JPH01128993A - Methyl-4,6-0-(7-hydroxy-3,7-dimethyl)octylidene-d-glycoside - Google Patents
Methyl-4,6-0-(7-hydroxy-3,7-dimethyl)octylidene-d-glycosideInfo
- Publication number
- JPH01128993A JPH01128993A JP62287073A JP28707387A JPH01128993A JP H01128993 A JPH01128993 A JP H01128993A JP 62287073 A JP62287073 A JP 62287073A JP 28707387 A JP28707387 A JP 28707387A JP H01128993 A JPH01128993 A JP H01128993A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- methyl
- formula
- dimethyl
- octylidene
- 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.)
- Granted
Links
- 239000000126 substance Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 48
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 abstract description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- 239000003205 fragrance Substances 0.000 description 34
- 230000014759 maintenance of location Effects 0.000 description 20
- 230000000694 effects Effects 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- WQZGKKKJIJFFOK-SVZMEOIVSA-N (+)-Galactose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-SVZMEOIVSA-N 0.000 description 4
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009965 odorless effect Effects 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- WPFVBOQKRVRMJB-UHFFFAOYSA-N hydroxycitronellal Chemical compound O=CCC(C)CCCC(C)(C)O WPFVBOQKRVRMJB-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- XFDQLDNQZFOAFK-UHFFFAOYSA-N 2-benzoyloxyethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOC(=O)C1=CC=CC=C1 XFDQLDNQZFOAFK-UHFFFAOYSA-N 0.000 description 1
- UADWUILHKRXHMM-UHFFFAOYSA-N 2-ethylhexyl benzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1 UADWUILHKRXHMM-UHFFFAOYSA-N 0.000 description 1
- 229940106004 2-ethylhexyl benzoate Drugs 0.000 description 1
- RIIHSWLVNNRVOK-UHFFFAOYSA-N 3-phenylpropyl 2-ethylbutanoate Chemical compound CCC(CC)C(=O)OCCCC1=CC=CC=C1 RIIHSWLVNNRVOK-UHFFFAOYSA-N 0.000 description 1
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 1
- 101150041968 CDC13 gene Proteins 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DUFKCOQISQKSAV-UHFFFAOYSA-N Polypropylene glycol (m w 1,200-3,000) Chemical class CC(O)COC(C)CO DUFKCOQISQKSAV-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- UADWUILHKRXHMM-ZDUSSCGKSA-N benzoflex 181 Natural products CCCC[C@H](CC)COC(=O)C1=CC=CC=C1 UADWUILHKRXHMM-ZDUSSCGKSA-N 0.000 description 1
- ORSXISLPWNELTJ-UHFFFAOYSA-N benzyl 2-phenoxyacetate Chemical compound C=1C=CC=CC=1COC(=O)COC1=CC=CC=C1 ORSXISLPWNELTJ-UHFFFAOYSA-N 0.000 description 1
- 229960002903 benzyl benzoate Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- WCMMKSYUPQLQKB-UHFFFAOYSA-N dihexyl 2,3-dihydroxybutanedioate Chemical compound CCCCCCOC(=O)C(O)C(O)C(=O)OCCCCCC WCMMKSYUPQLQKB-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- AMMPRZCMKXDUNE-UHFFFAOYSA-N trihexyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCOC(=O)CC(O)(C(=O)OCCCCCC)CC(=O)OCCCCCC AMMPRZCMKXDUNE-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Seasonings (AREA)
- Saccharide Compounds (AREA)
- Cosmetics (AREA)
- Fats And Perfumes (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、それ自体実質的に無臭の化合物であって、香
料の保留剤として極めて優れた保留効果を有する従来文
献未記載の新規化合物に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel compound which is substantially odorless in itself and which has an extremely excellent retention effect as a fragrance retention agent, and which has not been described in any prior literature. .
又、本発明は上記式（１）化合物の利用並びにその製法
にも関する。The present invention also relates to the use of the above compound of formula (1) and its production method.
更に詳しくは、本発明は下記式（１）
但し式中、波線はアクシアル又はエカトリアル結合を示
す、
で表される従来文献未記載の新規化合物のメチル−４，
６−０−（７−ヒドロキシ−３，７−ジメチル）オクチ
リデン−Ｄ−グリコシドに関する。More specifically, the present invention relates to a novel compound of the following formula (1), in which the wavy line represents an axial or equatorial bond, methyl-4,
6-0-(7-hydroxy-3,7-dimethyl)octylidene-D-glycoside.
