AT395363B - Process for controlling phytopathogenic fungi - Google Patents

Abstract

The invention relates to a process for controlling phytopathogenic fungi, characterized in that a fungicidally effective amount of a compound of the formula I in which Y represents CH or N, R1 represents C1- 5alkyl or C3-5cycloalkyl, R2 represents H or C1-5alkyl, R1 and R2 can be linked to each other forming a C3- 7cycloalkyl radical, R5 represents halogen and R6 represents H or halogen, and R7 represents hydrogen, C1- 5alkyl, C3-5alkenyl, benzyl or acetyl, in free form or in an agriculturally acceptable acid addition salt form, alkoxide form or metal complex form, is applied to the environment of these fungi. <IMAGE>

Description

10th

AT 395 363 B

The invention relates to a method for combating phytopathogenic fungi.

The GB-A-2064520o fenbarta-phenyl-a- (C3_gcycloalkylOi_3alkyl) -lH-I12,4-triazole-l-ethanol with anti-fungal activity. According to this patent application, the (cycloalkylakyl) meanings are preferably C3_gcyclo-alkylmethyl; specific examples are given for the α-cyclohexylmethyl and a-cyclopentylmethyl meanings.

It has now been found that a-aryl-a- (cyclopropylmethyl) -lH-azole-l-ethanols, in which the methyl group which links the cyclopropyl group to the ethano group is substituted or branched on the one adjacent to the C (OH) group Carbon atom, possess surprisingly favorable fungicidal properties.

The invention therefore relates to a method for combating phytopathogenic fungi, characterized in that a fungicidally effective amount of a compound of the formula I 15 u CH, ° R7 \ 6PlR2 20 25 in which Y is CH or N, Rj for C ^ alkyl or C3_5cycloalkyl, R2 for H is added to their habitat or Cj.5alkyl, where Rj and R2 can be linked together to form a C3_7cycloalkyl radical, R5 is halogen and Rg is H or halogen, and R7 is hydrogen, Cj ^ alkyl, C3_5alkenyl, benzyl or acetyl, in free form or in a »- Acid addition salt, alcoholate or metal complex form applied for agriculture.

Any alkyl substituents of the compounds according to the invention advantageously contain 1 to 4, preferably 1 to 2, in particular 1 carbon atom. Any cycloalkyl groups of the compounds according to the invention are in particular 3 to 5-membered, preferably 3-membered. Any halogen substituents of the compounds according to the invention stand for F, CI, Br or I.

The compounds of the invention can by reaction a * compound of the formula Π 30 y ~ 1Kir Π

M 35

wherein M represents hydrogen, a metal or a trialkylsilyl group and Y has the meaning given above, with a compound of the formula III 40 CH, Ιν / Ο ^ -Δ &quot; Ä. m 45 in which R j, R2, R5 and Rg have the above meanings, or are obtained with a reactive derivative thereof and any subsequent etherification or esterification of the ethanol compounds thus obtained.

The compounds of the formula I in which R7 is hydrogen can be prepared analogously to methods known for the preparation of azole-1-ethanols from an azole and an oxirane.

Ester and ether derivatives of the ethanol compounds according to the invention can be obtained by known esterification processes or etherification processes, starting from the corresponding ethanols. The connections of the

Formula I are obtained in the form of the free base or as a salt (acid addition salt or alcoholate) or metal complex. The salts or metal complexes can be prepared from the corresponding compounds in free form and vice versa. The end product can be isolated and purified from the reaction mixture by methods known per se. 55 If the preparation of the starting compounds is not described, they are known or can be prepared analogously to known methods.

