Mechanism and stereochemistry of domino reaction of 2,3-dichloroprop-1-ene with diphenyl dichalcogenides in the system hydrazine hydrate - KOH

Article abstract of DOI:10.1007/s11172-014-0659-7

A new scheme of the domino reactions of diphenyl dichalcogenides with 2,3-dichloroprop-1-ene in the system hydrazine hydrate - KOH was suggested, which included nucleophilic substitution of the allylic chlorine atom in dichloropropene, dehydrochlorination of the product obtained with the formation of an allene derivative, addition of a nucleophile to the allene system, allene-acetylene rearrangement, addition of a nucleophile to the triple bond with the formation of a Z-adduct, isomerization of a 2,3-dichalcogenide product to Z-1,2-dichalcogenylprop-1-enes, and isomerization of Z-adducts to E-isomers. The most plausible mechanisms of individual steps, involving carbanions stabilized by the α-chalcogen atom, were considered.

Full text of DOI:10.1007/s11172-014-0659-7

Russian Chemical Bulletin, International Edition, Vol. 63, No. 8, pp. 1722—1727, August, 2014
1722
Mechanism and stereochemistry of domino reaction of 2,3ꢀdichloropropꢀ1ꢀene
with diphenyl dichalcogenides in the system hydrazine hydrate—KOH
E. P. Levanova, V. S. Vakhrina, V. A. Grabel´nykh, I. B. Rozentsveig, N. V. Russavskaya,
A. I. Albanov, and N. A. Korchevin
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
1 ul. Favorskogo, 664033 Irkutsk, Russian Federation.
Fax: +7 (395 2) 41 9346. Eꢀmail: venk@irioch.irk.ru
A new scheme of the domino reactions of diphenyl dichalcogenides with 2,3ꢀdichloropropꢀ
1ꢀene in the system hydrazine hydrate—KOH was suggested, which included nucleophilic
substitution of the allylic chlorine atom in dichloropropene, dehydrochlorination of the prodꢀ
uct obtained with the formation of an allene derivative, addition of a nucleophile to the allene
system, alleneꢀacetylene rearrangement, addition of a nucleophile to the triple bond with the
formation of a Zꢀadduct, isomerization of a 2,3ꢀdichalcogenide product to Zꢀ1,2ꢀdichalcoꢀ
genylpropꢀ1ꢀenes, and isomerization of Zꢀadducts to Eꢀisomers. The most plausible mechaꢀ
nisms of individual steps, involving carbanions stabilized by the ꢀchalcogen atom, were conꢀ
sidered.
Key words: domino reactions, 2,3ꢀdichloropropꢀ1ꢀene, chalcogenꢀcontaining nucleophiles,
stable carbanions, hydrazine hydrate, stabilization, stereochemistry, mechanism.
A growing sphere of application of organosulfur1 and
ꢀselenium2 compounds continuously stimulates developꢀ
ment of synthetic methods of organochalcogen chemistry.
An important role in the synthesis of sulfur and selenium
organic derivatives is played by the chalcogenꢀcontaining
nucleophilic agents, which are easily obtained by reducꢀ
tive activation of available elementary chalcogens and orꢀ
ganic dichalcogenides.3 Among a large number of basic
reductive systems for the generation of chalcogenꢀconꢀ
taining nucleophiles, an important place is taken by the
systems based on hydrazine used as commercially availꢀ
able hydrazine hydrate.3 Using such systems, preparativeꢀ
ly simple methods for the synthesis of organic chalcoꢀ
genides and dichalcogenides were developed,3 as well as
oligomeric products containing chalcogen atoms in the
chain.4 This type of reactions use organic halides and diꢀ
halides as electrophiles in which halogen is attached to the
carbon atom in the sp3ꢀhybridization state.
atom attached to the sp3ꢀhybridized carbon atom is inꢀ
volved in the reaction). Bis(2ꢀchloropropꢀ2ꢀenꢀ1ꢀyl)
disulfide was obtained using the system hydrazine hyꢀ
drate—monoethanolamine from sulfur and dichloropropꢀ
ene 1.7 Selenium in both basic reductive systems formed
only bis(2ꢀchloropropꢀ2ꢀenꢀ1ꢀyl) selenide.8
The reaction of Ph2S2 (see Ref. 9) and Ph2Se2 (see
Ref. 10) with dichloropropene 1 proceeds through sequenꢀ
tial transformations, including nucleophilic substitution
of the chlorine atom at the sp3ꢀhybridized carbon atom,
dehydrochlorination of the product obtained with the forꢀ
mation of an allene derivative, alleneꢀacetylene rearrangeꢀ
ment, and addition of the PhS– and PhSe– anions to the
triple bond (domino reaction). In the last step, the adꢀ
dition product has the Zꢀconfiguration. The studies showꢀ
ed9,10 that the nature of the chalcogen atom in the PhY–
anion (Y = S, Se) has a considerable influence on the
course of individual steps of the domino reaction.