更に本発明は、該式（１）化合物が極めて優れた香料の
保留特性を有し、該式（１）化合物を有効成分として含
有する調合香料組成物の保留剤として極めて有用な新規
な香料組成物にも関する。Furthermore, the present invention provides a novel fragrance composition in which the compound of formula (1) has extremely excellent fragrance retention properties and is extremely useful as a retention agent for a blended fragrance composition containing the compound of formula (1) as an active ingredient. It also relates to things.
更に又、該式（１）化合物の製法にも関する。Furthermore, it also relates to a method for producing the compound of formula (1).
（従来の技術）
天然香料、合成香料は一般に揮発性が高いからこれらの
香料を調合して得られる調合香料は、経時的に調合香料
成分中のより揮発性の高い成分が揮発し、調合香料の成
分バランスがくづれ香調が著しく変化する場合がある。(Prior art) Since natural fragrances and synthetic fragrances are generally highly volatile, the compound fragrance obtained by blending these fragrances is difficult because the more volatile components in the compound fragrance components volatilize over time, resulting in The balance of ingredients may deteriorate and the fragrance tone may change significantly.
従来、この様な変化を防ぐために、香料物質の揮発性あ
るいは保留性を調整する各種保留剤が香料に有効成分と
して配合し利用されている。Conventionally, in order to prevent such changes, various retention agents that adjust the volatility or retention properties of perfume substances have been used as active ingredients in perfumes.
上記の保留剤として、通常例えば、ジエチルフタレート
、ベンジルベンゾエート、トリエチルシトレート、ジエ
チレングリコールモノエチルエーテル、イソプロピルミ
リステート、プロピレングリコール、ジプロピレングリ
コールなどが利用されている。As the above-mentioned retention agent, for example, diethyl phthalate, benzyl benzoate, triethyl citrate, diethylene glycol monoethyl ether, isopropyl myristate, propylene glycol, dipropylene glycol, etc. are usually used.
更に、近年には単独で稀釈剤、保留剤および安定化剤等
の効果を同時に兼ね備える種々の化合物が香料調整剤と
してＱｇされている。これらの化合物として、例えば２
−エチルへキシルベンゾエート、３−フェニルプロピル
−２−エチルブチレート（特開昭５５−１３３３０３）
、例えば、ベンジルフェノキシアセテート、ベンジル−
３−フェノキシプロビオネート（特開昭５５−１３３３
０４）、例えばエチレングリコールジベンゾエート、ジ
エチレングリ；−ルジベンゾエート（特開昭５５−１３
３３０５）、例えばジヘキシルタータレート、トリへキ
シルシトレート （特開昭５５−１３３３０６）などが
提案されている。Furthermore, in recent years, various compounds that have the effects of a diluent, a preservative, a stabilizer and the like simultaneously have been used as flavor modifiers. These compounds include, for example, 2
-Ethylhexylbenzoate, 3-phenylpropyl-2-ethylbutyrate (JP 55-133303)
, for example, benzyl phenoxy acetate, benzyl-
3-Phenoxyprobionate (JP-A-55-1333)
04), for example, ethylene glycol dibenzoate, diethylene glycol dibenzoate (JP-A-55-13
3305), for example, dihexyl tartrate, trihexyl citrate (Japanese Patent Application Laid-Open No. 133306/1983), etc. have been proposed.
（発明が解決しようとする問題点）
従来利用されている上述のジエチルフタレート・・・・
・・・・・・・ジプロピレングリコール類は、いずれも
香料の保留効果は、必ずしも満足できるものではない。(Problems to be solved by the invention) The above-mentioned diethyl phthalate that has been used in the past...
... Dipropylene glycols do not necessarily have a satisfactory fragrance retention effect.
又、上記の特許公開公報に記載される化合物類も、香料
の保留効果としては、満足できるものではない。In addition, the compounds described in the above-mentioned patent publication are also not satisfactory in terms of fragrance retention effect.
