JPH01186852A - Amide group-containing diphenyldiacetylene - Google Patents
Amide group-containing diphenyldiacetyleneInfo
- Publication number
- JPH01186852A JPH01186852A JP696888A JP696888A JPH01186852A JP H01186852 A JPH01186852 A JP H01186852A JP 696888 A JP696888 A JP 696888A JP 696888 A JP696888 A JP 696888A JP H01186852 A JPH01186852 A JP H01186852A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- diacetylene
- catalyst
- amide
- 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
- HMQFJYLWNWIYKQ-UHFFFAOYSA-N 1,4-diphenylbutadiyne Chemical group C1=CC=CC=C1C#CC#CC1=CC=CC=C1 HMQFJYLWNWIYKQ-UHFFFAOYSA-N 0.000 title claims description 8
- 125000003368 amide group Chemical group 0.000 title description 10
- 125000000962 organic group Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000009257 reactivity Effects 0.000 abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010949 copper Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 229920000015 polydiacetylene Polymers 0.000 abstract description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001868 cobalt Chemical class 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 abstract 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 229940045803 cuprous chloride Drugs 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000003863 metallic catalyst Substances 0.000 abstract 1
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 9
- 150000001408 amides Chemical class 0.000 description 8
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004455 differential thermal analysis Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- -1 ethynyl hydrogen, hypochlorite alkali salt Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000002140 halogenating effect Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UPTXFUAPHPIBJO-UHFFFAOYSA-N C(C)(=O)[P]C(C)=O Chemical class C(C)(=O)[P]C(C)=O UPTXFUAPHPIBJO-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 238000007096 Glaser coupling reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、アミド基含有ジフェニルジアセチレンに関す
るものであり、更に詳しくは、耐熱性、反応性及び結晶
性の高いアミド基台をジフェニルジアセチレンに関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to diphenyl diacetylene containing an amide group, and more particularly to diphenyl diacetylene having an amide base having high heat resistance, reactivity and crystallinity.
近年、固相重合によるトポケミカル反応による高分子単
結晶の合成は、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材料の開発がおこなわれている。In recent years, the synthesis of polymer single crystals by topochemical reactions through solid-state polymerization has attracted attention, and various materials with high elastic modulus are being developed using this method.
本発明者もまた、種々の機能性ジアセチレン化合物を合
成、開発してきた。The present inventor has also synthesized and developed various functional diacetylene compounds.
〔発明が解決しようとしている問題点〕しかしながら、
これまでに合成されてきたジアセチ・リン化合物の多（
は、ジアセチレン基の隣に−ＣＨ，−を有する物が多（
、そのために得られたポリマーは、耐熱性は低い。[Problem that the invention is trying to solve] However,
Many of the diacetyl phosphorus compounds that have been synthesized so far (
Many of them have -CH,- next to the diacetylene group (
, the resulting polymer has low heat resistance.
一方、耐熱性の高い芳香族を有するアミド基含有ジアセ
チレン化合物
も知られているが、ポリマーへの転化率が低かっそこで
本発明者らは、ジアセチレン基の反応性を落とさずに耐
熱性を上げる方法を検討した。耐熱性の点から見て、ジ
フェニルジアセチレン骨格、ジアセチレン基を反応しや
すい分子−配列にさせるアミド基の組合わせは好ましい
が、フェニル基がはいれば、ジアセチレン基の反応性は
、どうしても低下してしまう。そこで、本発明者らは、
電子吸引基であるカルボニル基側がベンゼン環についた
アミド基を導入することで、ジアセチレン基の反応性を
高める可能性を見出した。On the other hand, amide group-containing diacetylene compounds with aromatic groups that have high heat resistance are also known, but the conversion rate to polymers is low. We considered ways to raise it. From the viewpoint of heat resistance, a combination of a diphenyl diacetylene skeleton and an amide group that makes the diacetylene group form a molecular arrangement that makes it easy to react is preferable, but if a phenyl group is present, the reactivity of the diacetylene group will inevitably decrease. It will drop. Therefore, the present inventors
We discovered the possibility of increasing the reactivity of diacetylene groups by introducing an amide group whose carbonyl group, which is an electron-withdrawing group, is attached to a benzene ring.
