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Formation and reactivity of the addition products of alkoxides and thiolate anions to vinyl selenones
Te-rr&dron Vol. 42. No. 17, pp. 4897 Printi in Grd Britain.
to 4906.
0
FMTIOW
AK0 REACTIVITY AI0 TNIDLATE
MARCELLO
TlECCO.*
DONATELLA
OD4@-4020/86 1986 F’qamon
1986
DONATELLA
OF THE MolTToW
PRODUCTS
ANlowS
SELD(OIIES
CHIANELLI,
TO VINYL
MARCO TINGOLI,
S3.00 + .OO Journals Ltd.
OF ALKOKTDES
LORENZO
TESTAFERRI
and
BARTOLl
lstituto
di Chimica
Facolti
Organica,
di Farmacia,
Universita
di Perugia,
Italy.
(Received in UK I3 June 1986)
Abstract. product
Vinyl selenones of conjugate
On the contrary, conjugate
are
selenonyl
group.
MeOH and
in
is
making
acidic
the
nucleophilic
We have
The
reactions
previously
methoxide.
in
unactivated
observed
These
vinyl salenones
the
conjugate
inferred of
some
intermediates
in
these
were rapidly selenonyl
atoms.
products
group.
ways
alkyl
choice
of
These
of
and
the
results
the
it acts and
a
reagent
indicate
and
of
Useful
that
properties.
good
vinylic,
products.
nucleophilic
carbon-carbon as
the
in
bond
group
in
elimination
solvent
synthetic
the
Beside
double
leaving
and
the
both in
elimination
by
peculiar
the
phenyl
loss
and
followed
group.
affords
with
substitution
with
activates
aliphatic
the desired
vinyl
selenoxides
solvents,
halides,
to
however
2,3
could
allows
to
applications
of
of
of the
1,s
not
to give the products
the
and
giving the
sodium
methanethiolate
products
selenides.
of
starting
selenones
addition
because,
of intermolecular
b-9 4397
medium
their
functionalized
isolated
4
the
as well
salenones
under
the
at the e-
was aprotic
as
(DMF),
intermediates
as from
were
vinyl
vinylic
same conditions
additions
employed
products
sodium
than those with other
Under
formation
and
nucleophilic
rise to competitive
reaction
isolated;
Similar
further
were
sulphides
be
with
and occur much more easily
since
not
react
afford
behaviour
However,
products.
reactions
compounds
consumed
it
reagents
isomerization
reaction the
atoms
an ambidentic
bcarbon
from the observed the
from
reactions
group
are stereospecific
like vinyl
addition
of
species;
aprotic
-1 present
as well as at the
that
reactions
substrates
anions
are presented.
dipolar
1
substitution.
to give the
selenonyl
e-alkoxy
several
thus generated.
both
towards
These
in
derive
Michael
attracting
of anionic
appropriate
the reaction
these
selenone
substitution,
alkoxide
yields. react
observed
a-hydrogen
with
of the
with MeONa or MeSHa have been investigated
retro
electron
the addition
reactions.
from
out
excellent can
in methanol
displacement
carried
which
products
as
strong
a
in
reactions
of the vinyl
ArSeO2
direct
The
well
subsequent
reaction
compounds
Their
DMF.
substitution
and
products
stable
as
processes
towards
the same
addition
selenones
react with sodium methanethiolate
addition
also
with
the
structure
formulated
other
displacement
as
anionic
condi-Lions employed,
or intramolecular
was
they of the
M. TIECCU er al.
4898
The
reactions
investigated sulphur
in
can
be
isolated
observe
the
loss
of
addition good
nature
the
compounds 2 and
their
OMF support
the
nucleophiles
in
the
vinylic
the
addition
products
2.
lJhen alkoxide
The anionic
of
the
m-proton
group
with
the
z
give
the
MeSNa in
in
the
the at
the
oxygen
and
the
2
(Nu
the
o-carbon
to
the
The of
= OR)
one
can
a-proton give
the
substitution
paper
OK.
behaviour
to
reactions.
at
this
vinyl
6-carbon
several
attack
the
this
in
now
medium employed,
1,
MeOH and
of
to
been
With
at
compounds
structures
WC describe
the
occur. (Nu)
rise
attack
particular
interpretation
not
reaction
have
of
employed
selenone
and
3,
products.
McONa and
are
on the
vinyl
having
does
nucleophile
anions
and
BeSNa
nucleophilicity
the
selenones
products
cyclic
proposed
aprotic
give
give
of
(X-1
nucleophiles
afford
reaction
to
the
RONa and
substitution
alkyl
species
to
with
aryl
with
conditions
is
previously dipolar
these
selenones
and
the
to
vinyl
observed
yields.
10
j;
intramolecularly
Under
of
selenonyl
products
and
decreased
abstraction
substitution occur
solvents.
process
in
on the
selenoxides
greatly
only
conjugate
Depending
with
is
1 the
the
vinyl
protic
anions
selenones give
of
synthesis
results
vinyl
can of
obtained
in
selenones
with
solvents.’
R
R
R
b 67
SeO,Ph
Nu
I
E
.L
L
X-
w SeO,Ph
F
---INu
*
"h Nu
X
A
X=or#Nu
RESULTS AH) DISCUSSIUR
From the minute
reaction
amounts
mixture;
most
of of
of the
the
the
(E)-6-styryl
addition
phenyl
product
starting
product
a
could
remained
selenoxide be evidenced unchanged
SCHEME Ph L I
5
by
giving
rise
On the ice
bath,
similar of
the
yields
of
exclusively contrary,
from
addition
SeOPh
the
11
The reaction
deoxygenated
was formed
could
of be
which other
phenyl
L 7
with
product
(E)d-styryl
reaction
products
reaction
could
be found
different
course
PhyHCH,SeOPh
MeSNa_ MeOH
compound a. to
the
No conditions
the
Ph
when the
a precipitate way,
of
of
.!i
L 7
the
1).
analysis
presence
Me0
Ph
improve
H-nmr
MeOH the
1
2
to
HeONa in
1
(Scheme
MeONa, &OH
SeOPh
with
obtained
HeSNa took
j as
anions
(Scheme
a completely
1.
selenone
was identified alkoxide
SePh
2).
in
was treated
with
the
addition
the
Michael
corresponding
Compound e
was
MeONa in
product
alcohols, also
MeOH,
obtained
in
In a
%. high
an
yields
from
the
4899
Additionproductsof alkoxidwand thiotattanionsto vinylselcnoncs I#?)-isomer _I& The addition selcnone
product 12 was formed from the
with NeONa in &OH. These are the
11
SCHEME
Ph
L -N
first
of the
(EMt-styryl
methyl
in which the conjugate addition
examples
2
:~yseo2Ph
RONa_ ROH
SiqPil
reaction
S_a: R L:Me (95%)
u!!
@: R= Et (93%) 9,~ : R z CHMe, (92%) 9:
R = CH,CH=CH,
(86%)
S_e: R= CH,CH,OH
MeONa, PhLJseo2Ph MeOH
(83%)
$J (80%)
$J Ph L 7
MeO?Ja_ MeOH
Se&Me
Ph SeO,Me )-/ Med
?s, -
12 (86%)
products of an anionic species to vinyl selenones could be isolated. is straightforward
The course of these reactions
and is reported in Scheme 3 in the case of the addition
of sodium methoxide in
methanol:
SCHEME
PhCH=CHSeO~Ph
+ MeO-.;lcr
3
PhCH~~Se02Ph
MsCrHc
PhCHCH~~02P~
b Me 8910 -WW.
is
reversible.
catalytic
reversibility oxidation
Indeed,
amounts of
precipitation,
the
process
The reaction of the vinyl
as
ions are needed as catalysts
MeONa were employed. is completely
be discussed 12 selenides. selenone
in 1 h. the
to
mixture
com~unds
-lh
2
are
substracted
be obtained
by two products fi
The formation
and
of these
1_I!which abstracts
a proton from the solvent
l~methylthio,2-~enylselenonyl,l-phenylethane in the presence of a strong
to give methoxide anions and the E.
This
nucleophile
aryl
alkyl
selenone
by
were the
two products the carbanion
addition
however
such as the He5 anion,
by the
in MeOH
which
(35%)
in Scheme 4. Addition of the FleS anion to 3 gives
as indicated
for
(2 molar equivalents)
was constituted
(38%) (Scheme 4).
in which only
Further evidences
Compounds 2 can also
below.
1,2-bis(methylthio~phenylethane
1-phenyl,l-methoxy,Z-methylthioethane
only and that the process in the case
the right.
J! with sodium methanethiolate
The reaction
can be rationalized
since,
shifted
well also
since
Besides,
will
of the corresponding
at 0% was complete
isolated
e?
compound !& was obtained equally
the equilibrium of
identified
t)Me
E!
This mechasnism suggests that alkoxide
+ f@ieO-
it
product cannot
be
is rapidly
M. TIECCD er al.
4900
consumed
to
(Scheme
give
the
substitution
3) the methoxide
like 12,
product
-14.
ions react easily
On
product
SCHEME
SeO,Ph
hand,
as
Ph a==
been
product
1;
shown
this
above
selenone,
the MeS- is consumed
in
Me0 PhhSMe
l
E
!!
8 + MeS-
has
4
MeS
I
it
15a. Thus, whereas
PhhSMe
MeSNat MeOH
L 7
other
with 8 to give the addition
reacts with MeS- to give the observed
Ph
the
SeO,Ph
Ph MeOH, *
Y
SeO,Ph MeO-
l
t/
MeS
MeS 18
!z
MeS
A
MeO-
l
m
13 _
-#Qk
E
+ MeO-
1
MeS-
the substitution a catalytic
process
The results with
react
employed, the
isolated products this
faster
with
of j
they
deriving
selenone
reaction isolated selenones of the
is
the
in protic
are
Krief
instead and
substitution
ions are continuously
3 and 4 seem to indicate and oa
than
with
MeSNa
rapidly
process
consumed
than
E
and
in HeOH, consumed
98;
as
reaction
by
the ions
solvents at the
in competition
coworkers reactions
10
have
with
The
are completely
o-carbon
a
recently variety
of
j,
under
the
fact,
other
of
both
no products Attack
solvents that
nucleophiles
MeS
c
hand
alkyl
are
at
the
formation
of
all
to suppress the starting
Indeed
anions
and
when
2
the
(70%) was with
vinyl
from the addition at
the
bcarbon
employed.’
phenyl
including
be
compound RO
Thus,
cannot
In order
o-
conditions
1
deriving the
mathoxide
and
anion.
and
the
faster
be observed.
in which
methanethiolate
react the
under not
be avoided.
conditions
be observed. aprotic
whereas
(IO molar equivalents)
reactions
anions
products
the
in
to ! cannot
with
reported of
selenone
addition
regioselective;
atom could
when dipolar
the thiolate
matter
and
MeS-
to work
reaction
product.
a
with 8; this is
regenerated.
that
vinyl
the conjugate
of methoxide
the
the
in the reaction
of -17 and -ga with f!eO- could
it is necessary by
with
out with a large excess of MeSNa
sole
nucleophiles
the MCO- is only involved
from the reaction
with
are
x
by the addition
was carried as
8
deriving
reaction since
in Schemes
selenones
latter undesired
vinyl
atoms
aryl
products
of II and 2,
from which methoxide
reported
the alkyl
anions
from
reactions
selenones
HeONa
in
readily
MeOH
and
undergo PhSNa
in
Addition
ethanol.
