Claims
- 1. In the preparation of bis (2-cyanoacrylate) monomer represented by the General Formula VI ##EQU10## from 2-cyanoacrylic acid ester of the General Formula I ##EQU11## the steps comprising: a. introducing a blocking group by means of a Diels-Alder reaction in which a cyclic 1,3-diene is reacted with said cyanoacrylic ester of Formula I to give a compound of the General Formula II ##EQU12## b. converting said compound of General Formula II by hydrolysis to a compound represented by Formula III ##EQU13## converting the compound of Formula III to an acyl halide represented by the General Formula IV(B): ##EQU14## c. coupling two acyl groups of compounds of Formula IV(B) to each other through an -- O -- R -- O -- linkage by esterification with a difunctional alcohol to form a compound represented by the General Formula V ##EQU15## d. and then heating the compound of Formula V with maleic anhydride to displace said blocking groups and form said bis (2-cyanoacrylate) of Formula VI; wherein said blocking group ##SPC18##
- of Formula II, III, and V is any one of the group consisting of ##SPC19##
- where R.sub.1 and R.sub.2 are the same R.sub.1 and R.sub.2 are selected from the group consisting of H, an alkyl group of 1 to 5 carbons, phenyl, Br or Cl and where R.sub.1 and R.sub.2 are different, R.sub.1 is H and R.sub.2 is a member selected from any of the group consisting of an alkyl group of 1 to 5 carbons, phenyl, Br and Cl; ##SPC20##
- where R.sub.3 is H or CH.sub.3 ; and ##SPC21##
- wherein the organo linking group R of Formulas VI and V is the same and is any one of the group consisting of:
- --(CH.sub.2).sub.m --,
- where m is an integer of from 1 to 20 inclusive; ##EQU16## where n is an integer of from 0 to 18 inclusive, and R.sub.4 and R.sub.5 are independently hydrogen or a C.sub.1 to C.sub.5 alkyl group, R.sub.4 and R.sub.5 not simultaneously being hydrogen;
- --(CH.sub.2).sub.r --Z--(CH.sub.2).sub.s --,
- where Z is --O--, --S--, --CH=CH--; --C.tbd.C--; ##EQU17## and ##SPC22##
- where r and s are independent integers of from 1 to 10 inclusive and r and s total from 2 to 20, R.sub.6 and R.sub.7 are independently hydrogen or a straight or branched chain C.sub.1 and C.sub.5 alkyl group ##SPC23##
- where x and y are integers of from 1 to 6 inclusive; ##SPC24##
- where x and y are as hereinbefore defined;
- --CH.sub.2 --(CF.sub.2).sub.z --CH.sub.2 --,
- where z is an integer of from 1 to 10 inclusive; and ##EQU18## and wherein R' of Formula I and II is an alcohol moiety selected from C.sub.1 to C.sub.16 alkyl, cyclohexyl or phenyl.
- 2. A method according to claim 1 in which the cyclic 1,3 diene is selected from the group consisting of anthracene, 9-methylanthracene, 9-bromoanthracene, 9-phenylanthracene, 9,10-dimethylanthracene, 9,10-dibromoanthracene, 9,10-diphenylanthracene, cyclopentadiene, methylcyclopentadiene, and norbornadiene.
- 3. A method according to claim 2 in which the diene is cyclopentadiene.
- 4. A method according to claim 1 where the difunctional alcohol is of the formula
- Ho[r"].sub. t OH where when t is = to or > 1, R" is propylene, and when t is > 2, R" is propylene, tetramethylene and ethylene, and t is a range average such that the molecular weight is from about 76 to about 2000.
- 5. A method according to claim 1 wherein from 25 to 200 mole percent excess of maleic anhydride is employed.
- 6. A method according to claim 1 where the cyanoacrylic ester is isobutyl 2-cyanoacrylate.
- 7. A method according to claim 1 in which the diene is anthracene.
- 8. A method according to claim 1 wherein the glycol is HO--(CH.sub.2).sub.m --OH, where m is an integer of from 1 to 20 inclusive.
- 9. A method according to claim 1 in which the difunctional alcohol is selected from the group consisting of
- Ho--(ch.sub.2).sub.m --OH where m is an integer of from 1 to 20 inclusive; ##EQU19## where n is an integer of from 0 to 18 and R.sub.4 and R.sub.5 are independently selected from the group consisting of hydrogen and C.sub.1 to C.sub.5 alkyl, but R.sub.4, and R.sub.5 not simultaneously being hydrogen;
- Ho--(ch.sub.2).sub.r --Z--(CH.sub.2).sub.s --OH
- where Z is --O--, --S--, --CH=CH--, --C.tbd.C--, ##EQU20## and ##SPC25##
- where r and s are independent integers of from 1 to 10 inclusive and r and s total from 2 to 20, R.sub.6 and R.sub.7 being as heretofore defined; ##SPC26##
- where x and y are integers of from 1 to 6 inclusive; ##SPC27##
- where x and y are as hereinbefore defined;
- Ho--ch.sub.2 --(cf.sub.2).sub.z --CH.sub.2 --OH where z is an integer of from 1 to 10 inclusive; and
- Ho--ch.sub.2 --si(CH.sub.3).sub.2 --O--Si(CH.sub.3).sub.2 --CH.sub.2 --OH.
- 10. In the preparation of bis (2-cyanoacrylate) monomer represented by the General Formula VI ##EQU21## from 2-cyanoacrylic acid ester of the General Formula I ##EQU22## the steps comprising: a. introducing a blocking group D by means of a Diels-Alder reaction in which a cyclic 1,3-diene is reacted with said cyanoacrylic ester of Formula I to give a compound of the General Formula II ##EQU23## b. converting said compound of General Formula II by hydrolysis to a compound represented by Formula III ##EQU24## neutralizing the compound of Formula III with a metal base of which the designation M is the metal to form a metal salt compound of the General Formula IV(A): ##EQU25## c. coupling two carboxyl groups of compounds of Formula IV(A) to each other through an organo-linking group - R - by ester formation through reaction with a dihalide to form a compound represented by the General Formula V ##EQU26## and then heating the compound of Formula V with maleic anhydride to displace said blocking groups and form said bis (2-cyanoacrylate) of Formula VI; wherein said blocking group ##SPC28##
- of Formula II, III, IV(A) and V is any one of the group consisting of ##SPC29##
- where R.sub.1 and R.sub.2 are the same, R.sub.1 and R.sub.2 are selected from the group consisting of H, an alkyl group of 1 to 5 carbons, phenyl, Br or Cl and where R.sub.1 and R.sub.2 are different, R.sub.1 is H and R.sub.2 is a member selected from any of the group consisting of an alkyl group of 1 to 5 carbons, phenyl, Br and Cl; ##SPC30##
- where R.sub.3 is H or CH.sub. 3 ; and ##SPC31##
- wherein the organo linking group R of Formulas VI and V is the same and is any one of the group consisting of:
- --(CH.sub.2).sub.m --,
- where m is an integer of from 1 to 20 inclusive; ##EQU27## where n is an integer of from 0 to 18 inclusive, and R.sub.4 and R.sub.5 are independently hydrogen or a C.sub.1 to C.sub.5 alkyl group, R.sub.4 and R.sub.5 not simultaneously being hydrogen;
- --(CH.sub.2).sub.r --Z--(CH.sub.2).sub.s --,
- where Z is --O--, --S--, --CH=CH--;--C.tbd.C--; ##EQU28## and ##SPC32##
- where r and s are independent integers of from 1 to 10 inclusive and r and s total from 2 to 20, R.sub.6 and R.sub.7 are independently hydrogen or a straight or branched chain C.sub.1 to C.sub.5 alkyl group ##SPC33##
- where x and y are integers of from 1 to 6 inclusive; ##SPC34##
- where x and y are as hereinbefore defined;
- --CH.sub.2 --(CF.sub.2).sub.z --CH.sub.2 --,
- where z is an integer of from 1 to 10 inclusive; and ##EQU29## and wherein R' of Formula I and II is an alcohol moiety selected from C.sub.1 to C.sub.16 alkyl, cyclohexyl or phenyl.
- 11. A method according to claim 10 in which the dihalide is selected from the group consisting of
- X--(ch.sub.2).sub.m --X, where m is an integer of from 1 to 20 inclusive; ##EQU30## where n is an integer of from 0 to 18 and R.sub.4 and R.sub.5 are independently selected from the group consisting of hydrogen and C.sub.1 to C.sub.5 alkyl, but R.sub.4, and R.sub.5 not simultaneously being hydrogen;
- X--(ch.sub.2).sub.r --Z--(CH.sub.2).sub.s --X, where Z is --O--, --S--, --CH=CH--, --C.tbd.C--, ##EQU31## and ##SPC35##
- where r and s are independent integers of from 1 to 10 inclusive and r and s total from 2 to 20, R.sub.6 and R.sub.7 are independently hydrogen or a straight or branched chain C.sub.1 to C.sub.5 alkyl group ##SPC36##
- where x and y are integers of from 1 to 6 inclusive; ##SPC37##
- where x and y are as hereinbefore defined;
- X--ch.sub.2 --(cf.sub.2).sub.z --CH.sub.2 --X, where z is an integer of from 1 to 10 inclusive; and
- X--ch.sub.2 --si(CH.sub.3).sub.2 --O--Si(CH.sub.3).sub.2 --CH.sub.2 --X; and
- X is either independently selected from the halogens chlorine, bromine, and iodine.
- 12. A method according to claim 11 wherein the dihalide is X--(CH.sub.2).sub.m --X, where m is an integer of from 1 to 20 inclusive.
- 13. A method according to claim 10 in which the cyclic 1,3 diene is selected from the group consisting of anthracene, 9-methylanthracene, 9-bromoanthracene, 9-phenylanthracene, 9,10-dimethylanthracene, 9,10-dibromoanthracene, 9,10-diphenylanthracene, cyclopentadiene, methylcyclopentadiene, and norbornadiene.
- 14. A method according to claim 13 in which the diene is cyclopentadiene.
- 15. A method according to claim 10 wherein from 25 to 200 mole percent excess of maleic anhydride is employed.
- 16. A method according to claim 10 where the cyanoacrylic ester is isobutyl 2-cyanoacrylate.
- 17. A method according to claim 10 in which the diene is anthracene.
Parent Case Info
This application is a continuation-in-part of copending applications Ser. No. 308,375 filed Nov. 21, 1972, and Ser. No. 308,376, filed Nov. 21, 1972, both now abandoned.
US Referenced Citations (5)
Related Publications (1)
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Date |
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308376 |
Nov 1972 |
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Continuation in Parts (1)
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Number |
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308375 |
Nov 1972 |
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