DE2007160A1 - Biologically effective benzothiadiazoles - Google Patents

Description

DIpMnQ. Horst Auer aoooH * MBURai, August 17, 1970 Patent attorney TeWom 838221 Telegraph: 2-181587 ■ dpu d

P -20 07 16.0 * 7--. My file: PHN 3739

N. V. Philips'Gloeilampenfätirieken, E'indhoven / Hpllarid

Biologically active benzothiadiazoles

It would be found that compounds of general, Formol

jv \ der "," _, .- "■." ^ represents the group -OCHCOOR, ..obQi R. is a hydrogen atom or an alkyl group with up to 3 carbon atoms. "and R is a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms ,

000882/2201

£ *. '■■■ ■ / ■ ■ -2-. .; ■■ .. · -: ΐ "Wn% Τ39

Y is a chlorine atom or a bromine atom and Z is a hydrogen atom or a lower alkyl group represents and

η is equal to 0, 1, 2 or 3,

v "have a strong biological effect on plants. It has been found that these substances influence the growth and development of plants to a considerable extent and also induce significant changes in the properties of plants.

The deviations in the development and condition of _: Plants are very different and also show differences depending on the substance used and the plant species treated. The dosage also influences the type of deviation caused.

Within the above group of compounds of biological W efficacy were found on plants, for example, the following aspects »

Selective herbicidal action, including leaf burn;

Induction of morphogenetic deviations, such as leaf deformations, (e.g. funnel-shaped leaves, urn-shaped Leaves), leaf adhesions (reduced formation of parenchyma, thickening and increase in number the scars from collenchyma accumulation), changes in flowers (rudimentary flower formation, continued growth of the flower), Epinasty, fascination, connation (growing together) and changes in the root system (root space thickening,

009882/2201

-3- PHN.3739

changed sprout formation, stimulated root! branching, ' Induction of new roots, change of the mean root length),

Sterilization effects (formation of sterile seeds, reduction in semen production),

induction of parthenocarpic fruits (such as formation of seedless tomatoes),

Changes in the water balance (e.g. promoting leaf transpiration),

Changes in the rate of aging of plants (antisenescence effects) and

Changes in chlorophyll formation, e.g. Intensification of the green plant color result.

From this list of the active ingredients according to the invention brought about biological effects that is by no means to be regarded as complete, it emerges that the range of action of the active ingredients is almost unlimited and creates many possible uses.

This great variety of biological effects, which, moreover, as noted above, is different for each compound and each species of plant treated make an accurate estimate of the biological Effects of the individual compounds according to the invention. However, it is characteristic of the substances according to the invention, that they, after ingestion into the plant and transport within of the plant act selectively on the active vegetation centers, e.g. on the tissues suitable for division

009882/2201

-h- PHN.3739

and thereby cause a change in organ formation, tissue formation and cell division.

Furthermore, due to the deviations found in the formation of chlorophyll, the formation of seedless fruits, the water balance and the rate of aging Compounds according to the invention can also have a hormonal effect.

From the biological investigation that led to the invention, it was found that in particular the compounds the general formula

II

in the

X represents a _{-OCH 2} COOR group present in the h or 5-position of the ring system, in which R is a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms, Y is a chlorine atom and

η is 0, 1, 2 or 3,

have a strong biological effectiveness.

In particular, it has been found that the groups of compounds mentioned below are very interesting hormonal and have growth regulating properties: I compounds of the formula

009882/2201

-5- PHN. 3739

III

in the

R is a hydrogen atom or an ethyl group and

Y is a hydrogen atom, a chlorine atom in 5-> 6- or 7-position of the ring system, two chi or atoms in 5- and 6- or 5- and 7-positions of the ring system or three chlorine atoms represents in 5- »6- and 7-position of the ring system.

II compounds of the formula

ROOCH ₂ C

in the .

R is a hydrogen atom or an ethyl group and Y is a hydrogen atom, a chlorine atom in h-, 6- or 7-position of the ring system, two chlorine atoms in k- and 6- or k- and 7-position of the ring system or three chlorine atoms in ki- , 6- and 7-position of the ring system.

III. Compounds of the formula

OCH ₂ COOR

Cl
in the

. -6- PHN.3739

· R is a hydrogen atom or an alkyl group of 1 to 10 Carbon atoms, is. '

■■ Can also be mentioned because of their strong effectiveness

will:

4- (ethoxycarbohylmethoxy) -5i7-dichloro-2 _f 1 _f 3-benzthiadiazole,

Melting point 67.5-68.5 ° C

4 ~ (Hydroxycarbonylmethoxy) -5f7-dichloro-2,1,3-benzthhladiazole,

Melting point 173-17 ° C

4- (ethoxycarbonylmethoxy) -2,1,3-benzthiadiazole,

Melting point 74-75 ° C

4- (ethoxycarbonylmethoxy) -6-chloro-2,1,3-benzthiadiazole,

Melting point 102-103 ° C

4- (ethoxycarbonylmethoxy) -7-chloro.2,1,3-b © nzthiadiazole,

Melting point 103-10 ^ ⁰ C

5- (ethoxycarbonylmethoxy) -2,1,3-benzothiadlazole,

Melting point 108-1O9 ° C

5- (ethoxycarbonylmethoxy) -6-chloro-2,1,3-benzthiadiazole,

Melting point 122-123 ° C 5- (hydroxycarbonylmethoxy) -6-chloro-2,1,3-benzthiadiazole,

Melting point 198-199 ⁰ C.

5- (hydroxycarbonylmethoxy) -7-chloro-2,1,3-benzthiadiazole,

Melting point 192-19 ° C

5- (ethoxycarbonylmethoxy) -7-chloro-2,1,3-benzthiadiazole,

Melting point 1O2-1O3 ° C

k- (i-propoxycarbonylmethoxy) -5,7-dichloro-2,1,3-benzthiadiazole,

Melting point 98-99 ° C

4- (tert. Butoxycarbonylmethoxy) -5 »7-dichloro-2,1,3-benzthiadiazole, Melting point 68-69 ° C

4- (n-Butoxycarbonylmethoxy) -5t7-dichloro-2,1,3-benzthiadiazole,

Melting point 57-58 ° C

009882/2201

-7- PHN.3739

4- (methoxycarbonylmethoxy) -5f 7-dichloro-2, 1,3-benzthiadiazole ',

Melting point ko-h ^ C

k- (octoxycarbonylmethoxy) -5i 7-dichloro - 2 _t 1, 3-benzthiadiazole,

,. Melting point 50-52 ° C

Other active compounds according to the invention are:

