DE1543751A1 - Process for the preparation of alpha-haloacetanilides and their use as phytotoxic agents - Google Patents

Description

Process for the preparation of α-haloacetanilides and using the same as all paytotoxic agents

The present invention relates to pbytotoxic Connections and the control of plant systems, © Including all keiaeader seeds, giving up Seedlings and. fully developed plants, ait the same sorie paytotoxieohe putty and the creation of the same. . ■

. . · The Auedruok "phytotoxic compound" bsw. "pigrtotoxieciiee smock" is rerwtodet beer, u *. '.. Haterialiea «α beseiobneii, the one BOdüislesende ' Effect on the VacbAto »odev development: the Baben vegetation. Xu such.aodif! Victorious.

BAD ORIGINAL

Effects include, for example, the killing, the delay, the defoliation, the desiccation, the Regulation, stunting, equipping τοη ■ Grain, stimulation, dwarfism and other deviations from natural development. In in the same way the terms "phytotoxic" are used .. and "phytotoxicity" used to denote the species and the Designate the effectiveness of the smock according to the invention. .

Am aim of the present invention ie «the Creation of methods of combating vegetation. Another object of the invention is to provide a process for the production of certain α-halogen * acetanilide. Other aspects, objectives and benefit · of Invention will become apparent from the following disclosure. . . .., '

The erfindungsgeoässen pnytotoxisohen or Herbisid gowns contain a phytotoxic auxiliary gown and an α-haloacetanilide of the formula ',

909810 / 1ISi

wherein B ¹ and H ^{2 are} alkyl or alkoxy nit 1 to 10 carbon atoms, E, halogen, alkyl or. Alkoxy ait 1 to 10 carbon atoms, η a gonse number from 0 to 3,

A oxygen or sulfur, X chlorine, bromine or iodine and

12th
Z, Z and Z are hydrogen, alkyl, alkenyl, alkynyl, alkoxy or polyalkoxy with 1 to 18 carbon atoms, aryl with 6 to 24 carbon atoms, heterocyclic radicals with a maximum of 24 carbon atoms and 1 to 3

Eateroatonien mean or two of the substituents Z, 1 2 ^:

Z and Z with formation of an alternate alleylene residue are combined with 1 to 6 solenoids. -

1 9

One or more of the Z, Z and Z substituents

can old non-interfering substituents, including Halogen, hydroxyl, alkoxy, vitro, dialkylamino,

Carbalkoxy ,. Keto groups and the like.

be. Unless otherwise noted, "alkyl" is · used as a generic term and includes primaryι secondary and tertiary alkyl groups. '- *

Bapresentatives produced according to the invention Connections are, among other things, those «in those the groups in the above formula have the following meanings:

.Ε ² 'and R ² : methyl, ethyl, propyl, isopropyl, n-butyl, primary isobutyl, secondary isobutyl, tert-butyl, n-amyl _t branched aoyl groups and normal and ■

■: r

J-

909810/1181 ". Sad original

branched hoxyl, heptyl, octyl, konyl and decyl groups, Method, Propöxy, Butoaty, Pentyloxy, Beptyloxy and nonylo: ^; ·. '·.'.

R ^ i chlorine, bromine, iodine, fluorine .und the alkoxy groups given ^{for R 1 and E;} and

Z, Z ¹ and Z ² : hydrogen, methyl, ethyl, propyl, ieopropyl, n-butyl, primary leobutyl, secondary isobutyl, tert-butyl, the normal and branched arayl, heacyl, heptyl, ootyl, conyl -, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl groups, coloraiethyl, broaipropyl, iodobutyl, pluorheaiyl, hydroxyl, dihydroxypropyl, the alkoxy, alkoxy, naphthyl, naphthyl, naphthyl, naphthyl, naphthyl, and alkynyl groups corresponding to the alkyl groups listed above. ethylene, Triß3thyl "a _e .Tetramethylen, furfuryl, thiofuranyl, pyrrolyl, (Phiaäolyl, pyranyl, Oacmeinyl: Triasinyl and the like.

The present invention also relates to methods of influencing developed plants. germinating seeds and budding ploemas. changed die'Pflanzen that in such a manner, or EER ~ .stört, earth "and preventing the growth of seeds and seedlings \ ,, or modified by aan" ine effective amount of an a-Halogenasetamides applying the above formula to the same. . ^:

also concerns the. present invention:

'· ■ ·· ■■■' ■■ "■;"

Process for the preparation of the above compounds by Implementation of the corresponding IT-HalogenBethyl-arhalogenasetanilide old alcohols or thioalcohol "

The .developed process. at the'die. new compounds are produced by alcoholysis, runs generally geiaäes of the equation :.

♦ Z ^l -O ~ AS

♦ HT

where B ¹ »R ² , E ⁵ , n, X, S, Z ¹ , Z ² and A have the above *

ι '■ ■ have meanings and X is a halogen. The Beaktlon will preferably in the presence of an acid-binding agent executed. They used acyl halide adducts in this process. can «weofeaässis durah adding one Halapyl halides of K-ttethylaain are obtained * as stated in the HS patent document Hr »··» · «» ·····

BATH

Mr. 329 * 279 voa 9th Deseiaber. 1963) describedeii is..

