CA1221096A - Biocidal dialkyl (3,5-substituted hydroxayalkyl oxazolidines and hydrocarbylene polyoxymethyleneoxazolidines) - Google Patents
Biocidal dialkyl (3,5-substituted hydroxayalkyl oxazolidines and hydrocarbylene polyoxymethyleneoxazolidines)Info
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- CA1221096A CA1221096A CA000449010A CA449010A CA1221096A CA 1221096 A CA1221096 A CA 1221096A CA 000449010 A CA000449010 A CA 000449010A CA 449010 A CA449010 A CA 449010A CA 1221096 A CA1221096 A CA 1221096A
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- methyloxazolidine
- propyl
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Abstract
BIOCIDAL DIALKYL [3, 5 - SUBSTITUTED HYDROXYALKYL
OXAZOLIDINES AND HYDROCARBYLENE POLYOXYMETHYLENEOXAZOLIDINES]
ABSTRACT
This invention discloses a novel class of hydroxy-alkyl oxazolidines, and polyoxymethyleneoxazolidines to be used as bactericides in aqueous surface coating compositions.
The compounds have the following structural formulas:
I
II
wherein R is hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an aryl group of 6 to 10 carbon atoms; R1 represents hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl group of 6 to 10 carbon atoms containing alkyl, halogen, alkoxy, nitro or other substitutuents; R2 represents hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, or an aryl group of 6 to 10 carbon atoms; and n represents an integer in the range of 0 to 8.
OXAZOLIDINES AND HYDROCARBYLENE POLYOXYMETHYLENEOXAZOLIDINES]
ABSTRACT
This invention discloses a novel class of hydroxy-alkyl oxazolidines, and polyoxymethyleneoxazolidines to be used as bactericides in aqueous surface coating compositions.
The compounds have the following structural formulas:
I
II
wherein R is hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an aryl group of 6 to 10 carbon atoms; R1 represents hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl group of 6 to 10 carbon atoms containing alkyl, halogen, alkoxy, nitro or other substitutuents; R2 represents hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, or an aryl group of 6 to 10 carbon atoms; and n represents an integer in the range of 0 to 8.
Description
~Z~096 _ ~
BIOCIDAL DIALKYL [3, 5 - SUBSTITUTED HYDROXYALKYL
OXA20LIDINES AND HYDROCARBYLENE POLYOXYMETHYLENEOXAZOLIDINES]
TECHNICAL FIELD
This invention discloses a novel class of hydroxy alkyl oxazolidines, and polyoxymethyleneoxazolidines to be used as bactericides in aqueous surface coating compositions.
1~
The compounds have the following structural formulas:
R - R
R -fH-C~2-N ~ o R2-CH-CH -N ~ O
I Il wherein R is hydrogen, an alkyl group of l to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an aryl group of 6 to lO carbon atoms; R represents hydrogen, an alkyl group of l to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl group of 6 to lO carbon atoms, a substituted aryl group of 6 to lO
carbon atoms containing alkyl, halogen, alkoxy, nitro or other substituents; R2 represents hydrogen, an alkyl ~ group of l to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, or an aryl group of 6 to lO carbon atoms;
and n represents an integer in the range of O to 8, preferably 0-4.
` ~2~C~gl6 BACKGROUN~ OF THE INVENTION
Aqueous surface coating compositions such as paints, enamels, varnishes and their respective component materials are particularly susceptible to contamination by bacteria and other microorganisms.
Various mono- and bi- cyclic oxymethyleneoxazo-lidines exhibit biocidal and disinfectant activity and aredisclosed in various United States patents, including:
3,890,264; 3,962,~71; 4,012,261; 4,022,90~; 4,038,284;
4,088,655; 4,138,545; 4,1~8,905; 4,153,701. These known compounds are substituted at the 2 and in the 4 positions of the ring.
This invention provides a cla~s of hydroxyalkyl oxazolidines and polyoxymethyleneoxazolidines which are characterized by novel structures including substitution at the 3 and in the 5 positions of the ring. The hydroxy-alkyl oxazolidines and the resulting poloxymethylene-oxazolidines are highly effective as antibacterial agents.
SUMMARY_OF T~E INVENTION
This invention relates to a class of hydroxyalkyl oxazolidines and polyoxymethyleneoxazolidines having structural formulas which include novel substituents at the 3 and 5 positions of the ring:
122~096 R R
R -~ -CU2-N ~ o R2-C~-C~2-~ y o I II
wherein R is hydrogen, an alkyl group of l to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an aryl group of 6 to l0 carbon atoms; R1 represen~s hydrogen, an alkyl group of l to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl ~roup of 6 to l0 carbon atoms, a substituted aryl group of 6 to l0 carbon atoms containing alkyl, halogen, alkoxy, nitro or other substituents; R2 represents hydrogen, an alkyl group of l to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, or an aryl group of 6 to l0 carbon atoms;
and n represents an integer in the range of 0 to 8.
