JPH0641035A - Acetylene bromide compounds - Google Patents
Acetylene bromide compoundsInfo
- Publication number
- JPH0641035A JPH0641035A JP3037835A JP3783591A JPH0641035A JP H0641035 A JPH0641035 A JP H0641035A JP 3037835 A JP3037835 A JP 3037835A JP 3783591 A JP3783591 A JP 3783591A JP H0641035 A JPH0641035 A JP H0641035A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- acetylene
- brominated
- group
- chemical
- 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
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Indole Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pyrrole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、臭化アセチレン化合物
に関するものである。FIELD OF THE INVENTION The present invention relates to an acetylene bromide compound.
【０００２】[0002]
【従来の技術】従来よりアセチレン、及びジアセチレン
は架橋基として注目され、近年では、付加硬化型の樹脂
等に利用されつつある。例えばＴｈｅｒｍｉｄ（Ｇｕｌ
ｆｏｉｌ Ｃｈｅｍ）である。また、ジアセチレン基を
架橋基として、固相重合によるトポケミカル反応を用い
た単結晶ポリマーの合成が近年注目されており、この手
法を用いて種々の高弾性率を有する高結晶性高分子の開
発が試みられている。2. Description of the Related Art Acetylene and diacetylene have hitherto attracted attention as cross-linking groups, and in recent years, they are being used in addition-curable resins and the like. For example, Thermid (Gul
(Foil Chem). In addition, the synthesis of single-crystal polymers using a topochemical reaction by solid-state polymerization with a diacetylene group as a cross-linking group has attracted attention in recent years, and the development of highly crystalline polymers with various high elastic moduli using this technique Is being attempted.
【０００３】例えば、「有機非線形光学材料、シーエム
シー（１９８５）、マクロモレキユル ケミストリー
第１３４巻、２１９頁（１９７０）、ジャーナル オブ
ポリマー サイエンス 第Ｂ９巻、１３３頁（１９７
１）、ジャーナル オブ ポリマー サイエンス、ポリ
マー フイジクス エディション 第１２巻、１５１１
頁（１９７４）」しかしながら、これまでに研究された
ジアセチレン化合物は、そのほとんどがジアセチレン基
以外の架橋性基を有さず、またわずかに合成された例に
おいても、ＧＬＡＳＥＲカップリング法による対称系化
合物に限定されていた。For example, "Organic Nonlinear Optical Materials, CMC (1985), Macromolecules Chemistry"
134, 219 (1970), Journal of Polymer Science, B9, 133 (197)
1), Journal of Polymer Science, Polymer Physics Edition, Volume 12, 1511
However, most of the diacetylene compounds studied so far do not have a crosslinkable group other than the diacetylene group, and even in the slightly synthesized example, the symmetry by the GLASER coupling method is obtained. It was limited to system compounds.
【０００４】一方架橋成形により等方的高剛性体を得る
為には、素材分子中の架橋基の密度を飛躍的に向上させ
る事が必要である。そこで本発明者らは、ＣＡＤＩＯＴ
−ＣＨＯＤＫＩＥＷＩＣＺ カップリング反応を始め種
々の反応手法により、同一分子内に複数のジアセチレン
基や架橋性基を持たせた化合物を合成するための中間体
について鋭意研究した結果、本発明に到達した。On the other hand, in order to obtain an isotropic high-rigidity material by cross-linking molding, it is necessary to dramatically improve the density of cross-linking groups in the raw material molecule. Therefore, the present inventors
The present invention has been accomplished as a result of earnest research on an intermediate for synthesizing a compound having a plurality of diacetylene groups or a crosslinkable group in the same molecule by various reaction methods including the —CHODKIEWICZ coupling reaction.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、等方
的高剛性体を与えうるジアセチレン化合物の合成やアミ
ド等の化学修飾に有用な中間体としてのアセチレン系化
合物を提供することにある。DISCLOSURE OF THE INVENTION An object of the present invention is to provide an acetylene compound as an intermediate useful for the synthesis of a diacetylene compound capable of providing an isotropic and highly rigid body and for the chemical modification of amides. is there.
【０００６】[0006]
【課題を解決するための手段】すなわち本発明は、化２
式で表わされる臭化アセチレン化合物である。Means for Solving the Problems That is, the present invention provides
It is an acetylene bromide compound represented by the formula.
【０００７】[0007]
【化２】 [Chemical 2]
【０００８】（式中、Ｒ2 −は不飽和結合を有する炭化
水素基、−Ｘ−は炭素数が１から１３の有機基であ
る。）本発明の臭化アセチレン化合物は、化２式で示さ
れる様に不飽和結合を有する炭化水素基を持ち、末端の
エチニル基がハロゲン化された化合物である。この様な
化学構造のため、末端にエチニル基を持った化合物と容
易に反応し、一分子中に不飽和基とジアセチレン基を持
った化合物を与える。(In the formula, R 2 -is a hydrocarbon group having an unsaturated bond, and -X- is an organic group having 1 to 13 carbon atoms.) The acetylene bromide compound of the present invention has the formula As shown, the compound has a hydrocarbon group having an unsaturated bond, and the terminal ethynyl group is a halogenated compound. Due to such a chemical structure, it easily reacts with a compound having an ethynyl group at the terminal to give a compound having an unsaturated group and a diacetylene group in one molecule.
