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Патент USA US2408834

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2,408,833
Patented Oct. 8, 1946
UNITED STATES PATENT . OFFICE
2,408,833
METHODS
STEROIDAL COMPOUNDS AND
SAME
FOR OBTAINING THE
Romeo B. Wagner, State College, Pa., assignor to
Parke, Davis & Company, Detroit, Mich., a cor
poration of Michigan
No Drawing. Application May 15, 1944,
Serial No. 535,757
9 Claims. (Cl. 260—239.5)
1
2
groups. Similarly pseudo-rockagenin has .the allo
con?guration at C-5 and hydroxyls at 3, 12 and
This invention relates to the preparation of new
pseudo-sapogenins from new steroidal sapogenins
27. Pseudo-furcogenin is, however, of the “regu
lar” con?guration at C-5 and carries hydroxyls
some of which are described in my copending ap
plication, Serial No. 530,758, ?led May 15, 19%.
at C-3 and 27 with a ketone group at (3-12.
(See also J. Am. Chem. Soc. 65, 1199 (1943).)
The invention may be illustrated by the follow
These compounds are valuable as intermediates
ing example:
for the preparation of hormones of the sex hor
Pseudohecogenin.--A sealed tube containing 5
mone type and particularly of the ‘adrenal cortex
g. of hecogenin and 15 cc. .of acetic anhydride was
hormone type since they are oxygentated at posi
10 heated at 200° for‘10 hours. The solvent was re
tion 12 of the steroid nucleus.
moved in vacuo and the solid residue was treated
The reaction by which steroidal sapogenins are
with a solution of 5 g. of potassium hydroxide in
isomerized to. the pseudo-genins have been de
500 cc. ethanol for thirty minutes. The product
scribed in detail in the copending Patents Nos.
was ether extracted and the ethereal solution was
2,352,848 and 2,352,852,“ issued July 4, 1944. These
also include proof of structure of the pseudo
genin side chain.
This invention relates to the preparation of
pseudo-genins having the formula
Y’
.
CH3
omen,
‘0 DEL
A
Y”...
B
washed and evaporated. The acetone solution of
the residue after treatment with Norite was con
centrated and cooled to give white needles,'M. P.
189-191°; yield 2.6 g.
_
Anal.: Calc’d for Cal-14204: C, 75.3; H, 9.8.
C, 75.2; H, 9.9.
,
20 Found:
While for ease of manipulation and economy
the preferred isomerizing agent is acetic anhy
dride other lower aliphatic acid anhydrides may
also be used. The preferred temperature range
(Em
lies between 190° and 200° C. although the reac
25 tion also takes place as low at 170° or as high
as 230°. The example is intended as illustrative
and the invention is not necessarily limited to the
\
”\/\/
conditions and reactants therein cited.
where Y’ ' is
011
30
The above mentioned transformations can be
illustrated diagrammatically as follows:
0
CH5
or a group hydrolyzable to
011
CH;
CHr-CH:
CH: 2} 11-0
CHI-CH!
H
where Y’ is a member of the class
E
OH
Hecogenin
Acyl anhydride (e. g. acetic anhydride)
groups hydrolyzable to
on
H
at 200° 0. for 10 hours
45
and =0 and Y is a member of the class OH and
groups hydrolyzable to OH.
Speci?c examples of this type compound are
pseudo-hecogenin in which Y’ at 3 is
OH
50
Y’ at 12 is =0, Y at 27 is —OH, and the con?gu
ration at 0-5 is “allo.” In pseudo-hecogenin di
acetate both hydroxyls are acylated by acetyl 55
Pseudo hecogenin dlacylate (e. g. diacetate)
2,408,838
lAlkalinehydrolysis
0
CH!
CH:
CH1 ‘1:
_,
I
Acyl anhydride (0. g. acetic anhydrlde)
at 200° 0. for about 10 hours.
CHz-CH;
=0
\H
AN
5
OH-CH:
2
H OH
H
Ink/m)
—\Hl
10
H.011.
H1O Ac
A00
H
Pseudo hecogenin
15 ,7
Pseudo-furcogenin diacylate (e. g. diaeetate)
H0
CH
.
_
' JlH-C\
(EH-CH;
__
o_o§,
'
V
Alkaline l hydrolysis
CH CH: /CH:—CH:
a
2°
H
N
V
CH;
0
CH:
OH; 6
H
Ho~ ‘ Id
25
1'1
=C-CH2CH:
CHI-CH
\H
/\ N
1
HQOH
H
Ho‘k/ \)
Rockogem‘n
Ac lanh dride (e. . acetic anhydride)
l y at 2360" OJm-éeveral hours.
30
Pseudo-Iurcogenin -
A00
CH
CH (EH: /CH2|CH2
3
! C=C
I
\H l
/\
In addition to using ethanolic KOH solution
for hydrolyzing the acylated pseudogenin to the
‘
CH-CH;
35
2
H
.
7 A00
40
4
'
free genin, one can use any other suitable alka-'
line solution, for example one containing NaOH,
K2CO3, KHCOs, NazCOa, NaHCOa or the like, If
an alcohol is required to aid hydrolysis, this can
be methanol or other lower aliphatic alcohol in
CH 0A0
stead of ethanol.
‘
What I claim is:
1. A pseudo-sapogenin
formula
is‘:
Pseudo-rockogenin triacylate (e. g. triacetate)
compound 0; the
‘ 45
1 Alkaline hydrolysis
,
H0
,CH
50
CH CH: /CH:CH!_
’
' o=o
CH-CH:
HIOH
/\
where Y and Y" are members of the class
55,
HOL/I
Ylli/
OH
<11 '
I’!
60 and groups hydrolyzable to
Pseudo-rockogenin
CH o CH cm
‘
' $H_ \
H
cm-om
CH—CH;
65 and Y’ is a member of the class 0, v _ I,
\Hl O_C :
/\
'OH
H
‘
70
and groups hydrolyzable to
H0
OH
‘
Furcozenln
2,408,833
5
6
2. A pseudo-sapogenln compound of the for-
CH
mula'
Y’
CHa
CH;
CHs (IJ
/
=0
\
v
/\
Y, CH CH,
z
' o=o-oH,oH1
omen,
__
H-CH:
|CH=Y
\
H
5
H
/\
W
H
Y”
Y,,_
10
"V
H-CH:
H=Y
H
i
’\/i
H
where Y, Y' and
Y" are members of the class
where Y, Y’ and Y" are each members of the
<OH
class
<0_a°y1
H
OH
O
and
H
6. A: pseudo-furcogenm
compound or the
_
15
H
formula,
-
v
0
and groupshydrolyzable to
0H:
OH’ I OH’ (‘;____.C_CH,CH,
OH
20
—"\H
H-CH:
CH=Y
H
/\/ \/<;
3. A pseudo-sapcgenln compound of the for
mula
25
Y”
CH ‘)k
Y’ CH a (‘111:
0:0/CH2CH2
H-cm
_-'\
Where Y and 1'1Y” are members of the class
0H
(Pam
(|JH=Y
H
____
k
30
and
H
'7. Pseudo-hecogemn
the formula,
. havmg
.
/\/\/ \/\1H
Y":
011;
35
where Y and Y" are each members of the class
OH
40
H
and groups hydrolyzable to
8. Pseudo-rockogenin having the formula,
OH
HO
H
CH:
C=C-CH:CH:
\
and Y’ is a ketone oxygen group.
4. A pseudo-hecogenin compound of the for
mulaI
O
CH:
H
CH=Y
HO-
55
9. Pseudc-furcogenln having the formula,
O
I
tr
where Y and Y" are members of the class
l
I
H
Y]!
H-CH:
HQOH
V’Y
50
OH; H OH: C==C—CH:CH2
I
_—\
(DEF-CH:
H
CH:
CH3 I
60
CH:
\Jéi CH-CH:
H2011
<02! <0~8CY1
and
H
H
5. A pseudo-rockogenin compound of the
formula,
ROMEO B. WAGNER.
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