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Spiro[4,5]decenone - synthesis
0040-4039/78/0608-2127$02.00/o
Tetrahedron Letters No. 24, pp 2127 - 2130, 1978. OPergamn Press Utd. Printed in Great Britain.
SPIRD[4,5]DECENONE
-
P.
by Givaudan
Naegeli
Research
view
In put
of
on
tic
hyde
(215.
gave
pure
bond
at
with
a
[addition
hours
isomeric
and
60-70%
reduced
ketone
yield
cyclization.
A so
further for
calamenene131 of
In
trans-substituted
the
to
the
natural
would
amine
and
fractionation,
preceding
like
to
column
If
either
chloride being
and
then
or
(1.5 0.1
of
on
of
reduction
of
the
in
with
two
cold
formed
Jones
ketones
silicagel
reagent the
was total
main or
a,
treaconcen-
temperature
bicarbonate as
isopi-o-
furnished
equivalents; room
alde-
tetrahydrofurane
minutes1
at
with
were
chromatography
yield
these
molar
molar1
quenched
~101+~11) --
70%
a
5
cataly-
pressure
oxydation for
a
after
bromide
persists
with
[chilling
catalytic
Subsequent
yield.
6+1-solution
minutes1
minutes
vinylmagnesium
colour
stannic
ethyl-vinylether
SO
yield.
90%
of
for
of
85%
[81+[91 -
[after
we
for
2
to
solution
products
in
fractionation
the 40-50%
under
11.
with deal
the
with with
individual
formation the
compounds of
cis
and
(separated trans
by
preparative
substituted
described'cis-spiro[4,S]decenone
VPC)
spiroketones (121 -
clearly in
allowed
the
each
relative
21.
for
gained
sample
over
spiroketones
[table
which
30
in
of =
ketones
15O'C
without
excess
orange-red
solution
respectively
had
in
a,B-unsaturated
equivalents
at
or
[Al5 the
during
molar
tertiary
33fold
CL1
O'C
(table
was
and
at
confirmation (811 -
(41
and
Correlation
assignment,
a
(until
experiments one
2,5
autoclave a
of
field3.
with
with
benzenetether
pressure16,
that
this
with
in
conjugated
Hydrogenation showed
-5'C
benzene
3
two
to
molar
0,5
an
latter,
alcohols
cyclizatian
with
in
the
rg1
of
[II4 _
[315, _
ketones
tration
in
acid
of to
-10
B-unsaturated
cationic
neutralization
allylic
acetone
ted
alcohol
Reaction
double
on
experiences
phosphoric
after
gave,
penyl
own
allylic
of
10 March 1978; accepted fcr publication13 April 1978)
UK
reportsl,'
our
of
amount
drop1
in
recent
record
Treatment
in
Company
Switzerland
Ouebendorf, (Reoejved
SYNTHESIS
was
the
through
type a
identical product
series
we
of
substitution
and
for
3-step
transformation'
into
in
respects
for
all
isolated
we
prepared
from
except the
the
essential
missing
2121
spiroconfiguration racemic optical oil
spiroinverted
of
of
acorenoneg
(i.e.
[plus
rotation
with
European
acorus
compound
[IO1 -
[I51 -
an
al-
cis-isoauthentic calamus
in
L.
low yield
No. 24
2128
from
(111 -
by
as
well
by
comparative
formed
as
by
a described
in
the
same
The in
atom
observed the
cannot
the
the
as
well
observed
to
‘H-nmr as
assign
spectra. above
[see as
it
was
of
Therefore
into
table
the
possible
in
spiroconfigurationtothe
the 51”
a determination
y-effects
not
compound
describedn did of
allow
in
trans-substituted
cyclizationproducts ~111waschemicallytrans-
4 - epiacorenoneBandtrans-isoa distinction
spiroconfiguration
substituents
the
position
between
cis-
and
inthecis-series 1 and
4 on
the
by methy-
10.
stereochemistry
cationic
metal
be
out
ruled
series
all
k-nmrstudies
31.
of
Surprisingly
procedure’
products
interpretation carbon
of
J-step
[table
trans-substituted
lene
cis-substituted
analysis
the
calameneneU
procedurelo.
Table
of
the
cyclization
enolate-intermediates because
on reprotonation
products A and they
is
B [table would
best 4).
show the
explainedbyal,3-hydrideshift Cyclopropaneintermediates same stereochemicaloutcome.
1
a1
+/Pd-CaC03
bl
flMgX
snq 02
Table
2
though
NO. 24
2129
Table
4
WOM
h-
/
0
&o
-
I
A
aoM
*o
-
II
B
Table
5
Carbon/cpd.