The compounds of formula I in free form or in an agricultural salt form -2-

AT 395 363 B (acid addition salt or alcoholate) or in the form of a metal complex (hereinafter referred to as “compounds according to the invention”) are suitable for combating phytopathogenic fungi. The good fungicidal activity goes u. a. from in vivo tests against Uromyces appendiculatus (bean rust) on runner beans as well as against other rust fungi (Hemileia, Puccinia) on coffee, wheat, pelargonium and snapdragon and against Erysiphecichoracearum on cucumber and against other powdery mildew fungi (E. graminis f. sp. tritici, E. graminis, E. graminis f. sp.hordei, Podosphaera leucotricha, Uncinula necator) on wheat, barley, apples and vine at test concentrations of 0.0008 to 0.05%. Other interesting effects are u. a. in vitro against Ustilage maydis with concentrations of 0.8 to 200 ppm, in vivo against Rhizoctonia solani with concentrations of 10 to 160 ppm, calculated on the volume of the substrate. Since the tests also show good plant tolerance and good systemic behavior, the compounds according to the invention are therefore suitable for the treatment of plant and seed, and for the treatment of the soil for the purpose of combating phytopathogenic fungi, for example for combating Basidiomycetes, Ascomycetes, Deuteromycetes, in particular of Basidiomycetes of the order Uredinales (rust fungi), such as Puccinia spp, Hemileia ssp, Uromyces spp; from Ascomycetes of the order Erysiphales (powdery mildew), such as Erysiphe spp, Podosphaera spp and Uncinula spp., and of the order Pleosporales, such as Venturia spp, as well as from Phoma, Rhizoctonia, Helminthosporium, Pyricularia, Pellicularia (= Corticiumis) and Thielaviops spp.

The application amount depends on various factors; Such factors are, for example, the type of compound according to the invention, the subject of the treatment (plant, soil, seeds), the type of treatment (watering, spraying, spraying, dusting, dressing), the purpose of the treatment (prophylactic or therapeutic), the type of treatment * fungi to be treated and the application time.

In general, satisfactory results are obtained when a compound according to the invention is used in the case of a plant or soil treatment in an amount of about 0.0005 to 2, advantageously of about 0.01 to 1 kg / hectare; e.g. B. 0.04 to 0.125 kg of active ingredient / ha in crops such as cereals, or concentrations of 1 to 5 g of active ingredient / hl in crops such as fruit, vines and vegetables (with an application volume of 300 to 10001 / ha, depending on the size or leaf volume the cultures, which corresponds to an application amount of about 10 to 50 g of active ingredient / ha).

The treatment can be repeated if desired, e.g. B. in an 8 to 30 day interval. If the compound according to the invention is used in a seed treatment, satisfactory results are generally obtained if the compound is used in an amount of approximately 0.05 to 0.5, advantageously approximately 0.1 to 03 g / kg of seeds. The term "soil" includes any wax medium, i. H. Soil type, whether natural or artificial.

The compounds according to the invention can be used in a large number of crop plants, for example in soya, coffee, ornamental plants (including geranium, rose), vegetables (including pea, cucumber, celery, tomato and bean plants), sugar beet, sugar cane, cotton, flax, corn , Grapevine, pome and stone fruits (apples, pears, plums), and are particularly suitable for use with cereals (e.g. wheat, oats, barley, rice), in particular with wheat and apples.

Compounds according to the invention which are particularly suitable for the use according to the invention are compounds of the formula I which have one or more of the following structural elements: Y is N, R j is CH3, R2 is H or CH3.

The invention also encompasses fungicidal compositions comprising, as a fungicide, a compound according to the invention in free form or in an agriculturally acceptable salt form or as a metal complex and an inert agricultural diluent. They are made using known methods, e.g. B. by mixing a compound according to the invention with a diluent and optionally additional auxiliaries, such as surface-active substances.

The term diluent means liquid or solid materials which are acceptable in agriculture and are suitable for bringing the active substance into a form which is easier or easier to apply, or for diluting it to a useful or desired degree of efficiency. Examples of such diluents are talc, kaolin, diatomaceous earth, xylene or water. In particular, formulations which are used in the form of a spray, e.g. B. water-dispersible concentrates or wettable powders may contain surface-active compounds such as wetting or dispersing agents, e.g. B. the condensation product of formaldehyde with naphthalene sulfonate, an alkylaryl sulfonate, a lignin sulfonate, a fatty alkyl sulfate, an ethoxylated alkylphenol or an ethoxylated fatty alcohol.

In general, the formulations contain from 0.01 to 90 percent by weight of active substance, from 0 to 20 percent by weight of surface-active substances which are acceptable to agriculture and from 10 to 99.99% of diluent. Concentrated forms of formulations, e.g. B. Emulsion concentrates generally contain between about 2 and 90, most often between about 5 and 70 percent by weight of active ingredient. Application forms of such compositions generally contain between 0.00005 to 10 percent by weight of a -3-

AT395 363 B compound according to the invention as active ingredient. Typical spray suspensions can contain, for example, 0.0005 to 0.05, advantageously 0.001 to 0.02 percent by weight of active ingredient.

In addition to the usual diluents and surface-active substances, the formulations can contain other auxiliaries for special purposes, e.g. B. stabilizers, deactivators (for solid formulations on supports with an active surface), auxiliaries to improve the adhesion to plants, corrosion inhibitors, antifoams and dyes. In addition, other fungicides with similar or complementary fungicidal activity, e.g. B. sulfur, chlorothalonil, dithiocarbamates such as Mancozeb, Maneb, Zineb, Propineb, trichloromethanesulfenylphthalimide and analogues thereof, such as Captan, Captafol and Folpet, benzimidazoles such as benomyl, or other beneficial active ingredients, e.g. B. Insecticides, formulations are added.

Examples of fungicidal formulations which can be used in agriculture are described below: al wettable powder formulation 10 parts of a compound according to the invention are mixed with 4 parts of synthetic, fine silica, 3 parts of sodium lauryl sulfate, 7 parts of sodium lignin sulfate and 66 parts of finely divided kaolinite and 10 parts of diatomaceous earth milled long until the average particle size is below 5 microns. The spray liquid obtained can be used as a spray for the foliage and also for watering the roots. b) Granule formulation

0.5 part by weight of a binder (a nonionic surfactant) is sprayed onto 94.5 parts by weight of quartz sand in a drum mixer and the whole is mixed vigorously. 5 parts by weight of a compound according to the invention are then added and mixed vigorously to obtain a granule formulation with a particle range of 0.3 to 0.7 mm. The granules can e.g. B. by mixing with the soil in which the plants to be treated are grown, applied. cl emulsion concentrate 10 parts by weight of a compound according to the invention are mixed with 10 parts by weight of an emulsifier and 80 parts by weight of isopropanol. This concentrate is diluted with water to the desired concentration. D) Seed coating or seed treatment 45 parts by weight of a compound according to the invention are mixed with 1.5 parts of diamylphenol decaglycol ether, 2 parts of spindle oil, 51 parts of finely ground talc and 0.5 part of rhodamine B. The mixture is mixed ground in a contreplex mill at 10,000 rpm until the average particle size is less than 20 microns. The dry powder thus obtained has good adhesiveness and can be added to the seed, e.g. B. by mixing for 2 to 5 minutes in a slowly rotating kettle. In the following examples, which explain the invention in more detail but are not intended to restrict its scope in any way, all the temperatures are given in degrees Celsius. Rf values are on silica gel.

Example 1: 2- (4-chlorophenyl) -3-cyclopropyl-l- (lH-l, 2,4-triazol-l-yl) butan-2-ol (diastereomer genetically):

Stage 1: 7.6 g of l- (4-chloro-phenyl) -2-cyclopropylpropanone-l are dissolved in 120 ml of dry toluene at room temperature, 28.6 g of dodecyldimethylsulfonium methyl sulfate are added and the suspension is stirred for 15 minutes. Then it is mixed with 6.3 g of powdered KOH added and stirred at 35 ° for 18 hours After cooling, the reaction mixture is poured onto ice, a little dimethylformamide is added and the mixture is extracted with diethyl ether. The organic extracts are washed three times with water, then with saturated aqueous NaCl solution, dried over magnesium sulfate and evaporated in vacuo. The residue is an oil which, in addition to dodecylmethyl sulfide and dode-cen-1.25% 2- (4-chlorophenyl) - Contains 2- (l-cyclopropylethyl) oxirane.

Level 2:

The crude oxirane reaction product is added dropwise to a mixture of 4.2 g of 1,2,4-triazole and 15.4 g of K2CO3 in 80 ml of dry dimethylformamide, which is kept at 90 °, and the mixture is stirred at 90 ° for 2 hours Pouring the reaction mixture onto ice, extracting it with diethyl ether, washing the organic extracts with water and saturated aqueous NaCl solution, drying over MgSC> 4 and removing the solvent in vacuo. After chromatography on silica gel, the title compound is obtained as a colorless, -4-

AT 395 363 B thick viscous syrup (mixture of diastereomers) which slowly crystallizes on standing. The product is obtained in the form of colorless crystals by recrystallization from hexane / dichloromethane. Mp: 100-101 °. Rf values in a thin layer chromatogram (silica gel plate; mobile phase ethyl acetate): 5 diastereomers A: Rf value 0.30

Diastereomer B; Rf value 0.38

The mixture of isomers is separated into the pure 10 diastereomers by repeated chromatography on silica gel with diethyl ether / acetone (99/1) and diethyl ether / ethyl acetate (99/1 to 90/10) and crystallization from hexane / dichloromethane:

Example 1A:

Diastereomer A: mp: 109-110 ° 15 Example 1B:

Diasteromer B: mp: 123-127 °

Example IC;

A solution of 2.9 g of 2- (4-chlorophenyl) -3- is added to a mixture of 2 g of p-toluenesulfonic acid monohydrate in SO ml of toluene, which has been concentrated to a volume of S ml of 20, at room temperature. Cyclopropyl-l- (lH-l, 2,4-triazol-l-yl) butan-2-ol (mixture of diastereomers) was added dropwise in 35 ml of absolute toluene and left to stand for 15 hours. The crystals formed in toluene are stirred for a further 30 minutes after the addition of 20 ml of ether, then filtered off, washed with ether and dried at 60 ° in a high vacuum. Mp: 170-171 °.

The following acid addition salts of the same 25 triazole compound are prepared analogously to the process according to Example IC:

Example ID:

Hydrogen oxalate, mp: 180-182 ° 30 Example JE:

Hydrochloride, mp: 190-200 °

Bsispisia. 2- (4-chlorophenyl) -3-cyclopropyl-3-methyl-l- (lH-l, 2,4-triazol-l-yl) butan-2-ol: 35 Starting from l- (4-chlorophenyl) - 2-cyclopropyl-2-methylpropan-l-one is initially carried out analogously to that in

Example 1 (stages lund2). The title compound is purified, however, by crystallization from hexane to give colorless crystals (= racemate of the title compound).

Mp: 88-90 ° 40 Example 3:

The procedure is analogous to Example 1 (stage 2) and the following compounds of the formula I (Table A) are obtained by reacting an azole with the desired oxirane.

Table A 45 Example Ri * 2 R5'R6 Y Mp: 3.1 Cyclopropyl H 4-C1 N 84-86 ° 3.2 Cyclopropyl H 4-C1 CH 171.5-173.5 ° 3.3 CH3 H 2,4-diCl N 113-117 ° 3.4 ch3 ch3 2,4-diCl N 141-142 ° 3.5 ch3 H 4-C1 CH 95-96 ° (4 &gt; 3.6 ch3 H 4-C1 CH 147-148 ° (5) (4) mixture of diastereomers (5) diastereomer A, 50 -5- 55

AT 395 363 B

Example 4: 2- (4-Chloiphenyl) -2- (l-cyclopropylcyclopropyl) -l- (lH-IJ2,4-triazol-l-yl) ethan-2-ol (racemate):

Step 1;

To a suspension of 5.1 g of 80% sodium hydride in 50 ml of absolute tetrahydrofuran stirred under an atmosphere, first 133 g of dimethylsulfoxide and then within 133 minutes of 133 g4-chlorophenyl- (l-cyclopropylcyclopropyl) ketonin 50 ml of absolute tetrahydrofuran are added dropwise at room temperature. 15 g of trimethylsulfonium iodide are added to the resulting green suspension in portions and stirring is continued for 16 hours at room temperature and for 3 hours at 50 °. The reaction mixture is cooled to 0 to 5 °, a little water is added dropwise and, after the exothermic reaction has subsided, the product is extracted with ether. The organic phase is washed three times with water and once with brine, dried over magnesium sulfate and evaporated in vacuo at 60 °. The residue consists mainly of 2- (4-chloiphenyl) -2- (l-cyclopropylcyclopropyl) oxirane.

Level 2:

The crude oxirane from stage 1 is reacted with 1,2,4-triazole analogously to the process described in example 1, stage 2. After chromatography on silica gel and crystallization from hexane / dichloromethane, the pure title compound (racemate) is obtained. Mp: 110-112®. g.gispjgi, 5,;. 2- (4-chlorophenyl) -3-cyclopropyl-2-methoxy-3-methyl-l- (lH-l, 2,4-triazol-l-yl) butane: 0.8 g sodium hydride (80%) are added 25 ml of dimethylformamide submitted. A solution of 7.64 g of 2- (4-chlorophenyl) -3-cyclopropyl-3-methyl-l- (1H-l, 2,4-triazol-l-yl) butan-2-ol in is added dropwise at room temperature 50 ml of dimethylformamide and then stirred at 40 ° for 30 minutes. Then 3.76 g of methyl iodide are added dropwise at 5 °. The mixture is stirred at 20® for 18 hours, then poured onto 1 l of water and extracted with dichloromethane. The organic phases washed with water are dried over magnesium sulfate and concentrated on a rotary evaporator. The title binding is obtained in the form of white crystals after column chromatography on silica gel (ether / triethylamine = 10/2). Mp: 87-89®.

Example 6: 2- (4-chlorophenyl) -3-cyclopropyl-2-allyloxy-3-methyl-1 - (1 Η-1,2,4-triazol-1-yl) butane:

The title compound is obtained analogously to the process according to Example 5, using allyl bromide instead of CH3I and stirring the reaction mixture at 70® for 18 hours (instead of at 20 °). Mp: 58-60® (white crystals).

Example 7: 2- (4-chlorophenyl) -3-cyclopropyl-2-benzyloxy-3-methyl-l - (1H-1,2,4-triazol-1-yl) butane:

The title compound is obtained analogously to the process according to Example 6, using benzyl bromide instead of allyl bromide. Mp: 130-132® (white crystals).

Example 8: 2- (4-chlorophenyl) -3-cyclopropyl-2-acetoxy-3-methyl-l- (lH-l, 2,4-triazol-l-yl) butane:

The title compound is obtained analogously to the process according to Example 5, using acetyl chloride instead of CH3J, the reaction mixture being stirred at 70 ° for 24 hours; it crystallizes from diethyl ether. Mp: 117-119® (yellow crystals).

The compounds required as intermediates can be obtained as follows: A &gt; l-f4-chlorophenvB-2-cvclopropvlpropan-l-one: 15 g of 4-chlorophenyl (cyclopropylmethyl) ketone, dissolved in 80 ml of absolute dimethylformamide, become an under ^ atmosphere stirred suspension of 2.6 g of 80% sodium hydride in 30 ml of dimethylformamide was added dropwise and the mixture was further stirred at 25-35 ° for 2 hours. For this purpose, 153 g of CH3J are added dropwise within 15 minutes at room temperature with cooling, the mixture is mixed with cold water after 15 minutes of stirring at 25-30® and taken up in ether. After washing the organic extracts with water and saturated aqueous NaQ solution, drying over MgSC> 4 and evaporation, the crude title compound is purified by chromatography on silica gel with hexane / ethyl acetate (98/2).

The 4-chlorophenylcyclopropyl methyl ketone used as the starting compound can be prepared from the corresponding alcohol by Jones oxidation with GO3 in aqueous I ^ SO ^ acetone solution. -6-

AT 395 363 B B) l- (4-ChlorohenvlV2-cvcloOTOPvl-2-methvlDrc) pan-l-one;

The procedure is analogous to that described under A), but the reaction is carried out per equivalent of 4-chlorophenyl (cyclopropylmethyl) ketone with 2.4 equivalents of NaH and 3 equivalents of CH3J. The title compound chromatographed on silica gel with hexane / ethyl acetate (99/1) has: n ^ Op = 1.5390. 5 O 4-chlorophenvl-n -cvcloDronvlcvcloDroDvl ~) ketone:

23 3 g of 4-chlorophenyl (cyclopropylmethyl) ketone in 250 ml of absolute tetrahydrofuran are added dropwise under gentle reflux to a suspension of 4 g of 80% sodium hydride in 40 ml of absolute tetrahydrofuran in 40 ml of absolute tetrahydrofuran within 40 minutes and stirring is continued for 45 minutes under reflux. Then 15.8 ml of phenyl vinyl sulfoxide are slowly added dropwise at 10 20 ° using a syringe (exothermic reaction) and the mixture is stirred at 20 to 30 ° for 2.5 hours. The resulting intermediate (sulfoxide) is then cyclized by stirring under reflux for 18 hours to give the title compound. The reaction mixture is then cooled to 0 to 5 ° and, after the dropwise addition of 200 ml of water, extracted with ether. The organic phase is washed three times with water and once with brine. Dried over magnesium sulfate and evaporated in vacuo at 60 °. Chromatography 15 on silica gel with hexane / ethyl acetate (99/1) gives the pure product: n ^ p = 1.5605.

The title compound can also be obtained by replacing the phenylvinylsulfoxide with the corresponding sulfone or with a dimethylvinylsulfonium salt D) 1 - (4-ChloroDhenvP-2-cycloDropvlDroDan-1 -one: 20) The title compound can also be obtained from 4-chlorobenzyl cyanide Implementation with

Cyclopropyl methyl ketone in the presence of NaH, reduction of the l- (4-chlorophenyl) -l-cyano-2-cyclopropylpropene-1 thus obtained with Mg / CHjOH / NftyCl to l- (4-chlorophenyl) -l-cyano-2-cyclopropylpropane, followed by oxidation using O2 of this cyano compound under alkaline conditions in the presence of a phase transfer catalyst. Depending on the situation (price, environment, etc.), one or the other method may be preferred. 25th

Biological action / fungicidal use 1. Test results in the greenhouse 30 The following test results (obtained using the test methods described in GB 2064510A) illustrate the surprisingly favorable fungicidal action of the compounds according to the invention. The standard used is a- (cyclohexylmethyl) -a- (p-methylphenyl) -IH-l, 2,4-triazole-l-ethanol (example 2Z-22 in GB 2064520A). The results are expressed as EC 90, i.e. that is, as a concentration that allows 90% control of the infestation after spray application. 35 40 Compound according to Example 1+) 2 3.3 3.4 Standard fungus / culture Erysiphe / cucumber 5 8 1 <1 38 45 Erysiphe / wheat 3 4 5 3> 900 Podosphaera / apples 6 5 5 3 126 Uncinula / vines 4 6 15 2 46 Uromyces / Bean &lt; 1 &lt; 1 &lt; 1 1 &lt; 30 50 Septoria / Wheat 39 32 77 36 &gt; 900 +) mixture of diastereomers 55 2. Control of infestation under field conditions

The fungicidal activity of the compound according to Example 1 (mixture of diastereomers) was investigated further under field conditions: 62 g of active ingredient / ha allow more than 90% control of the powdery mildew and

Claims (8)

AT 395 363 B rust in cereals; and 2.6 g of active ingredient allow up to 99% control of the real mildew infestation in vines. Further studies suggest an effect of the compound according to Example 1 which is - equal to or better than that of propiconazole against powdery mildew in cereals and cucumbers and against rust 5 in cereals and coffee, or - equal to or better than fenarimol against powdery mildew in apples and vines and against Venturia in apples or - better than Triadimefon against u. a. Coffee grates. 10 PATENT CLAIMS 15 1. A method for combating phytopathogenic fungi, characterized in that an fungicidally effective amount of a compound of the formula I 20 25 I 30 wherein Y is CH or N, Rj is C 1.5 alkyl or C 1 ^ cycloalkyl, R2 is H or C ^ alkyl, where Rj and R2 can be linked together to form a C3.7 cycloalkyl radical, R5 is halogen and Rg is H or Halogen is, and R7 is hydrogen, C 1.5 alkyl, Cß ^ alkenyl, benzyl or acetyl, in free form or 35 in an acceptable form for agriculture addition salt, alcoholate or metal complex applied 2. The method according to claim 1, characterized in that compounds of the formula I are applied in which R7 is hydrogen 3. The method according to claim 1, characterized in that one applies the compound of formula I, wherein R2 &gt; Rg and R7 are hydrogen, Rj is methyl, R5 is chlorine and Y is N. 4. Move «! according to claim 1, characterized in that the compound of formula I is applied, wherein Rl and R2 are methyl, R5 is chlorine, Rg and R7 are hydrogen and Y is N. 45 5. Fungicidal composition comprising a compound of the formula I as defined in claim 1 in free form or in an acid addition salt which is acceptable for agriculture, alcoholate or metal complex form and an inert diluent which is acceptable for agriculture. 6. A fungicidal composition according to claim 5, wherein R7 is hydrogen 7. Fungicidal composition according to claim 5, wherein R2, Rg and R7 are hydrogen, Rj is methyl, R5 is chlorine and Y is N. A fungicidal composition according to claim 5, wherein R j and R2 are methyl, R5 is chlorine, Rg and R7 are hydrogen and Y are N. -8th-