JP3029731B2 - Method for producing primary chrysanthemic nitrile - Google Patents
Method for producing primary chrysanthemic nitrileInfo
- Publication number
- JP3029731B2 JP3029731B2 JP4081562A JP8156292A JP3029731B2 JP 3029731 B2 JP3029731 B2 JP 3029731B2 JP 4081562 A JP4081562 A JP 4081562A JP 8156292 A JP8156292 A JP 8156292A JP 3029731 B2 JP3029731 B2 JP 3029731B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- sulfone
- nitrile
- phenylprenyl
- solvent
- 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 - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は農薬の合成中間体として
有用な第一菊酸ニトリルの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing nitrile of primary chrysanthemum which is useful as a synthetic intermediate for agricultural chemicals.
【0002】[0002]
【従来の技術】第一菊酸ニトリルは加水分解することに
よって重要な農薬原料である第一菊酸へと導くことがで
きる。2. Description of the Prior Art Nitriles of primary chrysanthemum can be converted into primary chrysanthemic acid, which is an important raw material for agricultural chemicals, by hydrolysis.
【0003】フェニルプレニルスルホンとセネシオニト
リルを原料とする第一菊酸ニトリルの合成反応はすでに
知られている。例えば、Eesti NSV Tea
d.Akad.Toim.,Keem.,38(4),
238−41には、DMSO中、ナトリウムメトキシ
ド、もしくは水酸化カリウムの存在下にフェニルプレニ
ルスルホンとセネシオニトリルを1対3で反応させる方
法が報告されている。しかし、この方法による反応収率
は高々50%でしかない。また、この方法では過剰のセ
ネシオニトリルを必要とするが、セネシオニトリルは重
合しやすい性質を持っているため過剰に使うことは経済
的に不利である。[0003] A synthesis reaction of nitrile primary chrysanthemum using phenylprenyl sulfone and senecionitrile as raw materials is already known. For example, Esti NSV Tea
d. Akad. Toim. , Keem. , 38 (4),
238-41 reports a method of reacting phenylprenyl sulfone with sensionitrile in a ratio of 1: 3 in the presence of sodium methoxide or potassium hydroxide in DMSO. However, the reaction yield of this method is at most 50%. Further, this method requires an excessive amount of senecionitrile, but since senecionitrile has a property of being easily polymerized, it is economically disadvantageous to use it excessively.
【0004】その他、特公昭43−2344号公報に記
載されているように、塩基性物質存在下でフェニルプレ
ニルスルホンとセネシオニトリルを反応せしめ、第一菊
酸ニトリルを得る方法が知られている。しかし、この反
応の場合、金属アルコキシド、金属アミドなどの高価な
塩基性物質を使用しており、それをフェニルプレニルス
ルホンと当モル量用いる必要があることから、経済面で
問題がある。[0004] Other, as described in JP-B-43-2344, in the presence of a basic substance by reacting the phenyl prenyl sulfone and Seneshionitoriru, resulting Ru methods are known first chrysanthemic acid nitrile . However, in the case of this reaction, expensive basic substances such as metal alkoxides and metal amides are used, and it is necessary to use them in equimolar amounts with phenylprenyl sulfone, which is economically problematic.
【0005】[0005]
【発明が解決しようとする課題】本発明の目的は、フェ
ニルプレニルスルホンとセネシオニトリルを原料とする
第一菊酸ニトリルの合成方法について、従来にない経済
性と高収率を与える方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for synthesizing nitric acid nitrite using phenylprenyl sulfone and senecionitrile as raw materials, which provides unprecedented economical efficiency and high yield. It is in.
【0006】[0006]
【課題を解決するための手段】本発明者らはかかる課題
を解決するために種々の検討を行なった結果、下記式Means for Solving the Problems The present inventors have conducted various studies in order to solve the above problems, and as a result, the following formula has been obtained.
【0007】[0007]
【化4】 で示されるフェニルプレニルスルホンと下記式Embedded image A phenylprenyl sulfone represented by the following formula
【0008】[0008]
【化5】 で示されるセネシオニトリルを塩基性物質の存在下に極
性溶媒と共沸脱水用溶媒の混合溶液中で反応させること
により、下記式Embedded image By reacting in a mixed solution of a polar solvent and a solvent for azeotropic dehydration in the presence of a basic substance,
【0009】[0009]
【化6】 で示される第一菊酸ニトリルが高収率で得られることを
見出し、本発明に到達した。Embedded image The present inventors have found that the first nitric acid nitrile represented by the formula (1) can be obtained in high yield, and have reached the present invention.
【0010】本発明者において反応に使用される塩基性
物質の具体例は、水酸化ナトリウム、水酸化カリウムな
どのアルカリ金属もしくはアルカリ土類金属の水酸化物
などである。Specific examples of the basic substance used in the reaction in the [0010] present inventors, sodium hydroxide, alkali metal or alkaline earth hydroxide of a metal, such as potassium hydroxide
Do etc. it is.
【0011】反応に用いうる極性溶媒としては、DMS
O、DMF、THFなどであり、また共沸脱水用溶媒と
しては、トルエンなどの芳香族炭化水素、ヘキサン、シ
クロヘキサンなどの飽和炭化水素、ジイソブチレンのご
とき不飽和炭化水素、イソプロピルエーテルなどのエー
テル類を用いることができる。[0011] As the polar solvent usable in the reaction, DMS
O, DMF, THF, etc., and azeotropic dehydration solvents include aromatic hydrocarbons such as toluene, saturated hydrocarbons such as hexane and cyclohexane, unsaturated hydrocarbons such as diisobutylene, and ethers such as isopropyl ether. Can be used.
【0012】原料となるフェニルプレニルスルホンはプ
レニルクロライドとベンゼンスルフィン酸ナトリウムか
ら合成することができ、第一菊酸ニトリルの合成反応に
はその反応液をそのまま使用することもできる。The raw material phenylprenyl sulfone can be synthesized from prenyl chloride and sodium benzenesulfinate, and the reaction solution can be used as it is in the synthesis reaction of nitrile primary chrysanthemum.
【0013】また、もう一方の原料であるセネシオニト
リルはメタリルクロライドと青酸ナトリウムから合成す
ることができる。[0013] Senecionitrile, another raw material, can be synthesized from methallyl chloride and sodium cyanate.
【0014】より高収率で第一菊酸ニトリルを得るため
には、これらの原料を再結晶、蒸留などにより精製して
用いることが好ましい。In order to obtain nitrile primary chrysanthemum in a higher yield, it is preferable to use these raw materials after purification by recrystallization, distillation or the like.
【0015】当該反応は、30℃から100℃の温度範
囲で行うことができるが、50℃から90℃の範囲で行
うことがより好ましい。塩基性物質の好ましい使用量は
フェニルプレニルスルホン1mol に対して1〜3mol で
あり、セネシオニトリルは経済性の面からフェニルプレ
ニルスルホン1mol に対して1〜2mol 使用することが
好ましい。反応溶媒となる極性溶媒はフェニルプレニル
スルホンを溶解できる量であれば十分であり、すなわち
フェニルプレニルスルホンの0.5倍重量から2倍重量
あればよい。共沸脱水用溶媒は系内から水を共沸脱水で
きる量であれば十分であり、すなわち極性溶媒の0.5
倍重量から10倍重量である。[0015] The reaction can be carried out at a temperature in the range of 30 ° C to 100 ° C, more preferably in the range of 50 ° C to 90 ° C. The preferred amount of the basic substance used is 1 to 3 mol per 1 mol of phenylprenyl sulfone, and it is preferable to use 1 to 2 mol of senecionitrile per 1 mol of phenylprenyl sulfone from the viewpoint of economy. The polar solvent used as the reaction solvent is sufficient as long as it can dissolve phenylprenyl sulfone, that is, 0.5 to 2 times the weight of phenylprenyl sulfone. The solvent for azeotropic dehydration is sufficient as long as water can be azeotropically dehydrated from the system.
It is double weight to 10 times weight.
【0016】反応は、フェニルプレニルスルホンと極性
溶媒、共沸脱水用溶媒、塩基性物質を仕込み、加温した
ところにセネシオニトリルを添加することによって行
う。その時、系内から生成する水を共沸脱水用溶媒によ
って除くことによって反応は進行する。フェニルプレニ
ルスルホンの消失によって反応は終了する。The reaction is carried out by charging phenylprenyl sulfone, a polar solvent, a solvent for azeotropic dehydration, and a basic substance, and adding sensionitrile to a heated place. At that time, the reaction proceeds by removing water generated from the system by the azeotropic dehydration solvent. The reaction is terminated by the disappearance of phenylprenyl sulfone.
【0017】生成した第一菊酸ニトリルは蒸留によって
分離精製される。The produced nitric acid nitrite is separated and purified by distillation.
【0018】[0018]
【実施例】以下に実施例を挙げて、本発明をさらに具体
的に説明するが、本発明はこの実施例に限定されるもの
ではない。 実施例1 内容積300mlの3口フラスコに分留管、温度計、滴下
ロートを装着した後、50%苛性ソーダ水51.02
g、トルエン120.5g、DMSO80g、フェニル
プレニルスルホン89.3gを取り、減圧下還流する。
減圧度120mmHg、71℃でセネシオニトリル44.7
7gを5時間で滴下した。22時間反応を行った後、ト
ルエンによって水29gを系内より脱水した。反応系を
硫酸により中和し析出した固体をろ過し、エバポレート
して溶媒留去した後減圧蒸留することによって第一菊酸
ニトリル44.96gを得た。反応成績は以下のとおり
であった。 EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. Example 1 A three-necked flask having an inner volume of 300 ml was equipped with a fractionating tube, a thermometer, and a dropping funnel, and then 50% caustic soda water 51.02.
g, 120.5 g of toluene, 80 g of DMSO, and 89.3 g of phenylprenylsulfone, and refluxed under reduced pressure.
Senecionitrile 44.7 at a reduced pressure of 120 mmHg and 71 ° C.
7 g were added dropwise in 5 hours. After performing the reaction for 22 hours, 29 g of water was dehydrated from the system with toluene. The reaction system was neutralized with sulfuric acid, and the precipitated solid was filtered, evaporated, and the solvent was distilled off. The residue was distilled under reduced pressure to obtain 44.96 g of nitrile. The reaction results are as follows
Met.
【0019】 フェニルプレニルスルホン 転化率100% 第一菊酸ニトリル 選択率72.53% 実施例2 極性溶媒をDMFに代え、かつ反応時間を25時間とし
たこと以外は実施例1と同様の反応を行った。反応成績
は以下のとおりであった。 Phenylprenyl sulfone 100% conversion nitrile nitrous acid selectivity 72.53% Example 2 The polar solvent was changed to DMF and the reaction time was 25 hours.
Was except that reaction was carried out in the same manner as in Example 1. Reaction performance
Was as follows.
【0020】 フェニルプレニルスルホン 転化率100% 第一菊酸ニトリル 選択率 70.11% 実施例3 共沸脱水用溶媒をヘキサンに代え、かつ反応時間を32
時間としたこと以外は実施例1と同様の反応を行った。
反応成績は以下のとおりであった。 [0020] Instead of full E sulfonyl prenyl sulfone 100% conversion first chrysanthemic acid nitrile selectivity of 70.11 percent Example 3 azeotropic dehydration solvent in hexane, and the reaction time 32
The same reaction as in Example 1 was performed except that the time was changed.
The reaction results were as follows.
【0021】 フェニルプレニルスルホン 転化率100% 第一菊酸ニトリル 選択率 67.51% 実施例4 塩基性物質を水酸化カリウムに代える以外は実施例1と
同様の反応を行った。反応成績は以下のとおりであっ
た。 [0021] except for replacing the full E sulfonyl prenyl sulfone 100% conversion first chrysanthemic acid nitrile selectivity of 67.51% Example 4 basic substance potassium hydroxide was subjected to the same reaction as in Example 1. The reaction results were as follows:
Was.
【0022】 フェニルプレニルスルホン 転化率100% 第一菊酸ニトリル 選択率 65.10%The full E sulfonyl prenyl sulfone 100% conversion first chrysanthemic acid nitrile selectivity 65.10%
【0023】[0023]
【発明の効果】本発明によれば、フェニルプレニルスル
ホンとセネシオニトリルを塩基性物質の存在下に極性溶
媒と共沸脱水用溶媒の混合溶液中で反応させることによ
り、農薬の合成中間体として有用な第一菊酸ニトリルを
高収率で製造することができる。According to the present invention, phenylprenyl sulfone and senecionitrile are reacted in a mixed solution of a polar solvent and an azeotropic dehydration solvent in the presence of a basic substance to be useful as an intermediate for the synthesis of pesticides. The first nitric acid nitrile can be produced in a high yield.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭57−2238(JP,A) 特開 昭56−39042(JP,A) 特公 昭43−2344(JP,B1) (58)調査した分野(Int.Cl.7,DB名) C07C 255/48 C07C 255/45 C07C 253/30 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-57-2238 (JP, A) JP-A-56-39042 (JP, A) JP-B-43-2344 (JP, B1) (58) Field (Int.Cl. 7 , DB name) C07C 255/48 C07C 255/45 C07C 253/30
Claims (1)
性溶媒と共沸脱水用溶媒の混合溶液中で反応させること
を特徴とする下記式(III) 【化3】 で示される第一菊酸ニトリルの製造方法。1. A compound represented by the following formula (I): And a phenylprenyl sulfone represented by the following formula (II): Wherein Senecionitrile represented by the following formula is reacted in a mixed solution of a polar solvent and a solvent for azeotropic dehydration in the presence of a basic substance: The method for producing a primary chrysanthemic acid nitrile represented by the formula:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4081562A JP3029731B2 (en) | 1992-03-03 | 1992-03-03 | Method for producing primary chrysanthemic nitrile |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4081562A JP3029731B2 (en) | 1992-03-03 | 1992-03-03 | Method for producing primary chrysanthemic nitrile |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05246972A JPH05246972A (en) | 1993-09-24 |
JP3029731B2 true JP3029731B2 (en) | 2000-04-04 |
Family
ID=13749736
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4081562A Expired - Fee Related JP3029731B2 (en) | 1992-03-03 | 1992-03-03 | Method for producing primary chrysanthemic nitrile |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3029731B2 (en) |
-
1992
- 1992-03-03 JP JP4081562A patent/JP3029731B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH05246972A (en) | 1993-09-24 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
LAPS | Cancellation because of no payment of annual fees |