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Expansion of Six-Membered Rings in Cyclopentadienyl-Benzene-Metal -Complexes by Acylation.

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with N-chlorosuccinimide, 1-butyl hypochlorite, N-bromosuccinimidc, and other reagents are in progress in order to
confirm these findinqs.
Table 1. Chlorination of n-hcpcane at 98 "Cwith trichloromnhane
sulfonyl chloride or elemental chlorine
-
Chlorinating
agent
RlSnH
~
Composition of the monochloro-nheptane fraction 1% by wt.]
I-chloro- 2-chloro- 3.chloro- 4-cbloro-
Hours
Catalyst
CIz Ial
CCI3SOzCI [b]
2
CCIJSO2CIIc]
8
hv
GHsCOOOH
(5 mole- %)
CsHsCOOOH
(5 molayd
5
shown that this new synthcsis can be used in many ways and
that, besides radical-forming compounds, ZnCl2 is also a
suitable catalyst. Hydrogenation of the unsaturated groups
by the organotin hydrides. which takes place exclusively in
the absence of catalysts 121, is largely suppressed.
I
2.3
34.6
50.4
33.8
32.1
16.5
15.2
1.9
50.3
32.0
15.8
15.1
la] 14.2 g (0.2 mole) of Clz were passod into 100.2 g ( I mole) of
n-C?HI6 Over 2 hours; monochloroheptane fraction: 19.9 g.
Ibl 100.2 g ( I mole) of n-C7H16and 30.5 g (0.14 mole) of CCI3SO2CI;
monochloroheptane fraction: 12.8 g.
[cl 100.2 g ( I mole) of n-C7H16and 43.6 g (0.2 mole) of CCI3S02CI;
monochloroheptane fraction: 20.0 g.
The reaction product was charaperized by adsorption
chromatography substantially according to Asinger et al. [2].
The isomer composition of the monochloride fraction was
examined by gas chromatography. The separation and
quantitative estimation of the isomeric n-heptyl chlorides
was carried out using a column 16 m long containing 8 %
P.v-iminodipropionitrileon 60-80 mesh chromosorb R as
stationary phase (8O0C, He as carrier gas). The gas chromatography equipment was a model 600 instrument made by
Research Specialties Co., Richmond, Calif.
We thank Dr. Elisaheth Bendel for the gas chromatographic
investigations.
Received. December 18th. 1962 [Z 4l4/234 1 9
[I]Cf. F. Asinger: Chemie und Technologie der Paraffinkohbnwassentoffe. AkademieVerlag, Berlin 1956, p. 608 el seq.
121 F. Asinger, G. Griseler, and K. Schmiedel, Chem. Ber. 92,
3085 (1959).
Additions of Organotin Hydrides onto
Aldehydes, Ketones, and Azomethines
4.Priv.-Doz. Dr. W.P. Neumann
and cand. chem. E. Heymunn
Chemische.. lnstitut der Universitiit GieDen (Germany)
Addition of organotin hydrides onto carbonyl compounds
or azomethines leads to organic compounds containing the
Sn-0- and Sn--N- group, respectively [I]. It has now been
+ O=CR'Y' + R3Sn a-CHR'R" (R'can also be H)
R3SnH + R'. CH-N R" + R'-CH2--N(SnR3)R"
The compounds in Table I , and many others prepared by us,
are easily hydrolysed. In moist air, gradual formation of the
corresponding alcohol or secondary amine and of triethyl-tin
carbonate (R3Sn)zC03 (decomposes at 137- 140 O C with
evolution of CO2) occurs. Three additions of tributyltin
hydride onto ketones under the influence of ultraviolet
irradiation have recently bcen reported by R. Colas et al. [3].
- -.--
Received, Deeeniber 19th 1962
[Z415/233 1EI
[J] W. P.Neumonn, H. Niertiiann,and R. Sommer, Angew. Chem.
73, 768 (1961).
[2] J. G. Noltes and G. J. M.van der Kerk, Chem. and Ind. 1959,
294; H.G. Kuivila and 0. F. Beumel,jr., J. Amer. chem. SOC.83.
1246 (1961); J. Valade, M. Pereyre, and R. Calas, C. R. hebd.
Seances Acad. Sci. 253. 1216 (1961).
[3] R. Calas, J.Valade and 1. C. Poinmier, C. R. hebd. Seances
Acad. Sci. 255,1450 (1962).
