IL27610A - Biuracils and their use as herbicides - Google Patents
Biuracils and their use as herbicidesInfo
- Publication number
- IL27610A IL27610A IL27610A IL2761067A IL27610A IL 27610 A IL27610 A IL 27610A IL 27610 A IL27610 A IL 27610A IL 2761067 A IL2761067 A IL 2761067A IL 27610 A IL27610 A IL 27610A
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- IL
- Israel
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- carbon atoms
- butyl
- methyluracil
- group
- bromo
- Prior art date
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Classifications
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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
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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
- C07D239/545—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other 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
- C07D239/553—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other 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 with halogen atoms or nitro radicals directly attached to ring carbon atoms, e.g. fluorouracil
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
27610/2 o»a»y » eipa oa »iB»rm Novel biuracile and their use ae herbicides E.I. J>V POST m HBMOURS AHD COMPACT - la This invention relates to novel compounds, which for the sake of simplicity can be called WTuracils, and to their use as herbicides* She novel compounds of the invention are reoriented by the following etructural forotulai wherein R can be the same or different at the two positions indicated and is selected from the group consisting of alkyl of 3 to 8 carbon atoms, phenyl, benzyl, cycloalkyl of 5 to 8 carbon atoms and substituted cycloalkyl of 5 to 8 carbon atoms wherein said substituent(s) is selected from the group consisting of methyl and methoxy; Ri can be the same or different at the two positions indicated and is selected from alkyl of 1 to 3 carbon atoms ; X can be the same or different at the two positions indicated and is selected from the group consisting of methyl, chlorine, bromine, and iodine; and can be hydrogen provided the R on the same ring is cycloalkyl, and with the further oroviso that X can be joined with ^l, when X is methyl so that a trimethylene or tetra- methylene group is formed; and Z is selected from the group consisting of 0 0 0 R 0 0 0 " II It I II II II where Rg is hydrogen or alkyl of 1 to 4 carbon atoms and R^ is a divalent radical selected from alkylene of 1 through 12 carbon atoms, alkenylene of through 12 carbon atoms, cyclohexylene and phenylene.
Preferred compounds within the above formula are those where R, R^, and X are the same as above, however the compound is symmetrical and Z is 0 n (I tl -C-C-.
Exemplary of the preferred compounds are the following Ι,Ι'-oxalyl bis (3-sec . -butyl-5-bromo-6-methyluracil) Ι,Ι'-oxalyl bis (3-iso. -propyl- -bromo-6-methyluracil) Ι,Ι'-oxalyl bis (3-iso. -propyl-5-chloro-6-methyluracil) Ι,Ι'-oxalyl bis (3- ert . -butyl-5-chloro-6-methyluracil) Ι,Ι'-oxalyl bis <(3-cyclohexyl-6, 7-dihydro-5-cyclopenta(d) pyrimidine-2,4-(lH, 3H) -dione7 Ι,Ι'-oxalyl bis (3-ter .-butyl-5-bromo-6-methyluracil) There is the possibility that the Z-linkage occurs through the 2-positioned oxygens rather than through the 1-positioned nitrogens as shown in the formula above since uracils may react in their enol or keto form as: Absorption sp^ytrfol evidence (infra-red) for the Z-oxygen linkage is strongly suggested by the products of this "t invention where Z is derived from phosgene (Z=C=0). Thus both roducts (Z-nitrogen or Z-oxygen linkage) or mixtures of these linkages are considered within the scope of this invention.
For the sake of clarity or brevity however, the compounds will be named assuming the reaction to ha^e occurred on the 1-nitrogen.
The above compounds are useful as herbicides. They DETAILED DESCRIPTION OF THE INVENTION The compounds of this indention can be prepared by treating two equivalents of the sodio derivative of an appropriately substituted uracil with one equivalent of a bifunc- tional acid chloride as illustrated by the following reaction: e © second uracil, in which R, R , and X are not necessarily the same for the two uracil rings coupled together. This is illustrated by the following equation: 0 stituted uracil employed in step 1. (•v) 0 Reaction (^ is performed in the presence of any of several inert solvents, such as tetrahydrofuran, dioxane, dimethylformamide, chloroform or benzene to facilitate mixing of the reactants. The mixture of 2 molar equivalents of the al acid chloride is stirred from 2 to 4 hours at temperatures from 20° to 75eC The product can be isolated in any of several ways, such as (1) filtration, followed by a water wash to sodium salts remove / norganios leaving behind essentially pure product (2) vacuum stripping of the solvent, followed by treatment with base to remove uncoupled uracil, filtration and water wash as above. Purification, if necessary, is accomplished by recrystal-liEation from common organic solvents or by chemical extraction.
The first step of reaction jjfc) is performed in the presence of any of several inert solvents, such as tetrahydro-furan, dioxane, dimethylformamide, chloroform or benzene to facilitate mixing of the reactants. The mixture of bifunctional acid chloride, one equivalent of a sodio derivative of an appropriately substituted uracil is stirred for 1/2 to 24 hours at temperatures of from 0° to 75°C. To the above stirred mixture of l-((Jti-halooxygenatedhydrocarbo)uracil is added a second equivalent of an appropriately substituted uracil.
The second step of reaction (J/) involves stirring for from 2 to 24 hours at temperatures of from 20° to 7 °C Product isolation can be performed as described in reaction {¥) .
In order to more fully describe this invention the following additional examples are given. All parts are parts by weight unless otherwise indicated.
Example 1 1,1' -carbonyl bis ( -hromo-3-sec_-butyl-6-methyluracil) A total of 28 parts of 5-bromo-3-sec-butyl-6-methyluracil sodio derivative is suspended in 200 parts of tetrahydrofuran. Slowly with stirring 5 parts of phosgene are added. The temperature is allowed to rise autogenetically, then the reaction is stirred at room tem erature for 16 hours. treated at 0* with parts of sodium hydroxide contained in 100 parts of water. The solid is filtered, washed with water and dried and is essentially pure Ι,Ι'-carbonyl bis(5-¾>romo-3-sejc-butyl-6-methyluracil), m.p. 220*.
