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Heterocumulenes Reaction of C3O2 with Ketenylidenetriphenylphosphorane; Synthesis and Structure of a Spirobis(cyclobutanedione).

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Heterocumulenes: Reaction of C,O, with
Ketenylidenetriphenylphosphorane; Synthesis and
Structure of a Spirobis(cyc1obutanedione)""
Lucian0 Pandolfo,* Giacomo Facchin,*
Roberta Bertani, Paolo Canis,* and Giovanni Valle
Acylketenes (a-oxoketenes) are subject to increasing interest
and are used extensively as synthetic building blocks for a large
number of interesting compounds.['] Recently we reported'']
that the simplest stable bis(ketene), carbon suboxide (1)
reacts with stabilized phosphonium and arsonium y l i d e ~ [bear~]
ing a hydrogen atom on the ylidic carbon atom. Depending on
the ylide, bis(ylidic) malonil derivatives or zwitterionic pyrone
derivatives are formed, but Wittig-type reactions were never
observed.
Ketenylidenetriphenylphosphorane 2[51 is a readily accessible molecule containing both an ylidic and a ketenic function. In contrast to ketenes, 2 displays no tendency to dimerize,
and when it is protonated the resulting phosphonium ion shows
typical ketene behavior.[61 Thus protonated 2 can undergo
[2 + 2lcycloaddition with 2 to form, after reaction with base, the
bis(ylidic) cyclobutanedione 3.c7]Compound 3 reacts with carbony1 compounds yielding the cyclobutane-l,3-dione derivatives 4 by a Wittig-type process.[6,71 Moreover, cyclobutanedionic derivatives 5 have been obtained through [2 + 2]cycloaddition of 2 with ketenes.[*] Bestmann et al. reported the syntheses and determined the structures of the cyclobutanetrione 6 ,
obtained by oxidation of 3, and of the bicyclic bis(ylidic) derivative 7.L91
We report the synthesis of the bis(ylidic) spirocyclobutanedione 8 by the double [2 + 2lcycloaddition reaction of two molecules of 2 with one molecule of l [Eq. (a)]. The 31P{1H}NMR
-
2
+;c=c=o
Ph3P
2
+
c302
__c
1
8
0
0
3
4
5
7
6
0
0
8
[*I
[**I
Dr. L. Pandolfo
Dipartimento di Chimica Inorganicd, MetallorgdniCd e Analitica
Universitri di Padova
Via Marrolo I. 1-35131 Padova (Italy)
Fax: Int. code +(49)8275161
e-mail: pandolfo@rchim02.chin.unipd.it
Dr. G. Facchin. Dr. R. Bertani
Centro di Studio per la Chimica e Tecnologia dei Composti
Metallorganici degli Elementi di Transizione del CNR
Istituto di Chimicd Industriale
Universiti di Padova, Via Marzolo 9, 1-35131 Padova (Italy)
Fax: Int. code + (49)8275525
Prof. P. Ganis
Dipartimento di Chimica, Universiti dt Napoli
Via Meszocannone 4, 1-80134 Napoli (Italy)
Dr. G. Valle
Cenlro di Studio sui Biopolimeri. Padova (Italy)
This work was wpported by the Minister0 dell' Universiti e della Ricerca
Scientilica e Tecnologica (MURST) and by the Consiglio Nazionale delle
Ricerche (CNR)
A n x w . Chi,nr. In/..&I.
Engl. 1996, 35, No. 1
8
spectrum of 8 shows one singlet at 6 = - 2.91, which is in the
typical range for acyl ylides having a cyclobutane structure.[8-'01 The 13C{'H} NMR spectrum, in addition to resonances due to the phenyl groups, shows signals at 6 = 122.59
and 185.11 attributable to C-P and C=O groups, respectively.
A complex signal is also observed at S = 83.10. which agrees
with the values reported for the central carbon atom of related
spirocyclobutenones (6 = 79.7-84.8) . I l l 1
In the mass spectrum of 8 under electron impact ionization
conditions no molecular ion was detected; however, the protonated molecule was easily generated by fast atom bombardment
and detected at m/z 673. Accurate mass measurements with
PEG 500 as a standard gave a value of 673.1657 (+0.005), in
agreement with the proposed structure (C,,H,,O,P,,
calcd
673.1688). The fragmentation pattern in the mass spectrum will
be described elsewhere.
Single crystals of 8 suitable for X-ray structure analysis['21
were obtained by slow evaporation of a CH,CI, solution. The
independent structural unit consists of two molecules of 8 (A
and B). They differ mainly in the orientation of the phenyl
groups with respect to the molecular backbone. The structures
of these two nonequivalent molecules are shown in Figure 1 .
Although the molecules of 8 are in principle C,-symmetric,
owing to crystallographic demands they display a total absence
of symmetry. Thus, in 8 the molecular structures of four independent cyclobutanedione moieties can be compared.
The lengths of the ylidic P-C bonds, with an average value of
1.737(5) A, are indicative of substantial double bond Character
and in agreement with values given in several similar casC=O bonds, with the exception of C(1)B'e ~ . [ ' ~ "14]
, " The
~
O(1)B' (1.194(9) A), have an average length of 1.215(7) A,
which is virtually identical with the value reported in the literature (1.217(5) A) for a C = O bond having partial triple bond
character due to dipole formation (Ca+=06-)
. [ 1 3 1 For comparison, the length of a "normal" C = O bond is 1.230(5)A.[13c,d,
141
The distances between the P-substituted C atoms and the adjacent 0-substituted C atoms are in the range of 1.433(7)1.464(7) A. These values correspond with the lengths of C-C
bonds in conjugated systems such as C=C-C=C or C=CC-C, which are reported to be in the range of 1.43 1.48 A,['"
VCH Vrrlugsgr.se/hchu/t mbH, 0.69451 Weinhrim, 1996
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0
0
c
c
II
II
+
C
It
II
0
0
2 CH3CHO
-
8
suspension of 8 in CH,NO, is heated at 60 "C in a sealed vial
with two equivalents of CH,CHO, the solid dissolves rapidly.
The 31P{'H} NMR spectrum (CDCI,) of the sticky orange compound obtained by evaporation of the solvent shows a unique
signal at 6 = 27.84 due to OPPh,. The 'HNMR spectrum of
this compound presents two relevant signals at 6 = 4.40 (q,
3J(HH) = 6.1 Hz) and 1.19 (d, 3J(HH) = 6.1 Hz) in a 1 : 3 ratio,
which are attributed to the =CH and CH, protons, respectively.
In the IR spectrum of the new orange substance the band at
1622 cm- ' characteristic of 8 is gone and new intense absorptions at 1678 and 1553 cm-' are evident. These data indicate
that 8 undergoes a Wittig reaction to afford compound 9. At
present, the reactivity of compound 8 toward organic and
organometallic reagents is under investigation.
Fig. 1. Molecular structures of the two independent molecules A and B in a crystal
of 8; the two molecules have similar structural parameters and the pseudo-C,
symmetry. Selected bond lengths [A] for molecule A (top): P(l)A-C(2)A 1.736(5).
P(l)A-C(2)A 1.735(5), C(l)A-O(l)A 1.211(6), C(3)A-O(3)A 1.219(6), C(1)A0i1)A' 1.204(7), C(3)A'-0(3)A 1.215(7), C(l)A-C(Z)A 1.455(6), C(2)A-C(3)A
1.433(7), C(l)A-C(Z)A 1.457(7), C(2)A-C(3)A 1.462(7), CA-C(1)A 1.533(7), CAC(3)A 1.549(6). CA-C(1)A 1.558(6), CA-C(3)A 1.554(7); for molecule B (bottom):
P(1)B-C(2)B 1.741(5), P(1)B-C(2)B' 1.737(5), C(1)B-O(1)B 1.221(6). C(3)B-O(3)B
1.217(7), C(1)B'-O(1)B 1.194(9), C(3)B'-0(3)B' 1.217(7), C(l)B-C(2)B 1.@4(6),
C(2)B-C(3)B 1.447(8), C(l)B-C(Z)B' 1.458(8), C(2)B-C(3)B' 1.464(7), CB-C(1)B
1.540(7), CB-C(3)B 1.541(8), CB-C(1)B 1.541(7), CB-C(3)B' 1.558(8).
Experimental Procedure
8 : A solution of 1 in toluene (0.044 M. 15 mL, 0.66 mmol) was added at room
temperature to a stirred solution of 2 (0.395 g, 1.31 mmol) in 25 m L of toluene. A
yellow solid immediately precipitated, which was filtered, washed with acetone, and
dried under vacuum t o give 8 as creamy white crystals. Yield: 0.380 g (86%). M.p.
245-250°C (decomp); correct C, H analysis. IR (Nnjol): 1622 cm-' (vco);
' H N M R (200 MHz, CD,CI,, 25°C): S = 7.73-7.55 (m, C,H,); l3C{'H} N M R
(100 MHz, CD,CI,. 25 "C): 6 = 185.11 (dd. 'J(CP) = 5.3 Hz, 4J(CP) = 2.6 Hz,
C = O ) , 122.59 (d, 'J(CP) = 91.6 Hz. C=P), 83.10 (m, central C); ,'P('H} N M R
(80 MHz, CDCI,, 25'C): 6 = - 2.91 is); FAB MS in glycerol: m/; ("A):673 ( 3 )
[ M HI+. 672 (2) [ M I ' ; FAB MS in m-nitrobenzyl alcohol: 673 (30) [ M + HI+,
644 (4) [ M CO]'.
+
~
This structural data is consistent with formal resonance structures in which both mesomeric and inductive effects are supposed to operate (Scheme 1). In 8 the limiting resonance form a
seems to dominate; form c, suggested for compound 6,['] cannot
explain our data alone, since in this case the C=O bonds would
be somewhat longer than those in "normal" keto groups. The
other molecular parameters of molecules A and B, including
bond and torsion angles, are quite similar to those of analogous
they do not depend upon electronic factors
c o r n p o ~ n d s ;''I[ ~ ~
but are chiefly controlled by intramolecular steric requirements
and/or crystal field forces.
The ylidic character of 8 is in agreement with the results
obtained in the reaction with acetaldehyde [Eq. (b)]. When a
6-0
II
0-
I
Received: July 18, 1995 [Z8219IE]
German version: Angew. Chem. 1996, 108, 75-17
Keywords: carbon suboxide . heterocumulenes . ketenylidene
phosphoranes . spirocyclobutanes . strained rings
[l] a) T. T. Tidwell. Kerenes, Wiley, New York, 1995; b) M. A. McAllister, T. T.
Tidwell. J. Am. Chem. Soc. 1994, 116, 7233; c) A. D. Allen, M. A. McAllister,
T. T. Tidwell, Tetrahedron Lett. 1993, 34, 1095; d) C. 0. Kappe, G. Farber, C.
Wentrup. G. Kollenz, J. Org. Chem. 1992.57,7078; e) Tetrahedron Lett. 1992,
33. 4553; f ) H. J. Bestmdnn. G . Schmid, D. Sandmeier, C . Geismann, ;hid.
1980.21, 2401.
[2] a ) L. Pandolfo. G. Facchin, R. Bertani, P. Ganis, G. Valle, Angew. Chem.
1994, 106. 586; Angew. Chem. Int. Ed. Engl. 1994, 33, 576; b) R. Seraglia, P.
Traldi. R. Bertani. G. Facchin, L. Pandolfo, Org. Mass Specrrom. 1994,
26, 619; c) L. Pdndolfo, G.
Facchin, R. Bertani, L. Zanotto,
P. Ganis, G. Valle, R. Seraglia.
Inorg. Chim. Acra 1995, 237,
27.
[3] a) 0. Diels, B. Wolf, Ber. Deut.
Chem. Ges. 1906, 39. 689; b) T.
Kappe, E. Ziegler, Angew. Chem.
C
1974,86,529; Angens. Chem. Int.
Ed. Engl. 1974.13,491; c) G. Paiaro, L. Pandolfo, Comrnenrs In0
org. Chem. 1991, 12, 213.
[4] A. W. Johnson, Ylides andlmines
C
of Phosphorus, Wiley, New York,
1993. and references therein.
-
--
il
a
b
Scheme 1.
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VCH Verlugsgesellxh~rftmbH 0-69451 Wernherm, 1996
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Angew. Chem. Int. Ed. Engl. 1996, 35. N o . I
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were chosen and fixed on a p-tert-butylcalix[4]arene tetraoxo
a) C. N. Mattews, G. H . Birum, Tetrahedron Lert. 1966, 46. 5707; b) H. J.
Bestman. D. Sandmeier, Angew. Chem. 1975, 87, 630; Angew. Chem. Int. Ed.
matrix to give [ZrR,] ,I7][ZrR]+,t8]and [Zr(diene)] complexes.[g1
Engl. 1975. 14, 634; c) Chem. Ber. 1980, 113, 277.
The starting material, the functionalizable [ZrCl,] complex 2,
H. J. Bestmann, Angen. Chem. 1977,89, 361 : Angew. Chem. Inl. Ed. Engl. 1977.
was prepared in two steps from dimethoxy-p-tevt-butylcal16, 349.
i~[4]arene['~'
dianion (Scheme 1). Even very small amounts of
H. J. Bestmann, G. Schmid, D. Sandmeier, L. Kisielowski. Angew. Chem. 1977,
89. 275; Angem. Chem. Int. Ed. EngI. 1977, 16, 268.
G. H. Birum. C. N. Mattews, J Am. Chem. Soc. 1968, YO, 3842.
H. J. Bestmann, T. G. Furst, A. Schier, Angew. Chem. 1993,105,1783;Angew.
ce, ,ce
Chem. Inr. Ed Engl. 1993. 32, 1746.
H. J. Bestmann, B. Siegel, G. Schmid, Chem. Lett. 1986, 9, 1529.
S. Polanc. M. C. Lahille, Z. Janousek, R. Merknyi, M. Vermander, H. G.
Viehe, B. Tinant, J. Piret-Meunier. J. P. Declercq, New. J Chem. 1991, 15, 79.
Crystal strncture analysis of 8: C,,H,,O,P,: A4 = 672.65; crystal dimensions:
0.2 x 0.2 x 0.1 mm: Pbilips PW 1100 computer-controlled four-circle diffractometer: graphite monochromator, Mo,, radiation, I. = 0.71073 A, 298 K ;
8-28 scan method; the lattice constants were determined from 25 reflections:
2
1
Scheme 1.
u = 14.988(4), h =18.946(6), c = 12.905(3) A, a = 102.2(1), fl = 90.4(1),
.,, - 75.4(1) ; I.' = 3461.97 A3, space group P i , 2 = 2, pcalrd= 1.290 g ~ m - ~ ,
F(000) = 1400. p(MoKJ = 1.28cm-'; hkl range -1I<h<17, -22<k<22,
O < l < 12; of 11 397 independent reflections 6102 were considered "observed"
impurities in 1and 2 are particularly troublesome for the further
[F, 2 3(F0)];solution and refinement by standard Patterson methods and suhsefunctionalization. Scheme 2 shows how 2 was converted into a
quent Fourier recycling (SHELX-76); all non-hydrogen atoms were refined
number
of complexes in which organometallic functionalities
with anisotropic displacement parameters; all hydrogen atoms were located
are bonded to a polyoxo matrix. This scheme outlines a general
and refined isotropically; R (R,) = 0.050 (0.060 with M' =I/[o*(F,) + 3
x 10-3F:]), 241 parameters, maximum residual electron density 0.39 e k 3 .
entry to the organometallic chemistry of zirconium on a p-tertFurther details of the crystal structure investigation may be obtained from the
butylcalix[4]arenesupport. The present report concerns only the
Director of the Cambridge Crystallographic Data Centre, 12 Union Road,
synthesis and the characterization of the compounds; reactivity
GB-Cambridge CB21EZ (UK), on quoting the full journal citation.
studies will be conducted later.
a) D. R. Davies. J. J. Blum, Acta Crystullogr. 1955, 133, and references therein;
b) E. G. Cox. M. W. Dangill, G. A. Jeffrey, J. Chem. Soc. 1952,4854; c) Interulomir Di.stunce.5 Supplement, Chemical Society Special Publ., No. 18, London,
R
1965; d) Hundbook of Chemistry and Phvsics, 74th ed., 1993.
International Tuhlesjiir X-Ray Crysfullogruphy,Riedel. Boston, MA, 1983.
a) F. H. Allen, 0. Kennard, D. G. Watson, L. Bremmer, A. G. Orpen, R.
Taylor, 1 Chem. SOC.
Perkin Truns. 1987, 2, S 1 ; b) M. D. Harmony, V. W.
Laurie. R. L. Kuczowski. R. H. Schwendeman, D. A. Ramsay, F. J. Lovas,
W. J. Lafferty. A. G. Maki, J. Phjs. Chem. Ref: Duta, 1979, 8 , 619.
I @
R=H,8
R=Ph.9
The Organometallic Chemistry of Zirconium
on an 0 x 0 Surface Provided by
p-tert-Butylcalix[4]arene"*
T
b
2
R=Me,3
R = PhCH2,4
Luca Giannini, Euro Solari, Antonio Zanotti-Gerosa,
Carlo Floriani,* Angiola Chiesi-Villa, and
Corrado Rizzoli
The chemistry of calix[n]arenes and transition metal complexes"' is a very young and rather unexplored
Previous
applications of calix[n]arenes did not extend much beyond their
use as a conventional polyoxo coordination environment and,
in a few cases, for the endo coordination of substrates in their
ca~ity.[~-~]
Calix[n]arenes have never been exploited as polyoxo matrices
for reactive organometallic functionalities. Their use as ancillary ligands in organometallic chemistry is an interesting application due to their unique structural properties. In this context,
some target functionalities that are versatile in organic synthesis
[*I
[**I
Prof. Dr. C. Floriani, Dr. E. Solari, Dr. A. Zanotti-Gerosa, L. Giannini
Institut de Chimie Mintrale et Analytique
Universitk de Lausanne, BCH 3307, CH-I015 Lausanne (Switzerland)
Fax: Int. code +(21)692-3905
Prof. Dr. A. Chiesi-Villa, Dr. C. Rizzoli
Dipartimento di Chimica, Universita di Parma (Italy)
This work was supported by the Fonds National Suisse de la Recherche Scientifique (grant no. 20-40268.94)and by Ciba-Geigy SA (Basel, Switzerland). We
thank Dr. Marc Weydert for preliminary work on the synthesis of 2.
A n p w . Chem. Int. E d Engl. 1996, 35, N o . 1
0 VCH
b
R=Me,5
R = PhCH2,6
Scheme 2. a) MeLi, toluene, - 30 "C; PhCH,MgCI, toluene, - 35 "C. h) CO, benzene, 8 "C. c) [Cp,Fe]BPh,, toluene, -35°C. d) [Mg(C,H,)(thf),], toluene,
-25 "C; [Mg(C,,H,,)(thf),], toluene, -30 "C.
When reaction a was carried out with a 1 : 1 molar ratio of 2
and alkylating agent, a mixture of 2, 3, and the monoalkylated
analogue were obtained in an approximate 1 :1 :2 ratio (determined by 'H NMR spectroscopy). Furthermore, the same
1:1:2 mixture was obtained when equimolar solutions of 2
and 3 were mixed. Thus, under the conditions mentioned above,
the monoalkylated form cannot be obtained in pure form.
Both dialkyl derivatives 3 and 4 show high thermal stability
(65 "C for 14 h), while only 4 was found to be photolabile in
Verlu~sgesellschaftmhH. 0-69451 Wernheim, 1996
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structure, synthesis, heterocumulenen, reaction, cyclobutanedione, c3o2, spirobi, ketenylidenetriphenylphosphorane
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