JPH04208240A - Production of alicyclic diol - Google Patents
Production of alicyclic diolInfo
- Publication number
- JPH04208240A JPH04208240A JP2337369A JP33736990A JPH04208240A JP H04208240 A JPH04208240 A JP H04208240A JP 2337369 A JP2337369 A JP 2337369A JP 33736990 A JP33736990 A JP 33736990A JP H04208240 A JPH04208240 A JP H04208240A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- dialkyl ester
- general formula
- compound
- 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
- -1 alicyclic diol Chemical class 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 150000002148 esters Chemical class 0.000 claims abstract description 44
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 27
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 17
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 12
- 239000001530 fumaric acid Substances 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 7
- 238000005292 vacuum distillation Methods 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 17
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005698 Diels-Alder reaction Methods 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 3
- 229960004419 dimethyl fumarate Drugs 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction 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、−数式（■）：
及び、−数式（■）：
（但し、−数式、（ＩＶ）中の、ｎは１または２を表す
）で表される脂環式ジオールの製造方法に関する。Detailed Description of the Invention (Industrial Application Field) The present invention provides -mathematical formula (■): and -mathematical formula (■): (wherein -mathematical formula (IV), n is 1 or 2) This invention relates to a method for producing an alicyclic diol represented by:
（従来の技術）
上記−数式（Ｉ［）及び（ＩＶ）で表される脂環式ジオ
ールは、ポリエステルやポリカーボネート等のポリマー
構成成分として使用されており、そのバルキーな骨格か
らかかるポリマーに機械特性、光学特性等の特徴を付与
しつるものである。(Prior Art) Alicyclic diols represented by formulas (I[) and (IV) above are used as constituent components of polymers such as polyester and polycarbonate, and their bulky skeletons give such polymers mechanical properties. , which imparts characteristics such as optical properties.
従来より、上記−数式で表される脂環式ジオールの製造
方法としては、過剰量のシクロペンタジェンもしくはジ
シクロペンタジェンとフマル酸ジエチルエステルのディ
ールス・アルダ−反応によって得られる不飽和脂環式ジ
エチルエステルを原料として用い、水素化反応を２度行
う方法が知られていた。すなわち、従来方法では、まず
該不飽和脂環式ジエチルエステルをベンゼン等の溶媒中
、パラジウム系触媒の存在下に１００℃程度で水素化反
応を行い、予めオレフィン性二重結合を還元して脂環式
ジエチルエステル□とした後、さらにジオキサン等の溶
媒中、アドキンス型銅クロマイト触媒の存在下に、２０
０℃程度で水素化反応させてエチルエステル基をヒドロ
キシメチル基に還元させる２段階の水素化反応を行わな
ければならなかった。これは、アドキンス型銅クロマイ
ト触媒を用いる水素化反応では高温を要するため、−度
に水素化反応を行うとディールス・アルダ−反応が平衡
反応であるが故に、原料である不飽和脂環式ジエチルエ
ステルが分解してしまうと考えられていたためである（
Ｊ、Ｐｏｌｙｍ、Ｓｃｉ：Ｐｏｙｌｍ、Ｃｈｅｍ、Ｅｄ
、、１０．３１９１−３２０４ （１９７２））。Conventionally, as a method for producing an alicyclic diol represented by the above formula, an unsaturated alicyclic diol obtained by a Diels-Alder reaction between an excess amount of cyclopentadiene or dicyclopentadiene and fumaric acid diethyl ester has been used. A method has been known in which diethyl ester is used as a raw material and the hydrogenation reaction is carried out twice. That is, in the conventional method, the unsaturated alicyclic diethyl ester is first hydrogenated at about 100°C in the presence of a palladium-based catalyst in a solvent such as benzene, and the olefinic double bond is reduced in advance. After forming the cyclic diethyl ester □, in the presence of an Adkins type copper chromite catalyst in a solvent such as dioxane, 20
It was necessary to perform a two-step hydrogenation reaction in which the ethyl ester group was reduced to a hydroxymethyl group by hydrogenation reaction at about 0°C. This is because the hydrogenation reaction using an Adkins-type copper chromite catalyst requires a high temperature, and if the hydrogenation reaction is performed at -degrees, the Diels-Alder reaction is an equilibrium reaction. This is because it was thought that the ester would decompose (
J, Polym, Sci: Polym, Chem, Ed.
, 10.3191-3204 (1972)).
