p -Substituted Benzoylchlorides under Various Pressures Kinetics on the Reaction of Substituted Quinolines and 

Printed in the Republic of Korea

     p- 

 

*

  

(2003. 2. 27 )

Kinetics on the Reaction of Substituted Quinolines and p-Substituted Benzoylchlorides under Various Pressures

Jong-Wan Lim and Se-Kyong Kim*

Department of Chemistry, Hanyang University, Seoul 133-791, Korea

Received February 27, 2003)

.  (10, 15, 20, 25^oC) (1, 200, 500, 1000 bar)    p- (p-CH3, p-H, p-NO2)   (quinoline, 6-chloroquinoline)! "#$ %&'()* +,-. /0/ 1 !23 4 5(k2)6 7289. :;<= 3> ?@ AB=-?@ CD(Ea, ∆V
, ∆H
, ∆S
, ∆G
)6 728EF, G

Hammett"#5 ρX 0H! 0 IJ ρY6 7289. 4 5K    LM  LM28E F, NO P quinoline 0H / QR 0(p-NO²)M S TU VW LM 289. :X ?@ <Y(∆V
),

?@ Z);Y(∆S
)K [\ ]! ^E; _`aEF, [b  c . NO ! 0 I ρXK ]! ^

$ ρYK ! ^$ _`-d9. :>
4 efP 7 g /"fP "#h SN2 "#ij(k$ lF, :

LMm  gno@: p/qrDK "# ij(kE; pst$ u  vd9.

: , wx, 4 e

ABSTRACT. The reaction rates of substituted quinolines (6-Clqui., qui.) with p-substituted benzoylchlorides ( p-CH3, p-H, p-NO2) have been measured by conductometry in acetonitrile, and the rate constants are determined at various tem- peratures (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
, ∆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 acceptor substituents in substrate (p-NO2) with quinoline. The activation volume and the activation entropy are all neg- ative. And the Hammett ρ values are negative for nucleophile (ρX) and positive for the substrate (ρY) over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed through a typ- ical SN2 reaction mechanism and “associative SN2” favoring bond formation with increasing pressures.

Keywords: Pressure, Thermodynamics, Kinetics



Arnett¹ Brownyh 02.! alkylpyridine

! "#$ 3> +,-. 723 4 5 wx

AB=6 72z { |} I +,! ~@

J +,I! €@$ ‚28EF, Laidler

Eyring²h "# ƒ
/:5„6 723 "#ij (k$ …†289. :‡: NO@ "# 

4 ef 76 ˆ23 /:5„ 7 ‰‚ Šh  7M :‹r Dz vE_, <Œ! TU 02.

! 0 I_ +,I6 723 "#ij(k

$ …†2z v9.

Hyne³h z2. benzylchloride! M+, Œ "

# 
+,I6 728EF, Tokura, Kondo⁴y h pyridine, triethylamine benzyl bromide ethyliodide

! "# 
+,I6 z2. 7289. 

.    J "#4 6 Ž23 05„

 /:5„‘! <Y P ?@ <Y ∆V
6 g

mE;’ "#! /:5„ 7 23 Šh 

“6 ”$ M vR qd9.

Evans Polani⁵K ∆V
@H$ "#Π ! <Y

  +,Œ! 5•–+P /2—I !

<Y ; _˜r 728EF, Dickson⁶yh  M LM2™ /:5„. /2! / M špqr +,! /2—I! LM ! ?@ <YK ]

! ^E; qr VW †
/:5„7; qK ?

@ <Y!  !›@ 23 7289.

G
Hammett ρ^h gno@ J ρ^ gnA

œ J ρ^E; _˜r žŸ  vK  ρ^: 

! ^$ _`-™ /:5„. "#! ¡ ]! 2 /: p/t$ !B2z, ]! ^$ _`-™ "#!

¡ ! 2/: p/S ¢$ !B
9. . N O  0H!    J ρ^$ :+23 

  J /:5„ 76 gn! p/ ;. 

‚2z
9. £ 7.K S quinoline(quinoline, 6-chloroquinoline) p-  (p-CH3, p-H, p-NO2)! "# 
“9 ¤2z ¥fP "#i j(k$ 720 ¦23 3> 7‘(1, 200, 500, 1000 bar)  (10, 15, 20, 25^oC)  23 %&

'()*$ +,;23 /0/ 1E; "#4 5 6 g289. :§ "#4 5;<= ž 

 c. ?@ CD(Ea), ?@ <Y(∆V
), ?

