FI67209C - 2,6-DINITROANILINHERBICIDER - Google Patents

Description

R3F ^ I M fl «KUUI.UTUSJULICAISU ^ 70 Π Q

JSTa m 01) UTLÄCGNINCSSIUUFT 0 / 2U9 C Patent born 11 C2 1985

Patent title (51) K ^ flm.CL c 07 c 93/1 **, 87/62, A 01 N 33/18 FINLAND-FINLAND Φ) 76368 ** (22) WE ^ Wl-Amek *, *, 22.12 .76 '' (23) AMmHM — G ** Ma * · 22.12.76 (41) TaMKHUMfal-BavkaewdH 23.06.77

Prtwttl- and rekbtarihaHitM na «fcert | wo · h ΙοΜΜ ^ μι PMmD.ocH rtghtarrtywhw ^ £» dlfcrt! Ta! R7.bii ^ 31.10.8 ** (32) (32) (31) * n * anjf «witch— «« Gird prtertoat 22.12.75 1 * ». 06.76 USA (US) 6 ** 3226, 696Ο85 (71) American Cyanamid Company, Wayne, New Jersey, USA (US) (72) Albert William Lutz, Princeton, New Jersey, Robert Eugene Diehl,

Trenton, New Jersey, USA (llS) (7 **) Oy Kolster Ab (5 **) 2,6-dinitroane 1 inin herbicides - 2,6-dinitroane 1 inherbicider

There are a large number of substituted 2,6-dinitroaniline herbicides in the field of herbicides, which vary in their effectiveness.

U.S. Patent 3,332,769 discloses 4-substituted-N-sec-alkyl-2,6-dinitroaniline, and U.S. Patent 3,766,624 discloses 3-alkoxy-4-substituted-N-alkyl-2,6-dinitroaniline. anilines.

The present invention relates to certain 2,6-dinitroaniline compounds used as herbicides which have been found to be more effective than the compounds known in the art. These compounds have the formula H R0 N '0'νΛ ^ Ν02 ^ γ ^ ΟΗ2ΟΟΗ3

Y

26209 where 1 * 2 is isopropyl, 2-methoxy-1-methylethyl, sec-butyl or sec-pentyl, and Y is methyl, ethyl or isopropyl.

Of the compounds in this class of compounds, those in which the methoxymethylene substituent is in the meta position relative to the amino group are particularly preferred. This is based on an unexpected increase in herbicidal activity prior to germination, which is thought to be due to a methoxy substituent on the meta-methyl group. Regarding the utility of these compounds, the preferred compound in this category is N- (1-ethylnopyl) -2,6-dinitro-3-methoxymethyl-p-toluidine.

The herbicidal compositions of this invention are solid or liquid compositions containing an effective amount of one or more novel 2,6-dinitroaniline compounds as a herbicidal diluent, i. with a neutral carrier or other conventional excipient used in the mixture.

The novel compounds of this invention are applied by applying an effective amount of the compound, preferably as the herbicide mixture described above, to a soil containing seeds of controlled plants.

Typical mixtures are, for example, dusts, dust concentrates, powders, granules and the like. The applications carried out by conventional methods and devices take place in such a way that the active substance is applied from about 0.07 kg / ha to about 22 kg / ha and preferably from 0.28 to 9 kg / ha.

Dusts are generally prepared by co-grinding about 1 to 15% by weight of active ingredient with about 99 to 85% by weight of a solid diluent such as attaclay, kaolin, diatomaceous earth, effervescent clay, talc, pumice or the like.

Dust concentrates are prepared in the same way as dusts, except that they generally use about 15 to 95% by weight of active ingredient.

Granular mixtures can be prepared by applying a liquid solution of the active substance to sorbent granular carriers such as attaclay, kaolin or diatomaceous earth granules. Alternatively, they can be mixed with neutral carriers and applied to non-sorbent granules such as sand or limestone. Wetting agents are prepared by grinding the active ingredient 67209 with a solid carrier, such as the carrier used in dust compositions. The active ingredient is usually used in an amount of about 25 to 75% by weight and the solid carrier in an amount of about 73 to 23% by weight. In addition, about 1 to 5% by weight of a dispersant such as alkali metal salts of naphthalene sulfuric acid and mixtures of anionic and nonionic agents is usually added, and about 1 to 5% by weight of a surfactant such as polyoxyethylene alcohols, acids, adducts, sorbitan fatty acid esters and sorbitol esters. .

Thus, the herbicidal compositions of this invention will generally contain from about 1% to about 95% active ingredient, with the remainder being one or more herbicidal diluents or adjuvants. Particularly preferred amounts of the various types of mixtures are specified above. As mentioned, they are used in the usual manner as such or further diluted depending on the conditions.

Wettable powder mixtures are usually dispersed in water and applied as a liquid spray to the desired target.

When used before germination, dusts or liquid syringes containing the active substance can be applied to the soil shortly after planting or mixed into the soil by a method known as pre-planting mixing.

When used for seedling after emergence, application takes place in the press of unwanted plant species.

The compounds of this invention are prepared by a one-step nucleophilic substitution reaction between an alkali metal methylate and a 2-methyl-5-nitrobenzyl compound to form methyl 2-methyl-5-nitrobenzyl ether and its obvious equivalents. Ether is a useful intermediate in the preparation of meta-methoxymethylene compounds of formula (I).

This reaction can be represented graphically as follows: 4 67209 ρ ι ° 2

| l I + MOCHg ^ || I

CH 3 ch 3 (II) (III) (IV) wherein M is an alkali metal and X is a leaving benzyl substituent, preferably chlorine, bromine or tosyl. The preferred compound of formula (II) is 2-methyl-5-nitrobenzyl chloride. It is recommended to use methanol or a non-protic organic solvent such as dimethoxyethane or Bentene as the solvent in this reaction. The conversion can be conveniently carried out by stirring the reactants and heating the mixture to room temperature and temperatures between about 80 ° C. When using methanol, boiling is recommended to avoid the necessary transfer to closed containers.

Other reactions useful in the present invention are set forth in the descriptions below.

Sodium or potassium methylate is recommended as the base. The reaction is preferably carried out by heating the reactants in an organic solvent. An alcohol, e.g. methanol, can be used as the reaction medium.

Another way to synthesize various dinitroaniline compounds used in the practice of this invention involves the nucleophilic substitution of an I-substituent, such as a chlorine group, with a suitable substituted amine. Chlorine is the primary substituent; substituents such as bromine or iodine may also be used. The displacement reaction can be carried out without an organic solvent or using such, e.g. toluene, benzene or mainly xylene.

The reaction, shown graphically below, is carried out by heating the reactants, preferably between 50 ° C and 150 ° C.

67209 H R2

Cl N

° 2N NO 2 j. '> v ^ NH xylene ° 2N \ / ΧΝ5ν ^' Ν02

Tj -, - - LA

\ # ^ CH2OCH3 CH2OCH3 Y Ϊ (V) (VI) (I)

Chlorobenzene intermediates can be prepared by reacting an appropriately substituted aniline with ethyl chloroformate in benzene at about 10 to 50 ° C to give the correspondingly substituted N- (ethoxycarbonyl) -3,4-substituted aniline. .

This product is then treated with a cold solution of sulfuric acid and nitric acid, i.e. at about 0 to 20 ° C to give N- (ethoxycarbonyl) -3,4-disubstituted-2,6-dinitroaniline. When the product thus formed is reacted with sulfuric acid at a higher than normal temperature, mainly at about 100 to 150 ° C, the n = (ethoxycarbonyl) product is converted to 3,4-disubstituted-2,6-dinitroaniline. The amino group is replaced by a chlorine atom by first heating the compound with glacial acetic acid and diazotizing the amine with a mixture of sodium nitrite and sulfuric acid. This is followed by treatment of the diazotized mixture with a mixture of cuprous chloride and hydrochloric acid, followed by heating the resulting mixture at about 40 to 80 ° C to give the chlorinated compound.

When the above-mentioned dinitroaniline compounds have an asymmetric carbon atom, optical isomerism may occur. Accordingly, such compounds may be used as individual isomers or as a mixture, such as a racemic mixture. Unless otherwise indicated when referring to such a compound, the term isomerically undegraded compound. Separation of isomers »when desired, can be performed by conventional separation methods. A conventional method involves the incorporation of an optically active substituent, such as a (-) - sec-butylamino group, into a compound, e.g., by a ring substitution method.

6 67209 The present invention and the preparation of the active ingredients are further illustrated by the following examples and descriptions. Parts and percentages are, unless otherwise indicated, parts by weight and percentages by weight.

Description A

Preparation of methyl 2-methyl-5-nitrobenzyl ether 2-Methyl-5-nitrobenzyl chloride (16.2 g) was dissolved in methanol (180 ml) and then sodium methylate (5g) was added and the mixture was boiled. The reaction was monitored by plate chromatography (road) eluting with hexane / benzene, 75/25 v / v. Additional sodium methylate was added and heating was continued until the reaction was complete. Finally, the mixture was cooled and filtered. The filtrate was concentrated in vacuo and the residue was dissolved in methylene chloride and washed with water. The organic layer was then separated and dried over magnesium sulfate. After the desiccant was removed by filtration and the filtrate was concentrated in vacuo, 15.8 g of solid remained, which was recrystallized from 150 ml of hexane to give 11.5 g of a white solid, m.p. was 45-49 ° C. The second work-up gave a solid which, after recrystallization from hexane, gave a solid having a m.p. was 50-52 ° C. Elemental analysis of the product gave the following results:

Calcd for C 9 H 11 NO 2: C, 59.66; H, 6.12; N, 7.73.

Found: C, 59.65; H, 6.17; N, 7.64.

Description B

Preparation of 3- (methoxymethyl) -p-toluidine (intermediate)

Methyl 2-methyl-5-nitrobenzyl ether (11.5 g) was dissolved in 125 ml of anhydrous ethanol. To this was added a solution of sodium sulfide monohydrate (48.3 g) and sodium hydrogen carbonate (16.7 g) in 75 ml of water. The resulting mixture was boiled until plate chromatographic analysis (road) showed the disappearance of all starting material. The mixture was then concentrated in vacuo to an oily solid. Methylene chloride was added and the mixture was filtered. The methylene chloride layer was separated and dried. After removal of the desiccant, the solution was concentrated in vacuo to give 9.3 g of a mobile orange liquid which was used to prepare the compound of Description C.

7 67209

Description C

Effect of N- (1-ethylpropyl) -3- (methoxymethyl) -p-toluidine (intermediate)

A slurry of 3- (methoxymethyl) -p-toluidine (9.3 g) in 40 ml of diethyl ketone and a 5A molecular sieve (19 g) was stirred at room temperature for 15 hours. The mixture was then filtered and the filtrate was treated with an added portion of diethyl ketone (10-15 mL) and a fresh molecular sieve (10 g). After 40 minutes at 40-50 ° C, the mixture was filtered and evaporated to dryness in vacuo. The crude product (9.0 g) was dissolved in 50 ml of methanol and cooled to 10 ° C. Sodium borohydride (3.7 g) was then added in small portions. Additional methanol (25 mL) was added during the addition. Thirty minutes after the end of the addition, the mixture was acidified with 10% hydrochloric acid and ice.

The mixture was extracted with ether and the ether extracts were discarded. The aqueous extract was then basified and extracted with ether. After the ether extract was dried over magnesium sulfate, the desiccant was removed and the ether solution was concentrated to an orange oil (8.1 g) which was found to contain more than 75% of the second component using gas-liquid chromatography. Fractional distillation gave a sample with a boiling point of 25 ° C under a vacuum of 0.4-0.5 mm. The initial analysis of the product was as follows:

Calculated for C 75.97; H 10.47; N 6.33

Found: C, 75.87; H 10.62; N 6.24.

Description D

N- (1-ethylpropyl) -3- (methoxymethyl) -2,6-dinitro-p-to-luidiini; also called (1-ethylpropyl) -3- (methoxymethyl) -4-methyl-2,6-dinitroaniline A solution of N- (1-ethylpropyl) -3- (methoxymethyl) p-toluidine (2.13 g) was prepared. ) In 10 ml of dichloroethane and this was treated with a nitrate mixture of 3.78 g of nitric acid, 3.0 g of concentrated sulfuric acid and 1.4 g of water. The addition was performed at 30 ° C, -3 ° C, and the mixture was then maintained at this temperature for 3 hours. The crude product was poured into water and extracted with methylene chloride. The methylene chloride layer was separated and dried over magnesium sulfate. Removal of the drying agent by filtration and evaporation of the filtrate to dryness in vacuo left 3.2 g of residue O 100%). The crude product was purified by column chromatography on silica gel with benzene as eluent. All fractions, which were determined by plate chromatography to be the same compound, were combined to give 1.3 g of an orange solid, m.p. was 55-57 ° C. For analysis, a sample recrystallized from hexane m.p. was 56-57 ° C.

Its Elemental Analysis was:

Calculated: C 14 H 21 N 3 O 5: C H 6.80; N 13.50

Found: C, 54.00; H 6.69; N 13.44

Description E

Following the procedures of Descriptions AD, the appropriate 4-alkyl-nitrobenzene can be converted to methyl 2-alkyl-5-nitrobenzyl ether followed by reduction alkylation with the appropriate ketone followed by dinitration, or alternatively following Method UY using the appropriate 3-chloro-6- alkyl 2,4-dinitrobenzyl methyl ether and the appropriate amine to give the following compounds of formula (I):

R2 X Sp. ° C

C ^ H ^ -i. CHg orange oil C ^ Hg sec. CHg orange oil CH (CH3) C3H7-n CHg 31.5-32.5 ° CH (CH3) C3H7-d. CHg orange oil C3H2 -i ^ 2 ^ 5 orange oil C ^ Hg-sec. ^ 2 ^ 5 yellow-orange oil CH (CH3iCgH ^ -n ^ 2 ^ 5 orange oil CH (C2H5) 2 C2H5 27.5-29 ° C3H7-i C3H7 ~ i red-orange oil C ^ Hg-sec C3H7 ~ i red oil CH (CH3) C3H7 ~ n C3H7 ~ i red oil CH (C2H3) 2 C3H? -i red-orange oil 9 67209

Description S

Preparation of N-chloro-2-ethyl-5-nitrotoluene (intermediate) Paraformaldehyde (105.1 g) was added portionwise to a stirred solution of 620 ml of concentrated sulfuric acid and 720 ml of fuming sulfuric acid at 3 ° C to 10 ° C. Dry calcium chloride (252.5%) was then added portionwise, keeping the temperature of the mixture between 4 and 11 ° C. The mixture was stirred in an ice bath for 1.5 hours, and then 264.0 g of 4-ethylnitrobenzene was added dropwise so that the reaction temperature remained between 6 ° C and 9 ° C. The mixture was stirred at a temperature between 9 ° C and 18 ° C for 13 hours and then for 123 hours at a temperature between 18 and 20 ° C. The mixture was poured into a slurry of ice and water, and the crude product was extracted with chloroform. The chloroform layer was partially concentrated, shaken with 100 ml of potassium hydrogen carbonate and water, and mixed with magnesium sulfate. The filtered solution was concentrated in vacuo to give 317.6 g of a tan liquid. The crude product was fractionated by distillation in vacuo to give a pale yellow liquid, b.p. was 114-118 ° C under a vacuum of 0.2 mm Hg.

