Acrylic acid acid chloride synthesis

In 1972 Wright prepared 3-chlorothieno[3,2-6]thiophene-2-carbonyl chloride (94) in 11-13% yield by heating 3-(2-thienyl)acrylic acid, thionyl chloride, and pyridine, a method of synthesis of benzo[6]-thiophene-2-carbonyl chloride derivatives. " Methyl 3,5-dichloro-thieno[3,2-6]thiophene-2-carboxylate (95) and methyl 2-chloro-3-(5-chloro-2-thienyl)acrylate were also isolated. When fte reaction was carried out in refluxing toluene or chlorobenzene, the acid chloride (94)... 

These processes have supplanted the condensation reaction of ethanol, carbon monoxide, and acetylene as the principal method of generating ethyl acrylate [140-88-5] (333). Acidic catalysts, particularly sulfuric acid (334—338), are generally effective in increasing the rates of the esterification reactions. Care is taken to avoid excessive polymerisation losses of both acryflc acid and the esters, which are accentuated by the presence of strong acid catalysts. A synthesis for acryflc esters from vinyl chloride (339) has also been examined. 

Conversion of m-bromobenzonitrile to the tetrazole and addition of the elements of acrylic acid gives 7S, starting material for the patented synthesis of the antiinflammatory agent, bropera-mole (76). The synthesis concludes by activation with thionyl chloride and a Schotten-Baumann condensation with piperidine. 

Synthesis of dithieno[2,3-A2,3-,7]thiophene derivatives 122 has been accomplished through the Heck reaction of 3-(4-bromo-2-thienyl)acrylic acid 302 to afford 3-(2,4-thienylene)diacrylic acid 303 which was cyclized with thionyl chloride and a catalytic amount of pyridine to the dichloride 120 in 75% yield (Scheme 56) <2005MOL279>. 

The preparation of fluorinated alcohols was carried out in multistep routes according to the reported procedures.1012 The synthesis of acrylic and methacrylic esters as shown in Table 11.1 was carried out in a fluorocarbon solvent such as Freon 113 by the reaction of the respective fluorinated alcohol with acryloyl chloride or methacryloyl chloride and an amine acid acceptor such as triethyla-mine with examples shown in Scheme 1. Other attempts to esterify the fluoroalcohols directly with acrylic acid or acrylic anhydride were not successful.11 Product purification by distillation was not feasible because of the temperature required, but purification by percolation of fluorocarbon solutions through neutral alumina resulted in products of good purity identified by TLC, FTIR, and H-, 13C-, and 19F- FTNMRs. 

The synthesis of the moxifloxacin core (de Souza, 2006 Martel et al., 1997 Seidel et al., 2000) proceeds from a Grohe-Heitzer sequence as described earlier in the chapter. Unlike the traditional Grohe-Heitzer sequence, however, the opening step involved the reaction between acid chloride 101 with the mono potassium salt of malonic acid monoethyl ester (102) in the presence of triethylamine to deliver ketoester 103 (Scheme 4.18). Treatment of 103 with ethyl orthoformate furnished acrylate 104, which reacted with cyclopropyl amine to afford 105. Cyclization of 105 in the presence of sodium fluoride in DMF gave the moxifloxicin core 106. 

COPOLYMERIZATION WITH PARTICIPATION OF MULTIMONOMERS Synthesis of various multimonomers and their copolymerization with styrene, acrylonitrile or acrylic acid was described in a set of papers. Most of the early work on the copolymerization of multimonomers with vinyl monomers employed p-cresyl formaldehyde resins, esterified by methacryloyl chloride or acryloyl chloride, as one of the comonomers, and a simple vinyl monomer such as styrene or acrylonitrile as the other monomer. 

The hrst step in the preparation of the antidepressant maprotiline (33-5) takes advantage of the acidity of anthrone protons for incorporation of the side chain. Thus treatment of (30-1) with ethyl acrylate and a relatively mild base leads to the Michael adduct saponihcation of the ester group gives the corresponding acid (33-1). The ketone group is then reduced by means of zinc and ammonium hydroxide. Dehydration of the hrst-formed alcohol under acidic conditions leads to the formation of fully aromatic anthracene (33-2). Diels-Alder addition of ethylene under high pressure leads to the addition across the 9,10 positions and the formation of the central 2,2,2-bicyclooctyl moiety (33-3). The hnal steps involve the construction of the typical antidepressant side chain. The acid in (33-3) is thus converted to an acid chloride and that function reacted with methylamine to form the amide (33-4). Reduction to a secondary amine completes the synthesis of (33-5) [33]. 

Scheme 6 Synthesis of renewable oc,

Complex 3 was found to be inactive in the catalytic asymmetric hydrogenation of 2-(6,-methoxy-2 -naphthyl)acrylic acid. Since 3 accounted for a large portion of the mixed complexes, it was quite clear that the catalytic activity of the mixed species would be substantially increased if the formation of 3 could be avoided. It appeared that preventing the rupture of the phosphorus-naphthyl bond was most critical in an improved synthesis of the mixed Ru-BINAP-chloride catalysts. 

Under some conditions, ethylene and vinyl compounds (vinyl chloride, styrene, acrylic acid, chloroprene, etc.) can be copolymerized with S02 [63-65]. During synthesis of this type of polysulphone, carbon radical centres alternate with... 

Acrylic acid is an important material for the chemical Industry, either as such or in (he form of acrylates and acrylamides. The Union Oil synthesis of acrylic acid from ethylene is performed at 140-150 C, 77 atm, C2 H4/CO 1 (Otalyst 0.1% PdOj. 0.5% CUCI2 in the presence of lithium acetate and chloride). The solvent is a mixture of acetic acid and acetic anhydride (about 20%) 24. The chemical steps of this Wacker-type catalysis are outlined ... 

The synthon of the a-acrylate anion is available from a secondary a-keto carboxamide by the Shapiro reaction. The secondary a-ketoamide trisylhydrazones ate ptepar in a one-pot synthesis by reaction of the isocyanides with acid chloride, water and trisylhydrazine in sequence. In DME solvent, the hydra-zone (103) is smoothly metallated with BuLi to give Ae trianion (KH). Allylation of the trianion (104) gives the hydrazone (105). Alternatively, warming (104) up to room temperature yields the dianion (106) which can be intercepted with several electrophiles (Scheme 23). The adduct (107) is readily transformed into the rran -iodo lactone (108) stereospecifically (equation 56). This chemistry also has been applied to a new synthesis of -lactams (Scheme 24). ... 

The three-component Baylis-Hillman reaction was also performed on 2-chlorotrityl chloride resin by treating polymer-bound acrylic acid with aldehydes and sulfonamides in dioxane at 70 °C for 16 h under DABCO catalysis (Fig. 6.4). Both scaffolds, 3-hydroxy-2-methylidene propionic acids as well as 2-methylidene-3-aminoarylsulfonyl-propionic acids, are precursors for the synthesis of MCSLs. 

The synthesis (Fig. 8-15) of such a complex molecule is surprisingly straightforward. It involves the formation of a diacrylate ester from the corresponding alcohol and the acid chloride of acrylic acid. The acrylate, an a, (3-unsaturated ester, then undergoes the classic Michael addition, which is where a nucleophilic species, in this case the secondary amine of tetrahydropapaverine, attacks the activated P-carbon (Eq. 8.9). The net result is the addition of -N-H across the double bond. 

The synthesis of 2,5-dioxo-l,2-azaphospholanes 126 comprises a reaction of mixed P,C-acid chlorides with primary amines in the presence of a base [168,169] or acrylic and metacrylic acid amides with alkyl- and phenyldichlorophosphines in the presence of acetic acid [170], Both reactions resulted in the same intermediate product that subsequently cyclized to afford 126 (Scheme 75). 

Acrylic acid species 72, without activation, underwent aza-annulation with 71 to generate 73 almost entirely as the a isomer (eq. 18).32 Subsequent modification of 73 led to the total synthesis of ( )-vaIlesamidine 74. Treatment of 71 with cinnamic acid, which lacked the NO2 functionality, gave the corresponding aza-annulation product at higher temperature (145 °C) in 65% yield as a 6 1 ratio of diastereomeric products.32 Alternatively, treatment of 71 with cinnamyl chloride/NEt3,... 

Aza-annulation of 104 with a variety of acrylate reagents has been utilized in the synthesis of indoloquinoiizidine alkaloid skeletons (eq. 25). Aza-annulation of 104 was affected with acrylic acid (91%), acrylic acid/DPPA (95%), acryloyl chloride/DMAP (64, 63%), and methyl acrylate (37, 52%) to generate the pentacyclic eburnane skeleton 105.42 Carbonyl reduction gave Wenkert s enamine (106), which was carried on in the synthesis of ( )-apovincamine (107) and the clinically active synthetic analog ( )-Cavinton (108).42... 

Both enantiomers of lactic acid (2-hydroxypropanoic acid) are natural products and easily obtained by biotechnological methods, so there is no need for their synthesis in the laboratory. Even their esters with alkanols, e.g.. 1, are comparatively inexpensive and, therefore, convenient starting materials for derivatization to chiral reagents and auxiliaries. If necessary, such esters can be obtained by any convenient esterification technique. O-Acylated derivatives of lactic esters have been used very successfully as chiral auxiliaries in diastereoselective Diels-Alder reactions (Section D.1.6.1.1.1.1.2.). The acrylate 2 and methacrylate 31-3 and the fu-marate 43 give very high enantiomeric excesses. These are obtained from the lactic ester by treatment with an acid chloride. 

ORIGIN/INDUSTRY SOURCES/USES pesticides plastics perfumes colloidal forms of metals organic synthesis glycerin acrylic acid esters warning agent in methyl chloride refrigerant military poison mixtures aquatic herbicide liquid fuel algae and aquatic weed control slimicide in paper manufacture... 

The synthesis of manganese acetate tetra-p-aminophenylporphyrinate (MnAc-TAPhP) chemically immobilized on different polymeric supports was carried out, and its catalytic activity during cholesterol oxidation by molecular oxygen was studied [107]. Soluble porphyrin-containing polymers were obtained by copolymerization of methacrylate or 4-vinylpyridine with the product of interaction of acrylic acid chloride with MnAcTAPhP. Cholesterol oxidation was performed in a 1 1 mixture of ethanol and chloroform. The effective rate constants, / eff, were determined from the initial rate of product formation. 

At the beginning of the synthesis, a cis-sUyl-substituted acrylic acid is prepared from the corresponding alkynoic acid by reduction with a Lindlar catalyst, then activated with oxalyl chloride and reacted with Koga s auxiliary. 

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