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New Reactions in the Quinone and Heterocycle Series.

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(la]: X = 0-S02-R
(Ib): X = NH,
On the other hand, 2-(cyclopenten-l-yl)ethylamine and
cyclopenten-I-yl tosylate, on deamination or hydrolysis
respectively, afford predominantly bicycl0[3.2.0]heptan-l01. Derivatives of bicyclo[4,2,0]octan-l-ols ( 3 ) behave
anomalously: the p-nitrobenzoate yields, both o n pyrolysis
and by elimination reactions with strong bases, mainly
spiroI2.5Joct-4-ene (4).
satisfactorily. The measured (apparent) diffusion coefficients
of plasticizers in PVC exhibit a large discontinuity in the
glass transition range but are only slightly dependent upon
the concentration beyond this range, being proportional t o
the vapor pressure of the plasticizer at the temperature of the
experiment. This proportionality can be explained by the
fact that the limiting conditions assumed for measurements
of the diffusion of plasticizers out of plasticized PVC plates
are seldom fulfilled. The diffusion of the plasticizer is generally overlapped by processes that occur during the drying
of a porous systeni and which depend on the vapor pressure
of the volatile components.
A theory developed by G . Kanig [7] for the glass temperature
of plasticized polymers can account satisfactorily for some of
the values so far found by experiment and thus forms a good
starting point for further research.
[GDCh-Ortsverband Mulheirn/Ruhr, Miilheim/Ruhr
(Germany), March 31st, 19651
[VB 9321235 IE]
German version: Angew. Chem. 77,625 (1965)
[I]H. Luther and W. Stein, Z . Elektrochem. 60, 1115 (1956);
H . Luther, H. Meyer, and H . Lcew, Z . analyt. Chem. 170, 155
Allenes (such as (5), X=OSOzR or NH2) also rearrange
readily during solvolysis reactions to give cyclopropane
derivatives in good yields. These reactions may be compared
t o homoallyl rearrangements and afford aIkyl cyclopropyl
ketones (6). In strongly ionizing solvents, acetylenes such as
(7) can be cyclized with formation of cyclobutanones (8).
[GDCh-Ortsverband Freiburg-Sudbaden (Germany),
February 26th. 19651
[VB 9191225 IE]
German version: Angew. Chem. 77, 624 (1965)
Interactions of Plasticizers with
Poly(viny1 chloride)
[2] H . Luther and G. Weisel, Kolloid-2. 154, I5 (1957).
[3] H. Lutlrer, F. Glander, and E. Schleese, Kunststoffe 52, 7
(1 962).
[4] E. Schieese, Doctorate Thesis, Technische Hochschule Clausthal, 1962.
[ 5 ] G. Pessier, Doctorate Thesis, Technische Hochschiile Clausthal, 1962.
161 H. Luther and H . Meyer, Z. Elektrochem. 64, 681 (1960).
[7j G. Kanig, Kolloid-Z. 190, I (1963).
New Reactions in the Quinone and
Heterocycle Series
H . 4 . Triibrr, FrankfurtIMain (Germany)
o-Hydroxyphenethylamine derivatives are oxidized by
potassium nitrosodisulfonate to 5-hydroxyindoles, which on
further oxidation yield o-quinones. For instance, compound
( I ) affords red-violet 2-phenylindole-4,5-quinone(3) in an
overall yield of 80 %, vio the isolable intermediate (2) [I].
H. Luther, Clausthal (Germany)
The interactions of plasticizers with poly(viny1 chloride)
(PVC) were studied by infrared spectroscopy [I], N M R and
dielectric measurements [2] on the pure substances and their
solutions, microscopic observation of the swelling of PVC i n
individual plasticizers and mixtures of plasticizers [ 3 ] ; viscometric measurements of the solubility of PVC in plasticizers
using a rotation viscometer and the plastograph [4],infrared
spectroscopical observation of plasticizer separation [ 5 ] and
diffusion [6].
Plasticizers do not form associates of definite stoichiometric
composition with PVC but simply dissolve in the polymer.
Chloroform/plasticizer mixtures can serve as model systems
of low molecular weight; their heats of mixing are determined
from the shifts in the infrared bands of the plasticizers on
alteration of the concentration.
The solubility of PVC in esters of plasticizers with aliphatic
alcohols is greatest when the alcohols contain 3-4 carbon
atoms. N M R spectra reveal that the good solubility is due t o
dissociation of intramolecular associates of the esters as the
chain length of the alcohol component increases, for the
PVC can then undergo intermolecular association with the
ester. However, as the chain length increases, the intermolecular association is again suppressed.
When mixtures of plasticizers are used, the interactions
among them determine their solvent powers. The FloryHuggins interaction parameters d o not reflect this situation
If a tertiary phenethylamine such as (4) is used, the product
is a yellow cyclic quinone imine such as (5) or (6).
2,2,4-Trimethyl-1,2-dihydroquinoline(7) [2] also yields a
yellow p-quinone imine, viz. (8); however, when the p-position is substituted, the product is a red o-quinone imine,
e.g. (9).
[ I ] Experimental work in collaboration with 0.Glosauer.
[2] G. Reddelien and A.Thurm, Ber. dtsch. chem. Ges. 65, 1511
(1932); D. Craig, J. Amer. cbem. SOC. 60,I458 (1938); D. Craig
and E. C. Gregg, ibid. 75, 2252 (1953).
Angew. Chem. interifat.Edit. 1 Voi. 4 (1965) [ N o . 7
Fluoroisoprenols are used to synthesize fluoro-coenzyme 0.
e . g . FQt ( 9 ) .
(71 H
The only oxotetrahydrocarbazolenine that behaves like a
ketone is the 3-0x0 compound (10). 2-Oxotetrahydrocarbazolenine occurs in the form of the vinylogous amide
(111, I-oxotetrahydrocarbazolenine(12) is enolized in the
manner of a diosphenol and gives a blue color with ferric
chloride, and 4-oxotetrahydrocdrbazolenIne cannot be
isolated since a P-dicarbonyl cleavage occurs under the
conditions of its formation [31.
= F
(11). R = H
The dihydro derivative of enzyme FQI (10) is unstable and
undergoes an intramolecular redox reaction by an additionelimination mechanism t o yield coenzyme Q1 (11) and HF.
Fluoroisoprenols were converted into their pyrophosphates,
some of which are inhibitors of steroid biosynthesis.
[GDCh-Ortsverband Nordbdyern, May 7th, 1965
in Erlangen (Germany)]
[VB 9271232 IE]
German version: Angew. Chem. 77, 625 (1965)
Inorganic Ring Systems with Silicon and Nitrogen
Atoms as Ring Members
[GDCh-Ortsverband Leverkusen (Germany),
April 8th, 19651
[VB 930/233 IE]
German version: Angew. Chem. 77,624 (1965)
Synthesis and Reactions of
Organic Fluoro Compounds
H. Mucfileidt, Biberdch/Riss (Germany)
U. Wannagat [l], Graz (Austria)
1,3-Dihalogenodisilazanes X-SiRz-NR’-SiR2-X
( I ) are
excellent starting materials for the synthesis of inorganic
rings with Si-N units. They can be prepared by the following
a) By cleavage of cyclotrisilazanes, cyclotetrasilazanes, or
polysilazanes with hydrogen halides in yields of 40-70 ”/:
(X = F, CI, or Br):
Carbonyl olefinations of ketones or fluoroketones with ethyl
diethoxyphosphinoacetate or ethyl diethoxyphosphinofluoroacetate or their vinylogues lead to fluoro-substituted
a$-unsaturated esters of type ( I ) .
+ 3 HX
+ X-SiR2-NH-SiR2-X
-t NH4X
b) By intermolecular condensation of dialkylchloroaminosilanes in yields of 40% (based on the amount of chloroaminosilane charged) :
4 RZSi(NHR)CI --f
3- [R’NH3]CI
c) By equilibration of cyclotrisilazanes or cyclotetrasilazanes
with dimethyldichlorosilane by boiling in yields of 70 %[2] :
LiAIH4 reduces compounds of type ( I ) , X = F, n = 1, at
-78 “C to fluoroisoprenols. At higher temperature, a reductive elimination of the y-fluoro substituent occurs with partial
isomerization of the double bond to isoprenols of type (2).
At the same time, an intramolecular nucleophilic substitution
of the fluorine occurs which is largely independent of the
temperature and proceeds via ( 3 ) + ( 4 ) . Further reduction
leads to the cyclopropane derivative (5).
A similar substitution of fluorine is observed with P-keto
esters ( 6 ) , leading to dihydrofuran derivatives (7). Fluoro-Pketo esters of type (8) are stable.
[31 H.-J. Teuber, D.Cornelius, and E. Worbs, Tetrahedron Letters
1964,331 ; H.-G. Teuber and D. Cornelius, Chem. Ber., in press.
Angew. Chem. internat. Edit.
Vol. 4(1965)
No. 7
+ 3 RzSiC12
+ 3 CI-SiR2-NH-SiR2-CI
d) By the action of the adducts of silicon halides on cyclosilazanes:
+ SiF4(NH3)2+
+ 2 NH, + I / x [SiFz(NH)lx
The 1,3-dihaIogenodisilazanes are readily converted by
alcohols, amines, and hydrazines in the presence of triethylamine into the corresponding derivatives ( I ) , X = RO, RzN,
and R2NNH. Analogous reactions, some of which require
prior metallation of N H groups, lead to numerous new ring
systems. Compounds made include ( 2 ) from ( 1 ) plus water,
( 3 ) from ( I ) plus ammonia, ( 4 ) from ( I ) plus hydrazine,
(5) from ( I ) plus ethylene diamine, and ( 6 ) from ( I ) plus
bistrimethylsilylurea. The Si-N four-membered ring of (7)
is formed in surprisingly high yields during attempts to
produce dichlorotrisilazanes according to method (c) but with
different ratios of reagents [3].
111 In collaboration with E. Bogusch and G . Schreiner.
[Z] P. Geymayer and E. G. Rochow independently carried out this
reaction in a sealed tube (personal communication).
I31 P. Geymuyer and E. G . Rochow also obtained this compound
from ( I ) , X = C1, and sodium bistrimethylsilylamide (personal
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series, reaction, heterocyclic, quinone, new
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