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Bis-(1 5-cyclooctadiene)platinum(0).

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r-l( I )
Ntse"
The synthesis of ( I ) is analogous to the recently reported
one-step preparation of 1,2,5-thiadiazole 131. Ethylenediamine
dihydrochloride was allowed to react with selenium monochloride (molar ratio 1 : 8) in dimethylformamide, first for
1 h at -20 OC and then for 6 h at 0 OC. Subsequent steam
distillation of the reaction mixture afforded 7 % of 1,2,5selenadiazole.
IR-Spectrum (liquid film): 3030 (w), 1359 (s), 1230 (s), 1005
(m), 878 (s), 725 (s) cm-1 141.
The 12 eV mass spectrum of 1,2,5-selenadiazole displays a
signal at m/e 134 corresponding to 12CzH214N~fjoSe.Four
satellite molecular peaks at m/e 136,132,131, and 130appear
in proportion to the relative isotopic abundances of Se82,
Se78, Se77, and Se76. In the 70 eV mass spectrum, HCNSef,
HCN+, and Se+ appear as the major fragmentation products,
analogous to the fragmentation of 1,2,5-thiadiazole 151.
2'-Benzylidene-l'-methylchloroformohydrazine (3), which
can be recrystallized from ethanol, reacts readily with methyl
hydrazine to form an oily mixture; hydrolysis of this product
gave pure (5) in 23 % yield.
The reaction of methylhydrazine with phosgene in ether gave
(5) in less than 2 % yield. Attempts to synthesize (5) by the
reaction of diethyl carbonate with methylhydrazine were unsuccessful and gave only ethyl 2-methylcarbazinate 131.
The properties of 1,2,5-selenadiazole are compared with
those of 1,2,5-oxadiazole (furazan) 161 and 1,2,5-thiadiazole 13~71. The data indicate that 1,2,5-selenadiazole, like
1,2,5-thiadiazole and selenophene, is a thermally stable,
aromatic ring system.
1,2,5-Thiadiazole (71
B.p. ( "C)
94
98
M.p. ("C)
~
1,2,5-Selena.
diazole
138
-28
-50.1
20.5-21
2-10 (24 "C)
Procedure :
d (siml) (t)
1.168 (20°C)
1.268 (25 "C)
Phosgene (175 g) is passed into a stirred slurry of 473 g of
benzaldehyde methylhydrazone in 6 liter of ether for 8 h at a
temperature of 25-30 "C (external cooling). After standing at
room temperature for 15 to 18 h, the precipitate is separated
and washed with water to remove the hydrochloride of compound ( I ) . The water insoluble portion is dried and recrystallized from heptane to afford 465 g (89 % yield) of
1,5-bis(benzylidene)-2,4-dimethylcarbonohydrazide (2), m.p.
"D
Amax (mv)
[solvent]
1.4077 (20 "C)
1.5150 (25 "C)
1.6158(24"C)
only end
absorption [H201
253
7800 [CHjOH]
285
6300 ICH3OHI
1.34
199
1.24 [61
192 I61
0.72
188
HCNO+, HCN*
CzHzN+, NO+
HCNS+, HCN+,
Si I51
lCNSe+,HCN +,
Set
159-160 "C.
A mixture of 226 g of (2), 335 g of 2,4-dinitrophenylhydrazine, 5 liter of ethyl alcohol, and 165 ml of concentrated
hydrochloric acid is refluxed for 48 to 72 h, and benzaldehyde dinitrophenylhydrazone is removed by filtration.
The filtrate is evaporated to dryness in Y ~ C U Oand extracted
with water. The aqueous solution is neutralized, the water is
evaporated, and the dry residue recrystallized from ether o r
acetonitrile to afford pure 2,4-dimethyl carbohydrazide, m.p.
65 "C.
Received: February 6th, 1967
[Z 448 IE]
German version: Angew. Chem. 79, 315 (1967)
[*I Dr. L. Raphaelian, H. Hooks, and Dr. G. Ottmann
Olin Mathieson Chemical Corporation, Chemicals Division
275 Winchester Ave.
New Haven, Conn. 06504 (U.S.A.)
[I] M . Freundand F. Kub, Chem. Ber. 23,2831 (1890); S. Skinner
and S . Rubemann, J. chem. SOC.(London) 1888, 551; P. Cazeneuve and Moreau, C. R. hebd. Seances Acad. Sci. 129, 1256
(1899); E. Bamberger, Chem. Ber. 44, 3746 (1911); E . P. Nesynov
and P. S . Pel'kis, 2. obi-5. Chim. 34, 2672 (1964); M . Mistry and
P. C. Cuba, J. Indian chem. SOC.7, 793 (1930).
[2] Brit. Pat. No. 898419 (June 6th, 1962).
131 C.Tb. Pedersen, Acta chim. scand. 18, 2199 (1964).
[a1
JI3C-H (Hz)
Mass spectrum:
major fragmentation products
T
Ial Solvent: CCI4; tetramethylsilane as internal standard
[Z 450 IE]
Received: February 6th, 1967
German version: Angew. Chem. 79, 315 (1967)
[*] Dr. L. M. Weinstock, Mr. P. Davis, Dr. D. M. Mulvey, and
Mr. J. C. Schaeffer
Merck Sharp and Dohme, Research Laboratories
Rahway, New Jersey 07065 (U.S.A.)
111 D . Sbcw, Ph. D. Thesis, Indiana University, 1959; Dissertation, Abstr. 20, 1593 (1959).
[2] Y. E. Shealy, J. D. Clayton, G. J. Dixon, E. A . Dulmadge,
R. F. Pittillo, and D . E. Hunt, Biochem. Pharmacol. 15, 1610
(1966).
[3] L. M . Weinstock, P. Davis, B. Handelsman, and R.Tull,
Tetrahedron Letters 1966, 1263.
[4] w = weak, m = medium, s = strong.
[5] F. H . Marquardt, Ph. D. Thesis, Indiana University, 1960;
Dissertation Abstr. 21, 3272 (1961).
[6] R. A . Olofson and J . S. Miche[man, 3 . org. Chemistry 30,
1854 (1965).
[7] L. M . Weinstock, Ph. D. Thesis, Indiana University, 1958;
Dissertation Abstr., 19, 3136 (1959).
Bis-(1,5-cyclooctacliene)platinum(0)
1,2,5-SelenadiazoIe
By J . Miiller and P . Goser 1 *I
By L. M . Weinstock, P . Davis, D . M . Mulvey, and
J. C . SchaefferI*I
If CODPtC12Ill (COD = 1,5-cyclooctadiene) is treated with
a n excess of iso-C3H7MgBr in ethereal solution, under N2 at
3,4-Dicyanoselenadiazole111 and 4-amino-l,2,5-~elenadiazole- -40 "C, and in the presence of COD, a dark yellow solution
results when the mixture is stirred for 3 h. After methanolysis
3-carboxylic acid [21 are known. We have now synthesized the
at -5OoC, removal of the solvent by distillation, and cryspreviously unknown parent compound 1,2,5-selenadiazole (1).
364
Angew. Chem. internat. Edit.1 Vol. 6 (1967) No. 4
tallization of the residue from hexane at a low temperature,
an Almost colorless, well-crystallizing, light-sensitive compound CODPt(iso-C3H7)2 ( I ) can be isolated in 40 %, yield
(m.p. 54-56 “C).
If a solution of this product ( I ) in COD at 2OoC under Nz is
irradiated for 22 h with UV light (Hg high-pressure lamp
Hanau Q 81), subsequent distillation of the COD in a high
vacuum and chromatography of the residue on neutral
A1203 (“Woelm”, 7 % Hz0) with n-hexane as eluent gives a
colorless solution from which, on cooling to -78 “C, colorless
diamagnetic (COD)zPt(O) (2) [m.p. 110-111 OC (decamp.)]
crystallizes in 22% yield.
Compound (2) is the first purely olefinic complex of zerovalent platinum. For comparison we prepared the known [21
yellow nickel complex (C0D)zNi (3) [m.p. 140-142’ (decamp.)] in 13 % yield by treating anhydrous NiC12 under Nz
with an excess of iso-C3H7MgBr and C O D in ether and
irradiating the resulting dark brown solution with UV light
for 8 h. The compounds (2) and (3) have similar properties
but (2) is more resistant to atmospheric oxidation.
In the 1H-NMR spectrum of (2) in C6H6, two signals
(intensity ratio, 1 :2) appear at T = 5.82 (olefinic protons) and
T = 7.81 (methylene protons).
The corresponding signals of (3) are at T = 5.64 and 7.84.
The signal of (2) at T = 5.82 shows two satellites ( J = 5 5 Hz)
caused by 1H-195Pt coupling; the corresponding satellites of
the methylene protons signal are poorly resolved.
The mass spectrum of (3) (Atlas mass spectrometer CH4,
ion source T 0 4 , 50 eV) shows mainly the ions (COD)2Nif
(relative intensity Zr = 27.9), CODNi+ (Ir = 100.0), C&Ni+
(Ir = 65.9), and Ni+ (Ir = 8.2). Under similar conditions the
complex (2) gives an appreciably more complicated mass
spectrum; the principal ions (COD)2Pt+ and CODPt’ are
accompanied by several groups of less intense peaks arising
mainly by successive loss of C2 and C3 units from the molecular ion. The mass spectrum of the free ligand, which is
liberated on thermal decomposition of the complex, is also
detectable with both (2) and (3).
The IR spectrum of (2), which contains many lines, is
characterized by the following bands (KBr) : 2994, 2907,
2853, 2801, 1471, 1458, 1445, 1392, 1361, 1323, 1299, 1230,
1203, 1171, 1151, 1085, 1068, 1000, 990, 954, 879, 860, 845,
820, 813, 803, 779, 760, and 673 cm-1.
Attempts to prepare di(norbornadiene)platinum(O) have so
far failed. Treatment of nor-C7HsPtC12 (31 with an excess of
iso-C3H,MgBr in ether under N2 at -40 “C gave almost an
80 % yield of well-crystalline yellow nor-C7HsPt(iso-C3H7)2,
but UVirradiation of this material in norbornadiene did not
give the desired purely olefine complex.
Received: February 17th, 1967
[ Z 451 IE]
German version: Angew. Chem. 79, 380 (1967)
[*I Dr. J. Miiller and Dipl.-Chem. P. Goser
Anorganisch-Chemisches Laboratorium der
Technischen Hochschule
Arcisstr. 21
8 Munchen (Germany)
[l] J . Chatt, L. M. Vallarino, and L. M . Venanzi, J. chem. SOC.
(London) 1957, 2496.
[2] B. BogdunoviC, M . Kroner, and G. Wilke, Liebigs Ann. Chem.
699, 1 (1966).
131 E. W. Abel, M. A . Bennet, and G. Wilkinson, J. chem. SOC.
(London) 1959, 3178.
1,3-Cycloadditions of Mesoionic Oxazolones to
Carbonyl Compounds
By R . Huisgen and E. Funke [*I
The mesoionic oxazolone ( I ) is a very active azomethine
ylide; its 1,3-adducts with acetylene derivatives or with
olefins are stabilized by loss of carbon dioxide, yielding
Angew. Cliem. internat. Edit. Vol. 6 (1967)
1 No.4
pyrrole
o r 2-pyrroline derivatives, respectively [21. Aldehydes, a-diketones, and a-keto carboxylic esters can also
induce elimination of carbon dioxide from ( I ) , such reactions
yielding the N-benzoylalkenylamines (4) to (11).
c H,
C6H5
’
‘C.,N.<*
,C6H5
R
131
I Reac-
/K
R
Yield
tion
temp.
( %)
M.P. ( “ C )
I
H
H
H
H
H
CsH5
C02CH3
COiCzHs
80
[a1
33
37
36
100
20
20
48
45
32
49
59
66
73
49
66
46
52
45
60
51
57
93-94
139
110.5-1 11.5
140- 141
149-1 50
191
103-103.5
103-104.5
[a] From (15) at 120°C
Proofs of structure: (4) was hydrogenated to a product
identical with authentic N-methyl-N-(or-phenethy1)benzamide.
(5) and an acid solution of 2,4-dinitrophenylhydrazinegave
a 92 ”/, yield of the propiophenone derivative. Analogously
(6) was converted into deoxybenzoin 2,4-dinitrophenylhydrazone in 81 % yield. With 85 % phosphoric acid the
benzil adduct (9) afforded w,w’-dibenzoyltoluene in 65 %
yield; similar treatment of ( I I ) yielded acetophenone,
benzoic acid, methylamine, and CO2. The amide I bands of
( 4 ) to ( I I ) are at 1627-1655 cm-1.
If the oxazolone ( I ) is stirred slowly into an ethereal solution
of an excess of diethyl mesoxalate, addition of the dipolarophile to the intermediate ( 3 ) . which is a new cyclic azomethine ylide, competeswithring opening of this intermediate
t o give ( I I ) . The product is the bicyclic diadduct (12) which
on mild treatment with acid gives the p-lactone (13) (C=O at
1820, 1755, 1737 cm-1) and on energetic hydrolysis in the
presence of 2,4-dinitrophenylhydrazinegives phenylglyoxal
osazone. (12) decomposes at 160°C into mesoxalic ester and
80 % of (11).
Treating the oxazolone ( I ) with acetaldehyde at 0 ° C
afforded 73 % of a bisadduct (15), without loss of carbon
dioxide. Presumably here the intermediate (2) is trapped by
addition of the second molecule of acetaldehyde, which
yields (14). Ring opening thereof then explains the formation
of the oxazolidone derivative (15) [NMR (in CDCI-,),
2 CH--CH3 3.89 (4) and 8.44 (d) T, as well as 5.48 (9) and
8.83 (d) T; IR (KBr), ring C = O 1788, ester C=O 1715 cm-11.
365
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