JP2004244390A - 2-phenyl-4-naphthylimidazole compound - Google Patents
2-phenyl-4-naphthylimidazole compound Download PDFInfo
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- JP2004244390A JP2004244390A JP2003037482A JP2003037482A JP2004244390A JP 2004244390 A JP2004244390 A JP 2004244390A JP 2003037482 A JP2003037482 A JP 2003037482A JP 2003037482 A JP2003037482 A JP 2003037482A JP 2004244390 A JP2004244390 A JP 2004244390A
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- Prior art keywords
- compound
- phenyl
- acetonaphthone
- naphthylimidazole
- benzamidine
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Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、新規な2−フェニル−4−ナフチルイミダゾール化合物に関するものである。
【0002】
【従来の技術】
本発明に類似のイミダゾール化合物としては、例えば、非特許文献1に、4−(2−ナフチル)イミダゾールが、非特許文献2には2,4−ジフェニルイミダゾールが記載されている。
しかしながら、フェニル基およびナフチル基を同時に置換基として有するイミダゾール化合物は知られていない。
【0003】
【非特許文献1】
「Chemische Berichte」,1937年,第70巻,p.570
【0004】
【非特許文献2】
「Journal of the Chemical Society」,1948年,p.1960
【0005】
【発明が解決しようとする課題】
本発明は、新規な2−フェニル−4−ナフチルイミダゾール化合物を提供することを目的とする。このイミダゾール化合物は、エポキシ樹脂硬化剤や医薬品中間体として有用なものである。
【0006】
【課題を解決するための手段】
化2の一般式で示される2−フェニル−4−ナフチルイミダゾール化合物を提供する。
【0007】
【化2】
【0008】
【発明の実施の形態】
本発明の2−フェニル−4−ナフチルイミダゾール化合物は、2−フェニル−4−(1−ナフチル)イミダゾール及び2−フェニル−4−(2−ナフチル)イミダゾールである。
本発明のイミダゾール化合物は、公知の方法に準拠して合成することができる。即ち、化3の反応式に示されるように、ω−ハロゲン化アセトナフトン化合物及びベンズアミジン化合物を脱ハロゲン化水素剤の存在下、有機溶媒中で加熱反応させることにより得られる。
【0009】
【化3】
(但し、式中、Xは塩素原子、臭素原子又はヨウ素原子を表す。)
【0010】
即ち、ω−ハロゲン化アセトナフトン化合物と、該化合物に対して0.8〜1.5倍モル、好ましくは0.9〜1.1倍モルのベンズアミジン化合物及び1〜10倍当量の脱塩酸剤とを、溶媒中で室温ないし還流温度にて1〜10時間反応させることにより、2−フェニル−4−ナフチルイミダゾール化合物が生成する。
次いで、得られた反応液または溶媒を留去した後の反応物に、大量の水を加えることにより固体の粗製2−フェニル−4−ナフチルイミダゾール化合物を得ることができる。この粗製物は、再結晶操作により精製することができる。
【0011】
本発明の2−フェニル−4−ナフチルイミダゾール化合物の製造に用いられる代表的なω−ハロゲン化アセトナフトン化合物としては、ω−クロロ−1−アセトナフトン、ω−ブロモ−1−アセトナフトン、ω−ヨード−1−アセトナフトン、ω−クロロ−2−アセトナフトン、ω−ブロモ−2−アセトナフトン等が挙げられる。
【0012】
ベンズアミジン化合物としては、ベンズアミジン、ベンズアミジン酢酸塩等のベンズアミジンの有機酸塩、またはベンズアミジン塩酸塩等のベンズアミジン無機酸塩が挙げられる。
【0013】
脱ハロゲン化水素剤としては、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、炭酸ナトリウム、炭酸カリウム、炭酸カルシウム等の無機アルカリ類、トリエチルアミン、ピリジン、1,8−ジアザビシクロ〔5,4,0〕−7−ウンデセン(DBU)等の有機塩基類、ナトリウムメトキシド、カリウムt−ブトキシド等の金属アルコキシド化合物などが挙げられる。
【0014】
溶媒としては、エタノール、イソプロピルアルコール等のアルコール類、ヘキサン、トルエン等の炭化水素類、クロロホルム、クロロベンゼン等のハロゲン化炭化水素類、酢酸エチル等のエステル類、アセトニトリル等のニトリル類、テトラヒドロフラン、ジオキサン等のエーテル類、ジメチルホルムアミド(DMF)、ジメチルアセトアミド(DMAC)等のアミド類、ジメチルスルホキシド(DMSO)などが挙げられる。
【0015】
【実施例】
以下、本発明を実施例によって具体的に説明するが、本発明はこれらに限定されるものではない。
なお、実施例で使用した主要原料は以下のとおりである。
【0016】
[原料]
・ベンズアミジン塩酸塩(東京化成工業社製、試薬)
・ω−ブロモ−1−アセトナフトン(特開平9−286755号公報記載の方法により調製した)
・ω−ブロモ−2−アセトナフトン(東京化成工業社製、試薬)
【0017】
〔実施例1〕
<2−フェニル−4−(1−ナフチル)イミダゾールの合成>
ベンズアミジン塩酸塩31.3g(0.20mol)、ソジウムメチラート10.8g(0.20mol)及びテトラヒドロフラン150mlからなる懸濁液を1時間加熱還流した後、25℃まで冷却し、ω−ブロモ−1−アセトナフトン49.8g(0.2mol)及びテトラヒドロフラン100mlからなる溶液を、内温が30℃を越えないように滴下した。滴下終了後、ソジウムメチラート10.8g(0.20mol)を加え1時間加熱還流した。次いで、反応液を室温まで放冷して不溶物を濾去し、濾液を減圧乾固して取り出した乾固物を水洗し、引き続きアセトニトリルで洗浄した後、乾燥して目的物の粗結晶を22.0g(収率40.7%)得た。この粗結晶をアセトニトリルを使用して再結晶操作を行い、灰青色の精製結晶を得た。
【0018】
得られた結晶の融点、薄層クロマトグラフィーのRf値、NMR及びマススペクトルデータは、以下のとおりであった。
・mp.167−169℃
・TLC(シリカゲル,クロロホルム/酢酸エチル=9/1):Rf=0.60
・NMR (CD3OD):δ7.3−8.4(m)
・MS
m/z(%):270(M+,100),167(56),139(20),117(5),104(7),89(6).
これらのスペクトルデータから、得られた化合物は、化4で示される2−フェニル−4−(1−ナフチル)イミダゾールであるものと同定した。
【0019】
【化4】
【0020】
〔実施例2〕
<2−フェニル−4−(2−ナフチル)イミダゾールの合成>
ベンズアミジン塩酸塩31.3g(0.20mol)、ソジウムメチラート10.8g(0.20mol)及びテトラヒドロフラン150mlからなる懸濁液を1時間加熱還流した後、20℃まで冷却し、ω−ブロモ−2−アセトナフトン49.8g(0.2mol)及びテトラヒドロフラン100mlからなる溶液を、内温が30℃を越えないように滴下した。滴下終了後、ソジウムメチラート10.8g(0.20mol)を加え1時間加熱還流した。次いで、反応液を室温まで放冷して不溶物を濾去し、濾液を減圧乾固して取り出した乾固物を水洗し、引き続きトルエンで洗浄、乾燥して目的物の粗結晶を36.2g(収率67.0%)得た。この粗結晶をアセトニトリルを使用して再結晶操作を行い、無色の精製結晶を得た。
【0021】
得られた結晶の融点、薄層クロマトグラフィーのRf値、NMR及びマススペクトルデータは、以下のとおりであった。
・mp.230−232℃
・TLC(シリカゲル,クロロホルム/酢酸エチル=9/1):Rf=0.33
・NMR (CD3OD):δ7.4−8.3(m)
・MS
m/z(%):270(M+,100),243(5),166(11),139(21),117(10),89(6).
これらのスペクトルデータから、得られた化合物は、化5で示される2−フェニル−4−(2−ナフチル)イミダゾールであるものと同定した。
【0022】
【化5】
【0023】
【発明の効果】
本発明の2−フェニル−4−ナフチルイミダゾール化合物は、エポキシ樹脂硬化剤や医薬品中間体として有用なものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel 2-phenyl-4-naphthylimidazole compound.
[0002]
[Prior art]
Non-Patent Document 1 describes 4- (2-naphthyl) imidazole, and Non-Patent Document 2 describes 2,4-diphenylimidazole as the imidazole compound similar to the present invention.
However, an imidazole compound having a phenyl group and a naphthyl group simultaneously as a substituent is not known.
[0003]
[Non-patent document 1]
"Chemische Berichte", 1937, Vol. 70, p. 570
[0004]
[Non-patent document 2]
"Journal of the Chemical Society", 1948, p. 1960
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel 2-phenyl-4-naphthylimidazole compound. This imidazole compound is useful as an epoxy resin curing agent or a pharmaceutical intermediate.
[0006]
[Means for Solving the Problems]
Provided is a 2-phenyl-4-naphthylimidazole compound represented by the following general formula:
[0007]
Embedded image
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The 2-phenyl-4-naphthyl imidazole compounds of the present invention are 2-phenyl-4- (1-naphthyl) imidazole and 2-phenyl-4- (2-naphthyl) imidazole.
The imidazole compound of the present invention can be synthesized according to a known method. That is, as shown in the reaction formula 3, the ω-halogenated acetonaphthone compound and the benzamidine compound are heated and reacted in an organic solvent in the presence of a dehydrohalogenating agent.
[0009]
Embedded image
(In the formula, X represents a chlorine atom, a bromine atom or an iodine atom.)
[0010]
That is, an ω-halogenated acetonaphthone compound, a 0.8 to 1.5-fold molar amount, preferably 0.9 to 1.1-fold molar amount of the benzamidine compound and a 1- to 10-fold equivalent amount of a dehydrochlorinating agent relative to the compound Is reacted at room temperature to reflux temperature for 1 to 10 hours in a solvent to produce a 2-phenyl-4-naphthylimidazole compound.
Next, a large amount of water is added to the obtained reaction solution or the reaction product obtained by evaporating the solvent, whereby a solid crude 2-phenyl-4-naphthylimidazole compound can be obtained. This crude product can be purified by a recrystallization operation.
[0011]
Representative ω-halogenated acetonaphthone compounds used for producing the 2-phenyl-4-naphthylimidazole compound of the present invention include ω-chloro-1-acetonaphthone, ω-bromo-1-acetonaphthone, ω-iodo-1. -Acetonaphthone, ω-chloro-2-acetonaphthone, ω-bromo-2-acetonaphthone and the like.
[0012]
Examples of the benzamidine compound include benzamidine, an organic acid salt of benzamidine such as benzamidine acetate, and an inorganic acid salt of benzamidine such as benzamidine hydrochloride.
[0013]
Examples of the dehydrohalogenating agent include inorganic alkalis such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, triethylamine, pyridine, 1,8-diazabicyclo [5,4,0]. Organic bases such as -7-undecene (DBU) and metal alkoxide compounds such as sodium methoxide and potassium t-butoxide.
[0014]
Examples of the solvent include alcohols such as ethanol and isopropyl alcohol, hydrocarbons such as hexane and toluene, halogenated hydrocarbons such as chloroform and chlorobenzene, esters such as ethyl acetate, nitriles such as acetonitrile, tetrahydrofuran, dioxane and the like. Ethers, amides such as dimethylformamide (DMF) and dimethylacetamide (DMAC), and dimethylsulfoxide (DMSO).
[0015]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.
The main raw materials used in the examples are as follows.
[0016]
[material]
・ Benzamidine hydrochloride (Tokyo Chemical Industry Co., Ltd., reagent)
-Ω-bromo-1-acetonaphthone (prepared by the method described in JP-A-9-286755)
・ Ω-Bromo-2-acetonaphthone (Reagent, Tokyo Chemical Industry Co., Ltd.)
[0017]
[Example 1]
<Synthesis of 2-phenyl-4- (1-naphthyl) imidazole>
A suspension consisting of 31.3 g (0.20 mol) of benzamidine hydrochloride, 10.8 g (0.20 mol) of sodium methylate and 150 ml of tetrahydrofuran was heated under reflux for 1 hour, cooled to 25 ° C., and treated with ω-bromo- A solution consisting of 49.8 g (0.2 mol) of 1-acetonaphthone and 100 ml of tetrahydrofuran was added dropwise so that the internal temperature did not exceed 30 ° C. After completion of the dropwise addition, 10.8 g (0.20 mol) of sodium methylate was added, and the mixture was heated under reflux for 1 hour. Then, the reaction solution was allowed to cool to room temperature, and the insoluble material was removed by filtration. The filtrate was dried under reduced pressure, and the dried product was washed with water, then washed with acetonitrile, and then dried to obtain crude crystals of the desired product. 22.0 g (40.7% yield) was obtained. The crude crystals were subjected to a recrystallization operation using acetonitrile to obtain grayish blue purified crystals.
[0018]
The melting point of the obtained crystals, Rf value of thin layer chromatography, NMR and mass spectrum data were as follows.
・ Mp. 167-169 ° C
TLC (silica gel, chloroform / ethyl acetate = 9/1): Rf = 0.60
NMR (CD 3 OD): δ7.3-8.4 (m)
・ MS
m / z (%): 270 (M +, 100), 167 (56), 139 (20), 117 (5), 104 (7), 89 (6).
From these spectral data, the obtained compound was identified as 2-phenyl-4- (1-naphthyl) imidazole represented by Chemical Formula 4.
[0019]
Embedded image
[0020]
[Example 2]
<Synthesis of 2-phenyl-4- (2-naphthyl) imidazole>
A suspension consisting of 31.3 g (0.20 mol) of benzamidine hydrochloride, 10.8 g (0.20 mol) of sodium methylate and 150 ml of tetrahydrofuran was heated under reflux for 1 hour, then cooled to 20 ° C., and ω-bromo- A solution consisting of 49.8 g (0.2 mol) of 2-acetonaphthone and 100 ml of tetrahydrofuran was added dropwise so that the internal temperature did not exceed 30 ° C. After completion of the dropwise addition, 10.8 g (0.20 mol) of sodium methylate was added, and the mixture was heated under reflux for 1 hour. Next, the reaction solution was allowed to cool to room temperature, and insoluble materials were removed by filtration. The filtrate was dried under reduced pressure, and the dried product was washed with water, washed with toluene, and dried to obtain crude crystals of the desired product. 2 g (67.0% yield) was obtained. The crude crystals were recrystallized using acetonitrile to obtain colorless purified crystals.
[0021]
The melting point of the obtained crystals, Rf value of thin layer chromatography, NMR and mass spectrum data were as follows.
・ Mp. 230-232 ° C
TLC (silica gel, chloroform / ethyl acetate = 9/1): Rf = 0.33
NMR (CD 3 OD): δ 7.4-8.3 (m)
・ MS
m / z (%): 270 (M +, 100), 243 (5), 166 (11), 139 (21), 117 (10), 89 (6).
From these spectral data, the obtained compound was identified as 2-phenyl-4- (2-naphthyl) imidazole represented by Chemical Formula 5.
[0022]
Embedded image
[0023]
【The invention's effect】
The 2-phenyl-4-naphthylimidazole compound of the present invention is useful as an epoxy resin curing agent or a pharmaceutical intermediate.
Claims (1)
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005121101A1 (en) | 2004-06-10 | 2005-12-22 | Shikoku Chemicals Corporation | Phenylnaphthylimidazoles for use on copper surfaces during soldering |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005121101A1 (en) | 2004-06-10 | 2005-12-22 | Shikoku Chemicals Corporation | Phenylnaphthylimidazoles for use on copper surfaces during soldering |
US8183386B2 (en) | 2004-06-10 | 2012-05-22 | Shikoku Chemicals Corporation | Phenylnaphthylimidazole compound and usage of the same |
US8378116B2 (en) | 2004-06-10 | 2013-02-19 | Shikoku Chemicals Corporation | Phenylnaphthylimidazole compound and usage of the same |
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