【０００９】本発明において、Ｒ2 −は不飽和結合を有
する炭化水素基であり、炭素数に特に限定はないが、好
ましくは２５以下であり、炭素、水素以外に窒素、酸
素、硫黄等が構成原子として入っていても良く、又、ハ
ロゲン、ニトロ基、シアノ基、カルボニル基、カルボキ
シル基、水酸基、エーテル等で置換されていても良い。
例えば、化３などがある。In the present invention, R 2 − is a hydrocarbon group having an unsaturated bond, and the number of carbon atoms is not particularly limited, but is preferably 25 or less, and in addition to carbon and hydrogen, nitrogen, oxygen, sulfur and the like are included. It may be contained as a constituent atom, or may be substituted with halogen, nitro group, cyano group, carbonyl group, carboxyl group, hydroxyl group, ether or the like.
For example, there is a chemical formula 3.
【００１０】[0010]
【化３】 [Chemical 3]
【００１１】本発明において、−Ｘ−はアミド結合とエ
チニル基とを連結する基であり、炭素数が１から１３の
有機基である。−Ｘ−の例としては、例えば、化４及び
化５などである。In the present invention, -X- is a group connecting an amide bond and an ethynyl group, and is an organic group having 1 to 13 carbon atoms. Examples of -X- are Chemical formula 4 and Chemical formula 5, for example.
【００１２】[0012]
【化４】 [Chemical 4]
【００１３】[0013]
【化５】 [Chemical 5]
【００１４】これらが繰り返されたり、組み合されたり
しても良く、又、これらの炭化水素基が他の結合基で連
結されていてもよい。このような炭化水素基以外の他の
結合基としては、例えば、化６などであり、これらが組
み合さっていても、又、繰り返されていてもよい。These may be repeated or combined, and these hydrocarbon groups may be linked by another bonding group. Examples of the bonding group other than such a hydrocarbon group include, for example, Chemical formula 6 and the like, which may be combined or repeated.
【００１５】[0015]
【化６】 [Chemical 6]
【００１６】本発明の臭化アセチレン化合物を製造する
には、既知の有機化学反応を利用すれば容易に合成可能
である。例えば、Ｒ2 −ＣＯＯＨで表わされるカルボン
酸又はＲ2 −ＣＯＣｌで表わされる酸クロライドと化７
で表わされるアセチレン系アミノ化合物との脱水又は脱
塩化水素反応により化８で表わされるアセチレン系アミ
ド化合物を合成し、これをＮａＯＢｒと反応させ、化９
を合成する方法等がある。The acetylene bromide compound of the present invention can be easily produced by utilizing a known organic chemical reaction. For example, a carboxylic acid represented by R 2 —COOH or an acid chloride represented by R 2 —COCl
The acetylene-based amide compound represented by Chemical formula 8 was synthesized by dehydration or dehydrochlorination reaction with the acetylene-based amino compound represented by Chemical formula 9 and reacted with NaOBr.
There is a method of synthesizing.
【００１７】[0017]
【化７】 [Chemical 7]
【００１８】[0018]
【化８】 [Chemical 8]
【００１９】[0019]
【化９】 [Chemical 9]
【００２０】[0020]
【００２１】[0021]
【実施例１】３−シクロヘキセンカルボン酸０．２ｍｏ
ｌ（２５．２ｇ）とプロパルギルアミン０．２ｍｏｌ
（１１．０ｇ）をベンゼンに溶解し、還流下にて水を留
去し、その後、ベンゼンを濃縮し、黄白色物を得た。
（生成物Ａ） 次に、粉砕した氷２５ｇと１ＯＮ−ＮａＯＨ水溶液１５
ｍｌを入れた系内に、臭素０．１１５ｍｏｌ（２．９ｍ
ｌ）を入れ、均一になった後、上記生成物Ａ０．０５ｍ
ｏｌのテトラヒドロラン溶液を添加した。その後一定時
間の反応を続け、ＮＨ4 Ｃｌ ０．０７ｍｏｌ（３．８
ｇ）水溶液を入れた後、反応を停止した。その後系を濃
縮し、水洗、濾過を繰り返した後、減圧乾燥し、黄色粉
末を得た。（理論値の４３．６％） （分析結果） [Example 1] 3-cyclohexenecarboxylic acid 0.2mo
1 (25.2 g) and propargylamine 0.2 mol
(11.0 g) was dissolved in benzene, water was distilled off under reflux, and then benzene was concentrated to obtain a yellowish white product.
