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Stable Open-Chain 1 3-Dilithium Compounds by Reaction of Methylenecyclopropanes with Lithium Powder 2 4-Dilithio-1-butenes.

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Our investigations allow germanium to be added to the
already wide range of elements which can occupy T sites
in MFI frameworks. The unexpectedly high Ge contents
exceed the degrees of Si substitution achieved up to now.
The upper limit of the Si :Ge ratio of about 2 can be understood on the basis of the assumption that the formation of
Ge-0-Ge linkages is avoided; they have also not been detected in
Consequently, a pure Ge-MFI zeolite
is expected to be difficult to synthesize.
We have now found that methylenecyclopropane 3 also
reacts smoothly with lithium powder, both neat at its boiling point (lO°C, 1 h) and in diethyl ether at room temperature (1/2 h). However, cleavage of the weakest cyclopropane bond to form the extremely stable, Y-delocalized trimethylenemethane dianion 414]does not occur. Instead,
the 2,4-dilithio-l-butene 5, combining both vinyl and homoallyl character, is the sole product (Scheme 1).
-
Received: July 4, 1988;
Revised: September 23, 1988 [ Z 2841 IE]
German version: Angew. Chem. 101 (1989) 60
[I] W. S. Miller, F. Dachille, E. C. Shafer, R. Roy, Am. Miner. 48 (1963)
1024.
[2] B. 2. Shalumov, L. A. Zhukova, E. A. Ryabenko, N. G. Chernaya, Y. V.
Oboznenko, Izv. Akad. Nauk. SSSR Neorg. Muter. 22 (1986) 966.
[3] G. Gottardi, E. Galli, Natural Zeolites, Springer, Berlin 1985, p. 409.
[4] R. M. Barrer: Hydrothermal Chemistry of Zeolites, Academic Press, London 1982, p. 543.
[5] E. M. Flanigen, J. M. Bennett, R. W. Grose, J. P. Cohen, R. L. Patton, R.
M. Kirchner, J. V. Smith, Nature (London) 271 (1978) 512.
161 H. Gies, R. R. Gunawardane, Zeolites 7 (1987) 442.
[7] G. Perego, G. Bellussi, C. Corno, M. Taramasso, F. Bounomo, A. Esposito in Y. Murakami, A. Iijima, J. W. Ward (Eds.): New Developments in
Zeolite Science and Technology. Kodansha, Tokyo 1986, p. 129.
[8] Z. Gabelica, N. Blom, E. G. Derouane, Appl. Catal. 5 (1983) 227.
[9] J. L. Guth, H. Kessler, R. Wey in Y. Murakami, A. Iijima, J. W. Ward
(Eds.): New Developments in Zeolite Science and Technology, Kodansha,
Tokyo 1986, p. 121.
[lo] D. G. Hay, H. Jaeger, J . Chem. Soc. Chem. Commun. 1984. 1433.
[Ill Z. Gabelica, J. B. Nagy, P. Bodart, A. Nastro, Thermochim. Acta 93
(1985) 749.
[I21 M. Soulard, S. Bilger, H. Kessler, J. L. Guth, Zeolites 7 (1987) 463.
1131 J. B. Nagy, 2. Gabelica, E. G. Derouane, Chem. Lett. 1982, 1105.
[14] C . T. G. Knight, R. J. Kirkpatrick, E. Oldfield, J . Am. Chem. SOC. 109
(1987) 1632.
2 Li
4
4
3
Li
,
.:
:.C
or
I
I
2. Me,SiCI
.)
Me,SiCI
Polylithium organic compounds['] can be prepared by
reductive cleavage of a cyclopropane o bond with lithium,
provided that a resonance-stabilized system is formed; for
example, the dilithium "semibullvalenediide" 2 is obtained by treatment of semibullvalene 1 with lithium in
2 Li
THF, -78OC
2
THF or dimethyl ether at - 78"C.f21
The homologous barbaralane reacts analogously, that is, again with formation
of a bis(a1lyllithium) compound.[31
[*I Prof. Dr. A. Maercker, Dipl.-Chem. K.-D. Klein
Institut fur Organische Chemie der Universitat
Adolf-Reichwein-Strasse, D-5900 Siegen (FRG)
[**I Polylithium Organic Compounds, Part 9. This work was supported by
the Minister fur Wissenschaft und Forschung des Landes NordrheinWestfalen and by the Fonds der Chemischen 1ndustrie.-Part 8: A.
Maercker, F. Brauers, W. Brieden, M. Jung, H. D. Lutz, Angew. Chem.
100 (1988) 413; Angew. Chem. Inr. Ed. Engl. 27 (1988) 404.
Angew. Chem. Int. Ed. Engl. 28 (1989) No. I
t
E
An
9
S Me
10
a: E = MeS
b E = Me,Si
Scheme 1.
Table 1. Important physical data for the compounds 5 , 8, 9 a , b , and 10
[a].
5 : 'H NMR (SO MHz, [DIO]Et20):
6=6.03, 5.21 (2 d, br, '5'5.5
Hz; HIC=),
2.89 (t. br, 'J=7.2 Hz; CHIC), -0.75 (t. 'J=7.2 Hz; CH,Li) "C NMR (20.1
MHz, [DIO]Et20): 6=204.4 (=CLi), 119.8 (H,C=), 49.5 (CH'C), 11.4
(CH,Li). 6Li NMR (58.9 MHz, [Dln]Et20,standard I M LiCl in THF, external): 6 = 1.6 (s, br)
8: 'H NMR (80 MHz, [D6]DMSO): 6 = 12.27 (s, br; 2 C02H), 6.07, 5.62 (2 d,
Hz; H2C=), 2.43 ( 5 , br; 2 CHJ "C NMR (20.1 MHz,
hr, '5'1.5
[DeIDMSO): 6 = 173.5, 167.7 (2 COIH), 139.7 (=C), 124.6 (HzC=), 32.6, 26.7
(2 CHI). MS (70 ev): m / z 144 (M",2%), 226 (82), 98 ($00).69 (46). 55 (48), 53
(62). 45 (39). M.p. 128-133°C. Cf. [S]
-
1
7
Si Me3
C02H
By Adaibert Maercker* and Klaus-Dieter Klein
Dedicated to Professor Gerhard Hesse on the occasion of
his 80th birthday
1. MeSSMe
MeSSMe
8
Stable Open-Chain 1,3-Dilithium Compounds by
Reaction of Methylenecyclopropanes with
Lithium Powder: 2,4-Dilithio-l-butenes**
,
I
9 a : 'H NMR (80 MHz, CDCI,): 6=5.07,4.65 (2 s, br; H2C=), 2.76-2.38 (m;
2 CHI), 2.24, 2.12 (2 S ; 2 SCH,). "C NMR (20.1 MHz, CDCI,): 6=145.0
(=C), 104.8 (H2C=), 37.0,33.2 (2 CHI), 15.1, 14.1 (2 SCH,). MS (70 eV): m / z
148 (M",18%), 133 (28), 101 (23), 85 (15), 61 (IOO), 53 (14), 45 (15). B.p.
86-88"C/10 tom. Correct elemental analysis
9b: 'H NMR(80 MHz, CDCI,): 6=5.59, 5.30 (2 dt, 'J=3.0, 4J= 1.5, 1.1 Hz;
HIC=), 2.16 (m; CH2C), 0.62 (m: CH,Si), 0.11, 0.01 (2 s: 2 SiMe,). "C NMR
(100.6 MHz, CDCI'): 6 = 154.9 (=C), 122.3 (HZC=), 29.9, 16.1 (2 CHI), - 1.3,
- 1.7 (2 SiMe3). MS (70 ev): m/z 200 (Me,
8%), 113 (S), 112 (44),97 (33), 74
(18). 73 (IOO), 45 (14). B.p. 65-66"C/12 tom. Cf. [6]
10: 'H NMR (80 MHz, CDC13): 6=5.59, 5.39 (2 m; H2C=), 2.62-2.39 (m; 2
CHI), 2.13 (s: SCH,), 0.09 (s; SiMe,). "C NMR (100.6 MHz, CDCI,):
6= 150.7 (=C), 125.1 (H2C=), 35.6, 33.8 (2 CHI), 15.6 (SCH'), - 1.5 (SiMe,).
32%), 159 (100). 105 (74), 73 (68). 61 (37), 59 (16).
MS (70 ev): m/z 174 (M",
45 ( I 1). B.p. 75-76YYIO tom. Correct elemental analysis
[a] DMSO = dimethyl sulfoxide.
0 VCH Verlagsgesellschaf~mbH. 0-6940 Weinheim. 1989
0570-0833/89/0101-0083 $ 02.50/0
83
Derivatization of 5 with carbon dioxide, dimethyl disulfide, and chlorotrimethylsilane leads to formation of the
expected products 8 (50%), 9a (53%), and 9b (67%), respectively, which were characterized by NMR spectroscopy and mass spectrometry (Table 1); dimethyl sulfate affords 2-methyl-1-pentene in 68% yield. Since the two anionic centers of 5 differ in their reactivity, the reaction can
also be carried out stepwise with two different electrophiles, for example, first with one equivalent of dimethyl
disulfide and then with chlorotrimethylsilane. The formation of 10 (Scheme l, Table l ) in 25% yield proves that-as
expected-the homoallyl position is more reactive than the
vinyl position. This is further supported by the tandem
reaction with methanol and chlorotrimethylsilane, which
gives mainly 2-trimethyl~ilyl-l-butene[’~
(33%). However,
the presence of traces of 2-lithio-1-butene 11 always has to
be taken into consideration, since still unreacted 3 is in
part metalated by 5.
S
11
12
Compound 5 is remarkably stable toward diethyl ether
as solvent, a property already observed for 1,3-dilithiopropane[’] and, as in that case, presumably due to a doubly
bridged structure.[’] However, in contrast to 1,3-dilithiopropane,[*]which rapidly eliminates lithium hydride (halflife period of 1 h at room temperature), 5 does not display
such reaction behavior at all-neither 2-lithio-1,3-butadiene 6 nor its tautomer 7 (Scheme 1) could be detected. It
was therefore possible to carry out detailed N M R studies
on the orange-red solution of 5 (Table 1). However, no
conclusions could be drawn regarding association and
bridging, since the 6Li,’3C coupling constants could not be
derived from the spectra. The appearance of several signals in the 6Li N M R spectrum recorded between - 20 and
-80°C is not compelling evidence against a doubly
bridged structure, but might also indicate the simultaneous
presence of different aggregates. Unfortunately, the crystals obtained so far have not been suitable for an X-ray
structure analysis.
The reaction of 2,2-dimethylmethylenecyclopropane13
with lithium powder under the same conditions, yielding
17, provided clues as to the mechanism of cleavage of 3
with lithium (Scheme 2). The formation of 17 indicates
that, before ring-opening occurs to give 16, the initially
formed radical anion 14 reacts with a second lithium atom
to give the I-lithiomethylcyclopropyllithium 15. As a cyclopropylcarbinyllithium derivative, 15 then undergoes the
known[’”]anionic rearrangement with ring-opening to form
the primary homoallyllithium derivative 17.[’11
Experimental Procedure
Approximately 10% of a solution of 3 (8.0 g, 0.15 mol) I121 in 50 mL of diethy1 ether was added dropwise, initially at room temperature, to a suspension
of lithium powder (2.5 g, 0.36 mol, 2% sodium) in 50 mL of diethyl ether, the
reaction being carried out under argon. After the reaction had begun-the
reaction solution turned yellow and began to reflux-the remaining solution
of 3 was added at ice-bath temperature so as to avoid partial evaporation of
3 (b.p. 10°C). The reaction mixture was then stirred for 1/2 h at room temperature and the excess lithium was filtered off under inert gas. Yield: 7075% 5 ; very stable (half-life period of decomposition, 27 d at room temperature).
Received; July 22, 1988 [Z 2881 IE)
German version: Angew. Chem. 101 (1989) 63
[l] Review: A. Maercker, M. Theis, Top. Curr. Chem. 138 (1987) 1.
[2) M. J. Goldstein, T. T. Wenzel, G. Whittaker, S. F. Yates, J. Am. Chem.
SOC. 104 (1982) 2669; M. J. Goldstein, T. T. Wenzel, J . Chem. SOC.
Chem. Commun. 1984. 1654, 1655.
[3] R. Trinks, K. Mullen, Chem. Ber. 120 (1987) 1481.
[4) Reviews: J. Klein, Tetrahedron 39 (1983) 2733; ibid. 44 (1988) 503.
[5] J. Kagan, L. Tolentino, M. G . Ettlinger, J . Org. Chem. 40 (1975) 3085.
[6) P. Cros, C. Triantaphylides, G. Buono, J . Org. Chem. 53 (1988) 185.
[7] B.p. 30-32T/lIl torr; appropriate ’Hand I3C NMR and mass spectra.
Cf. Yu. K. Grishin, N. M. Sergeyev, Yu. A. Ustynyuk, Org. Magn. Reson. 4 (1972) 377.
[8] J. W. F. L. Seetz, G. Schat, 0. S. Akkerman, F. Bickelhaupt, J. Am.
Chem. SOC.104 (1982) 6848.
[9] P. von R. Schleyer, A. J. Kos, E. Kaufmann, J. Am. Chem. SOC.105
(1983) 7617.
[lo] Cf. P. T. Lansbury, V. A. Pattison, W. A. Clement, J. D. Sidler, J. Am.
Chem. SOC.86 (1964) 2247.
[ I l l The corresponding tetramethyl derivative of 3, on the other hand, leads
only to a monolithium compound, since, after ring-opening, the initially
formed product eliminated lithium hydride. The reason for this secondary reaction might be the formation of a tertiary homoallyllithium center
occurring for the f i n t time’
1121 R. Koster, S. Arora, P. Binger, Justus Liebigs Ann. Chem. 1973, 1219.
Structures of Quino[7,8-hlquinoline and
QuinoI8,7-h]quinoline**
By CIaus Krieger, Ian Newsom, Michael A . Zirnstein,
and Heinz A . Staab*
18
14
1s
P
P
16
17
Scheme 2
84
0 VCH Verlagsgesellschafl mbH. 0-6940 Weinheim, 1989
Recently, we described a new type of “proton sponge”,
quino[7,8-h]quinoline 1.121The two nitrogen atoms of 1 are
mutually oriented as in 1,s-bis(dimethy1amino)naphthalene (“proton sponge”); in contrast to the earlier “proton
sponges”, however, 1 lacks the hydrophobic shielding of
the basic centers and thus of the hydrogen bond in the
monoprotonated cation, which was responsible for the low
[*I
[**I
Prof. Dr. H. A. Staab, C . Krieger, Dr. I. Newsom,
Dip1.-Chem. M. A. Zirnstein
Abteilung Organische Chemie
Max-Planck-lnstitut fur medizinische Forschung
Jahnstrasse 29, D-6900 Heidelberg (FRG)
New “Proton Sponges”, Part 8.-Part 7: H. A. Staab, M. Hbne, C .
Krieger, Tetrahedron Lett. 29 (1988) 1905.
0570-0833/89/0101-0084 $ 02.50/0
Angew. Chem. Int. Ed. Engl. 28 (1989) No. 1
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