JPH0552307B2 - - Google Patents
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- Publication number
- JPH0552307B2 JPH0552307B2 JP27589185A JP27589185A JPH0552307B2 JP H0552307 B2 JPH0552307 B2 JP H0552307B2 JP 27589185 A JP27589185 A JP 27589185A JP 27589185 A JP27589185 A JP 27589185A JP H0552307 B2 JPH0552307 B2 JP H0552307B2
- Authority
- JP
- Japan
- Prior art keywords
- pyridyl
- pimelic acid
- pimelic
- hydrochloride
- acid hydrochloride
- 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.)
- Expired - Lifetime
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- Pyridine Compounds (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は４−（４−ピリジル）ピメリン酸塩酸
塩及びその製造法に関するものであり、４−（４
−ピリジル）ピメリン酸塩酸塩は農医薬の中間体
として、さらにポリマーの原料として有用であ
る。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to 4-(4-pyridyl)pimelic acid hydrochloride and a method for producing the same.
-pyridyl) pimelic acid hydrochloride is useful as an intermediate for agricultural chemicals and as a raw material for polymers.
従来技術
４位に置置換を有するピメリン酸誘導体として
は、例えば４−フエニルピメリン酸が知られてい
るが（R.H.Manske、J.A.C.S、1931、53、
1104）、４位にピリジル基を持つピメリン酸は全
く知られていない。Prior Art As a pimelic acid derivative having a substitution at the 4-position, for example, 4-phenylpimelic acid is known (RHManske, JACS, 1931, 53 ,
1104), pimelic acid with a pyridyl group at the 4-position is completely unknown.
発明が解決しようとする問題点
上記の従来技術によつて、４−（４−ピリジル）
ピメリン酸塩酸塩を製造しようとすると、ピリジ
ルマロン酸から出発して少なくとも８工程が必要
と思われる。然し、本発明では、はるかに短い工
程で新規４−（４−ピリジル）ピメリン酸塩酸塩
を製造することができる。Problems to be Solved by the Invention The above-mentioned prior art solves the problem of 4-(4-pyridyl)
It appears that at least eight steps are required to produce pimelic hydrochloride starting from pyridylmalonic acid. However, in the present invention, the new 4-(4-pyridyl)pimelic acid hydrochloride can be produced in a much shorter process.
問題点を解決するための手段
本発明者は、農医薬の中間体として、さらにポ
リマーの原料として有用な新規４−（４−ピリジ
ル）ピメリン酸塩酸塩の製造法について鋭意検討
を行つた結果ピリジルアセトニトリルにアクリル
酸をマイケル付加させた生成物を塩酸中で加水分
解と脱炭酸を同時に行わせる事によつて４−（４
−ピリジル）ピメリン酸塩酸塩を容易に製造出来
る方法を見出し本発明に到達した。Means for Solving the Problems The present inventor has conducted intensive studies on a method for producing a novel 4-(4-pyridyl)pimelic acid hydrochloride, which is useful as an intermediate for agricultural chemicals and as a raw material for polymers. 4-(4
-Pyridyl)pimelic acid hydrochloride was discovered and the present invention was achieved.
本発明の方法についてさらに詳しく述べると、
本発明の製造法は次に示す反応経路によつて実施
される。 To describe the method of the present invention in more detail,
The production method of the present invention is carried out by the reaction route shown below.
上記の反応経路におけるＲは前記と同じ置換基
を意味する。 R in the above reaction route means the same substituent as above.
（）とアクリル酸エステルとの反応は、有機
溶媒中または無溶媒ににおいて触媒として１，８
−ジアザビシクロ（5.4.0）−７−ウンデセン等の
塩基を用いて、室温〜50℃において反応させるこ
とにより、一般式（）の化合物を製造すること
ができる。 The reaction between () and acrylic ester is carried out in an organic solvent or in the absence of a solvent using a catalyst of 1,8
-Diazabicyclo(5.4.0)-7-Undecene or other base is used to react at room temperature to 50°C, thereby producing a compound of general formula ().
本発明化合物の（）は、（）を塩酸中で加
熱することにより、シアノ基の加水分解と脱炭酸
さらにはエステル基Ｒの加水分解を同時に行い製
造することができる。 The compound () of the present invention can be produced by heating () in hydrochloric acid to simultaneously perform hydrolysis of the cyano group, decarboxylation, and hydrolysis of the ester group R.
発明の効果
本発明により、農医薬中間体として有用であ
り、さらにピリジル基を含むポリマーの原料とし
て有用な新規４−（４−ピリジル）ピメリン酸塩
酸塩を製造できる。Effects of the Invention According to the present invention, it is possible to produce a novel 4-(4-pyridyl)pimelic acid hydrochloride that is useful as an agricultural and pharmaceutical intermediate and further useful as a raw material for a polymer containing a pyridyl group.
以下に実施例を示し、本発明をさらに詳細に説
明する。 EXAMPLES The present invention will be explained in further detail by way of Examples below.
実施例 １
４−（４−ピリジル）ピメリン酸塩酸塩
() ４−シアノ−４−（４−ピリジル）ピメリ
ン酸メチルエステル
アクリル酸メチル10.4ｇに、１，８−ジアザ
ビシクロ（5.4.0）−７−ウンデセン0.2ｇを加
え、水冷下撹拌しながら20〜40℃に保ち、４−
ピリジルアセトニトリル14.2ｇをアクリル酸メ
チル20.8ｇに溶解して加えた。Example 1 4-(4-pyridyl)pimelic acid hydrochloride () 4-cyano-4-(4-pyridyl)pimelic acid methyl ester To 10.4 g of methyl acrylate, 1,8-diazabicyclo(5.4.0)-7 -Add 0.2g of undecene, keep at 20~40℃ while stirring under water cooling, 4-
14.2 g of pyridylacetonitrile was dissolved in 20.8 g of methyl acrylate and added.
30分後、水浴を外しさらに室温で１時間撹拌
した。過剰のアクリル酸メチルを減圧留去した
のちシリカゲルカラムで精製して、４−シアノ
−４−（４−ピリジル）ピメリン酸メチルエス
テル35ｇを油状物として得た。 After 30 minutes, the water bath was removed and the mixture was further stirred at room temperature for 1 hour. After removing excess methyl acrylate under reduced pressure, the residue was purified using a silica gel column to obtain 35 g of 4-cyano-4-(4-pyridyl)pimelic acid methyl ester as an oil.
IR（Neat）：2950、2230、1760、1590、1430、
1200cm-1
NMR（100MHz、CCl4）；8.6δ（2H、ｍ）、7.4δ
（2H、ｍ）、3.58δ（6H、ｓ）、1.9〜2.7δ（8H、
ｍ）。 IR (Neat): 2950, 2230, 1760, 1590, 1430,
1200cm -1 NMR (100MHz, CCl 4 ); 8.6δ (2H, m), 7.4δ
(2H, m), 3.58δ (6H, s), 1.9~2.7δ (8H,
m).
(2) ４−（４−ピリジル）ピメリン酸塩酸塩
４−（４−ピリジル）ピメリン酸塩酸塩メチ
ルエステル13ｇを濃塩酸250mlに溶解し、14時
間加熱還流した。(2) 4-(4-pyridyl)pimelic acid hydrochloride 13 g of 4-(4-pyridyl) pimelic acid hydrochloride methyl ester was dissolved in 250 ml of concentrated hydrochloric acid and heated under reflux for 14 hours.
減圧下に濃塩酸を留去したのちシリカルカラ
ム及びエーテルで精製してmp174〜177℃の４
−（４−ピリジル）ピメリン酸塩酸塩を7.4ｇを
得た。 After distilling off concentrated hydrochloric acid under reduced pressure, it was purified using a silica column and ether, and then purified at mp174-177℃.
7.4 g of -(4-pyridyl)pimelic acid hydrochloride was obtained.
IR（KBr）：3600〜2400（巾広い吸収）、1720、
1630、1590、1230cm-1：
NMR（100MHz、D2O） 1.8〜2.5δ（ｍ、8H）、
3.0〜3.3δ（ｍ、1H）、
8.0〜8.2δ（ｍ、2H）、
8.7〜8.9δ（ｍ、2H）
実施例 ２
実施例１−(1)におけるアクリル酸メチルの代わ
りにアクリル酸エチルを用いて製造した４−シア
ノ−４−（４−ピリジル）ピメリン酸エチルエス
テル14ｇを濃塩酸250mlに溶解し、16時間加熱還
流した。 IR (KBr): 3600~2400 (wide absorption), 1720,
1630, 1590, 1230cm -1 : NMR (100MHz, D2O ) 1.8-2.5δ (m, 8H), 3.0-3.3δ (m, 1H), 8.0-8.2δ (m, 2H), 8.7-8.9δ (m, 2H) Example 2 14 g of 4-cyano-4-(4-pyridyl)pimelic acid ethyl ester produced using ethyl acrylate instead of methyl acrylate in Example 1-(1) was mixed with 250 ml of concentrated hydrochloric acid. and heated under reflux for 16 hours.
つぎに減圧下で塩酸を留去し、残渣をエーテル
で精製して、４−（４−ピリジル）ピメリン酸塩
酸塩を6.1ｇ得た。 Next, hydrochloric acid was distilled off under reduced pressure, and the residue was purified with ether to obtain 6.1 g of 4-(4-pyridyl)pimelic acid hydrochloride.
得られた化合物の融点、IR及びNMRの値は実
施例１−(2)で得たものと完全に一致した。 The melting point, IR and NMR values of the obtained compound were completely consistent with those obtained in Example 1-(2).
Claims (1)
される４−シアノ−４−（４−ピリジル）ピメリ
ン酸エステルを塩酸中で処理することによつて４
−（４−ピリジル）ピメリン酸塩酸塩を製造する
方法。[Claims] 1 4-(4-pyridyl)pimelic hydrochloride. 2 General formula () (wherein R represents a methyl or ethyl group) by treating 4-cyano-4-(4-pyridyl)pimelic acid ester in hydrochloric acid.
- A method for producing (4-pyridyl)pimelic acid hydrochloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27589185A JPS62135456A (en) | 1985-12-10 | 1985-12-10 | 4-(4-pyridyl)pimelic acid hydrochloride and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27589185A JPS62135456A (en) | 1985-12-10 | 1985-12-10 | 4-(4-pyridyl)pimelic acid hydrochloride and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62135456A JPS62135456A (en) | 1987-06-18 |
| JPH0552307B2 true JPH0552307B2 (en) | 1993-08-05 |
Family
ID=17561876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27589185A Granted JPS62135456A (en) | 1985-12-10 | 1985-12-10 | 4-(4-pyridyl)pimelic acid hydrochloride and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62135456A (en) |
-
1985
- 1985-12-10 JP JP27589185A patent/JPS62135456A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62135456A (en) | 1987-06-18 |
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