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Preparation of -Ionone from all-trans-Pseudoionone.

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considerable stability. Unlike the Zchloromethylpyridines, the 3- and 4-chloromethylpyridines cannot
be distilled. When attempts are made to evaporate
solutions of these compounds, a crystalline mass is
formed which probably consists of compounds of type
(7) and their decomposition products. This saltformation is exothermic and can take an extremely
vigorous course. Thus, 3-chloromethylpyridine (prepared by neutralization of an aqueous solution of its
hydrochloride with sodium carbonate and separation
of the oil precipitated reacts with itself or1 standing at
room temperature, developing heat until vigorous detonation occurs.
These halogenomethyl compounds cause intense inflammation of the skin, but this disappears after some
time. Moreover, the free bases (especially in coqiunction
with solvents) cause strong irritation of the eyes and
mucous membranes. When working with large quantities, it is therefore expedient to isolate not the halogenomethyl compounds, but rather their subsequent
Received. Auyust 14th. 1962
[A 271/75 IE]
Fluorosulfuryl Fluoroperoxide
This therefore suggests the following feasible new synthetic
By Dr. R. Gatti, Dr. E. H.Staricco, Dr. J. E. Sicre, and
Prof. Dr. H.J. Schumacher
route to polyarnidell;
Instituto Superior de Investigaciones, Facultad
de Quimica y Farmcia
Universidad Nacioml de La Plata (Argentine)
On irradiating a mixture of fluorine monoxide and sulfur
trioxide at room temperature with light of365 mp wavelength,
fluorosulfuryl fluoroperoxide ( I ) is obtained in almost quantitative yield.
For polyamide-12:
Compound (I) originates by stepwise reaction of a fluorine
atom and an FO radical; formed primarily by photolysis of
the fluorine monoxide, with a sulfur trioxide molecule. The
FSO3 radical is formed as an intermediate. The quantum
yield of the reaction is 1.0 molecule/hv.
Compound (I) is a pale yellow-green liquid, b. p. O°C; its
vapor pressure is given by log p(mm) 6.781 -1063p. It is
thermally stable at temperatures below 5OoC. Its infrared
spectrum,its behaviour in neutral solution, and its oxidation
value as measured against neutral aqueous KI solution all
indicate the above StNCtUre.
Received, October Eth, 1962
[Z 399/223 IEl
Undecanolactam and Laurolactam from
Cycloundecanoic Acid and Cyclododecanoic Acid
Received, October 10th. 1962
[I] L. Ruzicka, M.Kobelt. 0.Hdfliger. and V. Prelog, Helv. chim.
Acta 32,544 (1949); see also G. Wilkv and P. W. Borner, German
Pat.1075601 (March 31st, 1959)StudicngesellschaftKohlem.b.H.
[2] W. Ziegenbein, Chem. Ber. 94, 2989 (1961); R. Brockhaus.
unpublished results from Wissenschaftliches Laboratorium der
Chem. Werke Huls AG.; see also P. w o n t and Y. Bonnet,
French Pat. 1264032 (May 6th, IY60), SOC. des Usines Chim.
[3] 0. Glosauer, W. Schade. and W. Srhneider, unpublished
results from Wissenschaftliches Laboriitorium der Chem. Werke
Hiils AG.; see also G. Bo, P. Perrus, and Y. Colleuille, French
Pat. 1 286 803 (Jan. 25th, 1961). SOC.dcs Usines Chim. Rh6nePoulence.
By Dr. W.Ziegenbein and Dr. W.Lang
Preparation of y-Ionone
from all-trans-Pseudoionone
Wissenschaftliches Laboratorium der
Chemische Werke Hlils AG., Marl (Germany)
Lactams with 11 or 12 carbons in their rings were formerly
prepared from the cycloalkanones of corresponding ring size
via the oxime [I]. The lactam with 1 1 carbon atoms in the ring
is particularly difficult to obtain in this way. Starting from
cycloundecanoic acid ( I ) [2] or cyclododecanoic acid (2)
(prepared for example from 1,5,9-cyclodecatriene or cyclododecene via the formyl compound [31), which were nitrosated with equimolecular quantities of nitrosylsulfuric acid
in 1 5 3 0 % oleum at 65-7OoC in chloroform as solvent,
we obtained undecanolactam (azacyclododecan-2-one)(3) or
laurolactam (azacyclotridecan-2-one)(4) simply and in good
By Dr. G. Ohloff [*I and G. Schade
Max-Planck-lnstitut fUr Kohlenforschung
Abt. Strahlenchemie, M illheim/Ruhr (Germany)
We have found [I], that y-iononc (2) is formed in 33 %
yield, alongside a lot of a-ionone and traces of @-ionone,
when pure geranylideneacetone (all-fruns-pseudoionone)(1)
A d ,
( I ) , n = 10
(2), n = 11
(31, u = 10, m.p. 154,s "C,Yield: 16.5 %
(4). n- 11. m.p.
150°C. Yield: 88.5 %
Angew. Chem. internat. Edit. I Vol. 2 (1963) 1 No. 3
[Z 368/251 IE]
is treated for 1 hour at room temperature with an equimolecular amount of BF3etherate. If 60 % diethyl ether or about
38% dimethytformamide (DMF) is also added to the
reaction mixture, then the y-ionone fraction is increased to
over 60% of the cyclization product. Moreover, the composition of the product depends upon the reaction time: and
the temperature. Pure y-ionone, which was obtained by
fractional distillation of the reaction mixture through a
highly efficient packed column equipped with a vaporseparating head and an automatically adjustable reflux-ratio
device, isomerim under the conditions of the cyclization to
the same mixture of isomers as is obtained from (I). Addition
of more than 50% of dimethylformamide to the BF3etherate inhibits the total cyclization reaction.
Nerylideneacetone (3) cyclizes almost exclusively to a mixture of the stereoisomeric bicyclic ethers (4) [2].
y-hone, y-n-methylionone, y-iso-methylionone and y-allylionone were prepared from the corresponding open-chain
all-traits-ketones in an analogous way by the use of the new
cycliiation procedure.
Received. October 24th. 1962
[Z 377/231 IE]
[*] Communication No. 11 on Cyclizations; Communication
No. I: G. Ohloff,Liebigs Ann. Chem. 606, 100 (1957).
[I] Application has been made for patents covering several
variants of the process.
121 This anomalous cyclization reaction was observed on
pseudoirone by Y. R. Naves and P. Ardizio, C. R. hebd. Seances
Acad. Sci. 235, 579 (1952).
NH3 at 0°C to form the remarkably stable diamino compound (2).
o c
CH3-k-N \SiCH,h
(1). B.P. 98'C/13 m m Hg,
m. p. 72-76 *C
Heating (2) to 200°C results in isomerization to (3), which
partially condenses to (4), b.p. I23 OC/O.3 mm, n 8 = 1.4461,
(31, B.p. 4O0C/O.4 mm, n a
with elimination of ammonia. Careful hydrolysis of (I) or
(2) gives the thermally unstable compound N,N-bis-(trimethy1silyl)-methyldihydroxysilylamine(5), n n = 1.4580.
N,N-Bis-(trimethylsilyl)-phcnyldichlorosilylamine (6) (b.p.
115 "C/I mm, m.p. 3840°C) is prepared similarly to (1) and
reacts with NH3 to give primarily the monoamino compound
, 118 "C/l mm, nf$ = 1.5112; complete ammonolysis
to the diamino compound (a), b.p. 105OC/l mm, n g
1.5084, takes place only on prolonged treatment with NH3.
On heating to 200."C, bolh (7) and (8) rearrange by silyl
migration; condensation and fission reactions are also observed.
GHs-Si -N
Dimerisation of Chromone
Treatment of chromone in absolute ether at room temperature
with sodium ethoxide and decomposition of the reaction
product with dilute acetic acid yield yellow a-(chromon-3-yl)P-salicoylethylene ( I ) , m.p. 173-174 "C. Compound (I)
gives a positive ferric chloride reai3ion and yields salicylicacid
with hydrogen peroxide in alkaline medium. Treatment of
(I) in glacial acetic acid with concentrated sulfuric acid produces colorless 2-(chrom-on-3-yl)chromanone(2) of m.p.
154-155 "C. This conversion is reversible.
The infrared spectrum of (2) contains two carbonyl bands at
1685cm-1 (compare flavanone: VC=O
1680cm-1) and at
1638cm-1 (compare. 3-methylchromone: vc=o = 1640 cm-1).
The NMR spectra of ( I ) and (2) agree with the proposed
structures. Dimeric chromones of type ( I ) were also obtained
from 6-methylchromone and 7,8-benzochromone.
(8), R = NH2
(10). R
NH2. b.p. 101 "Cl0.5
With water and triethylamine in dioxan, (6) gives N,N-bis(trimethylsily1)-phenyldihydroxyilylamine ( I I ) , m.p. =
100-105 OC, which decomposes at ca. 80 "C with evolution of
Received, December 12th. 1962 [Z422/247 IEI
[I] U. Wannagat and H. Nii*derprum.Z . anorg. allg. Chem. 308,
337 (1961).
[2] Compounds (I), (2), (6), and (8) were prepared simultaneously and independently by U. Wannagat and H. Bijrger in
Graz, Austria (personal communication).
By Dr. U.Graf zu Stolberg [*]
lnstitut fUr Anorganische Chemie
der Universitiit Mllnchen (Germany)
The data concerning infrared spectra refer to compounds in
their crystalline state (pellets in KBr).
Received. December loth, 1962
n 8-
(9). R = CI, b. p. 123 OC/0.5 mm.
(7). R = CI
Fakultiit fUr Allgemeine Ingenieurwissenschaften
der Technischen UniversitBt Berlin (Germany)
k H 2 \Si(<:H313
By Prof. Dr. A. Schanberg and Dr. E. Singer
kHz \si(cHi)3
(2). B.P. = 101 %/I7 mm.
m.p. I50-53 'C
Sodium and dimethyldichlorosilane ( I ) in an autoclave are
said to give some dodecumethylcyclohexasilane (3), as well
as polymeric [Si(CH3)lX 121. Under similar conditions, we
found only polymeric products. However, treatment of (I)
or tetramethyldichlorodsilane(2) [3] with a Na/K alloy in
tetrahydrofuran produced (3) in high yield.
[Z418/244 IE]
Tris-silylamines Containing Si-Functional Groups
By Dr. H. NiederprUm
Anorganisch-wissenschafiliches Laboratorium
der Farbenfabriken Bayer AG., Leverkusen (Germany)
N,N-Bis-(trimethylsilyl)-methyldichlorosilylamine( I ) can be
preparedin 75 %yield fromC&Li, (CH3)3Si-NH-Si(CH&,
and CH3SiCla in a onestep reaction [1,2]. It reacts with
Reaction (a) takes place spontaneously when ( I ) is added
dropwise into a suspension of Na/K alloy in very pure. THF,
applying the dilution principle; 138 g of (1) gave 50 g (81 %)
of (3) and 8 g (13 %) of insoluble high molecular-weight substances. Reaction (b) docs not go to completion even after
Angew. Chem. internut. Edit. / Vol. 2 (1963)
/ Nu. 3
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preparation, ionone, pseudoionone, transp
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