JPH0232062A - Synthesis of 1,4(5)-dibenzyl-2-phenylimidazole - Google Patents
Synthesis of 1,4(5)-dibenzyl-2-phenylimidazoleInfo
- Publication number
- JPH0232062A JPH0232062A JP18127888A JP18127888A JPH0232062A JP H0232062 A JPH0232062 A JP H0232062A JP 18127888 A JP18127888 A JP 18127888A JP 18127888 A JP18127888 A JP 18127888A JP H0232062 A JPH0232062 A JP H0232062A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- mineral
- mineral acid
- formula
- phenylimidazole
- 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.)
- Pending
Links
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 37
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 34
- 239000011707 mineral Substances 0.000 claims abstract description 34
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 235000011007 phosphoric acid Nutrition 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 7
- IJJNTMLAAKKCML-UHFFFAOYSA-N tribenzyl borate Chemical compound C=1C=CC=CC=1COB(OCC=1C=CC=CC=1)OCC1=CC=CC=C1 IJJNTMLAAKKCML-UHFFFAOYSA-N 0.000 claims abstract description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 6
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 229940005657 pyrophosphoric acid Drugs 0.000 claims abstract description 5
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000003472 neutralizing effect Effects 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 6
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical class O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
- GIXFALHDORQSOQ-UHFFFAOYSA-N 2,4,6,8-tetrahydroxy-1,3,5,7,2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraoxatetraphosphocane 2,4,6,8-tetraoxide Chemical compound OP1(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)O1 GIXFALHDORQSOQ-UHFFFAOYSA-N 0.000 claims description 4
- AZSFNUJOCKMOGB-UHFFFAOYSA-N cyclotriphosphoric acid Chemical compound OP1(=O)OP(O)(=O)OP(O)(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-N 0.000 claims description 4
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 claims description 3
- -1 phosphorus halide Chemical class 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical class OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N phosphorus trioxide Chemical class O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007795 chemical reaction product Substances 0.000 abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004327 boric acid Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 abstract 3
- 150000001875 compounds Chemical class 0.000 abstract 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract 1
- 235000019445 benzyl alcohol Nutrition 0.000 abstract 1
- 239000004848 polyfunctional curative Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 4
- YATKABCHSRLDGQ-UHFFFAOYSA-N 5-benzyl-2-phenyl-1h-imidazole Chemical compound C=1C=CC=CC=1CC(N=1)=CNC=1C1=CC=CC=C1 YATKABCHSRLDGQ-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- MTCJSQBAMYTTPS-UHFFFAOYSA-N 4,5-dibenzyl-2-phenyl-1h-imidazole Chemical compound C=1C=CC=CC=1CC=1N=C(C=2C=CC=CC=2)NC=1CC1=CC=CC=C1 MTCJSQBAMYTTPS-UHFFFAOYSA-N 0.000 description 1
- 101150041968 CDC13 gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing 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−フェニルイミダゾール（以下２ＰＺと略称
する）あるいは１−ベンジル−２−フェニルイミダゾー
ル（以下ＩＢ２ＰＺと略称する）とトリベンジル−ボレ
ートを鉱酸共存下に加熱反応させることにより、１．４
（５）−ジベンジル−２−フェニルイミダゾール（以下
ＩＢ４８２ＰＺと略称する）を合成する方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is a method of combining 2-phenylimidazole (hereinafter abbreviated as 2PZ) or 1-benzyl-2-phenylimidazole (hereinafter abbreviated as IB2PZ) and tribenzyl-borate in the coexistence of a mineral acid. By heating reaction below, 1.4
(5)-Dibenzyl-2-phenylimidazole (hereinafter abbreviated as IB482PZ).
本発明の方法によってえられるＩＢ４８２ＰＺは液状エ
ポキシ樹脂との相溶性がよく、また液状酸無水物と混合
する際、ゲル状の塩を生成しないので、エポキシ樹脂硬
化剤または硬化促進剤として利用される。（特願昭６３
−７１６５０号）従来の技術
イミダゾールをベンジル化させる方法としては、本発明
者等が既に提案しているイミダゾールと塩化ベンジルを
反応させる方法（特願昭６３−７１６５０号）がある。IB482PZ obtained by the method of the present invention has good compatibility with liquid epoxy resins and does not generate gel-like salts when mixed with liquid acid anhydrides, so it can be used as an epoxy resin curing agent or curing accelerator. . (Special application 1986
(No. 71,650) Prior Art As a method for benzylating imidazole, there is a method of reacting imidazole with benzyl chloride, which has already been proposed by the present inventors (Japanese Patent Application No. 71,650/1982).
すなわち２ＰＺを２−フェニルイミダシリンの接触脱水
素で合成する際、副生成する２−フェニル−４−ベンジ
ルイミダゾール（以下２Ｐ４ＢＺと略称する）（澤 夏
雄二日化誌８９巻９号８６８〜８７２頁（１９６８））
を苛性アルカリと加熱し生成水を系外に留去させること
により２−フェニル−４−ベンジルイミダゾールのアル
カリ金属塩となし、そのものと塩化ベンジルとの反応で
ＩＢ４８２ＰＺを作っている。That is, when 2PZ is synthesized by catalytic dehydrogenation of 2-phenylimidacillin, 2-phenyl-4-benzylimidazole (hereinafter abbreviated as 2P4BZ) is produced as a by-product (Natsuo Sawa Nikikashi Vol. 89, No. 9, 868-872) page (1968))
The alkali metal salt of 2-phenyl-4-benzylimidazole is produced by heating it with a caustic alkali and distilling the produced water out of the system, and IB482PZ is produced by reacting the salt with benzyl chloride.
発明が解決しようとする課題
２Ｐ４ＢＺの供給源を副生成物に頼っている限りＩＢ４
８２ＰＺの自由な供給は制限される。その制限を解消す
るだめのＩＢ４８２ＰＺの新合成方法を導き出すことが
本発明が解決しようとする課題である。Problem to be Solved by the Invention 2As long as the source of P4BZ relies on by-products, IB4
The free supply of 82PZ is restricted. The problem to be solved by the present invention is to derive a new method for synthesizing IB482PZ that overcomes this limitation.
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、２
ＰＺあるいはＩＢ２ＰＺのうちいずれか一種とトリベン
ジル−ボレートをある種の鉱酸の共存下で加熱するとＩ
Ｂ４８２ＰＺ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。Means for Solving the Problems In view of the above circumstances, the inventors of the present invention have conducted intensive research and have found two solutions.
When either PZ or IB2PZ and tribenzyl-borate are heated in the coexistence of a certain mineral acid, I
We found that B482PZ can be obtained efficiently and were able to derive the present invention.
以下、本発明の実施の７７Ｊｊ様について述べる。Hereinafter, Mr. 77Jj who carried out the present invention will be described.
本発明を反応式で示せば次の通りである。The reaction formula of the present invention is as follows.
なおＨＡは鉱酸を示す。Note that HA indicates mineral acid.
式■及び式■の反応において、鉱酸は２ＰＺに対して少
なくとも等モル使用すべきであり、等モル以上部ち過剰
の鉱酸は本反応を妨害しない。In the reactions of formula (1) and formula (2), the mineral acid should be used in at least an equimolar amount relative to 2PZ, and an excess of the mineral acid in an equimolar or more amount will not interfere with the reaction.
鉱酸としては、塩化水素、臭化水素、沃化水素、正リン
酸、亜リン酸、次リン酸、次亜リン酸、ピロリン酸、ト
リメタリン酸、テトラメタリン酸等のいずれかを用いる
ことができる。鉱酸発生剤としてはオキシハロゲン化リ
ン（ｐｏｘい、ハロゲン化リン（ＰＸ、及びＰＸｓ）、
無水リン酸及び無水亜リン酸等のいずれかも鉱酸と同様
に使用できる。また反応において鉱酸を発生する鉱酸塩
も鉱酸と同様に使用できる。この場合の鉱酸塩としては
、正リン酸、亜ＩＪ−ン酸、次リン酸、次亜リン酸、ピ
ロリン酸、トリメタリン酸、及びテトラメタリン酸のア
ン千二つ１．塩、ナトリウム塩、カリウム塩、カルシウ
ム塩、バリウム塩及びマグネシウム塩のいずれかを使用
することができる。特に安価ム４二人手できる正リン酸
またはその塩が好適である。As the mineral acid, hydrogen chloride, hydrogen bromide, hydrogen iodide, orthophosphoric acid, phosphorous acid, hypophosphoric acid, hypophosphorous acid, pyrophosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, etc. can be used. can. Examples of mineral acid generators include phosphorus oxyhalides (POX, phosphorus halides (PX, and PXs),
Either phosphoric anhydride or phosphorous anhydride can be used in the same manner as mineral acids. Also, mineral acid salts that generate mineral acids in the reaction can be used in the same manner as mineral acids. In this case, the mineral acid salts include orthophosphoric acid, IJ-phosphoric acid, hypophosphorous acid, hypophosphorous acid, pyrophosphoric acid, trimetaphosphoric acid, and tetrametaphosphoric acid. Any of the salts, sodium, potassium, calcium, barium and magnesium salts can be used. Particularly suitable is orthophosphoric acid or its salt, which is inexpensive and can be prepared by two people.
本発明においてＬ述の如く、多種多様のリン酸及びぞれ
らの塩が使用できる。その理由として容易に考えられる
ことは、各鉱酸及びそれらの塩は加熱時にそれぞれ変化
し７、別の形の鉱酸またはその塩に姿を変えうると云・
うことである。即ち千谷利三著：新版無機化学、中巻、
７０２〜７３０頁（産業図書株式会社、昭和４８年）に
よれば、例えば無水リン酸（ｐ２ｏＳ）は水と反応し正
リン酸（１１３ＰＯ４）と亜リン酸（ｔｈＰＯ３）を与
える。水が不充分な場合はＩ・リンタリン酸（ＩＩＪ：
ｉｏＪとテトラメタリン酸（Ｈ４Ｐ ４０Ｉ７）を与え
る。正リン酸は２００〜３００°Ｃで水を放出しピロリ
゛／酸（ｌＩ４Ｐ２０７）を与え、ビロリン酸は更に水
を放出して多量化しポリリン酸となり、ポリリン酸も水
を放出してポリメタリン酸（１＋１１０．）ｎとなる。In the present invention, as mentioned above, a wide variety of phosphoric acids and their salts can be used. One possible reason for this is that mineral acids and their salts change when heated,7 and can transform into other forms of mineral acids or their salts.
That is true. Namely, Toshizo Chiya: New Edition Inorganic Chemistry, Volume 2,
According to pages 702-730 (Sangyo Tosho Co., Ltd., 1972), for example, phosphoric anhydride (p2oS) reacts with water to give orthophosphoric acid (113PO4) and phosphorous acid (thPO3). If there is insufficient water, I. Phosphoric acid (IIJ:
ioJ and tetrametaphosphoric acid (H4P 40I7). Orthophosphoric acid releases water at 200 to 300°C to give pyrrolidium/acid (lI4P207), birophosphoric acid further releases water and becomes more abundant, becoming polyphosphoric acid, and polyphosphoric acid also releases water to give polymetaphosphoric acid (1I4P207). 1+110.)n.
、二の一連の反応はいずれも可逆的である。Both of the two series of reactions are reversible.
次リン酸（ｌｌＪＰ２０６）は水と反応しと正すン酸、
工：亜すン酸含与える。三塩化リン（ＰＣｌ３）は水と
反応Ｌ／亜リン酸を９゜える。亜リン酸は水と反応して
正リン酸を与える。Hypophosphoric acid (llJP206) is a phosphoric acid that reacts with water.
Engineering: Contains sonic acid. Phosphorous trichloride (PCl3) reacts with water to yield 9° L/phosphorous acid. Phosphorous acid reacts with water to give orthophosphoric acid.
正リン酸の第１塩は加熱により水を放出しポリメタリン
酸の第１塩（ＭＰＯ３）−を与える。正リン酸の第２塩
は同じ（ビロリン酸の第２塩（Ｍ、Ｐ２＋１□０．）を
与え、正リン酸のアンモニウムとアルカリよりなる第２
塩はアンモニアを放出してメタリン酸の第１塩０ｔＰＯ
３）、を１１える。The first salt of orthophosphoric acid releases water upon heating to give the first salt of polymetaphosphoric acid (MPO3). The second salt of orthophosphoric acid is the same (the second salt of birophosphoric acid (M, P2+1□0.) is given, and the second salt of orthophosphoric acid is made of ammonium and alkali.
The salt releases ammonia and becomes the first salt of metaphosphoric acid 0tPO
3) Add 11.
以上の説明から、たとえ特定のある種のリン酸もしくは
その塩を本発明の実施に必要な鉱酸として使用したとし
ても、それらは反応時に加熱を受け、また水の出入りに
も遇うので、反応中、最初の形を維持しているか否かは
不明であると云・うことができる。ｔＡ言ずれば別のリ
ン酸もしくはその塩に変化しているかいなかは定かでな
い。From the above explanation, even if a certain type of phosphoric acid or its salt is used as the mineral acid necessary for carrying out the present invention, it will be heated during the reaction, and water will enter and exit the reaction. However, it can be said that it is unclear whether or not it has maintained its original form. In other words, it is unclear whether tA has changed to another phosphoric acid or its salt.
トリベンジル−ボレー） （（ＱＣｉｂＯ） ３８ ）
は１モルのホウ酸（ｌｌＪＯ３）と３モル以トのヘンシ
ルアルコールを１００°Ｃ以上で加熱し、生成水をアゼ
オ］・ローブ（＋ａｚｅｏｔｒｏｐｅ） （ｂ、Ｉ）
−９８”Ｃ＋ 水９１ ｗｔ％〕の形で系外に除去１．
たのち、残留物を減圧蒸留してえられるｂ−ｐ−：１１
９８〜２０５°Ｃの無色の液体である。tribenzyl-volley) ((QCibO) 38 )
1 mole of boric acid (llJO3) and 3 moles or more of Hensyl alcohol are heated at 100°C or higher, and the resulting water is converted into azeotrope (+azeotrope) (b, I).
-98"C + water 91 wt%] removed from the system 1.
Afterwards, the residue is distilled under reduced pressure to obtain b-p-:11
It is a colorless liquid with a temperature of 98-205°C.
本発明において生成水はホウ酸の形で固定されるので、
減圧は特に必要ではなく、２５０−３５０ ’Ｃの加熱
で、反応は１〜２時間で完結する。反応混合物をアルカ
リ （たとえば苛性アルカリまたはアンモニア）水溶液
で中和すれば、鉱酸は水溶液に移り、１Ｉ３４Ｂ２ＰＺ
、未反応２ＰＺ及び副反応生成物は油層ｃ！＝シて浮く
ので、それを捕集し、常法の単離、精製を行ってＩＢ４
８２ＰＺを得る。In the present invention, produced water is fixed in the form of boric acid, so
No special pressure reduction is required, and the reaction is completed in 1 to 2 hours by heating at 250-350'C. If the reaction mixture is neutralized with an aqueous alkali (e.g. caustic or ammonia) solution, the mineral acid will be transferred to the aqueous solution and 1I34B2PZ
, unreacted 2PZ and side reaction products are in the oil layer c! = Since it floats, it is collected and isolated and purified by conventional methods to obtain IB4.
Obtain 82 PZ.
本反応の副反応生成物は２−フェニル−４，５ジー＼ン
ジルイミダヅール（以下４８５Ｂ２ＰＺと略称する）及
び２−フェニル−４−ベンジルイミダゾールであるが、
それらの生成尾は僅かで副次的なものにＣ２か過ぎない
。The side reaction products of this reaction are 2-phenyl-4,5-benzylimidazole (hereinafter abbreviated as 485B2PZ) and 2-phenyl-4-benzylimidazole,
Their production tails are small and are only secondary to C2.
本発明の方法によってえられるｌＢ４Ｂ２ＰＺＮＭＲ（
ＣＤＣ１３） ： δニア、５１，７．３５，７．３
０，７゜０６．ｍ、１５１１；６゜５４．Ｓ、 １１１
；５．１１．Ｓ、２１１；３．９９．Ｓ、２１１Ｍａｓ
ｓ（ｍ／ｅ）： ３２４（Ｍ” ）、３２３，２４７，
２３３，２０５，１７９，１７８゜１５７ 、１４９．
１４８．１３０．１０５．１０３．９１ 、７８．７７
゜６７．６５５５，５４，５３，５２．５１，５０，４
３．４１．３９実施例１〜６
表１に示す各出発原料の各所定量及び各反応条件による
反応を行ない、得られた反応混合物をＮ ａ叶で中和、
水洗、乾燥後、ＴＬＣを検し７た。結果を表２に示す。lB4B2PZNMR obtained by the method of the present invention (
CDC13): δ near, 51, 7.35, 7.3
0.7°06. m, 1511; 6°54. S, 111
;5.11. S, 211; 3.99. S, 211 Mas
s(m/e): 324(M”), 323,247,
233, 205, 179, 178°157, 149.
148.130.105.103.91, 78.77
゜67.6555, 54, 53, 52.51, 50, 4
3.41.39 Examples 1 to 6 Reactions were carried out using the predetermined amounts of each starting material and each reaction condition shown in Table 1, and the resulting reaction mixture was neutralized with Na-Ko.
After washing with water and drying, TLC was performed. The results are shown in Table 2.
なおＴＩ、０の展開には、シリカゲルＧとクロロホルム
／メタノール−９： １ｖｏ１．を、発色にはコードを
用いた。ＩＢ２ＰＺのｌｉｔ’は０．７５−０．７９．
２ＰＺのＲｆは０．３６〜０．４０． Ｉ Ｂ ４
８２ Ｐ Ｚ ノＲｆは０゜８５〜０．８８ ２−フェ
ニル−４−ペンジルイミタソールのＲｆは０．５８〜０
．６９及び２−フェニル−４，５−ジベンジルイミダゾ
ールのそれは０．７５〜０．７９である。Note that for the development of TI, 0, silica gel G and chloroform/methanol-9: 1vol. A code was used for coloring. The lit' of IB2PZ is 0.75-0.79.
Rf of 2PZ is 0.36 to 0.40. I B 4
82 P Z Rf is 0°85-0.88 Rf of 2-phenyl-4-penzylimitasol is 0.58-0
．． 69 and that of 2-phenyl-4,5-dibenzylimidazole is 0.75-0.79.
表１
表２ ＴＬＣの結果
、中、小、微により、またスポットの発色強度を強１弱
、微により行った。Table 1 Table 2 The TLC results were categorized as medium, small, and fine, and the coloring intensity of the spot was graded as strong, 1 weak, and fine.
実施例７
２ Ｐ ＺＯ，１３モル（１８，７ｇ） 、正リン酸０
．１３モル（１２、７ｇ）及びトリベンジルボレー１−
０．１３モル（４２，９ｇ）の３者を常圧下２８０’Ｃ
で１時間加熱したのち、その温度で反応系を３０分間５
ｍｍ１１ｇの減圧に付し、ついで内容物を水酸化ナト
リウムメタノール溶液で中和し、メタノールを留去した
残留物を水洗したのち、それを減圧蒸留に付し、粗ｌ８
４Ｂ２ＰＺ （ｂｐｔ ２００〜２５５°Ｃ）を０．０
５２モル（１７，０ｇ） （４０モル％収率）得た。ま
た副反応物としてｂｐｓ１６２〜１７５°Ｃの留分（粗
Ｉ Ｂ ２ Ｐ Ｚ ） １４．３ｇ（４６モル％収率
）を得た。Example 7 2 PZO, 13 mol (18.7 g), orthophosphoric acid 0
．． 13 moles (12,7 g) and tribenzylboley 1-
0.13 mol (42.9 g) of the three components were heated at 280'C under normal pressure.
After heating for 1 hour, the reaction system was heated at that temperature for 30 minutes.
The contents were then neutralized with a methanol solution of sodium hydroxide, the methanol was distilled off, the residue was washed with water, and then subjected to vacuum distillation to give a rough solution of 18 g.
4B2PZ (bpt 200-255°C) 0.0
52 mol (17.0 g) (40 mol% yield) was obtained. In addition, 14.3 g (46 mol % yield) of a fraction (crude I B 2 P Z ) having a bps of 162 to 175°C was obtained as a side reaction product.
実施例８
１８２Ｐ２０．２モル（４６，８ｇ） 、正リン酸０．
２モル（１９，６ｇ）及びトリベンジル−ボレート０．
２モル（６６，０ｇ）の３者を常圧下３３０〜３５０°
Ｃで３時間加熱したのち、内容物を水酸化ナトリウムメ
タノール溶液で中和し、メタノールを留去したのち残留
物を水洗し、被水洗物のＴＬＣを検した結果は次のとお
りであった。ＩＢ４８２ＰＺ （大・強）。Example 8 182P 20.2 mol (46.8 g), orthophosphoric acid 0.
2 mol (19.6 g) and 0.3 mol (19.6 g) of tribenzyl-borate.
2 moles (66.0 g) of the three components were heated at 330 to 350° under normal pressure.
After heating at C for 3 hours, the contents were neutralized with a methanol solution of sodium hydroxide, the methanol was distilled off, the residue was washed with water, and the washed material was analyzed by TLC, and the results were as follows. IB482PZ (large/strong).
２ＰＺ （）］い弱）、ＩＢ２ＰＺ（中・弱）、４８５
８２ＰＺ （大・強）。2PZ ()] weak), IB2PZ (medium/weak), 485
82PZ (large/strong).
また、被水洗物を減圧蒸留に付し、粗ｌ８４Ｂ２ Ｐ
Ｚ （ｂｐｓ ２４５〜２８５°Ｃ）を０．５６モル（
２８モル％収率）得た。副反応物としてｂｐｚｓ〜２５
５ ’Ｃの留分（２ＰＺ、ＩＢ２ＰＺ及び２Ｐ４ＢＺの
混合物）１０．０ｇとＥｌｐ５２８５〜３２５°Ｃの留
分（ＩＢ４８２ＰＺと４８５Ｂ２ＰＺの混合物）を得た
。In addition, the washed material was subjected to vacuum distillation to obtain crude l84B2P
Z (bps 245-285°C) at 0.56 mol (
28 mol% yield) was obtained. bpzs~25 as a side reaction product
10.0 g of a 5'C fraction (a mixture of 2PZ, IB2PZ and 2P4BZ) and an Elp 5285-325°C fraction (a mixture of IB482PZ and 485B2PZ) were obtained.
