# US 4,394,322 A · Group VA ylides and process for preparing same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,394,322 A - Document ID: US4394322A - Status: Granted - Kind: A - Application number: 06/210,283 - Filed: 1980-11-25 - Granted: 1983-07-19 - Earliest claimed: 1980-08-18 - Assignees: Gulf Research & Development Company - Inventors: David L. Beach; James J. Harrison - Web page: https://patentgrep.com/patent/US4394322A ## CPC - C07F 15/04: Nickel compounds - C07F 9/5352: {Phosphoranes containing the structure P=C-} - C07F 9/72: Aliphatic compounds - C07F 9/74: Aromatic compounds - C07F 9/90: Antimony compounds - C07F 9/92: Aromatic compounds - C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22) ## Abstract There are provided novel Group VA ylides defined by the following Formula I: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are either alike or different members selected from the group consisting of hydrogen, alkyl radicals having from about one to about 24 carbon atoms, preferably from about one to about 10 carbon atoms; aryl radicals having from about six to about 20 carbon atoms, preferably from about six to about 10 carbon atoms; alkenyl radicals having from about two to about 30 carbon atoms, preferably from about two to about 20 carbon atoms; cycloalkyl radicals having from about three to about 40 carbon atoms, preferably from about three to about 30 carbon atoms; aralkyl and alkaryl radicals having from about six to about 40 carbon atoms, preferably from about six to about 30 carbon atoms; a halogen radical selected from the group consisting of fluorine, chlorine, bromine and iodine, preferably chlorine; a hydroxyl group; an alkoxy or aryloxy group; a hydrocarbyl group, such as defined above, carrying halogen, hydroxyl, alkoxy or aryloxy; and a sulfonato group (--SO.sub.3.sup.-) or an alkyl, aryl, alkenyl, cycloalkyl, aralkyl or alkaryl group carrying a sulfonato group; provided that at least one of R.sub.1, R.sub.2 and R.sub.3 is a sulfonato group or an alkyl, aryl, alkenyl, cycloalkyl, aralkyl or alkaryl, as defined above, carrying a sulfonato group; M is sulfur or oxygen, preferably oxygen; and F is phosphorus, arsenic or antimony, preferably phosphorus. The process for preparing these Group VA ylides comprises reacting a ligand defined by the following formula: ##STR2## with an alpha-substituted ketone or aldehyde or an alpha-substituted thioketone or thioaldehyde defined by the following formula: ##STR3## to obtain the salt defined by the following Formula II: ##STR4## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, F and M are as defined above and X is a halogen radical selected from the group consisting of fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, a tosyl group (a toluene sulfonate group), or an acetate group. This salt is reacted with a base to obtain the novel ylide defined by Formula I. ## Claims ### Claim 1 A Group VA ylide defined by the following formula: ##STR31## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are either alike or different members selected from the group consisting of hydrogen, alkyl radicals having from about one to about 24 carbon atoms, aryl radicals having from about six to about 20 carbon atoms, alkenyl radicals having from about two to about 30 carbon atoms, cycloalkyl radicals having from about three to about 40 carbon atoms, aralkyl and alkaryl radicals having from about six to about 40 carbon atoms, hydrocarbyl groups carrying halogen, hydroxyl, alkoxy or aryloxy, or an alkyl, aryl, alkenyl, cycloalkyl, aralkyl or alkaryl group carrying a sulfonato group, provided that at least one of R.sub.1, R.sub.2 and R.sub.3 is an alkyl, aryl, alkenyl, cycloalkyl, alkaryl or aralkyl carrying a sulfonato group; M is sulfur or oxygen; F is phosphorus, arsenic or antimony; and further provided that F is bonded to the groups R.sub.1, R.sub.2 and R.sub.3 through carbon. ### Claim 2 (depends on 1) An ylide as defined in claim 1 wherein F is phosphorus and M is oxygen. ### Claim 3 (depends on 1) An ylide as defined in claim 1 wherein each of R.sub.1, R.sub.2 and R.sub.3 is phenyl, one of which is substituted with a sulfonato group. ### Claim 4 (depends on 2) An ylide as defined in claim 2 wherein each of R.sub.1, R.sub.2 and R.sub.3 is phenyl, one of which is substituted with a sulfonato group. ### Claim 5 (depends on 1) An ylide as defined in claim 1 wherein R.sub.4 is hydrogen and R.sub.5 is phenyl. ### Claim 6 (depends on 2) An ylide as defined in claim 2 wherein R.sub.4 is hydrogen and R.sub.5 is phenyl. ### Claim 7 (depends on 3) An ylide as defined in claim 3 wherein R.sub.4 is hydrogen and R.sub.5 is phenyl. ### Claim 8 (depends on 4) An ylide as defined in claim 4 wherein R.sub.4 is hydrogen and R.sub.5 is phenyl. ### Claim 9 A process for preparing a Group VA ylide defined by the following formula: ##STR32## which comprises reacting a ligand defined by the following formula: ##STR33## with an alpha-substituted ketone or aldehyde or an alpha-substituted thioketone or thioaldehyde defined by the following formula: ##STR34## to obtain the salt defined by the following formula: ##STR35## and thereafter reacting the salt so obtained with a base, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are either alike or different members selected from the group consisting of hydrogen, alkyl radicals having from about one to about 24 carbon atoms, aryl radicals having from abut six to about 20 carbon atoms, alkenyl radicals having from about two to about 30 carbon atoms, cycloalkyl radicals having from about three to about 40 carbon atoms, aralkyl and alkaryl radicals having from about six to about 40 carbon atoms, hydrocarbyl groups carrying halogen, hydroxyl, alkoxy or aryloxy, or an alkyl, aryl, alkenyl, cycloalkyl, aralkyl or alkaryl group carrying a sulfonato group, provided that at least one of R.sub.1, R.sub.2 and R.sub.3 is an alkyl, aryl, alkenyl, cycloalkyl, alkaryl or aralkyl carrying a sulfonato group; M is sulfur or oxygen; F is phosphorus, arsenic or antimony; X is a halogen radical, a tosyl group or an acetate group; and further provided that F is bonded to the groups R.sub.1, R.sub.2 and R.sub.3 through carbon. ### Claim 10 (depends on 9) A process as defined in claim 9 wherein E and F are both phosphorus and M is oxygen. ### Claim 11 (depends on 9) A process as defined in claim 9 wherein each of R.sub.1, R.sub.2 and R.sub.3 is phenyl, one of which is substituted with a sulfonato group. ### Claim 12 (depends on 10) A process as defined in claim 10 wherein each of R.sub.1, R.sub.2 and R.sub.3 is phenyl, one of which is substituted with a sulfonato group. ### Claim 13 (depends on 9) A process as defined in claim 9 wherein R.sub.4 is hydrogen and R.sub.5 is phenyl. ### Claim 14 (depends on 10) A process as defined in claim 10 wherein R.sub.4 is hydrogen and R.sub.5 is phenyl. ### Claim 15 (depends on 11) A process as defined in claim 11 wherein R.sub.4 is hydrogen and R.sub.5 is phenyl. ### Claim 16 (depends on 12) A process as defined in claim 12 wherein R.sub.4 is hydrogen and R.sub.5 is phenyl. ### Claim 17 (depends on 16) A process as defined in claim 16 wherein X is chlorine. ### Claim 18 (depends on 9) A process as defined in claim 9 wherein the reaction between the ligand and the ketone or aldehyde is carried out at a temperature of about 20.degree. to about 200.degree. C. for about one to about 24 hours. ### Claim 19 (depends on 9) A process as defined in claim 9 wherein the reaction between the ligand and the ketone or aldehyde is carried out at a temperature of about 50.degree. to about 150.degree. C. for about two to about eight hours. ### Claim 20 (depends on 17) A process as defined in claim 17 wherein the reaction between the ligand and the ketone or aldehyde is carried out at a temperature of about 20.degree. to about 200.degree. C. for about one to about 24 hours. ### Claim 21 (depends on 17) A process as defined in claim 17 wherein the reaction between the ligand and the ketone or aldehyde is carried out at a temperature of about 50.degree. to about 150.degree. C. for about two to about eight hours. ### Claim 22 (depends on 9) A process as defined in claim 9 wherein said salt is converted to the corresponding ylide by reacting with a base at a temperature of from about room temperature to about 200.degree. C. for about one minute to about four hours. ### Claim 23 (depends on 9) A process as defined in claim 9 wherein said salt is converted to the corresponding ylide by reacting with a base at a temperature of from about room temperature to about 50.degree. C. for about one to about two hours. ### Claim 24 (depends on 17) A process as defined in claim 17 wherein said salt is converted to the corresponding ylide by reacting with a base at a temperature of from about room temperature to about 200.degree. C. for about one minute to about four hours. ### Claim 25 (depends on 17) A process as defined in claim 17 wherein said salt is converted to the corresponding ylide by reacting with a base at a temperature of from about room temperature to about 50.degree. C. for about one to about two hours.