Reactions of Acrylic Acids

Electron-deficient and electron-neutral cinnamic acids undergo decarboxylative coupling with iodobenzenes under palladium catalysis to produce stilbenes 

AgOAc (2 equiv) LiOAc (3 equiv) LiCI (1.5 equiv) 

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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). 

Isopropyl acrylate is produced by an acid catalyzed addition reaction of acrylic acid to propylene. The reaction occurs in the liquid phase at about100°C ... 

Unsaturated acrylic oligomers are made from unsaturated acrylic monomers. For example, an epoxy acrylate may be made by reaction of acrylic acid with epoxy resin. 

The much more stable MIL-lOO(Cr) lattice can also be impregnated with Pd(acac)2 via incipient wetness impregnation the loaded catalyst is active for the hydrogenation of styrene and the hydrogenation of acetylene and acetylene-ethene mixtures to ethane [58]. MIL-lOl(Cr) has been loaded with Pd using a complex multistep procedure involving an addition of ethylene diamine on the open Cr sites of the framework. The Pd-loaded MIL-lOl(Cr) is an active heterogeneous Heck catalyst for the reaction of acrylic acid with iodobenzene [73]. 

The fundamental concepts of enantioselective hydrogenation were introduced in Section 2.5.1 of Part A, and examples of reactions of acrylic acids and the important case of a-acetamido acrylate esters were discussed. The chirality of enantioselective hydrogenation catalysts is usually derived from phosphine ligands. A number of chiral phosphines have been explored in the development of enantioselective hydrogenation catalysts,21 and it has been found that some of the most successful catalysts are derived from chiral 1, l -binaphthyldiphosphines, such as BINAP.22... 

Acrylic, methacrylic and but-2-enoic acids react with sulfur tetrafluoride, hydrogen fluoride, and chlorine to afford condensation products, linear chlorofluoro ethers, and chlorofluoroalkanes. For example, the reaction of acrylic acid (15).242... 

The kinetics of the reaction of acrylic acid with aqueous ammonia giving -alanine have been investigated.73... 

The results obtained for reaction of acrylic acid (200 /iM) with tetrasulfide (1.25 mM 5 mM) as well as bisulfide (5 mM) are shown in Figurel. In the reaction with HS, the concentration of 3-MPA did not noticeably increase after treatment with TBP. If polysulfide ion was the actual reactive species in this reaction, then TBP treatment should have caused a significant increase of 3-MPA, in comparison to that without TBP. Therefore, these results indicate that HS was the reactive species in the sulfide medium. However, in the reaction of acrylate with the polysulfide ion, S42, determination of 3-MPA concentration after TBP treatment revealed a large increase, indicating that S42 reacted with acrylate to produce 3-tetrasulfidopropionic acid. The reactivity of tetrasulfide with acrylate was much higher than that of bisulfide. Similar results were also obtained for reaction of acrylonitrile with HS and S42 (Figure 2). The kinetic data are summarized in Table I. In the polysulfide senes low concentrations of 3-MPA were also observed without TBP treatment. It is possible that this 3-MPA was formed from uncatalyzed dissociation of the polysulfide addition product... 

Salts are made by reaction of acrylic acid with an appropriate base in aqueous medium. They can serve as monomers and comonomers in water-soluble or water-dispersible polymers for floor polishes and flocculants. 

Acrylic anhydride is formed by treatment of the acid with acetic anhydride or by reaction of acrylate salts with acryloyl chloride. Acryloyl chloride is made by reaction of acrylic acid with phosphorous oxychloride, or benzoyl or thionyl chloride. Neither the anhydride nor the acid chloride is of commercial interest. 

Amides. Reaction of acrylic acid with ammonia or primary or secondary amines forms amides. However, acrylamide (qv) is better prepared by... 

Table 32 Asymmetric Diels-Alder Reaction of Acrylic Acid and of Conjugated Aldehydes Catalyzed by a...

Conjugate reduction. The reagent generated from PhMejSiH, CuCl has practical application in the reduction of enones and enoic esters. Triphenylphosphine-coordinated CuF and [(PhjPlCuHlg can be used instead of CuCl. A more complex reducing system is made up of PhSiHj, Li, Nilj, and PhjP, and the reduction is assisted by ultrasound. Reductive aldol reaction of acrylic acid derivatives with arylaldehydes occurs when they are treated with (Ph3P) Pd, and HSiClj, and aldehydes. ... 

Derivation Reaction of acrylic acid or methyl acrylate with butanol. 

Figure 5. Upper Abiotic production of 3-mercaptoproplonate (MP) and an unknown thiol ( ) in deaerated seawater from reaction of acrylic acid (0.1 mM) with sodium sulfide (1.0 mM) at 60°C for 2 hours under argon detection by fluorescence derlvatization and HPLC. Middle Control = sodium sulfide (1.0 mM) alone in seawater under identical reaction conditions as above. Lower Control = seawater alone under identical reaction conditions as above.

It has been shown earlier that the kinetics of selective acrolein oxidation can be described by using a simple network of chemical reactions [7]. CO2, CO and acetic acid generated in small amounts can be lumped together into one pseudo-species ( by-products ). The network consists of the main reaction from acrolein to acrylic acid, a parallel reaction of acrolein to byproducts and the consecutive reaction of acrylic acid to by-products. 

Acrylate- and methacrylate guanidines (AG and MAG) were prepared with high yield (to 80%) by reaction of acrylic acids and guanidine according to method elaborated by authors of this article and described in work [1], Kinetics of AG and MAG monomers polymerization was studied by dilatometry method in bidistillated water (pH 6.5, 60°C) on low conversion degrees (< 5%) after preliminary degassing of reaction mixtures on vacuum equipment (103 millimeters of mercury). Ammonium persulfate (APS) was used as initiator. The degree of conversion of monomer into polymer was determined on the base of contraction values determined by densimetry method which for GA polymerization reaction in water was 10.8%, and for MAG - 7.0%. Intrinsic viscosities [r ] of polymers were determined IN solution of NaCl in water at 30°C. Relative viscosities r rei of reaction solutions were determined at 30°C. 

Amide formation. o-Halophenylboronic acids catalyze the Diels-Alder reaction of acrylic acid as well as condensation of carboxylic acids with amines at room temperature (in the presence of 4A-molecular sieves). ... 

Acrylic acid may readily polymerize at ambient temperature. Polymerization may be inhibited with 200 ppm of hydroquinone monomethyl ether (Aldrich 2006). In the presence of a catalyst or at an elevated tem-peratnre, the polymerization rate may accelerate, causing an explosion. The reactions of acrylic acid with amines, imines, and olenm are exothermic bnt not violent. Acrylic acid shonld be stored below its melting point with a trace quantity of polymerization inhibitor. Its reactions with strong oxidizing snbstances can be violent. 

Recently, the present authors have achieved a facile recycling method for both catalyst and reachon medium using F-626 in a Mizoroki-Heck arylation reaction of acrylic acids [11]. The procedure employed a fluorous carbene complex, prepared in situ from a fluorous imidazolium salt, palladium acetate as the catalyst and F-626 as a single reaction medium. When acrylic acid was used as a substrate, separation of the product from the reaction mixture was performed simply by filtration with a small amount of FC-72. The FC-72 solution containing the fluorous Pd-catalyst and F-626 was evaporated and the residue containing the catalyst and F-626 (96% recovery) can be recycled for the next run (Scheme 3.5-6). They tried to reuse the catalyst, and observed no loss of catalytic activity in five re-use cycles. 

Scheme 5.3-20 Pd-catalyzed Heck reaction of acrylic acid butyl ester with bromobenzene carried out in a phosphonium bromide salt.

In the Diels-Alder reaction of acrylic acid and E-pentadienoic acid, the temperature has a noticeable effect on the stereoselectivity (3.69). At low or moderate temperatures the endo adduct is the major product, but the proportion of the exo isomer increases as the temperature of the reaction increases. 

The catalytic activity of macroporous anionite and Amberlite gel in the reaction of acrylic acid esterification by epichlorohydrin was studied at 50- 90 C as a function of the catalyst concentration, molar ratio of reaction mixture components, counterion nature, reaction medium and catalyst particle size [36]. It was found that the reaction proceeds with an appreciable rate even in the presence of a very slight amount of catalyst. Furthermore, the product yield increased with an increment in the catalyst concentration and reaction temperature. The OH-form of ion-exchange resins was most active, and polar solvents promoted the process. 

Esterification. Esterifications with NAFION have been carried out in both the liquid and gas phase. The reaction of acrylic acid and ethanol at 68°C with the catalyst in tubular form (approximately 25 and 35 mils Inside and outside diameter, respectively) has been studied to obtain the forward rate constant in this second order reversible reaction (34). A rate constant of 4.2 x 10 M min was obtained from the analysis. Utilization of sulfuric acid in the same esterification reaction gave a kj = 6.15 X 10 M min at 82°C indicating that the polymeric catalyst was as good as 8280. ... 

An easy recycling method involving both catalyst and reaction medium was achieved in a Mizoroki-Heck arylation reaction of acrylic acid, using a fluorous carbene complex (prepared in situ fl om a fluorous ionic liquid and palladium acetate) as the catalyst and a fluorous ether solvent (F-626) as the reaction medium. Because of the very low solubility of arylated carboxylic acids in F-626, the products precipitated during the course of the reaction. After separation of the products and amine salts by filtration, the filtrate, which contained the fluorous Pd catalyst, could be recycled for several runs (Scheme 13). The Mizoroki-Heck reaction was effectively promoted by a fluorous SCS pincer palladium, which is discussed in Section 3.4.5. 

The Heck reaction is compatible with water, and water-soluble catalysts have successfully been employed (entry 10). Alkali metal salts (NaHCOj, K2CO3, and KOAc) are effective bases in the smooth reactions of acrylic acid with o-, m-, or p-iodobenzoic acid or p-iodophenol in which water-soluble salts are formed and very high yields are encountered (entry 11). Activated heteroaryl chlorides are good arylpalladium precursors (entry 12) while nonactivated aryl chlorides have to date been considered to be less useful in the Heck reaction. In entry 13, the recent protocol devised by Littke and Fu for arylation with nonactivated chlorobenzenes is shown. ... 

Acrylated epoxidised soybean oil (AESO) (Rg. 7.6) is synthesised from the reaction of acrylic acid with epoxidised triglycerides. Similarly malein-ated hydroxylated soybean oil (Rg. 7.6) can be obtained by the reaction of epoxidised oil with maleic anhydride. 

Epoxidised triglycerides can be found in natural oils, such as vernonia plant oil, or they may be synthesised from more common unsaturated oils, such as soybean or hnseed oil, by a standard epoxidation reaction. The reaction of acrylic acid with epoxidised soybean oil (ESO) occurs through a standard substitution reaction. Although the reaction of ESO with acrylic acid is partially acid catalysed by the acrylic acid itself, tertiary amines such as A,A-dimethylanihne, triethylamine and 1, 4-diazobicyclo[2.2.2]-octane are commonly used as the catalysts. 

Further, silica-supported poly-y-aminopropylsilane transition metal complexes derived from Ni(II), Cu(II) and Co(II) salts were probed in arylation reactions of acrylic acid (16), methyl acrylate (1) and styrene (2) using iodobenzene derivatives. The most efficient catalysis was again observed with the nickel-based recyclable catalyst [23,25]. 

Tabtiang and Venables [20] studied the reaction of acrylic acid with the surface of calcium carbonate. The coating was carried out by means of a dry method and their results again demonstrate the complexities that can be encountered. IR spectro-metric analysis of the coated fillers showed that all the acid was converted to the salt form, even when amounts well in excess of that required for a monolayer were used. However, the authors found no evidence of monolayer adsorption, with about half the added material becoming insoluble in xylene, a good solvent for calcium acrylate, at all levels of addition. They concluded that, with the method of coating employed, small droplets react with the filler to produce calcium acrylate, some of which is bound to the filler, or insolubilized in some way, while the rest remains as the free salt. 

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