A quantum chemical study of unexpected reaction of α-chloroacyl chlorides with 1,2-dichloroethylene in the presence of aluminum chloride

Computational and Theoretical Chemistry 1073 (2015) 116–122

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A quantum chemical study of unexpected reaction of a-chloroacyl chlorides with 1,2-dichloroethylene in the presence of aluminum chloride Vladimir A. Shagun, Galina G. Levkovskaya, Alexandr V. Popov, Igor B. Rozentsveig ⇑ A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 664033 Irkutsk, Russian Federation

a r t i c l e

i n f o

Article history: Received 14 July 2015 Received in revised form 3 September 2015 Accepted 14 September 2015 Available online 28 September 2015 Keywords: Haloenones 1,2-Dichloroethylene Chlorotropic rearrangement Quantum chemical calculations Potential energy surface

a b s t r a c t The reactions of acetyl chloride and chloroacetyl chloride with 1,2-dichloroethylene in the presence of aluminum chloride have been mechanistically studied at the M06/6-311+G(d,p) level of theory. The reaction with acetyl chloride proceeds via the classical channel to afford the expected 1,2-dichlorovinyl ketone. The reaction with chloroacetyl chloride occurs through the alternative channel delivering dichloromethyl-2-chlorovinylketone instead of anticipated chloromethyl-1,2-dichlorovinylketone. The quantum-chemical calculations have shown that the difference between classical and alternative channels is due to the competitive processes occurring at the first stage of the reaction, namely formation of adducts and elimination of hydrogen chloride. In the reaction involving acetyl chloride, the first channel is kinetically more favorable, whereas in the reaction with participation of chloroacetyl chloride, the second channel becomes preferable. Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction The reactions of acyl halides with acetylene, ethenes and chloroethenes in the presence of Friedel–Crafts catalysts are known to be widely used in the synthesis of polyhaloenones that are extensively applied in organic chemistry as versatile building blocks [1–8]. Halovinyl ketones are successfully employed for the preparation of functionalized alkenes [1–4], diverse hardly accessibly heterocyclic derivatives of oxazoles and pyrazoles [1–9], furans [10], dithioles, dithietane [5], and thiophene [11,12], etc. This stimulates the search of efficient and selective synthetic routes to novel haloenones [9–22], including large-scale synthesis [22], as well as investigations of their reactivity [1–27]. Among a range of halovinyl ketones only a limited number of representatives containing halogen atoms both in alkyl and in vinyl fragment is known. For instance, polyhalomethyl 2,2-dichlorovinyl ketones, dichloromethyl 1,2-dichlorovinyl ketone, and trifluoromethyl substituted 2-chloro-, 2,2-dichloro, 2,2-difluoro-, 2,2-dibromovinyl ketones are described [2,3,5–9,27–38]. 1,2-Dihalovinyl ketones are promising building-blocks for heterocyclic synthesis, but their chemistry is the least studied and

⇑ Corresponding author. Tel.: +7 395 251 1434, +7 395 241 9346; fax: +7 3952 419 346. E-mail address: [email protected] (I.B. Rozentsveig). http://dx.doi.org/10.1016/j.comptc.2015.09.017 2210-271X/Ó 2015 Elsevier B.V. All rights reserved.

restricted to earlier communications [2,27,28] and investigations of cyclic 1,2-dichloroenones [29–34]. It has been found [35] that the reactions of acyl chlorides with 1,2-dichloroethylene proceed via the formation of saturated adducts, 1,1,2-trichloroethyl alkyl ketones, to afford 1,2-dichlorovinyl ketones (Scheme 1). No other ketones have been detected [35]. Earlier, it has been reported that chloroacetyl chloride in the similar reaction with 1,2-dichloroethylene gives chloromethyl 1,2,2-trichloroethyl ketone, which delivers oxime or semicarbazone of chloromethyl 1,2-dichlorovinyl ketone under the action of hydroxylamine or semi-carbazide respectively (Scheme 2) [27,28]. Thus, it has been supposed [1–7,27,28,36–38] that the direction of the reactions between acyl chlorides and 1,2-dichloroethylene is easily predicted. The major products of such reactions are saturated adducts, the corresponding trichloroethyl ketones, which are readily (on heating or by treatment with bases) dehydrochlorinated to form 1,2-dichlorovinyl ketones. Keeping up our investigations in the field of chemistry of polyhaloenones, we have established for the first time that the reactions of a-chloroacyl chlorides 1a–c with 1,2-dichloroethylene 2 in the presence of aluminum chloride proceed in an unusual fashion to unexpectedly give 1,1-dichloroalkyl 2-chlorovinyl ketones 3a–c as a result of chlorotropic and prototropic rearrangements [39–42].

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O Alk

O

Cl Cl

+

Cl

Alk

Cl

O

O Cl

Alk

Cl

Cl Cl R

+

Cl

Cl

Cl 1a-c

Scheme 1. Reaction of acyl chlorides with 1,2-dichloroethylene.

2

Cl 5b,c

Cl

R -HCl

Cl Cl Cl 3b,c

O R Cl

-HCl

In the present work a quantum chemical study of possible mechanisms for the reactions of 1,2-dichloroethylene 2 with acetyl chloride 1d and chloroacetyl chloride 1a in the presence of aluminum chloride was carried out.

O Cl

Cl

O

Alk = Me, Et, Pr

Cl

R

Cl Cl

R = H (a), Me (b), Et (c)

4a-c

Scheme 3. Synthesis of polyhaloenones in reactions of chloroacyl chlorides with 1,2-dichloroethylene. Table 1 Reagents and yield of polychloroenones 3, 4.

2. Material and methods

Entry

The calculations were performed by M06 and B3LYP methods [43–47] using 6-311+G(d,p) basis set of Gaussian-09 package [48]. Relative stability of adducts and energy profiles of the reactions studied are given in DG scale. The pseudo-potentials were successfully used in mechanistic studies of the reactions of halo-containing compounds (see, for example, 49,50). Stationary points were identified by analysis of the Hesse matrix. Search and localization of the transition states TS were performed by the synchronic transit method [51] (QST). Analysis of vibration frequencies was carried out, and conformity of critical points to the gradient line connecting them was proved by the internal reaction coordinate (IRC) technique [52,53]. Solvation effects were assessed using SCRF = IPCM model with e = 2.14 (1,2-dichloroethylene). Reactions of a-chloroacyl chlorides 1a–c with 1,2-dichloroethylene 2 (mixture of cis and trans isomers) were carried out according to our methods [40–42] at various ratio of the reagents (a-chloroacyl chloride: AlCl3: 1,2-dichloroethylene = 1: 1: 1.5–6.5). All of the products 3b–d, 4a–d and 5b,c were isolated in a pure E-form. Spectral data and constants for the compounds synthesized are in accordance with Refs. [39–42].

1

3. Results and discussion Under the conditions employed for the synthesis of alkyl 1,2-dichlorovinyl ketones [35] and chloromethyl 1,2,2-trichloroethyl ketone [27,28], the reaction of chloroacetyl chloride 1a with 1,2-dichloroethylene 2 in the presence of aluminum chloride results in dichloromethyl 2-chlorovinyl ketone 4a as the only product similarly to Refs. [39,40] (Scheme 3, Table 1). The expected reaction products, chloromethyl 1,2,2-trichloroethyl ketone or chloromethyl 1,2-dichlorovinyl ketones 3a, are formed neither under the conditions described in the literature [27,28,35] nor at various ratio of the reagents (chloroacetyl chloride: AlCl3: 1,2-dichloroethylene = 1: 1: 1.5–6.5).

NH2OH

O Cl Cl

+

O

Cl

Cl Cl

OH Cl Cl

Cl

Cl Cl

N Cl

O O NH2NHCNH2

N

NH2 NH

Cl

Cl Cl

Scheme 2. Reaction of chloroacetyl chlorides with 1,2-dichloroethylene.

