Title of Invention	NOVEL AMIDO-AMINE BASED COMPOUNDS USEFUL AS SURFACTANTS
Abstract	ABSTRACT The present invention relates to novel amido-amine compounds represented by the Formula (I), the process of preparation of the same and the use of these novel amido-amine compounds as surfactants and as anti-microbial agents. Formula (I) wherein n represents alky] chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Br and I.

Title of Invention

NOVEL AMIDO-AMINE BASED COMPOUNDS USEFUL AS SURFACTANTS

Abstract

ABSTRACT The present invention relates to novel amido-amine compounds represented by the Formula (I), the process of preparation of the same and the use of these novel amido-amine compounds as surfactants and as anti-microbial agents. Formula (I) wherein n represents alky] chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Br and I.

Full Text	FORM 2 THE PATENT ACT, 1970 (39 OF 1970) AND THE PATENT RULES, 2003 COMPLETE SPECIFICATION (See section 10; rule 13) 1. TITLE OF THE INVENTION NOVEL AMIDO-AMINE BASED COMPOUNDS USEFUL AS SURFACTANTS 2. APPLICANT: (a). Name: Institute of Chemical Technology (b). Nationality: Indian (c).Address: Department of Chemical Engineering, N M Parekh Rd Matunga, Mumbai. 400 019. 3. PREAMBLE TO THE DESCRIPTION The following specification particularly describes the invention and the manner in which it is to be performed: FIELD OF THE INVENTION The present invention, in general, relates to novel compounds and process for the preparation of the same. The present invention, in particular, relates to novel amido-amine based compounds, the process for their preparation and the use of these novel amido-amine compounds as cationic Gemini surfactants. BACKGROUND OF THE INVENTION Gemini surfactants are known as dimeric surfactants, which contains two hydrophobic & two hydrophilic groups in the molecule, connected by a linkage near to the hydrophilic groups. These surfactants have dual hydrophilic & hydrophobic nature. They tend to concentrate at the interface of the solution. These compounds are classified as anionic, cationic, nonionic & zwitterionic as per their ionic behavior in the solution. The cafjorwc surfactant dimers with simple structure are referred to as m-s-m, 2X. Where m is the head group, s is the spacer. Most of the work was focused on the length & nature of alkyl chains. A number of Gemini surfactants are reported in the literature. E.g. F. M. Menger, C. A. Littau, et. al. Gemini Surfactants: a new class of self assembling molecule, J. Am. Chem. Soc. 115, 10083-10090 (1993). F. M. Menger, C. A. Littau, Gemini surfactants: Synthesis properties, J. Am. Chem. Soc. 113, 1451-1452 (1991). R. oda, I, Hac, S. J. candau, gemini surfactants, the effect of hydrophobic chain length & dissymmetry, Chem. Commun. 21, 2105-2106 (1997). S.D. Wettig, R.E. Verrall, Thermodynamic studies of aqueous m-s-m gemini surfactants system, j. Colloid Inter f. Sci. 247, 310-316 (2001). Xu Huang, Yuchun Han, Yingxiong Wang, Meiwen Cao, Yilin Wang, Aggregation properties of cationic gemini surfactants, with dihydroxyethyamino head group in aqueous solution, Colloid & Surfactants A: Physicochemical & Engineering Aspects. 325, 26-32 (2008). Hong Tan, Huining Xiao, Synthesis & antimicrobial characterization of Novel L-lysine gemini surfactants pended with reactive group, Tetrahedron letter 49, 1759-1761 (2009). Lionel Massi, Federic Guittard, Richard Levy, S. Geribaldi, Enhanced activity of fluorinated quaternary ammonium surfactants against pseudomonas aeruginosa, European journal of medicinal chemistry, 44, 1615-1622(2009). In the recent decades, several papers have been published addressing the synthesis of a 2 new type of cationic gemini surfactants. Diz, M.; Manresa A.; Pinazo, a; Erra, P.; (nfante, M R. J. Chem. Soc, perkin Trans.2, 1871 (1994). Fuhrhop, J. H.; SPiroski, D, D.; Boettcher, C. J. Am. Chem. Soc, 115, 1600 (1993). Pavlikava, M.; Ucko, I.; Devinsky, R; Mlynarcik, M. collect, czech. chem. commun., 60 1213 (1995). Currently these quarternary ammonium compounds (QACs) have attracted attention especially due to their unique solution properties such as very low cmc, high surface wetting capacity, high Solubilization, high detergency. Mahendra S Borse, Surekha Devi, Importance of head group polarity in controlling aggregation properties of cationic gemini surfactants, colloid and Interface Science 123-126 (2006). Many of these QACs are useful as a catalyst in regie-selective addition reactions, Jin RH, Nishikubo T. Synthesis 1: 28 (1993);. Katrizky AR, offerman RJ, wang Z. Langmuir; 5: 1087 (1989), as an antimicrobial agents, Davis b, Jordan p. In: karsa DR, editor, Industrial applications of surfactants; vol II. Cambridge: Royal society of chemistry; 195-216 (1990). Gemini surfactants are more surface active than the conventional monomeric surfactaints. The hydrophobic part of surfece chain molecules is generally derived from a hydrocarbon containing 11 to 21 carbon atoms. Gemini surfactants are remarkably superior to conventional surfactants in characteristic features. They have a much lower critical micellization concentration (cmc), much lower values of the concentration C20 required to lower the surface tension of water by 20 mN/m. In terms of concentration, they are about three orders of magnitude more efficient at reducing the surface tension of water and more than two orders of magnitude more efficient in interfacial performances than conventional surfactants. Therefore, a small quantity of gemini surfactant can have dramatic effects in applications. Gemini surfactants are of much interest to manufacturers of cosmetics, shampoos, lotions, and personal care products because of their mildness, soft feeling, and absence skin irritation. They may also used as a Corrosion Inhibition, Micellar Catalysis, Antimicrobial activite agents. There is a need to develop novel cationic Gemini surfactants which can be prepared by simple, economical and environmentally friendly process. SUMMARY OF THE INVENTION The present invention relates to novel amido-amine compounds of the general Formula I, 3 Y. ^a ,.YV HR/\ l,R2H K1 R2 R1 o Jn Formula I wherein n represents alkyl chain having from 2 to 22 carbon atoms; each Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 independently represent lower alkyl groups having 1-5 carbon atoms; and X is selected from F, CI, Br and I. The present invention specifically relates to the compounds of formula I, wherein n represents alkyl chain having from 4 to 16 carbon atoms; each Y represents alkyl chain having from 3 to 5 carbon atoms; Q represents alkyl chain having from 3 to 6 carbon atoms; R1 and R2 represent lower alkyl groups selected from Me, Et and Pr; and X is selected from CI, Br and I. The present invention further relates to a process for the preparation of novel amido-amine compounds of Formula I Formula (I) wherein n represents alkyl chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower aikyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Br and I; the method comprising the steps of: i. reacting compound of Formula II with compound of formula III in presence of an organic solvent to give amido-amine intermediate of formula IV O H H 3 Formula II "OH 2 I R1 Formula III O ^N--2 H R1 Formula IV ; and it) reacting the amido-amine intermediate of formula IV with dihalo alkane of formula V in presence of a solvent to give the amido-amine compounds of formula I Formula V The present invention also provides a composition comprising the novel amido-amine compounds of Formula I dispersed in water The present invention still further provides the use of novel amido-amine compound of Formula 1 as surfactant and as anti-microbial agents. BRIEF DESCRIPTION OF DRAWINGS For a more complete understanding of the invention, reference should now be made to the embodiments illustrated in greater detail in the accompanying drawings and described below by way of embodiments of the invention. It should be understood, of course, that the invention is not necessarily limited to the particular embodiments illustrated herein. FIGURE 1 is a graph illustrating plots of surface tension vs. logarithm of concentration of monomer. FIGURE 2 is a graph illustrating plots of surface tension vs. logarithm of concentration of Cationic Gemini Surfactants having propyl group as spacer. FIGURE 3 is a graph illustrating plots of surface tension vs. logarithm of concentration of Cationic Gemini Surfactants having hexyl group as spacer. DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel amido-amine compounds of the general Formula I. O x- X" O K1 R2 R1 wherein n represents alkyl chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Brand I. Example No. n Q 1 CgHi3 (CH2)3 2 CaHi7 (CH2)3 3 C10H21 (CH2)3 4 C12H25 (CH2)3 5 CigH33 (CH2)3 6 C6H13 (CH2)e 7 CaHi7 (CH2)6 8 C10H21 (CH2)6 9 Ci2H25 (CH2)6 10 C16H33 (CH2)6 In a specific embodiment of the invention, Y represents alkyl chain having 3 to 5 carbon atoms. In yet another specific embodiment of the invention, Q represents alkyl chain having 3 to 6 carbon atoms. In still another specific embodiment of the invention, each R1 and R2 independently represents Me, Et and Pr group. Further, the invention most specifically relates, but is not limited to the following compounds of Formula I: Octanoic acid [3-({3-[3-Octanoylamino-propyl)-dimethyl-amino}-dimethyl-amino)- propyl]-amide dihydrobromide Decanoic acid [3-{{3-[3-Decanoylamino-propyl)-dimethyl-amino}-dimethyl-amino)- propyl]-amide dihydrobromide Dodecanoic acid [3-({3-[3-dodecanoylamino-propyl)-dimethyl-amino}-dimethyl- amino)-propyl]-amide dihydrobromide. Tetradecanoic acid [3-({3-[3Tetradecanoylamino-propyl)-dimethyl-amino}-dirnethyl- 7 amino)-propyl]-amide dihydrobromide. Octadecanoic acid [3-({3-[30ctadecanoylamino-propyl)-dimethyl-amino}-dimethyl- amino)-propyl]-amide dihydrobromide. Octanoic acid [3-({6-[(3-Octanoylamino-propy\|)-dimethyl-amino]-hexyl}-dimethyl- amino)-propyl]-amide dihydrobromide. Decanoic acid [3-({6-[(3-Decanoylamino-propy\|)-dimethyl-amino]-hexyl}-dimethyl- amino)-propyl]-amide dihydrobromide. Dodecanoic acid [3-({6-[(3-Dodecanoylamino-propyl)-dimethyl-amino]-hexyl}- dimethyl-amino)-propyl]-amide dihydrobromide. Tetradecanoic acid [3-({6-[{3-Tetradecanoylamino-propyl)-dimethyl-amino]-hexyl}- dimethyl-amino)-propyl]-amide dihydrobromide. Octadecanoic acid i3-({6-[(3-Octadecanoylamino-propyl)-dimethyl-amino]-hexyl}- dimethyl-amino)-propyl]-amide dihydrobromide. Another embodiment of the present invention relates to a process for the preparation of novel amido-amine compounds of Formula I X" ^ 1ST >i ^f \ I "R2H R2 R1 n O LI Chi Formula (I) wherein n represents alky] chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Brand I; the method comprising the steps of: i. reacting compound of Formula II with compound of formula organic solvent to give amido-amine intermediate of formula IV in presence of an u H„CJ lit * MnXOH 2 I R1 Formula II Formula III -Y- H3C r"r^ O R2 I R1 Formula IV ; and iii) reacting the amido-amine intermediate of formula IV with dihalo alkane of formula V in presence of a solvent to give the amido-amine compounds of formula I Formula V A general method of the present invention is represented by the following representative scheme: n^H R1 ,. . ^n H I + Solwnt reflux IV Solvent reflux O x- X O H /\ I R2 H 2 I RT R2 R1 In an embodiment of the process of the present inventidn, the organic solvent in step 1) is selected from any conventionally used aromatic hydrocarbons such as benzene, toluene, xylene, acetonitrile; preferably toluene is used, for around 16-18 hrs. The step 2 of the process is carried out in a solvent selected from organic solvents such as acetone, ethanol, acetonitrile, isopropanol, chloroform for around 60 - 80 hrs. In a preferred embodiment, the process for the preparation of the novel amido-amine compounds of Formu\a I, is carried out in an inert atmospjiere. Another embodiment of the invention relates to an aqueous composition comprising the novel amido-amine compounds of Formula I in water or water miscible solvent. In a specific embodiment, the water miscible solvent can be selected from any of the conventionally used solvents such as lower ketones sucn as acetone, lower esters such as methyl acetate, ethyl acetate, lower alcohols such as methanol, ethanoi, etc. In another specific embodiment, the aqueous composition can optionally comprise additives selected from any of the conventionally used additives such as thickening agent, anti-foaming agent, viscocity modifying agent, flavoring agent, perfumes, sterilizing or disinfecting agent, pH modifying agents etc. Yet another embodiment of the invention involves the use of the novel amido-amine compounds of Formula I, as surfactants. These novel amido-amine compounds have excellent surface activity and are useful as emulsifiers, solubilizing agents, dispersing agents, foaming agents, dispersing agents etc. They can be used in compositions for fabric conditioning, detergent compositions, as washing agents, as adjuvants for agriculturally active compounds and pharmaceutically active compounds. Still another embodiment of the invention involves the use of the novel amido-amine compounds of Formula I, as anti-microbial agents. The graph of the surface tension (v) vs the molar concentration on a semi-logarithmic scale (log C), for the preparation of Cationic gemini surfactants at 25 °C are shown in Figures 1, 2, 3. The Critical micelle concentration (CMC) which is defined by a sharp break and static surface tension at cmc (surface tension at cmc , Ycmc) is obtained from Fig. 1, 2, 3. As expected, the gemini compound exhibits a cmc value far below that of the corresponding monomer (Gemini surfactants shows from 5 to 550 times approximately lower cmc value than that of corresponding monomer.) The values for the static surface tension at cmc are less for gemini surfactants with propyl group as a spacer, while in case of gemini surfactants with hexyl group as a spacer it is not meaningfully different on comparison between its corresponding monomers. As the chain length of carboxylic acid is increased, it was found that there is a decrease in the cmc value. Thus, longer the hydrophobic chain, lower is the cmc value. The surfactant concentration at which the surface tension of pure solvent is reduced by 20mN/m is called as C20 The C20 value for Gemini surfactants are from 1 to 100 times approximately lower than that of corresponding monomer. EXAMPLES: The following examples are intended to illustrate but not to limit the present invention. Without further elaboration it is belived that one skilled in the art can, based on the 11 description herein, utilize the present invention to its fullest extent. The aspects of the invention are now explained with the non-limiting examples below. Example 1: Octanoic acid [3-({3-[3-Octanoylamino-propyl)-dimethyI-amino}-dimethyl-amino)-propyl]-amide dihydrobromide. Stepl: (3-dimethyl amino-propyl)-amine (9.97 g) was added to octanoic acid (5.0 g) in toluene (50 mLJ.The mixture was refluxed for -14 - 16 h until the water was completely removed. Octanoic acid (3-dimethyl amino-propyl)-amide was formed. (Yield 71 %.) Step 2: 1, 3 dibromopropane (25mmol, 5.025g) in dry acetone (35 ml) was added drop wise to octanoic acid (3-dimethyl amino-propylj-amide, (50mmol, 11.4g) in dry acetone (60ml_).The mixture was refluxed for 55-65 h. A white precipitate was filtered from the solution and recrystallized it from diethyl ether several times. (Yield 70 %.). (1HNMR-300MHz, TMS, CD3OD) 5ppm: 0.96: t, J=6.6 Hz, 6H; 1.20: m, 4H; 1.35: m, 16H; 1.62: t, J=6.9 Hz, 4H; 3.15=3.19: s, 12H; 2.35: m, 2H; 2.22: t, J=7.7 Hz, 4H; 3.30: m, 8H. For most of the surfactants, peak corresponding to NH did not appear probably due to efficient relaxation by the attached nitrogen. (13CNMR- 300MHz, TMS, CD3OD) 5ppm: 14.99: 2C; 15.99: 1C; 23.88: 2C; 24.11: 1C; 24.48; 1C; 26.37=26.50: 2C; 30.79; 2C; 30.58: 2C; 33.35: 2C; 35.30: 2C; 44.11: 2C; 57.08: 4C; 62.14:1C; 62.46: 1C; 64.5:2C; 177.07=176.99:20. FTlR-(KBr pellet): 3459 (nN-H, Secondary Amine), 1639(Amide I band), 1560 (Amide II band). Ms (positive) theoretical: 287,10; observed: 286.27 Example 2: Decanoic acid [3-({3-[3-Decanoylamino-propyl)-dimethyl-amino}-dimethyl-amino)-propyl]- amide dihydrobromide. Stepl: (3-dimethyl amino-propylj-amine (4.15g) was added to decanoic acid (5.0g) in toluene (45- 50 mL).The mixture was refluxed for 15-16 h until the water was completely removed . 