JPH0780863B2 - 6-Ethyl-5-oxatricyclo [4.2.1 / 0 ▲ up3, up7 ▼] nonane-3-carboxylic acid ester and fragrance composition containing the same - Google Patents
6-Ethyl-5-oxatricyclo [4.2.1 / 0 ▲ up3, up7 ▼] nonane-3-carboxylic acid ester and fragrance composition containing the sameInfo
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- JPH0780863B2 JPH0780863B2 JP11229586A JP11229586A JPH0780863B2 JP H0780863 B2 JPH0780863 B2 JP H0780863B2 JP 11229586 A JP11229586 A JP 11229586A JP 11229586 A JP11229586 A JP 11229586A JP H0780863 B2 JPH0780863 B2 JP H0780863B2
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- ethyl
- oxatricyclo
- nonane
- carboxylic acid
- acid ester
- Prior art date
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は次の一般式（Ｉ） （式中、Ｒは低級アルキル基を示す） で表わされる6-エチル‐5-オキサトリシクロ〔4.2.1.0
3,7〕ノナン‐3-カルボル酸エステル及びこれを含有す
る香料組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides the following general formula (I): (In the formula, R represents a lower alkyl group) 6-ethyl-5-oxatricyclo [4.2.1.0
[3,7 ] Nonane-3-carboxylic acid ester and a fragrance composition containing the same.
従来、ビシクロ〔2.2.1〕ヘプタンカルボアルデヒドを
カニツツアロ反応に付して次式（１）〔特開昭57−4517
9号〕又は式（２）〔特開昭57−82330号〕のgem-ビス
（ヒドロキシメチル）構造を有する化合物を得ることが
知られている。Conventionally, bicyclo [2.2.1] heptanecarbaldehyde has been subjected to the Cannituaro reaction by the following formula (1) [JP-A-57-4517].
No. 9] or formula (2) [JP-A-57-82330], it is known to obtain a compound having a gem-bis (hydroxymethyl) structure.
しかし、これらの化合物を三環式化合物に誘導し、その
有用性について検討した報告はこれまで全くみあたらな
い。 However, no reports have been found so far regarding the induction of these compounds into tricyclic compounds and examination of their usefulness.
斯かる実情において、本発明者は、2,2-ビス（ヒドロキ
シメチル）‐6-エチリデンビシクロ〔2.2.1〕ヘプタン
から誘導される（Ｉ）式で表わされる三環式骨格を有す
る新規化合物が優れた香気を有することを見出し、本発
明を完成した。In such circumstances, the present inventor has found that a novel compound having a tricyclic skeleton represented by the formula (I) derived from 2,2-bis (hydroxymethyl) -6-ethylidenebicyclo [2.2.1] heptane The present invention has been completed by finding that it has an excellent fragrance.
すなわち、本発明は、（Ｉ）式で表わされる6-エチル‐
5-オキサトリシクロ〔4.2.1.03,7〕ノナン‐3-カルボン
酸エステルを提供するものである。本発明は、更にこれ
を含有する香料組成物を提供するものである。That is, the present invention provides 6-ethyl-
The present invention provides 5-oxatricyclo [4.2.1.0 3,7 ] nonane-3-carboxylic acid ester. The present invention further provides a fragrance composition containing the same.
本発明化合物（Ｉ）は、例えば、次の反応式に従つて、
2-エチリデンビシクロ〔2.2.1〕ヘプタン‐５（又は
６）‐カルボアルデヒド（II）をホルムアルデヒドとの
カニツツアロ反応に付してメチロール化して2,2-ビス
（ヒドロキシメチル）‐6-エチリデンビシクロ〔2.2.
1〕ヘプタン（III）となし、次いでこれを酸性条件下環
化させて6-エチル‐3-ヒドロキシメチル‐5-オキサトリ
シクロ〔4.2.1.03,7〕ノナン（IV）となし、次いでこれ
を酸化して6-エチル‐5-オキサトリシクロ〔4.2.1.
03,7〕ノナン‐3-カルボン酸（Ｖ）となし、更にこれを
エステル化することにより製造される。The compound (I) of the present invention can be produced, for example, according to the following reaction formula:
2,2-Bis (hydroxymethyl) -6-ethylidenebicyclo [2.2.1] heptane-5 (or 6) -carbaldehyde (II) is methylolated by the Canitzuaro reaction with formaldehyde. 2.2.
1] heptane (III) and then cyclized under acidic conditions to 6-ethyl-3-hydroxymethyl-5-oxatricyclo [4.2.1.0 3,7 ] nonane (IV), then Of 6-ethyl-5-oxatricyclo (4.2.1.
[0 3,7 ] Nonane-3-carboxylic acid (V), which is further esterified.
（式中、Ｒは前記と同じものを示す） 尚、（II）の化合物とホルムアルデヒドとのカニツツア
ロ反応において、（III）式の6-エチリデン体の他に（V
I）式の５−エチリデン体も生成されるが、次の環化反
応において、6-エチリデン体の環化条件では5-エチリデ
ン体の環化は生起しないので、環化反応に先立つて両者
を分離する必要はなく、そのまま当該反応に供すること
ができる。 (In the formula, R represents the same as the above.) In the Canitzuaro reaction of the compound of (II) with formaldehyde, in addition to the 6-ethylidene compound of the formula (III) (V
Although the 5-ethylidene derivative of the formula (I) is also produced, in the next cyclization reaction, cyclization of the 5-ethylidene body does not occur under the cyclization condition of the 6-ethylidene body, so both of them are cyclized prior to the cyclization reaction. It is not necessary to separate and can be directly used for the reaction.
化合物（II）から（III）を得る反応は公知であり、こ
れに従つて行われる。化合物（III）から（IV）を得る
には、（III）を硫酸、リン酸等の酸の存在下、イソプ
ロピルアルコール等の溶媒中加熱還流すればよい。化合
物（IV）から（Ｖ）を得るために使用される酸化剤とし
ては、クロム酸、過マンガン酸カリ等が挙げられ、反応
は自体公知の酸化条件下で行われる。化合物（Ｖ）のエ
ステル化は常法によつて行われる。The reaction for obtaining (III) from compound (II) is known and is carried out according to this. To obtain (IV) from compound (III), (III) may be heated under reflux in a solvent such as isopropyl alcohol in the presence of an acid such as sulfuric acid or phosphoric acid. Examples of the oxidant used to obtain the compounds (IV) to (V) include chromic acid and potassium permanganate, and the reaction is carried out under known oxidizing conditions. Esterification of compound (V) is carried out by a conventional method.
本発明化合物（Ｉ）は果実様の香気を有し、例えば、メ
チルエステル体〔（Ｉ）,R＝メチル〕は渋みのあるエス
テル的なフルーテイな香りを、エチルエステル体
〔（Ｉ）,R＝エチル〕はフルーテイ、スパイシーな香り
を、n-プロピルエステル体〔（Ｉ）,R＝ｎ−プロピル〕
はよもぎ様のグリン、フローラル、フルーテイな香りを
有する。The compound (I) of the present invention has a fruity odor, and for example, the methyl ester [(I), R = methyl] has an astringent, ester-like fruity scent and the ethyl ester [(I), R = Ethyl] has a fruity, spicy fragrance, n-propyl ester [(I), R = n-propyl]
Hayogi-like green, floral and fruity aroma.
本発明化合物（Ｉ）は、例えば高級な香料組成物、香
水、石鹸、シヤンプー、ヘアリンス、洗剤、化粧品、ス
プレー、芳香剤等の賦香を必要とされるものに広汎に使
用できる。The compound (I) of the present invention can be widely used in, for example, high-quality fragrance compositions, perfumes, soaps, shampoos, hair rinses, detergents, cosmetics, sprays, fragrances, and the like that require fragrance.
次に参考例及び実施例を挙げて本発明を説明する。 Next, the present invention will be described with reference to Reference Examples and Examples.