Example 2 1,1' -oxalyl bis (3-1ert . -but l-5-chloro-6-methyluracil) Two hundred parts of anhydrous tetrahydrofuran is placed in a 3-neck flask equipped with a stirrer, condenser and an additional funnel. Four and two tenths parts of a 6 # suspension of sodium hydride (in mineral oil) is charged into the stirring flask followed by 21.6 parts of 3-ter .- utyl-5- ambient chloro-6-methyluracil. This mixture is stirred at tmh-itde t temperature for 16 hours.
Oxalyl chloride, 6.3 parts is added drop-wise to the above vigorously stirred mixture. Stirring is continued for an additional four hours, then the reaction mixture is poured into 2000 parts of cold 2% aqueous sodium hydroxide solution. The precipitated solids collected by filtration, washed with water then recrystallized from ethanol gave essentially pure 1,1 '-oxalyl bis (3-tert . -butyl-5-chloro-6-methyluracil), m.p. 172-172.5°C.
Example 3 The following products can be prepared by substituting the appropriate amounts of the following uracil sodio derivatives and polyfunctional acid chlorides for 5-brorao-3-se^-butyl-6-methyluracil sodium salt and phosgene cited in Example 1 or the 3-tert. -butyl-5-chloro-6-me hyluracil sodium salt and oxalyl chloride of Example 2.
Substituted uracil Polyfunctional 1,11 -oxohy sodio derivatives acid chloride uracil 3-sec-butyl-5-bromo-6- oxalylchloride 1,1 ' -oxaly methyluracil sodio salt 6-methylur malonyldichloride 1,1 ' -malon 6-methylur '! succinyldichloride 1,1' -Bucci 6-methylur adipoyldichloride 1,1' -adipo -methylur sebacyldichloride 1,1 " -sebac 6-methylur ihthalyldichloride 1,1' -phtha 6-methylur iso hthalyldichloride 1,1' -isoph 6-raethy ur terephthalyldichloride 1,11 -tere> romo-6-me erhydroohthalyldi- 1,1' -perhy chloride -bromo-6- ^erhydroisophthalyl- 1,1' -perhy dichloride 5-brorao- - perhydroterephthalyl- 1,1' -perhy dichloride butyl-5-br Substituted uracil Polyfunctional 1, 1 ' -oxo sodio derivatives acid chloride uracil fumaryl chloride 1,1 '-fum methylur 3-sec-butyl-5-chloro-6- oxalylchloride 1,1' -oxa methyluracil sodio salt methylur 3-tert-butyl-5-chloro-6- oxalylchloride 1,1' -oxal ethyluracil sodio salt 6-ethylu 3-(iso-Propyl)-5- romo-6- oxalylchloride 1,1' -oxal methyluracil sodio salt 6-methylu 3-sec-butyl-5-chloro-6- oxalylchloride 1,1 '-oxa ethyluracil sodio salt e hylurac 3-tert-butyl-5-bromo-6- phosgene 1,1 * -carb n-prop luracil sodio salt 6-n-prop -iso-propyl-5-iodo-6- malonyldichloride 1,1 ' -mal iso-propyluracil sodio iso-prop salt 3-(3-pentyl)-5-bromo-6- oxalylchloride 1,11 -oxa methyluracil sodio salt methylur 3-n-butyl-5-methyl-6-methyl fumarylchloride 1,1» -fum uracil sodio salt u racil) 3- (n-hexyl) -5-chloro-6- phthalyldichloride 1,1' - ht ethyluracil sodio salt ethylurac 3- ( tert-octyl) -5-iodo-6- fumarylchloride ethylurracil sodio salt —ethylu Substituted uracil Polyfunctional 1,1* -oxohy sodio derivatives acid chloride uracil) 3-n-proi yl-5-methyl-6- 1,2,3,6 tetrahydro- 1, 11 -1, 2,3 ethyluracil sodio salt ;jhthalyl dichloride ( -n-:iropy 3-tert-butyl-5-chloro-6- aconityltrichloride l,r-aconit ethyluracil sodio salt 6-ethylura 3-(3-pentyl) -5-chloro-6- oxalylchloride 1, 1' -oxaly methyluracil sodio salt -methylur 3-sec-but l-5-iodo-6- succinyldichloride 1, 1' -succi methyluracil sodio salt 6-methylur 3-phenyl-5-bromo-6-methyl- Phosgene 1,1 ' -carbo uracil sodio salt methylurac 3-benzyl-c>-bromo-6-methyl- itaconyldichloride 1,1' -itaco uracil sodio salt raethylu ac 3-phenyl-5-chloro-6-ethyl- sebacyldichloride 1,1 ' -sebac uracil sodio salt ethylu aci 3-cyclopentyl-5-chloro-6- glutaconyldichloride 1,1» -gluta methyluracil sodio salt 6-methylur 3-cyclohexyl-5-bromo-6- ihosgene 1,1' -carbo methyluracil sodio salt 6-methylur 3-cycloheptyl-5-bromo-6- perhydroterephthaly1- 1,1' -perhy methyluracil sodio salt dichloride heOtyi- -b 3-cyclooctyl- -methyl-6- succinyldichloride 1,1' -succi n- rop luracil sodio salt 6-n- -> rουyl Substituted uracil Poly unctional 1,1' -oxohy sodio derivati es acid chloride uracil) 3-(2-methylcyclohexy1) -5- >hosgene 1, 1' -carbo bromo-6-ethyluracil sodio salt 5-bromo-6- 3-(2-methoxyeyelohexy1)-5- oxalylchloride 1,1' -oxaly ±odo-6-methyluracil sodio salt 5-iodo-6-m 3-( -methylcyclohexyl)-5- thapsyldichloride 1,1' -thaps chloro-6-methyluracil sodio salt -chloro-6- 3-cyclohexyl-6-methyluracil phosgene 1,1' -carbo sodio salt uracil) 3-cyclooctyl-6-ethyluracil oxalylchloride 1,1 ' -oxaly sodio salt uracil) 3-cyclopentyl-6-ethyluracil malonyldichloride 1,1' -malon sodio salt uracil) 