WO1995015330A1 - Formation of an n-fatty alkyl amidosugar - Google Patents
Formation of an n-fatty alkyl amidosugar Download PDFInfo
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- WO1995015330A1 WO1995015330A1 PCT/US1994/013764 US9413764W WO9515330A1 WO 1995015330 A1 WO1995015330 A1 WO 1995015330A1 US 9413764 W US9413764 W US 9413764W WO 9515330 A1 WO9515330 A1 WO 9515330A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C235/06—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
Definitions
- R 1 can be hydrogen or certain lower alkyl group- containing substituents
- R 2 can be fatty alkyl and Z is a polyhydroxyhydrocarbyl group
- n can range from 4 to 24, thus including fatty alkyl, R can be a hydroxyalkylene-containing substituent, and X is sodium, potassium, or hydrogen;
- m can range from 2 to 6 and R is a C 6 -C 18 alkyl group, such as fatty alkyl.
- R is a C 6 -C 18 alkyl group, such as fatty alkyl.
- the compounds shown in this French patent are said to be prepared by reaction of aldonic acid (which actually will not work) or the corresponding lactone (which will work) with the desired amine.
- Gluconolactone is the preferred reagent.
- Such a preparatory procedure requires the use of a relatively expensive starting material and is relatively more complex than desired;
- U.S. Patent No. 2,662,073 describes gluconamides which are prepared by condensing long chain aliphatic or cycloaliphatic primary amines with 5-gluconolactone; and 5.
- U.S. Patent No. 5,084,270 describes N- alkoxyalkylamides which are formed by reacting a specific type of amine compound with a carboxylic acid or lactone having a particular structure. It has been found that only the lactone reagent described for use in this patent will give an amidosugar. Use of the acid will not. Previously reported reactions between glucose, amines, and hydrogen cyanide or potassium cyanide are reported to give the ⁇ -aminonitrile derivatives of the sugar. (See H.
- the present invention relates to a process for forming N-fatty alkyl amidosugars by reacting an aldose, ketose, or mixture thereof with cyanide and fatty amine.
- N-fatty alkyl a idosugar compounds which are produced by the process of the present invention have the preferred formula
- R is fatty alkyl
- R' is either hydrogen or alkyl
- aldose as used herein is intended to cover those sugar molecules which contain an aldehyde group and one or more alcohol groups.
- reagents have the general formula RC(0)H where R is hydroxyalkyl, e.g., of 3 to 15 carbon atoms.
- Preferred species have the formula
- cyanide is to be construed as embracing those compounds which can supply cyanide anion, as a reagent, in the selected reaction medium in accordance with the claimed process.
- reagents of this type include the alkali metal and alkaline earth metal cyanide salts such as sodium or potassium cyanide, and HCN.
- fatty amine is to be construed as covering primary and secondary amines which contain at least one fatty alkyl substituent (e.g., a C 12 to C 24 alkyl group) .
- Representative fatty amines include dodecylamine, octadecylamine, cocoalkylamine, tallowalkylamine, oleylalkylamine, and soyalkylamine.
- the instant process in a preferred embodiment, used an aqueous reaction medium, most preferably one containing alcohol to promote the solubility of the amine.
- the process can be run by first dissolving the amine and aldose in the solvent with optional heating (e.g., 70°C to reflux) for a sufficient amount of time (e.g., about one hour) followed by cooling to ambient with addition of the cyanide reagent.
- the pH of the reaction medium is basic (e.g. , a pH of about 9-10) .
- An equivalent of acid is needed.
- Either an amino hydrohalide may be used or an acid or acid generating species (e.g., acetic acid, hydrochloric acid, or sodium bisulfite) may be added.
- amidosugar In general terms, it is necessary to have at least one equivalent of acid present to form the amidosugar.
- the acid can be added either, preferably, before or after the cyanide if a homologated acid has not been formed.
- Three routes are possible in forming the amidosugar: (1) the use of sodium bisulfite to form an adduct with the aldose, ketose, or mixture thereof (this process is less preferred since the yields of desired product tend to be low) ; (2) use of the amine hydrochloride as reagent or added hydrochloric acid; and (3) use of excess acetic acid (works well but the use of an acidic pH may evolve undesired hydrogen cyanide) .
