Process for producing aldehydes

Details Process for producing aldehydes Process for producing aldehydes

1999-09-27

2001-07-24

Padmanabhan, Sreeni (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S451000

Reexamination Certificate

active

06265620

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Technical Field
The present invention relates to a method for producing aldehydes. In particular, the present invention relates to a method for producing aldehydes by subjecting an olefinic compound to a hydroformylation reaction.
2. Background Art
A reaction which comprises reacting an olefinic compound with carbon monoxide and hydrogen in the presence of a catalyst to produce aldehydes or alcohols as their hydrogenated products, is known as hydroformylation reaction. As the catalyst for the hydroformylation reaction, it is common to use an element of Group 8 to 10 of the Periodic Table (hereinafter referred to as a “Group VIII metal”), such as rhodium, modified by a ligand containing phosphorus. It is known that the reaction activity and the selectivity of the product are substantially changed by the ligand used together with the metal component of the catalyst. Accordingly, in order to carry out the hydroformylation reaction industrially advantageously, it is important to improve the reaction activity and the selectivity of the product, and to suppress an olefin-reduced product by a side-reaction. Accordingly, various efforts to design the ligand have been made for this purpose. As such processes, hydroformylation processes employing various phosphine compounds, and hydroformylation processes employing various phosphite compounds, have been reported.
Very few examples have been reported wherein a phosphonite compound is used as the ligand for the hydroformylation reaction. Fewer examples have been reported wherein a phosphonite compound which is not monodentate is used. For example, U.S. Pat. No. 4,400,547 discloses that in a process for a hydroformylation reaction of an olefin employing a non-modified Rh metal as a catalyst, in a step of separating the catalyst, PhP(OPh)
2
or EtP(OPh)
2
is added as an organic phosphorus compound to stabilize rhodium. However, the ligand in the phosphonite compound is removed after the step of separating the catalyst, and it is not shown that the phosphonite ligand is effective for the oxo reaction system. Further, He Binglin et al. have reported an example wherein a hydroformylation reaction of diisobutylene is carried out by using an Rh catalyst and a phosphonite compound bonded to a polymer having many functional groups introduced thereto or to a styrene-divinylbenzene copolymer (<polymer>-P(OEt)
2
). This document describes that results of a degree of conversion of 64.3%, an yield of aldehyde of 60.8% and an yield of alcohol of 3.5%, were obtained at a reaction temperature of 110° C. under a reaction pressure of 100 atm for a reaction time of 6 hours (Sci. Cin. Ser. B(Engl. Ed.), 31(3), 269 (1988)). As mentioned above, a very few examples have been made wherein a hydroformylation reaction is carried out by using a phosphonite compound, and fewer examples have been made wherein a phosphonite compound which is not monodentate is used. Further, no example has been known, which reports that a homogeneous complex catalyst containing a bidentate phosphonite compound is effective for the hydroformylation reaction of an olefinic compound.
Further, the activity of the hydroformylation reaction employing a known phosphorus ligand such as a monodentate or bidentate phosphine or a monodentate or bidentate phosphite, has not necessarily been satisfied, and the formation of by-products has brought about an economical disadvantage to commercial production. Among such by-products, paraffins formed by reduction of an olefinic compound by hydrogen gas without a hydroformylation reaction, are particularly valueless. Accordingly, it has strongly been desired to develop a ligand which does not cause a side-reaction such as the hydrogenation reaction.
DISCLOSURE OF THE INVENTION
In the course of a search for an effective ligand to improve and maintain the reaction activity and the selectivity of the desired product in the hydroformylation reaction, the present inventors have found that by carrying out the hydroformylation reaction in the presence of a Group VIII metal compound having a phosphonite compound with a certain specific structure as a ligand, good results can be obtained with respect to the reaction activity and the selectivity of a straight chain isomer as an aldehyde product, and at the same time, the reduction reaction of the olefinic compound as a side-reaction can be suppressed. The present invention has been accomplished on the basis of these discoveries.
Namely, the present invention provides a method for producing aldehydes, which comprises reacting an olefinic compound with carbon monoxide and hydrogen, in the presence of a catalyst containing a metal of Group 8 to 10 (hereinafter referred to as “Group VIII metal”) and a trivalent organic phosphorus compound to produce the corresponding aldehydes, wherein a cyclic or non-cyclic, particularly a bidentate cyclic or bidentate non-cyclic, phosphonite compound of any one of the following general formulae (I) to (V), is employed, as the trivalent organic phosphorus compound:
wherein Z
1
is a substituted or unsubstituted hydrocarbon group, each of X
1
and Y
1
is a substituted or unsubstituted bivalent hydrocarbon group, substituents in X
1
and Y
1
may further together form a bond, Q
1
is a substituted or unsubstituted methylene group, and m is 0 or a positive integer;
wherein X
2
is a substituted or unsubstituted hydrocarbon group, each of Y
2
and Z
2
is a substituted or unsubstituted bivalent hydrocarbon group, substituents in X
2
and Y
2
may further together form a bond, Q
2
is a substituted or unsubstituted methylene group, and n is 0 or a positive integer;
wherein X
3
is a substituted or unsubstituted hydrocarbon group, and each of Y
3
and Z
3
is a substituted or unsubstituted aromatic hydrocarbon group;
wherein each of X
4
, X
5
, X
6
and X
7
is a substituted or unsubstituted bivalent hydrocarbon group, substituents in X
4
, X
5
, X
6
and X
7
may further together form a bond, Q
3
is a substituted or unsubstituted bivalent hydrocarbon group, each of Q
4
and Q
5
is a substituted or unsubstituted methylene group, and each of m1 and m2 is 0 or a positive integer;
wherein each of X
8
, X
9
, X
10
and X
11
is a substituted or unsubstituted hydrocarbon group, and Q
6
is a bivalent organic group.
In the hydroformylation reaction employing the phosphonite compound of the present invention, a high reaction activity and a high selectivity of a straight chain isomer as an aldehyde product, can be obtained, and the reduction of the olefinic compound as a side-reaction can be suppressed. Accordingly, the hydroformylation reaction can be carried out industrially advantageously.
BEST MODE FOR CARRYING OUT THE INVENTION
Now, the present invention will be described in detail.
The cyclic phosphonite compound represented by the general formula (I) to be used in the present invention, is a phosphonite compound having a cyclic structure containing a P—O bond in its molecule.
In the general formula (I), the substituted or unsubstituted hydrocarbon group represented by Z
1
may be a C
1-30
alkyl group which may be branched, a cycloalkyl group, an alkenyl group which may be branched, or a C
6-30
aryl group. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group or an octyl group. The cycloalkyl group may, for example, be a cyclopropyl group, a cyclopentyl group or a cyclohexyl group. The alkenyl group may, for example, be a vinyl group, an allyl group or a 2-cyclohexenyl group. The aryl group may, for example, be a phenyl group, a 1-naphthyl group or a 2-naphthyl group.
The substituted or unsubstituted bivalent hydrocarbon group represented by each of X
1
and Y
1
, may, for example, be a C
1-30
alkylene group, cycloalkylene group, alkenylene group or an arylene group or a C
6-30
arylene group. Specifically, it may, for example, be a methylene group, an ethylene group, a 1,2-phenylene group or a naphthylene group. The substituent for each of X
1
, Y
1
and Z
1
, may, for example, be a C
1-30
, prefer

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