Expansion of Six-Membered Rings in
Cyclopentadienyl-Benzene-Metal
z-Complexes by Acylation
By Prof. Dr. E. 0.Fischcr and DipLChem. S. Breitschafl
lnstitut f i r Anorganische Chemie
der Universitlt MLlnchen (Germany)
During experiments on thc acylation of CsH5CrChH6 [I] and
CsHsMnC6H6 [2] using AIC13 according to Friedel-Crafts,
we surprisingly obtained under mild conditions an approximately 10 % yield of cyclopentadienyl-metal sc-complexes
containing a substituted scven-membered ring as the second
complexed ligand instead of a substituted benzene. Thus,
acctylation in CS2 and subsequent hydrolysis led to stable
cations of empirical formulac [ C I ~ H I ~and
C ~[C13H14Mnl+.
I~
which could be precipitated as their hexafluorophosphates.
These no longer contain the oxygen of the acid halide. The
carbon atom which originally bore the oxygen is inserted
into the six-membered ring, expanding it to form a sevenmembered ring, while the methyl group bound to it becomes
P substituent of the. seven-membered ring.
Table 1. Product8 obtained from aldehydes, ketonw, or azomethinw
and triethyltin hydride between 40 and 90% (in the absence of air)
b. p,
Yield [c] of
pure compound I%l
Product
GdW3Sn-X. X=
Obtained from
['C/mmHg]
--O-CHZCH(CH~)Z
-0-CH2-GHs
isobutyraldehyde[a1
benzaldehyde [a]
150-155/14
80
[d]
-0- CHz-l!.
furfural [a1
121-125/12
[dl
anisaldehyde [a]
methyl ethyl ketone Ib]
132/0.04
93-96/12
75
95
69/0.1
61
95-96/11
0
-O-CH~--C~H~-OCHJ
-..O-CH(CH3)C2Hs
cyclohexanone Ib]
-o+>
-O--CH(CH3)-GH4--OCH~ pmelhoxyacatophcnone~bl 90-93/10-'
CsH4-CH3
benzal-p-toluidino [a, bl
142/10-3
-"
70
63
'CH~--C~H~
[a] Azoisobutyric dinitrile as catalyst
[cl Mostly small-scale experiments.
loo
[h] ZnClz as catalyst.
Id] Not determined.
(1). (2). ( 3 1 hli.=C1..1Wn;(4)i\le=Cr
Proof that the diamagnetic, pink, complexed Mn cation is
the cyclopentadienyl(melhylcycloheptatrienyl)manganese(l)
cation [C5H5MnC7Hh--CH,]" is provided by the NMRspettrum [3] of the hexulluorophosphate in acetone which
contains three signals with c-values of 5.53, 5.61. and 7.55 in
the ratio of 6:5:3. Thc greenish yellow, paramagnetic
[ C I J H I ~ C ~cation
]'~
(hexatluorophosphate, 2. I Bohr magAngew. Chem. iiit(.mcit. Edit. I
Yo/.2 (1963) I No. 2
straight-chain saturated and unsaturated mono-, di-, and trinetons, corresponding to one unpaired electron) has pracnitrosamines do not react under the conditions stated above.
tically the same infrared spectrunl us the Mn complex. The
However, transnitrosation was accomplished by addition of
Cr cation can be reduced with alkaline Na2S20.1 solution to
catalytic quantities of hydrochloric acid, which also induced
give a neutral, diamagnetic, blue-hlack complex (m.p. 78 "C),
dimethylnitrosamine to react.
for which an analogous structure, viz. cyclopentadienyl(methylcycloheptatrienyI)chromium(O) CsHsCrC7HdH3,
The N-N bond in diphenylnitrosamine is so weakened by
can be deduced on the basis of its NMR spectrum [3] in
the electron attraction of the phenyl rings on the one hand,
CsD6. which has r-values of 5.1 I. 6.83, and 8.00 in the ratio
and of the oxygen of the nitrosyl group on the other that it is
of 6:5:3.
more easily broken when the reactants come into contact
This novel ring expansion also proceeds successfully with
than the N-N bond in the aryl-aliphatic N-nitrosamine, in
aromatic acid halides. In this wily, we obtained. the cations
which the electron accepting property of the benzene ring is
[CsH5MnC7H6-C,&]+
and [CslisCrC7H6-C6Hs]+ from a
partly negated by the alkyl group. The failure of transnitrosation to occur with entirely aliphatic N-nitrosamines
reaction with C~HSCOCI/AICI~
rollowed by hydrolysis; the
second of these cations could again be reduced to a bright
without a catalyst may be attributed to the strengthening of
green, uncharged complex (m.p. YO -91 "C).
the N-N bond by electron donation from the alkyl groups.
The structure of these new five- and seven-membered ringReceived. January 2nd. 1963 [Z 419/250 IE]
metal compounds, which were for the fust time produced by
ring expansion of aryl-metal complexes, was confirmed with
chromium by an independent syni hesis. By using the method
Phenol as Humification Inhibitor in Protein
leading to CsHsCrC7H7 [4], wc were able to introduce
Hydrolyses
methyltropylidene and phenylt ropylidene as substituted
tropylium cations into CsHsCrC,,H6 by displacement of the
By Dr. F. Drawert and K.-H. Reuther
benzene and with attendant hydride elimination. During this
far Rebenziichtung Geilweilerhof, AbteiPrOCeSS, [C~HSC~C~H~-.CH$]+'
and [ C ~ H S C ~ C ~ H ~ - C ~ H S ]Forschunpinstitut
+
IungBiochemie undPhysiologie,Siebeldingen,Pfalz(Germany)
were formed in a smooth reaction in good yields and proved
to be identical with the complexes prepared by ring expansion
During complete hydrolysis of animal and -plant tissues
judging from their infrared spcctra and, after reduction,
with 6 N HCl for total amino acid analyses, considerfrom their NMR-spectra.
able formation of dark insoluble precipitatcs often occurs
Received, Deceinber 191h. 1962 [Z 417/232 IE]
(Maillard reaction; melanoidins, humic acids). In this way,
. -.
.
considerable quantities of amino acids escape detection by
[I1 E. 0. Fischer and H. P. K&k*r, Z . Neturforsch. 136. 197
(1958).
the analysis. Various methods, not all of them satisfactory,
121 S. Breitschaft, Diploma thesis. Universitiit Miinchen, 1962.
have been described for avoiding these undesirable side reactions [I]. We have found that addition of phenol at the
[3] Investigationsby H. P. Fritz.
commencement of the hydrolysis is quite effective.
[41 E. 0. Fischer and S. Brriisch&, Angew. Chem. internat.
Edit., in the press.
Thus, 4 ml of 80 % aqueous phenol are added to approximately 50 mg of dried and finely ground leaf material (vine
leaves) in a thick-walled boiling tube and warmed to 50 to
60°C for 5 min. After addition of 6 ml of 10 N HCI, the tube
Transnitrosation: a New Route to Oximes
is sealed off and heated for 20 hrs at 105 OC. After cooling,
By Dr. Carl Heinz Schmidt
the contents of the tube are transferred quantitatively to a
separation funnel and extracted exhaustively with ether. The
Chemisches Laboratorium der U niversitiit
ethcral solution of the phenol Is then reextracted with
Freiburg/Breisgau (Germany)
water. The combined aqueous phases are evaporated to
dryness, and the residue is redissolved to prepare a standard
When aromatic C-nitroso compounds and cyclopentadienes
solution for amino acid analysis.
react together, intensely colored I -azafulvenes are formed
es.:
-----
R = ci, c,115
On the other hand, surprisingly, uromatic N-nitroso compounds react with the reactive niethylene group of 1,2,3,4tetrachlorocyclopentadiene to form the oxime of the latter
and secondary amines, e.g. :
M a n s of several analyses using an automatic amino acid analyser
manufactured by Bender and Hobein, Miinchen (Germany)
with
The reaction proceeds without il catalyst on heating the
reactants together in a polar solvcnt such as lower alcohols
or glacial acetic acid, giving high yields. On passing from the
purely aromatic diphenylnitrowmine to the aryl-aliphatic
compound phenylmethylnitrosamine, we find that this reacts
more slowly, while the purely aliphatic derivative dimethylnitrosamine does not react at ill1 under these conditions.
Other compounds with active CH2-groups are also suitable,
e.g. pyrazolones, rhodanines, mlonic dinitrile, and barbituric acids. N-Nitrosamides and the majority of cyclic and
Angew. Chem. internut. EJit. 1 V d . 2 (1963) 1No. 2
6 N HCI
6NHCI
phenol
+
--
His
Lys
Arg
--
NH3
I 0.95 I 0.86 I 0.15 I -
Asp
I I I I - II I
Thr
1.85
0.54
0.85
1.80
Received. January 7th. 1963
SU
'1'+
0.2rl 0.6
~
2.45
I I I
Glu
I
Pro
pmoler
0.85 pmoles
[Z428/254 IE]
[I] E. Kofanyi, Hoppe Seylcra Z . physiol. Chem. 287,170(19$9);
J. P. Dustin, C. Czajkowska. S. Moore, and E. J . Bigwood, Analytic. chim. Acta 8,236 (1953); G. Krampitz, Z. Tierphysiol.Tierernllhrg. u. Futtermittelkunde IS, 227 (1960); G. Schramm and
J. Primosigh, Hoppe.-Seylers Z . physiol. Chcm. 283, 34 (1948).
101
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acylation, metali, membered, ring, complexes, six, cyclopentadienyl, benzenes, expansion
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