Title of Invention	PROCESS FOR MANUFACTUR OF QUATERNARY AMMONIUM TOSYLATES OF CINNAMIDOALKYLAMINES AND/OR BENZAMIDOALKYLAMINES
Abstract	A process for preparing quaternary ammonium tosylates of cinnamidoalkylamines and/or benzamidoalkylamines of Formula I, Formula I wherein; ArCO is selected from p-N,N-dimethylamino benzoyl or p-methoxy cinnamoyl; R1 is selected from H or alkyl groups containing from 1 to 6 carbon atoms; R2 and R3 are independently selected from alkyl groups containing from 1 to 12 carbon atoms; R4 is selected from alkyl or alkenyl groups containing from 8 to 22 carbons; n is an integer having values from 1 to 6; comprising steps of (i) quatemisation of 1.0 mole of cinnamidoalkylamine and / or benzamidoalkylamine of Formula II with 1.0 mole of fatty alkyl halides of Formula HI, wherein, Ri, R2, R3, R4 and n is same as that in the compound of said Formula I, with or without solvent, to obtain a quaternary ammonium halide of Formula IV;

Title of Invention

PROCESS FOR MANUFACTUR OF QUATERNARY AMMONIUM TOSYLATES OF CINNAMIDOALKYLAMINES AND/OR BENZAMIDOALKYLAMINES

Abstract

A process for preparing quaternary ammonium tosylates of cinnamidoalkylamines and/or benzamidoalkylamines of Formula I, Formula I wherein; ArCO is selected from p-N,N-dimethylamino benzoyl or p-methoxy cinnamoyl; R1 is selected from H or alkyl groups containing from 1 to 6 carbon atoms; R2 and R3 are independently selected from alkyl groups containing from 1 to 12 carbon atoms; R4 is selected from alkyl or alkenyl groups containing from 8 to 22 carbons; n is an integer having values from 1 to 6; comprising steps of (i) quatemisation of 1.0 mole of cinnamidoalkylamine and / or benzamidoalkylamine of Formula II with 1.0 mole of fatty alkyl halides of Formula HI, wherein, Ri, R2, R3, R4 and n is same as that in the compound of said Formula I, with or without solvent, to obtain a quaternary ammonium halide of Formula IV;

