Method for producing an omega-hydroxycarboxylic acid ester from a trioxane derivative

Abstract

The invention relates to a method for producing an omega-hydroxycarboxylic acid ester proceeding from a trioxane derivative.

Description

[0001] Process for the preparation of an omega-hydroxycarboxylic acid ester from a trioxane derivative

[0002] The present invention relates to a process for preparing an omega-hydroxycarboxylic acid ester starting from a trioxane derivative.

[0003] The object of the present invention was to provide a process for the preparation of omega-hydroxycarboxylic acid esters. This process should achieve a good yield and good selectivity (n:iso).

[0004] This object is achieved by a method according to claim 1.

[0005] Process comprising the process steps: a) introducing a trioxane derivative according to formula (I): where m is an integer from 1 to 10 and n is an integer from 0 to 8; b) adding a phosphine ligand; c) adding a Ru compound; d) adding H2O; e) supplying H2; f) heating the reaction mixture from a) to e), whereby the trioxane derivative is converted into an omega-hydroxycarboxylic acid ester according to formula (II):

[0006] Process steps a) to e) can be performed in any order. However, the addition of H2 usually occurs after the reactants in steps a) to d) have been introduced.

[0007] In a variant of the procedure, m stands for an integer from 5 to 9.

[0008] In a variant of the procedure, m stands for 7.

[0009] In a variant of the procedure, n stands for an integer from 0 to 4.

[0010] In a variant of the procedure, n stands for 0.

[0011] In a variant of the process, the compound according to formula (I) has the structure (1):

[0012] In a variant of the process, the phosphine ligand has the formula (III): and where R 1 , R 2 , R 3 are selected from: -(Ci-Ci2)-alkyl, -(C6-C2o)-aryl, -cyclohexyl.

[0013] The term (Ci-Ci2)-alkyl encompasses straight-chain and branched alkyl groups having 1 to 12 carbon atoms. These are preferably (Ci-Ca)-alkyl groups, particularly preferably (Ci-Ce)-alkyl, and most preferably (Ci-C4)-alkyl.

[0014] The term (Ce-C2o)-aryl encompasses mono- or polycyclic aromatic hydrocarbon radicals having 6 to 20 carbon atoms. These are preferably (Ce-Ci4)-aryl, particularly preferably (Ce-Cio)-aryl.

[0015] In a variant of the procedure, R 1 , R 2 , R 3 for -(Ce-C2o)-aryl.

[0016] In a variant of the process, the phosphine ligand is PPhs.

[0017] In a variant of the process, the Ru compound is selected from: RuCh x 3H2O, Ru3(CO)i2, RU(CI)2(DMSO)4, Ru(acac)3.

[0018] In a variant of the process, the Ru compound is RuCh x 3H2O.

[0019] In a variant of the process, the process comprises an additional process step d'): d') Addition of an organic solvent.

[0020] In one variant of the process, the organic solvent is an alcohol.

[0021] In a variant of the process, H2 is added at a pressure in the range of 1 MPa (10 bar) to 5 MPa (50 bar).

[0022] In a variant of the process, H2 is added at a pressure in the range of 1 MPa (10 bar) to 3 MPa (30 bar).

[0023] In a variant of the process, heating in process step f) takes place to a temperature in the range of 40 °C to 120 °C.

[0024] In a variant of the process, heating in process step f) takes place to a temperature in the range of 60 °C to 120 °C.

[0025] In the following, the invention will be explained in more detail using an exemplary embodiment.

[0026] Synthesis of trimethyl-10, 10', 10"-(1,3,5-trioxane-2,4,6-triyl)tris(decanoate) (1)

[0027] 150 ml (132 g) of methyl dec-9-enoate (2), 100 ml of absolute toluene, 320 mg of Pth (0.1 mol % with respect to (2)), 620 mg of xantphos (3) (0.15 mol % with respect to (2)) are placed in a 450 ml high-pressure autoclave (Parr Instruments) equipped with stirring and electronic pressure transducer under argon.

[0028] 40 bar of synthesis gas (H2:CO = 1 :1) is injected and the reaction is carried out at 60 °C with stirring (>500 min 1). The reaction time is 10 h. The gas consumption is adjusted so that the reaction takes place at approximately 40 bar. After 10 h, the reaction is stopped, the autoclave is cooled, the gas is vented, and the autoclave is purged four times with 30 bar nitrogen. The reaction solution is transferred to a 500 ml Schlenk flask.

[0029] A GC analysis is performed. The GC yield of methyl 1,1-oxoundecanoate (4) is 98% (selectivity: n: iso = 98.2: 1.8).

[0030] Then, in a fine vacuum at 10 -3 Distilled to 100°C (bp = 100°C). A colorless liquid (146 g = 96%) results.

[0031] This liquid crystallizes completely within 24 h to a solid, which is isolated as trimethyl-10,10',10"-(1,3,5-trioxane-2,4,6-triyl)tris(decanoate) (1) by means of 1 H-, 13 Identified by C NMR and MS analysis. The purity is >99%.

[0032] NMR (CDCl, 300 MHz):

[0033] 1 H: 4.75 t(3H, JHH = 5.3 Hz), 3.59 s(9H), 2.23(6H, JHH = 7.5 Hz), 1.6-1.5 m (12H) 1.38-1.16 m (36 H)

[0034] 13 C: 174.28s, 101.65s, 51.40s, 34.39s, 34.08s, 29.38s, 29.32s, 29.20s, 29.11s, 24.93s, 23.53s

[0035] MS (70 ev, MZ (%)): 186(18), 171 (44), 143(27), 139(65), 129(9), 121 (17), 111 (18), 98(36), 97(31), 87(78), 74(100), 69(43), 59(29), 57(17), 55(64).

[0036] Reaction conditions:

[0037] Ester (2), 0.1 mol% Pth, 0.15 mol% Xantphos (3), solvent: toluene, p(CO / H2): 40 bar, T: 60 °C, t: 10 h.

[0038] Synthesis of methyl 11-hydroxyundecanoate (5)

[0039] 53.6 g (250 mmol) of trimethyl 10,10',10"-(1,3,5-trioxane-2,4,6-triyl)tris(decanoate) (1), 250 ml of absolute MeOH, 36 ml of H2O, 260 mg of RuCh x 3H2O (0.4 mol % [Ru]), and 1050 mg of PPhs (1.6 mol %) are placed in a 450 ml high-pressure autoclave (Parr Instruments) equipped with a stirrer and electronic pressure sensor under argon. 20 bar of hydrogen are applied, and the reaction is carried out at 80 °C with stirring (>500 min). -1 ). The reaction time is 24 h. The gas consumption is adjusted so that the reaction takes place between 20 bar and 15 bar. After 24 h, the reaction is stopped, the autoclave is cooled, and the gas is vented. The autoclave is purged four times with 30 bar nitrogen. The reaction solution is transferred to a 500 ml Schlenk flask. A GC is used. The GC yield of methyl 11-oxoundecanoate is > 99% (selectivity = n:iso > 99:1).

[0040] Then, in a fine vacuum at 10 -3Distilled at 120 °C (BP = 120 °C). This yields a colorless liquid (50.2 g = 93%).

[0041] This liquid crystallizes within 24 h to a solid, which is isolated as methyl 11-hydroxyundecanoate (5) by means of 1 H-NMR, 13 Identified by C NMR and MS analysis. Purity is >99%.

[0042] NMR (CDCh, 300 MHz): 1 H: 3.66 s(3H), 3.63 t(2H, JHH = 6.6 Hz), 2.3 t(2H, JHH = 7.5 Hz), 1.7-1.5 m(4H) 1.4-1.2 m(13H).

[0043] NMR (CDCh, 75 MHz): 13 C: 174.38s, 63.02s, 51.46s, 34.1s, 32.77s, 29.49s, 29.37s, 29.33s, 29.21s, 29.11s, 25.91s, 24.93s.

[0044] Mass: 216.17 Reaction conditions:

[0045] Trioxane derivative (1), 0.4 mol% RuCh x 3H2O, 1.6 mol% PPhs, solvent: H2O, MeOH, p(H2): 20 bar, T: 80 °C, t: 24 h.

[0046] As the test results show, the problem is solved by the method according to the invention.

Claims

Patent claims 1 . A process comprising the process steps: a) introducing a trioxane derivative according to formula (I): where m is an integer from 1 to 10 and n is an integer from 0 to 8; b) adding a phosphine ligand; c) adding a Ru compound; d) adding H2O; e) supplying H2; f) heating the reaction mixture from a) to e), whereby the trioxane derivative is converted into an omega-hydroxycarboxylic acid ester according to formula (II):

2. The process according to claim 1, wherein m is an integer from 5 to 9.

3. Method according to one of claims 1 or 2, where n is an integer from 0 to 4.

4. A process according to any one of claims 1 to 3, wherein the compound according to formula (I) has the structure (1):

5. A process according to any one of claims 1 to 4, wherein the phosphine ligand has the formula (III): R1 R 3 P R 2 (Hi) and where R 1 , R 2 , R 3 are selected from: -(Ci-Ci2)-alkyl, -(Ce-C2o)-aryl, -cyclohexyl.

6. The method according to claim 5, wherein R 1 , R 2 , R 3 stand for -(Ce-C2o)-aryl.

7. A process according to any one of claims 1 to 6, wherein the phosphine ligand is PPhs.

8. The process according to any one of claims 1 to 7, wherein the Ru compound is selected from: RuCh x 3H2O, Ru3(CO)i2, Ru(Cl)2(DMSO)4, Ru(acac)3.

9. A process according to any one of claims 1 to 8, wherein the Ru compound is RuCh x 3H2O.

10. The process according to any one of claims 1 to 9, wherein the process comprises an additional process step d'): d') adding an organic solvent.

11. The process according to claim 10, wherein the organic solvent is an alcohol.

12. The method according to any one of claims 1 to 11, wherein the supply of H2 takes place at a pressure in a range of 1 MPa (10 bar) to 5 MPa (50 bar).

13. The method according to any one of claims 1 to 12, wherein the heating in process step f) is carried out to a temperature in the range from 40 °C to 120 °C.

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