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Generation of Carbonylcyclopropanes [Cyclopropyl idenemethanones] and Steric Course of Cyclodimerization to Dispiro[2.1.2

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Generation of Carbonylcyclopropanes and P w I a r a t i o n o f
Schetne I.
This manuscript is
to be cited as
Angew. Chem. Suppl.
1982,17-24
Dieses Manuskript ist
zu zitieren als
Angew. Chem. Suppl.
7982,17-24
t h e i r Dispiro[2.1.2.1loctan-4,8-dione
Dimers.
0 V e h g Chernte GmbH, D-6940Weinheim. 1982
072i-4227/82~0101-0017802
5010
Generation o f Carhonil c y c l opropanes [Cycl opropyl idenemethanones] and
a
.*
5 t e r i c Course of ..yclodimerization t o Oispiro[2.1.Z.l]octan-4,8-diones
H.M.R.
Hoffmann,
i
:an Michael W u l f f , Angela Kutz, and Rudolf Wartchow
L
I.
co2
2 . d i l H2SOI
S u b s t i t u t e d capbonylcyclopropanes and t h e i r dimers have h i t h e r t o n o t
heen described, a1 though t h e parent compound
la; ("dimethyleneketene")
sa
and thence .. have been obtained a few years ago by two independent
routes,
f l d s n vapour p y r o l y s i s o f t h e c y c l i c a c y l a l o f cyclopropane-
1.e.
1.1-dicarboxylic
a c i d a t 500"C[1a1 and p h o t o l y s i s o f t h e s u i t a b l y 9,lO-
bridged Giels-Alder adduct o f anthracene.[lbl
a
For work on a p r e p a r a t l v e
scale and a l s o f o r o b t a i n i n g carbonylcyclopropanes o t h e r than t h e
p r o t o t y p e the approaches t o l a [ " 2 1
a r e not s u i t a b l e . In searching f o r
a simple )route t c , these ketenes we f i r s t o f a l l t r i e d d e h y d r o c h l o r i n a t i o n
o f cyclopropanecarboxylic a c i d c h l o r i d e (13)
.
. w i t h t e r t i a r y amines
P r o f . H.M.R.
J.M. W u l f f , and Dipl.-Chem.
Hoffniann, Dip1.-Chem.
A. Kutr, I n s t i t u t f u r Organische Chemie, U n i v e r s i t a t Hannover,
Schneiderberg 1 6, 0-3000 Hannover;
8
P
Or. R. Wartchow, : n s t i t u t f u r Anorganische Chemie,
U n i v e r s i t a t Hannover, C a l I i n s t r a O e 9, 0-3000 Hannover;
**This work has been presented i n p a r t a t the I n t e r n a t i o n a l Symposium on
the Chemistry o f Carbocations i n Eangor, North Wales, Sept. 7-11,
1981.
We thdnk the Funds der Chemischen l n d u s t r i e for f i n a n c i a l support.
- 17 -
- 19 -
Table 1. DispirolZ.1.2.lloctan-4,8-diones
g-g[al
.
mp
13C NMR
'H NMR
1%1
IT1
ICDCl31
ICDCl31
IR
[cm-ll
45
145[c]
20.6 (CH3), 36.1 (CH2).
1.42 (8, 4CH3)
1723
42.1 (CMeZ), 59.7
1.92 ( 8 , 2CH2)
[CCl41
Yieldfb1
i n c l u d i n g t r i e t n y l a r n i n e , and s t e r i c a l l y hindered e t h y l d i i s o p r o p y l a m i n e ,
o n l y t o confirm t h a t the d e s i r e d
was n o t generated under these con-
hydrogen a t o the chlorocarbonyl f u n c t i o n a l i t y
in
le
44-60 -180Idl
1:
i s n o t a c i d i c enriugn. 2,6-Di-tert-butyl-4-methylpyridine, a h i g h l y
hindered S a ~ e , ' ~d' i d n o t r e a c t a t a l l w i t h
( s p i r o C), 2 0 7 . 7 (CO)
pg
d i t i o n ~ ! ~ 'Instedd, cyclopropanecarboxamides were formed, suggesting
t h a t t h ? tert.iary
gk
g$
20
187ldl
i n refluxing dichloro-
methane.
17.9 (CH3), 49.6 ($Mez), 1.39 ( 5 , 24H)
1715LeI
65.5 ( s p i r o C).207.6
[CC141
(CO)
20.3 (CH2), 20.9 (CHZ).
1.0-2.0
1728
36.9 ( C H I ,
(8CH2)
[CC141
60.6
( s p i r o C), 208.6
2.4-2.7
(CO)
(m, 4CH)
Anottier well-known approach t o ketenes i n v o l v e s metal-induced dehalogeoation o f
>-halogenocarboxylic a c i d h a l i d e s . 1 5 1 In the case a t hand,
the r e q u i r e d 1-bromocyclopropanecarboxylic
by l i t h i d t i o n of 1.1-dibromocyclopropanes
5L-d
acids
2b-d
.
..w i t h
were obtained
n-butyllithium i n
t e t r a h y d r o f u r a n - d i e t h y l ether-pentane a t -110" t o -1OO'C and c a r b o x y l -
[a] A l l compounds gave c o r r e c t microanalyses and molecular peaks i n the
MS.
I b l I s o l a t e d y i e l d s n o t y e t optimized.
[ c l Determined i n sealed tube; substance sublimes.
[ d l Decomposition.
a t i o n o t the r e s u l t i n g carbenoids, a s described by ~ r ~ ~ . Conversion
[ 6 1
of p
d i n t o I-bromocyclopropanecarboxylic a c i d c h l o r i d e s
ii-g
I e l 1708 b r [KBr].
with
t h i o n y l c h l o r i a e o r o x a l y l c h l o r i d e followed by dehalogenation w i t h
zinc-iilvfr
i . o ~ r . i ~ " ' oave. a f t e r aqueous work up, a l k y l a t e d d i s p i r o
12.1.2.1)oct~n-4,8-dione~ 80-4
.
. . as n i a j o r products and, i n t e r e s t i n g l y ,
a l s o some c y c l i c t r i m e r s .
The \ t r u c t u r e of t h e colorless, c r y s t a l l i n e cyclodimers
secured s p e c t r o s L o p i c a l l y (Table 1 ) . For example,
i n t h e I H NlR spectrum ( i n t e n s e 24 H s i n g l e t a t
simple "C
8b-g
was
shows but one s i g n d l
1.39
i=
PPm) and a l s o a
NMR <pectrum, c o n s i s t i n g o f t h r e e s i n g l e t s and one q u a r t e t .
- 18 -
-
20 -
Experimental.
Preparation of I -Bromo-?,2,3,3-
t?tramethylcyclopropanecarboxyl i c a c i d
(27).
(3~)'~'
1,1-Dibromo-2,2,3,3-tetramethylcyclopropane (5.12 9. 20 mmol)
was prepared according t o t h e Makosza method, d i c s o l v e d i n t e t r a h y d r o furan ( I 0 0 m l ) - d i e t h y l e t h e r ( 2 0 m1)-pentane (20 m l ) and cooled t o -1OOOC.
A 1.6 M s o l u t i o n of n - b u t y l l l t h i u m (12.5 m l , 20 m o l ) i n hexane was
added dropwise d u r i n g 20 min, and the r e s u l t i n g s o l u t i o n was s t i r r e d f o r
d
Cog the r e a c t i o n
f u r t h e r 30 m i n a t -100°C. A f t e r a d d i t i o n o f s o l i d
m i x t u r e was allowed t o reach r a m temperature and e x t r a c t e d w i t h aqueous
NaHCQ3. The aqueous phase was a c i d i f i e d w i t h d i l . H2S04, e x t r a c t e d w i t h
Sd.
F i g . 1 . S t r u c t u r e of
d i e t h y l ether, and the r e s u l t i n g phase was d r i e d (MgS04), f i l t e r e d and
evaporated t o leave
2.08 g (94%) o f k , nip 161°C ( l i g h t petroleum).
Selected bond lengths and atomic distances i n A, e r r o r c 0 . 0 1 A: C(4)-0
1.21,
Preparation o f $$.
C(3)-C(4) 1.49, C ( I ) - C ( 3 ) 1.54, C(3)-C(8) 1.49, C(?)-C(3) 1.53,
C ( l ) - C ( 2 ) 1.48,
C(4)
u n i t c e l l a.9.75,
...C(8)
b=10.65,
2.08,
c.12.31
C(3)
...C(5)
2.13.
2:
Space group Pbca,
i (orthorhombic),
2.4,
Dx=1.27 g
( 1 . 1 g. 5 mmol) and SOC12 ( 4 m l ) were s t i r r e d f o r 20 h a t room
temperature. The excess o f S0Cl2 was evaporated a t 25°C i n vacuo.
The c e n t r e of t h e molecule c o i n c i d e s w i t h an i n v e r s i o n c e n t r e o f t h e
Sublimation i n a Kugelrohr apparatus (60°C.
l a t t i c e . The packing o f t h e molecules can be d e r i v e d from the cubic
mp 154°C (decoinp.)
I n t e n s i t y data were recorded on a two c i r c l e
close-packed s t r u c t u r e .
diffractometer
(Stoe-Stadi
2):
r o t a t i o n a x i s [ 1 1 1 1 , 2710 r e f l e c t i o n s (876 unique). Structuce determination
by d i r e c t methods and refinement w i t h a n i s o t r o p i c temperature f a c t o r s
T o r r ) gave
$2
( 1 . 1 9, 92::).
tamethyl d i s p i r o [2.1.2.1 I octan-4 ,&di one
Preparation o f 1 . I ,2,2,6.6,7.7-0c
Mo Ka r a d i a t i o n , g r a p h i t e monochromator,
-1
(&).
$5
(240 mq. 1 m o l ) i n t e t r a h y d r o f u r a n ( 1 . 2 5 m l ) was s t i r r e d w i t h z i n c -
s i l v e r ~ o u p l e ~ ~ ~ ing.
( 1 0 1.5
0 mmol) f o r 3 h a t rooin temperature. The r e s u l -
f o r C and 0, R=0.053. SHELX Program, c a l c u l a t i o n s a t t h e Regionales
t i n g suspension was d i l u t e d w i t h e t h e r (ca. 5 m l ) and t r e a t e d w i t h d i l .
Rechenzentrum Hannover.
H2S04. The organic phase was separated. washed w i t h water and d r i e d
87
(MgS04). g i v i n q R8 nig o f crude product. 62 mg (50: ) o f
after
r e c r y s t a l l i z a t i o n froiii pentane.
- 21 -
H i t h e r t o , t h e r e have been no s e r i o u s attempts t o s:udy
course
Of
A p r i o r i , c y c l o d i m e r i z a t i o n of a ketoketene such as
the
a ) G.J. Baxter, R.F.C.
the s t e r i c
c y c l o d i m e r i z a t i o n of ketoketenes t o cyclobutane-l,3-diones.
meric cyclobutane-l,3-diones,
dimer
11 having
the
Xn.
23 -
-
4
15'
can g i v e two i s o -
dimer 1Q
.
.having CZv symmetry and
hedron L e t t .
Brown, F.W.
1x5, 4283;
b ) J.L.
Harrington, TeJtE
Eastwood, K.J.
R i p o l l , Tetrahedron 33
P. Schotz, P.M.
Strong, Helv.Chim.Acta
(1923)
6
291; see a l s o
___
G. Rouesseau, R . Bloch, P. Le Perchec, J.M. Conia, JCS Chem.Co:lim.
-
CPh symmetry (Scheme 2 ) .
1973, 795; R . Bloch, J.M. Denis, J.Erganometallic
R.F.
E. Lee-Ruff, R.M.
Southam, N.J.
note 21; see a l s o H.D.
C f . H.M.
9.
X-Ray c r y s t a l s t r u c t u r e a n a l y s i s (Fig. I ) shows t h a t
t o the l e s s encumbered
moieties are
trans t o
d i m e r i z a t i o n of
'b
to
& dimer
72
Turro, i b i d . 92
Walborsky, J.Am.Chem.So2.
678
7
4
L.A.
7108; D.R.
(1969)
(1952)
(1964)
(1970)
4349, f o o t -
87
(1975)
782.
4962; E. Buchta,
53; F.T. Williams,
S.C.
Baber, G. Comstock, L. Harrah, Chem.Abstr.
ref.
la.
4.G.
Anderson, P.J.
Stang, J.Org.Chem.
65
(1976)
(1966)
15243b;
3034.
a) D. Seebach, Methoden der Organischen Chemie, Houben-Weyl,
Vol. 4/4,
cyclodimerizes
@, i n which the two cyclohexane
p. 174, Thieme, S t u t t g a r t 1971; b ) 8. P a t a i , ed., The Chemistry o f
Ketenes, Allenes and Related Compounds, Wiley 8 Sons, Chichester,
each other.
It i s worthy o f note t h a t the c y c l o -
1980; c ) W.T.
Brady, Synthesis 1971, 415; W.T. Brady, Tetrahedron 37
i s again s t e r e o s e l e c t i v e (I3C NMR and GC: a t
l e a s t 95% of one isomer), and we assume t h a t t h e C Z h o r
anti dimer gb
(1981)
2949.
G. Kobrich, A . Schmidt, Tetrahedron L e t t .
1974,2561.
i s a l s o formed p r e f e r e n t i a l l y i n t h i s r e a c t i o n .
In sumnary, carbonylcyclopropanes
Lb-g
have been generated by
d
p r a c t i c a l procedure, and shown t o undergo ready c y c l o d i m e r i z a t i o n . The
R.D.
Clark. C.H. Heathcock, J.Org.Chem.
J.M.
Oenis, C. Girard, J.M. Conia, Synthesis,
P.S. S k e l l . A . Y .
Garner, J.Am.Chern.Soc.
41
7:
(1976)
1972,
(1956)
636; see a l s o
549.
5430.
i n t r i n s i c r e a c t i v i t y of the novel ketoketenes promises f u r t h e r r e a c t i o n s
of mechanistic and s y n t h e t i c i n t e r e s t .
- 22 -
Received: July 3,
-
24 -
C9;
Paquette,
Morton,
Becker, B. Ruge, Angew.Chem.
K. Geibel, L i e b i g s Ann.Chem.
Isomers from
91
Eizember, J.Am.Chem.Soc.
(1975)
Chem. 90
b ) Photochemical approaches t o carbonylcyclopropanes:
Scheme 2. Cyclobutan-1.3-dione
389.
(1977)
a) Attempts t o p r e p a r e l q go back t o H. Staudinger, H. Schneider,
198i
/Z
061a S /
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course, cyclopropyl, generation, sterin, carbonylcyclopropanes, cyclodimerization, dispiro, idenemethanones
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