12 Decanoic acid {3-dimethyl amino-propyl)-amide was formed. (Yield 75 %.) Step 2: The reaction was carried out under dry, oxygen free nitrogen condition.1, 3 dibromopropane {25mmol, 5.025g) in dry acetone (30 ml) was added dropwise to decanoic acid (3-dimethyl amino-propyl)-amide, (50 mmol, 12.85g) in dry acetone (70mL).The mixture was refluxed for 62-72 h. A white precipitate was filtered from the solution and recrystallized it from diethyl ether several times. (Yield 75%). (1H-NMR-300MHz, TMS, CD3OD) 5ppm: 0.86: t, J=6.30 Hz, 6H; 1.25=1.35: m, 24H; 1.60: m, 4H; 2.10: m, 4H; 2.35: t, J=6.75 Hz, 4H; 2.85: m, 2H; 3.15=3.19: m, 12H; 3.25=3.45: s, 12H. For most of the surfactants, peak corresponding to NH did not appear probably due to efficient relaxation by the attached nitrogen. (13CNMR- 300MHz, TMS, CD3OD) 5ppm: 16.14=16.22: 2C; 19.60: 1C; 24.90=25.05: 2C; 26.80: 2C; 28.08: 2C; 28.25: 2C; 31.48=31.60: 2C; 31.82=31.92: 2C; 32.03=32.14: 2C; 34.16=34.40: 2C; 38.66: 2C; 45.33: 2C; 54.11: 4C; 62.72:2C; 63.76: 2C; 178.18=178.76: 2C. FTIR-(KBr pellet): 3452 (nN-H, Secondary Amine), 1640(Amide I band), 1550 (Amide I! band). Ms (positive): theoretical: 553.73; observed: 553.4. Example 3: Dodecanoic acid [3-({3-[3-dodecanoylamino-propyl)-dimethyl-amino}-dimethyl-amino)-propyl]- amide dihydrobromide. Stepl: (3-dimethyl amino-propyl)-amine (3.58 g) was added to dodecanoic acid (5.0 g) in toluene (45-50 mL).The mixture was refluxed for 15-16 h until the water was completely removed. Dodecanoic acid (3-dimethyl amino-propyl)-amide was formed. (Yield 89 %.) Step 2: The reaction was carried out under dry, oxygen free nitrogen condition.1, 3 dibromopropane (25mmol, 5.025g) in dry acetone (35 ml) was added dropwise to dodecanoic acid (3-dimethyl amino-propyl)-amide, (50mmol, 14.25g) in dry acetone (60ml_).The mixture was refluxed for 50-65 h. A white precipitate was filtered from the solution and recrystallized it from diethyl ether several times. (Yield 74%). (1HNMR-300MHz, TMS, CD3OD) Gppm: 13 0.90: t, J=6.6 Hz, 6H; 1.20=1.40 m, 36H; 1.65: m, 4H; 2.35: t, J=7.3 Hz, 4H; 2.87: m, 2H; 3.05=3.20: m, 12H; 3.35: s, 12H. For most of the surfactants, peak corresponding to NH did not appear probably due to efficient relaxation by the attached nitrogen. (13CNMR- 300MHz, TMS, DaO) 5ppm: 16.23: 2C; 19.62: 1C; 25.09: 4C; 27.05: 2C; 28,30: 2C; 31.96: 2C; 32.06: 2C; 32.40: 4C; 34.47: 4C; 38.70: 2C; 45.52: 2C; 54.15: 4C; 62.74:2C; 63.78: 2C;178.07: 2C. FT1R-(KBr pellet): 3443 (nN-H, Secondary Amine), 1640(Amide I band), 1550 (Amide II band). Ms (positive): theoretical: 651.29; observed: 652. Example 4: Tetradecanoic acid [3-({3-[3Tetradecanoylamino-propyl)-dimethyl-amino}-dimethyl-amino)- propyl]-amide dihydrobromide. Stepl: (3-dtmethyl arr>ina-prQpyl)-amine (3,14 q) was added to tetradecanoic acid (5.0 g) ia toluene (45-50 mL).The mixture was refluxed for 16-18 h until the water was completely removed . Tetradecanoic acid (3-dimethyl amino-propyl)-amide was formed. (Yield 65 %) Step 2: The reaction was carried out under dry, oxygen free nitrogen condition.1, 3 dibromopropane (25mmol, 5,025g) in dry acetone (40 ml) was added dropwise to tetradecanoic acid (3- dimethy! amino-propyl)-amide, (SOmmol, 15.65 g) in dry acetone (70m!_).The mixture was refluxed for 65-70 h. A white precipitate was filtered from the solution and recrystalJized it from diethyl ether several times. (Yield 78%) (1HNMR-300MHz, TMS, CD3OD) 5ppm: 0.88: t, J=6.8 Hz, 6H; 1.25=1.45 m, 44H; 1.67: m, 4H; 2-2: t, J= 7.3 Hz, 4H; 2.77: m, 2H; 3.03.25: m, 12H; 3.40: s, 12H. For most of the surfactants, peak corresponding to NH did not appear probably due to efficient relaxation by the attached nitrogen. (13CNMR- 300MHz, TMS, CD3OD) 5ppm: 14.99: 2C; 17.15: 1C; 22.19: 2C; 24,13=24.71: 2C; 26,35:20; 27.37: 2C; 27.80.2C; 30.86; 6C; 31.71: 6C; 33.41=34.30: 2C; 35.90=37.50: 2C; 41.00: 2C; 44.12=44.74:2C; 54.37=55.04: 2C; 63.46:2C; 66.13: 2C; 177.42: 2C. FT\|R-(KBr pellet): 3447 (nN-H, Secondary Amine), 1647(Amide t band), 1549 (Amide II band). Ms (positive): theoretical: 372; observed: 371.27. 14 Example 5: Octadecanoic acid [3-({3-[30ctadecanoylamino-propy\|)-dimethyl-amino}-dimethyl-amino)- propyl]-amide dihydrobromide. Stepl: (3-dimethy! amino-propyl)-amine (2.5 g) was added to Octadecanoic acid (5.0 g) in toluene (45-50mL)The mixture was refluxed for 18 h until the water was completely removed . Octadecanoic acid (3-dimethyl amino-propyl)-amide was formed. (Yield 80 %.) Step 2: 1, 3 dibromopropane octadecanoic acid (3-dimethyl amino-propyl)-amide, (50mmol, 19.3g) in dry acetone (80mL).The mixture was refluxed for 60-71 h. A white precipitate was filtered from the solution and recrystallized it from diethyl ether several times. (Yield 60%). (1HNMR-300MHz, TMS, CD3OD) 6ppm: 0.96: t, J=6.9 Hz, 6H; 1.20=1.40 m, 56H; 1.65: m, 4H; 2.1; m, 4H; 2.30: t J=7.1 Hz, 4H; 2.90: m, 2H; 3.15: mr 4H; 3.40: s, 12H; 3.50: m, 8H; 8.10; s, 2H. (13CNMR- 300MHz, TMS, CD3OD) 5ppm: 15.066: 3C; 24.25: 2C; 24.51: 2C; 27.52: 2C; 27.97: 2C; 3.84: 2C; 30.99: 2C; 31.32: 16C; 33.58: 2C; 37.62: 2C; 38.56: 2C; 45.36: 2C; 52.34: 4C; 62.17: 2C; 64.50: 2C; 176.82=177.048: 2C. FTIR-(KBr pellet): 3458 (nN-H, Secondary Amine), 16^o(Amide I band), 1552 (Amide II band). Ms (positive): Expected. M/z: 407; observed: 406.38 Example 6: Octanoic acid [3-({6-[(3-Octanoylamino-propyl)-dimethyl-amino]-hexyl>dimethyl-amino)- propy1]-amide dihydrobromide. Step 1: (3-dimethyl amino-propyl)-amine (9.97g) was added to Octanoic acid (5.0 g) in toluene (45- 50 mLJ.The mixture was refluxed for 14-16 h until the water was completely removed . Octanoic acid (3-dimethyl amino-propyl)-amide was formed. (Yield 71 %.) Step 2: 1,6 dibromohexane (25mmo!, 5.025g) in dry acetone (30 ml) was added dropwise to Octanoic acid (3-dimethyl amino-propyl)-amide, (SOmmol, 9.42g) in dry acetone (60mL).The mixture was refluxed for 50-60 h. A white precipitate was filtered from the solution and recrystallized it 15 from diethyl ether several times. (Yield 70%) (1H-NMR-300MHz, TMS, CD3OD) 5ppm: 0.94: t, J=6.9 Hz, 6H; 1.30: m, 16H; 1.45: m, 4H; 1.60: p, J=7.3 Hz, 4H; 1.82: m, 4H; 2.0: m, 4H; 2.21: t, J=7.6 Hz, 4H; 3.15: s, 12H; 3.25: m, 4H; 3.35: m, 8H. For most of the surfactants, peak corresponding to NH did not appear probably due to efficient relaxation by the attached nitrogen. (13CNMR-300MHz, TMS, CD3OD) 5ppm: 14.945: 2C; 23.67: 2C; 24.120: 2c; 24.464: s2C; 27.043: 2C; 27.408: 2C; 30.57=30.77: 4C: 33.312: 2C: 37.624: 2C; 37.70: 2C; 51.97: 4C: 63.77:2C: 65.857: 2C; 176.987: 2C. FTIR-(KBr pellet): 3459 (nN-H, Secondary Amine), 1645(Amide I band), 1551 (Amide II band). Ms (positive: Expected. M/z> (M-2Br)/2+1 =271.36; observed: 271.33 Example 7: Decanoic acid [3-({6-[(3-Decanoylamino-propyl)-dimethyl-aminol-hexyl}-dimethyl-amino)- propylj-amide dihydrobromide. Stepl: (3-dimethyl amino-propyl)-amine (4.15g) was added to decanoic acid (5.0 g) in toluene (45- 50 mL).The mixture was refluxed for 15-16 h until the water was completely removed . decanoic acid (6-dimethyl amino-propyl)-amide was formed. {Yield 75 %.) Step 2: 1,6 dibromohexane (25mmol, 5.025g) in dry acetone (35 ml) was added dropwise to decanoic acid (3-dimethyl amino-propyl)-amide, (50mmol( 10.54g) in dry acetone (70mL).The mixture was refluxed for 55-63 h. A white precipitate was filtered from the solution and recrystallized it from diethyl ether several times. (Yield 65%). (1H-NMR-300MHz, TMS, CD3OD) 5ppm: 0.90: t, J=6.9 Hz, 6H; 1.30: m, 24H; 1.5: m, 4H; 1.60: m, 4H; 1.80: m, 4H; 2.0: p, J=7.6 Hz, 4H; 2.20: t, J=7.7 Hz, 4H; 3.15: s, 12H; 3.22: m, 4H; 3.35: m, 8H. For most of the surfactants, peak corresponding to NH did not appear probably due to efficient relaxation by the attached nitrogen. (13CNMR-300WIHz, TMS, CD3OD) 5ppm: 15.036: 2C; 23.69: 2C; 24.21: 2C; 24.50.2C; 27.053: 2C; 27.458:2C; 30.097: 4C; 30.978: 2C; 31.00: 2C; 33.517: 2C; 37.68: 2C; 37.756: 2C; 52.029: 4C; 63.80: 2C; 65.887:2C; 176.97: 2C. FTIR-(KBr pellet): 3460 (nN-H, Secondary Amine), 1641 (Amide I band), 1549 (Amide II 16 band). Ms (positive): Expected. M/z- (M-2Br)/2 = 321.4; observed-320.20. Example 8: Dodecanoic acid [3-({6-[(3-Dodecanoylamino-propy\|) amino)-propylj-amidedihydrobromide. Stepl: (3-dimethyl amino-propyl)-amine (3.57 g) was added to dodecanoic acid (5.0 g) in toiuene ( 45-50 mL).The mixture was refluxed for 15~16 h until the water was completely removed . Dodecanoic acid (3-dimethy! amino-propyl)-amide was formed. (Yield 89 %.) Step 2: 1,6 dibromohexane (25mmol, 5.025g) in dry acetone (40 ml) was added dropwise to dodecanoic acid (3-dimethy! amino-propyl)-amide, (SOmmol, 11.85g) in dry acetone (80mL).The mixture was refluxed for 58-68 h. A white precipitate was filtered from the solution and recrystaMed it from diethyl ether several times. [Yieid 70%). (1HNMR-300MHz, TMS, CD3OD) Sppm: 0.86: t, J=6.9 Hz, 6H; 1.25: m, 32H; 1.45=1.65: m, 8H; 1.90=2.1: m, 8H; 2.25: t, J= 7.3Hz, 4H; 3.0=3.35: m, 4H; 3.50: s, 12H; 3.75: m, 8H; 7.8; s, 2H. (13CNMR-300MHz, TMS, CD3OD) 5ppm: 14.11: 2C; 22.66: 2C; 23.09: 2C; 24.85: 2C; 25.88: 2C; 29.34: 2C; 29.47:2C; 29.56; 6C; 29.63: 2C; 29.69: 2C; 31.89: 4C; 36.14=36.41: 2C; 51.20: 4C; 62.53: 2C; 64.76: 2C; 174.44: 2C. FT\|R-(KBr pellet): 3460 (nN-H, Secondary Amine), 1645(Amide I band), 1550 (Amide II band). Ms (positive): Expected. M/z- (M-2Br) = 653; observed-6S5. Example 9: Tetradecanoic acid [3-({6-[(3-Tetradecanoylamino-propyl)-dimethyl-amino]-hexyl}-dimethyl- amino) -propyJJ-amjde d ihydrobromid e. Stepl: (3-dimethyl amino-propyl)-amine (3.14 g) was added to tetradecanoic acid (5.0 g) in toluene (45-50 mL).The mixture was refluxed for 16~18 h until the water was completely removed . Tetradecanoic acid (3-dimethyl amino-propyl)-amide was formed. (Yield 65 %.) Step 2: 17 1, 6 dibromohexane (25mmol, 5.025g) in dry acetone (35 ml) was added dropwise to tetradecanoic acid (3-dimethyl amino-propyl)-amide, (SOmmol, 12.84g) in dry acetone {60ml_).The mixture was refluxed for 55-65 h. A white precipitate was filtered from the solution and recrystallized it from diethyl ether several times. (Yield 80 %) (1HNMR-300MHz, TMS, CD3OD) 5ppm: 0,90: t, J=6.9 Hz, 6H; 1.35: m, 44H; 1.62: m, 4H; 1.90; m, 8H; 2.30=2.57: m, 4H; 2.95: t, J=7.7 Hz, 4H; 3.15: m, 4H; 3.35: m, 4H; 3.50: s, 12H. For most of the surfactants, peak corresponding to NH did not appear probably due to efficient relaxation by the attached nitrogen. (,3CNMR-300MHz, TMS, CD3OD) Oppm: 15.01: 2C; 22.20: 2C; 24.13=24.34: 2C; 24.54=24.71: 2C; 26.35=26.50: 2C; 27.33=27.44: 2C; 27.58=27.79: 2C; 28.70=28.83: 2C; 30.70: 2C; 30.86: 2C; 31.17: 2C; 33.46=33.99: 2C; 34.17=34.26: 2C; 34.80=35.33: 2C; 35.46=35.93: 2C; 37.57=38.63: 2C; 40.92: 2C; 46.09: 4C; 62.80=63.43: 2C; 66.10=67.57: 2C; 175.53: 2C. FTIR-fKBr pellet): 3438 (nN-H, Secondary Amine), 1650{Amide I band), 1549 (Amide ll band). Example 10: Octadecanoic acid [3-({6-[(3-Octadecanoylamino-propy\|)-dimethyl-amino]-hexy(}-dimethyl- amino)-propyt]-amidedihydrobromide. Stepl: (3-dimethyl amino-propyl)-amine (2.5 g) was added to octadecanoic acid (5.0 g) in toluene ( 45-50 mL).The mixture was refluxed for 18 h until the water was completely removed . Octadecanoic acid (3-dimethyl amino-propyl)-amide was formed. (Yield 80 %.) Step 2: 1,6 dibromohexane (25mmol, 5.025g) in dry acetone (35 ml) was added dropwise to octadecanoic acid (3-dimethyl amino-propyl)-amide, (SOmmol, 15.83g) in dry acetone (60mL).The mixture was refluxed for65-70h. A white precipitate was filtered from the solution and recrystallized it from diethyl ether several times. (Yield 60 %) (1HNMR-300MHz, TMS, CD3OD) Oppm: 0.90: t, J=6.9 Hz, 6H; 1.30: m, 60H; 1.50: m, 4H; 1.60: m, 4H; 1.80: m, 4H; 2.0; m, 4H; 2.20: t, J=7.5 Hz, 4H; 3.15: s, 12H; 3.30: m, 8H. For most of the surfactants, peak corresponding to NH did not appear probably due to efficient relaxation by the attached nitrogen. (13CNMR-300MHz, TMS, CD3OD) Oppm: 18 13.06: 2C; 21.83: 2C; 22.34: 2C; 22.70: 2C; 25.30: 2C; 25.58: 2C; 29.09=29.27: 6C; 29.40: 18C; 31.68: 2C; 35.80: 2C; 35.91: 2C; 50.07: 4C; 61.93: 2C; 64.01: 2C; 175.34: 2C. FTlR-(KBr pellet):3461 (nN-H, Secondary Amine), 1640(Amide I band), 1553 (Amide II band). For testing the surface activity of the novel amido-amines, the equilibrium surface tension measurements were made by the Wilhelmy vertical plate technique with a sandblasted platinum blade. The instrument was calibrated against distilled water. Sets of measurements were taken until the change in surface tension occurs. The graphs were plotted against surface tension values versus concentration of surfactant solution. The CMC (Critical Micelle concentration) values were taken during the sharp drop in the surface tension values. vmin refers to Surface Tension at cmc. These results are summarized in Table 1. Table 1: Compound No. CMC (m mol/l) Ymln (mN/m) C20 (m mol/l) Example 1 8.80 23.42 0.48 Example 2 0.41 23.19 0.003 Example 3 0.007 26.21 0.0007 Example 4 0.006 32.08 0.0013 Example 5 0.08 38.75 0.0015 Example 6 2.17 41.07 1.51 Example 7 0.86 38.91 0.009 Example 8 0.26 40.95 0.07 Example 9 0.80 23.73 0.0015 Example 10 0.18 34.52 0.01 Octanoic Monomer 26.1 33.75 1.46 Decanoic Monomer 6.57 25.73 0.32 Dodecanoic Monomer 0.92 23.52 0.007 Tetradecanoic Monomer 3.32 23.37 0.018 Octadecanoic 1.96 38.32 10.01 Monomer Antimicrobial activity Study: The antimicrobial activity of the synthesized compounds were determined by the Well-diffusion method. In this method, Escheria Coli (ATCC-25922), Bacillus cereus (ATCC-10702), Staphylococcus aureus (ATCC-6538), Pseudomonas aeruginosa (ATCC-8027) were used to investigate the antimicrobial activities. The bacterial liquid cultures were prepared in infusion broth for their activity tests. The compounds were dissolved in methanol at concentration of 1 mg/ml. Antimicrobial activity of methanol against the test organism was investigated, and was found to be nil. Approximately 1cm3 of 24 h broth culture containing 106 cfu cm3 was placed in sterile petri dishes. Molten nutrient agar (15 cm3), kept at 45 °C, was then poured into the petri dishes and allowed to solidify. Six millimeter diameter holes were then punched carefully using sterile cork borer and completely filled with test solutions. The plate were incubated for 24 h at 37 °C. After 24 hrs, the inhibition zone that appeared around the hole in each plate was measured. Antimicrobial activity was determined by measuring the diameter of inhibition zone. All the tests were performed in triplicate and the results were presented as an average. Activity of each compound was compared with CTAB standard. These results are summarized in table 2. Table 2: Compound No. E.Coli S.auerus B.subtilis P.acruge Example 1 — 11mm 10mm 11mm Example 2 — 19mm 12mm 12mm Example 3 — — 13mm - Example 4 - 16mm 15mm 13mm Example 5 - 9mm 8mm 9mm Example 6 — 12 mm 8mm Example 7 16 mm 20mm 18mm - Example 8 ~ 7 mm 10mm - Example 9 — 16 mm 15mm ~ Example 10 — — ~ - Octanoic Monomer 8mm Decanoic Monomer 13mm 10mm Dodecanoic Monomer 8mm Tetradecanoic Monomer 15mm 12mm 19mm Octadecanoic Monomer 8mm 8 mm CTAB 8mm 12mm 10mm — We Claim: 1. Novel amido-amine compounds represented by the Formula (I): Formula (I) wherein n represents alkyl chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Br and I. 2. The novel amido-amine compounds as claimed in claim 1, wherein Vhe compound is: Octanoic acid [3-{{3-[3-Octanoylamino-propyl)-dimethyl-amino}-dimethyl- amino)-propyl]-amidedihydrobromide Decanoic acid [3-({3-[3-Decanoylamino-propyl)-dimethyl-amino}-dimethyl- amino)-propyl]-amide dihydrobromide Dodecanoic acid [3-({3-[3-dodecanoylamino-propyl)-dimethyl-amino}- dimethyl-amino)-propyl]-amide dihydrobromide. Tetradecanoic acid [3-{{3-[3Tetradecanoylamino-propyl)-dimethyl-amino}- dimethyl-amino)-propyl]-amide dihydrobromide. Octadecanoic acid [3-({3-[30ctadecanoylamino-propyl)-dimethyl-amino}- dimethy!-amino)-propylj-amide dihydrobromide. 3. The novel amido-amine compounds as claimed in claim 1, wherein the compound is: Octanoic acid [3-({6-[(3-Octanoylamino-propyl)-dimethy!-amino]-hexyl}- dimethyl-amino)-propyl]-amide dihydrobromide. Decanoic acid [3-({6-[(3-Decanoylamino-propyl)-dimethyl-amino]-hexyl}- dimethyl-amino)-propyl]-amide dihydrobromide. Dodecanoic acid [3-({6-[(3-Dodecanoylamino-propyl)-dimethyl-amino]-hexyl}- dimethyi-amino)-propyl]-amidedihydrobromide. Tetradecanoic acid [3-({6-[(3-Tetradecanoylamino-propyl)-dimethyl-amino]- hexyl}-dimethyl-amino)-propyl]-amfdedihydrobromide. Octadecanoic acid [3-({6-[(3-Octadecanoylamino-propyl)-dirnethyl-amino]- hexyl}-dimethyl-amino)-propyl]-amidedihydrobromide. 4. A method of preparing the novel amido-amine compounds of Formula I, wherein n represents alkyl chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Br and I; the method comprising the steps of: i. reacting compound of Formula II with compound of formula III in presence of an organic solvent to give amido-amine intermediate of formula IV ; and b. reacting the amido-amine intermediate of Formula IV with dihalo alkane of formula V in presence of a solvent to give the amido-amine compounds of formula I Formula V 5. The method of preparing the novel amido-amine compounds as claimed in claim 1, wherein the organic solvent of step 1 is aromatic hydrocarbons selected from toluene, benzene, xylene and acetonitrile. 6. The method of preparing the novel amido-amine compounds as claimed in claim 1, wherein the solvent of step 2 is an organic solvent selected from acetone, ethanol and acetonitrile. 7. An aqueous composition comprising the novel amido-amine compounds of Formula I dispersed in water or water-miscible solvent. Formula (I) wherein n represents alkyl chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Br and I. 8. Use of the novel amido-amine compounds of Formula I as claimed in claim 1, as surfactants. Formula (I) wherein n represents alkyl chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Br and I. 9. Use of the novel amido-amine compounds of Formula I as claimed in claim 1, as antimicrobial agents. Formula (I) wherein n represents alkyl chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Br and I.

Full Text

FORM 2
THE PATENT ACT, 1970
(39 OF 1970)
AND
THE PATENT RULES, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)
1. TITLE OF THE INVENTION
NOVEL AMIDO-AMINE BASED COMPOUNDS USEFUL AS SURFACTANTS
2. APPLICANT:
(a). Name: Institute of Chemical Technology
(b). Nationality: Indian
(c).Address: Department of Chemical Engineering, N M Parekh Rd Matunga, Mumbai. 400 019.
3. PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed:

FIELD OF THE INVENTION
The present invention, in general, relates to novel compounds and process for the preparation of the same. The present invention, in particular, relates to novel amido-amine based compounds, the process for their preparation and the use of these novel amido-amine compounds as cationic Gemini surfactants.
BACKGROUND OF THE INVENTION
Gemini surfactants are known as dimeric surfactants, which contains two hydrophobic & two hydrophilic groups in the molecule, connected by a linkage near to the hydrophilic groups. These surfactants have dual hydrophilic & hydrophobic nature. They tend to concentrate at the interface of the solution. These compounds are classified as anionic, cationic, nonionic & zwitterionic as per their ionic behavior in the solution. The cafjorwc surfactant dimers with simple structure are referred to as m-s-m, 2X. Where m is the head group, s is the spacer. Most of the work was focused on the length & nature of alkyl chains. A number of Gemini surfactants are reported in the literature. E.g. F. M. Menger, C. A. Littau, et. al. Gemini Surfactants: a new class of self assembling molecule, J. Am. Chem. Soc. 115, 10083-10090 (1993). F. M. Menger, C. A. Littau, Gemini surfactants: Synthesis properties, J. Am. Chem. Soc. 113, 1451-1452 (1991). R. oda, I, Hac, S. J. candau, gemini surfactants, the effect of hydrophobic chain length & dissymmetry, Chem. Commun. 21, 2105-2106 (1997). S.D. Wettig, R.E. Verrall, Thermodynamic studies of aqueous m-s-m gemini surfactants system, j. Colloid Inter f. Sci. 247, 310-316 (2001). Xu Huang, Yuchun Han, Yingxiong Wang, Meiwen Cao, Yilin Wang, Aggregation properties of cationic gemini surfactants, with dihydroxyethyamino head group in aqueous solution, Colloid & Surfactants A: Physicochemical & Engineering Aspects. 325, 26-32 (2008). Hong Tan, Huining Xiao, Synthesis & antimicrobial characterization of Novel L-lysine gemini surfactants pended with reactive group, Tetrahedron letter 49, 1759-1761 (2009). Lionel Massi, Federic Guittard, Richard Levy, S. Geribaldi, Enhanced activity of fluorinated quaternary ammonium surfactants against pseudomonas aeruginosa, European journal of medicinal chemistry, 44, 1615-1622(2009).
In the recent decades, several papers have been published addressing the synthesis of a
2

new type of cationic gemini surfactants. Diz, M.; Manresa A.; Pinazo, a; Erra, P.; (nfante, M R. J. Chem. Soc, perkin Trans.2, 1871 (1994). Fuhrhop, J. H.; SPiroski, D, D.; Boettcher, C. J. Am. Chem. Soc, 115, 1600 (1993). Pavlikava, M.; Ucko, I.; Devinsky, R; Mlynarcik, M. collect, czech. chem. commun., 60 1213 (1995).
Currently these quarternary ammonium compounds (QACs) have attracted attention especially due to their unique solution properties such as very low cmc, high surface wetting capacity, high Solubilization, high detergency. Mahendra S Borse, Surekha Devi, Importance of head group polarity in controlling aggregation properties of cationic gemini surfactants, colloid and Interface Science 123-126 (2006). Many of these QACs are useful as a catalyst in regie-selective addition reactions, Jin RH, Nishikubo T. Synthesis 1: 28 (1993);. Katrizky AR, offerman RJ, wang Z. Langmuir; 5: 1087 (1989), as an antimicrobial agents, Davis b, Jordan p. In: karsa DR, editor, Industrial applications of surfactants; vol II. Cambridge: Royal society of chemistry; 195-216 (1990). Gemini surfactants are more surface active than the conventional monomeric surfactaints. The hydrophobic part of surfece chain molecules is generally derived from a hydrocarbon containing 11 to 21 carbon atoms.
Gemini surfactants are remarkably superior to conventional surfactants in characteristic features. They have a much lower critical micellization concentration (cmc), much lower values of the concentration C20 required to lower the surface tension of water by 20 mN/m. In terms of concentration, they are about three orders of magnitude more efficient at reducing the surface tension of water and more than two orders of magnitude more efficient in interfacial performances than conventional surfactants. Therefore, a small quantity of gemini surfactant can have dramatic effects in applications. Gemini surfactants are of much interest to manufacturers of cosmetics, shampoos, lotions, and personal care products because of their mildness, soft feeling, and absence skin irritation. They may also used as a Corrosion Inhibition, Micellar Catalysis, Antimicrobial activite agents.
There is a need to develop novel cationic Gemini surfactants which can be prepared by simple, economical and environmentally friendly process.
SUMMARY OF THE INVENTION
The present invention relates to novel amido-amine compounds of the general Formula I,
3

Y. ^a ,.YV
HR/\ l,R2H K1 R2 R1

o

Jn

Formula I wherein n represents alkyl chain having from 2 to 22 carbon atoms; each Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 independently represent lower alkyl groups having 1-5 carbon atoms; and X is selected from F, CI, Br and I.
The present invention specifically relates to the compounds of formula I, wherein n represents alkyl chain having from 4 to 16 carbon atoms; each Y represents alkyl chain having from 3 to 5 carbon atoms; Q represents alkyl chain having from 3 to 6 carbon atoms; R1 and R2 represent lower alkyl groups selected from Me, Et and Pr; and X is selected from CI, Br and I.
The present invention further relates to a process for the preparation of novel amido-amine compounds of Formula I

Formula (I) wherein n represents alkyl chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower aikyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Br and I;
the method comprising the steps of:

i. reacting compound of Formula II with compound of formula III in presence of an organic solvent to give amido-amine intermediate of formula IV
O

H H
3
Formula II

"OH

2 I
R1
Formula III

O
^N*--*2

H

R1

Formula IV
; and
it) reacting the amido-amine intermediate of formula IV with dihalo alkane of formula V in presence of a solvent to give the amido-amine compounds of formula I
Formula V
The present invention also provides a composition comprising the novel amido-amine compounds of Formula I dispersed in water
The present invention still further provides the use of novel amido-amine compound of

Formula 1 as surfactant and as anti-microbial agents.
BRIEF DESCRIPTION OF DRAWINGS
For a more complete understanding of the invention, reference should now be made to the embodiments illustrated in greater detail in the accompanying drawings and described below by way of embodiments of the invention. It should be understood, of course, that the invention is not necessarily limited to the particular embodiments illustrated herein.
FIGURE 1 is a graph illustrating plots of surface tension vs. logarithm of concentration of monomer.
FIGURE 2 is a graph illustrating plots of surface tension vs. logarithm of concentration of Cationic Gemini Surfactants having propyl group as spacer.
FIGURE 3 is a graph illustrating plots of surface tension vs. logarithm of concentration of Cationic Gemini Surfactants having hexyl group as spacer.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides novel amido-amine compounds of the general Formula I.
O x- X" O
K1 R2 R1
wherein n represents alkyl chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Brand I.

Example No. n Q
1 CgHi3 (CH2)3
2 CaHi7 (CH2)3
3 C10H21 (CH2)3
4 C12H25 (CH2)3
5 CigH33 (CH2)3
6 C6H13 (CH2)e
7 CaHi7 (CH2)6
8 C10H21 (CH2)6
9 Ci2H25 (CH2)6
10 C16H33 (CH2)6
In a specific embodiment of the invention, Y represents alkyl chain having 3 to 5 carbon atoms.
In yet another specific embodiment of the invention, Q represents alkyl chain having 3 to 6 carbon atoms.
In still another specific embodiment of the invention, each R1 and R2 independently represents Me, Et and Pr group.
Further, the invention most specifically relates, but is not limited to the following compounds
of Formula I:
Octanoic acid [3-({3-[3-Octanoylamino-propyl)-dimethyl-amino}-dimethyl-amino)-
propyl]-amide dihydrobromide
Decanoic acid [3-{{3-[3-Decanoylamino-propyl)-dimethyl-amino}-dimethyl-amino)-
propyl]-amide dihydrobromide
Dodecanoic acid [3-({3-[3-dodecanoylamino-propyl)-dimethyl-amino}-dimethyl-
amino)-propyl]-amide dihydrobromide.
Tetradecanoic acid [3-({3-[3Tetradecanoylamino-propyl)-dimethyl-amino}-dirnethyl-
7

amino)-propyl]-amide dihydrobromide.
Octadecanoic acid [3-({3-[30ctadecanoylamino-propyl)-dimethyl-amino}-dimethyl-
amino)-propyl]-amide dihydrobromide.
Octanoic acid [3-({6-[(3-Octanoylamino-propy|)-dimethyl-amino]-hexyl}-dimethyl-
amino)-propyl]-amide dihydrobromide.
Decanoic acid [3-({6-[(3-Decanoylamino-propy|)-dimethyl-amino]-hexyl}-dimethyl-
amino)-propyl]-amide dihydrobromide.
Dodecanoic acid [3-({6-[(3-Dodecanoylamino-propyl)-dimethyl-amino]-hexyl}-
dimethyl-amino)-propyl]-amide dihydrobromide.
Tetradecanoic acid [3-({6-[{3-Tetradecanoylamino-propyl)-dimethyl-amino]-hexyl}-
dimethyl-amino)-propyl]-amide dihydrobromide.
Octadecanoic acid i3-({6-[(3-Octadecanoylamino-propyl)-dimethyl-amino]-hexyl}-
dimethyl-amino)-propyl]-amide dihydrobromide.
Another embodiment of the present invention relates to a process for the preparation of novel amido-amine compounds of Formula I

X"
^
1ST >i ^f \ I "R2H R2 R1 n

O
LI

Chi

Formula (I) wherein n represents alky] chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Brand I;
the method comprising the steps of:

i. reacting compound of Formula II with compound of formula organic solvent to give amido-amine intermediate of formula IV

in presence of an

u
H„CJ lit
* MnXOH 2 I
R1
Formula II Formula III

-Y-
H3C
r"r^
O

R2
I
R1

Formula IV
; and
iii) reacting the amido-amine intermediate of formula IV with dihalo alkane of formula V in presence of a solvent to give the amido-amine compounds of formula I
Formula V
A general method of the present invention is represented by the following representative scheme:

n^H R1 ,. . ^n H I +
Solwnt
reflux IV
Solvent
reflux
O x- X O

H */\ I R2 H
2 I
RT R2 R1

In an embodiment of the process of the present inventidn, the organic solvent in step 1) is selected from any conventionally used aromatic hydrocarbons such as benzene, toluene, xylene, acetonitrile; preferably toluene is used, for around 16-18 hrs.
The step 2 of the process is carried out in a solvent selected from organic solvents such as acetone, ethanol, acetonitrile, isopropanol, chloroform for around 60 - 80 hrs.
In a preferred embodiment, the process for the preparation of the novel amido-amine compounds of Formu\a I, is carried out in an inert atmospjiere.
Another embodiment of the invention relates to an aqueous composition comprising the novel amido-amine compounds of Formula I in water or water miscible solvent.
In a specific embodiment, the water miscible solvent can be selected from any of the conventionally used solvents such as lower ketones sucn as acetone, lower esters such as methyl acetate, ethyl acetate, lower alcohols such as methanol, ethanoi, etc.
In another specific embodiment, the aqueous composition can optionally comprise additives selected from any of the conventionally used additives such as thickening agent, anti-foaming agent, viscocity modifying agent, flavoring agent, perfumes, sterilizing or disinfecting agent, pH modifying agents etc.

Yet another embodiment of the invention involves the use of the novel amido-amine compounds of Formula I, as surfactants.
These novel amido-amine compounds have excellent surface activity and are useful as emulsifiers, solubilizing agents, dispersing agents, foaming agents, dispersing agents etc. They can be used in compositions for fabric conditioning, detergent compositions, as washing agents, as adjuvants for agriculturally active compounds and pharmaceutically active compounds.
Still another embodiment of the invention involves the use of the novel amido-amine compounds of Formula I, as anti-microbial agents.
The graph of the surface tension (v) vs the molar concentration on a semi-logarithmic scale (log C), for the preparation of Cationic gemini surfactants at 25 °C are shown in Figures 1, 2, 3. The Critical micelle concentration (CMC) which is defined by a sharp break and static surface tension at cmc (surface tension at cmc , Ycmc) is obtained from Fig. 1, 2, 3. As expected, the gemini compound exhibits a cmc value far below that of the corresponding monomer (Gemini surfactants shows from 5 to 550 times approximately lower cmc value than that of corresponding monomer.)
The values for the static surface tension at cmc are less for gemini surfactants with propyl group as a spacer, while in case of gemini surfactants with hexyl group as a spacer it is not meaningfully different on comparison between its corresponding monomers. As the chain length of carboxylic acid is increased, it was found that there is a decrease in the cmc value. Thus, longer the hydrophobic chain, lower is the cmc value.
The surfactant concentration at which the surface tension of pure solvent is reduced by 20mN/m is called as C20 The C20 value for Gemini surfactants are from 1 to 100 times approximately lower than that of corresponding monomer.
EXAMPLES:
The following examples are intended to illustrate but not to limit the present invention. Without further elaboration it is belived that one skilled in the art can, based on the
11

description herein, utilize the present invention to its fullest extent. The aspects of the invention are now explained with the non-limiting examples below.
Example 1:
Octanoic acid [3-({3-[3-Octanoylamino-propyl)-dimethyI-amino}-dimethyl-amino)-propyl]-amide dihydrobromide. Stepl:
(3-dimethyl amino-propyl)-amine (9.97 g) was added to octanoic acid (5.0 g) in toluene (50 mLJ.The mixture was refluxed for -14 - 16 h until the water was completely removed. Octanoic acid (3-dimethyl amino-propyl)-amide was formed. (Yield 71 %.) Step 2:
1, 3 dibromopropane (25mmol, 5.025g) in dry acetone (35 ml) was added drop wise to octanoic acid (3-dimethyl amino-propylj-amide, (50mmol, 11.4g) in dry acetone (60ml_).The mixture was refluxed for 55-65 h. A white precipitate was filtered from the solution and recrystallized it from diethyl ether several times. (Yield 70 %.). (1HNMR-300MHz, TMS, CD3OD) 5ppm:
0.96: t, J=6.6 Hz, 6H; 1.20: m, 4H; 1.35: m, 16H; 1.62: t, J=6.9 Hz, 4H; 3.15=3.19: s, 12H; 2.35: m, 2H; 2.22: t, J=7.7 Hz, 4H; 3.30: m, 8H. For most of the surfactants, peak corresponding to NH did not appear probably due to efficient relaxation by the attached nitrogen.
(13CNMR- 300MHz, TMS, CD3OD) 5ppm:
14.99: 2C; 15.99: 1C; 23.88: 2C; 24.11: 1C; 24.48; 1C; 26.37=26.50: 2C; 30.79; 2C; 30.58: 2C; 33.35: 2C; 35.30: 2C; 44.11: 2C; 57.08: 4C; 62.14:1C; 62.46: 1C; 64.5:2C; 177.07=176.99:20.
FTlR-(KBr pellet): 3459 (nN-H, Secondary Amine), 1639(Amide I band), 1560 (Amide II band). Ms (positive) theoretical: 287,10; observed: 286.27
Example 2:
Decanoic acid [3-({3-[3-Decanoylamino-propyl)-dimethyl-amino}-dimethyl-amino)-propyl]-
amide dihydrobromide.
Stepl:
(3-dimethyl amino-propylj-amine (4.15g) was added to decanoic acid (5.0g) in toluene (45-
50 mL).The mixture was refluxed for 15-16 h until the water was completely removed .
12

Decanoic acid {3-dimethyl amino-propyl)-amide was formed. (Yield 75 %.) Step 2:
The reaction was carried out under dry, oxygen free nitrogen condition.1, 3 dibromopropane {25mmol, 5.025g) in dry acetone (30 ml) was added dropwise to decanoic acid (3-dimethyl amino-propyl)-amide, (50 mmol, 12.85g) in dry acetone (70mL).The mixture was refluxed for 62-72 h. A white precipitate was filtered from the solution and recrystallized it from diethyl ether several times. (Yield 75%). (1H-NMR-300MHz, TMS, CD3OD) 5ppm:
0.86: t, J=6.30 Hz, 6H; 1.25=1.35: m, 24H; 1.60: m, 4H; 2.10: m, 4H; 2.35: t, J=6.75 Hz, 4H; 2.85: m, 2H; 3.15=3.19: m, 12H; 3.25=3.45: s, 12H. For most of the surfactants, peak corresponding to NH did not appear probably due to efficient relaxation by the attached nitrogen.
(13CNMR- 300MHz, TMS, CD3OD) 5ppm:
16.14=16.22: 2C; 19.60: 1C; 24.90=25.05: 2C; 26.80: 2C; 28.08: 2C; 28.25: 2C; 31.48=31.60: 2C; 31.82=31.92: 2C; 32.03=32.14: 2C; 34.16=34.40: 2C; 38.66: 2C; 45.33: 2C; 54.11: 4C; 62.72:2C; 63.76: 2C; 178.18=178.76: 2C.
FTIR-(KBr pellet): 3452 (nN-H, Secondary Amine), 1640(Amide I band), 1550 (Amide I! band). Ms (positive): theoretical: 553.73; observed: 553.4.
Example 3:
Dodecanoic acid [3-({3-[3-dodecanoylamino-propyl)-dimethyl-amino}-dimethyl-amino)-propyl]-
amide dihydrobromide.
Stepl:
(3-dimethyl amino-propyl)-amine (3.58 g) was added to dodecanoic acid (5.0 g) in toluene
(45-50 mL).The mixture was refluxed for 15-16 h until the water was completely removed.
Dodecanoic acid (3-dimethyl amino-propyl)-amide was formed. (Yield 89 %.)
Step 2:
The reaction was carried out under dry, oxygen free nitrogen condition.1, 3 dibromopropane
(25mmol, 5.025g) in dry acetone (35 ml) was added dropwise to dodecanoic acid (3-dimethyl
amino-propyl)-amide, (50mmol, 14.25g) in dry acetone (60ml_).The mixture was refluxed for
50-65 h. A white precipitate was filtered from the solution and recrystallized it from diethyl
ether several times. (Yield 74%).
(1HNMR-300MHz, TMS, CD3OD) Gppm:
13

0.90: t, J=6.6 Hz, 6H; 1.20=1.40 m, 36H; 1.65: m, 4H; 2.35: t, J=7.3 Hz, 4H; 2.87: m, 2H;
3.05=3.20: m, 12H; 3.35: s, 12H. For most of the surfactants, peak corresponding to NH did
not appear probably due to efficient relaxation by the attached nitrogen.
(13CNMR- 300MHz, TMS, DaO) 5ppm: 16.23: 2C; 19.62: 1C; 25.09: 4C; 27.05: 2C; 28,30:
2C; 31.96: 2C; 32.06: 2C; 32.40: 4C; 34.47: 4C; 38.70: 2C; 45.52: 2C; 54.15: 4C; 62.74:2C;
63.78: 2C;178.07: 2C.
FT1R-(KBr pellet): 3443 (nN-H, Secondary Amine), 1640(Amide I band), 1550 (Amide II
band).
Ms (positive): theoretical: 651.29; observed: 652.
Example 4:
Tetradecanoic acid [3-({3-[3Tetradecanoylamino-propyl)-dimethyl-amino}-dimethyl-amino)-
propyl]-amide dihydrobromide.
Stepl:
(3-dtmethyl arr>ina-prQpyl)-amine (3,14 q) was added to tetradecanoic acid (5.0 g) ia toluene
(45-50 mL).The mixture was refluxed for 16-18 h until the water was completely removed .
Tetradecanoic acid (3-dimethyl amino-propyl)-amide was formed. (Yield 65 %)
Step 2:
The reaction was carried out under dry, oxygen free nitrogen condition.1, 3 dibromopropane
(25mmol, 5,025g) in dry acetone (40 ml) was added dropwise to tetradecanoic acid (3-
dimethy! amino-propyl)-amide, (SOmmol, 15.65 g) in dry acetone (70m!_).The mixture was
refluxed for 65-70 h. A white precipitate was filtered from the solution and recrystalJized it
from diethyl ether several times. (Yield 78%)
(1HNMR-300MHz, TMS, CD3OD) 5ppm:
0.88: t, J=6.8 Hz, 6H; 1.25=1.45 m, 44H; 1.67: m, 4H; 2-2: t, J= 7.3 Hz, 4H; 2.77: m, 2H;
3.0*3.25: m, 12H; 3.40: s, 12H. For most of the surfactants, peak corresponding to NH did
not appear probably due to efficient relaxation by the attached nitrogen.
(13CNMR- 300MHz, TMS, CD3OD) 5ppm:
14.99: 2C; 17.15: 1C; 22.19: 2C; 24,13=24.71: 2C; 26,35:20; 27.37: 2C; 27.80.2C; 30.86; 6C;
31.71: 6C; 33.41=34.30: 2C; 35.90=37.50: 2C; 41.00: 2C; 44.12=44.74:2C; 54.37=55.04: 2C;
63.46:2C; 66.13: 2C; 177.42: 2C.
FT|R-(KBr pellet): 3447 (nN-H, Secondary Amine), 1647(Amide t band), 1549 (Amide II
band).
Ms (positive): theoretical: 372; observed: 371.27.
14

Example 5:
Octadecanoic acid [3-({3-[30ctadecanoylamino-propy|)-dimethyl-amino}-dimethyl-amino)-
propyl]-amide dihydrobromide.
Stepl:
(3-dimethy! amino-propyl)-amine (2.5 g) was added to Octadecanoic acid (5.0 g) in toluene
(45-50mL)The mixture was refluxed for 18 h until the water was completely removed .
Octadecanoic acid (3-dimethyl amino-propyl)-amide was formed. (Yield 80 %.)
Step 2:
1, 3 dibromopropane octadecanoic acid (3-dimethyl amino-propyl)-amide, (50mmol, 19.3g) in dry acetone
(80mL).The mixture was refluxed for 60-71 h. A white precipitate was filtered from the solution
and recrystallized it from diethyl ether several times. (Yield 60%).
(1HNMR-300MHz, TMS, CD3OD) 6ppm:
0.96: t, J=6.9 Hz, 6H; 1.20=1.40 m, 56H; 1.65: m, 4H; 2.1; m, 4H; 2.30: t J=7.1 Hz, 4H; 2.90:
m, 2H; 3.15: mr 4H; 3.40: s, 12H; 3.50: m, 8H; 8.10; s, 2H.
(13CNMR- 300MHz, TMS, CD3OD) 5ppm: 15.066: 3C; 24.25: 2C; 24.51: 2C; 27.52: 2C;
27.97: 2C; 3.84: 2C; 30.99: 2C; 31.32: 16C; 33.58: 2C; 37.62: 2C; 38.56: 2C; 45.36: 2C;
52.34: 4C; 62.17: 2C; 64.50: 2C; 176.82=177.048: 2C.
FTIR-(KBr pellet): 3458 (nN-H, Secondary Amine), 16^o(Amide I band), 1552 (Amide II
band).
Ms (positive): Expected. M/z: 407; observed: 406.38
Example 6:
Octanoic acid [3-({6-[(3-Octanoylamino-propyl)-dimethyl-amino]-hexyl>dimethyl-amino)-
propy1]-amide dihydrobromide.
Step 1:
(3-dimethyl amino-propyl)-amine (9.97g) was added to Octanoic acid (5.0 g) in toluene (45-
50 mLJ.The mixture was refluxed for 14-16 h until the water was completely removed .
Octanoic acid (3-dimethyl amino-propyl)-amide was formed. (Yield 71 %.)
Step 2:
1,6 dibromohexane (25mmo!, 5.025g) in dry acetone (30 ml) was added dropwise to Octanoic
acid (3-dimethyl amino-propyl)-amide, (SOmmol, 9.42g) in dry acetone (60mL).The mixture
was refluxed for 50-60 h. A white precipitate was filtered from the solution and recrystallized it
15

from diethyl ether several times. (Yield 70%)
(1H-NMR-300MHz, TMS, CD3OD) 5ppm:
0.94: t, J=6.9 Hz, 6H; 1.30: m, 16H; 1.45: m, 4H; 1.60: p, J=7.3 Hz, 4H; 1.82: m, 4H; 2.0: m,
4H; 2.21: t, J=7.6 Hz, 4H; 3.15: s, 12H; 3.25: m, 4H; 3.35: m, 8H. For most of the surfactants,
peak corresponding to NH did not appear probably due to efficient relaxation by the attached
nitrogen.
(13CNMR-300MHz, TMS, CD3OD) 5ppm: 14.945: 2C; 23.67: 2C; 24.120: 2c; 24.464: s2C;
27.043: 2C; 27.408: 2C; 30.57=30.77: 4C: 33.312: 2C: 37.624: 2C; 37.70: 2C; 51.97: 4C:
63.77:2C: 65.857: 2C; 176.987: 2C.
FTIR-(KBr pellet): 3459 (nN-H, Secondary Amine), 1645(Amide I band), 1551 (Amide II
band).
Ms (positive: Expected. M/z> (M-2Br)/2+1 =271.36; observed: 271.33
Example 7:
Decanoic acid [3-({6-[(3-Decanoylamino-propyl)-dimethyl-aminol-hexyl}-dimethyl-amino)-
propylj-amide dihydrobromide.
Stepl:
(3-dimethyl amino-propyl)-amine (4.15g) was added to decanoic acid (5.0 g) in toluene (45-
50 mL).The mixture was refluxed for 15-16 h until the water was completely removed .
decanoic acid (6-dimethyl amino-propyl)-amide was formed. {Yield 75 %.)
Step 2:
1,6 dibromohexane (25mmol, 5.025g) in dry acetone (35 ml) was added dropwise to
decanoic acid (3-dimethyl amino-propyl)-amide, (50mmol( 10.54g) in dry acetone (70mL).The
mixture was refluxed for 55-63 h. A white precipitate was filtered from the solution and
recrystallized it from diethyl ether several times. (Yield 65%).
(1H-NMR-300MHz, TMS, CD3OD) 5ppm:
0.90: t, J=6.9 Hz, 6H; 1.30: m, 24H; 1.5: m, 4H; 1.60: m, 4H; 1.80: m, 4H; 2.0: p, J=7.6 Hz,
4H; 2.20: t, J=7.7 Hz, 4H; 3.15: s, 12H; 3.22: m, 4H; 3.35: m, 8H. For most of the surfactants,
peak corresponding to NH did not appear probably due to efficient relaxation by the attached
nitrogen.
(13CNMR-300WIHz, TMS, CD3OD) 5ppm: 15.036: 2C; 23.69: 2C; 24.21: 2C; 24.50.2C;
27.053: 2C; 27.458:2C; 30.097: 4C; 30.978: 2C; 31.00: 2C; 33.517: 2C; 37.68: 2C; 37.756:
2C; 52.029: 4C; 63.80: 2C; 65.887:2C; 176.97: 2C.
FTIR-(KBr pellet): 3460 (nN-H, Secondary Amine), 1641 (Amide I band), 1549 (Amide II
16

band).
Ms (positive): Expected. M/z- (M-2Br)/2 = 321.4; observed-320.20.
Example 8:
Dodecanoic acid [3-({6-[(3-Dodecanoylamino-propy|) amino)-propylj-amidedihydrobromide.
Stepl:
(3-dimethyl amino-propyl)-amine (3.57 g) was added to dodecanoic acid (5.0 g) in toiuene (
45-50 mL).The mixture was refluxed for 15~16 h until the water was completely removed .
Dodecanoic acid (3-dimethy! amino-propyl)-amide was formed. (Yield 89 %.)
Step 2:
1,6 dibromohexane (25mmol, 5.025g) in dry acetone (40 ml) was added dropwise to
dodecanoic acid (3-dimethy! amino-propyl)-amide, (SOmmol, 11.85g) in dry acetone
(80mL).The mixture was refluxed for 58-68 h. A white precipitate was filtered from the solution
and recrystaMed it from diethyl ether several times. [Yieid 70%).
(1HNMR-300MHz, TMS, CD3OD) Sppm:
0.86: t, J=6.9 Hz, 6H; 1.25: m, 32H; 1.45=1.65: m, 8H; 1.90=2.1: m, 8H; 2.25: t, J= 7.3Hz, 4H;
3.0=3.35: m, 4H; 3.50: s, 12H; 3.75: m, 8H; 7.8; s, 2H.
(13CNMR-300MHz, TMS, CD3OD) 5ppm:
14.11: 2C; 22.66: 2C; 23.09: 2C; 24.85: 2C; 25.88: 2C; 29.34: 2C; 29.47:2C; 29.56; 6C;
29.63: 2C; 29.69: 2C; 31.89: 4C; 36.14=36.41: 2C; 51.20: 4C; 62.53: 2C; 64.76: 2C; 174.44:
2C.
FT|R-(KBr pellet): 3460 (nN-H, Secondary Amine), 1645(Amide I band), 1550 (Amide II
band).
Ms (positive): Expected. M/z- (M-2Br) = 653; observed-6S5.
Example 9:
Tetradecanoic acid [3-({6-[(3-Tetradecanoylamino-propyl)-dimethyl-amino]-hexyl}-dimethyl-
amino) -propyJJ-amjde d ihydrobromid e.
Stepl:
(3-dimethyl amino-propyl)-amine (3.14 g) was added to tetradecanoic acid (5.0 g) in toluene
(45-50 mL).The mixture was refluxed for 16~18 h until the water was completely removed .
Tetradecanoic acid (3-dimethyl amino-propyl)-amide was formed. (Yield 65 %.)
Step 2:
17

