Linear and cyclic sucrose reaction products, their...

Details Linear and cyclic sucrose reaction products, their... Linear and cyclic sucrose reaction products, their...

1998-05-05

2001-08-28

Fonda, Kathleen Kahler (Department: 1623)

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

Organic compounds

Carbohydrates or derivatives

C536S123000, C536S123130, C127S046100

Reexamination Certificate

active

06281351

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to new and useful sucrose derivatives, the particular methods for their syntheses, and the use of the products.
BACKGROUND OF THE INVENTION
The most abundant pure organic chemical in the world is sucrose. See Kirk-Othmer,
Encyclopedia of Chemical Technology,
3d Edition, Volume 21, John Wiley & Sons, New York, pages 921-948 (1983). However, although sucrose produced from sugar cane and sugar beets is ubiquitous in its availability and is of relatively low cost, only a fraction of a percent by weight is consumed as a chemical feedstock. The potential value of sucrose as a raw material has been recognized for many years and has been the subject of considerable research.
Sucrose is a particularly appropriate material for use in the formation of esterified products produced currently from petroleum-based materials because (a) it is a naturally occurring, relatively abundant renewable material; (b) it is polyfunctional with three reactive primary alcohols that can readily be derivatized; (c) it is a nonreducing sugar and thus does not have the potential for the wide variety of side-reactions that reducing sugars have; (d) it has a relatively easily hydrolyzed glycosidic linkage that allow sucrose polymers to be potentially more biodegradable than polymers made with other carbohydrates, such as sugar alcohols; and (e) it is a naturally occurring sweet carbohydrate in common use and therefore potentially useful in the formation of potential non-absorbable, noncaloric sweeteners.
The usual technique for the synthesis of carbohydrate esters involves a reaction of the carbohydrate with an acid chloride or acid anhydride in a basic organic solvent, such as triethylamine, pyridine or quinoline. In a few instances, the organic base has been replaced by sodium hydroxide. However, the prior art teaches very little about the reaction of sucrose with polyfunctional reagents.
Although relatively few successful derivatives of sucrose have been commercialized, there has been substantial interest in developing sugar-based synthetic technology. Thus, in 1953, Sonntag, in
Chemical Reviews
52 at page 321, described a technique where a polyhydroxy compound was dissolved in a large excess of a tertiary amine, and by adding thereto an acid chloride, preferably in a solvent such as chloroform. However, only mixtures in low yields were obtained which were not easy to separate.
On the other hand, the preparation of pure regiospecific esters of polyhydric alcohols (carbohydrates) is a more complicated problem requiring special innovation, such as prior to reaction, the blocking of certain hydroxyl groups in the polyalcohol with easily removable groups.
In the patented literature, U.S. Pat. No. 2,927,919 relates to ether-esters of sucrose, U.S. Pat. No. 3,170,915 discloses sucrose ethers and U.S. Pat. No. 3,300,474 discloses the preparation of sucrose ether co-polymerizates.
SUMMARY OF THE INVENTION
It is accordingly one object of the present invention to provide a new group of ester and ether derivatives of sucrose.
It is a further object of the invention to provide a novel class of sucrose esters and ethers which are useful as food bulking agents, reduced calorie sweeteners, fat replacement agents for food products, stabilizing agents for food and beverage products, thickening and emulsifying agents for food products, adhesives, biodegradable plastics and films, sizing agents for paper and textiles, ethical pharmaceuticals and new fibers.
A still further object of the present invention is to provide a method for the preparation of sucrose esters which enables preparation of the sucrose esters in high yields and with improved specificity over methods known to the prior art.
Other objects and advantages of the present invention will become apparent as the description thereof proceeds.
The present invention comprises the use of various bifunctional reagents such as dicarboxylic acid dichlorides, epichlorohydrin, phosphorus oxychloride, and diphosphoryl tetrachloride for the formation of sucrose derivatives. The sucrose products disclosed herein are embraced by the following formula:
Suc—R(—Suc—R—)
x
Suc
wherein Suc is a sucrose molecule attached to a connector group R at the 6,6-, 6,6′-, or 6′,6′-positions of the sucrose in which x ranges from 0 up to about 500, and R is a radical which is the residue of a bifunctional acidic reactant. Preferably, R is a hydrocarbylacyl or hydrocarboyloxy radical or a phosphorous radical wherein the hydrocarbylacyl portion may be saturated or unsaturated aliphatic, cycloaliphatic, or aromatic, and may be further substituted by one, two, three or more other groups such as amino, hydroxyl, halogen, alkyl, alkyl substituted amino, or the like. By hydrocarbylacyl is meant a hydrocarbon portion of the type specified having two carbonyl functional groups attached to sucrose.
Preferably R is a radical selected from the group consisting of:
and the corresponding alkali metal and alkaline earth metal salts wherein m is 0 up to about 10, preferably 0 to about 6, and each of R
1
and R
2
independently is H, or C
1
-C
4
alkyl or one of R
1
and R
2
can also be OH or CH
2
OH.
To prepare the sucrose derivative of this invention, sucrose is reacted with a bifunctional reactant preferably of the formula X—R—X, wherein R is as defined above and X is a functionally reactive group such as a halogen, under special reaction conditions as described hereinafter. The preferred halogen is a chlorine group. The reaction is performed by the slow addition of a bifunctional reagent such as an acyl dichloride, dissolved in a substantially water immiscible organic solvent, to an alkaline aqueous solution of sucrose. The reaction proceeds at the interface between the two immiscible solutions to provide an interfacial condensation and produce the sucrose derivative or analogue. It has been discovered that this reaction at the interface of the organic solution and the aqueous solution imparts a specificity to the reaction for the 6 and the 6′ primary alcohol groups of sucrose.
It should be understood that equivalent reactants such as diepoxides and halohydrocarbyloxiranes such as epichlorohydrin also react in the process to provide new and useful sucrose esters.
It is a feature of the invention that the reaction can be controlled to produce at least four different types of compounds: a water-insoluble polymer, a water-soluble polymer, a sucrose dimer and a cyclic sucrose adduct. The relative amounts of each of these compounds can be selected by adjusting the conditions of the reaction. By the use of selected reaction conditions, yields of up to 95 to 100% of the desired product may be obtained. By appropriate selection of the type of acidic reactant, different structural groups with various chemical properties can be incorporated into the resulting sucrose compounds.
These sucrose reaction products have a wide range of potential uses as food bulking agents, reduced calorie sweeteners, fat replacement agents for food products, stabilizing agents for food and beverage products, thickening and emulsifying agents for food products, adhesives, paper and textile sizing, biodegradable plastics and films, ethical pharmaceuticals, and new fibers. When applied in these areas, the sucrose reaction products are combined with a non-reactive carrier in amounts of about 1 wt. % up to 99 wt. %.
DETAILED DESCRIPTION OF THE INVENTION
The present invention discloses reactions of certain acidic reagents with sucrose, the latter having the following structure and numbering system for the reactive hydroxyl groups and corresponding carbon atoms:
Formula 1
Sucrose
By the present invention it has been discovered that conducting the reaction of sucrose with a bifunctional acidic reactant or epoxide as described herein enables one to obtain specificity of the reaction at the 6 and 6′ positions of sucrose. The resulting products are novel sucrose condensation products wherein sucrose molecules are linked together by ester or ether linkages which may eit

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