We have
examined
MeSNa in MeOH and above
(Scheme
The reactions afforded
Apart
5). from
the
OW.
the
nucleophile
side
at
the
of
aryl
alkyl
9 with
the
of the
reaction, a-carbon
of
B-alkoxyalkyl
were
already
selenones
were
products
amounts
predominant
the
aryl
e
v
Ph
reactions
with the
from
accompanied mixture 5).
of
These
from the
the
vinyl
attack
reactions place selenone of
at are
but
the
anions of
second
selenone
8 and
has
gave
is
the
attack
of
products.
the The
SePh
1%
(5%)
(63%)
12
(58x)
1s z
(17%) (23%)
Ph
c
Et0
o-carbon
which
+
hOMe
Ph k
Me0
2,o (48%)
Ph
h OEt
the
+ Et0
in
at
the
the
out,
the
the
the
F
-9
is
of 98 similar
the to
of the
a different
with
EtONa.
the
ArSe02
group;
19
this
EtOH (Scheme directly
case
and
therefore
the 11
was
A similar
starting
carbanion
carried
responsable
g.
EtONa in
In
course.
product
results,
substitution
give
reaction
probably
took
substitution
o-methoxystyrene
MeONa or
i.e.
The same
the
quite of
and
the
reaction
a-proton
substitution
selenones
10 h)
as
with
equivalents
consequences. of
identified
E-hydrogen, at
(8 -
equivalents)
from
be carried
The attack
product
moiety
was
5 molar
slower
rolar
was obtained
using and
were
MeONa (4
also
no practical
only
alkyl
elimination
can
in competition.
it
group.
(82%)
Me0
alcohols
with
21 and g
reactions
the
in
>
compound
two products two
alkoxy
22 (42%)
alkoxide
a
3
the
12
Ph
EtOH
reaction by
compounds
of
t/ RO
9b
Thus
room temperature,
e : R = CH,CH,OH
c
EtONa
at
substitution
12 (34%)
SeO,Ph
described
intermediates.
1s
b:R=Et
9a
Et0
the
R
MeOH
Ph
case
l
MeONa
F
nature
in this give
reactions as
deoxygenated
the
Ph
a: R=Me
Me0
to
NeONa and
5
MeSNa MeOH
SeO,Ph
some
with
9 towards
the
intervene
in methanol
observed
selenone
alkyl
from to
with
changed
process
selenones
available proposed
together
SCHEME
Ph
phenyl
equivalents),
two products
the
4901
and thiolate anions to vinyl sclenones
MeSNa (2 molar
substitution
The relative this
behaviour
compounds
expected
of alkoxida
Some information
which
of
the
(Scheme
in
4) in
products
elimination
is
also
taking
out on the n-decyl phenyl 10 the particular structure for
the
occurrence
of
the
reaction.
The reactivity with
MeSNa (0°C.
the
(El-a-styryl
of
the
selenones
0.5
h),
together
with
the
substitution
sulphide
23,
was
isolated;
methyl
9 changed
on passing
from
methanol
products the
relative
to
a second amounts
OMF. From
the
compound,
identified
of
the
two
reactions
products
as
4902
M.
changed
with
the
bulkiness
of -Pa with
reaction
MeONa
mixture
was constituted
confirm
previous
strong
bases.
of
the
COY,
alkyl
0.5 h)
TIECCXI er al.
group
did
R
not
by the a-methoxystyrene
observations
that
alkoxide
in the
give
starting
any
substitution
-20 and the anions
in
selenones
product
Ph
SeO,Ph
MeSNa DMF
v RO
more
than
as
a: R=Me
Ph
SeOzPh
reaction
These
results
behave
as
Ph
c
L 7
l
RO
SMe
l&t
90% 1
SMe 23
place to afford by
the the
(36%) (42%)
Ph
Ph b
L 7
+
OMe
Me0
of compounds
23 and 24 clearly
(El-6-styryl MeS
of a proton
or from
the
phenyl Me0
selenone
s
This
anions.'
the solvent
from the equilibrium
indicates
that in OFF a retro
(Scheme reaction
7) which
addition
SCHEME
Ph
proceeds
of nucleophiles
nucleophilic
easily and
reaction
since,
the
in
selenone
takes
vinylic OMF,
the
8 can be _
.
This
at the o-position.'
7
Ph
SeO,Ph )A
Michael
suffers
by the anion -13 is difficult
by irreversible
(5%)
-
e:R=CH$H,OH
MeONa ) DMF
Me0
subtracted
24.
The
6
d:R = CHICH=CH2
Y
substitution
6).
the
nucleophiles
15dt45X) jTJ,oX)
abstraction
19;
(El-B-methoxystyrene
DM
(Scheme
1,13
SCHEME
The formation
!
L 7
s===
RO !z
l
SeO,Ph
k
I
Nu-
Ph L 7 Nu g:Nu=
MeS
24: NU z Me0
RO-
4903
Addition products of alkoxides and thiolate anions to vinyl selenones
interpretation
is
corroborated
of MeONacompound 8 can be isolated with some -20 and -24.
It
is
fact
by the
that
when %
from the reaction
interesting
to
note
of g with NeONa in DMF. The present
behaviour
vinyl
results
of
selenones
collected
in
towards
Scheme 6 show that
compounds
whereas
a-hydrogen
of
abstraction
of the a-hydrogen
in methanol also other
selenone
8;
The reaction proceeds
the
of g
epoxides
from
presence
the
to
the
from hydroxyselenones
contrary,
to
effect
the
case
does the
not
alkoxy
aryl
alkyl
has
been
produced
26
likely
from h
__
isolated
reaction rather
reaction
The results
aprotic
products
is
discussed
selenoxides
alkyl
likely
is
stage
initially
to
the the
occurring
of
the
conjugate
low
yields
the
vinyl
addition (45%).
carbanion
intramolecular for
the
tetrahydrofuran
in
formed
produced;
responsable with
ions
in water using
e
The gives
nucleophilic
observed
formation
of
potassium
displacement
to
with NaH in THF, did not give
afford
oxethanes.
On
any phenyl dioxane
29,
8
SeO,Ph
P
Ph I7 0
0-
2,s
Ph -
v
Ok \ CH$H,OH
\ CH,CH@-
product
to protic
very
being
the alkene
than as nucleophiles greatly
favoured
in the present
and vinyl
selenones. are
8-hydrogens;
very
and
?.!
as bases
dipolar
the
the
is
SeO,Ph
2,s
aryl
the
a-carbon
hydroxide
?..?
0
vinyl
the
>1-_ HO
Ph
elimination
of Thus,
the
and
although
intramolecular
!!”
only
work.’
from
t-butoxide in THF in the 698 that alkoxide ions shown by Kuwajima and coworkers
Ph HO-
of
at the i!J
that
selenones
a similar
SeO*P h
the
obtained
to 9 which is consumed by the
hydroxide
stop
anion
26 are very
Ph
behave
Q
process
-9a together
interpretation
previous
attacks
revert
addition
epoxide
SCHEME
l
unreacted
the
the
the
Michael
11 can easily
afford
the
like
give
the anion g,
L 7
attacks
retro
(Scheme 8) assuming
which
-27. Anions
reaction of 10 It belzaldehyde.
of
derived
from
affords
the
support in
MeS anion
out with potassium
in this
further
can be explained
B-hydroxyselenone
displacement
out
were carried
product formation
thus
quantity
(Scheme 5).
as a cosolvent. it
Me0 anion
the carbanion
carried
the reactions
but
case
processes were also
the
an insufficient
which contains
DMF given
DMF the
which initiates
but in this
irreversible
Experiments
9,
in
in
with
compounds -20 and -24 were also
results
alkoxides
treated
mixture
that
the reactions
is
selenones solvents;
Thus vinyl
versatile
30
and in the
by a
six
(82%). case
As suggested of
the
anion
membered transition
and in the previous’
paper indicate nucleophiles
changes
selenoxides,
intermediates
which
in reactivity
vinyl can
selenones be
easily
that
anions
the reactivity
changes
are also and
alkoxy
intramolecular
state.
with oxygen and sulphur similar
above -28 the
on passing
produced
their
transformed
in the case
conjugate into
of from
a
of
addition series
of
M. TIECCXJet al.
4904
valuable
compounds.
seleninyl
and
particular, the
the
these
reactions
selenonyl
groups
are
made
which
interesting
are
carried
out
characteristics;
reagents
and
and vinylic)
alkyl selenones
have acidic
choice
reagent
of
the
selenoxides,
vinyl
time and
and
of
group
peculiar
in nucleophilic
leaving
reactions.
solvent
The
bond
of
the
substituents.
In
substitutions
group
towards
shows the
group
in nucleophilic
Moreover
the a-hydrogen
in the
allows
addition
properties
vinylic ArSeO2
double
Thus, as anticipated
reaction
the
electron-attracting
solvents.
as a good
and their conjugate
containing
by
the carbon-carbon
it acts
the
strong
aprotic
in elimination
properties.
salenones
with loss of the selenium
dipolar
it activates
at same
(both aliphatic
in
possible
are
the ArSeO group acts as good leaving
reactions
anionic
All
to
direct
products
the
towards
addition
of
substitutions atoms
introduction,
when
several
in aryl
the appropriate
reactions
the desired
of
vinyl
derivatives
functions.
