Various alkoxycarbonylmethyl acrylates have been prepared by a unique method. Monochloroacetate and sodium acrylate or sodium methacrylate have been let to react in the presence of triethylamine as the catalyst at 100110°C in 38 hrs. The alkali-resistance of these esters is inferior to that of ethyl acrylate (EA), but the acid resistance is as good as that of EA. In the case of copolymerization between ethoxycarbonylmethyl acrylate (M1) and styrene (M2), r1 is 0.08±0.02 and r2 is 0.68±0.03. Q1 and e1 were 0.38 and 0.91 respectively.
Methyl acrylate is cony erted quantitatively to methyl α, β-dichloropropionate by chlorination at room temperature in the presence of 4 mol-% DMF as the catalyst. Methyl α, β-dichloropropionate is then methoxylated by reaction with an equimolar amount of Na-methylate in one hour without a catalyst at -20 to -35°C in mately 90% yield. Methyl α-chloro-β-methoxypropionate is let to react with an equimolar amount of potassiumcyanide at 30°C in a homogeneous solution. The yield is about 95%, but part of the produced α-cyano-β-methoxy propionate changes into poly-α-cyanoacrylate. Therefore, the true cyanation yield appears to be between 60 to 70%. Then crude methyl α-cyano-β-methoxypropionate is converted to methyl α-cyanoacrylate at rather high temperature, since the reaction involves the degradation of poly-α-cyanoacrylate. The reaction is carried out at 170250°C/39mmHg in a SO2 stream in the presence of 3 mole-% sulfuric acid and 100 g of DOP. Approximately 80% yield is attained.
Treatment of malononitrile in aqueous alkaline solutions afforded a dimer and a trimer depending on the reaction conditions. The dimer was identified as 1, 1, 3-tricyano-2-aminopropene(1). The trimer was found to be identical with “trismalononitrile I” of Schenck et al., and the structure was established to be 2, 4-diamino-3, 5-dicyano-6-cyanomethylpyridine(3) by the IR, mass, and MNR-spectra. The structure of “trismalononitrile II” of Schenck et al., was identified as ammonium salt of 1, 1, 3, 3-tetracyano-2-cyanomethylpropene(2), although Anderson et al., had reported it to be 2, 4-dicyanomethyl-5-cyano-6-amino-pyrimidine(5) and defined it as “the unstable form against heat.”
2-Oxocyclohexyl acrylate, phenacyl acrylate, α-trichloromethyl-β-carbomethoxyethyl acrylate and β, β, β-trichloroisopropyl acrylate have been prepared readily by the condensation of acryloyl chloride and the corresponding alcohol with the aid of triethylamine (equation A). CH2=CHCOCl + ROH N (C2H5)3→ CH2=CHCOOR (A) R=-H=O -CH2CO-_??_ -CHCH2COOCH3-CCl3, -CHCH3-CCl3 By the alcoholysis of methyl acrylate and methyl methacrylate with 2, 4, 4, 4-tetrachlorobutanol-1, 2, 4, 4, 4-tetrachlorobutyl acrylate and 2, 4, 4, 4-tetrachlorobutyl methacrylatehave also been prepared (equation B). CH2=CR'COOCH3 + ROH H2SO4→ CH2=CR'COOR (B) R=-CH2CHCH2CCl3-Cl, R'=H R=-CH2CHCH2CCl3-Cl, R'=CH3 These new acrylates and methacrylate have been polymerized in dioxane using 2, 2'-azobisisobutyronitrile as an initiator. Among others, the Polyacrylates and the polymethacrylates having three to four chlorine atoms in one unit of the polymer chain give films which do not burn.
A new preparative method of 9-phenanthrol was investgated. In the presence of cuprous bromide (22.6 g), 9-bromophenanthrene (50 g) was heated in an autoclave (500 cc) with 200% aq. sodium hydroxide (300 cc) for 5 hours at 230°C, and almost pure 9-phenanthrol was obtained in a quantitative yield (9599%). Among the catalysts examined, cuprous bromide and cuprous oxide gave the best results.