JPH0149713B2 - - Google Patents
Info
- Publication number
- JPH0149713B2 JPH0149713B2 JP6240481A JP6240481A JPH0149713B2 JP H0149713 B2 JPH0149713 B2 JP H0149713B2 JP 6240481 A JP6240481 A JP 6240481A JP 6240481 A JP6240481 A JP 6240481A JP H0149713 B2 JPH0149713 B2 JP H0149713B2
- Authority
- JP
- Japan
- Prior art keywords
- tetraoxacyclononane
- trioxane
- present
- cyclic
- molecular weight
- 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
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- RAWYHGCWSAHFGE-UHFFFAOYSA-N 1,3,5,7-tetraoxonane Chemical compound C1COCOCOCO1 RAWYHGCWSAHFGE-UHFFFAOYSA-N 0.000 description 5
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- SFXNZFATUMWBHR-UHFFFAOYSA-N 2-morpholin-4-yl-2-pyridin-3-ylacetonitrile Chemical compound C=1C=CN=CC=1C(C#N)N1CCOCC1 SFXNZFATUMWBHR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- -1 cyclic acetal Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は新規環状ホルマールに関するものであ
る。さらに詳しくは、
構造式
で表わされる環状ホルマールに関する。
一般に環状ホルマールで総称される化合物は多
く知られている。（例えば特公昭55−19941）しか
しながら、これら公知の環状ホルマールは、環構
成単位としての連続するオキシメチレン単位は１
個であることがほとんどであり、多くとも２個を
越えることはなかつた。特開昭53−86794号、53
−121849号、55−52338号などではトリオキサン
と
で示される一般式(2)の環状エーテル、又は環状ア
セタールとの共重合を報告している。（式中R1，
R2，R3およびR4は同一または異なるものであり、
そして水素原子、アルキル基またはハロゲンで置
換されたアルキル基を、R5はメチレン基または
オキシメチレン基または夫々アルキル基、ハロゲ
ン化アルキルで置換されたメチレン基またはオキ
シメチレン基（その際には０乃至３の整数）を意
味するかまたはR5は−（CH2）ｍ−OCH2−，−
（Ｏ−CH2−CH2）ｍ−OCH2−（この場合ｎは１
に等しくｍは１乃至３の整数）であることを意味
する）の化合物を意味する。
本発明の化合物１，３，５，７、テトラオキサ
シクロノナンは(2)式でのR1，R2，R3，R4が水素
原子であり、R5がオキシメチレン基、ｎが３の
化合物に相当するが、これまで、１，３，５，７
テトラオキサシクロノナンの存在を確認する報告
は一切ない。
本発明者らは鋭意検討の結果、３個の連続する
オキシメチレン単位を環構成単位として有する環
状ホルマールのひとつである、１，３，５，７−
テトラオキサシクロノナンの存在を確認すると共
に、これを合成、単離することに成功した。
本発明による１，３，５，７−テトラオキサシ
クロノナンは、それ自身、良好な開環重合の単量
体となると共に、ポリエーテル、オキシメチレン
共重合体などの共単量体として有用である。
本発明の新規環状ホルマールは、エチレンオキ
サイドとトリオキサンを、両者を共重合させうる
能力を有する触媒の存在下に反応させ、該反応を
共重合物の析出する前に停止させることによつて
得ることができる。
実施例
トリオキサン100重量部にエチレンオキシド５
重量部を溶解し、良く撹拌しながら70℃に保つ
た。これにトリオキサン１モルに対して７×10-5
モルに相当する三弗化硼素ジブチルエーテレート
をベンゼンで100倍に希釈したものを反応触媒と
して加え、良く撹拌した。３分後、触媒に対して
化学量論的に３倍量の水酸化カリウムを含むメタ
ノール溶液を加え、反応を停止した。得られた溶
液を常圧で150℃に加熱し、未反応のトリオキサ
ン及びメタノール、他の低沸点生成物を留去し
た。留去後の残液をさらに減圧下で分別蒸留し、
50mmHgにおいて105〜110℃で留出する１，３，
５，７−テトラオキサシクロノナンを純度約90％
で得た。このものは無色透明の液体でエチレンオ
キサイドからの収率は35％であつた。第１図に
は、さらに精製された１，３，５，７−テトラオ
キサシクロノナンのH1核磁気共鳴スペクトルを
示した。使用機器は日本電子社製JNMMH−100
型で、基準物質はテトラメチルシランを用いた。
このスペクトルは１，３，５，７−テトラオキサ
シクロノナンであることを示している。
さらに分子量を確認するため、ベンゼンにこの
化合物を溶解したときのベンゼンの凝固点降下を
測定した。測定は通常のベツクマン法により行な
つた。結果は表−１に示した通りである。算出さ
れた分子量は132〜136でありこの化合物が１，
３，５，７−テトラオキサシクロノナン（分子量
134）であることと良く一致する。
The present invention relates to a novel cyclic formal. For more information, see Structural Formula Regarding the cyclic formal represented by . Many compounds are generally known as cyclic formals. (For example, Japanese Patent Publication No. 55-19941) However, these known cyclic formals have one continuous oxymethylene unit as a ring constituent unit.
Most of the time there were only one, and there were never more than two at most. JP-A-53-86794, 53
−121849, 55-52338, etc., trioxane and Copolymerization with a cyclic ether or cyclic acetal of general formula (2) has been reported. (In the formula R 1 ,
R 2 , R 3 and R 4 are the same or different,
and R 5 is a hydrogen atom, an alkyl group, or an alkyl group substituted with a halogen; or R 5 is −(CH 2 )m−OCH 2 −, −
(O-CH 2 -CH 2 )m-OCH 2 - (in this case n is 1
m is an integer from 1 to 3)). In compounds 1, 3, 5, 7 and tetraoxacyclononane of the present invention, R 1 , R 2 , R 3 , and R 4 in formula (2) are hydrogen atoms, R 5 is an oxymethylene group, and n is 3 It corresponds to the compound of 1, 3, 5, 7
There are no reports confirming the existence of tetraoxacyclononane. As a result of extensive studies, the present inventors found that 1,3,5,7-
We confirmed the existence of tetraoxacyclononane, and succeeded in synthesizing and isolating it. The 1,3,5,7-tetraoxacyclononane according to the present invention is itself a good monomer for ring-opening polymerization, and is also useful as a comonomer for polyethers, oxymethylene copolymers, etc. be. The novel cyclic formal of the present invention can be obtained by reacting ethylene oxide and trioxane in the presence of a catalyst capable of copolymerizing both, and stopping the reaction before precipitation of the copolymer. Can be done. Example: 5 parts by weight of ethylene oxide in 100 parts by weight of trioxane
Part by weight was dissolved and kept at 70°C with thorough stirring. To this, 7×10 -5 per mole of trioxane
A mole of boron trifluoride dibutyl etherate diluted 100 times with benzene was added as a reaction catalyst, and the mixture was stirred well. After 3 minutes, a methanol solution containing potassium hydroxide in an amount stoichiometrically three times the amount of the catalyst was added to stop the reaction. The resulting solution was heated to 150° C. under normal pressure, and unreacted trioxane, methanol, and other low-boiling products were distilled off. The residual liquid after distillation is further fractionally distilled under reduced pressure,
1,3, which distills at 105-110℃ at 50mmHg
5,7-tetraoxacyclononane with a purity of approximately 90%
I got it from This product was a colorless and transparent liquid, and the yield from ethylene oxide was 35%. FIG. 1 shows the H 1 nuclear magnetic resonance spectrum of further purified 1,3,5,7-tetraoxacyclononane. The equipment used is JNMMH-100 manufactured by JEOL Ltd.
The reference material used was tetramethylsilane.
This spectrum shows that it is 1,3,5,7-tetraoxacyclononane. Furthermore, to confirm the molecular weight, the freezing point depression of benzene was measured when this compound was dissolved in benzene. Measurements were carried out using the usual Beckman method. The results are shown in Table-1. The calculated molecular weight is 132-136, and this compound has a molecular weight of 1,
3,5,7-tetraoxacyclononane (molecular weight
134).
【表】
として求めた。
[Table]
第１図は本発明１，３，５，７−テトラオキサ
シクロノナンのH1核磁気共鳴スペクトルを示す。
第１図中ピークＡ，Ｂ，Ｃはそれぞれ下記式に
おけるHA，HB，HCで示された水素のスペクト
ルを示す。
FIG. 1 shows the H 1 nuclear magnetic resonance spectrum of 1,3,5,7-tetraoxacyclononane of the present invention. In FIG. 1, peaks A, B, and C represent the spectra of hydrogen represented by HA, HB, and HC in the following formula, respectively.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6240481A JPS57179180A (en) | 1981-04-27 | 1981-04-27 | Novel cyclic formal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6240481A JPS57179180A (en) | 1981-04-27 | 1981-04-27 | Novel cyclic formal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57179180A JPS57179180A (en) | 1982-11-04 |
| JPH0149713B2 true JPH0149713B2 (en) | 1989-10-25 |
Family
ID=13199160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6240481A Granted JPS57179180A (en) | 1981-04-27 | 1981-04-27 | Novel cyclic formal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57179180A (en) |
-
1981
- 1981-04-27 JP JP6240481A patent/JPS57179180A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57179180A (en) | 1982-11-04 |
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