US2355837A - Substituted glyoxalidines - Google Patents
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D233/08—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms
- C07D233/12—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D233/16—Radicals substituted by nitrogen atoms
Definitions
- This invention relates to an improved method for making glyoxalidines (imidazolines) which have aminoalkyl or substituted amino-alkyl side chains in addition to containing higher aliphatic substituent radicals.
- the basic reaction with which. the invention is concerned involves the condensation of higher. fatty acid compounds, or mixtures of these, with polyalkylene polyamines having at least three amino groups, at least one of which is a secondary amino group in the 1,2 position to a. primary amino group, to produce substituted glyoxalidines.
- 1,2-disubstituted glyoxalidines may be regarded as dehydration products of substituted ethylene polyamides and fatty acids, or their amides and esters.
- the formation of the slyoxalidin or imidazoline ring from these substances may be considered as a two-step reaction involving, first, the formation of an amide and a molecule of water, and, second, the dehydration of this amide to yield a substituted glyoxalidine and a second molecule of water.
- a fatty acid such as oleic acid
- the new substances, and their salts and soaps, when used as emulsifyi agents, are particularly efilcacious for producing stable dispersions of mineral oils, or other oleaginous substances, and water.
- the production of the 1,2-disubstituted glyoxalidines may be accomplished by dehydrating fatty acid amides of various alkylene polyamines and their substitution products, or, more generally stated, by heating these amines with free fatty that may be used in the production of theglyoxalidines may include the fatty acids themselves, such as laurlc, oleic, linoleic, ricinoleic, stearic and palmitic acids, as well as their amides and esters.
- Z-Substltuted glyoxalidine which this invention is concerned involves the procurement of a high yield of the substituted glyoxalidines without resort to high temperatures, that is, to temperatures above 200 C. These high temperatures are undesirable because they promote the formation of side reactions, the decomposition of the alkylene polyamines, and the formation of tarry by-products. These difliculties become more troublesome in large scale operation because many of the substituted glyoxalidines are Other fatty acids and their esters naturally 00- I5 distillable only on a laboratory scale. which renders burdensome the removal of impurities from glyoxalidines produced at high temperatures of reaction. It has been found that the reaction may be carried out at temperatures below 200 (2.,
- the removal of the water of reaction under a reduced water vapor partial pressure may be effected by 'two procedures.
- One involve the maintenance of a vacuum over the reactants, accompanied, if desired, by the fiow of an inert gas over the reactants.
- I The second involves the removal of the'water as an azeotropic distillate with a water-immiscible, inert, volatile liquid, such as xylene, toluene, propylene dichloride or dibutyl ether.
- the water is separated from the water-removing agent and this liquid is returned to the reaction vessel.
- This invention is to be distinguished from those 1 processes wherein a mixture of ethylene diamine
- the basicity of the reaction medium is provided by the unreacted amino group ofthe polyalkylene polyamine and by the basicity of the resulting glyoxalidines.
- the baslclty of the reaction mixture is preferably assured by the use of amounts of the polyalkylene polyamine in excess of that stoichiometrically required, that is, in excess of one mol of the polyalkylene polyamine. for each fatty acid radicalvof the fatty acid compound, but this is not absolutely essential.
- Example 1 One mol of oleic acid, two mols of diethylene triamine and a quantity of xylene were heated together under a distillation column. The receiver for the distillate from this column was arranged to permit the return to the reaction vessel of one layer of two immiscible liquids. A distillate containing the binary azeotrope of xylene and water was removed continuously whil the reaction mixture was heated at 140 to 160 C., and the xylene which separatedinthe condensed distillate was continuously returned to the vessel. After '12 hours of heating, it was found that the reaction mixture contained 70% of the desired product, l-aminoethyl-Z-heptadecenyl glyoxalidine.
- the purified compound was found to be a pale yellow,-moderately viscous liquid which was practically odorless. It had a-boiling point of from about 246 to 251 C. at an absolute pressure of approximately 1 mm. of mercury. It was strongly basic, stable under most conditions, and soluble in water, 5% hydrochloric acid, and in hydrocar- This compound readily formed salts and soaps with mineral and organic acids.
- the oleic acid scan was found to be a heavy, oily, brownish liquid which was soluble in hydrocarbons.
- Example 2 One mol of distilled commercial cocoanut fatty acids having an equivalent weight of 209 was heated in a kettle having a distilling column with one and one-half mols of diethylene triamine in the presence of a substantial quantity of xylene. An azeotropic mixture of water and xylene was distilled off, the xylene being separated from the water and returned to the kettle as described in the foregoing example. During this operation the temperature gradually rose from 145 to 174 C. At the end of 17 hours, no more water dissoaps with mineral and organic acids.
- the pure base usable as'a commercial product. is obtained as a residueupon distilling off any excess polyalkylene polyamine, and the waterremoving agent, if such a liquid is employed.
- reaction may also be accelerated by the use of smalljamounts of catalysts, exemplified by inorganic fluoride salts; V
- Example 3 One and three-tenths (1.3) mols of tetraethylene pentamine and 0.7 mol of oleic acid were heated in the presence of about 1.2 mols of xylene in the manner described in the foregoing example. The reaction was completed in 7 hours, the temperature rising from an initial one of 130 C. to a final one of 200 C. and 1.3 mols of water being removed during this period. Upon removing the excess amine and the xylene by distilling the reaction mixture to a liquid 1 temperature of 240 C. at 3 mm. of mercury absolute pressure, an almost quantitative yield of l-(aminoethyl di-iminoethylene) 2-heptadecenyl glyoxalidine assess-r was obtained. The product was a clear light- .my copending application Serial No. 191,191, filed brown liquid which formed clear gels with water. It is useful as an inhibitor'of acid corrosion.
- Example 4 Twenty and seven-tenths (20.7) parts of diethylene triamine and 28.3 parts of oleic acid were placed-in a kettle having a distillation column. The charge was slowly heated to 165 C., and sufllcient xylene was added to permit moderate boiling in the kettle. An azeotropic mixture of water and xylene was distilled over, the xylene being returned to the .kettle after separation from the water, until at the end of 15 hours, 92% of the theoretical amount of water had been removed (1.84 mols per mol .of oleic acid). The excess polyamine and xylene were removed by distillation at 184 C. under 1 mm.
- Example 5 after reduced gradually to 1 mm. of mercury during an additional 4.5 hours. The total reaction time, with allowance for minor adjustments, was 6.5 hours and the amount of water removed was 1.86 mols per mol of fatty acid employed.
- the product, 1-aminoethy1-2-heptadecyl lyoxalidine was a yellow solid which was soluble in dilute hydrochloric acid. It also formed soluble salts and soaps with mineral and organic acids.
- Example 6 The apparatus was the same as that described in the preceding example. Sixty parts by weight of oleic acid and 33 parts by weight of diethylene triamine containing 0.022 part by weight of calcium fluoride as a catalyst were placed in the kettle and agitated for 15 minutes with nitrogen. The kettle was then heated to 165.5 C. in a period of three hours and some water was distilled over. To effect the removal of the remainder of the water, 111.5 parts by weight of xylene were then added to the receiver and kettle. The azeotropic distillation was continued for 3.75 hours. until a maximum kettle temperature of 167 C. and a column temperature of 143 C. were reached, at which time approximately 2 mols of water per mol of the fatty acid had been removed.
- Process for making 1,2-substituted glyoxalidines which comprises heating a mixture containing a polyalkylene polyamine having at least three amino groups, at least one of which is a secondary amino group in the 1,2 position relative to a primary amino group, and at least one of the group consisting of free fatty acids containing from 10 to 20 carbon atoms, amides of said acids, and esters of said acids, at least one mol of said polyamine being present for each fatty acid radical of one of said group; carrying out the reaction at temperatures between 140 C.
- Process for making 1,2-substituted glyoxalidines which comprises heating a mixture containing a polyaliwlene polyamine having at least three amino groups, at least one of which is a secondary amino group in the 1,2 position relative to a primary aminogroup, and at least one of the group consisting of free fatty acids containing from 10 to 20 carbon atoms, amides of said acids, and esters of said acids, at least one mol of said polyamine being present for each fatty acid radical of one of said group; carrying out the reaction at temperatures between 140 C.
- l-aminoethrl-Z-heptadecenyl giyoxalidine which comprises heating a mixture containing dlethylene triamine and oieic acid, the molar ratio of amine to acid being appreciably greater than one and said amine being substantially free from inorganic salt groups, the heating being carried out at a temperature between 140 and 200 C. and in the presence or a liquid aromatic hydrocarbon, the temperature and duration or said heating being so correlated so as to cause the splitting out 01 water in excess of 1.5 mols per moi of acid, and distilling at least 0.5 moi of such water from said mixture during such heating as an azeotropic composition with said hydrocarbon.
- Process for making i-aminoethyl-z-heptadecyl glyoxalidine which comprises heating a mixture containing diethylene triamine and stearic acid. the molar ratio of amine to acid being appreciably greater than one and said amine being substantially tree from inorganic salt groups, the heating being carried out at a temperature between 140 and 200 C. and win the presence of a liquid aromatic hydrocarbon. the temperature and duration oi said heating being so correlated so as to cause the splitting out of water in excess of 1.5 mols per moi of acid, and
- Process tor making i-aminoethyl-Z-undecyl giyoxalidine which comprises heating a mixture containing diethylene triamine and lauric acid, the molar ratio of amine to acid being appreciably greater than one and said amine bein substantially free from inorganic salt groups, the heating being carried out at a temperature between 140 and 200 C. and in the presence or a liquid aromatic hydrocarbon. the temperature and duration of said heating being so correlated so as to cause the splitting out of water in excess of 1.5 mols per mol of acid, and distilling at least 0.5 mol of such water from said mixture during such heating as an azeotropic composition with said hydrocarbon.
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Description
Patented Aug. 15, 1944 SUBSTITUTED GLYOXALIDINES Alexander L. Wilson, Sharpsburg, Pa, assignor to Carbide and Carbon Chemicals Corporation, a corporation of New York No Drawing. Application March 17, 1942,
Serial No. 435,049
6 Claims.
This invention'relates to an improved method for making glyoxalidines (imidazolines) which have aminoalkyl or substituted amino-alkyl side chains in addition to containing higher aliphatic substituent radicals. The basic reaction with which. the invention is concerned involves the condensation of higher. fatty acid compounds, or mixtures of these, with polyalkylene polyamines having at least three amino groups, at least one of which is a secondary amino group in the 1,2 position to a. primary amino group, to produce substituted glyoxalidines. While it is possible by this process to obtain trl-, or even tetrasubstituted glyoxalidines, the production of the 1,2-disubstituted glyoxalidines is the primary object of the invention.
These'compounds are characterized as being either high-boiling, viscous liquids, or low-meltcurring in such vegetable oils as olive, cocoanut. linseed and cottonseed oils, which have from 10 to carbon atoms in their molecule, may also be employed.
1,2-disubstituted glyoxalidines may be regarded as dehydration products of substituted ethylene polyamides and fatty acids, or their amides and esters. The formation of the slyoxalidin or imidazoline ring from these substances may be considered as a two-step reaction involving, first, the formation of an amide and a molecule of water, and, second, the dehydration of this amide to yield a substituted glyoxalidine and a second molecule of water. Thus, when a fatty acid, such as oleic acid, is employed, two molecules of water will be formed per molecule of the starting acid. This reaction is illustrated by the following scheme:
ing, waxy solids. They are highly polar, strongly 0 basic substances, which are soluble in water and 20 II in acids, such as dilute hydrochloric acid. 13- disubstituted glyoxalidines, when pure, are almost F n l 1 odorless, and they are stable under most condi- 2 tions.
The glyoxalidine compounds of this invention may be used for various purposes, and it has been found that they are especially valuable as emulsifying agents and detergents, as wetting, softening and scouring agents, and for other uses where their properties of surface activity can be em= ployed. The new substances, and their salts and soaps, when used as emulsifyi agents, are particularly efilcacious for producing stable dispersions of mineral oils, or other oleaginous substances, and water.
The production of the 1,2-disubstituted glyoxalidines may be accomplished by dehydrating fatty acid amides of various alkylene polyamines and their substitution products, or, more generally stated, by heating these amines with free fatty that may be used in the production of theglyoxalidines may include the fatty acids themselves, such as laurlc, oleic, linoleic, ricinoleic, stearic and palmitic acids, as well as their amides and esters.
I Alkylene polyamine Amide R-C HN R:N 5 H. R
1, Z-Substltuted glyoxalidine which this invention is concerned involves the procurement of a high yield of the substituted glyoxalidines without resort to high temperatures, that is, to temperatures above 200 C. These high temperatures are undesirable because they promote the formation of side reactions, the decomposition of the alkylene polyamines, and the formation of tarry by-products. These difliculties become more troublesome in large scale operation because many of the substituted glyoxalidines are Other fatty acids and their esters naturally 00- I5 distillable only on a laboratory scale. which renders burdensome the removal of impurities from glyoxalidines produced at high temperatures of reaction. It has been found that the reaction may be carried out at temperatures below 200 (2.,
' and a high yield of a pure substituted glyoxalidine obtained, if at least 0.5 mol of the water of reaction per mol of fatty acid compound is removed at a water vapor partial pressure reduced from that naturally prevailing at the surface of the reactants under the conditions of the reaction. If a free fatty acid is reacted, it is not necessary to reduce the water vapor partial pressure during the removal of the first mol of water per mol of the fatty acid. .but it is essential to remove in this manner the water split off in the glyoxalidineforming stage of the reaction, irrespective of whether the fatty acid employed is free or combined.
