JPH013143A - Method for producing 2-chloropropionaldehyde - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is directed to the production of 2-chloropropion produced from vinyl chloride, carbon monoxide and hydrogen according to the following reaction formula (1). This invention relates to a method for producing aldehydes.

2-Chloropropionaldehyde can be used as a useful intermediate for chemicals, agricultural medicines, etc.

(Prior Art and Problems to be Solved by the Invention) Methods for producing 2-chloropropionaldehyde using vinyl chloride, carbon monoxide and hydrogen as raw materials are known, for example, as described in French Patent No. L397,779 and Herhety's・KIMICA 7'KUTA (HELVETICA CIIIMIC
AACTA), Vol. 48, No. 5, pp. 1151-1157
Shown in summer. All of these methods use cobalt carbonyl as a catalyst, and for example, according to the above-mentioned French Patent No. 1,397,779, the reaction temperature is 110°C2.
The reaction was carried out for 90 minutes at a reaction pressure of 200 atm, and a conversion of vinyl chloride of 57.4% and a selectivity of 2-chloropropionaldehyde of 86.2% were obtained. However, in these methods using cobalt carbonyl as a catalyst, the catalytic activity per cobalt is extremely low, and for this reason, a large amount of cobalt carbonyl and a high reaction pressure of 160 to 200 atm are required, as well as a reaction temperature of 75 ~]90-1.20 at 25℃
A method is used in which the reaction is carried out over a period of minutes. The desired product, 2-chloropropionaldehyde, is a thermally unstable substance, and at such reaction temperatures and times, a considerable proportion of it is consumed in successive reactions, and this treatment is necessary to reduce the reaction yield. The process is not reproducible, and furthermore, this sequential reaction or other side reactions produce hydrogen chloride, which severely corrodes the reactor material and reacts with the cobalt carbonyl catalyst to form cobalt chloride, causing a loss of catalyst strength. It also has the problem of hindering reuse.

The present inventors have developed a method for improving these methods using Japanese Patent Application Laid-Open No. 61-1
No. 26046, JP-A-62-10038, JP-A-62
As shown in No. 22738 and Japanese Unexamined Patent Publication No. 62-96444, a method was discovered in which vinyl chloride, carbon monoxide, and hydrogen are reacted in the presence of a rhodium compound and a base. According to this method, the reaction proceeds at a lower temperature and pressure than the conventional method using a cobalt carbonyl catalyst, and sufficient selectivity to the target product can be obtained. In these methods, in the presence or absence of water, a base of the general formula P(R'R2R') (where P represents a phosphorus atom, R', R2, and R3 are an alkyl group, an aryl group, at least one compound represented by a cycloalkyl group, an alkoxy group, an aryloxy group, or a cycloalkoxy group, J2 and pea become 4,
A combination with 11 nitrogen-containing compounds is preferably used.

Among these nitrogen-containing compounds having a pKa of 4 to 11, pyridine compounds, quinoline compounds, imidazole compounds, triazole compounds, and morpholine compounds are particularly preferably used from the viewpoint of reaction results. Since they are also relatively expensive compounds, it is necessary to install, for example, a recovery device for them in order to minimize the amount of loss when using them industrially.

Furthermore, since these are all highly reactive compounds, they are gradually consumed during long-term use.

For this reason, it is necessary to carry out operations so as to suppress these losses as much as possible, but these operating conditions do not necessarily coincide with conditions favorable for the synthesis of 2-chloropropionaldehyde. For this reason, there is a problem in that the consumption of these and the reaction at a location slightly deviating from the optimum synthesis conditions have a considerable impact on the production cost of the target product, 2-chloropropionaldehyde. Also, pyridine compounds,
Many of the quinoline compounds and morpholine compounds have relatively low boiling points. Although it is a small amount, it is mixed into chloropropionaldehyde, which not only causes a decrease in the purity of the 2-chloropropionaldehyde product, but also significantly accelerates the oxidation reaction when 2-chloropropionaldehyde is oxidized to produce 2-chloropropionic acid. It also has the problem of being inhibited.

An object of the present invention is to provide a method for producing 2-chloropropionaldehyde that solves the problems of the prior art.

(Means and effects for solving the problems) The present inventors conducted detailed research to solve these problems. As a result, when producing 2-chloropropionaldehyde by reacting vinyl chloride, carbon monoxide, and hydrogen in the presence of a rhodium compound and a trivalent organic phosphorus compound or an oxide of a trivalent organic phosphorus compound, the reaction system The present inventors have discovered that if an ammonium salt of a weak acid is allowed to coexist with the reaction mixture, the reaction proceeds efficiently and the above-mentioned problems of the catalyst made of rhodium and a base can be solved, and the present invention has been completed.

That is, in the presence of a rhodium compound and a trivalent organic phosphorus compound or an oxide of a trivalent organic phosphorus compound,
A method for producing 2-chloropropionaldehyde, which comprises reacting vinyl chloride, carbon monoxide and hydrogen to produce 2-chloropropionaldehyde in the presence of at least one ammonium salt of a weak acid. be.

The trivalent organic phosphorus compound or the oxide of the trivalent organic phosphorus compound used in the method of the present invention is exemplified as follows.

That is, as a trivalent organic phosphorus compound, general 2P (R'
R''R') (where P represents a phosphorus atom, R1,
R2, R:l are each the same or different alkyl,
Examples include trivalent organic phosphorus compounds represented by aryl, cycloalkyl, alkoxy, aryloxy, or cycloalkoxy groups, specifically trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, and trioctylphosphine. , phosphines such as triphenylphosphine, tricyclohexylphosphine, trihensylphosphine,
Trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, trioctyl phosphite, triphenyl phosphite,
Examples include phosphites such as tricyclohexyl phosphite and tribenzyl phosphite.

In addition, as a special type of phosphine, the above general 2P
In addition to those represented by (R'R2R' ), diphosphines such as bisdiphenylphosphinomethane and bisdiphenylphosphinoethane, phosphines bonded to crosslinked polystyrene, and the like are also preferably used.

Further, as the oxide of the trivalent organic phosphorus compound, tributylphosphine oxide, tributylphosphine oxide, alkylphosphine oxide such as tributylphosphine oxide, arylphosphine oxide such as 1-rifhenylphosphine oxide, tri-1-lylphosphine oxide, or Examples include alkylarylphosphine oxides having both an alkyl group and an aryl group. In addition, alkyl or aryl phosphite oxides such as triethyl phosphite oxide, tributyl phosphite oxide, triphenyl phosphite oxide, and alkylaryl phosphite oxides having both an alkyl group and an aryl group can also be used. can. Furthermore, polydentate phosphine oxides such as bis-1,2-diphenylphosphite tumecune dioxide and the like can also be used.

Furthermore, the ammonium salt of a weak acid in the method of the present invention means a salt of a weak acid such as carboxylic acid, boric acid, carbonic acid, etc., and ammonia or an amine, or a quaternary ammonium salt of these weak acids.

Examples of these weak acids are as follows. Specifically, examples of carboxylic acids include formic acid, acetic acid, propionic acid,
Butyric acid, isobutyric acid, heptanoic acid, acrylic acid, methacrylic acid, crotonic acid, oxalic acid, malonic acid, methylmalonic acid,
aliphatic saturated or unsaturated mono- or polycarboxylic acids such as succinic acid, adipic acid, maleic acid, fumaric acid, muconic acid, 1,2,3-propanetricarboxylic acid and benzoic acid;
Toluic acid, 0-ethylbenzoic acid, 2,4-dimethylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 5-
Examples include aromatic or polyhydric carboxylic acids such as methyl isophthalic acid, trimellitic acid, l-rimesic acid, pyromellitic acid, and mellitic acid. Further, carboxylic acids in which a substituent such as a halogen, an amino group, or a hydroxyl group is attached to the alkyl group or aryl group of these carboxylic acids are also preferable.
Examples of these are monochloroacetic acid, 2-chloropropionic acid, 3-chloropropionic acid, monobromoacetic acid, 0
-Halogen-substituted carboxylic acids such as chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, O-fluorobenzoic acid, glycine, sarcosine, alanine, β-alanine, 4-aminobutyric acid, valine, serine, aspartic acid , amino acids such as glutamic acid, glycolic acid, lactic acid,
2-hydroxybutyric acid, glyceric acid, malic acid, tartaric acid, citric acid, p-hydroxybenzoic acid, salicylic acid, 2
．． Examples include hydroxycarboxylic acids such as 4-dihydroxybenzoic acid, 3-hydroxyphthalic acid, and hydroxyterephthalic acid. In addition, phenylacetic acid, pyruvic acid, acetoacetic acid, anisic acid, vanillic acid, 0-nitrobenzoic acid,
Preferred examples include carboxylic acids with substituents other than those mentioned above, such as cinnamic acid.

-4, the ammonium cation constituting the ammonium salt of a weak acid has the following general formula: (R'R"R3R'N)" (where R1, R2, R3 and R4 are each hydrogen,
or the same or different alkyl group, cycloalkyl group, alkylaryl group or hydroxyalkyl group), and specifically, in addition to ammonium cations, ammonium cations represented by:
Primary ammonium cations such as methylammonium, ethylammonium, propylammonium, isopropylammonium, heptylammonium, cyclohexylammonium or benzylammonium cations, secondary ammonium cations such as dimethylammonium, diethylammonium, dipropylammonium or dibutylammonium cations, trimethylammonium,
triethylammonium, tripropylammonium,
Examples include tertiary ammonium cations such as triisopropylammonium or tributylammonium cations, and quaternary ammonium cations such as tetramethylammonium, tetraethylammonium, tetrapropylammonium, methyltriethylammonium, benzyltrimethylammonium or heptyltriethylammonium cations.

It is preferable to use previously prepared ammonium salts of these weak acids. However, in some cases, ammonium salts of these weak acids are formed in the reaction system, for example by adding the weak acid and ammonia or amine separately, or by combining the weak acid and ammonium hydroxides such as tetramethylammonium hydroxide. It is also possible to use them by adding them separately.

Examples of the rhodium compound used in the method of the present invention include rhodium oxides, mineral acid salts, organic acid salts, and rhodium complex compounds. Among these various rhodium compounds, halogen-free rhodium compounds are particularly preferred. Examples of these include rhodium oxide, rhodium nitrate, rhodium sulfate, rhodium acetate, rhodium triacetylacetonate, rhodium dicarbonylacetylacetonate, dodecacarbonyl tetrarhodium, hexadecacarbonyl hexalhodium, etc. In addition to these rhodium complex compounds, complex compounds formed by rhodium and a base are also preferably used. The base may be a base such as a trivalent organic phosphorus compound or an oxide of a trivalent organic phosphorus compound preferably used in the method of the present invention, but other bases may also be used. Examples of these include, for example, hydridocarbonyltristriphenylphosphine rhodium (ljhH(CO)(PPh+)3), nitrosyltristriphenylphosphine rhodium (Rh(NO)(
PPh+)+ ), η-cyclopentadienylbistriphenylphosphine rhodium (Rh(C5H5)(P
Ph3)! ) etc. Furthermore, using a halogen-containing rhodium compound such as rhodium chloride, rhodium bromide, rhodium iodide, or dichlorotetracarbonyl dirhodium, an alkaline compound such as sodium hydroxide or water in an amount equivalent to or more than the halogen atom is added to the reaction system. Addition of potassium oxide, potassium carbonate, trimethylamine, triethylamine, etc. can also be used as a means for producing a halogen-free rhodium compound in the reaction system.

In the method of the present invention, the rhodium compound contains 0.000 rhodium atoms per liter of liquid phase in the reaction system.
1-1000 milligram atoms, preferably 0.001
It is used in amounts corresponding to a range of ~100 milligram atoms. Further, the base such as the trivalent organic phosphorus compound or the oxide of the trivalent organic phosphorus compound used in the method of the present invention is 0.1 to 50% per gram atom of rhodium, respectively.
It is used in an amount of 0 mol, preferably 0.5 to 100 mol.

Further, the ammonium salt of the weak acid used in the method of the present invention may have an amount of 0.1 to 200 mol per gram atom of rhodium,
In particular, it is preferable to use it in a range of 1 to 30 mol.

In the method of the present invention, the reaction proceeds without using a reaction solvent, but the reaction is usually carried out in the presence of a reaction solvent. Any reaction solvent can be used as long as it does not adversely affect the reaction. Hydrocarbons are particularly preferred as such solvents. More specifically, saturated hydrocarbons such as hexane, heptane, octane, nonane, and decane, and aromatic hydrocarbons such as benzene, toluene, and xylene are preferably used, and
These examples also include ligroin, kerosene, light oil, diesel oil, etc. which are obtained industrially as mixtures of hydrocarbons. In addition, examples of preferred solvents include ethers such as dipropyl ether and dibutyl ether, ketones such as diisobutyl ketone and holon, and esters such as butyl butyrate and butyl benzoate.

In the method of the present invention, a method in which water is allowed to coexist in the reaction system is more preferably carried out. By adopting such a method, the catalytic activity is further improved.

In the method of the present invention, there is no particular restriction on the amount of water present during the reaction, but if it is used in an extremely small amount, the effect will be small, and even if it is used in an extremely large amount, the reaction results will not improve beyond a certain level. Usually, the amount of water is preferably in the range of 0.01 or more and 1000 or less in terms of weight ratio to the vinyl chloride supplied to the reactor as a raw material. In particular, 0.1 to 1
A range of 00 is more preferably used.

The method of the present invention is usually carried out at a reaction temperature of 10 to 150° C. and a reaction pressure of 10 to 300 Kg/cM gauge, preferably 30 to 150 Kg/afl gauge. The reaction temperature is preferably low from the viewpoint of thermal stability of the 2-chloropropionaldehyde produced;
0°C is a particularly preferred temperature range. Further, the mixing molar ratio of raw materials carbon monoxide and hydrogen is usually in the range of 10 to 0.1, preferably in the range of 4 to 0.2. Carbon monoxide and hydrogen may be a mixed gas containing both components in the above-mentioned composition ratio, such as water gas, water gas and methane, etc.
A gas containing inert gas such as nitrogen or carbon dioxide is used. The other raw material, vinyl chloride, is used in the form of a gas, liquid, or solution dissolved in the solvent used for the reaction. The method of the present invention includes:
It can be carried out by any of the batch method, semi-batch method, and continuous method. For example, in the case of a batch method, an autoclave containing a rhodium compound, a trivalent organic phosphorus compound or an oxide of a trivalent organic phosphorus compound, an ammonium salt of a weak acid, and, if necessary, a reaction solvent and water,
The reaction proceeds by adding vinyl chloride in the form of a gas, liquid, or solution, introducing a gas containing carbon monoxide and hydrogen to a predetermined pressure, and heating, preferably with stirring. In addition, examples of continuous methods include rhodium compounds, trivalent organic phosphorus compounds or oxides of trivalent organic phosphorus compounds, ammonium salts of weak acids, and if necessary, reaction solvents and water, and the raw material vinyl chloride. , carbon monoxide and hydrogen are continuously supplied to one side of the pressure-resistant reactor, and the reaction mixture, unreacted vinyl chloride, carbon monoxide and hydrogen are continuously fed from the other side under stirring conditions at the reaction temperature. The reaction is carried out by withdrawing the sample. In the case of a continuous process, since it is difficult to continuously supply the ammonium salt of a weak acid to the reactor in solid form, it is supplied in the form dissolved in the reaction solvent or water, or as mentioned above, it is difficult to continuously supply the ammonium salt to the reactor. ammonia,
It is preferable to feed the amine or ammonium hydroxide etc. separately.

(Example) Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.

Example 1 After purging the inside of a stainless steel autoclave with an internal volume of 100 d and equipped with a stirring device with nitrogen gas, 36 mm of hexadecacarbonyl hexalodium (0.2 milligram atoms of Rh) and 157 mm of triphenylphosphine (0.6 mmol) were added. ), 483 mg (3 mmol) of triethylamine acetate and 20 g of water were added, and 1.8 g of vinyl chloride was added to the solution.
A solution of 20 g (30 mmol) of hinyl chloride in toluene was added. A mixed gas of carbon monoxide and hydrogen having a molar ratio of 1:2 was pressurized into this autoclave at room temperature until the pressure reached 120 Kg/c (IY gauge), and then the temperature was raised to 55° C. and reacted for 30 minutes. After the autoclave was cooled to room temperature and unreacted raw material mixed gas was collected in a gas sampling bag, the autoclave was opened and the reaction mixture containing the catalyst, solvent, and reaction product was taken out. As a result of quantifying the gas and liquid by gas chromatography, the conversion rate of vinyl chloride was 24.5%, and 2-
The amount of chloropropionaldehyde produced was 6.1 mmol (selectivity based on converted vinyl chloride was 83.0%).

Examples 2 to 5 Reactions were conducted in the method of Example 1 by changing the reaction temperature, reaction pressure, molar ratio of carbon monoxide to hydrogen, and reaction time. The results are shown in Table 1.

= 19-Examples 6 to 9 In the method of Example 1, the reaction temperature was 45 ° C., and the types of rhodium compound, trivalent organic phosphorus compound or trivalent organic phosphorus compound oxide, and ammonium salt of a weak acid were changed. The reaction was allowed to take place. The amount of rhodium compound was set to 0.2 milligram atom of rhodium in each case.

The results are shown in Table 2.

(Left below) Example 10 The reaction was carried out in the same manner as in Example 1 except for the absence of water.

As a result of the analysis, reaction results were obtained with a conversion rate of vinyl chloride of 8.1% and a selectivity of 2-chloropropionaldehyde of 80.2%.

(Effects of the Invention) According to the present invention, 2-chloropropionaldehyde can be produced in high yield at low temperature and low pressure using vinyl chloride, carbon monoxide, and hydrogen as raw materials. In particular, unlike conventional methods, the method of the present invention does not require equipment for recovering the base or removing the base mixed in 2-chloropropionaldehyde, and conditions must be selected to minimize the loss of base. It becomes possible to proceed with the reaction stably over a long period of time using a simple device.

Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (3)

[Claims] (1) In producing 2-chloropropionaldehyde by reacting vinyl chloride, carbon monoxide, and hydrogen in the presence of a rhodium compound and a trivalent organic phosphorus compound or an oxide of a trivalent organic phosphorous compound, the reaction is carried out. 1. A method for producing 2-chloropropionaldehyde, which is carried out in the coexistence of at least one ammonium salt of a weak acid. (2) The method according to claim 1, wherein the reaction is carried out in the presence of water. (3) The method according to claim 1 or 2, wherein the reaction is carried out at a temperature in the range of 20 to 80°C.