Patent GB-1035091-A (GB)
Title: Improvements relating to herbicides
Inventor: LOUX HARVEY MONROE
IPC: C07D239/54
Filed: 1962-12-07
Abstract: Compounds of the formula <FORM:1035091/C2/1> or the corresponding isomeric formula <FORM:1035091/C2/2> wherein X represents an oxygen or sulphur atom and R1, R2 and R3 are defined in one of paragraphs (A) to (D) below.  (A)  R1 represents an alkyl radical containing 1 to 10 carbon atoms, a substituted alkyl radical containing 1 to 8 carbon atoms, an aryl radical containing 5 to 10 carbon atoms, a substituted phenyl radical, an aralkyl radical containing 5 to 13 carbon atoms, a substituted aralkyl radical containing 5 to 13 carbon atoms, an alkenyl radical containing 3 to 8 carbon atoms, an alkynyl radical containing 3 to 8 carbon atoms, a cycloalkyl radical containing 3 to 12 carbon atoms, a cycloalkenyl radical containing 4 to 12 carbon atoms, a substituted cycloalkyl radical in which the cycloalkyl radical contains 3 to 12 carbon atoms, a substituted cycloalkenyl radical in which the cycloalkenyl radical contains 4 to 12 carbon atoms or a cyano radical; R2 represents a chlorine, fluorine, bromine or iodine atom, a methyl radical, an ethyl radical, a propyl radical, a butyl radical, a methoxy radical, an ethoxy radical, a propoxy radical, a butoxy radical, a nitro radical, an alkoxymethyl radical containing 2 to 6 carbon atoms, a hydroxy alkyl radical containing 1 to 6 carbon atoms, an alkenyl radical containing 3 to 6 carbon atoms, a thiocyanato radical, a cyano radical, a mercapto methyl radical, a methylthiomethyl radical, a phenylthiomethyl radical, an alkylthio radical containing 1 to 4 carbon atoms, a bromomethyl radical, a fluoromethyl radical, a chloromethyl radical or a carboxymethylthiomethyl radical; R3 represents a chlorine or bromine atom, an alkyl radical containing 1 to 5 carbon atoms, a chloroalkyl radical containing 1 to 4 carbon atoms, a bromoalkyl radical containing 1 to 4 carbon atoms, or an alkoxy radical containing 1 to 5 carbon atoms;  (B)  R1 represents a cycloalkyl radical containing 3 to 12 carbon atoms, a substituted cycloalkyl radical in which the cycloalkyl radical contains 3 to 12 carbon atoms, a cycloalkenyl radical containing 4 to 12 carbon atoms or a substituted cycloalkenyl radical in which the cycloalkenyl radical contains 4 to 12 carbon atoms; R2 represents a hydrogen atom; and R3 represents an alkyl radical containing 1 to 5 carbon atoms; (C)  R1 represents an alkyl radical containing 1 to 10 carbon atoms, a substituted alkyl radical containing 1 to 10 carbon atoms, an aryl radical containing 6 to 14 carbon atoms, a substituted aryl radical containing 6 to 14 carbon atoms, an aralkyl radical containing 7 to 15 carbon atoms, a substituted aralkyl radical containing 7 to 15 carbon atoms, an alkenyl radical containing 3 to 10 carbon atoms, an alkynyl radical containing 3 to 10 carbon atoms, a cycloalkyl radical containing 3 to 12 carbon atoms, a cycloalkenyl radical containing 4 to 12 carbon atoms, a substituted cycloalkyl radical in which the cycloalkyl radical contains 3 to 12 carbon atoms, a substituted cycloalkenyl radical in which the cycloalkenyl radical contains 4 to 12 carbon atoms or a cyano radical; and R2 and R3 together represent a divalent alkylene radical of formula (CH2)n where n is 3, 4 or 5; (D)  R1 represents an alkyl radical containing 1 to 10 carbon atoms, a substituted alkyl radical containing 1 to 10 carbon atoms, an aryl radical containing 5 to 14 carbon atoms, an aralkyl radical containing 5 to 15 carbon atoms, a substituted aralkyl radical containing 5 to 15 carbon atoms, an alkenyl radical containing 3 to 10 carbon atoms, an alkynyl radical containing 3 to 10 carbon atoms, a cycloalkyl radical containing 3 to 12 carbon atoms, a cycloalkenyl radical containing 4 to 12 carbon atoms, a substituted cycloalkyl radical in which the cycloalkyl radical contains 3 to 12 carbon atoms, a substituted cycloalkenyl radical in which the cycloalkenyl radical contains 4 to 12 carbon atoms or a cyano radical; R2 represents a hydrogen, chlorine, fluorine, bromine or iodine atom, a methyl radical, an ethyl radical, a propyl radical, a butyl radical, a methoxy radical, an ethoxy radical, a propoxy radical, a butoxy radical, a nitro radical, an alkoxymethyl radical containing 2 to 6 carbon atoms, a hydroxy alkyl radical containing 1 to 6 carbon atoms, an alkenyl radical containing 3 to 6 carbon atoms, a thiocyanato radical, a cyano radical, a mercaptomethyl radical, a methylthiomethyl radical, a phenylthiomethyl radical, an alkylthio radical containing 1 to 4 carbon atoms, a bromomethyl radical, a fluoromethyl radical, a chloromethyl radical or a carboxymethylthiomethyl radical; with the proviso that when R2 represents a hydrogen atom, R1 represents a cycloalkyl radical containing 3 to 12 carbon atoms, a substituted cycloalkyl radical in which the cycloalkyl radical contains 3 to 12 carbon atoms, a cycloalkenyl radical containing 4 to 12 carbon atoms, a substituted cycloalkenyl radical in which the cycloalkenyl radical contains 4 to 12 carbon atoms, and R3 represents a hydrogen atom; and metal salts of compounds as defined above, are prepared by methods known for the preparation of uracils, e.g. those disclosed in Specification 968,661.  Compounds of the above formulae in which X is oxygen, and (1) R1 is C3- 10 cycloalkyl which may be substituted, or C4- 10 cycloalkenyl which may be substituted, and R2 and R3 together represent (CH2)n where n is 3, 4 or 5, or (2) R1 is C3- 12 cycloalkyl which may be substituted, or C5- 12 cycloalkenyl which may be substituted, R2 is halogen, methyl, hydroxymethyl, methoxymethyl or nitro, and R3 is hydrogen, are claimed as novel.  The uracils as defined above are herbicides (see Division A5). Intermediates.-Malononitrile is reacted with (i) norbornylurea and triethyl orthoacetate and (ii) fenchylurea and triethyl orthoformate to give respectively [1-(3-norbornylureido)ethylidene] malonitrile and [(3-fenchylureido)methylene] malononitrile, which with methanolic NaOMe followed by acetic acid produce 3-norbornyl-6-methyl-5-cyanocytosine and 3-fenchyl-5-cyanocytosine respectively.  sec-Butylurea and 2-acetyl-4-butylbutyrolactone are reacted to produce 2-(2-hydroxyhexyl)-3-(3-sec-butylureido) -crotonic acid lactone.ALSO:Compounds of the formula <FORM:1035091/A5-A6/1> or the corresponding isomeric formula:  <FORM:1035091/A5-A6/2> wherein X represents an oxygen or sulphur atom and R1, R2 and R3 are defined in one of paragraphs (A) to (D) below.  (A) R1 represents an alkyl radical containing 1 to 10 carbon atoms, a substituted alkyl radical containing 1 to 8 carbon atoms, an aryl radical containing 5 to 10 carbon atoms, a substituted phenyl radical, an aralkyl radical containing 5 to 13 carbon atoms, a substituted aralkyl radical containing 5 to 13 carbon atoms, an alkenyl radical containing 3 to 8 carbon atoms, an alkynyl radical containing 3 to 8 carbon atoms, a cycloalkyl radical containing 3 to 12 carbon atoms, a cycloalkenyl radical containing 4 to 12 carbon atoms, a substituted cycloalkyl radical in which the cycloalkyl radical contains 3 to 12 carbon atoms, a substituted cycloalkenyl radical in which the cycloalkenyl radical contains 4 to 12 carbon atoms or a cyano radical; R2 represents a chlorine, fluorine, bromine or iodine atom, a methyl radical, an ethyl radical, a propyl radical, a butyl radical, a methoxy radical, an ethoxy radical, a propoxy radical, a butoxy radical, a nitro radical, an alkoxymethyl radical containing 2 to 6 carbon atoms, a hydroxy alkyl radical containing 1 to 6 carbon atoms, an alkenyl radical containing 3 to 6 carbon atoms, a thiocyanato radical, a cyano radical, a mercaptomethyl radical, a methylthiomethyl radical, a phenylthiomethyl radical, an alkylthio radical containing 1 to 4 carbon atoms, a bromomethyl radical, a fluoromethyl radical, a chloromethyl radical or a carboxy-methylthiomethyl radical; R3 represents a chlorine or bromine atom, an alkyl radical containing 1 to 5 carbon atoms, a chloroalkyl radical containing 1 to 4 carbon atoms, a bromoalkyl radical containing 1 to 4 carbon atoms, or an alkoxy radical containing 1 to 5 carbon atoms;  (B) R1 represents a cycloalkyl radical containing 3 to 12 carbon atoms, a substituted cycloalkyl radical in which the cycloalkyl radical contains 3 to 12 carbon atoms, a cycloalkenyl radical containing 4 to 12 carbon atoms or a substituted p cycloalkenyl radical in which the cycloalkenyl radical contains 4 to 12 carbon atoms; R2 represents a hydrogen atom; and R3 represents an alkyl radical containing 1 to 5 carbon atoms;  (C) R1 represents an alkyl radical containing 1 to 10 carbon atoms, a substituted alkyl radical containing 1 to 10 carbon atoms, an aryl radical containing 6 to 14 carbon atoms, a substituted aryl radical containing 6 to 14 carbon atoms, an aralkyl radical containing 7 to 15 carbon atoms, a substituted aralkyl radical containing 7 to 15 carbon atoms, an alkenyl radical containing 3 to 10 carbon atoms, an alkynyl radical containing 3 to 10 carbon atoms, a cycloalkyl radical containing 3 to 12 carbon atoms, a cycloalkenyl radical containing 4 to 12 carbon atoms, a substituted cycloalkyl radical in which the cycloalkyl radical contains 3 to 12 carbon atoms, a substituted cycloalkenyl radical in which the cycloalkenyl radical contains 4 to 12 carbon atoms or a cyano radical; and R2 and R3 together represent a divalent alkylene radical of formula (CH2)n where n is 3, 4 or 5.  (D) R1 represents an alkyl radical containing 1 to 10 carbon atoms, a substituted alkyl radical containing 1 to 10 carbon atoms, an aryl radical containing 5 to 14 carbon atoms, an aralkyl radical containing 5 to 15 carbon atoms, a substituted aralkyl radical containing 5 to 15 carbon atoms, an alkenyl radical containing 3 to 10 carbon atoms, an alkynyl radical containing 3 to 10 carbon atoms, a cycloalkyl radical containing 3 to 12 carbon atoms, a cycloalkenyl radical containing 4 to 12 carbon atoms, a substituted cy