IMPACT: International Journal of Research in Applied, Natural and Social Sciences (IMPACT: IJRANSS) ISSN(E): 2321-8851; ISSN(P): 2347-4580 Vol. 3, Issue 10, Oct 2015, 23-28 © Impact Journals SYNTHESIS OF QUATERNARY AMMONIUM SALTS HAVING PHENOXY ACETIC ACID MOIETY AND THEIR PLANT GROWTH RETARDANT ACTIVITY NIRUPMA SOOD 1, RAJINDER SINGH 2 & M. L. SHARMA 3 1 Department of Chemistry, Khalsa College for Women, Ludhiana, Punjab, India 2 3 Department of Chemistry, Punjab Agricultural University, Ludhiana, Punjab, India ABSTRACT Eight new quaternary salts of ammonia (1a-d and 2a-d), from different phenols were synthesized and tested as plant growth retardants. The structure of various tertiary amines and esters was established with the help of IR and NMR spectral studies. Biological activity of these compounds was tested using seed germination and seedling growth as bioassay of Oryza sativa . All the compounds showed plant growth retardant activity comparable to cycocel (CCC) at higher concentrations. KEYWORDS: Cycocel, Oryza Sativa, Tertiary Amine, Quaternary Ammonium Salts INTRODUCTION Plant growth retardants have been used for many years to manipulate the size, shape and overall quality of various crops. These compounds have been used to control the lodging, increasing the yield and producing compact plant in different crops. Quaternary ammonium salts have been found to possess plant growth retardant activity. In the present work eight new quaternary salts of ammonia from different phenols have been synthesized and tested as plant growth retardants MATERIAL AND METHODS Purity of analytical samples was checked by TLC. Silica gel G(13% gypsum) was employed for TLC plates of size(7.5 x2.5). The plates were developed in ether, benzene and ethyl acetate solvents of varying proportions. The spots were visualized by placing the plates for some time in chamber saturated with iodine .Drying of all organic extracts was done over anhydrous Na 2SO 4. Preparation of Phenylchloroacetate (7) A mixture of phenol (4.7g, 0.05 mol), chloroacetic acid (4.7g, 0.05 mol) and benzene (30 ml) in the presence of ’ acid catalyst (0.5ml, conc. H 2SO 4) was refluxed with the help of Dean and Stark s apparatus till the separation of water is stopped. The cooled reaction mixture was treated with saturated solution of NaHCO 3 and washed with water and extracted with benzene. Extract was dried over anhydrous Na 2SO 4 and solvent was removed by distillation. The residue was distilled o ,max 3060, 3005, 2959, 1761, 1595, 1494ט .under reduced pressure to give (7). Yield ;6.8 g( 90%) ,b.p 70-75 C/ 10-15 mm 1404, 1314, 1217, 1160, 1068,1022, 1004, 924, 902, 842, 767, 699, 550 and 496 cm -1. .δ ; 4.25 (2H, s, -Cl-CH2-COO-), 7.1-7.4 (5H, Ar-H) Impact Factor(JCC): 1.8207- This article can be downloaded from www.impactjournals.us 24 Nirupma Sood, Rajinder Singh & M. L. Sharma Preprartion of N-Butylchloroacetate (8) n-Butylchloroacetate was prepared as above. Yield ; 6.6 g, (85%), b.p 130 – 135 OC. -1 -,max ; 2963, 2875, 1756, 1464, 1415, 1386,1310,1186,1086,1019,958,844,787,698 and 575 cm . δ ; 0.9 (3H, t ,j=7Hzט OCH 2 CH 2 CH 2 CH 3), 1.3 (2H,m,-CH 2 CH 2 CH 2 CH 3) 1.6 (2H, m,-CH2 CH2 CH 2 CH 3), 3.9(2H, s, -ClCH2-CO ), 4.1 (2H, t , J= 7 Hz,-O-CH2CH 2CH 2CH 3). Figure 1 Prepration of 2-(2-Methylphenoxy) Ethanoic Acid (4a) O-cresol (5.4g, 0.05mol) and chloroacetic acid (5.7g, 0.06 mol) were melted together on water bath; NaOH (5.4g o in22.5 ml of H 2O, 6N) was added to it drop wise slowly with stirring and then the mixture was heated (60-70 C) for 3h with occasional shaking. It was diluted with water and acidified with conc. HCl. The precipitates thus formed were filtered, washed and dried to give 2-( 2-methylphenoxy) ethanoic acid. Yield; 6.6g (80%), m.p 124-12 δ5oC It gave characteristic tests for carboxylic acid group. Compound 2-(3-methylphenoxy) ethanoic acid (4b ’) was also prepared by similar procedure from m-cresol. Yield 7.4g (90%),m.p 98-99 oC. Compound 2-(4-methylphenoxy) ethanoic acid (4c) was obtained similarly from p-cresol. Yield 7.1g (86%) m.p 139-141 oC (lit 140-142 oC) Compound 2-(4-nitrophenoxy) ethanoic acid (4d) was also procured from 4-nitrophenol in the similar manner. Yield 8.8g (90%). Prepration of (3-N,N-Diethylamino-2-Hydroxypropyl)-2-(2-Methylphenoxy) Ethanoate (6a) 2-(2-Methylphenoxy) ethanoic acid (4a, 6.4g,.038 mol),anhydrous K 2CO 3 (11.4g) and epichlorohydrin (120 ml) was refluxed under stirring for 13 h. The reaction mixture was filtered, filtrate concentrated