These reactions allow one to obtain unsaturated organoꢀ
chalcogen compounds possessing a wide synthetic scope
for design of new, sometimes unique, chalcogenꢀcontainꢀ
ing structures.11
In the present work, we consider individual steps of
domino reactions from the point of view of their possible
mechanism. To obtain additional information on the inꢀ
fluence of the nature of the chalcogen atom in nucleophile
PhY–, we also studied the phenoxide anion obtained
by dissolution of phenol in the system hydrazine hyꢀ
drate—KOH (Scheme 1).
2,3ꢀDichloropropꢀ1ꢀene (1) is an dielectrophile, in
which two chlorine atoms are attached to the different
sp3ꢀ and sp2ꢀhybridized carbon atoms. A well known "inꢀ
ertness" of halogens at the double bond to nucleophilic
reactions5 considerably affects direction of the reaction
of dichloropropene 1 with the chalcogenꢀcontaining nuꢀ
cleophiles.
Earlier,6 we have shown that elementary sulfur actiꢀ
vated in the system hydrazine hydrate—KOH to anions
2–
S2 reacts with dichloropropene 1 with the formation of
bis(2ꢀchloropropꢀ2ꢀenꢀ1ꢀyl) sulfide (only the chlorine
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1722—1727, August, 2014.
1066ꢀ5285/14/6308ꢀ1722 © 2014 Springer Science+Business Media, Inc.

Mechanism of dominoꢀreaction
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 8, August, 2014
1723
Scheme 1
Zꢀisomers of compounds 6b,c upon prolongation of the
contact, which, in turn, slowly isomerize to the correꢀ
sponding Eꢀisomers. Based on this, we suggested a new
sequence for the steps of the process, as it is shown in
Scheme 3.
Reagent 2a was synthesized at the ratio phenol : KOH =
= 1 : 2.5. Excess of KOH corresponds to the amount of
the alkali used for the reductive cleavage of Ph2Y2 (Y = S,
Se).3 For obtaining reagents 2b,c, we used the ratio
Ph2Y2 : KOH = 1 : 5 (Scheme 2).9,10 Benzenechalcogenoꢀ
lates 2a—c were used in the reaction without isolation
from the solutions in hydrazine hydrate.
Step a of the domino reaction (see Scheme 3) virtually
is the only possible when reaction is carried out at the
temperatures from –25 to –35 C for PhS– anions (see
Ref. 9) and from –5 to –10 °C for PhSe– anions.10 At
temperatures within 30—35 C, only first three steps a—c
proceed, in which case the ratio of products 3—5 considꢀ
erably depends on the nature of the chalcogen atom.9,10
Step d and steps e—f are possible only at higher temperaꢀ
tures (60 C).
Scheme 2
Potassium phenoxide (2a) obtained in the system hydrꢀ
azine hydrate—KOH (see Scheme 1) virtually does not
react with 2,3ꢀdichloropropꢀ1ꢀene (1). Carrying out the
reaction at 0 C for 14 h gives the product of the first step
of the domino reaction (see Scheme 3), viz., 2ꢀchloroꢀ3ꢀ
phenoxypropꢀ1ꢀene (3a), in only ~2% yield.
Y = S (b), Se (c)
When the temperature of the process is raised to
30—35 C (4 h), compound 3a is formed only in trace
amounts, whereas at 60 C (19 h) the product 3a is absent.
These reactions lead to the products of alkylation of hyꢀ
drazine in 25—40% yield, mainly to (2ꢀchloropropꢀ1ꢀenꢀ
3ꢀyl)hydrazine (8) (Scheme 4).
A possibility of alkylation of hydrazine with dichloroꢀ
propene 1 presents itself when the reactivity of nucleoꢀ
philes present in the reaction mixture is low, which was
discussed by us earlier.6 A low reactivity of the PhO– anꢀ
ions (as compared to the PhS– and PhSe– anions) in the
nucleophilic substitution reactions is a well known fact.12
Step e is a nucleophilic addition of the PhY– anions to
allene chalcogenide 4b,c (Scheme 5). In this case, the
nucleophilic attack is directed on the central atom of the
allene fragment of molecule 4b,c with the formation of the
intermediate carbanion A, in which the negative charge is
concentrated on the carbon atom at ꢀposition to the sulꢀ
fur (or selenium) atom (antiꢀMarkovnikov addition).
According to the literature data,9,10 the domino reacꢀ
tion under consideration (Scheme 3) includes the formaꢀ
tion of 2ꢀchloroꢀ3ꢀphenylchalcogenylpropenes 3b,c (step a),
allene derivatives 4b,c (step b), 1ꢀphenylchalcogenylꢀ
propꢀ1ꢀynes 5b,c (step c), and Zꢀ1,2ꢀbis(phenylchalcoꢀ
genyl)propꢀ1ꢀenes Zꢀ6b,c (step d). By more detailed studꢀ
ies of the influence of the ratio Ph2Y2 : KOH and the reacꢀ
tion time, two more types of compounds were additionalꢀ
ly identified in the products: Eꢀ1,2ꢀbis(phenylchalcoꢀ
genyl)propꢀ1ꢀenes (Eꢀ6b,c) (the highest yields were 6 and
5% for Y = S and Se, respectively) and 2,3ꢀbis(phenylꢀ
chalcogenyl)propꢀ1ꢀenes (7b,c) (the highest yields were
2 and 8% for Y = S and Se, respectively).
The yields of the domino reaction products involving
three types of nucleophiles 2a—c under different condiꢀ
tions (taking into account the data in the works9,10) are
given in Table 1. It can be suggested that compounds 7b,c
are kinetically controlled products and transform to
Scheme 3
Y = O (a), S (b), Se (c)

1724
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 8, August, 2014
Levanova et al.
Table 1. The yields of products of domino reactions of nucleophiles PhY– from compounds 2a—c with dichloropropene 1
PhY–
Ratio (mol.)
T/C
/h
Product yields (%)
Ref.
KOH : Ph2Y2
Ph2Y2 : 1
3
4
5
Zꢀ6
Eꢀ6
7
PhS– (2b)
5 : 1d
5 : 1d
1 : 2
1 : 2
1 : 2
1 : 2
1 : 2
1 : 1
1 : 1
1 : 2
1 : 2
1 : 2
1 : 2
1 : 1
1 : 1
1 : 1
1 : 1
1 : 1e
1 : 1e
–(25—35)
–(5—10)
–(12—20)
30—35
60
60
60
–(5—10)
5—10
25
25
30—35
60
60
60
7.5
7
12
4
19
18
2
7.5
7.5
15
33
7
19
5
18
14
4
70
56
66а
15
—
—
—
85
81
—
—
36
—
—
—
12f
Traces
15
—
23
Traces
—
11
Traces
12
19
13
—
—
—
23
22
—
38
—
—
58
59c
8
—
—
—
—
—
—
—
—
—
40
47
24
—
—
—
—
—
60
54
50
—
—
—
—
—
—
—
6
—
—
—
—
—
—
2
—
—
—
—
—
5
19
19
19
19
19
2 : 1d
5 : 1d
5 : 1d
10 : 1d
5 : 1d
—
—
b
b
1
PhSе– (2с)
5 : 1d
—
—
—
—
—
Traces
1
5
—
—
10
10
10
10
10
5 : 1d
10 : 1d
10 : 1d
5 : 1d
43
—
—
—
5 : 1d
5 : 1d
—
b
b
8
5
—
—
—
10 : 1d
2.5 : 1d
2.5 : 1d
—
b
PhO– (2a)
0
—
—
b
b
30—35
Traces Seeg
—
a Conversion of Ph2S2 95%.9
b The data obtained in this work.
c 1ꢀPhenylselanylpropene (2—3%) was also identified in the reaction mixture.10
d The ratio KOH : PhOH.
e The ratio PhOH : 1.
f Chloropropenylhydrazine 8 was identified in 39% yield.
g Compound 8 was identified in 28% yield.10
Scheme 4
reagents contacted at 60 C for 2 h. In this case, allene
derivative 4b (~1% yield ) and acetylene sulfide 5b (38%
yield) remain unreacted in the reaction mixture (see Table 1).