更に上記の特開昭６０−１８８０３７、特開昭６０−１
８８０３９及び特公昭５６−４４０５５に記載されてい
るメチル−４，６−０−ベンジリデン−α、Ｄ−グリコ
ピラノシドが、甘味剤の合成中間体として利用でｉ、る
こと或いは該化合物のエーテル又はエステル誘導体を合
成する方法について記載されているが、本発明の式（１
）新規化合物及びその製法については、全く言及されて
いないし、更に香料の保留特性については、全熱記載も
示唆もされていない。Furthermore, the above-mentioned JP-A-60-188037 and JP-A-60-1
Methyl-4,6-0-benzylidene-α,D-glycopyranoside described in 88039 and Japanese Patent Publication No. 56-44055 can be used as a synthetic intermediate for sweeteners, or ether or ester derivatives of the compound. The method for synthesizing the formula (1) of the present invention is described.
) There is no mention of new compounds and their production methods, and there is no mention or suggestion of the retention properties of fragrances.
（問題点を解決するための手段）
木発明者らは、上記事情にかんがみ、香料及び調合香料
の保留剤として有用な新しいタイプの保留剤を開発すべ
く鋭意研究した結果、従来文献未記載の上記式（１）新
規化合物の合成に成功し、且つ該化合物が実質的に無臭
で化学的にも安定であるとともに皮膚安全性に優れ、各
種香料ならびにこれらの調合香料の保留剤として極めて
優れた保留効果を有することを発見した。更に上記式（
１）化合物が容易に合成できることも発見した。(Means for Solving the Problems) In view of the above circumstances, the inventors of the Wood Inventors conducted intensive research to develop a new type of retention agent useful as a retention agent for fragrances and blended fragrances, and as a result, discovered a new type of retention agent that has not been previously described in the literature. We have successfully synthesized a new compound of formula (1) above, which is substantially odorless, chemically stable, and has excellent skin safety, and is extremely excellent as a preservative for various fragrances and their blended fragrances. It was discovered that it has a holding effect. Furthermore, the above formula (
1) We also discovered that the compound can be easily synthesized.
従って、本発明の目的は、従来文献未記載の上記式（１
）新規化合物及びその製法を提供するにある。又、本発
明は、該式（１）化合物を香料ならびにこれらの調合香
料組成物に有効成分として含有することを特徴とする新
規な香料組成物を提供するにある。Therefore, an object of the present invention is to solve the above formula (1
) A new compound and a method for producing the same are provided. The present invention also provides a novel fragrance composition characterized in that the compound of formula (1) is contained as an active ingredient in a fragrance and a blended fragrance composition thereof.
本発明の下記式（１）
但し式中、波線はアクシアル又はエカトリアル結合を示
す、
で表されるメチル−４，６−ｍ−（７−ヒドロキシ−３
，７−ジメチル）オクチリデン−Ｄ−グリコシドを合成
するには、例えば、
下記式 （２）
但し式中、波線はアクシアル又はエカトリアル結合を示
Ｖ、
で表されるメチル−Ｄグリコシドを有機溶媒中、酸の存
在下に下記式（３）
で表されるヒドロキシシトロネラールジメチルアセクー
ルと接触させることにより容易に合成することができる
。The following formula (1) of the present invention, where the wavy line indicates an axial or equatorial bond, is represented by methyl-4,6-m-(7-hydroxy-3
,7-dimethyl)octylidene-D-glycoside is synthesized by, for example, the following formula (2), where the wavy line indicates an axial or equatorial bond, V, in an organic solvent, It can be easily synthesized by bringing it into contact with hydroxycitronellal dimethylacecool represented by the following formula (3) in the presence of an acid.
本発明の上記式（１）化合物を合成する方法を（２’Ｊ
＜ ３ ）本発明の式（１）化
合物を合成する！ＩＭ様を上記工程図の例に従って、以
下に詳細に述べる。The method for synthesizing the compound of formula (1) of the present invention is described by (2'J
<3) Synthesize the compound of formula (1) of the present invention! IM will be described in detail below according to the example of the process diagram above.
本発明の式（１）化合物の合成に必要な式（２）のメチ
ル−〇−グリコシドに包含される化合物としては、例え
ば、メチル−α。或いはβ、Ｄ−グルコピラノシド、メ
チル−α、或いはβ、Ｄ−ガラクトピラノシド、メチル
−α。或いはβ、Ｄ−マンノピラノシドなどのごときメ
チル６単零唐頻を例示することができる。Examples of compounds included in the methyl-0-glycoside of formula (2) necessary for the synthesis of the compound of formula (1) of the present invention include methyl-α. Or β, D-glucopyranoside, methyl-α, or β, D-galactopyranoside, methyl-α. Alternatively, methyl 6 monomers such as β, D-mannopyranoside and the like can be exemplified.
これらのピラノシド類は、市場で容易に入手可能な化合
物である。又、式（３）化合物も市場で容易に入手でき
る化合物であり、所望により容易に合成することも可能
である。・
合成する場合は、市場で容易に入手することのできるヒ
ドロキシシトロネラールを、例えば、メタノール中、ｐ
−）ルエンスルホン酸の存在下にオルトギ酸メチルと反
応させることにより、容易に合成することができる。These pyranosides are compounds that are easily available on the market. Further, the compound of formula (3) is also a compound that is easily available on the market, and can be easily synthesized if desired. - When synthesizing, hydroxycitronellal, which is easily available on the market, is prepared, for example, in methanol with p
-) It can be easily synthesized by reacting with methyl orthoformate in the presence of luenesulfonic acid.
本発明の式（１）化合物を合成するには、例えば式（２
）化合物を有機溶媒中、酸の存在下に式（３）化合物と
接触せしめることにより容易に安価且つ工業的に合成す
ることができる。この反応の温度は、適宜に選択変更す
ることができるが例えば、約４０〜約１５０°Ｃ程度の
温度範囲を好しく例示することができる。又、反応時間
も、適宜に選択して行うことができるが、例えば通常約
１〜約６時間程度の範囲の反応時間で行うことができる
。To synthesize the compound of formula (1) of the present invention, for example, the compound of formula (2)
) can be easily synthesized at low cost and industrially by contacting the compound of formula (3) in an organic solvent in the presence of an acid. The temperature of this reaction can be selected and changed as appropriate, and for example, a temperature range of about 40 to about 150°C can be preferably exemplified. Further, the reaction time can be selected as appropriate, and for example, the reaction time can be usually in the range of about 1 to about 6 hours.
上記反応に使用する存機溶媒としては、例えばジメチル
ホルムアミド、ジクロルエタン、酢酸エチル、ベンゼン
、トルエン、シクロヘキサンなどを好しく例示すること
ができる。これら存機溶媒の使用量には、特別の制限は
なく適宜選択して行うことができるが、例えば、式（２
）化合物に対して約１〜約５重景倍程度の範囲を例示す
ることができる。又、式（３）化合物の使用量としては
、例えば、式（２）化合物１モルに対して約０．５〜約
２モル程度の範囲が例示できる。又、使用する酸として
は、例えばｐ−トルエンスルホン酸、硫酸、リン酸など
を好しく例示することができる。Preferred examples of the organic solvent used in the above reaction include dimethylformamide, dichloroethane, ethyl acetate, benzene, toluene, and cyclohexane. There is no particular restriction on the amount of these organic solvents to be used, and they can be selected as appropriate.
) can be exemplified in a range of about 1 to about 5 magnifications relative to the compound. The amount of the compound of formula (3) to be used is, for example, about 0.5 to about 2 moles per mole of the compound of formula (2). Preferred examples of the acid used include p-toluenesulfonic acid, sulfuric acid, and phosphoric acid.
これらの酸の使用量としては、例えば式（２）化合物に
対して、例えば約０．１〜約５重景％程度の範囲の使用
量を例示できる０反応は、所、望により減圧下に行うこ
とができる。減圧の程度は、適宜に選択変更できるが、
通常、例えば約１０〜約６０ｍｍＨｇ程度の範囲で行わ
れる。The amount of these acids to be used is, for example, in the range of about 0.1 to about 5% based on the compound of formula (2). It can be carried out. The degree of decompression can be selected and changed as appropriate.
Usually, it is carried out in a range of, for example, about 10 to about 60 mmHg.
反応終了後は、例えば、反応液中に炭酸ナトリウムの適
当量を加え、減圧下に溶媒を留去し、残香をシリカゲル
を用いてカラムクロマトで精製して、目的化合物を容易
に得ることができる。After the reaction is completed, the target compound can be easily obtained by, for example, adding an appropriate amount of sodium carbonate to the reaction solution, distilling off the solvent under reduced pressure, and purifying the residual aroma by column chromatography using silica gel. .
かくして、上述の様にして得られた上記式（１）％式％
７−ジメチル）オクチリデン−Ｄ−グリコシドに包含さ
れる化合物としては、メチル−４，６−０−く７−ヒド
ロキシ−３，７−ジメチル）オクチリデン−α。或いは
β、Ｄ−グルコピラノシド、メチル−４，６−０−（７
−ヒドロキシ−３，７−ジメチル）オクチリデン−α、
或いはβ、Ｄ−ガラクトピラノシド、メチル−４，６−
０−（７−ヒドロキシ−３，７−ジメチル）オクチリデ
ン−α。或いはβ、Ｄ−マンノピラノシドなどを挙げる
ことができる。Thus, the compounds included in the formula (1)%7-dimethyl)octylidene-D-glycoside obtained as described above include methyl-4,6-0-7-hydroxy-3, 7-dimethyl)octylidene-α. or β, D-glucopyranoside, methyl-4,6-0-(7
-hydroxy-3,7-dimethyl)octylidene-α,
or β, D-galactopyranoside, methyl-4,6-
0-(7-hydroxy-3,7-dimethyl)octylidene-α. Alternatively, β, D-mannopyranoside, etc. can be mentioned.
これら式（１）化合物は、香料ならびに調合香料組成物
の保留剤として、従来にはない優れた効果を有し、その
使用量としては、特別限定されることなく適宜選択して
使用することができるが、例えば調合香料組成物の場合
にあっては、約５〜約５０重量％程度の範囲、好しくは
約１０〜約３０重量％程度の範囲の使用量を例示するこ
とができる。These compounds of formula (1) have unprecedented effects as preservatives for fragrances and blended fragrance compositions, and the amount used can be selected as appropriate without any particular limitations. However, in the case of a blended fragrance composition, for example, the amount used can be in the range of about 5 to about 50% by weight, preferably about 10 to about 30% by weight.
以下に本発明の実施態様について、実施例をあげて更に
詳細に説明する。The embodiments of the present invention will be described in more detail below with reference to examples.
（実施例）
（１）メチル−４，６−０−（７−ヒドロキシ−３，７
−ジメチル）オクチリデン−α、Ｄ−グルコピラノシド
の合成。(Example) (1) Methyl-4,6-0-(7-hydroxy-3,7
Synthesis of -dimethyl)octylidene-α,D-glucopyranoside.
フラスコにメチル−α、Ｄ−グリコピラノシド１４５．
６ｇ（０，７５モル）、ヒドロキシシトロネラールジメ
チルアセクール１１０ｇ（０，５モル）、ジメチルホル
ムアミド５００ｍ１．ｐ−トルエンスルホン酸２．５ｇ
を仕込み、減圧下（３０ｍｍＨｇ）に４０℃にて４時間
メタノールを留去しながら反応した。反応終了後、反応
液中に炭酸ソーダ３ｇを加え、溶媒を減圧下に留去し、
残香を５Ｋｇのシリカゲルを用いてカラムクロマト精製
（クロロホルム／メタノール＝９０／１０）Ｌ、工０３
ｇ（５９，１％収率）の目的化合物を得た。Methyl-α, D-glycopyranoside 145.
6 g (0.75 mol), 110 g (0.5 mol) of hydroxycitronellal dimethyl acecure, 500 ml of dimethylformamide. 2.5g p-toluenesulfonic acid
was charged and reacted under reduced pressure (30 mmHg) at 40° C. for 4 hours while distilling methanol off. After the reaction was completed, 3 g of sodium carbonate was added to the reaction solution, and the solvent was distilled off under reduced pressure.
Purify the residual fragrance by column chromatography using 5 kg of silica gel (chloroform/methanol = 90/10) L, Engineering 03
g (59.1% yield) of the target compound was obtained.
’Ｈ−ＮＭＲδ（ＣＤＣ］ｉ ） ｐｐｍ０、９１
（３Ｈ、ｄ 、 Ｊ −５，３Ｈｚ ）１．１ ９
（６）（、Ｓ）
１．１ ３ 〜１．７ ０ （ｌ ＩＨ，ｍ）３．
２ ２ 〜４．５ ８ （８Ｈ，ｍ）４、７ ３
（Ｉ Ｈ、ｄ 、 Ｊ ＝ ｊ、 ５ Ｈｚ ）（２
）メチル−４，６−０−（７−ヒドロキシ−３，７−ジ
メチル）オクチリデン−α、Ｄ−ガラクトピラノシドの
合成。'H-NMRδ(CDC]i) ppm0, 91
(3H, d, J -5, 3Hz) 1.1 9
(6) (, S) 1.1 3 ~ 1.7 0 (l IH, m) 3.
