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Патент USA US3020295

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United States vPater-11:0 "
3,020,285
IC€
Patented Feb. 6, 1962
2.
1
Alternatively, the reactants- may the. heatedrtogether. ‘in
the absence of a solvent andithe product rrecoveredrby
N-(CARBANILIDO)-3-O
3,020,285.
Y YRIDYL BETAINES _
recrystallization.
Seymour L. Shapiro, Hastings on Hudson, and Louis
Freedman, Bronxville, N.Y., assignors to U.S. Vitamin
& Pharmaceutical Corporation, a corporation ofi'Dela
The: betaine structural assignment: .hasbeenmadeon
the basisof the-strong ferric chloride reaction. (orange
color) indicating retention of the phenolic-"like-aoxygen
in the 3-position of therpyridineringr
ware
No Drawing. FiledApr. 13, 19.60,. Sen-No. 21,894
6. Claims.
It. is of interest’ that. similar reactions; of _3'=hydroxy~
((11. . 260—295)
pyridine withv naphthyl isocyanate, phenyl isothiocyanate,
This invention is concerned with certain novel reaction 10 or alkyl isocyanatessuch as butyl .isocyanate. failed :to
‘ give compounds of. the typesdescribed above...
which have been formulated as N-('carbanilido)'-3-oxy
The compounds of thisrapplication are stable, crystal:
products of aryl isocyanates and .3-hydroxy pyridine
pyridyl betains of the following formula:
line; white solids with no odor, and. indeed,‘this property
re?ects: one of the important utilities .ofthe compounds‘;
15 It is well known in the art that aryl isocyanates .are
’ relatively unstablematerialgand ‘i111v addition,- are power
: ful lachrymators. We have found that .with the-come
pounds of this application under suitable conditions the
noted reaction equation. is reversed and affords the iso
wherein R is selected. from the groupponsisting of hydro
gen, lower alkyl, halo, and lower alkoxy. In addition, 20
the invention includes compounds derived from diiso
cyanates wherein. a single isocyanate group is attached to
cyanate and 3'-hydroxypyridine.
'
Thus, on boiling with ethanol, the phenyl urethane is
‘ isolated, as for example, phenylurethane, from (I), R=H.
a phenyl ring, as for example, typicalproducts obtained
from 4,4"-diisocyanato-diphenylmethane and 4,4"-diiso
cyanato-3,3’-bitolyl formulated below-a
The compounds of this invention, therefore, provide
a. suitable‘ means of‘forming,aryl‘iSocyanates in situ for
reactions such as preparation of phenylurethane de
,_ rivatives.
In addition, the compounds herein described Show
pharmacological activity as potentiators of adrenalin, cen'
tral nervous system depressants and anti-in?ammatory
agents.
.
'
The process and‘v compounds? of this. invention will be
_ ' more clearly understood from a consideration of the fol
lowing speci?c examples which are given for the purpose
of illustration only and are not to be construed as limiting
35 the scope of the invention in any Way.
CH3
The compounds of this invention are conveniently pre
pared by reaction of substantially equivalent quantities of
the isocyanate and 3-hydroxypyridine at elevated tem
peratures in a solvent, such as acetonitrile.
The following equation is illustrative:
=C=0
EXAMPLE 1
A mixture of 3.9 g. (0.03 mole) of m-tolylisocyanate
and 2.8 g. (0.03 mole) of 3-hydroxypyridine was heated in
40
an oil bath, maintained at 195° for 0.5 hour. When cool,
the reaction product was dissolved in 35 ml. of acetoni
trile and after standing 24 hours 3.53 g. of product, M.P.
OH
+
—-—v (I)
120-121“, was obtained.
45
R
The compounds described in the table below were ob
tained in a similar manner.
Table
R
i‘ ‘1’
6B\
9
Analyses,‘i Percent
No.
R
M.P.,
Percent
° 03-5
Yield 6
Formula
Carbon
Calcd.
- Melting points are not corrected.
48
CuHmNzOz ..... -_
67.3
52
51
51
54
56
C13H12N202-C1aH12N2Oz._
0.3H5N202.CHHQCINZOZ
CuHnClNzOt.
68.1
68.1
68.1
58.0
58.0
Nitrogen
Calcd.
Fd.
Calcd.
4.7
12.2
12.2
12.2
11.3
11.3
67.7
68.1
68.4
68.3
58.2
58.2
5.7
5.7
5.7
3.7
3.7
4.6
5.4
5.2
5.2
3.8
3.7
‘13.1
Fd.
12.7
12.0
12.1
11.7
10.9
11.1
56
C|2H9O1N102 ____ .-
58.0
57.5
5.7
3.8
11.3
10.8
37
C13H12
63.9
63.4
5.0
5.1
11.5
11.2
2 5 ..... -.
55
CmHnNzOa- _
64. 0
5. 0
73
CuHzoNAOL-
68.2
67.3
4.6
5.1
12.7
13.2
44
C25H22N4O4 ..... -.
68.7
68.5
4.9
4.9
12.3
12.3
.
b Recrystallizing solvent was acetonitrlle in all cases.
I Yields are given for recrystallized product.
6 Analyses by Weller and Strauss Oxford, England.
I Bls-betaine from 4,4’-diisocyana
_
.
_
-
Fd
Hydrogen
5o-diphenylmethane.
I Bis-betalne from 4,4’-dlisocyanato-3,3’-bltolyl.
63. 9
4. 8
11. 5
11. 2
8,020,286
4
3
wherein R is selected from the group consisting of hydro
EXAMPLE 2
gen, lower alkyl, halogen, and lower alkoxy.
One g. of N-(carbanilido)~3-oxypyridyl betaine (table,
2. The compound
compound 1) was boiled with 20 ml. of ethanol and the
reaction mixture concentrated to 5 m1., and 5 ml. of water
and. 1.7 m1. of 3 N hydrochloric acid added. The formed 5
precipitate was separated and recrystallized from hexane.
The product so isolated melted 49-50° and did not depress
the melting point of authentic N-phenylurethane, mixed
3. The compound
M.P. 49-50°.
For therapeutic purposes the compounds of this inven 10
tion are formulated to contain 50-150 mg. of active in
gredient in a pharmaceutical extender which does not co
act with the active principles described herein.
It is to be understood that it is intended to cover all
changes and modi?cations of the example herein chosen 15
4. The compound
for the purposes of illustration which do not constitute
departure from the spirit and scope of the invention.
We claim:
1. A member of the group consisting of compounds 20
of the following formulae
6
25
\
is so
References Cited in the ?le of this patent
UNITED STATES PATENTS
35
(5e
2,909,528
Shapiro et a1. ________ .._ Oct. 20, 1959
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