JPH10130190A - Production of aldehyde compounds - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an aldehyde compound, enabling to produce the aldehyde compound in a high primary aldehyde selectivity and at a high reaction rate also from a low reactive olefin by hydroformylating an olefinic compound in the presence of a specific catalyst. SOLUTION: This method for producing an aldehyde compound comprises hydroformylating (B) an olefinic compound with (C) an aqueous gas e.g. at a temperature of 60-130 deg.C in a component C pressure of 5-100kg/cm<2> in the presence of (A) a catalyst comprising (Z1 ) a group VIII metal and (Z2 ) a compound of formula I [A is a (substituted) alkylene or (bis)arylene; C is a (substituted) alkylene or orthoarylene; B is C, a (substituted) bisarylene] (e.g. a compound of formula II) wherein Z1 and Z2 are contained in a Z1 metal atom/ Z2 phosphorus atom ratio of 1-4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing aldehydes by a hydroformylation reaction of an olefinic compound. According to the invention, primary aldehyde-rich aldehydes can be produced at high reaction rates even from generally less reactive olefins such as internal olefins, especially branched internal olefins.

[0002]

2. Description of the Related Art A method of producing an aldehyde by reacting an olefinic compound with hydrogen and carbon monoxide using a Group VIII metal catalyst is known as a hydroformylation method. In the prior art, when an internal olefin, particularly a branched internal olefin, is used as the olefinic compound, its reactivity is extremely low as compared with an alpha olefin, and hydroformylation occurs at an internal double bond site. The aldehyde with a branch at the carbon next to the formyl group was the major product.

[0003] For example, Journal of the Chemical Society of Japan 85 (3), 227
(1964) includes a method using rhodium carbonyl catalyst.
In the hydroformylation reaction of butene, it is described that the n / i ratio of the produced aldehyde is 0.16. It is also known that when a catalyst in which rhodium is modified with triphenylphosphine or a monodentate phosphite ligand is used, isomerization of a double bond of an internal olefin is suppressed and a branched aldehyde can be selectively obtained. (Japanese Unexamined Patent Publication No.
-51229, JP-A-59-51230). JP-A-5-178779 describes a method for hydroformylation of an olefinic compound using a catalyst modified with a polydentate phosphite ligand.
No method is disclosed for selectively causing a hydroformylation reaction at the terminal from internal olefins or branched olefins.

Further, when a hydroformylation reaction of an internal olefinic compound is carried out using a catalyst obtained by modifying rhodium with a bidentate phosphite ligand, a linear aldehyde can be obtained with relatively high selectivity. , Low reactivity, there was a problem in industrial implementation (Japanese Patent Application Laid-Open No. Sho 62-62).
No. 116587). JP-A-4-290551 discloses a method for producing an aldehyde from an olefin using a rhodium complex catalyst having bisphosphite as a ligand. However, this method is effective for propylene and internal olefins having a linear and low molecular weight such as butene-2. Turned out to be problematic.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide an internal olefin,
Particularly when a branched internal olefinic compound, for example, an olefin mixture obtained by oligomerization of propylene or butene is used as a raw material, a terminal hydroformylation reaction is selectively caused to produce a primary aldehyde-rich aldehyde at a high reaction rate. It is intended to provide a method of manufacturing.

[0006]

According to the present invention, according to the present invention, there is provided a compound of the type VIII
When an aldehyde is produced by a hydroformylation reaction of an olefinic compound in the presence of a catalyst containing a group metal and a phosphorus compound represented by the following general formula (1), the ratio of the phosphorus compound to the group VIII metal present in the reaction system To
The ratio of phosphorus atom to Group VIII metal atom is 1 or more and 4
When the content is less than 1, aldehydes rich in primary aldehyde can be produced from the internal olefinic compound at a high reaction rate.

[0007]

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In the formula, A represents an optionally substituted alkylene group, an arylene group or a bisarylene group, B represents an optionally substituted alkylene group, an orthoarylene group or a bisarylene group, and C represents a substituted Represents an alkylene group or an orthoarylene group which may be substituted.

In particular, according to the present invention, a mixed metal olefin containing a branched olefin obtained by oligomerization of an olefin having 4 or less carbon atoms is used as a raw material, and a group VIII metal and a phosphorus compound represented by the above general formula (1) are used. The aldehydes rich in primary aldehydes can be converted to a high level by performing a hydroformylation reaction by using a catalyst containing, and making the ratio of the phosphorus atom of the phosphorus compound to the Group VIII metal atom present in the reaction system 1 to less than 4. Can be manufactured at speed.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail. In the present invention, a Group VIII metal complex containing a phosphorus compound (bidentate phosphite ligand) represented by the above general formula (1) is used as a catalyst. . In the general formula (1), A
Represents an alkylene group, the alkylene chain preferably has 2 to 4 carbon atoms. When A represents an arylene group, A is usually a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group or the like.
Among these, an O-arylene group is preferable. When A represents a bisarylene group, those in which the ortho positions of the aryl groups are bonded directly or via a bonding group such as a hydrocarbon group, an oxygen atom, and a sulfur atom are preferable. Among them, those in which ortho-positions of a phenyl group or a naphthyl group are directly bonded are preferable.

In the general formula (1), when B represents an alkylene group, the alkylene chain has 2 to 4 carbon atoms.
It is preferred that When B represents an orthoarylene group, it is preferably an orthophenylene group or an orthonaphthylene group. When B represents a bisarylene group, those in which the ortho positions of the aryl group are bonded directly or via a bonding group such as a hydrocarbon group, an oxygen atom, and a sulfur atom are preferable, and among them, a phenyl group is preferable. Alternatively, those in which the ortho positions of the naphthyl group are directly bonded to each other are preferable. Most preferred as B is an orthophenylene group or an orthonaphthylene group.

In the general formula (1), when C is an alkylene group, the alkylene chain preferably has 2 to 4 carbon atoms. When C represents an orthoarylene group, it is preferably an orthophenylene group or an orthonaphthylene group. Most preferred as C is an orthophenylene group or an orthonaphthylene group. A, B and C in the general formula (1) may each have a substituent. Examples of such a substituent include an aryl group which may be substituted with an alkyl or alkoxy group having 1 to 20 carbon atoms, an alkyl or alkoxy group having 1 to 20 carbon atoms, and an alicyclic carbon having 3 to 20 carbon atoms. Hydrogen, cyano, halogen, nitro, trifluoromethyl, hydroxyl, amino, acyl, carbonyloxy, oxycarbonyl, amide, sulfonyl, sulfinyl, silyl, phosphonyl, thionyl And the like. Among them, an alkyl group or an alkoxy group having 1 to 4 carbon atoms is preferable. Some of such phosphorus compounds are illustrated in Table 1 below. In the formula, Me represents a methyl group, and t-Bu represents a tertiary butyl group.

[0013]

[Table 1]

[0014]

[Table 2]

[0015]

[Table 3]

[0016]

[Table 4]

[0017]

[Table 5]

The metal component VI of the catalyst used in the present invention
Group II metals include Ru_Three(CO) ₁₂, RuCl_Three, R
u (acac)_ThreeRuthenium compounds such as Pd (OA
c)_Two, PdCl_TwoPalladium compounds such as PtCl_Two
Platinum compounds such as Co_Two(CO)₈Cobalt compounds such as
Metal, rhodium metal supported on alumina, silica, etc., R
hCl_Three, Rh (NO_Three)_Three, Rh (OAc)_Three, Rh
(OHCO)_Three, Rh_TwoO _Three, Rh (acac) (C
O)_Two, [Rh (OAc) (COD)]_Two, Rh_Four(C
O)₁₂, [Rh (OAc) (CO)_Two]_TwoRhodium etc.
And the like. Rhodium among these
It is preferable to use a compound.

The amount of Group VIII metal used can vary widely, but usually the concentration in the hydroformylation reaction zone is in the range from 1 to 1000 ppm, preferably from 10 to 500 ppm, in terms of metal atoms. In the present invention, the amount of the phosphite ligand to be used with respect to the Group VIII element is 1 or more and less than 4 as a ratio of a phosphorus atom to a Group VIII metal atom (an atomic ratio of phosphorus / metal). When this ratio is 4 or more, the catalytic activity decreases. Conversely, when this ratio is less than 1, the terminal selectivity decreases. The preferred ratio of phosphorus / metal in the present invention is 1.5 to 3.5.

The olefinic compound used in the method of the present invention has 2 to 40 carbon atoms and one olefinic double bond.
Or two or more compounds. Preferably those having 8 or more carbon atoms are used. The method of the present invention can of course be applied to highly reactive olefins such as linear α-olefins, but branched olefins and internal olefins,
Particularly when applied to a branched internal olefin in which three or more carbon atoms are bonded to the olefin site, a more distinct effect is exhibited. Further, these olefin compounds have a substituent which does not essentially adversely affect the hydroformylation reaction, such as a carbonyl group, a carbonyloxy group, a hydroxyl group, an oxycarbonyl group, a halogen, an alkoxyl group, an aryl group, and a haloalkyl group. It may be.

Examples of some olefinic compounds include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-eicosene, and mixed α obtained by oligomerization of ethylene.
Α-olefins such as olefins; linear internal olefins such as cis and trans 2-butene, 2-hexene, 2-octene, 3-octene, 4-octene; isobutene, 2-methyl-2-butene, 3 Branched internal olefins having three or more carbon atoms bonded to olefinic moieties such as -methyl-3-heptene and 2,3-dimethyl-2-hexene; mixed olefins obtained by propylene oligomerization, and butenes obtained by butene oligomerization Α-olefins such as mixed olefins obtained by collimation of mixed olefins having 4 or less carbon atoms, internal olefins, branched internal olefins, etc .;
Crotonic acid, methyl crotonic acid, 3-pentenoic acid, 3-
Examples thereof include terminal or internal olefinic compounds having a substituent such as methyl pentenoate, 3-pentenonitrile, and 2,7-octadien-1-ol. The present invention is particularly applicable to the oligomerization of olefins having 4 or less carbon atoms, such as the hydroformylation of mixed olefins including branched olefins and internal olefins obtained by trimerization of propylene and dimerization of butene, The characteristics can be exhibited well.
Hydroformylates of these olefins are hydrogenated to alcohols and are useful as plasticizers for vinyl chloride.

In the hydroformylation method of the present invention, a solvent is not necessarily required, but in general, a solvent inert under the reaction conditions can be used. The amount of the solvent to be used is arbitrary, and for example, an amount necessary to dissolve the Group VIII metal and supply it to the reaction system may be used. As the solvent, benzene, toluene, xylene, aromatic hydrocarbons such as ethylbenzene, alkanes such as pentane, hexane, heptane, ethers such as diethyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, acetone, Methyl ethyl ketone, diethyl ketone,
Ketones such as methyl isopropyl ketone and ethyl-n-butyl ketone, and alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol and n-alkanol are used. Further, an aldehyde generated by the reaction, a condensation product thereof, a high-boiling substance obtained by separating the aldehyde generated from the reaction product liquid, and the like can also be used.

The reaction temperature can be selected from the range of room temperature to about 180 ° C., but it is more general to select the temperature range of about 50 to 150 ° C., and the temperature range of 60 to 130 ° C. is more preferable. . In general, in a temperature range lower than 50 ° C., the hydroformylation reaction rate is not sufficient, and when the temperature is higher than 150 ° C., deterioration of the activity of the catalyst, an increase in the boiling point of the product due to condensation, and hydrogenation of the olefin tend to occur.

The total pressure of the mixed gas (water gas) of hydrogen and carbon monoxide used in the reaction is from normal pressure to 200 kg / cm ^2.
5kg / cm ² to 100k
g / cm ² range is preferred. In addition to the water gas, it is possible to coexist a gas such as nitrogen, helium, or argon which is inert to the reaction. The molar ratio of hydrogen to carbon monoxide is usually 1:
It is in the range of 10-100: 1, preferably 1: 2 to 10: 1.

The reaction can be carried out using any conventional equipment such as a stirred type reaction vessel or a bubble column type reaction vessel, and the reaction can be carried out by any of the well-known methods such as a continuous system, a semi-continuous system and a batch system. obtain. Since the phosphite compound used as a ligand in the present invention is stably present in the reaction product solution, the catalyst component containing the phosphite compound and the hydroformylated product are separated from the reaction product solution by a known method, and the catalyst is removed. The components can be recycled to the hydroformylation reaction zone and reused as a catalyst.

[0026]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, the symbol showing the kind of phosphorus compound depends on Table-1.

Examples 1 to 7 and Comparative Examples 1 and 2 About 0.0977 mmol of Rh (a) were placed in a 200 ml stainless steel autoclave under a nitrogen gas atmosphere.
cac) (CO) ₂ , phosphite compound, 50 ml of 2-octene, 45 ml of heptane, and 5.0 ml of m-xylene as an internal standard for gas chromatography analysis. The reaction was continued at 100 ° C. for 2 hours while supplying a water gas having an H ₂ / CO molar ratio of 1 so as to maintain a constant pressure of 20 kg / cm ² G. The result of analyzing the reaction solution by gas chromatography is shown in Table-2.

[0028]

[Table 6]

As is clear from the comparison between Examples 1 and 2 and Comparative Examples 1 and 2, when the same phosphorus compound was used, P
When / Rh is 4 or more, the conversion rate is greatly reduced. Example 8 0.0977 mmol of Rh (ac) was placed in a 200 ml stainless steel autoclave under a nitrogen gas atmosphere.
ac) (CO) ₂ , 0.149 mmol of phosphite compound (P-1), 50 ml of octene (octene obtained by dimerization of a mixture of 1-butene and 2-butene, n-octenes, 3-methylheptenes and 2,3
-Mixture of dimethylbutenes), 45 ml of heptane and 5.0 ml of m-xylene. Water gas having an H ₂ / CO molar ratio of 1.0 was introduced at a pressure of 20 kg / cm ² G
The reaction was continued at 100 ° C. for 8 hours while supplying so as to maintain a constant pressure of. The results are shown in Table-3.

Example 9 The amount of Rh (acac) (CO) ₂ used was 0.245 ml.
And (P-10) as a phosphite compound in 0.2
The reaction was carried out in the same manner as in Example 8, except that 31 mmol was used. The results are shown in Table-3. Comparative Example 3 The following (P-20) was 0.1 as a phosphite compound.
The reaction was carried out in the same manner as in Example 8, except that 49 mmol was used. The results are shown in Table-3. Phosphite compound (P-20)

[0031]

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[0032]

[Table 7]

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 45/50 C07C 45/50 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Naomasa Sato Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa 1000 Mitsubishi Chemical Corporation Yokohama Research Laboratory

Claims (10)

[Claims] An aldehyde is produced by hydroformylation of an olefinic compound in the presence of a catalyst containing a Group VIII metal and a phosphorus compound represented by the following general formula (1). A method for producing aldehydes, wherein a ratio of a phosphorus compound to a group metal is 1 or more and less than 4 as a ratio of a phosphorus atom to a group VIII metal atom. Embedded image In the formula, A represents an optionally substituted alkylene group, an arylene group or a bisarylene group, B represents an optionally substituted alkylene group, an orthoarylene group or a bisarylene group, and C represents a substituted Represents an alkylene group or an orthoarylene group. 2. The method for producing an aldehyde according to claim 1, wherein A is a bisarylene group which may be substituted. 3. The method according to claim 2, wherein A is a bisarylene group which may be substituted, and two rings of the bisarylene group are directly bonded to each other without a bonding group.
A method for producing the aldehyde described in the above. 4. The method for producing an aldehyde according to claim 1, wherein B and C are each independently an optionally substituted O-arylene group. 5. A method for producing an aldehyde by hydroformylation of an olefinic compound in the presence of a catalyst containing a Group VIII metal and a phosphorus compound represented by the following general formula (2): A method for producing aldehydes, wherein a ratio of a phosphorus compound to a group metal is 1 or more and less than 4 as a ratio of a phosphorus atom to a group VIII metal atom. Embedded image (In the formula, each benzene ring constituting the diphenyl ring has C
₁ substituent selected from alkoxy groups of the alkyl group and C ₁ -C ₄ in -C ₄ may be bonded. Each O-phenylene ring bonded to a phosphorus atom may have a substituent selected from a C ₁ -C ₄ alkyl group and a C ₁ -C ₄ alkoxy group bonded thereto, or a butadienyl group They may combine to form a β, β-naphthylene group. ) 6. The method according to claim 1, wherein the ratio of the group VIII metal and the phosphorus compound present in the reaction system is 1.5 to 3.5 as a ratio of the phosphorus atom to the group VIII metal atom. 6. The method for producing an aldehyde according to any one of items 1 to 5. 7. The method for producing aldehydes according to claim 1, wherein the Group VIII metal is rhodium. 8. The method for producing aldehydes according to claim 1, wherein the olefinic compound has 8 or more carbon atoms. 9. The aldehyde according to claim 1, wherein the olefinic compound is a mixed olefin containing a branched olefin obtained by oligomerization of an olefin having 4 or less carbon atoms. Manufacturing method. 10. The method for producing aldehydes according to claim 1, wherein the olefinic compound is a mixed octene obtained by dimerization of butene.