(21
ri1
(11,
(Xl
:121 --
-
:151 -
[=I
58.3
57.5
50.5
56.2
1
58.0
54.6
60.1
54.3
2
26.0
20.9
28.1
26.0
25.2
25.1
25.1
29.2
3
23.9
31.7
30.2
31.9
31.5
31.0
30.3
32.2
4
46.4
43.4
46.2
45.0
4G.l
43.4
38.6
42.4
5
48.6
49.3
47.9
48.7
48.0
44.3
46.2
46.5
6
58.7
157.2
160.2
157.6
153.3
24.9
330.0
160.8
7
29.1
128.4
128.3
128.3
829.1
336.7
38.1
127.6
8
99.4
198.9
198.9
199.0
99.3
z12.1
211.3
197.7
9
34.7
34.6
35.0
34.8
35.6
$38.9
38.9
34.4
10
20.3
28.3
20.1
30.1
34.8
37.2
11
144.1
146.;
30.5
29.i
29.2
28.0
28.4
12
15.:
15.E
15.3
15.t
17.2
16.7
16.5
19.E
13
112.1
112.E
'22.5
*20.:
'20.4
'21.0
l21.4
l22.E
14
24.;
23.E
'22.7
'23.:
'23.8
l24.9
'24.2
'23.C
64-6S°C; .~“=1.4EEE: max:
bPo 2: czn.
Y
d with
ments
at
bPo
oo,:
55.
41.
m/e:
613.6-3.1
163,
65%;
v
150.
max
:
NPIR lA60Al:
bp08005: /e:
191.
Of
d with 6'1.68
2750.
173.
17/10/5.51: 13H.
145,
bP0.3:
180.
broad
3080,
centered
IlH. 97-99%
163, 6-5.34 sl:
135.
1728.
6-9.81
OO-05%.
at
ml;
11;
159. dnd
6-3.56
Ot
2725,
3.3
121=kJ*e 1470,
51:
peak.
1385,
6.1.64 vmsx:
145. 5.17 ppm
3400.
and
5.02
1100
3100.
sl.
79.
cm-'.
sl;
105.
1370,
67,
porn from
through
with
Eu
literature
@a*
1060, 51:
55,
1%.
TMS.
induced
[fod13-d27
(Assignshift
and
in
exusing
r~lesl~~.
assignments
Interchangeable.
and
cm
-1
: NtlR IVarian
PP"l 13H.
51.
ns:
A60Al:
A-9.67
rl+ Lit (78.
Illi. 51:
characteristfc
6-4.72 *rag-
41. char.
d with
1375,
93=base
895
6.1.58
rls: rI+ 180;
1440,
2,"); 6'4.81
periments the
in
made
3o.c
l3H.
6=0.91
1645.
121,
(2".
1440, 6=1.60
93.
broad
11331.
broad
ml;
shifts were
28.5
bl.8
1642,
107.
1365. 13H.
136.
l3H.
1725.
I,,,. broad
Chemical ments
1120,
P..
79.
4.7
12H.
frazm.
6.51: 1080. 1731, norrow
at m/e:
6-0.65 995. 67,
137,
119.
pprn (31,. d with 925,
55,
892
1451,
ml i 6.4.04
cm-'. 41.
IlH.
109.
*base
PIS: n*
206:
NPlR IA60Al: broad
p..
79. 67.
6.5).
q with
char.
6-5.90
fragm. Ilk,, dd
5.51;6-3.36,~.
2130
No.
3400. 119.
105.
d-4.03 bQ
Ebase
IlH.
oo,:
P..
q with
50%:
rls:'rl+ 204; r2H.
2d
(3H.
broad
char.
with
67.
41:
bPo
dd
p.,
6 and
so"ci
79,
at m/e:
213
66/67,
bP
dd
bp
0.005:
~msx
164,
150,
0.51;
[3H,
0.005:
4oDc;
fragm.
6-0.90
165.
1.39
I2".
bP o oo5: 179,
ppm nm
ml;
r,H. at
164.
150.
239
11;
241
at
I3H.
,440,
161,
6 and
149.
6.51:
6X0.62
ppm
,100,
119.
narrow
fragm.atm/*:
char.
190.
17/9.5/5.51:
,185,
p.,
[ZH.
n*206:
. NS:
d with
,375,
-134-base
1620.
-1
cm
d with
,405,
urnax: 1700/,665.
*m
135.
6.51;
(3H.
-1
6=5.32
and
(3tl. d with
995,990,
105.
ml:
77,
[1H.
