US3352662A - Method of inhibiting growth of undesired vegetation - Google Patents

Method of inhibiting growth of undesired vegetation Download PDF

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Publication number
US3352662A
US3352662A US343112A US34311264A US3352662A US 3352662 A US3352662 A US 3352662A US 343112 A US343112 A US 343112A US 34311264 A US34311264 A US 34311264A US 3352662 A US3352662 A US 3352662A
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methyl
oxazin
carbon atoms
dihydro
hydrochloride
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Hein L Klopping
Harvey M Loux
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to BR156168/64A priority Critical patent/BR6456168D0/pt
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US343112A priority patent/US3352662A/en
Priority to DE19641620107 priority patent/DE1620107A1/de
Priority to ES0296865A priority patent/ES296865A1/es
Priority to DE19641567016 priority patent/DE1567016A1/de
Priority to FR965260A priority patent/FR1394286A/fr
Priority to NO152166A priority patent/NO118883B/no
Priority to SE2363/64A priority patent/SE319478B/xx
Priority to CH236364A priority patent/CH450810A/de
Priority to NL646401832A priority patent/NL141358B/xx
Priority to GB8075/64A priority patent/GB1060741A/en
Priority to BE644357D priority patent/BE644357A/fr
Priority to DK94864AA priority patent/DK129683B/da
Priority to US637373A priority patent/US3454567A/en
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Priority to MY196830A priority patent/MY6800030A/xx
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/06—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings

Definitions

  • This invention relates to heterocyclic compounds and more particularly to such compounds having one oxygen atom and one nitrogen atom in the hetero-ring.
  • the compounds of this invention are useful in providing control against undesired vegetation. Some of the compounds are effective weed killing agents at rates even as low as one-half pound per acre of treated area. Furthermore the compounds of this invention are valuable as intermediates in the preparation of a large variety of uracil derivative compounds which are themselves useful as herbicides.
  • R is hydrogen, alkyl of 1 through 10 carbon atoms, substituted alkyl of 1 through 8 carbon atoms, aryl of 6 through 10 carbon atoms, substituted phenyl, aralkyl of through 13 carbon atoms, substitued aral-kyl of 5 through 13 carbon atoms, alkenyl of 3 through 8 carbon atoms, alkynyl of 3 through 8 carbon atoms, cycloalkyl of 3 through 12 carbon atoms, cycloalkenyl of 4 through 12 carbon atoms, cycloalkyl alkyl of 4 through 13 carbon atoms, cycloalkenyl alkyl of 5 through 13 carbon atoms, substituted cycloalkyl, substituted cycloalkenyl, (substituted cycloalkyl) alkyl of 4 through 14 carbon atoms, or (substituted cycloalkenyl) alkyl of 5 through 14 carbon atoms;
  • R is hydrogen, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy or tertbutoxy;
  • R is alkyl of 1 through 5 carbon atoms, chloroalkyl of 1 through 4 carbon atoms, or bromoalkyl of 1 through 4 carbon atoms, and
  • R and R can be joined together to form --(CH where n is a positive whole number from 3 through 5, i.e., 4 or 5.
  • substituted alkyl is intended to include such radicals as bromoalkyl of 1 through 8 carbon atoms,
  • alkoxyalkyl of 2 through 8 carbon atoms
  • alkoxy carbonyl alkyl of 3 through 8 carbon atoms and cyanoalkyl of 2 through 8 carbon atoms.
  • aryl and substituted phenyl embrace radicals such as
  • aralkyl and substituted aralkyl are intended to include such radicals as furfuryl benzyl phenylal-kyl of 8 through 11 carbon atoms (total) chlorobenzyl dichlorobenzyl alkylbenzyl of 8 through 11 carbon atoms (total) dialkylbenzyl of 9 through 13 carbon atoms (total) nitrobenzyl alkoxybenzyl of 8 through 11 carbon atoms (total), and naphthylmethyl
  • cycloalkyl, cycloalkenyl, cycloalkyl alkyl, and cycloalkenyl alkyl will include cyclohexyl cyclohexenyl cyclohexylalkyl cyclohexenylalkyl cyclopentyl cy'clopentenyl cyclopentylalkyl
  • the compounds of Formula 1 can conveniently be prepared in the form of salts with organic or inorganic acids.
  • the free base is highly unstable and the salts are therefore highly preferred.
  • Some examples of these preferred salts are the salts of such acids as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfamic acid, benzoic acid, acetic acid, phosphoric acid, phthalic acid, citric acid, succinic acid, maleic acid, trataric acid, propionic acid, dichloroacetic acid, trichloroacetic acid, alpha, alpha-dichloropropionic acid, and the like.
  • Step 1 React a substituted acetoacetamide with ammonia to form a substituted beta-aminorotonamide.
  • Step 2 React the beta-aminocrotonamide with phosgene to form the corresponding oxazin-Z-one hydrochloride salt.
  • R R and R have the same meaning as in Formula 1.
  • the acetoacetamides used in Step 1 are prepared either by reaction of an amine with diketene as described below or by reaction of a beta-keto ester with excess amine followed by treatment with aqueous acid.
  • the acetoacetamide used as the starting material can be prepared by reacting diketene with an amine according to the equation.
  • the acetoacetamide is then reacted with ammonia.
  • This reaction is carried out by admixing the ammonia with a solution of the acetoacetamide in water or an inert organic solvent such as ether, tetrahydrofuran, an alcohol, 1,1,2-trichloroethylene, or the like.
  • water used as the solvent, the ammonia can conveniently be added as an aqueous solution.
  • concentrated aqueous ammonia on the order of 28-30% by weight ammonia can be used as is.
  • an inert organic solvent is used, the ammonia can be introduced as a gas or as an undiluted liquid.
  • the reaction mass is stirred if desired to promote good mixing of the reactants.