2 2 ~ 4.5 8 (8H, m) 4, 7 3
(I H, d, J = j, 5 Hz) (2
) Synthesis of methyl-4,6-0-(7-hydroxy-3,7-dimethyl)octylidene-α, D-galactopyranoside.
実施例（１）において、メチル−α、Ｄ−グルコノピラ
ノシドの代りにメチル−α、Ｄ−ガラクトピラノシド１
４５．６ ｇ （０，７５モル）を用いた他は、実施例
（１）と同様に行って目的化合物１１５、３ ｇを得た
。（収率、 ６６．２％）’Ｈ−ＮＭＲδ（ＣＤＣ１３
）ｐｐｍ
０、８８ （３Ｈ、ｄ 、 Ｊ ＝ ５．１ Ｈｚ
）１．１８（６Ｈ，Ｓ）
１．１１〜Ｌ７０ （１１Ｈ，ｍ）
３．２０〜４．６０ （８Ｈ，ｍ）
４．６６ （ＩＨ，ｄ、Ｊ−４Ｈｚ）
（３）メチル−４，６−０−（７−ヒドロキシ−３，７
−ジメチル）オクチリデン−α、Ｄ−マンノピラノシド
の合成。In Example (1), methyl-α,D-galactopyranoside 1 was used instead of methyl-α,D-gluconopyranoside.
The same procedure as in Example (1) was conducted except that 45.6 g (0.75 mol) was used to obtain 115.3 g of the target compound. (Yield, 66.2%)'H-NMRδ (CDC13
) ppm 0,88 (3H, d, J = 5.1 Hz
) 1.18 (6H, S) 1.11-L70 (11H, m) 3.20-4.60 (8H, m) 4.66 (IH, d, J-4Hz) (3) Methyl-4, 6-0-(7-hydroxy-3,7
Synthesis of -dimethyl)octylidene-α,D-mannopyranoside.
実施例（１）において、メチル−α、Ｄ−グルコノピラ
ノシドの代りにメチル−α、Ｄ−マンノピラノシド１４
５．６ ｇ （０，７５モル）を用いた他は、実施例（
１）と同様に行って目的化合物１０８ｇを得た。（収率
； ６２．１％）’Ｈ−ＮＭＲδ（ＣＤＣＩ３ ） ｐ
ｐｍ０．９０ （３Ｈ’、ｄ、Ｊ＝５．３Ｈｚ）１．２
０ （６Ｈ，Ｓ’）
１．１０〜１．７０ （１１Ｈ，ｍ）
３．２０〜４．６０ （８Ｈ，ｍ）
４．７７ （ＩＨ，ｄ、Ｊ−２Ｈ２）
（応用例）
この応用例は、前記の実施例１〜３で得られた本発明の
化合物の香料の保留効果を示すものである。In Example (1), methyl-α,D-mannopyranoside 14 was used instead of methyl-α,D-gluconopyranoside.
Example (1) except that 5.6 g (0.75 mol) was used.
The same procedure as in 1) was carried out to obtain 108 g of the target compound. (Yield; 62.1%)'H-NMRδ(CDCI3) p
pm0.90 (3H', d, J=5.3Hz) 1.2
0 (6H, S') 1.10~1.70 (11H, m) 3.20~4.60 (8H, m) 4.77 (IH, d, J-2H2) (Application example) This application example 1 shows the fragrance retention effect of the compounds of the present invention obtained in Examples 1 to 3 above.
保留効果試験
後記の第１表に示す有効物質１２種からなるモデル調合
香料９０重量％と本発明の化合物または比較化合物を１
０重量％とを均一に溶解混合した調合香料を調整し、こ
れに調合香料の４倍重量のエチルアルコールを添加して
試料とする。Retention effect test: 90% by weight of a model compound fragrance consisting of 12 active substances shown in Table 1 below and 1% of the compound of the present invention or the comparative compound.
A sample is prepared by uniformly dissolving and mixing 0% by weight of ethyl alcohol, and adding 4 times the weight of ethyl alcohol to the blended fragrance.
匂い紙（９ｃｍｘ ９ ｃｍ、 ２．４ ｇ）にこの
試料又はモデル調合香料を０．５ｇ塗布し、次いで温度
２５℃、湿度５０％の恒温、恒温の部屋内で、調香技術
者５名からなる判定者により、塗布終了直後（０分）よ
り５０分、１８０分、３００分後迄の香りの変化の度合
いを後記第２表の判定基準に従って判定し、その結果を
Ｏ１Δ、Ｘ、ＸＸで示した。0.5 g of this sample or model blended fragrance was applied to scented paper (9 cm x 9 cm, 2.4 g), and then five fragrance technicians applied it in a constant temperature room with a temperature of 25°C and a humidity of 50%. The degree of change in scent from immediately after the application (0 minutes) to 50 minutes, 180 minutes, and 300 minutes after the application was judged by a judge according to the judgment criteria in Table 2 below, and the results were expressed as O1Δ, X, and XX. Indicated.
第１表 モデル調合香料
第２表 判定基準
第３表 保留効果の試験結果
第３表から明らかなように、前記本発明の化合物の香料
の保留効果は、極めて良好であり、そして公知の保留剤
よりも著しく優れている。Table 1 Model blended fragrance Table 2 Judgment criteria Table 3 Retention effect test results As is clear from Table 3, the retention effect of the fragrance of the compound of the present invention is extremely good, and the retention effect of the known retention agent significantly better than.
（効果）
本発明の上記式（１）化合物は、それ自体実質的に無臭
で化学的にも安定であるとともに皮膚安全性にも優れた
従来文献未記載の新規化合物である。そして該化合物が
各種香料およびこれらの調合香料組成物の保留剤として
、掻めて優れた効果を有し、該式（１）化合物をを効成
分として含有する新規な調合香料組成物を提供すること
ができ且つ該組成物は、化粧品類、香粧品類、飲食高鼾
などの広い分野に於て利用できる有用な化合物である。(Effects) The compound of formula (1) of the present invention is a novel compound that is substantially odorless, chemically stable, and excellent in skin safety, and has not been previously described in any literature. Further, the present invention provides a novel mixed fragrance composition in which the compound has an extremely excellent effect as a retention agent for various fragrances and mixed fragrance compositions thereof, and contains the compound of formula (1) as an active ingredient. The composition is a useful compound that can be used in a wide range of fields such as cosmetics, cosmetics, eating and drinking, etc.
Claims (1)
す、 で表されるメチル−４，６−Ｏ−（７−ヒドロキシ−３
，７−ジメチル）オクチリデン−Ｄ−グリコシド[Claims] 1. The following formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) However, in the formula, the wavy line indicates an axial or equatorial bond. Methyl-4,6-O represented by -(7-hydroxy-3
,7-dimethyl)octylidene-D-glycoside
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62287073A JP2512401B2 (en) | 1987-11-12 | 1987-11-12 | Methyl-4,6-0- (7-hydroxy-3,7-dimethyl) octylidene-D-glycoside |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62287073A JP2512401B2 (en) | 1987-11-12 | 1987-11-12 | Methyl-4,6-0- (7-hydroxy-3,7-dimethyl) octylidene-D-glycoside |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01128993A true JPH01128993A (en) | 1989-05-22 |
| JP2512401B2 JP2512401B2 (en) | 1996-07-03 |
Family
ID=17712705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62287073A Expired - Fee Related JP2512401B2 (en) | 1987-11-12 | 1987-11-12 | Methyl-4,6-0- (7-hydroxy-3,7-dimethyl) octylidene-D-glycoside |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2512401B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5320131A (en) * | 1992-07-16 | 1994-06-14 | R. J. Reynolds Tobacco Company | Method of providing an aroma and flavor precursor for smoking articles |
| WO1998050009A1 (en) * | 1997-05-02 | 1998-11-12 | Henkel Kommanditgesellschaft Auf Aktien | Use of depot preparations for targeted release of aromatic principles |
-
1987
- 1987-11-12 JP JP62287073A patent/JP2512401B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5320131A (en) * | 1992-07-16 | 1994-06-14 | R. J. Reynolds Tobacco Company | Method of providing an aroma and flavor precursor for smoking articles |
| WO1998050009A1 (en) * | 1997-05-02 | 1998-11-12 | Henkel Kommanditgesellschaft Auf Aktien | Use of depot preparations for targeted release of aromatic principles |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2512401B2 (en) | 1996-07-03 |
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