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Chemistry of Organic Peroxides.

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oxane. After a sufficiently long reaction time ( 3 days a t
80°C) most, but not all, of the compound ( I ) was consumed
Since separation of the product was difficult we hydrolyzed
the mixture ( I ) + (2) cautiously (1 N NaOH/acetone at room
temperature), whereupon the unchanged ePoxide (1)
remained unattacked and we obtained the acid (3) in 46 %
yield; it has m.p. 191-192°C and [or]';"= +57" (c = 1 in
CHCI,). Esterification with diazomethane gave the methyl
ester ( 4 ) (> 90 "/, yield), m.p. 164-166OC, [a]:: + 5 7 "
(c = 1 in CHCI,). The configuration assigned follows from
the N M R
(loo MHz, in CDC13, ppm with
reference t o T M V : H-1, 8 = 4.83 (singlet, J1.2 = 0[51); H-2,
H-3, = 2.12 ( h 3 = 9.1 Hz, cis); H-4,
1.9 Hz); H-7, 6 = 1.68 (53.7 = 4.6 Hz, troiis; 52.7
5.0 Hz, trans). In C6Ds: H-4, 6 = 3.14; H-5, 8 3.75 (54,5
9.0 Hz, diaxial).
hydrazine hydrate in ethanol (16 h, reflux) gives the hydrazide
= 1
(5) [quantitative yield, m.p. 236--238 "C, [a]',"= +42 " (c
in C H C ~ ~ ! C H 9:1)].
~ ~ HReaction of (3) with chloroformic
ester, triethylamine, and sodium azider61 afforded the azide
(6) [85 % yield, m.p. 100-10'1 "C, [a]: = +52' (c --= 1 i n
CHC13)], which yielded the urea derivative ( 9 ) [91 % yield,
m.p. 2 4 1 - 2 4 5 0 ~ ,
= +59.50 (c = 1 in CHC~,)], when
heated in anhydrous toluene for 1 h, treated with water, and
boiled for a further 16 h. Further hydrolysis of the acid (3)
proceded only as far as compound (7) [yield SOX, m.p.
133-134OC, [or]',"= + 5 O (c = 1 in CH3OH)I. The glycosidic
linkage is stable to 5 N HCl. Reducing the ester ( 4 ) with
LiAIH4 in tetrahydrofuran (1.5 h, reflux) gave the alcohol (8)
[74 % yield, m.p. 140-142°C, [a]: = +72' (c = 1 in CHC13)I.
Received: November 28, 1967
[Z 681 IE1
German version: Angew. Chem. 80, 152 (1968)
= OH
= OCH,
[*] Dr. W. Meyer zu Reckendorf and U. Kamprath-Scholtz
Of the wealth of reactions that are possible with (3) and ( 4 )
we have investigated the following: Treating ( 4 ) with
(2), R
(3), R
(4), R
(S), R
(6), R
Institut fur Pharmazeutische Chemie der UniversitSt
44 Munster, Hittorfstr. 58-62 (Germany)
[l] L. Horner, Fortschr. chem. Forsch. 7, 1 (1966).
[2] N . K . Richtmyer in R. L. Whistler and M . L. Wolfroriz:
Methods in Carbohydrate Chemistry. Academic Press, New
York, London 1962, Vol. I, p. 106.
[3] W. S. Wadsloorrh and W. D . Emmons, J. Amer. chem. SOC.
83, 1733 (1961).
141 We thank Dr. J . C. Jochims, Max-Planck-Institut fur Medizinische Forschung, Heidelberg, for measurement and interpretation of the 100 MHz spectra.
[ 5 ] The manno-configuration thus made probable was confirmed
by comparison with ( I ) (H-1, 6 = 5.0 ppm, doublet, J l , z = 2.5
Hz) and the corresponding manno-epoxide (H-1, 8 = 4.9 ppm,
singlet), which, having a configuration analogous to that of
( 4 ) , also shows no coupling between H-1 and H-2.
[6] J . Weinstock, J. org. Chemistry 26, 3511 (1961).
Chemistry of Organic Peroxides
The International Symposium on "The Chemistry of Organic
Peroxides" was held in Berlin-Adlershof during 13-15th
September 1967. It was arranged by the Institut fur Organische Chemie of the Deutsche Akademie der Wissenschaften
zu Berlin and by the Chemische Gesellschaft in der D D R .
Thirty-two papers were read and 250 participants from 20
countries were present.
P e r o x i d e Synthesis
In a review paper A . Rieche (Berlin-Adlershof) reported the
synthetic principles used by the Adlershof school for the
preparation of numerous peroxy compounds.
1. Addition of hydrogen peroxide or alkyl hydroperoxides t o
carbonyl compounds, nitriles, Schiff's bases, or ketene
acetals. With hydrogen peroxide in the presence of mineral
acid, triacetylmethane affords triacetylmethane peroxide
( I ) , which formed the symbol of the peroxide symposium.
2. Reactions of mesomerically stabilized carbonium ions
with H z 0 ~or HOOR. They lead particularly smoothly t o
peroxides containing a-situated N or 0 functional groups.
Angew. Chem. internat. Edit. 1 VoI. 7 (1968) 1 N0:2
3. Reactions of electrophilic agents such as halogens or
Hg(l1) acetate with olefins in the presence of hydrogen peroxide.
4. Substitution of R-OOo for functional groups (Cl, OR,
OH, NH2) in organometallic compounds of Sn, Ge, Pb, As,
or Sb.
Bond-breaking Reactions ; Trioxides, Tetroxides
According t o P. D. Bartlett (Cambridge, Mass.) t-butyl
hydroperoxide and lead(rv) acetate at -95 "C give a solution
of di-t-butyl tetroxide (Z), which is in equilibrium with the
hydroperoxy radical ( K = 5 x 10-5 at -95 "C, heat of dissociation 6 kcal/mole). At higher temperatures the tetroxide
evolves oxygen, and radical recombination leads to di-tbutyl trioxide (3), which is stable up t o -35 “C.
+ BuOO.
G. A . Rimell (Ames, Iowa) pointed out in his paper that
oxygen in the triplet ground state cannot add to a carbanion
in a one-stage reaction, since this would break the spin conservation rule. His observation that triphenylmethyl and diphenylmethyl anions nevertheless add oxygen very rapidly
requires a multistage mechanism for its interpretation:
+ 2 BuO-
+0 2
+ -0-0-BU
Electron transfer
Above -35 “C oxygen and di-t-butyl peroxide are formed as
stable end products. Following the radical concentration by
ESR spectroscopy over the whole temperature range shows
minima in the region where the tetroxide and trioxide exist.
N . A . Milas (Cambridge, Mass.) found that iodobenzene is
formed without evolution of oxygen on reaction of diacetoxy
iodobenzene with t-butyl hydroperoxide at -80 ‘C, so that
the tetroxide (2) must be present in these solutions. Cautious
warming leads at -70 “C to evolution of oxygen and formation of the trioxide (3), whence oxygen is again evolved
between -45 and -20 “C.
The temperature ranges in which the tetroxide and trioxide
appear agree well with those found by P . D. Bartlett.
I n the discussion there were various references to the importance of spin conservation for reaction mechanism. For
instance, a one-stage decomposition of the tetroxide (2) must
produce the 0 2 molecule as a singlet. However, T. G. Traylor
(San Diego, California) was able to exclude this one-stage
mechanism by comparison with the decomposition of di-tbutyl hyponitrite ( 4 ) . Compound (4) exists in the trans-form
and cannot yield a n 0-0 bond in one step; yet the almost
among the decompoidentical proportion of Bu-0-0-Bu
sition products from (2) and (4) indicates analogous decomposition mechanisms.
Bu - 0-0-BU
In the papers by Bartlett, Traylor, and Hiatt formation of 0 2
and a radical pair was assumed in place of a one-stage decomposition of the tetroxide (2). Here the spin conservation
rule permits formation of singlet 0 2 with a singlet radical
pair or formation of (normal) triplet 0 2 and a triplet radical
pair :
BuO’J. 0-0
(2) B u - 0 - 0 - 0 - 0 - B u
Spin reversal
+ R-OO:d
According to the acidity of the hydrocarbon, either the anion
formation (e.g. diphenylmethane) or the reaction of the
anion with 0 2 (fluorene) is rate-determining.
Owing to spin conservation, the occurrence of singlet oxygen
would be expected in reactions where oxygen is evolved,
which involve a polar mechanism. For instance, the singlet
oxygen (“doubly bonded” 0 2 ) that is evolved on reaction of
bromine with hydrogen peroxide as reported by W. A .
Waters (Oxford, England) could attack olefins with shift of
the double bond or undergo 1,4-addition to 1,3-dienes or to
hydrocarbons of the anthracene type. Singlet oxygen is thus
to be considered the key compound in the photosensitized
reactions of 0 2 discovered by G. 0. Schenck.
Connections with co-carcinogenesis were also referred to.
Mrs. S. K. Maizu, (Moscow, USSR) dealt with the role of
alkyl hydroperoxides and peroxy radicals in the liquid-phase
oxidation of organic compounds. For the process yielding
radicals, not only the decomposition of an alkyl hydroperoxide must be considered. but also the reaction
+ R.
+ RO- + H20
BuO.4 0-0
ft kOBu
W. Pritzkow (Merseburg, DDR) deduced from competition experiments that tertiary C-H bonds o n the cyclohexane
ring are autoxidized faster by a factor of at least 2 when in
equatorial than in axial positions. L. Novotnj (Prague, CSSR)
discussed the formation, by way of peroxidic intermediates,
of cr,P-unsaturated five-membered ring Iactones in plants
(various Petasites species).
According to A . G. Davies (London, England), autoxidation
of organometallic compounds occurs by way of a radical
chain :
P . D . Bartlerf pointed out that an experimental decision between the two possibilities was not yet possible, since reversal
of spin in the radical pairs is faster than coupling of the
radicals or their diffusion away, as shown by the identical
cage effects of “singlet” and “triplet” pairs of methyl or
cumyl radicals.
+ 0;q
as indicated by the dependence of the decomposition of the
hydroperoxide on the strength of the C-H bond in RH. The
influence of the reaction medium and of homogeneous catalysts (salts of metals of variable valence) was discussed.
Complexes of alkyl hydroperoxides with other components
of the reaction mixture play an important part. Studies of the
formation of epoxides in co-oxidation of olefins and organic
compounds showed that acylperoxy radicals are the epoxidizing agents.
+ M-R
+ R-00-M
+ R.
+ R-OO-
When R is optically active a-methylbenzyl and M is boron
complete racemization results, which makes direct introduction of 0 2 unlikely. An addition-elimination mechanism was
Angew. Chem. internat. Edit. 1 Vol. 7 (1968) J No. 2
Cleavage of Polar Peroxides
Organometallic Peroxides
I n a review paper G. A . Razuvayev (Gorki, USSR) gave an
insight into his own, very numerous, investigations of new
homolytic reactions of peroxy compounds. Many organometallic compounds react with diacyl peroxides even below
the decomposition temperature of the peroxides, the acylperoxy radical then not undergoing decarboxylation.
+ (R'C00)2
2 RnM + (R'C00)2
(M = A1 or TI)
-+ Rn-1M-0-CO-R'
+ 2 Rn-1M-0-CO-R'
+ 2 R.
Metal-metal bonds are cleaved by diacyl peroxides.
R3M-MR3 + (R'C00)z
(M = Sn or Pb)
+ 2 R2M-0-CO-R'
(RzM)zM'+ (R'C0O)z + 2 R3M-O-CO-R'+
( M = Si or Ge; M' = Hg, S, Se, or Te)
Dialkyl peroxides have appreciably greater difficulty in reacting with organometallic compounds; at room temperature only the following reaction with trialkylaluminum
occurs :
2 Alk,Al+ t-Bu202
A kinetic study of the reaction of amines with dibenzoyl peroxide (0. A . Tschaltykjun, Jerewan, USSR) showed that
amines are of two types, namely, those that react with the
0-0 bond either mainly heterolytically or mainly homolytically.
C. Riichardt (Miinchen, Germany) studied the thermal decomposition of substituted 9-decalyl perphenylacetates (7) in
polar and apolar solvents. By following the consumption of
the perester and the formation of radicals (trapping by
galvinoxyl) kinetically, he found that heterolysis and homolysis of the 0-0 bond of (7) are truly competitive reactions.
Radical formation is favored by electron-donor substituents
(e.g. p-OCH3).
+ 2 AlkZAl--O--Bu-t
-- 2 Alk-
Stable organometallic compounds such as tetraalkyl compounds of silicon and germanium react with dialkyl or diacyl
peroxides or peresters only above the decomposition temperatures of the latter. Then a reaction of the alkyl groups with
the free radicals occurs that involves attack o n the C-H
Peresters of the type R3M-CH2-CH2-CO-OOBu-t
prepared with M = Si or Ge, and the reactions of the radicals
formed o n their thermal decomposition were studied. Further, peroxides of composition RHgOOR' and RzT100R'
have been synthesized for the first time and studied.
For organic peroxy derivatives of tin and lead, V. A . Shushunov (Gorki, USSR) showed that alkylperoxy derivatives
of the type R3M-00-R'
decompose homolytically onIy
above 100 OC. However, heterolytic decomposition of acyl(M = Sn or
oeroxy derivatives of type R3M-00-CO-R'
Pb) is rapid even at room temperature. Both reactions
follow a kinetic Iaw of the first order. The influences of the
substituent, the metal, and the solvent on the decomposition
reactions were studied.
J . Dnlzlmann (Berlin-Adlershof, D D R ) reported the synthesis and decomposition o f bis(organometalIy1) peroxides
R3M-OO-MR3 (M = Ge, Sn, o r Pb). In the decomposition
o f tin peroxides, which occurs even below room temperature,
the kinetics and the influences of substituents, solvent, and
added tin compounds show that the decomposition is induced
by diorganotin oxides formed in the decomposition.
M . Schulz (Berlin-Adlershof, DDR) studied fragmentation of the system (8), his examples being the base-catalyzed
decomposition of acylated t-butyl peroxyglycosides, sugar
azohydroperoxides, and acetylated sugar peroxy esters.
The five-center fragmentation of peroxyglycosides has preparative importance as a sugar degradation reaction.
E. Schmitz (Berlin-Adlershof, DDR) gave several examples of heterolysis of nitrogen-containing peroxides,
whose fragmentation is started by presence of a basic N
atom or a deprotonated amide nitrogen in the y-position to
the peroxy group.
W. H. R. Richardson (San Diego, California) discussed the
decomposition of monochlorinated t-butyl hydroperoxide
by bases to yield acetone and formaldehyde by way of
an intermediate (9) containing a four-membered ring.
Kinetic data were adduced in favor of neighboring group
participation by the peroxide group.
R . L. Dunnley (Cleveland, Ohio) studied electrophilic substitution of aromatic compounds by nitrobenzenesulfonyl
peroxides (10). The reaction leads to phenols, in good yield,
by way of sulfonic esters.
According to G. Sosnovsky (Milwaukee, Wisconsin) reaction
of monochloro derivatives of tervalent phosphorus with
r-butyl hydroperoxide in pyridine gives a phosphate ester,
which is also obtained from:the
perphosphate ester and
RzSnO + R3SnOR
W . P. Neumann (Giessen, Germany) reported the reaction of
diacyl peroxides with organotin hydrides. It results from
attack of R3Sn radicals o n the peroxidic oxygen and chain
propagation by the acyloxy radicals thus formed. The stannyl
radical is nucleophilic and always attacks the electron-poorer
peroxidic oxygen.
Angew. Chem. infernat. Edit. / Vol. 7 (1968) 1 No. 2
+ Bu-OOH
+ (C&,)3P
Reactions of Ozone; Ozonides
P . S. Bailey (Austin, Texas) reviewed reactions of ozone with
organic compounds. Four types of reaction were distinguished: 1. Cycloaddition to olefins, yielding primary ozon-
ides; 2. electrophilic attack, for instance on phosphines and
amines; 3. nucleophilic attack, for instance on Schiffs bases;
and 4. 1,3-dipolar insertions into C-H bonds, for instance
with benzaldehyde. R . W. Murray (Murray Hill, New Jersey)
discussed the route from primary ozonide to ozonides on the
basis of extensive experimental material. The Criegee mechanism needs some extensions. The intermediate stages (IZ)
and (12) were brought into the discussion o n the basis of
stereochemical and crossing experiments, as well as labeling
experiments with deuterium or 1 8 0 .
-4 ? (12)
R . Criegee (Karlsruhe, Germany) showed that aldozonides
from styrene and substituted styrenes are cleaved t o aldehyde
and acid by some solvents, particularly rapidly by methanol.
A diozonide isomerizes under acid catalysis to a compound
that contains two peroxide groups and two acetal oxygen
[VB 104 IEI
non-monotonic course of any flow-driving force relation is
the kinetic principle.
Lecture at Kiel (Germany), on October 19, 1967
[VB 105 IE]
German version: Angew. Chem. 80, 156 (1968)
[*] Doz. Dr. W. Seidel
Institut fur Physikalische Chemie der Universitat
23 Kiel, Olshausenstr. (Germany)
[l] Cf. H . L. Heatcoat, Z . physik. Chem. 37, 368 (1901).
[Z] U . F. Franck, Ber. Bunsenges. physik. Chem. 68, 876 (1964).
[3] U. F. Franck, 2. physik. Chem. N.F. 3, 183 (1955).
[4] A. L . Hodgkin, A . F. Huxley, and B. Katz, J. Physiology 116,
424 (1952).
[51 K . F. Bonhoeffer, Naturwissenschaften 40, 301 (1953), and
further literature cited there.
[6] U . F. Franck, 2. Elektrochem. angew. physik. Chem. 55, 535
(1951); Chem.-1ng.-Techn. 38, 612 (1966); and further literature
cited there.
Condensation of D-Glucose with Aromatic Systems
in Liquid Hydrogen Fluoride
German version: Angew. Chem. 80, 125 (1968)
By F. &ficheel[*]
The Kinetic Principle of Excitable Systems
By W. Seidel[*J
About 70 years ago W . 0stwald“J noted in the behavior of
the system Fe/HNO3 remarkable analogies to phenomena
that were known in excitation physiology. This finding
suggested that a chemical kinetic principle exists that is
capable of generalizationand is not confined to living systems.
In fact, many such, so-called “kinetic” model systems are
known, and the analogies of their functioning to that of living
systems that can undergo excitation is so astonishingly
extensive that “no biological phenomenon of excitation is
known that cannot be simulated by a kinetic model” 121.
The most obvious characteristic of all these systems is an
“either-or” behavior that results from the ability of the
system t o exist in two different (stationary) states. Like the
living systems, the models are open systems in the thermodynamic sense; a stationary state arises only if an inward
flow from the environment compensates the outward flow
from the system. These flows are caused by driving forces that
originate from an energy or a potential difference. A superposition of the relations between flow and driving force for
the system and for its surroundings should make it possible
t o interpret the behavior observed.
It can be clearly shown[3J how, for instance, superposition
of a “load line” on a non-monotonic N-shaped characteristic
of a system leads to the existence of two stable stationary
states which are separated by a n unstable one. If the characteristic of the system can shift relative to the characteristic
of the evironment, because of the chemical kinetics, then an
“either-or” behavior can be explained.
In the nerve-cell membrane the phenomenon of excitability is
of electrochemical nature [41. Like most model systems, the
Fe/HNO3 system, later called the Ostwald-Lillie nerve model,
also belongs t o electrochemistry 151. As a typical electrode
having a passivating film, iron shows the requisite nonmonotonic course in its current-potential characteristic. The
Fe/HNO3 model can be used t o simulate the most varied
biological excitation phenomena 161. In all other cases a nonmonotonic characteristic of the system is found t o be significant. Doubtless, occurrence of such characteristics is not
confined to the particular set, “current-potential”. On the
contrary, excitable systems are to be expected whenever a
High polymers are formed by condensation, in nucleophilic
reactions, of polycyclic aromatic hydrocarbons 111 with
aldoses in liquid H F at room temperature. The site of substitution can be determined by condensation with [1-14C]-~glucose and oxidation to carboxylic acids. Carbazole gives a
polymer-homologous series of condensation products; C-C
bonds occur in all of these, and the OH groups of the sugar
residue can be acetylated.
Being aromatic systems, coals of various ages also give
condensation products (labeling with [l-14C]-~-glucose;
glycosidically bound D-glucose is removed by hydrolysis) 121.
Moreover, very pure graphite (99.999 % of C) condenses with
formation of covalent bonds (0.6-1.8 % of [ I - ~ ~ C I - D - ~ ~ U cose) (31. All the condensation products are free from watersoluble self-condensation products of D-glucose. Benzene and
[1-14C]-~-glucoseafford, amongst other condensation products, triphenylmethane whose labeled tertiary C atom is
derived from the D-glucose (yield: 15 %, calc. on D-glucose).
Toluene and [l-“T]-~-glucoseyield, as well as a methylanthracene, a hydrocarbon C24H24, [ a ]=~-44 ’(in benzene),
which fluoresces blue in solution and contains aliphatic
groups (yield: ca. 4 %, calc. o n D-glucose).
Lecture at Clausthal-Zellerfeld (Germany), on October 27, 1967
[VB 106 IE]
German version: Angew. Chem. 80, 156 (1968)
[ * ] Prof. Dr. F. Micheel
Organisch-Chemisches Institut der Universitat
44 Munster, Hindenburgplatz 55 (Germany)
[l] F. Micheel and L . Rensmann, Makromolekulare Chem. 65, 26
(1963); A . H . Haines and F. Micheel, ibid. 80, 7 4 (1964); F. Micheel and H . Licht, Tetrahedron Letters 1965, 3701; Makromolekulare Chem. 103, 91 (1967).
[Z] F. Micheel and D.Laus, Brennstoff-Chem. 47, 345 (1966).
131 F. Micheel, Lecture at the International Symposium on
Carbohydrate Chemistry, Kingston (Ontario), July 1967; Lecture at Osaka o n October 13, 1967.
Individual Steps in the Chemisorption of Gases on
By W . M . H. Sachtler[*l
The chemisorption of gases on metals is determined primarily,
not by the collective parameters of the metallic state Fermi level, holes in the d-band, e f c . - but by the chemical
Angew. Chem. internat. Edif. Vol. 7 (1968)
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