JPH0433770B2 - - Google Patents
Info
- Publication number
- JPH0433770B2 JPH0433770B2 JP26169586A JP26169586A JPH0433770B2 JP H0433770 B2 JPH0433770 B2 JP H0433770B2 JP 26169586 A JP26169586 A JP 26169586A JP 26169586 A JP26169586 A JP 26169586A JP H0433770 B2 JPH0433770 B2 JP H0433770B2
- Authority
- JP
- Japan
- Prior art keywords
- triptycenyl
- styrene
- compound
- added
- polymerization
- 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
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 47
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 229940125898 compound 5 Drugs 0.000 description 4
- 238000012690 ionic polymerization Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical group C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001454 anthracenes Chemical class 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KLYCPFXDDDMZNQ-UHFFFAOYSA-N Benzyne Chemical compound C1=CC#CC=C1 KLYCPFXDDDMZNQ-UHFFFAOYSA-N 0.000 description 1
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 description 1
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 101000632319 Homo sapiens Septin-7 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 102100027981 Septin-7 Human genes 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229940061627 chloromethyl methyl ether Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- -1 lithium aluminum hydride Chemical compound 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- PTVDYMGQGCNETM-UHFFFAOYSA-N trityl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OC(=O)C(=C)C)C1=CC=CC=C1 PTVDYMGQGCNETM-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明は、新規化合物である４−（９−トリ
プチセニル）スチレンに関し、さらに詳しく言う
と、それ自身で重合可能であり、また、他のビニ
ルモノマーと共重合することも可能であり、崇高
くて剛直な骨格を備えると共に耐熱性および化学
的安定性に優れたポリマーを得るのに有用なモノ
マーである４−（９−トリプチセニル）スチレン
に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a new compound, 4-(9-triptycenyl)styrene, and more specifically, it is polymerizable by itself and can be used with other vinyl The present invention relates to 4-(9-triptycenyl)styrene, which is a monomer that can be copolymerized with monomers and is useful for obtaining polymers with a noble and rigid skeleton and excellent heat resistance and chemical stability.
［従来の技術およびその問題点］
従来、トリチル基をペンダント基として有する
トリチルメタクリレートのポリマーが提案されて
いる（特開昭56−106907号公報参照）。[Prior art and its problems] Trityl methacrylate polymers having trityl groups as pendant groups have been proposed (see Japanese Patent Laid-Open No. 106907/1983).
トリチル基は崇高く、ポリトリチルメタクリレ
ートは、ほぼ完全にアイソタクチツクであり、耐
熱性に優れたポリマーである。 The trityl group is noble, and polytrityl methacrylate is an almost completely isotactic polymer with excellent heat resistance.
しかしながら、このポリトリチルメタクリレー
トは、エステル基を介してトリチル基がポリマー
主鎖に結合しているので、加溶媒分解される。し
たがつて、必ずしも科学的に安定なポリマーとは
言い難い。 However, this polytrityl methacrylate is solvolyzed because the trityl group is bonded to the polymer main chain via an ester group. Therefore, it cannot necessarily be said that it is a scientifically stable polymer.
［発明の目的］
この発明の目的は、トリチル基と類似するトリ
プチセニル基をペンダント基として側鎖に備える
ことにより、剛直なポリマー骨格を形成し、しか
も化学的に安定なポリマーを得るに有用な新規な
ノモマーを提供することである。[Objective of the Invention] The object of the present invention is to form a rigid polymer skeleton by providing a triptycenyl group similar to a trityl group as a pendant group in a side chain, and to create a novel chemically stable polymer. The objective is to provide a unique nomomer.
［前記目的を達成するための手段］
前記目的を達成するためのこの発明の構成は、
式
で示される４−（９−トリプチセニル）スチレン
である。[Means for achieving the above object] The structure of the present invention for achieving the above object is as follows:
formula 4-(9-triptycenyl)styrene represented by
この４−（９−トリプチセニル）スチレンは、
以下の諸物性により特長付けることができる。 This 4-(9-triptycenyl)styrene is
It can be characterized by the following physical properties.
