U.S. patent application number 14/447121 was filed with the patent office on 2015-09-03 for carbondisulfide derived zwitterions.
The applicant listed for this patent is Thomas P. Daly. Invention is credited to Thomas P. Daly.
Application Number | 20150246879 14/447121 |
Document ID | / |
Family ID | 54006447 |
Filed Date | 2015-09-03 |
United States Patent
Application |
20150246879 |
Kind Code |
A1 |
Daly; Thomas P. |
September 3, 2015 |
Carbondisulfide Derived Zwitterions
Abstract
Amines and amine derivatives that improve the buffering range,
and/or reduce the chelation and other negative interactions of the
buffer and the system to be buffered. The reaction of amines or
polyamines with various molecules to form polyamines with differing
pKa's will extend the buffering range, derivatives that result in
polyamines that have the same pKa yields a greater buffering
capacity. Derivatives that result in zwitterionic buffers improve
yield by allowing a greater range of stability.
Inventors: |
Daly; Thomas P.; (Arlington
Heights, IL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Daly; Thomas P. |
Arlington Heights |
IL |
US |
|
|
Family ID: |
54006447 |
Appl. No.: |
14/447121 |
Filed: |
July 30, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61946697 |
Feb 28, 2014 |
|
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|
Current U.S.
Class: |
544/315 ;
562/27 |
Current CPC
Class: |
B60R 21/272 20130101;
F42B 3/04 20130101; C07D 401/04 20130101; A01N 25/30 20130101; B60R
21/0132 20130101; B60R 2021/01272 20130101; C06D 5/02 20130101;
B60R 2021/01211 20130101; C07C 333/14 20130101 |
International
Class: |
C07C 333/14 20060101
C07C333/14; A01N 43/54 20060101 A01N043/54; C07D 401/04 20060101
C07D401/04 |
Claims
1. A dispersant of the following structure: ##STR00001## where A
and D are independently chosen from --CH.sub.3, --CH.sub.2CH.sub.3,
--CH.sub.2CH.sub.2CH.sub.3, --CH.sub.2OH.
2. The dispersant of claim 1 where A=D=--CH.sub.3.
3. The sodium salt of the dispersant of claim 1 where
A=D=--CH.sub.3.
4. The potassium salt of the dispersant of claim 1 where
A=D=--CH.sub.3.
5. The dicocomethyl amine (Akzo Armeen M2C or equivelent) salt of
the dispersant of claim 1 where A=D=--CH.sub.3.
6. The dispersant of claim 1 where A=D-CH.sub.2OH.
7. The sodium salt of the dispersant of claim 1 where
A=D=--CH.sub.2OH.
8. The potassium salt of the dispersant of claim 1 where
A=D=--CH.sub.2OH.
9. The dicocomethyl amine (Akzo Armeen M2C or equivelent) salt of
the dispersant of claim 1 where A=D=--CH.sub.2OH.
10. A dispersant of the following structure: ##STR00002## where A,
D and E are independently chosen from --H, --CH.sub.3,
--CH.sub.2CH.sub.3, --CH.sub.2CH.sub.2CH.sub.3, --CH.sub.2OH, where
R is alkyl, alkenyl, alkynal, branched or linear, saturated or
unsaturated.
11. The dispersant of claim 10 where A=--CH.sub.2OH,
D=E=--CH.sub.3.
12. The sodium salt of the dispersant of claim 10 where
A=--CH.sub.2OH, D=E=--CH.sub.3.
13. The potassium salt of the dispersant of claim 10 where
A=--CH.sub.2OH, D=E=--CH.sub.3.
14. The dispersant of claim 10 where A=D=E=--CH.sub.2OH.
15. The sodium salt of the dispersant of claim 10 where
A=D=E=--CH.sub.2OH.
16. The potassium salt of the dispersant of claim 10 where
A=D=E=--CH.sub.2OH.
17-18. (canceled)
19. The dispersant of claim 1 where A=--CH.sub.2CH.sub.3, and
D=--CH.sub.2OH.
20. A dispersant and its salts of the following structure:
##STR00003## where A is chosen from --H, --CH.sub.3,
--CH.sub.2CH.sub.3, --CH.sub.2CH.sub.2CH.sub.3, --CH.sub.2OH, and D
is chosen from --CH.sub.3, --CH.sub.2CH.sub.3,
--CH.sub.2CH.sub.2CH.sub.3, --CH.sub.2OH.
21. The dispersant of claim 20 where A=--H and
D=--CH.sub.2CH.sub.3.
22. The sodium salt of the dispersant of claim 20 where A=--H and
D=--CH.sub.2CH.sub.3.
Description
[0001] This applications is related to and claims priority to U.S.
Provisional Patent Application No. 61/946,697 filed Mar. 3, 2014.
application 61/946,697 is hereby incorporated by reference.
BACKGROUND
[0002] 1. Field of the Invention
[0003] The present invention relates generally to the field of
amines and more particularly to a classes of amino zwitterions.
