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Isomer Formation in the Monochlorination of n-Heptane with Phosphorus Pentachloride and with Phosphorus TrichlorideChlorine.

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Reaction of (2) under analogous conditions with an equimolar a mount of bromine, o n the other hand, leads t o
(3)
(21
( 1)
(3)
N-(alkylthiobromomethylene) sulfonamides (3), X = Br.
Moreover, when (2) is cleaved under th e sam e conditions
with a n equimolar am o u n t o f sulfuryl chloride, the product
is a n alkylthiochloromethylene sulfonamide (3), X = CI.
(4)
diborolidine ( 4 ) [31. Calculations using t h e LC A O - M O
method indicate a higher stability for the heterocycle ( 3 ) [41,
ar e however n o t free from contradictions [S].
Received: April 7 t h , 1965
IZ 9601786 IE]
German version: Angew. Chem. 77, 506 (1965)
[ I ] K. Niedenzu, P . Fritz, and J . W. Dawson, Inorg. Chem. 3, 1077
( 1964).
Rr
CI
CI
CI
C6H5
CH.3
CH3
CH,
68-69
52-53
C6H5
CH3
CH3
65-66
89-90
p-CH3-C6H4
39
74
93
89
T he structures of th e new compounds have been confirmed
by their infrared spectra. Th e alkylthiobromomethylene
sulfonamides have absorption bands at 6.5 an d 11.2 p that
a r e characteristic for th e C-bromoimide grouping, and t h e
alkylthiochloromethylene sulfonamides have bands between 6.4 a n d 6.6 p an d between 10.6 an d 10.9 p d u e t o the
chloroimido grouping. Satisfactory elemental analyses have
been obtained for all of th e halogeno compounds ( 3 ) .
121 Fields higher than that at which the reference signal occurs
(internal standard benzene, external standard BF~.O(CZH&)are
called positive and vice versa.
131 H . Noth and W. Regnet, Z. Naturforsch. 186, 1139 (1963);
K. Niedenzu, P . Fritz, and H. Jenne, Angew. Chem. 76, 535
(1964); Angew. Chem. internat. Edit. 3, 506 (1964).
[4] T . Balaban and A . Simon, Rev. roum. Chim. 9, 99 (1964).
[5] D. A . Bochvar and A . A . Bagaturyants, Izvest. Akad. Nauk.
SSSR, Otdel. khim. Nauk 1963, 785.
Isomer Formation in the Monochlorination of
n-Heptane with Phosphorus Pentachloride and
with Phosphorus Trichloride/Chlorine
By Dr. B. Fell
Received: May 5th, 1965
[ Z 9711797 IE]
German version: Angew. Chem. 77, 549 (1965)
[ I ] R. Neidlein and W. Haussmann, Tetrahedron Letters, in the
press.
121 R. Nridlein and W . Haussmann, Sudwestdeutsche Chemiedozententagung, Mainz (Germany), April 27th-30th, 1965.
131 R . Gompper and W. H i g e l e , Angew. Chem. 74, 753 (1962).
141 German Published Patent Application 1163802 (Aug. 27th,
1964), Farbenfabriken Bayer A G . , inventors: R. Gompper,
R . Wegler, K . Dickoree, and W. Hagele.
Institut fur Technische Chemie der
Technischen Hochschule Aachen (Germany)
n-Heptane was chlorinated with chlorine o r phosphorus
pentachloride (98°C; 2 moles of n-heptane, 0.2 mole of
chlorinating agent, 0. I mole of dibenzoyl peroxide) or with
PCI3/C12 (2 moles of n-heptane, 0.2 mole of PCI3,O.l mole of
dibenzoyl peroxide). T h e isomer composition of the monochloro-n-heptane fraction was determined gas chromatographically:
x-Chloro-n-heptane I % by weight]
By Doz. Dr. H. Noth an d Dipl.-Chem. G. Abeler
Institut fur Anorganische Chemie der Universitat Munchen
(Germany)
N-Metalation of triazaboradecalin ( I ) [ I ] with methyllithium in ether a n d subsequent reaction with symmetrical
bis(dimethy1amino)diboron dichloride gives 1,2-bis(dimethyl-
amino)perhydro-2a,5a,8a-triaza-l,2,8b-triboracenaphthylene
(2), b.p. 105 'Cjhigh vacuum, in ab o u t 30 yield. This compound is a derivative of the new B-N ring system 2,5-diaza1,3,4-triborolidine ( 3 ) .
j
1-
Synthesis of a 2,5-Diaza-l,3,4-triborolidine
Clz
15.1
PCl*
PCIJCI2
traces
1
2-
333.8
34.6
522
16.5
T h e results show that the hydrogen at o ms o f the methyl
groups react significantly more slowly with PCls than with
gaseous Cl2. It is particularlysurprising that the first methylene
group reacts more slowly with PCls than those further along
the molecule, whereas no such differences occur with gaseous
Cl2 [ I J . The effect found with PCls is even more marked in
the chlorination with Clz in t h e presence of excess PC13.
T h e cause of the different isomer distribution is probably t he
fact t h at different chlorine radicals act o n t h e n-heptane.
T h e chlorination employing PC15 or PCl>/C12 does not occur
via atomic chlorine (as in t h e reaction using chlorine alone),
but rather via complex, polarized Cl-containing radicals:
cf- + PcI3 +
The structure of (2) was confirmed by analysis, molecularweight determination, an d by infrared an d N M R spectroscopy. T he I H - N M R spectrum o f the substance in benzene
exhibits a triplet a t 3.85 p.p.m. (C), a triplet with a singlet superposedat4.35p.p.m.(A+D),andaquintupletat5.57p.p.m.(B),
the areas beingin t h e r a t i o o f 1 :4: 1. T h e JIB-signal of the B-B
group occurs a t -35 p.p.m., that of th e B a t o m of the BN3
group a t -28.4 p.p.m. [21.
The c om pound is being examined with regard t o th e question
of whether the system (3) is more stable than 2,3,S-triaza-1,4-
14--
6-
6+
[c13P:
--f
C1-I
Th e analogy with chlorination of a n n-alkane in benzene
with free chlorine, where the probability of substitution o n
the first secondary carbon a t o m is a h lower [2], supports
this hypothesis. A benzene-chlorine complex is formed [3]:
fi+
6-
C6H6 -cI
[Z 9621788 1El
Received: April 8th, 1965
German version: Angew. Chem. 77, 506 (1965)
111 F. Asinger and B. Fell, Erdol und Kohle 17, 74 (1964)
121 B. Fell and L . H . Kung, Chern. Ber., in press.
13) G. A . Russell, J. Arner. chem. SOC.80, 4987 (1958).
Angew. Chem. internut. E&.
1 Vol. 4 (1965)
No. 6
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trichloridechlorine, formation, heptane, isomers, phosphorus, monochlorinated, pentachloride
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