Kinetics on the Reaction of 6-Chloroquinoline and p -Substituted Benzoylchlorides under High Pressures 6- p-

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(1)Journal of the Korean Chemical Society 2002, Vol. 46, No. 3 Printed in the Republic of Korea. 6-

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(5) (2002 3. 22 ). †. †. Kinetics on the Reaction of 6-Chloroquinoline and p-Substituted Benzoylchlorides under High Pressures Eung-Ryul Kim, Jong-Wan Lim, Se-Kyong Kim* , and Young-Shin Ko† Department of Chemistry, Hanyang University, Seoul 133-791, Korea † Department of Science Education, Seoul National University of Education, Seoul 137-742, Korea (Received March 22, 2002). . (10, 15, 20, 25 C) (1, 200, 500, 1000 bar) p- (p-CH , p-H, !"#(6-chloroquinoline)$ %&' ()*+,- ./0 1213 $45 67 p-NO ) 6- (k )8 94:;. < => 5? @A BC>-@A DE(Ea, ∆V, ∆H, ∆S, ∆G)8 94:FG, H 2I $ 2 JK Hammett%&7 ρ8 94:;. 67L MN MN4:FG, OPQ R 6-chloroquinoline 2I 1 ST 2(p-NO )N U VW XY MN 4:;. <Z @A =[(∆V), @A \, [(∆S)L ]^ _$ `F abcFG, ]d e ρL $ `' ab0f;. <? 6ghR 9 i 1%hR %&j S 2 %&kl+m' nG, < MNo ipqA< r1stE L %& kl+mF ruv' w xf;. : 6g, , OPA %& o. 3. 2. 2. 2. N. ABSTRACT. The reaction rates of substituted 6-chloroquinoline, with p-substituted benzoyichlorides (p-CH 3, pH, p-NO2) have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10, 15, 20, 25 oC) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters (Ea, ∆V≠, ∆H≠, ∆S≠, and ∆G≠) and the pressure dependence of Hammett ρ values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron donor substituents in substrate (p-NO 2) with 6-chloroquinoline. When, the activation volume and the activation entropy are all negative. And the Hammett ρ values are positive for the substrate over the pressure and temperature range studied. The results of kinetic studies for pressure and substituent show that thease reactions proceed in typical S N2 reaction mechanism and “associative SN2” in bond formation favored with increasing pressures. Keywords: Kinetics, Pressure, Nucleophilic Substitution Reaction. 187.

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(7) . 188. Brown yj 24 $ alkylpyridine $ %&' 5? ./0 945 67 z {BC>8 94| }Q~ J ./$ A K ./J$ A' 4:FG, Laidler Eyring j %& 1<78 945 %&kl +m' 4:;. << OPA %& 6gh 98 45 1<7 9 j 9N <t E| xFa, =$ VW 24. $ 2 Ja ./J8 945 %&kl+m ' 4| x;. Hyne j |4 benzylchloride$ N./ % & ./J8 94:FG, Tokura, Kondo yj pyridine, triethylamine benzyl bromide ethyliodide$ %& ./J8 |4 94:;. . K %&68 45 27 1<7$ =[ R @A =[ ∆V8 ioF %&$ 1<7 9 45 j 8 ' N xT sf;. Evans Polani L ∆VAI' %& Q$ =[ ./$ 7.R 14J $ =[ at 94:FG, Dickson yj N MN4 1<7 14$ 1N rst ./$ 14J$ MN $ @A =[L _ $ `F st XY 1<79 sL @A =[$ $A 45 94:;. H Hammett ρ`j ipqA K ρ` ipB K ρ`F at ¡ xL¢ ρ`< $ `' ab0 1<7 %&$ £ _$ 4 1< r1v' $C4|, _$ `' ab0 %&$ £ $ 41< r1U ¤' $C;. O PQ 2I$ Q K ρ`' <.45 K 1<7 98 ip$ r1. 4| ;. ¥ 9 L 6-chloroquinoline p- (p-CH , p-H, p-NO )$ %& ; ¦4| §hR %&kl+m' 942 ¨45 5? 9(1, 200, 500, 1000 bar) (10, 15, 20, 25 C) 45 ()*+,-' ./ 45 1213F %&678 i4:;. <© %&67 => e @ A DE(Ea), @A =[(∆V), @A ª« Arnett1. 2. 3. 4. 7. 5. 6. 3. o. @A \¬[(∆H), @A \, [(∆S), @A DE(∆G) y$ @A BC>©' 94: FG, <© => OPQ 2I$ K Hammett %&7 ρ`' 94|, ¨$ ]d i©' ®p45 6ghF quinoline p- $ %& 1%hR %&kl+m Q K 1<7 9$ 8 94| ;. (∆β),. 2. . OPQ ¯.U 6-chloroquinoline 2IR benzoylchloride(p-H), p-methylbenzoylchloride (p-CH )L ]^ Aldrich(HPLC grade)8 ¯.4:FG, |r°~(10 ~10 torr)8 <.45 3± ²O degassing P O column' 45 vacuum transfer 45 4:FG, p-nitrobenzoylchloride(p-NO , Aldrich: HPLC grade)L CCl (Aldrich: HPLC grade) . ³´ ;_ µi 45 ¯.4:;. %&j ¥ 9¶. | 121·0 %&' ³¸FG, O PQ quinoline 2I(p-CH , p-H, p-NO )]^ ( )*+,- ./ § ¹5 OPQ 2I ]^ . /$ %&' ºE42 ¨45, »~.¼' ½©E ¾ | ¿ À ÁÂ Ã ¯.4:FG, 6chloroquinoline benzoylchloride Ä p-methylbenzoylchlorideL micro pipet(0.1~25 µl RAININ)' ¯.45 ¿ ' Å Æ4:FG, p-nitrobenzoylchlorideL »~.¼' ½©E ¾| ¿ À ÁÂ Ã ¯ . 4:;. <Z À$ 8 Ç ºE42 ¨4 5 2Ij 18 42 Å1 %& ³¸;. ¥ 9 ¯.U 6-chloroquinoline$ ÀL U 2I 10 ~10 M<fFG, 2I$ ÀL 10 ~10 M<f;.

(8) . 4 $ À K %&.¼$ 18 42 ¨45 ¥ 9¶ |1·, |.2 Ä |~ (Swiss, NOVA) 8 conductivity meter(YSI model 32 Ohio) recoder(KIPP È ZONNEN BD60, Holland) i45 5? (10, 15, 20, 25 C) (1, 200, 500, 1000 bar)4 1$ 8 4:;. ¥ %&©j Menschutkin %&$ i < Ast %&.¼$ 1N MN4T U;. <Z OPQ$ À 3. −5. −6. 2. 5. 2. 4. 3. −2. −4. 2. −3. −5. 8. o. 9. Journal of the Korean Chemical Society.

(9) 6- p- ! "# $% &'() *+. 8 2I$ À É ÊT45 ¯1Ë%&F r u ³Ì GuggenheimÍ $45 ¯1Ë %&67 (k .)8 i4:;. H U quinoline$ À K k . `F => 2Ë%&67(k )8 ;_ Í $45 94:;. 7. obs. obs. Table 1. Second-order rate constants (k2) for the reaction of pSubstituted benzoylchlorides with 6-chloroquinoline in acetonitrile at various temperatures and pressures. 2. kobs .=k2[6-CH3C9H7N]. Y-C6H4COCl. (1) p-CH3.

(10) . ¯1Ë %&6 7$ => 2Ë%&67(k )8 «Î4:F G, k L $ MN MN4G, 2I 1ST(p-NO ) 2N U VW k L XY MN o' w xf;. < K k $ 8 Table 1 ab0f;. H K k => ;_ Í (2) j 2 ËÍ$ « A, B, C `' 94|, Í (3~5) }4 5 @A =[(∆V, ∆V )8 945 Table 2 ab0 fFG, 2Ë67$ «8 25 C8 Ï Fig. 1 ab0f;.. p-Ha. 2. 2. 2. 2. p-NO2. 2. 2. 0. o. Quardratic Eq.: lnk=A+BP+CP2 ∆V= -RT(B+2CP) ∆V0= -RTB. (3). ≠. ∂ ∆V ∆β= –  --------------- = 2RTC  ∂P . (5). k2×103(L·mol-1s-1). Temp. (oC). 1. 200. 500. 1000 bar. 10 15 20 25 10 15 20 25 10 15 20 25. 0.120 0.208 0.330 0.595 0.239 0.415 0.624 1.041 0.964 1.471 2.022 3.423. 0.161 0.263 0.446 0.776 0.307 0.528 0.809 1.332 1.290 1.914 2.758 4.458. 0.212 0.394 0.624 1.032 0.411 0.708 1.091 1.766 1.735 2.819 3.845 6.035. 0.360 0.640 1.039 1.726 0.690 1.184 1.850 2.917 2.969 4.689 6.563 10.20. a. p-H: Benzoylchloride. %&2(V ) 1<7(V )¯<$ Ð=[ R ∆VL ]^ _(-)$ `' ab0t MN K %&6$ MN8 5Ñ| xFG, i. t. ∆V=Vt−Vi. (2) (4). 189. (6). L MN ÒÓ4|, MN MN4L VÔA' ab0| x;. MN |−∆V|L ÒÓ4| xFG, <L MN |−∆V|. Table 2. Activation volume parameters, for the reaction of p-substituted benzoylchlorides with 6-chloroquinoline in acetonitrile at various temperatures and pressures Y-C6H4-COCl. Temp. (oC). −∆V (mL · mole−1). −∆β×102(mL·mole-1·bar-1). 1a. 200. 500. 1000 bar. p-CH3. 10 15 20 25. 28.8 29.3 31.1 32.6. 27.4 30.8 31.5 27.5. 25.1 26.9 27.3 25.7. 21.4 20.6 20.4 22.8. 117.49 12.7 13.8 115.93. p-Hb. 10 15 20 25. 29.0 31.0 32.5 33.8. 25.6 25.6 27.3 26.3. 24.4 24.6 25.9 24.9. 22.4 22.9 23.5 22.7. 113.94 113.31 114.81 114.47. p-NO2. 10 15 20 25. 29.3 33.9 34.3 35.8. 27.9 31.4 31.8 28.2. 25.9 27.5 28.0 26.4. 22.4 21.1 21.6 23.4. 116.98 12.8 12.7 116.03. When the −∆V at 1atm apperas to −∆V 0 . p-H: Benzoylchloride. a. b. 2002, Vol. 46, No. 3.

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(12) . 190. L VWL %& <%&$ V« %& Þsa ;Ó %&< W) AÔ' ab0G, ∆V <−20 ml · mol $ `' ab0L VW <A< Û %&F |U Ã x;. ¥ 9 L 1 QhF ∆V`< _$ `' ab0| xFG, Éh Û _$ `' abßF 1QhF ipqAF istEL 1qhR S 2 %&$ àá' ab0| x FG, ./ $ 14 JN Ñ %& 5o' w x;. . OPQ U $ % & 2Ë67 => z{h @A BC >©(∆H, ∆S , ∆G , Ea)' «Î45 â Ï 25 C. $ z{h @A BC>©' Table 3 ab0f;. <Z ∆H`j MN ÒÓ4| xFG, p-CH >p-H>p-NO ãF ä»4T ÒÓ4| x_' w xf;. H ∆SL ]^ _$ `' ab0| x FG, |−∆S |L MN ÒÓ4| p-CH <p-H <p-NO ãF MN4| x_' w xfFG, ∆G `j |∆S |$ VÔA ¯4T aba| x_' w xf;. å Leffler yj ∆H ∆S ¯<$ y 6 «(isokinetic relation)8 ;_ Í (8) < a bæ xFG, 2 2 T .8 y6(isokinetic temperature) 4:;. −1. 0. N. o. 3. 2. 3. Fig. 1. Pressure dependence of lnk2 for the reaction of 6chloroquinoline with para-substituted benzoylchlorides in acetonitrile at 25 oC (−−: p-CH3, −− : p-H, −− : p-NO2).. 2. 15. %&2 =[ÒÓ }Q~ J$ MN K Ñ ¨ ./$ 14(electrostriction) J$ ÒÓ $ V V$ Ë<N ;Ó (E|, MN %&2 =[MN 14 JN MN45 V V$ Ë<N XY ÕE2 ZÖ<;. ∆VL %& × Q$ =[ (∆V ) 1<7 $ %&×I ./$ .' ab0L 14 J R . / $ µØz 2L =[ (∆V ) 9 ¡ x;. t. t. iso. δ∆H = Tiso. δ∆S. i. i. r. s. Table 3. Activation thermodynamic parameters, for the reaction of p-substituted benzoylchlorides with 6-chloroquinoline in acetonitrile at 25 oC under various pressures Y-C6H4COCl. Press. (bar). ∆H b. −∆S c. ∆G d. Eae. p-CH3. 1 200 500 1000. 71.62 71.19 70.67 70.36. 66.70 65.87 64.98 61.80. 91.43 90.77 90.07 88.79. 74.03 73.61 73.08 72.77. 1 200 500 1000 1 200 500 1000. 65.42 65.27 65.01 64.61 55.42 54.88 54.44 54.28. 83.17 80.58 79.56 76.66 106.6 106.2 104.9 101.1. 90.04 89.43 88.73 87.49 87.09 86.44 85.69 84.39. 67.84 67.69 67.43 67.03 57.84 57.30 56.86 56.70. 10,11. ∆V=∆Vr+∆Vs. (7). %& << AsÙa ÓÚ< taE ¾ L VWL %&× Q$ =[ $45 ∆VN isG, << 54L %& L ./$ µ Øz 2L =[ $ ∆VN iU;. <¤j <A ./$ =[ Û N x;| |st x;. H Sera , Lenoble , Laidler y $4 ∆V Ü0 <Ùa ∆V ≅ −5 ml · mol R VWL ip$ B N rusL %&kl+m Ý AÔ< Û %&A ' ab0G, ∆V ≅ −10 ml · mol $ `' NE. a. p-H. 11,12. 12. 12,14. p-NO2. 2. 0. −1. 0. 0. −1. (8). p-H: Benzoylchloride, bH: kJ · mole−1, c∆S: J · mole−1 · K−1 ∆G: kJ · mole−1, eEa: kJ · mole−1.. a. d. Journal of the Korean Chemical Society.

(13) 6- p- ! "# $% &'() *+. Fig. 2. Isokinetic relations for the reaction of 6-chloroquinoline with p ara-substituted benzoylchlorides in acetonitrile at various pressures.. δ∆G = δ∆H −T δ∆S. = Tiso. δ∆S − T δ∆S = (Tiso.−T) − δ∆S. (9). <Z y6(T .)N ¶ç(T) j VW ./ Ja 2JL è 4T %&67$ N éT sG, y6N ¶ç ; ÊT aba L VW %&6L Ñ \¬[ $ êsG, y 6N ¶ç ; T abaL VWL \, [ $ \, [ ê%&F ./J 2R ;L ¤F |st x;. ∆H ∆S$ y6 «L Fig. 2 < ë j Åì « xFG, Í (8)F => y6 (T .)8 9 i 6-chloroquinoline: p-CH (235.7 K), p-H(110.4 K), p-NO (164.3 K) aba ¶ç(283.15, 288.15, 293.15, 298.15 K) ; íT abcFG, @A DEL 2I 0 ÒÓo' w xfFG, 2IR VW p-CH > p-H > p-NO ãF M N4:;. < Z @A DE$ K $A' îhF 6-chloroquinoline benzoylchloride Fig. 3 ab0fFG, 1ËÍF 2 28 94 :;. iso. 16. iso. 3. 2. 3. 2002, Vol. 46, No. 3. 2. 191. Fig. 3. Pressure dependence of activation energy for the 6chloroquinoline with benzoylchloride (p-H) in acetonitrile at various pressures (− −: 1 bar, −− : 200, −− : 500, −− : 1000).. H |−∆S |` ∆G`< ÒÓ4 | xL VÔAj 5? 9© $ \, [ ê%&R 2 %&kl+mï' }M45 Ñ| x;. ¥ %&$ VW ∆S $ \, [ ê%& R 2 %&ï' w xf;. 1<7 14ðN taL %&$ VW ∆V ` ∆S`< Û _(-)$ `' abñ;| <C |s t x;. Eyring Sera yj ∆V8 %&A 9 }45 ∆VN Û _$ `' òL VW 1<7$ 14N r1U 7, Ý 14 7N ÕET v' $C4G, <Z ./ $ óÔ $45 ∆SN Û _$ `' ab0|, |−∆V|`< MN4 |−∆S| ` MN ;| |4:;. ¥ %&$ VW |−∆V| `$ MN |−∆S| ` MN4| x;. Menschutkin %&$ VW 1<7$ A< %&× ; Ê2 ZÖ 1<7 ∆VL 14ð $ ./$ 14 J $ ∆VL _$ `' a b0G, |−∆V| `< MN4 14 JN XY ÊT .45 ./$ ÒÓ |∆S| ` MN4T st 1<7$ N MN4L |−∆V| |−∆S|$ 7 «8 ¡ x;. â?a 17. 17-19.

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(15) . 192. %&× 1<7$ =[N 42 ZÖ ∆V` ô$ N õ ∆V ∆S$ 7 «L ;Ó ö¦¶4T s÷ ∆V ∆S$ 7 « L 2 $CN x_' w xf;. % &kl+m$ xt L 2 $ @A = [ (∆V )$ h.< .o' w xf;. ! "# Hammett ρ 67(k ) ;_ Í (10)' <.45 2I$ Q(ρ ) Hammett ρ `' Table 4 ab0fFG, â Hammett plot' 25 C Fig. 4 ab0f;. 2I %&7 ρL ipqA K ρ`(ρ>0) ipB K ρ`(ρ<0)F at ¡ x FG, Q$ %&$ Ò 14<. ø ù$ Ê28 abñ;. ρ`< (+)R V W 1<7$ %& £ _$ 41< r1st ip $ qA< W)o' $C4|, _(-)$ ρ`R VW %& $ £ $ 41< r1v' ú;. Table 4. ρ `j ]^ $ `' ab0| xFG, < MN o ρ ` 1QhF MN4| x;. <L 2 I$ %& £ _$ 41< r1U 1<7 98 $C4G, < MNo 2 $ 14< ø ù< XY MN45 2 ÒN XY Õû' abñ;. Hammett ρ $Íj ; _Í < abæ x;. ∂ρ ∂ ∆G ∆V =  ----------------- = – 2.303RTσ  ------  ∂P T  ∂P  T. (11). Table 4. Hammett ρ values for the reaction between substituted 6-chloroquinoline and p-substituted benzoylchlorides (YC6H4COCl) in acetonitrile at various temperatures and pressures. ∂ρ ∆V = 2.303RTσ ------  ∂P T. (12). 0. 2. Y. o. 20,21. ρ. X-C9H7N. Temp. (oC). 1. 200. 500. 1000 bar. 6-ClC9H7N. 10 15 20 25. 0.899 0.836 0.775 0.758. 0.905 0.849 0.787 0.760. 0.911 0.859 0.791 0.769. 0.917 0.866 0.800 0.777. ∆G = −2.303RT ρσ. (10). ≠. <? iL ∆V`F => 2 7 σN∂ρM  N¡ü |−∆V| `< MN45 Í (12)$ i -----∂P `< $ `<st N K ρ`$ MN8 5 Ñ| x;. <L < MNo 2$ 1 4<ø ù< MN45 ip$ qA< rsL %& kl+mF ¡ x;. H N MNo ρ`< ;Ó ÒÓ4L ¤ F abý ¤j $ MN $ þø< ;Ó @ÿ45ûF â %ÿ< ;Ó MN42 Z ÖR ¤F U;. ¥ ¶ç$ ]d VW %&67 k L < MNo MN4:FG, 2I 1 ST(p-NO ) QN sxL VW %&6L MN4:;. H y6(T .)N ¶ç ; T abc|, 1<7 ∆V ` ∆SL QhF Û _(-)$ `' abßF ¥ %&©$ 1<7 14ðN ta %&$ £ _$ 41< r1st ipqA< W)o' w xf;. H OP Q$ %& £L $ 41< r1st %& £ R IÓ$ (+)$ 41< r1v' w xf ;. H MN 14 J ÒÓ }Q ~ J$ MN |−∆V|, |−∆S| `j ÒÓ4 G, 14<ø ùj XY MN45 ρ`$ MN C-N ipqA< W) associative S 2 1<7 9 $ A< MN4L %&kl+mF str;. T. 2. 2. iso. 0. Fig. 4. Hammets plots rot the reaction of 6-chloroquinoline with p-substituted benzoylchlorides in acetonitrile at 25 oC.. N. Journal of the Korean Chemical Society.