6-5.15
175,
and
165.
6.5.0,
147. (2~.
136, 3m):
6.51.
965,
93/91.
6=3.29
169.
695
65.
broad
cm-':
55. ml;
lmax
41.
at
214
NllR IA60Al:
6=,.65
[3H,
nm
l99COl.
A-6.26
broad
51;
and6.23 6~q.57~~~
nm
147.
IlH.
d with
101:
6-4.65
a"d
51 and
6=2.33
Ymax: 107,
150,
vmax:
6-0.66
pprn 1%.
,420,
t24,123-base I,". ml: ,450,
CfH.
P.. (3". ppm
ml:
6=0.94
107.
ml;
,610,
,455, 94,
wm
,465.
69,
and
6.26
6.51.
,420,
,390.
101;
6=4.91 l6H.
965
(2H.
cm
-1
. rls: n’ ?35:
2d with
,360.
176/175,le2/1~,.
6=2.1-1.62
,420,
91,
55.
,325,
6 and
,260.
41;
[lH,
pseudo
q with
ml:
,195,
11. ~z=base
or 11;
6=1.72
A-5.78
,235.
,47.,74.123,1OC,
several
(1H. (3H.
,465.
107.
dq with
,420.
17H.
ml;
P..
6'4.77 51;
I,H.
,260,
1225,
55153.
41.
vn.all ml:
6-2.24-2.07
[3H,
6=4.19
broad
(,H.
sl:
(1".
6i7.71
ml;
,165.
,,60,655c,h',
NPlR IWH2701: I?".
broad
6~2.07-1.90
(3~.
6=6.6R
t wlth7.5,: ml:
6=,.90-
71.
,145.
695.
850,
6-6.55
17/6.5/51;
770
l,H.
cm
dd
-1
. NS:El*206;
with
6-2.01-1.73
10 apd
l5H.
ml:
char.
1.51;
fra6m.
6=6.01
6=,.66-1.29
at
(,H.
(4H.
dd
ml:
6.51.
,365,
79,
,345.
lWH2701:
d with
94/q,.
,360,
79. E/67-base
d with
,225,
NMR
,395.
62.
7 a"d l?H.
,375,
65,
ppm
1245.
95,
[JH.
d with
82.
,215.
69. 71:
,305,
109.
95.
(3H.
d with
,470,
6-2.10-1.67
995,985,
d with
,455.
d with
71:
,100.
69,
,255, 65.
,220,
55.
6=1.56-1.40
,175,
4,.
(IH.
,130.
690,
630.
NllR IWH2701:6=6.87 ml:
775
-1
cm
.MS:n'ZOG;
cl,+, d with
6=1.40-1.19
[fH.
ml;
. Pls:n+206;
char.
6=0.97
101: 6=5.97. I3H.
d with
6.51.
109.
95/94/93.
d with
(3H.
m/e:189,
(1H.
,7 a"d
6=0.95
6=2.06-1.60
1330.
106,
With
,610.
,335,
p..
,685,
(3H.
1360.
6-1.03
ppm
nmilll wintuolatl:
6=2.4,
P.,
d with
,390,,360.
,24,,23=base
and
,675.
71:
p.,
79,
h-O.66
-122=base
6.51;
dU ml:
,615.
91.
6.51:
t with
1470,
,676.
17/11.5/71
135.
,185,
NflR: 6=6.13
1620,
at
6 and
,615,
122.
IIH.
(1H.
94,
d with
,640,
6=6.04
1640,
134.
[,H.
6=1.46-1.26
pseudo
vmax:
,665.
16,.
dq with
41.
6=0.64
,660,
dd with
1365.
6.51.
176.
$1:
55,
char.frs~m.
101;
[ZH.
,395.
67,
6.51:
3100,
204;
,405.
77.
d with
d with
6-2.42
1465. p..
vmax:
rl5: n' IlH.
l2H.
ebase
6-0.94
6=0.69
urnax: 3100.
[109001;
137,
IE700);
-93=base
91;
d with
p,,
164.
6-1.36-1.,6
nm
1%.
238
,715.
147,
cm
12 and
13".
137.
YmaxZ
105.
"ll ~6,001.
760
[113001:
(1".
6-2.44 d with
121, 51:
240
6=0.66
19,.
6-2.62-2.24
d with
6-0.66
925
[It+. dd of
6-4.71
l65001:
9.5
6=,.39-1.19
152.
780.
broad
71;
147,
ml;
165,
1.39
and
152.
at
135, z=base
Amax
(3".
Amax 825.
(3H.
at m/~:
soot:
)i max
995.
41;
broad
dd with
: 50%;Ymex: 1720.
0.00,
179.
,365, 6~5.90
,620,
176/171.
136.
l3H.
6.5.9
6=2.55
101;
145.
17 and
at
d with
I,ti, d with
bP
169.
at "/e:
11:
4ooc:
10 and
6-0.97
51;
1645,
NPIR lWH2701:6=6.59
broad 6'0.98
10 and
6-1.70
with
71;
ml;
ml;
191,
char.
2.
(IH.
(,,,, dq with (2~.
m/B:
bp
865.
c,,ar.fragm.
with
A-2.54 1.72
163,
34.35Oc:
55/53,
I,".
~1' 204;
[,H.
broad
"rn 177501.
: 5o”c;Amax at 230
0.001
1385,
[ASOAI:
[,ti. dd with
6-1.62
895,
6-2.46
sl;
41:
mp:
,010,
6'1.52-1.30
ns:
1%.
b-5.75
at
Amax
,140,
broad
Nm
sl.
with
oo,:
,155.
41.
1700/1665,
char. fragm.at m/e:191, (IH,
1465.
1645.
55.
6-1.60
3100.
fragm.
6 and
70%:
bPo.01:
5.51;
YmaxZ
3100,
79.
24
62.
1365,
,150.
55.
41.
6-0.96
1240. 69.
6.51; 1225, 55,
4,.
,265, NMR
6=0.93
79,
69,
41.
(3H.
ml;
6-1.61-1.49
755
cm
l3H.
NRR
6.51:
,135.
-1
71;
775
cm
ml;
ppm
6-1.43-1.13
l3H.
l5H. ppm
. llS: N+
(1H.
ml;
. i-IS:M+
-1
6=0.86 -1
lWH2701:6=6.81
(4H.
cm
6=2.59-2.15
d with 895,
[+I.
6=0.66
750
[WH2701:
1'170, ,130,
64.
665.
(3,,. d with
,215,
55.
940.
NPlR (wH2701:6=2.56-2.27
dd
(3H.
(3H. 206:
with
ml;
d with
206; ml;
at m/e: (BH,
fragm.
6=2.00-1.62
d with
10 and
193. 6=1.61-
at m/e: (6H.
193.
ml: 6=1.55-
6.51.
fraem. 21:
(3H.
ml:
6.51.
char.
char.
6-1.06
fragm.
6=2.06-1.61
at m/e:
6-5.93
d with
191,
,114. dd 71;
6=1.05
170,
ilthlO (3".
6.51.
REFERENCES
1.
K.P.
Dastur,
J.
2.
J.L.
Cooper.
K.E.
3.
Swiss
4.
German
5.
See
6.
No
optimization
7.
W.
Oppolzer.
8. 9.
Patent
American
Patent
Nr.
H.
i;-Sane,
S.
11.
Compare
also
12.
H.
13.
N.H.
14.
IR
Wolf,
for
Bachmann, Wolf,
R.
J. S.
Kutschan. 0.0.
were
K.
3321
November
step K.
(19741 (19771
1972
spectra
truments
and
t-5 at
Yamada,
in 70
C.
ev
on
575
was
W.
2, N.
Rascher.
Grahdm,
double
Wetliforhlsexperimental
on
these
Chimica
Acta
reactions g.
2388
Communications
725
on with
focussing
[I9741 n.
SchrGder. Chemische
Tetrahedron
films
done
Chemical
(19771
[I9781
in
print
(19771
Synthesis
solution a
(21
Helvetica
Schiebel.
liquid
COCl3
to
Society.
",
H.-M.
as
[II DBttig,
Chemical
Claussen,
Syrdal,
measured
NMR
gratefultoFlr.P1.
the
Tetrahedron
Terashina,
trument,
I anvery
15th
flahalanabis.
Il. Kolleck,
Andersen. spectra
2605
data except
J.P.
10.
16606,
E. Letters
1082257
K.K.
W. Raacher.
Society
Tetrahedron
Application
phvsicochemical
F1. Pesaro.
Chemical
Harding,
PE
Letters, 157
TMS
Wolf,
Rerichte
as CEC
or
257
903
109.
Eerichte
41
LIV spectra on
spectrometer
skill and I thankores.
(1977)
(19721
standard E
110.1615 -
(19761
spectrometers.
internal 21-110
Chemische
a
Vat-ion with
an
E. BilleterandP1.
in
EtOHon
a Beckm3nOO-G
XL-lOOand/oraErukerWH27rl all-glass Pesaro
inlet
systematl'
forthaircollabor3tion.
‘“3-
insSJOC.
Tetrahedron Letters No. 24, pp 2127 - 2130, 1978. OPergamn Press Utd. Printed in Great Britain.
SPIRD[4,5]DECENONE
-
P.
by Givaudan
Naegeli
Research
view
In put
of
on
tic
hyde
(215.
gave
pure
bond
at
with
a
[addition
hours
isomeric
and
60-70%
reduced
ketone
yield
cyclization.
A so
further for
calamenene131 of
In
trans-substituted
the
to
the
natural
would
amine
and
fractionation,
preceding
like
to
column
If
either
chloride being
and
then
or
(1.5 0.1
of
on
of
reduction
of
the
in
with
two
cold
formed
Jones
ketones
silicagel
reagent the
was total
main or
a,
treaconcen-
temperature
bicarbonate as
isopi-o-
furnished
equivalents; room
alde-
tetrahydrofurane
minutes1
at
with
were
chromatography
yield
these
molar
molar1
quenched
~101+~11) --
70%
a
5
cataly-
pressure
oxydation for
a
after
bromide
persists
with
[chilling
catalytic
Subsequent
yield.
6+1-solution
minutes1
minutes
vinylmagnesium
colour
stannic
ethyl-vinylether
SO
yield.
90%
of
for
of
85%
[81+[91 -
[after
we
for
2
to
solution
products
in
fractionation
the 40-50%
under
11.
with deal
the
with with
individual
formation the
compounds of
cis
and
(separated trans
by
preparative
substituted
described'cis-spiro[4,S]decenone
VPC)
spiroketones (121 -
clearly in
allowed
the
each
relative
21.
for
gained
sample
over
spiroketones
[table
which
30
in
of =
ketones
15O'C
without
excess
orange-red
solution
respectively
had
in
a,B-unsaturated
equivalents
at
or
[Al5 the
during
molar
tertiary
33fold
CL1
O'C
(table
was
and
at
confirmation (811 -
(41
and
Correlation
assignment,
a
(until
experiments one
2,5
autoclave a
of
field3.
with
with
benzenetether
pressure16,
that
this
with
in
conjugated
Hydrogenation showed
-5'C
benzene
3
two
to
molar
0,5
an
latter,
alcohols
cyclizatian
with
in
the
rg1
of
[II4 _
[315, _
ketones
tration
in
acid
of to
-10
B-unsaturated
cationic
neutralization
allylic
acetone
ted
alcohol
Reaction
double
on
experiences
phosphoric
after
gave,
penyl
own
allylic
of
10 March 1978; accepted fcr publication13 April 1978)
UK
reportsl,'
our
of
amount
drop1
in
recent
record
Treatment
in
Company
Switzerland
Ouebendorf, (Reoejved
SYNTHESIS
was
the
through
type a
identical product
series
we
of
substitution
and
for
3-step
transformation'
into
in
respects
for
all
isolated
we
prepared
from
except the
the
essential
missing
2121
spiroconfiguration racemic optical oil
spiroinverted
of
of
acorenoneg
(i.e.
[plus
rotation
with
European
acorus
compound
[IO1 -
[I51 -
an
al-
cis-isoauthentic calamus
in
L.
low yield
No. 24
2128
from
(111 -
by
as
well
by
comparative
formed
as
by
a described
in
the
same
The in
atom
observed the
cannot
the
the
as
well
observed
to
‘H-nmr as
assign
spectra. above
[see as
it
was
of
Therefore
into
table
the
possible
in
spiroconfigurationtothe
the 51”
a determination
y-effects
not
compound
describedn did of
allow
in
trans-substituted
cyclizationproducts ~111waschemicallytrans-
4 - epiacorenoneBandtrans-isoa distinction
spiroconfiguration
substituents
the
position
between
cis-
and
inthecis-series 1 and
4 on
the
by methy-
10.
stereochemistry
cationic
metal
be
out
ruled
series
all
k-nmrstudies
31.
of
Surprisingly
procedure’
products
interpretation carbon
of
J-step
[table
trans-substituted
lene
cis-substituted
analysis
the
calameneneU
procedurelo.
Table
of
the
cyclization
enolate-intermediates because
on reprotonation
products A and they
is
B [table would
best 4).
show the
explainedbyal,3-hydrideshift Cyclopropaneintermediates same stereochemicaloutcome.
1
a1
+/Pd-CaC03
bl
flMgX
snq 02
Table
2
though
NO. 24
2129
Table
4
WOM
h-
/
0
&o
-
I
A
aoM
*o
-
II
B
Table
5
Carbon/cpd.
(21
ri1
(11,
(Xl
:121 --
-
:151 -
[=I
58.3
57.5
50.5
56.2
1
58.0
54.6
60.1
54.3
2
26.0
20.9
28.1
26.0
25.2
25.1
25.1
29.2
3
23.9
31.7
30.2
31.9
31.5
31.0
30.3
32.2
4
46.4
43.4
46.2
45.0
4G.l
43.4
38.6
42.4
5
48.6
49.3
47.9
48.7
48.0
44.3
46.2
46.5
6
58.7
157.2
160.2
157.6
153.3
24.9
330.0
160.8
7
29.1
128.4
128.3
128.3
829.1
336.7
38.1
127.6
8
99.4
198.9
198.9
199.0
99.3
z12.1
211.3
197.7
9
34.7
34.6
35.0
34.8
35.6
$38.9
38.9
34.4
10
20.3
28.3
20.1
30.1
34.8
37.2
11
144.1
146.;
30.5
29.i
29.2
28.0
28.4
12
15.:
15.E
15.3
15.t
17.2
16.7
16.5
19.E
13
112.1
112.E
'22.5
*20.:
'20.4
'21.0
l21.4
l22.E
14
24.;
23.E
'22.7
'23.:
'23.8
l24.9
'24.2
'23.C
64-6S°C; .~“=1.4EEE: max:
bPo 2: czn.
Y
d with
ments
at
bPo
oo,:
55.
41.
m/e:
613.6-3.1
163,
65%;
v
150.
max
:
NPIR lA60Al:
bp08005: /e:
191.
Of
d with 6'1.68
2750.
173.
17/10/5.51: 13H.
145,
bP0.3:
180.
broad
3080,
centered
IlH. 97-99%
163, 6-5.34 sl:
135.
1728.
6-9.81
OO-05%.
at
ml;
11;
159. dnd
6-3.56
Ot
2725,
3.3
121=kJ*e 1470,
51:
peak.
1385,
6.1.64 vmsx:
145. 5.17 ppm
3400.
and
5.02
1100
3100.
sl.
79.
cm-'.
sl;
105.
1370,
67,
porn from
through
with
Eu
literature
@a*
1060, 51:
55,
1%.
TMS.
induced
[fod13-d27
(Assignshift
and
in
exusing
r~lesl~~.
assignments
Interchangeable.
and
cm
-1
: NtlR IVarian
PP"l 13H.
51.
ns:
A60Al:
A-9.67
rl+ Lit (78.
Illi. 51:
characteristfc
6-4.72 *rag-
41. char.
d with
1375,
93=base
895
6.1.58
rls: rI+ 180;
1440,
2,"); 6'4.81
periments the
in
made
3o.c
l3H.
6=0.91
1645.
121,
(2".
1440, 6=1.60
93.
broad
11331.
broad
ml;
shifts were
28.5
bl.8
1642,
107.
1365. 13H.
136.
l3H.
1725.
I,,,. broad
Chemical ments
1120,
P..
79.
4.7
12H.
frazm.
6.51: 1080. 1731, norrow
at m/e:
6-0.65 995. 67,
137,
119.
pprn (31,. d with 925,
55,
892
1451,
ml i 6.4.04
cm-'. 41.
IlH.
109.
*base
PIS: n*
206:
NPlR IA60Al: broad
p..
79. 67.
6.5).
q with
char.
6-5.90
fragm. Ilk,, dd
5.51;6-3.36,~.
2130
No.
3400. 119.
105.
d-4.03 bQ
Ebase
IlH.
oo,:
P..
q with
50%:
rls:'rl+ 204; r2H.
2d
(3H.
broad
char.
with
67.
41:
bPo
dd
p.,
6 and
so"ci
79,
at m/e:
213
66/67,
bP
dd
bp
0.005:
~msx
164,
150,
0.51;
[3H,
0.005:
4oDc;
fragm.
6-0.90
165.
1.39
I2".
bP o oo5: 179,
ppm nm
ml;
r,H. at
164.
150.
239
11;
241
at
I3H.
,440,
161,
6 and
149.
6.51:
6X0.62
ppm
,100,
119.
narrow
fragm.atm/*:
char.
190.
17/9.5/5.51:
,185,
p.,
[ZH.
n*206:
. NS:
d with
,375,
-134-base
1620.
-1
cm
d with
,405,
urnax: 1700/,665.
*m
135.
6.51;
(3H.
-1
6=5.32
and
(3tl. d with
995,990,
105.
ml:
77,
[1H.
6-5.15
175,
and
165.
6.5.0,
147. (2~.
136, 3m):
6.51.
965,
93/91.
6=3.29
169.
695
65.
broad
cm-':
55. ml;
lmax
41.
at
214
NllR IA60Al:
6=,.65
[3H,
nm
l99COl.
A-6.26
broad
51;
and6.23 6~q.57~~~
nm
147.
IlH.
d with
101:
6-4.65
a"d
51 and
6=2.33
Ymax: 107,
150,
vmax:
6-0.66
pprn 1%.
,420,
t24,123-base I,". ml: ,450,
CfH.
P.. (3". ppm
ml:
6=0.94
107.
ml;
,610,
,455, 94,
wm
,465.
69,
and
6.26
6.51.
,420,
,390.
101;
6=4.91 l6H.
965
(2H.
cm
-1
. rls: n’ ?35:
2d with
,360.
176/175,le2/1~,.
6=2.1-1.62
,420,
91,
55.
,325,
6 and
,260.
41;
[lH,
pseudo
q with
ml:
,195,
11. ~z=base
or 11;
6=1.72
A-5.78
,235.
,47.,74.123,1OC,
several
(1H. (3H.
,465.
107.
dq with
,420.
17H.
ml;
P..
6'4.77 51;
I,H.
,260,
1225,
55153.
41.
vn.all ml:
6-2.24-2.07
[3H,
6=4.19
broad
(,H.
sl:
(1".
6i7.71
ml;
,165.
,,60,655c,h',
NPlR IWH2701: I?".
broad
6~2.07-1.90
(3~.
6=6.6R
t wlth7.5,: ml:
6=,.90-
71.
,145.
695.
850,
6-6.55
17/6.5/51;
770
l,H.
cm
dd
-1
. NS:El*206;
with
6-2.01-1.73
10 apd
l5H.
ml:
char.
1.51;
fra6m.
6=6.01
6=,.66-1.29
at
(,H.
(4H.
dd
ml:
6.51.
,365,
79,
,345.
lWH2701:
d with
94/q,.
,360,
79. E/67-base
d with
,225,
NMR
,395.
62.
7 a"d l?H.
,375,
65,
ppm
1245.
95,
[JH.
d with
82.
,215.
69. 71:
,305,
109.
95.
(3H.
d with
,470,
6-2.10-1.67
995,985,
d with
,455.
d with
71:
,100.
69,
,255, 65.
,220,
55.
6=1.56-1.40
,175,
4,.
(IH.
,130.
690,
630.
NllR IWH2701:6=6.87 ml:
775
-1
cm
.MS:n'ZOG;
cl,+, d with
6=1.40-1.19
[fH.
ml;
. Pls:n+206;
char.
6=0.97
101: 6=5.97. I3H.
d with
6.51.
109.
95/94/93.
d with
(3H.
m/e:189,
(1H.
,7 a"d
6=0.95
6=2.06-1.60
1330.
106,
With
,610.
,335,
p..
,685,
(3H.
1360.
6-1.03
ppm
nmilll wintuolatl:
6=2.4,
P.,
d with
,390,,360.
,24,,23=base
and
,675.
71:
p.,
79,
h-O.66
-122=base
6.51;
dU ml:
,615.
91.
6.51:
t with
1470,
,676.
17/11.5/71
135.
,185,
NflR: 6=6.13
1620,
at
6 and
,615,
122.
IIH.
(1H.
94,
d with
,640,
6=6.04
1640,
134.
[,H.
6=1.46-1.26
pseudo
vmax:
,665.
16,.
dq with
41.
6=0.64
,660,
dd with
1365.
6.51.
176.
$1:
55,
char.frs~m.
101;
[ZH.
,395.
67,
6.51:
3100,
204;
,405.
77.
d with
d with
6-2.42
1465. p..
vmax:
rl5: n' IlH.
l2H.
ebase
6-0.94
6=0.69
urnax: 3100.
[109001;
137,
IE700);
-93=base
91;
d with
p,,
164.
6-1.36-1.,6
nm
1%.
238
,715.
147,
cm
12 and
13".
137.
YmaxZ
105.
"ll ~6,001.
760
[113001:
(1".
6-2.44 d with
121, 51:
240
6=0.66
19,.
6-2.62-2.24
d with
6-0.66
925
[It+. dd of
6-4.71
l65001:
9.5
6=,.39-1.19
152.
780.
broad
71;
147,
ml;
165,
1.39
and
152.
at
135, z=base
Amax
(3".
Amax 825.
(3H.
at m/~:
soot:
)i max
995.
41;
broad
dd with
: 50%;Ymex: 1720.
0.00,
179.
,365, 6~5.90
,620,
176/171.
136.
l3H.
6.5.9
6=2.55
101;
145.
17 and
at
d with
I,ti, d with
bP
169.
at "/e:
11:
4ooc:
10 and
6-0.97
51;
1645,
NPIR lWH2701:6=6.59
broad 6'0.98
10 and
6-1.70
with
71;
ml;
ml;
191,
char.
2.
(IH.
(,,,, dq with (2~.
m/B:
bp
865.
c,,ar.fragm.
with
A-2.54 1.72
163,
34.35Oc:
55/53,
I,".
~1' 204;
[,H.
broad
"rn 177501.
: 5o”c;Amax at 230
0.001
1385,
[ASOAI:
[,ti. dd with
6-1.62
895,
6-2.46
sl;
41:
mp:
,010,
6'1.52-1.30
ns:
1%.
b-5.75
at
Amax
,140,
broad
Nm
sl.
with
oo,:
,155.
41.
1700/1665,
char. fragm.at m/e:191, (IH,
1465.
1645.
55.
6-1.60
3100.
fragm.
6 and
70%:
bPo.01:
5.51;
YmaxZ
3100,
79.
24
62.
1365,
,150.
55.
41.
6-0.96
1240. 69.
6.51; 1225, 55,
4,.
,265, NMR
6=0.93
79,
69,
41.
(3H.
ml;
6-1.61-1.49
755
cm
l3H.
NRR
6.51:
,135.
-1
71;
775
cm
ml;
ppm
6-1.43-1.13
l3H.
l5H. ppm
. llS: N+
(1H.
ml;
. i-IS:M+
-1
6=0.86 -1
lWH2701:6=6.81
(4H.
cm
6=2.59-2.15
d with 895,
[+I.
6=0.66
750
[WH2701:
1'170, ,130,
64.
665.
(3,,. d with
,215,
55.
940.
NPlR (wH2701:6=2.56-2.27
dd
(3H.
(3H. 206:
with
ml;
d with
206; ml;
at m/e: (BH,
fragm.
6=2.00-1.62
d with
10 and
193. 6=1.61-
at m/e: (6H.
193.
ml: 6=1.55-
6.51.
fraem. 21:
(3H.
ml:
6.51.
char.
char.
6-1.06
fragm.
6=2.06-1.61
at m/e:
6-5.93
d with
191,
,114. dd 71;
6=1.05
170,
ilthlO (3".
6.51.
REFERENCES
1.
K.P.
Dastur,
J.
2.
J.L.
Cooper.
K.E.
3.
Swiss
4.
German
5.
See
6.
No
optimization
7.
W.
Oppolzer.
8. 9.
Patent
American
Patent
Nr.
H.
i;-Sane,
S.
11.
Compare
also
12.
H.
13.
N.H.
14.
IR
Wolf,
for
Bachmann, Wolf,
R.
J. S.
Kutschan. 0.0.
were
K.
3321
November
step K.
(19741 (19771
1972
spectra
truments
and
t-5 at
Yamada,
in 70
C.
ev
on
575
was
W.
2, N.
Rascher.
Grahdm,
double
Wetliforhlsexperimental
on
these
Chimica
Acta
reactions g.
2388
Communications
725
on with
focussing
[I9741 n.
SchrGder. Chemische
Tetrahedron
films
done
Chemical
(19771
[I9781
in
(19771
Synthesis
solution a
(21
Helvetica
Schiebel.
liquid
COCl3
to
Society.
",
H.-M.
as
[II DBttig,
Chemical
Claussen,
Syrdal,
measured
NMR
gratefultoFlr.P1.
the
Tetrahedron
Terashina,
trument,
I anvery
15th
flahalanabis.
Il. Kolleck,
Andersen. spectra
2605
data except
J.P.
10.
16606,
E. Letters
1082257
K.K.
W. Raacher.
Society
Tetrahedron
Application
phvsicochemical
F1. Pesaro.
Chemical
Harding,
PE
Letters, 157
TMS
Wolf,
Rerichte
as CEC
or
257
903
109.
Eerichte
41
LIV spectra on
spectrometer
skill and I thankores.
(1977)
(19721
standard E
110.1615 -
(19761
spectrometers.
internal 21-110
Chemische
a
Vat-ion with
an
E. BilleterandP1.
in
EtOHon
a Beckm3nOO-G
XL-lOOand/oraErukerWH27rl all-glass Pesaro
inlet
systematl'
forthaircollabor3tion.
‘“3-
insSJOC.