ACTA POL YMERICA SINICA

10 2007 10 ACTA POL YMERICA SINICA No 10 Oct, 2007 3 33 ( 100871) 3 ( + )24,4 2 [ ( S)222 ]22 2 ( p2 BMVT) ( + )23,3 2 [ (S)222 ]22 2 ( m2bmvt) ( + )22,2 2 [ (S)222 ]2 2 ( o2bmvt) p2 m2bmvt ; o2bmvt,,,,,, [19 21 ], [1 4 ] ( + )24, 4 2 [ ( S)222 ]22 2 ( p2bmvt) [22 ], ( ) { ( + )24,4 2 [ ( S)222 ]22 2 } (P( p2bmvt) ) p2bmvt ( + )23,3 2 [ (S)222 [5 18 ] ( m2bmvt) ( + )22,2 2 [ ( S)222 ]22 2 ( o2bmvt),,, 1 ( ) ( ) 111 [18 ], (S)2(2)222 (99 %, TCI),2,52 (97 %,Acros) (99 %,Acros), N2 (NBS,99 %,Acros),22 (,Acros),32 (,Acros) (,Acros) (40 % ) PdCl 2 ( ) (BPO) 3 2007207202,2007207206 ; ( 20674001,20634010,20325415) ( 20060001029) ;33,E2mil :xhwn @pku edu cn 999

1000 2007 (m, 2H ; Ar) ; ( C 29 H 36 O 2 ) : C (AIBN) 83165 %,H 8165 % ; : C 83147 %,H 8186 % ; ( ) CH 2 ( EI, mπe, % reltive intensity) : 416 (M + ),, ( ) 346,276 (100),247,43 ; [ ] 25 365 = + 4015 (THF ) ( c = 012 gπdl,thf) ( + )232( (S)222 11212 ( + )22,2 2 [ (S)222 ) ( + )222( (S)222 ) ( o2bmmt) o2bmmt [22 p2bmvt ] 1 H2NMR Bruker ARX400 (400 MHz),CDCl 3, TMS (t,3h ;CH 3 ),0196 0197 (d,3h ;CH 3 ),1108 1112 Finnign2MAT ZAB2HS (m, 1H ; CH 2 ), 1122 1131 (m, 2H ; CH 2 ), 1148 Elementl Vrio EL 1152 (m,1h ;CH 2 ),1166 1169 (m,1h ;CH),1180 GPC 1183 (m,1h ;CH),2117 (s,3h ;Ar2CH 3 ),3165 3186 Wters 515 Wters Styrgel HT2 + (m, 4H ; OCH 2 ), 6194 7103 ( m, 4H ; Ar), 7118 HT3 + TH4 Wters 2410 7123 (m,2h ;Ar),7126 7133 (m,2h ;Ar),7137 35, 7141 (m,2h ;Ar),7146 (s,1h ;Ar) ; 110 mlπmin ( C 29 H 36 O 2 ) : C 83165 %, H 8165 % ; : C ( [ ] 25 365 ) JASCO Model P21030 83153 %, H 8181 % ; ( EI, mπe, % reltive 25 365 nm 10 cm intensity) : 416 (M + ),326,276,186,43 (100) ; THF ( c) 012 gπdl 2 [ ] 25 365 = + 3218 ( c = 012 gπdl,thf) Vrin Cry2300 11213 ( + )23,3 2 [ (S)222 JASCO J2810 ( m2bmvt) m2bmmt 011 mm (2108 g,5 mmol),nbs (0191 g,511 mmol) BPO 112 (24 mg,011 mmol) 25 ml 11211 ( + )23,3 2 [ (S)222 3 h, ( m2bmmt) ( + )232( (S)222 ) (912 g,44 mmol) 25 ml, ( 1131 g, 5 (01924 g,016 mmol) 250 ml mmol) 2 h 3 2,52 (510 g,20 mmol) (40 ml) 50 ml (20 ml) 70 ml 40 %, (119 molπl) (9 ml,10 wt %) 49 h 48 h 3,, 3Π1 Π 6Π1 Π m2bmvt 112 g 810 g, 56 % 1 H2NMR (CDCl 3 ) : 0193 96 % 1 H2NMR(CDCl 3 ) : 0193 0198 (t,6h ; 0199 (d,6h ;CH 3 ),1101 1105 (d,6h ;CH 3 ),1125 CH 3 ),1102 1105 ( d, 6H ; CH 3 ), 1125 1131 ( m, 1131 (m, 2H ; CH 2 ), 1158 1161 (m, 2H ; CH 2 ), 2H ;CH 2 ),1153 1160 (m,2h ; CH 2 ),1186 1191 1186 1191 ( m, 2H ; CH), 3176 3190 ( m, 4H ; (m,2h ;CH),2135 (s,3h ;Ar2CH 3 ),3174 3189 (m, OCH 2 ),5122 5125 (d,1h ; vinyl),5175 5180 ( d, 4H ;OCH 2 ), 6187 6193 (m, 4H ; Ar), 7116 7124 (m,2h ;Ar),7129 7136 (m,3h ;Ar),7144 7149 m2bmmt, 93 % 1 H2NMR (CDCl 3 ) : 0178 0182 (d,6h ;CH 3 ),0188 0191 1H ;vinyl),6175 6180 ( q,1h ; vinyl),6190 6195 (m,4h ;Ar),7118 7124 (m,2h ;Ar),7130 7132

