NL8002944A - SALTS OF HERBICIDE 1.2.4-THIADIAZOLYL-5-UREA DERIVATIVES AND THEIR USE. - Google Patents

Description

N.O. 29,083

Salts of herbicide 1,2,4-thiadiazolyl-5-urea derivatives and their use,

The invention relates to new salts of per se known herbicidally active 1,2,4-thiadiazolyl-5-urea derivatives, processes for their preparation, these derivatives as active substance-containing agents, as well as their use for the selective weed control in cultures of useful crops and for inhibiting plant growth.

Herbicide-active 1,2,4-thiadiazolyl-5-urea-derivafcen are known, for example from German Offenlegungsschrif-10 at 1,670,924, 2,037,474 and 2,113,035 and Belgian patent 679,158

It has now been found that the salts of the present invention significantly enhance the activity of the 1,2,4-thiadiazolyl-5-urea derivatives. The salts moreover show a better selectivity than the urea. They * can be used for weed control in cultures of useful plants, especially grains.

Furthermore, it has surprisingly been found that the salts according to the invention, when used in mixing combinations with certain herbicides from the classes of the phenylureas, triazina, thiocarbamates or others, show not only the expected additive activity of the individual components, but eliminates the deleterious effect of the herbicides on grains, such as wheat and barley, thus antagonizes the original phytotoxicity of the herbicide in the sense of a "safener". Such mixtures show no loss of action against harmful grasses and dicotyledons. They are additionally active in a broadly effective herbicide with simultaneous elimination of the phytotoxicity of the herbicide on wheat and other cereals. This opens up the possibility of using such mixtures as a broad spectrum post-emergence herbicide against the major mono- and dicotyledonous weeds occurring in wheat and other cereals.

33 The salts according to the invention of the 1,2,4-thiadiazolyl-5-urea derivatives have the formula 1, η η η o Λ /. /.

2 where ~ Mn ® is the cation equivalent of a base, M is an n-worthy alkali or alkaline earth metal cation or an ammonium radical of the formula 4-, n as an integer 1, or 2 corresponds to the valency of the cation 5, while R & , R ^, R, and R ^ independently of one another represent hydrogen, benzyl or an optionally substituted alkyl radical with 1 to 4 carbon atoms with -OH, -CN or alkoxy, having 1 to 4 carbon atoms, R alkyl having 1 to 8 carbon atoms, optionally interrupted once or 10 times by oxygen, sulfur or nitrogen, or substituted with halogen, cyano or phenyl, which in turn is up to three times with halogen, cyano, nitro, trifluoromethyl, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 - carbon atoms or alkylthio with 1 to 4-15 carbon atoms can be substituted, alkenyl with 5 to 8 carbon atoms, optionally halogen substituted, alkynyl with 3 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, phenyl, optionally substituted three times d with halo, cyano, nitro, trifluoromethyl, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or alkylthio with 1 to 4 carbon atoms, R 4 alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 -25 carbon atoms, R 2 alkyl with 1 to 4 carbon atoms and X represent the direct bond, sulfur, oxygen, a sulfinyl or sulfonyl group.

In this definition, alkyl means branched and straight chain alkyl radicals having the indicated number of carbon atoms. As alkyl radicals R, methyl and branched radicals such as isopropyl, sec. and tert-butyl is preferred, while the preferred alkyl radicals R 1 and R 2 are methyl and ethyl. Methoxy is preferred as the alkoxy radical R2.

The salts of the invention of the 1,2,4-thiadiazolyl-5-urea derivatives may exist in various tautomeric forms corresponding to the probable formula 5. Such salts have not yet been described. They are prepared according to the invention in that 4-0 is obtained on a 1,2,4-thiadiazolyl-5-urea derivative of the formula 2,800,29,444. $ 3 in the presence of a solubilizing agent, allows a substantially equimolar amount of a base of formula 3 to act. In the previous formulas, Μ, E, E ^, E2 and X have the meanings given in formula 1.

The reactions of the reactants take place at a temperature between 0 ° C and the boiling point of the reaction mixture, but generally at 0 ° C to 40 ° C, ie at ambient temperature. The conversion takes from 30 minutes to about 2 hours.

Depending on the use, organic, polar solvents can be used as solubilizing agents alone or diluted with water. As solvents or suspending agents, alkanols with a small number of carbon atoms, acid nitriles such as acetonitrile, ethers such as dimathyl ether, diethyl ether, tetrahydrofuran or dio-xan, further toluene, acid amides such as dimethylformamide, ketones such as acetone and others are suitable. The salts thus formed are isolated from the reaction mixture by concentration of the solvent mixture, by distillation under normal or reduced pressure or by precipitation in less polar solvents or solvent mixtures.

Example I

24 g of H- [3-Trifluoromethyl-1,2,4-thiadiazolyl- (5)] -H'.H'-dimethylurea are dissolved in 200 ml of methanol and cooled to about 5 ° C. Then 4 g of solid, powdered sodium hydroxide is added with stirring, stirred for half an hour and the solvent is distilled under reduced pressure.

The residual sodium salt is dissolved in slightly warm methanol and precipitated with diisopropyl ether with stirring. 23.6 g of the sodium salt of the H- [3-trifluoromethyl-1,2,4-thiadiazolyl- (5)] - N'.H'-dimethylurea which decomposes above 270 ° C are thus obtained.

Example II

To a solution of 12.8 g of N- [3-trifluoromethyl-1,2.4-33 thiadiazolyl- (3)] - H'-methyl-isomethoxyurea in 73 nil diisopropyl ether is added dropwise 4.3 ml of isopropylamine with stirring . The isopropylamine salt which precipitates first as an oil becomes crystalline after a short time. After stirring for 30 minutes, the precipitate is filtered off with suction, washed with diisopropyl ether 40 and dried. 14.3 g * Λ Λ ft Λ L h 4 isopropylammonium salt of N- [3-trifluoromethyl-1,2 # 4-thia-diazolyl- (5)] -N'-ethyl-N'-inethoxy-uric acid are obtained in this way, which melts at decomposition at 152 ° C.

The following salts of formula 1 are prepared analogously to these compounds:

No. tax ΝίϊΤ physical η i constants _____Csmpt.) 1 CF3 N (CH3) 2 After> 270 ° dec.

2 CF3 N (CH3) QCH3 NH3C3H7iso 1S2 * 0ntl.

3 CF3 N (CH3) QCH3 After> 270 ° dec.

4 C12CH NCOI ^ After 189 * -9l * dec.

5 C12CH N (CH3) OCH3 Na 169 * dec.

6 CH S N (CH3) OCH3 Na 7265 * 7 @ -CH, S N (Ca3) OCH3 Na 256 * dec.

8 CC13 N (CH3) a NH (CH3) 3 9 C19CH xN (CH3) QCH3 NH CH10 iso 133 "dec.

10 C12CF N (CH3) OCH3 After 190 µl.

11 G1CF9 N (CH3) OCH3 Na 249 "dec.

12 (CH3) 3C- N (CH3) 2 Na 13 (CH) C- N (CH3) OCH3 Na> 2 * 0 "14 (CH3) 3C- N (CH3) OCH3 NH CH? Iso 15 (CH ^ CH- N (CH3) 2 Na 16 (CH3J2CH N (CH3) OCH3 After 248 ° dec.

17 (ch3) 2ch n (ch3) och3: ra2 (c2a40H) 2 CH3 N <CH3) 2 Na 19 CH. N (CH.) 0CH. NH, C, H 2 O 20 CH 3 N (CH 3) OCH 3 Na 216 "dec.

21 © N (CH3) 9 Na 22 N (CH3) 2 HN (CH3) 3 1 23 © N (CH3) OCH3 Na 199 "dec.

24 C13C N (CH3) 2 Na 25 C13C N (CH3) OCH3 After 177 ° 0tl.

26 C13C N (CH3) 2 NH (CH3) 3

o η n o a AA

5 so. I ta nr R. fü “physical 12 1 constants _____ ____. (~ smnt,) _ 27 (^ V-CH., 0 N (CH3) OCH3 After 256 ° dec.

