JPH03367B2 - - Google Patents
Info
- Publication number
- JPH03367B2 JPH03367B2 JP60250980A JP25098085A JPH03367B2 JP H03367 B2 JPH03367 B2 JP H03367B2 JP 60250980 A JP60250980 A JP 60250980A JP 25098085 A JP25098085 A JP 25098085A JP H03367 B2 JPH03367 B2 JP H03367B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- metathesis
- cyclooctene
- catalyst
- solution
- 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 - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 18
- 150000001925 cycloalkenes Chemical class 0.000 claims description 10
- 238000005649 metathesis reaction Methods 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 12
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 9
- 239000004913 cyclooctene Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005686 cross metathesis reaction Methods 0.000 description 2
- QIOLVKNDAOPVBC-UHFFFAOYSA-N cyclohexadeca-1,3-diene Chemical compound C1CCCCCCC=CC=CCCCCC1 QIOLVKNDAOPVBC-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 2
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 1
- JKNILYPXFHDXTA-UHFFFAOYSA-N cyclotetradeca-1,3-diene Chemical compound C1CCCCCC=CC=CCCCC1 JKNILYPXFHDXTA-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000003282 rhenium compounds Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- RWWNQEOPUOCKGR-UHFFFAOYSA-N tetraethyltin Chemical compound CC[Sn](CC)(CC)CC RWWNQEOPUOCKGR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明はRe2O7／Al2O3から成る担体付触媒存
在下のシクロアルケンのメタセシス反応によつて
シクロアルカジエンを液相で製造する方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing cycloalkadienes in liquid phase by metathesis reaction of cycloalkenes in the presence of a supported catalyst consisting of Re 2 O 7 /Al 2 O 3 .
Re2O7／Al2O3触媒によるシクロオクテンのメ
タセシス反応によつてシクロヘキサデカジエンを
製造することは英国特許第1105565号によつて既
に知られている。それは好ましくはソツクスレー
の装置で固体抽出する方法で行われ、収率は導入
するシクロオクテンの量に関して６％と記載され
ている。 The preparation of cyclohexadecadiene by the metathesis reaction of cyclooctene with a Re 2 O 7 /Al 2 O 3 catalyst is already known from British Patent No. 1105565. It is preferably carried out by solid extraction in a Soxhlet apparatus, and the yield is stated to be 6%, based on the amount of cyclooctene introduced.
上記方法の基礎にある反応形式は出発物質の二
量化であると言うことができる。前記の不満足な
収率は最終的に、反応が二量化に関して不十分な
選択性で進行し大部分はより高度なオリゴマーが
生成するということに帰せられるべきではない。 The reaction type underlying the above process can be said to be the dimerization of the starting materials. The unsatisfactory yields mentioned above cannot ultimately be attributed to the fact that the reaction proceeds with insufficient selectivity with respect to dimerization and mostly higher oligomers are formed.
本発明者は、シクロアルケンのメタセシス反応
に於ては二量化段階、或は相異なる原料物質を導
入する場合の二量化に相当する段階を超える度合
は、出発物質の高度に希釈された溶液を使用して
反応を行う場合には非常に小さくなることを見出
した。 The inventor has determined that in the metathesis reaction of cycloalkenes, a highly dilute solution of the starting material is It has been found that the size becomes very small when the reaction is carried out using
本発明の対象は、シクロアルケンの0.01〜0.05
モル溶液をRe2O7／Al2O3から成る担体付触媒と
10〜100秒間接触させることを特徴とする、
Re2O7／Al2O3から成る担体付触媒存在下のシク
ロアルケンのメタセシス反応によつてシクロアル
カジエンを液相で製造する方法である。 The object of the present invention is 0.01 to 0.05 of cycloalkenes.
A molar solution is mixed with a supported catalyst consisting of Re 2 O 7 /Al 2 O 3 .
characterized by contact for 10 to 100 seconds,
This is a method for producing cycloalkadienes in a liquid phase through a metathesis reaction of cycloalkenes in the presence of a supported catalyst consisting of Re 2 O 7 /Al 2 O 3 .
本発明の方法は、シクロヘプテン或はシクロオ
クテンの二量化によるシクロテトラデカジエン−
１，８およびシクロヘキサデカジエン−１，９の
製造、ならびに、シクロヘプテンおよびシクロオ
クテン或はシクロペンテンおよびシクロドデセン
のメタセシスによつて得られるシクロペンタデカ
ジエン−１，８およびシクロヘプタデカジエン−
１，６の製造を特に目ざすものである。 The method of the present invention produces cyclotetradecadiene by dimerizing cycloheptene or cyclooctene.
1,8 and cyclohexadecadiene-1,9, and cyclopentadecadiene-1,8 and cycloheptadecadiene-1,8 obtained by metathesis of cycloheptene and cyclooctene or cyclopentene and cyclododecene.
It is especially aimed at manufacturing 1 and 6.
γ−Al2O3を担体物質とする担体付触媒が特に
使用される。この担体物質の比表面積は好ましく
はBET法で100〜300m2／ｇである。 Supported catalysts with γ-Al 2 O 3 as support material are particularly used. The specific surface area of this carrier material is preferably from 100 to 300 m 2 /g by the BET method.
担体物質は特に中空のより糸、球、円筒、立方
体、円すい等の形で使用される。 The carrier material is used in particular in the form of hollow threads, spheres, cylinders, cubes, cones and the like.
触媒の全重量に対するRe2O7の重量割合は好ま
しくは３〜20重量％、特に３〜７重量％である。 The weight proportion of Re 2 O 7 relative to the total weight of the catalyst is preferably from 3 to 20% by weight, in particular from 3 to 7% by weight.
Re2O7／γAl2O3から成り、さらにテトラアルキ
ルすずを共触媒として担持している担体付触媒を
使用することも本発明の範囲内で好ましいことで
ある。共触媒の量はRe2O7と共触媒のモル比が
５：１ないし１：１となるように測られる。 It is also preferred within the scope of the invention to use a supported catalyst consisting of Re 2 O 7 /γAl 2 O 3 and further carrying tetraalkyltin as a cocatalyst. The amount of cocatalyst is measured such that the molar ratio of Re 2 O 7 to cocatalyst is 5:1 to 1:1.
共触媒の例はテトラメチルすず、テトラエチル
すず、テトラｎ−ブチルすず等である。 Examples of cocatalysts are tetramethyltin, tetraethyltin, tetra n-butyltin, and the like.
本発明によつて使用される担体付触媒の製造は
それ自体公知であり、例えば担体物質を過レニウ
ム酸アンモニウムの水溶液で含浸し、続いて生成
物を熱処理してレニウム化合物を酸化物に変える
ことによつて行われる。 The preparation of the supported catalysts used according to the invention is known per se, for example by impregnating the support material with an aqueous solution of ammonium perrhenate and subsequently heat-treating the product to convert the rhenium compound into the oxide. It is carried out by.
Re2O7／γAl2O3触媒に共触媒を担持させるに
は、触媒物質を相当するテトラアルキルすずの脂
肪族または芳香族炭化水素溶液で処理するのが好
ましい。そのような溶媒の例は出発物質の希釈に
も使用されるメタセシス不活性溶媒、例えばペン
タン、ヘキサン、ヘプタン、シクロペンタン、シ
クロヘキサン、石油エーテル、塩化メチレン、ク
ロロホルム、四塩化炭素、クロルベンゼン、ｍ−
ジクロルベンゼン等である。 In order to support the cocatalyst on the Re 2 O 7 /γAl 2 O 3 catalyst, it is preferred to treat the catalyst material with an aliphatic or aromatic hydrocarbon solution of the corresponding tetraalkyltin. Examples of such solvents are metathesis inert solvents which are also used for diluting the starting materials, such as pentane, hexane, heptane, cyclopentane, cyclohexane, petroleum ether, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, m-
Dichlorobenzene, etc.
本発明によるメタセシス反応に付すべきシクロ
オレフインはメタセシス不活性溶媒中0.01〜0.05
モル、好ましくは0.01ないし0.03モルの溶液とし
て使用される。相異なるシクロアルカンを出発物
質として使用する共メタセシス（co−
metathesis）の場合には、この濃度についての記
載は出発物質の合計についてのものである。その
さい出発物質は１：１または約１：１のモル比で
使用される。 The cycloolefin to be subjected to the metathesis reaction according to the present invention is 0.01 to 0.05 in a metathesis inert solvent.
It is used as a molar, preferably 0.01 to 0.03 molar, solution. Co-metathesis (co-
metathesis), the statement regarding the concentration refers to the sum of the starting materials. The starting materials are used in a molar ratio of 1:1 or about 1:1.
メタセシス不活性溶媒の例としては特にペンタ
ン、ヘキサン、ヘプタン、シクロペンタン、シク
ロヘキサン、沸騰範囲30〜60℃の石油エーテル、
塩化メチレン、クロロホルム、四塩化炭素等があ
げられる。 Examples of metathesis inert solvents include, inter alia, pentane, hexane, heptane, cyclopentane, cyclohexane, petroleum ether with a boiling range of 30-60°C,
Examples include methylene chloride, chloroform, and carbon tetrachloride.
本発明方法は固定層配置で行われ、溶解された
シクロアルケンが触媒床を液相として通過させら
れる。本発明では、そのさいの流速は10ないし
100秒の滞留時間すなわち接触時間が保たれるよ
うに調節される。 The process according to the invention is carried out in a fixed bed configuration, in which the dissolved cycloalkene is passed through the catalyst bed as a liquid phase. In the present invention, the flow rate at that time is 10 to
Adjustments are made to maintain a residence or contact time of 100 seconds.
反応温度は普通０〜50℃の範囲内である。 The reaction temperature is usually within the range of 0 to 50°C.
この方法は例えば、触媒を充填した管状反応器
を垂直に配置しシクロアルケン溶液を上から下へ
通過させることによつて行われる。反応器から出
てくる反応混合物は蒸留装置に導かれ、個々の成
分に分離される。目的の生成物は比較的高沸点の
留分として得られる。実際には殆どの場合に連続
操業され、低沸点物質として回収される溶媒なら
びに、場合によつては、未反応出発物質を循環さ
せ、新しい出発物質を補給した後反応器に戻す。 This process is carried out, for example, by vertically arranging a tubular reactor filled with catalyst and passing the cycloalkene solution from top to bottom. The reaction mixture emerging from the reactor is led to a distillation apparatus and separated into its individual components. The desired product is obtained as a relatively high-boiling fraction. In practice, in most cases it is operated continuously, with the solvent recovered as low-boiling material and, if appropriate, unreacted starting material being recycled and returned to the reactor after being replenished with fresh starting material.
本発明の方法により、炭素原子数14ないし17を
有する大環状化合物を好収率で製造することがで
きる。反応の選択性は使用したシクロアルカンの
量の35ないし50％に及ぶ。この方法によつて、化
学的に自体得難い化合物を経済的な方法で製造す
ることができる。この方法の生成物は特に香料分
野で有用であり、例えば〓香香料を製造するため
の出発物質として有用である。 By the process of the invention, macrocyclic compounds having 14 to 17 carbon atoms can be produced in good yields. The selectivity of the reaction ranges from 35 to 50% of the amount of cycloalkane used. By this method, compounds that are chemically difficult to obtain per se can be produced in an economical manner. The products of this process are particularly useful in the perfumery field, for example as starting materials for the production of perfume fragrances.
以下実施例によつて本発明をさらに説明する
が、本発明はこれら実施例に限定されるものでは
ない。 The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples.
実施例 １
シクロヘキサデカジエン−１，９の製造
担体付触媒1.8Kgを充填した管状反応器（長さ
70cm、直径８cm）を垂直に立てて使用した。触媒
は3.5重量％のRe2O7と1.3重量％のテトラメチル
すずを含んでおり、担体としては中空のより糸状
に成型され190m2／ｇの比表面積を有するγ−酸
化アルミニウムを用いた。シクロオクテンのｎ−
ペンタン中0.018モル溶液をこの触媒床を通過さ
せた。混合物の滞留時間は60秒であり、触媒床中
の温度は15℃に調節された。Example 1 Production of cyclohexadecadiene-1,9 A tubular reactor (length:
70 cm, diameter 8 cm) was used by standing vertically. The catalyst contained 3.5% by weight of Re 2 O 7 and 1.3% by weight of tetramethyltin, and the carrier was γ-aluminum oxide formed into a hollow strand and having a specific surface area of 190 m 2 /g. cyclooctene n-
A 0.018 molar solution in pentane was passed through the catalyst bed. The residence time of the mixture was 60 seconds and the temperature in the catalyst bed was adjusted to 15°C.
反応器から出てくる反応混合物を蒸留装置に導
き、そこでｎ−ペンタンを蒸留してとり出し、新
しいシクロオクテンを補給して再び反応器へ戻し
た。 The reaction mixture coming out of the reactor was led to a distillation apparatus where the n-pentane was distilled off, replenished with fresh cyclooctene and returned to the reactor again.
蒸留によつて分離すると最終的に、使用したシ
クロオクテンから計算した理論値の33.5％の収率
でシクロヘキサデカジエン−１，９が得られた。
反応の選択性は37％であつた。 After separation by distillation, cyclohexadecadiene-1,9 was finally obtained in a yield of 33.5% of theory calculated from the cyclooctene used.
The selectivity of the reaction was 37%.
実施例 ２
シクロペンタデカジエン−１，８の製造
実施例１に記載した方法を、シクロオクテンの
ｎ−ペンタン中0.018モル溶液の代りにモル比
１：1.1のシクロオクテン／シクロヘプテン混合
物のｎ−ペンタン溶液を使用して繰り返した。そ
のさいシクロアルケンの合計濃度は0.019モル／
であつた。混合物の触媒床中の滞留時間は70秒
に保つた。Example 2 Preparation of cyclopentadecadiene-1,8 The process described in Example 1 was repeated using a cyclooctene/cycloheptene mixture in a molar ratio of 1:1.1 in n-pentane instead of a 0.018 molar solution of cyclooctene in n-pentane. Repeat using the solution. At that time, the total concentration of cycloalkenes was 0.019 mol/
It was hot. The residence time of the mixture in the catalyst bed was kept at 70 seconds.
反応混合物を蒸留によつて分離すると、それぞ
れ10.5％、10.9％および15.3％の収率でシクロテ
トラデカジエン−１，８、シクロペンタデカジエ
ン−１，８およびシクロヘキサデカジエンが得ら
れた。 The reaction mixture was separated by distillation to give cyclotetradecadiene-1,8, cyclopentadecadiene-1,8 and cyclohexadecadiene in yields of 10.5%, 10.9% and 15.3%, respectively.
Claims (1)
Re2O7／Al2O3から成る担体付触媒と10〜100秒間
接触させることを特徴とする、Re2O7／Al2O3か
ら成る担体付触媒存在下のシクロアルケンのメタ
セシス反応によつてシクロアルカジエンを液相で
製造する方法。1 0.01-0.05 molar solution of cycloalkene
For the metathesis reaction of cycloalkenes in the presence of a supported catalyst consisting of Re 2 O 7 /Al 2 O 3 , which is characterized by contacting with a supported catalyst consisting of Re 2 O 7 /Al 2 O 3 for 10 to 100 seconds. This is a method for producing cycloalkadienes in a liquid phase.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3442376.1 | 1984-11-20 | ||
| DE3442376 | 1984-11-20 | ||
| DE3524977.3 | 1985-07-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61129141A JPS61129141A (en) | 1986-06-17 |
| JPH03367B2 true JPH03367B2 (en) | 1991-01-07 |
Family
ID=6250757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60250980A Granted JPS61129141A (en) | 1984-11-20 | 1985-11-11 | Manufacture of cycloalkadiene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61129141A (en) |
-
1985
- 1985-11-11 JP JP60250980A patent/JPS61129141A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61129141A (en) | 1986-06-17 |
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