Title of Invention	PROCESS OF PREPARATION OF (S) - 2-CHLORO-3-(-4-BENZAMIDOACETPHENYL)-1-(4-BEXADECYLOXYBENZOYL)-BENZOATOPROPIONATE.
Abstract	A process for the preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl) -1- (4'-hexadecyloxybenzoyl) -benzoatopropionate which comprises in known method of nucleophilic substitution of -NH2 group from (S)-2-chloro-3- (4-hydroxyphenyl)-propionic acid by a chlorine atom via known diazonium salt formation, in presence of freshly pulverized sodium nitrate, to obtain crystals of (S)-2-chloro-3-(4- hydroxyphenyl)-propionic acid, (S)-2-chloro-3-(4-hydroxyphenyl)- propionic acid is reacted said l-chloro-2-benzamidoacetic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, benzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3-(4- benzamidoacetophenyl)-propionic; (S)-2-chloro-3-(4- benzamidoacetophenyl-propionic acid is refluxed with thionyl chloride to obtain (S)-l, 2-dichloro-3- (4-benzamidoacetophenyl)-propionic (S)-l,2- dichloro-3-(4-benzamidoacetophenyl)-propionic acid is reacted with 4- hydroxybenzoic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, behzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-benzoic acid; (S)-2- chloro-3-(4-benzamidoacetophenyl)-l-benzoic acid propionate is carried with thionyl chloride to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)- l-(l-chlorobenzoic acid), (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(l- chlorobenzoic acid) is reacted with 4-hydroxybenzoic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, behzene, methanol, dimethylformamide, diethyletner under inert atmosphere of nitrogen to obtain (S)-2-chloro-3-(4- benzamidoacetophenyl)- l-(4'-benzoic acid)-benzoatopropionate; (S)-2- chloro-3-(4-benzamidoacetopheryl)-l-4'- benzoic acid)- benzoatopropionate is reacted with thionyl chloride with constant stirring to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(4' -1-- chlorobenzoic acid)- benzoatopropionate, (S)-2-chloro-3-(4- benzamidoacetophenyl)-l-(4'-l-chlorobenzoic acid)-benoatopropionate is reacted with 1-hexadecanol in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, behzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(4'- octadecyloxybenzoyl)-benzoatopropionate;

Title of Invention

PROCESS OF PREPARATION OF (S) - 2-CHLORO-3-(-4-BENZAMIDOACETPHENYL)-1-(4-BEXADECYLOXYBENZOYL)-BENZOATOPROPIONATE.

Abstract

A process for the preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl) -1- (4'-hexadecyloxybenzoyl) -benzoatopropionate which comprises in known method of nucleophilic substitution of -NH2 group from (S)-2-chloro-3- (4-hydroxyphenyl)-propionic acid by a chlorine atom via known diazonium salt formation, in presence of freshly pulverized sodium nitrate, to obtain crystals of (S)-2-chloro-3-(4- hydroxyphenyl)-propionic acid, (S)-2-chloro-3-(4-hydroxyphenyl)- propionic acid is reacted said l-chloro-2-benzamidoacetic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, benzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3-(4- benzamidoacetophenyl)-propionic; (S)-2-chloro-3-(4- benzamidoacetophenyl-propionic acid is refluxed with thionyl chloride to obtain (S)-l, 2-dichloro-3- (4-benzamidoacetophenyl)-propionic (S)-l,2- dichloro-3-(4-benzamidoacetophenyl)-propionic acid is reacted with 4- hydroxybenzoic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, behzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-benzoic acid; (S)-2- chloro-3-(4-benzamidoacetophenyl)-l-benzoic acid propionate is carried with thionyl chloride to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)- l-(l-chlorobenzoic acid), (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(l- chlorobenzoic acid) is reacted with 4-hydroxybenzoic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, behzene, methanol, dimethylformamide, diethyletner under inert atmosphere of nitrogen to obtain (S)-2-chloro-3-(4- benzamidoacetophenyl)- l-(4'-benzoic acid)-benzoatopropionate; (S)-2- chloro-3-(4-benzamidoacetopheryl)-l-4'- benzoic acid)- benzoatopropionate is reacted with thionyl chloride with constant stirring to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(4' -1-- chlorobenzoic acid)- benzoatopropionate, (S)-2-chloro-3-(4- benzamidoacetophenyl)-l-(4'-l-chlorobenzoic acid)-benoatopropionate is reacted with 1-hexadecanol in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, behzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(4'- octadecyloxybenzoyl)-benzoatopropionate;

Full Text	FIELD OF INVENTION This invention relates to the compound (S')-2-chloro-3- invention is a novel room temperature ferroelectric liquid crystal (FLO which is useful in the applicational aspects such as polarisation controllers, switching attenuators and display devices. PRIOR ART Hitherto there are no processess of synthesizing these room temperature ferroelectric compounds made out of optically active (S)-2-amino-3-(4-hydroxyphenyl)-propionic acid. OBJECTS OF THE INVENTION The main object of the present invention is to provide a process for the synthesis of new ferroelectric liquid crystal compound, (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(4'-hexadecyloxybenzoyl)-benzoatopropionte, which ferroelectricity at ambient temperature. DESCRITPION OF INVENTION According to this invention there is provided A process for the preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl) -1- (4'- hexadecyloxybenzoyl) -benzoatopropionate which comprises in: i) known method of nucleophilic substitution of -NH2 group from (S)-2-chloro-3- (4-hydroxyphenyl)-propionic acid by a chlorine atom via known diazonium salt formation, in presence of freshly pulverized sodium nitrate, to obtain crystals of (S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid, ii) (S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid is reacted said l-chloro-2-benzamidoacetic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichlorome thane, behzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3-(4-benzamidoacetophenyl)-propionic; iii) (S)-2-chloro-3-(4-benzamidoacetophenyl-propionic acid is refluxed with thionyl chloride to obtain (S)-l, 2-dichloro-3- (4-benzamidoacetophenylj-propionic iv) (S)-l,2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid is reacted with 4-hydroxybenzoic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichloro me thane, behzene, methanol, dime thy Iformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-benzoic acid; v) (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-benzoic acid propionate is carried with thionyl chloride to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(l-chlorobenzoic acid), vi) (S)-2-chloro-3-(4-benzamidoacetophenyl)-1 -(1 -chlorobenzoic acid) is reacted with 4-hydroxybenzoic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, behzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2- chloro-3-(4-benzamidoacetophenyl)-1 -(4'-benzoic acid)- benzoatopropionate; vii) (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-4'- benzole acid)-benzoatopropionate is reacted with thionyl chloride with constant stirring to obtain (S)-2-chloro-3- (4- benzamidoacetophenyl)-l-(4' -l--chlorobenzoic acid)- benzoatopropionate, viii) (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(4'-l-chlorobenzoic acid)-benoatopropionate is reacted with 1-hexadecanol in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, behzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(4'-octadecyloxybenzoyl)-benzoatopropionate; According to the present invention, preparation of this material comprises a total of nine steps followed by various compositions under different conditions. The first step comprises: the process of nuclephilic substitution of -NH2 group from (S)-2-amino-3-(4-hydrooxyphenyl)-propionic acid by a chlorine atom via diazonium salt formation, in the presence of freshly pulverized sodium nitrate. stirring the reaction mixture for 6 hours at 0-4'C, extracting with a suitable organic solvent, dryinq the organic layer with an appropriate drying agent for 12 hours, removing the excess solvent under reduced pressure, separating the compound by column chromatography using a silica gel column and appropriate eluent mixture, followed by recystallization to get crystals of (S )---2~chloro--3-(4-hydroxyphenyl )-propionic acid. Second step of the process illustrates the preparation of l-chloro-2--benzamidoacet ic acid by reflux ing 2-ben;zamidoacetic acid with thionyl chloride at 75' for 8 hours, removing the excess organic solvent by vacuum distillation, washing the product with suitable cold solvent, drying the product over an appropriate desiccant for a period of 10 hours, separating the compound by column chromatography using a silica gel column and appropriate eluent mixture. Third step of the process describes the preparat ion of (S)-2-ch1oro-3-(4-benzamidoacetopheny1)- propionic acid by reacting (S)-2-chloro-3- Fourth step of the process describes the preparation of (S)-1, 2-di chloro—3-(4-benzamidoaceptopheny 1 ) -propionic acid by refluxing said (S)-2-chloro-~3-(4-benzamidoacetopheny1)—propionic acid with thionyl chloride at 60'C with constant stirring removing the excess organic solvent by vacuum distillation, washing the product with suitable cold solvent. Fifth step of the process describes the preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl) 1- benzole acid propionate by reacting (S)-1,2 di chloro~-3-(4---benzami doacetopheny 1)~propionic acid with 4-hydroxybenzoic acid in presence of a catalyst, and dry organic solvent under inert atmosphere, stirring the reaction mixture initially at room temperature for 4 hours, refluxing the reaction mixture for a period upto 18 hours, removing the excess organic solvent by vacuum distillation, washing the product with suitable cold solvent, drying the product over an appropriate desiccant for a period of 12 hours, separating the compound by column chromatography using a silica gel column and appropriate eluent mixture. Sixth step of the process describes the preparat ion of (S)-2-ch1oro-3-(4~benzami doacetopheny1) -1--(1-chlor ob enzoi c acid) propionate by reacting (S) --2-ch 1 oro-3- ( 4-benzam i doacetopheny 1 ) -1 -benzol c acid propionate with thionyl chloride with constant stirring, removing the excess organic solvent by vacuum distillation, washing the product with suitable cold solvent, drying the product over an appropriate desiccant for a period of 10 hours, separating the compound by column chromatography using a silica gel column and appropriate eluent mixture, followed by recrystal1ization to get c r y s t a 1 s o f C S) ••- 2 - c h 1 o r o 3 - C 4 - b e n;: a m i d o a c e t o p h e n y 1 ') -1 -C1-chlorobenzoic acid) propionate. Seventh step of the process describes the preparation of (S)-2-chloro-3-(4-benzamido-acetophenyl) -1-(4' -benzoic ac id)-benzoatopropionate by reacting (S )~2---chloro~-3-~ separating the compound by column chromatography usinq a silica gel column arid appropriate eluent mixture. Eighth step of the process describes the preparation of (S)-2-ch1oro»3-C4--benzamido-acetopheny1) -1-(4-1-c h 1 o r o be n 2 o i c acid) - be n 2z oa t o p r o p i o na t e by react i ng (S)-2-chloro-3- (4-bebenzamidoacetophenyl ) -1-(4 ' -benzo i c acid) -benzoatop rop i onate with thionylchloride with constant stirring, removing the excess organic solvent by vacuum distillation, washing the product with suitable cold solvent, drying the product over an appropriate desiccant for a period of 12 hours, separating the compound by column chromatography using a silica gel column and appropriate eluent mixture. Ninth step of the process describes the preparation of (S)-2-chloro™3-(4-benzamido-acetophenyl) ~-l---<:4 by reacting doacetopheny1 acid with in presence of a ceitalyst and dry organic solvent under inert atmosphere stirring the> reaction mixture initially at room temperature for 4 hours, re flux ing the reaction mixture for a period upto b hours, removing the excess organic solvent by vacuum distillation, washing the product with su i t a b 1 e c o 1 d so 1 ve n t, drying t he p r o clu c t ove r an appropriate desiccant for a period of 12 hours, separating the compound by column chromatography using a silica gel column and apropriate eluent mi xture. According to another feature of the present invention, the