METHOD FOR THE PREPARATION OF 2-ALKOXY CYCLOHEXANOL

Abstract

A method of preparing 2-alkoxycyclohexanol, a mixture comprising 2-alkoxycyclohexanol obtained via said method, and the use of said mixture for preparing 4-hydroxy-3-alkoxy-benzaldehyde.

Claims

1-15. (canceled)

16. A method of preparing a compound of formula (I) ##STR00022## wherein R.sub.1 is alkyl of 1 to 4 carbon atoms, comprising: (i) providing a liquid mixture comprising cyclohexene, an alcohol R.sub.1OH, hydrogen peroxide and optionally a solvent; (ii) reacting the cyclohexene with the hydrogen peroxide and the alcohol R.sub.1OH in the mixture provided as per (i) in the presence of a catalyst comprising a zeolitic material of framework structure MWW to obtain a mixture comprising the compound of formula (I), where the framework of the zeolitic material as per (ii) comprises silicon, titanium, boron, oxygen and hydrogen.

17. The method according to claim 16, wherein R.sub.1 is methyl or ethyl, preferably methyl.

18. The method according to claim 16, wherein the liquid mixture provided as per (i) has a molar ratio prior to the reaction as per (ii) of cyclohexene:R.sub.1OH in the range from 1:1 to 1:50, preferably from 1:3 to 1:30 and more preferably from 1:5 to 1:10, and of cyclohexene:hydrogen peroxide in the range from 1:1 to 5:1, preferably from 1.5:1 to 4.5:1, more preferably from 2:1 to 4:1, and while the mass ratio of hydrogen peroxide:zeolitic material of framework structure MWW at the start of the reaction as per (ii) is preferably in the range from 10:1 to 0.1:1, more preferably from 1:1 to 0.2:1, more preferably from 0.75:1 to 0.25:1.

19. The method according to claim 16, wherein the liquid mixture provided as per (i) comprises a solvent, preferably selected from the group consisting of C1-C6-alkyl nitriles, dialkyl ketones of the formula R.sub.2—CO—R.sub.3, where R.sub.2 and R.sub.3 are each independently selected from the group consisting of C1-C6-alkyl, and a mixture of two or more thereof, more preferably from the group consisting of C1-C3-alkyl nitriles, dialkyl ketones of the formula R.sub.2—CO—R.sub.3, where R.sub.2 and R.sub.3 are each independently selected from the group consisting of C1-C3-alkyl, and a mixture of two or more thereof, more preferably from the group consisting of acetonitrile, acetone and a mixture thereof, wherein the molar ratio of solvent:cyclohexene before the reaction as per (ii) is preferably in the range from 20:1 to 1:1, more preferably in the range from 15:1 to 1:1 and more preferably in the range from 10:1 to 1:1, subject to the proviso that where the solvent in said mixture is a mixture of two or more solvents, the molar ratio of solvent:cyclohexene is based on the mixture of said solvents.

20. The method according to claim 16, wherein the mixture provided as per (i) comprises no solvent.

21. The method according to claim 16, wherein the reaction as per (ii) is carried out at a temperature of the liquid mixture in the range from 40 to 150° C., preferably from 50 to 125° C., more preferably from 55 to 100° C., more preferably at the boiling point of the liquid mixture, preferably under reflux.

22. The method according to claim 16, wherein the duration of the reaction as per (ii) is in the range from 1 to 12 h, preferably from 1.5 to 10 h, more preferably from 2 to 8 h.

23. The method according to claim 16, wherein not less than 99% by weight, preferably not less than 99.5% by weight, more preferably not less than 99.9% by weight of the framework of the zeolitic material as per (ii) consists of silicon, titanium, boron, oxygen and hydrogen, wherein the molar ratio of B:Si is preferably in the range from 0.02:1 to 0.5:1, more preferably 0.05:1 to 0.15:1, and the molar ratio of Ti:Si is in the range from 0.01:1 to 0.05:1, preferably 0.017:1 to 0.025:1, and wherein the zeolitic material of framework structure MWW as per (ii) preferably has a boron content, reckoned as elemental B, in the range from 1.0% to 2.0% by weight, more preferably from 1.1% to 1.8% by weight, more preferably from 1.2% to 1.6% by weight, and preferably has a titanium content in the range from 1.0% to 2.0% by weight, more preferably from 1.1% to 1.8% by weight, more preferably from 1.2% to 1.6% by weight, all based on the overall weight of the zeolitic material.

24. The method according to claim 16, wherein the zeolitic material of framework structure MWW as per (ii) is characterized by an x-ray diffractogram having peaks at 2 theta angles of (7.2±0.1)°, (14.5±0.1)°, (22.1±0.1)°, (22.7±0.1)°, (23.0±0.1)°, (24.0±0.1)°, (25.3±0.1)°, (26.3±0.1)°, (27.3±0.1)°, (28.1±0.1)°, wherein the x-ray diffractogram preferably has additional peaks at 2 theta angles of (7.0±0.1)°, (8.1±0.1)°, (10.1±0.1)°, (14.3±0.1)°, (20.4±0.1)°, (21.9±0.1)°, (28.9±0.1)°, (33.8±0.1)°, (47.0±0.1)°, (65.4±0.1)°, (66.4±0.1)°.