- Example 2 repeats the process of Example 1 on the same molar scale of 0.03 mole with glucose used as a starting reagent rather than arabinose.
- the dodecylamine was added to the starting glucose-sodium bisulfite reaction mixture followed by reflux for one hour.
- the potassium cyanide was allowed to react for three to four hours after its addition.
- a 70:30 ethanol/water mixture (volume basis) was used as the solvent to dissolve amine and glucose.
- Example 2 utilizes the process of Example 1, on the same 0.03 mole scale, employing fructose as the sugar reagent rather than arabinose.
- the dodecylamine after addition to the fructose-bisulfite reaction medium, was reacted for fifteen minutes at room temperature.
- This Example illustrates an amine hydrochloride route for practice of the present invention.
- Dodecylamine hydrochloride (6.65 g, 0.03 mole) and glucose (5.4 g, 0.03 mole) were dissolved in aqueous ethanol (70:30 ethanol:water on a volume basis), and the solution was refluxed for 1.5 hours. The mixture was cooled to room temperature, and potassium cyanide (2.01 g, 0.03 mole) was added. The reaction was stirred at room temperature for three hours and then allowed to stand overnight. The product crystallized from the reaction mixture. One more crop of crystals was obtained by cooling the mother liquor. The last batch of product was obtained by stripping off the mother liquor.
- E Amidosugar, the desired product. t weight of amidosugar and potassium chloride.
- Example 7 was repeated with the reaction mixture containing amine hydrochloride and glucose being allowed to react for fifteen minutes at room temperature before potassium cyanide addition. The product was centrifuged and washed with water and then ethanol.
- Example 8 The process of Example 8 was carried out using two equivalents of the amine hydrochloride, an aqueous ethanol solvent, as described in Example 5, and refluxing the glucose-amine hydrochloride for 1.5 hours before potassium cyanide addition.
- Example 9 was repeated using anhydrous ethanol (35% solids) as the solvent for amine hydrochloride and glucose, a one hour reflux time, and four hours of potassium cyanide reaction at room temperature. Reaction techniques to substantially exclude moisture were employed.
- Example 11 was repeated with the same solvent at twice the amount (24% solids, rather than 13% solids by weight) .
- Example 9 The process of Example 9 was followed with the exception that the potassium cyanide reaction took place at 60-70-C for three hours rather than at room temperature overnight.
- This reaction utilizes fructose as the sugar reagent and the amine hydrochloride route for making the desired amidosugar.
- Fructose (5.4 g) and dodecylamine hydrochloride (6.65 g) were added to water at room temperature and were stirred allowed to stand for fifteen minutes. Then, potassium cyanide (2.0 g) was allowed to react at room temperature overnight.
- the product comprised the following:
- Example 14 The process of Example 14 was carried out using arabinose as the sugar reagent rather than fructose. The following product distribution was obtained:
- Example 15 The process of Example 15 was repeated using aqueous ethanol (70:30 ethanol:water) as the solvent, heating the arabinose-dodecylamine hydrochloride mixture at 80°C for 1.5 hours, and treating it with potassium cyanide for two hours at room temperature. The following results were obtained:
- Example 17 The general process of Example 17 was repeated with arabinose using 2:1 water:ethanol as the solvent rather than 4:1 water:ethanol.
- the product crystallized from the reaction mixture to give 71% yield that comprised 3.9 area% amine, 0.5 area% gluconic acid, no detectible arabinosylamine, 87.2 area% amidosugar, and 4.9 area% unknown.
Abstract
N-fatty alkyl amidosugars, for example, those of the general formula: HOCH2-(CHOH)mCON(R')-R where m is 3 to 9, R is fatty alkyl, and R' is either hydrogen or alkyl, can be formed by reaction of an aldose, ketose, or mixture thereof with cyanide and fatty amine.
Description
FORMATION OF AN N-FATTY ALKYL AMIDOSUGAR
BACKGROUND OF THE INVENTION
A wide variety of chemical compounds possessing surfactant properties are known to persons of ordinary skill in the art including those which possess hydroxyalkylene moieties and/or fatty alkyl amine moieties. Some representative prior art references which illustrate such compounds include:
1. U.S. Patent Nos. 5,174,927 and 5,188,769 which cover polyhydroxy fatty acid amides of the general formula
R1
/ R2C(0)N
\ Z
where R1 can be hydrogen or certain lower alkyl group- containing substituents, R2 can be fatty alkyl and Z is a polyhydroxyhydrocarbyl group;
2. U.S. Patent No. 5,004,564 which discloses certain glycaminoacetic acid/acetates of the formula
C„H2n+IN-CH2COO-X+ R
where, n can range from 4 to 24, thus including fatty alkyl, R can be a hydroxyalkylene-containing substituent, and X is sodium, potassium, or hydrogen; and
3. French Patent No. 2,523,962 which describes certain N-fatty alkyl amidosugars of the general formula
HOCH2-(CHOH)mCONH-R
where m can range from 2 to 6 and R is a C6-C18 alkyl group, such as fatty alkyl. The compounds shown in this French patent are said to be prepared by reaction of aldonic acid
(which actually will not work) or the corresponding lactone (which will work) with the desired amine. Gluconolactone is the preferred reagent. Such a preparatory procedure requires the use of a relatively expensive starting material and is relatively more complex than desired;
4. U.S. Patent No. 2,662,073 describes gluconamides which are prepared by condensing long chain aliphatic or cycloaliphatic primary amines with 5-gluconolactone; and 5. U.S. Patent No. 5,084,270 describes N- alkoxyalkylamides which are formed by reacting a specific type of amine compound with a carboxylic acid or lactone having a particular structure. It has been found that only the lactone reagent described for use in this patent will give an amidosugar. Use of the acid will not. Previously reported reactions between glucose, amines, and hydrogen cyanide or potassium cyanide are reported to give the α-aminonitrile derivatives of the sugar. (See H. Parekh et al., J. Indian Chem. Soc, Vol. 49, No. 11, 1972, pp. 1147-1150 and R. Kuhn et al., Justus Liebigs Ann. Chem., 1956, Vol. 600, pp. 115-124) .
SUMMARY OF THE INVENTION
The present invention relates to a process for forming N-fatty alkyl amidosugars by reacting an aldose, ketose, or mixture thereof with cyanide and fatty amine.
DESCRIPTION OF PREFERRED EMBODIMENTS
The N-fatty alkyl a idosugar compounds which are produced by the process of the present invention have the preferred formula
HOCH2-(CHOH)mC(0)N(R')-R
where m can range from about 3 to about 9, R is fatty alkyl, and R' is either hydrogen or alkyl.
The term "aldose" as used herein is intended to cover those sugar molecules which contain an aldehyde group and one or more alcohol groups. These reagents have the general formula RC(0)H where R is hydroxyalkyl, e.g., of 3 to 15 carbon atoms. Preferred species have the formula
HOCH2-(CHOH)mC(O)H
where m is as defined above. The term "ketose" is intended to cover those sugar molecules derived from ketones of the formula R2C=0, where R, which may be the same or different, is as defined above for the aldose reagent.
The term "cyanide" is to be construed as embracing those compounds which can supply cyanide anion, as a reagent, in the selected reaction medium in accordance with the claimed process. Representative, and preferred, reagents of this type include the alkali metal and alkaline earth metal cyanide salts such as sodium or potassium cyanide, and HCN.
The term "fatty amine" is to be construed as covering primary and secondary amines which contain at least one fatty alkyl substituent (e.g., a C12 to C24 alkyl group) . Representative fatty amines include dodecylamine, octadecylamine, cocoalkylamine, tallowalkylamine, oleylalkylamine, and soyalkylamine.
The instant process, in a preferred embodiment, used an aqueous reaction medium, most preferably one containing alcohol to promote the solubility of the amine. The process can be run by first dissolving the amine and aldose in the solvent with optional heating (e.g., 70°C to reflux) for a sufficient amount of time (e.g., about one hour) followed by cooling to ambient with addition of the cyanide reagent. The pH of the reaction medium is basic (e.g. , a pH of about 9-10) . An equivalent of acid is needed. Either an amino hydrohalide may be used or an acid or acid generating species (e.g., acetic acid, hydrochloric acid, or sodium bisulfite) may be added.