(16) 6- p- ! "# $% &'() *+. 1. Arnett, E. M.; Reich, J. Am. Chem. Soc. 1980, 102, 5892. 2. Glasstone, S.; Laidler, K. J.; Eyring, H. “The theory of Rate Processes,” McGraw-Hill, N.Y., 1941, p. 418. 3. Hyne, J. B. J. Am. Chem. Soc. 1966, 88, 2104. 4. Kondo, Y.; Tojima, H.; Tokura, N. Bull. Chem. Soc. Japan 1972, 45, 3579. 5. Evans, M. G.; Polanyi M. Trans. Faraday Soc. 1935, 31, 875. 6. Dickson, S. J.; Hyne, J. B. Can. J. Chem., 1971, 49, 2394. 7. Guggenheim, E. A. Phil. Mag. 1926, 2, 538. 8. Kwun, O. C.; Kyong, J. B. Bull. Korean Chem. Soc., 1985, 6, 259. 9. Menschutkin, N. Z. Phys. Chem. 1890, 5, 589. 10. Moelyn-Hughes, Kinetics in Solutions, 1947; p. 338. 11. Whalley, E. Advances in Physical Organic Chemistry,. 2002, Vol. 46, No. 3. 193. 2nd Ed.; Academic Press:N.Y. 1964; p. 93. 12. Sera, A.; Miyazawa, T.; Matsuda, T.; Togawa, Y.; Maruyama, K. Bull. Chem. Soc. Japan, 1973, 46, 3490. 13. Lenoble, W. J.; Yates, B. L.; Scaplehorn, A. W. J. Am. Chem. Soc. 1967, 89, 3751. 14. Asano, T.; LeNoble, W. J. Chem. Rev. 1978, 407. 15. Leffler, J. E.; Grunwald, E. Rate and Equilibria of Org. Reaction, John Wiley and Sons: N.Y. 1963; p. 327. 16. Harned, H. S.; Owen, B. B. Physical Chemistry of ElectrolyticSolution, 3rd Ed, Reinhold: New York, 1958; p. 369. 17. Weale, K. Chemical Reactions at High Pressures 1967, Spon, London. 18. Eckert, C. Rep. Prog. Phys. Chem. 1972, 23, 239. 19. Jenner, G. Angew. Chem. Int. Ed. 1975, 14, 137. 20. Rogne, O. J. Chem. Soc(B). 1969, 1294. 21. Lee, I.; Kim, N. I.; Sohn, S. C. Tetrahedron Lett. 1983, 23, 4723..

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Kinetics on the Reaction of 6-Chloroquinoline and p -Substituted Benzoylchlorides under High Pressures    6- p-

Kinetics on the Reaction of 6-Chloroquinoline and p -Substituted Benzoylchlorides under High Pressures 6- p-