@ —¨©(∆β
), ?@ ZªY(∆H
), ?@ Z)

;Y(∆S
), ?@ CD(∆G
) y! ?@ AB

=§$ 728EF, :§;<= NO  0H! 

 J Hammett "#5 ρX, ρY ^$ 72z, ¦!

[b g§$ «n23 4 efE; quinoline

p-  ! "# 
/"fP "#ij (k     J /:5„ 7!  6 72z
9.

   . NO ; ¬+S quinoline, 6- chloroquinoline 0HP benzoylchloride(p-H), p- methylbenzoylchloride(p-CH3)K [\ Aldrich(HPLC grade)6 ¬+28EF, zp­|(10⁻⁵~10⁻⁶ torr)6 : +23 3® ¯N degassing  P2O5 column$ ˆ 23 vacuum transfer23 …28EF, p-nitrobenzoyl- chloride(p-NO2, Aldrich: HPLC grade)K CCl⁴(Aldrich:

HPLC grade) + °± 9] ²g 23 ¬+28

9. "#h £ 7³. …–
z /0/ ´-

. "#$ °µEF, NO ; quinoline 0H(p- CH3, p-H, p-NO2)[\ %&'()* +, ¥ ¶ 3 NO  0H [\ +,! "#$ ·D20 ¦2 3, ¸|+¹$ º§D »z ¼€
½ ; ¾¿. À

; ¬+28EF, S quinoline benzoylchloride Á p-methylbenzoylchlorideK micro pipet(0.1~25µl

RAININ)$ ¬+23 ¼€
$ Â Ã28EF,

p-nitrobenzoylchlorideK ¸|+¹$ º§D »z ¼€

½ ; ¾¿. À; ¬+ 289. :X ½ !  6 Ä
·D20 ¦23 0Hh / 6 Ž20 Â/ "# °µ9.

£ 7. ¬+S S quinoline! ½ K 

S 0H  10⁻²~10⁻³M:dEF, 0H! ½ K 10⁻⁴~10⁻⁵ M:d9.

   .   2. žž! ½  J "#+¹! / 6 Ž20 ¦23 £  7³. …–
z/ ´, z+0 Á z|

(Swiss, NOVA)6 conductivity meter(YSI model 32 Ohio) recoder(KIPPÅZONNEN BD60, Holland)  g23 3>  (10, 15, 20, 25^oC) (1, 200, 500, 1000 bar)2. / !  6 Ž289. £ "#

§h Menschutkin⁸"#! g; : @qr "#

+¹! / M LM2R S9. :X NO ! ½ 6 0H! ½  ƍ ÇR23 ¬1È"#E; ps ° É GuggenheimÊ⁷ !23 ¬1È "#4 5(k^obs.) 6 g289. G
S quinoline! ½  

J kobs. ^E;<= 2È"#4 5(k2)6 9] Ê

!23 7289.

kobs.=k²[X-C9H7N] (1)

  

     . ¬1È "#4 5!  ; <= 2È"#4 5(k2)6 ©Ë28E F, :X 2È"#4 5K quinoline: 6-chloroquinoline

“9 ÇR _`a]$ u  vd9. k²K   

! LM  LM2F, 0H /QR(p-NO2) 

0M S TU k2K VW LMm$ u  vd9.

  J k²!  6 25^oC. Ì Í; Fig. 1

 _`-d9.   J k2;<= 9] Ê (2)

 ‡h 2ÈÊ! © A, B, C ^$ 72z, Ê (3~5) Ê {23 ?@ <Y(∆V
, ∆V0
)6 723 Table 1 _`-d9.

Quadratic Eq.: lnk = A + BP + CP² (2)

∆V
= -RT(B + 2CP) (3)

∆V0
= -RTB (4)

∆β
= (5)

"#0(Vi) /:5„(Vt)¬:! ŒÎ<Y  P

∆V
K [\ ](-)! ^$ _`-r  LM J

"#4 ! LM6 “3Ïz vEF,

∆V
= Vt−Vi (6)

|−∆V
|K  LM  ÐÑ2z,  LM 

 LM2K TÒ@$ _`-z v9.

 LM  |−∆V
|K ÐÑ2z vEF, :K

 LM  "#0 <YÐÑ { |} I

! LM J Ϧ +,Œ! /2—(electros- triction) I! ÐÑ ! Vt Vi! È:M 9Ñ –

%Dz,  LM  "#0 <YLM /2

∂∆V ^≠ ---∂P

 

 =2RTC –

Fig. 1. Pressure dependence of lnk₂ for the reaction of 6- chloroquinoline and quinoline with p-substituted benzoyl- chlorides in acetonitrile at 25^oC (6-Cl-qui.: -
-: p-CH3, -_-:

H, -_-: p-NO2,, qui.: -_-: p-CH3, - * -: H, --: p-NO2)

Table 1. 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)

1^a 200 500 1000 bar

p-CH3

10 28.8 27.4 25.1 21.4 7.49

15 29.3 30.8 26.9 20.6 12.7

20 31.1 31.5 27.3 20.4 13.8

25 32.6 27.5 25.7 22.8 5.93

p-H^b

10 29.0 25.6 24.4 22.4 3.94

15 31.0 25.6 24.6 22.9 3.31

20 32.5 27.3 25.9 23.5 4.81

25 33.8 26.3 24.9 22.7 4.47

p-NO2

10 29.3 27.9 25.9 22.4 6.98

15 33.9 31.4 27.5 21.1 12.8

20 34.3 31.8 28.0 21.6 12.7

25 35.8 28.2 26.4 23.4 6.03

aWhen the −∆V
at 1atm appears to −∆V0
.

bp-H: Benzoylchloride

— IM LM23 Vt Vi! È:M VW ÓD0 X Ô:9. ∆V
K "#Õ  ! <Y (∆Vr
) /:

5„.! "#ÕH +,! –+$ _`-K / 2— I; P
+, Œ! ²Öw. 0K <

Y (∆Vs
); 7ŒŸ  v9.^9,10

∆V
= ∆Vr
+ ∆Vs
(7)

"#. :: @q×_ ÑØ: r_D » K TUK "#Õ  ! <Y  !23 ∆V
M gqF, :: ƒ32K "#.K +,Œ! ² Öw. 0K <Y  !. ∆V
M gS9.

:¢h :@ +,Œ! <Y Ù  M v9z “ zqr v9.^10,11

G
Sera¹¹, Lenoble^11,13, Laidler² y !2™ ∆V0

Ú0 :×_ ∆V0
−5mL · mol⁻¹P TUK gn! A

œM psqK "#ij(k Û Œ @Ò: Ù "#

@$ _`-F, ∆V0
−10 mL · mol⁻¹  ! ^$ M DK TUK Œ "# :Œ"#! T© "#

Üq_ 9Ñ Œ "#: U&
@Ò$ _`-F,

∆V0
<−20 mL · mol⁻¹! ^$ _`-K TU :Œ@

: Ù "#E; “zS À v9. . £ 7.K / fE; ∆V
^: ]! ^$ _`-z vEF, Æ

f Ù ]! ^$ _`ÝE;’ / fE; gno@E

; gqrDK /ofP S^N2 "#! Þß$ _`- z vEF, +,Œ !
/2— IM Ï; "

# ƒ3m$ u  v9.

     !. žž! N O  S  ! "# 
2È4 5 ;<= wxf ?@ AB=§(∆H
, ∆S
, ∆G
, Ea)$ ©Ë23 Table 2 _`-d9.

:X ∆H
^h  LM  ÐÑ2z vEF,

p-CH3 > p-H > p-NO2 àE; á¸2R ÐÑ2z v]

$ u  vd9. G
∆S
K [\ ]! ^$ _`- z vEF, |−∆S
|K  LM  ÐÑ2z p-CH³

< p-H < p-NO2 àE; LM2z v]$ u  vdE F, ∆G
^h |−∆S
|! TÒ@ ¬2R _`_z v ]$ u  vd9.
â Leffler<sup>14</sup> yh ∆H
 ∆S
¬ :! y4 ƒ©(isokinetic relation)6 9] Ê (8) ‡ : _`ã  vEF, 0ä0 Tiso.6 y4  (isokinetic temperature) 289.

δ∆H
= Tiso. δ∆S
) (8) δ∆G
= δ∆H
− T δ∆S

= Tiso. δ∆S
− T δ∆S

= (Tiso. - T) · δ∆S
(9) :X y4 (T^iso.)M ³å (T) ‡h TU +, I_ 0IK æƒ2R "#4 5!  M çR qF, y4 M ³å “9 ÇR _`_

K TU "#4 K Ï; ZªY ! èqF, y 4 M ³å “9 –R _`_K TUK Z)

;Y !
Z);Y è"#E; +,I 0P

9K ¢E; “z qrv9.¹⁵

Ê (8)E;<= y4  (Tiso.)6 7
g

6-chloroquinoline: p-CH3(235.7 K), p-H(110.4 K), p-NO2

(164.3 K) :dEF, quinoline: p-CH³(221.1 K), p-H (273.3 K), p-NO2(241.3 K); _`_ ³å (283.15, 288.15, 293.15, 298.15 K) “9 éR _`aEF, ?@

CDK ê
NO  0H -. LM

 ÐÑm$ u  vd9. Û, NO P TU quinoline : 6-chloroquinoline “9 –R _`a]$ u  vd EF, 0HP TU p-CH³> p-H > p-NO2àE; LM2 89. : X ?@ CD!  J !›@$ ë

~

~

Table 2. Activation thermodynamic parameters^a for the reactions of p-substituted benzoylchlorides with substituted quinoline in acetonitrile at 25^oC under various pressures

X- C9H7N

Y-C6H4- COCl

∆H
^a −∆S
^b ∆G
^c Ea^d

1 200 500 1000^f 1 200 500 1000^f 1 200 500 1000^f 1 200 500 1000^f C9H7N p-CH3 67.05 66.68 66.30 65.92 76.19 75.08 73.27 71.18 89.74 89.05 88.12 87.10 69.47 69.09 68.71 68.33 p-H^e 62.42 62.00 61.60 61.18 87.45 86.51 84.91 83.06 88.52 87.82 86.96 85.96 64.84 64.41 64.01 63.60 p-NO2 50.75 50.49 49.95 49.55 116.5 115.0 113.6 111.3 85.41 84.70 83.77 82.66 53.16 53.16 52.36 51.96 6-Cl- p-CH3 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 C9H7N p-H^e 65.42 65.27 65.01 64.61 83.17 80.58 79.56 76.66 90.04 89.43 88.73 87.49 67.84 67.69 67.43 67.03 p-NO² 55.42 54.88 54.44 54.28 106.6 106.2 104.9 101.1 87.09 86.44 85.69 84.39 57.84 57.30 56.86 56.70

a∆H
: KJ · mole⁻¹, ^b∆S
: J · mole⁻¹· K⁻¹, ^c∆G
: KJ · mole⁻¹, ^dEa : KJ · mole⁻¹

ep-H: Benzoylchloride, ^fpressure: bar

fE; benzoylchloride . Fig. 2 _`-d9.

G
   |−∆S
|^ ∆G
^: ÐÑ2 z vK TÒ@h 3> 7§¹⁶ ! Z);Y  è"#P 2Œ "#ij(kì$ {L23 Ïz v9.

. £ "#! TU ∆S
 !
Z);Y è"#

P 2Œ "#ì$ u  vd9.

(∆∆∆∆V
)
 (∆∆∆∆S
)

∆V
 ∆S
! 5ƒƒ©6 6-chloroquinoline(25^oC, 1 bar)P TU6 Í; Fig. 3 _`-d9. /:5„.

/2ŒíM r_K "#! TU ∆V
^ ∆S
^:

Ù ](-)! ^$ _`î9z :B “zqr v9.<sup>16-18</sup> Eyring Sera yh ∆V
6 "#@ 7 {23 ∆V
M Ù ]! ^$ ïK TU /:5„! /2M p/S 5„, Û /2— 5„M ÓDR t$ !B2F, :X +, Œ! ðÒ !23 ∆S
M Ù ]! ^$ _`

-z, |−∆V
|^: LM2™ |−∆S
|^ LM
9z “ z289. £ "#! TU |−∆V
|^! LM 

|−∆S
|^ LM2z v9.