In general terms, it is necessary to have at least one equivalent of acid present to form the amidosugar. The acid can be added either, preferably, before or after the cyanide if a homologated acid has not been formed. Three routes are possible in forming the amidosugar: (1) the use of sodium bisulfite to form an adduct with the aldose, ketose, or mixture thereof (this process is less preferred since the yields of desired product tend to be low) ; (2) use of the amine hydrochloride as reagent or added hydrochloric acid; and (3) use of excess acetic acid (works well but the use of an acidic pH may evolve undesired hydrogen cyanide) . In regard to the hydrochloride route (2) , it is necessary to add the amine reagent prior to the cyanide to lessen the amount of homologated acid which is formed. Simultaneous addition of cyanide and amine to the sugar (e.g., aldose, ketose, or mixture thereof) will also increase the amount of homologated acid product.
The present invention is further illustrated by the Examples which follow.
EXAMPLE 1
This illustrates the use of sodium bisulfite as one of the reagents to practice the present invention.
Sodium bisulfite (3.12 g) was added to a solution of arabinose (4.5 g) in 50 ml of water at room temperature. After stirring for two hours, dodecylamine (5.51 g) was added, and, after fifteen minutes, potassium cyanide (2.0 g) was then added. Stirring was continued at room temperature overnight. The solid product was collected by filtration and washed with water. The following Table sets forth the results with all percent values for the respective product fractions being expressed as weight percents and the values for the products in each respective fraction being expressed as area percents from gas chromatography analysis (nd=not detectible) with trace by-product components being ignored:
Fraction Amine Gluconic Acid
Arabinosvla ine
Crystals* (4%) 0.6% 3.1% 0.6%
Crystals** (34%) 36.4% 4.1% 0.5%
Filtrate, stripped (62%) 3.9% 72.5% nd
Fraction(cont 'd) Amidosugar Unknown Crystals* (4%) 91.8% 0.6%
Crystals** (34%) 24.8% 31.5%
Filtrate, stripped (62%) 7.6% nd
* First crop. ** Second crop.
EXAMPLE 2
The process of Example 1 was repeated on the same scale (0.03 mole) with the sodium bisulfite-arabinose solution being stirred at 60°C for one hour. Dodecylamine was added and the resulting mixture stirred at 60°C for one hour followed by potassium cyanide addition as described in Example 1. The results obtained were as follows (* = first crystal crop; ** = second crystal crop; and filtrate was stripped) :
Fraction Amine Gluconic Acid Arabinosyla ine Crystals* (7%) 1.0% 1.3% nd Crystals** (33%) 38.4% 1.1% 2.9% Filtrate (60%) nd 79.2% nd
Fraction fcont'd) Amidosuαar Unknown Crystals* (7%) 73.7% 29.7% Crystals** (33%) 14.9% 30.4% Filtrate (60%) 23.2% nd
EXAMPLE 3
This Example repeats the process of Example 1 on the same molar scale of 0.03 mole with glucose used as a starting reagent rather than arabinose. The dodecylamine was added to the starting glucose-sodium bisulfite reaction mixture followed by reflux for one hour. The potassium cyanide was allowed to react for three to four hours after its addition. A 70:30 ethanol/water mixture (volume basis) was used as the solvent to dissolve amine and glucose.
The results obtained were as follows (* = first crystal crop; ** = second crystal crop; the filtrate was stripped; and "nd" = not detectible) :
Heptonic
Fraction Amine Acid Glucosvla ine Crystals* (19.1%) nd 15.0% nd Crystals** (40.4%) nd 15.3% nd Filtrate (35.6%) nd 47.6% 4.9%
Fraction(cont'd) Amidosuαar Unknown Crystals* (19.1%) 64.2% 4.3% Crystal** (40.4%) 54.9% 5.8% Filtrate (35.6%) 31.8% nd
EXAMPLE 4
This Example utilizes the process of Example 1, on the same 0.03 mole scale, employing fructose as the sugar reagent rather than arabinose. The dodecylamine, after addition to the fructose-bisulfite reaction medium, was reacted for fifteen minutes at room temperature.
The results obtained from analysis of the solid obtained from vacuum stripping the reaction mixture was as follows:
Compound Area %
Amine 60.2 Heptonic Acid 0.8
Fructosylamine 0.5
Amidosugar 33.7 Unknown 0.5
EXAMPLE 5
This Example illustrates an amine hydrochloride route for practice of the present invention.
Dodecylamine hydrochloride (6.65 g, 0.03 mole) and glucose (5.4 g, 0.03 mole) were dissolved in aqueous ethanol (70:30 ethanol:water on a volume basis), and the solution was refluxed for 1.5 hours. The mixture was cooled to room temperature, and potassium cyanide (2.01 g, 0.03 mole) was added. The reaction was stirred at room temperature for three hours and then allowed to stand overnight. The product crystallized from the reaction mixture. One more crop of crystals was obtained by cooling the mother liquor. The last batch of product was obtained by stripping off the mother liquor.
The Table, below, sets forth the weight percents of amine from the starting material, desired amidosugar, and by-products (glucoheptonic lactone and glucoheptonic acid) in each product batch (* = first crystal crop; ** = second crystal crop; the filtrate was stripped; and "nd" = not detectible) :
Mass Weight % Balance* B'
Crystals* (21%) 6.3 nd 1.6 92.0 Crystals** (35%) 6.3 5.6 29.1 55.0 Filtrate (44%) 24.8 nd 14.6 59.4
A = Dodecylamine.
B = Glucoheptonic lactone.
C = Heptonic acid.
D = Amidosugar, the desired product.
* weight of amidosugar and potassium chloride.
EXAMPLE 6
The process of Example 5 was repeated using twice the amount of aqueous ethanol solvent to dissolve amine hydrochloride and glucose. The following results were obtained (* = first crystal crop; ** = second crystal crop; and filtrate was stripped) :
Mass - Weight % -•
Balancet A! ϋ c! Ωl E!
Crystals* (30%) 3.8 nd 3.6 nd
88.8
Crystals** (28%) 8.0 nd 4.7 6.8
77.4
Filtrate (14%) 20.5 5.7 44.9 2.3
28.9
A = Dodecylamine.
B = Glucoheptonic lactone.
C = Heptonic acid.
D = Glucosylamine.
E = Amidosugar, the desired product. t weight of amidosugar and potassium chloride.
EXAMPLE 7
The process of Example 5 was used with water, rather than aqueous ethanol, being used to dissolve the amine hydrochloride and glucose followed by refluxing for one hour. then potassium cyanide was added at room temperature. The product was collected by filtration and was washed with ethanol, yield : 88%. The product contained the following compounds ("nd" = not detectible):
Compound Area % Amine 22.3
Heptonic Acid 23.8
Glucosylamine nd
Amidosugar 50.7
Unknown nd
EXAMPLE 8
Example 7 was repeated with the reaction mixture containing amine hydrochloride and glucose being allowed to react for fifteen minutes at room temperature before potassium cyanide addition. The product was centrifuged and washed with water and then ethanol.
The following results were obtained:
Heptonic
Fraction Amine Acid Glucosylamine
No. 1* 19.7 1.1 nd
No. 2** 17.1 nd nd
Fraction Amidosuqar Unknown No. 1* 76.0 0.8 No. 2** 80.4 2.5
* solid product collected by centrifuging and washing with ethanol.
** solid that crystallized from the ethanol used to wash the product.
EXAMPLE 9
The process of Example 8 was carried out using two equivalents of the amine hydrochloride, an aqueous ethanol solvent, as described in Example 5, and refluxing the glucose-amine hydrochloride for 1.5 hours before potassium cyanide addition.
The results were as follows (* = first crystal crop; ** = second crystal crop; the filtrate was stripped; and "nd" = not detectible) :
Fraction Amine Heptonic Acid
Glucosylamine Crystals* (15%) nd nd nd Crystals** (19%) 22.5 1.8 nd Filtrate (47.4%) 46.1 12.5 nd
Fraction(cont'd) A idosu ar Unknown Crystals* (15%) 86.8 13.2 Crystals** (19%) 57.9 13.0 Filtrate (47.4%) 39.0 1.7
EXAMPLE 10
Example 9 was repeated using anhydrous ethanol (35% solids) as the solvent for amine hydrochloride and glucose, a one hour reflux time, and four hours of potassium cyanide reaction at room temperature. Reaction techniques to substantially exclude moisture were employed.