参考例１ 2,2-ビス（ヒドロキシメチル）‐6-エチリデンビシクロ
〔2.2.1〕ヘプタン及び2,2-ビス（ヒドロキシメチル）
‐5-エチリデンビシクロ〔2.2.1〕ヘプタンの合成： 2-エチリデンビシクロ〔2.2.1〕ヘプタン‐５（又は
６）‐カルボアルデヒド300.4g（2mol）と37％ホルマリ
ン水溶液405.5g（5mol）及び480m1のメタノールを氷浴
下に攪拌し、20％水酸化ナトリウム水溶液16gを加え
た。しだいに室温にもどすと系は白濁してきた。１時間
40分後、さらに20％水酸化ナトリウム水溶液184gを１時
間10分で滴下した。内温は28℃まで上昇した。滴下終了
後20時間50℃に加熱攪拌した。加熱を止め再び氷水浴中
で攪拌した。水素化ホウ素ナトリウム7.56g（0.2mol）
を400gの20％水酸化ナトリウム水溶液に溶かした溶液を
１時間で滴下し、室温で１時間攪拌した。エーテルで３
回抽出した。エーテル層は4N塩酸で酸性し、飽和炭酸水
素ナトリウム水溶液及び水で洗浄の後、無水硫酸マグネ
シウムで乾燥した。溶媒を留去して粗生成物363g（収率
99.7％）を得た。Reference Example 1 2,2-bis (hydroxymethyl) -6-ethylidenebicyclo [2.2.1] heptane and 2,2-bis (hydroxymethyl)
Synthesis of 5-ethylidene bicyclo [2.2.1] heptane: 2-ethylidene bicyclo [2.2.1] heptane-5 (or 6) -carbaldehyde 300.4 g (2 mol) and 37% formalin aqueous solution 405.5 g (5 mol) and 480 ml Of methanol was stirred in an ice bath, and 16 g of 20% aqueous sodium hydroxide solution was added. The system became cloudy when gradually returned to room temperature. 1 hour
After 40 minutes, 184 g of 20% aqueous sodium hydroxide solution was further added dropwise over 1 hour and 10 minutes. The internal temperature rose to 28 ° C. After completion of dropping, the mixture was heated and stirred at 50 ° C. for 20 hours. The heating was stopped and the mixture was stirred again in the ice-water bath. Sodium borohydride 7.56g (0.2mol)
Was dissolved in 400 g of a 20% sodium hydroxide aqueous solution, and the solution was added dropwise over 1 hour, followed by stirring at room temperature for 1 hour. 3 with ether
Extracted twice. The ether layer was acidified with 4N hydrochloric acid, washed with saturated aqueous sodium hydrogen carbonate solution and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off to give 363 g of a crude product (yield
99.7%).
沸点:101〜118℃/0.1mmHg 元素分析C11H18O2として 計算値（％）:C;72.49,H;9.95 実測値（％）:C;72.42,H;10.00 IR（NaCl,cm-1）:3305（OH）,3040（ビニル基）,2950,1
450,1375（メチル基）,10201 H−NMR（δppm）:5.57〜4.9（1H,m）， 3.57（4H,br,m）,3.17（2H,br,s,OH）,1.55（3H,d,J＝6
Hz）,2.77〜1.0（8H,m） MS（相対強度）:182（M+,31％）,151（Ｍ−CH2OH,24
％）,79（54％）,57（100％） 参考例２ 6-エチル‐3-（ヒドロキシメチル）‐5-オキサトリシク
ロ〔4.2.1.03,7〕ノナンの合成： 2,2-ビス（ヒドロキシメチル）‐５（又は６）‐エチリ
デンビシクロ〔2.2.1〕ヘプタン5g（27.4mmol）を15m1
の水、15m1のイソプロピルアルコール及び5gの濃硫酸中
１時間加熱還流した。氷水に注ぎ、エーテルで抽出し
た。エーテル層は水、飽和炭酸水素ナトリウム水溶液及
び水で洗い、無水硫酸ナトリウムで乾燥した。溶媒を留
去した後、ヘキサン‐酢酸エチル（2:1）を溶媒として
シリカゲルカラマクロマトグラフイーにより標記アルコ
ールを単離した。Boiling point: 101 to 118 ° C. / 0.1 mmHg Elemental analysis C 11 H 18 O 2 Calculated (%): C; 72.49, H; 9.95 Found (%): C; 72.42, H; 10.00 IR (NaCl, cm - 1 ): 3305 (OH), 3040 (vinyl group), 2950,1
450,1375 (methyl group), 1020 1 H-NMR (δppm): 5.57 to 4.9 (1H, m), 3.57 (4H, br, m), 3.17 (2H, br, s, OH), 1.55 (3H, d, J ＝ 6
Hz), 2.77 to 1.0 (8H, m) MS (relative intensity): 182 (M + , 31%), 151 (M-CH 2 OH, 24
%), 79 (54%), 57 (100%) Reference Example 2 Synthesis of 6-ethyl-3- (hydroxymethyl) -5-oxatricyclo [4.2.1.0 3,7 ] nonane: 2,2-bis (Hydroxymethyl) -5 (or 6) -ethylidene bicyclo [2.2.1] heptane 5g (27.4mmol) 15m1
Of water, 15 ml of isopropyl alcohol and 5 g of concentrated sulfuric acid were heated under reflux for 1 hour. It was poured into ice water and extracted with ether. The ether layer was washed with water, saturated aqueous sodium hydrogen carbonate solution and water, and dried over anhydrous sodium sulfate. After the solvent was distilled off, the title alcohol was isolated by silica gel calama chromatography using hexane-ethyl acetate (2: 1) as a solvent.
