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| Germanium Home | Write To Karl Loren | Table Of Contents |
Note: Since Viva is an MLM they do not publish their prices on their web, and generally you cannot order from their web pages. However, I was able to find their price list:
| 104570 | VIVA Germanium (50mg/60 cap) | $68.89 | ||
| 104590 | VIVA Germanium (100mg/100 cap) | $186.67 |
For ease of comparison, Vibrant Life has a bottle of 100 capsules, 35 mg each, of authenticated Japanese Germanium, at $100, or $300 for four bottles.
Also, Vibrant Life has a bottle of 100 capsules, 150 mg each, of authenticated Japanese Germanium, at $250, or $750 for four bottles.
Also, Vibrant Life has a bottle of 100 grams of pure germanium powder, no additives, of authenticated Japanese Germanium, at $900, or four bottles for $2,700.
Vibrant Life is also the exclusive agent for Tokai Sangyo, Japan, the only Japanese exporter of germanium developed at the same time as the original Asai germanium.
Virtually all other germanium being sold in the US is from sellers who will not, or cannot, tell you where their material is manufactured. Viva may be the one exception since they have a patent in their own name for making germanium. However, their patent admits that they make their "germanium" with a very different process than that used in Japan, and than that sold by Vibrant Life.
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The immune system is your body's cellular defense mechanism, which includes the spleen, lymph nodes, skin and specialized blood cells. | |||||||||||||||||
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VIVA
Germanium Sesquioxide™
Premium immune system support. VIVA designed and tested this non-toxic, pure form of the rare trace mineral germanium to support your healthy immune system.
Stock #10457, 10458 |
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VIVA Germanium Sesquioxide is an advanced, non-toxic, form of the rare trace
mineral, germanium.
This rare trace element is found in a wide variety of plant
foods and has been studied for decades with regard to its attributes of
oxygen enrichment, antioxidant properties and supporting healthy functioning
of the immune system. Germanium Sesquioxide has been shown to help produce
the protein, interferon, known to help normalize immune system function.
Again, consuming the organic form of germanium is very important. You may
rest assured that the patented nutraceutical, VIVA Germanium Sesquioxide is
manufactured for purity, consistency and safety so that your body’s immune
system will receive the extra support it needs to function at its best. Directions: Take one (1) capsule daily before a meal. Supplement Facts:
*Daily Value not established. These statements have not been evaluated by the Food and Drug Administration. This product is not intended to diagnose, treat, cure, or prevent any disease. STOCK #10457, 10456
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| United States Patent | 5,386,046 |
| Arnold | January 31, 1995 |
Method for the preparation of pure carboxyethyl germanium
sesquioxide
Abstract
A synthetic method for generating pure carboxyethyl germanium sesquioxide in the absence of toxic impurities. In the method germanium dioxide and metallic germanium are not used as starting materials. The method involves the production of pure crystals of trichlorogermane propionic acid which are converted to carboxyethyl germanium sesquioxide. The product has an LD.sub.50 value of at least 5 g/kg.
| Inventors: | Arnold; Michael J. (Irvine, CA) |
| Assignee: | Viva America Marketing, Inc. (Costa Mesa, CA) |
| Appl. No.: | 204548 |
| Filed: | March 2, 1994 |
| Current U.S. Class: | 556/89; 556/87; 556/105 |
| Intern'l Class: | C07F 007/30 |
| Field of Search: | 556/87,105,89 |
References Cited [Referenced By]
U.S. Patent Documents
| 3793455 | Feb., 1974 | Asai et al. | 424/287. |
| 4066678 | Jan., 1978 | Sato et al. | 260/429. |
| 4473581 | Sep., 1984 | Ishida et al. | 424/287. |
| 4898882 | Feb., 1990 | Nagahama et al. | 514/492. |
| 4956272 | Sep., 1990 | Kakimoto et al. | 435/1. |
| 4973553 | Oct., 1990 | Miyao et al. | 435/206. |
| Foreign Patent Documents | |||
| 2222404 | Mar., 1990 | GB. | |
Primary Examiner: Dees; Jose G.
Assistant Examiner: Nazario-Gonzalez; Porfirio
Attorney, Agent or Firm: Cohen; Lawrence S.
Claims
I claim:
1. A method of preparing organic germanium in the absence of any toxic level of
germanium dioxide or metallic germanium comprising;
preparing trichlorogermane propionic acid as a crude reaction product from
germanium tetrachloride;
forming high purity crystals of trichlorogermane propionic acid from the said
crude reaction product of trichlorogermane propionic acid by a crystallization
process;
forming a germanium acrylate moiety as a reaction product from hydrolysis of the
high purity crystals of trichlorogermane propionic acid;
forming carboxyethyl germanium sesquioxide as a reaction product from
acidification of the germanium acrylate moiety.
2. A method of preparing organic germanium in the absence of any toxic level of
germanium dioxide or metallic germanium comprising;
reacting germanium tetrachloride, acrylic acid and tetramethly disiloxane to
obtain first reaction products in a first mixture;
removing volatiles from the first mixture to obtain a second mixture;
reacting the second mixture with at least an effective amount of hydrochloric
acid to obtain a third mixture consisting essentially of trichlorogermane
propionic acid and hydrochloric acid;
separating by extraction with an organic solvent trichlorogermane propionic acid
from hydrochloric acid in the third mixture to form a fourth mixture;
removing the extraction solvent from the fourth mixture to form a crude reaction
product of trichlorogermane propionic acid;
dissolving the crude reaction product with a non-polar alkyl solvent to form
high purity crystals of trichlorogermane propionic acid;
hydrolyzing the high purity crystals of trichlorogermane propionic acid in
ammonium hydroxide to form a fifth mixture;
reacting the fifth mixture with slow addition of concentrated sulfuric acid to
form carboxyethyl germanium sesquioxide.
3. The method of claim 2 wherein the organic solvent is a halogenated solvent.
4. The method of claim 3 wherein the solvent is selected from the group
consisting of dichloromethane, carbon tetrachloride and chloroform.
5. The method of claim 4 wherein the solvent is dichloromethane.
6. The method of claim 1 wherein the non-polar alkyl solvent is hexane.
7. The method of claim 1 wherein the acidifying step is slow addition of
concentrated sulfuric acid.
8. A method of preparing pure organic germanium in the absence of germanium
dioxide or metallic germanium comprising;
preparing trichlorogermane propionic acid as a crude reaction product from
materials not including either germanium dioxide or metallic germanium;
forming high purity crystals of trichlorogermane propionic acid from the said
crude reaction product of trichlorogermane propionic acid;
forming carboxyethl germanium sesquioxide as a reaction product from hydrolysis
of the trichlorogermane propionic acid.
Description
BACKGROUND
1. Field of the Invention
The present invention relates to a synthetic method for generating pure
carboxyethyl germanium sesquioxide, and in particular to a chemical method for
synthesizing carboxyethyl germanium sesquioxide that yields the carboxyethyl
germanium sesquioxide without trace amounts of germanium dioxide or metallic
germanium.
2. Description of the Prior Art
Carboxyethyl germanium sesquioxide (organic germanium) has been shown to have
chemotherapeutic value. Nakao Ishida, et. al., U.S. Pat. No. 4,473,581 teach
that carboxyethyl germanium sesquioxide can induce interferon production in
humans. Nagahama teaches in U.S. Pat. No. 4,898,882 that carboxyethyl germanium
sesquioxide can provide the human body resistance against the common cold. Asai
in U.S. Pat. No. 3,793,455 describes the use of carboxyethyl germanium
sesquioxide as an agent for treatment of hypertension. Although carboxyethyl
germanium sesquioxide is a well known compound, its molecular structure has been
shown to be dependent on the synthetic method employed.
For use as a chemotherapeutic agent, or as a food supplement, it is required
that carboxyethyl germanium sesquioxide be pure, free of unwanted and
potentially lethal contaminants germanium dioxide and metallic germanium. Many
known methods for synthesizing carboxyethyl germanium sesquioxide provide for
the production of germanium sesquioxide contaminated with trace amounts of
metallic germanium, or germanium dioxide, since these are used as the starting
materials. Trichlorogermanium acrylate moieties (trichlorogermanium acroyl
chlorides, trichlorogermanium acrylic acids, trichlorogermanium acroleins and
trichlorogermanium alkyl acrylates) are the key intermediates common to such
known synthetic routes. Entries described by the prior art to the
trichlorogermanium acrylate intermediates, utilize methods that require either
oxidation of metallic germanium with hydrochloric acid, or reduction of
germanium dioxide and, hence, the probability of the presence of trace amounts
of unreacted starting material (metallic germanium or germanium dioxide) in the
product is significant.
The present invention does not start with either metallic germanium or germanium
dioxide, but rather starts with germanium tetrachloride.
SUMMARY OF THE INVENTION
Accordingly, a major object of the present invention is the provision of a
synthetic method that is devoid of the aforementioned drawbacks which to date
have characterized this art.
It is the primary object of the present invention to provide a method whereby
carboxyethyl germanium sesquioxide can be prepared without contamination from
metallic germanium or germanium dioxide.
It is another object of the present invention to provide a method for the
production of a carboxyethyl germanium sesquioxide molecular species that is
completely non toxic to the human body.
It is another object of the present to provide a method for the production of a
carboxyethyl germanium sesquioxide molecular species that has an LD.sub.50 value
of at least 5 g/Kg.
The present method involves the isolation and purification of the intermediate
trichlorogermane propionic acid (hereafter referred to as TPA). In this method
reaction of germanium tetrachloride in the presence of acrylic acid takes place
under ambient conditions to form a mixture of polymeric material and TPA. This
mixture is then depolymerized with concentrated hydrochloric acid to form a
crude TPA reaction product, which is then recrystallized to a pure TPA form. The
pure TPA is then hydrolyzed to form carboxyethyl germanium sesquioxide.
DETAILED DESCRIPTION OF THE INVENTION
The method of the invention involves the steps of forming from the starting
material of germanium tetracholoride, an intermediate material, trichlorogermane
propionic acid, isolating and purifying the trichlorogermane propionic acid and
converting the TPA by hydrolysis to carboxyethyl germanium sesquioxide.
The specific steps of the process are described as follows:
a first mixture is obtained by reacting germanium tetrachloride with tetramethyl
disiloxane and acrylic acid. This first mixture consists essentially of
trichlorogermane propionic acid (TPA), a polymer and volatile by-products. The
reaction profile is: ##STR1##
The first mixture is subjected to vacuum distillation to remove the volatiles.
This results in a second mixture which consists essentially of TPA plus the
polymerized germanium acrylates (hereafter referred to as "polymer"). The
chemical profile of this steps is: ##STR2##
The second mixture is reacted with hydrochloric acid in sufficient amount,
preferably in excess, to completely react with the polymer for depolymization,
that is to convert the polymer to TPA providing a third mixture consisting
essentially of TPA and hydrochloric acid. The reaction essentially of TPA and
hydrochloric acid. The reaction profile is: ##STR3##
The third mixture is subjected to solvent extraction to separate the
hydrochloric acid from the TPA and provide a fourth mixture consisting
essentially of TPA and extraction solvent. The preferred solvent is a sufficient
amount, preferably in excess, of a halogenated solvent, specifically
dichloromethane being most preferred. Chloroform and carbotetrachloride might
also work. The reaction profile is: ##STR4##
The fourth mixture is subjected to vacuum distillation to remove the solvent
(H.sub.2 CCl.sub.2) resulting in a crude reaction product, consisting
essentially of TPA. That is, the TPA is in a form .or mixture presumed to be
insufficiently pure. The reaction profile is: ##STR5##
Next the crude TPA reaction product is purified and converted to carboxyethyl
germanium sesquioxide by the following steps:
The crude TPA reaction product is dissolved in a minimal amount of boiling
non-polar alkyl solvent, preferably hexane, to form upon cooling, high purity
crystals of TPA. The hexane is removed and the resulting crystals are washed
successively with hexane in order to yield fine pure crystals of TPA. The
reaction profile is: ##STR6##
This results in pure crystals of TPA.
Next the pure TPA crystals are reacted in a sufficient amount, preferably in
excess, of ammonium hydroxide, to form a fifth mixture consisting of hydrolyzed
TPA. Slow addition of concentrated sulfuric acid yields carboxyethyl germanium
sesquioxide. The chemical profile is:
Fifth mixture+H.sub.2 SO.sub.4 (conc).fwdarw.Ge.sub.2 C.sub.0 H.sub.10 O.sub.7
A one-pot synthesis of analytically pure organic germanium is described below.
To a 2 L round bottom flask purged with argon was added successively: germanium
tetrachloride (200 g [0.9346 mol]), tetramethyldisiloxane (125 g [0.93 mol]),
and acrylic acid (70.0 g [0.97 mol]). The reaction flask was purged with argon
then sealed by placement of a ground glass stopper with a teflon sleeve and
secured via teflon tape. The slightly cloudy mixture changed to a clear,
colorless homogeneous solution within about 2 hours, and this was stirred for
seven days at ambient temperature. The volatile components were removed via
vacuum (0.5 to 5 mmHg) while the product mixture was heated to an internal
temperature of 70.degree. C.-80.degree. C., where it was a homogeneous, clear
and colorless viscous solution (melt). Evacuation was continued until no more
distillate was observed (ca. 2 hours). This was cooled to an ambient temperature
to yield a white amorphous solid. To this was added 950 mL of concentrated HCl.
The resulting heterogeneous mixture was warmed to an internal temperature of
60.degree. C.-70.degree. C., and stirred for four hours. The cooled mixture was
extracted 3 times with 500 mL of dichloromethane. The combined extracts were
evaporated under reduced pressure via rotoryevaporator to give a white amorphous
solid. This was dissolved in ca. 1 L boiling hexane (until a clear colorless
homogeneous hot solution was obtained), and let cool gently to ambient
temperature. The product, trichlorogermanepropionic acid, was isolated via
suction filtration, washed once with hexane to give fine prisms, mp 75.degree.
C.-79.degree. C. This was immediately taken up (vigorous reaction), with careful
addition of 850 mL of ammonium hydroxide (29% ammonia). The resulting turbid
mixture was stirred for 4 days at ambient temperature (the mixture changes to a
clear, colorless homogeneous solution within 3 hours). To this homogeneous
solution was added dropwise over two hours through a reflux condenser 400 mL of
concentrated sulfuric acid. NOTE: This is a very vigorous reaction and should be
handled with extreme care. A white precipitate formed after addition of ca. 375
mL of acid. The pot was stirred for 48 hours, and then the while solid was
isolated via suction filtration, washed successively with 2.times.150 mL water,
1.times.150 mL acetone, and 1.times.200 mL of diethyl ether, then this brilliant
white solid was air dried overnight, and then taken up with 150 mL hot water,
then cooled and filtered to yield 78.84 g (50%) of analytically pure
carboxyethyl germanium sesquioxide.
Although particular embodiments of the invention have been described and
illustrated herein, it is recognized that modifications and variations may
readily occur to those skilled in the art, and consequently it is intended that
the claims be interpreted to cover such modifications and equivalents.
* * * * *
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