Process for preparing acetals of malondialdehyde

Details Process for preparing acetals of malondialdehyde Process for preparing acetals of malondialdehyde

2000-01-28

2002-05-28

Carr, Deborah D (Department: 1621)

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

Organic compounds

Fatty compounds having an acid moiety which contains the...

C554S227000, C568S603000

Reexamination Certificate

active

06395914

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a process for preparing acetals of malondialdehyde.
BACKGROUND OF THE INVENTION
Acetals of malondialdehyde of the formula (I):
in which R
1
, R
2
, and R
3
are the same or different alkyl groups, cycloalkyl groups, aralkyl groups or aryl groups, with up to 12 carbon atoms, R
4
is an alkyl group, cycloalkyl group, aralkyl group or represents R—CO— with R=alkyl, cycloalkyl, aralkyl or aryl, and R
5
and R
6
represent independently of each other H, a cycloalkyl group, an aralkyl group, or an aryl group with up to 12 carbon atoms, are used as intermediates for the preparation of heterocycles such as pyrazols, isoxazols, pyrimidines, 2-aminopyrimidines or pyrimidones. Aside from their use as organic intermediates, they also serve as hardener components for polyvinylalcohol- and polyvinylacetate-films (U.S. Pat. No. 4,655,841).
It is known that the malondialdehyde tetraalkylacetals namely 2-substituted and 2,2-di-substituted malondialdehyde tetraalkylacetals, respectively, can be synthesized by reacting orthoformates with alkylvinyl ethers and substituted alkylvinyl ethers (U.S. Pat. No. 2,527,533) or orthoformates and vinyl esters (U.S. Pat. No. 2,459,076) in the presence of suitable Lewis-acids as the catalyst.
In order to improve the economics of the process, it is desirable to run the reaction in the presence of a heterogeneous catalyst and, optionally, continuously. The use of heterogeneous catalysts for the reaction of orthoformates and vinyl ethers has in fact already been described earlier (U.S. Pat. No. 2,556,321). Also, it has been demonstrated that, for example, methyl vinyl ether and trimethyl orthoformate can be reacted continuously in a tubular reactor using dissolved FeCl
3
as the catalyst (EP 0058928).
However, it has been found that the—otherwise advantageous—use of heterogeneous catalysts for the reaction of orthoformates with alkylvinyl ethers leads to several practical problems if conducted conventionally. The most important one is related to catalyst lifetime. Commonly used heterogeneous Lewis acid catalysts, such as acidic montomorillonites and acidic zeolites, as well as otherwise homogeneous Lewis acids, when adsorbed on a suitable support (for example FeCl
3
on SiO
2
) were found to be deactivated after relatively short periods of time. For example, upon the use of montmorillonite K10® or zeolite. H-BEA 25® to catalyze the reaction of methyl vinyl ether with trimethyl orthoformate, the catalyst lost significant activity after only 3 hours. The yields dropped from 80% to <60% and the catalyst slowly darkened. Such short catalyst lifetimes are unacceptable under commercial conditions and, in fact, negate the advantages normally associated with the use of heterogeneous catalysts, i. e. reduced catalyst-costs, reduced disposal costs, and environmental friendliness.
In the cases where otherwise homogeneous Lewis acids like FECl
3
, AICl
3
or ZnCl
2
were supported on SiO
2
, Al
2
O
3
or montmorillonites or the commercially available Envirocats® were used, the catalysts quickly lost their activity, and the products were found to contain significant amounts of the catalyst-cations. This phenomenon is commonly referred to as ‘leaching’.
It is accordingly an object of the present invention to provide a process that provides the compounds of general formula I from orthoformates and alkylvinyl ethers or orthoformates and vinyl esters in the presence of heterogeneous catalysts without the drawback of unacceptably short catalyst lifetimes.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a process for preparing acetals of malondialdehyde of general formula I:
in which R
1
, R
2
, and R
3
are the same or different alkyl groups, cycloalkyl groups, aralkyl groups or aryl groups with up to 12 carbon atoms, R
4
is an alkyl group, cycloalkyl group, aralkyl group; aryl group, or represents R
7
—CO— with R
7
=alkyl, cycloalkyl, aralkyl, or aryl with up to 12 carbons, and R
5
and R
6
represent independently of each other H, an alkyl group, cycloalkyl group, aralkyl group or an aryl group with up to 12 carbon atoms, by reacting alkylvinyl ethers of general formula II or vinyl esters of general formula III:
 and ortho formates of general formula IV:
 wherein the reaction is carried out in the gas phase using a catalyst.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a process for preparing acetals of malondialdehyde of general formula I:
in which R
1
, R
2
, and R
3
are the same or different alkyl groups, cycloalkyl groups, aralkyl groups, or aryl groups with up to 12 carbon atoms, R
4
is an alkyl group, cycloalkyl group, aralkyl group, aryl groups, or represents R
7
—CO— with R
7
=alkyl, cycloalkyl, aralkyl, aryl with up to 12 carbon atoms, and R
5
and R
6
represent independently of each other H, an alkyl group, cycloalkyl group, arylalkyl group, or aryl group, with up to 12 carbon atoms which allows for the use of a heterogeneous catalyst under commercial conditions and which leads to superior selectivities.
In a preferred embodiment of the process according to the present invention, R
1
, R
2
and R
3
are identical. It is especially preferred that in the compound of formula I, R
1
, R
2
, R
3
and R
4
represent a methyl group. It is also especially preferred that in the compound of general formulas I, R
1
, R
2
and R
3
represent a methyl group and R
4
represent an acetyl group.
It has been found that improved catalyst-lifetimes of heterogeneous catalysts, as well as superior selectivities, can be achieved in a simple manner and that acetals of malondialdehyde of general formula I are obtained advantageously if alkyl vinylethers of general formula II or a vinylester of general formula III:
in which R
4
, R
5
and R
6
are as defined above and R
7
is an alkyl group, cycloalkyl group, aralkyl group, or aryl group, with up to 12 carbon atoms, are reacted with an orthoformate of general formula IV
 in the gas phase.
Acidic catalysts, preferably strong Lewis acids, such as ZnCl
2
on montmorillonite K-306®, ZnCl
2
on Al
2
O
3
, FeCl
3
on SiO
2
or Envirocats EPZG® and EPZ10® demonstrated relatively high reactivities and, therefore, are preferred.
In order to evaporate the starting materials and especially to avoid condensation of the products of general formula I and/or the starting materials of general formula II respective III and IV within the catalyst bed, it has been found to be advantageous to carry out the reaction under vacuum. In a preferred embodiment according to the present invention, the reaction is carried out at an absolute pressure between about 0.1 mm Hg and about 500 mm Hg, with a pressure of between about 1 mm Hg, and about 50 mm Hg being especially preferred.
While the compounds of general formula II respective III and IV can be reacted in the gas phase at temperatures as low as 20° C., it is advantageous to choose temperatures that are significantly higher than the ones that are ideal for the liquid phase. Above 250° C., however, the orthoformates of general formula IV were found to decompose to a significant extent, even on very short contact-times. The best yields of the compounds of general formula I were usually achieved in the temperature range of about 40° C. to about 150° C., and especially in the temperature range of about 70° C. to about 100° C.
Improved conversions of the starting materials of general formulas II and III are usually achieved if the ortho formates of general formula IV are used in excess, i.e., from about 1.1 to about 3-fold molar excess, preferably about 1.2-fold to about 1.5 fold.
In a preferred embodiment of the process according to the present invention, the reaction is carried out continuously. In practice, it does not matter if a mixture of the compounds of formulas II, III and IV are evaporated, or if individual vapor streams are passed through a common catalyst bed.
It is a special advantage of the process according to the present invention that the separati

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