BE644357A - - Google Patents

Description

  

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 EMI1.1
 



  It OXAZINONESO THEIR PREPARA'ION AND THEIR trnLI8A'tION ".

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   The present invention relates to novel heterocyclic cota-posites and, more particularly, to such compounds containing an oxygen atom and a nitrogen atom in the heterocyclic ring.
Many compounds according to the present invention are useful for combating unwanted vegetation. Certain compounds are effective herbicidal agents at doses of 0.565 kg per hectare of surface treated only. Furthermore, the compounds according to the present invention constitute. intermediate compounds which are valuable in the preparation of a large number of compounds of the uracil type which constitute themselves.

   herbicides *
The new compounds according to the present invention are the oxasinones of formula:
 EMI2.1
 whereby R1 denotes hydrogen, an alkyl radical containing 1 to 10 carbon atoms, substituted alkyl containing 1 to 8 carbon atoms, aryl containing 6 to 10 carbon atoms, substituted phenyl aralkyl containing 5 to 13 carbon atoms,

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 EMI3.1
 substituted aralkyl containing 13 atones 4.

   carbon,
 EMI3.2
 alkenyl containing 3 to 8 carbon atoms, alkynyl containing
 EMI3.3
 nant 3 AS carbon atoms, cycloolkyl containing 3 to 12 carbon atoms, cycloulkenyl containing 4 to 12 carbon atoms, cycloulkyl 41kyl containing 4 to 13 carbon atoms cyclorlkdnyl alkyl containing 5 to 13 carbon atoms, substituted cycloalkyl , eub8tttuated cycloolkenyl, (substituted cyclonl- kyl) alkyl containing 4 14 carbon atoms or (substituted cyclonlkenyl) alkyl containing 14 atoms of anbt4r R2 denotes hydrogen, chlorine, bromine or a methyl, ethyl, n- radical propyl, 18opropyl0. n-butyl, eec-butyl, tort-butyl, m4thoxy. ethoxy # n-propoxy. 1lopropoxy, n-butoxy, 'eec-butoxy or tert-butoxYJ denotes an alkyl radical with 1 4 j atom. curbont, ohloro-ulkyl & 1 to 4 carbon atoms or bromoalkyl.

   with 1 # 4 atoms
 EMI3.4
 of carbon;
 EMI3.5
 R2 and R3 can be joined to form a group - (CH2) ndnna which g is a positive integer from 3 to St o $ and. say 3t 4 or 5 * The expression "substituted alkyl * 4 embraces radicals
 EMI3.6
 such as t bromoolkyle with 1 to 8 carbon atoms,
 EMI3.7
 chlororlkyl & 1 to 8 carbon atoms, hydroxyolkyla 1 8 carbon atoms, olkcxynlkyl 2 to 6 carbon atoms, aikoxy curbonyl alkyl of 3 & 6 carbon atoms and cyanoulkyl 1 2 to 8 carbon atoms.



  .. -

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 EMI4.1
 From mAma, the expressions "aryl" and "phenyl substim tu '" describe radicals such as phenyl naphthyl biphenylyl chlorophenyl bromophenyl alkoxyphenyl dibromophenyl dichlorophenyl fluoroph6nyl trichlorophenyl
 EMI4.2
 alkylphenyl with 7 - 11 carbon atoms dlolkylphenyl with 8 12 carbon atoms chloronylkylphenyl k 7 # 10 carbon atoms nitrochlorophenyl nitrophenyl dichloronitrophenyl chloroaikoxyphenyl with 7 ## if carbon atoms tr'xuoromthyxixydronphenyl tetetrochlorophenyl and dichlorophenyl dichloronitrophenyl with 7 ## if carbon atoms tr'xuoromthyxixhydronphenyle



  The expressions "arttlkylt" and "arùlky1e aubatitudu denote radicals such as:
 EMI4.3
 furfuryl benzyl phenylalkyl with 8 - 11 curbone atoms (total) chlorobenzyl dichlorobenzyl
 EMI4.4
 11 carbon alkylbenzyl (total) 9 carbon alkylbenzyl - 13 carbon atoms (total) nitrobenzyl alkoxybenzyl A Ô 11 carbon atoms (total) and naphthylmethyl.



  Terms Iloyoloulkylouo "oyoloalk'ny2.8". aayola alkyl alkyl "and cya.aaikényl alkyl" include the radicals

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 EMI5.1
 cyclohexy18 cyolohexenyl
 EMI5.2
 cyclohoxylalkyl cyclohexenylolkyle cyclopentyle
 EMI5.3
 cyclopentenyl cyclopentylolkyle cyclopontenylalkyl
 EMI5.4
 norbornyl norbornenyl
 EMI5.5
 norbornylnlkylt norborndny.alkye
 EMI5.6
 bicycle (2,2,2) octyl
 EMI5.7
 bicyclo (2,2,2) octenyl
 EMI5.8
 bicyclo (2,2,2) octylolkyl
 EMI5.9
 bicyclo (2,2,2) octenylolky1.

   
 EMI5.10
 cyclopropyl cyclobutyl cyclobutylalkyl
 EMI5.11
 cyclobutenyl cyclobutdnylulkyle
 EMI5.12
 hexahydroindanyl
 EMI5.13
 t6trahydroindunyle
 EMI5.14
 hexuhydroindenyl
 EMI5.15
 hexahydroind <5nyl alkyl t6trahydroind4nyl alkyl hexthydroindanyl olkyle hexnhydro'-417 ′ -! thnnoindnyle tdtrahydro-447-mdthanoindanyl hexohydyo -., 7-mthanoindanyla hgxrhydro..6e-kyindyl-akylindanyl-alkydro-alkyl-4-hydroxyl-alkydro-alkyl 4-hydroxyl-methyl-4-hydroxyl-methyl-4-hydroxyl-alkyl 4-throky-4-hydroxyl-methyl-4-hydroxyl-methyl-4-hydroxyl-alkydyo-.,. hexahydro 4,7-m4thanolndcinyl alkyl
 EMI5.16
 decahydronuphthyle
 EMI5.17
 decohydronaphthyl alkyl

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   tetrahydronnphthyl tetrahydronuphthyl alkyl
 EMI6.1
 decahydro-1,4-methunonphtyle decahydro-lt4'-methttnonophtyl alkyl octuhydro-1,4-múthunonl1phtyle octahydro-l, 4-m6thtnontlphtyl alkyl décuhydro-l, 4-5, 8- <3 im6tmonō)

  4-5 Ô-dimithunonnphtyl nlkyle actuhydro l, t5,8dimbthinonuphtyle et oetnhydro-1 # 4-5ug-dim6thunonuphtyl alkyl res 13ubetituunte cyclic can be further substituted for ulkylo radicals containing i, at carbon atoms, methoxy, chlorine or bromine.



   The compost of formula 1 can advantageously be prepared in sole form with organic or inorganic acids. The free base is very unstable and the salts are therefore strongly preferred. As an example of these pre-
 EMI6.2
 and there may be mentioned the salts of acids such as hydrochloric, hydrobromic, hydriodic, sulfuric, benzoic, acetic, phosphoric, phtuliquo, citric and acetic acids.
 EMI6.3
 nic, meteic, turtric, propionic, dichloroacetic, tri-chloracotic, alphu, alphu-dichloropropionic, etc.



   In accordance with the present invention, the compounds of formula 1 given above can be prepared by a simple and remarkable two-step process, as follows:
 EMI6.4
 Step 3, Reaction of a substituted océtou6tumide with ammonia, so as to form a substituted beta-aminocrotonamide.



  µ & ag2 2: Reaction of beta-uminocrotonamide nveo with phosgene, so as to form the corresponding oxazine-2-one hydrochloride.



   The process proceeds according to the following equations}

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   Stage 1:
 EMI7.1
 In these formulated, R, R2 and R have the same meaning as
 EMI7.2
 dune formula 1, The aohoncdtnm1dl 'used in stage 1 are prepared by reacting an amine with a diketone such as
 EMI7.3
 Further described or pure reaction of a beta-edto ester with an excess of amine, followed by treatment with aqueous acid.
 EMI7.4
 



  A preferred exemplary procedure will now be described where R2 is hydrogen and R is methyl. The uketoacetumide used as a starting material can be prepared by making diedtene with a colon lead. 'equation
 EMI7.5
 This process is described in more detail in the patent of
 EMI7.6
 United States of America n 2 * 615 # 917 * The ketoncetamide is then reacted with lummoniac. This reaction is carried out by mixing ammonia with a solution of acetaminophen in water or in an inert organic solvent such as ether, tdtrahydrofuran, alcohol, 1,1,2-trichlorethylene or the like.

   When using water as a solvent, ammonia can be advantageously added in the form of an aqueous solution. Thus, a concentrated aqueous solution containing about
 EMI7.7
 29-30% by weight of ammonia. When using a solvent

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 inert organic, ammonia can be introduced as a gas or form an undiluted liquid, The mass relation-
 EMI8.1
 nelle is stirred, if desired, to promote a good mixture of reagents * The molar ratio of Itammonice to ao'toooetomide must be at least 1 ..

   The upper limit of the ammonia proportion depends largely on convenience and economics, but there is no reason to exceed a
 EMI8.2
 ummonlacSocétoucótum1de molar ratio of 5011 # a lower ratio of 10%. It is preferred.

   The use of an excess of ammonia gives an increased yield of betu-aminocrotonamide. The temperature at which its leaks 1 tm: ln / jt1on of acetoacetemlde is, in large part, a matter of convenience At ambient pressure, Temperatures above about 500 ° C are usually reduced, because of the unwanted loss of ammonia which occurs above this temperature. The reduction temperature is preferably between 3 ° and + 30 ° C,
The amination reaction generally takes 1 to 10 hours, depending on the reaction temperature and the system used.
 EMI8.3
 



  The resulting beta-eminocroton is recovered pure by suitable physical means, for example, by filtration, layer separation, solvent evaporation or the like. After recovery, the beta-ainocrotonamid. can be seohée and used directly so step 2 of the process! or, . if desired, it can be purified by conventional methods, for example by recrystallization.
 EMI8.4
 



  The bAt ± 1-tJm1nocrotonnm1de prepared in stode 1 is transformed into oxuzin * X'w) corresponding unsubstituted by reaction of ltrm3, de with phosgene. The preparation of 6-imino-3 6-dihydro-4-methyl-2H-1,3-oxaaln-2-one hydrochloride from beta-tminocrotonumide and phosgene will be de- @

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 EMI9.1
 orlt. Now on an ultratit basis.



  A solution of phosgene in an organic solvent
 EMI9.2
 Inert such as tetrehydrofurune, dioxin, noetonitrile, ltlt8 "trichlorodthylene or a similar solvent is prepared. A solution or suspension of betaM1nocrotonmlde in a solvent, preferably in the same oolvunt that the phosgbno # is mixed. phosgene solution One can use any amount of water.

   of beta-umlnoerotonamide and phosgene, but in order to obtain conditions of efficacy and improved economic conditions, it is preferred to use a large excess of phosgenes. Usually the amount of phoogôna used does not exceed 5 moles and does not exceed 5 moles. preferably not 2 moles pure mole of bfita-aminocreton-amides It is advantageous to add the solution or suspension of crotonamide to the solution of phosgene and to continue to
 EMI9.3
 add fuqon phongene to maintain an excess of phosgene and so that the solution remains saturated with phosgene. A pree "aion above atmospheric pressure can be advantageously used,
This reaction is highly exothermic and a large amount of heat is given off during the course of the mixture.
 EMI9.4
 beta-aminocrotonamide and phosgene.

   It is desirable to carry out the mixing at moderate temperatures, for example at about 25 to 50 ° C., so that the evaporation of the phosgene is minimal. External cooling means, such as a refrigerated condenser can be used, at need to keep the temperature within these limits.,
 EMI9.5
 When the mixing of the b'tn-ominocrotono # 1de and the phosgene is complete, the mixture which contains a solid material as a second phase is heated to a temperature collected between about 40 and 10,000, for a period of between about 30 minutes and 6 hours, to complete the reaction,

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 This gives rise to the formation of the desired hydrochloride of 6-imino-3,6-dihydro-4-methyl-2H-1,3-oxazin-2-one. This compound can be recovered by suitable means. any,

   for example by filtration or by decanting the liquid on * nngennt,
The hydrochloride can be converted into other salts of the oxazinone by conventional replacement reactions or pure hydrochloride conversion, for example by using silver oxide suspended in an inert solvent, such as sodium chloride. methylene, followed by filtering off the urgent chloride and adding the necessary acid to obtain the desired salt.

   Salts of acids weaker than hydrochloric acid can be prepared by suspending or dissolving oxazinone hydrochloride in an inert solvent (or, more simply, in the more weak acid, when that this is a liquid), adding the appropriate amount of the weaker acid and a sol of that acid, for example sodium sol, and then filtering off or otherwise removing the chloride from sodium formed,
Those of oxazinone, in which R 2 * and chlorine or bromine are prepared by conventional halogenation methods, for example pure reaction with halogen in glacial hectic acid or other solvent.

   

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   Oxazinone salts in general do not have a defined melting point. When heated, they lose chlorinated hydrogen and turn into the corresponding uracil, ¯ as described in more detail later in this present document. memory.



   Oxuzinone salts are soluble in water and somewhat soluble in highly polar organic solvents, such as acetic acid and alcohols, but they are insoluble in less polar organic solvents.



   Oxazinone salts have specific characteristics. distinctive or particular infrared absorption. These characteristics are (a) absence of absorption at the N-H frequency, (b) intense absorption at 1770-1810 cm, which can be attributed to the part
 EMI11.1
 0 NR Il fi -0-0-0- of the structure of formula 1, (c) multiple absorption between 1570 and 1660 cm "* 1 probably due to pure absorption ...... 0-,. . ::; CN-, and> G "0 | and (d) average intensity absorption at 1510-1515 cm-1 characteristic of monosubstituted amides. Nuclear magnetic resonance and ultra-violet light examinations confirm the nuclear structure attributed to oxazinone derivatives.



   The following three tautomeric structures are shown for the compounds by the information given above

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 EMI12.1
 
As already noted, many compounds of the present invention exhibit herbicidal activity. Due to their remarkable utility as herbicides for general use against broad-stemmed plants and weeds, it is preferred. salts of compounds of formula 1, in which R1 denotes anything other than hydrogen,
Particularly preferred due to their effectiveness as herbicides are the salts of the compounds of the following formula
 EMI12.2
 in which R1 is an alkyl radical with 1 - 10 carbon atoms,

     alkyl substituted with 1 8 carbon atoms, aryl with 6 - 10 carbon atoms, phenyl substituted, nrulkyl with 5 - 13 carbon atoms, substituted aralkyl containing 5 - 13 carbon atoms, alkenyl containing 3 - 8 carbon atoms, nlkynyl containing 3 to 8 (carbon atoms, cycloalkyl containing

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 EMI13.1
 3 to 12 carbon atoms, cycloolkdnylt containing 4 & 12 units of ourbone, cycloolkyl alkyl containing 1) carbon stream cyclot4lk4nyl ulkylt containing 5 to 13 carbon atoms, substituted cyc1oll1kyl.

   substituted cycloulkonyl, substituted cycloulkyl nlkyl containing 4 to 14 carbon atoms or cycloulkonyl substituted alkyl z 5 to 14 carbon atoms R2 is hydrogen, chlorine or bromine; B) is a methyl radical, and R2 and H3 can be joined together to form a group. (CI12), - in which n is', 4 or 5 (Ivec as condition only when R2 is hydrogen and R3 is a group methyl, RI is or-
 EMI13.2
 be a methyl or ethyl radical,
 EMI13.3
 As examples illuctratita of preferred compound yes.
 EMI13.4
 go to the invention, one can quote the salts and, in particular,
 EMI13.5
 the hydrochlorides or hydrobromides of the following oxozinonea 6-sec-butylimino-5-chloro -), 6-dihydro-4-methyl-2H-1 ,, - 0) (/ 1 Z in ... 2..ono 6-aec -buty11mino -, - bromo-3.6-d1hydro-4-methyl-2H-1 ". oxaitin-Z'-one 6-norbornylimino-3,6-d1hydro-4-mâthyl-2H-1,) - oxuI1n-2- we.

   



  6-norbornylmethylimlno-5-bromo -), 6-d1hydro-4-methyl-2H.l,). oxtlzin-2-one 6- (1-6thYlpropy11m1no) -5-bromo-3,6-d1hY9r6thyl-2H-l ,, - oxnzin-2-ono tt- 6- (1,3-dimethYlbutY11mOro -), 6-d1hYdro -4-m'thYl-2H- 1, J-oxazln-2.one -;, ... ,,, 6 ieopropyUmino-5-bromo-3 # 6-dihydro-4-methyl-2H-1p) - = zin- 2-rûnr '#' '"" 6 tert-butyl imino 5 broracH3,6-dihydro-4-ethyl-2H-1,3-oxuz in-
 EMI13.6
 2-one
 EMI13.7
 6-phnylimino-5-bromo-3,6-dlhydro-4-methyl-2H-l,) - oxDzln-2-one

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 EMI14.1
 3W 4, 'i ea tctrnhydro +' dthrno, ndan.ya, iaxino j .., 6 d, hydra.t + xndbhy H.1, axEz, r .. "ana bcyclahexyiim.na-5 bramo., É..di .hydra4rnsdthylrH ,, 3-oxasin 2-one ..cycl, ahaxyümina 4, âtrimthylne.3,6âihydro.2u1,3oxuxit
 EMI14.2
 2-one
 EMI14.3
 %> The preparation of the compounds according to the present invention is illustrated by the following special examples,

   i are given for explanatory and non-limiting purposes and in ¯¯a the portios t percentages soet by weight, unless otherwise indicated, E2igmolâ.1 6-aec hydrochloride '<butylimino-'3t6-'dihydro-4- < aethyl-'2H- 3, 3oxr z in.-ane.



  To 852 parts of N-aec-butyloketoacetamide, 540 parts (excess of z) of concentrated aqueous ammonia solution (29%) are added, the clear solution stirred and kept.
 EMI14.4
 substantially at room temperature, In order to avoid loss of
 EMI14.5
 excessive ammonia. After about 6 minutes, the solution becomes cloudy and an oil soon begins to separate. Crystallization is omitted by scraping the wall of the glass. After 4 hours, the precipitation of In b8to-om1no- N-08c-. butylcrotonmido is complete. A crystalline mass is filtered off and the whole solid is washed with gala- ced water and z6ch6o in a 55-60 ° 0 vacuum oven. The product obtained is weighed and it is found that the we get 696 parts (& 2% of theory) and it melts at g4-8.C.

   Rocriatolliantion in benzene increases the melting point to 89-90 C, Analysis calculates for CgH16N201 N 19; r found 1 1? R7;

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 EMI15.1
 Has a solution of 22 parts of phosgene in 100 per-
 EMI15.2
 ti4a of tetrahydrofurnnes is added dropwise and oi. Contains a 31.2 part solution of blt.am1no-N-8.o.butyloro. tonamide in 75 parts of trshyc1roluran. A solid precipitates and the temperature removed to 4'-0, the mixture is stirred and heated under reflux for 2 hours # then retro'-
 EMI15.3
 di and filter so that we obtain 27 portions of chlorhy-
 EMI15.4
 baecbutyl drate, mina 3br.dihydratmethyl, 2It-1,3 axaaine 2-one melting â 'r, 51, .6, â C nwith gas release Analyzes calculated for C9H1, C1NaO.

   N 13t2% found 11208%
 EMI15.5
 The infrared spectrum of this material is characterized
 EMI15.6
 por a strong point at, 6 microns, attributable the part
 EMI15.7
 -0-0-Out by a 3.7 micron A tip (amine hydrochloride) 0 m N 0
 EMI15.8
 and by the lack of absorption of NH in the region of 3 m1oronl, the solid is soluble in water at a rate.
 EMI15.9
 about 27% by weight & room temperature, When the aqueous solution is left or stood at room temperature for a
 EMI15.10
 For a prolonged period of time, C02 is released, this release being very much faster when the solution is heated.

   The solution can then be isolated from ammonium chloride and N-8tc.
 EMI15.11
 butylacetamide,
 EMI15.12
 Upon heating a etc to a temperature above the melting point, until gas degugomation followed by cooling, it forms a solid which does not lower the melting point of 3-sec-butyl-6-. methylurneils (PF l.g10C, This solid mntièro has an infrared spectrum identical to that of u1 "110118.



  When oxacinone is dissolved in dilute aqueous solutions of Hazan, Na2co3o, NOOOCCH3 or! 8 <hae of

 <Desc / Clms Page number 16>

 
 EMI16.1
 NOHO, 13 a virtually instantaneous rearrangement takes place in the manner of z, forming the above-mentioned uracil * This uracil which is present in the solution under volume of its sodium salt can be isolated by acidifying the solution, Lturuoil1
 EMI16.2
 separates us form a syrup which crystallizes by tritura-
 EMI16.3
 tion and it melts at, 1d.124C, after recrystallization of a
 EMI16.4
 mixture of alcohol and water,
 EMI16.5
 6¯19Qprotiyllmino 3t6 dlhydro * 4 * <-nethyl-2H li3 'oxazin-2-net hydrochloride To a 33.6 port 1 solution of H-1eopropylaoetoacd-. Amide of 33o6 parts of water, 29 # 3 parts c1'ummonia are added in concentrated aqueous solution (286f.

   The solution obtained is stirred at room temperature for 6 hours, during which the beta-amino-N-ilopropylcrotonamide precipitates under
 EMI16.6
 form of a white crystalline material. This material is re-
 EMI16.7
 picked by tiltrut.on, washed and air dried. One thus obtains 2. t part of materials melting at 142-144 ° Ct.
 EMI16.8
 is pure enough to be used as described later, but it can be further purified,
 EMI16.9
 if desired, by reoriatvl1110tion in ethyl acetute, which allows to obtain a more pure material melting A 144-145 duke, A solution of 56.8 parts of b'tu-lJm1no-N ..1sopropyl. crotonamide in 400 parts oxone is added over 5 minutes to a stirred solution of 436 parts phosgene in 200 parts dioxin.

   The reaction temperature rises to about 5000 # after which it begins to decrease,
 EMI16.10
 one so that it is necessary to apply heat. After
 EMI16.11
 2 hours of heating at 80-100.0, the yellow suspension is re-
 EMI16.12
 cold and the solid material is collected by filtration.

