JPH0144757B2 - - Google Patents
Info
- Publication number
- JPH0144757B2 JPH0144757B2 JP55032435A JP3243580A JPH0144757B2 JP H0144757 B2 JPH0144757 B2 JP H0144757B2 JP 55032435 A JP55032435 A JP 55032435A JP 3243580 A JP3243580 A JP 3243580A JP H0144757 B2 JPH0144757 B2 JP H0144757B2
- Authority
- JP
- Japan
- Prior art keywords
- fragrance
- present
- mixture
- compound
- aroma
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 claims description 16
- 239000003205 fragrance Substances 0.000 claims description 14
- ZWSMRUGTQTWTII-UHFFFAOYSA-N methyl 2-methyldecanoate Chemical compound CCCCCCCCC(C)C(=O)OC ZWSMRUGTQTWTII-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 11
- 239000003599 detergent Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N Benzyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 description 2
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000019568 aromas Nutrition 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- HQKQRXZEXPXXIG-VJOHVRBBSA-N chembl2333940 Chemical compound C1[C@]23[C@H](C)CC[C@H]3C(C)(C)[C@H]1[C@@](OC(C)=O)(C)CC2 HQKQRXZEXPXXIG-VJOHVRBBSA-N 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- YACSJCXELNXGRZ-UHFFFAOYSA-N methyl tricyclo[5.2.1.02,6 ]decane-2-carboxylate Chemical compound C1C2CCC1C1(C(=O)OC)C2CCC1 YACSJCXELNXGRZ-UHFFFAOYSA-N 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XHXUANMFYXWVNG-UHFFFAOYSA-N (+/-)-Menthyl acetate Chemical compound CC(C)C1CCC(C)CC1OC(C)=O XHXUANMFYXWVNG-UHFFFAOYSA-N 0.000 description 1
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- VPKMGDRERYMTJX-CMDGGOBGSA-N 1-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-1-penten-3-one Chemical compound CCC(=O)\C=C\C1C(C)=CCCC1(C)C VPKMGDRERYMTJX-CMDGGOBGSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- FACFHHMQICTXFZ-UHFFFAOYSA-N 2-(2-phenylimidazo[1,2-a]pyridin-3-yl)ethanamine Chemical compound N1=C2C=CC=CN2C(CCN)=C1C1=CC=CC=C1 FACFHHMQICTXFZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- SUAUILGSCPYJCS-UHFFFAOYSA-N Musk ambrette Chemical compound COC1=C([N+]([O-])=O)C(C)=C([N+]([O-])=O)C=C1C(C)(C)C SUAUILGSCPYJCS-UHFFFAOYSA-N 0.000 description 1
- 229940022663 acetate Drugs 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- GUUHFMWKWLOQMM-NTCAYCPXSA-N alpha-hexylcinnamaldehyde Chemical compound CCCCCC\C(C=O)=C/C1=CC=CC=C1 GUUHFMWKWLOQMM-NTCAYCPXSA-N 0.000 description 1
- GUUHFMWKWLOQMM-UHFFFAOYSA-N alpha-n-hexylcinnamic aldehyde Natural products CCCCCCC(C=O)=CC1=CC=CC=C1 GUUHFMWKWLOQMM-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 235000019717 geranium oil Nutrition 0.000 description 1
- 239000010648 geranium oil Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229940067137 musk ketone Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Description
【発明の詳細な説明】
本発明はトリシクロウンデカンカルボン酸エス
テルを香料として含有する組成物に関する。
本発明者らは、テルペン類の中で、多環構造を
有する化合物に優れた香気を有するものが多いこ
とに興味をもち、多環構造を有する化合物を種々
合成し、その香気を評価してきた。
その中で次の式（）で表わされるトリシクロ
〔５・２・１・02,6〕デカン−２−カルボン酸メチ
ルが優れた香気を有し、かつ酸性、アルカリ性の
ような苛酷な環境においても香気が減退すること
がなく、香料として極めて優秀なものであること
を見出し、本発明に至つた。
この化合物（）の香りは、大まかな分類によ
れば、草様の（Herbal）香りに分類されるもの
であるが、化合物（）には、式（ｘ）及び式
（ｎ）で表わされる２種の異性体がある。
式（ｘ）で表わされる異性体（エキソトリメ
チレン体）と式（ｎ）で表わされる異性体（エ
ンドトリメチレン体）とはそれぞれ若干異つた香
りを有し、それぞれ詳述すれば、前者は、松様
の、そして草様の香り（Piney−Green−
Herbal）、後者は、しようのう様の、草様の、は
つか様の香り（Camphoraceous−Herbal−
Minty）であると言える。
式（）で表わされる化合物は、上記の優れた
香りを有すると共に、酸性、アルカリ性のような
苛酷な環境下においてもその香調が減退又は変化
しないという点において特に優れている。即ち、
例えば、酸性洗浄剤、アルカリ洗浄剤等では、PH
が１〜４又は10〜13であり、通常の香料化合物に
とつては苛酷な条件下に置かれることとなり、温
度が高くなるに従い、保存中に香調が減退または
変化することが多い。
本発明は、酸、アルカリ、熱等に対する安定性
に優れたトリシクロ［5.2.1.02,6］デカン−２−カ
ルボン酸メチルを配合し草様香気を増した、香料
組成物の提供を目的として為されたものである。
本発明の化合物（）は、酸性、アルカリ性組
成物の香料成分として用いられる他に、通常の香
料が配合される組成物、例えば高級香料組成物、
香水、石鹸、シヤンプー、洗剤、化粧品、ワツク
ス等に使用することができることは勿論である。
本発明の化合物（）は、文献既知の物質であ
り、コツホ等（H.Koch and W.Haaf、Ann.
