DE2107715A1 - 1 (substituted hydrocarbyl) dl and trihalogenpyrazoles and their use as herbicides - Google Patents

Description

LAWYERS

DR. JUR. DIf ¹ L-CHnM. WALTER AT

ALFRED HOV.YSNER

DR. JUR. i'rtNS wii: \\ B £ 1L ■ "'leö.ia / l

FRA. '. OUTi AM MAY N-HOCHSF

Our ur.

! • he Upjohn Company Kaiaiu ·. : coo, ι <α1 eil. , V ". Öt. A.

l- (F.ua ^ titu i ^ i'J ^ j ^^^ ocjirbyl.) -di-_ una -t rihalogenp / .g-azoles and their Yerwenaun ^; as herbicides.

The invention relates to 1- (substituted-HydroG & .rbyl) ■ di- and -trihalCi. '; enpyr; i5iole uer Allgemeineil i'oruel:

in the

"n" ai-i ganae Zani U ₁ 1, 2 or 3, "X" a halo ^ eniixoüi, "m" (Jx - fermented number 2 or 3, where the halogen. · tome

109835/1710

are far from each other,

R ".ein" asBerstoiia-tüiü, an iilKyl ^ ruore with i to Iv carbon atoms ο α er an alkenyl ^ rupee -tit 2 to 10 carbon atoms, where the quinines of the ivorü. En material atoms in the

* -f ° η ^Η 2η -

no longer a.i.a U Cetr ^^ t, and

"a" aie carboxyl .Tupo ^ as well as neron aI.'c ^ Li uet & l] .-, träfet. alkali metal, iiiijaoniuni— οα- ^ r üniimalze, lie rivaroxv-

ißethylgrupcfc, a Hyciroxväietnyl-niea.- l! :: ariüHr _ö TUüpe suit i ris c Samens toi Ta lojaen iin niij-ier-ΛΐκνΙ-ree.t, a Üaruonsäux'e — niea.— ^ .Ικνΐ esueri.rur. oe; i; i;, L to ö ivonlen -'-: i; oi "iir.to ^ eii iiu nieaer-ülkyire -t, Jie

Cvano ^ rupoe oj.er eir: e _J arrjori: -: äurv;:. Iji.i ^ rupDe aer ror-

"0 '.-,
mel " .- ^a l , where R- un. ·. m- Vasser-

R ₂

stoffaxome o'ier following, voneina.naer anaoirjnifce suustituentengru'ouen show: a lower a.lkvlre? t.

with 1 to 8 KonlsnstGrfatoaen, an a Is: en ν Ire st with 3 Dis β jtohlenstoTratoaien, a ülkynylreet with 5 to 8 carbon ens toi "f atoms, a« .ralicylr ^ r-.t with 7 to 1'6 liohlenstoTi ' HCcmefi, an η aryl radical with 6 to IU Λ.οη1 ens.-coxfatomen, where R- ^ una up cannot be aryl, a cycloalkylreat with '5 to b Kohlänstot'faconiein, a CyclG'ilkenylrest with 4 to δ Konxent -toffcitomen and

the -N% group together consist of a / -e.saturated R ₂

heterocyclic imino group with 3 to 7 ring atoms with a total of no more than 15 Kohiens to Tiutomen, a / experienced for their production and their use as Herbicides, as well as wittel zur Re ^ oncrJ f? rum? of

109835/17 10
ν BAD ORIGINAL

ί f 1 ar.zenv:. ·! oh ^ t. \, i: iF.

I.en to aeu lower ülkylg-rapoen ndt "ι to 8 carbon Atoraen"; ren example hethyx, Atnyi, Prcpyl, .butyl, pentyl, Hexvl. Heotyl, Cctyl as well as their isomeric forms, iil-Kylferui>,: s with "1 to 10 C-atoms" are apart from the already mentioned, the _ ⁱ .onyl, Decyl soi ^ apren isomeric forms.

Aen to Alicenylgruppen with "5 BiB B C-Atoiiien" include, for example itllyl, 1-KethvlHllyl, 2-allyl kethyl (Letiiailyl), 2-.Butenyi (crotyl), "^ butenyl, 1,2-DiMethylallvL, 3-Kethy ] -2-Dutenyl, 3-Pentenv'J, 2, '1-Dirnetliv. L-2-D ^: \ tei: -yl, 1,1, -'-Trim-ithylaHyl, 1,5-Di _:! Etiiyl -2-butenyl, 1-eth.vl-2-butenyl, 4-kethyl-2-T: entenvl, 2-ethyl-2-oentenyl, 4, £ -iäi.niethyl-2-pentenv;:., 2- -; Her.tenyl, 2-octenyl, 5-üntenyl or 1,4-ßiiuetnyi-A-NEX / n i iienvlt Al: rU:> r: s issit IC C-Atcnien.!. "2 bi.""sim suiier aer. prepare auiVt-iühr-rii the Vinvl, 2-Ncnenvl oa ^ r 2-JJecenyl.

"u α en iilrOTivl ^ -rUi pen with" 5 Mn ü C atoms " _v .- _r / ·..> .., _n bei.";:> ej? .-- c ± 8 "; A-rr-.i. vnyl, 3-hutvn" l, 2-Pentynyi., l, l-Dir ^ ethvl-2-propynyi. 2-riexynyi, 2-het; tynyl, 2-uct ^ iv. / L or 1,1 "^ -T rim et: .-> \ L-4-pent vnyi.

For Λ- ^ η iii-ilkyl-crupper -nit "7 to 13 carbon atoms" see at? Oiel3v; eit: -e ± 5ensyl, Pnenäthvl, 1-Phenvläthvl, j-Püsnylurov-yl, 4-PhenylDu tvl, b -Phenylhexyl, S-phenyl-2-metalyli5entvl, benshyciryl, 1-iaphthylinethyl. 2- (l-l'Taph thvl ^ -ätnyl or 2, (2-Nar nthyl) -ätftyl.

The term "aryl with 6 to 10 carbon atoms" includes, for example, pnenyl, ax tolyle. the xyIyls, hesitvl, 4-tert.-isutylchenyl, 2,3-iJi cnl or hene yl, 3-anisyl, A-

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Ψ octyl.

Ethylphenyl, 3,4,5-trimethoxypheriyl, 4-bromo-2-methoxy phenyl or 2-chloro-4-tolyl.

"Cycloalkyl with 3 to b carbon atoms" includes, for example, cyclopropyl, 2-methylcyclopropyl, 2,2-Diiaethyicyclopropyl, 2,3 - Üiätnylcyclopropyl, 2-i3utyl cyclopropyl, CycloDutyl, 2-methylcyclobutyl, 3-irropyl cyclobutyl, 2, 3 ^ - Trimethylcyclobutyl, Cyclopentvl, 2,2-Dimethylcyclopentyl, Cyclohexyl, 3-Methylcyclohexyl, 2,2-Dimethylcyclohexyl, Cycloheptyl or Cyclo-

Gycloalicenyl groups "with 4 to 8 carbon atoms" are for example 2-cyclobutenyl, 3-cyclopentenyl, 3-cyclohexenyl or 2-ethyl-3-cyclohexenyl.

The "saturated heterocyclic AininogruTipe with up to 7 ring atoms and a total of not more than 15 carbon atoms" can z. ± s. present as aziridinyl, never alkyl aziridinyl such as 2-methyl aziridinyl, 2-ethylaziridinyl and 2-butylaziridinyl, poly-lower-acylaziridinyl such as 2,3-dimethylaziridinyl and 2,2-dimethylaziridinyl, azetidinyl, nieaetid-alkylaziridinyl 2-J> iethylazetidi- ψ nyl, 3-ftethylazetidinyl and 2-octylazetidinyl, poly-

niea.-Alkyiazetidinyl such as 2,2-dimet; hylazetiuiriyl, 3 »3-diethylazetidinyl such as 2,2-Lxinethylazetidinyl, 3» 3-diethylazetidinyl, 2,4,4- ^r iriiaethylazetidinyl and 2, 3, 4-Trimethylazetidinyl, pyrrolidinyl, lower-alkylpyrrolidinyl such as 2 ~ methylpyrrolidinyl, 3-butylpyrrolidinyl and 2-isohexylpyrrolidinyl, poly-lower-alkylpyrrolidinyl such as 2,3-dimethylpyrrolidinyl, 2,2-dimethylpyrrolidinyl, 2,5-diethylpyrrolidinyl and 2,3,5-trimethylpyrrolidinyl, .dino, nieäer-Alkylpiperidino like 2-Methylpiperidino, 3-Wethylpiperidino, 4-Methylpiperidino, 3-Isoproüyl -

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piperidino and 4 -tert.- butylpiperidino, poly-lower-alkylpiperidino such as 3,4-diethylpiperidino, 2-methyl-5-ethylpiperidino, 3,5-dipentylpiperidino, 2,4,6-trimethylpiperidino and 2,3, 5- ^r l'riäthylpiperidino, hexa - "methylenimino, lower-alkylhexamethyleneimino such as 2-ethylhexamethyleneimino, 4- tert- butylhexamethyleneimino and 3-heptylhexamethylenimino, poly-lower-alkylhexa - '.' ^

methyl enimino like 2,4-dimethylhexamethyl enimino, 3,3- ·. \ *, -

Dimethylhexamethyleneimino, 2,4,6-tripropylhexamethylene- "* ^{% <}

imino and 2,2-dibutylhexamethyl enimino, 4-never der-alkylpiperazinyl such as 4-methylpiperazinyl and 4-isopropyl piperazinyl, Poly-lower-alkylpiperazinyl such as 2,2,4,5,5-pentamethylpiperazinyl and 2,4, 5-trimethylpiperazinyl » Morpholine group, lower alkylmorpholine group such as 2-ethyl- '■ "

morpholine and 3-isobutylmorpholine groups, poly-lower-alkylmorpholines such as 2-ethyl-5-methylmorpholino, 3,3-dimethylmorpholino and 2,6-di- tert- butylmorpholino, thiamorpholino, lower-alkylthiamorpholino such as 3-methylthiamorpiiolino and poly -low.-alkylthiamorpholino such as 2,3 »6-trimethylthiamorpholino and 2,3,5,6-tetramethylthiamorpholino.

Those listed above, as well as many similar ge '' '<

saturated heterocyclic amino groups are within the scope of the invention. The saturated aminoheterocycle must not be present as alkyl amino, and there may be a second heteroatom in the ring, such as an oxygen atom, a sulfur atom or a second ring nitrogen atom. In general, the second heteroatom should be in the 4-position of a six-membered ring, but it can be are also in the 3 position. In view of the preceding meaning, "Taken together, the means

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^ R ₁
-N - G group a saturated heterocyclic amino

group with 5 to 7 ring atoms "it can be seen that the R ₁ -

how

- and R ₂ chain can be present as alkylene, oxadialkylene

III! ¹¹ I!

..C-C-O-C-C- or -C-O-C-C-C, thiadialkylene like

Mil'ill »

I ι ι I ι ι ι ι

-C-C-S-C-C- or -C-C-C-S-C-, or N-alkylazadi-I [Ij j j [I alkylene like

alkyl alkyl

Mill MlM

.C-C-N-C-C- or -C-C-C-N-C-.

Another jJinition for this is therefore the following:

fc Taken together, R ₁ and Rp mean as thin

with the jtf <C -. & tom saturated heterocyclic amino groups with 3 to 7 ring atoms, each G group not having more than one? has 15 carbon atoms and one of the ring atoms is carbon, oxygen, sulfur or a second nitrogen atom and the other ring atoms are carbon atoms, so that R ₁ - R _{2 represent} alkylene, oxadialkylenes, thiadialkylenes or N-alkylazauialkylers as a unit.

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The i- (substituted-hydrocarbyl) -di and -tri haiogenoyrazoles Formula 1 is obtained through conventional chemical reactions. The di- and trihalopyrazole-1-aikanoamides and -1-alkenoamides (compounds of the formula I in which "A" represents a carboxylic acid group) are prepared by conventional methods for the preparation of carboxamides. This group more inventive Compounds corresponds to the structural formula:

Yes

in the n, X, m, R, R-, and Rp meaning above
own.

For example, unsubstituted amides (compounds of the formula Ia in which R-j_ and R ₂ both represent a hydrogen atom) are obtained by reacting alkyl-d ± - or -trihalo-pyrazole-1-alkanoate or -1-alkenoate from di- oaer trihalo-pyrazole- l-alkanecarboxylic acid or -1-alkenecarboxylic acid chloride with ammonia. One saturates, for example
a solution of alkyl di- or trihalogenopyrazole-l-alkano-

at oaer -1-alkenoate in an organic solvent, preferably an alkanol such as ethanol, with ammonia and

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lets aas reaction mixture lane at about 25 G for several days or until they are fully implemented. To the implementation To accelerate, however, one can also heat the reaction mixture, with loss of ammonia through care must be avoided or refilled. The resulting di- or trihalogenopyrazole-1-alkanoainide or -1-alkenoxainide is obtained by removing the solvent and excess ammonia. The product can Purify using conventional methods, e.g. by distillation, column chromatography and recrystallization.

N-substituted amides (compounds of the formula Ia in which R-, and R _? Or one of these two represents one of the specified substituent groups) are obtained, for example, by preparing a di- or trihalogenopyrazole-1-alkanecarboxylic acid or -1-alkenecarboxylic acid halide, For example, a chloride or Bvomids, and by subsequent reaction of the same with a primary or secondary Umin. Di- and trihalogenpyrazole-1-alkarecarboxylic acid and -l-alkenycarboxylic acid chloride are obtained, for example, by heating a di- or trihalogenopyrazole-1-alkanecarboxylic acid or -1-alkenecarboxylic acid with thionyl chloride. The desired amide is prepared by slowly adding acid chloride to a solution of the selected amine and, if necessary, stirring the reaction mixture after the addition has taken place in order to complete the reaction.

VJwill be an effective implementation of the chosen Lorimera or secondary amine, then the reaction mixture can have a strongly basic acid acceptor, for example a tertiary ümin, for example a trialkylamine such as triethyl

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ami η, are added .. Suitable solvents for the The latter implementation includes benzene, toluene, diethyl ether and tetrahydrofuran. To obtain the desired fl-substituted di- or trihalogenpyrazole-1-alkanoamide or -1-alkenoamids is that which arose during the reaction Ainine hydrochloride washed out with water and removed the solvent. The product can be purified by Ulli crystallization.

In the aforementioned implementation, they end lower Amines are used and the reaction mixture is heated, then amine losses can occur from the reaction mixture be avoided by using a cooler or carrying out the reaction in a closed system.

The alkyl di- and trihalogen pyrazcl-l-alkanoate according to the invention and -1-alkenoate esters of the formula I. have the formula:

H "

RCC H ₂ -CO-lower-alkyl

Ib

U) _m

where n, X, m, R and lower-alkyl have the preceding meaning to have. Compounds of this formula Ib are obtained by reacting an alkali metal salt (preferably one ihitrium- your potassium salt) of a di- or trihalo ^ enoyrazole3 with an alkyl haloalkanoate or halogen -

Ί09835 / 1 71 0

-ι ©

alkenoate. The formula for suitable alkyl haloalkanoates and halogen alkenoates can be, for example:

H "

R-G-CH -C-O-nieaer-alkyl II

where n, R. and lower-Aikyl have the above meaning and X 'is a halogenator such as chlorine, bromine or iodine represents.

The alkali metal salt of trihalopyrazole is preferably prepared in situ - aaaurch that one Alkali metal, an alicalinietal alkoxide or an alkali metallhydria with a solution of the trihalopyrazole in a /! organic solvent mixed. The solution to the alkali metal trihalogenopyrazole thus obtained is subsequently obtained slowly with the chosen.-iicylhalo ^ enalkanol or halogen alkenoate eier formula II added, ta cn more complete Implementation can restrict the reaction mixture, acidified and then with the help of alkali metal ceroonate scxiwach -based. The desired «.Ικν-1-ai- or -trihalogenpyrazole-1-alkanoate or -1-alkenoa.tester is in a commercial manner e.g. by solvent extraction, Solvent processing, precipitation and recrystallization won and cleaned.

The new di- and trihalopyrazole-1-alkaricarboxylic acids and -1-alkenecarboxylic acids of j? ormel I (compounds, in which "A" is a carboxyl radical) -weraen by conventional alkaline hydrolysis from the corresponding α er. Esters

109835/1710 _PAD ORIGINAL

manufactured. If appropriate, the alkylai- or tri-hialo ^ enpyrazole-1-alkanoate oaer -1-alkenoate in the reaction mixture, in which it is formed with an alkali metal hydroxide hydrolyzed and the AlJcancarbon or Alice caronic acid obtained by using for .Neutralisierung aerase and for the precipitation of the di- or trihalopyrs.i-.ol-1-a.lkan- or -l-al ± cenoic acid adds a strong acid.

According to a preferred, novel, ^{fiction, contemporary process, the di- and i l} rihalogenpyrazole-lalkanecarboxylic and -1-alkenecarboxylic acids are prepared by first preparing a di- or trihalopyrazole in the presence of an alkali metal carbonate such as potassium or sodium carbonate and acetone with an Reacts alkyl haloalkanoate or haloalkenoate (according to formula II) and then hydrolyzes the resulting esters to form the corresponding acid.

The di- or trihalo pyrazole is dissolved in acetone and mixed with solid anhydrous alkali metal carbonate. The Gemitch is heated for a few minutes, then cooled and with the alkyl haloalkanoate or haloalkenoate offset. After further heating to the reflux tempera door and subsequent cooling becomes aqueous alkali metal hydroxide added, the acetone separated out and the reaction mixture brought to reflux temperature again, u "i To effect hydrolysis. The resulting solution, the di- or trihalogenopyrazole-1-alkanecarboxylic acid or -1-alkenecarboxylic acid alkali metal salt containing solution is acidified for the purpose of precipitation of the free acid. This free Acid is collected on a filter, washed to the Remove salts, and dried.

10 9 835/1710

BATH ORIGINAL

The di- um α l'rihalogenpyrazol-l-alkanecarbon and. -lal & enc - ;. rboxylic acids bilaen balze with alkali metals, alkaline earth metals, aminonia and amines. The salts are obtained by Nutralisierung aor Baure with an alkali metal hydroxide such as sodium, potassium or Lithiuranydroxid, with an alkaline earth metal hydroxide e vn calcium, barium or magnesium hydroxide, ammonia OAER with an amine such as I ^v ionosphere, di- and triethanolamine , Triethyiarain, Isopropanolamin, Iso ^ ropylamin, Piperidin una Korpholir .. Oil-soluble balze arise when using tert.-Alkyl-Orirn. amines, in which the aluminum substance is bonded to a tertiary carbon and has a tertiary all-carbon atom having up to about 22 0 atoms.

The production of. '5 , ^ -uihaio ^ enT. yr - jz '/ il-alkariols and -1-alkenols of the formula I (compounds in which "A" is a hydroxymethyl radical in aene) is expediently carried out using formula Ib, which is mixed with lithium aluminum hydride in an inert organic solvents such as dietary ether reacts -weraen; it köririer. aoer aucü anoere, ce / ai? 'afirjinanr known errands are used for the auctioning of esters to alcohols,', v'irci. on aie named consecration a tri-analog ester (connection of the formula Ib, i ;. aer m -jie Z- hl ar-i beueutetj reauziert, bo värd. aas Jaaloi-.enatoni in 4-position replaced by a V / asteroid atom.

3,4, 5-Q: i-j nalot'enpyrazoi-1-alkanols and. -1-alkenols aer j? 'or: ael I (VerDi ndungen, in aenen "a" an iyaroxyciethvire & t is; is obtained expediently by aem method aer Examples 40 and 41. here is a di- or trietio-enpyrazole with a haloalkyl or haloalkenyalkanoate to a lower alkanoate ester of a Lx- oaer trihalogenpyrazole-1-alicanolfi oaer -1-alkencli: (. r..z.h. example

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implemented, üas optionally to Di- oüer 'Irihalogen pyrazole-1-alkanol or -1-alkenol (see e.g. Example 41) can be hydrolyzed.

The di-una i ⁱ rihalo, -; enpyr & zol-l-alKa.nonitrile and -1-alkenonitriles according to formula I are obtained by mixing and heating an alkali metal salt of a diocer trihalo-Meivoyrazole with a chloro- or bromoalkanoni L-ril oaer -alkenoriitrii in an inert organic solvent such as toluene or benzene. The resulting dihalogenpyraiiol-1-alkanonitrile or -1-alkenonitrile is obtained by washing out the courtship formed during the reaction and any by-products, drying the organic phase and removing the solvent. The nitriles can be purified by conventional recrystallization.

The di- and trihalopyrazole-1-alkanonitriles and -1-alicenonitriles Eier formula I can also be N-unsubstituted. -Di and trihalo-pyrazole-1-alkanoamides and -1-aikenoamides getting produced. For this purpose, the amide is chi orid with phosphorus pentoxide or phosphorus oxy according to ORGANIC SYNTHESES, anthology 3, page 493 (1955). The wished Di- or trihalopvrazole-1-alkanonitrile or -1-alkenonitrile is obtained by distillation or solvent extraction and by precipitation.

Example 1:

Hö retel development of ethyl-3,4, ^ -tribr ompy razo l-l acetate.

A solution of 7.1 g (0.31 mol) of sodium in 300 ml of absolute ethanol was with vigorous stirring with 92 g (0.3 ■

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Mol) "3,4,5-tribromopyrazoi were added. When the mixture was completely mixed, 100 µl (0.6 mol) of ethylene oxide were added with continued stirring. The mixture was diluted with 200 ml of absolute ethanol and the whole thing was stirred for about 1½ hours at about 25 G. i-ian dyia-o te under reduced pressure a ^ n ^ roasting part Ji3 Äthr-r.ol "-jb, then added 100 ml of 6% hydrochloric acid to the residue and made this aqueous acid mixture alkaline with solid sodium carbonate. The aqueous solution was separated off and extracted three times with 60 ml of inhaler each time. The ether extracts were combined, washed three times with 40 ml of water each and dried over anhydrous amesium sulfide. Evaporate BachUn ₆ - of the ether under reduced pressure, a white plague was obtained. Uuikri crystallization from technically pure hexane (Skellysolve β, a mixture of isomeric hexanes with a boiling range between 61 and 69 ° 0) gave 96.0 g of ethyl 3,4 -.-tribromopyrazole-1-acetate with a melting point from lül-10? 0.

Analysis:

Calculated for C ₇ E ₇ Br, N ₀ O ₀ :

₇₇

G 21.51; H 1.81; N 7.17; Br 61, '55; found: G 21.79; H 1.62; N 6.96; Br oil, 56.

In the above procedure, the ethyl bromoacetate is carried out Methyl 2-bromopropionate, ethyl-5-broüiproOionat, Äthvl-4-bromobutyrat, Isopropyl bromoacetate, tert-butyl bromoacetate, Pentyl bromoacetate, octyl 2-bromopropionate, ethyl 2-bromo hexanoate, Ethyl 2-broinoctanoate, ethyl 2-broiudecanoate, Ethyl 2-bromododecanoate, ethyl 2-bromo-4-methylpentanoate

_kIAI 109835/1710

and ethyl-2-bro: u-9-doüeoylenat replaced, one obtains:

Methyl 3,4, ^ -tribroni-üc-niethylpyrazole-1-acetate, ethyl- ■ 5, / .., h-tribrorapyrazole-1-propionate, ethyl-3,4,5-tribromo pyrazoi-1-butyr; .t, Isopropyl-3 , A , b-tri broi & pyrazol -1-ae- ^ tat, t ert. l-acetate, Üctyl-J, 4,5-tri bromo-α-methyloyrazole-1-acetate, ethyl-3 »4, 5-tribroui-abutylpyrazole-1-acetate, Ät: iyl-3,4 ^ -tviDro- ii-a-hexylpvra-Zül-1-acetal, Ätnyl-3,4, ^ - tribiOm-a-octylovrazole-l-acetate, Äthvl-3,4, S-tribroiB-cc-aecylpyrazole-l-acetate, ethyl 3 _} 4, 5-tribromo-a-isoDu-üylpyrazol-1-acetate bzv ?. Ethyl 3,4,5-tribroiri-a- (7 aecenyl) -pyrazole-1 -'-acetate.

Example 2:

H-.rTs tellur & Vü.- , '),'; , b-'Jribroiüpyrazol-1-propionaäu-re.

A mixture of ^, 1 g (O, ü "^ luol) 3,4, 5-TriDrom p.vrv .-. ZoL una ö, lg (Ο, ΟΑ'ο --ιοί) Ethyl-'i-bromopropionate root underneath one i3ticKS "toi"i'atQiOt; pnary 24 bT.uno.on heated to 140 C. N ::: cn α em cooling wuiO.e a reaction mixture with 6ü 11.I aqueous: 0.5 η sodium hydroxia After further cooling and addition of aqueous hydrochloric acid to a pH value of 2, a precipitate formed which was composed of a mixture of ether and Technically pure hexane Uiiikris'-allisi -.- rt wurae. i ^v ian received 10.1 g of 3,4, ^ - tribromo-yyrazol-1-proOicns ^ ure with a melting point of 112 to 113 ° C.

10 9 8 3 5/1710

_ίΛ * Α0 ORIGINAL

Analysis:

Calculated for CgH ₁ -BrJSi ₂ O ₂ :

C 19.12; H 1.33; N 7.43; Br 63.61; sparked: C 19.31; H 1.54; H 7.44; Br 64.05.

Using the same procedure, one obtains using of 3,3-dichloropyrazole, 3,4,5-triiodopyrazole, 3 »4-jibroriipyrazole or 3j5-i) ibromo-4-chloropyrazole instead of 3,4,5-tribroiapyrazole the corresponding products:

3 »5-dichloropyra2, ol-1-propionic acid, 3, 4 ^ -lriiodopyr propionic acid, 3 »4-dibromopyrazole-1-propionic acid or 3,5-dibromo-4-chloropyrazole-1-propionic acid.

example 5:

Producible ung of 3,4, 5-Trib rompyrazol-l -acetic acid.

A suspension of 3.9 g (0.01 mol) Ethvl-3,4,5-tri bromopyrazole-1-acetst (from Example 1) in 20 ml of aqueous 0.5 η sodium hydroxide was refluxed for two hours. A clear solution formed which cooled became. After dilution with 50 ml of water and acidification to pH 2 by means of hydrochloric acid, a white precipitate was formed, This was filtered off, washed thoroughly with water and recrystallized from an ethanol / VJasser-G-emifich. 2.6 g of 3> 4,5-'iribromopyrai: ol-1-acetic acid were obtained with a melting point of 212 to 215 ° C.

Analysis:
Calculated for C

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-IfJ-

G 16.55; H 0.85; M 7.72; Br 66.08; found: G 16.62; H 0.89 N 7.81; Br 65.88.

By neutralizing this acid with sodium hydroxide, calcium hydroxide, ammonia, triethylamine or piperidine in aqueous Meoium and subsequent evaporation of the reaction mixture the sodium, calcium, ammonium, tri a thyl ammonium or piperidine salt is obtained under reduced pressure of 3,4,5-tribromopyrazole-1-acetic acid.

Example 4;

Production of ethyl-j, 4, 5 -tribromo-q-iaethylpyrazole-l-aoetat ,

After veri'anren example 1 was obtained under Use of ethyl 2-bronipropionate instead of ethyl bromoacetate the ethyl ^^ jb-tribrom-a-iaethylpyrazol-lacetat with a melting point of 64-66 ° C.

Analysis:

Calculated for C ₈ H ₉ Br ₅ N ₂ O ₂ :

C 23.73; H 2.24; N 6.92; Br 59.21; Found: C, 23.88; H 2.55; N 6.98; Br 59.07.

Example 5:

Manufacturing _of__3yy4. ^ -Tribromo-q-methylpyrazole-l-acetic acid. Following the procedure of Example 3, under

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Use of ethyl 3,4,5-tribromo-a-methylpyrazole-1-acetate (from Example 4) instead of ethyl 3,4,5-teLbrouipyrazol-1-aeetat the 3A , 5-tri bromo-a- methylpyrazole-1-acetic acid with a melting point of 162-103.5 C.

Analysis:

Calculated for G ^ H ₁ -Br ψ ₂ ° 2 ^:

C 19.12; H 1.34; ίί 7.43; Hr 63, oil; found: G 19.27; H 1.4 ?; N 7.34; Br 63.74.

Example 6;

Production of 3,4,5-Tribroiapyrazol-1-Bu.ttersäure "

Following the procedure of Example 2 gave under Use of ethyl 4-bromobutyrate instead of ethyl 3-bromopropionate 3,4,5-tribromopyrazole-1-butyric acid with a melting point of 128.5-13 ° G.

Anal yse:
Calculated for

G 21.51; H 1.81 ;. M 7.17ϊ Br 61.33; found: G 21.98; H 1.98; N 7.26; Br 61.45.

Example 7;

Following the procedure of Example 2 to give ethyl-3-Brora using ethyl 2-bromo-3-butenoate or

109835/1710

2-methylpropionate instead of ethyl-3-bromopropionate the 3,4,5-IVriDrompyrazol-a-vinyl-ess: LK acid or 3,4, *> - ^r J? Ri.-

—1-propiorisriur e.

At game 8;

In Verwenaung of i ^v iethylbromacetat, Propyibrom acetate, Butylbromaeetat, Isobutylbromaeetat ouf-r hexyl bromoacetate. instead of ethyl bromine acetate, the procedure resulted in aee example «1«

hethvl-3,4,5-tribromoyrazcl-1-acetate, Propvi-3, A, 5-t; ribrom;:, yra2ol-1-acetate, butyl-3,4, b-tribroiaeyraaol-1-acetate, isobutyl- 3, -, 5-tribrO'üOyrazol-l-acetate or ^Hexyi-3,4: --triuroacyrazol-l-acetate.

Example ^;

Hei -st el ment: νοι · 3,4, ^ - 'TriD ro- ^ pyrazoi-l-acetamia.

A solution of 1.7 g (½, 025 i-ol) ethyl 3,4,5-tribrointyrasoi-1-acetate in 250 ml ethanol was treated with iuanonia gas §; esatti; .t una three layers to about 25 G held. Most of the ethanol was then evaporated off under reduced pressure and the resulting solids were filtered off and recrystallized from an ethanol / water mixture. 8 g of 3,4,1-tribromocyrazole-1-aeetamide with a melting point of 234-236 ° C. are obtained.

Analysis:
Calculated for

LBrJ 109835/1710

BAD ORIGINAL Λ

G Ib, 60; H 1.11; N 11.61; Br b6.26: Found: C 16.58; H 1.15; N 11.54; Br 65.59.

Manufacture of 3, 4, 5-l'ribrum-II, I'I, _ üCj \ tjri.methy] J-yrü_zpl-l-_ acetamide.

A mixture of 70 g (ü, 16b hol) 3,4, S- ^; I ribroin-ak methylpyrazole-1-acetic acid and 70 ml of thionylchloric acid were heated for 3 to 5 hours under a flow of water. AnpohlieiJtnd vo.vj.- all excess thionyl chloride under reduced! Pressure evaporated. Jas obtained in this way ;;, 4 ■ /; - ^r iribror: .- a-metnylpyraKol-1-Tcetvlchlorid v / urae dissolved in 2uU ml dry benzene, and this solution became a solution of 70 ml Dimetüylamin in 300 ml dry benzene zugetropit. After the addition of acid chloride to the amine had ended, the reaction mixture was stirred for 0.5 hours at about 25 ° C. and then heated to the temperature of the flow rate for a further half hour. After cooling, the oil is washed three times with 75 ml of water and dried over anhydrous sodium sulphate. The benzene was evaporated under reduced pressure and the W Veisse solid from a mixture of benzene preserved and technically pure Hexran umkristallisxert. iian received 67 g of 3,4,5-tribromo-Ν, Ν, α-trimethylpyrazole-1-acetamide with a melting point of 130.5 Ms 132 ⁰ C.

Analysis;

Berecimet for C ₀ H ₁₀ Br, ü, 0:

1098 3 5/1710

C 23.7y; H 2.50; a 10.40; Br W, / 55: found: 0 23, Sl; H 2.40; I'l 10.43; -br 59.44.

When using l, l-I) imetnyl-2-propynylamine, isooropylainin, Diisopropyllauiin, Di butyl ami η, .üioentyl -

Jihexylamine, ßenüylaruin, dicyclohexylaiüin, 3-ueiitylaiiin, Pyrrolidine, piperiaine, hexaiuetnvlenimir. and gives l'tiaruorpholine instead of i-dimethylarain s Veri'an the ent spree hence

'3,4, S-TribiOni-xJ- (1, l-dimethyl-2-propynyl) -u-methylpyrazole-aceuaiiiid,

5, A) ^ -Tri'brom-ii-isoproDvl-a-EiethylT-yrazol-l-acetaniid, 3,4, rü-'iri bro-ii-ij, ri-diifioprooyl-u-iaethylpyrazol-l-acetamid, 3, 4, ^ -Tribron-Ii, Ij-dibutyl-a-iuethylpyrazol-l-aae bamid,

5 A , 5-'iTibrom-M, ΙΊ-dipentyl-a-mefchylpyrazol-1-acetainide, 3> 4, 5-Ti "ibroiu-ύ, E-ainexyl-ai ^ ethylpyrazul-1-ace tamide, 3,4 , ^ -Tribroia-ii-ben ^ .vl-üc-metnylpyrazol-l-acetaiaia, 3,4, ^ι 5-ΐriDrom-i ^v ], l · J-αiGyclohexyl-α-methyluyrazol-l-acetaπίlid,

3,4,5-tribroin-N- (3-cyclopentenyl) -a-methylpyrazole-lacetamide,

3,4, 5-Tribro (uN, M- (tetrainethylene) -a-iüethylpyrazol-1-acetamide, 3 A, 5-tribromo-] S, M- (ρentamethylene) -oc-methylpyrazol-1-acetamide, 3, 4,5-tribromo-l \ l, N- (hexamethylene) -a-methylpyrazole-l-acetamide or 3 »4» 5-tribromo-N »li- (3-" fchiapentamethylene) -a-methyl pyrazole-l -acetamide.

109835/1710 ORIGINAL BATHROOM

Example 11:

Creation of 'j _r 4 _f b-.Tribrofc-a, a-din.ethyl r.yrag ο] -1- aeetaaiid.

Using diethylamine instead of diraethylamine gave cias procedure aes b :: i ^r -uiels Iv 5, ^A , 'n- tri "urom-li _t a-dimethylpyrazzoi-1-acet ^r -imia with a bchine point of 226-2 . ^ Y ⁰ U.

Analysis:

Calculated for Cjn ^ hr.Jl _y O:

G 21.56; H 2.06; η lü, 7 /; br όΙ, Λ "-); gefunaen ι C 21.93; ti 2.01; ii IU, 09; br ol, ^ ^c j.

12:

Producible ung of 2,4, 5-Triorcni-K-metay l-a-a uh

acetainia.

Using 3,4, i-TriDrom-o.-äthylpyrazol-lesaigsäure and. of methylamine instead of üimethylamin gave the method aes Example 10 3,4, ¹ ^ -TrIbroia-iT-methyla-äthylpyrazol-1-acetamide having a melting point of 178-18O ⁰ C.

Analysis;

Calculated for CqB ₁ QBrJuUO:

C 23.79; H 2.50; N 10.40; Br 59.35; Found: C, 23.82; H 2.56; IV 10.42; Br ^ 9.64.

109835/1710 BAD Ä

Example Ij:

Manufacture of 3,4,5-i '";' i b'-o; fl -a-ineth ylpyroZoJ-l -acetamide.

Using .ammoniak instead of dimethyl amine er _f v; ac aas method according to Example 10}, 4, Si methylTnrrazol-1-aeetaniiü with a new ocbial melting point of Ib8-lc9 ° G.

Analyst;

At-eehnet for C ₆ HgBr-J ^ O:

C 19.17; η 1.61; W 11.17: Br 63.78; found G Γ-ι, 3ο; is l.bO: H 11.07: Br 63.5L.

For example. 14;

i ^ · von_3, ^A Λ .riProni-Ni ^ -diinetnyl-a-ijtny lpyrazol · -

Using Ί, & , '/ -'i>'ibromo-a-ethylpyrazole-1 acetic acid instead of 3,4-, ^ - iribromo-a-methylOyrazole-lessic acid gave aas failure of Example 10 3 »A, ¹ J brou-ü, iv-aia ^ et-iiyl-u-atnyluyrazol-l-ucetaiLid with a melting point of 6Ö, 5 - 90.5 G.

Analysis:

Calculated for C, H- _,? Br ^ H, O:

G 25.66: H 2.90; I ·: 10.05; Br 57.36; found: C, 26.00; E 2.96; jx 10.06; Br 57.56.

109835/1710

BATH ORIGINAL

Example 15?

• Preparation of 3 »4, 5-tribromo-N-methyl-l- -äthyl- q pyrazol -1-acetamide.

Using ethylamine instead of dirnethylamine obtained by the method of Example 10 3,4,5-tribromo-lY-ethyl-a-methylpyrazole-1-acetamide with a Melting point of 211-211.5 ° C.

H Analysis:

Calculated for CgH ₁₀ Br ₅ W ₅ O:

C 23.79; H 2.50; N 10.40; Br 59.35; found: C, 24.08; H 2.66; N 10.22; Br 59.41.

Example 16:

Production of 3 »4, 5-! Eribromo-U, K-diethyl-g-methyl-pyrazole -! - acetamide.

Using diethylamine instead of di-

ψ Diethylamine was obtained by following the procedure of Example 10

3,4, S-tribromo-iT ^ -diethyl-a-inethylpyrazole-1-acetamide with a melting point of 69-71 ° C.

Analysis:

Calculated for C ₁₀ H-, .BrJf ^ O:

C 27.80; H 3.26; N 9.72; Br 55.50; Found: C, 28.14; H 3.29; N 9.74; Br 55.50.

109835/1710

Example 17;

Production of 3,4,5-l'ri "bromo-l, IM, oc-triethylpyrazole-1-acetamide.

Using 3,4,5-tribromo-α-ethylpyrazole-lessetic acid instead of 3,4,5-tribromo-α-methylpyrazole-lessigic acid and diethylamine instead of bimethylamine gave 3.4 by following the procedure of Example 10 , 5-tribromo-N, li, a-triethylpyrazole-l-acetamide with a simmering point of 99-101 ⁰ G.

Analysis;

Calculated for O ₁₁ H-, ^ BtJSJD:

C 29.62; H 3.62; N 9.42; Br 53.75; found: G 29.78; H 3.92; 19.41; Br 53.85.

Example 18;

Preparation of 3,4,5- ^f jribromo-1 _t 3? If-dipropyl-a-methylpyrazole-1-acetamide.

Using dipropylamine instead of dimethylamine, the procedure of Example 10 gave 3,4,5- ^f iribromo-N, 1-dipropyl-α-methylpyrazal-1-acetamide with a melting point of 89.5-91 ° G .

Analysis;

Calculated for G _no K _Q Br, N, 0;

La -Lo jj

0 31.33; H 3.94; N 9.13; Br 52.12;

found j O 31.56; H 3.92; "W 9.16; Br 52.41.

109835/1710

Example 19:

Manufacture of 3,4,5-tribromo-M, M-dipropyl-g- ethy lp yrazol - 1-acetamide.

Using dipropylamine instead of XHmethylamine and 3 »4,5-tribromo-α-ethyl-pyrazole-1-acetic acid instead of 3,4,5-tribromo-oc-methylpyrazole-1-acetic acid was obtained by following the procedure of the example 10 3 »4,5-tri bromo-NjW-dipropyl-ce-ethylpyrazole-1-acetamide with a melting point of 66.5 - 68 C.

Analysis:

Calculated for Gr ^ Hp ₀ Br, N ^ Ü:

C 32.93; H 4.25; N 8.86; Br 50.57; found: G 32.85; H 4.41; N 8.70; Br 50.80.

Example 20:

Manufacture of 3 _? 4 ^ -tribromo-I ^ Nd imethylpyrazole-1-acetamide .

Using 3i4,5-iribromopyrazole-1-acetic acid instead of 3 »4» 5-tribromo-a-methylpyrazole -! - acetic acid , according to Example 10, 3,4,5 -tribromo-H, M-dimethylpyrazole- l-acetamide with a melting point of 176.5-177.5 ° 0.

Analysis;
Calculated for

IQ & 835 / V710

C 21.56; H 2.07; Ή 10.78; Br 61.49; found: C, 21.74; H 2.10; N 10.58; Br 61.75.

Example 21 ;

Preparation of 3,4,5-fribromo-N-allyl-q-methylpyrazole-lacetamide.

Using allylamine instead of dimethyl According to Example 10, 3,4,5-iribromo-N-allylcc-m were obtained ethyl pyrazole-1-acetamide with a melting point of 187-187.5 ° G.

Analysis;

Calculated for CgH ₁₀ BrJS "O:

G 25.99; H 2.42; N 10.10; Br 57.64; found ; G 2b, 19; H 2.43; N 10.04; Br 57.63.

Example 22;

Preparation of 3,4,5-tribromo-N _r N-diallyl-tt-methylpyrazole-lacetamide.

Instead of allylamine using J & amine of dimethyl was obtained according to Example 10 3 '4.5-Iribrom-! I, N-diallyl-a-metnylpyrazol-1-acetamide having a melting point of 72-74 ⁰ C.

Analysis; Calculated for

109835/1710

_; : ei'una m: G Ί, οΥ; .1 <!, '^ 7; I * £ ν ·· * ο; ßr ^ - '»/ b · At so lei 2j:

Manufacture γρη_ 5 »4, ^ .- Iri
ace t; gj uici.

Under Yervenuum ^ from 3 »4,"-j-'iriLrcin-cL".t:j" 1 ■. / 'Τ - ί: ο1-1-essifeöäure instead of 3,4, ^ -Vribroiit-a-iiicr , hvluyr .- ^ xl-l- length ESSIC-säiirs una of Jiallylamin instead of Jiirietnylaniin

. crniclt one ^ ernüä at -3 [J el 10 3, 4, ^ - ^r x'r.I fam; ".- ,, i ..- diaj.l; 7 ± - ^a-; .t: iy ] i, yr - i ^ oi.-l-feLGetaiüi ·! with a: - ^ e & ^ lz,., r: t 74 ^ü 0. '

.calculated l ^; ir 0-, rl rir..i. , 0:

1 '· Io j ι

: -'.- j, '//.', h 'jAj'i 1. c, V / -: ür ¹ ^ l, ul; , ~ exu.n-.en: C 355, k2; H i, 64; J 8, h2; Bi- ^ u, bs.

24:

Herste ^ lun _a of "j, /, ^'s-

under Verwenaung of .Birtylamin instead of Dinethyl amine so continuously to ^ emüti Example 10 3,4, ^ - Tribroit-u-buty-1-methylüyraziol acetamia with a bchnielzpunkt of 174 to 175.5 ⁰ C.

Analysis:

For C ₁₀ H ₁₄ Br ₅ K- ^ O;

109835/1710

C 27, you; fi 3.27; Λ 9.73; Br 55.50; found: O 27.9)? H 3.54; K 9.55; Br 55.75-

At GAME 25:

Production of ~ j>, 4, 5 - '. L'ribroii-iNl-tert-dutyl-q-methvl -

pyrazole- 1-ace tamicL .

Using tert- butylamine instead of dimethylamine, according to Example 10, 3, 4, 5-tribromine) i -tert was obtained. -butyl-q-xaetiiyl pyrazole-l-acetamjq with a shrink point of 200.5 - 201.5 ⁰ C.

Analysis:

Calculated for U- ,, _} η Br, M ^ O:

C 27, βΟ; H 5.27; JST 9.73; Hr 55.50; getunaen ': C, 27.97; η 3,5'ί; N 9, bb: Br 55, ö7.

Example 26:

Manufacture of 3 , 4, 5-'l'ribroi a-j, \ i-oyel ohexyl-a-methyl pyrazole - l -

Using cyclohexylamine instead of dimethyl according to example 10 $, 4, 5-tribromo-N-cyclohexyl-a-methylDyrazole-1-acetamide with a melting point of ⁰

Anal yse:
Calculated for

109835/1710

ORIGINAL

C 31.47; H 3.52; tf 4.17; ar ": ■?., -Λ-, found: G 31.57; H 5,4-y; W y, 23; Br 52.73.

Example 27:

Her Se ttings of 3,4, 5-bromo-FFRI u, i i- (3-ox apen tamethyl s) -amethylpyrazol-1-acetamide.

Using i'iorpholin instead of JDirnet ny ± - amine, according to Example 10 3, ^ , r>-'- ribron: -i <i, l: i- (3-oxapentamethylenej-a-niethylpyrazole-1-acetaciia with a melting point of 155.5-158.5 ° C.

Analysis:

calculated for ϋ- ^ Η- ^ ΒΓ-, Ν ^ Ορ:

G 26.93; H 2.71; N 9A2; br 53.76: found: G 27, OS); ή 2.59; Jk 9.65; Br 53.82.

»
Example 28:

Preparation of 3,4,5-Tribro m-N-methylpyrazole -l- acei: amide.

Using k ethyl amine instead of ammonia gave, according to 3 Bei-ciei V 3,4,5-Tribroii: -i \ ^T -inethyl-cyrazole-1-acetamia with a index of 242.5-243 , 5 G.

Analysis:

Calculated for C ^ E ^ Br ^ H, 0:

C 19.17; H 1, Dl; im 11.18; Br 63.78; found: G 19.26; ti 1.43; M 10, δ4; Br 64.28.

109835/1710

- 51 -

uijt.rr <! r: r..en'innis of j>, i, ^ -IribromDyrazol-l-propionsäui-e, ί, 'ΐ,'; - i ^1. -i broüipyrazol-1-butyric acid odr-r 3,4,4-ivaorOm-a-metnyliJvrazol-l-propionic acid -, parts before. ^ 4, IrJ. i) ro.i - a-iüet: -7l ^: -V \ 'raiiLi.li-esr'3 ^ ;. ^:: CDCR <- "ernicl t you gemKß iie: s: .iei iii:>'> - Ί ri BWI ^, ^ -αΐι.ι -: ΐ-.Ί.νΐcyr ^ zol-liter probiona -Jiia,;.,. <I, ", -iri. ο: ·.; ...-! · <, i '.- di..etri.vli, yr; i-2; ol-l-buty2 "amia bzi";.

'.ir ^ vo n Zsz ^ L ^ IHiP ^I "P ^; il ~! i ~ iii§ ^ lYlpj ^ razol-l-ess i.csä'-ire.

, Λ,, in

70 .Hl. ^ Ίΐ.ιη; - t-; l.) ^; -T una with 2.7b _ε ; (U, U ^ ι -.- ·: Χ 'l-? Tea, what- = ^ ivj. K-'li'jmcarbcnat ve ^ -aetsct. JDas G-en: i.-cii vtivae unüti · i-iV -r.ren iu ^ innte ;: a.ii RUcκ "■ 'lu.dte ^ ipp'rc iu-triikt un; ivj / v: adai-i-LuiI; .-. ^ i t- 2, L' eC -io.oll i .-- 'wi .; Ätnvl-2-or: - i!: rüDion ^ t vprsctz *:. x-ian heated the RearitioriStCeiai. ^ cn 1, ¹ ^ itanaen aui ".i.' -ekflujte.ü. eratur una offset -; j nacn ^ birönlan »- with an ov wäßf-i * -i. ^? n .iatri ^ anvaroxialcsun ^ (.0.S;, · in V-- nil .visier ). i) aö ACitc ·;: v; urae riL ^ estilxiert und lie back ^ naifre wäBsr. '. gelösuiii; ": 2 btuniPi. under ^ üc;: ilu.i heated, r,;: formed si cn iiiirf .il-Are Losaiv :, which ^ eKüri t un ~ was acidified with 2 η hydrochloric acid a .if 'etva pll 2 -Ai ^ -T-. The resulting vrei ^ c xäeaerscnl-ii, - -nxrae aofiltered, with V. 'as he ge \: z.schen UNU - etrockne ".-, -van received 5, ^ 5 g (yield 95 etc.) 5,4,5-Tribrüm-a-metüvloyrazol l e8si.-; Acid with an excess point of 162-104 ° G. Jas ProdUiCt was identical to that of the example.

^109835/1710

? 1Q7715

Analysis:

Calculated for ü, Jn ^ Br-J ^ O ^ ₁ :

C 19.12; £ 1.34; N 7.45; Br bi.bl; found: G 19.24; H 1.55; h 7.11; Br bi>, 71.

Example 31;

Her position of 3,4, 5-Tr ibro in-a-ätnylpyrazol l esaiffs äure.

Using ethyl-2-droabutyrate from Ä2-broiaproijionat one obtained. ^ Eiü ^ ß Example ^ O 3,4,4-tribromo-a-ethylpyrazole-1-acetic acid with a dohin melting point of 90 - IGO ⁰ G.

Analysis:

Calculated for Ο ^ ί-ν, ΗΓ-νΓ.'ρΟρί

G 21.51; hl, ol; h 7.17; br ei, 3 ^v >; ^. ^ funJ-en: C 2i, t>8; π 1.69; : ■; 6, ου: ar bl, 4 6.

Example 52:

Manufacture; of j, 4, 5-'jribromo-q-isopropylpyrazpl-l-essifr- * * acid.

Using ethyl 2-bromo-5-methylbutvrate instead of ethyl 2-bromopropionate was obtained according to the example 30 3,4,5-tribromo-a-isopropylnyrazole-1-es!: Iga acid with a bcmnelzturuct from 92-95 C.

109835/1710

Analysis:
Calculated for C

C 23.73; H 2.24; M 6.92; Br 59.21; found: C 2 \ 62; H 2.14: a 6.71; Br 5 ^C >, 41.

Example 53:

Preparation of 3j> 4, 5-Tribroiii-a-butylpyrazole-l-essi _i B; acid.

Using ethyl 2-bromohexanoate ethyl-2-DrompropionuT- instead of ■ one so continuously according to Example 30 3,4,5-tri bromo-oc-butylOyrazol-l-acetic acid with a scnmelzpunkt of 90-92 °.

a nalys e:

Calculated for CqHn ₁ Br-J ^ pGp:

C 29, «0; H 2.65; M 6.69: Br 57.23; Found: C, 25.93; H 2.79; IV 6.56; Br 57.31.

Example 34:

Production of ethyl 3,4,5 -trib roffl -a-butylpyrazole-l-acetate .

30.4 έί (0.1 iiol) 3,4,5-tribromopyrazole were in 500 ml Dissolved acetone and mixed with 27.6 g (0.2 Hol) of solid, anhydrous potassium carbonate. i) the mixture was under Rünren Heated for 10 minutes to jüickfluss Temperatur and after cooling mixed with 23.0 g (0.11 mol) of ethyl 2-bromohexanoate, the reaction mixture was kept under flow for 1.5 hours,

109835/1710

_ 34 -

Minite una filtered eo afterwards. The filtered solids were washed with acetone, the Acetorifil entered and Acetori water washer. Put to dryness under reduced pressure. After jyf-> Ktilli_ti.on of the residue received; m ^ n 4-1.0 g (92 ^J / oL _r - ~ yield; ethyl-3,4,5-tribromo-oc-butylpyr & zol-l-ace "did with a boiling point of 136-140 C at 0, 1 ¹ ^ min / Hg.

Analysis:

Calculate i'ü ^Λ C -.-, H-. r £ r _v ü '0,:

C 29.55; H 5.3β; is 6.27: Br found: C 29> 9ί; K -5.67; υ 6.13; He

Example 55:

Herste ll ung of Äthy l-5 »4, 5-triDroin-u- äthyloyr-arol -l-aoetat,

Using ethyl-2-orombutvx-ate instead of ethyl-2-bromonexanoate gave, according to Example 34, ethyl 3,4,5-triTDrom-oc-ethylpyrazole-1-acetate.

Analysis:

Calculated for CgH ₁₁₅₂₂

C 25.80; H 2.65; N δ, 6y; bv 57.23; g-efunaen: G 26.35; H 2.88; r, x 6.63; Br 57.04.

Example 36:

Hers tellung of Äth yl-5,4, 5-tribromo-a-isoprüpylp yrazol-lacetat.

109835/1710

2107T15

Lnter V'irvericuirig from Etnyl-2-brom-o- ^! i: etn.ylbutyral; annteLl- von Ätnvl-2-bruiühexanoat, was obtained according to Example f & d, 4, ^ -tribromo-u-isopropylpyrazole-1-acetate with a boiling point of 119 ° C to 0.05 now Hg.

Bei Piel 37:

Manufacture of ^, S- Dibrompyr azol-i-ä tnaiiol.

A solution of y.7 g (0.025 i ^v iol) etiivl-5.4, 5-tribroiuüyrazo ± -l-acetate in 12b: ul dry eti-tit eir auspensioii of l, yg (0.0? i ^v iol) lithium

uaiiiyaxäa in bO ml of dry ainer. The jieaK'cionsf ; -. aro.e two Ö tuna s on i <ückriuidtoiüüeratur er -

hi tzt uxixi 0iin: jiCL aDgeiöinlt. i ^ to put b KII ethyl acetate una anöchlieiiena 30 ml of water and decanted after e ^ 'fol.-ter jibsetzunf-: UEN Ätnertpii. The ether solution was

Washed once with 40; nl water and dried over anhydrous Ka χ riu Jisu ji; -t. After evaporation of the ether, the oily residue is treated with decayed heating coal and it crystallized -hus an.ii (iemiüch made of ethyl ether and petroleum (range 30-60 U), on aie! •• ■ e ^T iei £ se vuraen b, "?. g (yield 75%) 3 > 5-dicromopyrazole-1-ethenol with a; - obtained boiling point of c> 4-66 C;

.analysis;

Calculated for C ^ H ₆ -Br ₂ K ₂ O:

G 22.24; H 2.24; M 10.37; Br 5 ^, 20: found: (J 22.63; H 2.45; «10.52; Br 59.01.

109835/1710

Example 'jb ;

Manufacture_UKg ^ _von_ 3 ₁ ^ -Iti-bromo-ß- methylpyrazole - J. -ä tflan ol.

Using ethyl- '·), 4, *> - tribrorn-u-methyl cvrazol-i-acetal; instead of ii.th.yl-3, 4, ^ -tribromopvrazol-1-acetate obtained ffian according to Example 37 3, 5-Ιλbrom-ßmetnylpvrazol-1-ethanol with a boiling point of b3.5 to 4.5 ° C.

.analysis;

Calculates xur ü, n br _o ri _o U:

vj 2 * 5.30 ;, ti 2, ö4; Γ-; ^l i, b7; Br bb, 26: found: C 2 ¹ J, 53; -ti 2.42; ί: 9.65; br bb, « ¹ ?.

Example 39:

Preparation of J »_5 ^ 1) Brog.-a- methylpyrazol-1-essi. Rje ure.

In the course of 20 minutes, an increase of 2.8 g (, Ül i'iol), 5-JÜbroß: -ß-iiietnylpyrazol-1-atr.anol in 0.3 g (0.0075 r.ol ) Sodium hydroxide, una .o, ü ml V / water with a solution of Ί, z. g (0.0215 i'-ol) potassium manganate in 30 ml water. I added another 50 ail of water, mixed the reaction mixture 4 b tuna en at etv; ä 25 0, acidified uann with 6 η o cc -wef el acid and added iiatrium bisulfite until all the precipitated i '^ nganaioxiei in Löouni- · went. The aqueous solution is extracted arimally with 50 ml of ether, then combined ether extracts are washed with water and dried over anhydrous sodium sulfate.

109835/171 0

After evaporation of aee ether under reduced pressure and then uhroLaatograp / iie on silica under use a solution system consisting of benzene, chloroform and glacial acetic acid in a volume ratio of 65/10/5 a solid was obtained the und sr G-swinnung of ^ »S

acetic acid with a melting point of 124.5 - 126 ° G Acetone / fiexan was recrystallized.

Analysis ;

Calculated for G ^ E, Br ₀ JM ₀ O ₀ :

C 24.16; H 2.03; H 9.40: Br 53.64; found: G 23.96; H 2.06; h 9.63; Br 53.97.

Example 40;

Preparation of 3 , 4 ^ -Tiibromo pyrajzol-l-atnanol acetate (ester).

3, U4 g (0.01 JViOl) 3,4,5-iribromopvrazole were dissolved in 70 ml of acetone and treated with 2.76 g (0.02 mol) of solid, anhydrous potassium carbonate under doors for 10 minutes to the inflow temperature and added to it after it had cooled down. 1.85 g (0.011 χ · ..οΐ) 2-broiüätnylacetat. This reaction mixture was heated under pickle for 12 hours, cooled and filtered, and the acetone was removed under reduced pressure. The oil obtained in this way consisted of a mixture of the desired acetate and the corresponding alcohol. i * ian dissolved the u-emisch in 15 ml of pyridine una used it with 3.06 g (υ, 03 mol) of acetic acid anhydride at 0 G. This reaction

109835/1710

BATH ORIGINAL

. 2 ~> ^ ter.en, -. Ί ^ κώθγ · and then poured in 20 ml of ice water. The entstanaene Miederschlag wurae auraltri ert and. grant with yfasser. After drying and recrystallization from hydrogen, t car -.-. Π was obtained '5 »4,5-TriDrüiapyrazol-l-etiianolacf: tat (caters with egg

üc'iüelzp t xlct from 64-67 ° C • Analysis: Calculate for O ₇ E 2 ° 2 ^: G -21, 51;

; i \ i 7.17; i-sr el, 5 5: found: O 21, öö; ti 1.9 5; ii 7.14: ύτ oil, α 2.

.example 41;

Herst eil urip: before. '5, ^ - ^ -I'r'ibromiovrasol-l- ^ tiianol.

Aeetonf'reies el vrurae obtained according to Example 4ü with 20: fil ü, 5 η ätnanolisonei: · Sjatriu ^ nvarozid. behanaelt and 1.5 btunaen heated under iäicKiluß, jzm solution siaitt wurae under verminaerteiL Pressure <abseviarrroft and u.er Ki; castanet in Äth- = r solved. The Ätnerlösuru: '-mrift rait v7asser washed and dried, aer at-ier under vorrii ^ .- ^ rte:.!

Drunk off ^ eiampi't. The obtained '5,4,5-'TtJ bro £ irjvrazol-läthanol melted at 68-70 ° C.

Analysis;

Calculated for Cr- ^ r-Br. ^ LM ^ O:

C 17.21; .i 1.44; '& 0.03; Br 68.72; found: 0 17.2b; H 1.50; h b, 05: Br 6y, 17.

109835/1710

ßf-α : -, i &, 1 : _% / i UKo ^ of Li α ijvr- i i-an-tani 1- _o , 1 cij L-

Vui leffii-ioi] from IU - .: .O, ü2bo Λ.ο1.) 3,4, S-Tribroi-a-! '/ Lcvra ^ .ji-l-ef -'- i-acid (ner;: e;: · shares greüJiß example 5) I * ..! ul -i'-iiionyicrloriu v / urae "heated under reflux for 5, b hours. ^ '- Tilifiizrts niohtuni' ■ · ■ ..- ■ last thione chloride T.'ur-ie unt. ^ t v ^ 2in.ierte- ^; ! i Dvu.ck 'i Dgeaa ^ riOft urw the unpurified' -j, -., '-.- T'-it'LOa-a-iUetriylOyrazol-l-acetvicalo "i α in 2': - ml Jb ( -n2; o.! eiö :: t. v; nt.> r itüi ^ ren ver ^ etste uian a 'J - =: nit-eh. from ■ ι, -); „■ I ¹ J, ^ iOb jv .il j; _t 4-jJi: .- nl or ^ nilin,:>, U> (0, L-;.-oil) ü'-iä i-iiyiaasiii um lüü üil xroare; j-ffi benzol tro '.; ier.v : iron with

otvLrcr -Besollöpung. The ^ .e- K.ea, -ftion3f.eJiisori v-urcie t under i'or _*; ; e? exzteiu perform eiiui nalb e btunde ', tva 2S G ge ■ ii-ilteii. iteiiir. - ^ aη it a long half dtnnae under ÜäcicfluJ. After aem üicünlen --rx ^ e aer ^ eDilaete ftie-Jorschla ^ - aofijtriert, with Wascer ce-.VHscn.en and --us 95 % Atnanol u; ^ K: rir.t'-dlj-ipieri. ; ian ami el t IG ^ - 6, i , 5-iribro; ü- ■ 5 ', i'i' -aiciilor-a-nietnylpyrazol-l-acetanixi j. with eina ^v fi iiiKt from ^ 17-210 J.

0 27, b7; t 1, τ5; Ν 8.07: I rounds: C 27, cs4; .- 1.75: i ^l J 7.91.

Eacn ecleicheni method, jeaoch using iN-kfithyläthylainin, N-methylbenzylamin, li-methylanilin,

109 835/1710

BAD ORJGII4AL

N-allylaniline, M-methyl-p-toluidine, UJ jut yl -4 - 1 e rt. butylaniline, K-hetriyl-2, 5-aichloraniline, 2, b-linitro-4-trifluoroniethylaniline, 4-trifluoroniethylaniline, 2,6-HL-nitro-p-toluidine, 2,6-dinitroaniline, 4-gnlor-2, 6-dinitroaniline, 2-methylpyrroliclin, 2- sec- butylpyrrolidxn, 3, ώ-diniethylpyrrolicin, 5,4-diethylpyrrolicin, 2-ii.thyl-5-ynethylniorpholine, 2,6-DJuüetiiylmoTpjiolin, 3-wethylmoipholin, 3-wethylmoipholin, bi b-Tetraaiethyltjaiamorpholin, 4-Butylpiperazin, 2,2,4,5,5-Pentainethylpiperazin, Hexamethylenimin, 2-Ätnylhexaiaethyleniiain and 3-Heptylhexaraethylenimin instead of 3> 4-i) iehloranilin gets · α;? η the following products:

3 »4, 5-Tribromo-l \ ^T -ätnyl-H, a-diiiieth.ylpyrazol-l-acetainid,

3,4,5-'Iribromo-BT-benzyl-ii _t α-dimethylrjyrazole-1-acetamide,

3 »4,5-tribromo-lii, a-di / iiethylpyrazole-1-acetanilide,

3 »4, ^ -Tribroxn-ii-allyl-a-methylpyrazole-l-aeetanilid,

3,4, 5-Tribrorii-M, a-dim ethyl-4'-methylpyrazole-1-acetanilide,

3,4, ^ -Tribroiii-M-butyl-4 '- tert . -but yl-u-iaetnyloyrazol-1-acetanilide,

3 »4, ^ - tribromo-2 ', 5'-aichlor-N.a-dimethylpyrazole-l-acetanilide,

3,4,5-tribromo-2 ', 6'-dinitro-a-iaethyl-4' -triiluormethylpyrazole-1-acetanilide,

3,4,5-tribromo-a-ethyl-4 '-trifL uorffiethylpyrazole-1-acetanilide,

3,4, 5-Tribroüi-cc, 4 '-d.imethyl-2', b'-dinitropyrazole-1-acetanilia,

■ 3,4,5-tribromo-2 ', o'-dinitro-a-methylpyrazole-1-acet anilide,

109835/171 0

3,4,5-iribromo-4'-cblor-2 ¹ , 6'-dinitro-a-methylpyrazole-lacetanilide,

3,4, 5-tribromo-am ethyl -E, IM- (1-m ethyl tet ram ethylene) -pyrazole-1-acetamide,

3 »4, 5-tribromo-a-nie chyl-1, fl- (l -sec. -Butylt et ram ethylene) pyrazole-l-acetamide,

3,4,5-Tril3rom-a-methyl-lJ, li (2,3-dimethyltetramethylene) -pyrazole-1-acetamide,

3 »4,5-tribromo-oc-methyl-N, IM- (2,3-diethylpentamethylene) -pyrazole-1-ac etaini d,

3,4,5-Tribromo-a-niethyl-Li, li (4-ethyl-1-diethyl-3-oxapentajn ethyl en) -3 ^ yrazol-1-ac e tami d,

3,4,5-Tribromo-a-methyl-l \ i, N- (2,4-dimethyl-3-oxapentamethylene) -pyrazole-1-acetami d,

3,4,5-Tri bromo-a-m eth yl-H, M- (1-m ethyl ~ 3-oxap entamethylene) -pyrazole-1-acetamide,

3,4,5-Tribromo-a-methyl-1 \ i, N- (1,2,4,5-tetramethyl-3-thiapentamethylene) -pyrazole-1-acetamide,

3,4,5-Tri bromo-a-m ethyl ~ ϊί, N- (3-butyl-3-azap en tamethylene) pyrazole-1-acetamiα,

5,4,5-tribromo-a-methyl-N, N- (1,3,4,4-pentamethyl-3-azapentamethylene) -pyrazole-1-acetamide,

109835/1710

3,4, .5-TrUD rom-a-m ethyl-N, .ti- (η exam ethyl en) -pyrazol-1-aeetamid,

3,4, S-tribromo-a-methyl-r'jIn-Cl-ethylhexamethylene / pyrazole-lacetamide respectively.

3,4,5-Tribromo-a-methyl -1, H- (2-heptylhexariiethylene) -pyrazole-1-acetamide.

Example 43:

Preparation of 3,4,5-tribromo-5 ', 4'-dichloy & yrazole-lacetanilide.

? Under Verv ending of 3.4, 5-Tribroflipyrazol-l-acetic acid instead of 3 ^ -, 5-tribromo-a-Laethylpyrazol-l-acetic acid was obtained according to Example 42 3 »4.5-tribromo-3 ^f , 4 ^f dichloropyrazole-1-acetanilide with a Sehmel point of 232 - 232.5 ° ö.

Analysis:

Calculated for C ₁₁ H ₆ Br ₅ Gl ₂ N ₅ U:

C 26.07; H 1.19; H 8.29; found ': 0 26.13; H 0.94; N 8.43.

Example 44:

Preparation of 'j, 4, 5-tribromopyrazole-1- acetonitrile. A suspension of sodium hyaride (2.2 g of a

109835/1710

60.6 % - ± ΐζβη Difiperaion in mineral oil containing 0.055 Nat riumhy aria) and 60 hü. Toluene was crosslinked with a solution of 15.2 g (0.05 mol) 3, ^, 5-tribromopyrazole in 400 ml of hot toluene. 4.2 g (0.055 i'iol) of chloroacetonitrile were then added dropwise. The mixture was refluxed for three hours and then left to stand at about 25 ° C. for many hours, and 50 ml of passer was added. The toluene layer was separated off, washed twice with 80 μl of water each time and dried over anhydrous sodium sulfate. Removal of the toluene gave 14.4 g of 3,4,5-tribromopyrazole-1-acetonitrile as a white solid which was recrystallized from a mixture of ether and technically pure hexane.

Analysis;

Calculated for CcHpBr ^ N- ,:

C 17.46; H 0.59: N 12.22; Br b9.73; M Found: C 17.51; H 0.84; N 12.09; Br 69.69.

Using 3-chloropropionitrile, 3-chloro-2-methylpropioniuril, 3-bromovaleronitrile and 4-chlorobutyronitrile instead of chloroacetonitrile, 3 »4,5-tribromopyrazole-1-propionitrile, 3,4,5-TriDrom-α-methylpyrazole-1-propionitrile are obtained by the same process, 3,4,5-tribromo-ethylpyrazole-1-propionitrile Between 3,4,5-tribromopyrazole-1-butyronitrile.

Example 4 5:

Herst RECOVERY 3 »4.5-Tri" bromo-q-methylpyrazole-l-acetonitrile. Using 2-bromopropionitrile instead of

109835/1710

BATH ORIGINAL

_ 44 -

Chi o ^ acetonitrile was obtained according to Example 44 3,4,5-Tribroiii-a-methylpyrazole-1-acetonitrile with a melting point

from 100-102 ° G.
Analysis;

Calculated for G ^ H.Br ^ N ^:

C 20.14; H 1.13; N 11.74; Br 66.99; found: G 20.33; H 1.10; K 11.66; Br 66.96.

The! - (substituted-hydrocarbyl) -di- and trihalogenpyrazoles (compounds of the formula i) have herbicidal and plant growth regulators "Properties. They can be used in fields to prevent weed crop damage, and they can protect against unsightly and harmful weeds on lawns in the garden, on golf courses, Frieööfen, railroad areas and parks are used.

The compounds according to the invention were found very effective against broad-leaved as well as grass-like weeds, the compounds within a Grupüe somewhat different from each other in their respective effectiveness differ. For example, 3,4,5-Tribrora-I \ i, N, a-trimethylpyrazole-1-acetamide and 3,4,5-tribromo-α-methyl pyrazole-1-acetic acid particularly effective against weed species such as:

Crabgrass Digitaria Sanguinalis L.

Yellow foxtail - Setaria glauca L.

Wilöhafer -A vena fatua L.

Morning glory -Convolvulus arvensis L.

Johnson grass --orghum halepense L.

109835/1710

Ribwort plantain - Plantago lanceolata L.

Ruffles - Rumex crispus L.

Wild mustard - Bras si ca kaber DG.

Cabbage purslane - Portulaca oleraoea L. and

millet - Echinochloa crusgalli L.

The aforementioned weed species could be an example of this with the specified as well as with others according to the invention Compounds are destroyed in quantities of 1.12 to 14 kg / ha and their growth is considerably retarded. Depending on Type of unitraute to be destroyed, according to its stage of development, according to the extent of the infestation and the incidence or In the absence of ornamental or useful plants, the present compounds can be used in amounts of 0.28-0.56 kg / ha up to about 56 kg / ha on the ground, germinating weed seeds, weed seedlings, Plant growth media, growing plants or other selected locations for Weed control are applied. Usually the place of growth is the soil, but this expression is intended can be understood in the broadest sense, i.e. wherever the weed-wakefulness could be problematic, such as on Gravel roads, embankments, flat roofs, ponds, lakes, streams and canals. Pure water applications from about 2 to about 10,000 or more ppm are found to be effective.

The l- (substituted-HyarocarbyO-di- or -tri halogenpyrazoles of the formula I can be applied in a dispersible pure form, but dispersible preparations are preferred for herbicidal purposes. The dispersible preparations according to the invention consist of a 1- (substituted-hydrocarbyl) di- or -trihalogenpyrazol in homogeneous dispergi Erbar he mold and a homo-

10 9 8 3 5/1710

gene, dispersible carrier. Nil ft: substances ^T <vie surface-active agents, humectants, diapers -

lubricants, adhesives, corrosion inhibitors and foam retardants can be added.

Designation "more homogeneous, more dispersible! 'Rager" eats around a finely divided solid or a liquid Carrier as a diluent. I / ie connection can be considered resolved Substance or in the form of finely divided particles (suspension) be dispersed in a liquid diluent.

In the present case, "dispersible" is used to denote a substance in a liquid state or in a subtle hurry, so that it can be evenly distributed over a certain area or added to water in measured quantities, Both real solutions and dispersions are considered "liquid" refines urgent solids in a liquid. Emulsions of one liquid in another, such as oil-in-water, are also included as an active ingredient can be in the disperse phase, in the closed phase or in both phases. When using emulsions the active ingredient will usually predominantly be present in the disperse phase. As "f one-piece" are generally used finely divided individual particles or granular particles with a Particle size of 1.68 mm or even a little more, provided that the herbicidal agents are used accordingly makes the use of larger grain sizes appear advantageous.

The granular particles can be enclosed in an interstitial lattice, meaning that the active ingredient in is deposited or trapped in the interstices of a porous material. For example, the active ingredients can mixed with an elastomer, e.g. with natural rubber

109835/1710

Schuk, chloroprene, butyl rubber, polyether and polyester retnane oaer aer ^ l., which can be further processed according to the usual procedures in elastomer technology. These elastomer en katricee as well as conventional granules allow a slow, delayed release of the active seed nerbicide, so that herbicidal concentrations of the "active ingredient" can be obtained over a longer period of time in weed control.

To eat in connection with the excipients above Moisturizers mentioned include glycerin, diethyleniclycol or solubilized lignins (such as calcium lignin sulfonate). Dispersants include methyl cellulose, Polyvinyl alcohol or sodium lignosulfon ^ t. The iiaftoner adhesives include vegetable oils, of course occurring (fummir? or ivasein. A suitable corrosion inhibitor is chlorohydrin and a normal foam fuel ift stearic acid.

Examples of surface-active agents are alkyl sulfates and sulfonates, alkyl aryl sulfonates, sulfosuccinate esters, i ο j.voxyätnyl en sulfate, polyoxyethylene sorbitan monolaurate, jal'ivl ^ rvlttolyäthersulfate, alkylaryl polyether fatty acid, sulfate, aminated sulfate fatty acid, sulfate, sulfate-aminated fatty acid, glyphosulfate, sulfate, aminolated fatty acid, fatty acid, alkyl, amphthalene sulfonate, sulfate, sulfate, sulfate, sulfate, sulfate, sulfate, sulfonate, fatty acid, alkyl amphthalene Polyalkyl ether condensates of fatty acids or lignin sulfonates, etc. The preferred group of surface-active agents includes mixtures of sulfonated oils and polyalcohol carboxylic acid esters, mixtures of polyoxyethylene ethers and oil-soluble sulfonates, mixtures of alkyl aryl sulfonates and alkylphenoxypolyethoxyethanols, for example those made from approximately equal parts Sodium kerylbenzenesulfonate and isooctylphenoxypolyethoxavathanol with about 12 ethoxy groups and mixtures of gallium alkylarylsulfonates and polyethoxylating

109835/1710

BATH ORIGINAL

th vegetable oils. The pilot tenend proposed surfactant sulfates and sulfonates advertise preferably in the form of their lösliciien salts, for example used in form of their Nat ri u T ₁ s ze al. All these surface-active gowns are able to reduce the surface tension of the water to less than about 40 dynes in concentrations of about 1 hour or less. Dispersible powder preparations can optionally be produced with a mixture of the surface-active agents mentioned.

The concentration of the active substance according to the invention in the herbicidal preparations according to the invention usually not a critical, limiting factor in achieving the desired herbicidal effect. The most decisive factor is what kind of connection is made on a weed rough. tf pool is to be applied. It is easy to see that a large amount of a preparation with lower Active substance concentration or a relatively small one Some of these can be used with non-concentration can. Whether you opt for a low or a high concentration depends on the type of application, on the extent of the vegetation and the types of vegetation and also on how far-reaching the effect should be. The total amount to be used depends on the types of weeds and, if present, useful plants, according to the severity of the infestation, the stage of plant development and the season.

Homogeneous, dispersible preparations according to the invention are e.g. sprays, dusts and granulates. Sprays are used for applications on foliage as well as for evenly controlled soil applications preferred. Granules are usually made in strips that span the rows of seeds,

109835/1710 _BAD ORIGINAL

applied, a broad distribution is also appropriate, if it is worked into the soil and a longer-lasting effect is to be achieved.

The sprays according to the invention can be used as aqueous solutions, aqueous suspensions, water-in-oil emulsions, oil-in-water emulsions or oil solutions are produced. The concentration of the sprays is expediently about 0.1% by weight or less to about 50% by weight or even more, with the spray is applied in such a volume that an effective herbicidal amount of l- (substituted-hydrocarbyl) -di or trihalopyrazole is distributed over the treatment area. Me be an effective herbicidal treatment Sprays applied to foliage or soil containing about 7 g to about 7 kg of l- (substituted-hydrocarbyl) -di or trihalo pyrazole included on 75 to 150 1.

Concentrates for the preparation of sprays are preferably prepared by the fact that the fiction, contemporary Active ingredients dissolve in a solvent, or in a dispersible solid or liquid diluent dispersed as a carrier. For example, dissolve or disperse the present herbicidal l- (substituted-hydrocarbyl) -di or trihalopyrazoles in water or a suitable water-miscible or immiscible, inert, organic liquid. Examples of organic liquids miscible with water are acetone, methyl ethyl ketone, Dimethylformamide, alcohols, mono-alkyl ethers of Ethylene glycol or ethyl acetate. Examples of organic liquids that are practically immiscible with water (i.e. solvents carriers that are soluble in water at temperatures in the range from 20-30 ° 0 to less than 2.5 vol- #? are)

109835/1710

for the production of emulsifiable concentrates ε ± ηά Era oils, distillates, toluene, xylene, cumene and similar aromatic hydrocarbons, isoparaffin oil or mineral oil.

The concentration of the active ingredient in the emulsifiable concentrates (with or without a surface-active agent) is advantageously between about 5 and about 50, preferably between about 10 and about 40% by weight. A concentrate which contains cten dissolved in a water-immiscible solvent of the above type in an amount of 20 wt the resulting mixture contains 700 parts of active ingredient per million parts of liquid carrier. Similarly, 1 liter of a 20 % concentrate mixed with 160 liters of water yields about 1200 pom of active ingredient. Nöner-concentrated active ingredient solutions can also be prepared in the same way.

To produce dusts according to the invention, the active ingredient is dispersed in a dispersible pesticide by grinding a mixture of active ingredient and powdery solid carrier with one another. This is best achieved in a ball, hammer or air jet mill. The dusts can also be produced by dissolving the l- (substituted-hydrocarbyl) -ai- or -trihalogen pyrazole in a volatile solvent such as methylene chloride, mixing the solution with a powdery carrier solid, evaporating the solvent and the impregnated Powdered carrier. The final particle size is suitably less than 60 U,. Preferably , 95% of the particles are smaller than 50 m. And about 75 # 5 to 20 ^. Dusts with this degree of comminution are

109835/1710

pourable. Dust can be extracted particularly well from the outside air across ponds, lakes, perch, swamps, and marshy valleys Dredging holes are distributed.

Suitable powdery carrier solids are, for example, the natural toners such as china clay, Georgia clay, bard clay, attapulgus clay, kaolin and bentonite clay; Minerals in natural form as weraen ge gained from aeiii bottom - za talc, pyrophyllite, quartz, Diatomeenerae, Fullererae, chalk, phosphorites, mineral sulfates, calcium carbonates, Scnwefel, silica and silicates; chemically modified minerals such as washed bentonite, precipitated calcium phosphate, GaI ciuiiicarbonat and calcium silicate, synthetic i ^y i ^! ignesium silicate and Kolloicucieeelerae; organic flour such as wood, walnuiii-cnaif-n-, soyabon, cottonseed and tobacco flour ο, as well as rienelfänige, hydrophobic starches, üas proportion of powdery carrier material to l- (substituted-nydrocarbyl) -dioaer -trihalogenpyrazole can ever Depending on the plants to be processed, the application ratio and a. In general, the active ingredient content of dusts can be up to about 9% by weight. It is also possible to use dust with only 0.001% material, which is preferred, but amounts of active ingredient from about 0.5o% to about 20%.

It is advantageous if the dusts described above contain a surface-active agent. In an amount of about 0.1 to about 12 %, this promotes the dispersibility of the dust in water, facilitates the formation of aqueous sprays and increases the dispersibility of dusts that are deposited directly on water surfaces or water weeds.

10 9 8 3 5/1710 ** ■■ --— -

BAD ORiQlNAL

Powders containing a surfactant are known as dispersible or wettable powders. As mentioned above, dispersible or wettable powders can be mixed with water in an effective concentration of active ingredients. You can be about 10 to about 90% -, preferably about 30 to about 80 % of active ingredient.

A suitable dispersible powder is obtained by. 148.3 kg G-eorgia clay with 2.04 kg isooctylphen oxypolyäuhoxyäthanol as an IM wetting agent, 4.08 kg of a polymerized sodium salt of a substituted long-chain Benzoesulfonic acid as a dispersant and 51.25 kg of active ingredient are mixed and ground. This results in a preparation The following percentage composition (unless otherwise specified, this is Parts by weight).

Active ingredient 25 %

Ifcooctylphenoxypolyethoxyethanol I ^

Polymerized sodium salt of a
substituted, long-chain benzoesulfonic acid 2 "/ o

Georgia tone 72 %

By dispersing this preparation in a ratio of 1.2 kg per 100 liters in water, an opray preparation is obtained which contains about 0.3 1 » (3000 ppm) of active ingredient and which can be applied to weeds in an amount of 371 l / ha . This corresponds to a total amount of active ingredient of 1.12 kg / ha.

, The present new l- (substituted-hydrocarbyl) -

10 9 8 3 5/1710 SAD ORIGINAL

di- and -1-halo enpyrazole and especially the "5,4,5-tribromo-cc-methylpyrazole-1-acetic acid have a beneficial effect on plant growth. They correct the spike endomination normally observed and effect Bpinastia symptoms when they are in the growth stage in plants be used. They are suitable for understanding the lateral bud growth and the fruit-bearing ones To perish bodies.

Furthermore, certain preparations of the l- (substituted-hydrocarbyl) -di and trihalogenpyrazole with oil as particularly effective, and it comes to an improved herbicidal effectiveness of the compound. Any petroleum can be used provided that it is not is too viscous and therefore difficult to disperse. With a non-phytotoxic oil gives satisfactory results.

For spraying, it is expedient to mix a 50% wettable powder of the herbicidal active ingredient about 144 liters of water and 7.6 liters of oil. For the same purpose, however, you can also use about 7.6 l of oil with a 50 # wettable Premix the powder and then disperse in about 144 liters of water. Oil preparations of these have been found in field tests Kind of an improved herbicidal effect.

109835/1710

Claims (1)

Patent claims: 1- (substituted-hydrocarbyl) -di and -trihalo pyrazoles the formula in the "η" the whole number O, 1, 2 or 5, "X" is a halogen atom, "m" the integer 2 or 3 »where the halogen atoms are independent are from each other, "" R "is a hydrogen atom, an alkyl group with 1 to Carbon atoms or an alkenyl group having 2 to 10 carbon atoms, the sum of the carbon atoms in the group * is not more than 11, and "A" is the carboxyl group and its alkali metal, earth 109835/1710 alkali metal, ammonium or amine salts, the Hydroxymethylji-ruOue, a hydroxymethyl-lower-alkanoate group with 1 to 8 carbon atoms in the lower-alkyl radical, a carboxylic acid-lower-alkyl ester group with 1 to 6 Koni en tofatomen in the lower-alkyl rest, the Oyanogruppe or an Oarbonsäureamiagruppe of the formula OR ₁ K mean -wherein R ₁ and R _{9 are} hydrogen atoms or fol ^ enae, mutually independent substituent groups represent: a lower alkyl radical with 1 Dis 8 Konierstoffatomen, an alkenyl residue with 3 to fa Kohl eustoi fatomen, an alicynyl residue with 3 bit ü Koniiiüstoffatomen, an aralkyl radical with 7 to 13 ivoMenstoffatornen, a ^ .rylrest with 6 to Iu carbon atoms, where R, and Ry cannot be aryl at the same time, a cycloalkyl radical with 3 to 8 carbon atoms, a cycloalkenyl radical with 4 to 8 carbon atoms and the -m ^t "" group taken together is an -R ₂ saturated heterocyclic iouino group with 3 to 7 Ring atoms with no more than 15 carbon atoms in total. 2. Compounds according to claim 1, in which "X" means broai. 3. Compounds according to claim 2, in several "m" the Number 2 means. 109835/1710 BATH ORIGINAL 4. Bibromopyrazoles according to claim 3 »in which" n " the number O and "A" denote hyaroxymethyl. 5. 3 »5-jibromopyrazole-1-etiianol. 6. 3 »5-bromo-β-methylpyrazole-1-ethanol. 7. DiDroiüpyrazole according to claim 3 »in which" n " the number 0 and "A" represent a carboric acid group. 8. 3 »5- labrom-a-methylpyr ^ zoi-.l-acetic acid. 9. Compounds according to claim 2, in which "σι" the Number 3 "means. 10. Tribroiüpyrazole after AnsDriicn 9, in which "n" the number υ and "a" mean hyai-oxymethyl. 11. 3 »4 j b-tribrornopyrazole-1-ethanol. 12. Iribromoyra ^ ole according to Aneüruc · 9 »in which" n " the Z-; hl O and "a" mean a carboxamide group. 13 x 3,4,5-iribromo-3 '^' - aichloruyrazole-1-acetanilide 14. 3,4, 3-i ^l ri bromo-3 ·, 4 '-dicnlor-a-juethvlr> yrazole-lacetanilide. 15. 3 »4 ^ -tribroiupyrazole-1-acetamide. Ib. 3,4 ^ -trib 10 9 8 3 5/1710 BAD ORiGINAL 17. 3j4 ^ - ^, a-diniethylpyrazole-1-acetamide. 18. 3,4, ^ - l'ribromo-N-methyl-a-ethylpyrazole-1 acetamide. 19. 3.4,5-iribromo-JS, l \ [, a-trimethylpyrazole-lacetamide. 20. 3,4, ij-Tribrcjm-ii'.N-dimethyl-α-ethylpyrazole-lacetamide. . _ 21. 3,4, ^ -tribromo-H-ethyl-α-methylpyrazole-lacetamide. 22. 3,4,5-tri'bromo-N,]) f-diethyl-a-met] iylpyrazole-lacetamide. 23. 3 »4, ^ - Tribrom-NjNja-triäthylpyrazol-1-acetainid. 24. 3j4 j 5-TΓibromo-N, lί-dipropyl-α-methylpyrazole-laetamide. 25. 3 »4, ^ - Tribromo-N.N-dipropyi-a-ethylpyrazole-lacetamide. 26. 3,4, b-Tribromo-W, N-dimethylpyrazole-1-acetamide. 27. 3,4, 'p-TribiOm-N-allyl-α-methylpyrazole-lacetamide. 109835/171 - 50 - 28. 3,4,5-tribromo-N, F-d.iallyl-α-methyloyrazole-1 acetamide. 29. 3,4, ^ - Tribromo-N.jX'-diallyl-a-ether pyrazole-lacetamide. 30. 3,4,5-tribromo-li-butyl-α-methylt / yrazole-lacetamide. 31 3.4, ¹ J-TRJ bromo-H- t he t.-butyl-α-methyl TDY 1-acetamide. 32. 3,4,5-Tribroin-N-cycl ohexvl-a-ruethylpyrazole-lacetamide. 33 x 3, ^d , 5-tribromo-II, K- (3-oxapenta! Iiethylene) -amethylpyrazole-1-acetamide. 34. 3,4, ^ -tribromo-H-methylpyrazole-1-acetamide. 35. Tribromopyrazole according to spoke 9, in which "A" means the carboxyl group. 36. Tribromopyrazole e according to claim 3 ¹ ^, in which "n ^{n is} the number 0". 37. 3,4,5-tribromo-pyrazole-1-acetic acid. 38. 3,4 ^ -tribromo-u-ethyl-oyrazole-1-acetic acid. 39 x 3,4,5-tribromo-a-ruethylpvrazole-1-acetic acid. 109835/1710 - -59- 40. 3 »4,5-Tribrora-α-isopropylpyrazole-1-acetic acid. 41.5,4, ^ -Tribroni-oc-butylpyrszol-1-acetic acid. 42. 3,4, s-'i'ribromopyrazole-1-proionic acid. ■ ■ ■). 5,4, b-tribromopyrazole-1-butyric acid. 44. Tribrompyx ^ azoles according to claim 9 »in which" n " the numbers 0 and "A" represent a carboxylic acid ester group. 4b. Ethyl 3,4, b-tribronrpyrazole-1-acetate. 4b. Ethyl-5,4, ^ -tribroiü-a-iuetnylpyrazol-1-acetate. 47. Ethyl-3,4, S-tribromo-α-dutylpyrazole-1-acetate. 4ö. Etnvi-5.4, b-tribromo-a-ethyluyrazole-1-acetate. 49. Ethyl 3,4,5-tribroiü-α-isopropylpyrazole-lacetate. 50. Tribroinpyrazole according to claim 9, in which "A" the oyano group means. 51. Tribroiiipyrazole according to Anspi "uch 50, in which ^M n" means the number 0. 52. 5,4,5-tribromopyrazole-1-acetone "cril. 53 x 3,4, b-tribromo-a-methyltyrazole-1-acetonitrile. 54. Triürompyrazole according to claim 9, in which "A" denotes a hydroxymethyl lower alkanoate group. V ₁ 109835/1710 __ SAD ORIGINAL -6Q- 55.3,4,5-tribromopyrazole-1-ethanol acetate (ester). 5b. Process for the production of an aer di- and. Trihalogenpyrazole-l-alkanecarboxylic and -1-alkenecarboxylic acids Qjr formula RCC _n H _2n -G-OH According to claim 1, characterized in that a Dioasr Trihalopyrazole with an alkyl haloalkanoate or .alicylhal local alkenoate using acetone as a reaction agent eaiuuii in the presence of an anhydrous alkali metal carbonate bia heated to complete N-öuDεtituierung, the alkyl di- or trihalogenopyrazole-1-alytanoate thus obtained oaer -1-alkenoate with an aqueous alkali metal hydroxide with formation of a corresponding di- or 'fri halogenpyrazole-1-aliiancarDonoaer -1-alkenecarboxylic acid - ■ alkali metal salt hydrolyzed and the latter with formation the corresponding di- or trihalogenpyrazole-i-alkane carbon- or -1-alkenecarboxylic acid is acidified with an acid. 57. The method according to claim 5t> »characterized by that a Di- oaer tribromopyrazole with an ethyl 2-haloalkanoate heated in the presence of anhydrous potassium carbonate, adding aqueous sodium hydroxide, which 109835/1710 BAD ORiQfNAt Acetone removed and the alkaline aqueous reaction mixture while obtaining the corresponding di- or trihalopyrazole-1-alkanecarboxylic acid heated. 58. The method according to claim 57, characterized in that ethyl 2-bromopropionate is used as Atiayl-2-haloalkanoate used. 59. Use of one of the compounds according to claim 1 to 55 as an active ingredient in a herbicidal agent or in an agent for regulating plant growth. Pure: The Upjohn Company Lawyer 109835/1710