Acrylic acid reaction

Similarly, 3-(3-selenienyl)acrylic acid yields 30-40% 3,5-dichloro-selenopheno[2,3-6]thiophene-2-carbonyl chloride (103) and 15% 2-chloro-3-(2,4,5-trichloro-3-selenienyl)acryloyl chloride, together with other products [Eq. (33)]. (Experimental details for the 3-(3-furyl)and 3-(3-selenienyl)acrylic acid reactions were not given in ref. 83). 

If this mechanism is strictly followed the chain length and hence the value of 02-uptake (see below) increases linearly with the substrate concentration and (initiation rate)"1/2 (i.e., in radiolytic studies the dose rate) and in charged polymers also on the pH (cf. Ulanski et al. 1996a). In polymers, the chain reaction may mainly proceed intramolecularly (Ulanski et al. 1996a Janik et al. 2000). An example for an efficient intramolecular autoxidation is poly(acrylic acid) [reactions (34)-(36) Ulanski et al. 1996a], In these autoxidation reactions, hydroperoxides are formed which, in some cases, are quite unstable [e.g. reaction (37) see also Leitzke et al. 2001],... 

Added manufacturing cost for acrylic acid reaction 0.10/lb. Total cost of radiation curable resin = 0.44/lb. 

The production procedure of AESO is shown in Fig. 3. The double bonds are one of the active sites that can react with functional groups. Epoxy groups react with double bonds in an epoxidation reaction to form epoxidized soy oil [16] and the acrylic acid reaction with epoxidized soy oil occurs through a substitution reaction [7]. 

There are many examples for instance (i) formation of anhydrides in poly(acrylic acid) (reaction 40), and (ii) formation of acetals in poly(vinyl alcohol) (reaction 41)... 

The only study of the reaction of OH with the unsaturated organic acids is a relative rate study (Teruel et al, 2007) of the OH-acrylic acid reaction data are summarized in table VI-D-1. A value of = 1.7 x 10 cm molecule" is obtained, using updated reference rate data. An uncertainty of 30% is assumed. On the basis of this study, rate coefficients of approximately 2.5 x 10 cm molecule" s for reaction of OH with methacrylic and crotonic acid are estimated, with uncertainties of about a factor of 2. 

Apart from the thoroughly studied aqueous Diels-Alder reaction, a limited number of other transformations have been reported to benefit considerably from the use of water. These include the aldol condensation , the benzoin condensation , the Baylis-Hillman reaction (tertiary-amine catalysed coupling of aldehydes with acrylic acid derivatives) and pericyclic reactions like the 1,3-dipolar cycloaddition and the Qaisen rearrangement (see below). These reactions have one thing in common a negative volume of activation. This observation has tempted many authors to propose hydrophobic effects as primary cause of ftie observed rate enhancements. 

Asymmetric hydrogenation has been achieved with dissolved Wilkinson type catalysts (A. J. Birch, 1976 D. Valentine, Jr., 1978 H.B. Kagan, 1978). The (R)- and (S)-[l,l -binaph-thalene]-2,2 -diylblsCdiphenylphosphine] (= binap ) complexes of ruthenium (A. Miyashita, 1980) and rhodium (A. Miyashita, 1984 R. Noyori, 1987) have been prepared as pure atrop-isomers and used for the stereoselective Noyori hydrogenation of a-(acylamino) acrylic acids and, more significantly, -keto carboxylic esters. In the latter reaction enantiomeric excesses of more than 99% are often achieved (see also M. Nakatsuka, 1990, p. 5586). 

The key step in the total synthesis of rhizobitoxine is the Pd-catalyzed exchange reaction of the methyl alkenyl ether moiety in 4 with the functionalized alcohol, although the yield is low[3]. The enol pyruvate 6 (a-ethoxyacrylic acid) is prepared by the reaction of methyl a-methoxyacrylate or a-methoxy-acrylic acid (5) with ethanol catalyzed by PdCl2(PhCN)2 at room temperature in the presence of CuCli and NaH2P04[4],... 

As an application of this nucleophilic reactivity, 2-aminothiazole was used to partially convert into amide the polymer obtained from acrylic acid, benzene, and acetic anhydride (271). An aqueous medium is reported to favor the reaction between acetic anhydride and 2-aminothiazole (272). 

Acrylic Acid, Acrylates, and Acrylonitrile. Acryhc acid [79-10-7], and acrylates were once prepared by reaction of acetylene and... 

The significance of industrial acrolein production may be clearer if one considers the two major uses of acrolein—direct oxidation to acryUc acid and reaction to produce methionine via 3-methyhnercaptopropionaldehyde. In acryUc acid production, acrolein is not isolated from the intermediate production stream. The 1990 acryUc acid production demand in the United States alone accounted for more than 450,000 t/yr (28), with worldwide capacity approaching 1,470,000 t/yr (29). Approximately 0.75 kg of acrolein is required to produce one kilogram of acryUc acid. The methionine production process involves the reaction of acrolein with methyl mercaptan. Worldwide methionine production was estimated at about 170,000 t/yr in 1990 (30). (See Acrylic ACID AND DERIVATIVES AmINO ACIDS, SURVEY.)... 

The amide group is readily hydrolyzed to acrylic acid, and this reaction is kinetically faster in base than in acid solutions (5,32,33). However, hydrolysis of N-alkyl derivatives proceeds at slower rates. The presence of an electron-with-drawing group on nitrogen not only facilitates hydrolysis but also affects the polymerization behavior of these derivatives (34,35). With concentrated sulfuric acid, acrylamide forms acrylamide sulfate salt, the intermediate of the former sulfuric acid process for producing acrylamide commercially. Further reaction of the salt with alcohols produces acrylate esters (5). In strongly alkaline anhydrous solutions a potassium salt can be formed by reaction with potassium / /-butoxide in tert-huty alcohol at room temperature (36). 

This process yields satisfactory monomer, either as crystals or in solution, but it also produces unwanted sulfates and waste streams. The reaction was usually mn in glass-lined equipment at 90—100°C with a residence time of 1 h. Long residence time and high reaction temperatures increase the selectivity to impurities, especially polymers and acrylic acid, which controls the properties of subsequent polymer products. 

Dimer formation, which is favored by increasing temperature, generally does not reduce the quaHty of acryhc acid for most applications. The term dimer includes higher oligomers formed by further addition reactions and present in low concentrations relative to the amount of dimer (3-acryloxypropionic acid). Glacial acrylic acid should be stored at 16—29°C to maintain high quaHty. 

AUyl acetate can be obtained by the vapoi-phase reaction of propylene and acetic acid over a supported Pd catalyst (eq. 20) (110). Reaction of acrylic acid and propylene yields isopropyl acrylate (eq. 21), and catalytic reaction with acetic acid produces isopropyl acetate (eq. 22) (110). 

Acrylic Acid. In Europe some acryHc acid [79-10-7] and ester is manufactured by the Reppe reaction from acetjdene, methanol, and carbon monoxide (eq. 10) (see Aacrylic acid and derivatives). 

The addition of benzonitrile oxide to acrylic acid gave only the 4-carboxylic acid (441) (59MI41601), while addition to cis- and trans-cinnamic esters gave cis and trans diastereomeric pairs of 4-carboxylic acids (442) (Scheme 100) (59MI41600). Arbisono repeated the experiment and, when methyl c/s-cinnamate was used, in addition to the 4-carboxylic acid some 5-carboxylic acid (442) was isolated (66MI41600). The reaction of vinyl bromides with benzonitrile oxide yielded only an isoxazole and not a bromoisoxazoline (Scheme 101) (78JCR(S)192). 

Acrylic acid, -(3-benzo[f>]thienyl)-a -mercapto-reaction with iodine, 4, 764 Acrylic acid, o -cyano-y3-(2-thienyl)-ring opening, 4, 807 Acrylic acid, -formyl-in pyridazinone synthesis, 3, 46 Acrylic acid, furyl-rotamers, 4, 545 synthesis, 4, 658 Acrylic acid, 2-hydroxybenzoyl-chroman-4-one synthesis from, 3, 850 Acrylic acid, 5-(l-propynyl)-2-thienyl-methyl ester occurrence, 4, 909 Acrylonitrile... 

Low temperatures can cause a phase separation in stabilized solutions in which case one phase can become deficient in stabilizer and subject to runaway reactions. Acrylic acid can crystallize out of stabilized solution, and subsequent thawing of these essentially pure acrylic acid crystals can initiate runaway reactions, often with severe consequences. Thawing of crystallized (frozen) materials needs to be accomplished using established procedures in thaw boxes or similar devices. If established procedures are not available, a safety review needs to be conducted and a procedure developed prior to thawing the material. 

Efficiency means component 1 made per component 3 converted, all in molar units. Data show that 89.7% of the converted propylene was accounted for by the formed acrolein. An additional 9.8% efficiency is indicated for acrylic acid. Efficiency to total useftil product was 99.5% as long as ignition of homogeneous reaction could be avoided... 

The preparation and use of derivatized Meldrum s acid has led to an alternative preparation of 2-substituted quinolines (49 and 50) and the preparation of pyridopyrimidines (52). When Meldrum s acid derivatives are used (as shown in this example) decarboxylation occurred under the cyclization conditions. Three component coupling has been used to readily assemble the desired 3-anilino-acrylate from reaction of Meldrum s acid, (EtO)3CH and an aniline (e.g. 54 or 55).< ... 

The Diels-Alder reactions of the methyl or ethyl ester of benzenesulfonylindole-2-acrylic acid with several l-alkoxycarbonyl-l,2-dihydropyridines are reported and only a single stereoisomer was obtained, as in the case of l-methoxy(ethoxy)-carbonyl-1,2-dihydropyridines. However, when the Diels-Alder reaction of 17 was carried out with 8g[R = (CHsjsC], a mixture of two stereoisomers 18gand25were obtained in a 1 1 ratio (65% total yield). The bulky rerr-butyl group creates sufficient steric interference with the indole ring to cause the loss of stereochemistry ... 

The reaction of bromine with (pyrazol-4-yl)acrylic acid and its esters and the subsequent dehydrobromination of the products have been investigated by Finar and Okoh [73JCS(P1)2008]. Attempts to dehydrobrominate bromoacrylic acids (20) to 3-( 1 -phenylpyrazol-4-yl)propiolic acids 22 failed, but were successful when bromoesters 21 were used (Scheme 32). 

Heating the crystalline salt 2-aminopyridinium propiolate (346) at 100 °C in the solid state led to a 10 9 mixture of 2/f-pyrido[l,2-n]pyrimidin-2-one and ( )-3-(2-imino-l,2-dihydro-l-pyridyl)acrylic acid (347). Analysis of differental scanning calorimetry data shows unambiguously that the reaction takes place in the solid state. An endothermic peak at 81.1 °C corresponds to a solid state reaction, and a peak at 122-123 °C is attributed to melting. The product ratio of 2//-pyrido[l, 2-n]pyrimidin-2-one and 347 is 1 2.5 at 60°C, and 1 1.4 at 80°C (94MI12). 

Dehydrogenation of the later with Pd/C gave 329 (82AP901). On the other hand, reaction of indoline or 2-methylindoline with acrylic acid or crotonic acid by heating in presence of polyphosphoric acid gave 330 and 331 (79JHC949) (Scheme 59). 

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