28 C1 — H (^^ - CH20 S (CH3) 0CK3 Na 29 CH3S09 N (CH3) 9 Na 30 CH3S0, N (CH3) OCH3 NH3C3H? Iso 31 CH3S0 N (CH3) 2 Na 32 CH3S N (CH3) OCH3 After 121-123 ° 33 CCCHJ.SN (CH-) Na JJL34 C (CH3) 3S N (Ca3) 0CH3 NE ^ C ^ iso 35 cci3 n (ch3) och3 nh (ch3) 3 109 ° C.

36 CC13 'N (CH3) 0CH3 NH3C2H4OH 117-120 ° 37 isoC5K N (CH3) 0 Na 38 CgH17 N (CH3) 2 Na 39 isoC.Hu N (CH3) OCH3 Na 40 NiCH. ^ Na 41 CHgO N (CH3) 2 After 42N (CH3) 2 After 43 NiCH3 ^ 2 After 44 <2) ~ S ° 2 - N (GH3) 2 After 45 <2> "CH2S02 N (CH3) 2 After 46 CC13 N (CH3) OCH3 NH3C3H7iso 124-129 ° 6

The salts of formula 1 of the present invention are not very toxic to warm-blooded animals and their use presents no problems. They are stable compounds which are soluble in water and the usual organic solvents, such as alcohols, ketones, dimethylformamide and dimethyl sulfoxide. Usually application rates ranging from 0.1 to 5 kg / ha are required.

The salts of formula 1 have a herbicidal action in pre- and post-emergence use and can be used as herbicides in mono- and dicotyledonous cultures, alone or in combination with other herbicides, the phytotoxic activity of which may reduce them against beneficial plants antagonize.

The salts of formula I can be used as such or together with optionally too antigenic herbicides as well as together with suitable carriers and / or other additives. Suitable carriers and additives can be solid or liquid and correspond to the compounds customary in the formulation technique, such as, for example, natural or regenerated mineral products, solvents, dispersants, wetting, adhesives, thickeners and binders or fertilizers.

The active substance content in ready-to-use products is between 0.01 and 90%.

For use, the salts of formula 1 may be present in the following processing forms (the weight percentages in brackets representing effective amounts of active ingredient);

Solid prenarate forms: 30 Dusts and spreaders (up to 10% by weight), granules, coated granules, impregnated granules and homogeneous granules, granules (1 to 80% by weight);

Liquid prenarate forms: a) Water-dispersible concentrates, of the active substance:

Spray powder and pastes (25-90% by weight in the commercial packaging, 0.01 to 15% by weight in ready-to-use solution); emulsion and solution concentrates (10 to 50 wt%; 0.01 to 15 wt% in ready-to-use solution 4-0); 800 2 9 44 5 · 7 b) solutions (0.1 to 20% by weight), for example for pickling, aerosols.

For example, the salts of formula 1 according to the invention can be formulated as follows: Dusts:

For the preparation of a) 5% and b) 2% dusting agent, the following compound is used: a) 5 parts of salt or mixture of active substances, 95 parts of talc; b) 2 parts of salt or mixture of active substances, 1 part of highly dispersed silicic acid, 97 parts of talc.

The active compounds are mixed and ground with the carriers and can be sprayed in this form before use.

Granulate:

The following compounds are used to prepare a 5% granulate: 5 parts by weight of salt or mixture of active compounds, 0.25 parts by weight of epichlorohydrin, 0.25 parts by weight of cetyl polyglycol ether, 3.50 parts by weight of polyethylene glycol 91 parts of kaolin (particle size 0.3-0.8 mm).

The active product is mixed with epiclorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed on kaolin and then the acetone is evaporated under reduced pressure. Such a micro-granulate can be efficiently processed in seed furrows · Π Π 9 9 44 8

Spray powder:

The following ingredients are used to prepare a) 70 percent, b) 40 percent, c) and d) 25 percent, e) 10 percent spray powder: 5 a) 70 parts by weight of salt or mixture of active compounds, 5 parts by weight. parts of sodium dibutylnaphthyl sulfonate, 3 parts of naphthalene sulfonic acids-phenol sulfonic acids-formaldehyde condensation product 3: 2: 1, 10 parts of kaolin, 10 parts of champagne chalk; b) 40 parts of salt or mixture of active compounds, 5 parts of lignin sulfonic acid sodium salt, 1 part of dibutylnaphthalene sulfonic acid sodium salt, 54 parts of silicic acid; C) 25 parts of salt or mixture of active compounds, 4.5 parts of calcium lignin sulfonate, 1.9 parts of Champagne chalk / hydroxyethyl cellulose mixture (1: 1), 1.5 parts of sodium dibutylnaphthalene sulfonate, 20 19.5 parts parts of silicic acid, 19.5 parts of Ohampagne chalk, 28.1 parts of kaolin; d) 25 parts of salt or mixture of active compounds, 2.5 parts of isooctylphenoxy-polyoxyethylene ethanol, 25 parts of Champagne chalk / hydroxyethyl cellulose mixture (1: 1), 8.3 parts of sodium aluminum silicate, 16.5 parts of kieselguhr, 46 parts of kaolin; E) 10 parts of salt or mixture of active compounds, 3 parts of mixture of the sodium salts of saturated fatty alcohol sulfates, 5 parts of naphthalene sulfonic acid / formaldehyde condensation product, 82 parts of kaolin.

The active compounds are thoroughly mixed with the additives in suitable mixers and milled on suitable mills or rollers. Spray powders with excellent wettability and excellent floating properties are obtained, which can be diluted with water to give suspensions of the desired concentrations of 800 2 9 44 t -ff * 9.

Emulsifiable concentrates:

The following compounds are used to prepare a 25% emulsifiable concentrate: 5 parts by weight of salt or mixture of active compounds, 2.5 parts by weight of epoxidized plant oil, 10 parts by weight of an alkylarylsulfonate / fatty alcohol-polyglycol ether mixture, 5 parts by weight. parts of dimethylformamide, 57.5 parts of xylene.

From such concentrates, emulsions of any desired concentration can be prepared by dilution with water.

The new salts of the formula I have excellent herbicidal properties and are suitable for controlling grass-like and in particular broad-leaved weeds in various cultivated plantations. These active compounds also damage or destroy deep-rooting annual and perennial weeds in growth. For example, the new salts with formula-20 mule 1 can be used in small concentrations for selective weed control, for example for the control of chamomile species (Matricaria spp.), G-alium aparine, parsnip (Pastinaca sativa), foxtail species, for example Amaranthus spp., mustards (Sinapis spp.), grasses such as Echinochloa spp., Lolium spp., millets (Panicum spp.), are used in grain, corn, cotton, root crop and forage plants cultures. The salts of formula 1 can be used both before the emergence and after the emergence of the plants. In high concentrations, i.e., of about 5 kg of active compound per hectare, the new active compounds can serve for the complete killing and prevention of undesired plant growth. In small amounts used, some of the salts of formula 1 exhibit a growth-inhibiting effect.

The herbicidal activity (pre- and post-emergence) of the salts of formula 1 is tested according to the following test method.

Pre-emergence herbicidal action (germination inhibition)

In the greenhouse, immediately after sowing the 40 test plants in seed shells, the soil surface is treated with a water-based dispersion of the active compounds obtained from a 25% emulsion concentrate by dilution with water. concentration series used, corresponding to 4, 2, 1 and 0.5 kg of active product per ha. The seed shells are kept in the greenhouse at 22 - 25 ° C and a relative humidity of 50 - 70% and the test is carried out after Valued for 3 weeks and the results are rated according to the following scale: 1 = plants not germinated or completely dead 10 2-3 = very strong phytotoxic effect 4-6 = medium effect 7-8 low effect 9 s no effect (plants develop as untreated control plants).

15 Examples of test plants are: hordeum (barley) setaria italica triticum (wheat) echinochloa crus galli zea (maize) beta vulgaris sorghum hybr. (millet) sida spinosa 20 oryza (rice) sesbania exaltata glycine (soy) amaranthus retroflexus gossypium (cotton) sinapis alba avena fatua iponoea purpurea lolium perenne galium aparine 25 alopecurus myosuroides plastinaca sativa bromus tectorum rumex sp.

cyperus esculentus chrysanthemum leucum.

rottboellia exaltata abutilon sp.

digitaria sanguinalis solanum nigrum 30 Post-emergence herbicidal action (contact herbicide)

A fairly large number (at least 7) of weeds and cultivated plants, both monocotyledonous and dicotyledonous, were post-emergence (in the 4 to 6 leaf stage) with an aqueous dispersion of the active compound in dosages of 0.06; 0.125; 0.25 and 0.5 hg of active product per ha were sprayed onto the plants and stored at 24-26 ° C and a relative humidity of 45-60%. At least 15 days after treatment, the trial is rated and the result is graded on the same 40 scale as in the pre-emergence trial.