When a preꢀsynthesized sulfide 3b reacted with the
PhS– anions of compound 2b (60 C, 5 h), the yield of
compound 7b was 5%, the yield of the Zꢀisomer of comꢀ
pound 6b was 40%. However, acetylene derivative 5b was
obtained in this case in 33% yield. Thus, under these conꢀ
ditions, a considerable amount of compound 5b remains,
but the yield of compound 7b is only several percent beꢀ
cause of its rapid enough isomerization to Zꢀ6b.
Scheme 5
In the reaction of selenium derivative 3c with the PhSe–
anions of compound 2c (60 C, 18 h), as it was expected,
the formation of Zꢀisomer 6c was observed (63% yield).
The stereochemical direction of the process in this case is
determined by the same regularities as in the direct domiꢀ
no reaction of dichloropropene 1 with the PhSe– anions of
compound 2c (Eꢀisomer is virtually absent). This reaction
results also in the formation of 2,3ꢀbis(phenylselanyl)propꢀ
1ꢀene 7c in 26% yield, which isomerizes to the correꢀ
sponding Zꢀisomer slower than compound 7b.
A possibility of the isomerization processes 7c  Zꢀ6c
and Zꢀ6  Eꢀ6 was confirmed by independent experiꢀ
ments. Heating a mixture of compounds Zꢀ6c and 7c (3 : 1)
in the system hydrazine hydrate—KOH at 60 C for 19 h
led to a mixture of Zꢀ6c—Eꢀ6c—7c (18 : 3 : 1). This means
Step f of the domino reaction (see Scheme 3) is a well
known in chemistry of organosulfur compounds allylꢀproꢀ
penyl rearrangement.13 A possibility of isomerization of
allyl phenyl chalcogenides in the system hydrazine hyꢀ
drate—alkali was studied and it was shown that under the
same conditions, a sulfide isomerizes by 95%, whereas
a corresponding selenide by 53%. The isomerization deꢀ
gree of allyl phenyl telluride was only 3%.14 The propenyl
derivatives in the cases of sulfide and selenide are formed
predominantly as Zꢀisomers. In our systems, we observe
a similar pattern, namely, sulfide 7b undergoes isomerizaꢀ
tion to compound Zꢀ6b faster than the selenium derivaꢀ
tive. Compound 7b was detected (2% yield) only when

Mechanism of dominoꢀreaction
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 8, August, 2014
1725
that a 82% isomerization 7c  Zꢀ6c took place under
these conditions, whereas isomerization Zꢀ6c  Eꢀ6c ocꢀ
curs only by 14%. Under similar conditions, isomerizaꢀ
tion Zꢀ6b  Eꢀ6b took place by only 4.5%. An increased
stability of Zꢀisomers of compounds 6 can be interpreted
in the framework of the hypothesis,
which takes into account the presence of
the p—dꢀintramolecular interaction beꢀ
tween the sulfur atoms in the Zꢀposition
and the multiple bond with the formaꢀ
sulfur atom correspond better to pꢀorbitals of carbon atom
than selenium dꢀorbitals. This allows us to suggest that
carbanion B for Y = S is more stable than for Y = Se, and
the dehydrochlorination process in the case of sulfide is
easier to take place.
It is obvious that the vacant 5dꢀorbitals of tellurium
and 2pꢀorbitals of carbon differ even greater. Therefore, in
the case of Y = Te (see Scheme 6), there is virtually no
stabilization of anion B by the neighboring heteroatom.
It is possible that this is the reason that the reaction
of diphenyl ditelluride with dichloropropene 1 even at
45—50 C included only the first step of the domino reacꢀ
tion.18 Neither allene, nor acetylene derivative were deꢀ
tected in these studies.
Earlier,19 based on the quantitative data on deprotoꢀ
nation of different sulfides and selenides, a suggestion has
been made that anions, in which the negative charge is
concentrated on the orbital with a higher percentage of
pꢀcharacter (sp3ꢀhybridized orbital), are more efficiently
stabilized by sulfur atom than by selenium. But if the negꢀ
ative charge is concentrated on the orbital with higher
sꢀcharacter (for example, sp2ꢀhybridized orbital), the corꢀ
responding anion is better stabilized by selenium. Dehyꢀ
drochlorination according to Scheme 6 involves anion B,
in which the negative charge is concentrated on the sp3ꢀhyꢀ
bridized orbital, therefore this process should be more efꢀ
ficient for the case Y = S.
tion of the 6ꢀelectron structure.15 Apparently, such an
interaction in the case of selenium atoms is less efficient.
From the data in Tables 1, it is also seen that under
conditions of only first three steps (a—c) in the case of
selenium derivatives the processes of dehydrochlorination
with the formation of allene derivative 4c (step b) and
isomerization of the latter to acetylene selenide 5c (step c)
are considerably slower. The effects of the replacement of
sulfur atom with selenium one in these transformation we
interpreted taking into account the mechanisms of proꢀ
ceeding reactions.
Two mechanism can be considered for dehydrochloriꢀ
nation of compounds 3b,c: a synchronous E2 and a E1cB
mechanism, which are hardly distinguishable in kinetic
studies.12 In the early period of development of concepts
of organic reaction mechanisms, there was a suggestion
that the E1cB mechanism was applicable only in limited
cases,16 when a carbonyl or other electronꢀwithdrawing
group existed near the anionic center in the conjugate
base. In the examples studied,16 the leaving atoms and
groups were attached to the sp3ꢀhybridized carbon atoms.
In dehydrochlorination of monochalcogenide derivatives
3, the hydrogen atom leaves the sp3ꢀhybridized C atom,
whereas the Cl– anion leaves the sp2ꢀhybridized one.
Therefore, the most plausible mechanism of dehydrochlorꢀ
ination of compounds 3b,c is the E1cB mechanism, which
involves the conjugate base,12 the carbanion B (Scheme 6).
A possibility to effect the process in this case is determined
by stability of carbanion B.
The alleneꢀacetylene isomerization 4  5 (step c, see
Scheme 3) with the formation of acetylene chalcogenide
with the internal triple bond is a thermodynamically favorꢀ
able process,20 which also follows a carbanionic mechaꢀ
nism (Scheme 7).
Scheme 7
Scheme 6
The formation and stability of anion C are determined
by the same factors as those of anion B. However, in anion
C the negative charge is concentrated on the sp2ꢀhybridꢀ
ized orbital, therefore, according to the work,19 in the case
of Y = Se it should be more stable than for Y = S. It is
obvious that the rate of isomerization is determined by the
contribution of the resonance structure C´, which for Y = S
should be larger because of the reasons mentioned above.
In this connection, in the case of Y = Se the conversion
4  5 proceeds slower and allene derivative 4c has proved
more stable than in the case of the corresponding sulfurꢀ
containing compound.
A major factor, which defines stability of anion B, is
the nature of the chalcogen atom Y neighboring to the
anionic center. Since the electronegativities of sulfur and
selenium are close enough (according to Pauling scale: for
S 2.58, for Se 2.55; according to Allred—Rochow scale:
for S 2.44, for Se 2.48),17 the delocalization of the negaꢀ
tive charge should be determined by the involvement of
dꢀorbitals of the hetero atom. The smaller dꢀorbitals of
In conclusion, the schemes of possible mechanisms
suggested for the individual steps of domino reactions of

1726
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 8, August, 2014
Levanova et al.
Reactions of dichalcogenides Ph2S2 and Ph2Se2 with dichloroꢀ
propene 1 were carried out as described in the works.9,10 The
reaction conditions and the ratios of reagents are given in Table 1.
The mixtures of products were analyzed by GLC, IR spectroscoꢀ
py, NMR spectroscopy, and chromatoꢀmass spectrometry. Specꢀ
tral characteristics of compounds 4b,c, 5b,c and Zꢀ6b,c agree
with the literature data.9,10 Compounds Eꢀ6b,c and 7b,c are newꢀ
ly characterized.
Eꢀ1,2ꢀBis(phenylsulfanyl)propꢀ1ꢀene (Eꢀ(6b)) was obtained
in 6% yield by the reaction of Ph2S2 with dichloropropene 1 at
60 C (18 h) and characterized in a mixture with Zꢀisomer.
1H NMR, : 2.03 (d, 3 H, Me); 6.38 (q, 1 H, =CH, 4JHH = 1.0 Hz);
7.17—7.38 (m, 10 H, Ph). 13C NMR, : 29.67 (Me); 125.0—136.0
(C=C, Ph).
Isomerization of Zꢀ6b to Eꢀ6b. A mixture of KOH (2.26 g,
0.04 mol), hydrazine hydrate (7 mL), and a 11 : 1 mixture of
isomers Zꢀ6b and Eꢀ6b (1.04 g, 0.004 mol) was stirred for 19 h at
60 C. A workꢀup gave a colorless liquid (0.93 g), which was
a mixture of compounds Zꢀ6b and Eꢀ6b in the ratio 7.5 : 1. The
isomerization degree was 4.5%.
phenylchalcogenolate anions with dichloropropene 1 alꢀ
low us to explain the influence of the nature of the chalcoꢀ
gen atom on the ratio of products formed and predict their
stereochemistry.
The structures of compounds synthesized were conꢀ
firmed by a combination of IR spectroscopy, NMR specꢀ
troscopy (1H, 13C, 77Se), and chromatoꢀmass spectromeꢀ
try. The structures of Zꢀ and Eꢀisomers of compounds 6b,c
were established using a 2D NOESY procedure.21 The
spectra of Zꢀisomers exhibited the crossꢀpeaks between
the protons of the Me groups and the vinyl proton of the
=C—H group. The mass spectra of isomers Zꢀ, Eꢀ6 and 7
did not differ much. This can be due to the fact that moꢀ
lecular ions of three isomers under study have similar
structure, which is rapidly formed upon ionization of the
molecules.
Experimental
Eꢀ1,2ꢀBis(phenylselanyl)propꢀ1ꢀene (Eꢀ6c) was synthesized
in 5% yield by the reaction of Ph2Se2 with dichloropropene 1 at
60 C (18 h), the ratio Ph2Se2 : KOH = 10 : 1. 1H NMR, : 2.08
Monitoring of purity of the starting dichloropropene 1 and
analysis of products formed were carried out on a a LKhM
80ꢀMDꢀ2 chromatograph (2000×3ꢀmm column, liquid phase
Silicon ХEꢀ60 (5%) on Chromaton NꢀAWꢀHMDS, the column
temperature was programmed linearly from 30 to 230 C at
12 C min–1, carrier gas helium). 1H, 13C, and 77Se NMR specꢀ
4
(d, 3 H, Me); 6.71 (q, 1 H, =CH, JHH = 1.0 Hz); 7.18—7.48
(m, 10 H, Ph). 13C NMR, : 29.58 (Me); 121.90 (=CH),
125.0—136.0 (MeC=, Ph). 77Se NMR, : 369.1 (PhSeCH=);
491.6 (PhSeC(Me)=); for Zꢀisomer: 385.1 (PhSeCH=); 427.3
(PhSeC(Me)=, 3JSeC=CSe = 91.4 Hz).
tra were recorded on
a
Bruker DPXꢀ400 spectrometer
Isomerization compounds Zꢀ6c and 7c. A mixture of KOH
(1.6 g, 0.03 mol), hydrazine hydrate (7 mL), and a 3 : 1 mixture
of isomers Zꢀ6c and 7c (1.0 g) was stirred for 19 h at 60 C.
(400.13 (1H), 100.61 (13C), and 76.31 MHz (77Se)) in solutions
in CDCl3, internal standard Me4Si (Me2Se for 77Se).
1
Mass spectra were obtained on a Shimadzu GCMSꢀQP5050A
chromatoꢀmass spectrometer (a SPBꢀ5 column, 60000×0.25 mm),
the stationary phase film was 0.25 m thick; the injector temperꢀ
A workꢀup gave the product (0.83 g) containing (the H NMR
data) isomer Zꢀ6c (0.68 g), isomer Eꢀ6c (0.11 g), and compound
7c (0.04 g). The Z  E isomerization degree was 14%. The
isomerization degree of compound 7c  Zꢀ6c was 82%.
ature was 250 C, carrier gas helium, the flow rate 0.7 mL min–1
,
the temperature was programmed to increase from 60 to 260 C
at 15 C min–1, the detector temperature was 250 C, a quadruꢀ
pole mass analyzer, electron ionization, energy of electrons
70 eV, the source of ions temperature 200 C, the range of deꢀ
tecting masses 34—650 Da.
2,3ꢀBis(phenylsulfanyl)propꢀ1ꢀene (7b). A. A mixture of KOH
(3.21 g, 0.057 mol), hydrazine hydrate (14 mL), Ph2S2 (2.5 g,
11.4 mmol), and dichloropropene 1 (1.27 g, 11.4 mmol) was
heated for 2 h (60 C). The yield of the product was 2%. A workꢀ
up gave 1.48 g of the residue (a light brown liquid) containing
(1H NMR data) a mixture of compounds 4b, 5b, Zꢀ6b, Eꢀ6b, and
7b in the ratio 1.0 : 41.0 : 25.5 : 1.4 : 2.35. 1H NMR of compound
7b, : 3.61 (d, 2 H, CH2S, 4JHH = 1.2 Hz); 5.04 (s, 1 H, cisꢀCH=);
5.34 (t, 1 H, transꢀCH=, 4JHH = 1.2 Hz); 7.10—7.40 (m, 10 H, Ph).
B. The compound Ph2S2 (1.0 g, 4.6 mmol) was added to
a solution of KOH (1.3 g, 0.023 mol) in hydrazine hydrate (6 mL).
The reaction mixture was stirred for 2.5 h at 85—90 C and
cooled to 60 C, followed by a dropwise addition of compound
3b (1.69 g, 9.2 mmol) and stirring for 5 h at this temperature.
A workꢀup gave a light yellow liquid (1.55 g), which was a mixꢀ
ture of compounds 4b, 5b, Zꢀ6b, Eꢀ6b, and 7b in the ratio
1.0 : 47.2 : 57.5 : 3.0 : 7.0. The mixture contained compound 7b
(0.115 g, 5%).
2,3ꢀBis(phenylselanyl)propꢀ1ꢀene (7c). A. Diphenyl diseꢀ
lenide (2.0 g, 6.4 mmol) was added in portions to a solution of
KOH (1.8 g, 0.032 mol) in hydrazine hydrate (8 mL) at 40—50 C.
The reaction mixture was heated for 3 h at 85—90 C and cooled
to 60 C. Dichloropropene 1 (0.71 g, 6.4 mmol) was then added
dropwise at this temperature with stirring, and the stirring was
continued for 5 h. Then, the mixture was cooled and treated as
described in the work10 to obtain the product as a yellow liquid
Reaction of phenol with dichloropropene 1. 2ꢀChloroꢀ3ꢀphenꢀ
oxypropꢀ1ꢀene (3a). Phenol (9.42 g, 0.1 mol) was added to
a solution of KOH (14.0 g, 0.25 mol) in hydrazine hydrate
(60 mL) at 45 C. After the phenol was dissolved, the reaction
mixture was cooled to 0 C, followed by a dropwise addition of
dichloropropene 1 (11.1 g, 0.1 mol) with stirring. The reaction
mixture was stirred for 14 h at 0 C and extracted with dichloroꢀ
methane (3×50 mL). The extract was dried with MgSO4, the
solvent was evaporated. The residual light yellow liquid (4.36 g)
contained (1H NMR data) 0.3 g (~2% yield) of compound 3a
and 4.06 g (38% yield) chloropropenylhydrazine 8. Spectral charꢀ
acteristics of compound 8 are identical to those described in the
literature.6 Compound 3a was identified in the mixture accordꢀ
1
ing to the H NMR data, : 4.55 (s, 2 H, OCH2); 5.43 (s, 2 H,
=CH2); 5.53 (s, 2 H, =CH2); 6.88 (m, 2 H, Ho); 6.95 (m, 1 H,
Hp); 7.26 (m, 2 H, Hm). 13C NMR, : 69.89 (OCH2); 113.54
(=CH2); 115.10 (Co); 120.61 (Cp); 129.45 (Cm); 136.24 (=CCl–).
MS, m/z (Irel (%)): 170 [M+ for 37Cl] (1), 168 [M+ for 35Cl]
•
•
(4), 133 [M – Cl]+ (40), 105 [PhCO]+ (9), 94 [PhOH]+ (5),
79 (3), 77 [Ph]+ (6), 75 (3), 66 (3), 65 (10), 63 (5), 58 (4), 51 (7).
•
C9H9OCl. Calculated: M = 168.6225.

Mechanism of dominoꢀreaction
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 8, August, 2014
1727
(1.42 g), which contained compound 7c (0.18 g). 1H NMR,
: 3.66 (d, 2 H, CH2Se, 4JHH = 0.7 Hz, 2JSeCH = 12.3 Hz); 5.09
Chem. (Engl. Transl.), 2011, 81, 611 [Zh. Obshch. Khim.,
2011, 81, 516].
8. E. P. Levanova, V. A. Grabel´nykh, N. V. Russavskaya, A. I.
Albanov, A. V. Elaev, O. A. Tarasova, N. A. Korchevin,
Russ. J. Gen. Chem. (Engl. Transl.), 2011, 81, 1560 [Zh. Obshch.
Khim., 2011, 81, 1213].
9. E. P. Levanova, V. A. Grabel´nykh, A. V. Elaev, N. V. Rusꢀ
savskaya, L. V. Klyba, A. I. Albanov, O. A. Tarasova, N. A.
Korchevin, Russ. J. Gen. Chem. (Engl. Transl.), 2013, 83,
1341 [Zh. Obshch. Khim., 2013, 83, 1088].
4
(s, 1 H, cisꢀCH=); 5.46 (t, 1 H, transꢀCH=, JHH = 0.7 Hz,
3JSeC=CH = 16.3 Hz); 7.18—7.48 (m, 10 H, Ph). 13C NMR,
: 35.66 (SeCH2, 1JCSe = 64.7); 119.43 (=CH2, 1JCSe = 9.3), for
aromatic protons, first are reported signals for the Phꢀprotons of
the PhSeCH2 group, then those of the ring of the PhSe group at
the double bond: 127.48, 128.05 (Cp); 128.84, 129.13 (Cm);
133.38 (2JCSe = 9.9 Hz); 134.51 (2JCSe = 10.3 Hz) (Co); 138.89
1
(C=CH2, JCSe = 105.2 Hz). 77Se NMR, : 336.2 (CH2Se);
430.6 (SeC=).
10. E. P. Levanova, V. A. Grabel´nykh, V. S. Vakhrina, N. V.
Russavskaya, A. I. Albanov, L. V. Klyba, O. A. Tarasova,
I. B. Rozentsveig, N. A. Korchevin, Russ. J. Gen. Chem.
(Engl. Transl.), 2013, 83, 1660 [Zh. Obshch. Khim., 2013,
83, 1434].
B. Diphenyl diselenide (1.0 g, 3.2 mmol) was added in porꢀ
tions to a solution of KOH (0.9 g, 0.016 mol) in hydrazine hyꢀ
drate (4.5 mL) (40—50 C). The reaction mixture was stirred and
heated for 3 h at 85—90 C, then cooled to 60 C. 2ꢀChloroꢀ3ꢀ
phenylselanylpropꢀ1ꢀene (3c) (1.47 g, 6.4 mmol) was added
dropwise at this temperature, the mixture was stirred for 18 h at
60 C, cooled, and treated as described in the work10 to obtain
the product as a yellow liquid (2.0 g), which contained Zꢀisomer
of compound 6c (1.4 g, 63%) and compound 7c (0.6 g, 26%).
11. G. Perin, E. J. Lenardão, R. G. Jacob, R. B. Panatieri, Chem.
Rev., 2009, 109, 1277.
12. A. S. Dneprovskii, T. I. Temnikova, Teoreticheskie osnovy
organicheskoi khimii [Theoretical Principles of Organic Chemꢀ
istry], Khimiya,, Leningrad, 1991, 560 pp. (in Russian).
13. D. S. Tarbell, M. A. McCall, J. Am. Chem. Soc., 1952, 74, 48.
14. E. N. Deryagina, N. A. Korchevin, Russ. Chem. Bull.
(Engl. Transl.), 1996, 45, 223 [Izv. Akad. Nauk, Ser. Khim.,
1996, 231].
The work was carried out using facilities of the Baikal
Analytical Multiꢀuser Center of the Siberian Branch of
the Russian Academy of Sciences.
15. B. A. Trofimov, Geteroatomnye proizvodnye atsetilena [Heteroꢀ
atomic Derivatives of Acetylene], Nauka, Moscow, 1980,
320 pp. (in Russian).
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Received January 30, 2014;
in revised form March 18, 2014