Synthesis and Thermotropic Properties of New Liquid Crystalline Compounds;1,10-Bis[2,5-bis(4-alkyloxyphenoxycarbonyl)phenoxy]decane ; 1,10-Bis[2,5-bis(4-alkyloxyphenoxycarbonyl)phenoxy]decane

전체 글

(1)Journal of the Korean Chemical Society 2001, Vol. 45, No. 1 Printed in the Republic of Korea.

(2) . ;. 1,10-Bis[2,5-bis(4-alkyloxyphenoxycarbonyl)phenoxy]decane. *

(3) . (2000. 9. 15

(4) ). †. †. †. Synthesis and Thermotropic Properties of New Liquid Crystalline Compounds; 1,10-Bis[2,5-bis(4-alkyloxyphenoxycarbonyl)phenoxy]decane Joo-Hoon Park*, Eun-Young Kim, Ok-Byung Choi, Kie-Soo Kim, Bong-Keun So†, and Soo-Min Lee† School of Natural Science, Hoseo University, Choongnam 336-795, Korea † School of Natural Science, Hannam University, Taejon 306-791, Korea (Received September 15, 2000). . n=1-10 !" #$%& '()* (+,-.. /0 &1 2 34+5* DSC6 7&8/ 9: ;<=>?* @A,B @,-.. !" '()0 C DE F+/GH, @: #$%&, n=1-10, '()0 IJKL* MNOG.. P , '() 0C Q4 RS .T, UVWXY, 7Z[ @\, n, * ]7^* _ #$ %&O` a MNOG... ABSTRACT. A new homologous series with the general formula in which n is the longitudinal alkyloxy group, n=1-10, was synthesized. The thermotropic and liquid crystalline properties were studied by differential scanning calorimetry and on the hot-stage of a polarizing microscope. All of the new compounds were monotropic and texture observations proved that all investigated homologues with n=1-10 exhibited nematic phases. Also, the compounds showed pronounced alternation effects in the homologous series with constant lateral bridging group, oxydecamethyleneoxy, but increasing longitudinal chains, n.. 67.

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(6) . 68. &+ 34'() b cde (the rod fg _ 7h,. ij* Vorländer kl,-[, / ij` Lm, nC '()* (+ ,B o kl* ]p,-.. / nC &+ 34 '() q` )5/ Dewar 6 Meter ` ,B rHsG.. Dewar / '()0 IJK 34l4+` >t qu v6 wF a` ,B xyrzH, Meter {-< |t` @As}5 ~ !" IJK 34 )5 / A* k,-.. Vorländer` ,B kl: &+ like shape). 1. 2-5. 6. 7. 34 l4+` /0 wF t g` , B /> sGM, ` 4 ,B wF 7 / b 34l4 +` } * >tZ %1 xyrH. .. nC `, C ¡,B v: calamitic unit ¢£/ '()0/ ¤¥sG U, /0C ¦@\ 34 q(` §C D d'() ¨#,-.. ©M W¤ª 7Z`, v WXY L6 «C ¢£/ &+ 34 '()` ¬ r F%/.. ®¯, ` L6 «C b 34'()* (+,-H, /0 wF ° t ±²S, / '()0 b 6 34+³ L ´´% xyrz.. 9. 10-16. 9,17-19. . Series I.. 34b Q1 ijC c de fg _ 7 h /GM, T &+ 34b (+,-.. 8. . 2,5-Dimethylanisole, K CO , 1,10-dibromodecane, 2. 3. NaOH, p-methoxyphenol, p-ethoxyphenol, p-propoxyphenol, p-butoxyphenol, p-pentyloxyphenol, p-hexyloxy-. p-heptyloxyphenol 2 p-octyloxyphenolC @ Qµ¶* 4k ·/ © @A,-H, A¸ ¹º »` ®¯ 4k,B @A,-.. pNonyloxyphenol p-decyloxyphenolC E. Akiyama »` ®¯ (+,-H, /0 b<1 v6 ¼½* ` ,-.. 4-Nonyloxyphenol: ¾¿C 68.0%-H, ¼½C 69.4 C-.. IR(KBr, cm ): 3600-3300(O-H stretch), 3037 2919(aromatic aliphatic C-H stretch), 1459 phenol,. Aldrich. 20. 21. Series II.. /` ,S, 7Z t b 34+ =* , ~M, L '()C F+ IJK 34* d+,-.. B` 7,B, L '()0(Series I 2 Series II) ( de b (Series III) ,-[, mA1 S 1 S ` 34* F% / %7 ~.. Vorländer. o. −1. (-CH2- bend), 1375(-CH3 bend), 1241-1031(C-O stretch). 1. H-NMR(CDCl3, δppm): 0.80-0.91(t, 3H, -CH3), 1.15-. 1.55(m, 12H, -O(CH2)2 ( CH 2) 6 (CH2)6CH3), 1.60-1.80 (m, 2H, -OCH2 CH2 (CH2)6CH3), 3.80-3.92(m, 2H, -O CH 2 (CH2)7CH3), 4.60(s, 1H, -OH), 6.65-6.80(m, 4H, Ar). 4-Decyloxyphenol:. ¾¿C 73.5%-H, ¼½C. -.. IR(KBr, cm ): 3500-3300(O-H stretch), 3037 2919(aromatic aliphatic C-H stretch), 1459 o. 70.0 C. -1. (-CH2- bend), 1374(-CH3 bend), 1242-1032(C-O stretch). 1. H-NMR(CDCl3, δppm): 0.82-0.92(t, 3H, -CH3), 1.18-. 1.45(m, 14H, -O(CH2)2 ( CH 2) 7 CH3), 1.60-1.79(m, 2H, -OCH2 CH2 (CH2)7CH3), 3.84-3.92(m, 2H, -O CH 2 (CH2)8Series III.. CH3), 4.62(s, 1H, -OH), 6.68-6.82(m, 4H, Ar). Journal of the Korean Chemical Society.

