A method for raising the content glucids of the plants by means of derived from substitution the phénoxyalcoïques ones or cyclohexanedione.

.. ; hO^: of i - its^; uG-to-'ii FT-- :§^ d-R.^: ' ^ 0Ri|FRs © · β - 4 compounds of the class of derivatives phénoxyaIcahoïques and cyclohexane dione derivatives confectioneries sup T-ituants aromatic or heterocyclic have a highly selective activity against annual or perennial plants monoeotylédones, and a number of these compounds have acquired significance as herbicides in recent years. Examples include hereinafter a few publications in which compounds of this type have been described, examples of the I the of-bone 22, 23 894. 24, 17 487, 24, 33 067, 25, 31 643, 26, 49 706, 26, 17 804, 26, 23 558, 26, 28 384, 26, 40 730, 27, 58 002, 28, 22 304, 29, 14 300, 29, 21 567, 29, 05 458, 28, 30 066, 30, 04 770; the ep bone 000, 2246, 002, 1453, 000, 3114, 001, 8080 and 000, 3890; the prmniers fascicles published Japanese Patent 54 - 122 728 requests, 54 * 109 935 and 54 - 055 534; U.S. patents 4,192 669, 3,950 420 and 4 or 256 and the Belgian Patent^875 889.

Gold, the applicant has found, surprisingly, that can be enhanced by incorporating carbohydrates, and thereby raise the sugar content and starch, in a large number of plants. monoeotylédones dicotyledonous and deliberate application of some of the compounds having the structure described above ., at concentrations under-borne *

er.., ■

It is a fact well known that the application of certain herbicides in low concentrations, shortly before harvest, causes an increased formation of desired substances to plants; - such as carbohydrates. In this can. generally attributable to a reversal of the netabolism of the plant by the herbicidal composition, which runs at (sometimes accompanied by a vegetative growth retarded), there may be a pronounced incorporating sugar, starch and other produced significant metabolism. Some examples of compounds having said properties are described in the following publications: US patent 3,556 762, the of SA-of-bone 25, 28 867 and the 25, 57 139, but heretofore were previously not known such activity as regards substitution derivatives phénoxyaicanolques and 1 © cyclohexane dione derivatives.

the ID present invention concerned thereby proegiO for increasing the G content read assy plant, Catherines (MB characterized * act on plants uüg effective amount of a compound of formula I

or of formula II

(II)

or a salt thereof with an inorganic or organic base or a hydrate thereof. The eyiab © " the, in formulae 1 and IX, have the following meanings: a radical 2représente I-one © formulas:

Y represents an oxygen lifeless " group - HC₂ ~, - NH or n-alkyl c ^ ^ - C.,

A represents a direct bond or one of the groups

- HC₂ - HC5 ch-ch-and -=-,

B represents a radical having one of the formulae

RR

^ - COOH, - COSR ^, ^ ^ - OC-n-_I - oC-n-T--9

i-VBE1

10

X is oxygen or sulfur

E is CH " a nitrogen atom or a

?

n,

L represents CH AC a nitrogen atom,

Rj represents a halogen atom, a group c?₃ , CFjH, 0cf₃ , CN or n0₂ ,

R₂ represents hydrogen, fluorine or chlorine or CF₃ , CN or n0₂ "

R₃ represents a hydrogen atom, a fluorine atom, chlorine or bromine or CF₃ "

R₄atcrae represents a hydrogen or a saturated or unsaturated, cycloaliphatic, aromatic or heteroaromatic ring,

Rj is alkyl in the Cj ' GC, alkenyl in c₃ ~GC, benzyl, phenyl, chlorophenyl or a radical of formula

- CH2 - COORjj (RG represents),

RG is a hydrogen atom or an alkyl - the Cj^C 4 *

R7 denotes hydrogen, alkyl CJ Cjq, phenyl which may be mono - or disubstituê by chlorine and/or CH ^, or a radical of formula - CH2 - COOH (the rg) ^,

RG and "T are" with 1 * - has striptease ∂ 'nitrogen, a aoyaaâepyrcoLidiae, piperidine or morpholine, the R " represents the TCA® I'd' hydrogen or year groups in an HM₃ ,

of Rj_Q each represent a hydrogen atom or alkyl HFU and,

. may further be a group phênyle, represents a atom hydrogen /' alkyl■^ C. - C., or a cation equivalent of an inorganic or organic acid,

13 represents, D. " hydrogen, an aikyl © in The Cj c ^ - or a phenyl,

' 14■represents a atom hydrogen, a axeexy° carbpnyle in neck alkyl in and ' 15 represents a alkyl in a-c ^ ^ - C. or a phânÿifchi © (-Cj) alkyl, a (C. ^ " ^ ^ ^ CIT îaikyl c-C.₃ >alkyl or phénylsulfinyl-DC ^ ^ ^ CjJaikyleneot® © or a phénylsulfο π γ ≈ 1 (^ - ^ C. C.) alkyl, a or two alkyls in the Cj c ^ or a (^ - ^ C. C.) "slcoxycarfeôisfiê"

the formula it will only represent one of the possible tautomeric forms, of which 1" use.. the fact object of the present invention ©.

Alkyl radicals and aicénylesmentioned el " above and hereinafter may be linear or branched ©.

By "halogen" is understood to mean a fluorine atom, or bromine atom of ehiôr®. As cation-forming salt ©, I'm ©? iesmeiesme.nt primarily for alkali metal cations

(AD⁺ , K.⁺ .) and ammonium, cation equivalents-the ICAs tile earth-metals (1/2 AC ^, ^ mgs i/2} or DS® eâ " ing organic ammonium bases such as

⁺ THE NH (C.₂H₅ 5, * THE NH₂ (C.₂H₅ 5₂ ,⁺ HH-₃C₂H_O ,⁺ THE K (C.₂H_O ) ^ vBE1 wics₃ )_{the R} +^NR H3_C H2_C H2_Q HR,⁺ THE NH₂ (HM₂ HM₂ 0:00)₂ and⁺ M H ^

The radicals R may be in Poultry ^ all those whose derivatives hydrbxyiês {RBG} ©'d are able to form. esters with the free X-esaposiles_aeides " is here a few radicals suitable for R ^:

a aikyle in the Cj-c-P-^^tooling 1 to 3 be substituted by halogen, preferably fluorine, chlorine or the bromine "and/or by OH, a aa.lcoxy in the Cj GC-, alkylthio in a (the Cj GC-)" - (c2~cg) alkoxy " alkoxy, halo (the Cj c ^ Jalcoxy, methoxy-ethoxy-ethoxy, an alkylamino di - (^ - ^ C. C.) alkylamino groups, cm., a sulfonyl in cY~C.^, a sulfoxyl in c^ " C. ^, a (c-j is' a-c ^ Jalkyl-to-carbonylamino-, a phenyl, a oxirannyle, and/or a phégexy, which may be 1 or 2 halogen carrier * or the L or 2^the Cj-c-C6 alkyl; cycloalkyl GC or GC which can harbor a halogen or CH group₃ ;

a alcênyle c ^ - GC, halo - (the Cj GC-) alcênyle; a cycloalcênyle in GC or CG; a alcÿnyle in c₃ which can carry on board 1 or 2 the Cj GC-alkyl, a phenyl " D.⁸ a halogen or an alkoxy in the Cj or c2;

phenyl which may be carrying is the I the Cj-c-alkylated in three ^ " alkoxy in c ^ ^ - C., halogens, n§2 or CF a-j;

a furfuryl, a tetrahydrofurfuryl or a radical corresponding to one of the formulas

0, 0

" Hr C ' 16 W-W-c-≈ - ORjg "* C."

17

wherein s

The R g is H or a ^ aikyle c ^ - GC,

R_j7 represents H, a aikyle in UCN alcênyle in

C.² _^<" 6f ^a alkynyl c2 " GC or phenyl, had much Rjg and R₇ together are a chain pentamethylene, W represents a alkylënein The Cj-C.₃ , which can ITRs® of mono - or disubstituted with a group aikyle " c0ch₃ or COOR_j3•

R is H " a c ^~aikyle €|or a cation equivalent of an organic or inorganic base, and represents a aikyle in.

■among the compounds of formula 1 wherein b is preferred eeass represents group - COOH ^, and a watershed @ @ s at last those wherein Y represents an oxygen atom and Λ a direct bond.

