JP2004099582A - Synthetic method of diallyl cyanurate - Google Patents
Synthetic method of diallyl cyanurate Download PDFInfo
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- JP2004099582A JP2004099582A JP2002306398A JP2002306398A JP2004099582A JP 2004099582 A JP2004099582 A JP 2004099582A JP 2002306398 A JP2002306398 A JP 2002306398A JP 2002306398 A JP2002306398 A JP 2002306398A JP 2004099582 A JP2004099582 A JP 2004099582A
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- cyanurate
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- VSZARHUCMHICLD-UHFFFAOYSA-N 4,6-bis(prop-2-enoxy)-1h-1,3,5-triazin-2-one Chemical compound C=CCOC=1N=C(OCC=C)NC(=O)N=1 VSZARHUCMHICLD-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000010189 synthetic method Methods 0.000 title claims 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims abstract description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 5
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims 1
- 238000010586 diagram Methods 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical class [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- -1 allyl halide Chemical class 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002798 polar solvent Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- YZBBUYKPTHDZHF-KNVGNIICSA-N (3R)-7,2'-dihydroxy-4'-methoxyisoflavanol Chemical compound OC1=CC(OC)=CC=C1[C@H]1C(O)C2=CC=C(O)C=C2OC1 YZBBUYKPTHDZHF-KNVGNIICSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- UCBVELLBUAKUNE-UHFFFAOYSA-N 1,3-bis(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)NC(=O)N(CC=C)C1=O UCBVELLBUAKUNE-UHFFFAOYSA-N 0.000 description 1
- 0 C=CCOC(*C(C1)C1C1)N=C1OCC=C Chemical compound C=CCOC(*C(C1)C1C1)N=C1OCC=C 0.000 description 1
- PQIGMEBBXZWFGX-UHFFFAOYSA-N C=CCOC(CCCC(OCC=C)=N1)NC1O Chemical compound C=CCOC(CCCC(OCC=C)=N1)NC1O PQIGMEBBXZWFGX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
【課題】従来のシアヌル酸エステル類およびイソシアヌル酸エステル類の合成法の難点を改良し、汎用性の高い多機能性のジアリルシアヌレートの合成法を提供する。
【解決手段】一般式Ｉ（化１）で表される、非プロトン性極性有機溶剤中で水酸化アルカリとトリアリルシアヌレートとを接触させることを特徴とするジアリルシアヌレートの合成法。
【化１】
【選択図】 なしAn object of the present invention is to provide a method for synthesizing multifunctional diallyl cyanurate, which has high versatility and improves the difficulty of conventional methods for synthesizing cyanuric esters and isocyanuric esters.
A method for synthesizing diallyl cyanurate, comprising contacting an alkali hydroxide and triallyl cyanurate in an aprotic polar organic solvent represented by the general formula I (formula 1).
Embedded image
[Selection diagram] None
Description
【０００１】
【発明の属する技術分野】
本発明は、プラスチックス原料、潤滑剤、合成ゴム原料および電気絶縁材料などとして有用なジアリルシアヌレートの合成法に関する。
【０００２】
【従来の技術】
優れた耐熱性と耐薬品性を有するｓ−トリアジン環誘導体、特にトリアリルシアヌレート、トリアリルイソシアヌレートは、ポリマー原料として有用なものであるが、得られるポリマーは全く柔軟性がないという難点がある。これを補う技術として、ジアリルシアヌレート、ジアリルイソシアヌレートの開発などが進められてきた。これらの化合物は塩基存在下におけるシアヌル酸またはイソシアヌル酸とハロゲン化アリルの反応により直接合成されていたが、その方法では合成コストが高く、実用化は困難であった。
【０００３】
【発明が解決しようとする課題】
本発明は、シアヌル酸エステル類に係わる上記の難点を改良し、汎用性の高い多機能性のｓ−トリアジン環化合物を提供することを目的とする。ジアリルシアヌレートの合成法としては、上記で述べたシアヌル酸の部分的アリル化のほかに、トリアリルシアヌレートの部分的加水分解が考えられるが、水やアルコールなどのプロトン性極性溶媒中でのトリアリルシアヌレートの部分的加水分解は困難とされてきた。実際に、塩化シアヌルからトリアリルシアヌレートを経るジアリルシアヌレートのワンポット合成法を検討する一環として、アリルアルコール中でトリアリルシアヌレートの加水分解を行なったが、純度の良いジアリルシアヌレートを収率良く得ることは困難であった。また、先行文献を調査したところ、ジアリルシアヌレートの合成に、非プロトン性極性溶剤と水酸化アルカリを用いる本発明は、文献未記載の新規合成法である。
【０００４】
【課題を解決するための手段】
即ち、本発明は一般式Ｉ（化１）で表されるジアリルシアヌレートの新規合成法であり、本発明者らは、上記課題を解決するため、数多くの実験を重ね、鋭意分析・検討を加えた結果、トリアリルシアヌレートが非プロトン性極性溶剤中で水酸化アルカリと接触することにより、トリアリルシアヌレート分子から選択的に１分子のアリルアルコールが脱離するという知見を得て、本発明を完成するに至った。
【０００５】
【化１】
【０００６】
本発明において、非プロトン性極性溶剤と水酸化アルカリを使用することにより、トリアリルシアヌレートからアリルアルコールが１分子のみ脱離することを見出したことで、熱安定性、高周波電気特性の優れたポリマー材料であるジアリルシアヌレートを合成することが可能になった。この一連の合成操作で生成するのは、目的物質のジアリルシアヌレート、アリルアルコール、硫酸アルカリ金属塩である。アリルアルコールはトリアリルシアヌレートの合成に再利用することが可能であり、回収した溶媒も再利用できることから、低コストの反応を実現できる。また、上記のように原料が無駄にならないことと併せて、溶媒にジメチルスルホキシド（以下ＤＭＳＯと略す）などの毒性の低い溶剤を用いることで環境負荷の少ない合成法でもある。
【０００７】
本発明で使用する非プロトン性極性有機溶剤とは、ＤＭＳＯ、ジメチルホルムアミド（以下ＤＭＦと略す）、ジメチルアセトアミド（以下ＤＭＡＡと略す）、１−メチル−２−ピロリジノン、ジメチルイミダゾリジノン（以下ＤＭＩと略す）からなる群から選ばれた、少なくとも１種のものであり、水酸化アルカリとは、水酸化ナトリウムまたは水酸化カリウムから選ばれた、少なくとも１種のものである。
【０００８】
具体的には、ＤＭＳＯやＤＭＦなどの極性溶媒中に水酸化ナトリウムなどの水酸化アルカリを分散させ、そこへトリアリルシアヌレートを加えると、トリアリルシアヌレート分子の１つのアリルエステル部のみが加アルカリ分解され、ジアリルシアヌレートのモノアルカリ金属塩になる。この反応は、室温でも１５−１７時間でほぼ定量的に進行するが、６０℃程度の加熱を行なえば反応時間を短縮することができる。
【０００９】
この反応によって得られたジアリルシアヌレートのアルカリ金属塩の溶液から、アリルアルコールおよび溶媒を蒸留で除いた後、ジアリルシアヌレートアルカリ金属塩を水溶液とし、有機溶剤で分液操作を行なうことによって、未反応トリアリルシアヌレートやその他の微量不純物を有機層へ除くことができる。この分液操作の後、水溶液を当量の硫酸を用いて弱酸性にすることにより、晶析または有機溶剤による抽出で、フリーで純粋なジアリルシアヌレートを取り出すことが可能である。また、回収したアリルアルコールは原料であるトリアリルシアヌレートの合成原料に再利用することが可能となり、回収した溶媒も再利用することができる。
【００１０】
【発明の実施の形態】
以下、本発明を実施例によって説明する。
【実施例１】
四つ口フラスコ（５００ｍｌ）にＤＭＳＯ１００ｍｌ、ペレット状の水酸化ナトリウム６．０ｇ（１５０ｍｍｏｌ）、トリアリルシアヌレート３７．４ｇ（１５０ｍｍｏｌ）を仕込み、室温で１７時間撹拌した。減圧蒸留によって反応溶液からアリルアルコールおよびＤＭＳＯを除き、水１００ｍｌを加え、トルエン５０ｍｌを用いた分液操作を２回行い、未反応物質やその他の不純物をトルエン層に抽出させることによって除いた。水層に酢酸エチル８００ｍｌを加え、引き続いて硫酸７．３５ｇ（７５ｍｍｏｌ）／水２０ｍｌを加えて、遊離してきたジアリルシアヌレートを分液操作にて有機層に抽出した。有機層を水１００ｍｌを用いた分液洗浄を２回行ったのち、無水硫酸ナトリウムを用いて乾燥し減圧下で濃縮すると、ジアリルシアヌレートの結晶２９．２ｇを得た（収率９３％。表１−実験番号１）。
【００１１】
【表１】
【００１２】
尚、基本的反応操作および反応スケールは上記の実施例１に従い、反応溶媒をＤＭＳＯからＤＭＦ、ＤＭＡＡ、１−メチル−２−ピロリジノン、ＤＭＩにそれぞれ置き換えて行なった実験（表１−実験番号２〜５）、水酸化アルカリとして水酸化カリウムを使用した実験（表１−実験番号６）、６０℃での加熱条件下で反応を行なった実験（表１−実験番号７）についてのジアリルシアヌレートの収率は、表１にまとめて記した。
【００１３】
【実施例２】
四つ口フラスコ（５００ｍｌ）にＤＭＳＯ１００ｍｌ、ペレット状の水酸化ナトリウム６．０ｇ（１５０ｍｍｏｌ）、トリアリルシアヌレート３７．４ｇ（１５０ｍｍｏｌ）を仕込み、室温で１７時間撹拌した。減圧蒸留によって反応溶液からアリルアルコールおよびＤＭＳＯを除き、水２００ｍｌを加え、トルエン５０ｍｌを用いた分液操作を２回行い、未反応物質やその他の不純物をトルエン層に抽出させることによって除いた。水層に硫酸７．３５ｇ（７５ｍｍｏｌ）／水１００ｍｌをゆっくり加えて遊離してきた結晶をろ過で分離し、充分に乾燥させると、ジアリルシアヌレートの結晶２９．５ｇを得た（収率９４％）。
【００１４】
【比較例】
上記の実施例１に従い、反応溶媒のみＤＭＳＯをアリルアルコールに置き換えて反応を行なったところ、ジアリルシアヌレートの結晶が１７．８ｇ（収率５７％）しか得られなかった。
【００１５】
【発明の効果】
非プロトン性極性溶剤と水酸化アルカリを使用することにより、トリアリルシアヌレートからアリルアルコールを１分子のみ脱離することを見出したことで、多用途で高機能を有するジアリルシアヌレートを高収率、低コストで合成することが可能になった。本発明に関する技術は、ジアリルシアヌレートだけにとどまらず、そこから更に高い性能を持つ新しい誘導体へと導く可能性があり、その効果は多大である。
【図面の簡単な説明】
【図１】実施例１に示すジアリルシアヌレートの合成工程を表した図である。
【図２】実施例２に示すジアリルシアヌレートの合成工程を表した図である。
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for synthesizing diallyl cyanurate, which is useful as a raw material for plastics, a lubricant, a raw material for synthetic rubber, an electric insulating material, and the like.
[0002]
[Prior art]
S-Triazine ring derivatives having excellent heat resistance and chemical resistance, particularly triallyl cyanurate and triallyl isocyanurate, are useful as polymer raw materials, but have the disadvantage that the resulting polymer has no flexibility at all. is there. Development of diallyl cyanurate and diallyl isocyanurate has been promoted as a technique to supplement this. These compounds have been directly synthesized by the reaction of cyanuric acid or isocyanuric acid and allyl halide in the presence of a base, but the synthesis cost is high in this method, and practical use has been difficult.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to improve the above-mentioned difficulties relating to cyanuric esters and provide a highly versatile multifunctional s-triazine ring compound. As a method for synthesizing diallyl cyanurate, in addition to the partial allylation of cyanuric acid described above, partial hydrolysis of triallyl cyanurate can be considered, but in a protic polar solvent such as water or alcohol. Partial hydrolysis of triallyl cyanurate has been difficult. In fact, as part of studying a one-pot synthesis method of diallyl cyanurate from cyanuric chloride via triallyl cyanurate, triallyl cyanurate was hydrolyzed in allyl alcohol. It was difficult to get good. Further, when the prior literature was examined, the present invention using an aprotic polar solvent and an alkali hydroxide for the synthesis of diallyl cyanurate is a novel synthesis method not described in the literature.
[0004]
[Means for Solving the Problems]
That is, the present invention is a novel method for synthesizing the diallyl cyanurate represented by the general formula I (Chemical Formula 1). As a result, we obtained the finding that one molecule of allyl alcohol is selectively eliminated from triallyl cyanurate molecules by contacting triallyl cyanurate with alkali hydroxide in an aprotic polar solvent. The invention has been completed.
[0005]
Embedded image
[0006]
In the present invention, by using an aprotic polar solvent and an alkali hydroxide, it has been found that only one molecule of allyl alcohol is eliminated from triallyl cyanurate. It has become possible to synthesize diallyl cyanurate, a polymer material. The target substances diallyl cyanurate, allyl alcohol and alkali metal sulfate are produced by this series of synthesis operations. Allyl alcohol can be reused in the synthesis of triallyl cyanurate, and the recovered solvent can be reused, so that a low-cost reaction can be realized. In addition, as described above, in addition to the fact that the raw materials are not wasted, the use of a low-toxic solvent such as dimethylsulfoxide (hereinafter abbreviated as DMSO) as a solvent is a synthesis method with a low environmental load.
[0007]
The aprotic polar organic solvent used in the present invention includes DMSO, dimethylformamide (hereinafter abbreviated as DMF), dimethylacetamide (hereinafter abbreviated as DMAA), 1-methyl-2-pyrrolidinone, dimethylimidazolidinone (hereinafter DMI). Abbreviated), and the alkali hydroxide is at least one selected from sodium hydroxide or potassium hydroxide.
[0008]
Specifically, when an alkali hydroxide such as sodium hydroxide is dispersed in a polar solvent such as DMSO or DMF, and triallyl cyanurate is added thereto, only one allyl ester portion of the triallyl cyanurate molecule is added. Alkali is decomposed into a monoalkali metal salt of diallyl cyanurate. This reaction proceeds almost quantitatively in 15 to 17 hours even at room temperature, but heating at about 60 ° C. can shorten the reaction time.
[0009]
After removing allyl alcohol and the solvent from the solution of the alkali metal diallyl cyanurate obtained by this reaction by distillation, the diallyl cyanurate alkali metal salt is converted into an aqueous solution, and the liquid is separated using an organic solvent. Reaction triallyl cyanurate and other trace impurities can be removed to the organic layer. After this liquid separation operation, the aqueous solution is made weakly acidic with an equivalent amount of sulfuric acid, whereby free and pure diallyl cyanurate can be taken out by crystallization or extraction with an organic solvent. Further, the recovered allyl alcohol can be reused as a raw material for synthesizing triallyl cyanurate as a raw material, and the recovered solvent can also be reused.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described with reference to examples.
Embodiment 1
A four-necked flask (500 ml) was charged with 100 ml of DMSO, 6.0 g (150 mmol) of sodium hydroxide in pellet form, and 37.4 g (150 mmol) of triallyl cyanurate, and stirred at room temperature for 17 hours. Allyl alcohol and DMSO were removed from the reaction solution by distillation under reduced pressure, 100 ml of water was added, liquid separation was performed twice using 50 ml of toluene, and unreacted substances and other impurities were removed by extracting into the toluene layer. 800 ml of ethyl acetate was added to the aqueous layer, followed by 7.35 g (75 mmol) of sulfuric acid / 20 ml of water, and the released diallyl cyanurate was extracted into the organic layer by a liquid separation operation. The organic layer was separated and washed twice with 100 ml of water, dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 29.2 g of diallyl cyanurate crystals (93% yield, table). 1-Experiment number 1).
[0011]
[Table 1]
[0012]
The basic reaction procedure and reaction scale were the same as in Example 1 described above, except that the reaction solvent was changed from DMSO to DMF, DMAA, 1-methyl-2-pyrrolidinone, and DMI. 5), an experiment using potassium hydroxide as an alkali hydroxide (Table 1-Experiment No. 6), and an experiment in which the reaction was carried out under heating conditions at 60 ° C (Table 1-Experiment No. 7). The yields are summarized in Table 1.
[0013]
A four-necked flask (500 ml) was charged with 100 ml of DMSO, 6.0 g (150 mmol) of sodium hydroxide in pellet form, and 37.4 g (150 mmol) of triallyl cyanurate, and stirred at room temperature for 17 hours. Allyl alcohol and DMSO were removed from the reaction solution by distillation under reduced pressure, 200 ml of water was added, liquid separation was performed twice using 50 ml of toluene, and unreacted substances and other impurities were removed by extracting into the toluene layer. To the aqueous layer was slowly added 7.35 g (75 mmol) of sulfuric acid / 100 ml of water, and the separated crystals were separated by filtration and sufficiently dried to obtain 29.5 g of diallyl cyanurate crystals (94% yield). .
[0014]
[Comparative example]
According to Example 1 described above, when the reaction was carried out by substituting allyl alcohol for DMSO only for the reaction solvent, only 17.8 g (57% yield) of diallyl cyanurate crystals were obtained.
[0015]
【The invention's effect】
By using an aprotic polar solvent and an alkali hydroxide, it has been found that only one molecule of allyl alcohol is eliminated from triallyl cyanurate, so that diallyl cyanurate having a versatile and high performance can be obtained in high yield. , At low cost. The technology relating to the present invention is not limited to diallyl cyanurate, but may lead to a new derivative having higher performance, and the effect is enormous.
[Brief description of the drawings]
FIG. 1 is a diagram showing a synthesis process of diallyl cyanurate shown in Example 1.
FIG. 2 is a view showing a synthesis process of diallyl cyanurate shown in Example 2.
Claims (3)
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