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—
Patented Oct. 8, 1946 .
1
UNITED STATES 3 PATENT OFFICE 7
2,408,831
STEROIDAL COMPOUNDS AND METHODS
FOR OBTAINING THE SAME
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. 535,755
8 Claims. (Cl. 260—239.5)
ee aso J m hem. Soc 65, 1199 (1943)) 5 acetate However, pseudo-agavogemn forms a
are of
valuable
as intermediates
tetraaceta 42, since its group
for ese
thecompounds
preparation
hormones
of the sex
011 at C-12is
hormone type and particularly of the adrenal
cortex hormone type since they are oxygenated
<5
at position 1.2 of the ster10d nucleus‘
10
scribed in and
detail2,352,852,
in the copending
Patents Nos.
issued July 4, 1944.
2,352,848
The invention may be illustrated by the follow
ing examples.
Pseudomanogenin- _
-
pseudo-genin
side chain.
These also include
proof of structure of the 15 1 Amlxture 9f 10 g‘ of-manogenm dH-a'cetate and
is invention relates to the preparation of
pseudo-genius having the formula,
CH3 ,1,” CH3 [0H3 /OH2OH2
O=0
\/\H I
Y"=/\
needles of M. P. 168-171" 0.; yield is 6 grams of
0343B;
20 pseudomanogenin triacetate. I
CH=Y
Anal.: Calc’d. for 0231-14803! C, 69.2; H, 8.5%.
Found: C, 69.4; H, 8.3%.
/ \/\H
‘0
from
the triacetate.
Alkaline
hydrolysis gives free- pseudomanogenin
Yul
25
_\/
_
A solution of 5 g. of mexogenin in 15 cc. of
where Y and Y" are in each case members of
the class
0H ~
,
acetic anhydride is heated at 200° C. for 12 hours
in a sealed tube. The solvent is removed and the
30 residue is hydrolyzed with 200 cc. of boiling 5%
<
alcoholic potassium hydroxide for 30 minutes.
H
and groups hydrolyzable to
The hydrolysis mixture is extracted ‘with ether
and the
ethereal
solution
is appear
washed and
and isevapo
rated
until
crystals
start to
then
6H
35 cooled. The crystals are then separated and re
<
H
Pseudomemogem'n
crystallized from acetone, M. ~ P. 143—l45° C.
.
Yield is 3 grams of pseudomexogenin.
and Y’ 1s a member of the class =0, .
Found; c‘ 722; H, 9_4~
Anal: Calc’d. for C27H4205.‘ C, 72.6,‘ ~H,. 9.5%.
.
OH
40
By starting with mexogenin diacetate or like
lower fatty acid diacylate and treatin;r as de
H
and groups hydmh7Zable to
scribed above for manogenin diacetate, onecan
obtain
pseudomexogenin
triacylate
or triacetate
Agavogenin
can e similarly
treated
either to
OH
45 obtain pseudoagavogenin or its tetraacylate.
W ile for ease of manipulation and economy
the preferred
isomerizing
is acetic anhy
Speci?c examples 0f Hthis type Com ound are
dride,
other lower
aliphaticagent
acid anhydrides
may
p-seudo_manogenin in which y and-ml: two Y” I‘ also be used. The preferred temperature range‘
groups are each
OH
00 hes between 190° and 200 C. although the re
action also takes place as low as 170° or as high
<H
at C-27, 0-2 and C~3 of the nucleus, respectively, 55
as 230". The example is intended as illustrative
In addition to using ethanolic KOH solution for
2,408,831
4
hydrolyzing the acylated pseudogenin to the free
and groups hydrolyzable to
genin, one can use any other suitable alkaline so-
OH
lution, for example one containing NaOH, K2003,
KHCOz, NazCOa, NaHCOs or the like. If an alco-
H
hol
is required
‘to lower
aid hydrolysis,
this
can
be 5
.
methanol
Or other
aliphatic alcohol
instead
011
2. Compounds ofY’the formula,
formulas for pseudomanogenm, pseudoof The
ethanol.
mexogenin
and pseudoagavogenin described
above are:
'
CH, “ CH, \ ‘
10
‘3:0
""\
v
on O OH CH3
a \
CH CH
/
’
’
‘11-011’
011:‘!
1
= <E==c_omom
\-"\\__,__0
H\
'
I
'
Y”
15
v \/\H
Y”:\/\/
(DH-CH;
011,013
,
‘
where Y and Y" are in each case members oi the
HO
H
11
H0
OH
Class‘
H
20
‘Pseudmmanogenin
a
a
<
I
H
__
an
GH‘?CHCH’
er car oxy 0 ac
dlw
‘(E’C”CH’?H’
\\
0
(Ell-CH:
b
lyzable to
25
ll
es er groups
id
y ro
t
hd
OH
and Y’ is a member of the class =0,
HO "V
30
H
OH
<
. Pscudo-mexogenin
CH5
H
CH3 é a
HO
35 and lower carboxylic acid ester groups hydro
OH
==G-“CH2(‘3H’
\\H \
___O
E0
H0»
lyzable to
GEL-CH3
omon
<
\ \/\H
H
‘\/§\/
40
‘
3. A pseudo-manogenin
‘E compound of the for
'
Pseudo-agavogenln-
0
mula,
CH3.
CH’/“\CH3 (E:C_CE1CH2
The acylates ofthese, such as the acetates, have 4'"
the same formulas except that the OH groups'are
N
replaced by acyl or acetyl (CHSCOO).
What I claim is:
Y!
om.
,5
‘
'
v
Y”_
”
r50
1. Compoundsoi the formula,
CH3 \ CH“
(‘2 0/
__.._\H
Y
Y
omom
OH
__ on ,.
(\JHZY
V
H
~
~
-———O
\H
oH-om
___
23H”
\?
H
.'
It
where Y and Y are members of the class
'
/ \/\
V
OH
OH
55
'
O——acyl
<11 and <11
Y”:
4. A pseudo-mexogenin compound having the
formula,
where
class Y and Y" are in each
OH case members of the 00
.
CH‘)K
0 CH ’ CH:
(Ego-omen,
‘
\
-’_\H
H
(‘EH-CH;
_,_
omY
and groups hydrolyzable to
7
<OH
H
imay, is amemberoftheclass=o
OH
H
7
where Y and, Y" are members of the class
OH
<
H
O -acyl
and <
2,408,831
fcrmula,
5. A pseudo-agavogenin compound having the
7. Pseudo-mexogenln having the formula,
CH: 0 CH3 6CHa C CH CH
CH Y' OH CH:
3 I
3 é=C-CH3(|3H2
“\H
‘
Yl/_f\
\/]§\/
Y”
5
(BEECH:
O—acyl
.
Pseudo agavogenm having the formu a’
-
15
-
H
)k
HO
I
I
7
HOW
§/\
I ‘/\H
20
0H~0H8
CHaOH
=O_CH’('3H‘
_
=O-CHzC-H2
V‘;
1
CH; H0011, EH:
A
CH3 (j:CH:
HO
HO
25
2
CH-CH;
H
K
6Q Pseudo-manogenin having the formula,
O
0112011
I‘
H0
< and <
0H;
\/\
Hof
‘VB
10
Where Y, Y’ and Y” are members of the class
OH
2'
/\H
OH’Y
H
I
x * Q
‘
HBOH
OH-OH:
\/\H
,
1'1
ROMEO B. WAGNER.
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