JP4232342B2 - Dialkoxybenzyl acid derivative and gelling or solidifying agent using the same - Google Patents

Description

【０００９】
【発明の実施の形態】
以下に本発明の実施の形態を詳細に説明する。
【００１０】
本発明のジアルコキシベンジル酸誘導体は前記一般式（Ｉ）で表される。前記一般式（Ｉ）において、Ｒ^１，Ｒ^２は好ましくは各々独立に炭素数６〜１０のアルキル基、より好ましくは炭素数６〜１０の直鎖アルキル基であり、Ｒ^３としては好ましくはアルカリ金属、より好ましくはＮａまたはＫである。
【００１１】
このようなジアルコキシベンジル酸誘導体の具体例としては、次のような化合物が挙げられる。
【００１２】
【化３】

【００１３】
【化４】

【００１４】
【化５】

【００１５】
【化６】

【００１６】
本発明のジアルコキシベンジル酸誘導体は、例えば下記の方法で合成することができる。
▲１▼ ４，４’−ジヒドロキシベンジルの合成
４，４’−ジメトキシベンジル等の４，４’−ジアルコキシベンジルを出発原料として、これを酢酸等の溶媒に溶解し、臭化水素酸等のハロゲン化水素を添加して下記反応により４，４’−ジヒドロキシベンジルを合成する。
【００１７】
【化７】

【００１８】
この反応は出発原料である４，４’−ジアルコキシベンジルと臭化水素酸とを１：７０〜１００（モル比）程度の割合で用い、１００〜１５０℃で１〜５時間程度実施される。
【００１９】
▲２▼ ４，４’−ジアルコキシベンジルの合成
▲１▼で得た４，４’−ジヒドロキシベンジルを、水酸化ナトリウム等のアルカリとテトラブチルアンモニウムブロミド等の触媒の存在下にブロモオクタン等のハロゲン化アルキルＸＲ^１，ＸＲ^２（Ｘはハロゲンを表し、Ｒ^１，Ｒ^２は前記一般式（Ｉ）におけると同義である。）と下記のように反応させて、４，４’−ジアルコキシベンジルを合成する。
【００２０】
【化８】

【００２１】
この反応は、４，４’−ジヒドロキシベンジルとアルカリとハロゲン化アルキルとを１：２〜３：４〜５（モル比）程度の割合で用い、ジクロロメタン、クロロホルム、テトラヒドロフラン等の溶媒中にて室温下で１５〜３０時間程度行われる。
【００２２】
▲３▼ ４，４’−ジアルコキシベンジル酸誘導体の合成
▲２▼で得た４，４’−ジアルコキシベンジルを水酸化カリウム又は水酸化ナトリウム等のアルカリＭＯＨ（Ｍはアルカリ金属を表す。）と共に加熱することにより、ベンジル酸転移を生起させると共に、酸アルカリ反応で４，４’−ジアルコキシベンジル酸アルカリを合成する。
【００２３】
【化９】

【００２４】
この反応は、４，４’−ジアルコキシベンジル１モルに対してアルカリ２〜４モルを添加して、ｎ−ブタノール等の溶媒中５〜３０分程度加熱還流することにより行われる。
【００２５】
ここで、アルカリと共に、ハロゲン化アンモニウム塩ＸＮＲ^４Ｒ^５Ｒ^６（Ｘはハロゲンを表し、Ｒ^４，Ｒ^５，Ｒ^６は前記一般式（Ｉ）におけると同義である。）を用いることにより、下記のエステル反応で４，４’−ジアルコキシベンジル酸アンモニウムを得ることができる。
【００２６】
【化１０】

