【発明の詳細な説明】〔産業上の利用分野〕本発明は、６員環及び７員環の複素環化合物及びその製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a 6- and 7-membered heterocyclic compound and a method for producing the same.
含窒素複素環にチオ基（Ｒ′Ｓ基 Ｒ′は任含の首換基
を表す）を導入するにはハロゲン置換複素環とＲ′ＳＨ
の反応、チオキソ基を有する複素環のアルキル化もしく
はアリール化、アゾ化合物とＲ’ＳＨとのカップリング
反応が主なものである。しかし複素環のハロゲン化はそ
の制御条件が難しく、好ましくない反応が起こり、又好
ましくない反応生成物がしばしば得られる事が多く、目
的とするハロゲン置換複素環を得るのが困難な場合が多
い。さらにチオキソ体やジアゾニウム塩を合成する時に
それぞれの複素環に応した良い方法がなく、本発明のチ
オ基を有する複素環を合成する事は容易ではない。しか
もシアノ基を有する複素環を合成するのは非常に困難と
いわざるをえない。To introduce a thio group (R'S group, R' represents any substituent group) into a nitrogen-containing heterocycle, a halogen-substituted heterocycle and R'SH
The main reactions include the alkylation or arylation of a heterocycle having a thioxo group, and the coupling reaction between an azo compound and R'SH. However, in the halogenation of heterocycles, the control conditions are difficult, undesirable reactions occur, and undesirable reaction products are often obtained, and it is often difficult to obtain the desired halogen-substituted heterocycle. Furthermore, when synthesizing thioxo derivatives and diazonium salts, there is no suitable method suitable for each type of heterocycle, and it is not easy to synthesize the thio group-containing heterocycle of the present invention. Moreover, it must be said that it is extremely difficult to synthesize a heterocycle having a cyano group.
含窒素複素環化合物は農医薬、香料、ポリマーの原＃１
等に使用されている利用範囲の広い化合物群である。特
にシアノ置換複素環はシアノ基を他の官能基に変換出来
るので、きわめて価値があると考えらや、る。さらにチ
オ基の導入により置換反応を行なうことによって、チオ
基を他の求核試剤と置き変えることが可能となるため、
いっそうの有用性が期待されるものである。Nitrogen-containing heterocyclic compounds are the #1 raw material for agricultural medicines, fragrances, and polymers.
It is a group of compounds that have a wide range of applications and are used in In particular, cyano-substituted heterocycles are considered to be extremely valuable because they can convert the cyano group into other functional groups. Furthermore, by introducing a thio group and performing a substitution reaction, it becomes possible to replace the thio group with another nucleophile.
It is expected that it will be even more useful.
本発明はチオ基を有するモノシアノ復素環を実用的に製
造する方法を提供するものである。The present invention provides a method for practically producing a monocyano heterocycle having a thio group.
本発明は一船式ＣＩ］〔式中、Ｒはへテロ環で置換されていてもよいアルキル
基、アラルキル基、シクロアルキル基、アルケニル基又
は置換基を有してもよいアリール基を、ｎはＯ，ｌ、２
を、Ｒ’ は水素、シアノ基、カルボニル基Ｓ又は弐
ＣＯＯＲ３（式中、Ｒ３は水素、アルキル基、アラルキ
ル基又はアリール基を示す。）で表わされるノ、腎を、
Ｒ２はアルキルノル、置換基を有してもよいアリール基
、アルコキシカルボニル基又はオキソ基を、ｍは０．１
．２（ｍが２以上のときＲ２は同一であっても相異って
いてもよい。）を示し、二つのＲ２が一緒Ｇこなって環
を形成してもよい。ＺはＣ−Ｃ又はＣ−Ｃ−Ｃを示し、
供線は各結合が二重結合をとりうることを示す。）で表
わされる化合物及びその製造方法である。[In the formula, R is an alkyl group that may be substituted with a heterocycle, an aralkyl group, a cycloalkyl group, an alkenyl group, or an aryl group that may have a substituent, is O, l, 2
, R' is hydrogen, a cyano group, a carbonyl group S or 2COOR3 (in the formula, R3 represents hydrogen, an alkyl group, an aralkyl group or an aryl group);
R2 is alkylnor, an aryl group which may have a substituent, an alkoxycarbonyl group, or an oxo group, m is 0.1
．． 2 (when m is 2 or more, R2 may be the same or different), and two R2 may be combined with G to form a ring. Z represents C-C or C-C-C,
The connecting lines indicate that each bond can be a double bond. ) and its production method.
