Organic compounds -- part of the class 532-570 series – Organic compounds – Fatty compounds having an acid moiety which contains the...
Reexamination Certificate
1996-05-29
2001-03-13
Medley, Margaret (Department: 1714)
Organic compounds -- part of the class 532-570 series
Organic compounds
Fatty compounds having an acid moiety which contains the...
C554S149000, C554S156000, C554S218000, C508S501000
Reexamination Certificate
active
06201144
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a novel process for the production of previously unknown secondary ether fatty acids and secondary ether esters from either their equivalent fatty acids possessing an alcohol in the 4,5 or 6 position or, in the alternative, from their equivalent lactone precursors.
2. Description of the Prior Art
Production of hydroxy fatty acids and lactones utilizable as the starting material for the methods and products of the instant invention has been previously taught in the art.
U.S. patent application 08/534,810 filed Sep. 27, 1995, entitled “Method for Development of &dgr;-Lactones and Hydroxy Acids form Unsaturated Fatty Acids and Their Glycerides”, and herein incorporated by reference, teaches the formation of &dgr;-lactones and 5-hydroxy fatty acids.
U.S. Pat. No. 5,380,894 to Burg et al. teaches the formation of 5-,6- and 7-hydroxy fatty acids from the hydrolysis of estolides which were in turn produced from the reaction of one or a mixture of unsaturated fatty acids in the presence of a catalyst at elevated temperature and pressure.
Showell et al. (1968, J. Org. Chem., 33:2697-2704) disclose the production of &ggr;-lactones from oleic acid, undecylenic acid and erucic acid by perchloric acid isomerization. Hydrolysis of these &ggr;-lactones is subsequently carried out to yield 4-hydroxy fatty acids.
High yields of &dgr;-lactones have been achieved by the acid catalyzed reaction of a 4-hexenoic acid containing a carbocation stabilizing functionality as described by Fujita et al. (1982, J. Chem. Tech. Biotechnol., 32:476-484).
Ballantine et al. (“Organic Reactions Catalysed by Sheet Silicates: Ether Formation by the Intermolecular Dehydration of Alcohols and by the Addition of Alcohols to Alkenes”; J. Mol. Catal., 1984, 26, 37-56) teach that primary alcohols may be converted to ethers through the use of ion-exchanged montmorillonites as heterogenous catalysts in pressure vessels at 200° C. Secondary alcohols, in the presence of acid catalysts, typically undergo dehydration to their corresponding stable alkenes. As shown in Table 2 of Ballantine's article, ether yields from secondary alcohols in this reaction never exceeded 35% and were, except for a singular occurrence, below 10%.
SUMMARY OF THE INVENTION
We have now invented a process for the production of novel fatty ether esters and fatty ether acids, which possess low viscosity and low temperature melting point properties and may be used as viscosity modifiers in the creation of cosmetics and complete vegetable oil based biodegradable fluids such as hydraulic fluids and dielectric fluids. The fatty ethers are of the formula(I):
wherein R is selected from C
7
-C
17
aliphatic hydrocarbons which may be saturated or unsaturated, linear or branched, and may be optionally substituted, such as with one or more hydroxy groups; R
1
is selected from linear or branched C
1
-C
24
hydrocarbons which may be saturated or unsaturated, linear or branched, aliphatic or aromatic, and may be optionally substituted by one or more hydroxyl, halo, or amine groups; with the proviso that when R
1
is aromatic, it is limited to an optionally substituted six member carbon ring; and R
2
is selected from hydrogen or from linear or branched C
1
-C
24
hydrocarbons which may be saturated or unsaturated, linear or branched, aliphatic or aromatic, and may be optionally substituted by one or more hydroxyl, halo, or amine groups; with the proviso that when R
2
is aromatic, it is limited to an optionally substituted six member carbon ring; and x is an integer from 2 to 4.
