Note: Descriptions are shown in the official language in which they were submitted.
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Description of the Invention
This invention relates to novel chemical compounds
and to their use in controlling fungi and bacteria. More
particularly, the chemical compounds are certain keto oxime
carbona~es. Also, this invention relates to a method of
inhibiting the growth of sulfate reducing bacteria.
The compounds of the present invention are those
having the formula
ClCH2\
\C=N-O- 11 -O-R
ClCH /
in which R is alkyl having from l to 6 carbon atoms.
The compounds of the present invention can be pre-
pared by reacting a compound of the formula
ClCH2\
/C=NOH
ClCH2
with a compound of the formula
O
Halo-C-0-R
in which halo is chlorine or bromine and R is as defined.
Preferably, the reaction is carried out in the
presence of a base such as pyridine and in a solvent for the
reactants. Generally, the reaction is exothermic so no
heating is required. Cooling is sometimes required to control
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the reaction rate. The compounds of this invention can be
recovered from the mixture and purified by standard procedures.
Compounds of the formula
N-OH
ClCH2-C-CH2Cl
can be prepared by reacting
Cl-CH2-C-CH2Cl
with excess hydroxylamine hydrochloride or hydroxylamine
hydrobromide in ethanol and water. The reaction can be run
with heating under reflux for several hours. The desired
product is recovered and purified by conventional techniques.
Example 1
1,3-dichloroacetoneoxime
63.5 grams (0.50 mole) 1,3-dichloropropanone,
69.5 grams (1.00 mole) hydroxylamine hydrochloride, 250 ml.
ethanol and 25 ml. of water were combined and heated under
reflux for four hours. The cooled mixture was poured into
500 ml. of water. The aqueous solution was extracted with
three 100 ml. portions of chloroformr The chloroform phases
were combined and dried with anhydrous MgS04. The chlorofonm
was evaporated to give 66.3 g. (93.6% theory) of 1,3-dichloro-
acetoneoxime,
ClCH2
C=NOH
ClCH /
N30 = 1.5044.
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Example 2
1,3-dichloroacetoneoxim-e O-methyl carbonate
14.1 grams (0.10 mole) 1,3-dichloroacetoneoxime,
10.1 grams (0.13 mole) methylchloroformate were combined in
200 ml. of benzene. The mixture was stirred with cooling
at 13 to 14C. for 20 minutes with 18.1 ml. (0.13 mole) of
triethyl amine. The mixture was allowed to warm to room
temperature. The mixture was washed with two 100 ml. portions
of water. The benzene phase was dried with anhydrous MgSO4
and evaporated to give 9.7 g. of 1,3-dichloroacetoneoxime
O-methyl carbonate,
ClCH2 e
C=NOC-OCH3
ClCH2
N D = 1.4722.
The following is a table of certain selected
compounds that are preparable according to the procedure
described hereto. Compound numbers have been assigned to
each compound and are used throughout the remainder of the
application.
TABLE I
Compound No. R
l* methyl
2 ethyl
3 n-butyl
4 hexyl
*Prepared in Example 2
:` ~
~ 30
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In Vitro Vial Test
The following test illustrates utility of the
compounds in controlling fungi and bacteria. This test
measures the bactericidal and fungicidal properties of a
compound when in contact with a growing bacterium or fungus.
The test is conducted by partially filling two l-ounce vials
with malt broth and one l-ounce vial with nutrient broth.
Next the test compound is added to the vials at a certain
concentration, expressed in parts permillion, and mixed
with the broth. A water suspension of spores of the desired
fungi or cells of the desired bacteria (one organism per
vial) is added. The vials are then sealed and incubated for
one week; at this time the vials are examined and the results
recorded. Table II shows the results of various compounds
tested by the In Vitro Vial Test, partial control of the
test organism is indicated by parentheses. In such a case,
complete control was observed at the next higher concentration.
Table II
Concentration (p.p.m.) Which Inhibited Growth
Compound Aspergillus Penicillium Escherichia Staphylococcus
Numberniger italicum coli aureus
1(.25) (-25) >50 25
2.125 (.125) >50 5
3.125 (1) >50 25
Sulfate reducing bacteria are anaerobic, i.e. they
can thrive in the absence of free oxygen. They are described
as sulfate reducing since in their life metabolism they reduce
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the sulfate ion found in most waters to hydrogen sulfide.
Moreover, these bacteria are resistant or develop resistance
to many bacteriostatic and bactericidal agents. Frequently,
sulfate reducing bacteria multiply so rapidly, particularly
under moist, humid conditions and in a saline environment,
that the concentration of known bactericides, e.g., chlorine,
required for control becomes so high as itself to cause cor-
rosion of unprotected steel equipment.
The sulfate reducing bacteria generally include
the species Desulfovibrio desulfuricans, Desulfovibrio ori-
entis, Clostridium ni~rificans. Of these, the first is most
prevalent.
By "process water" is meant fresh water, slightly
saline water, sea water, or concentrated brines, which are
utilized in or result from various industrial treatments and
whlch-because of their source, mode of storage or utilization,
operate as culture media for sulfate reducing bacteria.
Typical industrial systems employing process water
are metallurgical operations employing cutting oils, latex
paint preparation and storage, oil production including sub-
surface disposal of water withdrawn from wells and water used
to repressurize wells for secondary oil recovery, packing
fluids employed as "dead" layers in the casing of "multiple
completion" oil well systems, and neutral drilling mud systems.
In general, any process water which remains quiescent or under
reduced rate of flow is subject to growth of sulfate reducing
bacteria.
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The harmful effects of growth of these bacteria
are enormous. In oil production, for example, the bacteria
cause injection well plugging and corrosion of iron and
steel pipes and equipment, necessitating expensive shut-down
for cleaning. Using the oil as their carbon source, the
bacteria reduce sulfate ion ~o hydrogen sulfide ("sour gas")
which in turn reacts with iron to form black particles of
suspended iron sulfide. These particles clog the injection
system and the once water-permeable oil-bearing formations.
The bacteria are often the sole cause of pitting type corro-
sion of drilling equipment, either by acting as cathode de-
polarizers or by producing corrosive hydrogen sulfide, but
more often they accelerate corrosion. See A. W. Baumgartner,
"Sulfate-Reducing Bacteria ... Their Role in Corrosion and
Well Plugging," presentation at West Texas Oil Lifting Short
Course, Texas Technological College, Lubbock, Texas, April 21-22,
1960.
Saline water, e.g. brine or sea water, is commonly
employed in primary and secondary oil recovery and as a packing
fluid in multiple completion oil well, particularly in coastal
areas. Saline water, however, greatly limits the choice of
bactericidal agents effective against sulfate reducing bacteria
since many of such agents, e.g., amines, quaternary compounds,
imidazolines, precipitate out in salt solutions. Others, e.g.,
silver and mercury compounds, such as phenyl mercuric acetate,
are precipitated by the sulfides resulting rom the metabolism
of the bacteria.
The problem of effective bactericides in brine systems
is further complicated by the fact that saline solutions encourage
bacterial growth by removing constituents deleterious to bacterial
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growth.
In metallurgical operations, shutdown of a plant
over a weekend, for example, has permitted the growth of sulfate
reducing bacteria in cutting oil tanks, causing unbearable odors
of hydrogen sulfide and loss of production time while the cutting
oils are replaced and tanks cleaned.
Several requirements for usefulness of a bactericide
against sulfate reducing bacteria in the process water must be
met. Thus, the antibacterial agent must not only rapidly and
effectively inhibit growth of sulfate reducing bacteria, but
control must be effective at economically low concentrations.
Additionally, the compound must be compatible with the process
water. In particular, it should not salt out in brine solutions
or react with other constituents so as to promote plugging. Nor
should it coat the filters used, for example, to separate
secondary oil from waterfloods. The antibacterial agent must
be non-toxic both to personnel and to livestock which may drink
from reservoirs. And finally, the agent remaining in the oil
separated from waterfloods must not poison the cracking catalysts
employed in refinin~ oil.
The unpredictability of activity of compounds
against sulfate reducing bacteria is well known. For example,
a wide variation in activity against the same and different
sulfate reducing bacterial strains has been noted for
imidazolines, quaternaries, chlorinated phenols, amines and
glutaraldehyde and hence it was not possible to predict the
activity of one bactericide from knowledge of activity of
another bactericide. See, for example, "Sulfate-Reducing
Bacteria: Their Relation to the Secondary Recovery of Oil",
Science Symposium, St. Bonaventure University October 23-24,
1058~9~
1957, particularly page 6~.
In accordance with the present invention a method
is provided for inhibiting the growth of sulfate reducing
bacteria, and the consequent fouling of process water containing
said bacteria, which comprises contacting said bacteria with
an effective amount of one of the following compounds:
1,3-dichloroacetoneoxime acetate
ClCH2 0
C=NO-C-CH3
ClCH2
1-3-dichloroacetoneoxime propionate
ClCH2 0
C=NO-C-C2H2
ClCH2 /
These compounds are known to be useful in controlling
aerobic bacteria as taught in U.S. 3,733,419.
The amount of compound for effective control will
depend on the particular system in which the process water
is employed. Oil well brines used in oil recovery require in
the order of 25 p.p.m. or less. Neutral drilling muds are
protected against growth of sulfate reducing bacteria by about
50 p.p.m. or less of one of the compounds. Amounts of 150 p.p.m.
less in cutting oils effectively prevent spoilage and offensive
odors therein. Generally, the compounds are effective in
quantities of the order of about 0.25 to 10,000 p.p.m.
The compounds of the invention may be added directly
to the process water in any suitable tank. However, even though
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the maximum concentrations used are small, the volumes are large
and uniform mixing is highly desirable. The most useful mode of
addition is to prepare a relatively smaller, but more concen-
trated solution than the final dilution desired. This solution
can then be metered by a proportioning pump or its equivalent
into a suitably agitated tank or flow of water as the latter is
being pumped to the point of use. Normal turbulent flow in the
conduit produces adequate mixing. In this way, accurate dosages
can be supplied and uniform dilutions obtained.
If desired, any of the numerous well known additives
may be employed with the compounds provided they are compatible
therewith. It may be useful to aid dispersion of a compound
by addition of conventional surfactants in order to prepare
concentrated suspensions or emulsions, aqueous or nonaqueous,
prior to addition to the process water. Suitable dispersions may
be prepared by agitating the compounds in the presence of a sur-
factant such as sodium lauryl sulfate, aliphatic and aromatic
sulfonates, e.g., sulfonated castor oil, or various alkaryl
sulfonates, e.g. the sodium salt of mono sulfonated nonyl
naphthalene. Non-ionic types of emulsifying agents such as the
higher molecular weight alkyl polyglycol ethers and analogous
thio ethers such as the decyl, dodecyl and tetradecyl polyglycol
ethers and thio ethers containing from about 25 to 75 carbon
atoms may be used. The concentration of surfactant in the
final emulsion should be sufficient to make the oil and water
phases readily dispersible. For purposes of forming a spray
emulsion, from about 0.02 to 3~ of the surfactant will be effec-
tive. In general, formulations containing a surface active agent
in the amount of from 1 to 20~ by weight of active ingredient
are satisfactory although such proportion may be varied over
a wide range of proportions depending upon the particular
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circumstance.
Adjuvants such as wetting agents or humectants may,
if desired, be employed particularly when compounding an
aqueous dispersion. Examples of humectants are glycerine,
diethylene glycol, polyethylene glycol and the like.
Sulfate Reducing Bacteria in Vitro Test
This test measures the bac~ericidal properties of
a compound when in contact with a sulfate reducing bacteria,
specifically Desulfovibrio desulfuricans. The test is con-
ducted by dissolving the test compound in acetone to give an
0.5~ solution. This toxicant is added to vials containing
sterile Sulfate API broth with tryptone under anaerobic con-
ditions at such levels to give final toxicant concentrations
of 1, 5, 10 and 50 ~g/ml. of solution. An inoculant solution
of 0.5 ml. of the growing organism, Desulfovibrio desulfuricans,
is added to the vials followed by sufficient sterile distilled
water to give a total of 10 ml. of solution in the vials. The
vials are incubated at room temperature for 3 to 5 days until
untreated controls show growth of the organism as indicated
by the black color development in the vials.
The following is a summary of the minimum inhibitory
concentration necessary to control the organism.
Compound Minimum Inhibitory Conc
~g/ml
1,3-dichloroacetoneoxime acetate 5
1,3-dichloroacetoneoxime propionate 1*
Compound Number 2 5
*lowest concentration tested
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As can be seen by the test results, the compounds
find particular utility as bactericides and fungicides. The
compounds can be applied in a variety of ways at various
concentrations. They can be combined with suitable carriers and
applied as dusts, sprays, or drenches. The amount applied will
depend on the nature of the utility. The rate of application
can also vary with the microbiological use intended.
The problems associated with sulfate reducing
bacteria and method of application for the control thereof
are described in U.S. 3,300,375.
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