JP3805437B2 - Process for producing cyclopropanecarbaldehyde - Google Patents
Process for producing cyclopropanecarbaldehyde Download PDFInfo
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- JP3805437B2 JP3805437B2 JP23388496A JP23388496A JP3805437B2 JP 3805437 B2 JP3805437 B2 JP 3805437B2 JP 23388496 A JP23388496 A JP 23388496A JP 23388496 A JP23388496 A JP 23388496A JP 3805437 B2 JP3805437 B2 JP 3805437B2
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- Prior art keywords
- cyclopropanecarbaldehyde
- reaction
- dihydrofuran
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Description
【０００１】
【産業上の利用分野】
本発明は、シクロプロパンカルバルデヒドの製造方法に関する。本発明により提供されるシクロプロパンカルバルデヒドは、医薬、農薬の合成中間体として、例えば、除草剤として有用なＮ−（シクロプロピルメチル）−２，６−ジニトロ−Ｎ−プロピル−４−（トリフルオロメチル）ベンゼンアミンの合成中間体として有用である。
【０００２】
【従来の技術】
従来、シクロプロパンカルバルデヒドの製造方法としては、２，３−ジヒドロフランを気相において３７５℃に加熱し、熱転位させる方法が知られている［ジャーナル オブ アメリカン ケミカル ソサエティ（Journal of American Chemical Society）、６９巻、３００２頁（１９４７年）参照］。かかる文献には、５００℃以上の高温で反応を行った場合には、副生成物であるクロトンアルデヒドが増加し、また、生成したシクロプロパンカルバルデヒドがプロピレンと一酸化炭素に熱分解するなどの副反応が起こり、シクロプロパンカルバルデヒドの収率が低下することが記載されている。一方、上記の製法の問題点を解決するために、４００〜５２５℃の範囲、より好ましくは４２０〜４８５℃の範囲で異性化反応を行う方法が提案されている［米国特許明細書第４２７５２３８号参照］。
【０００３】
【発明が解決しようとする課題】
上記米国特許明細書においては、実施例２では４６０℃、実施例３では４８０℃で異性化反応を行っているが、この時の空時収率を求めると、実施例２では０．７トン／ｍ3 ・日、実施例３では１．７トン／ｍ3 ・日といずれも低い。したがって、上記米国特許明細書記載の方法にしたがって工業的にシクロプロパンカルバルデヒドを製造する場合には、反応装置を大きくせざるを得ないという問題点を有していた。
しかして、本発明の目的は、選択性を保持しつつ、高い生産性で、シクロプロパンカルバルデヒドを工業的に有利に製造する方法を提供することにある。
【０００４】
【課題を解決するための手段】
本発明によれば、上記の目的は、２，３−ジヒドロフランを、大気圧下、気相において５０％以下の転化率で、５３０℃〜７００℃に加熱することを特徴とするシクロプロパンカルバルデヒドの製造方法を提供することにより達成される。
【０００５】
【発明の実施の形態】
本発明における反応は、大気圧下、５３０℃〜７００℃、好ましくは５６０℃〜６００℃の範囲の温度で行われる。５３０℃より低い温度では、本発明のような高い空時収率は達成されない。また、反応温度を７００℃より高い温度にするには特殊な装置が必要となり、好ましくない。
【０００６】
上記の熱反応に用いる装置は、均一に加熱できるように工夫されていればどのような装置であってもよく、例えば、セラミックボールを充填したステンレス製反応管や充填剤を電磁誘導により加熱できる反応管などが用いられる。
【０００７】
２，３−ジヒドロフランは、予め加熱し、気化させて熱反応装置に導入される。
【０００８】
本発明によれば、選択性を低下させることなく生産性を高めることができ、シクロプロパンカルバルデヒドの空時収率は従来法の０．７〜１．７トン／ｍ3 ・日から１桁高い約１０トン／ｍ3 ・日以上にも達する。
【０００９】
【実施例】
以下、実施例により本発明をさらに詳しく説明するが、本発明は実施例により何ら限定されるものではない。
【００１０】
実施例１
セラミックボールを充填した加熱領域の容積が１１０ｃｃのステンレス製反応管を電気炉により加熱し、ここに蒸発器を用いてガス化させた２，３−ジヒドロフランを１２０ｇ／ｈｒの速度で導入した。反応管内の最高温度が５６０℃になるように調整し、反応後のガスは凝縮器を用いて捕集した。温度が安定した後の３０分間に、シクロプロパンカルバルデヒド１６．４ｇを含む反応液５８．８ｇを得た。２，３−ジヒドロフランの転化率は３２．６％、シクロプロパンカルバルデヒドの選択率は８３．８％、空時収率は７．２ｔ／ｍ3・日であった。
【００１１】
実施例２
反応管内の最高温度が５６５℃になるように調整し、蒸発器を用いてガス化させた２，３−ジヒドロフランを１４５ｇ／ｈｒの速度で導入した以外は実施例１と同様に反応を行った結果、シクロプロパンカルバルデヒド２２．０ｇを含む反応液７１．１ｇを得た。２，３−ジヒドロフランの転化率は３７．６％、シクロプロパンカルバルデヒドの選択率は８０．６％、空時収率は９．６ｔ／ｍ3 ・日であった。
【００１２】
実施例３
反応管内の最高温度が５６７℃になるように調整し、蒸発器を用いてガス化させた２，３−ジヒドロフランを１５０ｇ／ｈｒの速度で導入した以外は実施例１と同様に反応を行った結果、シクロプロパンカルバルデヒド２２．９ｇを含む反応液７３．５ｇを得た。２，３−ジヒドロフランの転化率は３８．０％、シクロプロパンカルバルデヒドの選択率は８０．３％、空時収率は１０．０ｔ／ｍ3 ・日であった。
【００１３】
実施例４
反応管内の最高温度が５７０℃になるように調整し、蒸発器を用いてガス化させた２，３−ジヒドロフランを２００ｇ／ｈｒの速度で導入した以外は実施例１と同様に反応を行った結果、シクロプロパンカルバルデヒド２８．０ｇを含む反応液９７．５ｇを得た。２，３−ジヒドロフランの転化率は３３．７％、シクロプロパンカルバルデヒドの選択率は８３．１％、空時収率は１２．２ｔ／ｍ3 ・日であった。
【００１４】
実施例５
反応管内の最高温度が５８０℃になるように調整し、蒸発器を用いてガス化させた２，３−ジヒドロフランを２９１ｇ／ｈｒの速度で導入した以外は実施例１と同様に反応を行った結果、シクロプロパンカルバルデヒド４１．１ｇを含む反応液１４２．９ｇを得た。２，３−ジヒドロフランの転化率は３４．９％、シクロプロパンカルバルデヒドの選択率は８０．７％、空時収率は１７．８ｔ／ｍ3・日であった。
【００１５】
実施例６
反応管内の最高温度が５８６℃になるように調整し、蒸発器を用いてガス化させた２，３−ジヒドロフランを４６０ｇ／ｈｒの速度で導入した以外は実施例１と同様に反応を行った結果、シクロプロパンカルバルデヒド６７．５ｇを含む反応液２２５．４ｇを得た。２，３−ジヒドロフランの転化率は３５．９％、シクロプロパンカルバルデヒドの選択率は８１．８％、空時収率は２９．５ｔ／ｍ3・日であった。
【００１６】
実施例７
反応管内の最高温度が５９０℃になるように調整し、蒸発器を用いてガス化させた２，３−ジヒドロフランを５００ｇ／ｈｒの速度で導入した以外は実施例１と同様に反応を行った結果、シクロプロパンカルバルデヒド７７．８ｇを含む反応液２４２．５ｇを得た。２，３−ジヒドロフランの転化率は３９．１％、シクロプロパンカルバルデヒドの選択率は７９．６％、空時収率は３４．０ｔ／ｍ3・日であった。
【００１７】
【発明の効果】
本発明によれば、選択性を保持しつつ、高い生産性で、シクロプロパンカルバルデヒドを工業的に有利に製造することができる。[0001]
[Industrial application fields]
The present invention relates to a process for producing cyclopropanecarbaldehyde. The cyclopropane carbaldehyde provided by the present invention is an intermediate for the synthesis of pharmaceuticals and agricultural chemicals, for example, N- (cyclopropylmethyl) -2,6-dinitro-N-propyl-4- (tri-methyl) useful as a herbicide. It is useful as an intermediate for the synthesis of (fluoromethyl) benzeneamine.
[0002]
[Prior art]
Conventionally, as a method for producing cyclopropanecarbaldehyde, a method in which 2,3-dihydrofuran is heated to 375 ° C. in a gas phase and thermally rearranged is known [Journal of American Chemical Society]. 69, 3002 (1947)]. According to this document, when the reaction is performed at a high temperature of 500 ° C. or higher, crotonaldehyde as a by-product increases, and the produced cyclopropanecarbaldehyde is thermally decomposed into propylene and carbon monoxide. It is described that side reactions occur and the yield of cyclopropanecarbaldehyde decreases. On the other hand, in order to solve the problems of the above-mentioned production method, a method of performing an isomerization reaction in the range of 400 to 525 ° C., more preferably in the range of 420 to 485 ° C. has been proposed [US Pat. No. 4,275,238. reference].
[0003]
[Problems to be solved by the invention]
In the above US patent specification, the isomerization reaction is carried out at 460 ° C. in Example 2 and at 480 ° C. in Example 3. When the space time yield at this time is determined, 0.7 ton in Example 2 is obtained. / M 3 · day, and in Example 3, 1.7 ton / m 3 · day are both low. Therefore, in the case of producing cyclopropane carbaldehyde industrially according to the method described in the above-mentioned US patent specification, there has been a problem that the reactor must be enlarged.
Thus, an object of the present invention is to provide a method for producing cyclopropanecarbaldehyde industrially advantageously with high productivity while maintaining selectivity.
[0004]
[Means for Solving the Problems]
According to the present invention, the above object is achieved by heating 2,3-dihydrofuran to 530 ° C. to 700 ° C. at a conversion rate of 50% or less in the gas phase under atmospheric pressure. This is achieved by providing a method for producing aldehyde.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The reaction in the present invention is performed under atmospheric pressure at a temperature in the range of 530 ° C to 700 ° C, preferably 560 ° C to 600 ° C. At temperatures below 530 ° C., high space time yields as in the present invention are not achieved. In addition, a special apparatus is required to make the reaction temperature higher than 700 ° C., which is not preferable.
[0006]
The apparatus used for the thermal reaction may be any apparatus as long as it can be heated uniformly. For example, a stainless steel reaction tube filled with a ceramic ball or a filler can be heated by electromagnetic induction. A reaction tube or the like is used.
[0007]
2,3-dihydrofuran is preheated and vaporized before being introduced into the thermal reactor.
[0008]
According to the present invention, productivity can be increased without reducing selectivity, and the space-time yield of cyclopropanecarbaldehyde is one digit from 0.7 to 1.7 tons / m 3 · day of the conventional method. It reaches about 10 tons / m 3 · day or more.
[0009]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by an Example.
[0010]
Example 1
A stainless steel reaction tube having a heating area of 110 cc filled with ceramic balls was heated by an electric furnace, and 2,3-dihydrofuran gasified using an evaporator was introduced at a rate of 120 g / hr. The maximum temperature in the reaction tube was adjusted to 560 ° C., and the gas after the reaction was collected using a condenser. In 30 minutes after the temperature was stabilized, 58.8 g of a reaction solution containing 16.4 g of cyclopropanecarbaldehyde was obtained. The conversion rate of 2,3-dihydrofuran was 32.6%, the selectivity of cyclopropanecarbaldehyde was 83.8%, and the space-time yield was 7.2 t / m 3 · day.
[0011]
Example 2
The reaction was conducted in the same manner as in Example 1 except that the maximum temperature in the reaction tube was adjusted to 565 ° C., and 2,3-dihydrofuran gasified using an evaporator was introduced at a rate of 145 g / hr. As a result, 71.1 g of a reaction solution containing 22.0 g of cyclopropanecarbaldehyde was obtained. The conversion of 2,3-dihydrofuran was 37.6%, the selectivity for cyclopropanecarbaldehyde was 80.6%, and the space-time yield was 9.6 t / m 3 · day.
[0012]
Example 3
The reaction was carried out in the same manner as in Example 1 except that the maximum temperature in the reaction tube was adjusted to 567 ° C., and 2,3-dihydrofuran gasified using an evaporator was introduced at a rate of 150 g / hr. As a result, 73.5 g of a reaction solution containing 22.9 g of cyclopropanecarbaldehyde was obtained. The conversion of 2,3-dihydrofuran was 38.0%, the selectivity for cyclopropanecarbaldehyde was 80.3%, and the space-time yield was 10.0 t / m 3 · day.
[0013]
Example 4
The reaction was carried out in the same manner as in Example 1 except that the maximum temperature in the reaction tube was adjusted to 570 ° C., and 2,3-dihydrofuran gasified using an evaporator was introduced at a rate of 200 g / hr. As a result, 97.5 g of a reaction solution containing 28.0 g of cyclopropanecarbaldehyde was obtained. The conversion of 2,3-dihydrofuran was 33.7%, the selectivity of cyclopropanecarbaldehyde was 83.1%, and the space-time yield was 12.2 t / m 3 · day.
[0014]
Example 5
The reaction was carried out in the same manner as in Example 1 except that the maximum temperature in the reaction tube was adjusted to 580 ° C., and 2,3-dihydrofuran gasified using an evaporator was introduced at a rate of 291 g / hr. As a result, 142.9 g of a reaction solution containing 41.1 g of cyclopropanecarbaldehyde was obtained. The conversion of 2,3-dihydrofuran was 34.9%, the selectivity for cyclopropanecarbaldehyde was 80.7%, and the space-time yield was 17.8 t / m 3 · day.
[0015]
Example 6
The reaction was carried out in the same manner as in Example 1 except that the maximum temperature in the reaction tube was adjusted to 586 ° C., and 2,3-dihydrofuran gasified using an evaporator was introduced at a rate of 460 g / hr. As a result, 225.4 g of a reaction solution containing 67.5 g of cyclopropanecarbaldehyde was obtained. The conversion of 2,3-dihydrofuran was 35.9%, the selectivity for cyclopropanecarbaldehyde was 81.8%, and the space-time yield was 29.5 t / m 3 · day.
[0016]
Example 7
The reaction was carried out in the same manner as in Example 1 except that the maximum temperature in the reaction tube was adjusted to 590 ° C., and 2,3-dihydrofuran gasified using an evaporator was introduced at a rate of 500 g / hr. As a result, 242.5 g of a reaction solution containing 77.8 g of cyclopropanecarbaldehyde was obtained. The conversion of 2,3-dihydrofuran was 39.1%, the selectivity for cyclopropanecarbaldehyde was 79.6%, and the space-time yield was 34.0 t / m 3 · day.
[0017]
【The invention's effect】
According to the present invention, cyclopropanecarbaldehyde can be industrially advantageously produced with high productivity while maintaining selectivity.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23388496A JP3805437B2 (en) | 1996-09-04 | 1996-09-04 | Process for producing cyclopropanecarbaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23388496A JP3805437B2 (en) | 1996-09-04 | 1996-09-04 | Process for producing cyclopropanecarbaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1077242A JPH1077242A (en) | 1998-03-24 |
| JP3805437B2 true JP3805437B2 (en) | 2006-08-02 |
Family
ID=16962077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23388496A Expired - Fee Related JP3805437B2 (en) | 1996-09-04 | 1996-09-04 | Process for producing cyclopropanecarbaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3805437B2 (en) |
-
1996
- 1996-09-04 JP JP23388496A patent/JP3805437B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH1077242A (en) | 1998-03-24 |
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