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Патент USA US2406133

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Patented Aug‘.
1946‘
2,406,133 '
UNITED STATES PATENT OFFICE
PROCESS. FOR OBTAINING PROVITAMIN D
William S. Calcott, Woodstown, N. J., and George
‘E. Holbrook and Stockton G. Turnbull, Jr.,
Wilmington, De‘l., assignors to E. I. du Pont de
\ Nemours & Company, Wilmington, Del., a cor
pora‘tion of Delaware
' No Drawing. ‘Application July 11, 1942,
Serial No. 450,632
' 7 Claims.
This invention relates to a new and improved“
method for obtaining fat-soluble compounds and
more particularly refers to a process for separat
.
2
treatment of'imussels and other shell?sh with a
saponifying solution for a sufiicient period of time
and under such conditions as to release the pro
ing provitamin D from animal organisms contain
» ing the same.
-
(Cl. 167-81)
'
'
Heretofore fat-soluble substances generally,
and in particular provitamin D, were obtained‘
from animal organisms by treating them with a
saponifying agent which was generally an alco
vitamin ,D content the'reof into the saponifying
liquor, and the reuse of such liquor in the extrac
tion of provitamin D from additional mussels or
shell?sh. In a still more restricted sense this
invention isconcemed with a process whereby‘
hol-water solution-oi’ caustic soda. Where the 10 mussels or other shell?sh are crushed, the crushed
mass treated with a saponifying solution, the
animal organism was enclosed in a protective
shells and other insoluble constituents thereafter
shell as in the case of shell?sh, it was ?rst neces
sary to remove this shell before subjecting its ' removed from the reaction zone and additional
‘quantities of crushed mussels or shell?sh intro~
contents to the foregoing saponi?cation treat;
ment. Needless to say, this process was tedious 16 duced into said reaction zone for a similar treat
and expensive.
,
_
'
'
ment. The process is continued until the concen
A further disadvantage of the prior art was the
, tratlon of provitamin D in the saponifying liquor
ess because of increased handling charges, the
necessity of using extraordinarily large amounts
mussels to obtain therefrom their provitamin D
necessity of employing extremely large quanti- _ is sui?ciently high to render its subsequent han
dling and extraction with organic solvents eco
ties of saponii'ying solution for the recovery of a
small. amount of provitamin D. This, too, re 20 nomically feasible. In its preferred embodiment
this invention is concerned with the treatment of
sulted in a great increase in the cost of the proc
- of organic solvents for recovering the provitamin
content by washing, steaming and draining the
mussels, crushing the shells thereof and subject
D from the saponifying solution and the loss of 25 ing the resulting mass of cracked shell and meat
to the action of a saponifying solution of aqueous
appreciable amounts of these expensive agents.
sodium hydroxide solution for a su?icient period
It is an object of the present invention to over
come the aforesaid‘ disadvantages and other dis
of time and under such conditions as to release
substantially all the‘ provitamin D, removing the
advantages directly or; indirectly resulting there
from. A further object is to obtain fat-soluble 80 shells from said solution and repeating the proc-'
ess with additional mussels, treated as aforesaid,
constituents from'animal organisms containing
and the original saponifying solution until the
the same in a simple and more economical man
liquor becomes highly concentrated in provita
ner than was heretofore possible. A still further
object is to obtain solutions of provitamin D from
min D.
,
_
'
-
The invention may be more readily understood
shell?sh by means of a process wherein the ex 35
by a consideration of the following illustrative
pensive removal of the shell is avoided, the use
of alcohol is unnecessary and the amount of
chemical agents necessary is greatly reduced. I A
examples:
'
‘
>
v
.,
EXAMPLE 1
still further object is to obtain solutions of pro
' Production of provitamin D from the mussel,
vitamin D from mussels and other shell?sh in a 40
' Modiolus demissus (Dillwyn)
I more concentrated and cheaper manner than was
heretofore possible. Additional objects will be
come apparent, from a consideration of the fol~
lowing speci?cation and claims.
