JPS5817731B2 - Method for producing aldehydes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing aldehydes from carbon monoxide, water and olefins in a single step reaction.

The conventional method for synthesizing aldehydes from olefins is
There is a method of carrying out the hydroformylation reaction in the presence F of a dicobalt octacarbonyl catalyst.

The Shiri-Shiko method uses a mixed gas of carbon monoxide and hydrogen.
・There is a drawback to preparing this first.

In order to overcome the drawbacks of this conventional method, the present inventors have conducted extensive research, and as a result, they have succeeded in reacting olefins, carbon oxide, and water with the presence of a catalyst consisting of a certain type of organic phosphorus compound and a cobalt carbonyl compound. It was discovered that aldehydes can be obtained through a one-step tf reaction, and based on this knowledge, the present invention was developed.

That is, the present invention provides 1,2-bis(diphenylsulfino)ethane, 1,3bis(diphenylsulfino)propane, and cis-2,2-bis(diphenylphosphino).
A phosphorus compound selected from ethylene, 2-bis(diphenylphosphino)acetylene, bis(2-;phenylphosphinoethyl)phenylphosphine, and triphenylphosphine, and a cobalt carbonyl compound. The present invention provides a method for producing an alrahide, which is characterized by reacting carbon monoxide, water, and urefin in the presence of a catalyst.

In the method of the present invention, examples of the cobalt carbonyl compound to be coordinated with the organic phosphorus compound include 1, dicobalt octacarbonyl, tetracobano 1 tododecacarbonyl, and alkylidine tricobal 1 nonacarbonyl.

The method for preparing the catalyst used in the method of the present invention is as follows:
・2-bis(diphenylphosphino)cotane, ■・3bis(diphenylphosphino)propane, cysuto-2-bis(diphenylphospha))ethylene, ■・2-bis(
A method for preparing an organic phosphorus compound selected from diphenylphos:ino)acetylene, bis(2-diphenylphosphino)phenylphosphine, and triphenylphos:yne by mixing (preparing) a cobalt carbonyl compound in a solvent in advance, this book Under the reaction conditions of the invention, a cobalt compound that reacts with the -acid carbon to form a cobalt carbonyl compound is converted into 1,2-bis(diphenylphosphino)ethane, 1,
3bis(diphenylphosphino)furopane, cysuto2
- Charged into a reactor with an organic phosphorus compound selected from bis(diphenylphosphino)ethylene, 1,2-bis(diphenylphosphino)acetylene, bis(2-diphenylphosphino)phenylphosphine and hydriphenylphosphine. There is a method of preparing it on the spot before carrying out the aldehyde synthesis reaction.

The cobalt compounds used in this latter method include:
cobalt acetate, cobalt naphthenate, cobalt hydroxide,
Examples include cobalt carbonate.

1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)furopane, cis-1,2-bis(diphenylphosphino)ethylene, 1,2-bis( diphenylphosphino)
The amount of the organic phosphorus compound selected from acetin, bis(2-diphenylphosphino)phenylphosphine and triphenylphosphine is suitably 0.05 to 20 times the mole of the cobalt atom of the cobalt carbonyl compound; A range of .2 to 0.6 times the mole is particularly preferred.

In this case, if the amount exceeds twice the upper limit by mole, the catalytic activity will decrease considerably.

On the other hand, if the amount is less than the lower limit of 0.05 times the mole, the catalyst will be completely decomposed during the reaction, and cobalt metal will precipitate as an insoluble component in the solution.

The method of the invention can be carried out in a solvent.

The solvent at this time is triethylamine, γ-butyrolactone, acetone, acetonitrile, etc., and water.

Examples of soluble solvents include tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane,
- Chain and cyclic ethers such as 3-dioxolane are particularly preferred.

The method of the invention requires that it be carried out using water.

The amount of water is arbitrary as long as the three components (solvent, water, and olefin) do not undergo phase separation during mixing.

In addition, in the method of the present invention, the amount of catalyst is olefin (m
1 to 1 times (mmol) to 50 1 mol) is appropriate, and a range of 100 to 7 times (mmol) is preferable.If it is out of the above range, ketones and carboxylic acids that are by-products may be produced in large quantities. (As a result, the selectivity of aldehydes decreases considerably.

The method of the present invention in which carbon monoxide, water and olefin are reacted in the presence of the above-mentioned catalyst is generally carried out at a reaction temperature of 50 to 30°C.
0°C, preferably 120-200°C, carbon monoxide pressure,
Usually 1-300 kg/crA, preferably 5-100
kg/crtt.

As the raw material olefin in this case, those used in the conventional hydroformylation reaction using a hydrogen-carbon monoxide mixed gas can be used.

Examples of such olefins include propylene, -hexene, and -decene.

According to the method of the present invention, there is no need to first produce synthesis gas, and aldehydes can be produced directly through a one-step reaction.

In other words, according to the conventional method, in order to produce aldehydes from olefins, carbon monoxide, and water, synthesis gas is first produced by the reaction of carbon monoxide and water, and then aldehydes are produced by the reaction of synthesis gas and olefins. In contrast, the method of the present invention has the excellent effect of efficiently producing aldehydes through the direct reaction of carbon monoxide, water, and olefins.

Furthermore, in the method of the present invention, the catalyst can be used repeatedly, which has the advantage of simplifying the process and is extremely advantageous from the standpoint of industrial implementation.

Next, the present invention will be explained in more detail based on examples.

Example 1 Dicobalt octacarbonyl 0.61' (about 2 mmol
), 1 ・2-bis(diphenylphosphino)ethane 0
．． 79? (approximately 2 mmol), 1 ml of H2O, and 50 rILl of tetrahydrofuran as a solvent in an internal volume of 100 m
After charging the stainless steel electromagnetic oven (1) into a stainless steel autoclave and expelling the air with CO gas, 30 mmol of propylene was introduced as an olefin, and further CO4
Introducing 0 mmol, total pressure 21, Ic, g/crr
L (room temperature), and the reaction was carried out at 135°C.

After 17 hours of reaction, the pressure increased from 27 kg/crtl to 1
The weight decreased to 6 kg/cm.

The solution taken out from the autoclave was homogeneous, and analysis by gas chromatography revealed that the amount of aldehyde (n- and i-butyraldehyde) produced was 7.2 mmol.
, and no C4-alcohol was detected.

In addition, a reaction gas analysis confirmed the presence of trace amounts of propane.

Examples 2 to 5 In place of tetrahydrofuran in Example 1, ethylene glycol dimethyl ether (1), diethylene glycol dimethyl ether (2), ■4-dioxane (3)
Alternatively, the reaction was carried out in the same manner as in Example 1, except that the same amount of 1.3-dioxolane (4) was used as a solvent.

The results are summarized below and shown in Table 1. Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that the amount of water was increased from 1 ml to 5 TrLl. The reaction solution caused phase separation, and a considerable amount of noise from the catalyst [decomposed]. As a result, the total amount of aldehyde produced was only 0.01 m
It was less than mol.

Examples 6-7 In place of 1,2-bis(diphenylphosphino)ethane in Example 1, cis-1,2-bis(diphenylphosphino)ethylene [1], The reaction was carried out in the same manner as in Example 1 except that the same mole of fino)acetylene [2] was used as the coordination agent.

The results are summarized in Table 2.

Comparative Example 2 The reaction was carried out in the same manner as in Example 1 except that 1,2-bis(diphenylphosphino)ethane of Example 1 was not added, and the total amount of aldehyde produced was 2.1 mmol, but the catalyst was completely decomposed into metallic cobalt during the reaction.

In addition, such a cobalt-containing solution was put into the autoclave again, the same amount of CO and propylene as in Example 1 were introduced, and the reaction was carried out at 135°C for 17 hours, but no new generation of aldehyde was observed. .

Examples 8 to 11 The amount of 1,2-bis(diphenylphosphino)ethane in Example 1 was changed to 0.4i (about 1.0 mmol), 0.6
0P (about 1.5 mmol), 1.21 (about 3.0m
The reaction was carried out in the same manner as in Example 1, except that the amount was changed to 1.1' (about 4 mmol) or 1.1' (about 4 mmol).

The results are shown in Table 3.

Example 12 The reaction solution of Example 3 was charged into the same autoclave, and C
When 40 mmol of O and 30 mmol of propylene were reintroduced and reacted at 135°C for 17 hours, 9.3 mmol of aldehyde (n- and i-butyraldehyde) was newly added.
mol was obtained, and the catalytic effect was confirmed.

Compared to the case where phosphine is not added to the system (Comparative Example 2),
This is in contrast to the excellent catalytic activity in the case of reuse.

Example 13 The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 150°C and CO was 70 mmol. The obtained aldehyde was 11.8 mmol and the alcohol was 1.9 mmol.
It was l.

Example 14 The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 150°C and the CO pressure was 50 kg/crA (at the reaction temperature:
ol, alcohol was 0.34 mmol.

Example 15 Methynyl tricobalt nonacarbonyl 0.6079 (1,
When the reaction was carried out in the same manner as in Example 1 except that 33 mmol) was used, the total amount of aldehyde produced was 6.8 mmol, and the total amount of alcohol produced was 0.72 mmol.

Example 16 1-hexene 30 m instead of propylene in Example 1
When the reaction was carried out in the same manner as in Example 1 except that mol was used, aldehyde (n-heptanal + 2-methylhexanal + 2-ethylpentanal) 5.5 mm
ol was obtained.

Examples 17 to 19 In place of 1,2-bis(diphenylphosphino)ethane in Example 1, 1,3-bis(diphenylphosphino)furopane [3], bis(2-diphenylphosphinoethyl)phenyl Oxo-reaction of propylene was carried out in the same manner as in Example 1, except that phosphine [4] or triphenylphosphine 5] was used, the reaction temperature was 150°C, and the CO pressure was 50 kg/ca (constant at the reaction temperature). .

The results are summarized in Table 4.

In addition, in all cases, the catalyst solution after the reaction was uniform.

Comparative Example 3 The reaction was carried out in the same manner as in Examples 17 to 19 except that phosphine was not added, and the total amount of aldehyde produced was 2.
．． 5 mmol, and as in Comparative Example 2, the catalyst was completely decomposed after the reaction.

Claims (1)

[Claims] 11,2-bis(diphenylphosphino)ethane, l.
3-bis(diphenylphosphino)propane, cysuto-2-bis(diphenylphosphino)ethylene, 1,2-
Bis(diphenylphosphino)acetylene, bis(2-
Diphenylphosphinoethyl) is characterized by reacting carbon monoxide, water, and an olefin in the presence of a catalyst consisting of an organic phosphorus compound selected from phenylphosphine and triphenylphosphine and a cobalt carbonyl compound. A method for producing an aldehyde.