JPS6150936B2 - - Google Patents
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- Publication number
- JPS6150936B2 JPS6150936B2 JP20332883A JP20332883A JPS6150936B2 JP S6150936 B2 JPS6150936 B2 JP S6150936B2 JP 20332883 A JP20332883 A JP 20332883A JP 20332883 A JP20332883 A JP 20332883A JP S6150936 B2 JPS6150936 B2 JP S6150936B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- ester
- acid
- methylene
- general formula
- 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
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- 150000002148 esters Chemical class 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000004494 ethyl ester group Chemical group 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- -1 dicarboxylic acid monomethyl ester Chemical class 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ACXGEQOZKSSXKV-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O.CCCCCCCC(O)=O ACXGEQOZKSSXKV-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ADHNUPOJJCKWRT-JLXBFWJWSA-N (2e,4e)-octadeca-2,4-dienoic acid Chemical compound CCCCCCCCCCCCC\C=C\C=C\C(O)=O ADHNUPOJJCKWRT-JLXBFWJWSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は次の一般式で表わされるシクロヘキサ
ン環をもつジヒドロキシジカルボン酸及びジヒド
ロキシジカルボン酸エステルに関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to dihydroxydicarboxylic acids and dihydroxydicarboxylic acid esters having a cyclohexane ring represented by the following general formula.
一般式
（式中のｎ、n′は４〜10の数、Ｒ及びR′は水素原
子又は炭素数１〜４のアルキル基をそれぞれ示
す。またシクロヘキサン環に結合するCOOR′の
結合位置はシクロヘキサン環の２あるいは３位炭
素。）
従来、ヒドロキシカルボン酸又はそのエステル
としては直鎖カルボン酸の炭素鎖にヒドロキシル
基が結合した直鎖カルボン酸の誘導体が広く知ら
れている。一方、分子内に環式構造をもつポリカ
ルボン酸又はそのエステルとしては、リノール
酸、リシノール酸などを出発原料として合成され
たシクロヘキセン環をもつジカルボン酸やトリカ
ルボン酸及びそのエステルなどが良く知られてい
る。しかしながら上記の一般式で表わされるよう
なシクロヘキサン環及びヒドロキシ基をもつジカ
ルボン酸又はそのエステルは未だ明らかにされて
いない。 general formula (In the formula, n and n' are numbers from 4 to 10, R and R' each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Also, the bonding position of COOR' bonded to the cyclohexane ring is 2- or 3-position carbon.) Conventionally, derivatives of linear carboxylic acids in which a hydroxyl group is bonded to the carbon chain of linear carboxylic acids are widely known as hydroxycarboxylic acids or esters thereof. On the other hand, as polycarboxylic acids or their esters having a cyclic structure in the molecule, dicarboxylic acids and tricarboxylic acids and their esters having a cyclohexene ring synthesized from linoleic acid, ricinoleic acid, etc. as starting materials are well known. There is. However, a dicarboxylic acid having a cyclohexane ring and a hydroxyl group as represented by the above general formula or an ester thereof has not yet been clarified.
そのため本発明者らは該化合物の合成に関し検
討を加えた結果、既に明らかにされているシクロ
ヘキセン環をもつジカルボン酸又はそのエステル
を原料とし、これを公知の過酸化水素や過マンガ
ン酸カリ酸化法により処理し容易にシクロヘキサ
ン環をもつジヒドロキシジカルボン酸及びそのエ
ステルを得た。 Therefore, the present inventors investigated the synthesis of the compound, and found that using dicarboxylic acid or its ester having a cyclohexene ring, which has already been revealed, as a raw material, using the known hydrogen peroxide or potassium permanganate oxidation method. Dihydroxydicarboxylic acid having a cyclohexane ring and its ester were easily obtained.
本発明における化合物は上記の一般式で明らか
なように分子中央にシクロヘキサン環が存在し、
シクロヘキサン環のメチレン基の水素原子がヒド
ロキシル基、カルボキシル基、長鎖アルキル基な
どにより置換された極めて極性の大きい管能基性
化合物である。従つて本発明によるこの化合物は
合成樹脂原料、界面活性剤、有機反応素材などに
対して有要な用途がある。 As is clear from the above general formula, the compound in the present invention has a cyclohexane ring in the center of the molecule,
It is an extremely polar functional compound in which the hydrogen atom of the methylene group of the cyclohexane ring is substituted with a hydroxyl group, carboxyl group, long-chain alkyl group, etc. Therefore, this compound according to the present invention has important uses as raw materials for synthetic resins, surfactants, organic reaction materials, etc.
