# US 5,349,071 A · Process for preparing tertiary alkynols > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,349,071 A - Document ID: US5349071A - Status: Granted - Kind: A - Application number: 07/976,219 - Filed: 1992-11-25 - Granted: 1994-09-20 - Earliest claimed: 1992-11-25 - Assignees: Loyola University of Chicago - Inventors: James H. Babler - Web page: https://patentgrep.com/patent/US5349071A ## CPC - C07C 43/1782: {containing six-membered aromatic rings} - C07C 29/42: with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes - C07C 33/044: Alkynediols - C07C 43/315: containing oxygen atoms singly bound to carbon atoms not being acetal carbon atoms - C07C 2601/14: The ring being saturated - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract Processes for synthesizing tertiary alkynols by reacting carbonyl-group-containing compounds with alkynes in the presence of a basic catalyst are disclosed. Preferred products are 6,10,14-trimethyl-4-pentadecyn-6-ol compounds having the structure: ##STR1## A preferred, novel compound, 6,10,14-trimethyl-4-pentadecyne-2,6-diol, can be used in the synthesis of Vitamin E or Vitamin K.sub.1. ## Claims ### Claim 1 A process for synthesizing a tertiary alkynol comprising: a) forming a reaction mixture in a non-hydroxylic organic solvent containing: i) a carbonyl-group-containing compound of the formula RCH.sub.2 COCH.sub.2 R.sup.1 ; ii) an alkyne having the formula R.sup.11 C.dbd.CH; and iii) a catalytic amount of a base stronger than an alkali-metal carbonate; wherein R and R.sup.1 are alkyl or H or form part of an alicyclic ring; and R.sup.11 is an alkyl, alkenyl, alkoxyalkyl, hydroxyalkyl or the alkali-metal salt thereof, aryl or arylalkyl group, provided that when either R or R.sup.1 is H, said carbonyl-group-containing compound is slowly added to said reaction mixture, and when R or R.sup.11 contains a carbon-carbon double bond, the double bond is not conjugated with the carbonyl group of said carbonyl-group containing compound; and b) maintaining said reaction mixture until said tertiary alkynol is formed. ### Claim 2 (depends on 1) The process of claim 1 wherein said alkyne is 4-pentyn-2-ol or a 2-oxy derivative thereof, and wherein said tertiary alkynol is 6,10,14-trimethyl-4-pentadecyne-2,6-diol or a 2-oxy derivative thereof and said base is an alkoxide. ### Claim 3 (depends on 1) The process of claim 1 wherein the carbonyl-group-containing-compound is cyclohexanone. ### Claim 4 (depends on 1) The process of claim 1 wherein the carbonyl-group-containing-compound is 6-methyl-5-hepten-2-one. ### Claim 5 (depends on 1) The process of claim 1 wherein R, R.sup.1 or R.sup.11 is a group having an ether functionality. ### Claim 6 (depends on 1) The process of claim 1 wherein R, R.sup.1 or R.sup.11 is a group having an acetal functionality. ### Claim 7 (depends on 1) The process of claim 1 wherein R.sup.11 is a group having an unblocked 3.degree. alcohol functionality. ### Claim 8 (depends on 1) The process of claim 1 wherein said alkyne comprises 2-methyl-3-butyn-2-ol. ### Claim 9 (depends on 1) The process of claim 1 wherein R.sup.11 is a group having an alkoxide functionality. ### Claim 10 (depends on 1) The process of claim 1 wherein said alkyne comprises ##STR24## ### Claim 11 (depends on 1) The process of claim 1 wherein the alkyne has the structure: ##STR25## ### Claim 12 (depends on 1) The process of claim 1 wherein said carbonyl-group-containing compound is a C-13 ketone and said alkyne is 4-pentyn-2-ol. ### Claim 13 (depends on 1) The process of claim 1 wherein said carbonyl-group-containing compound is a C-13 ketone and said alkyne is the sodium salt of 4-pentyn-2-ol. ### Claim 14 (depends on 1) The process of claim 1 wherein said carbonyl-group-containing compound is cyclohexanone and said alkyne is 1-octyne. ### Claim 15 (depends on 1) The process of claim 1 wherein said carbonyl-group-containing compound is cyclohexanone and said alkyne is 1-hexyne. ### Claim 16 (depends on 1) The process of claim 1 wherein said carbonyl-group-containing compound is 3-pentanone and said alkyne is phenylacetylene. ### Claim 17 (depends on 1) The process of claim 1 wherein said carbonyl-group-containing compound is cyclohexanone and said alkyne is 2-methyl-3-butyn-2-ol. ### Claim 18 (depends on 1) The process of claim 1 wherein said carbonyl-group-containing compound is cyclohexanone and said alkyne is 3-[(tetrahydropyran-2-yl)oxy]propyne. ### Claim 19 (depends on 1) The process of claim 1 wherein said alkyne comprises an ether formed by reacting 4-pentyn-2-ol with a blocking agent. ### Claim 20 (depends on 19) The process of claim 19 wherein said blocking agent is benzyl chloride. ### Claim 21 (depends on 1) The process of claim 1 wherein said base is an alkali-metal alkoxide. ### Claim 22 (depends on 21) The process of claim 21 wherein said base is selected from the group consisting of potassium tertbutoxide, sodium tert-butoxide, potassium methoxide and mixtures thereof. ### Claim 23 (depends on 1) The process of claim 1 wherein said base comprises sodium tert-butoxide and a soluble potassium salt. ### Claim 24 (depends on 23) The process of claim 23 wherein said potassium salt is potassium acetate or potassium chloride. ### Claim 25 (depends on 1) The process of claim 1 wherein said base comprises powdered KOH. ### Claim 26 (depends on 1) The process of claim 1 wherein said base comprises an alkali-metal salt of said alkyne reactant. ### Claim 27 (depends on 1) The process of claim 1 wherein said base comprise an alkoxide of the formula: ##STR26## ### Claim 28 (depends on 1) The process of claim 1 wherein the reactant having the structure RCH.sub.2 COCH.sub.2 R.sup.1 is a C-13 carbonyl-group-containing compound. ### Claim 29 (depends on 1) The process of claim 1 wherein said organic solvent comprises a polar, aprotic liquid. ### Claim 30 (depends on 29) The process of claim 29 wherein the polar, aprotic solvent is selected from the group consisting of dimethyl sulfoxide, 1-methyl-2-pyrrolidinone and acetonitrile. ### Claim 31 (depends on 1) The process of claim 1 wherein said organic solvent comprises a non-polar organic liquid, further including the step: heating said reaction mixture to a temperature of less than 100.degree. C. ### Claim 32 (depends on 31) The process of claim 31 wherein said solvent is selected from the group consisting of tetrahydrofuran and benzene. ### Claim 33 (depends on 1) The process of claim 1, wherein said solvent comprises a polar, aprotic liquid, further including the step: heating said reaction mixture to a temperature from about 50.degree. C. to about 60.degree. C.