融点； 251〜252℃
NMR（CDC3、60MHz、ppm）；
Hb 5.33（1H，ｄ）
Hd 5.43（1H，ｓ）
Ha 5.85（1H，ｄ）
Hcおよび芳香環上の水素
6.63〜8.13（17H，ｍ）
ただし、前記Ha、Hb、Hc、Hdは次式に示す
水素原子である。 Melting point; 251-252°C NMR ( CDC3 , 60MHz, ppm); Hb 5.33 (1H, d) Hd 5.43 (1H, s) Ha 5.85 (1H, d) Hc and hydrogen on aromatic ring 6.63-8.13 (17H, m) However, the Ha, Hb, Hc, and Hd are hydrogen atoms shown in the following formula.
IR（KBr，cm-1）；1630、3068
UV（シクロヘキサン）；
λmax＝295nm（ε＝１，000）
この４−（９−トリプチセニル）スチレンは、
たとえば、第１図に示すように、ｐ−ブロモアセ
トフエノン２のカルボニル基を還元してアルコー
ル体３とし、このアルコール体３の水酸基を保護
基たとえばメトキシメチル基で保護してから、ア
ントロンとグリニヤール反応を行ない、次いで脱
水芳香族化によりアントラセン誘導体５とする。
このアントラセン誘導体５にベンザインを付加し
てトリプチセン骨格を導入した化合物６とし、こ
の化合物６の保護基を除去して水酸基を再生した
化合物７とし、さらに脱水することにより４−
（９−トリプチセニル）スチレン１が得られる。 IR (KBr, cm -1 ); 1630, 3068 UV (cyclohexane); λmax = 295 nm (ε = 1,000) This 4-(9-triptycenyl) styrene is
For example, as shown in Figure 1, the carbonyl group of p-bromoacetophenone 2 is reduced to give alcohol 3, the hydroxyl group of alcohol 3 is protected with a protecting group such as methoxymethyl group, and then anthrone and Grignard reaction is carried out, followed by dehydration and aromatization to obtain anthracene derivative 5.
Compound 6 is obtained by adding benzyne to this anthracene derivative 5 to introduce a triptycene skeleton, compound 7 is obtained by removing the protective group of compound 6 to regenerate the hydroxyl group, and further dehydration is performed to obtain 4-
(9-triptycenyl)styrene 1 is obtained.
この４−（９−トリプチセニル）スチレンは、
単独で重合させて４−（９−トリプチセニル）ス
チレンホモポリマーとすることもできるし、また
他のビニルモノマーと共重合させて４−（９−ト
リプチセニル）スチレンコポリマーとすることも
できる。 This 4-(9-triptycenyl)styrene is
It can be polymerized alone to form a 4-(9-triptycenyl)styrene homopolymer, or it can be copolymerized with other vinyl monomers to form a 4-(9-triptycenyl)styrene copolymer.
コポリマーとすることができる他のビニルモノ
マーとしては、たとえばスチレン、スチレン誘導
体、メタクリル酸エステル、エクリル酸エステル
などが挙げられる。 Other vinyl monomers that can be made into copolymers include, for example, styrene, styrene derivatives, methacrylic esters, ecrylic esters, and the like.
コポリマーは、ブロツク共重合体であつても、
またグラフト共重合体であつても良い。 Even if the copolymer is a block copolymer,
It may also be a graft copolymer.
この４−（９−トリプチセニル）スチレンは、
ラジカル重合、イオン重合のいずれによつても、
重合可能である。もつとも、イオン重合が好まし
い。 This 4-(9-triptycenyl)styrene is
Whether by radical polymerization or ionic polymerization,
Polymerizable. However, ionic polymerization is preferred.
イオン重合についてさらに説明する。 Ionic polymerization will be further explained.
重合触媒としてアニオン重合触媒が有効であ
り、好ましくアニオン重合触媒としては、たとえ
ば、ｎ−ブチルリチウム、sec−ブチルリチウム、
オリゴスチリルリチウムなどが挙げられる。 Anionic polymerization catalysts are effective as polymerization catalysts, and preferred anionic polymerization catalysts include, for example, n-butyllithium, sec-butyllithium,
Examples include oligostyryllithium.
イオン重合は、溶媒中で行なうことができる。 Ionic polymerization can be carried out in a solvent.
