DITHIOATE

Chemical Designations - Synonyms ZincO.O-di-n-butylphos phorodithioale Zinc dihexyldithio-phosphalc Zinc dihexylphosphoro-dithioate Chemical Formula [(RO)2PSS]2Zn where R=C4H,. Obs ahle Characteristics - Physical State (as normally shipped) Solid or liquid Color. Straw yellow yellow-green Odor Sweet, alcohol-like. 

Among the polyatomic ligands the dithiocarbamato ligand can stabilise high oxidation states of the transition metals in its complexes. like all 1,1-dithioates the a-donation and TT-back-donation of the sulfur atoms is assumed to be of the same order of magnitude. 

For convenience, the syntheses discussed in this section are divided into groups, depending on the structures of the starting materials, despite the fact that all of them contain C-N-N-C-O fragments. Therefore, 1,2-diacylhydrazines 109 are described as O-C-N-N-C-O components, acylhydrazones 110 as C-C-N-N-C-O components, while, for example, dithioates and similar compounds 111 are treated as S-C-N-N-C-O components. 

Sulfur may also be extracted from organic molecules and then support replication, as indicated by utilization of 0,0-diethylphosphorothioate and 0,0-diethylphosphoro-dithioate as sulfur sources by Pseudomonas acidovorans. 

Soil. In soil, malathion was degraded by Arthrobacter sp. to malathion monoacid, masphoro-dithioate. After 10 d, degradation yields in sterile and nonsterile soils were 8, 5, and 19% and 92, 94, and 81%, respectively (Walker and Stojanovic, 1974). Chen et al. (1969) reported that the microbial conversion of malathion to malathion monoacid was a result of demethylation of the 0-methyl group. Malathion was converted by unidentified microorganisms in soil to thiomalic acid, dimethyl thiophosphoric acid, and diethylthiomaleate (Konrad et al, 1969). 

Biological. Mixed cultures of microorganisms obtained from soil, raw sewage, activated sludge, and settled sludge were all able to degrade azinphos-methyl. When this dithioate pesticide was incubated in a stirred flask containing a mixed culture for 4 d, the concentration decreased from 99 to 40 mg/L (Barik et al., 1984). 

Barik, S., Mnnnecke, D.M., and Fletcher. J.S. Bacterial degradation of three dithioate pesticides. Agric. Wastes, 10 81-94,1984. 

Recently [251], the preparation of [3- F]trifluoropropylamine was achieved in three steps from iV-phthalimido-3-aminopropane dithioate by oxidative- F-fluorodesulfurization, then hydrazinolysis of the resulting iV-phthalimido-[i8F]trifluoropropylamine with an overall chemical yield of 40% and within 60 min from [ F]HF (Scheme 64). This new labelled precursor was used to synthesize the marker of hypoxia [ F] -EF-3. 

It Is well known that phosphorothlonate insecticides such as parathlon (, 0-diethyl p-nitrophenyl phosphorothloate) and malathion [0, -dimethyl -(l,2 -dlcarbethoxy)ethyl phosphoro-dithioate] are Intrinsically poor inhibitors of acetylcholinesterase and in vivo activation to the respective anticholinesterases paraoxon and malaoxon is required before animals exposed to the phosphorothionates are intoxicated. Since metabolic activation is essential to the biological activity of these thiono sulfur-containing organophosphorus insecticides, compounds of this type may be considered as propesticides or, more specifically, prolnsectlcldes. 

Hazel, J. P., Collin, R. L. The crystal structure of potassium O,0-dibenzylphosphoro-dithioate, KS2P(0-CH2-C6Hs)2. Acta cryst 525, 2279 (1972). 

More recently it has been shown (6, 7) that zinc dialkyl dithiophosphates also act as chain-breaking inhibitors. Colclough and Cunneen (7) reported that zinc isopropyl xanthate, zinc dibutyl dithiocarbamate, and zinc diisopropyl dithiophosphate all substantially lowered the rate of azobisisobutyronitrile-initiated oxidation of squalene at 60°C. Under these conditions, hydroperoxide chain initiation is negligible, and it was therefore concluded that inhibition resulted from removal of chain-propagating peroxy radicals. Also, consideration of the structure of these zinc dithioates led to the conclusion that no suitably activated hydrogen atom was available, and it was suggested that inhibition could be accounted for by an electron-transfer process as follows ... 

Thiophilic addition of Grignard reagents to methyl dithioates... 

The thiophilic addition of Grignard reagents was also carried out with S-allylic and propargylic dithioates. In these cases a [2, 3] sigmatropic rearrangement of the magnesiocarbanion occurred, and alkylation at sulfur yielded the dithioacetals of (i-unsaturated ketones [334] or of allenic ketones [335]. 

S-f(A,6-P iami no-sym-tr iaz n- 2-yl)-methyl] 0,O-dimethyl phosphoro-dithioate, AH98... 

In a recent series of studies focused on the synthetic utility of alkenyliodo-nium salts, ( )-/J-phenylethenyl(phenyl)- and ( )-l-hexenyl(phenyl)iodonium tetrafluoroborates, 22 and 23, were utilized for alkenylations of a range of soft, anionic nucleophiles (Scheme 45) [128-135]. In all cases but one, alkenylations with 22 occurred with retention of configuration, while alkenylations with 23 occurred with inversion of configuration. Only the dialkyl phosphoroselenolate salts gave mixtures of (Z)- and (fj)-products with 22 [132]. Furthermore, although cuprous iodide was used to catalyze the reactions of 22 and 23 with the phosphorothioate and -dithioate salts, the stereochemical results were the same [131,133]. It was generally assumed that retention was an outcome of the ligandcoupling or addition-elimination pathways, while stereochemical inversion was attributed to the vinylic... 

Amitrole heterocyclic nitrogen, triazole Ampropylfos phosphoro organic, phosphonic acid Ancymidol heterocyclic nitrogen, pyrimidine Anilazine heterocyclic nitrogen, triazine Anilofos phosphoro organic, phosphoro dithioate ANTU thiourea... 

Asulam carbamate, sulfonamide Atrazine heterocyclic nitrogen, triazine Azaconazole heterocyclic nitrogen, triazole Azamethiphos oxazole, phosphoro organic, phosphoro thioate, pyridine Azinphos-ethyl benzotriazine, phosphoro organic, phosphoro dithioate... 

Azinphos-methyl benzotriazine, phosphoro organic, phosphoro dithioate... 

Cacodylic acid organo arsenic Cadusafos phosphoro organic, phosphoro dithioate Camphechlor chlorinated hydrocarbon Captafol heterocyclic nitrogen, indoledione Captan heterocyclic nitrogen, indoledione Carbaryl carbamate... 

Dimethametryn heterocyclic nitrogen, triazine Dimethazone see Clomazone Dimethenamid heterocyclic sulfur, thiophene, amide Dimethipin heterocyclic sulfur, dithiin, sulfone Dimethirimol heterocyclic nitrogen, pyrimidine Dimethoate phosphoro organic, phosphoro dithioate, amide... 

Iprobenfos phosphoro organic, phosphoro dithioate Iprodione heterocyclic nitrogen, imidazolidinone IPSP phosphoro organic, phosphoro dithioate Isazofos phosphoro organic, phosphorothioate, triazole... 

Malathion phosphoro organic, phosphoro dithioate Maleic hydrazide heterocyclic nitrogen, pyridazinedione Mancozeb dithiocarbamate Maneb dithiocarbamate MCPA phenoxy carboxylic acid MCPA-Thioethyl (other) thioate MCPB phenoxy carboxylic acid Mecarbam phosphoro organic, phosphoro dithioate, carbamate... 

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