Method of producing &bgr;-hydroxyaldehydes

Details Method of producing &bgr;-hydroxyaldehydes Method of producing &bgr;-hydroxyaldehydes

1999-11-12

2001-01-30

Vollano, Jean F (Department: 1625)

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

Organic compounds

Oxygen containing

C568S483000

Reexamination Certificate

active

06180831

ABSTRACT:

CROSS-REFERENCE TO RELATED APPLICATION
This application is based on German Application DE 198 52 104.9, filed Nov. 12, 1998, which disclosure is incorporated herein by reference.
FIELD OF THE INVENTION
The invention relates to a method of producing &bgr;-hydroxyaldehydes.
BACKGROUND OF THE INVENTION
&bgr;-Hydroxyaldehydes are significant as starting compounds for the production of compounds such as, e.g., dicarboxylic acids and their derivatives. Furthermore, diols such as, e.g., 1,3-propane diols, can be produced by the hydrogenation of &bgr;-hydroxyaldehydes. 1,3-Propane diols can be used as monomeric structural units in the production of polyesters or polyurethanes, as starting materials for the synthesis of cyclic compounds as well as for a number of other substances.
It is known that &bgr;-hydroxyaldehydes can be produced by reacting 1,2-oxiranes with carbon monoxide and hydrogen in the presence of catalysts.
U.S. Pat. No. 3,463,819 describes a method for the production of &bgr;-hydroxypropionaldehyde and 1,3-propanediol in which, inter alia, ethylene oxide in the presence of toluene as well as in the presence of diethylether/benzene, 1,2-bis(diphenylphosphino)ethanedicobalt hexacarbonyl, carbon monoxide and hydrogen are reacted with each other.
U.S. Pat. No. 3,456,017 describes a method for the production of propanediol and &bgr;-hydroxypropionaldehyde in which ethylene oxide, a tertiary phosphino-modified cobalt carbonyl catalyst, carbon monoxide and hydrogen are reacted with each other.
U.S. Pat. No. 5,256,827 describes the hydroformylation of ethylene oxide in the presence of oxidized, tertiary phosphine-complexed carbonyl catalysts.
The known methods have the disadvantage that a very great amount of catalyst relative to the amount of ethylene oxide must be used, Furthermore, reaction promoters must be added.
The invention has the object of developing a method for the production of &bgr;-hydroxyaldehydes which does not have these disadvantages.
SUMMARY OF THE INVENTION
The invention provides a method of producing &bgr;-hydroxyaldehydes in which 1,2-oxiranes are reacted with carbon monoxide and hydrogen in the presence of transitional metal compounds which are modified with phosphorus-oxygen ligands or nitrogen-oxygen ligands and which act as catalyst.
According to the invention, 1,2-oxiranes (epoxides) are hydroformylated with carbon monoxide and hydrogen in the presence of a cobalt-carbonyl catalyst modified with phosphorus-oxygen chelate ligands or nitrogen-oxygen chelate ligands. The reaction products are essentially &bgr;-hydroxyaldehydes (and their oligomers) and, in small amounts, the corresponding 1,3-diols. When the term “&bgr;-hydroxyaldehydes” is used below it signifies the monomers as well as the dimers such as, e.g., 2-(2-hydroxyethyl)-4-hydroxy- 1,3-dioxane in the case of the hydroformylation of ethylene oxide as well as trimers and higher oligomers of the corresponding &bgr;-hydroxyaldehydes.
Oxiranes containing 2 to 30 carbon atoms can be used, for example, as the oxiranes. Epoxides having an oxygen bridge in the 1,2 position are preferably used.
Saturated hydrocarbons with vicinal epoxides with up to 10 carbon atoms can be used as oxiranes in the method of the invention. These compounds, also named epoxyalkanes, can have cyclic or acyclic, long-chain or branched-chain structures.
Acyclic epoxides can be those epoxides in which the carbon atoms of the epoxy unit are not a component of a carbocyclic ring. Such compounds are, e.g., ethylene oxide, propylene oxide, isobutylene oxide, 1,2-epoxypentane, 1,2-epoxy-4-methylpentane, 1,2-epoxyoctane, 3-cyclohexyl-1,2-epoxypropane, 3,4-epoxynonane, 1,2-epoxy-2,2,4-trimethylhexane and 1,2-epoxydecane.
Cyclic epoxides can be those epoxides in which the carbon atoms of the epoxy unit are part of a carbocyclic ring. Such epoxycycloalkanes can be, e.g.: cyclohexene oxide, cyclopentene oxide, cyclooctane oxide, 1,2-epoxy-4-methylcyclohexane, 4,5-dimethyl-1,2-epoxycyclohexane, 2,3-epoxy-decahydronaphthalene and 1,2-epoxy-4-propylcyclohexane.
In general, the use of acyclic epoxides is preferred. In particular, acyclic epoxides with a carbon-atom number up to 6 carbon atoms in which the epoxy group is terminal, such as, for example an acyclic 1,2-epoxyalkane, can be used. Of these compounds, ethylene oxide as well as propylene oxide are particularly preferred.
Cobalt-carbonyl catalysts modified with phosphorus-oxygen chelate ligands can be used as catalysts in the method of the invention.
For example, phosphine-phosphinic oxides can be considered as chelate ligands. Preferred phosphine-phosphinic oxides which correspond to formula (I) are preferred.
in which R
1
, R
2
, R
3
, R
4
are the same or different and represent an alkyl-, cycloalkyl- or aryl group of up to 30 carbon atoms, preferably up to 12 carbon atoms, or —CH
2
OH, and
Q represents an alkylidene bridge having 1-20 carbon atoms, preferably having 1-10 carbon atoms, a heteroatom such as, e.g., oxygen, or alkylidene compounds containing nitrogen.
Especially preferred substances corresponding to formula (I) are 1,2-bis(diphenylphosphino)methane monoxide (dppmO) and 1,2-bis(diphenylphosphino)ethane monoxide (dppeO).
These compounds are known from U.S. Pat. No. 4,429,161 and U.S. Pat. No. 3,426,021, as well as from N. A. Bondarenko, Synthesis 1991, 125.
The phosphinic oxides used in accordance with the invention are defined compounds characterized by a ratio of oxygen to phosphorus of equal to or greater than 0.5.
In a preferred embodiment the ratio of oxygen to phosphorus can be 0.5 to 2.0.
Furthermore, for example, aliphatic and aromatic phosphino carboxylic acids and their esters can be considered as ligands.
These compounds are known from K. Issleib and G. Thomas in Chem. Ber., 1960, (93), 803-808. They can be produced according to O. Stelzer et al., J. Organomet. Chem. 1996, 522, 69-76, as well as according to Rauchfuss, Inorg. Synth., 21, 1982.
The preferred ligands are represented by formulas (II) and (III)
in which
R
1
, R
2
can be the same or different and represent an alkyl-, cycloalkyl- or aryl group of up to 30 carbon atoms, preferably up to 12 carbon atoms, or —CH
2
OH,
R′ represents hydrogen or an alkyl- or cycloalkyl group of up to 30 carbon atoms, preferably up to 12 carbon atoms,
Q represents an alkylidene bridge having 1-20 carbon atoms, preferably having 1-10 carbon atoms,
X represents hydrogen in the case of phosphino carboxylic acids and an alkyl-, cycloalkyl- or aryl group in the case of the esters.
Diphenylphosphino acetic acid and diphenylphosphino methyl acetate are especially preferred substances according to formula (II).
o-Diphenylphosphino benzoic acid and o-diphenylphosphino methyl benzoate are especially preferred substances according to formula (III).
Moreover, cobalt-carbonyl compounds modified with nitrogen-oxygen chelate ligands can be used in the method of the invention.
For example, di-N-substituted amino carboxylic acids as well as their esters can be used.
Ligands which correspond to formula (IV), set forth below, are preferred,
in which:
R
1
, R
2
, R
3
, R
4
each represent hydrogen or an alkyl-, cycloalkyl or aryl group of up to 30 carbon atoms, preferably up to 12 carbon atoms, which can additionally carry other functionalities such as hydroxyl-, amino- or halogen groups.
R
1
and R
2
as well as R
3
and R
4
can also be included in a common cycloalkyl group with up to 20 carbon atoms, preferably 4-7 carbon atoms.
X represents hydrogen in the case of amino carboxylic acids, and an alkyl-, cycloalkyl or aryl group in the case of esters.
Especially preferred substances corresponding to formula IV are N,N-dimethyl glycine and its ethyl esters.
When R
3
≠R
4
, the compounds according to formula IV can be produced in the form of the pure enantiomers in order to transfer chiral information to corresponding chiral epoxides in this manner.
Furthermore, substances are preferred which correspond to formula V
in which
R
1
, R
2
, R
3
, R
4
each represent hydrogen or an alkyl-, cycloalkyl or aryl group of up to 30 car

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