DE2163228A1 - Phenol derivatives - Google Patents

Description

PATENT LAWYERS

DR. O. DlTTMANN K. L. SCHIFF DR. A. ν. FONBR DIPL. ING. P. StRBIIL

MÖNCHEN BO MARIATiILFPLATZ 2 & 8

DA-4605

Des c -h friction to the patent application
of the company

PROGIL
77, Rue de Miromesnil Paris 8e, France

concerning

Phenol derivatives ■.

l'rioi-ität: 1p. January 1971, Mr. 7102261, France

Ijifc Irf-'ndung refers to novel phenol derivatives, more precisely on new chloro-nitro-methoxvphenols, and their application 8.1b jiiocide.

It is known that chlorophenols, especially pentachlorophenol, have verbose biocidal properties. Still one is always eager to find new products that are products that are known for superior activity on one or the other have several biological areas.

It has now been possible to discover new phenolic compounds which have proven themselves as agents for destroying or inhibiting the development of numerous animal or plant parasites and whose fungicidal activity is superior to that of known pheriol derivatives, in particular of pentachloroxyhenol. ; t. Jjarau ;. it follows that the invention: according to chlorine n j. tro-j.-iothoxy phenols at an activity similar to that of Pen ta- _ ^ _

209839/1206

chlorophenol have a lower toxicity. These Properties make the products according to the invention "special valuable, especially for protecting wood and other cellulose materials.

The invention relates to new phenol derivatives from Pornel

OH

Cl

(D

in the R ₁ and Ii _? always represent different radicals and mean a chlorine atom or a -KOp-G group.

The products according to the invention are crystalline solids that are generally soluble in common solvents. Their melting points have the following values:

2,4-dichloro-3-mcthoxy-6-nitrophenol: 102 ⁰ C; 2, o-dichloro-o-methoxy-4-nitrophenol: 128 ° C.

The phenol derivatives according to the invention can be prepared by processes which make use of the general principles, see below, Horstteile of Chlox'phenolen. For example, they can be prepared from 1-uritro-2,3,5-tetrachlorobeniol by alkaline stranding in methanol and subsequent acidification of the alkali dichloromethoxynitrophenolates obtained, whereby the free phenol derivatives are obtained. If necessary, extraction ^ - and Um ^ riütallit-a i-ioiis voi .;. ^:: .i: ge. performed to each of the Isoinoreti dor erfindun ^ o ^ euiäßcn to isolate and purify compounds.

209839/1206

21B3228

The formation reactions of the products according to the invention can schematize!] can be represented as follows (in these formulas Me means an alkali metal ion):

Cl

O,

OMe

+ 6 HeOH + 2 CH ₅ OH

+ 4 MeCl

NO

+ Me

H-

OMe

According to one embodiment of the process according to the invention for producing the phenol derivatives, a methanolic solution of tetrachloronitrobenzene is refluxed and an aqueous solution of an alkali metal hydroxide is added to this solution. The reactants can be used in stoichiometric amounts; however, it is preferred to use an excess of the alkali hydroxide of "for example 10-50 ΗοΓ / ό, based on chloronitrobenzene. It is also advantageous to use a large excess of methanol, so that methanol" is used both as a reactant and as a solvent for the Reaction medium is used. After heating for a period of time sufficient for maximum conversion of the starting materials, the reaction mixture is cooled and filtered. The piltrate can be returned to the reaction. The solid product obtained is extracted with hot steam. The extract becomes with a strong iriora'JKüurc,, jYc Obloj-wasnors ¹ : tof f ^ Mirri :, uchwcf üloäure, Viioi · -

2u9839 / 120b

phosphoric acid. In this way a precipitate is obtained the predominant part is 2,4-dichloro-3-niethoxy-6-nitrophenol contains, by recrystallization from a suitable solvent, for example an aliphatic Alcohol, such as methanol, can be isolated. The residue obtained in the said extraction is also with a strong acid acidified, whereby a precipitate is obtained, which contains as the main product 2,6-dichloro-3-methoxy-4-nitrophenol. This compound can be recrystallized from a suitable

"th solvent, especially an aliphatic carboxylic acid, such as acetic acid, can be isolated in practically pure form. To another embodiment which is particularly important when the compounds according to the invention are used for pest control are determined, the connections are not isolated Form, but obtained in the form of a mixture as a crude product after acidification. This pail is used after filtering of the reaction mixture originating from the saponification, the solid fraction is suspended in water, acidified and the resulting Separated precipitate and then dried. In general it contains apart from the two desired isomers, a small amount of An Leu Io of trichloronitride phenols as by-products. The presence of this Impurities, however, interfere with the use of the refinement according to the invention Connections for the stated purposes are not.

However, the phenol derivatives of the formula I according to the invention can can also be produced by any other method.

As mentioned, the pheriolite derivatives according to the invention have valuable ones Properties as a parasiticide. You have special

209839/1206

_ 5 -

effective in destroying or inhibiting the growth of algae, Bacteria, to fight termites, nematodes, mollusks as well for protection against various water parasites such as bruozoarians, crustaceans and the like. Shown.

However, their activity is most pronounced in the Fungicide. This applies in particular to the 2,4-dichloro-isoicere. the The dose of this compound required to completely inhibit the development of fungi is much less than when using other known fungicides, in particular Pentachlorophenol.

The activity of these compounds makes them useful for numerous uses suitable. They can generally be used in all places and in or on all materials that are infected by the aforementioned parasites or are at risk of being infected. By way of illustration it can be said that they are particularly suitable for the treatment of water, for example of circulated industrial water, for combating aquatic parasites that usually cover structures that are submerged in water, for protecting a wide variety of types Materials "such as petroleum fractions, resins and elastomers, varnishes, paints, coatings, plants, Earth and especially for protecting cellulosic materials such as textile fibers and fabrics and especially wood in the form of Chips, agglomerates, boards, parmoles and the like.

The compounds according to the invention can be used as biocidal agents in the form of one or the other of the isomers, in their form Mixtures or in i'orm dos from the production of the raw product " al :; iiolcijo ;;, since υ a predominant part of this chlorine

209839/1206 BAD OBtGJNAL

contains phenolic compounds, apply as already described. In addition, these compounds can be used as such or in the form of customary preparations, depending on the intended use Intended use, use. For example, you can as such are incorporated into the materials to be treated after simple grinding, if these are liquid or viscous products, Coating compounds or molding compounds, such as resins and elastomers, represent. They can also be in the form of agglomerated solids

^ or dispersed in inert carriers, such as kaolin, are used. They can also be used as aqueous emulsions or suspensions, organic solutions, aqueous-organic solutions, which make it possible to protect the substance and in particular wood by spraying, sprinkling and dipping protection. The organic solvents which can be used are, for example Hydrocarbons, especially aromatic hydrocarbons such as toluene or xylene, petroleum cuts such as white oil, Alcohols, polyglycols or polyethers, such as condensation products of water or alcohols with alkylene oxides, ketones, such as acetone

* or methyl isobutyl ketone. These different types of liquid Preparations advantageously contain customary additives, such as penetration aids, fixatives or adhesives, polyvinyl alcohol, synthetic oils Resins, flocculants such as carboxymethyl cellulose, Alkali lignosulfonates, alginates, surface-active agents, in particular Condensation products of alkylene oxides and alcohols, vegetable oils and the like in structures that are immersed in water are intended to protect against water parasites, in addition to the active ingredients according to the invention, they contain classical substances Lieotandteile, in particular natural or synthetic before binders, like drying oils, rosin and deodorant derivatives ^ -7-

209839/1206

Polyvinyl compounds, polyacrylic compounds and the like, if necessary organic solvents, such as the solvents mentioned above, Whitening agents for polymers such as alkyl phthalates and pigments and other various known additives.

It should be emphasized that the active ingredients according to the invention also work together can be used with other, known biocides. If wood is to be protected by deep impregnation when treating wood, the method of injection can be used Liquid preparations described above can be selected from the classic vacuum-pressure methods, such as the method according to Rüping, Bethell, Tylor-Colquitt, Drilon etc.

The doses of the active ingredients to be used can vary within wide limits depending on the purpose of the protection sought and the type of preparation and application of these products. To give a general indication, however, it can be said that for the control of algae, bacteria, mollusks, proportions in the range between 1 and 100 parts by weight per 1 million parts by weight (ppm) of the substance to be protected generally lead to completely satisfactory results. Under the same conditions calculated doses in the range between 0.1 and 5 i "are effective against nematodes and termites. Experiments have shown that doses on the order of 10 to 100 parts by weight per million parts by weight in a culture medium inoculated with various fungi inhibited any development of these fungi. In practice, to protect wood, essentially against fungal attack, liquid formulations are used which contain 1 to 10 fi of the active ingredient? contain. The

-8-209839 / 1206 BAD OBlOiNAU

Wise proceeded that the phenol derivatives according to the invention are introduced into this in an amount of 0.5 to 8 kg / m of the wood. The coating compositions, such as paints or varnishes, preferably contain 1 "to 10 wt. ^ Of the chloro-nitromethoxyphenols according to the invention, based on their weight. If these preparations are intended for coating structures that are exposed to water parasites, it is advantageous to use Increase the proportion of the active ingredient, for example up to 40 fo, in order to strengthen the protection against drill worms (tarets) and / or to compensate for the losses caused by the leaching by water, in particular sea water When the substrate is deposited, it can vary between 200 and 400 g / m 2.

The subject of the invention is illustrated by the following examples made clear. Examples 1 and 2 relate to the preparation of compounds of the given formula, I, while the following Examples demonstrate the biocidal activity of these compounds.

example 1

In a flask equipped with a condenser and supply line were 785 g (3 mol) of 1-iUtro-2,3,4,5-tetrachlorobene ;; ol, dissolved in 5.2 l of methanol, heated to reflux. 480 g of sodium hydroxide solution (12 mol) dissolved in 320 g of v / water were then slowly added, the Boiling was maintained. The mixture was refluxed for a further -2 hours and the reaction mixture was then cooled and filtered. The Piltx'at was held in a second process which uses 3 »2 1 methanol; otherwise this was second

209839/1206 _BA D

Procedure carried out in the same way as the first.

The two filter cakes obtained were mixed, extracted with hot water, the extraction liquid separated and acidified with a 10% aqueous solution of hydrochloric acid (up to a χλΗ value of about 1). In this way, 800 g of a precipitate were obtained, the in Porin a yellow crystalline product with the melting point 93 ° C, was present. twice recrystallization from methanol was 625 g of a solid having · a melting point of 102 ⁰ C obtained by Eler.ientaranalyse and nuclear magnetic resonance as 2,4-dichloro -3-methox; y-6-nitrophenol has been identified.

The obtained in the extraction with hot water, in turn, solid residue was treated with a solution of Chlorwasserstoffsäurc, resulting in the formation of a 400 g at 110-115 ⁰ C melting IJri Eder shock track. Recrystallization from 50 / jiger acetic acid, 360 g of a solid having a Schraelzjjunkt of 128 ⁰ C obtained which was identified as 2,6-Dichljr-3-methoxy-4-riitrophenol.

The DünnnchichtchroLiatografie _y showed that the addition to the desired present PhenoJ.derivaten impurities in substantial 2,3; 4 ~ trichloro-6-nitrophenol and 2, 3> 6 ~ trichloro-4-nitro ph ο η ο 1 v / ar ο η.

Example 2

The experiment described above was repeated with the Modification that after the filtration the saponification

acri reaction mixes the filter cake in water from iiiLomporuivur suspondiort and with the help of a 10bigen -10-

209839/1206

- ίο -

aqueous solution of hydrochloric acid. About 1200 g of a precipitate was obtained which was approximately 90% by weight of the isomeric compounds of the formula I, while the remaining portion consists essentially of those mentioned Trichloraltrophenols existed.

Example 3

Solutions were prepared from each of the dichloromethoxynitrophenols according to the invention by first dissolving these compounds in a polyol known under the name "Polyglycol 400" (the product of the condensation of ethylene oxide on one mole of water, with an average molecular weight of 400) and then dissolving them The solution was diluted with water in such a way that concentrations of the active ingredients of 10, 50 and 100 respectively. Share ruf 1 million! Rush have been achieved. Thereafter, these solutions were inoculated with suspensions of the green alga Scenedesrnus crassuB, Nährextrakte added, and these mixtures at 25 ⁰ C for a period of 7 days 12 hours 24 hours

k exposed to artificial light. At the end of this period were made the following observations :,

the samples which contained 2,4-dichloro-3-methoxy-6 ~ nitrophenol, showed no detectable growth of algae at concentrations from 50 and 100 parts to 1 million parts during this Growth see as very little in comparison with an imbetiancif *! - ten comparative sample at a dose of 10 parts per million parts proved j

for the samples containing the second isomer, 50 Divide to 1 million parts a ccnr low growth and boi 100 parts to 1 million parts complete inhibition ...

209839/1206 BAD

watch out.

Example 4

Solutions of the active ingredients according to the invention in polyglycol 400 were in samples of nutrient broth mixed with the bacteriuin Staphylococcus aureus ". The addition took place in such that the concentration of the phenol derivatives "based on the medium, was 10, 50 or 100 parts per million parts". Kacli's 24 hour incubation at 37 ° C were as follows Observations made:

when using the 2,4-dichloroisomie took place in one dose from 10 parts to 1 million parts a very low bacterial growth "bum compared to an untreated comparison sample and no growth at a dose of 50 parts to 1 million Partj

when the 2,6-dichloro isomer was used, the result was reduced Growth in Doeen from 10 to 50 parts to 1 million parts and complete inhibition of dps growth at 100 parts to 1 Million parts.

A mixture of 2,4-dichloro-3-iaetl'Oxy-6-nitrophenol and a fluidizing agent based on Calciui.ilignosulfonat (which is known under the trade name "Agrinol") introduced. After cooling, the medium was inoculated with a colony of 5-day-old hernatodes of the species Cacnorhabditiii ο lagans.
When looking with a magnifying glass, the following findings -12-

209839/1206

BATH

- - 12 -

to be hit:

With a dose of the phenol derivative of 1.5 g per liter of the culture medium "ITematode mortality was about $ 50 after 48 Hours and $ 100 after 4 days;

"at a dose of 5 g / l there was almost complete mortality after 48 hours ^.:

Example 6

Each of the isomers of the present invention became after milling in the way in culture media based on malt and. Agar-agar introduced that samples with different concentrations of the active ingredient were obtained. For comparison purposes, samples of the same type as those according to the invention were prepared Products were replaced by pentachlorophenol. These media were then inoculated with certain strains of parasitic fungi. Observations, which are listed in Table 1 below, were carried out for about 5 days. It was the following Designation chosen:

- no growth
f ■

+ very slight growth

+ strong myeel or conidia growth

-13-2Ü9839 / 1206

Table 1

Mushroom stem Test pro
duct Dose of the active ingredient, related
on the medium (parts on
1 million parts) 50 100 A.
B.
C. 10 +
+ + Coriolus versicolor (L)
Source A.
• B
C. +
+
+ +
+ - Sterigmatocystis
nigra Y. Th. A.
B.
C. +
+
+ ± - Coniophora eerebella A.
B.
C. +
+ + - Chaetomium globοsum A.
B.
C. +
+ +
+ - Botrytis cinerea
(Sclerotinia Fuekelian
(äe By) Eck) +

χ = 2,4-dichloro-3-niethoxy-6-nitrophenol B s = 2,6-l) dichloro-5-methoxy-4-nitrophenol C = pentachlorophenol

These attempts make the compounds according to the invention effective clear, especially the superior effect of the 2,4-dichloro isomer, which reduces or inhibits the growth of fungi from a dose of 10 parts to 1 million parts.

209839/1206

Example 7.

Test specimens made from wood were

actin product from Example 2 impregnated in bulk in xylene. The impregnation method "consisted in that the test specimens in Solutions were immersed and successively for 20 min. A vacuum of a few millimeters Hg, then a pressure of 9 kg / -cm during 15-. Minutes. Make the draining were the specimens gradually dried over a period of 3 weeks, then they were brought into contact with fungal stems and in a humidity set at 24 ° C and S5 / S for 4 months Atmosphere kept. After this period, the growth of fungi was observed and the loss of mass assessed. These tests made it possible to determine the minimum dose at which no growth of parasitic fungi and no degradation of the More wood is done. These cans (indicated as a raw drug product) are listed in Table 2 below, based on the type of wood treated and the fungi tested.

Table 2

Type of wood Mushroom stem dose wood Pine sapwood Trametes trabea ^ _- 1 kg / m- ⁵ (Pers.) Bres. It beech Coriolus versicolor (L) "(P Source Il beech Chaetomium globosum # -2.5

For comparison purposes, tests were carried out under otherwise identical conditions carried out, but pentachlorophenol was used as a protective agent. In this case it was found that the

209839/1206

BUILDING

-Fighting the specified strain Coriolus versicolor required The minimum dose was approximately 10 kg / nr.

Example 8

A cellulose sample was soaked in a solution of the product from Example 2 in xylene in such a way that the active ingredient was present in an amount of 1 .fco, "based on the material, after which the solvent evaporated wu-r.de.

A termite colony of the species Retaculitermes lucifugus saintonensis was introduced into a glass tube containing moistened sand, above all , the tube was placed on the treated cellulose sample (this test corresponds to the regulations of the French standard Χ-41 · 5Ο5) · The percentage mortality of the · Animals was 86 fo after 24 hours and 97 $ after 5 days. In addition, the sample remained intact.

Example 9

The following formulation was produced in a ball mill: Product of Example 2 35 parts by weight

Iron oxide pigment 15 "

Polyvinyl acetate 2.5 "

Rosin * 14 »

Methyl isobuty! Ketone 13 »

Heavy weight 19 "

Octylptithalate 1.5 ^H

This coating composition was applied in an amount of 300 g / m 2 Sheet steel applied, which had previously been provided with a classic anti-corrosion layer. After immersion in the sea this sheet was practically not from water parasites infested. - _-j (; _

209839/1206

Claims (1)

Claims 1. Phenol derivatives of the formula in which R ₁ and Rp stand for chlorine atoms or nitro groups and represent different radicals. 2. A method for producing phenol derivatives according to claim 1, characterized in that 2,3j4,5-tetrachloro-1-nitrobenzene reacted in the presence of methanol with an aqueous solution of an alkali metal hydroxide and the obtained Pesticide is treated with a strong mineral acid ". 3. The method according to claim 2, characterized in that before the treatment with the acid, the solid product is extracted with hot water and that the liquid extract and the Extraction residue must be treated separately with a strong mineral acid. 4 · The method according to claim 3, characterized in that the the precipitate obtained by treating the liquid extract with acid is recrystallized from methanol. 5. The method according to claim 3 or 4, characterized in that which is obtained by treating the extraction residue with acid - The held precipitate is recrystallized from acetic acid. . Pesticides, characterized in that 209839/1206 they contain as active ingredient a Plaeiiolderivat according to claim 1 7 pesticides according to claim 6, characterized in that that they use Algicide, Saktericide, Molluskicide, Nematocide, Represent termiticides, fungicides or agents against water parasites. 8. Use of a pesticide according to claim or 7 to; Treating wood. 20983 9/1206