Production of 2-substituted 4-methyl-tetrahydropyrans from starting materials containing 2-alkyl-4,4-dimethyl-1,3-dioxanes

Patent metadata

Field	Value
Publication number	US-9994540-B2
Application number	US-201515304283-A
Country	US
Kind code	B2
Filing date	Apr 8, 2015
Priority date	Apr 14, 2014
Publication date	Jun 12, 2018
Grant date	Jun 12, 2018

Abstract

The invention relates to a method for producing 2-substituted 4-methyl-tetrahydropyrans of general formula (I) from starting materials containing at least one 2-substituted 4,4-dimethyl-1,3-dioxane of general formula (II).

First claim

The invention claimed is:

1. A method for preparing 2-substituted 4-methyltetrahydropyrans of the general formula (I)

in which
R 1 is a straight-chain or branched C 1 -C 12 -alkyl, straight-chain or branched C 2 -C 12 -alkenyl, unsubstituted or C 1 -C 12 -alkyl- and/or C 1 -C 12 -alkoxy-substituted cycloalkyl having a total of 3 to 20 carbon atoms or unsubstituted or C 1 -C 12 -alkyl- and/or C 1 -C 12 -alkoxy-substituted aryl having a total of 6 to 20 carbon atoms,
comprising
a) providing a starting material comprising at least one dioxane compound of the general formula (II)

where R 1 is as defined above,
b) subjecting the starting material to a reaction in the presence of a strong acid and/or an acidic ion exchanger, wherein, compared to the starting material, a product mixture depleted in the dioxane compound of the formula (II) and enriched in at least one of the compounds of the formulae (III.1), (III.2) or (III.3)

is obtained where R 1 is as defined above,
c) subjecting the product mixture obtained in step b) to a hydrogenation.

2. The method according to claim 1 , wherein a starting material is provided in step a) which additionally comprises at least one of the compounds of the formulae (III.1), (III.2) or (III.3),

in which
R 1 is a straight-chain or branched C 1 -C 12 -alkyl, straight-chain or branched C 2 -C 12 -alkenyl, unsubstituted or C 1 -C 12 -alkyl- and/or C 1 -C 12 -alkoxy-substituted cycloalkyl having a total of 3 to 20 carbon atoms or unsubstituted or C 1 -C 12 -alkyl- and/or C 1 -C 12 -alkoxy-substituted aryl having a total of 6 to 20 carbon atoms.

3. The method according to claim 1 , wherein, to provide the starting material in step a):
a1) 3-Methylbut-3-en-1-ol of the formula (IV)

is reacted in the presence of an acidic catalyst with an aldehyde of the formula (V)
R 1 —CHO  (V)

in which
R 1 is a straight-chain or branched C 1 -C 12 -alkyl, straight-chain or branched C 2 -C 12 -alkenyl, unsubstituted or C 1 -C 12 -alkyl- and/or C 1 -C 12 -alkoxy-substituted cycloalkyl having a total of 3 to 20 carbon atoms or unsubstituted or C 1 -C 12 -alkyl- and/or C 1 -C 12 -alkoxy-substituted aryl having a total of 6 to 20 carbon atoms,
wherein a reaction mixture is obtained comprising at least one dioxane compound (II), at least one of the compounds (111.1), (III.2) or (III.3) and at least one 2-substituted 4-hydroxy-4-methyltetrahydropyran of the general formula (VI)

wherein R 1 in formula (VI) is as defined above.

4. The method according to claim 3 , which further comprises
a2) subjecting the reaction mixture from step a1) to a separation to obtain at least one fraction enriched in 2-substituted 4-hydroxy-4-methyltetrahydropyrans of the general formula (VI) and a fraction comprising the dioxane compound (II) and at least one of the compounds (III.1), (III.2) or (III.3), and the reaction product obtained in step a1), or the fraction which is obtained in step a2) and which comprises the dioxane compound (II) and at least one of the compounds (III.1), (III.2) or (III.3), is used as starting material for preparing the 2-substituted 4-methyltetrahydropyrans of the formula (I).

5. The method according to claim 4 , wherein the reaction product from step a1) is subjected to a distillative separation in step a2).

6. The method according to claim 5 , wherein in step a2), an arrangement of distillation columns is used for the distillative separation of the reaction product from step a1), which arrangement comprises an upstream conventional distillation column and a downstream dividing wall column or a downstream interconnection of two thermally coupled conventional distillation columns, and
a21) the reaction mixture from step a1) is firstly subjected to a separation in the conventional distillation column, wherein a first top product is obtained, which is enriched in the dioxane compound (II) and in the compounds (III.1), (III.2) and (III.3) and essentially does not comprise any compounds of the general formula (VI), and a first bottom product is obtained, which is depleted in the compounds (III.1), (III.2) and (III.3) and the dioxane compound (II) and which comprises the majority of the compounds of the general formula (VI),
a22) the first bottom product from step a21) is subjected to a separation in the dividing wall column or in the two interconnected thermally coupled conventional distillation columns, wherein a second top product is obtained which comprises the compounds (III.1), (III.2), (III.3) and (II) not present in the first top product and also optionally low amounts of the compounds of the general formula (VI), and a sidestream is obtained essentially containing compound of the general formula (VI), and a second bottom product is obtained comprising the compounds of the general formula (VI) which are not present in the top product and not in the sidestream,
wherein the first top product and/or the second top product are used as starting material in step b).

7. The method according to claim 1 , wherein the residue R 1 is isobutyl or phenyl.

8. The method according to claim 3 , in which the reaction in step a1) and/or in step b) is effected in the presence of an acid, selected from hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid and strongly acidic cation exchangers.

9. The method according to claim 8 , in which the reaction in step a1) and/or in step b) is carried out in the presence of a strongly acidic cation exchanger.

10. The method according to claim 1 , wherein steps b) and c) are carried out at least partly simultaneously.

11. The method according to claim 1 , wherein the hydrogenation in step c) is effected in the presence of a hydrogenation catalyst, selected from homogeneous and heterogeneous catalysts comprising at least one metal component, selected from metals, metal oxides, metal compounds or mixtures thereof.

12. The method according to claim 1 , wherein the hydrogenation in step c) is effected in the presence of a hydrogenation catalyst, selected from palladium on carbon, platinum on carbon, Raney nickel or Raney cobalt.

13. The method according to claim 1 , wherein the hydrogenation product obtained in step c) is subjected to a distillative separation step d).

14. The method according to claim 13 , wherein a fraction enriched in 2-substituted 4-methyltetrahydropyrans (I) is isolated in step d) from the hydrogenation product obtained in step c), said fraction comprising dioxane compounds of the general formula (II) of not more than 2% by weight.

15. The method according to claim 13 , wherein a fraction enriched in 2-substituted 4-methyltetrahydropyrans (I) is isolated in step d) from the hydrogenation product obtained in step c), said fraction comprising dioxane compounds of the general formula (II) of not more than 1% by weight.

16. The method according to claim 13 , wherein a fracti

Assignees

• Basf Se

Inventors

• Rüdenauer Stefan
• Stork Timon

Classifications

• C07D309/04 Primary

  with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms · CPC title