Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
1998-10-27
2001-01-09
Vollano, Jean F (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S451000
Reexamination Certificate
active
06172267
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for producing aldehydes by hydroformylation of a mono-olefinic compound.
2. Discussion of Background
A process which comprises reacting an olefinic compound with water gas in the presence of a catalyst to produce aldehydes or alcohols as their hydrogenated products, is well-known as a hydroformylation process. As a catalyst for the hydroformylation reaction, it is common to use a soluble complex of Group VIII metal and an organic phosphorous compound as a ligand. In general, the ligand used together with the metal component of the catalyst gives a substantial influence to the catalytic reaction. Also in the hydroformylation reaction, it is well known that the catalytic activity and the selectivity are substantially influenced by the ligand. On the other hand, in order to carry out the hydroformylation reaction industrially advantageously, it is required not only to improve the catalytic activity and selectivity but also to maintain the ligand to be stable so as not to let a decomposition reaction of the ligand including a modification reaction such as a structural change take place during the entire process for the production of aldehydes. Accordingly, various efforts to design the ligand have been made for these purposes.
Various phosphite compounds are known as a group of phosphorus compounds which may be used as the ligands for the hydroformylation reaction. In addition to simple monophosphites such as trialkyl phosphites or triarylphosphites, various phosphite compounds such as polyphosphites having a plurality of coordinating phosphorus atoms in their molecules, have been proposed. For example, JP-A-62-116587 or JP-A-6-166694 discloses a hydroformylation reaction using a bisphosphite compound wherein one of the two phosphite groups has a cyclic structure, and JP-A-62-116535, JP-A-2-231497, JP-A-6-199728 or JP-A-6-199729 discloses a hydroformylation reaction employing a bisphosphite compound wherein both of the two phosphite groups have cyclic structures. In the bisphosphite compounds used in these prior art references, 6,6′-positions of the bisarylene group as the crosslinking moiety have no substituents.
JP-A-6-184036 discloses a method for producing 1,6-hexanedials by a hydroformylation reaction of a diene such as butadiene by using a bisphosphite wherein the 6,6′-positions of the bisarylene group as the crosslinking moiety have substituents, and both of the two phosphite groups have cyclic structures. However, nothing is disclosed with respect to the function of such a bisphosphite in the hydroformylation reaction of a mono-olefin, and there is no disclosure of the stability of the bisphosphite compound.
Thus, various phosphite compounds have been proposed as ligands to be used for the hydroformylation reaction, but none of them is fully satisfactory with respect to the stability or the reactivity for the hydroformylation reaction of a mono-olefinic compound.
As described above, heretofore, various bisphosphite compounds have been proposed as ligands to be used for the hydroformylation reaction, and in the hydroformylation reaction employing such compounds, it is possible to obtain characteristic results of the reaction depending upon the structures of the bisphosphite compounds. However, it has been impossible to simultaneously satisfy a high reaction rate and a high stability of the ligands and the economical efficiency tends to be poor in a commercial production. Therefore, there has been a problem that they can hardly be used as catalysts for industrial purposes. Accordingly, it has been desired to develop a bisphosphite ligand which has excellent stability of the ligand not only in the hydroformylation reaction zone but also in the entire process, while maintaining a high reaction rate.
SUMMARY OF THE INVENTION
In the course of a research for a ligand useful to improve or maintain the reaction activity in the hydroformylation reaction and the stability of the ligand not only in the hydroformylation reaction zone but also in the subsequent step, specifically the distillation step for separation of aldehydes, the present inventors have found that a bisphosphite compound having a specific structure is excellent particularly in the thermal stability, and when it is used as a component of the catalyst in the hydroformylation reaction i.e. as a ligand to be used together with the metal component of the catalyst, the reaction will proceed at a high speed, and the ligand will remain to be stable even in the distillation step for the recovery of aldehydes. The present invention has been accomplished on the basis of this discovery.
Namely, in the first aspect, the present invention provides a process for producing aldehydes, which comprises reacting a mono-olefinic compound with carbon monoxide and hydrogen in the presence of a Group VIII transition metal compound, wherein the reaction is carried out in the presence of a bisphosphite compound of the following formula (1) or (2) having a bisphenylene structural moiety connecting the two phosphite structures, said bisphenylene structural moiety being such that when it is represented by a structure of the following formula (I) as a model, and when, by the following calculation method, using a dihedral angle between the two aromatic rings of the structure of the formula (I) as a variable X (degrees), energy values are calculated by changing the dihedral angle X within a range of from 130 to 40 degrees, and relative energy values Y (kcal/mol) are calculated by subtracting the lowest calculated energy value from the energy values at the respective dihedral angles, whereupon the relation between the dihedral angle X and the relative energy value Y is represented by an approximate formula of Y=AX
2
+BX+C, the coefficient A satisfies A≧5×10
−4
:
wherein each of R
1
to R
6
which are independent of one another, is a group selected from an organic group, an inorganic group and a halogen atom, each of Ar
1
, Ar
2
, Ar
3
and Ar
4
which are independent of one another, is a substituted or unsubstituted arylene group, each of Q and Qu which are independent of each other, is a linking group selected from the group consisting of —CR
7
R
8
—, —O—, —S—, —NR
9
—, —SiR
10
R
11
— and —CO— (wherein each of R
7
to R
11
which are independent of one another, is a hydrogen atom, a C
1-12
alkyl group or an aryl group), and each of n and n′ which are independent of each other, is 0 or 1,
wherein R
1
to R
6
, Ar
1
to Ar
2
, Q and n are as defined in the formula (1), each of Z
1
and Z
2
which are independent of each other, is a C
1-20
alkyl group, a cycloalkyl group, a substituted or unsubstituted aryl group, an aralkyl group or a hetero aryl group,
Calculation Method
Calculation method: Molecular Mechanics Method
Program: CAChe Mechanics Release 3.9
Details of calculation: Optimization Method: Block-Diagonal
Newton Raphson Method
Converging condition: 0.001 kcal/mol.
In the second aspect, the present invention provides a process for producing aldehydes, which comprises reacting a mono-olefinic compound with carbon monoxide and hydrogen in the presence of a Group VIII transition metal compound, wherein the reaction is carried out in the presence of a bisphosphite compound of the following formula (1) or (2):
wherein each of R
1
and R
4
which are independent of each other, is a C
1-12
alkyl group, a cycloalkyl group, an alkoxy group, a silyl group, a siloxy group or a halogen atom, each of R
2
, R
3
, R
5
and R
6
which are independent of one another, is a hydrogen atom, a C
1-20
alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, a silyl group or a siloxy group, each of Ar
1
, Ar
2
, Ar
3
and Ar
4
which are independent of one another, is a substituted or unsubstituted arylene group, each of Q and Q′ which are independent of each other, is a linking group selected from the group consisting of —CR
7
R
8
—, —O—, —S—, NR
9
—, —SiR
10
R
11
— and —CO— (wherein each of R
7
to
Itagaki Hiroaki
Suzuki Naoki
Tanaka Yoshiyuki
Urata Hisao
Wada Yasuhiro
Mitsubishi Chemical Corporation
Vollano Jean F
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