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New Heterocyclic Ring Systems.

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The reactants are heated with aluminium chloride under
reflux, and the trimethylchlorosilane formed is continuously
removed.
fZ333/162 IE]
Received, August 20th, 1962
[l] W. Sundermeyer, 2. anorg. allg. Chern. 313, 290 (1962).
[2] L. Birkofer, A. Ritter, and P. Richter, Angew. Chem. internat. Edit. 1 , 267 (1962); cf. [5].
[3] Cf. E. Wiberg and H . Michaud, 2. Naturforsch.9b, 500 (1954).
[4) During publication N. Wiberg, F. Ruschig, and R. Sustmann
reported the successful preparation of diphenyldiazidosilane:
Angew. Chem. internat. Edit. I, 551 (1962).
[ 5 ] R. West and J . S. Thayer, J. Amer. chem. SOC.84, 1763 (1962).
161 N . Wiberg and F. Raschig, Angew. Chem. internat. Edit. I,
335 (1962).
[ *] w = weak, vs = very strong.
N-Sulphonyliminodithiocarbonic esters and
N-Sulphonyldithiourethanes
By Doz. Dr. R. Gompper and Dipl.-Chem. W.. Hagele
Institut fur Organische Chemie und Organisch-chemische
Technologie der Technischen Hochschule Stuttgart (Germany)
The reaction of sulphonamides with carbon disulphide has not
been described previously. It may proceed in the following
manner :
RS02NH-C
111
RSOzNHz
+ CS2 + 2 M O H +
1
Isoselenazole and 3-Methylisoselenazole
RX
2. HCI ,S-
By Prof. Dr. F. Wille, A. Ascherl, G. Kaupp, and L. Capeller
RSOzN=C\
I
11
5 2
s-
Institut fur Anorganische Chemie der Universiat Munchen
(Germany)
RX
/SR'
RSOzN=C
1v
MOH = base
[l] Prepared by Badische Anilin- & Soda-Fabrik, Ludwigshafen/Rhein (Germany).
/SR'
AS
1.
celluloses with basic substituents used hitherto. This may be
mainly attributed to the fact that a considerably higher nitrogen content (and hence capacity) can be achieved by impregnation of the cellulose rather than by substitution.
For example, a strip of Whatman No. 1 paper is soaked for
1-2 sec. in a 1-5 % solution of polyethyleneimine neutralised
with hydrochloric acid, air-dried, washed with distilled
water, and dried in a current of warm air.
The anion-exchanger paper thus obtained is excellently suited
for separating nucleotides and other phosphoric esters, for
example, AMP, ADP, and ATP can be separated in 12 min.
on polyethyleneimine-paper with 0.8 M sodium chloride
solution. This takes 15 to 20 hrs. on untreated paper (partition
chromatography), and on commercial ion-exchanger papers
(substituted celluloses) they cannot be separated at all with
neutral electrolytes.
Impregnated celluloses are also suitable for column and
thin-layer chromatography, separations being particularly
sharp in the latter case. A mixture of AMP, ADP, and
ATP can be completely resolved in 3-4min. on a polyethybneimine-cellulose layer with 0.8 M sodium chloride
solution.
The mild conditions of these separations seem particularly
noteworthy.
[Z 336/168 IEI
Received, August 30th, 1962
RS'
Suitable solvents include dimethylformamide, N-methylpyrrolidone, and dimethylsulphoxide, while conc. sodium or
potassium hydroxide may be used as base.
The salts I1 may be isolated or converted directly into I11 and
IV. Good yields can be obtained only if MOH and CSp are
added in portions to the solution of I (at first 1 equivalent of
MOH and 1 / p equivalent CSz, then 1/2 MOH and 114 CSp,
and so on). The alkylthio groups in 111 and IV undergo
nucleophilic substitution readily. As coreactants we have so
far used alcohols, ammonia, primary and secondary amines,
diamines, aminoalcohols, ethyleneimine, hydrazine, guanidine, and CH-acid compounds. Replacement of the second
alkylthio group in IV proceeds only under morevigorous conditions (e.g. with NH3 in phenol at l0OOC).
Oxidation of 111 gives N,N'-disulphonylisothiuram disulphides. Heating I11 in an inert solvent eliminates an alkylthiol; perhaps sulphonyl-mustard oils are also formed as
intermediates on heating in alcohol; these then react further
to form N-sulphonylthiocarbamic esters.
Received, August 30th, 1962
We recently reported that on treatment with ammonia 3thiocyano-acrolein is converted into isothiazole [I 1. An analogous cyclization occurs when 3-cyanoseleno-acrolein (I,
R=H) is treated with liquid ammonia. The product is the
hitherto unknown isoselenazole (11, R=H), a colorless liquid
with a pyridine-like odour (b.p. = 68"C/46mm.; n g =
1.603; Amax = 266 mp; E = 4680, in dioxane)
Ammonia and 3-cyanoselenobutenone (I, R=CH3) yield the
analogous 3-methylisoselenazole (11, R=CH3 ; b.p. = 51 to
51.5 OC/13 mrn; n 8 = 1.575; Amax = 268 mp; E = 3630, in
dioxane).
Cyanoseleno-acrolein (I, R = H; m.p. = 73-75 "C)is prepared by the addition of selenocyanic acid to propynal; 3cyanoseleno-butenone (I, R = CH3; m.p. = 50-53OC) is
obtained similarly from butynone.
Received, September 7th. 1962
[Z 337/167 IE]
[Z 335/166 IE]
[l] F. Wiiie, L. CupeZZer, and A . Steiner, Angew. Chem. Internat.
Edit. I, 335 (1962).
A Simple Method for Preparing Cellulose
Anion-exchanger Powders and Papers
New Heterocyclic Ring Systems
By Dr. K. Randerath
By Dr. K. Stach and Dr. F. Bickelhaupt
Institut fur Organische Chemie der Technischen Hochschule,
Darmstadt (Germany)
We have found that cellulose powder and chromatography
paper can be impregnated with polyethyleneimine [l] to produce anion-exchanger materials which give excellent resolution. These exchangers are markedly superior to
Augew. Chem. internat. Edit. 1 Voi. 1 11962)
NO.10
C. F. Boehringer & Siihne G.m.b.H.,
Mannheim-Waldhof (Germany)
7,12-Dihydro-6H-dibenzo[b,e]thiocin-l2-one
(I) (m.p. 149
to 149.5'C, from diethyl ketone) is prepared smoothly in
70 % yield within 30 min by dehydration with polyphosphoric
553
acid at 110 OC of o-(P-pheny1ethylmercapto)benzoicacid (11),
which is obtained by treatment of the sodium salt of methyl
thiosalicylate with P-phenylethyl bromide in boiling methanol,
followed by hydrolysis (m.p. 123 'C; yield: 85 %, based on
methyl thiosalicylate). I is also obtained in 45 % yield by
cyclisation of o-(phenylethy1mercapto)benzoyl chloride (b. p.
191-196 '(70.2 mm, obtained by treatment of I1 with thionyl
chloride) with aluminium chloride in a carbon disulfidenitrobenzene mixture.
The action of polyphosphoric acid on o-(P-phenyl-mercaptoethy1)benzoic acid - an isomer of I1 - affords only a 10 %
yield of I. This is remarkable, because ring systems containing one niethylene group less, viz. 6.1 1-dihydro[b,e]thiepin-11-one [l-31 or -oxepin-11-one [l] are produced in
80-90 % yield by cyclising o-(phenylmercaptomethy1)- or
o-(phenoxymethy1)-benzoic acid or their derivatives, respectively.
Reaction of I with Grignard reagents, e . g .
CIMg(CH2)3N(CH3)2, in tetrahydrofuran produces, as in
the cyclooctene [I c], thiepine [l c, 2,3], and oxepine series
[lc], the corresponding carbinol (m.p. 138.5 - 140 OC;
93 %), which is convertible by dehydration (e.g. with alcoholic hydrochloric acid) into 12-(3-dimethylaminopropylidene)-7.12-dihydro-6H-dibenzo[b,e]thiocine(b.p. 184-185 "C/
0.3 mm; 83 %I.
Received, August 31st. 1962
[Z 334/165
IE]
[I] a) K . Stach and H. Spingler, Angew. Chem. 74, 31 (1962).
b) K . Stuch and H . Spingler, Monatsh. Chem., in press; c) K .
Stach and F. Bickelhaupt, Monatsh. Chem., in press.
[2] M . Protiva, M . RajSner, V . Seidlovri, E. Adlerovri, and Z . J.
Vejdglek, Experentia 18, 326 (1962).
[3] Sandoz, Belg. Pat. 607503 (Aug. 24th, 1961; published,
Febr. 26th, 1962).
Inorganic Redoxites [*]
By Dr. B. Sansoni and DipLChem. 0. Sigmund
Chemisches Institut der Universitat Marburg/L. (Germany)
As the first purely inorganic counterpart to organic redox
resins the clay mineral Nontronit [l] was examined [2].
Aluminium in the rigid double-octahedron layers is partially
554
and isomorphously replaced by Fe2+/3+ ions. These are
capable, according to Weiss and Hofmann [3], of being
partially reduced or oxidised by sulphite or hydrogen
peroxide, respectively. This is therefore a redox ite according
to OUT definition [4].
Brittle, friable, greenish yellow aggregates from the pit at
Ficht/Opf. (Germany) were crushed, screened to 0.5-0.6 mm
and washed. Analysis: 3.83 % FezO3; 94.8 % Si02; about
1.1 % CaO and 0.6 % MgO; traces of AP+, K+, CI-. According to Debye-Scherrer diagrams the substance contains
large amounts of quartz. After reduction with aqueous
dithionite solution it is dark green, after oxidation with
highly dilute H202 it is honey yellow. The reflection spectra
of both forms show weakly marked bands, which correspond
approximately to solid Fe(I1) or Fe(II1) sulphate.
The redox capacity determined with a 0.2 M solution of
Fe(I1) sulphate in 0.01 N sulphuric acid is 0.16 mequiv./g or
0.19 mequiv./ml, corresponding to about 1/3 of the total iron.
It strongly decreases during five successive reductions and
oxidations owing to the partial extraction of the iron. By
potentiometric titration with a 0.1 N solution of titanium(II1)
chloride and ceric(1V) sulfate in 1 N H2SO4 the E50 %-potential was found to be 654 f 10 mV, i.e. about 27 mV lower
than the potential of Fe2+/3+ in the same solution. A third
method gave somewhat higher values [5]. During the determination slight decomposition occurs.
The exchange capacity of the reduced form for anions is
< 0.005 mequiv. Cl-/g. The exchange capacity for cations
(about 0.085 mequiv. 60Co2+/g)is approximately the same for
both the reduced and the oxidized forms. The low exchange
capacity of the Fe3+ form for anions is surprising: it is
< 0.005 mequiv. Cl-/g, 0.00004 mequiv. 131J-/g (partially
bound as IZ?) and 0.000009 mequiv. 87Br-/g [51.
Advantages as compared with organic redox resins are the
absence of irreversible oxidations, a relatively high reduction
rate (no gel diffusion), high temperature and radiation
stability; basic disadvantages are inferior redox capacity and
instability in strongly acidic or alkaline solution.
As further redoxites sodium polyvanadate and silicic acid
phenolic esters are being studied. The latter can be reduced
and oxidized on the surface in water free solvents 161.
Crystalline ammonium phosphomolybdate was reduced in
benzene by phenylhydrazine to a deep blue form, without
molybdenum blue going into solution,and was then reoxidized.
Received, August
6th, 1962
[Z 324/158 IE]
[*I XIIth Communication on "Redox-Exchangers".
[l] K. Jasmund: Die silikatischen Tonminerale. 2nd ed., Verlag
Chemie, Weinheim/Bergstr. 1955, p. 122.
[2] B. Sansoni, Lecture, GDCh-Hauptversammlung Stuttgart
(Germany) 1960; prediction of inorganic redoxites: lecture, Institute of Technology, Stockholm (Sweden) 1957.
[3] A . Weiss, U.Hofmann et al., Ber. dtsch. keram. Ges. 31, 301
(1954); Z. anorgan. allg. Chem. 284, 247 (1956).
[4]B. Snnsoni, Naturwissenschaften39,281 (1952); Ph. D. Thesis,
University Munich (Germany) 1956; Chem. Technik 10, 580
(1958).
[5] For a discussion of error see full publication.
[6] B. Sansoni and W . Schmidt, AbschluBarbeit, Regensburg 1953.
Angew. Chern. internat. Edit. / Vol. I (1962) / No. I0
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