JPS5859985A - Bicycloortho ester containing polar group - Google Patents
Bicycloortho ester containing polar groupInfo
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- JPS5859985A JPS5859985A JP56158625A JP15862581A JPS5859985A JP S5859985 A JPS5859985 A JP S5859985A JP 56158625 A JP56158625 A JP 56158625A JP 15862581 A JP15862581 A JP 15862581A JP S5859985 A JPS5859985 A JP S5859985A
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
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Abstract
Description
【発明の詳細な説明】
本発明は例えば重合性単量体として有用な新規化合物に
関するもので、本発明により提供される化金物はニトロ
基またはアミノ基を含有する下式〔1〕及び式〔2〕に
よって示される、ビシクロオルソエステル化合物である
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel compounds useful as, for example, polymerizable monomers, and the metal compounds provided by the present invention are compounds of the following formula [1] and formula [1] containing a nitro group or an amino group. 2] is a bicycloorthoester compound.
(式中B−は水1g原子、低級アルキル基又は7エ二ル
基を表わす。)
本発明の式〔1〕で示される化合物(以下化合物〔1〕
という)は、下式〔3〕で示されるトリアルキルオルソ
アシレート(以下化合物〔3〕という)とゝトリス(ヒ
ドロキシメチル)ニトロメタンの脱アルコール反応によ
って製造される。(In the formula, B- represents 1 g of water, a lower alkyl group, or a 7-enyl group.) The compound represented by the formula [1] of the present invention (hereinafter referred to as compound [1])
) is produced by the dealcoholization reaction of trialkyl orthoacylate represented by the following formula [3] (hereinafter referred to as compound [3]) and tris(hydroxymethyl)nitromethane.
R−0+0−R1)s (3)(式中
81はアルキル基を表わし、Rは式〔1〕Kおけるもの
と同じ水素原子、低級アルキル基またはフェニル基を表
わす0)
この反応を示すと以下のごとくになるONo、−0(−
OH,−0H)、−)−R−0÷0−Rl)、 −上
式〔3〕においてRがメチル基、エチル基、プロピル基
壇たはブチル基のごとき低級アルキル基である化合物〔
3〕の製造法に関しては、 81M。R-0+0-R1)s (3) (In the formula, 81 represents an alkyl group, and R represents the same hydrogen atom, lower alkyl group, or phenyl group as in formula [1]K0) This reaction is shown below. The ONo becomes like this, -0(-
OH, -0H), -)-R-0÷0-Rl), -A compound in the above formula [3] where R is a lower alkyl group such as a methyl group, ethyl group, propyl group or butyl group [
Regarding the manufacturing method of 3], 81M.
McB/vain and J、Walter Ne1
son、Journal ofAmerican Ch
emical 5ociety、 64.1825−1
827(1942)などに記載されている・
1N九式〔3〕において8が7↓ニル基である化合物の
製造方法に関しては、 80M0McBlvain、J
、T。McB/vain and J, Walter Ne1
son, Journal of American Ch.
chemical 5ociety, 64.1825-1
827 (1942) etc. Regarding the method for producing a compound in which 8 is a 7↓nyl group in the 1N9 formula [3], 80M0McBlvain, J.
,T.
Venerabje、 Joyrna/ of Ame
rican Obern1cm18ociety、 7
2.l5dl(1950)などに記載されている・
式〔3〕KおけるR’は炭素数1〜4程度の低級アルキ
ル基であることが好ましい。アルキル基がより大きくな
ると化合物の沸点が高くなり、蒸留による単一精製がよ
秒困難になるためである。本発明の新規な化合物〔1〕
は、トリス(ヒドロキシメチル)ニトロメタンと化合物
〔3〕とを、適当な溶媒1例えばジ−n−オクチル7タ
レート、ジ−n−ブチル7タレート等の溶媒中で、触媒
例えばp−トルエンスルホン酸等の存在下で脱アルコー
ルするととKより製造される。なお1反応の進行程度は
、留出アルコール量を計測することによって知ることが
できる他1反応液を例えば、液体クロマトグラフィで分
析することによっても知ることができる。Venerabje, Joyna/ of Ame
rican Obern1cm18ociety, 7
2. 15dl (1950) etc. R' in formula [3]K is preferably a lower alkyl group having about 1 to 4 carbon atoms. This is because the larger the alkyl group, the higher the boiling point of the compound, making single purification by distillation more difficult. Novel compound of the present invention [1]
In this method, tris(hydroxymethyl)nitromethane and compound [3] are mixed in a suitable solvent 1 such as di-n-octyl 7-talate, di-n-butyl 7-talate, etc., and a catalyst such as p-toluenesulfonic acid, etc. It is produced from K by dealcoholization in the presence of. The degree of progress of one reaction can be known by measuring the amount of distilled alcohol, and can also be known by analyzing one reaction solution by, for example, liquid chromatography.
