JPS5945661B2 - Stereoselective ring closure method from d-citronellal to l-isopulegol - Google Patents
Stereoselective ring closure method from d-citronellal to l-isopulegolInfo
- Publication number
- JPS5945661B2 JPS5945661B2 JP52030059A JP3005977A JPS5945661B2 JP S5945661 B2 JPS5945661 B2 JP S5945661B2 JP 52030059 A JP52030059 A JP 52030059A JP 3005977 A JP3005977 A JP 3005977A JP S5945661 B2 JPS5945661 B2 JP S5945661B2
- Authority
- JP
- Japan
- Prior art keywords
- isopulegol
- citronellal
- zinc
- ring closure
- 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.)
- Expired
Links
- ZYTMANIQRDEHIO-KXUCPTDWSA-N isopulegol Chemical compound C[C@@H]1CC[C@@H](C(C)=C)[C@H](O)C1 ZYTMANIQRDEHIO-KXUCPTDWSA-N 0.000 title claims description 21
- NEHNMFOYXAPHSD-UHFFFAOYSA-N beta-citronellal Natural products O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 7
- 238000006798 ring closing metathesis reaction Methods 0.000 title claims description 6
- 230000000707 stereoselective effect Effects 0.000 title claims description 5
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- -1 zinc halide Chemical class 0.000 claims description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 229940102001 zinc bromide Drugs 0.000 claims description 5
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims 1
- 229930195734 saturated hydrocarbon Natural products 0.000 claims 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000001871 (1R,2R,5S)-5-methyl-2-prop-1-en-2-ylcyclohexan-1-ol Substances 0.000 description 6
- 229940095045 isopulegol Drugs 0.000 description 6
- ZYTMANIQRDEHIO-UHFFFAOYSA-N neo-Isopulegol Natural products CC1CCC(C(C)=C)C(O)C1 ZYTMANIQRDEHIO-UHFFFAOYSA-N 0.000 description 4
- NOOLISFMXDJSKH-KXUCPTDWSA-N (-)-Menthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1O NOOLISFMXDJSKH-KXUCPTDWSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000002841 Lewis acid Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229940041616 menthol Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- ZYTMANIQRDEHIO-UTLUCORTSA-N (1s,2s,5r)-5-methyl-2-prop-1-en-2-ylcyclohexan-1-ol Chemical compound C[C@@H]1CC[C@@H](C(C)=C)[C@@H](O)C1 ZYTMANIQRDEHIO-UTLUCORTSA-N 0.000 description 1
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000010632 citronella oil Substances 0.000 description 1
- 229930003633 citronellal Natural products 0.000 description 1
- 235000000983 citronellal Nutrition 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明はｄ−シトラネラールから１−イソプレゴールヘ
の立体選択的閉環方法、更に詳細にはｄ−シトロネラー
ルを溶触中ハロゲン化亜鉛と反応せしめて１−イソプレ
ゴールを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for stereoselective ring closure of d-citronellal to 1-isopulegol, and more particularly to a method for producing 1-isopulegol by reacting d-citronellal with zinc halide during melt contact.
１−イソプレゴールは環元して１−メントールに導くこ
とができる、合成ハツカ工業上有用な中間体である。1-Isopulegol is an industrially useful intermediate for synthesis that can be converted into 1-menthol.
ｄ−シトロネラールはシトロネラ油の主要成分で、従来
より１−メントールを製造するための原料として使用さ
れており、これに関する多くの報告がなされている。し
かし、ｄ−シトロネラールを閉環反応せしめる、ときは
、１−イソプレゴールの他に各種の異性体が生成する欠
点がある。d-Citronellal is a major component of citronella oil, and has traditionally been used as a raw material for producing 1-menthol, and many reports have been made regarding this. However, when d-citronellal is subjected to a ring-closing reaction, there is a drawback that various isomers are produced in addition to 1-isopulegol.
例えば、特公昭３２−８８７５号はＢ−Ａｌ−Ｓｉの酸
化物、水酸化物あるいは塩類を使用する方法を報告して
いるが、この生成物の旋光度より計算すると、生成物は
１−イソプレゴールが６０係、ｄ−ネオイソプレゴール
が４０％である。また、清水らは無水酢酸により閉環し
、次いで鹸化して１−イソプレゴール５８％、ｄ−ネオ
イソプレゴール４２％を得た〔Ｂｕｌｌ、Ａｇｒ、Ｃｈ
ｅｍ、Ｓｏｃ、Ｊａｐａｎ、２４巻１４０２頁（１９６
０年）〕。更にまた、Ｇ、Ｏｈｌ−ｏｆｆらはｄ−シト
ロネラールを１８０℃で３０時間加熱して１−イソプレ
ゴｉル６０％および他の３種の異性体４０％を得ている
。〔Ｈｅｌｖ、Ｃｈ−ｉｍ、Ａｃｔａ、５０巻、１５３
頁（１９６７年）〕。以上の如く、従来法によるときは
、１−イソプレゴールの収率は最高６０％であり、しか
もこれには他の副生物を含有するので、純粋な１−イソ
プレゴールを得るには煩瑣な分離精製工程を必要とする
し、また粗製イソプレゴールを原料として、メントール
を製造した場合には異性体分割の操作が不可欠であつた
。斯る実情に鑑み、本発明者はｄ−シトロネラールから
１−イソプレゴールヘの立体節択的閉環を行わんと、各
種ルイス酸によるｄ−シトロネラーフ ルの閉環反応を
検討した結果、第１表に示すような結果を得た。For example, Japanese Patent Publication No. 32-8875 reports a method using B-Al-Si oxides, hydroxides, or salts. Calculating from the optical rotation of this product, the product is 1-isopulegol. is 60%, and d-neisopulegol is 40%. Furthermore, Shimizu et al. performed ring closure with acetic anhydride and saponification to obtain 58% of 1-isopulegol and 42% of d-neoisopulegol [Bull, Agr, Ch.
em, Soc, Japan, vol. 24, p. 1402 (196
0 years)]. Furthermore, G. Ohl-off et al. heated d-citronellal at 180° C. for 30 hours to obtain 60% of 1-isopulegol and 40% of the other three isomers. [Helv, Ch-im, Acta, vol. 50, 153
Page (1967)]. As mentioned above, when using the conventional method, the yield of 1-isopulegol is at most 60%, and since it contains other by-products, cumbersome separation and purification steps are required to obtain pure 1-isopulegol. Furthermore, when menthol was produced using crude isopulegol as a raw material, an operation for isomer separation was indispensable. In view of these circumstances, the present inventor investigated the stereoselective ring closure of d-citronellal to 1-isopulegol and the ring-closing reaction of d-citronellal full with various Lewis acids, as shown in Table 1. I got good results.
第１表（各種ルイス酸を用いて反応温度５〜１０℃でｄ
−シトロネラールの閉環反応を行つたときの生成物の比
較を示す）
第１表において、腐１〜７においてはイソプレゴールと
ネオイソプレゴール以外は樹脂状反応物で、未反応ｄ−
シトラネラールは回収できなかつた。Table 1 (using various Lewis acids at a reaction temperature of 5 to 10°C)
- Shows a comparison of the products obtained when the ring-closing reaction of citronellal is carried out) In Table 1, in the cases 1 to 7, except for isopulegol and neoisopulegol, the unreacted d-
Citranellal could not be recovered.
ＺｎＦ２の場合は低温では反応しないが、温度を上げる
と反応が行われる。腐９〜１１の場合は副生成物は少な
く、未反応のｄ−シトロネラールの大部分は回収された
。腐１２〜１４においてはＺｎＩ，の場合ｄ−シトロネ
ラールは回収されたが、ＺｎＣ＃２およびＺｎＢｒ，の
場合は回収されなかつたＯ第１表から明らかな如く、多
くのルイス酸の中でハロゲン化亜鉛が卓越した効果を示
し、これを使用するときは純度９５ｑ６以上の２−イソ
プレゴールが得られることを見出した。In the case of ZnF2, it does not react at low temperatures, but the reaction occurs when the temperature is raised. In the cases of Nos. 9 to 11, there were few by-products, and most of the unreacted d-citronellal was recovered. In Nos. 12 to 14, d-citronellal was recovered in the case of ZnI, but not in the case of ZnC#2 and ZnBr. It has been found that zinc exhibits an outstanding effect and that when zinc is used, 2-isopulegol with a purity of 95q6 or higher can be obtained.
本発明方法を実施するには、塩化亜鉛、臭化亜鉛、ヨウ
化亜鉛などのハロゲン化亜鉛を溶剤に懸濁させ、これに
ｄ−シトロネラールを滴下するか、またはハロゲン化亜
鉛を管に充填し、これにｄーシトロネラールの溶液を流
下させて反応させる。To carry out the method of the present invention, a zinc halide such as zinc chloride, zinc bromide, or zinc iodide is suspended in a solvent, and d-citronellal is added dropwise thereto, or the zinc halide is filled into a tube. , a solution of d-citronellal is allowed to flow down thereto for reaction.
溶剤としては、石油エーテル、ｎ−ヘキサン、シクロヘ
キサン、ベンゼン、トルエン等の飽和または不飽和の鎖
状または環状炭化水素；クロロホルム、四塩化炭素、塩
化メチレン等のハロゲン炭化水素が好ましく、またハロ
ゲン化亜鉛はｄ−シトロネラールに対して０．１〜１モ
ルを使用するのが好適である。反応温度は０〜５０℃、
特に１０℃附近が好ましい。ＺｎＦ，の場合は４０〜５
０℃において反応が行なわれる。反応時間は滴下時間を
含めて３０〜６０分位が好ましい。反応後は、ハロゲン
化亜鉛を除去し、次いで溶剤部を水洗した後溶剤を留去
し、減圧蒸留すれば９５％以上の純度の′−イソプレゴ
ールが収得される。Preferred solvents include saturated or unsaturated chain or cyclic hydrocarbons such as petroleum ether, n-hexane, cyclohexane, benzene, and toluene; halogen hydrocarbons such as chloroform, carbon tetrachloride, and methylene chloride; and zinc halides. is preferably used in an amount of 0.1 to 1 mol based on d-citronellal. The reaction temperature is 0-50℃,
Particularly preferred is around 10°C. For ZnF, 40 to 5
The reaction is carried out at 0°C. The reaction time is preferably about 30 to 60 minutes including the dropping time. After the reaction, the zinc halide is removed, the solvent part is washed with water, the solvent is distilled off, and the solvent is distilled under reduced pressure to obtain '-isopulegol with a purity of 95% or more.
尚ハロゲン化亜鉛は済過によつて９５％以上が回収され
、これは次の反応に再利用できる。以上の如く、本発明
によれば、ｄ−シトロネラールの立体選択的閉環によつ
て純度の高いｊ−イソプレゴールを得ることができるの
で、これを常法によつて還元すれば純粋な２−メントー
ルを得ることができ、合成ハツカ工業において極めて有
利である。次に実施例を挙げて具体的に説明する。Incidentally, more than 95% of the zinc halide is recovered by filtration, and this can be reused for the next reaction. As described above, according to the present invention, highly pure j-isopulegol can be obtained by stereoselective ring closure of d-citronellal, and pure 2-menthol can be obtained by reducing this by a conventional method. It is very advantageous in the synthesis industry. Next, a concrete explanation will be given with reference to examples.
実施例 １
塩化亜鉛２．７９をベンゼン１０ｍ１に懸濁し、ｄ−シ
トロネラール３．０ｇのベンゼン１０ｍ１溶液を、内温
１０℃で滴下する。Example 1 2.79 of zinc chloride is suspended in 10 ml of benzene, and a solution of 3.0 g of d-citronellal in 10 ml of benzene is added dropwise at an internal temperature of 10°C.
滴下終了後更に１０℃で１０分間攪拌し、反応液を済過
し、済液を冷水で洗浄後無水硫酸マグネシウムで乾燥す
る。溶剤を留去後減圧蒸留すれば、沸点５８〜５９℃／
５ｍｍＨｇ０）ｌ−イソプレゴール２．３９（収率７５
％）が得られる。これをガスクロマトグラフイ一で分析
した結果ｌ−イソプレゴールを９００１）以上含有して
いた。実施例 ２
臭化亜鉛８。After completion of the dropwise addition, the mixture was further stirred at 10° C. for 10 minutes, the reaction solution was filtered, and the filtered solution was washed with cold water and dried over anhydrous magnesium sulfate. If the solvent is distilled off and then distilled under reduced pressure, the boiling point will be 58-59℃/
5mmHg0) l-isopulegol 2.39 (yield 75
%) is obtained. Analysis of this by gas chromatography revealed that it contained more than 9,001) l-isopulegol. Example 2 Zinc Bromide 8.
８１をベンゼン２０ｍ１に懸濁し、これにｄ−シトロネ
ラール６．０９のベンゼン２０ｍ１溶液を約１０℃で滴
下する。81 was suspended in 20 ml of benzene, and a solution of d-citronellal 6.09 in 20 ml of benzene was added dropwise at about 10°C.
滴下後更に１０℃で２０分間撹拌し、反応液を沢過し、
沢液を水洗後無水硫酸ソーダで乾燥する。溶剤を留去後
減圧蒸留してｌ−イソプレゴール７９（収率８０％）を
得た。これをガスクロマトグラフイ一で分析した結果ｌ
−イソプレゴールを９５（ｆｌ）以上含有していた。実
施例 ３
内径１．５ＣｆｆＬ１長さ２０Ｃｒ１Ｌのガラス管下部
にグラスウールを詰め、臭化亜鉛のベンゼン懸濁液を流
して臭化亜鉛１０ｃ！ＲＬの層を形成させる。After the dropwise addition, the mixture was further stirred at 10°C for 20 minutes, and the reaction solution was thoroughly filtered.