, 'Into a vessel containing 20.5 parts of 15% (by
weight) caustic there was lowered a perforated
basket which contained the"‘crackings” (“crack
. These objects are attained in accordance with 45 ings” isaterm used to describe the animal after
the present invention wherein fat-soluble con-'
stituents are removed from animal organisms by
treating said organisms in the presence of such ,
protective coatings asthey may possess with a
it has been washed, steamed, drained and cracked
. or crushed) from 30.0 parts of whole mussels of
the species,‘ Modiolus demissus (Dillwyn). The
temperature of the caustic was kept at '95-97" C.
for one-half ‘hour, and then the basket, which
saponifying solution, removing the protective to
now contained nothing but shells, was raised from '
coating from the reaction zone and repeating the
process with additional organisms but the orig
inal saponii’ying liquor until a concentrated liquor
oi’ rat-soluble constituents is obtained. In a more
restricted sense this invention pertains to the 55
the vessel. The caustic liquor was allowed to
drain back into the saponi?cation vessel. The
basket and shells were then washed by immersion
2,406, 188
taining the provitamin D were isolated in almost
quantitative yield by crystallization from alcohol.
; To the caustic liquor in the saponi?cation ves
sel there was added 0.50 part of so ‘d ?ake caustic,
Exmrnn 5
and another saponi?cation operation was per
_
Provitamln D'frorm the giant conch, Stromb
formed on the “crackings" from 30.0 parts of
whole mussels. _ The shells after being stripped of
_
the meat'were washed in the same wash water
‘Y
, giyas, Linn.
f
The “crackings” from 15 batches of 30.0 parts
used after the previous saponi?cation. In the
each of the whole conch were processed as de
same manner, using the same caustic liquors and
> scribed in the previous examples to obtain almost
same wash water, throughout, the meat was re' 10 all of the provitamin D originally present mixed
moved from thirty batches of “crackings," each
with other sterols.
‘from 30.0 parts of whole mussels. After the last
batch of. “crackings” had been processed in this
manner, the caustic liquor in the saponi?cation
’
I
Exmrns 6
Prwitamin D from fresh water mussels
vessel was held at 95-97“ C. for four hours and
1was then withdrawn. The wash water liquor was
These mussels, which are all Lamellibranchia,
are of the family Unionidae, whichcomprises 60
su?lcient
,;then put into the saponification vessel,caustic
so
or more genera, among which may be listed the
j?ake caustic was added to give a 15%
Quadrula, Pleurobema, Unis, Anodonta, Lampsilis,
more batches of “crackings”
lution, and thirty
from 30 parts of whole mussels, were consecu 20 Tritigom'a,‘ Cyzilas,‘ Thepalia, etc. These are
known in various locations as niggerheads, sand
tively processed as outlined above.
shells, pig toes, maple leaves, buckhorns, wash
The saponi?cation liquor, after being heated at
boards, three ridges, pink elephant ears, pocket
. 95-97" C. was twice extracted with an appropriate
{ solvent such as ethyl ether, in the proportion of
books, etc.
’
The “crackings" from ten batches
of 30.0
parts
of caustic liquor to one part of ether.
25
each
of
a
mixture
of
these
fresh
water
mussels
‘ The combined ether extracts were washed .with
were treated as described previously, and the pro
water and the ether was removed by distillation.
vitamin D and other sterols were isolated in the
was obtained as an i
The unsaponiiiable matter
parts of hot
usual manner.
1 oily solid, which was dissolved in ten
On cooling, the sterols containing the
EXAMPLE 7
1 alcohol.
80
‘ 3 parts
provitamin D crystallized in beautiful white crys_
be further puri?ed by
These sterols may
Prmn'tamin D from the crab, Cancer pagwrus
'The "crackings” from ten batches of ‘50.0 parts,
‘ tals.
recrystallization, decolorization with charcoal or
animal black, conversion to esters, followed by
subsequent saponi?cation, chromatographic ad
sorption, etc. An essentially quantitative yield
‘
each of the‘ steamed crabs were exposed to the ac
35 tion of the same 15% caustic at 95-l00° C. for one
hour p'er batch. The caustic liquors, when proc
essed as described previously, yielded the sterols.
It is to be understood that the foregoing exam
(based on analytical methods‘ of assay) of pro
vitamin Dis obtained by this procedure. ~
I -
few of the many .
ples are illustrative merely of a
Exnlrts 2
modi?cations of which this invention is capable.
provitamin D from the periwinkle, 40 They may be varied widely both with respect to
Production of La'ttoriha littorea
‘
the individual reactants and the conditions of
reaction without departing from the scope of this
By the method outlined in Example 1, 20
batches of “crackings,” each from 30 parts of the
live univalve, Littorina litton-ea, were stripped of 45 In place of the mussels and other shell?sh re
ferred to in the examples, or in addition thereto,‘
the meat in 16 parts of 15% caustic. The saponi
any substance containing fat-soluble constituents
?cation liquor was then extracted with ether,
may be employed; in particular, any substance
which on concentration gave crude sterols.
containing provitamin D. Asa general rule it
‘These after one recrystallization from alcohol
may be stated that the use of shell?sh is more
50
gave almost colorless sterols with a 14% provita
desirable for the production of the largest quan
min D content determined by spectrographic
tity of ‘provitamin D at the most reasonable cost.
invention.~
assay.
_
‘
'
EXAMPLE 3‘
Provitamin D from the oyster drill,
cinereus
Urosalpinx
-
-
"
Among the many types of shell?sh which are
contemplated for use herein, in addition to those
may be ,
55 referred to in the‘ examples, mention
scallops, “coon”
made of oysters, clams, shrim ,
-
oysters, “Japanese oysters,"
By a repetition of the process outlined in Ex
sea snails‘, lobsters .
and the like. While the use of shell?sh gener-~
ample 1, 2,5 batches of “crackings,” each from 30
ally,
contemplatedithat
and musselsv particularly
other bonyis~preferred,,it
animals -or,,?sh=,»
parts of the oyster drill Urosalpinx oinereus, were
stripped of the meat in20'parts of _l5% caustic. 60 may be processed in accordance with the instru
The provitamin D, admixed with other sterols,
was .obtained quantitatively in the form of white
‘
tions hereof.
.
.
,
V
‘ 5.1
It is advisable to ?rst clean the shell?sh orothen;
sources or provitamin D; this, may be- don,, by,“
crystals by crystallization from alcohol.
Other oyster drills, such as the domestic drill
washing them thoroughly. ,Then ,theishellfish
Eupleura candata (Say) and the foreign hedge 65 may be treated with livesteam orqhotawater at
hog murex (Mm-ex erinaceus, Linn.) may be used
as sources of provitamins D.
,
atmospheric
steaming
it is desired
treatment
torelax
or superatmospheric
the
is particularly
muscles holding
pressure:
helpful
the shells
when ,
Exllmrts 4
The water which is “bound” in the
Provitamin D from the mussel, Mytz'lus ‘hamatus, 70 together.
animal may then be drained out in v‘order to pre
Say
.
vent undue dilution of the saponifying solution
The “crackings” from 20 batches of 30.0 parts
to be subsequently used. At this stage the mussel
each of these whole mussels, which are also known
as the hooked mussel, were processed by the
or other shell?sh maybe cracked in order to rup-v ,
sure its shell and permit more intimate contact
method given in Example 1. The sterols con-‘ 76
aforesaid steps may be changed 'and some 01' them 1
my be omitted entirely, if desired.
I'br instance.’
a1‘ may be steamed and cracked open
prior to washing. likewise, the
in: this reaction to completion maybe relied up
on, such as for example, auperatmospheric pres
10 sures.
etc.
,
'
I
' ‘
\ When the saponi?cation reaction is completed
. or brought to the deairedvdegree of partial com
pletion the provitamin D or other fab-soluble
‘constituents
may be removed therefrom in known
15
e earth groups;
with weak acids such
derstood that numerous other
as sodium acetate, sodium
binations thereof may likewise be used.
This latter extraction operation
carbonate, etc.; aqueous solutions 01' orsaniebases
such as tetramethyl ammonium hydroxide, pyri
' dine, etc. As strong'acids may be injurious
_
to the
fat-soluble constituents, their use is not ordinarily
advisable.
25
may be varied widely
in: the desirable results. As
30
In the same manner the process may be modi
fed by introducing iine streams oi’ warm. ben
mm below
the surface of the warm saponi?cation
35 liquor.
',
.
-
ble amount of provitamin D.
When the provitamin D and/or other tat-solu
ble constituents are released by the saponi'iying
solution the shells, it any, and/or other ‘insolu
ble constituents should be
‘
The rat-soluble constituents obtained in the
foregoing manner,
D. may be isolated and puri?ed,
'
action zone.
_
animal black, conversion to es
ters, followed by subsequent saponi?cation, chro
45
matographic adsorption and the like.
By means of the present invention prior‘ art
processes for the recovery oi’
other fat-soluble materials are greatly simplified
The operation may then be repeated using a
fresh supply of provitamin-D-containing mate
rials or of materials containing other fat-soluble 50
55 .
this solution now
understood, of
_
contains the fat-soluble con
stituents removed from the ?rst batch of shell
?sh or other raw materials. Likewise, this solu
tion may have added thereto additional saponiiy 60
group of materials
ing .agent in order to maintain its strength at
the optimum level.
_
able at an appreciable savings in cost. Likewise,
As previously mentioned, the process may be
numerous sources of these valuable materials
which formerly were unavailable because of the
prohibitive cost of treatment, are now made com
05 mercially
feasible.
As many apparently widelydiiferent embodi
ments of this
'
7o
de?ned in the appended-claims:
We claim:
than'ior a single operation.
1. A process for obtaining provitamin D rrom
en the saponiiication liquor contains the
desired amount or provitamin D and/or other rat 75 shellfish which comprises treating said shell?sh
' with
a saponifying solution
remove‘ therefrom,
'
asoensa
poniiyine liquor and reusing said liquor ‘for the
material containing provitamin D, ‘separating the
extraction of material containing provitamin D‘
‘ from additional mussels.
5. A process for obtaining provitamin D from
mussels which comprises treating crackedmus
shells from the .saponii'yingliquor and reusing
said liquor for-‘the extraction or material con-_
taming provitamin D from additonal' shell?sh.
sels, after they have been washed, steamed and
i 2. A process for vobtaining provitamin D I
shell?sh which comprises treating‘said shell?sh " drained, with a saponifying solution of aqueous
with a saponifying solution to remove therefrom
' tially all the material containing provitamin D,
separating the shells from the saponiiying liquor "
and reusing said liquor for the extraction or ma
material containing provitamin D, separating the
shells from the saponifying liquor and reusing
said. liquor tor'the extraction of material con
taining provitamin D from‘ additional shell?sh
terial containing provitamin D from additional
until a'concentrated solution of provitamin D is
mussels until a concentrated solution of provi
obtained.
h 3. A process for obtaining provitamin D from
tamin D is obtained.
7
‘ 6. A process for obtaining provitamin D from
mussels which comprises treating said mussels
mussels which comprises,v ‘treating cracked mus
with a saponiiying solution to remove therefrom
sels with a saponii‘ying- solution of aqueous so
‘
a
'
<.
-
all the material containing provi- '
_
shells from the saponir
tamin D, separating
the said liquor for the ex
reusing
‘tying liquor and
containing provitaminl- D
Ztraction of material
lirom additional mussels until a concentrated so-_
dium hydroxide to remove therefrom material
_ substantially
containing *provitamin D, and separating the
from the saponiiying liquor.
20 shells
‘ 7. In a process of obtaining the unsaponifiable
fraction from shell ?sh the step which comprises
treating the whole broken open shell ?sh with
4. A process for obtaining provitamin D from ‘ caustic alkali to saponify the saponi?able con»
treating cracked mus
stituents and liqueiy the shell ?sh meat.
‘mussels which comprises
have been washed, steamed and 25
WILLIAM S. CALCOT'I‘.
jiution of provitaminD is obtained.
; sels, after they
5 therefrom substantially all the material containing
GEORGE E. HOLBROOK.
' 1 drained, with a‘ saponifying solution to remove
provitamin'D, separating the shells from the sa-
‘
STOCKTON G. TURNBULL, JR.
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