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Catalytic Synthesis of 1 2-Diaza-1 5 9-cyclododecatrienes from Butadiene and Azines.

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CAS Registry numbers:
[(C,H,),NiC,H,IZNa,(THFli.
.~
~
equatorially, while in the case of the cis compound ( l b )
the forms ( I b)ea and ( I b)'te are in equilibrium.
57774-33-1
-
[I] K . Joniis. Angew. Chem 88. 51 (1976): Angen Chem. Int Ed. Engl.
IS. 47 (1976). rhirl. 85, 1050 (1973jand I:, 997 (1973).
[2] C. Kriiyw. and Y - H . Tsoj.. Angew. Chem. 85. 1051 (1973);Angew. Chem.
Int. Ed. Engl. I?, 998 (1973).
[3] K. Joiios, D J. Braiwr., C. Kriiger.. P. J . Kohwrs, and Y - H . Tsa!.. J .
Amer. Chem. SOC..in press.
[4] K . Fr.\~hc~r.K . Jorio. P. A4ishrrr.h. K. Strihhu, and G. WilLr. Angew.
Chem. 85. 1002 (1973); Angew. Chem. lnt. Ed. Engl. 12. 943 (1973).
J . Organometal. Chem.
[5] E. Miillw, J . K r o i r s e . and K S~Jimii.ilt.~iirc.ht.
44. 127 (1972).
[6] Na-Na: 3 7157k in the metal, 3.079A in the gas phase.
Catalytic Synthesis of 1,2-Diaza-l,5,Pcyclododecatrienes from Butadiene and Azines
By Paul Heimbach, Bernard Hugelin, Heinz Peter, Achim Rolofl,
and Eduard Trox/er[*]
Starting points in our investigations were, inter a h ,publications by Wilkel'] and Heimbach'" as well as an observation
by M e ~ w [ 'We
~ . have now found, in independent studies[4'51,
that 3,3,12,12-substituted 1,2-diaza-l,5,9-cyclododecatrienes
( / ) - ( / 2 ) are formed by catalytic co-oligomerization of ketazines or aldazines with butadiene. We employed nickel catalysts with and without added phosphane or phosphite; the
molar ratio of butadiene to azine was 3 : 1 to 10: 1 (see Table
1)'Y
(lbjCd
(1 a ) and (1 b ) differ greatly from each other, inter aliu,
in the coupling constants of the 'H-NMR spectra. This is
clearly seen from a section of the spectrum of the rigid form
f 1a ) e e .
Rigid form i I [I) cc:
J l , Z = l IHz: J i , ' = 2 H z , J j , , = 6 . 5
H'
H2
8'y
No-L
LR4
HZ
and f I b ) , , c :
Flexible forms ( I b)<&
J i , Z = 6 . 5 H z (mean value: 11+2); J , , 3 = 4 H r (mean value): J , .=6.SHz.
K3
5-4
(lbJdC
\
The IR spectrum of ( l a ) and ( I b ) shows only typical
bands for trans double bonds (at 1670 and 9 5 6 ~ 1 ~ - I )A.
( I ) - (12)
Table 1 . Prepared 1.2-diara-l,5.9-cyclododecatr1enes
( I i ~ i f 2 i . T h e y i e l d s a r based
e
onazine used. Molar ratio butadiene:azine=3- -10.1. Catalyst 'seeexperimental
procedure.
____-
cpd.
__-_______
Substituents
____
_ _ _ _ ~ . _ _
Reaction
temp. ["C]
Reaction
time [h]
-~
_--_____.__-___
80
80
90
60
30
80
80
________
___________
35
35
80
90
60
__---___
4
4
0.66
1
48
2.5
1.5
20
21
4
0 66
1
_---_
_
~
Yield
I'YJ
_---
83
72
16
79
78
50
84
80
82
93
55
51
_____
9 . p . ["CJorr]
M.p. ["C]
~
~
110;10 [a]
89- 92.0.03
60 -61 [b]
102 - 10.3 [b]
155 [h]
156 (dec.1 [b]
I 82, I34 r.1
124 [b]
138-1411 [h]
63- -65:0.02
1 0 3 ~- 104:0.4
62- -64
--
~~
[a] ( l u ) : ( I h ) = 5.6: I
[b] Only one isomer was prepared in pure form on recrystallization.
[c] Two isomers in the ratio 2.8: I .
The symmetric aldazines (R'=R3=alkyl or aryl;
R 2 = R 4 = H ) lead to two isomers; for instance, the trans compound ( I a ) is present almost exclusively in the practically
rigid conformation (I a ) e e with both substituents arranged
[*] Prof. Dr. P. Heimbach and DipLChem. A. Roloff
Universitit Essen--Gesamthochschule
43 Essen. Postfdch 6843 (Germany)
and Max-Planck-Institut fur Kohlenforschung
433 MiilheimiRuhr (Germany)
Dr. 9. Hugelin, Dr. H. Peter, and Dr. E. Troxler
Zentrale Forschungslaboratorien der Ciba-Geigy AG
CH-4000 Basel (Switzerland)
Anger.'. Chcm. Inr. Ed. Engl.
1 Vol. I S (1976) No. 1
band at 1675 cm-l in the Raman spectrum is indicative of
a trans arrangement of the -N=Ngrouping. If cyclic
ketones are used for the synthesis of symmetric ketazines
(R' =R2=R3=R4=alkyl) di-spiro compounds such as ( / 2 J
are formed on co-oligomerization with butadiene.
All compounds were identified and characterized by elemental analysis and 'H-NMR, IR, Raman, and mass spectra.
3,12-Dimethy/-1,2-diaza-1,5,9-cj~c~ododecatriene
(I)
A mixture of bis(2,4-pentanedionato)nickel (3.1 g; 12 mmol)
and triphenylphosphane (3.2g; 12 mmol) was treated with
toluene (42.7g) under inert gas in a 500ml ampoule and
49
reduced with ethoxydiethylaluminum (3.25g; 25 mmol) at 0°C.
Thecolor of the solution changed from green to red. A mixture
of acetaldehyde azine (47.8g; 0.5mol), butadiene (83g;
1.54mol), and toluene (77g) is prepared and added to the
catalyst solution. A contraction in volume of ca. 10% is
observed within 24h at 40°C. Deactivation of the catalyst
with an equivalent amount of sulfur and subsequent distillation
at lo-" torr affords 98g of ( I ) (83 yield w.r.t. azine used).
Separation into the isomers ( l a ) and ( 1 h ) was achieved
by preparative gas chromatography.
100-MHz 'H-NMR (solvent [DJ-toluene): ( 1 a), ~ = 5 . 0 5
(m), 6.16 (m),7.47-7.56(m), 8.12 (m), 8.89 ppm (d)(4 : 2 : 4 :4 : 6);
( I b). r=5.07 (m), 6.65 (m). 7.44-7.89 (m), 8.30 (m), 8.85 ppm
(d) (4:2:4:4:6).
been exploited12! Such use requires the availability of methods
for retransforming 2-isoxazolines into open-chain products.
We now describe the conversion of substituted isoxazolines
( I ) into unsaturated oximes (2) and thence into enones (3).
Treatment of 3,5-diphenyl-2-isoxazoline( 1 c ) with ethylmagnesium bromide (molar ratio 1 :2) at 8@85'C in diglyme
affords a 30 yield of the ring cleavage product (E,E)-chalcone
oxime ( 2 c ) . The yield of crystalline (2c) increases on use
of butyllithium, or even better lithium diisopropylamide, to
60%. The unsaturated oximes (2) listed in Table I are
obtained similarly, each in one stereoisomeric form only
(according to the NMR spectra the crude products are also
isomerically pure).
Received: October 23, 1975 [Z 338 1El
German version: Angew. Chem. XX. 29 (1Y76)
G . W i l k r , Angew. Chem. 75, 10 (1963): Angew. Chem. internat. Edit.
2 , I 11963): P. Hrinihacli. W P. Jolli., and G . Wilkr, Adv. Organomet.
Chem. X. 29 (1970).
a ) P. H ~ i i i i b u ~Angea.
h.
Chem. 85. 1035 (1973); h)Angew. Chem. internat.
Edit. 12, 975 (1973): c) Aspects Homogen. Catal. 2. 79 (1974).
R.-V- Mc,!.er. Dissertation. Universitlt Bochum 1973; see [2b]. p. 981.
B. Huqrlin and E. fio.~la..DOS 2330087 (1972). Ciba-Geigy AG.
A . R o k ~ fand
j
P. Hrinihach. unpublished.
Ifthecarbon atoms of 1.3-dienesaresubstituted by nitrogen, the perturbation of the reactive centers 1 and 4 will be lowest w,hen the nitrogen
is present in positions 2 and 3
12)
TCl~iH20IHCIiDMF
-
20"C.7-12 h
R'
R3&
'
R4 0
(3)
The crude products (2) of ring cleavage can be converted
directly and smoothly at room temperature into enones (3)
Table I . z,~-Unsaturatedoximes ( 2 ) and enones 1 3 ) k o m 2-isoxarolines ( I ) . The structures of compounds 121
and ( 3 ) [new: ( 2 h j and (ZP)] were established by IR and N M R spectra and by correct elemental analyses.
_--__
____________ ____
.~
Starting
R'
R2
R3
R'
compound
________
(I())
ilh)
1 I C )
(I(/)
flri
(If)
________
[a]
[h]
[c]
[d]
~
H
H
H
H
-
~
H
H
CH,
H
H
[''/,,I
102
42
59
59
93 [c]
70
[a]
m. p. ["C]
b. p. ["C:torr] [d]
_-_________
I14
114--115
124- 126
94
39- -40
36- 37
53 -55
125 -130.:
95/: to-'
lo-'
-
~-
_----__
-----_______
by treatment with an excess of titanium(1ii) chloride (15
aqueous solution in 4 % hydrochloric acid to which has been
added an equal volume of diniethylformamide)!3J (see Table
1).
e i d o -aiiioi1
The oxime formation occurs cia endo anion ( 4 ) ' 5 - 8 1as
shown, for example, by deuterolysis of ( 4 c ) . If ex0 hydrogen atoms are present in the c* position of the CN double
bond in ( ' I ) , then exo metalation competes with endo
metalation/ring cleavage (cf. yields in Table 1 ). Depending
upon the degree of substitution of the K.YO and erido positions this should also permit selective CC bond formation at the isoxazoline stoge and therefore considerably
?,id<,
50
["Cl
Yield based on i l l . Compounds f 2 i were not isolated.
Acetophenone is formed (NMR, 5- 9 ",,,J in a fragmentation occurring as side reaction [4].
Mixture of ( E ) , ( Z ) .3!{; i n the ratio 8 7 : 4 : 9 ( N M R ) .
Bulb-tube distillation. bath temperature.
By Volker Jager and Hartmut Grund[*l
Substituted 2-isoxazolines (4,5-dihydroisoxazoles) ( I ) are
readily accessible under mild conditions by 1,3dipolar cycloaddition of nitrile oxides to alkenes"! This represents a CC
bond forming process in which a substituted C t unit (nitrile
oxide) is combined with a (substituted) C , unit (alkene). By
suitable choice of reactants, which can be varied within wide
limits, a large number of carbon skeletons can be constructed.
However, synthetically the inherent possibilities have hardly
[**I
37 [b]
60 [b]
60 [b]
60
61
I-I
_______
Eliminative Ring Opening of 2-Isoxazolines: A New
Route to cqP-Unsaturated Ketones[**]
I'[
131
yield
~-
C,H,
C,H,
C,H,
C,H,
-iCH
-iCHZlJ-
___________ ______
m.p.
yield
[":,I
______
CH3
C,H5
C,Hs
C,Hi
ChH,
CH 3
~
1-71
*
Dr. V. .lager and Dip1.-Chem. H. Grund
fnstirut fui- Organische fhemie der Universitlt
63 Giessen, Heinrich-Buff-Ring 58 (Germany)
Syntheses r i n Isoxaroliiies. Part 1 : part of a lecture delivered at the
G D C h General Meeting. Cologne. September 1975.--This work was
supported by the Deufsche Forschungsgemeinschaft
Ai7glW'. Clirtri. In(. Ed. Enql.
;Vol. 15
(1976) No. I
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synthesis, azines, catalytic, cyclododecatriene, diaz, butadiene
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