JP3535637B2 - Method for producing cis-3,3,5-trimethylcyclohexanol - Google Patents
Method for producing cis-3,3,5-trimethylcyclohexanolInfo
- Publication number
- JP3535637B2 JP3535637B2 JP31163795A JP31163795A JP3535637B2 JP 3535637 B2 JP3535637 B2 JP 3535637B2 JP 31163795 A JP31163795 A JP 31163795A JP 31163795 A JP31163795 A JP 31163795A JP 3535637 B2 JP3535637 B2 JP 3535637B2
- Authority
- JP
- Japan
- Prior art keywords
- trimethylcyclohexanol
- cis
- reaction
- catalyst
- acid
- 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 - Fee Related
Links
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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、シス−３，３，５
−トリメチルシクロヘキサノールの製造方法に関する。
さらに詳しくは、３，３，５−トリメチルシクロヘキサ
ノン（別名、ジヒドロイソホロン）または３，３，５−
トリメチルシクロヘキセノン（別名、イソホロン）を接
触水添反応し、ついで酸の存在下に３，３，５−トリメ
チルシクロヘキサノールのトランス体を選択的に除去
し、シス体の存在比をさらに高めるシス−３，３，５−
トリメチルシクロヘキサノールの製造方法に関する。TECHNICAL FIELD The present invention relates to cis-3, 3, 5
-A method for producing trimethylcyclohexanol.
More specifically, 3,3,5-trimethylcyclohexanone (also known as dihydroisophorone) or 3,3,5-
Trimethylcyclohexenone (also known as isophorone) is subjected to catalytic hydrogenation reaction, and then the trans form of 3,3,5-trimethylcyclohexanol is selectively removed in the presence of acid to further increase the cis-form abundance. 3,3,5-
The present invention relates to a method for producing trimethylcyclohexanol.
【０００２】[0002]
【従来の技術】シス−３，３，５−トリメチルシクロヘ
キサノールは、原料物質として、例えば医薬品等の合成
中間体として有用な物質である。近年３，３，５−トリ
メチルシクロヘキサノールのシス体およびトランス体の
中でもシス体に対する要望が強い。イソホロンを接触水
添して３，３，５−トリメチルシクロヘキサノールを得
る方法は従来から知られている。例えば、特公昭４７−
４１３４７号公報等に開示されている。得られた生成物
はシス体とトランス体との混合物である。また、トラン
ス体からシス体への異性化反応については、ナトリウム
金属と加熱する方法（Chem,Ber,92,1130■1134(195
9))、アルミニウムイソプロボキシド触媒を用いる方法
(J.Org.Chem,26,3504■3506(1061))、アルカリ金属水酸
化物およびラネー系触媒の存在下に３，３，５−トリメ
チルシクロヘキサノールを生成させ、そのまま反応条件
を保持してトランス体からシス体への異性化反応を進め
る方法（特開昭６２−１１１９４０号公報）等が報告さ
れている。2. Description of the Related Art Cis-3,3,5-trimethylcyclohexanol is a useful material as a raw material, for example, as a synthetic intermediate for pharmaceuticals and the like. In recent years, among cis and trans isomers of 3,3,5-trimethylcyclohexanol, there is a strong demand for cis isomers. A method for catalytically hydrogenating isophorone to obtain 3,3,5-trimethylcyclohexanol is conventionally known. For example, Japanese Patent Publication Sho 47-
No. 41347 is disclosed. The product obtained is a mixture of cis and trans isomers. Regarding the isomerization reaction from trans isomer to cis isomer, a method of heating with sodium metal (Chem, Ber, 92, 1130 1134 (195
9)), Method using aluminum isopropoxide catalyst
(J.Org.Chem, 26,3504 3506 (1061)), 3,3,5-trimethylcyclohexanol was produced in the presence of an alkali metal hydroxide and a Raney catalyst, and the reaction conditions were maintained as they were. A method for promoting an isomerization reaction from a trans form to a cis form (Japanese Patent Laid-Open No. 62-111940) has been reported.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記の
方法は一般的にシス選択性が低く、あるいは操作が繁雑
であり、好ましい方法とは言えないものであった。本発
明は、シス選択性が高く、好収率、好純度にシス−３，
３，５−トリメチルシクロヘキサノールを得る方法の提
供を目的とする。However, the above-mentioned method is not a preferable method because the cis selectivity is generally low or the operation is complicated. INDUSTRIAL APPLICABILITY The present invention has a high cis selectivity, a good yield, and a good purity of cis-3,
It is intended to provide a method for obtaining 3,5-trimethylcyclohexanol.
【０００４】[0004]
【課題を解決するための手段】本発明は、下記ａおよび
ｂの工程からなることを特徴とするシス−３，３，５−
トリメチルシクロヘキサノールの製造方法を提供する。
a． ３，３，５−トリメチルシクロヘキサノンまたは
３，３，５−トリメチルシクロヘキセノンを接触還元用
触媒の存在下に接触水添反応させて得られた反応混合物
を、同条件下に反応を継続してシス体リッチの３，３，
５−トリメチルシクロヘキサノールを得る工程、
ｂ． 酸触媒の存在下に、３，３，５−トリメチルシク
ロヘキサノールのトランス体を選択的に除去し、シス体
の存在比をさらに高める工程。The present invention is characterized by comprising the following steps a and b: cis-3,3,5-
A method for producing trimethylcyclohexanol is provided. a. A reaction mixture obtained by subjecting 3,3,5-trimethylcyclohexanone or 3,3,5-trimethylcyclohexenone to a catalytic hydrogenation reaction in the presence of a catalyst for catalytic reduction was subjected to continuous reaction under the same conditions to obtain cis. Body rich 3,3
Obtaining 5-trimethylcyclohexanol, b. A step of selectively removing the trans form of 3,3,5-trimethylcyclohexanol in the presence of an acid catalyst to further increase the abundance ratio of the cis form.
【０００５】[0005]
【発明の実施の形態】本発明は、イソホロンあるいはジ
ヒドロイソホロンの接触水添反応に引き続き同条件下で
トランス体からシス体への異性化反応を進めてシス体リ
ッチの３，３，５−トリメチルシクロヘキサノールを得
（ａ工程）、ついで酸触媒の存在下にトランス体を選択
的に除去し、シス体の存在比を高める（ｂ工程）もので
ある。接触水添反応の終了有無は、水素の吸収有無で判
断される。本発明で使用される接触還元用触媒として
は、ルテニウム−カーボン、ルテニウム−アルミナ等の
ルテニウム系触媒が好適である。触媒使用量は、イソホ
ロンあるいはジヒドロイソホロンに対し一般に１〜５重
量％が好適である。接触水添反応時における水素分圧
は、５〜１００ｋｇ／ｃｍ2、好ましくは５〜３０ｋｇ
／ｃｍ2である。水素分圧の大小は、接触水添反応ある
いは引き続く異性化反応の遅速に影響するので上記範囲
から適宜選択することが必要である。反応温度は０〜３
００℃、好ましくは８０〜１８０℃である。上記範囲よ
りも低い温度では反応速度が遅く、高い温度では脱離反
応等の副反応が生ずる等の理由により好ましくない。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a catalytic hydrogenation reaction of isophorone or dihydroisophorone is followed by an isomerization reaction from a trans isomer to a cis isomer under the same conditions to promote cis isomer rich 3,3,5-trimethyl. Cyclohexanol is obtained (step a), and then the trans isomer is selectively removed in the presence of an acid catalyst to increase the abundance ratio of the cis isomer (step b). Whether or not the catalytic hydrogenation reaction has ended is determined by the presence or absence of hydrogen absorption. As the catalyst for catalytic reduction used in the present invention, ruthenium-based catalysts such as ruthenium-carbon and ruthenium-alumina are suitable. Generally, the amount of the catalyst used is preferably 1 to 5% by weight based on isophorone or dihydroisophorone. The hydrogen partial pressure during the catalytic hydrogenation reaction is 5 to 100 kg / cm 2 , preferably 5 to 30 kg.
