GB2205749A - Herbicidal composition and process for the preparation of the active ingredient components thereof - Google Patents
Herbicidal composition and process for the preparation of the active ingredient components thereof Download PDFInfo
- Publication number
- GB2205749A GB2205749A GB08814190A GB8814190A GB2205749A GB 2205749 A GB2205749 A GB 2205749A GB 08814190 A GB08814190 A GB 08814190A GB 8814190 A GB8814190 A GB 8814190A GB 2205749 A GB2205749 A GB 2205749A
- Authority
- GB
- United Kingdom
- Prior art keywords
- general formula
- mixture
- phenoxy
- moles
- nitro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- 239000004480 active ingredient Substances 0.000 title claims description 35
- 238000000034 method Methods 0.000 title claims description 24
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- APVPOHHVBBYQAV-UHFFFAOYSA-N n-(4-aminophenyl)sulfonyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 APVPOHHVBBYQAV-UHFFFAOYSA-N 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
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- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
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- 239000000600 sorbitol Substances 0.000 description 1
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- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/39—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups
- C07C205/42—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/44—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by —CHO groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
2205749 HERBICIDAL COMPOSITION AND PROCESS FOR THE PREPARATION OF THE
ACTIVE INGREDIENT COMPONENTS THEREOF This invention relates to herbicidal compositions of increased selectivity and a process for the preparation of both active ingredient components in one step.
According to an aspect of the present invention there is provided a herbicidal composition of increased selectivity comprJLsino as active ingredient at a 50:1-1:50 t ratio by weight a mixture of a 5-\subSL.^Lt,.lted phenoxy)-2 -nitro-benzaldehyde ol the general Formula I CF, 3 X C-] c 0 (wherein X stands for hydrogen or chlorine) and 5 (substituted phenoxy)-2-nitro-benzaide.l-ty,r4e diacetate of the general For,-,,ula II 6 y X Cl (C) r 0 Gy._ NO9 e e i n Y i s a s s t a- t e rd a. b cv e ,cccrd--r.g to a Lccr.t-her aspect o.L' the present in ej a her,-a'L ver-,it-on e2i-.pr-Ls on there Is Provi, c omp(-,s t r c as active -ngre-l.J.-nt a.-'Luted a /where-- t e n z a e 1-1 v j;-= --4 --:;cetate cf the general Formu.
further X -f'cr hydroGen cr cl-.-'or-Jne/. The I- - -- effective pr-c-,-=s e a tme nt. selectvel.
Y aza -' nst wee -- s app ly ing the al- ove c o:npos.-Lt -4 or 1 er. t s of generel Frm.j.
T a -- t -11 v e i n =. r-- e d - -: I anj c the starting materials of the ger-era-' Fc-m-.j-'a T'T anJ CP 3 X4C1 0 / -1 1,/ 0 COIC,I 1% H used in the prep3r@'Li-On thereof are known corDcunds disclosed in the prior art, new. The Lituted phenoxv'.
L il i 1 the general Formula 1, the preparation and herbicidal activity thereof is disclosed e.g. in US patent No.
4 5 306 900. The said compounds are prepared by a cl assical Ullmann-type ether synthesis by coupling 2-chlor-c-"'-tri fluoromethyl-phenol with 2-nitro-5-flucro-benzaldehyde in the presence of potassium carbonate in dimethyll su'Llicx-'ide.
In DOS No. 3,044,810 new substi cinnamic acid derivatives are disclosed which are pre, pared from the 5-(substituted phenoxy)-2-ni'kro-benza'-dehydes of the general Formula I as new intermiediatees. The ed phenoxy)-2-nitro-be7,za-ldehyd---s are nct prepare'd licwever according to Ullmann-synthesis but by subjecting a 3 -(substituted phenoxy)-benzaldehyljle diaceta-4k. the ger-,c=i7al :e cl Formula II to hydro!Lvsis. The reacticn is car-ied cut in a d; mixture ef methanol and Water with the aid of iluted aqueous sodium. hyLlrox-ide sG'Lu'Lon. AcCording t.c the DOS referred to above the 5-(substituted phenoxy)-2-n-'Ltro-benz aldehyde-diacetates are designated as new compounds, there is however no reference to any herbicidal activity thereof.
Pursuant to DOS No. 35044,810 the 5-(substituted phenoxy) are prepared by nitrating a 3-(substituted phe-cxyl-ben-C aldehyde of the general Formula III. The said n-,.lratJLc.n reaction is accomplisheC Lhe by reaCting the compound of - general Formul.2 TT I in the f irs' step in 'he p-esence of L a sc-lvent (e.g. methylene chloride) at a temperatUrE Of c C with acetic anhydr.JLile, nitrating the mixtire in the second stage with nitric acid at a temperature between 0 -10 C and +20 C and finally isolating the 5-\..--ubstituted phe.ncxy)-2-nitro-benzaldehyde diacetate thus obtained.
According to the teaching of the above DOS the 3-(substituted phenoxy)-benzaldehydes are new compounds and are prepared by reacting 3-hydroxy-be-.zaldehyde with 3,4,5-trichloro -benzotrifluoride in the presence of an acid binding agent (e.g. potassium methylate) in a solvent (e.g. dimethyl sulfcxide, toluene etc.',.
In DG'S Nc. 3,017,795 the 5-(substituted phenexy)-2- -nit--G-benzaidehydes of the general Formula I are disclosed as new intermediates never described hitherto in prior art.
These compounds are prepared by reacting a substituted 4 --.h,c2o-benzotri'.luoride and a 3-h.droxy-benzaidehyde.
Accordino to DOS No. 3,11.8, --(2-chlorc- or 2,6-dich'Loro-phe,noxy)-2-nitrG-benzaldehydes are prepa-:-e, Lly nitrating a 3-(2-chloro- or 2,6-d.Lch'Lorc-pil-lencxy-benz- alcJehde diacetale. Nitration is carried out in a solvent optionally in the presence of a catalyst by using 1-3 moles (preferably 1.2-1.5 moles) of nitric acid related to 1 mole P of substituted phenoxy-benzaldehyde diacetale. The nitro compound is recovered from the reaction mixture by known methods e.g. by adding a practically water non-miscible scIvent, separSting the organic phase, w-ashing it aci,-' free and e,,apcrating. In DOES No. 3.11E,3711 t';-le pre--arat-Jcn of' the 5 - 'E -ut -- t i t c t e d p ',--I en -- X. ' - 2. -r. it -1 C - =E r Z a 1 de h Y:J E d -- a -- e: ta -- e s of the general Formula II is set, forth as well.
The 3-(2-substituted phenoxy)-benzaidehydes of he general Formula III is reacted with acetic anhydride at a temperature in the range of 10-80 0 C in the presence of a solvent, (e.g. methylene chloride), whereupon the 3-(substituted phenoxy)-benzaldehyde diacetate thus obtained is nitrated with nitric acid at a temperature between -10 0 C and +20 OC, the reaction wiixture is diluted with water, the water non-miscible layer is separated or distilled off and the 5-(substitUt "ed pil,,enoxy,)-2-nitrc-"Uenzaldeh,de diacetate is isolated. The 3-(substitU'Led phenoxy)-benz aldehyde dlacetates can also be prepared by reacting a 3 (substituted phenoxy)-benzaldeillyde diaceta:e with a molar of acetic a- -(Houben-Weyl, Band VII/1, pace equivalent -id 443, (1958)7.
According tc DOS No. 3,100,167 the potassiurr, salt de-di of 3-hyd--.oxy-benza-dehy Lmethylacetale is reacted with f pc' 3,4-dichloro-benzotrifluoride in the presence o. Lassium carbonate and dimethyl sulfoxide, whereupon the 3-(2-chloro thus obtained is recovered by known methods, the product is dissolved in dioxane and concentrated sulfuric acid is added to the solution in portions. The mixture is hydrolysed at 30 OC for half an hour, the reaction mixture is poured on ice and the 3-(2-chloro-4-trifluorome-l.h,1-phenoxy)- -benzaldehyde thus obtained is isclated by ireth--ds knewn per se. The 5-(2,5-dich-ic,.-o-4-tri,-"luo.-or,.ethy'&.-pl,enc)xy)nitro-benza-Ld.e-.vde is prepared;n ar, analoccus m n n er 6 except that -ntrc-tenza-'--ehvze d,-'.Jace',a-e is in A acic as me,-",.;m.
In thle course of o,,.ir experiments directed to the preparation of 5-/subsl,ituted phenoxy/-2-n-'-ro-benzaldehy-es it has been iound that', when fi-Ltra't,-ing the compounds of the general FormuIla K! undler the molar ratio defined furtherGn no'- the expected 5-/substituted phenoxy/-2-nitro-be-,zaldehyde t-j-- the ciacetate therecf is formed.
lt, has been fo.jnC, that when the mclar ratio is care- fully selected the following compounis can be prepared:
- a phenox3/-2-n--tro-benzal-del-yde o" the zeneral Formula I, aceta-e - a 'tuted phe.-oxy/-4-r.-L.'.ro-lenzaidehylp--.-. - t c:O the general' Formula II, or in a surpris-ng manner c'L the- of the general - an cptJ--al z, u 1 -, i.
ae 1 and - i-cal stud-eE have reyea-..-e,- that F-,,-r'lh,er t clog 1 - a ir,x'L,,ire cf the compz,;njs of the general i and II shows an increased herbicidal selectivity over the compounds of the general Formula I and I! when use.
is' so much separately,.e. per se. This recognition the more sjrpr-4s-ing as in the prior, art 5-/s'u'L,,s,iuuted phenoxy/-2-n-tro-benzaidehyde-d2Laceta'.es cf the ge neral Formula III are disclosei merely as Jn',e-m.ed--aties o hert-- J, any re'erence act - The selectivity is c=ected w-.,.th the energy wkes p^pe 'n ce'-7-- 1.
Q of the plant and it - indirectly - relates to the inhitition of the adenosine triphosphatase (referred to furtheron as ATP-ase) activity, the 5-(sub5tituted phenox,-")nitro-benzaldehvde diace-ltates of the general Formula II also exhibit herbicidal aC+,iV-"'L-.
According to an aspect of the present invention there is provided a herbic-idali- composition of increased selectivity comprising as active ingredient at a 50:1 - 1:50 ratio by weight a mixture of a 5-(,substitu-lked phenox,--7 -nitrc-benzaidehyde of the general Formula I (whEre-in X stands for hydrogen or chlorine) and a 5-1'Isubst-itu41ed phenoxy,-9--nLtro-11..)enza-ldehyde diacetate of the peneral Formula IT (wherein X is @s stated above).
According to a furthEZ feature of the P:esen+l -inven- tion there is provided a her-bicidall COMPOSitiOn Je-d-ace- te a 5-\subs+,-,'LL;t--d phen,x)-2-n-,'..ro-benza Idehy, L, a of the cei-,eral tcrwlul_a T! (wherein X stancs fo:, o r r, h -; c n e ACCOrdIng to 2 Stii-1 feature of.the present invention there is provided a process for the preparation of a 50-1: 1-50 ratio mixture (in parts by weight) of a 5-(substituted phenoxy)-2-nitro-benzaldehyde of the general Formula I and a 5-(s,.'.,--,tituted phencxy,,-i-n'Lt4---b,--nzaldehyde- -r-mula II (wherein X - -diacetate of the general Fo. stands lor hydrogen or chiorine with the prc-iso that X has the eame meaning in the general Fo:,,-,ulae 'L and IT. n cne Ireazt on _o step wlijLch reacting 1 mcle of a p h a l cle h v de c. f c ene-- a l F cr.m u a 1 T -, - X stands fcr hydrc.gen or chlcrine,' in the p7esence of a L p,-,ei'erabl. dichloro methane - a o -, r. 'L e r7 e r 2 tu r e or at a 1Gwer with 4- 'L 1. m----i es c.f acet-ic annydr 'L de and a nitE2"L-. ng acid consisting of a mixture of 1.2-2.6 moles of nitric acid and 0.1-2.8 moles of sul'Lur--':
acid, isolating the mixture of the compounds of the ceneral Formulae I and II from the reaction m.
ixture by knsw, method= and, if desired, purifying the mixture thus obtained.
he 3-1 T 'substituted phe,)ox"'-'----nzaidE'-,de of L th e ge7era.i Fcrmcl P -1. ITL used as Starting material can, be prepared y cs.upling the potass-L.-'m salt of 3-hydroxy-benzaidehyde with r Ii ch 1 c r o - b e 3,4-l.ch-.oro-be.nzotriflucride or 3,4,5--1. zotri- 1 L1jc7icle, respectively.
n By appropriate selection cf the m-.!a:, ratio of t!-e reaction, components used in the nitration step, mixtures c -f t.-: e t w c. c s. rr, p c n e n t s c) ff t h e h, e r t -i c i d a 1 c c rint p c s i t i P. 5 a v i n c) increase:- selectivity ef the invention - Fia,-e"y r,-i xt-7es cf c!--,-..,pcjnds of the general Frormj! ae T and il L - L J.
of c.ptio-.al r2ti-- ca.---be cbta,,,ed.
According to the process of the present invention the starting material of the general Formula i'LI is at first dissclved. For this purpose any inert solvent can be used which does not intervene with the nitration reaction. As inert solvent preferably a chl-orinated hdrocarbon (e.g.
d.'chici,o methane) can be used. A mixture of dichloro methane an, ai:e',-ic can a' sc be used @5 scl,. n, selej-'- n 1 1 - a k-n. n ' E 2 t h e a r.-, c u ri t, c. 'L a,-,e'L-Jc anhy(.-ide it MiSt be t - 1 - T -,;n J C-. t - E f act-r E_ - ú c E - --' -- - a +1 t. '- - 1. l:: f i c a r t I,, e f -" e 5 9 ratio of the compounds of the general Formulae I and II even at a given molar ratio of sulfuric acid and n-Lt.'iC acid. After dissol-ving takes place a further amoint of acetic anhydride is added to the homogeneous solution which is then cooled and the addition of nitrating acid is slowly started, preferably at a temperature between -20 0 C and +5 OC. The said nitrating acid is prepared by admixing concentrated nitric acid (65%) and concentrated sulfuric acid (98%). The nitration and binding of Water formed in the reaction are strongly exothermic and for 'Lh4;.S reason care must be taken of proper cooling. Nitration is preferatly accomplished at a temperature between 0 0 C and +5 c C. The nitrating acid is usually added within an hour.
The system is then allowed to warm up, whereupon the reac tion mixture is warmed to 20-40 0 C - preferably to 25-35 0 C and 2'L,.Icwed to react -for a further period of some hours (about 2-4 hours). The reactio- mixture is pourezi; c:7, ice.
the phases are separated, the aqueous layer is extracted with the same solvent used for dissolving the startino material. The organic layers are united, washed neutral successively with a diluted aqueous sodium carbonate solu tion (2-5% by weight) and water, dried (e.g. over anhydrous magnesium sulfate), the drying agent is removed (e.g. by filtration) and the solvent is evaporated in vacuo. The product thus obtained (mainly consisting of a mixture of a I and 17., can be the compounds of the general Formul treatment with an orcar-%.
purified, if desired, e.g. b"V L 4c sol ven t, or so! vent mi xtu re ( e o chlor ornethane, tc -1 _erle etc.) or reCryS481-'i7atn.
I I The molar ratio Of sulf ur Lc acid, nitric acid anC-4 acetic anhydride - rel2te--J to the starting material of the general Formula III - has a strong influence On the ratio of the compounds of the general Formulae I and II formed in the process of the present invention. Thus an increase of the ap-cunt of sulfuric acid (0.1-2.3 moles,11 mole of a compound of the general Formula III) promotes the formation of the compound of the general Formula I, while an excess of acetic a-,-hydr.Jde (4-11 m--Ies/'l mole of 2 ccrpcj,-z! of J7 the general. Formula I') promotes an increase of the ratio of the compound of the general Formula II. An augmer-tation of the amcunt of nitric acid (1.4-1.7 moles/l mole of a compojnd cf the general Fcrmula III) results in an increase of the ratio of the compound of the general Formula I, to a smaller extent.
From the series of experiments we have drawn the high- ly valuable ccnc'Lus-on that if the molar ratio OIL acetic a,ihytride is 5 mcies/l mole of a compound of the general Formula III and the total molar ratio of nitric acid and sulfuric acid amounts to 2.9 moles/1 mole Of 2 compound of the general Formula III, on altering only the molar ratio of nitric acid and sulfuric acid in the range of 1.2/2.7 - - 1.55/2.35 the ratio of the compound of the general Formula I of the mixture thus obtained increases from 30% by weight to 100% by weiioFlt. and starts to decrease frcr. a MclLar ratio of 2.0/1.9. Thus by using a mclar ratio cf 1.2/2.7 1.5-5/2-35 zi a-it 2.2/11.8 - 2.611.3, respectiVely, 2 her.t.-J, cidal cor-,tination having increased selectivity of optional com-pcsiticcr can repared.
be p The compounds of the general Formulae I or II have been tested herbologically per se and it has been found that in a dose of 0.5 kg.ha- I the said compounds are not phytotoxical against the following cultivated plants:
from monocotyledons, tobacco, cotton, cabbage, flax, lettuce, carrot, muscat melon, pumpkin and plants belonging to the order of leguminous plants; from dicotyledons, barley, winter wheat, onion, maize, rice and oat.
On the other hand in the same dose (0.5 kg.ha- the said compounds are active against a number of dicotyledonous weeds shooting from seeds and against several monocotyledonous weed species.
The compounds of the general Formulae I or II, when used per se in a dose of 2.0-3.0 kg.ha- show a total effect against the following hardly contrcllabLe mono and dicotyledonous weed species (practically against most of the weed species).
From dicotyledons:
Abutilon theophrati (abutilon) Calystegia sepium L. (bell bine) Datura stramonium L. (jimson weed), Galium aparine L. (cleavers) and X2nthium strumarium L. (bur-weed).
12 Fi-c-,, monocotyledons:
Alopecurus m;--surc-ides Huds.,black cra-cs,., Apera spica-er-it.k L. (silky bent grass; Poa trivalis L. (wood meadow-grass) Sorghum Halepense L. (Johnson grass) Panicum capillare L.
At the same time on using the same dose '2-.0-3.0 kg.ha) all the cultivated plants are killed with the exception of soya and.perhaps winter wheat.
The ccmpounds of the general Formula: or II, be used against particularly resistant weed species only d L 1 - L L I in soya and sometimes in winter wheat cultures. Acifluor p11hen - i. e. sodium-5-(2-chlrro-4-'Lr..Fl.uc:rcme'Lhyl-phe..ncxy.- -benzoate - shows a sirrilarly narrow effect spectrum and is iseful exclusvely in the control of scya.
