IL42969A - Derivatives of 5-nitroquinoline,process for preparing them and compositions containing them - Google Patents

Description

NEW DERIVATIVES OF PROCESS FOR PREPARING THEM AND COMPOSITIONS CONTAINING THEM The present has as ts subject new derivatives lne of formula In which represents hydrogen or an al kyi radical containing from 1 to 6 carbon represents either an alkyi radical containing from to 6 carbon atoms differing from a methyl radical when represents a hydrogen or a lower alkoxy carbonyi radical 1n whi ch the al kyi radical contains from 1 to 6 carbon or an alkanoyl radi cal containing from 1 to 6 carbon or an thio radical in which the al kyi radical contains from 1 to 6 carbon or a phenyl thio radical or a cycloal kyl radical containing from 3 to 6 carbon or the tetrahydrofurfuryl radical In the compounds of formul a represents 1n particular a methyl ethyl propyl Isopropyl or radical represents 1n particular a methyl ethyl propyl radical a methoxycarbonyl propoxycarbonyl r acetyl phenyl cyclopenty or cyclohexyl Compounds I are endowed with interesting fungicidal or biocidal properties ch can be made evident in by tests on Alternaria Alternaria Botrytis Pusarium roseu Phytophtora Pseudomelia and Aerobacter These tests are described further on in the experimental Amongst compounds I one may mention in particular the compounds of Examples 1 to The invention has also as its subject a process for preparing compounds characterised in that one reacts in the presence of a basic agent with a carbamoyl chloride of in which and have The basic agent in the presence of which one carries out condensation of the carbamoyl chloride with quinoline is in particular triethylamine pyridine or hydride This condensation is carried out preferably in an organic solvent such as or The invention also comprises a variant of the process of the invention for preparing compounds I for which characterised in that one reacts with an isocyanate of of the isocyanate with quinoline is carried out preferably in the presence of a basic such as pyridine or triethylainine conveniently one operates in an organic solvent such as dimethylformamide or tetrahydrof The invention has also as its subject another variant of the process of the invention for preparing compounds I for which methyl and alkylthio or characterised in that one reacts quinoline in the presence of a basic agent with a halide of in which Rp represents an alkylthio radical or a phenylthio radical and Hal represents a halogen The basic agent in the presence of which one reacts e halide RpHal with quinoline may pyridine or The invention also relates to fungicidal or biocidal compositions containing as active material at least one compound of formula with one or more other pesticidal agents or with one or more products the growth of fungi or of These compositions may be in the form of solutions containing in in addition to the active anionic or inert powders such as a vehicle such as hydrocarbons or other a animal or vegetable For for fungicidal use one uses a wettable powder by of of Ekapersol product of sodium For use one for a wettable powder by of carbamoyl of Ekapersosl of Brecolane of ZeosH 39 and of Vercoryl The fungicidal compositions in from 10 to by of active material and the said blocidal compositions from 10 to by of active 1s described by PRATT and described 1n French Patent In French patent German Patent and Israeli Patents and there are described carbamic acid derivatives of quinoline which have a fungicidal and antiparasitic The present invention relates to fungicidal compositions of matter which are superior to those of the prior and which contain as active compounds of Formula herein The following Examples illustrate the Example One heats at 60 for eight hours a mixture of 38g of 500 ml of dimethyl of and 23g of dimethyl carbamoyl One pours the reaction mixture water and extracts with methylene One washes the organic phase an aqueous solution of sodium hydroxide and One dries the organic phase and one evaporates under reduced which provides 38g of in the form of a solid product melting at 154 Example sopropy carbamoyl ox One puts 38g of suspension of One drop by of One to return to ambient temperature and One with then with isopropyl ether and One thus obtains g of quinoline in the form of a solid product melting at The product can be in Analysis Calculated Found itro One puts 38 g of into suspension in 200 ml of tetrahydrofuran and 1 ml of One drop by 40 g of isocyanate and one heats at reflux for One evaporates under reduced washes the solid residue with 100 ml of isopropyl ether and which provides g of uinoline in the form of a solid product melting at 135 The product can be recristaiiised in Analsis 28 Calculated Found 1 Example 4 One agitates at for sixteen hours a mixture of 23 g of 300 ml of tetrahydrof ran and g of ethoxycarbonyl One filters the insoluble matter then one evaporates under reduced One dries the precipitate and obtains g of carbam oyloxy uinoline in the form of a solid product which melts at 116 It can be purified by dissolving in tetrahydrofuran and precipitating with isopropyl Analysis 4 Example uinoline mixes 62 g of and 36 g of triethylamine in ml of One drop by 55 g of chlori and 100 ml of One agitates for hours at ambient filters and evaporates under reduced pressure One dissolves the residue in methylene chloride and the organic phase with an aqueous solution of sodium hydroxide then with One dries the organic phase and one evaporates under reduced One recristallises the residue which provides g of a quinoIine in the form of a solid at 80 The product be recristallised in Analysis Calculated Found Example 6 tetrahydro urfurylcarb quinoline Operating as in Example starting with 20 g of oxyquinoline and 20 g of tetrahydrofurfuryl isocynnato and agitating at ambient temperature for one obtains g of quinoline in the form of a solid product which melts at The product obtained can be purified by dissolving in and precipitating with Calculated C H Found and leaving for seventeen hours at one obtains g of in the form of a solid product at The product can be recristallised in Analysis Calculated Found Example 8 quinoline To a solution of g of o in 600 3 of maintained at 17oC one adds progressively g of One whilst to and one drop by g of One continues heating for then one agitates for sixty hours at One pours the reaction mixture on to iced water and one extracts with methylene One washes the organic ith an aqueous solution of sodium hydroxide and with dries then one evaporates the One chromatographs the residue on silica gel by eluting with a chloride ethyl acetate mixture and obtains S of a yellow oil which cristallises in petroleum One obtains g of melting at Analysis 0 Calculated Example 9 l Operating as in Example but starting with 19 g of g of and of hyl cetyl carbamoyl chloride one after recristallising in 21 g of Calculated Found Example 10 Into a mixture of 45 g of diethyldisulphide and 4 ml of methylene chloride one drop by at C g of sulphuryl Then one at a solution of S to French Patent in 235 ml of One allows to retur to ordinary then one pours into a fixture of iced hydrochloric acid and methylene One washes the organic phase with one dries it and one evaporates it under reduced One dissolves the precipitate obtained in isopropyl ether and one precipitates with One recristallises the product in One thus obtains g of quinolin in the form of a product which melts at Analysis Calculated H S Found Example 11 oyloxy Operatin in Example but starting with 33 S diphenyldisulphide and g of sulphuryl one obtains 48 g of quinoline in the form of a product melting at This product can be purified in Analysis 12 Study of the fungicidal activity of quinoline of of and of The germination of spores of is studied in the presence of an aqueous suspension of the product to 1 of aqueous suspension of the product and 1 cur of suspension of the spores are The concentrations of the aqueous suspensions of the ranging products to be tested can from 75 of active The spore suspensions are up in the germination water and ajusted to spores The germination water is prepared in the following manner 10 g of 20 mg of potassium citrate and water in sufficient quantity to obtain a total weight of g are To g of this solution are added of the following solution 20 g of 6 g of pancreatic 1 g of yeast g of corn g of sodium 1 g of g of magnesium 10 mg of ferrous sulphate and water in sufficient quantity to obtain g Λ few of different suspensions are placed on Ranvier in chambers these strips are then put at for with s g of blue and g of acid The control is carried out by counting the germinated and The results are expressed in percentage Tests are carried in with ethylene The experimental results obtained are summarised in the following tables Alternaria solani Alternaria solani Alternaria oleracea of 0 20 10 active matter Compound C 100 80 70 100 0 solani Compounds C and are endowed with good fungicidal activity on Alte This activity is superior to that of The development of Botrytis spores on a liquid nutrient medium enriched by the product to be tested is car of liquid nutrient of suspension χ of the product to be tested and of spore suspension are The nutrient medium is prepared in the following manner g of oat g of sodium chloride and g of water are divided out into tubes and sterilised at The concentrations of the products to be tested range from 20 to The spore suspensions are made up in carrot juice and x adjusted to spores The control is carried out after keeping in an oven for 5 days at The fungistatic activity is noted as a function of the development of the fungus with reference to an u treated control The results are expressed in percentage Tests are carried in with The experimental results are summarised in the following tables Botrytis cinerea Conclusion Compounds C and F are endowed with good The development of a grown from spores in a medium containing agar with the addition of the compound to be studied is A suspension of the compound to be in le is into the nutrient containing agar at the rate of 5 of suspension per 45 cur of The mixture is divided out sterilely into two Petri After 4 cellulose lozenges enriched by a drop of spore are placed at four points in the Petri A suspension of roseum at the rate of 200 is The control is carried out at the end of seven clays by mea ring 8 colonies distributed in two The average diameter of the colonies serves as criterion with regard to a untreated The experimental results expressed in percentage are summarised in the following tables In the test compounds C and are endowed with good fungicidal activity respect to Fusarium Live Saint Pierre tomato leaves are treated and inoculated with drops of conidia Active natter concentrations of and of active are The tomato leaves are placed in Petri The treatments are carried out with a micro sprayer at the rate of per dish surface of 100 mm in To a spore suspension of Phytophora ns in sterile adjusted to conidia is Contamination is carried out at points per leaf and 5 leaves per concentration are After keeping for 5 at a reading is taken counting the spots of mildew which have appeared at the inoculation The experimental expressed percentage are summarised in the following tables of active matter 1 000 500 250 125 Compound 75 90 15 5 0 Conclusion In the test compounds C and are endowed with good fungicidal activity with respect to phtora Example Study of the biocidal activity of of auinoline and of Bacteriostatic activity Inhibiting the development of the bacteria on a liquid nutrient enriched by the experimental allows the bacteriostatic efficacy to be As nutrient a broth which is treated with an aqueous solution of the product to be studied The inoculum is prepared at the rate of 1 cm of bacterial strain 10 of There are 2 tests per The control is carried out after keeping for hours in an oven at It consists in percentage diminution 0f bacterial turbidity by comparison with a untreated in each concentration made After for hours at the percentage diminution of development is evaluated with reference to an untreated The experimental results obtained are the following tables Compound A Test on Pseudomona aeruginosa Bacteriostatic and bactericidal tests are carried out in manner similar to that used for Aerobacter The experimental results obtained are summarised in the following tables Compound A Compound D of active matter 50 10 5 Compound Study of activity on paper Inhibition of the growth of bacteria cultivated on a medium of paper pulp mixed with active principle shows the efficacy of this Paper in aqueous mixed with resin Contamination of the pulp is effected using a bacteria then it is incubated for twenty hours at A first count is then effected by counting the colonies which have The active principle to be tested is then introduced into three samples of the contaminated suspension at concentrations of and then it is put in the oven at From each of the three preceding samples are taken one four hours and seven hours after ing the active Thus nine Petri dishes containing an agar medium which is put in the oven at hours are Then the number of colonies which have appeared are By with tests in absence of the active the percentage of corrected The following table the expressed in percentage of corrected Compound A of active matter 200 100 50 0 0 H 0 7H 93 Conclusion The preceding studies allow the biocidal activity of compounds D and E to be brought to insufficientOCRQuality

Claims (1)

1. 42969/2 WHAT IS CLAIMED IS: 1 ) Derivatives of 5-n1troqu nol1ne of formula I: 1n which R, repress y rogen or an al kyl radical containing from 1 to 6 carbon atoms, R2 represents either an alkyl radical containing from 1 to 6 carbon atoms, R2 differing from a methyl radical when represents a hydrogen atom, or a lower al koxy-carbonyl radical 1n which the alkyl radical contains from 1 to 6 carbon atoms, or an al kanoyl radical containing from 1 to 6 carbon atoms, or an alkylthio radical 1n which the alkyl radical contains from 1 to 6 carbon atoms, or a phenyl thlo radical or a cycloalkyl radical containing from 3 to 6 carbon atoms, or the tetrahydrofurfuryl radical . 2) 5-n1tro 8-(n-butylcarbamoyloxy)qu1nol1ne. 3) 5-n1tro 8-(N-methyl N-acetyl carbamoyl oxy)quinoHne. 4) 5-n1tro 8-(carbethoxycarbamoyloxy)qu1nol 1ne. 5) 5-n1tro 8-(N-carbethoxy N-methyl carbamoyl o^y)qu1nol 1ne. 6) 5-n1tro 8-(N-methyl N-ethylth1ocarbamoyl oxy)qu1nol 1ne. 7) 5-nltro 8-(N-methyl N-phenyl th1ocarbamoylo y)qu1nol 1ne. 8) 5-n1tro 8- (tetrahydrofurfuryl carbamoyl oxy)qu1nol ine. 9) 5-nltro 8-(d1-n-butylcarbamoyloxy)qu1nol1ne. 10) 5-n1tro 8- (d1 -methyl carbamoyl oxy)qui no! ne. 11 ) A process for preparing compounds of formula I as defined 1n claim 1 , characterised In that one reacts 5-n1tro 8-hydroxyqu1nol 1ne, in the presence of a basic agent, with a carbamoyl chloride of formula: in which and R have tie mea i g , given in claim 1. 12) A variant of the process according o claim 11, for preparing compounds of formula I as defined in claim 1) in which R^ = H, characterised in that one reacts 5-F-i ro 8-hydroxyquinoline with an isocyanate of formula : in which Rp has the meaning given in claim 1. 13) A variant.. . of the process according to claim 11, for preparing compo\inds of formula I as defined in claim 1) in which ^ = methyl and Rp = alkylthio or phenylthio , characterised in that one reacts 5-nitro 8- (methylcarbam oyloxy ) quinoline,in the presence of a basic agent, with a halide of formula : R2-Hal in which p represents an alkylthio radical or a phenylthio radical and Kal represents a halogen atom.- 14) Fungicidal compositions containing as active matter at least one of the compounds of formula I as defined in claim 1. 15) Biocidal compositions containing as active matter at least one of the compounds of formula I as defined in claim

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