The results were as follows (* = solid product washed with water; ** = water wash, vacuum stripped; the filtrate was stripped; and "nd" = not detectible) :
Fraction Amine Heptonic Acid Glucosylamine Filtrate (39.9%) 63.2 nd 15.9 Solid 1* (23.5%) 30.9 23.9 nd Solid 2** (32.1%) nd 90.1 nd
Fraction(cont'd) Amidosu ar Unknown Filtrate (39.9%) nd nd Solid 1* (23.5%) 36.5 nd Solid 2** (32.1%) nd nd
EXAMPLE 11
The preceding Example was repeated using a 1.5 hour reflux with aqueous ethanol being used as the solvent for amino hydrochloride and glucose (13% solids) . The results were as follows (* = first crystal crop;
** = second crystal crop; the filtrate was stripped; and "nd" = not detectible) :
Fraction Amine Heptonic Acid Glucosylamine Crystals* (37%) 1.2 2.6 nd Crystals** (4%) 1.8 nd nd Filtrate (50%) 12.7 20.1 3.4
Fraction(cont'd) Amidosuαar Unknown Crystals* (37%) 96.2 nd Crystals** (4%) 14.2 82.7 Filtrate (50%) 60.7 0.8
EXAMPLE 12
Example 11 was repeated with the same solvent at twice the amount (24% solids, rather than 13% solids by weight) . The results were as follows (a single crystal crop; the filtrate was stripped; and "nd" = not detectible) :
Fraction Amine Heiptonic Acid
Glucosylamine
Crystals (43%) 2.5 2.4 nd
Filtrate (43%) 6.5 31.3 3.3
Fraction Amidosuqar Unknown
Crystals (43%) 89.3 5.0
Filtrate (43%) 52.5 1.5
EXAMPLE 13
The process of Example 9 was followed with the exception that the potassium cyanide reaction took place at 60-70-C for three hours rather than at room temperature overnight.
The following results were obtained (* = first crystal crop; ** = second crystal crop; the filtrate was stripped; and "nd" = not detectible) :
Fraction Amine Heptonic Ac 3id Crystals* (29%) 3.7 21.4 Crystals** (22%) 15.6 24.5 Filtrate (21%) 29.8 12.4
Fraction(cont'd) Glucosylamine Amidosuσar Crystals* (29%) nd 70.1 Crystals** (22%) nd 53.9 Filtrate (21%) nd 51.1
EXAMPLE 14
This reaction utilizes fructose as the sugar reagent and the amine hydrochloride route for making the desired amidosugar. Fructose (5.4 g) and dodecylamine hydrochloride (6.65 g) were added to water at room temperature and were stirred allowed to stand for fifteen minutes. Then, potassium cyanide (2.0 g) was allowed to react at room temperature overnight. The product comprised the following:
Compound Area %
Amine 34.4
Heptonic Acid 22.9
Fructosylamine nd Amidosugar 39.4
EXAMPLE 15
The process of Example 14 was carried out using arabinose as the sugar reagent rather than fructose. The following product distribution was obtained:
Compound Area %
Amine 7.7
Heptonic Acid 1.3
Glucosylamine nd
Amidosugar 84.2 Unknown 2.0
- 20 -
EXAMPLE 16
The process of Example 15 was repeated using aqueous ethanol (70:30 ethanol:water) as the solvent, heating the arabinose-dodecylamine hydrochloride mixture at 80°C for 1.5 hours, and treating it with potassium cyanide for two hours at room temperature. The following results were obtained:
Fraction Amine Gluconic Acid Arabinosylamine Crystals (29%) 0.7% 3.4 3.3 Filtrate (72% 1.0% 6.7 5.1 Residue (<1%) 2.0% nd nd
Fraction Amidosuqar Unknown Crystals (29%) 81.8 4.0 Filtrate (72%) 63.2 21.0 Residue (<1%) 43.7 26.3
EXAMPLE 17
This illustrates preparation of the amidosugar using glucose as the sugar reagent, the free amine, and acetic acid as an acidifying agent, a variant of the process shown in the Journal of the Indian Chemical Society, Vol. 49, No. 11, 1972, pp. 1147-1150, in which -aminonitriles, rather than amidosugars, were formed by condensing D- glucosecyanhydrin with certain aryl group-containing bases. Glucose (5.4 g) and potassium cyanide (2.01 g) were added to a 4:1 (v:v) ethanol:water solvent mixture and was stirred for fifteen minutes at room temperature. Then, acetic acid (1.7 mL) was added and the mixture was stirred for fifteen minutes at room temperature. Then, dodecylamine (5.57 g) was added and the resulting mixture was stirred at room temperature overnight.