638、111（1960）及び特開昭53−82765に記載され
ているが、これらは単に合成化学上の成果として
知られているか、又は抗ウイルス剤の中間体とし
て知られているに過ぎず、本発明の香料として使
用は全く考慮されていない。
化合物（）上記文献記載の方法に従つて製造
すれば良いが、これを説明すると、ジシクロペン
タジエン（）に酸触媒を用いて水を付加しさら
に水添して飽和水和物（）に導くか、水添触媒
を用いて不飽和結合の一方を水添して半水添物
（）を得、これにいわゆるコツホカルボキシル
化反応を行ない、カルボン酸混合物（ｘ及び
ｎ）を得、これをエステル化すれば良い。
カルボン酸混合物（ｘ及びｎ）は条件によ
つて、変わり得るが通常ほぼ１：１の混合物とし
て得られ、これをメチルエステルとした式（）
で表わされる化合物も（ｘ）と（ｎ）のほぼ
１：１の混合物として得られる。通常はそのま
ま、あるいは他の香料成分と調合して用いる。ま
た、ｘ又はｎのいずれか一方を多く含むもの
もしくは純品を望む場合は、その混合物を精密蒸
留するか、もしくは特開昭53−82765に記載され
た方法などによつて分離することもできる。
以下に本発明を実施例によつて説明するが、本
発明はこれらの実施例に限定されるものではな
い。
実験例
トリシクロ〔５・２・１・02,6〕デカン−２−
カルボン酸メチル（エキソトリメチレン体とエン
ドトリメチレン体のほぼ１：１混合物）を、PH
1.5の酸性洗剤、PH10.9のアルカリ洗剤にそれぞ
れ0.1重量％（対洗剤）添加した場合の保存中
（20日間）の香調の変化を調べた結果を以下の表
に示す。
【表】
【表】
実施例 １
洗剤用フローラルタイプ香料組成物
フエニルエチルアルコール 200
Ｐ−ｔ−ブチル−α−メチルハイドロシンナミツ
クアルデヒド 40
リナロール 50
メチルヨノン 40
メンタニルアセテート 20
α−ヘキシルシンナミツクアルデヒド 200
ベンジルサリシレート 40
スチラリルアセテート 20
ターピネオール 40
パチユリオイル 10
ゼラニウムオイル 20
セドリルアセテート 50
ベンジルアセテート 60
ムスクアンブレツト 20
ムスクケトン 20
クマリン 20
ゲラニオール 50
900
（単位はｇ（グラム）である）
上記の香気組成物900ｇに、トリシクロ〔５・
２・１・02,6〕デカン−２−カルボン酸メチル
（エキソトリメチレン体とエンドトリメチレン体
のほぼ１：１混合物）100ｇを加えることにより
やや草様の香りが増した調合香料が得られた。 DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition containing tricycloundecanecarboxylic acid ester as a fragrance. The present inventors were interested in the fact that among terpenes, many compounds with polycyclic structures have excellent aromas, and have synthesized various compounds with polycyclic structures and evaluated their aromas. . Among them, methyl tricyclo[5.2.1.0 2,6 ]decane-2-carboxylate, which is represented by the following formula (), has an excellent aroma and can be used in harsh environments such as acidic and alkaline environments. The inventors have discovered that the aroma does not deteriorate and is extremely excellent as a fragrance, leading to the present invention. The scent of this compound () is roughly classified as a herbal scent, but the compound () contains two compounds represented by formulas (x) and (n). There are isomers of species. The isomer represented by formula (x) (exotrimethylene form) and the isomer represented by formula (n) (endotrimethylene form) each have slightly different scents. , pine-like, and grass-like scent (Piney-Green-
Herbal), the latter has a camphoraceous-herbal-
Minty). The compound represented by formula () has the above-mentioned excellent aroma, and is particularly excellent in that the aroma tone does not diminish or change even under harsh environments such as acidity and alkalinity. That is,
For example, acidic cleaning agents, alkaline cleaning agents, etc.
is 1 to 4 or 10 to 13, which means that ordinary fragrance compounds are placed under harsh conditions, and as the temperature increases, the fragrance tone often decreases or changes during storage. The purpose of the present invention is to provide a fragrance composition containing methyl tricyclo[5.2.1.0 2,6 ]decane-2-carboxylate, which has excellent stability against acids, alkalis, heat, etc., and has an increased grass-like aroma. It has been done. In addition to being used as a fragrance component in acidic and alkaline compositions, the compound () of the present invention can also be used in compositions containing ordinary fragrances, such as high-grade fragrance compositions.
