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Capture of Benzynes by Acyldiazoalkanes.

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with aluminum alkyls to form AsR3 and SbR3, respectively,
in acceptable yields [3].
Finely powdered As203 (or SbzO3) is dispersed i n hexane,
and the trialkylaluminum is added slowly, the mixture then
being kept at 60 "C for 1-2 h. The trialkylarsines (or trialkylstibines) formed are then removed from the equilibrium mixture at highly reduced pressure:
2 AIR3
+
MzOi
AIR,
+ (R2M)zO +
2 RAlO
-5 2 MRs
+
3 RA10
In order to obtain fully alkylated arsines and stibines in satisfactory yields, excess trialkylaluminum has to be employed.
The yields of MR3 decrease in the following order:
M = Sb > As > Bi and
,n-GH9R = C ~ H S -:
> i-C4Hg- > i-C6HI)-
b.p. [ 'C/mnil
as can be seen from the following examples, where a molar
ratio AlR3: MzO3 = 3: 1 was employed:
62--62/0.05
46-47/0.0.5
(C2Hs)3Sb- 89 %; (n-C4Hg)3Sb - 87 %; ( i G H d 3 S b - 71 %;
(i-CsH1&Sb
-
62 %; (C2H5)3As
-
72 %; (i-C4Hs),As
-
32 %, and
4610.4
(n-C4H9)3Bi - 6 %.
Alkylation of AsZ03with higher aluminum alkyls (R 3 C,)
resulted mainly in dialkylarsine oxides. Some of thesewere
hitherto unknown, e.g. [ ( ~ - C ~ H ~ ) Z A (62
S ] ~%,
O b.p. 68 to
7O0C/O.05 mm).
Diisobutylarsine oxide was oxidized to the new compound
diisobutylarsinic acid (i-C4H9)2AsOOH, m.p. 135 "C.
Received, November lath, 1963 [ Z 626/451 I € ]
German version: Angew. Chem. 76, 99 (1964)
[a] Oil-bath temperature.
[b] Unstable.
[ c ] Decomposes o n distilldtioii.
Oxidation with excess monoperoxyphthalic acid in ether/
chloroform converts ( 4 a ) into N-butylpropanesultam-3-one
(6) [ 5 ] , whereas reduction with lithium aluminohydride in
ether causes ring fissure to give 3-(butylamino)propane-lthiol (7), b.p. 82-84OC/O.2 mm.
[ 11 E. Krause and A . Y . Grosse; Die Chemie der metallorganischen
Verbindungen. W. de Gruyter, Berlin 1937.
[2] German Patent Application K 20071 IVb/120 (April 5th,
1956), Kali-Chemie inventor: H . Jenkner.
[3] German Patent Application (November 16th, 1961),Stauffer
Chem. Co., inventors: W . Stamm and A . Breindel.
(4a)
acid
HS-C Hz-C Hz-C I ~ ~ - X l < -C:( € I 2 ) 3 - i: I l3
I 7,
Received, November 22nd, 1963 [Z 620/449 IE]
German version: Angew. Chem. 76, 51 (1964)
(+Chlorosulfenylalkylcarbonyl Chlorides
By Prof. Dr. A. Liittringhaus and Dr. Rupert Schneider
Chemisches Laboratorium der Universitat Freiburg/Breisgau
(Germany)
We were able to convert dithiaalkane-a,o-dicarboxylicacids
into the corresponding a,w-dicarbonyl chlorides ( 1 u), ( I b),
and ( 1 c) by treatment with thionyl chloride [l]. Chlorolysis
of these at -25°C in CCl4 according to the method of
Brinfzinger [2] produced the a-chlorosulfenylalkylcarbonyl
chlorides ( 2 n ) , (2b), and ( 2 c ) [3]. The yields were so good
(up to 90 %) that the cc14 solutions could be used directly for
further reactions, e.g. for the addition onto olefins to give pchloroalkyl thioethers which serve as evidence for the structures of (2). Thus, (2a) and ethylene formed 4-thia-6-chlorocaproyl chloride ( 3 ) , b.p. 80-81 OCj0.1 mm. Reaction of ( 2 a )
in CC14 with primary amines in the presence of pyridine and
with strict exclusion of moisture gave rise to the new N-alkylisothiazolidin-3-ones ( 4 a ) , ( 4 h ) , and (4c). Correspondingly,
(2b) formed ( 4 d ) , and (2c) gave the new N-alkyltetrahydro1,2-thiazin-3-ones (5.) and (5b).
[I] R. Schneider, Ph. D. Thesis, Universitiit Freiburg, 1963.
[2] H. Brinrzinger, K. Pfannensriel, H . Koddebusch, and K . E .
Kling, Chem. Ber. 83, 87 (1950).
[3] N. Kharrasch and B. Lungford, J. org. Chemistry 28, 1901
(1963), recently achieved the synthesis of 4-chlorothiobutyroyl
chloride (2c) by a different route.
[4] N. Kltorasclz: Organic Sulfur Compounds. Pergamon Press,
Oxford 1961, Vol. I, p. 351.
[ 5 ] The name propanesultam-3-one was proposed by H . Bagcrnz
and G. Dronsclt, Chem. Ber. 93, 784 (1960).
Capture of Benzynes by Acyldiazoalkanes
By Prof. Dr. W. Ried and Dip1.-Chem. M. Schon
Institut fur Organische Chemie der Universitiit
Frankfurt am Main (Germany)
Benzynes (dehydrobenzenes) are readily accessible [l], and are
trapped in the presence of acyldiazoalkanes to give substituted
indazoles as their conversion products. The reaction is
essenitally a 1,3-dipolar addition [2]. A solution of anthranilic
The heterocyclic compounds (4a), (4b), ( 4 c ) , (5a), and ( 5 h )
are colorless oils which decompose fairly rapidly on exposure
to moist air. Aqueous bases and acids hvdrolyse
the S-N
R2
.
.
bond almost instantaneously. They presumably [4] give rise R ~ - &
+
to intermediate carboxamides with a n w-sulfenic acid group,
N,:
for we always found disulfide-type products of disproportionNIB
ation of the latter, namely the diamides corresponding to ( I ) ,
among the subsequent products. Compound ( 4 4 , which is
also a colorless oil, has its sulfur atom bonded to a tertiary
carbon atom and is thus considerably more stable.
'
Angew. Chem. internut. Edit.
1 Vol. 3 (1964) / No. I
Monoperoxyphthalic
___-__
0- "-$*
D2
I ,
INq
/
-
I
R2
~1 =
acyl
R~ = H o r C &
Scheme 1.
67
acid in acetone was added dropwise to a boiling solution in
methylene chloride of a mixture of the diazo compound and
isoamyl nitrite.The indazoles thus prepared are listed inTable 1.
Table 1. Indazoles obtained according to Scheme 1
Diazo compound
i
Benzoyldiazomethane
m-Methylbenzoyldiazomethane
p-Chlorobenzoyldiazomethane
P-Naphthoyldiazomethane
Benzoyldiazomethane
Dehydrobenzene
Reaction product
I
M.p’
The structure of the new indazoles follows from their analyses, infrared spectra, and derivatives (e.g. 2,4-dinitrophenylhydrazones). Furthermore, some of the reaction products
have already been prepared by another route 131. These experiments, which have so far produced yields of over 70 ?(,
are being continued.
Yield
[“CI
[%I
3-benzoylindazole 131
189
88
3-(rn-methylbenzoyl)indazole
3-(p-chlorobenzoyl)indazole
3-(P-naphthoyl)indazole
3-benzoyl-5(6)bromoindazole
I57
81
202
79
20s
82
258259
71
Received, November Sth, 1963 [Z 624/454 IE]
German version: Angew. Chem. 76, 98 (1964)
~
_ _
[ I ] L. Friedman and F. M . Logullo, J. Amer. cheni. SOC.85, 1548
(1963); see also M . Stiles and R . G. Miller, ibid. 82, 3802 (1960);
M . Stiles, R . G. Miller, and U. Burkhardt, ibid. 85, 1792 (1963);
G. Wittig and R . W. Hoffmann, Angew. Chem. 73,435 (1961).
[2] R. Huisgen and R . Knorr, Naturwissenschaften 48, 716
(1962).
[3] J. Meisenheimer and A . Diedrich, Chem. Ber. 57, 1715
(1924).
C O N F E R E N C E REPORTS
~~
Therapy Congress and Pharmaceutical Exhibition
Karlsruhe (Germany), August 31st to September 7th, 1963
Nearly 8000 physicians, pharmacologists, and representatives
of the pharmaceutical chemical industry from Germany and
elsewhere assembled at the 15th German Therapy Week in
Karlsruhe. The program of lectures dealt with treatment of
the peripheral circulation and disturbances of the blood
supply to organs, with the therapy of bronchitis, bronchial
asthma, and emphysema of the lungs, with the esrly detection
and treatment of malignant tumors, with the clinical use of
steroids, with the therapeutic problems of geriatry, with the
importance in therapy of the water-electrolyte balance, and
with the treatment of diseases of the abdomen and the
maxillary sinus, efc. In his plenary lecture on “Scientifically
Eased Therapy”, Prof. Dr. H . Schifer, Heidelberg (Germany),
pointed out inter crliu that aithouglh the pathogenesis of
diseases was often known nowadays, the etiology, i. c. the
actual cause of illness, was usually still unknown, especially
in the case of internal disorders. Therapy of such diseases
must, therefore, still be confined largely to the treatment of
the symptoms.
Almost 250firms took part in the e x h i b i t i o n o f p h a r m a c e u t i c a l s . Of the many new preparations on show, only
those in which new chemical compounds are being put o n the
market receive mention below. No reference is made to new
presentations that are merely mixtures of known substances.
Knoll AG., Ludwigshafen (Germany), exhibited a new
coronary dilator, I s o p t i n ’ ” . This greatly increases the
supply of blood t o the coronary vessels for a long time, and
in particular ensures increased oxygenation of the heart
muscle without greater effort from the heart. Therapeutic
doses of Isoptin d o not influence any other blood vessels. The
active compound is 2-(3,4-dimethoxyphenyI)-5-(N-homoveratryl-N-methylamino)-2-is3propylvaleronitrile( I ) , mol.
wt. 454.62, a pale yellow oil of b.p. 243-246°C,’0.01 mni,
n55 = 1.5448. It is used in the form of its hydrochloride, a
‘ C (cori-.), which
white crystalline powder, m.p. 138.5-~140.5
is sparingly soluble in chloroform, readily soluble in methanol
and diniethylformamide, soluble in ethanol, isopropanol,
acetone, ethyl acetate, err., and 7.2 “4 soluble in water at
21 <c.
68
Another preparation for increasing coronary circulation is
I n t e n s a i n @ ,introduced by Cassella-Riedel Pharma GmbH.
Intensain is 3-(~-diethylaminoethyl)-7-ethoxycarbonylmethoxy-4-methyl-2-0~0-1,2-chromenehydrochloride (2), mol.
wt. 397.66, a white crystalline powder, ni. p. 159-160 “ C ,with
a slightly bitter taste. It is readily soluble in water, alcohol,
methylene dichloride, and chloroform. The free base is
insoluble in water. Oral or parenteral administration of
Intensain gives a degree of dilation of the coronary heart
vessels not previously attained, and this is maintained for
some hours. It has no effect on the blood pressure and causes
no vasodilation in the peripheral circulation.
P r e s i n o l s from Farbenfabriken Bayer is a new hypotensive
agent with the structure of (-)-3-(3,4-dihydroxyphenyl)-2methylalanine (3). (generic name: a-methyldopa). It melts at
292-293 “C and is soluble in water and in aqueous acids and
alkalis. Although Presinol causes ii large drop in the blood
pressure, it ensures sufficient circulation in the peripheral
system and vital organs. It is well tolerated and can be used
for extended treatments. rr.-Methyldopa is a structural analogue of the natural amino acid dihydroxyphenylalanine
(dopa). a precursor in the biosynthesis of noradrenaline.
Administration of a-methyldopa probably blocks the synthesis of noradrenaline by inhibiting dopa decarboxylase.
Cheiiiiewerk Homburg have brought out a circulation analeptic,Akrinor@,containingtwonew derivatives oftheophylline,
viz. (-)-7-[2-(R,-hydroxy-rr.-methyl- 3! - phenethylamino)ethyl]theophylline hydrochloride ( 4 ) , mol. wt. 393.9, m.p. 244 to
246 “C, and 7-{2-[2-(3,4-dihydroxyphenyl)-2-hydroxyethyliiiiiino]ethyl]theophylline hydrochloride (SJ, mol. wt. 41 1.9,
Angew. Chew. internat. Edit.
Vul. 3 (1964)
1 No. I
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