JPS5817181B2 - Production method of tertiary amine - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for synthesizing tertiary amines.

Specifically, the present invention relates to a method for synthesizing tertiary amines by reacting aldehydes, hydrogen and nitrogen-containing compounds in the presence of a catalyst composition.

Traditionally, tertiary amines have been produced in a wide variety of reactions utilizing various metal-containing compounds as catalysts.

For example, U.S. Pat. No. 3,091,641 reacts a secondary amine and an aliphatic ketone with carbon monoxide and water in the presence of an iron carbonyl catalyst such as iron pentacarbonyl or biscyclopentadienyl diiron tetracarbonyl. Discloses a method for making tertiary amines.

U.S. Pat. No. 3,497,310 discloses that unsaturated compounds, carbon monoxide, hydrogen and ammonia, can be hydrogenated using cobalt catalysts, although other catalysts with hydrogenation properties such as nickel, ruthenium, iron and copper may also be used. discloses the synthesis of tertiary amines which are reacted in the presence of .

U.S. Pat. No. 2,947,458 relates to a process for producing amines in which a nitrogen-containing compound and an olefin are reacted with carbon monoxide and water in the presence of a catalyst consisting of iron pentacarbonyl and a rhodium compound.

Similarly, U.S. Pat. No. 3,234,283 also converts olefins into carbon monoxide, carbon monoxide and
A method for producing trialkylamines by reacting them with hydrogen and dialkylamines is disclosed.

The hydrocarbon content of the catalyst is limited to trihydrocarbons with a total of about 30 carbon atoms and no more than 18 carbon atoms per hydrocarbon group.

Other prior art includes U.S. Pat. No. 3,758,586, in which ethylene is reacted with aliphatic secondary amines in the presence of rhodium or iridium catalysts to form tertiary amines in which one of the substituents is ethylene; ~Conjugates of secondary amines containing about 20 carbon atoms to aliphatic olefins containing about 2 to 20 carbon atoms with carbon monoxide and hydrogen and bifluorescent ligands containing phosphorus, arsenic, or antimony. No. 3,513,200, in which the production of tertiary amines is achieved by reacting in the presence of a composite catalyst comprising a group 8 noble metal hydride;
No. 3,412,158 for a process for producing aliphatic amines from the reaction of low molecular weight olefins with ammonia, in which the primary product is a primary amine rather than a tertiary amine; using an alkali metal catalyst such as sodium No. 2,501,5 for the production of amines by heating an ammonia-type compound with an olefinic compound, requiring the presence of a liquid organic diluent for the olefinic reactant.
No. 09; aliphatic compounds by reacting olefins, oxides of carbon, hydrogen and aminating agents in the presence of hydrogenation-dehydrogenation catalysts such as zinc chromate, zinc tungstate, chromium phosphate, cobalt oxide and iron oxide. There is US Pat. No. 2,422,631 which makes amines.

In contrast to the above reactions, the synthesis of tertiary amines by using specific rhodium- or ruthenium-containing catalysts provides economically attractive conversion of olefinic compounds and economically attractive conversions of olefinic compounds to the desired products. It is shown in detail below that certain selectivities can be obtained.

Tertiary amines are used in a wide variety of applications in the field of chemistry.

For example, these compounds are used in agricultural applications where they act as surfactants for herbicides; in corrosion protection in crude oil pipelines; in cosmetic formulations; leather processing; paint formulation; secondary oil recovery; ore separation. (cationic flocculation or flotation).

Certain compounds, namely tributylamine, are used as solvents, as intermediates in the production of other chemicals, and as inhibitors in hydraulic fluids.

Therefore, in view of these important chemical applications, it is necessary to produce tertiary amines in an economically facile manner, which involves a relatively quantitative conversion of the olefin used to form the desired compound. It must require a high percentage of selectivity.

These objectives are achieved using the process of the invention in which the reaction is carried out in the presence of certain catalyst compositions which are described in detail below.

It is therefore an object of the present invention to provide a method for the synthesis of tertiary amines.

It is a further object of the present invention to provide a method for the synthesis of tertiary amines which provides economically attractive yields of the desired products.

In one embodiment, embodiments of the invention provide aldehydes,
hydrogen and a nitrogen-containing compound having the general formula independently selected from the group consisting of rhoalkyl, aralkyl and alkaryl groups] are reacted under reaction conditions in the presence of a rhodium- or ruthenium-containing catalyst. A method for producing a tertiary amine comprising recovering the tertiary amine.

A particular embodiment of the invention is to react dodecanal, hydrogen and dimethylamine in the presence of a catalyst consisting of rhodium chloride at a temperature in the range of about 50 to 350°C and a pressure in the range of about 10 to 300 atmospheres; A method for producing a tertiary amine comprises recovering the dodecyldimethylamine obtained.

Other objects and embodiments will become apparent from the detailed description of the invention below.

As mentioned above, the present invention relates to a method for synthesizing tertiary amines.

The desired compounds are prepared by reacting aldehydes, hydrogen and nitrogen-containing compounds in the presence of certain catalyst compositions.

The reaction conditions used include temperatures ranging from about 50 to 350°C and pressures ranging from about 10 to 300 atmospheres.

In a preferred embodiment of the invention, the pressure used is the naturally occurring pressure resulting from the presence of hydrogen in the reaction mixture.

However, the pressure resulting from the use of hydrogen consists only of a partial working pressure, with the remainder being carbon monoxide and/or nitrogen,
It is also within the scope of the present invention to obtain substantially inert gases such as helium and argon into the reactor.

Additionally, other reaction conditions present during the synthesis of the tertiary amine include the molar ratios of the various components.

For example, an aldehyde is an aldehyde/nitrogen-containing compound.
:1 to 3:1, with the particular molar ratio used depending on the number of hydrogen atoms present available for alkylation.

Examples of aldehydes that can be used as one of the components of the reaction mixture are ethanol (acetaldehyde), propanal (
Open chain compounds containing from 2 to about 30 carbon atoms such as propionaldehyde), butanal (butyraldehyde), octanal, dodecanal and docosanal also contain side chain isomers such as benzaldehyde.

-NR where R is independently selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl, aralkyl and alkaryl groups.

Examples of the nitrogen-containing compounds that constitute the second component of the reaction mixture include primary amines such as ammonia, methylamine, ethylamine and aniline, and secondary amines such as dimethylamine, diethylamine and dianiline.

These aldehydes and nitrogen-containing compounds are merely representative of the types of compounds that can be used as reactants and are not intended to limit the invention.

The reaction between the above aldehyde and nitrogen-containing compound pair with hydrogen is carried out in the presence of a catalyst composition, which composition consists of a rhodium- or ruthenium-containing compound.

In a preferred embodiment of the invention, the rhodium- or ruthenium-containing compound consists of a metal, nitrate, halide, halocarbonyl, or carbonyl complex.

Particular examples of these compounds used are rhodium, rhodium nitrate, rhodium chloride, rhodium bromide, rhodium iodide, rhodium fluoride, chlorodicarbonyl rhodium dimer, rhodium carbonyl ochlorobis(ethylene) rhodium dimer, ruthenium, Includes ruthenium nitrate, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium fluoride, dichlorotricarbonyl ruthenium dimer and ruthenium carbonyl.

The process of the invention may be carried out in any suitable manner and may consist of either batchwise or continuous operation.

When a batch process is used, the nitrogen-containing compound, together with the aldehyde and the rhodium- or ruthenium-containing compound acting as catalyst, is placed in a suitable pressure-tight apparatus, such as a rotating, rocking or mixing type autoclave.

The aldehyde used as one of the starting components in this professional wrestling is an olefinic compound, a nitrogen-containing compound,
It is the product of a previous process involving the reaction of carbon monoxide and hydrogen, and is a by-product of the previous process where the major product is a tertiary amine.

After the components of the reaction are placed in the autoclave, it is sealed and charged with hydrogen until the desired pressure is reached.

Also, as mentioned above, when high pressure is used, a portion of this pressure is provided by introducing carbon monoxide or a substantially inert gas into the reaction zone.

After reaching the appropriate operating pressure, the device is heated to the desired operating temperature ranging from about 50 to 350°C and maintained at this temperature for a predetermined period of time ranging from about 0.5 to 10 hours. do.

At the end of the desired period of time, the heating is turned off and the apparatus and its contents are allowed to return to room temperature.

After separation from the catalyst, the reaction mixture is treated with conventional separation means, thereby separating the desired tertiary amine from unreacted starting materials and/or side reaction products formed;
to recover.

It is also within the scope of this invention to accomplish the synthesis of this tertiary amine using a continuous operation.

When continuous operation is utilized, the aldehyde and nitrogen-containing compound are continuously charged to a reaction zone maintained at appropriate operating conditions of temperature and pressure and containing the catalyst.

In addition to the continuous charge of reactants to the operating zone, hydrogen is also charged thereto.

As mentioned above, if a higher operating pressure than that afforded by the presence of hydrogen is desired, carbon monoxide and/or an inert gas may be charged to the reactor through separate lines or these gases may be added to the reactor. Mix before charging into the container,
The resulting gas mixture is charged to the reactor in a single stream.

At the end of the desired zone time in the reaction zone, the reactor effluent is continuously removed and treated by conventional separation means such as fractional distillation, thereby freeing the desired tertiary amine from unreacted starting material and/or or separated and recovered from unwanted side reaction products formed.

At the same time, unreacted starting materials are recycled to the reaction zone and form part of the feedstock.

Particular examples of tertiary amines produced by the process of the invention include propyldimethylamine, butyldimethylamine, dodecyldimethylamine, dodecyldiphenylamine, octyldimethylamine, tricosyldimethylamine, and di(pentadecyl)-butylamine. .

These tertiary amines are merely representative ones, and the present invention is not limited thereto.

Next, the present invention will be explained by examples.

However, the present invention is not limited to these Examples.

Example 1 Catalyst consisting of rhodium chloride 0. ．． 01: Ill was placed in the glass liner of the rotating Odo crepe.

Furthermore, dodecanol 14. Oi and 4 g of dimethylamine were placed in an autoclave.

Seal the autoclave and add 1:1 of carbon monoxide and hydrogen.
The mixture was charged into an autoclave until 150 atmospheres of mixed gas was applied.

The autoclave was heated to a temperature of 150'C and maintained at this temperature for 3 hours.

During this time, the pressure in the autoclave rose from 239 atmospheres to 245 atmospheres.

After 3 hours, heating was stopped and the autoclave was returned to room temperature.

When room temperature was reached, excess pressure was released and the reaction mixture was collected.

Analysis of the product by gas-liquid chromatography and elemental analysis showed 79.1% by weight selectivity to dodecyldimethylamine and 18.9% by weight to dodecyl alcohol with 100% conversion of aldehyde.

Example 2 Rhodium chloride 0.014,9. Dodecanal 14.
Put 04g and 4g of dimethylamine into the glass liner of a rotating autoclave, seal the autoclave,
150 atmospheres of hydrogen was charged.

The autoclave was then heated to a temperature of 150°C and kept at this temperature for 3 hours.

During this period, the pressure from the autoclave increased from 236 atm to 239 atm and then decreased to 236 atm.

After 3 hours, heating was stopped and the temperature was returned to room temperature.

Excess pressure was released, the autoclave was opened and the reaction mixture was collected.

Atmospheric chromatography and elemental analysis showed that there was 62.1% conversion of dodecanal, with a selectivity to dodecyldimethylamine of 88.2% by weight.

Example 3 To demonstrate in detail the necessity of the catalyst in the present invention, an experiment was conducted in which 13.91 g of dodecanal and 4 g of dimethylamine were placed in a glass liner of a rotating autoclave.

After the autoclave was sealed, it was pressurized with carbon monoxide and hydrogen in a molar ratio of 1:1 to a pressure of 150 atmospheres.

The autoclave was then heated to a temperature of 150°C and maintained at this temperature for 3 hours.

During this time, the pressure rose from 236 atmospheres to 250 atmospheres.

After 3 hours, heating was stopped, and after returning to room temperature, excess pressure was released.

The autoclave was opened and the reaction mixture was collected and subjected to gas-liquid chromatography and elemental analysis.

The conversion of aldehyde was only 27.3% and the selectivity to dodecyldimethylamine was up to 75%.

Example 4 A mixture of dimethylamine, octatool and a catalyst consisting of chlorodicarbonylrhodium; dimer was placed in an autoclave as described in the "Example"above;
It was sealed and charged with hydrogen until an initial operating pressure of 150 atmospheres was reached.

Then, heat the autoclave to a temperature of about 150°C,
This temperature was maintained for 4 hours, then heating was stopped and the temperature was returned to room temperature.

Excess pressure was released and the autoclave was opened. The reaction mixture was then subjected to gas-liquid chromatography and elemental analysis to determine the presence of the desired tertiary amine, octyldimethylamine.

Example 5 1 A mixture of catalyst consisting of aniline, butanal and chlorobis(ethylene)rhodium dimer was placed in a glass liner of a rotating autoclave, the autoclave was sealed and charged with hydrogen until an initial operating pressure of 150 atmospheres was reached.

After the autoclave was heated to a temperature of 150° C. for 3 hours to complete the reaction, the heating was stopped and the autoclave was returned to room temperature.

After releasing the excess pressure, the autoclave was opened and the reaction mixture was subjected to the above analysis to determine the presence of the desired compound, dibutylaniline.

- Example 6 A catalyst consisting of ruthenium black and an aldehyde consisting of dodecanal were placed in a glass liner of a rotating autoclave.

The autoclave was sealed and charged with ammonia and hydrogen until an initial operating pressure of 250 atmospheres was achieved.

Next, the autoclave was heated to a temperature of 150°C and kept at this temperature for 3 hours, after which heating was stopped and the autoclave was returned to room temperature.

After venting the excess pressure, the autoclave was opened and the reaction mixture was collected and subjected to gas-liquid chromatography and elemental analysis to determine the presence of a tertiary amine consisting of tridodecylamine.

Example 7 A mixture of dimethylamine and docosanal was placed in a glass liner of a rocking autoclave along with a catalyst consisting of rhodium carbonyl.

The autoclave was sealed and charged with a gas mixture consisting of carbon monoxide and dihydrogen in a 1:1 molar ratio until an initial operating pressure of 1.50 atmospheres was reached.

The autoclave was then heated to a temperature of 150°C and kept at this temperature for 3 hours.

At the end of 3 hours, heating was stopped and the temperature was returned to room temperature.

After releasing the excess pressure, the autoclave was opened and the reaction mixture was collected.

This mixture was subjected to gas-liquid chromatography and elemental analysis to determine the presence of tocosyldimethylamine.

Claims (1)

[Scope of Claims] 1 Aldehyde, hydrogen and a nitrogen-containing compound having the general formula where R is independently selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl, aralkyl and alkaryl groups, A process for the preparation of tertiary amines, comprising reaction in the presence of a catalyst selected from the group consisting of ruthenium nitrates, halides, carbonyls and halocarbonyls. 2. The method of paragraph 1, wherein the reaction conditions include a temperature in the range of about 50-350°C and a pressure in the range of about 10-300 atmospheres. 3. The method of item 1, in which the reaction is carried out in the presence of carbon monoxide. 4. The method of claim 1, wherein the catalyst is selected from the group consisting of rhodium chloride, chlorodicarbonyl rhodium timer, chlorobis(ethylene) rhodium dimer, ruthenium carbonyl, and ruthenium black. 5. The aldehyde is selected from the group consisting of dodecanal, octanal, butanal and docosanal, the nitrogen-containing compound is selected from the group consisting of dimethylamine, aniline and ammonia, and the tertiary amine is dodecyldimethylamine, octyldimethylamine, dibutyl The method of claim 1, wherein the compound is selected from the group consisting of aniline, tridodecylamine and dodecyldimethylamine.