しかし、上記方法で″は水素化反応工程が２度あること
に加えて、第１段階の水素化反応で得られた脂環式ジエ
チルエステルを、第２段階の水素化反応へ移行させるに
は、通常、触媒の濾過、減圧蒸留等の多（の操作が必要
であり、製造上の煩雑さを伴っていた。そのため目的物
である上記−数式で表される脂環式ジオールの製造には
非常に長い時間と多くの製造費用を要した。However, in the above method, in addition to having two hydrogenation reaction steps, it is difficult to transfer the alicyclic diethyl ester obtained in the first step hydrogenation reaction to the second step hydrogenation reaction. Usually, multiple operations such as catalyst filtration and vacuum distillation are required, which is complicated in production. Therefore, in order to produce the target alicyclic diol represented by the above formula, It took a very long time and a lot of manufacturing cost.
（発明が解決しようとする課題）
本発明は、上記−数式（ＩＩ）及び（ＩＶ）で表される
脂環式ジオールを効率よく製造する方法を提供すること
を目的とする。(Problems to be Solved by the Invention) An object of the present invention is to provide a method for efficiently producing the alicyclic diols represented by the above formulas (II) and (IV).
（課題を解決するための手段）
本発明者らは、上記従来技術の課題を解決すべく一般式
（ＩＩ）及び（ＴＶ ）で表される脂環式ジオールの製
造工程の簡略化について鋭意検討を重ねた結果、上記従
来の方法において、−数式（Ｉ）または（ｍ）で表され
る不飽和脂環式ジアルキルエステルのオレフィン性二重
結合を、予め還元して脂環式ジエチルエステルとする水
素化反応を行なわなくても、該不飽和脂環式ジアルキル
エステルをアドキンス型銅クロマイト触媒の存在下に、
−度水素化反応を行うだけで、オレフィン性二重結合と
ジアルキルエステルが還元され一般式（Ｉｔ）または（
ｒＶ）で表される脂環式ジオールを効率よ（製造しうる
ことを見出し本発明を完成するに至った。(Means for Solving the Problems) In order to solve the problems of the above-mentioned prior art, the present inventors have conducted extensive studies on simplifying the manufacturing process of alicyclic diols represented by general formulas (II) and (TV). As a result of repeated steps, in the above conventional method, the olefinic double bond of the unsaturated alicyclic dialkyl ester represented by formula (I) or (m) is reduced in advance to form an alicyclic diethyl ester. Even without performing a hydrogenation reaction, the unsaturated alicyclic dialkyl ester can be treated in the presence of an Adkins-type copper chromite catalyst,
By simply carrying out the hydrogenation reaction, the olefinic double bond and the dialkyl ester are reduced and the general formula (It) or (
The present inventors have discovered that it is possible to efficiently produce an alicyclic diol represented by (rV), and have completed the present invention.
すなわち、本発明は、
−８９式（Ｉ）：
（但し、−数式（１）中のＲは炭素数１〜１８のアルキ
ル基を表す）で表される不飽和脂環式ジアルキルエステ
ルを、アドキンス型銅クロマイト触媒を主成分とする触
媒の存在下で水素化還元することを特徴とする、−数式
（■）：
で表される脂環式ジオールの製造方法、および−数式（
ｍ）：
（但し、−６式（Ｉ）中のＲは炭素数１〜１８のアルキ
ル基を表し、ｎは１または２を表す）で表される不飽和
脂環式ジアルキルエステルを、アドキンス型銅クロマイ
ト触媒を主成分とする触媒の存在下で水素化還元するこ
とを特徴とする、−数式（ＩＶ）：
（但し、−数式（ｒｖ ）中のｎは１または２を表す）
で表される脂環式ジオールの製造方法に関する。That is, the present invention provides an unsaturated alicyclic dialkyl ester represented by formula (I): (wherein R in formula (1) represents an alkyl group having 1 to 18 carbon atoms) A method for producing an alicyclic diol represented by the -formula (■), characterized by carrying out hydrogenation reduction in the presence of a catalyst containing a type copper chromite catalyst as a main component, and -the formula (
m): (However, R in -6 formula (I) represents an alkyl group having 1 to 18 carbon atoms, and n represents 1 or 2.) Characterized by hydrogenation reduction in the presence of a catalyst containing a copper chromite catalyst as a main component, - Formula (IV): (However, n in - Formula (rv) represents 1 or 2)
The present invention relates to a method for producing an alicyclic diol represented by:
まず、本発明の原料として使用する前記−数式（１）ま
たは（ＩＩＩ）で表される不飽和脂環式ジアルキルエス
テルについて説明する。該不飽和脂環式ジアルキルエス
テルは、いずれもシクロペンタジェンもしくはジシクロ
ペンタジェンとフマル酸ジアルキルエステル及び／又は
マレイン酸ジアルキルエステルのディールス・アルダ−
反応等によって製造しつる。また、該反応生成物は通常
シクロペンクジエンとフマル酸ジアルキルエステルとの
１：１付加物、２：１付加物、３：１付加物及びシクロ
ペンタジェンの付加重合物からなる混合物であるため、
それぞれの化合物は該混合物を減圧蒸留、再結晶等の操
作で精製分離することにより得られる。First, the unsaturated alicyclic dialkyl ester represented by the above-mentioned formula (1) or (III) used as a raw material in the present invention will be explained. The unsaturated alicyclic dialkyl ester is a Diels-Alder mixture of cyclopentadiene or dicyclopentadiene and fumaric acid dialkyl ester and/or maleic acid dialkyl ester.