After washing the sap with water, dry it with anhydrous sodium sulfate. After the solvent was distilled off, the residue was distilled under reduced pressure to obtain l-isopulegol 79 (yield: 80%). The results of analyzing this using gas chromatography
- Contained 95 (fl) or more of isopulegol. Example 3 The bottom of a glass tube with an inner diameter of 1.5CffL and a length of 20Cr1L was stuffed with glass wool, and a benzene suspension of zinc bromide was poured into it to give 10c of zinc bromide! Form a layer of RL.
Claims (1)
せしめることを特徴とするｌ−イソプレゴールへの立体
選択的閉環方法。 ２ 溶剤が飽和もしくは不飽和炭化水素またはハロゲン
化炭化水素である特許請求の範囲第１項記載の方法。 ３ ハロゲン化亜鉛が塩化亜鉛、臭化亜鉛またはヨウ化
亜鉛である特許請求の範囲第１項記載の方法。[Claims] 1. A method for stereoselective ring closure to l-isopulegol, which comprises reacting 1 d-citronellal with zinc halide in a solvent. 2. The method according to claim 1, wherein the solvent is a saturated or unsaturated hydrocarbon or a halogenated hydrocarbon. 3. The method according to claim 1, wherein the zinc halide is zinc chloride, zinc bromide or zinc iodide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52030059A JPS5945661B2 (en) | 1977-03-18 | 1977-03-18 | Stereoselective ring closure method from d-citronellal to l-isopulegol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52030059A JPS5945661B2 (en) | 1977-03-18 | 1977-03-18 | Stereoselective ring closure method from d-citronellal to l-isopulegol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS53116348A JPS53116348A (en) | 1978-10-11 |
| JPS5945661B2 true JPS5945661B2 (en) | 1984-11-07 |
Family
ID=12293247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP52030059A Expired JPS5945661B2 (en) | 1977-03-18 | 1977-03-18 | Stereoselective ring closure method from d-citronellal to l-isopulegol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5945661B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0695509A2 (en) | 1994-07-29 | 1996-02-07 | Takasago International Corporation | Liquid l-n-menthol composition and process for its preparation |
| EP2390001A1 (en) | 2010-05-25 | 2011-11-30 | Takasago International Corporation | Organoaluminium compounds and their use as catalysts in the selective cyclisation of citronellal to isopulegol |
| WO2014077321A1 (en) | 2012-11-15 | 2014-05-22 | 高砂香料工業株式会社 | Aluminum catalyst |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06229476A (en) * | 1991-12-03 | 1994-08-16 | Hitachi Ltd | Sliding device, fluid device, compressor and method of manufacturing the same |
| DE4244021A1 (en) * | 1992-12-24 | 1994-06-30 | Henkel Kgaa | Process for the electrolytic alternating current coloring of aluminum surfaces |
| EP0926117A1 (en) * | 1997-12-22 | 1999-06-30 | Quest International B.V. | Preparation of isopulegol |
| EP1053974A1 (en) * | 1999-05-17 | 2000-11-22 | Quest International B.V. | Reactions using lewis acids |
| JP4676617B2 (en) | 2001-01-18 | 2011-04-27 | 高砂香料工業株式会社 | Method for producing isopulegol |
| DE102004057277A1 (en) | 2004-11-26 | 2006-06-01 | Basf Ag | Process for the preparation of menthol |
| DE102004063003A1 (en) * | 2004-12-22 | 2006-07-13 | Basf Ag | Process for the preparation of isopulegol |
-
1977
- 1977-03-18 JP JP52030059A patent/JPS5945661B2/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0695509A2 (en) | 1994-07-29 | 1996-02-07 | Takasago International Corporation | Liquid l-n-menthol composition and process for its preparation |
| EP2390001A1 (en) | 2010-05-25 | 2011-11-30 | Takasago International Corporation | Organoaluminium compounds and their use as catalysts in the selective cyclisation of citronellal to isopulegol |
| US8329931B2 (en) | 2010-05-25 | 2012-12-11 | Takasago International Corporation | Organoaluminum compound |
| WO2014077321A1 (en) | 2012-11-15 | 2014-05-22 | 高砂香料工業株式会社 | Aluminum catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53116348A (en) | 1978-10-11 |
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