LINEAR AMINO ACID SURFACTANTS HAVING SURFACE-ACTIVE PROPERTIES
Derivatives of amino acids that have surface-active properties are provided. The amino acid can be naturally occurring or synthetic, or they may be obtained via a ring-opening reaction of a lactam, such as caprolactam. The amino acid can be naturally occurring or synthetic, or they may be obtained via a ring-opening reaction of a lactam, such as caprolactam. The amino acid may be functionalized to form a compound that is surface-active and have advantageous surfactant characteristics. The compounds of the present disclosure have low critical micelle concentrations (CMC) as well as superior ability to lower the surface tension at an interface of otherwise immiscible phases of materials.
1 . A compound of Formula I, wherein the compound of Formula I can be a salt, below:
wherein Y is selected from formula (1-1), (1-2), or (1-3)
the wave-line denoting the connection to Formula I;
wherein
R 1 and R 2 form a ring that may be substituted or unsubstituted, saturated or unsaturated; optionally the ring may include one or more of oxygen, nitrogen, or sulfur atoms or groups that include at least one of these atoms at any suitable position on the ring, and the ring may be optionally substituted with one or more substituents selected from the group consisting of one of C 1 -C 6 alkyl, hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate;
wherein the ring formed from R 1 and R 2 is optionally linked and/or fused to a further ring;
R 3 is selected from the group consisting of hydrogen, one of C 1 -C 6 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 2 -C 12 ester, hydroxyl, C 1 -C 10 hydroxyl, aryl alkyl, C 2 -C 12 alkoxy alkyl ether, alkyl phosphate, C 3 -C 8 carboxylic acid, C 1 -C 10 alkyl benzoic acid, oxygen, and sulfur;
R 4 and R 5 may be the same or different, and are selected from the group consisting of hydrogen and one of C 1 -C 6 alkyl, wherein the C 1 -C 6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate;
R 6 is and is selected from the group consisting of C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 2 -C 12 ester, hydroxyl, aryl alkyl, C 2 C 12 alkoxy alkyl ether, alkyl phosphate, C 3 -C 8 carboxylic acid, C 1 -C 10 alkyl benzoic acid, amino, amido, and sulfur; wherein R 6 may optionally be substituted with one or more substituents selected from the group consisting of aryl, heteroaryl, hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate;
R 7 and R 8 may be the same or different, and are selected from the group consisting of hydrogen and one of C 1 -C 6 alkyl, wherein the C 1 -C 6 alkyl is substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate, or a salt thereof, wherein a counterion W associated with any of the hydroxyl, sulfonate, or carboxylate group is selected from Na, K or Ca;
X is selected from the group consisting of chloride, bromide, and iodide,
n is an integer in the range of 2 to 5; and
m is an integer in the range of 9 to 20.
2 . The compound of claim 1 , wherein Y is selected from piperidine, pyridine, pyrimidine, pyrrole, imidazole, pyrazole, piperazine, or morpholine.
3 . The compound of claim 1 , wherein Y is:
wherein:
R 15 is either not present, or an oxygen, hydrogen, one of C 1 -C 6 alkyl, or one of C 1 -C 6 heteroalkyl;
Z is 0, S, NR 16 R 17 , or CR 18 R 19
n is an integer in the range of 2 to 5 and m is an integer in the range of 9 to 20;
X is selected from the group consisting of chloride, bromide, and iodide; and
R 16 and R 17 are each independently hydrogen or one of C 1 -C 6 alkyl;
R 18 and R 19 are each independently either not present, or a hydrogen, or one of C 1 -C 6 alkyl;
are single bonds or double bonds; and
wherein the ring may be optionally substituted with one or more substituents selected from the group consisting of one of C 1 -C 6 alkyl, hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate.
4 . The compound of claim 1 , wherein R 3 and/or R 15 is oxygen.
5 . The compound of claim 1 , wherein R 3 and/or R 15 is C 1 -C 6 alkyl or C 1 -C 6 heteroalkyl.
6 . The compound of claim 1 , wherein R 3 and/or R 15 is C 1 -C 6 alkyl substituted with hydroxy.
7 . The compound of claim 3 , wherein R 17 is methyl.
8 . The compound of claim 3 , wherein R 19 is hydrogen.
9 . The compound of claim 1 , wherein Y is:
R 20 and R 21 are each independently methyl or a hydrogen;
n is an integer in the range of 2 to 5 and m is an integer in the range of 9 to 20;
X is selected from the group consisting of chloride, bromide, and iodide;
R 22 is selected from the group consisting of C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 2 -C 12 ester, hydroxyl, aryl C 1 -C 6 alkyl, C 2 -C 12 alkoxy alkyl ether, C 1 -C 6 alkyl phosphate, C 3 -C 8 carboxylic acid, C 1 -C 10 alkyl benzoic acid, amino, amido, and sulfur; wherein R 22 may optionally be substituted with one or more substituents selected from the group consisting of aryl, heteroaryl, hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate.
10 . The compound of claim 1 , wherein Y is selected from:
11 . The compound of claim 1 , wherein Y is selected from:
12 . The compound of claim 1 , wherein n is 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
13 . The compound of claim 1 , wherein n is 5.
14 . The compound of claim 1 , wherein the counterion is present and is selected from the group consisting of chloride, bromide, and iodide.
15 . The compound of claim 1 , wherein the counterion is chloride.
16 . The compound of claim 1 , wherein the counterion is iodide.
17 . The compound of claim 1 , wherein the compound is selected from the group consisting of:
1-(6-(dodecyloxy)-6-oxohexyl)pyridin-1-ium bromide:
4-(6-(dodecyloxy)-6-oxohexyl)-4-(3-hydroxypropyl)morpholin-4-ium iodide:
1-(6-(dodecyloxy)-6-oxohexyl)piperidin-1-ium chloride:
4-(6-(dodecyloxy)-6-oxohexyl)morpholin-4-ium chloride:
1-(6-(dodecyloxy)-6-oxohexyl)-4-methylpiperazine-1,4-diium dichloride:
4-(6-(dodecyloxy)-6-oxohexyl)morpholine 4-oxide:
N-allyl-6-(dodecyloxy)-N,N-dimethyl-6-oxohexan-1-aminium iodide:
6-(dodecyloxy)-N-(2-hydroxyethyl)-N,N-dimethyl-6-oxohexan-1-aminium iodide:
6-(dodecyloxy)-N-(2-ethoxy-2-oxoethyl)-N,N-dimethyl-6-oxohexan-1-aminium bromide:
6-(dodecyloxy)-N,N-dimethyl-6-oxo-N-(prop-2-yn-1-yl)hexan-1-aminium bromide:
6-(dodecyloxy)-N-(3-hydroxypropyl)-N,N-dimethyl-6-oxohexan-1-aminium iodide:
N-(2-(dimethylamino)-2-oxoethyl)-6-(dodecyloxy)-N,N-dimethyl-6-oxohexan-1-aminium iodide:
N-benzyl-6-(dodecyloxy)-N,N-dimethyl-6-oxohexan-1-aminium bromide:
6-(dodecyloxy)-N-(2-(2-methoxyethoxy)ethyl)-N,N-dimethyl-6-oxohexan-1-aminium bromide:
6-(dodecyloxy)-N,N-dimethyl-6-oxo-N-phenethylhexan-1-aminium iodide:
N-(2-(dimethylamino)-2-oxoethyl)-6-(dodecyloxy)-N-methyl-6-oxohexan-1-aminium chloride:
sodium 4-((6-(dodecyloxy)-6-oxohexyl)(methyl)amino)butane-1-sulfonate:
sodium 5-((6-(dodecyloxy)-6-oxohexyl)(methyl)amino)pentanoate:
sodium 5-((6-(dodecyloxy)-6-oxohexyl)amino)pentanoate:
sodium 4-((6-(dodecyloxy)-6-oxohexyl)amino)butane-1-sulfonate:
dodecyl 6-(2,3,4,5,6-pentahydroxy-N-methylhexanamido)hexanoate; and
combinations of the foregoing.
18 . A compound of Formula II, wherein the compound of Formula II can be a salt, below:
R 9 , R 10 , may be the same or different, and are selected from the group consisting of hydrogen and C 1 -C 6 alkyl, wherein the C 1 -C 6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate, optionally, R 9 and R 10 are linked or otherwise connected together to form a 4 to 20 membered ring that may be substituted or unsubstituted, saturated or unsaturated; optionally the ring may include one or more of oxygen, nitrogen, or sulfur atoms or groups that include at least one of these atoms at any suitable position on the ring, and the ring may be optionally substituted with one or more substituents selected from the group consisting of any one of C 1 -C 6 alkyl, hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate, wherein the ring formed from R 9 is optionally linked and/or fused to a further ring;
R 11 , R 12 are optionally present, and if present are the same or different, and are selected from the group consisting of hydrogen and C 1 -C 6 alkyl, wherein the C 1 -C 6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate;
if R 11 and R 12 are present, a counter ion Z is selected from the group consisting of chloride, bromide, and iodide.
R 13 is selected from the group consisting of one of C 1 -C 6 alkyl, wherein the C 1 -C 6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate;
Z is selected from the group consisting of chloride, bromide, and iodide.
n and z are, independently, an integer fin the range of 2 to 5; and
m is an integer in the range of 9 to 20.
19 . The compound of claim 18 , wherein R 9 and R 10 are linked or otherwise connected together to form a 4 to 20 membered ring that may be substituted or unsubstituted, saturated or unsaturated; optionally the ring may include one or more of oxygen, nitrogen, or sulfur atoms or groups that include at least one of these atoms at any suitable position on the ring, and the ring may be optionally substituted with one or more substituents selected from the group consisting of any one of C 1 -C 6 alkyl, hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate, wherein the ring formed from R 9 is optionally linked and/or fused to a further ring
20 . The compound of claim 18 , wherein n is 5 and m is 11.
21 . The compound of claim 18 , wherein Z is chloride or iodide.
22 . The compound of claim 18 , wherein the compound is selected from:
1,4-bis(6-(dodecyloxy)-6-oxohexyl)piperazine-1,4-diium dichloride:
didodecyl 6,6′-((2,3-dihydroxysuccinyl)bis(methylazanediyl))dihexanoate:
and 1,4-bis(6-(dodecyloxy)-6-oxohexyl)-1,4-dimethylpiperazine-1,4-diium diiodide:
and combinations of the foregoing.