layer was analyzed by gas chromatography. AS a mmol) of styrene and 15 ml of methanol were heated with result, the organic layer was a composition consisting of stirring at 100° C. for 12 hours in an argon atmosphere. After 70% of 4-methylhexa-1,5-dien-1-yl acetate, 25% of a regioi Styrene was recovered under reduced pressure, a part of the Somer and 5% of a cyclic dimer of dienes. residue was diluted with water and the organic layer was concentrated and distilled to obtain 42 mg of an objective Example 3 product (purity: 89.4%, regioisomer: 7.0%, cyclic dimer of Synthesis of 4-methylhexa-1,5-dien-1-yl acetate dienes: less than 1%). Boiling point: 120° C./1 mmfg. 4 mg (0.016 mmol) of (m-benzene) ruthenium (II) dichloride, 15 mg (0.058 mmol) of silver triflate and 11.2 mg H-NMR (200 MHz, CDC1): (0.052 mmol) of N-2-aminoethyl-p-toluenesulfonamide 81.20(3H, d, J=6.4 Hz), 2.1-2.5(3H, m), 4.9(1H, dm, were placed in a Sealed tube, which was then charged with J=10.6), 5.0(1H, dm, J=17.4 Hz), 5.6–5.8(1H, m), 5.7(1H, 2 ml (20 mmol) of isoprene, 2 ml (22 mmol) of vinyl acetate ddd, J=6.8, 10.6, 17.4 Hz), 6.5(1H, dm, J=11.8 Hz), 7.2-7.5 and 2 ml of methanol. The mixture was heated with stirring 15 (5H, m) at 100° C. for 6 hours in an argon atmosphere. The reaction Gas chromatography analysis: mixture was poured into water and the organic layer was Column: NB-1 (produced by G. L. Science) concentrated to obtain 0.17 g (yield: 6% based on isoprene) Measurement temperature: 60–160° C. (temperature was of a co-dimer (4-methylhexa-1,5-dien-1-yl acetate) (Purity: raised at a rate of 5 C/minute) 75%, regioisomer: 17%, cyclic dimer of dienes: 8%). Retention time=18.8 minutes (product), 17.4 minutes Example 4 (isomer) Synthesis of 4-methylhexa-1,5-dien-1-yl acetate Example 7 4.5 mg (0.014 mmol) of (m- pentamethylcyclopentadienyl) ruthenium (III) dichloride, 2 25 Synthesis of hexa-1,5-dien-1-yl pivalate ml of methanol, 2 ml (20 mmol) of isoprene and 2 ml (22 13.. 6 mg (0.037 mmol) of (m- mmol) of vinyl acetate were placed and the mixture was pentamethylcyclopentadienyl) (m"-norbornadiene) ruthe heated with stirring at 100° C. for 12 hours in an argon nium (II) chloride obtained in the Reference Example 2, 6 atmosphere. The reaction mixture was poured into water and ml (74 mmol) of 1,3-butadiene, 2 ml (13.5 mmol) of vinyl the Separated organic layer was analyzed by gas chroma pivalate and 2 ml of methanol were heated with Stirring at tography. As a result, the organic layer was a composition 100° C. for 15 hours in a butadiene atmosphere. The reaction consisting of 90% of 4-methylhexa-1,5-dien-1-yl acetate, mixture was diluted with water and the organic layer was 4% of a regioisomer and 6% of a cyclic dimer of dienes. concentrated to yield 1.1 g (yield: 45%) of a product. The Example 5 35 product was distilled to obtain 0.30 g (yield: 12%) of an addition product as a pure material. Synthesis of 4-methyl-1,5-hexadien-1-yl pivalate Boiling point: 110° C./15 mmHg 11.8 mg (0.035 mmol) of (m- H-NMR (200 MHz, CDC1): pentamethylcyclopentadienyl) (m"isoprene) ruthenium (II) 81.25(9H, s), 2.0–2.4(4H, m), 4.8–5.1(3H, m), 5.80(1H, chloride obtained in the Reference Example 1, 1 ml(10 40 ddd, J=6.4, 10.2, 16.8 Hz), 7.03(1H, dt, J=6.4, 1.2 Hz) mmol) of isoprene, 1 ml (6.7 mmol) of vinyl pivalate and 2 Gas chromatography analysis: ml of methanol were heated with stirring at 100° C. for 12 hours in an argon atmosphere. The reaction mixture was Column: NB-1 (produced by G. L. Science) diluted with water and the organic