JPS60248644A - Novel cyclobutane derivative - Google Patents
Novel cyclobutane derivativeInfo
- Publication number
- JPS60248644A JPS60248644A JP10422184A JP10422184A JPS60248644A JP S60248644 A JPS60248644 A JP S60248644A JP 10422184 A JP10422184 A JP 10422184A JP 10422184 A JP10422184 A JP 10422184A JP S60248644 A JPS60248644 A JP S60248644A
- Authority
- JP
- Japan
- Prior art keywords
- light
- formula
- irradiation
- compound
- mercury lamp
- 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
- 125000001995 cyclobutyl group Chemical class [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 title claims 3
- 125000004494 ethyl ester group Chemical group 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000004952 Polyamide Substances 0.000 claims description 10
- 229920002647 polyamide Polymers 0.000 claims description 10
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 2
- 239000005711 Benzoic acid Substances 0.000 claims 1
- 235000010233 benzoic acid Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052753 mercury Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 3
- 230000001678 irradiating effect Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- BFLGEZGYYCQWRT-DHZHZOJOSA-N 4-[(e)-3-oxo-3-phenylprop-1-enyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1\C=C\C(=O)C1=CC=CC=C1 BFLGEZGYYCQWRT-DHZHZOJOSA-N 0.000 abstract 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000539 dimer Substances 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 150000001930 cyclobutanes Chemical class 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000004427 diamine group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 2
- 238000011907 photodimerization Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- 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 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 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
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- -1 dithiol ester Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyamides (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は光照射にょる画像形成材等に有用な新規なシク
ロブタン誘導体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel cyclobutane derivative useful as an image forming material upon irradiation with light.
さらに詳しくは４−（５−オキソ−５−フェニル−１−
プロペニル） 安息香ａ （以下０ＰＰＢと略記する〕
又はそのエチルエステルを光トポケミカル過程にょ９二
量化して得られる新規なシクロブタン誘導体及び該シク
ロブタン誘導体とジアミンの反応に１９得られた画像形
成能を有する新規なポリアミドに関する。More specifically, 4-(5-oxo-5-phenyl-1-
propenyl) benzoin a (hereinafter abbreviated as 0PPB)
The present invention also relates to a novel cyclobutane derivative obtained by dimerizing its ethyl ester through a phototopochemical process, and a novel polyamide having image-forming ability obtained by reacting the cyclobutane derivative with a diamine.
［従来の技術及び問題点］
０ＰＰＢ誘導体が結晶状態での光反応にょシ高収率で二
量化することは本発明者等が発見した。この際、対称性
の異る下記（１）及び（１／で表わされる二種類の構造
をとりうる。[Prior Art and Problems] The present inventors have discovered that 0PPB derivatives dimerize in high yield during photoreaction in a crystalline state. At this time, two types of structures represented by the following (1) and (1/) having different symmetries can be taken.
Ｒ１Ｒ２
（Ｉｆ型化合物は、本発明者等の発見した方法によ６ｏ
ｐｐａメチルエステルの光二量化により得ることが出来
る。一方、（Ｉ） Ｍｌｉ化合物は感光性樹脂、生理活
性物質等の中間体として有用であるが、従来その存在、
製法が知られていなかった。R1R2 (If type compound is 6o by the method discovered by the present inventors)
It can be obtained by photodimerization of ppa methyl ester. On the other hand, (I) Mli compounds are useful as intermediates for photosensitive resins, physiologically active substances, etc., but their existence and
The manufacturing method was unknown.
本発明者は、（Ｉ）型の化合物の製法について鋭意検討
の結果、０ＰＰＢ又はそのエチルエステルの光二量化に
より高収率で（Ｉ）型化合物が得られることを発見し本
発明に到った。（極めて興味あることｌＣＯＰ Ｐ Ｈ
のメチル、プロピル、ブチル等のエステルでは（Ｉｔ型
が得られる）。As a result of intensive studies on the method for producing type (I) compounds, the present inventors discovered that type (I) compounds could be obtained in high yield by photodimerization of 0PPB or its ethyl ester, leading to the present invention. . (Extremely interesting thing lCOP PH
For esters such as methyl, propyl, butyl, etc. (the It form is obtained).
即ち、本発明は前記式（Ｉ）で表わされる二官能性シク
ロブタン誘導体を提供するものである。That is, the present invention provides a bifunctional cyclobutane derivative represented by the above formula (I).
本発明の前記式（Ｉ）で表わされる化合物は、０ＰＰＢ
又はそのエチルエステルに結晶状態で光を照射すること
により得ることが出来る。The compound represented by the formula (I) of the present invention is 0PPB
Alternatively, it can be obtained by irradiating the ethyl ester in a crystalline state with light.
照射は通常、原料結晶の粉末を水又は界面活性剤を含む
水に分散させ、高圧水銀灯の光な照射する方法で行われ
るが、これに限定されるものでなく、気体中に浮遊され
た状態で照射してもよ（、又光源も高王水鋏灯に限らな
い。Irradiation is usually carried out by dispersing raw material crystal powder in water or water containing a surfactant and irradiating it with light from a high-pressure mercury lamp, but is not limited to this method. (Also, the light source is not limited to the Takao Suisaku lantern.
本発明のポリアミドは化合物（１）又は（Ｉトとジアミ
ンが重縮合した構造（Ｉ［）又は−の化合物である。The polyamide of the present invention is a compound having a structure (I[) or - in which compound (1) or (I) and a diamine are polycondensed.
級のジアミンの２個の７ミノ基から１個づつの活性水素
を除いた残基）
本発明にかかるジアミン残基は飽和であってもよく又不
飽和であっても良い。又、二種以上のジアミン残基の混
合物であってもよい。The diamine residue according to the present invention may be saturated or unsaturated. Alternatively, it may be a mixture of two or more types of diamine residues.
下記にその一例を示す。An example is shown below.
これらのポリアミドから得られたフィルムは光開裂性の
シフ瞠ブタン環を有し又増感基であるベンゾイル基を有
するため高い感光性を有する。すなわち光四躬による分
子貴低下、薄色物質の生成等を利用して感光性フィルム
として用いることが出来る。Films obtained from these polyamides have a photocleavable Schiff-butane ring and a benzoyl group, which is a sensitizing group, and therefore have high photosensitivity. That is, it can be used as a photosensitive film by taking advantage of the reduction in molecular nobleness and the production of light-colored substances due to light absorption.
本発明のポリアミドは通常のジカルボン酸又はそのエス
テルとジアミンからポリアミドを得る方法により得るこ
とか出来る。例えば２−メルカプトベンゾチアゾールと
の反応で得たジチオールエステルとジアミンとの反応は
温和な条件で反応が進行するため姓ましい方法である。The polyamide of the present invention can be obtained by a conventional method for obtaining polyamide from dicarboxylic acid or its ester and diamine. For example, the reaction of a dithiol ester obtained by reaction with 2-mercaptobenzothiazole with a diamine is a preferable method because the reaction proceeds under mild conditions.
以下、実施例によシ本発明を具体的に説明するが、本発
明はこれらの実施例に限定されるものではない。EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.
実施例−１（ＯＰＰＨの合成）
苛性ソーダ水溶液（１２−８１ＮａＯＨ／ １１２ｄＨ
ｚＯ）にアセトフェノン１９．２７ｉｌおよびエタノー
ル１ｂｙｄを加え、温度を２０〜５０℃に保ちながら同
溶液にテレフタルアルデヒド酸２５ｇを８Ｃ１ｆｆｊの
ＤＭＦに溶かした溶液を加えた後、さらに同温度に５時
間だもつ。反応終了後、反応液に塩酸を添加して０ＰＰ
Ｂ （粗収率９４．９％）をえた。Example-1 (Synthesis of OPPH) Caustic soda aqueous solution (12-81NaOH/112dH
Add 19.27 il of acetophenone and 1 byd of ethanol to zO), add a solution of 25 g of terephthalaldehydic acid dissolved in 8C1ffj of DMF while maintaining the temperature at 20 to 50°C, and then keep at the same temperature for 5 hours. . After the reaction is complete, add hydrochloric acid to the reaction solution to reduce 0PP.
B (crude yield 94.9%) was obtained.
実施例−２（ＯＰＰＢエチルエステルの合成）ＯＰＰＢ
２５．９を７００１１１のエタノールに溶かし、塩化
水素ガスを通じながら５〜４時間還流した。反ろ液を濃
縮し、８４．５％の収率で０ＰＰＢエチルエステルの黄
色結晶を得た。ｎ−ヘキサンよシ再結晶して精製結晶を
得た。Example-2 (Synthesis of OPPB ethyl ester) OPPB
25.9 was dissolved in 700111 ethanol and refluxed for 5 to 4 hours while passing hydrogen chloride gas. The counterfiltrate was concentrated to obtain yellow crystals of 0PPB ethyl ester with a yield of 84.5%. Purified crystals were obtained by recrystallization from n-hexane.
実施例−５（（Ｉ）型の０ＰＰＢ二量体の合成〕メノウ
鉢で微粉化した５、０Ｉの０ＰＰＢを界面活性剤ＮＩＫ
ＫＯＬ−１ＯＦＦ １滴を添加した４００−の水に分散
させ、充分にスターラー攪拌しながら窒素ガス気流下室
温で５０時間パイレックスフィルターを装着した１００
Ｗ高圧水銀灯を用いて内部闇躬した。Example-5 (Synthesis of type (I) 0PPB dimer) 0PPB of 5,0I, which was pulverized in an agate pot, was mixed with the surfactant NIK.
KOL-1OFF was dispersed in 400-ml water to which 1 drop was added, and the 100-100 was equipped with a Pyrex filter for 50 hours at room temperature under a nitrogen gas stream with thorough stirring using a stirrer.
The interior was darkened using a W high-pressure mercury lamp.
反応後、固体を濾別し、ついで氷酢酸、水の順で洗浄し
アセトニトリルから再結晶すると２．８９の針状結晶が
得られた。ｍｐ ２５０−２５５．５℃、収率５６％で
あった。After the reaction, the solid was filtered, washed successively with glacial acetic acid and water, and recrystallized from acetonitrile to obtain 2.89 needle crystals. mp 250-255.5°C, yield 56%.
実施例−４（（■１型の０ＰＰＢ工チルエステルニ量体
の合成ｊ実施例−５と同様の方法でＯＰＰＢエチルエス
テルに光朋射した。２．５時間の照射後、固体をｒ別し
、エーテルで洗浄後エタノールかう再結晶した。９４％
の収率で二量体を得た。Example-4 ((■ Synthesis of type 1 0PPB engineered methyl ester dimer) OPPB ethyl ester was irradiated with light in the same manner as in Example-5. After irradiation for 2.5 hours, the solid was separated, After washing with ether, it was recrystallized in ethanol.94%
The dimer was obtained in a yield of .
実施例−５（（ＩＩ）型ポリアミドの合成）ＯＰＰＢ二
量体５，２０ ｊｌ （１０，５ｍ ｍｏｌｅ）に塩化
チオニル５０１＋Ｉｊと触媒としてピリジン１滴を加え
、１．０時間還流させた。ついで過剰の塩化チオニルを
除去した後テトラヒドロフラン（ＴＨＦ）８ （１１７
に溶解させ、さらにトリエチルアミン２，２６１ （２
２，４ｍ ｍｏｌｅ）を加えた。２−メルカプトベンゾ
チアゾール５．４５．９ （２０’、６ｍ ｍｏｌｅ）
をＴＨＦ８０−に溶解させ室温で攪拌しながら先に調整
した酸クロリドのＴＨＦ溶液を滴下し、２．０時間反応
させた。反応後３００−の水に注いだ。次いで生成物を
デ別し、アセトンで充分に洗浄することにより真珠色の
粉末６．０６１ （７，５５ｍ ｍｏｌｅ）を得た。収
率７５％。Example 5 (Synthesis of type (II) polyamide) Thionyl chloride 501+Ij and 1 drop of pyridine as a catalyst were added to 5.20 jl (10.5 mmole) of OPPB dimer, and the mixture was refluxed for 1.0 hour. Then, after removing excess thionyl chloride, tetrahydrofuran (THF) 8 (117
Triethylamine 2,261 (2
2.4 mmole) was added. 2-Mercaptobenzothiazole 5.45.9 (20', 6m mole)
was dissolved in THF80-, and while stirring at room temperature, the previously prepared THF solution of acid chloride was added dropwise, and the mixture was reacted for 2.0 hours. After the reaction, it was poured into 300ml of water. The product was then separated and thoroughly washed with acetone to obtain 6.061 (7.55 mmoles) of a pearl-colored powder. Yield 75%.
この粗生成物を塩化メチレンから再結晶すると真珠色の
微細針状結晶を得た。This crude product was recrystallized from methylene chloride to obtain pearl-colored fine needle-like crystals.
１２０．５ダ（１，０５５ｍ ｍｏｌｅ）のへキサメチ
レンジアミン（ＨＭＤＡ）をＮ−メチルピロリドン（Ｎ
ＭＰ）２，０ＷＬｌに溶解し、ついで８５１．５■（１
，０５５ｍ ｍｏｌｅ）のジチオ−ルエス７− ／ｌ／
ヲ加え、塞温で攪拌した。モノマーは発熱をともなっ
て徐々に溶解し、溶液は粘稠となった。２５時間後１２
５−の１％の炭酸ナトリウム水溶液に注いだ。沈殿した
ポリマーを濾別し、水、熱水、メタノールの順で洗浄し
、真空乾燥した。120.5 da (1,055 m mole) of hexamethylene diamine (HMDA) was added to N-methylpyrrolidone (N
MP) 2.0WLl, then 851.5■(1
,055m mole) of dithioles7-/l/
was added, and the mixture was stirred while keeping warm. The monomer gradually dissolved with exotherm, and the solution became viscous. 25 hours later 12
5-1% aqueous sodium carbonate solution. The precipitated polymer was separated by filtration, washed with water, hot water, and methanol in this order, and dried under vacuum.
収量０．６０９ （９９％）、η１ｎｈＯ，２７であっ
た。このポリアミドはメタノール、アセトンに不溶、ク
ロロホルムに難溶で、ＮＭＰ、’ＤＭＦ。The yield was 0.609 (99%), η1nhO,27. This polyamide is insoluble in methanol and acetone, slightly soluble in chloroform, and is suitable for NMP and 'DMF.
ＨＭＰＡ等の非プロトン性極性溶媒に可溶である。It is soluble in aprotic polar solvents such as HMPA.
又、ＮＭＰあるいは１，１．１．５，５，５−へキサフ
ルオロ−２−プロパツールからフィルムをキャストする
ことができる。Films can also be cast from NMP or 1,1.1.5,5,5-hexafluoro-2-propertool.
実施例−６（（至）型ポリアミドの合成）ＯＰＰＢメチ
ルエステルから実施例−４左同様の方法で光朋射後、メ
タノールから再結晶した二量体（Ｓ、ＯＯ＆）をギ酸（
１，ａ６Ｊｉｌ）、濃硫酸（５，１２，９）中、窒素気
流下９０−１００℃で５時間さらに１１０−１２０℃で
７時間加熱攪拌した。反応後ギ酸不溶物を濾別し、水洗
、真空乾燥し、加水分解二量体を得た。収率９４％。Example 6 (Synthesis of (to)-type polyamide) From OPPB methyl ester, the dimer (S, OO&) was recrystallized from methanol after irradiation with light in the same manner as on the left in Example 4.
1, a6 Jil) and concentrated sulfuric acid (5, 12, 9) under a nitrogen stream at 90-100°C for 5 hours and further heated and stirred at 110-120°C for 7 hours. After the reaction, formic acid insoluble matter was filtered off, washed with water, and dried under vacuum to obtain a hydrolyzed dimer. Yield 94%.
ついで実施例−５と同様の方法でヘキサメチレンジアミ
ンと重縮合しポリアミドを得た（収率９６％〕。Then, polycondensation with hexamethylene diamine was performed in the same manner as in Example 5 to obtain a polyamide (yield: 96%).
このポリマーとＮ−メチル−２−ピロリドンあるいは１
，１，１，５１５．５−へキサフルオロ−２−プロパツ
ールに溶解しガラス板上に耐着後乾燥してフィルムを得
た。これに１００Ｗの高圧水銀灯の光を４時間照射し着
色画像を得た。This polymer and N-methyl-2-pyrrolidone or 1
, 1,1,515.5-hexafluoro-2-propanol, adhered to a glass plate and dried to obtain a film. This was irradiated with light from a 100 W high pressure mercury lamp for 4 hours to obtain a colored image.
出願人代理人 古 谷 馨Applicant's agent Kaoru Furutani
Claims (1)
ン誘導体 ２．４−（５−オキソ−５−フェニル−１−プロベニル
ン安息香酸又はそのエチルエステルを光二量化すること
を特徴とする下記の式（Ｉ）で表わされるシクロブタン
誘導体の製造方法＆ 一般式（ＩＩ）又は（至）で示さ
れるボリアミド[Claims] 1. A bifunctional cyclobutane derivative represented by the following formula (IJ) characterized by photodimerizing 4-(5-oxo-5-phenyl-1-probenylene benzoic acid or its ethyl ester) A method for producing a cyclobutane derivative represented by the following formula (I) & a polyamide represented by the general formula (II) or (to)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10422184A JPS60248644A (en) | 1984-05-23 | 1984-05-23 | Novel cyclobutane derivative |
| JP5811792A JPH0649757B2 (en) | 1984-05-23 | 1992-03-16 | New polyamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10422184A JPS60248644A (en) | 1984-05-23 | 1984-05-23 | Novel cyclobutane derivative |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5811792A Division JPH0649757B2 (en) | 1984-05-23 | 1992-03-16 | New polyamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60248644A true JPS60248644A (en) | 1985-12-09 |
| JPH0460099B2 JPH0460099B2 (en) | 1992-09-25 |
Family
ID=14374903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10422184A Granted JPS60248644A (en) | 1984-05-23 | 1984-05-23 | Novel cyclobutane derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60248644A (en) |
-
1984
- 1984-05-23 JP JP10422184A patent/JPS60248644A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0460099B2 (en) | 1992-09-25 |
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