SUN LIGHT AS AN AVAILABLE AND UNENDING ENERGY SOURCE AND WATER AS A GREEN, CHEAP AND SAFE SOLVENT HAVE ATTRACTED A LOT OF ATTENTION FOR APPLICATION IN ORGANIC SYNTHESIS [1-2]. IN CONTRAST TO THE POPULARITY OF ‘TIO2 NANOPARTICLES’ IN PHOTOCATALYTIC TRANSFORMATIONS IN ORGANIC SOLVENTS, THEIR USE IN SELECTIVE ORGANIC SYNTHESIS IN WATER IS STILL NOT QUITE WIDESPREAD [3]. IN THIS WORK WE PRESENT A HIGHLY EFFICIENT AND GREEN PHOTOCATALYTIC SYSTEM FOR SELECTIVE REDUCTION OF THE NITRO GROUP UNDER SUNLIGHT IRRADIATION BASED ON IN-SITU MODIFICATION OF TIO2 P25 WITH B-CD IN WATER. WE BELIEVE THAT B-CD CAN ENHANCE THE DISPERSION OF TIO2 IN WATER, AND TOGETHER PRODUCE A ' HOST NANO-REACTOR SYSTEM', THAT WE CALL THE "GREEN NEST", IN ORDER TO COMPENSATE FOR THE LOW INTERACTION OF THE ORGANIC NITRO COMPOUND WITH THE SURFACE OF TIO2 IN AN AQUEOUS MEDIUM. THIS "GREEN NEST" SYSTEM SHOWED HIGH EFFICIENCY FOR THE REDUCTION OF NITRO COMPOUNDS TO THE CORRESPONDING AMINES, AND MORE INTERESTINGLY, ONE POT REDUCTIVE N-FORMYLATION AND N-ACYLATION FROM NITRO COMPOUNDS CAN BE CARRIED OUT IN THE PRESENCE OF TRIETHYL ORTHOFORMATE, ACETIC AND BENZOIC ANHYDRIDE.

COPPER NANOPARTICLES WERE PREPARED ACCORDING TO PREVIOUS REPORT BY SHARGHI ET AL [1]. A SERIES OF AROMATIC NITRO COMPOUNDS WERE REACTED WITH SODIUM BOROHYDRIDE IN THE PRESENCE OF THE COPPER NANOPARTICLES TO AFFORD THE AROMATIC AMINO COMPOUNDS IN GOOD YIELDS [2]. ADDITIONALLY, THE CATALYSTS SYSTEM CAN BE RECYCLED AND MAINTAIN A HIGH CATALYTIC EFFECT IN THE REDUCTION OF AROMATIC NITRO COMPOUNDS [3].

MONITORING OF TYPES AND LEVELS OF EXPLOSIVE SUCH AS NITROTOLUENE (NT), 2, 4, 6-TRINITROTOLUENE (TNT), CYCLOTRIMETHYLENETRINITRAMINE (RDX), DINITROTOLUENE (DNT), 2, 4, 6-TRINITROTOLUENE (TNT), TETRYL, CYCLOTRIMETHYLENETRINITRAMINE (RDX), ...

BACKGROUND: ORDERED MESOPOROUS SILICA MATERIALS HAVE RECEIVED CONSIDERABLE ATTENTION BECAUSE OF THEIR UNIQUE STRUCTURES WITH ORGANIZED POROSITYAND HIGH SPECIFIC SURFACE AREAWHICH MAKE THEM AVAILABLE TO A WIDE RANGE OF APPLICATIONS IN THE AREAS OF ADSORPTION, SEPARATION, AND CATALYSIS [1]. THE NANOPARTICLES DISPERSED ON THE SUPPORTS OFTEN EXHIBITED SPECIFIC PHYSICAL AND CHEMICAL PROPERTIES, AND GAVE RISE TO HIGH CATALYTIC ACTIVITY FOR THE REDUCTION OF A WIDE VARIETY OF NITROBENZENES. NI NANOPARTICLES IN PARTICULAR BEING CHEAP NEED MILD REACTION CONDITIONS FOR HIGH YIELD OF PRODUCTS IN SHORT REACTION TIMES [2-3].METHODS: NI-PVAM/KIT-6 COMPOSITE WAS SYNTHESIZED IN FOUR STEPS: SYNTHESIS OF KIT-6, PREPARATION OF POLYACRYLAMIDE /KIT-6, PREPARATION OF POLYVINYL AMINE/KIT-6, PREPARATION OF NI NANOPARTICLES POLYVINYLAMINE /KIT-6 RESULTS: THE XRD PATTERN SHOWS A SHARP INTENSE PEAK AT 2 Θ=0.95 CORRESPONDING TO (211) PLANE AND A HUMP FOR (220) AND (320) PLANES (FIG.1). THE XRD PATTERNS OF NI-PVAM/KIT-6 SAMPLE AT TWO TEMPERATURES. AFTER CALCINING AT 200OC (FIG.2A), XRD PATTERNS OF RESIDUE SHOWED THAT THE BROADENING AND LOWINTENSITY OF PEAKS COULD BE ATTRIBUTED TO NANO SIZE OF NI PARTICLES. NEVERTHELESS, THE PEAKS AT 2Θ=44.29, CORRESPONDING TO THE PLANE (111) OF FCC NICKEL, COULD BE OBSERVED. THE SAME PROCEDURE CAN BE SEEN IN FIG. 2B, NICKEL NANOPARTICLES PEAK IS SHOWN AT 2Θ=44.

CYANOHYDRINS ARE VERSATILE INTERMEDIATES, WHICH CAN EASILY BE CONVERTED INTO WIDE VARIETY OF VALUABLE CLASSES OF COMPOUNDS. CYANOHYDRINS ARE TYPICALLY PREPARED BY THE INTERACTION OF VARIOUS CARBONYL COMPOUNDS WITH A CYANIDE SOURCE SUCH AS TRIMETHYLSILYL CYANIDE (TMSCN) AS NUCLEOPHILE [1]. GENERALLY, IN THE ABSENCE OF A CATALYST, NO REACTION OCCURS BETWEEN TMSCN AND CARBONYL COMPOUNDS. THE CYANOSILYLATION IS PARTICULARLY SUITABLE SINCE THE SILYL PROTECTING GROUPS CAN BE REMOVED UNDER VERY MILD REACTION CONDITIONS [2].IN THIS REPORT 4-NITRO POTASSIUM PHTHALIMIDE (1) WAS SYNTHESIZED AND USED AS A NOVEL AND AN EFFICIENT ORGAN OCATALYST FOR CYANOSILYLATION OF CARBONYL COMPOUNDS UNDER MILD AND SOLVENT-FREE CONDITIONS AFFORDING VARIOUS CYANOHYDRIN TRIMETHYLSILYL ETHERS (SCHEME 1).SINCE THIS REACTION COULD BE PERFORMED WELL IN SOLVENT-FREE CONDITIONS AND HAS NO EFFECTS OF TOXIC SOLVENTS AND WASTES WITH ADDED ADVANTAGES OF RECYCLABILITY FOR THREE TIMES WITHOUT LOSS OF EFFICIENCY, THEREFORE HAS A GOOD POTENTIALITY FOR RECYCLING, IT HELP VALUABLE MATERIALS TO SUSTAIN. AS A RESULT, WASTES LOSS WILL BE DECREASED DRAMATICALLY MAKING THEM IN GOOD AGREEMENT WITH GREEN CHEMISTRY.