MICHAEL ADDITION OF ETHYL (X-CYANOBUTYRATE

TO BENZENE ANALOGUES OF CHALKONES

S.ToMA
Department oj Organic Chemistry,
Komensky University, Bratislava
2771
Received July 22nd, 1968
The addition of ethy11X-cyanobutyrate to chalkones is a first order reaction with respect to chal-
kone. log k can be well correlated with a constants. In the studied temperature range (25 - 45C) Q
does not depend on temperature. The a constants for ferrocenyl were determined: aa, = - 0'582,
up = -0'155 and am = - 0,002. 2 - F u r ~ 1 and 2-thienyl manifested themselves differently,
depending on whether they were bound to a carbonyl group carbon (aa, = 0,104, or - 0'058)
or to the l3-carbon of the double bond (aa, = -0'225, or - 0' 146). We calculated the coefficient
of the transfer through the double bond (/I = 0'641). The substitution of the phenyl group by
ferrocenyl causes a substantial diminution of the sensitivity of the reaction to the influence
of the substituent.
Ingold t proposed a mechanism for the Michael reaction in which he supposed that
the rate determining stage is the attack of the anion of the reagent on . the 13 carbon
atom of the multiple bond. These opinions of Ingold were confirmed in several
papers2 - 5. It was further established that the Michael addition is a first order re-
action with respect to the substrate (unsaturated compounds)6,7 and it was also
proved that the log k in the addition of ethyl cyanoacetate to ferrocenc analogues
of chalkone can be correlated with Hammett's ()' constants
8

In this study we carried out kinetic measurements of the addition of ethyl o:-cyano-
butyrate to benzene and ferrocene analogues of chalkones.
EXPERIMENTAL
Chemicals
All benzene analogues of chalkone were prepared by base catalysed aldol condensation of corres-
ponding aldehydes and ketones according t0
9
. Ferrocene analogues of chalk ones were also pre-
pared by base catalysed aldol condensation according to
10
,11. Chalkones were purified by repeat-
Collection Czechoslov. Chem. Commun. IVol. 341 (1969)
2772 Toma:
ed crystallization from ethanol , and the purity was controlled by elemental analysis, thin-layer
chromatography and comparison with literature data. Melting points of chalkones and literature
references are listed in Tables I - III. Ethyl Cl -cyanobutyrate was prepared analogously to ethyl
cyanoacetate
12
, its boiling point coincided with that from the literature
13
The purity was also
controlled by elemental analysis.
Apparatus and Measurement Methods
All measurements were carried out on a spectrophotometer Spektromon 201 (MOM, Budapest;
with a prism). The spectra were measured in 4. 10- 5M methanollc solutions. Methanol was of the
p.a. purity, purchased from Lachema. The spectrum of ethyl Cl-cyanobutyrate in methanol in the
absence of catalyst did not display any maximum in the region above 220 nm. After the addition
of the catalyst a maximum appeared at 245 nm, the log e of which depended on concentration.
At an ethyl Cl -cyanoacetate concentration of 1' 6 . 10- 2M and sodium methoxide concentration
of 56 . 10- 3 M log e = I '96; at an ethyl Cl-cyanobutyrate concentration 0' 8 . 10- 2M and sodium
methoxide concentration 28. 10- 3M log e = 186. We have checked further the validi ty of Lam-
bert-Beer's law at the Amax of chalkone and in the given concentration range, and also whether
the character of the spectrum of chalkone does not change in the neighbourhood of the maximum.
Kinetic measurements were carried out in methanol (dried over sodium, b.p. 655C). Concen-
tration of chalkone was 4 . 10-
5
M, of ethyl Cl-cyanobutyrate 4. 10-
2
M and of sodium me tho xi de
1' 4 . 10- 3M . The reaction was carried out at the following temperatures: 25, 30, 35, 40 and 45C
TABLE I
Reaction of Chalkones of the Type ArCH= CH- CO- C6H5 with Ethyl Cl-Cyanobutyrate
No
4
10
11
12
13
14
15
p-N(CH
3
h
p-NH
2
p-OCH
3
p-CH
3
H
p-F
p-Cl
m-Cl
p-CN
m-N0
2
p-Fc
m-Fc
Ar = 2-thienyl
Ar = 2-furyl
Ar = Fc
nm
420
397
340
320
308
310
312
299
302
290
347
286
338
342
325
a Refers only to melting points
log e
447
439
4'42
4'42
436
4' 39
446
434
4'56
4'39
4' 39
4' 34
435
445
421
10
3
. k, min-
1
25C 30C 35
c
C
79 07 10' 1 02 16' 4 03
7' 1 0' 2 106
0'2 160 04
16'4 1'4 23'6 0' 5 33-6
15
209 08 31'6 08 395 20
27'9 03 41'5 0'3 51' 7 22
41 28 592 02 666 48
60'2 2'8 832 24 ION 10
64'5
5-8
916
4-6 1186 8
196 53 298
: 5
425 18
231
1
326
7
357

5
226 08 30' 45 0'2 437 09
32'5 2' 5
477
16 62'4 0' 8
26'3 0'8 34' 1 2' 2 439 31
19'3 0'2 258
I-4 358 2'5
693 0'2 II31 04
17-9 0' 3
Collection Czechoslov. Chern. Commun. /Vo\. 34/ (1969)
Michael Addition of Ethyl cx-Cyanobutyrate 2773
(Ultrathermostat; accuracy 0-1 C)_ The course of the reaction was followed by the measurement
of the decrease in the absorbance of the 2 maximum of chalkone in samples withdrawn from the
reaction mixture at suitable time intervals_ The wave-lengths of maxima of chalkones at which
the measurements were carried out, together with log e and the calculated rate constants are
given in Tables I - III. In these tables the calculated values for activation energy and activation
entropy of the studied reactions are also presented_
RESULTS AND DISCUSSION
Additions of ethyl ex-cyanobutyrate were carried out with chalkones of the following
types: C
6
H
s
COCH=CHC
6
H
4
(X) (type A), (X)C
6
H
4
COCH=CHC
6
H
s
(type B),
FcCOCH=CHC
6
H
4
(X) (type C), (X)C
6
H
4
COCH=CHFc (type D), Fc = ferrocenyl
(C1oHgFe)- In order to make sure that in this case too the reaction is of the first
order with respect to chalkone, we carried out the addition of ethyl ex-cyanobutyrate
to unsubstituted chalkone at the following concentrations; 4 _ 1O-
4
M; 2 _ 10-
4
;'1;
4 _ 10- sM_ We found that the half-time of the reaction is independent of the starting
concentration of chalkone (tl/2 = 20-1 1 min; 19-4 0-8 min; 18-8 0-8 min)
and hence that the reaction is of the first order. As we did not isolate the products
TABLE I
(continued)
E - LlS* M_p_
Ref. a
40C 45C
kcal mol-
1
cal mol-'1 grad - 1
C
22-2 I-I 34-3 3-5 14-7 1-4 29-1 0-2 114 14
2N
0-6 30-9 0-4 13-9 0-4 31-9 0-1 151 15
45-9 2-0 62-2 0-6 12-5 0-1 34-9 0-7 77 16
53-3 0-9 74-7 2-2 11 -5 0-6 37-7 0-1 97 17
74-3 2 97-9 I-I 11-6 0-6 36-9 0-1 56 18
105-2 1-4 140-3 11-4 1-0 36-9 0-1 88 19
137-6 9 204