好ましい溶媒としては、たとえば、テトラヒド
ロフラン（THF）、トルエン、キシレンなとが挙
げられる。 Preferred solvents include, for example, tetrahydrofuran (THF), toluene, and xylene.
重合温度は、−70〜50℃、好ましくは−50〜30
℃の範囲で適宜に選択される。 Polymerization temperature is -70~50℃, preferably -50~30℃
It is appropriately selected within the range of °C.
前記触媒によるアニオン重合は、リビング重合
であるので、重合反応を終了させる際、アルコー
ル等で成長末端を封鎖することが必要である。 Since the anionic polymerization using the catalyst is a living polymerization, it is necessary to block the growing end with alcohol or the like when terminating the polymerization reaction.
重合によつて得られるポリマーの分子量は、
THFに溶解させてゲルパーミエーシヨン法
（GPC法）により測定すると、数平均分子量
（Mn）として１，000以上であり、分散度
（Mw／Mn）が1.5以下である。 The molecular weight of the polymer obtained by polymerization is
When dissolved in THF and measured by gel permeation method (GPC method), the number average molecular weight (Mn) is 1,000 or more and the dispersity (Mw/Mn) is 1.5 or less.
このポリ４−（９−トリプチセニル）スチレン
は、側鎖にトリプチセニル側を備えていて極めて
崇高く、剛直である。したがつて、耐熱性および
化学的安定性に優れて容易に加溶媒分解するもの
ではない。 This poly-4-(9-triptycenyl)styrene has a triptycenyl side in its side chain and is extremely noble and rigid. Therefore, it has excellent heat resistance and chemical stability and is not easily solvolyzed.
また、このポリ４−（９−トリプチセニル）ス
チレンは、強度の大きな成形品たとえばフイルム
やフイラメントに成形することができる。 In addition, this poly-4-(9-triptycenyl)styrene can be molded into strong molded products such as films and filaments.
［発明の効果］
この発明により、耐熱性、耐溶剤性等に優れた
ポリ４−（９−トリプチセニル）スチレンを得る
のに有用な４−（９−トリプチセニル）スチレン
を提供することである。[Effects of the Invention] The present invention provides 4-(9-triptycenyl)styrene useful for obtaining poly-4-(9-triptycenyl)styrene having excellent heat resistance, solvent resistance, and the like.
［実施例］
（実施例 １）
４−（９−トリプチセニル）スチレンの製造
窒素雰囲気とした反応容器内に仕込んだ800ml
の無水エーテルに5.17gのリチウムアルミニウム
ハイドライドを添加し、攪拌した。次いで、
24.38gのｐ−ブロモアセトフエノンを200mlの無
水エーテルに溶解した溶液を、前記反応容器内
に、1.5時間かけて滴下した。その後、30分間の
攪拌を続け、薄層クロマトグフラ（TLC）（展開
溶媒；ヘキサン／酢酸エチル＝4/1）によりｐ−
ブロモアセトフエノンの消失を確認してから、酢
酸エチルおよび水を添加し、無水硫酸ソーダで脱
水し、ろ過した。溶媒を留去することにより、第
１図に示す化合物３を23.90gを得た（収率97％）。[Example] (Example 1) Production of 4-(9-triptycenyl)styrene 800 ml charged in a reaction vessel with nitrogen atmosphere
5.17 g of lithium aluminum hydride was added to the anhydrous ether and stirred. Then,
A solution of 24.38 g of p-bromoacetophenone dissolved in 200 ml of anhydrous ether was added dropwise into the reaction vessel over 1.5 hours. After that, stirring was continued for 30 minutes, and p-
After confirming the disappearance of bromoacetophenone, ethyl acetate and water were added, dehydrated with anhydrous sodium sulfate, and filtered. By distilling off the solvent, 23.90 g of Compound 3 shown in FIG. 1 was obtained (yield 97%).
化合物３のNMRスペクトルデータを次に示
す。 The NMR spectrum data of Compound 3 is shown below.
