DE1793502A1 - Pyrancarboxylic anilides and their use as pesticides - Google Patents

Description

to the patent application Fw

Pyrancarboxylic anilides and their use as pesticides

(Addition to patent ......... corresponding to patent application P 16 68 Ü99.6 - Fw 5015.)

Subject of the patent * · ........ (patent application P 16 6ö 899.6

Is 2-methyl-5,6-dihydropyran-3-carboxylic acid anilide

and its preparation from 2-methyl-5iG-di acid. The subject of the patent is still a plant protection " agent, which 2-methyl-5, o-dihydropyran-O-carbonaaureanilid contains as an active ingredient.

In the further development of the invention, 2-methyl-5,6-di hydropyrÄn-3-carboxylic acid anilides of the general formula

Hl-

ClI

(1)

found in which II is an ethyl group or a wethoxy group

2 09811/1848

SAD ORIGf

represents, which is in each case in the meta-, ortho- or para-position of the benzene nucleus.

The invention also relates to plant protection products, which contain the mentioned carboxylic acid anilides as active ingredients.

Bs is known that compounds of similar constitution as 2,3-Dihydro-5-carboxanilido-6-methyl-l,% - oxathiin (II) and 2, S-Dihydro-S-carboxanilido-e-methyl-1,4-oxathiine-4-dioxide (III) have a fungicidal effect (cf. US Pat. No. 3,249 * ^ 99 and Belgian Pat. No. 679 * 964, pages 19 and 29) ·

(II) (HD

The known compound (II) has a good effect against plug fire types, However, only a low systemic action against rust diseases. The known compound (III) has good ones systemic and pickling action against rust diseases, proves however, in the fight against flying fire diseases as inadequate.

The new compounds are the known compound (II) with regard to the systemic effect and the pickling effect, The known compound (III) is surprisingly superior in terms of its effect in fighting aviation fires *

The process for the preparation of the 2-methyl-5,6-dihydropyran-3-carboxylic acid anilides is characterized in that either 2-methyl-5,6-dihydropyran-3-carboxylic acid with a Chlorinating agent converts 2-methyl-5t6-dihydropyran-3-o * rboxylic acid chloride and this with appropriately substituted anilines in (based on an inorganic or tertiary organic

209811/1848

ganisehen Β ···

or that 2-methyl-5,6-dihydropyran-3-carboxylic acid is old correspondingly substituted phenyliaocyanates bsi increased Temperature converts.

As a chlorination device, preference is given to using phosphorus trichloride, phosphorus pentachloride, thionyl chloride and phosphorus oxychloride. The chlorination is carried out at temperatures between -20 ° C and +100 ⁰ C) preferably iat a temperature range between ⁰ ° C and 30 ° C.

The chlorination is expediently carried out in an inert solution means such as carbon tetrachloride, chloroform, methylene chloride, ethylene chloride, toluene or benzene carried out

üie implementation of the SMurechlorida with those who are unsubstituted in the benzene core Anilines is used in the presence of an inorganic or tertiary organic baae carried out. AIa inorganic baaen caustic soda and potassium hydroxide come into consideration. Ala tertiary organic Baaen can triethylamine, Dimethylanilln or pyridine and its homologues can be used. Even an excess of substituted "aromatic amine can be used"

The implementation of 2-methyl-5,6-dihydropyran-3-carboxylic acid with Phenyl isocyanate takes place at temperatures between 80 ° C and 10 ° C, preferably between 1% 0 ° C and 170 ° C. After finished The reaction is advisable to remove the reaction product by washing with an inert solvent such as carbon tetrachloride or to free gasoline from tiberachuaigem phenyliaocyanate.

The 2-methyl-5,6-dihydropyran-3-carboxylic acid anilides according to Invention can be used as raw material in vegetable ash, above all «as fungicides. They are particularly effective against rust and smut fungi on cereals, e.g. B. g «g« n Weixengelbrost and Weimenbraunrost, Flugbrand, Steinbrand and Soil pills, such as rhlsoctomia. As a fungicide, the application Fig. both in pasx protection and in storage.

rv * ::. ^ - 2098 11/184 8

Active ingredient · According to the invention, Ik can be the usual Mixtures of old solid or liquid inert η carrier metal, ■ with adhesive, wetting, diapering and grinding aids as Wettable powders, emulsions, suspensions, dusts or granules be used. You can use other pesticides be mixed, with which they form compatible mixtures.

Ala carrier substances can be used mineral-free substances like aluainiuaiailicate, clays »kaolin, chalks, siliceous chalks, Talc, kieselguhr or hydrated silicic acid, or preparations made from special mineral substances Additives, e.g. B. Chalk greased with sodium stearate. AIa Carriers for liquid preparations can be all common ones and suitable solvents, such as toluene, Xylene, Olacetone Alcohol, Cyclohexanone, Isophorone, Benzine, Paraffin oils, dioxas, Dieethylforeaeid, Oiaethylsulfoacyd, Ethyl acetate, butyl acetate, tetrahydrofuran, chlorobenzene and others can be used.

All adhesives can contain lela-like cellulose products or mrviayl alcohol be used·

All suitable Seulgateren such as oxäthyllerte alkylphenols, salts of aryl or alkylarylsulfanoic acids, salts of Hethy Lt aurin can be used as Neteatoffe. Salts of Phenylkogasia ^ ulfemsAuren or soaps are used

As Olepergierstoffe cell pitch can be used (salts of Llgnlnsulfonaäure), salt · dw üaphtalinsulfonsäur "sowi · hydrated under Oiständen · lieaelsäure" or diatomaceous earth.

Suitable inorganic or organic salts, such as sodium sulphate, ammonium sulphate, sodium rfcemat, Sodium carbonate, sodium thiosulfate, sodium tearate or MatriiMiaeetat can be used.

Oureb the next "examples will explain the discovery". However, this does not apply to the subject matter of examples ^U1 2098 ί 1/1848

ORIGINAL

Example It

The preparation of the 2-methyl-5,6-dihydropyran-3-carbonic acid anilides of the invention is carried out as follows. 0.1 mol of 2-methyl-5,6-dihydropyran-3-carbonic acid is suspended in 25 ml of ethylene chloride, treated with 0.05 mol of phosphorus trichloride and left to stand for 1.5 hours at Ziemer temperature with exclusion of moisture. After the phosphorous acid, which forms the lower liquid layer in the reaction mixture, has been separated off, the solvent is distilled off under reduced pressure. The crude acid chloride obtained is added dropwise at ⁰ ° C to a solution of 011 mol of the corresponding aromatic amine substituted in the benzene ring and 0.12 mol of pyridine in 100 μl of benzene. the organic phase is washed with dilute hydrochloric acid and water and the solvent is distilled off.

In this way the following connections are made!

a) Using m-toluidine, 2-methyl-5,6-dihydropyran-3-carboxylic acid (m-methylanilide), Yield 78% of theory (based on the carboxylic acid used)) Melting point 96.5-

b) Using o-toluidine 2-methyl-5,6-dihydropyran-3-carboxylic acid (o-methylanilide), yield 75% of theory! Melting point 128 to 123.5 ⁰ C.

c) Using p-toluiditol, 2-methyl-5,6-dihydropyran-3-carboxylic acid (p-methylanilide), yield 80 % of theory | Melting point 125-126 ° C.

d) Using m-anisidine 2-methyl-5 _t 6-dlhydropyran-3-carboxylic acid m-0ethoxyanilide, yield 73 % of theory | • ohaela point 10% -105 ° C

e) Using o-anisidine 2-methyl-5,6-dihydropyran-

209811/1848 where «ueiMAL

3-carboxylic acid (o-methoxyanilide), yield 78% thorite, melting point ⁰

f) Using p-

3-carboxylic acid (p-methoxvanilide), yield 79 % of theory, melting point 153-156 ° C.

Example 2 ι

Wheat Plants Grown In The Greenhouse In Polka Dots were in the two-leaf stage with the compounds listed below according to the invention in active ingredient application rates van% OO, 200, 100 and 50 mg / 1 fuel »brühβ treated»

(A) »2-methyl-5» 6-dihydropyran-3-carbonic acid (m-methylanilide)

(B) »2-methyl-5i6-dihydropyran-3-ear» ottic acid- (o ~ methvlanilld)

(C) a-methyl-5,6-dihydropyran-3-carboxylic acid (p-methylanilide) (0) ■ 2-methyl-5,6-dihydropyran-3-carboxylic acid (m-methoxyanilide) (·) ■ 2-methyl-5,6-dihydropyran-3-carboxylic acid ~ (o ~ methoxyanilide) (P) ■ 2-methyl-5,6-dihydropyran-3-oarboaic acid (p-ethoxyanilide)

The compounds known as fungicides (Q) «2,3-Dlhydro-5-carboxanllido-6-methyl-1 ₍ % * oxathiine and (H) -zincethylene bis-dithiocarbamate were used in the same way and with the same active ingredient application rates control were a further number ron plants treated with tap water without agents ·

5 days after the treatment, both treated leaves were cut off from the stem. After 3 weeks, the newly grown leaves were heavily infected with a Sporeaeuepeneioa from Weizenschwarxroet, then placed in the humidity chamber for 12 hours and then generally brought to the Qewäehehaus.

• AD 209811/1848

heit «infestation judged.

As can be seen from Table I below, aalgea the compounds (A) - (P), according to the invention, have an superior to the well-known comparisons (Q) and (H) Ayateaic effect against Welaenroat. (Oaa comparisons » alttel (H) showed no ayatealceh · effect).

Beiaplel 3 ι

Weisenaatgut of the variety "Heine VII" was "with the compounds (A) - (P) according to the invention in the application aangea of 200, 100 and 10 g of active ingredient per 100 kg of seeds for 10 minutes in a Beiatreaaiel in the usual Velae. To · By comparison, weiaenaaatgut old of the known compound (Q) was treated in the same way * lh days after the treatment the seeds were cut and the Welaeapflaasen was laflied near there * emergence from the orel to four-leaf stage old savers Temvelaengelbroat.

% Week "after" the infection, 41 rflanaan were found to be infected tamd the degree of infestation arai «t« l%.

01 · attached to Table IX indicates 4 «a dir» 'connections (A) - (P) gaariU 4er Brfl «4« M | · 1 »· aofer ft · « yataa ^ aehe Iflriranf g «g« a Veiaeagelbreat la Beiarerfahren bealtaen. 9 Comparing agent (A), however, has no effect under the mentioned conditions *

Belayll k t

Oat seeds of the variety PlMaingatrvue * became old Speren τοη Haferflugbraawl (Oatilage avanae) «heavily infected. Da · infused Seed was used as the compounds (A) - (P) g-M of the rfimdumg la Awfweaaaeagan Ten 100, 90 and if g Acts «ff 4 100 kg of seeds for 10 complaints a Balatreaattl la «blleher tfelae belated. Xua comparison was known as seed old dea t, 3 Xfcrawif faf »aiaiillde« »^ - tkyl-t,» - aaathita. | -41eald (XXX) in gleithea iafiaaJatagea beeaa4 «lt · VMh 1% Tajea« ar4 · da ·

209811/1848 bad

Seed distributed · After the panicles had formed, the PfIan · εan on infestation old oat blight inactive.

From dar naohstahandan Taballa ΣΧΙ it can be seen that dafi dia Compounds (A) - (F) gaaäfi represent a significantly better invention Have an effect against plug fire than the ■ comparative (ZZI).

Table Z

!Link % Black rust infestation of catfish plants
Treatment «it ag active ingredient per liter of spritz
broth 200 100 5O 0 0 5 (A) 0 0 0 3 (B) O 15th 83 35 (C) 0 0 3 10 (O) 0 O 10 15th (B) 0 0 15th 25th (F) 0 33 60 100 ia) 10 100 100 100 (H) 100 100 100 100 [ubbehaj »4elt 100

link % rust infestation of Active ingredient ι way flans make hand lung old g 100 'per 100 kg of seeds 200 0 50 (A) 0 10 15th (B) 0 15th 31 (C) 0 3 33 (0) 0 13th SO (B) 0 33 ti (F) α 100 % e Ct) 100 100 100 thssSjIissMlelt 100 1 848 100 ZU3B I 1 /

BAD OftlGfNAL

Compound % flyburn of oats after treatment

with «active ingredient per 100 kg of seeds

100 50 25

(A) (B) (C) (D) (S) (F) (III) Untreated

0 0 0 0 0 0 0 0 5 0 0 '3 0 5 15th 0 0 5 0 ia 35 68 7i 6%

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Claims (1)

l) 2-methyl-5,6-dihydropyran-3-carbctte * 'ureaKilide der general fora ·! I. Ql 2 * ~ «» where R «in · methyl group or« in · methoxy group, di · aich each in meta, ortho or para position des B «nzolk« rna is located. 2) a-H * thyl-5,6-d ± hydropyran-3-c * rbona acid- (e - «* thylanilld) 3) 2-methyl-5,6-dihydropyran-3-carbonaic acid - (o-ethylanilide) k ) 2 * M "methyl-j>, 6-dihydropyran-3-carbonaMur" (p-ethylanilide) 5) 2-methyl-5,6-dihydropyran-3-carbonate »- (e-ethoxyanilide) 6) 2-methyl-5,6-dihydrojryran-3-carbo »» Mur * -io-aMithoxyanilid) 7) 2-methyl-5,6-dihydropyran-3-carbone acid «- (p-m * thoxyanilide) 3) Process for the preparation of 2-Hethyl-5,6-dihydropyraA-3-carbonaMureniliden the general »Forael Z where R represents a methyl group or a methoxy group, which is in the meta-, ortho- or para-position of the benzene nucleus, characterized by the fact that either 2-ethyl "5 _t 6-dihydropyran-3-carbonate With a chlorination agent et al. U 2> methyl-5,6-dihydro-pyran-3-carbonic acid chloride and di ···· with correspondingly 20981 1/1848 11 Fw 3611 a ■ ub * titui «rt« n aniline »in the presence« in an inorganic one or tertiary organic base, or daft un 2-methyl-5,6-dihydropyran-3-carboonic acid correspondingly substituted phenyl isocyanates at increased Temperature set 9) Plant protection «Medium * characterized by a content of 4-methyl-5,6-dihydropyran-3-carboxylic acid anilides General Forsiel 1 (Z) wherein R represents a methyl group or a methoxy group, they can be seen in meta-, ortho- or para-filling de · leasolkerme is ■ 209811/1848