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Патент USA US2117299

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2,117,299
Patented May 17, 1938
UNITED STATES PATENT OFFICE
CYCLOHEXENE DERIVATIVES
Walter G. Christiansen, Glen Ridge, N. J ., as
signor to E. R. Squibb & Sons, New York, N. Y.,
a corporation of New York
No Drawing.
Application September 15, 1934,
Serial No. 744,198
6 Claims.
(Cl. 260—33)
This invention relates to, and has for its object
the provision of, compounds having the general
formula
wherein X represents a halogen (especially bro
mine or chlorine), R represents an alkyl, an aryl
1 O (especially phenyl) , or an aralkyl, the Y’s repre
sent each alkoxy or together
00
wherein Z represents hydrogen, an alkyl (espe
cially methyl), or an alkali metal; compounds
.
Céz CX
CH:
cold solution of 3.06 g. sodium in 56 cc. absolute pl 0
alcohol; the mixture is re?uxed six hours in an
in vacuo; the residue is diluted with 200 cc. cold
water, and extracted with ether to- recover unre
-—NH/
having the general formula
CHX
22.0 g. ethyl Z-bromo A2'-cyclohexeny1 malonic
ester and 6.0 g. urea are successively added to‘ a
oil-bath at 120°; alcohol is removed by distilling
—NZ
15
malonic ester of that aryl, aralkyl, or other alkyl
(say phenyl, benzyl, or methyl, malonic ester, re
spectively) is employed instead of the ethyl ma
lonic ester in the foregoing example.
CH
CH2
wherein X represents a halogen (especially bro
2 Ul mine or chlorine) ; and methods for the prepara
tion of these compounds.
EXAMPLES
1,2-dib1‘0mo M-cyclohemene
100 g. 1,2,3-tribromo cyclohexane and 26.5 g.
crushed potassium hydroxide are heated in a
Claissen ?ask on a steam-bath while the system
is evacuated; a vigorous reaction ensues, with
acted ester; the aqueous alkaline solution is acidi
?ed with 50% acetic acid; and the precipitate, on
being Washed with water, dried in vacuo, and
crystallized from benzene, yields the compound
sought, a white crystalline substance melting at
225-226°, soluble in alcohol and acetone but
scantily soluble in water, benzene, and ether.
To procure an alkyl instead of a N-hydrogen
in the compound sought, the correspondingly
substituted urea (say methyl urea) is employed
instead of unsubstituted urea in the foregoing
example.
Compounds of this type have shown promise of
value as hypnotics.
Sodium salt of 5-cthyl 5-(2’-br0mo A2'-cyclohea:
enyl) barbituric acid
sodium hydroxide solution, on being evaporated to
dryness in vacuo and further dried in vacuo over
in ether and the solution dried over sodium sul
fate; and the solvent being removed and the
residual oil recti?ed, there is obtained the com
pound sought, a colorless oil boiling at 110-ll1°/'7
as a Water-soluble white powder.
Among the many other compounds that may
be prepared in accordance with the invention are:
Ethyl Z-bromo M-cyclohemenyl malom'c ester
33.3 g. ethyl malonic ester is added to a solu
tion, cooled to 30°, of 4.03 g. sodium in 75 cc. abso
lute alcohol, and while the temperature is main
tained at 30-35° 42 g. 1,2-dibromo A2 cyclohexene
is slowly added with stirring; the solution is re
?uxed six hours, and is then neutral to litmus;
the sodium bromide being ?ltered out, the alco
hol being removed from the ?ltrate, and the
residue being recti?ed, there is obtained the com
pound sought, a colorless oil boiling at
141.5-142.5°/1 mm.
To procure an aryl, an aralkyl, or some alkyl
55 other than ethyl in the compound sought, the
30
A solution of 10 g. 5-ethyl 5-(2’ bromo A2’
cyclohexenyl) barbituric acid in 31.6 cc. 1.0036 N
> distillation at 40 mm.; the distillate is dissolved
mm.
5
calcium chloride, yields the compound sought
5
5-isopropyl 5-(2'-bromo A2’-cyclohexenyl) bar 40
bituric acid
5 - normal-butyl 5-(2’-chloro nz-cyclohexenyl)
barbituric acid
5-phenyl 5-(2'»chloro A2’-cyclohexenyl) barbi
turic acid
'
Sodium salt of 5-methyl 5-(2’-bromo A2'-cyclo
hexenyl) barbituric acid
Sodium salt of 5-benzyl 5-(2'-chloro A2’-cyclo
hexenyl) barbituric acid
E-methyl 5-(2'-chloro zW-cyclohexenyl) N-eth
yl barbituric acid
5 - benzyl 5 - (2' - bromo zW-cyclohexenyl) N
methyl barbituric acid
It is to be understood that the foregoing exam
ples are merely illustrative and by no means limi
2
2,117,299
tative of the invention, which may be variously
otherwise embodied—as with respect to particular
substituents, reactants, and processes_within the
scope of the appended claims.
I claim:
alkyl, and Z represents a member of the class
consisting of hydrogen, an alkyl, and an alkali
metal.
3. Compounds having the general formula
1. Compounds having the general formula
C_Hz—CHz
/
10
’
CHK CH=CX/
011-0
|\
R CONH
CH1
clic aryl and monocyclic aralkyl, and Z represents
a member of the class consisting of hydrogen, al
15 kyl, and alkali metal.
2. Compounds having the general formula
CH:—CH2
20
CH=CX
CONZ
/cH_(|3\
/
R CONH
CO
wherein X represents a halogen, R represents an
c ONZ
011-0
on=ox
/00
wherein X represents a halogen, R represents a
member of the class consisting of alkyl, monocy
CH1
011E013,
CONZ
'
o
OONH/
C2135
10
wherein X represents a halogen and Z represents
a member of the class consisting of hydrogen, an
alkyl, and an alkali metal.
4. 5-ethyl 5-(2'-bromo A2’-cyclohexenyl) barbi
turic acid.
15
5. Sodium salt of 5-ethyl 5-(2’-bromo A2'-cyc1o
hexenyl) barbituric acid.
6. 5-methyl 5 - (2'-chloro A2'-cyclohexenyl) N
ethyl barbituric acid.
20
WALTER G. CHRISTIANSEN.
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