# US 5,332,838 A · Cyclization process utilizing copper aluminum borate as a catalyst > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,332,838 A - Document ID: US5332838A - Status: Granted - Kind: A - Application number: 07/174,822 - Filed: 1988-03-29 - Granted: 1994-07-26 - Earliest claimed: 1988-03-29 - Assignees: Amoco Corporation - Inventors: Patrick E. McMahon; Larry C. Satek - Web page: https://patentgrep.com/patent/US5332838A ## CPC - C07D 311/04: Benzo[b]pyrans, not hydrogenated in the carbocyclic ring - C07D 209/04: Indoles; Hydrogenated indoles - C07D 209/86: with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system - C07D 215/02: having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom - C07D 217/02: with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines - C07D 219/02: with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system - C07D 231/56: Benzopyrazoles; Hydrogenated benzopyrazoles - C07D 307/79: with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) ## Abstract The present invention is a cyclization process utilizing the catalyst copper aluminum borate which process comprises the step of contacting (1) a compound having a fragment in which a carbon-containing chain of at least three atoms in sequence is bonded at one end thereof to a nitrogen, oxygen, or sulfur atom, and at the opposite end to a carbon, nitrogen, oxygen, or sulfur atom, where the latter are bonded to at least one hydrogen atom; with (2) a catalyst comprising at least one member selected from the group consisting of copper aluminum borate and zero valent copper on a support comprising aluminum borate, under conditions sufficient to effect ring closure between the ends of the fragment to obtain a compound comprising a heterocyclic ring. ## Claims ### Claim 1 A cyclization process utilizing the catalyst copper aluminum borate which comprises the step of contacting (1) a compound having a fragment in which a carbon-containing chain of at least three atoms in sequence is bonded at one end thereof to a nitrogen, oxygen, or sulfur atoms, and at the opposite end to a carbon, nitrogen, oxygen, of sulfur atom, where the latter are bonded to at least one hydrogen atom; with (2) a catalyst consisting essentially of at least one member selected from the group consisting of (a) crystalline copper aluminum borate having the significant x-ray diffraction lines set forth in Table A and (b) zero valent copper on a support comprising at least one member selected from the group consisting of Al.sub.4 B.sub.2 O.sub.9 and said crystalline copper aluminum borate, the zero valent copper on the support being formed by the reduction of the crystalline copper aluminum borate, said cyclization process being conducted under conditions sufficient to effect ring closure between the ends of the fragment to obtain a compound comprising a heterocyclic ring. ### Claim 2 (depends on 1) The cyclization process of claim 1 wherein said chain of at least three atoms in sequence consists essentially of carbon atoms. ### Claim 3 (depends on 2) The cyclization process of claim 2, said chain having an --NH.sub.2 group bonded at one end thereof. ### Claim 4 (depends on 2) The cyclization process of claim 2, said chain having an --OH group bonded at one end thereof. ### Claim 5 (depends on 2) The cyclization process of claim 2, said chain having an --SH group bonded at one end thereof. ### Claim 6 (depends on 2) The cyclization process of claim 2 wherein said chain includes two contiguous carbon atoms constituting two adjacent carbons of a ring moiety. ### Claim 7 (depends on 6) The cyclization process of claim 6 wherein said ring moiety comprises a benzene ring. ### Claim 8 (depends on 6) The cyclization process of claim 6 wherein said chain of at least three atoms in sequence has bonded at one end thereof an --NH.sub.2 group. ### Claim 9 (depends on 6) The cyclization process of claim 6 wherein said chain of at least three atoms in sequence has bonded at one end thereof an --OH group. ### Claim 10 (depends on 6) The cyclization process of claim 6 wherein said chain of at least three atoms in sequence has bonded at one end thereof an --SH group. ### Claim 11 (depends on 8) The cyclization process of claim 8 wherein the heterocyclic compound formed is indole. ### Claim 12 (depends on 9) The cyclization process of claim 9 wherein the heterocyclic compound formed is benzofuran. ### Claim 13 (depends on 10) The cyclization process of claim 10 wherein the heterocyclic compound formed is benzothiofuran. ### Claim 14 A cyclization process utilizing copper aluminum borate catalyst which process comprises the step of contacting (1) a starting compound comprising at least one five- or six-membered ring having ring substituents comprising (a) a first substituent selected from (i) a methyl group and (ii) a hydrocarbyl-containing group comprising a continuous sequence of two or more atoms, said sequence having a first atom selected from carbon, nitrogen, oxygen and sulfur bonded directly to the ring, and a second atom selected from carbon, nitrogen, oxygen and sulfur, having at least one hydrogen atom bonded thereto and separated by not more than one sequence atom from said first atom; and (b) a second substituent ortho to the first and comprising nitrogen, oxygen, or sulfur bonded directly to the ring or separated therefrom by a continuous sequence of not more than two atoms; with (2) a catalyst consisting essentially of at least one member selected from the group consisting of (a) crystalline copper on a support comprising at least one member selected from the group consisting of Al.sub.2 B.sub.2 O.sub.9 and said crystalline copper aluminum borate, the zero valent copper on the support being formed by the reduction of the crystalline copper aluminum borate, said cyclization process being conducted under conditions sufficient to effect ring closure between said first and second substituents resulting in formation of a heterocyclic ring fused to the ring of the starting compound. ### Claim 15 (depends on 14) The cyclization process of claim 14 wherein the ring of the starting compound is a five-membered ring. ### Claim 16 (depends on 14) The cyclization process of claim 14 wherein the ring of the starting compound is a six-membered ring. ### Claim 17 (depends on 16) The cyclization process of claim 16 wherein the ring is aromatic. ### Claim 18 (depends on 1, 16) The cyclization process of claim 16 wherein said first substituent is selected from category (ii) of claim 1, said substituent being C.sub.2 to C.sub.20 hydrocarbyl. ### Claim 19 (depends on 18) The cyclization process of claim 18 wherein said second substituent comprises --NRR, --OR, or --SR bonded directly to the ring of the starting compound or separated therefrom by a straight chain of carbons no greater than two carbons in length, where R is H or lower alkyl. ### Claim 20 (depends on 19) The cyclization process of claim 19 wherein ring closure results in formation of a five membered heterocyclic ring fused to the ring of the starting compound. ### Claim 21 A cyclization process utilizing the catalyst copper aluminum borate which comprises the step of contacting (1) a starting compound having a fragment characterized by the general formula A or B below: ##STR29## wherein R.sub.1, R.sub.2 and R.sub.3, the same or different, are H or C.sub.1 to C.sub.8 hydrocarbyl and where R.sub.2 and R.sub.3 can be separate substituents or joined such that R.sub.2, R.sub.3, C.sub.1 and C.sub.2 constitute a ring; X is --NRR, --OR or --SR, such that the R groups, the same or different, are H or C.sub.1 to C.sub.8 hydrocarbyl and n=0 to 2; with (2) a catalyst consisting essentially of at least one member selected from the group consisting of (a) crystalline copper aluminum borate having the significant x-ray diffraction lines set forth in Table A and (b) zero valent copper on a support comprising at least one member selected from the group consisting of Al.sub.4 B.sub.2 O.sub.9 and said crystalline copper aluminum borate, the zero valent copper on the support being formed by the reduction of the crystalline copper aluminum borate, said cyclization process being conducted under conditions sufficient to effect ring closure between the substituent ortho to one another of general formula A and B, resulting in formation of a heterocyclic ring fused to the ring of the starting compound. ### Claim 22 (depends on 21) The cyclization process of claim 21 wherein the starting compound has the general formula A, where n=1 or 2. ### Claim 23 (depends on 21) The cyclization process of claim 21 wherein the starting compound has the general formula B, where n=0. ### Claim 24 (depends on 23) The cyclization process of claim 23 wherein X is --NH.sub.2. ### Claim 25 (depends on 23) The cyclization process of claim 23 wherein X is --OH. ### Claim 26 (depends on 23) The cyclization process of claim 23 wherein X is --SH. ### Claim 27 (depends on 24) The cyclization process of claim 24 wherein the heterocyclic compound formed is indole. ### Claim 28 (depends on 25) The cyclization process of claim 25 wherein the heterocyclic compound formed is benzofuran. ### Claim 29 (depends on 26) The cyclization process of claim 26 wherein the heterocyclic compound formed is benzothiofuran. ### Claim 30 A cyclization process utilizing the catalyst copper aluminum borate which comprises the step of contacting (1) a starting compound having the general formula below: ##STR30## wherein X is --NH.sub.2, --OH or SH; wherein the R' groups, being the same or different, are H or C.sub.1 to C.sub.4 hydrocarbyl; and the R groups, being the same or different, are H or substantially hydrocarbyl, and n=1 or 2; with (2) a catalyst consisting essentially of at least one member selected from the group consisting of (a) crystalline copper aluminum borate having the significant x-ray diffraction lines set forth in Table A and (b) zero valent copper on a support comprising at least one member selected from the group consisting of Al.sub.4 B.sub.2 O.sub.9 and said crystalline copper aluminum borate, the zero valent copper on the support being formed by the reduction of the crystalline copper aluminum borate, said cyclization process being conducted under conditions sufficient to effect ring closure resulting in the formation of a heterocyclic fused ring compound. ### Claim 31 (depends on 30) The cyclization process of claim 30 wherein n=2. ### Claim 32 (depends on 30) The cyclization process of claim 30 wherein n=1.