JPH0253778A - Method for synthesizing 2-phenyl-4(5)-methyl-benzylimidazole - Google Patents
Method for synthesizing 2-phenyl-4(5)-methyl-benzylimidazoleInfo
- Publication number
- JPH0253778A JPH0253778A JP20585388A JP20585388A JPH0253778A JP H0253778 A JPH0253778 A JP H0253778A JP 20585388 A JP20585388 A JP 20585388A JP 20585388 A JP20585388 A JP 20585388A JP H0253778 A JPH0253778 A JP H0253778A
- Authority
- JP
- Japan
- Prior art keywords
- phenyl
- formula
- expressed
- benzyl
- methylimidazole
- 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.)
- Granted
Links
- ZXTHWIZHGLNEPG-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC=C1 ZXTHWIZHGLNEPG-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 title claims description 10
- 230000002194 synthesizing effect Effects 0.000 title claims description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940073608 benzyl chloride Drugs 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- KKKDZZRICRFGSD-UHFFFAOYSA-N 1-benzylimidazole Chemical compound C1=CN=CN1CC1=CC=CC=C1 KKKDZZRICRFGSD-UHFFFAOYSA-N 0.000 claims description 4
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000011541 reaction mixture Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 description 1
- FBXGQDUVJBKEAJ-UHFFFAOYSA-N 4h-oxazin-3-one Chemical class O=C1CC=CON1 FBXGQDUVJBKEAJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- CWHFDTWZHFRTAB-UHFFFAOYSA-N phenyl cyanate Chemical compound N#COC1=CC=CC=C1 CWHFDTWZHFRTAB-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は２−フェニル−４（５）−メチル−５（４）−
ベンジルイミダゾール（以下２Ｐ４Ｍ５ＢＺと略称する
）の合成方法に関するものであり、本発明の方法によっ
て得られる２Ｐ４Ｍ５ＢＺはエポキシ樹脂の硬化剤とし
て有用な化合物である。（特開昭６２−３２１１３号公
報）
従来の技術
２Ｐ４Ｍ５ＢＺを合成する方法としては、イソオキサシ
ロンとフェニルシアナートを反応させて、あ・る種の環
縮合オキサジノンを合成しく収率３％）、そのものをＬ
ＩＡＩＨ＜で還元して２Ｐ４Ｍ５ＢＺを得る方法が知ら
れている。〔ケミカルアブストラクツ ２１２４５２．
第９９巻、 （１９８３年）〕しかしながら工業的に合
成する方法は未だ確立されていなかった。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to 2-phenyl-4(5)-methyl-5(4)-
This invention relates to a method for synthesizing benzylimidazole (hereinafter abbreviated as 2P4M5BZ), and 2P4M5BZ obtained by the method of the present invention is a compound useful as a curing agent for epoxy resins. (Japanese Unexamined Patent Publication No. 62-32113) The conventional method for synthesizing 2P4M5BZ is to react isoxacilone and phenyl cyanate to synthesize various ring-fused oxazinones (yield: 3%), and to synthesize 2P4M5BZ. L
A method for obtaining 2P4M5BZ by reduction with IAIH is known. [Chemical Abstracts 212452.
Volume 99, (1983)] However, a method for industrially synthesizing it had not yet been established.
発明が解決しようとする課題
２Ｐ４Ｍ５ＢＺを工業的に合成する方法を導き出すこと
が、本発明の課題である。Problems to be Solved by the Invention It is an object of the present invention to derive a method for industrially synthesizing 2P4M5BZ.
課題を解決するための手段
本発明者等はこのような事情に鑑み鋭意研究の結果、１
−ベンジル−２−フェニル−４（５）−メチルイミダゾ
ール塩酸塩または１．３−ジベンジル−２−フェニル−
４（５）−メチルイミダゾリウム−クロライドを加熱す
るか、あるいは２−フェニル−４−メチルイミダゾール
（以下２Ｐ４ＭＺと略称する）と塩化ベンジルを加熱す
るかのいずれかによって得られる反応混合物をアルカリ
で中和すれば２Ｐ４Ｍ５ＢＺが効率よく得られることを
見出し、本発明を導き出すことができた。２Ｐ４ＭＺは
、１，２−プロピレンジアミンとベンゾニトリルから、
特公昭３９−２４９６５号、同３９−２６４０５号及び
同４２−４５４８号公報に記載の方法により工業的に得
られるものである。また、イミダゾリウム−クロライド
は２Ｐ４ＭＺと塩化ベンジルを反応させて容易に合成す
ることができる。Means for Solving the Problems In view of the above circumstances, the inventors of the present invention have conducted intensive research and have found 1.
-benzyl-2-phenyl-4(5)-methylimidazole hydrochloride or 1,3-dibenzyl-2-phenyl-
The reaction mixture obtained either by heating 4(5)-methylimidazolium-chloride or by heating 2-phenyl-4-methylimidazole (hereinafter abbreviated as 2P4MZ) and benzyl chloride is neutralized with an alkali. It was discovered that 2P4M5BZ can be efficiently obtained by adding the above, and the present invention was achieved. 2P4MZ is made from 1,2-propylene diamine and benzonitrile,
It can be obtained industrially by the method described in Japanese Patent Publication No. 39-24965, Japanese Patent Publication No. 39-26405, and Japanese Patent Publication No. 42-4548. Further, imidazolium chloride can be easily synthesized by reacting 2P4MZ and benzyl chloride.
本発明の合成方法を反応式で示せば次のとおりである。The reaction formula for the synthesis method of the present invention is as follows.
式Ｈの反応を更に詳しく説明すれば、２Ｐ４ＭＺと塩化
ベンジルを約１００°Ｃで加熱すると、先ずＩ−ベンジ
ル−２−フェニル−４（５）−メチルイミダゾールの塩
酸塩と１，３−ジベンジル−２−フェニル−４（５）−
メチルイミダゾリウム−クロライドとが生じる。これを
反応式で示せば下記の通りである。To explain the reaction of formula H in more detail, when 2P4MZ and benzyl chloride are heated at about 100°C, first the hydrochloride of I-benzyl-2-phenyl-4(5)-methylimidazole and 1,3-dibenzyl- 2-phenyl-4(5)-
Methylimidazolium chloride is formed. This reaction formula is shown below.
（ｎ）
１−ベンジル−２−フェニル−４（５）−メチルイミダ
ゾールの塩酸塩も１．３−ジベンジル−２−フェニル−
４（５）−メチルイミダゾリウム−クロライドも夫々そ
のあとの加熱で目的物２Ｐ４Ｍ５ＢＺを与えるので、式
■と式■は本質的に同じ意味を持っている。(n) Hydrochloride of 1-benzyl-2-phenyl-4(5)-methylimidazole is also 1,3-dibenzyl-2-phenyl-
Since 4(5)-methylimidazolium chloride also gives the target product 2P4M5BZ upon subsequent heating, formulas (1) and (2) essentially have the same meaning.
前記の式Ｉと式■の反応は、２５０〜３５０’Ｃの加熱
により、１〜３時間で完結する。反応混合物をアルカリ
（例えば苛性アルカリまたはアンモニア）のメタノール
溶液で中和したのち、メタノールを留去し、残留物を水
洗し、被水洗物を減圧蒸留に付すことにより２Ｐ４Ｍ５
ＢＺが得られる。The reaction of formula I and formula (2) above is completed in 1 to 3 hours by heating at 250 to 350'C. After neutralizing the reaction mixture with a methanol solution of an alkali (for example, caustic alkali or ammonia), methanol is distilled off, the residue is washed with water, and the washed product is subjected to vacuum distillation to obtain 2P4M5.
BZ is obtained.
本発明によって得られる２Ｐ４Ｍ５ＢＺの性質を次示す
るや
ン＋ １２発色”）： Ｒｆ Ｏ，５６〜０．６３Ｍａ
ｓｓ：ｍ／ｅ ２４８（Ｍ’ ）、２３３，２０６，
１７０，１４４，１３０，１１５゜１０４、１０３，９
１．７７
ＮＭＲ（ＣＤｚＯＤ） ： δ７．８６〜６．９６．
ｍ、５１１；７．１Ｂ、Ｓ、５Ｈ；３．９２．Ｓ、２Ｈ
；２．１６．Ｓ、３Ｈ実施例１
２Ｐ４Ｍ２０．２モル（３１，６ｇ） と塩化ベンジル
０．２モル（２５，３ｇ）をフラスコ中、３００’Ｃで
３時間加熱したのち、内容物をＮａＯＨメタノール溶液
で中和し、メタノールを留去し、残留物を水洗し、被水
洗物を減圧蒸留に付し、粗目的物２Ｐ４Ｍ５ＢＺ（ｂｐ
Ｊ３２〜２４６°Ｃ）を０．１．１９モル（２９，６ｇ
、粗収率５９．６モル％）得た。The properties of 2P4M5BZ obtained by the present invention are as follows: Rf O, 56-0.63 Ma
ss: m/e 248 (M'), 233, 206,
170, 144, 130, 115° 104, 103, 9
1.77 NMR (CDzOD): δ7.86-6.96.
m, 511; 7.1B, S, 5H; 3.92. S, 2H
;2.16. S, 3H Example 1 20.2 mol (31.6 g) of 2P4M and 0.2 mol (25.3 g) of benzyl chloride were heated in a flask at 300'C for 3 hours, and then the contents were neutralized with a methanol solution of NaOH. Then, methanol was distilled off, the residue was washed with water, and the washed product was subjected to vacuum distillation to obtain the crude target product 2P4M5BZ (bp
0.1.19 mol (29.6 g
, crude yield 59.6 mol%) was obtained.
実施例２
１．３−ジベンジル−２−フェニル−４（５）−メチル
イミダゾリウム−クロライド０．０１モル（３，７ｇ）
をフラスコ中、３００°Ｃで２時間加熱したのち、内容
物をＮａ１ｌメタノール溶液で中和し、メタノールを留
去し、残留物を水洗し、被水洗物のガスクロマトグラフ
ィーを行った。その結果、２−フェニル−４（５）−メ
チル−５（４）−ベンジルイミダゾールは、０．００６
５６モル（１、６３ｇ 、 ６５．６モル／％）、１−
ベンジル−２−フェニル−４（５）−メチルイミダゾー
ルは０．０００５６モル（０，１３ｇ、５．６モル／％
）、２−フェニル−４−メチルイミダゾールは０．００
１９７モル（０，３１ｇ、 １９．７モル／％）を示し
た。Example 2 1.3-dibenzyl-2-phenyl-4(5)-methylimidazolium-chloride 0.01 mol (3.7 g)
After heating in a flask at 300°C for 2 hours, the contents were neutralized with Na11 methanol solution, methanol was distilled off, the residue was washed with water, and the washed product was subjected to gas chromatography. As a result, 2-phenyl-4(5)-methyl-5(4)-benzylimidazole was 0.006
56 mol (1.63 g, 65.6 mol/%), 1-
Benzyl-2-phenyl-4(5)-methylimidazole was 0.00056 mol (0.13 g, 5.6 mol/%
), 2-phenyl-4-methylimidazole is 0.00
It showed 197 mol (0.31 g, 19.7 mol/%).
なおガスクロマトグラフィーの測定条件は次に示すとお
り。The measurement conditions for gas chromatography are as follows.
本 装 置 ：品性製作所製
ガスクロマトグラフ”ＧＣ−１５Ａ （ＰＴＦ）”数値
処理装置：インチグレーター”Ｃ−１？５八”ガラスカ
ラム：φ３．０ＩＸ２ａ＋
充 填 剤 ＝２χシリコン０Ｖ−１７ｏｎ ユニボ
ート１１Ｐｓ（８０／１００メツシユ）、５ｉｌｌｙ−
８処理品
昇温条件 ：１０”Ｃ／分、空気５００ｄ／分キャリア
ガス：Ｎｚ＋ ５ｏｉｌ／分Equipment: Gas chromatograph “GC-15A (PTF)” manufactured by Konsei Manufacturing Co., Ltd. Numerical processing device: Inch Grater “C-1?58” Glass column: φ3.0IX2a+ Packing material = 2χ Silicon 0V-17on Unibot 11Ps ( 80/100 mesh), 5illy-
Temperature increase conditions for 8 processed products: 10”C/min, air 500d/min Carrier gas: Nz+ 5oil/min
Claims (3)
れる１−ベンジル−２−フェニル−４（５）−メチルイ
ミダゾール塩酸塩を加熱反応させたのちアルカリで中和
することを特徴とする 構造式 ▲数式、化学式、表等があります▼ で示される２−フェニル−４（５）−メチル−５（４）
−ベンジルイミダゾールの合成方法。(1) Heating 1-benzyl-2-phenyl-4(5)-methylimidazole hydrochloride represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [However, R represents a hydrogen atom or a benzyl group] 2-phenyl-4(5)-methyl-5(4), which is characterized by the reaction and then neutralization with an alkali, is represented by the structural formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼
- A method for synthesizing benzylimidazole.
メチルイミダゾリウム−クロライドを加熱反応させたの
ちアルカリで中和することを特徴とする 構造式 ▲数式、化学式、表等があります▼ で示される２−フェニル−４（５）−メチル−５（４）
−ベンジルイミダゾールの合成方法。(2) 1,3-dibenzyl-2-phenyl-4(5)-
2-phenyl-4(5)-methyl-5(4 )
- A method for synthesizing benzylimidazole.
ンジルを加熱反応させたのちアルカリで中和することを
特徴とする 構造式 ▲数式、化学式、表等があります▼ で示される２−フェニル−４（５）−メチル−５（４）
−ベンジルイミダゾールの合成方法。(3) 2-phenyl-4 represented by the structural formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ which is characterized by heating reaction of 2-phenyl-4-methylimidazole and benzyl chloride and then neutralizing with alkali. (5)-methyl-5(4)
- A method for synthesizing benzylimidazole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20585388A JP2802497B2 (en) | 1988-08-18 | 1988-08-18 | Method for synthesizing 2-phenyl-4 (5) -methyl-5 (4) -benzylimidazole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20585388A JP2802497B2 (en) | 1988-08-18 | 1988-08-18 | Method for synthesizing 2-phenyl-4 (5) -methyl-5 (4) -benzylimidazole |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0253778A true JPH0253778A (en) | 1990-02-22 |
| JP2802497B2 JP2802497B2 (en) | 1998-09-24 |
Family
ID=16513795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20585388A Expired - Fee Related JP2802497B2 (en) | 1988-08-18 | 1988-08-18 | Method for synthesizing 2-phenyl-4 (5) -methyl-5 (4) -benzylimidazole |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2802497B2 (en) |
-
1988
- 1988-08-18 JP JP20585388A patent/JP2802497B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2802497B2 (en) | 1998-09-24 |
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