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Organic sulfur compounds I: thermolysis of 2,2-dimethyl-1-(P-toluenesulfonylimino)thiochroman
Tetrahedron Letters No. 9,
pp 691 - 692, lY76.
ORGANIC THERMOLYSIS Masahiro
Printed in Great Britain.
pergamon Press.
SULFUR COMPOUNDS
I:
OF Z,Z-DIMETHYL-l-(P-TOLUE~~ESULFONYLIMINO)TN
Kise*, Masao Murase, Research
Masahiko
Laboratory,
Nishi-hachijo,
Kitano, Nippon
Toshio Tomita
Shinyaku
Minamiku,
and Hiromu Murai
Co. Ltd.,
Kyoto, Japan
(Beceivcdin Japan 13 December 1975; received in UK for publication 15 January 1976) Thermolysis
of acyclic
that the thermolysisl) @-hydrogens
known').
This prompts
sulfilimines.
one of cyclic
However,
membered
transition
sulfenamide product
is considered
Thermolysis
I.
3(4H)-methane
by column
xylene
the
to give 2-methyl-Z-
(IX)
data for the
by the thermolysis
scheme of these reactions
of V are
is illustrat-
is the following;
in benzene
Treatment
for one hour.
off, then an oily product
chromatography
The isomerization
of V to VIII
course of the preparation
with benzene
is also assumed
of V with p-TsOH
In addition,
After
was obtained.
the reaction, The product was
through a silica gel (Wakogel C-200) packed
quantitatively
shown in Fig. I are the first example sulfilimine.
the five The resulting
The physical
(X).
generated
The over-all
run of the reaction
column, and V was obtained ion (VII).
involving
(V) may be formed through
of I in benzene
was distilled
separated
The initial
(VIII), 3-methyl-2,5-dihydro-1-benzothiepin
I (2.3 mmO1.) was refluxed benzene
of
(VI), N,N-bis(Z-methylthiochroman-Z-
of these compounds
A typical
of
(V) quantitative-
data (Table I).
in refluxing
thermolysis
and 2,5-dihydro-l-benzothiepin-A
ed in Fig. I.
the thermolysis
ion (IV) as shown in Fig. I.
(p-toluenesulfonylaminomethyl)thiochroman
in Table
sulfen-
are little
on the thermolysis
to report
to be D-elimination
(II), then the compound
ylmethyl)-p-toluenesulfonamide assignment
having
N-[Z-(3-methyl-3-butenyl)phenyl-
is based on physical
(III) and episulfonium
also summarized
investigation we wish
-ylmethyl)-p-toluenesulfonamide
assignment
state
It is known
2,2-dimethyl-l-(p-toluenesulfonylimino)t~~iochroman
(V) further undergoes
structural
of cyclic sulfilimines
for one hour afforded
thio]-N-(2'-methylthiochroman-2' ly* step of this reaction
investigated.
and phenyl-M-p-tolylsulfonyl
us to do more detailed
I in benzene
The structural
olefins
thermolysis
In this communication,
sulfilimines,
(I). Refluxing
has been well
alkyl N-p-toluenesulfonylsulfilimines
give the corresponding
amide in high yields. cyclic
sulfilimines
of phenyl
as eluent.
to proceed
gave VI quantitatively. of 1,3-abnormal
691
These reactions
Pummerer-type
we found that the same reaction of the free sulfilimine
via episulfonium reaction
took place during
of 2,2_dimethylthiochroman
of the with
No. 9
692
0-mesitylenesulfonylhydroxylamine The detailed elsewhere
and further
3) .
studies of these reactions
will be published
in near future.
Acknowledgement-The authors wish to thank Professor S. Oae and Assistant ___ Professor N. Furukawa, The University of Tsukuba, for their helpful discussions. Table
Compound
Physical
I.
Data for the Structural
Assignment
of the Compounds
Generated by Thermolysis of I. __-~ IR Mass 'H-NMR (CDCl3) "maxi m/~ cm d (M )
V
16.50 523
VI VIII
3230 347 1330 1330 523
Ix= X
1155 1650 176 1650 176
1.50(3H,s),1.76(3H,br.s),1.85-2.~(4H,m),2.40(3H,s),2.55-3.10(4H,m), 3.82[2H,s),4.73(2H,br.s),6.95-7.26(8H,m),7.26(2H,d,J-8.5Hz),
* The structuralassignmentof IX and X was determinedby the nmr of the authentic samples produced by the k&-in's method4)_ Fig. I.
(VI) 80%
Over-all
Scheme of the Thermolysis
(VIII) 20%
(IX) 14%
of I.
(X) 14%
References 1) K. Tsujihara, N. Furukawa and S. Oae, Tetrahedron, 27, 4921 (1971). 2) a) M. M. Campbell, G. Johnson, A. F. Cameron and I. R. Cameron, J. Chem. Sot. Perkin I, 1975,1208. b) M. M. Campbell and G, Johnson, ibid, 1975, 1212. 3) Y. Tamura, K. Sumoto, J. ?linamikawa and M. Ikeda, Tetrahedron Lett.,1972,4137. 4) R. B: Morin, Il. 0. Spry and R. A. Mueller, Tetrahedron Lett., 1969, 849.
pp 691 - 692, lY76.
ORGANIC THERMOLYSIS Masahiro
Printed in Great Britain.
pergamon Press.
SULFUR COMPOUNDS
I:
OF Z,Z-DIMETHYL-l-(P-TOLUE~~ESULFONYLIMINO)TN
Kise*, Masao Murase, Research
Masahiko
Laboratory,
Nishi-hachijo,
Kitano, Nippon
Toshio Tomita
Shinyaku
Minamiku,
and Hiromu Murai
Co. Ltd.,
Kyoto, Japan
(Beceivcdin Japan 13 December 1975; received in UK for publication 15 January 1976) Thermolysis
of acyclic
that the thermolysisl) @-hydrogens
known').
This prompts
sulfilimines.
one of cyclic
However,
membered
transition
sulfenamide product
is considered
Thermolysis
I.
3(4H)-methane
by column
xylene
the
to give 2-methyl-Z-
(IX)
data for the
by the thermolysis
scheme of these reactions
of V are
is illustrat-
is the following;
in benzene
Treatment
for one hour.
off, then an oily product
chromatography
The isomerization
of V to VIII
course of the preparation
with benzene
is also assumed
of V with p-TsOH
In addition,
After
was obtained.
the reaction, The product was
through a silica gel (Wakogel C-200) packed
quantitatively
shown in Fig. I are the first example sulfilimine.
the five The resulting
The physical
(X).
generated
The over-all
run of the reaction
column, and V was obtained ion (VII).
involving
(V) may be formed through
of I in benzene
was distilled
separated
The initial
(VIII), 3-methyl-2,5-dihydro-1-benzothiepin
I (2.3 mmO1.) was refluxed benzene
of
(VI), N,N-bis(Z-methylthiochroman-Z-
of these compounds
A typical
of
(V) quantitative-
data (Table I).
in refluxing
thermolysis
and 2,5-dihydro-l-benzothiepin-A
ed in Fig. I.
the thermolysis
ion (IV) as shown in Fig. I.
(p-toluenesulfonylaminomethyl)thiochroman
in Table
sulfen-
are little
on the thermolysis
to report
to be D-elimination
(II), then the compound
ylmethyl)-p-toluenesulfonamide assignment
having
N-[Z-(3-methyl-3-butenyl)phenyl-
is based on physical
(III) and episulfonium
also summarized
investigation we wish
-ylmethyl)-p-toluenesulfonamide
assignment
state
It is known
2,2-dimethyl-l-(p-toluenesulfonylimino)t~~iochroman
(V) further undergoes
structural
of cyclic sulfilimines
for one hour afforded
thio]-N-(2'-methylthiochroman-2' ly* step of this reaction
investigated.
and phenyl-M-p-tolylsulfonyl
us to do more detailed
I in benzene
The structural
olefins
thermolysis
In this communication,
sulfilimines,
(I). Refluxing
has been well
alkyl N-p-toluenesulfonylsulfilimines
give the corresponding
amide in high yields. cyclic
sulfilimines
of phenyl
as eluent.
to proceed
gave VI quantitatively. of 1,3-abnormal
691
These reactions
Pummerer-type
we found that the same reaction of the free sulfilimine
via episulfonium reaction
took place during
of 2,2_dimethylthiochroman
of the with
No. 9
692
0-mesitylenesulfonylhydroxylamine The detailed elsewhere
and further
3) .
studies of these reactions
will be published
in near future.
Acknowledgement-The authors wish to thank Professor S. Oae and Assistant ___ Professor N. Furukawa, The University of Tsukuba, for their helpful discussions. Table
Compound
Physical
I.
Data for the Structural
Assignment
of the Compounds
Generated by Thermolysis of I. __-~ IR Mass 'H-NMR (CDCl3) "maxi m/~ cm d (M )
V
16.50 523
VI VIII
3230 347 1330 1330 523
Ix= X
1155 1650 176 1650 176
1.50(3H,s),1.76(3H,br.s),1.85-2.~(4H,m),2.40(3H,s),2.55-3.10(4H,m), 3.82[2H,s),4.73(2H,br.s),6.95-7.26(8H,m),7.26(2H,d,J-8.5Hz),
* The structuralassignmentof IX and X was determinedby the nmr of the authentic samples produced by the k&-in's method4)_ Fig. I.
(VI) 80%
Over-all
Scheme of the Thermolysis
(VIII) 20%
(IX) 14%
of I.
(X) 14%
References 1) K. Tsujihara, N. Furukawa and S. Oae, Tetrahedron, 27, 4921 (1971). 2) a) M. M. Campbell, G. Johnson, A. F. Cameron and I. R. Cameron, J. Chem. Sot. Perkin I, 1975,1208. b) M. M. Campbell and G, Johnson, ibid, 1975, 1212. 3) Y. Tamura, K. Sumoto, J. ?linamikawa and M. Ikeda, Tetrahedron Lett.,1972,4137. 4) R. B: Morin, Il. 0. Spry and R. A. Mueller, Tetrahedron Lett., 1969, 849.