Chavan, S S

Deshmukh, M B

Dhongade-Desai, Savita

IACS Institutional Repository

uHanJ- P h y s .l9  0 ),2 9 1 -2 9 9  (2005)^ n-vion^^%$  I J p >t—S yn th esis  an d  characterization  o f  tw o d erivatives o f  2 -m ercap to -3 -m -to ly l-3H -q u in azo lin -4 -on eM  B D eshm ukh, Savita Dhongjjide-Desai and S S Chavan*Oepartrnenl o f  Chcmislr^* Shivaji University, K olhapur-416 004 , ^4aharashtra, IndiaiE -m ail” sanjaych^@ >yahoo coini'R ece ived  25 M ay 2004, a rh ep ted  20  January 2005istract : Q uinazolinc derivatives are o f  special importance because of their versatile b iological and pharm acological activities The 2 -(2 -oxo-  >pyls»ilfanyl)-3-m -tolyl-3H -quina/olin-4-onc(Q A ) and 2-(4-oxo-3-m -to ly l-3 .4 -d ihydro-q iiinazo- lin-2-yI.sulfanyl)“propiom c acid m ethyl cstcr(Q P) rc synthesized by thiolating 2 -th ioxo-3-m -lo ly l-2 ,3 -d ih yd ro-1 H -quinazolm -4-onc by an easy and efficient m icrow ave-assisted method The structures the eotnpounds have been confirm ed on the basis o f  their IR, PMR spectral and elemental analyses Further, characterization for crystal parameters J line broadening effects have been done.•vwords Q uinazolinone, MW alkylation  , X-ray diffraction,r s  Nos. 6 l .1 0 .N z , 7 8 .30 .Jwiinazoline derivatives are o f  special im portance because of 'ir versatile biological and pharm acological activities 1 1 -6 ] pecially an ti-in flam m ato ry , a n ti-c o n v u lsa n t, hypno tic , themintic, hypotensive, antibacterial etc Avoiding organic Ivcnt, microwave irradiation in organic reactions is used for ort reaction tim e, operational sim plicity  and form ation o f ianer reaction products. The use o f  therm al energy source in nous organic reactions [7] is com m on and the use o f domestic icrowave oven in th is  regard  is now  a w ell-estab lished  >^cedure in microwave organic reaction enhancem ent (MORE)1 chemistry to obtain S-alkylatcd derivatives o f thioquinazoline mg different alkylating agents. A lkylation  using catalytic lount of dimethyl form am idc (D M F), the polar mi^lecule, •proves energy transfer and allows higher tem peratures [9, 10] d Jess time com pared  to the conven tional m ethod o f S- ^ylation which requires a longer reaction tim e at a regulated ^l)eraturefllj."^ 11 m.p's. were determ ined in open capillary tubes and are ‘Corrected. IR spectra w ere recorded in K B r on Shim adzu IR- 7 spectrophotometer and PM R spectra in CDC13 and DM SO- ' Perkin-Elmer R-32 spectrom eter using Trim cthylsilane aso^esponding Authoran internal standard. Thin layer chrom atographic plates coated with silica-gel-G were used to check the purity o f the compounds. M icrowave irradiation was carried out in the dom estic SH A R P microwave oven. The X-ray diffractogram s were recorded on Philips PW  3710 diffractom eter with scanning rate 2^/ min. attached to a digital com puter along with graphical