The removal of the water of reaction under a reduced water vapor partial pressure may be effected by 'two procedures. One involve the maintenance of a vacuum over the reactants, accompanied, if desired, by the fiow of an inert gas over the reactants. I The second involves the removal of the'water as an azeotropic distillate with a water-immiscible, inert, volatile liquid, such as xylene, toluene, propylene dichloride or dibutyl ether. -In this embodiment, the water is separated from the water-removing agent and this liquid is returned to the reaction vessel. This invention is to be distinguished from those 1 processes wherein a mixture of ethylene diamine The basicity of the reaction medium is provided by the unreacted amino group ofthe polyalkylene polyamine and by the basicity of the resulting glyoxalidines. The baslclty of the reaction mixture is preferably assured by the use of amounts of the polyalkylene polyamine in excess of that stoichiometrically required, that is, in excess of one mol of the polyalkylene polyamine. for each fatty acid radicalvof the fatty acid compound, but this is not absolutely essential. It is entirely surprising to, find that a ringforming reaction ofthis type would occur in a basic 'medium, and it it wholly unexpected'to discover that,y.under the appropriate conditionsfor removal of'the water of reaction, the reaction could be carried out at temperatures below 200C. .and high yields of a useful product obtained. It has been definitely established that the process of this invention results in a purer product obtained at a higher yield, than do those bons.
games? such as sodium fluoride, potassium fluoride and calcium fluoride.
The examples to follow will serve to illustrate the invention:
Example 1 One mol of oleic acid, two mols of diethylene triamine and a quantity of xylene were heated together under a distillation column. The receiver for the distillate from this column was arranged to permit the return to the reaction vessel of one layer of two immiscible liquids. A distillate containing the binary azeotrope of xylene and water was removed continuously whil the reaction mixture was heated at 140 to 160 C., and the xylene which separatedinthe condensed distillate was continuously returned to the vessel. After '12 hours of heating, it was found that the reaction mixture contained 70% of the desired product, l-aminoethyl-Z-heptadecenyl glyoxalidine.
The purified compound was found to be a pale yellow,-moderately viscous liquid which was practically odorless. It had a-boiling point of from about 246 to 251 C. at an absolute pressure of approximately 1 mm. of mercury. It was strongly basic, stable under most conditions, and soluble in water, 5% hydrochloric acid, and in hydrocar- This compound readily formed salts and soaps with mineral and organic acids. The oleic acid scan was found to be a heavy, oily, brownish liquid which was soluble in hydrocarbons.
Example 2 One mol of distilled commercial cocoanut fatty acids having an equivalent weight of 209 was heated in a kettle having a distilling column with one and one-half mols of diethylene triamine in the presence of a substantial quantity of xylene. An azeotropic mixture of water and xylene was distilled off, the xylene being separated from the water and returned to the kettle as described in the foregoing example. During this operation the temperature gradually rose from 145 to 174 C. At the end of 17 hours, no more water dissoaps with mineral and organic acids.
ther advantageof the improved process is that.
the pure base, usable as'a commercial product. is obtained as a residueupon distilling off any excess polyalkylene polyamine, and the waterremoving agent, ifsuch a liquid is employed.
Thus, no difllculty in separating the product from its salt is encountered. In addition, loss of the polyalkylene polyamine, which tends to occur through deammoniation caused by the mineral acid, is avoided.
of water removal employed. The reaction may also be accelerated by the use of smalljamounts of catalysts, exemplified by inorganic fluoride salts; V
tilled over, and after removal of the excess xylene and amine, a residue substantially consisting of l-aminoethyl-Z-undecyl glyoxalidine was obtained, 78% of which'w'as distillable at 2 mm. of mercury absolute pressure at a temperature under 210 C. When purified, this material was a yellow, viscous liquid, soluble in water and dilute hydrochloric acid, and it also formed salts and It boiled at from about to about C. at an absolute pressure of about 1 mm. of mercury.
Example 3 One and three-tenths (1.3) mols of tetraethylene pentamine and 0.7 mol of oleic acid were heated in the presence of about 1.2 mols of xylene in the manner described in the foregoing example. The reaction was completed in 7 hours, the temperature rising from an initial one of 130 C. to a final one of 200 C. and 1.3 mols of water being removed during this period. Upon removing the excess amine and the xylene by distilling the reaction mixture to a liquid 1 temperature of 240 C. at 3 mm. of mercury absolute pressure, an almost quantitative yield of l-(aminoethyl di-iminoethylene) 2-heptadecenyl glyoxalidine assess-r was obtained. The product was a clear light- .my copending application Serial No. 191,191, filed brown liquid which formed clear gels with water. It is useful as an inhibitor'of acid corrosion.
If larger quantities of fatty acid are employed than shown in this example, it is possible that at least small amounts of products which contain two glyoxalidine rings may be formed by condensation at both ends of the polyalkylene polyamine.
Example 4 Twenty and seven-tenths (20.7) parts of diethylene triamine and 28.3 parts of oleic acid were placed-in a kettle having a distillation column. The charge was slowly heated to 165 C., and sufllcient xylene was added to permit moderate boiling in the kettle. An azeotropic mixture of water and xylene was distilled over, the xylene being returned to the .kettle after separation from the water, until at the end of 15 hours, 92% of the theoretical amount of water had been removed (1.84 mols per mol .of oleic acid). The excess polyamine and xylene were removed by distillation at 184 C. under 1 mm.
.-.of mercury absolute pressure, and 33.56 parts of the product l-aminoethyl-2-heptadecenyl glyoxalidine were obtained at .a yield of 95.7%
of the theoretical.
Example 5 after reduced gradually to 1 mm. of mercury during an additional 4.5 hours. The total reaction time, with allowance for minor adjustments, was 6.5 hours and the amount of water removed was 1.86 mols per mol of fatty acid employed. The product, 1-aminoethy1-2-heptadecyl lyoxalidine was a yellow solid which was soluble in dilute hydrochloric acid. It also formed soluble salts and soaps with mineral and organic acids.
Example 6 The apparatus was the same as that described in the preceding example. Sixty parts by weight of oleic acid and 33 parts by weight of diethylene triamine containing 0.022 part by weight of calcium fluoride as a catalyst were placed in the kettle and agitated for 15 minutes with nitrogen. The kettle was then heated to 165.5 C. in a period of three hours and some water was distilled over. To effect the removal of the remainder of the water, 111.5 parts by weight of xylene were then added to the receiver and kettle. The azeotropic distillation was continued for 3.75 hours. until a maximum kettle temperature of 167 C. and a column temperature of 143 C. were reached, at which time approximately 2 mols of water per mol of the fatty acid had been removed. The xylene and excess polyamine were then removed by distillation at a maximum column temperature of 81 C. under 5 mm. of mercury absolute pressure. The product remaining as a residue, 1-aminoethyl-2-heptadecenyl glyoxalidine, amounted to 68.56 parts by weight. This corresponds to a yield of 92.5%.
This. application is a continuation-in-part of group consisting of free fatty acids containing from 10 to 20 carbon atoms, amides of said acids. and esters of said acids, at least one mol of said polyamine being present for each fatty acid radical of one of said group; carrying out the reaction at temperatures between C. and 200 0., under basic amine conditions in the absence of mineral acid salt groups attached to the polyamine, and in the presence of an inert waterimmiscible organic liquid and distilling an azeotropic mixture of the water formed in the reaction and said liquid from said mixture during said heating: the temperature and duration of said heating being so correlated as to cause the splitting out of water in excess of 1.5 mols for each mol of free fatty acid and in excess of 0.5 mol for each mol of combined fatty acid involved.
2. Process for making 1,2-substituted glyoxalidines which comprises heating a mixture containing a polyalkylene polyamine having at least three amino groups, at least one of which is a secondary amino group in the 1,2 position relative to a primary amino group, and at least one of the group consisting of free fatty acids containing from 10 to 20 carbon atoms, amides of said acids, and esters of said acids, at least one mol of said polyamine being present for each fatty acid radical of one of said group; carrying out the reaction at temperatures between 140 C. and 200 C., under basic amine conditions in the absence of mineral acid salt groups attached to the polyamine, and in the presence of xylene: and distilling an azeotropic mixture of the water formed in the reaction and xylene from said mixture during said heating; the temperature and duration of said heating being so correlated as to cause the splitting out of water in excess of 1.5 mols for each mol of free fatty acid and in excess of 0.5 mol for each mol of combined fatty acid involved.
3. Process for making 1,2-substituted glyoxalidines which comprises heating a mixture containing a polyaliwlene polyamine having at least three amino groups, at least one of which is a secondary amino group in the 1,2 position relative to a primary aminogroup, and at least one of the group consisting of free fatty acids containing from 10 to 20 carbon atoms, amides of said acids, and esters of said acids, at least one mol of said polyamine being present for each fatty acid radical of one of said group; carrying out the reaction at temperatures between 140 C. and 200 C., under basic amine conditions in the absence of mineral acid salt groups attached to the polyamine, and in the presence ofa catalytic amount of an inorganic fluoride salt and of an inert water-immiscible organic liquid; and distilling an azeotropic mixture of the water formed in the reaction and said liquid from said mixture during said heating; the temperature and duration of said heating being so correlated as to cause the splitting out of water in excess of 1.5 mols for each mol of free fatty acid and in excess of 0.5 mol for each mol of combined fatty acid involved.
4. as for making l-aminoethrl-Z-heptadecenyl giyoxalidine which comprises heating a mixture containing dlethylene triamine and oieic acid, the molar ratio of amine to acid being appreciably greater than one and said amine being substantially free from inorganic salt groups, the heating being carried out at a temperature between 140 and 200 C. and in the presence or a liquid aromatic hydrocarbon, the temperature and duration or said heating being so correlated so as to cause the splitting out 01 water in excess of 1.5 mols per moi of acid, and distilling at least 0.5 moi of such water from said mixture during such heating as an azeotropic composition with said hydrocarbon.
5. Process for making i-aminoethyl-z-heptadecyl glyoxalidine which comprises heating a mixture containing diethylene triamine and stearic acid. the molar ratio of amine to acid being appreciably greater than one and said amine being substantially tree from inorganic salt groups, the heating being carried out at a temperature between 140 and 200 C. and win the presence of a liquid aromatic hydrocarbon. the temperature and duration oi said heating being so correlated so as to cause the splitting out of water in excess of 1.5 mols per moi of acid, and
distilling at least 0.5 mol of such water from said mixture during such heating as an azeotropic composition with said hydrocarbon.
6. Process tor making i-aminoethyl-Z-undecyl giyoxalidine which comprises heating a mixture containing diethylene triamine and lauric acid, the molar ratio of amine to acid being appreciably greater than one and said amine bein substantially free from inorganic salt groups, the heating being carried out at a temperature between 140 and 200 C. and in the presence or a liquid aromatic hydrocarbon. the temperature and duration of said heating being so correlated so as to cause the splitting out of water in excess of 1.5 mols per mol of acid, and distilling at least 0.5 mol of such water from said mixture during such heating as an azeotropic composition with said hydrocarbon.
ALEXANDER L. WILSON.
CERTIFICATE OF CORRECTION. P tent No. 2,555,857. 7 August 1 1911;.
V ALEXANDER L. WILSON.
It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, sec- ,ond. column, line 7, for "poly a'mides read --po.1yamines--; page 2, first column, line 1+8, for "it it" read "it is--; and that the said Letters Patent should be read with this correction therein that the same may eonmm to the record of the case in the Patent Office.
Signed'and sealed this 3rd day of October, A. D. 19%.
Leslie Frazer (Seal) Acting Commissioner of Patents.
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US2484146A (en) * | 1945-04-07 | 1949-10-11 | Houghton & Co E F | Lubricating composition |
US2528380A (en) * | 1948-10-29 | 1950-10-31 | John J Mccabe Jr | Cycloimidine derivatives and methods for preparing them |
US2528379A (en) * | 1948-10-07 | 1950-10-31 | John J Mccabe Jr | Cycloimidine derivatives and methods for preparing them |
US2541825A (en) * | 1951-02-13 | Coating compositions containing | ||
US2567281A (en) * | 1948-02-06 | 1951-09-11 | Sun Chemical Corp | Flushed methyl violet inks |
US2568876A (en) * | 1949-11-14 | 1951-09-25 | Socony Vacuum Oil Co Inc | Reaction products of n-acylated polyalkylene-polyamines with alkenyl succinic acid anhydrides |
US2622067A (en) * | 1949-09-15 | 1952-12-16 | Socony Vacuum Oil Co Inc | Emulsifiable oil compositions |
DE1011580B (en) * | 1953-11-17 | 1957-07-04 | Ciba Geigy | Cationic shampoos |
US2874074A (en) * | 1956-05-08 | 1959-02-17 | Nat Aluminate Corp | 1, 2-substituted imidazolinium salt and treatment of cellulosic fibrous materials therewith |
US2950211A (en) * | 1957-03-06 | 1960-08-23 | Cincinnati Milling Machine Co | Heterocyclic asphalt additives |
US2974106A (en) * | 1955-12-02 | 1961-03-07 | Comcolloid Inc | Emulsifier-wax compositions |
US2995520A (en) * | 1956-06-11 | 1961-08-08 | Nalco Chemical Co | Treatment of fibrous materials and compositions therefor |
US3003969A (en) * | 1953-11-17 | 1961-10-10 | Ciba Ltd | Detergent compositions for the hair |
US3159502A (en) * | 1962-07-16 | 1964-12-01 | Houghton & Co E F | Soil resistant carpet fibers |
US3202674A (en) * | 1960-03-05 | 1965-08-24 | American Home Prod | Phenethylamine derivatives |
US3205092A (en) * | 1962-02-20 | 1965-09-07 | Geigy Chem Corp | Magnetic tape having improved antistatic properties |
US3216935A (en) * | 1962-08-22 | 1965-11-09 | Exxon Research Engineering Co | Lubricant |
US3231495A (en) * | 1962-08-22 | 1966-01-25 | Exxon Research Engineering Co | Finely divided calcium acetate particles and lubricating compositions thereof |
US3231494A (en) * | 1961-08-22 | 1966-01-25 | Exxon Research Engineering Co | Rust preventive prepared from sodium nitrite and the reaction product of fatty acid and imidazoline |
US3251853A (en) * | 1962-02-02 | 1966-05-17 | Lubrizol Corp | Oil-soluble acylated amine |
US3317556A (en) * | 1962-06-22 | 1967-05-02 | Nopco Chem Co | Amphoteric alpha-sulfo-imidazolines |
US3340206A (en) * | 1964-12-22 | 1967-09-05 | Exxon Research Engineering Co | Method of forming finely divided inorganic acid salts |
US3979323A (en) * | 1973-08-20 | 1976-09-07 | John Spahr | Method of making a bituminous emulsion |
DE2721847A1 (en) * | 1976-05-20 | 1977-12-01 | Procter & Gamble | PROCESS FOR THE PRODUCTION OF QUATERNAER IMIDAZOLINIUM SALTS, COMPOSITIONS FOR CONDITIONING TEXTILES AND TEXTILE CONDITIONING PROCESSES |
US4095941A (en) * | 1974-10-04 | 1978-06-20 | Hoechst Aktiengesellschaft | Fiber preparation agents to produce a marked separating capability |
US4212983A (en) * | 1977-12-22 | 1980-07-15 | Albright & Wilson Limited | Manufacture of imidazoline compounds |
FR2583752A1 (en) * | 1985-06-19 | 1986-12-26 | Kao Corp | PROCESS FOR THE PREPARATION OF 1,2-SUBSTITUTED IMIDAZOLINE COMPOUNDS |
US4752381A (en) * | 1987-05-18 | 1988-06-21 | Nalco Chemical Company | Upgrading petroleum and petroleum fractions |
US4758672A (en) * | 1987-05-18 | 1988-07-19 | Nalco Chemical Company | Process for preparing naphthenic acid 1,2-imidazolines |
US4827033A (en) * | 1987-05-18 | 1989-05-02 | Nalco Chemical Company | naphthenic acid amides |
US5334639A (en) * | 1992-01-30 | 1994-08-02 | Ppg Industries, Inc. | Starch oil sizing composition and glass fibers treated therewith |
US5393379A (en) * | 1990-12-05 | 1995-02-28 | Ppg Industries, Inc. | Wet laid fiberous thermoplastic material and aqueous dispersion for producing same |
US5466528A (en) * | 1992-08-21 | 1995-11-14 | Ppg Industries, Inc. | Chemically treated glass type substrates with vinyl polymer compatibility |
WO2014178737A1 (en) | 2013-05-02 | 2014-11-06 | Instytut Nafty I Gazu - Panstwowy Instytut Badawczy | Corrosion inhibitor for protection of crude oil extraction equipment, crude oil pipelines, and crude oil tanks as well as the method of its production |
WO2014178738A1 (en) | 2013-05-02 | 2014-11-06 | Instytut Nafty I Gazu - Panstwowy Instytut Badawczy | Water-soluble corrosion inhibitor for protection of lifting casings and natural gas pipelines as well as the method of its production. |
-
1942
- 1942-03-17 US US435049A patent/US2355837A/en not_active Expired - Lifetime
Cited By (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2541825A (en) * | 1951-02-13 | Coating compositions containing | ||
US2484146A (en) * | 1945-04-07 | 1949-10-11 | Houghton & Co E F | Lubricating composition |
US2567281A (en) * | 1948-02-06 | 1951-09-11 | Sun Chemical Corp | Flushed methyl violet inks |
US2528379A (en) * | 1948-10-07 | 1950-10-31 | John J Mccabe Jr | Cycloimidine derivatives and methods for preparing them |
US2528380A (en) * | 1948-10-29 | 1950-10-31 | John J Mccabe Jr | Cycloimidine derivatives and methods for preparing them |
US2622067A (en) * | 1949-09-15 | 1952-12-16 | Socony Vacuum Oil Co Inc | Emulsifiable oil compositions |
US2568876A (en) * | 1949-11-14 | 1951-09-25 | Socony Vacuum Oil Co Inc | Reaction products of n-acylated polyalkylene-polyamines with alkenyl succinic acid anhydrides |
US3003969A (en) * | 1953-11-17 | 1961-10-10 | Ciba Ltd | Detergent compositions for the hair |
DE1011580B (en) * | 1953-11-17 | 1957-07-04 | Ciba Geigy | Cationic shampoos |
US2974106A (en) * | 1955-12-02 | 1961-03-07 | Comcolloid Inc | Emulsifier-wax compositions |
US2874074A (en) * | 1956-05-08 | 1959-02-17 | Nat Aluminate Corp | 1, 2-substituted imidazolinium salt and treatment of cellulosic fibrous materials therewith |
US2995520A (en) * | 1956-06-11 | 1961-08-08 | Nalco Chemical Co | Treatment of fibrous materials and compositions therefor |
US2950211A (en) * | 1957-03-06 | 1960-08-23 | Cincinnati Milling Machine Co | Heterocyclic asphalt additives |
US3202674A (en) * | 1960-03-05 | 1965-08-24 | American Home Prod | Phenethylamine derivatives |
US3231494A (en) * | 1961-08-22 | 1966-01-25 | Exxon Research Engineering Co | Rust preventive prepared from sodium nitrite and the reaction product of fatty acid and imidazoline |
US3251853A (en) * | 1962-02-02 | 1966-05-17 | Lubrizol Corp | Oil-soluble acylated amine |
US3205092A (en) * | 1962-02-20 | 1965-09-07 | Geigy Chem Corp | Magnetic tape having improved antistatic properties |
US3317556A (en) * | 1962-06-22 | 1967-05-02 | Nopco Chem Co | Amphoteric alpha-sulfo-imidazolines |
US3159502A (en) * | 1962-07-16 | 1964-12-01 | Houghton & Co E F | Soil resistant carpet fibers |
US3216935A (en) * | 1962-08-22 | 1965-11-09 | Exxon Research Engineering Co | Lubricant |
US3231495A (en) * | 1962-08-22 | 1966-01-25 | Exxon Research Engineering Co | Finely divided calcium acetate particles and lubricating compositions thereof |
US3340206A (en) * | 1964-12-22 | 1967-09-05 | Exxon Research Engineering Co | Method of forming finely divided inorganic acid salts |
US3979323A (en) * | 1973-08-20 | 1976-09-07 | John Spahr | Method of making a bituminous emulsion |
US4095941A (en) * | 1974-10-04 | 1978-06-20 | Hoechst Aktiengesellschaft | Fiber preparation agents to produce a marked separating capability |
DE2721847A1 (en) * | 1976-05-20 | 1977-12-01 | Procter & Gamble | PROCESS FOR THE PRODUCTION OF QUATERNAER IMIDAZOLINIUM SALTS, COMPOSITIONS FOR CONDITIONING TEXTILES AND TEXTILE CONDITIONING PROCESSES |
US4212983A (en) * | 1977-12-22 | 1980-07-15 | Albright & Wilson Limited | Manufacture of imidazoline compounds |
FR2583752A1 (en) * | 1985-06-19 | 1986-12-26 | Kao Corp | PROCESS FOR THE PREPARATION OF 1,2-SUBSTITUTED IMIDAZOLINE COMPOUNDS |
US4752381A (en) * | 1987-05-18 | 1988-06-21 | Nalco Chemical Company | Upgrading petroleum and petroleum fractions |
US4758672A (en) * | 1987-05-18 | 1988-07-19 | Nalco Chemical Company | Process for preparing naphthenic acid 1,2-imidazolines |
US4827033A (en) * | 1987-05-18 | 1989-05-02 | Nalco Chemical Company | naphthenic acid amides |
US5393379A (en) * | 1990-12-05 | 1995-02-28 | Ppg Industries, Inc. | Wet laid fiberous thermoplastic material and aqueous dispersion for producing same |
US5334639A (en) * | 1992-01-30 | 1994-08-02 | Ppg Industries, Inc. | Starch oil sizing composition and glass fibers treated therewith |
US5466528A (en) * | 1992-08-21 | 1995-11-14 | Ppg Industries, Inc. | Chemically treated glass type substrates with vinyl polymer compatibility |
WO2014178737A1 (en) | 2013-05-02 | 2014-11-06 | Instytut Nafty I Gazu - Panstwowy Instytut Badawczy | Corrosion inhibitor for protection of crude oil extraction equipment, crude oil pipelines, and crude oil tanks as well as the method of its production |
WO2014178738A1 (en) | 2013-05-02 | 2014-11-06 | Instytut Nafty I Gazu - Panstwowy Instytut Badawczy | Water-soluble corrosion inhibitor for protection of lifting casings and natural gas pipelines as well as the method of its production. |
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