JPH07278040A - Production of aldehyde from inner olefinic compound - Google Patents

Abstract

PURPOSE:To selectively produce a linear aldehyde in high yield by putting a specific bisphosphite compound in a system and hydroformylating an inner olefin compound in the presence of a catalyst of a metal of the group VIII under a controlled condition. CONSTITUTION:An inner olefin compound is reacted with hydrogen and carbon dioxide in the presence of a catalyst of a metal of the group VIII under a controlled condition. In the reaction, a bisphosphite compound of formula I (W is an arylene which contains two or more mutually adjoining carbon atoms on an aromatic ring bonded to X atom and may contain a substituent group; X is O; Z1 to Z4 are each aryl which may contain a substituent group) exists and the reaction is carried out at 50-150 deg.C under a condition of total pressure of H2 and CO2 of <=40kgf/cm<2> to produce a hydroformyl compound rich in a linear aldehyde. Compounds of formula II and formula III may be cited as the compound of formula I. In this method, a linear aldehyde can be industrially and advantageously produced from an inner olefin industrially produced in a large amount as a new material.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a process for producing a linear aldehyde-rich hydroformylation product from an internal olefinic compound.

[0002]

2. Description of the Related Art A method for producing an aldehyde by reacting an olefinic compound with hydrogen and carbon monoxide using a Group 8 metal catalyst is known as a hydroformylation method. When an internal olefinic compound is used as the olefinic compound, in the prior art, a branched aldehyde in which the internal double bond is hydroformylated was the main product.

For example, Journal of the Chemical Society of Japan 85 (3) 227.
(1964), using a rhodium carbonyl catalyst 2
-In the butene hydroformylation reaction, it is stated that the n / i ratio of the product aldehyde is 0.16. It is also known that when a catalyst obtained by modifying rhodium with triphenylphosphine or a monodentate phosphite ligand is used, isomerization of the double bond of the internal olefin is suppressed, and a branched aldehyde is selectively obtained. (Japanese Patent Laid-Open No. 5
9-51229, JP-A-59-51230). Also,
JP-A-5-178779 describes a hydroformylation method of an olefinic compound using a catalyst modified with a polydentate phosphite ligand, but a linear aldehyde is selectively produced from an internal olefin. No method is disclosed.

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 good selectivity. However, since the induction period is long and the reaction activity is low, there was a problem in industrial implementation (JP-A-62-116587).

[0005]

The present invention has been made in view of the above circumstances, and an object thereof is to selectively produce a linear aldehyde from an internal olefinic compound in a high yield and industrially. An object is to provide a method for producing an aldehyde that can be advantageously produced.

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that internal olefinic compounds are present in the presence of a specific catalyst, specifically, JP-A-5-17877.
Among the compounds described in No. 9, a hydroformylation reaction is performed in the presence of a bisphosphite compound in which the A structure (W structure in the present invention) in the general formula is an arylene group to produce a linear aldehyde-rich compound. I got the knowledge that I can get things.

As a result, the structure A has an oxygen atom (X atom in the present invention) at a specific position in the arylene group.
The present invention has been completed by establishing a method of using a bisphosphite compound, which is an arylene group having a structure to bond with, as a catalyst and conducting a hydroformylation reaction under controlled reaction conditions. The gist of the present invention is to produce a hydroformylation product by reacting an internal olefinic compound with hydrogen and carbon monoxide in the presence of a Group 8 metal catalyst to produce a hydroformyl compound, in which the reaction system comprises the following general formula: (I)

[0008]

[Chemical 3]

(In the formula, W is an optionally substituted arylene group in which two carbon atoms on an aromatic ring bonded to the X atom are adjacent to each other, X is an oxygen atom, and Z ₁
To Z ₄ represent an aryl group which may have a substituent)
In the presence of a bisphosphite compound represented by
A method for producing aldehydes from an internal olefinic compound, characterized in that the reaction is carried out in the temperature range of 150 ° C. and under the condition that the total pressure of hydrogen and carbon monoxide is 40 kgf / cm ² or less.

