JPH04322743A - Catalyst for producing alkyladamantane and production of alkyladamantane using the same - Google Patents
Catalyst for producing alkyladamantane and production of alkyladamantane using the sameInfo
- Publication number
- JPH04322743A JPH04322743A JP3093989A JP9398991A JPH04322743A JP H04322743 A JPH04322743 A JP H04322743A JP 3093989 A JP3093989 A JP 3093989A JP 9398991 A JP9398991 A JP 9398991A JP H04322743 A JPH04322743 A JP H04322743A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- alumina
- alkyladamantane
- producing
- 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.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 31
- ORILYTVJVMAKLC-UHFFFAOYSA-N Adamantane Natural products C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 Alkyl adamantane Chemical compound 0.000 claims abstract description 16
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 11
- 238000011282 treatment Methods 0.000 claims description 24
- FZDZWLDRELLWNN-UHFFFAOYSA-N 1,2,3,3a,4,5,5a,6,7,8,8a,8b-dodecahydroacenaphthylene Chemical compound C1CCC2CCC3C2C1CCC3 FZDZWLDRELLWNN-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 10
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000000047 product Substances 0.000 description 17
- 238000000354 decomposition reaction Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- CWNOIUTVJRWADX-UHFFFAOYSA-N 1,3-dimethyladamantane Chemical compound C1C(C2)CC3CC1(C)CC2(C)C3 CWNOIUTVJRWADX-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 3
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 3
- 229940029284 trichlorofluoromethane Drugs 0.000 description 3
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- RTPQXHZLCUUIJP-UHFFFAOYSA-N 1,2-dimethyladamantane Chemical compound C1C(C2)CC3CC1C(C)C2(C)C3 RTPQXHZLCUUIJP-UHFFFAOYSA-N 0.000 description 1
- LXTHCCWEYOKFSR-UHFFFAOYSA-N 1-ethyladamantane Chemical compound C1C(C2)CC3CC2CC1(CC)C3 LXTHCCWEYOKFSR-UHFFFAOYSA-N 0.000 description 1
- JFTTWMPKEWWWJX-UHFFFAOYSA-N 2-chloro-1-fluoro-1-methyl-4-propan-2-ylcyclohexane Chemical class CC(C)C1CCC(C)(F)C(Cl)C1 JFTTWMPKEWWWJX-UHFFFAOYSA-N 0.000 description 1
- 229910018404 Al2 O3 Inorganic materials 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 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
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、高級な機能性高分子化
合物および医薬品などの原料として有用なアルキルアダ
マンタン類の製造用触媒およびこれを用いたアルキルア
ダマンタン類の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for producing alkyladamantanes useful as raw materials for high-grade functional polymer compounds and pharmaceuticals, and a method for producing alkyladamantanes using the catalyst.
【０００２】0002
【従来の技術】アルキルアダマンタン類は、既にいくつ
かの製造方法が開示されているが、これらはＨ−Ｙ型ゼ
オライトをイオン交換などの方法により修飾した固体酸
触媒を用いる方法（特公昭５２−１２７０６号など）、
並びにハロゲン化炭化水素溶媒中でハロゲン化アルミニ
ウム触媒により製造する方法（特開昭６３−１５９３３
０号、特開平２−１３８１３５号など）の２種に大別す
ることができる。ゼオライト系触媒を用いる方法は、ハ
ロゲン化アルミニウム触媒法のように大量の廃酸の発生
がなく、触媒と生成物の分離が容易であるなどの点で優
れた方法であるが、触媒活性が十分でないばかりか、開
環反応などにより分解生成物が生成するためアダマンタ
ン類への選択性が低いこと、さらに、触媒組成が複雑で
触媒コストが高くなるなどの問題点があった。特開昭６
０−２４６３３３号公報によれば、上述したゼオライト
系触媒を硫酸アンモニウム水溶液で処理し、これを焼成
して硫酸イオンを担持した触媒を用いることにより、ア
ダマンタン生成反応の選択性が向上するとの記載がある
が、硫酸イオンの担持による収率の向上は１．６倍にす
ぎず、また分解反応への選択率は記載されていない。ま
た、触媒組成が複雑であることは同様である。BACKGROUND OF THE INVENTION Several methods for producing alkyladamantanes have already been disclosed. 12706 etc.),
and a method of producing it using an aluminum halide catalyst in a halogenated hydrocarbon solvent (Japanese Patent Application Laid-open No. 63-15933
No. 0, JP-A No. 2-138135, etc.). The method using a zeolite catalyst is an excellent method in that it does not generate a large amount of waste acid unlike the aluminum halide catalyst method and it is easy to separate the catalyst and product, but the method does not have sufficient catalytic activity. In addition, there were other problems, such as low selectivity to adamantanes because decomposition products are produced by ring-opening reactions, etc., and the catalyst composition is complex, increasing catalyst cost. Tokukai Showa 6
According to Publication No. 0-246333, it is stated that the selectivity of the adamantane production reaction is improved by treating the above-mentioned zeolite catalyst with an aqueous ammonium sulfate solution and calcining it to support sulfate ions. However, the yield is only improved by 1.6 times due to the support of sulfate ions, and the selectivity for the decomposition reaction is not described. Similarly, the catalyst composition is complex.
【０００３】一方、ゼオライト以外の固体触媒を用いた
研究例としては、塩素処理したＰｔ／Ａｌ２ Ｏ３ 触
媒（Ｊ．Ｃｈｅｍ．Ｓｏｃ．，９３，２７９８（１９７
１））を挙げることができるが、触媒活性、触媒寿命と
も極めて低く、工業触媒として利用できるものではない
。以上述べたように、アルキルアダマンタン類を工業的
に安価に製造することを可能とする高活性で分解反応へ
の選択性が低く、かつ、組成が単純で触媒の製造も容易
である触媒は、未だ見いだされていない。On the other hand, as an example of research using a solid catalyst other than zeolite, a chlorinated Pt/Al2 O3 catalyst (J. Chem. Soc., 93, 2798 (197
1)), but both catalyst activity and catalyst life are extremely low and cannot be used as industrial catalysts. As mentioned above, catalysts that are highly active, have low selectivity for decomposition reactions, have a simple composition, and are easy to manufacture, enable the industrial production of alkyladamantanes at low cost. It has not been found yet.
【０００４】0004
【発明が解決しようとする課題】以上述べたように、ア
ルキルアダマンタン類を製造する触媒としてゼオライト
などの固体触媒を適用するにおいて、現状では触媒活性
が十分でないばかりか、開環反応などにより分解生成物
が生成するためアダマンタン類への選択性が低く、さら
に、触媒組成が複雑で調製法も簡便でなく触媒コストが
高くなるなどの問題点があった。したがって、本発明の
目的は、アルキルアダマンタン類を工業的に安価に製造
するにあたり、高活性・高選択性を有し、分解生成物の
生成もほとんど無く、かつ、触媒組成が単純で触媒コス
トも安価な工業的な使用に耐える触媒およびこの触媒を
用いたアルキルアダマンタン類の製造方法を提供するこ
とにある。[Problems to be Solved by the Invention] As stated above, when solid catalysts such as zeolites are used as catalysts for producing alkyl adamantanes, not only do they currently not have sufficient catalytic activity, but they also suffer from decomposition and formation due to ring-opening reactions, etc. There were other problems, such as low selectivity to adamantanes due to the formation of adamantane compounds, and the catalyst composition was complex, the preparation method was not simple, and the cost of the catalyst was high. Therefore, an object of the present invention is to industrially produce alkyladamantanes at low cost, with high activity and high selectivity, with almost no generation of decomposition products, and with a simple catalyst composition and low catalyst cost. The object of the present invention is to provide a catalyst that is inexpensive and durable for industrial use, and a method for producing alkyladamantanes using this catalyst.
【０００５】[0005]
【課題を解決するための手段】高活性・高選択率、かつ
、分解反応がほとんど進行しないこと、さらに触媒の組
成が単純でその製造が容易であることを目的として、本
発明者らは種々な固体触媒の活性と選択性を鋭意検討し
た。その結果、（１）γ−アルミナおよび／またはシリ
カ−アルミナを一般式（Ｉ）で示されるクロロフルオロ
メタンで処理した触媒は、アルキルアダマンタン類を工
業的に製造するに十分な活性と選択性を有し、この触媒
の調製は安価な原料を用い簡便なる方法で可能であるこ
と、（２）クロロフルオロメタンで処理する際の処理温
度を２００〜５００℃とすることにより、高活性で、か
つ分解反応の進行がほとんどみられず選択性の高い触媒
が得られること、（３）このようにして得られた触媒を
用い、窒素などの雰囲気下、５〜３０気圧に加圧し、温
度２００〜２７０℃で反応を行うことにより、高収率で
目的とするアルキルアダマンタン類を製造することがで
きることを見いだし本発明を完成した。[Means for Solving the Problems] The present inventors have developed various methods for achieving high activity and high selectivity, as well as for the decomposition reaction to hardly proceed, and for the composition of the catalyst to be simple and easy to manufacture. We have intensively investigated the activity and selectivity of solid catalysts. As a result, (1) the catalyst obtained by treating γ-alumina and/or silica-alumina with chlorofluoromethane represented by the general formula (I) has sufficient activity and selectivity for the industrial production of alkyladamantanes. (2) By setting the treatment temperature at 200 to 500°C during treatment with chlorofluoromethane, this catalyst can be prepared by a simple method using inexpensive raw materials, and it has high activity and (3) Using the catalyst thus obtained, the catalyst was pressurized to 5 to 30 atmospheres in an atmosphere such as nitrogen, and heated to a temperature of 200 to 30 atm. The inventors have completed the present invention by discovering that the desired alkyl adamantane can be produced in high yield by carrying out the reaction at 270°C.
【０００６】すなわち、本発明は、γ−アルミナおよび
／またはシリカ−アルミナを一般式（Ｉ）、ＣＨ４−（
ｎ＋ｍ） Ｃｌｎ Ｆｍ ───（Ｉ）（ただし、
ｎ，ｍは１〜３の整数であり、ｎとｍの和は３あるいは
４である）で示されるクロロフルオロメタンで処理した
ことを特徴とするアルキルアダマンタン類の製造用触媒
を提供するものである。That is, the present invention provides γ-alumina and/or silica-alumina with the general formula (I), CH4-(
n+m) Cln Fm ---(I) (However,
n and m are integers from 1 to 3, and the sum of n and m is 3 or 4). be.
【０００７】γ−アルミナおよび／またはシリカ−アル
ミナをクロロフルオロメタンで処理する際の処理温度は
２００〜５００℃であるのが好適である。[0007] The treatment temperature when treating γ-alumina and/or silica-alumina with chlorofluoromethane is preferably 200 to 500°C.
【０００８】本発明はまた、上記触媒を用いてパーヒド
ロアセナフテンの異性化により炭素数１２のアルキルア
ダマンタン類を製造する方法を提供するものである。こ
のとき、異性化反応を、５〜３０気圧、２００〜２７０
℃行なうのが好ましい。The present invention also provides a method for producing a C12 alkyl adamantane by isomerizing perhydroacenaphthene using the above catalyst. At this time, the isomerization reaction is carried out at 5 to 30 atmospheres and 200 to 270 atmospheres.
It is preferable to carry out the reaction at ℃.
【０００９】以下に、本発明をさらに詳細に説明する。
シリカ−アルミナをＣＣｌＦ３ のようなクロロフルオ
ロメンタンで処理することにより酸強度が増大すること
は、既に報告されている（例えば、Ａ．Ｋｕｒｏｓａｋ
ｉら、Ｂｕｌｌ．， Ｃｈｅｍ．， Ｓｏｃ．， Ｊｐ
ｎ．， ６３， ２３６３（１９９０））。本発明で用
いられるクロロフルオロメタン処理γ−アルミナおよび
／またはシリカ−アルミナ触媒はこのような超強酸触媒
を転用しようとするものである。The present invention will be explained in more detail below. It has already been reported that treatment of silica-alumina with chlorofluoromenthanes such as CClF3 increases acid strength (e.g. A. Kurosak et al.
i et al., Bull. , Chem. , Soc. , Jp
n. , 63, 2363 (1990)). The chlorofluoromethane-treated γ-alumina and/or silica-alumina catalyst used in the present invention is an attempt to repurpose such a super strong acid catalyst.
【００１０】ところで、アダマンタン転移反応が、一般
に、多量の強酸触媒を必要とすることはよく知られてい
るが、最適な酸強度範囲などについては何ら知られてい
ない。本発明者らは、γ−アルミナおよび／またはシリ
カ−アルミナをクロロフルオロメタンで処理するにあた
って、処理温度に好適範囲があるが、この範囲を逸脱す
ると活性・選択性とも低下することを見い出し本発明に
至ったものである。この理由については明らかではない
が、クロロフルオロメタンの担持状態や担持量が変化す
ることによって、表面状態が変化し、触媒の酸強度範囲
などが本反応の触媒にとって必要な最適範囲から逸脱す
るためと考えられる。Incidentally, although it is well known that the adamantane rearrangement reaction generally requires a large amount of strong acid catalyst, nothing is known about the optimum acid strength range. The present inventors have discovered that there is a suitable treatment temperature range for treating γ-alumina and/or silica-alumina with chlorofluoromethane, but that when it deviates from this range, both activity and selectivity decrease. This is what led to this. The reason for this is not clear, but as the supported state and amount of chlorofluoromethane changes, the surface state changes, and the acid strength range of the catalyst deviates from the optimal range required for the catalyst in this reaction. it is conceivable that.
【００１１】本発明で用いられる触媒原料のγ−アルミ
ナ、シリカ−アルミナは何ら限定的ではなく、種々な方
法により製造されたものを用いることができる。これら
触媒原料の形状は、反応器の形式にもよるが、粉末状、
顆粒状、あるいは適当な成形体など任意である。The γ-alumina and silica-alumina used as catalyst raw materials in the present invention are not limited in any way, and those produced by various methods can be used. The shape of these catalyst raw materials depends on the type of reactor, but the shape is powdery,
It can be in any form such as granules or a suitable molded body.
【００１２】本発明で用いるクロロフルオロメタンは、
下記の一般式（Ｉ）で示される。
ＣＨ４−（ｎ＋ｍ） Ｃｌｎ Ｆｍ ───（Ｉ）
（ただし、ｎ，ｍは１〜３の整数であり、ｎとｍの和は
３あるいは４である）この一般式（Ｉ）で示されるクロ
ロフルオロメタンとしては、トリクロロフルオロメタン
、ジクロロジフルオロメタン、クロロジフルオロメタン
等を例示することができる。The chlorofluoromethane used in the present invention is
It is represented by the following general formula (I). CH4-(n+m) Cln Fm ---(I)
(However, n and m are integers of 1 to 3, and the sum of n and m is 3 or 4.) Examples of the chlorofluoromethane represented by this general formula (I) include trichlorofluoromethane, dichlorodifluoromethane, Examples include chlorodifluoromethane.
【００１３】クロロフルオロメタン処理に用いる装置は
、何ら限定的ではないが、固定床流通式反応装置を用い
るのが簡便である。この場合、反応管に任意の量のγ−
アルミナおよび／またはシリカ−アルミナを充填し、ク
ロロフルオロメタン蒸気をそのまま、あるいは窒素など
の不活性ガスで希釈して流通させ、処理を行なえばよい
。処理時の圧力は減圧から加圧まで任意である。処理温
度は、既に述べたように、２００〜５００℃とする必要
があるが、処理時間は処理する際のクロロフルオロメタ
ンの種類や濃度等により異なる。例えば、顆粒状のシリ
カ−アルミナを窒素で濃度５０％に希釈したジクロロジ
フルオロメタンで３００℃で処理する場合、処理時間は
１〜６０分、さらに好ましくは３〜３０分が適当である
。[0013] The equipment used for the chlorofluoromethane treatment is not limited in any way, but it is convenient to use a fixed bed flow reactor. In this case, any amount of γ-
The treatment may be carried out by filling the chamber with alumina and/or silica-alumina and passing chlorofluoromethane vapor as it is or diluted with an inert gas such as nitrogen. The pressure during treatment can be any value from reduced pressure to increased pressure. As already mentioned, the treatment temperature needs to be 200 to 500°C, but the treatment time varies depending on the type and concentration of chlorofluoromethane used in the treatment. For example, when granular silica-alumina is treated at 300°C with dichlorodifluoromethane diluted with nitrogen to a concentration of 50%, the appropriate treatment time is 1 to 60 minutes, more preferably 3 to 30 minutes.
【００１４】これらの処理によって、アルキルアダマン
タン類の製造にさいし高活性・高選択性を示すクロロフ
ルオロメタン処理γ−アルミナおよび／またはシリカ−
アルミナ触媒を製造することができる。なお、触媒の形
状は、反応器の形式にもよるが、粉末状、顆粒状、ある
いは適当な成形体など任意である。[0014] Through these treatments, chlorofluoromethane-treated γ-alumina and/or silica which exhibits high activity and high selectivity in the production of alkyl adamantanes is obtained.
Alumina catalysts can be produced. The shape of the catalyst may be arbitrary, such as powder, granules, or a suitable molded body, depending on the type of reactor.
【００１５】本発明で用いられる原料のパーヒドロアセ
ナフテンは、通常、コールタール中に含まれるアセナフ
テンの全水添により得られるが、他の方法で製造したパ
ーヒドロアセナフテンを用いることもできる。The raw material perhydroacenaphthene used in the present invention is usually obtained by total hydrogenation of acenaphthene contained in coal tar, but perhydroacenaphthene produced by other methods can also be used.
【００１６】アルキルアダマンタン類の製造にさいし、
触媒は、パーヒドロアセナフテンに対し重量比で１／５
倍量以上用いればよいが、生産性や経済性の観点から１
／４〜４／１倍量が好ましい。反応はパーヒドロアセナ
フテンが気化しないよう５〜３０気圧で行うが、３０気
圧を越えると反応速度が低下してしまい好ましくない。
反応温度は２００〜２７０℃が好適である。２００℃未
満では反応速度が極めて遅く、２７０℃を越えると分解
生成物の生産量が多くなり、経済的でない。反応時間は
触媒量や反応温度にもよるが、１〜１０時間が適当であ
る。例えば、反応温度を２５０℃とし、触媒を原料に対
し１／３重量比用いた場合では、２〜４時間反応を行え
ば十分である。パーヒドロアセナフテンと触媒との接触
方式はオートクレーブなどによる回分式完全混合槽、加
圧流通式など任意である。[0016] In the production of alkyl adamantane,
The weight ratio of the catalyst to perhydroacenaphthene is 1/5.
It is sufficient to use more than double the amount, but from the viewpoint of productivity and economy,
/4 to 4/1 times the amount is preferred. The reaction is carried out at a pressure of 5 to 30 atm to prevent perhydroacenaphthene from vaporizing; however, if the pressure exceeds 30 atm, the reaction rate will decrease, which is not preferable. The reaction temperature is preferably 200 to 270°C. If it is less than 200°C, the reaction rate is extremely slow, and if it exceeds 270°C, the amount of decomposition products produced increases, making it uneconomical. Although the reaction time depends on the amount of catalyst and the reaction temperature, 1 to 10 hours is appropriate. For example, when the reaction temperature is 250° C. and the catalyst is used at a weight ratio of 1/3 to the raw material, it is sufficient to carry out the reaction for 2 to 4 hours. The method of contacting perhydroacenaphthene with the catalyst may be arbitrary, such as a batch complete mixing tank using an autoclave or the like, or a pressurized flow method.
【００１７】本発明の方法によれば、高い選択率でバー
ヒドロアセナフテンから炭素数１２のアルキルアダマン
タン混合物を製造することができるので、混合物として
使用する場合は非常に簡単な蒸留によって製品であるア
ルキルアダマンタン混合物を得ることができる。また、
反応生成物から特に有用な１，３−ジメチルアダマンタ
ンを得る場合には、これらのアルキルアダマンタン混合
物の内、１，３−ジメチルアダマンタンが最も熱力学的
に安定なため、生成物を精留して目的とする１，３−ジ
メチルアダマンタンを単離した後、蒸留残渣を反応器に
リサイクルして再度反応させることによって、高収率で
目的とする１，３−ジメチルアダマンタンを製造するこ
ともできる。According to the method of the present invention, a mixture of alkyl adamantane having 12 carbon atoms can be produced from barhydroacenaphthene with high selectivity, so that when used as a mixture, the product can be obtained by very simple distillation. Alkyladamantane mixtures can be obtained. Also,
In order to obtain particularly useful 1,3-dimethyladamantane from the reaction product, the product is rectified because 1,3-dimethyladamantane is the most thermodynamically stable of these alkyladamantane mixtures. After isolating the target 1,3-dimethyladamantane, the distillation residue can be recycled to the reactor and reacted again, thereby producing the target 1,3-dimethyladamantane in a high yield.
【００１８】[0018]
【実施例】以下、実施例に基づき本発明を具体的に説明
するが、本発明はこれに限定されるものではない。EXAMPLES The present invention will be specifically explained below based on Examples, but the present invention is not limited thereto.
【００１９】（実施例１）アルミニウムイソプロポキサ
イドより常法に従って調製したγ−アルミナを成形後、
粉砕して１〜２ｍｍ程度の顆粒としたもの１０ｇを固定
床常圧流通式反応装置の反応管に充填した。触媒層の温
度を４００℃とした後、窒素ガスで５０％に希釈したト
リクロロフルオロメタン蒸気を総流量１．２Ｌ／ｍｉｎ
で５分間接触させた。(Example 1) After molding γ-alumina prepared from aluminum isopropoxide according to a conventional method,
10 g of pulverized granules of about 1 to 2 mm were filled into a reaction tube of a fixed bed normal pressure flow reactor. After setting the temperature of the catalyst layer to 400°C, trichlorofluoromethane vapor diluted to 50% with nitrogen gas was added at a total flow rate of 1.2 L/min.
for 5 minutes.
【００２０】処理済みの上記触媒５ｇとパーヒドロアセ
ナフテン１５ｇとを容積５０ｍＬのステンレス製オート
クレーブにいれ、窒素置換後、窒素で１５気圧に加圧し
た。次に、オートクレーブを電気炉で加熱するとともに
反応液を攪拌した。反応はオートクレーブの内温が２５
０℃に到達してから２．５時間行った。反応終了後、反
応容器を冷却し、残ガスをパージして常圧に戻した。反
応生成物から触媒を濾過によって除去した後、生成物を
ガスクロマトグラフで分析した。その結果、パーヒドロ
アセナフテンの転化率は９４％であり、炭素数１２のア
ルキルアダマンタン（ジメチルアダマンタンとエチルア
ダマンタンの総和）への合計選択率は８９％であり、開
環反応などによって生成した分解生成物への選択率は０
．８％にすぎなかった。[0020] 5 g of the treated catalyst and 15 g of perhydroacenaphthene were placed in a stainless steel autoclave having a volume of 50 mL, and after the autoclave was purged with nitrogen, the autoclave was pressurized to 15 atmospheres with nitrogen. Next, the autoclave was heated in an electric furnace and the reaction solution was stirred. The reaction takes place when the internal temperature of the autoclave is 25
The test was carried out for 2.5 hours after reaching 0°C. After the reaction was completed, the reaction vessel was cooled, residual gas was purged, and the pressure was returned to normal pressure. After removing the catalyst from the reaction product by filtration, the product was analyzed by gas chromatography. As a result, the conversion rate of perhydroacenaphthene was 94%, and the total selectivity to alkyladamantane having 12 carbon atoms (the sum of dimethyladamantane and ethyladamantane) was 89%. Selectivity to product is 0
．． It was only 8%.
【００２１】（実施例２）トリクロロフルオロメタンの
処理温度を３００℃とした以外は実施例１と同様にして
処理、ならびに異性化反応を行った。生成物を分析した
結果、パーヒドロアセナフテンの転化率は９９％、アル
キルアダマンタンへの合計選択率は９２％、分解生成物
の選択率は１．２％であった。また、生成物の内、１，
３−ジメチルアダマンタンの選択率は３６％であった。(Example 2) The treatment and isomerization reaction were carried out in the same manner as in Example 1 except that the treatment temperature for trichlorofluoromethane was 300°C. Analysis of the product showed that the conversion of perhydroacenaphthene was 99%, the total selectivity to alkyladamantane was 92%, and the selectivity of decomposition products was 1.2%. Also, among the products, 1,
The selectivity for 3-dimethyladamantane was 36%.
【００２２】（実施例３）γ−アルミナの処理をクロロ
ジフルオロメタンとした以外は実施例２と同様にして触
媒の処理、異性化反応を行った。パーヒドロアセナフテ
ンの転化率は９４％、アルキルアダマンタンへの合計選
択率は９１％、分解生成物の選択率は１．１％であった
。(Example 3) Catalyst treatment and isomerization reaction were carried out in the same manner as in Example 2 except that γ-alumina was treated with chlorodifluoromethane. The conversion rate of perhydroacenaphthene was 94%, the total selectivity to alkyladamantane was 91%, and the selectivity to decomposition products was 1.1%.
【００２３】（実施例４）実施例２で得た触媒を用い、
実施例２の５倍のスケールで異性化反応を行った。反応
結果は実施例２と同様であった。理論段数２０段の蒸留
塔を用いて反応生成物から１，３−ジメチルアダマンタ
ンを精製したところ、２２．４ｇ（仕込んだパーヒドロ
アセナフテンの２９．９％に相当）の１，３−ジメチル
アダマンタンが得られた。次に、この蒸留残渣に２５ｇ
のパーヒドロアセナフテンを追加して、同じ触媒により
再度異性化反応を行った。その結果、パーヒドロアセナ
フテンの転化率は１００％、アルキルアダマンタンへの
合計選択率は９４％、分解生成物の選択率は０．９％，
１，３−ジメチルアダマンタンの選択率は４２％と第１
回目の反応結果と同様の結果が得られた。(Example 4) Using the catalyst obtained in Example 2,
The isomerization reaction was performed on a scale five times that of Example 2. The reaction results were similar to Example 2. When 1,3-dimethyladamantane was purified from the reaction product using a distillation column with 20 theoretical plates, 22.4g (corresponding to 29.9% of the charged perhydroacenaphthene) of 1,3-dimethyladamantane was obtained. was gotten. Next, add 25g to this distillation residue.
of perhydroacenaphthene was added and the isomerization reaction was performed again using the same catalyst. As a result, the conversion rate of perhydroacenaphthene was 100%, the total selectivity to alkyladamantane was 94%, the selectivity of decomposition products was 0.9%,
The selectivity of 1,3-dimethyladamantane was 42%, the first
Results similar to those of the second reaction were obtained.
【００２４】（実施例５）処理する触媒原料をシリカ−
アルミナとし、用いる処理剤をジクロロジフルオロメタ
ンとし、処理時間を２０分とした以外は実施例２と同様
にして触媒の処理、異性化反応を行った。パーヒドロア
セナフテンの転化率は９５％、アルキルアダマンタンへ
の合計選択率は８４％、分解生成物の選択率は０．４％
であった。(Example 5) The catalyst raw material to be treated was silica.
The catalyst treatment and isomerization reaction were carried out in the same manner as in Example 2, except that alumina was used, dichlorodifluoromethane was used as the treatment agent, and the treatment time was 20 minutes. The conversion rate of perhydroacenaphthene is 95%, the total selectivity to alkyladamantane is 84%, and the selectivity of decomposition products is 0.4%.
Met.
【００２５】（実施例６）処理温度を２００℃とした以
外は実施例５と同様にして触媒の処理、異性化反応を行
った。パーヒドロアセナフテンの転化率は８７％、アル
キルアダマンタンへの合計選択率７８％、分解生成物は
ほとんど生成しなかった。(Example 6) Catalyst treatment and isomerization reaction were carried out in the same manner as in Example 5 except that the treatment temperature was 200°C. The conversion rate of perhydroacenaphthene was 87%, the total selectivity to alkyladamantane was 78%, and almost no decomposition products were produced.
【００２６】（比較例１）何ら処理を行わずにγ−アル
ミナを触媒とした以外は実施例１と同様にして異性化反
応を行った。その結果、パーヒドロアセナフテンの転化
率は３％、アルキルアダマンタンへの合計選択率は１５
％、分解生成物の選択率は２．０％とほとんど反応しな
かった。(Comparative Example 1) An isomerization reaction was carried out in the same manner as in Example 1 except that γ-alumina was used as a catalyst without any treatment. As a result, the conversion rate of perhydroacenaphthene was 3%, and the total selectivity to alkyl adamantane was 15%.
%, and the selectivity of decomposition products was 2.0%, indicating that almost no reaction occurred.
【００２７】（比較例２）何ら処理を行わずにシリカ−
アルミナを触媒とした以外は実施例１と同様にして異性
化反応を行った。その結果、パーヒドロアセナフテンの
転化率は２３％、アルキルアダマンタンへの合計選択率
は４２％、分解生成物の選択率は１．３％とほとんど反
応しなかった。(Comparative Example 2) Silica without any treatment
An isomerization reaction was carried out in the same manner as in Example 1 except that alumina was used as a catalyst. As a result, the conversion of perhydroacenaphthene was 23%, the total selectivity to alkyl adamantane was 42%, and the selectivity of decomposition products was 1.3%, indicating that almost no reaction occurred.
【００２８】[0028]
【発明の効果】本発明の触媒を用いれば、高級な機能性
高分子化合物や医薬品の原料として注目されているアル
キルアダマンタン類を工業的に安価に製造することがで
きる。また、本発明で用いる触媒は原料が安価であり、
かつ単純な組成であるため調製法も簡便であるので、ア
ルキルアダマンタン類の製造方法として特にその工業的
意義が大きい。さらに、本発明によれば、炭素数１２の
アルキルアダマンタン類の内、特に有用な１，３−ジメ
チルアダマンタンも高収率で製造できる点も本発明の大
きな意義である。[Effects of the Invention] By using the catalyst of the present invention, alkyladamantanes, which are attracting attention as raw materials for high-grade functional polymer compounds and pharmaceuticals, can be produced industrially at low cost. In addition, the raw materials for the catalyst used in the present invention are inexpensive;
Moreover, since it has a simple composition and a simple preparation method, it has great industrial significance especially as a method for producing alkyl adamantanes. Furthermore, according to the present invention, 1,3-dimethyladamantane, which is particularly useful among alkyl adamantanes having 12 carbon atoms, can also be produced in high yield, which is a great significance of the present invention.
Claims (4)
アルミナを一般式（Ｉ）、 ＣＨ４−（ｎ＋ｍ） Ｃｌｎ Ｆｍ ───（Ｉ）
（ただし、ｎ，ｍは１〜３の整数であり、ｎとｍの和は
３あるいは４である）で示されるクロロフルオロメタン
で処理したことを特徴とするアルキルアダマンタン類の
製造用触媒。[Claim 1] γ-alumina and/or silica
Alumina is represented by the general formula (I), CH4-(n+m) Cln Fm ---(I)
(However, n and m are integers of 1 to 3, and the sum of n and m is 3 or 4.) A catalyst for producing alkyladamantanes, which is treated with chlorofluoromethane.
アルミナをクロロフルオロメタンで処理する際の処理温
度が２００℃〜５００℃である請求項１に記載のアルキ
ルアダマンタン類の製造用触媒。[Claim 2] γ-alumina and/or silica
The catalyst for producing alkyladamantanes according to claim 1, wherein the treatment temperature when treating alumina with chlorofluoromethane is 200°C to 500°C.
り炭素数１２のアルキルアダマンタン類を製造するにあ
たり、請求項１または２に記載の触媒を用いることを特
徴とするアルキルアダマンタン類の製造方法。3. A method for producing an alkyl adamantane, which comprises using the catalyst according to claim 1 or 2 in producing an alkyl adamantane having 12 carbon atoms by isomerizing perhydroacenaphthene.
圧、２００〜２７０℃で行う請求項３に記載のアルキル
アダマンタン類の製造方法。4. The method for producing alkyl adamantanes according to claim 3, wherein the isomerization reaction of claim 3 is carried out at 5 to 30 atm and 200 to 270°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3093989A JPH04322743A (en) | 1991-04-24 | 1991-04-24 | Catalyst for producing alkyladamantane and production of alkyladamantane using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3093989A JPH04322743A (en) | 1991-04-24 | 1991-04-24 | Catalyst for producing alkyladamantane and production of alkyladamantane using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04322743A true JPH04322743A (en) | 1992-11-12 |
Family
ID=14097814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3093989A Withdrawn JPH04322743A (en) | 1991-04-24 | 1991-04-24 | Catalyst for producing alkyladamantane and production of alkyladamantane using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04322743A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008546714A (en) * | 2005-06-17 | 2008-12-25 | アポジー・バイオテクノロジー・コーポレイション | Sphingosine kinase inhibitor |
| RU2504533C1 (en) * | 2012-06-19 | 2014-01-20 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | Method of producing 1,3-dimethyladamantane |
-
1991
- 1991-04-24 JP JP3093989A patent/JPH04322743A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008546714A (en) * | 2005-06-17 | 2008-12-25 | アポジー・バイオテクノロジー・コーポレイション | Sphingosine kinase inhibitor |
| RU2504533C1 (en) * | 2012-06-19 | 2014-01-20 | Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук | Method of producing 1,3-dimethyladamantane |
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