手続補正書 昭和６３年８月３０日Procedural amendment August 30, 1986
Claims (2)
あるいは鉱酸塩の共存下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１，４（５）−ジベンジル−２−フェニルイ
ミダゾールの合成方法。 〔但し、鉱酸は塩化水素、臭化水素、沃化水素、正リン
酸、亜リン酸、次リン酸、次亜リン酸、ピロリン酸、ト
リメタリン酸あるいはテトラメタリン酸であり、鉱酸発
生剤はオキシハロゲン化リン、ハロゲン化リン、無水リ
ン酸あるいは無水亜リン酸であり、また鉱酸塩は正リン
酸、亜リン酸、次リン酸、次亜リン酸、ピロリン酸、ト
リメタリン酸あるいはテトラメタリン酸のアンモニウム
塩、ナトリウム塩、カリウム塩、カルシウム塩、バリウ
ム塩あるいはマグネシウム塩である。〕(1) 2-Phenylimidazole and tribenzyl-borate represented by the structural formula ▲Mathematical formula, chemical formula, table, etc.▼ are reacted by heating in the presence of a mineral acid, a mineral acid generator, or a mineral salt, and then neutralized with an alkali. A method for synthesizing 1,4(5)-dibenzyl-2-phenylimidazole, which is represented by the structural formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. [However, mineral acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, orthophosphoric acid, phosphorous acid, hypophosphoric acid, hypophosphorous acid, pyrophosphoric acid, trimetaphosphoric acid, or tetrametaphosphoric acid, and mineral acid generators is phosphorus oxyhalide, phosphorus halide, phosphoric anhydride or phosphorous anhydride, and mineral salts are orthophosphoric acid, phosphorous acid, hypophosphorous acid, hypophosphorous acid, pyrophosphoric acid, trimetaphosphoric acid or tetraphosphoric acid. Ammonium, sodium, potassium, calcium, barium or magnesium salts of metaphosphoric acid. ]
トリベンジル−ボレートを鉱酸、鉱酸発生剤あるいは鉱
酸塩の共存下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１，４（５）−ジベンジル−２−フェ
ニルイミダゾールの合成方法。 〔但し、鉱酸、鉱酸発生剤あるいは鉱酸塩は前記と同様
である。〕(2) After heating and reacting 1-benzyl-2-phenylimidazole and tribenzyl-borate represented by the structural formula ▲numerical formula, chemical formula, table, etc. in the presence of a mineral acid, a mineral acid generator, or a mineral salt. A method for synthesizing 1,4(5)-dibenzyl-2-phenylimidazole, which comprises neutralizing with an alkali. [However, the mineral acid, mineral acid generator, or mineral salt is the same as above. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18127888A JPH0232062A (en) | 1988-07-19 | 1988-07-19 | Synthesis of 1,4(5)-dibenzyl-2-phenylimidazole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18127888A JPH0232062A (en) | 1988-07-19 | 1988-07-19 | Synthesis of 1,4(5)-dibenzyl-2-phenylimidazole |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0232062A true JPH0232062A (en) | 1990-02-01 |
Family
ID=16097899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18127888A Pending JPH0232062A (en) | 1988-07-19 | 1988-07-19 | Synthesis of 1,4(5)-dibenzyl-2-phenylimidazole |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0232062A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8342231B2 (en) | 2010-12-16 | 2013-01-01 | Kobe Steel, Ltd. | Cast strip withdrawing apparatus for continuous casting facility |
| US8387681B2 (en) | 2009-12-28 | 2013-03-05 | Kobe Steel, Ltd. | Strand guiding apparatus for continuous casting equipment |
-
1988
- 1988-07-19 JP JP18127888A patent/JPH0232062A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8387681B2 (en) | 2009-12-28 | 2013-03-05 | Kobe Steel, Ltd. | Strand guiding apparatus for continuous casting equipment |
| US8342231B2 (en) | 2010-12-16 | 2013-01-01 | Kobe Steel, Ltd. | Cast strip withdrawing apparatus for continuous casting facility |
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