Methyl acrylate, heats

Methyl acrylate heated 16 hrs. at 70° with diethyl fumarate in the presence of tricyclohexylphosphine under Ng in dioxane -> 1,2-diethyl 3-methyl 3-butene-1,2,3-tricarboxylate. Y 95.5%. F. e. s. K. Morita and T. Kobayashi, Bull. Chem. Soc. Japan 42, 2732 (1969). 

Barrelene was obtained via a double Diels-Alder reaction from a-pyrone with methyl acrylate (H.E. Zimmerman, I969A). The primarily forming bicyclic lactone decarboxylates in the heat, and the resulting cyclohexadiene rapidly undergoes another Diels-Alder cyclization. Standard reactions have then been used to eliminate the methoxycarbonyl groups and to introduce C—C double bonds. Irradiation of barrelene produces semibullvalene and cyclooctatetraene (H.E. Zimmerman. 1969B). 

Bromo-3-iodo-l-(4-methylphenylsulfonyl)indole (0.476 g, 1.00 mmol), methyl acrylate (0.108 g, 1.25 mmol), EtjN (0.127 g, 1.25 mmol) and Pd(OAc)2 (11 mg, 0.050 mmol) were mixed in a tube, purged with argon and the tube was sealed and heated to 100°C for 1 h. After cooling, it was opened and mixed with CH2CI2 (50 ml). The solution was washed with water and dried (Na SOJ. The residue was purified by chromatography on silica using 1 3 benzene-hexane for elution. The yield was 0.350 g (81%). 

Low Temperature Properties. Medium hardness compounds of average methyl acrylate, ie, VAMAC G, without a plasticizer typically survive 180° flex tests at —40° C. Such performance is good for a heat-resistant polymer. Low temperature properties can be greatly enhanced by the use of ester plasticizers (10). Careful selection of the plasticizer is necessary to preserve the heat resistance performance of the polymer. Plasticized high methyl acrylate grades lose only a few °C in flexibiUty, compared to grades with average methyl acrylate levels. 

More recently, in 1975, Du Pont introduced a terpolymer (Vamac) based on ethylene, methyl acrylate and a third monomer of undisclosed composition which contained a carboxylic acid group to provide a cure site for use with peroxides or amines. Both types of rubber exhibit good heat, oxygen and ozone resistance. 

Thus, condensation of isoniazide with acetone at the basic nitrogen gives the corresponding Shiff base (8). Catalytic reduction affords the antidepressant, iproniazid (9). Addition of the same basic nitrogen to methyl acrylate by Michael condensation leads to the 3-amino ester (10). This is converted to the amide, nialamide (11), on heating with benzylamine. 

Methyl acrylate, 28.0 g (0.4 mol) was added dropwise during one hour to a solution containing 54.8 g (0.4 mol) of isonicotinic acid hydrazide (isoniazid) and 10 ml of glacial acetic acid in 400 ml of tertiary butyl alcohol. The resulting solution then was heated for 18 hours on a steam bath. Concentration of the reaction mixture to 100 ml yielded 13.0 g of unreacted isonicotinic acid hydrazide. The filtrate was concentrated to a thick syrup which was triturated... 

Isayama described the coupling reaction of N-methylimine 157 and ethyl crotonate catalyzed by Co(acac)2 and mediated by PhSiH3 to produce Mannich product 158 in 82% with syn-selectivity (Scheme 41) [71]. The (i-laclam 159 was readily synthesized by heating 158. In 2002, Matsuda et al. reported cationic Rh complex [Rh(COD) P(OPh)3 2]OTf (1 mol%) as an active catalyst for the reductive Mannich reaction [72]. N-Tosylaldiminc 160 was coupled with methyl acrylate and Et2MeSiH (200 mol%) at 45 °C to give the b-amino ester 161 in 96% with moderate anti-selectivity 68%. 

Ratchford and Fisher found that methyl-acetoxypropionate decomposes on heating to form acetic acid and methyl acrylate ... 

Applying the concept of using solvents doped with ionic liquids in order to allow microwave heating to high temperatures (see Section 4.3.3.2), Leadbeater and Tore-nius studied the Diels-Alder reaction between 2,3-dimethylbutadiene and methyl acrylate (Scheme 6.91) [190]. This reaction is traditionally performed in toluene or... 

As depicted in Scheme 11, ylides 39 derived from 4-methyl-[l,2,3]triazolo[l,5- ]pyridine react with Michael acceptors, which, upon nucleophilic attack at C3 and ring opening, lead to nucleophilic displacement of nitrogen. The intermediate diradical led to a mixture of compounds, including alkenes and a cyclobutane derivative when methyl acrylate was used, and the indolizine 40 with methyl propiolate as the electrophile <1998T9785>. Heating 4-methyl triazolopyridine with benzenesulfonyl chloride in acetone also confirmed decomposition via a radical pathway. 

Polymerisation of methyl acrylate is catalysed by heat, light or peroxide. PolyMethylmethacrylate... 

General Procedure A (esterification of amine) 1 A 50 wt% methanol solution of methyl acrylate (17 g, 0.2 mol) was added to the methanolic solution of Jeffamine T-3000 (100 g, 0.033 mol). This reaction was allowed to stir at room temperature under a nitrogen atmosphere for 48 h. The reaction was then heated to 50°C for 1 h. methanol and excess methyl aerylate were removed by rotary evaporator. After the dialysis using membrane filter with a MWCO of 3 D in methanol, the product was obtained as a yellow viscous oil (6 g, 98%). H NMR (CDCl, 5),... 

Photolytic. Polymerizes on standing and is accelerated by heat, light, and peroxides (Windholz et al., 1983). Methyl acrylate reacts with OH radicals in the atmosphere (296 K) and aqueous solution at rates of 3.04 x 10 and 2.80 x 10 cmVmolecule-sec, respectively (Wallington et al, 1988b). 

The heat of an emulsion polymerization is the same as that for the corresponding bulk or solution polymerization, since AH is essentially the enthalpy change of the propagation step. Thus, the heats of emulsion polymerization for acrylic acid, methyl acrylate, and methyl methacrylate are —67, —77, and —58 kJ mol-1, respectively [McCurdy and Laidler, 1964], in excellent agreement with the AH values for the corresponding homogeneous polymerizations (Table 3-14). 

To investigate the internal plasticization of polystyrene (Tg = 105 C) by insertion of methyl acrylate (Tg = 4°C),the samples are run on a DSC.Therefore, approximately 15 mg of each of the well dried polymers are weighed into small aluminum pans and measured by two heat-cool runs in a DSC apparatus.The glass transition is found as a characteristic jump in the heat capacity in the system.The glass transition temperature is evaluated after the second heating from the DSC plot. 

To 0.2 mole of an olefin dissolved in 30 ml of glacial acetic acid is added 19.5 gm (0.3 mole) of sodium azide in 75 ml of water. The addition to acrolein and jf -nitrostyrene underwent rapid addition, requiring cooling with an ice-salt bath and slow addition of the sodium azide. Addition to methyl acrylate, acrylic acid, and acrylonitrile required 1-3 days at room temperature, a-vinyl pyridine and mesityl oxide required heating for 24 hr on a steam bath. Other olefins underwent no reaction even after 7 days of heating and were recovered unchanged. 

These binders possess properties which are very important for ease of manufacture and for obtaining a uniform product. Thus they have low viscosity on casting without sedimentation of solids, have sufficient reactivity for complete low-temperature cure and evolve little heat on polymerization (e.g. much lower than heat of polymerization of methyl acrylate). 

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