Methylenecyclopentane derivatives

Claim 2

A process for preparing a compound of the formula ##STR45## wherein Q 1 is ##STR46## wherein R 1 is hydrogen or alkyl of one to 4 carbon atoms, inclusive; wherein R 2 is tetrahydropyranyl, tetrahydrofuranyl, or a group of the formula ##STR47## wherein R 4 is alkyl of one to 18 carbon atoms, inclusive, cycloalkyl of 3 to 10 carbon atoms, inclusive, aralkyl of 7 to 12 carbon atoms, inclusive, phenyl, or phenyl substituted with one, 2, or 3 alkyl of one to 4 carbon atoms, inclusive, wherein R 5 and R 6 , taken together, are --(CH 2 ) b --O--(CH 2 ) c --, b is one, 2, or 3, and c is one, 2, or 3 with the proviso that b plus c is 2, 3, or 4, and wherein R 7 is hydrogen or phenyl; and wherein R 13 is ##STR48## wherein C g H 2 .sbsb.g is alkylene of one to 9 carbon atoms, inclusive, with one to 5 carbon atoms, inclusive, in the chain between --CR 14 R 15 -- and terminal methyl, wherein R 14 and R 15 are hydrogen, alkyl of one to 4 carbon atoms, inclusive, or fluoro, being the same or different, with the proviso that one of R 14 and R 15 is fluoro only when the other is hydrogen or fluoro and the further proviso that neither R 14 nor R 15 is fluoro when Z is oxa (--O--); wherein Z represents an oxa atom (--O--) or C j H 2 .sbsb.j wherein C j H 2 .sbsb.j is a valence bond or alkylene of one to 9 carbon atoms, inclusive, with one to 6 carbon atoms, inclusive between CR 14 R 15 -- and the phenyl ring; and wherein L is alkyl of one to 4 carbon atoms, inclusive, fluoro, chloro, trifluoromethyl, or --OR 16 -- wherein R 16 is alkyl of one to 4 carbon atoms, inclusive, and p is zero, one, 2, or 3, with the proviso that not more than two L's are other than alkyl and when p is 2 or 3 the L's are either the same or different; which comprises starting with a compound of the formula ##STR49## wherein Q 1 , R 2 , and R 13 are as defined above, and wherein R 12 is (1) silyl, --Si(A) 3 wherein A is alkyl of one to 4 carbon atoms, inclusive, phenyl, phenyl substituted with one or 2 fluoro, chloro, or alkyl of one to 4 carbon atoms, inclusive, or aralkyl of 7 to 12 carbon atoms, inclusive, the A groups being the same or different; or (2) carboxyacyl, represented by the formula ##STR50## wherein R 9 is hydrogen, alkyl of one to 19 carbon atoms, inclusive, or aralkyl of 7 to 12 carbon atoms, inclusive, wherein alkyl or aralkyl are substituted with zero to 3 halo atoms; and subjecting it to the steps of (a) oxidative decarboxylation by treating in solution with a copper (II) salt and a lead (IV) salt followed by thermal or photochemical decarboxylation to form a compound of the formula ##STR51## wherein Q 1 , R 2 , R 12 , and R 13 are as defined above; and (b) replacing the R 12 groups of the product of step "a" with hydrogen by base hydrolysis.

Claim 3

A process according to claim 1 wherein R 12 is silyl, --Si(A) 3 , as defined in claim 1.

Claim 4

A process according to claim 2 wherein R 12 is t-butyldimethylsilyl.

Claim 5

A process according to claim 1 wherein R 12 is carboxyacyl as defined in claim 1.

Claim 6

A process for preparing a compound of the formula ##STR52## wherein Q 1 is ##STR53## wherein R 1 is hydrogen or alkyl of one to 4 carbon atoms, inclusive; wherein R 2 is 1-ethoxyethyl or a group of the formula ##STR54## wherein R 4 is alkyl of one to 18 carbon atoms, inclusive, cycloalkyl of 3 to 10 carbon atoms, inclusive, aralkyl of 7 to 12 carbon atoms, inclusive, phenyl, or phenyl substituted with one, 2, or 3 alkyl of one to 4 carbon atoms, inclusive, wherein R 5 and R 6 are the same or different, being hydrogen, alkyl of one to 4 carbon atoms, inclusive, phenyl or phenyl substituted with one, 2, or 3 alkyl of one to 4 carbon atoms, inclusive, or, when R 5 and R 6 are taken together, --(CH 2 ) a -- wherein a is 3, 4, or 5, and wherein R 7 is hydrogen or phenyl; and wherein R 13 is ##STR55## wherein C g H 2 .sbsb.g is alkylene of one to 9 carbon atoms, inclusive, with one to 5 carbon atoms, inclusive, in the chain between --CR 14 R 15 -- and terminal methyl, wherein R 14 and R 15 are hydrogen, alkyl of one to 4 carbon atoms, inclusive, or fluoro, being the same or different, with the proviso that one of R 14 and R 15 is fluoro only when the other is hydrogen or fluoro and the further proviso that neither R 14 nor R 15 is fluoro when Z is oxa (--O--); wherein Z represents an oxa atom (--O--) or C j H 2 .sbsb.j wherein C j H 2 .sbsb.j is a valence bond or alkylene of one to 9 carbon atoms, inclusive, with one to 6 carbon atoms, inclusive between CR 14 R 15 -- and the phenyl ring; and wherein L is alkyl of one to 4 carbon atoms, inclusive, fluoro, chloro, trifluoromethyl, or --OR 16 -- wherein R 16 is alkyl of one to 4 carbon atoms, inclusive, and p is zero, one, 2, or 3, with the proviso that not more than two L's are other than alkyl and when p is 2 or 3 the L's are either the same or different; which comprises starting with a compound of the formula ##STR56## wherein Q 1 , R 2 , and R 13 are as defined above, and wherein R 12 is (1) silyl, --Si(A) 3 wherein A is alkyl of one to 4 carbon atoms, inclusive, phenyl, phenyl substituted with one or 2 fluoro, chloro, or alkyl of one to 4 carbon atoms, inclusive, or aralkyl of 7 to 12 carbon atoms, inclusive, the A groups being the same or different; or (2) carboxyacyl, represented by the formula ##STR57## wherein R 9 is hydrogen, alkyl of one to 19 carbon atoms, inclusive, or aralkyl of 7 to 12 carbon atoms, inclusive, wherein alkyl or aralkyl are substituted with zero to 3 halo atoms; and subjecting it to the steps of (a) oxidative decarboxylation by treating in solution with a copper (II) salt and a lead (IV) salt followed by thermal or photochemical decarboxylation to form a compound of the formula ##STR58## wherein Q 1 , R 2 , R 12 , and R 13 are as defined above; and (b) replacing the R 12 groups of the product of step "a" with hydrogen by base hydrolysis.

Claim 7

A process for preparing a compound of the formula ##STR52## wherein Q 1 is ##STR53## wherein R 1 is hydrogen or alkyl of one to 4 carbon atoms, inclusive; wherein R 2 is 1-ethoxyethyl or a group of the formula ##STR54## wherein R 4 is alkyl of one to 18 carbon atoms, inclusive, cycloalkyl of 3 to 10 carbon atoms, inclusive, aralkyl of 7 to 12 carbon atoms, inclusive, phenyl, or phenyl substituted with one, 2, or 3 alkyl of one to 4 carbon atoms, inclusive, wherein R 5 and R 6 are the same or different, being hydrogen, alkyl of one to 4 carbon atoms, inclusive, phenyl or phenyl substituted with one, 2, or 3 alkyl of one to 4 carbon atoms, inclusive, or, when R 5 and R 6 are taken together, --(CH 2 ) a -- wherein a is 3, 4, or 5, and wherein R 7 is hydrogen or phenyl; and wherein R 13 is ##STR55## wherein C g H 2 .sbsb.g is alkylene of one to 9 carbon atoms, inclusive, with one to 5 carbon atoms, inclusive, in the chain between --CR 14 R 15 -- and terminal methyl, wherein R 14 and R 15 are hydrogen, alkyl of one to 4 carbon atoms, inclusive, or fluoro, being the same or different, with the proviso that one of R 14 and R 15 is fluoro only when the other is hydrogen or fluoro and the further proviso that neither R 14 nor R 15 is fluoro when Z is oxa (--O--); wherein Z represents an oxa atom (--O--) or C j H 2 .sbsb.j wherein C j H 2 .sbsb.j is a valence bond or alkylene of one to 9 carbon atoms, inclusive, with one to 6 carbon atoms, inclusive between CR 14 R 15 -- and the phenyl ring; and wherein L is alkyl of one to 4 carbon atoms, inclusive, fluoro, chloro, trifluoromethyl, or --OR 16 -- wherein R 16 is alkyl of one to 4 carbon atoms, inclusive, and p is zero, one, 2, or 3, with the proviso that not more than two L's are other than alkyl and when p is 2 or 3 the L's are either the same or different; which comprises starting with a compound of the formula ##STR56## wherein Q 1 , R 2 , and R 13 are as defined above, and wherein R 12 is (1) silyl, --Si(A) 3 wherein A is alkyl of one to 4 carbon atoms, inclusive, phenyl, phenyl substituted with one or 2 fluoro, chloro, or alkyl of one to 4 carbon atoms, inclusive, or aralkyl of 7 to 12 carbon atoms, inclusive, the A groups being the same or different; or (2) carboxyacyl, represented by the formula ##STR57## wherein R 9 is hydrogen, alkyl of one to 19 carbon atoms, inclusive, or aralkyl of 7 to 12 carbon atoms, inclusive, wherein alkyl or aralkyl are substituted with zero to 3 halo atoms; and subjecting it to the steps of (a) oxidative decarboxylation by treating in solution with a copper (II) salt and a lead (IV) salt followed by thermal or photochemical decarboxylation to form a compound of the formula ##STR58## wherein Q 1 , R 2 , R 12 , and R 13 are as defined above; and (b) replacing the R 12 groups of the product of step "a" with hydrogen by base hydrolysis.

Claim 8

A process according to claim 5 wherein R 12 is silyl, --Si(A) 3 , as defined in claim 5.

Claim 9

A process according to claim 5 wherein R 12 is carboxyacyl, as defined in claim 5.