/ Cm 2 . The magnitude of the hydrogen partial pressure affects the slowness of the catalytic hydrogenation reaction or the subsequent isomerization reaction, so it is necessary to appropriately select from the above range. Reaction temperature is 0-3
The temperature is 00 ° C, preferably 80 to 180 ° C. If the temperature is lower than the above range, the reaction rate is slow, and if the temperature is higher than the above range, side reactions such as elimination reaction occur.
【０００６】接触水添反応および引き続く選択除去反応
においては、溶媒の使用を特に必要とはしない。しかし
ながら、反応容器からの反応生成物の取り出し、あるい
は触媒の濾別を実施するためには、溶媒を使用すること
が好ましい。溶媒としては、トルエン、キシレン等が好
ましく例示される。その使用量は、出発原料に対し２０
〜２００重量％の範囲が好ましい。本発明においては、
上記接触水添反応、引き続く異性化反応（ａ工程）に加
えて、酸触媒の存在下に、３，３，５−トリメチルシク
ロヘキサノールのトランス体からシス体への選択除去反
応（ｂ工程）を実施する。接触水添反応と引き続く異性
化反応を行うａ工程のみでは、トランス体に対するシス
体の比率は、特開昭６２−１１９４０号公報に報告され
ている方法の場合には、最高８７重量％程度である。こ
のため精密蒸留等の複雑な精製操作を実施する必要があ
る。しかし３，３，５−トリメチルシクロヘキサノール
は固体であり、蒸留中に固化するなどの問題が発生し易
い。本発明は選択除去反応（ｂ）工程を実施することに
より、シス体比率を高め、精製操作を容易簡便ならしめ
ると共に、出発原料からの収率を高めようとするもので
ある。本発明においては、ａ工程で使用する触媒の種類
を選択することにより、ａ工程終了後のシス体比率をよ
り一層高めることもできる。In the catalytic hydrogenation reaction and the subsequent selective removal reaction, it is not necessary to use a solvent. However, it is preferable to use a solvent in order to carry out the removal of the reaction product from the reaction vessel or the filtration of the catalyst. Preferred examples of the solvent include toluene and xylene. The amount used is 20 with respect to the starting material.
The range of up to 200% by weight is preferred. In the present invention,
In addition to the catalytic hydrogenation reaction and the subsequent isomerization reaction (step a), in the presence of an acid catalyst, a selective removal reaction (step b) from the trans form of 3,3,5-trimethylcyclohexanol to the cis form is carried out. carry out. The ratio of the cis form to the trans form is about 87% by weight in the case of the method reported in JP-A-62-11940 only in the step a in which the catalytic hydrogenation reaction and the subsequent isomerization reaction are performed. is there. Therefore, it is necessary to carry out a complicated purification operation such as precision distillation. However, since 3,3,5-trimethylcyclohexanol is a solid, problems such as solidification during distillation are likely to occur. The present invention is intended to increase the ratio of cis isomers to facilitate the purification operation and to increase the yield from starting materials by carrying out the selective removal reaction (b) step. In the present invention, by selecting the type of catalyst used in the step a, the cis isomer ratio after the step a can be further increased.
【０００７】好ましく使用される酸触媒としては、塩
酸、硫酸、リン酸、ｐ−トルエンスルホン酸およびカチ
オン交換樹脂等が例示される。酸触媒使用量はイソホロ
ンあるいはジヒドロイソホロンに対し１〜１００重量
％、好ましくは２〜２０重量％である。この使用量は、
用いる酸触媒の種類により適宜選択される。弱酸の場合
使用量が少ないと反応が遅く、強酸の場合使用量が多い
と脱水反応のトランス選択性が悪くなり好ましくない。
反応溶媒としては、ベンゼン、トルエン、キシレン、シ
クロヘキサン等の炭化水素系溶媒が好ましく、使用量は
原料に対して２０〜２００重量％が好適である。反応温
度は５０〜１５０℃、特に溶媒の還流温度が好ましく、
さらには反応で生成する水を共沸しながら行うと反応速
度が向上するので好ましい。得られた生成物は、従来周
知の分離、精製手段を用いることにより、純品を得るこ
とができる。例えば、濾過、蒸留、再結晶等である。Examples of the acid catalyst preferably used include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, cation exchange resin and the like. The amount of the acid catalyst used is 1 to 100% by weight, preferably 2 to 20% by weight based on isophorone or dihydroisophorone. This usage is
It is appropriately selected depending on the type of acid catalyst used. When the amount used is weak acid, the reaction is slow, and when the amount used is strong acid, the trans-selectivity of the dehydration reaction is deteriorated, which is not preferable.
The reaction solvent is preferably a hydrocarbon solvent such as benzene, toluene, xylene or cyclohexane, and the amount used is preferably 20 to 200% by weight based on the raw material. The reaction temperature is 50 to 150 ° C., particularly preferably the reflux temperature of the solvent,
Furthermore, it is preferable to carry out the reaction while azeotropically distilling the water generated in the reaction, because the reaction rate is improved. The obtained product can be obtained as a pure product by using conventionally known separation and purification means. For example, filtration, distillation, recrystallization and the like.
【０００８】[0008]
【実施例】以下本発明を実施例に基づいてより詳細に説
明する。EXAMPLES The present invention will now be described in more detail with reference to examples.
【０００９】[0009]
【実施例１】容量１リットルのオートクレーブに３，
３，５−トリメチルシクロヘキサノン３００ｇ（２．１
４モル）と５％ルテニウム−カーボン（Ｒｕ−Ｃ）３ｇ
を入れ、水素分圧１０ｋｇ／ｃｍ2、５℃／ｍｉｎで昇
温を開始し、１５０℃に到達した時点から５時間で水素
の吸収は止まった。引き続き３時間同条件で保持し、異
性化を行った。約４０℃に冷却後、オートクレーブ内に
トルエン１００ｇを入れ、反応生成物のオートクレーブ
からの取り出し、触媒の濾別を実施し、濾液４００ｇを
得た。反応生成物をガスクロマトグラフで測定したとこ
ろシス体／トランス体の比率は９１．７／８．３であっ
た。次に上記の濾液４００ｇにｐ−トルエンスルホン酸
１５ｇを加え、共沸条件下に５時間加熱還流を行った。
トランス体の３，３，５−トリメチルシクロヘキサノー
ルは、シス体とトランス体の合計量に対し０．６重量％
であった。ついで反応液を濃度５重量％のソーダ灰水溶
液２００ｇ中に注入した。分液操作の後、有機層を濃度
１０重量％の塩水で洗浄し、エバポレーターで濃縮し
た。得られた濃縮液（２９０ｇ）を減圧蒸留して、シス
−３，３，５−トリメチルシクロヘキサノール２００ｇ
（収率６７重量％）を得た。Example 1 In an autoclave having a volume of 1 liter,
3,5-Trimethylcyclohexanone 300 g (2.1
4 mol) and 5% ruthenium-carbon (Ru-C) 3 g
Then, the temperature started to rise at a hydrogen partial pressure of 10 kg / cm 2 and 5 ° C./min, and the absorption of hydrogen stopped 5 hours after the temperature reached 150 ° C. Then, the same conditions were maintained for 3 hours for isomerization. After cooling to about 40 ° C., 100 g of toluene was put in the autoclave, the reaction product was taken out from the autoclave, and the catalyst was filtered off to obtain 400 g of a filtrate. When the reaction product was measured by gas chromatography, the ratio of cis isomer / trans isomer was 91.7 / 8.3. Next, 15 g of p-toluenesulfonic acid was added to 400 g of the above filtrate, and the mixture was heated under reflux under azeotropic conditions for 5 hours.
Trans 3,3,5-trimethylcyclohexanol is 0.6% by weight based on the total amount of cis and trans isomers.
Met. Then, the reaction solution was poured into 200 g of an aqueous solution of soda ash having a concentration of 5% by weight. After the liquid separation operation, the organic layer was washed with brine having a concentration of 10% by weight and concentrated by an evaporator. The concentrate (290 g) thus obtained was distilled under reduced pressure to give 200 g of cis-3,3,5-trimethylcyclohexanol.
(Yield 67% by weight) was obtained.
【００１０】[0010]
【実施例２】容量１リットルのオートクレーブに３，
３，５−トリメチルシクロヘキセノン３００ｇ（２．１
７モル）と５％ルテニウム−カーボン（Ｒｕ−Ｃ）３ｇ
を入れ、水素分圧１０ｋｇ／ｃｍ2、５℃／ｍｉｎで昇
温を開始し、１５０℃に到達した時点から５時間で水素
の吸収は止まった。引き続き３時間同条件で保持し、異
性化を行った。約４０℃に冷却後、オートクレーブ内に
トルエン１００ｇを入れ、反応生成物のオートクレーブ
からの取り出し、触媒の濾別を実施し、濾液４００ｇを
得た。反応生成物をガスクロマトグラフで測定したとこ
ろシス体／トランス体の比率は９２．３／７．７であっ
た。次に上記の濾液４００ｇに濃硫酸１０ｇを加え、共
沸条件下に３時間加熱還流を行った。トランス体の３，
３，５−トリメチルシクロヘキサノールは、シス体とト
ランス体の合計量に対し０．７重量％であった。ついで
反応液をソーダ灰水溶液２００ｇ中に注入した。分液操
作の後、有機層を濃度１０重量％の塩水で洗浄し、エバ
ポレーターで濃縮した。得られた濃縮液（２８５ｇ）を
減圧蒸留して、シス−３，３，５−トリメチルシクロヘ
キサノール１８０ｇ（収率６０重量％）を得た。Example 2 In an autoclave having a capacity of 1 liter,
3,5-Trimethylcyclohexenone 300 g (2.1
7 mol) and 5% ruthenium-carbon (Ru-C) 3 g
Then, the temperature started to rise at a hydrogen partial pressure of 10 kg / cm 2 and 5 ° C./min, and the absorption of hydrogen stopped 5 hours after the temperature reached 150 ° C. Then, the same conditions were maintained for 3 hours for isomerization. After cooling to about 40 ° C., 100 g of toluene was put in the autoclave, the reaction product was taken out from the autoclave, and the catalyst was filtered off to obtain 400 g of a filtrate. When the reaction product was measured by gas chromatography, the ratio of cis isomer / trans isomer was 92.3 / 7.7. Next, 10 g of concentrated sulfuric acid was added to 400 g of the above filtrate, and the mixture was heated under reflux for 3 hours under azeotropic conditions. Transformer body 3,
3,5-Trimethylcyclohexanol was 0.7% by weight based on the total amount of the cis isomer and the trans isomer. Then, the reaction solution was poured into 200 g of a soda ash aqueous solution. After the liquid separation operation, the organic layer was washed with brine having a concentration of 10% by weight and concentrated by an evaporator. The obtained concentrated liquid (285 g) was distilled under reduced pressure to obtain 180 g of cis-3,3,5-trimethylcyclohexanol (yield 60% by weight).
【００１１】[0011]
【発明の効果】本発明によれば、シス体比率の高い３，
３，５−トリメチルシクロヘキサノールを容易に得るこ
とができる製造方法が提供される。本発明の方法によれ
ば、簡便な精製操作により、シス−３，３，５−トリメ
チルシクロヘキサノールを好収率で得ることのできる製
造方法が提供される。INDUSTRIAL APPLICABILITY According to the present invention, the ratio of cis isomers is 3,
Provided is a production method capable of easily obtaining 3,5-trimethylcyclohexanol. According to the method of the present invention, there is provided a production method capable of obtaining cis-3,3,5-trimethylcyclohexanol in a good yield by a simple purification operation.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (56)参考文献 特開 昭62−111940（ＪＰ，Ａ) 特開 昭48−4449（ＪＰ，Ａ) 特公 昭47−11744（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 29/145 B01J 23/46 301 B01J 31/02 103 C07C 29/88 C07C 35/08 C07B 61/00 300 ＢＥＩＬＳＴＥＩＮ（ＳＴＮ) ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI // C07B 61/00 300 C07B 61/00 300 (56) References JP 62-111940 (JP, A) JP 48 -4449 (JP, A) JP-B 47-11744 (JP, B1) (58) Fields investigated (Int.Cl. 7 , DB name) C07C 29/145 B01J 23/46 301 B01J 31/02 103 C07C 29 / 88 C07C 35/08 C07B 61/00 300 BEILSTEIN (STN) CA (STN) REGISTRY (STN)
Claims (3)
徴とするシス−３，３，５−トリメチルシクロヘキサノ
ールの製造方法、 a． ３，３，５−トリメチルシクロヘキサノンまたは
３，３，５−トリメチルシクロヘキセノンを接触還元用
触媒の存在下に接触水添反応させて得られた反応混合物
を、同条件下に反応を継続してシス体リッチの３，３，
５−トリメチルシクロヘキサノールを得る工程、 ｂ． 酸触媒の存在下に、３，３，５−トリメチルシク
ロヘキサノールのトランス体を選択的に除去し、シス体
の存在比をさらに高める工程。1. A method for producing cis-3,3,5-trimethylcyclohexanol, which comprises the following steps a and b: a. A reaction mixture obtained by subjecting 3,3,5-trimethylcyclohexanone or 3,3,5-trimethylcyclohexenone to a catalytic hydrogenation reaction in the presence of a catalyst for catalytic reduction was subjected to continuous reaction under the same conditions to obtain cis. Body rich 3,3
Obtaining 5-trimethylcyclohexanol, b. A step of selectively removing the trans form of 3,3,5-trimethylcyclohexanol in the presence of an acid catalyst to further increase the abundance ratio of the cis form.
ある請求項１記載のシス−３，３，５−トリメチルシク
ロヘキサノールの製造方法。2. The method for producing cis-3,3,5-trimethylcyclohexanol according to claim 1, wherein the catalytic reduction catalyst is a ruthenium-based catalyst.
ルエンスルホン酸およびカチオン交換樹脂から選ばれた
少なくとも一種である請求項１記載のシス−３，３，５
−トリメチルシクロヘキサノールの製造方法。3. The cis-3,3,5 according to claim 1, wherein the acid catalyst is at least one selected from hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid and a cation exchange resin.
-Method for producing trimethylcyclohexanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31163795A JP3535637B2 (en) | 1995-11-06 | 1995-11-06 | Method for producing cis-3,3,5-trimethylcyclohexanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31163795A JP3535637B2 (en) | 1995-11-06 | 1995-11-06 | Method for producing cis-3,3,5-trimethylcyclohexanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09124528A JPH09124528A (en) | 1997-05-13 |
| JP3535637B2 true JP3535637B2 (en) | 2004-06-07 |
Family
ID=18019671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31163795A Expired - Fee Related JP3535637B2 (en) | 1995-11-06 | 1995-11-06 | Method for producing cis-3,3,5-trimethylcyclohexanol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3535637B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10160009A1 (en) * | 2001-12-06 | 2003-06-18 | Haarmann & Reimer Gmbh | Process for the preparation of 3,3,5-trimethylcyclohexanol |
| ES2543643T3 (en) * | 2011-03-10 | 2015-08-20 | Zach System S.P.A. | Asymmetric reduction process |
| CN110878003B (en) * | 2019-09-11 | 2023-03-28 | 安徽圣诺贝化学科技有限公司 | Isofol and new method for coproducing isophorol and carvone |
-
1995
- 1995-11-06 JP JP31163795A patent/JP3535637B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09124528A (en) | 1997-05-13 |
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