JPS644512B2 - - Google Patents
Info
- Publication number
- JPS644512B2 JPS644512B2 JP56112632A JP11263281A JPS644512B2 JP S644512 B2 JPS644512 B2 JP S644512B2 JP 56112632 A JP56112632 A JP 56112632A JP 11263281 A JP11263281 A JP 11263281A JP S644512 B2 JPS644512 B2 JP S644512B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- dihydropyran
- alkoxytetrahydropyran
- ethoxytetrahydropyran
- potassium
- 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
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 15
- BTHLKLUTMYTDFM-UHFFFAOYSA-N 2-ethoxyoxane Chemical compound CCOC1CCCCO1 BTHLKLUTMYTDFM-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- HVHNQFALNKRKQY-UHFFFAOYSA-N 2-butoxyoxane Chemical compound CCCCOC1CCCCO1 HVHNQFALNKRKQY-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XTDKZSUYCXHXJM-UHFFFAOYSA-N 2-methoxyoxane Chemical compound COC1CCCCO1 XTDKZSUYCXHXJM-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- SZSMWWNXCCLLEK-UHFFFAOYSA-N dhp 3,4-dihydro-2h-pyran Chemical compound C1COC=CC1.C1COC=CC1 SZSMWWNXCCLLEK-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006049 ring expansion reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition 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
- Pyrane Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は２−アルコキシテトラヒドロピランを
カリウムでイオン交換したＡ型の合成ゼオライト
上で気相で熱分解することによつてジヒドロピラ
ンを製造する方法に関するものである。
目的生成物であるジヒドロピランは例えば、油
化学第29巻第11号第832頁（1980）等に記載があ
る如く、広い範囲の有機合成反応の原料として応
用され興味深い化合物である。従来、3.4−ジヒ
ドロ−2H−ピラン（ジヒドロピラン）の製造は
触媒として酸化アルミニウムを用いて、テトラヒ
ドロフルフリルアルコールを気相反応（脱水−環
拡大）させる方法等が知られている（Organic
Syntheses Coll.vol 第276頁（1955））。しか
しながら、これ等の方法では収率が66〜70％と低
く、必らずしも工業的に満足できる成積ではな
い。
本発明者らはジヒドロピランの新規な合成法に
ついて鋭意検討した結果、２−アルコキシテトラ
ヒドロピランをカリウムでイオン交換したＡ型の
合成ゼオライト上で熱分解することにより高収率
で、且つ経済的に有利なジヒドロピランが製造出
来ることを見い出した。
本発明に用いる触媒はＡ型の合成ゼオライトを
カリウムでイオン交換したものであり、具体的に
は次の商品名で市販されている。
モレキユラーシーブ3A（UCC社）、ゼオラムＡ
−３（東洋ソーダ社）バイリツトＳ（バイエル社）
等が好適に使用でき、また、モレキユラーシーブ
4A、ゼオラムＡ−４、バイリツトＴをカリウム
イオンにより交換吸着して使用することも出来
る。該合成ゼオライトは市販の成型品（ペレツ
ト）、粉末品をそのまま使用することができる。
この場合、カリウムでイオン交換されたＡ型の
ゼオライトは細孔径４Å以下を有しており、この
４Å以下であることが本反応に対して重要な意味
をもち、これ以上の細光径では副反応が起き、好
ましくない。
本発明における反応の一般式は次の通りであ
り、
（但し、Ｒは炭素数１〜６を有する低級アルキル
基を表わす。）
原料として使用される２−アルコキシテトラヒ
ドロピランは具体的には２−メトキシテトラヒド
ロピラン、２−エトキシテトラヒドロピラン、２
−プロポキシテトラヒドロピラン、２−ブトキシ
テトラヒドロピラン等が挙げられる。
本発明を実施する場合、反応温度は接触時間及
び使用する原料により異なるが、250〜400℃の範
囲が適当であり、接触時間は10〜60秒の範囲が適
当である。
反応方法は固定床、流動床等のいずれでも、又
常圧、減圧、加圧下のいずれの方法で行なつても
よいが、通常は操作の容易な固定床／常圧下で実
施すれば満足すべき成績が得られる。熱分解から
得られた反応生成物は冷却、凝縮された後、これ
を蒸溜分離することによつて、容易に目的生成物
を得ることができる。
次に、実施例により本発明を更に具体的に説明
する。
なお、各原料、生成物はガスクロマトグラフイ
で分析し、反応生績は次式で計算した。
変化率（％）＝反応２−アルコキシテトラヒドロ
ピラン（モル）／仕込２−アルコキシテトラヒドロピラ
ン（モル）×100
選択率（％）＝生成ジヒドロピラン（モル）／反
応２−アルコキシテトラヒドロピラン（モル）×100
収率（％）＝生成ジヒドロピラン（モル）／仕込
２−アルコキシテトラヒドロピラン（モル）×100
実施例 １
市販の粒径3.2mmφのモレキユラーシーブ3A60
mlを内径28mmφのステンレス製Ｕ字型反応管に充
填し、285℃（反応温度）に加熱した触媒上に２
−エトキシテトラヒドロピランを接触時間38秒に
なるように供給したところ、２−エトキシテトラ
ヒドロピランの変化率98.1％でジヒドロピランの
選択率97.9％であり、ジヒドロピランの収率96.0
％を得た。
実施例 ２
実施例１の反応温度を295℃及び接触時間を30
秒に変更した以外は同一の方法で反応した。結果
は２−エトキシテトラヒドロピランの変化率98.5
％でジヒドロピランの選択率99.1％でジヒドロピ
ランの収率97.6％を得た。
実施例 ３
実施例１と同一の触媒を用い、原料２−アルコ
キシテトラヒドロピランをヒドロピラン及び２−
ブトキシテトラヒドロピランに変更した以外は実
施例１と同一の方法で反応した。結果は次の通
り。
The present invention relates to a process for producing dihydropyrans by pyrolysis of 2-alkoxytetrahydropyrans in the gas phase on synthetic zeolites of type A ion-exchanged with potassium. The desired product, dihydropyran, is an interesting compound that can be used as a raw material for a wide range of organic synthesis reactions, as described, for example, in Yukagaku Vol. 29, No. 11, p. 832 (1980). Conventionally, 3,4-dihydro-2H-pyran (dihydropyran) has been produced by a method in which tetrahydrofurfuryl alcohol is subjected to a gas phase reaction (dehydration-ring expansion) using aluminum oxide as a catalyst.
Syntheses Coll. vol. 276 (1955)). However, these methods have low yields of 66 to 70%, and are not necessarily industrially satisfactory. As a result of intensive studies on a new method for synthesizing dihydropyran, the present inventors found that 2-alkoxytetrahydropyran can be thermally decomposed on A-type synthetic zeolite ion-exchanged with potassium in a high yield and economically. It has been found that advantageous dihydropyrans can be prepared. The catalyst used in the present invention is a type A synthetic zeolite ion-exchanged with potassium, and specifically, it is commercially available under the following trade name. Molecular sieve 3A (UCC), Zeorum A
-3 (Toyo Soda Co., Ltd.) Bayritt S (Bayer Co., Ltd.)
etc. can be used suitably, and molecular sieves can also be used.
4A, Zeolum A-4, and Bayritt T can also be used after being exchange-adsorbed with potassium ions. As the synthetic zeolite, commercially available molded products (pellets) or powder products can be used as they are. In this case, the A-type zeolite ion-exchanged with potassium has a pore diameter of 4 Å or less, and this 4 Å or less has an important meaning for this reaction; A reaction occurs and is not desirable. The general formula of the reaction in the present invention is as follows, (However, R represents a lower alkyl group having 1 to 6 carbon atoms.) Specifically, the 2-alkoxytetrahydropyran used as a raw material includes 2-methoxytetrahydropyran, 2-ethoxytetrahydropyran, 2-ethoxytetrahydropyran, and 2-alkoxytetrahydropyran.
-propoxytetrahydropyran, 2-butoxytetrahydropyran and the like. When carrying out the present invention, the reaction temperature varies depending on the contact time and the raw materials used, but is suitably in the range of 250 to 400°C, and the contact time is suitably in the range of 10 to 60 seconds. The reaction may be carried out in either a fixed bed or a fluidized bed, or under normal pressure, reduced pressure, or increased pressure, but it is usually satisfactory if the reaction is carried out in a fixed bed or under normal pressure, which is easy to operate. You can get the desired results. The reaction product obtained from the thermal decomposition is cooled and condensed, and then separated by distillation to easily obtain the desired product. Next, the present invention will be explained in more detail with reference to Examples. In addition, each raw material and product were analyzed by gas chromatography, and the reaction performance was calculated using the following formula. Change rate (%) = Reaction 2-alkoxytetrahydropyran (mol) / Charged 2-alkoxytetrahydropyran (mol) x 100 Selectivity (%) = Produced dihydropyran (mol) / Reaction 2-alkoxytetrahydropyran (mol) x 100 Yield (%) = Produced dihydropyran (mol) / Charged 2-alkoxytetrahydropyran (mol) x 100 Example 1 Commercially available molecular sieve 3A60 with a particle size of 3.2 mmφ
ml was filled into a stainless steel U-shaped reaction tube with an inner diameter of 28 mmφ, and placed on a catalyst heated to 285°C (reaction temperature).
- When ethoxytetrahydropyran was fed for a contact time of 38 seconds, the conversion rate of 2-ethoxytetrahydropyran was 98.1%, the selectivity of dihydropyran was 97.9%, and the yield of dihydropyran was 96.0%.
I got %. Example 2 The reaction temperature of Example 1 was changed to 295°C and the contact time was changed to 30°C.
I reacted in the same way except that I changed it to seconds. The result is a conversion rate of 2-ethoxytetrahydropyran of 98.5.
%, a selectivity of dihydropyran of 99.1% and a yield of dihydropyran of 97.6% were obtained. Example 3 Using the same catalyst as in Example 1, raw material 2-alkoxytetrahydropyran was converted into hydropyran and 2-
The reaction was carried out in the same manner as in Example 1 except that butoxytetrahydropyran was used. The results are as follows.
【表】
なお、シリカ−アルミナ触媒を用いて実施例１
に従つて２−エトキシテトラヒドロピランの熱分
解を行つたが、副反応が助長され、芳しい成績は
得られなかつた。[Table] In addition, Example 1 using a silica-alumina catalyst
Although 2-ethoxytetrahydropyran was thermally decomposed according to the method described above, side reactions were promoted and good results were not obtained.
Claims (1)
イトの存在下に、２−アルコキシテトラヒドロピ
ランを気相で熱分解することを特徴とするジヒド
ロピランの製造法。1. A method for producing dihydropyran, which comprises thermally decomposing 2-alkoxytetrahydropyran in the gas phase in the presence of synthetic A-type zeolite ion-exchanged with potassium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56112632A JPS5813581A (en) | 1981-07-17 | 1981-07-17 | Production of dihydropyran |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56112632A JPS5813581A (en) | 1981-07-17 | 1981-07-17 | Production of dihydropyran |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5813581A JPS5813581A (en) | 1983-01-26 |
| JPS644512B2 true JPS644512B2 (en) | 1989-01-25 |
Family
ID=14591582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56112632A Granted JPS5813581A (en) | 1981-07-17 | 1981-07-17 | Production of dihydropyran |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5813581A (en) |
-
1981
- 1981-07-17 JP JP56112632A patent/JPS5813581A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5813581A (en) | 1983-01-26 |
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