  • the mol ratio of ammonia to acetoacetamide should be at least 1 to 1.
  • the upper limit of ammonia is largely determined by convenience and economics but no reason is seen to exceed an ammonia to acetoacetamide mol ratio of 50 to 1 and a ratio of below 10 to 1 is preferred.
  • the use of an excess of ammonia results in an increased yield of beta-aminocroton-amide.
  • the temperature at which the amination of the acetoacetamide is carried out is largely a matter of convenience. Ordinarily at ambient pressure temperatures above about 50 C. are disadvantageous because of undesired loss of ammonia above this temperature.
  • the reaction temperature is preferably in the range from minus 30 to 30 C.
  • the amination reaction generally takes from about 1 to 10 hours, depending as will be understood upon the reaction temperature and the system employed.
  • the beta-aminocrotonamide product is recovered by any convenient physical means, such as by filtration, separation of layers, evaporation of the solvent, or the like. After recovery, the beta-aminocrotonamide product can be dried and used directly in step 2 of our process or can, if desired, be purified by customary methods such as recrystallization.
  • the beta-aminocrotonamide prepared according to Step 1 is converted into the corresponding substituted oxazin- 2-one hydrochloride by reaction of the former with phosgene.
  • the preparation of a 6-imino-3,6-dihydro-4-methyl- 2H-1,3-oxazin-2-one hydrochloride from a beta-aminocrotonamide and phosgene will now be described for purposes of illustration.
  • a solution of phosgene is prepared in a suitable insert organic solvent such as tetrahydrofuran, dioxane, acetonitrile, 1,1,2-trichloroethylene, or the like.
  • a solvent solution or slurry of the beta-aminocrotonamide, preferably in the same solvent as the phosgene, is admixed with the phosgene solution.
  • phosgene Equimolar amounts of betaarninocrotonamide and phosgene can be used but for improved efficiency and economy a slight excess of phosgene is preferred. Ordinarily the amount of phosgene used will not exceed 5 mols and preferably will not exceed 2 mols for each mol of beta-aminocrotonamide. It is .advantageousto add the crotonamide solution or slurry to the phosgene solution and maintain phosgene addition to keep the phosgene in, excess and the solution saturated with phosgene. Superatmospheric pressure can be used to advantage.
  • the mixture which now contains a solid as a second phase is heated at a temperature from about 40 to about C. for a period of from about 30 minutes to about 6 hours to complete the reaction.
  • the desired hydrochloride salt of the 6-imino-3,6-dihydro-4-methyl-2H-1,3-oxazin- 2-one is formed.
  • This compound can be recovered by any convenient means such as filtration or decantation of the supernatant liquid.
  • the hydrochloride salt can be converted to other salts of the oxazinone by conventional replacement reactions or by neutralization of the hydrochloride, for example by the use of silver oxide suspended in an inert solvent such as methylene chloride, followed by the filtration of the silver chloride and addition of the acid required for the desired salt.
  • Salts of acids weaker than hydrochloric acid can be prepared by suspending or dissolving the oxazinone hydrochloride in an inert solvent (or simply in the weaker acid if it is a liquid), adding the appropriate amount of the weaker acid and a salt of the Weaker acid, e.g. the sodium salt, and filtering off or otherwise removing the sodium chloride formed.
  • oxazinone salts where R is chlorine or bromine are prepared by conventional halogenation procedures, for example by reaction with the halogen in glacial acetic acid or other solvent.
  • the oxazinone salts in general do not have distinct melting points. On heating they lose hydrogen chloride and convert to the corresponding uracil as will be described in greater detail hereinafter.
  • the oxazinone salts are soluble in water and somewhat soluble in highly polar organic solvents such as acetic acid and alcohols but are insoluble in the less polar organic solvents.
  • R is alkyl of 1 through 10 carbon atoms, substituted alkyl of 1 through 8 carbon atoms, aryl of 6 through 10 carbon atoms, substituted phenyl, aralkyl of through 13 carbon atoms, substituted aralkyl of 5 through 13 carbon atoms, alkenyl of 3 through 8 carbon atoms, alkynyl of 3 through 8 carbon atoms, cycloalkyl of 3 through 12 carbon atoms, cycloalkenyl of 4 through 12 carbon atoms, cycloalkyl alkyl of 4 through 13 carbon atoms, cycloalkenyl alkyl of 5 through 13 carbon atoms, substituted cycloalkyl, substituted cycloalkenyl, (substituted cycloalkyl) alkyl of 4 through14 carbon atoms,
  • R is hydrogen, chlorine or bromine
  • R is methyl; and where R and R can be joined together to form (CH where n is 3, 4 or 5 and provided that, when R is hydrogen and R is methyl, R is other than methyl or ethyl.
  • Illustrative of preferred compounds of this invention are salts and particularly the hydrochlorides or hydrobromides of the following oxazinones:
  • Example I 6-sec-bmylimin0-3,6-dihydr0-4-methyl- 2H-L3-ovcazin-2-one hydrochloride -To 852 parts of N-sec-butylacetoacetamide are added 540 parts (70% excess) of concentrated (29%) aqueous ammonia. The clear solution is stirred and kept about room temperature in order to avoid an excessive loss of ammonia. After about 6 minutes, the solution turns cloudy and an oil begins to separate soon thereafter. Crystallization is induced by scratching the vessel wall. Precipitation of the product beta-arnino-N-sec-butylcrotonamide is complete in 4 hours.
  • the thick crystal mass is filtered and the solid is washed with ice water and dried in a vacuum oven at 5560 C.
  • the product is weighed and found to be 696 parts (82% of theory) and melts at 84-88 C. Recrystallization from benzene raises the melting point to 89-90" C.
  • the infrared spectrum of this material is characterized by a sharp peak at 5.6 microns ascribable to the 7 moiety, a peak at 3.7 microns (amine hydrochloride) and the absence of NH absorption in the 3 micron region.
