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Crystal Structure of 2-Hydroxy-4 9-methano[11]annulenone.

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W Henviy and H . Zviss. J. Amcr. Chem. Soc. 79. 6561 (1957)
[S] F . Ilciri and R .\, Z. Anorg. Allg. Chem. 7%. 145 (1958).
[ 6 ] W Hwwig and H. Zei.\.\.J Org Chem 23. 1404 (1958).
[7] G. Wiirry and R . Polsrtx Lrrbigs Ann. Chem. 5Y9. I (1956): H
Schriiidhiiirr and W EoiiicJi, Chem. Bcr. 101. 3556 (196x1.
[ X I We thank Dr. W Krilrc~s.UniversitHt Grrrfswald, for this mcasure-
[9] W. 7?oiirt.h. Dissertation, Univsrsitit Wurzburg 1968. p. 99.
[lo] C. E . Cnrirm. W . L. I f . C r w n , and K . Wide: Organometallic Compounds. Vol. II.Methuen, London 196X. p 39.
[ I I] E Kurrus and P. K/oir.sch. Monatshcr. Deut. Akad. Wiss. Bcrlin
6 , 735 (1964): G. W i l k r vf a/.. Angew. Chem. 75, 10 (1963): 78. 157
(1966): Angew. Chem. internat. Edit. 2. 105 (1963). 5, 151 11966).
Crystal Structure of 2-Hydroxy-4,9methano[ 1llannulenone
Fig. I. Crystal structure of 2~hydroxy-4,Y-methano[I l]annulenonc I I )
By D. U! J . Cruickshcink, G. Filippini,
and 0. S. M i l k [ * ]
We therefore suggest that considerable delocalization
occurs in that ring, more than in either 4,9-methano[l I]annulenone ( 2 ) (1.366-1.422 A) or in 1,6-methano[ I0]annulene-2-carboxylic acid ( 1.378-1 .426)I4J,and
more still than in cycloheptatriene ( 1.356-1.446 A)( I o l or
its derivatives ( e .9. 1.35-1.45 A)[' ' 1 .
The 'H-NMR values reported for (/)['I are in agreement
with our findings. The multiplet which extends over the
region t =2.5-3.2 is positioned similarly to that reported
for 1,6-methano[ l0]annulene[' 21 in which a delocalized
system is recognized (for bond lengths see ref. [S]), whereas
in cycloheptatriene values of T = 3.4-3.9 occur. Such delocalization might be expected to be associated with a
pronounced ring current and consequential difference in
absorption of the S J ' M and the anti protons of the methylene
group. The observed difference, 0.7 r-units, must be the
resultant of the deshielding effects of the ring current on
the one proton and of the C=O group on the other.
When comparison is made of the spectrum of ( I ) with
that of (Z), however, it is important to note the change
of shape between the two molecules;,(/) is more planar
than (2), possibly because the hydrogen bond is inrrcimolecular, in contrast to the case of crystalline trop o l ~ n e [ ~The
] . effect of this change of shape is to increase the transannular distance between the anti-omethylene hydrogen and the carbonyl carbon from 2.46 A in (2)
to 2.64 A in ( 1 ) .
Recently the synthesis of a number of 10 x-electron analogs
of tropone"] and of tropolone['], and structure analyses
of t w o [ I 1Jann~lenones1~.'Jhave been reported. In this
communication we present the essential structural results
for 2-hydroxy-4,9-methano[ 1 Ilannulenone ( I )I2][**I.
Compound ( / ) crystallizes in the triclinic system, space
group PI with a=8.448, h=8.184, c=7.803A; "J.= 110.10,
p = 69.09, y =92.38 .Thc analysis is based upon 1639 reflections measured on a computer-controlled diffractometer,
the structure was solved by direct methods and refined
by least-squares techniques: the final R is 6.3%.
In preparation for the discussion of ( 1) it should be noted
that definitive structural evidence now exists to show that
tropone itself exists as a near-planar (slightly-boat conformation) molecule with alternating single and double
bonds['], that its derivatived61 display similar features,
and that tropolone and substituted tropolones seem also
to manifest alternation of bond length[".
We find (see Figure I ) that in ( I ) there is evidence both
of an alternation of bond lengths and of delocalization
within the same molecule; the eight-membered ring, which
contains the 3-hydroxyketone group, has two formal double bonds whose (independent) lengths are 1.353A, little
more than the standard value for an isolated double bond[*].
The C-C bond lengths in the cycloheptatriene ring,
excluding those to the methylene bridge, however show
only a small variation in lengths between 1.376 and 1.399A.
[*] D W. J. Crurckshank
Dcpartmcnt o f C'hemrslry
Lniversity of Manchester Institute of Science and Technology
Manchestcr M60 IQD (England)
Ci Filippinr
prcsent address:
lstituto di Chimica Fisica
{Jnivcrsiti di Milano (Italy)
0 S Mills
Department of Chemistry
University of Manchestcr
Manchester M I 3 YPL (England)
[**I We are grateful to Prof. E .
of ( I i.
V O ~ C , /for supplying us with crystals
In the present analysis we have determined, and satisfactorily refined, the positions of all the hydrogen atoms and
we confirm from these direct observations, as well as
infer from the positions of the double bonds, that the
hydroxyl group is located on C-2['].
The overall structure has close to mirror symmetry perturbed only by the hydroxyl group. The C-0 distances
in the carbonyl and hydroxyl groups are in good agreement
with usually accepted values.
Received: J u l y 16. 1973 [7 X Y i I€,]
German version' Angcw. Chem. X.5. 870 11973)
[I] M' G'rrmnrr, J . Rrisdorff, M! Jiineinrmn. and E. V q d . J. Amer. Chem.
Soc. 92. 6335 11970).
[ 2 ] J . Reisdorff and E Lhgd, Angew. Chem. H4, 208 (1972): Angcw
Chcm. internat. Edit. / I , 218 (1972).
[3] D. &! Hiidsoii and 0. S Mills, Chem. Commun. 1971. 153.
[4] R . L. EC&~JC,.S
and 0. S. Mi//.\. Isr. J. Chcm. / I ) . 485 (1972)
I S ] M . J . &7rnJw. 0. S. Mi//s, and G . Fihppiiii, Chem Commun. IY73.
6 6 , M. Ogusuwu~u. 7 I i j i i i ~ ,and M. Kiniuru, Bull Chem Soc. Jap.
45. 3277 (1Y72).
[6] 7: Huro, H . S h r i i i i i n o w h i , and Y. Sosodri, Tetrahedron Lett IY6Y.
753: 0. U! J . Criir~~k.shirnk.
G Filippirii, and 0. S. M i l k . Chcm. Commun.
1977, 101 : K' I h u r ~ i .7: Hriiu. If. Shiiniinuiid~i, and Y. Sosudii. C'hem.
Commun. 1972, 339: D. J . U'utkin and 7: A. Hoinor, I Chem. SOC.
B1971. 2167: K. lhrito, H . Shimunoirchi, and Y So.sudu, Chem. Lett.
lap. 1973,269.
[7] S fro, Y. Fukazawu, and Y Irrnka, Tetrahedron Lett. 1972. 741.
745, H. Shimanmichi and Y. Sosudu, ibid. 1970, 2421 ; Acrd Crysldllogr.
B 2Y, 81 (1973).
[R] Chem. SOC (London), Spec. Publ. No. 18 (1965).
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[lo] M Trutwubrrg, J Amer Chem. SOC.K6. 4265 (1964).
[ I I] R . E . Dacis and A. Tulinsky,J. Amer. Chem. SOC.X K , 4583 (1966).
[I21 E. h q r l and H . D . Roth. Angew. Chem 76, 145 (1964): Angew.
Chem. internat Edit. 3, 228 (1964).
Of the various trihalogermanes, only HGeQ and HGeBr3
have been previously reported ; they tend to decompose
according to eq. (1b)['J or to GeX,, GeX, and H,[,].
Triiodogermane, HGe13, has been merely conjectured as
an intermediate in germylation reactions of olefins with
Ge12/50% aqueous
Since we succeeded in preparing pure, GeBr4-free HGeBr3
by dissolving GeBr21sl in anhydrous HBr, we have found
also that HGe13 is formed in quantitative yield when
anhydrous HI is condensed on pure GeI, [eq. ( 1 a)]:
The pale yellowish solution is stable below -50 C but
at room temperature decomposes gradually thus:
+ HI
+ Gela
+ Hz
50% after 7 days); dismutation to H2Ge12 and Ge14
was not observable. When the solvent HI is removed,
even at low temperature, only GeIz is left as solid residue
[eq. ( 1 b)]; and other attempts to prepare it-by
HGeCI3/HI, HGeC13/GeI4 or HGeCI3/HSiI3 as reactants-lead
also to Ge12. However, HGe13 is formed
smoothly when an excess of HI is condensed on GeBr2,
but in a suspension of Ge12 in 57 YOaqueous HI we could
not prove the formation of triiodogermane.
Thus HGe13 can exist only in liquid HI. But in such
solutions we could measure the Raman spectrum, and
this showed, as required for a CSr.molecule, three polarized
and three depolarized lines (Table 1). The frequencies are
in the expected regions, which can be derived from correlations and calculations for comparable vibrations for the
series HGeX3 (X =C1, Br['] or I) and HGeX3/GeX4.
Table I . Fundamental vibrations ( c m - ' ) from the Raman spectrum of
20hX (0.5, p)
203 (10. p)
93 (5. P)
260 (1.5. dp)
66 (6, d p )
643 (0.6, dp)
A-XOIO Graz. Stremayrgiisse 16 (Austria)
This work was supported by the Fonds zur Forderung der wissenschaftlichen Forschung, Vienna
Nucleophilic Ether Fissions by
By Gert Kiibrich and Annegrir Baurnann"]
Because of the role of ethereal solvents in reactions of
organometallic compounds, fission of ethers by organometallic and in particular organolithium compounds is very
important. According to earlier investigations it is normally
initiated by deprotonation at the 2- or P-carbon atom
of the ether"]; very recent
have uncovered
an interesting meshing of a-, 0-and, a',p-eliminations for
thecase ofdiethyl ether/alkyllithium. We propose to collect
together under the general expression "protophilic ether
fission" all those fissions that have proton abstraction
from the ether molecule in the first reaction step as their
common characteristic [eq. (I)]:
Protophilic ether fission:
- C-C
consecutibe reactions
We now report "nucleophilic ether fission" as a further
type of reaction. This is a nucleophilic replacement by
the organolithium compound [eq. (2)], in which an RO
group of the ether constitutes the leaving group, thus
playing the same role as do halogen atoms in the coupling
of alkyl halides.
Nucleophilic ether ,fission:
[*] Doz. Dr. F. Hofler and Dip].-lng. E. Brandstitter
lnstitut fur Anorganische Chemie der Technischen Hochschule
[5] M . D. Ciirirs and P. Wdbvr, Inorg. Chem. 1 J , 431 (1972).
[6] H. Sirherr -Anwendungender Schwingungsspektroskopieinder anorganischen Chemie. Springer, Heidelberg 1966.
.~ .
[ I ] E. Wiberg and E . Ainbrryrr. Hydrides of the Elements of Main
Groups I---IV. Elsevier, London 1971
[2] M . L. D e l w u u l l ~ J~., Phys. Chem. 56, 355 (1952).
[4] I' F . Mironol-, L. N . Kalinino, t;. M . Bvrliner, and 77 K . Cur, Zh.
Obshch. Khim. 40, 2597 (1970).
By Friedrich Hofler and Ernst Brandstatred']
+ HX &
Received: July 30. 1973 [Z X96 IE]
German version: Angew. Chem. KS, 870 (1973)
[3] P. ?ilu:rro//r.s and C . M a i w o l , Bull Soc. Chim. Fr. 1967. 251 I .
vGeH and GHGeI are slightly dependent on concentration,
being S-Scmhigher for very dilute solutions
In thereaction ofstoichiometric amounts of HI with GeBrz
or a GeBr4/Ge12 mixture there are formed, besides HGe13,
the trihalides HGeBr12 and HGeBrJ, which also cannot
be isolated but can be recognized from their main frequencies in the Raman spectrum (220 vs,p and 239 cm- V S , ~ ) .
If we let aside those reactions, formally similar but different
in kind, in which complex formation at the oxygen atom by
a Lewis acid is the first step, as with triphenylmethyl an[*] Prof. Dr. G Kobrich and Dip].-Chem. A. Baumann
lnstitut fur Organische Chemie der Tcchnischen L'niversitiit
3 Hannover, Schneiderberg I B (Germany)
This work was supported hy the Dcutsche Forschungsgemeinschaft
and the Fonds der Chemischcn Industrie.
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crystals, structure, annulenone, methane, hydroxy
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