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New Silacycloalkynes with up to Four 1 4-Disila-2-alkyne Units in the Ring.

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P. Chamberlain. G. H. Whitham, J. Chem. Soc. 81970, 1382; P. A.
Bartlett in J. D. Morrison (Ed.): Asymmetric Synthesis, Vol. 3. Academic Press, Orlando 1984, p. 430; A. R. Chamberlin, R. L. Mulholland, Tetrahedron 40 (1984) 2297.
[85] B. Giese, D. Bartmann, Tetrahedron Lett.. 26 (1985) 1197; Y. Matsaki,
M. Kodama, S. Ito, ibid. 1979. 2901; S . Thaisrivongs, D. Seebach, J.
Am. Chem. Soc. 105 (1983) 7407; K. E. Harding, R. Stephens, D. R.
Hollingsworth, Tetrahedron Lett. 25 (1984) 4631.
[86] B. Giese, K. Heuck, H. Lenhardt, U. Luning, Chem. Ber. 117 (1984)
2132.
[87] B. Giese, H. Harnisch, U. Luning, Chem. Ber., 118 (1985) 1345.
[88] R. Henning, H. Urbach, Tetrahedron Letr. 24 (1983) 5343.
1891 U. Liining, Dissertation. Technische Hochschule Darmstadt 1984.
[90] B. Giese. J. Meixner, Tetrahedron Lett. 1977. 2783; B. Giese, G.
Kretzschmar, Chem. Ber. 117 (1984) 3175.
[91] K. P. Zeller, H. Straub, H. Leditschke in Houben-Weyl-Miiller: Methd e n der organirchen Chemie, Bd. %111/26, 4th ed., Thieme, Stuttgart
1974. p. 201.
[92] B. Giese, W. Zwick, Chem. Ber. I12 (1979) 3766.
[93] a) B. Giese, W. Zwick, Tetrahedron Lett. 21 (1980) 3569; b) Chem. Ber.
1IS (1982) 2526.
1941 B. Giese, W. Zwick, Chem. Ber. 116 (1983) 1264.
[95] W. Zwick, Disserration. Technische Hochschule Darmstadt 198 I .
1961 B. Giese, H. Horler, W. Zwick, Tetrahedron Lett. 23 (1982) 93 I.
1971 D. Seebach, Angew. Chem. 91 (1979) 259; Anyew. Chem. Inr. Ed. Enyl.
18 (1979) 239.
[98] B. Giese, H. Horler, Tetrahedron Lett. 24 (1983) 3221; see also D. A.
Lindsay, J. Lusztyk, K. U. Ingold, J. Am. Chem. Soc. 106 (1984) 7087.
1991 A. N. Nesmeyanov, 0. A. Reutov, A. S. Loseva, M. Y. Khorlina, Izu.
Akad. Nauk. SSSR Ser. Khim. 1959. 50; Chem. Absrr. 53 (1959)
14965.
[IOO] B. Giese, U. Erfort, Angew. Chem. 94 (1982) 133; Angew. Chem. 1nr.
Ed. Engl. 21 (1982) 130; Angew. Chem. Suppl. 1982, 250.
[loll B. Giese, U. Erfort, Chem. Ber. 116 (1983) 1240.
[I021 B. Giese, R. Engelbrecht, U. Erfort, Chem. Ber., 118 (1985) 1289.
COMMUNICATIONS
7H3
y 3
H,C-Si-(CH,),-Si-CH,
I
c1
2
la-e
I
I
-Si-C=
C-Si-
\
/
I
I
-Si-CrC-Si-
New Silacycloalkynes with up to
Four 1,4-Disila-2-alkyne Units in the Ring**
By Else Kloster-Jensen* and Gudveig Aamdal Eliassen
The replacement of C by Si in the a,a' position of the
C = C bond of 3,3,n,n-tetramethylcycloalkynesinvolves the
consideration of the following factors: the greater steric
demand of the Si(CH3)2 group, the greater length of the
Si-C bond, and the smaller force constant for deformation
of the C-Si-C
angle. Accordingly, such disilacycloalkynes (number of chain links <S) should be more stable
than the corresponding cycloalkynes. We have now synthesized low-membered disilacycloalkynes in order to determine the minimum number of chain links.
The syntheses of angle-strained cycloalkynes are all
based on the introduction of the triple bond into the final
ring system and cannot be transferred to 1,4-disila-2-cycloalkynes. An alternative approach is the coupling twice
of an acetylene with an a,o-disilaalkane of sufficient chain
length that is reactive at both ends.
In analogy to the synthesis of 3,3,8,8-tetramethylcyclooctyne,"-'] the smallest stablel3l cycloalkyne, 2,7-dichloro-2,7-dimethyl-2,7-disilaoctane
ld["] was reacted with
bis(bromomagnesium)acetylide 2 (Scheme 1). However,
[*] Lektor Dr. E. Kloster-Jensen, G. A. Eliassen
Department of Chemistry, University of Oslo
Postfach 1033, Blindern N-0315 Oslo 3 (Norway)
[**I E. K.-J. thanks Professor W . Luttke (Gottingen) for stimulating discussions and Dr. D . Grace (Oslo) for recording the NMR spectra.
Angew. Chem. Inf Ed. Engl. 24 (1985) No. 7
(CH2)n
+
(CH2)n
/I
C
I
\
- Si-
+ 21
I
3
(CH,),-Si-
"[3
(CHZ),-Si-C=C-~i-(CHZ),
I
I
I
C
+ Ill
-3-
I
1
1
I
Ill
C
C
-Si-
I
I
I
-Si-C=
I
31
-Si-
-Si-
(CH,),
+
I
4
I
-Si -C-C-Si-
C
I
isic
C
uC
I
n[2
\
\
C
-Si-I
I
(CH2)n
>S!
I
I
(CHz),
I
-si-CGC
+
BrMgC-CMgBr
i
I
c1
I
+
I
LCH,,,J
"[l
C-Si- (CH,),
I
I
+
11
6
,[4 i 41
5
(CH,),Si
- (CH,),-
Si(CH&
7a-e
Scheme 1. a, n = l ; b, n = 2 ; c, n = 3 ; d , n = 4 ; e, n=O.
1,1,4,4-tetramethyl-1,4-disila-2-cyclooctyne "[ 1 + 1][51 6d,
which is formed from one pair of reactants, could be isolated in very small yield only; it was identified by its mass
spectrum (m/z 196 ( M + ) ) . The main product was "[2+2]
3d, which is formed from two pairs of reactants (Scheme
1).
Furthermore, we have investigated the dependence of
ring formation ability o n the chain length of 1 (n = 0-3).
0 VCH Verlagsyesellycha+ mbH. 0-6940 Weinheim. 1985
0570-0833/8S/0707-0565 $ 02.50/0
565
We were thereby able to isolate cyclic products containing
various numbers of coupled reactant pairs. However, 2,6dichloro-2,6-dimethyI-2,6-disilaheptane
lc,I4I in analogy to
Id, yielded mainly 3[2 21 312, formed from two pairs of
reactants, along with traces of 1,1,4,4-tetramethyl-1,4-disila-2-cycloheptyne 3[1 11 6c, identified by its mass spectrum ( m / z 182 ( M + ) ) .In contrast, lbl4]afforded *[2 + 2) 3b
as well as '[3 +3] 4b and a very small amount of '[4+4]
5b. Analogously, la14' gave the products '[2+2] 3a,I6l
'[3+3] 4a, and '[4+4] 5a.
The last member of the 1 series, l e (n = 0), 2,3-dichloro2,3-dimethyI-2,3-di~ilabutane,'~~
produced, as expected, octamethyl-l,2,5,6-tetrasila-3,7-cyclooctadiyne '[2 21 3e,
which is analogous to 1,5-~yclooctadiyne,~~~
as well as
'[3 31 4e. These two silacycloalkynes have recently been
synthesized in an alternative way by Sakurai et al.lS1The
compounds synthesized by us are summarized in Table 1.
+
+
+
+
Table 1. Synthesized silacycloalkynes of the type "[m+m] 151. For experimental procedure see [14].
n=4
6d
(traces)
n=3
6c
(traces)
3d
86-87
15
3c
162-1623
35
n=2
3b
122-123
4b
153-154
5b
135-137
25
n= 1
3a
103-104
4a
107- I08
5a
118-1 19
15
n=O
3e
139
(139 [gal)
4e
146- 147
(146-147 [Sc])
5
The silacycloalkynes described here are easily crystallizable and sublimable solids; they were obtained in a pure
state as shown by mass spectrometry. They are stable in air
and can be subjected to gas chromatography without decomposition. An oily residue, which makes u p a considerable portion of the crude products, could not be further
analyzed.['41
The high-resolution IR spectra of the isolated silacycloalkynes are very similar to each other and exhibit the
bands characteristic for these highly symmetrical compounds. The ' H - and I3C-NMR spectra (Table 2) of "[2 21
both chair and boat forms are present in the same crysta1.[9b1Low-temperature N M R spectra of 3a show conformational changes. The photoelectron spectra of '[2 21 3e
and '13 31 4e were recorded by Heilbronner et al. ;[''I they
are in accord with those of Gleiter, Sakurai et al."']
+
+
Received: February 4, 1985 [Z 1154 IE]
German version: Angew. Chem. 97 (1985) 587
CAS Registry numbers.
la, 5357-38-0; Ib, 13528-93-3; lc, 2295-06-9; Id, 14799-64-5; le, 4342-61-4;
2, 4301-15-9; 3a, 25202-43-1; 3b, 97071-87-9; 3c, 97071-86-8; 3d, 97071.852; 3e, 85263-68-9; 4a, 97071-89-1; 4b, 97071-88-0; 4e, 89571-48-2; 5a,
97071-91-5; 5b, 97071-90-4; 6s, 97071-84-6; 6d, 97071-83-5.
[ I ] Review: A. Krebs, J. Wilke, Top. Curr. Chem. 109 (1983) 189.
[2] A. Krebs, unpublished results.
[3] The lower homologue 3,3,7,7-tetramethylcycloheptyne is isolable but
unstable: A. Krebs, H. Kimling, Angew. Chem. 83 (1971) 540; Angew'.
Chem. Inr. Ed. Engl. I0 (1971) 509.
141 M. Ishikawa, M. Kumada, H. Sakurai, J. Organomer. Chem. 23 (1970)
63.
[ S ] The abbreviation "[m+m] indicates that n C H 2 units are linked between
the Si(CH3)2groups and that m each of the reactants are involved in ring
formation.
[6] G. Fritz, P. Schober, Z. Anorg. Allg. Chem. 372 (1970) 21.
[7] a) E. Kloster-Jensen, J . Wirz, Angew. Chem. 85 (1973) 723; Angew.
Chem. I n r . Ed. Engl. 12 (1973) 671; b) Helu. Chim. Acta 58 (1975) 162.
[S] a) H. Sakurai, Y. Nakadaira, A. Hosomi, Y . Eriyama, J . Am. Chem. Soc.
105 (1983) 3359; b j Chem. Lett. 7982, 1971; c) H. Sakurai, Y. Eriyama,
A. Hosomi, Y. Nakadaira, C. Kabuto, ibid. 1984, 595.
[9] a) C. Romming, unpublished results; b) 3a-d: C. Romming, G. A.
Eliassen, E. Kloster-Jensen, Acfa Chem. Scand.. in press.
[lo] E. Heilbronner, E. Honegger, unpublished results.
[I I ] R. Gleiter, W. Schafer, H. Sakurai, J. Am. Chem. Soc.. in press.
1121 Cf. H. Janke, G. Engelhardt, H. Kriegsmann, L. M. Volkova, N. W. Delazari, A. Andrianov, Z. Anorg. ANg. Chem. 402 (1973) 97.
113) L. H. Sommer, G. M. Goldberg, J. Gold, F. S . Whitemore, J. A m . Chem.
Soc. 69 (1947) 980.
[ 141 Experimental procedure: The reactions were carried nut i n anhydrous tetrahydrofuran (THF) under nitrogen on a 10- to 20-mmol scale. The
yields are unoptimized crude yields. l a - d and le were synthesized by
chlorodemethylation [4] of 7a 141, 7b (Flukaj, 7c 1121, 7d 1131, and 7e
(Fluka), respectively. To 2 in T H F at 55-60°C were added equivalent
amounts of 1 over 15 min with stirring. After stirring for 2 h at this temperature, the reaction mixture was hydrolyzed with 10% NH,CI solution
and extracted three times with pentane. The combined pentane extracts
were washed ten times with saturated NH,CI solution and dried over
MgS04. Removal of the solvent left a partly crystalline residue, which
was fractionally sublimed at ca.
torr. In some cases, additional
recrystallization was necessary. The purity was checked by gas chromatography (3% SP-2100, 190-260°C). 6c and 6d were characterized by
MS (isotope distribution corresponds to 2Si); the other products were
characterized by IR, 'H-NMR, and I3C-NMR spectroscopy.
+
+
Table 2. ' H - and "C-NMR spectra of silacycloalkynes of the type "[2+2] 3
(300 MHz, CDCI, (standard), 6 values). 3e: 'H-NMR: 6=0.25; "C-NMR:
6= 119.46 (-C=C-), 3.07 (CH,) @a].
CHI
3a
3b
3c
3d
'H-NMR
Si-CH2
0.19 (s) -0.14 (s, 4H)
0.15 (s)
0.67 (a, 8H)
0.14 (s) 0.67 (m, 8H)
0.13 (s) 0.61 (m, 8H)
C-CH,-C
C=C
114.95
113.62
1.59 (m, 4 H ) 113 51
1.50 (m, 8H) 113.97
"C-NMR
CH, Si-CHa
By RolfGleiter* and Wolfram Sander
Dedicated to Professor Rolf Huisgen on the occasion of
his 65th birthday
C-C-C
1.13 2.60 (2C)
-2.37
9.19 (4C)
- 1.56 21.09 (4Cj 18.70 (2C)
-1.56 27.84 (4C) 16.41 (4C)
3a-d are also very similar to one another and are in accordance with the structure given (3e['"]). An X-ray structure determination1'"] of '[2 21 3e confirmed the results of
Sakurai et aI.,[8a1which showed that the ring is planar, as
in 1,5-~yclooctadiyne.~~~
The homologue '[2 21 3a at
- 133" adopts a conformation analogous to cyclohexane;
+
+
566
0 VCH Verlagsgesellschaft m b H , 0-6940 Weinheim.
1985
Light-Induced I2 21 Cycloaddition Reactions of
Nonconjugated Dienes-the Effect of Through-Bond
Interaction**
+
Light-induced intramolecular [2 21 cycloaddition reactions of nonconjugated dienes, 1 , lead via parallel cycloaddition to 1,2-bridged cyclobutanes, 2a, or via cross
cycloaddition to 1,3-bridged cyclobutanes, 2b."' As
pointed out by Sriniuasan et al.,[I1the ratio of 2a to 2b de[*I Prof. Dr. R. Gleiter, Dr. w. Sander
Institut fur Organische Chemie der Universitat
Im Neuenheimer Feld 270, D-6900 Heidelberg (FRG)
['*I This work was supported by the Fonds der Chemischen lndustrie and
BASF AG, Ludwigshafen. W . S. thanks the Studienstiftung des
Deutschen Volkes for a stipend.
0570-0833/85/0707-0566 $ 02.50/0
Angew. Chem. I n t . Ed. Engl. 24 (1985) No. 7
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