JPH04164085A - Production of spiroorthocarbonate compound - Google Patents
Production of spiroorthocarbonate compoundInfo
- Publication number
- JPH04164085A JPH04164085A JP2289505A JP28950590A JPH04164085A JP H04164085 A JPH04164085 A JP H04164085A JP 2289505 A JP2289505 A JP 2289505A JP 28950590 A JP28950590 A JP 28950590A JP H04164085 A JPH04164085 A JP H04164085A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- reaction
- expressed
- alkyl
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract 3
- 150000002367 halogens Chemical class 0.000 claims abstract 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- 125000002560 nitrile group Chemical group 0.000 claims 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- KCFFRSKANGJGIF-UHFFFAOYSA-N [5-(hydroxymethyl)-5-bicyclo[2.2.2]oct-2-enyl]methanol Chemical compound C1CC2C(CO)(CO)CC1C=C2 KCFFRSKANGJGIF-UHFFFAOYSA-N 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000002994 raw material Substances 0.000 abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- AHJWSRRHTXRLAQ-UHFFFAOYSA-N tetramethoxymethane Chemical compound COC(OC)(OC)OC AHJWSRRHTXRLAQ-UHFFFAOYSA-N 0.000 abstract description 3
- RXCVUXLCNLVYIA-UHFFFAOYSA-N orthocarbonic acid Chemical compound OC(O)(O)O RXCVUXLCNLVYIA-UHFFFAOYSA-N 0.000 abstract description 2
- JLNNZTUPLGIUKM-UHFFFAOYSA-N [2-(cycloocten-1-yl)cycloocten-1-yl]methanediol Chemical compound C1CCCCCC(C(O)O)=C1C1=CCCCCCC1 JLNNZTUPLGIUKM-UHFFFAOYSA-N 0.000 abstract 1
- 150000002825 nitriles Chemical class 0.000 abstract 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 abstract 1
- -1 orthocarbonic acid ester Chemical class 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005580 one pot reaction Methods 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 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
- 238000001228 spectrum Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000009835 boiling Methods 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
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 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
- 239000011369 resultant mixture Substances 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
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はスピロオルソカーボネート化合物の製造方法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing spiroorthocarbonate compounds.
（従来の技術）
従来法は一般的工業製品としては非常に高価な打機スズ
化合物と、毒性が高く取扱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テするために、種々の問題点
を有しており、スピロオルソカーボネート化合物の工業
的製法としては現実性に乏しいものである。(Conventional technology) The conventional method uses a hammer tin compound, which is extremely expensive for a general industrial product, and carbon disulfide, which is highly toxic and difficult to handle, as raw materials, and the reaction process is complicated. However, since it is very difficult to separate and obtain the target product, this method has various problems and is impractical as an industrial method for producing spiroorthocarbonate compounds.
（発明が解決しようとする課題）
本発明は、取扱いが容品な原料から、−段反応で容易、
かつ効率よくスピロオルソカーボネート化合物を製造し
ようとするものである。(Problems to be Solved by the Invention) The present invention enables easy, one-step reaction from raw materials that are easy to handle.
The purpose of the present invention is to efficiently produce a spiroorthocarbonate compound.
（課題を解決するための手段）
本発明者らはスピロオルソカーボネート化合物■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■を反応させることによっ
て、−段反応で極めて容易に化合物■を製造できること
を見出し、本発明に到達した。(Means for Solving the Problem) As a result of various studies on a more advantageous method for producing spiroorthocarbonate compound (1), the present inventors found that the orthocarbonate ester represented by the above formula (1) (hereinafter referred to as compound ( The inventors have discovered that compound (1) can be produced very easily in a two-step reaction by reacting compound (1) with compound (1), and have arrived at the present invention.
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■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
ったのである。An example of the method of the present invention is shown in the following reaction formula,
Although there is a possibility that various compounds may be produced in the reaction of ortho carbonic acid ester and compound (1), it has become clear that compound (3) is actually produced very efficiently.
１、
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、Ｒ’１Ｒ２１Ｒ３お
よびＲ４は炭素数１〜８の直鎖または分岐状のアルキル
基が適切である。またＲ１−Ｒ４の有機基は互いに同一
でも異なっていてもよい。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−プチルオルソカーボネー
ト、テトラ−１ｓｏ−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。1. R1. in compound (1) used as a raw material in the method of the present invention. As R2, R3 and R4 become larger, the boiling point of the alcohol produced by the reaction becomes higher and it becomes more difficult to remove it from the reaction system. or branched alkyl groups are suitable. Further, the organic groups of R1 to R4 may be the same or different from each other. Specific examples of compound (1) include tetramethyl orthocarbonate, tetraethyl orthocarbonate, tetra-n-butyl orthocarbonate, tetra-1so-butyl orthocarbonate, and tetra-n-pentyl orthocarbonate.
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■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■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。Compound (1) which is a raw material in carrying out the method of the present invention
It is preferable to use Compound (1) as dry as possible, and Compound (2) is preferably used in a theoretical amount (2 moles) or slightly less than the theoretical amount relative to the orthocarbonate (1 mole). 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 examples include toluene, xylene, di-n-butyl phthalate, di-n-
Octyl phthalate and the like are used.
反応は触媒たとえばｐ−）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、加温杖態で行うことが望ましい。触
媒の使用量は原料化合物に対して一般に０．００１〜５
ｗｔ％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-)luenesulfonic acid or sulfuric acid, optionally using a solvent such as those mentioned above, in a heated state. The amount of catalyst used is generally 0.001 to 5% based on the raw material compound.
wt% is sufficient, 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っ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ィーで分析することによ
っ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を、濾
過することによっ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 filtering the resultant mixture.
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って重合性物質として有用な化合物
（３）を容易がり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 using a raw material that is extremely easy to handle and with simple operations.
（実施例）
次に本発明方法を実施例によってさらに詳細に説明する
。(Example) 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、攪拌機および窒素吹き込
み口管付きの三ツロフラスコに、テトラメチルオルソカ
ーボネー） （５，４５ｇ、 ０．０４０ ｍｏｌ）
、化合物（２）（２，２−ジヒドロキシメチルビシクロ
［２゜２．２］オクト−５−エン） （１２，１１ｇ、
０．０７２ ｍｏｌ）、ｐ−トルエンスルホン酸（０
，０４ｇ、 ２．１Ｘ１０−４ ｍｏｌ）およびキシレ
ン（４５ｍＬ）を入れ、窒素気流下９０℃で１時間、１
００℃で１時間、１１０℃で２時間反応させた。留出メ
タノールの量は３．４６ ｇであった。Example 1 Tetramethyl orthocarbonate (5.45 g, 0.040 mol) was placed in a three-way flask equipped with a moisture meter, a stirrer, and a nitrogen inlet tube equipped with a condenser.
, Compound (2) (2,2-dihydroxymethylbicyclo[2°2.2]oct-5-ene) (12,11g,
0.072 mol), p-toluenesulfonic acid (0
, 04g, 2.1X10-4 mol) and xylene (45mL), and heated at 90°C for 1 hour under a nitrogen stream.
The reaction was carried out at 00°C for 1 hour and at 110°C for 2 hours. The amount of distilled methanol was 3.46 g.
トリエチルアミン ０．０８ ｍＬ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、この固体を濾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後、クロロホ
ルムを用いて再結晶操作を行ない。収量８．７ ｇ１収
率７０％（化合物■のＲとＲ′が水素の場合の化合物を
基準として算出）で結晶を得た。この結晶は元素分析、
ＴＲ（赤外吸収）スペクトル、ＮＭＲ（核磁気共鳴）ス
ペクトルから化合物においてＲとＲ′が水素である化合
物Ｇ３）と同定された。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. The solid was then washed with acetone and then recrystallized using chloroform. Crystals were obtained in a yield of 8.7 g and a yield of 70% (calculated based on the compound in which R and R' of compound (1) are hydrogen). This crystal was analyzed by elemental analysis.
From the TR (infrared absorption) spectrum and NMR (nuclear magnetic resonance) spectrum, it was identified as compound G3) in which R and R' are hydrogen.
（発明の効果）
本発明の製造方法によれば、スピロオルソカーボネート
化合物が取扱いが極めて容易な原料から一段反応によっ
て、容易かつ効率よく製造することが可能であり、工業
的意義は大きい。(Effects of the Invention) According to the production method of the present invention, it is possible to easily and efficiently produce a spiroorthocarbonate compound from raw materials that are extremely easy to handle through a one-step reaction, which has great industrial significance.
Claims (1)
で示される２，２−ジヒドロキシメチルビシクロ［２，
２，２］オクト−５−エン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化
合物の製造方法。 ▲数式、化学式、表等があります▼（１） （ここでＲ＾１、Ｒ＾２、Ｒ＾３およびＲ＾４は直鎖ま
たは分岐状の炭素数が１〜８のアルキル基を示し、それ
ぞれ同一であっても異なっていてもよい。） ▲数式、化学式、表等があります▼（２） Ｒ、Ｒ′は水素、ハロゲン、アルキル基、アリール基、
ヒドロキシル基、アルコキシル基、カルボキシル基、シ
リル基、アミノ基、ニトロ基、ニトリル基のいずれかを
示す。 ▲数式、化学式、表等があります▼（３） 〔Ｒ、Ｒ′は水素、ハロゲン、アルキル基、アリール基
、ヒドロキシル基、カルボキシル基、シリル基、アミノ
基、ニトロ基、ニトリル基のいずれかを示す。〕[Claims] Ortho carbonate represented by the following formula (1) and the following formula (2)
2,2-dihydroxymethylbicyclo[2,
2,2] Oct-5-ene. A method for producing a spiroorthocarbonate compound represented by the following formula (3). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (Here, R^1, R^2, R^3 and R^4 represent a straight chain or branched alkyl group having 1 to 8 carbon atoms, (They may be the same or different.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) R and R' are hydrogen, halogen, alkyl group, aryl group,
Indicates any one of a hydroxyl group, an alkoxyl group, a carboxyl group, a silyl group, an amino group, a nitro group, and a nitrile group. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (3) [R and R' are hydrogen, halogen, alkyl group, aryl group, hydroxyl group, carboxyl group, silyl group, amino group, nitro group, or nitrile group. show. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2289505A JPH04164085A (en) | 1990-10-26 | 1990-10-26 | Production of spiroorthocarbonate compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2289505A JPH04164085A (en) | 1990-10-26 | 1990-10-26 | Production of spiroorthocarbonate compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04164085A true JPH04164085A (en) | 1992-06-09 |
Family
ID=17744139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2289505A Pending JPH04164085A (en) | 1990-10-26 | 1990-10-26 | Production of spiroorthocarbonate compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04164085A (en) |
-
1990
- 1990-10-26 JP JP2289505A patent/JPH04164085A/en active Pending
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