JPH107664A - Production of urazole or its salt - Google Patents
Production of urazole or its saltInfo
- Publication number
- JPH107664A JPH107664A JP8178475A JP17847596A JPH107664A JP H107664 A JPH107664 A JP H107664A JP 8178475 A JP8178475 A JP 8178475A JP 17847596 A JP17847596 A JP 17847596A JP H107664 A JPH107664 A JP H107664A
- Authority
- JP
- Japan
- Prior art keywords
- urazole
- salt
- reaction
- formula
- alkaline earth
- 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
- UDATXMIGEVPXTR-UHFFFAOYSA-N 1,2,4-triazolidine-3,5-dione Chemical compound O=C1NNC(=O)N1 UDATXMIGEVPXTR-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 150000003839 salts Chemical class 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 19
- -1 carbamoylhydrazocarboxylic acid Chemical compound 0.000 claims description 17
- 150000001340 alkali metals Chemical class 0.000 claims description 16
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 14
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- UJTTUOLQLCQZEA-UHFFFAOYSA-N 9h-fluoren-9-ylmethyl n-(4-hydroxybutyl)carbamate Chemical compound C1=CC=C2C(COC(=O)NCCCCO)C3=CC=CC=C3C2=C1 UJTTUOLQLCQZEA-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- OWIUPIRUAQMTTK-UHFFFAOYSA-M n-aminocarbamate Chemical compound NNC([O-])=O OWIUPIRUAQMTTK-UHFFFAOYSA-M 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PFLUPZGCTVGDLV-UHFFFAOYSA-N acetone azine Chemical compound CC(C)=NN=C(C)C PFLUPZGCTVGDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- ULUZGMIUTMRARO-UHFFFAOYSA-N (carbamoylamino)urea Chemical compound NC(=O)NNC(N)=O ULUZGMIUTMRARO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical compound [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Air Bags (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ウラゾール（ヒド
ラゾジカルボンイミド、１,２,４−トリアゾリジン−
３,５−ジオン）もしくはその塩の製造法に関する。本
発明のウラゾールもしくはその塩は、例えば自動車のエ
アバッグのガス発生剤のガス発生基剤等として有用であ
る。TECHNICAL FIELD The present invention relates to urazole (hydrazodicarbonimide, 1,2,4-triazolidine-
3,5-dione) or a salt thereof. The urazole or a salt thereof of the present invention is useful, for example, as a gas generating base of a gas generating agent for an automobile air bag.
【０００２】[0002]
【従来の技術】従来、一般式（２）で表されるウラゾー
ル化合物の製造法としては、例えば、以下のような方法
が知られている。 （１）Ａnn．Ｃhem.，３０３，１０１ （１８９８） ＮＨ2ＣＯＮＨＣＯＮＨＮＨ2で表されるアミノビューレ
ットを用いてウラゾールを得る方法であるが、原料のア
ミノビューレットの入手が困難であるという問題点があ
った。 （２）Ｉnorganic Ｓynthesis，５，５２ （１９５
７） ＮＨ2ＣＯＮＨＣＯＯＣＨ3で表されるアロファン酸メチ
ルとヒドラジンヒドラートを反応させてウラゾールのヒ
ドラジン塩を得、次いでアセトンと反応させてウラゾー
ルを得る方法であるが、ヒドラジンヒドラートを多量に
必要とし、中間体のウラゾールヒドラジン塩を単離する
２段反応であり、更にアセトンアジンが副生するという
問題点があった。また収率も７８％と低い。 （３）特開昭５６−８７５７２号 ＮＨ2ＣＯＮＨＮＨＣＯＮＨ2で表されるヒドラゾジカル
ボンアミドを高沸点溶媒中、１９０〜２２０℃という高
温で環化反応させてウラゾールを得る方法であるが、高
温反応及びそれに伴う分解反応のため、副生物が生成す
るという問題点があった。また収率も９０％である。 （４）特開昭６２−２６２７７号 ＮＨ2ＣＯＮＨＣＯＮＨ2で表されるビューレットとヒド
ラジンヒドラートを反応させてウラゾールのヒドラジン
塩を得、次いでアセトンと反応させてウラゾールを得る
方法であるが、原料のビューレットの入手が困難であ
り、ヒドラジンヒドラートを多量に必要とし、中間体の
ウラゾールヒドラジン塩を単離する２段反応であり、更
にアセトンアジンが副生するという問題点があった。ま
た収率も６３％と低い。 以上のように、従来のウラゾールの製造法はいずれも工
業的に十分に満足できるものではなかった。2. Description of the Related Art Hitherto, as a method for producing a urazole compound represented by the general formula (2), for example, the following method is known. (1) Ann. Chem., 303, 101 (1898) This is a method of obtaining urazole using an amino buret represented by NH 2 CONHCONHNH 2 , but there is a problem that it is difficult to obtain a raw material amino buret. (2) Inorganic Synthesis, 5, 52 (195
7) A method of reacting methyl allophanoate represented by NH 2 CONHCOOCH 3 with hydrazine hydrate to obtain a hydrazine salt of urazole and then reacting with acetone to obtain urazole, but requires a large amount of hydrazine hydrate. This is a two-step reaction for isolating an intermediate urazole hydrazine salt, and further has the problem that acetone azine is by-produced. The yield is as low as 78%. (3) JP-A-56-87572 This is a method in which a hydrazodicarbonamide represented by NH 2 CONNHNHCONH 2 is subjected to a cyclization reaction in a high boiling point solvent at a high temperature of 190 to 220 ° C. to obtain urazole. In addition, there is a problem that by-products are generated due to the decomposition reaction accompanying this. The yield is also 90%. (4) JP-A-62-26277 This is a method of reacting buret represented by NH 2 CONHCONH 2 with hydrazine hydrate to obtain a hydrazine salt of urazole and then reacting with acetone to obtain urazole. It is difficult to obtain the buret of the above, requires a large amount of hydrazine hydrate, is a two-step reaction for isolating the intermediate urazole hydrazine salt, and has the problem that acetone azine is by-produced. The yield is as low as 63%. As described above, none of the conventional methods for producing urazole is industrially sufficiently satisfactory.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、上記
の従来の製造方法に見られる欠点を克服し、容易に入手
が可能な原料から、温和な条件で、しかも１段階で、定
量的に、高純度のウラゾールもしくはその塩を製造し得
る方法を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to overcome the above-mentioned drawbacks of the conventional production method, and to obtain quantitatively in one step from mildly available raw materials under mild conditions. Another object of the present invention is to provide a method for producing high-purity urazole or a salt thereof.
【０００４】[0004]
【課題を解決するための手段】本発明は低級アルコール
中にて、一般式（１） ＮＨ2ＣＯＮＨＮＨＣＯＯＲ （１） （Ｒは炭素数１〜６のアルキル基、アリール基又はアラ
ルキル基を示す）で表されるカルバモイルヒドラゾカル
ボン酸エステルに、アルカリ金属、アルカリ土類金属、
アルカリ金属のアルコラート及びアルカリ土類金属のア
ルコラートから選ばれる少なくとも１種を作用させるこ
とを特徴とする一般式（２）で表されるウラゾールもし
くはその塩の製造法に係る。According to the present invention, in a lower alcohol, a compound represented by the general formula (1) NH 2 CONNHNHCOOR (1) (R represents an alkyl group, an aryl group or an aralkyl group having 1 to 6 carbon atoms). In the carbamoyl hydrazocarboxylic acid ester represented, an alkali metal, an alkaline earth metal,
The present invention relates to a method for producing urazole or a salt thereof represented by the general formula (2), wherein at least one selected from an alkali metal alcoholate and an alkaline earth metal alcoholate is allowed to act.
【０００５】[0005]
【化２】 Embedded image
【０００６】本発明者は、鋭意研究を重ねた結果、上記
の公知の製造法のように、合成が困難な出発原料を用い
るのではなく、塩酸セミカルバジド、カルバジン酸エス
テル等より容易に誘導できるカルバモイルヒドラゾカル
ボン酸エステルを出発原料とし、これに低級アルコール
中にてアルカリ金属、アルカリ土類金属、アルカリ金属
のアルコラート及びアルカリ土類金属のアルコラートか
ら選ばれる少なくとも１種を作用させることにより、高
純度のウラゾールもしくはその塩をほぼ１００％という
高収率で製造することができることを見いだした。As a result of intensive studies, the present inventor has found that carbamoyl which can be easily derived from semicarbazide hydrochloride, carbazate, etc., is not used as in the above-mentioned known production method, but using starting materials which are difficult to synthesize. High purity by reacting hydrazocarboxylic acid ester as a starting material with at least one selected from alkali metals, alkaline earth metals, alkali metal alcoholates and alkaline earth metal alcoholates in a lower alcohol. Can be produced in a high yield of almost 100%.
【０００７】[0007]
【発明の実施の形態】本発明において原料のカルバモイ
ルヒドラゾカルボン酸エステルは、米国特許第３４１８
２９４号に記載のように、例えば一般式（３） ＮＨ2
ＣＯＮＨＮＨ2・ＨＣlで表される塩酸セミカルバジドと
一般式（４） ＣｌＣＯＯＲ（Ｒは上記に同じ）で表さ
れるクロルギ酸エステルを反応させることにより得られ
る。BEST MODE FOR CARRYING OUT THE INVENTION The carbamoylhydrazocarboxylic acid ester used as a raw material in the present invention is disclosed in US Pat.
As described in No. 294, for example, the general formula (3) NH 2
It is obtained by reacting semicarbazide hydrochloride represented by CONHNH 2 .HCl with a chloroformate represented by the general formula (4) ClCOOR (R is the same as above).
【０００８】一般式（３）と一般式（４）の化合物の割
合は適宜選択できるが、通常一般式（３）の化合物１モ
ルに対して一般式（４）の化合物を１.０〜１.５モル程
度、好ましくは１.０〜１.１モル程度とすればよい。反
応は、必要に応じて撹拌しながら、無溶媒下又は溶媒中
にて行われるが、溶媒中、特に水中で行うのが好まし
い。反応は、通常０〜５０℃程度、好ましくは０〜３０
℃程度の温度下に行われる。反応時間は特に制限されな
いが、通常１〜１０時間程度、好ましくは３〜６時間程
度とすればよい。The ratio of the compounds of the general formulas (3) and (4) can be appropriately selected, but usually the compound of the general formula (4) is added in an amount of 1.0 to 1 per mole of the compound of the general formula (3). The amount may be about 0.5 mol, preferably about 1.0 to 1.1 mol. The reaction is carried out without solvent or in a solvent with stirring as necessary, but it is preferable to carry out the reaction in a solvent, particularly in water. The reaction is usually carried out at about 0 to 50 ° C, preferably 0 to 30 ° C.
It is performed at a temperature of about ° C. The reaction time is not particularly limited, but is usually about 1 to 10 hours, preferably about 3 to 6 hours.
【０００９】また、Ｂer.，４４，３０１８〜２７に記
載のように、一般式（５）ＮＨ2ＮＨＣＯＯＲ（Ｒは上
記に同じ）で表されるカルバジン酸エステルと式（６）
ＭＯＣＮ（式中Ｍはアルカリ金属を示す）で表される
シアン酸のアルカリ金属塩を反応させることによっても
得られる。シアン酸のアルカリ金属塩としては、例え
ば、シアン酸カリウム、シアン酸ナトリウム等を挙げる
ことができる。Also, as described in Ber., 44, 3018-27, a carbazate represented by the general formula (5) NH 2 NHCOOR (R is the same as described above) and a carbazate represented by the formula (6):
It can also be obtained by reacting an alkali metal salt of cyanic acid represented by MOCN (wherein M represents an alkali metal). Examples of the alkali metal salt of cyanic acid include potassium cyanate and sodium cyanate.
【００１０】一般式（５）と一般式（６）の化合物の割
合は適宜選択できるが、通常一般式（５）の化合物１モ
ルに対して一般式（６）の化合物を１.０〜１.５モル程
度、好ましくは１.０〜１.１モル程度とすればよい。反
応は、必要に応じて撹拌しながら、無溶媒下又は溶媒中
にて行われるが、溶媒中、特に水中で行うのが好まし
い。反応は、通常０〜５０℃程度、好ましくは０〜１５
℃程度の温度下に行われる。反応時間は特に制限されな
いが、通常３０〜１８０分程度、好ましくは３０〜１２
０分程度とすればよい。The ratio of the compounds of the general formulas (5) and (6) can be selected as appropriate, but usually the compound of the general formula (6) is used in an amount of 1.0 to 1 per mole of the compound of the general formula (5). The amount may be about 0.5 mol, preferably about 1.0 to 1.1 mol. The reaction is carried out without solvent or in a solvent with stirring as necessary, but it is preferable to carry out the reaction in a solvent, particularly in water. The reaction is generally carried out at about 0 to 50 ° C, preferably at 0 to 15 ° C.
It is performed at a temperature of about ° C. The reaction time is not particularly limited, but is usually about 30 to 180 minutes, preferably 30 to 12 minutes.
It may be about 0 minutes.
【００１１】本明細書において、上記炭素数１〜６のア
ルキル基としては、例えばメチル、エチル、プロピル、
ブチル、ペンチル、ヘキシル基の、各直鎖及び分岐状の
基を挙げることができ、これらの中でも炭素数１〜４の
直鎖及び分岐状アルキル基が好ましく、メチル基及びエ
チル基が特に好ましい。アリール基としては、フェニル
基、ナフチル基等を挙げることができる。アラルキル基
としては、ベンジル基等を挙げることができる。上記で
得られた一般式（１） ＮＨ2ＣＯＮＨＮＨＣＯＯＲで
表されるカルバモイルヒドラゾカルボン酸エステルに、
低級アルコール中にてアルカリ金属、アルカリ土類金
属、アルカリ金属のアルコラート及びアルカリ土類金属
のアルコラートから選ばれる少なくとも１種を作用させ
ることにより一般式（２）で表されるウラゾールもしく
はその塩が得られる。塩としては例えばナトリウム、カ
リウム、リチウム等のアルカリ金属塩、カルシウム、マ
グネシウム等のアルカリ土類金属塩等を挙げることがで
きる。In the present specification, the alkyl group having 1 to 6 carbon atoms includes, for example, methyl, ethyl, propyl,
Examples thereof include straight-chain and branched groups of butyl, pentyl, and hexyl groups. Among them, straight-chain and branched alkyl groups having 1 to 4 carbon atoms are preferable, and methyl group and ethyl group are particularly preferable. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include a benzyl group. The carbamoylhydrazocarboxylic acid ester represented by the general formula (1) NH 2 CONHNHCOOR obtained above is
By reacting at least one selected from an alkali metal, an alkaline earth metal, an alkali metal alcoholate and an alkaline earth metal alcoholate in a lower alcohol, urazole represented by the general formula (2) or a salt thereof is obtained. Can be Examples of the salt include alkali metal salts such as sodium, potassium and lithium, and alkaline earth metal salts such as calcium and magnesium.
【００１２】低級アルコールとしては例えばメタノー
ル、エタノール、プロパノール、ブタノール等を挙げる
ことができ、メタノール、エタノールが好ましい。アル
カリ金属としては例えばナトリウム、カリウム、リチウ
ム等を挙げることができる。アルカリ土類金属としては
例えばカルシウム、マグネシウム等を挙げることができ
る。アルカリ金属のアルコラートとしては例えば上記ア
ルカリ金属と上記低級アルコールとから得られるアルコ
ラートを挙げることができる。またアルカリ土類金属の
アルコラートとしては例えば上記アルカリ土類金属と上
記低級アルコールとから得られるアルコラートを挙げる
ことができる。これらの中でも、アルカリ金属、アルカ
リ金属のアルコラート（特にメチラート、エチラート）
が好ましい。低級アルコールの使用量は特に制限はな
く、広い範囲から適宜選択できるが、通常原料のカルバ
モイルヒドラゾカルボン酸エステルの１モルに対して
０.１〜２リットル程度、好ましくは０.５〜１.５リッ
トル程度とすればよい。アルカリ金属、アルカリ土類金
属、アルカリ金属のアルコラート、アルカリ土類金属の
アルコラートから選ばれる少なくとも１種の使用量は特
に制限はなく、広い範囲から適宜選択できるが、通常原
料のカルバモイルヒドラゾカルボン酸エステルの１モル
に対して１.０〜１.５モル程度、好ましくは１.０〜１.
１モル程度とすればよい。The lower alcohol includes, for example, methanol, ethanol, propanol, butanol and the like. Methanol and ethanol are preferred. Examples of the alkali metal include sodium, potassium, lithium and the like. Examples of the alkaline earth metal include calcium, magnesium and the like. Examples of the alkali metal alcoholate include an alcoholate obtained from the above alkali metal and the above lower alcohol. Alcoholates of alkaline earth metals include, for example, alcoholates obtained from the above alkaline earth metals and the above lower alcohols. Among them, alkali metals, alkali metal alcoholates (especially methylates and ethylates)
Is preferred. The use amount of the lower alcohol is not particularly limited and can be appropriately selected from a wide range. It may be about 5 liters. The amount of at least one selected from the group consisting of alkali metals, alkaline earth metals, alkali metal alcoholates, and alkaline earth metal alcoholates is not particularly limited and can be appropriately selected from a wide range, but is usually a carbamoylhydrazocarboxylic acid as a raw material. About 1.0 to 1.5 mol, preferably 1.0 to 1.0 mol, per 1 mol of the ester.
It may be about 1 mol.
【００１３】本反応は、通常５０〜１００℃程度、好ま
しくは６５〜８０℃程度の温度下に行われるが、低級ア
ルコール還流下に行うのが特に好ましい。反応時間は特
に制限されないが、通常３〜１０時間程度、好ましくは
５〜７時間程度とすればよい。本反応は、必要に応じて
撹拌しながら、行われる。得られるウラゾールの塩
（２）は通常の精製操作により単離することができる。
更に、例えば、ウラゾールの塩を硫酸、塩酸等の酸で中
和するという一般的な手段により、極めて容易にウラゾ
ールそのものを得ることができる。This reaction is usually carried out at a temperature of about 50 to 100 ° C., preferably about 65 to 80 ° C., but it is particularly preferable to carry out the reaction under reflux of a lower alcohol. The reaction time is not particularly limited, but is usually about 3 to 10 hours, preferably about 5 to 7 hours. This reaction is performed with stirring as necessary. The resulting urazole salt (2) can be isolated by ordinary purification procedures.
Further, for example, urazole itself can be obtained extremely easily by a general means of neutralizing a salt of urazole with an acid such as sulfuric acid or hydrochloric acid.
【００１４】[0014]
実施例１ カルバモイルヒドラゾカルボン酸メチル １３.３g（０.
１mol）とナトリウムメトキシド ５.４g（０.１mol）を
無水メタノール １００ml中で、５時間還流させ、冷却
後、析出塩を濾過分離し、乾燥させることにより、ウラ
ゾールナトリウム塩 １２.３g（収率 １００％）を得
た。得られたウラゾールナトリウム塩を水に溶解し、希
塩酸で中和すると、フリーのウラゾールに１００％変換
でき、この中和液より、析出結晶を濾過分離することに
より、ウラゾールが単離できた。 実施例２ 無水エタノール １００mlに金属ナトリウム ２.３g
（０.１mol）を溶解し、これにカルバモイルヒドラゾカ
ルボン酸エチル １４.７g（０.１mol）を加え、５時間
還流させ、引き続いて実施例１と同様に処理することに
より、ウラゾールナトリウム塩 １２.３g（収率１００
％）を得た。得られたウラゾールナトリウム塩を水に溶
解し、希硫酸で中和すると、フリーのウラゾールに１０
０％変換でき、この中和液より、析出結晶を濾過分離す
ることにより、ウラゾールが単離できた。Example 1 13.3 g of methyl carbamoylhydrazocarboxylate (0.1 g)
1 mol) and 5.4 g (0.1 mol) of sodium methoxide were refluxed in 100 ml of anhydrous methanol for 5 hours. After cooling, the precipitated salt was separated by filtration and dried to obtain 12.3 g (yield) of urazole sodium salt. 100%). When the obtained urazole sodium salt was dissolved in water and neutralized with dilute hydrochloric acid, 100% conversion to free urazole could be achieved. From this neutralized solution, the precipitated crystals were separated by filtration to isolate urazole. Example 2 2.3 g of metallic sodium in 100 ml of absolute ethanol
(0.1 mol) was dissolved therein, and 14.7 g (0.1 mol) of ethyl carbamoylhydrazocarboxylate was added thereto. The mixture was refluxed for 5 hours. 12.3 g (100 yield)
%). The resulting urazole sodium salt is dissolved in water and neutralized with dilute sulfuric acid to give free urazole.
0% conversion was possible, and urazole could be isolated from this neutralized solution by filtering and separating precipitated crystals.
【００１５】[0015]
【発明の効果】本発明においては、容易に入手が可能な
原料から、温和な条件で、しかも１段階で、定量的に、
高純度のウラゾールもしくはその塩を製造することがで
きる。According to the present invention, quantitatively, in a single step, under mild conditions from easily available raw materials,
High-purity urazole or a salt thereof can be produced.
Claims (1)
ルキル基を示す）で表されるカルバモイルヒドラゾカル
ボン酸エステルに、アルカリ金属、アルカリ土類金属、
アルカリ金属のアルコラート及びアルカリ土類金属のア
ルコラートから選ばれる少なくとも１種を作用させるこ
とを特徴とする一般式（２）で表されるウラゾールもし
くはその塩の製造法。 【化１】 1. A carbamoylhydrazocarboxylic acid represented by the general formula (1) NH 2 CONNHNHCOOR (1) in which R represents an alkyl group, an aryl group or an aralkyl group having 1 to 6 carbon atoms in a lower alcohol. Acid esters, alkali metals, alkaline earth metals,
A method for producing urazole or a salt thereof represented by the general formula (2), wherein at least one selected from an alkali metal alcoholate and an alkaline earth metal alcoholate is allowed to act. Embedded image
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8178475A JPH107664A (en) | 1996-06-18 | 1996-06-18 | Production of urazole or its salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8178475A JPH107664A (en) | 1996-06-18 | 1996-06-18 | Production of urazole or its salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH107664A true JPH107664A (en) | 1998-01-13 |
Family
ID=16049153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8178475A Pending JPH107664A (en) | 1996-06-18 | 1996-06-18 | Production of urazole or its salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH107664A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019214523A (en) * | 2018-06-12 | 2019-12-19 | 株式会社トクヤマ | Method for producing semicarbazide compound, and method for producing triazolidinedione compound |
-
1996
- 1996-06-18 JP JP8178475A patent/JPH107664A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019214523A (en) * | 2018-06-12 | 2019-12-19 | 株式会社トクヤマ | Method for producing semicarbazide compound, and method for producing triazolidinedione compound |
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