Of course, it can be used in perfumes, soaps, shampoos, detergents, cosmetics, waxes, etc. The compound () of the present invention is a substance known in the literature, as described by Koch et al. (H.Koch and W.Haaf, Ann.
638, 111 (1960) and JP-A-53-82765, but these are only known as synthetic chemical achievements or as intermediates for antiviral agents. No use as a perfume in the present invention is contemplated. Compound () can be produced according to the method described in the above literature, but to explain this, water is added to dicyclopentadiene () using an acid catalyst and further hydrogenated to lead to a saturated hydrate (). Alternatively, one of the unsaturated bonds is hydrogenated using a hydrogenation catalyst to obtain a hemihydride (), which is subjected to a so-called Kotsuho carboxylation reaction to obtain a carboxylic acid mixture (x and n), which is It can be esterified. The carboxylic acid mixture (x and n) may vary depending on the conditions, but it is usually obtained as a nearly 1:1 mixture, and this is expressed as a methyl ester by the formula ()
The compound represented by is also obtained as a mixture of (x) and (n) in an approximately 1:1 ratio. It is usually used as is or mixed with other fragrance ingredients. In addition, if a product containing a large amount of either x or n or a pure product is desired, the mixture can be precision distilled or separated by the method described in JP-A No. 53-82765. . EXAMPLES The present invention will be explained below using Examples, but the present invention is not limited to these Examples. Experimental example Tricyclo[5・2・1・0 2,6 ]decane-2-
Methyl carboxylate (approximately a 1:1 mixture of exotrimethylene and endotrimethylene) was
The table below shows the results of investigating changes in scent tone during storage (20 days) when 0.1% by weight (based on detergent) was added to acidic detergents with a pH of 1.5 and alkaline detergents with a pH of 10.9. [Table] [Table] Example 1 Floral type fragrance composition for detergent Phenylethyl alcohol 200 P-t-butyl-α-methylhydrocinnamic aldehyde 40 Linalool 50 Methylionone 40 Menthanyl acetate 20 α-hexyl cinnamic aldehyde 200 Benzyl salicylate 40 Styraryl acetate 20 Terpineol 40 Pachinko oil 10 Geranium oil 20 Cedryl acetate 50 Benzyl acetate 60 Musk ambrette 20 Musk ketone 20 Coumarin 20 Geraniol 50 900 (Units are g (grams)) To 900 g of the above fragrance composition, Tricyclo [5・
2.1.0 2,6 ] By adding 100 g of methyl decane-2-carboxylate (approximately 1:1 mixture of exotrimethylene and endotrimethylene), a blended fragrance with a slightly grass-like aroma was obtained. It was done.
Claims (1)
記の式で表されるトリシクロ［５，２，１，02,6］
デカン−２−カルボン酸メチルが0.1〜20重量部
配合された香料組成物。 [Claims] 1. Tricyclo[5,2,1,0 2,6 ] expressed by the following formula per 100 parts by weight of a commonly used fragrance composition.
A fragrance composition containing 0.1 to 20 parts by weight of methyl decane-2-carboxylate.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3243580A JPS56128710A (en) | 1980-03-14 | 1980-03-14 | Perfume composition |
| CH1522/81A CH654204A5 (en) | 1980-03-14 | 1981-03-06 | PERFUME COMPOSITIONS AND PROCEDURE FOR THEIR PREPARATION. |
| US06/241,855 US4374052A (en) | 1980-03-14 | 1981-03-09 | Perfume composition |
| DE3108867A DE3108867C2 (en) | 1980-03-14 | 1981-03-09 | Perfume composition and process for making the same |
| FR8104885A FR2477874B1 (en) | 1980-03-14 | 1981-03-11 | FRICTIONAL COMPOSITION BASED ON TRICYCLO (5.2.1.0.2,6) METHANE DECANE-2-CARBOXYLATE AND PROCESS FOR PREPARING THE SAME |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3243580A JPS56128710A (en) | 1980-03-14 | 1980-03-14 | Perfume composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56128710A JPS56128710A (en) | 1981-10-08 |
| JPH0144757B2 true JPH0144757B2 (en) | 1989-09-29 |
Family
ID=12358866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3243580A Granted JPS56128710A (en) | 1980-03-14 | 1980-03-14 | Perfume composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56128710A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4579509B2 (en) * | 2002-08-09 | 2010-11-10 | 花王株式会社 | Fragrance composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5527188A (en) * | 1978-08-12 | 1980-02-27 | Henkel Kgaa | Perfume made of or containing ester of tricyclo*5*2*1*02*6*decann3*4**carboxylic acid mixture |
-
1980
- 1980-03-14 JP JP3243580A patent/JPS56128710A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5527188A (en) * | 1978-08-12 | 1980-02-27 | Henkel Kgaa | Perfume made of or containing ester of tricyclo*5*2*1*02*6*decann3*4**carboxylic acid mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56128710A (en) | 1981-10-08 |
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