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Cyclopropane and Cyclobutane Derivatives by Rearrangement of Unsaturated Compounds.

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New Cleavage Reactions of Methylenediamine
Derivatives and x-Dialkylamino Ethers
H. Biihme, MarburgjLahn (Germany)
a-Halogenated amines are formed by cleavage of aminals
with acid halides. Analogously, N,N,N',N'-tetraalkylmethylenediamines react with sulfonic anhydrides t o yield dialkylmethyleneimonium sulfonates and dialkylsulfonamides.
Tetraethyl pyrophosphate reacts with aminals or a-dialkylamino ethers to produce carbimonium salts of diethylphosphoric acid and phosphoric ester amide or triester. The
carbimonium salts of diethylphosphorous acid, formed from
tetraethyl pyrophosphite, undergo a Michaelis-Arbusow rearrangement, whereby dialkylaminomethylphosphonic esters
can be isolated.
If mixed anhydrides are used for the cleavage reaction, the
imonium salt of the stronger acid present in the anhydride is
formed, together with the amide or ester of the weaker acid.
N - C H 2- N,
R, N-R3
E N = C H T @OR2+ R3-O-R1
R2, R3
R - C O - , R-SOz-, R-SO-, ( R 0 ) 2 P O - , ( R 0 ) z P -
On the other hand, the reactions of acetyl nitrate with aminals
yield dialkylnitramines and acetoxymethyldialkylamines
which are also obtainable by cleavage of aminals with
carboxylic anhydrides. When the reaction is carried out
using the mixed anhydride of acetic and formic acids, the
primary product ar-formyloxymethyldialkylamine is decarboxylated even at -20 "C and methyldialkylamine is formed.
Carbimonium halides which are usually considered to be
a-halogenated amines, on heating or on recrystallization
from aprotic polar solvents, yield dimers and trimers which
are also formed in the reaction of methylenediamine derivatives with methylene halides. Contrary to the monomers, the
dimers and trimers d o not possess the band of the C = N
double bond in the infrared spectrum at 5.95 p.
to theory, to be most pronounced for phosphorus. This is
the case particularly if the phosphorus carries a positive
charge. Three models were discussed for phosphonium salts
containing one to four p-dimethylaminophenyl groups, and
for phosphine oxides, phosphine sulfides, and phosphines
with one to three p-dimethylaminophenyl groups:
1. No participation of phosphorus d-orbitals.
2. Participation of a phosphorus d-orbital, with conjugation
across the phosphorus atom.
3. Participation of a phosphorus d-orbital, the phosphorus
atom inhibiting conjugation.
The ultraviolet absorption of all compounds investigated
could not be explained on the basis of models 1 and 2 or of
a model which had previously been suggested by other
authors [I]. On the other hand, all predictions based o n the
third model were found to be verified in the ultraviolet and
infrared spectra. An acceptor effect of phosphorus was
found experimentally which is greater than that of a CN
group in the salts, and which is nearly equal to C N in the
phosphines, oxides and sulfides. Increase of the electron
density at the phosphorus atom (replacement of C6H5 by
CH3; solvation of the phosphonium group; comparison of
the phosphines, oxides, and sulfides with onium salts) lessens
the acceptor effect. As borne out by the infrared spectra of
the oxides and sulfides, the same holds for the px-d, character of the P=O and P = S bonds: the frequency and intensity of
the PO- and PS-valence vibrations decrease (as would be expected according to model 3) with an increase of the donor
effect acting on the phosphorus.
The acceptor effect is not unambiguously discernible in compounds with unsubstituted phenyl groups; however, the small
participation of the phosphorus 3 p-orbital in the aromatic
z-bond systems of triphenylphosphine may be caused by a
counteraction of 3 p- and 3 d-orbital participation. As strong
electron donors demonstrated the participation of 3 dorbitals, it seemed possible that 3p-orbital participation
would be detected after introduction of strong acceptor
substituents. This was in fact the case, as indicated by the
properties of the phosphines (C~H~)ZP-C&-A@), where
A = N02, CN, CHO, COOCH3, COOH, CON(CH3)2, or
February 25th, 19651
[VB 917/216 IE]
German version: Angew. Chem. 77, 593 (1965)
Cyclopropane and Cyclobutane Derivatives by
Rearrangement of Unsaturated Compounds
M. Hunuck, Tubingen (Germany)
[GDCh-Ortsverband Sud-Wurttemberg,
Tubingen (Germany), February 19th, 19651 [VB 916/218 IE]
German version: Angew. Chem. 77, 594 (1965)
The Bond Character in Aromatic Phosphorus
Compounds - a Contribution to the Problem of
the Existence and Properties of p,-d, Bonds
G . P. Schiemenz, Kiel (Germany)
The participation of vacant d-orbitals of the valence electron
shell of hetero-atoms of the fifth main group in aromatic
x-bonding systems (p,-d,
bond) can be expected, according
Angew. Chem. internnt. Edit.
V d . 4(1965) [ No. 7
Open-chain homoallyl compounds are isomerized smoothly
to cyclopropylmethyl compounds, but yields are lower in the
case of cyclic homoallyl compounds. Here, the primarily
formed homoallyl cations are partly stabilized by hydride
shift. Thus, cyclohexen-4-yl tosylate is isomerized to an
extent of only 10 76 during acetolysis to yield the stereoisomeric bicyclo[3.1 .O]hex-2-yl acetates. On hydrolysis, cyclopenten-4-yl sulfonates yield 40 % cyclopenten-4-01 and 60 7;
cyclopenten-3-01. Similarly, the reaction of 4-bromocyclopentene with AgzO in water, proceeding by an SN1-mechanism, does not result in a bicyclic compound. The reduction
of cyclopenten-4-yl sulfonate with LiAIH4, on the other
hand, yields 4 % bicyclopentane, together with other hydrocarbons.
On hydrolysis, 2-(cyclohexen-l-yl)ethyl sulfonates ( l a ) isornerize, as does 2-(cyclohexen-l-yl)ethylamine ( I b ) during
deamination with nitrous acid, to form spiro[2.5]octan-4-ol
(2) and bicyclo[4.2.0]octan-1-ol(3) ;both alcohols can thus be
obtained in high yield.
[l] H . Goetz, Angew. Chem. 75, 675 (1963); Angew. Chem.
internat. Edit. 2, 552, (1963).
(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
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rearrangements, compounds, cyclopropane, unsaturated, derivatives, cyclobutane
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