収量1.58g（収率32％） 沸点110℃/0.06mmHg 元素分析C11H18O2として 計算値（％）:C;72.49,H;9.95 実測値（％）:C;72.55,H;9.80 IR（NaCl,cm-1）:3400（OH）,2955,2875,1460,1375（メ
チル基）,10201 H−NMR（δppm）:3.80（1H,d,J＝8Hz）,3.62（1H,b,J
＝8Hz）,3.48（2H,broad,s）,0.92（3H,t,J＝6Hz）,3〜
0.5（11H,m） MS（相対強度）:182（M+,100％）,151（Ｍ−CH2OH,63
％）,57（80％） 参考例３ 6-エチル‐5-オキサトリシクロ〔4.2.1.03,7〕ノナン‐
3-カルボン酸の合成： 無水クロム酸200g（2mol）を氷冷下攪拌しながら1600m1
の酢酸と200m1の水の中に加えた。その中へ200m1の酢酸
に溶かした参考例２で得たアルコール90g（0.5mo1）を
５℃以下に保ちながら滴下した。室温で２時間攪拌した
後一晩放置した。飽和食塩水1.5lを加えてクロロホルム
で抽出した。クロロホルム層は強アルカリ性の水酸化ナ
トリウム水溶液で抽出した。水層を塩酸で強酸性にもど
してエーテルで抽出した。エーテル層は水洗して無水硫
酸マグネシウムで乾燥した。溶媒を留去し減圧で蒸留し
て標記カルボン酸を得た。Yield 1.58g (Yield 32%) Boiling point 110 ° C / 0.06mmHg Calculated as elemental analysis C 11 H 18 O 2 (%): C; 72.49, H; 9.95 Actual value (%): C; 72.55, H; 9.80 IR (NaCl, cm -1 ): 3400 (OH), 2955,2875,1460,1375 (methyl group), 1020 1 H-NMR (δppm): 3.80 (1H, d, J = 8Hz), 3.62 (1H, b, J
= 8Hz), 3.48 (2H, broad, s), 0.92 (3H, t, J = 6Hz), 3 ~
0.5 (11H, m) MS (relative intensity): 182 (M + , 100%), 151 (M-CH 2 OH, 63
%), 57 (80%) Reference Example 3 6-Ethyl-5-oxatricyclo [4.2.1.0 3,7 ] nonane-
Synthesis of 3-carboxylic acid: Chromic anhydride 200g (2mol) with stirring under ice cooling 1600m1
Of acetic acid and 200 ml of water. 90 g (0.5 mol) of the alcohol obtained in Reference Example 2 dissolved in 200 ml of acetic acid was added dropwise thereto while keeping the temperature below 5 ° C. The mixture was stirred at room temperature for 2 hours and then left overnight. 1.5 l of saturated saline was added, and the mixture was extracted with chloroform. The chloroform layer was extracted with a strongly alkaline aqueous sodium hydroxide solution. The aqueous layer was acidified with hydrochloric acid and extracted with ether. The ether layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off and the residue was distilled under reduced pressure to obtain the title carboxylic acid.
収量52.77g（収率55％） 沸点116〜138℃/0.04mmHg 元素分析C11H16O3として 計算値（％）:C;67.32,H;8.22 実測値（％）:C;67.40,H;8.10 IR（NaCl,cm-1）:2960,2880,1700,3500〜21501 H−NMR（δppm）:9.42（1H,s）,4.10（1H,d,J＝8Hz）,
3.78（1H,d,J＝8Hz）,1.58（2H,q,J＝7Hz）,0.93（3H,
t,J＝7Hz）,2.7〜0.5（8H,m） MS（相対強度）:196（M+,68％）,165（33％）,151（Ｍ
−COOH,36％）,81（34％）,79（43％）,77（39％）,57
（100％）,55（37％）,41（37％） 実施例１ 6-エチル‐5-オキサトリシクロ〔4.2.1.03,7〕ノナン‐
3-カルボン酸メチル（I,R＝メチル）の合成： 参考例３で得たカルボン酸（I,R＝Ｈ）15g（0.077mol）
を50m1のメタノール中0.78gの濃硫酸（0.008mol）を触
媒として加えて10時間加熱還流した。溶媒を濃縮し、少
量の水を加えてエーテルで抽出した。飽和重ソウ水、水
で洗浄し、無水硫酸マグネシウムで乾燥した。溶媒を留
去し減圧で蒸留し標記化合物を得た。Yield 52.77g (55% yield) Boiling point 116-138 ℃ / 0.04mmHg Elemental analysis Calculated as C 11 H 16 O 3 (%): C; 67.32, H; 8.22 Measured value (%): C; 67.40, H ; 8.10 IR (NaCl, cm -1 ): 2960,2880,1700,3500 to 2150 1 H-NMR (δppm): 9.42 (1H, s), 4.10 (1H, d, J = 8Hz),
3.78 (1H, d, J = 8Hz), 1.58 (2H, q, J = 7Hz), 0.93 (3H,
t, J = 7Hz), 2.7 to 0.5 (8H, m) MS (relative intensity): 196 (M + , 68%), 165 (33%), 151 (M
-COOH, 36%), 81 (34%), 79 (43%), 77 (39%), 57
(100%), 55 (37%), 41 (37%) Example 1 6-Ethyl-5-oxatricyclo [4.2.1.0 3,7 ] nonane-
Synthesis of methyl 3-carboxylate (I, R = methyl): 15 g (0.077 mol) of carboxylic acid (I, R = H) obtained in Reference Example 3
Was added with 0.78 g of concentrated sulfuric acid (0.008 mol) as a catalyst in 50 ml of methanol, and the mixture was heated under reflux for 10 hours. The solvent was concentrated, a small amount of water was added, and the mixture was extracted with ether. The extract was washed with saturated sodium bicarbonate water and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off and the residue was distilled under reduced pressure to obtain the title compound.
収量12.96g（収率80％） 沸点136℃/14mmHg 元素分析C12H18O3として 計算値:C;68.55％,H;8.63％ 実測値:C;68.64％,H;8.51％ IR（NaCl,cm-1）:2970,2880,1725,1435,1360,1275,122
0,1120,10401 H−NMR（δppm）:4.00（1H,d,J＝8Hz）,3.70（1H,d,J
＝7Hz）,3.65（3H,s）,1.55（2H,q,J＝7Hz）,0.93（3H,
t,J＝7Hz）,2.6〜0.7（8H,m） MS（相対強度）:210（M+,39％）,179（31％）,151（36
％）,150（51％）,79（45％）,77（33％）,57（100％） 実施例２ 6-エチル‐5-オキサトリシクロ〔4.2.1.03,7〕ノナン‐
3-カルボン酸エチル（I,R＝エチル）の合成： 実施例１と同様にしてエチルエステル体（I,R＝エチ
ル）を合成した。Yield 12.96 g (80% yield) having a boiling point 136 ° C. / 14 mmHg Elemental analysis C 12 H 18 O 3 Calculated: C; 68.55%, H; 8.63% Found: C; 68.64%, H; 8.51% IR (NaCl , cm -1 ): 2970,2880,1725,1435,1360,1275,122
0,1120,1040 1 H-NMR (δppm): 4.00 (1H, d, J = 8Hz), 3.70 (1H, d, J
= 7Hz), 3.65 (3H, s), 1.55 (2H, q, J = 7Hz), 0.93 (3H,
t, J = 7Hz), 2.6 to 0.7 (8H, m) MS (relative intensity): 210 (M + , 39%), 179 (31%), 151 (36
%), 150 (51%), 79 (45%), 77 (33%), 57 (100%) Example 2 6-Ethyl-5-oxatricyclo [4.2.1.0 3,7 ] nonane-
Synthesis of ethyl 3-carboxylate (I, R = ethyl): An ethyl ester compound (I, R = ethyl) was synthesized in the same manner as in Example 1.
収率84％ 沸点136〜137℃/14mmHg 元素分析C13H20O3として 計算値:C;69.61％,H;8.99％ 実測値:C;69.55％,H;9.02％ IR（NaCl,cm-1）:2975,2890,1730,1365,1280,1220,112
0,10401 H−NMR（δppm）:4.08（2H,q,J＝7Hz）,4.00（1H,d,J
＝8Hz）,3.70（1H,d,J＝8Hz）,1.55（2H,q,J＝7Hz）,1.
23（3H,t,J＝7Hz）,093（3H,t,J＝7Hz）,2.6〜0.5（8H,
m） MS（相対強度）:224（M+,36％）,151（49％）,150（57
％）,79（50％）,77（33％）,57（100％） 実施例３ 6-エチル‐5-オキサトリシクロ〔4.2.1.03,7〕ノナン‐
3-カルボン酸n-プロピル（I,R＝ｎ−プロピル）合成： 実施例１と同様にしてｎ−プロピル体（I,R＝ｎ−プロ
ピル）を合成した。Yield 84% boiling point 136~137 ℃ / 14mmHg elemental analysis C 13 H 20 O 3 Calculated: C; 69.61%, H; 8.99% Found: C; 69.55%, H; 9.02% IR (NaCl, cm - 1 ): 2975,2890,1730,1365,1280,1220,112
0,1040 1 H-NMR (δppm): 4.08 (2H, q, J = 7Hz), 4.00 (1H, d, J
= 8Hz), 3.70 (1H, d, J = 8Hz), 1.55 (2H, q, J = 7Hz), 1.
23 (3H, t, J = 7Hz), 093 (3H, t, J = 7Hz), 2.6 ~ 0.5 (8H,
m) MS (relative intensity): 224 (M + , 36%), 151 (49%), 150 (57
%), 79 (50%), 77 (33%), 57 (100%) Example 3 6-Ethyl-5-oxatricyclo [4.2.1.0 3,7 ] nonane-
3-Carboxylic acid n-propyl (I, R = n-propyl) synthesis: In the same manner as in Example 1, an n-propyl derivative (I, R = n-propyl) was synthesized.
収率82％ 沸点148〜150℃/15mmHg 元素分析C14H22O3として 計算値:C;70.56％,H;9.30％ 実測値:C;70.51％,H;9.30％ IR（NaCl,cm-1）:2970,2880,1725,1460,1375,1275,122
0,1120,10401 H−NMR（δppm）:4.00（2H,t,J＝6Hz）,4.03（1H,d,J
＝7Hz）,3.72（1H,d,J＝7Hz）,0.93（6H,t,J＝6Hz）,2.
6〜1.2（12H,m） MS（相対強度）:238（M+,29％）,151（59％）,150（56
％）,79（51％）,77（28％）,57（100％）,43（36％）,
41（42％） 実施例４ フルーテイタイプシヤンプー用香料 ベルガモツトベース 80（重量部） レモンベース 100 アリルヘプタノエート 10 ベンジルアセテート 40 シトロネロール 40 シトロネリルアセテート 20 ゲラニオール 60 フエニルエチルアルコール 100 リリアール（１） 30（重量部） リラール（２） 40 ヘキシルシンナミツクアルデヒド 150 メチルジヒドロジヤスモネート 40 γ‐メチルイオノン 25 アセチルセドレン 50 ボルニルメトキシシクロヘキサノール 30 ガラクソライド（３） 100 （50％ジエチルフタレート溶液） γ‐ウンデカラクトン ５ p-ヒドロキシフエニルブタノン 20 ベンゾインレジノイド 40 980 上記調合香料980部に、エチル 6-エチル‐5-オキサト
リシクロ〔4.2.1.03,7〕ノナン‐3-カルボキシレート20
部を加えることによりフレツシユなフルーテイ感の増し
たフルーテイタイプのシヤンプー用香料が得られた。Yield 82% boiling point 148-150 ° C. / 15 mmHg Elemental analysis C 14 H 22 O 3 Calculated: C; 70.56%, H; 9.30% Found: C; 70.51%, H; 9.30% IR (NaCl, cm - 1 ): 2970,2880,1725,1460,1375,1275,122
0,1120,1040 1 H-NMR (δppm): 4.00 (2H, t, J = 6Hz), 4.03 (1H, d, J
= 7Hz), 3.72 (1H, d, J = 7Hz), 0.93 (6H, t, J = 6Hz), 2.
