JP2013147448A - Campholenic derivative and fragrance composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound capable of giving a floral or muguet-like aromatic odor, and to provide a fragrance composition containing them.SOLUTION: A compound expressed by formula (1) is provided. In the formula, n is 1 to 3; Rand Reach represents a hydrogen atom, or a methylene group is formed together with Rand R; and a dashed line (----) represents a single bond or a double bond, and when representing a double bond, n is 3. However, when the dashed line (----) represents a double bond, Rand Rdo not exist.

Description

（式中、ｎは１から３であり、Ｒ₁及びＲ₂は水素原子を表すか、Ｒ₁とＲ₂とでメチレン基を形成し、点線（----）は単結合又は二重結合を表すが、二重結合を表す場合ｎは３である（ただし、点線（----）が二重結合を表す場合、Ｒ₁及びＲ₂は存在しない）。） The present invention relates to a novel camphorenic derivative. More specifically, it relates to the aldehyde represented by the formula (1) and its use in the perfume field.

(In the formula, n is 1 to 3, R ₁ and R ₂ represent a hydrogen atom, or R ₁ and R ₂ form a methylene group, and the dotted line (----) is a single bond or a double bond. Represents a bond, and n represents 3 when representing a double bond (provided that R ₁ and R ₂ are not present when the dotted line (----) represents a double bond).

  In the production of fragrances, floral, mugue-like fragrance compounds are very useful. In addition, camphoric aldehyde derived from inexpensive α-pinene has long been used as a perfume raw material. Many of the conventional techniques are used to develop a fragrance having a sandalwood type fragrance. On the other hand, there are almost no examples of camphorenic derivatives having floral and Mugue-like fragrances. Regarding camphorenic derivatives having a floral, mugue-like scent, only camphorenic derivatives having a 4-hexenyl group at the 1'-position are known (WO 2008/068310). According to WO 2008/068310, for example 6- (2,2,3-trimethyl-3-cyclopenten-1-yl) -4-hexenal, (+)-(1R) -6- (2,2 , 3-trimethyl-3-cyclopenten-1-yl) -4-hexenal, 6- (2,2,3-trimethylcyclopentan-1-yl) -4-hexenal and the like have a Mugue-like fragrance. It is described. Also, camphorenic derivatives whose side chain is an aldehyde are 4- (2,2,3-trimethyl-3-cyclopenten-1-yl) butanal (US Pat. No. 4,052,341) and 3- (2,2, Only 3-trimethyl-3-cyclopenten-1-yl) propanal (Journal of Organic Chemistry (1962), 27, 3562-3564) is known, but there is no mention of aroma.

International Publication No. 2008/068310 US Pat. No. 4,052,341

Journal of Organic Chemistry (1962), 27, 3562-3564

On the other hand, in recent years, with the diversification of products such as various cosmetics, health and hygiene materials, pharmaceuticals, etc., in cosmetics and hygiene materials, as well as pharmaceutical fragrances, they have strong diffusibility, unique fragrances, and tastes. The development of perfume materials that have high properties, strong retention, good stability, and high safety has been demanded. In particular, there is a shortage of fragrance materials that satisfy these requirements for fragrance materials having floral and mugue-like fragrances, and in addition to conventional fragrance materials, development of new fragrance materials that satisfy the above characteristics is expected. Has been.
Accordingly, an object of the present invention is to provide a novel compound capable of imparting a floral and mugue-like fragrance that satisfies the above requirements, and a fragrance composition containing them.

（式中、ｎは１から３であり、Ｒ₁及びＲ₂は水素原子を表すか、Ｒ₁とＲ₂とでメチレン基を形成し、点線（----）は単結合又は二重結合を表すが、二重結合を表す場合ｎは３である（ただし、点線（----）が二重結合を表す場合、Ｒ₁及びＲ₂は存在しない）。）
また、本発明は式（１）で表される化合物の立体配置が１’Ｓ−体である、上記化合物を提供する。
更に、本発明は式（１）で表される化合物の立体配置が１’Ｒ−体である、上記化合物を提供する。
また、本発明は式（１）で表される化合物を少なくとも１種含有する香料組成物を提供する。
また、本発明は式（１）で表される化合物の立体配置が１’Ｓ−体である、請求項４に記載の香料組成物を提供する。
さらに、本発明は式（１）で表される化合物の立体配置が１’Ｒ−体である、請求項４に記載の香料組成物を提供する。
また、本発明は上記の香料組成物を含有する飲食品、香粧品、芳香剤、日用・雑貨品、口腔用組成物、ヘアケア製品、スキンケア製品、身体洗浄剤、衣料用洗剤、衣料用柔軟仕上げ剤、トイレタリー製品、繊維・繊維製品、衣料品又は医薬品を提供する。 In such a situation, the present inventors conducted extensive research, and as a result, synthesized propanal, butanal and pentanal derivatives derived from camphorenic aldehydes, and these compounds have a strong floral, Mugue-like fragrance, It discovered that it could become a useful fragrance | flavor, and completed this invention. That is, this invention provides the compound represented by Formula (1).

(In the formula, n is 1 to 3, R ₁ and R ₂ represent a hydrogen atom, or R ₁ and R ₂ form a methylene group, and the dotted line (----) is a single bond or a double bond. Represents a bond, and n represents 3 when representing a double bond (provided that R ₁ and R ₂ are not present when the dotted line (----) represents a double bond).
Moreover, this invention provides the said compound whose steric configuration of the compound represented by Formula (1) is 1'S-isomer.
Furthermore, this invention provides the said compound whose steric configuration of the compound represented by Formula (1) is 1'R-isomer.
The present invention also provides a fragrance composition containing at least one compound represented by the formula (1).
Moreover, this invention provides the fragrance | flavor composition of Claim 4 whose steric configuration of the compound represented by Formula (1) is 1'S-isomer.
Furthermore, this invention provides the fragrance | flavor composition of Claim 4 whose steric configuration of the compound represented by Formula (1) is 1'R-isomer.
The present invention also includes foods and drinks, cosmetics, fragrances, daily and miscellaneous goods, oral compositions, hair care products, skin care products, body cleaners, garment detergents, garment softeners containing the fragrance composition described above. Provide finishing agents, toiletry products, textile and textile products, clothing or pharmaceutical products.

  The compound of the present invention is a very useful fragrance material having high palatability, excellent fragrance imparting properties, and excellent diffusibility and residual fragrance properties. By blending these compounds of the present invention, an aroma imparting agent with high palatability can be provided.

（式中、ｎは１から３であり、Ｒ₁及びＲ₂は水素原子を表すか、Ｒ₁とＲ₂とでメチレン基を形成し、点線（----）は単結合又は二重結合を表すが、二重結合を表す場合ｎは３である（ただし、点線（----）が二重結合を表す場合、Ｒ₁及びＲ₂は存在しない）。）
式（１）で表される化合物は、好ましくは立体配置が１’Ｓ−体又は１’Ｒ−体である。 The compound of the present invention (camphorenal derivative) is represented by the formula (1).

(In the formula, n is 1 to 3, R ₁ and R ₂ represent a hydrogen atom, or R ₁ and R ₂ form a methylene group, and the dotted line (----) is a single bond or a double bond. Represents a bond, and n represents 3 when representing a double bond (provided that R ₁ and R ₂ are not present when the dotted line (----) represents a double bond).
The compound represented by the formula (1) preferably has a steric configuration of 1′S-form or 1′R-form.

まず、カンフォレニックアルデヒドに、（メトキシメチル）トリフェニルホスホニウムクロリドと塩基から調整したリンイリドを反応させることによりエノールエーテル体を合成する。得られたエノールエーテル体を酸触媒の存在下で加水分解することによりプロパナール誘導体を容易に合成できる。 The propanal derivative in which n is 1 in the formula (1) is synthesized by, for example, the following method (Scheme 1), but the synthesis method is not limited to the following method.
(Scheme 1)

First, an enol ether is synthesized by reacting camphoric aldehyde with (methoxymethyl) triphenylphosphonium chloride and phosphorus ylide prepared from a base. A propanal derivative can be easily synthesized by hydrolyzing the obtained enol ether in the presence of an acid catalyst.

まず、カンフォレニックアルデヒドに、ホスホノ酢酸トリメチルを塩基条件下で反応させることによりブテン酸エステル体を合成する。得られたブテン酸エステル体のオレフィンを水素化することによりブタン酸エステルを得る。次に、水素化ジイソブチルアルミニウムを用いて、還元反応を行うことによりブタナール誘導体を容易に合成できる。 The butanal derivative in which n is 2 in the formula (1) is synthesized by, for example, the following method (Scheme 2), but the synthesis method is not limited to the following method.
(Scheme 2)

First, a butenoic acid ester is synthesized by reacting campholic aldehyde with trimethyl phosphonoacetate under basic conditions. Butanoic acid ester is obtained by hydrogenating the olefin of the resulting butenoic acid ester. Next, a butanal derivative can be easily synthesized by performing a reduction reaction using diisobutylaluminum hydride.

まず、スキーム２で得られたブタン酸エステルをアルコール体に還元し、次いでハロゲン化した後、例えばマグネシウムとグリニャール試薬を調製する。グリニャール試薬とホルムアミド類を反応させることによりペンタナール誘導体を容易に合成できる。 The pentanal derivative in which n is 3 in formula (1) is synthesized by, for example, the following method (Scheme 3), but the synthesis method is not limited to the following method.
(Scheme 3)

First, the butanoic acid ester obtained in Scheme 2 is reduced to an alcohol form and then halogenated, and then, for example, magnesium and a Grignard reagent are prepared. A pentanal derivative can be easily synthesized by reacting a Grignard reagent with formamides.

まず、１，２−ジクロロエタン、ジエチル亜鉛とジヨードメタンからなる溶液に４−（２，２，３−トリメチル−３−シクロペンテン−１−イル）ブタン酸エステルを滴下し、反応させることで、１，１，２−トリメチルビシクロ［３．１．０］ヘキサン骨格を有するブタン酸エステルが得られる。さらに、水素化ジイソブチルアルミニウムを用いて、還元反応を行うことによりブタナール誘導体を容易に合成できる。 In formula (1), n is 2, and a butanal derivative having a 1,1,2-trimethylbicyclo [3.1.0] hexane skeleton is synthesized by, for example, the following method (Scheme 4). The synthesis method is not limited to the following method.
(Scheme 4)

First, 4- (2,2,3-trimethyl-3-cyclopenten-1-yl) butanoic acid ester is dropped into a solution consisting of 1,2-dichloroethane, diethylzinc and diiodomethane, and reacted to give 1,1 , 2-trimethylbicyclo [3.1.0] butanoic acid ester having a hexane skeleton is obtained. Furthermore, a butanal derivative can be easily synthesized by performing a reduction reaction using diisobutylaluminum hydride.

The compound of the present invention thus obtained can be isolated and purified as necessary. Examples of isolation and purification methods include column chromatography, vacuum distillation and the like, and these can be performed alone or in combination.
The compound represented by the formula (1) contained in the fragrance composition of the present invention has R and S stereoisomers due to the configuration at the 1 ′ position. Both these two isomers have a good aroma, in particular the Mugue aroma. When the compound of formula (1) is used in the fragrance composition, a racemate may be used, but an optically active substance having an excess of R or S may be used. When the optically active substance is used, the optical purity is 20% ee to 99.9% ee, preferably 50% ee to 99.9% ee. The optical purity can be measured, for example, by various chromatography using NMR and / or chiral columns.

The fragrance composition of the present invention contains at least one compound represented by the formula (1). Although the compounding quantity to the fragrance | flavor composition of the compound represented by Formula (1) is not specifically limited, It is 0.01 to 60 weight% with respect to a fragrance | flavor composition, It is 0.1 to 40 weight% especially. preferable.
Moreover, the compounded fragrance | flavor normally used can be mix | blended with the fragrance | flavor composition of this invention. The fragrance composition obtained in this way can provide fragrance imparting with high palatability. In addition, with the fragrance composition of the present invention as a fragrance component, foods and drinks, cosmetics, fragrances, daily and miscellaneous goods, oral compositions, hair care products, skin care products, body cleaners, detergents for clothing, flexible for clothing It can be added to finishing agents, toiletry products, textiles / textile products, clothing or pharmaceutical products. That is, shampoos, rinses, perfumes, colons, hair nicks, hair creams, pomades and other cosmetics for hair, soaps, dishwashing detergents, laundry detergents, softeners, disinfecting detergents, deodorant detergents, indoors This industry includes fragrances, furniture, disinfectants, insecticides, bleaches, various other hygiene detergents, toothpastes, mouthwashes, toilet paper, and fragrances for ease of taking medicines. By adding the amount usually added, the unique aroma can be given and the commercial value can be increased.

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In addition, the measurement of the product in a synthesis example and an Example was performed using the following apparatus apparatus.
NMR: DRX500 (manufactured by Bruker)
GC / MS: GCMS-QP2010 (manufactured by Shimadzu Corporation)
Column: RTX-1 (length 30 m × inner diameter 0.25 mm, liquid phase film thickness 0.25 μm)
GC purity: HP6890 (manufactured by HEWLETPACKARD)
Column: Capillary column DB-1 of J & W Scientific (length 30 m × inner diameter 0.25 mm, liquid phase film thickness 0.25 μm)
Injection temperature 250 ° C, detection temperature 250 ° C
100 ° C-10 ° C / min-300 ° C (5 min)
Optical purity: GC-2010 (manufactured by Shimadzu Corporation)
Column: Rt-β-DEXse (manufactured by RESTEK, length 30 m × inner diameter 0.25 mm, liquid phase film thickness 0.25 μm)
Injection temperature 250 ° C, detection temperature 250 ° C
70 ° C (1 minute) -0.5 ° C / minute -150 ° C

窒素気流下、撹拌装置、滴下ロート、温度計のついた５００ｍｌフラスコに、塩化メトキシメチルトリフェニルホスホニウム（５０ｇ、０．１４６ｍｏｌ）、テトラヒドロフラン（１００ｍｌ）を入れ、０℃に冷却した。滴下ロートにカリウムｔ−ブトキシド（１６．４ｇ、０．１４６ｍｏｌ）のテトラヒドロフラン（１００ｍｌ）溶液を入れ、０℃を保つように滴下した。滴下終了後、同温度のまま１時間撹拌した後、（Ｒ）−２−（２，２，３−トリメチル−３−シクロペンテン−１−イル）アセトアルデヒド（８２％ｅｅ、１８．５ｇ、０．１２２ｍｏｌ）を３０分かけて滴下した。滴下終了後、２０℃に温度を上げ、６時間撹拌を続けた。次に、飽和塩化アンモニウム水溶液（１００ｍｌ）を加え１０分間撹拌した後、水層を分液した。有機層を水（５０ｍｌ）で２回洗浄し、減圧下、溶媒を回収した。析出した白色の固体をろ過し、シリカゲルカラムクロマトにより精製を行い、（Ｒ）−４−（３−メトキシアリル）−１，５，５−トリメチル−１−シクロペンテン（１３．５ｇ、０．０７５ｍｏｌ、収率６１％）を得た。
次に、窒素気流下、撹拌装置、還流管、温度計の付いた１００ｍｌに、上記で得られた、（Ｒ）−４−（３−メトキシアリル）−１，５，５−トリメチル−１−シクロペンテン（１０．０ｇ、０．０５５ｍｏｌ）、アセトニトリル（１０ｍｌ）、２％硫酸水溶液（５０ｍｌ）を入れ、６０℃で８時間撹拌した。冷却後、有機層を分液し、水層をトルエン（２５ｍｌ）で２回抽出した。有機層を合わせて水洗を行い、減圧下溶媒を除去した。得られた粗生成物をシリカゲルカラムクロマトにより精製を行い、３−（（１Ｓ）−２，２，３−トリメチル−３−シクロペンテン−１−イル）−プロパナール（５．２ｇ、０．３１ｍｏｌ、収率５７％、純度９５％）を得た。光学純度は８２％ｅｅであった。
１００ｍｌオートクレーブに、上記で得られた３−（（１Ｓ）−２，２，３−トリメチル−３−シクロペンテン−１−イル）プロパナール（３．０ｇ、０．０１８ｍｏｌ）、５％Ｐｄ／Ｃ（０．１５ｇ）を入れ、水素圧１ＭＰａ、４０℃で３時間反応させた。触媒をろ過し、シリカゲルカラムクロマトにより精製を行うことで、３−（（１Ｒ）−２，２，３−トリメチルシクロペンチル）プロパナール（２．７ｇ、０．０１６１ｍｏｌ、収率８９％、純度９５％）を得た。光学純度は８２％ｅｅであった。 Example 1
Synthesis of 3-((1R) -2,2,3-trimethylcyclopentyl) propanal

Under a nitrogen stream, methoxymethyltriphenylphosphonium chloride (50 g, 0.146 mol) and tetrahydrofuran (100 ml) were placed in a 500 ml flask equipped with a stirrer, a dropping funnel and a thermometer, and cooled to 0 ° C. A solution of potassium t-butoxide (16.4 g, 0.146 mol) in tetrahydrofuran (100 ml) was added to the dropping funnel and added dropwise so as to maintain 0 ° C. After completion of dropping, the mixture was stirred at the same temperature for 1 hour, and then (R) -2- (2,2,3-trimethyl-3-cyclopenten-1-yl) acetaldehyde (82% ee, 18.5 g, 0.122 mol) ) Was added dropwise over 30 minutes. After completion of dropping, the temperature was raised to 20 ° C. and stirring was continued for 6 hours. Next, a saturated aqueous ammonium chloride solution (100 ml) was added and stirred for 10 minutes, and then the aqueous layer was separated. The organic layer was washed twice with water (50 ml), and the solvent was recovered under reduced pressure. The precipitated white solid was filtered and purified by silica gel column chromatography, and (R) -4- (3-methoxyallyl) -1,5,5-trimethyl-1-cyclopentene (13.5 g, 0.075 mol, Yield 61%).
Next, under a nitrogen stream, (R) -4- (3-methoxyallyl) -1,5,5-trimethyl-1- (R) -4- (3-methoxyallyl) obtained above was added to 100 ml with a stirrer, a reflux tube and a thermometer. Cyclopentene (10.0 g, 0.055 mol), acetonitrile (10 ml), 2% aqueous sulfuric acid solution (50 ml) were added, and the mixture was stirred at 60 ° C. for 8 hours. After cooling, the organic layer was separated, and the aqueous layer was extracted twice with toluene (25 ml). The organic layers were combined and washed with water, and the solvent was removed under reduced pressure. The obtained crude product was purified by silica gel column chromatography, and 3-((1S) -2,2,3-trimethyl-3-cyclopenten-1-yl) -propanal (5.2 g, 0.31 mol, Yield 57%, purity 95%). The optical purity was 82% ee.
To a 100 ml autoclave, 3-((1S) -2,2,3-trimethyl-3-cyclopenten-1-yl) propanal (3.0 g, 0.018 mol) obtained above, 5% Pd / C ( 0.15 g) was added, and the mixture was reacted at a hydrogen pressure of 1 MPa and 40 ° C. for 3 hours. The catalyst was filtered and purified by silica gel column chromatography to obtain 3-((1R) -2,2,3-trimethylcyclopentyl) propanal (2.7 g, 0.0161 mol, yield 89%, purity 95%). ) The optical purity was 82% ee.

GC / MS
168 (M ⁺ , 5%), 153 (40), 135 (20), 124 (35), 109 (65), 97 (25), 84 (75), 69 (100), 55 (30), 41 (30)
1H (500MHz, CDCl3)
0.53 (s, 3H), 0.84 (d, 3H), 0.88 (s, 3H), 0.92-0.99 (m, 1H), 1.11-1.19 (m, 2H), 1.28-1.34 (m, 2H), 1.46-1.53 (m, 1H), 1.70-1.78 (m, 2H), 2.38-2.46 ( m, 2H), 9.80 (s, 1H)
13C (125MHz, CDCl3)
14.1, 14.5, 23.1, 25.8, 28.2, 30.2, 42.6, 43.6, 45.4, 50.6, 203.4

実施例１で用いた（Ｒ）−２−（２，２，３−トリメチル−３−シクロペンテン−１−イル）アセトアルデヒドを（Ｓ）−２−（２，２，３−トリメチル−３−シクロペンテン−１−イル）アセトアルデヒド（５５％ｅｅ）に代えて、実施例１と同様の方法により、３−（（１Ｓ）−２，２，３−トリメチルシクロペンチル）プロパナールを合成した。光学純度は５５％ｅｅであった。 (Example 2)
Synthesis of 3-((1S) -2,2,3-trimethylcyclopentyl) propanal

The (R) -2- (2,2,3-trimethyl-3-cyclopenten-1-yl) acetaldehyde used in Example 1 was converted to (S) -2- (2,2,3-trimethyl-3-cyclopentene- Instead of 1-yl) acetaldehyde (55% ee), 3-((1S) -2,2,3-trimethylcyclopentyl) propanal was synthesized by the same method as in Example 1. The optical purity was 55% ee.

GC / MS
168 (M ⁺ , 5%), 153 (40), 135 (20), 124 (35), 109 (65), 97 (25), 84 (75), 69 (100), 55 (30), 41 (30)
1H (500MHz, CDCl3)
0.53 (s, 3H), 0.84 (d, 3H), 0.88 (s, 3H), 0.92-0.99 (m, 1H), 1.11-1.19 (m, 2H), 1.28-1.34 (m, 2H), 1.46-1.53 (m, 1H), 1.70-1.78 (m, 2H), 2.38-2.46 ( m, 2H), 9.80 (s, 1H)
13C (125MHz, CDCl3)
14.1, 14.5, 23.1, 25.8, 28.2, 30.2, 42.6, 43.6, 45.4, 50.6, 203.4

窒素気流下、撹拌装置、滴下ロート、温度計のついた１Ｌフラスコに、６０％水素化ナトリウム（８．０ｇ、０．２ｍｏｌ）、トルエン（８００ｍｌ）を入れ、室温にて滴下ロートよりホスホノ酢酸トリメチル（３６．４ｇ、０．２ｍｏｌ）を滴下した。滴下終了後、１時間撹拌を続け、発泡がなくなったことを確認した。次に、室温にて（Ｒ）−２−（２，２，３−トリメチル−３−シクロペンテン−１−イル）アセトアルデヒド（８２％ｅｅ、３０．４ｇ、０．２ｍｏｌ）を３０分かけて滴下した。滴下終了後、３時間撹拌を続けた。その後、水（１００ｍｌ）を加え、分液し、有機層を水（１００ｍｌ）で２回洗浄した。減圧下で溶媒を除去し、減圧蒸留で精製し、メチル ４−（（１Ｓ）−２，２，３−トリメチル−３−シクロペン−１−イル）−２−ブテノエート（沸点８５℃／２．０ｍｍＨｇ、３０．５ｇ、０．１４７ｍｏｌ、収率７３％）を得た。
次に、１００ｍｌオートクレーブに、上記で得られたメチル ４−（（１Ｓ）−２，２，３−トリメチル−３−シクロペン−１−イル）−２−ブテノエート（１５．８ｇ、０．０７６ｍｏｌ）、５％パラジウム／炭素（０．５ｇ）を入れ、水素圧３．０ＭＰａ、６０℃で３時間反応させた。冷却後、触媒をろ過し、減圧蒸留にて精製し、メチル ４−（（１Ｓ）−２，２，３−トリメチルシクロペンチル）ブタノエート（沸点６５℃／０．５ｍｍＨｇ、１５．０ｇ、０．０７１ｍｏｌ、収率９３％）を得た。
次に、窒素気流下、撹拌装置、滴下ロート、温度計のついた１００ｍLフラスコに、上記で合成したメチル ４−（（１Ｓ）−２，２，３−トリメチルシクロペンチル）ブタノエート（１０．６ｇ、０．０５ｍｏｌ）、トルエン（２５ｍｌ）を入れ、−７８℃に冷却した。滴下ロートより水素化ジイソブチルアルミニウム（１．０ｍｏｌ／L トルエン溶液、５０ｍｌ、０．０５ｍｏｌ）を１時間かけて滴下した。反応溶液を、０℃に冷却した５％塩酸水溶液（１７５ｍｌ）に入れ、３０分間撹拌を続けた。水層を分液し、有機層を水（２５ｍｌ）で３回洗浄した。減圧下で溶媒を除去した後、シリカゲルカラムクロマトにより精製し、４−（（１Ｓ）−２，２，３−トリメチルシクロペンチル）ブタナール（７．５９ｇ、０．０４２ｍｏｌ、収率８３％、純度９６％）を得た。光学純度は８２％ｅｅであった。 (Example 3)
Synthesis of 4-((1S) -2,2,3-trimethylcyclopentyl) butanal

Under a nitrogen stream, 60% sodium hydride (8.0 g, 0.2 mol) and toluene (800 ml) were placed in a 1 L flask equipped with a stirrer, a dropping funnel and a thermometer, and trimethylphosphonoacetate from the dropping funnel at room temperature. (36.4 g, 0.2 mol) was added dropwise. After completion of the dropping, stirring was continued for 1 hour, and it was confirmed that foaming disappeared. Next, (R) -2- (2,2,3-trimethyl-3-cyclopenten-1-yl) acetaldehyde (82% ee, 30.4 g, 0.2 mol) was added dropwise at room temperature over 30 minutes. . After completion of dropping, stirring was continued for 3 hours. Then, water (100 ml) was added and liquid-separated, and the organic layer was washed twice with water (100 ml). Solvent was removed under reduced pressure and purified by distillation under reduced pressure to give methyl 4-((1S) -2,2,3-trimethyl-3-cyclopent-1-yl) -2-butenoate (boiling point 85 ° C./2.0 mmHg). 30.5 g, 0.147 mol, yield 73%).
Next, in a 100 ml autoclave, methyl 4-((1S) -2,2,3-trimethyl-3-cyclopent-1-yl) -2-butenoate (15.8 g, 0.076 mol) obtained above, 5% Palladium / carbon (0.5 g) was added and reacted at a hydrogen pressure of 3.0 MPa and 60 ° C. for 3 hours. After cooling, the catalyst was filtered, purified by distillation under reduced pressure, and methyl 4-((1S) -2,2,3-trimethylcyclopentyl) butanoate (boiling point 65 ° C./0.5 mmHg, 15.0 g, 0.071 mol, Yield 93%) was obtained.
Next, methyl 4-((1S) -2,2,3-trimethylcyclopentyl) butanoate (10.6 g, 0) was synthesized in a 100 mL flask equipped with a stirrer, a dropping funnel and a thermometer under a nitrogen stream. 0.05 mol) and toluene (25 ml) were added and cooled to -78 ° C. Diisobutylaluminum hydride (1.0 mol / L toluene solution, 50 ml, 0.05 mol) was added dropwise from the dropping funnel over 1 hour. The reaction solution was placed in a 5% aqueous hydrochloric acid solution (175 ml) cooled to 0 ° C., and stirring was continued for 30 minutes. The aqueous layer was separated, and the organic layer was washed 3 times with water (25 ml). After removing the solvent under reduced pressure, the residue was purified by silica gel column chromatography. 4-((1S) -2,2,3-trimethylcyclopentyl) butanal (7.59 g, 0.042 mol, yield 83%, purity 96%) ) The optical purity was 82% ee.

GC / MS
182 (M ⁺ , 5%), 167 (10), 149 (20), 139 (5), 123 (20), 109 (30), 95 (30), 84 (70), 69 (100), 55 (60), 41 (60)
1H (500MHz, CDCl3)
0.49 (s, 3H), 0.82 (d, 3H), 0.85 (s, 3H), 1.04-1.08 (m, 1H), 1.12-1.20 (m, 2H), 1.31-1.42 (m, 2H), 1.42-1.54 (m, 2H), 1.64-1.75 (m, 2H), 1.76-1.85 ( m, 1H), 2.37-2.45 (m, 2H), 9.76 (s, 1H)
13C (125MHz, CDCl3)
13.9, 14.4, 21.5, 25.6, 28.2, 30.1, 30.2, 42.3, 44.4, 45.2, 50.8, 203.0

実施例２で用いた（Ｒ）−２−（２，２，３−トリメチル−３−シクロペンテン−１−イル）アセトアルデヒドを（Ｓ）−２−（２，２，３−トリメチル−３−シクロペンテン−１−イル）アセトアルデヒド（５５％ｅｅ）に代えて、実施例２と同様の方法で４−（（１Ｒ）−２，２，３−トリメチルシクロペンチル）ブタナールを合成した。光学純度は５０％ｅｅであった。 Example 4
Synthesis of 4-((1R) -2,2,3-trimethylcyclopentyl) butanal

The (R) -2- (2,2,3-trimethyl-3-cyclopenten-1-yl) acetaldehyde used in Example 2 was converted to (S) -2- (2,2,3-trimethyl-3-cyclopentene- Instead of 1-yl) acetaldehyde (55% ee), 4-((1R) -2,2,3-trimethylcyclopentyl) butanal was synthesized in the same manner as in Example 2. The optical purity was 50% ee.

GC / MS
182 (M ⁺ , 5%), 167 (10), 149 (20), 139 (5), 123 (20), 109 (30), 95 (30), 84 (70), 69 (100), 55 (60), 41 (60)
1H (500MHz, CDCl3)
0.49 (s, 3H), 0.82 (d, 3H), 0.85 (s, 3H), 1.04-1.08 (m, 1H), 1.12-1.20 (m, 2H), 1.31-1.42 (m, 2H), 1.42-1.54 (m, 2H), 1.64-1.75 (m, 2H), 1.76-1.85 ( m, 1H), 2.37-2.45 (m, 2H), 9.76 (s, 1H)
13C (125MHz, CDCl3)
13.9, 14.4, 21.5, 25.6, 28.2, 30.1, 30.2, 42.3, 44.4, 45.2, 50.8, 203.0

窒素気流下、撹拌装置、滴下ロート、温度計のついた１Ｌフラスコに、水素化リチウムアルミニウム（２．４３ｇ、０．０６４ｍｏｌ）、テトラヒドロフラン（３００ｍｌ）を入れ、０℃に冷却した。そこへ、実施例２と同様の方法で合成した中間体メチル ４−（（１Ｓ）−２，２，３−トリメチルシクロペンチル）ブタノエート（３１．１ｇ、０．１４８ｍｏｌ）を滴下ロートより滴下した。滴下終了後、同温度で１時間撹拌を続け、ＧＣにて原料の消失を確認した。３Ｎ塩酸水溶液（２５０ｍｌ）を氷冷下で滴下した。滴下終了後、１時間撹拌し、分液した。有機層を水（１００ｍｌ）で３回洗浄し、有機層を硫酸マグネシウムで乾燥させた。ろ過後、減圧下で溶媒を除去し、減圧蒸留にて精製し、４−（（１Ｓ）−２，２，３−トリメチルシクロペンチル）ブタン−１−オール（沸点９０℃／１．０ｍｍＨｇ、２３．７ｇ、０．１３ｍｏｌ、収率８７％）を得た。
次に、窒素気流下、撹拌装置、滴下ロート、温度計のついた１Ｌフラスコに、上記で得られた、４−（（１Ｓ）−２，２，３−トリメチルシクロペンチル）ブタン−１−オール（２２．３６ｇ、０．１２ｍｏｌ）、トリエチルアミン（１２．８ｇ、０．１３ｍｏｌ）、トルエン（１５０ｍｌ）を入れ５℃に冷却した。そこへ、塩化メタンスルホニル（１４．４ｇ、０．１３ｍｏｌ）を１時間かけて滴下した。滴下終了後、１時間撹拌を続け、ＧＣにて原料の消失を確認した。水（１５０ｍｌ）を加え、分液し、有機層を水（１５０ｍｌ）で３回洗浄した。減圧下溶媒を除去し、メシルエステル体を得た。
次に、撹拌装置、温度計の付いた５００ｍｌフラスコに、上記で得られたメシルエステル、ＤＭＳＯ（４０ｍｌ）、ＬｉＢｒ（１０．４ｇ、０．１２ｍｏｌ）を入れ、３５℃で２０時間撹拌した。反応溶液にトルエン（１００ｍｌ）、水（１００ｍｌ）を入れ、分液した。有機層を水（５０ｍｌ）で２回洗浄し、減圧下で溶媒を除去した。減圧蒸留で精製し、（２Ｓ）−２−（４−ブロモブチル）−１，１，５−トリメチルシクロペンタン（沸点８０℃／２．０ｍｍＨｇ、２４．７ｇ、０．１０ｍｏｌ、収率８３％）を得た。
次に、滴下ロート、還流管、温度計、撹拌装置の付いた５００ｍｌフラスコに、マグネシウム（２．８８ｇ、０．１２ｍｏｌ）、ＴＨＦ（２５０ｍｌ）、ヨウ素（１０ｍｇ）を入れ、４０℃に加熱した。そこへ、上記で得られた（２Ｓ）−２−（４−ブロモブチル−１，１，５−トリメチルシクロペンタン（２４．７ｇ、０．１０ｍｏｌ）をゆっくり滴下した。滴下終了後、８時間、同温度で撹拌を続けた後、０℃に冷却した。そこへ１−ピペリジンカルバルデヒド（１３．５ｇ、０．１２ｍｏｌ）を滴下し、滴下終了後、１時間撹拌を続けた。次に、３Ｎ塩酸水溶液（７５ｍｌ）を加え、分液した。有機層を１０％食塩水（５０ｍｌ）で洗浄し、溶媒を減圧下除去した。減圧蒸留で精製を行い、５−（（１Ｓ）−２，２，３−トリメチルシクロペンチル）ペンタナール（１４ｇ、０．０７１ｍｏｌ、収率５９％、純度９８％）を得た。光学純度は８１％ｅｅであった。 (Example 5)
Synthesis of 5-((1S) -2,2,3-trimethylcyclopentyl) pentanal

Under a nitrogen stream, lithium aluminum hydride (2.43 g, 0.064 mol) and tetrahydrofuran (300 ml) were placed in a 1 L flask equipped with a stirrer, a dropping funnel and a thermometer, and cooled to 0 ° C. Thereto, an intermediate methyl 4-((1S) -2,2,3-trimethylcyclopentyl) butanoate (31.1 g, 0.148 mol) synthesized in the same manner as in Example 2 was dropped from a dropping funnel. After completion of dropping, stirring was continued for 1 hour at the same temperature, and disappearance of the raw material was confirmed by GC. 3N aqueous hydrochloric acid (250 ml) was added dropwise under ice cooling. After completion of dropping, the mixture was stirred for 1 hour and separated. The organic layer was washed 3 times with water (100 ml) and the organic layer was dried over magnesium sulfate. After filtration, the solvent was removed under reduced pressure, and the residue was purified by distillation under reduced pressure to give 4-((1S) -2,2,3-trimethylcyclopentyl) butan-1-ol (boiling point 90 ° C./1.0 mmHg, 23. 7 g, 0.13 mol, yield 87%).
Next, in a 1 L flask equipped with a stirrer, a dropping funnel, and a thermometer under a nitrogen stream, 4-((1S) -2,2,3-trimethylcyclopentyl) butan-1-ol ( 22.36 g, 0.12 mol), triethylamine (12.8 g, 0.13 mol), and toluene (150 ml) were added and cooled to 5 ° C. To this, methanesulfonyl chloride (14.4 g, 0.13 mol) was added dropwise over 1 hour. After completion of dropping, stirring was continued for 1 hour, and disappearance of raw materials was confirmed by GC. Water (150 ml) was added for liquid separation, and the organic layer was washed 3 times with water (150 ml). The solvent was removed under reduced pressure to obtain a mesyl ester.
Next, the mesyl ester, DMSO (40 ml) and LiBr (10.4 g, 0.12 mol) obtained above were put into a 500 ml flask equipped with a stirrer and a thermometer, and stirred at 35 ° C. for 20 hours. Toluene (100 ml) and water (100 ml) were added to the reaction solution, followed by liquid separation. The organic layer was washed twice with water (50 ml) and the solvent was removed under reduced pressure. Purification by distillation under reduced pressure gave (2S) -2- (4-bromobutyl) -1,1,5-trimethylcyclopentane (boiling point 80 ° C./2.0 mmHg, 24.7 g, 0.10 mol, yield 83%). Obtained.
Next, magnesium (2.88 g, 0.12 mol), THF (250 ml), and iodine (10 mg) were placed in a 500 ml flask equipped with a dropping funnel, a reflux tube, a thermometer, and a stirrer, and heated to 40 ° C. Thereto was slowly added dropwise (2S) -2- (4-bromobutyl-1,1,5-trimethylcyclopentane (24.7 g, 0.10 mol) obtained above. Stirring was continued at a temperature, and then the mixture was cooled to 0 ° C. 1-piperidinecarbaldehyde (13.5 g, 0.12 mol) was added dropwise thereto, and the stirring was continued for 1 hour after completion of the dropwise addition. An aqueous solution (75 ml) was added and the layers were separated, the organic layer was washed with 10% brine (50 ml), the solvent was removed under reduced pressure, purified by distillation under reduced pressure, and 5-((1S) -2,2, 3-trimethylcyclopentyl) pentanal (14 g, 0.071 mol, yield 59%, purity 98%) was obtained, and the optical purity was 81% ee.

GC / MS
196 (M ⁺ , 10%), 181 (25), 163 (25), 152 (15), 135 (25), 123 (25), 110 (35), 84 (75), 69 (100), 55 (55), 41 (50)
1H (500MHz, CDCl3)
0.49 (s, 3H), 0.78 (d, 3H), 0.81 (s, 3H), 1.02-1.08 (m, 2H), 1.09-1.17 (m, 2H), 1.19-1.26 (m, 2H), 1.29-1.38 (m, 1H), 1.38-1.45 (m, 1H), 1.48-1.55 ( m, 2H), 1.70-1.80 (m, 2H), 2.53 (t, 2H), 9, 77 (s, 1H)
13C (125MHz, CDCl3)
13.9, 14.4, 22.5, 25.14, 25.7, 28.4, 28.5, 30.2, 30.3, 42.3, 44.0, 50.7, 203. 0

１００ｍｌオートクレーブに、実施例４と同様の方法で合成したメチル ４−（（１Ｒ）−２，２，３−トリメチル−３−シクロペンテン−１−イル）−２−ブテノエート（１５．８ｇ、０．０７６ｍｏｌ）、ラネーニッケル（０．５ｇ）を入れ、水素圧３．０ＭＰａ、６０℃で３時間反応させた。触媒をろ過し、減圧蒸留にて精製し、メチル ４−（（１Ｒ）−２，２，３−トリメチル−３−シクロペンテン−１−イル）ブタノエート（沸点６５℃／０．５ｍｍＨｇ、１６．０ｇ、０．０７３ｍｏｌ、収率９６％）を得た。
上記で得られたメチル ４−（（１Ｒ）−２，２，３−トリメチル−３−シクロペンテン−１−イル）ブタノエートを実施例５と同様の方法で、還元、ブロモ化、グリニャール反応を行い、５−（（１Ｓ）−２，２，３−トリメチル−３−シクロペンテン−１−イル）ペンタナール（１４ｇ、０．０７１ｍｏｌ、収率５９％、純度９８％）を得た。光学純度は８１％ｅｅであった。 (Example 6)
Synthesis of 5-((1R) -2,2,3-trimethyl-3-cyclopentenyl) pentanal

Methyl 4-((1R) -2,2,3-trimethyl-3-cyclopenten-1-yl) -2-butenoate (15.8 g, 0.076 mol) synthesized in the same manner as in Example 4 in a 100 ml autoclave ) And Raney nickel (0.5 g) were added and reacted at a hydrogen pressure of 3.0 MPa and 60 ° C. for 3 hours. The catalyst was filtered, purified by distillation under reduced pressure, and methyl 4-((1R) -2,2,3-trimethyl-3-cyclopenten-1-yl) butanoate (boiling point 65 ° C./0.5 mmHg, 16.0 g, 0.073 mol, yield 96%) was obtained.
The methyl 4-((1R) -2,2,3-trimethyl-3-cyclopenten-1-yl) butanoate obtained above was subjected to reduction, bromination and Grignard reaction in the same manner as in Example 5. 5-((1S) -2,2,3-trimethyl-3-cyclopenten-1-yl) pentanal (14 g, 0.071 mol, yield 59%, purity 98%) was obtained. The optical purity was 81% ee.

GC / MS
194 (M ⁺ , 25%), 179 (100), 161 (75), 150 (5), 135 (15), 119 (60), 107 (20), 95 (75), 81 (25), 67 (30), 55 (25), 41 (25)
1H (500MHz, CDCl3)
0.75 (s, 3H), 0.97 (d, 3H), 1.22-1.32 (m, 2H), 1.36-1.45 (m, 2H), 1.55-1. 62 (m, 2H), 1.61 (s, 3H), 1.64-1.74 (m, 2H), 2.20-3.10 (m, 1H), 2.41-2.48 ( m, 2H), 5.2 (m, 1H), 9.8 (s, 1H)
13C (125MHz, CDCl3)
12.8, 19.9, 22.7, 26.1, 28.6, 30.0, 35.8, 44.2, 46.9, 50.4, 121.9, 149.0, 203. 1

１００ｍｌオートクレーブに、上記実施例２と同様の方法で合成したメチル ４−（（１Ｓ）−２，２，３−トリメチル−３−シクロペンテン−１−イル）−２−ブテノエート（１５．８ｇ、０．０７６ｍｏｌ）、ラネーニッケル（０．５ｇ）を入れ、水素圧３．０ＭＰａ、６０℃で３時間反応させた。触媒をろ過し、減圧蒸留にて精製し、メチル ４−（（１Ｓ）−２，２，３−トリメチル−３−シクロペンテン−１−イル）ブタノエート（沸点６５℃／０．５ｍｍＨｇ、１５．０ｇ、０．０７１ｍｏｌ、収率９４％）を得た。
次に、窒素気流下、撹拌装置、温度計、滴下ロートの付いた５００ｍｌフラスコに、１，２−ジクロロエタン（２８７ｍｌ）、１．１０Ｍジエチル亜鉛ヘキサン溶液（７９．８ｍｌ、１．５ｍｏｌ）を入れ、滴下ロートよりジヨードメタン（３６．０ｇ、２．３ｍｏｌ）を２０℃で滴下した。滴下終了後、３０分撹拌を続け、上記で得られたメチル ４−（（１Ｓ）−２，２，３−トリメチル−３−シクロペンテン−１−イル）ブタノエート（１２．３ｇ、０．０５８ｍｏｌ）を１時間かけて滴下した。滴下終了後、１時間撹拌した。次に、２０％炭酸カリウム水溶液（６０ｍｌ）を加え、分液した。有機層を硫酸マグネシウムで乾燥し、減圧下で溶媒を除去した。シリカゲルカラムクロマトにより精製を行い、メチル ４−（（３Ｓ）−１，２，２−トリメチルビシクロ［３．１．０］ヘキサン−３−イル）ブタノエート（１０．８２ｇ、０．０４８ｍｏｌ、収率８３％）を得た。
次に、窒素気流下、滴下ロート、温度計、撹拌装置のついた２００ｍｌフラスコに、上記で得られたメチル ４−（（３Ｓ）−１，２，２−トリメチルビシクロ［３．１．０］ヘキサン−３−イル）ブタノエート（１０．５ｇ、０．０４６ｍｏｌ）、トルエン（３１．５ｍｌ）を入れ、−７８℃に冷却した。滴下ロートより１．０Ｍ水素化ジイソブチルアルミニウム ヘキサン溶液（４８．５ｍｌ、０．０５ｍｏｌ）を２時間かけて滴下した。滴下終了後、−７８℃で１時間撹拌し、５Ｎ塩酸水溶液（２００ｍｌ）中に反応溶液を滴下した。有機層を水（１５０ｍｌ）で３回洗浄を行い、硫酸マグネシウムで乾燥後、減圧下で溶媒を除去した。シリカゲルカラムクロマトにより精製し、４−（（３Ｓ）−１，２，２−トリメチルビシクロ［３．１．０］ヘキサン−３−イル）ブタナール（６，９１ｇ、０．０３６ｍｏｌ、収率７６％）を得た。光学純度は８２％ｅｅであった。 (Example 7)
Synthesis of 4-((3S) -1,1,2-trimethylbicyclo [3.1.0] hexane-3-yl) butanal

In a 100 ml autoclave, methyl 4-((1S) -2,2,3-trimethyl-3-cyclopenten-1-yl) -2-butenoate (15.8 g, 0. 1) was synthesized in the same manner as in Example 2 above. 076 mol) and Raney nickel (0.5 g) were added and reacted at a hydrogen pressure of 3.0 MPa and 60 ° C. for 3 hours. The catalyst was filtered, purified by distillation under reduced pressure, and methyl 4-((1S) -2,2,3-trimethyl-3-cyclopenten-1-yl) butanoate (boiling point 65 ° C./0.5 mmHg, 15.0 g, 0.071 mol, yield 94%).
Next, 1,2-dichloroethane (287 ml) and 1.10 M diethylzinc hexane solution (79.8 ml, 1.5 mol) were placed in a 500 ml flask equipped with a stirrer, a thermometer, and a dropping funnel under a nitrogen stream. Diiodomethane (36.0 g, 2.3 mol) was added dropwise at 20 ° C. from the dropping funnel. After completion of the dropwise addition, stirring was continued for 30 minutes, and methyl 4-((1S) -2,2,3-trimethyl-3-cyclopenten-1-yl) butanoate (12.3 g, 0.058 mol) obtained above was added. The solution was added dropwise over 1 hour. It stirred for 1 hour after completion | finish of dripping. Next, a 20% aqueous potassium carbonate solution (60 ml) was added to separate the layers. The organic layer was dried over magnesium sulfate and the solvent was removed under reduced pressure. Purification was performed by silica gel column chromatography, and methyl 4-((3S) -1,2,2-trimethylbicyclo [3.1.0] hexane-3-yl) butanoate (10.82 g, 0.048 mol, yield 83). %).
Next, methyl 4-((3S) -1,2,2-trimethylbicyclo [3.1.0] obtained above was placed in a 200 ml flask equipped with a dropping funnel, thermometer, and stirrer under a nitrogen stream. Hexane-3-yl) butanoate (10.5 g, 0.046 mol) and toluene (31.5 ml) were added and cooled to -78 ° C. 1.0 M diisobutylaluminum hydride hexane solution (48.5 ml, 0.05 mol) was added dropwise from the dropping funnel over 2 hours. After completion of the dropwise addition, the mixture was stirred at -78 ° C for 1 hour, and the reaction solution was dropped into 5N hydrochloric acid aqueous solution (200 ml). The organic layer was washed 3 times with water (150 ml), dried over magnesium sulfate, and then the solvent was removed under reduced pressure. Purified by silica gel column chromatography, 4-((3S) -1,2,2-trimethylbicyclo [3.1.0] hexane-3-yl) butanal (6,91 g, 0.036 mol, 76% yield) Got. The optical purity was 82% ee.

GC / MS
194 (M ⁺ , 5%), 179 (25), 161 (30), 153 (15), 135 (20), 121 (30), 109 (35), 95 (30), 82 (100), 69 (50), 55 (60), 41 (55)
NMR data
¹ H-NMR (500 MHz, CDCl ₃ ):
δ 0.00-0.03 (m, 1H), 0.41-0.43 (m, 1H), 0.75 (s, 3H), 0.88 (s, 3H), 0.95-0 .99 (m, 1H), 1.03 (s, 3H), 1.02-1.07 (m, 1H), 1.07-1.13 (m, 1H), 1.27-1.33 (M, 1H), 1.33-1.38 (m, 1H), 1.45-1.50 (m, 1H), 1.61-1.68 (m, 1H), 1.75-1 .79 (m, 1H), 2.39-2.42 (m, 2H), 9.75 (t, 1H)
¹³ C-NMR (125 MHz, CDCl ₃ ):
δ 13.97 (CH ₂ ), 17.36 (CH ₃ ), 19.69 (CH ₃ ), 21.58 (CH ₂ ), 22.56 (CH), 22.94 (CH ₃ ), 29. 84 (CH ₂ ), 31.45 (C), 32.36 (CH ₂ ), 41.33 (C), 44.28 (CH), 44.31 (CH ₂ ), 202.72 (CHO)

(Example 8: Evaluation of aroma quality)
For the compound synthesized in Example 1-6, sensory evaluation was performed. The quality of the fragrances was examined by 10 expert panelists who had more than 5 years of experience. The results are shown in Table 1 below.

(Example 9: Strength comparison between stereoisomers)
A comparative experiment was conducted regarding the difference in strength between stereoisomers for the compounds synthesized in Example 3 and Example 4. The evaluation was performed by 10 expert panelists who had experienced for 5 years or more, and the strength was evaluated by 10-level (minimum 0 to maximum 10 points) evaluation, and the average value was taken. The results are shown in Table 2 below. In comparison between the 1′-S form and the 1′-R form, the 1′-R form was evaluated to be stronger.

(Comparative Example 1)
Synthesis and sensory evaluation of 6-((1R) -2,2,3-trimethyl-3-cyclopenten-1-yl) -4-hexenal According to the method described in WO2008 / 068310, 6-((1R) -2,2,3-Trimethyl-3-cyclopenten-1-yl) -4-hexenal (55% ee, purity 98%) was synthesized and evaluated by 5 expert panelists who have experienced over 5 years. The results are shown in Table 3 below.

(Comparative Example 2)
The strengths of the compound synthesized in Example 1-7 and the compound synthesized in Comparative Example 1 were compared. The evaluation was carried out by 10 expert panelists who had more than 5 years of experience. For comparison of strength, 6-((1R) -2,2,3-trimethyl-3-cyclopenten-1-yl) -4-hexenal synthesized in Comparative Example 1 was evaluated on a five-point scale and averaged. The results are shown in Table 4 below. All the compounds were the same as or stronger than the compounds synthesized in Comparative Example 1, and in particular, the compounds of Examples 3 and 4 were high in strength.

官能評価は５年以上経験した４人の専門パネラーが行い、その結果、実施例４の化合物を含有するミューゲ調香料組成物は比較例１の化合物を含有するミューゲ調香料組成物と比べてミューゲ様がはっきりと認められる強いフローラル香気を有し、また拡散性においても優れているとパネラー全員が判断した。 (Example 10: Fragrance composition)
In accordance with the formulation shown in Table 5 below, a fragrance composition for perfume was prepared using the compound synthesized in Example 4 or the compound of Comparative Example 1.

The sensory evaluation was performed by four expert panelists who had experienced for more than 5 years. As a result, the Mugue flavor composition containing the compound of Example 4 was compared with the Mugue flavor composition containing the compound of Comparative Example 1. All the panelists judged that it had a strong floral fragrance with a clearly recognized appearance and excellent diffusivity.

官能評価は５年以上経験した４人の専門パネラーが行い、実施例５の化合物を含有するマリーン調香料組成物は比較例１の化合物を含有するマリーン調香料組成物と比べてオゾン感が強くはっきりと認められ、拡散性に優れたマリーン調を有しているとパネラー全員が判断した。 (Example 11: Fragrance composition)
In accordance with the formulation shown in Table 6 below, a fragrance composition for perfume was prepared using the compound synthesized in Example 5 or the compound of Comparative Example 1.

The sensory evaluation was conducted by four expert panelists who had experienced for more than 5 years, and the marine fragrance composition containing the compound of Example 5 had a stronger feeling of ozone than the marine fragrance composition containing the compound of Comparative Example 1. All panelists judged that it was clearly recognized and had a marine tone with excellent diffusivity.

(Example 12: Shampoo)
A shampoo (100 g) containing 1.0% of the fragrance composition of Example 10 was prepared according to the formulation shown in Table 7 below. The sensory evaluation of this was performed by four expert panelists who had experienced for more than five years, and all four judged that the results were highly palatable and excellent in fragrance.

(Example 13: Body shampoo)
A body shampoo (100 g) flavored with the fragrance composition of Example 11 was prepared according to the formulation in Table 8 below. The sensory evaluation of this was carried out by four expert panelists who had been experienced for more than five years, and all four persons judged that the marine tone with a clean feeling could be clearly recognized, the taste was high, and the result was excellent in fragrance.

Claims (7)

The compound represented by Formula (1).

(In the formula, n is 1 to 3, R ₁ and R ₂ represent a hydrogen atom, or R ₁ and R ₂ form a methylene group, and the dotted line (----) is a single bond or a double bond. Represents a bond, and n represents 3 when representing a double bond (provided that R ₁ and R ₂ are not present when the dotted line (----) represents a double bond).   The compound of Claim 1 whose steric configuration of a compound represented by Formula (1) is 1'S-isomer.   The compound of Claim 1 whose steric configuration of a compound represented by Formula (1) is 1'R-isomer. A fragrance composition containing at least one compound represented by formula (1).

(In the formula, n is 1 to 3, R ₁ and R ₂ represent a hydrogen atom, or R ₁ and R ₂ form a methylene group, and the dotted line (----) is a single bond or a double bond. Represents a bond, and n represents 3 when representing a double bond (provided that R ₁ and R ₂ are not present when the dotted line (----) represents a double bond).   The fragrance | flavor composition of Claim 4 whose steric configuration of the compound represented by Formula (1) is 1'S-isomer.   The fragrance | flavor composition of Claim 4 whose steric configuration of the compound represented by Formula (1) is 1'R-isomer.   Food / beverage products, cosmetics, fragrances, daily and miscellaneous goods, oral compositions, hair care products, skin care products, body cleaning agents, detergents for clothing, softeners for clothing containing the fragrance composition according to claim 4 , Toiletry products, textile / textile products, clothing or pharmaceuticals.