10 : 1001 (d,1h ; Ar),7134 7138 (m,2h ; Ar),7152 7155 (q,1h ;Ar),7183 7184 (d,1h ;Ar) ; 0116 g 76 % (C 30 H 36 O 2 ) : C 84111 %, H 8141 % ; : C 83198 %, H 8140 % ; ( EI, mπe, % reltive intensity) : 428 (M + ),358,288,71,43 (100),29 ; [ ] 25 365 = + 3312 ( c = 012 gπdl,thf) 11214 ( + )22,2 2 [ (S)222 ( + )2(S)222 2,52 ( o2bmvt) o2bmvt Suzuki p2bmmt m2 m2bmvt BMMT o2bmmt NBS 16 % 1 H2NMR (CDCl 3 ) : 0177 0181 (d,6h ; Wittig p2bmvt m2bmvt o2bmvt p2 CH 3 ),0186 0190 (t,3h ;CH 3 ),0194 0196 (d,3h ; CH 3 ),1106 1111 (m,1h ; CH 2 ), 1119 1136 (m, 2H ;CH 2 ), 1145 1152 ( m, 1H ; CH 2 ), 1163 1170 (m,1h ;CH),1179 1184 (m,1h ;CH),3165 3187 (m,4h ;OCH 2 ),5106 5109 (d,1h ; vinyl),5163 5168(d,1H ;vinyl),6155 6162 (q,1h ;vinyl),6195 7105 (m,4h ;Ar),7120 7122 (q,1h ;Ar),7124 7126(d,1H ; Ar),7129 7133 (m,2h ; Ar),7141 7143 (q,1h ;Ar),7145 7148 (q,1h ;Ar),7187 ( d, 1H ;Ar) ; (C 30 H 36 O 2 ) : C 84111 %, H 8141 % ; : C 83175 %,H 8121 % ; ( EI, mπe, % reltive intensity) : 428 (M + ),358,287,71, 43(100),29 ; [ ] 25 365 = + 2815 ( c = 012 gπdl,thf) 113 310 10 4 1 m2bmvt { ( + )23,3 2 [ (S)222 } (P( m2bmvt) ) 1 H2NMR p2bmvt 1 H2NMR 60 = 01214 g (015 mmol), 0 212 CH 2 CH 41 L AIBN 10 mgπml, 1 ml 3, o2bmvt 60 24 h 20 ml THF 200 ml, 2 211 1 BMVT m2bmvt 4,4 2 56 % o2bmvt 16 % m2bmmt m2bmvt P ( m2bmvt) p2 m2bmvt, 1 4 24 h 50 %, Scheme 1 Synthetic route of p2bmvt, m2bmvt nd o2bmvt

1002 2007 Fig 1 1 H2NMR spectr of m2bmvt () nd its polymer (b) using CDCl 3 s solvent nd TMS s reference 212 21211 P( m2bmvt) p2bmvt P( p2bmvt) [22 ] 1 m2bmvt 60 90 m2 BMVT [ ] 25 365 + 3312, m2bmmt [ ] 25 365 + 4015 [ ] 25 365 P ( m2bmvt), [22 P( p2bmvt) ] Tble 1 Free rdicl polymeriztion results of m2bmvt Smple T( ) Solvent M n 10-4 PDI Yield( %) [ ] 25 365 1 60 Anisole 717 2103 5611 8716 2 60 Benzene 1015 1189 5911 8810 3 90 Anisole 310 3109 7813 9310 4,4 2 3, 2 () m2bmmt, m2bmvt P( m2bmvt) 3 2 2,2 2, 2 212 263 nm o2bmvt m2bmvt 2 3 m2bmvt o2bmvt 245 nm 22 CD 2 (b) [23 ] 9,102 195 nm 22 8,92 Cotton 188 nm [1, n ] 2 9,102 Cotton 230 300 nm [23 ] Lewis 32, CD CD 32 Cotton 77 K,2,62 Polymeriztion condition : concentrtion, 015 mol L - 1 ; inititor, zobisisobutyronitrile (AIBN) for 60 nd benzoyl peroxide for 90 (015 %,bsed on totl molr numbers of monomers) ; time,24 h m2bmvt p2bmvt 2 [ ] 25 365 P( p2bmvt) [ ] 25 365 210 ;P( m2bmvt) [ ] 25 365 o2bmvt 42 22 50 Lewis, Cotton 2 4,4 3,3 2 [21 ] ; 2,2 2,

10 : 1003 [ ] 25 CD Cotton P ( p2bmvt) P ( m2 BMVT) Tble 2 Free rdicl polymeriztion results of solvents t 60 Solvent 365 p2bmvt in different M n 10-4 PDI Yield( %) [ ] 25 365 10 30 (cm) THF 215 2149 8217-10814 518 CHCl 3 212 1199 5114-11416 318 Heptne 2110 1145 7716-14618 0 Anisole 1016 1183 7614-9619 412 Toluene 1017 1192 6313-8812 110 Benzene 1419 1165 6817-7014 0 Polymeriztion condition : concentrtion, 015 mol L - 1 ; inititor, zobisisobutyronitrile (AIBN) (015 %, bsed on totl molr numbers of monomers) ; time,24 h Tble 3 Free rdicl polymeriztion results of tempertures p2bmvt t different Solvent Heptne Anisole T( ) M n 10-4 PDI Yield( %) [ ] 25 365 60 2110 1145 7716-14618 70 1117 1172 4717-19714 80 810 2150 9518-21110 90 617 2173 9712-20119 60 1016 1183 7614-9619 70 612 1191 8515-11219 80 719 2131 7713-12910 90 1518 1181 9318-16111 Fig 2 UV2visible bsorption () nd CD (b) spectr of m2bmmt (2), m2bmvt ( - - - ), P ( m2bmvt) ( ), nd P ( p2bmvt) ( ) Mesured in n2hexne t 25, c = 112 gπl Polymeriztion condition : concentrtion, 015 mol L - 1 ; inititor, zobisisobutyronitrile (AIBN) for 60 nd 70,nd benzoyl peroxide for 80 nd 90 (015 %, bsed on totl molr numbers of monomers) ; time, 24 h 80 4 21212 P ( p2bmvt) [ ] 25 365 1 P( m2bmvt) [ ] 25 365 Okmoto [ ] 25 ( PTrMA) 365 P ( m2 BMVT) PTrMA P( p2bmvt) [ ] 25 365 [24 ], 2 [ ] 25 365 ; [ ] 25 365 [24 ], P ( p2 BMVT), 3, P ( p2bmvt)

1004 2007 Tble 4 Free rdicl polymeriztion results of p2bmvt with different concentrtions Solvent c(molπl) M n 10-4 PDI Yield( %) [ ] 25 365 Heptne Anisole 0125 817 2114 9314-23517 015 810 2150 9518-21110 1 1112 1199 9811-18019 0125 619 2116 7512-13413 015 719 2131 7713-12910 1 911 2104 9811-12518 Polymeriztion condition : concentrtion, 015 mol L - 1 ; temperture, (80 015) ; inititor, benzoyl peroxide (015 %, bsed on totl molr numbers of monomers) ; time,24 h, p2 m2bmvt P ( p2bmvt) o2bmvt, REFERENCES 1 Okmoto Y,Hond S,Okmoto I,Yuki H,Murt S,Noyori R,Tky HJ Am Chem Soc,1981,103 :6971 6973 2 Yuki H,Okmoto Y,Okmoto IJ Am Chem Soc,1980,102 :6356 6358 3 Reggelin M,Schultz M,Holbch M Angew Chem Int Ed,2002,41 :1614 1617 4 Pu L Tetrhedron :Asymmetry,1998,9 :1457 1477 5 Li B S,Cheuk K KL,Ling L,Chen J,Xio X,Bi C,Tng B Z Mcromolecules,2003,36 :77 85 6 Cheuk K KL,Lm J W Y,Chen J,Li L M,Tng B Z Mcromolecules,2003,36 :5947 5959 7 Lm J W Y,Dong Y,Cheuk K KL,Tng B Z Mcromolecules,2003,36 :7927 7938 8 Cheuk K KL,Lm J W Y,Li L M,Dong Y,Tng B Z Mcromolecules,2003,36 :9752 9762 9 Lm J W Y,Dong Y,Cheuk K KL,Lw C C W,Li L M,Tng B Z Mcromolecules,2004,37 :6695 6704 10 Ren C,Chen C,Xi FJ Polym Sci Prt A :Polym Chem,1998,36 :2127 2133 11 Vogl O,Xi F,Vss F,Ute K,Nishimur T,Htd K Mcromolecules,1989,22 :4660 4662 12 Ren C Y,Chen C F,Xi FJ Polym Sci Prt A :Polym Chem,1998,12 :2127 2133 13 Chen Chunfu( ),Liu Weihong( ),Chen Yongming( ),Ren Chngyu( ),Xi Fu( ) Act Polymeric Sinic( ),1996, (1) :126 128 14 Ren C Y,Chen C F,Xi F Chinese J Polym Sci,1994,12 :379 383 15 Wng Yuechun( ),Ding Mengxin( ),Hu Huizhen( ),Wng Fosong( ) Science in Chin,Ser B( B ), 1992,10 :1161 1166 16 Wng Yuechun( ),Ding Mengxin( ),Xu Jingzhe( ),Wng Fosong( ) Act Polymeric Sinic ( ),1988, (4) :317 320 17 Fujiki MJ Am Chem Soc,1994,116 :6017 6018 18 Nkno T,Okmoto Y Chem Rev,2001,101 :4013 4038 19 Green M M,Peterson N C,Sto T,Termoto A,Cook R,Lifson S Science,1995,268 :1860 1866 20 Rmos E,Bosch J,Serrno J L,Sierr T,Vecin J J Am Chem Soc,1996,118 :4703 4704 21 Med K,Okmoto Y Mcromolecules,1998,31 :1046 1052 22 Yu Z N,Wn X H,Zhng H L,Chen X F,Zhou Q F Chem Commun,2003,(8) :974 975 23 Lewis F D,Zuo X,Gevorgyn V,Rubin MJ Am Chem Soc,2002,124 :13664 13665 24 Nkno T,Mtsud A,Okmoto Y Polym J,1996,28(6) :556 558

10 : 1005 INFL UENCE OF CHEMICAL STRUCTURE AND POLYMERIZAION CONDITIONS ON CHIROPTICAL PROPERTIES OF BUL KY VINYL POLYMERS CAO Hongqing, LIU Anhu, YU Zhenning, ZHANGJie, WAN Xinhu, CHEN Xiofng, ZHOU Qifeng ( Beijing Ntionl Lbortory for Moleculr Sciences, Key Lbortory of Polymer Chemistry nd Physics of Ministry of Eduction, College of Chemistry nd Moleculr Engineering, Peking University, Beijing 100871) Abstrct Three chirl bulky vinyl monomers, ( + )24,4 2bis [ ( S)222methylbutoxy ]22 2vinyl2pr2terphenyl ( p2 BMVT), ( + )23, 3 2bis [ ( S)222methylbutoxy ]22 2vinyl2pr2terphenyl ( m2bmvt) nd ( + )22, 2 2bis [ ( S)222 methylbutoxy ]22 2vinyl2pr2terphenyl ( o2bmvt) were synthesized The lter two were new molecules The dependence of polymerizbilities of monomers on the chemicl structures nd the dependence of chiropticl properties of polymers on the chemicl structures nd rection conditions were systemticlly studied p2bmvt nd m2bmvt were redily polymerized by rdicl mechnism to produce opticlly ctive helicl polymers Moving the chirl lkoxy groups on terphenyl by just distnce of one bond length inversed the direction of opticl rottion o2bmvt ws obtined with quite low yield nd couldn t undergo rdicl polymeriztion Using polr romtic solvent nd polr liphtic solvent, incresing rection temperture, nd reducing monomer concentrtion fvored the formtion of polymers with higher specific opticl rottion Key words pr2terphenyl, Helicl structure, Chirlity, Chiropticl property, Free rdicl polymeriztion, Rectivity, Vinyl polymer