Alkoxycarbonylation of trivinylcyclohexane

Abstract

To provide a method for alkoxycarbonylation of trivinyl cyclohexane.SOLUTION: A method includes the step in which trivinyl cyclohexane, a ligand (L) of the following formula, a compound including Pd, a C1-12 alcohol, and CO are supplied and heated, and the resultant product is changed into triester.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a process for the alkoxycarbonylation of trivinylcyclohexane. [Background technology]

[0002] Alkoxycarbonylation of ethylenically unsaturated compounds is a process that is becoming increasingly important. Alkoxycarbonylation is understood to be the reaction of ethylenically unsaturated compounds, such as olefins, with carbon monoxide and an alcohol in the presence of a metal or metal complex and a ligand to give the corresponding ester. [ka] Summary of the Invention [Problem to be solved by the invention]

[0003] The problem addressed by the present invention was to provide a process for the alkoxycarbonylation of trivinylcyclohexane, which allows the conversion of all three vinyl groups to esters. It is further an object to provide fast gelling plasticizers for plastics, particularly polyvinyl chloride (PVC), which allow for low processing temperatures. [Means for solving the problem]

[0004] This object is achieved by the method according to claim 1. The process is as follows: a) initially introducing one of compounds (i), (ii), (iii) or a mixture of at least two of these compounds, [ka] b) adding a ligand (L) and a compound containing Pd, or a complex containing Pd and the adding a ligand (L); [ka] c) adding an alcohol having 1 to 12 carbon atoms; d) supplying CO; e) heating the reaction mixture of a) to d) to convert the compound or mixture of a) into a triester. The method according to claim 1,

[0005] In one variant of the process, in step a), said compound (i) is introduced first.

[0006] In one variant of the process, in step a), said compound (ii) is introduced first.

[0007] In one variant of the method, in step c), the alcohol does not contain any further heteroatoms other than oxygen and does not have any multiple bonds.

[0008] In one variation of the method, in step c), the alcohol is methanol, ethanol, n Butanol, methylpropanol, n Pentanol, iso Pentanol, 2-methylbutanol, 3-methylbutanol, n Hexanol, iso Hexanol, n Heptanol, iso Heptanol, n Octanol, iso Octanol, 2-ethylhexanol, n Nonanol, iso Nonanol, n Decanol, iso decanol, 2-propylheptanol.

[0009] In one variation of the process, in step c), the alcohol is methanol.

[0010] In one variation of the method, in step d), the CO is supplied to a pressure in the range of 20 bar to 60 bar.

[0011] In one variation of the method, in step d), the CO is supplied to a pressure in the range of 30 bar to 50 bar.

[0012] In one variation of the method, in step e), the heating is carried out at a temperature in the range of 90°C to 130°C.

[0013] In one variation of the method, in step e), the heating is carried out at a temperature in the range of 100°C to 120°C.

[0014] In one variation of the method, the method includes the additional step of: f) purifying the triester. has.

[0015] In one variation of the method, the method includes the additional step of: g) reacting the purified triester with NaOMe and H2 to obtain a triol has.

[0016] In one variation of the method, in step g), the reaction is catalyzed with Ru-MACHO-BH.

[0017] In one variation of the process, in step g), the reaction is carried out at a H2 pressure ranging from 30 bar to 70 bar.

[0018] In one variation of the process, in step g), the reaction is carried out at a H2 pressure ranging from 40 bar to 60 bar.

[0019] In one variation of the process, in step g), the reaction is carried out at a temperature in the range of 80°C to 120°C.

[0020] In one variation of the process, in step g), the reaction is carried out at a temperature in the range of 90°C to 110°C.

[0021] In addition to the method, compounds are also claimed. A compound according to formula (1). [ka] The compounds are preferably prepared according to the methods described herein. A compound prepared by the above method. EXAMPLES

[0022] The present invention will now be described in detail with reference to examples. Trimethyl 3,3',3''-(cyclohexane-1,2,4-triyl)tripropyl Synthesis of onate (1) ("triester") [ka] TIFF0007610054000006.tif80170[Pd(acac)2] (15.2 mg, 0.1 mol%), Ligand (L) (103 In a 100 mL steel autoclave, MeOH (30 mL), trivinylcyclohexane (i) (8.1 g, 50 mmol) and paratoluenesulfonic acid (PTSA, 143 mg, 1.5 mol%) were placed under argon atmosphere. MeOH (30 mL), and trivinylcyclohexane (i) (8.1 g, 50 mmol) were then injected via syringe. The autoclave was flushed with CO three times and then pressurized with 40 bar CO pressure. The reaction was carried out at 110° C. for more than 10 hours. The autoclave was then cooled to room temperature and depressurized. The desired product was obtained by distillation (165° C., 10 -3 Purified by HPLC using a HPLC-MS / MS microscope. 1 H-NMR, 13 Characterized by C-NMR and HR-MS (15.6 g, 91% yield). 1H-NMR(300MHz,C6D6)δ=3.39-3.37(m,9H), 2.24-1.86(m,7H),1.48-0.27(m,14H) 13 C-NMR(75MHz,C6D6)δ=173.68-173.54(m),51.04,40.60-40.47(m),38.24,38.14,37.51,37.07,36.54,36.10,35.52,35.14,33.87,32.70,32 .55,32.51,32.38,32.29,32.23,32.08,31.97,31.86,31.76,31.68,3 1.63,31.43,30.98,30.79,30.75,29.31,28.52,28.47,28.34,28.13,2 8.11, 27.13, 26.58, 25.12, 20.79, 19.74. MS(EI):311(13.40),293(3.65),269(75.76),237(60.40),219(25.13),205(100),191(17.62),177(14.83),145(24.59) HR-MS(ESI): Calculated value C 18 H 30 O6 [M+H] + : 343.21152, Actual value: 343.21113

[0023] 3,3',3''-(Cyclohexane-1,2,4-triyl)tris(propane- Synthesis of 1-ol (2) ("triol") [ka] Ru-MACHO-BH (59 mg, 2 mol%) and NaOMe (27 mg, 10 mol%) were placed in a 25 mL steel autoclave under an argon atmosphere. MeOH (8 mL) and the triester (1) (1.93 g, 5.67 mmol) were then injected via syringe. The autoclave was flushed with H2 three times and then pressurized with 50 bar H2 pressure. The reaction was carried out at 100°C for more than 10 h. The autoclave was then cooled to room temperature and depressurized. The desired product was purified by filtration over silica gel, 1 H-NMR, 13 Characterized by C-NMR and HR-MS (1.4 g, 96% yield). 1 H-NMR(400MHz,CD3OD)δ=3.32-3.30(m,6H),1.85-1.77(m,2H),1.63-0.62(m,19H) 13 C-NMR(100MHz,CD3OD)δ=63.53-63.29(m),42.69,42.53,42.39,42.31,40.34,40.24,39.28,38.89,38.12,38.02,37. 58,37.27,35.89,34.78,34.72,34.53,34.37,33.17,31.52,31.50,31.40,31.38,31.05,30.60,30.48,30.41,30.32, 30.24, 30.17, 28.77, 28.22, 26.61, 22.53, 21.45 MS(EI):222(1.06),194(1.14),181(2.96),163(11.54),135(9.81),121(17.04),107(15.25),93(32.69) HR-MS(ESI): Calculated value C 15 H 30 O3 [M+H] + : 259.22677, Actual value: 259.2269

[0024] Preparation of plastisol A PVC plastisol was prepared, such as that used in the manufacture of topcoat films for flooring. The values ​​in the plastisol formulations are in parts by weight. The formulation of the polymer composition is shown in Table 1. [Table 1]

[0025] Weigh out the liquid ingredients first, then the powdered ingredients into a PE beaker. The mixture is manually stirred with an ointment spatula to ensure that no unwetted powder is present. The mixing beaker is then clamped to the clamping device of a dissolver stirrer. After switching on the stirrer, the speed is slowly increased to about 2,000 rpm. Meanwhile, the plastisol is carefully degassed, keeping the pressure below 20 millibars. As soon as the plastisol reaches a temperature of about 30° C., the speed is reduced to about 350 rpm. The plastisol is then degassed for 9 minutes at said speed and at a pressure of less than 20 mbar. This ensures that the plastisol is homogenized at the specified energy input. The plastisol is then immediately equilibrated to 25.0° C. in a temperature-controlled cabinet for further study.

[0026] The gelling properties of plastisols. The gelling properties of the pastes were investigated on a Physica MCR 101 operating under shear stress control in oscillatory mode using a parallel plate analytical system (PP25). An additional heating hood was connected to the system to achieve uniform heat distribution and uniform sample temperature. The following parameters were set: Mode: Temperature Gradient Starting temperature 25℃ End temperature 180℃ Heating / cooling rate 5℃ / min Frequency 4-0.1Hz logarithmic ramp Period frequency ω:10 1 / s Number of measurement points: 63 Duration of measurement point: 0.5 min Automatic gap adjustment F:0N Duration of a constant measurement point Gap width: 0.5mm

[0027] Analytical procedures A spatula is used to apply a few grams of the paste to be analyzed, without any air bubbles, onto the lower plate of the analytical system, so that after the analytical system is assembled, some paste seeps out of the analytical system uniformly (no more than 6 mm in any direction). The heating hood is then placed over the sample and the analysis is started. The complex viscosity of the paste is measured as a function of temperature after 24 hours (the paste is stored at 25° C. in a Memmert temperature-controlled cabinet). A clear increase in the complex viscosity is taken as a measure of gelation. The comparison value used is therefore the temperature at which a paste viscosity of 1,000 Pa·s is reached. The experiment was repeated with three comparative plastisols, each using a different plasticizer. [Table 2]

[0028] The target value of 1,000 Pa·s could be achieved with the compound (1) of the present invention at 65° C. Such low gelling temperatures are advantageous in processing procedures. They allow plastisol processing at lower temperatures.

Claims

1. A method for obtaining a triol, comprising the steps of: The following steps: a) introducing one of compounds (i), (ii), (iii) or a mixture of at least two of these compounds; 【Chemistry 1】 b) adding a ligand (L) and a compound containing Pd, or adding a complex containing Pd and the ligand (L); 【Chemistry 2】 c) adding an alcohol having 1 to 12 carbon atoms; d) providing CO; e) heating the reaction mixture obtained through steps a) to d) to convert the compound or mixture of a) into a triester; f) purifying the triester; g) Reacting the purified triester with NaOMe and H 2 to obtain a triol.

2. The method according to claim 1 , wherein in step a), compound (i) is introduced.

3. The method according to claim 1 , wherein in step a), compound (ii) is introduced.

4. 4. The process according to claim 1, wherein in step c) the alcohol does not contain any further heteroatoms other than oxygen and does not have any multiple bonds.

5. In the step c), the alcohol is methanol, ethanol, n Butanol, methylpropanol, n Pentanol, iso Pentanol, 2-methylbutanol, 3-methylbutanol, n Hexanol, iso Hexanol, n Heptanol, iso Heptanol, n Octanol, iso Octanol, 2-ethylhexanol, n Nonanol, iso Nonanol, n Decanol, iso The process according to any one of claims 1 to 4, wherein the alcohol is selected from the group consisting of decanol and 2-propylheptanol.

6. The process according to any one of claims 1 to 5, wherein in step c) the alcohol is methanol.

7. 7. The method of any one of claims 1 to 6, wherein in step d) the CO is supplied to a pressure in the range of 20 bar to 60 bar.

8. The method according to any one of claims 1 to 7, wherein in step e), the heating is carried out at a temperature in the range of 90 to 130°C.

9. 9. The method according to claim 1, wherein in step g), the reaction is catalyzed by Ru-MACHO-BH.

10. In step g), the reaction is carried out at a pressure of H 2 The method according to any one of claims 1 to 9, which is carried out under pressure.

11. 11. The process according to any one of claims 1 to 10, wherein in step g), the reaction is carried out at a temperature in the range of 80 to 120°C.

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