  • The-solid is soluble in water to the extent of about 27% by weight at room temperature. On prolonged standing of the aqueous solution at room temperature, or
  • uracil Upon dissolving the oxazinone in dilute aqueous solutions of NaOH, Na CO NaOOCCH or even NaHCO virtually instantaneous rearrangement to the just-mentioned uracil takes place.
  • This uracil which is present in the solution in the form of its sodium salt, can be isolated by acidifying the solution. The uracil separates.
  • Example 2.6-isopropylimin0-3,6-dihydr0-4-methyl- 2H-l,3-0xazin-2-0ne hydrochloride To a solution of 33.6 parts of N-isopropylacetoacetamide in 33.6 parts of water is added 29.3 parts of concentrated (28%) aqueous ammonia. The resulting solution is stirred at ambient temperature for 6 hours during which time beta-amino-N-isopropylcrotonamide precipitates as a white crystalline solid. It is collected by filtration, Washed and air dried to give 28.4 parts of material melting at l42l44- C. This material is sufficiently pure for use as next described but if desired can be further purified by recrystallization from ethyl acetate to obtain a purer material melting at 144l45 C.
  • Example 3.6-phenyliminc-3,6-dihydro-4-methyl- 2H-1,3-0xazin-2-0ne hydrochloride To a stirred solution of 88.6 parts of acetoacetanilide in 1500 parts of water and parts of methanol at 73 C. is added 67 parts of concentrated (28%) aqueous ammonia. After several minutes an oil forms and crystallizes after initiation by scratching the wall of the vessel. After 2 hours the slurry is cooled in ice and filtered. The solid is washed, with 400 parts of cold water and dried in a vacuum oven at 60 C., leaving 69 parts of beta-amino-N-phenylcrotonamide (78% of theory) melting at 1405-1423? C.
  • a solution of 8.8 parts of the.beta-a-mino-N-phenylcrotonamide in 40 parts of tetrahydrofuran is added over a 10 minute period to a solution of 5.5 parts of phosgene in 25 parts of tetrahydrofuran.
  • the slurry is heated at 60-70 C. for 2 hours, then cooled and the solid collected by filtration, washed with tetrahydrofuran and air dried to give 7.6 parts of ,6-phenylimino-3,6- dihydro-4-methyl-2H-1,3-oxazin 2 one hydrochloride melting at 23 8-244 C. with gas evolution.
  • Examples 4-25 The products of the following Examples 4-16 are prepared according to the procedure of Example 3 by replacing the acetoacetanilide of that example with molecular equivalents of the acetoacetamides indicated to obtain the specified betaaminocrotonamide and finally phosgene in 200 parts of dioxane.
  • the reaction tempera- 40 the identified product.
  • 11 N-methylacetoacctamide Beta-amino-N-methylcrotonamide G-methylimtrio-3,6-dihydro-4-rnethy1-2H-1,3-
  • oxazin-Z-one hydrochloride 12 N-o-fluorophenylacctoacetamide Beta-arnino-N-o-fiuorophenylcrotonamide. 6-(o-fiuorophenyllmino)-3,6-dihydro-4-methyl-- 2H-l,3-oxazin-2-one-hydrochloride. 13 N-norbornylmethylacetoacetamide Beta-amino-N-norhornylmethylcrotonfi-norbornylmethylirnino-3,6-dihydroA-rncthylamide. 2H-1,3-oxazin-2-one hydrochloride.
  • N-(l-cthylpropyl)aeetoacetamide Beta-amino-N-(LethylpropyDeroton- 6-(l-ethylpropylimino)-3,6-dihydro-4-methylamide.
  • Ell-1,3mxazin-2-one hydrochloride 15 N-(1,3-dimetl1ylbutyl)acetoacetamide.- Beta-amino-N-(1,3-dirnethylbutyl)croton- 6-(1,3-dirnethylbutylin1ino)-3,6-dihydro-4- amide. methyl-QH-l,3-0xazin-2-one hydrochloride.
  • N-(3-methoxypropy1)-acetoaeetamide Beta-amino-N-(3-methoxypropy1)- 6-(3-methoxypropylimino)-3,6-dihydro-4-methy1- crotonamide.
  • 2H-1,3-oxazin-2-one hydrochloride 20
  • Beta-amino-N-sec-butyl-4-bromocroton- 6-sec-butylimin0-3,6-dihydroA-bromomethylamide 2H-l,3-oxazin-2one hydrochloride.
  • octen-Z-amide butoxy-2H-1,3-oxazin-2-one hydrochloride. N-cyclooctyl-Q-ketocycloheptane-carbox- Q-amiuo-N-cyclooctyl-cycloheptenecarboxfi-cyclooctylimino-3,6-dihydro-4,5-pentanethylamide. amide. ene-ZH-LS-oxazin-Q-oue hydrochloride.
  • Example 26 -6-sec-butylimino-3,6-dihydro-4-methyl- 2H-1,3-oxazin-2-one
  • a slurry of 6-sec-butylimino-3,6-dihydro-4-methyl-2H- 1,3-oxazin-2-one hydrochloride in methylene chloride is stirred with an excess of silver oxide and filtered after 3 minutes.
  • the solution of the free oxazinone thus obtained is placed immediately in a recording infrared spectrophotometer and the region between 5.5 and 6.1 microns is recorded.
  • the spectrum shows a characteristic oxazinone peak at 5.7 microns (a shift of 0.1 micron to higher wavelength due to neutralization of the HCl salt), but no peak at 5.85 microns which is characteristic of the corresponding 3-sec-butyl-6-methyluracil.
  • the solution is left in the infrared machine and the same region is recorded at various time intervals.
  • the 5.7 micron peak gradually diminishes While a peak at 5.85 microns forms and becomes larger.
  • the oxazinone peak is all but vanished while the uracil peak is very strong.
  • no trace of the oxazinone peak is left while the uracil peak has reached maximum intensity.
  • the infrared spectrum is similar to that of the starting material (sharp peak at 5.6 microns) and contains a peak at 15 microns ascribable to the S-bromo substituent.
  • the bromo compound can be converted to the corresponding 5-bromo-3-sec-butyl-6-methyluracil (MP. 157- 159.5 C.) by the same methods described above for the starting material.
  • the bromo compound is less Water soluble than the corresponding chloro compound.
  • Examples 36-40 The products of the following Examples 36-40 are prepared according to the procedure of Examples by replacing the 6-sec-butylimino-3,6dihydro-4-methyl- 2H-1,3-oxazin-2-one hydrochloride of that example with molecular equivalents of the oxazinones indicated to obtain the specified 5-bromo compound.
  • oxazinones such as those in the following tabular examples can be prepared by the procedure of Example 26.
  • Example 35 6-sec-butylimino-5-br0mo-3,6-dihydr0-4- methyl-ZH-I,3-0xazin-2-0ne hydrobromide
  • 6-sec-butylimino-3,6- dihydro-4-methyl-2H-1,3-oxazin-2-one hydrochloride is added dropwise 17.6 parts of bromine while stirring. A precipitate forms.
  • Example 41 -6-sec-butylimin0-5-chZora-3,6-dihydr0-4- methyl-2H-1,3-oxazin-2-one hydrochloride
  • a slurry of 15 parts by weight of 6-sec-butylimino-3,6 dihydro-4-methyl-2H-1,3-oxazin-2-one hydrochloride in milliliters of glacial acetic acid is stirred at room temperature while chlorine gas is introduced.
  • the slurry becomes thinner at first, and then a thick white precipitate forms which is filtered, washed with acetic acid and acetone, and dried. It weighs 12 parts and melts at 144 C.
  • the infrared spectrum of this product is very similar to that of the starting material (sharp peak at 5.6 microns). It contains an additional peak at 14.5 microns ascribable to the 5-chloro substituent.
  • the chloro compound is converted to the corresponding S-chlorouracil (MP. 152- 153.5 C.) in the same manner as described above for the starting oxazinone by heating above the melting point or treatment with dilute aqueous solutions of NaOI-l, Na CO NaOOCCH or NaHCO
  • the water solubility of the 5-chloro oxazinone is about 8% by weight at room temperature.
  • Examples 42-46 The products of the following Examples 4246 are prepared according to the procedure of Example 41 by replacing the 6-sec-butylimino-3,6-dihydro-4-methyl-2H- 1,3-oxazin-2-one hydrochloride of that example with molecular equivalents of the oxazinones indicated to obtain the specified S-chloro compound.
  • the conversion of the oxazinone derivative can be carried out using the slurry of the oxazinone hydrochloride salt formed as described above in step 2 of our process from the phosgenation ofthe aminocrotonamide or, in the alternative, where the oxazinone salt has been recovered in solid crystalline form, the oxazinone salt can be admixed wtih a suitable inert liquid such as water or organic solvent to form a solution or slurry.
  • a suitable inert liquid such as water or organic solvent
  • the slurry from either source is admixed with suflicient aqueous base, such as sodium hydroxide, potassium hydroxide, sodium carbonate, etc. to neutralize the acid salt to pH 7 or above and preferably to bring the pH within the range of about 8 to 10.
  • suflicient aqueous base such as sodium hydroxide, potassium hydroxide, sodium carbonate, etc.
  • suflicient aqueous base such as sodium hydroxide, potassium hydroxide, sodium carbonate, etc.
  • the oxazinone can be directly converted to the uracil by admixing With the oxazinone in the liquid system just sufficient base to neutralize the salts, i.e. one mol of base per mol of the oxazinone salt. With weak bases such as sodium bicarbonate, excess base still allows recovery of the free uracil.
  • Step A Reacting a substituted acetoacetamide of the formula where R R and R have the same meaning as in Formula 1, with ammonia to produce a beta-aminocrotonamide of the formula
  • Step B -Reacting the beta-aminocrotonamide with phosgene O Cl-Ql-Cl to obtain a reaction product
  • Step C Reacting the reaction product of Step B with an inorganic base and, if necessary, an acidifying agent to produce a uracil of the formula
  • the preceding overall process is carried out with the preliminary step of preparing the beta-aminocrotonamide from diketene and an amine.
  • our process involves reacting diketene with an amine according to the following:
  • acetoacetamide is then reacted with ammonia in a suitable reaction medium, preferably using from 1 to 10 mols of ammonia for each mol of acetoacetamide, at a temperature in the range from 30 to +30 C. as follows:
  • the aminocrotonamide is next phosgenated in suitable medium, preferably using from 1 to 2 mols of phosgene for each mol of aminocrotonamide, at a temperature in the range from 40 to C. for /26 hours to produce the oxazinone hydrochloride in the system as follows:
  • the oxazinone derivative is next converted at pH 9-10 with a base such as sodium hydroxide to form the corre-.
  • Example 47 To a stirred solution of 10.9 parts of phosgene in 50 parts of tetrahydrofuran is added, over a 15 minute period at ambient temperature, a solution of 15.6 parts of beta- 13 amino-N-sec-butylcrotona-mide prepared as described in Example 1, in 40 parts of tetrahydrofuran. The temperature rises during the addition to about 50 C. and a yellow slurry forms. This slurry is heated at reflux for 2 hours. The solid present in the slurry at this point is 6- sec butyl imino-3,6-dihydro-4-methyl-2H-1,3-oxazin-2- one hydrochloride.
  • the slurry is then poured into 200 parts of 2 N aqueous sodium hydroxide, with stirring.
  • the resulting solution is extracted twice with 100 parts of methylene chloride to remove alkali-insoluble organic impurities.
  • the aqueous portion is then acidified with concentrated hydrochloric acid and the resulting 3-secbutyl-6-methyluracil is isolated by extracting four times with 100 parts each of methylene chloride. Evaporation of the solvent leaves 13.4 parts of the uracil.
  • Example 48 A solution of 9.6 parts of beta-amino-N-phenyl-crotonamide (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 over a 15 minute period. After the initial exothermic reaction has subsided, the mixture is heated at 63-67 C. for 2 hours. It is then cooled and poured into 200 parts of 2 N aqueous sodium hydroxide. After extraction twice with 150 parts each of methylene chloride to remove impurities, the aqueous solution is acidified with concentrated hydrochloric acid. The product is isolated by extraction six times with 100 parts each of methylene chloride, followed by evaporation of the methylene chloride. There is obtained 7.5 parts of 3-phenyl-6 methyluracil, melting at 224250 C.
  • the compounds of Formula 1 and especially those indicated to be preferred are effective herbicides. They exert herbicidal action against both broadleaf and grass weeds, are effective against hard-tokill nutsedge and perennial grasses such as quack grass, Johnson grass, and Bermuda grass, and are effective on highly adsorptive substrates such as railroad ballast, heavy clay soil, and soils high in organic matter.
  • Certain of the compounds of this invention also exhibit selective herbicidal action in crops.
  • an oxazinone of the invention and a rate and time of application, annual grass and broadleaf seedlings in such crops as asparagus, corn, flax, sugar cane, pineapple, safflower, peanuts, citrus, alfalfa, strawberries, gladiolus, stone fruits and cucurbits can be controlled.
  • certain of the oxazinones can also be used to control weeds growing in dormant crops. 1
  • oxazinones to be used in any given situation will, of course, vary according to the particular end result desired, the use involved, the plant and soil involved, the formulation used, the mode of application, prevailing weather conditions, foliage density and like factors. Since so many variables play a role, it is not possible to indicate a rate of application suitable for all situations. Broadly speaking, the compounds are used at levels of about 4 pound per acre to about 25 pounds peracre. For selective weed control in crops, rates of A to 8 pounds per acre will generally be used. More of the active material'can be used to control difficultto-kill species growing under adverse conditions. Economic factors, such as inaccessibility of the area to betreated, e.g., fire breaks in forests, may also favor higher rates, with less frequent treatments.
  • the herbicidal compounds of this invention can be formulated as dusts, as wettable powders, or as soluble owders. In these formulations, care must be taken that diluents, surface active agents, and other pesticidal additives are neutral in pH and are particularly free of reserve alkalinity. It is also important that the formulation ingredients are dry and that during handling of the ingredients, preparation of the compositions, and storage of the compositions, water be rigidly excluded. Insofar as possible, the diluents and surfactants and other additives should also be inert chemically and should be reasonably free of active OH groups.
  • Percent Active ingredient 3060
  • Non-ionic surfactant 0.1-10 Remainder-inert diluents to 100 Substantially anhydrous.
  • substantially anhydrous is meant that the maximum amount of water present is 1% by weight based on the weight of the oxazinone salt present.
  • Suitable diluents for the preparation of dusts and wettable powders are finely divided, pulverulent solids, with neutral or slightly acidic surface reactions such as synthetic fine silicas, diatomaceous earths, and acidic kaolinite clays. Examples of the above are Hi-Sil, Celite 209, Continental clay, Barnet clay, and Pikes Peak clay 9T66.
  • Other diluents which can sometimes be used may be inert vegetable flours, such as Redwood flour, walnut shell flour, and the like.
  • the active ingredient When such diluents are to be used in the preparation of herbicidal dusts, the active ingredient will preferably be present in amounts ranging from 0.5 to 15%, with the remainder primarily being one or more of the abovenamed diluents.
  • the active ingredient When the composition to be prepared is a wettable powder, the active ingredient may be present in amounts ranging from 10 to about the remainder being diluent except for the presence of from about 0.1 to 5% or 10% of one or more of the surfactants described below.
  • the surfactants for these compositions can be of the anionic, cationic, and non-ionic type, although anionic surfactants are preferred and non-ionic surfactants are very much preferred. It is important that the anionic surfactants not be highly alkaline, and with this limitation, surfactants such as salts of alkyl aryl sulfonic acids, and petroleum sulfonates and salts of fatty alcohol sulfates can be used. A list of such surfactants is shown in Detergents and Emulsifiers Up-to-date, 1962, by John -W. McCutcheon, Inc. Other anionic surfactants that can be used may be salts of dialkyl esters of sulfosuccinates and of fatty acid esters of isethionic acids. In some instances, the free acid instead of the salt can also be advantageously used.
  • non-ionic surfactants are polyethylene glycol fatty esters, and polyoxyethylene 'ethers and thioethers.
  • Other non-ionic compounds are alkylphenoxypolyethyleneoxyethanols, such as nonylphenyl adducts with ethylene oxide, trimethylnonylpolyethylene glycol ethers, polyethylene oxide adducts of fatty and rosin acids, polyethylene oxide adducts of sorbitan esters of fatty and rosin acids, and long chain alkyl mercaptan adducts with ethylene oxide.
  • Particularly preferred may be polyglycol ethers in which both terminal alcohol groups have been esterified with fatty acids such as lauric, oleic, palmitic, or stearic acids.
  • compositions consist of from 75 to of the active ingredient with the remainder being from one or more of the abovementioned surface active agents.
  • the diluent and/ or the surfactant is blended with the active ingredient in the conventional manner in a ribbon blendor or similar device, and the mixture is p then ground. As stated above, care must be taken to exelude moisture.
  • the herbicidal compositions of this invention can be formulated to contain two or more of the oxazinone alts. They can also be formulated to contain other known herbicides in addition to the oxazinones to give compositions which have advantages over the individual components.
  • 2,2-dichloropropionic acid and its salts Mixed in a 1:4 to 8:1 ratio, preferably a 1:2 to 4:1 ratio.
  • N,N-di(n-propyl)thiolcarbamic acid ethyl ester N,N-di(n-propyl)thiolcarbamic acid, nropyl ester Nethyl-N-(n-butyl)thiolca-rbarnic acid, ethyl ester N-ethyl-N-(n-butyl)thiolcarbamic acid, n-propyl ester Mixed in a 1:2 to 24:1 ratio, preferably a 1:1 to 12:1 ratio.
  • N-phenylcarbamic acid isopropyl ester N-(m-chlorophenyl)ca'rbamic acid, isopropyl ester N-(m-chlorophenyl)carbamic acid, 4-chloro-2-butynyl ester Mixed in a 1:2 to 24:1 ratio, preferably a 1:1 to 12:1 ratio.
  • 2,3,6-trichl0rophenylacetic acid and its salts Mixed in a 1:12 to 8:1 ratio, preferably a 1:4 to 4:1 ratio.
  • Sodium tetraborate hydrated, granulated Sodium metaborate Sodium p abqrate 17 Polyborchlorate Unrefined borate ore such as borascu Mixed in a 3:1 to 1500:1 ratio, preferably a 6:1 to 1000:1 ratio.
  • E Ammonium thiocyanate Mixed in a 1:10 to 20:1 ratio, preferably a 1:5 to :1 ratio.
  • B 3-arnino-1,2,4-triazole Mixed in a 1:20 to 20:1 ratio, preferably a 1:5 to 5:1
  • 3,6-endoxohexahydrophthalic acid Mixed in a 1:3 to 20:1 ratio, preferably a 1:2 to :1 ratio.
  • 2,4-dichloro-4'-nitrodiphenyl ether Mixed in a 1: 10 to 30:1 ratio, preferably a 1:5 to'20zl ratio.
  • Example 49 Percent 6, norbornylmethylimino 3,6-dihydro-4-methyl-2H- 1,3-oxazin-2-one hydrochloride 8O Polyethylene glycol dioleate 5 Hi-Sil 15 The ingredients are blended and ground in a hammer mill until the particle size of substantially all the active ingredients is below 50 microns.
  • This Wettable powder is used for the control of annual broadleaf and grass weeds growing around telephone poles and highway markers.
  • An application of 5 pounds of active ingredient per acre in 40 gallons of Water gives excellent control of crab grass, water grass, black-eyed susan, carpetweed, and chickweed.
  • Example 50 Percent 6 tert butylimino 5-bromo-3,6-dihydro-4-methyl- 2H-l,3-oxazin-2-one hydrobromide 80.0 Sodium lauryl sulfate 0.6 Partially desulfonated sodium lignin sulfonate 1.0
  • a Wettable powder is prepared by blending the com- Example 51 Percent 6 isopropylimino bromo-3,6-dihydro-4-methyl- 2H-1,3-oxazin-2-one hydrobromide 80.0 Sodium lauryl sulfate 0.6 Sodium lignin sulfonate 2.0
  • This wettable powder is used as a general purpose weed killer on industrial sites and railroad ballast. Ten to twenty pounds of active ingredient per acre in 100 gallons of water gives excellent control of goldenrod, evening primrose, pokeweed, ox-eye daisy, cocklebur, goose. grass, crab grass, and love grass.
  • Example 52 Percent 6 sec butylimino 5 bromo-3,6-dihydro-4-methyl- 2I-I-1,3-oxazin-2-one hydrobromide 95 Polyethylene glycol ester of fatty and rosin acids concreted with urea 5
  • Example 53 Percent 6 norbornylmethylimino 3,6-dihydro-4-methyl-2H- 1,3-oxazin-2-one hydrochloride 40 Soya lecithin 3 Substantially aliphatic, low viscosity mineral oil, e.g.,
  • the oil suspension is prepared by pregrinding the active material and mixing it with the other components with agitation, or by blending all the components together, then pebble-milling or sand-milling them to. reduce. the particle size of the active component.
  • the product is suitable for dilution with weed oils to form an oil spray.
  • This formulation is diluted with 80 gallons of an.
  • herbicidal oil such as Lion He'rbicidal Oil No. 6 and applied at 12 pounds of active ingredient per acre for general overall weed control along cyclone fences and railroad ballast.
  • Example 54 Percent 6 cyclohexylimino 5-chloro-3,6-dihydro-4-methyl- 2H-1,3-oxaZin-2-one hydrochloride 90.0 Alkyl naphthalene sulfonate, Na salt 2.0 Low viscosity methyl cellulose 0.3 Attapulgite clay 7.7
  • This formulation gives excellent weed control when ap plied pre-emergence or post-emergence at rates of 4 pounds per acre to crab grass, wild oats, wild mustard, volunteer alfalfa, foxtail and lambs quarters.
  • Example 55 Percent 6 sec butylimino S-chloro-3,6-dihydro-4-methyl- 2H-1,3,-oxazin-2-one hydrochloride 10 Cclite 209 10 Kaolinite clay (acidic) 80
  • the active ingredient and the Celite are blended and ground in a hammer mill until the mixture is uniform and the particle size of substantially all of the material is below 50 microns.
  • This dust concentrate is then mixed with the kaolinite clay and the mixture is deagglomerated in a.
  • This composition is used for the control of mixturesof annual and perennial weeds growing around farm buildings.
  • An application of 15 pounds of active material per acre gives excellent control of pepper grass, wild mustard, burdock, quack grass, and crab grass.
  • Example 56 Percent 6 sec butylimino 5-brorno-3,6-dihydro-4-methyl- 2H-l,3-oxazin-2-one hydrobromide 25
  • Granular 815 mesh attapulgite clay A granular composition is prepared by suspending the active ingredient in acetone and spraying this solution 011 the attapulgite granules while they are tumbled. The resulting granules are then dried.
  • the granules are applied by hand for spot treatment of undesirable bunch grasses growing in agricultural areas.
  • An application of 20 to 30 pounds of active ingredient per acre gives good control of Dallis and vasey grass.
  • R is selected from the group consisting of hydrogen; alkyl of 1 through 10 carbon atoms; substituted alkyl of 1 through 8 carbon atoms wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy, alkoxycarbonyl, and cyano; aryl of 6 through 10 carbon atoms; substituted phenyl wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, alkoxy of 1 through 5 carbon atoms, alkyl of 1 through 6 carbon atoms, nitro, trifluoro-.
  • R is selected from the group consisting of hydrogen, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec.-butoxy, and tert.-butoxy; and
  • R is selected from the group of alkyl of 1 through 5 carbon atoms, chloroalkyl of 1 through 4 carbon atoms, and bromoalky-l of 1 through 4 carbon atoms; with the proviso that R and R can be joined together to form (CH where n is a positive whole number from 3 through 5; and acid salts of said compound.
  • R is selected from the group consisting of alkyl of 1 through 10 carbon atoms; substituted alkyl of 1 through 8 carbon atoms wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy, alkoxycarbonyl, and cyano; aryl of 6 through 10 carbon atoms; substituted phenyl wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, alkoxy of 1 through carbon atoms, alkyl of 1 through 6 carbon atoms, nitro, trifluoromethyl, 1,2- tetramethylene, and 1,2-trimethylenylene; aralkyl of 5 to 13 carbon atoms, substituted aralkyl of 5 through 13 carbon atoms wherein said substituent is selected from the group consisting of chlorine, nitro, alkyl and alkoxy; alkenyl of 3 through 8 carbon atoms; alkynyl of 3 through 8 carbon atom
  • R is selected from the group consisting of hydrogen
  • R is methyl; with the proviso that R and R can be joined together to form (CH where n is a positive whole number of 3 through 5; and with the further proviso that when R is hydrogen, R is other than methyl and ethyl; and acid salts of said compound.
  • the method of inhibiting growth of undesired vegetation comprising applying to the locus to be treated a herbicidally etfective amount of 6-sec.-butylirnino-5- chloro-3,6-dihydro-4-methyl-2H-1,3-oxazin-2-one hydrochloride.
  • the method of inhibiting growth of undesired vegetation comprising applying to the locus to be treated a herbicidally effective amount of 6-sec.-butylimino-5- bromo-3,6-dihydro-4-methyl-2I-I-1,3-oXazin-2-one hydrobromide.
  • the method of inhibiting growth of undesired vegetation comprising applying to the locus to be treated a herbicidally effective amount of 6-norbornylimino-3,6- dihydro-4-methyl-2H-1,3-oxazin-2-one hydrochloride.
  • the method of inhibiting growth of undesired vegetation comprising applying to the locus to be treated a herbicidally effective amount of 6-norbornylmethylimino- 5-bromo-3,6-dihydro-4-methyl-2H-1,3-oxazin-2-one hydrobromide.
  • the method of inhibiting growth of undesired vegetation comprising applying to the locus to be treated a herbicidally effective amount of 6-(1-ethylpropylimino)- 5-bromo-3,6-dihydro-4-methyl-2H-1,3-oxazin-2-one hydrobromide.
  • the method of inhibiting growth of undesired vegetation comprising applying to the locus to be treated a herbidicidally eifective amount of 6-(1,3-dimethylbutylimino) 5 chloro 3,6 dihydro 4 methyl 2H 1,3- oxazin-Z-one hydrochloride.
  • the method of inhibiting growth of undesired vegetation comprising applying to the locus to be treated a herbicidally eifective amount of 6-isopropylimino-5- bromo-3,6-dihydro-4-methyl-2H-1,3-oxazin-2-one hydnobromide.
  • the method of inhibiting growth of undesired vegetation comprising applying to the locus to be treated a herbicidally eflective amount of 6-tert.-butylimino-5- bromo-3,6-dihydro-4-methyl-2H-1,3-oXazin-2-one hydrobromide.
  • the method of inhibiting growth of undesired vegetation comprising applying to the locus to be treated a herbicidally efiective amount of 6-phenylimino-5-bromo-3,6-dihydro-4-methyl-2H-1,3-oxazin-2-one hydrobromide.
  • the method of inhibiting growth of undesired vegetation comprising applying to the locus to be treated a herbicidally effective amount of 6-(3a,4,7,7a-tetrahydro 4,7 methanoindan 2 ylimino) 3,6 dihydro 4- methyl-2H-1,3-oxazin-2-one hydrochloride.
  • the method of inhibiting growth of undesired vegetation comprising applying to the locus to be treated a herbicidally effective amount of 6-cyclohexylimino-5- bromo 3,6 dihydro 4 methyl 2H 1,3 oxazin 2- one hydrobromide.
  • the method of inhibiting growth of undesired vegetation comprising applying to the locus to be treated a herbicidally effective amount of 6-cycloheXylimino-4,5- trimethylene-3,6-dihydro-2H-1,3-oxazin-2-one hydrochloride.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
US343112A 1963-02-27 1964-02-06 Method of inhibiting growth of undesired vegetation Expired - Lifetime US3352662A (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
BR156168/64A BR6456168D0 (pt) 1963-02-27 1964-01-17 Compostos heterociclicos e processo para fazer os mesmos
US343112A US3352662A (en) 1963-02-27 1964-02-06 Method of inhibiting growth of undesired vegetation
ES0296865A ES296865A1 (es) 1963-02-27 1964-02-25 Metodo de inhibiciën del desarrollo de vegetaciën indeseada
DE19641567016 DE1567016A1 (de) 1963-02-27 1964-02-25 Heterocyclische Verbindungen und ihre Anwendung
DE19641620107 DE1620107A1 (de) 1963-02-27 1964-02-25 Verfahren zur Herstellung von heterocyclischen Verbindungen
CH236364A CH450810A (de) 1963-02-27 1964-02-26 Herbicid
NO152166A NO118883B (en)) 1963-02-27 1964-02-26
SE2363/64A SE319478B (en)) 1963-02-27 1964-02-26
FR965260A FR1394286A (fr) 1963-02-27 1964-02-26 Procédé de préparation d'oxazinones
NL646401832A NL141358B (nl) 1963-02-27 1964-02-26 Werkwijze om herbicide preparaten te bereiden.
GB8075/64A GB1060741A (en) 1963-02-27 1964-02-26 Improvements in or relating to oxazinone derivatives
BE644357D BE644357A (en)) 1963-02-27 1964-02-26
DK94864AA DK129683B (da) 1963-02-27 1964-02-26 Middel til bekæmpelse af uønsket plantevækst.
US637373A US3454567A (en) 1963-02-27 1967-05-10 Oxazinone compounds
MY196830A MY6800030A (en) 1963-02-27 1968-12-31 Improvements in or relating to oxazinone derivatives

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3442640A (en) * 1966-11-22 1969-05-06 Givaudan Corp Methods of destroying weeds with substituted tetralins
US3451802A (en) * 1966-06-27 1969-06-24 Gulf Research Development Co Triazine herbicides
US3529952A (en) * 1968-09-17 1970-09-22 Du Pont Plant control with 5-oxo-1,4,2-dioxazines
US3839010A (en) * 1970-05-19 1974-10-01 Exxon Research Engineering Co Thiocarbamic acid ester pesticides
US4632698A (en) * 1983-09-02 1986-12-30 Union Carbide Corporation Biocidal 2-aryl-1,3-cyclopentanedione enol ester compounds

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19604582A1 (de) * 1996-02-08 1997-08-14 Bayer Ag Verfahren zur Herstellung von substituierten Cyanophenyluracilen, neue substituierte Aminoalkensäure-cyanophenylamide als Zwischenprodukte hierfür und Verfahren zu deren Herstellung

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2329619A (en) * 1941-09-04 1943-09-14 American Cyanamld Company mu-substituted oxazolines, mu-substituted pentoxazolines, and methods for their preparation
US2447822A (en) * 1946-02-25 1948-08-24 Commercial Solvents Corp 5-nitrotetrahydro-1, 3-oxazines and method for preparing them
US2758994A (en) * 1956-08-14 Production
US2797217A (en) * 1957-06-25 Dihydro oxazine diones
US3022150A (en) * 1960-02-23 1962-02-20 Du Pont Herbicidal composition and method employing mixtures of substituted ureas and triazines
US3037853A (en) * 1958-04-04 1962-06-05 Du Pont Herbicidal composition and method employing a mixture of ethyl n, n-dipropylthiolcarbamate and a herbicidal s-triazine
US3210355A (en) * 1963-03-06 1965-10-05 Ciba Geigy Corp Pyrimidinones and process of preparing same
US3223707A (en) * 1963-12-23 1965-12-14 Stauffer Chemical Co 2-(trifluorobutenylmercapto)-pyrimidines
US3235357A (en) * 1959-08-14 1966-02-15 Du Pont Method for the control of undesirable vegetation

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2758994A (en) * 1956-08-14 Production
US2797217A (en) * 1957-06-25 Dihydro oxazine diones
US2329619A (en) * 1941-09-04 1943-09-14 American Cyanamld Company mu-substituted oxazolines, mu-substituted pentoxazolines, and methods for their preparation
US2447822A (en) * 1946-02-25 1948-08-24 Commercial Solvents Corp 5-nitrotetrahydro-1, 3-oxazines and method for preparing them
US3037853A (en) * 1958-04-04 1962-06-05 Du Pont Herbicidal composition and method employing a mixture of ethyl n, n-dipropylthiolcarbamate and a herbicidal s-triazine
US3235357A (en) * 1959-08-14 1966-02-15 Du Pont Method for the control of undesirable vegetation
US3022150A (en) * 1960-02-23 1962-02-20 Du Pont Herbicidal composition and method employing mixtures of substituted ureas and triazines
US3210355A (en) * 1963-03-06 1965-10-05 Ciba Geigy Corp Pyrimidinones and process of preparing same
US3223707A (en) * 1963-12-23 1965-12-14 Stauffer Chemical Co 2-(trifluorobutenylmercapto)-pyrimidines

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3451802A (en) * 1966-06-27 1969-06-24 Gulf Research Development Co Triazine herbicides
US3442640A (en) * 1966-11-22 1969-05-06 Givaudan Corp Methods of destroying weeds with substituted tetralins
US3529952A (en) * 1968-09-17 1970-09-22 Du Pont Plant control with 5-oxo-1,4,2-dioxazines
US3839010A (en) * 1970-05-19 1974-10-01 Exxon Research Engineering Co Thiocarbamic acid ester pesticides
US4632698A (en) * 1983-09-02 1986-12-30 Union Carbide Corporation Biocidal 2-aryl-1,3-cyclopentanedione enol ester compounds

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DK129683C (en)) 1975-04-21
DK129683B (da) 1974-11-11
GB1060741A (en) 1967-03-08
DE1620107A1 (de) 1970-03-05
BE644357A (en)) 1964-08-26
NL141358B (nl) 1974-03-15
SE319478B (en)) 1970-01-19
ES296865A1 (es) 1964-05-01
CH450810A (de) 1968-04-30
BR6456168D0 (pt) 1973-08-09
MY6800030A (en) 1968-12-31
DE1567016A1 (de) 1970-04-16
NO118883B (en)) 1970-02-23
NL6401832A (en)) 1964-08-28

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