assem bly o f Cuk^ radiation source observed at Cu-Ni 40 kV / 40 mA.2 -(2 -O xo -p ro p y lsu lfa n y l )-3 -m -to ly l~ 3 H -q u in a zo l in -4 -o n e  (QA) :2.68 g (10 mmol) of 2-lhioxo-3-m-tolyi-2,3-dihydro- IH-quinazolin- 4-one, 1.84 g (20 mmol) o f chloroacetone and 0.5 ml o f D M F and powdered NaOH (0.5 g), sm oothly mixed and placed inside a Pyrex-glass and the mixture was irradiated with microwaves (900 W /2450 M Hz frequency) for 8 m inutes, the m ixture was then added with 2N HCl (10 ml). The solid separated was filtered, conveniently dried and recrystallized from ethanol to get 2 .27g of (QA),yield 69.5%, mp. 142‘X2, IR(KBr): 1725(C = O), 1675(cyclic C =0). 1620cm-HC=N), PMR (DMSO-d^): 2.4(3H,s,-COCH3), 3.6- 4 .0 (2H ,s, -SCH ^), 7 .2-8-2  (8H ,m ,A r-H ). A nal. C a lcd  fo r C,gH,gN202S: C,*^66.23; H , 5.56; N, 8.58 %; Found; C, 66.2; H , 5.55; N, 8.6 %>.298 M  B Deshmukh, Savita Dhongade-D esai and  S S Chavan  ylsuifanyi)2-(4-oxo-’3-m ‘tolyl-J,4-dihydro-cfuinazolin- 2 propionic acid methyl ester (Q P) :2.68 g (10 mmol) of 2-thioxo-3-m-tolyI-2,3-dihydro-1 H-quinazolin- 4-one, 2-44 g(20 mmol) of methyl 2-chloropropionate and 0.5 ml o f DM F and powdered NaOH (0.5 g), were smoothly mixed and placed inside a Pyrex-glass and the m ixture was irradiated with m icrowaves (900 W /2450 M Hz frequency) for 5 m inutes, the mixture was added with 2N IlCI ( 10 ml). The solid .separated was filtered, conveniently dried and recrystallized from ethanol to get 2.67g of (QP), yield 75.2%, mp. 145‘XT, IR (KBr): 1755(C=0), 1710(cyclicC =0), 1620(C=N), 1060cm'^ (-O -).PM R (DMSO- d ,^): 1.4(3H, d, J=7Hz., C H 3), 2.35(3H , s, A r-C H ,), 3.75(3H, s, OCH3), 4.3( IH, q, J=7.5Hz., S-CH), 7.2-S.2 (8H, m, Ar-H) Anal. Calcd for C, 64.02; H, 5.66; N, 7.86 %; Found: C,Ci4.0;H, 5.64; N, 7.9%..The proposed structures o f  (QA) and (QP) are presented in Figure 1 on the basis o f IR, PM R spectral and elemental analyses.The X-ray diffraction pattern o f (Q A ) and (QP) with respect to their prom inent peaks have been indexed using com puter trial and error method f 1 2 1 , for a good fit between observed and calculated d  values. The relative intensities corresponding tothe prom inent peaks have been calculated by normalizing ther with respect to their maxima.The indexing o f diffractogram o f (QA) and (QP) are presenfe in Table 1 . The indexing o f  diffractogram  o f both the compound are nearly identical and it can be proposed that the compound belong to sam e structural class. The com parison of the value ( V/' reveals that there is good agreem ent between the calcuLuc and observed  value  o f  on the basis  o f  assumption  ^orthorhombic crystal structure f 13-16 j. The compound (QA) ImTabic 1. X-ray diffraction data o f  2 -(2 -oxo-propylsu lfanyl)-3- 2-ylsuIfanyl)-propionic acid m ethyl ester (Q P)m -loIyl-3H - quinazt)lin-4-onc (Q A ) and 2-(4-oxt>“ 3-m -tolyI-3, 4-dihydio- qum.j/o!!"Q A Q PP ea k 2 0 d„,„ d .., h k i K /  % P eak 2 0 d ... h k i A7 'No. deg . No. d e g1 13 180 9 .9 7 5 9 .9 7 5 0 2 0 10 4 1 ) 1 6 0 0 1 1 .3 2 8 1 1 3 2 8 0 1 0 10 52 1 3 .9 2 0 9 .4 4 7 9 .4 4 7 1 1 0 1 00 2 12 6 9 0 10 3 5 9 1 0 .3 5 9 J 0 0 10(13 1 4 .2 3 5 9 .2 3 9 9 .2 3 9 0  0  1 8 .4 3 1 4 .4 1 0 9 .1 2 8 0 .1 2 8 0 I 1 :i '■4 1 8 .6 4 5 7 .0 6 7 7 .0 0 1 1 0  1 2 8 .2 4 1 9 .3 0 5 6 .8 2 7 6 .8 4 8 1 1 1 1245 1 9 .6 8 0 6 .6 9 9 6  651 0 3 0 24 .1 5 2 3 .4 4 5 5 .6 3 4 5 .6 6 4 0 2 0 41 :6 2 0 .2 0 0 6 .5 2 8 6 .6 0 5 1 1 1 5 0 6 2 6 .2 9 5 5 0 3 3 4 .9 7 0 1 2 0 () 27 2 4 .6 6 5 5 .3 6 0 5 .3 6 3 2 0  0 3 .4 7 2 9 .2 1 5 4 .5 3 9 4 .5 6 4 0 2 2 -12H 2 6 .8 1 5 4 .9 3 7 4 .9 8 7 0 4 0 2 3 .4 8 2 9 .7 4 5 4 .4 6 0 4 .5 0 4 2 1 1 2'i ’9 2 7 -4 4 5 4 .8 2 6 4 8 2 2 1 3 1 7 .0 9 3 0 .3 5 5 4 .3 7 2 4 .2 9 9 2 0 2 0 410 2 8 .0 5 0 4 .7 2 4 4 .7 2 3 2 2 0 1 0 .2 10 31 4 5 5 4 .2 2 3 4 .2 6 4 1 1 3 i :n1 1 2 9 .0 7 0 4 .5 6 1 4 .5 2 3 1 4  0 3 .6 1 1 35 4 7 5 3 .7 5 7 3 .7 7 6 0 3 0 4 7 '12 2 9 .5 9 5 4 .4 8 2 4 .5 0 0 0  I 2 14 .5 12 3 7 .6 8 0 3 .5 4 5 3 .5 4 7 1 3 0 IS s13 3 0 .3 6 0 4 .3 7 2 4 .3 8 9 0  4  1 4 .5 1 3 4 0 .4 9 0 3 3 0 8 3 .3 0 3 3 I 0 6 ^14 3 5 .1 8 5 3 .7 8 7 3 .7 9 4 0  3 2 1 6 .2 14 4 2 .9 9 0 3 .1 2 4 3 .1 5 1 3 0 21 5 3 6 .0 3 0 3 .7 0 1 3 .7 3 9 1 5 0 1 0 .4 15 4 5 .1 4 0 2 9 8 2 2 .9 8 2 2 1 4 (1  ^ ;16 3 6 .4 1 5 3 .6 6 4 3 .6 6 3 0  5 I 1 7 .7 16 4 6 .4 6 5 2 9 2 0 2 .9 1 9 1 3 31 417 3 6 .5 4 5 3 .6 5 1 3 .6 5 2 2 4  0 1 9 .618 3 7 .8 9 0 3 .5 2 6 3 .5 2 0 3 1 0 7 .219 3 8 .8 1 0 3 .4 4 5 3 .4 4 7 2 1 2 5 .82 0 4 3 .2 3 5 3 .1 0 7 3 .0 9 8 2 3 2 9 .021 4 4 .5 9 0 3 .0 1 7 3 .0 1 9 0  5 2 5 .8 _____-Synthesis and characterization of two derivatives etc 299I ijitice constants a = 10.7267 A,h=  19.9514 A, c = 9.2398 A and1977.43 A ’ and the compound (QP) has lattice constants a jo 3 5 9  A, 6 = 11.328 A, c =15.412 A and V =  1808.76 A \lespectively.The experimental density values of the (QA) and (QP) determined by specific gravity method, are found to be 0.9567 and l g cm-3, respectively. The number of molecules (n) per unit cell was calculated (p = n m /N V )  and are found to be 4. With this number theoretical density was fixed and are 1.0489 cm ' Ibr (QA) and 1.2576 g cm’^  for (QP), respectively. The other parameters such as pore fraction, packing fraction, thickness of particle and radius of molecule were calculated. By using experimental and theoretical density of (QA) and (QP), the pore iiaction was computed and it comes out to be 39.48 and 31.76 %, icspectively. The radius and the volume of molecules of (QA) and (QP) were calculated and are found to be 3.792 and 3.662 A and228.481 and 205.780 A*^, respectively. The packing fraction were calculated using volume of molecule and volume of unit cell of (QA) and (QP) and are found to be 46.21 and 45.51%,le.spectively.The particle size of the samples under study was determined using the equation t = 0.9 A/BcosP and are found to be 168 and I7f) A for (QA) and (QP), respectively. This parameter makes possible to distinguish between natural particle size and particle M/,c due to broadening effect by calculating full width at half maximum (B) corresponding to its Bragg's 0 .  