EXPERlKNfAL Structural
attributions
were
Proton nmr
spectra
recorded
were
made
by
carbon-13
proton,
at 90 Mz
nmr
on a Varian
were recorded
at 20.15 MHz on a Bruker WP 80 SY instrument
with
decoupling
proton
experiments. on a Carlo
CDCl Erba
phenyl
1106
Elemental
some
cases
and TMS as Analizer.
were
assignments
Elemental
analyses
were
elemental
carbon-13 made
by
analyses
performed
and
11
were
prepared
1, a-methoxystyrene
&I,
as
described
(E)-bstyryl
in the
methyl
analyses. nmr
spectra mode
off-resonance
were
on a
previous
sulphide
been described. of the (El-6-styryl phenyl selenone 8 with alkoxides. To the selenone 8 (5 mmol), dissolved in methanol or in ethanol
3
by
in the Fourier transform
operating
reference.
Glc
and
carried
out
Hewlett-Packard
with a 20 in. 10% UCW 982 column.
5, S, lo,
selenide
In
was used as solvent de1 la,
5830 A chromatograph Compounds
throughout.
spectra
EM 390 instrument;
B
paper.'
(E)-s-Styryl (E)-bmethoxystyrene
and
have already
Reactions bath,
sodium
solution
metho;de
of the
alcohol
alkoxide
reaction
times
chloroform.
After
was purified solid
were as
containing
in
ethoxide
in the
and the selenone
mixtures
the
or
alcohol %,
follows:
was
with
with at
white
water
light
room
was
added
prepared
the chloroform
hydride
on
water
can
resulting
in an ice cases a
other
(5 mmol)
and
and evaporated.
purification
the
the
to
the
was monitored by glc. The h; %, 12 h. The reaction
4.5
Poured
was dried
cooling
and
sodium
h; W,
were
Further
petroleum.
temperature
ml) and cooled In
adding
2.5
9
(15
stirring.
of the reaction
4 h; B,
products
under
by
The progress
2 h; s,
insoluble
washing
ethanol
mnol)
B was then added.
the
by washing
(5
extracted
The
be effected
solution
in
solid
with
residue
by dissolving an
ice
bath.
9a was similarly prepared starting from 10. The reaction of the (E)-B-styryl methyl selenone swith MaONa in MaOH was carried out in ayimilar way. Reaction yields are given under spectral and analytical data are reported the Results and Discussion section (Scheme 2); physical, Compound
below.
enylselemnylethane,
1-Phenyl,lathoxy,2-ph 7.5 (m, 3 H), 7.3br Hz),
3.6
(s, 5 H), 4.95
(dd, 1 H, J = 12.5 and
129.1, 127.1, 5.00. Found:
126.6,
3.0 Hz),
77.2 (C-l), 66.8
C, 55.81;
19.8 Hz), 3.6.(dd,
5 H),
C-nmr 6133.8,
129.8, H
3,
129.1,
129.0, 127.2,
(s, 5H),
3.6 (dd, 1 H, J ~~12.5
5.2
(m, 2 H),
7.7 -
C-nmr
(s, 3 H).
56.6
(Me).
Anal.
m.p.
136-8'C.
6
Calcd
143.9, for
137.2,
133.9,
C15H1603Se:
* 'H-nmr 6 8.15 - 7.95
129.8,
C, 55.73;
(m, 2 H),
126.5, 75.4
H,
7.7 -
$,
(C-l), 66.7 (C-2), 64.6
(CH2). 14.7 (Me)*
C, 57.02; HI 5:33.
m.p.
(dd, 1 H, J = 10.5
H-nmr 6 8.1 - 7.95 (m, 2 H), 7.7 2.7 Hz), 3.95 (dd, 1 H, J = 12.5 and
145-7’C. and
and 2.7 Hz), 3.5 (spt, 1 H, J = 6 Hz), 1.1 (d, 3 H, J = 6.0
C-nmr 0.85 (d, 3 H, J = 6.0 Hz). (C-I), 69.7 (cH), 66.6 (c-2), 22.9 C, 58.00;
6 8.1 - 7.9
5.05
1-Phenyl,l-isopro~x~~2$henylsolemflylethane,
Found:
3.15
(C-2).
0 Se: C. 56.97: H, 5.39. Found:
- 7.5 (m, 3 H), 7.3br
HZ),
H-nmr
(dd, 1 H, J = 10.8 and 3.0 Hz), 3.9 (dd, 1 H, J = 12.5 and 1 H, J = 12.5 and 3.0 Hz), 3.3 (q, 2 H, J = 7.2 Hz), 0.95 (t, 3 H, J = 7.2 Hz). (s,
Anal. Calcd for C
10.5
1
m.p. 171-3OC.
H, 4.97.
1-Phenyl,l_ethoxy,2-phenylselenonylethane, 7.55 (m, 3 H), 7.3br
1,
(dd, 1 H, J = 10.8 and 3,g Hz), 3.9 (dd, 1 H, J = 12.5 and 10.8
8 144.2, 138.5,
133.7,
129.7,
129.0,
128.9,
(Me), 20.6 (Me). Anal. Calcd for C17H2003Se:
127.1,
126.6,
C. 58.11;
Hz)* 72.5
H. 5.75.
H, 5.74. 'H-nmrb 8.1 - 7.95 (m, 2 H), 7.65 W, m.p. 107-8°C. (s, 5 H), 5.65 (ddt, 1 H, J = 18.0, 9.0 and 5.4 Hz), 5.15 - 4.9 (m, 2 H), 5.1
l~yl,l_allyloxy,2-phanylselenonylethme, 7.5 (m, 3 H), 7.3br
(dd, 1 H, J = 10.5 and 3.0 HZ), 3.95 (dd, 1 H,,J = 12.5 and 10.5 Hz), 3.8 (dt, 2 H, J = 5.4 and C-nmr 6 143.9, 137.4, 133.8, 133.5 (vin-C), 129.9, 1.2 HZ), 3.65 (dd, 1 H, J = 12.5 and 3.0 Hz). 129.2, 127.3, 126.7, 117.5 (vin-C), 75.0 (C-l), 69.9 (CH2), 66.7 (C-2). Anal. C&d for
C17H1803Se: C, 58.45; H, 5.20. Found: C, 58.51; H, 5.23.
4905
Addition products of alkoxides and thiolatc anions to vinyl selenones
I-hyl,l-(2_hydroxy)ethoxy,Z~lselenonylethane, 2 H), 7.7 12.5 and 130.2, C
H
e,
m.p. 118-2OY.
'ii-nmr 6 8.15
- 7.95
(m,
(s, 5 H), 5.25 (dd, 1 H, J = 10.8 and 3.0 Hz), 4,y (dd, 1 H, J = (dd, 1 H, 3 = 12.5 and 3.0 HZ), 3.7 - 3.3 (m, 5 H). C-nmr 6 134.2,
(m, 3 H), 7.35br
- 7.5 10.8
Hz),
129.2,
3.75
127.0,
0 Se: C
126.6,
54.39. H
74.9
(C-l),
5.14. Found:
70.5
(CH ),
66.8
(C-2),
60.6
(CH2).
Anal.
Calcd
for
C, 54.42; H, 5.12.
1 m.p. 127-9'C. H-nmr 6 7.35br (s, 5 H), 4.9 (dd, 1 H, J = lo.8 and 3.0 HZ), 3.8 (qq, 1 H, J = 12.5 and 10.8 Hz), 3.45 (dd, 1 H, J = 12.5 and 3.0 Hz),
11&l~yf,la;t(o~,2~;hyl,l_le~,
&?,
C-nmr
3.3 (s, 3 H), 3.25 (s, 3 H). 45.7 (Me). Anal. Calcd for C o
6 137.0,
129.2,
Se: C, 45.90;
1 selemne
Reactions of the (Ebbstyryi TO a solution of 8 (5 mrol)
in HeOH
126.7,
77.3
H, 5.41. Found:
(C-l),
65.0
C, 46.00;
(C-2),
56.7
(OMe),
H, 5.43.
8 uith Ibs)(a in IhOH.
(15 ml),
cooled
in an
ice bath,
solid
MeSNa
(10 mol)
was
added. The starting selenone was consumed in 1 h. The reaction was worked up as described above and the residue was chromatographed on a silica gel column using a mixture of light Petroleum and ether
(97:3)
as eluant.
Reaction
products
and
reaction
yields
are
given
under
the
Results
and
section (Scheme 4); physical, spectral and analytical data of the isolated products are below. Under the same conditions the reaction of S (5 mmol) with excess Mesa (50 mmol)
Discussion
given
afforded
compound
14 only.
1,2-Bis(athylthio)phaylethane, 6.5 Hz),
3.1 - 2.9
(c-l), 40.3 60.47;
(c-2),
14,
(m, 2 H), 16.3
1
oil.
H-nmr
1.95
(s, 3 H),
14.6
(Me). Anal.
(me),
1.9
6 7.4 - 7.1 @, 5 H), 3.05 (dd, 1 H, J = 8.5 and C-nmr 6 128.4, 127.9, 127.4, 51.5 (s, 3 H).
Calcd
for C10H14S2:
C, 60.55;
H, 7.13.
l-Phenyl,l-rthoxy,2-mthylthioethane,
+,
oil. 'H-nmr
6 7.35br
(s, 5 H), 4.4
and 5.7 HZ), 3.25 (~~~3 H), 2.9 (dd, 1 H, J = 13.2 and
7.5 Hz),
2.65
C,
(dd, 1 H, J = 7.5
(dd, 1 H, J = 13.2 and
C-nmr 6140.8, 128.3, 127.8, 126.6, 83.9 (C-l), 56.7 (OMe), 41.8 Hz), 2.05 (s, 3 H). (SMe). Anal. Calcd for CIOH 40S: C, 65.88; H, 7.76. Found: C. 65.79: H, 7.68.
i yl pheny 1 selennnes
Reactions of the 64koxyal TO a solution The
Found:
H, 7.16.
mixture
reaction
of 9 (5 mmol), stirred
was
at
in methanol
room
9 with HeSRaor lbolla in CboH.
(15 ml), MeSNa
temperature
times were 2 - 6 h in the case
until
of HeSNa
the
and
(IO mnol) or NeONa starting
Under these conditions
reaction
mixtures
deactivated Discussion reported
deriving
alumina section
below.
a-alkoxystyrenes
from the reactions
column. (Scheme
Compounds
the
Reaction
products
selenone
8 - 10 h in the
was poured on water, extracted with chloroform, worked up in through a silica gel column using mixtures of light petroleum eluant.
the
are partially
with MeONa
were
and reaction
case
usual
therefore
yields
and
(from
converted
l_Phenyl,l_ethoxy,2athylthioetham,,
e,
oil. 2.9
H-nmr 6 7.35br (dd, 1 H, J = 11.2
(tic);
The mixture
chromatographed
97:3 to 9O:lO)
into acetophenone.
chromatographed
are given
under
the
, spectral and analytical data of the isolated have already,been described.
and 5.7 Hz), 3.35 (q, 2 H, J = 7.0 Hz),
was added.
consumed
of NeONa.
way
and ether
(20 mol) was
5); physical 15a and g
5.7
(C-2), 16.5
as The
through
a
Results
and
products
are
(s. 5 H), 4.4 (dd, 1 H, J = 7.5 and 7.5 HZ), 2.65 (dd, 1 H. J =
13.2 and 5.7 Hz), 2.1 (s, 3 H), 1.2 (t, 3 H, J = 7.0 Hz). C-nmr 6 141.7, 128.4, 127.9, 126.7, 82.3 (C-l), 64.5 (CH ), 42.1 (C-2), 16.7 (We), 15.3 (Me). Anal. Calcd for C11H160S: C, 67.29: H, 8.23. Found:
C, 67.3$; H, 8.26.
l-f%nyl,l-(2_hydroxy)ethoxy,2*thylthioethme,
l&
oil.
1
67.3br (s, 5 H), 4.4 (dd, 1 H, 2.9 (dd,,] H, J = 13.8 and 8.1 HZ), 2.75br (s, 1 H), 2.65 (dd, 1 H, J = 13.8 and 5.1 Hz), 2.1 (s, 3 H). C-nmr 6 128.5, 127.9, 126.4, 82.0 (C-l), 70.3 (CH2), 61.7 (CH2), 42.1 (C-2). 16.4 (Me). Anal. Calcd for CllH1602S: C, J = 8.1 and 5.1 Hz), 3.8 - 3.55
62.22;
H, 7.61. Found:
l-Phenyl,l~thoxy,2+l (m, 2 H), 7.3br = 12.0 and 128.6, those
126.8,
reported
3.55
- 3.35
C, 62.26; H, 7.58.
enylselenoethane,
l&,
oil
3.25
(s, 3 H),
126.7,
3.1
83.3 4s -I),
H-nmr (m, 2 H),
14 1 b.p. 181-2'%/8 mm). H-nmr 6 7.55 - 7.35 (dd, 1 H, J = 7.8 and 51.34Hz), 3.4 (dd, 1 H, J
(Lit.
(s, 5 H), 7.25 - 7.1 (m, 3 H), 4.35
7.8 Hz),
128.1,
(m, 2 H),
(dd, 1 H, J = 12.0 and 57.0
(Me),
35.4
(C-2).
5.4 Hz). The proton
C-nmr 6 nmr data
132.6, 129.0, correspond to
in the literature.
l-Phenyl,l4thoxy,2-phenylselen0ethane,
llJ, oil. 'H-nmr 6 7.55 - 7.4 (m, 2 H), 7.25br (s, 5 H), (dd, 1 H, J = 8.1 and 5.4 Hz), 3.4 (q, 2 H. J = 7.2 Hz), 3.35 (% 1 H, J = 12.3 and 8.1 Hz), 3.05 (dd, 1 H, J = 12.3 and 5.4 Hz), 1.15 (t, 3 H, J = 7.2 Hz). C-nmr 6 141.7, 132.6, 129.0, 128.5, 128.0, 126.8, 126.7, 81.6 (C-l), 64.7 (CH2), 35.7 (C-2), 15.3 (Me).
7.2 - 7.0 (m, 3 H), 4.45
Anal.
Calcd for C16H 80Se: C, 62.94;
to an authentic
samp 1e prepared
H, 5.95. Qund:
C, 62.07;
H, 5.90.
This
product
is identical
independently.
l-f%enyl,l-(2~ydroxy)ethoxy,2-phenylselenoethane, 18s. oil. 'H-nmr 6 7.5 - 7.3 (m, 2 H), 7.25 7.0 (m, 8 H), 4.4 (dd, 1 H, J = 8.7 and 4.8 Hz), 3.7 - 3.3 (m, 4 Hi3 3.25 (dd, 1 H, J = 12.6 and 8.7 HZ), 3.05 (dd, 1 H, J = 12.6 and 4.8 Hz), 2.5br (s, 1 H). C-nmr 4 141.0, 132.6, 129.0, 128.5, 1213.0, 126.9, 126.4, 81.8 (C-l), 70.4 (CH ), 61.6 (CH2), 35.7 (C-2). Anal. Calcd for C H 0 Se: C 59.81; H. 5.66. Found: C, 59.77; H, 5.70. llq-QBstatho~y)ph~yIsthane, 19, oil. H-nmr 6 ?33br (s, 5 H), 4.4 (dd, 1 H, J = 7.8 and 4.2 Hz), 3.0 - 3.2 (m, 2 H), 3.4 (s, 3 H), 3.3 (s, 3 H). C-nmr 6139.0, 128.4, 127.9, 126.9, 83.0 (C-l), 77.3 (C-2), 59.1 (Me), 56.9 (Ne). Anal. Calcd for C10H1402: C, 72.24; H. 8.51. Found: C, 72.30; H, 6.55.
4906
M. Tuxm
et ~1.
1,2-Bis(ethoxy)ph~lethsna,
2J, oil. 'H-nmr 67,jbr (s, 5 HI, 4.45 (dd, 1 H, J = 7.5 and 4.5 Hz), 3.75 - 3.25 (m, 6 HI, 1.2 (t, 6 H, J = 7.2 Hz). C-nmr 6140.3, 128.3, 127.7. 126.9, 81.5 (C-l), 75.5 (C-2). 66.8 (CH ), 64.5 (CH2), 15.4 (Me), 15.1 (Me). Anal. Calcd for C12H1802:~C, 74.17; Hi 9.36. Found:
C, 74.1 6; H, 9.25,5
tithoxystyrene,
21,
oil
(Lit.
b.p.
109-12Y/30
nun). 'H-nmr
6 7.7 - 7.5
(m, 2 H),
7.35
(m, 3 H), 4.6 (d,31 H, J = 2.5 Hz), 4.2 (d, 1 H, J = 2.5 Hz), 3.9 (q, 2 H, J = 7.2 Hz), H, J = 7.2 Hz). !CH 1, 14.5
C-nmr
(He).
d 160,16 (vin-C),
The
proton
and
136.8,{ipso-C),
carbon-13
nmr
128.4,
data
128.1,
125.5,
correspond
to
(t, 3
(vin-C),
82.2
those
- 7.15
1.4
reported
63.3 in
the
literature.
Reactions
of the
Lalkoxyalkyl phony1 selemonrs 9 with Ib5Na or PlsClMain DW. of 9 (5 mmol), in DMF (15 ml), cooled at O°C in an ice bath,
To a solution MeONa
(IO mmol) was added under stirring.
up in the
usual
the case
of the
under
the
already
The reactions
were complete
way. The product isolated by column chromatography reactions
Results
and
with
MeSNa
Discussion
been described.
or MeONa,
section
respectively)
(Scheme
The data of compound
6).
Compounds
the
MeSNa
0.5 h and
(on silica
and
15d are reported
after
gel
reaction
&,
e,
g,
(6 mrol) were
or
worked
or on alumina in yields are given 23,
and
24
have
below.
1-Phenyl,l-allyloxy,2-rethylthioetbane, l!iJ, oil. H-nmr 67.35br (s, 5 H), 5.85 (ddt, 1 H, J = 18.0, 10.2 and 5.4 Hz), 5.2 (ddt, 1 H, J = 18.0, 2.4 and 1.5 Hz), 5.1 (ddt, 1 H, J = 10.2, 2.4 and 1.2 HZ), 4.45 H, J = 13.2 134.8
(dd, 1 H, J = 7.2 and 5.7 Hz), 3.9 (ddd, 2 H, J = 5.4, 1.5 and and 7.2
(vin-C),
128.4,
Anal. Calcd for C
Reaction
Hz),
of the
H
2.65
127.9, 126.8,
116.7
phony1 solenone
8 (5 mmol) was added
ml) and the mixture
(vin-C),
was
stirred
8 with
to a solution
at 50°C for
5.7 Hz),
2.05
81.6 (C-l), 69.7
OS: C, 69.17; H, 7.76. Found:
(&$-8%tyryl
The selenone
(dd, 1 H, J = 13.2 and
1.2,~~).
(s, 3 H).
(CH2),
2.9
(dd, 1
C-nmr 6 141.2, (C-2). 16.7 (Me).
41.9
C, 69.23; H, 7.80.
KOHin TRF. of KOH
(7.5 mm011
18 h. The mixture
in water
was poured
(7 ml) and
on water
and
THF
(3
extracted
through a silica gel with chloroform. After the usual work up the residue was chromatographed column using chloroform as eluant. The phenylethylene oxide 27 was obtained in 45% yields. Glc retention time and proton nmr spectrum were identical to those of the commercial product. Reaction of 1-phenyl,l-(24ydroxy)ethoxy,2-phemylselenonyleth 9e with NaH in THF. Sodium hydride (5 mm011 was added to a solution of 9a (5 mmol) in THF (15 ml) and the mixture was
stirred
purified ether
at
room
by column
temperature
for
IO h. After theYusual work up the reaction product on deactivated alumina using a mixture of light petroleum
chromatography
(95:5) as eluant.
Compound
a-(244ydroxy)ethoxystyrene,
30,
30 "7s obtained
was and
in 82% yields.
ox.
H-nmr 6 7.65 - 7.45 (m, 2 H), 7.3 - 7.15 (m,,] HI, 4.65 (d, 1 H, J = 2.5 Hz), 4.2 (d, 1 H, J = 2.5 Hz), 3.9br (s, 4 H), 2.4br (s, 1 HI. C-nmr 6 159.8 (vin-C), 136.3 (ipso-c), 128.5, 128.1, 125.4, 83.0 (vin-C), 69.1 (CH2), 61.2 (CH2). Anal. Calcd for C10H1202:
C, 73.13;
kknouled~nts.
H, 7.38. Found: C, 73.18;
H, 7.35.
We gratefully
acknowledge
financial
della
Istruzione,
Italy.
Pubblica
support
from
the
CNR,
Rome
and
Minister0
REFERENCESA)I) ROTES I) Preceding
paper.
2) M. Tiecco,
L. Testaferri,
M. Tingoli,
D. Chianelli,
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M. Tingoli,
D. Chianelli,
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M. Tingoli,
and D. Chianelli,
J.
Org. them.,
48, 4289
(1983). 3) M. Tiecco,
M. Montanucci,
Tetrahedron
Lett.,
25,
4975 (1984). 4) L. Testaferri,
M. Tiecco,
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M. Shimizu,
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Tetrahedron,
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a mixture
M. Tingoli,
26, 5571 (1965). tructural
attribution
was made by comparison
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T. Aoai,
16) A. P. Uijttewaal,
(1984).
and J-N. Denis, J. Chem. Sot. Chem. Cornnun., 571 (1985).
H-nmr spectrum and coworkers,
14) A. Toshimitsu,
Tetrahedron
57, 2897
45, 4063 (1980).
D. Chianelli,
and F. Maiolo,
Synthesis,
478 (1982).
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to 4906.
0
FMTIOW
AK0 REACTIVITY AI0 TNIDLATE
MARCELLO
TlECCO.*
DONATELLA
OD4@-4020/86 1986 F’qamon
1986
DONATELLA
OF THE MolTToW
PRODUCTS
ANlowS
SELD(OIIES
CHIANELLI,
TO VINYL
MARCO TINGOLI,
S3.00 + .OO Journals Ltd.
OF ALKOKTDES
LORENZO
TESTAFERRI
and
BARTOLl
lstituto
di Chimica
Facolti
Organica,
di Farmacia,
Universita
di Perugia,
Italy.
(Received in UK I3 June 1986)
Abstract. product
Vinyl selenones of conjugate
On the contrary, conjugate
are
selenonyl
group.
MeOH and
in
is
making
acidic
the
nucleophilic
We have
The
reactions
previously
methoxide.
in
unactivated
observed
These
vinyl salenones
the
conjugate
inferred of
some
intermediates
in
these
were rapidly selenonyl
atoms.
products
group.
ways
alkyl
choice
of
These
of
and
the
results
the
it acts and
a
reagent
indicate
and
of
Useful
that
properties.
good
vinylic,
products.
nucleophilic
carbon-carbon as
the
in
bond
group
in
elimination
solvent
synthetic
the
Beside
double
leaving
and
the
both in
elimination
by
peculiar
the
phenyl
loss
and
followed
group.
affords
with
substitution
with
activates
aliphatic
the desired
vinyl
selenoxides
solvents,
halides,
to
however
2,3
could
allows
to
applications
of
of
of the
1,s
not
to give the products
the
and
giving the
sodium
methanethiolate
products
selenides.
of
starting
selenones
addition
because,
of intermolecular
b-9 4397
medium
their
functionalized
isolated
4
the
as well
salenones
under
the
at the e-
was aprotic
as
(DMF),
intermediates
as from
were
vinyl
vinylic
same conditions
additions
employed
products
sodium
than those with other
Under
formation
and
nucleophilic
rise to competitive
reaction
isolated;
Similar
further
were
sulphides
be
with
and occur much more easily
since
not
react
afford
behaviour
However,
products.
reactions
compounds
consumed
it
reagents
isomerization
reaction the
atoms
an ambidentic
bcarbon
from the observed the
from
reactions
group
are stereospecific
like vinyl
addition
of
species;
aprotic
-1 present
as well as at the
that
reactions
substrates
anions
are presented.
dipolar
1
substitution.
to give the
selenonyl
e-alkoxy
several
thus generated.
both
towards
These
in
derive
Michael
attracting
of anionic
appropriate
the reaction
these
selenone
substitution,
alkoxide
yields. react
observed
a-hydrogen
with
of the
with MeONa or MeSHa have been investigated
retro
electron
the addition
reactions.
from
out
excellent can
in methanol
displacement
carried
which
products
as
strong
a
in
reactions
of the vinyl
ArSeO2
direct
The
well
subsequent
reaction
compounds
Their
DMF.
substitution
and
products
stable
as
processes
towards
the same
addition
selenones
react with sodium methanethiolate
addition
also
with
the
structure
formulated
other
displacement
as
anionic
condi-Lions employed,
or intramolecular
was
they of the
M. TIECCU er al.
4898
The
reactions
investigated sulphur
in
can
be
isolated
observe
the
loss
of
addition good
nature
the
compounds 2 and
their
OMF support
the
nucleophiles
in
the
vinylic
the
addition
products
2.
lJhen alkoxide
The anionic
of
the
m-proton
group
with
the
z
give
the
MeSNa in
in
the
the at
the
oxygen
and
the
2
(Nu
the
o-carbon
to
the
The of
= OR)
one
can
a-proton give
the
substitution
paper
OK.
behaviour
to
reactions.
at
this
vinyl
6-carbon
several
attack
the
this
in
now
medium employed,
1,
MeOH and
of
to
been
With
at
compounds
structures
WC describe
the
occur. (Nu)
rise
attack
particular
interpretation
not
reaction
have
of
employed
selenone
and
3,
products.
McONa and
are
on the
vinyl
having
does
nucleophile
anions
and
BeSNa
nucleophilicity
the
selenones
products
cyclic
proposed
aprotic
give
give
of
(X-1
nucleophiles
afford
reaction
to
the
RONa and
substitution
alkyl
species
to
with
aryl
with
conditions
is
previously dipolar
these
selenones
and
the
to
vinyl
observed
yields.
10
j;
intramolecularly
Under
of
selenonyl
products
and
decreased
abstraction
substitution occur
solvents.
process
in
on the
selenoxides
greatly
only
conjugate
Depending
with
is
1 the
the
vinyl
protic
anions
selenones give
of
synthesis
results
vinyl
can of
obtained
in
selenones
with
solvents.’
R
R
R
b 67
SeO,Ph
Nu
I
E
.L
L
X-
w SeO,Ph
F
---INu
*
"h Nu
X
A
X=or#Nu
RESULTS AH) DISCUSSIUR
From the minute
reaction
amounts
mixture;
most
of of
of the
the
the
(E)-6-styryl
addition
phenyl
product
starting
product
a
could
remained
selenoxide be evidenced unchanged
SCHEME Ph L I
5
by
giving
rise
On the ice
bath,
similar of
the
yields
of
exclusively contrary,
from
addition
SeOPh
the
11
The reaction
deoxygenated
was formed
could
of be
which other
phenyl
L 7
with
product
(E)d-styryl
reaction
products
reaction
could
be found
different
course
PhyHCH,SeOPh
MeSNa_ MeOH
compound a. to
the
No conditions
the
Ph
when the
a precipitate way,
of
of
.!i
L 7
the
1).
analysis
presence
Me0
Ph
improve
H-nmr
MeOH the
1
2
to
HeONa in
1
(Scheme
MeONa, &OH
SeOPh
with
obtained
HeSNa took
j as
anions
(Scheme
a completely
1.
selenone
was identified alkoxide
SePh
2).
in
was treated
with
the
addition
the
Michael
corresponding
Compound e
was
MeONa in
product
alcohols, also
MeOH,
obtained
in
In a
%. high
an
yields
from
the
4899
Additionproductsof alkoxidwand thiotattanionsto vinylselcnoncs I#?)-isomer _I& The addition selcnone
product 12 was formed from the
with NeONa in &OH. These are the
11
SCHEME
Ph
L -N
first
of the
(EMt-styryl
methyl
in which the conjugate addition
examples
2
:~yseo2Ph
RONa_ ROH
SiqPil
reaction
S_a: R L:Me (95%)
u!!
@: R= Et (93%) 9,~ : R z CHMe, (92%) 9:
R = CH,CH=CH,
(86%)
S_e: R= CH,CH,OH
MeONa, PhLJseo2Ph MeOH
(83%)
$J (80%)
$J Ph L 7
MeO?Ja_ MeOH
Se&Me
Ph SeO,Me )-/ Med
?s, -
12 (86%)
products of an anionic species to vinyl selenones could be isolated. is straightforward
The course of these reactions
and is reported in Scheme 3 in the case of the addition
of sodium methoxide in
methanol:
SCHEME
PhCH=CHSeO~Ph
+ MeO-.;lcr
3
PhCH~~Se02Ph
MsCrHc
PhCHCH~~02P~
b Me 8910 -WW.
is
reversible.
catalytic
reversibility oxidation
Indeed,
amounts of
precipitation,
the
process
The reaction of the vinyl
as
ions are needed as catalysts
MeONa were employed. is completely
be discussed 12 selenides. selenone
in 1 h. the
to
mixture
com~unds
-lh
2
are
substracted
be obtained
by two products fi
The formation
and
of these
1_I!which abstracts
a proton from the solvent
l~methylthio,2-~enylselenonyl,l-phenylethane in the presence of a strong
to give methoxide anions and the E.
This
nucleophile
aryl
alkyl
selenone
by
were the
two products the carbanion
addition
however
such as the He5 anion,
by the
in MeOH
which
(35%)
in Scheme 4. Addition of the FleS anion to 3 gives
as indicated
for
(2 molar equivalents)
was constituted
(38%) (Scheme 4).
in which only
Further evidences
Compounds 2 can also
below.
1,2-bis(methylthio~phenylethane
1-phenyl,l-methoxy,Z-methylthioethane
only and that the process in the case
the right.
J! with sodium methanethiolate
The reaction
can be rationalized
since,
shifted
well also
since
Besides,
will
of the corresponding
at 0% was complete
isolated
e?
compound !& was obtained equally
the equilibrium of
identified
t)Me
E!
This mechasnism suggests that alkoxide
+ f@ieO-
it
product cannot
be
is rapidly
M. TIECCD er al.
4900
consumed
to
(Scheme
give
the
substitution
3) the methoxide
like 12,
product
-14.
ions react easily
On
product
SCHEME
SeO,Ph
hand,
as
Ph a==
been
product
1;
shown
this
above
selenone,
the MeS- is consumed
in
Me0 PhhSMe
l
E
!!
8 + MeS-
has
4
MeS
I
it
15a. Thus, whereas
PhhSMe
MeSNat MeOH
L 7
other
with 8 to give the addition
reacts with MeS- to give the observed
Ph
the
SeO,Ph
Ph MeOH, *
Y
SeO,Ph MeO-
l
t/
MeS
MeS 18
!z
MeS
A
MeO-
l
m
13 _
-#Qk
E
+ MeO-
1
MeS-
the substitution a catalytic
process
The results with
react
employed, the
isolated products this
faster
with
of j
they
deriving
selenone
reaction isolated selenones of the
is
the
in protic
are
Krief
instead and
substitution
ions are continuously
3 and 4 seem to indicate and oa
than
with
MeSNa
rapidly
process
consumed
than
E
and
in HeOH, consumed
98;
as
reaction
by
the ions
solvents at the
in competition
coworkers reactions
10
have
with
The
are completely
o-carbon
a
recently variety
of
j,
under
the
fact,
other
of
both
no products Attack
solvents that
nucleophiles
MeS
c
hand
alkyl
are
at
the
formation
of
all
to suppress the starting
Indeed
anions
and
when
2
the
(70%) was with
vinyl
from the addition at
the
bcarbon
employed.’
phenyl
including
be
compound RO
Thus,
cannot
In order
o-
conditions
1
deriving the
mathoxide
and
anion.
and
the
faster
be observed.
in which
methanethiolate
react the
under not
be avoided.
conditions
be observed. aprotic
whereas
(IO molar equivalents)
reactions
anions
products
the
in
to ! cannot
with
reported of
selenone
addition
regioselective;
atom could
when dipolar
the thiolate
matter
and
MeS-
to work
reaction
product.
a
with 8; this is
regenerated.
that
vinyl
the conjugate
of methoxide
the
the
in the reaction
of -17 and -ga with f!eO- could
it is necessary by
with
out with a large excess of MeSNa
sole
nucleophiles
the MCO- is only involved
from the reaction
with
are
x
by the addition
was carried as
8
deriving
reaction since
in Schemes
selenones
latter undesired
vinyl
atoms
aryl
products
of II and 2,
from which methoxide
reported
the alkyl
anions
from
reactions
selenones
HeONa
in
readily
MeOH
and
undergo PhSNa
in
Addition
ethanol.
We have
examined
MeSNa in MeOH and above
(Scheme
The reactions afforded
Apart
5). from
the
OW.
the
nucleophile
side
at
the
of
aryl
alkyl
9 with
the
of the
reaction, a-carbon
of
B-alkoxyalkyl
were
already
selenones
were
products
amounts
predominant
the
aryl
e
v
Ph
reactions
with the
from
accompanied mixture 5).
of
These
from the
the
vinyl
attack
reactions place selenone of
at are
but
the
anions of
second
selenone
8 and
has
gave
is
the
attack
of
products.
the The
SePh
1%
(5%)
(63%)
12
(58x)
1s z
(17%) (23%)
Ph
c
Et0
o-carbon
which
+
hOMe
Ph k
Me0
2,o (48%)
Ph
h OEt
the
+ Et0
in
at
the
the
out,
the
the
the
F
-9
is
of 98 similar
the to
of the
a different
with
EtONa.
the
ArSe02
group;
19
this
EtOH (Scheme directly
case
and
therefore
the 11
was
A similar
starting
carbanion
carried
responsable
g.
EtONa in
In
course.
product
results,
substitution
give
reaction
probably
took
substitution
o-methoxystyrene
MeONa or
i.e.
The same
the
quite of
and
the
reaction
a-proton
substitution
selenones
10 h)
as
with
equivalents
consequences. of
identified
E-hydrogen, at
(8 -
equivalents)
from
be carried
The attack
product
moiety
was
5 molar
slower
rolar
was obtained
using and
were
MeONa (4
also
no practical
only
alkyl
elimination
can
in competition.
it
group.
(82%)
Me0
alcohols
with
21 and g
reactions
the
in
>
compound
two products two
alkoxy
22 (42%)
alkoxide
a
3
the
12
Ph
EtOH
reaction by
compounds
of
t/ RO
9b
Thus
room temperature,
e : R = CH,CH,OH
c
EtONa
at
substitution
12 (34%)
SeO,Ph
described
intermediates.
1s
b:R=Et
9a
Et0
the
R
MeOH
Ph
case
l
MeONa
F
nature
in this give
reactions as
deoxygenated
the
Ph
a: R=Me
Me0
to
NeONa and
5
MeSNa MeOH
SeO,Ph
some
with
9 towards
the
intervene
in methanol
observed
selenone
alkyl
from to
with
changed
process
selenones
available proposed
together
SCHEME
Ph
phenyl
equivalents),
two products
the
4901
and thiolate anions to vinyl sclenones
MeSNa (2 molar
substitution
The relative this
behaviour
compounds
expected
of alkoxida
Some information
which
of
the
(Scheme
in
4) in
products
elimination
is
also
taking
out on the n-decyl phenyl 10 the particular structure for
the
occurrence
of
the
reaction.
The reactivity with
MeSNa (0°C.
the
(El-a-styryl
of
the
selenones
0.5
h),
together
with
the
substitution
sulphide
23,
was
isolated;
methyl
9 changed
on passing
from
methanol
products the
relative
to
a second amounts
OMF. From
the
compound,
identified
of
the
two
reactions
products
as
4902
M.
changed
with
the
bulkiness
of -Pa with
reaction
MeONa
mixture
was constituted
confirm
previous
strong
bases.
of
the
COY,
alkyl
0.5 h)
TIECCXI er al.
group
did
R
not
by the a-methoxystyrene
observations
that
alkoxide
in the
give
starting
any
substitution
-20 and the anions
in
selenones
product
Ph
SeO,Ph
MeSNa DMF
v RO
more
than
as
a: R=Me
Ph
SeOzPh
reaction
These
results
behave
as
Ph
c
L 7
l
RO
SMe
l&t
90% 1
SMe 23
place to afford by
the the
(36%) (42%)
Ph
Ph b
L 7
+
OMe
Me0
of compounds
23 and 24 clearly
(El-6-styryl MeS
of a proton
or from
the
phenyl Me0
selenone
s
This
anions.'
the solvent
from the equilibrium
indicates
that in OFF a retro
(Scheme reaction
7) which
addition
SCHEME
Ph
proceeds
of nucleophiles
nucleophilic
easily and
reaction
since,
the
in
selenone
takes
vinylic OMF,
the
8 can be _
.
This
at the o-position.'
7
Ph
SeO,Ph )A
Michael
suffers
by the anion -13 is difficult
by irreversible
(5%)
-
e:R=CH$H,OH
MeONa ) DMF
Me0
subtracted
24.
The
6
d:R = CHICH=CH2
Y
substitution
6).
the
nucleophiles
15dt45X) jTJ,oX)
abstraction
19;
(El-B-methoxystyrene
DM
(Scheme
1,13
SCHEME
The formation
!
L 7
s===
RO !z
l
SeO,Ph
k
I
Nu-
Ph L 7 Nu g:Nu=
MeS
24: NU z Me0
RO-
4903
Addition products of alkoxides and thiolate anions to vinyl selenones
interpretation
is
corroborated
of MeONacompound 8 can be isolated with some -20 and -24.
It
is
fact
by the
that
when %
from the reaction
interesting
to
note
of g with NeONa in DMF. The present
behaviour
vinyl
results
of
selenones
collected
in
towards
Scheme 6 show that
compounds
whereas
a-hydrogen
of
abstraction
of the a-hydrogen
in methanol also other
selenone
8;
The reaction proceeds
the
of g
epoxides
from
presence
the
to
the
from hydroxyselenones
contrary,
to
effect
the
case
does the
not
alkoxy
aryl
alkyl
has
been
produced
26
likely
from h
__
isolated
reaction rather
reaction
The results
aprotic
products
is
discussed
selenoxides
alkyl
likely
is
stage
initially
to
the the
occurring
of
the
conjugate
low
yields
the
vinyl
addition (45%).
carbanion
intramolecular for
the
tetrahydrofuran
in
formed
produced;
responsable with
ions
in water using
e
The gives
nucleophilic
observed
formation
of
potassium
displacement
to
with NaH in THF, did not give
afford
oxethanes.
On
any phenyl dioxane
29,
8
SeO,Ph
P
Ph I7 0
0-
2,s
Ph -
v
Ok \ CH$H,OH
\ CH,CH@-
product
to protic
very
being
the alkene
than as nucleophiles greatly
favoured
in the present
and vinyl
selenones. are
8-hydrogens;
very
and
?.!
as bases
dipolar
the
the
is
SeO,Ph
2,s
aryl
the
a-carbon
hydroxide
?..?
0
vinyl
the
>1-_ HO
Ph
elimination
of Thus,
the
and
although
intramolecular
!!”
only
work.’
from
t-butoxide in THF in the 698 that alkoxide ions shown by Kuwajima and coworkers
Ph HO-
of
at the i!J
that
selenones
a similar
SeO*P h
the
obtained
to 9 which is consumed by the
hydroxide
stop
anion
26 are very
Ph
behave
Q
process
-9a together
interpretation
previous
attacks
revert
addition
epoxide
SCHEME
l
unreacted
the
the
the
Michael
11 can easily
afford
the
like
give
the anion g,
L 7
attacks
retro
(Scheme 8) assuming
which
-27. Anions
reaction of 10 It belzaldehyde.
of
derived
from
affords
the
support in
MeS anion
out with potassium
in this
further
can be explained
B-hydroxyselenone
displacement
out
were carried
product formation
thus
quantity
(Scheme 5).
as a cosolvent. it
Me0 anion
the carbanion
carried
the reactions
but
case
processes were also
the
an insufficient
which contains
DMF given
DMF the
which initiates
but in this
irreversible
Experiments
9,
in
in
with
compounds -20 and -24 were also
results
alkoxides
treated
mixture
that
the reactions
is
selenones solvents;
Thus vinyl
versatile
30
and in the
by a
six
(82%). case
As suggested of
the
anion
membered transition
and in the previous’
paper indicate nucleophiles
changes
selenoxides,
intermediates
which
in reactivity
vinyl can
selenones be
easily
that
anions
the reactivity
changes
are also and
alkoxy
intramolecular
state.
with oxygen and sulphur similar
above -28 the
on passing
produced
their
transformed
in the case
conjugate into
of from
a
of
addition series
of
M. TIECCXJet al.
4904
valuable
compounds.
seleninyl
and
particular, the
the
these
reactions
selenonyl
groups
are
made
which
interesting
are
carried
out
characteristics;
reagents
and
and vinylic)
alkyl selenones
have acidic
choice
reagent
of
the
selenoxides,
vinyl
time and
and
of
group
peculiar
in nucleophilic
leaving
reactions.
solvent
The
bond
of
the
substituents.
In
substitutions
group
towards
shows the
group
in nucleophilic
Moreover
the a-hydrogen
in the
allows
addition
properties
vinylic ArSeO2
double
Thus, as anticipated
reaction
the
electron-attracting
solvents.
as a good
and their conjugate
containing
by
the carbon-carbon
it acts
the
strong
aprotic
in elimination
properties.
salenones
with loss of the selenium
dipolar
it activates
at same
(both aliphatic
in
possible
are
the ArSeO group acts as good leaving
reactions
anionic
All
to
direct
products
the
towards
addition
of
substitutions atoms
introduction,
when
several
in aryl
the appropriate
reactions
the desired
of
vinyl
derivatives
functions.
EXPERlKNfAL Structural
attributions
were
Proton nmr
spectra
recorded
were
made
by
carbon-13
proton,
at 90 Mz
nmr
on a Varian
were recorded
at 20.15 MHz on a Bruker WP 80 SY instrument
with
decoupling
proton
experiments. on a Carlo
CDCl Erba
phenyl
1106
Elemental
some
cases
and TMS as Analizer.
were
assignments
Elemental
analyses
were
elemental
carbon-13 made
by
analyses
performed
and
11
were
prepared
1, a-methoxystyrene
&I,
as
described
(E)-bstyryl
in the
methyl
analyses. nmr
spectra mode
off-resonance
were
on a
previous
sulphide
been described. of the (El-6-styryl phenyl selenone 8 with alkoxides. To the selenone 8 (5 mmol), dissolved in methanol or in ethanol
3
by
in the Fourier transform
operating
reference.
Glc
and
carried
out
Hewlett-Packard
with a 20 in. 10% UCW 982 column.
5, S, lo,
selenide
In
was used as solvent de1 la,
5830 A chromatograph Compounds
throughout.
spectra
EM 390 instrument;
B
paper.'
(E)-s-Styryl (E)-bmethoxystyrene
and
have already
Reactions bath,
sodium
solution
metho;de
of the
alcohol
alkoxide
reaction
times
chloroform.
After
was purified solid
were as
containing
in
ethoxide
in the
and the selenone
mixtures
the
or
alcohol %,
follows:
was
with
with at
white
water
light
room
was
added
prepared
the chloroform
hydride
on
water
can
resulting
in an ice cases a
other
(5 mmol)
and
and evaporated.
purification
the
the
to
the
was monitored by glc. The h; %, 12 h. The reaction
4.5
Poured
was dried
cooling
and
sodium
h; W,
were
Further
petroleum.
temperature
ml) and cooled In
adding
2.5
9
(15
stirring.
of the reaction
4 h; B,
products
under
by
The progress
2 h; s,
insoluble
washing
ethanol
mnol)
B was then added.
the
by washing
(5
extracted
The
be effected
solution
in
solid
with
residue
by dissolving an
ice
bath.
9a was similarly prepared starting from 10. The reaction of the (E)-B-styryl methyl selenone swith MaONa in MaOH was carried out in ayimilar way. Reaction yields are given under spectral and analytical data are reported the Results and Discussion section (Scheme 2); physical, Compound
below.
enylselemnylethane,
1-Phenyl,lathoxy,2-ph 7.5 (m, 3 H), 7.3br Hz),
3.6
(s, 5 H), 4.95
(dd, 1 H, J = 12.5 and
129.1, 127.1, 5.00. Found:
126.6,
3.0 Hz),
77.2 (C-l), 66.8
C, 55.81;
19.8 Hz), 3.6.(dd,
5 H),
C-nmr 6133.8,
129.8, H
3,
129.1,
129.0, 127.2,
(s, 5H),
3.6 (dd, 1 H, J ~~12.5
5.2
(m, 2 H),
7.7 -
C-nmr
(s, 3 H).
56.6
(Me).
Anal.
m.p.
136-8'C.
6
Calcd
143.9, for
137.2,
133.9,
C15H1603Se:
* 'H-nmr 6 8.15 - 7.95
129.8,
C, 55.73;
(m, 2 H),
126.5, 75.4
H,
7.7 -
$,
(C-l), 66.7 (C-2), 64.6
(CH2). 14.7 (Me)*
C, 57.02; HI 5:33.
m.p.
(dd, 1 H, J = 10.5
H-nmr 6 8.1 - 7.95 (m, 2 H), 7.7 2.7 Hz), 3.95 (dd, 1 H, J = 12.5 and
145-7’C. and
and 2.7 Hz), 3.5 (spt, 1 H, J = 6 Hz), 1.1 (d, 3 H, J = 6.0
C-nmr 0.85 (d, 3 H, J = 6.0 Hz). (C-I), 69.7 (cH), 66.6 (c-2), 22.9 C, 58.00;
6 8.1 - 7.9
5.05
1-Phenyl,l-isopro~x~~2$henylsolemflylethane,
Found:
3.15
(C-2).
0 Se: C. 56.97: H, 5.39. Found:
- 7.5 (m, 3 H), 7.3br
HZ),
H-nmr
(dd, 1 H, J = 10.8 and 3.0 Hz), 3.9 (dd, 1 H, J = 12.5 and 1 H, J = 12.5 and 3.0 Hz), 3.3 (q, 2 H, J = 7.2 Hz), 0.95 (t, 3 H, J = 7.2 Hz). (s,
Anal. Calcd for C
10.5
1
m.p. 171-3OC.
H, 4.97.
1-Phenyl,l_ethoxy,2-phenylselenonylethane, 7.55 (m, 3 H), 7.3br
1,
(dd, 1 H, J = 10.8 and 3,g Hz), 3.9 (dd, 1 H, J = 12.5 and 10.8
8 144.2, 138.5,
133.7,
129.7,
129.0,
128.9,
(Me), 20.6 (Me). Anal. Calcd for C17H2003Se:
127.1,
126.6,
C. 58.11;
Hz)* 72.5
H. 5.75.
H, 5.74. 'H-nmrb 8.1 - 7.95 (m, 2 H), 7.65 W, m.p. 107-8°C. (s, 5 H), 5.65 (ddt, 1 H, J = 18.0, 9.0 and 5.4 Hz), 5.15 - 4.9 (m, 2 H), 5.1
l~yl,l_allyloxy,2-phanylselenonylethme, 7.5 (m, 3 H), 7.3br
(dd, 1 H, J = 10.5 and 3.0 HZ), 3.95 (dd, 1 H,,J = 12.5 and 10.5 Hz), 3.8 (dt, 2 H, J = 5.4 and C-nmr 6 143.9, 137.4, 133.8, 133.5 (vin-C), 129.9, 1.2 HZ), 3.65 (dd, 1 H, J = 12.5 and 3.0 Hz). 129.2, 127.3, 126.7, 117.5 (vin-C), 75.0 (C-l), 69.9 (CH2), 66.7 (C-2). Anal. C&d for
C17H1803Se: C, 58.45; H, 5.20. Found: C, 58.51; H, 5.23.
4905
Addition products of alkoxides and thiolatc anions to vinyl selenones
I-hyl,l-(2_hydroxy)ethoxy,Z~lselenonylethane, 2 H), 7.7 12.5 and 130.2, C
H
e,
m.p. 118-2OY.
'ii-nmr 6 8.15
- 7.95
(m,
(s, 5 H), 5.25 (dd, 1 H, J = 10.8 and 3.0 Hz), 4,y (dd, 1 H, J = (dd, 1 H, 3 = 12.5 and 3.0 HZ), 3.7 - 3.3 (m, 5 H). C-nmr 6 134.2,
(m, 3 H), 7.35br
- 7.5 10.8
Hz),
129.2,
3.75
127.0,
0 Se: C
126.6,
54.39. H
74.9
(C-l),
5.14. Found:
70.5
(CH ),
66.8
(C-2),
60.6
(CH2).
Anal.
Calcd
for
C, 54.42; H, 5.12.
1 m.p. 127-9'C. H-nmr 6 7.35br (s, 5 H), 4.9 (dd, 1 H, J = lo.8 and 3.0 HZ), 3.8 (qq, 1 H, J = 12.5 and 10.8 Hz), 3.45 (dd, 1 H, J = 12.5 and 3.0 Hz),
11&l~yf,la;t(o~,2~;hyl,l_le~,
&?,
C-nmr
3.3 (s, 3 H), 3.25 (s, 3 H). 45.7 (Me). Anal. Calcd for C o
6 137.0,
129.2,
Se: C, 45.90;
1 selemne
Reactions of the (Ebbstyryi TO a solution of 8 (5 mrol)
in HeOH
126.7,
77.3
H, 5.41. Found:
(C-l),
65.0
C, 46.00;
(C-2),
56.7
(OMe),
H, 5.43.
8 uith Ibs)(a in IhOH.
(15 ml),
cooled
in an
ice bath,
solid
MeSNa
(10 mol)
was
added. The starting selenone was consumed in 1 h. The reaction was worked up as described above and the residue was chromatographed on a silica gel column using a mixture of light Petroleum and ether
(97:3)
as eluant.
Reaction
products
and
reaction
yields
are
given
under
the
Results
and
section (Scheme 4); physical, spectral and analytical data of the isolated products are below. Under the same conditions the reaction of S (5 mmol) with excess Mesa (50 mmol)
Discussion
given
afforded
compound
14 only.
1,2-Bis(athylthio)phaylethane, 6.5 Hz),
3.1 - 2.9
(c-l), 40.3 60.47;
(c-2),
14,
(m, 2 H), 16.3
1
oil.
H-nmr
1.95
(s, 3 H),
14.6
(Me). Anal.
(me),
1.9
6 7.4 - 7.1 @, 5 H), 3.05 (dd, 1 H, J = 8.5 and C-nmr 6 128.4, 127.9, 127.4, 51.5 (s, 3 H).
Calcd
for C10H14S2:
C, 60.55;
H, 7.13.
l-Phenyl,l-rthoxy,2-mthylthioethane,
+,
oil. 'H-nmr
6 7.35br
(s, 5 H), 4.4
and 5.7 HZ), 3.25 (~~~3 H), 2.9 (dd, 1 H, J = 13.2 and
7.5 Hz),
2.65
C,
(dd, 1 H, J = 7.5
(dd, 1 H, J = 13.2 and
C-nmr 6140.8, 128.3, 127.8, 126.6, 83.9 (C-l), 56.7 (OMe), 41.8 Hz), 2.05 (s, 3 H). (SMe). Anal. Calcd for CIOH 40S: C, 65.88; H, 7.76. Found: C. 65.79: H, 7.68.
i yl pheny 1 selennnes
Reactions of the 64koxyal TO a solution The
Found:
H, 7.16.
mixture
reaction
of 9 (5 mmol), stirred
was
at
in methanol
room
9 with HeSRaor lbolla in CboH.
(15 ml), MeSNa
temperature
times were 2 - 6 h in the case
until
of HeSNa
the
and
(IO mnol) or NeONa starting
Under these conditions
reaction
mixtures
deactivated Discussion reported
deriving
alumina section
below.
a-alkoxystyrenes
from the reactions
column. (Scheme
Compounds
the
Reaction
products
selenone
8 - 10 h in the
was poured on water, extracted with chloroform, worked up in through a silica gel column using mixtures of light petroleum eluant.
the
are partially
with MeONa
were
and reaction
case
usual
therefore
yields
and
(from
converted
l_Phenyl,l_ethoxy,2athylthioetham,,
e,
oil. 2.9
H-nmr 6 7.35br (dd, 1 H, J = 11.2
(tic);
The mixture
chromatographed
97:3 to 9O:lO)
into acetophenone.
chromatographed
are given
under
the
, spectral and analytical data of the isolated have already,been described.
and 5.7 Hz), 3.35 (q, 2 H, J = 7.0 Hz),
was added.
consumed
of NeONa.
way
and ether
(20 mol) was
5); physical 15a and g
5.7
(C-2), 16.5
as The
through
a
Results
and
products
are
(s. 5 H), 4.4 (dd, 1 H, J = 7.5 and 7.5 HZ), 2.65 (dd, 1 H. J =
13.2 and 5.7 Hz), 2.1 (s, 3 H), 1.2 (t, 3 H, J = 7.0 Hz). C-nmr 6 141.7, 128.4, 127.9, 126.7, 82.3 (C-l), 64.5 (CH ), 42.1 (C-2), 16.7 (We), 15.3 (Me). Anal. Calcd for C11H160S: C, 67.29: H, 8.23. Found:
C, 67.3$; H, 8.26.
l-f%nyl,l-(2_hydroxy)ethoxy,2*thylthioethme,
l&
oil.
1
67.3br (s, 5 H), 4.4 (dd, 1 H, 2.9 (dd,,] H, J = 13.8 and 8.1 HZ), 2.75br (s, 1 H), 2.65 (dd, 1 H, J = 13.8 and 5.1 Hz), 2.1 (s, 3 H). C-nmr 6 128.5, 127.9, 126.4, 82.0 (C-l), 70.3 (CH2), 61.7 (CH2), 42.1 (C-2). 16.4 (Me). Anal. Calcd for CllH1602S: C, J = 8.1 and 5.1 Hz), 3.8 - 3.55
62.22;
H, 7.61. Found:
l-Phenyl,l~thoxy,2+l (m, 2 H), 7.3br = 12.0 and 128.6, those
126.8,
reported
3.55
- 3.35
C, 62.26; H, 7.58.
enylselenoethane,
l&,
oil
3.25
(s, 3 H),
126.7,
3.1
83.3 4s -I),
H-nmr (m, 2 H),
14 1 b.p. 181-2'%/8 mm). H-nmr 6 7.55 - 7.35 (dd, 1 H, J = 7.8 and 51.34Hz), 3.4 (dd, 1 H, J
(Lit.
(s, 5 H), 7.25 - 7.1 (m, 3 H), 4.35
7.8 Hz),
128.1,
(m, 2 H),
(dd, 1 H, J = 12.0 and 57.0
(Me),
35.4
(C-2).
5.4 Hz). The proton
C-nmr 6 nmr data
132.6, 129.0, correspond to
in the literature.
l-Phenyl,l4thoxy,2-phenylselen0ethane,
llJ, oil. 'H-nmr 6 7.55 - 7.4 (m, 2 H), 7.25br (s, 5 H), (dd, 1 H, J = 8.1 and 5.4 Hz), 3.4 (q, 2 H. J = 7.2 Hz), 3.35 (% 1 H, J = 12.3 and 8.1 Hz), 3.05 (dd, 1 H, J = 12.3 and 5.4 Hz), 1.15 (t, 3 H, J = 7.2 Hz). C-nmr 6 141.7, 132.6, 129.0, 128.5, 128.0, 126.8, 126.7, 81.6 (C-l), 64.7 (CH2), 35.7 (C-2), 15.3 (Me).
7.2 - 7.0 (m, 3 H), 4.45
Anal.
Calcd for C16H 80Se: C, 62.94;
to an authentic
samp 1e prepared
H, 5.95. Qund:
C, 62.07;
H, 5.90.
This
product
is identical
independently.
l-f%enyl,l-(2~ydroxy)ethoxy,2-phenylselenoethane, 18s. oil. 'H-nmr 6 7.5 - 7.3 (m, 2 H), 7.25 7.0 (m, 8 H), 4.4 (dd, 1 H, J = 8.7 and 4.8 Hz), 3.7 - 3.3 (m, 4 Hi3 3.25 (dd, 1 H, J = 12.6 and 8.7 HZ), 3.05 (dd, 1 H, J = 12.6 and 4.8 Hz), 2.5br (s, 1 H). C-nmr 4 141.0, 132.6, 129.0, 128.5, 1213.0, 126.9, 126.4, 81.8 (C-l), 70.4 (CH ), 61.6 (CH2), 35.7 (C-2). Anal. Calcd for C H 0 Se: C 59.81; H. 5.66. Found: C, 59.77; H, 5.70. llq-QBstatho~y)ph~yIsthane, 19, oil. H-nmr 6 ?33br (s, 5 H), 4.4 (dd, 1 H, J = 7.8 and 4.2 Hz), 3.0 - 3.2 (m, 2 H), 3.4 (s, 3 H), 3.3 (s, 3 H). C-nmr 6139.0, 128.4, 127.9, 126.9, 83.0 (C-l), 77.3 (C-2), 59.1 (Me), 56.9 (Ne). Anal. Calcd for C10H1402: C, 72.24; H. 8.51. Found: C, 72.30; H, 6.55.
4906
M. Tuxm
et ~1.
1,2-Bis(ethoxy)ph~lethsna,
2J, oil. 'H-nmr 67,jbr (s, 5 HI, 4.45 (dd, 1 H, J = 7.5 and 4.5 Hz), 3.75 - 3.25 (m, 6 HI, 1.2 (t, 6 H, J = 7.2 Hz). C-nmr 6140.3, 128.3, 127.7. 126.9, 81.5 (C-l), 75.5 (C-2). 66.8 (CH ), 64.5 (CH2), 15.4 (Me), 15.1 (Me). Anal. Calcd for C12H1802:~C, 74.17; Hi 9.36. Found:
C, 74.1 6; H, 9.25,5
tithoxystyrene,
21,
oil
(Lit.
b.p.
109-12Y/30
nun). 'H-nmr
6 7.7 - 7.5
(m, 2 H),
7.35
(m, 3 H), 4.6 (d,31 H, J = 2.5 Hz), 4.2 (d, 1 H, J = 2.5 Hz), 3.9 (q, 2 H, J = 7.2 Hz), H, J = 7.2 Hz). !CH 1, 14.5
C-nmr
(He).
d 160,16 (vin-C),
The
proton
and
136.8,{ipso-C),
carbon-13
nmr
128.4,
data
128.1,
125.5,
correspond
to
(t, 3
(vin-C),
82.2
those
- 7.15
1.4
reported
63.3 in
the
literature.
Reactions
of the
Lalkoxyalkyl phony1 selemonrs 9 with Ib5Na or PlsClMain DW. of 9 (5 mmol), in DMF (15 ml), cooled at O°C in an ice bath,
To a solution MeONa
(IO mmol) was added under stirring.
up in the
usual
the case
of the
under
the
already
The reactions
were complete
way. The product isolated by column chromatography reactions
Results
and
with
MeSNa
Discussion
been described.
or MeONa,
section
respectively)
(Scheme
The data of compound
6).
Compounds
the
MeSNa
0.5 h and
(on silica
and
15d are reported
after
gel
reaction
&,
e,
g,
(6 mrol) were
or
worked
or on alumina in yields are given 23,
and
24
have
below.
1-Phenyl,l-allyloxy,2-rethylthioetbane, l!iJ, oil. H-nmr 67.35br (s, 5 H), 5.85 (ddt, 1 H, J = 18.0, 10.2 and 5.4 Hz), 5.2 (ddt, 1 H, J = 18.0, 2.4 and 1.5 Hz), 5.1 (ddt, 1 H, J = 10.2, 2.4 and 1.2 HZ), 4.45 H, J = 13.2 134.8
(dd, 1 H, J = 7.2 and 5.7 Hz), 3.9 (ddd, 2 H, J = 5.4, 1.5 and and 7.2
(vin-C),
128.4,
Anal. Calcd for C
Reaction
Hz),
of the
H
2.65
127.9, 126.8,
116.7
phony1 solenone
8 (5 mmol) was added
ml) and the mixture
(vin-C),
was
stirred
8 with
to a solution
at 50°C for
5.7 Hz),
2.05
81.6 (C-l), 69.7
OS: C, 69.17; H, 7.76. Found:
(&$-8%tyryl
The selenone
(dd, 1 H, J = 13.2 and
1.2,~~).
(s, 3 H).
(CH2),
2.9
(dd, 1
C-nmr 6 141.2, (C-2). 16.7 (Me).
41.9
C, 69.23; H, 7.80.
KOHin TRF. of KOH
(7.5 mm011
18 h. The mixture
in water
was poured
(7 ml) and
on water
and
THF
(3
extracted
through a silica gel with chloroform. After the usual work up the residue was chromatographed column using chloroform as eluant. The phenylethylene oxide 27 was obtained in 45% yields. Glc retention time and proton nmr spectrum were identical to those of the commercial product. Reaction of 1-phenyl,l-(24ydroxy)ethoxy,2-phemylselenonyleth 9e with NaH in THF. Sodium hydride (5 mm011 was added to a solution of 9a (5 mmol) in THF (15 ml) and the mixture was
stirred
purified ether
at
room
by column
temperature
for
IO h. After theYusual work up the reaction product on deactivated alumina using a mixture of light petroleum
chromatography
(95:5) as eluant.
Compound
a-(244ydroxy)ethoxystyrene,
30,
30 "7s obtained
was and
in 82% yields.
ox.
H-nmr 6 7.65 - 7.45 (m, 2 H), 7.3 - 7.15 (m,,] HI, 4.65 (d, 1 H, J = 2.5 Hz), 4.2 (d, 1 H, J = 2.5 Hz), 3.9br (s, 4 H), 2.4br (s, 1 HI. C-nmr 6 159.8 (vin-C), 136.3 (ipso-c), 128.5, 128.1, 125.4, 83.0 (vin-C), 69.1 (CH2), 61.2 (CH2). Anal. Calcd for C10H1202:
C, 73.13;
kknouled~nts.
H, 7.38. Found: C, 73.18;
H, 7.35.
We gratefully
acknowledge
financial
della
Istruzione,
Italy.
Pubblica
support
from
the
CNR,
Rome
and
Minister0
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