JPH07206740A - Novel alicyclic diol and method for producing the same - Google Patents
Novel alicyclic diol and method for producing the sameInfo
- Publication number
- JPH07206740A JPH07206740A JP267194A JP267194A JPH07206740A JP H07206740 A JPH07206740 A JP H07206740A JP 267194 A JP267194 A JP 267194A JP 267194 A JP267194 A JP 267194A JP H07206740 A JPH07206740 A JP H07206740A
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- JP
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- Prior art keywords
- tricyclo
- decane
- formula
- dicarboxylic acid
- alkyl
- 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.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は式〔１〕で表されるFIELD OF THE INVENTION The present invention is represented by the formula [1].
【０００２】[0002]
【化４】 [Chemical 4]
【０００３】新規脂環式ジオール及びその製造法に関す
る。式〔１〕で表される脂環式ジオールは高分子、特に
ポリエステルの原料として利用できる。The present invention relates to a novel alicyclic diol and a method for producing the same. The alicyclic diol represented by the formula [1] can be used as a raw material for polymers, particularly polyester.
【０００４】[0004]
【従来の技術】従来の脂環式ジオールとしては、ペルヒ
ドロ−１，４：５，８−ジメタナフタレン−８，９−ジ
メタノールをモノマーとするポリエステルがガラス転移
温度が高く、寸法安定性に優れ、写真用フィルムのベー
ス等に用いられることが知られている（米国防衛特許第
８９６０３３号）。しかし、そのジオールの製造収率は
低く、実用的な問題点を抱えていた。As a conventional alicyclic diol, polyester having perhydro-1,4: 5,8-dimetanaphthalene-8,9-dimethanol as a monomer has a high glass transition temperature and is dimensional stable. It is excellent and is known to be used as a base for photographic films (US Defense Patent No. 896033). However, the production yield of the diol was low, and it had a practical problem.
【０００５】本発明者らは、すでに工業的に安価なジシ
クロペンタジエンから高収率で、ノルボルナン骨格を有
するトリシクロ〔５．２．１．０2,6 〕デセ−３−エン
−８，９−ジカルボン酸誘導体を製造する方法を見出し
ている。（特公平４−６０１００，特公平２−３２２６
７，特公平５−２６７４） 即ち、以下の反応式で示すように安価な原料であるジシ
クロペンタジエン（ＤＣＰＤ）、一酸化炭素及びアルコ
ールを触媒及び酸化剤の存在下に反応させることによっ
て、高収率でトリシクロ〔５．２．１．０2,6 〕デセ−
３−エン−８，９−ジカルボン酸ジエステル（ＴＣＤ
Ｅ）を得ることができる。The present inventors have already obtained tricyclo [5.2.1.0 2,6 ] dece-3-ene-8, having a norbornane skeleton in high yield from industrially inexpensive dicyclopentadiene. A method for producing a 9-dicarboxylic acid derivative has been found. (Japanese Patent Publication 4-60100, Japanese Patent Publication 2-3226
7, Japanese Examined Patent Publication No. 5-2674) That is, as shown in the following reaction formula, by reacting dicyclopentadiene (DCPD), which is an inexpensive raw material, carbon monoxide and alcohol in the presence of a catalyst and an oxidizing agent, Tricyclo [5.2.1.0 2,6 ] dece
3-ene-8,9-dicarboxylic acid diester (TCD
E) can be obtained.
【０００６】又、このジエステル化反応に於て特定のア
ルコール、例えば第３級アルコール、アリルアルコー
ル、エチレングリコールを用いることによって一挙にジ
シクロペンタジエン（ＤＣＰＤ）よりトリシクロ〔５．
２．１．０2,6 〕デセ−３−エン−８，９−ジカルボン
酸無水物（ＴＣＤＡ）が得られる。ＴＣＤＥは、加水分
解することによってトリシクロ〔５．２．１．０2,6 〕
デセ−３−エン−８，９−ジカルボン酸（ＴＣＤＣ）が
得られる。ＴＣＤＣは、脱水することによってＴＣＤＡ
が得られる。又、ＴＣＤＣは、エステル化することによ
って種々のＴＣＤＥに誘導できる。In the diesterification reaction, a specific alcohol such as a tertiary alcohol, an allyl alcohol, or ethylene glycol is used to convert tricyclo [5.
2.1.0 2,6 ] Dec-3-ene-8,9-dicarboxylic acid anhydride (TCDA) is obtained. TCDE is hydrolyzed to give tricyclo [5.2.1.0 2,6 ].
Dece-3-ene-8,9-dicarboxylic acid (TCDC) is obtained. TCDC is dehydrated by TCDA
Is obtained. Also, TCDC can be induced into various TCDEs by esterification.
【０００７】[0007]
【化５】 [Chemical 5]
【０００８】更に本発明者らは特願平５−２０１４４９
号に於いて、上述のＴＣＤＥ、ＴＣＤＣ及びＴＣＤＡを
還元し同様に高収率でトリシクロ〔５．２．１．
０2,6 〕デカン−８，９−ジカルボン酸誘導体を得るこ
とを見出している。Further, the present inventors have filed Japanese Patent Application No. 5-201449.
In the same manner, the above TCDE, TCDC and TCDA were reduced to give tricyclo [5.2.1.
It has been found that a 0 2,6 ] decane-8,9-dicarboxylic acid derivative is obtained.
【０００９】[0009]
【化６】 [Chemical 6]
【００１０】[0010]
【発明が解決しようとする課題】本発明者らは先に述べ
た従来より公知の脂環式ジオールの製造における収率が
低いという実用的な問題点が無い、脂環式ジオールを見
出すことを課題とした。その結果、本発明者らは上述し
たＴＣＤＥ或いはＤＨ−ＴＣＤＥ等を用い、新規な脂環
式ジオールを高収率に得る方法を見出した。即ち、本発
明の目的はポリエステル樹脂等の原料として有用な新規
な脂環式ジオールを提供することにある。DISCLOSURE OF THE INVENTION The present inventors have found out an alicyclic diol which does not have the practical problem of low yield in the production of the previously known alicyclic diol described above. It was an issue. As a result, the present inventors have found a method for obtaining a novel alicyclic diol in high yield by using the above-mentioned TCDE or DH-TCDE. That is, an object of the present invention is to provide a novel alicyclic diol useful as a raw material for polyester resins and the like.
【００１１】[0011]
【課題を解決するための手段】即ち、本発明は、式
〔１〕で表されるThat is, the present invention is represented by the formula [1].
【００１２】[0012]
【化７】 [Chemical 7]
【００１３】８，９−ジヒドロキシメチル−トリシクロ
〔５．２．１．０2,6 〕デカンに関する。更に、式
〔２〕で表される化合物It relates to 8,9-dihydroxymethyl-tricyclo [5.2.1.0 2,6 ] decane. Furthermore, the compound represented by the formula [2]
【００１４】[0014]
【化８】 [Chemical 8]
【００１５】（Ａは、−ＯＨ基、−ＯＲ基（Ｒはアルキ
ル基、不飽和アルキル基、シクロアルキル基、ベンゼン
置換アルキル、ベンゼン置換不飽和アルキルでアルキル
及び不飽和アルキルはＯ，Ｎ原子を含んでいてよい。）
又は、一緒になって＞Ｏ（酸素原子）を表す。） トリシクロ〔５．２．１．０2,6 〕デセ−３−エン−
８，９−ジカルボン酸誘導体、又は式〔３〕で表される
トリシクロ〔５．２．１．０2,6 〕デカン−８，９−ジ
カルボン酸誘導体を還元することを特徴とする上記式
〔１〕で表される８，９−ジヒドロキシメチル−トリシ
クロ〔５．２．１．０2,6 〕デカンの製造法に関する。(A is an -OH group, -OR group (R is an alkyl group, an unsaturated alkyl group, a cycloalkyl group, a benzene-substituted alkyl, a benzene-substituted unsaturated alkyl, and an alkyl and an unsaturated alkyl are O and N atoms. May be included.)
Alternatively, they together represent> O (oxygen atom). ) Tricyclo [5.2.1.0 2,6 ] dece-3-ene-
An 8,9-dicarboxylic acid derivative or the above formula [3] wherein the tricyclo [5.2.1.0 2,6 ] decane-8,9-dicarboxylic acid derivative represented by the formula [3] is reduced. 1] and a method for producing 8,9-dihydroxymethyl-tricyclo [5.2.1.0 2,6 ] decane.
【００１６】以下、本発明をさらに詳細に説明する。本
発明に用いられる原料としては、先に述べたジシクロペ
ンタジエン（ＤＣＰＤ）をジエステル化反応によって得
られるトリシクロ〔５．２．１．０2,6 〕デセ−３−エ
ン−８，９−ジカルボン酸ジエステル、そのジエステル
を加水分解によって得られるトリシクロ〔５．２．１．
０2,6 〕デセ−３−エン−８，９−ジカルボン酸、前記
カルボン酸の酸ハライドであるトリシクロ〔５．２．
１．０2,6 〕デセ−３−エン−８，９−ジカルボン酸ハ
ライド、或いは前記ジカルボン酸を脱水して得られるト
リシクロ〔５．２．１．０2,6 〕デセ−３−エン−８，
９−ジカルボン酸無水物、さらにこれらの化合物の水素
化物であるトリシクロ〔５．２．１．０2,6 〕デカン−
８，９−ジカルボン酸ジエステル、トリシクロ〔５．
２．１．０2,6 〕デカン−８，９−ジカルボン酸ハライ
ド及びトリシクロ〔５．２．１．０2,6 〕デカン−８，
９−ジカルボン酸無水物が挙げられる。The present invention will be described in more detail below. As a raw material used in the present invention, tricyclo [5.2.1.0 2,6 ] dece-3-ene-8,9-obtained by diesterification reaction of dicyclopentadiene (DCPD) described above is used. Dicarboxylic acid diester, tricyclo [5.2.1.
0 2,6 ] Dec-3-ene-8,9-dicarboxylic acid, and tricyclo [5.2.
1.0 2,6 ] Dec-3-ene-8,9-dicarboxylic acid halide or tricyclo [5.2.1.0 2,6 ] dece-3-obtained by dehydrating the dicarboxylic acid. EN-8,
9-dicarboxylic acid anhydride and tricyclo [5.2.1.0 2,6 ] decane-which are hydrides of these compounds.
8,9-dicarboxylic acid diester, tricyclo [5.
2.1.0 2,6 ] decane-8,9-dicarboxylic acid halide and tricyclo [5.2.1.0 2,6 ] decane-8,
9-dicarboxylic acid anhydride is mentioned.
【００１７】次に、本発明に適用できる還元方法として
は、以下に述べる還元方法が適用出来る。 （１）金属水素化物を用いる方法 金属水素化物としては、ＡｌＨ3 、ＬｉＡｌＨ4 、Ｌｉ
ＡｌＨ4 −ＡｌＣｌ3、ＬｉＡｌＨ（ＯＣＨ3 ）3 、Ｎ
ａＡｌＨ2 （ＯＣＨ2 ＣＨ2 ＯＣＨ3 ）3 、ＡｌＨ（ｎ
−Ｃ4 Ｈ9 ）2 、ＡｌＨ（ｉ−Ｃ4 Ｈ9 ）2 、ＢＨ3 、
ＮａＢＨ4 、ＮａＢＨ4 −ＡｌＣｌ3 及びＮａＢＨ（Ｏ
ＣＨ3 ）3 等が挙げられる。 （２）接触水素化法 触媒としては、銅クロマイト、酸化レニウム、酸化ロジ
ウム、パラジウム、ニッケル、ルテニウム及びクロム等
が挙げられる。 （３）ナトリウム還元法 アルコールの存在下にナトリウムにより還元する方法。 （４）電解還元法 カルボン酸は電解還元法によりアルコールを合成するこ
とができる。Next, as a reduction method applicable to the present invention, the reduction method described below can be applied. (1) Method using metal hydride As the metal hydride, AlH 3 , LiAlH 4 , Li
AlH 4 -AlCl 3, LiAlH (OCH 3) 3, N
aAlH 2 (OCH 2 CH 2 OCH 3 ) 3 , AlH (n
-C 4 H 9) 2, AlH (i-C 4 H 9) 2, BH 3,
NaBH 4 , NaBH 4 -AlCl 3 and NaBH (O
CH 3 ) 3 and the like. (2) Catalytic hydrogenation method Examples of the catalyst include copper chromite, rhenium oxide, rhodium oxide, palladium, nickel, ruthenium and chromium. (3) Sodium reduction method A method of reducing with sodium in the presence of alcohol. (4) Electrolytic reduction method Carboxylic acid can synthesize alcohol by electrolytic reduction method.
【００１８】金属水素化物を用いる場合は、通常行われ
る方法が適用できる。金属水素化物の使用量は基質に対
して金属水素化物を理論量に対し０．５〜１．５倍量用
いる。反応は、ヘキサン、トルエン、テトラヒドロフラ
ン、ジオキサン等を溶媒として用い、−４０℃から５０
℃、好ましくは氷冷下から室温の温度範囲で行う。工業
的な方法としては、触媒の存在下に水素による接触還元
法が好ましく、触媒としては銅クロマイト触媒が一般的
であり、他の金属、例えばパラジウム、ルテニウム及び
ロジウム等を含む触媒系も有効である。When a metal hydride is used, a commonly used method can be applied. The amount of metal hydride used is 0.5 to 1.5 times the theoretical amount of metal hydride with respect to the substrate. The reaction uses hexane, toluene, tetrahydrofuran, dioxane or the like as a solvent, and the temperature is from -40 ° C to 50 ° C.
C., preferably under ice-cooling to room temperature. As an industrial method, a catalytic reduction method using hydrogen in the presence of a catalyst is preferable, a copper chromite catalyst is generally used as a catalyst, and a catalyst system containing other metals such as palladium, ruthenium and rhodium is also effective. is there.
【００１９】上記触媒を用いる水素による接触還元反応
は、１００〜３００℃の範囲、好ましくは１５０〜２５
０℃の範囲で、水素圧力は４０，０００ｋＰａ以下、好
ましくは５，０００〜３５，０００ｋＰａの範囲であ
る。反応時間は、温度、水素圧の条件により異なるが、
２０分〜５０時間の範囲で、好ましいくは３０分〜１０
時間の範囲である。The catalytic reduction reaction with hydrogen using the above catalyst is in the range of 100 to 300 ° C., preferably 150 to 25.
In the range of 0 ° C., the hydrogen pressure is 40,000 kPa or less, preferably 5,000 to 35,000 kPa. The reaction time varies depending on the temperature and hydrogen pressure conditions,
20 minutes to 50 hours, preferably 30 minutes to 10 hours
It is a range of time.
【００２０】また、接触還元反応は原料を溶解し、触媒
との分離が容易で、反応に関与しない有機溶媒を用いる
ことが好ましい。有機溶媒としては、ジオキサン、テト
ラヒドロフラン及び１，２−ジメトキシエタン等のエー
テル類、シクロヘキサンやヘプタン等の炭化水素類、メ
タノール、エタノール等のアルコール類等が挙げられ
る。触媒の使用量は、基質に対し１〜３０重量％、好ま
しくは３〜２０重量％である。In the catalytic reduction reaction, it is preferable to use an organic solvent that dissolves the raw materials, is easy to separate from the catalyst, and does not participate in the reaction. Examples of the organic solvent include ethers such as dioxane, tetrahydrofuran and 1,2-dimethoxyethane, hydrocarbons such as cyclohexane and heptane, alcohols such as methanol and ethanol. The amount of the catalyst used is 1 to 30% by weight, preferably 3 to 20% by weight, based on the substrate.
【００２１】以下、実施例により本発明をさらに具体的
に説明するが本発明はこれらによって限定されるもので
はない。Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
【００２２】[0022]
実施例１ テトラヒドロフラン（ＴＨＦ）３０ｍｌ中に氷冷下、リ
チウムアルミニウムハイドライド１．０ｇ（２６ｍｍｏ
ｌ）を懸濁させた。その攪拌液へ、トリシクロ〔５．
２．１．０2,6 〕デカン−８，９−ジカルボン酸ジメチ
ルエステル５．０ｇ（２０ｍｍｏｌ）をＴＨＦ２０ｍｌ
に溶解した溶液を１０℃以下で滴下した。その後ゆっく
り室温に戻し、２５℃で３時間攪拌を行った。反応終了
後再び氷冷し、６Ｎ塩酸１２ｍｌを注意深く滴下した。
続いてろ過により残査を除去した後、ろ液に酢酸エチル
を加え抽出した。この溶液を水洗後、無水芒硝で脱水し
た後、濃縮乾燥すると純白結晶３．４ｇが得られた。こ
の結晶をガスクロマトグラフィーで分析の結果単一のピ
ークであった。Example 1 1.0 g (26 mmo of lithium aluminum hydride in 30 ml of tetrahydrofuran (THF) under ice cooling.
l) was suspended. To the stirring liquid, tricyclo [5.
2.1.0 2,6 ] decane-8,9-dicarboxylic acid dimethyl ester 5.0 g (20 mmol) was added to THF 20 ml.
The solution dissolved in was added dropwise at 10 ° C or lower. Thereafter, the temperature was slowly returned to room temperature, and the mixture was stirred at 25 ° C for 3 hours. After completion of the reaction, the mixture was ice-cooled again, and 12 ml of 6N hydrochloric acid was carefully added dropwise.
Subsequently, the residue was removed by filtration, and ethyl acetate was added to the filtrate for extraction. This solution was washed with water, dehydrated with anhydrous sodium sulfate, and concentrated and dried to obtain 3.4 g of pure white crystals. The crystals were analyzed by gas chromatography and found to have a single peak.
【００２３】更に以下の分析を行った。 マススペクトル（ｍ／ｅ（％））：１９７〔Ｍ＋Ｈ〕+
（７７）、１７７（９１）、１６１（１００）1 Ｈ−ＮＭＲ（ＣＤＣｌ3 ）：４．０６、３．７９、
３．７７、３．７５、３．５５、３．５４、３．５３、
３．５２、２．３７、２．２２、２．２０、１．８４、
１．６５、１．６４、１．６２、１．６０、１．５７、
１．４８、１．４６、１．３１、１．２９13 Ｃ−ＮＭＲ（ＣＤＣｌ3 ）：７７．３、７７．０、７
６．８、６４．４、４５．７、４１．１、３９．７、２
９．０、２６．７ 融点： １１５〜１１７℃ 以上から本結晶は、目的とする８，９−ジヒドロキシメ
チル−トリシクロ〔５．２．１．０2,6 〕デカンである
ことが判明した。 実施例２ トリシクロ〔５．２．１．０2,6 〕デカン−８，９−ジ
カルボン酸ジメチルエステル５．０ｇ（２０ｍｍｏ
ｌ）、銅クロマイト触媒０．５ｇとジオキサン５０ｍｌ
を１００ｍｌのオートクレーブに仕込み、窒素置換後水
素圧を２００００ｋＰａにし反応温度２００℃で４時間
攪拌を行った。Further, the following analysis was conducted. Mass spectrum (m / e (%)): 197 [M + H] +
(77), 177 (91), 161 (100) 1 H-NMR (CDCl 3 ): 4.06, 3.79,
3.77, 3.75, 3.55, 3.54, 3.53,
3.52, 2.37, 2.22, 2.20, 1.84,
1.65, 1.64, 1.62, 1.60, 1.57,
1.48, 1.46, 1.31, 1.29 13 C-NMR (CDCl 3 ): 77.3, 77.0, 7
6.8, 64.4, 45.7, 41.1, 39.7, 2
9.0, 26.7 Melting point: 115-117 ° C From the above, it was found that the present crystal was the target 8,9-dihydroxymethyl-tricyclo [5.2.1.0 2,6 ] decane. Example 2 5.0 g (20 mmo) of tricyclo [5.2.1.0 2,6 ] decane-8,9-dicarboxylic acid dimethyl ester
l), 0.5 g of copper chromite catalyst and 50 ml of dioxane
Was charged into a 100 ml autoclave, the atmosphere was replaced with nitrogen, the hydrogen pressure was adjusted to 20000 kPa, and the mixture was stirred at a reaction temperature of 200 ° C. for 4 hours.
【００２４】冷却後、ろ過により触媒を除去し、そのろ
液を濃縮、乾燥すると粗結晶３．３ｇが得られた。この
結晶をガスクロマトグラフィーで分析の結果、純度９
６．８％の目的とする８，９−ジヒドロキシメチル−ト
リシクロ〔５．２．１．０2,6〕デカンの結晶であるこ
とが判った。After cooling, the catalyst was removed by filtration, and the filtrate was concentrated and dried to obtain 3.3 g of crude crystals. The crystals were analyzed by gas chromatography and found to have a purity of 9
It was found to be 6.8% crystals of the target 8,9-dihydroxymethyl-tricyclo [5.2.1.0 2,6 ] decane.
【図１】 実施例１で得られた８，９−ジヒドロキシメ
チル−トリシクロ〔５．２．１．０2,6 〕デカンの 1Ｈ
−ＮＭＲによるチャート 1 H of 8,9-dihydroxymethyl-tricyclo [5.2.1.0 2,6 ] decane obtained in Example 1
-NMR chart
【図２】 実施例１で得られた８，９−ジヒドロキシメ
チル−トリシクロ〔５．２．１．０2,6 〕デカンの13Ｃ
−ＮＭＲによるチャート[2] obtained in Example 1 8,9-dihydroxy methyl - tricyclo [5.2.1.0 2,6] decane 13 C
-NMR chart
Claims (2)
１．０2,6 〕デカン。1. A compound represented by the formula [1]: 8,9-Dihydroxymethyl-tricyclo [5.2.
1.0 2,6 ] decane.
アルキル基、シクロアルキル基、ベンゼン置換アルキ
ル、ベンゼン置換不飽和アルキルでアルキル及び不飽和
アルキルはＯ，Ｎ原子を含んでいてよい。）又は、一緒
になって＞Ｏ（酸素原子）を表す。） トリシクロ〔５．２．１．０2,6 〕デセ−３−エン−
８，９−ジカルボン酸誘導体、又は式〔３〕で表される 【化３】 （Ａは前記と同じ） トリシクロ〔５．２．１．０2,6 〕デカン−８，９−ジ
カルボン酸誘導体を還元することを特徴とする請求項１
記載の式〔１〕で表される８，９−ジヒドロキシメチル
−トリシクロ〔５．２．１．０2,6 〕デカンの製造法2. A compound represented by the formula [2]: (A is -OH group, -OR group (R is an alkyl group, an unsaturated alkyl group, a cycloalkyl group, a benzene-substituted alkyl, a benzene-substituted unsaturated alkyl, and the alkyl and the unsaturated alkyl include O and N atoms. Or together they represent> O (oxygen atom).) Tricyclo [5.2.1.0 2,6 ] dece-3-ene-
8,9-dicarboxylic acid derivative or a compound represented by the formula [3]: (A is the same as above) Tricyclo [5.2.1.0 2,6 ] decane-8,9-dicarboxylic acid derivative is reduced.
Process for producing 8,9-dihydroxymethyl-tricyclo [5.2.1.0 2,6 ] decane represented by the above formula [1]
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00267194A JP3844789B2 (en) | 1994-01-14 | 1994-01-14 | Novel alicyclic diol and process for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00267194A JP3844789B2 (en) | 1994-01-14 | 1994-01-14 | Novel alicyclic diol and process for producing the same |
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| Publication Number | Publication Date |
|---|---|
| JPH07206740A true JPH07206740A (en) | 1995-08-08 |
| JP3844789B2 JP3844789B2 (en) | 2006-11-15 |
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ID=11535783
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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