本発明の化合物に６いて、チオ基とシアン）５を同時に
複素環に導入するためには、下記−殺伐（［１で示され
る、３（１ンにＲ３基（Ｒは…■記と同し意味を示す。In order to simultaneously introduce 6, thio group and cyanogen 5 into the heterocycle in the compound of the present invention, the following method is used: and indicate the meaning.
）をもつ２．３−ジアミノアクリロニトリル（以下ＤＡ
ＡＮと略記する。）、Ｎ ＣＣＮ Ｈ□あるいはその有機塩（ｐ−トルエンスルホン酸塩等）、
無機塩（塩酸塩等）を出発原料として用いる。) with 2,3-diaminoacrylonitrile (hereinafter referred to as DA
Abbreviated as AN. ), N CCN H□ or an organic salt thereof (p-toluenesulfonate, etc.),
Inorganic salts (such as hydrochloride) are used as starting materials.
（］） ピピランの製造法（ＩＩＩ） （ＩＶ）式中、Ｒは
ｉ：Ｉ記と同し意味を示し、Ｒ’、ｒｒ５ は夫々水素
、アルキル基、アラルキル基、アリール基又はアルコキ
シカルボニル基を示す。(]) Method for producing pipyran (III) (IV) In the formula, R has the same meaning as i:I, and R' and rr5 each represent hydrogen, an alkyl group, an aralkyl group, an aryl group, or an alkoxycarbonyl group. show.
反応（６媒はエタノールのようなアルコール（１、酢酸
エチルのようなエステル類、アセトニトリルのようなニ
トリル類、トルエン等の炭化水素ｉｎが用いられるが、
それらのものの混合物でもよい。Reaction (6 solvents used are alcohols such as ethanol (1), esters such as ethyl acetate, nitriles such as acetonitrile, and hydrocarbons such as toluene,
A mixture of these may also be used.
（２）ノオキソピラジンの製造法＜ ｖ ） 〔Ｖｌ ］式中、Ｒ
は（１；Ｉ記と同し意味を示す。Ｒ６は塩素又；よイミ
ダヅール基を示す。(2) Method for producing nooxopyrazine <v) [Vl] where, R
(1; has the same meaning as in Section I. R6 represents chlorine or imidazyl group.
反応、溶媒はジオキサンのようなエーテル類、クロロポ
ルムのようなハロゲノ化炭化水素類、トルエ／ヤクロロ
ヘンゼンのような芳香族ｔｌ￥が用いられる。For the reaction, ethers such as dioxane, halogenated hydrocarbons such as chloroporm, and aromatic tl such as toluene/yachlorohenzene are used.
（３）ジアゼピンの製造法式中、Ｒは１１り記と回し意味を示す。Ｒ” Ｒ１＋
はアルキル基、アリール基又はＲ’ Ｒθが一緒に
なってＩ（スを示す。(3) Method for producing diazepine In the formula, R indicates the meaning in numerals. R” R1+
represents an alkyl group, an aryl group, or R' Rθ taken together.
反応溶媒はエタノールのようなアルコールｔ′ｎ、酢酸
エチルのようなエステル類、アセトニド“ノルのような
ニトリルｊｌＴ、トルエン等の炭化水素類が用いられる
が、それらのものの混合物でもよい。As the reaction solvent, alcohols such as ethanol, esters such as ethyl acetate, nitriles such as acetonide, and hydrocarbons such as toluene are used, but mixtures thereof may also be used.
触媒はシュウ酸、ρ−トルエンスルホン酸のような有機
酸、硫酸や五酸化リンのような無機酸が用いられる。The catalyst used is an organic acid such as oxalic acid or ρ-toluenesulfonic acid, or an inorganic acid such as sulfuric acid or phosphorus pentoxide.
（４）ジヒド「Ｊジアゼピンの製造法式中、Ｒは１ｊ１１記と同じ意味を示す。Ｒ９ＲｌＧは
アルキル基又はアリール基を示す。(4) Method for producing dihydro "J diazepine In the formula, R has the same meaning as in 1j11. R9RlG represents an alkyl group or an aryl group.
反応溶媒、触媒は、（３）ジアゼピンの製造法の項で記
載された反応溶媒、触媒が用いられる。As the reaction solvent and catalyst, those described in the section (3) Method for producing diazepine are used.
本発明の化合物のスルフィドは、酸化反応により、ｍ−
クロロ過安息香酸や過酸化水素等の有■及び無機の酸化
剤を用いて相当するスルホキシドやスルホ／を得ること
ができる。又反応を円滑に進行するために適当な触媒を
用いることができる。The sulfide of the compound of the present invention can be converted to m-
The corresponding sulfoxides and sulfonyl compounds can be obtained using organic and inorganic oxidizing agents such as chloroperbenzoic acid and hydrogen peroxide. Further, an appropriate catalyst can be used to smoothly proceed the reaction.
又シアノ基を加水分解、脱炭酸することにより、カル・
ｈモ・イル基、カルボキシル基を経て水素に変換するこ
とができる。In addition, by hydrolyzing and decarboxylating the cyano group, cal-
It can be converted to hydrogen via an h-mo-yl group or a carboxyl group.
反応終了後は通常の後処理を行うことにより目的物を得
ることができる。After the reaction is completed, the desired product can be obtained by carrying out usual post-treatments.
本発明の化合物の構造は、［Ｒ，ＮＭＲ，Ｍａ ｓＳ等
から決定した。The structure of the compound of the present invention was determined from [R, NMR, MasS, etc.
次に実施例を挙げ本発明化合物を更に説明する。Next, the compounds of the present invention will be further explained with reference to Examples.
実 施 例 １２−シアノ−５６−ジフェニル−３−フェニルチオピラ
ジン（化合物番号１）ｎ−ヘキサンから再結晶を行い７．６ｇ（収率７０％）
の結晶を得た。ｍ、 ｐ、 １３７−１３８ ’ＣＮＭ
Ｒ，ｌ Ｒ，Ｍａ ｓ ｓスペクトルの結果は目的物の
構造を支持するが既知化合物への導入によりさらに確認
した。すなわち目的物とメチラートとの反応により得ら
れた生成物はＪ、 ｌｌｅｔｅｒｏｃｙｃｌｉｃＣｈｅ
ｍ、、＋７４５５（１９８０）に記載されている既知物
質である２−シアノ−３−メトキシ−５６−ジフェニル
ピラジンと全く同じものである。Example 1 2-cyano-56-diphenyl-3-phenylthiopyrazine (compound number 1) Recrystallized from n-hexane to give 7.6 g (yield 70%)
crystals were obtained. m, p, 137-138'CNM
The R,lR,Mass spectrum results supported the structure of the target product, which was further confirmed by incorporation into known compounds. That is, the product obtained by the reaction of the target substance and methylate is J, lleterocyclicChe.
It is exactly the same as 2-cyano-3-methoxy-56-diphenylpyrazine, which is a known substance described in J. M., +7455 (1980).
（Ｐｈ：フェニル基を示す。）２．３−ジアミノ−３−フェニルチオアクリロニトリル
（以下Ｐｈ５−ＤＡＡＮと略記する。） ５．７ｇ（
０，０２９８モル）をエタノール１００ｍ Ｎにとかし
、ヘンシル６、Ｉ ｇ （０，０２９モル）を加え、
室温で２時間撹拌した。析出した結晶を濾過し、ヘンゼ
ン実 施 例 ２２−シアノ−５，６−シメチルー３−フェニルチオピラ
ジン（化合物番号２）ＰｈＳ−ＤＡＡＮＩ９．Ｉ ｇ （０，１モル）を酢
酸エチル４００ＩＩＩβにとかしたＣ６液に無水硫酸マ
グネシウム３ｇを加え、撹拌しながら８．６ｇ （０
，１モル）のジアセチルを滴下し、室温で１時間撹拌し
た。反応混合物に活性炭１ｇを加えｆｊＩ遇し、濾液を
減圧下溜去すると・２３ｇの黄色結晶が残るので、ベン
ゼン−ｎ−ヘキサン（１：１）から再結晶を行い２０．
５１Ｔの白色結晶を得た。収率８５％ｍ、 ｐ、 ＋０９−１１０°Ｃ実 施 例 ３２−シアノ−３−メチルチオピラジン（化合物番号３）ＣＩｌ山ＤＡＡＮ ・＋＋ ｓ Ｏ３−＜矛Σ山６
ｇ （０，０２モル）と４０％グリオキヂール２．９
ｇ （０，０２モル）を １００ｍ１のエタノール中
、５０〜６０゛ｃで２時間撹１′トしたエタノールを溜
去後酢酸エチル１００ｍ ｌ加え、不溶物を濾過しでか
ら溶液を希塩酸で洗浄し、無水硫酸マグネシウムで乾燥
した。酢酸エチルを溜去後践る残、査をｎ−ヘキサンが
ら再結晶を行うと１．５ｇ （収率５０％）の結晶が得
られた。(Ph: indicates a phenyl group.) 2.3-diamino-3-phenylthioacrylonitrile (hereinafter abbreviated as Ph5-DAAN) 5.7 g (
0,0298 mol) was dissolved in 100 mN ethanol, Hensyl 6, Ig (0,029 mol) was added,
Stirred at room temperature for 2 hours. The precipitated crystals were filtered and added to Hensen's Example 2 2-cyano-5,6-dimethyl-3-phenylthiopyrazine (Compound No. 2) PhS-DAANI9. 3 g of anhydrous magnesium sulfate was added to a C6 solution prepared by dissolving I g (0.1 mol) in 400 IIIβ ethyl acetate, and while stirring, 8.6 g (0
, 1 mol) of diacetyl was added dropwise, and the mixture was stirred at room temperature for 1 hour. 1 g of activated carbon was added to the reaction mixture, and the filtrate was distilled off under reduced pressure. 23 g of yellow crystals remained, so they were recrystallized from benzene-n-hexane (1:1).
White crystals of 51T were obtained. Yield 85% m, p, +09-110°C Example 3 2-cyano-3-methylthiopyrazine (compound number 3) CIl mountain DAAN ・++ s O3-< Σ mountain 6
g (0.02 mol) and 40% glyochidyl 2.9
g (0.02 mol) was stirred in 100 ml of ethanol at 50-60°C for 2 hours. After distilling off the ethanol, 100 ml of ethyl acetate was added, the insoluble matter was filtered, and the solution was washed with dilute hydrochloric acid. , dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, the residue was recrystallized from n-hexane to obtain 1.5 g (yield: 50%) of crystals.
ｍ、 ｐ、 ８１．５〜８２．５°Ｃ実施 例 ４シアノ−５−メチルメチルチオピラジン（化合物番号４）Ｎ Ｍ ＲｌＩ Ｒ１Ｍａｓｓスペクトルの結果は目的
物の構造を支持づる。m, p, 81.5-82.5°C Example 4 Cyano-5-methylmethylthiopyrazine (Compound No. 4) N M RlI R1Mass spectrum results support the structure of the target product.
目的物の脱ソアノ化物はＪ ＯＣ２９４１５（＋９６４
）に記載のある２−ヒドロキシ−６−メチルピラジンを
塩素化し２−クロロ−６−メチルピラジンとしメチルメ
ルカプチド （Ｃ１ｌ、５Ｎａ） との反応で得られ
る２−メチルチオ−６−メチルピラジンと全く同しもの
であった。The desoanated product of the target product is JOC29415 (+964
) is exactly the same as 2-methylthio-6-methylpyrazine, which is obtained by chlorinating 2-hydroxy-6-methylpyrazine to produce 2-chloro-6-methylpyrazine and reacting it with methylmercaptide (C1l, 5Na). It was a servant.
をアセトニトリル２００ｍ １２ に懸濁させ、トリエ
チルアミン３．１ｇ （０，０３モル）を加えた。均一
？ｗ液になってから４０％ピルビックアルデヒド５，４
ｇ（０，０３モル）を加え、２時間室温で撹拌した。ア
セトニトリルを溜去して残る残漬にベンゼンを加え、不
７容物を濾過し、飽和食塩水で洗浄し無水硫酸マグ名シ
ウムで乾燥した。ベンゼンを溜去すると５ｇのネ■生成
吻が残るので、ソリカゲル力うムクロマトグラフィー（
流出溶媒ベンゼン）で精製した。３．６ｇ （収率７
３％）の黄色斜状結晶が得られた。ｍ、 ｐ、８３〜８
４．５°Ｃ実 施 例 ５５ Ｇ−ジメチル−３−フェニルチオピラジン２−カル
ボキサミド（化合物番号３１）２−シアノ−５，６−シ
メチルー３＝フエニルチオピラジンｌｏｇを濃硫酸６０
ｍ ｌ中に加え１日撹（！シた。反応混合物を５００ｍ
βの氷水中乙こあけ析出した結晶を１．ｌ＃過し、水で
充分洗浄し乾す・”Ｊした。was suspended in 200 m 12 of acetonitrile, and 3.1 g (0.03 mol) of triethylamine was added. Uniform? 40% pyruvic aldehyde 5,4 after turning into w liquid
g (0.03 mol) and stirred at room temperature for 2 hours. Benzene was added to the residue left after acetonitrile was distilled off, and the residue was filtered, washed with saturated saline, and dried over anhydrous magnesium sulfate. When the benzene is distilled off, 5 g of the nephrogenic residue remains, so it is subjected to solica gel chromatography (
The effluent solvent was benzene). 3.6g (yield 7
3%) of yellow oblique crystals were obtained. m, p, 83-8
4.5°C Example 5 5 G-dimethyl-3-phenylthiopyrazine 2-carboxamide (compound number 31) 2-cyano-5,6-dimethyl-3=phenylthiopyrazine log was dissolved in concentrated sulfuric acid 60
ml and stirred for 1 day.The reaction mixture was
1. Pour the precipitated crystals of β into ice water. Wash thoroughly with water and dry.
１０ｇ（収率９３％）の目的物を得た。10 g (yield 93%) of the target product was obtained.
ｍ、 ｐ、 ２０８−２０９．５°Ｃ（酢酸エチルから
再結晶）。m, p, 208-209.5 °C (recrystallized from ethyl acetate).
実 施 例 ６５６−ツメチルー、゛３−フェニルチオピラジン２−カ
ルボン酸（化合物番号３３）ェニルチオピラジンー２＝カルボキサミド５ｇを［５％
塩酸８０ｍ２に）」口え加熱還ｌんを３時間行った。Example 6 56-Thmethyl-,3-phenylthiopyrazine-2-carboxylic acid (Compound No. 33) 5g of phenylthiopyrazine-2=carboxamide was added to [5%
The mixture was heated and refluxed in 80 m2 of hydrochloric acid for 3 hours.
反応混合物を酢酸エチルで抽出した後、減圧下で溶媒を
溜去して残る残渣をカセイソーダでアルカリ性にすると
結晶が析出するから濾別し、この結晶を０＝塩酸で処理
すると一旦とけてすくに白色結晶が析出した。水で充分
洗浄して乾燥した。１．２ｇ（収率２４％）の目的物を
得た。After extracting the reaction mixture with ethyl acetate, the solvent is distilled off under reduced pressure, and the remaining residue is made alkaline with caustic soda. Crystals precipitate, so they are filtered out. When these crystals are treated with 0=hydrochloric acid, they dissolve once and are easily drained. White crystals precipitated. It was thoroughly washed with water and dried. 1.2 g (yield 24%) of the target product was obtained.
ｍ、 ｐ、 １２＝Ｌ５−１２６’Ｃ。m, p, 12=L5-126'C.
実 施 例 ７５．６−ジメチル−３〜フエニルチオピラジン２−カル
７１εン酸エチル（化合物番号３４）実施例６で得られ
た５、６−ジメチル−３−フェニルチオ−２−ピラジン
カルボン酸１ｇを濃硫酸を触媒にして５０ｍ １．エタ
ノール中で５時間加熱還７・ンした。アルコールを溜去
すると結晶が残るので・＼／ゼンーｎ−ヘキサンから再
結晶を行い１ｇ実施例５で得られた５、６−ノメチルー
３−フ（９０％）の目的物を得た。Example 7 5,6-dimethyl-3-phenylthiopyrazine 2-car71eethyl ester (Compound No. 34) 5,6-dimethyl-3-phenylthio-2-pyrazinecarboxylic acid obtained in Example 6 50ml using 1g of concentrated sulfuric acid as a catalyst 1. The mixture was heated to reflux in ethanol for 5 hours. When the alcohol was distilled off, crystals remained, so recrystallization was performed from n-hexane to obtain 1 g of the desired product, 5,6-nomethyl-3-f (90%) obtained in Example 5.
ｍ、 ｐ、 ７９−８０°Ｃ実 施 例 ８２−シアノ−３−フェニルスルホニルピラジン（化合物
番号２２）実 施 例 ９２３−ツメチル５−フェニルチオピラジン（化合物層５じ−３７）１０ｇの２−シアノ−３−フエニルチオピラジンヲ２０
０ｍｆｆ１のクロロホルムに溶解し、１０°Ｃ以下に冷
やしたところへｍ−クロル過安息香酸１７ｇを少喰ずつ
加え、１０°Ｃ以下に保った。加え終わったらそのまま
室温にもどし、３時間撹１′ドシた。析出した結晶（ｍ
−クロロ安息香酸）を濾過し、ａ液を炭酸すトリウム水
で３度洗浄した後、飽和食塩水で洗浄した。有殿層を分
離した後、無水硫酸マグ７シウムで乾燥し、減圧４縮し
た。エタノール、または、クロロホルム−〇−ヘキサン
で再結晶したｆ＆９．１ｇの白色結晶を得た。（収率７
９％）ｍ、 ｐ、 １２０．５−１２１．５°Ｃ５，６
−シメチルー３−フェニルチオピラジン−２−カルホキ
４ノミド １．３ｇを１５％塩酸５０ｍ ｌ中ＣＺ ？
、 Ｑさせ、３時間加熱還流した。その間不拘−から均
一な溶液に変化した。反応混合液を分液ロートに移し、
飽和食塩水を入れると白濁するから、酢酸エチル１００
ｍ Ｅを入れて抽出を行った。m, p, 79-80°C Example 8 2-cyano-3-phenylsulfonylpyrazine (Compound No. 22) Example 9 23-Tmethyl5-phenylthiopyrazine (Compound Layer 5-37) 10g of 2 -Cyano-3-phenylthiopyrazine 20
The mixture was dissolved in 0 mff1 of chloroform and cooled to below 10°C, and then 17 g of m-chloroperbenzoic acid was added in small portions and the temperature was kept below 10°C. After the addition was complete, the mixture was returned to room temperature and stirred for 3 hours. The precipitated crystals (m
-chlorobenzoic acid) was filtered, and the solution a was washed three times with thorium carbonate water and then with saturated saline. After separating the precipitate layer, it was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. Recrystallized from ethanol or chloroform-〇-hexane, 9.1 g of white crystals were obtained. (yield 7
9%) m, p, 120.5-121.5°C5,6
-Simethyl-3-phenylthiopyrazine-2-calphoky4nomide 1.3 g in 50 ml of 15% hydrochloric acid CZ?
, Q, and heated under reflux for 3 hours. During that time, the solution changed from uncontained to a homogeneous solution. Transfer the reaction mixture to a separatory funnel;
If you add saturated saline, it will become cloudy, so add 100% ethyl acetate.
Extraction was performed by adding mE.
０．４ｇの目的物を得た。 収率４０％ｎ ｏ ：１．
６１９２その他の生成物は５．６−ノツチルー３−フェ
ニルチオピラジン−２−カルボン酸であった。0.4 g of the target product was obtained. Yield 40% no: 1.