3-(2-methyIcyclohexy1) -6- isophthalyldichloride 1,1' -isoph methyluracil sodio salt 6-methylur 3-(3-methoxyeyelohex 1)-6- oxalylchloride 1,1' -oxaly ethyluracil sodio salt 6-ethylura 3-sec-butyl-5-methyl-6-iso- succinyldichloride 1,1 ' -succi propyluracil sodio salt iso-oropyl 3-(2-methylcyclohexy1) -5»6, ohosgene 1,1' -carbo 7,8-tetrahydro-2, -(lH,3H)- 5,6,7,B-te quinazolinedione sodio salt dione*7 Substituted uracil Polyfunctional 1, 1 ' -oxohy sodio derivatives acid chloride uracil) 3-cyclohexy1-6,7-dihydro- - Dhosgene 1,1' -carbo cyclopenta/37 pyrimidine- 5-cyclonen 2,4-/lH rdione sodio salt dione7 3-tert-buty1-5,67,8-tetra- oxalylchloride 1, 1 ' -oxaly hyHro¾,4-/ΪΗ,3tf7-quinazo- tet ahydro linedione sodio salt 3-iso-propyl-5*6,7,8-tetra- malonyldichloride 1,1' -malon hydO-2, -/IH,W-quinazo- tetrahydro linedione sodio salt 3-phenyl-5,6,7,8-tetrahydro- phthalyldichloride 1,1' -nhtha 2,4-/ΪΗ,5H -quinazolinedione hydro-2, ;* -sodio salT 3-sec-t>utyl-5,6,7,8-tetra- phosgene l,l'-carbo hy3ro-2, -/ΪΗ,¾7-quinazo- tetrahydro linedione sodio salt 3-eyclooctyl-5,6,7,8-tetra adir>oyldichloride 1,1' -adi^>o hydro-2, - TH,W-quinazo- tetrahydro linedione sodio salt 3-sec-butyl-6,7-dihydro-5- oxalylchloride 1,1' -oxaly cyclopenta/T/ yrimidine- fi-cyclo en 2,- H,W:rd one sodio dione7 salt 3-iso-p ropy1-6,7-dihydro-5- citraconyldichloride 1,1 '-cltra cyc openta/d"^yrimidine- -cyclo en 2,4-/TH,3H7-" ione sodio dione7 salt ~" Substituted uracil Polyfunctional 1, 11 -oxohy sodio derivatives acid chloride uracil) 3-cyclohexyl-6,7-dihydro-5- oxalylchloride 1,1' -oxaly cyclopenta dione/ phosgene 1,11 -carbo -cyclopen TH^E^-dione sodio salt 3-sec-butyl-5-iodo-6-methyl- phosgene 1,1 ' -carbo uracil sodio salt methylurac 3-tert-butyl-5-chloro-6- phosgene 1,1'-carbo raet yluracil sodio salt 6-methylur 3-tert-butyl-5-bromo-6- oxalylchloride 1,1' -oxaly methyluracil sodio salt 6-methylur 3-(2-penty1)-5-bromo-6- oxalylchloride 1,1 ' -oxaly methyluracil sodio salt 6-methylur 3-sec-butyl-5-chloro-6- phosgene 1,1 '-carbo ethyluracil sodio salt 6-ethylura 3- ert- utyl-5- romo-6-n- malonyldichloride 1,1' -malon propyluracil sodio salt 6-n- ropyl 3-iso- ropyl-5-iodo-6-l3o- oxalylchloride 1,1 ' -oxaly propyluracil sodio sa!i iso- trooyl 3-(3-pentyl)-5-bromo-6- phosgene 1,1' -carb methyluracil sodio salt 6-methylu Substituted uracil Polyfunctional 1,1' -oxohy sodio derivatives acid chloride uracil) 3-n-butyl-5-methyl-6- glutaryldichloride 1, 1 ' -gluta methyluracil sodio salt uracil) 3- (n-hexyl) -5-chloro- suberyldichloride 1,1' -suber 6-ethyluracil sodio salt ethyluraci 3-tert-octyl)-5-iodo-6- azelaiyldichloride 1,1 ' -azela ethyiuracil sodio salt 6-ethylura 3-n-propyl-5-methyl-6- pimelyldichloride 1,1 '-pimel eihyluracil sodio salt 6-ethylura 3-tert-butyl-5-chloro-6- phosgene 1,1 '-carbo ethyluracil sodio salt 6-ethylura 3-(3-pentyl)-5-chloro-6- phosgene 1,1 ' -carbo methyluracil sodio salt 6-methylur 3-sec-butyl-5-iodo-6- phosgene 1,1 '-carbo methyluracil sodio salt 6-methylur 3-thenyl-5-bromo-6-methyl- phosgene 1,1 '-carbo uracil sodio salt methylurac 3-benzyl-5-bromo-6-methyl- oxalylchloride 1,1" -oxaly uracil sodio salt methylurac 3-phenyl-5-chloro-6- oxalylchloride 1,1 ' -oxaly ethyluracil sodio salt ethyluraci 3-cyclopentyl-5-chloro-6- oxalylchloride 1, 1 ' -oxaly methyluracil sodio salt e-methylur Substituted uracil Polyfunctional 1, 1 ' -oxohy sodio derivatives acid chloride uracil) 3-cyclohexyl-5-bromo-6- oxalylchloride 1, 1 ' -oxaly methyluracil sodio salt 6-methylur 3-cycloheptyl-5-bromo-6- phosgene 1, 11 -carbo methyluracil sodio salt 6-methylur 3-cyclooctyl-5-methyl-6-n- r-hosgene 1,1' -carbo ropyluracil sodio salt 6-n-propyl 3-(2-methylcyclohexy1) -5- oxalylchloride 1,1' -oxaly bromo-6-ethyluracil sodio 5-bromo-6-salt 3-(2-methoxycyclohexy1) -5- ohosgene 1, 1 ' -carbo iodo-6-methyluracil sodio 5-iodo-6-m salt 3-(3-inethylcyclohexyl) -5- malonyldichloride 1,1' -malon chloro-6-methyluracil 5-chloro-6 sodio salt 3-eyelohexy1-6-methyluraci1 pimelyldichloride 1,1' -pimel sodio salt uracil) 3-cyclooctyl-6-ethyluracil succinyldichloride 1,1'-succi sodio salt uracil) 3-cyclopentyl-6-ethyluracil phthalyldichloride 1,1' -phtha sodio salt uracil) 3-(2-methylcyclohexy1) -6- phosgene 1,1' -carbo raethyluracil sodio salt 6-methylur Substituted uracil Polyfunctional 1,1' -oxohy sodio derivatives acid chloride uracil) 3- (3-methoxycyclohexy1)-6- phosgene 1-, 1 ' -carbo ethyluracil sodio salt 6-ethylura 3-sec-butyl-5-methy1-6-iso- phosgene 1,1' -carbo ropyluracil sodio salt 6-lso- op 3- (2-methylcycloheryl) - oxalylchloride 1,1 ' -oxaly 5, ,7,8-tetrahydro-2,4- 5,6,7,8-te lH,3l£7-quinazolinedione linedione7 sodio salt 3-cyclohexyl-627-dihydro- sebacyldichloride 1,1 ' -sebac 5-cyclopenta 3T¾yrimidine- dihydro-5- 2^-/TH,3¾7-cTfbne sodio salt 2, -(lH,3H 3-tert-buty1- ,6,7,8-tetra- 3,3-dimethylglutaryldi- 1,1'- (3,3- hydro^ ,h-/¾,3iV-quinazo- chloride butyl-5,6, linedione sodio salt quinazolin 3-iS£-Propyl-5,6,7,8-tetra- phosgene 1,1 ' -carbo hy^ro-2,k-/IS,3tf/-quinazo- tetrahydro linedione sodio salt dione7 3-phenyl-5,6,7,8-tetrahydro- phosgene 1,1' -carbo 2,k-/TH,3H/-quinazolinedione tetrahydro sodio sa.lT dione7 3-seen /TH^i^-dione sodio salt dione7 3-(3-pentyl)-6,7-dihydro-5- phthalyldichloride 1,1' -phtha cyclopenta/j pyrimidine-2,1!■· dihydro-5-/TH,3I^-dione sodio salt (lH,3H)-di 3-sec-butyl-5-iodo-6-methyl- oxalylchloride 1,1' -oxaly uracil sodio salt methylurac 3-tert-butyl-5-chloro-6- oxalylchloride 1, 11-oxal methyluracil sodio salt 6-methylur 3-tert-buty1-5-bromo-6- phosgene 1,1 '-carbo meihyluracil sodio salt 6-meth lur 3-(2-pentyl)-5-bromo-6- traumatyldichloride 1, 1 '-traum methyluracil sodio salt 6-meth lur Example 4 -bromo-3-sec-butyl-l-(5-bromo-2-tej-t-butyl- 1 ,2, 3, -te^rahydro-6-me hy1- , -dTo o-1-pyrimidiny1 carbonyl)-6-methyluracil A total of 14 parts of 5-bromo-3-sec-butyl-6-methyl uraeil sodium salt is suspended in 200 parts of tetrahydrofuran and stirred for a short time. Slowly, with stirring, is added parts of phosgene at temperatures between 10° and 0°C, then allowed to stir at these temperatures for 2 hours. Slowly, wit stirring, is then added 14 parts of 5-¾romo-3-tert-butyl-6-methyluracil sodium salt and the temperature is allowed to rise to a temperature not greater than 75°, usually 35° is maximum.
This mixture is allowed to stir for 2 hours at 25eC. The solvent is removed at reduced pressure and the residue treated at C° with parts of sodium hydroxide contained in 100 parts of water. Filtration and water wash yields essentially pure 5-bromo-3-seC-butyl-l-(5-bromo-3-tert-butyl-l,2,3j4,-tetrahydro- 6-methyl-2,4-dioxo-l-oyrimidinyl carbonyl)-6-methyluracil .
Exam le 5 The following products can be prepared by substituting carbyl the appropriate amounts of l-((jj-haloo genatedhydro9¾" BHe-- 5 j6-trisubstituted)uracil for the In situ generated 1-chlorocarbonyl 3-sec-butyl-5-bromo-6-methyluracil and 3-tert-butyl-5-bromo-6-methyluracil sodium salt givenin Example 4. 1-( -halooxygenated-hydrocarbo)-3,5j6- 3,5,6-trisubstituted trisubstituted uracil uracil, sodio derivatives l-chlorocarbonyl-3- ert- 3-tert-butyl-5-chloro- 3-tert* butyl-5-bromo-6-methyl- 6-me'thylurac11 sodio 3-tert uracil salt meT yT- carbony l-chlorooxalyl-3-sec-butyl- 3-tert-butyl-5-chloro- 3-1ert-5-bromo-6-methyluracil 6-methyluracil sodio butyl-5 salt 6-methy oxalyl) l-chlorocarbonyl-3-sec- 3-(2-methylcyclohexyl) - 3- (2-me buty1-5-bromo-6-methyl- 5,b,7i8-tetrahydro-2,4- butyl-5 uracil IH,3H7-q inazolinedione 6-methy sodio salt carbony 3H/ l-chloromalonyl-3-tert- 3-(2-pentyl)-5-t>romo-6- 3- (2-pe butyl-5-chloro-6-methyl- methyluracil sodio salt butyl-5 uracil 6-methy malonyl l-chlorooxalyl-3-tert- 3-sec-butyl-5-bromo-6- 3-sec-b butyl-5-bromo-6-methyl- methyluracil sodio salt 5-bromo uracil dioxo-l methylu l-chlorocarbonyl-*3-sec- 3-cyclohexyl-6-methyl- -cyc1o butyl-5-chloro-6-methyl' uracil sodio salt chloro-uracil 1-pyrim uracil 1- ( -halooxygenated- ydrocarbo)-5,5»6~ 3,5,6-trisubstituted trisubetituted uracil uracil, sodio derivatives l-chlorocarbonyl-3-phenyl- 3-benzyl-5-bromo-6- 3-benzy -chloro-6-methyluracil methyluracil sodio salt l,2,35¾ pyrimidi Exam le 6 1,1' -(1-oxoethylene) bis (5-hromo-3-iso propyJ-6-methyl- uracil) Two hundred parts of dry tetrahydrofuran is placed in a reactor equipped with an agitator and a reflux condenser. A 6o# suspension of sodium hydride(in mineral oil), 4.2 parts is charged into the stirring reactor followed by 24.7 parts of -bromo-3-ijso propyl-6-methyluracil. This mixture is stirred ambient at ¾mb1dflint, temperature for 16 hours.
Chloroacetyl chloride 5-6 parts is added gradually to the above stirring mixture. After the addition is complete, the reaction mixture is stirred an additional 4 hours then poured into 2000 parts of ice-cold 2% aqueous sodium hydroxide solution. The precipitated solid collected by filtration, washed with water until alkali-free is technical grade bis (5-bromo-2-iso propyl-6-methyluracil) which can be purified by recrystallization from ethanol.
Equivalent amounts of the corresponding reagents (appropriate ^-halogenated acid chlorides and uracils) can be substituted for the chloroacetyl chloride and 5-bromo-3-iso propyl-6-methyluracil of the procedure above and the following compounds of this invention can be prepared: 1, 11 - (1-oxoethylene) bis-( -bromo-3-sec . -butyl-6-methyl- uracil) 1,1' -(l-oxo-2-methylethylene) bis-(5-bromo-3-sec . -butyl- 6-methyluracil) 1,1· - (l-oxo-2-methylethylene) bis- (5-chloro-3-cyclohexyl-6- methyluracil) 1,1' - (1-oxoethylene) bis-/ -chloro-3- ( 1-ethyl ropyl) -6- methyluracil7 1,1' -(l-oxo-2-methylethylene) bis-(5-chloro-3-tert . -butyl- 6-methyluracil) 1,1' -(1-oxoethylene) bis-(5-bromo-3-tert . -butyl-6-methyl- 1,1 (1-oxoethylene) bis-( -5-chloro-3-benzyl-6-methyluracil) ι,ι (1-oxoethylene) bis-( 5-tiromo-3- ^henyl-6-methyluracil) 1,1 (l-oxo-2-butylethylene) bis- (5-chloro-3-isopropyl- 6-methyluracil) 1,1 (l-oxo-2-ethylethylene) bis- (5-bromo-3-isopyopyI- 6-me hyluraci1) ι,ι (l-oxo-2-methylethylene) bis- ( 5-iodo-?-isog>ropyl-6- · meth lu acil) 1,1 (1-oxoethylene) bis- (j?-cyclohexyl-6-methyluracil) 1,1 (•1-oxoethylene) bis- (6-methyl-3-norbornyluracil) ι,ι (1-oxoethylene) bis- (5,6-dimethyl-3-cyclohexyluracil) ι,ι (1-oxoethylene) bis- 5-cyclohexyl-6,7-dihydro-5-cyclo- penta (d) oyrimidine-2,4-(lH,3H)-dione7 The compounds of the Invention can be admixed with pest control adjuvants or modifiers to provide herbicidal compositions in the form of dusts, granules, pellets, water-dispersible powders, high-strength concentrates, and emulsions and solutions or dispersions in organic liquids.
Thus, the compounds of this invention can be used with a carrier or diluent agent such as a finely divided solid, an organic liquid, a wetting agent, a dispersing agent, or any suitable combination of these.
Compositions containing the compounds of the invention, especially liquids and wettable powders, contain as a conditioning agent one or more surface-active agents, sometimes called surfactants, in amounts sufficient to render the composition readily dlspersible in water or in oil.
The surface-active agent used can be a wetting, dispersing or an emulsifying agent which will assist dispersion of the compound. The surface-active agent or surfactant can include such anionic, cationic and non-ionic agents as have heretofore been generally employed in plant control compositions of similar type. Suitable surface-active agents are set forth, for example, in "Detergents and Emulsifiers" 1965 Annual by John . McCutcheon, Inc.
In general, less than 10$ by weight of the surface-active agent will be used and ordinarily the amount of surface-active agents will range from 1-5$ but may even be less than 1$ by weight.
Additional surface-active agents can be added to the formulations to increase the ratio of surfactant : active ingredient up to as high as 5:1 by weight. Such compositions have a greater herbicidal effectiveness than can be expected from a When used at higher rates it is prefered that the surfactant be present in the range of one-fifth to five parts surfactant for each one part of active agent.
Wettable powders are water-dispersible compositions containing the active material, an inert solid extender, and one or more surfactants to provid rapid wetting and prevent heavy flocculation when suspended in water.
The classes of extenders suitable are the natural clays, diatomaceous earths, and synthetic mineral fillers derived from silica and silicates. Most preferred fillers are kaolinites, attapulgite clay, montmorillonite clays, synthetic silicas, synthetic magnesium silicate and calcium sulfate di-hydrate.
Wettable powder formulations will contain from about 25 to 90 weight per cent active material, from 0.5 to 2.0 weight per cent wetting agent, from 0.25 to 5.0 weight per cent dispersant, and from 9.25 to 7^ .2 weight per cent inert extender, as these terms are described above.
High-strength compositions generally consist of 90 to 99 - 5$ active ingredient and 0.5 to 10$ of a liquid or solid surfactant such as those described by McCutcheon in "Detergents and Emulsifiers" 1965 Annual. Such high-strength compositions can often be used in a manner similar to the wettable powders but they are also suitable for further formulation.
The organic liquid suspension concentrates are prepared by mixing together and sandgrinding a slurry of oil-insoluble active ingredient in the presence of dispersing agents.
These organic liquid suspension concentrates will contain from 15 to h of active ingredient, from 5 to 70$ organic liquid such as kerosene, mineral oil and certain weed Dusts are dense powder compositions which are intended for application in dry form in accordance with the preferred compositions and methods of the invention. Dusts are characterized by their free-flowing and rapid settling properties so that they are not readily windborne to areas where their presence is not desired. They contain primarily an active material and a dense, free-flowing, solid extender but may also contain grinding aids and surfactants.
Thus, the dust compostions will comprise about 5 to 20 weight per cent active material, 5 to 50 weight per cent absorptive clay filler, 0 to 1.0 weight per cent wetting agent, and about 30 to 9 weight per cent dense, free-flowing dust diluent, as these terms are used herein.
Emulsifiable oils are usually solutions of active material in non-water miscible solvents together with a surfactant .
For the compounds of this invention, emulsifiable oils can be made by mixing the active ingredient with a solvent and surfactant. Suitable solvents for the compounds of this invention are aromatic hydrocarbons including many weed oils, chlorinated solvents, and non-water miscible ethers, esters, or ketones .
Thus, emulsifiable oil compositions will consist of from about 15 to 50 weight per cent active material, about ^O to 82 weight per cent solvent, and about 1 to 10 weight per cent emulsifier, as these terms are defined and used above.
Granules and pellets are physically stable, particulate compositions containing a compound of this invention which adheres to or is distributed through a basic matrix of a co-herent, inert carrier with macroscopic dimensions. In order to aid leaching of the active ingredient from the granule or pellet, a surfactant can be present.
For the compounds of this invention, the inert carrier is preferably of mineral origin, and the surfactant is a compound known to the art as a wetting agent.
There are two suitable types of carriers for the granule compositions containing compounds of the invention as an active material. The first are porous, absorptive, preformed granules, such as preformed and screened granular attapulgite or heat expanded, granular, screened vermiculite. On either of these, a suspension of the active agent can be sprayed and can be absorbed at concentrations up to 25 weight per cent of the total weight. The second, which are also suitable for pellets, are initially powdered kaolin clays, hydrated attapulgite, or bentonite clays in the form of sodium, calcium or magnesium bentonites. Water-soluble salts, such as sodium salts, may also be present to aid in the disintegration of granules or pellets in the presence of moisture. Theseingredients are blended with the active components to give mixtures that are granulated or pelleted, followed by drying, to yield formulations with the active component distributed uniformly throughout the mass. Such granules and pellets can also be made with 25 to 30 weight per cent active component, but more frequently a concentration of about 10 weight per cent is desired for optimum distribution. Granular compositions are most useful in a size range of 15 - 30 mesh.
Thus, the preferred granular or pelleted formulations comprise about 5 to 30 weight per cent active material, about 0 to 5 weight per cent wetting agent, and about 65 to 95 weight per cent inert mineral carrier, as these terms are used herein. general purpose weed killers or soil sterilants for control of vegetation on industrial sites and railroad ballast particularly in areas o-f high rainfall.
These compounds also exhibit selective herbicidal action in crops. By properly selecting a bis-uracil of the invention and a rate and time of application, weeds growing in such crops as blackberries, asparagus and sugar cane can be controlled .
The amount of bis-uracil herbicide to be used in any instance will be governed by such factors as climate, the type of weed to be controlled, soil conditions, and the like, and so it is not possible to give a rate of application suitable for all situations. Generally speaking, one uses the bis-uracils at levels of 0 .25 to 8 pounds per acre for selective control in crops. Rates of 5 to 40 pounds per acre are satisfactory for general weed control.
The following examples better illustrate the manner in which the compounds of this invention are formulated and used as herbicidal agents.
Example 7 1, 1 ' -carbonylbis( 5-bromo-3-sec-butyl-6- methyluracil) 25.0$ attapulgite clay 69 . 5$ synthetic silica 2.0$ dioctyl sodium sulfosuccinate 2.0$ sodium lignin sulfonate 1 . 5$ The above ingredients are blended, micropulverized to a particle size essentially below 50 microns and then re-blended.
The above material is suspended in water at the rate This material is applied pre-emergence to areas in a tank farm at rates of 50 to 100 gallons per acre. The exact volume applied is predicated on the plant species to be controlled and the duration of control desired. Such weeds as crabgrass (Dlgitaria spp . ) , barnyard grass (Echinochloa crusgalli) , lambsquarter (Chenopodium album), dog fennel (Helenium tenui-folium) , Johnson grass seedlings (Sorghum halepense), bluegrass (Poa spp.), wild garlic (Allium vineale), dock (Rumex spp.), peppergrass (Lepidium virginicum) and poison ivy seedlings (Rhus radicans) are controlled for an extended period.
All of the other compounds of the invention can be formulated and applied in like manner.
Example 8 1,1 '-oxalylbis(5-bromo-3-sec-butyl-6- Qo.0 methyluracil) montmorillonite clay 14. $ synthetic silica 2.0$ sodium alkyl napthalene sulfonate 3.0$ methylated cellulose 0. $ The above ingredients are blended, micropulverized to a particle size essentially below 50 microns and then reblended.
The formulation is suspended in water to provide a ratio of 14 pounds of active ingredient in 50 gallons of water which is applied on one acre of a grass rhizone barrier strip encircling citrus orchards. The chemical is thoroughly incorporated by disking or rototilling to a depth of8 inches within 2 hours after application. Control of torpedo grass (Panicum repens) , Bermuda grass (Cynodom dactylon), Johnson grass (Sorghum halepense), and centipede grass (Eremochola ophiuroldes) is obtained. There is no injury to the citrus The following compounds can be formulated and applied in like manner: Ι,Ι'-oxalyl bis (3-isopropyl-5-bromo-6-methyluracil) l,l'-oxalyl bis (3-tert-butyl-5-chloro-6-methyluracil) Ι,Ι'-oxalyl bis /5-cyclobexyl-6,7-dihydro-5-cyclopenta(d) pyrimidine-2",4- (1H,J>E) -dione7 Ι,Ι'-malonyl bis (3-sec-butyl-5-bromo-6-methyluracil) Ι,Ι'-terephthalyl bis (3-sec-butyl-5-bromo-6-methyluracil) 1,1 ' -perhydroterephthalyl bis (3-sec-butyl-5-bromo-6- methyluracil) Ι,Ι'-oxalyl bis (5-tert-butyl-5-bromo-6-methyluracil) Example 9 3-tert-butyl-5-chloro-l-(5-bromo-3-tert- &utyl-l,2j2.4-tetrahydro-6-met yT^2,4- dioxo-l-pyrimidinyl carbonyl) -6-methyluracil 25$ kaolinite 69# calcium sulfate dihydrate 2% nonyl phenyl polyethylene glycol ether 3$ sodium lignin sulfonate 1 The above ingredients are blended, micropulverized to a particle size essentially below 50 microns and then reblended.
A 25$ wettable powder formulation is suspended in water and applied with a tractor mounted sprayer so that 2 to 4 lbs. of active ingredient is applied on one acre of asparagus in the spring before the spears emerge. Good control of lambs quarters (Chenopodium album) , ragweed (Ambrosia antemisifolia) , mustard (brassica nigra), chickweed (stellaria media), orabgrass (digitaria spp. ) and goosegrass (Eleusine indica) is obtained through the cutting season. No crop injury is experienced.
The following compounds can be formulated and applied in like manner: (1-oxoethylene) bis (5-bromo-3-sec-butyl-6-methyl- uracil) l-oxo-2-methylethylene) bis- (5-chloro-3-tert butyl -methluracil) Example 10 -oxalylbis(3-tert-butyl-5~chloro-6- methyluracil") calcium lignin sulfonate plus wood sugars 9.' dioctyl sodium sulfosuccinate 0. $ -30 mesh attapulgite 85.0$ The active material, the calcium lignin sulfonate plus wood sugars and the wetting agent are micropulverized to a particle size substantially less than 100 microns. This product is suspended in water and sprayed on the granules of attapulgite which are tumbled in a mixer. Following drying, the granules are ready for application.
Twenty pounds of the above granular formulation (equivalent to 4 lb. /acre of active ingredient) are spread on an acre of Louisiana sugar cane in the spring just after off baring. Good control of crabgrass (Digitaria spp.), barnyard grass (Echinochloa crusgalll), mustard (Brassica spp.), r?hl/»kweed (stellaria media), lambsquarter (Chenopodium album), and Johnson grass (Sorghum halepense) s-eedlings is obtained with no significant injury to the crop.
Example 11 1,1' -phthalylbis/3-phenyl-5a6,7,8- tetrahydro-"2",4-(lH,3H)-quinzao- linedione7 10$ diatomaceous silica 5$ micaceous talc 85$ The above dust is prepared by blending and grinding the active material with the minor diluent then blendin the The above dust formulation is applied with a dust blower to general weedy vegetation around the swampy edge of a pond so that 20 lbs. of active ingredient are applied on one acre. Good control of general weed species is obtained permitting a freer flow of water, and thus reducing areas of impounded water that provide breeding grounds for mosquitos.
Example 12 1,11 -oxalylbis (5-bromo-3-tert-butyl- 6-methyluracil) 10$ sodium sulfate, anhydrous 10$ calcium lignin sulfonate 5$ kaolinite 75$ The above components are ground to pass a 50 mesh screen, moistened with water and extruded and cut to form pellets approximately 1/16 x 3/32 in size. The pellets are dried and can be used as such or can be further subdivided into granules in the 15-60 mesh range.
The above pellets or granules are applied with an auger spreader on railroad rights of way so that 20 lbs. of active ingredient are applied on one acre of actually treated area. Good control of foxtail (Setaria spp.), broomsedge (Andropogon ylrginlcus) , Bermuda grass (Cynodon dactylon) , and raarestail (Erigeron canadensis) is obtained.
Example 13 1, 1 * -sebacylbis (3-sec-butyl-5-bromo- 6-methyluracil) 1 $ alkylaryl polyethylene glycol ether $ isophorone 80$ The above emulsifiable oil is prepared by mixing the components with agitation until a homogeneous solution The formulation is extended with water or herbicidal oil in the proportion of 8 lbs. of active ingredient per 100 gallons of carrier and sprayed with a low pressure, large droplet forming sprayer on utility rights of ways. The general vegetation is sprayed thoroughly to wet both stems and foliage. Good control of maple (Acer spp.), Virginia pine (pinus vir-glnana) , sweet gum (liquidambar styraciflua) , tulip poplar (Lirlodendron tulipifera) , broomsedge (Andropogon virglnicus ) , mountain laurel (Kalmia latlfolia), and poison ivy (Rhus radicans) is obtained.
Example I 1,11 -carbonylbis(5-bromo-3-tert-butyl- 6-methyluracil) sodium lauryl sulfate sodium lignin sulfonate attapulgite clay synthetic silica The above components are blended, micropulverized to a particle size below 50 microns and reblended.
A mixture is made with water using the formulation mentioned above to provide a concentrate of 8 lbs. of active ingredient in 50 gal. of carrier and is sprayed on one acre of blackberries. The spray mixture is directed toward the base of the plant on to freshly cultivate soil just prior to the time new leaves emerge in the canes in the spring. A repeat application of lbs. per acre one month later provides full season weed control. Good control of chickweed (stellaria media), henbit (Lamium amplexicaule) , lambsquarter (Chenopodium album), field eress (Rorippa austriaca), wild mustard (Brassica sp . ) , crabgrasa (Digitaria spp.) or goosegrass (Eleusine indiea) is 4 Example 15 1, 11 -carbonylbis (5-sec-butyl- 5-chloro- 6-ethyluracil) 0$ soya lecithin 2.% mineral oil 6 # sorbitan hexaoleate 5$ The above oil suspension is prepared by first grinding the active compound to pass a 40 mesh screen. All the components are then mixed and sand ground to a particle size substantially below 5 microns. The product is characterized by its extremely small particle size so that when diluted with weed oil or emulsified in water and sprayed, plant foliage is uniformly coated.
The above formulation is suspended in herbicidal oil to form a concentrated homogeneous suspension. The suspension containing 20 lbs. of active ingredient in 50 gallons of carrier is applied by high pressure sprayer mounted on a helicopter and distributed over one acre of area for fire-break maintenance.
Good control of crabgrass (Digitaria spp . ) , foxtail (setaria spp . ) , broomsedge (Andropogon virginicus), maple (Acer spp . ) sprouts and mountain laurel (Kalmia latifolia) sprouts is obtained.
Example 16 1, 1 '-carbonylbis- (5-bromo-5-sec-butyl- 6-methyluracil) 91 alkylarly polyethylene glycol ether > The above components are blended and ground to pass a 20 mesh screen. This composition is suitable for further formulation or under some circumstances can be used directly a& a granular material. 4 granules uniformly. Two pounds of the partially granulated mixture is spread evenly over 1,000 square feet of crushed rock, sand, gravel or ballast before applying an asphalt road surface. Good control of Bermuda grass (cynodon dactylon), Johnson grass (Sorghum halepense) and torpedo grass (Panicum repens) is obtained.
Claims (11)
1. A method for the control of undesirable vegetation, said method comprising applying to a locus to be protected from said vegetation a herbicidally effective amount of a compound of the formula wherein R is selected from the group consisting of alkyl of 5 through 8 carbon atoms, phenyl, benzyl, cycloalkyl of 5 through 8 carbon atoms, and substituted cycloalkyl of 5 through 8 carbon atoms wherein said sub- stituent is selected from the group consisting of methyl and methoxy; R-^ is alkyl of 1 through 3 carbon atoms; X is selected from the group consisting of iodine methyl, chlorine, bromine, and /¾y4*egefi¾ with the proviso that X can be hydrogen when the R on the same ring is a cycloalkyl group, and with the further proviso that X can be joined with R^ when X is methyl to form a trimethylene or tetramethylene group ; and Z is selected from the group consisting of 0 0 0 R 0 0 0 tl !l II I II II II -C-, -C-C-, -CH-C-, and -C-(R^)-C-, where Rg is hydrogen or alkyl of 1 through ½ carbon atoms and R, is alkylene of 1 through 12 carbon atoms, ^ 2 alkenylene of through 12 carbon atoms, cyclohexylene, or phenylene.
2. A method for the control of undesirable vegetation, said method comprising applying to a locus to be protected from said vegetation a herbicidally effective amount of a symmetrical compound of the formula wherein R is selected from the group consisting of alkyl of 3 through 8 carbon atoms, phenyl, benzyl, cycloalkyl of 5 through 8 carbon atoms, and substituted cycloalkyl of 5 through 8 carbon atoms wherein said sub- stituent is selected from the group consisting of methyl and methoxy; R^ is alkyl of 1 through 3 carbon atoms ; and X is selected from the group consisting of methyl, chlorine, bromine, and with the proviso that X can be hydrogen when the R on the same ring is a cycloalkyl group, and with the further proviso that X can be joined with R when X is methyl to form a trimethylene or tetramethylene group.
3. The method of Claim 2 wherein the compound is
4. . The method of Claim 2 wherein the compound is ,1' -oxalylbls(5-bromo-3-tert-butyl-6-methyluracil) .
5. The method of Claim 2 wherein the compound is ,1' -oxalylbis/5-bromo-3- (3-pentyl ) -6-methyluracil7.
6. The method of Claim 2 wherein the compound is , 1 '-oxalyIbis (3-sec-butyl-5-chloro-6-methyluracil) .
7. The method of Claim 2 wherein the compound is ,1 '-oxalyIbis (3-tert-butyl-5-chloro-6-methyluracil) .
8. The method of Claim 1 wherein the compound is ,1' -carbonylbis ( 5-bromo-3-sec-butyl-6-methyluracll) .
9. The method of Claim 1 wherein the compound is , 11 -carbonylbis ( 5-bromo-3-tert-butyl-6-methyluracil ) .
10. The method of Claim 1 wherein the compound is ,1 ' -malonylbis(5-bromo-3-sec-butyl-6-methyluracil) .
11. A compound of the formula wherein R is selected from the group consisting of alkyl of 3 through 8 carbon atoms, phenyl, benzyl, cycloalkyl of 5 through 8 carbon atoms, and substituted cycloalkyl of 5 through 8 carbon atoms wherein said substituent is selected from the group consisting of methyl and methoxy; is alkyl of 1 through 3 carbon atoms; X is selected from the group consisting of iodine methyl, chlorine, bromine, and kydyogotv, with the roviso that X can be h dro en when the R on the same ring is a cycloalkyl group, and with the further proviso that X can be joined with R1 when X is methyl to form a trimethylene or tetramethylene group; and Z is selected from the group consisting of 0 0 0 R 0 0 0 M tl 11 t C II II II -C- , -C-C-, -CH-C-, and -C-(R,)-C-, where R2 is hydrogen or alkyl of 1 through 4 carbon atoms and R^ is alkylene of 1 through 12 carbon atoms, alkenylene of through 12 carbon atoms, cyclohexylene, or p nylene. Dat*d thie 14th March 1967 For the Applicanter D *R·. RE'lrfHiL,D COHN & I
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US53967366A | 1966-04-04 | 1966-04-04 | |
| US62246967A | 1967-03-13 | 1967-03-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| IL27610A true IL27610A (en) | 1971-03-24 |
Family
ID=27066167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL27610A IL27610A (en) | 1966-04-04 | 1967-03-15 | Biuracils and their use as herbicides |
Country Status (13)
| Country | Link |
|---|---|
| BE (1) | BE696551A (en) |
| BR (1) | BR6788225D0 (en) |
| CH (2) | CH507256A (en) |
| DE (1) | DE1620169C3 (en) |
| DK (1) | DK128833B (en) |
| ES (1) | ES338910A1 (en) |
| GB (1) | GB1160028A (en) |
| IL (1) | IL27610A (en) |
| MY (1) | MY7200008A (en) |
| NL (1) | NL6704755A (en) |
| NO (1) | NO118770B (en) |
| OA (1) | OA02404A (en) |
| SE (1) | SE354864B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57156466A (en) * | 1981-03-24 | 1982-09-27 | Mitsui Toatsu Chem Inc | Uracil derivative and medicinal composition containing the same |
-
1967
- 1967-03-15 IL IL27610A patent/IL27610A/en unknown
- 1967-03-30 NO NO167496A patent/NO118770B/no unknown
- 1967-03-31 DK DK191867AA patent/DK128833B/en unknown
- 1967-04-03 CH CH1430169A patent/CH507256A/en not_active IP Right Cessation
- 1967-04-03 OA OA52890A patent/OA02404A/en unknown
- 1967-04-03 SE SE04580/67A patent/SE354864B/xx unknown
- 1967-04-03 DE DE1620169A patent/DE1620169C3/en not_active Expired
- 1967-04-03 CH CH467667A patent/CH506947A/en not_active IP Right Cessation
- 1967-04-04 GB GB15436/67A patent/GB1160028A/en not_active Expired
- 1967-04-04 BE BE696551D patent/BE696551A/xx unknown
- 1967-04-04 ES ES338910A patent/ES338910A1/en not_active Expired
- 1967-04-04 NL NL6704755A patent/NL6704755A/xx unknown
- 1967-05-31 BR BR188225/67A patent/BR6788225D0/en unknown
-
1972
- 1972-12-31 MY MY19728A patent/MY7200008A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CH506947A (en) | 1971-05-15 |
| NL6704755A (en) | 1967-10-05 |
| DK128833B (en) | 1974-07-15 |
| BE696551A (en) | 1967-09-18 |
| DE1620169B2 (en) | 1974-10-10 |
| NO118770B (en) | 1970-02-09 |
| GB1160028A (en) | 1969-07-30 |
| BR6788225D0 (en) | 1973-12-26 |
| ES338910A1 (en) | 1968-08-16 |
| MY7200008A (en) | 1972-12-31 |
| DE1620169C3 (en) | 1975-06-05 |
| DE1620169A1 (en) | 1970-03-12 |
| SE354864B (en) | 1973-03-26 |
| CH507256A (en) | 1971-05-15 |
| OA02404A (en) | 1970-05-05 |
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