Process for the preparation of substituted...

Details Process for the preparation of substituted... Process for the preparation of substituted...

2001-03-14

2003-05-20

Barts, Samuel (Department: 1621)

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

Organic compounds

Oxygen containing

Reexamination Certificate

active

06566557

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to “A process for the preparation of substituted trans-cinnamaldehyde, a natural yellow dye, from phenylpropane derivatives” in which trans-cinnamaldehyde (e.g. 2,4,5-trimethoxycinnamaldehyde where R
1
is —CH═CH—CHO, R
2
═R
4
═R
5
is —OMe and R
3
═R
6
is H; p-methoxycinnamaldehyde where R
1
is —CH═CH—CHO, R
2
═R
3
═R
5
═R
6
is H, R
4
is —OMe and 3,4-dimethoxycinnamaldehyde where R
1
is —CH═CH—CHO, R
2
═R
5
═R
6
is H and R
3
═R
4
is —OMe etc) of the formula I as shown below:
These compounds can be obtained by oxidation of (R
2
—R
3
—R
4
—R
5
—R
6
)phenylpropane derivatives (wherein R
2
to R
6
equal or different, being hydrogen or hydroxy or alkyl or methylenedioxy or alkoxy groups, etc) which is, in fact, a reduced product of readily available natural phenylpropene (methyl chavicol, anethole, eugenol, methyl isoeugenol, safrole, toxic &bgr;-asarone etc) bearing essential oil or the like.
BACKGROUND OF THE INVENTION
Cinnamaldehyde and its substituted derivatives (e.g. p-methoxy cinnamaldehyde, 3,4-methylenedioxycinnamic aldehyde, coniferyl aldehyde etc) possess an aromatic ring bearing one or more hydroxy or dioxymethylene or alkoxy groups or the like, attached to the &agr;,&bgr;-unsaturated aldehyde (i.e. CH═CH—CHO) which contribute significantly to the taste and flavour of many foods and drinks (Harbome, J. B. and Baxter, H., In: Phytochemical Dictionary, A Handbook of Bioactive Compounds from Plants, Taylor & Francis Ltd., London WC1N 2ET, 472-488 (1993)). In addition, cinnamaldehyde derivatives serve as a raw material for the preparation of a number of other perfumery aromatics. Morever, the selective reduction of the aldehyde group gives cinnamyl alcohol which possesses a pleasant and long-lasting spicy odor and complete reduction of the side chain gives phenyl propyl alcohol and its oxidation give hydrocinnamic acid (Muller, A. J., Bowers Jr, J. S., Eubanks, J. R., Geiger, C. C. and Santobianco, J. G., U.S. Pat. No. 5,939,581)) which, along with its ester, finds usage in perfumery composition. Cinnamaldehyde and its derivatives are not only found to be highly effective to prevent skin from darkening caused by irradiation of ultraviolet rays from the sun (Tomoshi, K. and Makoto, F., JP Pat. No. 58055414A2)) but also proved to be excellent in preventing falling-off of hair and also provide hair growth (Watanabe, T., Komeno, T. and Hatanaka, M., JP Pat. No. 6312916A2)). In addition, cinnamaldehyde in combination with the manure controls injurious microorganisms present in soil without any adverse effect on manure-decomposing microorganisms (Saotome, K., JP Pat. No. 58201703A2)). Further, cinnamaldehyde derivatives are useful as an intermediate for synthesis of various drugs such as anti-viral pharmaceuticals, particularly HIV protease inhibitors (Castelijns, A. M. C. F., Hogeweg, J. M. and van Nispen, S. P. J. M., U.S. Pat. No. 5,811,588) and also used in cosmetics, dyes, agrochemicals, alkaloids (Parmar, V. S., Jain, S. C., Bisht, K. S., Jain, R., Taneja, P., Jha, A., Tyagi, O. D., Prasad, A. K., Wengel, J., Olsen, C. E. and Boll, P. M., Phytochemistry, 46(4): 597-673 (1997)), perfumes, etc.
Cinnamaldehyde is identified for the first time in the year 1833 during steam distillation of Ceylon bark of cinnamon (
Cinnamomum zeylanicum
, family: Lauraceae) which is still one of the main source of cinnamaldehyde. It also occurs in dozens of flowers and essential oils such as Hyacinthus spp., Narcissus spp., Lavandula spp.,
Pogostemon cabline
and Commiphora spp. and others. However, substituted cinnamaldehyde (coniferyl aldehyde or coniferaldehyde or ferula aldehyde or ferulaldehyde) occurs in a number of other plants such as Quercus spp.,
Acer saccharinum
which, imparts a phenolic-spicy, sweet balsamic odour and is used extensively in flavour compositions. Similarly, sinapaldehyde (3,5-dimethoxy-4-hydroxycinnamaldehyde) occurs in
Juglans nigra, Senra incana
and p-methoxycinnamaldehyde in
Acorus gramineu
etc. Mostly, substituted cinnamaldehydes are yellow in color; therefore, the applicability of cinnamaldehyde can be further increased with the possibities of their uses in the area of natural dyes. However, the limited percentage of substituted cinnamaldehydes present in the plant kingdom is not sufficient to fulfill the world demand. As a result, the major amounts of cinnamaldehydes are made synthetically.
A number of proceses have been proposed to produce cinnamaldehyde and its derivatives (such as p-methoxycinnamaldehyde, dimethoxycinnamaldehyde, sinapaldehyde, trimethoxycinnamaldehyde and methylenedioxy cinnamaldehyde etc). For the most part, these methods involve reaction of the substituted benzaldehyde (such as p-methoxybenzaldehyde etc) with acetaldehyde in the presence of acid or better with alkali. Cinnamaldehyde can also be prepared by hydrolysis of cinnamylidene chloride. Good yields have been obtained by the Rosenmund reduction of cinnamic acid chloride with palladinium catalyst (March, J., In: Advanced Organic Chemistry, Reactions, Mechanisms and Structure, Wiley Eastern Ltd., New Delhi, 396-397, (1987)). Catalytic dehydrogenation of cinnamic alcohol at high temperature under reduced pressure has given good yields of cinnamaldehyde. Dry distillation of the calcium salts of cinnamic and formic acid also yields aldehyde. Isomerization of phenylethynyl carbinol in the presence of acid produces good yields of aldehyde. A practical method of producing a range of &agr;,&bgr;-unsaturated aldehyde is to treat an olefin with carbon monoxide under pressure and in the presence of a catalyst (Brown, H. C. and Tsukamoto, A., J. Am. Chem. Soc., 86: 1089 (1964)) and Bedoukian, P. Z., In: Perfumery and Flavoring Synthetics, Allured Publishing Corporation, Wheaton, Ill., USA, 98-105 (1986)). Though such methods have been proven to be useful, they suffer from one or more process deficiencies. For example, in some instances processes of this type necessarily involve resort to sub-ambient temperatures, which of course, involves some considerable process control and in some cases, the reaction is effected only at a relatively high pressures and lead to reaction mixtures.
Typical prior art references include U.S. Pat Nos. 2,529,186; 2,794,813; 3,028,419 and German Patent Nos. 97,620; 1,114,798 and Soviet Union Pat. No. 1451139A1 and Czechoslovakia Pat. No. 8405411A1.
It, therefore, becomes an object of invention to provide a process for producing cinnamaldehydes such as p-methoxycinnamaldehyde, 3,4-dimethoxycinnamaldehyde, 3,4-methylenedioxycinnamaldehyde, 3,4-methylenedioxy-5-methoxycinnamaldehyde, 1-ethoxy-2-acetoxycinnamaldehyde, 1-ethoxy-2-hydroxycinnamaldehyde, sinapaldehyde, 2,5-dimethoxy-3,4-methylenedioxycinnamaldehyde, 2-methoxy-4,5-methylenedioxy cinnamaldehyde, coniferyl aldehyde, 3,4,5-trimethoxycinnamaldehyde, 2,3-dimethoxy-4,5-methylenedioxycinnamaldehyde and 2,4,5-trimethoxycinnamaldehyde or the like, by means which eliminate the above discussed disadvantages and others.
Other objectives will appear hereinafter.
OBJECTIVES OF THE INVENTION
The main object of the present invention is to develop a simple industrial process for the preparation of substituted cinnamaldehyde (such as p-methoxycinnamaldehyde, 3,4-dimethoxycinnamaldehyde, 2,4,5-trimethoxycinnamaldehyde etc) in one step with high yield from phenylpropane derivatives (such as dihydro methylchavicol, dihydro methyleugenol, 2,4,5-trimethoxyphenylpropane etc) which is, in fact, the hydrogenated product of readily available natural phenylpropenes (such as, methyl chavicol or anethole, methyl eugenol, highly toxic &bgr;-asarone etc.)
In another object of the invention is to develop a simple process for the preparation of substituted cinnamaldehyde in high purity without any contamination of corresponding cinnamicacid and alcohol.
Yet another object of the present invention is to develop a process for the preparation of trans-cinnamaldehyde exclusively in a single step from phenylpropane

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