A kind of preparation method of mixed tridecaldehyde

Abstract

The present invention relates to the technical field of organic synthesis, and in particular to a method for preparing a mixed tridecanal. The present invention provides a method for preparing a mixed tridecanal, comprising the following steps: under the conditions of carbon monoxide and hydrogen, a rhodium catalyst, an organic phosphine oxygen ligand, a mixed dodecene and a solvent are mixed, and then reacted to obtain a mixed tridecanal. In the present invention, the target product can be synthesized efficiently and selectively by regulating the catalyst with an organic phosphine oxygen ligand, and the conversion rate of the substrate and the yield of the product are both high, which has good industrial prospects. At the same time, compared with the high-pressure cobalt method, the preparation method provided by the present invention has milder conditions and is easy to operate, avoiding the problems of catalyst deactivation and difficult circulation.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for preparing mixed tridecaldehyde. Background Art

[0002] 1-Butene or mixed C4 olefins can generate C8 dimer olefins and C12 trimer olefins (US4225743, US5414160), which can be further converted into high value-added chemicals. For example, C12 trimer olefins can undergo a "hydroformylation-hydrogenation" tandem reaction to generate a mixture of isomeric tridecanols. Since the product olefins of butene trimerization are mostly trisubstituted or tetrasubstituted highly branched olefins, the product alcohol of the tandem reaction also has a highly branched characteristic, which also leads to isomeric tridecanols having good wettability, permeability and emulsification properties, and has a very wide range of applications in the textile, leather industry and metal processing industry; on the other hand, the isomeric tridecanol mixture can be further converted into a surfactant with fast degradation speed and low toxicity, which is widely used in the field of daily chemicals, especially super concentrated laundry detergents, etc. It can be seen that mixed tridecanols are the most important intermediates in the production of isomeric tridecanol mixtures. How to prepare mixed tridecanols with high selectivity by mixed dodecene hydroformylation is particularly important.

[0003] Mixed dodecene is a mixture of highly branched tri-substituted or tetra-substituted olefins. Currently, the hydroformylation reaction is very difficult. In addition, mixed tridecaldehyde has a higher boiling point than low-carbon aldehydes, and its separation energy consumption is increased. Therefore, it is particularly important to obtain the product in high yield. Summary of the invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide a method for preparing mixed tridecaldehyde, wherein both the conversion rate of the substrate and the yield of the product are high.

[0005] The present invention provides a method for preparing a mixed tridecaldehyde, comprising the following steps:

[0006] Under the condition of carbon monoxide and hydrogen, a rhodium catalyst, an organic phosphine oxygen ligand, mixed dodecene and a solvent are mixed and reacted to obtain a mixed tridecaldehyde.

[0007] Preferably, the rhodium catalyst comprises hydrated rhodium trichloride, rhodium acetate, dicarbonyl acetylacetonate rhodium, dodecacarbonyl tetrarhodium or 1,5-cyclooctadiene rhodium chloride dimer;

[0008] The molar ratio of the rhodium catalyst to the mixed dodecene is 1:1 to 10000.

[0009] Preferably, the method for preparing mixed dodecene comprises the following steps:

[0010] 1-Butene undergoes trimerization under the catalysis of heterogeneous nickel catalyst to obtain mixed dodecene;

[0011] The molar ratio of the rhodium catalyst to the mixed dodecene is 1:5000.

[0012] Preferably, the organic phosphine oxygen ligand has a structure shown in Formula I or Formula II;

[0013]

[0014] Among them, R 1 , R 1 ' and R 1 " is independently selected from C1-C8 alkyl, substituted or unsubstituted C6-C18 aromatic, cyano or ether; or R 1 , R 1 ' and R 1 "Independently forms a substituted or unsubstituted C4-C18 heterocycle with the ring in which it is located;

[0015] R 2 Selected from C1-C8 alkyl, C1-C8 alkoxy, substituted or unsubstituted C6-C18 aromatic group;

[0016] The linking group in formula II is selected from alkynyl or phenoxytolyl.

[0017] Preferably, the organic phosphine oxygen ligand is selected from one of L1 to L12;

[0018]

[0019] The molar ratio of the organic phosphine oxygen ligand to the rhodium catalyst is 1 to 10000:1.

[0020] Preferably, the molar ratio of the organic phosphine oxygen ligand to the rhodium catalyst is 10:1.

[0021] Preferably, the solvent includes at least one of toluene, n-hexane, tetrahydrofuran, N,N-dimethylformamide and anisole.

[0022] Preferably, the volume ratio of carbon monoxide to hydrogen is 1-10:1-10;

[0023] The gas pressure of the reaction is 0.1-20 MPa.

[0024] Preferably, the reaction temperature is 25 to 200° C., and the reaction time is 1 to 48 hours;

[0025] After the reaction, the process further comprises: distillation under reduced pressure.

[0026] Preferably, the volume ratio of carbon monoxide to hydrogen is 1:1;

[0027] The gas pressure of the reaction is 5 MPa, the reaction temperature is 150° C., and the reaction time is 20 h.

[0028] The present invention provides a method for preparing a mixed tridecanal, comprising the following steps: under the conditions of carbon monoxide and hydrogen, a rhodium catalyst, an organic phosphine oxygen ligand, a mixed dodecene and a solvent are mixed, and then reacted to obtain a mixed tridecanal. In the present invention, the target product can be synthesized efficiently and selectively by regulating the catalyst with an organic phosphine oxygen ligand, and the conversion rate of the substrate and the yield of the product are both high, with good industrialization prospects, wherein the use of triphenylphosphine oxide to regulate the rhodium catalyst can catalyze a substrate conversion rate greater than 60%, and the separation yield of the product mixed tridecanal is greater than 50%. At the same time, the preparation method provided by the present invention is milder than the high-pressure cobalt method, easy to operate, and avoids the problems of catalyst deactivation and difficult circulation. In addition, the mixed tridecanal obtained by the present invention can be further hydrogenated to obtain a mixture of isomeric tridecanols, and the product has a very wide range of applications in the textile, leather industry and metal processing industry; at the same time, it also has important applications in the field of daily chemicals, especially in the field of super concentrated laundry detergents. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 GC spectrum of mixed dodecene in the embodiment of the present invention;

[0030] Figure 2 This is the H NMR spectrum of mixed dodecene in the embodiment of the present invention;

[0031] Figure 3 This is the NMR carbon spectrum of the mixed dodecene in the examples of the present invention. DETAILED DESCRIPTION

[0032] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] The present invention provides a method for preparing a mixed tridecaldehyde, comprising the following steps:

[0034] Under the condition of carbon monoxide and hydrogen, a rhodium catalyst, an organic phosphine oxygen ligand, mixed dodecene and a solvent are mixed and reacted to obtain a mixed tridecaldehyde.

[0035] The mixed tridecanal is a mixture of straight / branched chain aldehydes containing thirteen carbon atoms.

[0036] In certain embodiments of the present invention, the rhodium catalyst comprises hydrated rhodium trichloride (RhCl 3 ·xH 2 O), rhodium acetate (Rh(OAc) 3 ), dicarbonyl acetylacetonate rhodium (Rh(acac)(CO) 2 ), tetrarhodium dodecacarbonyl (Rh 4 (CO) 12 ) or 1,5-cyclooctadiene rhodium chloride dimer ([RhCl(cod)] 2 ); preferably dicarbonyl acetylacetonate rhodium (Rh(acac)(CO) 2 ).

[0037] The molar ratio of the rhodium catalyst to the mixed dodecene is 1:1 to 10000, preferably 1:1000 to 5000, and more preferably 1:5000.

[0038] In certain embodiments of the present invention, the organic phosphine oxygen ligand has a structure shown in Formula I or Formula II;

[0039]

[0040] Among them, R 1 , R 1 ' and R 1 " is independently selected from C1-C8 alkyl, substituted or unsubstituted C6-C18 aromatic, cyano or ether; or R 1 , R 1 ' and R 1 "Independently forms a substituted or unsubstituted C4-C18 heterocycle with the ring in which it is located;

[0041] R 2 Selected from C1-C8 alkyl, substituted or unsubstituted C6-C18 aromatic group;

[0042] The linking group in formula II is selected from alkynyl or phenoxytolyl.

[0043] Specifically, R 1 , R 1 ' and R 1 " is independently selected from phenyl, methyl substituted phenyl, halogen substituted phenyl, methyl, cyano or butyl. Halogen may be bromine or fluorine;

[0044] R 2 Selected from ethoxy or phenyl.

[0045] More specifically, the organic phosphine oxygen ligand is selected from one of L1 to L12;

[0046]

[0047] In certain embodiments of the present invention, the molar ratio of the organic phosphine oxygen ligand to the rhodium catalyst is 1 to 10000:1; preferably 1 to 100:1; more preferably 10:1.

[0048] In certain embodiments of the present invention, the mixed dodecene is a mixture of highly branched tri-substituted or tetra-substituted olefins. Specifically, the mixed dodecene comprises:

[0049]

[0050] The sum of the amounts of the above components is 100%.

[0051] More specifically, the mixed dodecene comprises:

[0052]

[0053]

[0054] In the present invention, the preparation method of the mixed dodecene comprises the following steps:

[0055] 1-Butene undergoes trimerization under the catalysis of heterogeneous nickel catalyst to obtain mixed dodecene.

