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Dicyclopropyldiazomethane.

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tion, polymerization with simultaneous loss of sulfur dioxide occurs within a few hours under the influence of
daylight at room temperature; the same occurs when the
substance is warmed to 90-100 OC. IR spectrum: v(CN)2190,
vas (NSO) 1260, vs (NSO) 1170, S(NS0) 620 cm-1.
Compound (1) reacts exothermally with an ethereal solution
of 2,3-dimethylbutadiene to give the cyclic product (2).
The thiazine derivative (2) forms colorless crystals (m.p.
97-98 ' C , yield 90 %).
Treating (1) with bis(trimethylsily1)methylamine in ether at
-70 "C gives bis(trimethylsily1)carbodiimide (yield cu. 80 %),
as well as N-methylthionylimide (which forms polymers).
Thionylcyanamide (Caution during the preparation - explosive
decomposition possible - use u protective shield!) :
7.15 g (61 mmoles) of thionyl chloride is added dropwise to
11.2 g (60 mmoles) of bis(trimethylsily1)carbodiimide 131 a t
-7O"C, with stirring, over a period of 5-10 min. The
reaction mixture is then allowed to warm to 0°C within
about 45 min. The chlorotrimethylsilane is at once distilled
off under oil-pump vacuum and the residue is fractionally
mm; m.p.
distilled. Yield 3.2 g (60%); b.p. 23-24'C/4
-37'.
A brown polymeric solid remains as distillation
residue. If bis(trimethylsily1)carbodiimide is added dropwise
to a large excess of thionyl chloride, again only thionylcyanamide is formed.
Received: June 19th, I967
[ Z 534 IEI
German version: Angew. Chem. 79, 691 (1967)
[*I Priv.-Doz. Dr.
0. J. Scherer and cand. chem. R. Schmitt
Institut fur Anorganische Chemie der Universitat
Rontgenring 11
87 Wurzburg (Germany)
[I] 0. J. Scherer and P. Hornig, Angew. Chem. 78, 776 (1966);
Angew. Chem. internat. Edit 5, 729 (1966); 0. J. Scherer and
R . Schmitt, Z . Naturforsch. 226, 224 (1967).
[2] G . C. Demitras, R . A. Kent, and A. G. MacDiarmid, Chem.
and Ind. 1964, 1712; W. Sundermeyer, Angew. Chem. 79, 98
(1967); Angew. Chem. internat. Edit. 6, 90 (1967).
[3] Prepared according to: L . Birkofer, A. Ritter, and P . Richter
Tetrahedron Letters 1962, 195.
R
4-Hydroxyphenyl
3-Chloro-4-hydroxyphenyl
3-Chloro-6-hydroxyphenyl
2-Hydroxy-3,5-dimethylphenyl
2-Hydroxy-5-formylphenyl
4-H ydrox yphenyl
4-Hydroxyphenyl
4-Hydroxynaphthyl
H
H
H
95
88
90
H
86
H
CH.7
75
95
78
91
C6Hs
H
330
295-296
340 (decomp.)
300-303
295-297
310
150 (decomp.)
298
These products have hitherto been accessible, if at all, only
by total synthesis involving several steps [41.
5-(4-HydroxybenzyI)uracil: 5-Hydroxymethyluraci1 (1 g) and
then concentrated hydrochloric acid or trifluoroacetic acid
(0.3 nil) are added to molten phenol (15 9). The mixture is
stirred for 0.5 to 1 h at 80 to 100°C. Dissolution occurs after
a few minutes, then a thick precipitate separates. After the
mixture has been cooled, precipitation is completed by
addition of ether. Yield 1.45 g (95 %); recrystallized from
70 % ethanol or water, the product has m.p. 330OC.
5- (4-Hydroxybenzyl)-3-(2,3,5- tri-0-benzoyl - p - D -ribofurunosyl)uracil: 5-(Hydroxymethyl)-3-(2,3,5-tri-U-benzoyl-~-~-ribofuranosy1)uracil (0.5 g ) and concentrated hydrochloric or
trifluoroacetic acid (0.2ml) are added to molten phenol (20 g).
The mixture is kept for 1 h at 80 to 100 "C, then treated with
water (1 liter) and decanted; the precipitate is dissolved in a
little methanol and the solution is allo-ed to flow into water
(ca. 800 nil). Yield, 0.40 g (71 %). Recrystallized from
methanol, the pioduct has m.p. 155 O C (decomp.).
Received: May 26th and June 20th, 1967
[Z 535 IE]
German version: Angew. Chem. 79, 691 (1967)
[*] Priv.-Doz. Dr. R. Brossmer
Max-Planck-Institut fur Medizinische Forschung
Institut fur Chemie
Jahnstr. 29
69 Heidelberg (Germany)
[l] Pyrimidines, Part V. - Part IV: R. Brossmer and D. Ziegler, Angew. Chem. 79,322 (1967); Angew. Chern. internat. Edit.
6,369 (1967).
[2] R . E . Cline, R . M . Fink, and K . Fink, J. Amer. chem. S O C .81,
2521 (1959); R . Brossmer and E. Rohm, Liebigs Ann. Chem. 692,
119 (1966).
[3] Chromatographically uniform substance.
[4]5-Benzyluracil: T . B. Johnson and J . C. Ambelang, J . Amer.
chem. SOC.60, 2941 (1938). - Substituted 2-amino-5-benzyluracils: E. A. Falco, S . DuBreuil, and G . H . Hitchings, J. Amer.
chem. SOC.73, 3758 (1951).
Dicyclopropyldiazomethane
G C Condensations with the Uracilylmethyl
Cation 1' I
By R. B r o s s m e r ~ * ]
5-Arylmethyl derivatives of uracil can be simply prepared:
In statu nascendi, the cation that is readily formed from 5(hydroxymethy1)uraciI [21 by catalytic amounts of acid reacts
smoothly (forming a C-C bond) with phenols and naphthols
and their derivatives and with compounds that can be
substituted electrophilically. 5-Benzyl- and 5-(naphthylmethyl)-uracils (1) result. The condensation is not hindered
by fairly large substituents R', e.g. phenyl, o n C-4 of uracil.
Analogous reactions occur with free nucleosides or those
protected in the sugar portion.
702
By H. M. Ensslin and M. Hanackc*1
There have been two recent reports [1,*1 on the preparation
of cyclopropyldiazomethane. Dicyclopropyldiazomethane
can also be obtained; its preparation is indeed simpler than
that of cyclopropyldiazomethane. A solution of freshly
distilled dicyclopropyl ketone hydrazone ( I ) (24 g; readily
accessible [31 from dicyclopropyl ketone and 80 % hydrazine
hydrate in presence of barium oxide) in anhydrous ether is
cooled to 0 ' C and added rapidly, with stirring at 0 OC, to a
suspension of yellow mercuric oxide (56.2 g, 1.33 equivalents)
in ether (20 ml) containing 3 M ethanolic sodium hydroxide
(10 drops). The solution becomes deep red instantaneously;
after 5 min it is filtered and dried over KOH at -40 ' C . The
I R spectrum of the etheral solution shows a weak band at
Angew. Chem. internat. Edit.
1 Vol. 6 (1967)
No. 8
2260 cm-1, which is characteristic of a diazo group[l*41.The
cyclopropane rings are indicated by a band at 3090 cm-1. If
the ether is pumped off at -2O"C, the product (2) remains
as a brick-red oily liquid with a n odor of decay. The IR
spectrum of (2) in CDC13 at -20 "C shows an intense diazo
band at 2225 cm-1. Compound (2) begins to decompose even
while the spectrum is being measured; at -15OC decomposition sets in with violent evolution of nitrogen. However,
it can be kept for several days in ether at -50 "C.
The ethereal solution of (2) was added dropwise to a solution
of acetic acid in ether at -20°C. The course of the reaction
could be followed by the evolution of nitrogen; it yielded
dicyclopropylmethyl acetate (3), whose 1R spectrum and
retention time in the gas chromatograph agreed with those
of a n authentic specimencsl.
Received: June 8th. 1967
[Z 536 IE]
German version: Angew. Chem. 79, 687 (1967)
[*] Dr. H. M. Ensslin and Priv.-Doz. Dr. M. Hanack
Chemisches Institut der Universitat
Wilhelmstr. 31
74 Tubingen (Germany)
[l] H. A . Moss and F. C . Shulman, Chem. Commun. 1966, 373.
[2] P. B. Shevlin and A. Wo/f;J. Amer. chem. SOC.88,4736 (1966).
[3] M. Hanack and K . Corler, unpublished; cf. H . Hart and
0 . Curtis, J. Amer. chem. SOC.78, 112 (1956).
141 P.Yates, B. L. Shapiro, N.Yoda, and J. Fugger, J. Amer.
chem. SOC.79, 5756 (1957).
[5] M. Hanack and H . Eggensperger, Liebigs Ann. Chem. 663,
31 (1963).
x= 2
x= 3
x= 4
x= 5
88.5-89
66.5-67
81-82
128-129
74
75
9
7.5
trans-l,2-Cyclohexanedithiol ( 1 )
reacts with dichloromonosulfane or iodine with ring formation, if the dilution
method is used.
kSH
+ C1-S-C1 + HSfi
1-Substituted 1,2-cyclohexanedithiols d o not give cyclic
compounds on reaction with SxC12; nor does o-benzenedithiol.
Preparation of ( 4 ) :
0.2 mole of 1,2-cyclohexanedithiol and 0.2 mole of S,C4 are
dissolved separately, each in 100 ml of an anhydrous ether/
carbon disulfide mixture ( 3 : l ) . The solutions are added
simultaneously from two dropping funnels, during a period
of 12 h at room temperature and with stirring, to 3.5 liters of
anhydrous ether. Finally, the HCI is removed in a stream of
nitrogen, insoluble polymeric products are filtered off, and
the solution is concentrated to 100 ml. The stable crystals
that separate are recrystallized from ether. - Compounds
(2) and ( 3 ) are obtained similarly.
-4 HI
H
____
[*] Prof. Dr. F. Fehkr and Dip1.-Chem. B. Degen
Institut fur Anorganische Chemie der Universitat
Zulpicher Str. 47
5 Koln (Germany)
[l] S. M. Iqbal and L. N . Owen, J. chem. SOC.(London) 1960,
1034.
[2] B. Degen, Dissertation, Universitat Koln, 1967.
[3] F. FehPr, J . Goebell, and F. R . Minz, 2. anorg. allg. Chem.
342, 146 (1966).
s-s-s
1)
3.75
Received: June 13th, 1967
[Z 537a IE]
German version: Angew. Chem. 79, 690 (1967)
By F. F e h h and B. Degen[*]
+ C1-S-C1 + HSH
3.65; 3.24
3.92; 3.48
3.70; 3.26
In the mass spectra, fragments appear at mass numbers that
correspond to compounds (2), (3), and ( 4 ) ; in addition, key
fragments are found that are formed by successive loss of one
sulfur atom at a time. From compounds (4) with x = 3, 4,
or 5, a metastable fragment with mass number 131 is found.
In the 400 to 500 cm-1 region of the I R spectrum the bands
due to S-S stretching vibrations are well developed. The
IH-NMR spectra of ( 4 ) are appreciably more complicated
than that of cyclohexane.
New Sulfur-containing Cyclic Compounds
a H S H
232; 277
231 ; 278
232; 279
288
(2)
~
S
-
S
Preparation of Diimidazolylsulfanes and
Di(aziridiny1)sulfanes
D
s-s
By F. Fehdr and B. Degenl*I
(3)
(2)
(3)
216-218
191.5-192
j j
5~
Silylation of imidazole by hexamethyldisilazane affords
N-(trimethylsily1)irnidazole ( I ) [11. The silylated heterocycle
( I ) is suitable for reaction with chlorosulfanes (2) [21, since
the chlorotrimethylsilane formed thereby is readily removed
from the reaction mixture; furthermore, n o side reactions
occur. The diimidazol-1-ylsulfanes (3) are precipitated in
analytically pure form.
274
242
It yields perhydrodibenzo-1,2,3,6,7,8-hexathiecin(2) and
perhydrodibenzo-l,2,5,6-tetrathiocin
(3), respectively, which
are stable, colorless substances that can be recrystallized
from chlorobenzene. They can also be obtained by reaction
of bis(2-chlorocyclohexyl)-trisulfaneor - d i d f a n e with sodium
trisulfide or disulfide, respectivelyrzl, but then only in poor
yield.
Reaction of the dithiol(l)withchlorosulfanesSxC1~ (x 2 2) 131
in very dilute solution gives bicyclic sulfur compounds ( 4 ) .
(41
Angew. Chem. internat. Edit. 1 Vol. 6(1967) 1 No. 8
(3), m.p. ("C)
(31, yield (%)
I 1
111
92
91-92
90
88
82
1 :: 1
73-74 (decomp.)
70
If stoichiometric amounts of compounds (1) and (2) in
anhydrous benzene are used under a nitrogen atmosphere
with exclusion of moisture, higher chlorosulfanes (x 2 3)
being dissolved in a little anhydrous carbon disulfide, then
the sulfanes separate at once in pure crystalline form.
703
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