JP3044383B2 - Method for producing nitrogen-containing 6-membered ring compound - Google Patents
Method for producing nitrogen-containing 6-membered ring compoundInfo
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- JP3044383B2 JP3044383B2 JP2131758A JP13175890A JP3044383B2 JP 3044383 B2 JP3044383 B2 JP 3044383B2 JP 2131758 A JP2131758 A JP 2131758A JP 13175890 A JP13175890 A JP 13175890A JP 3044383 B2 JP3044383 B2 JP 3044383B2
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- membered ring
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は含窒素６員環化合物の製造方法に関する。The present invention relates to a method for producing a nitrogen-containing 6-membered ring compound.
［発明の背景］ 含窒素６員環化合物は酸化防止剤等に用いられ、ま
た、種々の有用な化合物を製造するための中間体として
用いられている。BACKGROUND OF THE INVENTION Nitrogen-containing 6-membered ring compounds are used as antioxidants and the like, and are also used as intermediates for producing various useful compounds.
含窒素６員環化合物の一般的な合成方法として、従
来、下記の方法が知られていた。As a general method for synthesizing a nitrogen-containing 6-membered ring compound, the following method has been conventionally known.
しかしながら、上記の合成方法ａ）及びｂ）は収率よ
く含窒素６員環化合物が得られる反面、ジビニル体およ
びハロゲン化物の入手が困難であり、低コストで製造す
る方法としては好ましくない。また、ジビニル体および
ハロゲン化物は毒性が非常に高く、出発原料として用い
る場合、作業の安全上好ましくない。 However, the above synthesis methods a) and b) provide a nitrogen-containing 6-membered ring compound in good yield, but it is difficult to obtain a divinyl compound and a halide, which is not preferable as a low-cost production method. Further, divinyl compounds and halides are very toxic, and when used as starting materials, they are not preferred in terms of work safety.
［発明の目的］ したがって本発明の目的は、作業安全性に問題がな
く、低コスト、高収率で純度の高い含窒素６員環化合物
を製造することができる含窒素６員環化合物の製造方法
を提供することにある。[Object of the Invention] Therefore, an object of the present invention is to produce a nitrogen-containing 6-membered ring compound which can be produced at a low cost, a high yield and a high purity without any problem in work safety. It is to provide a method.
［発明の構成］ 本発明の上記目的は以下によって達成された。[Constitution of the Invention] The above object of the present invention has been achieved by the following.
一般式［Ｉ］で表される化合物と一般式［VI］で表さ
れる化合物を反応させて一般式［IV］及び／又は一般式
［Ｖ］で表される化合物を得、該一般式［IV］及び／又
は一般式［Ｖ］で表される化合物を単離することなく一
般式［II］で表される化合物を反応させることを特徴と
する一般式［III］で表される含窒素６員環化合物の製
造方法。The compound represented by the general formula [I] and the compound represented by the general formula [VI] are reacted to obtain a compound represented by the general formula [IV] and / or the general formula [V]. A compound represented by the general formula [III] characterized by reacting a compound represented by the general formula [II] without isolating the compound represented by the formula [IV] and / or [V] A method for producing a 6-membered ring compound.
一般式［Ｉ］ 一般式［II］ R9−NH2 一般式［III］ 一般式［Ｉ］、［II］、［III］において、R1〜R8は
水素原子、アルキル基、またはアリール基を表す。Ｘ
は、 を表す。R9、R10はアルキル基またはアリール基を表
す。General formula [I] General formula [II] R 9 -NH 2 General formula [III] In the general formulas [I], [II] and [III], R 1 to R 8 represent a hydrogen atom, an alkyl group or an aryl group. X
Is Represents R 9 and R 10 represent an alkyl group or an aryl group.