【００２７】
また、下記反応によりベンジル酸転移のみを生起させた場合には、４，４’−ジアルコキシベンジル酸を得ることができる。
【００２８】
【化１１】

【００２９】
反応生成物中に未反応の原料や副生成物が残存する場合には減圧蒸留、溶媒分別などの公知の手段で精製することができる。例えば、生成物の精製は、減圧下での未反応物質などの除去、酢酸エチルやヘキサンなどの有機溶媒による再結晶、活性白土、活性炭、シリカゲル、アルミナなどの吸着処理、その他により行うことができ、必要に応じてこれらを単独でもしくは組み合わせて適用すればよい。
【００３０】
本発明のジアルコキシベンジル酸誘導体は、塗料、インク、潤滑油、農業、水産、化粧品および各種電池の電解質や、医薬品、繊維、樹脂、高分子、ゴム、金属等の加工分野を含む産業分野において利用される各種有機液体のゲル化または固化剤として有用である。
【００３１】
ここで有機液体としては、大豆油、菜種油、コーン油、サフラワー油、ヒマワリ油、綿実油、オリーブ油、パーム油、ヒマシ油、魚油、豚脂、牛脂等の動植物油脂類、ミリスチン酸イソプロピル、トリ−２−エチルヘキサン酸グリセリド、ミリスチン酸２−オクチルドデシル等のエステル類、メタノール、エタノール、オクタノール等のアルコール類、ジエチルエーテル等のエーテル類、灯油、重油、流動パラフィン、イソパラフィン等の炭化水素系油剤、またヘキサン、シクロヘキサン、ドデカン、ＤＭＳＯ、クロロホルムといった有機溶剤や廃食用油、廃潤滑油、廃金属加工油剤等のいわゆる廃油類を対象とすることができる。
【００３２】
本発明のゲル化または固化剤の使用法には、特に制限はなく、例えば、前記有機液体１ｍｌに対し、本発明のゲル化または固化剤を、ジアルコキシベンジル酸誘導体として１〜５０ｍｇ、好ましくは２〜２０ｍｇ添加し、均一状態になるまで攪拌した後静置すれば、ゲル化物または固化物を調製することができる。なお、攪拌時には、必要に応じて３０〜２０℃程度に加熱しても良いが、本発明のジアルコキシベンジル酸誘導体では、室温で十分にゲル化または固化を行うことができる。
【００３３】
このような本発明のゲル化または固化剤は単独でも使用できるが、本発明の目的を逸脱しないかぎり、従来公知のゲル化剤、天然ワックスまたは合成ワックス等の固化剤等を適量併用してもよい。
【００３４】
【実施例】
以下に実施例を挙げて本発明をより具体的に説明する。
【００３５】
実施例１：ジアルコキシベンジル酸誘導体の合成
次の手順で、４，４’−ジオクチロキシベンジル酸カリウムを合成した。
【００３６】
［４，４’−ジヒドロキシベンジルの合成］
【００３７】
【化１２】

【００３８】
４，４’−ジメトキシベンジル２．０ｇ（７．４ｍｍｏｌ）を、酢酸（１５ｍｌ）に溶かし加熱攪拌した。還流し始めたところで、臭化水素酸（４７％）を２０ｍｌずつ５回に分けて合計１００ｍｌ加えた。更に、２．５時間加熱還流し、溶液を室温まで放冷した後、氷水に注ぎ３０分間攪拌した。沈殿を濾取し、カラムクロマトグラフィー（酢酸エチル：ヘキサン＝１：１）に付し、淡黄色の粉末を得た。この粉末の分析結果は以下の通りであり、４，４’−ジヒドロキシベンジル１．５６ｇ（収率８７％）であることが確認された。
m.p. ; 255-257℃
I.R.(KBr, cm^−１) ; 3404, 1646, 1572, 1512, 1449, 1369, 1336, 1293, 1223, 1171, 878, 850
FAB-MS (MH^＋) ; 243
1H-NMR (270 MHz, DMSO-d6) ; δ＝6.93(d, 4H, J=7.2), 7.74(d, 4H, J=7.2), 10.80(s, 2H)
【００３９】
［４，４’−ジオクチロキシベンジルの合成］
【００４０】
【化１３】

