83846-35-9

Upstream product

• 28273-55-4 potassium salt of 2-nitropropane 
• 42009-04-1 2-bromo-2-methyl-1-(4-nitrophenyl)propan-1-one 
• 10326-99-5 2-methyl-1-(4-nitrophenyl)propan-1-one 
• 83846-29-1 2-chloro-2-methyl-3-(p-nitrophenyl)-3-propanone 
• 609-08-5 Diethyl methylmalonate 
• 1443-80-7 4-cyanophenyl methyl ketone 
• 3958-63-2 lithium 2-nitropropane 
• 79-46-9 2-nitropropane 
• 83846-30-4 4-(2-Chloro-2-methyl-propionyl)-benzonitrile 
• 98-07-7 Benzotrichlorid 
• 67-64-1 acetone 
• 1122-60-7 1-nitrocyclohexane 
• 105-53-3 diethyl malonate 

Relevant academic research and scientific papers

Monosubstituted and polysubstituted functional group aromatic ketone compounds, and preparation method and photopolymerization initiator thereof

The invention belongs to the field of radiation curing new materials, and relates to an aromatic ketone compound, in particular to a monosubstituted or polysubstituted polyfunctional group aromatic ketone compound, a preparation method thereof and a photopolymerization composition containing an ethylenically unsaturated compound system, which takes the compound as an effective component. The invention provides monosubstituted and polysubstituted polyfunctional group aromatic ketone compounds. The polyfunctional group aromatic ketone compounds have a general formula structure as shown in (I). The invention also discloses a preparation method and an application of the polyfunctional aromatic ketone compound. According to the invention, industrial-grade raw materials which are low in cost and easy to obtain are used as a starting point to prepare the monosubstituted or polysubstituted functionalized aromatic ketone compound in a breakthrough way, and the compound is applied to a photoinitiator in radiation curing, so that the problems of toxicity and VOCs pollution of the photoinitiator are solved, and the economic competitiveness of the photoinitiator is strived; the overall cost is reduced, and the photo-initiation efficiency is improved.

Alkylation of Nitrile Anions by Tertiary α-Halo Ketones and Nitriles

Potassium salts of nitriles bearing carbethoxy, cyano, or phenyl groups at the α carbon react with tertiary α-halo ketones and nitriles (1-5) in DMSO or HMPA to provide the alkylated β-keto- or β-cyano-β,β-dialkyl nitriles 6-10 in useful yields. (PhCHCN)(-) undergoes cyclization with p-XC6H4COCCl(CH3)2 to produce 2(5H)-furanone 11.Reaction of (Ph2CCN)(-) with PhCOCCl(CH3)2 affords the hydrolyzed ketone 12a and recovered carbon acid, while the anion undergoes oxidative dimerization to NCCPh2CPh2CN with p-O2NC6H4COCCl(CH3)2 with concomitant formation of the reduced ketone p-O2NC6H4COCH(CH3)2 and the hydrolyzed ketone 12b.The alkylations of (-) and (-) with p-O2NC6H4COCX(CH3)2 take place by the SRN1 process.

Reaction ofα- Halo Ketones with Nucleophiles

p-Nitro- or p-cyanophenacyl chloride or the 1,1-dimethyl derivatives react with the anion of 2-nitropropane to form the C-alkilation product by a radical chain mechanism (SRN1).With the 1,1-dimethyl derivatives, the free radical substitution is photostimulated and occurs in competition with ionic reactions leading to the oxiranes 5 and hydroxy ketones 6.When K+ is used as the counterion, the SRN1 process is favored by complexation with 18-crown-6. p-Nitro-1,1-dimethylphenacyl chloride gives substitution products with diethyl malonate or diethyl mthylmalonate anions via the SRN1 process, but with PhS- or p-MeC6H4SO2-, substitution occurs by competing ionic and radical processes.Propylacetylenide anion reacts to form the oxirane 13a while diethyl phosphite or thiophosphite anions yield the enol phosphate 14a or thiophosphate 14b. 1,1-Dimethylphenacyl chloride reacts by nonradical processes to give the oxirane with acetylenide anions, the substitution products with PhS- or p-MeC6H4SO2- and a mixture of the enol phosphate, and oxirane 16 with diethyl phosphite anion.With Me2C==NO2-K+, mainly the oxirane is formed in Me2SO but mainly substitution via the SRN1 chain is observed in HMPA.