layer was concentrated Measurement temperature: 60–160° C. (temperature was and distilled to yield 1.1 g (yield: 84%) of a product. No 45 raised at a rate of 5 C/minute) distillation residue, Such as polymers, was observed and the Retention time=13.5 minutes (product) reaction proceeded selectively (purity: 94.6%, regioisomer: 4.7%, cyclic dimer of dienes: less than 1%). Example 8 Boiling point: 110° C./10 mmHg 50 Synthesis of 8-methyl-4-vinyl-nona-1,7-dien-1-yl H-NMR (200 MHz, CDC1): pivalate 81.01(3H, d, J=6.4 Hz), 1.25(9H, s), 2.0–2.4(3H, m), 14.6 mg (0.040 mmol) of (m- 4.8–5.0(1H, m), 4.93(1H, dm, J=10.4 Hz), 4.98(1H, dm, pentamethylcyclopentadienyl) (m"-norbornadiene) ruthe J=17.2 Hz), 5.75(1H, ddd, J=6.8, 10.4, 17.2 Hz), 7.04(1H, nium(II) chloride obtained in the Reference Example 2, 1.5 dim, J=6.4 Hz) 55 ml (78%, 10 mmol) of 7-methyl-3-methylene-1,6-octadiene Gas chromatography analysis: (myrcene), 1.5 ml (10 mmol) of vinyl pivalate and 2 ml of Column: NB-1 (produced by G. L. Science) methanol were heated with stirring at 100° C. for 15 hours Measurement temperature: 60–160° C. (temperature was in an argon atmosphere. The reaction mixture was diluted raised at a rate of 5 C/minute) with water and the organic layer was concentrated and Retention time = 15.2 minutes (product), 16.2 minutes 60 distilled to obtain 0.75 g (yield: 41%) of an addition product (isomer) as a pure material. Example 6 Boiling point: 110° C./0.5 mmHg Synthesis of 1-phenyl-4-methylhexa-1,5-diene H-NMR (200 MHz, CDC1): 65 81.25(9H, s), 1.2–1.6(2H, m), 1.58(3H, s), 1.68(3H, s), 55 mg (0.16 mmol) of (m-pentamethylcyclopentadienyl) 1.9-2.4(5H, m), 4.7-5.2(4H, m), 5.60(1H, ddd, J=8.0, 11.0, (m"-isoprene) ruthenium (II) chloride obtained in the Ref 16.0 Hz), 7.03(1H, dm, J=6.4 Hz) US 6,239,324 B1 29 30 Gas chromatography analysis: sulfuric acid (10 ml) and the mixture was stirred for 16 hours Column: NB-1 (produced by G. L. Science) at room temperature. The resulting mixture was poured into Measurement temperature: 60–160° C. (temperature was an aqueous Saturated Sodium bicarbonate carefully and raised at a rate of 5 C./minute) and the temperature was Subjected to an extraction using an ether. The extract was raised up to 250 C. at a rate of 10° C./minute. 5 concentrated, to which was added an aqueous acetic acid solution (acetic acid (10 ml) was mixed in water (20 ml)) Retention time=25.9 minutes (product), 26.6 minutes and the mixed solution was stirred under heating at 100 C. (isomer) for 2 hours to complete hydrolysis. The reaction mixture was Example 9 poured into an aqueous Sodium bicarbonate Solution care Synthesis of 8-acetoxy-8-methyl-4-vinyl-1-nonen-1- fully and Subjected to an extraction using an ether. The ether yl acetate layer was washed with an aqueous Saturated Sodium bicar bonate Solution, water and a Saturated brine in this order 122 mg (0.033 mmol) of (m- once, followed by drying using Sodium Sulfate anhydride. pentamethylcyclopentadienyl) (m"-norbornadiene) ruthe The resulting Substance was concentrated and distilled to nium (II) chloride obtained in the Reference Example 2, 1.5 15 obtain 4.2 g (yield: 66%) of the objective compound. g (7.6 mmol) of 2-methyl-6-methylene-7-octen-2-yl acetate (myrcenyl acetate), 2 ml (22 mmol) of vinyl acetate and 2 ml H-NMR (200 MHz, CC1): 81.02(3H, d, J-6 Hz), 1.10(s, of methanol were heated with stirring at 100° C. for 15 hours 9H), 1.5(2H, m), 2.2(3H, m), 4.8–5.0(2H, m), 5.4–5.8(1H, in an argon atmosphere. The reaction mixture was diluted m), 7.5(1H, t, J=4 Hz). with water and the organic layer was concentrated and The resulting product is a transparent liquid which has a distilled to obtain 1.1 g (yield: 50%) of an addition product high diffusibility, and a strong and fresh green fruit-like as a pure material. fragrance. Boiling point: 120° C./0.5 mmHg H-NMR (200 MHz, CDC1): Example 13 81.2–1.8(4H, m), 1.41(4H, s), 1.96(3H, s), 2.15(3H, s), 25 1.9-2.4(3H, m), 4.7-5.1(3H, m), 5.57(1H, ddd, J=8.0, 11.0, 16.2 Hz), 7.03(1H, dm, J=6.4 Hz) Preparation of an apple type blending perfume Gas chromatography analysis: Column: NB-1 (produced by G. L. Science) (Ratio by weight) Measurement temperature: 60–160° C. (temperature was Y-undecalactone 60 raised at a rate of 5 C./minute) and the temperature was L-citronellal 65 1,1-dimethyl-2-phenylethyl acetate 22O raised up to 250 C. at a rate of 10° C./minute. Ethylheptoate 6 Retention time=27.4 minutes (product), 27.9 minutes Cis-3-hexen-1-ol 25 (isomer) Cis-3-hexenyl acetate 5 35 Trans-2-hexenyl acetate 16 Example 10 Hexyl acetate 18O Hydratropaldehyde (2-phenylpropanal) 3 Synthesis of 4-methylhexa-1,5-dien-1-yl acetate C-ionone 3O Isoamyl butylate 110 (p-Cymene)ruthenium dichloride dimer (27.8 mg, 0.091 Methyl 2-methylbutylate 70 mmol Ru) and sodium triflate (80 mg, 0.464 mmol) were 40 Ethylene brassylate 110 dissolved in 10 ml of methanol. To the mixed solution were added isoprene (3 ml) and vinyl acetate (5 ml) and the 900 mixture was stirred under heat at 100° C. for 14 hours. The resulting product was poured into water and extracted using toluene and the extract was Subjected to a GLC analysis. AS 45 To 900 parts of the above blending perfume was added a result, it was confirmed that a co-dimer was produced with 100 parts of 4-methyl-5-hexen-1-all obtained in the Example the conversion rate being 10% and the ratio of an isomer 12 to obtain an apple type blending perfume having a fresh being 17:3. and green fruit-like Scent. For comparison, 100 parts of Example 11 cis-3-hexenal, a Similar fragrant compound, was used in 50 place of 4-methyl-5-hexen-1-all to prepare a perfume com Synthesis of 4-methyl-1,5-hexadien-1-yl pivalate position. The both perfumes were evaluated by five panelists (Benzene)ruthenium dichloride dimer (14 mg., 0.056 in an acceptability test. As a result, five panelists all pre mmol Ru), silver triflate (20 mg, 0.078 mmol) and 2,2- ferred the perfume containing 4-methyl-5-hexen-1-all and methylenebis(4-phenyl-2-oxazoline) (17.8 mg, 0.058 mmol) evaluated it as a desirable perfume composition for well were dissolved in 2 ml of methanol. To the mixed Solution 55 balanced shampoos which had a mild and fruity fragrance. were added isoprene (2 ml) and vinyl pivalate (1 ml) and the mixture was stirred under heat at 100° C. for 10 hours. The Example 14 resulting product was poured into water and the Separated organic layer was Subjected to a GLC analysis. As a result, it was confirmed that a co-dimer was produced with the 60 conversion rate being 72% and the ratio of an isomer being Herbal green type blending perfume 4:1. (Ratio by weight) Example 12 Allylamyl glycolate 3O Synthesis of 4-methyl-5-hexen-1-al Armoise oil 8O 65 Basil oil 1OO 4-Methyl-1,5-hexadien-1-yl (8.8 g., 57 mmol) was dis 3-damascon 1O solved in methanol (50 ml), to which was added 20% US 6,239,324 B1 31 32 water and the organic layer was analyzed by gas chroma -continued tography to confirm that the title compound (addition product) having a purity of 76% (regioisomer: 26%) was Herbal green type blending perfume produced at a conversion rate of 17%. (Ratio by weight) Example 17 Estragon oil 40 Galbanum oil 3O Synthesis of 4-vinyl-8-methyl-7-nonenal from 4 1,3-benzodioxy-5-yl-2-methylpropanal 150 Cis-3-hexen-1-ol 40 Vinyl-8-methyl-1,7-nonadienyl acetate Linalool 370 Dimethyl tetrahydrobenzaldehyde 1OO 4.8 g (21.6 mmol) of 4-vinyl-8-methyl-1,7-nonadienyl acetate obtained in Example 16 was dissolved in 10 ml of 950 methanol, to which was added 2 ml of 20% sulfuric acid and the mixture was stirred at room temperature for 16 hours. The resulting mixture was poured into water and the Solution To 950 parts of the above blending perfume was added 50 15 was Subjected to an extraction using an ether. The extract parts of 4-methyl-5-hexen-1-all obtained in the Example 12 was washed with an aqueous Saturated Sodium bicarbonate to obtain a herbal green type blending perfume having a Solution and with a Saturated Salt brine. The resulting extract green Smelling. For comparison, 50 parts of trans-2-hexenal, was concentrated, to which acqueous acetic acid (prepared by a similar fragrant compound, was used in place of 4-methyl adding 20 ml of water and 10 ml of tetrahydrofuran to 10 ml 5-hexen-1-all to prepare a perfume composition. The both of acetic acid) was added. The mixture was heated with perfumes were evaluated by ten panelists in an acceptability stirring at 100° C. for 2 hours to complete hydrolysis. The test. As a result, nine panelists preferred the perfume con reaction mixture was poured into water and the resulting taining 4-methyl-5-hexen-1-al. Their conclusion was based reaction mixture was Subjected to an extraction using an on the finding that the inventive composition was relatively ether. The ether layer was washed with an aqueous Saturated odorless and had a mild and herbal green fragrance. They 25 Sodium bicarbonate Solution, water and a Saturated Salt brine further evaluated that it was a perfume composition Suitable in this order, followed by drying using Sodium Sulfate for well-balanced men's cosmetics. anhydride. The dried Substance was concentrated and dis tilled to obtain 1.1 g (yield: 28%) of the title compound. Example 15 Boiling point: 120° C./5 mmHg Synthesis of 4-vinyl-8-methyl-1,7-nonadienyl IR: 1726 cm (CHO) acetate H-NMR (200 MHz, CDC1): 30 mg (0.079 mmol) of (m-pentamethylcyclopenta 80.8–2.1(7H, m), 1.58(3H, s), 1.66(3H, s), 2.3–2.5(2H, m), 4.8–5.2(3H, m), 5.45(1H, t, J=9.7, 11.1, 16.6 Hz), dienyl) (m"-norbornadiene) ruthenium(II) chloride obtained 35 in the Reference Example 2, 10 ml (78%, 46 mmol) of 9.78(1H, s) myrcene, 10 ml (109 mmol) of vinyl acetate and 15 ml of The resulting product was a transparent liquid which had methanol were heated with stirring at 70° C. for 23 hours in a high diffusibility and a strong aliphatic aldehyde-like an argon atmosphere. The reaction Solution was diluted with fragrance emanating Simultaneously a slightly citrus- and water and the organic layer was fractionated. The organic 40 rose-like fragrance. layer was concentrated and distilled to obtain 4.8 g (yield: 47%) of the title compound (addition product) as a pure Example 18 product. Synthesis of 4-vinyl-8-methyl-7-nonenal from 4 Boiling point: 110° C./0.5 mmHg vinyl-8-methyl-1,7-nonadienyl pivalate H-NMR (200 MHz, CDC1): 45 81.2–1.6(2H, m), 1.58(3H, s), 1.68(3H, s), 1.9-2.4(5H, The above 4-vinyl-8-methyl-1,7-nonadienyl pivalate m), 2.18(3H, s), 4.7-5.2(4H, m), 5.60(1H, ddd, J=8.0, 11.0, obtained in Example 17 instead of 4-vinyl-8-methyl-1,7- 16.0 Hz), 7.03(1H, dm, J=6.4 Hz) nonadienyl acetate obtained in Example 18 was hydrolyzed Gas chromatography analysis: in the same conditions as in Example 18 to obtain the title 50 compound, 4-Vinyl-8-methyl-7-nonenal. Measurement temperature: 60–160° C. (temperature was raised at a rate of 5 C/minute) and then 160 to 250° C. Example 19 (temperature was raised at a rate of 10° C./minute) Retention time=23.1 minutes (23.1 minutes, 96% purity, 23.9 minutes for an isomer) 55 Citrus type blending perfume: Example 16 (Ratio by weight) Synthesis of 4-vinyl-8-methyl-1,7-nonadienyl 1-Decanal 7 pivalate Citral 2O 60 Citronelliol 950 1O 23.7 mg (0.055 mmol) of (N-2-aminomethyl-p-toluene C-damascon 2 sulfonamide) (m-benzene) ruthenium (II) chloride obtained Dihydromyrcenol 3O Ethyl 2-methylbutyrate 1. in the Reference Example 4 and 17.5 mg (0.068 mmol) of Grape fruit oil 3O silver triflate were mixed in 2 ml of methanol, to which were Lemon oil 160 added 2 ml (purity: 78%, 1.25 g, 9.2 mmol) of myrcene and 65 Lime oil 2OO 1.73 g (13 mmol) of vinyl pivalate. The mixture was stirred Linalool 3O at 70° C. for 6 hours. The reaction mixture was diluted with US 6,239,324 B1 33 34 group which may have a Substituent; R represents a -continued phenyl group which may have a C-C lower alkyl group, or a C-C acyloxy group which may have a Citrus type blending perfume: phenyl group, a naphthyl group or a benzyl group as a (Ratio by weight) Substituent, the wavy line showing a cis-isomer, a Orange Oil 490 trans-isomer or mixture thereof; R is a hydroxy group which reversibly forms an aldehyde group through shifting of the position of the double bond adjacent to 1O Said hydroxy group, Said process at least comprising To 980 parts of the above blending perfume was added 20 the Step of reacting a 2-Substituted-1,3-butadiene rep parts of 4-vinyl-8-methyl-7-nonenal to obtain a citrus type resented by the following general formula (I): blending perfume having a fresh and green Smelling or feeling. (I) 15 R1 Example 20 N-N

Green type blending perfume: wherein R' is defined as indicated above; (Ratio by weight) with a terminal olefin represented by the following general 1% dipropylene glycol solution of 2O 2-trans-6-cisnomadienal formula (II): Benzyl salicylate 8O Cis-3-hexenol 0.5 25 (II) Cyclamenaldehyl 2O R2 Kovanol 2OO L-laurynal 40 Melonal 1.5 Methyl ionone 2O Phenylethyl alcohol 296 Hexylcinnamic aldehyde 3OO wherein R is defined as indicated above;

978 in a hydrophilic Solvent in the presence of a ruthenium compound. 2. A process for producing a diene compound according To 978 parts of the above blending perfume was added 22 35 parts of 4-vinyl-8-methyl-7-nonenal to obtain a melon and to claim 1, wherein said R in the formula (II) is a C-C, cucumber type blending perfume having a green Smelling or acyloxy group which may have a phenyl group, a naphthyl feeling. group or a benzyl group as a Substituent. Although the invention has been described with reference 3. A process for producing a diene compound according to particular means, materials and embodiments, it is to be 40 to claim 1, wherein Said ruthenium compound comprises a understood that the invention is not limited to the particulars ruthenium catalyst represented by the following formula disclosed and extends to all equivalents within the Scope of (III): the claims. The present disclosure relates to Subject matter contained 45 (III) in priority Japanese Application Nos. HEI-10-240413, HEI 10-321700, HEI-11-025781 and HEI-11-194185, filed on Aug. 26 and Nov. 12, 1998, and Feb. 3 and Jul. 8, 1999, respectively, which are herein expressly incorporated by reference in their entireties. 50 While the invention has been described in detail and with reference to specific embodiments thereof, it will be appar ent to one skilled in the art that various changes and modifications can be made therein without departing from wherein R", R, R, R7 and R, which may be the same or the Spirit and Scope thereof. 55 different, represent a hydrogen atom or a C-C lower What is claimed is: alkyl group, or two adjacent groups among R', R, R, 1. A process for producing a diene compound represented R" and R may be bonded to each other so as to form by the formula (IX): a five- or six-membered ring; W represents a 1,3- butadiene group, an isoprene group, a myrcene group, (DX) 60 a 1,5-cyclooctadiene group, a norbornadiene group, a R1 2,3-dimethyl-1,3-butadiene group or a halogen atom; and X' represents a halogen atom. N-N-N- 4. A proceSS for producing a diene compound according 65 to claim 1, wherein Said ruthenium compound comprises a wherein R represents a hydrogen atom, a C-C alkyl ruthenium catalyst formed by mixing a ruthenium com group which may have a Substituent or a C-C alkenyl pound represented by the following formula (IV): US 6,239,324 B1 36 bidentate ligand represented by the following formula (VII): (IV) 9 (VII) R | R15 R10 R14 N A O-X R16 R11 R13 N ln O / R12 2 V R17 wherein R, R', R', R, R and R', which may be the Same or different, represent a hydrogen atom or a wherein R and R', which may be the same or different, C-C lower alkyl group, or two adjacent groups 15 represent an aryl group which may have a C-C lower among R, R', R', R', RandR'' may bond to each alkyl group, a C-C lower alkyl group, an aralkyl other So as to form a five- or six-membered ring; X" group or a C-C lower alkenyl group as a Substituent; represents a halogen atom; R' and R' represent a R° and R', which may be the same or different, hydrogen atom, a C-C lower alkyl group, a C-C, represent an aryl group which may have a C-C lower cycloalkyl group, or a phenyl group, a naphthyl group alkyl group, a C-C lower alkyloxy group which may or a benzyl group, each of which may be Substituted have a substituent or a hydrogen atom; R and R or with a C-C lower alkyl group or with a halogen atom, R'' and R' may form a ring which may include an or R' and Rare combined with each other to form Oxygen atom; r, S, t and u respectively denote 0 or 1, a C-C alkylene group; R represents a hydrogen and R to R", which may be the same or different, atom, a C-C lower alkyl group, a C-C, cycloalkyl 25 respectively represent a hydrogen atom, a C-C lower group, a lower alkyl halide, or a phenyl group, a alkyl group or a C-C lower alkenyl group, or any two naphthyl group or a benzyl group, each of which may groups among R to R' may be bonded to each other be substituted with a C-C lower alkyl group or with So as to form a five- or six-membered ring which may a halogen atom; and n denotes 0 or 1, have one or more Substituents, with salts represented by the following formula (V): to Said ruthenium catalyst So that the activity of Said ruthe M(X), (V) nium catalyst is controlled. 7. A proceSS for producing a diene compound according wherein M represents a mono-, di-, or tri-cation; X to claim 1, wherein said hydrophilic Solvent comprises at represents an anion; a denotes 1 when M is a mono least one Solvent Selected from the group consisting of cation, 2 when M is a di-cation or 3 when M is a 35 methanol, ethanol, a mixture of methanol and water and a tri-cation. mixture of ethanol and water. 5. A process for producing a diene compound according 8. A proceSS for producing a diene compound according to claim 1, wherein Said ruthenium compound comprises a to claim 1, wherein Said 2-Substituted-1,3-butadiene is at ruthenium catalyst formed by mixing a ruthenium com least one compound Selected from the group consisting of pound represented by the following formula (VI): 40 a) isoprene b) butadiene; and (VI) R9 c) myrcene represented by the formula (VIII): 45 R10 Cox,R14 (VIII) R11 R13 R12 50

wherein R,R,R,R,R, and R', which may be the Same or different, represent a hydrogen atom or a N-1s C-C lower alkyl group, or two adjacent groups 55 among R, R', R'', R', R', and R' may bond to 9. A process for producing 4-methyl-5-hexen-1-all repre each other So as to form a five- or six-membered ring, sented by the formula (X): and X' represents a halogen atom; with a salt represented by the following formula(V): (X) M(X), (V) 60 wherein M represents a mono-, di-, or tri-cation, X n represents an anion, and a denotes 1 when M is a mono-cation, 2 when M is a di-cation, or 3 when M is a tri-cation. 65 Said process comprising the Steps of: 6. A process for producing a diene compound according a) preparing a diene compound represented by the for to claim 1, wherein the process comprises adding a nitrogen mula (IX): US 6,239,324 B1 37 38 a) reacting myrcene represented by the formula (VIII): (DX) (VIII) N-N-N- wherein R represents a methyl group; R represents a C-C acyloxy group which may have a phenyl 1O group, a naphthyl group or a benzyl group as a S1S substituent, R is a hydroxy group which reversibly forms an aldehyde group through shifting of the with a vinyl acylate represented by the following position of the double bond adjacent Said hydroxy formula (XII): group; and the wavy line shows a cis-isomer, a 15 trans-isomer, or a mixture thereof; (XII) by reacting 2-Substituted-1,3-butadiene represented by the following formula (I): N O (I) R1 wherein R represents a hydrogen atom, a C-C lower alkyl group, a phenyl group, a naphthyl group or a benzyl group, each of which may have a C-C, N-N 25 lower alkyl group as a Substituent; in a hydrophilic Solvent in the presence of a ruthenium compound, So as to form a 4-vinyl-8-methyl-1,7- wherein R' represents a methyl group; nonadienyl acylate represented by the following for with a terminal olefin represented by the following for mula (XIII): mula (II): (XIII) (II) R2 35

wherein R represents a C-C, acyloxy group which may have a phenyl group, a naphthyl group or a benzyl group as a Substituent; 40 in a hydrophilic Solvent in the presence of a ruthenium compound, to obtain a corresponding diene compound; wherein R represents a hydrogen atom, a C-C lower and alkyl group, a phenyl group, a naphthyl group or a b) hydrolyzing said diene compound. 45 benzyl group, each of which may have a C-C, lower alkyl group as a Substituent; and 10. A process for producing 4-vinyl-8-methyl-7-nonenal b) hydrolyzing Said 4-vinyl-8-methyl-1,7-nonadienyl acy represented by the formula (XI): late. 11. A process for producing 4-vinyl-8-methyl-7-nonenal (XI) 50 (XI) according to claim 10, wherein said ruthenium com pound comprises a ruthenium catalyst represented by the following formula (III):

(III) 55

CHO

60

Said process comprising the Steps of:

65 US 6,239,324 B1 39 40 wherein R", R, R, R7 and R, which may be the same or different, represent a hydrogen atom or a C-C lower (VI) alkyl group, and two adjacent groups among R', R, R9 R, R and R may be bonded to each other so as to form a five- or six-membered ring; W represents a 5 1,3-butadiene group, an isoprene group, a myrcene Oux, group, a 1,5-cyclooctadiene group, a norbornadiene group, a 2,3-dimethyl-1,3-butadiene or a halogen atom; and X' represents a halogen atom. R12 12. A process for producing 4-vinyl-8-methyl-7-nonenal 1O according to claim 10, wherein Said ruthenium compound wherein R,R,R,R,R, and R' which may be the comprises a ruthenium catalyst formed by mixing a ruthe Same or different, represent a hydrogen atom or a nium compound represented by the following formula (IV): C-C lower alkyl group, or two adjacent groups 15 among R. R. R. R. R', and R' may bond to (IV) each other So as to form a five- or six-membered ring, R9 H 17 and X' represents a halogen atom; R with a salt represented by the following formula (V): 10 14 R R N M(X), (V) }HRuxV R16 2O wherein M represents a mono-, di-, or tri-cation, X2 R11 R13 N ln represents an anion, and a denotes 1 when M is a / mono-cation, 2 when M is a di-cation, or 3 when M is R12 Os, a tri-cation. R17 14. A process for producing 4-vinyl-8-methyl-7-nonenal 25 according to claim 13, wherein the process comprises add ing a nitrogen bidentate ligand represented by the following wherein R,R,R,R, R and R', which may be the formula (VII): Same or different, represent a hydrogen atom or a C-C lower alkyl group, or two adjacent groups (VII) among R, R'R'', R, R and R' may be bonded 30 to each other So as to form a five- or six-membered ring; X' represents a halogen atom; R' and R' represent a hydrogen atom, a C-C lower alkyl group, a C-C7 cycloalkyl group, a phenyl group, a naphthyl group or a benzyl group, each of which may be 35 Substituted with a C-C lower alkyl group or with a halogen atom, or R' and R'' are combined with each other So as to form a C-C alkylene group; R' represents a hydrogen atom, a C-C lower alkyl 40 group, a C-C7 cycloalkyl group, a lower alkyl halide wherein R and R', which may be the same or different, group, a phenyl group, a naphthyl group or a benzyl represent an aryl group which may have a C-C lower group, each of which may be Substituted with a C-C, alkyl group, a C-C lower alkyl group, an aralkyl lower alkyl group or halogen atom; and n denotes 0 or group or a C-C, lower alkenyl group as a Substituent; 1, 45 R° and R', which may be the same or different, represent an aryl group which may have a C-C lower with a salt represented by the following formula (V): alkyl group as a Substituent, a C-C lower alkyloxy group which may have a Substituent or a hydrogen M(X), (V) atom; R and R' or R'' and R' may form a ring which may include an oxygen atom, r, S, t and ul 50 respectively denote 0 or 1; and R to Rf. which may wherein M represents a mono-, di- or tri-cation, X be the same or different, represent a hydrogen atom, a represents an anion; a denotes 1 when M is a mono- C-C lower alkyl group or a C-C lower alkenyl cation, 2 when M is a di-cation or 3 when M is a group, or any two groupS among R33 to R40 may be tri-cation. bonded to each other So as to form a five- or six 13. A process for producing 4-vinyl-8-methyl-7-nonenal 55 membered ring which may have Substituents, according to claim 10, wherein Said ruthenium compound to Said ruthenium catalyst So that the activity of Said ruthe comprises a ruthenium catalyst formed by mixing a ruthe nium catalyst is controlled. nium compound represented by the following formula (VI): k . . . .