Indian Patents. 279095:CATIONIC GUAR-GUM ALKYL AMINE DERIVATIVES AND PROCESS OF PREPARATION THEREOF

Title of Invention	CATIONIC GUAR-GUM ALKYL AMINE DERIVATIVES AND PROCESS OF PREPARATION THEREOF
Abstract	There is disclosed novel cationic guar gum alkyl amine and its acid amide derivatives of formula I wherein X is CH2, n has a value of 3 or 4, R2 is one of H or COR3 and y denotes polymer linking, as well as their process of preparation following green chemistry approach.

Full Text	Cationic Guar-Gum Alkyl Amine, Its Derivatives and Process of Preparation Thereof Field of Invention: This invention relates to novel cationic Guar gum alkyl amine (GAA) and its amide derivatives. This invention also relates to a process for preparation of such novel Guar-gum alkyl amine (GAA) and its derivatives following green chemistry approach. BackGround of the Invention: Guar gum is extracted from the guar bean. Chemically, guar gum is a polysaccharide composed of the sugars galactose and mannose. The backbone is a linear chain of ß 1,4-linked mannose residues to which galactose residues are 1,6-linked at every second mannose, forming short side- branches. It has a chemical structure : Cationic polysaccharides are known to be having good conditioning properties and used frequently as industrial additives. Cationic derivatives of guar gum are widely used for the preparation of shampoos, hair conditioners, personal and household care detergents as well as in pulp and paper , food processing and pharmaceutical industries. US Patent 3589978 discloses the use of cationic guar gum derivatives. US Patent 4061602 discloses use of cationic guar gum in preparation of shampoo. Guar 2 hydroxypropyl trimethyl ammonium chloride and their preparatory methods are also known. However, both the above compounds are hazardous and may form carcinoma due to the presence of free quarternary ammonium group present in the reactant 2-3 epoxypropyl trimethyl ammonium chloride. US patent publication US 2010/0036114 provides a process for preparation of a purified guar 2 hydroxy 3 (trimethylammonium) propyl ether chloride. However, these compounds , though useful, are difficult to produce and structurally complex . Therefore there is a need of synthesizing a structurally simpler cationic guar gum and Its derivatives as well as their simple preparation process, following green chemistry approach, which does not have the drawbacks of the prior art cationic guar gum derivatives and their preparatory methods. The novel cationic Guar Gum alkyl amine and its derivatives could not be synthesized previously because all prior art synthetic methods of guar gum were heavily dependent on use of high amount of sodium hydroxide (alkali) causing chain breaking of guar polymer affecting quality of the product and often non specific substitution. Moreover for synthesis of cationic guar gum, higher temperature was necessary in media. The inventor has synthesized Guar gum alkyl amine(GAA) compounds in simple preparatory method , which were not known hitherto before and has also synthesised various amide derivatives of such GAA compounds as well as has elucited their method of synthesis. The new Guar gum alkyl amine and derivatives may be used for removal of molecules and ions from aqueous environments, tissue fluids as well as from terrestrial water resources. The novel Guar gum alkyl amine and derivatives are excellent drug delivery devices namely as, excipients in solid dosage forms, excipients in liquid dosage forms like emulsions and suspensions, nanoparticle delivery devices, wound dressings, dentistry and mucoadhesives. The novel Guar gum alkyl amine and derivative biopolymers of the present invention can be used in cosmetics as formulation stabilizers, hair conditioners, preservatives and gelling agents, as well. Objects of the Invention: It is a primary object of the invention to provide a novel Guar gum alkyl amine (GAA) compound with a simpler structure. It is another object of the invention to provide novel amide derivatives of GAA. It is yet another objective of the invention is to provide a simple reaction scheme to produce GAA and its derivatives. It is a further object of the invention to provide GAA and its amide derivatives which are simpler in structure but at least as effective as the known Cationic Guar Gum derivatives. It is yet further objective of the invention is to provide a process for synthesis of novel GAA and its derivatives following green chemistry approach. This and other objects of the invention are described in the detailed description of the invention. Summary of the Invention: Accordingly the present invention provides Cationic guar gum alkyl amine and its amide type/ corresponding amide derivatives of general formula I wherein X is CH2, n has a value of 3 or 4, R2 is one of H or COR3 and y denotes polymer linking. Said R3 is selected from an alkyl or allyl or aryl group R3 is methyl, ethyl, propyl , stearyl, olealyl or benzoyl. Preferably the said compound has a degree of substitution in the range of 0.18 to 0.52. The present invention also provides a process for preparing a guar gum akyl amine and its corresponding amide/ amide derivatives of formula I wherein X , n , R2 , R3and y are as defined above,comprising reacting (l) guar gum with suitable haloalkylating agent in aqueous ammonia to produce guar gum alkyl amine of general formula II and optionally (ii) reacting the resultant guar gum alkyl amine of general formula II with corresponding acetate or a acid halide in aqueous alkali to produce guar gum alkyl amide or acetamide derivatives. Preferably the said haloalkylating agent is selected from epichlorhydrin, epibromohydrin , 4-chloro 1,2-epoxybutane and 4-bromo 1,2-epoxybutane Preferably in step (i) the reaction is carried out in an alcoholic medium such as n- propanol, isopropanol, n-butanol ,amyl alcohol, ethanol or methanol. Preferably in step (i) the reaction is carried out at a basic pH range between 7.5 to 11 and temperature range 30-90 ° C. Brief Description of the Accompanying Drawings: Fig 1 is F-T I R Spectra of Guar-Gum (GG). Fig 2 is F-T I R Spectra of Guar-Gum alkyl amine (GAA) . Fig 3 is FT-IR Spectra of Guar gum alkyl amine benzoate( GAAB) . Fig 4 illustrates C13 NMR of Guar gum . Fig 5 illustrates C13 NMR of Guar gum alkyl amine (GAA) Fig 6 illustrates C13 NMR of Guar gum alkyl amine benzoate. Fig 7 illustrates Guar gum alkyl amine (GAA) , phenol adsorption studies in U.V region. Fig 9 illustrates Guar gum alkyl amine oleate (GAA) , B.S.A complexation studies in U.V region. Detailed Description of the Invention: The present invention discloses a novel Guar Gum Alkyl Amine (GAA) and its corresponding amide and amide derivatives according to the General formula I X is CH2, n has a value of 3 or 4,R2 is one of H or COR3, R3 is selected from an alkyl or allyl or aryl group.R3 may be an alkyl group and may be selected from methyl, ethyl, propyl, stearyl, olealyl. R3 may also be benzoyl group. And y denotes polymer linking. The novel Guar gum alkyl amine (GAA) of the present invention has a chemical structure denoted by General formula II, Guar gum n butyl amine Degree of substitution in the novel compounds are in the range of 0.18 to 0.52 . By degree of substitution, It Is meant the substitution of catlonic group on the equatorial hydroxyl groups on ring 1 & 3 of Guar, measured by means of CHNS analysis described in detail later. The equatorial -OH groups of position 6 in manose and galactose unit of guar gum are being substituted by hydroxyalkyl amine group to produce the catlonic guar gum alkyl amine (GAA) of the invention. The alkyl moeity of the substituted hydroxyalkyi amine group may be hydroxypropyl when n in the formula I is 3 or butyl when n in the general formula I is 4. It will be well understood by a person skilled in the art that guar gum alkyl amine and its derivatives of the present invention can have varied molecular weight depending on the guar gum source, the degree of polymerization and the degree of substitution. Depending on the substitution of at the terminal amino group, various acid amide derivatives are synthesized such as Guar Gum Alkyl Amine Benzamide (GAAB) Of chemical structure Guar gum alkyl amine propionate of chemical structure The inventor has been able to synthesize the Guar Gum alkyl amine (GAA) by replacing aqeuous alkali induced high pH of the prior art synthesis by using high amount of ammonia to provide mild alkaline medium , which has facilitated suitable haloalkylating agents to attach to the equatorial hydroxyl group of Guar Gum without affecting the polymer chain. Use of high amount of ammonia in place of sodium hydroxide provided mild alkali environment for in situ transformation of haloalkylating agent adduct to new cationic guar gum alkyl amine. The novel GAA and their acid amide derivatives of the present Invention can be prepared by simple green chemistry approach and can be described by following general reaction scheme. The guar gum alkyl amine and its acid amide derivatives of formula I above can be prepared by reacting (1) guar gum with suitable haloalkylating agent in aqueous ammonia to produce guar gum alkyl amine of formula I and optionally (ii) reacting the resultant guar gum alkyl amine of formula I with corresponding acid halides in aqueous alkali medium to produce guar gum alkyl acid amide derivatives. The haloalkylating agents of step (i) may be selected from epichlorhydrin , epibromohydrin , 4- chloro 1,2-epoxybutane or 4-bromo 1,2-epoxybutane. In step (I) the reaction is carried out in an alcoholic medium such as n- propanol, isopropanol n- butanol amyl alcohol, ethanol or methanol. Reaction is preferably carried out at a basic pH range between 7.5 to 11 and temperature range 30-90o C. The acid halides of step (ii) above may be selected from acetyl chloride/bromide or acetic anhydride, sodium acetate and hydrochloric acid combination , propyl chloride/bromide, stearyl chloride/bromide , benzoyl chloride , benzoyl bromide, oleic acid chloride or bromide and the like depending on the exact acid amide derivatives. step (ii) of the reaction scheme is preferably carried out in sodium hydroxide solution to maintain a strong alkaline pH of a range 8-11 and the reaction of step (ii) is also carried out at a temperature range of 30-70 ° C. The following examples will described the preparatory methods of novel Guar gum alkyl amine and its derivatives according to the present invention. Preparatory Example 1. Synthesis of Guar-Gum alkyl amine (GAA) :- Guar-gum 25 grams, was taken in a 500 ml round bottom flask placed on a rotamantle and 100 ml of Isopropanol was then added with mechanical stirring. 50 ml of ammonium hydroxide was added to this suspension with continuous mechanical stirring. 50 ml 1-chloro- 2 ,3 -epoxypropane (epichloro hydrine) was then added drop wise to this yellowish slurry. The addition time was 1 hour. After the complete addition stirring was continued for one and half hours maintaining the reaction temperature at 55 - 60 ° c. The pH of the reaction mixture was maintained throughout between 8 and 9 by adding ammonium hydroxide time to time. The reaction mixture was then cooled and the light yellow solid was separated by the filtration in a Buckner funnel. The precipitate was washed twice with 80% of isopropanol and then finally with ethanol: water (1:1) and finally dried in a vacuum desicator. The yield recorded wasl9 grams. Solid state 13 C NMR , MAS, for Guar gum provided sugar C2, C3, C4 and C5 -CHOH being equivalent responded at 70.9, while the C1 sugar ether responded at 100.5 ppm, and the equatorial C6 carbon responded at 63.2 ppm. In case of Guar Gum alkyl amine a new peak due to -CH2 NH2 carbon appeared at 80.63 ppm. Preparatory Example 2. Synthesis of Guar-gum Alkyl Amine Acetate (GAAC) 2 Grams of GAA was dissolved in 2(M) cold aqueous HCl in a three necked round bottom flask placed on a rotamantle fitted with a mechanical stirrer, a condenser and a tube for purging in nitrogen from a cylinder. Then 20 grams of the hydrated sodium acetate was introduced in the reaction mixture followed by 20 ml of acetic anhydride with vigorous mechanical stirring over an ice bath until the smell of acetate disappears. The white solid acetyl derivative separated on standing was filtered in a Buckner funnel washed in 1:1 ethanol water and dried in vacuum desiccators. The Yield recorded was 1.1 grams. Acetylation of Guar Gum alkyl amine resulted in GAAC which ketone responded in solid state MAS at 171 with typical methyl carbon presence at 18 ppm. Preparatory Example 3. Synthesis of Guar-Gum alkyl amine Benzoate (GAAB): 5g of GAA was suspended in 100 ml of 5% Sodium Hydroxide solution. 10 ml of benzoyl chloride was then added portion wise with vigorous stirring. Temperature of reaction mixture was maintained to 30°C. The alkalinity of pH mixture was maintained using NaOH(10%). After completion of addition stirring was continued for 1hour. Then the solid GAAB was filtered off and subsequently washed with warm water and then ethanol. The product was dried in vacuum desicator. Before characterization the product was again purified by dialysis. The Yield recorded was 4 grams. Benzoylation of Guar Gum alkyl amine resulted in GGBA which ketone responded in solid state MAS at 191 ppm while the aromatic carbons responded at 165 ppm. Preparatory Example 4. Synthesis of Guar-gum Alkyl Amine Stearate (GAAS) : 5g of GAA was suspended in 100 ml of 5% Sodium Hydroxide solution. 10 ml of freshly prepared stearyl chloride was then added portion wise with vigorous stirring. Temperature of reaction mixture was maintained to 30°C. The alkalinity of pH mixture was maintained by adding 10 % w/v NaOH time to time. After completion of addition stirring was continued for 1hour more. Then the solid GAAS was filtered off and subsequently washed with warm water and then with 95 % ethanol. The product was dried in vacuum desicator. Before characterization the product was again purified by dialysis. The Yield recorded was 3.2 grams. The stearyl amide of Guar Gum alkyl amine resulted in GAAS which ketone responded in solid state MAS at 175 ppm while the straeyl carbons responded strongly at 30.3 ppm with typical observation of the end methyl carbon at 13 ppm. Preparatory Example 5. Synthesis of Guar-gum Alkyl Amine Oleate (GAAO) : 5g of GAA was suspended in 100 ml of 5% Sodium Hydroxide solution.10 ml of freshly prepared Oleic acid halide was then added portion wise with vigorous stirring. Temperature of reaction mixture was maintained to 30oC. The alkalinity of pH mixture was maintained by adding 10 % w/v NaOH time to time. After completion of addition stirring was continued for Ihour more. Then the solid GAAO was filtered off and subsequently washed with warm water and then with 95 % ethanol. The product was dried in vacuum desicator. Before characterization the product was again purified by dialysis. The Yield recorded was 3 grams. The oleayl amide of Guar Gum alkyl amine resulted in GAAO which ketone responded in solid state MAS at 174 ppm while the oleayl carbons responded at 30 ppm. Preparatory Example 6. Synthesis of Guar-gum Alkyl Amine Propionate (GAAP) : 5g of GAA was suspended in 100 ml of 5% Sodium Hydroxide solution. 10 ml of freshly prepared propyl chloride was then added portion wise with vigorous stirring. Temperature of reaction mixture was maintained to 30°C. The alkalinity of pH mixture was maintained by adding 10 % w/v NaOH time to time. After completion of addition stirring was continued for Ihour more. Then the solid GAAP was filtered off and subsequently washed with warm water and then with 95 % ethanol. The product was dried in vacuum desiccators. Before characterization the product was again purified by dialysis. The Yield recorded was 3.4 grams. The propionate amide of Guar Gum alkyl amine resulted in GAAP which ketone responded in solid state MAS at 174 ppm while the propionyl carbons responded at 23 ppm. DMSO, NaOH may used as a solvent instead of water, NaOH. Alternatively GAA may be reacted with benzoic acid methylate or ethylate ester and dicyclohexyl carbodimide (DCC) in polar organic solvents like ethanol/etanol/acetonitile/DMSO/THE DMSO may used as a solvent instead of water for in the preparation of acetate derivative . The new guar gum alkyl amine benzamides have significantly altered solubility GAAB, and GAAO are all completely insoluble in water but are soluble in DMSO. This new property may be useful for development of improved guar based films and therefore be applicable in paper and textile industry. This has resulted due to hydrophobization of surface -OH groups of guar gum hindering access of water to it. Element percentage composition analysis for CHNS Percentage C,H,N,S analysis was carried out by combustion technique in the CHNS analyzer model CHNS -932, M/s Leco corporation, U.S.A to understand for presence of C,H,N. and S in general . Samples weighed in semi micro balance Paul Bunge , model 23, Humburg , Germany were tal Evolving element oxides were monitored in instrument IR device and compared against standard supplied samples of acetophenon, and cystene supplied by Leco corporation . Determination of degree of substitution for GAA : 0.3 gm of the GAA sample was accurately weighed and half of the sample was taken in a dry iodine fiask, 6ml of cold acetic anhydride and pyridine (1 : 3) mixture was then added and the stopper was inserted. The mixture was cooled (4°C) and allowed to stand for 5 minutes at room temperature with gentle agitation. Then 10 ml of water was run down the stopper and wall of the flask. The content of the flask was swirled and the side of the flask was rinsed with 15 ml of n- butanol. The reaction mixture was immediately titrated against standard 0.5 (N) alcoholic NaOH solution to the appearance of a definite blue color by adding few drops of mixed indicator(5 parts of the 0.1%bromocresol green in acetic acid and one part 0.1% methyl red in methanol) A blank titration without the GAA sample was also performed simultaneously. The remaining half portion of washed GAA was dried in a oven at 102 °C to constant weight. This weight was taken as equal to the sample weight in titration. The Degree of substitution (D.S) was calculated using following formula W= Weight of the washed material taken for test, calculated on dry material basis. V0 = Volume of the NaOH needed for blank titration without GAA sample V1 = Volume of the NaOH needed for titration of the test sample T = Titre of the 0.1 (N) NaOH . M1= Molecular weight of the unsubstituted monomer unit = 162 . M2 = Molecular weight of the substituting unit = 59 . Determination of degree of substitution for GAAB : Degree of substituted compound GAAB was carried out similarly. 0.3 gm of the GGBA (IV) sample was accurately weighed and half of the sample was taken in a round bottomed flask. 100ml of IN Hydrochloric acid was added into it and the mixture was put to reflux over an water bath for one hour. The mixture was then cooled to room temperature and transferred quantitatively into a separator washing the contents in 25ml of solvent ether. The entire mixture was extracted in 4 successive quantities of ether 25 ml each and the combined ether layer was washed with 20ml. of water. The ether layer was evaporated over water bath and the residue was dissolved in 100 ml of 1 N NaOH. The excess NaOH was back titrated against standard HCl, methyl red as Indicator. Degree of substitution was then calculated as described earlier. The degree of substitution for all other compounds were determined similarly and were tabulated in table I. Solubility studies; Solubility quality of Guar gum and its derivatives were studied using 10mg weighed quantities in 2ml different solvents using water, hydrochloric acid, sodium hydroxide, N,N, Dimethyl formamide and phosphoric acid mixture (DMF/H3PO4) , Dichloromethane and Chloroform in order to have a systematic chemical understanding of the working biopolymer and its surface modified variants The detailed results of CHNS analysis, degree of substitution and solubility studies have been given in Table 1 below. Spectroscopy and characterization of new guar gum derivatives: FT- IR Studies FT-IR study was performed in the instrument FTIR JASCO® 670Plus. Dry powcer of each Guar gum derivative was palletized in 1: 100 w/w potassium bromide and were scanned over the mid IR range of 400 - 4000cm-1.Guar gum backbone was mostly constituted of sugar backbone C-C linkage associating with ether link that was represented at 1058cm'^ stretching vibration when recorded in potassium bromide pellets (Figure I) . Sugar hydroxyl group is highly hydrogen bonded that appeared at 3407 cm-1 When substituted in CMG distinct carboxyl group peak appeared at 1609 cm-1 in addition to hydrogen bonded -OH starching shifting up field at 3429 cm-1 1 possibly due to additional hydrogen bonding interactions due to the attached COOH function in vicinity. Thus establishing carboxymethyl guar gum (CMG) having additional -COOH functionality on the guar gum backbone. In GAA identifiable NH stretching at 2924 cm-land CN stretching at 1261 cm -1 in addition to sugar OH vibrations shifted at 3433cm-1 and the polymeric ethereal oxygen vibrations at 1022cm- 1 . Thus confirming the structural attachment of - CH2 NH2 functions. F-T I R Spectra of Guar-Gum (GG) Is shown in Fig 2 . F-T I R Spectra of Guar-Gum alkyl amine (GAA) is shown in Fig 3. FT I R Spectra of Carboxy methyl Guar-Gum (CMG) is shown in Fig 4. FT-IR Spectra of Guar gum alkyl amine benzoate( GAAB) is shown in Fig 5. FT-IR studies provided for appearance of CH2-NH2 & -CH2C00H on synthesized products . Therefore compound GAA and compound CMG were confirmed . C13 NMR studies Solid state magic angle NMR were recorded for representative compounds at 25 degree C and the data were presented In Fig 6-8. The Solid state 13 C NMR, for Guar gum provided C2, C3, C4 and C5 response at 70.9, and the saccharide C1 response at 100.5 ppm. The equatorial C6 carbon responded at 63.2 ppm. In case of Guar Gum alkyl amine a new peak due to -CH2 NH2 carbon appeared at 80.63 ppm. In case of Guar Gum alkyl amine acetate, the ketone carbon responded in solid state MAS at 171 with additional adjoining methyl carbon response at 18 ppm. The propionate amide of Guar Gum alkyl amine resulted in GGPA which ketone responded in solid state MAS at 174 ppm while the propionyl carbons responded at 23 ppm. In Guar Gum alkyl amine stearate, the ketone carbon responded in solid state MAS at 175 ppm while the straeyl chain carbons responded strongly at 30.3 ppm with typical observation for the end methyl carbon at 13 ppm. The Guar Gum alkyl amine benzoate, GGBA, ketone responded in solid state MAS at 191 ppm while the aromatic carbons responded at 165 ppm. The Guar Gum alkyl amine oleate, ketone carbon responded in solid state MAS at 174 ppm while the oleayl carbons responded at 30 ppm. Some of the above results are shown in Fig 5-7. Absorption of phenolic and polyplienolic compounds from aqueous environment The cationic guar gum alkyl amine derivatives interact with phenolics and polyphenolics such as phenol, catechol, cresol, catechol, picric acid, 4-nonylphenol, Propofol, Estradiol, Xynelol's, Bisphenol's, serotonin, dopamine, noradrenaline and polyphenols like gallic acid, Resorcinol, hydroquinone, epicatachin, catachin, quercitin etc. This property can be used for removal of similar agents from different sources. In one experiment Guar Gum Alkyl amine (GAA) at a concentration of 1X 10-7 M in water dispersion was added with different concentrations of phenol in a concentration range of 1x10-5 M Phenol to 9x 10-5M were stirred and the mixture was compared in UV scan in the range of phenol absorption at 276nm. Adsorption of phenol In GAA was recorded In all concentration ranges. The absorption equilibrium constant is presented in table - III and absorption and removal of phenol from aqueous environment by GAA was possible up to 1 ppb level. The chemical equilibrium for removal of phenolics was attributed due to charge transfer and hydrogen bonding interaction to GAA. This is attributed for the fact that GAA is a cationic polymer and phenol is a strong anion in aqueous environment. Absorption spectra of Guar gum alkyl amine (1x10-7 M) and Phenol complex at different concentrations against corresponding Phenol absorption scan.[1x10-5 M Phenol{-} to 9x 10-5 M {-}] is shown in Fig 8. Absorption of protein substances from aqueous environment Similarly protein materials are also BOD contributors and therefore are potential pollutants in environment. Proteins like whey protein, soluble proteins from biological and fermentation sources can be removed up to ppm levels from aqueous environments using different newer guar gum alkyl amine and derivatives. In one experiment Bovine serum albumin solution in water at different concentration were mixed with new guar gum alkyl amine derivatives and the BSA absorption were measured in each case. Compound VI was most active In absorption of BSA from aqueous environment followed by Guar gum alkyl amine acetate. Absorption spectra of Guar gum alkyl amine (1x10-7 M) and BSA complex at different concentrations with corresponding BSA absorption scan. [1x10-6 M BSA {-} to 9x 10-6 M {-}] and for complex {-}to {-}] is shown in Fig 9. The kinetic equilibrium constant K, is a determinant of the nature and efficiency of interaction and easily be determined from the formula, K= [DA]/ ([D].[A]). Where D, is the active concentration of the donor, protein and A, is the active concentration of the acceptor guar biopolymer and DA, is the active concentration of donor - acceptor complex at equilibrium. The same equation can now be derived as K= x/[(C1 -x)(C2 -x)]. Whereby x, represent the equilibrium concentration of complex DA, which can be obtained graphically from the UV response plot, and C1 represent the initial concentration of the donor, protein used and C2 represent the initial concentration of the acceptor, guar gum biopolymer used. Absorption and removal of soluble anionic components from aqueous environment Anionic components like phosphate, sulfate, cyanide, fluoride, chloride can be removed from soil and water environment. For example the removal of phosphate was effected at a 0.001 % to 1 % w/v solution of sodium phosphate in water against 0.5 gm of new guar gum alkyl amine derivative. The mixture was shaken in rotary shaker for 12 hours at 25 oC. The mixture was centrifuged at 5000 rpm for 10 mints and the supernatant was analyzed as follows.: In 1 ml of aliquot 2ml of reagent A and 17 ml. of water was added and left in dark to develop. Samples of this solution was then examined in a spectrophotometer at 822nm. The results were compared to a standard sample of phosphate prepared in water for determination of phosphate content. The order of efficiency of phosphate removal were rated as II > III > VI > V > IV . Removal of other anions were carried out similarly. Reagent A : 1.584 gm of Ascorbic acid is added in 300 ml of Reagent I. Reagent I : 6 gm ammonium molybdate, 0.146 gm antimony potassium tartrate, 72 ml sulfuric acid and the volume is made up to 1 Liter with distilled water. Absorption and removal of soluble anionic components from tissue fluid environment Similarly, anionic components like phosphate, sulfate, cyanide, fluoride, chloride can be removed from soil and water environment. For example the removal of phosphate, a 0.001 % to 1 % solution of sodium phosphate in water is added with 0.5 gm of new guar gum alkyl amine derivative and the mixture was shaken In rotary shaker for 12 hours at 25 OC. The mixture was centrifuged at 5000 rpm for 10 mints and the supernatant was analyzed as follows.: In 1 ml of aliquot 2ml of reagent A and 17 ml. of water was added and left in dark to develop. Samples of this solution was then examined in a spectrophotometer at 822nm. The results were compared to a standard sample of phosphate prepared in water for determination of phosphate content. The order of efficiency of phosphate removal were rated as II > III > VI > V > IV . Removal of other anions were carried out similarly. Reagent A : 1.584 gm of Ascorbic acid is added in 300 ml of Reagent I. Reagent I : 6 gm ammonium molybdate, 0.146 gm antimony potassium tartrate, 72 ml sulfuric acid and the volume is made up to 1 Liter with distilled water. Metal ion removal with CCMG resin in water In an equilibrium experiment Pb(NO3)2 and Cu(NO3)2 and Cd(NO3)2 in five different concentrations ranges were prepared from their respective stock solutions. 100 mg batch of the prepared resin (CCMG) ,11.1 was then added in each solution concentration of Pb(NO3)2 and Cu(NO3)2 and Cd(NO3)2 taken in different conical flasks . Flasks were then placed on a mechanical shaker with the temperature controlled at 27° C+2°C . The solutions were then centrifuged in Remi cooling centrifuge , model C30 at 10.000 r.p.m at 0°c . The supernatant solutions were decanted and metal concentrations were measured in Atomic absorption spectrophotometer , model AAS100 Perkin Elmer.USA before and after addition of CCMG resin . Entire experiment was performed in demineralized water .and the results were tabulated in table 3. The above experiments, results obtained there from indicate the Guar gum alkyl amine and its derivatives of the present invention have several utilities and therefore have industrial applicability. While the invention has been described with the help of few preferred embodiments, it would be readily apparent to a person sl departing from the scope and spirit of this invention as described above and defined in the appended set of claims. Claims: 1. Cationic guar gum alkyl amine and its derivatives of general formula I wherein X is CH2, n has a value of 3 or 4, R2 is one of H or COR3 and y denotes polymer linking. 2. A compound as claimed in claiml, wherein R3 Is selected from an alkyl or allyl or aryl group . 3. A compound as claimed in claim 2 , wherein R3 is methyl, ethyl, propyl or stearyl. 4. A compound as claimed in claim 2, wherein R3 is olealyl. 5. A compound as claimed in claim 2, wherein R3 is benzoyl. 6. A compound as claimed in any preceding claim, wherein the said compound has a degree of substitution in the range of 0.18 to 0.52. 7. A process for preparing a guar gum alkyl amine and its derivatives of formula I wherein X is CH2, n has a value of 3 or 4, R2 is one of H or COR3 and y denotes polymer linking, comprising reacting (i) guar gum with suitable haloalkylating agent in aqueous ammonia to produce guar gum alkyl amine of general formula II and optionally (ii) reacting the resultant guar gum alkyl amine of general formula II with corresponding acid halide In aqueous alkali to produce guar gum alkyl amine acetamide derivatives. 8. A process as claimed in claim 7, wherein R3 is selected from an alkyl or allyl or aryl group such as methyl, ethyl, propyl, stearyl, olealyl and benzoyl. 9. A process as claimed in claim 7, wherein the said haloalkylating agent is selected from epichlorhydrin , epibromohydrin , 4-chloro 1,2-epoxybutane or 4-bromo 1,2-epoxybutane. 10. A process as claimed in any preceding claim, wherein in step (i) the reaction is carried out in an alcoholic medium such as n- propanol, isopropanol, butanol ,amyl alcohol, ethanol or methanol. 11. A process as clamed in any of the preceding claim 7 to 10 wherein in step (i) the reaction is carried out at a basic pH range between 7.5 to 11 and temperature range 40-90 ° C. There is disclosed novel cationic guar gum alkyl amine and its acid amide derivatives of formula I wherein X is CH2, n has a value of 3 or 4, R2 is one of H or COR3 and y denotes polymer linking, as well as their process of preparation following green chemistry approach.