1, 6 dibromohexane (25mmol, 5.025g) in dry acetone (35 ml) was added dropwise to
tetradecanoic acid (3-dimethyl amino-propyl)-amide, (SOmmol, 12.84g) in dry acetone
{60ml_).The mixture was refluxed for 55-65 h. A white precipitate was filtered from the solution
and recrystallized it from diethyl ether several times. (Yield 80 %)
(1HNMR-300MHz, TMS, CD3OD) 5ppm:
0,90: t, J=6.9 Hz, 6H; 1.35: m, 44H; 1.62: m, 4H; 1.90; m, 8H; 2.30=2.57: m, 4H; 2.95: t,
J=7.7 Hz, 4H; 3.15: m, 4H; 3.35: m, 4H; 3.50: s, 12H. For most of the surfactants, peak
corresponding to NH did not appear probably due to efficient relaxation by the attached
nitrogen.
(,3CNMR-300MHz, TMS, CD3OD) Oppm: 15.01: 2C; 22.20: 2C; 24.13=24.34: 2C;
24.54=24.71: 2C; 26.35=26.50: 2C; 27.33=27.44: 2C; 27.58=27.79: 2C; 28.70=28.83: 2C;
30.70: 2C; 30.86: 2C; 31.17: 2C; 33.46=33.99: 2C; 34.17=34.26: 2C; 34.80=35.33: 2C;
35.46=35.93: 2C; 37.57=38.63: 2C; 40.92: 2C; 46.09: 4C; 62.80=63.43: 2C; 66.10=67.57: 2C;
175.53: 2C.
FTIR-fKBr pellet): 3438 (nN-H, Secondary Amine), 1650{Amide I band), 1549 (Amide ll
band).
Example 10:
Octadecanoic acid [3-({6-[(3-Octadecanoylamino-propy|)-dimethyl-amino]-hexy(}-dimethyl-
amino)-propyt]-amidedihydrobromide.
Stepl:
(3-dimethyl amino-propyl)-amine (2.5 g) was added to octadecanoic acid (5.0 g) in toluene (
45-50 mL).The mixture was refluxed for 18 h until the water was completely removed .
Octadecanoic acid (3-dimethyl amino-propyl)-amide was formed. (Yield 80 %.)
Step 2:
1,6 dibromohexane (25mmol, 5.025g) in dry acetone (35 ml) was added dropwise to
octadecanoic acid (3-dimethyl amino-propyl)-amide, (SOmmol, 15.83g) in dry acetone
(60mL).The mixture was refluxed for65-70h. A white precipitate was filtered from the solution
and recrystallized it from diethyl ether several times. (Yield 60 %)
(1HNMR-300MHz, TMS, CD3OD) Oppm:
0.90: t, J=6.9 Hz, 6H; 1.30: m, 60H; 1.50: m, 4H; 1.60: m, 4H; 1.80: m, 4H; 2.0; m, 4H; 2.20:
t, J=7.5 Hz, 4H; 3.15: s, 12H; 3.30: m, 8H. For most of the surfactants, peak corresponding to
NH did not appear probably due to efficient relaxation by the attached nitrogen.
(13CNMR-300MHz, TMS, CD3OD) Oppm:
18

13.06: 2C; 21.83: 2C; 22.34: 2C; 22.70: 2C; 25.30: 2C; 25.58: 2C; 29.09=29.27: 6C; 29.40: 18C; 31.68: 2C; 35.80: 2C; 35.91: 2C; 50.07: 4C; 61.93: 2C; 64.01: 2C; 175.34: 2C. FTlR-(KBr pellet):3461 (nN-H, Secondary Amine), 1640(Amide I band), 1553 (Amide II band).
For testing the surface activity of the novel amido-amines, the equilibrium surface tension measurements were made by the Wilhelmy vertical plate technique with a sandblasted platinum blade. The instrument was calibrated against distilled water. Sets of measurements were taken until the change in surface tension occurs. The graphs were plotted against surface tension values versus concentration of surfactant solution. The CMC (Critical Micelle concentration) values were taken during the sharp drop in the surface tension values. vmin refers to Surface Tension at cmc.
These results are summarized in Table 1.
Table 1:

Compound No. CMC (m mol/l) Ymln
(mN/m) C20
(m mol/l)
Example 1 8.80 23.42 0.48
Example 2 0.41 23.19 0.003
Example 3 0.007 26.21 0.0007
Example 4 0.006 32.08 0.0013
Example 5 0.08 38.75 0.0015
Example 6 2.17 41.07 1.51
Example 7 0.86 38.91 0.009
Example 8 0.26 40.95 0.07
Example 9 0.80 23.73 0.0015
Example 10 0.18 34.52 0.01
Octanoic
Monomer 26.1 33.75 1.46
Decanoic Monomer 6.57 25.73 0.32
Dodecanoic Monomer 0.92 23.52 0.007
Tetradecanoic Monomer 3.32 23.37 0.018

Octadecanoic 1.96 38.32 10.01
Monomer
Antimicrobial activity Study:
The antimicrobial activity of the synthesized compounds were determined by the Well-diffusion method. In this method, Escheria Coli (ATCC-25922), Bacillus cereus (ATCC-10702), Staphylococcus aureus (ATCC-6538), Pseudomonas aeruginosa (ATCC-8027) were used to investigate the antimicrobial activities. The bacterial liquid cultures were prepared in infusion broth for their activity tests. The compounds were dissolved in methanol at concentration of 1 mg/ml. Antimicrobial activity of methanol against the test organism was investigated, and was found to be nil. Approximately 1cm3 of 24 h broth culture containing 106 cfu cm3 was placed in sterile petri dishes. Molten nutrient agar (15 cm3), kept at 45 °C, was then poured into the petri dishes and allowed to solidify. Six millimeter diameter holes were then punched carefully using sterile cork borer and completely filled with test solutions. The plate were incubated for 24 h at 37 °C. After 24 hrs, the inhibition zone that appeared around the hole in each plate was measured. Antimicrobial activity was determined by measuring the diameter of inhibition zone. All the tests were performed in triplicate and the results were presented as an average. Activity of each compound was compared with CTAB standard. These results are summarized in table 2.

Table 2:

Compound No. E.Coli S.auerus B.subtilis P.acruge
Example 1 — 11mm 10mm 11mm
Example 2 — 19mm 12mm 12mm
Example 3 — — 13mm -
Example 4 - 16mm 15mm 13mm
Example 5 - 9mm 8mm 9mm
Example 6 — 12 mm 8mm
Example 7 16 mm 20mm 18mm -
Example 8 ~ 7 mm 10mm -
Example 9 — 16 mm 15mm ~
Example 10 — — ~ -
Octanoic Monomer 8mm
Decanoic Monomer 13mm 10mm
Dodecanoic Monomer 8mm
Tetradecanoic Monomer 15mm 12mm 19mm
Octadecanoic Monomer 8mm 8 mm
CTAB 8mm 12mm 10mm —

We Claim:
1. Novel amido-amine compounds represented by the Formula (I):

Formula (I) wherein n represents alkyl chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Br and I.
2. The novel amido-amine compounds as claimed in claim 1, wherein Vhe compound is:
Octanoic acid [3-{{3-[3-Octanoylamino-propyl)-dimethyl-amino}-dimethyl-
amino)-propyl]-amidedihydrobromide
Decanoic acid [3-({3-[3-Decanoylamino-propyl)-dimethyl-amino}-dimethyl-
amino)-propyl]-amide dihydrobromide
Dodecanoic acid [3-({3-[3-dodecanoylamino-propyl)-dimethyl-amino}-
dimethyl-amino)-propyl]-amide dihydrobromide.
Tetradecanoic acid [3-{{3-[3Tetradecanoylamino-propyl)-dimethyl-amino}-
dimethyl-amino)-propyl]-amide dihydrobromide.
Octadecanoic acid [3-({3-[30ctadecanoylamino-propyl)-dimethyl-amino}-
dimethy!-amino)-propylj-amide dihydrobromide.
3. The novel amido-amine compounds as claimed in claim 1, wherein the compound is:
Octanoic acid [3-({6-[(3-Octanoylamino-propyl)-dimethy!-amino]-hexyl}-
dimethyl-amino)-propyl]-amide dihydrobromide.
Decanoic acid [3-({6-[(3-Decanoylamino-propyl)-dimethyl-amino]-hexyl}-
dimethyl-amino)-propyl]-amide dihydrobromide.
Dodecanoic acid [3-({6-[(3-Dodecanoylamino-propyl)-dimethyl-amino]-hexyl}-

dimethyi-amino)-propyl]-amidedihydrobromide.
Tetradecanoic acid [3-({6-[(3-Tetradecanoylamino-propyl)-dimethyl-amino]-
hexyl}-dimethyl-amino)-propyl]-amfdedihydrobromide.
Octadecanoic acid [3-({6-[(3-Octadecanoylamino-propyl)-dirnethyl-amino]-
hexyl}-dimethyl-amino)-propyl]-amidedihydrobromide.
4. A method of preparing the novel amido-amine compounds of Formula I,

wherein n represents alkyl chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Br and I;
the method comprising the steps of:
i. reacting compound of Formula II with compound of formula III in presence of an organic solvent to give amido-amine intermediate of formula IV

; and b. reacting the amido-amine intermediate of Formula IV with dihalo alkane of formula V in presence of a solvent to give the amido-amine compounds of formula I

Formula V
5. The method of preparing the novel amido-amine compounds as claimed in claim 1, wherein the organic solvent of step 1 is aromatic hydrocarbons selected from toluene, benzene, xylene and acetonitrile.
6. The method of preparing the novel amido-amine compounds as claimed in claim 1, wherein the solvent of step 2 is an organic solvent selected from acetone, ethanol and acetonitrile.
7. An aqueous composition comprising the novel amido-amine compounds of Formula I dispersed in water or water-miscible solvent.

Formula (I)
wherein n represents alkyl chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Br and I.
8. Use of the novel amido-amine compounds of Formula I as claimed in claim 1, as surfactants.

Formula (I) wherein n represents alkyl chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Br and I.
9. Use of the novel amido-amine compounds of Formula I as claimed in claim 1, as antimicrobial agents.

Formula (I) wherein n represents alkyl chain having from 2 to 22 carbon atoms; Y represents alkyl chain having from 2 to 8 carbon atoms; Q represents alkyl chain having from 2 to 10 carbon atoms; each R1 and R2 represent lower alkyl groups having 1 - 5 carbon atoms; and X is selected from F, CI, Br and I.

Documents:

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Patent Number

269441

Indian Patent Application Number

2393/MUM/2010

PG Journal Number

44/2015

Publication Date

30-Oct-2015

Grant Date

21-Oct-2015

Date of Filing

27-Aug-2010

Name of Patentee

INSTITUTE OF CHEMICAL TECHNOLOGY

Applicant Address

DEPARTMENT OF CHEMICAL ENGINEERING, N M PAREKH RD MATUNGA, MUMBAI. 400 019.

Inventors:

#	Inventor's Name	Inventor's Address
1	GHUMARE, ANANT KANHOBA	DEPARTMENT OF CHEMICAL ENGINEERING, N M PAREKH RD MATUNGA, MUMBAI. 400 019.
2	BHAGWAT ,SUNIL SUBHASH	DEPARTMENT OF CHEMICAL ENGINEERING, N M PAREKH RD MATUNGA, MUMBAI, 400 019.

PCT International Classification Number

C07C 231/12, C07C 233/36

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA