Process for preparing alcohols and/or aldehydes from olefins

Details Process for preparing alcohols and/or aldehydes from olefins Process for preparing alcohols and/or aldehydes from olefins

1999-01-07

2000-08-29

Richter, Johann

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

Organic compounds

Oxygen containing

556482, 556485, C07C 2903

Patent

active

06111149&

DESCRIPTION:

BRIEF SUMMARY
This is a 371 of application No. PCT/EP97/03742, filed Jul. 14, 1997.
The present invention relates to a process for preparing alcohols and/or aldehydes from olefins by cross-metathesis of olefins with alcohols whose molecule includes at least one C.dbd.C double bond over catalysts of the formula (I)
Alcohols are valuable solvents or intermediates in organic syntheses, for example for preparing phthalates, acrylates or sulfonates. The aldehydes are used, for example, as intermediates for preparing the corresponding alcohols or acids.
A widely known and technically widespread reaction of olefins is catalytic olefin metathesis. A general overview of olefin metathesis is given, for example, by K. Weissermel and H. -J. Arpe in Industrielle Organische Chemie, 4th Edition, 1994, VCH Verlagsgesellschaft Weinheim, on pages 94 to 98.
Olefin metathesis corresponds formally to the exchange of the alkylidene groups of two olefin molecules. The reaction mechanism is usually formulated as metal-catalyzed scission of the double bonds in the original olefins and their subsequent reformation to give the products. The reaction is reversible. A general, formal equation which highlights the exchange of the substituents labeled R.sup.A, R.sup.B, . . . R.sup.H but does not take into account the actual cis/trans stereochemistry is given below: ##STR1##
In general a distinction is made between self-metathesis, in which one olefin is converted to a mixture of two olefins differing in molar mass, an example being the transformation of two molecules of propene into one of ethene and one of 2-butene, and cross-metathesis, where two different olefins are converted to two new olefins, an example being the transformation of propene and 1-butene into ethene and pentene.
Metathesis reactions of functionalized olefins, that is those composed of additional elements as well as just carbon and hydrogen, are described much more rarely than metathesis reactions of pure hydrocarbon olefins. The most frequent examples relate to metathesis reactions of unsaturated ethers, esters and halides. For example, J. C. Mol and E. F. G. Woerlee in J. Chem. Soc., Chem. Commun., 1979, 330-331, describe the self-metathesis of ethers and formyl esters of unsaturated alcohols, with elimination of ethylene, over a tin-promoted rhenium oxide catalyst on an alumina support. U.S. Pat. No. 5,342,985 discloses the self-metathesis of ethers and esters of unsaturated alcohols over special organorhenium oxides.
GB-A-2 131 429 describes the self- or cross-metatheses, which it refers to generally as dismutation, of functionalized olefins. In accordance with all of the rest of the prior art, preference is given therein--on page 1, lines 49 to 52--to those oxygen substituents which are not hydroxyl. The suitability, in principle, of hydroxy-substituted olefins for metathesis reactions cannot be inferred from this document. .alpha.-Olefins .alpha.-substituted by hydroxyl, such as 4-penten-1-ol, in which olefins the hydroxyl group is further away from the double bond than if it were in the allyl position, can be metathesized with a specific ruthenium catalyst according to P. Schwab, R. H. Grubbs and J. W. Ziller, J. Am. Chem. Soc. 118 (1996) 100-110. .alpha.-Olefins of this kind with an .omega. hydroxyl group do not, however, display the high reactivity known for olefins having an allylic hydroxyl, especially not their propensity to allyl isomerization.
In the metathesis of an .alpha.-olefin with a hydroxyalkene where the oxygen substituent is further away from the double bond than if it were in the allyl position, at least two carbons are added onto the original .alpha.-olefin. On the basis of the common industrial .alpha.-olefins with a particular number of carbons, therefore, it is not possible by means of metathesis reactions with such hydroxyalkenes to obtain the alcohols or aldehydes having a carbon framework which originates from the original carbon framework of the .alpha.-olefin by addition of exactly one carbon. However, it is precisely such alcohols and aldehydes ob

REFERENCES:
patent: 5342985 (1994-08-01), Herrmann et al.
Ind. Org. Chem., 4.sup.th Ed. 1994, pp 94-98.
J. Chem. soc., Chem. Commun. 1979, 330-331.
J. Am. Chem. Soc., vol. 118,1996, 100-110.

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