The substitutions permit the hydroxyalkyl oxazolidines and polyoxymethyleneoxazolidines to act as highly effective biocidal agents in aqueous surface coating compositions~
DESCRIPTION OF THE INYENTION
The biocidal compounds of this invention are prepared according to the following method:
Preparation of Oxazolidines The oxazolidines of this invention are prepared ~ lZZ1096 by the reaction of an hydroxylated amine having the general formula:
BIOCIDAL DIALKYL [3, 5 - SUBSTITUTED HYDROXYALKYL
OXA20LIDINES AND HYDROCARBYLENE POLYOXYMETHYLENEOXAZOLIDINES]
TECHNICAL FIELD
This invention discloses a novel class of hydroxy alkyl oxazolidines, and polyoxymethyleneoxazolidines to be used as bactericides in aqueous surface coating compositions.
1~
The compounds have the following structural formulas:
R - R
R -fH-C~2-N ~ o R2-CH-CH -N ~ O
I Il wherein R is hydrogen, an alkyl group of l to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an aryl group of 6 to lO carbon atoms; R represents hydrogen, an alkyl group of l to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl group of 6 to lO carbon atoms, a substituted aryl group of 6 to lO
carbon atoms containing alkyl, halogen, alkoxy, nitro or other substituents; R2 represents hydrogen, an alkyl ~ group of l to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, or an aryl group of 6 to lO carbon atoms;
and n represents an integer in the range of O to 8, preferably 0-4.
` ~2~C~gl6 BACKGROUN~ OF THE INVENTION
Aqueous surface coating compositions such as paints, enamels, varnishes and their respective component materials are particularly susceptible to contamination by bacteria and other microorganisms.
Various mono- and bi- cyclic oxymethyleneoxazo-lidines exhibit biocidal and disinfectant activity and aredisclosed in various United States patents, including:
3,890,264; 3,962,~71; 4,012,261; 4,022,90~; 4,038,284;
4,088,655; 4,138,545; 4,1~8,905; 4,153,701. These known compounds are substituted at the 2 and in the 4 positions of the ring.
This invention provides a cla~s of hydroxyalkyl oxazolidines and polyoxymethyleneoxazolidines which are characterized by novel structures including substitution at the 3 and in the 5 positions of the ring. The hydroxy-alkyl oxazolidines and the resulting poloxymethylene-oxazolidines are highly effective as antibacterial agents.
SUMMARY_OF T~E INVENTION
This invention relates to a class of hydroxyalkyl oxazolidines and polyoxymethyleneoxazolidines having structural formulas which include novel substituents at the 3 and 5 positions of the ring:
122~096 R R
R -~ -CU2-N ~ o R2-C~-C~2-~ y o I II
wherein R is hydrogen, an alkyl group of l to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an aryl group of 6 to l0 carbon atoms; R1 represen~s hydrogen, an alkyl group of l to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl ~roup of 6 to l0 carbon atoms, a substituted aryl group of 6 to l0 carbon atoms containing alkyl, halogen, alkoxy, nitro or other substituents; R2 represents hydrogen, an alkyl group of l to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, or an aryl group of 6 to l0 carbon atoms;
and n represents an integer in the range of 0 to 8.
The substitutions permit the hydroxyalkyl oxazolidines and polyoxymethyleneoxazolidines to act as highly effective biocidal agents in aqueous surface coating compositions~
DESCRIPTION OF THE INYENTION
The biocidal compounds of this invention are prepared according to the following method:
Preparation of Oxazolidines The oxazolidines of this invention are prepared ~ lZZ1096 by the reaction of an hydroxylated amine having the general formula:
2 7 OH OH
with an aldehyde having the general formula:
R -CH=O
The reaction is carried out in an inert solvent, which forms an azeotrope with water, at reflux. Equimolar portions of amine and aldehyde are preferred. The water of reaction is normally continuously removed. The solvent is removed and the product is distilled at reduced pressure.
The starting hydroxylated amines have the general formula:
H
1H O~
wherein R represents hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an aryl group of 6 to 10 carbon atoms; and R2 represents - hydrogen, an alkyl group of 1 to 6 carbon atoms, a cyclo-alkyl group of 3 to 8 carbon atoms, or an aryl group of 6
with an aldehyde having the general formula:
R -CH=O
The reaction is carried out in an inert solvent, which forms an azeotrope with water, at reflux. Equimolar portions of amine and aldehyde are preferred. The water of reaction is normally continuously removed. The solvent is removed and the product is distilled at reduced pressure.