一般式［IV］ 一般式［Ｖ］ 一般式［IV］及び［Ｖ］において、Ｒ′はアルキル
基、アリール基又はヒドロキシル基を表す。R11〜R24は
水素原子、アルキル基又はアリール基を表す。Ｘは一般
式［Ｉ］におけるＸと同義である。General formula [IV] General formula [V] In the general formulas [IV] and [V], R ′ represents an alkyl group, an aryl group or a hydroxyl group. R 11 to R 24 represent a hydrogen atom, an alkyl group or an aryl group. X has the same meaning as X in formula [I].
一般式［VI］ Ｒ′SO2Y 一般式［VI］において、Ｙはヒドロキシル基又はハロ
ゲン原子を表す。Ｒ′は前記一般式［IV］におけるＲ′
と同義である。In the general formula [VI] R'SO 2 Y formula [VI], Y represents a hydroxyl group or a halogen atom. R ′ is the same as R ′ in the general formula [IV].
Is synonymous with
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
一般式［Ｉ］、一般式［II］及び一般式［III］にお
いて、R1〜R10で表されるアルキル基としては、炭素数
１〜24の直鎖又は分岐のアルキル基（例えばメチル基、
エチル基、イソプロピル基、ｔ−ブチル基、２−エチル
ヘキシル基、ドデシル基、ｔ−オクチル基、ベンジル
基）が好ましい。In the general formulas [I], [II] and [III], the alkyl group represented by R 1 to R 10 is a linear or branched alkyl group having 1 to 24 carbon atoms (eg, a methyl group ,
Ethyl, isopropyl, t-butyl, 2-ethylhexyl, dodecyl, t-octyl, benzyl).
R1〜R10で表されるアリ−ル基としては、例えばフェ
ニル基、ナフチル基が挙げられる。Examples of the aryl group represented by R 1 to R 10 include a phenyl group and a naphthyl group.
R1〜R10で表されるこれら各基は、更に置換基を有す
るものも含み、置換基としては、ヒドロキシル基、アル
コキシ基、アリ−ル基、アシルアミノ基、スルホンアミ
ド基、アリ−ルオキシ基、アルキルチオ基、カルバモイ
ル基、スルファモイル基、アルキルスルホニル基、ニト
ロ基、シアノ基、アリ−ルスルホニル基、ハロゲン原
子、カルボキシ基、アミノ基、アリ−ルアミノ基、アル
キルアミノ基、アルコキシカルボニル基、アシル基、ア
シルオキシ基等が挙げられる。Each of these groups represented by R 1 to R 10 includes those further having a substituent. Examples of the substituent include a hydroxyl group, an alkoxy group, an aryl group, an acylamino group, a sulfonamide group, and an aryloxy group. , Alkylthio, carbamoyl, sulfamoyl, alkylsulfonyl, nitro, cyano, arylsulfonyl, halogen, carboxy, amino, arylamino, alkylamino, alkoxycarbonyl, acyl And an acyloxy group.
本発明の一般式［Ｉ］で表される化合物を出発原料と
して得られる中間体は、下記一般式［IV］で表されるス
ルホン酸エステル誘導体化合物及び／または下記一般式
［Ｖ］で表されるジビニル化合物である。The intermediate obtained by using the compound represented by the general formula [I] of the present invention as a starting material is represented by a sulfonic ester derivative compound represented by the following general formula [IV] and / or a general formula [V]: Divinyl compound.
一般式［IV］ 一般式［Ｖ］ 式中、Ｒ′はアルキル基、アリ−ル基又はヒドロキシ
ル基を表し、R11〜R24は水素原子、アルキル基又はアリ
−ル基を表わす。Ｘは一般式［Ｉ］におけるＸと同義で
ある。General formula [IV] General formula [V] Wherein, R 'is an alkyl group, ant - represents a group or a hydroxyl group, R 11 to R 24 is a hydrogen atom, an alkyl group or ants - represents Le group. X has the same meaning as X in formula [I].
