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Dimers of Ketenylidene- and N-Phenylketeniminylidene-triphenylphosphorane.

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H
CHzR
. . - . . N H . ~ ” ~ ~ ~ , OH
oc-0
Both the resynthesized toxins were identical with the starting
compounds (1 a) and ( 1 b ) in all the properties examined:
CD spectra as in [’I, RF [TLC on Merck 60 FZs4 silica gel
plates in chloroform/methanol/water (65 :25 :4 v/v)]:
( I a)= 0.31, ( 1 b ) =0.24, UV difference spectra in the presence
of actin as in [61, toxicity in white mouse (LDSo)of (I a ) :
2 mg/kg, and of ( I b ) 2.5 mg/mg[’].
Th. Wieland, Science 159, 946 (1968).
Th. Wwland, I . Sang/, Justus Liebigs Ann. Chem. 671, 160 (1964).
F. Fahrenholz, H . Fuulstich, Th. Wielunrl, Justus Liebigs Ann. Chern.
743, 83 (1971); H. Filulstich, E . Nebelin, Th. Wieland, ibid. 1973, 50;
H. Heber, H . Faulstich, Th. Wieland, lnt. .I.Pept. Protein Res. 6, 381
(1974).
H. Faulstich, Th. Wieland, Europ. J. Blochem. 22, 79 (1971).
Th. Wieland, J . X . d e Vries, A. Schafer, H . Faulstich, FEBS-Lett. 54,
7 3 (1975).
Procedures :
Production of ( 2 a ) and ( 3 a ) from ( I a): A solution of
(I a) (l.Og, 1.27mmol) in trifluoroacetic acid (250ml)+water
(250 ml) is stirred for 15 h at 20°C and then evaporated down
in uacuo. The residue is chromatographed on Sephadex G-I 5
(column 5.5 x 184cm) with 0.1 N acetic acid. Of the 27.0ml
fractions,Nos. 118-190 afford 780 mg (78 %) of the trifluoroacetate of ( 2 a ) . No (1 a) could be detected with cinnamaldehyde-HC1 in the TL chromatogram of a sample applied in
concentrated form. Conversion into ( 3 a ) was accomplished
by passing (2 a)-trifluoroacetate (SOOrng, 0.63 mmol) dissolved
in 0.004 N ammonium hydroxide through Sephadex LH-20
(column 2.2 x 245 cm). On elution with the same solvent (3 a)
appears in Nos. 33-80 of the 6.5ml fractions; evaporation
in uucuo affords (3 a) (418 mg, 82 %) which is homogeneous
on electrophoresis.
Cyclization of (3 a ) : To a stirred solution of (3 a) (390mg,
0.48 mmol) in dimethylformamide (DMF) (51 ml) tetrahydrofuran (THF) (38ml) at -10°C are added a 1 % solution
of trifluoroacetic acid in THF (3.52 ml) and 5min later a
1 % solution of isobutyloxycarbonyl chloride in THF (6.63ml).
After 25min the solution is rapidly poured into a mixture
of DMF (194ml) and a 1 % solution of N-methylmorpholine
in THF (13.3ml) cooled to 0°C. The mixture is stirred for
2 h at 0°C and for 12h at 20°C. After evaporation in uucuo
the residue is chromatographed with 0.2% N H 4 0 H on
Sephadex LH-20 (column 2.2 x 245 cm) with collection of
6.0ml fractions. The last third of the first UV absorbing peak
(Nos. 121-170) is chromatographed once more on Sephadex
LH-20 (column 1.8 x 147 cm) in the same solvent. Compound
( I a ) (33mg = 8.7 %) appears in Nos. 38-54 of the 7.3 ml
fractions; it is identical with the original sample of ( l a )
in each of the above-mentioned properties.-Both procedures
can be applied to the phallisin series.
+
Received: February 15, 1977 [ Z 677 IE]
German version: Angew. Chem. 89,274 (1977)
CAS Registry numbers:
( 1 u ) , 17466-45-4; (1 b ) , 19774-69-7; ( 2 ~ ) .62015-97-8; (2h), 62015-99-0;
(3a), 35222-17-4; (361, 62046-08-6[I]
268
Constituents of the Green Deathcup Toodstool, Part 52.-Part
Guuhe. Th. Wieland, Justus Liebigs Ann. Chem. 1977, in press.
51 : A
Dimers of Ketenylidene- and
N-Phenylketeniminylidene-triphenylphosphorane
By Hans Jiiryen Bestmann, Giintrr Schmid, Dieter Sandmeier,
and Lothar Kisielowski“]
Ketenylidenetriphenylphosphorane(I a) and the N-phenylketeniminylidenetriphenylphosphorane ( I b ) are monomeric[’], strongly nucleophilic ketene derivatives that do not
dimerize. Their dimers ( 4 ) , which can be described by the
resonance formulas ( 4 A ) t--t ( 4 B ) , are therefore of interest,
since their mesomeric form ( 4 B ) represents yet another type
of “push-pull” cyclobutadiene[21.We have been able to synthesize the compounds ( 4 ) via the route shown in the following
reaction scheme.
Slow addition of ‘/2 equivalent of HCl to a solution of
the heterocumulene ylides (I a) or (I b ) leads via protonation
at the ylidic C-atom to their transformation into the phosphonium salts ( 2 a ) or ( 2 b ) , which are now “real” ketenes
or ketenimines having ambident dipolar character, i. e. nucleophilic at C, and electrophilic at CPC3].
They undergo spontaneous cycloaddition with non-protonated ( I ) to give the
1,3-cyclobutanedione derivatives ( 3 a ) and (3 b), respective( 3 a ) : m.p. 270°C (sinters); ‘H-NMRrS1(CDCI3):
~=3.85
IY[~’.
(d, JpH=8Hz, P’-CH); 31P-NMR[51(CDC13): 6 = -18.95
(d, P’-CH),
1.36 ppm (d, PQ - C<, J,, = 5.72 Hz); IR:
l760,1645cm-‘ (CO); yield 96%. (3b): m.p. 236 to 238°C;
31P-NMR[51(d6-DMSO):6 = -22.04 (d,P@-CH, JP,=5Hz),
f4.08ppm (broad s, P@-<); IR: l608,1572crn-’ (C=N);
yield 82 %.
Reaction of the phosphonium salts (3) with bases, particularly sodium bis(trimethylsilyl)amide[61,
leads to the bisylides
( 4 ) , which can be regarded as dimers of ( 1 ) . Evidence of
participation of the cyclobutadiene resonance formula ( 4 B )
is afforded by the position of the C O frequencies in the IR
spectrum of ( 4 a ) at 1650 and 1610 cm-’ and that of the
C=N bands of ( 4 b ) at 1563 and 1527cm-’.
+
[*I
Prof. Dr. H. J. Bestmann, Dr. G. Schmid, DipLChem. D. Sandmeier,
Dipl.-Chem. L. Kisielowski
Institut fur Organische Chemie der Universitat Erlangen-Nurnberg
Henkestr. 42, D-8520 Erlangen (Germany)
Aiigew. Chem. lnt. Ed. Engl. 16 (1977) N o . 4
0
X
- HCI
=C
0:s
PPh,
PPh,
R C H=CH-C =C -C OOC H,
I
I
:0: PPh,
0"
@
(11)
(a): X = 0
( b ) : X = NC,H,
( 4 a): yellow crystalline powder, m. p. 278 to 280°C (charring) 3'P-NMR[51 (CDC13): 6 = +9.48ppm (s); yield 83 %.
( 4 b ) : yellow crystalline powder, m.p. 178°C (dec.); MS:
m/e=754 (M'), 492 [M' -262 (Ph,P)]; yield 63%.
The following, in part preparatively useful reactions confirm
the structure of the compounds ( 4 ) : Reaction with HCl
regenerates the phosphonium salts (3). Reaction of ( 4 a ) and
( 4 b ) with methyl iodide affords the known phosphonium
salts ( 5 a ) and (5b)c7"1. On reaction of ( 4 a ) and ( 4 b ) with
p-nitrobenzaldehyde the phosphoranes ( 6 ~ ) [ ~and
" 1 (6b)[7b1
are formed (R= p-NO2C6H4). Hydrolysis of (4b)['"] in
aqueous methanol affords the monoylide (7) [m.p. 221 "C,
'H-NMR (d5-pyridine):T = 8.18 (s,CH2);MS: m/e =494 (M ');
yield 52%]. Oxidation of ( 4 a ) with the adduct of ozone
and triphenylphosphite[Sblleads to the cyclobutanetrione derivative (8) [m.p. 258°C (dec.); 31P-NMR[51(CDCI3): 6=
-7.60 ppm (s),IR: 1769,1651,1629 cm-l (CO)], which reacts
with benzylidenetriphenylphosphoraneto give ( 6 ) , R =C6H5,
[m.p. 192°C; "P-NMR['I (CDC13): 6 = -0.43ppml. ( 4 a )
reacts with methanol with ring opening to give the bisylide
(9)"l [m.p. 247°C; yield 79x1, whose two ylide functions
differ in reactivity. ( 9 ) is hydrolyzed by water to the acetylmethoxycarbonylmethylenetriphenylphosphorane (10)"
and reacts with p-nitrobenzaldehyde to give the phosphorane ( 1 1 ) (R=p-NOZC6H4) [m.p. 205°C; yield 69 %].
Received: February 3, 1977 [Z 676 IE]
German version: Angew. Chem. 89, 275 (1977)
CAS Registry numbers:
( 1 a ) , 15596-07-3; ( I b ) , 21385-80-8; ( 2 a ) , 62126-70-9; ( Z b ) , 62085-93-2;
( 3 a ) , 62085-94-3; ( 3 b ) , 62085-95-4; ( l a ) , 62085-96-5; ( 4 b ) , 62085-97-6;
(7), 62085-98-7; ( X ) , 62085-99-8; ( 9 ) , 4895-59-4; ( l l ) , 62086-00-4
Crystal structure of { l a ) : 1. J . Duty, P. Wheatky, J. Chem. SOC. A
1966, 1703; of f J b ) : H . Burzlaf, E . Wilhelm, H . 3. Bestmann, Chem.
Ber., in press.
[2] R . Gompper, G . Seybold, Angew. Chem. 80, 804 (1968); Angew. Chem.
Int. Ed. Engl. 7, 824 (1968); R . Gompper, S. Mensch, G. Sej~bold,ibid.
87, 711 (1975) and 14, 704 (1975), resp.; R . Gompper, J . Kroner, G.
[I]
Angew. Chem. I t i t . E d . Engl. 16 ( 1 9 7 7 ) No. 4
Seybold, H.-U. Wagner, Tetrahedron 32, 629 (1976) and literature cited
therein.
Cf. L. Ghosez, M. 3. 0 ' D o n n r l in Murchand, Lehrr Pericyclic Reactions,
Vol. 11. Academic Press, New York 1977, in press.
In the Scheme we have given the betaine form for compounds ( 3 )
and ( 5 ) - f I l ) since this is the most likely mesomeric form according
to IR spectroscopic findings.
100 MHz, PFT-Technique, H 3 P 0 4 as external standard.
Cf. H . 3. Bestmann, W. Stransky, 0. Vostrowsky, Chem. Bet. 109, 1694
(1976).
a) G. H . Birum, C . N. Matthews, J. Am. Chem. Sac. 90, 3842 (1968);
H . 3. Besrmann, R . Besold, D. Sandmeier, Tetrahedron Lett. 1975, 2293;
b) H . 3. Bestmann, G . Schmrd, Angew. Chem. 86, 479 (1974); Angew.
Chem. Int. Ed. Engl. 13, 473 (1974).
a) For hydrolysis of phosphorylidenes cf. H . 3. Bestmann, Angew. Chem.
77, 609, 651, 850 (1965); Angew. Chem. Int. Ed. Engl. 4, 583, 645,
830 (1955); b) H . 3. Besrmann, L. Kisielowski, W Disrler, ibid. 88, 297
(1976) and 1 5 , 298 (1976).
P . A. Chopard, J . Org. Chem. 31, 107 (1966).
G. M i r k l , Chem. Ber. 94, 3005 (1961).
Synthesis of Acyldiarylphosphane Oxides-Key Compounds in the Oxidation of Acyldiarylphosphanes with
Molecular Oxygen[**]
By Ekkehard Lindner, Hans-Dieter Ebert, Hans Lesiecki, and
Gottfried Vordermaier"l
By slow oxidation of the acylphosphane RC(0)P(C6H5)2
with O2 under rigorous exclusion of water we have been
able to isolate for the first time the previously only postulated[']
or unsatisfactorily describedc2] acyldiarylphosphane oxides
(1 ).
[*I
Prof. Dr. E. Lindner, Dr. H.-D. Ebert, Dip1.-Chem. H. Lesiecki, Dipl..
Chem. G. Vordermaier
lnstitut fiir Anorganische Chemie der Universitat
Auf der Morgenstelle 18, D-7400 Tiibingen 1 (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie.
269
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