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Lithium Phthalocyaninatomanganate(I) and (0).

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COMMUNICATIONS
Synthesis of Substituted Acetylenic Compounds
to the scheme below to give ( I ) and (2) as bright and dark
green crystals, respectively.
By Dr. H. G.Viehe [ I ]
MnPc iLizBzph
Union Carbide European Research Associates,
Brussels (Belgium)
Li[MnPrl.6THF
The preparation of the ynamine ( I ) in 86 '% yield opens not
only the way to this otherwise rather inaccessible class of
compounds [2], but also offers a general method for the
synthesis of mono- and disubstituted acetylenic compounds.
2 LiN(C2H& in ether
-10 min at -80 "C,
30 min at - 20 "C
C~HSCH=CCIF
> CsHsC= C-N(CIHS)~
(IJ
The elemental analysis and the infrared spectrum establish
structure ( I ) in agreement with the results of 121.
By means of this reaction, which is the result of previous
findings [I],we succeeded in preparing a number of other
heterosubstituted acetylenes. The indicated yields are derived
from preliminary experiments and may be open to improvement.
M
=
alkali metal or the like, X
=
->
TH F
-~+
I.i~MnPcl~6TIHF
4 LiBzph
Liz[MnPcl.6rHF
+ LiRzph
(/j
(2)
On thermal degradation in vu('iio, they both liberate tetrahydrofuran quantitatively; in air, they decompose immediately with darkening in color and cvolution of tetrahydrofuran.
In addition to their solubility i n tetrahydrofuran, the two
compounds also dissolve i n acetonitrile, giving intensely violet
solutions. Iodine in tetrahydrofuran oxidizes them quantitatively to Lil and MnPcl. The ionic nature of ( I ) and (2) was
established by transport experiments in acetonitrile. Their
magnetic moments, measured :it 293 "K,were p e ~ =
. 2.86
Bohr magnetons corresponding l o two unpaired electrons for
( I ) , and p e ~=
. 4.13 Bohr magnctons corresponding to three
unpaired electrons for (2), thus confirming the even and odd
total number of electrons to bc expected for one- or twostage reduction of MnPc. Formally one can ascribe the
oxidation numbers -I I and 0, respectively, to the central
manganese atoms i n ( I ) and ( 2 ) .
[Z 507/344 IE]
Received, M a y 14th. 1963
German versi~ii~:
Angew. Chem 75, 639 (1963).
+ 2 RM + R - C E C - R + (RH + MX + MF)
(a) RCH=CXF
+ LizBzph
TH F
halogen
Examples:
Photoisomerisation of 1,3-Cyclohexadienes
2 Li-n-butyl
r -
By Doz. Dr. H. Prinzbach and Dipl.-Chem. J. H. Hartenstein
-+
I
C~HS-CH=CCIF
Chemischcs Labordtorium der 1Jnivcrsitit Freiburg/Breisgau
(Germany)
I-
2 KOC(CHT:
Diazomethane-sensitized intramolecular photoisomerisation
l'henyl- and methyl-lithium gave analogous reactions with
low yields.
HCH=CCIF
2 KOC(CH3)
+ 2 RM
(b) RCX=CXP
-A HC=C-OC(CH3)3, yield cu. 20 %
R-CEC-R
+ (RX + MX + MF)
--f
Exumples :
C6HSCBr=CCIF
2 LiC6HS
~
--->
~
C ~ H S - - C ~ C - C ~ Hyield
S , cu. 70 %
Phenylmagnesium bromide gives only traces of tolane,
whereas phenyl- and methyl-lithium react well.
FCCI=CCIF
3 Lic6H~
->
C ~ H S - C ~ C - C ~ Hyield
S,
CU.
of dimethyl I ,3-cyclohexadiene- I,4 dicarboxylate ( / a ) to give
dimethyl bicyclo[2.2.0]hex-2-enc-I ,4-dicarboxylate ( 2 a ) [I]
is not limited by the specific geoinctrical or optical properties
of the ester groups. Under the same conditions, irradiation of
a solution in ether of the dinitrile (Zh) (Amax in ethanol =
306 mp, E--- I 1 100; 296 mp, E - 1 1 150; proton magnetic
resonance spectrum: singlets at T 3.25,2 protons and z =
7.45, 4 protons) in the presence of diazomethane gives
bicyclo[2.2.0]hex-2-ene-l,4
dicarbonitrile (2h), in about
70 %, yield as a colorless oil, b. p. 90 -9 I "C/O.OOl mm, only
terminal absorption at 220 mp; proton magnetic resonance
spectrum: singlet at z = 4.63 and a AzBz-multiplet at T =
8.57;in the infrared spectrum, n ( = C ~H)
- of cyclobutene lies
30 %, cr. 131
It
Received, Jan. 2nd, 1963
[Z 519/352 IE]
Publication withheld until now at the author's request
German version: Angew. Chem. 75, 638 (1963).
[ I ] Communication No. V on Heterosubstituted Acetylenes;
Communication No. IV: H . G . Viehe and E. Franchiinont, Chem.
Ber. 95, 319 (1962).
[ 2 ] V. Wolfand F. Kowitz, Liebigs Ann. Chem. 638, 33 (1960).
[ 3 ] D. Seyferth, D. E.WeIch and G . Raab,, J. Amer. chem. SOC.
84, 4261 (1962).
=
$
(4)
I
a ) -COzCHs
b) -CN
C ) -H
(3)
R
Lithium Phthalocyaninatomanganate(1)and (0)
By Dr. R. Taube and cand. chem. H. Munke
Institut fur Anorganische Chemie
der Universitit Greifswald (Germany)
Manganese phthalocyanine (MnPc) and a solution of
dilithiobenzophenone (LiZBzph) in tetrahydrofuran (THF)
react together on exclusion of oxygen and moisture according
Angew. Chem. internat. Edit. / Vol. 2 (1963) No. 8
at 741 cm-' (21). However, ( / a ) and ( 1 b) behave differently
on unsensitized irradiation (Hanau Q 81 high-pressure mercury lamp). Compound ( 1 h) undergoes ring opening to give
471
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