Patent GB-1013441-A (GB)
Title: Novel 2,6-dihalophenyl heterocyclic compounds and compositions containing them
Inventor: YATES JOHN
IPC: C07D277/22
Filed: 1961-10-19
Abstract: Wax compositions comprise a wax such as beeswax, paraffin wax, Montan wax or a chlorinated mineral wax, together with a compound of formula <FORM:1013441/C4-C5/1> where the C and N atoms are linked by a double bond, or by a single bond with hydrogen atoms filling the other valancies; R is 2,6-dihalophenyl; Y is O, S or N, in the last case being joined to Z by a double bond, or to Z and R1 by single bonds, R1 being hydrogen or phenyl; and Z is an organic group which completes a heterocyclic ring (see Division C2) or an acid addition salt thereof.  The compositions are pesticidal in action (see Division C5).ALSO:The invention comprises compounds of formula <FORM:1013441/C2/1> where the C and N atoms are linked by a double bond, or by a single bond with hydrogen atoms filling the other valencies; R is 2,6-dihalophenyl; Y is O, S or N, in the last case being joined to Z by a double bond, or to Z and to R1 by single bonds, R1 being hydrogen or phenyl; Z makes up a heterocyclic ring; and acid addition salts thereof.  Specified values of Z are alkylene, alkylene-oxy, alkylene-carbonyl or alkenylene of up to 4C, which may be substituted by alkyl, haloalkyl, chlorophenoxyalkyl, phenyl, halophenyl or alkoxycarbonyl; and phenylene, tetrahydrophenylene, = C(SH)-S-, -C(NH2) = N-and-CO-O-Tautomeric forms of the compounds may exist.  Preparation.-(i) Compounds in which Z is a substituted or unsubstituted alkylene or alkylene-oxy group, by reacting at elevated temperature a 2,6-dihalothiobenzamide, 2,6-dihalobenzimidic ester, 2,6-dihalobenzamidine or 2,6-di halobenzamidoxime with a compound XZX1, where X and X1 are each a halogen atom or sulphuric ester group.  (ii) Compounds in which Z is alkenylene, by reacting a 2,6-dihalobenzimidic ester, 2,6-dihalothiobenzamide or 2,6-dihalobenzamidine with (iii) a compound <FORM:1013441/C2/2> produced as in (ii) using ClCH2COCH2Cl may be reacted with carboxylic acid salts to produce the corresponding esters, or with alkali or alkaline earth metal phenoxides to produce phenyl ethers, e.g. the 2,4-dichlorophenyl ethers. (iv) Compounds in which Z contains a <FORM:1013441/C2/3> residue, by reacting a 2,6-dihalobenzimidic ester, 2,6-dihalothiobenzamide or 2,6-dihalobenzamidine with an a -halocarboxylic ester, chloride or anhydride.  (v) Compounds in which Y is S or O, by cyclizing RCONHZOH by treatment with P2S5 or with P2O5, polyphosphoric acid or other dehydrating agent.  (vi) Compounds in which Z is <FORM:1013441/C2/4> or -CO-O- and Y is -N = or -NH-, by cyclizing RC(NH2)=NO.CO.R0 (R0 being alkyl or haloalkyl) or RC(NH2)=NO.CO.O.Alkyl by heating.  (vii) Compounds in which Z is =C(SH)-S- and Y is N, by condensing a 2,6-dihalobenzamidoxime with CS2 at elevated temperature. (viii) Imidazole compounds, by condensing (a) a 2,6-dihalobenzaldehyde with an a -diketone such as benzil, in the presence of ammonia or an ammonium salt; (b) a 2,6-dihalobenzamidine with an a -halo- or a -hydroxyketone, or with an a -dicarbonyl compound. (ix) Tetrahydrothiazoles, by condensing RCHO with an aliphatic b -aminothiol (e.g. 1-amino-2-mercaptopropionic acid), and 2,3-dihydrobenzthiazoles, by condensing RCHO with 2-aminothiophenol; e.g. 2-(2,6-dichlorophenyl)-2,3-dihydrobenzthiazole, which is oxidized by alkaline K3Fe(CN)6 to the 2-(2,6-dichlorophenyl)-benzthiazole, itself also obtainable by oxidizing RCSNHPh with alkaline K3Fe(CN)6. (x) 1,2-Dihydrobenzimidazoles and 2,3-dihydrobenzoxazoles by condensing RCHO with o-phenylenediamine or 2-aminophenol.  (xi) Benzimidazoles, by reacting RCHO with o-phenylenediamine in the presence of cupric acetate.  (xii) Thiadiazoles, by dehydrative cyclization of RCONHNHCSNH2, or by the mild oxidation, e.g. with FeCl3, of RCH = NNHCSNH2.  (xiii) Triazoles, by condensing RCOOH with guanidine or a substituted guanidine, e.g. amino- or nitroguanidine. (xiv) RCH = N-N = CHR with P2S5 gives. <FORM:1013441/C2/5> Additional methods are used in examples and additional products are named in the Provisional Specification.  The compounds of the invention are herbicides, fungicides and bacteriostats (see Division A5), and some possess metabolic depressant properties.  R.C(NH2) = N.O.COOEt is obtained from RC(NH2) = NOH and ClCOOEt (R being 2,6-dichlorophenyl).ALSO:The invention comprises compositions containing a compound of formula <FORM:1013441/A5-A6/1> where the C and N atoms are linked by a double bond, or by a single bond with hydrogen atoms filling the other valencies; R is 2, 6-dihalophenyl; Y is O, S or N, in the last case being joined to Z by a double bond, or to Z and to R1 by single bonds, R1 being hydrogen or phenyl; and Z is an organic group which completes a heterocyclic ring (see Division C2), or an acid addition salt thereof; together with a carrier or surface active agent or both; and a method for eradicating weeds from areas to be used for growing crops by applying to the areas a compound or composition as refined above.  The compositions may be dusts, wettable powders, emulsifiable concentrates, or aqueous emulsions or dispersions. Specified carriers are hydrated silica, calcium silicates, sulphur, carbon, resins, waxes (see Division C5), petroleum fractions, ketones, alcohols, aromatic hydrocarbons, chlorinated hydrocarbons, polyalkylene glycol ethers and esters and fertilisers.  Suitable surface-active agents are listed. Other additives may also be present, e.g. sodium polyphosphates, cellulose ethers, EDTA, other herbacides or pesticides, and stickers such as a non-volatile oil. Some of the compounds defined above are also fungicides or bacteriostats.