DE1768799A1 - New urethanes, processes for their manufacture and their uses - Google Patents

Description

CIBAAK TI ί NGESELLSCHAFT ₁ BAS EXi (SC HWEIZ)

Case 6223 / E

Germany

New urethanes, processes for their production and their uses.

of the present inventions are new Urethanes of the general formula

103883/1869

/ JO —GO — NH-R

wherein X is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or an alkoxy group, Y a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group or an R-NH-CO-O- radical, Z a hydrogen atom, a halogen atom, an alkyl or phenyl group and R is an alkyl, haloalkyl, alkenyl, cycloalkyl or an optionally substituted phenyl group. In the case where R represents a substituted phenyl group, a halogen atom, a haloalkyl group, an alkyl group or an alkoxy group are preferred substituents. Preferred urethanes conform to the formula

ττ L- Il ^v Il Ί

JO — NH-Ή

where X _{1 is} a hydrogen atom * a halogenated, a hydroxyl group or an alkyl group with 1 to. 4 carbon atoms,

¥ ,, a Massstoffatoia, a halogen atom, a hydroxyl group

or a K, -NiH-CO-O- radical, Z, a hydrogen atom, a Ha-I © genafcom> a phenyl group or an alkyl group with 1 to

109883/1869

4 carbon atoms and R, an alkyl group with 1 to 12 carbon atoms or a residue of the formula

where U and V are each a hydrogen atom, a halogen atom ^ one Represent trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms or an alk.oxy group.

Among the urethanes of the formula (2), compounds of the following formulas (3) to (5) claim a very special one Interest: ■

0-NH

-R ₁

OH O OH

\ J— 0 — CO-MR ₁

0 OH ■

U — 0 — CO — NH-R- '

10988 3/1869

In the formulas (3) to (5): X _p , Y_ and Zp each denote a hydrogen atom, a halogen atom or an alkyl group with 1 to 4 carbon atoms, Y., a hydrogen atom, a halogen atom. ,, or an alkyl group with 1 up to 4 carbon atoms, Z-, a hydrogen atom, a halogen atom, an alkyl group with 1 to 4 carbon atoms or an R ₁ -NH-CO-O- radical. R ₁ has the meaning given.

For example, a suitable urethane of the formula (5) corresponds to the formula

OH-- IiJ-O - CO-NH-

Among the urethanes of the formulas (3) to (.5) are in turn the urethanes of the formula

0OH
(7) - j

wherein U and V have the meaning given, very particularly preferred, urethanes _: the. are derived from the formula (7) correspond, for example, to the formulas

109883/18 69

O QH

U-O — CO — NH-

Eq

Il

A -— o-

OH

ι — GO — ί

O OH

I — GO — NH-C_J

O OH

y. ^ TJ-0 — GO — NH-

or

The urethanes of the formula (I) can be obtained by the processes customary for the production of urethanes.

The urethanes of the formula (I) are prepared by reaction of 1 mole of a compound of the formula

! 09883/1869

-G-

with 1 or »2 mol of a compound of the formula

R-B

her, where A and B mean residues, ■ which under condensation or addition, the bridge -O-C-NH- are able to form and

0 R, X, Y and Z have the meaning given.

One embodiment of this process consists in the fact that a phenol of the formula

with an isocyanate of the formula

R - NCO

converts, where R, X, Y and Z have the meaning given.

Depending on the starting materials and molar ratios, the reaction can take place, for example, according to the following scheme:

10 9 8 8 3/1869

R-NOO

i-CO-NH-R

R-HN-OC-O

HO O

OH

O-NH-R

Isocyanates are preferably reacted with the corresponding phenols. The phenols used as starting materials are either known or can be produced by methods known per se. The isocyanates used are, for example: 4-chloro-3 -trif luorme thy! phenyl isocyanate, 3,5-Dl- (trif luoromethyl) phenyl isocyanate, 3,4-di (chloro) phenyl isocyanate or phenyl isocyanate. ··

The reaction can be carried out in a solvent, e.g. Benzene, toluene, xylene, dioxane.

To accelerate and complete the reaction, it is advantageous to work in the presence of a tertiary Base such as triethylamine, 1,4-diazabicyclo- (2,2,2) -octane (= "triethylenediamine") etc.

In another embodiment of the method you can use a reactive derivative of carbonic acid, e.g. phosgene, with an amine of the formula (13) [B = NHp] and a

1 09883/186 9

Convert phenol of formula (l4) in any order, what can be shown in a formula:

+ R

(2-n)

COGl

(n-1)

η = 1 or 2

Urethane of formula (I) + HCl

The urethanes of the formula (I) show two effects at the same time, namely as stabilizers and above all as an agent against harmful microorganisms. The urethanes of the formula (l) can therefore be used as stabilizers for organic materials, e.g. as protective agents against ultraviolet radiation and oxidative influences, and at the same time in particular as Agents for combating harmful microorganisms on or in these organic materials can be used. The organic materials are thereby against the harmful effects of microorganisms and / or optionally Ultraviolet radiation, heat, air and oxygen protected that one the urethanes, the formula (I) the materials to be protected incorporated, applied to the surface or a filter layer upstream.

109883/1869

The means of combating harmful microorganisms, which contain urethanes of the formula (I) can be can be produced and used in a manner known per se. The breadth of the new means is particularly valuable antibacterial spectrum of activity, which in many compounds is both gram-positive and gram-negative Bacteria stretches. This is in application engineering Regarding the odorlessness and colorlessness of the urethanes of the formula (1) of particular value. The present invention thus also includes de.r.en. Use in pest control in general. The use is possible on a very broad basis, especially for protecting organic Substrates against attack by destructive and pathogenic (also phytopathogenic) microorganisms. The compounds of the formula (I) are accordingly suitable both as preservatives as well as a disinfectant for textiles and technical products of all kinds, in crop protection, in agriculture, in veterinary medicine and in the Cosmetics.

Among the technical products that can be preserved with the help of compounds of formula (I), the following are selected as examples: Textile auxiliaries or finishing agents, glues, binders, paints, Color * · or * printing pastes and similar preparations based on organic and inorganic dyes or * pigments, including those used as admixtures

109883/1869

Contain casein or other organic compounds. Wall and ceiling coatings, e.g. those that contain a protein Parb binders contain an additive the new compounds are protected from pest infestation. It can also be used for wood protection.

Furthermore, compounds of the formula (I) can be used for preserving and disinfecting fibers and textiles are used, whereby they can be applied to natural and artificial fibers and there a permanent Develop an effect against harmful (also pathogenic) organisms, e.g. fungi and bacteria. The addition can be before, at the same time as, or after treating these textiles with other substances, e.g. dye or printing pastes, Finishes, etc. take place.

Textiles treated in this way also have protection against the occurrence of sweat odor, such as that caused by Microorganisms is due to.

The compounds of the formula (I) can also be used as preservatives in the pulp and paper industry are used, among other things, to prevent the well-known slime formation caused by microorganisms in the for Apparatus used to make paper.

Furthermore, one arrives at the combination of compounds of the formula (I) with detergent or surface-active substances Substances for detergents and cleaning agents with excellent

109883/1869

antibacterial or antifungal, effect. The connections of formula (1) can be incorporated into soaps, for example, with soap-free, detergent or surface-active substances or can be combined with mixtures of soaps and soap-free detergent substances, in these combinations retain their full antimicrobial effectiveness remain. .- "■.:.

Cleaning agents containing compounds of the formula (I ^ can be used in industry and households as well as in the food industry. e.g. dairies. Breweries, slaughterhouses. .Also as part of preparations, which are used for cleaning or disinfection, the urethanes of the formula (1) can be used.

The effect can also be used in preserving and disinfecting finishes for plastics. When using plasticizers, it is advantageous to use the Compounds of the formula (I) dissolved in the plastic in the plasticizer to be added or dispersed. It is expedient to ensure that distribution in the plastic is as uniform as possible wear. The plastics with antimicrobial properties can be used for everyday objects of all kinds where a Effectiveness against a wide variety of germs, such as bacteria and mushrooms, if desired, can be used, e.g. in doormats, bathroom curtains, seating, step grids in swimming pools, wall coverings. By introducing

10 9 8 83/1869 "

-12- ¹⁷⁶⁸⁷

When using wax and polishing compounds, floor and furniture care products with a disinfectant effect are obtained.

The compounds of the formula (I) can open to protective;: - Textile materials applied in various ways e.g. by impregnating or spraying with solutions or suspensions containing the compounds mentioned contained as an active ingredient. The active ingredient content can here Depending on the application, between 1 and 30 g of active ingredient per liter of treatment liquid. Mostly will be

also textile materials both synthetic as. / of natural origin, with an active ingredient content of $ 0.1 to $ 3, is adequately protected against fungal and bacterial attack. The active ingredient can be used together with other textile auxiliaries such as finishing agents, anti-crease finishing, etc.

The use forms can correspond to the customary formulations of pesticides, for example agents that contain a compound of the formula (1), optionally also additives such as carriers, Contain solvents, thinners, dispersants, wetting agents or adhesives etc. as well as other pesticides.

Also with the help of the formula (I) described In principle, compounds can be stabilized and protected by all such organic materials that are The influence of ultraviolet rays in any form

109883 / .1869

damaged or destroyed »Such damage by exposure to the same cause, namely ultraviolet radiation, can be very different. Have an impact, for example Color change, change in mechanical properties ■ (Brittleness, liquidity, tensile strength, flexural strength, Abrasion resistance, elasticity, aging), initiation of undesired chemical reactions (decomposition of sensitive chemical substances, e.g. drugs., photoehemically in- · induced rearrangements, oxidation, etc. (for example of unsaturated: .. fatty acids containing oils), release of Burns and irritations (e.g. on human skin) etc. The application is of great importance of the compounds of the formula (I) for the protection of polycondensation products and polyaddition products against the effects of ultraviolet rays. In addition, a number of the compounds defined above in addition to said ultraviolet protective effect also have a stabilizing effect Exposure to oxygen and heat.

The organic materials to be protected can be in a wide variety of processing states and states of aggregation present ^ while their common feature is in one There is sensitivity to ultraviolet radiation.

If the protective agents of the formula (l) to be used for difc treatment of textiles, organic materials more natural or of synthetic origin, e.g. textile fabrics;

are to be used, the same can be used in every phase of the final processing, such as finishing, anti-crease finishing, Dyeing process, other finishing by means of fixing processes similar to dyeing processes on the substrate to be protected be applied.

The new stabilizers of the formula (I) to be used are preferably the materials to r or added or incorporated during their deformation »So may they are used, for example, in the production of films, foils, tapes or moldings of the molding compound or injection molding compound add or dissolve, disperse or otherwise finely distribute in the spinning mass before spinning. The means of protection can also use the starting substances, reaction mixtures or intermediate products for the production of fully or semi-synthetic Organic materials are added, so also before or during the chemical reaction, for example in the case of a polycondensation (i.e. also precondensation acts), in a polymerization (including prepolymers) or a polyaddition.

From the above, it goes without saying that in addition to protecting the substrate or the carrier substance, which contain the ultraviolet absorber, at the same time also achieve the protection of other accompanying substances of the substrate wir'di, for example, dyes, Äiitiöxydantiehi Desiftfektiönszusäätz, Antistatics and other Apgrotu ^ ehi Vfeicil-

i ö 9 ä s 3/1 § S i

makers and fillers.

Depending on the type of substance to be protected or stabilized, its sensitivity or the application-related form of protection and stabilization, the amount of stabilizer required can vary within wide limits, for example between about 0.01 and 10 percent by weight, based on The amount of substance to be protected. For most practical purposes, however, amounts of about 0.05 to 2% are sufficient.

The following procedure for protecting organic materials from exposure of ultraviolet radiation and heat consists in the fact that the compounds defined above are homogeneously in the organic materials to be protected distributed, superficially applied to these materials or the to be protected Materials are coated with a filter layer which contains the specified compounds.

Should the substance of the formula (I) to be used be applied superficially to the substrate to be protected, e.g. a Fiber material (fabric); are applied, this can be advantageous done in such a way that the substrate to be protected is introduced into a liquor which dissolves the UV absorber. or contains dispersed. Suitable solvents can e.g. methanol, ethanol, acetone, ethyl acetate, methyl ethyl ketone, Be cyclohexanol or especially water. The to be treated

1 0 9 8 8 3 // ISSrn 8 3 fc 0 «

The substrate is left in the liquor for a certain period of time, similar to the dyeing process - usually 10 minutes to 2K hours at 10 to 120 ° C, which can be moved if necessary. The material is then rinsed, optionally washed and dried.

The parts and percentages given in the examples below are weight units.

109883/1869

example 1

10.7 parts of 2,4-dihydroxy-benzophenone are in ISO parts of benzene dissolved at 70 ° C. After adding 0.2 part 1,4-diazabicyclo-E2,2,2] -oGtan is omitted Stirring at 60 ° C. 11.1 parts of 4-chloro-5-trifluoromethyl-phenyl add isocyanate dropwise over the course of 20 minutes. The mixture is stirred for a further 3 hours at the same temperature and then cooled 1-5 ° C and only refrains from the colorless reaction product.

After recrystallizing once from toluene-hexane, 18 parts of the urethane of the formula (8) are obtained. Melting point l62 to 163 ° C.

The urethanes of the formulas (6)> (9) to (11) and (ΐβ) to (38) produced, their Melting points are listed on Table I.

Legend to Table I:

Column I.
Column II
Column III

Column IV

= Formula number

) in the formula

_ TD

= Melting point in ° C

CO-EH-R

109883/1869

Table I.

II

III

IV

CF,

162-163 145-146

10

CP

186-187

11

Cl

188-189

16

c _? - σι

191-192

17 194-195

18th

195 - 196

19th

I.
Cl

159-160

20th

I.
CF,

163-164

109883/1869

II III

21

Oil

Cl

180-181

22nd

Cl

CF,

104-105

^ 3 CH,

"σι

143-144

H CO

CH.

Cl

173-174

-CH.

107-108

63-64

27 83-84

28 -CH ₂ -CH = CH ₂

78-79

29

HCO

189-190

30th

HCO

Cl

-Cl

192-193

109883/1869

II

III

IV

31

H "C0 3 CF. -σι

175 -

η σο

i » 3

205 -

σι -σι

209 -

OF.

OF.

197 -

CM) OF. -Oil

198 -

01

GF.

GF.

185 -

^Η 3?

OF.

OF.

163 -

OH

σι-

-MH-O

σι -σι

184 -

FO

• ΝΗ-σ

CF.

CF.

199 -

1 09883/1 869

Determination of the minimum inhibitory concentration (MIC) against bacteria and fungi in the dilution test

The MIC (minimal inhibitory concentration) is determined according to a standard based on standards Examination that approximates absolute minimum inhibitory values of an active ingredient allowed.

With the active ingredients a 0.4 $ and a 0.12 # solution prepared in dimethyl sulfoxide. 0.25 ml each the solutions become 9 * 75 ml sterile Brain Heart Infusion Broth (bacteria) or wort solution (fungi) are given. the two rows obtained by continuous dilution to ten times each are combined and thereby in the following continuous dilution series transferred;

100, 30, 10, 3, 1 ppm active substance,

The solutions are made with the bacterium Staphylococcus aureug and the fungus Rhizopus nigricans, then inoculated is incubated in bacteria for 48 hours at 37 ° C (bacterial stasis) and in fungi for 72 hours at 30 ° C.

After the times mentioned, the minimum inhibition values (ppm) in Table II result.

10988 371869

Table II

Connection of
Formula No. Minimum Inhibitory Concentration (MIC) Rhiζοpus nigricans (8th)
(10)
(11) Staphylococcus aureus <100
> 100
<100 0.1
0.3
0.1

109883/1869

Example 3

A film of approximately 6θμ thickness is produced from a 10 ^ igen acetone acetyl cellulose solution which, calculated on acetyl cellulose, contains 2 % of the compound of the formula (9). After drying, the following values are obtained for the percentage of light transmission

Table III

wavelength
in πιμ light transmission in $> exposed
(lOO hour fadeometer) 280 to 340
350
360
370 unexposed 0
4th
15th
45 0
4th
15th
45

Similar results are obtained, for example, with the compounds of the formulas (8), (10), (11) or others in the description contain said compounds according to the invention, provided that these compounds are dissolved in the acetyl cellulose.

109883/186 9

Example 4

χ ppm of the compounds of the formula (1) are added to the still liquid brain in a suitable formulation Heart Infusion Agar (BHIA) was added. This liquid mixture is applied to a basic agar layer (BHIA) without active ingredients, which was previously set at an angle to solidify, poured and allowed to solidify.

The germs to be tested are used for inoculation Pasteur pipette applied linearly perpendicular to the gradient.

After incubating for 24 hours at 37 ° C, the The length of the germs grown on the vaccination line was measured and expressed in ppm active ingredient. The following results were obtained according to this test method:

Table IV

Test organism Minimal Inhibition concentration (8th.) (10) the formula (ppm) 0.4 0.2 (11) link 2 30th 2 Streptococcus mitis 25th 25th 4th (6) Trichophyton interdigi
tale 3 5 Triciiophyton menta-
grophytes 2 2

109883/1869

Example 5

Samples of 100 g Baumwo11 cretonne are included a 0, l $ igen isopropanol or dioxane solution of the compounds of formula (l) impregnated at 20 ° C on the poulard and ' then squeezed with a 100 ^ igen PIottenaufnähme.

Contain tissues dried at 30 to 40 ° C 0 * 1 $ active ingredient, based on its own weight.

To test the effect against bacteria, rounds ^- with a diameter of 10 mm of the impregnated tissue are not watered and, after watering for 24 hours at 29 ° C, are placed on Brain Heart Infusion Agar plates, which are pre-inoculated with Staphylococcus aureus. The plates are then incubated at yj ° G for 24 hours.

On the one hand, the inhibition zone (HZ in mm) around the discs and on the other hand, what is microscopically detectable is assessed. Growth (W in %) under or on the tissue.

Table V

Connection no. not watered 'W in fo watered ¥ in $ 8th UZ in mn}. 0 HZ in mm 0 10 1 0 1 · * 0 11 Q 0 0 0 1 1

109883/186 9

Claims (4)

P at e nt ans check 1. Urethanes of the general formula ■ KH — R wherein X is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or an alkoxy group, Y a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group or an R-NH-CO-O- radical, Z is a hydrogen atom, a halogen atom, an alkyl or Pheny! Group, and R is an alkyl, haloalkyl, alkenyl, Cycloalkyl or an optionally substituted phenyl group, 2, urethanes of the formula 0 OH I / -0-00-NH-R wherein X _{1 is} a hydrogen atom, a halogen atom, a hydroxyl group or an alkyl group with 1 to 4 carbon atoms, Y, a hydrogen atom, a halogen atom, a hydroxyl group or an R ₁ ^ -NH-CO-O- radical, Z-, a hydrogen atom, a hat 109883/1 869 halogen atom, a pheny group or an alkyl group with 1 to 4 carbon atoms and R, an alkyl group with 1 to 12 carbon atoms or a radical of the formula wherein U and V each represent a hydrogen atom, a halogen atom, a Trifluoromethyl group, an alkyl group containing 1 to 4 carbon atoms or represent an alkoxy group. 3. Urethanes of the formula 00-KH- wherein X _pJ, Y _p , and Z _p each represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms and R- has the meaning given in claim 2. 4. Urethanes of the formula OH CO — HE — R - wherein Y, a hydrogen atom, a halogen atom or an alkyl group with! up to 4 carbon atoms, 'Zk- a water 1 Q 9 8 8 3/18 6 9 substance atom, a halogen atom, an alkyl group with 1 to Carbon atoms or an R, -NH-CO-O- radical and in which R has the meaning given in claim 2. 5 * urethanes of the formula OH D-CO-MH-R "1 wherein R has the meaning given in claim 2. 6. Urethanes of the formula OH IIJ 0 — CO — NH- wherein U and V have the meaning given in claim 2. The urethane of the formula ■ CO — NH 109883/1869 Ji768799 The urethane of the formula 0 OH The urethane of the formula OP, O OH Q- * The urethane of the formula 0 — NH— <Q— rOl Oil 109883/1869 ORIGINAL IrKBFECTED