Starting chloroacyl chloride 1

Polychloroenone 3 (yield, %)

O Cl

O Cl

O

Cl

Cl

1a 2

Polychloroenone 4 (yield, %)

Cl

Cl 3a (0)

Cl Cl

O

O

O Cl Cl 1b

Cl

Cl

Cl

Cl

4a (70-84)

Cl Cl

4b (49)

3b (15) 3

Cl Cl 1c

O

O

O

Cl

Cl Cl

Cl

Cl Cl

4c (16)

3c (34)

2-Chloropropanoyl chloride 1b or 2-chlorobutanoyl chloride 1c react with 1,2-dichloroethylene 2 in two directions. The first way is the formation of anticipated 1,2,2-trichloroethyl 1-chloroalkyl ketones 5b,c and 1-chloroalkyl 1,2-dichlorovinyl ketones 3b,c. The next one is unexpected synthesis of 1,1-dichloroalkyl 2-chlorovinyl ketones 4b,c [41,42]. It has been noted that with elongation of the alkyl chain of the starting 2-chloroacyl chloride 1a–c the yield of unexpected 1,1dichloroalkyl 2-chlorovinyl ketones 4a–c decreases, while the yield of the expected 1,2-dichlorovinyl ketones 3a–c simultaneously increases (Table 1). Since the addition of acyl chlorides to ethenes has a significant importance both for theoretical and synthetic organic chemistry, investigation of the unexpected formation of 2-monochlorovinyl ketones 4a–c in the reaction of a-chloroacyl chlorides 1a–c with 1,2-dichloroethylene 2 is an urgent challenge. In the present work, we have unambiguously found that 1,1-dichloroalkyl 2-chlorovinyl ketones 4 cannot be formed from 1-chloroalkyl trichloroethylketones 5b,c or 1,2-dichlorovinyl ketones 3b,c on heating in the presence of AlCl3. At the same time, the reaction mechanism proposed by us previously [40] is not valid since it does not allow one to explain the formation of the corresponding chloroketones 4b,c from 2-chloropropanoyl chloride 1b or 2-chlorobutanoyl chloride 1c [41,42]. Therefore, to elucidate the reasons and a tentative mechanism of the unexpected formation of chloroenone 4, we carried out a quantum chemical investigation of potential energy surface (PES) for the reactions of 1,2-dichloroethylene 2 with acetyl chloride 1d and chloroacetyl chloride 1a (Scheme 4). The quantum chemical study was performed to determine the possible reasons of the unexpected alteration of the reaction channel on going from acyl chlorides to chloroacyl chlorides. The comparative study of gradient channels for the classical and alternative mechanisms of the reaction is performed on the

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O

O R

R=H

Cl 1a,d + Cl

Cl

Cl

Cl -HCl Cl 5d

AlCl3

Cl

traditional channel

3d

O

R = Cl -HCl

2

O

Cl

Cl

alternative channel

Cl 4a

Cl

R = Cl (a), H (d) Scheme 4. Traditional and alternative channels in reactions of 1,2-dichloroethylene with acetyl chloride and chloroacetyl chloride.

example of acetyl chloride 1d and chloroacetyl chloride 1a in the presence of aluminum chloride, that lead to monoproducts, methyl 1,2-dichlorovinyl ketone 3d and dichloromethyl 2-chlorovinyl ketone 4a, respectively (Scheme 4). When interacted with the catalyst, the starting compounds 1 and 2 are capable to form different stable adducts due to the coordination bonding of aluminum atom with heteroatoms of the partners (Scheme 5). The calculations have shown that the stability of the adducts 6a, b, 7a–c, 8a,b varies significantly (Table 2). Structures stabilized by coordination interaction Al- - -O (6b and 7c) are significantly more stable. Relative stability of adduct 6b is by 11.4 kcal/mol higher than that of the chlorine-coordinated analog 6a. This value for adduct 7c exceeds that for analogues 7a and 7b by 9.0 kcal/mol and 6.8 kcal/mol, respectively (Table 2). The thermal effect of the formation of adduct 8b formation (calculated as difference between the total energy of isolated optimal states of the starting compounds and adduct) is lower than that of 6b and 7c by 10.7 kcal/mol and 8.3 kcal/mol. Taking into account these results one can assume that the most probable reaction routs to 1,2-dichlorovinyl ketone 3d and dichloromethyl 2-chlorovinylketone 4a run via adducts 6b and 7c. Thus, adducts 6b and 7c were used as the starting structures for further analysis of the reaction mechanisms. The optimal molecular structures for 6b and 7c shown in Fig. 1. The difference between classical and alternative channels (Scheme 4) is likely due to the competitive processes occurring at the first stage of the reaction, namely formation of saturated ketones, chloromethyl(1,2,2-trichloroethyl)ketone or methyl-1,2,2