化合物〔5〕とトリス(ヒドロキシメチル)ニトロメタ
ンの反応比は1等モルないしいずれかをやや過剰とすれ
ば曳く、反応は窒素ガスのごとき不活性ガス雰囲気中加
熱下に、一般的には80〜b
合物〔1〕はその物性に応じて減圧蒸留法あるいは再結
晶法によって1反応生成液から分離することができる・
また本発明の式〔2〕で示される化合物(以下化合物〔
2〕という)は化合物〔1〕におけるニトロ基の還元反
応によって製造される・
この反応を示すと以下のごとくになる〇化合物〔2〕は
化合物〔1〕を適当な溶媒1例えばジオキナン、ジエチ
ルエーテル等の溶媒中で、触媒例えば酸化白金等の存在
下で水素と反応させることKよりjl造される・なお1
反応の進行騙度は反応液を例えば、I1体クり!トゲラ
フで分析するととによって知る仁とができる・
反応温jlK格別の制限はないが一般KO〜100℃で
行なわれる・
反応液からの化合物〔2〕の分離権得は1例えば沈でん
物を一過し溶媒を留去後、残査を目的物の物性に応じて
減圧蒸留するかあるいは再結晶するなどの手段によって
行ない得る0
本発W14に係る化合物〔1〕及び化合物〔2〕が属す
るビシクロオルソエステル類の一部は、W、J。The reaction ratio of compound [5] and tris(hydroxymethyl)nitromethane is 1 equimolar or a slight excess of either one, and the reaction is generally carried out under heating in an inert gas atmosphere such as nitrogen gas, at a ratio of 80 to 80 molar. b Compound [1] can be separated from the reaction product solution 1 by vacuum distillation or recrystallization depending on its physical properties. Also, the compound represented by formula [2] of the present invention (hereinafter referred to as compound [
2) is produced by the reduction reaction of the nitro group in compound [1]. This reaction is shown as follows. Compound [2] is produced by converting compound [1] into a suitable solvent 1 such as dioquinane, diethyl ether, etc. It is prepared from K by reacting it with hydrogen in the presence of a catalyst such as platinum oxide in a solvent such as 1.
The degree of progress of the reaction is as follows: For example, the reaction solution is I1 body! Analyzing with a Togelaf can yield results that can be determined by the reaction temperature. Although there is no particular restriction on the reaction temperature, it is generally carried out at KO to 100°C. The right to separate compound [2] from the reaction solution is 1. For example, the precipitate can be temporarily separated. After distilling off the solvent, the residue may be distilled under reduced pressure or recrystallized depending on the physical properties of the target product. Some of the esters are W, J.
Ba1jey and K、8aigo *
American Ohemicaj8ociety
、 Diマi 5ion of Polymer O
hemistry eInc、21(1)、 4〜5(
1980)等に記載されている・本発明の化合物は上記
文献記載の化合物同様開環重合するが、単にそれだけで
はなくて、かかる文献記載の化合物等に比し1重合に上
る体積膨張が大きいという予想外の知見を得た。Ba1jey and K, 8aigo *
American Ohemicaj8ociety
, Di My 5ion of Polymer O
hemistry eInc, 21(1), 4-5(
1980) etc. The compound of the present invention undergoes ring-opening polymerization like the compounds described in the above-mentioned literature, but it is said that it not only undergoes ring-opening polymerization, but also has a larger volume expansion per polymerization than the compounds described in such literature. I gained unexpected knowledge.
本発明に係る化合物の重合は次のような機構によって進
むものと考えられる。It is thought that the polymerization of the compound according to the present invention proceeds by the following mechanism.
〇
Y(−0−OHr−0−OH,−)−0OHr−0−0
−R
慟
(式中Xはニトロ基又はアミノ基を表わす・)本発明の
化合物〔1〕及び化合物〔2〕のカチオン重合は一般に
よく知られている方法、すなわちカチオン重合開始剤の
存在下例えば紫外線、赤外線、熱ま九はマイクロ波など
によって行なう−。〇Y(-0-OHr-0-OH,-)-0OHr-0-0
-R (in the formula, X represents a nitro group or an amino group) The cationic polymerization of the compound [1] and compound [2] of the present invention can be carried out by a generally well-known method, that is, in the presence of a cationic polymerization initiator, e.g. Ultraviolet rays, infrared rays, and heat radiation are carried out using microwaves, etc.
そのカチオン重合触媒としては1例えばBP、 。The cationic polymerization catalyst is 1, for example, BP.
