JP4116103B2 - Method for producing pentamethine compound and quaternary salt compound - Google Patents
Method for producing pentamethine compound and quaternary salt compound Download PDFInfo
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- JP4116103B2 JP4116103B2 JP10626495A JP10626495A JP4116103B2 JP 4116103 B2 JP4116103 B2 JP 4116103B2 JP 10626495 A JP10626495 A JP 10626495A JP 10626495 A JP10626495 A JP 10626495A JP 4116103 B2 JP4116103 B2 JP 4116103B2
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
- C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >CH- groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Description
【0001】
【産業上の利用分野】
本発明は、写真用色素中間体として有用な素材である3−メチル−2,4−ペンタジエニリデン誘導体を安価で且つ高収率で製造する方法を提供するものである。
【0002】
【従来技術】
3−メチル−2,4−ペンタジエニリデン誘導体の合成法には、J.Chem.Soc.,960(1947)に記載されるBrCNを使用する方法、Zh.Org.Khim.,702(1986)に記載されるSi化合物を経由する方法、J.Org.Chem.USSR,1 640(1965)に記載されているジヒドロピランより合成する方法等があり、又更にLieb.Annal.Chem.,333,296(1904)に記載されている2,4−ペンタジエニリデン誘導体の合成による方法がある。これらの方法は、毒性の強いBrCNを使用したり、高価なSi化合物や特殊な原料を使用しなければならないことに加えて、収率が30%前後と低いこと等、3−位にメチル基を有するペンタメチン色素の合成条件として慣用するための工業的製造方法としては安全性及び経済性の面で多くの問題を含んでいるのが現状である。
【0003】
【発明が解決しようとする課題】
従って、本発明の目的は、従来の方法における製造適性および経済性に関する上記の問題点を排除し、簡便にして高収率な3−メチル−2,4−ペンタジエニリデン誘導体の製造方法を提供することにある。
【0004】
【課題を解決するための手段】
上記目的は、下記構成により達成された。
2,4−ジニトロクロロベンゼンを、pKa25℃ =2.5〜5.0のカルボン酸の存在下で4−ピコリンと反応させることを特徴とする下記式〔1〕で表される4級塩の製造方法。
【0005】
【化4】
【0011】
本発明の態様を更に詳しく説明する。本発明の要点は、カルボン酸共存下における4−ピコリンの4級化であり、また、σ値を規定したアニリンによる3−メチル−2,4−ペンタジエニリデン誘導体の合成方法である。この3−メチル−2,4−ペンタジエニリデン誘導体と類似構造を持つ2,4−ペンタジエニリデン誘導体の合成法は公知であり、例えば、Lieb.Annal.Chem.,333,296(1904)およびJ.Chem.Soc.,189(1933)等に記載されているような反応系で目的物を高収率で得ることができる。しかし、2,4−ジニトロベンゼンとの反応による4−ピコリンの4級化においては、上記の反応系を用いても低収率で、使用できるものではなかった。これは生成する4級塩のメチル基が活性となり、副反応生成物が生じるためである。副反応生成物は質量分析測定により、4級塩と2,4−ジニトロクロロベンゼンとが反応した下記式〔4〕の構造であると推測している。この副反応生成物は塩基を添加して反応することにより、増加することが確認された。
【0012】
【化7】
【0013】
上記の結果から、反応系の塩基性を低下させることにより、この副反応を抑制できるものと推測した。そこで、この反応時に酸を共存させたところ、定量的に目的物を得ることができることを見出した。共存させる酸の種類としては、25℃の水中で2.5〜5.0のpKa値を示すカルボン酸である。このようなカルボン酸としては、蟻酸、酢酸、プロピオン酸、酪酸、吉草酸、シュウ酸、マロン酸、コハク酸、安息香酸、モノクロル酢酸、ピバリン酸等の有機酸が好ましい。カルボン酸の使用量は、2,4−ジニトロクロロベンゼンに対して0.5〜2.0倍モルが好ましい。また本合成法における反応は室温(例えば20℃)でも進行するが、より高温、例えば例示の溶媒の沸点のほうが迅速に進行する。
【0014】
また上記4級化の反応は、溶媒を添加して行うことができる。その溶媒としては、酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル類、ノルマル−ヘキサン等が挙げられる。
【0015】
この上記式〔1〕で表される4級塩を下記一般式〔2〕で表されるアニリン又はその誘導体と反応させた結果、高収率で3−メチル−2,4−ペンタジエニリデン誘導体を合成することが可能となった。この反応は溶媒を添加して行うことができる。その溶媒としては、メタノール、エタノール、イソプロピルアルコール等のアルコール類、酢酸エチル、酢酸ブチル等のエステル類、アセトン、メチルエチルケトン等のケトン類、トルエン、キシレン等の芳香族炭化水素、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド等の非プロトン性極性溶媒、アセトニトリル等が挙げられる。なお、アニリンの使用量は、4級塩に対して2.0〜2.8倍モルが好ましい。また本合成法における反応温度は0〜50℃が好ましい。本発明の式〔1〕で表される4級塩化合物でメチル基をエチル基他の低級アルキル基(炭素数1〜4の直鎖及び分岐鎖を含む)とした同族体も同様に製造できる。これらの同族体を用いて、下記一般式〔3〕のメチル基が対応する低級アルキル基であるペンタメチン化合物を製造することができる。
【化5】
(式中、Rはハメット則のσ値が0を越えないメタ又はパラ位の置換基を表わす。)
上記式中のRとしては、具体的には、ハメット則のσ値が0〜−0.4の範囲にある水素原子、メチル、エチル、プロピル等のアルキル基、メトキシ、エトキシ等のアルコキシ基等を表す。Rとして特に好ましくは水素原子、メチル基、メトキシ基である。
【0016】
【発明の効果】
本発明により、写真用色素中間体として重要な3−メチル−2,4−ペンタジエニリデン誘導体を、毒性のある試薬を使用せずとも、安価且つ安定に供給することが可能となった。
【0017】
【実施例】
以下、本発明を更に詳しく説明するために実施例を示すが、これは本発明を限定するものではない。
実施例1 1−(2,4−ジニトロフェニル)−4−メチルピリジニウムクロライド(化合物No.1)の合成
2,4−ジニトロクロロベンゼン405.1gと酢酸145.6gを酢酸エチル1200mlに溶解し、この溶液に4─ピコリン223.6gを室温にて添加し、80℃で4時間反応させた。反応後、20℃まで冷却して生成した結晶を濾過、酢酸エチル100mlで洗浄し、化合物No.1を585.5g(収率99%)得た。融点は161〜163℃であった。
【0018】
参考例1 ベンゼンアミン,N−〔3−メチル−5−(フェニルアミノ)−2,4−ペンタジエニリデン〕−ハイドロクロライド(化合物No.2)の合成
実施例1で合成した化合物No.1を88.7g、アニリン67.1g、イソプロピルアルコール900mlを混合し、攪拌下20〜25℃で6時間反応させた。反応終了後、生成した結晶を濾過、アセトン300mlで洗浄し、化合物No.2を53.8g(収率60%)得た。融点は、146〜147℃であった。
【0019】
参考例2 ベンゼンアミン,4−メトキシ−N−〔3−メチル−5−(4−メトキシフェニルアミノ)−2,4−ペンタジエニリデン〕−ハイドロクロライド(化合物No.3)の合成
実施例1で合成した化合物No.1を5.91g、p−アニシジン5.92g、イソプロピルアルコール60mlを混合し、攪拌下20〜25℃で6時間反応させた。反応混合物を実施例2と同様に処理して化合物No.3を5.30g(収率74%)得た。融点は、149〜150℃であった。
【0020】
以下、化合物No.1の合成について比較例を挙げる。
比較例1 1−(2,4−ジニトロフェニル)−4−メチルピリジニウムクロライド(化合物No.1)の合成
2,4−ジニトロクロロベンゼン10.1g、酢酸エチル130ml溶液に、4─ピコリン5.6gを室温にて添加し、80℃で4時間反応させた。反応生成物中に副生成物が多く、目的物は結晶として単離できなかった。なお、この副生成物のTLC−MSスペクトルの測定値はm/z 426(M+ )であった。
【0021】
参考比較例1 1−(2,4−ジニトロフェニル)−4−メチルピリジニウムクロライド(化合物No.1)の合成
2,4−ジニトロクロロベンゼン10.1gの酢酸エチル30ml溶液に、4─ピコリン5.6gを添加し、20℃で12時間反応させた。反応生成物を濾過、酢酸エチルで洗浄し、化合物No.1を3.4g(収率23%)得た。
【0022】
上記に示すように、本発明の実施例1〜3では、3−メチル−2,4−ペンタジエニリデン誘導体を高収率で得られるのに対して、カルボン酸を用いない比較例1、2では、副生成物が多くて単離できなかったり、収率が低くなってしまった。[0001]
[Industrial application fields]
The present invention provides a method for producing a 3-methyl-2,4-pentadienylidene derivative, which is a material useful as a photographic dye intermediate, at low cost and in high yield.
[0002]
[Prior art]
As a method for synthesizing 3-methyl-2,4-pentadienylidene derivatives, J. et al. Chem. Soc. , 960 (1947), the method using BrCN, Zh. Org. Khim. , 702 (1986). Org. Chem. USSR, 1 640 (1965), and a method of synthesizing from dihydropyran. Anal. Chem. , 333 , 296 (1904), there is a method by synthesis of 2,4-pentadienylidene derivatives. These methods require the use of highly toxic BrCN, the use of expensive Si compounds and special raw materials, as well as the low yield of around 30%. As an industrial production method for commonly used as a synthesis condition for a pentamethine dye having a colorant, there are many problems in terms of safety and economy.
[0003]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to eliminate the above-mentioned problems relating to production suitability and economy in the conventional method, and to provide a simple and high-yield method for producing a 3-methyl-2,4-pentadienylidene derivative. It is to provide.
[0004]
[Means for Solving the Problems]
The above object has been achieved by the following constitution.
2,4-dinitrochlorobenzene is reacted with 4-picoline in the presence of a carboxylic acid having a pKa 25 ° C. of 2.5 to 5.0, which is a quaternary salt represented by the following formula [1] Manufacturing method .
[0005]
[Formula 4]
[0011]
The embodiment of the present invention will be described in more detail. The main point of the present invention is the quaternization of 4-picoline in the presence of a carboxylic acid, and a method for synthesizing a 3-methyl-2,4-pentadienylidene derivative with aniline having a defined σ value. A method for synthesizing a 2,4-pentadienylidene derivative having a structure similar to that of this 3-methyl-2,4-pentadienylidene derivative is known, for example, see Lieb. Anal. Chem. , 333, 296 (1904) and J.A. Chem. Soc. , 189 (1933), etc., the target product can be obtained in high yield. However, in the quaternization of 4-picoline by reaction with 2,4-dinitrobenzene, even if the above reaction system is used, it cannot be used in a low yield. This is because the methyl group of the quaternary salt to be produced becomes active and a side reaction product is generated. The side reaction product is presumed to have a structure of the following formula [4] in which a quaternary salt and 2,4-dinitrochlorobenzene have reacted by mass spectrometry. This side reaction product was confirmed to increase by adding a base to react.
[0012]
[Chemical 7]
[0013]
From the above results, it was estimated that this side reaction can be suppressed by reducing the basicity of the reaction system. Thus, it was found that the target product can be obtained quantitatively when an acid is allowed to coexist during this reaction. The acid to be coexisted is a carboxylic acid having a pKa value of 2.5 to 5.0 in water at 25 ° C. As such carboxylic acid, organic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, benzoic acid, monochloroacetic acid, and pivalic acid are preferable. The amount of the carboxylic acid used is preferably 0.5 to 2.0 times the mole of 2,4-dinitrochlorobenzene. The reaction in this synthesis method proceeds even at room temperature (for example, 20 ° C.), but proceeds more rapidly at a higher temperature, for example, the boiling point of the exemplified solvent.
[0014]
The quaternization reaction can be performed by adding a solvent. Examples of the solvent include esters such as ethyl acetate, propyl acetate, and butyl acetate, and normal-hexane.
[0015]
The above formula (1) the result of the quaternary salt was reacted with aniline or its derivative represented by the following general formula [2] represented, in high yield 3-methyl-2,4 Pentajieni It has become possible to synthesize redene derivatives. This reaction can be performed by adding a solvent. Solvents include alcohols such as methanol, ethanol and isopropyl alcohol, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as toluene and xylene, N, N-dimethylformamide And aprotic polar solvents such as N, N-dimethylacetamide, acetonitrile and the like. The amount of aniline used is preferably 2.0 to 2.8 moles compared to the quaternary salt. The reaction temperature in this synthesis method is preferably 0 to 50 ° C. The quaternary salt compound represented by the formula [1] of the present invention can be produced in the same manner as a homologue in which the methyl group is an ethyl group or other lower alkyl group (including linear and branched chains having 1 to 4 carbon atoms). . Using these congeners, a methyl group of the following general formula [3] can be produced pentamethine compound is a lower alkyl group corresponding.
[Chemical formula 5]
(In the formula, R represents a meta or para substituent whose σ value of Hammett's rule does not exceed 0.)
Specific examples of R in the above formula include a hydrogen atom having a Hammett's rule σ value in the range of 0 to −0.4, an alkyl group such as methyl, ethyl, and propyl, and an alkoxy group such as methoxy and ethoxy. Represents. R is particularly preferably a hydrogen atom, a methyl group, or a methoxy group.
[0016]
【The invention's effect】
According to the present invention, 3-methyl-2,4-pentadienylidene derivatives important as photographic dye intermediates can be supplied inexpensively and stably without using toxic reagents.
[0017]
【Example】
Hereinafter, examples will be shown to describe the present invention in more detail, but this does not limit the present invention.
Example 1 Synthesis of 1- (2,4-dinitrophenyl) -4-methylpyridinium chloride (Compound No. 1) 405.1 g of 2,4-dinitrochlorobenzene and 145.6 g of acetic acid were dissolved in 1200 ml of ethyl acetate. To the solution, 223.6 g of 4-picoline was added at room temperature and reacted at 80 ° C. for 4 hours. After the reaction, the crystals formed upon cooling to 20 ° C. were filtered and washed with 100 ml of ethyl acetate. 1 was obtained in an amount of 585.5 g (99% yield). The melting point was 161-163 ° C.
[0018]
Reference Example 1 Synthesis of Benzeneamine, N- [3-Methyl-5- (phenylamino) -2,4-pentadienylidene] -hydrochloride (Compound No. 2) Compound No. 1 synthesized in Example 1 18.7 was mixed with 68.7 g of aniline and 900 ml of isopropyl alcohol, and reacted at 20-25 ° C. for 6 hours with stirring. After completion of the reaction, the produced crystals were filtered and washed with 300 ml of acetone. 23.8g (yield 60%) of 2 was obtained. The melting point was 146-147 ° C.
[0019]
Reference Example 2 Synthesis of benzenamine, 4-methoxy-N- [3-methyl-5- (4-methoxyphenylamino) -2,4-pentadienylidene] -hydrochloride (Compound No. 3) Example 1 Compound no. 1 was mixed with 5.91 g, p-anisidine 5.92 g, and isopropyl alcohol 60 ml, and reacted at 20 to 25 ° C. for 6 hours with stirring. The reaction mixture was treated as in Example 2 to give compound no. 3.30 g (yield 74%) of 3 was obtained. The melting point was 149-150 ° C.
[0020]
Hereinafter, Compound No. A comparative example is given for the synthesis of 1.
Comparative Example 1 Synthesis of 1- (2,4-dinitrophenyl) -4-methylpyridinium chloride (Compound No. 1) To 10.1 g of 2,4-dinitrochlorobenzene and 130 ml of ethyl acetate, 5.6 g of 4-picoline was added. It added at room temperature and made it react at 80 degreeC for 4 hours. There were many by-products in the reaction product, and the target product could not be isolated as crystals. In addition, the measured value of the TLC-MS spectrum of this by-product was m / z 426 (M + ).
[0021]
Reference Comparative Example 1 Synthesis of 1- (2,4-dinitrophenyl) -4-methylpyridinium chloride (Compound No. 1) In a 30 ml ethyl acetate solution of 10.1 g of 2,4-dinitrochlorobenzene, 5.6 g of 4-picoline Was added and reacted at 20 ° C. for 12 hours. The reaction product was filtered and washed with ethyl acetate. 3.4 g (23% yield) of 1 was obtained.
[0022]
As shown above, in Examples 1 to 3 of the present invention, a 3-methyl-2,4-pentadienylidene derivative can be obtained in high yield, while Comparative Example 1 without using a carboxylic acid is used. In 2, the by-product was too much to be isolated or the yield was low.
Claims (4)
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JP10626495A JP4116103B2 (en) | 1995-04-28 | 1995-04-28 | Method for producing pentamethine compound and quaternary salt compound |
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JP10626495A JP4116103B2 (en) | 1995-04-28 | 1995-04-28 | Method for producing pentamethine compound and quaternary salt compound |
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JP4116103B2 true JP4116103B2 (en) | 2008-07-09 |
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