Full Text

Cationic Guar-Gum Alkyl Amine, Its Derivatives and Process of Preparation Thereof
Field of Invention:
This invention relates to novel cationic Guar gum alkyl amine (GAA) and its amide derivatives.
This invention also relates to a process for preparation of such novel Guar-gum alkyl amine (GAA)
and its derivatives following green chemistry approach.
BackGround of the Invention:
Guar gum is extracted from the guar bean. Chemically, guar gum is a polysaccharide composed
of the sugars galactose and mannose. The backbone is a linear chain of ß 1,4-linked mannose
residues to which galactose residues are 1,6-linked at every second mannose, forming short side-
branches. It has a chemical structure :

Cationic polysaccharides are known to be having good conditioning properties and used frequently
as industrial additives. Cationic derivatives of guar gum are widely used for the preparation of
shampoos, hair conditioners, personal and household care detergents as well as in pulp and
paper , food processing and pharmaceutical industries.
US Patent 3589978 discloses the use of cationic guar gum derivatives. US Patent 4061602
discloses use of cationic guar gum in preparation of shampoo. Guar 2 hydroxypropyl trimethyl
ammonium chloride and their preparatory methods are also known. However, both the above
compounds are hazardous and may form carcinoma due to the presence of free quarternary
ammonium group present in the reactant 2-3 epoxypropyl trimethyl ammonium chloride. US
patent publication US 2010/0036114 provides a process for preparation of a purified guar 2
hydroxy 3 (trimethylammonium) propyl ether chloride.
However, these compounds , though useful, are difficult to produce and structurally complex .
Therefore there is a need of synthesizing a structurally simpler cationic guar gum and Its
derivatives as well as their simple preparation process, following green chemistry approach, which
does not have the drawbacks of the prior art cationic guar gum derivatives and their preparatory
methods. The novel cationic Guar Gum alkyl amine and its derivatives could not be synthesized
previously because all prior art synthetic methods of guar gum were heavily dependent on use of
high amount of sodium hydroxide (alkali) causing chain breaking of guar polymer affecting
quality of the product and often non specific substitution. Moreover for synthesis of cationic guar
gum, higher temperature was necessary in media. The inventor has synthesized Guar gum alkyl
amine(GAA) compounds in simple preparatory method , which were not known hitherto before
and has also synthesised various amide derivatives of such GAA compounds as well as has
elucited their method of synthesis. The new Guar gum alkyl amine and derivatives may be used
for removal of molecules and ions from aqueous environments, tissue fluids as well as from
terrestrial water resources. The novel Guar gum alkyl amine and derivatives are excellent drug
delivery devices namely as, excipients in solid dosage forms, excipients in liquid dosage forms like
emulsions and suspensions, nanoparticle delivery devices, wound dressings, dentistry and
mucoadhesives. The novel Guar gum alkyl amine and derivative biopolymers of the present
invention can be used in cosmetics as formulation stabilizers, hair conditioners, preservatives and
gelling agents, as well.
Objects of the Invention:
It is a primary object of the invention to provide a novel Guar gum alkyl amine (GAA) compound
with a simpler structure.
It is another object of the invention to provide novel amide derivatives of GAA.
It is yet another objective of the invention is to provide a simple reaction scheme to produce GAA
and its derivatives.
It is a further object of the invention to provide GAA and its amide derivatives which are simpler
in structure but at least as effective as the known Cationic Guar Gum derivatives.
It is yet further objective of the invention is to provide a process for synthesis of novel GAA and
its derivatives following green chemistry approach.
This and other objects of the invention are described in the detailed description of the invention.
Summary of the Invention:
Accordingly the present invention provides Cationic guar gum alkyl amine and its amide type/
corresponding amide derivatives of general formula I
wherein X is CH2,
n has a value of 3 or 4,
R2 is one of H or COR3 and y denotes polymer linking.
Said R3 is selected from an alkyl or allyl or aryl group R3 is methyl, ethyl, propyl , stearyl,
olealyl or benzoyl.
Preferably the said compound has a degree of substitution in the range of 0.18 to 0.52.
The present invention also provides a process for preparing a guar gum akyl amine and its
corresponding amide/ amide derivatives of formula I

wherein X , n , R2 , R3and y are as defined above,comprising reacting (l) guar gum with suitable
haloalkylating agent in aqueous ammonia to produce guar gum alkyl amine of general formula II

and optionally (ii) reacting the resultant guar gum alkyl amine of general formula II with
corresponding acetate or a acid halide in aqueous alkali to produce guar gum alkyl amide or
acetamide derivatives.
Preferably the said haloalkylating agent is selected from epichlorhydrin, epibromohydrin , 4-chloro
1,2-epoxybutane and 4-bromo 1,2-epoxybutane
Preferably in step (i) the reaction is carried out in an alcoholic medium such as n- propanol,
isopropanol, n-butanol ,amyl alcohol, ethanol or methanol.
Preferably in step (i) the reaction is carried out at a basic pH range between 7.5 to 11 and
temperature range 30-90 ° C.
Brief Description of the Accompanying Drawings:
Fig 1 is F-T I R Spectra of Guar-Gum (GG).
Fig 2 is F-T I R Spectra of Guar-Gum alkyl amine (GAA) .
Fig 3 is FT-IR Spectra of Guar gum alkyl amine benzoate( GAAB) .
Fig 4 illustrates C13 NMR of Guar gum .
Fig 5 illustrates C13 NMR of Guar gum alkyl amine (GAA)
Fig 6 illustrates C13 NMR of Guar gum alkyl amine benzoate.
Fig 7 illustrates Guar gum alkyl amine (GAA) , phenol adsorption studies in U.V region.
Fig 9 illustrates Guar gum alkyl amine oleate (GAA) , B.S.A complexation studies in U.V region.
Detailed Description of the Invention:
The present invention discloses a novel Guar Gum Alkyl Amine (GAA) and its corresponding amide
and amide derivatives according to the General formula I

X is CH2, n has a value of 3 or 4,R2 is one of H or COR3,
R3 is selected from an alkyl or allyl or aryl group.R3 may be an alkyl group and may be selected
from methyl, ethyl, propyl, stearyl, olealyl. R3 may also be benzoyl group.
And y denotes polymer linking.
The novel Guar gum alkyl amine (GAA) of the present invention has a chemical structure denoted
by General formula II,
Guar gum n butyl amine
Degree of substitution in the novel compounds are in the range of 0.18 to 0.52 . By degree of
substitution, It Is meant the substitution of catlonic group on the equatorial hydroxyl groups on
ring 1 & 3 of Guar, measured by means of CHNS analysis described in detail later.
The equatorial -OH groups of position 6 in manose and galactose unit of guar gum are being
substituted by hydroxyalkyl amine group to produce the catlonic guar gum alkyl amine (GAA) of
the invention. The alkyl moeity of the substituted hydroxyalkyi amine group may be
hydroxypropyl when n in the formula I is 3 or butyl when n in the general formula I is 4.
It will be well understood by a person skilled in the art that guar gum alkyl amine and its
derivatives of the present invention can have varied molecular weight depending on the guar gum
source, the degree of polymerization and the degree of substitution.
Depending on the substitution of at the terminal amino group, various acid amide derivatives are
synthesized such as Guar Gum Alkyl Amine Benzamide (GAAB) Of chemical structure
Guar gum alkyl amine propionate of chemical structure

The inventor has been able to synthesize the Guar Gum alkyl amine (GAA) by replacing aqeuous
alkali induced high pH of the prior art synthesis by using high amount of ammonia to provide mild
alkaline medium , which has facilitated suitable haloalkylating agents to attach to the equatorial
hydroxyl group of Guar Gum without affecting the polymer chain.
Use of high amount of ammonia in place of sodium hydroxide provided mild alkali environment for
in situ transformation of haloalkylating agent adduct to new cationic guar gum alkyl amine.
The novel GAA and their acid amide derivatives of the present Invention can be prepared by
simple green chemistry approach and can be described by following general reaction scheme.
The guar gum alkyl amine and its acid amide derivatives of formula I above can be prepared by
reacting
(1) guar gum with suitable haloalkylating agent in aqueous ammonia to produce guar gum alkyl
amine of formula I and optionally
(ii) reacting the resultant guar gum alkyl amine of formula I with corresponding acid halides in
aqueous alkali medium to produce guar gum alkyl acid amide derivatives.
The haloalkylating agents of step (i) may be selected from epichlorhydrin , epibromohydrin , 4-
chloro 1,2-epoxybutane or 4-bromo 1,2-epoxybutane.
In step (I) the reaction is carried out in an alcoholic medium such as n- propanol, isopropanol n-
butanol amyl alcohol, ethanol or methanol.
Reaction is preferably carried out at a basic pH range between 7.5 to 11 and temperature range
30-90o C.
The acid halides of step (ii) above may be selected from acetyl chloride/bromide or acetic
anhydride, sodium acetate and hydrochloric acid combination , propyl chloride/bromide, stearyl
chloride/bromide , benzoyl chloride , benzoyl bromide, oleic acid chloride or bromide and the like
depending on the exact acid amide derivatives.
step (ii) of the reaction scheme is preferably carried out in sodium hydroxide solution to maintain
a strong alkaline pH of a range 8-11 and the reaction of step (ii) is also carried out at a
temperature range of 30-70 ° C.
The following examples will described the preparatory methods of novel Guar gum alkyl amine
and its derivatives according to the present invention.
Preparatory Example 1. Synthesis of Guar-Gum alkyl amine (GAA) :-
Guar-gum 25 grams, was taken in a 500 ml round bottom flask placed on a rotamantle and 100
ml of Isopropanol was then added with mechanical stirring. 50 ml of ammonium hydroxide was
added to this suspension with continuous mechanical stirring. 50 ml 1-chloro- 2 ,3 -epoxypropane
(epichloro hydrine) was then added drop wise to this yellowish slurry. The addition time was 1
hour. After the complete addition stirring was continued for one and half hours maintaining the
reaction temperature at 55 - 60 ° c. The pH of the reaction mixture was maintained throughout
between 8 and 9 by adding ammonium hydroxide time to time. The reaction mixture was then
cooled and the light yellow solid was separated by the filtration in a Buckner funnel. The
precipitate was washed twice with 80% of isopropanol and then finally with ethanol: water (1:1)
and finally dried in a vacuum desicator. The yield recorded wasl9 grams. Solid state 13 C NMR ,
MAS, for Guar gum provided sugar C2, C3, C4 and C5 -CHOH being equivalent responded at
70.9, while the C1 sugar ether responded at 100.5 ppm, and the equatorial C6 carbon responded
at 63.2 ppm. In case of Guar Gum alkyl amine a new peak due to -CH2 NH2 carbon appeared at
80.63 ppm.
Preparatory Example 2. Synthesis of Guar-gum Alkyl Amine Acetate (GAAC)
2 Grams of GAA was dissolved in 2(M) cold aqueous HCl in a three necked round bottom flask
placed on a rotamantle fitted with a mechanical stirrer, a condenser and a tube for purging in
nitrogen from a cylinder. Then 20 grams of the hydrated sodium acetate was introduced in the
reaction mixture followed by 20 ml of acetic anhydride with vigorous mechanical stirring over an
ice bath until the smell of acetate disappears. The white solid acetyl derivative separated on
standing was filtered in a Buckner funnel washed in 1:1 ethanol water and dried in vacuum
desiccators. The Yield recorded was 1.1 grams. Acetylation of Guar Gum alkyl amine resulted in
GAAC which ketone responded in solid state MAS at 171 with typical methyl carbon presence at
18 ppm.
Preparatory Example 3. Synthesis of Guar-Gum alkyl amine Benzoate (GAAB):
5g of GAA was suspended in 100 ml of 5% Sodium Hydroxide solution. 10 ml of benzoyl chloride
was then added portion wise with vigorous stirring. Temperature of reaction mixture was
maintained to 30°C. The alkalinity of pH mixture was maintained using NaOH(10%). After
completion of addition stirring was continued for 1hour. Then the solid GAAB was filtered off and
subsequently washed with warm water and then ethanol. The product was dried in vacuum
desicator. Before characterization the product was again purified by dialysis. The Yield recorded
was 4 grams. Benzoylation of Guar Gum alkyl amine resulted in GGBA which ketone responded in
solid state MAS at 191 ppm while the aromatic carbons responded at 165 ppm.
Preparatory Example 4. Synthesis of Guar-gum Alkyl Amine Stearate (GAAS) :
5g of GAA was suspended in 100 ml of 5% Sodium Hydroxide solution. 10 ml of freshly prepared
stearyl chloride was then added portion wise with vigorous stirring. Temperature of reaction
mixture was maintained to 30°C. The alkalinity of pH mixture was maintained by adding 10 % w/v
NaOH time to time. After completion of addition stirring was continued for 1hour more. Then the
solid GAAS was filtered off and subsequently washed with warm water and then with 95 %
ethanol. The product was dried in vacuum desicator. Before characterization the product was
again purified by dialysis. The Yield recorded was 3.2 grams. The stearyl amide of Guar Gum alkyl
amine resulted in GAAS which ketone responded in solid state MAS at 175 ppm while the straeyl
carbons responded strongly at 30.3 ppm with typical observation of the end methyl carbon at 13
ppm.
Preparatory Example 5. Synthesis of Guar-gum Alkyl Amine Oleate (GAAO) :
5g of GAA was suspended in 100 ml of 5% Sodium Hydroxide solution.10 ml of freshly prepared
Oleic acid halide was then added portion wise with vigorous stirring. Temperature of reaction
mixture was maintained to 30oC. The alkalinity of pH mixture was maintained by adding 10 % w/v
NaOH time to time. After completion of addition stirring was continued for Ihour more. Then the
solid GAAO was filtered off and subsequently washed with warm water and then with 95 %
ethanol. The product was dried in vacuum desicator. Before characterization the product was
again purified by dialysis. The Yield recorded was 3 grams. The oleayl amide of Guar Gum alkyl
amine resulted in GAAO which ketone responded in solid state MAS at 174 ppm while the oleayl
carbons responded at 30 ppm.
Preparatory Example 6. Synthesis of Guar-gum Alkyl Amine Propionate (GAAP) :
5g of GAA was suspended in 100 ml of 5% Sodium Hydroxide solution. 10 ml of freshly prepared
propyl chloride was then added portion wise with vigorous stirring. Temperature of reaction
mixture was maintained to 30°C. The alkalinity of pH mixture was maintained by adding 10 % w/v
NaOH time to time. After completion of addition stirring was continued for Ihour more. Then the
solid GAAP was filtered off and subsequently washed with warm water and then with 95 %
ethanol. The product was dried in vacuum desiccators. Before characterization the product was
again purified by dialysis. The Yield recorded was 3.4 grams. The propionate amide of Guar Gum
alkyl amine resulted in GAAP which ketone responded in solid state MAS at 174 ppm while the
propionyl carbons responded at 23 ppm.
DMSO, NaOH may used as a solvent instead of water, NaOH. Alternatively GAA may be reacted
with benzoic acid methylate or ethylate ester and dicyclohexyl carbodimide (DCC) in polar organic
solvents like ethanol/etanol/acetonitile/DMSO/THE DMSO may used as a solvent instead of water
for in the preparation of acetate derivative . The new guar gum alkyl amine benzamides have
significantly altered solubility GAAB, and GAAO are all completely insoluble in water but are
soluble in DMSO. This new property may be useful for development of improved guar based films
and therefore be applicable in paper and textile industry. This has resulted due to
hydrophobization of surface -OH groups of guar gum hindering access of water to it.
Element percentage composition analysis for CHNS
Percentage C,H,N,S analysis was carried out by combustion technique in the CHNS analyzer
model CHNS -932, M/s Leco corporation, U.S.A to understand for presence of C,H,N. and S in
general . Samples weighed in semi micro balance Paul Bunge , model 23, Humburg , Germany
were tal Evolving element oxides were monitored in instrument IR device and compared against standard
supplied samples of acetophenon, and cystene supplied by Leco corporation .
Determination of degree of substitution for GAA :
0.3 gm of the GAA sample was accurately weighed and half of the sample was taken in a dry
iodine fiask, 6ml of cold acetic anhydride and pyridine (1 : 3) mixture was then added and the
stopper was inserted. The mixture was cooled (4°C) and allowed to stand for 5 minutes at room
temperature with gentle agitation. Then 10 ml of water was run down the stopper and wall of the
flask. The content of the flask was swirled and the side of the flask was rinsed with 15 ml of n-
butanol. The reaction mixture was immediately titrated against standard 0.5 (N) alcoholic NaOH
solution to the appearance of a definite blue color by adding few drops of mixed indicator(5 parts
of the 0.1%bromocresol green in acetic acid and one part 0.1% methyl red in methanol) A blank
titration without the GAA sample was also performed simultaneously. The remaining half portion
of washed GAA was dried in a oven at 102 °C to constant weight. This weight was taken as equal
to the sample weight in titration.
The Degree of substitution (D.S) was calculated using following formula

W= Weight of the washed material taken for test, calculated on dry material basis.
V0 = Volume of the NaOH needed for blank titration without GAA sample
V1 = Volume of the NaOH needed for titration of the test sample
T = Titre of the 0.1 (N) NaOH . M1= Molecular weight of the unsubstituted monomer unit = 162 .
M2 = Molecular weight of the substituting unit = 59 .
Determination of degree of substitution for GAAB :
Degree of substituted compound GAAB was carried out similarly. 0.3 gm of the GGBA (IV) sample
was accurately weighed and half of the sample was taken in a round bottomed flask. 100ml of IN
Hydrochloric acid was added into it and the mixture was put to reflux over an water bath for one
hour. The mixture was then cooled to room temperature and transferred quantitatively into a
separator washing the contents in 25ml of solvent ether. The entire mixture was extracted in 4
successive quantities of ether 25 ml each and the combined ether layer was washed with 20ml. of
water. The ether layer was evaporated over water bath and the residue was dissolved in 100 ml
of 1 N NaOH. The excess NaOH was back titrated against standard HCl, methyl red as Indicator.
Degree of substitution was then calculated as described earlier. The degree of substitution for all
other compounds were determined similarly and were tabulated in table I.
Solubility studies;
Solubility quality of Guar gum and its derivatives were studied using 10mg weighed quantities
in 2ml different solvents using water, hydrochloric acid, sodium hydroxide, N,N, Dimethyl
formamide and phosphoric acid mixture (DMF/H3PO4) , Dichloromethane and Chloroform in order
to have a systematic chemical understanding of the working biopolymer and its surface modified
variants
The detailed results of CHNS analysis, degree of substitution and solubility studies have been
given in Table 1 below.
Spectroscopy and characterization of new guar gum derivatives:
FT- IR Studies
FT-IR study was performed in the instrument FTIR JASCO® 670Plus. Dry powcer of each Guar
gum derivative was palletized in 1: 100 w/w potassium bromide and were scanned over the mid
IR range of 400 - 4000cm-1.Guar gum backbone was mostly constituted of sugar backbone C-C
linkage associating with ether link that was represented at 1058cm'^ stretching vibration when
recorded in potassium bromide pellets (Figure I) . Sugar hydroxyl group is highly hydrogen
bonded that appeared at 3407 cm-1 When substituted in CMG distinct carboxyl group peak
appeared at 1609 cm-1 in addition to hydrogen bonded -OH starching shifting up field at 3429 cm-1
1 possibly due to additional hydrogen bonding interactions due to the attached COOH function in
vicinity. Thus establishing carboxymethyl guar gum (CMG) having additional -COOH functionality
on the guar gum backbone.
In GAA identifiable NH stretching at 2924 cm-land CN stretching at 1261 cm -1 in addition to
sugar OH vibrations shifted at 3433cm-1 and the polymeric ethereal oxygen vibrations at 1022cm-
1 . Thus confirming the structural attachment of - CH2 NH2 functions.
F-T I R Spectra of Guar-Gum (GG) Is shown in Fig 2 .
F-T I R Spectra of Guar-Gum alkyl amine (GAA) is shown in Fig 3.
FT I R Spectra of Carboxy methyl Guar-Gum (CMG) is shown in Fig 4.
FT-IR Spectra of Guar gum alkyl amine benzoate( GAAB) is shown in Fig 5.
FT-IR studies provided for appearance of CH2-NH2 & -CH2C00H on synthesized products .
Therefore compound GAA and compound CMG were confirmed .
C13 NMR studies
Solid state magic angle NMR were recorded for representative compounds at 25 degree C and the
data were presented In Fig 6-8. The Solid state 13 C NMR, for Guar gum provided C2, C3, C4 and
C5 response at 70.9, and the saccharide C1 response at 100.5 ppm. The equatorial C6 carbon
responded at 63.2 ppm. In case of Guar Gum alkyl amine a new peak due to -CH2 NH2 carbon
appeared at 80.63 ppm. In case of Guar Gum alkyl amine acetate, the ketone carbon responded
in solid state MAS at 171 with additional adjoining methyl carbon response at 18 ppm. The
propionate amide of Guar Gum alkyl amine resulted in GGPA which ketone responded in solid
state MAS at 174 ppm while the propionyl carbons responded at 23 ppm. In Guar Gum alkyl
amine stearate, the ketone carbon responded in solid state MAS at 175 ppm while the straeyl
chain carbons responded strongly at 30.3 ppm with typical observation for the end methyl carbon
at 13 ppm. The Guar Gum alkyl amine benzoate, GGBA, ketone responded in solid state MAS at
191 ppm while the aromatic carbons responded at 165 ppm. The Guar Gum alkyl amine oleate,
ketone carbon responded in solid state MAS at 174 ppm while the oleayl carbons responded at 30
ppm. Some of the above results are shown in Fig 5-7.
Absorption of phenolic and polyplienolic compounds from aqueous environment
The cationic guar gum alkyl amine derivatives interact with phenolics and polyphenolics such as
phenol, catechol, cresol, catechol, picric acid, 4-nonylphenol, Propofol, Estradiol, Xynelol's,
Bisphenol's, serotonin, dopamine, noradrenaline and polyphenols like gallic acid, Resorcinol,
hydroquinone, epicatachin, catachin, quercitin etc. This property can be used for removal of
similar agents from different sources. In one experiment Guar Gum Alkyl amine (GAA) at a
concentration of 1X 10-7 M in water dispersion was added with different concentrations of phenol
in a concentration range of 1x10-5 M Phenol to 9x 10-5M were stirred and the mixture was
compared in UV scan in the range of phenol absorption at 276nm. Adsorption of phenol In GAA
was recorded In all concentration ranges. The absorption equilibrium constant is presented in
table - III and absorption and removal of phenol from aqueous environment by GAA was possible
up to 1 ppb level. The chemical equilibrium for removal of phenolics was attributed due to charge
transfer and hydrogen bonding interaction to GAA. This is attributed for the fact that GAA is a
cationic polymer and phenol is a strong anion in aqueous environment. Absorption spectra of
Guar gum alkyl amine (1x10-7 M) and Phenol complex at different concentrations against
corresponding Phenol absorption scan.[1x10-5 M Phenol{-} to 9x 10-5 M {-}] is shown in Fig 8.
Absorption of protein substances from aqueous environment
Similarly protein materials are also BOD contributors and therefore are potential pollutants in
environment. Proteins like whey protein, soluble proteins from biological and fermentation
sources can be removed up to ppm levels from aqueous environments using different newer guar
gum alkyl amine and derivatives. In one experiment Bovine serum albumin solution in water at
different concentration were mixed with new guar gum alkyl amine derivatives and the BSA
absorption were measured in each case. Compound VI was most active In absorption of BSA from
aqueous environment followed by Guar gum alkyl amine acetate.
Absorption spectra of Guar gum alkyl amine (1x10-7 M) and BSA complex at different
concentrations with corresponding BSA absorption scan. [1x10-6 M BSA {-} to 9x 10-6 M {-}]
and for complex {-}to {-}] is shown in Fig 9. The kinetic equilibrium constant K, is a determinant
of the nature and efficiency of interaction and easily be determined from the formula, K= [DA]/
([D].[A]). Where D, is the active concentration of the donor, protein and A, is the active
concentration of the acceptor guar biopolymer and DA, is the active concentration of donor -
acceptor complex at equilibrium. The same equation can now be derived as K= x/[(C1 -x)(C2 -x)].
Whereby x, represent the equilibrium concentration of complex DA, which can be obtained
graphically from the UV response plot, and C1 represent the initial concentration of the donor,
protein used and C2 represent the initial concentration of the acceptor, guar gum biopolymer used.
Absorption and removal of soluble anionic components from aqueous environment
Anionic components like phosphate, sulfate, cyanide, fluoride, chloride can be removed from soil
and water environment. For example the removal of phosphate was effected at a 0.001 % to 1 %
w/v solution of sodium phosphate in water against 0.5 gm of new guar gum alkyl amine
derivative. The mixture was shaken in rotary shaker for 12 hours at 25 oC. The mixture was
centrifuged at 5000 rpm for 10 mints and the supernatant was analyzed as follows.: In 1 ml of
aliquot 2ml of reagent A and 17 ml. of water was added and left in dark to develop. Samples of
this solution was then examined in a spectrophotometer at 822nm. The results were compared to
a standard sample of phosphate prepared in water for determination of phosphate content. The
order of efficiency of phosphate removal were rated as II > III > VI > V > IV . Removal of other
anions were carried out similarly.
Reagent A : 1.584 gm of Ascorbic acid is added in 300 ml of Reagent I. Reagent I : 6 gm
ammonium molybdate, 0.146 gm antimony potassium tartrate, 72 ml sulfuric acid and the
volume is made up to 1 Liter with distilled water.
Absorption and removal of soluble anionic components from tissue fluid environment
Similarly, anionic components like phosphate, sulfate, cyanide, fluoride, chloride can be removed
from soil and water environment. For example the removal of phosphate, a 0.001 % to 1 %
solution of sodium phosphate in water is added with 0.5 gm of new guar gum alkyl amine
derivative and the mixture was shaken In rotary shaker for 12 hours at 25 OC. The mixture was
centrifuged at 5000 rpm for 10 mints and the supernatant was analyzed as follows.: In 1 ml of
aliquot 2ml of reagent A and 17 ml. of water was added and left in dark to develop. Samples of
this solution was then examined in a spectrophotometer at 822nm. The results were compared to
a standard sample of phosphate prepared in water for determination of phosphate content. The
order of efficiency of phosphate removal were rated as II > III > VI > V > IV . Removal of other
anions were carried out similarly.
Reagent A : 1.584 gm of Ascorbic acid is added in 300 ml of Reagent I. Reagent I : 6 gm
ammonium molybdate, 0.146 gm antimony potassium tartrate, 72 ml sulfuric acid and the
volume is made up to 1 Liter with distilled water.
Metal ion removal with CCMG resin in water
In an equilibrium experiment Pb(NO3)2 and Cu(NO3)2 and Cd(NO3)2 in five different concentrations
ranges were prepared from their respective stock solutions. 100 mg batch of the prepared resin
(CCMG) ,11.1 was then added in each solution concentration of Pb(NO3)2 and Cu(NO3)2 and
Cd(NO3)2 taken in different conical flasks . Flasks were then placed on a mechanical shaker with the
temperature controlled at 27° C+2°C . The solutions were then centrifuged in Remi cooling
centrifuge , model C30 at 10.000 r.p.m at 0°c . The supernatant solutions were decanted and metal
concentrations were measured in Atomic absorption spectrophotometer , model AAS100 Perkin
Elmer.USA before and after addition of CCMG resin . Entire experiment was performed in
demineralized water .and the results were tabulated in table 3.

The above experiments, results obtained there from indicate the Guar gum alkyl amine and its
derivatives of the present invention have several utilities and therefore have industrial
applicability.
While the invention has been described with the help of few preferred embodiments, it would be
readily apparent to a person sl departing from the scope and spirit of this invention as described above and defined in the
appended set of claims.
Claims:
1. Cationic guar gum alkyl amine and its derivatives of general formula I

wherein X is CH2,
n has a value of 3 or 4,
R2 is one of H or COR3 and y denotes polymer linking.
2. A compound as claimed in claiml, wherein R3 Is selected from an alkyl or allyl or aryl group .
3. A compound as claimed in claim 2 , wherein R3 is methyl, ethyl, propyl or stearyl.
4. A compound as claimed in claim 2, wherein R3 is olealyl.
5. A compound as claimed in claim 2, wherein R3 is benzoyl.
6. A compound as claimed in any preceding claim, wherein the said compound has a degree of
substitution in the range of 0.18 to 0.52.
7. A process for preparing a guar gum alkyl amine and its derivatives of formula I

wherein X is CH2,
n has a value of 3 or 4,
R2 is one of H or COR3 and y denotes polymer linking,
comprising reacting (i) guar gum with suitable haloalkylating agent in aqueous ammonia to
produce guar gum alkyl amine of general formula II

and optionally
(ii) reacting the resultant guar gum alkyl amine of general formula II with corresponding
acid halide In aqueous alkali to produce guar gum alkyl amine acetamide derivatives.
8. A process as claimed in claim 7, wherein R3 is selected from an alkyl or allyl or aryl group such
as methyl, ethyl, propyl, stearyl, olealyl and benzoyl.
9. A process as claimed in claim 7, wherein the said haloalkylating agent is selected from
epichlorhydrin , epibromohydrin , 4-chloro 1,2-epoxybutane or 4-bromo 1,2-epoxybutane.
10. A process as claimed in any preceding claim, wherein in step (i) the reaction is carried out in
an alcoholic medium such as n- propanol, isopropanol, butanol ,amyl alcohol, ethanol or methanol.
11. A process as clamed in any of the preceding claim 7 to 10 wherein in step (i) the reaction is
carried out at a basic pH range between 7.5 to 11 and temperature range 40-90 ° C.

There is disclosed novel cationic guar gum alkyl amine and its acid amide derivatives of formula I

wherein X is CH2, n has a value of 3 or 4, R2 is one of H or COR3 and y denotes polymer linking,
as well as their process of preparation following green chemistry approach.

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Patent Number

279095

Indian Patent Application Number

778/KOL/2010

PG Journal Number

02/2017

Publication Date

13-Jan-2017

Grant Date

11-Jan-2017

Date of Filing

19-Jul-2010

Name of Patentee

MUKHERJEE ARUP

Applicant Address

DEPARTMENT OF CHEMICAL TECHNOLOGY, CALCUTTA UNIVERSITY, 92, A.P.C. ROAD KOLKATA-700 009, WEST BENGAL, INDIA

Inventors:

#	Inventor's Name	Inventor's Address
1	MUKHERJEE ARUP	DEPARTMENT OF CHEMICAL TECHNOLOGY, CALCUTTA UNIVERSITY, 92, A.P.C. ROAD KOLKATA-700 009, WEST BENGAL, INDIA

PCT International Classification Number

C08L21/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA