BICYCLIC 2-IMINOTHIAZOLIDINE OXIMES AND METHODS OF PREPARING SAME

Abstract: Certain bicyclic 2-iminothiazolidine oximes, which are useful as intermediates for the preparation of insecticidal compounds and compositions, have the general formula:- wherein R₁ and R₂ are the same or different and are individually hydrogen, C₁-C₆ alkyl or halogen; n = 0, 1 or 2; X = -N-OH including E&Z isomers; and A is an acyclic, cyclic, or bicyclic alkylene or alkenylene group, or an ortho-substituted phenylene group which forms an unsaturated five, six or seven membered heterocyclic ring which can also contain oxygen, sulfur, nitrogen, or carbonyl in addition to the two nitrogens, said alkylene, alkenylene, or phenylene ring systems being optionally substituted with one or more C₁-C₄ alkyl, cyclohexyl alkoxy, phenoxy, alkyl­ thio, halogen, amido, alkylamido, nitrile, acyl, or nitro groups.

Description: "SICYCLIC 2-IMINOTHIAZOLIDINE OXIMES AND METHODS OF PREPARING SAME" This Invention relates to certain bicyclic 2iminothiazolidine oximes and methods of preparing same. More particularly, this invention relates to compounds of the formula EMI1.1 wherein R1 and R2 are the same or different and are ndividually hydrogen, C1-C6 alkyl or halogen; n = 0, 1 or 2; X = -N-OH including E & isomers; and A is acyclic, cyclic or bicyclic aikylene or alkeny- lene group, or an ortho-substituted phenylene group which forms an unsaturated five, six or seven membered heterocyclic ring which can also contain oxygen, sulfur, nitrogen, or carbonyl in addition to the two nitrogens, said aikylene, alkenylene, or phenylene ring systems being optionally substituted with one or more C1-C4 alkyl, cyclohexyl, alkoxy, phenoxy, alkylthio, halogen, amido, alkylamido, nitrile, acyl, or nitro groups. compounds falling within the above generic formula have utility as intermediates and/or pre cursors for the formation of compounds which exhibit biological activity as insecticides. Compounds and compositions which can be made from the coinpounds dis closed herein are disclosed in our copendiAg Serial No. which is filed concurrently herewith. For the purpose of completeness, the disclosure of Application Serial No. is incorporated herein by reference. In general, the 2-iminothiazolidine oximes of this invention can be conveniently prepared by reacting a cyclic thiourea with the dichloro-oxime as described below, in which Rl, R2, and A are as described previously. Method I ,/ EMI3.1 The reaction of Method I can be conducted in aqueous or organic solvents with an appropriate acid acceptor. The acid acceptor in the conduct of the reaction of Method I may be either an organic or inorganic base. Aromatic and aliphatic tertiary amines, such as triethylamine, pyridine, 1,4-diazobicyclo[2.2.2] octane and the like are representative of the organic bases. Bases such as sodium hydroxide, potassium carbonate, sodium bicarbonate or the like are illustrative of the inorganic bases which are useful in the con duct of this reaction. When an inorganic base is used phase transfer agents may be used to facilitate the transfer of the base across the organic/inorganic phase interface. Illustrative of useful phase transfer agents are crown ether compounds, quaternary ammonium halide compounds or the like. The reactions are preferably carried out in methanol using sodium bicarbonate as the acid acceptor. The temperature is preferably held between -78 C and 0 during addition of starting materials and the mixture is slowly allowed to warm to 250 C, The time of reaction varies between 16 hours and 3 days. The insecticidal compounds which utilize the oxime compounds of this invention as precursors can be prepared by a variety of methods. The methods are illustrated by the reaction schemes set forth below. Method II EMI5.1 Method V EMI6.1 In the above reactions methods, R1, R2 and A are as indicated previously: n = 0, 1 or 2; R3 and R4 may be the same or different and are individually hydrogen, C1-C4 alkyl or C1- C4 alkanoyl which can be substituted with one or more halogens and in the case when R3 is alkyl R4 can also be (S)y-R5 wherein: Y = 1 or 2; R5 = a) C1-C18 alkyl, C3-Cg cycloalkyl or perhaloalkyl. b) dialkyl amino, piperidino, pyrrolidino, or a morpholino group each of which may be unsubstituted or substituted with one or two alkyl groups; or c) a phenyl group which may be unsubstituted or substituted with one or more alkyl, chloro, fluoro, cyano, nitro, alkoxy, trifluoromethyl,/alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxy alkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, or dialkylamino: or d) a group of the formula: EMI7.1 wherein: R6 is: 1) C1-C12 alkyl, alkoxyalkyl, or a phenylalkyl group; or 2) a phenyl group which may be unsubstituted or substituted with one or more C1-C12 alkyl, chloro, fluoro, alkoxy, alkylthio, alkylthioalkyl, alkylsulfinyl, alkylsulfinylalkyl, alkylsulfonyl, alkyl sulfonylalkyl, alkynyloxy, dialkylamino, alkoxy imino, formamidino, cyano, dioxolanyl, or dithiolanyl groups in any combina t,on; or 3) a naphthyl, tetrahydronaphthyl, dihydrobenzo furanyl, benzodioxolanyl, or benzothienyl group all of which may be unsubstituted or substituted with one or more alkyl groups; or 4) a group of the formula EMI8.1 wherein: R7 is chloro, alkyl alkoxy, alkylthio, cyanoalkylthio, amidoalkylthio or cyano group; or R7 is hydrogen provided R8 is not hydrogen; R8 is an alkyl, alkylthio, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthioalkyl, cyanoalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkoxyalkyl, nitroalkyl, hydroxyalkyl, haloalkyl or phenyl group; said phenyl group may contain one or more alkyl chloro or fluoro groups in any combination; or R8 is hydrogen provided R7 is not hydrogen; B is a divalent aliphatic chain completing a five or six membered heterocyciic ring structure, said aliphatic chain having from 2-to 24 aliphatic carbon atoms, said ring structure may include in any combination one, two or three divalent oxygen, sulfur, sulfinyl, or sulfonyl groups and may further include one group selected from a divalent amino group, a Cl-Cg divalent alkylamino group, or a divalent carbonyl group; with the proviso that when R6 is a phenyl group substituted with an alkyl group, no single alkyl or alkylene moiety in any R5, R6, R7, or R8 group can include more than eight carbon atoms except where indicated. The reactions illustrated in Methods II to VI are conducted in inert solvents. Any inert solvent such as methylene chloride, chloroform, acetonitrile, benzene, toluene, xylene, dioxane, tetrahydrofuran or a mixture of these solvents can be used in these reactions. Preferably these reactions are conducted in methylene chloride or methylene chYoride/acetonitrile, depending on solubility characteristics of the starting oxime. Reaction temperatures are not critical and can be varied over 2 wide range depending to a large extent on solubility of the reactants. The reactions are preferably conducted at a temperature of -10" to 50"C. Reaction pressures are not critical. For con venience these reactions are usually conducted at atmospheric or autogeneous pressure. The reaction illustrated in Method II is preferably conducted in the presence of a quantity of a catalyst sufficient to provide a suitable and reason able rate. In general, any conventional catalyst of the type commonly employed to promote reactions between isocyanate compounds and compounds that contain an active hydrogen can be used. Preferred catalysts are tertiary gamines such as triethylamine, trimethylamine, pyridine or the like and dibutylzin diacetate. The reaction illustrated in Method III is conducted in the presence of one equivalent of a base such as triethylamine, trimethylamine, pyridine, potassium hydroxide or the like. When an inorganic base is used phase transfer agents may be used to facilitate the transfer of the base across the organic inorganic phase interface. Illustrative of useful phase transfer agents are crown ether compounds, quaternary ammonium halide compounds pr the like. The chloro compound starting reactant i5 commercially available or easily prepared from known procedures. The reaction illustrated in Method IV is an oxidation reactipn of the product of Method III. The peracetic acid is admixed with the starting reactant and stirred in ethyl acetate at room temperature until the product is produced. The reaction illustrated in Method V is conducted in the presence of an acid acceptor. The molar ratio of acid acceptor to either reactant is usually unity although a slight excess of acid acceptor may be employed, if desired. The acid acceptor utilized in the conduct of the reaction of Method V may be either an organic or inorganic base. Aromatic and aliphatic tertiary amines, such as triethylamine, pyridine, 1,4 diazobicyclo[2.2.2]octane and the like are representative of the organic bases. Bases such as sodium hydroxide potassium carbonate or the like are illustrative of the inorganic bases which are useful in the conduct of this reaction. When an inorganic base is used phase transfer agents may be used to facilitate the transfer of the base across the organic/inorganic phase interface. Illustrative of useful phase transfer agents are crown ether compounds, quaternary ammonium halide com pounds or the like. The alkylsulfenyl compounds of Method VI are prepared by reacting the products of Method I with an alkylsulfenylchloride in the presence/of an organic or inorganic base. Aromatic and aliphatic tertiary amines, such as triethylamine, pyridine, 1,4-diazobicyclo [2.2.2] octane and the like are representative of the organic bases. Bases such as sodium hydroxide, potassium hydroxide or the like are illustrative of the inorganic bases which are useful in the conduct of this reaction. When an inorganic base is used phase transfer agents may be used to facilitate the transfer of the base across the organic/inorganic phase interface. Illustrative of useful phase transfer agents are crown ether compounds, quaternary ammonium halide compounds or the like. The 2-chlorohydroxamoyl chloride compounds of Method I can be prepared by the method described in Ogloblin et al, J. Gen. Chem. USSR, 34, 1225 (1964). The sulfenylated reactant of Method V can be conveniently prepared by reacting hydrogen fluoride with an alkyl isocyanate to form the N-alkylcarbarnoyl fluoride compound which is then reacted with an appropriate sulfenyl chloride, e.g. with sulfur dichloride (SCl2) to form the bis-(N-alkyl-N-fluorocarbonylamino)sulfide. This particular material is then reacted with one equivalent of an appropriately substituted alcohol or oxine in the presence of an acid acceptor to form the ccrrespcnding mono-flcoro adduce. The carbamoyl fluorides are described in U.S. Patents 4.0/91.016 and U.S. 3,639,471 ; Belgium Patents 848,914 and 848,910 ; and Germany Often. 2,813,374. The thioureas used as reactants in Method I are known naterials which can be obtained fre co..,erciai sources or prepared in accordance with conventional methods known to those skilled ir. the art. The following compounds are representative of compounds which come within the contents o tre generic formula and which can be prepared according to Method I. 2.2-Dimethyl-3-hydroxyimino-[5,8]-methano-2,3,5,6,7,8 hexahydrothiazolo[3,2-a] [l,3]diazepine; 2,2-Dimethyl-3-hydroxyimino-[5.8]-methano-2,3,5,8 tetrahydrothiazolo[3,2-a][1,3] diazapine ; 2,2-Dimethyl-3-hydroxyimino-5-oxo-2,3,5,6,7,8-hexahydro thiazolo[3,2-a]benzimidazole; 2,2-Dimethyl-3-hydroxyimino-2,3,4,5,6,7-hexahydrothiazolo [3,2-c][1,3,5]thiadiaz-ne; 2,2-Dimethyl-3-hydroxyimino-2,3-dihydro-9H-chiazolo [3,2-a]quinazoline ; 5,6-Dichloro-2,2-dimethyl-3-hydroxyimino-2,3-dihydro imidazo [2,1-b]thiazole; 5,6-Dicyano-2,2-dimethyl-3-hydroxyimino-2,3-dihydroimidazo[2,1-b]thiazole; 2,2-Dimethyl-3-hydroxyimino-5-oxo-2,3-dihydro-5Hthiazolo[3,2-a]pyrimidine; 5,5-Dimethyl-6-hydroxyimino-2,3-dihydrothiazolo[3,2-d] tetrazole; ; 2,2-Dimethyl-3-hydroxyimino-2,3,4a,6,7,7a-hexahydro-5Hcyclopenta[4,5]imidazo[2,1-b]thiazole; 2,2-Dimethyl-3-hydroxyimino-2,3-dihydro-6H-thiazolo [3,2-b][1,2,4]oxadizole ; 7,7-Dichloro-2,2-dimethyl-3-hydroxyimino-2,3-dihydrothiazolo[3,2-a]pyrimidine ; 6,6-Dichloro-2,2-dimethyl-3-hydroxyimino-2,3,5,6tetrahydro-7H-thiazolo[3,2-a]pyrimidine ; 2,2-Dimethyl-3-hydroxyimino-5,7-dioxo-2,3-dihydro-5H 7H-thiazolo[3,2-c]oxadiazine ; 2,2-Dimethyl-5-methoxy-3-hydroxyimino-2,3-dihydroimidazo[2,1-b]thiazole ; 3-Hydroxyimino-2,3,5,6-tetrahydro-7H-thiazolo[3,2-a] pyrimidine ; 2-Ethyl-3-hydroxyimino-2,3-dihydroimidazo[2,1-b]thiazole ; 2-Trichloromethyl-3-hydroxyimino-2,3-dihydroimidazo [2,1-b]thiazole ; 2-Isopropyl-3-hydroxyimino-2,3,5,6-tetrahydro-7H thiazolo[3,2-a]pyrimidine ; and 2,2-Dimethyl-3-hydroxyimino-2,3-dihydroimidazo[2,1-b] thiazole-1,1-dioxide. The following insecticidally active compounds are representative of compounds which can be prepared from the compounds of this invention by selecting appropriate starting materials for use in the procedures described above. 2,2-Dimethyl-3-[0-(methylcarbamoyl)oximino] -[5,8]-methano-2,3,5,6,7,8-hexahydrothiazolo[3,2-a] [1,3] diazepine. 2,2-Dimethyl-3-[0-(methylcarbamoyl)oximino] -[S,8]-n;ethano-2,3,5,8-tetrahydrothiazolo [3,2-a] fl,3] diazepine. 2.2-Dimethyl-3-[0-(methylcarbamoyl)oximino] -5-oxo-2,3,5,6,7,8- hexahydrothiazolo [3,2-a] benzimidazole. 2,2-Dimethyl-3-(0-(methylcarbamoyl)oximino] 2,3,4,5,6,7-hexahydrothiazolo [3,2-c] 1,3,5] thiadiazine. 2,2-Dimethyl-3-(0-(methylcarbamoyl)oximino] -2.3-dihydro-9H-thiazolo [3.2-a] quinazoline. 5,6-Dichloro-2,2-dimethyl-3-[0-(methylcarbamoyl) oximino]-2,3-dihydroimicazo [2,1-b] thiazole. 5,6-Dicyano-2,2-dimethyl-3-[0-(methylcarbamoyl) oximino]-2,3-dihydroimidazo [2,1-b] thiazole. 2,2-Dimethyl-3-[0-(methylcarbamoyl)oximino] -5-oxo-2,3-dihydro-5H-thiazolo[3,2-a] pyrimidine. 5,5-Dimethyl-6-[0-(methylcarbamoyl)oximino] -2,3-dihydrothiazolo[3,2-d] tetrazole. 2,2-Dimethyl-3-[0-methylcarbamoyl)oximino] -2,3,4a,6,7,7a-hexahydro-5H-cyclopenta [4,5] imidazo [2,1-b] thiazole. 2,2-Dimethyl-3-[0-(methylcarbamoyl)oximino] -2,3-dihydro-6H-thiazolo [3,2-b] [1,2,4] oxadiazole. 7,7-Dichloro-2,2-dimethyl-3-[0-(methylcarbamoyl) oximino]-2,3-dihydrothiazolo [3,2-a] pyrimidine. 6,6-Dichloro-2,2-dimethyl-3-[0-(methylcarbamoyl) oximino]-2,3,5,6- tetrahydro-7H-thiazolo ;3,2-a] pyrimidine. 2.2-Dimethyl-3-[0-(methylcarbamoyl)oximino] -5,7-dioxo-2,3-dihydro-5H,7H-thiazolo [3,2-c] oxadiazine. 2.2-Dimethyl-5-methoxy-3-[0-(methylcarbamoyl) oximino]-2,3-dihydroimidazo [2,1-b] thiazole. 3-[0-(methylcarbamoyl)oximino]-2,3,5,6-tetrahydro-7H-thiazolo [3,2-a] pyrimidine. 2-Ethyl-3-[0-(methylcarbamoyl)oximino]-2,3 dihydroimidazo [2,1-b] thiazole. 2-Trichloromethyl-3-[0-(methylcarbamoyl)oximino]2,3- dihydroimidazo [2,1-b] thiazole. 2-Isopropyl-3-[0-(methylcarbamoyl)oximino] -2,3,5,6-tetra.hydro-7H-thiazolo [3,2-a] pyrinidine. 2.2-Dimethyl-3-[0-(methylcarbamoyl)oximino]-2,3dihydroimidazo[2,1-b] thiazole-1,1-dioxide. 2.2-Dimethyl-2,3,5,6-tetrahydro-7H-3-[(0 [N-methyl-N-(N'-methyl-N'-((2-methyl-2-(methylthio propylidene) aminooxycarbonyl) aminosulfenyl) carbamoyl oximino]] thiazolo[3,2-a] pyrimidine. 2,2-Dimethyl-2,3 dihydro-3[(0-[N-methyl-N (N'-methyl-N'-(2,3-dihydro-2,2-dimethylbenzofuran-7-oxo carbonyl) aminosulfenyl) carbamoyl] oximino]] midazo [2,1-b] thiazole. 2,2-Dimethyl-2,3-dihydro-3-[(0-[N-methyl-N (N'-methyl-N'- ((1-N,N-dimethylcarbamoyl-1-methylthio methylidene-aminooxycarbonyl)) aminosulfenyl)carbamoyl] oximino]]imidazo [2,1-b] thiazole. 2,2-Dimethyl-2,3,5,6-tetrahydro-7H-3{[0-[Nmethyl-N'-(N'-methyl-N'-(1-N,N-dimethylcarbamoyl-2-methoxy iminopropylideneamino oxycarbonyl) aminosulfenyl) carbamoyl] oximino]} thiazole [3,2-a] pyrimidine. 2,2-Dimethyl-2,3-dihydro-3[[0-[N-methyl (morpholinosulfanyl)carbemoyl] oximino]] imidazo [2,1-b] thiazole. 2,2-Dimethyl-2,3,5,6-tetrahydro-7H-3 {[0-[Nmethyl-N-(4-tert-butylphenyl sulfenyl) carbamoyl] oximino]] thiazolo [3,2-a] pyrimidine. 2,2-Dimethyl-2,3-dihydro-3 [(0-[N-methyl-N (4-methylthio phenyl sulfenyl) carbamoyl] oximino]} imidazo [2,1-b] thiazole. 2.2-Dimethyl02,3,5,6-tetrahydro-7H-3 {[0 [N-methyl-N-(N'-methyl-N'-((tert-butoxycarbonyl))emin@ sulfenyl)carbamoyl]oximino]}thiazolo [3,2-a] pyrimidine. 2,2-Dimethyl-2,3-dihydro-3-{[0-[N-methyl-N (tert-butylthiosulfanyl)carbamoyl]oximino]}imidazo [2,1-b] thiazole. 2,2-Dimethyl-2,3,5,6-tetrahydro-7H-3-{[0-[N methyl-N-(4-tert-bucylphenylthiosulfenyl)carbamoyl] oximino]]thiazolo [3,2-a] pyrimidine. 2,2-Dimethyl-3-[0-carbamoyloximino]-. 2,3-dihydroimidazo [2,1-b] thiazole, 3-[2,2-Dimethyl-2,3-dihydroimidazu (2,1-b) thiazol-3-ylidenamino-oxycarbonyl methylaminothiosulfenylmethyl carbamoyloxyimino]-2,2-dimethyl-2,3dihydroimidazo [2,1-b] thiazole. All compounds within the purview of the above generic formula can be used as precursors for the preparation of insecticidal compounds which exhibit insecticidal activity to a lesser or greater extent. Sorne of the insecticidal compounds exhibit very powerful insecticidal activity in extremely small dosages while others require larder dosages to be insecticidally effective. Preferred because of their use in preparing insecticidal compounds which exhibit high levels of insecticidal activity are those of the above generic structurel formula wherein R1 and R2 are individually C1-C6 alkyl and most preferably methyl; n is 0 or 1 and A is an acyclic aikylene or alkerylene group, or an ortho-substituted phenylene group which forms an unsaturated five, six or seven membered heterocyclic ring which also may contain nitrogen or carbonyl in addition to the two nitrogens, said alkylene, alkenylene, or phenylene ring systems being optionally substituted with on tor more C1-C4 alkyl or cyclohexyl; Most preferably A would constitute part of tae following ring systems, pyrimidine, diazepine, triazole, inidazole, and benzidazole. The following specific examples are presented to more particularly illustrate this invention. Examples I-IX show the preparation of the compounds of the instant invention whereas Examples X to XX show insecticidal compounds produced from the compounds of the instant invention. Example I Preparation of 2, 2-Dimethyl-3-hydroxyimino-2,3,5,6 tetrahydroimidazo [2,1-b] thiazole A 10.2g (65.4 mmol) of 2-chlorohydroxamoyl chloride was dissolved in 200 ml of methanol and immediately cooled in an ice bath tc 00. To this solution was added 6.68g (65.4 mmol) of 2-imidazolidinethione in one portion. After the reaction mixture was stirred at 0 for ca. 10 min., 11.09 g (132 mmol) of sodium bicarbonate was added in portions. The reaction mixture was allowed to stir at 25 C overnight before the solvent was removed in vacuo. The residue was extracted with absolute ethanol and the ethenolie extracts were concentrated in vacuo. The residue was triturated with cold acetonitrile- hexane. The insoluble solid (22%) was identified as the desire product: mp: 188-191 . nmr (5% DMSO-d6) µ 9.75 (b@, l, NOH), 4.10 (brs, 4, -N-CH2CH2N-), 3.50-3.30 (m,4,2H20), 1.67 (s,6, gem-direthyl). ir (CH2Cl2) 3570, 1670, 1620, 1200, 920 cm-Ú The following Exarples II-IX were prepared n a manner similar to Example I. The nomenclature and structure of the compounds of each example are as follows: EMI20.1 Example <SEP> Nomenclature <SEP> Structure <tb> II <SEP> 2,2 <SEP> - <SEP> Dimethyl-3-hydroxyimino-2,3,5,6 <SEP> - <SEP> # <tb> tetrahydro <SEP> - <SEP> 74 <SEP> - <SEP> thiazolo <SEP> # <tb> [3,2-a] <SEP> pyrimidine <tb> III <SEP> 2,2,5,5,8,8 <SEP> - <SEP> Hexomethyl-3-hydroxyimino <SEP> # <tb> 2,3,5,6,7,8 <SEP> - <SEP> hexahydro <SEP> # <tb> thiazolo <SEP> [3,2-a] <SEP> [1,3] <SEP> diazepine <tb> EMI21.1 Example <SEP> Nomenclature <SEP> Structure <tb> IV <SEP> 6,6 <SEP> - <SEP> Dimethyl-5-hydroxyimino <SEP> - <SEP> 5,6 <SEP> - <SEP> # <tb> dihydrothiazolo <SEP> [2,3-c] <SEP> 1,2,4 <SEP> - <SEP> triazole <tb> V <SEP> 2,2 <SEP> - <SEP> Dimethyl-3-hydroxyimino <SEP> - <SEP> 2,3 <SEP> - <SEP> # <tb> dihydroimidazo <SEP> [2,1-b] <SEP> thiazole <tb> VI <SEP> 6,6 <SEP> - <SEP> Dimethyl-3-hydroxyimino <SEP> - <SEP> 2,3 <SEP> - <SEP> # <tb> dihydrothiazolo <SEP> [3,2-a] <SEP> benzimidazole <tb> EMI22.1 Example <SEP> Nomenclature <SEP> Structure <tb> VII <SEP> E <SEP> - <SEP> 2,2 <SEP> - <SEP> Dimethyl-3-hydroxyimino <SEP> - <SEP> 7-oxo <SEP> - <SEP> # <tb> 2,3 <SEP> - <SEP> dihydro <SEP> - <SEP> 7H <SEP> - <SEP> thiazolo <tb> [3,2-a] <SEP> pyrimidine <tb> VIII <SEP> 2,2 <SEP> - <SEP> Dimethyl-3-hydroxyimino <SEP> - <SEP> 5-oxo <SEP> - <SEP> # <tb> 2,3 <SEP> - <SEP> dihydro <SEP> - <SEP> 5H <SEP> - <SEP> thiazolo <tb> [3,2-a] <SEP> pyrimidine <tb> IX <SEP> Z <SEP> - <SEP> 2,2 <SEP> - <SEP> Dimethyl-3-hydroxyimino <SEP> - <SEP> 7-oxo <SEP> - <SEP> # <tb> 2,3 <SEP> - <SEP> dihydro <SEP> - <SEP> 7H <SEP> - <SEP> thiazolo <SEP> [3,2-a] <tb> pyrimidine <tb> The physical data for. these compounds are as indicated in Table I. TABLE I EMI23.1 <tb> <SEP> nmr/Anal <tb> Example <SEP> MP-OC <SEP> calcd <SEP> " <SEP> Found <tb> <SEP> II <SEP> 191-193" <SEP> c-48.22 <SEP> 47.72 <tb> <SEP> H- <SEP> 6.57 <SEP> 6.30 <tb> <SEP> N-21.09 <SEP> 21.04 <tb> <SEP> III <SEP> 161-163 <SEP> nmr <SEP> (5% <SEP> DMSO-d6) <SEP> a' <tb> <SEP> 1.90-1.50 <SEP> (m,lO,singlet <SEP> at <tb> <SEP> 1.60S <SEP> for <SEP> gem-dirthy1) <tb> <SEP> 1.35 <SEP> (s,6, <tb> <SEP> CH3 <SEP> CH3 <tb> <SEP> 1.18 <SEP> (s,6, <SEP> =N <SEP> < <tb> <SEP> CH3 <SEP> CH3 <tb> <SEP> IV <SEP> 202-204" <SEP> nrnr <SEP> (DMSO-d6) <tb> <SEP> 12.00 <SEP> (s.l,NOH) <tb> <SEP> 9.20 <SEP> (s,l,C-H) <tb> <SEP> 1.82 <SEP> (s,6,gem-dime.hyl) <tb> <SEP> V <SEP> 202.5-204" <SEP> C-45.88 <SEP> C-46.17 <tb> <SEP> H- <SEP> 4.95 <SEP> H- <SEP> 4.83 <tb> <SEP> N-22.93 <SEP> N-23.08 <tb> <SEP> VI <SEP> - <SEP> nmr <SEP> (DMSO.d6) & BR< <tb> <SEP> 11.72 <SEP> (s,l,NOH) <tb> <SEP> 8.30-7.10(m,4, <SEP> aromatic) <tb> <SEP> 1.82(s,6, <SEP> gem <SEP> dimethyl) <tb> <SEP> VII <SEP> > 240" <SEP> C-45.48 <SEP> C-45.56 <tb> <SEP> H- <SEP> 4.29 <SEP> H- <SEP> 4.20 <tb> <SEP> N-19.88 <SEP> N-20.23 <tb> nmr/Anal Example MP- C calcd Found VIII 132-143 C-45.48 C-45.47 H- 4.29 H- 4.26 N-19.89 N-19.99 IX - nmr (DMSO-d6)# 12.12 (s,l,OH) 8.90 (d,l,CO CH=CH, J=8 Hz) 6.00 (d,l,CO CH=CH, J=8 Hz) 1.78 (s,6, gem-dimethyl) Example X Preuaration of 2,2-Dimethyl-3-[0(methylcarbamoyl) oximino]-2,3,5,6-tetrahydroimidazo [2,1-b] thiazole. To a solution of 2,63g (14.2 mmol) of 2,2-dimethyl-3-hydroxyimino-2,3,5,6-tetrahydroimidazo [2,1-b] thiazole (I) in 200 ml of a 1:1 mixture of methylene chloride:acetonitrile, taken in a pyrex pressure bottle, was added 1.13 ml (15 mmol) of methylisocyanate and two drops of di-butyltindiacetate. After standing at 25 for 24 hours the solvent was removed in vacuo and the resulting oil was crystallized from hexane/toluene to afford 1.5g (44%) of the product. mp 142-147 . Calc'd for C9H14N402S: C, 44.61; 4, 5.82; N, 23.12. Found: C, 44.24; 4, 5.81; N, 23.11 The following examples XI-XVII were prepared in a manner similar to Example X. The nomenclature and structure of the compounds of each example are as follows: EMI26.1 Example <SEP> Nomenclature <SEP> Structure <tb> XI <SEP> 2,2 <SEP> - <SEP> Dimethyl-3-[0-(methyl- <SEP> # <tb> carbamoyl)oximino] <SEP> -2,3,5,6tetrahydro-7H-thiazolo <SEP> [3,2-a] <tb> pyrimidine <tb> XII <SEP> 2,2,5,5,8,8-Hexamethyl-3-[0- <SEP> # <tb> (methylcarbamoyl)oximino] <SEP> 2,3,5,6,7,8-hexahydrothiazolo <tb> [3,2-a] <SEP> [1,3] <SEP> diazepine <tb> EMI27.1 Example <SEP> Nomenclature <SEP> Structure <tb> XIII <SEP> 6,6-Dimethyl-5-[0-(methylcarbomoyl)- <SEP> # <tb> oximino]-5,6-dihydrothiazolo <tb> [2,3-c] <SEP> 1,2,4-triazolo <tb> XIV <SEP> 2,2-Dimethyl-3-[0-(methylcarbamoyl)- <SEP> # <tb> oximino]-2,3-dihydroimidazo <SEP> [2,1-b] <tb> thiazole <tb> EMI28.1 Example <SEP> Nomenclature <SEP> Structure <tb> XV <SEP> 2,2-Dimethyl-3-[0-(methylcarbamoyl)- <SEP> # <tb> oximino]-2,3-dihydrothiazolo <SEP> [3,2-a] <tb> benzimidazole <tb> XVI <SEP> 2,2-Dimethyl-3-[0-(methylcarbamoyl)- <SEP> # <tb> oximino]-7-oxo-2,3-dihydro-7Hthiazolo <SEP> [3,2-a] <SEP> pyrimidine <tb> EMI29.1 Example <SEP> Nomenclature <SEP> Structure <tb> XVII <SEP> 2,2-Dimethyl-6N-cyclohexyl-3-[0- <SEP> # <tb> (methylcarbamoyl)oximino] <tb> 2,3,5,6-tetrahydro-7H-thiazolo <tb> [3,2-a] <SEP> triazine <tb> The physical data for these compounds are as indicated in Table II. TABLE II nmr/Anal Example MP- C calcd Found XI 142.5-1440 C-46.85 C-46.96 H- 6.29 H- 6.39 H-21.86 N-22.19 XII 141-1430 C-55.18 C-55.04 H- 8.03 H- 8.05 N-17.16 N-17.53 XIII 167-171 C-39.82 C-39.71 (dec) H- 4.60 H- 4.76 N-29.03 N-26.07 XIV 133-141 C-44.98 C-44.41 H- 5.04 H- 5.10 N-23.32 N-22.10 XV 192-195 C-53.77 C-53.25 H- 4.86 H- 4.77 N-19 30 N-19.05 XVI 146-149 C-44.76 C-43.70 (dec) H- 4.51 H- 5.54 XVII 158-161 C-53.07 C-51.03 H- 7.42 H- 7.18 N-20.63 N-20.76 The following examples XVIII to XXII further illustrate preparation of additional insecticidal compounds with Examples XIX and XXII being prepared in a manner similar to Example XVIII by adding one equivalent of appropriately substituted alcohol or oxime to the bis-(N-alkyl-N-fluorocarbonylamino) sulfide in the presence of an acid acceptor followed by an equivalent of oxime. The nomenclature and structure of the compounds of each example are as indicated below. ExamDle XVIII Preparation of 3-[2,2-Dimethyl-2,3-dihydroimidazo [2,1-b] thiazol-3-ylidenamino-oxycarbonyl methylaminosulfenylmethyl carbamoyloxyimino]-2,2-dimethyl 2, 3-dihydroimidazo 12.1-b] thiazole A 3.0g (16.4 mmol) quantity of 2,2-dimethyl-3hydroxyimino-2,3,5,6-tetrahydroimidazo [2,1-b] thiazole (I) was dissolved in 300 ml of methylene chloride containing 2.28 ml (16.4 mmol) of triethylamine. To this mixture was added 1.5g (8.2 mmol) of bis-(N-alkyl-Nfluorocarbonylamino) sulfide and the reaction mixture was stirred overnight. The reaction mixture was washed with water (2 x 200 ml), dried (MgSO4). and concentrated in vacuo to give a solid residue which was recrystallized from ethylacetate. The final product crystallized with one equivalent of solvent (ethylacetate or acetone) per two equivalents of compound. Yield 3.24g (65%); mp. 177-180 . Calcd for [C18H22N804S3]2 C4H802;C,43.30, H,4-73; N,20.20 Found C,42.82, H,4.70; N,20.1 EMI32.1 Example <SEP> Nomenclature <SEP> Structure <tb> XIX <SEP> 2,2-Dimethyl-2,3-dihydro-3-[[0-[N-methyl- <SEP> # <tb> N-(N'-methyl-N'-(1-methylthio-ethylidene <tb> aminooxycarbonyl) <SEP> aminosulfenyl) <tb> carbamoyl]oximino]] <SEP> imidazo <SEP> [2,1-b] <SEP> thiazole <tb> XX <SEP> 2,2-Dimethyl-2,3-dihydro-3-[[0-[N-methyl-N- <SEP> # <tb> (N'-methyl-N'-(naphthaleneoxy <SEP> carbonyl)amino <tb> sulfenyl)carbamoyl]oximino]]imidazo <SEP> [2,1-b] <tb> thiazole <tb> EMI32.2 EMI33.1 Example <SEP> Nomenclature <SEP> Structure <tb> XXI <SEP> 2,2-Dimethyl-2,3-dihydro-3-[[0-[N-methyl-N- <SEP> # <tb> (N'-methyl-N'-(3,4,5-trimethylphenoxycarbonyl) <tb> amino <SEP> sulfenyl)carbamoyl]oximino]]imidazo <tb> [2,1-b]thiazole <tb> XXII <SEP> 2,2-Dimethyl-2,3-dihydro-3[0-[N-methyl-N- <SEP> # <tb> (N'-methyl-N'-(4-n-nonelphenoxycarbonyl) <tb> aminosulfenyl)carbamoyl]oximino]imidazo <tb> [2,1-b]thiazole <tb> TABLE III Analysis Example MP Calc Found XIX 50-55 C-38.87 C-38.19 H- 4.66 H- 4.83 N-19.43 N-18.56 XX 85 (dec) C-53.48 C-52.91 . H- 4.49 H- 4.65 N-14.85 N-14.00 131.5-134 C-51.81 C-51.61 H- 5.44 H- 5.41 N-15.11 N-15.09 XXII gummy solid C-57.01 C-56.64 H- 6.81 H- 6.86 N-12.79 N-12.60 Example XXIII Preparation of 2.2-Dimethyl-2,3-dihydro-3 [0 (dimethyl carbemoyl) oximino]-imidazo-[2,1-b] thiazole To a solution of 330 mg (13.6 mmol) of sodium hydride in 150 ml of dry tetrahydrofuran was added 2.50g (13.6 mmol) of 2,2-dimephyl-3- hydroxyimino-2,3-dihydroimidazo-[2,1-b]thiazole. The reaction mixture was stirred at 250 for 1 hour and cooled in an ice bath before 1.54g (14.3 mmol) of dimethylcarbamoyl chloride was added. After stirring for 12 hours at 250, the solvent was removed in vacuo and the residue washed with hexane, dissolve in methylene chloride. The methylene chloride solution was washed with water, dried (MgS04), and concentrated in vacuo to give 2.94g (85%) of desired product. m.p. 99-102.5 . Anal. Calc'd for C10H14N402S: C, 47.23; H, 5.55; N, 22.03 Found: C, 47.65; H, 5.71; N, 21.89 The following examples XXIV-XXVI further illustrate preparation of additional insecticidal compounds. Example XXIV was prepared according to the procedure of Example XXIII. Example XV was prepared according to the procedure of Example X and Example XXTJI was prepared according to the procedure of Example XVIII. The nomenclature and structure of each example are as indicated below. EMI36.1 Example <SEP> Nomenclature <SEP> Structure <tb> XXIV <SEP> 2,2-Dimethyl-2,3-dihydro-3- <SEP> # <tb> [0-(N-methyl-N-pentanoyl <tb> carbamoyl)oximino]-imidazo <tb> [2,1-b]thiazole <tb> XXV <SEP> 2,2-Dimethyl-2,3-dihydro-3- <SEP> # <tb> [0-(N-propyl <SEP> carbamoyl)oximino]imidazo[2,1-b]thiazole <tb> EMI37.1 Example <SEP> Nomenclature <SEP> Structure <tb> XXVI <SEP> 2,2-Dimethyl-2,3-dihydro-3[0- <SEP> # <tb> (N-methyl-N- <SEP> (4-tert-butylphenylthiosulfenyl)carbamoyl)oximino]imidazo[2,1-b]thiazole <tb> The physical data for Examples XXIV-XXVI are as indicated in Table IV. TABLE IV Elemental Anal. Example MP- C calcd Found XXIV . C-51.83 C-51.87 H- 6.21 H- 6.23 N-17.27 N-16.88 XXV 103.5-105 C-49.23 C-49.26 N- 6.01 R- 5.96 N-20.88 N-21.13 XXVI C-52.26 C-51.53 H- 5.54 H- 5.50 N-12.83 N-12.66 Example XXVII Preparation of 2,2-Dimethyl-3-[0-(methylcarbamoyl] oximino]-2,3-dihydromidazo [2,1-b] thiazole-1-oxide A 2.0g (8.32 mmol) quantity of 2,2-dimethyl3-[0-(methyl carbamoyl) oximino]-2,3-dihydroimindazo [2,1-b] thiazole was dissolved in 300 ml of ethyl- acetate. The solution was cooled to -15 before 1.33g (17.5 mmol) of peracetic acid was added. The reaction mixture was allowed to warm to 25 and stirred for 1 d, followed by concentration to ca. 100 ml and placing in the freezer overnight. The precipitate was collected to give 1.5g (70%) of product m.p. 147.5-149 . Anal. calc'd for C9H12N4O3S: C. 42.18 ; H, 4.72 ; N, 21.85. Found: C, 41.91; H, 4.75 ; N, 21.65. Selected new compounds were evaluated to determine their pesticidal activity against mites, nematodes, and certain insects, including an aphid, a caterpillar, a beetle and 2 fly. Suspensions of the test compounds were prepared by dissolving one gram of compound in 50 milliliters of acetone in which had been dissolved 0.1 gram (10 percent of the weight of compound) of an alkylaryl polyether alcohol surfactant, as an emulsifying or dispersing agent. The resulting solution was mixed into 150 milliliters of water to give roughly 200 milliliters of a suspension containing the compound in finely divided form. ine thus-prepared stock suspension contained 0.5 percent by weight of compound. The concentrations in parts per million by weight employed in the tests described below were obtained by appropriate Llricns of the stock suspension wit water. The test procedures were as follows: Aduits and nymphal stages of the bean aphid (Aphis fabse Soop.) reared on ported dwarf nastuttive plants at 65-70 F. and 50 + 5 percent relative humidity, constituted with test insects. Por testing purposes, the number of aphids per pot was standardized to 100-150 by trimming plants containing excess aphids. The test compounds were fo...ulated b diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. The potted plants (one pot per compound tested) infested with 100-150 aphids, were placed on a revolving turntable and sprayed with 100-110 milliliters of test. comound formulation by use of a DeVilbiss spray gun set at 40 psig. air pressure. This application; which lasted 25 seconds, was sufficient to wet the plants to run-off. As a control, 100-110 milliliters of a water-acetone-emulsifier solution containing no test compound were also sprayed on infested plants. After spraying, the pots were placed on their sides on a sheet of white standard mimeograph paper which had been previously ruled to facilitate counting. Temperature and humidity in the test room during the 24 hour holding period were 65-700F. and 50-70 percent, respectively. Aphids which fell onto the paper and were unable to remain stanching after being uprighted were considered dead. Aphids remaining on the plants were observed closely for movement and those which were unable to move the length of the body upon stimulation by prodding were considered dead. Larvse of the southern armyworn (Spodoptare eridania, (Cram.)), reared on Tendergreen bean plants at a temperature of 80 T 50F. and a relative humidity of 50 + 5 percent, constituted the test insects. The test compounds were formulated by diluring the stock suspension wit water to give a suspension con tailing 500 parts of test compound per million parts of final formulation. Potted Tendergreen bean plants of standard height and age were placed on a revolving turntable and sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at 10 psig air prcssure. This application, which lasted 25 seconds, was sufficient to et plants to run-off. As a control, 100-110 milliliters of a water acetone-emulsifier solution containing no test compound were also sprayed on infested plants. WhenX'dry, the paired leaves were separated and each one was placed in a 9 centimeter Petri dish lined with moistened filter paper. Five randomly selected larvae were introduced into each dish and the dishes were closed. The closed dishes were labeled and held at 80-850F. for three days. Although the larvae could easily consume the whole leaf within twenty-four hours, no more food was added. Lanac which were unable to nove the length of the body. even upon stirulation by prodding, were considered dead. Fourth ins tar larvae of the Mexican bean beetle (Enilachne varivestis, Muls.), reared on Tendergreen bean plants at a temperature of 80 + 5 F. and 50 + 5 percent relative humidity, were the test insects. Tne test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. Potted Tendergreen bean plants of standard height and age were placed on a revolving turn- table and sprayed with 100-110 milliliters of test com- pound formulation by use of a DeVilbiss spray gun set at 10 psig air pressure. This application, which lasted 25 seconds, was sufficient to wet plants to run-off. As a control, 100-110 milliliters of a water-acetone-emulsifier solution containing no test compound were also sprayed on infested plants. When dry, the paired leaves were separated and each was placed in a 9 centimeter Petri dish lined with moistened filtcr paper. Five randomly selected larvae were introduced into each dish, and the dishes were closed. The closed dishes were labeled and held at a temperature of 80 + 5 F. for three days. Although the larvae could easily consume the leaf within 24 to 48 hours, no more food was added. Larvae which were unable to move the length of the body, even upon stimulation, were considered dead. Four to six day old adult house flies (usca domestica, L.), reared according to the specificaticns of the Chemical Specialties Manufacturing Association (Blue Book, McNair-Dorland Co., N. Y. 1954; pages 243-244, 261) under controlled conditions of 80 + 5'F. and 50 #5 percent relative humidity, were the test insects. Tne flies were immobilized by anesthetizing with carbon dioxide and twenty five immobilized individuals, males and females, were transferred to a cage consistirg of a standard food strainer about five inches in diameter which was inverted over a wrapping-paper-covered surface The test compounds were formulated by diluting the stock suspension with a 10 percent (by weight) sugar solution to give a suspension containing 500 parts of test compoun per million parts of final formulation. by weight. Ten milliliters of the test formulation ere added to a souffle cup containing a one-inch square of an absorbent cotton pad. This bait cut was introduced and centered on the blotting paper under the food strainer prior to admitting the anesthetized flies. The caged flies were allowed to feed on the bait for twenty four hours, 'at a temperature of 80 + 5 F. and the relative humidity of 50 + 5 percent. Flies which showed no sign of movement on prodding were considered dead. Adults and nymphal stages of the two-spotted nite (Tetranvchus urticae (Koch)), reared on Tendergreen bean plar.ts at 80 + 5 percent relative humidity, were the test organisms. Infested leaves from a stock culture were placed on the primary leaves of two bean plants six to eight inches in height, growing in a two-and-ahalf inch clay pot. 150-200 Mites, a sufficient nur:ber for testing, transferred from the excised leaves to the fresh plants in a period of twenty-four hours. Following the twenty-four hour transfer period, the excised leaves were removed from the infested plants. The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. 'lne potted plants (one pot per compound) were placed on a revolving turn- table and sprayed with 100-110 milliliters o test compound formulation b use of a DeVilbiss spray gun set at 40 psig. air pressure. This application, which lasted 25 seconds, was sufficient to wet the plants to run-off. As a control, 100-110 milliliters of water solution containing acetone and emulsifier in the same concentration as the test compound formulaticn, but containing no test compound, were also sprayed cn infested plants. The sprayed plants were held at 80 t 5 percent relative humidity for six days, after which a mortality count oL mobile forms was made. Microscopic examination for motile forms was made on the leaves of the test plants. Any individual which was capable of locomotion upon prodding was considered living. The results of these tests are set forth in Table III below. In these tests the pesticidal activity. of the compounds at the indicated dosage rate against aphid, mite, Southern Armyworm, Bean Beetle and house fly was rated as follows: A = excellent control B = partial control C = no control TABLE IV Biological Data B@an Mite Southem Armyworm South@m Armyworm Mexican Bean House Example Aphid Adult Larvac Egg Beetle Fly I C C C C C C VII C C C C C C X A A C A A A XI A A A A A A XII A C C C C B XIII A B B C A A XIV A A A A A A XV B C C C C C XVI C C B C C C XVII C C B C C A XVIII A A A A A A XIX A A A A A A XX A A A A A A XXI A A A A A A XXII B C A C A A TABLE IV (continued) Mite Southern Armyworm Southern Armyworm Mexican Bean House Example Bean Aphid Adult Larvac Egg Beetle Fly XXIII A A A C A A XXIV A A A C A A XXV A A A B A A XXVI A A A C A A XXVII A A A C A A It will be understood that the plant species employed in the above tests are merely representative of a wide variety of plant pest that can be controlled by the use of the compounds of this invention. The compounds contemplated in this invention may be applied as mite ovicides and miticides according to methods known to those skilled in the art. Pesticidal compositions containing the compounds as the sctive toxicant will usually comprise a carrier and/or diluent, either liquid or solid. Suitable liquid diluents or carriers include water, petroleum distillates, or other liquid carriers with or without surface active agents. Liquid concentrates may be prepared by dissolving one of these compounds wir a nonphytotoxic solvent such as acetone, xylene, or nitrobenzene and dispersing the toxicants in water with the aid of suitable surface active emulsifying ano dispersing agents. The choice of dispersing and emulsifying agents and the amount employed is dictated by the a=ure of the composition and the ability of the agent to facilitate the dispersion of the toxicanc. Generally, it is desirable to use as little of the agent as is possible, consistent with the desired dispersion of the toxicant in the spray so that rain does not reemulsify the toxicant after it is applied to the plant and wash it off the plant. Nonionic, anionic, amphoteric or cationic dispersing and emulsifying agents may be employed; for example, the condensation products of alkylerie oxides with phenol and organic acids, alkyl aryl sulfonates, complex ether alcohols, quaternary ammonium compounds, and the like. In the preparation of wettable powder or dust or granulated compositions, the active ingredient is dispersed in and on an appropriately divide% solid carrier such as clay, talc, bentonite, diatomaceous earth. fullers earth, and the like. In the formulation of the wettable powders the aforementioned dispersing agents as well as lignosulfonates can be included. The recuired amount of,-the toxicants contemplated herein may be applied per acre treated in from 1 to 200 gallons or more of liquid carrier and/or diluent or in from about 5 to 500 pounds of inert solid carrier and/or diluent. The concentration in the liquid concenrate will usually very from about 10. to 95 percent by weight and in the solid formulations from about 0.5 to about 90 percent by weight. Satisfactory sprays, dusts, or granules for general use contain from about 1/4 to 15 pounds of active toxicant per acre. The pesticides contemplated herein prevent attack by insects and mites upon plants or other material to which the pesticides are applied, and they have relatively high residual toxicity. With respect to plants, they have a high margin of safety in that when usec in sufficient amount to kill or repel the insects, they co not burn or injure the plant, and they resist weathering which includes wash-off caused by rain, decomposition b ultraviolet iight, oxidation, or hydrolysis in the presence of moisture or, at least such decomposition, oxidation, and hydrolysis as would materially decrease the desirable pesticidal characteristic of the toxicants or impart undesirable characteristic for instance, phytotoxicity, to the toxicants. The toxicants are so chemically inert that they are compatible with substantially an other constituents of the spray schdule, and they may be used in the soil, upon the seeds, or the roots o± plants without injuring either the seeds or roots of plants. They may also be used in combination with other pesticidally active compounds. When used as miticides they will normally be applied to the foliage of the plants to be treated. It will be appreciated that the compounds of this invention can also be used in combination with other biologically active compounds.

Claims: CLAIMS:- 1. A bicyclic 2-iminothiazolidine oxime of the general formula: EMI51.1 wherein R1 and R2 are the same or different and are individually hydrogen, C -C6 alkyl or halogen; n = 0 , 1 or 2; X = -N-OH including E & isomers; and A is an acyclic, cyclic, or bicyclic alkylene cr alkenylene group or an ortho-substituted phenyiene group which forms an unsaturated five, six or seven membered heterocyclic ring which can also contain oxygen, sulfur, nitrogen, or carbonyl in addition to the two nitrogens, said alkylene, alkenylene, or phenylene ring systems being optionally substituted with one or more C1-C4 alkyl, cyclohexyl alkoxy, phenoxy, alkylthio, halogen, amid6, alkylamidc, nitrile, acyl, or nitro groups. 2. An oxime as claimed in claim 1 wherein Px1 and R2 can be the same or different and are individually Cl-C6 alkyl. 3. An oxime as claimed in claim 2 wherein R1 and R2 are methyl. 4. An oxime as claimed in any ozone of claims 1 to 3 wherein n is O. 5. An oxime as claimed in any one of the preceding claims wherein A is an acyclic., cyclic, or bicyclic alkylene or alkenylene group, or an ortho-substituted phenylene group which forms an unsaturated five, six or seven membered heterocyclic ring which also may contain nitrogen or carbonyl in addition to the two nitrogens, said alkylene, alkenylene, or phenylene ring systems being optionally substituted with one or more C1-Ca alkyl or cyclohexyl. 6. An oxime as claimed in claim 5 wherein A is selected from the group consisting of pyrimidine, diazepine, triazole, imidazole, and benzimidazole. 7. 2,2-Dimethyl-3-hydroxyimino-2,3,4,6-tetrahydroimidazo /2,1-b/ thiazole. 8. 2,2-Dimthyl-3-hydroxyimino-2,3,4,6-tetra- hydro-74-thiazole [3,2-a] pyrimidine. 9. 2,2,5,5,8,8-Hexamethyl-3-hydroxyimino- 2,3,5,6,7,8-hexahydrothiazolo /3,2-a7 /1,3/ diazepine. 10. 6,6-Dimethyl-5-hydroxyimino-5,6-dihydrothiazolo /2,3-c/ 1,2,4-triazole. 11. 2,2-Dimethyl-3-hydroxyimino-2 ,3-dihydroimidazo /2,1-b/ thiazole. 12. A method of producing bicyclic 2-iminothiazolidine oxime of the general formula: EMI53.1 which comprises reacting a compound of the formula EMI53.2 with a compound of the formula EMI54.1 in the presence of an acid acceptor wherein R1 and R2 are the same or different and are individually hydrogen, C1-C6 alkyl or halogen; n = 0, 1 or 2; X = -N-OH including E &commat; Z isomers; and A is an acyclic, cyclic, or bicyclic alkylene or alkenylene group, or an ortho-substituted phenylene gr which forms an unsaturated five, six or seven membered heterocyclic ring which can also contain oxygen, sulfu. nitrogen or carbonyl in addition to the two nitrogens, said alkylene, alkenylene, or phenylene ring systems being optionally substituted with one or more C1-C4 al cyclohexyl alkoxy, phenoxy, alkylthio, halogen, amido, alkylamido t nitrile, acyl, or nitro groups.

Inventors: BUSHEY, DEAN FRANKLIN, D'SILVA, THEMISTOCLES DAMASCENO JOAQUIM
Applicants: UNION CARBIDE CORPORATION
Application year: 1981
Main classification: C07D513
IPC codes: C07D513