inert atmosphere may be maintained by using nitrogen. According to yet another feature of the present invention, the catalyst used is such as triethyiamine. According to yet another feature of the present invention, the dry organic solvent used is such as dicloromethane, benzene, methanol, dimethylformamide, diethylether. According to yet another feature of the present invention, organic solvent used for purification of compound by column chromatography is such as actone, acetonitrile, petroleum ether, d i c h 1 o r ome t hane . According to yet another feature of the present invention, drying agent used is such as sodium sulphate, phosphorous pentoxide, calcium chloride. A step wise process for the preparation of a room temperature ferroelectric liquid crystal compound, (S)-2-chloro-3-(4- benzamidoacetophenyl)-l-(4-hexadecyloxybenzoyl)-benzoatopropionate, is presented as follows: Step 1 (S)-2-amino-3-(4-hydroxyphenyl)-propionic acid (S)-2- chloro-3-(4-hydroxyphenyl)-propionic acid (S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid was prepared by a known method and is described first 5.43 gram (30.0 mmol) of (S)-2-amino-3-(4-hydroxyphenyl)-propionic acid was dissolved in 20 ml of 6.0 N HCI and the solution was brought to 0°C. 2.72 gram (32.0 mmol) of freshly pulverised sodium nitrate was added to the solution in small portions with vigorous stirring while maintaining the reaction temperature between 0 and 5°C. The reaction mixture was stirred for 16 h. The solution was then extracted with 40 ml of diethylether and the etherial layer was dried over anhydrous sodium sulphate for 12 h. (S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid obtained as an yellow product on removing the excess solvent by distillation under reduced pressure was washed repeatedly with cold benzene, seperated by chromatography through a silica gel column using a mixture of diethylether : acetone (5:1 v/v) as eluent. The product was recrystallized from hot dichloromethane and dried over P2O5for 12 h. to get an yield of 3.2 gram (53.2%). Step 2 2-benzamidoacetic acid l-chloro-2-benzamidoacetic acid l-chloro-2-benzamidoacetic acid was prepared by mixing together 4.48 gram (25.0 mmol) of 2-benzamidoacetic acid and 3.0 ml (40.0 mmol) of thionyl chloride in 40 ml of dry benzene under nitrogen atmosphere and kept the reaction mixture under reflux with continuous stirring at 75°C for 8 h. After the evalution of SO2 gas was ceased, the volume of the resulting solution was reduced by vacuum distillation of get an yellow solid product which was suction filtered, washed several times with cold methanol and dried over anhydrous calcium chloride for l0h. The product was purified by passing through a silica gel column using a mixture of petroleum ether: acetonitrile (5:1 v/v) as eluent to get 2.6 gram (52.6%) of l-chloro-2-benzamidoacetic acid. Step 3 l-chloro-2-benzamidoacetic acid + (S)-2-chloro-3-(4-hydroxyphenyl)- propionic acid (S)-2-chloro-3-(4-benzamidoacetophenyl)- propionic acid 3.95 (20.0 mmol) of l-chloro-2-benzamidoacetic acid prepared as illustrated in step 2 and 5.0 gram. (25.0 mmol) of (S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid prepared as described in step 1 were magnetically stirred in 40 ml dry dichloromethane at ambient temperature for 2 h. 0.5 ml (3,6 mmol) of triethylamine was then added to the reaction mixture drop wise and the reaction mixture was refluxed at 60°C with constant stirring for 12 h. The yellow coloured (S)-2-chloro-3-(4-benzamidoacetophenyl)-propionic acid obtained on cooling the reaction mixture to room temperature was filtered off, washed repeatedly with cold methanol and recrystallised from hot acetone and dried over P2O5 for 12 h. The resultant product was further purified by chromatography through a silica gel column using a mixture of diethylether: acetone (5:1 v/v) as eluent to get an yield of 2.81 gram (69.82%). Step 4 (S)-2-chloro-3-(4-benzamidoacetophenyl)-propionic acid (S)- 1,2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid (S)-l,2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid was prepared by dissolving 5.84 gram (16.2 mmol) of (S)-2-chloro-3-(4-benzamidoacetophenyl)-propionic acid prepared as illustrated in step 3 in 40 ml of absolute dichloromethane and to it added 2.5 ml (21.2 mmol) of thionylchloride with constant stirring. The reaction mixture was then heated to 60°C and the stirring was continued till the evalution SO2 ceased. On cooling the reaction mixture to room temperature (S)-l,2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid was separated as a white solid which was filtered off and washed several times with cold chloroform and the final product was recrystallized from hot benzene solution. The product was further purified by column chromatography through a silica gel column using a mixture of petroleum ether and acetone in 5:1 v/v as eluent to get 4.22 gram (68-84%) of (S)-l,2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid. Step -5 (S)-l, dichloro-3-(4-benzamidoacetophenyl)-propionic acid+ 4- hydroxybenzoic acid (S)-2-chloro-3-(4-benzamidoacetophenyl)- 1 -benzoic acid-propionate (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-benzoic acid-propionate prepared by mixing together absolute dichloromethane solution of (S)-l, 2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid (4.81 gram/12.7 mmol in 20ml of dry dichloromethane) prepared as described in step 4 and 4-hydroxybenzoic acid (1.8 gram/13.0 mmol in 20 ml of dry dichloromethane) in equimolar ratio and the reaction mixture was stirred for 4 h at room temperature. 0.4 ml (3.1 mmol) of triethylamine was then added to the reaction mixture drop wise with constant stirring. The reaction mixture was then refluxed at 75°C for 18 h. The yellow coloured solution containing (S)-2-chloro-3-(4-benzamidoacetophenyl)-1 -benzoic acid-propionate was reduced by vacuum distillation and the product was washed repeatedly with cold acetonitrile solution. The product was separated by column chromatoghaphy through a silica gel column using a mixture of petroleum ether and acetonitrile in 5 : 1 v/v as eluent. The yield obtained was 3.74 gram (63.17%). Step 6 (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-benzoic acidproprionate (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(l-chlorobenzoic acid)- propionate (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(l-chlorobenzoic acid)- propionate was prepared by dissolving 3.32 g (7.11 mmol) of (S)-2-chloro- 3-(4-benzamidoacetophenyl)-l-benzoic acid-propionate prepared as described in step 5 in 40 ml of absolute dichloromethane and to it added 0.76 ml (10.4 mmol) of thionylchloride with constant stirring under nitrogen atmosphere. The reaction mixture was then heated to 60° C and the stirring was continued till the evalution of SO2 ceased. On cooling the reaction mixture to room temperature (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-benzoic acid-propionate was separated as a white product which was filtered off and washed repeatedly with cold chloroform and the product was purified by passing through a silica gel column using a mixture of petroleum ether and acetonitrile in 5: 1 v/v as eluent. The final product was recrystallized from hot benzene solution to get 1.86 gram (52.32%) of (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(l-benzoic acid-propionate. Step 7 (S)-2-chloro-3-(4-benzamidoacetophnyl-1 -(1 -chlorobenzoic acid)- propionate + 4-hydroxybenzoic acid (S)-2-chloro-3-(4- benzamidoacetophenyl)-l-(4'-benzoid acid )- benzoatopripionate. (S)-2-chloro-3-(4-benzamidoacetophnyl-1 -(4'-benzoic acid)- benzoatopropionate was prepared by mixing togther absolute dichloromethane solutions of (S)-2-chloro-3-(4-benzamidoacetophnyl-l-(1-chlorobenzoic acid)-propionate (2.65 gram/5.3 mmol in 20 ml dry dichloromethance) prepared as illustrated in step 6 and 4-hydroxybenzoic acid (0.95 gram/68 mmol in 15 ml of dry dichloromethane) and the reaction mixture was stirred at ambient temperature for 4 under nitorgen atmosphere. 0.45 and (3.2 mmol) of trienthylamine was then added to the reaction mixture drop wise and refluxed the reaction mixture at 75 °C with constant stirring for 22h. The yellow coloured solid of (S)-2-chloro-3-(4-benzamidoacetophnyl-l-(4'-benzoic acid)-benzoatopropionate was separated by removing the excess solvent by vacuum distillation, washed twice with cold ethanol and chromatographed through a silica gel column using a mixture of petroleum ether : acetone (5 : 1 v/v) as eluent. The product was recrystallized from hot benzene solution. The yield obtained was 1.64 gram (51.48%). Step 8 (S)-2-chloro-3-(4-benzamidoacetophnyl-l-(4' benzoic acid)- benzoatopropionate (S)-2-chloro-3-(4- benzamidoacetophnyl-1 -(4'-chlorobenzoic acid)-benzoatopropionate (S)-2-chloro-3-(4-benzamidoacetophnyl-1 -(1 -chlorobenzoic acid)- benzoatopropionate was prepared by dissolving 2.08 gram (3.3 mmol) of (S)-2-chloro-3-(4-benzamidoacetophnyl-l-(4'-benzoic acid)- benzoapropionate prepared as described in step 7 in 40 ml of absolute dichloromethane and to it added 0.65 ml (4.7 mmol) of thionychloride with constant stirring under nitrogen atmosphere. The reaction mixture was then heated to 60 °C and the stirring was continued till the evalution of SO2 ceased. On cooling the reaction mixture to room temperature (S)- 2-chloro-3-(4-benzamidoacetophnyl-1-(4'-chlorobenzoic acid)- benzoatopropionate was separated as a white colour product which was filtered off, washed repeatedly with cold chloroform and dried over vacuum for 12 h. (S)-2-chloro-3-(4-benzamidoacetophnyl-l-(4'-chlorobenzoic acid)-benzoatopropionate was purified by column chromatography through a silica gel column using a mixture of petroleum ether: acetone ( 5: 1 v/v) as eluent. The product was recrystallized from hot dichloromethane solution to get an yield of 1.13 gram (52.64%). Step 9 (S)-2-chloro-3-(4-benzamidoacetophnyl-l-(4'-chlorobenzoic acid)- benzoatopropionate + 1-hexadecanol (S)-2-chloro-3-(4- benzamidoacetophnyl- l-(4'-benzamidoacetophenyl)-1-(4'-hexadecyloxybenxoyl)-benzoatopropioante) (S)-chloro-3-(4-benzamidoacetophenyl)l-(4'-hexadecyloxybenzoyl)-benzoatopropionate was prepared by mixing together absolute dichloromethane solutions of (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(4'-chlotobenzoic acid)-benzoatopropionate (2.3 gram/3.8 mmol in 20 ml of dry dichloromethane) prepared as described in step 8 and 1-hexadecanol (1.01 gram/1.2 mmol in 15 ml of dry dichloromethane) under nitrogen atmosphere and the reaction mixture was stirred at ambient temperature for 4h 0.4 ml (3.3 mmol) of triethylamine was added then added to the reaction mixture drop wise and the reaction mixture was refluxed at 60 °C with constant stirring for 6 h. The read coloured solution contained (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(4'-hexadecyloxybenzoyl)-benzoatopropionate was isolated as red gelly product after removing the excess solvent by vacuum distillation, washed repeatedly with cold benzene solution and dried over vacuuo for 12 h. the crude product was then chromatographed through a silica get column using a mixture of petroleum ther " acetone (5 : 1 v/v) as eluent. The yield obtained was 1.52 gram (49.60 %). The room temperature ferroelectric liquid crystal compound prepared by the process of this invention exhibit characteristic ferroelectric properties in and around room temperatures which is a rare phenomena, as the most of the reported ferroelectric compounds used for the appl icational purrposes are the mixtures of more than one component . The room temperature ferroelectric liquid crystal compound of the invention is therefore useful for both fundamental as well as applied research aspects including for the no n- linear optical applications. Further, such room temperature ferroelectric liquid crystal compound can be used as host materials for the preparation of other FLC mi xtures. The need for this type of room temperature ferroelectric materials as strongly felf because the preparation and characterisation of FLC mixtures is time consuming as well as expensive. These compounds prepared as per the process of this invention can be directly used i the applicational aspects such as polarisation controllers, switching attenuators, display devices etc. The study of the fundamental ferroelectric properties viz., spontaneous polarisation, tilt angle, time response etc., of the present invented compound reveals that he magnitudes of these parameters are found to be of in good agreement with those of commercially available multi-component materials. In fact some of the above properties envisage that this compound showed better physical characteristics tha n the commer c i a 11y available c om pounds. WE CLAIM: 1. A process for the preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl) -1- (4'-hexadecyloxybenzoyl) -benzoatopropionate which comprises in: i) known method of nucleophilic substitution of -NH2 group from (S)-2-chloro-3- (4-hydroxyphenyl)-propionic acid by a chlorine atom via known diazonium salt formation, in presence of freshly pulverized sodium nitrate, to obtain crystals of (S)-2-chloro-3~ (4-hydroxyphenyl)-propionic acid, ii) (S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid is reacted said l-chloro-2-benzamidoacetic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, benzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3-(4-benzamidoacetophenyl)-propionic; iii) (S)-2-chloro-3-(4-benzamidoacetophenyl-propionic acid is refluxed with thionyl chloride to obtain (S)-l, 2-dichloro-3- (4-benzamidoacetophenyl)-propionic iv) (S)-l,2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid is reacted with 4-hydroxybenzoic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, behzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-benzoic acid; v) (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-benzoic acid propionate is carried with thionyl chloride to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(l-chlorobenzoic acid), vi) (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(l-chlorobenzoic acid) is reacted with 4-hydroxybenzoic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, behzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2- chloro-3-(4-benzamidoacetophenyl)-l-(4'-benzoic acid)- benzoatopropionate; vii) (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-4'- benzole acid)-benzoatopropionate is reacted with thionyl chloride with constant stirring to obtain (S)-2-chloro-3- (4- benzamidoacetophenyl)-l-(4' -l--chlorobenzoic acid)- benzoatopropionate, viii) (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(4'-l-chlorobenzoic acid)-benoatopropionate is reacted with 1-hexadecanol in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, befizene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(4'-octadecyloxybenzoyl)-benzoatopropionate; 2. A process as claimed in claim 1 wherein said first step comprises nuclephilic substitution of -NH2 group form (S)-2amino-3-(4-hydrophenyl)-propionic cid by a chlorine atom via diazonium salt formation, in the presence of freshly pulverized sodium nitrate, stirring the reaction mixture at 0-4 °C extracting with a suitable organic as solvent as herein described reduced pressure separating the compound by column chromatography using a silica gel column and eluent mixture comprising diethylether and acetane followed by recrystallization to get crystals of (S)-2- chloro-3-(4-hydroxyphenyl)-propionic acid. 3. A process for the preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl) -1- (4'-hexadecyloxybenzoyl) -benzoatopropionate, substantially as herein described and exemplified in the examples.

Full Text

FIELD OF INVENTION
This invention relates to the compound (S')-2-chloro-3- invention is a novel room temperature ferroelectric
liquid crystal (FLO which is useful in the applicational aspects such as polarisation controllers, switching attenuators and display devices.
PRIOR ART
Hitherto there are no processess of synthesizing these room temperature ferroelectric compounds made out of optically active (S)-2-amino-3-(4-hydroxyphenyl)-propionic acid. OBJECTS OF THE INVENTION
The main object of the present invention is to provide a process for the synthesis of new ferroelectric liquid crystal compound, (S)-2-chloro-3-

(4-benzamidoacetophenyl)-l-(4'-hexadecyloxybenzoyl)-benzoatopropionte, which ferroelectricity at ambient temperature.
DESCRITPION OF INVENTION
According to this invention there is provided A process for the
preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl) -1- (4'-
hexadecyloxybenzoyl) -benzoatopropionate which comprises in:
i) known method of nucleophilic substitution of -NH2 group from (S)-2-chloro-3- (4-hydroxyphenyl)-propionic acid by a chlorine atom via known diazonium salt formation, in presence of freshly pulverized sodium nitrate, to obtain crystals of (S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid,
ii) (S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid is reacted said
l-chloro-2-benzamidoacetic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichlorome thane, behzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3-(4-benzamidoacetophenyl)-propionic;

iii) (S)-2-chloro-3-(4-benzamidoacetophenyl-propionic acid is refluxed with thionyl chloride to obtain (S)-l, 2-dichloro-3- (4-benzamidoacetophenylj-propionic
iv) (S)-l,2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid is reacted with 4-hydroxybenzoic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichloro me thane, behzene, methanol, dime thy Iformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-benzoic acid;
v) (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-benzoic acid
propionate is carried with thionyl chloride to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(l-chlorobenzoic acid),
vi) (S)-2-chloro-3-(4-benzamidoacetophenyl)-1 -(1 -chlorobenzoic
acid) is reacted with 4-hydroxybenzoic acid in presence of a
catalyst triethylamine and in dry organic solvent such as
dichloromethane, behzene, methanol, dimethylformamide,
diethylether under inert atmosphere of nitrogen to obtain (S)-2-
chloro-3-(4-benzamidoacetophenyl)-1 -(4'-benzoic acid)-
benzoatopropionate;

vii) (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-4'- benzole
acid)-benzoatopropionate is reacted with thionyl chloride with
constant stirring to obtain (S)-2-chloro-3- (4-
benzamidoacetophenyl)-l-(4' -l--chlorobenzoic acid)-
benzoatopropionate,
viii) (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(4'-l-chlorobenzoic acid)-benoatopropionate is reacted with 1-hexadecanol in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, behzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(4'-octadecyloxybenzoyl)-benzoatopropionate;
According to the present invention, preparation of this material comprises a total of nine steps followed by various compositions under different conditions.
The first step comprises: the process of nuclephilic substitution of -NH2 group from (S)-2-amino-3-(4-hydrooxyphenyl)-propionic acid by a chlorine atom via diazonium salt formation, in the presence of freshly pulverized sodium nitrate.

stirring the reaction mixture for 6 hours at 0-4'C, extracting with a suitable organic solvent, dryinq the organic layer with an appropriate drying agent for 12 hours, removing the excess solvent under reduced pressure, separating the compound by column chromatography using a silica gel column and appropriate eluent mixture, followed by recystallization to get crystals of (S )---2~chloro--3-(4-hydroxyphenyl )-propionic acid.
Second step of the process illustrates the preparation of l-chloro-2--benzamidoacet ic acid by reflux ing 2-ben;zamidoacetic acid with thionyl chloride at 75' for 8 hours, removing the excess organic solvent by vacuum distillation, washing the product with suitable cold solvent, drying the product over an appropriate desiccant for a period of 10 hours, separating the compound by column chromatography using a silica gel column and appropriate eluent mixture.
Third step of the process describes the preparat ion of (S)-2-ch1oro-3-(4-benzamidoacetopheny1)-

propionic acid by reacting (S)-2-chloro-3- Fourth step of the process describes the preparation of (S)-1, 2-di chloro—3-(4-benzamidoaceptopheny 1 ) -propionic acid by refluxing said (S)-2-chloro-~3-(4-benzamidoacetopheny1)—propionic acid with thionyl chloride at 60'C with constant stirring removing the excess organic solvent by vacuum distillation, washing the product with suitable cold solvent.

Fifth step of the process describes the preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl)
1- benzole acid propionate by reacting (S)-1,2
di chloro~-3-(4---benzami doacetopheny 1)~propionic acid with 4-hydroxybenzoic acid in presence of a catalyst, and dry organic solvent under inert atmosphere, stirring the reaction mixture initially at room temperature for 4 hours, refluxing the reaction mixture for a period upto 18 hours, removing the excess organic solvent by vacuum distillation, washing the product with suitable cold solvent, drying the product over an appropriate desiccant for a period of 12 hours, separating the compound by column chromatography using a silica gel column and appropriate eluent mixture.
Sixth step of the process describes the preparat ion of (S)-2-ch1oro-3-(4~benzami doacetopheny1) -1--(1-chlor ob enzoi c acid) propionate by reacting (S) --2-ch 1 oro-3- ( 4-benzam i doacetopheny 1 ) -1 -benzol c acid propionate with thionyl chloride with constant stirring, removing the excess organic solvent by

vacuum distillation, washing the product with suitable cold solvent, drying the product over an appropriate desiccant for a period of 10 hours, separating the compound by column chromatography using a silica gel column and appropriate eluent mixture, followed by recrystal1ization to get c r y s t a 1 s o f C S) ••- 2 - c h 1 o r o 3 - C 4 - b e n;: a m i d o a c e t o p h e n y 1 ') -1 -C1-chlorobenzoic acid) propionate.
Seventh step of the process describes the preparation of (S)-2-chloro-3-(4-benzamido-acetophenyl) -1-(4' -benzoic ac id)-benzoatopropionate by reacting (S )~2---chloro~-3-~
separating the compound by column chromatography usinq a silica gel column arid appropriate eluent mixture.
Eighth step of the process describes the preparation of (S)-2-ch1oro»3-C4--benzamido-acetopheny1) -1-(4-1-c h 1 o r o be n 2 o i c acid) - be n 2z oa t o p r o p i o na t e by react i ng (S)-2-chloro-3- (4-bebenzamidoacetophenyl ) -1-(4 ' -benzo i c acid) -benzoatop rop i onate with thionylchloride with constant stirring, removing the excess organic solvent by vacuum distillation, washing the product with suitable cold solvent, drying the product over an appropriate desiccant for a period of 12 hours, separating the compound by column chromatography using a silica gel column and appropriate eluent mixture.
Ninth step of the process describes the preparation of (S)-2-chloro™3-(4-benzamido-acetophenyl) ~-l---<:4 by reacting doacetopheny1 acid with in presence of a ceitalyst and dry organic solvent under inert atmosphere stirring the>
reaction mixture initially at room temperature for 4 hours, re flux ing the reaction mixture for a period upto b hours, removing the excess organic solvent by vacuum distillation, washing the product with su i t a b 1 e c o 1 d so 1 ve n t, drying t he p r o clu c t ove r an appropriate desiccant for a period of 12 hours, separating the compound by column chromatography using a silica gel column and apropriate eluent mi xture.
According to another feature of the present invention, the inert atmosphere may be maintained by using nitrogen.
According to yet another feature of the present invention, the catalyst used is such as triethyiamine.
According to yet another feature of the present invention, the dry organic solvent used is such as dicloromethane, benzene, methanol, dimethylformamide, diethylether.
According to yet another feature of the present invention, organic solvent used for

purification of compound by column chromatography is such as actone, acetonitrile, petroleum ether, d i c h 1 o r ome t hane .
According to yet another feature of the
present invention, drying agent used is such as
sodium sulphate, phosphorous pentoxide, calcium
chloride.

A step wise process for the preparation of a room temperature
ferroelectric liquid crystal compound, (S)-2-chloro-3-(4-
benzamidoacetophenyl)-l-(4-hexadecyloxybenzoyl)-benzoatopropionate, is presented as follows:
Step 1
(S)-2-amino-3-(4-hydroxyphenyl)-propionic acid (S)-2-
chloro-3-(4-hydroxyphenyl)-propionic acid
(S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid was prepared by a known method and is described first 5.43 gram (30.0 mmol) of (S)-2-amino-3-(4-hydroxyphenyl)-propionic acid was dissolved in 20 ml of 6.0 N HCI and the solution was brought to 0°C. 2.72 gram (32.0 mmol) of freshly pulverised sodium nitrate was added to the solution in small portions with vigorous stirring while maintaining the reaction temperature between 0 and 5°C. The reaction mixture was stirred for 16 h. The solution was then extracted with 40 ml of diethylether and the etherial layer was dried over anhydrous sodium sulphate for 12 h. (S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid obtained as an yellow product on removing the excess solvent by distillation under reduced pressure was washed repeatedly with cold benzene, seperated by chromatography through a silica gel column using a mixture of diethylether : acetone (5:1 v/v) as eluent. The product was recrystallized from hot dichloromethane and dried over P2O5for 12 h. to get an yield of 3.2 gram (53.2%).
Step 2
2-benzamidoacetic acid l-chloro-2-benzamidoacetic acid
l-chloro-2-benzamidoacetic acid was prepared by mixing together 4.48 gram (25.0 mmol) of 2-benzamidoacetic acid and 3.0 ml (40.0 mmol) of thionyl chloride in 40 ml of dry benzene under nitrogen atmosphere and kept the reaction mixture under reflux with continuous stirring at 75°C

for 8 h. After the evalution of SO2 gas was ceased, the volume of the resulting solution was reduced by vacuum distillation of get an yellow solid product which was suction filtered, washed several times with cold methanol and dried over anhydrous calcium chloride for l0h. The product was purified by passing through a silica gel column using a mixture of petroleum ether: acetonitrile (5:1 v/v) as eluent to get 2.6 gram (52.6%) of l-chloro-2-benzamidoacetic acid.
Step 3
l-chloro-2-benzamidoacetic acid + (S)-2-chloro-3-(4-hydroxyphenyl)-
propionic acid (S)-2-chloro-3-(4-benzamidoacetophenyl)-
propionic acid
3.95 (20.0 mmol) of l-chloro-2-benzamidoacetic acid prepared as illustrated in step 2 and 5.0 gram. (25.0 mmol) of (S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid prepared as described in step 1 were magnetically stirred in 40 ml dry dichloromethane at ambient temperature for 2 h. 0.5 ml (3,6 mmol) of triethylamine was then added to the reaction mixture drop wise and the reaction mixture was refluxed at 60°C with constant stirring for 12 h. The yellow coloured (S)-2-chloro-3-(4-benzamidoacetophenyl)-propionic acid obtained on cooling the reaction mixture to room temperature was filtered off, washed repeatedly with cold methanol and recrystallised from hot acetone and dried over P2O5 for 12 h. The resultant product was further purified by chromatography through a silica gel column using a mixture of diethylether: acetone (5:1 v/v) as eluent to get an yield of 2.81 gram (69.82%).
Step 4
(S)-2-chloro-3-(4-benzamidoacetophenyl)-propionic acid (S)-
1,2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid
(S)-l,2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid was prepared by dissolving 5.84 gram (16.2 mmol) of (S)-2-chloro-3-(4-benzamidoacetophenyl)-propionic acid prepared as illustrated in step 3 in 40 ml of absolute dichloromethane and to it added 2.5 ml (21.2 mmol) of thionylchloride with constant stirring. The reaction mixture was then

heated to 60°C and the stirring was continued till the evalution SO2 ceased. On cooling the reaction mixture to room temperature (S)-l,2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid was separated as a white solid which was filtered off and washed several times with cold chloroform and the final product was recrystallized from hot benzene solution. The product was further purified by column chromatography through a silica gel column using a mixture of petroleum ether and acetone in 5:1 v/v as eluent to get 4.22 gram (68-84%) of (S)-l,2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid.
Step -5
(S)-l, dichloro-3-(4-benzamidoacetophenyl)-propionic acid+ 4-
hydroxybenzoic acid (S)-2-chloro-3-(4-benzamidoacetophenyl)-
1 -benzoic acid-propionate
(S)-2-chloro-3-(4-benzamidoacetophenyl)-l-benzoic acid-propionate
prepared by mixing together absolute dichloromethane solution of (S)-l, 2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid (4.81 gram/12.7 mmol in 20ml of dry dichloromethane) prepared as described in step 4 and 4-hydroxybenzoic acid (1.8 gram/13.0 mmol in 20 ml of dry dichloromethane) in equimolar ratio and the reaction mixture was stirred for 4 h at room temperature. 0.4 ml (3.1 mmol) of triethylamine was then added to the reaction mixture drop wise with constant stirring. The reaction mixture was then refluxed at 75°C for 18 h. The yellow coloured solution containing (S)-2-chloro-3-(4-benzamidoacetophenyl)-1 -benzoic acid-propionate was reduced by vacuum distillation and the product was washed repeatedly with cold acetonitrile solution. The product was separated by column chromatoghaphy through a silica gel column using a mixture of petroleum ether and acetonitrile in 5 : 1 v/v as eluent. The yield obtained was 3.74 gram (63.17%).
Step 6
(S)-2-chloro-3-(4-benzamidoacetophenyl)-l-benzoic acidproprionate
(S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(l-chlorobenzoic acid)-
propionate
(S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(l-chlorobenzoic acid)-
propionate was prepared by dissolving 3.32 g (7.11 mmol) of (S)-2-chloro-

3-(4-benzamidoacetophenyl)-l-benzoic acid-propionate prepared as described in step 5 in 40 ml of absolute dichloromethane and to it added 0.76 ml (10.4 mmol) of thionylchloride with constant stirring under nitrogen atmosphere. The reaction mixture was then heated to 60° C and the stirring was continued till the evalution of SO2 ceased. On cooling the reaction mixture to room temperature (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-benzoic acid-propionate was separated as a white product which was filtered off and washed repeatedly with cold chloroform and the product was purified by passing through a silica gel column using a mixture of petroleum ether and acetonitrile in 5: 1 v/v as eluent. The final product was recrystallized from hot benzene solution to get 1.86 gram (52.32%) of (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(l-benzoic acid-propionate.
Step 7
(S)-2-chloro-3-(4-benzamidoacetophnyl-1 -(1 -chlorobenzoic acid)-
propionate + 4-hydroxybenzoic acid (S)-2-chloro-3-(4-
benzamidoacetophenyl)-l-(4'-benzoid acid )- benzoatopripionate.
(S)-2-chloro-3-(4-benzamidoacetophnyl-1 -(4'-benzoic acid)-
benzoatopropionate was prepared by mixing togther absolute dichloromethane solutions of (S)-2-chloro-3-(4-benzamidoacetophnyl-l-(1-chlorobenzoic acid)-propionate (2.65 gram/5.3 mmol in 20 ml dry dichloromethance) prepared as illustrated in step 6 and 4-hydroxybenzoic acid (0.95 gram/68 mmol in 15 ml of dry dichloromethane) and the reaction mixture was stirred at ambient temperature for 4 under nitorgen atmosphere. 0.45 and (3.2 mmol) of trienthylamine was then added to the reaction mixture drop wise and refluxed the reaction mixture at 75 °C with constant stirring for 22h. The yellow coloured solid of (S)-2-chloro-3-(4-benzamidoacetophnyl-l-(4'-benzoic acid)-benzoatopropionate was separated by removing the excess solvent by vacuum distillation, washed twice with cold ethanol and chromatographed through a silica gel column using a mixture of petroleum ether : acetone (5 : 1 v/v) as eluent. The product was recrystallized from hot benzene solution. The yield obtained was 1.64 gram (51.48%).
Step 8
(S)-2-chloro-3-(4-benzamidoacetophnyl-l-(4' benzoic acid)-
benzoatopropionate (S)-2-chloro-3-(4-
benzamidoacetophnyl-1 -(4'-chlorobenzoic acid)-benzoatopropionate

(S)-2-chloro-3-(4-benzamidoacetophnyl-1 -(1 -chlorobenzoic acid)-
benzoatopropionate was prepared by dissolving 2.08 gram (3.3 mmol) of
(S)-2-chloro-3-(4-benzamidoacetophnyl-l-(4'-benzoic acid)-
benzoapropionate prepared as described in step 7 in 40 ml of absolute
dichloromethane and to it added 0.65 ml (4.7 mmol) of thionychloride
with constant stirring under nitrogen atmosphere. The reaction mixture
was then heated to 60 °C and the stirring was continued till the evalution
of SO2 ceased. On cooling the reaction mixture to room temperature (S)-
2-chloro-3-(4-benzamidoacetophnyl-1-(4'-chlorobenzoic acid)-
benzoatopropionate was separated as a white colour product which was filtered off, washed repeatedly with cold chloroform and dried over vacuum for 12 h. (S)-2-chloro-3-(4-benzamidoacetophnyl-l-(4'-chlorobenzoic acid)-benzoatopropionate was purified by column chromatography through a silica gel column using a mixture of petroleum ether: acetone ( 5: 1 v/v) as eluent. The product was recrystallized from hot dichloromethane solution to get an yield of 1.13 gram (52.64%).
Step 9
(S)-2-chloro-3-(4-benzamidoacetophnyl-l-(4'-chlorobenzoic acid)-
benzoatopropionate + 1-hexadecanol (S)-2-chloro-3-(4-
benzamidoacetophnyl- l-(4'-benzamidoacetophenyl)-1-(4'-hexadecyloxybenxoyl)-benzoatopropioante)
(S)-chloro-3-(4-benzamidoacetophenyl)l-(4'-hexadecyloxybenzoyl)-benzoatopropionate was prepared by mixing together absolute dichloromethane solutions of (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(4'-chlotobenzoic acid)-benzoatopropionate (2.3 gram/3.8 mmol in 20 ml of dry dichloromethane) prepared as described in step 8 and 1-hexadecanol (1.01 gram/1.2 mmol in 15 ml of dry dichloromethane) under nitrogen atmosphere and the reaction mixture was stirred at ambient temperature for 4h 0.4 ml (3.3 mmol) of triethylamine was added then added to the reaction mixture drop wise and the reaction mixture was refluxed at 60 °C with constant stirring for 6 h. The read coloured solution contained (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(4'-hexadecyloxybenzoyl)-benzoatopropionate was isolated as red gelly product after removing the excess solvent by vacuum distillation, washed repeatedly with cold benzene solution and dried over vacuuo for 12 h. the crude product was then chromatographed through a silica get column using a mixture of petroleum ther " acetone (5 : 1 v/v) as eluent. The yield obtained was 1.52 gram (49.60 %).

The room temperature ferroelectric liquid crystal compound prepared by the process of this invention exhibit characteristic ferroelectric properties in and around room temperatures which is a rare phenomena, as the most of the reported ferroelectric compounds used for the appl icational purrposes are the mixtures of more than one component .
The room temperature ferroelectric liquid crystal compound of the invention is therefore useful for both fundamental as well as applied research aspects including for the no n- linear optical applications. Further, such room temperature ferroelectric liquid crystal compound can be used as host materials for the preparation of other FLC mi xtures.
The need for this type of room temperature ferroelectric materials as strongly felf because the preparation and characterisation of FLC mixtures is time consuming as well as expensive. These

compounds prepared as per the process of this invention can be directly used i the applicational aspects such as polarisation controllers, switching attenuators, display devices etc.
The study of the fundamental ferroelectric properties viz., spontaneous polarisation, tilt angle, time response etc., of the present invented compound reveals that he magnitudes of these parameters are found to be of in good agreement with those of commercially available multi-component materials. In fact some of the above properties envisage that this compound showed better physical characteristics tha n the commer c i a 11y available c om pounds.

WE CLAIM:
1. A process for the preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl) -1- (4'-hexadecyloxybenzoyl) -benzoatopropionate which comprises in:
i) known method of nucleophilic substitution of -NH2 group from (S)-2-chloro-3- (4-hydroxyphenyl)-propionic acid by a chlorine atom via known diazonium salt formation, in presence of freshly pulverized sodium nitrate, to obtain crystals of (S)-2-chloro-3~ (4-hydroxyphenyl)-propionic acid,
ii) (S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid is reacted said
l-chloro-2-benzamidoacetic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, benzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3-(4-benzamidoacetophenyl)-propionic;

iii) (S)-2-chloro-3-(4-benzamidoacetophenyl-propionic acid is refluxed with thionyl chloride to obtain (S)-l, 2-dichloro-3- (4-benzamidoacetophenyl)-propionic
iv) (S)-l,2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid is reacted with 4-hydroxybenzoic acid in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, behzene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-benzoic acid;
v) (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-benzoic acid
propionate is carried with thionyl chloride to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(l-chlorobenzoic acid),
vi) (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(l-chlorobenzoic
acid) is reacted with 4-hydroxybenzoic acid in presence of a
catalyst triethylamine and in dry organic solvent such as
dichloromethane, behzene, methanol, dimethylformamide,
diethylether under inert atmosphere of nitrogen to obtain (S)-2-
chloro-3-(4-benzamidoacetophenyl)-l-(4'-benzoic acid)-
benzoatopropionate;

vii) (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-4'- benzole
acid)-benzoatopropionate is reacted with thionyl chloride with
constant stirring to obtain (S)-2-chloro-3- (4-
benzamidoacetophenyl)-l-(4' -l--chlorobenzoic acid)-
benzoatopropionate,
viii) (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(4'-l-chlorobenzoic acid)-benoatopropionate is reacted with 1-hexadecanol in presence of a catalyst triethylamine and in dry organic solvent such as dichloromethane, befizene, methanol, dimethylformamide, diethylether under inert atmosphere of nitrogen to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(4'-octadecyloxybenzoyl)-benzoatopropionate;
2. A process as claimed in claim 1 wherein said first step comprises nuclephilic substitution of -NH2 group form (S)-2amino-3-(4-hydrophenyl)-propionic cid by a chlorine atom via diazonium salt formation, in the presence of freshly pulverized sodium nitrate, stirring the reaction mixture at 0-4 °C extracting with a suitable organic as solvent as herein described

reduced pressure separating the compound by column chromatography using a silica gel column and eluent mixture comprising diethylether and acetane followed by recrystallization to get crystals of (S)-2- chloro-3-(4-hydroxyphenyl)-propionic acid.
3. A process for the preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl) -1- (4'-hexadecyloxybenzoyl)
-benzoatopropionate, substantially as herein described and exemplified in the examples.

Documents:

943-del-1998-abstract.pdf

943-del-1998-claims.pdf

943-del-1998-correspondence-others.pdf

943-del-1998-correspondence-po.pdf

943-del-1998-description (complete).pdf

943-del-1998-drawings.pdf

943-del-1998-form-1.pdf

943-del-1998-form-19.pdf

943-del-1998-form-2.pdf

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Patent Number

232029

Indian Patent Application Number

943/DEL/1998

PG Journal Number

13/2009

Publication Date

27-Mar-2009

Grant Date

15-Mar-2009

Date of Filing

15-Apr-1998

Name of Patentee

THE SECRETARY, DEPARTMENT OF ELECTRONICS, GOVT. OF INDIA,

Applicant Address

ELECTRONICS NIKETAN, 6, CGO COMPLEX, NEW DELHI-110003.

Inventors:

#	Inventor's Name	Inventor's Address
1	DR. VENKATA G.M.K. PISIPATI	CENTRE FOR LIQUID CRYSTAL RESEARCH AND EDUCATION FACULTY OF PHYSICAL SCIENCES, NAGARJUNA UNIVERSITY, NAGARJUNA NAGAR 522510 (ANDHRA PRADESH).ALL INDIAN NATIONALS,INDIA
2	SHRI POLURI ANJANA KUMAR	CENTRE FOR LIQUID CRYSTAL RESEARCH AND EDUCATION FACULTY OF PHYSICAL SCIENCES, NAGARJUNA UNIVERSITY, NAGARJUNA NAGAR 522510 (ANDHRA PRADESH).ALL INDIAN NATIONALS,INDIA

PCT International Classification Number

G02F 1/133

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA