Claims
- 1. A process for preparing a compound of the formula ##STR45## wherein Q.sub.1 is ##STR46## wherein R.sub.1 is hydrogen or alkyl of one to 4 carbon atoms, inclusive; wherein R.sub.2 is tetrahydropyranyl, tetrahydrofuranyl, or a group of the formula ##STR47## wherein R.sub.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.sub.5 and R.sub.6, taken together, are --(CH.sub.2).sub.b --O--(CH.sub.2).sub.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.sub.7 is hydrogen or phenyl; and wherein R.sub.13 is ##STR48## wherein C.sub.g H.sub.2.sbsb.g is alkylene of one to 9 carbon atoms, inclusive, with one to 5 carbon atoms, inclusive, in the chain between --CR.sub.14 R.sub.15 -- and terminal methyl, wherein R.sub.14 and R.sub.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.sub.14 and R.sub.15 is fluoro only when the other is hydrogen or fluoro and the further proviso that neither R.sub.14 nor R.sub.15 is fluoro when Z is oxa (--O--); wherein Z represents an oxa atom (--O--) or C.sub.j H.sub.2.sbsb.j wherein C.sub.j H.sub.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.sub.14 R.sub.15 -- and the phenyl ring; and wherein L is alkyl of one to 4 carbon atoms, inclusive, fluoro, chloro, trifluoromethyl, or --OR.sub.16 -- wherein R.sub.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.sub.1, R.sub.2, and R.sub.13 are as defined above, and wherein R.sub.12 is (1) silyl, --Si(A).sub.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.sub.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.sub.1, R.sub.2, R.sub.12, and R.sub.13 are as defined above; and
- (b) replacing the R.sub.12 groups of the product of step "a" with hydrogen by base hydrolysis.
- 2. A process according to claim 1 wherein R.sub.12 is silyl, --Si(A).sub.3, as defined in claim 1.
- 3. A process according to claim 2 wherein R.sub.12 is t-butyldimethylsilyl.
- 4. A process according to claim 1 wherein R.sub.12 is carboxyacyl as defined in claim 1.
- 5. A process for preparing a compound of the formula ##STR52## wherein Q.sub.1 is ##STR53## wherein R.sub.1 is hydrogen or alkyl of one to 4 carbon atoms, inclusive; wherein R.sub.2 is 1-ethoxyethyl or a group of the formula ##STR54## wherein R.sub.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.sub.5 and R.sub.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.sub.5 and R.sub.6 are taken together, --(CH.sub.2).sub.a -- wherein a is 3, 4, or 5, and wherein R.sub.7 is hydrogen or phenyl; and wherein R.sub.13 is ##STR55## wherein C.sub.g H.sub.2.sbsb.g is alkylene of one to 9 carbon atoms, inclusive, with one to 5 carbon atoms, inclusive, in the chain between --CR.sub.14 R.sub.15 -- and terminal methyl, wherein R.sub.14 and R.sub.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.sub.14 and R.sub.15 is fluoro only when the other is hydrogen or fluoro and the further proviso that neither R.sub.14 nor R.sub.15 is fluoro when Z is oxa (--O--); wherein Z represents an oxa atom (--O--) or C.sub.j H.sub.2.sbsb.j wherein C.sub.j H.sub.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.sub.14 R.sub.15 -- and the phenyl ring; and wherein L is alkyl of one to 4 carbon atoms, inclusive, fluoro, chloro, trifluoromethyl, or --OR.sub.16 -- wherein R.sub.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.sub.1, R.sub.2, and R.sub.13 are as defined above, and wherein R.sub.12 is (1) silyl, --Si(A).sub.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.sub.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.sub.1, R.sub.2, R.sub.12, and R.sub.13 are as defined above; and
- (b) replacing the R.sub.12 groups of the product of step "a" with hydrogen by base hydrolysis.
- 6. A process according to claim 5 wherein R.sub.12 is silyl, --Si(A).sub.3, as defined in claim 5.
- 7. A process according to claim 5 wherein R.sub.12 is carboxyacyl, as defined in claim 5.
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a division of copending application Ser. No. 764,332, filed Jan. 31, 1977 now abandoned, which was a continuation-in-part of then copending application Ser. No. 691,792 filed June 1, 1976 and since abandoned.
US Referenced Citations (3)
Number |
Name |
Date |
Kind |
3867375 |
Alvarez et al. |
Feb 1975 |
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3980642 |
Hess et al. |
Sep 1976 |
|
3987087 |
Bundy |
Oct 1976 |
|
Non-Patent Literature Citations (3)
Entry |
Stork et al., J.A.C.S. 97(1975), pp. 4745-4746. |
Stork et al., J.A.C.S. 98(1976), p. 6747. |
Stork et al., J.A.C.S. 97(1975), pp. 6260-6261. |
Divisions (1)
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Number |
Date |
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Parent |
764332 |
Jan 1977 |
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Continuation in Parts (1)
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691792 |
Jun 1976 |
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