25. The method according to claim 16, wherein the zeolitic material of framework structure MWW as per (ii) is obtained as per a method comprising: (a) providing an aqueous synthesis mixture comprising a silicon source, a boron source, a titanium source and an MWW-templating compound, wherein the temperature of the aqueous synthesis mixture is not more than 50° C.; (b) heating the aqueous synthesis mixture provided as per (a) from the temperature of not more than 50° C. to a temperature in the range from 160 to 190° C. in the course of a period of at most 24 h; (c) subjecting the synthesis mixture as per (b) to hydrothermal synthesis conditions under autogenous pressure in a closed-off system at a temperature in the range from 160 to 190° C. to obtain a precursor to the zeolitic material of framework structure MWW in its mother liquor; (d) separating the precursor to the zeolitic material of framework structure MWW off from its mother liquor; and (e) calcining the MWW framework structure zeolitic material precursor separated off as per (d) to obtain the zeolite of framework structure MWW.

26. The method according to claim 16, wherein the catalyst as per (ii), preferably in the form of a molding, comprises a binder, preferably a silica binder, in addition to the zeolitic material of framework structure MWW.

27. The method according to claim 16, wherein the mole percentage for the compound of formula (I) in the mixture obtained from the reaction as per (ii), based on the sum total of mole percentages for the compounds of formulae (I), (II), (III), (IV) and (V) ##STR00023## in the mixture obtained from the reaction as per (ii) is not less than 85%, preferably not less than 90%.

28. The method according to claim 16, wherein the mixture obtained from the reaction as per (ii) comprises the compounds of formulae (I) and (II) and optionally at least one of the compounds as per formulae (III), (IV) and (V) ##STR00024## and wherein the mole percentage for the compound of formula (II) in the mixture, based on the sum total of mole percentages for the compounds of formulae (II), (III), (IV) and (V) in the mixture is preferably not less than 70%, more preferably not less than 75%, and more preferably not less than 80%, comprising: (iii) separating the compound of formula (II) off from the mixture obtained from the reaction as per (ii) to obtain a mixture depleted with respect to the compound of formula (II); and (iv) optionally separating the compound of formula (I) off from the mixture obtained from the reaction as per (ii) or from the mixture obtained from the separating step as per (iii) as being depleted with respect to the compound of formula (II).

29. A mixture comprising a compound of formula (I) ##STR00025## wherein R.sub.1 is alkyl of 1 to 4 carbon atoms, obtained as per the method according to claim 16, wherein the mole percentage for the compound of formula (I) in the mixture, based on the sum total of mole percentages for the compounds of formulae (I), (II), (III), (IV) and (V) ##STR00026## in the mixture is not less than 85%, preferably not less than 90%.

30. A method of using the mixture according to claim 29 in the manufacture of a compound of formula (VI) ##STR00027##

Description

SHORT DESCRIPTION OF FIGURES

[0313] FIG. 1 shows the .sup.11B solid state NMR spectrum of the zeolite according to Example 1, as measured according to Reference Example 1. The .sup.11B chemical shift (in ppm) is shown on the x-axis, while the intensity (*10.sup.6) is shown on the y-axis. The scale divisions on the x-axis are, from left to right, at 40, 20, 0, −20. The scale divisions on the y-axis are, from bottom to top, at 0, 1, 2, 3, 4.

[0314] FIG. 2 shows the .sup.29Si solid state NMR spectrum of the zeolite according to Example 1, as measured according to Reference Example 2. The .sup.29Si chemical shift (in ppm) is shown on the x-axis, while the intensity (*10.sup.6) is shown on the y-axis. The scale divisions on the x-axis are, from left to right, at −90, −100, −110, −120, −130. The scale divisions on the y-axis are, from bottom to top, at 0, 20, 40, 60, 80, 100.

[0315] FIG. 3 shows the FT-IR spectrum of the zeolite according to Example 1, as measured according to Reference Example 4. The wavelength (in cm.sup.−1) is shown on the x-axis and the extinction is shown on the y-axis. The scale divisions on the x-axis are, from left to right, at 4000, 3500, 3000, 2500, 2000, 1500. The scale divisions on the y-axis are, from bottom to top, at 0.00, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, The wavenumbers indicated on the individual peaks in cm.sup.−1 are, from left to right, 3748, 3719, 3689, 3623, 3601, 3536, 1872.

[0316] FIG. 4 shows the x-ray diffraction pattern (copper K-alpha radiation) of the zeolite according to Example 1, measured according to Reference Example 5. The degree values (2 theta) are shown on the x-axis and the intensity (Lin (counts)) are shown on the y-axis. The scale divisions on the x-axis are, from left to right, at 2, 10, 20, 30, 40, 50, 60, and 70. The scale divisions on the y-axis are, from bottom to top, at 0 and 3557.

LITERATURE CITED

[0317] GB 2 252 556 A [0318] A. Corma et al., “Activity of Ti-Beta Catalyst for the Selective Oxidation of Alkenes and Alkanes”, Journal of Catalyis (1994), vol. 145, pp. 151-158 [0319] Y. Goa et al., “Catalytic Performance of [Ti, Al]-Beta in the Alkene Epoxidation Controlled by the Postsynthetic Ion Exchange”, Journal of Physical Chemistry B 2004, vol. 108, pp. 8401-8411 [0320] E. G. Derouane et al., “Titanium-substituted zeolite beta: an efficient catalyst in the oxy-functionalisation of cyclic alkenes using hydrogen peroxide in organic solvents”, New. J. Chem., 1998, pp. 797-799 [0321] M. A. Uguina et al., J. Chem. Soc., Chem. Commun., 1994, p. 27