Manufacture of symmetrical or unsymmetrical monoacetals of aromatic 1,2-diketones

Claim 2

A process for the manufacture of monoacetals of aromatic 1,2-diketones, of the formula (I) ##STR3## where A 1 and A 2 are identical or different aromatic radicals each of which has 6 to 12 carbon atoms and may or may not bear from one to four hydrocarbon readicals of 1 to 10 carbon atoms, alkoxy radicals of 1 to 10 carbon atoms, alkoxyalkyl radicals of 2 to 10 carbon atoms, alkylthio radicals of 1 to 6 carbon atoms and/or halogen as substituents, and R 1 and R 2 are identical or different hydrocarbon radicals 1 to 12 carbon atoms in which the chain may or may not be interrupted by --O-- or --S-- or bear a halogen, which comprises reacting aromatic 1,2-diketones of the formula (II) ##STR4## in an organic solvent with an acid ester of the formula (R.sup.1).sub.n X as alkylating agent and an alcoholate (R.sup.2 O).sub.m Me where A 1 , A 2 , R 1 and R 2 have the above meanings, n and m are integers from 1 to 3, X is a monobasic, dibasic or tribasic acid radical and Me is a metal of main groups 1 to 3 of the periodic table of the elements.

Claim 3

A process as set forth in claim 1, wherein the alcoholate is introduced into a reaction mixture consisting of the aromatic diketone, the alkylating agent and the solvent.

Claim 4

A process as set forth in claim 1, wherein an organic sulfate or a sulfonic acid ester is used as alkylating agent.

Claim 5

A process as set forth in claim 3 wherein the alkylating agent is selected from the group consisting of dimethyl sulfate, diethyl sulfate, dihexyl sulfate, diallyl sulfate, dicrotyl sulfate, di-(β-phenylethyl) sulfate, di-(γ-phenylallyl) sulfate, di-(2-methoxyethyl) sulfate, di-(2-phenoxyethyl) sulfate, di-(methylthioethyl) sulfate and di-(2-phenylthioethyl) sulfate.

Claim 6

A process as set forth in claim 1 wherein the alkylating agent is an ester of a hydrohalic acid.

Claim 7

A process as set forth in claim 5 wherein the alkylating agent is benzyl bromide or allyl bromide.

Claim 8

A process as set forth in claim 1, wherein the alcoholate is a sodium or potassium alcoholate.

Claim 9

A process as set forth in claim 1, wherein the organic solvent is dioxane or dimethylformamide.

Claim 10

A process as set forth in claim 1, wherein from 1/n to 10/n mole of the alkylating agent and from 1/m to 10/m mole of the alcoholate are used per mole of the aromatic 1,2-diketone.

Claim 11

A process as set forth in claim 1, wherein the reaction is carried out at a temperature from about -50° C. to +150° C.

Claim 12

A process for the manufacture of symmetrical monoacetals of aromatic 1,2-diketones, of the formula (I) ##STR5## where A 1 and A 2 are identical or different aromatic radicals each of which has 6 to 12 carbon atoms and may or may not bear from one to four hydrocarbon radicals of 1 to 10 carbon atoms, alkoxy radicals of 1 to 10 carbon atoms, alkoxyalkyl radicals of 2 to 10 carbon atoms and/or halogen as substituents and R 1 and R 2 are identical hydrocarbon radicals of 1 to 12 carbon atoms in which the chain may or may not be interrupted by --O-- or --S-- or bear a halogen, which comprises reacting aromatic 1,2-diketones of the formula (II) ##STR6## in an organic solvent with an acid ester of the formula (R.sup.1).sub.n X as alkylating agent and a corresponding alcoholate (R.sup.2 O).sub.m Me where A 1 , A 2 , R 1 and R 2 have the above meanings, n and m are integers from 1 to 3, X is a monobasic, dibasic or tribasic acid radical and Me is a metal of main groups 1 to 3 of the periodic table of the elements.

Claim 13

A process for the manufacture of symmetrical monoacetals of aromatic 1,2-diketones, of the formula (I) ##STR5## where A 1 and A 2 are identical or different aromatic radicals each of which has 6 to 12 carbon atoms and may or may not bear from one to four hydrocarbon radicals of 1 to 10 carbon atoms, alkoxy radicals of 1 to 10 carbon atoms, alkoxyalkyl radicals of 2 to 10 carbon atoms and/or halogen as substituents and R 1 and R 2 are identical hydrocarbon radicals of 1 to 12 carbon atoms in which the chain may or may not be interrupted by --O-- or --S-- or bear a halogen, which comprises reacting aromatic 1,2-diketones of the formula (II) ##STR6## in an organic solvent with an acid ester of the formula (R.sup.1).sub.n X as alkylating agent and a corresponding alcoholate (R.sup.2 O).sub.m Me where A 1 , A 2 , R 1 and R 2 have the above meanings, n and m are integers from 1 to 3, X is a monobasic, dibasic or tribasic acid radical and Me is a metal of main groups 1 to 3 of the periodic table of the elements.

Claim 14

A process as set forth in claim 11, wherein the alcoholate is introduced into a reaction mixture consisting of the aromatic diketone, the alkylating agent and the solvent.

Claim 15

A process as set forth in claim 11, wherein an organic sulfate or sulfonic acid ester is used as alkylating agent.

Claim 16

A process as set forth in claims 13 wherein the alkylating agent is selected from the group consisting of dimethyl sulfate, diethyl sulfate, dihexyl sulfate, diallyl sulfate, dicrotyl sulfate, di-(β-phenylethyl) sulfate, di-(-phenylallyl) sulfate, di-(2-methoxyethyl) sulfate, di-(2-phenoxyethyl) sulfate, di-(methylthioethyl) sulfate and di-(2-phenylthioethyl) sulfate.

Claim 17

A process as set forth in claim 11, wherein the alcoholate is a sodium or potassium alcoholate.

Claim 18

A process as set forth in claim 11, wherein the organic solvent is dioxane.

Claim 19

A process as set forth in claim 11, wherein the organic solvent is dimethylformamide.

Claim 20

A process as set forth in claim 11, wherein from 1/n to 10/n mole of the alkylating agent and from 1/m to 10/m mole of the alcoholate are used per mole of the aromatic 1,2-diketone.

Claim 21

A process as set forth in claim 11, wherein the reaction is carried out at a temperature from about -50° C. to +150° C.

Claim 22

A process for the manufacture of unsymmetric monoketals of aromatic 1,2-diketones having the formula (I) ##STR7## where A 1 and A 2 are identical or different aromatic radicals each of which having from 6 to 12 carbon atoms which may or may not bear from one to four substituents selected from the group consisting of hydrocarbon radicals having 1 to 10 carbon atoms, alkoxy radicals having 1 to 10 carbon atoms, alkoxyalkyl radicals having 2 to 10 carbon atoms, alkylthio radicals having 1 to 6 carbon atoms and halogen; and R 1 and R 2 are different hydrocarbon radicals 1 to 12 carbon atoms in which the chain may or may not be interrupted by --O-- or --S-- or bear a halogen, which comprises reacting aromatic 1,2-diketones of the formula (II) ##STR8## in an organic solvent with an acid ester (R 1 ) n X as alkylating agent and an alcoholate (R 2 O) m Me, where A 1 , A 2 , R 1 and R 2 have the above meanings, n and m are integers from 1 to 3, X is a monobasic, dibasic or tribasic acid radical and Me is a metal of main groups 1 to 3 of the periodic table of the elements.

Claim 23

A process for the manufacture of unsymmetric monoketals of aromatic 1,2-diketones having the formula (I) ##STR7## where A 1 and A 2 are identical or different aromatic radicals each of which having from 6 to 12 carbon atoms which may or may not bear from one to four substituents selected from the group consisting of hydrocarbon radicals having 1 to 10 carbon atoms, alkoxy radicals having 1 to 10 carbon atoms, alkoxyalkyl radicals having 2 to 10 carbon atoms, alkylthio radicals having 1 to 6 carbon atoms and halogen; and R 1 and R 2 are different hydrocarbon radicals 1 to 12 carbon atoms in which the chain may or may not be interrupted by --O-- or --S-- or bear a halogen, which comprises reacting aromatic 1,2-diketones of the formula (II) ##STR8## in an organic solvent with an acid ester (R 1 ) n X as alkylating agent and an alcoholate (R 2 O) m Me, where A 1 , A 2 , R 1 and R 2 have the above meanings, n and m are integers from 1 to 3, X is a monobasic, dibasic or tribasic acid radical and Me is a metal of main groups 1 to 3 of the periodic table of the elements.

Claim 24

A process as set forth in claim 20, wherein the alcoholate is introduced into a reaction mixture consisting of the aromatic diketone, the alkylating agent and the solvent.

Claim 25

A process as set forth in claim 20, wherein an organic sulfate, or sulfonic acid ester or ester of a hydrohalic acid is used as alkylating agent.

Claim 26

A process as set forth in claim 22, wherein the alkylating agent is selected from the group consisting of dimethyl sulfate, diethyl sulfate, dihexyl sulfate, diallyl sulfate, dicrotyl sulfate, di-(β-phenylethyl) sulfate, di-(-phenylallyl) sulfate, di-(2-methoxyethyl) sulfate, di-(2-phenoxyethyl) sulfate, di-(methylthioethyl) sulfate and di-(2-phenylthioethyl) sulfate.

Claim 27

A process as set forth in claim 22, wherein the alkylating agent is benzyl bromide or allyl bromide.

Claim 28

A process as set forth in claim 20, wherein the alcoholate is a sodium or potassium alcoholate.

Claim 29

A process as set forth in claim 20, wherein the organic solvent is dioxane or dimethylformamide.

Claim 30

A process as set forth in claim 20, wherein from 1/n to 10/n mole of the alkylating agent and from 1/m to 10/m mole of the alcoholate are used per mole of the aromatic 1,2-diketone.

Claim 31

A process as set forth in claim 20, wherein the reaction is carried out at a temperature from about -50° C. to +150° C.