DE2011052C3 - Diiodomethyl sulfones and their uses - Google Patents

Description

C ₁ - to

Alkylphenyl, di- (C ₁ - to C ₄ -; "
phenyl, dichlorophenyl, chloromethyl-phenyl or bromomethyl- ^X 5 phenyl or

η = 1 and R naphthyl- (2), p-methoxyphenyl, fluorophenyl, chlorophenyl, bromophenyl, C ₁ - to C ₄ -alkylphenyl, dimethylphenyl

are.

Use of the compounds according to Claim 1 as fungicidal and bactericidal active ingredients

is kept close to the neutral point, they yield ee'inge yields. The presence of the yellow Color serves as a simple indicator of the desired pH value. . .

After the end of the iodination, the Reak acidified tion mixture, e.g. with hydrochloric acid, in order to decarboxj the iodinated compound Heren.

According to a third method, the iodination is b ι η meth low temperature ¹⁰ with iodine in a weak on a 'chlorine acidic pH buffered reaction mixture carried out. The sulfonylacetic acid is dissolved in buffered acetic acid or in an aqueous solvent. Iodine is added Chlorine is preferably only added after all of the iodine is in solution and at least some of it has reacted. The iodized and decarboxylated product is precipitated and obtained by known methods.

The solution can be buffered by sodium hydroxide, ammonium hydroxide or basic Am monium phosphate. The solution of the iodine can be obtained by adding small amounts of a solution by means of, e.g., tetrahydrofuran or methanol

be lightened in coating compounds for agricultural and * 5,
industrial substrates. 1 »in general, during the iodination ·

Step temperatures above about 50 "C are avoided. The preferred temperature for preparation of the iodine compounds is between 12 and 15 ° C

30 towards the end of the reaction, a temperature of

20 to 25 ° C can be used.

The pH during iodination is about 2.5 to about 6, preferably 3 to 4.
From US-PS 24 84 489 is the as vegetable The Dijodmethylsulfone according to the invention can

Fungal compound 3,4-dichlorophenylsene for the protection of latex paints, vinyl tiles bk I d FRPS fil d flien vinyl foams textile mat

films or foils, vinyl foams, textile materials, Wood, filters, seeds from growing crops and plasticizers, e.g. from soybean oils, be used. They are particularly effective against cellulose-destroying fungi. According to the invention Compounds show towards numerous fungi, ζ. B. against Chaetomium globosum (ATCC 6025) Myrothecium verrucaria (ATCC 9095), Aspergillus versicolor (FA 483), Penicilhum citrmum (ATCC

tribromomethyl sulfone known. In FR-PS 14 73 116 are benzyl dichloromethyl sulfones and in Chem. Abstr. Vol. 54, 5519 Phenyl-iodomethylsulfone described.

The invention relates to the diiodomethyl sulfones defined in the claim.

The alkyl radicals in the formula can be straight-chain
or be branched. For η = 0, R are the
Meanings of 4-chloro- and 4-bromophenyl, 4-methoxyphenyl, 4-chloro-2-methylphenyl, 3,4-dichloro-45 10105), Fusarium oxysporum (ATCC 7601), alterphenyl and 2-methyl-4-tert.- butylphenyl preferred, naria Sp. and Rhizopus nigricans, a better effect than the well-known compound 3,4-dichlorophenyl-tribromomethyl-sulfone.

The amount and concentration of the compounds according to the invention used vary with the application. About 0.1 to about 2 percent by weight can be used in latex paints. The application on a textile material can be made from a solvent, from which after it

According to another method, a water evaporation of more than about Vio to about 1% of a reaction mixture is used, which deposit the corresponding compound according to the invention on the textile fibers ^ sulfonylacetic acid and about 3 moles of alkali metal hydroxide. If Verbinenthält according to the invention, with slightly more than 2 moles of iodine monochloride fertilize introduced at about neutral to seeds and growing plants placed under semi 4O ⁰ C under stirring, resulting in a coating of only 10 ppm pH in order. Preferably the pH is between ⁶ o excellent protection, although taller people 6 and 8 can apply up to about 5 g per liter in certain cases. Some of the less soluble compounds can be used. The effectiveness against the addition of a small amount of a solution over some microorganisms is less than by means of, e.g. B. tetrahydrofuran, make necessary. 1 ppm.

The less soluble reagents can also be emulsified be greeted. Known preparations are used,

The regulation of the pH of the reaction z. B. in solutions, emulsifiable concentrations, eemischs is essential and if the value non-wettable powders and dusts.

for υ = 0, R has the meanings 4-methoxyphenyl and 3,4-dimethylphenyl are preferred.