O Cl

O

AlCl3

AlCl3

O Cl

Cl

6a

O

Cl

Cl 7b

AlCl3 Cl

Cl3Al

7a

6b

Cl

O AlCl3

Cl

Cl Cl

Cl

AlCl3

8a

7c

8b

Cl

AlCl3

Scheme 5. Adducts of AlCl3 with acetyl chloride, chloroacetyl chloride, and 1,2-dichloroethylene. Table 2 Relative stability of adducts 6a,b, 7a–c, 8a,b, calculated with M06/6-311+G(d,p) method (298.15 K and 1 atm).

a b c

Compound

DG

Compound

DG

6a 6b 7a 7b

0.0 11.4a 0.0 2.2b

7c 8a 8b

9.0b 0.0 1.8c

Relative to adduct 6a. Relative to adduct 7a. Relative to adduct 8a.

-trichloroethylketone, from adduct (6b or 7c) and 1,2dichloroethylene, and elimination of hydrogen chloride in adduct (6b or 7c). The chemical experiments have shown that in the classical channel (with participation of acetyl chloride 1d), elimination takes place at the last stage of the reaction to give intermediate stable chloromethyl(1,2,2-trichloroethyl)ketone (Scheme 4, structure 5d). In the alternative channel involving chloroacetyl chloride 1a, no traces of saturated ketone are detected among the reaction products (NMR monitoring). Obviously, hydrogen chloride is eliminated at the stage of adduct 7c formation. The alteration of the reaction channel topology (from classical to alternative) is mainly owing to a higher acidity of the chloromethyl group proton as compared to acidity of the methyl group proton. At structural level, this effect is observed in different lengths of the CAH – bonds in adducts 6b (RCAH = 1.090 Å) and 7c (RCAH = 1.095 Å) (Fig. 1). In the classical channel (Scheme 4), the interaction of adduct 6b with 1,2-dichlorovinyl ketone leads to stabilization of pre-reaction molecular system 6b-2 by 9.5 kcal/mol (Fig. 3). The stabilizing effect, in particular, is due to more stable coordination bonding Al- - -O in molecular system 6b-2 as compared to isolated adduct 6b [1.944 Å (6b-2), 1.971 Å (6b)] (Figs. 1 and 2). The formation of adduct 5d
AlCl30 (Fig. 2) in molecular system 6b-2 (classical channel) represents a concerted process. Aluminum chloride promotes 1,3-chlorotropic shift (Scheme 6). The value of activation barrier of the reaction (6b-2 ? 5d
AlCl30 ) TS1 (Fig. 2) is 33.0 kcal/mol (Fig. 3, Table 3). As for the role of the catalyst, it should be emphasized that non-catalytic process (1d + 2 ? 5) proceeds with overcoming the activation barrier of 43.2 kcal/mol. Thermodynamic stability of adduct 5d AlCl30 , obtained from the reaction (6b-2 ? 5d
AlCl30 ), is by 7.6 kcal/mol higher than that of the starting state of molecular system 6b-2 (Fig. 3). Thermodynamically controlled structural reorganization of adduct 5d
AlCl30 occurs through two channel. The first one involves elimination of hydrogen chloride (5d
AlCl30 ? 3d
AlCl3
HCl). The second one assumes migration of the catalysts (coordinatively bonded with compound 5d) from chlorine to oxygen atom (5d
AlCl30 ? 5d
AlCl300 ) (Fig. 2). In the first channel [similar to the reaction (6b-2 ? 5d
AlCl3)], the catalyst plays the role of molecule-mediator promoting elimination of hydrogen chloride via six-centered transition state (Scheme 7). Elimination of hydrogen chloride in the reaction (5d
AlCl30 ? 3d
AlCl3
HCl) proceeds via the transition state TS2 (Fig. 2) with overcoming the activation barrier of 17.0 kcal/mol (Fig. 3, Table 3). As a consequence, thermodynamic stability of the molecular system (3d
AlCl3
HCl) increases by 16.0 kcal/mol (Fig. 3). Compared to non-catalytic elimination (5d ? 3d, DE# = 48.1 kcal/mol), in this case, the activation barrier decreases by almost 3 times. The second channel of structural reorganization of adduct (5d
AlCl30 ) with alternated coordination center of aluminum chloride (5d
AlCl30 ? 5d
AlCl300 ) involves overcoming the activation barrier of 4.9 kcal/mol (TS20 , Fig. 2) thus increasing the stability of adduct (5d
AlCl300 ) by 16.6 kcal/mol (Table 3). Noteworthy, thermodynamic and kinetic parameters of addition and dehydrohalogenation (within 0.2 kcal/mol) do not depend upon conformation (cis-, trans-) of 1,2-dichloroethylene. In comparison with the above reaction (6b-2 ? 5d
AlCl30 ), the formation (experimentally unproved) of chloromethyl-1,2,2-trichloroethyl ketone 9 in the reaction of adduct 7c with dichloroethylene 2 (7c-2 ? 9
AlCl3) proceeds with overcoming a higher activation barrier TS10 (37.3 kcal/mol, Fig. 3). Structure of the transition state is depicted in Fig. 2. The elimination of hydrogen chloride in adduct 7c (Fig. 1) via alternative reaction channel (Scheme 4) (7c ? 10
AlCl3
HCl) proceeds through the transition state TS3 (Fig. 5) with overcoming the activation barrier of 28.1 kcal/mol (Fig. 4). Subsequent

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6a

1d

1a

7a

6b

7c

7b

Fig. 1. The molecular structures and the main geometry characteristics for the starting compounds 1a, 1d and for the most stable adducts 6a,b, 7a–c, formed by 1a,d with AlCl3. The calculations were performed using M06/6-311+G(d,p) method. The bond lengths are given in Å, values of angles are in degrees.

6b-2

TS2

5d.AlCl3’’

5d.AlCl3’

TS1

3d.AlCl3.HCl

TS2'

TS1'

9.AlCl3

Fig. 2. The molecular structures and the basic geometry of the key molecular system states in the classical reaction channels (6b-2 ? 5d
AlCl3 ? 3d
AlCl3
HCl) and (7c-2 ? 9
AlCl3), calculated using M06/6-311+G(d,p) method. The lengths of the bonds are given in Å.

thermodynamically controlled interaction of adduct 10
AlCl3 with 1,2-dichloroethylene occurs via the transition state TS4 (Fig. 5) to afford adduct 4a
AlCl3 (Fig. 5). Enthalpy of the reaction (10
AlCl3-2 ? 4a
AlCl3) is 40.9 kcal/mol (Fig. 4).

To compare the kinetic characteristics of potentially competitive reactions of hydrogen chloride elimination in adducts 7c and 6b, the transition state TS30 (Fig. 5) was found and a barrier of hydrogen chloride elimination in adduct 6b was calculated

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V.A. Shagun et al. / Computational and Theoretical Chemistry 1073 (2015) 116–122 Table 3 The imaginary or lowest harmonic frequency (iw/x1, cm1) and relative energies (DG, kcal/mol) of the key states of molecular systems in the formation of compounds 5d, 3d and 4a, calculated by M06/6-311+G(d,p) method (298.15 K and 1 atm).

Cl Cl 6b-2

Al

Cl

Me

Cl H

5d AlCl3

O Cl

Cl

H

Scheme 6. 1,3-Chlorotropic shift promoted by AlCl3.

(6b ? 10
AlCl3
HCl). The value of activation barrier for TS30 is by 5.6 kcal/mol higher than that of barrier for TS3 of elimination reaction in adduct 7c (pbc.4). It should be noted that similar to the classical channel, in the alternation channel of the reaction, the catalyst also plays the role of molecule-mediator for lowactivated overcoming the activation barriers TS3, TS30 and TS4. The calculated values of the activation parameters for the reactions (TS1, TS30 ) and (TS10 , TS3) (Table 3) demonstrate kinetically controlled advantages of the classical channel in the reaction involving acetyl chloride and benefits of the alternative channel in the processes with participation of chloroacetyl chloride that is in good agreement with experimental data. For comparative assessment of the solvation effect on kinetic characteristics of the formation of saturated ketone, methyl-1,2,2 -trichloroethylketone 5d and chloromethyl-1,2,2-trichloroethylke tone 9, in the reactions [(6b-2 ? 5d
AlCl30 ) TS1 and (7c-2 ? 9
AlCl3) TS10 ], as well as on hydrogen chloride elimination in the reaction [(7c ? 10
AlCl3
HCl) TS3 and (6b ? 11
AlCl3
HCl) TS30 ], we have performed the calculations using SCRF = IPCM (e = 2.14, 1,2-dichloroethylene) method. The calculated values of activation barriers (TS1, TS10 ) and (TS3, TS30 ) taking into account the solvation effect c are given in Figs. 3 and 5 (round brackets). The calculations have shown that consideration of the solvation effect

System

iw/x1

DG

System

iw/x1

DG

6b-2 TS1 5d
AlCl30 TS2 3d
AlCl3
HCl TS20 5d
AlCl300 7c-2 TS10 9
AlCl3

23 i203 20 i692 25 i68 13 17 i320 26

0.0 33.0a 7.6a 24.6a 8.4a 12.5a 9.0a 0.0 37.3b 3.8b

7c TS3 10
AlCl3
HCl 10
AlCl3-2 TS4 4a
AlCl3 6b TS30 11
AlCl3
HCl

26 i80 18 12 i172 16 30 i662 41

0.0 28.1c 26.9c 0.0 41.6d 40.9d 0.0 33.7e 24.6e

a b c d e

Relative Relative Relative Relative Relative

to to to to to

molecular system 6b-2. molecular system 7c-2. adduct 7c. molecular system 10
AlCl3-2. adduct 6b.

does not lead to inversion of the results obtained in gas-phase state. The values of activation barriers (TS1 and TS10 ) decrease by 7.6 kcal/mol and 6.6 kcal/mol, respectively (Fig. 3). In the processes of hydrogen chloride elimination, the activation barriers (TS3 and TS30 ) decrease less significantly (by 1.1 kcal/mol and 0.5 kcal/mol, correspondingly, Fig. 5). With the growth of the alkyl chain of the starting 2-chloroacyl chloride 1a, acidity of the chloroalkyl group proton drops thus augmenting a barrier of hydrogen chloride elimination (TS3), and hence increasing the competitive ability of the classical channel. Obviously, this effect leads to the formation of the expected products in the reaction involving chloroanhydrides of 2-chloropropane 1c and 2-chlorobutane 1b acids (Table 1).

Fig. 3. A mechanism of compounds 3d, 5d and 9 via classical reaction channel according to M06/6-311+G(d,p) calculations. The values of activation barriers for TS1 and TS10 taking into account the solvation effect are given in brackets [SCRF(IPCM), e = 2.14].

O

H Cl Cl

Me Cl

Al

H Cl

Cl

H

Cl

H

Cl

Me

Al Cl

Cl

O

Cl

Cl

Me

Al

H

O

Cl

Cl

Al

Cl

Scheme 7. Elimination of hydrogen chloride via six-centered transition state.

Cl

H

Cl

Cl

V.A. Shagun et al. / Computational and Theoretical Chemistry 1073 (2015) 116–122

121

Fig. 4. A mechanism of compounds 4a, 10 and 11 formation via the alternative reaction channel according to M06/6-311+G(d,p) calculations. The values of activation barriers for TS3 and TS30 taking into account the solvation effect are given in brackets [SCRF(IPCM), e = 2.14].

TS3

4a.AlCl3

10.AlCl3.HCl

TS3'

TS4

11.AlCl3.HCl

Fig. 5. The molecular structures and the basic geometry characteristics for the key states in the alternative reaction channel (7c ? 4a
AlCl3) and (6b ? 11
AlCl3
HCl), calculated by M06/6-311+G(d,p) method. The lengths of the bonds are given in Å.

Acknowledgment Spectral and analytical data were obtained with equipment of Baykal analytical center for collective use SB RAS. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.comptc.2015.09. 017. References [1] N.K. Kochetkov, Chemistry of b-chlorovinylketones, Uspekhi Khim. 24 (1955) 32–51. Chem. Abstr. 49 (1955) 7544c. [2] A.E. Pohland, W.R. Benson, b-Chlorovinyl ketones, Chem. Rev. 66 (1966) 161– 197. [3] M.B. Rybinskaya, A.N. Nesmeyanov, N.K. Kochetkov, b-Oxovinylation, Uspekhi Khim. 38 (1969) 961–1008. Chem. Abstr. 71 (1969) 48884j. [4] I.D. Sadekov, b-Telluroacroleins and tellurovinyl ketones: synthesis, reactions and structures, Russ. Chem. Rev. Engl. Transl. 71 (2002) 929–941.

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