【００４１】
水酸化ナトリウム１．２ｇ（３０ｍｍｏｌ）を溶かした水（５０ｍｌ）に、ジクロロメタン（５０ｍｌ）を加えた後、４，４’−ジヒドロキシベンジル２．４ｇ（１０ｍｍｏｌ）、１−ブロモオクタン８．７ｇ（４５ｍｍｏｌ）、テトラブチルアンモニウムブロミド６４４ｍｇ（１．９ｍｍｏｌ）を加え、ＤＣスターラーを用いて室温下で２４時間攪拌した。ジクロロメタン相を水（５０ｍｌ×５回）で洗浄し、硫酸マグネシウムで乾燥した後、減圧下で溶媒を留去した。残渣をカラムクロマトグラフィー（ジクロロメタン：ヘキサン＝１：１）に処し、クロロホルム−ヘキサンの混合溶媒で再結晶して、無色の針状結晶を得た。この結晶の分析結果は以下の通りであり、４，４’−ジオクチロキシベンジル２．５ｇ（９．４ｍｍｏｌ，収率６５％）であることが確認された。
m.p. ; 67.0-67.8℃
I.R.(KBr, cm^−１) ; 2924, 2850, 1668, 1603, 1576, 1510, 1466, 1422, 1385, 1310, 1296, 1255, 1230, 1166, 1122, 1063, 1016
FAB-MS (MH^＋) ; 467
1H-NMR (270 MHz, CDCl_３) ; δ＝0.86-0.90(m, 6H), 1.22-1.36(m, 16H), 1.43-1.47(m, 4H), 1.78-1.81(m, 4H), 4.02(t, 4H, J=6.5), 6.93-6.95(m, 4H), 7.91-7.93(m, 4H)
【００４２】
［４，４’−ジオクチロキシベンジル酸カリウムの合成］
【００４３】
【化１４】

【００４４】
水酸化カリウム（０．５８ｇ）をｎ−ブタノール（３ｍｌ）に溶かし加熱攪拌し、還流し始めたところで４，４’−ジオクチロキシベンジル２．０７ｇ（４．４ｍｍｏｌ）を加えた。２０分間加熱還流し、室温まで放冷した。反応溶液を水（５ｍｌ×３回）で洗浄し、硫酸マグネシウムで乾燥させた後、減圧下で溶媒を留去した。残渣を酢酸エチルで洗浄し、白色の粉末を得た。この白色粉の分析結果は以下の通りであり、４，４’−ジオクチロキシベンジル酸カリウム１．９５ｇ（３．７３ｍｍｏｌ，収率８４％）が得られたことが確認された。
I.R.(KBr, cm^−１) ; 3100, 2924, 2854, 1656, 1613, 1584, 1512, 1468, 1385, 1307, 1250, 1184, 1120, 1063
13C-NMR (400 MHz, solid state) ; δ＝14.49, 23.23, 27.21, 30.81, 32.64, 68.88, 83.94, 113.86, 129.11, 136.11, 137.95, 176.22
【００４５】
実施例２〜５：ジアルコキシベンジル酸誘導体によるゲル化
５ｍｌのガラス製サンプル瓶に、実施例１で合成した４，４’−ジオクチロキシベンジル酸カリウムを１０ｍｇ入れ、表１に示す有機液体１ｍｌを各々加えた後、室温で振盪機で攪拌したところ、いずれも均一なゲル状態が確認された。また、このゲル状態は室温で放置しても安定に保持された。
【００４６】
【表１】

【００４７】
【発明の効果】
以上詳述した通り、本発明によれば、前記一般式（Ｉ）で示される新規ジアルコキシベンジル酸誘導体が提供され、このジアルコキシベンジル酸誘導体を有効成分とする本発明のゲル化もしくは固化剤によれば、動植物油脂、エステル、アルコール、エーテル、炭化水素系油剤や有機溶剤等、あるいは廃食用油、廃潤滑油、廃金属加工油剤等の廃油類といった幅広い有機液体に対して、少量の添加で、均一かつ安定で良好なゲル化物または固化物を調製することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel dialkoxybenzylic acid derivative useful as a gelling or solidifying agent for organic liquids and a gelling agent containing this compound as an active ingredient. The gelling or solidifying agent of the present invention is used in industrial fields including paints, inks, lubricants, agriculture, fisheries, cosmetics, various battery electrolytes, pharmaceuticals, fibers, resins, polymers, rubbers, metals, and other processing fields. Available.
[0002]
[Prior art]
In general, the organic liquids (animal and vegetable oils and fats, esters, polyols, ethers, alcohols, hydrocarbons, etc.) used in the industrial field have a function of gelling or solidifying, such as 12-hydroxystearic acid, dibenzylidene sorbitol, Alkali metal salts and alkaline earth metal salts of fatty acids are known.
[0003]
Of these, 12-hydroxystearic acid is inexpensive, but there are few types of organic liquids that can be gelled or solidified, and the temperature at which the resulting gel softens is low. On the other hand, although dibenzylidene sorbitol forms a strong gel with a small amount of addition, it has the disadvantage of liberating benzaldehyde, and it is unsuitable for solidifying low-boiling short-chain alcohols, etc. due to its high melting point. is there. Alkali metal salts and alkaline earth metal salts of fatty acids require a large amount of addition for gelation or solidification, and have limitations such as limited usable conditions.
[0004]
[Problems to be solved by the invention]
As described above, any of the conventional gelling or solidifying agents has some disadvantages and cannot be said to be sufficiently satisfactory.
[0005]
Therefore, the object of the present invention is that it can be easily produced, and various organic liquids can be gelled or solidified with a small amount of addition, uniform and stable against long-term storage and temperature change. The object is to provide a highly organic liquid gelling or solidifying agent.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have synthesized a novel dialkoxybenzyl acid derivative and found that it has excellent gelation or solidification performance for various organic liquids. The present invention has been completed.
[0007]
That is, the present invention provides a dialkoxybenzyl acid derivative represented by the following general formula (I) and a gelling or solidifying agent containing the dialkoxybenzyl acid derivative as an active ingredient.
[0008]
[Chemical formula 2]

[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
[0010]
The dialkoxybenzyl acid derivative of the present invention is represented by the general formula (I). In the general formula (I), R ¹ and R ² are preferably each independently an alkyl group having 6 to 10 carbon atoms, more preferably a linear alkyl group having 6 to 10 carbon atoms, and R ³ is preferably Alkali metal, more preferably Na or K.
[0011]
Specific examples of such dialkoxybenzyl acid derivatives include the following compounds.
[0012]
[Chemical 3]

[0013]
[Formula 4]

[0014]
[Chemical formula 5]

[0015]
[Chemical 6]

[0016]
The dialkoxybenzyl acid derivative of the present invention can be synthesized, for example, by the following method.
(1) Synthesis of 4,4'-dihydroxybenzyl Using 4,4'-dialkoxybenzyl such as 4,4'-dimethoxybenzyl as a starting material, this was dissolved in a solvent such as acetic acid, Hydrogen halide is added to synthesize 4,4′-dihydroxybenzyl by the following reaction.
[0017]
[Chemical 7]

[0018]
This reaction is carried out at 100 to 150 ° C. for about 1 to 5 hours using 4,4′-dialkoxybenzyl as a starting material and hydrobromic acid in a ratio of about 1:70 to 100 (molar ratio). .
[0019]
(2) Synthesis of 4,4'-dialkoxybenzyl The 4,4'-dihydroxybenzyl obtained in (1) is converted to bromooctane or the like in the presence of an alkali such as sodium hydroxide and a catalyst such as tetrabutylammonium bromide. A halogenated alkyl XR ¹ , XR ² (X represents a halogen, R ¹ and R ² are as defined in the general formula (I)) and 4,4′-dialkoxy are reacted as follows. Synthesize benzyl.
[0020]
[Chemical 8]

[0021]
In this reaction, 4,4′-dihydroxybenzyl, alkali, and alkyl halide are used in a ratio of about 1: 2 to 3: 4 to 5 (molar ratio), and the reaction is performed at room temperature in a solvent such as dichloromethane, chloroform, and tetrahydrofuran. Under about 15 to 30 hours.
[0022]
(3) Synthesis of 4,4′-dialkoxybenzylic acid derivative 4,4′-dialkoxybenzyl obtained in (2) is converted to an alkali MOH such as potassium hydroxide or sodium hydroxide (M represents an alkali metal). When heated together, benzylic acid transfer occurs, and an alkali 4,4′-dialkoxybenzylate is synthesized by an acid-alkali reaction.
[0023]
[Chemical 9]