更に、凝集性の向上、置換基の種類等、耐熱性、反応性
に係わる因子を鋭意検討の結果、本発明に到達した。Furthermore, as a result of extensive studies on factors related to heat resistance and reactivity, such as improvement in aggregation properties and types of substituents, the present invention was achieved.
すなわち本発明は、
構造式が、
（ここで、Ｒ，Ｒ’は炭素数が１から２０までの一価の
有機基を示し、ｘ、ｘ’は水素原子、ハロゲン原子、炭
素数が１から６までの一価の有機基を示す、）
を有するアミド基含有ジフェニルジアセチレンを提供す
るものである。That is, in the present invention, the structural formula is amide group-containing diphenyl diacetylenes having up to 6 monovalent organic groups).
本発明において、Ｒ，Ｒ’は、炭素数が１から２０まで
の一価の有機基を示し、その具体例としては、ＣＨｓ
、ＣｔＨｓ 、ＣｔＨｓ 、Ｃ４Ｈ９。In the present invention, R and R' represent monovalent organic groups having 1 to 20 carbon atoms, and specific examples thereof include CHs
, CtHs, CtHs, C4H9.
ＣｓＨ＋＋＋ ＣｔｏＨｚｔ＋ Ｃｔｚ−Ｈｚｓ＋れる
。また、これらの有機基１’２．Ｒ’の水素原子のいく
つかが、ハロゲン原子、ニトロ基、水酸基、シアノ基、
カルボニル基、アミノ基、アミド基、エステル基、アル
コキシル基等に置換されていても良い。CsH+++ CtoHzt+ Ctz-Hzs+. Moreover, these organic groups 1'2. Some of the hydrogen atoms of R' are halogen atoms, nitro groups, hydroxyl groups, cyano groups,
It may be substituted with a carbonyl group, an amino group, an amide group, an ester group, an alkoxyl group, etc.
これらのＲ，Ｒ’のうち、ジアセチレン基の反応性を高
めるためには、ＣＨｓ 、ＣｚＨｓ 。Among these R and R', in order to increase the reactivity of the diacetylene group, CHs and CzHs are used.
また、本発明のアミド基含有ジフェニルジアセチレンに
おいて、Ｒ，Ｒ’は、同種、異種でもよい、同種の場合
は、合成のしやすさ、結晶性の高さ等に優れており、異
種の場合には、合成はしにく（なるもののジアセチレン
基の電荷密度を片寄らせるために生まれる電気的又は光
学的特性から好ましく、また液晶形成の点からも興味が
持たれる。In addition, in the amide group-containing diphenyl diacetylene of the present invention, R and R' may be the same type or different types; Although it is difficult to synthesize, it is preferable because of the electrical or optical properties created by biasing the charge density of the diacetylene group, and it is also interesting from the point of view of liquid crystal formation.
本発明において、ｘ、ｘ’は水素原子、ハロゲン原子、
炭素数が１から６までの一価の有機基を示し、その具体
例を示すならば、Ｈ，ＣＩ、Ｂｒ。In the present invention, x and x' are hydrogen atoms, halogen atoms,
Specific examples of monovalent organic groups having 1 to 6 carbon atoms include H, CI, and Br.
１、Ｃ）Ｉｓ 、ＣｔＨｓ 、Ｃ５Ｈｑ 、Ｃ４Ｈ９。1, C) Is, CtHs, C5Hq, C4H9.
これらのｘ、ｘ’のうち、水素結合での凝集性向上によ
るジアセチレン基の反応性アンプからＨが特に好ましい
。Among these x and x', H is particularly preferable because it increases the reactivity of the diacetylene group due to improved cohesiveness due to hydrogen bonding.
本発明のアミド基含有ジフェニルジアセチレンの合成方
法としては、Ｒ，Ｒ’が同一である時、のような金属触
媒と酸素ガスを用いて酸化カップリングさせることによ
り合成できる。（グレイサー カップリング）
一方、ＲとＲ′が同一でない時
Ｏ
をハロゲン化してから、酢酸銅のような金属触媒クロス
カップリング反応させることにより、合成できる。As a method for synthesizing the amide group-containing diphenyl diacetylene of the present invention, when R and R' are the same, it can be synthesized by oxidative coupling using a metal catalyst such as the following and oxygen gas. (Glaser Coupling) On the other hand, when R and R' are not the same, it can be synthesized by halogenating O and then carrying out a cross-coupling reaction with a metal catalyst such as copper acetate.
上記合成例において、酸化カップリング反応の触媒とし
ては、銅、マンガン、コバルト塩を用いることができ、
必要に応じて、３級アミン、オキシム等の助触媒を共存
させてもよい。触媒としてはＣｕＣ１，ＣｕＣ１ｔ 、
Ｃｕ Ｉｔ 、Ｃｕ （００ＣＣＩ（３）意１Ｍｎ Ｃ
１ｚ、 Ｍｎ ｃｏｄ、 ＣＯＣｉｔなどをもちいるこ
とができる。In the above synthesis example, copper, manganese, and cobalt salts can be used as catalysts for the oxidative coupling reaction,
If necessary, a co-catalyst such as a tertiary amine or oxime may be present. As a catalyst, CuC1, CuC1t,
Cu It, Cu (00CCI(3) meaning 1Mn C
1z, Mn cod, COCit, etc. can be used.
上記合成例の酸化カンプリング反応において用いる金属
触媒のモル数は、基質に対し、０．０１当量から１当量
、酸素の流量は、基質１モルあたりｌＯ〜１０００ｓｄ
／ｍｉｎが好ましい。この反応に用いる溶媒としては、
例えばピリジン、アセトン、メタノール等があげられ、
他の第二の溶媒を共存させてもよい。反応時間、温度に
ついては制限はないが、好ましくは反応時間は１０分か
ら１２時間、反応温度は一２０℃から１００℃の間であ
る。The number of moles of the metal catalyst used in the oxidative camping reaction in the above synthesis example is 0.01 to 1 equivalent relative to the substrate, and the flow rate of oxygen is 10 to 1000 sd per mole of substrate.
/min is preferable. The solvent used for this reaction is
Examples include pyridine, acetone, methanol, etc.
Other second solvents may also be present. There are no restrictions on the reaction time and temperature, but preferably the reaction time is 10 minutes to 12 hours and the reaction temperature is between -20°C and 100°C.
のエチニル水素をハロゲン化するときには、常法に従っ
て、次亜塩素酸アルカリ塩、次亜臭素酸アさせればよい
。When halogenating ethynyl hydrogen, hypochlorite alkali salt and hypobromite alkali salt may be used according to a conventional method.
を常法のショツテン、バウマン反応させることにより、
大量かつ容易に合成できる。By performing the conventional Schotten and Bauman reaction,
Can be easily synthesized in large quantities.
ジャーナル ポリマー サイエンス ポリマーケミスト
リー エデイシラン 第１９巻、第１１５４頁（１９８
１）に記載されている。Journal Polymer Science Polymer Chemistry Edysilane Volume 19, Page 1154 (198
1).
〔発明の効果〕
本発明のアミド基含有、ジフェニルジアセチレンは、反
応性が高く、そして高いポリマー転化率を示し、耐熱性
の優れたポリジアセチレンを与える。[Effects of the Invention] The amide group-containing diphenyl diacetylene of the present invention has high reactivity, exhibits a high polymer conversion rate, and provides polydiacetylene with excellent heat resistance.
特に、得られたポリジアセチレンが、単結晶または結晶
性の高い場合、該ジアセチレンアミドは有機フィラー、
光学材料、導電性材料の原料として有用である。In particular, when the obtained polydiacetylene is single crystal or highly crystalline, the diacetylene amide may contain an organic filler,
It is useful as a raw material for optical materials and conductive materials.
以下、本発明の実施例を挙げるが、本発明が、以下の実
施例に限定されるものではない。Examples of the present invention will be described below, but the present invention is not limited to the following examples.
〔実施例１〕
１０％メチルアミン水溶液１瞳に１ｍｏｌの一を、室温
で一気に加え、３０分間攪拌した０反ろ過にて単離した
。その収率は、定量的であった。[Example 1] 1 mol of 1 mol of 10% methylamine aqueous solution was added at once at room temperature, stirred for 30 minutes, and isolated by zero-filtration. The yield was quantitative.
このアミド０．５ｍｏｌをＮ−メチルピロリドン１００
−に溶かし、これを、０．０５ｍｏｌの塩化銅を含むピ
リジン溶液に加え、酸素ガスを導入しながら８時間反応
させた０反応後、反応物を大量の水に注ぎ、得られた目
的物を吸引ろ過にて単離した。その収率は、９６％であ
った。その同定を赤外吸収スペクトル、ＮＭＲスペクト
ルにより行った結果、目的物であることが確認された。Add 0.5 mol of this amide to 100 mol of N-methylpyrrolidone.
This was added to a pyridine solution containing 0.05 mol of copper chloride, and reacted for 8 hours while introducing oxygen gas. After the reaction, the reaction product was poured into a large amount of water, and the obtained target product was Isolated by suction filtration. The yield was 96%. As a result of its identification by infrared absorption spectrum and NMR spectrum, it was confirmed that it was the desired product.
Ｉ Ｒ（Ｋ Ｂ ｒ 、 ０１−’） ３０８６ｃｍ−
”、 １６３５（Ｊｌ−’。I R (K B r , 01-') 3086 cm-
", 1635 (Jl-'.
１５４２Ｃ１１−’、 １２１０（Ｊ−’得られたアミ
ドは、示差熱分析（ＤＴＡ）により３７６℃までは分解
せず、しかも２００℃で１０時間アニーリングすると少
なくとも５６％以上重合した。1542C11-', 1210(J-') The resulting amide did not decompose up to 376°C according to differential thermal analysis (DTA), and was polymerized by at least 56% after annealing at 200°C for 10 hours.
〔実施例２〕
１０％メチルアミン水溶液の代りに１０％エチルアミン
水溶液を用いた以外は、実施例１を繰り返した。得られ
たアミドの酸クロライドからの総数率は、９６％であっ
た。Example 2 Example 1 was repeated except that 10% ethylamine aqueous solution was used instead of 10% methylamine aqueous solution. The total number ratio of the obtained amide from acid chloride was 96%.
Ｉ Ｒ（Ｋ Ｂ ｒ 、 ａｍ−’） ３０８６ａｌ−
’、 ２９３０ｃ＋ａ−’。I R (K B r , am-') 3086al-
', 2930c+a-'.
１６３５ｃｓｌ−’、 １５４６ｃｍ−’１２１０ｃｍ
−鳳
又、ＮＭＲ（ｄ６−ＤＭＳＯ）の溶液によりエチル基の
吸収が見られた。1635csl-', 1546cm-'1210cm
-Hotomata: Absorption of ethyl group was observed by NMR (d6-DMSO) solution.
得られたアミドは、ＤＴＡ分析により３８６℃までは分
解せず、しかも２００℃で１０時間アニーリングすると
少なくとも６０％以上は重合した。The obtained amide did not decompose up to 386°C according to DTA analysis, and moreover, at least 60% or more was polymerized after annealing at 200°C for 10 hours.
〔実施例３〕
１０％メチルアミン水溶液の代りに２ｗｏｌのアニリン
を含むアセトン溶液３００−を用いた以外は、実施例１
を繰り返した。得られたアミドの酸クロライドからの収
率は、７６％であった。[Example 3] Example 1 except that an acetone solution 300 containing 2 wol of aniline was used instead of the 10% methylamine aqueous solution.
repeated. The yield of the obtained amide from acid chloride was 76%.
Ｉ Ｒ（Ｋ Ｂ ｒ 、 ｃｍ−’） ３
０７２Ｃ１ｌ−’、 １６１２ｃｍ −諺。I R (K B r , cm-') 3
072C1l-', 1612cm - Proverb.
１６００（Ｊ−’、 １５３１ｃｍ−烏。1600 (J-', 1531cm-crow.
１４３６Ｇ−１
このアミドは、ＤＴＡ分析により４３６℃までは分解せ
ず、２５０℃、１０時間アニーリングすると、少なくと
も３８％以上は重合した。1436G-1 This amide did not decompose up to 436°C according to DTA analysis, and at least 38% polymerized when annealed at 250°C for 10 hours.
〔実施例４〕 実施例３の合成途中で得られる 。[Example 4] Obtained during the synthesis of Example 3.
の次亜臭素酸ソーダ液１００−中で、４８時間攪拌する
ことにより、
た。このブロム化物０．０２０ｍｏｌをｎ−ブチルアミ
ン３０ｄ、Ｎ−メチルピロリドン６０−の混合溶媒中、
酢酸銅０．００２＋ｍｏｌを共存させ、空気中で１６時
間反応させた０反応後、反応物を水に注ぎ、析出した目
的物をろ別して単離した。得られたアミドの収量は、０
．００１８ａ＋ｏｌであった。その同定を赤外吸収スペ
クトル、ＮＭＲスペクトルにより行った結果、目的物で
あることが確認された。The mixture was stirred for 48 hours in a 100% sodium hypobromite solution. 0.020 mol of this bromide was added to a mixed solvent of 30 d of n-butylamine and 60 d of N-methylpyrrolidone.
After 0.002+ mol of copper acetate was allowed to coexist and reacted in air for 16 hours, the reaction product was poured into water, and the precipitated target product was isolated by filtration. The yield of the obtained amide was 0.
．． It was 0018a+ol. As a result of its identification by infrared absorption spectrum and NMR spectrum, it was confirmed that it was the desired product.
Ｉ Ｒ（Ｋ Ｂ ｒ 、 ａｍ−’） １６３８ｃｎ−
’、 １６２６ｃ１１−’。I R (K B r , am-') 1638cn-
', 1626c11-'.
１５９６ｃａ＋−’。1596ca+-'.
Claims (1)
有機基を示し、Ｘ、Ｘ′は水素原子、ハロゲン原子、炭
素数が１から６までの一価の有機基を示す。） を有するアミド基含有ジフェニルジアセチレン[Claims] The structural formula is ▲a mathematical formula, a chemical formula, a table, etc.▼ (Here, R and R' represent a monovalent organic group having 1 to 20 carbon atoms, and X and X' are hydrogen amide group-containing diphenyl diacetylene (representing an atom, a halogen atom, or a monovalent organic group having 1 to 6 carbon atoms)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP696888A JPH01186852A (en) | 1988-01-18 | 1988-01-18 | Amide group-containing diphenyldiacetylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP696888A JPH01186852A (en) | 1988-01-18 | 1988-01-18 | Amide group-containing diphenyldiacetylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01186852A true JPH01186852A (en) | 1989-07-26 |
| JPH0576938B2 JPH0576938B2 (en) | 1993-10-25 |
Family
ID=11653000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP696888A Granted JPH01186852A (en) | 1988-01-18 | 1988-01-18 | Amide group-containing diphenyldiacetylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01186852A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4987257A (en) * | 1986-05-16 | 1991-01-22 | Director-General Of Agency Of Industrial Science And Technology | Diacetylene compound having double bond and shaped article thereof |
| US5175307A (en) * | 1986-05-16 | 1992-12-29 | Agency Of Industrial Science & Technology | Diacetylene compound having double bond and shaped article thereof |
| US5248748A (en) * | 1986-05-16 | 1993-09-28 | Dir. General Of Agency Of Industrial Science And Technology | Diacetylene compound having double bond and shaped article thereof |
-
1988
- 1988-01-18 JP JP696888A patent/JPH01186852A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4987257A (en) * | 1986-05-16 | 1991-01-22 | Director-General Of Agency Of Industrial Science And Technology | Diacetylene compound having double bond and shaped article thereof |
| US5175307A (en) * | 1986-05-16 | 1992-12-29 | Agency Of Industrial Science & Technology | Diacetylene compound having double bond and shaped article thereof |
| US5248748A (en) * | 1986-05-16 | 1993-09-28 | Dir. General Of Agency Of Industrial Science And Technology | Diacetylene compound having double bond and shaped article thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0576938B2 (en) | 1993-10-25 |
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