JPS62267278A - 6-ethyl-3-phenyl-5-oxatricyclo(4.2.1.03,7)nonane and perfume composition containing same - Google Patents
6-ethyl-3-phenyl-5-oxatricyclo(4.2.1.03,7)nonane and perfume composition containing sameInfo
- Publication number
- JPS62267278A JPS62267278A JP61111232A JP11123286A JPS62267278A JP S62267278 A JPS62267278 A JP S62267278A JP 61111232 A JP61111232 A JP 61111232A JP 11123286 A JP11123286 A JP 11123286A JP S62267278 A JPS62267278 A JP S62267278A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- ethyl
- oxatricyclo
- nonane
- compound
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims description 10
- 239000002304 perfume Substances 0.000 title abstract description 3
- KXHQKKOZNURFTJ-UHFFFAOYSA-N 3-ethyl-6-phenyl-4-oxatricyclo[4.2.1.03,7]nonane Chemical compound C1OC2(CC)CC(C3)CC2C13C1=CC=CC=C1 KXHQKKOZNURFTJ-UHFFFAOYSA-N 0.000 title 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 16
- 239000003205 fragrance Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010992 reflux Methods 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 238000005705 Cannizzaro reaction Methods 0.000 abstract description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 229940032330 sulfuric acid Drugs 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- GPWNWKWQOLEVEQ-UHFFFAOYSA-N 2,4-diaminopyrimidine-5-carbaldehyde Chemical compound NC1=NC=C(C=O)C(N)=N1 GPWNWKWQOLEVEQ-UHFFFAOYSA-N 0.000 description 3
- 241000207199 Citrus Species 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000020971 citrus fruits Nutrition 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- -1 hair rinses Substances 0.000 description 3
- BGEBZHIAGXMEMV-UHFFFAOYSA-N 5-methoxypsoralen Chemical compound O1C(=O)C=CC2=C1C=C1OC=CC1=C2OC BGEBZHIAGXMEMV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- PNZVFASWDSMJER-UHFFFAOYSA-N acetic acid;lead Chemical compound [Pb].CC(O)=O PNZVFASWDSMJER-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- UWKAYLJWKGQEPM-LBPRGKRZSA-N linalyl acetate Chemical compound CC(C)=CCC[C@](C)(C=C)OC(C)=O UWKAYLJWKGQEPM-LBPRGKRZSA-N 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YBUIAJZFOGJGLJ-SWRJLBSHSA-N 1-cedr-8-en-9-ylethanone Chemical compound C1[C@]23[C@H](C)CC[C@H]3C(C)(C)[C@@H]1C(C)=C(C(C)=O)C2 YBUIAJZFOGJGLJ-SWRJLBSHSA-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
- DBMJZOMNXBSRED-UHFFFAOYSA-N Bergamottin Natural products O1C(=O)C=CC2=C1C=C1OC=CC1=C2OCC=C(C)CCC=C(C)C DBMJZOMNXBSRED-UHFFFAOYSA-N 0.000 description 1
- 101150064066 CTSL gene Proteins 0.000 description 1
- 229920001744 Polyaldehyde Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ZUSQJEHVTIBRNR-UHFFFAOYSA-N aluminum;lithium;oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[Al+3] ZUSQJEHVTIBRNR-UHFFFAOYSA-N 0.000 description 1
- 229960002045 bergapten Drugs 0.000 description 1
- KGZDKFWCIPZMRK-UHFFFAOYSA-N bergapten Natural products COC1C2=C(Cc3ccoc13)C=CC(=O)O2 KGZDKFWCIPZMRK-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229940067137 musk ketone Drugs 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- Fats And Perfumes (AREA)
- Furan Compounds (AREA)
- Cosmetics (AREA)
Abstract
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）
テ表ワサレる６−エチル−３−フェニル−５−オキサト
リシクロ［４，２，１，０）ノナン及びこれを含有する
香料組成物に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to the following general formula (I): 6-ethyl-3-phenyl-5-oxatricyclo[4,2,1,0] The present invention relates to nonane and fragrance compositions containing the same.
