Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2000-07-26
2002-04-02
Shippen, Michael L. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
Reexamination Certificate
active
06365788
ABSTRACT:
FIELD OF THE INVENTION
The present invention concerns a process for the production of a substituted or unsubstituted 1,2-bis(4-hydroxyphenyl)-hydroxyaliphatic from a substituted or unsubstituted 1,2-bis(4-hydroxyphenyl)-haloaliphatic. More particularly, the present invention concerns a process for the production of 1,2-bis(4-hydroxyphenyl)-2-hydroxypropane from 1,2-bis(4-hydroxyphenyl)-2-chloropropane.
BACKGROUND AND SUMMARY OF THE INVENTION
Compounds such as 4,4′-dihydroxy-&agr;-methylstilbenes are often useful as intermediates in the production of liquid crystal thermosets and thermoplastics. The aforementioned stilbenes are often prepared from compounds such as 1,2-bis(4-hydroxyphenyl)-2-chloropropanes. Unfortunately, however, compounds such as 1,2-bis(4-hydroxyphenyl)-2-chloropropanes must be stored in dilute concentrations at low temperatures (<15° C.) or decomposition will occur. Moreover, the process for converting the 1,2-bis(4-hydroxyphenyl)-2-chloropropane to the corresponding stilbene is disadvantageous in that hydrogen chloride, a difficult to handle co-product, is produced.
Alternate processes would be desirable in order to overcome the aforementioned problems associated with using the starting material 1,2-bis(4-hydroxyphenyl)-2-chloropropane when making stilbenes, i.e., the problems of storage and producing hydrogen chloride co-product. One alternate process would involve the dehydration of a substituted or unsubstituted 1,2-bis(4-hydroxyphenyl)-hydroxyaliphatic such as 1,2-bis(4-hydroxyphenyl)-2-hydroxypropane. In contrast to 1,2-bis(4-hydroxyphenyl)-2-chloropropane, compounds such as 1,2-bis(4-hydroxyphenyl)-2-hydroxypropane are often storable at ambient conditions and would only produce water as a co-product when preparing 4,4′-dihydroxy-&agr;-methylstilbenes. Unfortunately, however, there are no prior synthetic methods of preparing discreet compounds such as 1,2-bis(4-hydroxyphenyl)-2-hydroxypropane.
A prior method of preparing 1,2-bis(4-hydroxyphenyl)-2-hydroxypropane is described in Spivack, Leib and Lobos in
The Journal of Biological Chemistry
, Volume 269, No. 10, pages 7323-7329 (1994). The complex chemical and biological route described by Spivack et al. first involved the production of 1,2-bis(4-methoxyphenyl)-2-propanol in an unspecified yield via reaction of 4-methoxyphenyl magnesium bromide and 4-methoxyphenylacetone in dry tetrahydrofuran. Spivack et al. could not demethylate the 1,2-bis(4-methoxyphenyl)-2-propanol without substantial dehydration of the product to 4,4′-dihydroxy-&agr;-methylstilbene. Therefore, in order to obtain 1,2-bis(4-hydroxyphenyl)-2-hydroxypropane Spivack et al. conducted a biochemical demethylation in the presence of the fungus,
Aspergillus parasiticus
. Isolation methods to recover the product from the biologic medium are not given, but are expected to be complex and to produce low yields of an impure product, based on their reported isolation of 1,2-bis(4-hydroxyphenyl)-2-hydroxypropane as a bisphenol A metabolite in a biologic medium.
Therefore, it would be desirable to discover a synthetic process to prepare 1,2-bis(4-hydroxyphenyl)-hydroxyaliphatics such as 1,2-bis(4-hydroxyphenyl)-2-hydroxypropane in a simple manner with a good yield.
Advantageously, the present invention pertains to a process to prepare 1,2-bis(4-hydroxyphenyl)-hydroxyaliphatics such as 1,2-bis(4-hydroxyphenyl)-2-hydroxypropane in a simple manner with a good yield. The inventive process relates to producing a compound having the structural Formula I
wherein R is independently selected from the group consisting of hydrogen, a hydrocarbyl group having from 1 to about 12 carbon atoms, a hydrocarbyloxy group having from 1 to about 12 carbon atoms, a halogen atom, and a nitro group, and R
1
is a hydroxyl substituted aliphatic group having from 3 to about 8 carbon atoms. The process comprises reacting a compound having the structural Formula II,
wherein R is as described above and R
2
is a halogen substituted aliphatic group having from 3 to about 8 carbon atoms with a base and water, and wherein
(1) the base is selected from the group consisting of an alkali metal carbonate, alkaline earth metal carbonate, an alkali metal bicarbonate, an alkaline earth metal bicarbonate, and mixtures thereof;
(2) the equivalent ratio of base to halogen in the aliphatic group is from about 0.9:1 to about 5:1; and
(3) the amount of water is from about 20 to about 500 percent by weight of the combined weight of the compound of Formula II and water.
The present invention also relates to novel, synthetic, compounds having structural Formula V
wherein R is independently selected from the group consisting of hydrogen, a hydrocarbyl group having from 1 to about 12 carbon atoms, a hydrocarbyloxy group having from 1 to about 12 carbon atoms, a halogen atom, and a nitro group; R
3
is an alkylene group having from 3 to about 8 carbon atoms substituted with one or more hydroxyl groups. In a particular aspect, if all R groups are hydrogen then R
3
is not—C(CH
3
)(CH
2
OH)—, —CH
2
C(OH)(CH
2
OH)—, —C (CH
2
OH)(CH
2
OH)—.
DETAILED DESCRIPTION OF THE INVENTION
As used herein, the term “hydrocarbyl” means any substituted or unsubstituted aliphatic, cycloaliphatic, aromatic, aryl substituted aliphatic, aryl substituted cycloaliphatic, aliphatic substituted aromatic, or cycloaliphatic substituted aromatic group. The aliphatic or cycloaliphatic group groups can be saturated or unsaturated. The aliphatic groups can be straight chain or branched. Suitable substituents include any substituent which does not substantially interfere with the reaction.
As used herein, the term “hydrocarbyloxy” means a hydrocarbyl group having an oxygen linkage between it and the atom to which it is attached.
As used herein, the term “hydroxyl substituted aliphatic” or “hydroxyaliphatic” means an aliphatic group, such as alkylene or alkenylene, which is substituted with one or more hydroxyl groups and is divalent, i.e., has two attachment points as shown for R
1
in Formula I. Similarly, the term “halogen substituted aliphatic” or “haloaliphatic” means an aliphatic group, such as alkylene or alkenylene, which is substituted with one or more halogen groups and is divalent, i.e., has two attachment points as shown for R
2
in Formula II.
As used herein, the term “polar protic solvent” means a compound which serves as a solvent and has a high dielectric constant and strong polarity. For the purpose of the present invention, “polar protic solvent” means that the compound contains at least one hydroxyl group.
As used herein, the term “synthetic” means that the compound is prepared via a non-biological route, i.e., the compound is not prepared, for example, via bacterial metabolism.
Generally, the inventive process relates to producing a compound having the structural Formula I
wherein R is independently selected from the group consisting of hydrogen, a hydrocarbyl group having from 1 to about 12 carbon atoms, a hydrocarbyloxy group having from 1 to about 12 carbon atoms, a halogen atom, and a nitro group, and R
1
is an hydroxyl substituted aliphatic group having from 3 to about 8 carbon atoms. Preferably R is hydrogen and R
1
is a hydroxyl substituted alkylene group. Preferable alkylene groups include propylene, and butylene. Preferable substituted alkylene groups include —C(CH
3
)(OH)CH
2
— and —C(CH
2
OH)(CH
2
OH)—.
The process comprises reacting a compound having the structural Formula II with a base and water,
wherein R is as described above and R
2
is a halogen substituted aliphatic group having from 3 to about 8 carbon atoms. Preferably R is hydrogen and R
2
is a halogen substituted alkylene group. Preferable alkylene groups include propylene and butylene. Preferable halogens include chlorine and bromine. Preferable substituted alkylene groups include —C(CH
3
)(X)CH
2
— and —C(CH
2
X)(CH
2
X)—, wherein X represents —Cl, —Br, or —I.
A particularly preferred embodiment is a process for producing a compound
having the structural Formula III
by reacting a compound having the struct
Black Lance L.
Clement Katherine S.
Hefner, Jr. Robert E.
Walker Louis L.
Shippen Michael L.
The Dow Chemical Company
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