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Cleavage of -Halogeno--phenylalkanes by Sodium Hydrazide.

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the cyclohexyl ring. The I R spectrum (Nujol suspension)
contains the characteristic bands of I-cyclohexyltetrazole,
except for the v(CH) vibration 171.
The red solution of [As(csH5)4] [Au(N3)4] in tetrahydrofuran
rapidly becomes colorless in daylight, a n intramolecular
redox reaction occurring:
The diazidoaurate(1) complex [decomp. at 127 O C ; vas(N3) =
2039 cm-1, vs(N3) = 1285 cm-1, KBr disk] is precipitated in
crystalline form by petroleum ether. It can also be obtained
directly from Au(I)CI, NaN3, and [ A s ( C ~ H ~ ) ~inI C
CH2C12.
~
Received: November 21st, 1966
[Z 385 IE]
German version: Angew. Chem. 79, 146 (1967)
[*] Doz. Dr. W. Beck
Dip1.-Chem. W. P. Fehlhammer
Anorganisch-Chemisches Laboratorium
der Technischen Hochschule
8 Munchen 2 (Germany)
[l] W . Beck and H . Smedal, Angew. Chem. 78, 267 (1966); Angew. Chem. internat. Edit. 5, 253 (1966).
[2] W. Beck, K . Feldl, and E. Schuierer, Angew. Chem. 77, 458
(1965); 78, 267 (1966); Angew. Chem. internat. Edit. 4, 439
(1965); 5, 249 (1966).
[3] K . Feldl, Dissertation, Technische Hochschule Miinchen,
1966.
[4] F. Sommer, Ber. dtsch. chem. Ges. 48, 1833 (1915); E. Lieber,
C . N . PilIai, J . Ramachandran, and R. D . Hites, J. org. Chemistry
22, 1750 (1957).
[ 5 ] Cf. R. Huisgen, Angew. Chem. 75, 604 (1963); L . Birkhofer
and P . Wegner, Chem. Ber. 99, 2512 (1966).
[6] H . B. Jonassen, J. O.Terry, and A . D . Harris, J. inorg.
nuclear Chem. 25, 1239 (1963); J. Amer. Chem. SOC.85, 2927
(1963).
[7] G . L. Gilbert and C . H. Brubaker jr., Inorg. Chem. 2, 1216
(1963).
Reactant
Type
(I) :
Phenethyl chloride,
bromide, iodide
P-Methylphenethyl
bromide
a-Methylphenethyl chloride, bromide, iodide
T y p e (4) :
a-Methylbenzyl bromide
a-Ethylbenzyl bromide
60
Toluene 74, 80, 67
35
Ethylbenzene 67
35
Toluene 89, 85, 73
35
35
Toluene 2, ethylbenzene 35
Toluene 1, phenylpropane 41
35
Toluene 16, 3-phenylpropylhydrazine 47, phenylpropane 6.
Type (5) :
3-Phenylpropyl bromide
For cleavage of compounds of type ( I ) we must consider
not only the route via the olefin (7), but also that via the
hydrazine derivative (8), since hydrazines of this type decompose in the presence of sodium hydrazide according
to (8) + (2) + (3)[41.
In favor of the route via (7) are the facts that P,B-dimethylphenethyl chloride (6), which cannot yield a styrene derivative
by elimination of HHal, gives no trace of isopropylbenzene
on treatment with sodium hydrazide in ether at 35 "C or in
benzene at 60°C, but remains largely unattacked (22 % or
8 % resp. of t-butylbenzene being formed).
(8)
Received: November 21st, 1966
[Z 386 IE]
German version: Angew. Chem. 79, 147 (1967)
[*I Prof. Dr. Th. Kauffmann, Dip1.-Ing. W. Burkhardt, and
Cleavage of P-Halogeno-u-phenylalkanesby
Sodium Hydrazide
By Th. Kauffmann, W . Burkhardt, and E. Rauchr*I
On reaction with sodium hydrazide, phenylalkyl halides of
types ( I ) , (4), and (5) [21 formally should be convertible by
elimination of hydrogen halide into olefins that can be
cleaved by the hydrazide [ll.If theelimination of HHal is faster
than competing reactions, then the action of sodium hydrazide should lead to scission between the C atoms that
are a and 8 to the phenyl group and thus to formation of a
hydrocarbon (2) and a hydrazone (3).
We have found that under the conditions of hydrazidolysis
of C = C bonds[ll (in a hydrazine/ether mixture at 35 OC or
in a hydrazine/benzene mixture at 6OoC; excess of sodium
hydrazide) this cleavage does occur to a large extent with
halides of type ( I ) . With (4) or (5) it occurs only to a small
extent, the main reactions being replacement of the halogen
by hydrogen, or a hydrazine group respectively.
H
Hal
la I p
C6H5-C-C I
I
1) 2NaNH-NH2
2) HzO
-
H
I
C&-C-H
I
Dip1.-Ing. E. Rauch
Organisch-Chemisches Institut der Universitat
Hindenburgplatz 55
44 Munster (Germany)
[l] Cf. Th. Kauffmann, Angew. Chem. 76, 214 (1964); Angew.
Chem. internat. Edit. 3, 349 (1964); Th. Kauffmann, H. Henkler,
E. Rauch, and K. Lotzsch, Chem. Ber. 98, 912 (1965).
[2] When an olefin containing a @,y-doublebond with respect
to a phenyl group is treated with sodium hydrazide, an a,@double bond results which is subsequently cleaved.
[3] Molar ratio; halide: NaNH-NH2:NHz-NHz
= 1:5:5-15.
[4] Th. Kauffmann, K . Lotzsch, and D. WOKChem. Ber. 99, 3148
(1966).
Stereoselective Synthesis of 1-Butene with Lithium
Sulfate as Elimination Catalyst
By H . Noller, M . Rosa-Brusin, and P. Andrdu[*I
In our studies of the elimination of hydrogen halide on solid
catalysts we have always obtained mixtures of the three linear
trans 2-butene
butenes from n-butyl chloride or bromide&
being formed in large excess 121. Recently, however, using
lithium sulfate and a microcatalytic technique (a pulse
technique) a t temperatures between 320 and 370 O C , we
obtained I-butene exclusively from n-butyl bromide [31; at
390 "C some 10 %, and at 42OoC some 50 %, of 2-butene
was formed.
+
H2N,
+
C'
A nitrogen stream (35 ml/min),saturated at 70 OC with n-butyl
bromide, was passed through a horizontal glass tube (inner
diameter 2 cm) holding ca. 50 g of catalyst, then through a
170
Angew. Chem. internat. Edit.
Vol. 6 (1967)
1 No. 2
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phenylalkanes, cleavage, halogen, sodium, hydrazide
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