The following results were obtained (* = first crystal crop; ** = second crystal crop) :
Fraction Amine Heptonic Acid
Glucosylamine
Crystals* (32%) 15.5% 1.9% nd
Crystals** (10%) 20.4% nd nd
Fractionfcont' -dj. Amidosuqar Unknown
Crystals* (32%) 78.9% 3.0%
Crystals** (10%) 76.4% 3.3%
EXAMPLE 18
The general process of Example 17 was repeated with arabinose using 2:1 water:ethanol as the solvent rather than 4:1 water:ethanol. The product crystallized from the reaction mixture to give 71% yield that comprised 3.9 area% amine, 0.5 area% gluconic acid, no detectible arabinosylamine, 87.2 area% amidosugar, and 4.9 area% unknown.
The foregoing Examples are presented for illustrative purposes only and for that reason should not be construed in a limiting sense. The scope of protection sought is set forth in the claims which follow.
Claims
1. A process for the formation of an N-fatty alkyl amidosugar which comprises the reaction of an aldose, ketose, or mixture thereof with cyanide and fatty amine to form the N-fatty alkyl amidosugar.
2. A process as claimed in Claim 1 wherein the aldose is of the formula RC(0)H where R is hydroxyalkyl.
3. A process as claimed in Claim 2 wherein R contains from about 3 to about 15 carbon atoms.
4. A process as claimed in Claim 1 wherein the aldose is of the formula RC(0)H where R is hydroxyalkyl containing from about 3 to about 15 carbon atoms.
5. A process as claimed in Claim 1 wherein the fatty amine contains from about 12 to about 24 carbon atoms.
6. A process as claimed in Claim 2 wherein the fatty amine contains from about 12 to about 24 carbon atoms.
7. A process as claimed in Claim 3 wherein the fatty amine contains from about 12 to about 24 carbon atoms.
8. A process as claimed in Claim 4 wherein the fatty amine contains from about 12 to about 24 carbon atoms.
9. A process as claimed in Claim 8 wherein the cyanide is an alkali metal cyanide.
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| US15939093A | 1993-11-30 | 1993-11-30 | |
| US08/159,390 | 1993-11-30 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0757054A1 (en) * | 1995-07-13 | 1997-02-05 | Akzo Nobel N.V. | Polysaccharide acid amide comprising fatty alkyl group in amide |
| EP2149539A1 (en) * | 2007-05-23 | 2010-02-03 | Kowa Company. Ltd. | Boron adsorbent utilizing sugar amide derivative, and boron removal method |
-
1994
- 1994-11-28 WO PCT/US1994/013764 patent/WO1995015330A1/en active Application Filing
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| Title |
|---|
| CARBOHYDRATE RESEARCH, Vol. 143, 1985, ALBARRAN et al., "Limitations of the Aminonitrile Synthesis, New Products from D-Glucose, D-Galactose and D-Mannose", pages 117-128. * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0757054A1 (en) * | 1995-07-13 | 1997-02-05 | Akzo Nobel N.V. | Polysaccharide acid amide comprising fatty alkyl group in amide |
| EP2149539A1 (en) * | 2007-05-23 | 2010-02-03 | Kowa Company. Ltd. | Boron adsorbent utilizing sugar amide derivative, and boron removal method |
| EP2149539A4 (en) * | 2007-05-23 | 2011-05-11 | Kowa Co | Boron adsorbent utilizing sugar amide derivative, and boron removal method |
| US8236180B2 (en) | 2007-05-23 | 2012-08-07 | Kowa Company, Ltd. | Boron removal method utilizing sugar amide derivative |
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