(7) !; 1,10-Bis[2,5-bis(4-alkyloxyphenoxycarbonyl)phenoxy]decane. 69. (CDCl3, δppm): 1.16-1.40(m, 12H, -O(CH2)2 (CH 2 )6 (CH2)2O-), 1.78-1.92(m, 4H, -OCH2 CH 2 (CH2)6 CH 2 O-), 3.84-3.92(m, 12H, -OCH3), 4.10-4.23(m, 4H, -O CH2 (CH2)8 CH 2 O-), 6.90-8.10(m, 22H, Ar). Anal. Calcd. for C54H54O14 : C, 69.98; H, 5.83%. Found: C, 69.89; H, 5.86%. n=2(9), 3(10), 4(11), 5(12), 6(13), 7(14), 8(15), 9(16). Scheme 1. Synthetic route of series III compounds.. 2 10(17)C n=1(8)'() #Q, (+,-[, JZc F%` Ò') (7)` p-methoxyphenol o ` n=2(9) p-ethoxyphenol, n=3(10)C p-propoxyphenol, n=4(11)C p-butoxyphenol, n=5(12)C p-pentyloxyphenol, n=6(13)C p-hexyloxyphenol, n=7(14) pheptyloxyphenol, n=8(15) p-octyloxyphenol, n=9 (16) p-nonyloxyphenol, n=10(17)C p-decyloxyphenol m^.. ®¯, n=2(9), 3(10), 4(11), 5(12), 6(13), 7(14), 8(15), 9(16) 2 10(17) '()C ¾¿, ¼½, b<1 bá â¤bá vÄ* ` ,-.. 1,10-Bis[2,5-bis(4-ethoxyphenoxycarbonyl)phenoxy]-. . '() À +) 1,10-bis[2,5-bis(4alkyloxyphenoxycarbonyl)phenoxy]decane (+? Scheme 1 «[, q³ '() (7)ÁZ ¹º »* ®Â.. À +)C DE «C » ` ®¯ (+,-Ã, n=1(8)` (+?Ä* Å1 ,-... ¾¿C 86.0%-H, ¼½C 133 C-.. IR (KBr, cm ): 3070 2919(aromatic aliphatic C-H. 1,10-Bis[2,5-bis(4-methoxyphenoxycarbonyl)phenoxy]. 3.82-3.91(m, 4H, -O CH 2 (CH2)8 CH2 O-), 4.01-4.12(m,. 9. decane(8).. 5¤ Æ,`. 1,10-bis(2,5-dicarboxy-. * Ç 4k. SOCl 30 ml` ÈH, DMF E É* Ê7,B 4³ #l ÆË Ì, SOCl ÍÎ]Æ,B kÏ ,H, Bb SOCl petroleum ether @A,B k Ï,-.. Ð}Ñ Ò') (7)* 20 ml THF6 15 mL ÓTÔ A¸` ¼ Ì, p-methoxyphenol(0.744 g, 6 mmol)* THF 15 ml` ¼/H, ice-bath ,` Ò ') A3` 7,B ÕÖ` 20³, 60 C` 1 ³ Ì ÕÖÁZ ×Ø.. L A3* 5% NaHCO A3` } v4* ÐC Ì 0.1 N HCl ]Æ B ÙÚ ÛÜ Ì `ÝÞ THF ß( A¸(4/1, v/v) àv4,-.. ¾¿C 0.759 g(82.0%)[, ¼½C 94.6 C-.. IIR(KBr, cm ): 3061 2920(aromatic aliphatic C-H stretch),1723(C=O stretch), phenoxy)decane (6) (0.502 g, 1.00 mmole) 2. 2. 2. o. 3. o. -1. 1. 1390(-CH3), 1292-1029(ether C-O stretch). H-NMR 2001, Vol. 45, No. 1. o. decane (9).. −1. stretch), 1725(C=O stretch), 1391(-CH3), 1293-1027 (ether C-O stretch). 1H-NMR(CDCl3, δppm): 1.18-1.29 (m, 12H, -O(CH2)2 ( CH 2) 6 (CH2)2O-), 1.30-1.38(m, 12H, -CH3), 1.70-1.82(m, 4H, -OCH2 CH 2 (CH2)6- CH 2 CH2O-), 8H, -O CH 2 CH3), 6.84-8.10(m, 22H, Ar). Anal. Calcd. for C58H62O14: C, 70.88; H, 6.31%. Found: C, 70.85; H, 6.28%. 1,10-Bis[2,5-bis(4-propoxyphenoxycarbonyl)phenoxy]-. ¾¿C 80.0%-H, ¼½C 116 C.. IR(KBr, cm ): 30746 2932(aromatic aliphatic o. decane (10).. −1. C-H stretch), 1725(C=O stretch), 1389(-CH3), 12931065(ether C-O stretch).. H-NMR(CDCl3, δppm):. 1. 0.97-1.10(m, 12H, -CH3), 1.18-1.58(m, 12H, -O(CH2)2 ( CH 2) 6 (CH2)2O-), 1.75-1.92(m, 12H, -OCH2- CH2 CH3, -OCH2 CH 2 (CH2)6 CH 2 CH2O-), 3.83-4.02(m, 8H, -O CH 2 CH2CH3), 4.12-4.23(m, 4H, -O CH 2 - (CH2)8 CH 2 O-), 6.92-8.08(m, 22H, Ar), Anal. Calcd. for C62H70O14: C, 71.68; H, 6.74%. Found: C, 71.75; H,6.75%. 1,10-Bis[2,5-bis(4-butoxyphenoxycarbony)phenoxy]decane (11).. ¾¿C 90.5%-H, ¼½C 122 C-.. o.

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(9) . 70 FT-IR(KBr, cm−1): 3050. 2915(aromatic aliphatic. (m, 8H, -O CH 2 (CH2)5CH3), 4.10-4.25(m, 4H, -O CH 2. C-H stretch), 1730(C=O stretch), 1375(-CH3), 1290-1030. (CH2)8 CH 2 O-), 6.91-8.10(m, 22H, Ar), Anal. Calcd.. (ether C-O stretch). H-NMR (CDCl3, δppm): 0.89-1.10. for C78H102O14: C, 74.17; H, 8.08%. Found: C, 74.28;. (m, 12H, -CH3), 1.18-1.65(m, 20H, -O(CH2)2 CH 2 CH 3,. H,8.10%.. 1. -O(CH2)2 ( CH 2) 6 (CH2)2O-), 1.71-1.95(m, 12H, -OCH2 CH 2. 1,10-Bis[2,5-bis(4-octyloxyphenoxycarbonyl)phenoxy]-. 8H, -O CH 2 (CH2)2CH3), 4.08-4.20(m, 4H, -O CH2. ¾¿C 85.5%-H, ¼½C 76.7 C.. IR(KBr, cm ): 3081 2924(aromatic aliphatic. (CH2)8 CH 2 O-), 6.85-8.05(m, 22H, Ar), Anal. Calcd. C-H stretch), 1724(C=O stretch), 1391(-CH3), 1292-1043. for C66H78O14: C, 72.39; H, 7.13%. Found: C, 71.94;. (ether C-O stretch). 1H-NMR(CDCl3, δppm): 0.80-. H, 7.08%.. 0.99(m, 12H, -CH3), 1.15-1.58(m, 52H, -O(CH2)2 (CH 2 )5. CH2CH3, -OCH2 CH 2 (CH2)6 CH 2 CH2O-), 3.85-4.05(m,. 1,10-Bis[2,5-bis(4-pentyloxyphenoxycarbonyl)phenoxy]-. ¾¿C 82.0%-H, ¼½C 101 C.. IR(KBr, cm ): 3057 2931(aromatic aliphatic o. decane (12).. −1. o. decane(15).. −1. CH3, -O(CH2)2 (CH 2 )6 (CH2)2O-), 1.73-1.92(m, 12H, -OCH2 CH 2 (CH2)5CH3, -OCH2 CH 2 (CH2)6 CH 2 CH2O-), 3.824.05(m, 8H, -O CH 2 (CH2)6CH3), 4.08-4.23(m, 4H, -O CH 2. C-H stretch), 1726(C=O stretch), 1387(-CH3), 1290-. (CH2)8 CH 2 O-), 6.90-8.08(m, 22H, Ar), Anal. Calcd.. H-NMR (CDCl3, δppm):. for C82H110O14: C, 74.66; H, 8.35%. Found: C, 74.56;. 1063(ether C-O stretch).. 1. 0.90-1.00(m, 12H, -CH3), 1.22-1.59(m, 28H, -O(CH2)2 ( ( CH 2) 2 CH3, -O(CH2)2 ( CH2 )6 (CH2)2O-), 1.73-1.95(m,. H, 8.26%. 1,10-Bis[2,5-bis(4-nonyloxyphenoxycarbonyl)phenoxy]-. CH2 CH2O-), 3.92-4.05(m, 8H, -O CH 2 (CH2)3CH3),. ¾¿C 80.5%-H, ¼½C 74.8 C-. . IR(KBr, cm ): 3080 2921(aromatic aliphatic C-. 4.13-4.23(m, 4H, -O CH2 (CH2)8 CH 2 O-), 6.90-8.05 (m,. H stretch), 1725(C=O stretch), 1392(-CH3), 1291-1063. 22H, Ar), Anal. Calcd. for C70H86O14: C, 73.04; H,. (ether C-O stretch). 1H-NMR (CDCl3, δppm): 0.79-. 7.48%. Found: C, 73.14; H,7.39%.. 0.99(m, 12H, -CH3), 1.17-1.59(m, 60H, -O(CH2)2 (CH 2 )6. 12H, -O CH 2 CH 2 (CH 2 ) 2 C H 3 , -OCH 2 CH 2 (CH 2 ) 6. 1,10-Bis[2,5-bis(4-hexyloxyphenoxycarbonyl)phenoxy]-. o. decane(16).. −1. CH3, -O(CH2)2 ( CH 2) 6 (CH2)2O-), 1.71-1.91 (m, 12H, -OCH2. ¾¿C 91.0%-H, ¼½C 103 C-.. IR (KBr, cm ): 3084 2924(aromatic aliphatic C-H. 4.05(m, 18H, -O CH 2 (CH2)7CH3), 4.08-4.21(m, 4H, -O CH 2. stretch), 1729(C=O stretch), 1394(-CH3), 1292-1036. (CH2)8 CH2 O-), 6.88-8.09(m, 22H, Ar), Anal. Calcd.. (ether C-O stretch). H-NMR(THF-d8, δppm): 0.85-0.92. for C86H118O14: C, 75.11; H, 8.59%. Found: C, 75.23;. (m, 12H, -CH3), 1.15-1.57 (m, 36H, -O(CH2)2 ( CH 2) 3. H,8.62%.. o. decane(13).. −1. 1. CH 3, -O(CH2)2 ( CH 2) 6 (CH2)2O-), 1.59-1.79 (m, 12H,. CH 2 (CH2)6CH3, -OCH 2 CH2 (CH 2)6 CH2 CH2O-), 3.85-. 1,10-Bis[2,5-bis(4-decyloxyphenoxycarbonyl)phenoxy]-. 3.78-3.95(m, 8H, -O CH 2 (CH2)4CH3), 3.99-4.18(m, 4H,. ¾¿C 90.1%-H, ¼½C 69.1 C.. IR(KBr, cm ): 3071 2921(aromatic aliphatic. -O CH 2 (CH2)8 CH 2 O-), 6.78-7.95(m, 22H, Ar), Anal.. C-H stretch), 1726(C=O stretch), 1393(-CH3), 1292-. Calcd. for C74H94O14: C, 73.63; H, 7.79%. Found: C,. 1031(ether C-O stretch).. 73.68; H,7.76%.. 0.78-0.98(m, 12H, -CH3), 1.16-1.58(m, 68H, -O(CH2)2. -OCH2 CH2 (CH2)3CH3, -OCH2 CH2 (CH2)6 CH 2 CH2O-),. 1,10-Bis[2,5-bis(4-heptyloxyphenoxycarbonyl)phenoxy]-. o. decane(17).. −1. H-NMR(CDCl3, δppm):. 1. ( CH 2) 7 CH3, -O(CH2)2 ( CH 2) 6 (CH2)2O-), 1.68-1.90 (m,. ¾¿C 83.0%-H, ¼½C 90.9 C-.. IR(KBr, cm ): 3085 2927(aromatic aliphatic C-H. 12H, -OCH2 CH2 (CH2)7CH3, -OCH2 CH 2 (CH2)6 CH 2. stretch), 1727(C=O stretch), 1391(-CH3), 1292-1064 (ether. (m, 4H, -O CH 2 (CH2)8 CH 2 O-), 6.84-8.10(m, 22H, Ar),. o. decane(14).. −1. CH2O-), 3.82-4.05 (m, 8H, -O CH 2 (CH2)8CH3), 4.07-4.20. C-O stretch). H-NMR(CDCl3, δppm): 0.83-0.97(m,. Anal. Calcd. for C90H126O14: C, 75.52; H, 8.81%. Found:. 12H, -CH 3), 1.20-1.59(m, 44H, -O(CH2)2 ( CH 2) 4 CH 3,. C, 75.49; H,8.83%.. 1. -O(CH2)2 CH2 (CH2)2O-), 1.76-1.92(m, 12H, -OCH2 CH 2 (CH2)4CH3, -OCH2 CH2 (CH2)6 CH 2 CH2O-), 3.89-4.03. . m F%` Ð}Z '() À +)0 bá 2 C 1ãä å b<b Journal of the Korean Chemical Society.

(10) !; 1,10-Bis[2,5-bis(4-alkyloxyphenoxycarbonyl)phenoxy]decane. á»(Perkin-Elmer IR Spectrophotometer 710B) 2 æ çp |t( H-NMR, Varian Associates EM 360A) /A,-H, â¤báC Eager 200 Elemental Analyser` ,B ¨,Bè...

(11) . '() &1Ï#C 5¤ Æ,` Du Pont DSC 910* @A,B 7& 2 é ê 10 C/min xyrz.. Ö r4 L{/` &1 ë* Ð ,B, ì(indium)* Ü )5 @A,-H, '() < 7&8 (Mettler Hot Stage FP-2)/ 9: ;<=>?(Leitz, Ortholux)* @A,B @,-.. 1. o. 71. bá ¨,-H, À +) Å1 IR HNMR ÷ùúû* Fig. 1 2` MNOG[, /0 {1 IR H-NMR ÷ùúû ü+1 å ý6 â¤báv Õþ (+ b` 1 MNOG..

(12) . 1,10-Bis[2,5-bis(4alkyloxyphenoxycarbonyl)phenoxy]decane #$ %& '() &1 Ï# L{/ ¨#* Ù¦@&bá 1. 1. wFt @\* '()C .í t ` î,B rigid core` flexibility 7,Ã ¼½* ïðH, l4 b ñ&* òZó ∆H ë * ïðÃ 34d+` ô* õ ~. ®¯ , ` UVWXY v ¡, B E ¥ W¤ª ¢£/ '() wF t a 6 ´öZ} xyrz.. / ,B E ¥ W¤ª `÷ø de m. 2-13,16. Fig. 2. 1H-NMR spectrum of 1,10-bis[2,5-bis(4-heptyloxyphenoxycarbonyl)phenoxy]decane (14) (CDCl3).. 1,10-bis[2,5-bis(4-alkoxyphenoxycarbonyl)phenoxy]. %& '()* (+,-H, /0 &1Ï# < xyrz.. . wF t @\* À +) 1,10-bis[2,5-bis(4-alkyloxyphenoxycarbonyl)phenoxy]decane #$ %& '() C Scheme 1 (+?` ®¯ (+,-.. '( )0 báC â¤bá IR 2 H-NMR b< decane. 1. Fig. 1. IR spectrum of 1,10-bis[2,5-bis(4-octyloxyphenoxycarbonyl)phenoxy]decane (15) (KBr). 2001, Vol. 45, No. 1. Fig. 3. DSC thermograms of Series III (n=1-10) compounds. Both heating and cooling rates were 10 oC/min..

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(14) . 72. (DSC) R4,B Fig. 3` /0 &bá M NOG.. Fig. 3` r ±6 «/, /0C DE 7&` Hv4ÿ+ 3 {/(T )` , C ¼ {/ Ó/ MNOGH, /0 ¼ å & Ó/ î1/G[, Z} n=1, 4, 6-10 '()C t .q Ó/ rB¦G.. / =LC / '()0/ ,M v4 r. nC v4 d+ . /.. , /0C v4 Le` .q v4(polymorphic crystal) /[, / =LC B '()` MNMH ~.. P. /0C &b7 Q}M {` ¼ {/ Ó/ ã` .í } Ó/ rB ¦Z z.. é ` / '()0C

(15) C Ó/ ,MÄ* rB ¦H ~U, /C + 3ÿ34(T ) {/ MNO /[ 34ÿHv4 {/ rB¦ Z z.. / =LC A Le 34/ é ` mesophase glass` © Hd', _¹/... 10 C/min é ê` ¦}Ñ '()0C © 0 34Le` Hd'sGH, ÕÖÁZ ×Ø* _ v4'sZ Ã 34ÿHv4` , {/ Ó/ rB¦Z /.. / =LC =>? ´` ,B g ~G.. P , /0 '( ) < 6 &{/ ¨#* 7&8/ 9: ;< =>? ´,-U, /0C DE 7&` H v4ÿ+ 3 L{/7 sGH, é` + 3` 34Le d+,-[, ÕÖÁZ ×ØM /L L{/ Q}MZ z.. /L Ù¦@&bá6 7&8/ 9: ;<=>? v (,B _, /0 '()C 7&` 34 * d+t M, é` 34L* d+, F+ 34* ~G.. Fig. 4 n=4 '() < é 78.0 C` ÐGU IJK 34 üò Schlieren texture rB ¦GH, Fig. 5 n=5 ;<=>? @Ñ é 75.1 C` ÐG [ threaded texture rB¦} IJK 34L * g ~G.. (+: D '()0C é `Ä 34L* d+, F+ IJK34 /G.. 7&` v4Hÿ+ 3 {/(T ), é + 3ÿ34(T ) {/` , Ö Table 1` MNOGH, @\ /, n Fig. 6` MNOG.. Fig. 6` r ±6 « /, v4Hÿ+ 3 {/ Ö(T ) m. 8,9,19. i. '() {/Ö7 '()r. z.. / =LC Q 1 n/ ´sG[, a(packing effect)` ,B ps}Z[, - a rBÜ.. P ò,H ¶ ; +* 7Z _¹` W` UÕ /7 ]7,S Table 1 2 Fig. 6` r ±6 «/ T (¼ {/ Ö)7 Í¤, * ~.. P + 3` 34 {/(T ) Q1 #$%& '()` MN.. / =LC '() length-to-width î ` ,B ps}5 ~U, : Ý¤ @\ t : Ý¤ @\ t` î,B length-towidthî7 ]7, _¹` ïC {/Ö MNOH, Ý¤ @\ t C {/ Ö MNO} 2-6,10-16,24. m. i. o. Fig. 4. Photomicrograph of the series III compound with n=4 taken at 78.0 oC(magnification: 100×).. o. 22,23. o. 22,23. 22,23. m. i. m. Fig. 5. Photomicrograph of the series III compound with n=5 taken at 75.1 oC(magnification: 100×). Journal of the Korean Chemical Society.

(16) !; 1,10-Bis[2,5-bis(4-alkyloxyphenoxycarbonyl)phenoxy]decane. 73. Table 1. Thermal properties and thermodynamic data for the phase transitions of the Series III compoundsa). Tm, oC 94.6 133 116 122 101 103 90.9 76.7 74.8 69.7. n 1(8)0 2(9)0 3(10) 4(11) 5(12) 6(13) 7(14) 8(15) 9(16) 10(17) a) b). Ti, oC (56.6) (89.4) (71.0) (88.0) (84.9) (88.1) (77.0) (79.5) (66.3) (72.9). ∆Hm, kJ/mol. ∆Hi, kJ/mol. 47.3 39.7 24.9 46.8 74.0 90.8 78.8 79.8 79.4 82.1. (0.88) (2.17) (1.39) (3.30) (1.99) (4.85) (3.86) (6.72) (8.61) (4.16). LC propertyb) Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo. Optical Texture Nematic Nematic Nematic Nematic Nematic Nematic Nematic Nematic Nematic Nematic. Values in the parentheses are those obtained from the cooling DSC thermograms. Mo designates monotropic formation of liquid crystal phases.. '() UÕ .T Series III'()C, &+ 34b Series I '() « / )}Ñ bde fg _ 7h,[, 7Z t 34+ =* . Vorländer ij` }*M bde/.. ©M Table 1` _ /0 '()C Q #$%&` MNM &1 {/ ¨#* rB ¦H ~[, Weissflog C Series II'() î+ '( ) 1,4-bis-[4-n-alkyloxybenzoyloxy]-2-n-alkylbenzenes ` /0 , n @\ , m ´% ,ØU, Fig. 7` r ±6 «/ @\, m ` L´·/ , n ] 7`Ä * - n@\ /7 }5 . #$ %& O` a(alternation effect) rB¦H ~.. / =LC Demus, Maier 6 Gray ` ,B rHsGU, @\ }#` . b î+ /'` .H p,.. ®¯, qu` UÕ .T Series III#$ %& '() Fig. 6` r ±6 « /, Fig. 7 «C &{/ ¨#* rB¦H ~.. Q 1 ° t 34'() 3 4L l4 cD" b qu b +( C) ;0 ]7 _¹` RS b³ 1/ 2 ZÃ ]7 .. ®¯ Series I'()C L / ò` 7,B W¤ª/ b | Ç ñ& Series II. . Fig. 6. The dependence of transition points Tm ( ) and Ti ( ) on the longitudinal alkyloxy groups, n, in the Series III compounds.. . - a”¯ =L* rBÜ.. 6 ´: 0 de ú÷` H de {` ¶ 3.4 kJmol ` , î1 ïC `Z |* 7Z _¹` ò,.. ®¯, 34 Le` @\C Ö !d _¹` D 7h. de ß() à,Ã, /L1 { ú÷ de ³¬g ·.. C Ö` H de "/ ïC Ö` r. n* /[, WX` UÕ @\/7 }#` ®¯ /de ]7g /.. P b@/ ! $ÏT bT ]7% &ák(diluent)

(17) A, _¹` b³ ' î+* Í¤%[, 34L * ( l4'Ë.. ®¯ Fig. 6` r ±6 «/ @\ /7 }ZS @\ Í¤ : î+ _¹` + 3' {/ Ö7 Í¤ , /.. W¤ª 7Z` UÕ 2-6,10-16,24-26. “. −1. 6,24. 24. 2001, Vol. 45, No. 1. 26,27. 25. 26,27. 6,24. 28. 29.

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(19) . 74. . Fig. 7. Clearing temperatures in several homologous series of 1,4-bis[4-n-alkyloxybenzoyloxy]-2-n-alkylbenzenes.. ,B ¢+ 34* d+,-H, Series II6 Series III '()C RS UÕ _¹` F+ 34* d+,-... E ¥ `÷ø W¤ª* v, .T U VWXY 7Z[, wF t !" de #$ %& 34 '( )* (+,-.. /0 6 34+³ L´´% 3 |, ,B n=1-10 ÁZ ±²S &1 +5 34+* 6 ´ö Z} @,-.. /0 '()0C DE IJKL* M NOG[, é` 34L* d+, F+ 34 /G.. 7& v4Hÿ+ 3 {/(T )6 é + 3ÿ34(T ) L{/` a¯ =L* rB¦G[, ò,H ¶. ;+* 7Z 6 @\ Í¤: î+ _¹` 7 ]7g . { / Ö7 Í¤,-.. m. i. 1. Vorländer, D. Chemische Kristallograpie der Flussigkeiten; Akadem Verlagsgesellschaft: Leipzig, 1924. 2. Demus, D.; Demus, H.: Zaschke, H. Flussige Kristalle in Tabellen; VEB Deutscher Verlag fur Grundstoffindustrie: Leipzig, 1974. 3 Demus, D.; Zaschke, H. Flussige Kristalle in Tabellen II, VEB Deutscher Verlag fur Grundstoffindustrie: Leipzig, 1984. 4. Gray, G. W. Molecular Structure and the Properties of Liquid Crystals; London-New-York, 1962. 5. Kelker, H.; Hatz, R. Handbook of Liquid Crystals; Verlag chemie: Weinheim. Deerfield Beach, Florida, 1980. 6. Dewar, M. J. S.; Goldberg, R. S. J. Org. Chem. 1970, 35(8), 2711. 7. Van Meter, J. P.; Klanderman, B. H. U. S. Patent. 1976, 3,971,824. 8. Park, J.-H.; Lee, J.-K.; Choi, O.-B.; So, B.-K.; Lee, S.-M.; Lee, J.-W.; Jin, J.-I. J. Korea Chem. Soc. 2000, 44(2), 127. 9. Park, J.-H.; Jin, J.-I. J. Korea Chem. Soc. 1998, 42(3), 315. 10. Jin, J.-I.; Chung, Y. S.; Lenz, R. W.; Ober, C. Bull. Korea Chem. Soc. 1983, 4(3), 143. 11. Jin, J.-I.; Park, J.-H. Mol. Cryst. Liq. Cryst. 1984, 110, 293. 12. Jin, J.-I. Mol. Cryst. Liq. Cryat. 1995, 267, 249. 13. Liquid Crystals and Plastic Crystals; Gray, G. W.; Winsor, P. A. Eds. John Wiley and Sons Inc.: London, 1974. Vol. 1. 14. Kim, J.-H.; Lee, S.-M.; Jin, J.-I. J. Korea Chem. Soc. 1998, 42(6), 679. 15. Choi, E.-J.; Choi, B.-K.; Kim, J.-H.; Jin, J.-I. Bull. Korea Chem. Soc. 2000, 21(1), 110. 16. Imrie, C. T. Structure and Bonding; Springer: Heidelberg, 1999, Vol. 95, 150. 17. Griffin, A. C.; Buckley, N. W.; Hughes, W. E; Werta, D. L. Mol. Cryst. Liq. Cryst. Lett. 1981, 64, 139. 18. Weissflog, G.; Demus, D.; Diele, S.; Nitschke, P.; Wedler, W. Liq. Cryst. 1989, 5, 111. 19. Huh, S.-M.; Jin, J.-I.; Achard, M.-F.; Hardouin, F. Liquid Crystals, 1998, 25(3), 285. 20. Armarego, W. L. F.; Peron, D. D. Purification of Laboratory Chemicals, 4th Ed.; Butterworth-Heinmann: Oxford, 1996. 21. Akiyama, E.; Ohtomo, M.; Nagase, Y.; Koide, N. Macromol. Chem. Phys, 1995, 196, 3391. 22. Demus, D. Textures of Liquid Crystals; Verlag Chemie: Journal of the Korean Chemical Society.

(20) !; 1,10-Bis[2,5-bis(4-alkyloxyphenoxycarbonyl)phenoxy]decane N.Y., 1978. 23. ; : , 1986. 24. Demus, D.; Goodby, J.; Gray, G. W.; Spiess, H.-W.; Vill. S. W. Handbook of Liquid Crystals, Vol. 1, WileyVCH, 1998. 25. Demus, D. Z. Chem. 1975, 15, 1 26. Weissflog, W.; Demus, D. Crystal Res. & Technol.. . 2001, Vol. 45, No. 1. 75. 1983, 18(1), k21. 27. Weissflog, W.; Demus, D. Crystal Res. & Technol. 1984, 19, 55. 28. Maier, W.; Saupe, A. Z. Naturforsch. 1958, 13a, 564; 1960, 15a, 287. 29. Gray, G. W. The Molecular Physics of Liquid Crystals London-New York, 1979, P.1..

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Synthesis and Thermotropic Properties of New Liquid Crystalline Compounds;1,10-Bis[2,5-bis(4-alkyloxyphenoxycarbonyl)phenoxy]decane ; 1,10-Bis[2,5-bis(4-alkyloxyphenoxycarbonyl)phenoxy]decane  

Synthesis and Thermotropic Properties of New Liquid Crystalline Compounds;1,10-Bis[2,5-bis(4-alkyloxyphenoxycarbonyl)phenoxy]decane ; 1,10-Bis[2,5-bis(4-alkyloxyphenoxycarbonyl)phenoxy]decane