The compounds according to the invention can be prepared in various ways.

The corresponding sulfonylacetic acid can thus be mixed with sodium hypoiodite in an aqueous alkaline solution Iodate and then decarboxylate by adding hydrochloric acid.

20 1

Manufacturing examples

Example 1 p-Methoxyphenyl-diiodomethyl-sulfone

11.5 g (0.05 mol) of p-methoxyphenylsulfonylacetic acid are dissolved in 40 ml of 5% aqueous sodium hydroxide (0.05 mol). A solution of sodium hypoiodite was by adding 19.5 g (0.12 mol) Iodine monochloride made up to 200 ml of 5% sodium hydroxide solution. The hypoiodite became the Sulfonylacetic acid solution was added at room temperature, and when the addition was complete, the The mixture was stirred for a further 2 hours. It was then acidified with 22 ml of concentrated hydrochloric acid and Stirred a further 2 strokes at room temperature, during which carbon dioxide evolved. The mixture became alkaline with 50% sodium hydroxide solution

eight and stirred for 15 minutes. The yellow-brown product was filtered off, washed with water, triturated with sodium bisulfite solution to remove the color, filtered and washed again. The raw dried p-methoxyphenyldiiodomethyl sulfone weighed 18.5 g and was recrystallized from acetone-water; F. 132 to 134 ° C.

Aalysis:

Calculated for C ₈ H ₈ I ₂ O ₃ S:
C21.93 ° / o; Hl, 84%; I57.95 »/ o;

found:

C 21.85 »/ o; H2, 11%; 157.97%.

The following compounds were prepared in a corresponding manner:

Compound melting point ° C R-SO ₂ -CHJ ₂
R means:

4-tolyl 145 to 149

4-aminophenyl 180-182

4-chlorophenyl 132 to 134

4-tert-butylnphenyl 129 to 130

3-tolyl 104 to 105

2-tolyl 123 to 124

2-methyl-4-chlorophenyl 110 to 111

α-naphthyl 138 to 141

2-methyl-4-bromophenyl 114 to 115

3-methyl! -4-bromophenyl 136-139

2,4-dimethylphenyl 114 to 117

3,4-dichlorophenyl 144 to 146

2-methyl-4-tert-butylphenyl .. 127 to 128

2-isopropylphenyl 120 to 121

Cyclohexyl 126 to 128

052 J

R-CH ₂ -SO ₂ -CHJ ₂

R means:

4-chlorophenyl 138 to 141

4-methylphenyl 165 to 167

4-fluorophenyl 119 to 121

4-bromophenyl 149 to 151

4-methoxyphenyl 168 to 170

3-chlorophenyl 182 to 184

3-bromophenyl 192 to 194

2-naphthyl 172-174

3,4-dimethylphenyl 175 to 184

Example 2
^ao production of p-bromophenyl-diiodomethyl-sulfone

To a slurry cooled to 12 ° C 337 g (1.21 mol) of p-bromophenylsulfonylacetic acid in 1.1 kg of glacial acetic acid and 400 ml of water were added to 1.5 moles of aqueous ammonium hydroxide (about 15 percent by weight Solution) with stirring, the temperature of the mixture to below about Held 15 ° C. Cooling was continued until the clear solution reached a temperature of about 10 ° C 310 g (1.22 mol) of iodine and 50 ml of tetrahydrofuran were then added. It was stirred vigorously to suspend the iodine particles.

When the reaction mixture had cooled down again to about 12 ° C after the addition of iodine, became a second portion of 1.5 moles of dilute aqueous ammonium hydroxide at such rate admitted that the temperature did not exceed 14 ° C. After about 3 hours, the iodine particles were solved. During this period the pH of the reaction mixture was between 3 and 4, generally around 3.5.

Now 88 g (1.24 mol) of chlorine were added within 2 hours and until the dark brown color the reaction mixture had changed to a yellowish color, was added. The stirring was then continued for about an hour. The product started to precipitate by adding 10 g of anhydrous potassium carbonate in 25 ml of water was continued in 15 to 20 minutes. One gave

Add sodium bisulfite solution to the reaction mixture until it was practically colorless and turned yellow never reappeared.

It was then filtered at about 12 ° C., the product was washed with 300 ml of 20% acetic acid and dried at 45 ° C. in a vacuum oven. The yield was about 560 g (95 ⁰ O of theory); F. 132 to 133 ⁰ C.

Usage examples
Example 3

This example explains the use of compounds according to the invention in coating compositions for textiles that come into contact with the ground, e.g. when used for sandbags or tents will. The test was carried out in accordance with the US Federal Specifications, Textiles Testing, CCC-T-19Ib, method described.

20 Π 052

Frayed strips of cotton cloth that had been finished without sizing were used as test strips was used. The test compound was applied to the tissue from acetotube solution, whereby a 0.5% uptake by the tissue took place. 5 test strips were treated with each compound. These were buried in soil along with five untreated test strips. Located in the earth numerous microorganisms. The soil was kept at 30 ± 2 ° C.

After 12 days, the tensile strength of the strips was measured. The results obtained are in Table I listed. The untreated test tires had completely dissolved.

Table I.

Resistance of cotton fabric to
Decomposition by microorganisms

connection Medium
fracture
firm
speed Beib
hold
strength kg / cm "/O 4-tolyl-diiodomethyl-sulfone 51.4 73.0 4-chlorophenyl diiodomethyl sulfone 63.0 ■ 90.0 4-tert-butyl-phenyl-diiodo-
methyl sulfone 83.00 100 4-methoxyphenyl-diiodomethyl-
sulfone 55 78.0 2-methyl-4-chlorophenyl-diiodo-
inethyl sulfone 52 74.0 Untreated sample - the
Exposed earth 0 Untreated sample - no
4 earth exposed 70.2 4-aminophenyl-diiodomethyl-
fulfill 55.2 78.0 1,4-dimethylphenyl-diiodomethyl-
♦ sulfone 70.7 99.9 J ^ -Dichlorophenyl-diiodomethyl-
• sulfone 68.0 96.0 Cyclohexyl diiodomethyl sulfone 74.5 100 4-bromobenzyl diiodomethyl sulfone 67.0 94.4 4-methoxybenzyl-diiodomethyl-
lulfone 67.0 94.4 S, 4-dimethylbenzyl-diiodo-
ethyl sulfone 58.0 81.7 Untreated sample - the
.Exposed to earth 0 Untreated sample - no
exposed to the earth 71

sulfone, which is light-sensitive, is particularly favorable for this application because the compounds are all colorless while other compounds commonly used for this purpose, e.g. B. copper 8-hydroxyquinolinate, that is green will stain the fabric, which is often undesirable.

Example 4

This example illustrates the preparation and properties of latex paints according to the invention Connections included.

The preservation of exterior paints made from latex paints against the effects of microorganisms is of great importance especially in southern latitudes. In order for such an application to be suitable, the active ingredient must be non-toxic to humans and animals; it should preferably be be colorless and in any case not change color over time, and it must protect against leaching and be resistant to light decomposition. Appropriately, it has a temperature of about 66 to 71 ° C low volatility.

The following latex paint was produced:

kg

Water 136

Potassium tripolyphosphate

(Dispersant) 0.45

Octylphenoxypolyethoxyethanol

(Wetting agent) 1.8

Titanium dioxide (primer pigment) .. 91

Talc (extender) 68

Propylene glycol (wetting agent) ... 13.6

Hydroxyethyl cellulose (thickener and protective colloid) 1.8

Polyvinyl acetate dibutyl fumarate copolymer emulsion (carrier) 147

Polymerized sodium and potassium salts of alkylnaphthalenesulfonic acids (Dispersant) 0.9

Trimethylpentadiol monoisobutyrate

(Coalescing agent) 1.8

The compounds listed in Table I are, with the exception of 4-aminophenyldiiodomethyl-Zu the above paint preparation was 1 percent by weight of a compound according to the invention

dung admitted. Then two coats of each coating mass were made on a wooden panel from the south Yellow pine applied and this a direct weathering test in South Florida on test frames, which were set up at an angle of 45 ° and facing south. For comparison panels with paint without preservatives and with paint that 1% Phenyl mercury acetate coated. The plates were after 3 months and again after 6 months in terms of color change, retention of dirt, the presence of mold and of the general overall appearance. The results are shown in Table II.

Table II

Ajistrichsmassen - weathering test

connection 3 months dirt Mould General 6 months dirt Mould General Color back mine Color back mine modification attitude Look modification attitude Look little little Well little moderate pretty much 4-tolyl-diiodomethyl- ge ge Well sulfone bleaches little moderate pretty much bleaches little moderate bad 4-tert-butyl-phenyl- ge Well ge diiodomethyl sulfone bleaches little track very bleaches little track Well 4-bromophenyl-diiodo- ge Well ge methyl sulfone bleaches little no out bleaches little little very good 4-methoxyphenyl-di- ge draws ge iodomethyl sulfone bleaches little no out bleaches little little very good 2-methyl-4-chlorophenyl ge draws ge diiodomethyl sulfone bleaches little moderate bad bleaches little moderate pretty much a-naphthyl-diiodomethyl- ge ge Well sulfone bleaches little moderate bad bleaches little moderate pretty much S-MethyM-bromophenyl- ge ge Well diiodomethyl sulfone bleaches little track very bleaches little moderate Well 2,4-dimethylphenyl ge Well ge U diiodomethyl sulfone bleaches little little pretty much bleaches little moderate pretty much 2-methyl-4-tert-butyl ge Well ge Well phenyl diiodomethyl sulfone bleaches little track very bleaches little moderate pretty much 4-chlorobenzyl-diiodo- ge Well ge Well methyl sulfone bleaches little moderate pretty much bleaches moderate moderate pretty much 2-isopropylphenyl ge Well ge Well diiodomethyl sulfone bleaches no no out bleaches little moderate very 4-chlorophenyl-diiodo- ge draws ge Well methyl sulfone bleaches _ few out very bleaches moderate moderate bad Comparison - without strength shapes bad moderate additive Discoloration exercise little moderate bad moderate moderate bad Comparison - with queck strength strength silver-containing additive Ver Ver coloring coloring

Key: color change - no change, bleached, minor discoloration, moderate discoloration, severe discoloration. Dirt retention - none, little, traces, moderate, excellent. Mold - none, little, traces, moderate, excellent.
General appearance - excellent, very good, good, fairly good, bad.

Example 5

This example illustrates the coating of seeds with compounds according to the invention.

A certain amount of the material intended for seed treatment was first distributed in this way evenly as possible on the inner surface of a glass jar. Then flaxseed became in that Glass vessel initially circulated by hand for 1 minute and mechanically for a further 5 minutes. The applied The amount of the compound according to the invention was from 10 to about 125 ppm.

1800 g of air-dry sand were mixed with 80 ml of tap water until the mixture was evenly moistened was and made a bed out of it on a mat. Two furrows were made at a distance from 2.5 cm. Twenty seeds about 6 mm deep were placed in each furrow. 2wipe the two Rows of the treated seeds were 10 kernels of barley, those with R. solani, one occurring in the soil Plant pathogens that were infected were planted about 6 mm deep. The rootstock with the bed was placed in a plastic bag and sealed until the seedlings opened. After rising the beds were cultivated to 20 ° C until the experiment was ended 7 to 10 days later. A sterile one Control trial and an untreated control trial were also carried out.

The sprouted seeds are shown in table ΙΠ (A) and the percentage survival rate (Ü) such « Percentage of seeds that had sprouted.

ίο

Table III

Coated Seeds - Germination and Survival Rate

Compound 10 ppm 20 ppm 45 ppm 90 to Sterile Untreated

ppm control delter

try control

attempt

A Ü A Ü A Ü AÜAÜAÜ

100 84 100 27 31

77 100 67 35

77 100 67 35

83 100 18 46

83 100 18 46

84 100 27 31 76 100 46 16

85 76 80 41 57

67 64 22 5

58 100 30 29

4-tolyl-diiodomethyl-sulfone 84 100 89 100 85 100 4-chlorophenyl-diiodo-
methyl sulfone 81 100 81 100 83 100 4-tert-butyl-phenyl-
diiodomethyl sulfone 78 100 86 100 86 100 4-bromophenyl-diiodo-
methyl sulfone 86 100 87 100 77 100 4-methoxyphenyl-diiodo-
methyl sulfone 83 100 85 100 83 100 2-methyl-4-chlorophenyl
diiodomethyl sulfone 86 100 93 100 86 100 a-naphthyl-diiodomethyl-
sulfone 80 100 76 95 81 100 2-methyl-4-bromophenyl-
diiodomethyl sulfone 3,4-dichlorophenyl-diiodo-
methyl sulfone 78 100 2-methyl-4-tert-butyl
phenyl-diiodomethylphenyl 48 53

Claims (1)

Patent claims:
1. Diiodomethyl sulfones of the formula R- (CH ₂ ) ,, -SO ₂ -CHJ ₂ , in the »= OundRCydohe ^ UNaphtfayK