Full Text	FORM 2 THE PATENTS ACT, 1970 (39 of 1970) COMPLETE SPECIFICATION (See Section 10 : Rule 13) TITLE Process for manufacture of quaternary ammonium tosylates of cinnamidoalkylamines and / or benzamidoalkylamines APPLICANT Galaxy Surfactants Ltd., C-49/2, TTC Industrial Area, Pawne, Navi-Mumbai 400 703, Maharashtra, India. A Public Limited Company Registered under Indian Company's Act - 1956 The following specification particularly describes the nature of this invention and the manner in which it is to be performed :- ORIGIANL 21-8-2003 GRANTED 8-1-2004 Field of Invention : This invention relates to an improved process for manufacture of cationic, quaternary ammonium tosylate salts of cinnamidoalkylamines and / or benzamidoalkylamines. This invention particularly relates to the synthesis of tailor made non-hydrolyzable, non-irritating compounds having substantivity to cotton, wool, skin and hair and UV-radiation absorbing properties useful in personal care and fabric care formulations. Background and Prior Art: US patent 5,427,773 (1995) discloses preparation of cationic substantive photofilters like dodecyl dimethyl amino benzamido propyl dimethyl ammonium tosylate. In this process, a primary amino group of iV.iV-dimethyl propyl diamine is reacted with dimethyl amino benzoic acid to form an amidoamine and then the tertiary amino group of the amidoamine is quatemised with alkyl tosylate. Similarly, US Patent 6,613,340 (2003) discloses cationic tosylate salts from cinnamidoalkylamines following the same methodology. The procedures described in both patents are very tedious where alkyl tosylates used for quaternisation are prepared from fatty alcohols and tosyl chloride. This reaction is done in a suitable solvent using stoichiometric quantities of tertiary amine bases like triethylamine or pyridine. The organic bases mop up the hydrochloric acid generated and the subsequent hydrochloride-base salt that is formed as a by¬product has to be removed by washing the reaction mixture with water. This significantly increases the effluent load. Another disadvantage of this process is that the reaction of preparation of alkyl tosylate is carried out in halogenated solvents like dichloromethane or aromatic solvents. Purification of alkyl tosylate also results in significant loss of yield and simultaneous increase in effluent treatment. This is mainly due to the presence of unconverted fatty alcohols. The quaternisation of cinnamidoalkylamines and / or benzamidoalkylamines with alkyl tosylate does not give quantitative conversion and hence the after purification step the isolated yields of quatemised UV-absorbers range between 65 to 70 %. In summary, all these factors make the process for making quatemised UV-absorbers not only tedious and expensive but also non-environment friendly. Hence, there is a need for a simple, quantitative and eco-friendly process for making these substantive UV-absorbers. Object of the invention : The main object of the present invention is to make the process of synthesizing the tosylate quaternary salts of cinnamidoalkylamines and / or benzamidoalkylamines simple, quantitative and eco-friendly. Summary of the invention : The present invention provides a process for preparing quaternary ammonium tosylates of cinnamidoalkylamines and / or benzamidoalkylamines of Formula I, Formula I wherein; ArCO is selected fromp-Af,Af-dimethylamino benzoyl and / or p-methoxy cinnamoyl; Ri is selected from H or alkyl groups containing from 1 to 6 carbon atoms; R2 and R3 are independently selected from alkyl groups containing from 1 to 12 carbon atoms; R4is selected from alkyl or alkenyl groups containing from 8 to 22 carbons; n is an integer having values from 1 to 6; comprising steps of (i) quatemisation of 1.0 mole of cinnamidoalkylamine and / or benzamidoalkylamine of Formula II with 1.0 mole of alkylating compound of Formula HI, wherein, R\, R2, R3, R4 and n is same as that in the compound of said Formula I, with or without solvent, to obtain a quaternary ammonium halide of Formula IV; (ii) treating the aqueous solution of quaternary ammonium halide of Formula IV obtained in step (i) with stoichiometric quantity of sodium p-toluene sulphonate to get water insoluble quaternary ammonium tosylate of Formula I; Formula IV and the products made by the process. Detailed description of the invention : The process of making compounds of Formula I described in the present invention comprises of two steps, a) synthesis of quaternary ammonium halides of Formula IV and b) conversion of water soluble quaternary compounds of Formula IV to water-insoluble quaternary ammonium tosylates. In the process described in the present invention, the cinnamidoalkylamines and / or benzamidoalkylamines of Formula HI are synthesised as per the literature procedures [US patent 5,427,773 (1995), US Patent 6,613,340 (2003)]. These UV-absorbing amidoamines are quaternised using commercially available alkyl halides of Formula III in aqueous / alcoholic medium to give quantitative generation of corresponding water-soluble, UV-absorbing, quaternary ammonium halides of Formula IV. The reaction can be carried out in water, alcohols or mixtures thereof. The quaternisation reaction can be conveniently done in a pressure reactor as well as in an open system. The temperatures suitable for pressure reaction range from about 100 - 135°C with the pressures up to 50 psi. The pressures are governed by the amount of solvent and the temperature selected for the reaction. The conditions of reaction in an open vessel also get dictated by the choice of solvent. The progress of the reaction is monitored by measuring the amount of unreacted alkylating agent by chromatography or by estimation of unquaternized amidoamine or by estimation of X", the halide anion. Alternately, quaternisations can be carried out by directly reacting cinnamidoalkylamines and / or benzamidoalkylamines of Formula II with alkyl halides of Formula HI at from about 100 to 140°C for 4 to 24 hours without any solvent and in an inert atmosphere of nitrogen. The progress of the reaction is monitored by estimation of unquaternised tertiary amine as well as by the estimation of liberated halide. In another embodiment, the process of the present invention relates to manufacture of quaternary ammonium tosylates of Formula I, in which ArCO is selected from p-JV.iV-dimethylamino benzoyl and / or p-methoxy cinnamoyl; R1 is selected from H or alkyl groups containing from 1 to 6 carbon atoms, R2 and R3 are independently selected from alkyl groups containing from 1 to 12 carbon atoms; R4 is selected from alkyl or alkenyl groups containing from 8 to 22 carbons; n is an integer having values from 1 to 6; from the compounds of Formula II, m, IV and sodium p-toluene sulphonate, with respective substituents ArCO, R1, R2, R3, and n of Formula n, R4 of Fonnula HI and ArCO, R1 R2, R3, R4, and n of Formula IV as defined for the compounds of Formula I in this embodiment. In another embodiment, the process of the present invention relates to manufacture of a quaternary ammonium tosylate of Formula I, in which ArCO = p-methoxy cinnamoyl, Ri = H, R2, R3 = -CH3, R4 = -C12H25 and n = 3, from the compound of Formula II (p-methoxy cinnamidopropyl dimethylamine, ArCO = p-methoxy cinnamoyl, R1 = H, R2, R3 = -CH3, n = 3) quaternised with compound of Formula HI (lauryl chloride, R4 = -C12H25, X" = chloride anion) forming the quaternised compound of Formula rv (p-methoxy cinnamidopropyl dimethyl lauryl ammonium chloride, R1 = H, R2, R3 = -CH3, R4 = -C12H25, n = 3, X" = chloride anion), aqueous solution of which is then treated with stoichiometric quantity of sodium p-toluene sulphonate. The process of preparation of such compound is given in Example I. In another embodiment, the process of the present invention relates to manufacture of a quaternary ammonium tosylate of Formula I, in which ArCO = p-A/,Af-dimethylamino benzoyl, R1 = H, R2, R3 = -CH3, R4 = -C12H25 and n = 3, from the compound of Formula II (p-N,N-dimethylamino benzamidopropyldimethylamine, ArCO = p-A/,AT-dimethyl aminobenzoyl, R1 = H, R2, R3 = -CH3, n = 3) quaternised with compound of Formula HI (lauryl chloride, R4 = -C12H25, X" = chloride anion) forming the quaternised compound of Formula IV (p-MiV-dimethylamino benzamido propyldimethyllauryl ammonium chloride, R1 = H, R2, R3 = -CH3, R4 = -C12H25, n = 3, X" = chloride anion), aqueous solution of which is then treated with stoichiometric quantity of sodium p-toluene sulphonate. The process of preparation of such compound is given in Example Examples Alkyl halides were obtained from Henkel. p-Toluene sulphonic acid was obtained from Aldrich. p-Methoxy cinnamidopropyldimethylamine and p-Af,7V-dimethylamino benzamidopropyl dimethylamine were synthesised as per literature procedures [US patent 5,427,773 (1995), US Patent Application No. 20030064083 April, 2003]. Example I Process for preparation p-methoxy cinnamidopropvldimethvllaurvl ammonium tosylate : The compound of Formula I, wherein, ArCO = p-methoxy cinnamoyl; Ri = H; R2, R3 = CH3; n = 3; R4 = -C12H25. a) Preparation of p-methoxv cinnamidopropyldimethyllaurfl ammonium chloride : A mixture of lauryl chloride (7.8 g, 38.17 mmol) and p-methoxy cinnamidopropyldimethyl amine (10.0 g, 38.17 mmol) was stirred under blanket of nitrogen at 110°C for 20 hours. The progress of reaction was monitored by estimation of unquaternised amine. Estimated chloride ion and free amidoamine was found to be 7.6 % and 0.12 % respectively. On cooling, the reaction yielded the quaternary ammonium compound (17.78 g, 99.9 %) as pale yellow solid. b) Preparation of p-methoxy cinnamidopropyldimethyllauryl ammonium tosylate : p-Methoxy cinnamidopropyldimethyllauryl ammonium chloride (17.78 g, 38.11 mmol) was dissolved in water to make 30 % solution. To this stirred solution, sodium p-toluene sulphonate (7.4 g, 38.14 mmol) was added and the separated pale yellow coloured solid was subsequently washed with water, filtered and dried to yield the corresponding tosylate (22.9 g, 99.83 %) as off-white solid, m.p. 128 - 130°C. Chloride ion was totally absent in the product. IR (CH2C12): 3465, 3286, 3052, 2920, 1659, 1617 cm"1. *H NMR (CDCI3, 300 MHz) : 8 0.87 (3H, t, J = 6.3 Hz), 1.18 (18H, broad signal), 1.58 (2H, unresolved multiplet), 2.10 (2H, unresolved multiplet), 2.32 (3H, singlet, methyl of tosyl), 3.13 (6H, singlet, two methyl on nitrogen), 3.20 (2H, unresolved multiplet), 3.45 (2H, unresolved multiplet), 3.68 (2H, unresolved multiplet), 3.78 (3H, singlet, OCH3), 6.52 (1H, d, J = 15.6 Hz), 6.76 (2H, d, J = 8.4 Hz), 7.14 (2H, d, J = 6.0 Hz), 7.31 (2H, d, J = 8.6 Hz), 7.48 (1H, d, J = 15.6 Hz), 7.78 (2H, d, J = 7.8 Hz). 13C NMR (125 MHz, CDC13) : 5 14.10, 21.27, 22.69, 26.35, 29.23, 29.34, 29.51, 29.64, 31.93, 36.38, 50.67, 55.24, 62.47, 64.24, 114.10, 119.43, 125.83, 127.92, 128.89, 129.47, 139.56, 143.87, 160.67, & 167.25. The molar extinction coefficient, G was found to be 25,000 at Xmax 310 nm in methanol. The final compound was analysed on HPLC using ion-pairing technique. The mobile phase employed for ion-pairing comprised of 0.1 M octane sulphonic acid in aqueous methanol (80 : 30). Reversed phase column Chromspher C8 was used with mobile phase flow rate of 1.0 ml / min. The detection was done at 280 nm. The purity of final compound from this analysis^was found to be 99.9 %. The spectral and chromatographic data were in total agreement with the reported values. Example II Process for preparation of p-JV.iV-dimethvlamino benzamidopropyldimethyl lauryl ammonium tosylate: The compound of Formula I, wherein, ArCO = p-N,N-dimethylamino benzoyl; R1 = H; R2,R3 = CH3; n = 3; R4 = -C12H25. a) Preparation of p-N,N-dimethvlamino benzamidopropyl dimethyl lauryl ammonium chloride : A mixture of lauryl chloride (2.46 g, 12.05 mmol) and p-N,N-dimethylamino benzamido propyldimethyl amine (3.0 g, 12.05 mmol) was stirred under blanket of nitrogen at 110°C for 20 hours. The progress of reaction was monitored by estimation of unquaternised amine as well as chloride ion. Estimated chloride ion and free amidoamine was found to be 7.83 % and 0.15 % respectively. On cooling, the reaction yielded the quaternary ammonium compound (5.455 g, 99.9 %) as pale yellow solid. b) Preparation of p-N,N-dimethylamino benzamidopropyl dimethyl lauryl ammonium chloride tosylate: p-N,N-Dimethylamino benzamidopropyldimethyllauryl ammonium chloride (5.455 g, 12.03 mmol) was dissolved in water to make 30 % solution. To this stirred solution, sodium p-toluene sulphonate (2.34 g, 12.06 mmol) was added and the separated pale yellow coloured solid was subsequently washed with water, filtered and dried to yield the corresponding tosylate (7.08 g, 99.93 %) as pale yellow coloured solid. Chloride ion was totally absent in the product. The spectral data (UV, IR and 1H NMR) was found to be identical with the one obtained by literature route. Reversed phase HPLC showed it to be 99.9 % pure. A process for preparing quaternary ammonium tosylates of cinnamidoalkylamines and / or benzamidoalkylamines of general Formula I from cinnamidoalkylamines and / or benzamidoalkylamines, fatty alkyl halides and sodium p-toluene sulphonate, substantially as herein described, in the text and in the examples. Advantages of the process : The quatemised UV-absorbers of the present invention containing cinnamidoalkylamine and / or benzamidoalkylamine moieties absorb very strongly in UV-B region. They are very substantive to skin, hair and fabric and due to the long alkyl chain they provide softening / conditioning effect. The processes described for above molecules in US Patent 5,427,773 (1995) and US Patent 6,613,340 (2003) are multi-step, low yielding and non eco-friendly. They involve use of p-toluene sulphonyl chloride as well as halogenated solvents. Since the synthetic routes described in these patents go via sulphonyl chloride, it necessitates use of an organic base. Thus, use of solvents, generation of by-products like salt of organic base-hydrochloride and the necessary purification steps that result in not only lower yield of isolated product but heavy load on effluent treatment. This can be easily eliminated by the new process described in the present invention. The process of the present invention is a simple one with quantitative conversions and does not generate effluents and hence environment friendly. This is achieved through designing this novel process that avoids solvents including halogenated ones, reagents like p-toluene sulphonyl chloride and organic bases. We claim 1. A process for preparing quaternary ammonium tosylates of cinnamidoalkylamines and/or benzamidoalkylamines of Formula I, Formula I wherein; ArCO is selected from p-N,N-dimethylamino benzoyl or p-methoxy cinnamoyl; R1 is selected from H or alkyl groups containing from 1 to 6 carbon atoms; R2 and R3 are independently selected from alkyl groups containing from 1 to 12 carbon atoms; R4 is selected from alkyl or alkenyl groups containing from 8 to 22 carbons; n is an integer having values from 1 to 6; comprising steps of (i) quatemisation of 1.0 mole of cinnamidoalkylamine and / or benzamidoalkylamine of Formula II with 1.0 mole of fatty alkyl halides of Formula HI, wherein, Ri, R2, R3, R4 and n is same as that in the compound of said Formula I, with or without solvent, to obtain a quaternary ammonium halide of Formula IV; (ii) treating the aqueous solution of quaternary halide of Formula IV obtained in step (i) with stoichiometric quantities of sodium p-toluene sulphonate to get water insoluble quaternary ammonium tosylate of Formula I. Formula IV 2. A process as claimed in step (i) of claim 1, wherein, the quatemisation of 1.0 mole of cinnamidoalkylamine or benzamidoalkylamine of Formula II is carried out with 1.0 mole of alkyl halide of Formula HI at 100 - 150°C for 10 to 24 hours to give quaternary ammonium halides of cinnamidoalkylamines or benzamidoalkylamines of Formula IV. 3. A process as claimed in step (ii) of claim 1, wherein, 30 % w/w aqueous solution of 1.0 mole of quaternary ammonium halide of cinnamidoalkylamine or benzamidoalkylamine of Formula IV is stirred with 1.0 mole of sodium p-toluene sulphonate at room temperature for four hours to give quaternary ammonium tosylates of cinnamidoalkylamines or benzamidoalkylamines of Formula I. 4. A process as claimed in claim 1, wherein, ArCO is p-methoxy cinnamoyl, R1 is H, R2 and R3 is -CH3, R4 is -C12H25 and n is 3, X" is tosylate anion. 5. A process as claimed in claim 1, wherein, ArCO is p-N,N-dimethyl amino benzoyl, R1 is H, R2 and R3 is -CH3, R4 is -C12H25 and n is 3, X" is tosylate anion. 6. A process for preparing quaternary ammonium tosylates of cinnamidoalkylamines and / or benzamidoalkylamines of general Formula I from cinnamidoalkylamines and / or benzamidoalkylamines, fatty alkyl halides and sodium p-toluene sulphonate, substantially as herein described, in the text and in the examples. 1 Dated this 21st day of August, 2003. Signatory (Shanbhag Shashikant) Galaxy Surfactants Limited. C-49/2, TTC Indl. Area, Pawne, Navi Mumbai - 400 703 (Applicant)

Full Text

FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
COMPLETE SPECIFICATION
(See Section 10 : Rule 13)
TITLE
Process for manufacture of quaternary ammonium tosylates of cinnamidoalkylamines and / or benzamidoalkylamines
APPLICANT
Galaxy Surfactants Ltd.,
C-49/2, TTC Industrial Area, Pawne, Navi-Mumbai 400 703, Maharashtra, India.
A Public Limited Company Registered under Indian Company's Act - 1956
The following specification particularly describes the nature of this invention and the manner in which it is to be performed :-

ORIGIANL

21-8-2003

GRANTED

8-1-2004

Field of Invention :
This invention relates to an improved process for manufacture of cationic, quaternary ammonium tosylate salts of cinnamidoalkylamines and / or benzamidoalkylamines. This invention particularly relates to the synthesis of tailor made non-hydrolyzable, non-irritating compounds having substantivity to cotton, wool, skin and hair and UV-radiation absorbing properties useful in personal care and fabric care formulations.
Background and Prior Art:
US patent 5,427,773 (1995) discloses preparation of cationic substantive photofilters like dodecyl dimethyl amino benzamido propyl dimethyl ammonium tosylate. In this process, a primary amino group of iV.iV-dimethyl propyl diamine is reacted with dimethyl amino benzoic acid to form an amidoamine and then the tertiary amino group of the amidoamine is quatemised with alkyl tosylate. Similarly, US Patent 6,613,340 (2003) discloses cationic tosylate salts from cinnamidoalkylamines following the same methodology. The procedures described in both patents are very tedious where alkyl tosylates used for quaternisation are prepared from fatty alcohols and tosyl chloride. This reaction is done in a suitable solvent using stoichiometric quantities of tertiary amine bases like triethylamine or pyridine. The organic bases mop up the hydrochloric acid generated and the subsequent hydrochloride-base salt that is formed as a by¬product has to be removed by washing the reaction mixture with water. This significantly increases the effluent load. Another disadvantage of this process is that the reaction of preparation of alkyl tosylate is carried out in halogenated solvents like dichloromethane or aromatic solvents. Purification of alkyl tosylate also results in significant loss of yield and simultaneous increase in effluent treatment. This is mainly due to the presence of unconverted fatty alcohols. The quaternisation of cinnamidoalkylamines and / or benzamidoalkylamines with alkyl tosylate does not give quantitative conversion and hence the after purification step the isolated yields of quatemised UV-absorbers range between 65 to 70 %.
In summary, all these factors make the process for making quatemised UV-absorbers not only tedious and expensive but also non-environment friendly. Hence, there is a need for a simple, quantitative and eco-friendly process for making these substantive UV-absorbers.
Object of the invention :
The main object of the present invention is to make the process of synthesizing the tosylate quaternary salts of cinnamidoalkylamines and / or benzamidoalkylamines simple, quantitative and eco-friendly.

Summary of the invention :
The present invention provides a process for preparing quaternary ammonium tosylates of cinnamidoalkylamines and / or benzamidoalkylamines of Formula I,
Formula I

wherein;
ArCO is selected fromp-Af,Af-dimethylamino benzoyl and / or p-methoxy cinnamoyl;
Ri is selected from H or alkyl groups containing from 1 to 6 carbon atoms;
R2 and R3 are independently selected from alkyl groups containing from 1 to 12 carbon atoms;
R4is selected from alkyl or alkenyl groups containing from 8 to 22 carbons;
n is an integer having values from 1 to 6;
comprising steps of
(i) quatemisation of 1.0 mole of cinnamidoalkylamine and / or benzamidoalkylamine of Formula II with 1.0 mole of alkylating compound of Formula HI, wherein, R\, R2, R3, R4 and n is same as that in the compound of said Formula I, with or without solvent, to obtain a quaternary ammonium halide of Formula IV;

(ii) treating the aqueous solution of quaternary ammonium halide of Formula IV obtained in step (i) with stoichiometric quantity of sodium p-toluene sulphonate to get water insoluble quaternary ammonium tosylate of Formula I;
Formula IV

and the products made by the process.
Detailed description of the invention :
The process of making compounds of Formula I described in the present invention comprises of two steps, a) synthesis of quaternary ammonium halides of Formula IV and b) conversion of water soluble quaternary compounds of Formula IV to water-insoluble quaternary ammonium tosylates.
In the process described in the present invention, the cinnamidoalkylamines and / or benzamidoalkylamines of Formula HI are synthesised as per the literature procedures [US patent 5,427,773 (1995), US Patent 6,613,340 (2003)]. These UV-absorbing amidoamines are quaternised using commercially available alkyl halides of Formula III in aqueous / alcoholic medium to give quantitative generation of corresponding water-soluble, UV-absorbing, quaternary ammonium halides of Formula IV. The reaction can be carried out in water, alcohols or mixtures thereof.
The quaternisation reaction can be conveniently done in a pressure reactor as well as in an open system. The temperatures suitable for pressure reaction range from about 100 - 135°C with the pressures up to 50 psi. The pressures are governed by the amount of solvent and the temperature selected for the reaction. The conditions of reaction in an open vessel also get dictated by the choice of solvent. The progress of the reaction is monitored by measuring the amount of unreacted alkylating agent by chromatography or by estimation of unquaternized amidoamine or by estimation of X", the halide anion.
Alternately, quaternisations can be carried out by directly reacting cinnamidoalkylamines and / or benzamidoalkylamines of Formula II with alkyl halides of Formula HI at from about 100 to 140°C for 4 to 24 hours without any solvent and in an inert atmosphere of nitrogen. The progress of the reaction is monitored by estimation of unquaternised tertiary amine as well as by the estimation of liberated halide.
In another embodiment, the process of the present invention relates to manufacture of quaternary ammonium tosylates of Formula I, in which ArCO is selected from p-JV.iV-dimethylamino

benzoyl and / or p-methoxy cinnamoyl; R1 is selected from H or alkyl groups containing from 1 to 6 carbon atoms, R2 and R3 are independently selected from alkyl groups containing from 1 to 12 carbon atoms; R4 is selected from alkyl or alkenyl groups containing from 8 to 22 carbons; n is an integer having values from 1 to 6; from the compounds of Formula II, m, IV and sodium p-toluene sulphonate, with respective substituents ArCO, R1, R2, R3, and n of Formula n, R4 of Fonnula HI and ArCO, R1 R2, R3, R4, and n of Formula IV as defined for the compounds of Formula I in this embodiment.
In another embodiment, the process of the present invention relates to manufacture of a quaternary ammonium tosylate of Formula I, in which ArCO = p-methoxy cinnamoyl, Ri = H, R2, R3 = -CH3, R4 = -C12H25 and n = 3, from the compound of Formula II (p-methoxy cinnamidopropyl dimethylamine, ArCO = p-methoxy cinnamoyl, R1 = H, R2, R3 = -CH3, n = 3) quaternised with compound of Formula HI (lauryl chloride, R4 = -C12H25, X" = chloride anion) forming the quaternised compound of Formula rv (p-methoxy cinnamidopropyl dimethyl lauryl ammonium chloride, R1 = H, R2, R3 = -CH3, R4 = -C12H25, n = 3, X" = chloride anion), aqueous solution of which is then treated with stoichiometric quantity of sodium p-toluene sulphonate. The process of preparation of such compound is given in Example I.
In another embodiment, the process of the present invention relates to manufacture of a quaternary ammonium tosylate of Formula I, in which ArCO = p-A/,Af-dimethylamino benzoyl, R1 = H, R2, R3 = -CH3, R4 = -C12H25 and n = 3, from the compound of Formula II (p-N,N-dimethylamino benzamidopropyldimethylamine, ArCO = p-A/,AT-dimethyl aminobenzoyl, R1 = H, R2, R3 = -CH3, n = 3) quaternised with compound of Formula HI (lauryl chloride, R4 = -C12H25, X" = chloride anion) forming the quaternised compound of Formula IV (p-MiV-dimethylamino benzamido propyldimethyllauryl ammonium chloride, R1 = H, R2, R3 = -CH3, R4 = -C12H25, n = 3, X" = chloride anion), aqueous solution of which is then treated with stoichiometric quantity of sodium p-toluene sulphonate. The process of preparation of such compound is given in Example

Examples
Alkyl halides were obtained from Henkel. p-Toluene sulphonic acid was obtained from Aldrich. p-Methoxy cinnamidopropyldimethylamine and p-Af,7V-dimethylamino benzamidopropyl dimethylamine were synthesised as per literature procedures [US patent 5,427,773 (1995), US Patent Application No. 20030064083 April, 2003].
Example I
Process for preparation p-methoxy cinnamidopropvldimethvllaurvl ammonium tosylate :
The compound of Formula I, wherein, ArCO = p-methoxy cinnamoyl; Ri = H; R2, R3 = CH3; n =
3; R4 = -C12H25.
a) Preparation of p-methoxv cinnamidopropyldimethyllaurfl ammonium chloride :