80 0 2 9 44 11

The salts of formula 1 tested showed a pronounced effect on pre- and post-emergence against, in particular, bipedal plants and weeds, while preserving grains such as wheat, rice and corn. A good herbicidal effect was obtained with the salt. 25 reached.

Surprisingly, the salts of formula 1 also have the property of protecting cultivated plants against the attack of aggressively aggressive plant chemicals, in particular against herbicides of the most diverse compound class, including 1,3,5-triazines, 1,2,4-triazinones, phenylureas, carbamates, thiol carbamates, haloacetanilides, halophenoxyacetic acid esters, etc., insofar as these are not or insufficiently culture tolerant.

Depending on the application purpose for the pre-treatment of seed of cultivated plants (pickling of the seed or the cuttings), a salt of formula 1 15 can be used as an antidote or antidote, or added before or after sowing in the soil either alone or together with the herbicide be applied before or after the emergence of the plants. The treatment of the plants or the seed with the antidote can therefore in principle take place independently of the time of application of the phytotoxic chemical.

However, it can also be performed simultaneously (tank mixture). Pre-emergence treatment includes both the treatment of the cultivated surface before sowing and the treatment of the sown, but not vegetated, surface.

The amounts of the antidote used relative to the herbicide are mainly directed to the mode of application. Insofar as a treatment is carried out in the field, the amounts of the antidote salt of formula 1 to the phytotoxic chemical range as 1: 100 to 5 1, preferably 1:20 to 1: 1. However, in seed pickling and similar targeted protections, considerably smaller amounts of antidote salt compared to the herbicide amounts used, for example, per hectare to be cultivated later per hectare (e.g. about 1: 3000 to 1: 1000) are required. As a rule, protective measures as well as seed pickling with the antidote salt of formula 1 and possibly later 800 2 9 44 Ύά field treatments with agricultural chemicals are only in loose connection. Pre-treated seed and plate material can come into contact with various chemicals later in agriculture, horticulture and forestry.

The antimicrobial activity for cultivation against strong herbicidal antagonistic activity was investigated by the following tests: Antidote action with separate application (antidote before Q-occurrence. Herbicide after-emergence)

General method: 10 Small flower pots (top diameter 6 cm) are filled with sandy loam soil, in which the cultivated plant is sown. After covering the seed, the product to be tested as an antidote is sprayed in a dilute solution in an amount on the surface, which corresponds to 4 kg of active substance per hectare. The pots are then kept at 20-23 ° C and a relative humidity of 60-70%. When the plants have reached the 2- to 3-leaf stage after 10 days, they are treated with the appropriate amount of herbicide as indicated below. treated.

14 days after the herbicide application is rated on a linear scale from 1 to 9, with 1 representing total plant damage and 9 representing unaffected plant growth. Plants without antidote protection serve as a control.

25 Pre-emergence antidote orphan (soil test)

General methodology:

Small flower pots (top diameter 6 cm) are filled with garden soil, in which the plant culture is sown, covered and slightly pressed. The product to be tested as an antidote is then sprayed on as a dilute solution in an amount corresponding to 4 kg of active product per hectare. Immediately thereafter, the herbicide is sprayed in a corresponding manner. After 18 days of storage at about 20-23 ° C and a relative humidity of 60-70%, it is rated on a linear scale from 1 to 9, 1 representing total plant damage and 9 representing unaffected plant growth. Plants without antidote protection serve as a control.

In this test, the salt according to the invention No. 2 40 cultivated millet against the phytotoxic activity of the herbicide N- (1'-methyl-2'-methoxyethyl) -if-chloroacetyl used in excess dosage. Protect -2-ethyl-6-methyl-aniline. Antidotum nroef bi.i seed swelling (seed drenching)

IR 8 rice seeds are soaked with solutions of the test products at 10, 100 or 1000 ppm for 48 hours. The seeds are then dried for about 2 hours until they no longer stick. Rectangular plastic pots (8 x 8 cm, height 10 cm) are filled up to 2 cm below the rim with sandy loam soil. 4 g Seeds are sown in pots per -10 and covered only very weakly (about the diameter of the seed grain). The soil is kept in a moist (not soaked) condition. A herbicide is then used in a dilute solution and in an amount equivalent to 1.5 kg of active product per 15 ha. When the plants have sprouted and grown to a height of about 5, they are transplanted into a seed bowl, the soil of which is covered with about 2 cm of water above. 7 and 18 days after transplanting, the condition of the plants is measured on a linear scale, 1 representing total plant damage and 9 representing unaffected plant growth.

Compounds 1, 2 and 5 in this test were able to protect the rice sprouts from the phytotoxic action of the chloroacetanilide herbicide used.

800 2 9 44

Claims (10)

14- 1. Salts of 1,2,4-thiadiazolyl-5-urea derivatives of formula 1, wherein ® Let cation equivalent of a base, M is an n-worthy alkali or alkaline earth metal cation 5 or an ammonium residue of formula 4, n as an integer 1, or 2 corresponds to the valency of the cation, while R, R 4, Rc and R 4 independently of one another hydrogen, benzyl or an alkyl radical optionally substituted with OH, CN or alkoxy having 1 to 4 carbon atoms with 1 to 4 carbon atoms, 1 alkyl of 1 to 8 carbon atoms, optionally interrupted once or several times by oxygen, sulfur or nitrogen or substituted with halogen, cyano or phenyl, which in turn is up to three times with halogen, cyano, nitro, trifluoromethyl, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, or alkylthio of 1 to 4 carbon atoms may be substituted, 20 alkenyl of 3 to 8 carbon atoms, optionally substituted with halogen, alkynyl of 3 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, phenyl, optionally substituted up to three times with halo-25, cyano, nitro, trifluoromethyl, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, or alkylthio of 1 to 4 carbon atoms, R 1 | alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, R 2 alkyl of 1 to 4 carbon atoms and X represent a direct bond, sulfur, oxygen, a sulfinyl or sulfonyl group. 2. The sodium salt of N- [3-trifluoromethyl-1,2,4-thia-diazolyl- (3)] -N ', N'-dimethylurea. 3. The sodium salt of N- [3-trifluoromethyl-1,2,4-thiadiazolyl- (5)] -N'-methyl-N'-methoxy-urea. 4. The sodium salt of N- [3-trichloromethyl-1,2,4-thia-diazolyl- (5)] -U1-methyl-N'-methoxy-urea. 5. Process for preparing 1,2,4-thiadiazolyl-5-40 urea derivative salts, characterized in that 800 2 9 44 15 are the salts of formula 1, wherein the symbols have the meanings given in claim 1 , prepared in a manner known per se. 6. Process for the preparation of 1,2,4-thiadiazolyl-5-5 urea derivative salts, characterized in that salts of formula 1, wherein the symbols are as claimed in claim. 1, meanings are prepared in that, in the presence of a solubilizing agent, a substantially equimolar amount of 1,2,4-thiadiazolyl-5-urea derivative of formula 2, in which B1 and S have the meanings stated in formula 1, is let a base of formula 3, in which M has the meaning stated in formula 1, act and isolate the salt thus formed from the reaction mixture in a manner known per se. 15 Herbicidal agent, characterized in that the active compound contains at least one salt of the formula 1. 8. A process for preparing a herbicidal agent, characterized in that an active compound of the formula 1 is brought into a form suitable for such use. 9. A method for the selective control of weeds in cultures of useful plants, characterized in that an effective amount of a salt of formula 1 is applied alone or together with a herbicide to the fields to be cultivated with useful plants. 10. Use of salts of formula 1 or agents containing these salts as a selective herbicide in cultures of cereals, corn, rice, cotton, soy and sugar beets. 800 2 9 44 1 1 1 1 1 1 - ~] 0 R * || -Ï R9 II 1 I2 1 un Θ n. JUjh-c-n-r, * 'm V 11 1 n o l RT ~ | I2 Nv / —NH-C-N-R, V II 1 0 A MOH i Θ * b Rc 5. RXirï i2 1 in © y V "* 1 '" M 800 2 9 44