35233-69-3Relevant articles and documents
Cyanide-Free One-Pot Synthesis of Methacrylic Esters from Acetone
Koyama, Minoru,Kawakami, Takafumi,Okazoe, Takashi,Nozaki, Kyoko
supporting information, p. 10913 - 10917 (2019/08/02)
Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF3CH2, and n-C6F13CH2CH2 esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C6F13CH2CH2 esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d6 and MeOH-d4, with DBU in acetonitrile afforded deuterated MMA (MMA-d8) in 70 % yield.
Synthesis of [13C] and [2H] susbstituted methacrylic acid, [13C] and [2H] substituted methyl methacrylate and/or related compounds
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Page/Page column 1; 3; sheet 1/2, (2010/11/27)
The present invention is directed to labeled compounds of the formulae wherein Q is selected from the group consisting of —S—, —S(═O)—, and —S(═O)2—, Z is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure wherein R1, R2, R3, R4 and R5 are each independently selected from the group consisting of hydrogen, a C1-C4 lower alkyl, a halogen, and an amino group selected from the group consisting of NH2, NHR and NRR′ where R and R′ are each independently selected from the group consisting of a C1-C4 lower alkyl, an aryl, and an alkoxy group, and X is selected from the group consisting of hydrogen, a C1-C4 lower alkyl group, and a fully-deuterated C1-C4 lower alkyl group. The present invention is also directed to a process of preparing labeled compounds, e.g., process of preparing [13C]methacrylic acid by reacting a (CH3CH2O—13C(O)—13CH2)— aryl sulfone precursor with 13CHI to form a (CH3CH2O—13C(O)—13C(13CH3)2)— aryl sulfone intermediate, and, reacting the (CH3CH2O—13C(O)—13C(13CH3)2)— aryl sulfone intermediate with sodium hydroxide, followed by acid to form [13C]methacrylic acid. The present invention is further directed to a process of preparing [2H8]methyl methacrylate by reacting a (HOOC—C(C2H3)2— aryl sulfinyl intermediate with CD3I to form a (2H3COOC—C(C2H3)2)— aryl sulfinyl intermediate, and heating the(2H3COOC—C(C2H3)2)— aryl sulfinyl intermediate at temperatures and for time sufficient to form [2H8]methyl methacrylate.
METHOD FOR PRODUCING DEUTERATED METHYL METHACRYLATE
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Page/Page column title page; 7; 10, (2008/06/13)
A method for producing MMA-d8 which includes a step of exchanging D in hydroxyl group of methanol-d4 represented by the formula: CD3OD with H to prepare the methanol-d3 represented by the formula CD3OH and simultaneously recovering a deuterium-containing compound, and a step of reacting methanol-d3 with sulfuric acid salt of methacrylic acid amide represented by the formula CD2=(CD3)CO(NH2·H2SO4) to prepare MMA-d8 represented by the formula: CD2=(CD3)COOCD3.
MANUFACTURING METHOD OF DEUTERATED METHYL METHACRYLATE
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Page/Page column 9, (2010/02/11)
PROBLEM TO BE SOLVED: To provide an economical manufacturing method of methyl methacrylate-d8 (C5D8O2) which is excellent in both the deuteration rate and the chemical purity and is useful as a raw material for plastic optical fibers and optical waveguide materials having a low transmission loss.SOLUTION: Methyl methacrylate-d8 is manufactured using as raw materials readily available methanol-d4 and acetone-d6 with all hydrogen atoms thereof deuterated, where methanol-d4 is converted into methanol-d3 with its methyl group fully deuterated and methyl methacrylate-d8 is obtained from the thus-obtained methanol-d3 with its methyl group fully deuterated and acetone cyanhydrin-d6 prepared from acetone-d6. A deuterium-containing compound, recovered when methanol-d4 is converted into methanol-d3 with its methyl group fully deuterated, is reutilized as a part of raw materials for manufacturing methanol-d4 and acetone-d6.
LIVING POLYMERIZATION OF METHACRYLIC ESTERS WITH ALUMINIUM PORPHYRIN INITIATORS. AXIAL LIGAND EXCHANGE ACTIVITIES OF ALKYL- AND ENOLATE-ALUMINIUM PORPHYRINS IN RELATION TO THE POLYMERIZATION MECHANISM
Aida, Takuzo,Sugimoto, Hiroshi,Kuroki, Masakatsu,Inoue, Shohei
, p. 249 - 257 (2007/10/02)
Polymerization of methacrylic esters such as benzyl methacrylate using as initiator an-equimolar mixture of methylaluminium 5,10,15,20-tetraphenylporphine and 2,7,12,17-tetramethyl-3,8,13,18-tetramethylporphine proceeded from both initiators, affording a unimodal polymer of narrow molecular weight distribution, although the reactivities of (TPP)AlMe and (EtioP)AlMe are very different from each other. 1H NMR studies on a mixture of two different (porphinato)aluminium enolates, the growing species, and a mixture of a (porphinato)aluminium enolate and an alcoholate, in the absence and presence of methyl methacrylate (MMA or MMA-d8), indicated an acyclic transition state polymerization mechanism by the participation of two aluminium porphyrin molecules, where the growing species always exchange their enolate ligands whenever it grows.
