JPH0545597B2 - - Google Patents
Info
- Publication number
- JPH0545597B2 JPH0545597B2 JP58232242A JP23224283A JPH0545597B2 JP H0545597 B2 JPH0545597 B2 JP H0545597B2 JP 58232242 A JP58232242 A JP 58232242A JP 23224283 A JP23224283 A JP 23224283A JP H0545597 B2 JPH0545597 B2 JP H0545597B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- reaction
- represented
- following formula
- orthocarbonate
- 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 - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AHJWSRRHTXRLAQ-UHFFFAOYSA-N tetramethoxymethane Chemical compound COC(OC)(OC)OC AHJWSRRHTXRLAQ-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LFMXSZSVDQJYDU-UHFFFAOYSA-N 1-(tripropoxymethoxy)propane Chemical compound CCCOC(OCCC)(OCCC)OCCC LFMXSZSVDQJYDU-UHFFFAOYSA-N 0.000 description 1
- DSHXMENPUICESR-UHFFFAOYSA-N [5-(hydroxymethyl)-5-bicyclo[2.2.1]hept-2-enyl]methanol Chemical compound C1C2C(CO)(CO)CC1C=C2 DSHXMENPUICESR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- RXCVUXLCNLVYIA-UHFFFAOYSA-N orthocarbonic acid Chemical compound OC(O)(O)O RXCVUXLCNLVYIA-UHFFFAOYSA-N 0.000 description 1
- -1 orthocarbonic acid ester Chemical class 0.000 description 1
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- CWLNAJYDRSIKJS-UHFFFAOYSA-N triethoxymethoxyethane Chemical compound CCOC(OCC)(OCC)OCC CWLNAJYDRSIKJS-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
【発明の詳細な説明】
前記の式〔３〕で示される化合物（以下化合物
〔３〕という）は既知であり、その製造方法は
Journal of Polymer Science、Polymer
Chemistry Edition、13、2525（1975）で報告さ
れている３，９−ジメチレン−１，５，７，11−
テトラオキサスピロ〔5.5〕ウンデカンの製造方
法と同様である。すなわち、前記の式〔２〕で示
される化合物（以下化合物〔２〕という）をジ−
ｎ−ブチルスズオキサイドおよび二硫化炭素と反
応させることにより化合物〔３〕を得ている。[Detailed Description of the Invention] The compound represented by the above formula [3] (hereinafter referred to as compound [3]) is known, and the method for producing it is
Journal of Polymer Science, Polymer
3,9-dimethylene-1,5,7,11- reported in Chemistry Edition, 13 , 2525 (1975)
The method is similar to the method for producing tetraoxaspiro[5.5]undecane. That is, the compound represented by the above formula [2] (hereinafter referred to as compound [2]) is di-
Compound [3] is obtained by reacting with n-butyltin oxide and carbon disulfide.
しかし、この従来法は一般的工業製品としては
非常に高価な有機スズ化合物と、毒性が高く取扱
いが困難な二硫化炭素とを原料にしており、反応
工程が複雑であることに加えて、目的物の分離取
得も非常に困難であるために、種々の問題点を有
しており、化合物〔３〕の工業的製法としては現
実性に乏しいものである。 However, this conventional method uses organic tin compounds, which are extremely expensive for general industrial products, and carbon disulfide, which is highly toxic and difficult to handle, as raw materials, and the reaction process is complicated. Since it is also very difficult to separate and obtain the compound, it has various problems and is impractical as an industrial method for producing compound [3].
本発明者らは化合物〔３〕のより有利な製法に
ついて種々検討した結果、取扱いが容易な前記の
式〔１〕で示されるオルソ炭酸エステル（以下化
合物〔１〕という）と化合物〔２〕を反応させる
ことによつて、一段反応で極めて容易に化合物
〔３〕を製造できることを見出し、本発明に到達
した。 As a result of various studies on more advantageous methods for producing compound [3], the present inventors found that the orthocarbonic acid ester represented by the above formula [1] (hereinafter referred to as compound [1]), which is easy to handle, and compound [2] It has been found that compound [3] can be produced extremely easily in a one-step reaction by causing the reaction, and the present invention has been achieved.
本発明方法の一例を反応式で示せば次のごとく
であり、オルソ炭酸エステルと化合物〔２〕との
反応では種々の化合物を生成する可能性があるに
もかかわらず、実際には化合物〔３〕を非常に効
率よく生成することが明らかになつたのである。 An example of the method of the present invention is shown in the following reaction formula, and although there is a possibility that various compounds may be produced in the reaction of ortho carbonic acid ester and compound [2], in reality, compound [3] ] was found to be produced very efficiently.
