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Патент USA US2408830

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Patented ‘Oct. 8, 1946
2,408,829
UNITED STATES PATENT OFFICE
2,408,829‘
'
.
‘
STERGIDAL COMPOUNDS AND METHODS Y
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, 1344,
Serial No. 535,753
5 Claims.
'
.(Cl. 260—239.5) V
l
2
The invention relates to the preparation of new
foseudo-sapogenin compounds from steroidal sa
jcogenin compounds such as the lilagenin type
at about 200° C. for 12 hours. The acetic anhy
dricle is removed by distillation and the residue
taken up in methanol and the resulting solution
treated with decolorizing charcoal and then
crystallized from the methanol by concentration
and the yuccagenin type described in my copend
ing application, Serial No. 535,748, ?led May 15,
.1944.
The new pseudo compounds are useful as
and cooling. The crystals are ?ltered oif and
dried to give a product of M. P. 146° C. which also
melts at ‘146° C. when mixed with pseudo-yucca
intermediates for preparations of physiologically
active compounds, such as sex hormones.
The reaction by Which steroidal sapogenins are
genin triacetate from Example 1. It gives the
isomerized to the pseudo-genius have been de 10 correct analysis for C33H4s07 and can be hydro
scribed in detail in the copending Patents Nos.
lyzed like the triacetate of Example 1 to give
2,352,848 and 2,352,852, issued July 4, 1944. These
‘ pseudo-yuccagenin of M. 'P_ 182° C. '
also include proof of structure of the pseudo
The transformations of these examples can be
genin side chain.
represented as follows:
The present invention relates more particularly 15
OHa
CH2—CHz
to the preparation of pseudo-sapogenin com
CH3
013a |
/ I
r pounds by way of isomerization of the corre
A
CH-—C
CHI-CH3 '
sponding sapogenin. The new compounds have
\
O—-——C :
‘
H
the formula,
CH3
CH3
.
20
0:0-01120131
Yl=l\/
4
H
1
A,O_/\ /W/
H
AcO‘L/V
' “
Yuccagenin diacetate
25
on
3
on ‘EH’ /O_—O\H’
3
/\
\
Where Y and Y’ are members of the class
30
.
.
oH-o
\H
—
a sum
anhydride
AcO-
N \/\H
(e. g. A090)
ag?lal'pgt
and groups hydrolyzable to
OH
A O
.
35
C
Lilagenin diacetate
A020 at about 200° 0.
i!
The invention is illustrated by the following
examples.
40
Example 1
CH3
A mixture of 10 grams of yuccagenin diacetate
and 15 cc. of acetic anhydride contained in a
sealed tube is heated at 200° C. for 10 hours.
After removal of the acetic anhydride and treat- 45 A00
merit of a methanol solution of the residue with
charcoal (“Norite” brand), the product is then
crystallized from methanol to give a product of
M. P. lei-145° C. Recrystallization from meth
anol raises the melting point to 145—147° C. This
The triacetate can be hydrolyzed with dilute
alkali, extracted with ether and crystallized from 55
other to give needles of pseudo-yuccagem'n of
M, P. i8l-i82° C.
Example 2
29 grams of lilagenin diacetate (J. Amer. Chem.
Soc. 62, 2620 (1940)) melting at 156° C. and 30 cc. 60
of acetic anhydride are heated in a sealed tube
/\
C=O
CH——CHa
I
\
OHnOAc
H
/\/ \/\H 0
A"°‘\/\/
Pseudo-yuccagenin triacylate (e. g. triacetate)
Alkaline l hydrolysis
50
is pseudo-yuccagenin triacetate.
Anal; Calc’d for (3331314807! C, 71.2; H, 8.7%.
Found: C, 71.5; H, 9.0%.
CH3 C CHzCHz
CH3 I
CH3
CHa |
CH3
CHJOHZ
/\
C=O
(EH-CH3
I
\
OHzOH
H
—O
H0_l/\/\l/\/ H
H°‘\/\/
Pseudo-yuccagenin
(DH-CH3
H 2- CH 2
2,408,829
Whilefor easeyof. manipulation ‘and economy
and; organic carboxylic acid ester groups hy
the preferred isomerizing agent is acetic anhydride, other lower aliphatic acid anhydrides may
drolyzable to
0H
also be used. The preferred temperature range
<
lies between 190° and 200° C. although the reaca 5
tion also takes place as low as 170° or as high as '
,
'
H
'
230°. The example is intended as illustrative and
the invention is not necessarily limited to the
3. Compounds having the formula,
conditions and reactants therein cited.
CH,
What I claim is:
1. Compounds having the formula,
CH;
CH;
/\
CH:
1
c =C-CHICH!
-
15
~
:1 '
Y’
.
Y,_/\/\/ \/\H
_
_
.
W
where Y and Y’ are lower fatty acid ester groups.
Y’—
4. Pseudo-
My
20 formula,
Where Y and Y’ are members of the class
OH
'
<11
.
'
and groups hydrolyzable to
"
_
if
'
>
.
'
W
cca enin tr'ace ate
g
‘ 5
W g
h
t e
—
2(‘3112 CH
l
2
oHloilc
_
,
‘ "
l
VV
'5. Pseudo-yuccagenin having the formula,
OH: I
A
ore-omen, .
I
_
CH,
‘EH-OH‘
CH,
‘ 35
CH‘ e=o
OHSY
Y,=/\/\/ \/\H
____
-
—\/
I
40
where Y and Y’ are members of the class
OH
\
/CH2CI;HI
oH-cm
OH OH
H
\
'
ha ‘n
A
A00 ‘
30
‘CH:
7
t
AcO—/\/\/\/\
2. Compounds having the formula,_
Y,_
l
OH:
CH‘ (|J—-C CH CH
(EH3
25
<OH
CH;
CH=Y
Y,=/\
F--0
1
(BEECH:
O
CH=Y
.
O=O~OHAIJH|
—\H .
'
(‘m-0H;
Y,
CH, Hm‘
, l0
’
EGAN \/ :H
l
t
HO_\/\/
ROMEO B. WAGNER.
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