NMR（CDC3、60MHz、ppm）；
CH3 1.33（3H，ｄ）、OH 3.83（1H，
ｓ）
CH 3.50〜3.83（1H，ｍ）
芳香族Ｈ 7.00〜7.47（4H，ｍ）
窒素雰囲気とした反応容器内に仕込んだ500ml
の塩化メチレンに、23.50gの前記化合物３および
65.0mlのエチルジイソプロピニアミンを添加し、
攪拌した。そこへ、20.0mlのクロルメチルメチル
エーテルを５分間で滴下し、そのまま攪拌を継続
した。24時間の経過後、攪拌を停止し、水を加
え、反応器の内容物を塩化メチレンで抽出した。
有機層を無水硫酸ソーダで脱水してから、溶媒を
留去し、シリカゲルカラムクロマトグラフ（展開
溶媒；ベンゼン）により精製することによつて、
第１図に示す化合物４を25.10g（収率88％）得た。 NMR (CDC 3 , 60MHz, ppm); CH 3 1.33 (3H, d), OH 3.83 (1H,
s) CH 3.50-3.83 (1H, m) Aromatic H 7.00-7.47 (4H, m) 500ml charged in a reaction vessel with nitrogen atmosphere
of methylene chloride, 23.50 g of the above compound 3 and
Add 65.0 ml of ethyldiisopropyniamine;
Stirred. Thereto, 20.0 ml of chloromethyl methyl ether was added dropwise over 5 minutes, and stirring was continued. After 24 hours, stirring was stopped, water was added, and the contents of the reactor were extracted with methylene chloride.
The organic layer was dehydrated with anhydrous sodium sulfate, the solvent was distilled off, and the organic layer was purified by silica gel column chromatography (developing solvent: benzene).
25.10 g (yield 88%) of Compound 4 shown in FIG. 1 was obtained.
化合物４のNMRスペクトルデータを以下に示
す。 NMR spectrum data of compound 4 is shown below.
NMR（CDC3、60MHz、ppm）；
CH3 1.38（3H，ｄ）
OCH3 3.25（3H，ｓ）
CH2＋CH 4.37〜4.82（3H，ｍ）
芳香族Ｈ 7.07〜7.48（4H，ｍ）
窒素雰囲気下の反応容器内に仕込んだ35mlの無
水THF中で、0.6mgのMgと5.30の化合物４とでグ
リニヤール試薬を合成した。０℃に冷却下に、こ
のグリニヤール試薬に4.66gのアントロンを添加
し、室温で攪拌した。24時間の経過後、反応器の
内容物を氷中に注ぎ、6Nの塩酸10mlを加えてか
ら、エーテルで抽出した。有機層を、重炭酸ソー
ダ水溶液をおよび食塩水で洗浄し、無水硫酸ソー
ダで脱水してから、溶媒を留去した。その後、40
mlのピリジンと20mlの無水酢酸を加えて、100℃
で12時間攪拌し、未反応のアントロンをアセチル
化した。反応容器の内容物を氷中に注ぎ、6Nの
塩酸80mlを加えてから、クロロホルムで抽出し、
有機層を無水硫酸ソーダで脱水後、溶媒を留去し
た。残留物をシリカゲルカラムクロマトグラフ
（展開溶媒；ヘキサン／酢酸素エチル＝７／１）
で精製した。その結果、第１図に示す化合物５を
2.42g（収率；33％）得た。 NMR (CDC 3 , 60MHz, ppm); CH 3 1.38 (3H, d) OCH 3 3.25 (3H, s) CH 2 +CH 4.37-4.82 (3H, m) Aromatic H 7.07-7.48 (4H, m) Nitrogen atmosphere Grignard reagent was synthesized with 0.6 mg of Mg and 5.30 of compound 4 in 35 ml of anhydrous THF charged in the lower reaction vessel. 4.66 g of anthrone was added to the Grignard reagent while cooling to 0° C. and stirred at room temperature. After 24 hours, the contents of the reactor were poured into ice, 10 ml of 6N hydrochloric acid were added, and then extracted with ether. The organic layer was washed with aqueous sodium bicarbonate and brine, dried over anhydrous sodium sulfate, and then the solvent was evaporated. Then 40
Add ml pyridine and 20 ml acetic anhydride and heat to 100°C.
The mixture was stirred for 12 hours to acetylate unreacted anthrone. The contents of the reaction vessel were poured into ice, 80 ml of 6N hydrochloric acid was added, and then extracted with chloroform.
After dehydrating the organic layer with anhydrous sodium sulfate, the solvent was distilled off. The residue was subjected to silica gel column chromatography (developing solvent: hexane/ethyl acetate = 7/1).
It was purified with As a result, compound 5 shown in Figure 1 was obtained.
2.42g (yield: 33%) was obtained.
この化合物５のNMRスペクトルを以下に示
す。 The NMR spectrum of this compound 5 is shown below.
NMR（CDC3、60MHz、ppm）；
CH3 1.67（3H，ｄ）、
OCH3 3.47（3H，ｓ）
CH2＋CH 4.71〜5.13（3H，ｍ）
芳香族Ｈ 7.10〜8.47（4H，ｍ）
窒素雰囲気下の反応容器内に仕込んだ７mlの無
水塩化メチレン中に、500mgの化合物５と0.35ml
の亜硝酸ｎ−ブチルとを加えて、加熱還流した。
そこへ、400mgの０−アミノ安息香酸を1.5mlの無
水THFに溶解した溶液を、15分間かけて滴下し
た。３時間の経過後に、再度0.35mlの亜硝酸ｎ−
ブチルを加え、400mgのＯ−アミノ安息香酸の無
水THF（1.5ml）溶液を５分間かけて滴下し、さ
らに３時間加熱還流した。その後、溶媒を留去し
てから、得られる反応物をエーテルに溶解し、重
炭酸ソーダ水溶液および水で洗浄し、無水硫酸ソ
ーダで脱水した。溶媒を留去してから、シリカゲ
ルカラムクロマトグラフ（展開溶媒；シクロヘキ
サン／酢酸エチル＝９／１）で精製した。その結
果、第１ずに示す化合物６を270mg（消費された
５に対する収率；85％）得た。 NMR (CDC 3 , 60MHz, ppm); CH 3 1.67 (3H, d), OCH 3 3.47 (3H, s) CH 2 +CH 4.71-5.13 (3H, m) Aromatic H 7.10-8.47 (4H, m) Nitrogen 500 mg of compound 5 and 0.35 ml were added to 7 ml of anhydrous methylene chloride in a reaction vessel under atmosphere.
of n-butyl nitrite was added thereto, and the mixture was heated to reflux.
A solution of 400 mg of 0-aminobenzoic acid dissolved in 1.5 ml of anhydrous THF was added dropwise thereto over 15 minutes. After 3 hours, add 0.35 ml of nitrite n-
Butyl was added, and a solution of 400 mg of O-aminobenzoic acid in anhydrous THF (1.5 ml) was added dropwise over 5 minutes, followed by heating under reflux for an additional 3 hours. Thereafter, the solvent was distilled off, and the resulting reaction product was dissolved in ether, washed with an aqueous sodium bicarbonate solution and water, and dried over anhydrous sodium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (developing solvent: cyclohexane/ethyl acetate = 9/1). As a result, 270 mg of Compound 6 (yield based on consumed 5: 85%) was obtained.
この化合物６のNMRスペクトルを以下に示
す。 The NMR spectrum of this compound 6 is shown below.
NMR（CDC3、60MHz、ppm）；
CH3 1.45〜1.73（3H，ｍ）
OCH3 3.48（3H，ｓ）
CH2＋CH 4.72〜5.12（3H，ｍ）
トリプチセン橋頭位Ｈ
5.42（1H，ｓ）
芳香族Ｈ 6.77〜8.23（16H，ｍ）
窒素雰囲気下の反応容器内に仕込んだ４mlの無
水THFに、120mgの化合物６と1.0mlの6N塩酸と
を加え、50℃で２時間攪拌した。その後、反応容
器の内容物を重炭酸ソーダ水溶液および食塩水で
洗浄し、無水硫酸ソーダで脱水してから、溶媒を
留去した。その結果、第１図に示す化合物７を
102mg（収率；92％）得た。 NMR (CDC 3 , 60MHz, ppm); CH 3 1.45-1.73 (3H, m) OCH 3 3.48 (3H, s) CH 2 +CH 4.72-5.12 (3H, m) Triptycene bridgehead H 5.42 (1H, s) Aromatic Group H 6.77-8.23 (16H, m) 120 mg of compound 6 and 1.0 ml of 6N hydrochloric acid were added to 4 ml of anhydrous THF charged in a reaction vessel under a nitrogen atmosphere, and the mixture was stirred at 50°C for 2 hours. Thereafter, the contents of the reaction vessel were washed with aqueous sodium bicarbonate solution and brine, dried over anhydrous sodium sulfate, and then the solvent was distilled off. As a result, compound 7 shown in Figure 1 was obtained.
102 mg (yield: 92%) was obtained.
この化合物５のNMRスペクトルを以下に示
す。 The NMR spectrum of this compound 5 is shown below.
NMR（CDC3、60MHz、ppm）；
CH3＋OH 1.57〜2.32（4H，ｍ）
CH 4.92〜5.25（1H，ｍ）
トリプチセン橋頭位Ｈ
5.42（1H，ｓ）
芳香族Ｈ 6.77〜8.23（16H，ｍ）
ｏ−キレシン５mlに80mgの化合物７と33mgの
KHSO4と30mgのフエニル（１−ナフチル）アミ
ンとを加えて、２時間加熱還流した。その後、溶
媒を留去してから、薄層クロマトグラフ（展開溶
媒；ベンゼン／シクロヘキサン＝１／３）で精製
することにより、表記の４−（９−トリプチセニ
ル）スチレン（第１図中の１）を65mg（収率；87
％）得た。 NMR (CDC 3 , 60MHz, ppm); CH 3 +OH 1.57-2.32 (4H, m) CH 4.92-5.25 (1H, m) Triptycene bridgehead H 5.42 (1H, s) Aromatic H 6.77-8.23 (16H, m ) 80 mg of compound 7 and 33 mg of o-chiresin in 5 ml
KHSO 4 and 30 mg of phenyl(1-naphthyl)amine were added, and the mixture was heated under reflux for 2 hours. Thereafter, the solvent was distilled off, and purification was performed using thin layer chromatography (developing solvent: benzene/cyclohexane = 1/3) to obtain 4-(9-triptycenyl)styrene (1 in Figure 1). 65 mg (yield; 87
%)Obtained.
この４−（９−トリプチセニル）スチレンの諸
物性は、前述のとおりである。 The physical properties of this 4-(9-triptycenyl)styrene are as described above.
（実施例 ２）
ポリ４−（９−トリプチセニル）スチレンの製
造
十分に精製した４−（９−トリプチセニル）ス
チレン99mgと充分に精製したベンゼン５mlとを高
減圧下の重合容器内に仕込み、次いでｓ−ブチル
リチウムのベンゼン溶液１ml（0.014mmo）を
添加し、室温で12時間重合反応を行なつた。(Example 2) Production of poly-4-(9-triptycenyl)styrene 99 mg of sufficiently purified 4-(9-triptycenyl)styrene and 5 ml of sufficiently purified benzene were charged into a polymerization vessel under high vacuum, and then s -1 ml (0.014 mmo) of a benzene solution of butyllithium was added, and a polymerization reaction was carried out at room temperature for 12 hours.
その後、重合反応溶液を30mlのメタノールに投
入して、精製したポリマーを沈殿させた。ろ取し
たポリマーをメタノールで充分に洗浄し、60℃で
減圧乾燥した。ポリマーの収量は99mg（収率；
100％）であつた。GPC法により測定したこのポ
リマーの分子量（Mn）は11000であり、分散度
（Mw／Mn）は1.15であつた。また、このポリー
は、以下のスペクトルデータから、次式
で示されるポリ４−（９−トリプチセニル）ス
チレンである。 Thereafter, the polymerization reaction solution was poured into 30 ml of methanol to precipitate the purified polymer. The filtered polymer was thoroughly washed with methanol and dried under reduced pressure at 60°C. The yield of polymer was 99 mg (yield;
100%). The molecular weight (Mn) of this polymer measured by GPC method was 11000, and the degree of dispersion (Mw/Mn) was 1.15. Also, this poly can be calculated from the following spectral data using the following formula: It is poly-4-(9-triptycenyl)styrene represented by
ポリマーのスペクトルデータ
IR（KBr，cm-1）；2852，3066
UV（THF）；
λmax＝275nm（ε＝２，000）
また、このポリ４−（９−トリプチセニル）ス
チレンの熱重量分析によると、分解温度は400℃
であり、その場合の重量損失は10％であつた。 Polymer spectral data IR (KBr, cm -1 ); 2852, 3066 UV (THF); λmax = 275 nm (ε = 2,000) Also, according to thermogravimetric analysis of this poly 4-(9-triptycenyl) styrene, Decomposition temperature is 400℃
The weight loss in that case was 10%.
第１図は４−（９−トリプチセニル）スチレン
の合成工程を示す工程説明図である。
FIG. 1 is a process explanatory diagram showing the synthesis process of 4-(9-triptycenyl)styrene.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26169586A JPS63115832A (en) | 1986-11-01 | 1986-11-01 | 4-(9-triptycenyl)styrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26169586A JPS63115832A (en) | 1986-11-01 | 1986-11-01 | 4-(9-triptycenyl)styrene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63115832A JPS63115832A (en) | 1988-05-20 |
| JPH0433770B2 true JPH0433770B2 (en) | 1992-06-04 |
Family
ID=17365425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26169586A Granted JPS63115832A (en) | 1986-11-01 | 1986-11-01 | 4-(9-triptycenyl)styrene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63115832A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4590637B2 (en) * | 2006-02-16 | 2010-12-01 | 国立大学法人 千葉大学 | Method for producing benzene derivative |
| JP6927975B2 (en) | 2016-08-03 | 2021-09-01 | 株式会社シード | Polymerizable triptycene derivative compound |
-
1986
- 1986-11-01 JP JP26169586A patent/JPS63115832A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63115832A (en) | 1988-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wiltshire et al. | Degradable star polymers with high “click” functionality | |
| US5081191A (en) | Functionalized polymers prepared by anionic polymerization | |
| Kobatake et al. | Nitroxide‐mediated styrene polymerization initiated by an oxoaminium chloride | |
| US4975491A (en) | Functionalized polymers prepared by anionic polymerization | |
| JPH0248584A (en) | Trialkylsilyloxy-1, 1-diphenyl ethylene and polymer produced therefrom | |
| EP0351859B1 (en) | Preparation process of block copolymers and resulting block copolymers | |
| Shiohara et al. | Asymmetric anionic polymerization of alkyl-substituted N, N-diphenylacrylamide derivatives | |
| JP2850432B2 (en) | Copolymer and method for producing the same | |
| Sugiyama et al. | Synthesis of block copolymers and asymmetric star-branched polymers comprised of polyacetylene and polystyrene segments via ionic bond formation | |
| CN110092849A (en) | Cationic chain transfer agent and application thereof | |
| JPH0447683B2 (en) | ||
| JPH0374683B2 (en) | ||
| US5214105A (en) | Preparation of graft copolymers from macromolecules containing reactive tertiary structures | |
| JPH0678405B2 (en) | Living block copolymer | |
| JPS63115832A (en) | 4-(9-triptycenyl)styrene | |
| JP2862720B2 (en) | Narrowly dispersible polyhydroxystyrene partially esterified with t-butoxycarbonyl group and method for producing the same | |
| JP4325097B2 (en) | Optically active poly (N-methylbenzylmaleimide) and process for producing the same | |
| JP3729599B2 (en) | Narrowly dispersible poly (p-hydroxy-α-methylstyrene) and process for producing the same | |
| Hsiao et al. | End‐functionalization of syndiotactic polystyrene by vinylsilane inducing selective chain transfer reactions | |
| JPH0617480B2 (en) | Method for producing dimethylsiloxane block copolymer | |
| JP3816690B2 (en) | Saturated hydrocarbon polymer having carboxylic acid group derivative at terminal and method for producing the same | |
| JP2575958B2 (en) | Method for producing polyhydroxystyrene | |
| JP3237235B2 (en) | Styrene polymer and method for producing the same | |
| JPH0441684B2 (en) | ||
| JP2707687B2 (en) | Polysilane block copolymer compound |