一般式［IV］で表されるスルホン酸エステル誘導体
は、一般式［Ｉ］で表される化合物と下記一般式［VI］
で表されるスルホニルハライド類及び／または無機ある
いは有機の酸とを反応させることによって製造すること
ができる。The sulfonic acid ester derivative represented by the general formula [IV] includes a compound represented by the general formula [I] and a compound represented by the following general formula [VI]
By reacting with a sulfonyl halide represented by the formula (1) and / or an inorganic or organic acid.
この場合、一般式［VI］で表される化合物の添加量は
一般式［Ｉ］で表わされる化合物１モル当たり0.1〜10
モルの範囲であり、好ましくは0.5〜５モルの範囲であ
る。In this case, the amount of the compound represented by the general formula [VI] is 0.1 to 10 per mol of the compound represented by the general formula [I].
Mole range, preferably 0.5 to 5 moles.
一般式［VI］ Ｒ′SO2Y 式中、Ｙはヒドロキシル基又はハロゲン原子を表す。
Ｒ′は前記一般式［IV］におけるＲ′と同義である。In the general formula [VI] R'SO 2 Y formula, Y represents a hydroxyl group or a halogen atom.
R 'has the same meaning as R' in formula [IV].
反応溶媒は使用しても、使用しなくてもよい。 A reaction solvent may or may not be used.
使用し得る反応溶媒としては、例えばエ−テル類（例
えばジエチルエ−テル、ジイソプロピルエ−テル）、ハ
ロゲン化炭化水素類（例えばクロロホルム、四塩化炭
素）、芳香族炭化水素類（例えばトルエン、キシレ
ン）、脂肪族炭化水素類（例えばヘキサン、ヘプタ
ン）、エステル類（例えば酢酸エチル）、鉱酸類（例え
ば硫酸）、有機酸（例えば酢酸）及びこれらの混合溶媒
を挙げることができる。反応温度は０〜100℃であり、
好ましくは10〜80℃である。Examples of the reaction solvent that can be used include ethers (eg, diethyl ether, diisopropyl ether), halogenated hydrocarbons (eg, chloroform, carbon tetrachloride), and aromatic hydrocarbons (eg, toluene, xylene). And aliphatic hydrocarbons (eg, hexane, heptane), esters (eg, ethyl acetate), mineral acids (eg, sulfuric acid), organic acids (eg, acetic acid), and mixed solvents thereof. The reaction temperature is 0-100 ° C,
Preferably it is 10-80 degreeC.
一般式［Ｖ］で表されるジビニル化合物は一般式［I
V］で表される化合物を塩基でビニル化することによっ
て製造することができる。The divinyl compound represented by the general formula [V] is represented by the general formula [I
V] can be produced by vinylating a compound represented by the formula [V] with a base.
使用される塩基には特に限定はないが、例えば苛性ア
ルカリ金属、アルカリ金属の炭酸塩、アルカリ金属の酢
酸塩、アルカリ金属の重炭酸塩及びそれらの水溶液、ア
ミン類（例えばトリエチルアミン、ジメチルアニリン、
ピリジン）を使用することができる。添加量は、一般式
［IV］で表される化合物１モル当り0.1〜５モルの範囲
であり、好ましくは0.5〜５モルの範囲である。反応温
度は０〜60℃であり、好ましくは０〜40℃である。The base used is not particularly limited, but includes, for example, caustic alkali metals, alkali metal carbonates, alkali metal acetates, alkali metal bicarbonates and aqueous solutions thereof, and amines (eg, triethylamine, dimethylaniline,
Pyridine) can be used. The amount of addition is in the range of 0.1 to 5 mol, preferably 0.5 to 5 mol, per 1 mol of the compound represented by the general formula [IV]. The reaction temperature is 0 to 60 ° C, preferably 0 to 40 ° C.
一般式［IV］および［Ｖ］で表される化合物はゼラチ
ンなどの高分子化合物の架橋剤として有用であり、ま
た、各種化合物の合成に用いる中間体として有用であ
る。The compounds represented by the general formulas [IV] and [V] are useful as a cross-linking agent for a high molecular compound such as gelatin, and are also useful as intermediates used for synthesizing various compounds.
一般式［IV］において、Ｒ′がメチル基、フェニル
基、４−メチルフェニル基またはヒドロキシル基であ
り、またＸが−SO2−であるものが中間体として好まし
い。In the general formula [IV], R 'is a methyl group, a phenyl group, a 4-methylphenyl group or a hydroxyl group, and X is -SO 2 - Preferred is that as an intermediate.
一般式［II］において、R9がフェニル基であるものが
合成原料として好ましい。In the general formula [II], a compound in which R 9 is a phenyl group is preferable as a raw material for synthesis.
本発明の一般式［III］で表される含窒素６員環化合
物を製造する場合、一般式［IV］で表される化合物を直
接一般式［II］で表される化合物と反応させてもよい
が、一般式［Ｖ］で表される化合物を一般式［II］で表
される化合物と反応させることが好ましい。When the nitrogen-containing 6-membered ring compound represented by the general formula [III] of the present invention is produced, the compound represented by the general formula [IV] may be directly reacted with the compound represented by the general formula [II]. It is preferable to react the compound represented by the general formula [V] with the compound represented by the general formula [II].
本発明の一般式［III］で表される含窒素６員環化合
物を製造する場合に、通常、溶媒が用いられる。When producing the nitrogen-containing 6-membered ring compound represented by the general formula [III] of the present invention, a solvent is usually used.
反応溶媒としては特に限定はないが、例えば、エ−テ
ル類（例えばジエチルエ−テル、ジイソプロピルエ−テ
ル）、ハロゲン化炭化水素類（例えばクロロホルム、四
塩化炭素）、芳香族炭化水素類（例えばトルエン、キシ
レン）、脂肪族炭化水素類（例えばヘプタン、デカ
ン）、エステル類（例えば酢酸エチル）、アルコ−ル類
（例えばメタノ−ル、エタノ−ル、ｎ−ブタノ−ル）、
水及びこれらの混合溶媒を挙げることができる。反応温
度は40〜200℃であり、好ましくは60〜150℃である。The reaction solvent is not particularly limited, and examples thereof include ethers (eg, diethyl ether and diisopropyl ether), halogenated hydrocarbons (eg, chloroform, carbon tetrachloride), and aromatic hydrocarbons (eg, toluene). , Xylene), aliphatic hydrocarbons (eg, heptane, decane), esters (eg, ethyl acetate), alcohols (eg, methanol, ethanol, n-butanol),
Water and a mixed solvent thereof can be exemplified. The reaction temperature is 40-200 ° C, preferably 60-150 ° C.
本発明の一般式［III］で表される含窒素６員環化合
物は、酸化防止剤として有用であり、また、各種化合物
の合成に用いる中間体として有用である。The nitrogen-containing 6-membered ring compound represented by the general formula [III] of the present invention is useful as an antioxidant and also as an intermediate used for synthesizing various compounds.
次に一般式［Ｉ］で表される化合物の代表的具体例を
示すが、本発明の一般式［Ｉ］で表される化合物はこれ
らに限定されるものではない。Next, typical specific examples of the compound represented by the general formula [I] are shown, but the compound represented by the general formula [I] of the present invention is not limited thereto.
次に、一般式［II］で表される化合物の代表的具体例
を示すが、本発明の一般式［II］で表される化合物はこ
れらに限定されるものではない。 Next, typical examples of the compound represented by the general formula [II] are shown, but the compound represented by the general formula [II] of the present invention is not limited thereto.
次に、一般式［III］で表される含窒素６員環化合物
の代表的具体例を示すが、本発明の一般式［III］で表
される含窒素６員環化合物はこれらに限定されるもので
はない。 Next, typical specific examples of the nitrogen-containing six-membered ring compound represented by the general formula [III] are shown, but the nitrogen-containing six-membered ring compound represented by the general formula [III] of the present invention is not limited thereto. Not something.
［実施例］ 以下に本発明の具体的実施例を記載するが、本発明は
これらに限定されない。 [Examples] Specific examples of the present invention will be described below, but the present invention is not limited thereto.
実施例 （例示化合物III−５の合成） Ｉ−１ 30gをクロロホルム150cc中で攪拌懸濁し、室
温でゆっくりとクロロスルホン酸49.8gを滴下した。さ
らに滴下後、１時間約60℃に加温した。クロロホルムを
減圧留去し、油状の残渣（一般式［IV］に相当する化合
物、NMRおよびマススペクトルより確認した。）に水100
ccをゆっくりと加えて油状物を溶解した。その水溶液に
内温10℃以下に保持されるようにして20％苛性ソ−ダ水
溶液をpHが約９になるまで滴下した。（一般式［Ｖ］に
相当する油状物生成、NMR、マススペクトルおよびガス
クロマトグラフィ−より確認した。）次に反応液に１−
ブタノ−ル150cc、II−５ 18gを加え、５時間還流し
た。Example (Synthesis of Exemplified Compound III-5) 30 g of I-1 was stirred and suspended in 150 cc of chloroform, and 49.8 g of chlorosulfonic acid was slowly added dropwise at room temperature. After the addition, the mixture was heated to about 60 ° C. for 1 hour. Chloroform was distilled off under reduced pressure, and an oily residue (a compound corresponding to the general formula [IV], confirmed by NMR and mass spectrum) was added with 100 parts of water.
cc was added slowly to dissolve the oil. A 20% aqueous solution of caustic soda was added dropwise to the aqueous solution until the internal temperature was kept at 10 ° C. or lower until the pH reached about 9. (The formation of an oil corresponding to the general formula [V] was confirmed by NMR, mass spectrum and gas chromatography.)
150 cc of butanol and 518 g of II-518 were added, and the mixture was refluxed for 5 hours.
反応後、冷却し、析出した結晶を濾取し、冷メタノ−
ルと水で洗浄した。得られた結晶をアセトニトリルによ
り再結し、目的物37.5gを得た。（収率85％、融点156〜
157℃） 液体クロマトグラフィ−により純度を求めたところ、
99.0％の高純度のものであった。化合物の同定は、NMR
スペクトル、マススペクトルで行ない、目的の化合物で
あることを確認した。After the reaction, the mixture was cooled, and the precipitated crystals were collected by filtration, and cooled with methanol.
And water. The obtained crystals were recrystallized with acetonitrile to obtain 37.5 g of the desired product. (Yield 85%, melting point 156 ~
157 ° C) When the purity was determined by liquid chromatography,
High purity of 99.0%. Compound identification by NMR
Spectra and mass spectra were obtained to confirm that the compound was the target compound.
一般式［III］で示される他の化合物についても同様
の合成法により合成することができる。Other compounds represented by the general formula [III] can be synthesized by the same synthesis method.
［発明の効果］ 本発明によれば作業安全性に問題がなく、安価に高収
率で純度の高い含窒素６員環化合物を製造することがで
きる含窒素６員環化合物の製造方法を提供することがで
きる。[Effects of the Invention] According to the present invention, there is provided a method for producing a nitrogen-containing 6-membered ring compound which can produce a high-purity nitrogen-containing 6-membered ring compound at a low cost and with high yield without any problem in work safety. can do.
フロントページの続き (72)発明者 水倉 登 東京都日野市さくら町１番地 コニカ株 式会社内 (72)発明者 ▲高▼部 紘一 東京都日野市さくら町１番地 コニカ株 式会社内 (56)参考文献 特開 昭63−95439（ＪＰ，Ａ) 特開 昭61−60685（ＪＰ，Ａ) 特開 昭57−42679（ＪＰ，Ａ) 米国特許3834902（ＵＳ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07D 295/02 C07D 295/04 C07D 241/04 C07D 279/12 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)Continuing on the front page (72) Inventor Noboru Mizukura 1 Sakura-cho, Hino-shi, Tokyo Inside Konica Corporation (72) Inventor ▲ Taka ▼ Koichi 1-Sakuracho, Hino-shi, Tokyo Inside Konica Corporation (56) References JP-A-63-95439 (JP, A) JP-A-61-60685 (JP, A) JP-A-57-42679 (JP, A) US Patent 3,384,902 (US, A) (58) Int.Cl. 7 , DB name) C07D 295/02 C07D 295/04 C07D 241/04 C07D 279/12 CA (STN) REGISTRY (STN)
Claims (1)
［VI］で表される化合物を反応させて一般式［IV］及び
／又は一般式［Ｖ］で表される化合物を得、該一般式
［IV］及び／又は一般式［Ｖ］で表される化合物を単離
することなく一般式［II］で表される化合物を反応させ
ることを特徴とする一般式［III］で表される含窒素６
員環化合物の製造方法。 一般式［Ｉ］ 一般式［II］ R9−NH2 一般式［III］ 一般式［Ｉ］、［II］、［III］において、R1〜R8は水
素原子、アルキル基、またはアリール基を表す。Ｘは、 を表す。R9、R10はアルキル基またはアリール基を表
す。 一般式［IV］ 一般式［Ｖ］ 一般式［IV］及び［Ｖ］において、Ｒ′はアルキル基、
アリール基又はヒドロキシル基を表す。R11〜R24は水素
原子、アルキル基又はアリール基を表す。Ｘは一般式
［Ｉ］におけるＸと同義である。 一般式［VI］ Ｒ′SO2Y 一般式［VI］において、Ｙはヒドロキシル基又はハロゲ
ン原子を表す。Ｒ′は前記一般式［IV］におけるＲ′と
同義である。A compound represented by the general formula [IV] and / or a compound represented by the general formula [V] is obtained by reacting a compound represented by the general formula [I] with a compound represented by the general formula [VI]. Wherein the compound represented by the general formula [II] is reacted without isolating the compound represented by the general formula [IV] and / or the compound represented by the general formula [V]. Nitrogen-containing 6 represented
Method for producing a membered ring compound. General formula [I] General formula [II] R 9 -NH 2 General formula [III] In the general formulas [I], [II] and [III], R 1 to R 8 represent a hydrogen atom, an alkyl group or an aryl group. X is Represents R 9 and R 10 represent an alkyl group or an aryl group. General formula [IV] General formula [V] In the general formulas [IV] and [V], R ′ is an alkyl group,
Represents an aryl group or a hydroxyl group. R 11 to R 24 represent a hydrogen atom, an alkyl group or an aryl group. X has the same meaning as X in formula [I]. In the general formula [VI] R'SO 2 Y formula [VI], Y represents a hydroxyl group or a halogen atom. R 'has the same meaning as R' in formula [IV].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2131758A JP3044383B2 (en) | 1990-05-22 | 1990-05-22 | Method for producing nitrogen-containing 6-membered ring compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2131758A JP3044383B2 (en) | 1990-05-22 | 1990-05-22 | Method for producing nitrogen-containing 6-membered ring compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0426683A JPH0426683A (en) | 1992-01-29 |
| JP3044383B2 true JP3044383B2 (en) | 2000-05-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2131758A Expired - Fee Related JP3044383B2 (en) | 1990-05-22 | 1990-05-22 | Method for producing nitrogen-containing 6-membered ring compound |
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| JP (1) | JP3044383B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| AR034206A1 (en) * | 2001-02-16 | 2004-02-04 | Solvay Pharm Bv | A PROCEDURE FOR THE PREPARATION OF MESILATES OF PIPERAZINE DERIVATIVES AND SUCH MESILATES |
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1990
- 1990-05-22 JP JP2131758A patent/JP3044383B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
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| JPH0426683A (en) | 1992-01-29 |
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