Menschutkin "#! TU /:5„! ~@: "#Õ

“9 Ç0 XÔ /:5„. ∆V
K /2Β !

+,! /2— I ! ∆V
K ]! ^$ _

`-F, |−∆V
|^: LM2™ /2— IM VW Ç R –+23 +,Œ!  ÐÑ  |−∆S
|^ LM2R qr /:5„! † M LM2K |−∆V
|

|−∆S
|! 5ƒƒ©6 ‚ Ÿ  v9. Ì>_     "#Õ /:5„! <YM 20 XÔ

∆V
^ ñ‘!  M ò ∆V
 ∆S
! 5ƒƒ©

K 9Ñ ó¤³2R qô; ∆V
 ∆S
! 5ƒƒ©K

0. !BM v]$ u  vd9. . "#

ij(k! ‰‚ vr.K 0.! ?@ <Y

 (∆V0
)! f+: +m$ u  vd9.

   Hammett ρρρρ

4 5(k²) 9] Ê (10)$ :+23 ž   

. 0H!  (ρY) 
Hammett ρY ^ N O !  (ρX) 
Hammett ρX^$ ©Ë23 Table 3 _`-dEF, Ì ƒ
Hammett plot$

25^oC . ëfE; Fig. 4 _`-d9.

0H 
"#5 ρK gno@ J ρ^(ρ>0)

 gnAœ J ρ^(ρ<0)E; _˜r žŸ  v

EF,^19,20  !   
"#! Ð ; /2:

ê õ! Ç06 _`î9. . ρ^: (+)P T U /:5„! "# ¡ ]! 2/: p/qr gn Fig. 2. Pressure dependence of activation energy for the 6-

chloroquinoline and quinoline with benzoylchloride in ace- tonitrile at various pressures (6-Cl-qui.: - *-: 1 bar, --: 200, -+-: 500, -−-1000, qui.: ö
ö^{: 1,} öö^{: 200,} öö^{: 500,} ö
ö^{: 1000).}

Fig. 3. The relation of activation entropy vs. activation vol- ume for the reaction of 6-chloroquinoline and quinoline with p-substituted benzoylchlorides in acetonitrile at 25^oC, 1 bar.

(−: 6-Cl-quinoline, ö: quinoline).

! o@: U&m$ !B2z, ](-)! ρ^P TU "#

! ¡ ! 2/: p/t$ ÷
9. Table 3.

ρY ^h [\ ! ^$ _`-z vEF, : LM

m  ρY ^ / fE; LM2z v9. :K 0 H! "# ¡ ]! 2/: p/S /:5„ 76

!B2F, : LMm  0 !
/2:

ê õ: VW LM23 0 
Ð M VW Óø$ _`î9. Hammett ρ 
 !›Êh 9 ] Ê ‡: _`ã  v9.

∆G
= −2.303RT ρσ (10)

∆V
= T=−2.303RT σ T (11)

∆V
= 2.303RTσ T (12)

:>
gK ∆V
^E; <= 0 5 σM L MŸù |−∆V
| ^: LM23 Ê (12)! g (∂ρ/∂P)T

^: ! ^:qr  LM J ρ^! LM6 “ 3 Ïz v9. :K : LMm  0! / 2:ê õ: LM23 gn! o@: špqK "#

ij(kE; ‚Ÿ  v9.

NO ! 0 I 
ρX ^h [\ ]! ^

$ _`-z vEô; NO ! "# ¡K ! 2 /: p/qF, 0H! ρY ^ ƍ |-ρX|^: Ù ¢h /:5„. "#¡ úP HÑú! ! 2/

: 5Üû p/t$ ÷2F, NO ! /2:ê õ:

"# ,U €m$ !B
9. G
 M LMm

 ρY, ρX ^: 9Ñ ÐÑ2K ¢E; _`ü ¢h  ! LM  Œ! ýê: 9Ñ ?þ23øE;

’ Ì "þ: 9Ñ LM20 XÔP ¢E; žS9.

. £ 7.  S  

! "# 
"#4 K 6-chloroquinoline < quinoline àE; LM2F, £ ³å! [b TU. "#4 5  k2K   : LMm  LM28EF, 0 H /QR(p-NO²)  M qv×_, NO

 /ÏR  M qvK TU "#4 K L M289. G
y4  (Tiso.)M ³å “9 –R _`az, /:5„. ∆V0
^ ∆S
K  fE;

∂∆G ^≠ ---∂P

 

  ∂ρ

∂P---

  

∂ρ

∂P---

  

Table 3. Hammett ρY and ρX values for the reaction between substituted benzoylchlorides(Y-C6H4COCl) and quinolines(X- C9H7N) in acetonitrile at various temperatures and pressures X-C9H7N Temp.

(^oC)

ρY

1 200 500 1000 bar

C9H7N

10 0.918 0.920 0.923 0.940 15 0.848 0.852 0.867 0.889 20 0.787 0.792 0.800 0.813 25 0.769 0.771 0.776 0.795

6-ClC9H7N

10 0.899 0.905 0.911 0.917 15 0.836 0.849 0.859 0.866 20 0.775 0.787 0.791 0.800 25 0.758 0.760 0.769 0.777

Y-C6H4COCl Temp.

(^oC)

−−−−ρ^X

1 200 500 1000 bar

p-CH3C6H4COCl

10 1.629 1.974 2.060 1.832 15 1.551 1.952 1.919 1.675 20 1.564 1.905 1.965 1.709 25 1.387 1.739 1.848 1.581

C6H4COCl

10 1.678 2.089 2.203 1.936 15 1.595 2.015 2.126 1.866 20 1.619 2.008 2.105 1.817 25 1.457 1.927 2.045 1.791

p-NO2C6H4COCl

10 2.132 2.705 2.821 2.566 15 2.194 2.593 2.602 2.374 20 2.246 2.588 2.659 2.377 25 2.033 2.426 2.522 2.279

Fig. 4. Hammets plots for the reaction of 6-chloroquinoline and quinoline with p-substituted benzoylchlorides in aceto- nitrile at 25^oC(6-Cl-qui.: -_-: p-CH3, - -: p-H, --: p-NO2, qui.: öö^{: p-CH3,} öö^{: p-H,} öö^{: p-NO2).}

Ù ](-)! ^$ _`ÝE;’ £ "#§! /:5„

. /2ŒíM r_ "#! ¡ ]! 2/: p/

qr gno@: U&m$ u vd9. G
NO !

"# ¡K ! 2/: p/qr "# ¡úP HÑú! (+)! 2/: p/t$ u  vd9. G

 LM  /2— I ÐÑ { |}

I! LM  |−∆V
|, |−∆S
| ^h ÐÑ2F, / 2:ê õh VW LM23 ρY^ |−ρX| ^! LM

  C-N gno@: U&
associative S^N2 /:

5„ 7! @ÿ: LM2K "#ij(kE; ‚

qrp9.

   

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. Menschutkin, N. Z. Phys. Chem. 1890, 5, 589.

9. Moelyn-Hughes, Kinetics in Solutions, 1947; p338.

10. Whalley, E. Advances in Physical Organic Chemistry, 2nd Ed.; Academic Press:N.Y. 1964; p. 93.

11. A. Sera, A.; Miyazawa, T.; Matsuda, Y.; Togawa, Y.;

Maruyama,K. Bull. Chem. Soc. Japan, 1973, 46, 3490.

12. Lenoble, W. J.; Yates, B.L.; Scaplehorn, A. W. J. Am.

Chem. Soc. 1967, 89, 3751.

13. Asano, T.; LeNoble, W. J. Chem. Rev. 1978, 407.

14. Leffler, J. E.; Grunwald, E. Rate and Equilibria of Org.

Reaction, John Wiley and Sons: N.Y. 1963; p327 15. Harned, H. S.; Owen, B. B. Physical Chemistry of

ElectrolyticSolution, 3rd Ed, Reinhold: New York, 1958; p369.

16. Weale, K. Chemical Reactions at High Pressures 1967, Spon, London.

17. Eckert, C. Rep. Prog. Phys. Chem. 1972, 23, 239.

18. Jenner, G. Angew. Chem. Int. Ed. 1975, 14, 137.

19. Rogne, O. J. Chem. Soc(B). 1969, 1294.

20. Lee, I.; Kim, N.I.; Sohn, S.C. Tetrahedron Lett. 1983, 23, 4723.