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Патент USA US2408833

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Patented Oct. 8, 1946
' 7
,
UNITED" STATES PATENT} OFFICEy
rsnvnoknyrroennm AND ITS DIACETATE
Romeo B. Wagner, State College, Pa., assig'nor to
Parke, Davis & Company, Detroit, Mich., a cor-'- '
poration of Michigan - -
-
No Drawing. Application May 15, 1944,
Serial No. 535,756
4 Claims. (Cl. 260-2395)
This invention relates to the preparation of
new pseudo-sapogenins from certain steroidal
sapogenins which are described in J. Am. Chem.
Soc. 65, 1199 (1943). These compounds are
valuable as intermediates for the preparation of 5"
hormonesv of the sex hormone type and particularly of the adrenal cortex hormone type since
they are oxygenated at position 12 of the steroid
nucleus.
The reaction by which steroidal sapogenins are 10'
in a sealed tube for 10 hours. The solvent is
removed in vacuo and the residue hydrolyzed with
excess potassium bicarbonate (or alcoholic
potash) in aqueous ethanol. The product is ether
extracted, crystallized from acetone and then re
crystallized from ether to give pseudokryptogenin,
M. P. 189—192‘’ C. A mixture of this product with
kryptogenin melts at 162—167° C,
AnaL:C,Calc’d.
for9.8%.
C27H40O3: C, 78.6; H, 9.8%.
Found:
78.5; H,
isomerized to the pseudo-genins have been described in detail in the copending Patents Nos.
2,352,848 and 2,352,852, issued July 4, 1944. These
Treatment of pseudo-kryptogenin with hot
ethanolic hydrochloric acid converts it back into
kryptogenin. The pseudo-kryptogenin of this
also include proof of structure of the pseudogenin side chain.
examplehas the formula,
15 .
_
This invention relates to the preparation of
0H:
pseudo-genin compounds having the formula,
0H:
'
on, (gon 0 CH dB
=
—
3-
'
'
a
;
HY
'
"
20
__ H
.
-
I
where Y and Y' are-918mm“ °f the glass
5'
‘
I
‘I;
Pseudo-kryptogenin
25
Pseudolcryptogenin ‘(from pennogem'n)
I
of anhydride
6 grams ofispennogenin
acetate
in
18Acc.mixture
of acetic
heated at 200°
0. for
_
v: 10 hours.
<11
The mixture is evaporated in vacuo
‘30 on the steam bath and then re-evaporated with
-»
>
ethanol to remove the remaining acetic anhy
dride.
Afterwith
decolorizing
methanolbrand)‘,
solutionthe
of
the
residue
charcoal a(“Norite”
mid gm?“ hydrolyzable to
0H
HzOH
_V
I
.
0H
’
‘
éH-OH:
‘_
OH ’
H-
Q
‘
‘
_c
‘
3
__l
pl
,
011,011,
_
3
on.
_
CH,
‘
,
‘
product is crystallized from methanol and has
35 M. P. 68-73° C.v It is further puri?ed by hy
H
I have found that three sapogenins, Penno-
‘drolysis with 5% ethanolic potash and crystalli
, - to give a_
zation from ether and then
methanol
genin,‘ n'olog'enin and kryptogenin (see J. Am. _~ gigggggeggnn?'fribg?gglgied M' P'_Wlth pseudo.
Chem. Soc., 65 1199~,~~1943),_when treated under
.
.~
.
'
.
.
'
-
the
conditions described in Patents Nos. 2,352,848 4“ FoAunnglf'ccggcgd%€ogcg7go§"
C’ -7§'6,%’
H’ 93%‘
and 2352 852 for isomerizing to pseudo-genins,
' . ’
' . .’
’ '
'
I
I
’
’
.
.
are pseudo-kryptogenin.
converted
into
the same pseudo-genm,
name‘1y,
The diacetate
prepared,
re?uxing
krypbogenin
withis.acetic
a. 1 by
ydride,
and pseudo.
crystaL
from“
to‘ give material
of M; ,P.
T.“ inventifn' may be illustrated by the ml‘ 45 lized
120-125“
'0.‘methanol
‘Recrystallization
‘from methanol
1°Wmg exam!’ esgives material of M. P. 115-125 and 124-126° c.
pseudokrw togenin ( fTom hrw to 9enin)
H,AnaL:
9.2%. Found:
Calc’d 0,
for72.5;
C31H4405-CH3OH:
H, 8.6%.
C,
Asolution of 5 grams of kryptogenin diacetate
In a second run, the product from 20 g. of
m 15 cc. of acetic anhydride is heated at 200° C. 50 pennogenin acetate and 25 cc. of acetic anhydride
2,408,832
3
NaOH, K2003, KHCO3, NazcOs, NaHCOa or the
like. If an alcohol is required to aid hydrolysis,
is hydrolyzed directly and then crystallized from
acetone to give 11 g. of pseudokryptogenin.
this can be methanol or other lower aliphatic
The transformations of this example may be
illustrated as follows:
on ’
alcohol instead of ethanol.
What I claim is:
1. Compounds having the formula,
oH-oH.
CH;
CH1 I
CH:
C=C--CHz-CH1
A *‘
13-011,
10
‘
CHY
.
Pennogenin acetate
‘Pl/o
where Y and Y’ are members of the class con
A020 lat 200° 0.
sisting of
'
on
CHsCHg
on
a
on i CH‘
‘/
v H~CH|
HPO A0
20
H
and groups hydrolyzable to
OH
25
Hydrolysis
(alcoholic KOH)
AcO
2. Compounds having the formula.
CH:
Pscudo-kryptogenin,diacetate.
CH"
CH:
CH1
C/
/\
all?
who
l omen
CH‘ t ._——= c r: onr on3
30
\
(‘m-on,
__.__
oaY
N
Y’
35
where Y and Y’ are members of the class con
sisting of
on
Pseudorkryptogenin
Pseudokryptogenm (from noloyem'n)
40
This example is carried out under the same
conditions as the other examples but starting
with nologenin diacetate which has the formula,
CH1
H
and organic carboxylic acid ester groups hydro
lyzable to
45
OH
‘
HO .
H
CH:
3. Pseudokryptogenin having the formula,
\bnl '
50
CH:ACH: EH’
/CH,CHI
=0
H-om
-_\
lkcoi/ \J
55
HIOH
\/"
Nologenin diac‘etats
The same products, pseudokryptogenin and its
HO
4. Pseudokryptogenin diacetate having the
the preferred isomerizing agent is acetic anhy 60 formula,
CH;
CHzCHs
dride, other lower aliphatic acid anhydrides may
on, on, a =C /
H-CHl
also be used. The preferred temperature range
diacetate are obtained.
'
While for'ease of manipulation and economy
‘
lies between 190° and 200° C. although 'thefreac
tion also takes place as low as 170° or as high
as 230"‘. The example is intended as illustrative
and the invention is not necessarily limited to
“5
the conditions and reactants therein cited.
In addition to using ethanolic KOH solution
kaline solution, for example one containing
\f“
A00
for hydrolyzing the acylated pseudogenin to the
free genin, one can use any other suitable al
HIOAO
70
ROMEO B. WAGNER.
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