and the residue taken up in benzene. The organic phase was washed successively with 10% NaOH, water, saturated aqueous NaCl, dried and concentrated to afford the epoxide compound (5a). Index Copernicus Value: 3.0 - Articles can be sent to [email protected] Synthesis of Quaternary Ammonium Salts Having Phenoxy Acetic 25 Acid Moiety and Their Plant Growth Retardant Activity The above epoxide (1.6g) and diethylamine (5ml) was refluxed in absolute alcohol (50ml) for 4h cooled and alcohol was distilled off. The residual oil thus obtained was distilled under reduced pressure to give (6a).Yield 1.76g (81%),b.p. 108-110 oC/7-8mm. -1 max (cm ) ; 3364, 2927, 1754, 1604,1494, 1464, 1227, 1190, 1124, 1065, 930, 827, 756 and700. δ ; 1.3 [6H, t, j=7ט Hz,- N(CH 2CH 3), 2.2 (3H, s, Ar-CH 3),2.9 [6H,m, -CH 2N (CH 2CH 3)2], 3.65 [3H, m, -OCH 2CH(OH)-], 4.4 (2H, s,- OCH 2COO-), 6.7-7.0 (4H, Ar-H ). (3-N,N-Diethylamino-2-hydroxypropyl)-2-(3-methylphenoxy) ethanoate (6b ’) was also prepared similarly by taking (4b ’, 6.4g, 0.045mol).Yieid; 3.52g (81%) b.p 104- 106 0C/5-6 mm. -1 .max (cm ) ;3435,2970,2815,1735,1669,1469,1386,1292,12021163,1064and 773ט δ ; 1.15[ 6H, t, j = 7Hz ; N(CH 2CH 3)2], 2.3 (3H, s, Ar- CH 3), 2.69 -2.76 [6H, m, CH 2N(CH 2CH 3)2], 3.8 [ 1H, m, - CH(OH)], 4.25 (2H, s, ArOCH 2), 4.45 (2H, d, j=7.5Hz,-COOCH 2CH(OH)], 6.5-8.5 (4H, Ar-H). (3-N,N-Diethylamino 2-hydroxypropyl)-2-(4-methylphenoxy) ethanoate (6c) was also prepared similarly by taking (4c, 14.7g, 0.045 mol) Yield; 3.7g (80%), b.p 114-116 oC/8-9mm. (3-N, N-Diethylamino-2-hydrpxypropyl)-2-(4-nitrophenoxy) ethanoate (6d) was also prepared similarly by taking (4d, 7.5g, 0.045 mol). Yield; 3.7g (80%), b.p 114-116 oC/8-9mm Quaternary Salt of (3-N, N-Diethylamino - 2- Hydroxypropyl) - 2- ( 2- Methylphenoxy) Ethanoate ( 1a) A mixture of tertiary amine ( 6a, 0.5g ) and phenylchloroacetate (7, 0.5g ) dissolved in acetonitrile ( 30ml ) was refluxed for 14h. Excess of the solvent was distilled off and residue was scratched by adding anhydrous ether. The unreacted tertiary amine and chloroester (7) being soluble in dry ether were decanted to get quaternary salt of ammonia a thick liquid which was stored in vacuum desiccators. Being hygroscopic in nature, the spectral studies of the salt (1a) could not be done. However it gave a positive test with copper wire . Quaternary salts of (3-N,N-diethylamino-2- hydroxypropyl) -2-(3-methylphenoxy) ethanoate (1b) , ( 3- N,N- Diethylamino -2- hydroxypropyl) -2-(4-methylphenoxy) ethanoate (1c) and ( 3-N,N-Diethylamino -2 -hydroxypropyl -2- (4-nitrophenoxy ) ethanoate (1d) were obtained similarly from corresponding tertiary amine (6b-d) in quantitative yield (about 90%). Quaternary Salt of (3-N, N-Diethylamino- 2-Hydroxypropyl) -2- (2-Methylphenoxy) Ethanoate (2a) A mixture of tertiary amine (7, 0.5 g) and n-buylchloroacetate (18, 0.5g) dissolved in acetonitrile (30 ml) as refluxed for 14h. Excess of the solvent was distilled off and residue was scratched by adding anhydrous ether. The unreacted tertiary amine and chloroester (18) being soluble in dry ether were decanted to get quaternary salt of ammonia as a thick liquid which was stored in vacuum desiccators. Being hygroscopic in nature, the spectral studies of the salt (2a) could not be done. However it gave a positive test with copper wire. Yield; 0.68g (89%) Quaternary salts of (3-N,N- diethylamino -2- hydroxypropyl) -2-(3-methylphenoxy) ethanoate (2b), (3-N,N- diethylamino -2 -hydroxypropyl) -2-(4-methylphenoxy ) ethanoate (2c) and (3- N,N -diethylamino -2- hydroxypropyl)-2- (4- nitrophenoxy) ethanoate ( 2d ) were also prepared similarly by taking tertiary amines (6a-d) in 90% yield. Impact Factor(JCC): 1.8207- This article can be downloaded from www.impactjournals.us 26 Nirupma Sood, Rajinder Singh & M. L. Sharma BIOLOGICAL TESTING Quaternary salts of ammonia were tested on Oryza sativa (PR 116). To test on rice, twenty seeds in each replication were placed on a filter paper laid on bottom of a petridish of 9cm diameter to which 7ml of test solution of different concentration (25, 50, 100, 200, 400,500 micro g /ml ) of the compounds had been poured. Each dish was kept at 28 + 2oC for 7 days and there after the seed germination (%), root length and shoot length were measured. Separate control treatments with water, cycocel and ABA were also recorded simultaneously. RESULTS AND DISCUSSIONS Plant growth retardants have been used for many years to manipulate the size, shape and overall quality of various crops.