^ (e1hoxycarbonylmeöiylmethoxy) -5,7-dichloro-2, 1, 3-benzthiadiazole,

Melting point 62-6h ° C

^ - (Hydroxycarbonylmethoxy) -2,1,3-benzthiadiazole,

Melting point 159-16O ° C

Melting point 1 ° 3-195 ° C

Melting point 210-2-11 ⁰ C

4- (hydroxycarbonylmethoxy) -6-chloro-2,1,3-benzthiadiazole,

Melting point 177-179

h- (Hydroxycarbonylmethoxy) -7-chloro-2,1,3-benzthiadiazole,

Melting point

5- (hydroxycarbonylmethoxy) -2,1,3-benzthiadiazole,

Melting point

5- (hydroxycarbonylmethoxy) -4-chloro-2,1,3-benzthiadiazole,

Melting point 198-20O ⁰ C

5- (ethoxycarbonylmethoxy) -4-chloro-2,1,3-benzthiadiazole, . Melting point 98-99 ° C

5- (ethoxycarbonylmethoxy) -h, 7-dichloro-2,1,3-benzthiadiazole,

Melting point 132-133 ° C

5- (ethoxycarbonylmethoxy) -4,6,7-trichloro-2,1,3-benzthiadiazole,

Melting point 109-110 ° C

5- (hydroxycarbonylmethoxy) -4 ₍ 6,7-trichloro-2,1,3-benzthiadiazole,

Melting point 176-178 ° C

5- (ethoxycarbonylmethoxy) -k, 6-dichloro-2,1,3-benzthiadiazole,

Melting point 74-75 ° C

5- (hydroxycarbonylmethoxy) -4,6-dichloro-2,1,3-benzthiadiazole,

Melting point 215-216 ° C

4- (ethoxycarbonylmethoxy) -5f6,7-trichloro-2,1 »3-benzthiadiazole,

Melting point 125-126 ⁰ C.

009882/2201

-8- PHN. 3739

4- (hydroxycarbonylmethoxy) -5 »6» 7-trichloro-2 _t 1,3-benzthiadiazole,

Melting point 198-2OO ° C

7- (ethoxycarbonylmethoxy) -4,5-dichloro-2,1,3-benzthiadiazole, •. Melting point 124-125 ° C

7- (hydroxycarbonylmethoxy) -4,5-dichloro-2,1,3-benzthiadiazole,

Melting point 2O5-2O6 ° C

4- (octoxycarbonylmethoxy) -5,7-dibromo-2,1,3-benzthiadiazole,

Melting point 64-65 ° C

4- (ethoxycarbonylmethoxy) -5 »7-dibromo-2,1,3-benzthiadiazole,

Melting point 72-73 ° C

ν 4-hydroxycarbonylmethoxy) -5-chloro-2,1,3-benzthiadiazole,

Melting point 199-2OO ° C

4- (hydroxycarbonylmethoxy) -5 »6-dichloro-2,1,3-benzthiadiazole,

Melting point 215-216 ° C

4- (ethoxycarbonylmethoxy) -5 »6-dichloro-2,1,3-benzthiadiazole,

Melting point 76-77 ⁰ C

4- (ethoxycarbonylmethoxy) -5-methyl-7-chloro-2,1,3-benzthiadiazole, Melting point 80-82 ° C

4- (Hydroxycarbonylmethoxy) -5-niethyl-7-chloro-2, 1, 3-benzthiadiazole, Melting point 195-197 ° C

In the biological evaluation study, the compounds according to the invention have been examined using various test methods, a test method often comprising several series of experiments. For example, some of the test methods used and the results obtained are given below: I test for herbicidal activity ;

Crops such as turnips, oats, French beans and tomatoes, as well as various weeds, e.g. chickweed, arable park, small nettle, ragwort, black foxtail, sticky herb, Street grass and knotweed are after emergence of the plants (post-emeTge'nce'-TerwenTiung) with the invention

fr I L- II ··

PHN. 3739

according to active ingredients in a dosage of 10 kg / ha; acts.

In a second series of experiments, seeds of Weed plants (yellow mustard, street grass, chickweed, peach-leaved knotweed and garden cress) with the inventive Compounds, also treated at a dosage of 10 kg / ha (pre-emergence use).

Finally, in a third series of experiments, various aquatic plants such as salvinia and duckweed are used and algae, with the active ingredients in the same dosage of 10 kg / ha treated. The results show that the active ingredients have a selective herbicidal effect on dicotyledonous plants. It has also been found that in the group of dicots exerted a strong selective effect being, with certain plant species by treating with the individual connections seriously and others not or almost not be damaged.

The compounds of the general formula OCH ₂ COOR

in the ,

R is a hydrogen atom or an alkyl group, generally very potent poet emergence herbicidal activity chickweed, arable park, stinging nettle, strasaerigras, Knotweed and turnip on while the herbicidal action

009882/2201

-10- * PHN. 3739

considerably lower on garden cress and black foxtail is. It has also been found that benzothiadiazole derivatives, containing a carboxylic acid ester group, a have a stronger effect than corresponding compounds with a carboxylic acid group.

! ". In particular, it has been found that the benzothiadiazole

derlvate, which in the k- position is an alkoxycarbonylmethoxy-

fc · and have a chlorine atom in the 5- and 7-positions, a very have strong herbicidal activity. The results also show that the "pre-emergence" herbicidal effect considerably less than the "post-emergence" herbicidal effect

is.

II. Test for morpholonetic deviations ;

Various weeds and useful plants, such as the plants listed above under I, were with acetone Solutions of the active ingredients in doses of 0.5 - 5 kg / ha ■ treated. In a second series of attempts, the Dosage increased to 10 kg / ha. Assessing the morphogenetic Deviations in this second series of tests is made more difficult by the fact that the herbicidal effect is at

! this high dosage plays a very important role.

The results of both series of experiments indicate that the morphogenetisehen deviations in the use of the compounds of the general formula II given above at most, while in particular the compounds of the aforementioned formulas III, IV, and V have a very interesting morphogenetisehe effect.

009882/2201

- ■ f ί -11- ». PHN. 3739

The morphogenetic deviations found in Plants after treatment with compounds according to the invention are in many cases the following:

1. Agglomeration of leaves and / or parts of flowers that are opposite or close to one another (connation and fasciation). Most of the time, the parts that have grown together can still be recognized as such, but in extreme cases a completely

It _ '

Overgrown funnels, an urn or pipes, sometimes even a completely closed bubble.

Induced by reduced parenchymal formation. Reduction of the leaf surface from slight deviations on Leaf margin to a completely linear leaf. 3. Thickening of the scars and their number. The thickening is essentially due to large amounts of collenchyma brought about. Due to unilateral deposition of the collenchyma, club-shaped or spiral-shaped forms are often formed rolled up leaves. The course of the scars is often irregular with numerous anastomoses.

The above-mentioned deviations usually only become visible some time after the treatment, because the substances on very young leaf or flower systems in the top meristem attack. Depending on the dosage, this influence takes place longer or shorter. Ultimately, the plant can after the substance has ceased to work ^ back to normal continue to grow, but it also happens that the apex meristem is still a single, mostly completely abnormal organ forms and is then exhausted,

009882/2201

-12-, PHN. 3739

It turns out that the morphogenetic activity, like the herbicidal activity, is highly selective. To illustrate the specific character of the raorphogenetic effect of the substances, the results of experiments are given below in which various weeds and cultivated plants were examined for their morphogenetic reaction with respect to a number of active ingredients. The dosage of the active ingredients varied between 0.5 Ψ

and 5 kg / ha.

a) active ingredient ; 5- (ethoxycarbonylmethoxy) -2,1,3-benzthia-

diazole.

Results on ragwort: Urheniform modifications

at h kg / ha.

Chickweed: Slight modifications to come

catch, then normal growth.

Nettle: urn-shaped fused together

ne lace leaves; at all

Dosages differing texture

Bindweed knotweed: normal.

Glutinous herb: Bud-shaped modifications

at the top, at k kg / ha.

peach-leaved knotweed: urn-shaped modifications,, at 2 and h kg / ha.

b) Active ingredient: 5- (ethoxycarbonylmethoxy) -U-chloro-2,1,3-

benzthiadiazole.

i ··: * »■■

Ragwort: Curled leaves at 2 and

k kg / ha.

009882/2201

PHN.3739

Chickweed: nettle:

No deviations.
No deviations.

Active ingredient ; 5- (hydroxycarbonylmethoxy) -2,1,3-benzthia-

diazole. ,

Ragwort: chickweed:

Stinging nettle:

Normal.

Fascination with top leaves at k kg / ha.

Urn-shaped overgrown tip leaves, further grain deviations and club-shaped leaves with smoldering tips at k kg / ha.

Bindweed, sticky herb, peach-leaved knotteries and winch: normal.

Active ingredient : ^ - (Methoxycarbonylmethoxy) -7-chloro-2,1,3-benzthiadiazole

Kreuskraut:

Chickweed:

Stinging nettle:

Bindweed knot severe damage at all dosages; Internodes shortened, buds thickened, smoldering, curled or club-shaped leaves. In all dosages, the leaves are linear, no further growth, little flowering and the flowers are badly disfigured. Severely damaged at 2 and k kg / ha; The leaf stalks are elongated, the leaves narrow, and the stigma is abnormal. At all dosages, the leaf is narrow, lanceolate or with. bizarre disfigured tip. Serious damage results at the largest dose.

8 8 2/2201

-U- PHN. _v 3739

Button herb:

Glutinous herb: growth inhibition.

peach-leaved knotweed: many at all dosages

urn-shaped adhesions of the youngest leaves; at 2 and * f kg / ha also linear leaf. All treated plants are longer than the untreated plants due to a strong lengthening of the internodes; Flowering low and late, flowers disfigured. A long-lasting effect. cylindrical narrow leaves. The flower stalk is at ^ "kg / ha longer than with untreated plants; but proportionally shortened at the higher dosages.

Leaf modifications at 1 and 3 kg / ha. Very strong leaf modifications and initially considerable growth inhibition 4- (Hydroxycarbonylmethoxy) -7-chloro-2,1 , 3-benz-

Plantain: Hawkweed:

Tomato: Winch j

thiadiazole.

Ragwort: Vogelraier · ι

Polyurne-shaped and curled leaves.

At all dosages: leaves linear, no further growth, little Blossom, blossoms badly defaced; often blistered together Lace leaves

009882/2201

-15- PHN. 3739

Nettle and knotweed: the same effect as

mentioned under d).

peach-leaved knotweed! At 2 and k kg / ha are

a number of pairs of leaves linearly grown together.

Sticky herb; Button herb, plantain, hawkweed and

Tomato: normal.

f) Active ingredient : 4- (ethoxycarbonylmethoxy) -2,1,3-benzthiadiazole. Ragwort: At h kg / ha the leaf is curled. Chickweed: At all dosages, many bubble

pointed leaves that have grown together in a shape.

Nettle: leaf modifications.

Knotweed: leaves overgrown.

Glutinous herb: growth inhibition.

Tomato: Significant leaf modifications.

peach-leaved knotweed: the same effect as

mentioned under d).

Buttonwort, plantain, hawkweed and bindweed:

N. normal «.

g) Active ingredient : U- (Hydroxycarbonylmethoxy) -2,1,3-benzthiadiazole. Ragwort: modifications at k kg / ha. Chickweed: some modifications.

Stinging nettle; Urn-shaped fused

Pointed leaves, peach-leaved knotweed: same effect as

mentioned under e).

00θ 8 82/2201

PHN. 3739

Voge line: stinging nettle:

Knotweed: sticky herb:

Button herb:

Plantain: Hawkweed:

Tomato: bindweed:

Knotweed; Stickwort, buttonwort, plantain, hawkweed and tomato: No deviations.

h) active ingredient ; 4- (ethoxycarbonylmethoxy) -5,7-dichloro-2,1,3-

benzthiadiazole.

Ragwort: Leaves at all dosages

. ruffled and urn-shaped, tips

often club-shaped and smoldering. No significant modifications. Few modifications, but strong ones Stunted growth.

Few modifications, but severe damage.

Narrowed at 1 / ^, ■ £ and 1 kg / ha Leaves, stunted growth and damage.

At £, 1 and 2 kg / ha: stays low, numerous modifications. Little flowering and fruiting. Modification as mentioned under d). At £ »1 and 2 kg / ha: No bloom occurs in any of the treatments. Only at 2 kg / ha »growth inhibition. Significant leaf modifications. Strong leaf modifications and growth inhibition.
Cotton, cucumber, cranesbill and sunflower:

Strong leaf modifications, even with very low dosages as a paste (30 p.p.m.).

009682/2201.

III. Tea with regard to the influence of the active ingredients on the transpiration of leaves . ''

Procedure ;

As soon as the first leaf of oat seedlings grown in the greenhouse has a leaf length of 10 cm, this becomes Cut the leaf and immediately place it in an agglutination tube introduced, in which an aqueous 3 p.p.m. solution of the to be examined is located. At various times after the sheets have been inserted, the Sheet volume of evaporated liquid determined by measuring the height of the liquid level in the tube. The results show that the active ingredients according to the invention generally have a perspiration-promoting effect, with the effect of 130 to 400 # in terms of leaf evaporation the transpiration of untreated leaves varies.

It has been found that some compounds have an inhibitory effect Have an effect on perspiration, with the effect of evaporation varies from $ 45 to $ 85 in terms of transpiration of untreated leaves.

Because of their properties, the compounds according to the invention can be used for many purposes after processing into the customary preparations. The compounds according to the invention can thus be used particularly advantageously for keeping vegetation down. Where the vegetation is not completely destroyed because of the danger of erasion, and, on the other hand, rapid plant growth is wi r13chaf-til ± ci ^ - ^r r * aeii fce i Γi g . How? ..be i el or vegetation

Road embankments, the compounds according to the invention can be used advantageously »The compounds are also suitable for use in regulating the flowering period of crops, retarding aging, promoting fruit formation, the formation of seedless plants or plants with sterile seeds and the promotion of growth the root system of plants.

The compounds are processed into preparations in the usual way for the various applications. In these preparations The active substance is mixed with solid or liquid inert carrier material, the auxiliary substances, such as surface-active substances Substances, disintegrants, lubricants and adhesives can be added. Examples of preparation forms according to the invention! Solution of the active ingredients in water, if appropriate in the presence of an emulsifier; Oil solutions and Ο · 1emulsions of the active ingredients; mixable oils, pastes, Dust powder, granules, invert emulsions, smoke candles and aerosol preparations.

Wettable powders, pastes and mixable oils are preparations in concentrated form, which are diluted with water before or during application.

The invert emulsions are mainly used in application used in the air, when large surfaces are treated with a relatively small amount of the preparation. The invert emulsion can be used shortly before odor even during the spraying in the spray gun door dädnr.-l ·. be produced that water in an oil solution or pjh.t

BADORtQINAL

0 0 S 8 3 2/2 2 0 1

Oil dispersion of the active ingredient is emulsified. Below For example, some preparation forms are described in more detail, it should be noted that those skilled in the art. in the preparation of this and similar preparations known per se will not experience any difficulties,

Granular preparations are made by E.g. the active ingredient taken up in a solvent and with the resulting solution, optionally in the presence of a Binder granular carrier material, such as porous grains (e.g. pumice stone and attaclay), mineral non-porous grains (sand or ground marl), organic grains (e.g. dried coffee grounds and cut tobacco stalks) impregnated will"

A granular preparation can also be produced thereby that in the presence of lubricants and binders the active ingredient is compressed together with powdered minerals and the compressed material is disintegrated to the desired grain size and sieved out. .

Dusting powder can be obtained in that the active ingredient is intimately mixed with _t an inert solid carrier material, for example in a concentration of 1-50 wt.%. Examples of suitable solid support materials are talc, kaolin, pipe clay, diatomaceous earth, dolomite, gypsum, chalk, bentonite, attapulgite and colloidal SiO or mixtures of these and similar substances. Organic carrier materials, such as ground walnut shells, can also be used.

Wettable powders are made by having 10-80

«Jf-Vi-V- I * -J <-« »■■»

009882/2201

& * '■■■'

Place by weight of a solid inert carrier material, such as the carrier materials mentioned above, with 10 to 80 parts by weight of the active ingredient, 1-5 parts by weight of a dispersant, such as, for example, the lignin sulfonates or alkylnaphthalene sulfonates known for this purpose, and preferably also with 0.5-5 parts by weight of a wetting agent, such as fatty alcohol sulfates, alkylarylsulfonates or fatty acid condensation products, (e.g. those commercially available under the tradename "Igepon") are mixed.

To produce miscible oils, the active ingredient is dissolved or finely divided in a suitable solvent, which is preferably poorly miscible with water, and an emulsifier is added to the solution. Suitable solvents are, for example, xylene, toluene, aromatic petroleum distillates, e.g. Liquids. Examples of emulsifiers that can be used are alkylphenoxy polyglycol ethers, polyoxyethylene sorbitan esters of fatty acids or polyoxyethylene sorbitan esters of fatty acids. The concentration of the active ingredient in these miscible oils is not restricted to narrow limits and can vary between 2 and 50% by weight, for example A solution of the active ingredient in a liquid that is readily miscible with water, such as acetone, can also be used as a liquid and highly concentrated primary preparation, a dispersant and optionally a wetting agent being added to the solution Splashing is then an aqueous DIs-

009882/2201

BATH ORIGINAL

I «

■ *

1 ■ C

t ■

f I

-21- <-w ι ιυυ _pHNt

persion of the active ingredient received. ·

An aerosol preparation according to the invention is customary Way obtained by the fact that the active ingredient, if necessary in a solvent, in a volatile liquid to be used as a propellant gas, such as the tint he used in the trade name "Freon" commercially available mixture of chlorine-fluorine derivatives of methane and ethane is added.

Smoke candles or smoke powder, ie preparations which can develop a pesticide smoke when burned, are obtained by absorbing the active ingredient in a combustible mixture which, for example, is used as fuel, sugar or wood, _for example in ground form, a substance to maintain the combustion , such as ammonium nitrate or potassium chlorate, and also a substance to delay combustion, such as kaolin, bentonite and / or colloidal silica.

In addition to the ingredients mentioned above, the Agents according to the invention also contain other substances known for use in these agents.

E.g. a lubricant such as calcium or magnesium stearate can be added to a wettable powder or a mixture to be granulated. can be added. For example, "adhesives" such as polyvinyl alcohol cellulose derivatives or other colloidal materials, such as casein, may be added to ensure the adhesion of the Improved pesticide agent on the surface to be protected will.

As a result of the highly selective biological effect of the

009882/2201

Compounds according to the invention can advantageously be other biologically active substances, such as herbicidal substances, are included in the preparations according to the invention. In this way it is achieved that the range of action of the preparation is expanded and that synergistic effects are obtained. It has been found that the following herbicidal substances are advantageously included in the preparations according to the invention can:

Herbicidal compounds with growth effects, such as: 2,4-dichlorophenoxy-acetic acid (2,4-D) 2, U, 5-trichlorophenoxy-acetic acid (2, ^, 5-T) 2-methyl - ^ - chlorophenoxy-acetic acid (ΜΟΡΑ) c / \ - (2-Methyl-4-chlorophenoxy) propionic acid (MCPP) Quaternary herbicides, such as :

1.1 • -Aethylen-2,2'-dipyridilium-dibroraid (diquat), 1,1'-dimethyl ^, k '-diperidilium dibromide (paraquat) triazines. like :

2-chloro-U, 6-bisäthylamino ~ s-triazdn (simazine) 2-chloro-4-ethylamino-6-isopropylamino-s-triazine (atrazine) 2-chloro - ^, 6-bisisopropylaminO "S-triazine (propazine) Urea derivatives such as ;

1-phenyl-3,3-dimethylurea (fenuron) 1 - (^ »_ chlorophenyl) -3,3-dimethylurea (Monuron) 1 »(Z | i-chlorophenyl) -3-methoxy-3-methylurea (monolinuron) 1 _ (^ i_Chlorphenyl) -3- r3- (butyne-i) J-3-niethylurea (Buturon) 1- (if «-Bromophenyl) -3-methoxy-3-methylurea (Metobromuron) 1- (3 », 4'-dichlorophenyl) -3,3-dimethylurea (diuron)

009882/2201

\ -23- 2 OO 7> 6.0 ^ΡΗΝ · ³⁷³⁹ ^

! - (3 ¹ , 4 ^l -Dichlorophenyl) -3-methoxy-3-methylurea (Linuron) '1- (3 ·, k ' -Dichlorophenyl) -3-butyl-3-methylurea (Neburon) 1— (3 » -Chlor-4 »-bromophenyl) -3-methoxy-3-methylurea (C 6313) 1- (31-trifluoromethylphenyl) -3,3-dimethylurea (fluometuron) phenols ;

2,6-dichloro-4-cyanophenol (chloroxynil) 2, o-dibromo - ^ - cyanophenol (bromoxynil) 2,6-diiodo-4-cyanophenol (loxynil) 4,6-dinitro-orthocresol (DNOC) 2-sec. -Butyl-4,6-dinitrophenol (Dinoseb) Pentachlorophenol (PCP) Chlorinated fatty acids : Monochloroacetic acid (SMCA) Trichloroacetic acid (TCA) &, <λ -Dichloropropionic acid (Dalapon) d , ά , <h -Trichloropropionic acid (TCP) Others;

3-Amino-1,2,4-triazole (Amitrole) 3,6-endoxohexalhydrophthalic acid (Endothal) Maleic hydrazide (ΜΗ) 2,3,6-trichlorobenzoic acid (TBA) 2-methoxy-3,6-dichlorobenzoic acid (Dicamba) l- (3, 4'-dichlorophenyl) -3-methyl-2-pyrrolidinone (BV 201) 1- (3'-chloro-4'-methylphenyl) -3 ~ niethyl-2-pyrrolidinone (BV 207) N, N-dimethyl-2,2-diphenylacetonide (diphenamide) 2,3,5-trichloropyridone-4 (Daxtron) 4-amino-3, 5,6-trichloro-M-picolinic acid ^ Tordon)

009882/2201

5-amino-4-chloro-2-phenyl-3 (2H) -pyridazinone (pyramin) 3-cyclohexyl-5,6-trimethyleneuracil (Lenacil) 2,6-Dinitro-N, N-dipropyl- <*, c ^, -trifluoro-p-toluidine

(Trifluralin)

2,6-Dinitro-4-methylsulfonyl-N, N-dipropylaniline (Planadin) 5-BroBM6-methyl-3- (1-methylpropyl) -uracil (Bromacil) 3-amino-2,5-dichlorobenzoic acid (Amiben)

_t 2 _t 3 »6-trichlorophenylacetic acid (Fenac)

fc 2,6-dichloro-3-methoxybenzoic acid (Mediben) N- (3-chlorophenyl) isopropyl carbamate (CIPC) 2,6-dichlorobenzonitrile (dichlobenil).

The dosage of the preparation according to the invention upon application depends to a considerable extent on the field of application and the active ingredient used. Also influence within an application area, e.g. weed control various factors determine the dosage necessary to achieve a satisfactory effect, such as the type of to combating weeds, the state of the cultivated plant, clit = ·

^w Preparation form in which the active ingredient is used.

In general, however, it can be said that to control weeds, a dosage of the active ingredient of 1-20 kg / ha gives the desired effect. Using the active ingredients on the basis of their morphogenetic properties Properties, a smaller dosage of the active ingredient, e.g. up to 10 kg / ha, is usually sufficient.

If the connections in water cultures, 2.B. to the Stimulation of the root growth or to promote the Leaf transpiration, used, are with a

008882/2201.

Concentration from 1 - 100 p.p.m. of the active ingredient in general achieved satisfactory results

The compounds according to the invention are new substances, excluding the compounds of the formula

OCH "COOR ₂

in the

R _{2 is} a hydrogen atom, a methyl or an ethyl group and

Y represents a chlorine or bromine atom

The latter connections were made by VG »Peson es. in Zhurnal Obschej Khimii %%, pp. IO96-11-0.1 f 1752 - 1759 (1963). These substances have a biological effectiveness

in relation to plants is not known.

The compounds according to the invention can by Methods are prepared which are known for the preparation of similar compounds or are analogous to these methods. The connections according to the invention can thus be established be that compound of formula

in the

009882/2201

A «ine hydroxyl group, Y is a chlorine or bromine atom, Z represents a hydrogen atom or a lower alkyl group

represents and

η is equal to 0, 1, 2 or 3,

with a compound of the formula

Hal - QH - COOR

in the

R _{1 is} a hydrogen atom or 1 to 3 carbon atoms

containing alkyl group,

R represents an alkyl group containing 1 to 10 carbon atoms and Hal represents a halogen atom,

is reacted in the presence of an acid binder. Suitable acid binders are, for example, organic bases such as pyridine, collidine, and inorganic bases such as alkali carbonates and Hydroxides. The reaction is preferably carried out in the presence of a catalytic amount of an alkali metal iodide, e.g., KJ, and carried out a solvent. Suitable solvents are, for example, ketones such as acetone. The reaction temperature can vary between 20 and 100 ° C and preferably corresponds to the boiling point of the inert solvent used.

The starting materials for the above-described reaction can be obtained from the corresponding methoxy-2,1,3-benzothiadiazoles

' i

by means of hydrolytic ether cleavage after the calibration of the reaction

009882/2201

-27- 2007Ί60 ^{ΡΗΝ 3739}

+ atark anorga

can be obtained. In these formulas, Y, Z and η have the
meaning mentioned above. The hydrolysis can be carried out with concentrated NgSOji (9056). Other reagents, such as, for example, pyridine-HCl, HBr, can also be used for the hydrolysis reaction. The reaction temperature can be between 100 and 120 G
vary. The reaction can be carried out without a solvent, the acid used at the same time acting as a diluting liquid. .
Various processes can be used to prepare the methoxy-2,1,3-benzothiadiazoles mentioned, such as: 1) Ring closure of o-phenylenediamines, for example according to the reaction equation

H_GO v, "

bf ^ T H ₃ CO ^

The ring closure is in the presence of an acid binder, such as
Triethylamine. ·

2) Halogenation of methoxy-2,1,3-benzothiadiazoles after
the reaction equation

H "CO

S + halogenating agent

009882/2201

• ι

• t

*) 1 I.

-28-

. 2007 160 PHN. 3739

In these formulas, Yi, Z and η have the aforementioned meanings. All halogenating agents can be used Cig, ^Br 2 'bromeuocinimide in a strongly acidic medium such as sulfuric acid.

3) Nucleophilic substitution of a halogenated 2,1,3-Benüthiadiazole after

In these formulas, Y, Z and η have the aforementioned meanings. The reaction can be carried out with sodium ethylate in methanol at reflux temperature or at a higher temperature, ζ.Β »130 C, be carried out in an autoclave. You can also use sodium methylate in a high-boiling solvent such as Dlglyme (i6o C), to be worked »It was also found that the reaction in aprotic solvents takes place smoothly goes. So the reaction in SuIfolan went very quickly at low temperature,

Furthermore, the compounds according to the invention can be prepared by a process which is characterized in that is that a compound of formula

009882/2201

I I

I I. it I

2007 160 ^PHN 3739

.Ti

in the

X represents the group -OCHCOOR in which R _{1 is} a hydrogen atom or an alkyl group containing 1 to 3 carbon atoms and R is an alkyl group containing 1 to 10 carbon atoms,

and Z represents a hydrogen atom or a lower alkyl group is treated with a chlorinating or brominating agent.

Suitable Halogierungsmlttel are * eg Cl ₂ and Br ₂ The reaction is performed optionally in the presence of an acid binder _r such as organic or inorganic bases such as pyridine, collidine and alkali metal carbonates and hydroxides, performed. The reaction is preferably carried out in a “solvent, such as chlorinated hydrocarbons, alcohols and organic acids, and at a reaction temperature between 20 and 80 ° C. :

According to another method, the inventive Connections are made by having a connection de? Formula.

009882/2201

in the _R

X is the group -OCHCOOR in which R _{1 is} a hydrogen atom or an alkyl group of 1 to 3

Carbon atoms and R is an alkyl group containing 1 to 10 carbon atoms represents

Y is a chlorine or bromine atom,

Z represents a hydrogen atom or a lower alkyl group and

η is 0, 1, 2 or 3,

is hydrolyzed, converting the ester group into a carboxylic acid group.

The hydrolysis can be carried out with the reagents known for this purpose. Suitable reagents are, for example, inorganic acids such as H ₂ SO. , HCl, HBr. The reaction temperature can vary between 20 and 100 ° C.

The invention is explained in more detail below using a few exemplary embodiments. 1. Production of ** - (ethoxycarbonylmethoxy) -2.1.3-benz thiadiazole

U ₁ O g of 4-hydroxy-2,1,3-benzthiadiazol were dissolved in 100 ml of acetone. An excess of potassium carbonate and 0.3 g of potassium iodide were added to the solution and the deep red solution obtained was boiled with a slight excess of ethyl bromoacetate until complete decolouration was achieved. The reaction mixture was poured into water and the precipitate was filtered off with suction, with water

009882/2201

washed and dried. The product was crystallized from ligroin. Yield 5 »O g of 4- (ethoxycarbonylmethoxy) -2,1,3-benzthiadiazole. Melting point 7 ^ -75 ° C,

Z, In the manner described in Example 1, the compounds indicated in Table I below were prepared according to the invention.

The starting materials used in the manufacture of the The substances listed in Table I are mentioned in Table Ia. In Tables I and Ia are the starting material and the end product made from it with the same number.

- Table I ~

009882/2201

-32-Table I.

, 3739

No. End product Melting point in ° C 1 4- (ethoxycarbonylmethoxy) -6-chloro-benz- thiadiazole-2,1,3 102-103 2 4- (ethoxycarbonylmethoxy) -7-chloro-benz- thiadiazole-2,1, 3 103-104 3 4- (ethoxycarbonylmethoxy) -5 »7-dlchlor- benzthiadiazole-2,1,3 67.5-68.5 4th 5- (ethoxycarbonylmethoxy) -benzthiadiazole- 2.1.3 108-109 5 4- (chloro-5- (ethoxycarbonylmethoxy) -benz- thiadiazole-2,1,3 98-99 6th 5- (ethoxycarbonylmethoxy) 6-chloro-benz- thiadiazole-2,1,3 122-123. 7th 5- (ethoxycarbonylmethoxy) -7-chloro-benz- thiadiazole-2,1,3 102-103 8th 5- (ethoxycarbonylmethoxy) -4,7-dichloro- benzthiadiazole-2,1,3 132-133 9 "- (ethoxycarbonylmethoxy) -k, 6 , 7-trichloro- benzthiadiazole-2,1,3 109-110 10 5- (ethoxycarbonylmethoxy) -4,6-dichloro- benzthladiazole-2,1,3 74-75 11 4- (ethoxycarbonylmethoxy) -5,6,7-trichloro- benzthiadiazole-2,1,3 125-126 12th 7- (ethoxycarbonylmethoxy) -4,5-dichloro- benzthiadiazole-2,1,3 124-125 13th 4- (t-butoxycarbonylmethoxy) -5,7-dichloro- benzthiadiazole-2,1,3 68-69 14th 4- (i-propoxycarbonylmethoxy) -5,7-dichloro- benzthiadlazole-2,1,3 98-99 15th 4- (octoxycarbonylmethoxy) -5,7-dibromo-benz- thiadiazole-2,1,3 64-65 16 4- (ethoxycarbonylmethoxy) -5 »7-dibromo- benzthiadiazole-2,1,3 72-73 17th 4- (ethoxycarbonylmethoxy) -5-chloro-benz- thiadiaasol-2, 1.3 99-100 18th 4- (ethoxycarbonylmethoxy) -5 »6-dichloro- benzthiadiazole-2,1,3 76-77 009882/2201

200716 & N. 3739 Table I (continued)

No. ι 19th End product Melting point in OC 20th 4- (ethoxycarbonylmethoxy) -7-chloro-benz- 80-82 thiadiazole-2,1,3 21st 4- (n-Butoxycarbonylmethoxy) -5 »7-dichloro- benzthiadiazole-2,1,3 57-58 22nd 4- (n-hexoxycarbonylmethoxy) -5 »7-dichloro- benzthiadiazole-2,1,3 46-47 23 4- (n-Octoxycarbonylmethoxy) -5 »7-di.chlor- benzthiadiazole-2,1,3 50-52 ^ - (AethoxycarbonylmethoxyJ-S ^ -dichlor- benzthiadiazole-2,1,3 62-64

009882/2201

PHN. 3739

SH

Table 1a Raw material

1 ^ -Hydroxy 2 4-hydroxy 3 4-hydroxy k 5-hydroxy 5 U-chlorine-5 6th 5-hydroxy 7th 5-hydroxy 8th 5-hydroxy 9 5-hydroxy 10 5-hydroxy 11 ^ -Hydroxy 12th 7-hydroxy 13th 4-hydroxy 1k U-hydroxy 15th 4-hydroxy 16 ^ -Hydroxy 17th 4-hydroxy 18th '»-Hydroxy 19th U-hydroxy 20th U-hydroxy 21st 4-hydroxy 22nd U-hydroxy 23 4-hydroxy

> 6-chloro ~ benzthiadiazole-2 _t 1,3 y-chloro-benzthiadiazole - ?, 1,3 ■ 5 t 7-dicshlor-benzthiadiazole-2,1,3 ■ benzthiadiazole-2,1,3 • hydroxy-benzthiadiazole- 2,1,3 • 6-chloro-benzthiadiazole-2,1,3 • 7-chloro-benzthiadiazole-2,1,3 • 4,7-dichloro-benzthiadiazole-2,1,3 ■ 4,6,7- trichlorobenzthiadiazole-2,1,3 • k , 6-dichlorobenzthiadiazole-2,1,3 ■ 5,6,7-trdchlor-benzthiadiazole-2,1,3 • k , 5> dichlorobenzthiadiazole-2, 1,3 • 5 »7-dichloro-benzthiadiazole-2,1,3 • 5» 7-dichloro-benzthiadiazole-2,1,3 ■ 5 f 7-dibromo-benzothiadiazole-2,1,3 • 5,7- dibromobenzthiadiazole-2,1,3 • 5-chlorobenzthiadiazole-2 _f 1,3 • 5,6-dichlorobenzthiadiazole-2,1,3 ■ 7-chlorobenzothiadiazole-2,1,3 • 5, 7-dichloro-benzthiadiazole-2,1,3 • 5,7-dichloro-benzthiadiazole-2,1,3 '5 »7-dichloro-benzthiadiazole-2,1,3 • 5» 7-dichloro-benzthiadiazole-2, 1.3

009882/2201

3 · Preparation of 'U- (Hydroxycarbonylmethoxy) -2. T. 3-benzthia diazole .

3 * 0 g of 4- (ethoxycarbonylmethoxy) -2,1,3-benzthiadiazole, prepared according to Example 1, were dissolved in 50 ml of concentrated sulfuric acid and 5 ml of water. The solution was heated on the steam bath for an hour and then poured into water. The solid obtained was filtered off with suction, washed with water and dried. Yield 2, k g. Melting point 159-16O ° C.

k. The substances given in Table 2 below were produced in the manner described in Example 3. The starting materials for the production of these substances are mentioned in Table 2a, the starting material and the end product obtained therefrom being given the same number.

009882/2201

-39- Table 2

PHN. 3739

No. End product Melting point in ⁰ C 1 4- (Hydroxycarbonylmethoxy) -6-chloro-benzthiadiazole- 2.1.3 177-179 2 U ^ hydroxycarbonylmethoxy) -7-chloro-benzthiadiazole- 2.1.3 193-195 3 •
b- (Hydroxycarbonylmethoxy) -5 »7-dichloro-benzthia- diazole-2,1,3 173-174 5- (Hydroxycarbonylmethoxy) -benzthiadiazole-2,1,3 210-21 1 5 5- (Hydroxycarbonylmethoxy) -4-chlorobenzthiadiazole- 2.1.3 198-200 6th 5- (Hydroxycarbonylmethoxy) -6-chlorobenzthiadiazole- 2.1.3 198-199 7th 5- (Hydroxycarbonylraethoxy) -7-chloro-benzthiadiazole- 2.1.3 192-194 8th 5- (hydroxycarbonylmethoxy) -k , 6,7-trichloro-benz- thiadiazole-2,1,3 176-178 9 5- (Hydroxycarbonylmethoxy) -k, 6-dichior-benzthla- diazole-2,1,3 215-216 10 4- (hydroxycarbonylmethoxy) -5 »6,7-trichloro-benz- thiadiazole-2,1,3 198-200 11 7- (hydroxycarbonylmethoxy) -k _t 5-dichloro-benzthia- diazole-2,1,3 205-206 12th U- (Hydroxycarbonylmethoxy) -5-chloro-benzthiadia- zol-2.1.3 199-200 13th * ♦ - (Hydroxycarbonylme thoxy) -5, 6-dichl or-benz- " thiadiazol-2, 1.3 215-216 1U ^ - (Hydroxycarbonylmethoxy) -7-chloro-benzthia- diazole-2,1,3 195-197

009882/2201

PHN. 3739

Table 2a

Raw material

h- (ethoxycarbonylmethoxy) · k " (ethoxycarbonylmethoxy) · 4- (ethoxycarbonylmethoxy) ■

5- (ethoxycarbonyl methoxy) ■ 5 (ethoxycarbonyl methoxy) 5- (ethoxycarbonyl methoxy) 5- (Aethoxyc arbonylme thoxy) 5- (ethoxycarbonyl methoxy)

5- (ethoxycarbonylmethoxy) - k ~ (ethoxycarbonylmethoxy) -7- (ethoxycarbonylmethoxy) -

U- (Aethoxycarbonylme thoxy) · k- (Aethoxycarbonylme thoxy) ■

k- (Aethoxyc arbonylrae thoxy) -6-chloro-benzthiadiazole-2,1,3 7-chloro-benzthiadiazole-2 \ 1,3 5,7-di.chlor-benzthiadiazole-

2.1.3

benzthiadiazole-2,1,3
4-chloro-benzthiadiazole-2,1,3 6-chloro-benzthiadiazole-2,1,3 7-chloro-benzthiadiazole-2, 1.3 k _t 6 _t 7-trichloro-benzothiadiazole-

2,1,3 kι 6-dichloro-benzothiadiazole-

2,1,3 5,6,7-trichlorobenzthiadiazole-

2,1,3 k , 5-dichlorobenzothiadiazole

2.1.3

5-chloro-benzthiadiazole-2,1,3 5,6-dichloro-benzthiadiazole-

2,1,3 7-chloro-benzthiadiazole-2,1,3

009882/2201

The preparation of the starting materials mentioned in Table I is carried out by processes that are already in this Description (see pages 27 and 28) are given.

The production of such starting materials is explained in more detail with reference to the following exemplary embodiments.

a) Preparation of 4-hydroxy-6-chloro-benzothiadiazole-2, 1 _t 3 46 g of 4,6-dichloro-2,1,3-benzthiadiazole were in a

Solution of 7 g of sodium taken up in 500 ml of methanol. This solution was heated in an autoclave at 120 ° C. for 18 hours, after which the solvent was evaporated and then water was added. The solid obtained was filtered off with suction, washed with water and dried. After crystallization from ligroin, 27 g of the substance were obtained, which was purified by column chromatography (silica gel with benzene as the mobile phase). The 4-methoxy-6-chlorobenzthiadiazole-2,1,3 purified in this way has a melting point of 114-115 C. The 4-methoxy-6-chlorobenzthiadiazole-2,1,3 was then in 400 ml ψ Dissolved 90 ^ sulfuric acid and heated it on the steam bath for 18 hours. The mixture was then poured onto ice and the solid was filtered off with suction. The crude reaction product was taken up in an aqueous bicarbonate solution and the solution was treated with Norit, filtered and acidified. The 4-hydroxy-6-chloro-benzothiadiazole-2,1,3 obtained was isolated by suction.

b) Preparation of 4-Hydroxy-7-chloro-benzthiadiazole-2.1.3 41.0 g of 4,7-dichloro-2,1,3-benzthiadiazole were put together

with an equivalent amount of sodium in 750 ml diglyme sus-

009882/2201

pending. The reaction mixture was boiled (160 ° C.) for 8 hours, then poured into 3 liters of water, after which the obtained Precipitate was suctioned off and dried. Yield 25 g of crude product.

The crude product was purified by column chromatography (silica gel with benzene / petroleum ether (1: 1) as the eluent). Yield 15 g of ^ -methoxy-7-chloro-2,1,3-benzthiadiazole. Melting point 13 ^ -135 ° C. In the manner described under a), the product obtained was converted into ^ -hydroxy-T-chlorobenzthiadiazole-2,1,3.
Melting point 158-16O ° C.

c) Preparation of 5.7-dichloro-fr-hydroxy-benzthiadiazole-2,1.3 177 g of 2,4-dichloroanisole (1.0 raol) were added dropwise at 60 ° C. to a mixture of 600 ml of concentrated sulfuric acid and 600 ml of fuming nitric acid (specific weight 1.50) added.

The mixture was subsequently stirred at 60 ° C. for one hour. The reaction mixture was poured onto ice and the solid obtained was filtered off with suction, washed with water, dried and recrystallized twice from ethanol. Yield 55 g of pure 2,4-dichloro-Siö-dinitroanisole.
Melting point 67-68 ⁰ C.

The dinitro compound was reduced to the diamine with the aid of iron and hydrochloric acid in methanol.

The diamine was in benzene with thionyl chloride and triethylamine cyclized to 5,7-dichloro-4-methoxy-2,1,3-benzthiadiazole.

Melting point 120 ° C,

009882/2201

In the manner described under a), the product was converted into 5 »7-dichloro-4-hydroxy-benzthiadiazole-2,1,3. Melting point iU3-ifc7 ° C.

d) Preparation of U-chlorine - ^ - hydroxy-benzthiadiazole-2,1,3 31 ^ β 5-methoxy-2,1,3-benzthiadiazole were in 100ml

Acetic acid dissolved. Chlorine gas was passed through at 20 ° C. until no more precipitate formed. The solid was filtered off with suction and dried. Yield 3.0 g of 1-4 chloro-5-methoxy-2,1,3-benzthiadiazole.

In the manner described under a), 4-chloro-5-hydroxy-benzthiadiazole-2,1,3 was obtained therefrom. Melting point 19U-196 ⁰ C.

e) Production of 5-hydroxy-6-chloro-benzothiadiazole-2.T.3 4-chloro-2-nitro-5-methoxyaniline was -on catalytic

Reduced routes with palladium / carbon as a catalyst. That Diamine was cycled in the usual manner. The crude 5-chloro-6-methoxy-2,1,3-benzthiadiazole was purified by steam distillation. Melting point 137-138 C. The product was on converted into S-hydroxy-o-chloro-benzothiadiazole-2,1,3 in the manner described under a).

f) Production of 5-hydroxy-7-chloro-benzothiadiazole. 2.1 _t 3 25 g of 2-chloro-6-nitrophenylazide were added spoon-wise

65 ml of 30 η sulfuric acid were added at 50-55 ° C. Nitrogen evolved and the solution turned dark. The mixture was stirred for 15 minutes, after which the mixture was poured out in water. The product was isolated by ether extraction. Yield 23 g of dark brown fabric.

009882/2201

Melting point 19 ^ ⁰ C.

The p-hydroxyaniline was with the help of sodium methylate and Methyl iodide methylated to 2-chloro-4-raethoxy-6-nitroaniline.

Melting point 120 ° C.

Reduction and cyclization gave 5-methoxy-7-chloro-2,1,3-benzthiadiazole obtain.

Melting point 110-120 ° C.

In the manner described under a), 5-hydroxy -7-chloro-benzothiadiazole-2,1,3. Melting point iifO-i42 ° C.

g) Preparation of 5-hydroxy-4.6.7-trichlorobenzthiadiazole

2, T.3

53 »7 6 ² tons of 3,5-trichloro-4-methoxyacetanilide were added spoon-wise to 100 ml of fuming nitric acid (specific gravity 1.50) at 0-5 ° C. The mixture was then stirred for half an hour. The reaction mixture was poured onto ice, the solid was filtered off with suction and washed with water. The still wet product was dissolved in 250 ml of concentrated sulfuric acid and heated to 85 ° C. for 20 minutes. After pouring onto ice, filtering off the solid with suction, washing and drying, ^ 3 »9 e brown-red material was obtained.
Melting point of the pipe product 5O-6O C.

This nitroaniline was reduced in methanol with iron and hydrochloric acid and cyclized in the usual way. Yield 22.5 g k _t 6, 7-trichloro-5-methoxy-2,1,3-benzthiadiazole. Melting point 127-128 ° C.

In the manner described under a) this would result in 5-hydroxy - ^, 6, 7-trichlorobenzthiadiazole-2,1 3 prepared,

Melting point 222-1 "i-'u

BATH ORIGINAL

Claims (1)

PATENT CLAIMS : 1 · Compounds of the general formula in the J X represents the group -OCHCOOR in which Typically a hydrogen atom or an alkyl group of 1 to 3 Carbon atoms and R is a hydrogen atom or 1 to 10 carbon atoms containing alkyl group, Y is a chlorine or bromine atom and Z represents a hydrogen atom or a lower alkyl group and η is equal to 0.1 £ or 3, with the proviso that R represents an alkyl group with 3 to 10 carbon atoms when the substituent X is in the 4-position of the ring system the substituent Y is both 5- »and 7-positions and the substituent R _{1 is} a hydrogen atom. 2. Compounds of the general formula 009882/2201 Vl in the X is a _{-OCH 2} COOR group present in the k- _t or 5-position of the ring system, in which R represents a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms, Y is a chlorine atom and η is 0, 1, 2 or 3, with the proviso that R represents an alkyl group having 3 to 10 carbon atoms when the substituent X is present in the ^ position of the ring system and Y is both 5- »as also occupies the 7-position * 3 «compounds of the general formula OCH ₂ COOR in the R is a hydrogen atom or an ethyl group and Y is a hydrogen atom, a chlorine atom in the 5-, 6- or 7-position of the ring system, two chlorine atoms in the 5- and 6-position of the ring system or three chlorine atoms in the 5-, 6- and 7- Position of the ring system represents k. Compounds of the general formula 009882/2201 in the R is a hydrogen atom or an ethyl group and Y is a hydrogen atom, a chlorine atom in k- , 6- or 7-position of the ring system, two chlorine atoms in 4- and 6- or k- and 7-positions of the ring system or three chlorine atoms in k- , 6- and 7-position of the ring system. 5. Compounds of the formula OCH ₂ COOR in the R is an alkyl group of 3 to 10 carbon atoms 6. Compound of the formula OCH ₂ COOC ₂ H 7. Compound of the formula OCH ₂ COOC ₂ H Cl 8. Compound of Formula 009882/2201 HS PHN. 3739 Ji 9. Compound of Formula H ₅ C ₂ OOCH ₂ CO 10. Compound of the formula HOOCH ₂ CO _ 11. Compound of Formula H ₅ C ₂ OOCH ₂ CO Cl - ~ ^! 12. Compound of the formula HOOCH ₂ CO Cl 13. Compound of Formula HC ₀ OOCH ₀ CO
52 ζ Cl 009882/2201 ^ k. Compound of formula OCH ₂ COOiC ₃ H ₇ 15. Compound of formula OCH ₀ COOnC-H- 16. Compound of Formula OCH ₂ COOt. Cl 17 · Compound of formula OCH ₂ COOn. Cl 1
Cl 18. Compound of Formula OCH ₂ COOC ₆ H ₁₃ 009882/2201 N.V. Philips'Gloeilampenfabrieken ^ uu / ι ου 19. Compound of Formula S Cl 009882/2201