Description T

Preparation of 2-ethyl-5-nitrobenzyl methyl ether (intermediate) Sodium methylate (44.7 g) was added portionwise to a solution of 150.0 g of chloro-2-ethyl-5-nitrotoluene in 1.15 l of methanol, maintaining the temperature between 18 and 30 ° C. The mixture was boiled for 2 hours, cooled to 3 ° C and filtered. The filtrate was concentrated in vacuo and the resulting slurry was shaken with saturated aqueous sodium chloride solution and methylene chloride. The methylene chloride layer was washed, filtered through sodium sulfate, and mixed with magnesium sulfate. The filtered solution was concentrated in vacuo to give 133.89 g of a dark brown liquid. The crude product was fractionated by vacuum distillation to give a yellow liquid with a boiling point of 113 ° C at 0.35 mm Hg and which turned into solid pale yellow prisms with a melting point of 21.5-23.5 ° C.

10 67209

Description u Preparation of H-ethyl-N- (I-ethylpropyl) -Ck-methoxy-m-toluidine (intermediate)

A mixture of 10.0 g of 2-ethyl-5-nitrobenzylmethyl ether, 10.38 g of 3-pentanone, 0.23 g of 2-naphthalenesulfonic acid and 0.60 g of 5% platinum-carbon catalyst was shaken under a hydrogen atmosphere 2 hours at room temperature and 4 hours at 48-60 ° C. The mixture was diluted with 200 ml of ether, filtered and the filtrate was shaken with 2.5% aqueous sodium hydroxide solution, washed with water, filtered through sodium sulfate and stirred with magnesium sulfate. The filtered solution was concentrated in vacuo to give 10.76 g of a tan liquid which was pure by gas-liquid and plate chromatographic analysis.

Description V

Preparation of 4-ethyl-N- (1-ethylpropyl) -α-methoxy-2,6-dinitro-m-toluidine

A solution of 13.0 g of concentrated nitric acid, 10.75 g of concentrated sulfuric acid and 4.88 g of water was added dropwise over 2.3 hours to a stirred solution of 7.75 g of 4-ethyl-N- (1-ethylpropyl). ) - d-methoxy-m-toluidine in 35 ml of 1,2-dichloroethane. The temperature of the mixture was maintained between 18-21 ° C during the addition and for a further 44 hours. The mixture was poured onto 30 g of ice and then extracted with methylene chloride. The extracts were combined with the dichloroethane layer, the combined organic layers were washed with 2.5% aqueous sodium hydroxide solution and water, and mixed with magnesium sulfate. The filtered solution was concentrated in vacuo to give 10.86 g of a dark brown solid. Purification by chromatographic means gave yellow-orange crystals of m.p. was 28-29 ° C.

Description Y

Preparation of 4-ethyl-N-methoxy-N- [1- (2-methoxy-1-methylethyl] -2,6-dinitro-m-toluidine

Benzyl ether (5 g) and 1- (2-methoxy-1-methylethyl) amine (4.1 g) were dissolved in toluene (100 ml) and heated to boiling. After 20 hours, the reaction mixture was cooled, washed with dilute hydrochloric acid, water and then dried. After passing the solution through a column of neutral alumina, the toluene was removed in vacuo to leave 3.7 g of an orange oil which crystallized on standing. Recrystallization from methane gave the pure product, m.p. 62-64 ° C.

Description AB

3

Preparation of Ct-methoxy-N- (2-methoxy-1-methylethyl) -3,4-xylidine (intermediate)

A mixture of methyl 2-methyl-5-nitrobenzyl ether (12 g, 0.066 mol), methoxyacetone A20 g (used as solvent, β-naphthalenesulfonic acid (0.3 g) and 5% Pt / C catalyst shake in a Parr hydrogenator, keeping the temperature below 40 ° C with external cooling, a theoretical amount of hydrogen is consumed (0.26 moles) and further absorption is complete after 2 hours, the reaction mixture is filtered and the excess methoxyacetone is removed in vacuo to give a red oil. This oil was purified on a silica gel column eluting with Bentene to give 7.6 g (52%) of a colorless oil.

Analysis; calculated: C 69.91%; H 9.48%; N 6.26% found: C 69.88%; H 9.19%; N 6.36%

Description AC

Preparation of 3-methoxy-N- (2-methoxy-1-methylethyl) -2,6-dinitro-3,4-xylidine

A nitration mixture of concentrated sulfuric acid (1.4 g), water (0.7 g) and 70% nitric acid (1.8 g) is added at 25 ° to a solution of (k-methoxy-N- (2 g) -methoxy-1-methylethyl-3,4-xylidine (1.0 g, 0.004 mol) in 10 ml of dichloroethane After stirring the reaction mixture at 25 ° for one hour and then at 40 ° for 1 hour, The desired product is recovered by extraction with chloroform and isolation as an orange oil, which is purified using a silica gel column and eluting with hexane / benzene (90/10) to give a solid which is crystallized from a small amount of metal to give 0.8 g. (64%) pale yellow crystals melting at 54.5-56 DEG C. Calculated: C 49.83%, H 6.11%, N 13.41% Found: C 49.77%, H 5 , 90%, N 13.24% 12 67209

Description AD

Following the AC method of the description, dinitrate was appropriate

O

oL-methoxy-3,4-xylidine or 4-chloro-Ok-methoxy-m-toluidine to give the following compound of formula (I); r2 Y Sp. ° c CH (CH3iCH2OCH2Cl2H2-1) orange oil

Example 1

The selective herbicidal effect of the treatment during pre-emergence treatment was demonstrated by the following experiments, in which the seeds of various monocotyledonous and dicotyledonous plants were mixed separately in the planting soil and planted in separate pots of about 0.6 liters. After implantation, the pots were injected with selected aqueous acetone solutions containing the test compound. The treated pots were then placed on greenhouse benches, watered and treated by conventional greenhouse methods. Three or four weeks after treatment, the experiments are stopped and each pot is examined and the results are evaluated using the evaluation system shown below.

Evaluation system

Evaluation system Growth difference compared to control% *) _ 0 - no effect 0 1 - possible effect 1-10 2 - weak effect 11-25 3 - mild effect 26-40 5 - clear effect 41-60 6 - herbicidal effect 61-75 7 - good herbicidal effect 76-90 8 - almost complete destructive effect 91-99 9 - complete destructive effect 100 4 - abnormal growth, i.e. physiological malformation, but the overall effect is less than in the assessment scale in section 5.

*) Based on visual determination of plant position, size, strength, color whitening, abnormal growth and overall appearance.

13 67209 Using this evaluation system and the following plant species: sesbania, mustard, amaranth, Ambrosia weed, morningglo-ry, yarrow, creeping grass, green punt, weed, corn, cotton, soybeans, rice and velvet leaf - were tested (l-etopyl) 3-methoxymethyl-1-methyl-2,6-dinitroaniline by spraying it into pots planted with seeds of the above-mentioned plant species. The treatment was performed so that the amount of test compound was 1.12 kg / ha to 0.07 kg / h-Taari. The selective herbicidal activity of the test compound, when applied to the seedling, is shown in the table below.

Abbreviations of plant names: SE - Sesbania (Sesbania exaltata) MU - Mustard (Brassica kaber) PI - Amaranth (Amaranthus retroflexus) RW - Ambrosia (Ambrosia artemisiifolia) MG - Morningglory (Ipomoea purpurea) BA - Grasshopper (Echinochloa crusgus crusgus) (Digitaria sanguinalis) F0 - Green headland (Setaria viridis) TW - Blackberry (Sida spinosa) VL - Velvet leaf (Abutilon theophrasti) CN - Maize (Zea mays) CO - Cotton (Gossypium hirsutum) SY - Soybean (Glycine max)

Rl - Rice (Oryza sativa).