本発明において用いられる原料はシクロヘキセ
ン環をもつ脂肪酸誘導体で次の一般式に示す構造
をもつものである。 The raw material used in the present invention is a fatty acid derivative having a cyclohexene ring and has the structure shown in the following general formula.
一般式
（式中のｎ、n′は４〜10、Ｒ及びR′は水素原子又
は炭素数１〜４のアルキル基をそれぞれ示す。ま
たシクロヘキセン環に結合するCOOR′の結合位
置はシクロヘキセン環の２あるいは３位炭素。）
この一般式に示される分子構造をもつシクロヘ
キセン環をもつ脂肪酸誘導体は従来、共役オクタ
デカジエン酸或いはそのエステルへのアクリル酸
或いはアクリル酸エステルのDiels−Alder付加に
より合成されているが他の方法により合成された
誘導体も本法の原料として適用される。なおこの
誘導体におけるｎ、n′はともに４〜10のものが適
合するが通常は４〜７のものが多く用いられる。
またアルキル基のＲ及びR′はその炭素数が同じ
ものでも異なつたものでもよい。なおこのシクロ
ヘキセン環をもつ脂肪酸誘導体はその一般式に於
いて示したように、シクロヘキセン環に結合する
COOR′の結合位置の違いにより２種の異性体が
存在するがヒドロキシル化の原料としては、それ
ぞれ異性体の単独のものでもまた混合したもので
もよい。 general formula (In the formula, n and n' are 4 to 10, and R and R' each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Also, the bonding position of COOR' bonded to the cyclohexene ring is 2 or 2 of the cyclohexene ring. 3-position carbon.) Fatty acid derivatives having a cyclohexene ring and having the molecular structure shown in this general formula have conventionally been synthesized by Diels-Alder addition of acrylic acid or acrylic acid ester to conjugated octadecadienoic acid or its ester. However, derivatives synthesized by other methods can also be used as raw materials in this method. In this derivative, n and n' are both preferably 4 to 10, but 4 to 7 are usually used.
Further, R and R' of the alkyl group may have the same or different carbon numbers. As shown in the general formula, this fatty acid derivative with a cyclohexene ring is bonded to the cyclohexene ring.
Two types of isomers exist depending on the bonding position of COOR', and the raw material for hydroxylation may be either a single isomer or a mixture thereof.
以下実施例につき説明する。なお実施例に於け
る原料はさきの一般式で表わされる構造のシクロ
ヘキセン環を有する脂肪酸誘導体であるが式中の
ｎ、n′及びＲ、R′については、それぞれの実施例
中に示した。 Examples will be explained below. The raw material used in the examples is a fatty acid derivative having a cyclohexene ring having the structure represented by the general formula shown above, and n, n', R, and R' in the formula are shown in each example.