6192 Other product was 5,6-notty-3-phenylthiopyrazine-2-carboxylic acid.
実 施 例 １０５−ノアノー６−フェニルチオ−２３−ビラジンノカル
ボン酸ンエチル（化合物番号３５）０．９６ ｇのＰｈ
５−ＤＡＡＮを２０ｍ ｌのエタノールに溶解した中に
室温で、ジオキソ酒石酸ジエチル１．０１ｇを滴下した
。室温で１時間撹拌した後加熱還流を２時間行なった。Example 10 Ph of 0.96 g of ethyl 5-noano-6-phenylthio-23-virazinenocarboxylate (Compound No. 35)
1.01 g of diethyl dioxotartrate was added dropwise to a solution of 5-DAAN in 20 ml of ethanol at room temperature. After stirring at room temperature for 1 hour, the mixture was heated under reflux for 2 hours.
エタノールを減圧留去し、残渣を水にあけ酢酸エチルを
抽出、無水硫酸マグネシウムで乾燥後、酢酸エチルと減
圧留去した。カラム績製（クロロホルム）により１．３
４ ｇの黄色結晶を得た。（収率７５％）ｍ、 ｐ、 ８３〜８４°Ｃ実 施 例 １１５−シアノ−２，３−ジオキソー６−フエニルチオ−１
，２，３，４−テトラヒドロピラジン（化合物番号３６
）シュウ酸クロリド１．３ｇを２０ｍ ｌのジオキサンに
７容かしたｌ容、・夜に１２〜１５°ＣでＰｈ５−ＤＡ
ＡＮ １．９ ｇのジオキサン？８ｉｆｆ１２Ｏｎ／
！を滴下した。滴下後室温で３０分撹拌し、さらに５０
°Ｃで９０分加熱した （発生する ＨＣＩを除去）
ＴＬＣＴ：ＤＡＡＮの消失を確認した後反応溶液を
ロータリーエバポレーク−で減圧下ジオキサンを留去し
た。杓１．７９ｇの粗生成物が得られた。この粗生成物
を飽和炭酸ソーダ水に溶かし不ｌ容物を濾過した後、４
Ｈｃ＋にて中和し１ｇの生成物を得た。Ethanol was distilled off under reduced pressure, and the residue was poured into water to extract ethyl acetate. After drying over anhydrous magnesium sulfate, ethyl acetate was distilled off under reduced pressure. 1.3 by column preparation (chloroform)
4 g of yellow crystals were obtained. (Yield 75%) m, p, 83-84°C Example 11 5-cyano-2,3-dioxo-6-phenylthio-1
, 2,3,4-tetrahydropyrazine (compound number 36
) 1.3 g of oxalyl chloride in 7 volumes of 20 ml of dioxane, Ph5-DA at 12-15°C at night.
AN 1.9 g of dioxane? 8iff12On/
! was dripped. After dropping, stir at room temperature for 30 minutes, and then stir for 50 minutes.
Heated at °C for 90 minutes (removes generated HCI)
TLCT: After confirming the disappearance of DAAN, dioxane was distilled off from the reaction solution under reduced pressure using a rotary evaporator. A ladle of 1.79 g of crude product was obtained. After dissolving this crude product in saturated sodium carbonate water and filtering off the insoluble matter,
Neutralization with Hc+ gave 1 g of product.
収率４１％ ｍ、 ｐ、 ２５０°Ｃ以上。Yield 41% m, p, 250°C or higher.
実 施 例 １２２−シアノ−５７−シメチルー３−フェニルチオ−１’
、４，６Ｈ−ジアゼピン（化合物番号４０）ρｈｓ、Ｄ
ＡＡＮ１．９１ ｇをヘンぎン２０ｍ ｆ！に懸濁し
、アセデルアセトン１．１ｇとンユウ酸０．０３ｇを加
え、加熱コ流下、共沸脱水により水を留去しながら３時
間反応した。反応終了後、反応液を冷却し、不（古物を
除）ｆした後、溶媒を留去した。残渣をシリカゲル力ラ
ムクロマトグラフィークこよθＦ＋’ｔ ’１４して「
］的１ｉ １．２ ｇ ＜： ｆ５ タ。Ｉｆ！１ＬＩ
７．１％ｍ、 ｐ、 ｌｌｌ−１１１，５’Ｃ実
施 例 １３２− ノアノー５．６−シヒドロー７−メチル２〕−フ
ェニル−３−フェニルチオ−１，４，４Ｆ＋ジアゼピン
（化合物番号４３）ＰｈＳ−ＤＡＡＮ １．９１ ｇのエタノール？容液
にヘンデルアセトノ１．４６ｇを加え、次いで濃硫酸０
．０５ｇを加え室温にて３時間反応した。反応終了後反
応液を水にあけて、酢酸エチルで抽出し、酢酸エチル層
を水洗後無水硫酸マグ不ノウムで乾燥した後、溶媒を留
去した。残渣をシリカゲルカラムクロマトグラフィーに
より情調して目的物２．７ｇを得た。Example 12 2-cyano-57-dimethyl-3-phenylthio-1'
, 4,6H-diazepine (compound number 40) ρhs, D
AAN1.91g 20m f! 1.1 g of acedelacetone and 0.03 g of phosphoric acid were added, and the mixture was reacted for 3 hours while water was distilled off by azeotropic dehydration under heating. After the reaction was completed, the reaction solution was cooled and filtered (old materials were removed), and then the solvent was distilled off. The residue was subjected to silica gel force column chromatography θF+'t'14.
] Target 1i 1.2 g <: f5 ta. If! 1LI
7.1% m, p, lll-111,5'C real
Example 13 2-Noano5,6-sihydro7-methyl2]-phenyl-3-phenylthio-1,4,4F+Diazepine (Compound No. 43) PhS-DAAN 1.91 g of ethanol? Add 1.46 g of Handel acetonate to the solution, then add 0.0 g of concentrated sulfuric acid.
．． 05 g was added and reacted at room temperature for 3 hours. After the reaction was completed, the reaction solution was poured into water and extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was analyzed by silica gel column chromatography to obtain 2.7 g of the desired product.
収・ト８５％ ｎｏ ： １．６５８（１−１−記実施
例の化合物もなめて 本発明化合物の代表例を第１表、
第２表Ｑこ示す。Yield: 85% No.: 1.658 (including the compounds of Examples 1-1-) Representative examples of the compounds of the present invention are shown in Table 1.
Table 2 shows Q.
第表〔発明の効果〕本発明の化合物は、農医薬、香料、染料、」ミリマー等
の原料ないし中間体として任用であり、ＤＡ Ａ Ｎを
出発原料として工業的に有利に製造できる。Table 1 [Effects of the Invention] The compounds of the present invention can be used as raw materials or intermediates for agricultural medicines, fragrances, dyes, millimers, etc., and can be advantageously produced industrially using DAAN as a starting material.
出代理人人（４３０）日本曹達株式会社（７１２５） 横 山 吉 美果１頁の続き■Ｉｎｔ、 Ｃ１，’識別記号庁内整理番号″［相］発［相］発明明者者波田多崎野裕こ４己７日美治神奈川県小田原市高田字柳町３４５ 日本曹達株式会
社小田原研究所内岡山県倉敷市児島塩生字新浜２７６７−１２ 日本曹
達株式会社水島工場内Representative (430) Nippon Soda Co., Ltd. (7125) Yoshi Yokoyama Mika Continued from page 1 ■Int, C1,' Identification code Internal reference number "[Ai] From [Ai] Inventor Hiroshi Hata Tasakino 4/7 days Miji 345 Yanagimachi, Takada, Odawara City, Kanagawa Prefecture Odawara Research Institute, Nippon Soda Co., Ltd. 2767-12 Niihama, Kojima Shio, Kurashiki City, Okayama Prefecture Inside the Mizushima Factory of Nippon Soda Co., Ltd.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23362888AJPH0249775A (en) | 1988-05-19 | 1988-09-20 | Heterocyclic compound having 6-membered or 7-membered ring and production thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-120729 | 1988-05-19 | ||
| JP12072988 | 1988-05-19 | ||
| JP23362888AJPH0249775A (en) | 1988-05-19 | 1988-09-20 | Heterocyclic compound having 6-membered or 7-membered ring and production thereof |
| Publication Number | Publication Date |
|---|---|
| JPH0249775Atrue JPH0249775A (en) | 1990-02-20 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23362888APendingJPH0249775A (en) | 1988-05-19 | 1988-09-20 | Heterocyclic compound having 6-membered or 7-membered ring and production thereof |
| Country | Link |
|---|---|
| JP (1) | JPH0249775A (en) |
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