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2,408,066
Patented Sept. 24, 1946
[UNITED STATES PATENT OFFICE
P-AMINO-IBENZENE-SULPHAMIDE
‘DERIVATIVES
.Winfrid Hentrich, Rodleben, near 'Dessau-Ross
’lau, Anhalt, and Erik Schirm,'Dessau, Anhalt,
Germany; vested‘ in the Alien Property Custo
dian
_ No Drawing. Application June‘ 3, 1939, Serial No.
_ 277,300. In Germany May 5, 1938 _
1
6 Claims. (01. zen-397.7)
;
It hasv been found that technically valuable p
amino-benzol-sulphimides of the general for
2
.
.
conversion of the groups contained in the mole
cule, which allow of being conveyed into amino
groups, is also performed to methods known in
themselves.
The .nitro-, azo- or azoxy-group
respectively is converted into an‘ amino-group by
reduction, and the acyl-amino-group by saponi
are obtainable in causing the reaction of benzol
?cation.
sulpho-halogenides, which in p-position contain
'
.
Y
The’ sulphimides obtainable accordingv to the
a substituent transformable into an amino group,
present method are excelling by the fact that
upon alkali-compounds of ' acid-amides of the 10 with alkalis, ammonia and numerous organic
bases they givewater-soluble salts, the solutions
general formula R,—X-‘—NI-Iz, or alkali-com
pounds of benzol-sulphamides, which in p-posi
of which react neutrally, which is of great im
portance for their being ‘applied-particularly in
amino group, upon acid-halogenides of the gen
the pharmaceutical domain-eas remedies against
eral formula R,—X-—Hal, and in forming then in 15 strepto- and staphylo-bacteria infections. It is
the condensation-product the free ‘amino group
true that similarly constituted sulphimides could
already be produced, whereat the amino-group
in a way known in itself.
tion contain a substituent transformable into an
In the aforementioned general formulas R
means any acyclic or cyclic hydrocarbon residue
of the amino-benzol-sulpho-residue was, how
ever, not arranged in para-, but in meta-position.
which may also contain hetero-atoms or hetero 20 Thosecompounds are of quite a different char
atom groups such as oxygen, sulphur, nitrogen,
acter and they did not prove e??cient as medical
halogen, hydroXyl-, sulpho-, ether-, amino-, sub
remedies andparticularly not against strepto
stituted amino groups such as acylamino-, nitro-, ~
and ‘staph‘ylo-bacteria infections;
'
azo-, azoxy-, ester-,Iacid-arnide groups and the
Example 1
like; X means the groups S02 or CO, and Hal 25
means a halogen-atom and particularly a chloro
_ 200 weight parts of, p-nitrobenzol-sulphochlo
atom. By the groups ‘which according to well
ride are dissolved in 1000*volume-parts of toluol.
known methods are easily converted into an am
Into this solution 193 weight-parts of p-toluol
ino group and which, in the benzol-sulphohalo
sulphamide-sodium are brought in the form of a
genides or benzol-sulphamides respectively, ought 30 ?ne powder. Then the mixture is heated at the
to be arranged in p-position to the sulpho-group,
re?ux-cooler While stirring, until the toluol be
we mean acyl-amine groups, the nitro-group, the
gins to boil and at this temperature the mixture
azo-group, the azoxy-group and the like.
is kept for about 5 hours under permanent stir
As to the acid-amides of the general formula
ring. After cooling down the separated reaction
R-—X—NH2 or, respectively, acid-halogenides of ' product is ?ltered oil’, then washed with a little
the general formula R.—X—Hal there are to be
considered for the present method e. g. the
amount of alcohol and dissolved in a solution of
150 weight-parts of calcinated soda in 2500
weight-parts of water while warming. The hot
solution is cleared by ?ltration and the ?ltrate is
amides or halogenides respectively of the follow
ing acids: acetic acid, butyric acid, lauric acid,
stearic acid, methane-, ethane-, ethylene-, do 40 cooled in ice. After a several hours’ standing
decane, hexadecane-, sulpho-acid, further the
the sodium salt of the di-sulphimide abundantly
benzoic acid, its homologues and substitution
precipitating in the form of small crystal ?akes
products, the phenyl-acetic acid, the phenoxy
turning into a thickish crystal-mass, is sharply
acetic acid, the naphthoic acid, the picolic and
sucked off or pressed off, then covered with some
nicotinic acid, the benzol-sulpho-acid, its homo
logues and substitution products such as 2,5-di
45 ice-water and ?nally dried in the warmth.
ory) of p-nitro-p'-methyl-dibenzol-sulphimide
acid, the naphthaline-sulpho-acids etc.
sodium. In working-up the mother-lye further
amounts of the condensation-product may be
The mixing of those acid-amides or -halogen
ides respectively with the p-substituted benzol
sulpho-chlorides or -amides respectively is per
formed to well known methods either directly
or in the presence of an indifferent diluent such
as benzol, toluol, xylol, chloro-benzol, tetra-chlo
We
thus obtain 262 weight-parts (=77% of the the
chloro-aniline-ll-sulpho-acid, ‘the benzyl-sulpho
50
gained.
‘
.
262 weight-parts of this nitro-compound are
stirred, within half an hour at 60 to 65° 0., into
a solution of 183 weight-parts of crystallized so
dium-sulphide (NazS.9H2O) and 25 weight
ro-hydrocarbon or the like. The subsequent 55 parts of sulphur in 1000 Weight-parts of water.
2,408,066
4
3
precipitated out, filtered in the cold and puri
?ed by dissolving and precipitating from diluted
Then We stir for a further half an hour at 65°,
whereupon we warm up to 80° in keeping this
temperature for one hour. When the reaction
alcohol.
Example 3
is ?nished an exceeding of sodium-sulphide will
still be traceable. The thus obtained solution
236 weight-parts of the sodium salt of the p
is then cooled in ice. After a rather long stand
acetyl-amino-benzene-sulphamide are suspend
ing in the cold the meanwhile developed crystal
mass is ?ltered 01f.
ed in 150 volume-parts of toluene. To the sus
From the ?ltrate a further
amount of reduction-product is separating after
an addition of common salt.
pension 128 weight-parts of ethyl sulphonic acid
chloride are added while stirring and the mix
10 ture is heated under re?ux for 5 hours. The re
action mixture is cooled down and ?ltered, the
residue is washed and dissolved in warm 5% soda
For puri?cation the united precipitates are re
crystallized from a little amount of water, where
at the eventual yellow aspect can be eliminated
lye. The solution is boiled until the acetyl group
by an addition of a little amount of sodium hy
is split off. After working up in the manner as
drosulphite. The portions left dissolved are pre
in Example 2 the p-amino-benzene-(ethyl) cipitated from the mother-lye by common salt.
sulphimid of the formula
Now the precipitates are dissolved in much water
whereupon we acidify with muriatic acid and
?lter off the white precipitate, which we sub
is obtained.
sequently dissolve and precipitate from a large
The sulphonamide derivatives obtained by the
amount of boiling Water. After drying the sub
prescribed processes having an alkyl sulphon res
stance obtained forms a white micro-crystalline
idue in the molecule such as p-amino-benzene
powder with a flash-point of 231 to 232° C. (non
methyl - sulphimid, p _ amino - benzene-ethyl
corrected), which in a sodium-solution, while
sulphimid, p - amino-benzene-propyl-sulphimid,
forming a neutrally reacting sodium salt of the 25 p-amino-benzene-butyl-sulphimid and the like
formula
are especially valuable as they have a very good
compatibility with the body.
We claim:
N9.
'
1. Compounds having the general formula
is soluble. In the same way salts with organic 30
bases are soluble e. g. salts with tri-ethanol
amine.
Example 2
wherein R is an aliphatic radical and Z is se
236 Weight-parts of the sodium salt of the p 35 lected from the group consisting of hydrogen
and alkalis, ammonia, and organic basic form
acetamino-benzene-sulphamide are suspended in
ing salts in combination with the rest of the
1000 volume-parts of xylol; then 133 weight
molecule.
parts of benZoyl-chloride are added, whereupon
2. An alkali metal salt of an Nl-alkylsulphonyl
themixture is heated up at the re?ux-cooler for
3 "to 4 hours until the xylol begins to boil. The 40 sulphanilamide.
3. An Nl-alkylsulphonyl sulphanilamide.
mixture is ?ltered after being cooled down, the
4. An Nl-butylsulphonyl sulphanilamide
residue is Washed with a little amount of alco
5. An Nl-octylsulphonyl sulphanilamide.
hol and taken in a warm exceeding 5%-sodium
6. An Nl-methylsulphonyl sulphanilamide.
carbonate solution. The ?ltered solution is then
boiled until the acetyl group is split off. By 45
acidifying with muriatic acid the obtained N
(p' - amino - benzene-sulphonyl-)benzamide is
W'INFRID HEN’I'RICH.
ERIK SCHIRM.
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