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New Syntheses of the Adamantane Ring System.

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despite their lower molecular weights, the carbon compounds
(2u)-(2c) are less volatile and higher melting than the
corresponding silicon analogues.
Received: December 15th, 1964 [Z 883/706 IEI
German version: Angew. Chem. 77, 169 (1965)
[ I ] Cf. H . Schmidbaur and W . Findeiss, Angew. Chem. 76, 753
(1964); Angew. Chem. internat. Edit. 3, 696 (1964); H. Schmidhaur, J . A. Perez-Garcia, and H. Hussek, unpublished results.
[2] The only gallosiloxane known heretofore was tris(trimethy1siloxy)galliurn: see H. Schmidbaur, Chem. Ber. 96, 2696 (1963).
[3] H. Schmidbnur, J. organometal. Chem. 1, 28 (1963); J. Amer.
chem. SOC.85, 2336 (1963); H . Schmidbaur and M . Schmidf, ibid.
arithmetic mean 5 of the two coupling constants is almost
exactly equal to the values found for the isosters: hexamethyldisiloxane: I 18.0; hexamethyldigermoxane: 125.5 cps
12.31.
II
1
I
84, 1069 (1962).
(41 E. G . Hoflmann and W.Tornau, Angew. Chem. 73,578 (1961).
[ 5 ] G. E. Coates and R . G. Hayrer, J. chem. SOC.(London) 1953,
25 19; G. E. Coates: Organometallic Compounds. Methuen, Lolldon 1960.
[6] Measured in CC14 as solvent on a Varian A 60 instrument with
60 Mc. 8 is in cps relative to tetramethylsilane as internal standard.
Trimethylaluminum Trimethylphosphorus Oxide
and Trimethylarsenic Trimethylgallium Oxide
By Dr. F. Schindler, Priv.-Doz. Dr. H. Schmidbaur, and
cand. chem. G. Jonas
Institut fur Anorganische Chemie
der Universitat Marburg/Lahn (Germany)
Trimethylphosphine oxide reacts rapidly in benzene with
trimethylaluminum etherate to form a 1 : 1 adduct with a
P-0-A1 bond.
The homologous ethyl compounds (2)-(4) are also formed
readily, and so is the analogous compound (5) with an
As-0-Ga
grouping obtained from trimethylarsenic oxide
and trimethylgallium etherate.
The chemical and spectroscopic properties of (1)-(5) indicate them to be isosteric with the hexaalkyldisiloxanes
RsSi-O-SiR3 (6) and hexaalkyldigermoxanesR3Ge-0-GeR3
(7). All the new compounds are surprisingly stable to heat
and exhibit no tendency to dissociate or to undergo intramolecular redox reactions up to about 150 'C. Cryoscopic
and osmometric determinations of their molecular weights in
benzene revealed that they are all monomeric. Because the
polarity of the P-0-A1 grouping is much stronger than that
of Si-0-Si or Ge-0-Ge bridges, the melting and boiling
points of the new oxides lie by more than 100°C above
those of the corresponding disiloxanes or digermoxanes.
The solubilities of (Z)-(4) in non-polar solvents other
than benzene are also lower than those of (6) or ( 7 ) . However
( 5 ) is much more soluble in such solvents than (1)-(4),
but cannot be distilled without decomposition.
The number, multiplicity, and area ratios of the proton
signals in the nuclear magnetic resonance spectra [ l ] of the
new compounds were invariably in accordance with the
theoretical expectations. The isosterism of the new oxides
with (6) and (7) is particularly obvious on comparison of
the coupling constants J(lH-13C). For ( I ) and for ( 5 ) , the
Angew. Chem. internat. Edit. 1 VOI.4 (1965)
1 NO. 2
108,s
I27
I27
-
-
109.0
134.5
n7.0-
I
1
Received. December 15th, 1964 [Z 8841707 (€1
German version: Angew. Chem. 77, 170 (1965)
[I] Measured in benzene as solvent on a Varian A 60 instrument,
60 Mc. The mean error for J(H-C) is about i- 1 cps.
[2] H . Schmidbaur, J. Amer. chem. SOC.85, 2336 (1963).
[3] H. Schmidbaur and I. Ruidisch, Inorg. Chem. 3, 599 (1964).
New Syntheses of the Adamantane Ring System
By Prof. Dr. H. Stetter, Dip1.-Chem. J. Gartner, and
Dr. P. Tacke
Institut fur Organische Chemie
der Technischen Hochschule Aachen (Germany)
3-Methylenebicyclo[3,3,l]nonan-7-one ( I ) [ l ] readily undergoes cyclization in the presence of acids to give I-hydroxyadamantane derivatives substituted at the 3-position.
(I/
(21,X = OH
(31, x = c1
(41, X = OC2H,
I jJ ,
X = NH-Ac
l6), X = NHZ
1,3-Dihydroxyadamantane (2) is obtained in almost quantitative yield from ( I ) with dilute sulfuric acid. Treatment
of ( I ) with hydrochloric acid produces 1 -chloro-3-hydroxyadamantane (3), m.p. 205.5 "C, while acids in ethanol lead
to 1 -ethoxy-3-hydroxyadamantane (4), m. p. 77.5 "C. Acetonitrile reacts with ( I ) under the conditions of a Ritter reaction
to give 1-acetamido-3-hydroxyadamantane(5), m. p. 220 OC.
The reaction of ( I ) with aqueous ammonia in a sealed tube
at 130 OC yields I-amino-3-hydroxyadamantane(6), m. p.
267 ' C .
The same principle can be applied to prepare polyethers (7)
of adamantdne by treating ( 1 ) with acids in inert solvents.
The same approach can be used to prepare adamantane
derivatives from 3,7-dimethylenebicyclo[3,3,l]nonane (a),
m.p. 75OC, which can be obtained from ( I ) in a Wittig
reaction; ring closure of (8) with acids gives l-methyladamantanes containing substituents at the 3-position.
Thus, I-hydroxy-3-methyladamantane(9), m.p. 131 'C, and
l-methyl-3-methoxyadamantane(l0), b.p. 99- 100 "Cjl3 mm,
153
117.8
-.
.
125.8
are readily obtained from (8) in water or methanol by
acidic catalysis. Similarly, 1-acetamido-3-methyladamantane
( I ] ) , m.p. 112 O C , and l-methyl-3-(p-methoxyphenyl)adamantane (12), b.p. 145 OCj5 mm, are obtained with acids in
acetonitrile and anisole, respectively.
It seems remarkable that the hydrocarbon (8) forms 7rcomplexes with metal salts; the complex formed with CuCI,
m.p. 196-198 "C, is unusually stable.
Received: December 16th, 1964 [ Z 881/702 IE]
German version: Angew. Chem. 77, 171 (1965)
[ I ] H. Stetter and P.Tacke, Angew. Chem. 74, 354 (1962); Angew. Chem. internat. Edit. I , 333 (1962); Chern. Ber. 96, 694
(1963).
The compounds (2) are all soluble in water. If 5-10 % solutions of (2) in water are mixed with an equal volume of a
40 %, solution of HBF4, beautiful crystals of the tetrafluoroborates precipitate out. None of the compounds (2) absorbs
between 2600 and 3100 cm-J. Their maxima in the ultraviolet are at shorter wavelengths than those of the compounds ( I ) , e.g. for (Za), Amax = 293 mp, log E = 3.55,
whereas for ( l a ) , Amax = 339 mp, log E = 4.32 in ethanol.
The triazenes ( I ) can be reobtained from (2) bytreatment
with NazS204 i n alkaline solution.
131
By analogy t o the reaction of ( I ) , dehydrogenation of I-phenyl-3-(1-isoquinolyl)triazene, m.p. 136 "C, Amax = 397 mp,
log E = 4.28 in ethanol, leads t o a 53 % yield of 3-phenyl-6bromotetrazolo[5,l-alisoquinolinium bromide ( S ) , m. p.
292OC, Amax = 293 mp, log E = 3.95 in ethanol. To our
knowledge, compound (3) is the first tetrazolo[5,1-a]isoquinoline prepared.
Received: December 16th, 1964 [ Z 886/709 IE]
German version: Angew. Chem. 77, 171 (1965)
Synthesis of 3-Phenyltetrazolopyridinium
Bromides and 3-Phenyl-6-bromotet~azolo[5,l-a]isoquinolinium Bromide
[I] A . ETschtschibabin, J. russ. phys. chem. SOC.57, 301 (1925);
Chem. Abstr. 20, 2499 (1926).
[2] A . Messmer, J. Varady, and I . Pinter, Acta chim. Acad. Sci.
hung. 15, 183 (1958); Chem. Abstr. 53, 3200e (1959).
By Dr. A. Messmer and Dip1.-Chem. A. Gellkri
Central Research Tnstitute of Chemistry, Hungarian Academy of Sciences, Budapest (Hungary)
We have found that I-(cc-pyridyl)-3-aryltriazene( I n ) , RI =
R2 = H [l], is dehydrogenated in ethyl acetate at room temperature by 2,4,4,6-tetrabromocyclohexadien-l-one[2] t o
give 3-phenyltetrazolopyridinium bromide (Za), R1 =
R2 = H, m. p. 278-280 OC, in 87% yield; the BFf salt of (20)
melts at 246 "C.
Further derivatives (lb)--(lf) of compound ( I ) were prepared by azo coupling of or-aminopyridines and the corresponding benzenediazonium salts.
OCH3, m.p. 188-189"C, 48%
H,
RZ
=
( l c ) , R1 - H,
R2
- CI,
R2
Br,
m.p. 206-207 "C, 39 ?(,
H,
m.p. 2O9-21O0C, 29uL
Br,
m.p. 206-208 " C , 46O.;
( I b ) , R1
:.
( l a ) , R1
=
H,
(le), RJ
--
CH3, R2
(If), Rl
--
CH3, R2
.
i
2
89 "/o ; BF; salt: m. p. 179 "C
(2r), m.p. 306-307 " C , 85 :4; BF; salt: m.p. 227 "C
(Zd), m.p. 310-311 " C , 84y0; BF; salt: m.p. 249°C
(2e/, m.p. > 360 "C,
78 96 ; BF; salt: m. p. 198 "C
(Zf), m.p. > 360°C,
92O:,; BFY salt: m.p. 228 "C
154
By Doz. Dr. E. Uhlemann and Dip1.-Chem. Helmut Muller
Institut fur Anorganische Chemie der Universitat Leipzig
(Germany)
Thio derivatives of P-dicarbonyl compounds can be obtained
by acid- or base-catalysed reaction of the oxygen compounds
with hydrogen sulfide [1,2]. With highly unsymmetrical P-dicarbonyl compounds, the point of attack of the hydrogen sulfide is largely determined by the constitution of the starting
material, whereas for P-diketones with only slightly different
substituents two isomeric thio derivatives are t o be expected.
We have found that P-thioxo ketones of uniform structure can
be readily obtained by a Claisen-type condensation of ketones with dithioic esters or thionic esters. Yields of over 50 %
are obtained.
Monothiodibenzoyimethnne
m.p. 195-196"C, 427;
All these compounds contain an intramolecular hydrogen
bond (characteristic broadening of the infrared bands between 2600 and 3100 cm-1) and o n cyclodehydrogenation
yield the following derivatives (Zb)-(Zf) :
(26), m. p. > 360 "C;
Synthesis of $-Thioxo Ketones by Condensation of
Ketones with Thionic Esters
Acetophenone (40 g or 0.33 mole) is added slowly with stirring t o a suspension of 13 g of sodamide (0.33 mole) in 200 ml
of ether. After 15 minutes, a solution of 24 g of 0-methyl
thiobenzoate (0.16 mole) in 50 ml of ether is added dropwise.
The mixture is stirred for 3 h at room temperature and left
standing overnight. The precipitate is dissolved by adding
ice-water, and the aqueous solution is extracted with ether.
On passing carbon dioxide into the aqueous solution,
monothiobenzoylmethane separates out in the form of
shiny red crystals, m.p. 82-83 'C. The yield is 26 g or 68%.
Received: December 21st, 1964
[ Z 885/708 IE]
German version: Angew. Chem. 77, 172 (1965)
[l] S. K . Mitra, J. Indian chem. SOC.10, 11 (1933).
[2] R . Muyer et al., Angew. Chern. 75, 1011 (1963); Angew.
Chem. internat. Edit. 2, 370 (1963).
Angew. Chem. internat. Edit. Vol. 4 (1965) / No. 2
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