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Dimerisation of Piperidinoacetonitrle under the influence of a Grignard Reagent.

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below 0.7 V. Stronger oxidizing agents in the usual analytical
concentrations slowly attack the resins on prolonged exposure. The Table shows the characteristics of the resins
after four oxidation-reduction cycles.
Resins 1 and 2 both have a redox potential of & = 175 & 1
mV. Oxidative titration was carried out with Ce4+ in 0.1 N
sulfuric acid in the presence of 1 % anthraquinone-2-sulfonic
acid. The index potentials are 14 mV. The titration curve
corresponds to a reversible bivalent redox system.
Received, October Sth, 1962 [Z 362/189 IE]
[l] G . Manecke and W. Storck, Chem. Ber. 94, 3239 (1961).
[2] A. Btienne, G. Izoret, and F. Moritz, C. R.hebd. SCances Acad.
Sci. 249, 708 (1959).
[3] M. Fernandez-Refojo, Yue-Liang Pan, K. A . Kuhn, and H. G.
Cassidy, J. org. Chemistry 25, 416 (1960).
[4]L. W. Butz, E. W. J. Butz, and A . M . Gaddis, J. org. Chemistry
5, 171 (1940).
[ 5 ] G. Manecke, 2.Electrochem., Ber. Bunsenges. physik. Chem.
57, 189 (1953).
Reactive Silyl-substituted Alkyl Sulfanes
By Dr. M. Wieber and Prof. Dr. M. Schmidt
Institut fur Anorganische Chemie
der Universitat Marburg/Lahn (Germany)
On cleavage with dry hydrogen chloride, 1,1,4,4-tetramethyl1,4-disila-2,5-disulfacyclohexane[I] gives quantitatively 2
moles of dimethylchlorosiiylmethylthioi(I), a highly reactive
organofunctional chlorosilane.
CH3
I
I
CH3
It is oxidised by sulfuryl chloride to the disulfide (11)
according to the equation:
CH3
+
2 (0 sozc1z -+
Forschungslaboratorium der Dewey & Almy AG.,
Zurich (Switzerland)
Earlier work has shown that butadiene dioxide (I) adds onto
compounds with active hydrogen atoms, e. g. primary or
secondary amines, exclusively in 1,4-position. It therefore
appeared possible that addition of hydrazine or substituted
hydrazines onto butadiene dioxide would yield 4,5-dihydroxypiperidazines.
\o/
\\
-+
/
\o/
+ so2-t 2 HCl
AH3
+ ClS,Cl+
(I) + 2 HCI
CH3
CH3
CH3
CHI
I
I
+ CI-Si-CH2-S-S,-S-CHZ-Si-CI
I
Compound I1 and its higher homologues are colorless liquids
(yellow a t increased sulfur content); only I1 can be distilled
without decomposition (b.p. 14OoC/1 mm). The new sulfane derivatives react with many other compounds because
of the labile nature of the silicon-halogen bond. Thus,
hydrolysis results in the formation of sulfur chains of definite
composition joined by disiloxane bridges:
- CH3
I
.I
CH3
--ii4-ii-CHz-Sy-CH2-
,/
CH2-CH-CH-CHz
(ID
Condensation with chlorosulfanes leads to higher sulfane
derivatives:
(I)
By Dr. R. Gabler and Dr. H. R. Meyer
CH3
c~-$i<Hz-s-s-cH2sli.<~
kH3
Ring-closure Reaction of Butadiene Dioxide with
Hydrazines to Give New Pyrazolidine and
Piperidazine Derivatives
(I)
Cl-Si-CH2-SH
RHN-NHR
Ill
HO-,,,NH
AH,
AH3
Received, October 8th. 1962
HO,in/CH1OH
-
IZ 365/194 IEI
[l] M. Schrniur and M . Wieber, Inorg. Chem., I , 909 (1962).
"
13)
I
I
OH Li
(4)
R
Dimerisation of Piperidinoacetonitrile under the
Influence of a Grignard Reagent
reduction
2 H3CNHz
_ _ j CH2-CH-CH-CHzOH
CHz-CH-CH-CHz
ci
4
AH
I
I
&€I
b H NH
LHJ
CH3
By Prof. Dr. H. Thies, Priv.-Doz. Dr. H. Schonenberger,
and y.Qasba
(5)
With hydrazine itself in aqueous soIution at 20°C, 4 3 dihydroxypiperidazine was in fact obtained and identified
by reductive ring cleavage to give 1,4 - diaminobutane
2,3-diol. Starting from (f)-butadiene dioxide, trans-4,5-dihydroxypiperidazine (2) is formed (m. p. 233 "C, decornp.),
while the meso-compound gives rise to the cis-isomer.
Unexpectedly, the addition of sym-dimethylhydrazine onto
(&)-butadiene dioxide led to a 1:l-adduct not identical with
the compound obtained by N,N'-methylation of (2) with
formaldehyde. Investigation of the structure showed that 1,3a d d i t i o n had taken place here, giving the pyrazolidine
derivative (3), R = CH3, in 80 % yield. The 5-membered
ring structure of (3) was indicated by reductive opening of the ring to give (5), m.p. 110 "C, which proved to be
identical with the reaction product obtainable from 1,3-dichlorobutane-2,4-dioI (4) and methylamine.
N,N'-Diethylhydrazine and hydrazobenzene also form 1 :1adducts with meso- or (f)-butadiene dioxide in yields of
70-80 %, so that a general and preparatively interesting ring
closure reaction seems to occur. Determination of the constitution of the last two adducts has not yet been completed,
but there are many indications that they also have 5-membered
ring (pyrazolidine) structures.
Institut fur Pharmazie und Lebensmittelchemie
der Universitat Mtinchen (Germany)
-
Received, October Sth, 1962
660
[Z 370/199 IEI
Reaction of piperidinoacetonitrile (1) with t-butylmagnesium
chloride unexpectedly gave rise to a hitherto unknown
(2), an oil
compound, 3-amino-2,4-dipiperidinocroto~itrile
which distils without decomposition in vacuo, b.p. 169 "C/0.3
mm Hg and which crystallizes in the cold to form colorless
rhombic platelets (m.p. 86-87 "C) when crystallized from
isopropanol (yield 71 %). Compound (2) is formed from (I)
by dimerization, the C-atom of the C = N group of one m o l e
cule becoming linked to the a-C-atom of the second molecule.
Ill
Ill
N
N
(11
(2)
131
Its constitution is indicated by its infrared spectrum, its
behaviour with nitrous acid, and its synthesis by the method
of Thompson [l].
Angew. Chem. internat. Edit.
Vol. I (1962) I No. I2
The infrared spectrum shows two typical NH2 vibrational bands at 3495
and 3380 cni I and a C-C vibrational band at 1641 cm-1, which are not
i l l the spectrum OF the starting material, and the C s N band at 2186 cm.-I
is about 5 0 cm-1 lower than that in the starting material owing to
conjugation of the C E N group with the C-C group. The substance
evolves 1.04 mole Nz with HN02, in agreement with formula ( 2 ) , which
contains a primary amino group.
Adipodinitrile gave 2-amino-I-cyanocyclopent-I-ene by the method of
7 I i o n i p ~ v n[ I ] using sodium t-butoxide as condensing agent. In the same
manner. ( 2 ) can also be obtained from piperidinoacetonitrile. This
conlirms that ( 2 ) contains the same enaminonitrile grouping
N C C C NH2 as does 2-amino-I-cyanocyclopent-I-ene( 3 ) .
This new course of reaction seems to be of general importance. I t can be attributed to the bulky nature of the organic
component in t-butylmagnesium chloride, for n-butylmagnesium chloride and piperidinoacetonitrile d o not yield
the dimer, the Grignard reagent adding o n normally to give
n-butyl piperidinomethylketone in 64 "/, yield.
N C11:
C CJH.
I1
0
Received, October 8th. 1962
[ Z 382/205 IEI
[ I1 Q . E. Thoinpsun, J. Amer. chem. SOC.80, 5485 (1958).
Condensation Reactions with Monochlorinated
Trimethylsilanol
By Dr. M.Wieber and Prof. Dr. M . Schmidt
lnstitut fur Anorganische Chemie
der Universitiit Marburg/Lahn (Germany)
Mixtures of chloromethyl-methylpolysiloxanes have already
been prepared by equilibrating cyclic dimethylpolysiloxanes
with chloromethyldimethylchlorosilane[l].
The availability of chloromethyldimethylsilanol (1) - synthetired by hydrolysis of 1,3-bischlorometbyltetramethylCH,
I
ClCH:Si
I
(m.p.
OH
(I)
~
n $'=
-
6 ' C ; b.p. 47 "C/5 nim;
1.4402; d&
CHI
1.071)
Introduction of Cystine Bridges into Collagen I*]
By Dr. F. Schade and Prof. Dr. H. Zahn
Deutsches Wollforschungsinstitut
an der Technischen Hochschule Aachen (Germany)
Nitrophenyl esters are generally suitable for introducing
mono- and poly-functional carboxylic acids into proteins
such as insulin, wool keratin, silk fibroin, and collagen [I].
We have been able to build authentic cystine bridges into
tendon collagen by treating it with the bis-(o-nitrophenyl
ester) of bis(carbobenzyloxy)cystine, to the extent of 5.5 or
1 1 millimoles of disulfide groups per gram of collagen. A
bifunctional reaction of the bis(nitropheny1 ester) is indicated
by the raising of the transition temperature (shrinking
temperature) from 64 "C (control experiment) to 69 "C, and
by the clear relationship between the transition temperature
and the number of disulfide groups during reduction and reoxidation: reduction with thioglycolic acid splits the disulfide
links and lowers the transition temperature,while re-oxidation
with air raises both the disulfide content and the transition
temperature. lrreversible destruction of the disulfide groups
by oxidation with performic acid lowered the transition
temperature. This lends support to the cross-linking theory
of tanning 121.
Experimental: 1 g of tendon collagen [3] was treated with a
solution of 0.5 g of the bis-(o-nitrophenyl ester) of bis(carbobenzy1oxy)cystine (made from bis(carbobenzy1oxy)cystine and o-nitrophenol with dicyclohexyl carbodiimide,
m.p. 125-126 "C) in 200 ml of dimethylformamide and 40 ml
of water for 100 hours at 20°C. The product was washed
with dimethylformamide. Excess bis(nitropheny1 ester) and
salt-like derivatives were removed by extraction at room
temperature with ether for 60 hours and with 0.1 N ammonia
for 24 hours. The disulfide content was estimated by the
method of Zahn and Traumann [4]. The disulfide bonds were
reduced with 1 N thioglycolic acid (distilled) adjusted to
p H 9.2 with ammonia for 4 hours at 20°C. Thiol group
analysis was carried out according to Zuhn, Gertksen, and
Meichelbeck [5]; performic acid oxidation of disulfide groups
was performed by the method of T/iompson [6]; shrinkage
temperature estimations were made according to Zahn and
Wegerle 171.
Received, October 15th, 1962
disilazane which has recently been prepared [2] -- enabled us
to prepare definite members of this series in quantitative
yields.
Thus, compound I reacts with dimethyldichlorosilane in
ether i n the presence of stoichiometric quantities of triethylamine to form 1,5-bischloromethyl-hexamethyltrisiloxane
(b.p. 109 'C/lO mm, nfy = 1.4304, d& = 1.023).
CH3
'
CH,
CH,
I
CICH2Si-0 -Si--O-Ai-CH2CI
I
CH,
l
CH,
l
+ 2[HN(C*H&]CI
CH,
Chlorosiloxanes form higher homologues correspondingly.
Compound I reacts in the same manner with dimethyldichlorogermane, giving germanosiloxane.
CHI
CHI
[Z 372/200 I € ]
[*] Communication No. 6 on collagen; communication No. 5 :
H. Zahn, F. Growitz, and G . C. yon Hey/, Kolloid-2. 180, 26
(1962).
[l] F. Schade, Ph. D. thesis, Aachen 1962; reported briefly by
KI. Ziegler at the Informal Discussion on Fibrous Proteins and
Related Peptides of the Faraday Society on May 29th, 1962 in
Maidenhead, England.
121 See K . H . Gutstavson: The Chemistry and Reactivity of Collagen. Academic Press, New York 1956; W. Grassman, Das Leder
12, 165 (1961).
[3] Kindly supplied by the firm C. Freudenberg, WeinheimiBergstr., Germany.
[4] H.Zahn and K . Traumann, Melliand Textilber. 35,1069 (1954).
[5] H. Zahn, T. Gerthsen, and H. Meichelbeck, Melliand Textilber. 43, 1179 (1962).
[6] E. 0. P. Thompson, Aust. J. biol. Sci. 12, 282,490 (1959).
[7] H. Zahn and D . Wegerle, Kolloid-Z. 172, 30 (1960).
CHI
1
1
I
I
I
I
C'I CH2 SI 0 G e 0 S I - C H , -CI
(b p 95-98 "C/2 mm ,
The System Potassium AmideIAmmonia
By Prof. Dr. P.W. Schenk and cand. chem. H.Tulhoff
The use of dimethyldichlorostannane does not lead to the
corresponding stannosiloxane but to condensation of I to
I ,3-bischloromethyl-tetramethyldisiloxane.
Received October 8th, 1962
[Z 366/195 IE]
[ I ] J . L. Sparer, J . Amer. chem. SOC.71,273 (1949).
[2] M . Schtniclf and M . Wieber, Inorg. Chem., I , 909 (1962),
Atr~c~w
Chem.
.
itrtcrrrtrt. Edit.
Vul.
I (1962) 1 No. I2
lnstitut fur Anorganische Chemie
der Freien Universitiit Berlin (Germany)
Only few data are available on the solubilities of alkali metal
amides in liquid ammonia. According to Kraus [I],KN Hz is
more soluble than NaNH2, and Franklin [2] reports that a
saturated solution of KNH2 at -33.5 "C contains 45 g of
66 1
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