The surprisingly good activity of the halogonatoas in comparison with the absence of chemical activity in the halogenation 2 enables the production of the hot α-haloacetacilides in high yields. In addition, in order to achieve the highest yields, it is desirable that the alcohol or thioalcohol be present in at least an equioolar amount, preferably in an excess of the equimolar amount, in one of the amounts of the acyl halide adducts. She reaction is zwectoäsolg at Rauiatemperatur "ie about 20 run to 25 ⁰ C *; however, higher or lower temperatures may be used as the temperature is not of critical importance. The acid-binding gown, which is preferably used in one of the Hezxge of Halogenwaseeratof t , the formation of which in the reaction is expected, in at least an equimolar amount, can be used. Any e & ur-binding agent, such as xB a tertiary alkyne, for example triacthylaoin, TriKthylaain, pyridine, quaternire aeaonium hydroxides and alcoholates, metal alcoholates and the like, inorganic bases, for example Hatriuehjdroxyd, Kaliuahydroxyd in vaerium, etc. In lohlenwaeseretofnööungsmittel ,.

like s.B. Bensolt foluene, xylene, hexane or the like,

bath

</. 15A3751

but Ιδείich and can · by known crystallization- or vacuum distillation processes are cleaned *

The compounds produced according to the invention are useful as herbicides, fungicides, insecticides, Threadwurk-killing coats, algae-killing coats, Bactericidal, bacterial and antifungal agents Middle; However, the vast majority of the compounds are primarily al3 Hsrbitide, in particular as herbicides for pre-emergence use, and all herbicides for use at low application rates Can be used after rising.

The invention is also applied to the following detailed description of specific examples the same become more clearly understandable ...; ·. ■

Example 1 ·

This example describes the production of S'-tort.-Butyl-S-chior-H-awthoxyoetbyl-e'-methylacetanilld. 20 g 2 ^! -tört.-Butyl ~ 2-chloro-Bf-chlormothyle'-methylacetanilide were placed in a glass beaker and ^{mixed with 100 cm 5} methyl amine in methanol (25% solution). An exothermic reaction occurred immediately, and that Product «dft« eich said goodbye, was insoluble in water and therefore not a quaternary * »SaIs. Sa «methanol

Excess irimethylaain was evaporated, residue was burned off with water, and the oil was extracted with hexane. The hexane layer containing the desired product was placed in a refrigerator, and an icrystalline product separated out. The solids were filtered off, washed with cold hexane and air dried. This white solid substance ecniaola sharp at 77 to 78 ¹ C and weighed 12.5 U *. The elemental analysis of this product gave the following results:

Calculates fito> C

% C 63.5 63.5

⁰ AU . X 7.9; ■ 7 »8.

5S Cl 12.5 12.5

Example 4

•. ■ This example beschreibt'die Preparation of 2-Broia "2.Vtert rbutyl _f * ^li-l methoxyiacthyl-6 -" ethylacetanilid. Ca «, 1414 g (7 Hol) bromotylbronide and 0.95 liters of dry toluene were placed in a 5 liter four-necked flask, and approx. 1200 g (6.86 'mol) of tert-butyl methyl-H- methylenaniline were allaaMioh for a period of. given for one hour; while soian kept the temperature in the range of 50 to 50 per cent . Sa's reaction turned into one

909l8ö / 1t8t

Maintained at a temperature of approximately 4-5 K for approximately 1 hour and left at a temperate temperature for approximately 16 hours. Heated to 40 K , transferred to a separating funnel and added in six portions with 750 g of 50% triethylamine in methanol, whereby one. was Das.Gesieoh the temperature svischen 35 and 40 held X · The Jteaktionsgeaiech was stirred an additional hour at .One temperature of 45 to> 0 K. and then cooled dann.Bit five portions of water (per ea. 1500 car), dried and approx. 0.47 liters of chlorinated benzene were sugeaet * t _s . To facilitate the separation of the heavy product, the total amount of the solvent was increased. by distillation at 20 m pressure and a «Xnde at Oj2. aa pressure and 60 ¹ C removed from the product layer. The mixture was diluted with 1 liter of toluene and 1 liter Wethylcyolohexen and bgekühlt to -40 ⁹ C ", Ban .indes the piston bit dry uagab. A portion of the resulting solidified cash box was isolated, dissolved in hexane, bit dry ice cooled, filtered, bit cold hexane washed and dried in the loft $ 1.9 to 52 % schBOls and had the following analysis ^:! ·

f ^a

1891iO / 1181

- ίο -

• Ai Λ ·. Found Calculated for ( ^ ₅ B ₂ JjBrBU, % 3 54.91 54.88
Λ, fi Sr 6.75 6.76 24.34 24.37 Example 3 '

Example describes the production of vozi 2 '-tert. -Butyl-α-iodine-H-me ^ boxymethyl-ö ¹ - «ethylacetanilide. 105 β iodaoetyl chloride and 100 g dry toluene were placed in a 1 liter four-neck flask. See flask was gassed bit dry »nitrogen, and. 87.5 g (0.5 wt kept below 20 % . The hardening structure was cooled to 50 % _for 15 ° C, and 53 g of triethylamine in 100 twr dry kethenol were placed in the flask, with the. Temperature below 15 X held. The kethenol and the triethylamine were given over a half-length. Little vtres developed during this suga> e. The piston and its intel * were over a leitrmu »τοπ> 5 lUnotes to o *. 50 raised. Oar flask and if the "contents are" cooled down then "it three Ifrrtione" toö ^ OO m ?. Waaa # r awake.

The oil layer was separated from the water and the solvent at 30 sa "up to a flask" temperature of 60 "C evaporated. Heating up 60 <V at a vacuum of 0.5 to 0.15 »» pressure was continued for another half hour. The residual material in the flask became a small one A sample was taken and dissolved in a Tqluol-heptane mixture and the solution was brought into dry ice. It kelp precipitate was obtained. The rest of the RÜokstandSDiaterieles in the flask was in 300 car benzene dissolved and mixed with 250 cm ^ hexane. This solution was filtered to remove a small amount of insoluble material. The Fi! Stepped under again Evaporated in vacuo. A thick brown oil weighing 168 g was obtained. Sine Elementaranalyae this Product gave the following results * C 49.5 g, ..

. This example describes the production of N-Butoxy ca © thy 1-2'-tert-butyl-2-ChIoJS-O ¹ -iB «t hy 1-acetanilide. 60 g chloroacetyl chloride and 100 g n-heptane

J '. ' ^l /' * '"· ■ ■■' · ^ßAD ORIGINAL

were placed in a 1 liter four-necked flask. Under nuiren. were 6 * 7.5 β (0.5 mole) of a-tert-butyl-o-metliylll-icithylenanillü segeben into the flask over a period of 10 minutes and the temperature rose from 20 "C to ¹ C. Y5 Dor The contents of the flask were briefly heated to 103 "C flask temperature and cooled to 30 ° C., using a drying tube on the cooler to remove moisture. Next, 296 g (k KoI) n-butanol, the 60 g triethylamine The mixture was poured into the flask, and the mixture was stirred for 15 minutes. During this period the temperature rose to 35 " and some solid matter was visible; the reaction mixture was poured into 750 cy} icaltae water by shaking the flask mixed, and a * layer of oil separated out *. The solvent was removed from the oil layer by ^: Dactillation. When the above half of the solvent had been removed, a voluminous bottom of fine triethylate pin hydrochloride needles formed and was filtered through ent removed * The * Pil joined was bsi 25 * "· temperature distilled at Prucle to a piston 75 * C, Dan left vrog · 'product 175 S" and this product was treated with 200 on ⁵ toluene. The flask "containing the toluene solution ^: the product" was over. Night in. A ».

iiti

'· ■■■■■ ·.' 154375t

Freezer placed. The next morning the "precipitate" visible in the flask was removed from the toluene solution by filtration, and the precipitate was washed with n-heptane. The Piltrat was taken under 10 at the pressure up to a piston temperature of 105 ° C. The weight of the Ρτο-ί product obtained was 156 g. The product was cloudy and 200 oar heptane and 5 β activated carbon were added to the product. The coal was Filtration.entfernt, and the desire product enthalteudo Piltrat was evaporated under Vakuun, wherein "to the _Elndanpfung: 0.07» ended ο pressure and 130 K Kolbenteaperatur, and it was a .'durchscheinendes, dark amber oil mi ^ obtained the refractive index njp 1.5252. When using vacuum distillation. a Vigreux column distilled the main fraction as a colorless oil over, which boiled at 0.0% of mercury between 150 and 155 ° C and the refractive index> n | ^{5 had} 1.5210. The infrared analysis confirmed the ^r

Molecular analysis and the elementary analysis4 yielded ■ - '. ■

* .. »■ * ·. the following result -. ·. .

Found 'rebuilt for

66.1 ·> · ■ · ■ · .-. 66Λ

8.5 ^v ■ '. ·; " ^: ' 8, r ^% ■ ··

io. 9; 10.9

909810/11 ^ 1

'Mi * f

Example 5

This example describes the preparation of 2-chloro-2 *, 6 * -diEthyl-N- (e # thoxyoethyl) -aoetanilide. About 1.82 kol (206 g) of chlorecetylochloride and about 210 g of bensol were placed in a 2 liter Yierbal * * * flask, and about 293 β (1.82 mol) of 2,6-diethyl-N-ethylene aniline were added to the mixture added with stirring over a period of 25 minutes · Duron the exothenae reaction, the temperature of the reaction gefflisohea rose to about 90 JC. After the Oefflischeß had cooled down to approx. 35%, approx. 250 osr trookenoe methanol were added. While the reaction was boiling under reflux, an excess of triethylaein (approximately 190 g) was added dropwise. During this addition, the Teaperatur of Oemliohes stiog to approximately? 0 ¹ C. These Tenpevatur was aufreohterhalten about 10 minutes and then reduced to approximately 30 ^ C. After cooling down, the geeiech eit was washed in portions of 500 or * Waaser. ■ The product was -befand layer in a heavy Sligen "the rom by Vakuuadeetillatlon boiling IiOsunguittel freed" with a Xndkolbenteaperatur of about "95 ⁹ C has been achieved. ' .

