JPH0283378A - Production of 8,12-epoxy-13,14,15,16-tetranorlabdane - Google Patents
Production of 8,12-epoxy-13,14,15,16-tetranorlabdaneInfo
- Publication number
- JPH0283378A JPH0283378A JP63232555A JP23255588A JPH0283378A JP H0283378 A JPH0283378 A JP H0283378A JP 63232555 A JP63232555 A JP 63232555A JP 23255588 A JP23255588 A JP 23255588A JP H0283378 A JPH0283378 A JP H0283378A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- formula
- organic solvent
- high yield
- reaction
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- YPZUZOLGGMJZJO-LUYZLQTOSA-N (3ar,5ar,9as,9br)-3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-1h-benzo[e][1]benzofuran Chemical compound CC([C@H]1CC2)(C)CCC[C@]1(C)[C@@H]1[C@]2(C)OCC1 YPZUZOLGGMJZJO-LUYZLQTOSA-N 0.000 title 1
- -1 zinc halide Chemical class 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- AIALTZSQORJYNJ-UHFFFAOYSA-N 1-(2-hydroxyethyl)-2,5,5,8a-tetramethyl-3,4,4a,6,7,8-hexahydro-1h-naphthalen-2-ol Chemical compound OCCC1C(C)(O)CCC2C(C)(C)CCCC21C AIALTZSQORJYNJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 13
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 9
- 235000005074 zinc chloride Nutrition 0.000 abstract description 5
- 239000011592 zinc chloride Substances 0.000 abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 4
- XVULBTBTFGYVRC-HHUCQEJWSA-N sclareol Chemical compound CC1(C)CCC[C@]2(C)[C@@H](CC[C@](O)(C)C=C)[C@](C)(O)CC[C@H]21 XVULBTBTFGYVRC-HHUCQEJWSA-N 0.000 abstract description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 abstract description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 abstract description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 abstract description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 abstract description 4
- 239000003205 fragrance Substances 0.000 abstract description 3
- XVULBTBTFGYVRC-UHFFFAOYSA-N Episclareol Natural products CC1(C)CCCC2(C)C(CCC(O)(C)C=C)C(C)(O)CCC21 XVULBTBTFGYVRC-UHFFFAOYSA-N 0.000 abstract description 2
- LAEIZWJAQRGPDA-UHFFFAOYSA-N Manoyloxid Natural products CC1(C)CCCC2(C)C3CC=C(C)OC3(C)CCC21 LAEIZWJAQRGPDA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 2
- 229940102001 zinc bromide Drugs 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 3
- 239000002304 perfume Substances 0.000 abstract 2
- YPZUZOLGGMJZJO-UHFFFAOYSA-N ambrofix Natural products C1CC2C(C)(C)CCCC2(C)C2C1(C)OCC2 YPZUZOLGGMJZJO-UHFFFAOYSA-N 0.000 description 9
- YPZUZOLGGMJZJO-LQKXBSAESA-N ambroxan Chemical compound CC([C@@H]1CC2)(C)CCC[C@]1(C)[C@@H]1[C@]2(C)OCC1 YPZUZOLGGMJZJO-LQKXBSAESA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IMKJGXCIJJXALX-SHUKQUCYSA-N Norambreinolide Chemical compound CC([C@@H]1CC2)(C)CCC[C@]1(C)[C@@H]1[C@]2(C)OC(=O)C1 IMKJGXCIJJXALX-SHUKQUCYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IMKJGXCIJJXALX-UHFFFAOYSA-N ent-Norambreinolide Natural products C1CC2C(C)(C)CCCC2(C)C2C1(C)OC(=O)C2 IMKJGXCIJJXALX-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229940096995 sclareolide Drugs 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、アンバー様香気を有し香料物質として有用な
８，１２−エポキシ−１３，１４，１５１６−チトラノ
ルラブダンの新規な製法に関する。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a novel method for producing 8,12-epoxy-13,14,1516-titranorlabdan, which has an amber-like aroma and is useful as a fragrance substance. .
更に詳しくは、本発明は下記式（２）
で表される２、５，５．８ａ−テトラメチル−１−（２
−ヒドロキシエチル）−２−ヒドロキシデカリンを有機
溶媒中、ハロゲン化亜鉛と接触反応させることを特徴と
する下記式（１）で表される２、５，５．８ａ−テトラ
メチル−１−（２−ヒドロキシエチル）−２−ヒドロキ
シデカリンを有機溶媒中、ハロゲン化亜鉛と接触反応さ
せることを特徴とする下記式（１）
で表される８、１２−エポキシ−１３，１４゜１５．１
６−チトラノルラブダンの製法。More specifically, the present invention relates to 2,5,5.8a-tetramethyl-1-(2
2,5,5.8a-tetramethyl-1-(2 8,12-epoxy-13,14゜15.1 represented by the following formula (1), characterized in that 2-hydroxydecalin (hydroxyethyl)-2-hydroxydecalin is catalytically reacted with zinc halide in an organic solvent.
6-Production method of titranollabdan.
３、発明の詳細な説明
で表される８、１２−エポキシ−１３，１４，１５，１
６−チトラノルラブダンの新規な製法に関する。3. 8,12-epoxy-13,14,15,1 expressed in the detailed description of the invention
The present invention relates to a new method for producing 6-titranorlabdane.
（従来の技術）
従来、上記式（２）の２．５，５，８ａ−テトラメチル
−１−（２−ヒドロキシエチル）−２−ヒドロキシデカ
リンから上記式（１）の８，１２−エポキシ１３，１４
，１５．１６−チトラノルラブダン（以下、アンブロッ
クスという）を合成する方法としては、例えば、線式（
２）の化合物をＡｌ２Ｏ３またはナフタレンスルホン酸
を脱水触媒として、加熱脱水して線式（１）のアンブロ
ックスを得る方法（香料化学総覧、広角書店、昭和４７
年発行、７０７頁）、同じく線式（２）化合物の脱水剤
として、活性白土、アルミナ、シリカゲルなどのごとき
固体酸の表面にブレンステッド酸を吸着させた固体酸触
媒を使用したもの（特開昭６１−３３１８４号）あるい
は同じく脱水剤として、塩化チタンを使用する方法（特
公昭６１−１４３２号）などの提案がなされている。(Prior art) Conventionally, 8,12-epoxy 13 of the above formula (1) was converted from 2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-2-hydroxydecalin of the above formula (2). ,14
, 15.16-Titranorlabdane (hereinafter referred to as Ambrox) can be synthesized using, for example, the linear method (
A method of heating and dehydrating the compound of 2) using Al2O3 or naphthalene sulfonic acid as a dehydration catalyst to obtain ambrox of the linear formula (1) (Fragrance Chemistry Complete Guide, Kokaku Shoten, 1972)
(Published in 2010, p. 707), and also as a dehydrating agent for the linear formula (2) compound, a solid acid catalyst in which Brønsted acid is adsorbed on the surface of a solid acid such as activated clay, alumina, or silica gel (Unexamined Japanese Patent Publication No. (Japanese Patent Publication No. 61-1432) has been proposed, as well as a method using titanium chloride as a dehydrating agent.
（発明が解決しようとする課題）
上述の従来提案の方法は、反応操作が煩雑であり、収率
が低く、更に工業的には適さないなどの問題点がある。(Problems to be Solved by the Invention) The conventionally proposed methods described above have problems such as complicated reaction operations, low yields, and are not industrially suitable.
（課題を解決するための手段）
本発明者らは、上述の如き不利益乃至欠点を回避すべく
脱水剤について鋭意研究を行ってきた。(Means for Solving the Problems) The present inventors have conducted intensive research on dehydrating agents in order to avoid the disadvantages and disadvantages described above.
その結果、ハロゲン化亜鉛が前記式（２）化合物の脱水
環化触媒として、優れた機能を有するこを見出した。す
なわち、該触媒を使用すれば副生成物がほとんど生成さ
れず、高純度且つ高収率で工業的に前記式（１）の化合
物を製造できることが判明した。As a result, it has been found that zinc halide has an excellent function as a dehydration cyclization catalyst for the compound of formula (2). That is, it has been found that by using this catalyst, the compound of the formula (1) can be produced industrially with high purity and high yield, with almost no by-products being produced.
すなわち、本発明者らは、下記式（２）で表される２、
５，５．８ａ−テトラメチル−１−（２−ヒドロキシエ
チル）−２−ヒドロキシデカリンを有８１溶媒中、ハロ
ゲン化亜鉛と接触反応させることにより、下記式（１）
で表されるアンブロックスが容易に高純度且つ高収率で
合成できることを見出した。That is, the present inventors found that 2, represented by the following formula (2),
By contacting and reacting 5,5.8a-tetramethyl-1-(2-hydroxyethyl)-2-hydroxydecalin with zinc halide in a 81 solvent, Ambrox represented by the following formula (1) can be obtained. It has been found that it can be easily synthesized with high purity and high yield.
従って、本発明の目的は上記従来提案に比べて、上記式
（１）のアンブロックスを容易な操作で工業的に高純度
且つ高収率で安価に製造できる方法を提供するにある。Therefore, an object of the present invention is to provide a method for producing Ambrox of the formula (1) industrially with high purity and high yield through easy operations and at low cost compared to the conventional proposals.
本発明の上記式（１）のアンブロックスの製造の態様を
、上記式（２）の化合物の製造例を含めて工程図で示す
と、以下のように表すことができる。The mode of production of Ambrox of the above formula (1) of the present invention can be expressed as follows when shown in a process diagram including a production example of the compound of the above formula (2).
本発明の上記式（１）のアンプコックスの製造方法を以
下に詳細に説明する。The method for manufacturing the amplifier cox of the above formula (1) of the present invention will be explained in detail below.
本発明の原料である上記式（２）の２．５．５．８ａ−
テトラメチル−１−（２−ヒドロキシエチル）−２−ヒ
ドロキシデカリンは、市場でも人手可能であるが、例え
ば、スクラレオールを酸化剤と処理してノルアンプレノ
ライドを合成し、つぎに、これを還元して容易に合成す
ることもできる。2.5.5.8a- of the above formula (2) which is a raw material of the present invention
Tetramethyl-1-(2-hydroxyethyl)-2-hydroxydecalin can be produced manually on the market, but for example, noamprenolide is synthesized by treating sclareol with an oxidizing agent, and then this is reduced. It can also be easily synthesized by
例えば、上述のようにして合成することのできる上記式
（２）化合物から本発明の上記式（１）のアンブロック
スを合成するには、線式（２）の化合物を有機溶媒中、
ハロゲン化亜鉛と接触反応することにより容易に合成す
ることができる。For example, in order to synthesize Ambrox of the above formula (1) of the present invention from the above formula (2) compound that can be synthesized as described above, the compound of the linear formula (2) is mixed in an organic solvent,
It can be easily synthesized by catalytic reaction with zinc halide.
該反応の条件としては、例えば、反応温度は、室温程度
で進行するので特に制約はないが、約−１０℃〜約５０
℃程度の範囲が特に好ましい例として挙げられる。反応
時間は、上記条件によっても異なるが、例えば、約８時
間〜約２０時間程度の反応時間が好ましく挙げられる。Conditions for the reaction include, for example, the reaction temperature, which is not particularly limited since it proceeds at about room temperature, but is about -10°C to about 50°C.
A particularly preferable example is a range of about .degree. Although the reaction time varies depending on the above conditions, for example, a reaction time of about 8 hours to about 20 hours is preferably mentioned.
上記反応の脱水環化に使用されるハロゲン化亜鉛として
は、例えば、臭化亜鉛、ヨウ化亜鉛、フッ化亜鉛、塩化
亜鉛などが使用されるが、特に塩化亜鉛が安価であり、
また取り扱いが容易であるので好ましい、このようなハ
ロゲン化亜鉛の使用量には特別の制限はなく適宜選択す
ればよいが、例えば、上記式（２）の化合物に対して、
約０゜１〜約２重量％程度の範囲が好ましく使用される
また、反応は有機溶媒中で行うのが好ましく、このよう
な有機溶媒としては、例えば、ジクロルメタン、四塩化
炭素、トルエン、ベゼン、エーテル、テトラヒドロフラ
ンなどを例示することができる。これら有機溶媒の使用
量には特別の制約はなく幅広く使用することができるが
、例えば、上記式（２）の化合物に対して約１〜約５０
重量倍程度の範囲を例示することができる。As the zinc halide used in the dehydration cyclization in the above reaction, for example, zinc bromide, zinc iodide, zinc fluoride, zinc chloride, etc. are used, but zinc chloride is particularly cheap,
The amount of zinc halide, which is preferred because it is easy to handle, is not particularly limited and may be selected as appropriate; for example, for the compound of formula (2) above,
The range of about 0.1 to about 2% by weight is preferably used. Furthermore, the reaction is preferably carried out in an organic solvent, such as dichloromethane, carbon tetrachloride, toluene, bezene, Examples include ether and tetrahydrofuran. There are no particular restrictions on the amount of these organic solvents to be used, and they can be used in a wide range of amounts, but for example, about 1 to about 50
An example is a range of about twice the weight.
反応終了後は、常法に従って水洗浄を行い、アルカリで
中和後、溶媒を除去して高収率で本発明の上記式（１）
のアンブロックスを得ることができる。After the reaction is completed, washing with water is carried out according to a conventional method, and after neutralization with an alkali, the solvent is removed to obtain the above formula (1) of the present invention in high yield.
You can get Ambrox.
以下に本発明の態様につき、参考例及び実施例をあげて
更に詳細に説明する。Aspects of the present invention will be described in more detail below with reference to Reference Examples and Examples.
（参考例）
２．５，５．８ａ−テトラメチル−１−（２−ヒドロキ
シエチル）−２−ヒドロキシデカリン［式（３）］の合
成。(Reference Example) Synthesis of 2.5,5.8a-tetramethyl-1-(2-hydroxyethyl)-2-hydroxydecalin [Formula (3)].
反応フラスコにスクラレオライド１００ｇ、乾燥トルエ
ン４００ｇを入れ、内温３０〜４０℃を保ちながらく少
し冷却する）７０％ＮａＡＩＨ（ＯＣＨ２ＣＨ２０ＣＨ
３）２ １４６ｇと乾燥トルエン１４６ｇの溶液を１時
間で加え、同温で２時間撹拌を続けた。次いで、酢酸エ
チル３０ｇ（０，３４モル）を３５℃、１５分間で加え
（約半分＠滴下まで発熱があるので冷却する）、同温で
３０分間撹拌を続けた。Put 100 g of sclareolide and 400 g of dry toluene into a reaction flask, and cool slightly while maintaining the internal temperature of 30 to 40°C) 70% NaAIH (OCH2CH20CH
3) A solution of 146 g of 2 and 146 g of dry toluene was added over 1 hour, and stirring was continued at the same temperature for 2 hours. Next, 30 g (0.34 mol) of ethyl acetate was added at 35° C. over 15 minutes (about half of the dropwise addition was cooled as there was an exotherm), and stirring was continued at the same temperature for 30 minutes.
冷却後、１０％ＮａＯＨ水溶液５００ｇ中に反応液を注
入した（約３３〜４０℃まで発熱）。さらに１０％Ｎａ
ＯＨ水溶液５００ｇ中で洗浄、温水（約７０℃）で３回
洗浄後、溶媒を回収し、粗製物１０２ｇを得た。After cooling, the reaction solution was poured into 500 g of 10% NaOH aqueous solution (exothermic to about 33-40° C.). Additionally 10% Na
After washing in 500 g of an OH aqueous solution and three times with warm water (approximately 70° C.), the solvent was recovered to obtain 102 g of a crude product.
この粗製物にトルエン２００ｇを加えて、加熱溶解後、
冷却して結晶化させ、白色結晶８７ｇ（収率；８５．６
）を得た。このものの純度は９８％であった（ＧＬＣ）
。Add 200g of toluene to this crude product, heat and dissolve,
It was cooled and crystallized to give 87 g of white crystals (yield: 85.6
) was obtained. The purity of this material was 98% (GLC)
.
（実施例） アンブロックス［式（１）］の合成。(Example) Synthesis of Ambrox [Formula (1)].
反応フラスコ中に塩化亜鉛４４ｇ、塩化メチレン４８４
ｇを入れ、内温２８℃で式（２）の化合物を４４ｇを１
０分間で加えた。その後、２５〜３０℃で４．５時間か
くはんした。反応終了後、反応油Ｆ！液を水洗浄２回行
い、重曹水溶液で洗浄した後、硫酸マグネシウムで乾燥
し溶媒を回収して粗製物４０ｇを得た。44 g of zinc chloride, 484 g of methylene chloride in the reaction flask
g of the compound of formula (2) at an internal temperature of 28°C.
Added in 0 minutes. Thereafter, it was stirred at 25-30°C for 4.5 hours. After the reaction is complete, the reaction oil F! The liquid was washed twice with water, washed with an aqueous sodium bicarbonate solution, dried over magnesium sulfate, and the solvent was recovered to obtain 40 g of a crude product.
ｍ製物にエタノール４０ｇを加えて加熱溶解した後、冷
却して結晶化させ、白色結晶３０ｇ（収率；７０％、Ｇ
ＬＣ純度９９．８％、 ｒａ点；７４℃［α］Ｄ ＝−
２５，２°）を得た。G
LC purity 99.8%, ra point; 74°C [α]D = -
25,2°) was obtained.
（発明の効果）
前記式（２）の化合物から本発明の前記式（１）のアン
ブロックスを製造する方法において、脱水環化するに際
し、ハロゲン化亜鉛を使用することにより、従来法に比
べて高純度且つ高収率で工業的に製造できる優れた方法
が提供できる。(Effects of the Invention) In the method for producing Ambrox of the formula (1) of the present invention from the compound of the formula (2), zinc halide is used during dehydration and cyclization, compared to conventional methods. An excellent method for industrial production with high purity and high yield can be provided.
特許出願人 長谷川香料株式会社Patent applicant: Hasegawa Fragrance Co., Ltd.
Claims (1)
−ヒドロキシエチル）−２−ヒドロキシデカリンを有機
溶媒中、ハロゲン化亜鉛と接触反応させることを特徴と
する下記式（１）▲数式、化学式、表等があります▼（
１） で表される８，１２−エポキシ−１３，１４，１５，１
６−テトラノルラブダンの製法。[Claims] 1. 2,5,5,8a-tetramethyl-1-(2
-Hydroxyethyl)-2-hydroxydecalin is reacted with zinc halide in an organic solvent by the following formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼
1) 8,12-epoxy-13,14,15,1 represented by
6-Production method of tetranorlabdane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63232555A JPH0745487B2 (en) | 1988-09-19 | 1988-09-19 | Process for producing 8,12-epoxy-13,14,15,16-tetranorlabdane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63232555A JPH0745487B2 (en) | 1988-09-19 | 1988-09-19 | Process for producing 8,12-epoxy-13,14,15,16-tetranorlabdane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0283378A true JPH0283378A (en) | 1990-03-23 |
| JPH0745487B2 JPH0745487B2 (en) | 1995-05-17 |
Family
ID=16941162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63232555A Expired - Lifetime JPH0745487B2 (en) | 1988-09-19 | 1988-09-19 | Process for producing 8,12-epoxy-13,14,15,16-tetranorlabdane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0745487B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5268355A (en) * | 1992-03-06 | 1993-12-07 | Firmenich S.A. | Furan esters and their use as perfuming ingredients |
| US5292902A (en) * | 1991-08-02 | 1994-03-08 | Givaudan-Roure Corporation | Process for the manufacture of odorants and intermediates used therein |
-
1988
- 1988-09-19 JP JP63232555A patent/JPH0745487B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5292902A (en) * | 1991-08-02 | 1994-03-08 | Givaudan-Roure Corporation | Process for the manufacture of odorants and intermediates used therein |
| US5268355A (en) * | 1992-03-06 | 1993-12-07 | Firmenich S.A. | Furan esters and their use as perfuming ingredients |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0745487B2 (en) | 1995-05-17 |
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