本発明方法において原料とされる化合物〔１〕
におけるR1、R2、R3およびR4が大きくなるに伴
ない、反応により生成するアルコール（ROH）
の沸点が高くなり、反応系外への除去がより困難
になるため、R1、R2、R3およびR4は炭素数１〜
８の直鎖または分枝状のアルキル基が適切であ
る。またR1〜R4の有機基は互いに同一でも異な
つていてもよい。化合物〔１〕の具体例としては
テトラメチルオルソカーボネート、テトラエチル
オルソカーボネート、テトラ−ｎ−プロピルオル
ソカーボネート、テトラ−ｎ−ブチルオルソカー
ボネート、テトラ−iso−ブチルオルソカーボネ
ート、テトラ−ｎ−ペンチルオルソカーボネート
等があげられる。 Compound used as a raw material in the method of the present invention [1]
As R 1 , R 2 , R 3 and R 4 become larger, the alcohol (ROH) produced by the reaction increases.
R 1 , R 2 , R 3 and R 4 have 1 to 1 carbon atoms, so that their boiling point becomes higher and removal from the reaction system becomes more difficult.
Straight-chain or branched alkyl groups of 8 are suitable. Moreover, the organic groups of R 1 to R 4 may be the same or different. Specific examples of compound [1] include tetramethyl orthocarbonate, tetraethyl orthocarbonate, tetra-n-propyl orthocarbonate, tetra-n-butyl orthocarbonate, tetra-iso-butyl orthocarbonate, tetra-n-pentyl orthocarbonate, etc. can be given.
本発明方法を行なうにあたり、原料である化合
物〔１〕および化合物〔２〕は出来るだけ乾燥し
たものを使用するのが良く、又化合物〔２〕はオ
ルソ炭酸エステル（１モル）に対し理論量（２モ
ル）又は理論量よりやや少なめに用いるのが好適
である。反応系における溶媒の存否は本質的なも
のではないが、溶媒を使用する方が反応を円滑に
行なうことが出来る場合がある。使用できる溶媒
としては、本反応に不活性であれば特に制限され
ず例えば、トルエン、キシレン、ジ−ｎ−ブチル
フタレート、ジ−ｎ−オクチルフタレート等が用
いられる。 In carrying out the method of the present invention, it is preferable to use the raw materials Compound [1] and Compound [2] as dry as possible, and compound [2] should be used in a theoretical amount ( 2 mol) or slightly less than the theoretical amount. Although the presence or absence of a solvent in the reaction system is not essential, the reaction may be carried out more smoothly if a solvent is used. The solvent that can be used is not particularly limited as long as it is inert to this reaction, and for example, toluene, xylene, di-n-butyl phthalate, di-n-octyl phthalate, etc. can be used.
反応は触媒たとえばｐ−トルエンスルホン酸あ
るいは硫酸のごとき触媒の存在下に、また所望に
より上記のような溶媒を使用して、加温状態で行
なうことが望ましい。触媒の使用量は原料化合物
に対して一般に0.001〜5wt％で足り、また反応温
度は通常50〜180℃が適当である。反応温度が低
すぎると反応速度が遅く、一方高温にすぎると生
成物の分解が起こり好ましくない。 The reaction is preferably carried out in the presence of a catalyst such as p-toluenesulfonic acid or sulfuric acid, optionally using a solvent such as those mentioned above, and at elevated temperatures. The amount of catalyst used is generally 0.001 to 5 wt% based on the raw material compound, and the reaction temperature is usually 50 to 180°C. If the reaction temperature is too low, the reaction rate will be slow, whereas if the reaction temperature is too high, the product will decompose, which is undesirable.
本発明方法は既述したように脱アルコール反応
を利用するものであり、生成するアルコールは系
外に留出させるのが一般的である。反応の進行の
程度は留出アルコール量を計測することによつて
知ることができる他、反応液を例えば、液体クロ
マトグラフイで分析することによつても知ること
ができる。 As mentioned above, the method of the present invention utilizes a dealcoholization reaction, and the produced alcohol is generally distilled out of the system. The degree of progress of the reaction can be determined not only by measuring the amount of alcohol distilled out, but also by analyzing the reaction solution using, for example, liquid chromatography.
生成した化合物〔３〕は、反応終了後酸触媒を
塩基性物質で中和し、氷水で反応液をしばらく冷
却したのち、ロ過することによつて固体として分
離できる。 The generated compound [3] can be separated as a solid by neutralizing the acid catalyst with a basic substance after the reaction, cooling the reaction solution with ice water for a while, and then filtering it.
本発明によれば、取扱いが極めて容易な原料か
ら簡単な操作で一段反応によつて重合性物質とし
て有用な化合物〔３〕を容易かつ効率よく製造す
ることが可能である。 According to the present invention, it is possible to easily and efficiently produce compound [3] useful as a polymerizable substance through a one-step reaction from raw materials that are extremely easy to handle and with simple operations.
次に本発明方法を実施例によつてさらに詳細に
説明する。 Next, the method of the present invention will be explained in more detail with reference to Examples.
実施例 １
冷却器を付けた水分定量受器、撹拌機およびチ
ツ素吹込み口管付きの３つ口フラスコに、テトラ
メチルオルソカーボネート5.45ｇ（0.0400mol）、
化合物〔２〕（５−ノルボルネン−２，２−ジメ
タノール）11.09ｇ（0.0719mol）、ｐ−トルエン
スルホン酸0.040ｇ（2.1×10-4mol）およびキシ
レン45mlを仕込み、チツ素気流下90℃で１時間、
100℃で１時間、110℃で２時間反応させた。留出
メタノールの量は3.72ｇであつた。トリエチルア
ミン0.08mlを添加して反応を停止させた後、内容
物を氷水で３時間冷却し固体を充分析出させ、こ
の固体をロ過により反応液より分離した。ついで
アセトンを用いてこの固体を洗浄したのち、クロ
ロホルムを用いて再結晶操作を行ない、収量8.8
ｇ、収率77％（化合物〔２〕を基準として算出）
で無色棒状結晶を得た。この結晶はNMR（核磁
気共鳴）スペクトルおよびIR（赤外吸収）スペク
トルから化合物〔３〕と同定された。Example 1 5.45 g (0.0400 mol) of tetramethyl orthocarbonate was added to a three-necked flask equipped with a water metering receiver equipped with a condenser, a stirrer, and a nitrogen inlet tube.
Compound [2] (5-norbornene-2,2-dimethanol) 11.09 g (0.0719 mol), p-toluenesulfonic acid 0.040 g (2.1 x 10 -4 mol) and xylene 45 ml were charged, and the mixture was heated at 90°C under a nitrogen stream. 1 hour,
The reaction was carried out at 100°C for 1 hour and at 110°C for 2 hours. The amount of distilled methanol was 3.72 g. After terminating the reaction by adding 0.08 ml of triethylamine, the contents were cooled with ice water for 3 hours to extract a solid, which was separated from the reaction solution by filtration. After washing this solid with acetone, recrystallization was performed using chloroform to obtain a yield of 8.8
g, yield 77% (calculated based on compound [2])
Colorless rod-shaped crystals were obtained. This crystal was identified as compound [3] from the NMR (nuclear magnetic resonance) spectrum and the IR (infrared absorption) spectrum.
Γ融点265〜270℃ ΓNMR；（第１図参照、CDCl3） δ（ppm） プロトン 0.8〜1.0 ｆ（2H） 1.35〜1.65 ｄ、ｅ（6H） 2.7〜3.0 ｂ（4H） 3.55〜4.1 ａ（8H） 6.0〜6.25 ｃ（4H） ΓIR；（第２図参照、KBr法） 1215cm-1、1020cm-1（Ｃ−Ｏ−Ｃ）Γ melting point 265-270℃ ΓNMR; (see Figure 1, CDCl 3 ) δ (ppm) Proton 0.8-1.0 f (2H) 1.35-1.65 d, e (6H) 2.7-3.0 b (4H) 3.55-4.1 a (8H) 6.0-6.25 c (4H) ΓIR; (See Figure 2, KBr method) 1215cm -1 , 1020cm -1 (C-O-C)
第１図は実施例１で得た化合物〔３〕のNMR
スペクトル図であり、第２図は同化合物のIRス
ペクトル図である。
Figure 1 shows NMR of compound [3] obtained in Example 1.
FIG. 2 is an IR spectrum diagram of the same compound.
Claims (1)
下式〔２〕で示される５−ノルボルネン−２，２
−ジメタノールとを反応させることを特徴とする
下式〔３〕で示されるスピロオルソカーボネート
の製造方法。 （こゝでR1、R2、R3およびR4は直鎖または分枝
状の炭素数が１〜８のアルキル基を示す。） [Scope of Claims] 1 Ortho carbonate represented by the following formula [1] and 5-norbornene-2,2 represented by the following formula [2]
- A method for producing spiroorthocarbonate represented by the following formula [3], which comprises reacting with dimethanol. (Here, R 1 , R 2 , R 3 and R 4 represent a linear or branched alkyl group having 1 to 8 carbon atoms.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58232242A JPS60126288A (en) | 1983-12-10 | 1983-12-10 | Production of spiroorthocarbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58232242A JPS60126288A (en) | 1983-12-10 | 1983-12-10 | Production of spiroorthocarbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60126288A JPS60126288A (en) | 1985-07-05 |
| JPH0545597B2 true JPH0545597B2 (en) | 1993-07-09 |
Family
ID=16936195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58232242A Granted JPS60126288A (en) | 1983-12-10 | 1983-12-10 | Production of spiroorthocarbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60126288A (en) |
-
1983
- 1983-12-10 JP JP58232242A patent/JPS60126288A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60126288A (en) | 1985-07-05 |
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