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Cycloadditions of Keteneimines of Ynamines.

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Fig. 1. IR spectra of Ba12 . 2 H 2 0 (l),BaBr, . 2 H 2 0 (2), BaCIZ . 2 H 2 0
(3), SrCl, . 2 H 2 0 (4), SrC1, . 6H,O (S), SrBr, . 6 H 2 0 (6).
SrC12 . H 2 0 and SrI, H,O could not be identified X-ray crystallographically. Thus, as has already been established in the case
of alkaline earth metal hydroxides[*], compounds of the above
type that cannot be identified by X-ray crystallography can be
unequivocally characterized by their IR spectra. Just the close
range order of a few cells apparently suffices for observation
of the lattice vibrations of a structure.
The alkaline earth metal halide monohydrates were prepared by
dehydration of hexa- or dihydrates in vacuum at 75-100°C.
T h e preparation of samples for IR spectroscopic measurements
(nujol, KBr; Beckman IR 10) and X-ray (powder) crystallography (CuKu) was carried out in a dry-box because some of
the compounds are very hygroscopic.
Table. Crystallographic data of alkaline earth metal halide monohydrates
(‘9.
BaBr,-H,O‘”
BahH2O
SrBr2.H20
[*j Prof. Dr. H. D. Lutz, Dipl.-Chem. H.-J. Kliippel, and G. Kho
Institut fur Anorganische Chemie der Universitat
5 Koln 1, Ziilpicher Str. 47 (Germany)
[l] Lattice vibration spectra, Part 6. -This work was supported by the
Fonds der Chemischen Industrie and the Stiftung Volkswagenwerk. Part
5: H. D. Lutz, R. Heider, and R.-A. Becker, Spectrochim. Acta, inpress.
[2] H. D. Lutz, R. Heider, and R.-A. Becker,Z. Naturforsch. 246,1657
(1969).
[3] H D. L o 9 Spectrochim. Acta 24A, 2107 (1968); H. D. Lutz and
R.Heider, Z. Naturforsch. 24a, 476 (1969).
[4] A. T. Jensen, Struct. Rep. 8 133 (1940); Kgl. Danske Videnskab.
Selskab. Mat.-Fys. Medd. 17, 1 (1940); 20, 1 (1942); 22, 3 (1945).
(51 E. Bang, Kgl. Danske Videnskab. Selskab. Mat.-Fys. Medd. 33,23
(1961).
[6] 0. Miigge, Neues Jb. Mineralog. Geolog. Palaontol., Abh., 1, 174
(1889).
[7] B. K . VajnSteinand 2. G. Pinsker, Zh. Fiz. Khim. 23, 1058 (1949).
4.73
4.88
9.92
8.96
11.59
12.15
11.47
Received: November 11,1970 [ Z 332 IE]
German version: Angew. Chem. 83, 170 (1971)
184
Fig. 2. IR spectra of BaCl,. H,O (l), BaBr, . H 2 0 (2), Bar2. H,O
(3), SrC1, . H 2 0 (4), SrBr, . H 2 0 (S), Sr12 . H 2 0 (6).
Cycloadditions of Keteneimines to Ynamines[**I
By L6on Ghosez and Cecilia de Perez[*]
Experience[’] has well substantiated Woodward and Hoffmann’s suggestion [*I that ketenes ( l a ) owe their reactivity in
Angew. Chem. internat. Edit. / Vol. 10 (1971) / N o . 3
(2+2) cycloadditions to their ability to behave electronically
as “pseudo” vinyl cations (Za).
;c=c=x
-
f 1)
(a),X
= 0;
0 0
)c=c-x
(2)
(b), X = N-R
Substitution of a nitrogen atom bearing various substituents (Ib)
for the oxygen atom in the ketene molecule would offer the
interesting possibility of varying the vinylium character of the
f 7)
(6)
(a), R = R ‘ = CH,
(b) , R = C&5; R‘ = CH3
(c) , R = R‘ = C &
( d ) , R = CH3; R‘ = CsH5
n .p-( “C
n/e
( yield (%);
uv
NMR
Icl
[bl
256(M+)
314 (4.12)
309 (3.17)
!23 (44.7)
1.0516 Methyl-Hlt);
1.35(6 Methyl-Hld);
2.45(3 Methyl-Hls);
3.32(4 Methylene-H+l
Methine-H/m); 7.40
(2 arom. H/m); 7.90
(2 arom. H/m)
380(M+)
322 (5.2)
$09 (4 17)
134 (52.7)
1.01(6 Methyl-Hlt);
2.38(3 Methyl-Hls);
3.30(4 Methylene-H/q);
5.92(1 Methine-Hls);
7.45(12 arom. Hlm);
8.0(2 arom. H l m )
442(M+)
322 (4.5)
!34 (54.2)
0.92(6 Methyl-Hlt);
2.87(4 Methylene-H/q);
5.45(1 Methine-His);
7.00-8.3(19 arom. H l m )
318(M+) 320 (4 33)
!30 (46.4)
318(M+)
207
205
113
-
525(M+)
455
318
207
-
0.95(6 Methyl-H/t);
123(6 Methyl-H/d);
2.90(4 Methylene-H +
1 Methine-Hlm; 2 7.40
(7 arom. Hlm), = 8.10
(2 arom. H/m)
0.83(6 Methyl-Hlt);
2.13(3 Methyl-Hls);
3.20(4 Methylene-Hlq);
3.26(3 Methyl-Hls),
= 7.30(10 arom. H l m )
0.5016 Methyl-Hlt);
1.66(3 Methyl-Hls);
2.30(2 Methylene-Hlq);
2.70(3 Methyl-H+ 2Met,hylene-Hls + 9); 3 22
(3 Methyl-Hls); 6.807.70(20 arom. H l m )
Ia’B.p 140- 142”C/0.7-0.9 torr
‘” ,Imax(nm),
lo‘’ (in cyclohexane).
values, TMS internal standard (in CDCI’).
EX
“I S
Angew. Chem. internat. Edit./ Vol. 10 (1971)/ N o . 3
cumulene (2b) and studying the consequences on its behavior
in cycloadditions.
This preliminary report describes the stepwise polar cycloaddition of N-aryl and N-alkyl-substituted keteneimines to the
strongly nucleophilic aminoacetylenes. We have found that Nphenylketeneimines (3a) and (36) cycloadd to ynamines
(4a)-(4b) at room temperature to yield the 4-aminoquinoline
derivatives (7a) to (7d) as the sole isolable adducts. This provides a simple synthetic route toward these heterocyclic systems.
In contrast the reaction of N-methyl-diphenylketeneimine(3c)
with (4a) in acetonitrile is sluggish (7 days) and yields both 1 : 1
and 2 : 1 adducts for which structures (9)and (10)are proposed
mainly on the basis of mass spectral data.
In each case, solvents with high dielectric constant were shown
to accelerate the reaction: monitoring the reaction by IR showed
that, in ether, the formation of (7d) required about 3 days,
whereas in acetonitrile it was essentially completed after 6-7
h. It is worth noting that these cycloadditions proceed much
more slowly than the corresponding reactions involving ket e n e ~ [ ~Roughly,
].
it can be said that the reactivity sequence parallels the “vinylium” character of the cumulene:
C=C=OSC=C=N-aryl > C=C=N-alkyl.
Our observations are consistent with a cycloaddition mechanism
involving the initial formation of a stabilized 1,4 dipole (5) or
(8) which either cyclizes to 6 or 4 membered rings (6) or (9),
or is trapped by a second molecule of keteneimine to yield (10).
Z-Benzhydry1-4-diethylamino-3-phenylquinoline(7c). A mixture of (4b)(0.329g, 1.9 mmole) and (36)(0.431 g, 1.6mmole)
in acetonitrile (10 ml) was allowed to stand under nitrogen at
room temperature; after 10 hours, 0.318 g of crystalline (7c)
could be filtered off. A further crop of (7c) was obtained by
evaporation of the filtrate and recrystallization of the resulting
residue from ether/pentane. Total yield 0.431 g (61%).
Received: January 4, 1971 [Z 333 IE]
German version: Angew. Chem. 83, 171 (1971)
[*] Prof. Dr. L. Ghosez and C. de Perez
Laboratoire d e Chimie Organique de Synthkse
Universite de Louvain, Naamsestraat 96
B-3000 Louvain (Belgium)
[**I
This work was supported by the Fonds d e la Recherche Fondamentale Collective.
[I] A. Roussel, E. Cossement,and L. Ghosez, unpublished; M. Rey, S.
Roberfs, A. Dieffenbacher, and A. S. Dreiding, Helv. Chim. Acta 53,
417 (1970); W. T Brady, R. Roe Jr., E. F. Hoff, and E H. Parry, J.
Amer. Chem. SOC.9 2 , 1 4 6 (1970); W. T. Brady, F. H. Parry, R. Roe Jr.,
and E. F. Hoff Jr., Tetrahedron Lett. 1970, 819; P. R. Brook, T. M .
Harrison, and A . J. Duke, Chem. Commun. 1970,589; M. Rey, S. Roberts, A. s. Dreiding, A. Roussel, H. Vanlierde, and L. Ghosez, unpublished; L. Ghosez, R. Montaigne, A. Roussel, H. Vanlierde,a n d P. Mollet, Tetrahedron, in press.
[2] R. B. Woodward and R. Hoffmann,Angew. Chem. 8 1 , 7 9 7 (1969);
Angew. Chem. internat. Edit. 8, 781 (1969).
[3] M. Delaunois and L. Ghosez, Angew. Chem. 8 I , 3 3 (1969);Angew.
Chem. internat. Edit. 8, 72 (1969); M. E. Kuehne and P. J. Sheehan,
J. Org. Chem. 33, 4406 (1968).
185
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