Organic compound manufacturing method and organic compound manufacturing apparatus

Abstract

Provided is a method for producing an organic compound, said method including a step for repeating an operation in which a liquid containing an organic solvent is passed through a packed column packed with magnesium, a material containing an organic halide being added to the liquid before it is passed through. Further provided is a device for producing an organic compound, said device comprising: a packed column which is packed with magnesium; a liquid passing unit which repeats an operation in which a liquid containing an organic solvent is passed through the packed column; and a material adding unit which adds a material containing an organic halide to the liquid before it is passed through.

Description

[Technical Field]

[0001] The present invention relates to a method for producing an organic compound and an apparatus for producing an organic compound. [Background technology]

[0002] Organomagnesium halides are organometallic compounds used in the Grignard reaction, which is a carbon-carbon bond-forming reaction that is widely used in the synthesis of various organic compounds (see, for example, Patent Documents 1 and 2). Generally, organomagnesium halides have high reactivity but low stability.

[0003] Known methods for producing organomagnesium halides include a batch-type production method in which magnesium is dispersed in an organic solvent and then a solution containing an organomagnesium halide is added dropwise (see, for example, Patent Documents 1 and 2). Here, the reaction between the organomagnesium halide and magnesium is a solid-liquid reaction, and therefore, magnesium particles with an average particle size of approximately 2 mm or less are used to improve the reaction rate. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-114166 [Patent Document 2] Patent No. 3779452 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the reaction between an organic halide and magnesium generates a large amount of heat, which increases the temperature of the reaction system, making it difficult to control the reaction. Furthermore, if magnesium remains in the reaction system, it can cause a side reaction in the next reaction, which necessitates the use of an excessive amount of organic halide, resulting in a decrease in the conversion rate of the organic halide.

[0006] An object of the present invention is to provide a method and an apparatus for producing an organic compound that can suppress a temperature rise in the reaction system and improve the conversion rate of an organic halide. [Means for solving the problem]

[0007] In one aspect of the present invention, in a method for producing an organic compound, the method comprises a step of repeatedly passing a liquid containing an organic solvent through a packed tower packed with magnesium, and a raw material containing an organic halide is added to the liquid before passing the liquid through the packed tower.

[0008] In the above-mentioned method for producing an organic compound, the operation of passing the liquid through the single packed column may be repeated.

[0009] The raw material may further contain a ketone compound or a silane compound.

[0010] In the method for producing the organic compound, when the total amount of organic halide added to the liquid before passing is A [mol] and the amount of magnesium packed in the packed tower is B [mol], the following formula can be used: A / B×α (wherein α is 0.9 or more and 1.2 or less.) The number of times to repeat the operation may be determined by:

[0011] Another aspect of the present invention is an organic compound production apparatus comprising: a packed tower packed with magnesium; a liquid passing section that repeatedly passes a liquid containing an organic solvent through the packed tower; and a raw material adding section that adds a raw material containing an organic halide to the liquid before passing the liquid through the packed tower.

[0012] The liquid passing section may repeatedly pass the liquid through a single packed tower.

[0013] The raw material may further contain a ketone compound or a silane compound. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a method and an apparatus for producing an organic compound that can suppress a temperature rise in the reaction system and improve the conversion rate of an organic halide. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 is a diagram illustrating an example of an apparatus for producing an organic compound according to an embodiment of the present invention. [Figure 2] FIG. 10 is a diagram showing another example of the organic compound production apparatus of the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0016] Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

[0017] [Method of producing organic compounds] The method for producing an organic compound of this embodiment includes a step of repeatedly passing a liquid containing an organic solvent through a packed column packed with magnesium (hereinafter referred to as a liquid passing operation), and adding a raw material containing an organic halide to the liquid before passing the liquid through the packed column. During this process, the magnesium reacts with the organic halide to produce an organic magnesium halide.

[0018] When the method for producing an organic compound according to the present embodiment is used, the temperature of the reaction system can be controlled by adjusting the rate at which the raw material containing an organic halide is added to the liquid before passing it through, thereby suppressing a temperature rise in the reaction system. Furthermore, by adjusting the rate at which the raw material containing an organic halide is added to the liquid before passing it through, depending on the amount of magnesium packed into the packed column through which the liquid is passed and the temperature of the liquid, it is possible to react almost the entire amount of the organic halide, thereby improving the conversion rate of the organic halide.

[0019] In the present specification and claims, the term "organic compound" includes organometallic compounds. Repeatedly passing a liquid through a packed column includes two or more times of passing a liquid through a single packed column, one time of passing a liquid through each of a plurality of packed columns, and two or more times of passing a liquid through each of a plurality of packed columns.

[0020] In the method for producing an organic compound of this embodiment, it is preferable to repeat the liquid passing operation through a single packed column in terms of simplifying the apparatus.

[0021] When the liquid passing operation is repeated for a plurality of packed towers, the raw material is added to the liquid before passing it through each packed tower.

[0022] Furthermore, when adding the raw material to the liquid before passing it through, the raw material may be added continuously or intermittently.

[0023] When the raw material is a solid, the raw material is dissolved in an organic solvent and added to the liquid before passing it through. When the raw material is a liquid, the raw material may be added alone to the liquid before passing it through, but it is preferable to add the raw material dissolved in an organic solvent. Here, the organic solvent in which the raw material is dissolved may be the same as or different from the organic solvent contained in the liquid to be passed through.

[0024] The raw material may further contain a compound capable of reacting with the organomagnesium halide, such as a ketone compound or a silane compound. When the raw material contains a ketone compound, magnesium reacts with the organomagnesium halide to generate the organomagnesium halide, and then the organomagnesium halide reacts with the ketone compound to generate a tertiary alcohol. As described above, the temperature rise in the reaction system is suppressed, and the conversion rate of the organomagnesium halide is improved. When the raw material contains a silane compound, magnesium reacts with the organomagnesium halide to generate the organomagnesium halide, and then the organomagnesium halide reacts with the silane compound to generate an organosilicon compound. As described above, the temperature rise in the reaction system is suppressed, and the conversion rate of the organomagnesium halide is improved.

[0025] Here, the amount of the ketone compound or silicon compound used may be appropriately determined taking into consideration the reactivity with the resulting organomagnesium halide, and the molar ratio of the ketone compound or silicon compound to the organomagnesium halide is usually 1 or more and 2.5 or less.

[0026] When the product of the step of repeatedly passing a liquid through a packed column contains a tertiary alcohol or an organosilicon compound, the method for producing an organic compound of this embodiment may further include a step of adding an acid to decompose unreacted organomagnesium halide, and a step of purifying the tertiary alcohol or organosilicon compound.

[0027] When the product of the step of repeatedly passing a liquid through the packed column contains an organomagnesium halide, the method for producing an organic compound of the present embodiment may further include a step of reacting the organomagnesium halide with a compound capable of reacting with the organomagnesium halide, such as a ketone compound or a silane compound.

[0028] The packed tower may be filled with magnesium partially or entirely inside and may have any shape that allows liquid to pass through it, but it is preferable that the cross section is circular and the structure is linear without branches or bends.

[0029] The inner diameter of the packed tower is not particularly limited, but is, for example, 1 cm or more and 50 cm or less.

[0030] The length of the packed tower is not particularly limited, but is, for example, 30 cm or more and 150 cm or less.

[0031] The material of the packed tower is not particularly limited, but from the viewpoint of chemical resistance, examples include fluororesins such as polytetrafluoroethylene, stainless steel, and the like.

[0032] The average particle size of the magnesium particles packed into the packed tower is not particularly limited, but is, for example, 1 mm or more and 20 mm or less.

[0033] The shape of the magnesium is not particularly limited, and examples thereof include pellets, shot, mesh, and rod shapes.

[0034] The filling rate of magnesium packed into the packed tower is not particularly limited, but is, for example, 30% or more and 99% or less.

[0035] The flow rate of the liquid to be passed is not particularly limited, but is, for example, 10 ml / min or more and 2000 ml / min or less.

[0036] The temperature of the liquid to be passed through is not particularly limited, but is, for example, from -20°C to 100°C.

[0037] The rate at which the raw material is added to the liquid before passing it through is not particularly limited, but is, for example, 10 mmol / min or more and 1,000 mol / min or less.

[0038] The number of times the liquid is passed through the packed tower is not particularly limited, but is, for example, from 2 to 10 times.