14 67209 id en

cn M

Φ Ρί o o o o o 3 _______ 4-> -

Ä X

id (Λ cd o o σ o Ά ____

nJ

-H o O CM o o o o G___ >>

rH S

O) O lo o o o o 4-> + J--

• H O

en P- <en en en cd en: id ___

Oh

Pi • H O en en en en σι -H _

G -H

• H -H <O τη cp σ> cd en en cd H id _____—

> H

k -H J

id>> ro m en [s ra cn ..__________ G id M Q) Ai 13 en h co oo co oi h O X _____ rX 3

Ai Ί- »O

G 3 Scnr ~ -rHocz> H Ai _

3 -H

rd id IS

Ε-ι> Ρίι ^ -οοσο> s ____

Ai a: m G P-ι en cd en en cx>> .__ S _ ° 3 rG S CD CD CD CD r- o 3 id ----- c_i m

id en W

A! 3 en en en r- cn o

Ai O ______ • H G ----

CU G

G H id CU H (d en cu + -> • H E Λ> · Η ad Q) • Hid GrGcMcooocot '' • H4J Jd \ H m n r! o -M: id M "" "" n

AiG SAiHoooo

(U <D

rH G CD "'" ~~

CU G ^ CD

eo cu lo K

E CM δ

CS | _ O

o 2 _p *. I> = {»

I> I / ~ S

CM

o 67209

Examples 2-17

Following the procedure of Example 1, the compounds listed in the following Table 2 were tested with the results reported in the table.

16 67209

K

nJ CQ

tn en tn ----- <D 'j ^ j ^ οοσοοοοιοσσοοοοοοοσ

O

φ Ooooooooooooo oo o o o o

P

en ----

•B

Ώ ^ O O O O O CD OOOOOOr — ιοοοοο>. ° #v

2j 0-d-rHOOOOCSIOOOOOOOOOOO

m P bs 3 -H ----

O TO

^ '' j. en σι en en οι λ σι σι σι σι σι Γ 'οι oi cnun o o

»—I tM

<u · Η O

rH> ---- i — I to g id ^ * ρί σισκηοισιοισισιεησισισισιςησκοωο eg ---- S cncncnc ^ cNCNcncncncnr ^ oioocnco <x> cn o ä_ _

CO. ΓΜΠ r-10t ^ CDCNi — IrHOCNOOOOO

s s "^ ---

tl CM O

U O CM ^ (J) CT) ω t.N CO CO CSJ O O O CM ooooo% 2 g g CM, £ ^ _____ O t es. \ / y ce) <ω ncMHooo cnooooooooooo 1 Ϊ * ~ ^) 'jj3 otcooooooooooooooooo S * ------

o HenenOJOOh ‘OHJ) CJ) OOiOOMDNOOO

3 ---- '£ j ^ aa en o o • 5 JE___ • 3

j? W oor ^ coooo c-cnoo O O O O O O O

O? ajJjScNtooocor cOCNCooocot ^ ^ ^ is rocNeoooior

Vi H Λ HWNHOOHWWrIOOHUHNHOO

p jgjjPrHOOOOOrHOOOOOr-IOOOOO

T.H. | -H | m ^ r- δ

s; K te I

& co co

S O O

I -! -! ---? ω 2 Jl ci -hi ’, d CN r- ~ OO rh Ά K te te. . Ή CO · Η CO * ri i I «|

M fj tn to L

i S te a) x S

af-S s .a s .a o ^ iS S a 5 iS3

I I I

17 67209

S

SCO

co CO ----- CD 'i — I> t ^ cOoooooooooooccnooo c

| j O O O O OOOOOOOOCMOOOOO

-μ CO ----

•B

§ CO i — 1 O O O O OOOOOCOJOJOOOO 3 QcoCMr-tiHOOr-IOOOOOCMOOOOO

3 Ti —---

g V

<D ^ b σισ) θ) σ) οοωσιωσ) ωίΐοασισισισισ) σι r-H ’> ----

r! W

.j! j K σι σι mo) oo oo σι σι σι σι en co ro σι σι en σι en JS ----- jjj ^ o en oi m> cc O) ω (N cm o σ> σ> en m en cm ^ C. 1. - - - ---- rt 5

8 ® -t ^ -CDOoroOOOOcDiHOOOOOr-rOi-100

M co tr μ 33 «ττ>> rt R Ö ----

e-1 tj CM O

O CM r — C-'t ^ C -'- r ^ LOOOOOr ^ COOOOOOOOOr'-CNr — ΙΟ J 2 s _3___

Π ^ OJ \ J

8 y Oi) .....— <-n OLOpHOOO OOOOOOCOCOCNOOO

ίι ^ -ζΎ- 1 ——--

Jg ^ Y '/ _η LO CO O O O O oooooooooooo tr> 0) j «• rt ^ I j j, j σι f' t 'id to cm Ien cd cd cm o o en oo co cm o oi 2 ° J * ----

•B

ti Sc-'i'-oocncocoo en en en cm o • 5 _Ξ ___ • 2 jy ^ Γ'-γ ^ ι-οοοοοοοοοοοοοογ'Γμομοο

C

CU -J) j3 CM CD CO (O c ^ CO CM CD OO CO Γ '(O CM ID OO CD CO

V .MC'HLOCMrHOOiHLDCMHOOrHLOCNHOO

Q? \ R \ fc r λ λ r a r> a (\ r \ r r> n a y \ ^ e • P g lOOOOOrHOOOOOi — looooo t "H | CO | sh lo tC rs

e. ^ K O tC

§> r «M t CO

f VV

g _____ 1 § g 8 ci * · m aT ~ co o S j v ‘d -d 0J L I s” f ΐ | ps i § k s

"H te 'o CO -H

V W ö rcq O CO

I W I W I w 18 67209

LO lO CM O O O

<5 CQ

en tn ro · - ----- rH f /} ooooooooooooooooo 0 ^ S ^ oooooooooooo ooo

+ J

ro ----

•B

S § ^ • '^ • fHOOO ooooooooooo

> 1 H

fil CO LO LO LO

3 Ol ° ** <^ ** OOOOOOCNOOOO

cg 4j 3 H rH o o

1 V

I — i pL | CD CD CD CD CD [--- CDCDCDCDCDr'-CDCDCDCDUJ

«J -HO

H> ---- Q) irt ro E (V cn σι σι σι cn · cncnocncncDcncncncnco ‘5 O co # ---- r-

§ -gCnCDCO-OOLOCDCDCDCOOOOCDCDCOHO

JÖ <D oo r-

y _ m η300 00 ·· γ-10O-tOOOOOOC- ^ CNCNIOO

p S ___ O. + J .-. ° 1 oo oo ^ 2 5i ►r S · oo co oo o coaor-cMOOoocococxio * 9 Ärt h 00 oo cm £ * -> ____ O (5, ^ \ / o Ä nJ 't * / _ \ en ω j · «oo ooooooooooo

3 $ + * jJj / \ 2 rHO

t J. // ™

Ju H V ·. J CO LO · rH O O O OOOOOOCOOOOO

H 0) / K oj ϋ / ---- • H oo co o

cn, -o M> ooco · ν · o) omooo (dmdcnH

g ^ P_ oo_LO rH___ • H oo oo ro + J o · »oo · oo o en o o o enenenoo C g CD CO J-

•B

• H lo

> (jjCO.CMCM.OCMOOOOOCDOOOO

Sh co cm δ ajj rt W £ £ CM U3 to (β f '(O M to CO (i) [ΌΟ N CO CD [ΌΟ

M M \ HiDNHOO Hme ^ HOOHNHOO

Ί3 aä M .......

gXrHOOOOOrHOOOOOr-HOOOO

Irt LO

E M K

H CM CM CM

e> Vuo

g III

Ό ---: --- I i Ή "ra 'e— o

«K 00 CO g rH

^ _CM 00 CO Ä J2 rv Ό

►C S Ή | 2 oo X

cT I V- 6 δ δ ρΓ 2 -S S -S

v a v a γ a 19 67209 os

53 CQ

m co W ------ α>.

H jHOOOOOO ^ 'OOOOG-'100OOa H CO "O__O_ S O o

Ooooooo ^ oooocoooooo CO ---- • H is 33 Zoooooo * '^ 0o oo hl * ci □ 1 ci o, A, O co r — ii — r>) ____ Λ 53 oooooo-r ^ c-- _ 3 o ^^^ ooorHooooa ^ -HS cn oo

O TO

G dj lo lo lo i-OrH c ~ · c '' H U <cn cd cd «>»> «cn σ> cd cd« «ο m σι oi *", jU -HCD r-cCrH co co f "cd

> H En lo lo lo CT) CD CN | C/O

JB g PS «ΓαΓαΓ ^ ® J3 —---- lhlo os γίο ω co C"

G • ζσισισ ^ '' '' a ma> '' '' '' rcncn''cor'T

<D ffl jiO co co id 4 co (4 / —NC - -.. I. «. II ...!. - · ιι.ι .. ... ...! ~ —- Mi '- - S i lolo nioaiNH t '_

p J .- £> cn / m ooc ^ -LocotHr ^ LOO

P Ö -------

w P fS * Cis. _ i LO LO LO LO OO LO CO CT) 00 t "CO

3 Fri * 2 r ~ - «n« L λ ro O «·>" Λ »> '00" ID * 1 — t o

g "Q p 1 CO rl o coaor-cocoot ^ CM

Q Ä. fJN \ _ / co lo r- t ~ - -¾ .53 1 /. \ CD O O O O O O Λ ·> ·> o O O. H -o o o o

A f i, / \ £ J-Csio O I

'ä \\ V “^ ooooo o o o o CM o o o o oi, 53 rH) -> Q J 00 H OJ f« ^

tj -T- ΓΡ. [ö ΜΛΗΟΟΟΟ γΙ co LO

• H fsj .n «ΌΟΟ« '. • »» «[' F -H o O

M q cocominwH® ϊ 33 _El____1

LT) LO LO LO J f — 1 CO CO

£ 3 p'1-10000 ^ vvc: 0 ^ 000 • S J = l! ___

0 LO

• H „OCOJd-OOLO

H 00r ^ r-LOCTJrH LOCO

_ SJ -jp [5 CM U3 00 (D CO CM (D 00 [M f 'O (N ID to o- m

Xi .y-GrHLOCM ^ OOrHLOCNrHOOr-11LOCMrHOO

** ö λ n rv fc n r> rv rt rv r rt rv rv rv rv r

-p g ^ rHOOCDOOrHOOOOOiHOOOOO

3 n ---- 5 b ™ CO nj ° | »Δ δ? ? o

£ -¾ -H

g ---: --- ω ^ 3 aj 0) w 1 § 1 d a 3 11 ^ w _, ΟΜ ν.ΗΌΛί

• H ^ * H Ί5 m MO

-k vo 5 ω S Ä • H | M K M I f-ι lo

I H N C CT) CD HM

«" G o | k e li ci h v; Ξ j · -H o cn

rJ r ™ -H K · Η O CO H

Ä υ ω o ω Ί W

I W I W -k -k K K -x -: c 20 6 7 2 0 9 - - - ------- - - · - '"- -1 n · j. -. - - CD co o o o o

<5 CQ

to 00 CO -------------- - - Q) 1

rH

H J / 3OOOOOO CN OJ o ooc o o o o __ H § billion ooc o o o o o to ----- T1 ^ oo c ^ * r ^

ϋ F) *> rt ~ o O LO CD CD CXDC rH CD CD CD CD CD

W CM CN H H

· * Rrj oo oo oo 3 ηΛΠΗ "" "o) nno ooc oo cm ιΗ o o o o CO 4_ * S Ο Ο Ό 3 -rH ----

8 CO

H l ·. σι σ) σι σι σι "cncncnm cncncr σι ohjuo r- to cm V · Η CD 00 H> ---- - H CO ^ 8 ^ ρ / σισισισισι οσισισισι σχησ1 en cr> en t— r— o cm • H o co fi ----- c cd oo

S <j «^ rv rv CT> CT) CD CD CT> CT) C CD CD CD CO i—! O

c3 en en en co r- oo J I o γη _ joo oo "m» o oooiioin cnioc co co co h H o o Ä S δ L> -—-----

^ P C * CO OO CO CO

3 2 —Τ '* a "" OO "CO« CD Γ 00 CD O e 00 Γ- CO LD CO H H

z K G co co t— rH

CM ^ 2 ---- Q A \ / t— co co co

jZ tö * 7 “/ 'Λ rn" "CD CM" "CD O- O O OOC CO H O O O O O

2 -P J, / \ 3? t— .a- oo * 3 S »/) c ^ Γιο rH V_J rn cd" "· ό o cd e o o ooc en o o o o o o f-4 4) f βζ j cm o • H 2L. to to r- tn o l_i "coco" e— «σι en σι co cocnc en e— e— cd rl o o g ° _a« oo_t- h___ • H ld

+ J D CO CD OO (D "rH CDCDCDCDcO CDCOOOOOO

5 * ____ o • rt Γ— r- t— co

> fJ "" "" Or-ICncOCD OOC CO CD OM CM O O O

L · CO C— C— CD LO

S aO iti

to LXjCNCDOOt— C— COCMCMCDCO C — Γ — CT CM CM CD OO C— C— CO

Jk 90 - ^ HlOCMHOO "H CD CM HOC" H o CM H O O

P M r λ λ r λ j— {«v <\ n λ ä v r — j n rt n rt« n rt 2'— IOOOOO HHOO oo e hhooooo t "H | · Η |

I I CO

Γ— Γ- JC

£ ^ * co V

s o o

Q I I

? ω

5 ^ to CO

S § 2 CD § ID

• r) in H CM H CM H

cv! öc cm H nr *

* ~ -H Ö -H S -H

3 "| different s" 1

of ‘g I s 1 s I

I W I W I w 21 i 67209

B

S g to --- 0) 3 ^ o o o o o o

O

$ Poooooo • μ ra —_

•B

2 o cd cd cd cd o f, _____ a

5 qCDOOOOOO

ra μ 3 3 · μ-- O · γ ~) C ® οωωσισισιω <»-H U> H> - £ ^ pj cncnoimwoito f ^ -— S gj cncncDCDcofjDCsi / ^. 2 ——— S ΊΟΙΟΟΓ ^ ΟόΟΟΟ # & a:> Ώ S Ö--

• n <M O

n- '-3 O cn cncnoooocvjoo

"2 ^ S P

0 t K ~ W ---- 1 RK / h * -—— iö rH V_J rn 0) 000000 ^ «/ _« _ .¾ 2 ra i_i en o> en oi cm <no 2 ° -si- • rl «Μ en o cm ooo • S _E_

• S

> JaJCOCsIOOOOO

h en S sfl nj ra ί ji (NtNiDcoM ^ n

M; f3 "i-IlOCNIi-100

P 3d Mrl "1 '*' '' 11 'jJ 2. ^^ 1-100000

TLO

> 4 <M

j? i 00

ίν ^ ~ CnI H

δ -h

/ —N V

en 2 § 1 ci ac -h oi o ra I w 22 67209

Example 18

Evaluation of the herbicidal effect after treatment after seedling

The efficacy of the herbicide after treatment after seedling emergence is demonstrated by the following experiments in which various monocotyledonous and dicotyledonous plants are treated with test compounds dispersed in aqueous acetone mixtures. By seeding, planted plants are grown in flat baskets for about 2 weeks in experiments. The test compounds are dispersed in acetone / water mixtures (50/50) containing 0.5% of polyoxyethylene sorbitan monolaurate surfactant in sufficient quantity to give about 11.2 kg of active substance per hectare after treatment of the plants through a spray nozzle which operates at a pressure of 275 kPa for a predetermined time. After spraying, the plants are placed on greenhouse benches and treated in the usual way by methods commonly used in greenhouses. Plants are examined and evaluated 4-13 weeks after treatment according to the evaluation system shown below. The values obtained are given in the table below.

Evaluation system: Growth difference compared to control,% *) 0 - no effect 0 1 - possible effect 1-10 2 - weak effect 11-25 3 - mild effect 26 - 40 5 - clear effect 41 - 60 6 - herbicidal effect 61 - 75 7 - good herbicidal effect 76 - 90 8 - almost complete destructive effect 91 - 99 9 - complete destructive effect 100 4 - abnormal growth, that is, a certain physiological malformation but the overall effect is less than in point 5 of the rating scale.

Based on visual determination of plant position, size, strength, color whitening, growth abnormality and overall appearance.

67209 2'3

Abbreviations of plant names: SE - Sesbania (Sesbania exaltata) MU - Mustard (Brassica kaber) PI - Amaranth (Amaranthus retroflexus) RW - Ambrosia (Ambrosia artemisiifolia) MG - Morningglory (Ipomoea purpurea) BA - Grasshopper (Echinochloa crusgus crusgus) (Digitaria sanguinalis) F0 - Green headland (Setaria viridis) W0 - Wild oat (Avena fatua) TW - Blackberry (Sida spinosa) VL - Velvet leaf (Abutilon theophrasti).

24 „67209

O

IS OT

O

P-t oo I pe: • H O cd

(ti P

„<Ro CQ oo CO________

C/O

0) S

G H j-

P

Λ ----- πi p pj (¾ -H> oo rd · η__

P tO

H U

£ PS * · >>> __

i — I CO

Q) iti S

P X M o

P • H

CO H

: rrf Cd cm Λί__

• H D

P S ot G ____ OO · Η

O W

O -H tn j- ^> & ----- ------ ---- -...........

d <ti -h H Pi G G rti iti CU iti fn CO p

M rC

G »ti <U

P P ^ cg G: r0 \ ~

MG: rti bO rH

• H CU Σ5 M i — f cd Q)

> M

Po i — I

M »ti-- M · Γ-> CM ro d, ^ cc S 3 ^ ° c ^ Cl5

g g v CM O CM

o co cu os M

MG p ^ / 0 O o CO K l / G G -H 9 y = \ ro

Pc Ό i / \ rd 13 s K / - • H CU> - pr: fi 55

CM

o e • H · co O oo

W S H

25 6 7 2 0 9

Examples 19-30

Evaluation of the herbicidal effect after treatment after seedling emergence

Following the procedure of Example 1¾ above, the herbicidal activity of the compounds shown in the table below was evaluated after treatment after emergence on the seedling with the following results.

26 6 7 2 0 9 ^ ooooooooo

CQ

m ^ ^ c-'C'-lococoococoo I — 1 11 '' '---------' - -__ -. - - -----------

2 & ^ LOLOrOrHi — IlOlOlO

so • H ".......... - --'ll .... ............. - ...» ------- ^ ooooooooo rt ΟΓ- ^ ο ^^ γ-, η, οοοοοοο 3 LO LO LO __

C "LO ^ O LO COCOCMOOOCMrrtO

3 _ __ CiJ _____ _____________ Ό -rt C '· ^ o ”tn to r'-c ^ r-'t ^ -ooc ^ oo

|! ll Pj O LO

rt · ο o p, rt ----------------— rt H <

-μ · Η tQo-LOLOLOLOCOt ^ LDCOOOt- ^ LOO

C ω ------------->, rt »H ^ h lo ~ rt ___ ZL ——__________

^ ["LO LO LO LO CmlOCOCOlOlOLOCOLO

• rt E-c lo co ro: rt X ---------—-

^ X P U ^ LOLOLOLOlOLOIOLOLOCMLOlOlO

O -rt CM CM LO

X -H O X -------------

Λ! G rt <M 'Z O CD

rt * rt CO Ph X / Ph (—i rrt O CO I> T \ rt -rt rt s / \ r—

rt> H X— <x /> -> H M d- LO ^ LO LO

H s 3 __rt______

e e S5 P

S! —Τ'1 rt- CO LO LO LO CO 00 00 00 CO COlOOO

CO rt o X -H -: --------- rt co w

^ ^ LO LO LO

rt τ> ------------ ^ LO 00 LO 00 LO 00 * rt · ^ "P '| 2cmcmcmcmcmcmlocmc \ ilocmcmlocn * 0 H cl #n λ # \ λ CLcv # s * Nr» r \ #% r> r »

·> 10 ^^ .HHHHHrrtOOHOOrHOO

S ^ rrtHrrtrrtHH rrt rrt

rX «Si-I

>: e 1 ---—--------

Ci 0)

>, <D

β Λ! O rrt X = rt O -n -rt | * Rt | rt i i

CjC s r ^ r ^ LO lo lo lo 3 3 »H“ e ^

S3 S Y Y Y Y γ Y Y Y

• HO G -----: ------ 05 C S f1 -rt | | f aT e f «e-, 00 K e-

E ϋ O m X

CO rt I r- \ O CM CO., LTD

O -rt m n o Λ O

<N r-N I 1 X CO LO r-V

Ph co t "en ö X X · Η I oo

S X X M / G CM I X

CO d- x My o ö M-r O O Ό X My X w

S 1 1 v 7 S o ”S

____I__35__35__35__35__X___L___I__ * &

• S en O i — I CM CO LO CO

jVJ i — I CM CM CM CM CM CM CM

27 67209

M

Pioooooooooooooto o o α> ______

r-i CO

i — I C / ϋ α> is — δδ — TS — ts — tttj — rs — rs — rs — o g g> H cd o o o o

• H CO '00 CN CO i-H

O o * cm H q ““ S ^ ^ °° lÖT ~ cö in P Ϊ3 cb o O m in m ί ro OJ ---- en 2

0) qOOOOOOOOOOOOOOOO

QO - 1 tji '......— 3 oooooo .oooooooooo

μ 3 rH

"S" ΐ7 oo rH rH O O CN "co LO CM rH O O O O

0 * TD mn 'h μ μ “K" cm cm uo m ~ F ^ iö cö i = | oo • H o ^ tH OOO 00 c «I — j ___ CP: U? _Ci._ ^ ^ ^ ooooo ^^ coooHe ^ cocMooo d) · Η CQ CD d- μ> ______: _ xj rn

. Jlj ^ jLOCOCMrHOOOCMtP-COCOCOCOLnCNOO

^ w Ai C> CO LO

nj: ixJ co_____ o il cc

CJ 2: CO iHOOOoOUOOOCOlOCOCOOOOO

μ · Α ^ E-1 t'-cO ^ i-LO

[rj + J CM CM Γ-CO ^ rLO

• no; O td ----

ν_ ^ · Η S O CJ3c300000000 <OrHOCOOOOOO

d- -H θΓ V— / __ ^ __

Ai rt § — y N

3 n \ J _____

I-1 Q) / HH

3 ω 'O.

rt Ai ^

En 3 CM ----

_p O j-jOOOOOlOCOCOCOlOCMOOOOO

S OO 00 r ~ - CM

* H ________ - - - -----------— ““ rt w> co>) _____

Oh____

Ai C ad rt

^ ^ 'CMcooocor'CMcooocor ^ cMcoaocor'-co g * S "5? Br- | L0CMr-) CDrHL0CMrHOi-HLnCMr- | OO

K «(g CmJ r> r \ r r # ·» r

O I-H SAir-tOOOOrHOOOOr-IOOOOO

x ITÖ --------- O -n 3 μ a <d 3

Ai w

Ai 3

fd 2 ^ CO CO CO

E g g | Ύ i i

^ CN

• h | n; 0 "ai CM J CM en

cd t- O I

rri V- * σ>

oo rd K

I V_I_ „j £ _ £ • H Γ-- OO CT)

tn CM CM CM

W

4 28 67209 a «

C/O

• H ΊΓ n3 --- ^ o <d u CO ------

CO S

<U G

M § Ä S co rd --- A Cm d- nJ tl ω ^ ^ ~ 7- ^ <d «G rH O d" >> -H__ i I S '^ + J ___ <d Ή ° ω e.

Ai sd> J- -M .X J10 ---- rd K s • n * H ^. [G J-

v_, 4_) CN O

Γ · O CM-- * -H Z K M, 5 * f LJ -—

I S § ~ ö ~ * S J

H f S »

Sί S

3 CM -

+ j ° S

3 “* · λ: g • H Q) -

(3 CU W

> Ai CO d ·

l> i H

A! : rd ---

Ai -n G: gj rä> i G g id cm £ 3 ra "m. *> O« g »d rG 3 ^ ^ 1-1

O O

3 G O

G?

rd 0> H

Ai 1H -rH I -3 ϋ H l '5

• H U) Cm t - CO

«E w B

o * g 's g__Jj

(3 <M

To S

CC Td cm 3 CM 8 £ * S 7 —L ---— | 4 | ύ ° -: c fl 67209 29

To demonstrate the advantageous properties of the compounds of the present invention over prior art compounds, comparative use experiments were also performed using compounds known from U.S. Pat. Nos. 3,332,769 and 3,764,624.

Comparative experiments: Evaluation of the herbicidal effect after treatment before germination

Seeds of monocotyledonous and dicotyledonous plants were planted in small plastic pots to a depth of about 1.2 cm, and test compounds were sprayed on top as a solution. Spraying was carried out on dry soil through nozzles designed so that the amount of solution to be sprayed per hectare was 804 liters and the amount of test compound per hectare was 0.017 to 4.48 kg. After treatment, the pots were marked, transferred to a greenhouse and watered. Three weeks after treatment, results were evaluated using the same system described on page 21.

The results are shown in Table 5. The experimental plants and their abbreviations were the same as in the list on page 21, and in addition the following experimental plants were used: LA - Chenopodium album W0 = wild oats (Avena Fatua) SB = sugar beet (Beta vulgaris) 30 6 720 9 - Γ -— i -: -'-- (fl iCM C oc cl c ^ jcsioccro co; -k & OOoC'C o ° ° 5 -K °

8 ooocc ooocco • H

. --------------

o a °° o ° cc CO O oc c O

• HO) Ö> LO .______

(M

Goo SrOi-IrHCCOOCMCSICCO

0) CO * -K 4C

CO _____________ V CO t-T. U1 pro 8 cn cn co cr c cnoocr> i> j-Ln aS ________ ill— rd 3 lt tco • H ^ (J) CD [N t £ c cn cn cp OC CO c gj —-------- ----- S "H-1 ^ 1-0 Q'H Stooooocococncn · 4-> CU 03 00 Γ'- P- 0 + -> -s * 3 C ___ _________ § fj ------- 3 Ä S CNOCCC ιΟ ^ ΗΟΟΟ H Ip ^ w * K ic

£ - (CO -P

CD Irt ---------- δ id S 04

Opp § [S3 ^ coococcoLocvjrHocD

• r | CO h *. » v »* ♦> a> 3 S \, * y ^ \ ^ ---------- SM t U s cd co on oca ^ co ^ cncoo i — I CO f ·" sll ~ ^ QP cd tn O ^ Lncor-occnt ^ cocooo cn p · η w -s * * 5 3 cS - _ 3 | g ^ 1ϋ'- c ^ hoc ρ - '^ μοοο ^ ¾¾ * - 1 y4 - ^ ·· * Η »> 1 ·>

l || J,, I

sm I

> CM _____ CD C CD _ ° Q) ί ^ «3 M OI ^ LD o (¾ SI 34 3 h3‘> § ”

/ B I

U

c cn cn a) (U CD co Ό p a. r- & (m jz ω w co | d

• H S CM CM .X

Ό co co, £ CO co -5 = co co 67209 31 1 I I I I <si r ~~ 'a CM o o o o o • 8 18 18 18 -8 "" ”- - - - -

CO tS, r-i O O O

CO .¾ 1 '8 "- - - - m coooo ooooooo co .j-« «« «g« e: -se <8 —— - - - - - ^

O

O coooo ooooooo * 8 -8 18 1 «« · Κ «1 ___’ 1 - - - - ιλ ro cm δ CSOOOO ΓΟΗΟΟΟΟΟ • 8 -8 · «-1 <« · «-8 18 -8 18 ___

10 tO 04 CO

§C f — I O O o CNrHOOOOO

-8 «« <i -8 18 '8 1 -K

“LO l0 ro ro —— - -j. to SO) C '' to 4- Η Ο σ1 cn 03 CD CO O o C1 ~ lO r — t o * 8 1 «1K 1« K «8 18 18 18 1 • CO 03 -3"

Ph CT CD (D CO to O 03 03 CD CD CO CO 10 03 03 Γ “- CM

CJ -8-8-8-8 <s «se <4e -ec« ee -s «

'LO f--. CO LO CM tD

<! σ r ^ · CO UD O 03 03 CO 00 f -> - t-O O r- rH C O

CO 18 -8 -8 18 18 · «-8 18 ·« -¾ uo ^ ro σι ^ Μ Ο Η Ο ΟΟΜΛ ^ ΟΟΟ> 18 · «18 · κ -t! · Κ -8 -8 -8 Ä ^ CO n tD CO 00 3 CO OD J oo o o H -8 ·! Β -8 -8 -8 -8 csj "” “^ 5 7h To 7ö ^ o ....

3 2 M CD croooo d-CMOoooo g K / X 1 -8 -8 18 18 · «-8 -8 4, N / - s 1 \ JT1 —________ illllll_____ LO LOLO LO C ^ d-OcO ^ · OZM co tv lo j- cm co co lo to ho ^ CM O. -8 -8 -8 1 -8-8-8-8-8-8 § o ______________——--- £ 2 r— rj- cm cd

^ S CO CO MO H O

<-8 «18 -8 -8 <8 H,, ------------------« "• J co ώ J ^ • 8 -8 18» 8

to 03 lO

W p-. = J- CM rH O O O

C / J -8-8-8-8-8-8 __,. - —— ^ uO ”——— - 30 5 Csl L £> CO t> - CM (Ό CO ^ [- CO H (N LO CO ί HÄ CM rH LO CM rH O i — I LO CM rH OOOHU) CM rl wj bp cm i — iooooi — ioo, oooo r-loo1z> «= f

CM

δ ___I___ en co co s. K x x * n Ö o o i i _____! _

"CM

CM CM CJ

r-s / —v I

LO LO

E X ® o 'cm cm m w o υ o? ? 5

03 CD

LO iO CO., LTD

^ ^ 8 tn O. CM rH / O-H O1 cm .Lm co co rH> (Q CO co X 2CO => co CD «H 0) £ oo w oa; _ 67209 32 a1 I o, |, = | r --- στ ------ j $ rr rH o c o co co co o o UJ h; hi He He w οοοοαο λ-οοι ooooooo _-__ iL. it- Ä. jSL Jt__Jii - 4t__JJL. Λ ______ R o oooao 0 0 0 3 o o ooooo ^ «« «« «Ηβ Ηβ Ηβ HC« ί «

lO lO i_Q

5 0 i-Η O O O O H MOD O O COOOOO

• tC * * K_ 4C__JLjSLli__He______

LO

So rH O o O O iHOOO O O CMOOOO

• X ►: «* X« R «55» X -X «Hi______

^ CD in UO UD LO LO -O

P * OI UD Csi O O O CD cn. CD ^ CO CD CO CD r- o ^ cd «X * x He ne I He hc hc: c hc He He [ne« *

ΙΛ CM CO CO -D

^ cn co co ω j- H h cncncnj) on co σι σ> cn σ> d __A iL. £ - &. 3L. t -a. 3 £ - K— A. & __ H6-tfS.a, a-.

^ cs <CM /> in lo

^ CD Xl M- LO CSJ O O CTJ CH CO UD lO CO 00 Γ "- Γ- O

___: iL £. 3 ___ a-ja-s ^ Jg_4c ___ fo-fo fe-g- lo tn fcj lirHOOO CO Ο ΓΟ Η Ο Ο ΓΟΟΟΟΟ ne -x He · »hc« κ h «He κ Ηβ Ηβ m lo n in § oo c ^» n rS o ~ _______ | «K -'A« see y «x« X_____

lD LO

^ OOOOO iHrHoboOuOOOOO

^ ^ -_ - - -g - * t- «B - ie --- ie. it. ·. * ft .. ______ S ^

Jxi O I O o o O I — 1 O O O O O

P g Ht -X ne s He Ht

• I—> ~~ 1 fsi W CP I ~ lo ίο ”~ - T

M »/ I | · · · F I · *

n 07 CO O co O O 100''-HOOCOf ^ LO-OO

lo ^ HeseHCHeHe | HeHeHece <eHe

O <LO LO LO J

2? COIDOOCliOoooboO

qj * - | He He He> x ne 3 - - - - - H ^ co co j o o oor ^ r ^ r ^ o * - * -k: e tt ne ne

LO LO

W lo -n o o o o - -. _______ μκ __ ^ _ äS__ijj ______ Φ JÖ co j-> j (£ (Xd-pv (M xxj-rs. co ί m ω ω ί

CM -H m O H O rH LO CM H O O M H 07 MH

® 7 J M H O QO O H! O O O O O CM rH O O O

-——-- Ί i j i- 4 --— LXj—

C/O

M X i l K

__! ? CO i CO co

X ^ | S S

»| y I co I, ω I -Hl

rs CD CD H- I

05 a: X a; .d "oo V o o! _ 1 __! -! - 1 s» s ft n x * g ^

a i dll | S I

J_ \ 2! a-as "! 67209 33 3 οοοσοσοοοοο en co o o o o o o o _______________________ o o o o o o oooooooo oo o o o o o o o o

00 ^ ft £;: · £ 46 -K 4C 4c 46 46 46 -K

o o n o o o o o o o o o o i o ι o o o o o o α a o O .¾ κ -k »« 4 * 46 4e 46 48 ”-. - - - - - - - - ^ 2

O OO O O O O rJ-r-H OOOOCN MO O O o O OOOO

ft 46 48 U 46__48 46 4? _ 46 ^ 4 £ _ H6 ft 46 ft ___ __ ___

"LO

§ OO OOOO O CM M OOMOO OO O - ^ 4 «« 48 · :; 46 ft ft ft ft ____ to lo lo ln O cd en en h co H cd co cooocdo id j hot <d <d co oco

Ua 45 * 46 46 Vi 46 46 46 46 48 45 46 45 46 4 «46

lOlOlO lOlOlO lOlOlO

qC, ... ... ...

O cd cd en r-- <x> o σ> en co cd h en en cd cd h · iocd ot σι r- * id cm □ _ 46 46 46 46 k 46__Ä-j ^ - Ä ----- -----

lO iO O LO LO LO LO

^ CD CD CD J- O O CO CO h o CD OT CO LO CM O CD CD CD Γ "" OMOO

_ 46 46_46_ 46 K6 4; __ 46_ Ä_46_ 46 __ <46 46 46 46____ L -_ __

lO lO lO lD

· · ·· ro oo oooo

> CM H OOOO 003 OOlO ^ TO oo V

__46 46 46 4C 4: 4: __ £ _ iL · - £ -. £. .46 - * - —--------

to LO lO

M r- oo M o o o oor-oiior ^ r ^ ooooo

to I

o

O O OOOO OHD OOOO] 0 oo OOO O OOOO

^ 46 46 K 46 46_ * _ .'6 4C 46 46 ft ft 46 <6 46 j________

1 s ~ "·’! I

to | * * 16 * ** _._____ * T * y - jSLk-J £ -—L ----- r-

lOlO lO lO O lO lO

, - 3 uD J CM O coao> · J3- mo Cote LO ι — I O O £ - «· 3 ο I I OO

“-0 -5i.; J ► :? -: c 46 46 ft 45 46 U 46 46 46 46 46 46 _ _ .___ 8 a lo i 2 rHr-Hoooo oil ωι ω ο qoooo oo ^ _. * _ * - * - * _: «- * - -: -------------- in [2i oo t ~ - ro, -toj _________ * I ·:. · I___________

LD

m CO r-l O O O O OOOO OOCOCNO OOOO

· :; -K * * _ «__ * ________ L — l _____ j ----- in i! I m ιο cm.

adiö cm ictoJ- · 'ro a- cm ioooii-CM: o co> a} - | tMco cn ιο a) [a; g J H

G χ (H inpj rI: 3 O CM H LOCMHr-iiO CMr — l oo rjjIM | H OOO

IQ | r-H 0 (003 O CM ^ OOO r- ^ O O ~ Q | O O Hj O O; '0,0 <Q O

ro co

δ S

NO _ O χ N K N Ö j s s? ι__J__t

-r ---- 1 __— “I I

CO {. ffi o ^ S δ V i __J _! _ ι ---—-- ei cl ail Οί -H | C r I S CM% r ~ ro x tr X nO co ro p—

d ”δ ~ δ δ-δ V

ι ι ^ _ι __’__

--ϋ σϊ * D

0) _ -Μ Ο _ -H io

+ J ati e N »d C

C /> M (Q · Η C3m Μ ίΟ «H Ρ-»> <- '• r4M> cn CO OJ M> W W S'

Q-rlcuX Dm τι Cji D> {S I

iSwMOJ co ω Μ φ W ΟΛί W OX co 5 ___ ro ί I —----- i 67209 34 nrPTiTmrrmTXiirari ____Q_j_ _j___ ΓΠ __________ * IT! i I L Γ tλ wo * opoop cooopob ooooooo L: tT -----

U o o o o o ota o o ορ o o o ooooooo Z

Oooooooo ooooooo ooooooo o hi oi ffi 5i mi λ n m ®> ό a o onaocooooo «

U (Pi (Tl (71 _71 71 C71 (71 ((ι (Τι (Ν Ο ΟΙ Λ Ji ΙΛ NC O

cS o \ m Τι τι ti (oio omcn ^ ir'r-'O m »so rn ooo ----------------! --------- ►3 > 00ΌΓΜΟΟΟΟ ΓΜΟΟΟΟΟΟ OOOOOOO Si cocoiomooo Γ ~ tN Ο Ο Ο Ο Ο ΓΜΟΟΟΟΟΟ o

X ooooooo OOOOOOO OOOOOOO

/ • —I ..-- I - - - - - - - - - “- -

I S I

p K OOOOOOO OOOOOOO OOOOOlOO

ό ____________________: _______ n? G <r ^ w> vnr ** oo | 0 tv r- * o *. oto o 1100 * 10 0 1 iTT-t + lL ---------- £ 1 — H --- i --------- P ------- Ρ ω

W INOOOOOO (MOOOOOO OOOOOOO

<8 mr · ini'- j 1/1 i— (PiC NDM if (5 r- ((N iD (O if> | m -H C'i <X1 Vx> Tf Γ * ΓΟ.-4 Λ \ H / 1 N Η Ο Ο Ο ΗΛΓΙΜΟΟΟ ΗΙΛΙΝΗΟΟΟ gj ^.-Llolooloiolo —I) Q jo O | o> QPH ololo oooaman

K CJ K

n y ο υ 0 rn o • St υ ___I_____ t ^ nn> <33 M tfi v I y__v

(OF

in aa r1 v

K u V V

^ K X

San ______V__V______v 01 «O μ S. g • H cm ^ r-i> cd & j · «· • d w Ό Ti 4) JZ no S 0 * 31 o- ______M______________