JPH09227532A - Production of 2-nitroiminohexahydro-1,3,5-triazines - Google Patents
Production of 2-nitroiminohexahydro-1,3,5-triazinesInfo
- Publication number
- JPH09227532A JPH09227532A JP3934096A JP3934096A JPH09227532A JP H09227532 A JPH09227532 A JP H09227532A JP 3934096 A JP3934096 A JP 3934096A JP 3934096 A JP3934096 A JP 3934096A JP H09227532 A JPH09227532 A JP H09227532A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- tetrahydrofuryl
- nitroimino
- triazine
- 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.)
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- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は２−ニトロイミノヘ
キサヒドロ−１，３，５−トリアジン類の製造法に関す
る。本発明は農薬（特に殺虫剤）の分野において利用さ
れる化合物またはその中間体の合成に際して有用であ
る。TECHNICAL FIELD The present invention relates to a method for producing 2-nitroiminohexahydro-1,3,5-triazines. INDUSTRIAL APPLICABILITY The present invention is useful in the synthesis of compounds used in the field of agricultural chemicals (particularly insecticides) or intermediates thereof.
【０００２】[0002]
【従来の技術】２−ニトロイミノヘキサヒドロ−１，
３，５−トリアジン類が農薬（特に殺虫剤）またはその
中間体として有用であることは良く知られている（ＷＯ
９１／０１９７８号公報、特開平３−２１８３７０号公
報、特開平３−２９１２６７号公報、特開平４−２４３
８７６号公報、特開平４−２７３８６３号公報、特開平
４−３３００４９号公報、特開平４−３４６９８４号公
報、特開平７−１７３１５７号公報、特開平７−１７９
４４８号公報等）。１，３，５−三置換−２−ニトロイ
ミノヘキサヒドロ−１，３，５−トリアジン類の製造法
としては次のものが挙げられる。2. Description of the Prior Art 2-Nitroiminohexahydro-1,
It is well known that 3,5-triazines are useful as pesticides (particularly insecticides) or their intermediates (WO
91/01978, JP-A-3-218370, JP-A-3-291267, JP-A-4-243.
No. 876, No. 4-273863, No. 4-330049, No. 4-346984, No. 7-173157, No. 7-179.
No. 448, etc.). Examples of the method for producing 1,3,5-trisubstituted-2-nitroiminohexahydro-1,3,5-triazines include the following.
【０００３】二置換ニトログアニジンを一級アミンと
ホルマリンで環化して得る反応式（１）（化４）の方
法。（ＷＯ９１／０１９７８号公報、特開平３−２１８
３７０号公報、特開平４−２４３８７６号公報、特開平
４−３４６９８４号公報。）A method of reaction formula (1) (formula 4) obtained by cyclizing a disubstituted nitroguanidine with a primary amine and formalin. (WO91 / 01978, JP-A-3-218
370, JP-A-4-243876, and JP-A-4-346984. )
【化４】 Embedded image
【０００４】１，５−二置換−２−ニトロイミノヘキ
サヒドロ−１，３，５−トリアジンを塩基の存在下、式
（４）（化５）1,5-disubstituted-2-nitroiminohexahydro-1,3,5-triazine was prepared in the presence of a base to give a compound of formula (4)
【化５】 （式中、Ｒ6は水素原子、アルキル基を示し、Ｂは芳香
環を示し、Ｍは脱離基を示す。）で表される化合物を反
応させて得る反応式（２）（化６）の方法。（特開平３
−２１８３７０号公報、特開平４−２４３８７６号公
報、特開平４−２７３８６３号公報、特開平４−３３０
０４９号公報、特開平４−３４６９８４号公報、特開平
７−１７３１５７号公報。）Embedded image (In the formula, R 6 represents a hydrogen atom or an alkyl group, B represents an aromatic ring, and M represents a leaving group.) A reaction formula (2) (Formula 6) obtained by reacting a compound represented by the formula the method of. (Japanese Unexamined Patent Publication
-218370, JP-A-4-243876, JP-A-4-273863, and JP-A-4-330.
049, JP-A-4-346984, JP-A-7-173157. )
【化６】 [Chemical 6]
【０００５】１，５−二置換−２−ニトロイミノヘキ
サヒドロ−１，３，５−トリアジンを塩基の存在下、式
（５）（化７）1,5-Disubstituted-2-nitroiminohexahydro-1,3,5-triazine was prepared in the presence of a base to give a compound of formula (5)
【化７】 （式中、Ｒ9はアルキル基を示し、Ｍは脱離基を示
す。）で表される化合物を反応させて得る反応式（３）
（化８）の方法。（特開平４−２４３８７６号公報、特
開平４−２７３８６３号公報、特開平４−３４６９８４
号公報、特開平７−１７３１５７号公報、特開平７−１
７９４４８号公報。）Embedded image (In the formula, R 9 represents an alkyl group, and M represents a leaving group.) Reaction formula (3) obtained by reacting a compound represented by
The method of (Chemical Formula 8). (JP-A-4-243876, JP-A-4-273863, JP-A-4-346984
JP-A-7-173157, JP-A7-1
No. 79448. )
【化８】 Embedded image
【０００６】方法においては原料となる非環状の二置
換ニトログアニジンの合成が容易でなく、非対象の場合
は更に困難であり、工業的な製造法としては不適当であ
る。方法は容易に反応しうる芳香環のα位に脱離基を
有する場合の製造法であり、一般的なアルキル基の場合
と同列に論ずることはできない。の方法は実施例の記
載では、塩基が水素化ナトリウムに限られており、工業
的製法としては不適当である。In the method, it is not easy to synthesize the acyclic disubstituted nitroguanidine as a raw material, and it is more difficult if it is not a target, and it is unsuitable as an industrial production method. The method is a production method in the case of having a leaving group at the α-position of an aromatic ring which can be easily reacted, and cannot be discussed in the same manner as in the case of general alkyl groups. In the description of the examples, the method of 1 is limited to sodium hydride as the base, and is not suitable as an industrial production method.
【０００７】[0007]
【発明が解決しようとする課題】本発明が解決しようと
する課題は１，３，５−三置換−２−ニトロイミノヘキ
サヒドロ−１，３，５−トリアジン類を高選択率、高収
率で工業的に容易に製造しうる方法を提供する事にあ
る。The problem to be solved by the present invention is to provide 1,3,5-trisubstituted-2-nitroiminohexahydro-1,3,5-triazines with high selectivity and high yield. It is to provide a method that can be easily manufactured industrially.
【０００８】[0008]
【課題を解決するための手段】本発明者らは１，５−二
置換−２−ニトロイミノヘキサヒドロ−１，３，５−ト
リアジン類のアルキル化を鋭意検討した結果、水酸化ア
ルカリ金属の存在下、特定のアルキル化剤を用いると、
５位窒素の置換基がメチル基の場合、目的化合物への選
択率が悪く低収率であるのに対し、５位窒素の置換基を
炭素数２〜１０のアルキル基に代えることによって、選
択率が大巾に向上し収率が改善され、また品質が高純度
になることを見出し、本発明を完成させた。The present inventors have diligently studied the alkylation of 1,5-disubstituted-2-nitroiminohexahydro-1,3,5-triazines. In the presence of a particular alkylating agent,
When the substituent at the 5-position nitrogen is a methyl group, the selectivity to the target compound is poor and the yield is low, while the substitution at the 5-position nitrogen is changed to an alkyl group having 2 to 10 carbon atoms for selection. The inventors have found that the rate is greatly improved, the yield is improved, and the quality is high purity, and the present invention has been completed.
【０００９】即ち、本発明は式（１）（化９）That is, the present invention uses the formula (1) (formula 9)
【化９】 （式中、Ａは置換されていてもよい芳香族または非芳香
族の炭化水素環、置換されていてもよい芳香族または非
芳香族の複素環、水素原子、置換されていてもよいアル
キル基またはアルケニル基、アルキニル基を示し、Ｒは
置換されていても良い炭素数２〜１０の鎖状または環状
のアルキル基を示す。）で表される化合物と式（２）
（化１０）Embedded image (In the formula, A is an optionally substituted aromatic or non-aromatic hydrocarbon ring, an optionally substituted aromatic or non-aromatic heterocycle, a hydrogen atom, and an optionally substituted alkyl group. Or an alkenyl group or an alkynyl group, and R represents an optionally substituted chain or cyclic alkyl group having 2 to 10 carbon atoms) and the formula (2).
(Chemical formula 10)
【化１０】 （式中、Ｒ1は炭素数１〜３のアルキル基を示し、Ｒ2は
置換されていてもよい炭素数１〜３のアルキル基、置換
されていてもよいフェニル基、炭素数１〜３のアルコキ
シ基を示す。）で表される化合物を水酸化アルカリ金属
類の存在下に反応させることを特徴とする式（３）（化
１１）Embedded image (In the formula, R 1 represents an alkyl group having 1 to 3 carbon atoms, R 2 is an optionally substituted alkyl group having 1 to 3 carbon atoms, optionally substituted phenyl group, 1 to 3 carbon atoms Of the formula (3) (Chemical Formula 11), characterized in that the compound represented by the formula (3) is reacted in the presence of an alkali metal hydroxide.
【化１１】 （式中、Ａ、Ｒ、Ｒ1は上記の意味を示す。）で表され
る化合物の製造法である。Embedded image (In the formula, A, R, and R 1 have the above meanings.).
【００１０】[0010]
【発明の実施の形態】上記式中のＡの典型的な例として
はフェニル基、３−ニトロフェニル基、３−シアノフェ
ニル基、３−クロロフェニル基、３−トリフルオロメチ
ルフェニル基、シクロペンチル基、シクロヘキシル基、
３−メチルシクロペンチル基、４−メチルシクロヘキシ
ル基、２−ピリジル基、３−ピリジル基、２−クロロ−
５−ピリジル基、２−メチル−５−ピリジル基、２−メ
トキシ−５−ピリジル基、５−チアゾリル基、２−クロ
ロ−５−チアゾリル基、２−メチル−５−チアゾリル
基、２−クロロ−５−ピリミジル基、２−クロロ−５−
オキサゾリル基、２−メチル−５−オキサゾリル基、３
−フリル基、２−フリル基、３−テトラヒドロフリル
基、２−テトラヒドロフリル基、２−メチル−４−テト
ラヒドロフリル基、２−エチル−４−テトラヒドロフリ
ル基、２−イソプロピル−４−テトラヒドロフリル基、
２−ｔ−ブチル−４−テトラヒドロフリル基、２，２−
ジメチル−４−テトラヒドロフリル基、水素原子、メチ
ル基、エチル基、イソプロピル基、ｔ−ブチル基、メト
キシメチル基、メチルチオメチル基、クロロメチル基、
トリフルオロメチル基、フェニルメチル基、ビニル基、
エチニル基等が挙げられる。Ｒの典型的な例としてはエ
チル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブ
チル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、２−
ペンチル基、３−ペンチル基、ネオペンチル基、２−ヘ
キシル基、３−ヘキシル基、２−メチル−２−ペンチル
基、３−メチル−３−ペンチル基、４−ヘプチル基、４
−オクチル基、５−ノニル基、５−デシル基、４−ｎ−
プロピル−４−ヘプチル基、シクロプロピル基、シクロ
ブチル基、シクロペンチル基、シクロヘキシル基、ベン
ジル基等が挙げられる。Ｒ1の典型的な例としてはメチ
ル基、エチル基、ｎ−プロピル基等が挙げられる。Ｒ2
の典型的な例としてはメチル基、エチル基、トリフルオ
ロメチル基、フェニル基、４−トリル基、メトキシ基、
エトキシ基等が挙げられる。アルキル化剤の具体例とし
ては、ジメチル硫酸、ジエチル硫酸、メタンスルホン酸
メチル、メタンスルホン酸エチル、エタンスルホン酸メ
チル、エタンスルホン酸エチル、トリフルオロメタンス
ルホン酸メチル、プロパンスルホン酸メチル、イソプロ
ピルスルホン酸メチル、ベンゼンスルホン酸メチル、ベ
ンゼンスルホン酸ｎ−プロピル、トルエンスルホン酸メ
チル、トルエンスルホン酸エチル、トルエンスルホン酸
ｎ−プロピル、４−クロロフェニルスルホン酸メチル等
が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION Typical examples of A in the above formula are phenyl group, 3-nitrophenyl group, 3-cyanophenyl group, 3-chlorophenyl group, 3-trifluoromethylphenyl group, cyclopentyl group, Cyclohexyl group,
3-methylcyclopentyl group, 4-methylcyclohexyl group, 2-pyridyl group, 3-pyridyl group, 2-chloro-
5-pyridyl group, 2-methyl-5-pyridyl group, 2-methoxy-5-pyridyl group, 5-thiazolyl group, 2-chloro-5-thiazolyl group, 2-methyl-5-thiazolyl group, 2-chloro- 5-pyrimidyl group, 2-chloro-5-
Oxazolyl group, 2-methyl-5-oxazolyl group, 3
-Furyl group, 2-furyl group, 3-tetrahydrofuryl group, 2-tetrahydrofuryl group, 2-methyl-4-tetrahydrofuryl group, 2-ethyl-4-tetrahydrofuryl group, 2-isopropyl-4-tetrahydrofuryl group ,
2-t-butyl-4-tetrahydrofuryl group, 2,2-
Dimethyl-4-tetrahydrofuryl group, hydrogen atom, methyl group, ethyl group, isopropyl group, t-butyl group, methoxymethyl group, methylthiomethyl group, chloromethyl group,
Trifluoromethyl group, phenylmethyl group, vinyl group,
Examples thereof include an ethynyl group. Typical examples of R are ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, 2-
Pentyl group, 3-pentyl group, neopentyl group, 2-hexyl group, 3-hexyl group, 2-methyl-2-pentyl group, 3-methyl-3-pentyl group, 4-heptyl group, 4
-Octyl group, 5-nonyl group, 5-decyl group, 4-n-
Examples thereof include a propyl-4-heptyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a benzyl group. Typical examples of R 1 include methyl group, ethyl group, n-propyl group and the like. R 2
As typical examples of, methyl group, ethyl group, trifluoromethyl group, phenyl group, 4-tolyl group, methoxy group,
Examples thereof include an ethoxy group. Specific examples of the alkylating agent include dimethyl sulfate, diethyl sulfate, methyl methanesulfonate, ethyl methanesulfonate, methyl ethanesulfonate, ethyl ethanesulfonate, methyl trifluoromethanesulfonate, methyl propanesulfonate, methyl isopropylsulfonate. , Methyl benzene sulfonate, n-propyl benzene sulfonate, methyl toluene sulfonate, ethyl toluene sulfonate, n-propyl toluene sulfonate, methyl 4-chlorophenyl sulfonate, and the like.
【００１１】式（１）の化合物は公知の方法で合成で
き、例えば、下記の反応式（４）（化１２）により製造
することができる。（特開平４−２７３８６３号公報
等。）The compound of the formula (1) can be synthesized by a known method and can be produced, for example, by the following reaction formula (4) (formula 12). (JP-A-4-273863, etc.)
【化１２】 （式中、Ａ及びＲは前記の意味を示す。）即ち、式
（６）で表される一置換ニトログアニジンを式（７）で
表されるアミン及びホルマリンと反応させて容易に製造
できる。Embedded image (In the formula, A and R have the above-mentioned meanings.) That is, it can be easily produced by reacting the monosubstituted nitroguanidine represented by the formula (6) with the amine represented by the formula (7) and formalin.
【００１２】原料となる一置換ニトログアニジンも公知
の方法で容易に合成でき、例えば、下記の反応式（５）
（化１３）により製造することができる。（Ｊ．Ａｍ．
Ｃｈｅｍ．Ｓｏｃ．，６９，３０２８（１９４７）、特
開平３−１５７３０８号公報等。）The monosubstituted nitroguanidine as a raw material can be easily synthesized by a known method. For example, the following reaction formula (5)
It can be produced by (J. Am.
Chem. Soc. , 69 , 3028 (1947), JP-A-3-157308, and the like. )
【化１３】 （式中、Ａは前記の意味を示し、Ｘは酸素原子、硫黄原
子、−ＮＨ−を示し、Ｒ 12は水素原子又は低級アルキル
基を示す。）即ち、式（８）で表されるニトログアニジ
ンまたはニトロイソ尿素誘導体と式（９）で表されるア
ミンを反応させて容易に製造できる。Embedded image(In the formula, A represents the above meaning, X represents an oxygen atom, a sulfur source
Child, -NH-, R 12Is a hydrogen atom or lower alkyl
Represents a group. ) That is, the nitroguanidinium represented by the formula (8)
Or a nitroisourea derivative and an amine represented by the formula (9).
It can be easily produced by reacting min.
【００１３】本発明の反応に使用される水酸化アルカリ
金属類としては水酸化リチウム、水酸化ナトリウム、水
酸化カリウム等が挙げられる。使用される水酸化アルカ
リ金属類の量は式（１）の化合物に対して１当量以上で
あれば良いが、通常１〜３当量が使用され、好ましくは
１〜２当量である。Examples of the alkali metal hydroxide used in the reaction of the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. The amount of alkali metal hydroxide used may be 1 equivalent or more with respect to the compound of the formula (1), but usually 1 to 3 equivalents are used, and preferably 1 to 2 equivalents.
【００１４】本発明の反応に使用されるアルキル化剤の
量は式（１）の化合物に対して１当量以上であれば良い
が、通常１〜２当量が使用され、好ましくは１〜１．５
当量である。水酸化アルカリ金属類及びアルキル化剤の
装入順序に制限は無いが、アルキル化剤と水酸化アルカ
リ金属類の性質上、いずれかを最後にする方法が好まし
い。The amount of the alkylating agent used in the reaction of the present invention may be 1 equivalent or more based on the compound of the formula (1), but it is usually 1 to 2 equivalents, preferably 1 to 1. 5
Is equivalent. The order of charging the alkali metal hydroxide and the alkylating agent is not limited, but a method in which either one is the last is preferable in view of the properties of the alkylating agent and the alkali metal hydroxide.
【００１５】本発明のアルキル化反応は溶媒中で実施さ
れる。使用される溶媒としてはベンゼン、トルエン等の
芳香族炭化水素類、ヘキサン等の脂肪族炭化水素類、ジ
メチルホルムアミド、ジメチルスルホキシド、１，３−
ジメチル−２−イミダゾリジノン、１−メチル−２−ピ
ロリジノン等の非プロトン性極性溶媒、ジエチルエーテ
ル、１，２−ジメトキシエタン、テトラヒドロフラン、
ジオキサン等のエーテル類、アセトニトリル等のニトリ
ル類、ジクロロメタン、１，２−ジクロロエタン等のハ
ロゲン化炭化水素類等が挙げられ、好ましくはジメチル
ホルムアミド、ジメチルスルホキシド、１，３−ジメチ
ル−２−イミダゾリジノン、アセトニトリル、ジクロロ
メタン、特に好ましくはアセトニトリル、ジクロロメタ
ンが挙げられる。The alkylation reaction of the present invention is carried out in a solvent. Examples of the solvent used include aromatic hydrocarbons such as benzene and toluene, aliphatic hydrocarbons such as hexane, dimethylformamide, dimethylsulfoxide, 1,3-
Aprotic polar solvents such as dimethyl-2-imidazolidinone, 1-methyl-2-pyrrolidinone, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran,
Examples thereof include ethers such as dioxane, nitriles such as acetonitrile, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, and the like, preferably dimethylformamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. , Acetonitrile, dichloromethane, particularly preferably acetonitrile, dichloromethane.
【００１６】反応温度及び時間は広範囲に変化させうる
が、一般的に反応温度は−３０乃至１５０℃であり、好
ましくは−２０乃至１００℃である。反応時間は一般的
に０．０１乃至５０時間であり、好ましくは０．１乃至
２４時間である。反応終了後の処理については、常法に
従って行う事が可能である。例えば、無機塩を濾過し、
濾液から溶媒を減圧留去することによって取り出す事が
できる。あるいは分液抽出によって取り出すこともでき
る。必要に応じて晶析等の精製を行えば、より純度の高
いものを得ることができる。The reaction temperature and time can be varied over a wide range, but generally the reaction temperature is -30 to 150 ° C, preferably -20 to 100 ° C. The reaction time is generally 0.01 to 50 hours, preferably 0.1 to 24 hours. The treatment after completion of the reaction can be performed according to a conventional method. For example, filtering inorganic salts,
It can be taken out by distilling off the solvent from the filtrate under reduced pressure. Alternatively, it can be extracted by liquid separation extraction. If necessary, purification such as crystallization can be performed to obtain a product with higher purity.
【００１７】式（１）、式（３）等ニトロイミノ基を有
する化合物は異性体（ｓｙｎ−及びａｎｔｉ−異性体）
並びに互変異性体として存在しうる。また、式（３）に
おいてＡが３−テトラヒドロフリル基の場合、テトラヒ
ドロフラン環の３位に不斉炭素が存在し、光学活性異性
体、ラセミ体及び任意の割合の混合物として存在しう
る。この種の全ての異性体及び互変異性体、並びにその
混合物も本発明に使用しうる。このようにして得られる
式（３）で表される化合物を加水分解すれば、対称また
は非対称の二置換ニトログアニジンを得ることができ
る。Compounds having a nitroimino group such as formula (1) and formula (3) are isomers (syn- and anti-isomers).
As well as tautomers. Further, in the formula (3), when A is a 3-tetrahydrofuryl group, an asymmetric carbon atom is present at the 3-position of the tetrahydrofuran ring, and the compound can be present as an optically active isomer, a racemate and a mixture in any proportion. All isomers and tautomers of this type, and mixtures thereof, may also be used in the present invention. By hydrolyzing the compound represented by formula (3) thus obtained, a symmetrical or asymmetrical disubstituted nitroguanidine can be obtained.
【００１８】[0018]
【実施例】以下、実施例、比較例及び参考例を挙げて、
本発明の内容を具体的に説明する。The following examples, comparative examples and reference examples are given below.
The contents of the present invention will be specifically described.
【００１９】実施例１ ５−イソプロピル−２−ニトロイミノ−１−（３−トリ
フルオロメチルフェニル）メチルヘキサヒドロ−１，
３，５−トリアジン１．７３ｇ、９５％水酸化カリウム
０．３０ｇをジクロロメタン１５ｍｌに懸濁させ、氷冷
下でジメチル硫酸０．５８ｇを滴下した。同温度で３０
分、室温で２．５時間攪拌した後、不溶物を濾別し、濾
液を２４．１ｇ得た。この濾液を高速液体クロマトグラ
フィー（以下、ＨＰＬＣと略する）で分析したところ、
目的とする５−イソプロピル−３−メチル−２−ニトロ
イミノ−１−（３−トリフルオロメチルフェニル）メチ
ルヘキサヒドロ−１，３，５−トリアジン濃度は７．２
％であった。収量１．７３ｇ。Example 1 5-Isopropyl-2-nitroimino-1- (3-trifluoromethylphenyl) methylhexahydro-1,
1.73 g of 3,5-triazine and 0.30 g of 95% potassium hydroxide were suspended in 15 ml of dichloromethane, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. 30 at the same temperature
After stirring for 2.5 minutes at room temperature for 2.5 hours, the insoluble matter was filtered off to obtain 24.1 g of a filtrate. When this filtrate was analyzed by high performance liquid chromatography (hereinafter abbreviated as HPLC),
The target concentration of 5-isopropyl-3-methyl-2-nitroimino-1- (3-trifluoromethylphenyl) methylhexahydro-1,3,5-triazine was 7.2.
%Met. Yield 1.73g.
【００２０】実施例２ ５−イソプロピル−２−ニトロイミノ−１−（２−クロ
ロ−５−ピリジル）メチルヘキサヒドロ−１，３，５−
トリアジン１．５７ｇ、９５％水酸化カリウム０．３０
ｇをジクロロメタン１５ｍｌに懸濁させ、氷冷下でジメ
チル硫酸０．５８ｇを滴下した。同温度で３０分、室温
で２．５時間攪拌した後、不溶物を濾別し、濾液を２
２．４ｇ得た。この濾液をＨＰＬＣで分析したところ、
目的とする５−イソプロピル−３−メチル−２−ニトロ
イミノ−１−（２−クロロ−５−ピリジル）メチルヘキ
サヒドロ−１，３，５−トリアジン濃度は６．８％であ
った。収量１．５３ｇ。Example 2 5-Isopropyl-2-nitroimino-1- (2-chloro-5-pyridyl) methylhexahydro-1,3,5-
Triazine 1.57g, 95% potassium hydroxide 0.30
g was suspended in 15 ml of dichloromethane, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble material was filtered off, and the filtrate was washed with 2
2.4 g was obtained. When this filtrate was analyzed by HPLC,
The desired concentration of 5-isopropyl-3-methyl-2-nitroimino-1- (2-chloro-5-pyridyl) methylhexahydro-1,3,5-triazine was 6.8%. Yield 1.53g.
【００２１】実施例３ ５−イソプロピル−２−ニトロイミノ−１−（２−クロ
ロ−５−チアゾリル）メチルヘキサヒドロ−１，３，５
−トリアジン１．６０ｇ、９５％水酸化カリウム０．３
０ｇをジクロロメタン１５ｍｌに懸濁させ、氷冷下でジ
メチル硫酸０．５８ｇを滴下した。同温度で３０分、室
温で２．５時間攪拌した後、不溶物を濾別し、濾液を２
２．７ｇ得た。この濾液をＨＰＬＣで分析したところ、
目的とする５−イソプロピル−３−メチル−２−ニトロ
イミノ−１−（２−クロロ−５−チアゾリル）メチルヘ
キサヒドロ−１，３，５−トリアジン濃度は６．７％で
あった。収量１．５２ｇ。Example 3 5-Isopropyl-2-nitroimino-1- (2-chloro-5-thiazolyl) methylhexahydro-1,3,5
-Triazine 1.60 g, 95% potassium hydroxide 0.3
0 g was suspended in 15 ml of dichloromethane, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble material was filtered off, and the filtrate was washed with 2
2.7 g were obtained. When this filtrate was analyzed by HPLC,
The target concentration of 5-isopropyl-3-methyl-2-nitroimino-1- (2-chloro-5-thiazolyl) methylhexahydro-1,3,5-triazine was 6.7%. Yield 1.52g.
【００２２】実施例４ ５−イソプロピル−２−ニトロイミノ−１−（２−テト
ラヒドロフリル）メチルヘキサヒドロ−１，３，５−ト
リアジン１．３６ｇ、９５％水酸化カリウム０．３０ｇ
をジクロロメタン１５ｍｌに懸濁させ、氷冷下でジメチ
ル硫酸０．５８ｇを滴下した。同温度で３０分、室温で
２．５時間攪拌した後、不溶物を濾別し、濾液を２２．
０ｇ得た。この濾液をＨＰＬＣで分析したところ、目的
とする５−イソプロピル−３−メチル−２−ニトロイミ
ノ−１−（２−テトラヒドロフリル）メチルヘキサヒド
ロ−１，３，５−トリアジン濃度は６．２％であった。
収量１．３７ｇ。Example 4 1.36 g of 5-isopropyl-2-nitroimino-1- (2-tetrahydrofuryl) methylhexahydro-1,3,5-triazine, 0.30 g of 95% potassium hydroxide
Was suspended in 15 ml of dichloromethane, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble matter was filtered off, and the filtrate was added to 22.
0 g was obtained. When the filtrate was analyzed by HPLC, the target concentration of 5-isopropyl-3-methyl-2-nitroimino-1- (2-tetrahydrofuryl) methylhexahydro-1,3,5-triazine was 6.2%. there were.
Yield 1.37g.
【００２３】実施例５ ５−エチル−２−ニトロイミノ−１−（３−テトラヒド
ロフリル）メチルヘキサヒドロ−１，３，５−トリアジ
ン１．２９ｇ、９５％水酸化カリウム０．３０ｇをジク
ロロメタン１５ｍｌに懸濁させ、氷冷下でジメチル硫酸
０．５８ｇを滴下した。同温度で３０分、室温で２．５
時間攪拌した後、不溶物を濾別し、濾液を２１．２ｇ得
た。この濾液をＨＰＬＣで分析したところ、目的とする
５−エチル−３−メチル−２−ニトロイミノ−１−（３
−テトラヒドロフリル）メチルヘキサヒドロ−１，３，
５−トリアジン濃度は４．６％であった。溶媒を減圧留
去し、残渣を乾燥して目的物を１．２５ｇ含む油状物を
１．５７ｇ得た。Example 5 1.29 g of 5-ethyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine and 0.30 g of 95% potassium hydroxide were suspended in 15 ml of dichloromethane. It was made turbid, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. 30 minutes at the same temperature, 2.5 at room temperature
After stirring for an hour, the insoluble material was filtered off, and 21.2 g of a filtrate was obtained. When this filtrate was analyzed by HPLC, the desired 5-ethyl-3-methyl-2-nitroimino-1- (3
-Tetrahydrofuryl) methylhexahydro-1,3,
The 5-triazine concentration was 4.6%. The solvent was distilled off under reduced pressure, and the residue was dried to obtain 1.57 g of an oily substance containing 1.25 g of the desired product.
【００２４】実施例６ ５−ｎ−プロピル−２−ニトロイミノ−１−（３−テト
ラヒドロフリル）メチルヘキサヒドロ−１，３，５−ト
リアジン１．３６ｇ、９５％水酸化カリウム０．３０ｇ
をジクロロメタン１５ｍｌに懸濁させ、氷冷下でジメチ
ル硫酸０．５８ｇを滴下した。同温度で３０分、室温で
２．５時間攪拌した後、不溶物を濾別し、濾液を２６．
３ｇ得た。この濾液をＨＰＬＣで分析したところ、目的
とする５−ｎ−プロピル−３−メチル−２−ニトロイミ
ノ−１−（３−テトラヒドロフリル）メチルヘキサヒド
ロ−１，３，５−トリアジン濃度は６．１％であった。
溶媒を減圧留去し、残渣を乾燥して目的物を１．６０ｇ
含む油状物を１．８６ｇ得た。この油状物は放置すると
結晶した。Example 6 1.36 g of 5-n-propyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine, 0.30 g of 95% potassium hydroxide
Was suspended in 15 ml of dichloromethane, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble matter was filtered off, and the filtrate was mixed with 26.
3 g were obtained. When this filtrate was analyzed by HPLC, the target concentration of 5-n-propyl-3-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine was 6.1. %Met.
The solvent was distilled off under reduced pressure, the residue was dried, and 1.60 g of the desired product was obtained.
An oily substance containing 1.86 g was obtained. The oil crystallized on standing.
【００２５】実施例７ ５−イソプロピル−２−ニトロイミノ−１−（３−テト
ラヒドロフリル）メチルヘキサヒドロ−１，３，５−ト
リアジン１．３６ｇ、９５％水酸化カリウム０．３０ｇ
をジクロロメタン１５ｍｌに懸濁させ、氷冷下でジメチ
ル硫酸０．５８ｇを滴下した。同温度で３０分、室温で
２．５時間攪拌した後、不溶物を濾別し、濾液を２１．
２ｇ得た。この濾液をＨＰＬＣで分析したところ、目的
とする５−イソプロピル−３−メチル−２−ニトロイミ
ノ−１−（３−テトラヒドロフリル）メチルヘキサヒド
ロ−１，３，５−トリアジン濃度は６．４％であった。
溶媒を減圧留去し、ジエチルエーテルで結晶化させて濾
取し、目的物を１．３６ｇを得た。Example 7 1.36 g of 5-isopropyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine, 0.30 g of 95% potassium hydroxide
Was suspended in 15 ml of dichloromethane, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble matter was filtered off, and the filtrate was added to 21.
2 g were obtained. When the filtrate was analyzed by HPLC, the target concentration of 5-isopropyl-3-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine was 6.4%. there were.
The solvent was distilled off under reduced pressure, and the residue was crystallized with diethyl ether and collected by filtration to obtain 1.36 g of the desired product.
【００２６】実施例８ ５−ベンジル−２−ニトロイミノ−１−（３−テトラヒ
ドロフリル）メチルヘキサヒドロ−１，３，５−トリア
ジン１．６０ｇ、９５％水酸化カリウム０．３０ｇをジ
クロロメタン１５ｍｌに懸濁させ、氷冷下でジメチル硫
酸０．５８ｇを滴下した。同温度で３０分、室温で２．
５時間攪拌した後、不溶物を濾別し、濾液を２９．５ｇ
得た。この濾液をＨＰＬＣで分析したところ、目的とす
る５−ベンジル−３−メチル−２−ニトロイミノ−１−
（３−テトラヒドロフリル）メチルヘキサヒドロ−１，
３，５−トリアジン濃度は５．１％であった。収量１．
５０ｇ。Example 8 1.60 g of 5-benzyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine and 0.30 g of 95% potassium hydroxide were suspended in 15 ml of dichloromethane. It was made turbid, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. 30 minutes at the same temperature, 2.
After stirring for 5 hours, the insoluble matter was filtered off, and the filtrate was 29.5 g.
Obtained. When this filtrate was analyzed by HPLC, the desired 5-benzyl-3-methyl-2-nitroimino-1-
(3-tetrahydrofuryl) methylhexahydro-1,
The 3,5-triazine concentration was 5.1%. Yield 1.
50 g.
【００２７】実施例９ ５−シクロヘキシル−２−ニトロイミノ−１−（３−テ
トラヒドロフリル）メチルヘキサヒドロ−１，３，５−
トリアジン１．３７ｇ、９５％水酸化カリウム０．３０
ｇをジクロロメタン１５ｍｌに懸濁させ、氷冷下でジメ
チル硫酸０．５８ｇを滴下した。同温度で３０分、室温
で２．５時間攪拌した後、不溶物を濾別し、濾液を２
５．０ｇ得た。この濾液をＨＰＬＣで分析したところ、
目的とする５−シクロヘキシル−３−メチル−２−ニト
ロイミノ−１−（３−テトラヒドロフリル）メチルヘキ
サヒドロ−１，３，５−トリアジン濃度は５．３％であ
った。収量１．３２ｇ。Example 9 5-Cyclohexyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-
Triazine 1.37 g, 95% potassium hydroxide 0.30
g was suspended in 15 ml of dichloromethane, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble material was filtered off, and the filtrate was washed with 2
5.0 g were obtained. When this filtrate was analyzed by HPLC,
The target 5-cyclohexyl-3-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine concentration was 5.3%. Yield 1.32g.
【００２８】実施例１０ ５−ｔ−ブチル−２−ニトロイミノ−１−（３−テトラ
ヒドロフリル）メチルヘキサヒドロ−１，３，５−トリ
アジン１．４３ｇ、９５％水酸化カリウム０．３０ｇを
ジクロロメタン１５ｍｌに懸濁させ、氷冷下でジメチル
硫酸０．５８ｇを滴下した。同温度で３０分、室温で
２．５時間攪拌した後、不溶物を濾別し、濾液を１９．
８ｇ得た。この濾液をＨＰＬＣで分析したところ、目的
とする５−ｔ−ブチル−３−メチル−２−ニトロイミノ
−１−（３−テトラヒドロフリル）メチルヘキサヒドロ
−１，３，５−トリアジン濃度は６．８％であった。収
量１．３５ｇ。Example 10 1.43 g of 5-t-butyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine, 0.30 g of 95% potassium hydroxide and 15 ml of dichloromethane Then, 0.58 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble matter was filtered off, and the filtrate was added to 19.
8 g were obtained. When this filtrate was analyzed by HPLC, the target concentration of 5-t-butyl-3-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine was 6.8. %Met. Yield 1.35g.
【００２９】実施例１１ ５−（４−ノニル）−２−ニトロイミノ−１−（３−テ
トラヒドロフリル）メチルヘキサヒドロ−１，３，５−
トリアジン１．７８ｇ、９５％水酸化カリウム０．３０
ｇをジクロロメタン１５ｍｌに懸濁させ、氷冷下でジメ
チル硫酸０．５８ｇを滴下した。同温度で３０分、室温
で２．５時間攪拌した後、不溶物を濾別し、濾液を２
３．５ｇ得た。この濾液をＨＰＬＣで分析したところ、
目的とする５−（４−ノニル）−３−メチル−２−ニト
ロイミノ−１−（３−テトラヒドロフリル）メチルヘキ
サヒドロ−１，３，５−トリアジン濃度は７．１％であ
った。収量１．６７ｇ。Example 11 5- (4-nonyl) -2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-
Triazine 1.78 g, 95% potassium hydroxide 0.30
g was suspended in 15 ml of dichloromethane, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble material was filtered off, and the filtrate was washed with 2
3.5 g were obtained. When this filtrate was analyzed by HPLC,
The desired concentration of 5- (4-nonyl) -3-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine was 7.1%. Yield 1.67g.
【００３０】実施例１２ ５−（４−デシル）−２−ニトロイミノ−１−（３−テ
トラヒドロフリル）メチルヘキサヒドロ−１，３，５−
トリアジン１．８５ｇ、９５％水酸化カリウム０．３０
ｇをジクロロメタン１５ｍｌに懸濁させ、氷冷下でジメ
チル硫酸０．５８ｇを滴下した。同温度で３０分、室温
で２．５時間攪拌した後、不溶物を濾別し、濾液を２
５．２ｇ得た。この濾液をＨＰＬＣで分析したところ、
目的とする５−（４−デシル）−３−メチル−２−ニト
ロイミノ−１−（３−テトラヒドロフリル）メチルヘキ
サヒドロ−１，３，５−トリアジン濃度は６．６％であ
った。収量１．６７ｇ。Example 12 5- (4-decyl) -2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-
Triazine 1.85 g, 95% potassium hydroxide 0.30
g was suspended in 15 ml of dichloromethane, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble material was filtered off, and the filtrate was washed with 2
Obtained 5.2 g. When this filtrate was analyzed by HPLC,
The target concentration of 5- (4-decyl) -3-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine was 6.6%. Yield 1.67g.
【００３１】実施例１３ ５−イソプロピル−２−ニトロイミノ−１−（３−テト
ラヒドロフリル）メチルヘキサヒドロ−１，３，５−ト
リアジン１．３６ｇ、９５％水酸化ナトリウム０．２１
ｇをジクロロメタン１５ｍｌに懸濁させ、氷冷下でジメ
チル硫酸０．５８ｇを滴下した。同温度で３０分、室温
で２．５時間攪拌した後、不溶物を濾別し、濾液を２
０．８ｇ得た。この濾液をＨＰＬＣで分析したところ、
目的とする５−イソプロピル−３−メチル−２−ニトロ
イミノ−１−（３−テトラヒドロフリル）メチルヘキサ
ヒドロ−１，３，５−トリアジン濃度は５．６％であっ
た。収量１．１６ｇ。Example 13 1.36 g 5-isopropyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine, 95% sodium hydroxide 0.21
g was suspended in 15 ml of dichloromethane, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble material was filtered off, and the filtrate was washed with 2
0.8 g was obtained. When this filtrate was analyzed by HPLC,
The target concentration of 5-isopropyl-3-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine was 5.6%. Yield 1.16g.
【００３２】実施例１４ ５−イソプロピル−２−ニトロイミノ−１−（３−テト
ラヒドロフリル）メチルヘキサヒドロ−１，３，５−ト
リアジン１．３６ｇ、９５％水酸化カリウム０．３０ｇ
をジクロロメタン１５ｍｌに懸濁させ、氷冷下でｐ−ト
ルエンスルホン酸メチル０．９１ｇを滴下した。同温度
で３０分、室温で２．５時間攪拌した後、不溶物を濾別
し、濾液を２０．７ｇ得た。この濾液をＨＰＬＣで分析
したところ、目的とする５−イソプロピル−３−メチル
−２−ニトロイミノ−１−（３−テトラヒドロフリル）
メチルヘキサヒドロ−１，３，５−トリアジン濃度は
６．８％であった。収量１．４０ｇ。Example 14 1.36 g of 5-isopropyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine, 0.30 g of 95% potassium hydroxide
Was suspended in 15 ml of dichloromethane, and 0.91 g of methyl p-toluenesulfonate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble matter was filtered off to obtain 20.7 g of a filtrate. When this filtrate was analyzed by HPLC, the desired 5-isopropyl-3-methyl-2-nitroimino-1- (3-tetrahydrofuryl) was obtained.
The methylhexahydro-1,3,5-triazine concentration was 6.8%. Yield 1.40 g.
【００３３】実施例１５ ５−イソプロピル−２−ニトロイミノ−１−（３−テト
ラヒドロフリル）メチルヘキサヒドロ−１，３，５−ト
リアジン１．３６ｇ、９５％水酸化カリウム０．３０ｇ
をジクロロメタン１５ｍｌに懸濁させ、氷冷下でメタン
スルホン酸メチル０．５４ｇを滴下した。同温度で３０
分、室温で２．５時間攪拌した後、不溶物を濾別し、濾
液を１９．６ｇ得た。この濾液をＨＰＬＣで分析したと
ころ、目的とする５−イソプロピル−３−メチル−２−
ニトロイミノ−１−（３−テトラヒドロフリル）メチル
ヘキサヒドロ−１，３，５−トリアジン濃度は７．１％
であった。収量１．４０ｇ。Example 15 1.36 g of 5-isopropyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine, 0.30 g of 95% potassium hydroxide
Was suspended in 15 ml of dichloromethane, and 0.54 g of methyl methanesulfonate was added dropwise under ice cooling. 30 at the same temperature
After stirring for 2.5 minutes at room temperature, the insoluble matter was filtered off to obtain 19.6 g of a filtrate. When this filtrate was analyzed by HPLC, the desired 5-isopropyl-3-methyl-2-
Nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine concentration was 7.1%
Met. Yield 1.40 g.
【００３４】実施例１６ ５−イソプロピル−２−ニトロイミノ−１−（３−テト
ラヒドロフリル）メチルヘキサヒドロ−１，３，５−ト
リアジン１．３６ｇ、９５％水酸化カリウム０．３０ｇ
をジクロロメタン１５ｍｌに懸濁させ、氷冷下でジエチ
ル硫酸０．８１ｇを滴下した。同温度で３０分、室温で
２．５時間攪拌した後、不溶物を濾別し、濾液を２０．
６ｇ得た。この濾液をＨＰＬＣで分析したところ、目的
とする５−イソプロピル−３−メチル−２−ニトロイミ
ノ−１−（３−テトラヒドロフリル）メチルヘキサヒド
ロ−１，３，５−トリアジン濃度は７．３％であった。
収量１．５０ｇ。Example 16 1.36 g of 5-isopropyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine, 0.30 g of 95% potassium hydroxide
Was suspended in 15 ml of dichloromethane, and 0.81 g of diethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble matter was filtered off, and the filtrate was added to 20.
6 g were obtained. When the filtrate was analyzed by HPLC, the target concentration of 5-isopropyl-3-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine was 7.3%. there were.
Yield 1.50g.
【００３５】実施例１７ ５−イソプロピル−２−ニトロイミノ−１−メチルヘキ
サヒドロ−１，３，５−トリアジン１．０１ｇ、９５％
水酸化カリウム０．３０ｇをジクロロメタン１５ｍｌに
懸濁させ、氷冷下でジメチル硫酸０．５８ｇを滴下し
た。同温度で３０分、室温で２．５時間攪拌した後、不
溶物を濾別し、濾液を１８．２ｇ得た。この濾液をＨＰ
ＬＣで分析したところ、目的とする５−イソプロピル−
２−ニトロイミノ−１，３−ジメチルヘキサヒドロ−
１，３，５−トリアジン濃度は５．７％であった。収量
１．０４ｇ。Example 17 5-Isopropyl-2-nitroimino-1-methylhexahydro-1,3,5-triazine 1.01 g, 95%
0.30 g of potassium hydroxide was suspended in 15 ml of dichloromethane, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble matter was filtered off to obtain 18.2 g of a filtrate. This filtrate is HP
When analyzed by LC, the desired 5-isopropyl-
2-nitroimino-1,3-dimethylhexahydro-
The 1,3,5-triazine concentration was 5.7%. Yield 1.04g.
【００３６】実施例１８ ５−イソプロピル−２−ニトロイミノ−１−アリルヘキ
サヒドロ−１，３，５−トリアジン１．１４ｇ、９５％
水酸化カリウム０．３０ｇをジクロロメタン１５ｍｌに
懸濁させ、氷冷下でジメチル硫酸０．５８ｇを滴下し
た。同温度で３０分、室温で２．５時間攪拌した後、不
溶物を濾別し、濾液を１８．７ｇ得た。この濾液をＨＰ
ＬＣで分析したところ、目的とする５−イソプロピル−
３−メチル−２−ニトロイミノ−１−アリルヘキサヒド
ロ−１，３，５−トリアジン濃度は６．２％であった。
収量１．１７ｇ。Example 18 1.14 g of 5-isopropyl-2-nitroimino-1-allylhexahydro-1,3,5-triazine, 95%
0.30 g of potassium hydroxide was suspended in 15 ml of dichloromethane, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble matter was filtered off to obtain 18.7 g of a filtrate. This filtrate is HP
When analyzed by LC, the desired 5-isopropyl-
The concentration of 3-methyl-2-nitroimino-1-allylhexahydro-1,3,5-triazine was 6.2%.
Yield 1.17g.
【００３７】実施例１９ ５−イソプロピル−２−ニトロイミノ−１−プロパルギ
ルヘキサヒドロ−１，３，５−トリアジン１．１３ｇ、
９５％水酸化カリウム０．３０ｇをジクロロメタン１５
ｍｌに懸濁させ、氷冷下でジメチル硫酸０．５８ｇを滴
下した。同温度で３０分、室温で２．５時間攪拌した
後、不溶物を濾別し、濾液を１９．８ｇ得た。この濾液
をＨＰＬＣで分析したところ、目的とする５−イソプロ
ピル−３−メチル−２−ニトロイミノ−１−プロパルギ
ルヘキサヒドロ−１，３，５−トリアジン濃度は６．１
％であった。収量１．２０ｇ。Example 19 1.13 g of 5-isopropyl-2-nitroimino-1-propargylhexahydro-1,3,5-triazine,
95% potassium hydroxide 0.30 g in dichloromethane 15
It was suspended in ml and 0.58 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble matter was filtered off to obtain 19.8 g of a filtrate. When this filtrate was analyzed by HPLC, the target concentration of 5-isopropyl-3-methyl-2-nitroimino-1-propargylhexahydro-1,3,5-triazine was 6.1.
%Met. Yield 1.20g.
【００３８】実施例２０ ５−イソプロピル−２−ニトロイミノ−１−（３−テト
ラヒドロフリル）メチルヘキサヒドロ−１，３，５−ト
リアジン１．３６ｇ、９５％水酸化カリウム０．３０ｇ
をアセトニトリル１５ｍｌに懸濁させ、氷冷下でジメチ
ル硫酸０．５８ｇを滴下した。同温度で３０分、室温で
２．５時間攪拌した後、不溶物を濾別し、濾液を３０．
６ｇ得た。この濾液をＨＰＬＣで分析したところ、目的
とする５−イソプロピル−３−メチル−２−ニトロイミ
ノ−１−（３−テトラヒドロフリル）メチルヘキサヒド
ロ−１，３，５−トリアジン濃度は４．３％であった。
収量１．３３ｇ。Example 20 1.36 g of 5-isopropyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine, 0.30 g of 95% potassium hydroxide
Was suspended in 15 ml of acetonitrile, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble matter was filtered off, and the filtrate was washed with 30.
6 g were obtained. When the filtrate was analyzed by HPLC, the target concentration of 5-isopropyl-3-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine was 4.3%. there were.
Yield 1.33g.
【００３９】実施例２１ ５−イソプロピル−２−ニトロイミノ−１−（３−テト
ラヒドロフリル）メチルヘキサヒドロ−１，３，５−ト
リアジン１．３６ｇ、９５％水酸化カリウム０．３０ｇ
を１，３−ジメチル−２−イミダゾリジノン１５ｍｌに
懸濁させ、氷冷下でジメチル硫酸０．５８ｇを滴下し
た。同温度で３０分、室温で２．５時間攪拌した後、不
溶物を濾別し、濾液を３２．３ｇ得た。この濾液をＨＰ
ＬＣで分析したところ、目的とする５−イソプロピル−
３−メチル−２−ニトロイミノ−１−（３−テトラヒド
ロフリル）メチルヘキサヒドロ−１，３，５−トリアジ
ン濃度は４．０％であった。収量１．３０ｇ。Example 21 1.36 g of 5-isopropyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine, 0.30 g of 95% potassium hydroxide
Was suspended in 15 ml of 1,3-dimethyl-2-imidazolidinone, and 0.58 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble matter was filtered off to obtain 32.3 g of a filtrate. This filtrate is HP
When analyzed by LC, the desired 5-isopropyl-
The concentration of 3-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine was 4.0%. Yield 1.30g.
【００４０】[0040]
【表１】 [Table 1]
【００４１】[0041]
【表２】 [Table 2]
【００４２】比較例１ ５−メチル−２−ニトロイミノ−１−（２−クロロ−５
−ピリジル）メチルヘキサヒドロ−１，３，５−トリア
ジン１．４３ｇ、９５％水酸化カリウム０．３４ｇをジ
クロロメタン１５ｍｌに懸濁させ、氷冷下でジメチル硫
酸０．６６ｇを滴下した。同温度で３０分、室温で２．
５時間攪拌した後、不溶物を濾別し、濾液を２０．８ｇ
得た。この濾液をＨＰＬＣで分析したところ、目的とす
る３，５−ジメチル−２−ニトロイミノ−１−（２−ク
ロロ−５−ピリジル）メチルヘキサヒドロ−１，３，５
−トリアジン濃度は５．０％であった。収量１．０４
ｇ。Comparative Example 1 5-Methyl-2-nitroimino-1- (2-chloro-5
1.43 g of -pyridyl) methylhexahydro-1,3,5-triazine and 0.34 g of 95% potassium hydroxide were suspended in 15 ml of dichloromethane, and 0.66 g of dimethylsulfate was added dropwise under ice cooling. 30 minutes at the same temperature, 2.
After stirring for 5 hours, the insoluble matter was filtered off, and the filtrate was 20.8 g.
Obtained. When this filtrate was analyzed by HPLC, the target 3,5-dimethyl-2-nitroimino-1- (2-chloro-5-pyridyl) methylhexahydro-1,3,5 was obtained.
-The triazine concentration was 5.0%. Yield 1.04
g.
【００４３】比較例２ ５−メチル−２−ニトロイミノ−１−（２−クロロ−５
−チアゾリル）メチルヘキサヒドロ−１，３，５−トリ
アジン１．４６ｇ、９５％水酸化カリウム０．３４ｇを
ジクロロメタン１５ｍｌに懸濁させ、氷冷下でジメチル
硫酸０．６６ｇを滴下した。同温度で３０分、室温で
２．５時間攪拌した後、不溶物を濾別し、濾液を２１．
２ｇ得た。この濾液をＨＰＬＣで分析したところ、目的
とする３，５−ジメチル−２−ニトロイミノ−１−（２
−クロロ−５−チアゾリル）メチルヘキサヒドロ−１，
３，５−トリアジン濃度は４．９％であった。収量１．
０３ｇ。Comparative Example 2 5-Methyl-2-nitroimino-1- (2-chloro-5
1.46 g of -thiazolyl) methylhexahydro-1,3,5-triazine and 0.34 g of 95% potassium hydroxide were suspended in 15 ml of dichloromethane, and 0.66 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble matter was filtered off, and the filtrate was added to 21.
2 g were obtained. When this filtrate was analyzed by HPLC, the desired 3,5-dimethyl-2-nitroimino-1- (2
-Chloro-5-thiazolyl) methylhexahydro-1,
The 3,5-triazine concentration was 4.9%. Yield 1.
03 g.
【００４４】比較例３ ５−メチル−２−ニトロイミノ−１−（２−テトラヒド
ロフリル）メチルヘキサヒドロ−１，３，５−トリアジ
ン１．２２ｇ、９５％水酸化カリウム０．３４ｇをジク
ロロメタン１５ｍｌに懸濁させ、氷冷下でジメチル硫酸
０．６６ｇを滴下した。同温度で３０分、室温で２．５
時間攪拌した後、不溶物を濾別し、濾液を１９．３ｇ得
た。この濾液をＨＰＬＣで分析したところ、目的とする
３，５−ジメチル−２−ニトロイミノ−１−（２−テト
ラヒドロフリル）メチルヘキサヒドロ−１，３，５−ト
リアジン濃度は４．７％であった。収量０．９０ｇ。Comparative Example 3 1.22 g of 5-methyl-2-nitroimino-1- (2-tetrahydrofuryl) methylhexahydro-1,3,5-triazine and 0.34 g of 95% potassium hydroxide were suspended in 15 ml of dichloromethane. It was made turbid, and 0.66 g of dimethylsulfate was added dropwise under ice cooling. 30 minutes at the same temperature, 2.5 at room temperature
After stirring for an hour, the insoluble material was filtered off to obtain 19.3 g of a filtrate. When this filtrate was analyzed by HPLC, the target 3,5-dimethyl-2-nitroimino-1- (2-tetrahydrofuryl) methylhexahydro-1,3,5-triazine concentration was 4.7%. . Yield 0.90g.
【００４５】比較例４ ５−メチル−２−ニトロイミノ−１−（３−テトラヒド
ロフリル）メチルヘキサヒドロ−１，３，５−トリアジ
ン１．２２ｇ、９５％水酸化カリウム０．３４ｇをジク
ロロメタン１５ｍｌに懸濁させ、氷冷下でジメチル硫酸
０．６６ｇを滴下した。同温度で３０分、室温で２．５
時間攪拌した後、不溶物を濾別し、濾液を１８．９ｇ得
た。この濾液をＨＰＬＣで分析したところ、目的とする
３，５−ジメチル−２−ニトロイミノ−１−（３−テト
ラヒドロフリル）メチルヘキサヒドロ−１，３，５−ト
リアジン濃度は４．８％であった。収量０．９１ｇ。Comparative Example 4 1.22 g of 5-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine and 0.34 g of 95% potassium hydroxide were suspended in 15 ml of dichloromethane. It was made turbid, and 0.66 g of dimethylsulfate was added dropwise under ice cooling. 30 minutes at the same temperature, 2.5 at room temperature
After stirring for an hour, the insoluble material was filtered off to obtain 18.9 g of a filtrate. When this filtrate was analyzed by HPLC, the target 3,5-dimethyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine concentration was 4.8%. . Yield 0.91g.
【００４６】比較例５ ５−メチル−２−ニトロイミノ−１−（３−テトラヒド
ロフリル）メチルヘキサヒドロ−１，３，５−トリアジ
ン１．２２ｇ、６０％水素化ナトリウム０．２２ｇをジ
クロロメタン１５ｍｌに懸濁させ、氷冷下でジメチル硫
酸０．６６ｇを滴下した。同温度で３０分、室温で２．
５時間攪拌した後、不溶物を濾別し、濾液を１９．１ｇ
得た。この濾液をＨＰＬＣで分析したところ、目的とす
る３，５−ジメチル−２−ニトロイミノ−１−（３−テ
トラヒドロフリル）メチルヘキサヒドロ−１，３，５−
トリアジン濃度は３．９％であった。収量０．７４ｇ。Comparative Example 5 1.22 g of 5-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine and 0.22 g of 60% sodium hydride were suspended in 15 ml of dichloromethane. It was made turbid, and 0.66 g of dimethylsulfate was added dropwise under ice cooling. 30 minutes at the same temperature, 2.
After stirring for 5 hours, the insoluble material was filtered off, and the filtrate was 19.1 g.
Obtained. When this filtrate was analyzed by HPLC, the target 3,5-dimethyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-
The triazine concentration was 3.9%. Yield 0.74g.
【００４７】比較例６ ５−メチル−２−ニトロイミノ−１−（３−テトラヒド
ロフリル）メチルヘキサヒドロ−１，３，５−トリアジ
ン１．２２ｇ、６０％水素化ナトリウム０．２２ｇをジ
クロロメタン１５ｍｌに懸濁させ、氷冷下でメタンスル
ホン酸メチル０．５４ｇを滴下した。同温度で３０分、
室温で２．５時間攪拌した後、不溶物を濾別し、濾液を
２４．３ｇ得た。この濾液をＨＰＬＣで分析したとこ
ろ、目的とする３，５−ジメチル−２−ニトロイミノ−
１−（３−テトラヒドロフリル）メチルヘキサヒドロ−
１，３，５−トリアジン濃度は３．１％であった。収量
０．７６ｇ。Comparative Example 6 1.22 g of 5-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine and 0.22 g of 60% sodium hydride were suspended in 15 ml of dichloromethane. It was made turbid, and 0.54 g of methyl methanesulfonate was added dropwise under ice cooling. 30 minutes at the same temperature,
After stirring at room temperature for 2.5 hours, the insoluble matter was filtered off to obtain 24.3 g of a filtrate. When this filtrate was analyzed by HPLC, the desired 3,5-dimethyl-2-nitroimino-
1- (3-tetrahydrofuryl) methylhexahydro-
The 1,3,5-triazine concentration was 3.1%. Yield 0.76g.
【００４８】比較例７ ５−メチル−２−ニトロイミノ−１−（３−テトラヒド
ロフリル）メチルヘキサヒドロ−１，３，５−トリアジ
ン１．２２ｇ、ｔ−ブトキシカリウム１．２４ｇをジク
ロロメタン１５ｍｌに懸濁させ、氷冷下でジメチル硫酸
０．６６ｇを滴下した。同温度で３０分、室温で２．５
時間攪拌した後、不溶物を濾別し、濾液を２０．０ｇ得
た。この濾液をＨＰＬＣで分析したところ、目的とする
３，５−ジメチル−２−ニトロイミノ−１−（３−テト
ラヒドロフリル）メチルヘキサヒドロ−１，３，５−ト
リアジン濃度は０．０％であった。収量０．００ｇ。Comparative Example 7 1.22 g of 5-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine and 1.24 g of potassium t-butoxide were suspended in 15 ml of dichloromethane. Then, 0.66 g of dimethylsulfate was added dropwise under ice cooling. 30 minutes at the same temperature, 2.5 at room temperature
After stirring for an hour, the insoluble material was filtered off, and 20.0 g of a filtrate was obtained. When this filtrate was analyzed by HPLC, the desired 3,5-dimethyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine concentration was 0.0%. . Yield 0.00g.
【００４９】比較例８ ５−メチル−２−ニトロイミノ−１−（３−テトラヒド
ロフリル）メチルヘキサヒドロ−１，３，５−トリアジ
ン１．２２ｇ、ナトリウムメトキシド０．６０ｇをジク
ロロメタン１５ｍｌに懸濁させ、氷冷下でジメチル硫酸
０．６６ｇを滴下した。同温度で３０分、室温で２．５
時間攪拌した後、不溶物を濾別し、濾液を１８．７ｇ得
た。この濾液をＨＰＬＣで分析したところ、目的とする
３，５−ジメチル−２−ニトロイミノ−１−（３−テト
ラヒドロフリル）メチルヘキサヒドロ−１，３，５−ト
リアジン濃度は３．８％であった。収量０．７１ｇ。Comparative Example 8 1.22 g of 5-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine and 0.60 g of sodium methoxide were suspended in 15 ml of dichloromethane. Then, 0.66 g of dimethylsulfate was added dropwise under ice cooling. 30 minutes at the same temperature, 2.5 at room temperature
After stirring for an hour, the insoluble material was filtered off to obtain 18.7 g of a filtrate. When this filtrate was analyzed by HPLC, the desired 3,5-dimethyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine concentration was 3.8%. . Yield 0.71 g.
【００５０】比較例９ ５−メチル−２−ニトロイミノ−１−（３−テトラヒド
ロフリル）メチルヘキサヒドロ−１，３，５−トリアジ
ン１．２２ｇ、９５％水酸化カリウム０．３４ｇをジク
ロロメタン１５ｍｌに懸濁させ、氷冷下でヨウ化メチル
０．８６ｇを滴下した。同温度で３０分、室温で２．５
時間攪拌した後、不溶物を濾別し、濾液を２０．５ｇ得
た。この濾液をＨＰＬＣで分析したところ、目的とする
３，５−ジメチル−２−ニトロイミノ−１−（３−テト
ラヒドロフリル）メチルヘキサヒドロ−１，３，５−ト
リアジン濃度は２．０％であった。収量０．４０ｇ。Comparative Example 9 1.22 g of 5-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine and 0.34 g of 95% potassium hydroxide were suspended in 15 ml of dichloromethane. It was made turbid, and 0.86 g of methyl iodide was added dropwise under ice cooling. 30 minutes at the same temperature, 2.5 at room temperature
After stirring for an hour, the insoluble material was filtered off to obtain 20.5 g of a filtrate. When this filtrate was analyzed by HPLC, the target 3,5-dimethyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine concentration was 2.0%. . Yield 0.40 g.
【００５１】比較例１０ ５−メチル−２−ニトロイミノ−１−（３−テトラヒド
ロフリル）メチルヘキサヒドロ−１，３，５−トリアジ
ン１．２２ｇ、９５％水酸化カリウム０．３４ｇをジク
ロロメタン１５ｍｌに懸濁させ、氷冷下でメタンスルホ
ン酸メチル０．５４ｇを滴下した。同温度で３０分、室
温で２．５時間攪拌した後、不溶物を濾別し、濾液を２
３．５ｇ得た。この濾液をＨＰＬＣで分析したところ、
目的とする３，５−ジメチル−２−ニトロイミノ−１−
（３−テトラヒドロフリル）メチルヘキサヒドロ−１，
３，５−トリアジン濃度は４．０％であった。収量０．
９４ｇ。Comparative Example 10 1.22 g of 5-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine and 0.34 g of 95% potassium hydroxide were suspended in 15 ml of dichloromethane. It was made turbid, and 0.54 g of methyl methanesulfonate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and at room temperature for 2.5 hours, the insoluble material was filtered off, and the filtrate was washed with 2
3.5 g were obtained. When this filtrate was analyzed by HPLC,
Target 3,5-dimethyl-2-nitroimino-1-
(3-tetrahydrofuryl) methylhexahydro-1,
The 3,5-triazine concentration was 4.0%. Yield 0.
94 g.
【００５２】比較例１１ ５−メチル−２−ニトロイミノ−１−（３−テトラヒド
ロフリル）メチルヘキサヒドロ−１，３，５−トリアジ
ン１．２２ｇ、９５％水酸化カリウム０．３４ｇをアセ
トニトリル１５ｍｌに懸濁させ、氷冷下でジメチル硫酸
０．６６ｇを滴下した。同温度で３０分、室温で２．５
時間攪拌した後、不溶物を濾別し、濾液を３１．１ｇ得
た。この濾液をＨＰＬＣで分析したところ、目的とする
３，５−ジメチル−２−ニトロイミノ−１−（３−テト
ラヒドロフリル）メチルヘキサヒドロ−１，３，５−ト
リアジン濃度は３．３％であった。収量１．０３ｇ。 比較例１２Comparative Example 11 1.22 g of 5-methyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine and 0.34 g of 95% potassium hydroxide were suspended in 15 ml of acetonitrile. It was made turbid, and 0.66 g of dimethylsulfate was added dropwise under ice cooling. 30 minutes at the same temperature, 2.5 at room temperature
After stirring for an hour, the insoluble material was filtered off to obtain 31.1 g of a filtrate. When this filtrate was analyzed by HPLC, the target 3,5-dimethyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine concentration was 3.3%. . Yield 1.03g. Comparative Example 12
【００５３】５−メチル−２−ニトロイミノ−１−（３
−テトラヒドロフリル）メチルヘキサヒドロ−１，３，
５−トリアジン１．２２ｇ、９５％水酸化カリウム０．
３４ｇを１，３−ジメチル−２−イミダゾリジノン１５
ｍｌに懸濁させ、氷冷下でジメチル硫酸０．６６ｇを滴
下した。同温度で３０分、室温で２．５時間攪拌した
後、不溶物を濾別し、濾液を３５．５ｇ得た。この濾液
をＨＰＬＣで分析したところ、目的とする３，５−ジメ
チル−２−ニトロイミノ−１−（３−テトラヒドロフリ
ル）メチルヘキサヒドロ−１，３，５−トリアジン濃度
は２．４％であった。収量０．８４ｇ。5-methyl-2-nitroimino-1- (3
-Tetrahydrofuryl) methylhexahydro-1,3,
5-triazine 1.22 g, 95% potassium hydroxide 0.
34 g of 1,3-dimethyl-2-imidazolidinone 15
It was suspended in ml and 0.66 g of dimethylsulfate was added dropwise under ice cooling. After stirring at the same temperature for 30 minutes and room temperature for 2.5 hours, the insoluble matter was filtered off to obtain 35.5 g of a filtrate. When this filtrate was analyzed by HPLC, the target 3,5-dimethyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine concentration was 2.4%. . Yield 0.84g.
【００５４】[0054]
【表３】 [Table 3]
【００５５】参考例１ （３−テトラヒドロフリル）メチルニトログアニジン
１．８８ｇ、３７％ホルマリン水溶液１．７９ｇをエタ
ノール２０ｍｌに懸濁し、シクロヘキシルアミン１．０
９ｇを滴下した。濃塩酸一滴を加えて３時間加熱還流し
た後、氷冷し、生じた沈澱を濾取して５−シクロヘキシ
ル−２−ニトロイミノ−１−（３−テトラヒドロフリ
ル）メチルヘキサヒドロ−１，３，５−トリアジン１．
６８ｇを得た。Reference Example 1 (3-Tetrahydrofuryl) methylnitroguanidine (1.88 g) and 37% aqueous formalin solution (1.79 g) were suspended in ethanol (20 ml) to prepare cyclohexylamine (1.0 ml).
9 g was added dropwise. After adding 1 drop of concentrated hydrochloric acid and heating under reflux for 3 hours, the mixture was cooled with ice, the precipitate formed was collected by filtration and 5-cyclohexyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5. -Triazine 1.
68 g were obtained.
【００５６】参考例２ （３−テトラヒドロフリル）メチルニトログアニジン
０．８３ｇ、３７％ホルマリン水溶液０．７９ｇを水５
ｍｌに懸濁し、イソプロピルアミン０．２９ｇを滴下し
た。室温で３時間攪拌した後、氷冷し、生じた沈澱を濾
取してイソプロピルアルコール１０ｍｌで洗浄し、５−
イソプロピル−２−ニトロイミノ−１−（３−テトラヒ
ドロフリル）メチルヘキサヒドロ−１，３，５−トリア
ジン０．９４ｇを得た。Reference Example 2 (3-Tetrahydrofuryl) methylnitroguanidine 0.83 g, 37% aqueous formalin solution 0.79 g were added to water 5
It was suspended in ml and 0.29 g of isopropylamine was added dropwise. After stirring at room temperature for 3 hours, the mixture was cooled with ice, the precipitate formed was collected by filtration, and washed with 10 ml of isopropyl alcohol.
0.94 g of isopropyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine was obtained.
【００５７】参考例３ （３−テトラヒドロフリル）メチルニトログアニジン
１．８８ｇ、３７％ホルマリン水溶液１．７９ｇを水１
０ｍｌに懸濁し、ｔ−ブチルアミン０．８１ｇを滴下し
た。室温で３時間攪拌した後、氷冷し、生じた沈澱を濾
取してイソプロピルアルコール２０ｍｌで洗浄し、５−
ｔ−ブチル−２−ニトロイミノ−１−（３−テトラヒド
ロフリル）メチルヘキサヒドロ−１，３，５−トリアジ
ン２．３１ｇを得た。Reference Example 3 (3-Tetrahydrofuryl) methylnitroguanidine (1.88 g) and a 37% aqueous formalin solution (1.79 g) were added to water (1).
It was suspended in 0 ml and 0.81 g of t-butylamine was added dropwise. After stirring at room temperature for 3 hours, the mixture was cooled with ice, the precipitate formed was collected by filtration and washed with 20 ml of isopropyl alcohol,
2.31 g of t-butyl-2-nitroimino-1- (3-tetrahydrofuryl) methylhexahydro-1,3,5-triazine was obtained.
【００５８】[0058]
【発明の効果】以上の様に本発明によれば、農薬（特に
殺虫剤）またはその中間体として有用である１，３，５
−三置換−２−ニトロイミノヘキサヒドロ−１，３，５
−トリアジン類を安価に収率良く製造する事ができ、工
業的製造法として優れている。As described above, according to the present invention, 1,3,5 which is useful as an agricultural chemical (particularly an insecticide) or an intermediate thereof.
-Trisubstituted-2-nitroiminohexahydro-1,3,5
-Triazines can be produced inexpensively and in good yield, which is an excellent industrial production method.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 (Ｃ０７Ｄ 401/06 213:61 251:08） (Ｃ０７Ｄ 405/06 251:08 307:06） (Ｃ０７Ｄ 417/06 251:08 277:32） (72)発明者 福入 靖 福岡県大牟田市浅牟田町30番地 三井東圧 化学株式会社内 (72)発明者 山本 紀之 福岡県大牟田市浅牟田町30番地 三井東圧 化学株式会社内 (72)発明者 脇田 健夫 千葉県茂原市東郷1144番地 三井東圧化学 株式会社内 (72)発明者 小澤 修二 福岡県大牟田市浅牟田町30番地 三井東圧 化学株式会社内 (72)発明者 海宝 龍夫 福岡県大牟田市浅牟田町30番地 三井東圧 化学株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location (C07D 401/06 213: 61 251: 08) (C07D 405/06 251: 08 307: 06) ( (C07D 417/06 251: 08 277: 32) (72) Inventor Yasushi Fukuiri, 30 Asamu-cho, Omuta-shi, Fukuoka Mitsui Toatsu Chemical Co., Ltd. (72) Noriyuki Yamamoto 30, Asamu-cho, Omuta-shi, Fukuoka Address Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Takeo Wakita 1144 Togo, Mobara-shi, Chiba Prefecture Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Shuji Ozawa 30 Asamu-cho, Omuta City, Fukuoka Mitsui Toatsu Chemical Co. Inside the company (72) Inventor Tatsuo Kaiho Mitsui Toatsu Chemical Co., Ltd. 30 Asamu-cho, Omuta-shi, Fukuoka
Claims (2)
族の炭化水素環、置換されていてもよい芳香族または非
芳香族の複素環、水素原子、置換されていてもよいアル
キル基またはアルケニル基、アルキニル基を示し、Ｒは
置換されていても良い炭素数２〜１０の鎖状または環状
のアルキル基を示す。）で表される化合物と式（２）
（化２） 【化２】 （式中、Ｒ1は炭素数１〜３のアルキル基を示し、Ｒ2は
置換されていてもよい炭素数１〜３のアルキル基、置換
されていてもよいフェニル基、炭素数１〜３のアルコキ
シ基を示す。）で表される化合物を水酸化アルカリ金属
類の存在下に反応させることを特徴とする式（３）（化
３） 【化３】 （式中、Ａ、Ｒ、Ｒ1は上記の意味を示す。）で表され
る化合物の製造法。(1) Formula (1) (Formula 1) (In the formula, A is an optionally substituted aromatic or non-aromatic hydrocarbon ring, an optionally substituted aromatic or non-aromatic heterocycle, a hydrogen atom, and an optionally substituted alkyl group. Or an alkenyl group or an alkynyl group, and R represents an optionally substituted chain or cyclic alkyl group having 2 to 10 carbon atoms) and the formula (2).
(Chemical formula 2) [Chemical formula 2] (In the formula, R 1 represents an alkyl group having 1 to 3 carbon atoms, R 2 is an optionally substituted alkyl group having 1 to 3 carbon atoms, optionally substituted phenyl group, 1 to 3 carbon atoms The compound represented by the formula (3) is reacted in the presence of an alkali metal hydroxide. (In the formula, A, R, and R 1 have the above meanings.) A method for producing a compound represented by the formula.
３−テトラヒドロフリル基を示し、Ｒが置換されていて
もよい炭素数２〜１０の鎖状または環状のアルキル基で
ある請求項１記載の方法。2. In the above formulas (1) and (3), A represents a 3-tetrahydrofuryl group, and R is an optionally substituted chain or cyclic alkyl group having 2 to 10 carbon atoms. The method of claim 1, wherein:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3934096A JP3387723B2 (en) | 1996-02-27 | 1996-02-27 | Method for producing 2-nitroiminohexahydro-1,3,5-triazines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3934096A JP3387723B2 (en) | 1996-02-27 | 1996-02-27 | Method for producing 2-nitroiminohexahydro-1,3,5-triazines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09227532A true JPH09227532A (en) | 1997-09-02 |
| JP3387723B2 JP3387723B2 (en) | 2003-03-17 |
Family
ID=12550369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3934096A Expired - Lifetime JP3387723B2 (en) | 1996-02-27 | 1996-02-27 | Method for producing 2-nitroiminohexahydro-1,3,5-triazines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3387723B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998056764A1 (en) * | 1997-06-09 | 1998-12-17 | Novartis Ag | Method for producing nitroguanidine derivatives |
| KR100354291B1 (en) * | 2000-04-21 | 2002-09-28 | (주)닥터스텍 | Ascorbic acid composition for epidermal dosaging |
-
1996
- 1996-02-27 JP JP3934096A patent/JP3387723B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998056764A1 (en) * | 1997-06-09 | 1998-12-17 | Novartis Ag | Method for producing nitroguanidine derivatives |
| KR100354291B1 (en) * | 2000-04-21 | 2002-09-28 | (주)닥터스텍 | Ascorbic acid composition for epidermal dosaging |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3387723B2 (en) | 2003-03-17 |
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