Vines produced by reactions, etc. In addition, since the reaction product is usually a mixture consisting of a 1:1 adduct, a 2:1 adduct, a 3:1 adduct of cyclopencdiene and a fumaric acid dialkyl ester, and an addition polymer of cyclopentadiene,
Each compound can be obtained by purifying and separating the mixture through operations such as vacuum distillation and recrystallization.
ここに出発原料であるフマル酸ジアルキルエステル及び
／又はマレイン酸ジアルキルエステルのアルキル基とし
ては、たとえばメチル基、エチル基、ｎ−プロピル基、
イソプロピル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−
ヘキシル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシ
ル基、ｎ−ウンデシル基、ｎ−ドデシル基、ｎ−トリデ
シル基、ｎ−テトラデシル基、ｎ−ペンタデシル基、ｎ
−ヘキサデシル基、ｎ−ヘプタデシル基、ｎ −オクタ
デシル基等があげられる。これらアルキル基のなかでも
メチル基、エチル基、ｎ−プロピル基、イソプロピル基
が好ましい。特に蒸留、再結晶等の取り扱いの点を考慮
すればメチル基がより好ましい。Examples of the alkyl group of the fumaric acid dialkyl ester and/or maleic acid dialkyl ester which are the starting materials include methyl group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, n-pentyl group, n-
Hexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n
-hexadecyl group, n-heptadecyl group, n-octadecyl group, etc. Among these alkyl groups, methyl, ethyl, n-propyl, and isopropyl groups are preferred. In particular, a methyl group is more preferable in consideration of handling such as distillation and recrystallization.
かかる前記−数式（Ｉ）または（Ｉｌｌ）で表される不
飽和脂環式ジアルキルエステルを製造するにあたっての
反応条件は特に制限されず、従来公知の方法を採用すれ
ばよいが、出発原料の仕込量はフマル酸ジアルキルエス
テル及び／又はマレイン酸ジアルキルエステル１モル部
に対し、ジシクロペンタジェン１モル部未満を反応させ
るのがより
い。ジシクロペンタジェンが１モル部以上の場合にはシ
クロペンタジェンの付加重合物等の副生成物が多くなり
、目的物である一般式（１）または（Ｉ［］）で表され
る不飽和脂環式ジアルキルエステルの選択率、収率、純
度が低下するため好ましくない。すなわち、反応混合物
から目的物である一般式（１）または（Ｉｎ）で表され
る不飽和脂環式ジアルキルエステルの純度を上げんとし
て精留操作を行った場合には、該化合物の低熱安定性に
より熱分解が生じるため、通常の簡単な蒸留操作を採用
しつるにすぎず、結局は該化合物の高純度化は困難とな
る。一方、該不飽和脂環式ジアルキルエステルを水素化
した後、反応系から多量の副生成物を除去する場合には
多大な労力を要すること、更には該化合物の純度が低い
ため水素化の選択率も悪くなるなどの不利があり、ディ
ルース・アルダ−反応時に副生物を十分抑制しておくこ
とが肝要とされる。The reaction conditions for producing the unsaturated alicyclic dialkyl ester represented by the above-mentioned formula (I) or (Ill) are not particularly limited, and conventionally known methods may be adopted, but the preparation of the starting materials It is preferable that less than 1 mol part of dicyclopentadiene be reacted with 1 mol part of fumaric acid dialkyl ester and/or maleic acid dialkyl ester. If the amount of dicyclopentadiene is 1 mole part or more, by-products such as addition polymers of cyclopentadiene will increase, and the unsaturated product represented by general formula (1) or (I[]), which is the target product, will increase. This is not preferred because the selectivity, yield, and purity of the alicyclic dialkyl ester decrease. That is, when a rectification operation is performed to increase the purity of the target unsaturated alicyclic dialkyl ester represented by the general formula (1) or (In) from the reaction mixture, the low thermal stability of the compound Since thermal decomposition occurs due to the chemical properties, ordinary simple distillation operations are simply employed, and it becomes difficult to achieve high purity of the compound. On the other hand, after hydrogenating the unsaturated alicyclic dialkyl ester, it takes a lot of effort to remove a large amount of byproducts from the reaction system, and furthermore, the purity of the compound is low, so hydrogenation is not an option. There are disadvantages such as a decrease in reaction rate, so it is important to sufficiently suppress by-products during the Diluce-Alder reaction.
また、前記−数式（ＩＩＩ）で表される不飽和脂環式ジ
アルキルエステルを製造する方法としては、上記方法に
制限されず、たとえば前記−数式（Ｉ）で表される不飽
・和脂環式ジアルキルエステルにジシクロペンタジェン
を反応せさる方法によってもよい。かかる方法による場
合にもジシクロペンタジェンの使用量は、シクロペンタ
ジェンの付加重合物等の副生成物を極力抑えるために、
−数式（１）で表される不飽和脂環式ジアルキルエステ
ルを合成するのに使用したフマル酸ジアルキルエステル
及び／又はマレイン酸ジアルキルエステル１モル部に対
し、ジシクロペンタジェンの総使用量を１モル部未満と
するのがよい。なお、−数式（１）で表される不飽和脂
環式ジアルキルエステルは一般式（ｍ）で表される不飽
和脂環式ジアルキルエステルを合成した際の反応回収物
であってもよく、また未反応のジシクロペンタジェンを
含有していてもよい。Furthermore, the method for producing the unsaturated alicyclic dialkyl ester represented by the above-mentioned formula (III) is not limited to the above-mentioned method, and for example, the unsaturated alicyclic dialkyl ester represented by the above-mentioned formula (I) A method in which a dialkyl ester of the formula is reacted with dicyclopentadiene may also be used. Even when using this method, the amount of dicyclopentadiene used is determined to minimize by-products such as addition polymers of cyclopentadiene.
- The total amount of dicyclopentadiene used is 1 mole part of fumaric acid dialkyl ester and/or maleic acid dialkyl ester used to synthesize the unsaturated alicyclic dialkyl ester represented by formula (1). It is preferable that the amount is less than molar parts. In addition, the unsaturated alicyclic dialkyl ester represented by the formula (1) may be a reaction recovery product when synthesizing the unsaturated alicyclic dialkyl ester represented by the general formula (m), or It may contain unreacted dicyclopentadiene.
本発明では前記−数式（Ｉ）または（ＩＩＩ）で表され
る不飽和脂環式ジアルキルエステルを水素化するにあた
り、アドキンス型銅クロマイト触媒を使用することを必
須とする。アドキンス型銅クロマイト触媒とは酸化銅と
酸化クロムを主成分としてなるものである。また、該触
媒は酸化マンガン、酸化バリウム等の助触媒を含有して
いるものであってもよい。かかる触媒としては各種公知
のものが使用でき、たとえば、市販品としては（商品名
Ｎ ２ Ｃ１１，日揮化学■製）、（商品名Ｎ２Ｏ２、
日揮化学■製）、（商品名Ｎ２Ｏ３゜日揮化学■製）、
（商品名ＣＢ−２．堺化学■製）、堺化学■製）、（商
品名Ｃ−５，堺化学■製）、（商品名Ｃ−１００，堺化
学■製）、（商品名ＣＢ−５００．堺化学（割裂）、（
商品名ＣＢ−７００．堺化学■製）、（商品名Ｇ−２２
．日産ガードラー（割裂）、（商品名Ｇ−２３．日産ガ
ードラー■製）、（商品名Ｇ−８９．日産ガードラー■
製）、（商品名Ｇ−９９．日産ガードラー■製）等があ
げられる。In the present invention, it is essential to use an Adkins type copper chromite catalyst in hydrogenating the unsaturated alicyclic dialkyl ester represented by formula (I) or (III). The Adkins type copper chromite catalyst is mainly composed of copper oxide and chromium oxide. Further, the catalyst may contain a co-catalyst such as manganese oxide or barium oxide. Various known catalysts can be used as such catalysts. For example, commercially available products include (trade name N2C11, manufactured by JGC Chemical Corporation), (trade name N2O2,
(manufactured by JGC Chemical ■), (product name N2O3゜manufactured by JGC Chemical ■),
(Product name CB-2, manufactured by Sakai Chemical ■), (Product name C-5, manufactured by Sakai Chemical ■), (Product name C-100, manufactured by Sakai Chemical ■), (Product name CB- 500. Sakai Chemical (Warisaki), (
Product name CB-700. (manufactured by Sakai Chemical Co., Ltd.), (product name G-22)
．． Nissan Girdler (Warisaki), (Product name G-23. Made by Nissan Girdler), (Product name G-89. Nissan Girdler ■
(manufactured by Nissan Girdler), (trade name G-99. manufactured by Nissan Girdler ■), etc.
すなわち本発明では、前記一般式（Ｔ）または（ＩＩＩ
）で表される不飽和脂環式ジアルキルエステルを前記触
媒の存在下で水素化反応することにより、オレフィン性
二重結合とジアルキルエステルを−度に還元して、本発
明の目的物である一般式（ＩＩ）または（■）で表され
る脂環式ジオールを製造する。That is, in the present invention, the general formula (T) or (III
) by hydrogenating the unsaturated alicyclic dialkyl ester represented by the above catalyst in the presence of the catalyst, the olefinic double bond and the dialkyl ester are reduced to a degree of An alicyclic diol represented by formula (II) or (■) is produced.
反応は、通常、回分式のオートクレーブ中で行い、前記
不飽和脂環式ジアルキルエステル１００重量部に対して
、前記触媒を通常１〜３０重量部程度、好ましくは５〜
２０重量部を使用する。また、反応温度は通常１００〜
３００℃程度、好ましくは１８０〜２５０℃であり、水
素圧力は通常１００〜３００Ｋｇ７ｃｍ２程度、好まし
くは１５０〜２５０ Ｋｇ／ｃｍ”の条件である。尚、
かかる水素化反応に際しては無溶媒下で行ってもよ（、
ジオキサン、トルエン等の溶媒中で行ってもよい。The reaction is usually carried out in a batch autoclave, and the catalyst is usually about 1 to 30 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the unsaturated alicyclic dialkyl ester.
20 parts by weight are used. In addition, the reaction temperature is usually 100~
The temperature is about 300°C, preferably 180 to 250°C, and the hydrogen pressure is usually about 100 to 300 kg/cm2, preferably 150 to 250 kg/cm.
Such hydrogenation reaction may be carried out without solvent (
It may be carried out in a solvent such as dioxane or toluene.
上記水素化反応により得られた反応生成物中における一
般式（ＩＩ）または（ｒＶ）で表される脂環族ジオール
の、−数式（１）または（ｍ）で表される不飽和脂環族
ジアルキルエステルからの選択率は通常７０〜９５モル
％程度（ガスクロマトグラフィーによる測定結果より）
である。The unsaturated alicyclic diol represented by formula (1) or (m) of the alicyclic diol represented by general formula (II) or (rV) in the reaction product obtained by the above hydrogenation reaction. Selectivity from dialkyl ester is usually about 70 to 95 mol% (based on measurement results by gas chromatography)
It is.
該反応生成物は、触媒（無溶媒下の反応の場合は溶媒に
溶解した後）を濾過し、溶媒を除去した後にアセトン、
酢酸エチル等により再結晶を行い精製し、各種用途に供
される。The reaction product is obtained by filtering the catalyst (after dissolving it in a solvent in the case of a solvent-free reaction), removing the solvent, and then adding acetone,
It is purified by recrystallization with ethyl acetate and used for various purposes.
（発明の効果）
（１）本発明の製造方法によれば、従来２度行われてい
た水素化工程を一度行うだけで目的物である一般式（Ｉ
Ｉ）または（ＴＶ ）で表される脂環式ジオールを効率
よく製造することができ時間を大幅に短縮できる。また
、製造の中途段階で触媒の濾過、減圧蒸留等の操作が不
要となり製造が非常に簡略化した。(Effects of the invention) (1) According to the production method of the present invention, the hydrogenation step, which was conventionally performed twice, can be performed only once, and the target product, the general formula (I)
The alicyclic diol represented by I) or (TV) can be efficiently produced, and the time can be significantly shortened. In addition, operations such as catalyst filtration and vacuum distillation are no longer required in the middle of production, greatly simplifying production.
（２）さらに、原料である一般式（’Ｉ ）または（Ｉ
ｌｌ）で表される不飽和脂環族ジアルキルエステルを特
定方法により製造することにより、−数式（ＩＮ また
は（ＴＶ）で表される脂環式ジオールを効率よ（製造す
ることができようになった。(2) Furthermore, the general formula ('I ) or (I
By producing the unsaturated alicyclic dialkyl ester represented by the formula (II) by a specific method, it becomes possible to efficiently (manufacture) the alicyclic diol represented by the formula (IN or (TV)). Ta.
（実施例）
以下に、参考例、実施例をあげて本発明をさらに詳細に
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。(Examples) The present invention will be described in more detail below with reference to reference examples and examples, but the present invention is not limited to these examples.
参考例１
フマル酸ジメチル２９０ｇ、ジシクロペンタジェン２９
２ｇをオートクレーブ中に加え、２２０℃で２時間反応
させ、反応混合物５８２ｇ得た。Reference example 1 290 g of dimethyl fumarate, 29 g of dicyclopentadiene
2g was added into an autoclave and reacted at 220°C for 2 hours to obtain 582g of a reaction mixture.
次いで、得られた反応混合物を減圧蒸留して、１７０〜
ｂ
ンタジェンとフマル酸ジアルキルエステルとの２．１付
加物を主成分とする留分、−８Ω式（１）においてｎ＝
１．Ｒ−メチル基）２７０ｇを得た。ガスクロマトグラ
フィーによる２：１付加物の純度は７８重量％であった
。Then, the obtained reaction mixture was distilled under reduced pressure to give 170~
b Distillate mainly composed of 2.1 adduct of ntadiene and fumaric acid dialkyl ester, -8Ω In formula (1), n=
1. 270 g of R-methyl group) were obtained. The purity of the 2:1 adduct by gas chromatography was 78% by weight.
参考例２
フマル酸ジメチル２９０ｇ、ジシクロペンタジェン２１
２ｇをオートクレーブ中に加え、２２０℃で２時間反応
させ、“反応混合物５０２ｇ得た。Reference example 2 290 g of dimethyl fumarate, 21 dicyclopentadiene
2g was added into an autoclave and reacted at 220°C for 2 hours to obtain 502g of a reaction mixture.
次いで、得られた反応混合物を減圧蒸留して、１７０〜
１８００Ｃ／６Ｔｏｒｒの留分（シクロペンタジェンと
フマル酸ジアルキルエステルとの２＝１付加物を主成分
とする留分、−数式（ＩＩＩ）においてｎ＝１．Ｒ＝メ
チル基）２３８ｇを得た。ガスクロマトグラフィーによ
る２：ｌ付加物の純度は９４重量％であった。Then, the obtained reaction mixture was distilled under reduced pressure to give 170~
238 g of a 1800 C/6 Torr fraction (a fraction mainly composed of a 2=1 adduct of cyclopentadiene and fumaric acid dialkyl ester, n=1.R=methyl group in formula (III)) was obtained. The purity of the 2:l adduct by gas chromatography was 94% by weight.
参考例３
フマル酸ジメチル２９０ｇ、ジシクロペンタジェン１３
３ｇをセパラブルフラスコ中に加え、１７０℃で１時間
反応させた後、２００℃に昇渇し、同温度でジシクロペ
ンタジェン７９ｇを滴下しながら４時間反応を続けて反
応混合物５０２ｇ得た。Reference example 3 290 g of dimethyl fumarate, 13 dicyclopentadiene
After adding 3 g into a separable flask and reacting at 170° C. for 1 hour, the temperature was raised to 200° C., and the reaction was continued for 4 hours while adding 79 g of dicyclopentadiene dropwise at the same temperature to obtain 502 g of a reaction mixture.
次いで、得られた反応混合物を減圧蒸留して、初留分：
（シクロペンタジェンとフマル酸ジアルキルエステルと
の１：１付加物を主成分とする留分、−１１Ｑ式（Ｉ）
においてＲ＝メチル基）１９３ｇ （ガスクロマトグラ
フィーによる１：１付加物の純度は８５重量％）、
１７０〜ｂ
ンタジェンとフマル酸ジアルキルエステルとの２：１付
加物を主成分とする留分、−数式（１）においてｎ＝１
．Ｒ＝メチル基）２３９ｇ （ガスクロマトグラフィー
による２：１付加物の純度は９９重量％）、および残渣
分６５ｇを得た。Then, the obtained reaction mixture was distilled under reduced pressure to obtain the first distillate: (a fraction whose main component is a 1:1 adduct of cyclopentadiene and fumaric acid dialkyl ester, -11Q formula (I)
(where R = methyl group) 193 g (purity of 1:1 adduct by gas chromatography is 85% by weight), 170-b fraction mainly composed of 2:1 adduct of entadiene and fumaric acid dialkyl ester, - In formula (1), n=1
．． 239 g (R = methyl group) (purity of the 2:1 adduct by gas chromatography was 99% by weight) and 65 g of a residue were obtained.
残渣分６５ｇは、Ｎ、Ｎ−ジメチルホルムアミド３２５
ｍ１に加熱溶解した後、５℃で７２時間放置し、シクロ
ペンタジェン重合物の結晶を濾別した。次いで濾液から
Ｎ、Ｎ−ジメチルホルムアミドを減圧蒸留で除いてから
、エタノール２２０ｍ１と１００ｍ１で２回再結晶を行
い３：１付加物−数式（１）においてｎ＝２．Ｒ−メチ
ル基）２２ｇ（ガスクロマトグラフィーによる３：１付
加物の純度は９８重量％）を得た。65 g of residue is 325 g of N,N-dimethylformamide.
After heating and dissolving the solution in ml, it was left to stand at 5°C for 72 hours, and the crystals of the cyclopentadiene polymer were filtered off. Next, N,N-dimethylformamide was removed from the filtrate by vacuum distillation, and then recrystallized twice with 220 ml and 100 ml of ethanol to obtain a 3:1 adduct with n=2. 22 g of R-methyl group (purity of 3:1 adduct by gas chromatography: 98% by weight) was obtained.
実施例１
２００ｍ１容の撹拌式オートクレーブ中に参考例１で得
られた２：１付加物（−数式（ＩＩＩ）においてｎ＝１
、Ｒ＝メチル基）４０ｇ、アドキンス型銅クロマイト触
媒（商品名Ｃ−１００、堺化学■製）６ｇ、溶媒として
１．４−ジオキサン８０ｍ１を仕込み、水素圧力２００
Ｋｇ／ｃｍ２．反応温度２５０℃の条件下で水素化還元
し、脂環式ジオール（−数式（ｒＶ）においてｎ＝１）
３４ｇを得た。該化合物のガスクロマトグラフィーによ
る選択率は７２モル％であった。Example 1 The 2:1 adduct obtained in Reference Example 1 (-n=1 in formula (III)) was placed in a 200 ml stirred autoclave.
, R = methyl group), 6 g of Adkins type copper chromite catalyst (trade name C-100, manufactured by Sakai Kagaku ■), 80 ml of 1,4-dioxane as a solvent, and a hydrogen pressure of 200.
Kg/cm2. Hydrogenation reduction is carried out at a reaction temperature of 250°C to produce an alicyclic diol (- n = 1 in the formula (rV))
34g was obtained. The selectivity of this compound by gas chromatography was 72 mol%.
実施例２
実施例１において２＝１付加物を参考例２で得られたも
のに代えた他は実施例１と同様に行い脂環式ジオール（
−数式（ｒｖ ）においてｎ＝１）３２ｇを得た。該化
合物のガスクロマトグラフィーによる選択率は８５モル
％であった。Example 2 The procedure of Example 1 was repeated except that the 2=1 adduct in Example 1 was replaced with that obtained in Reference Example 2, and the alicyclic diol (
- In the formula (rv), n=1) 32 g was obtained. The selectivity of this compound by gas chromatography was 85 mol%.
実施例３
実施例１において２：１付加物を参考例３で得られたも
のに代えた他は実施例１と同様に行い脂環式ジオール（
−数式（ｒｖ ）においてｎ＝１）３２ｇを得た。該化
合物のガスクロマトグラフィーによる選択率は８７モル
％であった。Example 3 The procedure of Example 1 was repeated except that the 2:1 adduct in Example 1 was replaced with that obtained in Reference Example 3, and the alicyclic diol (
- In the formula (rv), n=1) 32 g was obtained. The selectivity of this compound by gas chromatography was 87 mol%.
実施例４
実施例１において参考例１で得られた２・ｌ付加物を参
考例３で得られたｌ ｌ付加物に代え、反応温度を２１
０’Ｃに代えた他は実施例１と同様に行い脂環式ジオー
ル（−数式（ＩＩ））２９ｇを得た。該化合物のガスク
ロマトグラフィーによる選択率は９４モル％であった。Example 4 In Example 1, the 2·l adduct obtained in Reference Example 1 was replaced with the l·l adduct obtained in Reference Example 3, and the reaction temperature was set to 21
The same procedure as in Example 1 was carried out except that 0'C was used to obtain 29 g of an alicyclic diol (-formula (II)). The selectivity of this compound by gas chromatography was 94 mol%.
実施例５
実施例１において参考例１で得られた２：１付加物を参
考例３で得られた３：１付加物に代え、反応温度を２５
０℃に仕えた他は実施例１と同様に行い脂環式ジオール
（−数式（ｒｖ ）においてｎ＝２）１７ｇを得た。該
化合物のガスクロマトグラフィーによる選択率は７５モ
ル％であった。Example 5 In Example 1, the 2:1 adduct obtained in Reference Example 1 was replaced with the 3:1 adduct obtained in Reference Example 3, and the reaction temperature was set to 25
The procedure was carried out in the same manner as in Example 1 except that the temperature was maintained at 0° C. to obtain 17 g of an alicyclic diol (n=2 in the formula (rv)). The selectivity of this compound by gas chromatography was 75 mol%.
特許出願人 株式会社 り ラ し 荒川化学工業株式会社Patent applicant: RiRashi Co., Ltd. Arakawa Chemical Industry Co., Ltd.
Claims (1)
キル基を表す）で表される不飽和脂環式ジアルキルエス
テルを、アドキンス型銅クロマイト触媒を主成分とする
触媒の存在下で水素化還元することを特徴とする、一般
式（II）：▲数式、化学式、表等があります▼ で表される脂環式ジオールの製造方法。 ［２］一般式（III）： ▲数式、化学式、表等があります▼ （但し、一般式（III）中のＲは炭素数１〜１８のアル
キル基を表し、ｎは１または２を表す）で表される不飽
和脂環式ジアルキルエステルを、アドキンス型銅クロマ
イト触媒を主成分とする触媒の存在下で水素化還元する
ことを特徴とする、一般式（IV）： ▲数式、化学式、表等があります▼ （但し、一般式（IV）中のｎは１または２を表す）で表
される脂環式ジオールの製造方法。 ［３］前記一般式（ I ）または（III）で表される不飽
和脂環式ジアルキルエステルが、フマル酸ジアルキルエ
ステル及び／又はマレイン酸ジアルキルエステル１モル
部とジシクロペンタジエン１モル部未満とを反応させて
得られる化合物である請求項１または２記載の製造方法
。 ［４］前記一般式（III）で表される不飽和脂環式ジア
ルキルエステルが、前記一般式（ I ）で表される不飽
和脂環式ジアルキルエステルにジシクロペンタジエンを
反応せさて得られる化合物である請求項２または３記載
の製造方法。[Claims] [1] General formula (I): ▲There are numerical formulas, chemical formulas, tables, etc.▼ (However, R in general formula (I) represents an alkyl group having 1 to 18 carbon atoms) The general formula (II) is characterized by hydrogenating and reducing the unsaturated alicyclic dialkyl ester obtained by There is a method for producing an alicyclic diol represented by ▼. [2] General formula (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R in general formula (III) represents an alkyl group having 1 to 18 carbon atoms, and n represents 1 or 2) General formula (IV) characterized by hydrogenating and reducing an unsaturated alicyclic dialkyl ester represented by in the presence of a catalyst containing an Adkins type copper chromite catalyst as a main component: ▲Mathematical formula, chemical formula, table ▼ (However, n in general formula (IV) represents 1 or 2) A method for producing an alicyclic diol. [3] The unsaturated alicyclic dialkyl ester represented by the general formula (I) or (III) contains 1 mol part of fumaric acid dialkyl ester and/or maleic acid dialkyl ester and less than 1 mol part of dicyclopentadiene. The manufacturing method according to claim 1 or 2, which is a compound obtained by reaction. [4] A compound in which the unsaturated alicyclic dialkyl ester represented by the general formula (III) is obtained by reacting the unsaturated alicyclic dialkyl ester represented by the general formula (I) with dicyclopentadiene. The manufacturing method according to claim 2 or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2337369A JPH04208240A (en) | 1990-11-30 | 1990-11-30 | Production of alicyclic diol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2337369A JPH04208240A (en) | 1990-11-30 | 1990-11-30 | Production of alicyclic diol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04208240A true JPH04208240A (en) | 1992-07-29 |
Family
ID=18307975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2337369A Pending JPH04208240A (en) | 1990-11-30 | 1990-11-30 | Production of alicyclic diol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04208240A (en) |
-
1990
- 1990-11-30 JP JP2337369A patent/JPH04208240A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5198554A (en) | 5-(2,4-Dioxotetrahydro-3-furanylmethyl)norbornane-2,3-dicarboxylic acid anhydride and process for production thereof | |
| JP2002003474A (en) | Method of manufacturing piperidine | |
| JPH04208240A (en) | Production of alicyclic diol | |
| JPS58131979A (en) | Manufacture of phthalide | |
| US2794811A (en) | Production of cis-cyclohexane-1, 2-dicarboxylic anhydride | |
| JPH0236174A (en) | Production of 2, 2, 4-trimethyl-1, 2- dihydroquinoline oligomer | |
| JP3038271B2 (en) | Method for producing 3-aminopropanol | |
| JP3210148B2 (en) | Method for hydrogenating dialkyl naphthalenedicarboxylate | |
| US3403170A (en) | Process for the preparation of hexahydrophthalic acid and anhydride | |
| JPH03236372A (en) | Preparation of n-substituted pyrrolidone-2- one | |
| JPH0359887B2 (en) | ||
| US3742063A (en) | Dihydroxybutanones | |
| JP3031033B2 (en) | Method for producing trans-1,4-cyclohexanedimethanol | |
| JP2639496B2 (en) | Method for producing dimorpholino diethyl ether compound | |
| JPH0250101B2 (en) | ||
| JP2683809B2 (en) | Process for producing 1-benzyl-3-benzylaminopyrrolidines | |
| JP3841870B2 (en) | Method for producing alicyclic dicarboxylic acid derivative | |
| JPS63198645A (en) | Production of brassylic acid lower alkyl ester | |
| JP3178000B2 (en) | Method for producing aromatic polyhydric alcohol | |
| JPH0725797A (en) | Production of condensed ring-containing compound | |
| JPS6383033A (en) | Production of alkyltetralin | |
| JP2996713B2 (en) | Process for producing 2,3-cyclohexenopyridine | |
| US5473098A (en) | Process for the preparation of stilbenedicarboxylate esters | |
| JPS5934189B2 (en) | Method for producing diisobutenyl succinic anhydride | |
| JP2721554B2 (en) | Method for producing perhydro-1,4: 5,8-dimethanonaphthalene-2,3-dimethanol |