The starting hydroxylated amines have the general formula:
H
1H O~
wherein R represents hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an aryl group of 6 to 10 carbon atoms; and R2 represents - hydrogen, an alkyl group of 1 to 6 carbon atoms, a cyclo-alkyl group of 3 to 8 carbon atoms, or an aryl group of 6
3~ to 10 carbon atoms. Preferably, R and R2 are hydrogen, or lower alkyls of 1 to 6 carbon atoms, particularly methyl, ethyl, propyl or butyl. Specific useful hydroxylated amines are: diethanolamine, diisopropanolamine, diisobutanolamine, diisoamylalcoholamine, diisohexanolamine.
~ 2~096 The starting aldehydes have the general formula:
Rl--CH=O
wherein Rl represents hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl group of 6 to 10 carbon atoms containing alkyl, halogen, alkoxy, nitro or other substituents. Preferably, Rl is a lower alkyl. Specific useful aldehydes are formaldehyde, paraformaldehyde, acetaldehyde, or propionaldehyde.
Preparation of Oxazolidine-Formaldehyde Adducts The oxazolidines of this invention are prepared according to the above method. Then, one mole of the oxazolidine starting material is reacted with one to eight moles of aqueous formaldehyde and/or paraformaldehyde.
The reaction is preferably carried out in an aqueous solution at 25 to 100 C.
The hydroxyalkyl oxazolidines and polyoxymethy-leneoxazolidines prepared according to the above methods are advantageously used as biocidal agents in aqueous surface coating compositions. The concentration of the bactericide in the surface coatinq composition is in the range of 0.005% to 1.0%, preferably 0.05 to 0.35~.
The following Table lists various oxazolidines 3G of this invention. The Table is not limiting in scope, and is intended for the purpose of illustration only.
.2 2 ~
Compound n R Rl R2 1~ (Example 2) C~3 B C~3 2. (Example 3) 1 CH3 ~ c~3 3. (~xample 4) 2 C~3 ~ c~3
~ 2~096 The starting aldehydes have the general formula:
Rl--CH=O
wherein Rl represents hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl group of 6 to 10 carbon atoms containing alkyl, halogen, alkoxy, nitro or other substituents. Preferably, Rl is a lower alkyl. Specific useful aldehydes are formaldehyde, paraformaldehyde, acetaldehyde, or propionaldehyde.
Preparation of Oxazolidine-Formaldehyde Adducts The oxazolidines of this invention are prepared according to the above method. Then, one mole of the oxazolidine starting material is reacted with one to eight moles of aqueous formaldehyde and/or paraformaldehyde.
The reaction is preferably carried out in an aqueous solution at 25 to 100 C.
The hydroxyalkyl oxazolidines and polyoxymethy-leneoxazolidines prepared according to the above methods are advantageously used as biocidal agents in aqueous surface coating compositions. The concentration of the bactericide in the surface coatinq composition is in the range of 0.005% to 1.0%, preferably 0.05 to 0.35~.
The following Table lists various oxazolidines 3G of this invention. The Table is not limiting in scope, and is intended for the purpose of illustration only.
.2 2 ~
Compound n R Rl R2 1~ (Example 2) C~3 B C~3 2. (Example 3) 1 CH3 ~ c~3 3. (~xample 4) 2 C~3 ~ c~3
4. ~Example 5) 3 c~3 CH3
5. (Example 6) 4 CH3 c~3
6. 0 2 5 C~3 C2H5
7. 0 ~ C~3 C3H7
8. 0 C~Hg CB3 C
EXAMPLES
The following example~ are illustrative and are set forth for the purpose of ~llustration only and are not to be construed a~ limiting the scope of the invention in any manner.
ExamPle 1 A mixture containing 46,6 9 lO.3~ m) of diiso-propanolamine, 10.8 9 (0.35 m) of 97% paraformaldehyde, and 100 cc of toulene was refluxed unt~l 6.3 cc of water wa~ collected in a Barrett tube. The toluene was distil-led off ~nd the re~aining product was distilled at 78C
at a pressure o~ 4O5 mm Hg. The resulting yield of 3-(2-hydroxy)propyl-5-methyloxazolidine starting material was 96.6~.
Elemental analysis of the product showed the following:
~ C % ~ % N ~ o Calculated 57.9 10.34 9.65 22.11 Found 58.12 10~83 9.62 ~1.43 ~22:1 U~6 Example 2 A mixture containing 29 g (0.2 m) of 3~2-_ hydroxy)-propyl-5-methyloxazolidine, 6.6 g (0.2 m) of 91%
paraformaldehyde, and 34.4 g of water was refluxed for one hour. The product obtained was an aqueous solution ` containing 50% water and 50% 3-(2-hydroxymethylene oxy)propyl-5-methyloxazolidine.
.~
Elemental analysis of the product showed the following:
,.~ .
% C % H % N% 0 Calculated 27.43 10.41 4.00 58.15 Found 27.2110.45 3.96 58.38 .,~
Example 3 I A mixture containing 29 g (0.2 m) of 3- f 2 hydroxy)propyl-5-methyloxazolidine, 13.2 g (0.4 m) of 91%
paraformaldehyde and 39.8 g of water was stirred at reflux for 30 minutes. The product obtained was an aqueous - 25 solution containing 50% water and 50% 3-(2-! [hydroxymethyloxymethyleneoxy])propyl-5-methyloxazolidine.
.
Elemental analysis of the product showed the following:
~ 30 -~ % C % H % N% 0 `~ Calculated 26.34 10.18 3.42 60.05 :' Found 26.16 10.21 3.39 60.24 ~2Z~1396 Example 4 A mixture containing 29 g (0.2 m) 3-(2 hydroxy-) propyl-5-methyloxazolidine, 18.5 g (0.6 m) of 97%
paraformaldehyde and 46.5 9 of water was stirred at reflux for one hour. The product obtained was an aqueous solution containing 50% water and 50% 3-[2-(hydroxymethyl-dioxymethyleneoxy)propyl3-5-methyloxazolidine.
Elemental analysis of the product showed the following: ~
% C _ % N % O
Calculated 25.53 10.02 2~98 61.46 Found 25.29 10.08 2.8361.80 ExamPle 5 A mixture containing 29 g (0.2 m) of 3-(2-hydro-xy)propyl-5-methyloxazolidine, 33 g (1.0 m) of 91%
paraformaldehyde and 56 g of water was stirred at reflux for one hour. The product obtained was an aqueous solution containing 50~ water and 50% 3-[2-(hydroxymethyl-tetra(oxymethylene)oxy)propyl]-5-methyloxazolidine.
Elemental analysis of the product showed the following:
-% C ~ H % N % O
_ _ _ Calculated 24.41 9.792.37 63.42 Found 24.49 9.72 2.3463.45 xample 6 A mixture containing 29 g (0.2m) of 3~(2-hydroxy)-" lZZ1096 propyl-5-methyloxazolidine, 26.4g (0.8 m) of 91~
paraformaldehyde and 50.6g of water was stirred at reflux for 45 minutes. The product obtained was an aqueous solution containing 50% water and 50~ 3-[2-(hydroxymethyl-tri(oxymethylene)oxy)propyl]-5-methyloxazolidine.
Elemental analysis of the product showed the following:
% C % H % N ~ O
Calculated 24.90 9.89 ~ 2.64 62.56 Found 24.94 9.86 2.6162.59 EXample 7 The Minimum Inhibitory Concentration Test against Pseudomonas Aeruginosa was carried out under the following conditions. The compounds of this invention were added to sterile nutrient broth at 0.l~ (1009 ppm) concentration. Each mixture was sequentially diluted with sterile broth to yield various levels of concentrations (500 ppm, 250 ppm, 125 ppm, 62 ppm).
One drop of an actively-growing 24-hour culture of the bacteria was added to each level and the mixture was incubated at 30C. After 24 hours of incubation, an aliquot from each tube was placed on nutrient agar and observed for growth. The results appear in Table 1.
Table I also indicates the results of a test run to show the concentration of test compound required to kill Pseudomonas Aeruginosa in 24 hours.
~L2%10gi~
TABLE I
_ological Data on Oxazolidine Derivatives Minimum Inhibitory Concentration against Pseudomonas _ Aeruginosa .~ LEYEL PPM
;~ - 101)0 500 250125 62 l:l Molar Ratio* ~ + +
10 1: 2 Molar Ratio -- -- -- + +
3 Molar Ratio -- -- -- ~ +
l:4 Molar Ratio -- -- -- -- +
l:5 Molar Ratio -- -- -- -- +
Oxazolidine** -- -- -- + +
Concentration Required to Kill Pseudomonas Aeruginosa in 24 Hrs.
r LEVEL PPM
l:l Molar Ratio* -- -- + + +
, l:2 Molar Ratio -- -- + + +
A~ 1 3 Molar Ratio -- -- -- +
l:4 Molar Ratio -- -- -- + +
25 1: 5 Molar Ratio -- -- + + +
Oxazolidine** -- -- -- + +
LEGEND: - = No Growth , + = Growth , ~
.~
* = In each instance the molar ratio is for the compound to paraformaldehyde ** = 3-(2-hydroxy)propyl-5-methyloxazolidine `~ 122i(~96 Example 8 The anti-bacterial properties of paints contain-ing the compounds of this invention were subsequently evaluated. A latex paint was prepared by following the order of addition listed in the paint formulations in Table II.
