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Efficient Synthesis of Heteroradialenes by SN Reaction.

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calculated positions bith l',,,,
= 1.3 L',,, for parent atoms. Final R = 0.095.
R' = 0 070 Further dctails of the crystal structure investigations are available
on request from the Direclor of the Cambridge Crystallographic Data Centre.
quotlllg the full joUrn;,icita12 Union Roud. Gllnbridge CB? I E Z ( U K )
tioii.
[ 7 ] C. Schide. P. b o i l R. Schleyer. A r h Orgaiionicr. C'/iivi. 1987. 27. 169
[XI P. B. Hltchcock, M b- Lappert. w-P. Leulip. L. Dianshenp. T. Shun. J. Chriii.
Soc. Chimi. C o i i i i n i i i i . 1993. 1386.
[9]S. S. Al-Juaid. C. Eaborn. P B. Hitchcock. C. A. McGear), J. D. Smith. J.
c / ~ sot.
~ , c/j~Jiii
~ ~ ~
CiJillnlull
,
1989. 273.
[lo] F. Glockling. N. S. Hosmanc. V. B. Mahale,J. J. Swnidall, L. Mapos.T. J. King.
J. Chiziir. Xr.s. 1977. (S) 116. ( M )1201
[l I ] M . Westerhausen. R. Radsmacher. W. Poll, J. Oiyuiioiiic~l.Chcii~.1991. 421.
175.
[I21 N . H . Bultrus. C . Eaborn. P. B Hitchcock. J. D. Smith. A. C Sullivan. J.
c/irill.
sol.c~/IpIiI.
c~liiiiiiliii
198s. I 3x0.
[I31 2: Crystal data CZ,H,,NaSi,. :M = 440.8. monoclinic. space group <.(,.
( I = 9.413(5). h =15.749(9). i' = 3 3 21 l(18). /i
= 91 46(5). V = 4921 X. Z = 8.
p = 1 . 1 9 g c m ~ ' . F ( 0 0 0 ) =IXXX,Mo,,rudiation./. =0.71069A./i = 2 . l c m - I .
T = 1 7 3 K. 4707 unique reflection5 measured and 2742 with IP'I z 2 o ( F ' )
used. Absorption correction (DIFABS) 1.36 max.. 0.65 min. Structure analysis
and refinement as for 1 Final R = 0.082, R' = 0.075.
[I41 H. Kostcr. E.Wciss. J. ~ l ' , ~ ~ i i i ~ J i l i C/x,iii.
131.
1979. / 6 8 , 273.
1151 C. Eaborn. P. B. Hitchcock. J. D. Smith. A C' Sullivm. J. C'hcziii. Six Chmi.
c l l ~ l l19x3.
~ l I~m.
l~~~.
[I61 C . Eaborn. P B. Hitchcock. K . Izod, A. J. Jaggai-.J. D. Smith. O r g u i i o i w r d
/ I < , \ . 1994. 13. 753.
[I71 H. Bock, K . Ruppei-t. Z. Havlas. D Fenske, An,y:cw. C'/iiw. 1990. 102. 1095;
.Iil,qpii Clioii lilt. Ed. Etlgi. 1990. 29. 1042.
[I81 H. Bock. K Ruppcrt. D Fenske. ,4iig<,11,( ' / i e i t i 1989. / ( I / . 1717: .4n,qPlr.
Cheiii. / i i / . 6 1 . Di'yi. 1989. 28. 1685.
1191 13. Schinidbaui-,U. Deschler. B Milebrkl-Mahrla. R. Zimmcr-Gasser. C/icwi.
B ~ , 1981,
~ . 114. 608.
[20] S. Corbelin. _I Kopf, N . P. Lorenzen. E. Weiss. A n g ~ w C/iiwr.
.
1991. /03. 875:
A i i g m C I i n i i / i f / . Ed. EngI. 1991. 30. 825.
Treatment of 2,5-dimethyl-2.5-dichloro-3-hexyne( I ) with
N ~ , S. A ~ , o , [ ~does
I
not react by nucleophilic substitution at
the ProPargYl
atom to the expected octamethyl-l,6-dithia3.8-cyclodecadiyne (2), but to the methyl derivatives of
thia[3]radialene (3) and dithia[6]radialene (4). These two compounds were first synthesized by Ando et al, by another procedure.151This unexpected
can be explained by an
mechanism (Scheme 1). We assume that substitution of chloride
c
'"
2
I
I
4
3
Schemc 1
with the sulfide anion by the SN' reaction leads to compound 5
as an intermediate, which cyclizes in a further step either intramolecularly to 3 or intermolecularly to 4.
The reaction of I with other nucleophiles yields 2.3-disubstituted 1, I .4,4-tetramethyl-l.3-butadienes.
As an example the reactions of I-lithio-I-hexyne and NaCN . A120, are shown in
Scheme 2. They lead exclusively to the SN' products 6 and 7.
Efficient Synthesis of Heteroradialenes
by SN' Reaction**
Rolf Gleiter,* Harald Rockel, H e r m a n n Irngartinger,
a n d T h o m a s Oeser
Dedicated
011
l o Pmfessor Margor Becke-Goeliring
ihc ocrtisiori o/ her 80th hirthduj
Radialenes, a relatively new class of compounds first mentioned in the sixties, are not only aesthetically pleasing. but are
also interesting objects of study for theoretical chemists or researchers in material science because of their electronic properties.['] Over the last few years new and simple synthesis have
made alicyclic radialenes readily accessible. Photoelectron
spectroscopic studies have shown that permethylated alicyclic
radialenes have energetically high-lying occupied molecular orb i t a l ~ . ' They
~ ' should therefore be suitable as electron donors in
donor -acceptor complexes. These complexes have aroused inHeteroraditerest as conductors and organic ferr~magnetics.'~]
alenes have been investigated by Maercker et al.[41and Ando
et aI.['l Thiaradialenes, however. could so far only be synthesized by a multistep procedure.'" which may be the reason why
so little is known about their physical-chemical properties. We
now report a synthesis affording thiaradialenes from simple and
easily accessible starting materials.
Scheme 2
Consequently now, in addition to earlier work of H ~ p f , "2.3~
dialkynyl-substituted 1,3-butadienes are readily available by
this easy synthesis. Both products 6 and 7 have interesting crossconjugated multiple-bond systems and are promising starting
materials for reactions at the conjugated triple bonds, or at the
diene system.
[*] Prof Dr. R . Gleiter. Dipl. Chcm. H . Riickcl, Prof. Dr. H. lrngaitinper.
Dr. T. Oeser.
Organisch-chemisches Institut der Universitat
I m Neuenhcnner Feld 270. D-69120 Heidelbcrp (FRG)
Telefax: Int. code +((,??I) 564205
[**I
This work w!iis supported by the Deutsche Forschuiiesgemeinschsft. the Fonds
der Chemischen Industrie. and the RASF AG. Ludwigshafen
8
Scheme 3
'
9
'
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isopropylidene-1,6-dithia-3,8-cyclodecadiyne(9) (Scheme 3).
Diyne 9 may also be considered as an expanded
dithia[6]radialene. As is apparent from Figure 1 the ten-membered ring in 9 adopts chair conformation.[81The transannular
distance between the triple bonds is 3.085(2) A. The minor de-
r]:
Fig. 1 Cr-ystiil structurr of 9; selected bond lengths [A] and angles
ClGC2
1.430(3). C'2 - C 3 1.201(3). C3-C4 1.426(3). C4 - C 5 1.346(3). C l - C 8 1.346(2).
S - C l 1.792(2). S-C4'1.798(2); Cl-S -C4 102.6(1). S-C4'-C5' 121.4(l),S-Cl-C8
121.9(1). S-C1-CZ 115.0(1), S-C4-C3' 115.1(1). Cl-C2-C3 173.9(2). C2-C3-C4
173.6(2). C2-C 1-C8 123.0(2). C3-C4-C5 123.3(2). C6-C5-C7 115.6(2). C9-C 8c'10 115 112).
We consider that the reaction of 2,7-dimethyl-2,7-dichloro3,s-octadiyne (8) with Na,S . A1,0, has particular scope. It is
similar to the preceding reactions and furnishes 2,5,7,1 O-tetra-
crease in this distance relative to that in the structurally related
1.6-dithia-3,8-~yclodecadiyne,[~~
for which a transannular distance of 3.102(2) A is reported, is probably due to the exchange
of the four sp'-carbon atoms for sp2-carbon atoms in 9. The
bond angles at the sp centers are 173.6(2)" and 173.9(2) ; hence,
the linear arrangement of the triple bonds is bent by 6.4(2) and
6.1 (2)", respectively. Similar deformations have been observed
The torsfor all ten-membered diyne systems known to
ion angle of the two isopropytidene groups along the triple bond
is 66.9(3)" ( C S - C 4 . . . C I - C 8 ) .
By photoelectron spectroscopy (PE) and cyclic voltammetry
(CV) it is possible to verify that the obtained radialenes. especially 3 and 4, are indeed electron-rich 7c systems. At the top of
Figure 2 the He(1)-PE spectrum of 3 is shown and iit the bottom
the cyclic voltammograms of 3 and 4. In Table 1 the first vertical
ionization energies are listed.
Table 1. Vertical ionization energies and oxidation potentials of radialcnea 3 and 4.
thia[3]radiaIene (3)
dithia[6]radialene (4)
ionization energies
8.0 eV
8.3 eV
10.5 eV
11.1 eV
oxidation potentials [a]
1600 mV
7.1 eV
7.5 eV
8.3 eV
9.1 eV
lll5mV
[a] The oxidation potentials were measured with a HEKA potentiostat (PG 28) in
CH,CI, as solvent and (nBu),N PF, as electrolyte. The working electrode was a
Metrohm disk electrode (radius = 3 mm) and reference electrode a saturated
calomel electrode (SCE), which was separated from the call by a frit and a luggin
capillary. The oxidation potential of ferrocene/ferrocenium (480 m V ) W B S taken a s
standard.
The PE spectrum of 3 shows a sharp band at 8.0 eV, assigned
to the sulfur 3p lone pair. The following band at 8.3 eV represents the HOMO of the tetramethyl butadiene fragment. The
next two bands at 10.5 and 11.1 eV are assigned to Walsh-like
orbitals arising from the 3 p orbital of sulfur and the two carbon
atoms of the three-membered ring. While the first ionization
energy of 3 is similar to that of other sulfides,["I there is a
significant decrease to 7.1 eV in the case of 4 that can be explained by interaction of the sulfur 3 p lone pairs with the
butadiene system. The relatively high-lying HOMO is also observable by cyclic voltammetry. Thiat3lradialene 3 shows an
irreversible oxidation at 1600 mV, as is common for alicyclic
radialenes,['] but 4 shows a reversible single-electron oxidation
at 1115 mV (vs SCE).
The reactions described in this paper allow the investigation
of the chemistry of a number of new radialenes. Furthermore
they have made possible the simple synthesis of 2.3-dialkynyl1.3-butadienes, a class of interesting compounds that have thus
far been difficult to investigate.
80.00
40 00
t
0
1hA
-40 00
0
-
Experimenral Procedure
1.000
E/V
Fig. 2. Top: He(1)-PE spectrum of 3. I = count rate. Bottom: Cyclic voltammograms of 3 and 4 in CH,Cl,;(nBu),N PF,,, scan rate: 100 mV/s-'. reference
electrode. saturated calomel electrode.
Angelic ('hem. I I I I .Ed. Engl. 1994. 33, N o . 12
3 a n d 4 : T o a suspensionofNa,S~AI20,(19.2g)[6]inX0mLTHF~DMPU
(10:l.
DMPU = N,N'-dimethyl-2,6-diazacyclohexanone) was added dropwjise undcr rcflux 1 (1.78 g. 10 mmol) dissolved in 30 m L of the solvent. After I?. h thc solution
was distilled under reduced pressure to recover the starting material (50%) After
chromatography of the residue (silicakyclohexane) 3 (420 mg. 3 mmol) and 4
YCH Y ~ r / f ~ ~ s g e s e l / s ~n/~i rbrHf f0-694.51
,
Wt'in/ieini, 1994
0570-01133~94~1212-1271
S lfl.OO+ . X ( l
1271
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(300mg, 1.07 mmol)wereisolated.3: ' H N M R : 6 =3.98(s. 6H).2.07(s36H); I3C
N M R : 6 = 22.64. 23.00, 111.37. 115.00; €1-MS: nl;:: 140 ( M ' ) : 4: ' H N M R :
d = 1 . 8 4 ( ~6. H ) . 1.67(s, 6H); " C N M R : s = 21.06.21.90, 125.55. 130.43:EI-MS.
111;z. 280 ( M ' )
6 (see also ref. [12]): I-Hexyne (1.64 g. 20 mmol) was dissolved in T H F (50 mL) at
-78 C and deprotonated with ii-butyllithiuni (1.6 u in rr-hexane). This solution was
added dropwise to a refluxing solution 1 (890 mg. 5 mmol) in THF;DMPU (5.2)
60 mL. After 12 h the reaction was quenched with water and extracted with ether
(3 x 50 mL). dried over Na,SO,, and purified by chromatography (si1ica:cyclohexane). Isolated yield of b: 150 mg (0.55 mmol. 11%). ' H N M R : d = 0.89 (I. 6H.
' J = 7 . 1 H z ) , 1.38-1.59 ( m . 8 H ) . 1.64 ( s . 6 H ) . 1.93 ( s . 6 H ) . 2.33 (t. 4 H .
' J = 6.9 Hz}; "C N M R : d =13.66. 19.39, 20.62, 21.97. 22.62. 31-15. 79.54. 92.20.
116.56. 141.12: El-MS: n i ; z 270 ( M ' )
7: Hexyne I (1.78 g. 10 mmol) dissolved in 30 mL of the solvent mixture was added
to a suspension of NaCN . AI,O, (1 : 1 4.0 g) in THFlDMPU (10: 1) 80 mL under
reflux within 5 h. After 12 h the solution was worked up as above. After chromatogyclohexane) 7 was isolated as a colorless liquid. Yield: 976mg
(6.2mmol.61%). ' H N M R : 6 = 1 . 8 8 ( s . 6 H ) . 2 . l h ( a . 6 H ) ;
24.04. 103.05. 116.06. 160.45; ELMS: ni;:: 160 (M')
'3CNMR:d=21.36.
9: To a suspension of Na,S . AI,O, in the solvent mixture described above, 8 (2.03 g.
10 mmol) in 30 mL of the solvent was added. and the mixture was heated at reflux
for 12 h. 9 was isolated as above in 10% yield (328 mg) after chromatography
(silica,cyclohexane). ' H N M R . (5 = 2.04 (s. 12H). 2.08 (s. 12H): " C N M R :
6 = 21.97. 24 11, 93.56. 111.58. 147 14: CI-MS:
328 ( M + ) .The crystals for
X-ray analy,is piecipilatcd from CH2CI, at -30
New Types of Metal-Stabilized Cyclobutadiene
Superphanes**
Rolf Gleiter, * Heinrich Langer, and Bernhard Nuber
The metal-catalyzed trimerization of alkynes to aromatic compounds is a useful reaction." - 31 Cobalt-catalyzed [2 + 2 + 21
cycloadditions are sometimes accompanied by a side reaction,
the dimerization to metal-stabilized cyclobutadiene complexes.
These complexes are considered inert towards further cycloaddition r e a c t i ~ n s . ' ~If]cyclic diynes are used as starting materials,
the tricyclic cyclobutadiene complexes are usually the main
product.[', 61 In the case of the reaction of [CpCoL,] (Cp = '1'cyclopentadienyl; L, = 2 C 0 , 1,5-cyclooctadiene (cod)) with
1,6-cyclodecadiyne, 1-8-cyclotetradecadiyne, or 1,lO-cyclooctadecadiyne an intermolecular reaction is even possible,
which leads to CpCo-stabilized superphanes such as 1.16]These
species are not only aesthetically attractive, but also useful for
preparing cage compounds such as the fourfold bridged derivatives of tricycl0[4.2.0.0~~
5]octa-3,7-diene (2). its isomer (3). and
the cubane derivative (4).[61
Received: January 4. 1994 [Z 6670 IE]
German version: Angrir. Ctiern. 1994. 106. 1340
[ l ] H. Hopf. G. Maas. Airgeir. Cheni. 1992, 104. 953-1122: A I ~ ~ c ICliein.
I ~ . f n f .GI.
Engl. 1992. 31. 931 -954.
[ 2 ] T. Bally. E. Haselbach. H r h . Chim. .4cfu 1978. 61. 754-761.
[3] T. Sugimoto. H. Awaji. Y Misaki. 2. Yoshida. Y. Kai, H. Nakagawa. N. Kasai.
J. A m . Chem Soc. 1985. 107. 5792-5793.
[4] A. Maercker, W. Brieden. C h n . Bcv. 1991, 124. 933-938. and references
therein.
[5] W. Ando. Y. Haniu. T. Takata. T~~i-u/~~w/roi.ni
Lrrf. 1981. 22. 4835-4816, W.
Ando. Y. Haniu. T. Takata, K. Ueno. ibid. 1985, 26. 3019-3022.
[6] B Czech. S. Quici. S. L. Regen. $rnlhesi.$ 1980. 113
[7] H. Hopf, H. Lipka. Chrm. Err. 1991. 124, 2075-2084.
[S] X-Ray analysis of 9: colorless crystals from CH,CI,: crystal size 0.45 x 0.45 x
0.15 m m , monoclinic: space group P2,lc; 2 = 2; the molecule is positioned
upon a crysta1~ographlccenter of symmetry; u = 9.042(1) A, h = 12.713(2) A,
c' = 8.248(1) A. 0 = 99.54(1)-; V = 934.9(4) A3; pcd,cd
= 1.17 M g r ~ - 2H,,,
~;
= 56 : Mo,,; i = 0.71071 A; graphite monochromator: ('J 20 scan; T =
293 K : 2371 measured reflections, 2371 independent reflections, 1477 observed
[ I > 2 . 5 0 ( / ) ] . Lp-correction. numerical absorptioncorrection p = 0.268 mm-'
(T,,, = 0 958. T,,, = 0.807); direct methods (MULTAN). MolEN program
package (Enraf Nonius); full-matrix least squares refinement ( F ' ) ) . S and C
atoms were refined anisotropically, H atoms were refined isotropically, variables = 148. R = 0.037, R , = 0.045. S = 1.734. (A;U),"> = < 0.01, (Ap),,. =
0.175 e k ' : ( A P ) ~ , "= 0.159 e k ' . Further details of the structure investigation are available on request from the Fachinformationszentrum Karlsruhe.
D-76344 Eggenstein-Leopoldshafen on quoting the depository number CSD380017.
[9] G . Eglinton, I. A . Lardy, R. A. Raphael. G. A. Sim. J. Chrm Soc. 1964, 11541158; R. Gleiter. S. Rittinger. H. Irngartinger. C/iwn. Brr. 1991. 124, 365369.
[ l o ] R. Gleiter. Angeti. Chm.ni.1992, 104, 29-46. Anpic. Cheni. 1/11. Ed. Engl. 1992.
31. 27 -44.
[ l l ] R. Gleiter. J. Spanget-Larsen. 7op. Curr. Chem. 1979. 86. 139-195. and references therein.
[12] Another synthesis of 2,3-dialkynyl-1.3-butadienes
and some reactions of these
w m of conmounds have been reDorted recently: H. HoDf. M. Theurig,
new t_.
Angw. Chem. 1994, 106, 1173; Angrw. Cheni. Int. Ed. Engl. 1994 73,
1099.
..
2
3
Scheme 1. Ox
[**I
('1
VCH Verlug~ge~ellsrliuft
mhH, 0-69451 Wernheim,1994
4
oxidation
In connection with mechanistic investigations of the photochemistry of 2 we wanted to synthesize superphanes with different chain lengths. To this end the recently published stepwise
path to metal-stabilized superphanes seemed appropiate.['] In
this paper we report on the first verification of this concept to
yield a CpCo-stabilized cyclobutadiene superphane with different chain lengths. In addition we describe another new type of
superphane and a novel CpCo complex of a fourfold bridged
bicyclo[4.2.0]octa-2,4,7-triene.
Starting point of our synthesis is 6-undecynol (S),[*I which
was converted into the tricyclic cyclobutadiene complexes (6) by
reaction with [CpCo(cod)] in 70% yield (Scheme 2). The mixture of the isomeric alcohols 6 was oxidized to the diketone 7 by
the Oppenauer procedure with acetone in 83 YOyield. In the next
step the diketone 7 was transformed into the bisselenadiazoles 8a/8b in 35% yield with a procedure first devised by
Lalezari et al. .['I Without further purification the mixture 8a/
8b was treated with nBuLi at -40 "C to give a 1 : 1 mixture of
the tricyclic diynes 9a/9b in 70% yield.
[*I
1272
=
Prof. Dr. R. Gleiter, Dipl.-Chem. H. Langer
Organisch-chemisches Instrtut der Universitdt
Im Neuenheimer Feld 270, D-69120 Heidelberg (FRG)
Telefax: lnt code + (6221)56-4205
Dr. B. Nuber
Anorganisch-chemischzs Institut der UniversitPt Heidelberg
This work was supported by the Deutscbe Forschungsgemeinschaft (SFB 247),
the Fonds der Chemischen Industrie. and the BASF Aktiengesellschaft (Ludwigshafen)
U570-0833!94/12/2-1272$ lO.OO+ ,2510
Ang~rr.Chem. Int. Ed. Engl. 1994, 33, No. 12
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