Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acids and salts thereof
Patent
1985-04-18
1987-05-05
Killos, Paul J.
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acids and salts thereof
562508, 568377, 568657, 568813, C07C 6504
Patent
active
046634789
DESCRIPTION:
BRIEF SUMMARY
FIELD OF THE INVENTION
This invention relates to a process for producing a para-substituted phenol derivative. More particularly, the present invention is concerned with a process for producing a para-substituted phenol derivative which comprises reacting a phenol compound with an organic halide selected from the group consisting of a haloform, a carbon tetrahalide and a substituted or unsubstituted allyl halide in the presence of an alkali metal hydroxide, using as a catalyst a fixed cyclodextrin having hydroxyl groups crosslinked with a bivalent hydrocarbon group having free valences at its both ends.
DESCRIPTION OF THE PRIOR ART
It is known that 2,5-cyclohexadienone derivatives having a dihalomethyl group at the 4-position, 2,5-cyclohexadienone derivatives having a substituted or unsubstituted allyl group at the 4-position, para-hydroxybenzoic acid derivatives, or para-hydroxybenzaldehyde derivatives are prepared by reacting a phenol with a haloform under alkaline conditions. The products thus obtained are extremely valuable compounds as pharmaceuticals, agricultural chemicals, or raw materials for polymers, various physiologically active substances such as agricultural chemicals and pharmaceuticals, and dyes.
However, known reaction processes have serious disadvantages or extremely low selectivity and therefore poor yield. Accordingly, the known processes cannot be advantageously used in practice.
For example, para-hydroxybenzaldehyde which, nowadays, is of increasing importance as an anticarcinogen or a raw material for pharmaceuticals, agricultural chemicals and dyes, has conventionally been synthesized by reacting phenol with chloroform in the presence of an alkali. In the reaction, however, para-hydroxybenzaldehyde is obtained in a selectivity as low as about 30%, and a large amount of salicylaldehyde is formed as a by-product. Therefore, the production of para-hydroxybenzaldehyde in accordance with this process requires not only a large amount of raw materials but also a complicated operation for separation.
2,4-Dihydroxybenzaldehyde, nowadays, is also of increasing importance in view of its interesting behaviors such as cancer-controlling effect, plant root growth-promoting effect, antibacterial effect and photophosphorylation-controlling effect in chloroplast. For the production of 2,4-dihydroxybenzaldehyde, known is a process in which 1,3-dihydroxybenzene is reacted with chloroform in the presence of an alkali. However, in this known process, a large amount of 2,4-dihydroxy-3-formylbenzaldehyde is formed as a by-product, and 2,4-dihydroxybenzaldehyde which is the intended product is obtained only in low yield and with low selectivity. Accordingly, for producing 2,4-dihydroxybenzaldehyde by this process, not only large amounts of raw materials but also a complicated operation for separation is required.
As to the production of para-hydroxybenzoic acid which, nowadays, is of increasing importance as a raw material for heat resistant polymers, agricultural chemicals and pharmaceuticals, known is the Kolbe-Schmitt reaction in which para-hydroxybenzoic acid is synthesized by treating phenol with potassium hydroxide and potassium carbonate, followed by heating together with carbon dioxide under pressure. The reaction, however, has disadvantages that a costly pressure resistant apparatus is required because of high pressure applied during the reaction, and that much energy is required for the achievement a highly anhydrous condition which is indispensable to the reaction. Also known is another process in which phenol is reacted with carbon tetrachloride in the presence of an alkali to prepare para-hydroxybenzoic acid. In the process, however, the selectivity for the formation of para-hydroxybenzoic acid is 57%, and the reaction gives a large amount of salicylic acid as a by-product. Therefore, the process also requires not only large amounts of raw materials but also a complicated operation for separation.
2,5-Cyclohexadienone derivatives having an allyl group at the 4-position are also highly rea
REFERENCES:
patent: 4523031 (1985-06-01), Hirai et al.
JACS, vol. 105, No. 7, 2018-2021 (1983).
JACS, vol. 106, No. 1, 174-178 (1984).
Tetrahedron Letters, No. 20, 1645-1646 (1976).
Hirai Hidefuni
Komiyama Makoto
Sugiura Izuru
Hirai Hidefuni
Killos Paul J.
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