FssOj口、 8nOj* 、 8bR、Tie/a
4等のルイス酸多BFa01tm 、 BFs−アニリ
ンコンプレックス等ノコときルイス酸と0.8.Nなど
を有する化合物との配位化合物已(0,H,)、δ〕・
BP、−、OH,−0,ルーN=N−BP;、 ((
OJ(、)aO]−BP、”’等ノコトキルイx酸のオ
キノニウム塩、ジアゾニクム塩、カルlニクム塩t L
s IBr等のハロゲン化合物、混合ハロゲン化合物
蔓ま九は(n −Bu )a Notα等の過ハpゲン
酸誘導体などがあけられる。FssOj mouth, 8nOj*, 8bR, Tie/a
When Lewis acids such as BFa01tm, BFs-aniline complex etc. are mixed with Lewis acids such as 0.8. Coordination compounds with compounds containing N etc.(0,H,), δ]・
BP, -, OH, -0, Roux N=N-BP;, ((
OJ(,)aO]-BP, "'Oquinonium salt, diazonicum salt, calnicum salt of nocotokylic acid t L
Halogen compounds such as sIBr, mixed halogen compounds, and perhalogen acid derivatives such as (n-Bu)a Notα can be used.
また紫外線照射の場合のカチオン重合触媒としニウム塩
蓼
0H10
φ−N”−OH・−も−φ・・BP;
αL
等の周期律表第Va族元素の芳香族オニウム塩基■1族
元素の芳香族オニウム塩;
表JI I a −”i a族元素のジカルボニル錯化
合物等が使用されうる・
触媒の使用量は一般に重合しようとする単量体に対し、
α001〜10wt%好ましくはα1からSwt%の範
囲が好適である。重合温度に関する制@Fi4IKない
が、通常常温〜200′oで一行なわれる@
重合時に溶媒を使用する場合は、生長カチオンと反応し
てその活性を低下させない化合物を選ぶことが望ましい
・使用に適した溶媒としては、へキナン、オクタン等の
脂肪族炭化水素基トルエン。In addition, in the case of ultraviolet irradiation, aromatic onium bases of group Va elements of the periodic table such as nium salts 0H10 φ-N"-OH・- also -φ・・BP; αL ■ aroma of group 1 elements Group onium salts; Table JI Ia-"Dicarbonyl complex compounds of group Ia elements, etc. can be used. The amount of catalyst used is generally based on the monomer to be polymerized,
The range of α001 to 10 wt%, preferably α1 to Swt%, is suitable. There are no restrictions on polymerization temperature @Fi4IK, but it is usually carried out at room temperature to 200'oC.@ When using a solvent during polymerization, it is desirable to select a compound that does not react with the growing cation and reduce its activity. Examples of solvents include hequinane, octane, and other aliphatic hydrocarbon groups such as toluene.
キシレン勢の芳香族炭化水素蓚塩化メチレン。Methylene chloride is an aromatic hydrocarbon in the xylene group.
11−ジクロルエタン等の^ログン化脚化水素その他が
ある。There are ^logonated hydrogen hydrides such as 11-dichloroethane and others.
化合物〔1〕及び化合物〔2〕の重合に際しては。When polymerizing compound [1] and compound [2].
前記反応式に示されるごとくビシフレオルソエステル環
の一環がお辷り、エーテル、エステル結合が生成し重合
物を与える。As shown in the above reaction formula, a part of the bisifre orthoester ring falls off, forming ether and ester bonds to give a polymer.
従来のカチオン重合性モノマーは下表−1に示すように
1重合時に非常に天きな体積IllLmを伴う・表−1
従来モノマーの開環重合における体積収縮率の例
このように重合時の体積収縮が大きいと1例えば成形材
料として使用した場合に寸法精度がでないとか、枝部材
料として利用し九場合にはうめζみ物に収縮によるひず
みがかかるとか、Wとの接着力の低下や隙間が生じるな
どの問題がある。また、j!!料として使用し走場合、
内部ひずみによる塗板との密着性の低下やそ抄がおこる
とか、11着剤として使用した場合、内部ひずみKよる
接着力の低下やそり、変形などの使用上の問題を生ずる
・これに対して1本発明に係る化合物例えば化合物〔1
〕をカチオン重合させた時の体積変化を求めると、1−
メチル−4−ニトロ−2,6,7−トリオ中ナビシクロ
C2,2,2)オクタンは体**張率本釣、5%であり
、また1−エチル−4−二トロー2.47−)リオキサ
ビシクロ〔42,2〕オクタンは体積膨張本釣7.4%
であって、おどろくべきことに体積膨張が認められた・
化合物〔1〕及び化合物〔2〕に最も近い下式の公知化
合物は、カチオン重合に際して体積膨張を示さないので
あって、これと対比すると、化合物〔りが上記のように
重合時に体積膨張する事実は、誠に予想外である。Conventional cationic polymerizable monomers have a very large volume IllLm during one polymerization as shown in Table 1 below.Table 1
Example of volumetric shrinkage rate in ring-opening polymerization of conventional monomers If the volumetric shrinkage during polymerization is large, for example, dimensional accuracy may be poor when used as a molding material, or when used as a branch material. There are problems such as distortion being applied to the ornament due to shrinkage, a decrease in adhesive strength with W, and the formation of gaps. Also, j! ! If you use it as a fee,
When used as an adhesive, internal strain may cause problems such as reduced adhesion to the coated plate and warpage, and when used as an adhesive, internal strain K may cause problems such as reduced adhesion, warping, and deformation. 1 Compounds according to the present invention, such as compound [1
] is cationically polymerized, the volume change is 1-
Methyl-4-nitro-2,6,7-trio (nabicycloC2,2,2) octane has a body** dilatation of 5%, and 1-ethyl-4-nitro-2,2,2) Rioxabicyclo[42,2]octane has a volume expansion of 7.4%
Surprisingly, volumetric expansion was observed.
The known compounds of the formulas below, which are closest to compound [1] and compound [2], do not exhibit volumetric expansion during cationic polymerization; in contrast, the fact that compound [2] exhibits volumetric expansion during polymerization as described above. is truly unexpected.
OH,−0
なお体積収縮率(%)は〔1−(化合物の比重/化合物
から得九重合体の比重) ) x 1ooで、また体積
膨張率(%)は〔(化合物の比重/化合物から得た重合
体の比重)−1)Xtooで示される@上述のように本
発明の化合物〔1〕及び化合物〔2〕は容島に製造する
ことができ、しかも重合によ争1体積**するという特
長をもっている・従って本発明の化合物〔1〕及び化合
物〔2〕は、成形材料、複合材料、接着剤、注雇材料、
塗料などに使用して極めて有用な化合物である・
以下に実施例および参考例を示して、本発明をさらに詳
細かつ具体的に説明する0
実施例1
冷却器を付は喪水分定量受器、攪拌機および窒素吹込皐
管付き3つロフラスコにトリス(ヒドロキシメチル)ニ
トロメタン4!1t3F((15モル)及びトリエチル
オルソ7オーメート4B、F3f(α33モル)を仕込
み、窒素気流中で90〜100℃で2時間反応させ、次
にジ−n−オクチル7タレート600 f及UP−トル
エンスルフォン酸α5fを加え、150℃でさらに5時
間反応させてエチルアルコールを主成分とする留出物的
145tを得念・
この反応液にトリエチルアミンα6uを加え触媒を中和
した。次に結晶の析出を防ぐためにリボンヒーターモ蒸
留管を加熱しながら減圧蒸留して。OH, -0 The volume shrinkage rate (%) is [1-(specific gravity of the compound/specific gravity of the nonapolymer obtained from the compound)) x 1oo, and the volumetric expansion rate (%) is [(specific gravity of the compound/specific gravity of the nonapolymer obtained from the compound) specific gravity of the polymer) -1) Xtoo @ As mentioned above, the compound [1] and compound [2] of the present invention can be produced in Yojima, and moreover, the specific gravity of the polymer can be produced by polymerization with a volume of 1** Therefore, the compounds [1] and [2] of the present invention can be used as molding materials, composite materials, adhesives, injection materials,
It is an extremely useful compound for use in paints, etc. The present invention will be explained in more detail and concretely below with reference to examples and reference examples.0 Example 1 A water loss metering receiver with a cooler, Tris(hydroxymethyl)nitromethane 4!1t3F ((15 mol) and triethyl ortho7ohmate 4B,F3f (α33 mol) were charged into a three-bottle flask equipped with a stirrer and a nitrogen blowing tube, and the mixture was heated at 90 to 100°C in a nitrogen stream. 600 f of di-n-octyl 7-talate and 5 f of UP-toluenesulfonic acid were added, and the reaction was further carried out at 150°C for 5 hours to obtain 145 t of distillate whose main component was ethyl alcohol. Triethylamine α6u was added to this reaction solution to neutralize the catalyst.Next, vacuum distillation was carried out while heating a ribbon heater distillation tube to prevent precipitation of crystals.
淡黄色固体を得た。この固体についてア七トンーn−ヘ
キナン系による再結晶精製を行ない、白色結晶状の4−
ニトロ−2,6,7−)リオキナビシクロ(2,2,2
)オクタン96I(収率18%)を得九〇
その物性値は下記の通りである・
・融点!132℃
・赤外吸収スペクトル(以下IRと略記する0)154
53 、 1565cm ”(−NOJl 150−1
160cm−” 、 1028C1ml−’ (0−0
−0)・核磁気共鳴スペクトル(以下NMRと略記する
)
(ODOj、中) −−−−−−−−(図1参W&)
J(ppm) G5Mo(1H,s、 0−H)4.5
7(6H,s、 0−OH,−0)実施例2
実施例1と同様な装置に、トリス(ヒドロキシメチル)
ニトロメタン9α6f(α6モル)%トリエチルオルソ
アセテート107.01 (α66−Tニル)、ジ−n
−オクチルフタレート400を及びjulとしてp−ト
ルエンスルフオシ酸α51を仕込み、攪拌下窒素ガスを
通しながら徐々に昇温し140℃にした。仁の温度で4
時間反応を継続し。A pale yellow solid was obtained. This solid was purified by recrystallization using an a7ton-n-hexane system, and white crystalline 4-
nitro-2,6,7-)rioquinabicyclo(2,2,2
) Octane 96I (yield 18%) was obtained.90 Its physical properties are as follows: -Melting point! 132°C ・Infrared absorption spectrum (hereinafter abbreviated as IR) 154
53, 1565cm” (-NOJl 150-1
160cm-", 1028C1ml-' (0-0
-0)・Nuclear magnetic resonance spectrum (hereinafter abbreviated as NMR) (ODOj, middle) --------------------- (See Figure 1 W&)
J (ppm) G5Mo (1H, s, 0-H) 4.5
7(6H,s, 0-OH,-0) Example 2 In an apparatus similar to Example 1, tris(hydroxymethyl)
Nitromethane 9α6f (α6 mol)% triethyl orthoacetate 107.01 (α66-T-nyl), di-n
-Octyl phthalate 400 and p-toluenesulfosic acid α51 as jul were charged, and the temperature was gradually raised to 140° C. while stirring and passing nitrogen gas. 4 at the temperature of the kernels
Continue the reaction for an hour.
エタノールを主成分とする留出物的711を得たOこの
反応液にトリエチルアにンα4 mlを加えて触媒を中
和し菱・次に結晶の析出を防ぐためにすIンヒーターで
蒸留管を加熱しながら減圧蒸留して、淡黄色固体62.
7ft得7to仁の固体についてアセトン−n−ヘキナ
ン系による再結晶精製を行ない、白色結晶状の1−メチ
ル−4−ニトロ−λ47−ドリオキサピシクロ〔λλ2
〕オクタン417F(収率4o%)を得たりなお留出温
度は127C/IMHfであツタ〇
その物性値は下記の通りである。Distillate 711 containing ethanol as the main component was obtained. To this reaction solution, 4 ml of triethylamine was added to neutralize the catalyst. Next, the distillation tube was heated with an in-heater to prevent the precipitation of crystals. Distillation under reduced pressure while heating yields a pale yellow solid 62.
The 7ft solid obtained was purified by recrystallization using an acetone-n-hexane system to obtain white crystalline 1-methyl-4-nitro-λ47-drioxapicyclo[λλ2
]Octane 417F (yield 4o%) was obtained, and the distillation temperature was 127C/IMHf.The physical properties are as follows.
・沸点;127υ/ 1 wa H#
・融点;128℃
・比重;t427/25℃
・I Ri 1560cmm−’ (−NO,)112
5cIm”−” 、 1027cm+−’ (0−0−
0)・NMR(ODOZ、中)・・曲・・・叩・・ (
図2参照)’ (1)pm) ! 4.38 (6H,
s、 OH* −0)t 5 D (3H,m 、
0Ha)なお、上記における比重の測定は、空気比較式
比重計930形〔ベックマンジャパン((転)製〕を用
いて行なった(以下の各例も同様である)・実施例3
実施例1と同様な装置にトリス(ヒドロキシメチル)ニ
トロメタン9α6f(α6モル)、 )リエチルオルソ
プ簡ビオネート116.2f(α66モル)、ジーn−
オクチルフタレート2401及びp−)ルエンスル7オ
ン酸α6fを仕込み、攪拌下窒素ガスを通しながら徐々
に昇温し140℃にした。この温度で4時間反応を継続
し、エタノールを主成分とする留出物的651を得た。・Boiling point: 127υ/1 wa H# ・Melting point: 128℃ ・Specific gravity: t427/25℃ ・I Ri 1560cm-' (-NO,) 112
5cIm"-", 1027cm+-' (0-0-
0)・NMR (ODOZ, middle)・・Song・・Tap・(
(See Figure 2)' (1) pm)! 4.38 (6H,
s, OH* −0)t 5 D (3H, m,
0Ha) The above specific gravity measurements were carried out using an air comparison type hydrometer 930 type [manufactured by Beckman Japan] (the same applies to the following examples).Example 3 Example 1 and In a similar apparatus, tris(hydroxymethyl)nitromethane 9α6f (α6 mol), ) ethyl orthoprobeonate 116.2f (α66 mol), di-n-
Octyl phthalate 2401 and p-)luenesulfonate α6f were charged, and the temperature was gradually raised to 140° C. while stirring and passing nitrogen gas. The reaction was continued at this temperature for 4 hours to obtain distillate 651 containing ethanol as a main component.
この反応液にトリエチルアミンt、2mjを加え触媒を
中和した・次に結晶の析出を防ぐためにリボンヒーター
で蒸留管を加熱しながら減圧蒸留して。Triethylamine t, 2mj was added to this reaction solution to neutralize the catalyst.Next, in order to prevent the precipitation of crystals, distillation was carried out under reduced pressure while heating the distillation tube with a ribbon heater.
淡黄色固体的107tを得九〇この固体をn−ヘキナン
による再結晶精製を行ない、白色結晶状の1−エチル−
4−二) 0−2.へ7−ドリオキサビシクロ(2,2
,23オクタン4tot(収率36%)を得た・
なお留出温度は11゛0℃/15■Hfであった@この
化合物の物性値は以下のようである。107t of pale yellow solid was obtained.90 This solid was purified by recrystallization with n-hexane to obtain white crystalline 1-ethyl-
4-2) 0-2. to7-dryoxabicyclo(2,2
, 4 tot of 23 octane (yield 36%) was obtained.The distillation temperature was 11°0°C/15■Hf.The physical properties of this compound are as follows.
・融点茶78℃
・比重11440/25℃
・IR−m−・−・(図3参照)
1558a111″″” (−NO,)1120m−”
、 1027c1111−’ (0−0−0)−NM
R(ODOt、中)・−・・・・・・・・・・(図4参
照)’ (ppm) i 4−29(6H,s、 00
Hz−0)t72 (2H,g、 0−0Hs )/
α95(3H,t、 −OH,)
実施例4
500mj用スデステンレス製オートクレーブ施例1で
得念4−ニトロー2,6.7−1オキサヒシクロ(2,
2,2)オクタン51(51ミリモル)。・Melting point tea 78℃ ・Specific gravity 11440/25℃ ・IR-m-・-・(See Figure 3) 1558a111″″” (-NO,)1120m-”
, 1027c1111-' (0-0-0)-NM
R (ODOt, medium) --- (See Figure 4)' (ppm) i 4-29 (6H, s, 00
Hz-0) t72 (2H, g, 0-0Hs) / α95 (3H, t, -OH,) Example 4 500 mj stainless steel autoclave Example 1 yielded 4-nitro 2,6.7- 1 oxahiclo (2,
2,2) Octane 51 (51 mmol).
ジオキサン100ml及び触媒として酸化白金Q、3f
を加え、攪拌しながら水素を吹込み、水素圧2.51q
i、6−約30℃において24時間反応させた・この反
応液を一過し、P液を脱溶剤後、アセトン−n−ヘキサ
ン系で再結晶精製を行ない、白色結晶状の4−アミノ−
2,47−ドリオキサビシクE”(2,2,2)オクタ
ン五2fC収率78%)を得たO
この化合物の物性値は以下のようである◎・融点!12
0℃
@ I Ri 3550c#−” −3290”’
、15100m (−NHI)1152c=m 、
1022Cai (0−0−0)拳NMR(重アセト
ン中)
五7 (6H,0−OH,−0)
2.2 (2H,−NH,)
実施例5
実施例4と同様な装置に実施例2で得た1−メチル−4
−ニトロ−2,47−)9オキサビシクロ(2,2,2
)オクタン2α0f(1114モル)。100ml of dioxane and platinum oxide Q, 3f as a catalyst
was added and hydrogen was blown into the tank while stirring until the hydrogen pressure was 2.51q.
i, 6 - Reacted at about 30°C for 24 hours - This reaction solution was passed through, and after removing the P solution, recrystallization was carried out using an acetone-n-hexane system to obtain white crystalline 4-amino-
2,47-Dryoxabisic E” (2,2,2)octane 2fC yield 78%) was obtained. The physical properties of this compound are as follows: ◎・Melting point! 12
0℃ @ I Ri 3550c#-”-3290”’
, 15100m (-NHI)1152c=m ,
1022Cai (0-0-0) Fist NMR (in heavy acetone) 57 (6H, 0-OH, -0) 2.2 (2H, -NH,) Example 5 An example was applied to the same apparatus as Example 4. 1-methyl-4 obtained in 2
-nitro-2,47-)9oxabicyclo(2,2,2
) Octane 2α0f (1114 mol).
ジオキサ7500ml及び触媒として酸化白金CL5f
を加え、実施例4と同様に反応させた。7500ml of dioxa and platinum oxide CL5f as a catalyst
was added, and the reaction was carried out in the same manner as in Example 4.
この反応液を一過し、F液を脱溶剤後、アセトン−n−
ヘキサン系で再結晶精製を行ない、白色結晶状の1−メ
チル−4−アミノ−2,t4i、7−)リオキサビシク
ロ(2,2,2)オクタン1五8f(収率83%)を得
九〇
この化合物の物性値は以下のとおりであるO融点112
0℃
比重富1.592/25℃
IR,・・・・・・・・・・・(図5参照)5570c
m 、3310cm 、1620cm (−NH
,)1123(a 、1050cat (0−0−0
)NMR(重アセトン中)・1曲(図6参照)’ (p
I”” ) i 5−74 (6H,s 、0−0Ht
−0)15 (2H,−NH雪)
128(3H,s、 −0H−)
実施例6
実施例4と同様な装置に実施例3で得た1−エチル−4
−ニトロ−2,47−)リオキナビシクロC2,2,2
)オクタン5F(26ミリモル)、ジオキサン100m
l及び触媒として酸化白金α31を加え実施例4と同様
に反応させた。This reaction solution was passed through, and after removing the solvent, acetone-n-
Recrystallization purification was performed in hexane system to obtain white crystalline 1-methyl-4-amino-2,t4i,7-)lioxabicyclo(2,2,2)octane 158f (yield 83%). 90 The physical properties of this compound are as follows: O melting point: 112
0℃ Specific gravity richness 1.592/25℃ IR,・・・・・・・・・・・・(See Figure 5) 5570c
m, 3310cm, 1620cm (-NH
, ) 1123 (a , 1050cat (0-0-0
) NMR (in heavy acetone), 1 track (see Figure 6)' (p
I””) i 5-74 (6H,s, 0-0Ht
-0) 15 (2H, -NH snow) 128 (3H, s, -0H-) Example 6 1-ethyl-4 obtained in Example 3 was added to the same apparatus as Example 4.
-nitro-2,47-)rioquinabicycloC2,2,2
) Octane 5F (26 mmol), dioxane 100m
1 and platinum oxide α31 as a catalyst were added, and the reaction was carried out in the same manner as in Example 4.
この反応液を一過し、P液を脱溶剤後、アセトン−n−
ヘキサン系で再結晶精製を行ない、白色結晶状の1−エ
チル−4−アミノ−2,6,7−)リオキサビシクロ〔
2,λ2〕オクタン2.8f(収率68%)を得た。After passing through this reaction solution and removing the solvent, acetone-n-
Recrystallization was carried out in hexane system to obtain white crystalline 1-ethyl-4-amino-2,6,7-)lioxabicyclo[
2,λ2]octane 2.8f (yield 68%) was obtained.
この化合物の物性値は以下のようである・O融点;62
℃
・IR−−・−・・・−(図7参照)
35703−” −330DC”l−’ 、16 lO
Rm−” (−NH*)1145cm−” 、 111
[csa−’ 、 1067Cj″(0−0−0)・
NMR(重アセトン中);
J(ppm)s五72(6H,0−0HI−0)2.0
(2H,−NH,)
t56(2H,g、−0−OHj)
/
α96C5H,t、 −OH烏 )
参考例1
実施−例2の化合物(1)(1−メチル−4−二トW−
2,47−ドリオキナビシクロ〔2,λ2〕オクタン)
K1重合触媒としてBF−モノエチルア建ン錯体2モル
%を添加し、150℃で1峙間ついで180υで2時間
重合させ友。その結果、かつ色で半固体状の重合物が得
られ7t。The physical properties of this compound are as follows: ・O melting point: 62
°C ・IR--・-- (see Figure 7) 35703-"-330DC"l-', 16 lO
Rm-” (-NH*)1145cm-”, 111
[csa-', 1067Cj'' (0-0-0)・
NMR (in heavy acetone); J (ppm) s572 (6H, 0-0HI-0) 2.0
(2H, -NH,) t56 (2H, g, -0-OHj) / α96C5H, t, -OH) Reference Example 1 Compound (1) of Example 2 (1-methyl-4-ditoW-
2,47-Dolioquinabicyclo[2,λ2]octane)
2 mol % of BF-monoethylamine complex was added as a K1 polymerization catalyst, and polymerization was carried out at 150°C for 1 hour and then at 180υ for 2 hours. As a result, a colored, semi-solid polymer was obtained, weighing 7 tons.
この重合物の分子量は約1000であつ喪。また重合物
の比重は1466(25℃)であり、この値から算出さ
れ九重合による体積膨張率は約45%で6つ九。この重
合物のIR分析より11585m−’のピークが消失し
、 5400cIIl−” 。The molecular weight of this polymer is approximately 1,000. The specific gravity of the polymer is 1466 (25°C), and the volumetric expansion rate due to nonapolymerization calculated from this value is approximately 45%, which is 6x9. IR analysis of this polymer revealed that the peak at 11585m-' disappeared and the peak was 5400cIIl-''.
175Qcsi−’ 、 1250υ1ml ’のピー
クが生成し友。A peak of 175Qcsi-' and 1250υ1ml' was generated.
参考例2
実施例3の化合物[1) (1−エチル−4−二ト薗−
“2.へ7−ドリオキサビシク四(2,2,2)オクタ
ン)K重合触媒として、 BP、・モノエチルアンン錯
体2モル%を添加し%150℃で1時間ついで180℃
で2時間重合させた〇その結果、かつ色の粘稠な重合物
が得られた。Reference Example 2 Compound [1] of Example 3 (1-ethyl-4-nitozono-
2. Added 2 mol% of BP, monoethylamne complex as a 7-dryoxabisictetra(2,2,2)octane)K polymerization catalyst, heated at 150°C for 1 hour, and then heated to 180°C.
Polymerization was carried out for 2 hours. As a result, a colored and viscous polymer was obtained.
この重合物の分子量は約2000であった0またその比
重は1341(25υ)であり1重合による体積***
は約7.4%であった・The molecular weight of this polymer was about 2000, and its specific gravity was 1341 (25υ), and the volume of one polymerization***
was approximately 7.4%.
図1は実施例1で得た化合物のNMRIIIであり。
図2は実施例2で得た化合物のNMR図であり、s3は
実施例3で得た化合物のIRgであa、−tた図4は同
化合物のNMR図であり、wJ5は実施例5で得た化合
物のIR図であり、i九図6は同化合物のNMR図であ
抄、さらに図7は実施例6で得喪化合物のIR図である
・
手続補正書
昭和56年12月ダ日
特許庁長官 島 1)春 樹 殿
1、事件の表示
昭和56年特許願第158625号
2、発明の名称
極性基含有ビシクロオルソエステル
3、補正をする者
事件との関係 特許出願人
住所 東京都港区西新橋1丁目14番1号4、補正の
対象
明細書の発明の詳細な説明の欄
5、補正の内容
(1) FIA細書第3頁10行目にrJovrna
tJと(3)明細書筒8頁4行目に
(4) 明細書第16頁3行目、第19頁7行目に(
2H,f、)C−C山)とあるを
(2H,q、)C−CH,)と補正する〇以上FIG. 1 shows NMR III of the compound obtained in Example 1. Figure 2 is an NMR diagram of the compound obtained in Example 2, s3 is the IRg of the compound obtained in Example 3, and Figure 4 is an NMR diagram of the same compound, and wJ5 is the IRg of the compound obtained in Example 3. Figure 6 is an excerpt of the NMR diagram of the compound obtained in Example 6, and Figure 7 is the IR diagram of the compound obtained in Example 6. Procedural amendment dated December 1982. Commissioner of the Japan Patent Office Shima 1) Haruki Tono1, Indication of the case Patent Application No. 158625 of 1982, Name of the invention Bicycloorthoester containing a polar group3, Person making the amendment Relationship to the case Patent applicant address Port of Tokyo Nishi-Shinbashi 1-14-1-4, Detailed explanation of the invention column 5 of the specification subject to amendment, Contents of the amendment (1) rJovrna on page 3, line 10 of the FIA specification
tJ and (3) on page 8, line 4 of the specification cylinder (4) on page 16, line 3 of the specification, and on page 19, line 7 of the specification (
2H, f,) C-C mountain) is corrected to (2H, q,) C-CH,) 〇 or more
Claims (1)
。 (式中Xはニトロ基またはアミノ基を表わし、Rは水嵩
原子、低級アルキル基または7エ二ル基を表わす。)[Claims] t A polar group-containing bicycloorthoester represented by the following formula. (In the formula, X represents a nitro group or an amino group, and R represents a water bulk atom, a lower alkyl group, or a 7-enyl group.)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56158625A JPS5859985A (en) | 1981-10-07 | 1981-10-07 | Bicycloortho ester containing polar group |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56158625A JPS5859985A (en) | 1981-10-07 | 1981-10-07 | Bicycloortho ester containing polar group |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5859985A true JPS5859985A (en) | 1983-04-09 |
JPH0213675B2 JPH0213675B2 (en) | 1990-04-04 |
Family
ID=15675792
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP56158625A Granted JPS5859985A (en) | 1981-10-07 | 1981-10-07 | Bicycloortho ester containing polar group |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5859985A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4965257A (en) * | 1985-09-24 | 1990-10-23 | The Regents Of The University Of California | Pesticidal compounds |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3686224A (en) * | 1970-02-24 | 1972-08-22 | Gulf Research Development Co | 2,6,7-trioxabicyclo(2.2.2)octane compounds |
-
1981
- 1981-10-07 JP JP56158625A patent/JPS5859985A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3686224A (en) * | 1970-02-24 | 1972-08-22 | Gulf Research Development Co | 2,6,7-trioxabicyclo(2.2.2)octane compounds |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4965257A (en) * | 1985-09-24 | 1990-10-23 | The Regents Of The University Of California | Pesticidal compounds |
Also Published As
Publication number | Publication date |
---|---|
JPH0213675B2 (en) | 1990-04-04 |
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