Formation of these fatty ether compounds is by reaction of the appropriate hydroxy fatty acid or lactone with a nucleophilic alcohol in the presence of an acid catalyst to produce fatty ether esters. Following their formation, the fatty ether esters may be recovered for subsequent use, or in the alternative, they may either be hydrolyzed to produce fatty ether acids or transesterified with a different nucleophilic alcohol in the presence of an acid catalyst to produce alternate ester variants.
In accordance with this discovery, it is an object of the invention to provide novel fatty ether compounds having utility as viscosity modifiers, hydraulic fluids and dielectric fluids.
It is a further object of the invention to provide a method of making these fatty ether compounds.
Other objects and advantages of the invention will become readily apparent from the ensuing description.
DETAILED DESCRIPTION OF THE INVENTION
Starting materials for use in the instant invention include one or a mixture of 4,5 or 6 hydroxy fatty acids of the formula (II):
wherein R is selected from C
7
-C
17
hydrocarbons which may be saturated or unsaturated, linear or branched, and may contain other substituents, such as one or more hydroxy groups; and x is an integer from 2 to 4; or one or more of a mixture of &ggr;-, &dgr;- or &egr;-lactones of the formula (III):
wherein R is selected from C
7
-C
17
hydrocarbons which may be saturated or unsaturated, linear or branched, and may contain other substituents, such as one or more hydroxy groups, and x is an integer from 2 to 4;
The hydroxy fatty acids and lactones of formulas (II) and (III) may be acquired from natural sources or synthesized by means readily known to those of skill in the art. Useable fatty acid source materials, which may be converted by art-disclosed means into the hydroxy fatty acid and lactone starting materials of formulas (II) and (III), include the &Dgr;
5
and &Dgr;
6
unsaturated fatty acids in either the free or glyceryl ester form. These occur naturally in a variety of plant oils and may be conveniently obtained for use therefrom. Meadowfoam oil, having a high content of &Dgr;
5
unsaturated fatty acids is particularly preferred as a source material for preparation of the starting materials of the instant invention. Without being limited thereto, other oils such as pine oils, marsh-marigold oils, or oils of the carrot family (i.e. coriander, dill and fennel) may be used as sources.
Any monounsaturated vegetable oil including soybean oil, rapeseed oil, canola oil, sunflower oil, peanut oil and cottonseed oil may also be converted into its corresponding &ggr;-lactone by means of an acid catalyzed isomerization at 100° C. and thus also be used as a source material for preparation of the starting materials of the instant invention.
As starting materials in the reaction of the invention, the hydroxy fatty acids and/or lactones may be provided in substantially pure form or, in the alternative, as a mixture and/or in an impure form.
The novel fatty ether esters of the invention are prepared by a reaction of one or more of the fatty acids of formula (II)
wherein R is selected from C
7
-C
17
hydrocarbons which may be saturated or unsaturated, linear or branched, and may contain other substituents, such as one or more hydroxy groups; and x is an integer from 2 to 4; and/or one or more of a mixture of &ggr;-, &dgr;- or &egr;-lactones of formula (III):
wherein R is selected from C
7
-C
17
hydrocarbons which may be saturated or unsaturated, linear or branched, and may contain other substituents, such as one or more hydroxy groups, and x is an integer from 2 to 4; with a primary or secondary alcohol in the presence of a suitable acid catalyst under suitable conditions of temperature, pressure, reactant ratios and time to form fatty ether esters of formula (IV):
wherein R is selected from C
7
-C
17
hydrocarbons which may be saturated or unsaturated, linear or branched, and may contain other substituents, such as one or more hydroxy groups; each R
1
is identical and is selected from linear or branched C
1
-C
24
hydrocarbons which may be saturated or unsaturated, linear or branched, aliphatic or aromatic, and may be optionally substituted by one or more hydroxy, halo, aromatic or amine groups; with the proviso that when R
1
is aromatic, it is limited to an optionally substituted six member carbon ring; and x is an integer from 2 to 4.
Preferred fatty ether esters i
Isbell Terry A.
Mund Melissa S.
Fado John D.
Lipovsky Joseph A.
Medley Margaret
Silverstein M. Howard
The United States of America as represented by the Secretary of
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