JPH0548217B2 - - Google Patents
Info
- Publication number
- JPH0548217B2 JPH0548217B2 JP59237739A JP23773984A JPH0548217B2 JP H0548217 B2 JPH0548217 B2 JP H0548217B2 JP 59237739 A JP59237739 A JP 59237739A JP 23773984 A JP23773984 A JP 23773984A JP H0548217 B2 JPH0548217 B2 JP H0548217B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- aromatic aldehydes
- present
- group
- examples
- 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 - Fee Related
Links
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- WTWBUQJHJGUZCY-UHFFFAOYSA-N cuminaldehyde Chemical compound CC(C)C1=CC=C(C=O)C=C1 WTWBUQJHJGUZCY-UHFFFAOYSA-N 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- UIFVCPMLQXKEEU-UHFFFAOYSA-N 2,3-dimethylbenzaldehyde Chemical compound CC1=CC=CC(C=O)=C1C UIFVCPMLQXKEEU-UHFFFAOYSA-N 0.000 description 1
- VDEAMZDXUCYOQJ-UHFFFAOYSA-N 2-acetylbenzaldehyde Chemical compound CC(=O)C1=CC=CC=C1C=O VDEAMZDXUCYOQJ-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- SFNWXOPQLKYXHN-UHFFFAOYSA-N 2-cyclohexylbenzaldehyde Chemical compound O=CC1=CC=CC=C1C1CCCCC1 SFNWXOPQLKYXHN-UHFFFAOYSA-N 0.000 description 1
- IMPIIVKYTNMBCD-UHFFFAOYSA-N 2-phenoxybenzaldehyde Chemical compound O=CC1=CC=CC=C1OC1=CC=CC=C1 IMPIIVKYTNMBCD-UHFFFAOYSA-N 0.000 description 1
- LCRCBXLHWTVPEQ-UHFFFAOYSA-N 2-phenylbenzaldehyde Chemical compound O=CC1=CC=CC=C1C1=CC=CC=C1 LCRCBXLHWTVPEQ-UHFFFAOYSA-N 0.000 description 1
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- -1 aromatic carboxylic acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical class ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000543 intermediate Substances 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 239000008096 xylene Substances 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
〔産業上の利用分野〕
本発明は各種有機合成反応の中間体として有用
な芳香族アルデヒド類の製造方法に関する。
〔従来技術とその問題点〕
置換芳香族アルデヒド類の製造には従来からさ
まざまな方法が行なわれてきた。例えば、置換ト
ルエン類のハロゲン化−加水分解法、置換安息香
酸クロリドの選択的還元法、置換ベンジルアルコ
ールの酸化法等が挙げられる。しかしながらこれ
らの方法はいずれも高価な原料を要し、多量の当
量反応試薬を用いるためコスト高となり、しかも
生成アルデヒドの純度が悪く綿密な精製を必要と
する等の問題点を有していた。一方、最近酸化ジ
ルコニウムを触媒に用いると、安息香酸の直接水
素化によりベンズアルデヒドが生成することが報
告されたが、触媒活性が低く、反応に高温を要す
るため、比較的不安定な物質である置換芳香族ア
ルデヒド類の製造にそのまま応用することは不可
能であつた。
〔問題点を解決するための手段〕
本発明者はかかる問題点を解決すべく鋭意検討
を続けた結果、芳香族カルボン酸エステル類を水
素化して芳香族アルデヒド類を製造するに際し、
触媒として、クロム、コバルト、インジウムおよ
びレニウムから選ばれた一種以上の元素を必須元
素として含む酸化ジルコニウムを用いることによ
り、触媒活性が著しく高まり、比較的低温におい
ても反応を実施することが可能になることを見出
し、本発明を完成した。
以下に本発明方法を詳細に説明する。
本発明方法により製造される芳香族アルデヒド
類は、
一般式
で示される。ここでｎは１または２であり、
[Industrial Application Field] The present invention relates to a method for producing aromatic aldehydes useful as intermediates in various organic synthesis reactions. [Prior art and its problems] Various methods have been used to produce substituted aromatic aldehydes. Examples include halogenation-hydrolysis of substituted toluenes, selective reduction of substituted benzoic acid chloride, and oxidation of substituted benzyl alcohol. However, all of these methods require expensive raw materials and a large amount of equivalent reaction reagents, resulting in high costs, and have problems such as the resulting aldehyde having poor purity and requiring careful purification. On the other hand, it has recently been reported that when zirconium oxide is used as a catalyst, benzaldehyde is produced by direct hydrogenation of benzoic acid. It was impossible to apply it directly to the production of aromatic aldehydes. [Means for Solving the Problems] As a result of intensive studies to solve these problems, the present inventor found that when producing aromatic aldehydes by hydrogenating aromatic carboxylic acid esters,
By using zirconium oxide, which contains as an essential element one or more elements selected from chromium, cobalt, indium, and rhenium, the catalytic activity is significantly increased, making it possible to carry out the reaction even at relatively low temperatures. They discovered this and completed the present invention. The method of the present invention will be explained in detail below. The aromatic aldehydes produced by the method of the present invention have the general formula It is indicated by. Here n is 1 or 2,
【式】は置換基、例えば、アルキル基、シク
ロアルキル基、アリール基、アルコキシ基、アリ
ールオキシ基、ハロゲン原子、ヒドロキシル基、
ホルミル基、アシル基等を有してもよいベンゼン
環を表わす。
具体的な化合物としては、例えばトルアルデヒ
ド、ジメチルベンズアルデヒド、シクロヘキシル
ベンズアルデヒド、クミンアルデヒド、ビフエニ
ルアルデヒド、アニスアルデヒド、フエノキシベ
ンズアルデヒド、クロロベンズアルデヒド、テレ
フタルアルデヒド、ヒドロキシベンズアルデヒ
ド、アセチルベンズアルデヒド等が挙げられる。
これらの芳香族アルデヒド類は対応する
一般式
で示される芳香族カルボン酸またはそのエステル
類を水素化して製造される。ここでｎおよび
[Formula] represents a substituent, such as an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, a hydroxyl group,
Represents a benzene ring that may have a formyl group, acyl group, etc. Specific compounds include, for example, tolualdehyde, dimethylbenzaldehyde, cyclohexylbenzaldehyde, cuminaldehyde, biphenylaldehyde, anisaldehyde, phenoxybenzaldehyde, chlorobenzaldehyde, terephthalaldehyde, hydroxybenzaldehyde, acetylbenzaldehyde, and the like.
These aromatic aldehydes have the corresponding general formula It is produced by hydrogenating the aromatic carboxylic acid shown or its esters. where n and
以上、本発明によれば、クロム、コバルト、イ
ンジウムおよびレニウムから選ばれた一種以上の
元素を必須元素として含む酸化ジルコニウムを触
媒として用い、芳香族カルボン酸またはカルボン
酸エステル類の水素化反応を行なうことにより、
触媒活性が著しく高まり、芳香族アルデヒド類を
従来の方法に比較し高収率で得ることができる。
〔実施例〕
次に本発明を実施例を挙げて更に具体的に説明
するが、本発明はその要旨を逸脱しない限り、以
下の実施例に限定されるものではない。
実施例 １〜８
ガラス製反応管に第１表に示す組成の触媒５ml
を充填して加熱し、水素と共に芳香族カルボン酸
エステルを導入した。所定の時間水素化反応を行
なつた後、生成物を捕集し分析を行なつた。結果
を第１表に示す。
尚、実施例１〜８において、芳香族カルボン酸
エステルの融点が高いものは、ベンゼンもしくは
キシレン溶液として反応器に供給した。
As described above, according to the present invention, a hydrogenation reaction of aromatic carboxylic acids or carboxylic acid esters is carried out using zirconium oxide containing as an essential element one or more elements selected from chromium, cobalt, indium, and rhenium. By this,
Catalytic activity is significantly increased, and aromatic aldehydes can be obtained in higher yields than conventional methods. [Examples] Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it departs from the gist thereof. Examples 1 to 8 5 ml of catalyst having the composition shown in Table 1 in a glass reaction tube
was charged and heated, and aromatic carboxylic acid ester was introduced together with hydrogen. After carrying out the hydrogenation reaction for a predetermined period of time, the products were collected and analyzed. The results are shown in Table 1. In Examples 1 to 8, aromatic carboxylic acid esters with high melting points were supplied to the reactor as benzene or xylene solutions.
【表】【table】
Claims (1)
基を表わし、【式】は置換基を有してもよい ベンゼン環を表わす。但し、ｎ＝２のときＲは互
に異なつていてもよい。） で示される芳香族カルボン酸エステル類を水素化
して 一般式 （式中、ｎおよび【式】は式（）における 定義と同様。） で示される芳香族アルデヒド類を製造するに際
し、クロム、コバルト、インジウムおよびレニウ
ムから選ばれた一種以上の元素をジルコニウムに
対する原子比で0.0001ないし0.5含む酸化ジルコ
ニウムを触媒として用いることを特徴とする芳香
族アルデヒド類の製造方法。[Claims] 1. General formula (In the formula, n is 1 or 2, R represents a hydrocarbon residue, and [Formula] represents a benzene ring which may have a substituent. However, when n = 2, R is different from each other. ) is hydrogenated to form the general formula (In the formula, n and [formula] are the same as the definitions in formula ().) When producing aromatic aldehydes represented by 1. A method for producing aromatic aldehydes, characterized in that zirconium oxide containing a ratio of 0.0001 to 0.5 is used as a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59237739A JPS61115043A (en) | 1984-11-12 | 1984-11-12 | Preparation of aromatic aldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59237739A JPS61115043A (en) | 1984-11-12 | 1984-11-12 | Preparation of aromatic aldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61115043A JPS61115043A (en) | 1986-06-02 |
| JPH0548217B2 true JPH0548217B2 (en) | 1993-07-20 |
Family
ID=17019752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59237739A Granted JPS61115043A (en) | 1984-11-12 | 1984-11-12 | Preparation of aromatic aldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61115043A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63179845A (en) * | 1986-08-14 | 1988-07-23 | Idemitsu Kosan Co Ltd | Production of carboxylic acid ester |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60152434A (en) * | 1984-01-18 | 1985-08-10 | Mitsubishi Chem Ind Ltd | Production of aromatic aldehyde |
| JPS60243037A (en) * | 1984-05-17 | 1985-12-03 | Mitsubishi Chem Ind Ltd | Production of aromatic aldehyde |
| JPS61115042A (en) * | 1984-11-08 | 1986-06-02 | Mitsubishi Chem Ind Ltd | Preparation of aromatic aldehyde |
-
1984
- 1984-11-12 JP JP59237739A patent/JPS61115043A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60152434A (en) * | 1984-01-18 | 1985-08-10 | Mitsubishi Chem Ind Ltd | Production of aromatic aldehyde |
| JPS60243037A (en) * | 1984-05-17 | 1985-12-03 | Mitsubishi Chem Ind Ltd | Production of aromatic aldehyde |
| JPS61115042A (en) * | 1984-11-08 | 1986-06-02 | Mitsubishi Chem Ind Ltd | Preparation of aromatic aldehyde |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61115043A (en) | 1986-06-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |