close

Вход

Забыли?

вход по аккаунту

?

An Unsual Double Intramolecular CyclizationЧStructural Analysis of 2 6-Dibromo-4 8-dimethyltetracyclo[3.3.0.02 8

код для вставкиСкачать
Even at 20 “ C the benzylideneammonium ions (12) generated from (5) and aromatic aldehydes, ring-expand to the
pyrrolinium ions (13), which on loss of benzylamine, stab i k e by formation of the ~ ~ r r o l e(7)s [or P)-(IIA. The
ring-expansion of (12) probably proceeds equally rapidly
and analogously to N-benzylidene(l,2,2-triphenylcyclopro(91, A r y l = 4-N02-C6H4, R3 I
(100). A r y l = 4-N02-CsH4. R3 =
(lohj. A r y l = 2,4,6-(CH3),C,H,,
RSf i A
%ry!
i i l a ) . Aryl = 4-N02-CsH4, R’
: . T I ~ - c ~ H ~( I l h ) . ArY! = 2,4,6-(CH3),C,H2.
R’
K3
-
R5 = H, R4 = CH,
CH1. R‘ = R 5 = H
R 3 = CH,, R4 = R5 = H
‘
R = H, R5 = CH,
R3 = R‘ = H. R5 = CH,
An Unusual Double Intramolecular CyclizationStructural Analysis of 2,6-Dibromo-4,8-dimethyltetracyclo[3.3.0,02~8.0476]octane-3,7-dioner**1
By Krystina Kratzat, Franzw.Nuder, and
Thea Schwar$’]
Dedicated to Professor Karl Freudenberg on the occasion
of his 95th birthday
In our investigations of the structural chemistry of cumulenes”], we sought a route to bisallene- 1,6-dicarboxylic
acid derivatives. The most promising appeared to be the
Table I. Yields of isolated products, physical constants, and ‘H-NMR data in CDCI, of the 2-arylpyrroles (7). (9), ( I O j , (11) obtained from trans-(5)-2HBr. The
data of the pyrrole protons and the methyl groups at the pyrrole ring were optimized using the LAOCOON 111 program.
Cpd.
m. p. [“C]
(b. p. [“C/torr])
(7a) [a1
(103-105/10-’)
(7b)
Yield
“1
Pyrrole ring
3-H
4-H
5-H
53.4
J3.s
Me
JH.M<
N-CH2
Aryl-H
54.5
[Hzl
Aryl
group
suhstituents
78
6.43
6.37
6.55
3.55
1.87
2.79
-
4.18
6.7-7.4
51
6.44
6.32
6.85
3.67
1.88
2.13
-
5.22
6.9-8.3
(7c)
125
75, 70 [b] 6.17
6.24
6.68
3.54
1.81
2.85
-
5.09
6.6-8.5
2.45 (2Me)
(74
67-68
95
6.10
6.39
6.66
3.49
1.69
2.81
-
4.45
6.9 - 8.5
1.95 (2 Me),
2.15 (Me)
(7e)
(90 [ c ] / ~ O - ~ )
(9)
(110 [c]/lo-2)
55
6.60
6.22
6.78
3.73
1.83
2.14
-
5.76
6.7-8.2
62
6.28
-
6.61
-
1.91
-
2.13
0.51
0.94
5.12
1.O -8.5
iI0a)
79-80
38
-
6.16
6.15
-
-
2.71
2.05
0.54
5.05
6.1-8.5
(lob)
(90 [c]/IO-~)
(110)
119-120
[dl
-
6.10
6.69
-
-
2.68
1.95
0.48
4.65
6.8-7.5
29
6.41
6.11
-
3.63
-
-
2.18
J4.HM e 0.84
5.20
6.7 -8.5
(Ilb)
(90 [cl/lO-’)
Id1
5.91
6.04
-
3.36
-
-
2.21
0.91
4.80
6.8-7.5
105
J?-H.M~
J5-H.Me
1.86 ( 2 Me),
2.30 (Me)
1.82 (2 Me),
2.26 (Me)
~~
[a] ‘H-NMR spectrum in C6D6. [b] From cis-(Sa). [c] Bath temperature during the distillation in a sublimation apparatus with cold finger at - 195°C. [dl 57% of a
7 :3 mixture of (lob)and (Ilb).
py1)amines via trimethylene intermediate^^^]. The present
pyrrole synthesis provides an impressive example of the
great acceleration of 1,3-shifts in vinylcyclopropanes by
amino and alkoxide groups (LiO-, KO--)I6’ attached to
the migrating carbon atom. Despite the abundance of
known pyrrole chemistry, novel and simple pyrrole syntheses are of timely interest”].
Received: January 15, 1981 [ Z 789 IE]
German version: Angew. Chem. 93,619 (1981)
[I] H. Quast, J. Slawitz, Tetrahedron Lett. 1976, 3803.
[2] T. H. Fife, A. M. Pellino, J. Am. Chem. SOC.102, 3062 (1980); J. B. Lambert. M. W . Majchrzak, rbid. 101, 1048 (1979).
[3] Unsubstituted 1,2-cyclopropanediamineshave been synthesized by Curtius-degradation: H. A. Staab, F. Vogrle, Chem. Ber. 98, 2691 (1965); T.
Shono, T. Morikawa. R.-1. Okayama, R. Oda, Makromol. Chem. 81, 142
(1965); D. T. Witiak, H . J. Lee, H. D. Goldman, B. S. Zwilling, J. Med.
Chem. 21, I194 (1978).
[4] By analogy to P. Rosenmund. K . Griibel, Angew. Chem. 80, 702 (1968);
Angew. Chem. Int. Ed. Engl. 7, 733 (1968).
IS] P. Caramella, R. Huisgen, B. Schmolke. J. Am. Chem. SOC.96,2997,2999
(1974); K . H . Schroder. Dissertation, Universitat Munchen 1975.
[61 R. L. Danheiser. C. Martinez-Davila, J . M. Morin, Jr.. J. Org. Chem. 45,
1340 (1980) and literature cited therein.
[71 N. Engel. W. Steglich. Angew. Chem. 90, 719 (1978); Angew. Chem. Int.
Ed. Engl. 17, 676 (1978); B. M. Trost, E . Keinnn. J. Org. Chem. 45, 2741
(1980); B. Merah. F. Texier, Bull. SOC.Chim. Fr. 1980,552; T. L. Gilchrisr,
B . Parton. 3. A. Stevens, Tetrahedron Lett. 1981, 1059; J.-E. Backuall. J.E. Nysrrom, J. Chem. SOC.Chem. Commun. 1981, 59.
Angew. Chem. Int. Ed. Engl. 20 (1981) No. 6/7
classic synthesis of allenes from 1,l-dihalocyclopropanes
after Doerind21. By means of this route, pentatetraene~‘~~],
in addition to numerous allene derivative^'^"], were first
synthesized ; furthermore, both acyclic-14a1
and cyclic-bisall e n e ~ ‘have
~ ~ ’ been prepared. A synthetic route to the bisallene-dicarboxylic acid diester (5) starting from the tetrabromobicyclopropyl dicarboxylic acid esters (2) and (3)
should therefore also be feasible.
Double dibromocarbene addition to dimethyl (Z.Z)-2,5dirnethylm~conate~~~
(1) occurred in approximately 20% total yield under phase-transfer catalysis at 50-70°C. In addition to the expected stereoisomers rneso-(2) and (+)-(3),
two further diastereomeric adducts, which were formed as
a consequence of partial isomerization of (Z,Z)-(Z)to
(E,E)-(l),could be obtained in pure form by column chromatographic separation. Configurational assignments were
carried out by spectroscopic and chemical methodsI6].
Reaction of (3) with tert-butyllithium (tBuLi) or lithium
diisopropylamide at -60°C in ether produced a crystalline compound, which after elemental analysis and mass
spectroscopy, proved to have the empirical formula
CIoHsBr2O2.On the basis of the NMR spectroscopic data,
this compound must have a symmetrical structure. The ‘HNMR spectrum contains only two singlets in the ratio 1 :3,
[‘I
[**I
Priv.-Doz. Dr. F. W. Nader, Dr. K. Kratzat, T. Schwarz
Organisch-chemisches Institut der Universitat
Im Neuenheimer Feld 270, D-6900 Heidelberg I (Germany)
This work was supported by the Deutsche Forschungsgemeinschaft
0 Verlag Chemie GmbH, 6940 Weinheim, 1981
0570-0833/81/0707-0589 $ 02.50/0
589
CH300C&cH3
-
COOCH,
+
2 CBr2
+
___)
H3C
Br
ill
Br
rneso- (2)
which are indicative of aliphatic methine protons (6= 3.15)
and methyl groups (6=1.48); the signals are similar to
those of the corresponding educt (3). The I3C-NMR spectrum shows signals arising from five different C atoms. By
virtue of their position and off-resonance decoupling, the
following assignments could be made: 6 0 (6= 196.75),
methine C-H (40.21), CH3 (13.46), in addition to two aliphatic, quaternary C atoms (43.66 and 37.19). Metalation
of (3) leading to formation of an allene system can therefore be excluded. On the contary, the product must result
from an intramolecular condensation of the intermediate
dicarbanions, formed by metalation of (3) with both ester
functionalities. If this condensation occurs on the a-bromocarbanion intermediate (4), the two structures (6) and
(7) could result; if the carbanion attacks the ester group on
the same respective cyclopropyl moiety the highly strained
bisbicyclobutanone (6) is formed, while attack at the other
ester group results in formation of the tetracycle (7).
(5)- 13)
would be expected for a cyclopropanone) and from the investigation of analogous reactions on a model compoundL7'.
An X-ray structure a n a l y d 8 ] of the product confirmed
the suggested structure (7). which has approximate C2symmetry. Due to the influence of the @-esterfunctionL7],the
carbanionic intermediate (4) is so stable-even at high
temperatures-that it does not spontaneously a-eliminate
to the carbene; furthermore, although sterically hindered,
it can react via double intramolecular cyclization to give
(7).
The structural analysis also proves that the stereochemical assignment of the starting material (3) was correct,
since only in the (+)-diastereomer do the ester functions
occupy positions from which double intramolecular cyclization is possible. In contrast, the mesocompound (2) can
only cyclize to the tricyclic cyclopentanone (8). In this latter compound both cyclopropane rings are trans to each
other and hence the second coupling step is, for steric reasons, impossible. In fact, (8)can be obtained by metalation
of (2); an allene is not formed here either.
The structure (6) can most probably be excluded from its
C=O vibrational frequency of 1748 cm-' (ca. 1850 cm-'
Metalation of (3) with tBuLi at 0 ° C in cyclohexane results, in addition to the tetracycle (7). in isolation of a second crystalline compound, which on the basis of analytical
and spectroscopic data''], is assigned the structure of the
tricyclo-[3.1.0.02.4Jhexanederivative (9); under these conditions a second coupling variation-coupling of both CBr2
groups of (3)-is possible, which leads to the formation of
cyclobutane and hence to the "chair-analogous'' structure
(9).
Received: December 9, 1980 [Z 785 IE]
German version: Angew. Chem. 93,61 I (1981)
CAS Registry numbers:
(Z,Z)-(l), 24407-02-1; meso-(2), 77944-46-8; (+)-(3), 77983-48-3; (+)-(6).
77965-66-3; (7). 77944-47-9; (+)-(8). 77944-48-0; (+)-(9), 7794449-1
'1
0
Fig. 1 . Bond lengths [pm] and angles
(7).
590
I"] (average values) of the tetracycle
0 Verlag Chemie GmbH, 6940 Weinheim. 1981
[I] L. Leiserowitz, F. Nuder. Angew. Chem. 85, 150 (1973); Angew. Chem.
Int. Ed. Engl. 12, 158 (1973); 2. Berkouifch-Yellin,L. Leiserowifz, F. Nader. Acta Crystallogr. B 33, 3670 (1977).
[2] W. von E. Doering, A. K . Hoffmann. J. Am. Chem. SOC.76, 6162 (1954).
(31 a) L. Skattebd Tetrahedron 23, 1107 (1967); J. Org. Chem. 31, 2789
(1966); W. R. Moore, H . R . Ward. ibid. 27,4179 (1962); b) J . C. Jochims,
G. Karich, Tetrahedron Lett. 1974, 4215.
141 a) K . Kleveland, L. Skarrebd Acta Chem. Scand. B 29, 191 (1975); b) E.
V. Dehmlou. G. C. Ezimora, Tetrahedron Lett. 1970, 4047; L. Skattebd,
0570-0833/81/0707-0590 .S 02.50/0
Angew. Chem. I n t . Ed. Engl. 20 (1981) No. 6/7
Acta Chem. Scand. 17, 1683 (1963); R. Baker. P. J. Garratr, K . C. Nicolaon. F. Sondheimer, Tetrahedron Lett. 1972, 3425.
[5] J. A . Elurdge. R . P. Linstead, B. A. Orkin, P. Sinis, H . Baer. D . B. Pattison, J. Chem. SOC.1950,2232.
161 K . Kratzat. Dissertation, Universitat Heidelberg 1979.
[71 As a model compound, 2,2-dibromo-l -methylcyclopropanecarboxylic
acid was reacted with tBuLi under the same conditions. Only one stereospecific Br/H-exchange process, leading to ethyl trans-2-bromo- I-methylcyclopropanecarboxylate,occurred. This shows that an extraordinary
stable carbanion is formed syn to the ester function, a fact which is in accord with the stereochemistry of both cyclization products (7) and (9).
[8] Space group P2,/c; a=801.4, b = 1073.7, c= 1221.4 pm, p=97.55"; Z = 4 ,
=2.04 g.cm-'. The structure was solved by direct methods with a
multi-solution technique. [ G . Gemtain, M . M . Woolfon. Acta Crystallogr.
B24,91 (1968); see also H . W. Kaufmann, L. Leiserowitz, ibid. 826,442
(1970)l. The positions of the H atoms were obtained from the IFo- F,I difference map. The refinement with 2531 reflections (of which 589 were
unobserved) converged to an R-factor of 5.2%.
191 Elemental Analysis and mass spectrum (molecular peak at m/e=380)
gave the summation formula C12H12BrZ04.
'H-NMR: 6=1.35 (s, 3H,
C H 3 ) , 2.69 (s, 1 H), 3.81 (s, 3H, O m > ) ;"C-NMR: 6= 169.40 ( M ) ,
52.19 (OCH,), 49.60 (quart. C), 45.71 (quart. C), 39.02 (CH),19.01
(a,).
A Diorganotin Oxide
with a Planar Tin-Chalcogen Six-Membered Ring[**'
By Heinrich Puff, WiIIi Schuh, Rolf Sievers,
and Rene Zimmer"]
Dedicated to Professor Rolf Appel on the occasion of his
60th birthday
The properties of most diorganotin oxides would indicate polymeric structures"]. Although molecular weight determinations indicated presence of trimers in solution in
the case of di-tert-butyltin oxide"] Chu and Murray assumed a polymeric structure in the solid state on account
of the sparing solubility of the sample.
O n reaction of tBu2SnC12 with sodium hydroxide in
boiling toluene we were able to obtain a form of the ditert-butyltin oxide which is readily soluble in organic solvents in the cold and is therefore obviously of low molecular weight.
The compound crystallizes hexagonally in the space
group Rk-D;,, a = 1035, c=5144 pmc3].The unit cell contains six molecules (tBu2SnO)3. As shown by the X-ray
structure analysis[41( R = 0.045), tin and oxygen atoms are
coupled to a planar six-membered ring.
there are either puckered ~ix-rnembered[~~I
or four-memberedLsblrings, or open chainsiSC1.The Sn-0 bond lengths
are of about the same order of magnitude as in comparable
compounds with distinctly tetravalent tin, e. g.
Ph3Sn-0-SnPh,
(195 to 196 pm)16]. In contrast to other
S n O - c o m p ~ u n d s [a~n~association
,
of the molecules with an
increase in the bond numbers of tin and oxygen is not observed; the shortest intermolecular Sn-0 distance is 644
Pm.
Received: August 5, 1980 [Z 792 IE]
German version: Angew. Chem. 93, 622 (1981)
[I] W. P. Neumann: Die Organische Chemie des Zinns, F. Enke Verlag,
Stuttgart 1967, p. 133.
121 C. K . Chu. J. D . Murray, J. Chem. SOC.A 1971, 360.
[3] The same compound was obtained by A. Tzschach and M . Driger(private
communication).
[4] Measurements at - 85°C; four-circle diffractometer CAD 4, program
system X-RAY 76, IBM/370-168 computer at the Regionales Hochschulrechenzentrum, Universitat Bonn.
[S] Cf. a) A . Blecher. M. Drager. Angew. Chem. 91, 740 (1979); Angew.
Chem. Int. Ed. Engl. 18,677 (1979); and references cited therein.-b) H.
PuH.R. Gatfermayer, R. Hundt, R . Zimmer, ibid. 89, 556 (1977) and 16,
547 (1977);-c) H. puff; A. Bongartz, R . Sieuers, R . Zimmer. ibid. 90,995
(1978) and 17, 939 (1978).
[6] C . Glidewell, D . Liles. Acta Crystallogr. B 34, 1693 (1978).
[7] Compounds of type [(RRSnX)20]z:P. G. Harrison, M . J. Begley. K . C .
Molloy, J . Organomet. Chem. 186, 213 (1980): R = R = C H 3 , X=CI; H.
Pufi E. Friedrichs, F. Vise!, Z. Anorg. Allg. Chem., in press:
R=R=CH(CH3)2,X=CI and R=C(CH,),, R=CH2Si(CH3),,X=OH.
Coordination of Dimethyl(thionitroso)amine to
Pentacarbonylchromium via the Sulfur Atom[**]
By Herbert W. Roesky, Ray Emmert, William Clegg,
Wilhelm Isenberg and George M. Sheldrick"'
Dedicated to Professor Josef Goubeau on the occasion
of his 80th birthday
In all complexes of acyclic sulfur-nitrogen compounds
known so far the N-S ligands are coordinated to the metal via nitrogen atoms[''. Reaction of the unstable dimethyl(thionitroso)amine (1/[21-prepared from dimethylhy//S
H3C,
N-N
H&'
Bond length [pm]
196
219
Sn-0
Sn-C
Angle ["I
0-Sn-0
Sn&Sn
C-Sn-C
106.9
133.1
119.9
Such a planar arrangement has so far not been detected
in the case of diorganotin-chalcogen compounds; in the
analogous sulfur, selenium, and tellurium compounds
[*I Prof. Dr. H. Puff, Dr. R. Sievers, Dr. R. Zimmer, W. Schuh
[*'I
Anorganisch-chemisches Institut der Universitat
Gerhard-Domagk-Str. I, D-5300 Bonn (Germany)
This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
Angew. Chem. Int. Ed. Engl. 20 (1981) No. 6/7
+ ( C O ) S C r - T H F +(CH3)2N2S-Cr(CO)S + T H F
(1)
(2)
drazine and sulfur-with (CO)&r, T H F in tetrahydrofuran
(THF) affords the 1 : 1 complex (2), which we isolated as
ruby-red crystals, stable at room temperature. As shown by
a n X-ray structure analysis[31,the SN ligand in (2) is bound
to chromium via the sulfur atom (Fig. 1).
[*I Prof. Dr. H. W. Roesky ['I, R. Emmert
Anorganisch-chemisches Institut der Universitat
Niederurseler Hang, D-6000 Frankfurt am Main 50 (Germany)
Prof. Dr. G . M. Sheldnck, Dr. W. Clegg, DipLChem. W. Isenberg
Anorganisch-chemisches Institut der Universitat
Tammannstr. 4, D-3400 Gottingen (Germany)
['I
Author to whom correspondence should be addressed. Present address:
Anorganisch-chemisches Institut der Universitat, Tammannstr. 4, D3400 Gottingen (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft and
Hoechst AG.
0 Verlag Chemie GmbH, 6940 Weinheim. 1981
0570-0833/81/0707-0591 $ 02.50/0
591
Документ
Категория
Без категории
Просмотров
0
Размер файла
315 Кб
Теги
intramolecular, dibromo, double, analysis, dimethyltetracyclo, cyclizationчstructural, unsual
1/--страниц
Пожаловаться на содержимое документа