A mixture of lauryl chloride (7.8 g, 38.17 mmol) and p-methoxy cinnamidopropyldimethyl amine (10.0 g, 38.17 mmol) was stirred under blanket of nitrogen at 110°C for 20 hours. The progress of reaction was monitored by estimation of unquaternised amine. Estimated chloride ion and free amidoamine was found to be 7.6 % and 0.12 % respectively. On cooling, the reaction yielded the quaternary ammonium compound (17.78 g, 99.9 %) as pale yellow solid.
b) Preparation of p-methoxy cinnamidopropyldimethyllauryl ammonium tosylate :
p-Methoxy cinnamidopropyldimethyllauryl ammonium chloride (17.78 g, 38.11 mmol) was dissolved in water to make 30 % solution. To this stirred solution, sodium p-toluene sulphonate (7.4 g, 38.14 mmol) was added and the separated pale yellow coloured solid was subsequently washed with water, filtered and dried to yield the corresponding tosylate (22.9 g, 99.83 %) as off-white solid, m.p. 128 - 130°C. Chloride ion was totally absent in the product.
IR (CH2C12): 3465, 3286, 3052, 2920, 1659, 1617 cm"1.
*H NMR (CDCI3, 300 MHz) : 8 0.87 (3H, t, J = 6.3 Hz), 1.18 (18H, broad signal), 1.58 (2H, unresolved multiplet), 2.10 (2H, unresolved multiplet), 2.32 (3H, singlet, methyl of tosyl), 3.13 (6H, singlet, two methyl on nitrogen), 3.20 (2H, unresolved multiplet), 3.45 (2H, unresolved multiplet), 3.68 (2H, unresolved multiplet), 3.78 (3H, singlet, OCH3), 6.52 (1H, d, J = 15.6 Hz), 6.76 (2H, d, J = 8.4 Hz), 7.14 (2H, d, J = 6.0 Hz), 7.31 (2H, d, J = 8.6 Hz), 7.48 (1H, d, J = 15.6 Hz), 7.78 (2H, d, J = 7.8 Hz).
13C NMR (125 MHz, CDC13) : 5 14.10, 21.27, 22.69, 26.35, 29.23, 29.34, 29.51, 29.64, 31.93, 36.38, 50.67, 55.24, 62.47, 64.24, 114.10, 119.43, 125.83, 127.92, 128.89, 129.47, 139.56, 143.87, 160.67, & 167.25.
The molar extinction coefficient, G was found to be 25,000 at Xmax 310 nm in methanol.
The final compound was analysed on HPLC using ion-pairing technique. The mobile phase employed for ion-pairing comprised of 0.1 M octane sulphonic acid in aqueous methanol (80 : 30). Reversed phase column Chromspher C8 was used with mobile phase flow rate of 1.0 ml / min. The detection was done at 280 nm.
The purity of final compound from this analysis^was found to be 99.9 %.
The spectral and chromatographic data were in total agreement with the reported values.
Example II
Process for preparation of p-JV.iV-dimethvlamino benzamidopropyldimethyl lauryl ammonium tosylate:
The compound of Formula I, wherein, ArCO = p-N,N-dimethylamino benzoyl; R1 = H; R2,R3 = CH3; n = 3; R4 = -C12H25.

a) Preparation of p-N,N-dimethvlamino benzamidopropyl dimethyl lauryl ammonium chloride : A mixture of lauryl chloride (2.46 g, 12.05 mmol) and p-N,N-dimethylamino benzamido propyldimethyl amine (3.0 g, 12.05 mmol) was stirred under blanket of nitrogen at 110°C for 20 hours. The progress of reaction was monitored by estimation of unquaternised amine as well as chloride ion. Estimated chloride ion and free amidoamine was found to be 7.83 % and 0.15 % respectively. On cooling, the reaction yielded the quaternary ammonium compound (5.455 g, 99.9 %) as pale yellow solid.
b) Preparation of p-N,N-dimethylamino benzamidopropyl dimethyl lauryl ammonium chloride tosylate:
p-N,N-Dimethylamino benzamidopropyldimethyllauryl ammonium chloride (5.455 g, 12.03 mmol) was dissolved in water to make 30 % solution. To this stirred solution, sodium p-toluene sulphonate (2.34 g, 12.06 mmol) was added and the separated pale yellow coloured solid was subsequently washed with water, filtered and dried to yield the corresponding tosylate (7.08 g, 99.93 %) as pale yellow coloured solid. Chloride ion was totally absent in the product.
The spectral data (UV, IR and 1H NMR) was found to be identical with the one obtained by literature route. Reversed phase HPLC showed it to be 99.9 % pure.
A process for preparing quaternary ammonium tosylates of cinnamidoalkylamines and / or benzamidoalkylamines of general Formula I from cinnamidoalkylamines and / or benzamidoalkylamines, fatty alkyl halides and sodium p-toluene sulphonate, substantially as herein described, in the text and in the examples.

Advantages of the process :
The quatemised UV-absorbers of the present invention containing cinnamidoalkylamine and / or benzamidoalkylamine moieties absorb very strongly in UV-B region. They are very substantive to skin, hair and fabric and due to the long alkyl chain they provide softening / conditioning effect.
The processes described for above molecules in US Patent 5,427,773 (1995) and US Patent 6,613,340 (2003) are multi-step, low yielding and non eco-friendly. They involve use of p-toluene sulphonyl chloride as well as halogenated solvents. Since the synthetic routes described in these patents go via sulphonyl chloride, it necessitates use of an organic base. Thus, use of solvents, generation of by-products like salt of organic base-hydrochloride and the necessary purification steps that result in not only lower yield of isolated product but heavy load on effluent treatment. This can be easily eliminated by the new process described in the present invention. The process of the present invention is a simple one with quantitative conversions and does not generate effluents and hence environment friendly. This is achieved through designing this novel process that avoids solvents including halogenated ones, reagents like p-toluene sulphonyl chloride and organic bases.

We claim
1. A process for preparing quaternary ammonium tosylates of cinnamidoalkylamines and/or benzamidoalkylamines of Formula I,
Formula I

wherein;
ArCO is selected from p-N,N-dimethylamino benzoyl or p-methoxy cinnamoyl;
R1 is selected from H or alkyl groups containing from 1 to 6 carbon atoms;
R2 and R3 are independently selected from alkyl groups containing from 1 to 12 carbon atoms;
R4 is selected from alkyl or alkenyl groups containing from 8 to 22 carbons;
n is an integer having values from 1 to 6;
comprising steps of
(i) quatemisation of 1.0 mole of cinnamidoalkylamine and / or benzamidoalkylamine of Formula II with 1.0 mole of fatty alkyl halides of Formula HI, wherein, Ri, R2, R3, R4 and n is same as that in the compound of said Formula I, with or without solvent, to obtain a quaternary ammonium halide of Formula IV;

(ii) treating the aqueous solution of quaternary halide of Formula IV obtained in step (i) with stoichiometric quantities of sodium p-toluene sulphonate to get water insoluble quaternary ammonium tosylate of Formula I.
Formula IV
2. A process as claimed in step (i) of claim 1, wherein, the quatemisation of 1.0 mole of cinnamidoalkylamine or benzamidoalkylamine of Formula II is carried out with 1.0 mole of alkyl halide of Formula HI at 100 - 150°C for 10 to 24 hours to give quaternary ammonium halides of cinnamidoalkylamines or benzamidoalkylamines of Formula IV.
3. A process as claimed in step (ii) of claim 1, wherein, 30 % w/w aqueous solution of 1.0 mole of quaternary ammonium halide of cinnamidoalkylamine or benzamidoalkylamine of Formula IV is stirred with 1.0 mole of sodium p-toluene sulphonate at room temperature for four hours to give quaternary ammonium tosylates of cinnamidoalkylamines or benzamidoalkylamines of Formula I.
4. A process as claimed in claim 1, wherein, ArCO is p-methoxy cinnamoyl, R1 is H, R2 and R3 is -CH3, R4 is -C12H25 and n is 3, X" is tosylate anion.
5. A process as claimed in claim 1, wherein, ArCO is p-N,N-dimethyl amino benzoyl, R1 is H, R2 and R3 is -CH3, R4 is -C12H25 and n is 3, X" is tosylate anion.
6. A process for preparing quaternary ammonium tosylates of cinnamidoalkylamines and / or benzamidoalkylamines of general Formula I from cinnamidoalkylamines and / or benzamidoalkylamines, fatty alkyl halides and sodium p-toluene sulphonate, substantially as herein described, in the text and in the examples.
1

Dated this 21st day of August, 2003.

Signatory
(Shanbhag Shashikant) Galaxy Surfactants Limited. C-49/2, TTC Indl. Area, Pawne, Navi Mumbai - 400 703
(Applicant)

Documents:

835-mum-2003-cancelled pages(08-01-2004).pdf

835-mum-2003-claim(granted)-(8-1-2007).doc

835-mum-2003-claims(granted)-(08-01-2004).pdf

835-mum-2003-correspondence(28-01-2004).pdf

835-mum-2003-correspondence(ipo)-(21-05-2007).pdf

835-mum-2003-form 1(21-08-2003).pdf

835-mum-2003-form 19(21-08-2003).pdf

835-mum-2003-form 2(granted)-(08-01-2004).doc

835-mum-2003-form 2(granted)-(08-01-2004).pdf

835-mum-2003-form 3(21-08-2003).pdf

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Patent Number

207066

Indian Patent Application Number

835/MUM/2003

PG Journal Number

42/2008

Publication Date

17-Oct-2008

Grant Date

21-May-2007

Date of Filing

21-Aug-2003

Name of Patentee

GALAXY SURFACTANTS LIMITED

Applicant Address

GALAXY SURFACTANTS LIMITED, C-49/2, TTC INDL. AREA, PAWNE, NAVI MUMBAI - 400 703,

Inventors:

#	Inventor's Name	Inventor's Address
1	1)KOSHTI NIRMAL 2)NAIK SHUBHANGI 3) PARAB BHARAT 4)JADHAV TANAJI	GALAXY SURFACTANTS LIMITED., GALAXY SURFACTANTS LIMITED, C-49/2, TTC INDL. AREA, PAWNE, NAVI MUMBAI - 400 703,

PCT International Classification Number

A01N 33/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA