Compounds useful for the preparation of various agrochemicals and markers thereof

A compound having a general structure which is one of, G1;

• DD1;
• DD2;
• DD3;
• DD4;
• and DD5;
• analogues;
• isomers;
• salts, N-oxides;
• and esters thereof,
• wherein, each Rβ, Qα, Qβ, Rπ, Aα, Aβ, nα, and Rζ are selected such that the compound has a structural formula selected from the group of D;
• DD6;
• DD7;
• DD8;
• DD9;
• DD10;
• and DD11.

An agricultural product selected from group of

• (a) agricultural product 17 comprising a composition of an 2′-fluoro-1-methyl-2-oxo-4-[3-(trifluoromethyl)phenyl]pyrrolidine-3-carboxanilide such as, Tetflupyrolimet, characterized in that the rate at which conversion to the compound of the following formula,
• including any isomer, enantiomer, or mixture thereof, occurs during storage, is minimized, wherein said product is adapted to limit, reduce, or minimize the time and extent or to avoid exposure to sunlight of said composition within said product during storage, wherein said minimization is as compared to an agricultural Tetflupyrolimet product without said adaptation and
• (b) agricultural product 18 comprising a Tetflupyrolimet composition protected to a detectable degree against sunlight-mediated conversion to the corresponding Storage Marker compound of the following formula,
• during manufacturing, packaging, labeling, transportation, or storage, of said composition, characterized in that the product comprises said composition contained within and/or shielded by substantially light-resistant, preferably, opaque packaging and/or a container-closure system that protects the contents from the effects of sunlight by virtue of the specific properties of the material of which it is composed, including any coating applied to it, including clear and colorless or translucent container made light-resistant by means of an opaque covering or by use of secondary packaging, or within amber colored containers.

A Tetflupyrolimet composition as selected from:

• (a) Tetflupyrolimet composition 19 characterized by a minimized rate or extent of sunlight-mediated conversion of Tetflupyrolimet to the compound of formula D,
• comprising at least one of, ingredient, excipient, adjuvant, carrier or additive that can mitigate the converting effect of exposure to sunlight or reduce the rate at which said conversion would occur on exposure to sunlight absent said ingredient, excipient, adjuvant, carrier or additive;
• (b) Tetflupyrolimet composition 110 stabilized to at least a measurable degree against sunlight-mediated conversion to the compound of formula D, during manufacturing, packaging, labeling, transportation, and storage, characterized in that said composition comprises at least one of, ingredient, excipient, adjuvant, carrier or additive that can mitigate the converting effect of exposure to sunlight and/or reduce the rate at which said conversion occurs absent said ingredient, excipient, adjuvant, carrier or additive and
• (c) Tetflupyrolimet composition 112 stabilized to at least a measurable degree against conversion to the compound of formula D or displaying a measurably reduced rate of conversion to the compound of formula D during manufacturing, packaging, labeling, transportation, and storage, as compared to the standard calibrating rate of conversion in one or more reference compositions comprising the Tetflupyrolimet, characterized in that said composition comprises at least one component which is any, some or all, of:
• i. a buffer which maintains the pH of the composition to 7±1;
• ii. a UV absorber;
• iii. an ingredient etc. that exhibits the absorption spectra substantially similar to that of the Tetflupyrolimet such as a dye, colorant or pigment;
• iv. an ingredient etc. capable of reducing the amount of sunlight impinging on the material (Tetflupyrolimet);
• v. an opacifier;
• vi. a reflecting pigment such as titanium dioxide;
• vii. a light protecting coating over a least a portion of said Tetflupyrolimet in said composition;
• viii. a complex of Tetflupyrolimet with a complexing agent exemplified by an inclusion complex such as with a cyclodextrin;
• wherein said reference compositions comprise Tetflupyrolimet absent said component.

A product (Embodiment I11) comprising a Tetflupyrolimet composition shielded against sunlight-mediated conversion to the compound of formula D during any of, manufacturing;

• packaging;
• labeling;
• transportation;
• or storage;
• of said composition, characterized in that the product comprises said Tetflupyrolimet composition contained within substantially light-resistant, preferably, opaque packaging, wherein the Tetflupyrolimet is in a liquid, solution, emulsion, or suspension composition, preferably as an aqueous composition.

A procedure for preparing reference compositions for establishing standard calibrating rates of conversion of Tetflupyrolimet to the compound of formula D and thus calibrating the pH dependency of formation of the compound of formula D on exposure of Tetflupyrolimet to sunlight comprising:

• a. suspending three lots of about 50 mg of Tetflupyrolimet in about 2 ml of a 2% solution of acetonitrile in water each, and sonicating for about 20 minutes
• b. adding 0.1 ml of buffer pH=4, pH=7, and pH=10 to each suspension respectively
• c. filtering the three buffered solutions
• d. introducing each buffered solution into a quartz tube
• e. exposing said tube to natural sunlight for approximately 2 months
• f. analyzing each buffered solution by HPLC-MS to show the formation of the corresponding Storage Marker in each solution in pH related concentrations.