Patent GB-1031490-A (GB)
Title: New pyrazolyl carbamic acid derivatives and processes for their production
IPC: C07D231/20
Filed: 1964-03-20
Abstract: The invention comprises carbamic acid esters of formula <FORM:1031490/C2/1> in which A represents a straight or branched chain alkylene radical which may be substituted by halogen, R1 represents a C1-C4 alkyl radical, R2 represents hydrogen or a C1-C4 aliphatic hydrocarbon radical, R3 represents a C1-C4 aliphatic hydrocarbon radical; and R4 represents the group -OR5 in which R5 represents hydrogen, an aliphatic hydrocarbon radical which may be substituted by halogen or in which the carbon chain may be interrupted by an oxygen or sulphur atom, or the group <FORM:1031490/C2/2> in which R6 and R7 each represents hydrogen, an aliphatic or aromatic hydrocarbon radical or together with the adjacent nitrogen atom form a heterocyclic ring; and their salts with organic and inorganic acids. The esters may be prepared by reacting at 50-150 DEG  C. a pyrazole derivative of formula <FORM:1031490/C2/3> with a compound of formula <FORM:1031490/C2/4> in which Y is an alkenyl radical, optionally halogen-substituted, capable of forming the radical A after the addition reaction, and reacting the product <FORM:1031490/C2/5> so obtained at 50-150 DEG C. with a carbamic acid halide of formula <FORM:1031490/C2/6> in which Z is a halogen atom, e.g. chlorine or bromine.  The intermediate <FORM:1031490/C2/7> may alternatively be formed by reacting a compound of the formula YCN at 50-150 DEG  C. with a compound of Formula II <FORM:1031490/C2/8> and converting the product into the desired intermediate by saponification and/or esterification in the presence of an inorganic acid.  These intermediates may also be obtained by condensing hydrazine or derivatives thereof with the cyanide YCN, then condensing with a b -ketocarboxylic acid ester or diketene and saponifying and/or esterifying the cyano group; or by the reaction of hydrazine or its derivatives with a compound of formula YCOR4 and subsequent condensation with a b -keto-acid ester or diketene.  In another method of preparation the pyrazole starting material of formula given above may be reacted with <FORM:1031490/C2/9> at 50-150 DEG  C. to form the corresponding carbamic acid ester and then with the compound of Formula YCOR4.  In another modification a compound of formula <FORM:1031490/C2/100> is reacted with <FORM:1031490/C2/111> and the product of formula <FORM:1031490/C2/122> is reacted with the carbamic halide <FORM:1031490/C2/133> Instead of the compound a mixture of <FORM:1031490/C2/144> <FORM:1031490/C2/155> and phosgene may be used. If desired, the new carbamic esters may be converted into their salts by reaction with organic or inorganic acids.ALSO:Carbamic acid esters of general formula <FORM:1031490/A5-A6/1> in which A is a straight or branched-chain alkylene radical which may be substituted by halogen, R1 is a C1-C4 alkyl radical, R2 is hydrogen or a C1-C4 aliphatic hydrocarbon radical, R3 is a C1-C4 aliphatic hydrocarbon radical, and R4 is the group-OR5 in which R5 represents hydrogen, an aliphatic hydrocarbon radical which may be substituted by halogen or in which the carbon chain may be interrupted by an oxygen or sulphur atom, or the group <FORM:1031490/A5-A6/2> in which R6 and R7 each represents hydrogen, an aliphatic or aromatic hydrocarbon radical or together with the adjacent nitrogen atom form a heterocyclic ring, and their salts with organic and inorganic acids are used in pesticidal compositions.  The esters may be used in the forms of powders, emulsions, pastes and solutions with conventional carriers and may be used in conjunction with succinic acid dibutyl ester, pipeionyl butoxide, DDT active substance, olive oil, peanut oil or phosphoric acid esters.  They may also be used with substances acting as bait e.g. sugar or mixed with other insecticides.