The Deatillatioüerüclcatand was then in 500 approx? Trimethylpentane dissolved and from it by cooling

909Ü50 / 16S1

Dry ice crystallizes. The product thus obtained had a melting point (corrected) of * 3β »5 to 59.5 * c and the following analyzer

Found Calculated IOC 62.20 62.33

^c fi Cl 13.3'i 13 »! ² * £ H 5> 21 5.19

Examples 6 to 34

The folsönden compounds were essentially by repeating de? general procedures given in the above examples

oethylacetanilide. '' - ..

7 · N- (Allyloxyaietnyl) -2-toroei-2 ^l <-parti ⁱ 1i »« butyl-6'-methylacetane llide. ...

8. 2-star butyl "
(2-propynoxymethyl) acetanilide.

* .9. 2-Broo-2'-tert-butyl-6 ^l -i (2-propynoxymethyi) -acetanilide,

Sthoacymetbyl) - c'-methylacetanilide.

11. 2-Brora-2'-tert-butyl-N ~ [2- (2 «r

12. S-bromo-2 ^l -tert.-butyi-N- (2,3-dlhy {lPoocypropo;: yK3thyl) - £ '-inethylacetanilide.

13. 2 ^l -tert-butyl-2-chloro-N- (l *> dichloro-2-propoxyinethyl) -6 * -mefchylacotanilide.

Ik. 2-Brcun-2'-tert-butyl-N- (l,> dlbro- isopropoxyethyl) · 6'-mothylacetanide.

15. 2-bromo-£ '-tert-butyl-N- (2,3-dlbro »- allyloxyaethy1) -6 -oethylacetanllld

16. 2-Broa-2'-tert-bvtyl-N- (futfuryloxyoothyl) -6 ^l -methylacetanilide.

17. 2 * -tert-butyl-2-obloivN-inethoxymethyl-4 ' , ß ^ dinwtliylaeotanilid.

18. 2'-tert. -Butyl-2-chloro-N-methoxymetby 1-6 '»methoxyacetanilld.

19 · S-Clolor-S'-tePt.-ftfflyl-.N-ethoxymethyl-6 * -iBGthylaoetanllld. .

20. 2-Bromo-2 ', 6'-diethyl-N- (ethoxymethyl) -acetanIII.

21. 2-J-od-2 ', 6'-dieth71-N * (methoxy »ethyl) acetanilide. ;

■ 22. 2-chloro-2 ^t, 6'-di8thyl-N- (EthC "cymethyl). aoetanilide.

23. 2-chloro-2 '
acetanllide.

24. 2-

• -

■ ethyl) -acetanilld

909850/1 ^ 51

- ir -

25. 2 * -tort.-Butyl-S-.ohlor-N- (2-methoxy-Utho: tynmthyl) »6'-ethyl cotanilide.

26. 2-BrOd ^ '- fceirt ^ butyl-N- ί (2.2,2-tri- ·. fluoroethoxyj-mötbylj-o-acetotoiuldld.

27. 2 ~ chloro-2 ', 6' -dimethyl-N- (methaxyaethyi) ·. acetanilide.

28. 2-ChIor-N- (isobutojcymethyl ) -2 *, 6 * -. acetoxylidide. . -

29-2-aoGtahllid.

30. 2-chloro-2 ', e'-aoetanllide. -

31 · N- (Allyloxymotbyl) -2-Qiiloiv2 ^t , 6 ^l -diKthylaoetanilid, '

32. 2-chloro-2 ^l , 6 ^l -dlaethyl-N- (ieopropoxymethyl) -ao "tanIIIide. ...

.33 · 2-Brott-2 ^f -tert.-tmtyl-6'-a «thoxy-N-

3 ^. 2-chloro-2 ^l , 6 ^t -diithyl-N- (kthanone-ethoxymethyU-acetanilide.

To illustrate the advantages of the present invention, it would be phytotoxic or herbicidal Reviews of representative α-haloacetanilides for the effect before giving up in weight

909 · ί0 / Ι · $ Γ

-18.-.

Hausvorsuchen best! sect, where a specific Number of sa <nons of a number of different plants » of (ions each represented a main botanical type " were planted in shallow boxes »those in habit-» houses used for growing seedlings.

A good Huou variety was made in aluminum trays brought and down to a low β of '9 * 5 to 12 »7 Jwn compacted from the upper edge of the shell. Above on the humus a previously steared one was made. Number of seeds of different types of plants. Both Surface applications, the sows were covered * in, to which the bowl was overfilled and the same smoothed. The measured amount of the chemical in a suitable solvent or in the form of a wettable powder was applied to the surface

the braohti In the treatments where / chemicals

. in the. Earth were incorporated »" Became the earth »the required »over the Scöalen neoh de» lakes to · to be filled at the top, weighed into a bowl »a well-known one Amount of chemical in a solution & agent. or applied in .grain of a wettable powder »the earth-thoroughly geeisch and as a top layer for the beaSten shells are used. Kacb the treatment the bowls were placed on a Cew cabinet table brought »where al · were watered from below, like it

§09850 / 1 * 51

• i - 19 -. '

was required «to have adequate humidity for to give rise to germination and growth.

Approximately 14 days after sowing and treating We shall observe the plants and record the results. The phytotoxic rating was obtained using a fixed scale - that on the average percent germination of each batch of seeds was based. The ratings are defined as follows:

0 No phytotoxicity

1 Low Phytotoxic Tat

2 Massive phytotoxicity.

3 Severe phytotoxicity

The herbicidal effect of the a-haloacetanilide the application before rising is shown in Table I for different application ratios ^ Registered application on the surface as well as when incorporated into the earth. In Table X are the various seeds represented by letters as follows:. ·. :

Winch D. Wild oats E. Trespe F. Lolch 0 radish H Sugar beet.

^J - ,. * ·. ■ BAD ORIGINAL

I. cotton J Times K Foxtail L. Chicken millet M. Blood millet N Goosefoot 0 Soybean P. • Bindweed knotweed Q Tomato R. Millet S. rice

The individual damage ratings for Each type of plant is indicated. The overall damage assessment for everyone. Grass plants and the overall damage assessment for all pulpy leaves Plants are also indicated. In the rait "remarks" titled column means (1) the application of the herbicide to the surface and (2) the incorporation of the herbicide into the soil. The data in Table I illustrate the excellent

General and selective phytotoxic effects of the suitable et-haloacetanilide.

⁷ 9O906O / KS1

link Kr. 1 lot Herbicides WArkun-j bßj. A. _k ty ,; O ναι 3 H S. Grass ; pe - "PfIr ·." - at. ill ' I. cn of example Mr.. "* ^.: kß / ha. CVIO CVIO 1 OVK I 12 ■ fs)
<*>. W.
M. CO Hp. 3 Plant type 1
1 2
2 3 .3 27
17th 16
Ö cn Mr.
Mr. 5 1.12
0.056 ^ m * ^ rf XSt Jr ^ X L2. a V ·· f "* M. K O
1 ρ- 2
3
1 3 3
3 27
.22 Q
Y Mr. 6th 0 * 056 3333232333
12 13 1 30 13 3 3 3
2 O
O
O 2 1
0 3
3
1 3
0 27
-.26. 11
7-
"7 1.12
0.28 '3 3 3 3321333
0233000023 UlUl 3
1 6th 1.
O. 2
0 2 O 27
25th
Ϊ2 11
O [I] 909 · Ιί Kr. .β- i 1.12
0.28
1.12
0.056 OM
UlUl
UIUI
UiVK
OO
MW
OO
WVK
UIUI
uiui 3 3
3 0
0 O 3
1 3 2 18th
.10 3 ill α » NT.
* .5.6 - ·.
1.12 0333220333
1 3 3 3 1 1 OI 3 3
1333030153
OIIIOIOO32 3
3
3 3
2 0
0 2
C.
. $ ΙΛΗ 3
3 2 18th
23- 18th
3- Hp. 16 5.6
0.056 ·. 2 33312 3
O OO 0 0 0 OO 3 2 3
3 O .3 1
.0 2 UJUl 3 27-
22nd 21>
8th 11] \ Uvt
0.056 .83 * 3.3.2 3 3
2333000033 3 ϊ MfO 2
O 3
3 3 18th ¹ p 5.6
1.12 '3333331333
0233000033 3 WUl O 26th
21 BATH 0.28 3 3 3 3 3.3 3
1333 10 0033 3 3 ■ l ' ORIGIN) 8333220233
03232 0033 3 3 I. > »
Γ " . · ■ "

15 4 3 7 5 T

3
j-.

to

ο
ο 3

4Λ 4- »

δ «>

WS
O <Ι)

!
I.

Wi K-

1-1 Oh
D.

approx
al

CUCV) CUCM CUCJ

C-CJ

CiCU

«Ι

a, | ho

O {CUO

“I tACU

CViO

KSKN

Ml
O |
Cti |

Qj

H
IOH

CUO

K \ <M

• ϊί O
CUCU

KNCU

KMO

OO

OO

OO

WHERE

KN K \

KNCU

KNKN

OO

OO

OO

OO

KNKN

ΚΝΚΛ

oo σ \

KNH

OO OH

ϋ | CUH OO

KNKN CU

KNCU H CU

HO HKN KNO KNO KNO CUOI

- 22 -

S.
I.

ϋ ^

VO

cute cum

HCU HO

HO HO H.O

in
«I.

St.

• Χ ■

- 23 -

The contact efficiency of representative o.-Kalogonacetanilie was determined in greenhouse experiments. The compound to be tested was applied in the form of a spray to plants of the same types of grass and broad-leaved plants as used in the above pre-emergence experiments at a given age, and the same number of seeds of the same plants were planted in aluminum trays. After the plants were of the desired age, each aluminum sole was sprayed with a given volume of a solution of the chemical to be tested at a concentration of 0.5% corresponding to an amount of approximately 11.2 kg per hectare. This solution was made from an aliquot of a 2% solution of the test compound in acetone, a known amount of a mixture of cyclohexanone and emulsifier, and enough water to make the desired volume. The emulsifier was j6 by weight contained a mixture. £ 35 weight Butylamindodecylbenzolsulforiat and 65 of a condensation.] Tion product of ethylene oxide with tall oil and about 6 moles of ethylene oxide per mole of tall oil. The damage to the plants was then observed approximately 14 days later and are shown in Table IX. specified. These ratings are the same as above.

■ ■ ■■ · * "■ · ■. ■ -r" - ■

, - ORIGINAL BATHROOM

909850/1651

from Tabel II It . 1 Qr & ser Broad biathlon
plants η U 2 3 2 Phytotoxic 1 η ti . 8th 1 2 link Il ι
contacteffectiveness of α-haloacetanilides Il 9 2 2 link η Il 13th 1 3 B. Il Il 14th 1 2 Il Example no Il 15th 1 1 N Il Il 16 1 1 N Il 1 Il Il. η n Il t> Ii Il

The above data are merely illustrative; the other indicated a- »haloacet ~ > anilides have equally favorable properties.

The phytotoxic agents of the invention.
are either special substances consisting of individual parts or liquid concentrates, ^ dIe. the host substance and ''.,

either »ine from single cells .consisting · Plague substance i

or contain a liquid auxiliary agent; which

the latter an aid for attachment or a
Conditioning agent is that it. be mixed i kannKun carrier to be in a shape overall ι braoht that an immediate assimilation, - allows the media · leioht with a suitable solid or liquid

; · - "'/ ■ * / » ■ •; - ^:. ■ · ;;. · -Τ ..; ■■ Ί = - 9099te / 19ti:

made possible by the plants. Include accordingly the means according to the invention not only the concentrates, which contain the active substance and the auxiliary also poisonous substances applied to your field and contain the concentrate (i.e. active substance plus auxiliary) and the carrier.

As demonstrated above, by modifying the method of using the compositions of the present invention very different effects can be obtained. So an unusual grass specificity can be found at lower Application rates can be achieved, while at higher application rates a more general phytotoxic one Effect or sterilization of the earth takes place. Hence the establishment of the means forms so that they become a evenly predetermined application of the agent to the environment of the plant to achieve the desired Allow effect, an essential part of the invention, ■ '.; '. '

Phytotoxlβoh · auxiliaries used in the manufacture The concentrates that can be used include solid or liquid components consisting of individual parts Extenders, such as solvents or diluents, in which the active substance is dissolved, suspended or distributed. Wetting agents or emulsifiers that * gleiehraäasige dispersions or solutions are used for this

y * - BAD CfBGlNAL

; ; -: 154375t

to deliver the active substances in the extenders,

ι and adhesives or spreading agents that the ;; Improve the contact between the wort and the soil or plant surfaces. All erflndungsge-cash contain at least one of the above types of supplies and usually contain _<r because of the nature of the physical properties of a-Halogenaoetanilide an extender and a network; '. . medium 'or an emulsifier. >

In general, the α-haloacetanilides are insoluble in water and in many organic solvents. The active substance does not need to be dissolved in the extender, but can only be dispersed or suspended. Examples of organic solvents suitable for use as extenders are hexane, benzene, toluene, acetone, cyclohexanone, methyl ethyl ketone, laopropenol, butane: diol. Methanol, ", diacetone alcohol, xylene, dioxane,, isopropyl ether, ethylene dichloride, tetraulfoethane," r "hydrogenated naphthalene, heavy benzene, petroleum" - """fractions (e.g. kerosene, etc.) and the like. When using mixtures of organic solvents eg Oeaischen of xylene and cyclohexanone ia comparison] ■ hlltnis lsi and 1:; | \> - 2, can eohte solutions mfd · - ■..

•does

; V. / ^: Si.

f.

{■ '

9O9t $ 0 / 1l | f

Extenders consisting of individual parts are in the practical implementation of the present one Invention also very useful. The effective subatanx is either on the finely divided solid material » adsorbed or dispersed in the finely divided solid material. Suitable solid extenders are natural clays; such as china clay, bentonite

and attapulgites, other minerals in natural

Condition, kio e.g. Tallc, pyropnyllite, quarr, diatomaceous earth, Puller earth, chalk, phosphorite, kaolin, diatomite, volcanic ash, salt and sulfur, chemically modified Minerals such as acid-washed bentonite precipitated "; Calcium phosphate, precipitated Calolumo carbonate, neutralized magnesia oxide and colloidal silica, and other solid materials, such as powdered cork »powdered wood and powdered pecan or walnut shells. These Materials have been cut into pieces, at least in a size of 0.15 to 0.833 mm, preferably in a much finer size.

The solid concentrates, which consist of individual parts, are applied to the Srde la mixture bit Solid carrier material consisting of individual parts or powder wettable in formulas for use a · liquid carrier · applied. If that

^J. lOllM / tUt

the latter method is used, the concentrate ' a wetting agent or a surface-active smock suae-ietzt, UD the fixed consisting of individual characters -. Make extender wettable by water, creating a constant aqueous dispersion of the suspension is obtained that ι for the use of ale spray is suitable.

V The surface-active agent in which he « fine: mgsgeaaBsen means is used to equal « massive dispersions of all components of the approach both liquid and dust-free agents in the applied concentrates as well as in the applied poisonous agents can be anionactive, cation active or non-ionic or a mixed type. Suitable surfactants for the production of both solid and liquid agents • are the baked soaps, such as salts of long-chain carboxylic acids, sulfonated · animal,.:,. vegetable and mineral oils quaternary salt - /, of high molecular weight acids, rosin elves,:,;

such as salts of abietic acid, sulfuric acid salts «. · [

of organic compounds with high "molecular weight;"

weight, algae soaps, with fatty cures · alkylphenols

and meroaptans, condensed ethylene oxide and other simple and polyamic materials, both hydro-V ''' ¹ . '*

. . ^ BATH

phllen as well as hydrophobic functions.

The liquid concentrate agents according to the invention preferably contain oa. 5 to approx. 95 öew.-jS the active substance and, as the rest, the aid «just that can be a liquid extender or a surface-active agent (including glue), but preferably a combination of liquid extender and surfactant. However, it is preferred that the herbicidal adjuvant predominate Represents part of the remedy. Preferably the surfactant makes up approximately 0.1 to approx. 15 Qew .- $ of the total concentrate agent, the remainder of the agent being liquid diluent.

Because the a-Halogenaeetanilide are very toxic and are usually applied in small amounts, • in order to obtain selectivity, the concentration, the active substance in the dusts has such low values like 1 Qew.- £ or less. When the dust means are used for the sterilization of the earth should, it is desirable to have a high concentration ' have, and the active ingredient can so. large quantities like ' Make up 5 to 98 pounds by weight of the total composition. Of the The remainder of the agent consists of the excipients. .

That for the equal distribution of the '; a-HAlog »n * oetanilide · used in effective amounts ..

909850 /

Carrier material can either be a liquid or a solid material made up of individual parts. Usually the carrier material is the main component of the applied funds and makes up more than 50 Gsw.-i «of the middle. For reasons of economy Water is the preferred liquid carrier for both the liquid concentrate compositions and for the concentrates consisting of wettable powders. Suitable solid supports are those given above extenders consisting of individual parts, including solid fertilizers such as ammonium nitrate, urea and Superphofcphat, as well as other materials in which Plant organisms take root and grow, such as compost, manure, humus, sand and the like.

The agents according to the invention can also other additives such as fertilizers and pest control agents contain «the support materials or used in combination with support materials will.

Phytotoxic agents which are useful in combination with the compounds described above, are e.g. 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, S-methyl - ^ - chlorophenoxyacetic acid and the salts. «Esters and eels of them,. > Triaain derivatives such as s.B. 2,4-Bie ^ (j-B «thoxypropylaniino) -

909I50 / 1SS1

6-mathylthio-s-ti \ i.EZin, g-

propylar.; ir.o-a-trlazin and S-ethylamino-A-isopropyletrino-ö-K.ctliylr.icrcopto-ß-triasin, Urea derivatives, ινίσ e.g.> (3,4-Diehlophenyl) ~ l, l-dimethylurea and J-ip-ChlorpheiiylJ-lil-'diiaethylurea, Acetanilide ^ such as N-isopropyl-a-chloroacetanide, N-ethyl-a-chloro-2-methylaoetanilide and 2-tert.-butyl-2'-chloro-6-mochylacetanilide, and acetamides, e.g. NiN-Dlfaliyl-a-chloroacetamide, N ~ (cc-chloroacetyl) -hexamethyleneimine and Ν, Ν-diethyl-a-bromacctamld and like that. "

The funds according to the invention can be found under Use of motor-driven or by hand actuated devices for the distribution of dusts and the spraying of liquids, by additive to irrigation water and by means of other common ones 'Procedure to be applied to the foliage of growing plants. The funds can also be used as dust . or spray are applied from airplanes, as they are effective in very low doses.

The dosage to be applied to the plant depends not only on the special a-halogen acetanillide from, but also from the special plant species that

should be influenced, and the growth period

the same as well as the part of the plant that begins with dta

909850/1151 bad original

Olft should be brought into contact. At nioht selective foliage treatments will be the most inventive ·. This means usually in a quantity of approximate -

"EIEE 5.6 bia 56 kg α-Halogenaoetanilid fro ha placed on overall ■ '■ but lind lower in some cases or * grosserβ amounts suitable. With nloht eelective Be * ·. In action before the sprout, the agents are usually applied in about a smaller amount, but within the same general range, ie 1.12 to 28 kg per hectare According to the invention, an aterilla atlon of the earth is usually achieved in an amount in the range of 1.12 to 11.2 kg per na · When applied selectively to the vapors before they rise, a dose of 0.056 to 5 * is usually used. 6 kg of active substance per hectare applied, but in other cases smaller or larger amounts can be used. Ea is assumed, 4a «a oW fa ^ aaee« e) ^ '

The above information elnaohlleealleh er BeiapieU lileh ^ | |

the og "la" te i ', which is "objectionable" in every special hall

•. · ■■ ..-... · -τ;: -: -; -. Μ · Amount can determine. · · '- "' _: ■; '.

Although the founding "it Beaug on." apeal Let the ear shapes be observed, all of which Binalities not old in "ahrgJhen" anajeeetMA warHn.,

9098S0 / 16S1

It is advantageous in the preparations according to the invention as ^ -haloacetanilide 2 ^i: -tert-butyl-2-chloro-III-methoxyaethyl-6'-nethylacetanilide, 2'-tert-butyl-2-chloro-N- (2-propynyloi: methyl) -6'-ethylacetanilide, 2'-tert-butyl-2-chloro-N- (allyloxyEiethyl) -6'-methyl-acetanilide, 2'-tert-butyl-2-broia-K-ir.ethoxymethyl-6 '- methylacetanilide, 2'-tert-butyl-2-bromo-N- (2-propynyloxynethyl) -6'-raethylacetanilide, 2-chloro-2, 6-diethyl-N-methoxymethyl-acetanilide, 2 '-tert-butyl-2 -bromo-N- (allyloxy2iethyl) -6 ^l -methylacetanilide, 2 · tert-butyl-2-chloro-N- (2-aiethoxyethoxymethyl) -6 · methylacetanilide, 2 · tert-butyl-2-bromo-N - (2-methoxyethoxymethyl) -6'-methylacetanilide, 2-bromo-2'-tert-butyl-N- (2,3-dihydroxypropoxymethyl) -6-methylacetanilide and 2-chloro-2 '»6 ¹ -dimethyl- Contain N- (isopropoxymethyl) acetanilide.

90 98S0 / 1681. bad original

Claims (12)

- 34 claims 1. Phytotoxic or herbicidal agent, which is a Contains phytotoxic adjuvant and an aniline derivative, characterized in that as aniline derivative a β-haloacetanilide of the formula Z
¹ 1 .CH ₀ -ACZ C-CH ₉ X
0 1 2
is contained in which R and R are alkyl or alkoxy with 1 to 1ü carbon atoms, R, halogen, alkyl or alkoxy with 1 to 10 carbon atoms, η is an integer from 0 to 3, A is oxygen or sulfur, X is chlorine, bromine or 1 ? Iodine and Z, Z and Z hydrogen, alkyl, alkenyl, alkynyl, Alkoxy or polyacoxy with 1 to 18 carbon atoms, aryl with 6 to 24 carbon atoms, heterocyclic radicals with a maximum of 24 carbon atoms and 1 to 3 hetero- 1 2 atoms or two of the substituents Z, Z and Z to form a divalent alkylene radical with 1 to 6 Carbon atoms are combined. One or more of the 12th
Substituents Z, Z and Z can be provided with non-interfering substituents including halogen, hydroxyl, alkoxy, nitro, dialkylamino, carbalkoxy, keto groups and the like. 9098S0 / 1.651. ^ÖAD * J %. Process for the preparation of compounds of general formula t ι -ACZ ¹ R ^a _n R ^a O rewarded by the fact that a compound of the general formula. CKtX is implemented : i, with a compound of the general formula: · "'2 ■ - ■■'.: .. ■." ■■ .i '' ■■ where t; halogen, R ¹ and Rf alkyl -odtr alkoxy ait 1 ble 10 carbon atoms, R · halogen, alkyl or alkoxy with 1 bit 10 carbon atoms, η a whole number of 0 bit 3 »A oxygen or sulfur» X chlorine, Bromine or iodine and Z, Ϊ ¹ UaA 2 * W * ie "retpff, AIk ^ l, Alkenyl * :: Alkii" jrl, Alkoxy or Polrallcory alt 1 to 18 carbon atoms, aryl silt 6 to 24 cabbage "netQffato" en, ne'teröcycliiehe radicals with ¹ at most 24 carbon atoms and 1 to 3 heteroatom ·! » ', mean or ewei of the substituents Z, I and Z are purified to form a divalent alkylenet with 1 to 6 carbon ethers. ■ 1 . BATH ORIGINAL