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Patented Nov. 5, 1946
. ZiAlJiZ
UNITED STATES PATENT OFFIQE
2,410,772
PREPARATION OF NEW SULPHONAMIDE
DERIVATIVES
Gordon 'Cecil Butler, Ottawa, Ontario, Ezra
Lozinski, Westmount, Quebec, and Arthur
Duston Odell, Su?ield, Alberta, Canada
No Drawing. Original application January 12, I
1942, Serial No. 426,470. Divided and this ap- ’
plication April 7,1945, Serial No. 587,202. In
Canada December 24, 1941
2 Claims. (or. 260-397.?)
1
.
This invention relates to sulphonamide derivatives and has for its object the preparation of new
therapeutically useful para-amino-benzene sul
phonamide derivatives of substituted naphthols
by
reacting
is preferably carried out in an atmosphere of
para-acylaminobenzenesulphonyl
benzenesulphonyl chlorides with the requisite
amino-naphthalene derivatives followed by hy
'-
IITH-C—CH3
l. n +
(‘>11
.
—CH;—CH=OH2
a
0:‘ =0
,
NH:
1
(II)
(III)
_
NH-o-cm on
1
The invention is further illustrated by the fol
lowing examples of procedures which may be fol
lowed in the preparation of N-(para-amino-ben
—CH2—OH=CH1
1|
zene-sulphonylyl) - 2 - a1ly1-4-amino-l-naphthol,
and N-(para-amino-ber1zene-su1ph0nylyl) -l-hy
20
derstood, however, that the invention is not lim
ited to the exact details given in these examples:
,
-
n
‘(130,7
.7
The solution is cooled and the crystals are then
?ltered off and washed thoroughly on the ?lter
with alcohol. By this procedure there results
Example 1
50 grams of 2-a11y1-‘l-amino-1-naphtho1hydro
chloride (Formula I) (prepared according to
Fieser, Campbell and Fry, J. A. C. S. 61, 2213,
ing the water. to boiling temperature.
l
0=s=o
droxy-_4-amino-2-naphthoic acid. It is to be un
1939) are dissolved in one litre of water by bring
2
nitrogen
chlorides with the amino group of 4-amino-naph
thols containing an organic substituent attached
to the nucleus at position 2.
This application is a division of parent appli
cation Serial No. 426,470, ?led January 12, 1942. 10
The new compounds contemplated by this in
vention are prepared by reacting para-acylamino
drolysis of the acyl group.
'
cedure, as represented by the following reaction,
N ~(para - acetamino - benzene - sulphonylyl) - 2
allyl-‘l-amino-l-naphthol (Formula IV), which
melts at 240° C. with decomposition.
In order to achieve the hydrolysis of the acetyl
30
group of this compound (Formula IV), 60 grams
of it are re?uxed for two hours with four litres
of alcohol and 300 cc. of concentrated aqueous
hydrochloric acid, as represented by the following
35 reaction:
‘u’
NH2.H G1
NH-C-C‘Ha
OH
(I)
60 grams of sodium acetate (3H2O) are then 40
added to the solution to precipitate free amine,
the reactions involved being substantially as rep
resented by the following equation:
OH
OH
|
I
CHrCH=CH2
'‘
45
2%
(IV)
-CH2—CH=CH1
-—->
+ NaCl
+ CHa-COONa
NHgHCl
,
+ CHa-CO OH
NHa
'50
(II)
on
'
Q @GHPOH=CH2
3
addition of ‘700 cc. of lA-dioxane and 49 grams
mula III) are then added during a ?ve minute
11TH:
0:8 _--—NH
The amine (Formula II) is re-dissolved by the
of p-acetamino-benzene-sulphonyl chloride (For
_
55
(V)
When the alcohol is removed by distillation and
the residue is crystallized from 50% aqueous al
period With continual stirring. Stirring is con
tinued for a further ?fteen minute period, during
c'ohol there is obtained a product which, on fur
which time a large amount of crystalline product
ther recrystallization from 50% aqueous alcohol
separates from the reaction mixture. This pro 60 yields N -(para - amino - benzene-sulphonylyl) -2
v.
4
3
allyl-4-amino-l-naphthol (V). This compound
trated hydrochloric acid. After 2 hours re?ux
ing, charcoal is added to the solution, boiling con
melts with decomposition at 195° C.
Example 2
_ tinued for 5 minutes and the solution is ?ltered
' .
hot. The ?ltrate is reduced to about one-quarter
of its original volume and chilled. The N -(para
10 grams of 1-hydroxy-4-aminoé2-naphthoic'
acid (VI) is dissolved in 1 litre of water con
taining 4.15 grams of sodium bicarbonate. After
solution has been effected 6.7 grams of sodium
acetate (31-120) are added followed by 500 cc. di
oxane.
amino-benzene-sulphonylyl)-1-hydroxy-4 - ami
no-2-naphthoic acid hydrochloride (VIII) sepa
rates as colourless needles which are ?ltered o?
and washed with alcohol. After drying the crys
tals do not melt but decompose slowly between
240 and 250° C. The free amine prepared from
11.5 grams p-acetamino benzene sul
phonyl chloride (I11) are added in small portions
to the above solution over 15 minutes with con
the above hydrochloride (VIII), after crystallisa
tion from alcohol, melts at 225° C. with decompo
sition.
tinuous stirring and warming to 50° C. Stirring
is continued another 15 minutes to complete the
reaction; the solution is. then cooled and made
slightly acid by the addition of hydrochloric acid
when the N-(para-acetamino-benzene-sulphon
ylyl)-1-hydroxy-4-amino-2-naphthoic acid (VII)
separates in the form of ?ne needles. This is ?l
tered off and washed thoroughly on the ?lter, with 20
water and alcohol. Further puri?cation is
achieved by digesting the crystals with hot alco
hol, cooling, ?ltering and Washing with alcohol.
After drying, the product melts at 240° C. with
decomposition.
We claim: 7
I
1. A process for the preparation of N-(para
amino - benzene-sulphonylyl)-1-hydroxy-4-ami
30 no-2-naphthoic acid by the interaction of para-
acetamino-benzene-sulphonyl chloride and l-hy
droxy-4-amino-2-naphthoic acid followed by hy
drolysis of the acylamino group in the resultant
35
(v1)
'
ivii)
For hydrolysis of the acetyl group 20 grams of
the N- (para-acetamino-benzene-sulphonylyl) ~1
hydroxy-li-amino-2-naphthoic acid (VII) are re
?uxed with 2 litres alcohol and 100 cc. concen 40
product.
'
1
>
2. The new compound N-(para-amino-ben
zene - sulphonylyl) -1-hydroxy-4-amino-2-naph
thoic acid.
.
-
GORDON CECIL BUTLER.
EZRA LOZINSKI.
ARTHUR DUSTON ODELL.
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