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Synthesis of Heterocyclic Cyclopolyaromatics Containing Similar Kinds of Nuclei.

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Of particular interest are the syntheses of the o-bis(trimethy1silyl) derivatives ( 3 r ) and ( 4 e ) . Although quite strained, these
compounds form in relatively high yield because bistrimethylsilylacetylene does not trimerize under the reaction conditions[ld.91. Thus, slow addition of the diyne (1) to the alkyne
( 2 ) in this case leads to more efficient cocyclization, although
side reactions are not entirely suppressed.
Compounds ( 3 r ) and ( 4 e ) are key intermediates in the
synthesis of other functionalized indans and tetralins, and
can be converted to derivatives of type ( 5 ) by high yield
stepwise detrimethylsilylation with electrophilesl'O1, or (6)
by treatment with dilute acid'' 'I.
5,6-Bis(trimeth~dsil~lindan)
( 3 e)
To 5gofrefluxing (2), RL=R2=Si(CH3)3(5g,
large excess)
in dried and degassed n-octane (70ml) under nitrogen was
added a solution of 1,6-heptadiyne ( I ), n = 3 (0.46g, 5 mmol)
and C ~ C O ( C O(20
) ~pl) in dried and degassed n-octane (10ml).
The addition was controlled by means of a syringe pump
over 36h. Vacuum transfer of solvent, excess (reusable) (2),
and catalyst gave a dark oily residue that was chromatographed on silica (1 50g). Eluting with petroleum ether (4060°C. 200ml fractions) gave fraction 2--4 containing a colorless oil. Crystallization from ether gave 650mg (36') as colorless crystals.
c 5 115
[XI
See. for instance, E. Miiller. Synthesis I Y 7 4 , 761 ; E. Miillrr. A . Schrllrr.
Pi: W'iit~cr,F . Wugtirr. and Ii. Meier, Chem.-Ztg. YY. 155 ( I 975).
[9] N. Sakttrai and J . Ha,vashi, J. Organomeral. Chem. 711. 85 I 1974).
[ 101 a ) The high efficiency of the stepwise displacement is due to steric
acceleration ofthe first step [ I d. lob]. Kineticmeasurementsofdeuteriodesilylation in CF,C02DK'D,C0,D/CCI, (56: 27: 17) reveal displacement of the respective first silyl groups 37 ( 3 e ) and 36 (46,) times
faster than the second: h) C. Ertborri. D. K. W M.b//oi~.and D J .
fi~iing. J. Chem. SOC. B 1969, 15; c) For instance treatment of ( 3 e J
or ( 4 c ) with bromine followed by ICI gives (>90";,) 1 . 5 ) . n = 2 , 3:
E ' = B r , €'=I.
[ I I] D. Srlferrh and D.L. IVhitc, J. Am. Chem. Soc. Y4. 3132 (1972).
Synthesis of Heterocyclic Cyclopolyaromatics Containing Similar Kinds of Nucleir']
By Thomas Kaufmann, B e r d Crecing, Johann Konig, Alfred
Mitschker, and Annegret Woltermann[*l
Owing to the large number of known carbo- and heterocyclic
aromatic compounds thousands of cyclic combinations of
aromatics (cyclopolyaromatics[21)are conceivable. As far as
those with heterocyclic ring members are concerned our knowledge is extremely scanty apart from the exceptional case
of triplet combinations such as ( 1 ) I 3 J which are assigned
to the condensed aromatic compounds: combinations of two
aromatics, e.g. (2jL4I, are known only in few cases, and of
the corresponding compounds having four and 'more ring
members apparently only cyclotetrathiophene (3)l5l has been
described so far.
Received: J u l y 14. 1975 [ Z 291 I€]
<;errnun version: Angew. Chem. 87. 714 (1975)
CAS Regi\lry numbers
( 1 ) . f i = 3 . 2396-63-6: / I ) ,t t = 4 . X71-X4-1 : ( 2 0 ) , 762-42-5:
i 2 b l . 536-74-3: f2c I . 501-65-5. i 2 d l . 629-05-0: /2c,.i, 14631)-40-1:
12 I i . 6224-91-5: f3u). 5659X-67-5: f 3 h I . 56598-68.6:
f.?c I . 56508-69-7; 1 3 d i . 54889-55-3. f.?c). 56598-70-0. f 4 < t ) . 51510-78-2:
14hJ. 41284-X8-2; 1 4 ~ ' ) 5659X-71-1
.
: / 4 d ) , 56598-72-2: , 4 e i , 5(1598-73-3;
( 4 / ). 56598-74-4;(6). l t = 3 . 56598-75-5: (6).11=4. 56598-76-6:
~tic~irhi~iiylcyc1opentadienqIcoh;~lt.
12078-28-X
[I] a ) K . f'. <. C't~//hrtid!and R. G. Bc,rgmoii. J. Am. Chem. Soc. 96. 4996
(1974): h) K . P. C. Kd/hurdr. J . E. Bercaw, and R. G. Brrginun, J.
Am. Chem. Soc. Yh. 4998 (1974): c)The use of carhonql (phosphane)nickel
catalysts for the ~.opol~.i~trrr~uriot7
of terminal unconjugatcd diynes uith
alkylacetqlenes has been reported In these reactions 5-alkylindans seem
to he formed in low yield and in difficultly sepal.abic mixtiircs with
other oligomers; E. C. Co///titp and L. S. Meriiwfht~r.J. Org. Chem.
26. 5 169 I1961 1: d ) M: G. L Ait/ber*brr<g. A . J . B'rrkol-id. R. L. F ~ t r i h .
R. 1. Hiilord 111. and K P 'C k i / / / i o r d f ..I Am. Chem. Soc.. in pres?
[2] All isolated new compounds reported gave satisfactory ana1ytic;J and
spectral data.
[ 3 ] K . 4/i/n. R. M i t d w s . M! Krrttte. and P. Wirr:. l-ichigs Ann. Chem.
627. 59 I1959).
[4] S. Bwbit/(wii and M. Gorrlo, Annlele Univ. C. I. Parhon. Ser. Stiint.
Nat. 10, 151 (1961): Chem. Ahstr. j Y , 1506h(1963).
[ 5 ] J . P. M'rhoiti and B. P o r t l i ~ ,Rec Trav. Chim. Pays-Bas 77. 792 (1958).
[6] J r . S. 1'0kr0~ skrij(t and R. J o . Ssuachrschik. Lh. Obshch. Chim. / I .
170 (1941).
[7] In I-eactions with ( 2 ) . R 1 = R ' = C , , H , stilhene is also formed. In reactions involvins ( 2 ) . R' = R z = S i ( C H 4 ) , the following cobalt complex
:wise\ ( i i = 3 or 4) 121:
We have now accomplished an entry into the heterocyclic
cyclopolyaromatics on a fairly broad front and wish to report
a number of syntheses whose yields are, however, not yet
entirely satisfactory.
Nucleophilic heteroaromutics: Oxidative coupling of acetylenes uiu organocopper derivatives has proved to be a key
reaction in the synthesis of annulenes. It can already be seen
that the corresponding coupling of aromatic systems will play
a similar role in the synthesis of carbo-r61 and heterocyclic
cyclopolyaromatics. Starting from the compounds ( 4 ) [ ' l ,
/6)r*1, and (X)r91, use of this reaction afforded the cyclotetraaromatics ( 5 ) (m, p. 2 3 3 T ) , (7) (m. p. 30&301 "C),and ( 9 )
(dec. 421-424°C).
The synthesis of ( 3 ) " ) gave a small amount of a (not
yet completely pure) cyclohexathiophene (dec. above 420°C)
as by-product. Since its 'H-NMR spectrum is almost identical
to that of ( 3 ) , it clearly has the centrosymmetric structure
( 1 0 ) and not a helical structure['!
[*] Prof. Dr. Th. Kauffmann, Dip1 -Chem. B. Greving, DipLChem. J . Konig.
Dr. A. Mitschker, and A. Woltermann
Organisch-Chemisches lnstitut der Universitiit
44 Mitnster. Orleans-Ring 23 (Germany)
713
[I]
[2]
( 5 ) (14%)
16I
(7) ( 2 3 % )
[3]
[4]
[S]
[6]
( 8 ) (52%)
[7]
[S]
[Y]
[lo]
[1 I]
Protophanes and polyaromatics, Part 20. This work was supported
by the Deutsche Forschungsgemeinschaft and the Fonds der Chcmischen
Indurtrie.-Part 19: Th. Kuuffmarin. Forschungsber. des Landes Nordrhcin-Westfalen, No. 2450 (1975).
We have proposed extension of the class name "arene" t o include
heteroaromatic compounds. Not wishing to anticipate a decision by
the IUPAC Commisqion. we have still retained the term ":irom:it~c"
in the present work. -In naming unbranched chains made up of identical
ring systems. ILJPAC Rule A-54. I prescribes use of the numerical prefixes
hi, ter, quater, quinque, sexi, etc. Since most of the possible polyaromatics
fail to meet these requirements and expressions like sexiaromatic or
cyclosexifuran are not without comical undertones, we employ the
usual prefixes di, tri, tetra, c'tc.
A . Mitschker, U . B r m d / , and Th. Kauffmonn,
Tetrahedron Lett. 1Y74,
2343.
P. J . Gurrurt and K. P. C . Vo!/hurdt, Chem. Commun. l Y 7 0 , 109:
J. Am. Chem. Soc. 94, 7087 (1972).
B. Grrcing, A. Woltrrmann, and Th. KouSfmunn, Angew. Chem. X6.
475 (1974): Angew. Chem. internat. Edit. 13,467 (1974).
Cf. G. Witrig and K:D. Riimpler, Liebigs Ann. Chem. 751, I (1971):
L. Ernst. A . Munnschreck, and K . - D . Runipler, Org. Magn. Reson. 5,
125 (1973).
G. M. Ducies and P. S . Duuies, Tetrahedron Lett. 1972, 3507.
S. Gronowit;. Acta Chem. Scand. 15, 1393 (1961).
A less favorable synthesis of ( 8 ) ( I 1 'I;, yield) IS described by L. J .
Pondj,a. D. S . Roo, and B. D. Ti/& J. Sci. Ind. Res. (India) BIX,
516 (1959); Chem. Abstr. 54, 17391 d (1960).
A. J . Clarke, S. McNumaru, and 0.Meth-C'ohn. Tetrahedron Lett.
1974, 2373.
Cf. S . Gronowifz and J . Rue, Acta Chem. Scand. 19, 1741 (1965).
(9) (11")
Electrophilic heterouromatics: In order to become
acquainted with cyclic combinations of such systems we first
prepared the hitherto unreported 5,5'-bipyrimidinyl(1 I ) (m. p.
196-1 97 "C)" and reacted it with lithium diisopropyla-
Synthesis of Heterocyclic Cyclopolyaromatics Containing Different Kinds of Nuclei[']
By Thomus Kauffmann, Bernd Muke, Rolf' Otter, and Dieter
Tigler[*]
mide[lOl.The reaction afforded the cyclotetrapyrimidine f 13)
(dec. 362- 365 "C) as by-product ; the major product tetrapyrimidine (12) (m. p. 25&-252°C) was also cyclized to ( I S )
[yield 38 based on reacted (12)] by renewed reaction with
lithium diisopropylamide.
The classical aromatic systems possess predominantly nucleophilic (e. 8. benzene, furan) or predominantly electrophilic
character (e. g. pyridine, pyrimidine). Expectedly, "ArNU--ArE,
linkage" proved particularly useful in syntheses cia organometallic compounds[']. However, attempts to cyclize the resulting
di-, tri-, and tetraaromatic compounds themselves by Ar,,Ar,, linkage have so far merely led to alternative reactions.
It is therefore to be regarded as a step forward that reaction
of the dilithiated triaromatic (1 ) I 3 ] with quinoxaline not only
Br
(12) (38%)
(13) ( 12%)
Analogous reaction with 3,3'-bipyridyl afforded the expected
cyclotetrapyridine (14) (dec. 339-341 " C )in only 0.77, yicld.
Elucidation of the other products is still in progress.
The structures of the new compounds, which are all colorless
and crystalline, follow from elemental analysis, mass, 'HNMR, and UV spectra. A11 yields given are based upon weights
of starting materials.
Received: July 16. 1975 [Z 293a IE]
German version: Angew. Chem. 87. 745 (1975)
CAS Regi5try nnmhers
/ - ! I . 57757-43-0: 141. 56598-41-5, ( 5 ) . 5659X-42-6; f6). 5556-13-8:
f 7). 56598-43-7: (X). 40306-93-2: (9). 56598-44-8: ( 1 0 ) . 5h598-45-9:
( I l l . 5659R-46-0; i I 2 j . 56598-47-1 : ( 1 3 ) . 56598-48-2; 114). 56598-49-3:
3.3'-hipyridql. 587-46-4
714
( 2 ) ( L8"b)
( 3 ) (GY'?L)
yielded (3) (m. p. 333 "C) but also afforded the cyclotetraaromatic compound (2) (m.p. 307°C) by double ArNu-ArEl
linkage. Since only cyclization reactions occurred in this case
it may be presumed that, owing to crowding in the conforma[*] Prof. Dr. Th. Kauffmann, Uip1.-Chem. B. Muke, DipLChem. R. Otter,
and 1Xpl:Chem. D. Tigler
Organisch-Chemisches Institut der Universitit
44 Munster, OrlEans-Ring 23 (Germany)
Angew. Chem. iniernot. Edit.
C b l . 14 llY75)
i No. 10
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