JP3276405B2 - Method for producing borate of guanidine compound - Google Patents
Method for producing borate of guanidine compoundInfo
- Publication number
- JP3276405B2 JP3276405B2 JP19389992A JP19389992A JP3276405B2 JP 3276405 B2 JP3276405 B2 JP 3276405B2 JP 19389992 A JP19389992 A JP 19389992A JP 19389992 A JP19389992 A JP 19389992A JP 3276405 B2 JP3276405 B2 JP 3276405B2
- Authority
- JP
- Japan
- Prior art keywords
- guanidine
- guanidine compound
- borate
- compound
- producing
- 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 - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はグアニジン化合物のホウ
酸塩を製造する方法に関する。The present invention relates to a method for producing a borate of a guanidine compound.
【０００２】[0002]
【従来の技術】グアニジン化合物のホウ酸塩は不活性ガ
スまたは還元性ガス雰囲気下において高温加熱すること
により、窒化アルミニウムに転化することができセラミ
ックスの原料として極めて有用な化合物である。このグ
アニジン化合物のホウ酸塩の製造方法としては先に（化
１）で示されるグアニジン化合物を水溶液中でホウ酸常
温〜１００℃の温度において反応させることにより得る
方法がある。2. Description of the Related Art A borate of a guanidine compound can be converted into aluminum nitride by heating at a high temperature in an inert gas or reducing gas atmosphere, and is a very useful compound as a raw material for ceramics. As a method for producing the borate of the guanidine compound, there is a method obtained by reacting the guanidine compound represented by the above formula (1) in an aqueous solution at a temperature of boric acid normal temperature to 100 ° C.
【０００３】[0003]
【発明が解決しようとする課題】しかし、上記方法によ
る水系での製造方法では結晶を得る操作において減圧濃
縮を行うが、加熱によるグアニジン化合物のホウ酸塩の
分解が起きてホウ酸が析出する。これを防止する目的で
通常はグアニジン化合物をホウ酸の当量以上、好ましく
は１．５倍量以上過剰に存在させた条件下で濃縮を行
う。このためグアニジン化合物のホウ酸塩の結晶にグア
ニジン化合物が混合されるため最終的に精製工程が必要
になる。However, in the aqueous production method according to the above method, concentration under reduced pressure is carried out in the operation of obtaining crystals, but the guanidine compound borate is decomposed by heating, and boric acid is precipitated. In order to prevent this, the guanidine compound is usually concentrated under conditions in which the guanidine compound is present in excess of the equivalent of boric acid, preferably 1.5 times or more. For this reason, since the guanidine compound is mixed with the borate crystals of the guanidine compound, a purification step is finally required.
【０００４】[0004]
【課題を解決するための手段】本発明者等はこれらの問
題を解決するため鋭意研究の結果、本発明を完成するに
到った。すなわち、本発明のグアニジン化合物のホウ酸
塩の製造方法は下記一般式（化２）Means for Solving the Problems The present inventors have made intensive studies to solve these problems, and as a result, have completed the present invention. That is, the method for producing a borate of a guanidine compound of the present invention is represented by the following general formula (Formula 2)
【０００５】[0005]
【化２】 （式中、Ｒ1 、Ｒ2 、Ｒ3 及びＲ4 はそれぞれ水素、ア
ルキル基、アリール基、アルキルアリールまたはヒドロ
キシアルキル基を示す。又、Ｒ1 はアミノ基であっても
よい）で表されるグアニジン化合物とアルコキシホウ素
等の有機ホウ素化合物を有機溶媒中で、当量の水を加え
て非水溶液系で反応させることを特徴とするものであ
る。Embedded image (Wherein, R 1 , R 2 , R 3 and R 4 each represent hydrogen, an alkyl group, an aryl group, an alkylaryl or a hydroxyalkyl group, and R 1 may be an amino group). A guanidine compound and an organic boron compound such as alkoxyboron in an organic solvent, by adding an equivalent amount of water, and reacting in a non-aqueous solution system.
【０００６】本発明に於いて使用するグアニジン化合物
は、上記一般式（化２）で表されるが、具体的な例とし
ては、Ｒ1 及びＲ4 が全て水素であるグアニジンのほか
に、1-メチルグアニジン、1,1-ジメチルグアニジン、1,
3-ジメチルグアニジン、1,1,3-トリメチルグアニジン、
1,1,3,3-テトラメチルグアニジン、1-エチルグアニジ
ン、1-フェニルグアニジン、1-シクロヘキシルグアニジ
ン、1-べンジルグアニジン、1-メチロールグアニジン、
1-アミノグアニジン、1,3-エチルグアニジン、1,3-ジフ
ェニルグアニジン、1,3-ジシクロヘキシルグアニジン、
1,3-ジベンジルグアニジン、1,3-ジメチロールグアニジ
ン等が挙げられる。The guanidine compound used in the present invention is represented by the above general formula (Formula 2). Specific examples include guanidine in which R 1 and R 4 are all hydrogen, -Methylguanidine, 1,1-dimethylguanidine, 1,
3-dimethylguanidine, 1,1,3-trimethylguanidine,
1,1,3,3-tetramethylguanidine, 1-ethylguanidine, 1-phenylguanidine, 1-cyclohexylguanidine, 1-benzylguanidine, 1-methylolguanidine,
1-aminoguanidine, 1,3-ethylguanidine, 1,3-diphenylguanidine, 1,3-dicyclohexylguanidine,
Examples include 1,3-dibenzylguanidine, 1,3-dimethylolguanidine and the like.
【０００７】これらの各種のグアニジン化合物の中でも
グアニジン化合物のホウ酸塩の原料としては、特にグア
ニジン、1-メチルグアニジン、1,1-ジメチルグアニジ
ン、1,3-ジメチルグアニジン、1-エチルグアニジンまた
は1-メチロールグアニジンが好ましく用いられる。[0007] Among these various guanidine compounds, the raw materials for the borate of the guanidine compound include guanidine, 1-methylguanidine, 1,1-dimethylguanidine, 1,3-dimethylguanidine, 1-ethylguanidine or 1-ethylguanidine. -Methylolguanidine is preferably used.
【０００８】また、グアニジンが入手しにくいばあいに
は、水酸基型に再生した強塩基性陰イオン交換樹脂を充
填したカラムに各種のグアニジン塩、例えば炭酸グアニ
ジン、スルファミン酸グアニジン等の水溶液を通した
後、減圧濃縮によって脱水し、アルコールに溶解させ
る。もう一方の原料であるアルミニウムアルコレートも
アルコールに溶解させる。When guanidine is difficult to obtain, an aqueous solution of various guanidine salts, for example, guanidine carbonate, guanidine sulfamate, or the like is passed through a column packed with a strongly basic anion exchange resin regenerated to a hydroxyl group. Thereafter, the solution is dehydrated by concentration under reduced pressure and dissolved in alcohol. The other raw material, aluminum alcoholate, is also dissolved in the alcohol.
【０００９】本発明によるグアニジン化合物のホウ酸塩
を製造する方法としては、例えば、トリブトキシホウ酸
のブタノール溶液とグアニジンのブタノール溶液を混合
したものに水を加え常圧下、常温〜１００℃において通
常数分〜数時間攪拌してグアニジン化合物のホウ酸塩の
白色結晶を得る。As a method for producing the borate of a guanidine compound according to the present invention, for example, water is added to a mixture of a butanol solution of tributoxyboric acid and a butanol solution of guanidine, and water is added at normal pressure to normal temperature to 100 ° C. Stir for several minutes to several hours to obtain white crystals of borate salt of guanidine compound.
【００１０】他のグアニジン化合物のホウ酸塩の場合に
も同様の操作を応用することによりグアニジン化合物の
ホウ酸塩を得ることが出来る。A borate of a guanidine compound can be obtained by applying the same operation to a borate of another guanidine compound.
【００１１】本発明のグアニジン化合物のホウ酸塩は、
その原料であるグアニジン化合物やアルコキシホウ素の
段階で精製しておけば不純物の非常に少ないものを合成
できる。The borate of the guanidine compound of the present invention is
By purifying at the stage of the guanidine compound or alkoxyboron, which is a raw material, a compound having very few impurities can be synthesized.
【００１２】[0012]
【実施例】以下、実施例により本発明を更に具体的に説
明する。EXAMPLES The present invention will be described more specifically with reference to the following examples.
【００１３】実施例１ アルコキシホウ素としてトリブトキシホウ酸２３ｇをｎ
−ブチルアルコール１０００ミリリットルが入った容器
に加え充分に攪拌した。一方、遊離グアニジンは炭酸グ
アニジン（三井東圧化学製）を水で３回再結晶して９０
０℃における強熱残渣を１００ｐｐｍ以下に精製した高
純度炭酸グアニジンを原料として用いた。すなわち、高
純度炭酸グアニジン５０．０グラムを１リットルの蒸留
水に溶解し、あらかじめ水酸基型に再生してある強塩基
性陰イオン交換樹脂（商品名、レバチットＭ−６００）
０．２リットルを充填したガラスカラムを通して炭酸根
を除去する。カラムに通液する際に、濃度の低い初期の
通過液の一部を分け、比較的濃度の高いグアニジン水溶
液を減圧乾燥容器に入れ減圧下５０℃の条件で脱水を続
け、濃縮の終わり頃には真空ポンプを用いて乾燥を行
い、グアニジンの濃縮液３１．９ｇを得た。本濃縮液を
液体クロマトグラムで測定した結果、グアニジン濃度は
８８．０％であった。Example 1 23 g of tributoxyboric acid as n-alkoxyboron
-Butyl alcohol was added to a container containing 1000 ml and stirred sufficiently. On the other hand, free guanidine is obtained by recrystallizing guanidine carbonate (manufactured by Mitsui Toatsu Chemicals) three times with water, and
High-purity guanidine carbonate obtained by purifying an ignition residue at 0 ° C. to 100 ppm or less was used as a raw material. That is, 50.0 g of high-purity guanidine carbonate is dissolved in 1 liter of distilled water, and a strongly basic anion exchange resin (trade name, Levatit M-600) which has been regenerated in a hydroxyl group form in advance.
The carbonate is removed through a glass column filled with 0.2 liter. When passing through the column, a part of the initial low-concentration liquid is divided, a relatively high-concentration aqueous solution of guanidine is placed in a reduced-pressure drying vessel, and dehydration is continued at 50 ° C. under reduced pressure. Was dried using a vacuum pump to obtain 31.9 g of a guanidine concentrated solution. As a result of measuring the concentrated solution by liquid chromatography, the guanidine concentration was 88.0%.
【００１４】このグアニジン濃縮液１０ｇを前記トリブ
トキシホウ酸のｎ−ブチルアルコール溶液に加えて攪拌
する。更に水５ｇを添加すると瞬時に微細白色固体が生
成した。常温にて１時間攪拌を続けた後、グラスフィル
ターを用いて濾過を行い、ｎ−ブチルアルコール溶液よ
り固形物を分離し、得られた固形物は少量のｎ−ブチル
アルコールを用いて洗浄した。６０℃で３時間乾燥の後
１３．４ｇの粉末が得られた。Ｘ線分析の結果、この粉
末は結晶性のない固体であり、その他の性質として水に
可溶（アルコールに溶け難い）のアルカリ性物質である
ことが分かった。また得られた物の元素分析を行い、以
下の結果を得た。（重量％） Ｃ＝１０．８％、 Ｈ＝７．０％、 Ｎ＝３２．８％、
Ｂ＝９．３％10 g of this guanidine concentrated solution is added to the above-mentioned solution of tributoxyboric acid in n-butyl alcohol and stirred. When 5 g of water was further added, a fine white solid was instantaneously formed. After stirring at room temperature for 1 hour, filtration was performed using a glass filter, a solid was separated from the n-butyl alcohol solution, and the obtained solid was washed with a small amount of n-butyl alcohol. After drying at 60 ° C. for 3 hours, 13.4 g of powder was obtained. As a result of X-ray analysis, the powder was found to be a solid without crystallinity, and as other properties, an alkaline substance soluble in water (insoluble in alcohol). The obtained product was subjected to elemental analysis, and the following results were obtained. (% By weight) C = 10.8%, H = 7.0%, N = 32.8%,
B = 9.3%
【００１５】[0015]
【発明の効果】本発明の方法によれば，有機溶媒中でグ
アニジン化合物のホウ酸塩が高純度で得られることか
ら、精製工程が不要となり、低コストでの生産が可能と
なる。According to the method of the present invention, a borate of a guanidine compound can be obtained in an organic solvent with high purity, so that a purification step is not required and production at low cost becomes possible.
Claims (1)
ルキル基、アリール基、アルキルアリール基またはヒド
ロキシアルキル基を示す。又、Ｒ1 はアミノ基であって
もよい）で表されるグアニジン化合物と有機ホウ素化合
物を有機溶媒中で反応させることを特徴とする、グアニ
ジン化合物のホウ酸塩の製造方法。1. A compound of the general formula (1) (Wherein, R 1 , R 2 , R 3, and R 4 each represent hydrogen, an alkyl group, an aryl group, an alkylaryl group, or a hydroxyalkyl group; and R 1 may be an amino group). A method for producing a borate of a guanidine compound, comprising reacting the guanidine compound with an organic boron compound in an organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19389992A JP3276405B2 (en) | 1992-07-21 | 1992-07-21 | Method for producing borate of guanidine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19389992A JP3276405B2 (en) | 1992-07-21 | 1992-07-21 | Method for producing borate of guanidine compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0641048A JPH0641048A (en) | 1994-02-15 |
| JP3276405B2 true JP3276405B2 (en) | 2002-04-22 |
Family
ID=16315598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19389992A Expired - Fee Related JP3276405B2 (en) | 1992-07-21 | 1992-07-21 | Method for producing borate of guanidine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3276405B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6919036B2 (en) | 2000-01-21 | 2005-07-19 | U.S. Borax Inc. | Nonaborate compositions and their preparation |
-
1992
- 1992-07-21 JP JP19389992A patent/JP3276405B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0641048A (en) | 1994-02-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |