Title of Invention

"A PROCESS FOR THE PREPARATION OF (S) -2-CHLORO-3-(4-BENZAMIDOACETOPHENYL) -1-(4-OCTADECYLOXYBENZOYL)-BENZOATOPROPIONATE"

Abstract This invention relates to a process for the preparation of (S)-2-chloro-3- (4-benzamidoacetophenyl) -l-(4'-octyloxybenzoyl)-benzoatopropionate which comprises in the step of Nucleophilic substitution of -NH2 group from (S)-2-amino-3- (4-hydroxyphenyl)-propionic acid by a chlorine atom via diazonium salt formation is carried in presence of freshly pulverized sodium nitrate stirring the reaction mixture at 0-4°C extracting with organic solvent selected from diclorome thane, benzene, methanol, dimethyl or memide, diethylether, drying the organic layer with removing the excess solvent under reduced pressure separating the compound by column chromatography using a silica gel column and eluent mixture comprising diethyl ether and acetone followed by recrystallization to get the said product, preparing l-chloro-2-benzamidoacetic acid by refluxing 2-benzamidoacetic acid with thionyl chloride, reacting said (S)- 2-chloro~3-(4 hydroxyphenyl)-propionic acid with said l-chloro-2- benzamidoacetic acid to obtain crystals of (S)-2-chloro-3-(4- benzamidoacetophenyl)-propionic acid; refluxing said (S)-2-chloro-3-(4- benzamidoacetophenyl-propionic acid with thionyl chloride to obtain (S)- 1, 2-dichloro-3- (4-benzamidoacetophenyl)-propionic acid; reacting said (S)-l ,2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid with 4- hvdroxybenzoic acid in presence of catalyst triethylamine to obtain (S)-2- chloro-3- (4-benzamidoacetophenyl)-l-benzoic acid propionate, reacting said (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-benzoic acid propionate with thionyl chloride to obtain (S)-2-chloro-3-(4-benzamidoacetophenyl)- l-(l-chlorobenzoic acid) propionate, reacting said (S)-2-chloro-3-(4- benzamidoacetophenyl)-l-(l-chlorobenzoic acid) propionate with 4- hydroxybenzoic acid in presence of said catalyst to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)- 1 -(4'-benzoic acid)-benzoatopropionate, reacting (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-4'-benzoic acid)- benzoatopropionate with thionyl chloride to obtain (S)-2-chloro-3- (4- benzamidoacetophenyl)-l-(4' -l--chlorobenzoic acid)- benzoatopropionate, reacting said (S)-2-chloro-3-{4- benzamidoacetophenyl)- 1 -(4'- 1 -chlorobenzoic acid)-benoatopropionate with 1-octariol in presence of a catalyst to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(4'-octadecyloxybenzoyil)-benzoatopropionate.
Full Text FIELD OF INVENTION
This invention relates to a process for the preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(4'-octyloxybenzoyl)benzoatopropionate. The compound of the present invention is a novel room temperature ferroelectric liquid crystal (FLC) which is useful in the application aspects such as polarization controllers, switching attenuators, display devices.
PRIOR ART
Hitherto there are no processes 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)-1-(4' octyloxybenzoyl)-

i i ) p r e p a r a i n g 1 ••••• c h 1 o r o 2 - b e n z a m i d o acetic: a c: i d by
re fluxing 2-denzamidoacetic acid with thionyl
chlor i de.
i i i ) p r e pa r a i n g C S > -2~ c h 1 o r o-3- (. 4- be n z am i doa c e t o p he ny 1 )
prop ionic acid by reacting said (S )~2-chlor o-3-(4~
hydroxyphenyl)-prop ionic acid with said 1-chloro-2-
b e n z a m i d o a c e t i c a c i d t o o b t a i n crystals of C S > - 2 -
chloro-3-(4-benzamidoacetopheny1)-propionic ac i d.
i v ) o b t a i n i n g C S )-1 ,2 - d i c h 1 o r o - 3 - C 4 -
benzam i doacep t opheny 1 )--prop ionic acid by re flux ing said
C S )- 2 -- c h 1 o r o - 3 - with thiony1 c h1o ride. v ') p r e p a r i n g C S ) - 2 - c h 1 o r o -•• 3 -••
.!. •- d e n z o i c acid p r o p i o n a t e by reacting said f. S) -1 , 2:
d i c h 1 o r o -- 3 - 4 hydroxybenzoi c: acid in presence of a catalyst.
v i ) p r e p a r i n g (S > •••- 2 -- c h 1 o r o 3 - (4 - b e n z a m i d o a c e t o p h e n y 1 )
.... i.... (i....,-1-., j c, r o I-, e n z o j ,- a,.. j c|;, p r,-, p i Q n a t e b y re a c t i n g said
C S) - 2 -- c h 1 or o - 3 - C 4 •- b e n z a rn i d o a c e t o p h e n y 1 ') --1 - b e n z o i c acid p r o p i o n a. t e w i t h t h i o n y 1 c: h lor id e.
v i i > p r e p a r i n g (S)- 2 c h 1 o r o - 3 - (4 - b e n z a f n i d o - a c e t o p h e n y 1) -1-( 4 ' - b e n z o i c a c i d ) - b e n z o a t o p r o p i o n a t e b y reacting
benzoatopropionate, which exhibits ferroelectricity at ambient temperature. According to the present invention, preparation of this material comprises a total of nine steps followed by various compositions under different conditions.
DESCRIPTION OF THIS INVENTION
According to this invention there is provided a process for the
preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl) -l-(4'-
octyloxybenzoyl) benzoatopropionate which comprises in the step of:
i) Obtaining crystals of (S)-2-chloro-3- (4-hydroxyphenyl)-propionic acid by the step of nucleophilic substitution of -NHa group from (S)-2-amino-3- (4-hydroxyphenyl)-propionic acid by a chlorine atom via diazonium salt formation in the presence of freshly pulverized sodium nitrate,
ii) Preparing l-chloro-2-benzamidoacetic acid by refluxing 2-benzamidoacetic acid with thionyl chloride,
iii) preparing (S)-2-chloro-3-(4-benzamidoacetophenyl)-propionic acid by reacting said (S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid with said l-chloro-2-benzamidoacetic acid to obtain crystals of (S)-2-chloro-3-(4-benzamidoacetophenyl)-propionic acid ;
iv) obtaining (S)-l, 2-dichloro-3- (4-benzamidoacetophenyl)-propionic acid by refluxing said (S)-2-chloro-3-(4-benzamidoacetophenyl-propionic acid with thionyl chloride;

v) preparing (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-benzole acid propionate by reacting said (S)-l,2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid with 4-hydroxybenzoic acid in presence of catalyst triethylamine,
vi) preparing (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(l-chlorobenzoic acid) propionate by reacting said (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-benzoic acid propionate with thionyl chloride,
vii) preparing (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(4'-
benzoic acid)-benzoatopropionate by reacting said (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(l-chlorobenzoic acid) propionate with 4-hydroxybenzoic acid in presence of said catalyst,
viii) preparing (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(4' -1--chlorobenzoic acid)- benzoatopropionate which comprises reacting (S)-2-chloro-3-(4-benzamidoacetophenyl)-1 -4'-benzoic acid)-benzoatopropionate with thionyl chloride,
ix) preparing (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(4'-
octadecyloxybenzoyl)-benzoatopropionate by said (S)-2-chloro-
3-(4-benzarnidoacetophenyl)-l-(4'-1-chlorobenzoic acid)-
benoatopropionate with 1-octadecanol in presence of a catalyst.
In accordance with this invention the first step comprises the process of nucleophilic substitution of-NHa group from (S)-2-amino-3-(4-hydroxyphenyl)-propionic acid by a chlorine atom via diazonium salt formation in the presence of freshly pulverised sodium nitrate, stirring the reaction

m i x t u. r e f o r 6 h o u r s at 0 -• 4 ' C , e x t r a c t i n g wit h a s u. :i t a b 1 e o r g a n i c: s o 1 v e n t ? d r y i n g t h e o r g a n i c layer with an appropriate drying agent for 12 hours, removing the excess solvent under reduced pressure, separating the compound by column chromatography using a s i1i c a ge1 co1urn n a nd a p p r o p r i a t e eluent mi x t u r e, followed by recrystal1ization to get crystals of C S > -• 2 -• c h 1 o r o - 3 ~ (4 -• h y d r o x y p h e n y 1 ) — p r o p i o n i c acid.
Second step of the process illustrates the p r e p a r a t i o n o f i -••• c h lor o - 2 -~ b e n z a m i d o a c e t i c a c i d by r e f 1 u x i n g 2 •••- b e n z a m i d o a c e t i c a c i d w i t h t h i ID n y 1 chloride at 75*C for 8 hours, removing the excess or gan i c so1v en t tay vac uum d i s t i11a t i o n, wash i n g t he product with suitable cold solvent, drying the pro d u ct ove r an ap p r o p r i at e des i c can t f o r a per i od of 10 hi o u r s, s e p a r a t i n g t h e c o m p o u n d by c o 1 u m n chromatography using a silica gel column and appropriate eluent mixture.
T hi r d step of the pr oc ess des c r i bes the
p r e p a r a t i o n o f (. S) -•- 2 -• c h 1 o r o •-3 •- (. 4 - b e n z a m i d o a c e t o p h e n y 1 )

-propionic acid which comprises by reacting said (S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid with said l-chloro-2-benzamidoacetic acid in presence of a catalyst, in dry organic solvent under inert atmosphere, stirring the reaction mixture initially at room temperature for 2 hours, refluxing the reaction mixture for a period upto 12 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 followed by recrystallization to get crystals of (S)-2-chloro-3-(4-benzamidoacetophenyl)-propionic acid.
Fourth step of the process describes the preparation of (S)-l,2-dichloro-3-(4-benzamidoaceptophenyl)-propionic acid which comprises by refluxing said (S)-2-chloro-3-(4-benzamidoacetophenyl)-propionic acid with thionyl chloride at 60'C with constant stirring, removing the excess organic

s o 1 v e n t b y v a c u LI m d i s t illation, w a s h ing t hi e p r o duct w 11 h e; u i t a b 1 e c o 1 d solvent, d r y i n g the? p r o d u c t over an appropriate d ess ice ant for a period of 10 h o u r s , s e p a r a t i n g t h e c o m p o u n d b y c o 1 u m n c h r o m a t o g r a p h y using a s i 1 i c a g e 1 c o 1 u rn n a n d appropriate e1uent m i x t ur e, f o11owed by r e c r y stall! z a t i o n t o g e t crystals o f C S ) -1 , 2 --d i c h 1 o r o ••••• 3 -• C 4 -•• b e n 2 a. m i d o a c e t o p h e n y 1 ) — p r o p i o n i c a c i rJ.
Fi f t h st ep o f the p r o cess des c r ibes the p r e pa r a t i o n o f (S)'-2- c h lor o - 3 - C 4 - b e? n 2 a m i d o a c e t o p h e n y 1 ') -1- ben zoic acid propionate by reacting said CS )•••-!, 2
ci i c n i o r o -- 3 (4 - b e n 2 a m i d o a c e t o p h e n y 1 ) - p r o picnic acid wit h
4-hydroxybensoic acid in presence of a catalyst, in ci r y o r g a n i c: s o 1 v e n t u. n d e r i n s e r t at rn o sphere, stirring the reaction mixture initially at room t e m p e r a t u r e f o r 4 h o u r s , r e f 1 u x i n g t h e r e a c t i o n m i x t u r e f or a pe r r i od u pt o 18 hour s, r emov i ng the excess organic solvent by vacuum distillation, washing the pr o du ct with su i t able cold solve nt, d r y i n g t he p r o d u c: t o v e r a n a p p r o p r i a t & d e? s i c c a n t f o r a p e r i o d of 12 hous, separating the compound by column chromatography using a silica gel column and appropriate eluent mixture.

Sixth step of the process describes the preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(l-chlorobenzoic acid) propionate by reacting said (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-benzoic acid propionate with thionyl chloride at 60'C 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 recrystallization to get crystals of (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(l-chlorobenzoic acid) propionate.
Seventh step of the process describes the preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(4'benzoicacid) benzoatopropionate by reacting said (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(l-chlorobenzoic acid) propionate with 4-hydroxybenzoic acid in presence of catalyst, in dry organic solvent under inert atmosphere, stirring the

v e a c 11 o n in i x i- u r e initially a t r o o m t e m p e r a t u r e f o r 4 h o u. r B y r e f 1 u. x ing t h e r e a c t i o n m i x t u r e f o r a p e r i o d u. p t o 2 2 h o u r s, r e? m o v i n g the e x cess o r g a n i c s o 1 v e n t by vacuum distillation, washing the product with suitable cold solvent, drying the product over an appropriate ciesiccant for a period of 12 hours, separating the c o m p o u n d b y c o 1 u m n c IT r o m a t o g r a p h y u s i n g a silica g e 1 c o1um n a n d a p p r o p ri a t e e1ue n t mixture.
Eighth s t ep of t he p r ocess des cribes the
p r e p a r a 11 o n o f (S) - 2 ••••• c h 1 o r o - 3 - (4 be n zaamid o - a c e t o p h e n y 1 )
.... i.... (; 4 >.... i --,- h 1 o r o b e n z o i c acid) •••- b e n s o a t o p r o p i o n ate w h i c h compr ises reacting N i nth s te p of t he process describes the

p r e p a r a t i o n of C S ) - 2 - c h 1 o r o - 3 - (4 -• b e n z a m i d o -••• a. c: e t o p h e n y 1 ) ... ^.... ,;4 i> o,:;: i y i o x y b E? n z o y 1 > ••••• b e n z o atop r o p i o n a t e by said C S ) -2 -•- c h I o r o •••- 3 - (4 - b e n z a m i c i o a c e t o p h e n y 1 ) •••-1 •••- C 4 ' -1 •••-c: hi 1 o r o tie n z o i c: acid ) - b e n z o a t o p r o - p i o n ate with. 1 - o c t a n o 1 in presence of a catalyst in dry organic solvent under inert atmosphere, stirring the reaction mixture i n i t i a 1 1 y a t r o o rn t e m p e r a b u re f o r 4 h o u r s , r e f 1 u x i n g t h e r e a ct i o n m i x t u r e f or a peri o d u p t o 26 hour s, removing the excess organic solvent by vacuum distillation, washing the product with suitable cold s o1ve nt, dr y i n g the pr oduc t ov e r a n approp r i at e d e s i c c a n t f o r a p e? r i o d of 12 h o u r s, separating the? compound by column chromatography using a silica g e 1 c o 1 u m n s. n d a p p r o p r i a t e el u e n t m i x t u r e .
A c cor di n g t o ano ther fea tu r e of t he present invention, the inert atmosphere may be maintained by u s i n g n i t r o g e n .
According to yet another feature of the present invention, the catalyst used is such as tr i et hy1 amine »

A c c o r d :i. n g t o ye t a not her feat u r e o f the p r e s e n t inventio n , the dry organic s o 1 v e n t u s ed is s u c h a s d i c 1 o r o m e t h a n e , b e n sens, met h a. n o 1 , d i m e t h y 1 f o r f n a m i d e , d i e t h y 1 e t h e r .
According to yet another feature of the present invention, organic solvent used for p u r i f i c a t i o n o f c o m p o u n d b y c o 1 u m n c: h r o m a t o g r a p h y is such as act one, ace ton i tr i le, petroleum ether, a i c h 1 o r ome t ha ne .
A c c o r d i n g t o y e t a n o t h e r f e a t u r e o f the
present invention, drying agent used is such as
sodium sulphate, phosphorous pent oxide, calcium
chlor i de .
Further objects and advantages of this invention
w ill b e mo r e a p p a r en t f r o m t h e ens u ing e x a m pie.
The ensuing example is not intended to impart any
1 i m i t a t i o n o n t h e s c o p e o f t h e i n v e n t ion.
STEP. 1_
(S)..... '2 -• ami n o - 3 - ( 4 ..... h y d r o xyphenyl ) -• p r o p i o n i c aci d ................... .........
..... ----------- ........ ----------------- : ( S ) •••- 2 - c h 1 o r o -- 3 •- C 4 ••- h y d r o x y p h e n y 1 ) •••- p r o p i o n i
a c i d

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) oHreshly pulverised sodium nitrate was added to the solution in small portions with vigorous stirring while maintaining lite reaction temperature between 0 and 5 °C. The reaction mixture was stirred for 16 h. 'Hie solution was then extracted with 40 ml of diethylcther and the eiheriai layer was dried over anhydrous sodium sulphate ibr 12 h. (S)-2-chloro-3-(4-hydroxyphc;iy!)-propionic acid obtained a.s an yellow product on removing the excess solvent by distillation under reduced pressure was washed repealediy vvilh cold benzene, separated by chio;aatography through a silica gel column using a mixture of diethylether : acetone (5:1 v/v) as eluent. The product was recrystalli/ed from hot dichloromethane anil dried over P20j for 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 tiiionyl chloride in 40 ml of dry benzene under nitrogen atmosphere and kept the reaction mixture wider refiux wilh continuous stirring at 75 °C for 8 h. Alter the cvalution of SO^ gas was ceased, She volume of the resulting solution was- reduced by vacuum distillation to get an yellow solid product winch was suction filtered, washed several times with cold methanol and dried over anhydrou.s calcium chloride for 10 h. The product was purified by¬passing through a silica gel column using a mixtue of petroleum ether : acetonitrile (5 : 1 v/v) as eluent to get 2.6 gram (52.6 %) of l-chIoro-2-benzamidoacetic acid.

Si oj) 3
l-chloro-2-ben.zamidoacetic acid t (S)-2-cliloro-3-(4-hydroxyplienyl)-propionic acid
(S)-2-ch]oro-3-(4-benzamidoacetophenyl)-piopionic ncid
3.95 (20.0 mmol) of l-chloro-2-benzamido-acetic acid prepared as illustrated in step 2 and 5.0 grain. (25.0mmol) of (S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid prepared as described in step 1 were magnetically stirred in 40 nil dry dichloromelhane at ambient lemperatme (or 2 h. 0.5 nil (3,6 nunol) of ui ethyl amine was then added to the reaction mixture drop wise and the reaction mixture was refliixed at 60 °C with constant stirring for 12 h. The yellow colomed (S)-2-diloro-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 chromaioai aphy tiirougli a silica gel column using a mixture of dieihylether : acetone (5:1 v/v) as elnenf to get an yield of 2.81 grain (69.82
Step 4
(S)-2-chloro-3-(4-beir7.aniidoacetopheny!)-propionic acid (S)-l,2-dichloro-3-(4-
benzamdoacetophenyl)-propionic acid
(S)-l,2-dichloro-3-(4-bcnzamidoacetopheriyl)-propionic acid was prepared by disolving 5.84 gram (16.2 mmol) of (S)-2-chloro-3-(4-ben7Jimidoacetopheiiyl)-propionic acid prepared as illustrated in step 3 in 40 ml of absolute dichloromelhane and to it added 2.5 ml (21.2 mmol) of thionyldiioride wilh constant stiiring. 'Hie reaction milure was then heated to 60 °C nnd the siirring was continued till the evalution of SO^ ceased. On cooling the reaction mixture to room temperature (S)-l(2-dichloro-3-(4-bei)zamidoacetophenyi)-propionic acid was separated as a white solid which was filtered off and washed several times with cold chloroform and the final product was rcciysialli/ed fi'oni hot ben/ene solution, The product was further purified by column chromatoghaphy through a silica gel column using a mixture of petroleum ether and acetone in 5 : 1 v/v as eluent to gci 4.22, gram (68.84 %) ot'(S)-l,2-dichh)io-3-(4-benzamidoacetophenyl)-propioiiic acid

Step 5
(S)-l,2-dichloro-.l-(4-berizaniidoacetophenyl)-propionic acid + 4-liydroxyl)onzoic acid
(S)-2-chloro-3-(4-ben7,amidoacetophenyl)-l-bni'(Mc acid-
propionate
(S)-2-chloro-3-(4-benzarnidoacetophenyl)-l-benzoic acidpropionate prepared by mixing together absolute dichloromethaiie solutions of (S)-l,2-dicliloi-o-3-('l-benzaiuidoacolot>liciiyl)-piopioiiic and (4.81 gram/12.7 mrnol in 20 ml of dry dichlorornethaiie) prepared as described in step 4 and 4-liydroxybenzoic acid (1.8 grai7i/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 trielhylainine was then added to the reaction mixture drop wise with constant stirring, The reaction mixture was then reiluxed at 75 °C for 18 h. The yellow coloured solution containing (S)-2-chioro-3-(4-ben:'.amidoacetophenyl)-l-ben/oic acid-propionate was reduced by vacuum distillation and the product was washed repeatedly with cold acetonitrile solution. The product was separated by column chromatogluiphy through a silica gel column using a mixture of petroleum ether and acetonitrile. in 5 : 1 v/v as eluent. 'Hie yield obtained was 3.74 grain (63.17 %).
Step 6
(.S)~2-cliloio-3-(4-ben/;miidoucetoplienyl)-J -ben/.oic acidpiopionate (S)-2-cliloio-
3-(44>enzaniidoacetophenyl)-l-(l-chloro-ben/,oic acid)-propionate
(.S)-2-f!iloro-3-(4-benz
Step 7 (S)-2^1iloro-3-(4-beiiz;m]idoacetophenyl)-l-(l-chloroben7.oic aeid)-pi opioiiate t 4-hydro\ybc>nx,oic
acid (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(4'-ben7.oic acid)-
benzoatopi opionate
(.S)-2-cl]lc)ro-3-('1-ben/.ajiiidoacetophenyl)-l-('1 '-ben/.oic acid)-benzoatopropion;ite was prcpaiod by mixing together absolute dichtoromcthaiic solutions ol (S)-2-chloro-3-(4-beii7:imidoacetophenyl)-l-(l-chlorobeiizoic acid)-propionate (2.65 gram/5.3 mmol in 20 nil diy dichloromethane) prepared as illustrated in step 6 and 4-hydroxybenzoic acid (0.95 gram/68 minol in 15 ml ol'diy dichloromethane) and (lie reaction mixture was stirred at ambient temperature for 4 li under nitt ogeii atmosphere. 0/15 ml (3.2 nuuol) of trietliylamine was then added to the reaction mixture drop wise and reiluxed the reaction mixture at 75 °C with constant stirring for 22 h. The yellow coloured solid of (S)-2-chloro-3-(4-bcn:'.amidoacetophenyl)-l-(4'-benzoic acid)-benzoatopropionate was separated by removing the excess solvent by vacuum distillation, washed twice with cold elhanol and chi oinatographed through a silica gel column using a mixture of petroleum ether : acetone (5 : 1 v/v) as eluent. The product was rmysfallized from hot benzene solution, The yield obtained was 1.64 gram (51/18 %).
Step 8
(.S)-2-clil()ro-3-(4-ben7iunidoacetophenyl)-l-(4'-benzoic acid)-ben/oatopropionate
(S)-2-chloro-3 (4-beiizajnidoaceto])!'i'iiyl)-J-(4'-l-chlorobenzoic 'icidj-ben/.oatopropioiuite
(.S)-2-chioro-3- -benzamidoacetoplienyl)-l-(4'-l-chlorobeii7.oic at'id)-beii7.oalopropionate was prepaied by disolving 2.08 grain (3.3 inrnol) of (S)-2-chloro-3-(4-beii7.ainidoacetophenyl)-l-(4'-benzoic 5icid)-ben7Joatopropionate prepai'ed as described in step 7 in 40 ml of absolute dicliloroiiiethane and to it added 0.65 ml {4.7 minol) of Ihionylchloride willi constant stirring under nitrogen atmosphere. The reaction miture was then heated to 60 °C and the stirring was continued till the evalution of SO2 ceased. On cooling the reaction mixture to room tempeiatuie (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(4'-l-chlorobenzoic acid)-benzoatopropionate was separated as a white colour product which was filtered off, washed repeatedly with cold chloroform and dried over vacuiio lor 12 h. (S)-2-cliloro-3-(4-benzainidoacetophenyl)-l-(4'-l-chlorobeiix,oic acid)-bcii7.oulopro-pionale was purified by column chromafography through a silica gel column using a mixtuie of petroleum ether : acetone (5 : 1 v/v) as eluent. '1,'he product was- recivstallized iiom hot dichloroniethane solution lo get an yield of 1.13 gram (52.64 %).

Step 9
(.S)-2-cliloro-3-(4-benx;unidoacetophenyI)-l-(4'-l-dilorobenzoic acid)-ben/o;ifopropionate I I-
ocfonol (S)-2-chloro-3-(4-l>enzamidoacetophenyl)-1 -('I '-oclyloxybenzoyl)-
benzoalopropionale
(.S)-2-cliIoro-3-(4-ben7.ainidoacetophenyl)-l-(4'-ocryloxybenzoyl)-benzoalopropioHate was prepared by stirring the reaction mixture containing (S)-2-chloro-3-(4-beii7aiuidoacetophenyl)-l-(4s-l-chlorobenzoic acid)-beii7,oalopropionate (2.35 gram/3.8 inniol in 15 nil of dry dichloromellmne) prepared as described in step 8 and 1-octanol (0.8 ml/5.1 mmol in 10 nil of dry dichloromethane) under nitrogen atmosphere tor 4 li a! room temperature. To it added 0.4 ml (3.3 mmol) of tiielliylnmine drop wise and the reaction mixture was refluxed at 75 °C for 26 h. Hie yellow coloured solution containing (S)-2-chloro-3-(4-benza]i}idoacetophenyl)-l-(4'-octyloxybenzoyl)-beii7,oatopropionafe was isolnted as a gelly product alter removing the excess solvent by vacuum distillation and the product was further purified by column chromatography through a silica gel column using a mixture of petroleum ether : acetonitrile (5 : 1 v/v) as eluenl. The yield obtained was 1.54 grarn (56.9 %).

T h e r o o m t e m p e r a t u r e f e r r o e 1 e c t r i c liquid crystal compound prepared by the process of this i n v e n 11 o n e x h i b i t c h a r a c: t e r i s t i c f e? r r o e 1 e c: t r i c properties in and around room temperatures which is a rare? phenomena, as the most of the reported ferroelectric compounds used for the applicational p u r r p o s e s are t h e m i x t u r e s o f m or e than o n e 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 non-linear optical a p p i i •:;: a t i o n s . F u r t h e r , s u c h r o o m t e m p e r a t u r e f e r r o e 1 e c t r i i:: 1 i q u i d c r y s t a I c o m p o u n d c a n b e u s e d as nost materials for the preparation of other FLC mix tures.
T h e n e e d f o r t h i s t y p e o f r o o m t e? rn p e r a t u r e 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 in the applicational as pe ct s such as po1 ar i sa tio n c ontrollers, switching attenuators, display devices etc.
T h e s t u d y o f t h e f u n cl a m e n t a 1 f e r r o e 1 e c t r i c properties viz,, spontaneous polarisation, tilt angle, 11 m e r e s p o n s e e t c . , o f t h e p r e s e n t i n v e n t e d c o f n p o u n d reveals that he magnitudes of these parameters are found to be of in good agreement with those of c o m m e r c i a .1. 1 y a v a i 1 a b 1 e m u. 11 i ••- c o m p o n e n t m a. t e r i a 1 s « 1 n fact some of the a bove pr opert i es e nvi s age that this compound showed better physical characteristics t h a n t h e c o m m e r c i a 11 y a v a i 1 a b 1 e c o m p o u n d s .


WE CLAIM;
1. A process for the preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl) -l-(4'-octyloxybenzoyl)-benzoatopropionate which comprises in the step of:
i) Nucleophilic substitution of -NH2 group from (S)-2-amino-3- (4-hydroxyphenylj-propionic acid by a chlorine atom via diazonium salt formation is carried in presence of freshly pulverized sodium nitrate stirring the reaction mixture at 0-4°C extracting with organic solvent selected from dicloromethane, benzene, methanol, dimethyl or memide, diethylether, drying the organic layer with removing the excess solvent under reduced pressure separating the compound by column chromatography using a silica gel column and eluent mixture comprising diethyl ether and acetone followed by recrystallization to get the said product,
ii) preparing l-chloro-2-benzamidoacetic acid by refluxing 2-benzamidoacetic acid with thionyl chloride,
iii) reacting said (S)-2-chloro-3-(4-hydroxyphenyl)-propionic acid with said l-chloro-2-benzamidoacetic acid to obtain crystals of (S)-2-chloro-3-(4-benzamidoacetophenyl)-propionic acid ;
iv) refluxing said (S)-2-chloro-3-(4-benzamidoacetophenyl-propionic acid with thionyl chloride to obtain (S)-l, 2-dichloro-3- (4-benzamidoacetophenyl)-propionic acid;

v) reacting said (S)-l,2-dichloro-3-(4-benzamidoacetophenyl)-propionic acid with 4-hydroxybenzoic acid in presence of catalyst triethylamine to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-benzoic acid propionate,
vi) reacting said (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-benzoic acid propionate with thionyl chloride to obtain (S)-2-chloro-3-(4-benzamidoacetophenyl)-1 -(1 -chlorobenzoic acid) propionate,
vii) reacting said (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(l-chlorobenzoic acid) propionate with 4-hydroxybenzoic acid in presence of said catalyst to obtain (S)-2-chloro-3-(4-benzamidoacetophenyl)- l-(4'-benzoic acid)-benzoatopropionate,
viii) reacting (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-4'-benzoic acid)~benzoatopropionate with thionyl chloride to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(4' -1—chlorobenzoic acid)- benzoatopropionate,
ix) reacting said (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(4'-l-chlorobenzoic acid)-benoatopropionate with 1-octanol in presence of a catalyst to obtain (S)-2-chloro-3- (4-benzamidoacetophenyl)-l-(4'-octadecyloxybenzoyl)-ben7X)atopropionate.

2. A process for the preparation of (S)-2-chloro-3-(4-benzamidoacetophenyl)-l-(4' -octyloxybenzoyl)-benzoatopropionate, substantially as herein describes and exemplified in the example.



Documents:

940-del-1998-abstract.pdf

940-del-1998-claims.pdf

940-del-1998-correspondence-others.pdf

940-del-1998-correspondence-po.pdf

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

940-del-1998-drawings.pdf

940-del-1998-form-1.pdf

940-del-1998-form-19.pdf

940-del-1998-form-2.pdf

940-del-1998-form-3.pdf

940-del-1998-gpa.pdf

940-del-1998-petition-124.pdf


Patent Number 232027
Indian Patent Application Number 940/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.
Applicant Address GOVT. OF INDIA. ELECTRONICS NIKETAN, 6, CGO COMPLEX, NEW DELHI-110003.
Inventors:
# Inventor's Name Inventor's Address
1 SHRI POLURI ANJANA KUMAR CENTRE FOR LIQUID CRYSTAL RESEARCH AND EDUCATION (CLCRE), FACULTY OF PHYSICAL SCIENCES, NAGARJUNA UNIVERSITY, NAGARJUNA NAGAR-522510 ANDHRA PRADESH, INDIA.
2 DR. VENKATA G.M.K. PISIPATI CENTRE FOR LIQUID CRYSTAL RESEARCH AND EDUCATION (CLCRE), FACULTY OF PHYSICAL SCIENCES, NAGARJUNA UNIVERSITY, NAGARJUNA NAGAR-522510 ANDHRA PRADESH, 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