JPH0643409B2 - Glycidyl compound incorporation complex - Google Patents
Glycidyl compound incorporation complexInfo
- Publication number
- JPH0643409B2 JPH0643409B2 JP23068885A JP23068885A JPH0643409B2 JP H0643409 B2 JPH0643409 B2 JP H0643409B2 JP 23068885 A JP23068885 A JP 23068885A JP 23068885 A JP23068885 A JP 23068885A JP H0643409 B2 JPH0643409 B2 JP H0643409B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- glycidyl
- compound
- complex
- glycidyl compound
- 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 - Fee Related
Links
- -1 Glycidyl compound Chemical class 0.000 title claims description 15
- 238000010348 incorporation Methods 0.000 title description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- WXTPRAZNOXQAFY-UHFFFAOYSA-N 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C#CC#CC(O)(C=1C=CC=CC=1)C1=CC=CC=C1 WXTPRAZNOXQAFY-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-UHFFFAOYSA-N 0.000 description 1
- KDSVXIGJVLFKOE-UHFFFAOYSA-N 2-(ethylsulfanylmethyl)oxirane Chemical compound CCSCC1CO1 KDSVXIGJVLFKOE-UHFFFAOYSA-N 0.000 description 1
- QYYCPWLLBSSFBW-UHFFFAOYSA-N 2-(naphthalen-1-yloxymethyl)oxirane Chemical compound C=1C=CC2=CC=CC=C2C=1OCC1CO1 QYYCPWLLBSSFBW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- URYGFDRDSYOMTO-UHFFFAOYSA-N oxiran-2-ylmethyl 2-naphthalen-1-yloxyacetate Chemical compound C=1C=CC2=CC=CC=C2C=1OCC(=O)OCC1CO1 URYGFDRDSYOMTO-UHFFFAOYSA-N 0.000 description 1
- JUVGLPRIQOJMIR-UHFFFAOYSA-N oxiran-2-ylmethyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OCC1CO1 JUVGLPRIQOJMIR-UHFFFAOYSA-N 0.000 description 1
- XRQKARZTFMEBBY-UHFFFAOYSA-N oxiran-2-ylmethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1CO1 XRQKARZTFMEBBY-UHFFFAOYSA-N 0.000 description 1
- YLNSNVGRSIOCEU-UHFFFAOYSA-N oxiran-2-ylmethyl butanoate Chemical compound CCCC(=O)OCC1CO1 YLNSNVGRSIOCEU-UHFFFAOYSA-N 0.000 description 1
- YEARBAZDKOUUAM-UHFFFAOYSA-N oxiran-2-ylmethyl naphthalene-1-carboxylate Chemical compound C=1C=CC2=CC=CC=C2C=1C(=O)OCC1CO1 YEARBAZDKOUUAM-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- QNAJAJLBHMMOJB-UHFFFAOYSA-N oxiran-2-ylmethyl propanoate Chemical compound CCC(=O)OCC1CO1 QNAJAJLBHMMOJB-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 （発明の技術分野） 本発明はグリシジル化合物を取り込んで生成する、安定
であると共に容易にグリシジル化合物を放出できるグリ
シジル化合物取り込み錯体（いわゆる包接化合物）に関
する。TECHNICAL FIELD OF THE INVENTION The present invention relates to a glycidyl compound-incorporating complex (so-called clathrate compound), which is formed by incorporating a glycidyl compound, is stable and can easily release the glycidyl compound.
（従来技術） 有機化合物間の取り込み錯体は既にいくつか知られてお
り、これらの錯体については取り込まれた化合物（ゲス
ト(guest)化合物）の反応性が自由な時の状態の反応性
と異なることに興味がもたれている。また一方、化合物
の精製単離を目的としてこの種の錯体を利用しようとす
る試みもある。(Prior Art) Several incorporation complexes between organic compounds are already known, and the reactivity of the incorporated compound (guest compound) is different from the reactivity of the complex when it is free. Interested in. On the other hand, there are also attempts to utilize this type of complex for the purpose of purifying and isolating the compound.
本発明者らは1,1,6,6−テトラフェニルヘキサ−2,4−ジ
イン−1,6−ジオールをホスト(host)化合物として種々
の化合物と結晶性の錯体を形成させたことを既に報告し
た(Tetrahedron Lett.1968,3695、1981,22,3865、J.Chem.
Soc.Jpn 1983,239)。しかしながら、本発明のようなフ
ェノール誘導体とグリシジル化合物との組合せによる取
込み錯体については全く知られていない。グリシジル化
合物は有機合成化学上重要な中間体であり、また高分子
合成化学においても重要なモノマーである。これらのグ
リシジル化合物は種類によっては高純度で得ることは必
ずしも容易ではない。またグリシジル化合物の重合反応
における取込み錯体の効果も新規なポリマーを製造する
上で非常に関心がもたれるところである。The present inventors have already shown that 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol was used as a host compound to form a crystalline complex with various compounds. Reported (Tetrahedron Lett. 1968, 3695, 1981, 22, 3865, J. Chem.
Soc. Jpn 1983, 239). However, the incorporation complex by the combination of the phenol derivative and the glycidyl compound as in the present invention is not known at all. Glycidyl compounds are important intermediates in synthetic organic chemistry and also important monomers in synthetic polymer chemistry. It is not always easy to obtain these glycidyl compounds with high purity depending on the kind. The effect of the incorporation complex on the polymerization reaction of the glycidyl compound is also of great interest in producing a new polymer.
（発明の目的） 本発明は有機合成化学上各種の応用が考えられる、特に
高純度の中間体もしくは重合用モノマーとしてのグリシ
ジル化合物を得るための、または新しい反応性を示す中
間体もしくは重合用モノマーとしての新規なグリシジル
化合物取り込み錯体を提供することを目的とする。(Object of the invention) The present invention is considered to have various applications in synthetic organic chemistry, particularly for obtaining a glycidyl compound as a high-purity intermediate or a monomer for polymerization, or an intermediate or a monomer for polymerization showing a new reactivity. An object of the present invention is to provide a novel glycidyl compound-incorporated complex as.
（発明の構成） 本発明は、下記一般式（Ｉ）で示されるグリシジル化合
物 （但し、（Ｉ）式において、Ｒは水素原子又はメチル基
を表わす。Ｘはヒドロキシ基，アルコキシ基，アシル
基，アシルオキシ基，アルコキシカルボニル基，フェノ
キシ基，Ｏ−メチルフェノキシ基，ナフトキシ基，シア
ノ基及びアルキルチオ基から選ばれる基又はハロゲン原
子を表わす。）と下記式（II）で示される1,1−ビス
（ｐ−ヒドロキシフェニル）−シクロヘキサン とによって形成されてなるグリシジル化合物取り込み錯
体である。(Structure of the Invention) The present invention provides a glycidyl compound represented by the following general formula (I). (In the formula (I), R represents a hydrogen atom or a methyl group. X represents a hydroxy group, an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a phenoxy group, an O-methylphenoxy group, a naphthoxy group, a cyano group. Group or a group selected from an alkylthio group or a halogen atom) and 1,1-bis (p-hydroxyphenyl) -cyclohexane represented by the following formula (II) It is a glycidyl compound incorporation complex formed by and.
本発明においてゲスト化合物となるグリシジル化合物と
しては、グリシドール，エピクロルヒドリン，エピブロ
モヒドリン，β−メチルエピクロルヒドリン，アリルグ
リシジルエーテル，ブチルグリシジルエーテル，フェニ
ルグリシジルエーテル，Ｏ−メチルフェニルグリシジル
エーテル，ナフチルグリシジルエーテル，酢酸グリシジ
ル，プロピオン酸グリシジル，酪酸グリシジル，安息香
酸グリシジル，ケイ皮酸グリシジル，アクリル酸グリシ
ジル，メタクリル酸グリシジル，ナフトエ酸グリシジ
ル，ナフトキシ酢酸グリシジル，エチルグリシジルチオ
エーテル，ω−エポキシ酪酸エチルなどが挙げられる。Examples of the glycidyl compound serving as a guest compound in the present invention include glycidol, epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, O-methylphenyl glycidyl ether, naphthyl glycidyl ether, acetic acid. Examples thereof include glycidyl, glycidyl propionate, glycidyl butyrate, glycidyl benzoate, glycidyl cinnamate, glycidyl acrylate, glycidyl methacrylate, glycidyl naphthoate, glycidyl naphthoxyacetate, ethyl glycidyl thioether, and ethyl ω-epoxybutyrate.
本発明においてホスト化合物となる（II）式化合物は既
に知られており、シクロヘキサンとフェノールを酸触媒
で縮合させることによって容易に製造できる［J.Am.Che
m.Soc.61 1785(1939)］。The compound of formula (II) which serves as a host compound in the present invention is already known, and can be easily produced by condensing cyclohexane and phenol with an acid catalyst [J. Am.
m.Soc.61 1785 (1939)].
本発明において（Ｉ）式化合物と（II）式化合物から錯
体を形成させるには、これら両者を直接混合してもよい
し、溶媒を用いて反応させてもよい。溶媒としては脂肪
族炭化水素類，芳香族炭化水素類，エーテル類の単独も
しくはこれらの混合物が適当である。反応温度や反応時
間は上記（Ｉ）式，（II）式の化合物の組合わせによっ
て異なるが、通常室温乃至溶媒の還流温度の範囲が適当
である。反応時間は錯体形成による沈澱によって容易に
定められる。In the present invention, in order to form a complex from the compound of formula (I) and the compound of formula (II), they may be mixed directly or may be reacted using a solvent. Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons and ethers, either alone or as a mixture thereof. The reaction temperature and the reaction time vary depending on the combination of the compounds of the above formulas (I) and (II), but usually a range of room temperature to the reflux temperature of the solvent is suitable. The reaction time is easily determined by precipitation due to complex formation.
錯体は使用する（Ｉ）式化合物と（II）式化合物の組合
わせによって異なるが、通常（Ｉ）式化合物と（II）式
化合物のモル比が３：１〜１：３の割合の化合物として
生成する。The complex varies depending on the combination of the formula compound (I) and the formula compound (II) used, but is usually a compound having a molar ratio of the formula compound (I) and the formula compound (II) of 3: 1 to 1: 3. To generate.
得られた錯体は固態結晶であり、これを再結晶によって
精製することが可能である。またこの錯体を加熱蒸溜、
極性溶媒による置換、クロマトグラフィーなどの手段に
よって分解させて特異な性質を有するグリシジル化合物
を取り出すこともできる。The obtained complex is a solid crystal and can be purified by recrystallization. Also, this complex is heated and distilled,
It is also possible to take out a glycidyl compound having a unique property by decomposing it by means such as substitution with a polar solvent or chromatography.
（発明の効果） 本発明の錯体は新規な化合物であり、安定性に優れると
共に通常の手段によって特異な性質をもった有用なグリ
シジル化合物を極めて容易に放出することができる。(Effects of the Invention) The complex of the present invention is a novel compound, which is extremely stable and can release a useful glycidyl compound having a unique property by an ordinary means very easily.
（実施例） 実施例１ 1,1−ビス（ｐ−ヒドロキシフェニル）−シクロヘキサ
ン2.0gをグリシドール20mlに加熱溶解し、その後室温で
12時間放置したところ無色針状結晶2,2gが析出した。こ
の結晶は融点175〜181℃で原料化合物のモル比が１：１
の錯体であることが確められた。Example 1 Example 1 2.0 g of 1,1-bis (p-hydroxyphenyl) -cyclohexane was dissolved by heating in 20 ml of glycidol, and then at room temperature.
When left for 12 hours, 2.2 g of colorless needle crystals were precipitated. This crystal has a melting point of 175 to 181 ° C and a molar ratio of raw material compounds of 1: 1.
It was confirmed to be a complex of
実施例２〜５ 表１に示すグリシジル化合物を用いた以外は実施例１と
同様にして錯体を製造した。なお、これらの錯体はいず
れも分解のため融点が不明確であった。Examples 2 to 5 Complexes were produced in the same manner as in Example 1 except that the glycidyl compound shown in Table 1 was used. The melting point of each of these complexes was unclear due to decomposition.
上記実施例１〜５によって得られた錯体の赤外線吸収ス
ペクトルを第１図〜第５図に示した。 The infrared absorption spectra of the complexes obtained in Examples 1 to 5 are shown in FIGS. 1 to 5.
第１図〜第５図はそれぞれ実施例１〜実施例５によって
得られた錯体の赤外線吸収スペクトルである。1 to 5 are infrared absorption spectra of the complexes obtained in Examples 1 to 5, respectively.
Claims (1)
合物と式（II）で示される１，１−ビス（ｐ−ヒドロキ
シフェニル）−シクロヘキサンとによって形成されてな
るグリシジル化合物取り込み錯体。 （但し、（Ｉ）式において、Ｒは水素原子又はメチル基
を表わす。Ｘはヒドロキシ基，アルコキシ基，アシル
基，アシルオキシ基，アルコキシカルボニル基，フェノ
キシ基，Ｏ−メチルフェノキシ基，ナフトキシ基，シア
ノ基及びアルキルチオ基から選ばれる基又はハロゲン原
子を表わす。）1. A glycidyl compound-incorporating complex formed by a glycidyl compound represented by the following general formula (I) and 1,1-bis (p-hydroxyphenyl) -cyclohexane represented by the formula (II). (In the formula (I), R represents a hydrogen atom or a methyl group. X represents a hydroxy group, an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a phenoxy group, an O-methylphenoxy group, a naphthoxy group, a cyano group. Represents a group or a halogen atom selected from a group and an alkylthio group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23068885A JPH0643409B2 (en) | 1985-10-16 | 1985-10-16 | Glycidyl compound incorporation complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23068885A JPH0643409B2 (en) | 1985-10-16 | 1985-10-16 | Glycidyl compound incorporation complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6289675A JPS6289675A (en) | 1987-04-24 |
| JPH0643409B2 true JPH0643409B2 (en) | 1994-06-08 |
Family
ID=16911750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23068885A Expired - Fee Related JPH0643409B2 (en) | 1985-10-16 | 1985-10-16 | Glycidyl compound incorporation complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0643409B2 (en) |
-
1985
- 1985-10-16 JP JP23068885A patent/JPH0643409B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6289675A (en) | 1987-04-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |