JPH0569826B2 - - Google Patents
Info
- Publication number
- JPH0569826B2 JPH0569826B2 JP1048943A JP4894389A JPH0569826B2 JP H0569826 B2 JPH0569826 B2 JP H0569826B2 JP 1048943 A JP1048943 A JP 1048943A JP 4894389 A JP4894389 A JP 4894389A JP H0569826 B2 JPH0569826 B2 JP H0569826B2
- Authority
- JP
- Japan
- Prior art keywords
- carboxylic acid
- benzyl
- group
- reaction
- acid
- 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
Links
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 44
- -1 imidazole compound Chemical class 0.000 claims description 34
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 27
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 9
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 125000005907 alkyl ester group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 7
- 150000001735 carboxylic acids Chemical class 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 5
- 229940073608 benzyl chloride Drugs 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BWYQCNUKLXIXOK-UHFFFAOYSA-M 1,3-dibenzylimidazol-1-ium;chloride Chemical compound [Cl-].C1=C[N+](CC=2C=CC=CC=2)=CN1CC1=CC=CC=C1 BWYQCNUKLXIXOK-UHFFFAOYSA-M 0.000 description 1
- 150000004963 1-benzylimidazoles Chemical class 0.000 description 1
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
産業上の利用分野
本発明は１位未置換イミダゾール化合物をベン
ジル化して１−ベンジルイミダゾール化合物を合
成する方法に関するものであり、本発明の方法に
よつて得られる１−ベンジルイミダゾール化合物
はポリエポキシ樹脂の硬化剤及び硬化促進剤とし
て有用である。
従来の技術
１位未置換イミダゾール化合物と塩化ベンジル
とをHCl受容体（acceptor）の存在下、活性水素
をもたない適当な溶剤中で反応させる方法が知ら
れている。
発明が解決しようとする課題
１位未置換イミダゾール化合物に塩化ベンジル
を反応させてベンジル化する方法においては、次
のような問題がある。即ち、１位未置換イミダゾ
ール化合物と塩化ベンジルの反応によつて生じた
１−ベンジルイミダゾール化合物は、未反応の塩
化ベンジルと反応して１，３−ジベンジルイミダ
ゾリウム−クロライド化合物となり易いので、不
要なイミダゾリウム−クロライドが多量に副生成
し、また塩化ベンジルは催涙性を有するので取扱
いが困難であつた。
本発明方法はこのような難点を解消するために
為されるものである。
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位未置換イミダゾール化合物とベンジル
アルコールをカルボン酸、カルボン酸無水物、そ
れらのベンジルエステルあるいはそれらの低級ア
ルキルエステルの共存下に加熱反応させ、反応生
成物をアルカリ中和することにより、１−ベンジ
ルイミダゾール化合物が効率よく得られることを
見い出し、本発明を導き出すことができた。
また本発明者等は、１位未置換イミダゾール化
合物とカルボン酸ベンジルエステルとを反応さ
せ、反応生成物をアルカリ中和することによつて
同様に１−ベンジルイミダゾール化合物が得られ
ることを知見した。
発明の合成方法を反応式で示せば次の通りであ
る。
〔〕
Industrial Application Field The present invention relates to a method for synthesizing a 1-benzylimidazole compound by benzylating an unsubstituted imidazole compound at the 1-position, and the 1-benzylimidazole compound obtained by the method of the present invention is a polyepoxy resin. It is useful as a curing agent and curing accelerator. Prior Art A method is known in which a 1-position unsubstituted imidazole compound and benzyl chloride are reacted in the presence of an HCl acceptor in a suitable solvent without active hydrogen. Problems to be Solved by the Invention In the method of benzylating a 1-position unsubstituted imidazole compound by reacting it with benzyl chloride, there are the following problems. That is, the 1-benzylimidazole compound produced by the reaction of the 1-position unsubstituted imidazole compound and benzyl chloride is unnecessary because it easily reacts with unreacted benzyl chloride to form a 1,3-dibenzylimidazolium chloride compound. A large amount of imidazolium chloride is produced as a by-product, and benzyl chloride has lachrymatory properties, making it difficult to handle. The method of the present invention is intended to overcome these difficulties. Means for Solving the Problems In view of the above circumstances, the present inventors have conducted intensive research and found that a 1-position unsubstituted imidazole compound and benzyl alcohol can be converted into a carboxylic acid, a carboxylic acid anhydride, a benzyl ester thereof, or a lower alkyl thereof. It was discovered that a 1-benzylimidazole compound can be efficiently obtained by carrying out a heating reaction in the presence of an ester and neutralizing the reaction product with an alkali, thereby leading to the present invention. The present inventors also discovered that a 1-benzylimidazole compound can be similarly obtained by reacting a 1-position unsubstituted imidazole compound with a benzyl carboxylic acid ester and neutralizing the reaction product with an alkali. The synthesis method of the invention is shown in the following reaction formula. []
【化】[ka]
【式】 〔〕【formula】 []
【化】[ka]
前記反応式〔〕において、カルボン酸、カル
ボン酸無水物、それらのベンジルエステルあるい
はそれらの低級アルキルエステルは、イミダゾー
ル化合物1.0モルに対して通常0.01ないし1.0モル
の範囲で使用されるが、特に好ましい範囲は0.05
ないし0.4モルである。またベンジルアルコール
は、イミダゾール化合物1.0モルに対して通常
1.05ないし1.5モルの範囲で使用される。反応温
度は200ないし300℃の範囲であるが、特に230な
いし260℃の範囲が好適であり、この場合反応は
４時間以内で完結する。本反応は常圧下あるいは
ベンジルアルコールが留出しない程度の減圧下で
行つてもよい。生成水はアゼオトロープ（b.p.98
℃）の形で系外に留出する。系内における少量の
残留水分を除去するために反応が充分進行した段
階で600mmHg程度の減圧にするか、または不活性
ガスを用いて掃気してもよい。
本反応において、カルボン酸、カルボン酸無水
物、それらのベンジルエステルあるいはそれらの
低級アルキルエステルは触媒作用を示すが、これ
は一つの新しい知見と言える。
反応混合物にカルボン酸成分を中和するのに必
要な量の水酸化アルカリを加え、減圧蒸留を行え
ば粗目的物１−ベンジルイミダゾール化合物が得
られる。
粗目的物に未反応のイミダゾール化合物に相当
するモル数の水酸化アルカリを加え、再び減圧蒸
留を行えば、未反応イミダゾール化合物を殆ど含
まない目的物が得られる。
本発明において使用されるカルボン酸、カルボ
ン酸無水物、それらのベンジルエステルとして
は、安息香酸、フタル酸、トリメリツト酸、ピロ
メリツト酸、イソフタル酸、テレフタル酸、コハ
ク酸、マレイン酸、アジピン酸、それら酸無水物
及びそれらのベンジルエステルである。（ポリカ
ルボン酸の場合はセミエステルも含む）
前記の各種カルボン酸のベンジルエステルは、
ベンジルアルコールと対応するカルボン酸無水物
あるいはカルボン酸とを加熱して得られるもので
ある。従つて、本発明の実施に際し予め別に準備
したカルボン酸エステルを使用する代わりに、カ
ルボン酸とベンジルアルコールを併用することも
できる。
また、カルボン酸の低級アルキルエステルは熱
時にベンジルアルコールと容易にエステル交換し
て（低沸点アルコールは系外に留去される）ベン
ジルエステルを与えることが知られている。
従つて、本発明の実施に際して、カルボン酸の
各種低級アルキルエステル、例えばメチルエステ
ル、エチルエステル、プロピルエステル、イソプ
ロピルエステル及びブチルエステル等を使用する
ことができる。
前記反応式〔〕で示される製法においては、
カルボン酸ベンジルエステルは、イミダゾール化
合物に対して当量あるいは当量よりやや過剰に使
用すべきである。また、反応温度は通常200ない
し300℃の範囲であるが、特に230ないし260℃の
範囲が好ましく、この場合反応は４時間以内で完
結する。反応混合物のカルボン酸成分を水酸化ア
ルカリで中和したのち、有機溶剤（例えばアセト
ン）を加え、濾過を行い、瀘液を減圧蒸留すれば
粗目的物１−ベンジルイミダゾール化合物が得ら
れる。粗目的物に未反応のイミダゾール化合物の
モル数に相当する水酸化アルカリを加え、再び減
圧蒸留を行えば、未反応イミダゾール化合物を殆
ど含まない目的物が得られる。
ベンジルエステルを合計するために使用される
代表的なカルボン酸としては、安息香酸、フタル
酸、トリメリツト酸、ピロメリツト酸、イソフタ
ル酸、テレフタル酸、コハク酸、マレイン酸、ア
ジピン酸及びそれら酸無水物である。
前記の各種カルボン酸のベンジルエステル（セ
ミエステルも含める）は、ベンジルアルコールと
対応するカルボン酸無水物あるいはカルボン酸と
を生成水を系外に留去させながら加熱して得られ
るものである。
本発明において使用される代表的なイミダゾー
ル化合物は２−メチルイミダゾール（以下2MZ
で表わす）、２−エチルイミダゾール（以下2EZ
で表わす）、２−イソプロピルイミダゾール（以
下2IZで表わす）、２−フエニルイミダゾール（以
下2PZで表わす）及び２−エチル−４−メチルイ
ミダゾール（以下2E4MZで表わす）である。
本発明の方法によつて得られる各種の１−ベン
ジルイミダゾールの性質を表１に示す。
但し、TLCの展開はシリカＧとクロロホル
ム／メタノール、メタノールあるいはアセトンの
いずれかを用いて行つた。
In the above reaction formula [], the carboxylic acid, carboxylic acid anhydride, benzyl ester thereof, or lower alkyl ester thereof is usually used in an amount of 0.01 to 1.0 mol per 1.0 mol of the imidazole compound, but a particularly preferred range is is 0.05
to 0.4 mole. Also, benzyl alcohol is usually used per 1.0 mole of imidazole compound.
It is used in a range of 1.05 to 1.5 mol. The reaction temperature is in the range of 200 to 300°C, particularly preferably in the range of 230 to 260°C, in which case the reaction is completed within 4 hours. This reaction may be carried out under normal pressure or under reduced pressure to the extent that benzyl alcohol is not distilled off. The produced water is azeotrope (bp98
It is distilled out of the system in the form of In order to remove a small amount of residual moisture in the system, the pressure may be reduced to about 600 mmHg after the reaction has sufficiently progressed, or the system may be scavenged using an inert gas. In this reaction, carboxylic acids, carboxylic acid anhydrides, their benzyl esters, or their lower alkyl esters exhibit catalytic activity, which can be said to be a new finding. A necessary amount of alkali hydroxide to neutralize the carboxylic acid component is added to the reaction mixture, and vacuum distillation is performed to obtain the crude target 1-benzylimidazole compound. By adding alkali hydroxide in the number of moles corresponding to the unreacted imidazole compound to the crude target product and performing vacuum distillation again, the target product containing almost no unreacted imidazole compound can be obtained. Carboxylic acids, carboxylic acid anhydrides, and their benzyl esters used in the present invention include benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, isophthalic acid, terephthalic acid, succinic acid, maleic acid, adipic acid, and these acids. anhydrides and their benzyl esters. (In the case of polycarboxylic acids, semi-esters are also included) The benzyl esters of the various carboxylic acids mentioned above are:
It is obtained by heating benzyl alcohol and the corresponding carboxylic acid anhydride or carboxylic acid. Therefore, in carrying out the present invention, a carboxylic acid and benzyl alcohol can be used in combination instead of using a separately prepared carboxylic ester. Furthermore, it is known that lower alkyl esters of carboxylic acids easily transesterify with benzyl alcohol when heated (the low-boiling alcohol is distilled out of the system) to give benzyl esters. Accordingly, various lower alkyl esters of carboxylic acids, such as methyl esters, ethyl esters, propyl esters, isopropyl esters, and butyl esters, can be used in the practice of this invention. In the production method shown by the above reaction formula [],
The carboxylic acid benzyl ester should be used in an equivalent amount or in slightly excess amount relative to the imidazole compound. Further, the reaction temperature is usually in the range of 200 to 300°C, particularly preferably in the range of 230 to 260°C, in which case the reaction is completed within 4 hours. After neutralizing the carboxylic acid component of the reaction mixture with an alkali hydroxide, an organic solvent (for example, acetone) is added, filtration is performed, and the filtrate is distilled under reduced pressure to obtain the crude target 1-benzylimidazole compound. By adding alkali hydroxide corresponding to the number of moles of unreacted imidazole compound to the crude target product and performing vacuum distillation again, the target product containing almost no unreacted imidazole compound can be obtained. Typical carboxylic acids used to sum benzyl esters include benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, isophthalic acid, terephthalic acid, succinic acid, maleic acid, adipic acid and their acid anhydrides. be. The benzyl esters (including semi-esters) of various carboxylic acids mentioned above are obtained by heating benzyl alcohol and the corresponding carboxylic acid anhydride or carboxylic acid while distilling the produced water out of the system. A typical imidazole compound used in the present invention is 2-methylimidazole (hereinafter referred to as 2MZ
), 2-ethylimidazole (hereinafter referred to as 2EZ
), 2-isopropylimidazole (hereinafter referred to as 2IZ), 2-phenylimidazole (hereinafter referred to as 2PZ) and 2-ethyl-4-methylimidazole (hereinafter referred to as 2E4MZ). Table 1 shows the properties of various 1-benzylimidazoles obtained by the method of the present invention. However, TLC development was performed using Silica G and either chloroform/methanol, methanol, or acetone.
【表】
実施例 １〜24
１位未置換イミダゾール0.1モルとベンジルア
ルコール0.11モル、所定量のカルボン酸、カルボ
ン酸無水物あるいはカルボン酸低級アルキルエス
テルを混合し、所定の条件で加熱反応させたの
ち、反応混合物にアルカリを加えて中和塩析し、
生じた油層を分液採取し、その抽出液をそのまま
あるいはNaOHの共存下で減圧分留して、粗目
的物の１−ベンジルイミダゾール化合物を得た。
これらの試験条件及びその結果は表２に示したと
おりであつた。
なお、ベンジルアルコールのカルボン酸エステ
ル化反応を予め行つたのち、１位未置換イミダゾ
ール化合物を反応系に加え、改めて加熱反応を行
つた場合は、備考欄にエステル化先行と注記し
た。
得られた各粗目的物はTLC（シリカＧ）／アセ
トンで調べたところ、極く僅かの未反応イミダゾ
ールを含むのみであつた。[Table] Examples 1 to 24 0.1 mol of 1-position unsubstituted imidazole, 0.11 mol of benzyl alcohol, and a predetermined amount of carboxylic acid, carboxylic acid anhydride, or carboxylic acid lower alkyl ester were mixed and reacted by heating under predetermined conditions. , add an alkali to the reaction mixture for neutralization and salting out,
The resulting oil layer was separated and collected, and the extract was subjected to vacuum fractional distillation as it was or in the presence of NaOH to obtain the crude target 1-benzylimidazole compound.
These test conditions and results were as shown in Table 2. In addition, when the 1-position unsubstituted imidazole compound was added to the reaction system after the carboxylic acid esterification reaction of benzyl alcohol was carried out in advance, and the heating reaction was carried out again, it was noted that esterification preceded in the notes column. When each crude target product obtained was examined by TLC (Silica G)/acetone, it was found that it contained only a very small amount of unreacted imidazole.
【表】【table】
【表】
実施例 25〜33
１位未置換イミダゾール0.1モルにカルボン酸
ベンジルエステルをイミダゾール化合物に対して
当量（但し実施例32においては3.3当量）用い、
所定条件で加熱反応させたのち、反応混合物をア
ルカリで中和塩析して生じた油層を分液採取した
のち、必要に応じてアルカリ中和した混合物を減
圧乾固したのちメタノールを抽出し、減圧分留を
行い、粗目的物の１−ベンジルイミダゾール化合
物を得た。これらの試験条件及びその結果は表３
に示したとおりであつた。なお粗目的物は、前記
実施例と同じ薄層クロマトグラフ分析の結果、不
純物として極く僅かな未反応イミダゾールを含む
のみであつた。[Table] Examples 25 to 33 Using 0.1 mole of unsubstituted imidazole at the 1-position, an equivalent amount of carboxylic acid benzyl ester to the imidazole compound (3.3 equivalents in Example 32),
After heating and reacting under predetermined conditions, the reaction mixture is neutralized and salted out with an alkali, the resulting oil layer is separated and collected, and if necessary, the mixture is neutralized with an alkali, the mixture is dried under reduced pressure, and methanol is extracted. Fractional distillation under reduced pressure was performed to obtain a crude target 1-benzylimidazole compound. These test conditions and results are shown in Table 3.