11-6 0-4 35-5 0-1 114 15
173

6 221

11-6 0-9 35-3 0-1 75 20
515

23 723 42
11-9 0-7 32-1 0-1 156 21
927

4 822 59
11-3 1-4 33-9 0-2 148 15
59-I 3 75-1 1-2 11-5 0-3 37-1 0-1 135 - 138 11
78-9 6-9 104

4-4 10-7 0-1 39-5 0-1 150- 153 It
57-8 3-5
72-5
4-7 9-6 0-8 34-5 0-3 57 23
60-8 1-2 66-9 9-2 11-9 0-3 36-8 0-1 37 24
27-2
0-5 41-9 16-7 0-7 22-5 0-1 135 22
Collection Czechos!ov_ Chern_ Commun_ IVol. 341 (l969)
2774 Toma:
of the addition and could not determine A", Guggenheim's method
29
was used
for the calculation of rate constant, which is suitable for such reactions
3
o. Logarithms
of the calculated rate constants were correlated with (J' constants
31
. Working up the
results according to Jaffee
32
gave for chalkones of the type A the results given in Table
IV. These results were obtained when the value for p-dimethylamino derivative was
not taken into account. If the (J'-value according to Jaffee ((J'p = -0' 600) was taken
for it, we obtained at 25C e = 1'091, r = 0'991, Sq = ,0'051 and S = 0' 072, and
at 45C e = 1'032, r = 0'983, sa = 0067 and s = 0,095;-these results are very close
to those given above (Fig. 1).
In the case of chalkones of the type B the results given in Table IV were obtained.
For the computation of the above given values we did not take for corrdation
p-dimethylamino derivative and m-methoxy derivative (points No 1 and 7 in Fig. 2).
If both these derivatives were taken for correlation, but for p-dimethylamino deriv-
ative the value (J' = -0.600
32
was employed, we obtained at the temperature 25C
e = 1'690, r = 0'996, sa = 0043 and s = 0'066, and at 45C e = 1 622, r = O' 995
TABLE n
Reaction of Chalkones of the Type ArCO-CH= CH--C
6
H
s
with Ethyl IX-Cyanobutyrate
No
4
10
11
12
13
14
15
16
17
18
p-N(CH
3
)2
p-NH
2
p-OCH
3
p-CH
3
H
p-F
m-OCH
3
p-CI
p-Br
m-CI
m-Br
m-N0
2
p-N0
2
p-Fc
m-Fc
Ar = 2-thienyl
Ar = 2-fury\
Ar= Fc
11m
390
367
319
308
308
308
308
310
310
312
310
315
318
325
307
322
320
306
a Refers only to melting points.
10
3
k, min-
1
log e - - - - - - . ~ - - - - - - - - - - - ~ ~ - - - - -
25C 30C 35C
4'41
z.s
04 3-6

04
309+ 0'1
430 2'5 03 3'2

0'2 36 0'1
4'51 8' 6
03 12'1

00 162
4-39
17-4 0'3 20'4

312 00
436 279 03 415

56 51'7 2'2
442 4O'2 2' 5 49

6'2 70' 5 2' 9
4'40 32-4 46 42-2

46 592 2'9
4'42 713 23 104-8
1O
141

6
4'34 84-4 13 1086

1 154

425
107-8 6 147

1 189

4' 33 126

8 167
6
118
12
4'34 465 14 655
1l
791 27
4'30 690

9 838

9 1074 37
4' 34 173 09 2286 0'5 31'1 15
4' 47 33' 7 1'8 41'2

1,2 54'9 1'1
4'49 249 0'7 32

0'4 42'5 06
448
44-8
09 65-3

57 77-6 1-4
4'35 3'1 0'1 4'2

0'1 6'0 0'2
Collection Czechoslov. Chern. Comrnun. IVol. 341 (1969)
Michael Addition ~ f Ethyl cx-Cyanobutyrate 2775
SQ = 0050 and S = 0076. These values are close to the above mentioned. In all
instances the correlation is good.
In the case of ferrocene analogues of chalkones the measurements were carried
om only at 45C. The following values were obtained for chalkones of the type C
and D respectively: C - (} = 0'673, r = 0'877, s(1 = 0102 and s = 0'102; D - (! =
= 1'383, r = 0'946, sl! = 0328 and S = 0368 (Fig. 3). The correlation is worse
than in the case of benzene derivatives, because the reactions are slower and they
proceed rapidly toward the equilibrium, so that our readings were relatively less
accurate. In both types of ferrocene analogues of chalkones the sensitivity of the
reaction to the influence of the substituents is rather decreased. This is caused by the
ferrocenyl group which by its electron-donor effect saturates the electron-acceptor
property of the carbonyl group, so that the influence of other substituents cannot
manifest itself to a great extent.
The values given in Table IV were utilized for the calculation of the coefficient
of transfer through the double bond. We obtained the value 11 = 0641 0'016,
TABLE II
(continued)
E - ~ S * M.p.
Ref."
__ 0 _ ________ ______
kcal. mol-'
l
cal mol--
1
grad -1
C
40C 45C
4-9 03
9'1 0'1 10'1 2'1 46'6 0' 7 165 25
57 0' 2 99 03 12-4 2'1 39'4 03 108 20
22'9 08 30'3 2'6 11-8 0'1 38'6 0'1 105 26
42-3 0'1 58-4 04 11 8 08 373 0'1 59 26
743 97' 9 1' 1 11 6 1'5 36' 9 0' 1 56 18
93'9 19 135

6'5 11'5 0'7 36'6 01 78 27
79- 1 01 107

0'1 11 1 0'5 384 00 44 27
189' 3 1 2584 24 11' 9 0'3 34' 1 0'1 97 20
186

2'3 270
17 107 0'5 37-6 0'1 104 20
258

221

8 10' 5 0'2 37-9 0'1 94 27
272

4 412

6 10'S 0' 8 376 01 95 20
964
58 1395 58 9-6 10 38' 1 01 129 20
1328
1O
1890 128 9'3 0'1 38'4 0' 1 146 20
409 26 52-4 1'5 10' 9 1-1 399 0'2 175-178 11
731 1'4 97'1 26 10'1 04 41'7 01 166- 168 11
556 23
10'6
18 99 0'6 42-8 0'1 83 28
939 . 15 153'2 1'5 106 1'2 39' 4 02 89 24
7-6
02
102 0' 2 113 0'4 41 3 0' 1 139 22
COllection Czechoslov. Chern. Commun. IVol. 341 (1969)
2776 Toma:
which is in good agreement with the value given by Jaifee
32
(n = 0'683). We have
further utilized these values (e, r) together with the rate constant values for the
calculation of (J values for both heterocyclesandferrocenyl. Using the values determined
for chalkones of the type A we obtained the results given in Table V, and -on employ-
ing the values determined for chalkones of the type B the results given in the same
table were attained. Fc = fcrrocenyl, (Ja. is the (J constant if the substituent is bound
directly to the reaction center, i.e. if the entire substituted phenyl is substituted by
ferrocenyl. We suppose that (JC6
H
S = O. '
Constants u for ferrocenyl were already determined by the measurement of dissociation con-
stants of acids
3
3- 35, phenols
J3
and protonation of anilines
3
3. The up value ( - 0'155) calculated
by us is close to that determined by the measurement of the dissociation constants of acids ( - 0 18
TABLE III
Reaction of Chalkones Containing Ferrocene Nucleus with Erhyl ex-Cyanobutyrate at 45C
--------_._ - - - --.--_._ ... -
No X log e 10
4
. k , min-
1
M.p., DC
nm (ref. 10)
Fc-CO-CH=CH-C
6
H
4
(X)
p-OCH
3
338 4'31 9'8 150
p-CH
3
316 429 132 1' 5
172-173
3 H 306 438 15'3 1-3 139
4 p-F 308 4'34 163 0'4 152
p-Cl 310 4'44 19'9 160
m-Cl 299 4'32 25'1 2 136-138
p-CN 303 441 41'2 08 225
p-N0
2
318 440 56'3 22 198
(X)C
6
H
4
CO-CH= CH- Fc
p-OCH
3
328 4'40 11'1
19 153-154
10 p-CH
3
325 4'27 18-4 2 141-143
11 H 325 423 260 135
12 p-F 330 4'24 25-4 3'1
157-158
13 m-OCH
3
325 4'27 286 36 93- 94
14 p-Cl 330 4'29 387 5'5
166- 168
15 p-Br 330 4'30 408 163-165
16 m-Cl 330 4'22 147' 1 37 115- 116
17 m-Br 330 4'21 94-8
63 116-118
18 p-CN 330 4'20 1988 10'7 168-169
19 m-N0
2
335 419 2638 34 149
20 p-N0
2
335 4'20 242,4 206 221
Collection Czechoslov. Chem. Commun. /Vol. 34/ (1969)
Michael Addition of Ethyl ex-Cyanobutyrate 2777
or -- 0'17), while the value obtained by other methods are considerably lower ( - 0'05 or - 0'03).
0"", constant which we determined is equal to that obtained by the measurement of the protonation
of anilines. By measuring the dissociation constants of acids higher values were obtained ( - 0'15
FIG. 1
Dependence of log 10
3
k on 0" for Chalko-
nes of the Type C
6
H
s
-CO-CH= CH-
- C
6
H
4
(X)
The numbering corresponds to that
in Table I. Straight lines for 30 and 40C
are shifted to higher values by 0'7. Indication
of temperatures: e 25C, .. 35C, 45<:=,
() 30C. 0 40C.
TABLE IV
36 ,-
log 10J_k
30
,
24 I
0
0
18
12/?:
- 08
7
56
l
jl
4
II
-0-4
Characteristics of the Correlations of log k and 0" for Chalkones of Type A and B
Temperature
C
25
30
35
40
45
25
30
35
40
45
1'103
1092
1-041
1'032
1'054
1687
1695
1-693
1624
1'597
Type A
0992
0991
0'989
0990
0'986
Type B
0'997
0991
0998
0'998
0'997
Collection Czechoslov. Chem. Commuil. IVo\. 341 (1969)
S(!
0059 0'065
0035 0' 044
0'070 0088
0017 0022
0'068 0'085
0039 0053
0'075 0'101
0037 0049
0033 0'044
0040 0054
8
I
110
0-4 08
2778
11
2-4
12
loglO'k
10
8
.
9
2 0 .
e

l6
1.7
6
3 4.
5
.
5
12
0
2
-02 02
()4 OS
"
OS
FIG. 3
Dependence of log 10
4
. k on a for Chalkones
FcCOCH= CHC
6
H
4
(X) 0 and FcCH=
= CHCOC
6
H
4
(X) at 45C
The indication of points corresponds to
that in Table III, Fc = ferrocenyl.
Toma:
FIG. 2
Dependence oflog }O3 . k on a for Chalkones
of the Type (X)C
6
H
4
-CO-CH= CH-
-C
6
H
S
The numbering corresponds to that in
Table II. The straight lines for 30C and
40C are shifted to higher values by 0'7.
Indication of temperatures: e 25C, 0 35C,
45C, __ 30C, f) 40C.
1-1 2 18
1
06
FIG. 4
12 18
13
12
24 )0
log 10)k
25
,
Dependence of log 10
3
. k
4S
on log }O3 . k
2S
for Chalkones C
6
H
5
CH= CHCOC
6
H
4
(X)
and (X)C
6
H
4
CH= CHCOC
6
H
s
0
The numbering of points corresponds
to that in Table I and II. The straight line 0
is shifted to higher values by 03.
Collection Czechoslov. Chern. Commun. /Vol. 34/ (1969)
Michael Addition Of Ethyl ct-Cyanobutyrate 2779
or - 0' 07). Constants ua; known from the literature are much lower (-0'23 to - 0'44) than those
calculated by us ( - 0' 582).
In order to ascertain that all chalk ones of the type A as well as those of the type B
(includingferrocene, thiophene and furan analogues) can be considered as belonging
to one reaction series, and hence, that Hammett's equation can be applied to them,
we carried out the test described by Exner36. We plotted log "45 against log /(2 5
(Fig. 4). A linear relationship was obtained for chalkones of type A, b = 0'947,
r = 0' 999, Sb = 0'016, S = 0026 (calculated for points 1-10). For chalkones of type
B we obtained b = 0'958, r = 0' 999, Sb = 0010 and S = 0026 (calculated for points
1-13). As the order of substituents is not changed, the application of Hammett's
equation is substantiated. The only exception is substance No 15 of type A, where
ferrocenyl is bound directly to the of the double bond, which is the site
of the attack of the reagent. This point is rather deviated from the straight line, and
therefore the given derivative cannot be inserted into the reaction series and we
TABLE V
Calculated Constants for Chalkones of the Type A and B
Temperature
2-Thienyl (u(%) 2-Furyl (u
a
) Fc(u
a
) Fc(u
p
) Fc(u
rn
)
DC

Type A
25
- 0,086
- 0' 205 ( - 0'602) - 0'144 - 0'004
30 - 0'132 - 0-241 (-0'563) - 0'176 - 0-009
35 - 0-143 - 0226 ( - 0-509) - 0-145 - 0-000
40 -0-168 - 0,221
( - 0'479)
-0,159 -0,040
45 - 0-201 -0,233
(- 0' 420) - 0'187 - 0'020
Average -0-146 - 0' 225 (-0'515) - 0-162 - 0-014
0'042 0-013 0'073 0'015 0-016
Type B
25
- 0,050
+ 0' \04 - 0'582 - 0-140 + 0'030
30 - 0'050 + 0'130
- 0-561 - 0'134 + 0-014
35 - 0'053 + 0' 101 - 0553 - 0'133 +0'013
40 -0'065 + 0-074 - 0'595 - 0'147 + 0'008
45 - 0'070 + 0' 111 - 0' 620 - 0'179 - 0'012
Arerage - 0,058
+ 0' 104 - 0' 582 - 0'147 + 0' 010
0'009 0'020 0'026 0'019 0'015
Collection Czechoslov. Chern. Cornmun. /Vol. 34/ (969)
2780 Torna:
cannot calculate a constants for it. (a constants in Table V are in brackets.) The
anomalous position of this derivative is further corroborated by the relatively large
value of E and by the very small value (in comparison with other substances) of
- l'lS* (Table 1). We explain this by the fact that ferrocenyl bound to the carbon
atom which is the site of the attack of the reagent represents a steric hindrance to the
course of Michael addition.
The magnitude of the value b (0947 for type A and 0958 for type B) is a proof
that in the given temperature range the Michael addition 'is not temperature sensitive
(Q == constant). The calculated E values and -l'lS* values which we calculated
according t0
37
also point to this conclusion.
On comparison of the calculated a constants we found that ferrocenyl, if bound
to the reaction center, be the latter the carbon atom of the carbonyl group or the
atom of the double bond, has strong electron donor properties, stronger
than 2-furyl or 2-thienyl. However, these latter two substituents behave in a different
manner, depending on whether they are bound to the carbonyl group carbon atom
or to the atom of the multiple bond. In the first case 2-thienyl has only
very weak electron donor properties and 2-furyl has relatively strong electron acceptor
properties. If both are attached to the of the multiple bond they have electron
donating properties, 2-furyl behaving as a stronger electron donor. We explain this
difference in behaviour by their I-effect which manifests itself strongly if they are
bound to the carbonyl carbon atom. In the entire chalkone molecule the carbonyl
group is primarily responsible for the polarity of bonds as well as of the whole mole-
cule. Electron accepting properties of this group are saturated by the polarisation
of the very mobile n-electrons of the double bond, which is also supported in the case
of Michael addition by the attack of the reagent. Thus, if heterocycles are bound
to the carbonyl group, this does not exhaust the electrons from them. This is also
supported by the fact that the carbonyl group functions as a partial insulator of the
conjugation
38
If heterocycles are bound to the atom, they are practically
at the end of the conjugated system and also on the carbon carrying a positive charge,
and therefore their M effect becomes manifest. The 2-furyl group behaves similarly
to the methoxy group. If this is in para-position + M effect predominates, if in meta-
position - I effect plays a greater role. Ferrocene, when bound to a benzene nucleus,
has approximately the same electron donating effect as the methyl group.
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kladatelstvi CSAV, Prague 1957.
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Chirn. 1965, 1983.
Collection Czechoslov. Chern. Cornmun. IVol. 34{ (1969)
Michael Addition ~ f Ethyl o:-Cyanobutyrate 2781
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11. Toma S., Perjessy A.: Chem. zvesti, in press.
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Translated by 1. Prochazka.
Collection Czechoslov. Chern. Cornmun. IVol. 341 (1969)