M-menthenone and process for its production

Claim 2

A process for the production of a cyclohex-3-en-1-one of the formula ##STR24## comprising contacting at a temperature of from about 0° C to about 130° C an epoxy compound of the formula ##STR25## wherein R 1 , R 2 and R 3 are selected from the group consisting of methyl, ethyl, n-propyl and isopropyl, and where R 5 , R 5 ', R 6 and R 6 ' are selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-butyl, phenyl, cyclohexyl and a 5,6 fused six membered ring, in a dry inert organic solvent with an effective amount of a Lewis acid for a time sufficient to produce said cyclohex-3-en-1-one having R 1 , R 2 , R 3 , R 5 , R 5 ', R 6 and R 6 ' substituents identical to those selected for said epoxy compound.

Claim 3

The process as set forth in claim 1 wherein contacting comprises: (a) dissolving said epoxy compound in a first portion of said solvent to form a first reactant mixture; (b) mixing said Lewis acid in a second portion of said solvent to form a second reactant mixture; and (c) adding said first and said second reactant mixtures together to form a reaction mixture.

Claim 4

The process as set forth in claim 2 additionally comprising purifying said cyclohex-3-en-1-one.

Claim 5

The process as set forth in claim 3 wherein dissolving additionally comprises providing said epoxy compound in an amount sufficient to produce a concentration of from about 1 to about 20 wt.% of said epoxy compound in said first reactant solution and wherein mixing additionally comprises providing said Lewis acid in an amount sufficient to produce from about 100 to about 20 fold mole excess of epoxy compound over Lewis acid in said reaction mixture.

Claim 6

The process as set forth in claim 4 wherein adding comprises admixing said first reactant solution to said second solution.

Claim 7

The process as set forth in claim 5 wherein purifying comprises: (a) washing said reaction mixture with a series of aqueous solutions to remove water soluble components of said reaction mixture; and (b) separating said cyclohex-3-en-1-one from the washed reaction mixture.

Claim 8

The process as set forth in claim 6 wherein separating comprises: (a) drying said washed reaction mixture; (b) thermally removing a portion of said solvent to give a product mixture; and (c) fractionating said product mixture to isolate said cyclohex-3-en-1-one.

Claim 9

The process as set forth in claim 7 wherein fractionating comprises injecting said product mixture into a vapor phase chromatography apparatus and collecting said cyclohex-3-en-1-one as eluted from said apparatus.

Claim 10

The process as set forth in claim 8 wherein washing comprises successively washing said reactant mixture with two volumes of water, one volume of saturated aqueous sodium bicarbonate and one volume of saturated aqueous sodium chloride, and wherein said volumes are calculated to be not greater than that of said reaction mixture.

Claim 11

The process as set forth in claim 9 additionally comprising taking up said reaction mixture in from about a 3-fold to about a 10-fold volume excess of a readily removable, movable, compatible organic solvent prior to said successively washing.

Claim 12

The process as set forth in claim 10 wherein drying comprises exposing said washed reaction mixture to anhydrous sodium sulfate in an amount and for a time, sufficient to dry said washed reaction mixture.

Claim 13

A process for the production of a cyclohex-3-en-1-one of the formula ##STR26## comprising: (a) dissolving a sufficient amount of an epoxy compound of the formula ##STR27## wherein R 1 , R 2 and R 3 are selected from the group consisting of methyl and ethyl and R 5 , R 5' , R 6 and R 6' are selected from the group consisting of hydrogen, methyl and ethyl, in a first dry, inert organic solvent to form a first reactant mixture having a concentration of from 1-20 wt.% in said epoxide compound; (b) mixing a sufficient amount of a Lewis acid in said first, dry, inert organic solvent to form a second reactant mixture having a molar concentration of said Lewis acid of from about 1 to about 20 percent of that for said epoxide compound in said first reactant mixture; (c) adding said first reactant mixture to said second reactant mixture to form a reaction mixture; (d) allowing said epoxide compound and said Lewis acid in said reaction mixture to react to form said cyclohex-3-en-1-one; (e) taking up said reacted reaction mixture in from about a 3-fold to about a 10-fold excess of a readily removable, compatible second organic solvent; (f) washing the diluted reaction mixture with a water solution to remove water soluble components; (g) drying said washed reaction mixture; and (h) separating said cyclohex-3-en-1-one from other components of said reaction mixture.

Claim 14

A process for the production of a cyclohex-3-en-1-one of the formula ##STR26## comprising: (a) dissolving a sufficient amount of an epoxy compound of the formula ##STR27## wherein R 1 , R 2 and R 3 are selected from the group consisting of methyl and ethyl and R 5 , R 5' , R 6 and R 6' are selected from the group consisting of hydrogen, methyl and ethyl, in a first dry, inert organic solvent to form a first reactant mixture having a concentration of from 1-20 wt.% in said epoxide compound; (b) mixing a sufficient amount of a Lewis acid in said first, dry, inert organic solvent to form a second reactant mixture having a molar concentration of said Lewis acid of from about 1 to about 20 percent of that for said epoxide compound in said first reactant mixture; (c) adding said first reactant mixture to said second reactant mixture to form a reaction mixture; (d) allowing said epoxide compound and said Lewis acid in said reaction mixture to react to form said cyclohex-3-en-1-one; (e) taking up said reacted reaction mixture in from about a 3-fold to about a 10-fold excess of a readily removable, compatible second organic solvent; (f) washing the diluted reaction mixture with a water solution to remove water soluble components; (g) drying said washed reaction mixture; and (h) separating said cyclohex-3-en-1-one from other components of said reaction mixture.

Claim 15

The process as set forth in claim 12 wherein washing comprises successively washing said reaction mixture with two volumes of water, one volume of saturated sodium bicarbonate and one volume of saturated sodium chloride, and wherein said volumes are calculated to be not greater than that of said reaction mixture.

Claim 16

The process as set forth in claim 13 wherein separating comprises: (a) distilling a portion of said first and said second solvent from said reaction mixture to give a concentrated product mixture; and (b) fractionating said concentrated product mixture chromatographically to yield purified said cyclohex-3-en-1-one.

Claim 17

The process as set forth in claim 14 additionally comprising selecting said Lewis acid from the group consisting of aluminum trichloride, boron trifluoride, tin (IV) tetrachloride, zinc chloride and, zinc bromide.

Claim 18

The process as set forth in claim 15 additionally comprising restricting said first organic solvent to a dry, inert solvent.

Claim 19

The process as set forth in claim 16 wherein said dry inert solvent is selected from the group consisting of diethyl ether, C 5 to C 8 alkanes, benzene and toluene.

Claim 20

The process as set forth in claim 17 wherein said Lewis acid is zinc bromide and additionally comprising maintaining said reaction mixture at a temperature of from about 80° C to about 110° C immediately after adding said first reactant mixture to said second reactant mixture.

Claim 21

The process as set forth in claim 18, additionally comprising heating said second reactant mixture to a temperature of from about 80° C to about 110° C, vigorously stirring said heated second reactant mixture to disperse said zinc bromide, and wherein said adding is done at a rate sufficiently slow to minimize the temperature change caused by said adding.

Claim 22

The process as set forth in claim 16 wherein said Lewis acid is stannic chloride, said first solvent is benzene and wherein the temperature of said reaction mixture is not greater than about 5° C.

Claim 23

A process for the production of 2-methyl-4-isopropylcyclohex-3-en-1-one comprising: (a) providing 2,3 epoxycarane; (b) dissolving said 2,3 epoxycarane in a sufficient amount of a dry, inert solvent to form a first reactant mixture having a concentration of from about 1 to about 20 wt.% of said 2,3 epoxycarane; (c) mixing a sufficient amount of a Lewis acid in said first, dry, inert hydrocarbon solvent to form a second reactant mixture having a molar concentration of said Lewis acid of from about 1 to about 20% of that for said 2,3 epoxycarane in said first reactant mixture; (d) adding said first reactant mixture and said second reactant mixture together to form a reaction mixture; (e) allowing said 2,3 epoxycarane and said Lewis acid reaction mixture to interact for a time sufficient to form said 2-methyl-4-isopropylcyclohex-3-en-1-one product; (f) taking up said reaction mixture containing said product in a 3 to 10-fold excess of a second inert solvent; (g) extracting water-soluble components from said reaction mixture by washing with an aqueous solution; (h) drying said washed reaction mixture; and (i) separating said 2-methyl-4-isopropylcyclohex-3-en-1-one from other components of said reaction mixture.

Claim 24

A process for the production of 2-methyl-4-isopropylcyclohex-3-en-1-one comprising: (a) providing 2,3 epoxycarane; (b) dissolving said 2,3 epoxycarane in a sufficient amount of a dry, inert solvent to form a first reactant mixture having a concentration of from about 1 to about 20 wt.% of said 2,3 epoxycarane; (c) mixing a sufficient amount of a Lewis acid in said first, dry, inert hydrocarbon solvent to form a second reactant mixture having a molar concentration of said Lewis acid of from about 1 to about 20% of that for said 2,3 epoxycarane in said first reactant mixture; (d) adding said first reactant mixture and said second reactant mixture together to form a reaction mixture; (e) allowing said 2,3 epoxycarane and said Lewis acid reaction mixture to interact for a time sufficient to form said 2-methyl-4-isopropylcyclohex-3-en-1-one product; (f) taking up said reaction mixture containing said product in a 3 to 10-fold excess of a second inert solvent; (g) extracting water-soluble components from said reaction mixture by washing with an aqueous solution; (h) drying said washed reaction mixture; and (i) separating said 2-methyl-4-isopropylcyclohex-3-en-1-one from other components of said reaction mixture.

Claim 25

The process as set forth in claim 21 wherein said Lewis acid is selected from the group consisting of aluminum trichloride, boron trifluoride, tin tetrachloride and zinc bromide.

Claim 26

The process as set forth in claim 22 wherein said first and said second inert solvents are selected from the group consisting of toluene, benzene, diethyl ether, and C 5 -C 8 alkanes.

Claim 27

The process as set forth in claim 23 wherein said first solvent is toluene and said Lewis acid is zinc bromide.

Claim 28

The process as set forth in claim 23 wherein said first solvent is benzene and said Lewis acid is zinc bromide.

Claim 29

The process as set forth in claim 23 wherein said first solvent is benzene and said Lewis acid is tin tetrachloride.

Claim 30

The process as set forth in claim 24 additionally comprising heating said second reactant mixture to reflux prior to said adding.

Claim 31

The process as set forth in claim 27 wherein adding comprises admixing said first reactant mixture to said second reactant mixture such that said temperature of said second solution is maintained proximate to the reflux temperature.

Claim 32

The process as set forth in claim 25 additionally comprising heating said second reactant mixture to reflux prior to said adding and wherein adding comprises admixing said first reactant mixture to said second reactant mixture at a rate such that the temperature of said reaction mixture is maintained proximate to reflux.

Claim 33

The process as set forth in claim 25 additionally comprising cooling one of said reactant mixtures to a temperature not greater than about 10° C and wherein adding comprises admixing the other said reactant mixture with said cooled reactant mixture at a rate such that the temperature of said reaction mixture is maintained at not greater than about 10° C.

Claim 34

The process as set forth in claim 21 wherein providing comprises epoxidizing 2,3 carene.

Claim 35

The process as set forth in claim 31 wherein epoxidizing comprises: (a) treating 2,3 carene with an excess of m-chloroperbenzoic acid at a temperature not greater than 10° C for about 1-2 hours to form an epoxidation solution; (b) raising the temperature of said epoxidation solution to ambient for about 1-2 hours; (c) removing water soluble components from said epoxidation solution; and (d) concentrating said dried epoxidation solution to yield 2,3 epoxycarane.

Claim 36

A process for the production of 2-methyl-4-isopropylcyclohex-3-en-1-one from 2,3 epoxycarane comprising contacting said 2,3 epoxycarane with a Lewis acid selected from the group consisting of aluminum chloride, boron trifluoride, tin tetrachloride and zinc bromide in a dry, inert solvent for a time sufficient to produce said 2-methyl-4-isopropylcyclohex-3-en-1-one.

Claim 37

A process for the production of 2-methyl-4-isopropylcyclohex-3-en-1-one from 2,3 epoxycarane comprising contacting said 2,3 epoxycarane with a Lewis acid selected from the group consisting of aluminum chloride, boron trifluoride, tin tetrachloride and zinc bromide in a dry, inert solvent for a time sufficient to produce said 2-methyl-4-isopropylcyclohex-3-en-1-one.

Claim 38

The process as set forth in claim 33 wherein said Lewis acid is zinc bromide or tin tetrachloride.

Claim 39

The process as set forth in claim 34 wherein said solvent is benzene or toluene.