TABLE II
- PAINT FORMULA~TION
RAW MATERIAL LBS. PER 100 GALLONS
Water 200 Ethylene Glycol20 Cellulosic Thickener 3 Dispersant 6 Surfactant 2 Defoamer 20 Bactericide 2.3 Titanium Dioxide 250 Magnesium Silicate 150 Water 20 Coalescing Agent 8 25 Defoamer Vinyl Acrylic Emulsion 468 _ 1131.30 The bactericide was incorporated before the pigment (titanium dioxide, magnesium silicate) as part of the grind. After 20 minutes, the remaining paint ingre-dients were added at a slow speed. The paint prepared in this manner contained a 0.2~ concentration of oxazolidine or derivatives, as a 50% aqueous solution.
-` ~22~096 The paints containing the oxazolidines were inoculated with a mixed bacterial culture containing Escherichia Coli, Pseudomonas Aeruginosa, Proteu~ Mira-bilis, and Enterobacter Aero~enes. Biocidal performancewas evaluated at various time intervals by applying a streak of each paint to nutrient agar and recording the results on a growth/no growth basis. The results are listed on Table III.
~2Z1~3~
TABLE III
Anti-Bacterial Evaluation of Oxazolidine Derivatives at 0.2% Versus A Mixed Bacterial Culture of Pseudomonas Aeruginosa, Escherichia Coli, Proteus Mirabilis, Ent~robacter Aerogenes FIRST INOCULATION
~ J
- HRS HRS HRS HRS DAYS
Blank 4 4 4 4 4 ^`~ 10 1:1 Molar Ratio* 2 0 0 0 0 1:2 Molar Ratio 0 0 0 0 0 1:3 Molar Ratio 0 0 Q 0 0 ~ 1:4 Molar Ratio 0 0 0 0 0 ~t 1:5 Molar Ratio 0 0 0 0 0 i 15 Oxazolidine** 0 0 i SECOND INOCULATION
HRS HRS HRS HRS DAYS
20 Blank 3 4 4 4 4 1:1 Molar Ratio* 3 0 0 0 0 1:2 Molar Ratio 2 0 0 0 0 ~i 1:3 Molar Ratio 0 0 0 0 j 1:4 Molar Ratio 0 0 0 0 0 1:5 Molar Ratio 0 0 0 0 0 25 Oxazolidine** 4 4 4 4 4 - LEGEND: 0 = no microbial growth .1 = slight microbial growth `~2 = moderate microbial growth `~3 = heavy microbial growth `:~4 = very heavy microbial growth * = In each instance the molar ratio is for the compound to paraformaldehyde ** = 3-(2-hydroxy)propyl-5-methyloxazolidine Example 9 The physical characteri~tics of the paint containing the oxazolidines were recorded. A 3 mil wet film drawdown using a Bird Applicator comparing the blank paint (no bactericide) versus the paint containing the biocide was made, and a visual determination of color differences was observed. The results are shown in Table IV.
TABLE IV
PAINT PHYSICAL CHARACTERISTICS OF OXAZOLIDINE DERIVATIVES AT
A LEVEL OF 0.2~ BIOCIDE ON TOTAL PAINT WEIGHT
VISCO-SITY(KU) p~ FILM APPEARA~CE
Blank 78 7.5 OK
l:l Molar Ratio* 75 7.5Slight Yellow 1:2 Molar Ratio 78 7.6Slight Yellow 1:3 Molar Ratio 78 7.6 OK
l:4 Molar Ratio 78 7.6 OK
l:5 Molar Ratio 78 7.5 OK
Oxazolidine** 76 7.5Slight Yellow _ * = In each instance the ratio is for the compound to paraformaldehyde ** = 3-(2-hydroxy)propyl-5-methyloxazolidine
EXAMPLES
The following example~ are illustrative and are set forth for the purpose of ~llustration only and are not to be construed a~ limiting the scope of the invention in any manner.
ExamPle 1 A mixture containing 46,6 9 lO.3~ m) of diiso-propanolamine, 10.8 9 (0.35 m) of 97% paraformaldehyde, and 100 cc of toulene was refluxed unt~l 6.3 cc of water wa~ collected in a Barrett tube. The toluene was distil-led off ~nd the re~aining product was distilled at 78C
at a pressure o~ 4O5 mm Hg. The resulting yield of 3-(2-hydroxy)propyl-5-methyloxazolidine starting material was 96.6~.
Elemental analysis of the product showed the following:
~ C % ~ % N ~ o Calculated 57.9 10.34 9.65 22.11 Found 58.12 10~83 9.62 ~1.43 ~22:1 U~6 Example 2 A mixture containing 29 g (0.2 m) of 3~2-_ hydroxy)-propyl-5-methyloxazolidine, 6.6 g (0.2 m) of 91%
paraformaldehyde, and 34.4 g of water was refluxed for one hour. The product obtained was an aqueous solution ` containing 50% water and 50% 3-(2-hydroxymethylene oxy)propyl-5-methyloxazolidine.
.~
Elemental analysis of the product showed the following:
,.~ .
% C % H % N% 0 Calculated 27.43 10.41 4.00 58.15 Found 27.2110.45 3.96 58.38 .,~
Example 3 I A mixture containing 29 g (0.2 m) of 3- f 2 hydroxy)propyl-5-methyloxazolidine, 13.2 g (0.4 m) of 91%
paraformaldehyde and 39.8 g of water was stirred at reflux for 30 minutes. The product obtained was an aqueous - 25 solution containing 50% water and 50% 3-(2-! [hydroxymethyloxymethyleneoxy])propyl-5-methyloxazolidine.
.
Elemental analysis of the product showed the following:
~ 30 -~ % C % H % N% 0 `~ Calculated 26.34 10.18 3.42 60.05 :' Found 26.16 10.21 3.39 60.24 ~2Z~1396 Example 4 A mixture containing 29 g (0.2 m) 3-(2 hydroxy-) propyl-5-methyloxazolidine, 18.5 g (0.6 m) of 97%
paraformaldehyde and 46.5 9 of water was stirred at reflux for one hour. The product obtained was an aqueous solution containing 50% water and 50% 3-[2-(hydroxymethyl-dioxymethyleneoxy)propyl3-5-methyloxazolidine.
Elemental analysis of the product showed the following: ~
% C _ % N % O
Calculated 25.53 10.02 2~98 61.46 Found 25.29 10.08 2.8361.80 ExamPle 5 A mixture containing 29 g (0.2 m) of 3-(2-hydro-xy)propyl-5-methyloxazolidine, 33 g (1.0 m) of 91%
paraformaldehyde and 56 g of water was stirred at reflux for one hour. The product obtained was an aqueous solution containing 50~ water and 50% 3-[2-(hydroxymethyl-tetra(oxymethylene)oxy)propyl]-5-methyloxazolidine.
Elemental analysis of the product showed the following:
-% C ~ H % N % O
_ _ _ Calculated 24.41 9.792.37 63.42 Found 24.49 9.72 2.3463.45 xample 6 A mixture containing 29 g (0.2m) of 3~(2-hydroxy)-" lZZ1096 propyl-5-methyloxazolidine, 26.4g (0.8 m) of 91~
paraformaldehyde and 50.6g of water was stirred at reflux for 45 minutes. The product obtained was an aqueous solution containing 50% water and 50~ 3-[2-(hydroxymethyl-tri(oxymethylene)oxy)propyl]-5-methyloxazolidine.
Elemental analysis of the product showed the following:
% C % H % N ~ O
Calculated 24.90 9.89 ~ 2.64 62.56 Found 24.94 9.86 2.6162.59 EXample 7 The Minimum Inhibitory Concentration Test against Pseudomonas Aeruginosa was carried out under the following conditions. The compounds of this invention were added to sterile nutrient broth at 0.l~ (1009 ppm) concentration. Each mixture was sequentially diluted with sterile broth to yield various levels of concentrations (500 ppm, 250 ppm, 125 ppm, 62 ppm).
One drop of an actively-growing 24-hour culture of the bacteria was added to each level and the mixture was incubated at 30C. After 24 hours of incubation, an aliquot from each tube was placed on nutrient agar and observed for growth. The results appear in Table 1.
Table I also indicates the results of a test run to show the concentration of test compound required to kill Pseudomonas Aeruginosa in 24 hours.
~L2%10gi~
TABLE I
_ological Data on Oxazolidine Derivatives Minimum Inhibitory Concentration against Pseudomonas _ Aeruginosa .~ LEYEL PPM
;~ - 101)0 500 250125 62 l:l Molar Ratio* ~ + +
10 1: 2 Molar Ratio -- -- -- + +
3 Molar Ratio -- -- -- ~ +
l:4 Molar Ratio -- -- -- -- +
l:5 Molar Ratio -- -- -- -- +
Oxazolidine** -- -- -- + +
Concentration Required to Kill Pseudomonas Aeruginosa in 24 Hrs.
r LEVEL PPM
l:l Molar Ratio* -- -- + + +
, l:2 Molar Ratio -- -- + + +
A~ 1 3 Molar Ratio -- -- -- +
l:4 Molar Ratio -- -- -- + +
25 1: 5 Molar Ratio -- -- + + +
Oxazolidine** -- -- -- + +
LEGEND: - = No Growth , + = Growth , ~
.~
* = In each instance the molar ratio is for the compound to paraformaldehyde ** = 3-(2-hydroxy)propyl-5-methyloxazolidine `~ 122i(~96 Example 8 The anti-bacterial properties of paints contain-ing the compounds of this invention were subsequently evaluated. A latex paint was prepared by following the order of addition listed in the paint formulations in Table II.
TABLE II
- PAINT FORMULA~TION
RAW MATERIAL LBS. PER 100 GALLONS
Water 200 Ethylene Glycol20 Cellulosic Thickener 3 Dispersant 6 Surfactant 2 Defoamer 20 Bactericide 2.3 Titanium Dioxide 250 Magnesium Silicate 150 Water 20 Coalescing Agent 8 25 Defoamer Vinyl Acrylic Emulsion 468 _ 1131.30 The bactericide was incorporated before the pigment (titanium dioxide, magnesium silicate) as part of the grind. After 20 minutes, the remaining paint ingre-dients were added at a slow speed. The paint prepared in this manner contained a 0.2~ concentration of oxazolidine or derivatives, as a 50% aqueous solution.
-` ~22~096 The paints containing the oxazolidines were inoculated with a mixed bacterial culture containing Escherichia Coli, Pseudomonas Aeruginosa, Proteu~ Mira-bilis, and Enterobacter Aero~enes. Biocidal performancewas evaluated at various time intervals by applying a streak of each paint to nutrient agar and recording the results on a growth/no growth basis. The results are listed on Table III.
~2Z1~3~
TABLE III
Anti-Bacterial Evaluation of Oxazolidine Derivatives at 0.2% Versus A Mixed Bacterial Culture of Pseudomonas Aeruginosa, Escherichia Coli, Proteus Mirabilis, Ent~robacter Aerogenes FIRST INOCULATION
~ J
- HRS HRS HRS HRS DAYS
Blank 4 4 4 4 4 ^`~ 10 1:1 Molar Ratio* 2 0 0 0 0 1:2 Molar Ratio 0 0 0 0 0 1:3 Molar Ratio 0 0 Q 0 0 ~ 1:4 Molar Ratio 0 0 0 0 0 ~t 1:5 Molar Ratio 0 0 0 0 0 i 15 Oxazolidine** 0 0 i SECOND INOCULATION
HRS HRS HRS HRS DAYS
20 Blank 3 4 4 4 4 1:1 Molar Ratio* 3 0 0 0 0 1:2 Molar Ratio 2 0 0 0 0 ~i 1:3 Molar Ratio 0 0 0 0 j 1:4 Molar Ratio 0 0 0 0 0 1:5 Molar Ratio 0 0 0 0 0 25 Oxazolidine** 4 4 4 4 4 - LEGEND: 0 = no microbial growth .1 = slight microbial growth `~2 = moderate microbial growth `~3 = heavy microbial growth `:~4 = very heavy microbial growth * = In each instance the molar ratio is for the compound to paraformaldehyde ** = 3-(2-hydroxy)propyl-5-methyloxazolidine Example 9 The physical characteri~tics of the paint containing the oxazolidines were recorded. A 3 mil wet film drawdown using a Bird Applicator comparing the blank paint (no bactericide) versus the paint containing the biocide was made, and a visual determination of color differences was observed. The results are shown in Table IV.
TABLE IV
PAINT PHYSICAL CHARACTERISTICS OF OXAZOLIDINE DERIVATIVES AT
A LEVEL OF 0.2~ BIOCIDE ON TOTAL PAINT WEIGHT
VISCO-SITY(KU) p~ FILM APPEARA~CE
Blank 78 7.5 OK
l:l Molar Ratio* 75 7.5Slight Yellow 1:2 Molar Ratio 78 7.6Slight Yellow 1:3 Molar Ratio 78 7.6 OK
l:4 Molar Ratio 78 7.6 OK
l:5 Molar Ratio 78 7.5 OK
Oxazolidine** 76 7.5Slight Yellow _ * = In each instance the ratio is for the compound to paraformaldehyde ** = 3-(2-hydroxy)propyl-5-methyloxazolidine
Claims (16)
1. A class of polyoxymethyleneoxazolidines having the structural formula:
wherein R is an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an aryl group of 6 to 10 carbon atoms; R1 represents a hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl group of 6 to 10 carbon atoms, or a substituted aryl group of 6 to 10 carbon atoms containing alkyl, halogen, alkoxy, or nitro substituents, R2 represents an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, or an aryl group of 6 to 10 carbon atoms; and n represents an integer in the range of 1 to 8.
wherein R is an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an aryl group of 6 to 10 carbon atoms; R1 represents a hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl group of 6 to 10 carbon atoms, or a substituted aryl group of 6 to 10 carbon atoms containing alkyl, halogen, alkoxy, or nitro substituents, R2 represents an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, or an aryl group of 6 to 10 carbon atoms; and n represents an integer in the range of 1 to 8.
2. A polyoxymethyleneoxazolidine according to claim 1 wherein R and R2 represent lower alkyl, and R1 represents hydrogen or lower alkyl.
3. The polyoxymethyleneoxazolidine according to claim 1 comprising 3-(2-hydroxymethyleneoxy)propyl-5-methyloxazolidine.
4. The polyoxymethyleneoxazolidine according to claim 1 comprising 3-[2-(hydroxymethyloxymethyleneoxy)-propyl]-5-methyloxazolidine.
5. The polyoxymethyleneoxazolidine according to claim 1 comprising 3-[2-(hydroxymethyl-di(oxymethylene)oxy)-propyl]-5-methyloxazolidine.
6. The polyoxymethyleneoxazolidine according to claim 1 comprising 3-[2-(hydroxymethyl-tri(oxymethylene)oxy)-propyl]-5-methyloxazolidine.
7. The polyoxymethyleneoxazolidine according to claim 1 comprising 3-[2-hydroxymethyl-tetra(oxymethylene)oxy-propyl]-5-methyloxazolidine.
8. A method for inhibiting bacterial growth in aqueous surface coating compositions which comprises treating the composition with a bactericidally effective amount of an hydroxypropyl oxazolidine having a structural formula:
wherein R is an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an aryl group of 6 to 10 carbon atoms; and R1 represents a hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl group of 6 to 10 carbon atoms, or a substituted aryl group of 6 to 10 carbon atoms containing alkyl, halogen, alkoxy, or nitro substituents.
wherein R is an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an aryl group of 6 to 10 carbon atoms; and R1 represents a hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl group of 6 to 10 carbon atoms, or a substituted aryl group of 6 to 10 carbon atoms containing alkyl, halogen, alkoxy, or nitro substituents.
9. A method for inhibiting bacterial growth in aqueous surface coating compositions which comprises treating the composition with a bactericidally effective amount of a polyoxymethyleneoxazolidine having a structural formula:
wherein R is an alkyl group of l to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an aryl group of 6 to 10 carbon atoms; R1 represents a hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl group of 6 to 10 carbon atoms, or a substituted aryl group of 6 to 10 carbon atoms containing alkyl, halogen, alkoxy, or nitro substituents; R2 represents an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, or an aryl group of 6 to 10 carbon atoms; and n represents an integer in the range of 1 to 8.
wherein R is an alkyl group of l to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms or an aryl group of 6 to 10 carbon atoms; R1 represents a hydrogen, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl group of 6 to 10 carbon atoms, or a substituted aryl group of 6 to 10 carbon atoms containing alkyl, halogen, alkoxy, or nitro substituents; R2 represents an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, or an aryl group of 6 to 10 carbon atoms; and n represents an integer in the range of 1 to 8.
10. The method according to claim 8 or 9, wherein the concentration of the bactericide in the aqueous surface coating composition is in the range of 0.005% to 1.0%.
11. The method according to claim 8, wherein the hydroxypropyl oxazolidine is 3-(2-hydroxy)propyl-5-methyloxazolidine.
12. The method according to claim 9, wherein the polyoxymethyleneoxazolidine is 3-(2-hydroxymethyleneoxy)propyl-5-methyloxazolidine.
13. The method according to claim 9, wherein the polyoxymethyleneoxazolidine is 3-[2-(hydroxy methyloxymethyleneoxy)]propyl-5-methyloxazolidine.
14. The method according to claim 9, wherein the polyoxymethyleneoxazolidine is 3-[2-(hydroxymethyl-di(oxymethylene)oxy]propyl-5-methyloxazolidine.
15. The method according to claim 9, wherein the polyoxymethyleneoxazolidine is 3-[2-(hydroxymethyl-tri(oxymethylene)oxy]propyl-5-methyloxazolidine.
16. The method according to claim 9, wherein the polyoxymethyleneoxazolidine is 3-[2-(hydroxymethyl-tetra(oxymethylene)oxy]propyl-5-methyloxazolidine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000449010A CA1221096A (en) | 1984-03-07 | 1984-03-07 | Biocidal dialkyl (3,5-substituted hydroxayalkyl oxazolidines and hydrocarbylene polyoxymethyleneoxazolidines) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000449010A CA1221096A (en) | 1984-03-07 | 1984-03-07 | Biocidal dialkyl (3,5-substituted hydroxayalkyl oxazolidines and hydrocarbylene polyoxymethyleneoxazolidines) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1221096A true CA1221096A (en) | 1987-04-28 |
Family
ID=4127352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000449010A Expired CA1221096A (en) | 1984-03-07 | 1984-03-07 | Biocidal dialkyl (3,5-substituted hydroxayalkyl oxazolidines and hydrocarbylene polyoxymethyleneoxazolidines) |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1221096A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237412A (en) * | 2015-09-14 | 2016-01-13 | 南京红宝丽醇胺化学有限公司 | N-methyl diisopropanolamine preparation method |
-
1984
- 1984-03-07 CA CA000449010A patent/CA1221096A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237412A (en) * | 2015-09-14 | 2016-01-13 | 南京红宝丽醇胺化学有限公司 | N-methyl diisopropanolamine preparation method |
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