従来、ビシクロ（２，２，１３へブ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（Ｉ）〔特開昭５７
−４５１７９号〕又は式（２）〔特開昭５７−８２３３
０号〕のｇｅｎｌ−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(2,2,13-hebutanecarbaldehyde was subjected to Canitzaro reaction to obtain the following formula (I)
-45179] or formula (2) [JP-A-57-8233
It is known that a compound having a genl-bis(hydroxymethyl) structure of No. 0 can be obtained.
しかし、これらの化合物を三項式化合物に酵導し、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, there have been no reports on the fermentation of these compounds into trinomial compounds and 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
）ヘプタンから訪導される（Ｉ）式で表わされる三項式
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。Under such circumstances, the present inventor discovered that 2,2-bis(hydroxymethyl)-6-ethylidenebicyclo[2,2,1
The present invention was completed based on the discovery that a novel compound having a trinomial skeleton represented by formula (I) derived from heptane has an excellent aroma.
すなわち、本発明は、（■）式で表わされる６−エチル
−３−フェニル−５−オキサトリシクロ［４，２，１，
０Ｅノナン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-3-phenyl-5-oxatricyclo[4,2,1,
It provides 0E nonane. The present invention further provides a fragrance composition containing the same.
本発明化合物（Ｉ）は、例えば、次の反応式に従って、
２−エチリデンビシクロ［２，２，１）へブタン−５（
又は６）−力ルボアルデヒド（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（Ｉｌｌ）となし、次いでこ
れを酸性粂件下壌化させて６−エチル−３−ヒドロキシ
メチル−５−オキサトリシクロ［４，２，１，０）ノナ
ン（転）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（４，２，１，０）ノナン−３−カ
ルボン酸（Ｖ）となし、更にこれに四酢酸鉛の存在下ベ
ンゼンを反応させることにより製造される。The compound (I) of the present invention can be prepared, for example, according to the following reaction formula:
2-ethylidenebicyclo[2,2,1)butane-5(
or 6) - methylolation of carbaldehyde (II) by subjecting it to Canitzaro reaction with formaldehyde to produce 2,
2-bis(hydroxymethyl)-6-ethylidenebicyclo[2,2,1)heptane (Ill), which was then converted to 6-ethyl-3-hydroxymethyl-5-oxatrin under acidic conditions. cyclo[4,2,1,0)nonane (transformation), which is then oxidized to 6-ethyl-5
-Oxatricyclo(4,2,1,0)nonane-3-carboxylic acid (V) and further reacting this with benzene in the presence of lead tetraacetate.
（Ｉｔ） （ＩＩＩ） （
Ｖｌ）（ＩＶ）
（Ｖ）
（［）
尚、（■）の化合物とホルムアルデヒドとのカニッツア
ロ反応において、（■）式の６−エチリデン体の他に（
Ｖｌ）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、環化反応に先立っ
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。(It) (III) (
Vl) (IV) (V) ([) In addition, in the Cannizzaro reaction between the compound (■) and formaldehyde, in addition to the 6-ethylidene compound of the formula (■), (
Although the 5-ethylidene form of formula Vl) is also produced, in the next cyclization reaction, cyclization of the 5-ethylidene form does not occur under the cyclization conditions for the 6-ethylidene form, so both should be combined before the cyclization reaction. There is no need to separate it, and it can be used as is for the reaction.
化合物（ＩＩ）から＋ＩＩＩ）を得る反応は公知でおり
、これに従って行われる。化合物（ｍ）から（ＩＶ）を
得るには、（■）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（ｆＶ）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けられ、
反応は自体公知の酸化条件下で行われる。化合物（Ｖ）
から本発明化合物（Ｉ）を得るには、（■）を四酢酸鉛
の存在下ベンゼンと反応させる。The reaction for obtaining +III) from compound (II) is known and carried out according to this method. In order to obtain (IV) from compound (m), (■) 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. Oxidizing agents used to obtain (V) from compound (fV) include chromic acid, potassium permanganate, etc.
The reaction is carried out under oxidizing conditions known per se. Compound (V)
To obtain the compound (I) of the present invention, (■) is reacted with benzene in the presence of lead tetraacetate.
本発明化合物はグレープフルーツ様のシトラスな香りを
有し、例えば高級な香料組成物、香水、石鹸、シャンプ
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 of the present invention has a grapefruit-like citrus aroma and is widely used in products that require fragrance, such as high-grade fragrance compositions, perfumes, soaps, shampoos, hair rinses, detergents, cosmetics, sprays, and fragrances. Can be used.
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 explained 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
３へブタンの合成：２−エチリデンビシクロ［２，２，
１）へブタン−５Ｃ又は６）−力ルポアルデヒド３００
．４ ｆ（２ｍａｔ ）と３７％ホルマリン水溶液４０
５．５ ｔ（５ｍｏｌ ）及び４８０ ｍｌのメタノー
ルを水浴下に攪拌し、２０％水酸化ナトリウム水溶液１
６Ｆ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チ水酸化ナトリウム水
溶液１８４ｔを１時間１０分で滴下した。Reference Example 1: 2,2-bis(hydroxymethyl)-6-ethylidenebicyclo[2,2,1)heptane and 2,2-bis(hydroxymethyl)-5-ethylidenebicyclo[2,2,1
Synthesis of 3hebutane: 2-ethylidenebicyclo[2,2,
1) Hebutane-5C or 6)-Polyaldehyde 300
．． 4 f (2mat) and 37% formalin aqueous solution 40
5.5 t (5 mol) and 480 ml of methanol were stirred in a water bath, and 20% sodium hydroxide aqueous solution 1
Added 6F. When the temperature was gradually returned to room temperature, the system became cloudy. After 1 hour and 40 minutes, 184 tons of 20% sodium hydroxide aqueous solution was added dropwise over 1 hour and 10 minutes.
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。The internal temperature rose to 28°C. 50℃ for 20 hours after completion of dropping
The mixture was heated and stirred. Heating was stopped and the mixture was stirred again in an ice water bath.
水素化ホウ素ナトリウム７、５６ ｆ（０，２ｍｏｔ）
を４００ｆの２０％水酸化ナトリウム水溶液に泪かした
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塩酸で酸性にし、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３
６３Ｆ（収率９９，７チ）を得た。Sodium borohydride 7,56 f (0,2mot)
A solution prepared by diluting 400f of 20% sodium hydroxide aqueous solution was added dropwise over 1 hour, and the mixture was stirred at room temperature for 1 hour. Extracted with ether three times. The ether layer was made acidic with 4N hydrochloric acid, washed with a saturated aqueous sodium bicarbonate solution and water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain crude product 3.
63F (yield: 99.7%) was obtained.
沸点：１０１−１１８℃７０．１ ｍａｙ元素分析ＣＩ
ＩＨＩ畠Ｏ１として
計算値ｃ％） ： Ｃ： ７２−４９ 、 Ｈ＊ ９．
９５実測値Ｃ％） ： ｃ ： ７２．４２ 、 ｎ
； １ｏ、 ｏ 。Boiling point: 101-118℃ 70.1 may elemental analysis CI
Calculated value c% as IHI Hatake O1): C: 72-49, H* 9.
95 Actual value C%): c: 72.42, n
; 1o, o.
ＩＲ（ＮａＣ１，ｃｍ−’ ）： ３３０５ （ＯＨ）
、３０４０ （ビニル基）、２９５０，１４５０．１３
７５（メチル基）。IR (NaCl, cm-'): 3305 (OH)
, 3040 (vinyl group), 2950, 1450.13
75 (methyl group).
”Ｈ−ＮＭＲ（δｐｐｍ）：ｂ、５７−４．９（ＩＨ，
ｍ）、３．５７（４Ｈ，ｂｒ、ｍ）、３．１７（２Ｈ，
ｂｒ、ｓ、ＯＨ）。"H-NMR (δppm): b, 57-4.9 (IH,
m), 3.57 (4H, br, m), 3.17 (2H,
br, s, OH).
１．５５（３Ｈ，ｄ、Ｊ＝６Ｈｚ）、２．７７＝１．０
（８Ｈ，ｍ）ＭＳ（相対強度）：１８２（Ｍ＋、３１％
）、１５１（Ｍ−ＣＨ鵞ＯＨ，２４チ）、７９（５４％
）、５７（Ｉ００チ）参考例２
６−ニチルー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］へブタン５ ｆ （２
７，４ｍｍｏｔ）を１５−の水、１５ｍ／のイソプロピ
ルアルコール及び５ｆの濃硫酸中１時間加熱還流した。1.55 (3H, d, J=6Hz), 2.77=1.0
(8H, m) MS (relative intensity): 182 (M+, 31%
), 151 (M-CH Goose OH, 24 Chi), 79 (54%
), 57 (I00chi) Reference Example 2 Synthesis of 6-nity-3-(hydroxymethyl)-5-oxatricyclo[4,2,1,03°7]nonane: 2.2-bis(hydroxymethyl)- 5 (or 6)-ethylidenebicyclo[2,2,1]hebutane 5 f (2
7.4 mmot) was heated under reflux for 1 hour in 15 m/m of water, 15 m/m of isopropyl alcohol, and 5 m/m of concentrated sulfuric acid.
氷水に注ぎ、エーテルで抽出した。エーテルｊ−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
す） Ｉ）ラムで乾燥した。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
ムクロマトグラフィーにより標記のアルコールを単離し
た。It was poured into ice water and extracted with ether. Ether j- is water,
Washed with saturated aqueous sodium bicarbonate solution and water, dried with anhydrous sulfuric acid (I) rum. After distilling off the solvent, the title alcohol was isolated by silica gel column chromatography using hexane-ethyl acetate (2:1) as a solvent.
収音１．５８ ｔ （収率３２％）
沸点１１０℃／ ０．０６ ｉｕ＋Ｈｆ元素分析ＣＩＩ
ＨＩＩＯＩ＋として
計算値（％） ： Ｃ： ７２．４９ 、 Ｈ； ９．
９５実測値ｃ％）：Ｃ；７２．５５ 、Ｈ：９．８０Ｉ
Ｒ（ＮａＣｔ、ｃｒｎ−” ）： ３４００ （ＯＨ）
、 ２９５５ 。Sound collection 1.58 t (yield 32%) Boiling point 110℃/0.06 iu+Hf elemental analysis CII
Calculated value as HIIOI+ (%): C: 72.49, H; 9.
95 actual value c%): C; 72.55, H: 9.80I
R(NaCt, crn-”): 3400 (OH)
, 2955.
２８７５．１４６０．１３７５（メチル基）、１０２０
”Ｈ−ＮＭＲ（Ｊｐｐｍ）：３．８０（ＩＴ（、ｄ、Ｊ
＝８Ｈｚ）。2875.1460.1375 (methyl group), 1020
"H-NMR (Jppm): 3.80 (IT (, d, J
=8Hz).
３．６２（ＩＨ，ｄ、Ｊ＝８Ｈｚ）、３．４８ （２Ｈ
、ｂｒｏａｄ。3.62 (IH, d, J=8Hz), 3.48 (2H
, broad.
Ｓ）、０．９２（３１（、ｔ、Ｊ−６１（Ｚ）、３〜０
．５（Ｉ１１（。S), 0.92(31(, t, J-61(Z), 3-0
．． 5(I11(.
ｍ）
ＭＳ（相対強度）：１８２（Ｍ”、１００チ）、１５１
（Ｍ−ＣＨ２０Ｈ、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／−３−カルボン酸の合成：無水クロム酸２
００ ？ （２ｍｏｔ） ｋ水冷下撹拌しながら１６０
０ＩＩＩ／の酢酸と２００ ｄの水の中に加えた。その
中へ２００ｍ／の酢酸に渚かした参考例２で得たアルコ
ール９０ Ｓ’ （０，５ｍｏｌ ）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−晩装置した
。飽和食塩水１．５ｔ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。m) MS (relative strength): 182 (M", 100ch), 151
(M-CH20H, 63%), 57 (80%) Reference Example 3 6-ethyl-5-oxatricyclo[4,2,1°03
°7] Synthesis of nona/-3-carboxylic acid: chromic anhydride 2
00? (2mot) 160 k while stirring under water cooling.
of acetic acid and 200 d of water. Alcohol 90 S' (0.5 mol) obtained in Reference Example 2, which had been soaked in 200 m/ml of acetic acid, was added dropwise into the solution while maintaining the temperature at 5°C or lower. After stirring for 2 hours at room temperature, it was stored overnight. 1.5 t of saturated saline was added and extracted with chloroform. The chloroform layer was extracted with a strongly alkaline aqueous sodium hydroxide solution. The aqueous layer was made strongly acidic with hydrochloric acid and extracted with ether.
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、残圧で蒸留して標記のカルボン酸を得
た。The ether layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was removed and distillation was performed under residual pressure to obtain the title carboxylic acid.
収１ｊｋ５２．７７９（収率５５％）
沸点１１６〜１３８℃／ ０．０４ ｉｕ＋Ｈｆ元素分
析Ｃ１５ＨｓａＯｎとして
計算値ｃ％） ： Ｃ； ６７．３２ 、 Ｈ； ８２
２実測値（％） ： Ｃ： ６７．４ Ｕ 、 Ｈ；
８．１０ＩＲ（ＮａＣｔ、ｃＩｎ）： ２９６０ 、２
８８０ 、１７００ 。Yield 1jk52.779 (yield 55%) Boiling point 116-138℃/0.04 iu+Hf Elemental analysis Calculated value as C15HsaOn c%): C; 67.32, H; 82
2 Actual value (%): C: 67.4 U, H;
8.10IR (NaCt, cIn): 2960, 2
880, 1700.
３５００〜２１５０
”Ｈ−ＮＭＲ（δＩ）Ｉ）ｍ） ： ９−４２ （Ｉ）
ｆ ９８ ） ？ ４．１０ （Ｉ Ｈ９ｄ 、Ｊ−８
Ｈｚ ） ＋ ３−７８ （Ｉ Ｈ、ｄ ＋ Ｊ ＝８
Ｈｚ ） ｔｌ、５８（２Ｈ，Ｑ、Ｊ＝７Ｈｚ）、０
．９３（３Ｈ，ｔ 、Ｊ＝７ Ｈｚ ） ＋ ２−７〜
０．５ （８Ｈ＋ ｒｎ ）ＭＳ（相対強度）：１９６
（Ｍ”、６８％）、１６５（３３％）。3500-2150 "H-NMR (δI)I)m): 9-42 (I)
f98)? 4.10 (I H9d, J-8
Hz) + 3-78 (I H, d + J = 8
Hz) tl, 58 (2H, Q, J=7Hz), 0
．． 93 (3H, t, J=7 Hz) + 2-7~
0.5 (8H+rn) MS (relative intensity): 196
(M”, 68%), 165 (33%).
１５１（Ｍ−Ｃ００Ｈ，３６％）、８１（３４％）、７
９（４３％）、７７（３９チ）、５７（Ｉ００係）、５
５（３７慢）、４〜３７％）
実施例１
６−エチル−３−フェニル−５−オキサトリシクロ（４
、２、１、０３°７〕ノナンの合成：参考例３で得たカ
ルボン酸１５ ｔ （０，０８ｍｏｔ又四酢酸鉛４０
？ （０，０８ｍｏｔ）及びピリジン９．４８ｆ （０
，１２ｍｏｌ ）を１６０−のベンゼン中で７時間加熱
還流した。アルミナで固形物を戸別した。151 (M-C00H, 36%), 81 (34%), 7
9 (43%), 77 (39chi), 57 (I00 section), 5
Example 1 6-ethyl-3-phenyl-5-oxatricyclo(4-37%)
, 2, 1, 03°7] Synthesis of nonane: 15 t (0,08 mot) of the carboxylic acid obtained in Reference Example 3
? (0,08mot) and pyridine 9.48f (0
, 12 mol) was heated under reflux for 7 hours in 160-benzene. Solids were separated from door to door using alumina.
固形物はエーテルでよく洗浄した。有機層を４Ｎ塩酸、
飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥した
。溶媒を留去し、粗生成物１２Ｆを得た。The solids were washed well with ether. The organic layer was treated with 4N hydrochloric acid,
It was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain crude product 12F.
粗生成物を２００艷のエーテルに溶かした溶液？に素化
アルミニウムリチウム２１．５５９（０，０７ｍｍｏｔ
）を８０ｍ／のエーテルに加えた溶液に３０分で滴下し
た。１時間加熱還流した後水浴中で過剰の水素化アルミ
ニウムリチウムを酢酸エチルによｐ分解し、４Ｎ塩酸を
加えて士１−をデカンテーションした。飽イ１１恵ソウ
水、飽和水塩水及び水で洗浄し、無水硫酸マグネシウム
で乾燥した。溶媒を留去し、ヘキサン−酢酸エチル（４
：１）を溶媒としてシリカゲルカラムクロマトグラフィ
ーにより標記化合物を分１１ｔｎｊＪ！！ｔ、た。A solution of the crude product in 200 liters of ether? Lithium aluminum dioxide 21.559 (0.07 mmot
) was added dropwise to a solution of 80 m/ml of ether over 30 minutes. After heating under reflux for 1 hour, excess lithium aluminum hydride was decomposed with ethyl acetate in a water bath, 4N hydrochloric acid was added, and the lithium aluminum hydride was decanted. It was washed with water, saturated brine and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off and hexane-ethyl acetate (4
The title compound was purified by silica gel column chromatography using 1) as a solvent for 11 minutes. ! T, ta.
収量４．７２９ （収率２６％）
沸点１１４℃／ ２２ ｍ５Ｈｙ
元素分析Ｃｔｓｌ（ｚｏｏとして
計算値（チ） ： Ｃ； ８４．１６ 、 Ｈ： ８．
８３実測値（％） ： Ｃ： ８４．１９ 、 Ｈ；
８．８５ＴＲ（ＮａＣＬ、ｃｍ−”）： ３０６０．２
９６０．２８５５ 。Yield 4.729 (yield 26%) Boiling point 114°C/22 m5Hy Elemental analysis Ctsl (calculated value as zoo): C; 84.16, H: 8.
83 Actual value (%): C: 84.19, H;
8.85TR (NaCL, cm-”): 3060.2
960.2855.
１６００．１４４０，１３７０．１０５５”Ｈ−ＮＭＲ
（δｐｐｍ）ニア、２０（５Ｈ，ｓ）、３．９５（ＬＨ
。1600.1440, 1370.1055”H-NMR
(δppm) Near, 20 (5H, s), 3.95 (LH
.
ｄ、Ｊ＝８Ｈ，）、３．６５（口１．ｄ、、１−８Ｈｚ
）ｖｏ、９７（３Ｈ，ｔ 、Ｊ＝７Ｈｚ）、２．８〜１
．２（ＩＯＨ，ｍ）ＭＳ（相対強度）：２２８（Ｍ”、
５４％）、９１１１００％）。d, J=8H,), 3.65 (mouth 1.d,, 1-8Hz
) vo, 97 (3H, t, J=7Hz), 2.8-1
．． 2 (IOH, m) MS (relative intensity): 228 (M”,
54%), 911100%).