(Product A) Next, 25 g of crushed ice and 1 ON-NaOH aqueous solution 15
In the system containing ml, 0.115 mol of bromine (2.9 m
l) was added and after homogenization, the product A 0.05 m
ol of tetrahydrolane was added. After that, the reaction was continued for a certain period of time, and NH 4 Cl 0.07 mol (3.8
g) After adding the aqueous solution, the reaction was stopped. After that, the system was concentrated, washed with water and filtered repeatedly, and then dried under reduced pressure to obtain a yellow powder. (43.6% of theoretical value) (Analysis result)
【００２２】[0022]
【実施例２】アクリロイルクロライド０．２ｍｏｌ（１
８．０９ｇ）をクロロホルムに溶解した（Ａ液）。プロ
パルギルアミン０．２ｍｏｌ（１１．０ｇ）とＮａＯＨ
０．２ｍｏｌ（８．０ｇ）を水に溶かした（Ｂ液）。
次にＡ液にＢ液を氷冷下に徐々に加え、しばらく攪拌す
る。反応後、水とクロロホルムを分離し、水層をさらに
クロロホルム抽出し、クロロホルム溶液をボウ硝にて乾
燥後、濃縮した。その後実施例１と同様にハロゲン化を
行なった。（理論値の５３．６％） （分析結果） Example 2 Acryloyl chloride 0.2 mol (1
8.09 g) was dissolved in chloroform (solution A). 0.2 mol (11.0 g) of propargylamine and NaOH
0.2 mol (8.0 g) was dissolved in water (solution B).
Next, solution B is gradually added to solution A under ice cooling and stirred for a while. After the reaction, water and chloroform were separated, the aqueous layer was further extracted with chloroform, and the chloroform solution was dried over Glauber's salt and concentrated. After that, halogenation was carried out in the same manner as in Example 1. (53.6% of theoretical value) (Analysis result)
【００２３】[0023]
【化１０】 [Chemical 10]
【００２４】[0024]
【発明の効果】本発明の臭化アセチレン化合物は、末端
の臭素の反応性を利用し、例えばＣＡＤＩＯＴ−ＣＨＯ
ＤＫＩＥＷＩＣＺカップリング反応等によりこれまでに
知られていない不飽和結合を合わせ持つ新しいタイプの
ジアセチレン化合物を合成するのにきわめて重要な中間
体となり、そのジアセチレン化合物の架橋物は、特に良
好な耐熱性を示し、かつ等方的高剛性体を与える。The acetylene bromide compound of the present invention utilizes the reactivity of terminal bromine, and for example, CADIOT-CHO.
It becomes an extremely important intermediate for synthesizing a new type of diacetylene compound having an unknown unsaturated bond by the DKIEWICZ coupling reaction and the like, and the crosslinked product of the diacetylene compound has particularly good heat resistance. It shows the property and gives an isotropic high rigidity body.
Claims (1)
ン化合物。臭化アセチレン化合物。 【化１】 （式中、Ｒ2 −は不飽和結合を有する炭化水素基、−Ｘ
−は炭素数が１から１３の有機基である。）1. A acetylene bromide compound represented by the following chemical formula 1. Acetylene bromide compound. [Chemical 1] (In the formula, R 2 — is a hydrocarbon group having an unsaturated bond, —X
-Is an organic group having 1 to 13 carbon atoms. )
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61110906A JPS62267262A (en) | 1986-05-16 | 1986-05-16 | Halogenated acetylene compound |
| JP3037835A JPH0688954B2 (en) | 1986-05-16 | 1991-02-08 | Acetylene bromide compound |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61110906A JPS62267262A (en) | 1986-05-16 | 1986-05-16 | Halogenated acetylene compound |
| JP3037835A JPH0688954B2 (en) | 1986-05-16 | 1991-02-08 | Acetylene bromide compound |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61110906A Division JPS62267262A (en) | 1986-05-16 | 1986-05-16 | Halogenated acetylene compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0641035A true JPH0641035A (en) | 1994-02-15 |
| JPH0688954B2 JPH0688954B2 (en) | 1994-11-09 |
Family
ID=26376982
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61110906A Granted JPS62267262A (en) | 1986-05-16 | 1986-05-16 | Halogenated acetylene compound |
| JP3037835A Expired - Lifetime JPH0688954B2 (en) | 1986-05-16 | 1991-02-08 | Acetylene bromide compound |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61110906A Granted JPS62267262A (en) | 1986-05-16 | 1986-05-16 | Halogenated acetylene compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JPS62267262A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH635828A5 (en) * | 1978-08-30 | 1983-04-29 | Ciba Geigy Ag | N-SUBSTITUTED IMIDES AND BISIMIDS. |
-
1986
- 1986-05-16 JP JP61110906A patent/JPS62267262A/en active Granted
-
1991
- 1991-02-08 JP JP3037835A patent/JPH0688954B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0372213B2 (en) | 1991-11-18 |
| JPH0688954B2 (en) | 1994-11-09 |
| JPS62267262A (en) | 1987-11-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |