Method for preparing trioxane derivatives

Abstract

To provide a method for preparing trioxane derivatives that achieves a good yield.SOLUTION: An ester of formula (I) (where m is an integer from 1 to 10 and n is an integer from 0 to 8) is converted to a corresponding trioxane derivative by heating in the presence of a specific catalyst.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] The object of the present invention was to provide a process for the preparation of trioxane derivatives, the intention being to achieve good yields. [Background technology]

[0003] U.S. Patent Application Publication No. 2017 / 0233366 describes a method for preparing trioxane. In this method, aqueous formaldehyde is converted to trioxane in the presence of methanesulfonic acid at 105° C. Table 1 shows that a 40% formaldehyde conversion was achieved.

[0004] This object is achieved by the method according to claim 1. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] US Patent Application Publication No. 2017 / 0233366 Summary of the Invention

[0006] 1. A method comprising the following method steps: a) firstly charging the ester of formula (I):

[0007] [ka]

[0008] In the formula, m is an integer of 1 to 10, n is an integer from 0 to 8; b) adding a compound of formula (II):

[0009] [ka]

[0010] In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 -H, -(C1-C 12 )-Alkyl, -(C6-C 20 )-aryl; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 Ga-(C6-C 20 )-aryl, the aryl ring is -(C-C 12 )-alkyl, -O-(C1-C 12 )-alkyl; c) adding PtI2; d) supplying CO and H2; e) heating the reaction mixture of a) to d) to convert the ester to a compound of formula (III):

[0011] [ka]

[0012] A method comprising:

[0013] In this method, process steps a) through e) can be performed in any desired order, however, the addition of CO and H2 typically occurs after the co-reactants are first charged in steps a) through c).

[0014] (C1-C 12The expression (C1-C8)-alkyl embraces straight-chain and branched alkyl groups having 1 to 12 carbon atoms. These are preferably (C1-C8)-alkyl groups, more preferably (C1-C6)-alkyl and most preferably (C1-C4)-alkyl.

[0015] (C6-C 20 The term (C6-C)-aryl embraces monocyclic or polycyclic aromatic hydrocarbon radicals having 6 to 20 carbon atoms. These are preferably (C6-C 14 )-aryl, more preferably (C-C 10 )-aryl.

[0016] In one variation of this method, R 2 , R 3 , R 5 , R 6 , R 7 , R 8 is -(C1-C 12 )-Alkyl, -(C6-C 20 )-aryl.

[0017] In one variation of this method, R 5 , R 6 , R 7 , R 8 is -(C6-C 20 )-aryl.

[0018] In one variation of this method, R 5 , R 6 , R 7 , R 8 is -Ph.

[0019] In one variation of this method, R 2 and R 3 is -(C1-C 12 )-alkyl.

[0020] In one variation of this method, R 2 and R 3 is -CH3.

[0021] In one variation of this method, R 1 and R 4 is -H.

[0022] In one variation of the method, compound (II) has the structure (2):

[0023] [ka]

[0024] It has.

[0025] In one variation of this method, m is an integer from 5 to 9.

[0026] In one variation of this method, m is 7.

[0027] In one variation of this method, n is an integer from 0 to 4.

[0028] In one variation of this method, n is 0.

[0029] In one variation of the method, the ester has the structure (1):

[0030] [ka]

[0031] It has.

[0032] In one variation of this method, CO and H2 are supplied at a pressure in the range of 1 MPa (10 bar) to 6 MPa (60 bar).

[0033] In one variation of this method, CO and H2 are supplied at a pressure in the range of 3 MPa (30 bar) to 5 MPa (50 bar).

[0034] In one variation of this method, the reaction mixture is heated to a temperature in the range of 40°C to 100°C.

[0035] In one variation of this method, the reaction mixture is heated to a temperature in the range of 50°C to 80°C.

[0036] In one variant of the method, the method comprises the following additional method step d'): d') Adding a solvent.

[0037] In one variation of the method, the solvent is selected from THF, MTBE, DCM, ACN, heptane, DMF, toluene, xylene, mesitylene, dibenzyltoluene.

[0038] In one variation of this method, the solvent is toluene.

[0039] In addition to the method, compounds are also claimed.

[0040] A compound of formula (IV):

[0041] [ka]

[0042] In the formula, x is an integer of 1 to 10, The compound, wherein y is an integer of 0 to 8.

[0043] In one embodiment, x is an integer from 5 to 9.

[0044] In one embodiment, x is 7.

[0045] In one embodiment, y is an integer from 0 to 4.

[0046] In one embodiment, y is 0.

[0047] In one embodiment, the compound of formula (IV) has the structure (4):

[0048] [ka]

[0049] It has. DETAILED DESCRIPTION OF THE INVENTION

[0050] The invention is explained in more detail below with reference to exemplary embodiments. [Example]

[0051] Synthesis of trimethyl 10,10',10"-(1,3,5-trioxane-2,4,6-triyl)tris(decanoate) (4) 150 ml (132 g) of methyl dec-9-enoate (1), 100 ml of anhydrous toluene, 320 mg of PtI (0.1 mol % relative to (1)), and 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 an electronic pressure transducer.

[0052] The autoclave was pressurized to 40 bar with synthesis gas (H2:CO = 1:1) and stirred for >500 min. -1 The reaction is carried out at 60°C. The reaction time is 10 hours. The gas consumption is readjusted so that the reaction takes place at approximately 40 bar. After 10 hours, the reaction is stopped, the autoclave is cooled, the gas is vented and the autoclave is flushed four times with 30 bar nitrogen. The reaction solution is transferred to a 500 ml Schlenk vessel.

[0053] Run GC. The GC yield of methyl 11-oxoundecanoate (3) is 98% (n:iso selectivity = 98.2:1.8).

[0054] [ka]

[0055] The mixture was then -3 Thor (K PDistill under fine vacuum (=100°C). A colorless liquid is obtained (146 g = 96%).

[0056] This liquid crystallized completely within 24 hours. 1 H-NMR, 13 C-NMR and MS analysis yield a solid identified as trimethyl 10,10',10"-(1,3,5-trioxane-2,4,6-triyl)tris(decanoate) (4). The purity is >99%.

[0057] NMR (CDCl3, 300MHz): 1 H:4.75 t(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) 13 C:174.28s,101.65s,51.40s,34.39s,34.08s,29.38s,29.32s,29.20s,29.11s,24.93s,23.53s 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).

[0058] [ka]

[0059] [ka]

[0060] Reaction conditions: Ester (1), 0.1 mol% PtI2, 0.15 mol% Xantphos (2), solvent: toluene, p(CO / H2): 40 bar, T: 60°C, t: 10 h.

[0061] As shown by the experimental results, the objective is achieved by the method according to the invention.

Claims

1. 1. A method comprising the following method steps: a) firstly charging the ester of formula (I): [Chemical (I)] In the formula, m is an integer from 1 to 10; n is an integer from 0 to 8; b) adding a compound of formula (II): 【Chemistry (II)】 In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ is -H, -(C １ -C １２ )-alkyl, -(C ６ -C ２０ )-aryl; and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ But-(C ６ -C ２０ )-aryl, the aryl ring is -(C １ -C １２ )-alkyl, —O—(C １ -C １２ )-alkyl; c) PtI ２ adding; d) CO and H ２ supplying; e) heating the reaction mixture of a)-d) to convert the ester to a compound of formula (III): 【Chemistry (III)】 A method comprising:

2. In the formula, R ２ , R ３ , R ５ , R ６ , R ７ , R ８ But -(C １ -C １２ )-alkyl, -(C ６ -C ２０ )-aryl, The method of claim 1.

3. In the formula, R ５ , R ６ , R ７ , R ８ But -(C ６ -C ２０ )-aryl; 3. The method according to claim 1 or 2.

4. In the formula, R ２ and R ３ But -(C １ -C １２ )-alkyl; The method according to any one of claims 1 to 3.

5. In the formula, R １ and R ４ is -H, The method according to any one of claims 1 to 4.

6. The compound (II) has the structure (2): 【Chemistry (2)】 having The method according to any one of claims 1 to 5.

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

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

9. The ester has the structure (1): 【Chemistry (1)】 having The method according to any one of claims 1 to 8.

10. CO and H ２ is supplied at a pressure in the range of 1 MPa (10 bar) to 6 MPa (60 bar), The method according to any one of claims 1 to 9.

11. The following additional method step d'): d') adding a solvent; The method according to any one of claims 1 to 10.

12. A compound of formula (IV): 【Chemistry (IV)】 In the formula, x is an integer from 1 to 10; A compound wherein y is an integer from 0 to 8.

13. wherein x is an integer from 5 to 9.

13. The compound of claim 12.

14. wherein y is an integer from 0 to 4.

14. A compound according to any one of claims 12 and 13.

15. The compound of formula (IV) has the structure (4): 【Chemistry (4)】 having The compound according to any one of claims 12 to 14.

Images