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The Synthesis Of 1, 3 - Dihydroxyacetone Research

Posted on:2013-02-07Degree:MasterType:Thesis
Country:ChinaCandidate:S L PangFull Text:PDF
GTID:2241330395959679Subject:Applied Chemistry
Abstract/Summary:PDF Full Text Request
1,3-Dihydroxyacetone is an important chemical, pharmaceutical intermediate. Itis widely used in food, cosmetic and pharmaceutical industries, the market demand isextensive, it has very high application value.At present about the synthesis of1,3-dihydroxyacetone, biological method is themain method. Biological method has been studied and has certainly researchedprogress but synthesis technique is not very mature, it needs breeding of good strains.Strain problems remain to be solved. Chemical method for synthesis of1,3-dihydroxyacetone has been reported rarely and does not have development value.In the view of synthesis, we design three original synthetic routes. The synthesismethod has some breakthrough. This paper mainly includes the following contents:1.1,3-Dihydroxyacetone is synthesized using1,3-dichloro acetone and ethyleneglycol as main raw materials, through carbonyl protection、 etherification、hydrogenolysis and hydrolyzation. We study of the effect of different conditions onthe reaction.1,3-dichloro acetone and ethylene glycol reflect in toluene and dehydrateto generate1,3-dioxolane-2,2-bis(chloromethyl), then it is heated with benzyl alcoholsodium in DMF to get2,2-bis((benzyloxy)methyl)-1,3-dioxolane. And then1,3-dioxolan-2,2-diyldimethanol is synthesized after hydrogenation, Pd/C as catalyst.And then in hydrochloric acid it is removed ethylene glycol protection for preparing1,3-dihydroxyacetone. The synthetic route of synthesis of1,3-dihydroxyacetone useseasily available raw materials, and the reaction conditions are mild. The Pd/C catalystcan be reused. It has important application value.2.1,3-Dihydroxyacetone is synthesized using1,3-dichloro acetone and methanolas main raw materials, through carbonyl protection、etherification、hydrogenolysisand hydrolyzation.We study of the effect of different reaction conditions on thereaction.1,3-dichloro acetone with excess anhydrous methanol under the conditionsof water absorbing agent react to synthesize1,3-dichloro-2,2-dimethoxypropane, it isheated with benzyl alcohol sodium in DMF to get1,3-bis((benzyloxy)methyl)-2,2-dimethoxypropane. And then2,2-dimethoxy-propane-1,3-diol is synthesized after hydrogenation, Pd/C as catalyst. And in hydrochloric acid it isremoved methanol protection for preparing1,3-dihydroxyacetone. We change thecarbonyl protection agents from ethylene glycol to methanol, so that1,3-dihydroxyacetone can be easily separated. It has important application value.3.1,3-Dihydroxyacetone is synthesized using acetone, methanol and chlorine orbromine as main raw materials. We study of the effect of different conditions on thereaction. Acetone, methanol and chlorine gas or bromine through “one-pot” methodreaction to synthetise1,3-dichloro-2,2-dimethoxypropane or1,3-dibromo-2,2-dimethoxypropane, and it is heated with benzyl alcohol sodium to get1,3-bis((benzyloxy)methyl)-2,2-dimethoxypropane. And then1,3-dihydroxyacetone issynthesized through hydrogenolysis and hydrolyzation. This reaction is under mildconditions."One-pot" reaction can avoid the use of higher cost of irritation of1,3-dichloro acetone. So the cost is low. It is more suitable for research and has greatdevelopment value.4. In this paper, we attempt to synthesize1,3-dihydroxyacetone through anothertwo routes.1,3-diacetoxyacetone is synthesized using1,3-dichloro acetone andsodium acetate as main raw materials via condensation reaction, and then throughhydrolysis reaction to synthesize1,3-dihydroxyacetone. We find that it mainlygenerate a monosubstituted product1-acetoxy-3-chloroacetone,1,3-diacetoxyacetoneyield is low. So the1,3-dihydroxyacetone yield is low. This needs to be studiedfurther;1,3-diacetoxyacetone is synthesized using glycerol and benzaldehyde as mainraw material through condensation, oxidation and hydrolysis. We through experimentsfind that glycerol and benzaldehyde formate of benzaldehyde glyceryl acetal isomersare not easily separated. So the product yield is low, it needs explore a bettercondition.
Keywords/Search Tags:1,3-dichloroacetone, 1,3-dihydroxyacetone, etherification, hydrogenolysis, carbonyl protection, glycerol benzaldehyde acetal, synthesis
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