実施例 １
原料（ｎ＝５、n′＝７、Ｒ及びR′＝CH3）の
7.55ｇをギ酸50mlとともに100ml丸底フラスコに
秤取し、これを24−25℃に保ちながら撹拌下、過
酸化水素溶液（29.6W/V%）の３mlを10分間にわ
たり滴下した。適下後、約30分撹拌を続けた後反
応温度を40℃に上げ3.5時間反応を行つた。反応
後、反応液を水中にあけ分離した反応生成物をエ
ーテルで抽出した。抽出物は次にアルカリ溶液
（NaOH5ｇ／H2O70ml）とともに95〜100℃で2.5
時間還流し、けん化を行つた。ケン化後、生成し
たセツケンを塩酸（１：１）で分解し遊離したヒ
ドロキシ酸をエーテルで抽出した。このエーテル
抽出物は7.65ｇ（収率99.6％）得られ、この構造
検討の分析結果は次のとおりであつた。中和価：
28.90（理論値290.3）、ヒドロキシル価：291.7
（理論値290.3）、IRスペクトル（cm-1）：3200−
3600（ヒドロキシル基）1720（カルボニル基）、
1H−NMRスペクトル（ppm）：0.89（末端メチ
ル基）、1.32（メチレン基）、2.27（カルボキシル
基のα−メチレン基、3.5（ヒドロキシル基の置
換したメチレン基）。13C−NMRスペクトル
（ppm）：14.2（末端メチル基）、23.4〜32.7（メ
チレン基）34.2（カルボキシル基のα−メチレン
基）、82.1（ヒドロキシル基に置換されたメチレ
ン基）、175.7〜177.6（カルボキシル基）。Example 1 Raw materials (n=5, n'=7, R and R'=CH 3 )
7.55 g was weighed into a 100 ml round bottom flask along with 50 ml of formic acid, and 3 ml of hydrogen peroxide solution (29.6 W/V%) was added dropwise over 10 minutes while stirring while maintaining the temperature at 24-25°C. After the addition, stirring was continued for about 30 minutes, and then the reaction temperature was raised to 40°C, and the reaction was carried out for 3.5 hours. After the reaction, the reaction solution was poured into water and the separated reaction product was extracted with ether. The extract was then incubated with alkaline solution (5 g NaOH/70 ml H 2 O) at 95-100 °C for 2.5
The mixture was refluxed for a period of time to perform saponification. After saponification, the produced ester was decomposed with hydrochloric acid (1:1) and the liberated hydroxy acid was extracted with ether. 7.65 g (yield: 99.6%) of this ether extract was obtained, and the analysis results of this structural study were as follows. Neutralization value:
28.90 (theoretical value 290.3), hydroxyl number: 291.7
(Theoretical value 290.3), IR spectrum (cm -1 ): 3200−
3600 (hydroxyl group) 1720 (carbonyl group),
1 H-NMR spectrum (ppm): 0.89 (terminal methyl group), 1.32 (methylene group), 2.27 (α-methylene group of carboxyl group, 3.5 (methylene group substituted with hydroxyl group). 13 C-NMR spectrum (ppm) ): 14.2 (terminal methyl group), 23.4 to 32.7 (methylene group), 34.2 (α-methylene group of carboxyl group), 82.1 (methylene group substituted with hydroxyl group), 175.7 to 177.6 (carboxyl group).
以上の結果から反応生成物は次の構成をもつ８
−〔２（または３）−カルボキシ−４−ヘキシル−
５・６−ジヒドロキシ−１−シクロヘキシル〕オ
クタン酸であることを確認した。 From the above results, the reaction product has the following structure8
-[2 (or 3)-carboxy-4-hexyl-
It was confirmed that it was 5,6-dihydroxy-1-cyclohexyl]octanoic acid.
また、この酸の2.50ｇを常法によりメチルエス
テル化しエステルを製取（2.64ｇ、収率98.5％）
した。このエステルの分析値はエステル価268.5
（理論値270.7）、ヒドロキシル価：266.7（理論値
270.7）、IRスペクトル（cm-1）：3200〜3600（ヒ
ドロキシル基）、1740（メチルエステル）、1H−
NMRスペクトル（ppm）：0.90（メチル基）、
1.30（メチレン基）、2.20〜2.40（エステルのα−
メチレン基）、3.50（ヒドロキシル基の置換した
メチレン基）、3.70（メチルエステル）を示し上
記の酸のジメチルエステル（次式）の生成を認め
た。 In addition, 2.50 g of this acid was methyl esterified using a conventional method to produce ester (2.64 g, yield 98.5%).
did. The analytical value of this ester is ester value 268.5
(Theoretical value 270.7), Hydroxyl number: 266.7 (Theoretical value
270.7), IR spectrum (cm -1 ): 3200-3600 (hydroxyl group), 1740 (methyl ester), 1 H-
NMR spectrum (ppm): 0.90 (methyl group),
1.30 (methylene group), 2.20-2.40 (ester α-
methylene group), 3.50 (methylene group substituted with hydroxyl group), and 3.70 (methyl ester), and formation of dimethyl ester (the following formula) of the above acid was observed.
さらに、さきに得られた酸の2.50ｇを常法によ
りエチルエステル化し次のジエチルエステルを得
た（2.64ｇ収率99.0％）。 Furthermore, 2.50 g of the acid obtained earlier was ethyl esterified by a conventional method to obtain the following diethyl ester (2.64 g, yield 99.0%).
なおこのものの分析値は次のとおりであつた。
エステル価：248.2（理論値253.5）、ヒドロキシ
ル価：248.5（理論値253.5）、IRスペクトル
（cm-1）：3200〜3600（ヒドロキシル基）、1740
（エチルエステル）、1H−NMRスペクトル
（ppm）：4.00〜4.30（エチルエステル）、他の吸
収は上記のジメチルエステルと同様であつた。 The analytical values for this product were as follows.
Ester value: 248.2 (theoretical value 253.5), hydroxyl value: 248.5 (theoretical value 253.5), IR spectrum (cm -1 ): 3200-3600 (hydroxyl group), 1740
(ethyl ester), 1 H-NMR spectrum (ppm): 4.00-4.30 (ethyl ester), other absorptions were similar to the above dimethyl ester.
実施例 ２
原料（ｎ＝５、n′＝７、Ｒ＝C2H5、R′＝Ｈ）
の5.60ｇとテトラブチルアンモニウムブロマイド
0.25ｇをメチレンクロライド80mlに溶し、これを
０℃に保ち撹拌しながら過マンガン酸カリのアル
カリ溶液（過マンガン酸カリ7.0ｇ／20wt％苛性
ソーダ水溶液200ml）を滴下し約７時間反応（撹
拌）を行つた。次に過剰の酸性亜硫酸ソーダ水溶
液を反応液に加えた後、6N塩酸で酸性とし生じ
た油状物と水溶液を分離、油状物は蒸留し混在す
るメチレンクロライドを除いた。この残留物は更
にエーテルに溶し水洗、エーテルを留去し反応生
成物を得た（5.70ｇ、収率93.4％）。この反応生
成物の分析結果は次のとおりであつた。中和価：
133.5（理論値135.3）、ヒドロキシル価：272.2
（理論値270.7）、IRスペクトル（cm-1）：3200〜
3600（ヒドロキシル基）、1720（カルボキシル
基）、1740（エチルエステル）1H−NMRスペクト
ル（ppm）：0.89（メチル基）、1.28〜1.30（メ
チレン基）、2.32〜2.40（カルボキシル基及びエ
ステル基のα−メチレン）、3.60（シドロキシル
基の置換したメチレン）、4.20（エチルエステ
ル）、11.10（カルボキシル基）。したがつて此の
反応生成物は８−〔２（または３）−カルボキシ−
４−ヘキシル−５・６−ジヒドロキシ−１−シク
ロヘキシル〕オクタン酸エチルであることを認め
た。 Example 2 Raw materials (n=5, n'=7, R=C 2 H 5 , R'=H)
5.60g of and tetrabutylammonium bromide
Dissolve 0.25 g in 80 ml of methylene chloride, and while stirring while keeping the solution at 0°C, add dropwise an alkaline solution of potassium permanganate (7.0 g of potassium permanganate/200 ml of 20 wt% aqueous solution of caustic soda) and react for about 7 hours (stirring). I went to Next, an excess of acidic sodium sulfite aqueous solution was added to the reaction solution, which was then acidified with 6N hydrochloric acid to separate the resulting oily substance and aqueous solution, and the oily substance was distilled to remove the mixed methylene chloride. This residue was further dissolved in ether, washed with water, and the ether was distilled off to obtain a reaction product (5.70 g, yield 93.4%). The analysis results of this reaction product were as follows. Neutralization value:
133.5 (theoretical value 135.3), hydroxyl number: 272.2
(Theoretical value 270.7), IR spectrum (cm -1 ): 3200 ~
3600 (hydroxyl group), 1720 (carboxyl group), 1740 (ethyl ester) 1 H-NMR spectrum (ppm): 0.89 (methyl group), 1.28-1.30 (methylene group), 2.32-2.40 (carboxyl group and ester group) α-methylene), 3.60 (methylene substituted with cidroxyl group), 4.20 (ethyl ester), 11.10 (carboxyl group). Therefore, this reaction product is 8-[2(or 3)-carboxy-
It was confirmed that it was ethyl 4-hexyl-5,6-dihydroxy-1-cyclohexyl]octoate.
実施例 ３
原料（ｎ＝５、n′＝７、Ｒ＝H′、R′＝CH3）の
5.0ｇを実施例２と同様に処理し、反応生成物と
して次の構造をもつジカルボン酸のモノメチルエ
ステル4.88ｇ（収率89.3％）を得た。 Example 3 Raw materials (n=5, n'=7, R=H', R'=CH 3 )
5.0 g was treated in the same manner as in Example 2 to obtain 4.88 g (yield: 89.3%) of dicarboxylic acid monomethyl ester having the following structure as a reaction product.
なおこのものの分析値は次のとおりであつた中
和価：134.2（理論値140.1）、ヒドロキシル価：
273.4（理論値280.2）、IRスペクトル（cm-1）：
3200〜3600（ヒドロキシル基）、1720（カルボキ
シル基）、1740（エチルエステル）、1H−NMRス
ペクトル（ppm）：0.89（メチル基）、1.30（メ
チレン基）、2.30〜2.40（カルボキシル基及びエ
ステルのα−メチレン）、3.60（ヒドロキシル基
の置換したメチレン）、3.70（メチルエステル）、
10.50（カルボキシル基）。 The analytical values for this product were as follows: Neutralization number: 134.2 (theoretical value 140.1), Hydroxyl number:
273.4 (theoretical value 280.2), IR spectrum (cm -1 ):
3200-3600 (hydroxyl group), 1720 (carboxyl group), 1740 (ethyl ester), 1H -NMR spectrum (ppm): 0.89 (methyl group), 1.30 (methylene group), 2.30-2.40 (carboxyl group and ester) α-methylene), 3.60 (hydroxyl-substituted methylene), 3.70 (methyl ester),
10.50 (carboxyl group).
８−〔２（または３）−カルボメトキシ−４−ヘ
キシル−５・６−ジヒドロキシ−１−シクロヘキ
シル〕オクタン酸。 8-[2(or 3)-carbomethoxy-4-hexyl-5,6-dihydroxy-1-cyclohexyl]octanoic acid.
Claims (1)
子又は炭素数１〜４のアルキル基をそれぞれ示
す。またシクロヘキサン環に結合するCOOR′の
結合位置はシクロヘキサン環の２あるいは３位炭
素。）で表されるシクロヘキサン環をもつジヒド
ロキシジカルボン酸及びそのエステル。[Claims] 1. General formula (In the formula, n and n' are numbers from 4 to 10, and R and R' each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Also, the bonding position of COOR' bonded to the cyclohexane ring is Dihydroxydicarboxylic acid and its ester having a cyclohexane ring represented by carbon number 2 or 3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20332883A JPS6094937A (en) | 1983-10-28 | 1983-10-28 | Dihydroxydicarboxylic acid having cyclohexane ring and its ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20332883A JPS6094937A (en) | 1983-10-28 | 1983-10-28 | Dihydroxydicarboxylic acid having cyclohexane ring and its ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6094937A JPS6094937A (en) | 1985-05-28 |
| JPS6150936B2 true JPS6150936B2 (en) | 1986-11-06 |
Family
ID=16472187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20332883A Granted JPS6094937A (en) | 1983-10-28 | 1983-10-28 | Dihydroxydicarboxylic acid having cyclohexane ring and its ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6094937A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021117369A1 (en) | 2019-12-12 | 2021-06-17 | パナソニックＩｐマネジメント株式会社 | Electrode catalyst for fuel cell, electrode catalyst layer for fuel cell, membrane/electrode assembly, and fuel cell |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101082257B1 (en) * | 2007-05-29 | 2011-11-09 | 미쓰비시덴키 가부시키가이샤 | Method of connecting elevator ropes |
-
1983
- 1983-10-28 JP JP20332883A patent/JPS6094937A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021117369A1 (en) | 2019-12-12 | 2021-06-17 | パナソニックＩｐマネジメント株式会社 | Electrode catalyst for fuel cell, electrode catalyst layer for fuel cell, membrane/electrode assembly, and fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6094937A (en) | 1985-05-28 |
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