L It has been IL3und on the other hand that mixtures of ncs of the general Foi-rr,,-llae I and II ha\ inc a the present invention in 2 rl--se of 2.C-3.0 pc s L t4 on c. - 1 k h a k i 11 'L he a b.-\ em entioned wee i es be in c d i f f i c!,,. t tO C071trOl. (practically most of the weed species) while al.
the same time the said compositions within certain ratio ranges are nct phytotoxical against many cultivated plants species particularly on leguminous plants (Examples 41-46). According to our test results the combination of the compounds of the general Formulae I and II having the CGMPOSitiCr Cf the p7ese-+1 in,ent.cr-. can be selectivey us-ed in. sc a and w-ir-,te: cul ",,jres but alsc e.c. in bear-s. cDksheadc-, pea-Lts, pea,--,es, 1 leritilS, broad beans, medics, clovers i.e. generally in cultu.res of leguminous plants.
In addition to the hernOlogical tests 45 and 46) also biological tests (Example 471) show that the compounds of the general Formulae I and II and particular ly combinations thereof according to t'he invention represent a mode of action being in connection with the energy produc ing procedures which take place in the root cells c.' the plants and is - indirectly related to the inhibition of ATP-ase. Our tests are directed to ascert. L L. -ain whether mixtures of the said compounds having different compcs-itions cause any change in the ATP-ase activity and phytc'tox-Lci-ty.
It has been found that, contrary to the results obtained with the four compounds used per se, the 16:1 - 1:16 mixtures of the present invention induce a significant inhibition of activity when used already in a dose of 1 kz.ha- Outstanding -inhibition dat ta are achieved when using the compounds of the general Formulae I and ILI in a r2tiC Of about 8:1.
The compositions of the present invention are suit- able both for pre-emergent and post-emergent application.
The active ingredient dose may vary between 0.2 and 9.0 kg.ha- 1, preferably 0.5-3.0 kg.ha 1, depending on the quality of the soil, the meterological conditions etc. For spraying purposes it is preferred to use 200-500 1.ha- 1 of water.
The invention mixtures of the cenpounds Df tlie ge,-.eral Formulae 1 and I! can be fc-.r7!-,'a'.ed i-1 USJall 'GrIMIS L- kr-c)v.,ri per se. 'I hus ore ray prepare e.-c. wettanle powders WP sLspensJ on conce n ttr ate s (SC', w a ter- m i scil- l e Eo- ut i o n L J_ L. L EC), granule.
ccricentrates (SL'), emull sif iable cE7,ze-,,',ra'tes applicable without water (S'), dust-ing powders (DP) or oily suspension concentrates (F0). The active ingredient mixtures can be applied in ULV forms as well. In the said composi tions the mixture of the active ingredients is admixed with solid or liquid carriers or diluents and optionally with other auxiliary agents. The said auxiliary agents may be e.g.
surfactants, wetting agents, sQspenk,.,i-ng agents, dispersing aents, emulsifiers, anti-agglomerating agents, anti-caking agents, adhesive agents, spreaders, penetration increasing agents, substances capable of maintaining cr increasing the biological aCtiVity, antifoam agents etc. From the proup of solid carriers and diluents the following substances can be mentioned: rninerals e.g. China-clay, varicus kaolin tpes, attapUIC:'i-Le, montmorillonit, mica slate, pyrophil lite, bent tonite, diator-naceous earth or highly dispersed synthetic silicic acids, calcium carl--,.nate, callcinatedl macnes-ur., oxide, dolomite, gypsum, tricalcium phosphate, Fuller's earth.
Suitable further solid carriers and diluents are ground tobacco leaf stem, wood flour etc.
Suitable liquid diluents and solvents are the follow- terials: water; organic solvents; mixtures of organic ing Mat L sclvents and those formed with water e.g. methanol, ethanol, -,-p7opanol, diiacetone alcohol, benzy! alcohol; eEters of the said @!c--hcls e.g. rnE4Lhyl cellosc.lve; ketones ketone et h 1 ket23-ie, me 1h is c b L, E. C. CL -r L- - L ketone. cyclopentan-ne, cvc'ohexancne etc.; ethyl acetate, L, L i, - I I I n- and isobutyll acetate, amyl acetate, isopropyl miristate, dioctyl phthalate, tihexyl phth2late etc.; aromatic, aliphatic and 2licyclic hydrocarbons e.g. parafffdne hydro carbons, cyclohex@ne, kerosene, gasoline, benzene, toluene, xylene, tetraline, decaline etc.; m,,'xtures of alkyl benzenes; chlorinated hydrocarbons e.g. trichloro ethane, dichloro methane, perchloro ethylene, dichloro propane, chloro benzene etc.; lactones e.g. butyrolactcne etc.; 130tames e.q. N-methyl-pyrrclidone, N-cyclohexyl pyrrolidone; acid amides e.g. dimethyl forma....mide etc.; oils of vegetable or anim2l origin e.g. sunflower oil, olive cil, soya oil, castor oil etc.
The suitable wetting, dispersing, emulsifying, adhesing, anii-aggregating, anti-caking and spreading agents may be of ionic or ncn-ionic character. The ionic surfactants may be e.g. salts of various saturated cr unsaturated carboxylic acids; sulfonates of aliphatic, aromatic, or fates of alkyl, ary' araliphatic hydrocarbons; sull or aralkyl alcohols; sulfonates of alkyl, aryl or aralkyl acids, esters and ethers; sulfonates of condensation products of phenol cresol. and naphthalene; sulfatated vegetable and animal oils; alkyl, aryl and aralkyl phosphate esters; salts of the above compounds formed with alkali or alkaline earth metals or organic bases (e.g. various aminesalkancl amines factants etc.). As preferred representatives of the above sLjr.L the following compcunds can be mentioned: sodium lauryl sulfate, sodium-2-ethyl-hexyl-sulf. ate, sotium, etiEnoll a-.ine, 16 - cl - E G n c -- a.-,, in e, t - j e t 1- 2. n c 1 a mine, an o p ro a L L L 1 - -L - L L. n e salt of' dodecyl benzene sLl'Lonic aci; M3P0 and diis,-rcpyinap'iLnalenE SUIllonate; sodijm salt of napil.,talene sulfonic acid, sodiurr, diisorctyisulfosucci,,-iate; sodium xy'Lene-sul.i"onate; sodium or calcium salt of petroleum sulfonic acid; soaps; sodium, calcium, aluminium, -earat magnesium sI. le etc. The phcsphate esters may be e.g.
ethers of phosphatated al kyl phencls or fatty alcohols X Lc-rr-ed with pcI,c:lycc?l @7d forms thereof partially i t t 4 cr cGr-.pletel, neu'L.-21-zec W. Lh Lhe al-,.,vei7e7,tione,.' C2t Lons ther ives of or crg,3nJ--- bases. As furt SUitLa"-'e repi7esentat- anionic surflactants dis,-durn-N-octacecyl-sulLosucci-n8Le, so- hl-tauride and various lignosulfonates can be mentioned.
Suitable non-ionic WEtL ting, dispersing and emulsify- in acents are the ethers cf Ethylene oxide formed wilth c,O-- e.g. Etearyl p--'Lyoxy ethylene, cleyl-poly n alcohols, L cxy ethylene etc.; ethErs fc-.med With alkyl phe-.,-!s e.g.
ethers fc-med with tertiary butl, octyl and nonyl phenol etc.; esters of various acids e.g. poly ethylene glycol ester of stearic acid or miristic acid or pGlyethylene glycol oleate etc.; block polymers of ethylene oxide and propylene oxide; partial esters of fatty and oil acids formed with hexitol anhydrides;esters c-Lr sorbitol.
P c7rr.ed with oil acid or stearicacid; condensation products cf the c-np3unds fcrned with ethlene oxide; -'LerLi@r' t c I c. r r E thyl s e.g. 3.6-dir-e'Lh,"--' ---C Lin-3,6-d- r - 4:: J e - 7 - c e t h e C C C I t E t'_1 e 7 E e d -:
ester c-f dodecyl mercaptane forme- with pc- ' t, - i y e ene c c L etc As adhesive agents e.g. alkaline Earth metal scaps; salts 01" sulfosuccinic acid ester; natural or artificial water soluble macromolecules e.g. caseine., starch, Arabian gum. cellulose ethers, mei:hyl cellulose. hydroxy cellulose, polyvinyl pyrrclidcne and polyvinyl alcohol etc. may be used.
Suitable antifoam agents are -Lower P-'"LVCXY ethylene and polycxy propylene block polymers (wherein the number of octyl nony! and phenyl-polyoxy ethylene/ethylene oxide units is 4 5); lorg chain a1cchols e.g. octyl alcohol, special silicon oils etc.
By using SUitable adc-itives fo--mulated I compcsilons of the present inventicn can be made colloid - cher-ically !1P8tL-Jtle with various fertilizers.
C-Or .poS4 ions Of the nTesert The selective herbicidal _t- r Cor invention may comp-rise know- pesticides and./ol, nutrit've components, if necessary.
Wettable powdeps (WP)' can be prepared e.o. by admixing the mixtures of the active ingredients, the auxiliary agent(s) and the surfactant(s) with the carriers, grinding and finally homogenizing the mixture. Liquid surfactants may be applied e.g. by spraying on the solid organic or inorganic carrier'(s) or onto a powder mixture comprising the solid active ingredient. If a licuid s--r-facta-,t is use one may also proceed ty suspending the p:'evJ1c--,s1v sclid cc-;D---,ents ir. an crcaric sl ve7+ I Ihis suspensiGn can ue dried e.g.!3 pu"L.c-r4Lza- -"acta7-t is ap-Plied onto the sj.-face of Thus the úcr., 11 t -t-,e sclid e ingrei--.er-.,t MiY LU.._e and the solid. diluent A sellf-emulsifiable liquid suitable for the prepara- t (so-called emulsifiable of aqueous dispersed emulsions concentrate /EC/) can be prepared by dissolving the active in a water non-misci"ble ingredient. or a mixture there= The emulsifiable concentrate thus obtained forms with water spontaneously or under slight mechanical effect L a er-.'U'ILS.JC)r-. which remains ur,,--hpnged and stable eve-i aftE7 Icng StCrins.
A suspension cc,-,,entrS'Le (SC) car, be prepared by dissziving the wetting and dispersing agents in 2 Mixture -p.1 of watter preferably ion-exchanged water) and an antifoam ccrr,ponent (preferably ethylene glycol or glycerol) if neEeesary under warming. To the solLtion thus obtained a r- t f the solid (powdered or c:,stalline active i'X L L r e o L st4rrng and, if desirec, is ad-uled under constant L. - 1 L a-n n,component (e g. Aerosil 200" is 2dded. The slurry thus obtained (solid particle - liquid phase) is g,-c)und in a wet mill (e.g. a closed Dyno mill) to the des.ired particle size. -L preferably to a maxima' particle size of 5 /um. After grinding an antifoam, agent and a thickening component (e.g. Ke1zan) is added under homogeniza P, tion. One may also proceed by changing the order of succession c-if the additicr. of the componerts cr by addins furthe., agentE ""Jcn tc Eclid carriers one may, al e.g. c,es. in, add-i-t.- 1 s. use -- ' d water nc---7 i scibl e cr wa -,- -, sc i ".-le act 1 ve in-,:- e-- e- tE as combination partners. Solid active inoredients ha,,.jng a low melting pEint can @'.so be introduced in the form, of a melt without or admixed with an emulsif ier.
ULV compositions can be prepared in a similar manner to EC formulations (or in certain cases to SIC compositions).
Granules suitable for direct use (G) can be prepare,-; by extrusion, lamination, by applying onto a granular (e.c. ground limestone) or by absorbing a liquid Carl ler component in a carrier having sorpti3n capacity.
1 L Granules being appl'cable for spraying purposes (WG) can be prepared starting from WP and/or SC with the aid of an agglomeration technclogy e.g. in a drag6e pan by using a bind-inc agent.
A spray or dusting powde.T suitable for use in the a' ions acriculture can be obtained f-rcr-,, t D-Uve ccTPosi,..
by know.ri methods by dilution with waller or, an ine7t 50Lid carrier. The active ingredient Content 01 the said Feady- for itions is generally below 5% by weight, - L -use com.pos i - preferably 0.01-3% by weight. One ray also proceed by preparing different sprays comprising one active ingredient each and uniting the said sprays before use.
Further details of the process and compositions according to the present invention are to be found in the Examples without limiting the scope of protection to the said Examples.
In the Exa-l-es the following ab"--rev-ia-t,ions are used:
CHO compcund of the genera., Fo7r.u.,a ITT, A- 2 0 acetic anhydride; (I) compound of the general Forr-,.L-ia 1; (II) compound of the general Formula II; (Ia) 5-(2-chloro-4-trifluoromethvl-phenoxy)-2-nitro-benzaldehyde; (IIa) 5-(2-chloro-4-1tri"-uoromethl-pheroxy,)-2 -nitro-benzaldehyde-diacetate; (2 6 - r \Ib) 5-' -dichlGr---4-4L -.fluorore-,hy'-,-,-henoxy)-''-r"-4LrO- -benzaldehyde; I lb) 5-(2 6 -di chlorc-4-tri'f -,--nii'LI'C)- -ben,-aldehyde-dJLacetate; a.i. active ingredient; ATP-ase adenosine tr-iphcspha"Lase; % by weight.
Exam ples_1-9.
Into a 50 m11 re..jrd-bottcmed flas:k euipped With a stirrer, thermcrnieter and drop;:-"no funnel 6.0 g '0.02 mole) of 3-(2-chlorc-4--'Lrifluoromethyl-phe--.ox,",enza.Lde,,'lyde are weighed in and dissolved in dichloro methane having the same volume as the calculated amount of acetic anhydride. To the homogenous solution the acetic anhydride is added.
position (65% nitric The nitrating acid of the suitable acid and 96% sulfuric acid) is prepared and cooled to 0 C To the rear--tir-,c: r _; x ture the ni trat i r-C ac i -f i s added unde v i gc- 3u s s t i - r i ng a n d i n t e ns i,. e cc -- 1 J ng. A E- tl:-: g 1 y reactio- 4C. a',-,Es;Dll ace 2-,C14 ' mE at- e 7 i ses by several degrees alread after the atdi+L-;-C- Of Lhe fst drops of the n' t rat i ng acid. The external tempera ture is a d kept at -20 cC and t',E _t4L cn takes about L5 mi-utes.
The addition having been completed the ccolinp is stopped and the reaction mixture is stirred at 30 CC for 3 hours.
The mixture is poured onto 75 g of ice, the organic phase is separated and the aqueous layer is extracted twice with ml of dichloro methane each. The combined organic layers are washed twice with 75 mIL of a 3% sodium hytrogen carbonate soluticn each and With Water, and dried over magnesium sulfate. The COFIpCS.4tion of the solution is determ.ined ty gas chromatography.
GLC: SE-30, 10 m ca,---i1!2ry cclumn. 150-300 C, 10 C./min., F I D On eVa!Uat4Ln-- the chrom2toorams the ccr-.posi'icn is L modi.LL -Lors otttained by using sta7idards f-'ed by area fae-I The qualitative analysis of the crude rr..'XL is u erm- ed U e e- inet oas chromatography and mass spectrc by means of comtz photomet,ry.
On usino the above process at a molar ratio Of CHO/HN0 3/Ac2 0 = 1/1.6/5 on modifying the amount of sulfuric acid the product compositions shown in Table 1 are obtained.
Z alqel u pas--lj -sp aie p@LT2qo snq suo,Tsodwo3 1,jnpoid aqi 'L19'111 G P2T;Tpow ST C19111 = 0 Z3V/c ONH/OH3 OTel lelOw GL daoxg 6-1 saldwex3 G 5U1P10302 SP993ojd quo gi-ol -112X3 0 no-1 c ' z U - z 96 9 1 9 96 t7, 1 9 0,1 6 c 9 0 9 is PS 7 0 c z L 9 z c 0 7 9 z z z 0 1 (e/II) ON inpold O43/ 09 H 4,12 X 9i4 jo 9 1 C/9,i/1 = 0 Z1 V/C ON4104.3:OTel 121OW L + t. &.7 - 1 i alE?1 - 3Z - 23 Table 2
Effect of the amount cf sull-firic acid . L -- M-nlar ratiC: CH0iHNCO /A L -L 1 c2 U 3 Example H 2 so 4 /CHO Composition of the product (%) N o molar ratio (I/a) (II/a) 0.1 5 95 i i 0, 5 95 12 0.4 4 96 -$ 1 0.8 4 1116 L.,., 14 1.2 5 9 5 1.6 5 115 16 2.0 6 94 17 2.8 2 3 E_xar.--,!-es 19-24 One proceeds according to --9 except that.
on using a molar ratio of CHD/HNO 3 /H 2 so 4 = 1/1.6/0.2 the molar ratio of Ac 2 O/CHO is altered. The product composition thus obtained is shown in Table 3. -- Tabl.e 3 Effect of the ar?cu-,,t of acetic M-Ular -a-,ic,: CHC.,'HNC 1/1.6110.2 /H 2504 = 3 Example Ac, 2 O/CHO C.omposition of the product N o. molar ra'LJLO a (11/2) 19 4 19 BI L 5 15 E5 21 6 22 7 5 95 23 9 5 95 24 11 3 5-1 1 One proceeds accc.--ding to 1-9 except that on usin2 a mclar ratic of CH03/H 50 /Ac 0 1/0.2/5 the 2 4 2 mclar ratic of HN 03 /CHD is modified. The product siticns thus obtained are summarized in Table 4.
T a '-- 1 e 4, w E fl -,f e c t c. f t 1; e a -, 2 u r t c f r -: t: i c 2 c - cl Mclar ratio: CHD/H Sn iAC -i ' U L, 41 2 2 Example HNO CHO COMPCsi'iDn C. the product 3 L.
-- N o. (II/a) molar ratio (I/a) 1.4 16 64 26 1.5 17 83 27 1.6 22 78 28 1 1 25 7 5 Exarr.,l-es 29-37 une proceed-s ac-cr,,j-ing to Examples -hat 1-9 ex:ept t on usLns a mola: ratio oil CH-O/AC2 0 1/5 the mola-- ratio of h'140./H,c-0 i s d; i - -ns -Lhus ^ied. The eit -1 4 obtained are shown in Tal,-.,.-,e 55. - - - Tale 5 Effect c', the mclar ralio cf HNO 3 Molar ratio: "C9C. = L 3.
Example HNO 3 /H 2 504 Com,-osit.on cf the product N o. molar ratio I a (II1a) - 29 1 2 / 2-. 7 30 70 1 11/2 5 "B 42 31 1 5/ 22 4 67 13 32 1.55/2.35 U 0 33 1.60/2.31,0 lOC 0 34 1 - B/ 21 - 1 i ro 0 0 2.0/1.9 100 C! 36 2. 4/1. 5 42 8 37 2.6,11.3 26 74 Example 3E
Wettable pwder conce-trate Component Amount, by weight 8:1 parts by weL mixture of active inQredients H/a) and (II/a) 96 Cab-O-Sil M5 1 D-spe7g-er,-.-ttel 1494 3 24,3 c c'L r.-4xti,re cf,' tt-,e a--t.J\e previously in a a blade are affinixed 1 27 - wit h 2. 5. 9 c f- C a b-O- S i 'L M.5 (S i L iC a C a rr i er ' 2 5 c c "' J 4 i tTel 1494 dispersing agent (so-dium salt c--,^ e U ispergie.-rr.-i ted crescl and f c.rmalc'eh, de C In- r, d e. 5 a t.' 0 n rC.dUCt Cf SUlf3n2L in a mortar.]he powder thus obtained is groind in an eddy -current Mill. (Alpine JMRS-80) at an injector air pressure eed of 5 bar and a grinding air pressure. of 4.5 bar; the 1.
ing rate amcunts to 250 g/h. Although the wettable powder thus obtained contains no added wetting agent it is readilly we'L-,'.able, and has a maximal particle size of 20 /un, The f-44 1 ity of the wettable powder in a spray LIng ab.!-. 1 a ccncentr2L-ion of 10 g/l affter 30 minutes at 30 C amounts to 840, - r CT 0 -11 IPALC standard 0 water; and 91% in CIPAC standard A water.
According to the present Example any of the pro., cts m.x'LUreS of the active ingredients) ef Examples 1-317 car b e f o r ru l a t. e d, i r, t o w e t t a b 1 e p o w, d e r s.
E.xa:Pple 39 (.2.0 EC) Component Amount. % b\, w-.ioht Active ingredient (II/a) 20 2-ethoxye'Lhancl 10 Cyclohexanone 35 Emulsogen EL 360 7 Tensiofix CD 5 Xy l ene 25 28 37 g Of 2-ethex--ethancl.. 137 g of and 51-1 g of vyiene are wElched in a 5-00 mi. e-.ame'-,-',ec! Euto- th a st4r:er.
clave equipped w.J. I n e sc I v e - t t L,:, e lier hox\.isted castc, 26 g of Emulsogen EL 360 emulsil (e+ and 11 9 of Tensiofix CD 1 emulsifying agent (ethoxylated cocoa-alcohol) are dissolved. The emulsi.
Piers are added to the melt (at 60-70- OC). Finally 75.5 g c..P the active ing-7edient (III/a) are added and the mixture is stirred for 2 hours. Thus a clear transparent so--1u'Licn is otta-.ned.
J c the p-7esen-',. E x a-ple pr- cr-icct ', a-- 7 Jxture CL-ta Jned ar-crding to Examp-es l-37 c:, e di e n t m L i. - car, be formulated as an concentrate.
Exe,m.- e 40 Emullsiflable ccn--en..t:-ate (5 EC'/ C c. - A:+.ive ingredient ('-"Llb) C clolhexanone 110 Te-,-c,ofix CG 21 2 Tensiofix B 7453 8 Xylene 1-5 6 9 of Tensiofix CG 21 (mixture of e+hoxylated fatty L, L alcohol and ethcxylated nonyl phencl ank-11 the phcsph;ates thereof) and 24 g cf Tensio-fix B 7453 emL!sif-llng agent a s c 1 u t ii c. n c.' c a Il c rn n- c -4 e c y en z en, e s:-. -- f e, e z h a e-- pliencl and - n. r, -, L: 1 a - c 'I ' a:- e J - - c, e d, - a r- i x ', - e: f 3 c: c -7 c:: -,: - 1 1 - active hexanone and 133 g of xylene. Finally 104 g- o L ingredient ( II.1b) are added and dissolved in the liquid comprising the tensides.
According to the present Examples the products (active ingredient mixtures) obtained according to any of Examples 1-37 can be converted into emulsifiable concentrates (35 EC) Example 41
Aoueous suspension concentrate Componert Am:,-L-t. bv we-ich-- --- 1, Mixture of active ingredients (1) 0 4J.0 Propylene glycol 7.D Tensiofix XN6 (2) 2.0 Tensiofix 8 7245 (3) 4.0 Rhodopol S 23 (4) n,.05 Silicon SRE (5) 0.5 Water (ion-exch2r-.ged/' 4C 45 1 Any active inGre-4'Len4;-. mixture prepared by the process of the present invention having Optional composition (weight ratio of the components) can be used.
(2) Ethoxylated nonyl phenol and ethoxyllated nonyl phenol phosphate ester.
(3) A solution of calcium dodecyl benzene sulfonate, ethoxylated ncnl phenol and prZ-,,CX"L24Led nonyl phlencl in:-butanol.
( -1,) X a r, t 1 a n e g,, r- ' t h -' c Ir, e rt i n g 2 71 e r t.
1 ( r C WU 5 C r.j -111 5 i C n c.L' d i met h; s 1 1 j c n_ n c, 11 Into a 20 1 vessel, equipped wi th a dissc-,,.er disc stir rer 5 1 Of iOn exc'i",ar,.-ed watei. are we c-ed. in. wher t- - - 1 e upon BOO 9 of propylene glycol and a mixture of '40 o of Tensiofix XN6 and 480 g of Tensiofix B 74,25 heated to 0 C is added at a rate that the temperature should not exceed 35 0 C. Stirring is continued for 20 mj'.nutes where upon an emulsion of 30 9 of silicon SRE and 30 g of water is added to the suspe-sicn. under stirring.
Wet crinding is carried out in tw-. steps. In the first stage the suspension is led through a Fryma blk, 5 Lype colloid rrill equipped with a corundum disc until the Particle size becomes lower- than 190 /urn. Fine grinding is effected in a Dyno KG 5 type pearl mill to a particle size below 8 /um. Grinding having been finished a gel containing r, 2L; g cfRhod--pc! B 23 xanthane gum, 400 c cf prcp'ene g-.,vco'L and 500 Q of water is distributed in the crs-,nd U L - mi x t ure Example 42
Oily suspenision concentrate (F0) Component Amount. % by weicht 1:1 mixture of active ingredients (I/b) and II/b) 32.7 Cosnetical grade liquid petrolatum 4e.8 Tensiolix AS 4 Sapcgenat 7-0800 4.5 E th 1 e n e c c E C. r 11. i c c. n, 5 R PE 13. 5 o of 5--- p G c en, at]-D eC' ernu is I f i ng a ge-it et,"'I C X 1 at - ed tributyl phencl) melt at EO C 2 n d 12 9 Of AS emulsifying ace-.t (a Of calcium dodecyl benzene sulfonate and ethoxV13ted nony! phenol in n-butancl) n.elt at a temperature not exceeding 60 OC are added to 145 g of cosmetical grade liquid petrolatum war.med to 60 C in a Molinex 075 laboratory pearl mill. To the tenside oil mixture -1ded and the components are g of ethylene glycol are aU homogenized by stirring for 10 minutes. 98.1 g of the mixture of the active ingredients Previously -L finely gr-UUn-j in a mortar are all-ded to the liquid mixture. After Stirring for 5 minutes grinding is continued for 2 hours at 15-00 r.p.m. by using glass pearl-S having a diameter of 1 mm/350 g of gri-nd-ing bodies). Thereafter 1.5 g of Silicon SRE anti foam agent (30% emulsion Of diMethyl silicon oil.) are distributed in the oily suspension under StIrring for 3 minutes.
A-cording to the present Ex;-::,nple any active i.-.9--.ed-Len-lt mixture can be formulated into an oily sispension -.cncen-'Lrate.
Example 43
ULV composition Component Amount, % by weight Active ingredient (II/a) 27.5 Isophoron 30 2-ethoxye+Lhano-, Soya oil (or sunfiswer oil) 312.5 32 Intc an anhydrous enamelled autor-lave 7, 5.001 g o.E isophcron and 2500 a of 2-ethoxyet',,,ano!L are weighed in.
6875 g of active ingredient (II/a) pre-ground on a ha-imer mill are added to the solvent mixture, stirring is simultaneously started and the temperature is raised to 45-50 OC by turning on the jacket heating of the autoclave.
An hour later when all the active ingredient has entered into solution 8125 9 of soya oil (or sunflower oil) are introduced into the autoclave, stirring is continued for P a further pe:-.Jod of 290 minutes and the temperature is rediGed to 20 0 C. The UILV composition is directly applied in undiluted form without adding water.
According to the present Examples any active ingredinet or active ingredient mixture can be transformed into a ULV composition.
Exa-;:_-e L.4 Dustinp p)wder-'.-iavSnq 2r_2.C'L-jVe iroredient cortent of 1% by we _; oht _( OF ') C c) mp 2 n e n t A m. -n u n t % -b \ w e i- c h t Active incredlent (I/b) 1.0 Ultrasil VN 3 3.0 China-clay 16.0 T a 1 c 80.0 510 9 of Chira-c"a In a 50 1 ribbon-type rpixer 9 L.
are, adrixed with!En.,2 g of Ultrasil VN' 3 s y h e c s -- 'I silicate. tc the rr,.xtl-.-.e 6C--, c cf ac:±E 33 ingredient (I/b) previously ground in a hammer mill are added and stirring is continued for a further period off minutes. The active ingredient premix is grownt in an Ultraplex 250 type mill at a feeding rate of 20 Q/h to a degree that the ratio of the fraction having a particle size above 44 /um should not exceed 0.5% by weight. After grinding the active ingredient premix is admixed with talc in a Loedige 300 type eddy-current mixer at a ratio of 1:4 under stirring for 10 minutes.
According tc the present Example any active ingrezie", mixture can be converted into a dusting pcwter.
ExarDie 45 According to this Example the herbicidal activity and increased selectivity of the active ingredient mixtures of the present invention /-mixtures of W/a) + QW) 2nc Q/b) + QI/b), respectivel,7 are stown.
into Petri dishes an identical nuMtEl Of SeetS (20-50) is sown - depending on the plant species - at 2 SOW4 depth of 0.5 cm, whereupon after Lng the soil is waterecl.
Treatments are carried out by the pre-emergent method at a dose of 3 kg Mij.ha_ 1. The soil is w atered every day.
Evaluation is accomplished on the 10th day after emergence.
The results are expressed as the percentage of devastation and summarized in Tables 6 and 7.
No. 1-6 appearing in the Taties designate the fcllow- ing weeds:
1 = Abuti lon theophrasti 2 = Amarantus retroflexus 3 = Calystegia sepium 4 = Datura stramonium = Galium aparine 6 = Xanthium strumarium T a b I. e 6 Ac,tive.iriqredi.ent 0 e t e r i o r a t j o n No. Dose- Ratio soya bean pea broad-bean 1upine 1 2 3 4 5 6 1 (kq. ha) [/a 3.o - 0 65 25 70 50 50 100 100 100 100 100 1/a+11/a 2.075+0.125 23:1 0 55 15 60 50 50 100 100 100 1,00 100 1/a+11/a 2.75+0.25 11:1 0 20 0 1.5 20 70 100 100 100 100 100 1/a+II/a 2.5+0.5 5:1 0 10 0 5 1.0 100 1,00 100 100 100 100 1/a+II/a 2.0+1.0 2:1 0 10 10 1.0 1-0 90 1.00 100 100 1.00 1.00 1/.i+II/a 1.5+1.5 1:1 0 20 10 15 15 90 100 100 100 100 100 1/a411/a 1.0+2.0 1:2 0 35 15 35 25 90 100 300 100 100 100 T/a+11/3 11.5+2.5 1:5 1) 45 15 40 30 90 100 100 100 11.10 100 IlatIlla 0.25+2.75 1:11 0 50 20 50 35 90 95 95 101) 100 100 f/a411/,-1 0.1252.075 1:23 0 60 20 65 40 90 95 95 100 100 1110 fl/a 3.0 0 65 25 75 115 90 95 9 5 100 100 100 Arloor ac rell -7,0Cii(lm 3.0 0 70 30 70 60 100 100 95 95 1011 100 Control 0 0 0 0 0 0 0 0 0 0 0 T a b 1 e 7 Active, ingredient 0 e t e r i o r a t j n n No. Dose- Ratio soya bean ppa broad-bean lupine 1 2 3 4 5 6 f/h 3.0 - 0 115 1 fl 60 60 90 90 95 95 100 100 Iffi4-11/b 2.875+0.125 23:1 0 45 10 50 40 95 95 100 100 100 100 I/b+II/b 2.75+0.25 11:1 0 20 10 10 1-5 100 100 100 100 1.00 1.00 [/13+11/t) 2.54.0.5 5:1 0 10 0 0 10 1.00 100 100 100 Ino 100 Iffi411/b 2.0+1.0 2:1 0 15 10 10 10 100 1110 100 100 ion 100 f/b411/b 1.5+1.5 1:1 0 20 10 1.0 20 100 100 100 100 100 100 Iffi+II/t) 1.0+2.0 1:2 0 40 jo 10 30 100 100 100 100 100 100 1/b+11/b 0.5+2.5 1.5 0 40 1.0 30 40 100 1.00 100 100 1.00 1.00 W a) 1/b+11/b 0.25+2.75 1:11 0 40 15 65 40 90 90 100 100 WO 100 1 1/b411/b 0.125+2.875 1:23 0 110 20 65 40 60 80 95 95 95 95 TI/b 3.0 - 0 40 20 70 40 60 85 95 100 95 95 ac i r 1 (for foll-so d i LIFT 3.0 0 70 30 70 60 100 95 95 95 100 100 Untreated 0 0 0 0 0 0 0 a 0 37 Examz)1e 46 In the present Example t he refer en c e E x am. p 1 e) ( I T 1 @). T, b " an d herticlidal activity of compzunds (I/a), \ L. 1. l! 1 (II/b) (active ingredient components) is shcwn as a function of the doses used.
The tests are carried out in an analoguous manner to Example 45 except that the herbicidal activity ef the compounds is determined in three doses /1.0, 3.0 and 9.0 kg of (a.i.).ha- 1 /. As standard ac-i-fluorphen sodium is used.
The results are disclosed in 1,a-'Le 6.
Tab I f. 8 v p 1. p r i o r a t i (1 rl FArtilvn in rdipnt N cj Dose Soya bean pca broad-bean lopine 1 2 3 4 5 6 (kg.ha- 1 /a 1 0 50 1 D 60 40 40 BO 90 130 so 61) 3 0 65 25 70 50 50 100 100 100 10(1 100 9 10 70 40 60 60 60 100 1.00 100 100 100 114 1 0 50 10 60 35 75 85 85 65 85 90 3 0 6 5 25 75 45 90 95 95 100 100 1 M3 9 10 75 45 B 5 55 100 100 100 100 1011 100 0 30 5 50 40 7(3 70 70 75 70 70 0 45 1.0 61) 61) 90 90 95 95 101) 95 9 10 () f) 30 70 70 100 100 100 1.00 101) 1110 1 0 n 5 11) 60 30 70 70 70 80 80 115 z ' 3 a 40 20 70 40 81) 80 85 95)00 95 9 10 QI 40 80 50 100 100 100 Ion 1 Of) 111(1 i t 1 t in r f f-n- 1 0 50 11) 65 50 80 91) 85 65 135 9C 3 1 -.( 1(1 i 1 lin 3 0 71) 30 -70 60 100 100 95 95 1 (30 WO 3 29 10 75 50 65 80 100 100 1 fjo 10(1 1 (X) 100 Untreated 0 0 0 0 0 0 0 0 0 n Control 39 -lts of the ticlogical -e it appears '-OM the resu t -ts d --SC losed JIL n E-Ex-amples 45, and 46 that the se lect- ivi- 't y c, the m ixtures of compounds /I/a/ + /.L on the one hand, and /'L/b/ + /I!/b/ on the other hand according -c the present invention is significantly improved while at the same time the herbicidal effect is not decreasel-rroreover it is even increased if the active ingredients are used in a weight ratio of 25:1 1:1. The above mixtures of both herbicidal comnpound groups exhibit ap antagonistic effect W Jvty of on legunninous cultivated plants whereby the act-' - Jdoted by the other. Simultaneously each component is ant.
the active ingredient combinations of the present invention show a synergistic activity on weeds. Thus mixtures /I/a/ + + /!I/a/ anJ /I/-b/ + /ITUb/ jand/or /!/a/ + /III/b/ and /I/b/ + /II/a/, respectively7 can be used not cnly in soya for pre-emergert weed control but also in other cultivated plants, cc,-'rary to the components when per se.
1- -ing activit The degree of the mutual ant-'dot- L- -1y between the active ingredients can be seen from the data of Tables A and B. Table A contains evaluated data of Table 6 dis closed in the c oloumns of bean, pea, broad---bean and 1upine and in Table B the respective data of Table 7 are set forth.
The symbols in TablEs A and B are as follows:
Ta: absolute surplus effect ference of the dete Methot of calculation: difL rcration per cent of the active i-nf,:re.4i^:ents - and of the det ei --rat i:n per c ent of the compositions containing a,.r.J-x'-ure of act ve -:-,gre.'-, ents lative surplus effect W re Method oil calculation: 'La is divided by the deterioration per cent value of the composition containing one act7e ingredient and the resultis multiplied by 100.
41 -ia,-'e A. /on the basis of the data of 7 a t. e 6 Weight ratio Referential bean pea broad-bean lupine of active ingr, compound % a/ % % it /I/a: II/a/ Ta Tr Ta Tr I'a Tr Ta Tr 23:1 I/a 10 15 10 40 10 14 0 0 11: 1 I/a 45 69 25 'LOO '1 5 79 30 60 5:1 I/a 55 85 25 100 65 93 40 eo 2:1!/a 55 85 15 60 60 86 40 S0 1:1 I/a 45 69 15 60 -,1 719 35 70 1: 2,r 30 46 10 4 C, 35 50 25 50 1/a 1: 1-5 I/a 20 31 10 40 30 43 20 40 1: 1. 1 I/a 15 23 5 20 20 9-1-9 i _ 3 0 1: 23 I/a 5 8 5 20 5 7 10 20 2-3:1 Ii/a 10 15 -10 40 1-5 20 0 0 11:1 rI/a 45 69 25: 100 60 E-, 25 56 5: 1 II/a 55 e 5 2, C, 0 70 9 3 3 7 G 8 2:1 K/a 55 85 15 60 65 87 35 78 1:1 II/a 45 69 15 60 60 801 30 67 1:2 II/a 30 46 10 40 40 53 20 44 1:5 II/a 20 31 10 40 35 47 15 33 1:11 II/a 15 23 5 20 25 33 10 22 1:23 II/a 5 8 5 20 10 13 5 11 1;n t -: /cn the ta-s-'s of the data c' 7atc 7/ WFht-ra Referential bean pea broac-buean -!,jn--:ne e-.
off active ingr, c om, pound % % 011. 7.
/I/b:II/b/ T a T r T a TI r T a T r T a T r 23: 1 I/b 0 0 0 0 10 17 20 33 I/b 2 5 5 6 0 0 50 83 45 7 'S 5:1 I/b 35 78 10 10 60 50 83 7 3.0 67 C 8-, 2 83 /b 7 I/b 25 56 0 0 50 E3 40 67 - 1:2 I/b 11 0 0 50 83 30 50 1:5 5 37 0 0 30 50 20 33 i/b 5 -1. - - - - 20 33 ":23 i/b - 20 3 3 23:1 ----/b 0 20 E7 21 2zI 0 0 11: 5 - 20 6,17 6 C', 8,- 25 63 5: TT/b 3 0 1, S.' 3 C, 100 7 ICI 1 D 0 3 C, 7 5 2:1 -r- -, 1, 5 63 C 67 6 I' 86 - 7 2 G 3 1:1 II/b 20 50 20 67 60 86 20 50 1:2 II/b 0 0 20 67 60 86 10 25 1:5 II/b 0 0 20 67 AO 57 0 0 1:11 II/b 0 0 15 50 5 7 0 0 1:23 II/b 0 0 10 33 5 7 0 0 43 - 4.7 In the present Examples the c-a-ia-e c.' activity cf plants ATP-ase /adenosine triphosphat.ase/ and 7.0di.
f'i C ation of phytotoxicity caused by treat ".ment with the active ingredient compositions of the present invention -/I/a/ + /I!/a/ and /I/'-/ + /!I/b/, respectively.,7 -JS dis closed.
e 2-3 leave-stage cat', plant's /Avi-=ra sa'.-va/ ar- treat- ed wi lth mixt. ures of the act ive ingred 2.ent s 01 d Lff ere nt ratio at a rate of 1 kg /a.-L./ ha- i. On the 3rd an I'Lowing the pcs',-ern.er7-ent treatment. J day fo 1 he act-.v-ty change of A7-P-ase an- phyto'Lcx-icity are u-eter:n-2ned.
ATP-ase enzye is extracted from the roots of oat C W. Weltrup, /-!/. En--yme activity is plant by the method c.
1 - -- determined' ty the of.A. Solim,::.-nd et a!. 121.
--th in TableS 9 and -t can - he resul's are - f be seen from the data of the saic- Tables that on treat-Ing oat with the four ccin,-,cu-ds J/1/a/, /!!/a/, /I/D/, al-d /II/b/, respect-Jveli and a 1-16:16-1 weight mixture c.
two com.pounds each:/I/a/ + /II/a/ and /I/b/ -- /II/b/7, respectively-7 the highest ATP-ase activity inhibition and phytotoxicity are observed when a 8:1 mixture /weight ratio/ of /I/a/ + /II/a/ and /I/b/ + /II/b/, respectively is used.
- 4 If - 7 1.
1 --,eratire:
be i n v vc a n-- 2-4.
1. W. 'We';.ru-: Th in, eff-ects i::.f Ca J + fr om bar ley r oot and A! AT?-ases tr--tion 6 /,", / Journal of Plant N. 1 33,49-361 /1983/.
2. S.A. Scliman, A.K.A. El Refaie, A.H. El-Sellae and Z id: Tcxicit insecticides to drv Wooi M. Ir. Z_ e i - 1, v of s ome r -1tes Clyptctermes 1-,revis /Walker/ in relation to , e rm -L 1- k, - - AIP-ase and AChE inhibition.
in+.ern-'--.,-c,r,a-2 Peest Control 1,981.
T a t., 1 e Q.
iPhytotoxicity ATP-ase activity Weight rat10 1 in',Lbition in % of control (I/a): (II/a) 3. 5. 3. 5 day day 1 - 38 51 10 15 16 1 60 63 26 40 8 1 85 100 35 70 4 1 B1 05 28 40 2 1 64 90 22 35 1 1 56 65 16 2 19 1 2 45 60 10 20 1 4 40 55 + 15 1 8 36 50 + 10 16 2 40 + 32 1 n 38 + 8 + S_1 ight inhibi tion T a L' l e 10 Weight ratio Phytotoxicity ATP-ase activity inhilbition in of control (I/b) (II/b) 3. 5. 3. 5.
day day 1 - 40 55 15 20 16 1 85 -15 31 43 8 1 90 10 1, 4 LO 78 4 1 E3 98 3 2 45 2 1 6 5: 0 C 5 40 1 1 2 1 1 55 76)o 30 L 1 2 52 62 13 25 1 4 45 58 5 18 1 8 45 52 10 1 16 4 i 45 15 - 1 32 40 10 slight inhibition 47 ir adGil llo the mutual antid.oting effect between the ac+..;ve 4ngrer,;ents in the case cf' Iezu.m-4n,,-s plants - - -L - - c; a futIher synergistlc herbicidal activity increase can be observed. The degree c.' the synergis tic surplus effect can be seen from the data of Tables C and D, which are based on the results shown in I'ables 9 and 10. The values of Ta and -1r are calculated as described in Examnle 46.
1 - 48 - 1 the ba _z is of the data c.." - a t 1 e- 9 1 - a t 1 e C i c-i Active ingr. Weight ratio Ta/%/ Tr/%/ a/ % Tr/%/ /referential of active calculated. on calculated on compound in ingredient the basis of the basis of brackets/ phytotOX-4z-ity phytolloxicity on the 3rd day on the 5th dav I/a: II/a 16:1 22 58 12 24.
/I/a/ 8:1 50 132 49 96 4:1 3 113 1.4 86 2:1 26 6e 39 76 l is 47 14 27 :1 -1: 2 17 1 e 9 i a 1: 4 2 5 1:8 1: 16 - - - - 16:1 - ell 2-5 66 3c -LUO 8:1 55 163 62 163 4:1 51 170 '1 150 -7 2:1 34 113 52 137 1: 1 26 87 27 " 1 1 1: 2 15 50 22 58 1: 4 10 33 17 45 1: 8 6 20 12 32 1:16 2 7 2 5 a) I e D /cr, the basis oll' the data C-5, 7 a t I = I C;/ Active ing Weight ratio Ta/V T r 01'c a Tr/%t/ C- r /referential of active calculated, on calculated on compound in ingredient the basis of the basis of brackets/ phytotoxicitv phytotoxicity on the__3rd day on the 5th I/b: II/b 16:1 45 113 20 36 /T/b/ 8:1 50 12155 45 82 4: 1 3 1 n p 4. - -,8 i 2: 1 25 63 14 0 '7 3 f 1: 1 15 38 21 38 1: 2 12 30 T 13 t 1: 4 5 13 3 5 1: 8 5 13 1: 16 1 L/b: T-. /b 16:l 53 c, es /17 1 / b 58 1,j 6 G -15 0 4:1 51 - 1 ' 1 145 2:1 33 103 55 138 1: 1 23 72 36 9 0 1: 2 20 63 22 55 1: 4 13 41 18 45 1: 8 13 41 12 3 '01 1: 16 2 6 C 13 I- the present Example the syner-cJcl-r herb-ci,-al :-- --L - L act v J ty of the combination of the compcunds according to the inventicn /TL/a + II/a/ and /I/b + II/b/ is shown.
The tests were carried out in four repetiticns 2 Lerial on 250 mi size plots on a soil of 2.44 % organic mall c c- e nt.
Picneer 3978 type r,-,-aize seeds were sown in 5-6cm dep-th into the soilperfectly prepared for scwing in a q,,;ant-ty off 83 '1 p r i -I 4ct-ve ingreci "C).OOC, plant-s/ha on 5th, k ents I/a, TT/a, 1/b and I1/b and the com-,-".nal,-ion c." the active ingrede-ints I/a and!I/a as well as IL/b and TT/b were sprayed In a ratio cf 9:1 onto the scill at a dose of 0.2c-57 and 0.50 kg/ha by means of a Hafil nger spraver on 6th April.
The resjIts obtained were eva'Luatei on ISS- t h J., n e ty determining thie de--er-or;-::t-Lon o value c.' the different 1 j L -re a' weei species on size picts for each ' Lment.
Cn the tested area the following weed species were 7. Echinochloa crus-galli 8. Setaria viridis 9. Capsella bures-pastoris 10. Thlaspi arvense 11. Portulaca clexaceae 12. Polygonum aviculare I. r c'l ex us 13. Amarant thus ret 1L. Stellaria Me- LCI -he resjl+s c-- t,o- test are sj-7.ar. zed in Tatle -". -1.
51 - In t the last column oA the Table the % value of weed killing related to all weect is given. From. these da'-.a it can be calculated that the relative surplus effect of the conPo sitions containing combined active ingredients compared to the compositions containing only one active ingredient is 25-35% at a dose of 0.5 kg.ha- 1 and 5.0 - 6 55 % at a dose of 0.25 kg.ha- 1.
Table. 11
Active ingr,ectient/s/ Coveredness by weed e, t, e, r i o- No. Dose -41 it 1.) 44 To al at. i on kg. ha 1/0 0,5 5 5 3 0,5 0 0 0 14,5 79 0,25 (3 7 5 2 1 0,5 0,5 0,5 24,5 65 1 1/a 0,5 7 6:p. 0,5 1 0,5 0 0 17,0 7 8 0,25 9 7 G 3 1,5 0,5 0,5 0,5 2f), 0 60 I/a + 11/8 0,5 0 0 0 U 0 0 0 0 100 0,25 1 0,5 0 0 0 0 0 0 913 I/b 0,5 4 3 4 2 0 0 0 13,0 01 0,25 10 5 6 3 0,5 O's 0,5 o's 26.0 63 II/b 0,5 5 6 3 1 0 0 0 0 15,0 76 0,25 0 7 6 3 1 0,5 0,5 o's, 26.5 62 I/b + 1 I/b 0,5 0 0 0 0 0 0 100 0,25 o's 0,5 0 0 0 0 0 0 1,0 99 Untreated 22 14 9 8 5 5 5 2 70,0 0 control 53
Claims (1)
- CLAIMS l.) Herbicidal composition of increased se'lec'LiVity c o m p r i si n g as active ingredient at a 50:1 - 1:50 ratio by weight a mixture of a 5-(substituted phenoxy)-2 -nitro-benzaldehyde of the general Formula I CP 3 X Cl 0 0 0 1% H (wherein X stands for hydrogen or chlorine) and a 5 -substituted phenoxy)-2-riit-ro-benzaidehyde d-ia---tate cf L the general Formula II W 3 -0 X Cl 2 E C. 2 54 (wherein X is as stated above).2) Composition according to Claim 1, cor.-,prisJLng the compounds cf the general Formulae I and II a ratio of 20:1 - 1:1 (parts by weight).3) Composition according to Claim 1 or 2 c c m p r i s i n g as compound of the general Formula I 5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitro-ben,zaldehyde and as a compound of the general Formula II 5-(2-chloro 4-trifluo.-ome'Lh.1-phenoxy)-2-nitro-benzaldehyde-diacetate.41) Composition accordLng to Claim 1 or 2 c c m p r i s i n g as compcund of the general Formula I 5-2,6-dich,lorc-4-trifluoro,,ne41h),'L-phenoxy)-2-nitro-benz- aldehyde and as compound of the general Formula 11 5-(2,6 -,.,ichlorc-4-trifluoromethyl-phenoxy)-2-nitro-benzaldehyde d.acetate.511 Process for the preparation of a 50:1 - 1:50 ratio mixture (in parts by weight,, of a 5-(subSjLitu'ked phenoxy) CF 3 XCl (I) 0 c NO - and a 5-(subs-',.-itU-'Led phenoxy) -2-nitro-benzal dehy-4e-di acetate of the general Formula II OP 3 x4c, - (II) 0 0 NO 2 CH(C, C 0 CH 3)2 (wherein X stands for hydrogen or chlorine with the prov.Lso th2t X. has the same meaning Ln the general Formulae I and II) in one reaction step wh-ch c o m p r i s e s reacting 1 mole of a 3-(substituted phenoxy)-benzaldehyde of the general Formula III CP 3 Co x C1 0 CO" C 0 56 - (wherein X stands for hydrogen cr chlorine) in the presence of a solvent - preferably bichlorc methane - at room temperature or at a lower temperature with 4-11 moles of acetic anhydride and a nitrating acid consisting of a mixture of 1.2-2.6 moles of nitric acid and 0.1-2.6 moles of sulfuric acid, isolating the mixture of the compounds of the general Formulae I and II from the reaction mixture by known methods and, if desired, purifying the mixtures thus obtained.6) Process according to Claim 5 for the preparat -ion of a 50:1 - 1:6 mixture of the compounds of the gerieral Formulae I and II (wherein X has the Same meaning as stated in Claim 5) in one reaction step which c o m p r i s e s reacting 1 mole of a 3-(substituted phenoxy)-benzaldehyde of the general Formula III (wherein X stands for hydrogen or chlorine) in the presence of a solvent - preferably dichloro methane - with 5-6 moles of acetic anhydride and a nitrating acid consisting of a mixture of 1.5-1.7 moles of nitric acid and 0.1-1.8 moles of sulfuric acid.7) Process according to Claim 5 for the preparation of a 1:2 - 1:25 mixture of compounds of the general Formulae I and II (wherein X had the same meaning as stated in Claim 5) in one reaction step which c o m p r i s e s reacting 1 mole of a 3-(substituted phenoxy)-benzaldehyde of the general Formula III (wherein X stands for hydrogen or chlorine) in the presence of a solvent - preferably d.jchloro methane - with 6-7 moles of acetic anhydride and nitrating acid consist'Lng cf a m'Lxture of 1.5-1.7 mc, les 57 of nitric acid and 0.1-2,8 moles c." sulfuric acid.8/ Herbicidal compos.1tion c o m p r i s i n g a d 5-/substituted phencxy/-2-n-;.'uro-benzaidehy,.'e - 'aceta e of the general Formula II /wherein X stands for hydrogen or chlorine/.g/ Herbicidal composition according to claim 8 c o m p r i s i n g a 55--/2-chloro-4-'Lr--f 1.-oromethy.jrphen oxy/-2-nitro-benzaidehyde diacetate as active ingredient.10/ A 50:1 - 1:1.50 mixture of 5-/subs'--i-uted phenoxy/-2-,-.,l.tro-benzaidehyde of the general Formula I CF 3 X 1 cl i 0 "C 0 NO 2 H /wherein X stands for hydrogen or chlorine/ and a 5-/substituted phenoxy/-2-n-tro-benza'-,dehvde diacetate of the general Formula II 5E c F 3 X 1 c 1 0 / r 1 1 L 1 c F. / o c 0 c; 3 / 2 N 0 2 /w he -. e --' n X - s as s t a t e Id' at v e /.-.-4xl,,ure as g-^yen 'n ca- 7C 12,1 A 11- e r t i c i d a 1. r., e t h -j c f ''. r e a ' mem n t s el e t i v e 'L y effective against weeis, W 'n i c 171 c c m p r -: s e s the step of a22!Y-J--7- a co-pc-sition as c a d _n clainj 1 t 0 cu, I t i v a t e d s rb - c a 1 r, e t 1- 0 d c' 1-1reatze, - select effect.Z.ve aga nst weedS, w h --z c h c c m p r JJ. s e s the step cf a--71j,ng a com-Licst-Lcn as 2n to cul--'vate P.ants.14/ A herbicidal method of treatment selectively effective against weed's, w h i c h c o m p r i s e s the step c," applying a COMPOSition as c-!a-,--ej in claim 8 to cultivated plants.15/ A herbicidal method c.r treatment selectively effective a-:za-nst weeds, w h i c h c c = p r i s e s the ste- cf- applyIng a as c';:-:ne,4 -n c--a-m 9 1 59 16. A p rocess substantial l y as hereinbefore described in any one c, Examples 1 to 37.17. A herbicidal coritpos-Lton substantially as hereinbefore described in any one of Examples 38 to 44.28. A herbicidal method as claimed in any one of claims 12 to 15 substantially as hereinbefore described in any one of Examples 45 to 48.Pu^vlls]7.ed 1966 at The Fw.cr.t 5zate Ec,,-se- 66 High ililborr,. London WC3.P. 4TP Furt-el, c-nes inay be obtained from The Pawnt Office, Sa.:es E-ranch. S, M7v C: y. C)rpng-,o.,-. Yent BRE 3RD Prunei by Multiplex tech=-,q,-úz,!,d. S: Mary Cray. Kent. Con 1 87
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU872718A HU200538B (en) | 1987-06-16 | 1987-06-16 | Herbicidal compositons with improves selectivity and process for producing the two active ingredients in one reaction step |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8814190D0 GB8814190D0 (en) | 1988-07-20 |
| GB2205749A true GB2205749A (en) | 1988-12-21 |
Family
ID=10960801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08814190A Withdrawn GB2205749A (en) | 1987-06-16 | 1988-06-15 | Herbicidal composition and process for the preparation of the active ingredient components thereof |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS6419003A (en) |
| DD (2) | DD271051A5 (en) |
| DE (1) | DE3817343A1 (en) |
| FR (1) | FR2616623A1 (en) |
| GB (1) | GB2205749A (en) |
| HU (1) | HU200538B (en) |
| IT (1) | IT8820978A0 (en) |
| PL (1) | PL273089A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6028219A (en) * | 1995-09-13 | 2000-02-22 | Zeneca Limited | Process for the nitration of diphenylethers |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0125506A1 (en) * | 1980-11-28 | 1984-11-21 | Bayer Ag | 5-(2,6-Dichloro-4-trifluoromethyl-phenoxy)-2-nitrobenzaldehyde-diacetacylal |
-
1987
- 1987-06-16 HU HU872718A patent/HU200538B/en not_active IP Right Cessation
-
1988
- 1988-05-20 DE DE3817343A patent/DE3817343A1/en not_active Withdrawn
- 1988-06-13 FR FR8807868A patent/FR2616623A1/en not_active Withdrawn
- 1988-06-15 PL PL27308988A patent/PL273089A1/en unknown
- 1988-06-15 GB GB08814190A patent/GB2205749A/en not_active Withdrawn
- 1988-06-15 IT IT8820978A patent/IT8820978A0/en unknown
- 1988-06-16 DD DD88316838A patent/DD271051A5/en unknown
- 1988-06-16 DD DD88320212A patent/DD273626A5/en unknown
- 1988-06-16 JP JP63149226A patent/JPS6419003A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0125506A1 (en) * | 1980-11-28 | 1984-11-21 | Bayer Ag | 5-(2,6-Dichloro-4-trifluoromethyl-phenoxy)-2-nitrobenzaldehyde-diacetacylal |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6028219A (en) * | 1995-09-13 | 2000-02-22 | Zeneca Limited | Process for the nitration of diphenylethers |
Also Published As
| Publication number | Publication date |
|---|---|
| DD273626A5 (en) | 1989-11-22 |
| DE3817343A1 (en) | 1989-01-05 |
| PL273089A1 (en) | 1989-06-12 |
| FR2616623A1 (en) | 1988-12-23 |
| DD271051A5 (en) | 1989-08-23 |
| IT8820978A0 (en) | 1988-06-15 |
| JPS6419003A (en) | 1989-01-23 |
| GB8814190D0 (en) | 1988-07-20 |
| HU200538B (en) | 1990-07-28 |
| HUT47201A (en) | 1989-02-28 |
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Legal Events
| Date | Code | Title | Description |
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| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |