Process for preparation of trioxane derivatives

Abstract

The present invention relates to a process for the preparation of trioxane derivatives.

Description

Technical Field

[0001] The present invention relates to a process for preparing trioxane derivatives.

[0002] The object of the present invention is to provide a process for preparing trioxane derivatives, wherein good yields should be achieved. Background Art

[0003] US 2017 / 0233366 A1 describes a method for preparing trioxane. Here, aqueous formaldehyde solution is converted into trioxane in the presence of methanesulfonic acid at 105° C. According to Table 1, a formaldehyde conversion of 40% is achieved. Summary of the Invention

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

[0005] The method comprises the following steps:

[0006] a) Pre-loading of an ester according to formula (I):

[0007]

[0008] wherein m is an integer from 1 to 10, and

[0009] n is an integer from 0 to 8;

[0010] b) adding a compound according to formula (II):

[0011]

[0012] where R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Selected from: -H, -(C1-C 12 )-alkyl, -(C6-C 20 )-aryl;

[0013] And when R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 -(C6-C 20 )-aryl, the aromatic ring may have a member selected from -(C1-C 12 )-alkyl, -O-(C1-C 12)-alkyl substituents;

[0014] c) adding PtI2;

[0015] d) supplying CO and H2;

[0016] e) heating the reaction mixture from a) to d), thereby converting the ester into a compound according to formula (III):

[0017]

[0018] In this process, process steps a) to e) can be carried out in any order. However, the addition of CO and H2 is usually carried out after the pre-charging of the co-reactants in steps a) to c).

[0019] Expression (C1-C 12 )-Alkyl includes straight-chain and branched alkyl groups having 1 to 12 carbon atoms. These are preferably (C1-C8)-alkyl, more preferably (C1-C6)-alkyl, most preferably (C1-C4)-alkyl.

[0020] Expression (C6-C 20 )-Aryl includes monocyclic or polycyclic aromatic hydrocarbon groups having 6 to 20 carbon atoms. These are preferably (C6-C 14 )-aryl, more preferably (C6-C 10 )-aryl.

[0021] In one variation of this approach, R 2 、R 3 、R 5 、R 6 、R 7 、R 8 Selected from: -(C1-C 12 )-alkyl, -(C6-C 20 )-aryl.

[0022] In one variation of this approach, R 5 、R 6 、R 7 、R 8 Yes-(C6-C 20 )-aryl.

[0023] In one variation of this approach, R 5 、R 6 、R 7 、R 8 Yes - Ph.

[0024] In one variation of this approach, R 2 and R 3 Yes-(C1-C 12)-alkyl.

[0025] In one variation of this approach, R 2 and R 3 It is -CH3.

[0026] In one variation of this approach, R 1 and R 4 Yes -H.

[0027] In one variation of this method, compound (II) has structure (2):

[0028]

[0029] In one variation of the method, m is an integer from 5 to 9.

[0030] In one variation of this method, m is 7.

[0031] In one variation of the method, n is an integer from 0 to 4.

[0032] In one variation of this method, n is zero.

[0033] In one variation of this method, the ester has the structure (1):

[0034]

[0035] In one variant of the process, the supply of CO and H 2 is carried out at a pressure of 1 MPa (10 bar) to 6 MPa (60 bar).

[0036] In one variant of the process, the supply of CO and H 2 is carried out at a pressure of 3 MPa (30 bar) to 5 MPa (50 bar).

[0037] In one variant of the process, heating is to a temperature of 40°C to 100°C.

[0038] In one variant of the process, heating is to a temperature of 50°C to 80°C.

[0039] In one variant of the method, the method comprises the additional method step d'):

[0040] d') Adding solvent.

[0041] In one variant of the process, the solvent is selected from the group consisting of: THF, MTBE, DCM, ACN, heptane, DMF, toluene, xylene, mesitylene, dibenzyltoluene.

[0042] In one variation of the process, the solvent is toluene.

[0043] In addition to the process, compounds are also claimed.

[0044] Compounds according to formula (IV):

[0045]

[0046] where x is an integer from 1 to 10, and

[0047] y is an integer from 0 to 8.

[0048] In one embodiment, x is an integer from 5 to 9.

[0049] In one embodiment, x is 7.

[0050] In one embodiment, y is an integer from 0 to 4.

[0051] In one embodiment, y is 0.

[0052] In one embodiment, the compound according to formula (IV) has structure (4):

[0053] DETAILED DESCRIPTION

[0054] The present invention will be described in more detail below with reference to examples.

[0055] Synthesis of 10,10',10"-(1,3,5-trioxane-2,4,6-triyl)tri(decanoic acid)trimethyl ester (4)

[0056] 150 ml (132 g) of dec-9-enoic acid methyl ester (1), 100 ml of anhydrous toluene, 320 mg of PtI2 (0.1 mol % based on (1)), and 620 mg of Xantphos (2) (0.15 mol % based on (1)) were placed in a 450 ml autoclave (Parr Instruments) equipped with a stirrer and an electronic pressure sensor under argon. Synthesis gas (H2:CO=1:1) at 40 bar was introduced and the mixture was stirred for >500 min. -1 The reaction was carried out at 60°C under a pressure of 10 bar. The reaction time was 10 hours. The gas consumption was readjusted so that the reaction proceeded at approximately 40 bar. After 10 hours, the reaction was stopped, the autoclave was cooled, the gas was vented, and the autoclave was flushed four times with 30 bar nitrogen. The reaction solution was transferred to a 500 ml Schlenk flask.

[0057] The GC was run. The GC yield of methyl 11-oxoundecanoate (3) was 98% (normal:isoselectivity = 98.2:1.8).

[0058]

[0059] Then at 10 -3 Distillation under high vacuum conditions (K P =100°C). A colorless liquid (146 g = 96%) was obtained.

[0060] The liquid completely crystallized into a solid within 24 hours. 1 H-NMR, 13 C-NMR and MS analysis identified it as trimethyl 10,10',10"-(1,3,5-trioxane-2,4,6-triyl)tris(decanoate) (4). The purity was >99%.

[0061] NMR (CDCl3, 300MHz):

[0062] 1 H:4.75t(3H,J HH =5.3Hz),3.59s(9H),2.23(6H,J HH =7.5Hz),1.6-1.5m(12H)1.38-1.16m(36H)

[0063] 13 C:174.28s,101.65s,51.40s,34.39s,34.08s,29.38s,29.32s,29.20s,29.11s,24.93s,23.53s

[0064] MS(70ev,MZ(%)):186(18),171(44),143(27),139(65),129(9),121(17),1 11(18),98(36),97(31),87(78),74(100),69(43),59(29),57(17),55(64).

[0065]

[0066] Reaction conditions:

[0067] Ester (1), 0.1 mol% PtI2, 0.15 mol% Xantphos (2), solvent: toluene, p(CO / H2): 40 bar, T: 60°C, t: 10 h.

[0068] Experimental results show that the method of the present invention achieves the above-mentioned purpose.

Claims

1. A method comprising the following steps: a) Pre-loading of an ester according to formula (I): wherein m is an integer from 1 to 10, and n is an integer from 0 to 8; b) adding a compound according to formula (II): where R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Selected from: -H, -(C1-C 12 )-alkyl, -(C6-C 20 )-aryl; And when R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 -(C6-C 20 )-aryl, the aromatic ring may have a member selected from -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl substituents; c) adding PtI2; d) supplying CO and H2; e) heating the reaction mixture from a) to d), thereby converting the ester into a compound according to formula (III):

2. The method according to claim 1, where R 2 、R 3 、R 5 、R 6 、R 7 、R 8 Selected from: -(C1-C 12 )-alkyl, -(C6-C 20 )-aryl.

3. The method according to any one of claims 1 or 2, where R 5 、R 6 、R 7 、R 8 Yes-(C6-C 20 )-aryl.

4. The method according to any one of claims 1 to 3, where R 2 and R 3 Yes-(C1-C 12 )-alkyl.

5. The method according to any one of claims 1 to 4, where R 1 and R 4 Yes -H.

6. The method according to any one of claims 1 to 5, Wherein compound (II) has structure (2):

7. The method according to any one of claims 1 to 6, wherein m is an integer from 5 to 9.

8. The method according to any one of claims 1 to 7, wherein n is an integer from 0 to 4.

9. The method according to any one of claims 1 to 8, Wherein the ester has the structure (1):

10. The method according to any one of claims 1 to 9, The supply of CO and H2 is carried out at a pressure of 1 MPa (10 bar) to 6 MPa (60 bar).

11. The method according to any one of claims 1 to 10, wherein the method comprises the additional method step d'): d') Adding solvent.

12. Compounds according to formula (IV): wherein x is an integer from 1 to 10, and y is an integer from 0 to 8.

13. The compound according to claim 12, wherein x is an integer from 5 to 9.

14. The compound according to any one of claims 12 or 13, wherein y is an integer from 0 to 4.

15. The compound according to any one of claims 12 to 14, wherein the compound according to formula (IV) has structure (4):

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