Acrylic acids or esters

Acetylene forms acrylic acid or esters in excellent yield in the presence of [Ni(CO)4].126 The reaction can be catalytic or may require the use of a stoichiometric amount of [Ni(CO)4] under mild reaction conditions. 

Nickel catalysts are utilized for the industrial synthesis of acrylic acid or esters either in a semicatalytic process with Ni(CO>4 or a catalytic process with NiBft (equation 44).73 The reaction is carried out in THF containing water or alcohol (to avoid acetylene detonation at 60 bar). 

In the 1930s, the Reppe group developed commercial processes for the production of carboxylic acids and esters by the carbonylation of alkynes and alkenes using metal carbonyls [4], In particular, an industrial process for producing acrylic acid or ester by the carbonylation of highly explosive acetylene, catalysed by extremely toxic Ni(CO)4, was established (eq. 1.3). 

The carbonylation of acetylene to produce acrylic acid or ester (22) catalysed by Ni(CO)4 was a historical industrial process developed by Reppe. 

Acetylene-Based Routes. Walter Reppe, die father of modem acetylene chemistry, discovered the reaction of nickel carbonyl with acetylene and water or alcohols to give acrylic acid or esters (75,76). This discovery7 led to several processes which have been in commercial use. The original Reppe reaction requires a stoichiometric ratio of nickel carbonyl to acetylene. The Rohm and Haas modified or semicatalytic process provides 60 —80% of the carbon monoxide from a separate carbon monoxide feed and the remainder from nickel carbonyl (77—78). The reactions for the synthesis of ethyl acrylate are... 

Enantioselective hydrogenation of certain a- and 3-(acylamino)acrylic acids or esters in alcohols under 1-4 atm H2 affords the protected a- and 3-amino acids, respectively (eqs eq 3 and eq 4). Reaction of N-acylated 1-alkylidene-1,2,3,4-tetrahydroisoquinolines provides the IR- or 15-alkylated products. This method allows a general asymmetric synthesis of isoquinoline alkaloids (eq 5). ... 

Prochiral a-(acylamino)acrylic acids or esters are hydrogenated under an initial hydrogen pressure of 3-4 atm to give the protected amino acids in up to 100% ee (eq 16). The BINAP-Rh catalyst was used for highly diastereoselective hydrogenation of a chiral homoallylic alcohol to give a fragment of the ionophore... 

Either PA-6 or PA-6,66, was blended with 1-50 wt% of a PA/LDPE laminated film scrap. As a compatibilizer, either an ethylene-acrylic acid-r-alkyl acrylate, ethylene-glycidyl acrylate, allyl glycidyl ether-t-alkyl acrylate, ethylene-acrylic acid (or ester)-MA, or EMA, was used. 

Simplified structure for copolymer of octylacrylamide, t-butylaminoethyl methacrylate, acrylic acid (or ester), and methacrylic acid (or esters)... 

Graft copolymerization Side chains can be grafted on c. in the presence of a peroxide or a redox system. Thus, styrene, acrylic acid or esters can be added. However, industrial applications of these polymers are limited up to now. 

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