All parfciculièrement © L-e are compounds of formula I in which R ^ represents fluorine, chlorine, bromine or CF ^ and Rj atom'd ' hydrogen and chlorine, or in which % represents a radical of d® formula X yen₀

The compounds of formulae I and hence he peuveat be present as racemic isomer had opfci - " er. For the use according to the invention are suited the d optically active d-drilled that the optically inactive compounds described above.

Examples include the following few exaaples'd © compounds of formula I:

- the 2 "/4 -■{6 - c hr 1 gold O 2 Be-n-zexa o 1 1 ex-Y-Y-} ° phên © kv7"pr © piônats! alkyl in the Cj c ^,

the 2 - 4 - / - {6 a-chlofo and 2 a-benzothiazolyloxy) - phenoxy? " © propi⁰ * nate alkyl in the Cj c ^,

the 2 - 4 - / - (6 fluoro-2 a-benzoxazolvloxy5phënosy7propi © aste==alkyl in the Cj c ^,

the 2 - 4 - / - (6 a-IFFT luoranéthyl-to-XY-2~benzotmas0lyl ©) - phënexy/C alkyl propionate ^ - ^ C.,

the 2 - 4 - / - (4 a-trifluoraniéthylphénoxy}" © propioRâfe ^ / phenoxy alkyl in the Cj c ^,

the 2 - 4 - / - {4 a-trifluororaêthylphénoxy)" / ^ ^ phinoKyacétoôiiae ^ esters,

the 2 - 4 - / - (3 ,S and dichlcro and 2 a-pyridyloxy derivatives) - ^ / phénoîîypropionsfee of C alkyl ^ - ^ restorative,

- the 2 - / 4 a-£5-to-trifluorQméthyl and 2 a-pyridyIoxy) - phêaûxy7 " C alkyl propionate ^ - ^ C.,

the 2 - 4 - / - (6 fluoro-2 a-benzothiazolyloxyîphênoxy / - C alkyl propionate_{the L} - C._(J. ,

the 2 - 4 - / - {6 a-brcrao and 2 a-benzothiazolyloxy) - 7 - ρτο ρΜηοχ ^ 0=ΐο· nate of C alkyl ^ - ^ C.,

the 2 - 4 - / - {6-chloro 2 a-quinolinyloxy) ^ ^ ρΜηοχ 7 0 1 ρ ≈ ρΐΤ οηΒ℮ θ of C alkyl - ^|C.,

the 2 - 4 - / - (6 chloro-2 a-quinazoléinyloxy} - propionate/phénexy C alkyl₁ THE C ^ -,

among the compounds of formula 11 those are preferred wherein the V 'which' '

represents ethyl or ailyle,

Of Rj-J is C alkyl ^ - ^ C.,

R_} ^ represents H or méthoxyearbonyle and

R_I represents two alkyls in the Cj c ^ or an alkyl thio - (C._{the L} - C.₃ ) - aikyle,

or their * alkali metal salts.

The compounds of the invention provide for increasing the carbohydrate content in a large number of monocotyledonous and dicotyledonous plants, or their fruits. Examples include, for example, cane sugar confectioneries, sugar beet, grapes, melon, fruit, the ponune earth, corn, the various species millet (nervosum) and the fillings (clover and alfalfa). It in solvent borne coating if TE to elevated sucrose content in the case of sugar cane, sugar beet and species millet, the fructose content in the case of fruits and grapes, and the starch content in the case of other plants. The advantages thus achieved are obvious and do not require further details.

Their application for for influencing the content

in carbohydrates occurs at a later stage of plant growth that for their application as herbicides, since, at this stage the plants are much less sensitive to the action of herbicides at the stage of the lift, then they are supporting higher doses without damage. Advantageously, the active compounds are applied about one week confectioneries five months before harvest. After the lapse of time, the degree of maturity caused by the active material and, by consê° quvïit, the carbohydrate content, have reached a maximum. Π note that growth rate and duration of vegetation of different cultures can vary within wide limits. Thus the cane I-suere requires, depending on a locus and the climate, of 1 has 3 years to reach maturity. It must therefore assume the time. application to these conditions, time which may be between! and 13 weeks prior to réeolt © iaao the case of; sugarcane and sorghum soft "

ii ^ AE-to-active materials of formula 9.ï © STRs may applied as forme.de powders mouillabies, d-® e transformer " degrees centered iaulsionnables, of spraying,, I-⁹ has=effecagents powdering or granules,, in the forsMiatloas " usual, the. proportion of active materials in SEA formulation depending on their nature and ' which may range from 2 s at 95% "

Wettable powders are e<O-® POSs £aces can disperse uniformly in water® The QT mistletoe *, © its addition to the active material and a diluent © " a chasrfô inert_Receive contain wetting ., by exeaplepolyêfchoxylës alkylphenols, of oleyl - or stiarylasiaes # polÿêtfeoxyiéss Peppers © e alkane sulfonates or alkyl°fe © bsêne° sulfonate? and dispersants, example L © © the sodium alkyl glyceryl sulfonate, sodium salt of cyclopentan - © diaaphtfl³ 2.2 "raêthaneisuI of £oniqu e 6" 6', or © I-s i seâiq& i^O oleyl-methyl " of taurine.

The concentrates énulsionnables&ermostfeobfc if not dissolving the aatière rgôsai° that active into a solvent®, such as butanol, cyclohexanone, the disôthyl^{THE CT}formaaide, the xylënes or hydrocarbons ERAs®;⁰ ticks higher boiling point, and adding the I⁰ my non-ionic wetting, for example a allsyipihô! © ©, or @ ëthoxylê d°un oléylaaine or stëaryiêüisaéthoxyXëe © "

SAL agent-dusting are obtained by Fe-yafe @ of the active material with solid bodies 21asaoaè targeted, by exeapî © of talc, clays aate © llGO_C. © su° mth kaolin or bentonite, the pyrophill&tee grams®4g diatomaceous earth "

Can be manufactured by spray die the aatière active on a support fgasmli adsorb, - either by the application of concentrated IF® the dairy activates, at ' adhesives, such as ale © ©! vinyl, sodium polyacrylate or eneor © confectioneries © feiloo O-mineral, on the surface of media, such ' as the natural © 2, 0 and the kaoiinifeæMo, or a granulated inert material © *, hwcm s * y activesqui materials suitable for the bridge also, optionally by combining them with fertilizer, resorting to the methods ordinarily applied for manufacturing granulated fertilizer-d *.

The concentration of active substance of commercial formulations can vary within wide limits.

In wettable powders it is such as between about 10 and 951, balance formulation additives indicated above. In the emulsifiable concentrates it is between about 10 and 801. In the dusting agents it oscillates between 5 and H ealth spangle 201. In the content of active substance depends on, among other things, the physical state (liquid or solid) of said active material and the nature granulation agents, fillers andc, involved.

For the application, commercial products as concentrates are optionally diluted in the usual manner, for example with water in the case of wettable powders and of the emulsifiable concentrate. The dusting agents and, as well as spraying, do not need to be diluted with other inert substances prior to application.

The dose to be applied depends on external conditions, such as temperature, humidity and particularly the species the DS treated plant and its stage of development. Chroma in general, an amount such that the active material occurs in the natural growth process of the plant without being harmful to it. The dose may therefore vary in extended intervals, for example between 0,005 and 10 kg of active material per hectare. It may even be higher. In the case of plants latlfoliées, that are not endommaqées by the compounds of formula I, or which are only very little, the amount is preferably between 0.1 and 5, in particular between 0.5 and 2 kg/acre, while concentrations generally lower, ranging between 0.01 and 1 kg/acre, suffice in I® case of monocotyledonous plants.

If desired, the products can be associated th'd ' at very herbicidal, insecticidal and fungicidal.

Sxenpies regarding the formulation ii

The parts and percentages of materials extend by weight, unless otherwise indicated.

WITH ESEHPLE.

Emulsifiable concentrate is obtained from I-back .1.5 portions of active material,

75 parts of cyclohexanone as solvent, and

10 parts of nonylphenol poiyéthoxylé (I to 10 ethylene units-oxy-) as emulsifier.

l-gSEMPLg.

A wettable powder is obtained which is easily dispersed in water by mixing:

2S portions of active material with

64 parts quartz containing kaolin, as m * tit° REs inert,

10 parts of liqnine-to-year average * onate potassium, and

1 part of the sodium salt of 1 'oiéyl-methyl-taurlne, as wetting agents and dispersants,

and grinding the mixture in a mill I-toothed rings..

' smms

A dusting agent is obtained by mixing the n # T- 10 parts of active material and

§0 parts of talc as inert material,

and grinding all in a mill T- spider.

EXBJPLE gms.

A granule consists for example of about the I 2 to 15 parts of active material, and

98 to 85 parts of a granular inert material, the brand of® that attapulgite, pumice or sand da and the quartz. ,_{the R}Examples blolbglddeè

The method according to the invention is illustrated in the following examples by increasing the sucrose content " without being limited I-the application described.

Example 1

TB•|thode_dfessai

Plants are cultivated sugar cane in pots in a greenhouse at 25, 1 35 reign uu^I C and a humidity of approximately 65%. Suspending, in water containing about 251 of a surfactant (nonylphenol), various amounts of the products according to the invention formulated.

Is applied each time the plants 0.3 ml of slurry using a syringe in the region of the pod at the last limbus viewable ("dewlap") (10 seedlings per concentration). Removed the sheets of treated plants as well as indicators (untreated) after 3 weeks at the time of harvesting, and internode segments analyzed by groups, to determine their sucrose content. The results are collected in Table I.

TABLE I

Active material content (%) sugar

at the time of harvesting

Legend; ·

The X {+ D.} - 9.ï ethyl 2 - 4 - ^ (6 a-chioro-a 2 a-ben20xazoXyloxy) phenoxy - ^ Receive methylpropanoate, :■. " ;•

It: ethyl 2 - / 4 - (6 chloro-2 a-bénzothiazolyloxy) phenoxy - ^ / methylpropanoate,

IIIî racemate of the compound I,

VI s-propyl 2 - ^ 4 - (6 chloro-2 a-ben2oxa2olylpxy) - phênoxyj ^ methylpropanoate,

V. S 2 - Bfchyl ^ -, / 4 - (6 "platinic 2 a-quinpxaiinyloxy) phenoxy - ^ /" " methylpropanoate,

Ethyl 2 - wh_< 4 - / (6 a-chIoro-a 2 a-quinolinyloxy) phenoxy - ^ - */ methylpropanoate,

2 ID-U-£thoxyiminoVlXi) - butyl 5 - (2 a-ethylthio) - propyl-L, 3 - ' dioxocyclohexane,

VIII-ii 2 / - " (L AIlyloxyiiBino) - butyi7-to-4-methoxycarbonyl-5.5~

d-PLA thy a 1 - 3 - oxo-c which yc lohex -1 - e no. 1 sodium.

Example 2

Is the active ingredients formulated in suspension in water in the manner described to the example L with 0.25% of a surfactant, and is applied, for each preparation and each concentration, 0.3 ml of a suspension at pod 10 I-sugar cane plants.

Age of seedlings was 18 months at the time of non-application.

Harvested plants after 5 weeks, bone removes the sheets and by analyzing 14 PeoPles labeling © *? flagstones superior groups to determine their content sucrose and the purity of the juice, by method called® "méthode press assembly"Tanimoto. ^ 'T, Hawaiian is Planters Exhibit timetable, 57, 133 {IS64)_ 7

The content of sugar by polarimétri © and expressed in terms of " % by cane PolI", the numbers thus obtained corresponding to the content I in sucrose solution, assuming that sucrose is the only substance which, in the sugar solution, which deflects the plane of polarization of the light. This method of détemiastioh of^has The pol % by cane " is a recognized method to determine the sugar content of the cane sugar 8.

Table 3 9.ï

Dose applied purity of the aluminum content of the lo % 4>sacchasOsseaaR ©₌/

Are cultivated beets in of PETS 15 filled with silt sandy placed in greenhouse, by adding âc high quantities of nitrogen. At the age of 14 weeks is RIST&Q in the plants with the active material II in confectioneries dose

1.25 kg/acre, is harvested 5 weeks after this treatment and examined to determine their sugar content " 20 - the results are collected in Table III, expressed in % compared to indicators.

TABLE 3

Beet yield seero indicators 100,100

It spring much of the test result

that the method according to the invention produces significant augmenta° except the content and the yield sacettarose in the treated plants.