Hydroxyalkyl acrylates

Acrolein, acrylamide, hydroxyalkyl acrylates, and other functional derivatives can be more hazardous from a health standpoint than acryhc acid and its simple alkyl esters. Furthermore, some derivatives, such as the alkyl 2-chloroacrylates, are powerful vesicants and can cause serious eye injuries. Thus, although the hazards of acryhc acid and the normal alkyl acrylates are moderate and they can be handled safely with ordinary care to industrial hygiene, this should not be assumed to be the case for compounds with chemically different functional groups (see Industrial hygiene Plant safety Toxicology). 

Hydroxyalkyl acrylates and polyols are acetoacetylated with diketene to give comonomers used in adhesives, polymers, and coatings, especially the new low solvent coatings, and for emulsion polymeri2ation. The most widely used compound is 2-acetoacetoxyethyl methacrylate (A ARM A) (152). 

Acrylic Esters. A procedure has been described for preparation of higher esters from methyl acrylate that illustrates the use of an acid catalyst together with the removal of one of the products by azeotropic distillation (112). Another procedure for the preparation of butyl acrylate, secondary alkyl acrylates, and hydroxyalkyl acrylates using -toluenesulfonic acid as a catalyst has been described (113). Alurninumisopropoxide catalyzes the reaction of amino alcohols with methyl acrylate and methyl methacrylate. A review of the synthesis of acryhc esters by transesterification is given in Reference 114 (see... 

BAYLIS - HILLMAN Vinyl alkylation Amine catalyzed converelon of acrylates to a-(hydroxyalkyl) acrylates or of vinyl ketones to a-(hydroxyalkyO vinyl ketones. 

Papageorgiou and Benezra204 treated chiral r-butyl (-)-(S)- and ( + )-(R)-2-(p-tolylsulfinyl)propionate with an aldehyde, then pyrolyzed the mixture and obtained chiral a-(hydroxyalkyl)acrylate in 75% e.e. Similarly, condensation of the anion of ( + )-(R)-3-(p-tolylsulfinyl)propionic acid 159 with aldehydes was found to give the diastereomeric [i-sulfinyl-y-lactones, (+)-(Sc4,Rc5,Ps)-160a and ( + )-( c4,Sc5,l s)-160b in an approximate ratio of 60 40205. 

Hydroperoxides, as optically active oxidizing agents 289-291 Hydrosulphonylation 172 /J-Hydroxyacids 619 a-Hydroxyaldehydes, synthesis of 330 a-Hydroxyalkyl acrylates, chiral 329 j -Hydroxycarboxylic esters, chiral 329 3-Hydroxycycloalkenes, synthesis of 313 Hydroxycyclopentenones, synthesis of 310 -Hydroxyesters 619 synthesis of 616 Hydroxyketones 619, 636 Hydroxymethylation 767 a-Hydroxysulphones, synthesis of 176 / -Hydroxysulphones 638, 639 reactions of 637, 944 electrochemical 1036 synthesis of 636 y-Hydroxysulphones 627 synthesis of 783... 

Reaction of optically active a-sulphinyl acetate 298a with prochiral carbonyl compounds proceeds with a high asymmetric induction - , the degree of which depends on the nature of substituents at the carbonyl group (equation 252 Table 22) . The jS-hydroxy sulphoxides 422 formed may be transformed to optically active p-hydroxycarboxylic esters 423 (equation 253) and optically active long-chain lactones 424 99 (equation 254). Corey and coworkers have used this method to introduce a chiral centre at C-3 in their synthesis of maytansin °°, and Papageorgiou and Benezra for the synthesis of chiral a-hydroxyalkyl acrylates 425 ° (equation 255). 

Free-radical multicomponent copolymerization of dialkylstannyl maleates or dialkylstannyl dimethacrylates with methallyl alcohol (or (J-hydroxyalkyl acrylates) and vinyl monomers (sryrene, methacrylic acid or methacrylamide) yields polymeric powders. Due to their storage and thermal stability and impact strength they are used as protective coatings 79). 

The present procedure involving homogeneous catalysis is operationally simple and takes advantage of the easy availability of 2-(l -hydroxyalkyl )-acrylic esters. A two-step procedure Involving kinetic resolution of the racemic starting material with an optically active hydrogenation catalyst, followed by a further reduction with an achiral catalyst, leads to diastereomerically pure products in 4. 97t ee. 

The use of organomagnesium reagents as bases leads to complexation of the nitrile imines (e.g., 141), which has been found to have a strong effect in promoting syn selectivity in reactions with methyl 2-(l-hydroxyalkyl)acrylates via coordination of the metal atom with the alcoholic oxygen (e.g., leading to the formation of 142). Lithium complexation had little effect (78). 

Vinyl ester resins arc manufactured through an addition reaction of an epoxy resin with an acrylic monomer, such as acrylic acid, methaciylic add. or the half-ester product of an hydroxyalkyl acrylate and anhydride. In contrast, the polyester resins are condensation products of dibasic acids and palyhydric alcohols. The relatively low-molecular-weight precise polymer structure of the vinyl ester resins is in contrast to the high-molecular-weight random structure of the polyesters. 

Coupling of aldehydes and acrylates. In the presence of DABCO as catalyst, aldehydes couple with acrylates at the a-position to form 2-(l-hydroxyalkyl)acrylates (equation 1). These products are readily converted into a-methylene-P, y-unsaturated es-... 

Esters. Most acrylic acid is used in the form of its methyl, ethyl, and butyl esters. Specialty monomeric esters with a hydroxyl, amino, or other functional group are used to provide adhesion, latent cross-linking capability, or different solubility characteristics. The principal routes to esters are direct esterification with alcohols in the presence of a strong acid catalyst such as sulfuric acid, a soluble sulfonic acid, or sulfonic acid resins addition to alkylene oxides to give hydroxyalkyl acrylic esters and addition to the double bond of olefins in the presence of strong acid catalyst (19,20) to give ethyl or secondary alkyl acrylates. 

Phenylmenthyl acrylate has been used as a component in an asymmetric Baylis-Hillman reaction. Treatment of the acrylate with 1,4-Diazabicyclo[2.2.2]octane and benzaldehyde at 8 kbar of pressure delivers the a-(hydroxyalkyl)acrylate (eq 8). The product obtained has an 86% de. Menthyl acrylate is superior to the phenylmenthyl acrylate in this particular application. In a radical-mediated addition, phenylmenthyl acrylate gives rise to the a-pyridyl sulfide in 68% yield (eq 9). The final product is isolated with a 56% de. 

The selected monomers are acrylonitrile (ACN), styrene, a-methyl styrene methylmethacrylate, hydroxyalkyl acrylates and methacrylates, vinyl chloride and others [1-10, 13-18]. The most favoured monomers for industrial production of graft polyether polyols are ACN and styrene [1-10, 18-29]. The resulting products from the radical polymerisation of vinylic monomers in polyethers are opaque, generally white dispersions (except those derived from ACN, which are yellow dispersions). A graft polyether polyol has three polymeric components ... 

Acrylic polyols represent a special group of amorphous polyols, of molecular weight (MW) of 8000-13000 daltons, obtained by radical copolymerisation of acrylic monomers (ternary or quaternary copolymers), such as acrylic or methacrylic acids and esters. The source of hydroxyl groups in these acrylic polyols is the utilisation in the radical copolymerisation reaction of hydroxyalkyl acrylates or hydroxyalkyl methacrylates [1,2] as comonomers. The acrylic polyols are used in high performance polyurethane (PU) coatings. 

The general radical copolymerisation reaction for synthesis of acrylic polyols is shown in reaction 10.1. It is obligatory that one of the comonomers is a hydroxyalkyl acrylate or hydroxyalkyl methacrylate (mainly hydroxyethylacrylate and hydroxyethylmethacrylate) in order to introduce hydroxyl groups (as lateral groups, not as terminal groups) available for the reaction with -NCO groups of diisocyanates (reaction 10.1). 

Organocopper reagents prepared from the more readily available organozincs have found much use in the synthesis of highly functionalized molecules. For example, Ni-catalyzed hydrozincation of allylic alcohols initiates the preparation of a-(4-hydroxyalkyl)acrylates when the cuprate intermediates are used in the coupling with the a-bromomethylacrylic esters." ... 

Z)-3-Iodo-2-(hydroxyalkyl)acrylates. propynoate and a carbonyl compound in the pr to the Baylis-Hillman reaction, with the diffen... 

---