[0024]
This reaction is carried out by adding 2 to 4 moles of alkali to 1 mole of 4,4′-dialkoxybenzyl and heating to reflux in a solvent such as n-butanol for about 5 to 30 minutes.
[0025]
Here, by using an ammonium halide salt XNR ⁴ R ⁵ R ⁶ (X represents a halogen, and R ⁴ , R ⁵ , and R ⁶ have the same meaning as in the general formula (I)) together with an alkali. Ammonium 4,4′-dialkoxybenzylate can be obtained by the following ester reaction.
[0026]
[Chemical Formula 10]

[0027]
Further, when only benzyl acid transfer is caused by the following reaction, 4,4′-dialkoxybenzyl acid can be obtained.
[0028]
Embedded image

[0029]
When unreacted raw materials and by-products remain in the reaction product, they can be purified by a known means such as distillation under reduced pressure or solvent fractionation. For example, the product can be purified by removing unreacted substances under reduced pressure, recrystallization with an organic solvent such as ethyl acetate or hexane, adsorption treatment of activated clay, activated carbon, silica gel, alumina, etc. These may be applied alone or in combination as necessary.
[0030]
The dialkoxybenzylic acid derivative of the present invention is used in industrial fields including paints, inks, lubricants, agriculture, fisheries, cosmetics, various battery electrolytes, pharmaceuticals, fibers, resins, polymers, rubbers, metals and other processing fields. It is useful as a gelling or solidifying agent for various organic liquids used.
[0031]
Examples of organic liquids include soybean oil, rapeseed oil, corn oil, safflower oil, sunflower oil, cottonseed oil, olive oil, palm oil, castor oil, fish oil, lard, beef tallow and other animal and vegetable oils, isopropyl myristate, tri- Esters such as 2-ethylhexanoic acid glyceride and 2-octyldodecyl myristate, alcohols such as methanol, ethanol and octanol, ethers such as diethyl ether, hydrocarbon oils such as kerosene, heavy oil, liquid paraffin and isoparaffin, Further, organic solvents such as hexane, cyclohexane, dodecane, DMSO, and chloroform, and so-called waste oils such as waste edible oil, waste lubricant oil, and waste metal processing oil can be targeted.
[0032]
The method of using the gelling or solidifying agent of the present invention is not particularly limited. For example, 1 to 50 mg of the gelling or solidifying agent of the present invention as a dialkoxybenzylic acid derivative, preferably 1 ml of the organic liquid, If 2-20 mg is added and it stirs until it becomes a uniform state, it will stand still and a gelled material or a solidified material can be prepared. In addition, at the time of stirring, you may heat to about 30-20 degreeC as needed, but the dialkoxy benzylic acid derivative of this invention can fully gelatinize or solidify at room temperature.
[0033]
Such a gelling or solidifying agent of the present invention can be used alone, but an appropriate amount of a conventionally known gelling agent, a solidifying agent such as natural wax or synthetic wax, or the like may be used in combination without departing from the object of the present invention. Good.
[0034]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples.
[0035]
Example 1 Synthesis of Dialkoxybenzyl Acid Derivatives Potassium 4,4′-dioctyloxybenzylate was synthesized by the following procedure.
[0036]
[Synthesis of 4,4′-dihydroxybenzyl]
[0037]
Embedded image

[0038]
4,4′-Dimethoxybenzyl (2.0 g, 7.4 mmol) was dissolved in acetic acid (15 ml) and stirred with heating. When it began to reflux, hydrobromic acid (47%) was added in 20 ml portions and added in a total of 100 ml. The solution was further heated to reflux for 2.5 hours, and the solution was allowed to cool to room temperature, then poured into ice water and stirred for 30 minutes. The precipitate was collected by filtration and subjected to column chromatography (ethyl acetate: hexane = 1: 1) to obtain a pale yellow powder. The analysis result of this powder is as follows, and it was confirmed that it was 1.56 g (yield 87%) of 4,4′-dihydroxybenzyl.
mp; 255-257 ℃
IR (KBr, cm ^-1 ); 3404, 1646, 1572, 1512, 1449, 1369, 1336, 1293, 1223, 1171, 878, 850
FAB-MS (MH ⁺ ); 243
1H-NMR (270 MHz, DMSO-d6); δ = 6.93 (d, 4H, J = 7.2), 7.74 (d, 4H, J = 7.2), 10.80 (s, 2H)
[0039]
[Synthesis of 4,4′-Dioctyloxybenzyl]
[0040]
Embedded image

[0041]
Dichloromethane (50 ml) was added to water (50 ml) in which 1.2 g (30 mmol) of sodium hydroxide was dissolved, and then 2.4 g (10 mmol) of 4,4′-dihydroxybenzyl and 8.7 g (45 mmol) of 1-bromooctane were added. ), 644 mg (1.9 mmol) of tetrabutylammonium bromide was added, and the mixture was stirred at room temperature for 24 hours using a DC stirrer. The dichloromethane phase was washed with water (50 ml × 5 times), dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was subjected to column chromatography (dichloromethane: hexane = 1: 1) and recrystallized with a mixed solvent of chloroform-hexane to obtain colorless needle crystals. The analysis result of this crystal was as follows, and it was confirmed that it was 2.5 g (9.4 mmol, yield 65%) of 4,4′-dioctyloxybenzyl.
mp; 67.0-67.8 ℃
IR (KBr, cm ^-1 ); 2924, 2850, 1668, 1603, 1576, 1510, 1466, 1422, 1385, 1310, 1296, 1255, 1230, 1166, 1122, 1063, 1016
FAB-MS (MH ⁺ ); 467
1H-NMR (270 MHz, CDCl ₃ ); δ = 0.86-0.90 (m, 6H), 1.22-1.36 (m, 16H), 1.43-1.47 (m, 4H), 1.78-1.81 (m, 4H), 4.02 (t, 4H, J = 6.5), 6.93-6.95 (m, 4H), 7.91-7.93 (m, 4H)
[0042]
[Synthesis of potassium 4,4′-dioctyloxybenzylate]
[0043]
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[0044]
Potassium hydroxide (0.58 g) was dissolved in n-butanol (3 ml), heated and stirred, and when reflux was started, 2.07 g (4.4 mmol) of 4,4′-dioctyloxybenzyl was added. The mixture was heated to reflux for 20 minutes and allowed to cool to room temperature. The reaction solution was washed with water (5 ml × 3 times), dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was washed with ethyl acetate to give a white powder. The analysis result of this white powder was as follows, and it was confirmed that 1.95 g (3.73 mmol, yield 84%) of potassium 4,4′-dioctyloxybenzylate was obtained.
IR (KBr, cm ^-1 ); 3100, 2924, 2854, 1656, 1613, 1584, 1512, 1468, 1385, 1307, 1250, 1184, 1120, 1063
13C-NMR (400 MHz, solid state); δ = 14.49, 23.23, 27.21, 30.81, 32.64, 68.88, 83.94, 113.86, 129.11, 136.11, 137.95, 176.22
[0045]
Examples 2 to 5: Gelation with dialkoxybenzylic acid derivative 10 mg of potassium 4,4′-dioctyloxybenzylate synthesized in Example 1 was placed in a 5 ml glass sample bottle, and 1 ml of organic liquid shown in Table 1 After each was added, the mixture was stirred with a shaker at room temperature, and a uniform gel state was confirmed in all cases. Further, this gel state was stably maintained even when left at room temperature.
[0046]
[Table 1]

[0047]
【The invention's effect】
As described above in detail, according to the present invention, a novel dialkoxybenzyl acid derivative represented by the above general formula (I) is provided, and the gelling or solidifying agent of the present invention comprising this dialkoxybenzyl acid derivative as an active ingredient. According to the above, a small amount is added to a wide range of organic liquids such as animal and vegetable fats and oils, esters, alcohols, ethers, hydrocarbon oils and organic solvents, and waste oils such as waste edible oils, waste lubricants and waste metal processing oils. Thus, a uniform, stable and good gelled product or solidified product can be prepared.

Claims (2)

Dialkoxybenzyl acid derivatives represented by the following general formula (I).

A gelling or solidifying agent comprising the dialkoxybenzylic acid derivative according to claim 1 as an active ingredient.