[0004] 2. Description of the Problem Solved by the Invention
[0005] Amines are extremely useful compounds in the buffering of
biological systems. Each class of amine has various limitations
which require choosing an amine based on multiple factors to select
the best amine. For example, pH buffering range is typically most
important, but issues of chelation, pH range stability, and
solubility also come into play. Typically, a suboptimal buffer will
result in yields that are well below the potential yield. The
present invention improves the yields in fermentation and
purification, and improves shelf stability of proteins and amino
acids.
SUMMARY OF THE INVENTION
[0006] The present invention relates to amines and amine
derivatives that improve the buffering range, and/or reduce the
chelation and other negative interactions of the buffer and the
system to be buffered. The reaction of amines or polyamines with
various molecules to form amine derivatives and polyamines and
derivatives with differing pKa's extend the buffering range;
derivatives that result in polyamines that have the same pKa yield
a greater buffering capacity. Derivatives that result in
zwitterionic buffers improve yield by allowing a greater range of
stability and reduced conductivity.
DESCRIPTION OF THE FIGURES
[0007] Attention is now directed to the following figures that
describe embodiments of the present invention:
[0008] FIGS. 1-2 show the synthesis of zwitterion type buffers from
nitroparaffins.
[0009] FIG. 3 shows the synthesis of dithicarbamates from a series
of biolgically active amines.
[0010] FIG. 4 shows the synthesis of xanthates from
nitroparaffins.
[0011] FIG. 5 shows the synthesis of derivatives of
dithiocarbamates of biologically active amines.
[0012] FIG. 6 shows the synthesis of derivatives of aromatic
dithiocarbamates.
[0013] FIG. 7 shows the synthesis of a range of derivatives based
on dithiocarbmates of dopamine.
[0014] FIG. 8 shows the synthesis of dithiocarbamate dispersants
and polyamine dithiocarbamate derivatives.
[0015] FIG. 9 shows dithiocarbamates from multifunctional secondary
amines.
[0016] FIG. 10 shows the synthesis of pharmacologically interesting
diothiocarbamates.
Several drawings and illustrations have been presented to aid in
understanding the invention. The scope of the present invention is
not limited to what is shown in the figures.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The reaction of carbon disulfide with nitroparaffins or
nitroalcohols form an intermediate from which xanthate and primary
amine functionality can be present in the same molecule through
relatively simple, and high yield reactions. FIGS. 1, 2 and 4
depict the route to nitro xanthates, which have utility as cross
linking agents and vulcanizing agents and rubber. The nitro
functionality improves adhesion of the rubber to the cord in steel
belted radial tires and fiber reinforced tire applications as well
as other reinforced rubber applications. The nitroxanthates can be
utilized as intermediates in the manufacture of primary amine
functional xanthates for biological systems, agriculture and
antimicrobials as well as many other applications. It should be
noted that here, as well as in other embodiments of the invention
where a reduction takes place when a xanthate or dithiocarbamate
functionality is present, the reduction of the nitro to the amine
must be done under relatively mild conditions to limit the
co-products of reducing the xanthate functionality. The xanthates
and dithiocarbamates have additional functionality in agriculture.
The traditional uses such as chelants, and dispersants, are
complimented by their use as antifungal, antimicrobial as well as
growth regulators as promoters as well as phytocides and
insecticides. Often the effects are more pronounced when produced
as metal salts, such as zinc, tin, copper or any other transition
metal salts.
[0018] FIG. 3 shows the synthesis of dithiocarbamtes from a range
of biologically interesting amines. The dithiocarbamates of the
alaphatic and aminoalcohols are a low cost dispersant, cross
linker, with uses in agricultural, antimicrobial, chelant, mining
collector and buffer. While the aromatic amine based
dithiocarbamates are useful in the above applications, the cost
makes them less commercially viable in those applications, however,
they show great promise as therapies for diseases of the nervous
system, such as multiple sclerosis, Alzheimer's, and Parkinson's
diseases. The potential exists for these molecules and their
derivatives to be useful therapies as channel blockers as well,
which is believed to be the mechanism by which the molecules of the
present invention act as an MS therapy. Additionally, the
dithiocarbamates are anti-oxidants and have potential as
nutritional supplements as well as cancer therapies.
[0019] FIGS. 5, 6 and 7 show the synthesis of several classes of
derivatives of the dithiocarbamates previously discussed. Several
of the derivatives, particularly the pyridine containing
derivatives, are biologically active and potential therapies for
mood disorders, multiple sclerosis, Alzheimer's disease, and
Parkinson's disease. The carboxcylic acid and ester containing
derivatives primarily increase the dispersing capability of the
underlying dithiocarbamtes, reduce the chelating, or reduce the
cost of manufacture. The molecules of FIGS. 6 and 7 that contain
aromatic rings and require reduction, must be done under mild
conditions, such as iron with turnings or under very mild
conditions with sponge metal catalysts at ambient temperatures and
pressures of less than 400 psi. The molecules of of FIG. 7 are
typically simple one-pot syntheses. FIG. 8 contains several
dispersants that are more surfactant in nature, with the higher
carbon chain values of R being foam formers. The
di-dithiocarbamates from diamines are strong chelants that are of
the class bidentate, but tend to undergo ring closure if not kept
under basic aqueous conditions. FIG. 9 further expands on these
bidentate chelants by introducing other chelant groups. Thus
allowing for a wider range of substrates for chelation and
dispersion. FIG. 10 teaches a family of aminopyridine derived
dithiocarbamates as well as a dopamine diamine derived
dithiocarbamates all of which are biologically/ pharmacologically
interesting. Similar to those in FIGS. 6 and 7, the reduction steps
must be undertaken under mild conditions to minimize the reduction
of the aromatic groups.
[0020] In the case of the derivatives that are produced as an ionic
molecule, the pure zwitterion may be obtained through ion exchange
as is routinely carried out on an industrial scale. While the
derivatives also show only one dithiocarbamate group, in many cases
a second dithiocarbamate group may be obtained as disclosed in the
earlier figures. The analogous disubstituted derivative, or
mono-substituted analogs are embodiments of the invention.
Additionally, where ethylene oxide is shown as a reactant, one
skilled in alkoxylations will immediately recognize that ethylene
oxide could be substituted with propylene oxide, butylene oxide or
any other alkoxylate to generate the analogous product. All of
these analogs are within the scope of the present invention. For
the derivatives where an amine group results, such as when
acrylonitrile is reacted with the nitro xanthates or
dithiocarbamates, the amine group can further be derivatized with
monochloroacetic acid, allylic acids, sodium vinyl sulfonate,
sultones, alkoxylated or phosphonated as shown in my previous
patent application Ser. No. 14/079,369. It is further understood by
one skilled in the art that higher sultones beyond propane sultone
may be substituted and result in the analogous product with
additional carbon or carbons between the sulfur and sulfonate
group. All of these compounds are also part of the present
invention.
[0021] The xanthates and dithiocarbamates taught here are most
stable and most easily made as salts. The salts are most commonly
sodium salts due to the cost effectiveness and availability of
sodium hydroxide. While not shown as salts in the figures, it is
understood that the salts are within the scope of the invention
taught here. The free zwitterions or neutral forms are obtainable
via ion exchange, and are what are typically shown in the figures.
This is shown explicitly in FIG. 9, in the top reaction series. The
salts are not generally shown in the figures to make it clear that
all salts, are included in the invention, not just sodium salts.
Other bases can be utilized to drive the formation of the xanthates
and dithiocarbamates. The resulting salts are within the scope of
this invention. Of particular note are the use of tertiary amines
to drive the xanthate or dithiocarbamate formation. Not only are
small, volatile tertiary amines useful, but so are fatty tertiary
amines, monoalkyl tertiary amines, such as the ADMA amines by
Lonza, di- and trialkyl tertiaryamines, including tertiary ether
amines, such as those produced by Air Products, formerly Tomah
Products. Also useful are the tertiary amines that result from
alkoxylating primary and secondary amines and ether amines, but
care has to be taken not to cause addition to the terminal hydroxyl
group. This is controlled by adding the alkoxylated amines in a way
that there is a very slight excess of carbon disulfide at all times
versus the alkoxylated amine and the amine to be converted to the
dithiocarbamate.
[0022] The mineral bases such as lime, calcium hydroxide or
potassium hydroxide and all others enable the production of the
molecules taught, but without sodium. This is particularly
important in agricultural applications. The agricultural
applications also benefit from the fatty tertiary amines in that
they help the dithiocarbamates or xanthates penetrate the target
organism that is to be controlled. If desired, the dithiocarbamates
can be made with the starting amine as the counter ion. In this
case, two molar equivalents of the amine needs to be utilized to
one molar equivalent of carbon disulfide during manufacture.
[0023] While much of the benefits of these molecules have been
recognized in biological systems, the zwitterions and derivatives
are also known to be beneficial as dispersants, chelants,
cross-linkers, antimicrobials, preservatives of organic systems,
and pH buffers in oilfield drilling systems and hydraulic
fracturing. Additionally, the molecules of the present invention
find utility as collectors in mining and as depressants. Further,
in ball milling, the dispersant characteristics improve the
characteristics of ore pellets. The zwitterionic molecules of the
present invention also find utility in high energy storage systems,
such as lithium ion and lithium polymer batteries as a means of
improving charge transport and as acting as a salt bridge in other
battery applications.
[0024] Several descriptions and illustrations have been presented
to enhance understanding of the present invention. One skilled in
the art will know that numerous changes and variations are possible
without departing from the spirit of the invention. Each of these
changes and variations are within the scope of the present
invention.
* * * * *