JPS6024088B2 - Method for producing isobutyryl fluoride - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the liquid phase production of acyllium anion products (acyllium fluoride), particularly isobutyryl fluoride, which process comprises the steps of: carbon monoxide and anhydrous hydrofluoric acid; The supercritical region on the liquid phase of the liquid mixture of
The acylium anion product, disisobutyryl fluoride, is formed by supplying carbon monoxide and propylene to the al region.

The prior art, such as US Pat. It emphasizes that.

In these methods, extremely irreversible polymerization occurs;
Moreover, since the aqueous acid medium is corrosive, expensive equipment is required. In the known art, such as Koch US Pat. No. 2,831,877, acid fluorides are formed in low yields by reacting olefins with carbon monoxide and hydrofluoric anhydride in a two-phase reaction.

There, carbon monoxide is in a gas phase, and olefins and hydrogen fluoride are in a liquid phase. This now results in dimerization or polymerization of the olefins, which must be expelled from the reaction system and require separation from the product. Problems in the prior art are overcome by following the reaction conditions described herein, and the methods described herein provide acyllium anion products and their corresponding carboxylic acids or esters in fairly high yields. I can do it. Isobutyryl fluoride, an acyllium anion product (acyllium fluoride), is a liquid that combines carbon monoxide, anhydrous hydrofluoric acid (hydrogen fluoride), and propylene, an organic compound that can add carbon monoxide. while carbon monoxide and propylene are reacted in the gas phase above the liquid reaction mixture at a rate substantially equal to the rate at which carbon monoxide, propylene, and anhydrous hydrofluoric acid form diisobutyryl fluoride. and maintaining the temperature and pressure of the gas phase of the mixture above the liquid phase at values such that carbon monoxide is in a supercritical fluid phase state and propylene is dissolved therein. Ru.

Here, the term "supercritical fluid phase" refers to a gas that cannot become a liquid even when compressed, but has properties different from those of the gas or liquid itself. This reaction is carried out under conditions such that isoptyryl fluoride is formed in appreciable yield. The isobutyryl fluoride is separated and reacts with water to form a carboxylic acid, an isoacid, or with an alcohol to form a carboxylic acid ester, such as methyl isobutyrate, or the product mixture itself reacts with water. It is also possible to react with carboxylic acids or alcohols to form carboxylic acid esters. The present invention
carbon monoxide and propylene to which carbon monoxide can be added;
A novel method for producing isobutyryl fluoride from an acid anhydride disclosed herein.

Carbon monoxide, acid anhydride, and propylene are combined in a liquid mixture under conditions such that isoptyryl fluoride is produced in appreciable yield, i.e., less than 10% of the formation of polymeric products or other undesirable by-products. It is made to react internally.

After initiation of the reaction, carbon monoxide and propylene enter the gas phase above the liquid reaction mixture at a rate substantially equal to the rate at which carbon monoxide, propylene, and acid anhydride react to form isobutyryl fluoride (i.e. , 15 preferably <10 mol%). The temperature and pressure of the gas phase of the mixture above the liquid mixture are maintained such that the carbon monoxide in the gas phase of the mixture is in a supercritical fluid phase state and the propylene is dissolved therein. Preferably, the temperature and pressure are such that propylene is dissolved in a supercritical fluid phase of carbon monoxide and that both carbon monoxide and propylene are transferred into the reaction mixture at a rate, thereby inhibiting side reactions such as polymerization. is maintained at a point where it does not occur. The rate is the same rate at which carbon monoxide, acid anhydride, and propylene react to form isobutyryl fluoride. The acylium anion product, such as isobutyryl fluoride, obtained according to the present invention is separated from the reaction mixture and then further reacted with water or an alcohol under conditions such that the corresponding carboxylic acid or carboxylic acid ester is formed. You can be forced to do so.

Alternatively, the product mixture containing the acylium anion product, such as isobutyryl fluoride, formed can be further reacted with water or an alcohol under conditions such that the corresponding carboxylic acid or carboxylic acid ester is formed.

Carbon monoxide can be of any origin, but
In order to maintain the reaction mixture anhydrous, it must be substantially free of water.

The carbon monoxide can be diluted with other substances that do not interfere with the reaction, such as hydrogen, propane, or non-reactive hydrocarbons. For example, dry syngas can be used as the carbon monoxide source. However, it is preferred to use anhydrous carbon monoxide itself. The organic compound capable of reacting with carbon monoxide is propylene, which olefin may be substituted with substituents that do not interfere with the process of the invention.

A suitable anhydrous acid for the process of the invention is hydrofluoric anhydride.

Provided that the acid anhydride system is maintained, a small amount, i.e. 0.02
It is possible to use anhydrous hydrofluoric acid containing up to % by weight of water. Z The reaction of carbon monoxide, propylene, and the above-mentioned hydrofluoric acid anhydride is 26 to 9 p○,
Preferably, it can be carried out at a temperature of about 40-70°C. The pressure at which this reaction is carried out can vary from about 112.5 to 351.5 kg/earth absolute [109 to 340 bar (1600 to 500 sig)], preferably the pressure is about 175.6 to 203 .9k9/enemy absolute pressure [169
~197 bar (2500-290 sig)]. Pressure and temperature are increased depending on the solubility of carbon monoxide in the anhydrous acid and to maintain a supercritical fluid phase of carbon monoxide. The above range is from an economic and industrial perspective.
It is defined by taking into consideration the reaction rate, product yield, formation of by-products (second base bodies, etc.), and this point has particular significance. For example, if a reaction temperature of 2 or 0 is used and the Examples described below are repeated, the reaction rate becomes slow, which is not preferred from an industrial standpoint. Regarding pressure, the basis for setting it is clear from the following example. The propylene is dissolved in the supercritical fluid phase above the liquid phase of the reaction medium.

As used herein, the term "vapor" is synonymous with "gaseous" or "gas." The final mole percent of hydrofluoric anhydride to propylene in the reaction mixture is between 1:1 and 1.
Should be 00:1, but typically 10:1-2
0:1, preferably about 12:1 to 16:1.

The molar ratio of carbon monoxide to propylene is from 1:1 to 25:1 or higher, preferably from 15:1 to 25:1. The carbon monoxide and anhydrous hydrofluoric acid are thoroughly mixed to form a single liquid phase, after which propylene and carbon monoxide are fed into the reactor as needed.

The propylene itself can be mixed with carbon monoxide or an inert diluent (e.g. propane) before being added to the reactor.
Can be diluted. It is critical that the addition of carbon monoxide and propylene to the reactor occur at a rate substantially equal to the rate at which the carbon monoxide, propylene, and acid anhydride react. That is, the addition rate should be within 1 & preferably 10 mole percent of the rate at which the reactants react to form isobutyryl fluoride. If the rate of addition of carbon monoxide is faster than the rate of addition of propylene, no adverse effects generally occur, but if the rate of addition of carbon monoxide is much slower than the rate of addition of propylene, the yield of isobutyryl fluoride will decrease. Decrease. This is generally due to the occurrence of deleterious side reactions such as polymerization of the double bonds of unsaturated compounds and carbonylation of oligomers or oligomers. It is thus very important that propylene is added at a rate substantially equal to the rate at which it is consumed, or if the carbon monoxide addition rate is slow, the propylene addition rate must also be slow. The appropriate rate of addition is determined by taking a certain amount of isobutyryl fluoride that is formed under the given reaction conditions or by determining the amount of carbon monoxide used and then determining the rate of formation of the acylium anion or the amount of carbon monoxide used. It can be easily adjusted by increasing or decreasing the addition rate depending on the carbon addition rate.

It is important to incubate the liquid phase reaction mixture as rapidly as possible to ensure sufficient mixing and dilution of the propylene added and to transfer the carbon monoxide and propylene from the vapor or gas phase to the liquid phase. be.

The reaction of isoptyryl tufftide with water or alcohol is carried out at a temperature of about 1.033 to 351.5.
It can be carried out at a pressure of about 35.1 to 210.9 k9/absolute (5 k9), but usually at a temperature of 40 to 70 qo.
It occurs under 40 pressures of 0.00 to 300 imitation sja). Temperature and pressure are set so that initial product decomposition does not occur. Alternatively, after the carbonylation is complete, the reaction mixture itself is reacted with water or alcohol.

The entire amount of water or alcohol is injected into the reaction mixture after the carbonylation reaction is completed. Since hydrolysis or esterification is an exothermic process, cooling is required. The carboxylic acid or ester is then separated. After completion of the carbonylation reaction, 1 to 100% of the stable isobutyryl fluoride produced is separated from the product mixture.

Preferably 80-100% of the stable isobutyryl fluoride is separated and the remaining product mixture is recycled for reaction as in the process of the present invention. Furthermore, 1 to 1
00% (preferably 80-100%) of the acid anhydride is separated from the product mixture and recycled for further mixing with the carbon monoxide in the liquid phase.

The separation method in the present invention may be any known separation method, such as distillation or extraction. The process of the invention can be carried out in any suitable reactor, such as a continuous tank reactor (CSTR).

In the present invention, it is extremely important to maintain an appropriate amount of carbon monoxide in the solution.

The amount of anhydrous hydrogen fluoride or carbon monoxide that can be dissolved in the reaction mixture under a particular temperature and pressure can be readily determined experimentally by one skilled in the art. For example, about 210
49k9/arc absolute pressure (300shipsia) and 80ko○
Under these conditions, about 4.082 k9 (91 bs) of carbon monoxide can be dissolved in about 45.36 k9 (1001 bs) of hydrogen fluoride. Based on the molar amount of propylene to be reacted, the amount of carbon monoxide required for the reaction can be determined. For example, as mentioned above, the preferred molar ratio range of propylene to carbon monoxide to anhydrous hydrofluoric acid is from 1:1 to 25:1 to 100;
Preferably it is 1:25:14. Other necessary information is the predetermined reaction conditions, ie the pressure and temperature of the reactor.

From this we can determine the mole percent of carbon monoxide dissolved in the hydrofluoric acid and from this the amount of hydrofluoric acid solution required to provide sufficient carbon monoxide to react with propylene. amount can be determined. The following examples (Examples and Comparatives) illustrate the method of the invention.

Carbonylation reactor 300cc Autoclape Engineers Magnedrive Hastelloy (AutMlav
e E increase ineeN N is gnedriVe Zaiseste
lloy) C with a turbine lamp, a carbon monoxide inlet, a propylene inlet, an outlet for depressurizing the reactor and an external heater.

The reactor was first flushed with carbon monoxide and then approximately 150 g (7.5 moles) of anhydrous hydrogen fluoride was charged into the reactor.

The hydrogen fluoride was then pumped to bring the reactor to a preselected temperature while carbon monoxide was introduced into the reactor to a preselected pressure. After the carbon monoxide pressure stabilizes,
A supercritical mixture of propylene and carbon monoxide is formed by feeding propylene into the gas phase of the liquid mixture, which is a mixture of carbon monoxide and hydrogen fluoride, above the liquid phase. It was to so.

The mixture passed into the liquid phase. Propylene was fed via a metering pump while carbon monoxide was added to maintain the reactor pressure at the preselected pressure. After the completion of the reaction, i.e. after adding the predetermined amounts of propylene and carbon monoxide, the reactor is allowed to cool for another 15-30 minutes, and then the reactor is cooled to about 120 q0 with an acetone dry ice mixture. Then, with further cooling, 38.5 mL of water was pumped into the reactor over 5 to 1 minute.

The reactor was then evacuated and opened, and the product mixture was further diluted with ice water until the hydrogen fluoride was approximately 1% by weight of the mixture. Then 400 min of sodium sulfate (Na2S04)
was added, and 4 types of volumes (40
0, 300, 200, 200) of cyclohexane. Combine the cyclohexane extracts and gask. The product was analyzed by chromatography and separated by distillation.
The percent yield of isobutyric acid produced was determined based on the amount of propylene added. Table 1 shows the results of adjusting the feed rates of propylene and carbon monoxide at various temperatures and pressures.

The first column shows the example (example and comparative example) number; the second column is the pressure range of the reaction in psia; the third column is the temperature range of the reaction in °C; the fourth column is the The complete propylene addition time; column 5 is the addition rate per hour. represents the number of moles of pyrene; column 6 represents the apparent reaction time, based on the propylene addition time plus the additional time required for stabilization of the carbon monoxide pressure; column 7
The column shows the % yield of isobutyric acid based on the total amount of propylene added. The examples shown in Table 1 were carried out with a molar ratio of hydrogen fluoride to propylene of 15:1, and the ratio of carbon monoxide to propylene fed to the reaction mixture was 1.1:1. Example 3
, 4, 5, 6, 7, 8, 9 and 13 (Examples),
The propylene addition rate is substantially the rate used (6.
It can be easily seen that when the reaction rate is less than 0 mol/hour), isobutyryl fluoride is formed in a substantial theoretical yield of about 90% or more. Other examples (comparative examples)
isobutyryl fluoride in much lower yields if the propylene addition rate is too slow, the pressure is too low, the gas phase is not above the critical point, or the solubility of carbon monoxide in hydrogen fluoride is too low. It shows that it gives. TABLE 1 Although the invention has been described with particular reference to certain illustrative embodiments, the invention is in no way limited thereby, but only by the details set forth in the claims.

Claims (1)

[Claims] 1. A method for producing isobutyryl fluoride from carbon monoxide, hydrofluoric anhydride, and propylene, which comprises: producing isobutyryl fluoride from carbon monoxide, hydrofluoric anhydride, and propylene, comprising: Reacting hydrofluoric anhydride and propylene,
while supplying carbon monoxide and propylene into the gas phase above the liquid reaction mixture at a rate substantially equal to the rate at which carbon monoxide, propylene, and hydrofluoric anhydride form isobutyryl fluoride; is added at a rate of less than 6.0 mol/hour, and the gas phase above the liquid phase is such that carbon monoxide in the gas phase is in a supercritical liquid phase state and the propylene is in the fluid phase. The temperature and pressure are maintained at such a temperature and pressure that the material is melted, and the temperature is in the range of 26 to 90°C, and the pressure is in the range of about 112.5 to 351.5 kg/cm.
^2 absolute pressure, the final molar ratio of hydrofluoric anhydride to propylene in the reaction mixture is 1 to 100 moles of hydrofluoric anhydride to 1 mole of propylene, and the molar ratio of carbon monoxide to propylene is 1 to 100 moles of hydrofluoric anhydride to 1 mole of propylene. A method for producing isobutyryl fluoride, characterized in that the amount of carbon monoxide is in the range of 1 to 25 moles per mole. 2 The temperature is within the range of 40 to 70℃ and the pressure is approximately 17℃.
5.6 to 203.9 kg/cm^2 absolute pressure, and the final molar ratio of hydrofluoric anhydride to propylene in the reaction mixture is 1 mole of propylene to 10 to 20% of hydrofluoric anhydride. molar range, and the molar ratio of carbon monoxide to propylene is in the range of 15 to 25 moles of carbon monoxide per mole of propylene. the method of. 3. isobutyryl fluoride is separated from the reaction mixture;
The method according to claim 2.