It was as shown in . The crude target product was found to contain only a very small amount of unreacted imidazole as an impurity as a result of the same thin layer chromatography analysis as in the above example.
【表】【table】
Claims (1)
ル基またはフエニル基を表わし、R4は水素原子
またはメチル基を表わす。〕 で示される１位未置換イミダゾール化合物とベン
ジルアルコールをカルボン酸、カルボン酸無水
物、それらのベンジルエステルあるいはそれらの
低級アルキルエステルの共存下で加熱反応させ、
反応生成物をアルカリで中和することを特徴とす
る一般式 【式】 〔但し、R2とR4は前記のとおり。〕 で示される１−ベンジルイミダゾール化合物の合
成方法。 ２ 一般式【式】 〔但し、R2はメチル基、エチル基、イソプロピ
ル基またはフエニル基を表わし、R4は水素原子
またはメチル基を表わす。〕 で示される１位未置換イミダゾール化合物とカル
ボン酸ベンジルエステルとを加熱反応させ、反応
生成物をアルカリで中和することを特徴とする一
般式 【式】 〔但し、R2とR4は前記のとおり。〕 で示される１−ベンジルイミダゾール化合物の合
成方法。[Claims] 1 General formula [Formula] [However, R 2 represents a methyl group, ethyl group, isopropyl group or phenyl group, and R 4 represents a hydrogen atom or a methyl group. ] The 1-position unsubstituted imidazole compound shown by and benzyl alcohol are heated and reacted in the coexistence of a carboxylic acid, a carboxylic acid anhydride, their benzyl ester or their lower alkyl ester,
General formula [Formula] characterized in that the reaction product is neutralized with an alkali [However, R 2 and R 4 are as described above. ] A method for synthesizing a 1-benzylimidazole compound shown in the following. 2 General Formula [Formula] [However, R 2 represents a methyl group, ethyl group, isopropyl group, or phenyl group, and R 4 represents a hydrogen atom or a methyl group. [However, R 2 and R 4 are the above-mentioned As of. ] A method for synthesizing a 1-benzylimidazole compound shown in the following.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1048943A JPH02225470A (en) | 1989-02-28 | 1989-02-28 | Method for synthesizing 1-benzylimidazole compound |
| CA000610304A CA1337428C (en) | 1988-09-06 | 1989-09-05 | Process for preparation of 1-benzylimidazole compound, and novel compound |
| KR1019890012841A KR970005532B1 (en) | 1988-09-06 | 1989-09-06 | Process for preparation of 1-benzylimidazole compound, and novel compound |
| EP89309024A EP0358484B1 (en) | 1988-09-06 | 1989-09-06 | Process for preparation of 1-benzylimidazole compound, and its compound |
| DE68916725T DE68916725T2 (en) | 1988-09-06 | 1989-09-06 | Process for the preparation of 1-benzylimidazole and its compound. |
| US07/403,460 US5021584A (en) | 1988-09-06 | 1989-09-06 | Process for preparation of 1-benzylimidazole compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1048943A JPH02225470A (en) | 1989-02-28 | 1989-02-28 | Method for synthesizing 1-benzylimidazole compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02225470A JPH02225470A (en) | 1990-09-07 |
| JPH0569826B2 true JPH0569826B2 (en) | 1993-10-01 |
Family
ID=12817360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1048943A Granted JPH02225470A (en) | 1988-09-06 | 1989-02-28 | Method for synthesizing 1-benzylimidazole compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02225470A (en) |
-
1989
- 1989-02-28 JP JP1048943A patent/JPH02225470A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02225470A (en) | 1990-09-07 |
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