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Disubstituted Dithiane Rings.

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New Nitrogen-Iodine Compounds
By DOL. Dr. .I.Jander, Dipl.-Chem. U. Engelhardt, and
Ilipl.-Chem. G . Weber
Attempts to prepare dialkylphosphorus tribromide from ( I )
led to compounds of the type R2PBrs (111, yield about 80 2,).
even when the molar ratio ( I ) : Br2 was varied. Apparently,
the reaction
K ? l ' H r l + Br?
Chemisches Laboratorium der Universitit Freiburg/Br. (Germany), Anorgdnische Abteilung
A new preparative method for a n already known [I, 21, red
N I compound has been found. It may be prepared alongside NH41 as a difficultly soluble, finely divided material from
a small quantity of iodine (.c 0.1 g.) and a n excess of liquid
ammonia at -78 "C. The conversion to the green compound
NI3.3 NH3 [ I , 31,which is produced directly by starting from
more iodine ( 2 5 g.), takes place via rust-red, brown, and
green-brown intermediates. After isolation, the red material
turns black while the ammonia is pumped off under high
vacuum between 105 and -90 OC. (the process is reversible);
the N : I ratio is then equal to I . An infrared investigation of
the structure is being carried out.
The brown NI3.NH3 compound [llyields: 1.Anorange-yellow
form C H J N I ~ C H ~ N
by analysisand its infrared
spectrum) which is obtained at --75"C. with a n excess of
amine (CH3NH2), and which is produced by way of a n insoluble, deep-green intermediate. 2. Yellow (CH3)zNI at
75°C. with excess (CH3)z N H ; this compound has been
previously prepared by another route [4].3. A dark-green solution with excess pyridine at -40 "C. The starting material
can be recovered unchanged by pumping off the pyridine at
25 "C.
proceeds much faster than the reaction of the dialkylphosphorus thiobromides RZP(S)Br [2] with bromine in an analogous manner to equation (2).
(CzH5)ZPBrs. m.p. 103.5 "C, and ( C ~ H ~ ) ~ P Bm.p.
T S .87.5 OC,
were obtained as orange-red needles, which melt without decomposing and which are quickly hydrolyzed with water
according to
+ 2 HzO - > R z P ( 0 ) O H + 3 H B r + R r r
The solubility of (11) and ( I l l ) in polar solvents, 3s well
as the results of conductivity measurements in dirnethylformamide, indicate a n ionic structure for these substances
- and [RZPBrz]' Br3 -.
according to [R~PCIZ]+[R~PCI.+~
Received October 31, 1961
[Z 175/14 IE]
[ I ] M . J. Kabatschnik and J . S. Shepelewm, lzvestiya Akad. Nauk
S.S.S.R. 1949, 56.
121 W . Kuchen and H . Buchwald. Angew. Chem. 7 1 , 162 (1959).
[3] P . J . Christen, L. M . van der Linde, and F. N . Hooge, Recueil
Trav. chim. Pays-Bas 78, 161 (1959).
[4] K . Issleib and A. Tzschach, Chem. Ber. 92,704 (1959).
[Z lSZ/S IE]
Disubstituted Dithiane Rings
[ I ] J . Juncliv and E. Srhmid, Z. anorg. allg. Chem. 304, 307
By Dr. B. Hirsch and Dipl.-Chem. H. Fink
Received October 26, 1961
( 1960).
[2] J . Junrler and E. Schmid, Angew. Chem. 7 1 , 31 (1959).
(31 J . Junder and E. Schmid, Z. anorg. allg. Chem. 292, 178
14) F. Roschig, Liebigs Ann. Chem. 230, 223 (1885).
Simple Process for Preparing Dialkyl Phosphorus
Halides RZPC13 and R2PBrS
lnstitut fur Farbenchemie
der Technischen Universitit Dresden (Germany)
R . Tschesche [ I ] obtained a crystalline product from y-acetylmercaptopentene-(2) acid ethyl ester by the reaction of
methanolic sodium hydroxide solution and described this as
acid. We have studied
this reaction in more detail.
a,@-Unsaturated compounds o f the type
By Doz. Dr. W. Kuchen and Dipl.-Chem. K. Strolenberg
Institut fur Anorganische Chemie und Elektrochemie der
T. H. Aachen (Germany)
a) COOCzHs
b) COOCzHs
Ilialkylphosphorus trichlorides (11) were obtained in about
80 yc: yield by reacting the readily available tetraalkyldiphosphine disulfides [l-41 R2P(SJ--P(S)Rz (I) with Clz in CCI4
according to the reactions
(I) ( I )
+ C'I,
+ 4 Clz -+ 2 R2PCls + 2 SC12
+ RCI;
+ 2 HlO
> R?P(O)OH
were brominated in the ally1 position with N-bromosuccinimide (Wohl-Ziegler method) and allowed to react at room
temperature in benzene solution with methanolic potassium
thioacetate solution. y-Acetylmercapto compounds (11) are
formed in yields of 90 to 95 %. They are colorless to light
yellowish oils with a weak but persistent odor.
since Cy2H5PC12was obtained in the thermal decomposition of
(C2H5)2PCI3. Water causes instantaneous hydrolysis:
c) C-H
d) CN
2 K?I'(S)CI
.- RPCI2
.* 2 RzP(S)CI
The dialkylphosphorus thiochlorides, formed primarily according to Equation ( l ) , could be recovered under suitable
conditions. Dialkylphosphorus trichlorides are colorless
crystalline substances which liquefy instantaneously on contact with atmospheric moisture. At room temperature, and
with the exclusion of moisture, they show no changes even
after standing for a month. They are thermally very unstable.
For example, (CzH5)2PC13 decomposes above 65 'C., and
(CjH7)2PC13 above 55 "C. with effervescence, presumably
according to the equation
+ 3 HCI.
Deep red solutions are formed if sufficient methanolic sodium
hydroxide to saponify the acetylmercapto group (possibly
also R1 = COOCzH5) is slowly added to an approximately
Angew. Chem. internal. Edit. I Vol. I (1962)
No. I
30 %' methanolic solution of I1 at room temperature and
under a nitrogen atmosphere (PH always < 8-9).
The solutions are allowed to stand overnight and are then
diluted with water, acidified with dilute H2S04, ethered out,
and the solvent evaporated o@. In addition to large quantities
of ill-smelling,yellow to red-brown viscous products, colorless
crystalline substances are obtained with I I a and IId whose
IR-spectra, analyses, and molecular weight determinations
point to dithiane substances.
p-nitrobenzalazine [4], and 57-67 % of the azidinium salt
(111) [5] determined optically as dye (IV) which is formed with
excess 1-phenyl-3-methylpyrazolone-(5) [5 1.
Rl -CHz-CH111
VI n=O
Yield 22.7 %; m.p. (sub].) 180°C.
Yield 22.0 %; m.p. 184OC.
I I c gives a colorless polymer only soluble in dimethylformamide and no longer gives any aldehyde reactions.
I1 b and IIe yield no crystalline products.
The addition of the intermediary free mercapto group to the
double bond of an adjacent molecule with the formation of
dithiane rings appears to be favored if; a) a primary mercapto
group can form; b) the polarization of the double bond by a
carbonyl or nitrile group in a conjugated position is strong
enough or; c) if no other reaction course (e.g. reaction of the
mercapto group and aldehyde group) is possible.
Received November 6, 1961
When (11) is heated to 110 "C.,the triaza-trimethine cyanine
V (55 %) and monoaza-cyanine VI (24 %), each determined
optically, are both formed and nitrogen is evolved. This is
further support for the structure of (11).
The formation of compound (11) is the cause of the purple
color which was obtained by E. Besthorn [6]from (I) with
NaNO2 in a weakly acidic medium, and which was observed
by G. Hensecke and G . Hanisch [7]when solutions of (I) and
(111) were mixed. Presumably, the excess azidinium salt (111)
is the dehydrogenating agent [8]. Accordingly, both symmetrical and unsymmetrical penta(aza)-pentamethine cy anines, for example (VII), can be builf up from azidinium saIts
and "hydrazones" having a different heterocyclic ring.
[Z 167/9 1EJ
[I] R. Tschesche, H. Barkemeyer, and G. HenschkeZ, Chem. Ber.
88, 1261 (1955).
VII Amax.
579 rnfi in acetonitrile
Received November 6, 1961 [Z 162 3 IE]
Penta(aza)-Pentamethine Cyanine Dyes
By Prof. Dr. S. Hunig [l], Dozent Dr. H. Balli, and
DipLChem. H. Quast [2]
Chemisches Institut der Universitat Marburg
und Institut fur Organische Chemie der Universitat Miinchen
It has been possible for some time to synthesize tetra(aza)pentamethine cyanines 131, and we now report the isolation
of the penta(aza)-pentamethine cyanines. The bis-O-methylbenzthiazol-2-yl)-derivative (11) is formed as a purple dye
salt in the oxidation of 3-methylbenzthiazolone-2-hydrazone
fluoborate (Ia) with lead tetraacetate in a weakly acidic
methanol solution.
[I] New address: Wiirzburg, Chemisches Institut der Universitat, Rontgenring 11.
[2] From the Diploma-Thesis of H. Quast, University of Marburg, 1961.
[3] S. Hiinig and K . H. Frittch, Liebigs Ann. Chem. 609, 172
[4]S.Hiinig and H . Balli, Liebigs Ann. Chem. 609,160 (1957).
[S] H. Ealli. Angew. Chem. 70, 442 (1958).
161 E. Besthorn, Ber. dtsch. Chem. Ges. 43, 1524 (1910).
[7]G. Henseke and G. Hanisch, Liebigs Ann. Chem. 643, 184
181 H. BaZZi, Habilitationsschrift, University of Marburg, 1960.
Trithiocarbonic Acid H2CS3
By Priv.-Doz. Dr. G. Gattow and cand. chem. B. Krebs
Anorganisch-chemisches Institut der Universitat Gottingen
Trithiocarbonic acid is formed as a highly refractive red oil
when solid BaCS3 is introduced into ice cold 10% hydrochloric acid [l, 21. The substance has now been accurately
characterized. The molecular weight, determined cryoscopically in bromoform, is 109.9 f 0.5 (theoretical: 110.2).
Molecular weight determinations just above the melting
point seem to indicate a partial association. Density, determined with a micropycnometer: di5 = 1.476 f 0.003 g./ml. ;
d$O = 1.483 0.003 g./ml.; refractive index: nB = 1.8225
0.0005; melting point: -26.9 "C. (* 0.2'); boiling point:
+57.8 "C. (extrapolated). The infrared spectra of the free
acid as well as of the solution in CCl4 show strong bands
with absorption maxima at 2580, 1508, 1120, 990, 879, 798,
and 466 cm-1.
Compound (11) forms metallic, shiny green, needles from
acetonitrile at very low temperatures (Amax. 552 mp; E =
55500 in acetonitrile). If it is titrated with Tic13 in acetonitrile until colorless, two reduction equivalents are absorbed. The reduction yields 81-87 % (I), isolated as the
Angew. Chem. internat. Edit.
Vol. 1 (1962) I NO.I
The decomposition pressures of H2CS3 were determined by
direct measurement (isoteniscope). The decomposition equation [3]
H2S(gas) + CS2(dissoIved)
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disubstituted, ring, dithian
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