JPS625141B2 - - Google Patents
Info
- Publication number
- JPS625141B2 JPS625141B2 JP11723378A JP11723378A JPS625141B2 JP S625141 B2 JPS625141 B2 JP S625141B2 JP 11723378 A JP11723378 A JP 11723378A JP 11723378 A JP11723378 A JP 11723378A JP S625141 B2 JPS625141 B2 JP S625141B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- acid
- yield
- oxygen
- present
- 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
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000071 diazene Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 150000001299 aldehydes Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 4
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 2
- -1 saturated aliphatic aldehydes Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- YNKMHABLMGIIFX-UHFFFAOYSA-N benzaldehyde;methane Chemical compound C.O=CC1=CC=CC=C1 YNKMHABLMGIIFX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 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
- 239000012071 phase Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明はアルデヒドの液相酸素酸化による有機
過カルボン酸の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing organic percarboxylic acids by liquid phase oxygen oxidation of aldehydes.
従来、アルデヒドの液相酸素酸化による有機過
カルボン酸の製造はエステル等の非プロトン性溶
媒中で行なわれるのが一般的であり、カルボン酸
溶媒中で行なう収率の良い方法は殆んど見い出さ
れていない。 Conventionally, the production of organic percarboxylic acids by liquid-phase oxygen oxidation of aldehydes has generally been carried out in aprotic solvents such as esters, and very few methods with high yields have been found that carry out the process in carboxylic acid solvents. Not yet.
アルデヒドを酸化して有機過カルボン酸を製造
する際には、必ず対応するカルボン酸が相当量副
生するので、特に、原料アルデヒドに対応するカ
ルボン酸を反応溶媒として使用した場合には製造
プロセスが簡略化され、工業的に非常に有利であ
る。 When an organic percarboxylic acid is produced by oxidizing an aldehyde, a considerable amount of the corresponding carboxylic acid is always produced as a by-product, so the production process is particularly difficult when the carboxylic acid corresponding to the raw material aldehyde is used as a reaction solvent. It is simplified and industrially very advantageous.
カルボン酸溶媒中でアルデヒドを酸素酸化する
方法としては、銅塩とジアミンの錯体を触媒とし
て使用する方法が知られているが、有機過カルボ
ン酸の収率は依然として不十分であり、本発明者
らは収率が高く且つ実質的に重金属触媒を使用し
ない有機過カルボン酸の製造方法について探索を
行なつた。その結果、芳香族複素環を構成する共
役α−ジイミン化合物の存在下にアルデヒドを液
相で酸素酸化すれば収率よく有機過カルボン酸が
得られることを見い出し、本発明に到達したもの
である。 As a method for oxidizing aldehydes with oxygen in a carboxylic acid solvent, a method using a complex of a copper salt and a diamine as a catalyst is known, but the yield of organic percarboxylic acid is still insufficient, and the present inventors searched for a method for producing organic percarboxylic acids with high yield and substantially without the use of heavy metal catalysts. As a result, it was discovered that an organic percarboxylic acid can be obtained in good yield by oxygen-oxidizing an aldehyde in a liquid phase in the presence of a conjugated α-diimine compound constituting an aromatic heterocycle, leading to the present invention. .
以下に本発明を詳細に説明する。 The present invention will be explained in detail below.
本発明方法において原料として使用し得るアル
デヒドはアセトアルデヒド、プロピオンアルデヒ
ド、ｎ−ブチルアルデヒド、イソブチルアルデヒ
ド、ヘプタナール、２−エチルヘキサナール等の
飽和脂肪族アルデヒド、アクロレイン、メタクロ
レイン等の不飽和脂肪族アルデヒド、ベンズアル
デヒド、トルイルアルデヒド等の芳香族アルデヒ
ドなどであり、本発明方法によりそれぞれ対応す
る有機過カルボン酸が得られる。 Aldehydes that can be used as raw materials in the method of the present invention include saturated aliphatic aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, heptanal, and 2-ethylhexanal, unsaturated aliphatic aldehydes such as acrolein and methacrolein, and benzaldehyde. , aromatic aldehydes such as tolylaldehyde, and the corresponding organic percarboxylic acids can be obtained by the method of the present invention.
本発明方法においては芳香族複素環を構成する
共役α−ジイミン化合物が触媒として使用され
る。共役α−ジイミン化合物の具体例としては、
２・2′−ビピリジル、１・10−フエナンスロリ
ン、バソフエナンスロリン等の分子内に〓〓Ｎ〓
〓Ｃ〓〓Ｃ〓〓Ｎ〓〓で表現される部位を有する
化合物が挙げられる。特に６−位および6′−位に
置換基を有さない２個のピリジン環を有する共役
α−ジイミン化合物が好ましい。共役α−ジイミ
ン化合物の使用量は微量でよく、通常、反応液中
に0.1〜1000ppm、好ましくは１〜100ppm存在す
る程度で十分である。 In the method of the present invention, a conjugated α-diimine compound constituting an aromatic heterocycle is used as a catalyst. Specific examples of conjugated α-diimine compounds include:
〓〓N〓 in the molecule of 2,2'-bipyridyl, 1,10-phenanthroline, bathophenanthroline, etc.
Compounds having a moiety expressed as 〓C〓〓C〓〓〓N〓〓 can be mentioned. In particular, a conjugated α-diimine compound having two pyridine rings without substituents at the 6-position and the 6'-position is preferred. The amount of the conjugated α-diimine compound to be used may be very small, and it is usually sufficient that it is present in the reaction solution in an amount of 0.1 to 1000 ppm, preferably 1 to 100 ppm.
本発明方法を実施するにあたつては、原料アル
デヒドに対応するカルボン酸を溶媒として使用す
ることが好ましいが、場合により酢酸等の低級脂
肪族カルボン酸を溶媒として使用してもよい。 When carrying out the method of the present invention, it is preferable to use a carboxylic acid corresponding to the raw material aldehyde as a solvent, but in some cases, a lower aliphatic carboxylic acid such as acetic acid may also be used as a solvent.
反応温度は−20℃〜100℃、好ましくは０℃〜
70℃の範囲内で適宜選択され、反応圧力は常圧な
いしは若干の加圧条件が選ばれるが、特に制限は
ない。 The reaction temperature is -20℃~100℃, preferably 0℃~
The temperature is appropriately selected within the range of 70°C, and the reaction pressure is selected from normal pressure or slightly pressurized conditions, but there are no particular limitations.
分子状酸素としては純粋な酸素のほか空気等の
不活性なガスで希釈された酸素を使用することも
できるが、ガス相が爆発組成を形成しないように
留意することが好ましい。酸素は通常、原料アル
デヒドに対して過剰に使用される。 As molecular oxygen, in addition to pure oxygen, oxygen diluted with an inert gas such as air can also be used, but it is preferable to take care that the gas phase does not form an explosive composition. Oxygen is usually used in excess with respect to the raw material aldehyde.
反応を行なうにあたつては気液接触効果を良好
にするために撹拌、振盪などの操作を行なうこと
が好ましい。 When carrying out the reaction, it is preferable to perform operations such as stirring and shaking in order to improve the gas-liquid contact effect.
実施例 １
ヘキセン−１のヒドロホルミル化反応により得
られたC7アルデヒド混合物（ｎ−体：ｉ−体＝
１：１）0.5ｇのおよび酢酸10mlをガラス製偏平
反応器に仕込み、次いで２・2′−ビピリジルを反
応液に対して5ppm添加したのち60℃に加熱し、
酸素雰囲気中で激しく撹拌した。反応終了後、反
応生成物を分析した結果、C7過カルボン酸およ
びC7カルボン酸の収率はそれぞれ62.1％および
29.2％であつた。Example 1 C7 aldehyde mixture obtained by hydroformylation reaction of hexene-1 (n-form: i-form =
1:1) 0.5 g of acetic acid and 10 ml of acetic acid were placed in a flat glass reactor, then 5 ppm of 2,2'-bipyridyl was added to the reaction solution, and then heated to 60°C.
Stir vigorously in an oxygen atmosphere. After the reaction was completed, the reaction products were analyzed and the yields of C7 percarboxylic acid and C7 carboxylic acid were 62.1% and 62.1%, respectively.
It was 29.2%.
比較例 １
２・2′−ビピリジルを使用しなかつたこと以外
は実施例１と同様に反応を行なつたところ、C7
過カルボン酸の収率は32.0％であつた。Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that 2,2'-bipyridyl was not used .
The yield of percarboxylic acid was 32.0%.
実施例 ２
イソブチルアルデヒド0.5ｇおよびイソ酪酸10
mlをガラス製偏平反応器に仕込み、反応液に対し
て10ppmの２・2′−ビピリジルを添加したのち、
40℃で実施例１と同様に酸化反応を行なつた。そ
の結果、過イソ酪酸の収率は51.8％、イソ酪酸の
収率は43.0％であつた。Example 2 0.5 g of isobutyraldehyde and 10 g of isobutyric acid
ml was placed in a flat glass reactor, and 10 ppm of 2,2'-bipyridyl was added to the reaction solution.
An oxidation reaction was carried out at 40°C in the same manner as in Example 1. As a result, the yield of perisobutyric acid was 51.8% and the yield of isobutyric acid was 43.0%.
比較例 ２
反応液中に酢酸銅5ppmを更に添加したこと以
外は実施例２と同様に反応を行なつた。その結
果、過イソ酪酸の収率は24.0％であつた。Comparative Example 2 The reaction was carried out in the same manner as in Example 2 except that 5 ppm of copper acetate was further added to the reaction solution. As a result, the yield of perisobutyric acid was 24.0%.
実施例 ３
プロピオンアルデヒド0.5ｇおよび酢酸10mlを
ガラス製偏平反応容器に仕込み、１・10−フエナ
ンスロリンを反応液に対して50ppm添加したの
ち60℃で実施例１と同様に反応を行なつた。その
結果、過プロピオン酸の収率は26.1％であつた。Example 3 0.5 g of propionaldehyde and 10 ml of acetic acid were placed in a flat glass reaction vessel, and after adding 50 ppm of 1,10-phenanthroline to the reaction solution, the reaction was carried out at 60° C. in the same manner as in Example 1. As a result, the yield of perpropionic acid was 26.1%.
比較例 ３
１・10−フエナンスロリンを使用しなかつたこ
と以外は実施例３と同様に反応を行なつたとこ
ろ、過プロピオン酸の収率は5.0％であつた。Comparative Example 3 The reaction was carried out in the same manner as in Example 3 except that 1,10-phenanthroline was not used, and the yield of perpropionic acid was 5.0%.
Claims (1)
合物の存在下にアルデヒドを液相で分子状酸素に
より酸化することを特徴とする有機過カルボン酸
の製造方法。1. A method for producing an organic percarboxylic acid, which comprises oxidizing an aldehyde with molecular oxygen in a liquid phase in the presence of a conjugated α-diimine compound constituting an aromatic heterocycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11723378A JPS5543058A (en) | 1978-09-22 | 1978-09-22 | Production of organic peracid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11723378A JPS5543058A (en) | 1978-09-22 | 1978-09-22 | Production of organic peracid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5543058A JPS5543058A (en) | 1980-03-26 |
| JPS625141B2 true JPS625141B2 (en) | 1987-02-03 |
Family
ID=14706671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11723378A Granted JPS5543058A (en) | 1978-09-22 | 1978-09-22 | Production of organic peracid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5543058A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3677793B2 (en) * | 1993-11-16 | 2005-08-03 | 住友化学株式会社 | Process for producing aromatic percarboxylic acids |
-
1978
- 1978-09-22 JP JP11723378A patent/JPS5543058A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5543058A (en) | 1980-03-26 |
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