The plot of Bcos0 W7S//V s\n0 was found to be straight line for both samples, parallel to X axis indicating the absence of any strains caused b\ inhomogeneous lattice distortions and compositional fluctuations. It is concluded that the compounds under investigation are homogeneous with respect to the particle size distribution.AcknowledgmentsAuthors thank the In-charge, CFC, Shivaji University, Kolhapur for providing X-ray analysis facility.R e fe re n c e sHI[21[3iI K]f (5)[ 6 ]L7]18J[9]MO]HU112][13]114][15]116]W Reid and C Hirsh ./ Orj/ C hem . 33 143 (P>66)Moskalenko N Yu. L N Yakhoniov, G P Zhikharera, G N Pershm. V V Peters, M 1 Euslratova and 1 M Muhkovskaya Z/i. Khimfarm 20 437 (1986), C h v m  A b s tr . 106 3297v (1987)S S T iw ari and M P Pandey A c ta  C ic n c in  I n d ic a  C h v m . 16c 251(1990), C h v m  A h u r  116 2355557q (1992)R lyagi, B (joel, V K Srivastava and A Kumai In d ia n  J. P h a n n .  S r i  60 283 (1998)A Kumar, R S Verma. H t* Jaju and J N .Sinha ./ In d ia n  C h e m  S n e  67 920 (1990)L S G oodm an and A (iilm an  T h e  P h a r m a n d o y i r a t  B a s is  o f  T h era p e u tic s^  (7th edn) (London : Collii M acM illan) (1985)S C iiddick T e t r a h c d n m  51 10403 (1995), R S Varma G r e e n  C h e m is tr y  43 (1999)A K Bose, B K Banik, N Lavlinskaia, M Jayaram an and M S Manhas C h c m te c h  27 18 (1997)M S u tirc /, A L oupy, E .Salfritn, L M oran and E R o lan d o  H e te r n c y d e s  51 21 (1999)H M aiquc/, A Plulin, Y R oditgue/, E Perc/ and A Loupy S \n th  C o m m u n . 30 1967 (2000)M B Deshmukh, M A Shelar, J S Jadhav, B S Shinde and S H Patil In d ia n  J  l l e i e r o  C h e m  6 181(1997)S S Chavan, P P Hankarc. A H Jagtap and R T Pattar In d ia n  J  P h ys  75A 269 (2001)R T Pattar, K R Ghoukimath and V G Tulsigeri In d ia n  J. P h vs  73A 343 (1999)B D Cullity E le m en ts  o f  X -r a y  D iffra c tio n , (Massachusetts: Addison W esley) (1956)H P Klug and L E Alexander X -r a y  D iffra c tio n  P ro c e d u r e  fo r  P o ly c ry s ta lh n e  a n d  A m o rp h o u s  M a te r ia ls  (New York : John Wiley London) (1974)H S Pei.ser, H P Rookshy and A J C V>li\son X -r a y  D iffra c tio n  b y  P o ly c ry s ta llin e  M a te r ia l  (Institute o f Physics, London) (1956)

Synthesis and Characterization of Two Derivatives of 2-Mercapto-3-M-Tolyl-3H-Quinazolin-4-One

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Synthesis and Characterization of Two Derivatives of 2-Mercapto-3-M-Tolyl-3H-Quinazolin-4-One

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