The present invention will be described in detail below. The bisphosphite compound used in the present invention has the following general formula (I).
It is represented by.

[0011]

[Chemical 4]

In the above general formula (I), W is an optionally substituted arylene group in which two carbon atoms on the aromatic ring bonded to the X atom are adjacent to each other. Examples thereof include a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, a pyrylene group and a coronylene group, and among them, a 1,2-phenylene group and a 1,2-phenylene group.
A naphthylene group or a 2,3-naphthylene group is preferable.

As the substituent of W, an alkyl group,
An aryl group, which may have an alkyl group having 1 to 20 carbon atoms or an alkoxyl group having 1 to 20 carbon atoms as a substituent, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, and a carbon number. 3 to 20 alicyclic hydrocarbon groups,
Or, cyano group, halogen, nitro group, trifluoromethyl group, hydroxyl group, amino group, acyl group, carbonyloxy group, oxycarbonyl group, amide group, sulfonyl group, sulfinyl group, silyl group, phosphonyl group, thionyl group, etc. Is mentioned.

Among the above-mentioned substituents of W, the number of carbon atoms is 1 to 1.
An aryl group which may have a 12-alkyl group or a C1-C20 alkoxyl group as a substituent, a C1-C12 alkyl group, and a C1-C10 alkoxyl group, and a C3-C3 It is preferable to use one selected from 12 alicyclic hydrocarbon groups. In addition, Z _{1 to} Z ₄ in the general formula (I) represent an aryl group which may have a substituent, and as the aryl group, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyryl group, Examples thereof include coronyl group and azuryl group.

The substituent of Z has 1 to 2 carbon atoms.
An aryl group which may have an alkyl group having 0 or an alkoxyl group having 1 to 20 carbon atoms as a substituent, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, and an alkyl group having 3 to 20 carbon atoms Alicyclic hydrocarbon group, or cyano group, halogen, nitro group, trifluoromethyl group, hydroxyl group, amino group, acyl group, carbonyloxy group, oxycarbonyl group, amide group, sulfonyl group, sulfinyl group, silyl group , A phosphonyl group, a thionyl group and the like.

Among the above Z _{1 to} Z ₄ , a phenyl group represented by the following general formula (II) or a β-naphthyl group represented by the following general formula (III) is preferable, and a substituent at least in the ortho position is used. A phenyl group or β
-The naphthyl group is preferred.

[0017]

[Chemical 5]

In the above general formulas (II) and (III), Y _{1 to} Y ₈
Is an aryl group which may have hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkoxyl group having 1 to 20 carbon atoms as a substituent, an alkyl group having 1 to 20 carbon atoms, and an alkoxyl group having 1 to 20 carbon atoms. Represents a group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a substituent selected from a hydroxyl group, an acyl group, a carbonyloxy group and an oxycarbonyl group.

Among the above Y ₁ to Y ₈ , hydrogen, an aryl group which may have an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms as a substituent,
It is preferable to use a substituent selected from an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and an alicyclic hydrocarbon group having 3 to 12 carbon atoms. As Z _{1 to} Z ₄ in the above general formula (I), it is preferable to specifically use the following compounds.

[0020]

[Chemical 6] Respectively.

Of the above-mentioned general formula (I), it is preferable to use those in which both W and Z have the respective preferable structures described above. Further, examples of the bisphosphite compound of the present invention represented by the general formula (I) include the following.

[0022]

[Chemical 7]

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

The amount of the bisphosphite compound of the present invention to be used is selected from the range of 0.1 to 100 mol per gram atom of Group 8 metal present in the reaction medium, but hydroformylation is industrially carried out. In this case, it is not economically preferable to use an excess of free phosphite ligand. With the bisphosphite ligand of the present invention, an excess of free ligand is not necessary and is preferably 0.3
Even when used in an extremely small amount of ˜50 mol, more preferably 0.5˜10 mol, the effect is substantially obtained.

In the present invention, the bisphosphite compound is preferably used by forming a complex with the Group 8 metal compound in advance. The Group 8 metal complex is a Group 8 metal compound,
For example, hydride, halide, organic acid salt, inorganic acid salt,
It can be easily prepared from an oxide, a carbonyl compound, an amine compound and the like and the phosphite compound by a known complex formation method. In some cases, the Group 8 metal compound and the phosphite compound may be supplied to the hydroformylation reaction zone to form a complex there for use.

Examples of the Group 8 metal compound include Ru₃
(CO)₁₂, Ru (NO₃)₃, RuCl₃(Ph
₃P)₃, Ru (acac)₃Ruthenium compounds such as
PdCl ₂, Pd (OAc)₂, Pd (acac)₂,
PdCl₂(COD), PdCl ₂(Ph₃P)₂Etc.
Palladium compound, OS₃(CO)₁₂, OsCl₃Etc.
Osmium compound, Ir_Four(CO)₁₂, IrSO_FourEtc.
Iridium compound, K₂PtCl_Four, PtCl₂(Ph
CN)₂, Na₂PtCl₆・ 6H₂Platinum compound such as O
Thing, CoCl₂, Co (NO₃)₂, Co (OA
c)₂, Co₂(CO)₈Cobalt compounds such as aluminum
Rh metal, R supported on a carrier such as sodium, silica or activated carbon
hCl₃, Rh (NO₃)₃, Rh (OAc)₃, Rh
(OHCO)₃, Rh ₂O₃, Rh (acac) (C
O)₂Rh chelating compounds such as rhodium chloride
Of rhodium, such as thorium and potassium rhodium chloride
Inorganic or organic acid salt, [Rh (OAc) (CO
D)]₂, Rh_Four(CO)₁₂, Rh₆(CO) ₁₆, Μ,
μ'-RhCl₂(CO)_Four, RhH (CO) (Ph₃
P)₃, [Rh (OAc) (CO)₂]₂, [RhCl
(COD)]₂, [Rh (μ-s-t-Bu) (CO)
₂] Rhodium compounds such as Rh carbonyl complex compounds
(Where acac is an acetylacetonate group and Ac is
Cetyl group, COD is 1,5-cyclooctadiene, Ph
Each represents a phenyl group), among which
It is preferable to use a rum compound.

The amount of the Group 8 metal compound used is not particularly limited, and may be arbitrarily used so as to obtain desired results in terms of catalyst activity and economic efficiency. In the present invention, the hydroformylation reaction is usually used. The concentration in the zone is 0.
It is selected from the range of 05 mg to 5 g, preferably 0.5 mg to 1 g.

The concentration of the Rh complex catalyst in the reaction medium is 1 to 1000 ppm in terms of atom, preferably 10 to 500 p.
pm, and more preferably within the range of 25 to 350 ppm. As the internal olefinic compound used in the method of the present invention, an internally unsaturated compound having a linear or branched structure can be used, and a compound having 2 to 20 carbon atoms can be usually used. . In addition, these internal olefinic compounds are essentially substituents that do not adversely affect the hydroformylation reaction, such as carbonyl group, carbonyloxy group, oxy group, hydroxyl group, oxycarbonyl group, halogen, and C1-18 An alkoxyl group,
It can have an aryl group, a haloalkyl group, and the like.
As the internal olefinic compound, specifically, 2-butene, 2-pentene, 2-hexene, 3-hexene, 2
-Straight chain internal olefinic compounds such as heptene, 2-octene, 3-octene, 4-octene, 2-decene, 2-tetradecene, 2-octadecene, or 2-methyl-2-butene, 2,3- Dimethyl-2-butene, 4-
Branched internal olefinic compounds such as amyl-2-decene and 4-methyl-2-tridecene, or propylene dimer, propylene trimer, propylene tetramer, butene dimer, butene trimer, etc. Examples include mixed olefinic compounds, and substituted internal olefinic compounds such as crotyl alcohol, crotonic acid, methyl crotonic acid, 3-pentenoic acid, methyl 3-pentenoate, and 3-pentenenitrile. In the present invention, 2-, which may have a substituent, is particularly preferable.
Butene, 2-pentene, 2-hexene, 2-heptene,
It is effective when a linear internal olefinic compound such as 2-octene is used.

A solvent is not always necessary in the hydroformylation method of the present invention, but in general, a solvent inert under the reaction conditions can be used. The amount of solvent used is not critical and may be sufficient to dissolve the required amount of Group 8 metal in the reaction medium. Examples of the solvent include aromatic hydrocarbon compounds such as benzene, toluene, xylene and dodecylbenzene, aliphatic hydrocarbon compounds such as pentane, methylcyclohexane and heptane, ketones such as acetone, diethyltoken and methyl ethyl ketone, tetrahydrofuran, dioxane and the like. Ethers, ethyl acetate, esters such as di-n-octyl phthalate, etc., liquid aldehyde which is the same as or different from the liquid aldehyde produced in the reaction, or a condensation product thereof, and an excess of the olefinic compound as a starting material. Amounts can be used. It is also possible to use mixtures of these compounds.

The hydroformylation reaction of the present invention is carried out at a reaction temperature of 50 to 150 ° C., preferably 70 to 1
It can be effectively carried out at 30 ° C. In the temperature region lower than 50 ° C, the hydroformylation rate is not sufficient, and
If the temperature is higher than 0 ° C., the activity of the catalyst deteriorates and the boiling point increases due to condensation, hydrogenation and the like occur, which is not preferable in the hydroformylation reaction of the present invention. Also, optionally a linear aldehyde, and, in order to produce a high yield, the total pressure of hydrogen and carbon monoxide (water gas) of 40 kgf / cm ² or less, preferably 30 kgf / cm ² or less, Particularly preferably 15 kg
It is important to react under the condition of f / cm ² or less. The lower limit of pressure is not particularly critical and is basically determined by the total amount of reaction components required to maintain the reaction. Molar ratio of hydrogen and carbon monoxide (H ₂ / CO)
Is usually 1:10 to 100: 1, preferably 1: 1 to 1
It is within the range of 0: 1.

As a reaction system for the hydroformylation reaction, a stirring reaction tank, a bubble column reaction tank or the like is used, and any of continuous operation, semi-batch operation and batch operation can be easily carried out. Since the phosphite compound used in the present invention is stable even after the hydroformylation reaction, the catalyst component containing the phosphite compound and the hydroformylation product are separated by a known method, and a part or all of the catalyst components are hydroformylated. It can be recycled to the reaction zone and reused as a catalyst.

[0034]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Examples 1 to 6 In a stirring autoclave having an internal volume of 200 ml, 0.27 mol of trans-2-butene was added to 55 ml of toluene.
And m-xylene as an internal standard in 5 ml of Rh
The hydroformylation reaction was carried out for 5 hours under the conditions shown in Table 1 in the presence of a mixture of (acac) (CO) ₂ and the bisphosphite ligand of the formula (7). The results of analysis of the reaction product by gas chromatography are shown in Table-1.
It was shown to.

[0035]

[Chemical 11]

[0036]

[Table 1]

Examples 7 to 9 and Comparative Examples 1 to 4 Hydroformylation reactions were carried out in the same manner as in Examples 1 to 6 except that phosphorus compounds and reaction conditions shown in Table 2 were used. In Table 2, phosphorus compounds (1), (9), and (12) correspond to the compounds having the numbers exemplified above, and phosphorus compound (13) includes triphenylphosphine (TPP) and phosphorus compounds (14) and (15). ) Represents a compound represented by the following formula. The analysis results of reaction products are shown in Table 2.

[0038]

[Chemical 12]

Example 10 A hydroformylation reaction was carried out in the same manner as in Examples 1 to 6 except that about 0.16 mol of 2-octene was used as a raw material olefin and the conditions shown in Table 2 were used. .
The analysis results of the reaction products are shown in Table-2.

[0040]

[Table 2]

From the results shown in Tables 1 and 2, when the hydroformylation reaction was carried out by the method of the present invention, the aldehyde yield and the n-aldehyde content were excellent, and
It can be seen that the induction period of the reaction is substantially negligible and the initial reaction rate is large.

[0042]

INDUSTRIAL APPLICABILITY By carrying out a hydroformylation reaction of an internal olefinic compound using the method of the present invention, a linear aldehyde can be selectively produced in a high yield. When a bisphosphite compound is used as a ligand, the induction period required for the formation of active species by the catalyst metal and the ligand is substantially negligible, and the initial reaction rate is large, which is industrially advantageous. The reaction can be carried out.

Conventionally, linear aldehydes are mainly α-
Although it was produced from olefin as a raw material, it is possible to selectively obtain a linear aldehyde from a new raw material called internal olefin that is industrially produced in large amounts, and therefore, the production method of the present invention is industrial. High utility value.

Claims (7)

[Claims] 1. A method for producing an aldehyde which comprises reacting an internal olefinic compound with hydrogen and carbon monoxide in the presence of a Group 8 metal catalyst to produce a hydroformylated product, wherein the reaction system comprises the following general formula (I): ) [Chemical 1] (In the formula, W is an optionally substituted arylene group in which two carbon atoms on an aromatic ring bonded to an X atom are adjacent to each other, X represents an oxygen atom, and Z _{1 to} Z ₄ Represents an aryl group which may have a substituent) in the presence of a bisphosphite compound at a temperature range of 50 to 150 ° C. and a total pressure of hydrogen and carbon monoxide of 40 k.
A method for producing an aldehyde from an internal olefinic compound, which comprises performing the reaction under a condition of gf / cm ² or less. 2. W may optionally have a substituent 1,2
-Phenylene group, 1,2-naphthylene group or 2,3-
The method for producing an aldehyde according to claim 1, which is a naphthylene group. 3. W is an aryl group which may have an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms as a substituent, an alkyl group having 1 to 12 carbon atoms, and a carbon number 1 10 to 10 alkoxyl groups and 3 to 3 carbon atoms
The method for producing an aldehyde according to claim 1, which is an arylene group which may have a substituent selected from the alicyclic hydrocarbon group of 12. 4. The method according to claim 1, wherein Z _{1 to} Z ₄ are each a phenyl group represented by the following general formula (II) or a β-naphthyl group represented by the following general formula (III). Method for producing aldehydes. [Chemical 2] (In the general formulas (II) and (III), Y _{1 to} Y _{8 each} represent hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group which may have an alkoxyl group having 1 to 20 carbon atoms as a substituent. A substituent selected from an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a hydroxyl group, an acyl group, a carbonyloxy group, and an oxycarbonyl group. Represents a group) 5. Y _{1 to} Y _{8 each} is hydrogen, an aryl group which may have an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms as a substituent, and an alkyl group having 1 to 1 carbon atoms.
12 alkyl groups, C1-10 alkoxyl groups,
The method for producing an aldehyde according to claim 4, which is a substituent selected from an alicyclic hydrocarbon group having 3 to 12 carbon atoms. 6. The internal olefinic compound is a compound selected from optionally substituted 2-butene, 2-pentene, 2-hexene, 2-heptene, and 2-octene. The method for producing an aldehyde according to any one of 1. 7. The use amount of the bisphosphite compound represented by the general formula (I) is in the range of 0.5 to 10 mol per gram atom of Group 8 metal present in the reaction system. 7. The method for producing an aldehyde according to any one of 6 to 6.