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 EMI17.1
 



  It * and washed with the aid of dioxane and ether and adohde under vacuum at 25-3O * C, in aorta which one obtains 60 # 6 parts of chlorine. hydrate of â iaaprnpylimina 3, b-dihydro t, .. mgthyl2tl.l ,, 3 axa. tin-2'ne melting at 156 lb0 C with evolution of gas, Analysis: calculated for CsH13C1N2021 N 13.69% found 1 bzz
 EMI17.2
 EXAMPLE?
 EMI17.3
 Hydrochloride do Er .. hân limino. ô..dih dra eth 1H1 .. oxazin-2-one.



  ,. a stirred solution of aS, 6 parts of ac4touo'tan1- lide in 1500 parts of water and 150 parts of methanol at 73 $ C # 67 pprtien of concentrated aqueous solution (26%} of omonia is added After a few minutes, an oil forms, which begins to crystallize, when we scratch the purity of the real
 EMI17.4
 reaction pient. After 2 hours, the suspension is cooled on ice and filtered. The solid matter is coiled with
 EMI17.5
 400 parts of cold euu and rbch6a in a vacuum tower at 60 ° C, 69 parts of b8to-nm1no-N-phenylcrotonomide (according to theory) are thus obtained, melting at 140.5-142.3 ° C.



  A solution of 6.8 parts of beta-amino- * N-phenylcrotonmide of 40 parts of t6tr "hydroturene, is added over 10 minutes to a solution of 4.5 parts of phoagen in 25. parts of tetrahycirofurtme The suspension is
 EMI17.6
 heated to 60-70'C for 2 hours, then cooled, after which
 EMI17.7
 the batch solid material collected by filtration, coiled with t6ttIJhydroturone and adahia in air. This gives 7.6 parts? Phâny2imina hydrochloride, b dihydro.t, nithyl2H 13 oxazin "2'-one, mp 23 ° S44 ° C with evolution of gas.



  Analysis calculated for C11H11C1N2O2 'N z found t 11.72 Jt The products of Examples 4 to 25 are prepared by

 <Desc / Clms Page number 18>

 
 EMI18.1
 opting from the first described * in lt # XemPli 3t but in replacement. qnnt itoketoncetanilide of this example by equivalents of the nc'toae6tQmtdee indicated so as to obtain the opacified bOtu-uminocrotonm1de and finally the product
 EMI18.2
 identified
 EMI18.3
 E !! 1.1.Pj.,. Acé.? Tame, Aminocrotonom14e r fr9dY1
 EMI18.4
 4 N-Dllylu ketol1 cd .. b8tn-umino-N- Shyid ullylcrotonamide hydrochloride 6-allylimino-J, 6dihdrO-4-methYl- 2H-1, 3-'oxnxin-'2-on 5 N "(p'- tolyl) <'cto <- beta-an) ino-N- uctnm1de (p-tolyl) cro- (p-tolyliraino) -3 6r- tonumide d1hrdr0-4-methyl- 2H-,) - oxuzin-2- hydrochloride
 EMI18.5
 
<tb> one
<tb>
 
 EMI18.6
 6 N-octylac4toaett .. bGto-omino-N ..

   6 .. tomid octylerotonn-octyliMino-3t6- hydrochloride dihdr o-4, -m6,6h t 2 H-I, 3-oxn z in-2-
 EMI18.7
 
<tb> one
<tb>
 
 EMI18.8
 7 N-norbomylacdte- b8ta-amino-N- Acetamide norbornylcroton-6-norbornylimîno-amide hydrochloride J, 6-dihydro-4- mlthyl-2H-l, 3- n! Ethyl-2H-l, 3- OXAI n- 2-one 8 N-chloroethylacdto- beta-amlno-N- Hydrochloride
 EMI18.9
 
<tb> acetamide <SEP> chloroethyl- <SEP> 6-chloroethyl-
<tb>
 
 EMI18.10
 crotonamide imino-Ji6-d hydre-4-m4thyi.2H 1.3. oxazin-2'-cne 9 N-bent lacitc- b8ta-am1no-N- Benzyloroton acetamide hydrochloride- '6-bontylimino-3 6- amide dihydro-4- idthyi- 2H-l, J-oxazin-2-
 EMI18.11
 
<tb> one
<tb>
 
 EMI18.12
 10 K-cyclohexenyl <* beta-aminc-H.

   6- Acetoacetamide cyclohexenyl-cyclohexényi-imicrotonamide hydrochloride 'nO-J, 6-dihrdro-4-methrl-2H- .J-
 EMI18.13
 
<tb> oxazin-2-one
<tb>
 
 EMI18.14
 11 N-mithylacitc b4ta-amino-N. Acetamide methylcroton- 6- <nethylimino * 'amide 3t6tdihydro''4 "mthrl.2H-l, j- OXAI n-2-one hydrochloride

 <Desc / Clms Page number 19>

 
 EMI19.1
 12 N-o-tluorophClyl. B't .... lI11no-N- 4-a toiteae4taeide o-fluoroph6nyl- (o-tluoro-ph6ny1- crotonamide 1m1no) -3, 6t.d1hßdro hydrochloride ...



  , Glthyl, 2x .. w xasin-2-oni f, \ oxaIi n-2-onl 1J N.norborn11mthyl. b'ta-ano-N- 6- ac6toao'tam1à hydrochloride. norbornylm6thy1- norbornylimino 60 crotonamid, d1hydro-4-mthyl-2H- 1,3oxaeinane 14 N-11-éthlpropyl) b4t & -amino-N- 6- (1- IcioaceaSmidS7 (1-ethylpropyl) 'thylpropyl-crotonamide) hydrochloride 6dhydra-rdthy.w, t1, oxa $ in2one 15 N-fl.3-d1methylbutyl) blta- 6- aoetoacdtamide hydrochloride amino-N- (l., - (1 3-dimethy but d1m'thylbutyl) 1m1no) -J , 6-d1hydro-crotonamide k-methyx2H1, oxaw zin-2-one 16 N- (Ja, 4.7,7a-b'ta-am1no-N.

   6- tdtrahydro4 hydrochloride, t3W4? R? Atd (J..4.7.7a-t'trahr- méthano1ndan-2-yl) tranydro-4.7- dro-4.?-methano1naan- acetoacetamide mdthanoindrn2 .. 2ylim, noj, 3 , 6d1 yl) crotonamide h; ro-meth i 2H-oxa-oxalin-2-one 17 N-naphthyl-alpha-beta-aminohydrochloride 6-m4thyl-aedto. alpha-methyl-N- naphthylimino - ;. 6- acetamide naphthylcroton- dihydrate, 5-imethyl amide 21i1, 3..oxaxin2one 18 2-keto-N-ieo- 2-nm1no-N- 6- propyl-cyclo- hydrochloride isopropyl-1-isopropyliminopentane carbox- cyclopentane- 3,6dihydrot, S amide carboxamide trimÓthylaine-2H-1, J-oxa xin2one 19 Nt3mdthfixy b8ta-amino- 6 (e-propyl) -aceto-N- hydrochloride (;

  -m6thoxy- mthoxypropy11m1nl) - acetamide propy.) cro îidi ydro.45mdthyl tonamide H..1,3-oxazinone 20 N-sec-butyl-4- bta-am1no.N- 6-etc- bromo-3 hydrochloride -ceto- secHcutyl-4- butylimino-J 6-dihy- butyramide bromocrotonamide dro4bramomthyl2H 1,3axazin ane

 <Desc / Clms Page number 20>

 
 EMI20.1
 21 N-eyolopropyl * bAta amino-N- 6-ring- 3-oeto '-' 2 <- <! Tethyl "cyclopropyl-2. Propyl mino-'16-d1hßùro-butyram1de mxthylerote 4! 'Wd1mthYl-iH- hydrochloride 1JJ-oxa.

   amide 1 n-2-one 22 N-propynyl-2- b'ta-amino-ft- 6-propy- bu.tyl'-3-c <to "propynyl-2-nyliotino <-3.6 'hydrochloride * dihydro''4 "butyramlde buty7, axtan mdthylw-uty-2H l, amide oxagrn-2-ont 23 N-octan 2 yi-4 b't-amino-N- 6-0 hydrochloride and in chl0ï'o- '3-'c4to'-2 "octen-'2-'yl'-4 *' 2 -1-imino-3 0-dih droas chloro-3-càto-2-octen-2-yl-4- 2 - 1-iminO -,! 6-d1hYdro- methoxybutylamide chloro-2-metho- 4-chloroalkyi-5 m4thoxy- - xyerotonamide H-1,3oxaeir2 ona 24 N''cyclobut'Snyl "2 '' beta-amino-N- Hydrochloride of 6-ring-butoxy-3-keto cyclobutenyl-2-but "* nylimino-3,6-dihy octanamide butoxyocten-2-dro-4''pentyl'-5-butoxy-'2H" amide 1,; ioxazin- 2 ane 25 N-cyclooatyl. 2 ..

   S'-amino-M-'cycIo- '6-cu- ketocycloheptane- octyl-cyclonep- eloaet limi, no, 3,6..d3 carboxamide tanecarboxamide' nin 2rane lene-2H-1, J-xaI1n-2 -one
 EMI20.2
 EXAMPLE 26
 EMI20.3
 .sec-butvlimino-3.6-dihvdro-.ethvl-2H-1.3-oxazin-e.



  A suspension of 6-aeo-butyllmino-3 # 6 dihydro-4-tnethyl-2H-1,3-oxaein-2-one hydrochloride in
 EMI20.4
 methylene is stirred with excess silver oxide and filtered after 3 minutes. The solution of free oxazinone thus obtained
 EMI20.5
 The nude is immediately placed in an infrared recording apectrophotometer and the region between 5 # 5 and 6.1 microns is recorded. The spectrum reveals a characteristic peak of oxazinone at 5.7 microns (shift of
 EMI20.6
 0.1 micron at a higher wavelength due to neutral
 EMI20.7
 lization of the H01 salt), but no peak at 5.85 microns characteristic of the corresponding 3-eeo-butyl-6-methyluracil.
 EMI20.8
 



  The (solution is left in the machine and the same region is recorded at various time intervals. The 5.7 peak

 <Desc / Clms Page number 21>

 
 EMI21.1
 microns gradually decreases, while a peak and forms to 5 # 05 microns and becomes larger and larger, After 45 a, bare test the oxasinone peak almost disappeared, while the uracil peak is very large. After 1 hour and 15 May, there is no trace of the point of AI1andi. that the uracil points u reaches its maximum inetnaitè C.c4 shows the existence. similar to the relative instability of oxazinone. free according to the present invention.



  Other oxal1nonea. such as those cited below can. prepare by the same operating mode as in
 EMI21.2
 example 26.
 EMI21.3
 



  P.M.R. OxaziQ9 "'27 6-phenylm1no-, 3,6-d1hydro-4-methyl-2H-l ,, - oxa zin-2-one 20 6-8ec-butylim1no-bromo-J.6-dihydro-4. Mfohyl -2H-1 # 3-oxazin-2-ent 29 6-lsopropylirainO "5i" Chloïio-5 | 6 <dihy (Jro - /> t! Tëthyl-2H-'l, 3-oxazin "2-OM 30 6- norborny11minn-j, 6-d1hydro - m4thyl- 2H''l, 3-oxaxin <* 2''n <t 31 6..cyclohexylim1no -, - bromo - ,, 6-d1hydr0-4- methyl-2H-lJ -oxQzin-2-one 32 6-tert-buty11mlno -, - bromo - ,. 6-d1hydro-4- methyl-2H-l 3-oxazin 2-one 33 6-imino-3,6-dihydro 4-raethyl 2H X, 3 oxazîn-2-ont J / r 34 6- (2-mthylcyclohexy11m1no) -'- chloro.,. 6- d1hydro-4-m6thyl-2H-l, J-oxaJ1n-2 .... n1

 <Desc / Clms Page number 22>

   EXAMPLE 3,
 EMI22.1
 6 aec.butyl hydrobromide, iminaS bxoma, 6rd, ihydra! -Rdthyl 2H-l, 3-oxaain-2 ono # Has a solution of 11 parts of 6 aec-buty hydrochloride., Mïnaw, 6 di, hydrowt, methylNl , axeainw2ana in 45 milliliters of water,

   17.6 parts of bromine are added dropwise while stirring. A precipitate forms. After filtration, washing with water and with ether and drying, the solid material is obtained in an amount by weight of 8 parts. By recrystallization from acetic acid, 6.5
 EMI22.2
 parts of large white crystals melting 6.131-154; 0 en and de- component.



  Analysis; calculated for C9 "14Br2N2021 N 8.2 found 1 6.0%
The infra-red spectrum is similar to that of the starting material (sharp peak at 5.6 microns) with a peak at 15 microns attributable to the bromine atom in position 5. The bromine compound can be transformed into '-brama-
 EMI22.3
 secbutylw6, cathy, uraci3, e corresponding (M.P. 5.59r5 by the same methods described above as those used for the starting material. The bromine compound is less soluble in water than the corresponding chlorinated compound.



     EXAMPLES 36-40
The following products of Examples 36-40 are prepared as described in Example 35, replacing
 EMI22.4
 baaa..butylirnino, 6dihydro..mGhyl21 hydrochloride.



  193-oxasîn-2-one of this example by Molecular equivalents of the oxazinonea indicated to form the 5-brominated compound indicated *

 <Desc / Clms Page number 23>

 
 EMI23.1
 xern ", Q, 3:. ':.: L, ti 36 6-tort- Brorahydratt hydrobromide of 6 t> t * fc-butyJ,'. butyl m1no-J, 6-d1hydro-iaino 5bromo3,6 d3hydra lt -m "thyl-2H -; ..

   J-oXiI intererethylHwl, 3dxeinr
 EMI23.2
 
<tb> 2-one <SEP> in $
<tb>
 
 EMI23.3
 4 7 6-Phenyl-hydrobromide 6-ph'ny11m1no-imlno-3 6-dihydro-4- 5-bromo-1, 6-dihydro. * 4-methyl-H 1,3..axain .. thyl-2H-1,3-oxaein-2-one
 EMI23.4
 
<tb> 2-one
<tb>
 
 EMI23.5
 6-iso hydrobromide -1sop1-opYl-propy.imminu.3,6dihydr4 .mi o.5bromo.3,6 à.hydra.t..m3thyl-2H- ,, 3-oxa ain-tmthyl 2H1 hydrobromide. 3 oxaain-2 2 -one ('1 ne 39 6-methyl hydrobromide- 6 * methyllrai- lmtno-3,6-dlhydro-4- no-S-'bromo (3t6-dihydro-4-methyl-2H -1,3-oxazin-methyl-2H-1,3-oxazin-2-one
 EMI23.6
 
<tb> 2-one
<tb>
 
 EMI23.7
 40 Bzz hydrobromide.

   6 (103-damedimethylbutyliminoo) - thylbutyliminb) 5bromo 3, b 3,6-dihydro-4 m hydrobromide Sthyl- dihydrot, -mCthyl2Hw1,3
 EMI23.8
 
<tb> 2H-l, 3-oxazin-2-one <SEP> oxazin-2-one
<tb>
 
 EMI23.9
 EXAMPLE 41
 EMI23.10
 B sea butyiimino5ahloro-3 r6dihydro hydrochloride ... adthylw 2H-1, 3-oxazln-2-one
 EMI23.11
 A suspension of 15 parts by weight of hydrochloride
 EMI23.12
 6ea.butylicino, ô.àihydxo ... mthyi2H1,3oxAin 2-one drate in 75 milliliters of glacial nt4tl4u * acid is stirred
 EMI23.13
 at room temperature, while gaseous chlorine is introduced therein.

   The suspension first becomes more fluid, after which
 EMI23.14
 a thick white precipitate forms, which is filtered, washed with
 EMI23.15
 using acetic acid and acetone and dried * This gives
 EMI23.16
 12 parts of a material melting at 144-1500el Analysis: calculated for C9 "14C12N202 1 N z found 1 iolg%

 <Desc / Clms Page number 24>

 
The infrared spectrum of this product is very similar to that of the starting material (strong peak at 5.6 microns). It reveals an additional peak at 14.5 microns attributable to the 5-chloro substituent.

   The chlorine compound is
 EMI24.1
 transformed into the corresponding 5-chlorouracl (pu '. 152-153 # 500) as described above for the starting oxazinone by heating to a temperature above the melting point or by treating with dilute aqueous solutions of NaOH,
 EMI24.2
 of Na2CO3 # of NaOCCt or NaHCO. The solubility in water of 5-chlorooxazinone is about 8% by weight at room temperature.



     EXAMPLES 42-46 The products of the following Examples 42-46 are prepared as described in Example 41, replacing the hydrochloride.
 EMI24.3
 drate of faec..butylim, no 3rb.di.hydra.tmethyl2H. ,,, 3 oxaai.n 2-one with molecular equivalents of the oxazinonea indicated, so as to obtain the 5-chlorinated compound indicated.
 EMI24.4
 
<tb> Example <SEP> Oxazinons <SEP> of <SEP> desert <SEP> product},
<tb>
 
 EMI24.5
 42 6-isopropylisopropylimino-16- 1mino - chloro-J, 6-d1hydrodihydrc'-4-'nëthyl'-2H "4-methyl-2H-ll3-oxa8in-2K hydrochloride> n 8 1,3 -oxazin-2-one 43 6- Hydrochloride 6.4thylimino-ethyliniino-3,6-.dihy-. 5 chloro-3, 6-dihydro-4-roethyldro-4-methyl-2H-1, J- 2H -1, 3-oxazin-2-one
 EMI24.6
 
<tb> oxazin-2-one
<tb>
 
 EMI24.7
 44 Hydrochloride of 6.

   6-imino-5- imino-Jt6-dihy- chloro-J, 6-dihydro-4-methyl- dre-4-methyl-2H-l | 3 2H-1 # 3 oxacin-z-one hydrochloride
 EMI24.8
 
<tb> oxazin-2-one
<tb>
<tb> 45 <SEP> Hydrochloride <SEP> of <SEP> 6- <SEP> Hydrochloride <SEP> of <SEP> 6-norbornyl-
<tb>
 
 EMI24.9
 norbornyllmino-3 6 <lmino-5-chloro-3 # 6-dihydro- dihydro-4-m6thyl "2H 4-> m4thyl-2ri l f3-oxa in 2-one 1, 3-oxazin-2-one

 <Desc / Clms Page number 25>

 
 EMI25.1
 46 Hydrochloride dt 6-teft "6-t rt-bux butyliMiM-3,6-dihydM hydrochloride" imino-J-chloro, 6-dihydro-4w k.ra hyl, 2H, in methyl 2H l, 3-oxaain- 2 one
 EMI25.2
 
<tb> 2-one
<tb>
 
The compounds of formula 1 easily convert into uraoile, which is a very important field of use of these compounds.



   The transformation of the oxasinone derivative can be carried out, using the suspension of the oxasinone hydrochloride formed as described above in step 2 of the procedure.
 EMI25.3
 process and derived from the phosgenation of amincorotonsoid; or, when the oxazinone salt has been recovered in the form of crystals, this oxatinone salt can be mixed with a suitable inert liquid, such as water or an organic solvent, so as to form a solution or suspension.



   The suspension from either source is mixed with a sufficient amount of an aqueous base such as sodium hydroxide, potassium hydroxide, sodium carbonate, etc., to neutralize the solution. acidic salt at a pH of 7 or more and preferably to bring the pH to a value between about 8 and 10. This results in almost immediate transformation into a solution of the uraacil salt, which is in turn easily converted into the corresponding uracil, with the aid of an acid, such as sulfuric acid, hydrochloric acid or the like. Other acids, such as acetic acid, formic acid, etc. . are also satisfactory, as will be understood, but they are obviously more expensive.

   Uracils are isolated by filtration; or, . Since in some cases they are soluble in the aqueous medium, they are isolated by extraction with a suitable solvent, such as methylene chloride, ether or the like.

 <Desc / Clms Page number 26>

 
 EMI26.1
 



  Instead of proceeding with the formation of the urn soil, followed by an Ilc1ditic "'t: Lon, it is obvious that 1. Oxalinone: can be transformed directly into uracil by mixing with ox / lainone, into phose: Liquid, a quantity just sufficient of bise to neutralize the eele, that is to say, re 1 mole of bese for mole of salt dt oxnz1nono ,. With bitaceous laws fuiblea, such as sodium bicarbonate the use of an excess of bridle still makes it possible to recover the free urooil, both in the cns where the oXlz1none is transformed directly into urocil and in the eus where the soil of rUr'i'cuè is first formed, to then obtain uracil by tJcid1ft .. ontion, it was found that the yields of uracil, by rnp- port ru canposd of oxuzinone used, are almost qutin-
 EMI26.2
 fictitious.
 EMI26.3
 



  It emerges from the above that the demnndereee8 o, according to another aspect invented a globular process which can be carried out by an adrio do of separate or combined atodes and
 EMI26.4
 which constitutes a particularly effective method for In
 EMI26.5
 preporntion of urucilea from offset materials that are
 EMI26.6
 commercially available and relatively inexpensive.
 EMI26.7
 



  This globular process comprises the following steps: A 8 Reaction of a substituted océtoncétnmide of
 EMI26.8
 
 EMI26.9
 wherein R1- R2 and R. have the meaning given in formula 1 # with ltLlml'l1oniDc- so as to form a beta .. iiminocrotorwmide of formula

 <Desc / Clms Page number 27>

 
 EMI27.1
 Stage B: Reaction of beta-aminocrotonamide with phosgene
 EMI27.2
 so as to obtain a reaction product, and Stage C:

   Reaction of the reaction product of Step 8 with an inorganic base and, if necessary, an acidifying agent, to form a uracil of the formula
 EMI27.3
 
In a preferred procedure, the gosbal process described above is carried out with the preliminary step of preparing beta-aminocrotonamide from diketene and an amine.



   In a particularly preferred embodiment, the method consists of reacting diketene with an amine according to equation! :
 EMI27.4
   The acet @ acetamide is then reacted with ammonia in a suitable reaction medium, preferably using 1 to 10 moles of ammonia per mole of acetoacetamide, at a temperature between -30 and +30 for 1-10 hours, so as to form a beta-aminocrotonamide as follows $

 <Desc / Clms Page number 28>

 
 EMI28.1
 The acetoacetquide then phosgenes in an appropriate medium preferably,

     using 1 to 2% * phosgene per mole of aminocrotonamide, at a temperature of 40 ° C to 100 ° 0, for 1 / 2-6 hours, so as to form! * the oxazinone hydrochloride in the system, according to the following equation:

   
 EMI28.2
 The oxazinone derivative is then transformed at a pH of 9-10 with a base, such as sodium hydroxide, so as to form the corresponding uracil salt which in turn is transformed by treatment with an acid. , such as sulfuric lucid in corresponding uracil of formula
 EMI28.3
 
The class of 3-substituted uracils and 5-halogenated and 3-substituted uracils are particularly outstanding herbicides for the extraordinarily effective control of unwanted vegetation at economical doses.



   The above-described process for the preparation of uracils and, in particular, uracils of formula 4 is advantageous because it constitutes a rapid process and of high yield.

 <Desc / Clms Page number 29>

 for the synthesis of interesting uracils, starting from the only
 EMI29.1
 essential reagents of summer, amines of the phonogen and an alkali None of these starting materials have to be transformed with difficulty and in an expensive way into special intermediates, before being used in the process according to the invention .



   The following examples illustrate the transformation
 EMI29.2
 of oxasinones in corresponding uracils! either directly or via the uracil sol, while they also illustrate the overall process of preparing uracils via the corresponding oxazinone.



   These examples are also given purely by way of illustration and are not limiting. Unless otherwise indicated, the parts and percentages are given therein by weight.



   EXAMPLE 47
To a stirred solution of 10.9 parts of phosgene in 50 parts of tetrahydrofuran is added over 15 minutes at room temperature a solution of 15.6
 EMI29.3
 parts of beta-'amino-4! '- seo'-butylcrotonamide prepared as described in example z., in 40 parts of tetrahydrofuran.



   The temperature rises during the addition to approx. 50 C and a yellow suspension forms. This suspension is heated at reflux for 2 hours. The solid material present in the suspension at this time is 6-sec- hydrochloride.
 EMI29.4
 buty, i, asino r6d, hYdrowtmithylxH .. ,, .axaeintone. The suspension is then poured into 200 parts of a 2H aqueous solution of sodium hydroxide, while stirring. The solution obtained is extracted twice with 100 parts of methylene chloride, to remove organic impurities insoluble in alkalis.

   The aqueous fraction is then acidified.
 EMI29.5
 based on concentrated hydrochloric acid and JHteaf '

 <Desc / Clms Page number 30>

   6-butyl-methyluracil obtained by extraction 4 times with 100 parts of methylene chloride. Evaporation of the solvent gives 13.4 parts of uracil.



   EXAMPLE 48
A solution of 9.6 parts of beta-amino-N-phenylcrotonamide (prepared as in Example 3) in 40 parts of tetrahydrofuran is added to a stirred solution of 5.5 parts of phosgene in 25 parts of tetrahydrofuran in After 15 minutes, when the initial exothermic reaction has ceased, the mixture is heated to 63-67 C for 2 hours. It is then cooled and poured into 200 parts of a 2N aqueous solution of sodium hydroxide. After extraction twice with 150 parts of methylene chloride to remove impurities, the aqueous solution is acidified with concentrated hydrochloric acid.

   The product is isolated by extraction with 6 fractions each formed from 100 parts of methylene chloride, these extractions being followed by evaporation of methylene chloride. 7.5 parts of 3-phenyl-6-methyluracil are thus obtained, melting at 224-250 ° C.



   As indicated above, the compounds of formula 1 and, in particular, those which are indicated as preferred are effective herbicides. They exert a herbicidal action both against very stubborn weeds of the Cyperus type and against perennial weeds such as: Agropyron repens, Sorghum halepense and Cynodon dactylon. These compounds can be used on highly adsorbent substrates, such as railroad ballast, heavy clay soils and soils with a high organic content.



   This set of properties makes the compounds in question usable in cases where it is a question of combating

 <Desc / Clms Page number 31>

 weeds in general, for example in industrial land, railroad tracks and neighboring fields of cultivated fields.



   Some of the compounds according to the present invention also exhibit a selective herbicidal action in cultivated fields. By suitably choosing an oxazinone according to the invention, its dose and the time of its application, the seeds of annual * leafy weeds can be controlled. broad and narrow-leaved in crops of aspea, maize, jute, sugarcane, pineapple, saffron, peanuts, citrus fruits, alfalfa, strawberries, gladioli, stone fruits and turbites.



   By choosing the right dose and time of application, some oxazinones can also be used to control weeds growing in dormant crops,
The precise amounts of oxazinones to be used in a given situation will obviously vary according to the desired end result, according to the intended purpose, according to the plant and the ground one is present, according to the composition used, according to the mode of application, according to the atmospheric conditions present depending on the density of foliage and similar factors.



  Since such a large number of variable factors play a role, it is not possible to give a suitable application rate in all cases. Generally, the compounds are used at doses of about 0.28 kg / hr. approximately 28.35 kg / hectare. To selectively control weeds in cultivated fields, rates of 0.28 to 9.04 kg / hectare are generally used. A larger amount of active ingredient can be used to combat stubborn species growing under conditions.

 <Desc / Clms Page number 32>

 unfavorable.

   Economic factors, such as the inaccessibility of the area to be treated, for example in forest fire breaks, may also require the use of higher doses allowing less frequent treatments.



   The herbicidal compounds according to the present invention can be incorporated into compositions in the form of optionally wettable or soluble powders. In such compositions care should be taken that the diluents, surfactants and other pesticide adjuvants are pH neutral and particularly free from potential alkalinity. It is also important that the ingredients of the compositions be dry and that, during handling of the ingredients, preparation of the compositions and storage thereof, the presence of water is rigorously excluded.

   Diluents, surfactants and other adjuvants should also be chemically inactive to the extent possible, while they should also be reasonably free of active OH groups.



   In view of the foregoing considerations, particularly advantageous results are obtained with the following composition, in which the percentages of the ingredients are given by weight.
 EMI32.1
 
<tb> Active <SEP> ingredient
<tb>
<tb> (<SEP> oxazinone <SEP> salt) <SEP> 3.0-60 <SEP>% <SEP>
<tb>
<tb>
<tb>
<tb> Agent <SEP> surfactant <SEP> non-ionic <SEP> 0.1-10 <SEP>%
<tb>
<tb>
<tb>
<tb> Inert <SEP> diluents <SEP> 100 <SEP>% <SEP>
<tb>
<tb>
<tb>
<tb> substantially <SEP> anhydrous <SEP> q.s. <SEP> ad.
<tb>
 



   The expression “substantially anhydrous” means that the maximum proportion of water present is 1% by weight, relative to the weight of the oxazinone sol in the presence.

 <Desc / Clms Page number 33>

 



  Appropriate diluents for the so-called
 EMI33.1
 Optionally wettable8 dres are finely divided powdery materials exhibiting neutral * or slightly acidic surface reactions, such as synthetic silicas, earths. diatoms and acid clays of the kuolinite type. Examples of diluent tala include
 EMI33.2
 produced referred to as "Hi-Sil", "velite" 209, Continental clay, Burnat clay and nrgilr P1k.,. Pet <k 9T66, Other diluents which can sometimes be used are inert vegetable flours, such as redwood flour, walnut shell flour, etc.



   When these diluents are to be used in the preparation of herbicidal powders, the active ingredient is
 EMI33.3
 preferably present in amounts between bzz and 15% # '? the remainder consisting mainly pure one or more of the abovementioned diluents, When the composition To be prepared
 EMI33.4
 is a soft powder, the active ingredient can be present in amounts of between 10 and 85% approximately, the remainder being constituted by a diluent, except that the composition consists.
 EMI33.5
 still holds about 0.1 to 5% or 106 of one or more of the tene1o-oct: Lfa agents described below.



  The ngenta tena10-hct1fe for these compositions can be cationic or nonionic ionic type, although unionic surfactants are preferred and nonionic surfactants are highly preferred.
 EMI33.6
 It is important that anionic surfactants are not strongly alkaline.

   In view of this limitation,
 EMI33.7
  Tenioactive cents, such as single olkylaryl tallow salts, of IUlfonnt8. petroleum and fatty alcohol sulfate salts can be used. A list of these

 <Desc / Clms Page number 34>

 surfactants is given in the book "Détergente and
 EMI34.1
 Emullifierl Up-to-data, 1962 ". By John W, NoCutchéont Ino, As other onionic surfactants which can be used, mention may be made of the salts of d101kylic esters of eultolUAC1netel and of acid entera. Ali, phatiquea des ethyl acids ..



    In a certain case. the free acid can also be used advantageously rather than the salt.
 EMI34.2
 



  Among the very pre-6161 nonionic tenlio-ootits agents, mention may be made of the uliphutiquee esters of polyethylene glycol and the ethera and thioether of polyoxyethylene. Another nonionic compound are ulkyl-ph6noxypoly'thylàneoxy. ethunclet such as nonylphenyl derivatives of ethyl oxide.

   lenet trimithylnonylpolydthylene glycol ethers, polyethylene oxide adducts and crane acids and rosin, eatera polyethylene oxide adducts of crane acids and crane acids rosin and
 EMI34.3
 The adducts of long-chain alkyl mercuptane with ethylene oxide. Particularly preferred are polyglycolic ethers in which the terminal alcohol groups have been esterified by large acids, such as acids. lauric, oleic, palmitic or stearic.



   It is often also desirable to use the compounds according to the invention as soluble solids. In such compositions, there is 75-95% active ingredient with the remainder being one or more of the tenaio agents. - aforementioned assets.

   To prepare these compositions, the diluent
 EMI34.4
 and / or the used surfactant are mixed with the active ingredient in the usual manner in a tape mixer or the like, after which the mixture is ground. As indicated above, care should be taken to exclude the mixture. 'humidity,   @

 <Desc / Clms Page number 35>

 
 EMI35.1
 Others dare @ teneio-actitl dispersant, such as low viscosity methyloellulose or lipoeulto-
 EMI35.2
 substantially neutral sodium notes are also used.
 EMI35.3
 bloop in particular in the compositions in poudra mou11l.1. '
 EMI35.4
 according to the invention.
 EMI35.5
 The herbicidal compositions according to the present invention
 EMI35.6
 
 EMI35.7
 tion may also contain two or more than two., 1a of exa.

   titanium, It can also contain other known herbicides in addition to oxuzinonea, so as to form the composition @ exhibiting certain avuntugee pure compared to those of constituents
 EMI35.8
 individual. Among the known herbicides which may be mixed
 EMI35.9
 qux compounds of formula Ip include the following 1
 EMI35.10
 Ureas will substitute.
 EMI35.11
 



  3 - <(? 3 Iwdichiaraphnyi) -1, 1-diraethylurea 3- (4-ohlorophdnyl) -lpl-dimethylurde 3wphdnylwl, i.dimthy, urea wf 3,4-d.chloraphdnyl.3wm3thaxy ,, ldimdthyiurde 3w f, .. chl, csraphny. ) .. 3..m3thaxy.1, lwdimtthylurEia 3wf 3, 4-diohloraphdny, -l, nwbutyl.,. Methylurde 3wf 3.4dichloraphdny. ) i.mthoxy3.methylureas 3- (4-chlorophenyl) -l-methoxy-1-methylurei 3 (3, -d, ch.araphdnyl 'l, l, 3trimthyl, urda 3- (3 # 4-dichlorophenyl) -l , l-diethylurae 3w f, wah.araphânaxyphényl i 1 ,, ldi.mbthy7.ursa These ureas can be mixed uux oxatinonte itself the invention in proportions ranging from 114 to 411 respectively, the proportion expressed being IS2 A 211 * Substituted triazlnes. 2wchlarat, reach dthy, cm, no, triaine '..ch, ara.t + thylunino 6..3, eopropy.ani, na, tria:

  ine

 <Desc / Clms Page number 36>

 
 EMI36.1
 2-chloro-4tO-bie (methoxypropyloMino) -B-tria <tine "mdthacy 4, wb, e (iaaprapy.amina ', triaatne 2wdidthyxnmina twiaoprapy.s ctam, dothaxy, tsiasina 2 isopropylnethyl -µtino-oxy-metoH-metoH-meto trloiint cndthylavarcpta-4rbie (iaapropylanina jw, trieaine 2-m'thylm.rcapto-4,6-bi. (ethyl.m1no) -trl'llne 2..mdthylmdrcapto-dthy.emina.w6.iaoprapylamino, tr.asins 2- methoXY-4,6-bie (ethylamino) -trluzin 2-methoxy-4-dthylumino-6-isopropylamino - triaxine 2..chl.oxo..tr, b..bia (iaopropy.umino g.triaxina These tria groins can be mixed with any compound according to the invention in proportions of between H4 and 4 <1, respectively, the preferred ratio being 1 $ 2 to 281.

   
 EMI36.2
 Phenol
 EMI36.3
 Dinitro-o-AlQ-butylph6nol and its salts Pentcichlorophenol and its salts
 EMI36.4
 These phenols can be mixed with the compounds itself.
 EMI36.5
 vunta the invention dune the proportions from 1810 to 2011 roopecti vement, the preferred ratio being from IS5 to 5 he Acids ctlrOUe8 Mt their derivatives
 EMI36.6
 The following carboxylic acids and derivative may be mixed uux compound according to the invention in the propor-
 EMI36.7
 indicated in A.

   2,3,6-Trichlorobenzo ± qua acid and unsalted rr5rbtëtrrchlorobaxrotua acid and uncelled Mathoxywr5,6trichlarobensaQua acid and its salts Tnthoxyw acid, r6diahl.arobanzosua and its salts 3mina acid, 5-dichlorobnxaiq, ua acid and its salts 2-nitro-dlchlorobensoic and its such Acid 2.mdthylr, â..diohlorobenxoqua and its ealsl Acid 2, trwdi, chlorophdnnxyrcdtiqua and aee such and *% tors

 <Desc / Clms Page number 37>

 
 EMI37.1
 2, .5-tr1chloroph'noXYQc'tic acid and its sois and "t'I'I Acid (2-ffl6thyl-4-chlorophéno5cy) ocôtiqut and its salts and entera Acid - (2, k, 5 trichloroph3noxy) propionic and its salts and avatar (4, â txl.chlarophdnoxy) ethyi-2, xdich7, oropropionate! (2Idichlorophroxy) butyric acid and its that and esters T ,, .. (.. m6thy1.4achlorophbnoxy) butyriqua and salts and esters 2,

  3 6-triehlorobenzyloxyproponol Mixed in a ratio of is16 to gtlp, preferably a ratio of 1: 4 in 4: 1.



  , 206-dichlorobentonitrile Mlungé in a ratio of 1! 4 to 491 # preferably a ratio of 1: 3 to 3: 1.
 EMI37.2
 



  C, Trichloroucetic acid and its salts
 EMI37.3
 Mixed in a ratio of 1: 2 to 25: 1, preferably a ratio of 1: 1 in Oslo
 EMI37.4
 D, 2,2-Dichloropropionic acid and its salts
 EMI37.5
 Mixed in a ratio of 1: 4 to 6: 1, preferably
 EMI37.6
 a ratio of 1: 2 to 4: 1.
 EMI37.7
 



  E, N, N-di (n-proPY1) ethyl bult NtN-dî (, n-prop ,, l) ja-propyl thiolcorbum N-6thyl-N- (n-butyl) ethyl n-turbumote N- ethyl-N- (n-butyl) thiolcarbnmste de n.propy.1 1.All'ngêe in a ratio of 1: 2 to 2411 # of pr't4re, ... this ratio of 1: 1 to 1211 #, N-ph6nylcurb ± 1mat. aopropyl.



  N- (m-chlorophenyl) ct4rbumate c1'1.opropy18 N- (m-chlorophenyl) corbumate 4-chloro-2-butynyl Mixed at a ratio of .t2 6 2411, preferably a ratio of U1 To 1281. a, 2,3,6-Trichlorophenyloketic acid and its salts Mixed in a ratio of 1:12 to dilp, preferably a ratio of 114 to 411.

 <Desc / Clms Page number 38>

 
 EMI38.1
 H, 2wchloro.N, N. ialaaitamide Maleic hydrazide
 EMI38.2
 Mixed in a ratio of 1 * 2 to 10: 1, preferably a ratio of 1 to 5 if Inorganic salts of mixed inorMniauee-orMniouea.



   The following salts can be mixed with oxazinones in the * proportions indicated} A, Calcium propylorson
 EMI38.3
 Diodium methylorethyl-doddcylammonium methyloroin dimethyloroinic acid Mixed in a ratio of 184 to 4tl # preferably 112 to 2: 1.



  B. Sodium arsenite
 EMI38.4
 Mixed at a ratio of US to 40tl # preferably 114 to 25: 1.



    C, Lead arsenate calcium arsenate
 EMI38.5
 Mixed in a ratio of 150H & 600: 1, preferably a ratio of 100: 1 & 400: 1.



  D. sodium tetraborate hydrate, granulated sodium metuborate
 EMI38.6
 sodium pentmborate polyborchlorate ore unrefined borate, such as borascu
 EMI38.7
 Mixed at a ratio of 3 µl to 1t30s, preferably a ratio of 6: 1 to 1000: 1.
 EMI38.8
 



  Ammonium hiacyanrta Mixed in a ratio of 1:10 to 20: 1, preferably a ratio of.



  F. Sodium chlorate

 <Desc / Clms Page number 39>

 
 EMI39.1
 Mixture in a ratio of 1 1 to 40: 1, preferably 1'3P. port of 211, 20: 1.



  00 Ammonium Sultumute Mixed in a ratio of 1: 1 to 10081 # preferably a ratio of 1: 1 to 50ils & Urge b2Cblgidge grgiinlgâu # These organic herbicides can be mixed with these in the proportions indicated and A, D1bromufe of? T6 -dihydyo - '(4At6A) "dipyï'ido <' (lt8't 2 ', 11.0) pyrQmn1um Mixed in a ratio of lt20.16tl # preferably an intake of 1 su to 5 35 ,, se 3wcmina ,, 2, ttriwo, o Mixed in a ratio of 1820 To 2011 # preferably a ratio of 115 5 A 51 C, 3,6-endoxohaxohydrophthulic acid Mixed in a ratio of 183 To 20.1. preferably a ratio of 1: 2 to 10: 1 , D, Hexnohloroucétone Mélungâ in a ratio of usa to 16: 1, preferably a ratio of 111 A:

  1, Eo Diphnylacetonitrile N, N-dimethyl-a.a-diph6nylac'tomide N, N d. n-prapyl. 2, 6..d, nitro.r trit'iuoroadthy, aniiina N, N di, .npropyl2, b dinitraw4methylcniline Mixed with a ratio of 1110 & 30110 of lenderer a ratio of 11 'to 20sl, F . a (, 4diahlarophdnyll Omâthylwiaopropylphamphoro 13midothiute 2 ,,, 6tâtruchiorotér6phta.ots of dimethyl Mdlongée dune a ratio of 1 4 4 2081, preferably a ratio of 11 3 & 15 si.

 <Desc / Clms Page number 40>

 
 EMI40.1
 



  O. 2,1. -nitrodiph'11yl ethep Mixed therefore a ratio of 1810 to 3011o, preferably a ratio of 115 to 20119 substituted gracils These dfoxatinonse salts can be mixed with substituted uracils in the proportions indicated below. Toua.
 EMI40.2
 the reports indicated are by weight 1.

   Processes for the preparation of the cited uracils are described in the applications.
 EMI40.3
 of patents filed in United States of America under lni 23 # 952 # on October 29, 1962, under nt 241ol4lo on November 30, 1962, under born 21, d9t) on September 6, 1962, under n '232.311 on October 22 1962 and we nl 217,521, read August 17, 1962) A. 3-cyclohexyl-6-methyluracil 3''cyclohexyl'-6-'ëthylurocile 3-cyclohoxyl-6-ooo-butylurne 3-norbornyx.b methyluraaile
 EMI40.4
 3-cyclopentyl-6-methyluracil
 EMI40.5
 3 "cyclohexyl'-6'-i eopropyluro cil e Mixed in a ratio of I14 to 4SI preferably a ratio of 1: 2 to 2:

  1, B, 3ayolohexyl-5 triméthyineurnai.la 3-see butyl "'5,6¯i tpimethyleneuracilo 3 ieopropy., 6.tr, mothyineuraaile 3-isopropylm5o6-tetramethyleneurocile 3wieorropy .., ôpentombthylangneur of Aaitne.e report 6 it preferably has a ratio of 184 to 4SI * C. 3-cyolohexyl-5-bromourocil 3aya.ohexy ....

   ahiorourucil 3 iaopropyi ... bramouraaile 3-6ec'-butyl'-5 "bromourûcile
 EMI40.6
 3-sec-butyl-5-chlorouracil

 <Desc / Clms Page number 41>

 
 EMI41.1
 Mixed in a ratio of 196 to 6slo preferably a ratio of ls2 to 2il, "ilopropyl-1-trichlorom'thylthio -, - bromo-6-mthyl-uracil 3-cyclohexyl i fcrlchlorora (5thylthio-5-bromO'- 6- ethyl uracil 3-sac-butyl-l-Hcetyl-5-brorao-6-fflâthylurucil 3-i8opropyl-l-acetyi-5-brcKno-6-m6thylurooilt 3-iDopropyl-l-trichlorom'thylthio-5-chloro- 6-m4thy1- uracil Mixed in a ratio of 1: 4 to 4: 1, preferably a ratio of 1: 2 to 2 µl,
 EMI41.2
 Bu, 3-86c-butyl-5-bromo-6- 6thylurQcil t 3-isopropyl-5-bromo-6-methyluraoile 3-eec-butyl-5-ehloro''6''mëthylurooil 3-phny1-S-bromo- 6-mJ1uracil.



  ) - (1,3-dimethylbutyl) -, - bromo-Ó-m'thYlur, oil.



  3- (1-ethylpropyl) -5-chloro-6-ciethyluracilt 3-cyclohexyl-S-bromo-6-m6thylurac111 Mlun6s in a ratio of U4 to 4, lender in a ratio of 1: 2 to 2: 1.



   So that the interest of the present invention in the herbicidal field appears more. the following illustrative examples are still given.



   EXAMPLE 49
 EMI41.3
 6-Norornylm'tbyll # ino - ,, 6-Iy4't11 hydrochloride.



  2H. l, xu xin..2drie 80% ntol'ate dtr poyxhyl8 e glycol
 EMI41.4
 
<tb> "Hi-Sil" <SEP> 15%
<tb>
 

 <Desc / Clms Page number 42>

 The ingredients are mixed and crushed in a grinder
 EMI42.1
 z marteoux, until the size of the particles of senate * element all the active ingredients is less than 50 microns *
This wettable powder is used to control annual weeds with narrow and broad leaves that grow around telephone towers or poles and
 EMI42.2
 punneuux road signs.

   An application of !!, $ 6 kg of ingredient act3,! '/ Hacbuo l,' liters of water allows com. thresh the following herbs together 1 Digitrriu sp., Echinochloo sp., Rudbeckia, Mullogo vertieillate and Stellaris sp.
 EMI42.3
 6.tett-butyllmino-5-bromo- 3,6-àlhydro-4-methyl-2H-1,3-oxaz1n-2-one soto% hydrobromide
 EMI42.4
 
<tb> Louryl <SEP> sodium <SEP> sulfate <SEP> 0.6 <SEP>%
<tb>
<tb>
<tb> Lignin <SEP> sulfonote <SEP> of <SEP> sodium <SEP> partially
<tb>
<tb> or <SEP> background <SEP> 1.0 <SEP>%
<tb>
 
 EMI42.5
 Montmorillonoi non-swelling calcined clay from (Pïkes Peak cl;

  .- y) 18, / t 1 "A wettable powder is prepared by Mixing the
 EMI42.6
 component and then multiplying them until and substantially all of the particles are less than 50 microns in size.
This composition is used at a dose of 22.6 kg of active ingredient per hectare in 378 liters of water, to control the weeds which grow on the ballast of railway tracks and around the storage tanks. produced oil * An excellent result obtained in the fight against
 EMI42.7
 the weeds following the test Agropyron repent # Digitarin op ## Potentille on serina, Sorghum ha18pen .., yrencxye, Chryaanfche- num leueanthenum Erigeron cunndeneia, Chinese scrub,

   maple and willow

 <Desc / Clms Page number 43>

 
 EMI43.1
 At 4086 of 3309 Ksi of active ingredient per hectare per contact treatment, excellent results are obtained in weed control. , root * proton * such as weeds of types Convolvulus and
 EMI43.2
 Cirl1um arvense.



  EXAMPLE 51.
 EMI43.3
 



  6-1eopropylim1no-5-bromo-3,6wc1 hydrobromide + tndthyl "Ei7,, woxaei, nroria 600%
 EMI43.4
 
<tb> Luuryl <SEP> sodium <SEP> sulfate <SEP> 0.6 <SEP>%
<tb>
 
 EMI43.5
 Sodium Lignin Sulphonute $ 200
 EMI43.6
 
<tb> Clay <SEP> with <SEP> kaolin <SEP> 17.4 <SEP>%
<tb>
 
 EMI43.7
 These ingredients are mixed and raioropul truths until all the particles have substantially a ca-
 EMI43.8
 free less than 50 microns. The mixture then remixed until it is homogeneous.



   This wettable powder is used as a general herbicide on industrial land and ballast of roadways. A dose of 11.3 to 22.6 kg of active ingredient per hectare in 378 liters of water gives excellent results
 EMI43.9
 in the control of the following weeds flowing 8 Solidago sp., Oenothera, Phytolacoa americana, Chryaonthemum leucanthenum, Xanthium, Potentilla anaarira, Digitaria and Eragroctis pect1nace ..



   A dose of 22.6 kg of active ingredient per hectare in 189 liters of water provides excellent control of weeds of the Cyperus type.



     EXAMPLE 52
 EMI43.10
 6-aec-butylimino hydrobromide 5 browo-3 6- d, hydrotmthyl2H.1,3-oxoxin .on 95%
 EMI43.11
 
<tb> Eeter <SEP> of <SEP> polyethylene <SEP> glycol <SEP> of fatty acids <SEP> <SEP> and
<tb>
 
 EMI43.12
 rosin ucid solidified with urea $ 5
The ingredients are mixed and crushed, after which they can be mixed with water, with a view to rapid application as a spray solution *

 <Desc / Clms Page number 44>

 
 EMI44.1
 This composition is used at the rate of 1.13 to 2.26 kg of active ingredient per hectare in 113,

  4 suitable for controlling annual weeds in sugarcane fields near emergence * Directed spraying destroys the following seeds and weeds)
 EMI44.2
 Dig1torio ap.

   Echinochloa. sp., Amaranthus and Chenopodium ul. bum,
EXAMPLE 53
 EMI44.3
 6-Norbornylm6thylimino-3t6- dihydro-it-methyl-2H-1,3-oxuzin-2-one hydrochloride 40%
 EMI44.4
 
<tb> Lecithin <SEP> from <SEP> soju
<tb>
 
 EMI44.5
 Substantially aliphotic mineral oil with
 EMI44.6
 
<tb> low <SEP> viscosity <SEP> pure <SEP> example <SEP> kerosene <SEP> or
<tb>
<tb> oil <SEP> dieael <SEP> 57 <SEP>%
<tb>
 
The oily suspension is obtained by first grinding the active material and mixing it with the other constituents, while stirring, or else by mixing all the constituents and then grinding them with sand or balls, to give the particles of the constituent active the desired caliber. The product is suitable for dilution with oils to form an oily spray product.



   This composition is diluted with 302.4 liters of a herbicidal oil such as "Lion Herbicidal Oil No 6" and applied at the rate of 13.56 liters of active ingredient per hectare to combat, in general, all the weeds which grow along the palisades or barriers of protection against cyclones, as well as on the ballasts of the railway tracks.



   A good result is obtained for several months. The following weeds are effectively combated 'Agropyron repens, Bromus secalinus, Panicum capillare, Diodia teres and Datura stramonium,

 <Desc / Clms Page number 45>

 
 EMI45.1
 XlPi 5
 EMI45.2
 6 ayolahaxyl a, na rahl, ora hydrochloride, 6. dlhydro i | -ciethyl-2H l, 3 ox zln-2-> on 900% Alkyl nyphtulfene aultonote de Na 200 Mdthyl cellulose low viscosity 00)% Attapulgite clay 707 0
 EMI45.3
 These conditions are reduced and micropulved as long as the urocillin particles have the size ... a diameter of about 10 microns, after which they die.

   Again the conatituuntet This composition allows to fight ett1cuoem, nt, nvunt and uprèa entergence, ll'is M4UVMiOig following herbs @, to dee endowed with w, 52 kg / heotoro! 1 Di: 1turilA ope # Avenu tutua, Bruse1ca kaber, oltallo vulgure, Alopteurue and Chénopodim olbmo z
 EMI45.4
 6 aec-butylimino-5-chloro hydrochloride 3 | 6 dlhydro-î 4-methyl-2H-1,) - oxuz1n-2-one io 0 ticelitet, 209 10 i Clay k / Jo11nite (acid) go%
 EMI45.5
 The active ingredient and the ncolite # are mixed and crushed with a murteuuxi grinder until the mixture is uniform and until the size of the ua.i.totul1t '
 EMI45.6
 of particles is less than 50 Will negate the concentrated powder
 EMI45.7
 obtained is then md.rëa J clay of the kpolinite type and the melunge is dâsugg1om6r4 in an apparatus such as that of "named tI !!:

  ntolet.r ", so as to obtain a uniform powder and
 EMI45.8
 homogeneous flowing like a fluid,
 EMI45.9
 This composition is used to combat medi-
 EMI45.10
 langea of perennial and annual weeds growing around farm buildings. Excellent results can be obtained on the following weeds .., using rates of
 EMI45.11
 17 kg of active ingredient per hectare! Lepidium, Br ... 10. knbor # Arctium, Agropyron repens and Digituria sp,

 <Desc / Clms Page number 46>

 
 EMI46.1
 mrouli â-6
 EMI46.2
 6 µec-butyllmino-5-brotno- hydrobromide.



  J.6-dihydro-4-methyl-2H-.) - oxozin-2-onl,. 25% Granular tittopulgite clay (gr (nulometry8 2.3c'-l, 3 mm) 75%
 EMI46.3
 A granular composition is prepared by suspending the active ingredient in acetone and pulverizing the solution obtained with the otepulg1te granules, while stuck together are stirred * The granules obtained are then dried *
 EMI46.4
 These granules are applied by hand to tufts of grass. undesirable. growing in cultivated fields, a good result is obtained on the following grass, using a dose of 22.6 to 33.9 kg of pure active ingredient hecta-
 EMI46.5
 re t Paspolum dilatatume

 

Claims (1)

EMI47.1 Bmclg6, rIgN8 # 1.- As a new compound a, lis ogaiinonta responds to the following formula: EMI47.2 in which R1 denotes hydrogen, an alkyl radical containing 1 to 10 carbon atoms, substituted alkyl containing 1 to 8 carbon atoms, aryl containing 6 to 10 carbon atoms, substituted phenyl, aralkyl containing 5 to 13 carbon atoms , oral- EMI47.3 substituted kyl containing 5 13 carbon atoms, alkdnyl containing 3.6 carbon atoms, alkynyl containing 3 to 8 carbon atoms, cycloulkyl containing 3 to 12 carbon atoms, cycloolkdnyl containing 4 to 12 atoms. carbon, cycloolkyl alkyl containing 4 to 13 carbon atoms, cyaloalkArrr1 alkyl containing 5 to 13 carbon atoms, substituted cycloalkyl cy- EMI47.4 substituted cloulkenyl, (substituted cycloolkyl) alkyl containing 4 to 14 atoms. carbon or (substituted cycloalkenyl) olkyl containing 5 to 14 carbon atoms; R2 denotes hydrogen, chlorine, bromine or a radical EMI47.5 methyl, ethyl, n-propyl, isopropyl, n-butyl, trabutyta, tsrt-butyl, methoxy, ithoxy n-propoxy, 1.opropoxy, nbutoxy, sac-butoxy or tert-butoXY8 113 denotes an n, lyl 1 to 5 radical carbon atoms, chlorine * u, 1 to 1 carbon kyl or 4 1 * 4 atom brorooolkyl. of carbon; EMI47.6 Rg and R can be united to form a "(cH2) n- group in which n is a positive integer of 3 4 5, as well as the salts of these compounds. <Desc / Clms Page number 48> 2.- Compounds according to claim 1. characterized in that R1 has the meaning indicated above and denotes something other than hydrogen 3.- Compound according to claim 2, characterized in EMI48.1 that R3 is a methyl radical, provided that when n2 is hydrogen, R1 is a radical other than methyl or ethyl. 4.- As new compounds, the compounds of formula! EMI48.2 EMI48.3 in which R denotes a group DJ "ky18. contains 1 to 10 carbon atoms, substituted alkyl containing 1 to 8 carbon atoms, aryl containing 6 to 10 carbon atoms, phenyl sub- EMI48.4 etitudo aralkyl containing 5 to 13 carbon atoms # atalkyl substituted containing 5 to 13 carbon atoms, olkenyl count. nant 3 A carbon atoms, alkynyl containing 3 & 8 carbon atoms, cycloalkyl containing 3 to 12 carbon atoms # cycloulk6nyl containing 4 to 12 carbon atoms, oyoloalkyl ah kyle containing 4 to 13 carbon atoms, cycloolkenyl alkyl EMI48.5 containing 13 carbon atoms, ayolaelkyld substituted cy- cloalkdnyle substituted (cycloulkyl substitute) alkyl containing 4 to 14 carbon atoms and (cyclolkenyl lubeti.tu6) ulkyl aan holding 5 to 14 atoms of et-rbonel R2 denotes hydrogen, chlorine or bromine, <-and R3 is a methyl radical, R2 and R3 possibly being combined to form a radical - (CH2) n-. in which n is a positive integer between 3 and 5, it being understood that when EMI48.6 R2 and hydrogen, I is not methyl or thY18. thus the salts of these compounds, <Desc / Clms Page number 49> EMI49.1 $ # * 6-aeo-butyli hydrochloride <! Tino-3''chloro <-3t6 * dihydro <* 4-mdthyi il, 3 oxuzin-2one, 6, "6. * aec-butylimînc hydrobromide> -5- beomo.3 # 6.deydrc) - r.mSthyl H.1, âXazinwone, $ 7 - â..norborny.i.minor3rôdi.hydrodxhyi 2H l, 3 oxrzin-2.one hydrochloride. and, "Bron-hydrate of 6 ... norbornylmethy11mino - ,. btomo-3.6- dihydro4mGthyl2tLl, 3 oxrzin2..one, 9t- Bw.ethyl.propylimino-5-broatc hydrobromide, b .. dihydro-4methyl-2H l, .oxfxinone. 10, - 6- (1,3'-DiethylbutylitnjLno) -5''cM.oro "rb..dihydro.l + .. mdthyl2iI Z, 3oxuxiu.2one hydrochloride. 11, - 6.ieopropylimina5broso3,6..dihydro 4mthyx2H1, 3axxin2a e hydrobromide, 12, - 6 "tert-butylimino .So-3,6.dihydrate mtthyl2Fi, 1,3.doxrzin-2..one hydrobromide. 13, B.phtnylimino-bracc hydrate, 6.dihydra methyl, 2H-1, 3oxrazin2ong, 14. "'6 t3o hydrochloride, r.ir'uwtetrahydro4, iéthnrio, n- d <' n'-2-ylimino) -3 r dihydro.t ,, .. methyl.2H 1, 3-oxa8in-2-on, 15, - Dromhydrate de 6cyG3.ohdxy.imi, nobromo3, dihydyo 4.mdthyl.2N.1, 3oxz, nx.ane . 16, - 6-CyclohexyliMino-4t5-triNethylenw- 3, .. di.hydro..2N 1,, 3 oxrzin2wone, 17 hydrochloride, 17.- Process for preparing a compound of tonw1e, 1 EMI49.2 EMI49.3 dt-ne which Ri denotes hydrogen an alkyl group EMI49.4 containing 1 to 10 carbon atoms, substituted alkyl <Desc / Clms Page number 50> EMI50.1 containing from 1 k 8 otarbone atoms, nryl containing 6 to 10 carbon tomos, phdnyl substituted urvlkyle containing 5 & 13 tomes of tSralkyl substituted cirbones containing 5 to 13 carbon atoms, ikenyl containing 3 to 0 curbone atoms , al.- kynyl containing 3 to 6 atoms of ourbone, cyclonlkyle containing 3 to 12 carbon ototnea, cyolonlkenyl containing 4 to 12 corbonet cyc1o'lkyl tJ1ky1e atomea containing 4 to 14 carbon utomes, cyoloilkÓnyl ulkyle contenunt 5 z 13 carbon atoms, cyclotilkyla subatitu4 # cyclo dk3nyle subetitude (cycloilkyl EMI50.2 substituted) ulkyl containing 4 to 14 carbon atoms and (cyclo- EMI50.3 11; substituted 6ny1) caikyl containing z 14 carbon atoms; R2 denotes hydrogen, chlorine, bromine or a methyl, ethyl, n-propyl, isopropyl, n-butyl, eec-butyl, tert-butyl, methyloxy, ethoxy, n-propoxy, iaopropoxy, n-butoxy, EMI50.4 sec-butoxy or tert-butoxy; and EMI50.5 R3 denotes an ulkyle group containing 1 to 4 carbon atoms, chloroulkyle containing 1 to 4 (curbone and bromoulkyle atoms containing 1 to 4 corbonel atoms R2 and R3 which can be linked, so as to form a cluster - (CH2) n - in which n is a positive integer from 3 to 5 # characterized in that s (1) one fnit reacts a substituted ketoooetum1de of formula 8 EMI50.6 EMI50.7 uvee ammonia to form a substituted β-aminocrotonem1de of formula 1 EMI50.8 EMI50.9 dima which R1 'He and R have the 81gnit1cat1ons' 1nd1qu4 .. longer EMI50.10 up and <Desc / Clms Page number 51> EMI51.1 (2) the bltu-uminocrotonumide is r'uS1r with phosgene so as to form the oxoz1none compound * in question in the Process for the purification of a compost of mule iron OXal1none EMI51.2 EMI51.3 of which Ri denotes hydrogen, an olkyl radical coint "lnr..nt 1 to 10 carbon atoms, substituted alkyl containing 1 1 E3 carbon atoms, nryl containing 6 to 10 carbon atoms @ substituted phenyl, arulkyl containing 3 13 carbon substituted tirulkyl containing 13 carbon atoms, s1, lryla containing 3 to 8 carbon atoms, alkynyl containing 3 to 9 carbon atoms, cyclotdkyl containing 3 to 12 carbon atoms, cycloulkyl containing 4 to 12 atom. carbon, cyclo-alkylalkyl containing 4 to 13 carbon atoms, cycloulkenyl olkyl containing 5 to 13 vtomo8 of curbone, substituted cycloulkyl, substituted cyclotllk6nyl, (substituted cyolkyl) ulkyl containing EMI51.4 4 to 14 atoms of curbone or (substituted cycloulkenyl) ulkyl EMI51.5 containing 5 to 14 volumes of curbone. reliability in quten 1 "I: l.t {1) react a u c & toncetum1de of formula EMI51.6 EMI51.7 with omonipc, so as to form a bltu-ominocrotonu- EMI51.8 mide of formula EMI51.9 EMI51.10 wherein Ai has the meaning given above, and (2) this bbtti-aminocrotonomide was reddened with phoege "ne, to form the toxoid compound in question. <Desc / Clms Page number 52> EMI52.1 19000 Process for preparing a composition. ' o.1 no. of EMI52.2 formula EMI52.3 EMI52.4 where R 1 denotes hydrogen. a Hlkyle radical containing 1 to 10 carbon atoms, substituted alkyl containing 1 to 8 curbone atoms, ury1e containing 6 to 10 titomtis of gold. substituted phenyl bonts vrulkyl containing ', 13 carbon atoms, substituted urulkyl containing 3 to 13 carbon atoms and nlkenyl containing 3 to 8 carbon atoms, alkynyl containing 3 to 8 carbon cyclorlkyl containing 3 to 12 carbon atoms, cycloulkenyl containing 4 At 12 carbon atoms, cycloalkyl olkyl containing 4 to 13 carbon atoms Cyclovlk4nyl nlkyl containing 5 to 13 carbon atoms, substituted cycloalkyl, substituted cycloulkenyl, (substituted cycloulkyl) olkyl containing 4 to 14 carbon atoms or (cycloulkenyl substituted) alkyl containing 5 to 14 carbon atoms, characterized in that EMI52.5 (1) reacting diketene with an amine of the formula EMI52.6 NH2R11 so as to form an oOÓtouc'tum1de of formula! EMI52.7 EMI52.8 where R1 has the meaning above, (2) this acetoactum1de ovec of ammonia is reacted, so as to form a beta-uminoorotonumide of formula EMI52.9 EMI52.10 in which Fit u In the meaning indicated above, and <Desc / Clms Page number 53> EMI53.1 U) this bata nminoorotonumide is reacted with phoe. 1Zeneo so as to form the compound dtoxacinone in question 20, - Process for the prepurution of an hampered oxatinent halo compound of formula EMI53.2 in which R1 denotes hydrogen, an alkyl radical EMI53.3 containing z, z. 10 carbon atoms substituted alkyl containing 1 to 8 carbon atoms, aryl containing 6 to 10 carbon atoms, substituted phenyl urolkyl containing 5 to 13 carbon atoms EMI53.4 carbon, uru, substituted kyl containing 5 to 13 carbon atoms, ulkdnyl containing 3 to 8 curbon atoms, alkynyl containing 3 to 8 carbon atoms, cyclo4lkyl containing 3 to 12 atoms. carbon cyc1ou1kny1. containing 4 to 12 atoms of ourbone, cycloulkyl u1kyle containing 4 to 13 carbon atoms, cycloelkenyl alkyl containing 5 to 13 carbon atoms * (substituted cycicalkyl) as. kyl containing 4 to 14 atoms of ovrbone or (cyoloulkenyl euh- etitue) 111ky18 containing 5 to 14 carbon utomen, R3 is an alkyl radical containing 114 atom. carbon, ch7.aoe, kyla containing 1 to 4 carbon atoms, bromoalkyl containing 1 to 4 carbon atoms and X ce a halogen atom, characterized by EMI53.5 where a leakage agent reacts with one of the halogenating conditions, with an oxasinone compound of the formula EMI53.6 whereby R1 and R2 have the meanings given above. <Desc / Clms Page number 54> 21, - 'A method of preventing the growth of undesirable vegetation, characterized in that a sufficient quantity is applied to the place to be treated to obtain a herbicidal effect of a compound according to one or more of claims 1 to 16. 22. Substantially anhydrous composition consisting of 1 a compound according to claim 3 and 0.1 to 10 parts by weight of a nonionic surfactant EMI54.1 23. * - A herbicidal composition containing an effective amount of a mixture of a compound according to claim 3 and at least one compound selected from herbicidal substituted ureas) herbicidal substituted triazines $ herbicidal phenols, carboxylic acids and their derivative herbicides) lee sole - inorganic herbicides, herbicidal uracils, dibromide EMI54.2 of 5,6-dihydro '' (4A, 6A) -dipyrido '' (l, 2-A2 ', l'-C) pyrasiniumj le 3wrmino ,, 2, ttriao.e, 3 # 6-endoxohexahydrophtmliques acid 1hexvch , oraaatone, diphenyloc6tonitr11e, MON-dimethyl alpha, ulpha-diphenyl..uc6tnmide, N, N dinpropya2, .. dini tro-4-triflucrometh-ylonilines N, N-di-n-propyl-2,6-dinitro-4 - methylonilinop 0- (2 4-dichlorophenyl) -0-methyl-isopropylphos phoroomidothiote and ,,, 6rtâtraahZorotdriphtnlüta from dimdthy.a, 24.- Method for preventing the growth of undesirable vegetation, characterized in that one applies at the place to be protected against this vegetation, an amount sufficient to obtain a herbicidal effect of a composition according to claim 23, EMI54.3 25- A process for converting a compound of the type oXüt.1none according to claim 4 into corresponding urucil, characterized in that said oxazinone compound is brought into contact with a basic material at a pH greater than about 7. <Desc / Clms Page number 55> 26, - Process for the preparation of a uracil characterized in that one carries out the steps defined in claim 17 and the compound of the oxazinone type is then brought into contact with a basic material up to a pH greater than about 7. 27. A process for the preparation of uracil, characterized in that the steps defined in claim 18 are carried out and the oxazinone-type compound is then brought into contact with a basic material to a pH greater than about 7. 28.- Process for the preparation of a uracil, characterized in that the steps defined in claim 19 are carried out and the oxazinone type compound is then brought into contact with a basic material up to a pH greater than about 7. 29.- Process for preparing a uracil, characterized in that the steps defined in claim 20 are carried out and the compound of the oxazinone type is then brought into contact with a basic material up to a pH greater than about 7 . 30.- New compounds their preparation * their transformation into uracil and their use, in substance, as described above, in particular in the examples