METHOD FOR PREPARING TRIOXANE DERIVATIVES

Abstract

Method for preparing trioxane derivatives.

Claims

1. Method comprising the method steps of: a) initially charging an ester of the formula (I): ##STR00010## where m is an integer from 1 to 10 and n is an integer from 0 to 8; b) adding a compound of the formula (II): ##STR00011## where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are selected from: H, -(C.sub.1-C.sub.12)-alkyl, -(C.sub.6-C.sub.20)-aryl; and, when R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are -(C.sub.6-C.sub.20)-aryl, the aryl ring may have substituents selected from: -(C.sub.1-C.sub.12)-alkyl, -O-(C.sub.1-C.sub.12)-alkyl; c) adding PtI.sub.2; d) supplying CO and H.sub.2; e) heating the reaction mixture from a) to d), resulting in conversion of the ester into a compound of the formula (III): ##STR00012##

2. Method according to claim 1, where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are selected from: -(C.sub.1-C.sub.12)-alkyl, -(C.sub.6-C.sub.20)-aryl.

3. Method according to claim 1, where R.sup.5, R.sup.6, R.sup.7, R.sup.8 are -(C.sub.6-C.sub.20)-aryl.

4. Method according to claim 1, where R.sup.2 and R.sup.3 are -(C.sub.1-C.sub.12)-alkyl.

5. Method according to claim 1, where R.sup.1 and R.sup.4 are H.

6. Method according to claim 1, where the compound (II) has the structure (2): ##STR00013##

7. Method according to claim 1, where m is an integer from 5 to 9.

8. Method according to claim 1, where n is an integer from 0 to 4.

9. Method according to claim 1, where the ester has the structure (1): ##STR00014##

10. Method according to claim 1, where CO and H.sub.2 are supplied at a pressure within a range from 1 MPa (10 bar) to 6 MPa (60 bar).

11. Method according to claim 1, where the method includes an additional method step d) of: d) adding a solvent.

12. Compound of the formula (IV): ##STR00015## where x is an integer from 1 to 10 and y is an integer from 0 to 8.

13. Compound according to claim 12, where x is an integer from 5 to 9.

14. Compound according to claim 12, where y is an integer from 0 to 4.

15. Compound according to claim 12, where the compound of the formula (IV) has the structure (4): ##STR00016##

Description

[0046] The invention will be elucidated in more detail hereinbelow with reference to an exemplary embodiment.

Synthesis of trimethyl 10,10, 10-(1,3,5-trioxane-2,4,6-triyl)tris(decanoate) (4)

[0047] 150 ml (132 g) of methyl dec-9-enoate (1), 100 ml of absolute toluene, 320 mg of PtI.sub.2 (0.1 mol % relative to (1)), 620 mg of Xantphos (2) (0.15 mol % relative to (1)) are placed under argon in a 450 ml high-pressure autoclave (Parr Instruments) equipped with stirring and electronic pressure transducer. The autoclave is pressurized to 40 bar with synthesis gas (H.sub.2:CO=1:1) and the reaction is carried out at 60 C. with stirring (>500 min.sup.1). The reaction time is 10 h. The gas consumption is readjusted so that the reaction takes place at approx. 40 bar. After 10 h, the reaction is stopped, the autoclave is cooled down, the gas is vented and the autoclave is flushed 4 times with 30 bar of nitrogen. The reaction solution is transferred to a 500 ml Schlenk vessel.

[0048] A GC is run. The GC yield of methyl 11-oxoundecanoate (3) is: 98%, (n:iso selectivity=98.2:1.8).

##STR00008##

[0049] The mixture is then distilled under fine vacuum at 10.sup.3 torr (K.sub.P=100 C.). A colourless liquid is obtained (146 g =96%).

[0050] This liquid crystallizes completely within 24 h to a solid identified by .sup.1H-NMR, .sup.13C-NMR and MS analysis as trimethyl 10,10,10-(1,3,5-trioxane-2,4,6-triyl)tris(decanoate) (4). The purity is >99%.

[0051] NMR (CDCl.sub.3, 300 MHz):

[0052] .sup.1H: 4.75 t (3H, J.sub.HH=5.3 Hz), 3.59 s (9H), 2.23 (6H, J.sub.HH=7.5 Hz), 1.6-1.5 m (12H) 1.38-1.16 m (36H) .sup.13C: 174.28 s, 101.65 s, 51.40 s, 34.39 s, 34.08 s, 29.38 s, 29.32 s, 29.20 s, 29.11 s, 24.93 s, 23.53 s

[0053] MS (70 ev, MZ (%)): 186(18), 171(44), 143(27), 139(65), 129(9), 121(17), 111(18), 98(36), 97(31), 8(78), 74(100), 69(43), 59(29), 57(17), 55(64).

##STR00009##

Reaction Conditions:

[0054] Ester (1), 0.1 mol % PtI.sub.2, 0.15 mol % Xantphos (2), solvent:toluene, p(CO/H.sub.2): 40 bar, T: 60 C., t: 10 h.

[0055] As shown by the experimental results, the object is achieved by the method according to the invention.