Synthesis of functionally substituted 2-cyanoacrylates

Russian Chemical Bulletin, Vol. 43, No. 4, April, 1994 595 Organic Chemistry Synthesis of functionally substituted 2-cyanoacrylates T. I. Guseva,* N. G. Senclienya, K. A. Mager, V. A. Ilsyryapkin, and Yu. G. Gololobov A. N. Nesmeyanov Institute of Organoelemeni Compounds, Russian Academy of Sciences, 26’ ul. Vavilova, 117813 Moscow, Russian Federation. Fax: +7(095) 135 5328 The conditions for the Knoevcnagel synthesis of 2-cyanoacrylates containing double and triple bonds in the alkoxycurbonyl group have been studied. it was found that the esters are formed in 10-70 96 yields by the condensation of the respective cyanoacetates with formaldehyde in the l : 1 ratio in the presence of piperidine, followed by the pyrolysis of the oligomers formed in vacuo at 170-200 “C in the presence ofpara—toluenesulfonic acid. The compounds synthcsizccl readily undergo polymerization at room temperature and can be used as the basis for thermostable rapidly polymerizing adhesives. Key words: cyanoacetates, 2-cyanoacrylates, pamform, formaldehyde, 2-cyanoacrylates. 2-Cyanoucrylates (CA) serve as the base for adhe~ sives, quickly polymerizing at room temperature.‘ Of these compounds, the nlltyl esters are used most widely.‘ The use of alkoxyalkyl .7.—cyanoacrylatcs for this purpose has been reported.“ The low thermal stability of cyzmzterylnte adhesives based on esters of this type is their main disadvzmtage. A possible way to increase the thermal stability of cynnacrylate adhesives is the use of CA ccmtainirig multiple bonds in the alkoxycarbonyl group as the hast: for these adhesives. The present work deals with the synthesis of CA (l COOR n N C .4. nCH2=|C—COOR 1-10 n=;cH2cH=ci—g(1); CH2OH2OCH2CH=CH2(2): CH2CH2CH20CH2C'"'=Ctb: 0H20H20CH2CH200H20H=CH2