JPH06256233A - Side chain alkalation of alkyl-substituted aromatic hydrocarbon - Google Patents
Side chain alkalation of alkyl-substituted aromatic hydrocarbonInfo
- Publication number
- JPH06256233A JPH06256233A JP4115993A JP4115993A JPH06256233A JP H06256233 A JPH06256233 A JP H06256233A JP 4115993 A JP4115993 A JP 4115993A JP 4115993 A JP4115993 A JP 4115993A JP H06256233 A JPH06256233 A JP H06256233A
- Authority
- JP
- Japan
- Prior art keywords
- alkyl
- substituted aromatic
- aromatic hydrocarbon
- side chain
- catalyst
- 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.)
- Pending
Links
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- -1 aliphatic monoolefin Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 12
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 11
- 230000029936 alkylation Effects 0.000 claims abstract description 8
- 150000003298 rubidium compounds Chemical class 0.000 claims abstract description 7
- 230000002152 alkylating effect Effects 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 10
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 5
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- FIPKSKMDTAQBDJ-UHFFFAOYSA-N 1-methyl-2,3-dihydro-1h-indene Chemical compound C1=CC=C2C(C)CCC2=C1 FIPKSKMDTAQBDJ-UHFFFAOYSA-N 0.000 description 2
- XPCLINDRYZAPTJ-UHFFFAOYSA-N 1-methyl-4-(2-methylbutyl)benzene Chemical compound CCC(C)CC1=CC=C(C)C=C1 XPCLINDRYZAPTJ-UHFFFAOYSA-N 0.000 description 2
- LGKMWHPZOZYYTQ-UHFFFAOYSA-N 1-methyl-4-pentylbenzene Chemical compound CCCCCC1=CC=C(C)C=C1 LGKMWHPZOZYYTQ-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- UZILCZKGXMQEQR-UHFFFAOYSA-N decyl-Benzene Chemical compound CCCCCCCCCCC1=CC=CC=C1 UZILCZKGXMQEQR-UHFFFAOYSA-N 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SECAQUZEXAHWBA-UHFFFAOYSA-N 1-ethyl-2,3-dihydro-1h-indene Chemical compound C1=CC=C2C(CC)CCC2=C1 SECAQUZEXAHWBA-UHFFFAOYSA-N 0.000 description 1
- PMPBFICDXLLSRM-UHFFFAOYSA-N 1-propan-2-ylnaphthalene Chemical compound C1=CC=C2C(C(C)C)=CC=CC2=C1 PMPBFICDXLLSRM-UHFFFAOYSA-N 0.000 description 1
- OTTZHAVKAVGASB-HYXAFXHYSA-N 2-Heptene Chemical compound CCCC\C=C/C OTTZHAVKAVGASB-HYXAFXHYSA-N 0.000 description 1
- OTTZHAVKAVGASB-UHFFFAOYSA-N 2-heptene Natural products CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 1
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- YKNMBTZOEVIJCM-UHFFFAOYSA-N dec-2-ene Chemical compound CCCCCCCC=CC YKNMBTZOEVIJCM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/72—Addition to a non-aromatic carbon atom of hydrocarbons containing a six-membered aromatic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
(57)【要約】
【構成】 アルキル置換芳香族炭化水素を脂肪族モノオ
レフィンにより側鎖アルキル化する方法において、アル
カリ金属をルビジウム化合物からなる担体に担持した触
媒を用いることを特徴とするアルキル置換芳香族炭化水
素の側鎖アルキル化方法。
【効果】 原料のアルキル置換芳香族炭化水素よりも炭
素数を増したアルキル置換芳香族炭化水素を短時間で効
率よく得ることができる。(57) [Summary] [Structure] Alkyl substitution characterized by using a catalyst in which an alkali metal is supported on a carrier composed of a rubidium compound in a method for side-chain alkylating an alkyl-substituted aromatic hydrocarbon with an aliphatic monoolefin. Method for side chain alkylation of aromatic hydrocarbons. [Effect] An alkyl-substituted aromatic hydrocarbon having a carbon number higher than that of the starting alkyl-substituted aromatic hydrocarbon can be efficiently obtained in a short time.
Description
【０００１】[0001]
【産業上の利用分野】本発明はアルキル置換芳香族炭化
水素を脂肪族モノオレフィンにより側鎖アルキル化し、
医薬、農薬等の製造中間体として有用な、更に炭素数を
増やしたアルキル置換芳香族炭化水素を製造する方法に
関する。This invention relates to side chain alkylation of an alkyl-substituted aromatic hydrocarbon with an aliphatic monoolefin,
The present invention relates to a method for producing an alkyl-substituted aromatic hydrocarbon which is useful as an intermediate for the production of pharmaceuticals, agricultural chemicals, etc.
【０００２】[0002]
【従来の技術】アルキル置換芳香族炭化水素と脂肪族モ
ノオレフィンを反応させ側鎖アルキル化する従来の技術
としては、アルカリ金属をγ−アルミナ担体に担持した
触媒（特開昭５０−９３９２５）、あるいは、アルカリ
金属を炭酸カリウムに担持した触媒（英国特許明細書１
２６９２８０号、特開昭６１−２２１１３３）等を用い
た方法が知られている。2. Description of the Related Art As a conventional technique for reacting an alkyl-substituted aromatic hydrocarbon with an aliphatic monoolefin to carry out side-chain alkylation, a catalyst in which an alkali metal is supported on a γ-alumina carrier (JP-A-50-93925), Alternatively, a catalyst in which an alkali metal is supported on potassium carbonate (UK Patent Specification 1
Methods using 269280, JP-A-61-221133) and the like are known.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、従来の
方法においては触媒の活性が不充分であり、目的化合物
を短時間で効率よく得ることが困難であった。However, in the conventional method, the activity of the catalyst was insufficient, and it was difficult to efficiently obtain the target compound in a short time.
【０００４】[0004]
【課題を解決するための手段】本発明者等は上記課題に
鑑み、アルキル置換芳香族炭化水素の脂肪族モノオレフ
ィンによる側鎖アルキル化の方法について鋭意検討を行
った結果、触媒としてアルカリ金属を特定のアルカリ金
属化合物担体に担持したものを用いることにより、上記
課題を解決することができることを見い出し本発明に到
達した。In view of the above problems, the inventors of the present invention have conducted extensive studies on a method of side chain alkylation of an alkyl-substituted aromatic hydrocarbon with an aliphatic monoolefin, and as a result, have found that an alkali metal as a catalyst is used. The inventors have found that the above problems can be solved by using a carrier supported on a specific alkali metal compound carrier, and have reached the present invention.
【０００５】すなわち、本発明の要旨は、アルキル置換
芳香族炭化水素を脂肪族モノオレフィンにより側鎖アル
キル化する方法において、アルカリ金属をルビジウム化
合物からなる担体に担持した触媒を用いることを特徴と
するアルキル置換芳香族炭化水素の側鎖アルキル化方法
に存する。以下、本発明を詳細に説明する。That is, the gist of the present invention is characterized in that, in a method of side-chain alkylating an alkyl-substituted aromatic hydrocarbon with an aliphatic monoolefin, a catalyst in which an alkali metal is supported on a carrier made of a rubidium compound is used. It exists in a method for side-chain alkylation of alkyl-substituted aromatic hydrocarbons. Hereinafter, the present invention will be described in detail.
【０００６】本発明で用いる触媒はアルカリ金属をルビ
ジウム化合物からなる担体に担持したものである。アル
カリ金属は特に限定はなく、リチウム、ナトリウム、カ
リウム、ルビジウム、セシウム等いずれも使用すること
ができるが、好ましくはナトリウムである。担体として
用いるルビジウム化合物は、ルビジウムの炭酸塩、リン
酸塩、硫酸塩等に代表される酸塩および塩化物、酸化
物、水酸化物等であり、好ましくはルビジウムの炭酸
塩、リン酸塩である。The catalyst used in the present invention comprises an alkali metal supported on a carrier composed of a rubidium compound. The alkali metal is not particularly limited, and any of lithium, sodium, potassium, rubidium, cesium and the like can be used, but sodium is preferable. The rubidium compound used as the carrier is an acid salt and a chloride represented by rubidium carbonate, phosphate, sulfate and the like, an oxide, a hydroxide, and the like, preferably rubidium carbonate and phosphate. is there.
【０００７】担体形状としては、粉末、球状成形品、押
出成形品等のいずれの形態でもよい。なお、アルカリ金
属を担持する前に窒素等の不活性気体の雰囲気下、通常
２００〜７００℃で数時間焼成し、無水の状態にするこ
とが好ましい。アルカリ金属の担持量は、通常、ルビジ
ウム化合物からなる担体に対して、通常０．１〜２０重
量％、好ましくは０．５〜１０重量％である。担持量を
増やした方が一般に活性を高くする傾向があるが、担持
量が多すぎる場合、特に２０重量％を越えるような場合
は均一な担持が困難である他、場合によっては副生物の
生成が顕著になる。The shape of the carrier may be any of powder, spherical molded product, extruded product and the like. In addition, before carrying an alkali metal, it is preferable to perform firing at 200 to 700 ° C. for several hours in an atmosphere of an inert gas such as nitrogen to make it anhydrous. The amount of the alkali metal supported is usually 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the carrier composed of the rubidium compound. Generally, increasing the loading amount tends to increase the activity, but if the loading amount is too large, especially if it exceeds 20% by weight, uniform loading is difficult and in some cases by-products are formed. Becomes noticeable.
【０００８】触媒の調製方法としては、通常、アルゴン
等の不活性気体雰囲気下、ルビジウム化合物とアルカリ
金属を充分攪拌混合し、均一に分散担持する。この際の
温度条件は、通常、アルカリ金属の融点以上であれば良
いが、好ましくは６０〜３００℃である。また、攪拌速
度は毎分５０〜１０００回転程度が好ましく、調製時間
は、通常１分〜５時間、好ましくは３０分〜３時間であ
る。調製時間が短か過ぎると分散が不充分で均一に担持
されず、一方、長過ぎると成形した担体を用いた場合等
は触媒が破砕する可能性があるので好ましくない。The catalyst is usually prepared by thoroughly stirring and mixing a rubidium compound and an alkali metal in an atmosphere of an inert gas such as argon to uniformly disperse and support them. The temperature condition at this time is usually not lower than the melting point of the alkali metal, but is preferably 60 to 300 ° C. The stirring speed is preferably about 50 to 1000 rpm, and the preparation time is usually 1 minute to 5 hours, preferably 30 minutes to 3 hours. If the preparation time is too short, the dispersion will be insufficient and the particles will not be supported uniformly, while if the preparation time is too long, the catalyst may be crushed when a shaped carrier is used, which is not preferable.
【０００９】上記のような方法によって調製した触媒を
用いて、アルキル置換芳香族炭化水素の脂肪族モノオレ
フィンによる側鎖アルキル化反応を実施する。本発明の
方法では、反応原料のアルキル置換芳香族炭化水素の通
常、側鎖アルキル基のα位炭素にアルキル基が付加する
ので、α位炭素に結合した水素原子を１個以上有するア
ルキル置換芳香族炭化水素であれば、非常に容易に側鎖
アルキル化が進行する。A side chain alkylation reaction of an alkyl-substituted aromatic hydrocarbon with an aliphatic monoolefin is carried out using the catalyst prepared by the above method. In the method of the present invention, since the alkyl group is usually added to the α-position carbon of the side chain alkyl group of the alkyl-substituted aromatic hydrocarbon as the reaction raw material, the alkyl-substituted aromatic hydrocarbon having at least one hydrogen atom bonded to the α-position carbon. If it is a group hydrocarbon, the side chain alkylation proceeds very easily.
【００１０】また、アルキル基を２個以上有する場合に
はより大きいアルキル基にアルキル基が付加し易い。ア
ルキル置換芳香族炭化水素のアルキル基の大きさは特に
限定されないが、側鎖アルキル化を受けるアルキル基の
主鎖の炭素数が１〜４程度であることが好ましい。Further, in the case of having two or more alkyl groups, the alkyl group is likely to be added to a larger alkyl group. The size of the alkyl group of the alkyl-substituted aromatic hydrocarbon is not particularly limited, but it is preferable that the main chain of the alkyl group that undergoes side chain alkylation has about 1 to 4 carbon atoms.
【００１１】以上のアルキル置換芳香族炭化水素の具体
例としては、トルエン、エチルベンゼン、ｎ−プロピル
ベンゼン、ｉ−プロピルベンゼン、ｎ−ブチルベンゼ
ン、ｓｅｃ−ブチルベンゼン、ｉ−ブチルベンゼン、ｎ
−デシルベンゼン、キシレン、メシチレン、テトラメチ
ルベンゼン等のアルキル置換ベンゼン、メチルナフタレ
ン、ジメチルナフタレン、イソプロピルナフタレン等の
アルキル置換ナフタレンおよびメチルインダン、エチル
インダン等のアルキル置換インダン等である。Specific examples of the above alkyl-substituted aromatic hydrocarbons include toluene, ethylbenzene, n-propylbenzene, i-propylbenzene, n-butylbenzene, sec-butylbenzene, i-butylbenzene and n.
-Alkyl-substituted benzenes such as decylbenzene, xylene, mesitylene and tetramethylbenzene, alkyl-substituted naphthalenes such as methylnaphthalene, dimethylnaphthalene and isopropylnaphthalene, and alkyl-substituted indans such as methylindane and ethylindane.
【００１２】一方、本発明で用いる脂肪族モノオレフィ
ンは、主鎖の炭素数が、通常２〜１０、好ましくは２〜
６程度が好ましいが特に限定されない。具体的にはエチ
レン、プロピレン、１−ブテン、２−ブテン、イソブテ
ン、１−ペンテン、２−ペンテン、１−ヘキセン、２−
ヘキセン、３−ヘキセン、１−ヘプテン、２−ヘプテ
ン、２−オクテン、２−デセン、３−メチル−１−ブテ
ン、２−メチル−２−ブテン、４−メチル−１−ペンテ
ン等であり、好ましくはエチレン、プロピレン、１−ブ
テン、２−ブテン、イソブテンである。On the other hand, the aliphatic monoolefin used in the present invention has a main chain carbon number of usually 2 to 10, preferably 2 to
About 6 is preferable but not particularly limited. Specifically, ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-
Hexene, 3-hexene, 1-heptene, 2-heptene, 2-octene, 2-decene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1-pentene and the like, preferably Are ethylene, propylene, 1-butene, 2-butene and isobutene.
【００１３】本発明の側鎖アルキル化反応の条件として
は、脂肪族モノオレフィンに対するアルキル置換芳香族
炭化水素の仕込みモル比が通常０．０５〜１０、好まし
くは０．１〜７であり、反応原料のアルキル置換芳香族
炭化水素に対する触媒の重量比は、通常０．０１〜１、
好ましくは０．１〜０．５である。また、反応を行うに
当たり、必要に応じて、例えばベンゼン、ヘキサン等の
反応溶媒を用いてもよい。The conditions for the side chain alkylation reaction of the present invention are that the charged molar ratio of the alkyl-substituted aromatic hydrocarbon to the aliphatic monoolefin is usually 0.05 to 10, preferably 0.1 to 7, The weight ratio of the catalyst to the raw material alkyl-substituted aromatic hydrocarbon is usually 0.01 to 1,
It is preferably 0.1 to 0.5. In carrying out the reaction, a reaction solvent such as benzene or hexane may be used, if necessary.
【００１４】反応様式は回分方式、流通方式いずれも可
能で特に限定されるものではない。脂肪族モノオレフィ
ンの導入法としては、所定温度到達後導入する方法、昇
温前にあらかじめ導入しておく方法等が考えられるが特
に限定されるものではない。反応温度は、通常１２０〜
３００℃、好ましくは１５０〜２３０℃であり、反応圧
力は、通常常圧から２００気圧、好ましくは１０〜１５
０気圧であり、また、反応時間は、通常１分〜２０時間
である。反応後、濾過等により触媒を除去した後、蒸
留、晶析等の公知の分離法により目的生成物の分離を行
うことができる。The reaction mode may be either a batch system or a distribution system and is not particularly limited. As the method for introducing the aliphatic monoolefin, a method of introducing the aliphatic monoolefin after reaching a predetermined temperature, a method of introducing the aliphatic monoolefin in advance before raising the temperature, and the like can be considered, but the method is not particularly limited. The reaction temperature is usually 120-
The temperature is 300 ° C, preferably 150 to 230 ° C, and the reaction pressure is usually atmospheric pressure to 200 atm, preferably 10 to 15 atm.
It is 0 atm, and the reaction time is usually 1 minute to 20 hours. After the reaction, the catalyst can be removed by filtration or the like, and then the desired product can be separated by a known separation method such as distillation or crystallization.
【００１５】[0015]
【実施例】以下、本発明を実施例により具体的に説明す
るが、本発明は下記の実施例に限定されるものではな
い。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
【００１６】実施例１ 市販品の炭酸ルビジウムを窒素雰囲気下、５００℃で２
時間焼成して得た無水の炭酸ルビジウム１７．６ｇと金
属ナトリウム０．４０ｇとを、アルゴン雰囲気下、２０
０ｍｌ丸底フラスコに入れ、１７０℃で２時間攪拌し、
触媒を調製した。この触媒全量とｐ−キシレン３６ｇ
を、窒素雰囲気下、２００ｍｌオートクレーブに仕込
み、攪拌しながら２００℃に昇温した。これに１−ブテ
ン５５ｇを窒素により圧入し反応系内圧力を４３ｋｇ／
ｃｍ2 とした。１−ブテン導入後、８分間、反応を継続
した。その後、室温まで冷却した後、反応内容物をガス
クロマトグラフィーにより分析した。仕込みのｐ−キシ
レンを基準としたｐ−キシレン転化率は１７．２％、生
成物中の選択率は２−メチル−１−（ｐ−トリル）−ブ
タンが６７．６％、１−（ｐ−トリル）−ペンタンが
７．５％であった。Example 1 Commercially available rubidium carbonate was added at 500 ° C. for 2 hours in a nitrogen atmosphere.
Anhydrous rubidium carbonate (17.6 g) and metallic sodium (0.40 g) obtained by calcination for 20 hours under argon atmosphere
Place in a 0 ml round bottom flask and stir at 170 ° C. for 2 hours,
A catalyst was prepared. The total amount of this catalyst and 36 g of p-xylene
Was charged into a 200 ml autoclave under a nitrogen atmosphere and heated to 200 ° C. with stirring. Into this, 55 g of 1-butene was press-fitted with nitrogen so that the pressure in the reaction system was 43 kg /
It was set to cm 2 . After introducing 1-butene, the reaction was continued for 8 minutes. Then, after cooling to room temperature, the reaction contents were analyzed by gas chromatography. The conversion of p-xylene based on the charged p-xylene was 17.2%, and the selectivity in the product was 2-methyl-1- (p-tolyl) -butane 67.6%, 1- (p -Tolyl) -pentane was 7.5%.
【００１７】比較例１ 実施例１において無水炭酸ルビジウム１７．６ｇの代わ
りに無水の炭酸カリウム１０．５ｇを用いた以外は実施
例１と同様に触媒を調製した。次に、実施例１と同じ条
件下で反応を開始し、２時間反応を継続した。反応後、
反応内容物について分析したところ、仕込みのｐ−キシ
レンを基準としたｐ−キシレン転化率は７．０％、生成
物中の選択率は２−メチル−１−（ｐ−トリル）−ブタ
ンが６８．２％、１−（ｐ−トリル）−ペンタンが１
４．４％であった。Comparative Example 1 A catalyst was prepared in the same manner as in Example 1 except that 10.5 g of anhydrous potassium carbonate was used instead of 17.6 g of anhydrous rubidium carbonate. Next, the reaction was started under the same conditions as in Example 1, and the reaction was continued for 2 hours. After the reaction
When the reaction contents were analyzed, the conversion of p-xylene based on the charged p-xylene was 7.0%, and the selectivity in the product was 68 for 2-methyl-1- (p-tolyl) -butane. .2%, 1- (p-tolyl) -pentane 1
It was 4.4%.
【００１８】[0018]
【発明の効果】本発明によれば、アルキル置換芳香族炭
化水素の脂肪族モノオレフィンによる側鎖アルキル化反
応が従来の方法よりも短時間に進行するので、目的とす
る炭素数を増やしたアルキル置換芳香族炭化水素を効率
よく得ることができる。According to the present invention, since the side chain alkylation reaction of an alkyl-substituted aromatic hydrocarbon with an aliphatic monoolefin proceeds in a shorter time than the conventional method, an alkyl having a desired number of carbon atoms is increased. A substituted aromatic hydrocarbon can be efficiently obtained.
Claims (1)
ノオレフィンにより側鎖アルキル化する方法において、
アルカリ金属をルビジウム化合物からなる担体に担持し
た触媒を用いることを特徴とするアルキル置換芳香族炭
化水素の側鎖アルキル化方法。1. A method for side-chain alkylating an alkyl-substituted aromatic hydrocarbon with an aliphatic monoolefin,
A method for side-chain alkylation of an alkyl-substituted aromatic hydrocarbon, which comprises using a catalyst in which an alkali metal is supported on a carrier made of a rubidium compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4115993A JPH06256233A (en) | 1993-03-02 | 1993-03-02 | Side chain alkalation of alkyl-substituted aromatic hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4115993A JPH06256233A (en) | 1993-03-02 | 1993-03-02 | Side chain alkalation of alkyl-substituted aromatic hydrocarbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06256233A true JPH06256233A (en) | 1994-09-13 |
Family
ID=12600647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4115993A Pending JPH06256233A (en) | 1993-03-02 | 1993-03-02 | Side chain alkalation of alkyl-substituted aromatic hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06256233A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019209221A (en) * | 2018-05-31 | 2019-12-12 | 三菱瓦斯化学株式会社 | Base composition, production method of base composition, and production method of amino-group-containing alkyl-substituted aromatic compound |
-
1993
- 1993-03-02 JP JP4115993A patent/JPH06256233A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019209221A (en) * | 2018-05-31 | 2019-12-12 | 三菱瓦斯化学株式会社 | Base composition, production method of base composition, and production method of amino-group-containing alkyl-substituted aromatic compound |
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