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Condensation of Methyldichlorophosphine with Dithiols.

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T he usual route for the synthesis of nitrile oxides, viz. chlorination of the oximes ( 1 ) t o afford th e hydroxamyl chlorides
f S ) , followed by dehydrohalogenation of (8) with base, was
found totally unsuitable for the preparation of ( 2 0 ) - ( 2 d ) ,
since chlorine always substituted simultaneously in th e g r o u p
R. However, the alkali salts of th e oximes ( f c / ) - ( / d ) were
readily dehydrogenated with alkyli hypobromite at 0-10 O C
t o afford the nitrile oxides (2a)-(2c/) in excellent yields. Th e
melting points a nd yields of compounds (2) an d ( 5 ) -(8) ar e
given in T a ble 1.
Table I . Melting points and yields of the nitrile oxides ( 2 ) and their reaction
products ( 5 ) - ( 8 ) .
Compound
ibl
114
97 [6
120
(5)
160
91
247
94
300
79
M.p. [ T I
Yield [ %]
(6)
94
98
175
88
312
M.P. I T ]
(71
245
306
-
M.p. ["C]
Yield [ % I
(2)
M.p. [ " C ]
Yield 1x1
169-170
65
98 161
95
[*I
['I
160-170
79
199
85
[*I
['I
[*I
Received, June 5th, 1964
[Z 751jS85 IE]
German version: Angew. Chem. 76, 647 (1964)
98
86
[51
124-126
81
is left as residue. Th e compound Kj[AI(SCN)6] (2) is obtained
free from acetonitrile by heating ( J ) at 140 "C in a stream of
nitrogen.
Both ( I ) an d ( 2 ) dissolve in water t o give a clear, colorless
solution with an acidic reaction, and in liquid ammonia t o
give a bright yellow solution. On evaporation of the ammonia,
a mixture of an ammonate of aluminum thiocyanate a n d potassium thiocyanate results. Accordingly, (1) an d f2) behave
like potassium hexathiocyanatotitinate(1V) [I].
T h e reaction of 3 moles of potassium thiocyanate with 1 mole
of anhydrous aluminum chloride in acetonitrile leads t o precipitation of only 2 moles of potassium chloride with formation of a solution of the complex K[AI(SCN)3Cl] (3). This
complex is stable only in solution. It is assumed that t h e complex ion still retains acetonitrile as a ligand bound t o t he
Th e residue obtained
AP+, e . g . as [AI(SCN),CI(NCCH,)$.
after evaporation of t h e acetonitrile consists of a mixture of
potassium chloride a n d a n adduct of acetonitrile an d aluminum thiocyanate. On adding this mixture t o acetonitrile,
it dissolves t o reform complex (3).
[I] 0. Schmitz-DuMunr and B. Ross, Angew. Chem. 76, 304
(1964): Angew. Chem. internat. Edit. 3, 315 (1964).
-
A New Synthesis of Germylsilane [ *]
Aliphatic nitrile oxides a r e by far more transient th a n their
aromatic counterparts; their most stable representative seem$
t o be t-butylnitrile oxide [7], b u t even this compound dimerizes completely t o the furoxan within 2-3 days [3]. To obtain
really stable aliphatic nitrile oxides, even bulkier groups will
be required next to the - C - N + O
grouping. We ar e at
present engaged in preparing such compounds.
Received, June 5th, 1964
[Z 759/571 IE]
German version: Angew. Chem. 76, 682 (1964)
[ I ] Nitrile Oxides, Part 11. - Part I : Ch. Grundinann, Angew.
Chem. 75, 450 (1963); Angew. Chem. internat. Edit. 2, 260
(1963).
[2] This work was supported by Public Health Service Research
Grafit CA-07272-01 of the National Cancer Institute, Bethseda,
Md (U.S.A.).
[3] For the rate of dimerization of known aromatic nitrile oxides,
cf. A . Quilico: The Chemistry of Heterocyclic Compounds. Interscience, New York 1962, Vol. 17, p. 21, Table 11.
[I] For previous unsuccessful attempts to prepare terephthalobisInitrile oxide), cf. R . H . Wiley and B. J . Wakefield, J . org.
Chemistry 25, 546 (1960). Oxalobis(nitri1e oxide) has been obtained so far only in solution [I].
[5] Not determined.
[6] For infrared spectra, see S. Califano, R. Moccia, R . Scarpati,
and G. Speroni, .I. chem. Physics 26, 1777 (1957).
[7] S . Califano, R . Scarpati, and G . Speroni, Atti Accad. naz. 1.hcei, Rend., CI. Sci. fisiche, mat. natur. [8] 23, 263 (1958); Chem.
