JPH03206061A - Production of alkylcyclohexanone - Google Patents
Production of alkylcyclohexanoneInfo
- Publication number
- JPH03206061A JPH03206061A JP2002172A JP217290A JPH03206061A JP H03206061 A JPH03206061 A JP H03206061A JP 2002172 A JP2002172 A JP 2002172A JP 217290 A JP217290 A JP 217290A JP H03206061 A JPH03206061 A JP H03206061A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- compound
- formula
- liquid phase
- alkali metal
- 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 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007791 liquid phase Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- -1 alkyl phenol Chemical compound 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexyloxide Natural products O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims 3
- 239000000126 substance Substances 0.000 claims 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 2
- 239000003504 photosensitizing agent Substances 0.000 abstract description 2
- 239000003317 industrial substance Substances 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 2
- NGFPWHGISWUQOI-UHFFFAOYSA-N 2-sec-butylphenol Chemical compound CCC(C)C1=CC=CC=C1O NGFPWHGISWUQOI-UHFFFAOYSA-N 0.000 description 2
- CCOQPGVQAWPUPE-UHFFFAOYSA-N 4-tert-butylcyclohexan-1-ol Chemical compound CC(C)(C)C1CCC(O)CC1 CCOQPGVQAWPUPE-UHFFFAOYSA-N 0.000 description 2
- 229940091886 4-tert-butylcyclohexanol Drugs 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YKFKEYKJGVSEIX-UHFFFAOYSA-N cyclohexanone, 4-(1,1-dimethylethyl)- Chemical compound CC(C)(C)C1CCC(=O)CC1 YKFKEYKJGVSEIX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZUYKJZQOPXDNOK-UHFFFAOYSA-N 2-(ethylamino)-2-thiophen-2-ylcyclohexan-1-one;hydrochloride Chemical class Cl.C=1C=CSC=1C1(NCC)CCCCC1=O ZUYKJZQOPXDNOK-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- RQXTZKGDMNIWJF-UHFFFAOYSA-N 2-butan-2-ylcyclohexan-1-one Chemical compound CCC(C)C1CCCCC1=O RQXTZKGDMNIWJF-UHFFFAOYSA-N 0.000 description 1
- KYCSDQLAIZIRAG-UHFFFAOYSA-N 2-butan-2-ylhexan-1-ol Chemical compound C(CCC)C(CO)C(CC)C KYCSDQLAIZIRAG-UHFFFAOYSA-N 0.000 description 1
- IXVGVVQGNQZQGD-UHFFFAOYSA-N 2-propan-2-ylcyclohexan-1-ol Chemical compound CC(C)C1CCCCC1O IXVGVVQGNQZQGD-UHFFFAOYSA-N 0.000 description 1
- SDJUYPUXVFDUFF-UHFFFAOYSA-N 2-propan-2-ylcyclohexan-1-one Chemical compound CC(C)C1CCCCC1=O SDJUYPUXVFDUFF-UHFFFAOYSA-N 0.000 description 1
- ZRYDPLOWJSFQAE-UHFFFAOYSA-N 2-tert-butylcyclohexan-1-one Chemical compound CC(C)(C)C1CCCCC1=O ZRYDPLOWJSFQAE-UHFFFAOYSA-N 0.000 description 1
- ZAFWZDBEWAFVLL-UHFFFAOYSA-N 2-tert-butylhexan-1-ol Chemical compound CCCCC(CO)C(C)(C)C ZAFWZDBEWAFVLL-UHFFFAOYSA-N 0.000 description 1
- CYEKUDPFXBLGHH-UHFFFAOYSA-N 3-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1 CYEKUDPFXBLGHH-UHFFFAOYSA-N 0.000 description 1
- JNBWOHHOZSSXLY-UHFFFAOYSA-N 3-tert-butylhexan-1-ol Chemical compound CCCC(C(C)(C)C)CCO JNBWOHHOZSSXLY-UHFFFAOYSA-N 0.000 description 1
- VIRMBSNUQKKLJW-UHFFFAOYSA-N 4-ethyl-5,5-dimethylhexan-1-ol Chemical compound CCC(C(C)(C)C)CCCO VIRMBSNUQKKLJW-UHFFFAOYSA-N 0.000 description 1
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005292 vacuum distillation 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)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、アルキルシクロヘキサノンを高純度、高選択
率で工業的に製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for industrially producing alkylcyclohexanone with high purity and high selectivity.
アルキルシクロヘキサノンは、医薬中間体、工業薬品原
料、光増感剤原料等として有用な化合物である。Alkylcyclohexanone is a compound useful as a pharmaceutical intermediate, a raw material for an industrial drug, a raw material for a photosensitizer, and the like.
［従来の技術コ
アルキルシクロヘキサノンを工業的に製造する方法とし
ては、パラジウム系触媒の存在下、アルキルフェノール
を液相で水素化することにより一段で製造する方法は既
に提案ざれており、具体的には、次の方法等が例示ざれ
る。[Conventional technology As a method for industrially producing corekylcyclohexanone, a method has already been proposed in which alkylphenol is hydrogenated in a liquid phase in the presence of a palladium-based catalyst. , the following methods are exemplified.
（１）独特の方法により調製ざれたパラジウムー活性炭
触媒の存在下に液相で水素化する方法（特公昭４４−２
６６５７号）
（２）パラジウム触媒の存在下、水中で水素化する方法
（特開昭５７−４９３２号）
これらの液相一段法にあいては、適当な溶媒を用いて反
応せしめることが高純度の目的物を高い選択率で得る上
で好ましい条件であると考えられていた。例えば、上記
（１）の方法に基づいてシクロヘキサノン類を製造する
方法においては、溶媒として酢酸、シクロヘキサン、ジ
オキサン等が使用ざれている。又、（２）の方法にあっ
ては、大量の水（例えば、置換フェノール１モル当り０
． ５〜２０ｉの水〉の中で反応せしめている。(1) Hydrogenation method in the liquid phase in the presence of a palladium-activated carbon catalyst prepared by a unique method (Japanese Patent Publication No. 44-2
(No. 6657) (2) Method of hydrogenation in water in the presence of a palladium catalyst (JP-A No. 57-4932) In these one-step liquid phase methods, it is possible to achieve high purity by using an appropriate solvent for the reaction. These conditions were thought to be favorable for obtaining the desired product with high selectivity. For example, in the method for producing cyclohexanones based on the method (1) above, acetic acid, cyclohexane, dioxane, etc. are used as a solvent. In addition, in the method (2), a large amount of water (for example, 0 per mole of substituted phenol) is used.
．． The reaction was carried out in 5 to 20 liters of water.
［発明が解決しようとする課題］
しかしながら、上記（１） 、（２）に記載ざれた技術
の如く、反応溶媒を大量に用いた場合には、１ロット当
りの目的物の収量が少なく作業性に劣り、工業的な製造
方法としての観点からは、尚、改善の余地が認められる
。[Problems to be Solved by the Invention] However, when a large amount of reaction solvent is used as in the techniques described in (1) and (2) above, the yield of the target product per lot is low and the workability is low. However, from the viewpoint of an industrial manufacturing method, there is still room for improvement.
上記（１）の方法において、液相無溶媒下で反応するこ
とができるとの記戟もあるが、この方法においては溶媒
中で液相水素化した場合以上の反応率、選択率が得られ
るものではないと考えられていた。In method (1) above, there is a record that the reaction can be carried out in a liquid phase without a solvent, but in this method, a reaction rate and selectivity higher than that obtained by liquid phase hydrogenation in a solvent can be obtained. It was thought that it was not a thing.
本発明者らは、上記の各提案方法と同様な液相一段法に
おいて、特定の溶媒を用いることなく、高純度、高選択
率でアルキルシクロヘキサノンを製造することができる
工業的に優れた技術を確立すべく鋭意検討の結果、
｛１）反応溶媒を何ら適用することなく所期の目的を達
戒するためには、特定の反応圧力を選択することが非常
に重要であり、更には、
（２）上記反応条件下において、アルカリ金属化合物を
配合することにより、大幅に選択性を向上し得ることを
見い出し、斯かる知見に基づいて本発明を完或するに至
った。The present inventors have developed an industrially superior technology that can produce alkylcyclohexanone with high purity and high selectivity without using a specific solvent in a liquid phase one-step method similar to the methods proposed above. As a result of intensive study to establish {1) it is very important to select a specific reaction pressure in order to achieve the desired purpose without applying any reaction solvent; 2) It has been discovered that selectivity can be significantly improved by incorporating an alkali metal compound under the above reaction conditions, and the present invention has been completed based on this finding.
即ち、本発明は、高純度のアルキルシクロヘキサノンを
工業的規模で経済的に製造し得る新規な方法を提供する
ことを目的とする。That is, an object of the present invention is to provide a novel method that can economically produce high-purity alkylcyclohexanone on an industrial scale.
［課題を解決するための手段］
本発明に係るアルキルシクロヘキサノンの製造方法は、
一般式（Ｉ＞で表わされるアルキルフェノールをパラジ
ウム系触媒の存在下、液相水素化して一般式（ＩＩ＞で
表わされるアルキルシクロヘキサノンを製造するに際し
、反応溶媒を用いずに、アルカリ金属化合物の存在下、
常圧乃至４ Ｋｇ／ ｃｕｔＧ以下の加圧下で液相水素
化することを特徴とする。[Means for Solving the Problems] The method for producing alkylcyclohexanone according to the present invention includes:
When producing alkylcyclohexanone represented by general formula (II>) by liquid phase hydrogenation of alkylphenol represented by general formula (I> in the presence of a palladium-based catalyst, it is possible to produce an alkylcyclohexanone represented by general formula (II>) without using a reaction solvent, in the presence of an alkali metal compound. ,
It is characterized by carrying out liquid phase hydrogenation under pressure ranging from normal pressure to 4 kg/cutG or less.
［式中、 Ｒは炭素数２〜５のアルキル基を表わす。[In the formula, R represents an alkyl group having 2 to 5 carbon atoms.
］
０
［式中、Ｒは一般式（Ｉ）と同じである。］本発明にあ
いて、原料として適用されるアルキルフェノールのアル
キル基の種類としては、エチル基、プロビル基、イソプ
ロビル基、ブチル基、ｔｅｒｔ−ブチル基、ペンチル基
等が例示ざれ、その置換位置は問わない。] 0 [Wherein, R is the same as in general formula (I). ] In the present invention, examples of the alkyl group of the alkylphenol used as a raw material include ethyl group, probyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, etc., and the substitution position is No question.
パラジウム系触媒としては、水素化触媒として従来公知
の各種の触媒が提示ざれ、具体的には、金属パラジウム
を活性炭、グラフ７イト、シリカ、アルミナ、炭酸カル
シウム等に例示される担体に０．１〜１０重量％、好ま
しくは０．５〜８重量％程度担持させたものが推奨され
る。As palladium-based catalysts, various catalysts conventionally known as hydrogenation catalysts have been proposed. Specifically, metallic palladium is deposited on a carrier such as activated carbon, graphite, silica, alumina, calcium carbonate, etc. at 0.1%. It is recommended to carry about 10% by weight, preferably 0.5 to 8% by weight.
液相水素化反応に際して適用ざれる上記パラジウム系触
媒の添加量は、原料であるアルキルフェノールに対して
、通常、０．２〜３重量％程度、好ましくは０．５〜２
重量％程度である。The amount of the palladium-based catalyst applied in the liquid phase hydrogenation reaction is usually about 0.2 to 3% by weight, preferably 0.5 to 2% by weight, based on the alkylphenol raw material.
It is about % by weight.
本発明に係る製造方法において、水素化反応時の水素圧
力を一定の範囲内で制御することは非常に重要であり、
具体的には、常圧乃至４Ｋ’ｊ／ｃｒＡＧ以下、好まし
くは１．５〜３Ｎｇ／ｒｍＧの範囲内で適宜選択ざれる
。アルキル基の炭素数が増加するに従って好ましい水素
圧力も上記範囲内で増加する傾向にある。減圧下では水
素化の進行が非常に緩慢となるため工業的には適用し難
い。又、４ Ｋｉ／ｏ＋ｆＧを越えた条件下で水素化し
た場合には目的物の選択率が低下して好ましくない。In the production method according to the present invention, it is very important to control the hydrogen pressure during the hydrogenation reaction within a certain range,
Specifically, the pressure is appropriately selected within the range of normal pressure to 4 K'j/crAG, preferably 1.5 to 3 Ng/rmG. As the number of carbon atoms in the alkyl group increases, the preferred hydrogen pressure also tends to increase within the above range. Hydrogenation progresses very slowly under reduced pressure, making it difficult to apply it industrially. Furthermore, when hydrogenation is carried out under conditions exceeding 4 Ki/o+fG, the selectivity of the target product decreases, which is not preferable.
水素化反応に用いる水素は、従来の水素化反応に用いら
れるものであれば足り、具体的には、純水素、又は水素
と窒素等の不活性ガスとの混合ガスが用いられる。The hydrogen used in the hydrogenation reaction may be any hydrogen used in conventional hydrogenation reactions, and specifically, pure hydrogen or a mixed gas of hydrogen and an inert gas such as nitrogen is used.
当該水素化反応は、６０〜１８０℃程度、好ましくは１
００〜１５０℃の加熱下で充分に進行する。The hydrogenation reaction is carried out at a temperature of about 60 to 180°C, preferably 1
The process progresses satisfactorily under heating at 00 to 150°C.
本発明方法において、アルカリ金属化合物の存在下で液
相水素化することにより、選択率が改善ざれる結果、当
該水素化反応が促進ざれ、反応時間が短縮ざれるため、
その工業的見地からの意義は大きい。In the method of the present invention, by carrying out liquid phase hydrogenation in the presence of an alkali metal compound, the selectivity is improved, the hydrogenation reaction is accelerated, and the reaction time is shortened.
Its significance from an industrial standpoint is great.
アルカリ金属化合物として、具体的には、水酸化ナトリ
ウム、炭酸ナトリウム等が奏効上好ましい。Specifically, sodium hydroxide, sodium carbonate, etc. are preferable as the alkali metal compound in terms of effectiveness.
このアルカリ金属化合物の適用量は、所定の促進効果が
得られる限り特に限定されるものではないが、具体的に
は、原料のアルキルフェノールに対して、１０〜２００
０ｐｐｍ、好ましくは５０〜１０００ｐｐｍ程度が適当
である。１０Ｃｌｍ未満では所定の効果が得られにくく
、２０００ｐｐｍを越えて添加しても特に効果上の有意
差は認められない。The amount of the alkali metal compound applied is not particularly limited as long as a predetermined promoting effect is obtained, but specifically, the amount of the alkali metal compound applied is 10 to 200
A suitable amount is 0 ppm, preferably about 50 to 1000 ppm. If it is less than 10 Clm, it is difficult to obtain the desired effect, and even if it is added in excess of 2000 ppm, no significant difference in effectiveness is observed.
本発明に係る水素化反応は、通常、５〜１２時間程度で
完結する。選択する条件によって当該時間で反応が完結
しない場合には、更に同一条件下で水素化反応を続行す
ればよい。The hydrogenation reaction according to the present invention is usually completed in about 5 to 12 hours. If the reaction is not completed within the specified time due to the selected conditions, the hydrogenation reaction may be further continued under the same conditions.
以下に、アルキルシクロヘキサノンの具体的な製造方法
を示す。A specific method for producing alkylcyclohexanone is shown below.
まず、所定のオートクレープ中に原料であるアルキルフ
ェノール、パラジウム系触媒及び好ましくはアルカリ金
属化合物を所定量仕込み、反応雰囲気を水素に置換した
後、原料であるアルキルフェノールの融点以上の温度に
加熱する。このとき、従来の方法の如き反応溶媒を使用
する必要はない。First, a predetermined amount of alkylphenol as a raw material, a palladium-based catalyst, and preferably an alkali metal compound are charged into a predetermined autoclave, the reaction atmosphere is replaced with hydrogen, and then heated to a temperature equal to or higher than the melting point of the alkylphenol as a raw material. At this time, there is no need to use a reaction solvent as in conventional methods.
所定の温度条件下で撹拌しながら水素ガスを反応系内に
導入し、所定の圧力下で液相承素化する。Hydrogen gas is introduced into the reaction system while stirring under a predetermined temperature condition, and the hydrogen gas is converted into a liquid phase under a predetermined pressure.
反応完結後、触媒を濾別し、必要に応じて減圧蒸留、溶
剤抽出等の精製処理を施す。かくして高純度のアルキル
シクロヘキサノンを、高選択率で工業的に得ることがで
きる。After the reaction is completed, the catalyst is filtered off, and if necessary, purification treatments such as vacuum distillation and solvent extraction are performed. In this way, highly pure alkylcyclohexanone can be obtained industrially with high selectivity.
上記工程で分別ざれた触媒は、再使用することができる
。The catalyst separated in the above step can be reused.
［実施例］
以下に実施例及び比較例を掲げて、本発明を詳しく説明
する。[Example] The present invention will be described in detail with reference to Examples and Comparative Examples below.
尚、以下の各例において、反応物の組成は、ガスクロマ
トグラフィーにより算定した。又、選択率は反応に関与
した原料のアルキルフェノールに対する生或したアルキ
ルシクロヘキサノンのモル％で粋出した。In addition, in each of the following examples, the composition of the reactant was calculated by gas chromatography. Moreover, the selectivity was determined by the mol% of the alkylcyclohexanone produced relative to the alkylphenol of the raw material involved in the reaction.
実施例１
電磁式撹拌装置、温度計及び水素ガス導入口を備えた０
．５Ｊのオートクレープに４ − ｔｅｒｔ−プチルフ
ェノール１００ｇ、炭酸ナトリウム０．０３５ｇ及び５
重量％パラジウム／カーボン触１１９を仕込み、これを
１００〜１１５℃の加熱下に撹拌しながら０．５Ｋｇ／
ＣＩＩｉＧの加圧下で１４時間液相水素化した。その結
果、９４．０％の選択率で純度９１．２％の４ − ｔ
ｅｒｔ−プチルシク口ヘキサノンを得た。尚、反応物中
には５．６％の４一ｔｅｒｔ−プチルシクロヘキサノー
ル及び３．０％の４ − ｔｅｒｔ−プチルフェノール
が認められた。Example 1 0 equipped with an electromagnetic stirrer, a thermometer and a hydrogen gas inlet
．． In a 5J autoclave, 100 g of 4-tert-butylphenol, 0.035 g of sodium carbonate, and 5
% by weight palladium/carbon catalyst 119 was charged, and this was heated at 100 to 115°C while stirring to give 0.5 kg/kg.
Liquid phase hydrogenation was carried out under pressure in CIIIiG for 14 hours. As a result, 4-t with a purity of 91.2% with a selectivity of 94.0%
Ert-butyl hexanone was obtained. In addition, 5.6% of 4-tert-butylcyclohexanol and 3.0% of 4-tert-butylphenol were observed in the reaction product.
実施例２
実施例１と同一のオートクレープに、２ − ｔｅｒｔ
一ブチルフェノール１００ｇ、炭酸ナトリウム０．０３
５ｇ及び５重量％パラジウム／カーボン触媒１．０ｇを
仕込み、これを１２０〜１５０℃の加熱下に撹拌しなが
ら２〜３ Ｋ’ｊ ／ ｃｉ Ｇの加圧下で８時間液相
水素化した。その結果、１００％の選択率で純度９５．
９％の２ − ｔｅｒｔ−プチルシク口ヘキサノンを得
た。Example 2 In the same autoclave as in Example 1, 2-tert
Monobutylphenol 100g, sodium carbonate 0.03
5 g and 1.0 g of a 5 wt % palladium/carbon catalyst were charged, and this was subjected to liquid phase hydrogenation for 8 hours under a pressure of 2 to 3 K'j/ci G while stirring and heating at 120 to 150°C. As a result, the purity was 95% with a selectivity of 100%.
9% of 2-tert-butylcyclohexanone was obtained.
尚、反応物中には３．６％の２ − ｔｅｒｔ−プチル
シク口ヘキサノールが認められた。In addition, 3.6% of 2-tert-butyl hexanol was observed in the reaction product.
実施例３
実施例１と同一のオートクレープに、３ − ｔｅｒｔ
−ブチルフェノール１００ｇ、炭酸ナトリウム０．０５
ｇ及び５重量％パラジウム／カーボン触１１．０ｇを仕
込み、これを１２０℃の加熱下に撹拌しながら２Ｋｇ／
ｃｒｉＧの加圧下で６時間液相水素化した。その結果、
９０．８％の選択率で純度８９．３％の３−ｔｅｒｔ−
プチルシク口ヘキサノンを得た。Example 3 In the same autoclave as in Example 1, 3-tert
-Butylphenol 100g, sodium carbonate 0.05
g and 11.0 g of 5 wt.
Liquid phase hydrogenation was carried out under pressure of criG for 6 hours. the result,
3-tert- with 90.8% selectivity and 89.3% purity
Butylic hexanone was obtained.
尚、反応物中には８．２％の３ − ｔｅｒｔ−プチル
シク口ヘキサノール及び１．６％の３ − ｔｅｒｔ−
ブチルフ工ノールが認められた。In addition, 8.2% of 3-tert-butyl hexanol and 1.6% of 3-tert-
Butylphinol was detected.
実施例４
実施例１と同一のオートクレープに、２ −ｓｅｃ−プ
チルフェノール１ ００ｇ、炭酸ナトリウム０．０５ｇ
及び５重量％パラジウム／カーボン触媒１．０４を仕込
み、これを１２０〜／１５０℃の加熱下に撹拌しながら
２〜３Ｋｇ／ｔｒｉ！Ｇの加圧下で１１時間液相水素化
した。その結果、９６．４％の選択率で純度９５．９％
の２ − ｓｅｃ−プチルシクロヘキサノンを得た。Example 4 Into the same autoclave as in Example 1, 100 g of 2-sec-butylphenol and 0.05 g of sodium carbonate were added.
and 5 wt% palladium/carbon catalyst 1.04, and heated at 120 to 150°C while stirring at a rate of 2 to 3 kg/tri! Liquid phase hydrogenation was carried out under pressure of G for 11 hours. As a result, the purity was 95.9% with a selectivity of 96.4%.
2-sec-butylcyclohexanone was obtained.
尚、反応物中には２．２％の２ − ｓｅｃ−プチルシ
ク口ヘキサノール及び０．０５％の２ − ｓｅｃプチ
ルフェノールが認められた。In addition, 2.2% of 2-sec-butyl hexanol and 0.05% of 2-sec-butylphenol were observed in the reaction product.
実施例５
実施例１と同一のオートクレープに、２−イソプロビル
フェノール１００ｇ、炭酸ナトリウム０．０５９及び５
重量％パラジウム／カーボン触媒１．０ｇを仕込み、こ
れを１２０〜／１５０℃の加熱下に撹拌しながら２〜３
ＫＩ／ｃｕｆＧの加圧下で１２時間液相水素化した。そ
の結果、１００％の選択率で純度９６．１％の２−イソ
プロビルシクロヘキサノンを得た。Example 5 In the same autoclave as in Example 1, 100 g of 2-isopropylphenol, 0.059 g of sodium carbonate, and 5
1.0g of wt% palladium/carbon catalyst was charged, and heated at 120~/150°C while stirring for 2~3 hours.
Liquid phase hydrogenation was performed under pressure of KI/cufG for 12 hours. As a result, 2-isopropylcyclohexanone with a purity of 96.1% was obtained with a selectivity of 100%.
尚、反応物中には３．４％の２−イソプロビルシクロヘ
キサノールが認められた。In addition, 3.4% of 2-isopropylcyclohexanol was observed in the reaction product.
比較例１
液相水素化圧力を５ Ｋ！ｊ／ ｃｔＡ Ｇとした外は
、実施例１に準じて４ − ｔｅｒｔ−プチルシク口ヘ
キサノンを調製した。その結果、８０．２％の選択率で
純度７６．２％の４−ｔｅｒｔ−プチルシクロヘキサノ
ンを得た。Comparative Example 1 Liquid phase hydrogenation pressure was 5K! 4-tert-butylsichexanone was prepared according to Example 1, except that 4-tert-butylsichexanone was used. As a result, 4-tert-butylcyclohexanone with a purity of 76.2% was obtained with a selectivity of 80.2%.
尚、反応物中には１６．３％の４ − ｔｅｒｔ−プチ
ルシクロヘキサノール及び５．３％の４−ｔｅｒｔ−プ
チルフェノールが認められた。In addition, 16.3% of 4-tert-butylcyclohexanol and 5.3% of 4-tert-butylphenol were observed in the reaction product.
比較例２
アルカリ金属化合物｛炭酸ナトリウム｝を添加しない外
は実施例１に準じて４ − ｔｅｒｔ−プチルシクロヘ
キサノンを調製した。その結果、７５．］％の選択率で
純度６９．４％の４ − ｔｅｒｔ−プチルシク口ヘキ
サノンを得た。Comparative Example 2 4-tert-butylcyclohexanone was prepared according to Example 1 except that the alkali metal compound {sodium carbonate} was not added. As a result, 75. 4-tert-butylsichexanone with a purity of 69.4% was obtained with a selectivity of ]%.
尚、反応物中には１４．３％の４ − ｔｅｒｔ−プチ
ルシク口ヘキサノール及び６．０％の４−ｔｅｒｔプチ
ルフェノールが認められた。In addition, 14.3% of 4-tert-butyl hexanol and 6.0% of 4-tert-butylphenol were observed in the reaction product.
［発明の効果］
本発明に係る方法により、工業的に優位な条件下で高純
度のアルキルシクロヘキサノンを高選択率で製造するこ
とができる。[Effects of the Invention] By the method according to the present invention, highly pure alkylcyclohexanone can be produced with high selectivity under industrially advantageous conditions.
Claims (1)
パラジウム系触媒の存在下、液相水素化して一般式（I
I）で表わされるアルキルシクロヘキサノンを製造する
に際し、反応溶媒を用いずに、アルカリ金属化合物の存
在下、常圧乃至４Ｋｇ／ｃｍ＾２Ｇ以下の加圧下で液相
水素化することを特徴とするアルキルシクロヘキサノン
の製造方法。 ▲数式、化学式、表等があります▼（ I ） ［式中、Ｒは炭素数２〜５のアルキル基を表わす。 ▲数式、化学式、表等があります▼（II） ［式中、Ｒは一般式（ I ）と同じである。］[Claims] 1. Alkylphenol represented by the general formula (I) is hydrogenated in the liquid phase in the presence of a palladium-based catalyst to form the alkylphenol represented by the general formula (I).
When producing the alkylcyclohexanone represented by I), the alkyl cyclohexanone is hydrogenated in a liquid phase under normal pressure to 4 kg/cm^2G or less in the presence of an alkali metal compound without using a reaction solvent. Method for producing cyclohexanone. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R represents an alkyl group having 2 to 5 carbon atoms. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In the formula, R is the same as in the general formula (I). ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002172A JPH0798771B2 (en) | 1990-01-08 | 1990-01-08 | Method for producing alkylcyclohexanone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002172A JPH0798771B2 (en) | 1990-01-08 | 1990-01-08 | Method for producing alkylcyclohexanone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03206061A true JPH03206061A (en) | 1991-09-09 |
| JPH0798771B2 JPH0798771B2 (en) | 1995-10-25 |
Family
ID=11521948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002172A Expired - Fee Related JPH0798771B2 (en) | 1990-01-08 | 1990-01-08 | Method for producing alkylcyclohexanone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0798771B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5977402A (en) * | 1995-07-20 | 1999-11-02 | Sumitomo Chemical Company, Limited | Processes for preparing 4-tert.-butylcyclohexanol and 4-tert.-butylcyclohexyl acetate |
-
1990
- 1990-01-08 JP JP2002172A patent/JPH0798771B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5977402A (en) * | 1995-07-20 | 1999-11-02 | Sumitomo Chemical Company, Limited | Processes for preparing 4-tert.-butylcyclohexanol and 4-tert.-butylcyclohexyl acetate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0798771B2 (en) | 1995-10-25 |
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