6 to 1.2 (12H, m) MS (relative intensity): 238 (M + , 29%), 151 (59%), 150 (56
%), 79 (51%), 77 (28%), 57 (100%), 43 (36%),
41 (42%) Example 4 Perfume for fruity type shampoo Bergamot base 80 (parts by weight) Lemon base 100 Allyl heptanoate 10 Benzyl acetate 40 Citronellol 40 Citronellyl acetate 20 Geraniol 60 Phenylethyl alcohol 100 Liliar (1) 30 (Parts by weight) Liral (2) 40 Hexylcinnamic aldehyde 150 Methyl dihydrodiasmonate 40 γ-Methylionone 25 Acetyl Cedrene 50 Bornyl methoxycyclohexanol 30 Galaxolide (3) 100 (50% diethyl phthalate solution) γ-Undeca Lactone 5 p-Hydroxyphenylbutanone 20 Benzoinresinoid 40 980 980 parts of the above-prepared fragrance is mixed with ethyl 6-ethyl-5-oxatricyclo [4.2.1.0 3,7 ] nonane-3-carboxylate 20.
By adding the parts, a fruity type shampoo fragrance with an increased freshness and fruity feeling was obtained.
注（１）：ジボダン社商品名 p-t-ブチル‐α‐メチルハイドロシンナミツクアルデヒ
ド （２）:IFF社商品名 4-（4-ヒドロキシ‐4-メチルペンチル）‐3-シクロヘキ
セン‐1-カルボキシアルデヒド （３）:IFF社商品名 1,3,4,6,7,8-ヘキサハイドロ‐4,6,6,7,8,8-ヘキサメチ
ルシクロペンタ‐γ‐2-ベンゾピランNote (1): Givaudan's trade name pt-butyl-α-methylhydrocinnamaldehyde (2): IFF's trade name 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde ( 3): IFF company product name 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran
Claims (2)
3,7〕ノナン‐3-カルボル酸エステル。1. The following formula (I) (In the formula, R represents a lower alkyl group) 6-ethyl-5-oxatricyclo [4.2.1.0
3,7 ] Nonane-3-carboxylic acid ester.
3,7〕ノナン‐3-カルボル酸エステルを含有することを
特徴とする香料組成物。2. The following formula (I) (In the formula, R represents a lower alkyl group) 6-ethyl-5-oxatricyclo [4.2.1.0
3,7 ] Nonane-3-carboxylic acid ester-containing perfume composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11229586A JPH0780863B2 (en) | 1986-05-16 | 1986-05-16 | 6-Ethyl-5-oxatricyclo [4.2.1 / 0 ▲ up3, up7 ▼] nonane-3-carboxylic acid ester and fragrance composition containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11229586A JPH0780863B2 (en) | 1986-05-16 | 1986-05-16 | 6-Ethyl-5-oxatricyclo [4.2.1 / 0 ▲ up3, up7 ▼] nonane-3-carboxylic acid ester and fragrance composition containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62270571A JPS62270571A (en) | 1987-11-24 |
| JPH0780863B2 true JPH0780863B2 (en) | 1995-08-30 |
Family
ID=14583110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11229586A Expired - Lifetime JPH0780863B2 (en) | 1986-05-16 | 1986-05-16 | 6-Ethyl-5-oxatricyclo [4.2.1 / 0 ▲ up3, up7 ▼] nonane-3-carboxylic acid ester and fragrance composition containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0780863B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6600116B1 (en) * | 2019-07-19 | 2019-10-30 | 高砂香料工業株式会社 | Fragrance composition |
-
1986
- 1986-05-16 JP JP11229586A patent/JPH0780863B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62270571A (en) | 1987-11-24 |
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