Abstr. 52, 12557 f (1958); G. Zinner and H . Gunther, Angew.
Chem. 76,440(1964); Angew. Chem. internat. Edit. 3,383 (1964).
Preparation of Anhydrous Potassium
Hexathiocyanatoaluminateand Its Behavior
in Liquid Ammonia
By Prof. Dr. 0. Schmitz-DuMont an d Dipl.-Chem. B. Ross
Anorganisch-Chemisches Institut der Universitat Bonn
(Germany)
When 1 mole of anhydrous aluminum chloride is added t o a
solution of 6 moles of potassium thiocyanate in acetonitrile,
potassium chloride is precipitated. If th e potassium chloride
is filtered off a n d t h e filtrate evaporated t o dryness in vucuo
a t room temperature with exclusion of moisture, a pale pink,
crystalline thiocyanato complex K3[AI(SCN)6].CH3CN ( I )
586
By R. Varma and A. P. Cox
Mallinckrodt Chemical Laboratory, Harvard University,
Cambridge, Mass. (U.S.A.)
Previously, silylpotassium H3SiK [ l ] has been used t o only a
limited extent in inorganic synthesis. Silylpotassium was prepared by the reaction (a) of disilane SilH6 with a slight excess
of potassium hydride in 1,2-dimethoxyethane over a period
of 24 hours at r o o m temperature. After removing volatile
products - mainly monosilane, monoglyme, some hydrogen,
a n d a very small quantity of disilane
an excess of germyl
chloride was distilled in an d allowed t o react with t he
H3Si I< at r o o m temperature for 15 minutes (b). The germyl-
Si2H6 ,- K H
--f
HASiK 7 - SiH?
H 6 i K t GeH3CI + GeHJSiH3
(a)
(b)
silane GeH3SiH3 [Z] produced was purified by fractionation
o n a low-temperature column kept a t approximately 115 OC
in order t o separate it from Si2H6 a n d G q H , , and was o btained in ca. 20 72 yield.
Its infrared an d mass spectra agree with those cited in reference [Z] for GeH3SiH3. In addition, its microwave spectrum
[3] strongly supports this identification.
~-
[Z 757/573 IE]
Received, June 8th, 1964
German version: Angew. Chem. 76, 649 (1964)
[*I Part of the research was made possible by support extended
to Harvard University by the Office of Naval Research.
[l] M . A . Ring and D . M . Ritter, J. Amer. chem. SOC.83, 802
(1961).
[2] E. J. Spanier and A . G . MacDiarmid, Inorg. Chem. 2, 215
(1963).
[3] R . Varma and A. P. Cox, unpublished results.
Condensation of Methyldichlorophosphine
with Dithiols
By Dr. M. Wieber, Dipl.-Chem. J. Otto, and
Prof. Dr. Max Schmidt
Institut fur Anorganische Chemie der Universitlt
MarburglLahn (Germany)
Methyldichlorophosphine ( I ) reacts in ether in the presence
of triethylamine (2) with dithioglycol or 3,4-dimercaptotoluene in very good yields t o f o r m 2-methyl-l,3,2-dithiaAngew. Chem. internot. Edit.
Vol. 3 (1964) 1 No. 8
phospholane (3) or 2,7-dimethylbenzo[d]-1,3,2-dithiaphospholanc ( 4 ) , and triethylammonium chloride (5).
sodium acetate, and by treatment of ( 3 b ) with aluminum
chloride in nitrobenzene or with concentrated sulfuric acid
were unsuccessful. When the ester ( 3 0 ) was boiled with acetic
anhydride/acetic acidlzinc chloride, only the anhydride of
( 3 b ) was formed.
4)
Analogously, propane- 1,3-dithiol produces the six-membered
heterocycle 2-methyl- 1,3,2-dithiaphosphane (6), but only in
moderate yield (ca. 30 %), the remainder forming a polymer of
the same composition. All three derivatives [ ( 3 ) , m.p. -5 "C,
b.p. 90"C/5 mm; ( 4 ) , b.p. 110-114"C/2 mm; and (6), b.p.
102 "Cj5 mm] distil undecomposed and are oils of unpleasant
odor; they are readily soluble in organic solvents, and easily
hydrolysed by water. As nucleophilic reagents, they react with
sulfur and selenium, yielding cyclic esters of methyltrithiophosphonic or methyldithioselenophosphonic acid, e. g .
We have now found that the reaction of ( 3 0 ) with acetic anhydride and aluminum chloride gives an uncharacterized
intermediate which is converted into ( 4 0 ) in good yield with
)
be cyclized with
alkali. Halogeno derivatives of ( 3 ~ can
acetic anhydride/acetic acid/zinc chloride. Thus, for example,
the monoethyl ester ( 3 c ) obtained from 2,7-dichlorofuorenone by Stobbe condensation gives, in addition t o the anhydride of the dicarboxylic acid ( 3 d ) , the intermediate (4h),
which on hydrolysis yields 4,9-dichloro-3-hydroxyfluoranthene-I-carboxylic acid (4c), a compound we had already
prepared by another route [3].
[ Z 756/586IEI
Received, June Sth, 1964
German version: Angew. Chem. 76, 648 (1964)
Thus, (3) and S afford 2-sulfo-2-methyl-l,3,2-dithiaphospholane, m.p. 74"C, b.p. 132-134'C/Zmm; (3) and Se form
the corresponding selenophospholane, m. p. 68 "C, b. p.
148'C/2 mm; (4) and S or Se yield the sulfophospholane (7)
or selenophospholane respectively; but neither can be distilled
unchanged. Finally (6) and S produce the corresponding
sulfophosphane, m.p. 121 " C .
An attempt to oxidize (3) to the dithiophosphonic ester with
oxygen at room temperature failed; warming led to a violent
explosion.
Received, June 8th, 1964
[ Z 753/584IE]
German version: Angew. Chem. 76, 648 (1964)
The Synthesis of Fluoranthene Derivatives from
Monoethyl 4,4-(o,o'-Biphenylene)itaconate
By Prof. Dr. A. Sieglitz and Dipl.-Chem. P. Bohme
Institut fur Chemische Technologie der Farbstoffe und Kunststoffe, Technische Hochschule Miinchen (Germany)
Some time ago, Borsche [l] obtained I-hydroxy-4-phenyl-3naphthoic acid (2b) from the ester (2a), which was synthetized by cyclizing monoethyl 4,4-diphenylitaconate (I) with
acetic anhydride and sodium acetate; ( I ) was derived in turn
from benzophenone by Stobbe condensation [2].
Numerous derivatives of ( 2 b ) can be prepared by this route.
3-Hydroxyfluoranthene-I-carboxylicacid ( 4 0 ) [ 3 ] should be
accessible by a similar route from fluorenone via the monoethyl ester ( 3 a ) of 4,4-(o,o'-biphenylene)itaconic acid ( 3 b ) .
However, attempts by Campbell and Fairfitl[4] to close the
fluoranthene ring by reaction Of (3~7)with acetic anhydride/
Angew. Chem. internat. Edit. 1 Vol. 3 (1964) 1 No. 8
[ I ] W. Borsche, Liebigs Ann. Chem. 526, I (1936).
[2] H . Stobbe, Liebigs Ann. Chrm. 308, 67 (1899).
[3] A . Sieglitz, H . TrBster, and P . Bohme, Chem. Ber. 95, 3013
(1962).
[4] N . Campbe// and A. E. S. Fairficl, J. chem. SOC.(London)
1949, 1102.
Non-Enzymatic Reduction of Methylene Blue and
2,6-Dichlorophenolindophenolby Reduced Di- and
Triphosphopyridine Nucleotides
By Dip1.-Chem. F. Wagner, Prof. Dr. J. Convit,
E. Bernt, and Dr. M. Nelbock
Escuela Jose Vargas, Hospital Vargas, Caracas (Venezuela),
and Biochemische Abteilung, C. F. Boehringer & Soehne
GmbH, Tutzing (Germany)
Contrary to expectations, methylene blue (MB) is stoichiometrically decolorized to leuco-methylene blue (MBH2) by
the reduced di- and triphosphopyridine nucleotides D P N H
and T P N H on irradiation with light w i t h o u t addition of
enzymes. The most effective wavelengths are those between
600 and 700 my.
The DPN or TPN thereby formed is fully active in enzymatic
reactions, c.g. with the DPN-dependent enzymes lactic dehydrogenase and alcohol dehydrogenase, and the TPNdependent enzymes glutathione reductase and glucose-6phosphate dehydrogenase.
2,6-Dichlorophenolindophenolis similarly reduced, but triphenyltetrazolium chloride is not.
The same reactions were carried out with absolutely pure
DPNH and TPNH. Traces of proteins were removed by dialysis, and possible traces of enzymatic activity were destroyed
by heating the coenzyme solutions at 100 "C. Any enzymatic
reaction (e.g. of diaphorase) was thus excluded.
Flavin adenine dinucleotide ( 4 10-5
~ M ) accelerates the reoxidstion of MBH2 to M B by atmospheric oxygen, and thus
leads to a faster oxidation of DPNH. Glutathione (10-4 M )
and ferric chloride (3 Y 10-5 and 3 x 10-4 M) did not affect the
reaction rate.
587
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