JPH03258768A - Preparation of 1,3,5-perhydrotriazine-2,4,6-trithione derivative - Google Patents
Preparation of 1,3,5-perhydrotriazine-2,4,6-trithione derivativeInfo
- Publication number
- JPH03258768A JPH03258768A JP5577990A JP5577990A JPH03258768A JP H03258768 A JPH03258768 A JP H03258768A JP 5577990 A JP5577990 A JP 5577990A JP 5577990 A JP5577990 A JP 5577990A JP H03258768 A JPH03258768 A JP H03258768A
- Authority
- JP
- Japan
- Prior art keywords
- perhydrotriazine
- high pressure
- derivative
- triethylamine
- benzene
- 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.)
- Granted
Links
- -1 isothiocyanic acid ester Chemical class 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 27
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 240000007594 Oryza sativa Species 0.000 abstract description 2
- 235000007164 Oryza sativa Nutrition 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 150000007973 cyanuric acids Chemical class 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 235000009566 rice Nutrition 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 201000010099 disease Diseases 0.000 abstract 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 abstract 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 6
- LGDSHSYDSCRFAB-UHFFFAOYSA-N Methyl isothiocyanate Chemical compound CN=C=S LGDSHSYDSCRFAB-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000002540 isothiocyanates Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HBNYJWAFDZLWRS-UHFFFAOYSA-N ethyl isothiocyanate Chemical compound CCN=C=S HBNYJWAFDZLWRS-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、１，３．５−パーヒドロトリアジン−２゜４
．６−ドリチオン誘導体の製造法に関するもので。DETAILED DESCRIPTION OF THE INVENTION The present invention provides 1,3,5-perhydrotriazine-2゜4
．． This invention relates to a method for producing a 6-dorithione derivative.
より詳細にはこれらの化合物を、イソチオシアン酸エス
テルを塩基の存在下に高圧で反応させることにより簡単
かつ収率よく製造する方法に関するものである。More specifically, the present invention relates to a method for producing these compounds simply and with high yield by reacting isothiocyanate esters at high pressure in the presence of a base.
１．３．５−トリメチル−１，３，５−パーヒドロトリ
アジン−２，４，６−ドリチオンは、稲の病菌に有効で
ある（Ｇｅｒ、０ｆｆｅｎ、 ２８４７４３０（１９７
９））。またこれらの化合物の酸素同族体であるイソシ
アヌル酸の誘導体は樹脂の改質剤などとして広く工業的
に用いられており、これらの化合物も類似の効果が期待
できる。1.3.5-Trimethyl-1,3,5-perhydrotriazine-2,4,6-dolithione is effective against rice pathogens (Ger, Offen, 2847430 (197
9)). Further, derivatives of isocyanuric acid, which is an oxygen homolog of these compounds, are widely used industrially as modifiers for resins, and similar effects can be expected from these compounds.
このように１．３．５−パーヒドロトリアジン−２゜４
．６−ドリチオンの誘導体は有用な化合物であり。Thus 1.3.5-perhydrotriazine-2゜4
．． Derivatives of 6-dolithione are useful compounds.
イソチオシアン酸エステルとエポキシド及びトリエチル
アミンとの反応が知られているが、副生成物が一緒に生
成する。三級アミン触媒では高温が必要であり、低温で
はインチオシアン酸エステルの三量化反応はほとんど進
行しないなどの問題があった。Reactions of isothiocyanate esters with epoxides and triethylamine are known, but by-products are also produced. Tertiary amine catalysts require high temperatures, and the trimerization reaction of inthiocyanate esters hardly progresses at low temperatures.
したがって、本発明の目的は１，３．５−パーヒドロト
リアジン−２，４，６−ドリチオン誘導体の効率的な製
造方法を開発することである。Therefore, an object of the present invention is to develop an efficient method for producing 1,3,5-perhydrotriazine-2,4,6-dolithione derivatives.
本発明者らは、高圧条件下にイソチオシアン酸エステル
を塩基の存在下に反応させることにより１．３．５−パ
ーヒドロトリアジン−２，４，６−）−リチオンの誘導
体を高収率で製造できることを見出し、本発明を完成す
るに至った。The present inventors produced a derivative of 1,3,5-perhydrotriazine-2,4,6-)-lithion in high yield by reacting isothiocyanate ester in the presence of a base under high pressure conditions. We have discovered that this can be done, and have completed the present invention.
すなわち本発明は
一般式
％式％（１）
（式中Ｒはアルキル基又はアリール基を表す）で示され
るイソチオシアン酸エステルを塩基の存在下、高圧をか
けて反応させることを特徴とする一般式
（式中Ｒは前記と同じ。）で示される１、３．５パーヒ
ドロトリアジン−２，４，６−ドリチオン誘導体の製造
方法を提供するものである。That is, the present invention provides a general formula characterized by reacting an isothiocyanate ester represented by the general formula % (1) (wherein R represents an alkyl group or an aryl group) under high pressure in the presence of a base. The present invention provides a method for producing a 1,3.5 perhydrotriazine-2,4,6-dolithione derivative represented by the formula (wherein R is the same as above).
次に本発明における目的化合物（２）の生成経路を塩基
としてトリエチルアミンを用いたインチオシアン酸メチ
ルの反応を例にとれば下記の式（３）のように表現でき
る。Next, if the reaction of methyl inthiocyanate using triethylamine as a base is taken as an example, the production route of the target compound (2) in the present invention can be expressed as shown in the following formula (3).
ＣＩ（。CI(.
本発明の反応は通常、第三級アミン触媒の存在下にて高
圧条件下で行われる。例えばトリエチルアミン、Ｎ−メ
チルモルホリン、ピリジン等が触媒として用いられた。The reaction of the present invention is typically carried out under high pressure conditions in the presence of a tertiary amine catalyst. For example, triethylamine, N-methylmorpholine, pyridine, etc. were used as catalysts.
圧力は高圧はど好ましいが、一般には５００〜９０００
Ｋｇ／Ｃｉの範囲で選択される。反応温度は特くに制約
されないが、副反応の進行を抑制する意味では室温〜１
００℃の温度の採用が好ましい。反応時間は圧力、温度
等に左右されるが、通常５〜５０時間で十分である。High pressure is preferable, but generally 500 to 9000
Selected within the range of Kg/Ci. The reaction temperature is not particularly limited, but in order to suppress the progress of side reactions, it should be between room temperature and 1.
Preferably, a temperature of 00°C is employed. The reaction time depends on pressure, temperature, etc., but usually 5 to 50 hours is sufficient.
反応混合物から溶媒を留去したのち再結晶することによ
り本発明の目的化合物が純度よく得られる。かくして得
られた目的化合物はＩＲ，ＮＭＲｌＭＳを分析すること
によりその構造を確認できる。The target compound of the present invention can be obtained with high purity by distilling off the solvent from the reaction mixture and then recrystallizing it. The structure of the target compound thus obtained can be confirmed by IR and NMRMS analysis.
本発明方法によれば１，３．５−パーヒドロトリアジン
−２，４，６−ドリチオン誘導体を高収率かつ効率的に
製造することができる。According to the method of the present invention, 1,3,5-perhydrotriazine-2,4,6-dolithione derivatives can be produced efficiently with high yield.
次に本発明を実施例に基づきさらに詳細に説明する。 Next, the present invention will be explained in more detail based on examples.
実施例１゜
テフロンチューブにイソチオシアン酸メチル０．３７ｇ
、 トリエチルアミン０．０５ｇ及びベンゼン３ ｍ
Ｑを封入し、８０００ｋｇ／ｃｎｒに加圧して１００
℃で２０時間反応した。常圧に戻したのち反応物をとり
だし、ベンゼンを留去した。残留物をエタノールで再結
晶することにより１，３．５−トリメチル−１，３，５
，−パーヒドロトリアジン−２，４，６−ドリチオンを
７６％の収率で得た。この化合物のスペクトルデータは
文献の報告（Ｊ、Ｃｈｅｍ、ｓｏｃ、（Ｃ）、１９６６
、９０９）と一致した。Example 1 0.37g of methyl isothiocyanate in a Teflon tube
, triethylamine 0.05 g and benzene 3 m
Q is sealed and pressurized to 8000 kg/cnr to 100
The reaction was carried out at ℃ for 20 hours. After returning to normal pressure, the reaction product was taken out and benzene was distilled off. By recrystallizing the residue with ethanol, 1,3,5-trimethyl-1,3,5
,-perhydrotriazine-2,4,6-dolithione was obtained in a yield of 76%. The spectral data of this compound are reported in the literature (J, Chem, soc, (C), 1966
, 909).
ｍ、 ｐ ： １６９．１℃（文献値１６７．６℃）Ｉ
Ｒ： １０９０．１２７５ａ＋＋−１Ｎ Ｍ Ｒ：
４．１８（ｓ、９Ｈ，３ＣＨ３）ＭＳ ：２１９
同様の反応を封管中で行うと目的物はまったく得られな
かった。m, p: 169.1°C (literature value 167.6°C) I
R: 1090.1275a++-1N M R:
4.18 (s, 9H, 3CH3) MS: 219 When a similar reaction was carried out in a sealed tube, the target product was not obtained at all.
実施例２゜
前記と同様にしてイソチオシアン酸メチル０．３７ｇ、
トリエチルアミン０．０５ｇ及びべンゼン３ｍ１２を封
入し、８０００ｋｇ／ｄ、に加圧して４０’Ｃで２０時
間反応させた。ヘキサデカン０．１ｇを内部標準として
加え、ＧＬＣ分析により求めた１、３，５−）−リッチ
ルー１，３．５−パーヒドロトリアジン−２，４，６−
ドリチオンの収率は６６％であった。Example 2゜Methyl isothiocyanate 0.37g in the same manner as above,
0.05 g of triethylamine and 3 ml of benzene were sealed, and the reactor was reacted at 40'C for 20 hours under pressure of 8000 kg/d. 1,3,5-)-Richleu 1,3.5-perhydrotriazine-2,4,6- was determined by GLC analysis by adding 0.1 g of hexadecane as an internal standard.
The yield of dorithione was 66%.
実施例３゜
前記と同様にしてイソチオシアン酸メチル０．３７ｇ、
ピリジン０．０５ｇ及びベンゼン３朧Ωを８０００ｋｇ
／ｃｊ、１００℃で２０時間反応させた。ヘキサデカン
０．１ｇを内部標準として加え、ＧＬＣ分析により求め
た１、３．５−トリメチル−１，３，５−パーヒドロト
リアジン−２，４，６−ドリチオンの収率は７８％であ
った。Example 3゜Methyl isothiocyanate 0.37g in the same manner as above,
0.05g of pyridine and 8000kg of benzene 3Ω
/cj, and reacted at 100°C for 20 hours. 0.1 g of hexadecane was added as an internal standard, and the yield of 1,3,5-trimethyl-1,3,5-perhydrotriazine-2,4,6-dolithione determined by GLC analysis was 78%.
実施例４゜
前記と同様にしてイソチオシアン酸メチル０．３７ｇ、
トリエチルアミン０．０５ｇ及びアセトニトリル３ｍ１
２を８０００ｋｇ／ａ１．１００℃で２０時間反応させ
た。ヘキサデカン０．１ｇを内部標準として加え、ＧＬ
Ｃ分析により求めた１゜３．５−トリメチル−１，３，
５−パーヒドロトリアジン−２，４，６−ドリチオンの
収率は４３％であった。Example 4 0.37 g of methyl isothiocyanate was prepared in the same manner as above,
Triethylamine 0.05g and acetonitrile 3ml
2 was reacted at 8000 kg/a1.100°C for 20 hours. Add 0.1 g of hexadecane as an internal standard and GL
1゜3.5-trimethyl-1,3, determined by C analysis
The yield of 5-perhydrotriazine-2,4,6-dolithione was 43%.
実施例５゜
前記と同様にしてイソチオシアン酸エチル０．４４ｇ、
トリエチルアミン０．０５ｇ及びベンゼン３ｍ１２を８
０００ ｋｇ／ｄ、１００℃で２０時間反応させた。反
応物はシリカゲルを用いたカラムクロマトグラフィー（
ベンゼン）により１゜３．５−パーヒドロトリアジン−
２，４，６−）−リチオンを単離した。収率８９％
ＩＲ：１０９０． １２７５Ｃ！１１１１−１１ＨＮ
： ４．９７ （ｉｕａｌ、６Ｈ５３ＣＨ２）１．３
６ Ｄｔ ９Ｈ１３ＣＨ，）
”ＣＮＭＲ： １７０．２、５２．５、１０．６実施例
６゜
前記と同様にしてイソチオシアン酸ブチル０．５６ｇ、
トリエチルアミン０．０５ｇ、ベンゼン３ｍＱを８００
０ｋｇ／ｃＪ、１００℃で２０時間反応させた。反応物
からシリカゲルを用いたカラムクロマトグラフィー（ベ
ンゼン）により１゜３．５−トリメチル−１，３，５−
パーヒドロトリアジン−２，４，６−ドリチオンを単離
した。収率７％Ｉ Ｒ： １１００． １６８３ａ＋＋
−１１ＨＮＭＲ： ０．９７ （ｔ 、 ９）１．３Ｃ
Ｈ，）１．１〜１．６ （ｍ、 ６）１−３ＣＨ２）１
．５〜２．１ （ｍ、 ６Ｈ，３Ｃｆ（２）４．７５〜
５．１０ （ｍ、６Ｈ２３ＧＨｚ）Ｍ Ｓ ： ３４
５
５３Example 5 0.44 g of ethyl isothiocyanate was prepared in the same manner as above,
0.05g of triethylamine and 3m12 of benzene
000 kg/d and 100° C. for 20 hours. The reaction product was analyzed by column chromatography using silica gel (
benzene) to 1°3.5-perhydrotriazine-
2,4,6-)-lithion was isolated. Yield 89% IR: 1090. 1275C! 1111-11HN
: 4.97 (iual, 6H53CH2) 1.3
6 Dt 9H13CH,) "CNMR: 170.2, 52.5, 10.6 Example 6゜Butyl isothiocyanate 0.56 g in the same manner as above,
800 g of triethylamine, 3 mQ of benzene
The reaction was carried out at 0 kg/cJ and 100° C. for 20 hours. The reaction product was subjected to column chromatography (benzene) using silica gel to obtain 1°3.5-trimethyl-1,3,5-
Perhydrotriazine-2,4,6-dolithione was isolated. Yield 7%IR: 1100. 1683a++
-11HNMR: 0.97 (t, 9) 1.3C
H,)1.1~1.6 (m, 6)1-3CH2)1
．． 5~2.1 (m, 6H,3Cf(2)4.75~
5.10 (m, 6H23GHz) MS: 34
5 53
Claims (1)
Ｒは、アルキル基またはアリール基を示す。）で示され
るイソチオシアン酸エステルを塩基の存在下、高圧をか
けて反応させることを特徴とする一般式 ▲数式、化学式、表等があります▼・・・・・・・・・
（２） （式中Ｒは前記と同じ。）で示される１，３，５−パー
ヒドロトリアジン−２，４，６−トリチオン誘導体の製
造方法。(1) An isothiocyanate ester represented by the general formula RNCS (R in the formula represents an alkyl group or an aryl group) in the presence of a base. , general formulas characterized by reactions under high pressure▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(2) A method for producing a 1,3,5-perhydrotriazine-2,4,6-trithione derivative represented by the formula (wherein R is the same as above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5577990A JPH03258768A (en) | 1990-03-07 | 1990-03-07 | Preparation of 1,3,5-perhydrotriazine-2,4,6-trithione derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5577990A JPH03258768A (en) | 1990-03-07 | 1990-03-07 | Preparation of 1,3,5-perhydrotriazine-2,4,6-trithione derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03258768A true JPH03258768A (en) | 1991-11-19 |
| JPH0567630B2 JPH0567630B2 (en) | 1993-09-27 |
Family
ID=13008380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5577990A Granted JPH03258768A (en) | 1990-03-07 | 1990-03-07 | Preparation of 1,3,5-perhydrotriazine-2,4,6-trithione derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03258768A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111205424A (en) * | 2013-07-08 | 2020-05-29 | 旭化成株式会社 | Modified resin and resin composition |
| CN113328142A (en) * | 2021-05-26 | 2021-08-31 | 恒大新能源技术(深圳)有限公司 | Electrolyte additive, electrolyte and lithium ion battery |
-
1990
- 1990-03-07 JP JP5577990A patent/JPH03258768A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111205424A (en) * | 2013-07-08 | 2020-05-29 | 旭化成株式会社 | Modified resin and resin composition |
| CN111205424B (en) * | 2013-07-08 | 2022-04-08 | 旭化成株式会社 | Modified resin and resin composition |
| CN113328142A (en) * | 2021-05-26 | 2021-08-31 | 恒大新能源技术(深圳)有限公司 | Electrolyte additive, electrolyte and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0567630B2 (en) | 1993-09-27 |
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