７７（４０％、ｐｈ）
実施例２ シトラスコロンタイプ調合香姐しモン油イタ
リーベルガプテンフリー １５０（重量部）リモネ
ン ４７０リナリルアセテート
２００ブチグレン７山ビガラード
２０ミユーゲペース ５０アセチルセ
ドレン ５０ムスクケトン
２０上記調合香料９６０部に、６−エチル−３
−フェニル−５−オキサトリシクロ［４，２，１゜３．
７
０ 〕ノナンを４０部加えることにより、グレープフル
ーツ的甘さの加わったシトラスコロンタイプ調合香料が
得られた。77 (40%, ph) Example 2 Citrus cologne type formulation Incense oil Italy Bergapten free 150 (parts by weight) Limonene 470 Linalyl acetate
200 Butiguren 7 Mountain Bigarado
20 Miuge Pace 50 Acetyl Cedrene 50 Musk Ketone
20 To 960 parts of the above blended fragrance, add 6-ethyl-3
-Phenyl-5-oxatricyclo[4,2,1°3.
70] By adding 40 parts of nonane, a citrus cologne type blended fragrance with grapefruit-like sweetness was obtained.
以上
手続補正書（自発）
昭和６１年６月１７［１
１、事件の表示
昭和６１年特許願第 １１１２３２ 号２、 発明の名
称
香料組成物
３、補正をする者
事件との関係 出願人
名称 （０９１）花王株式会社
４、代理人
氏 名 （８６３２）弁理士 小 野 信 夫１．１．
″Ｉ６、補正の対象
明細書の「発明の詳細な説明」の欄
７、補正の内容
（Ｉ） 明細書中、第２頁下から第２行の弐Ｏ）およ
び（２）全以下のとおりに訂正する。Written amendment to the above procedure (voluntary) June 17, 1985 [1 1, Indication of the case Patent Application No. 111232 of 1988 2, Name of the invention Fragrance composition 3, Person making the amendment Relationship to the case Name of applicant ( 091) Kao Corporation 4, agent name (8632) Patent attorney Nobuo Ono 1.1.
``I6, Column 7 of "Detailed Description of the Invention" of the specification to be amended, Contents of the amendment (I) In the specification, 2nd line from the bottom of page 2, (2) and (2) are all as follows. Correct.
［ 」[ ”
Claims (1)
リシクロ〔４．２．１．０＾３＾，＾７〕ノナン。 ２、次式（ I ） ▲数式、化学式、表等があります▼（ I ） で表わされる６−エチル−３−フェニル−５−オキサト
リシクロ〔４．２．１．０＾３＾，＾７〕ノナンを含有
することを特徴とする香料組成物。[Claims] 1. 6-ethyl-3-phenyl-5-oxatricyclo [4.2.1.0 ^3^,^7] Nonane. 2. 6-ethyl-3-phenyl-5-oxatricyclo[4.2.1.0^3^,^7] represented by the following formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) ] A fragrance composition characterized by containing nonane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61111232A JPS62267278A (en) | 1986-05-15 | 1986-05-15 | 6-ethyl-3-phenyl-5-oxatricyclo(4.2.1.03,7)nonane and perfume composition containing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61111232A JPS62267278A (en) | 1986-05-15 | 1986-05-15 | 6-ethyl-3-phenyl-5-oxatricyclo(4.2.1.03,7)nonane and perfume composition containing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62267278A true JPS62267278A (en) | 1987-11-19 |
Family
ID=14555909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61111232A Pending JPS62267278A (en) | 1986-05-15 | 1986-05-15 | 6-ethyl-3-phenyl-5-oxatricyclo(4.2.1.03,7)nonane and perfume composition containing same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62267278A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52171314U (en) * | 1976-06-17 | 1977-12-26 | ||
| JPS6157208U (en) * | 1984-09-20 | 1986-04-17 |
-
1986
- 1986-05-15 JP JP61111232A patent/JPS62267278A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52171314U (en) * | 1976-06-17 | 1977-12-26 | ||
| JPS6157208U (en) * | 1984-09-20 | 1986-04-17 |
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