[0056] In certain embodiments of the present invention, the heterogeneous nickel catalyst is NiSO 4 / Al 2 O 3 The catalyst operating temperature (i.e. trimerization temperature) is 130-190°C, the operating pressure (i.e. trimerization pressure) is 3.0-7.0 MPa, and the volume space velocity is 0.5-3.0 h -1 Specifically, the catalyst is used at a temperature of 150°C (i.e. trimerization temperature), a pressure of 5.0 MPa (i.e. trimerization pressure), and a volume space velocity of 1.0 h -1 .

[0057] In certain embodiments of the present invention, the solvent includes at least one of toluene, hexane, tetrahydrofuran (THF), N,N-dimethylformamide (DMF) and anisole; preferably toluene. The ratio of the solvent to the mixed dodecene is 20-50 mL: 40-100 mmol; specifically, it can be 50 mL: 100 mmol.

[0058] In the present invention, the reaction is carried out under the condition of a mixed gas; the mixed gas includes carbon monoxide and hydrogen. In certain embodiments of the present invention, the volume ratio of carbon monoxide to hydrogen is 1-10:1-10; preferably 1-5:1-5; more preferably 1:1. In certain embodiments of the present invention, before the reaction, it also includes: purging the reaction container with the mixed gas.

[0059] In certain embodiments of the present invention, the gas pressure of the reaction is 0.1-20 MPa, preferably 1-10 MPa, and more preferably 5 MPa.

[0060] In certain embodiments of the present invention, the reaction temperature is 25-200°C, preferably 100-200°C, more preferably 150°C; the reaction time is 1-48h, preferably 10-24h, more preferably 20h.

[0061] In certain embodiments of the present invention, after the reaction, the step further comprises: distillation under reduced pressure.

[0062] The present invention has no particular limitation on the sources of the raw materials used above, and all of them can be commercially available.

[0063] In order to further illustrate the present invention, a method for preparing a mixed tridecaldehyde provided by the present invention is described in detail below in conjunction with examples, but it should not be construed as limiting the scope of protection of the present invention.

[0064] The chemical reagents involved in the examples were purchased from Shanghai Haohong Biopharmaceutical Technology Co., Ltd.

[0065] Gas chromatograph used for gas chromatography analysis: Agilent-7820;

[0066] Gas chromatography column and test conditions: 0.25mm×30m HP-5 capillary column, detector FID, vaporization chamber temperature 250℃, column box temperature 250℃, FID detector temperature 300℃, argon flow rate 2.0mL / min, hydrogen flow rate 30mL / min, air flow rate 400mL / min, injection volume 0.2μL. The conversion rate of olefins and the selectivity of products were calculated using the area normalization method. Heating program: preheat to column temperature 50℃, hold for 5min, increase from 40℃ to 250℃ at a rate of 15℃ / min, and hold for 5min.

[0067] Gas chromatography-mass spectrometer: Agilent7890B GC-MS;

[0068] NMR analyzer: Bruker400M.

[0069] The preparation method of mixed dodecene comprises the following steps:

[0070] 1-Butene over heterogeneous nickel catalyst NiSO 4 / Al 2 O 3 Under the catalytic action of -1 The trimerization reaction was carried out at a reaction pressure of 5.0 MPa and a reaction temperature of 150°C to obtain mixed dodecene.

[0071] The mixed dodecene comprises:

[0072]

[0073] The mixed dodecene was subjected to gas chromatography analysis, and the results were as follows: Figure 1 shown. Figure 1 GC spectrum of mixed dodecene in the embodiment of the present invention. Figure 1 It can be seen that the retention time of mixed dodecene is distributed in the range of 11 to 15 minutes.

[0074] The H NMR spectrum of the mixed dodecene was analyzed. Figure 2 shown. Figure 2 : is the H NMR spectrum of mixed dodecene in the embodiment of the present invention. Figure 2 It can be seen that the chemical shift of 4.5 to 5.5 ppm is the hydrogen signal peak on the unsaturated carbon atom.

[0075] The NMR carbon spectrum of the mixed dodecene was analyzed, and the results were as follows: Figure 3 shown. Figure 3 This is the NMR carbon spectrum of the mixed dodecene in the example of the present invention. It can be seen that the chemical shift of 110-140 ppm is the carbon signal of the multi-substituted unsaturated carbon atom.

[0076] Embodiments 1 to 5

[0077] 0.02mmol of rhodium catalyst, 0.2mmol of organic phosphine oxygen ligand (triphenylphosphine oxide, i.e. L1), 100mmol of mixed dodecene and 50mL of toluene were added to the reaction bottle in sequence, and the reaction bottle was placed in a high-pressure reactor. The reactor was cleaned by charging and discharging a mixed gas (carbon monoxide and hydrogen, volume 1:1) of 0.2MPa three times, and then the mixed gas (carbon monoxide and hydrogen, volume 1:1) was charged to 5.0MPa. The autoclave was placed in a constant temperature oil bath pot, and after reacting at 150℃ for 20h, the substrate conversion rate and product selectivity were determined by gas chromatography analysis, and the mixed tridecane was separated by vacuum distillation to calculate the yield. Table 1 shows the experimental results of preparing mixed tridecane by hydroformylation of mixed dodecene catalyzed by different rhodium catalysts.

[0078] Table 1 Experimental results of preparing mixed tridecaldehyde by hydroformylation of mixed dodecene catalyzed by different rhodium catalysts

[0079]

[0080] In Table 1, b The results of gas chromatography analysis.

[0081] Embodiments 6 to 16

[0082] Add 0.02mmol of rhodium catalyst (dicarbonyl acetylacetonate rhodium), 0.2mmol of organic phosphine oxygen ligand, 100mmol of dodecene and 50mL of toluene to the reaction bottle in sequence, put the reaction bottle into a high-pressure reactor, fill and discharge the reactor with 0.2MPa of mixed gas (carbon monoxide and hydrogen, volume 1:1) three times to clean the reactor, and then fill the mixed gas (carbon monoxide and hydrogen, volume 1:1) to 5.0MPa, place the autoclave in a constant temperature oil bath, react at 150℃ for 20h, determine the substrate conversion rate and product selectivity by gas chromatography, and separate the mixed tridecaldehyde by vacuum distillation to calculate the yield. Table 2 shows the experimental results of preparing mixed tridecaldehyde with different organic phosphine oxygen ligands.

[0083] Table 2 Experimental results of preparing mixed tridecaldehyde with different organic phosphine oxygen ligands

[0084]

[0085]

[0086] In Table 2, b The results of gas chromatography analysis.

[0087] Examples 17 to 21

[0088] Rhodium catalyst (dicarbonyl acetylacetonate rhodium) 0.02mmol, (triphenylphosphine oxide, i.e. L1) 0.2mmol, mixed dodecene 100mmol and solvent 50mL were added to the reaction bottle in sequence, the reaction bottle was placed in a high-pressure reactor, 0.2MPa mixed gas (carbon monoxide and hydrogen, volume 1:1) was filled and discharged three times to clean the reactor, and then the mixed gas (carbon monoxide and hydrogen, volume 1:1) was filled to 5.0MPa, the autoclave was placed in a constant temperature oil bath, reacted at 150℃ for 20h, and the substrate conversion rate and product selectivity were determined by gas chromatography analysis, and the mixed tridecaldehyde was separated by vacuum distillation to calculate the yield. Table 3 shows the experimental results of preparing mixed tridecaldehyde with different solvents.

[0089] Table 3 Experimental results of preparing mixed tridecaldehyde with different solvents

[0090]

[0091] In Table 3, b The results of gas chromatography analysis.

[0092] Experimental results show that in the method for preparing the mixed tridecaldehyde provided by the present invention, the conversion rate of the substrate is not less than 21%, and the yield of the product is not less than 16%.

[0093] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a mixed tridecaldehyde, comprising the following steps: Under the condition of carbon monoxide and hydrogen, a rhodium catalyst, an organic phosphine oxygen ligand, mixed dodecene and a solvent are mixed and reacted to obtain a mixed tridecaldehyde; The rhodium catalyst is dicarbonyl acetylacetonate rhodium or 1,5-cyclooctadiene rhodium chloride dimer; The organic phosphine oxygen ligand is selected from L1 or L2; The mixed dodecene comprises: The sum of the amounts of the above components is 100%; The molar ratio of the rhodium catalyst to the mixed dodecene is 1:1000-5000; The molar ratio of the organic phosphine oxygen ligand to the rhodium catalyst is 1 to 100:1; The solvent is toluene or anisole; The reaction temperature is 25-200°C and the gas pressure is 0.1-20MPa; The volume ratio of carbon monoxide to hydrogen is 1-5:1-5.

2. The preparation method according to claim 1, characterized in that: The preparation method of the mixed dodecene comprises the following steps: 1-Butene undergoes trimerization under the catalysis of heterogeneous nickel catalyst to obtain mixed dodecene.

3. The preparation method according to claim 1, characterized in that: The reaction time is 1 to 48 hours; After the reaction, the process further comprises: distillation under reduced pressure.

4. The preparation method according to claim 1, characterized in that: The volume ratio of carbon monoxide to hydrogen is 1:1; The gas pressure of the reaction is 5 MPa, the reaction temperature is 150° C., and the reaction time is 20 h.

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