[0039] If the total amount of organic halide added to the liquid before passing it through is A [mol] and the amount of magnesium packed in the packed tower is B [mol], then the formula A / B×α (wherein α is 0.9 or more and 1.2 or less.) The number of times the operation is repeated for the packed column can be determined by

[0040] After repeating the liquid passing operation through the packed tower, the liquid passing operation may be carried out without adding any raw materials in order to react the unreacted raw materials.

[0041] [Organic compound manufacturing equipment] FIG. 1 shows an example of an apparatus for producing an organic compound according to this embodiment.

[0042] The organic compound production apparatus 10 includes a packed tower 11 filled with magnesium 11a, a liquid passing section 12 that repeatedly passes a liquid through the packed tower 11, and a raw material adding section 13 that adds a raw material containing an organic halide to the liquid before passing it through.

[0043] The liquid passing section 12 includes, for example, a buffer tank for holding the organic solvent, and a pump for transferring the organic solvent from the buffer tank and repeatedly passing the organic solvent through the packed tower 11. The organic solvent that has passed through the buffer tank returns to the buffer tank, containing the product and unreacted raw materials.

[0044] The raw material adding section 13 includes, for example, a raw material tank that holds a solution in which an organic halide is dissolved in an organic solvent, and a pump that transfers the solution from the raw material tank and adds it to the liquid before passing it through.

[0045] Here, instead of a solution in which an organic halide is dissolved in an organic solvent, a solution in which an organic halide and a ketone compound are dissolved in an organic solvent, or a solution in which an organic halide and a silane compound are dissolved in an organic solvent may be used.

[0046] The organic compound production apparatus 10 may further include a liquid cooling section (for example, a heat exchanger) between the packed tower 11 and the liquid passing section 12 for cooling the passed liquid.

[0047] FIG. 2 shows another example of the organic compound production apparatus of this embodiment.

[0048] The organic compound production apparatus 20 includes packed towers 21A, 21B, and 21C filled with magnesium 21a, a liquid passing section 22 that repeatedly passes a liquid through the packed towers 21A, 21B, and 21C, and raw material addition sections 23A, 23B, and 23C that add a raw material containing an organic halide to the liquid before passing it through the packed towers 21A, 21B, and 21C, respectively.

[0049] Packed towers 21A, 21B and 21C are similar to packed tower 11.

[0050] The liquid passage section 22 is similar to the liquid passage section 12 except that the organic solvent passed through it does not return to the buffer tank.

[0051] The raw material adding sections 23A, 23B and 23C are similar to the raw material adding section 13.

[0052] The organic compound production apparatus 20 may further include liquid cooling units (e.g., heat exchangers) for cooling the liquid passed through between the packed towers 21A and 21B and between the packed towers 21B and 21C.

[0053] [Organic halides] The organic halide is not particularly limited as long as it can react with magnesium, and examples thereof include organic chlorides, organic bromides, and organic iodides.

[0054] Examples of organic halides include alkyl halides; alkenyl halides; aryl halides such as chlorobenzene, α-chlorotoluene, bromobenzene, α-bromotoluene, iodobenzene, and α-iodotoluene; alkylene dihalides; and arylene dihalides such as o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-diiodobenzene, m-diiodobenzene, and p-diiodobenzene.

[0055] Examples of the alkyl group in the alkyl halide include linear or branched alkyl groups having 1 to 8 carbon atoms.

[0056] Specific examples of alkyl halides include chloromethane, chloroethane, chloropropane, 2-chloropropane, 1-chloro-2-methylpropane, 2-chloro-2-methylpropane, 2-bromo-2-methylpropane, chlorobutane, bromobutane, chloropentane, chlorocyclopentane, chlorohexane, bromomethane, bromoethane, bromopropane, 2-bromopropane, 1-bromo-2-methylpropane, bromobutane, bromopentane, bromocyclopentane, bromohexane, iodomethane, iodoethane, iodopropane, 2-iodopropane, 1-iodo-2-methylpropane, 2-iodo-2-methylpropane, iodopentane, iodocyclopentane, and iodohexane.

[0057] Examples of the alkenyl group in the halogenated alkenyl include linear or branched alkenyl groups having 2 to 8 carbon atoms.

[0058] Specific examples of the alkenyl halide include chloroethylene, 3-chloro-1-propene, bromoethylene, 3-bromo-1-propene, iodoethylene, and 3-iodo-1-propene.

[0059] The alkylene group in the dihalogenated alkylene group may be, for example, a linear or branched alkylene group having 1 to 8 carbon atoms.

[0060] Specific examples of dihalogenated alkylenes include 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,3-diiodopropane, 1,4-diiodobutane, and 1,5-diiodopentane.

[0061] Among the organic halides, alkyl halides and alkylene dihalides are preferred, and alkyl bromides and alkylene dibromides are more preferred, because they are useful as Grignard reagents.

[0062] [Organic solvents] The organic solvent is not particularly limited as long as it can dissolve the raw materials, and examples thereof include ether solvents.

[0063] Specific examples of the ether solvent include diethyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, etc., and two or more of them may be used in combination. Among these, tetrahydrofuran is preferred because it is easily available industrially and has a high boiling point.

[0064] Since organomagnesium halides are deactivated by reacting with water, the content of water in the organic solvent is preferably less than 500 ppm, and more preferably less than 100 ppm.

[0065] The amount of the organic solvent to be used may be determined appropriately taking into consideration the scale of the production equipment, the heat removal efficiency, and the like.

[0066] [Ketone compounds] The ketone compound is not particularly limited as long as it is capable of reacting with the organomagnesium halide, and examples thereof include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, ethyl propyl ketone, dipropyl ketone, methyl butyl ketone, ethyl butyl ketone, propyl butyl ketone, dibutyl ketone, methyl isopropyl ketone, ethyl isopropyl ketone, diisopropyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, diisobutyl ketone, propyl isobutyl ketone, methyl vinyl ketone, cyclohexanone, 2-methylcyclopentanone, acetophenone, benzophenone, and the like, and two or more of these may be used in combination.

[0067] [Silane compounds] The silane compound is not particularly limited as long as it is capable of reacting with an organomagnesium halide. Examples thereof include chlorosilane compounds such as dimethyldichlorosilane, methyltrichlorosilane, trimethylchlorosilane, methyldichlorosilane, vinyltrichlorosilane, phenyltrichlorosilane, and trichlorosilane; and alkoxysilane compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and octyltriethoxysilane; and the like, and two or more of these may be used in combination. [Example]

[0068] Examples of the present invention will be described below, but the present invention is not limited to these examples. [Examples 1-1 to 1-3] Propylmagnesium bromide was produced using an organic compound production apparatus 10 (see FIG. 1) in which a heat exchanger was installed between a packed tower 11 and a liquid passage section 12.

[0069] A cylindrical packed tower with an inner diameter of 2.2 cm and a height of 100 cm was packed with 350 g of magnesium pellets with an average particle size of 6 mm, giving a packing ratio of 80%.

[0070] Here, the particle size of magnesium was defined as the longest diameter of a triaxial measurement. The longest diameter of a triaxial measurement is the length of the longest side of a hypothetical rectangular parallelepiped circumscribing an irregular particle (see, for example, Junichiro Tsubaki, Michitaka Suzuki, and Yoshiteru Kanda; Introduction to Particle and Powder Technology, 2nd Revised Edition, Nikkan Kogyo Shimbun, Inc. (2016)). The particle's longest diameter was measured using an optical microscope with magnifications ranging from 10x to 200x. The average particle size was calculated by taking the number average of the longest diameters of 50 randomly selected particles.

[0071] A predetermined amount of 1-bromopropane (BP) was dissolved in a predetermined amount of tetrahydrofuran (THF) (water content: 10 ppm) to obtain a raw material solution.

[0072] Five liters of tetrahydrofuran (water content: 10 ppm) was placed in the buffer tank of the liquid-passing section 12, and the buffer tank and lines were heated to 40°C. The tetrahydrofuran was circulated for 30 minutes at a flow rate of 400 ml / min using a plunger pump with a liquid-contacting part made of polytetrafluoroethylene. Next, the raw material solution was placed in the raw material tank of the raw material adding section 13. The raw material solution was then continuously added to the circulating tetrahydrofuran at a predetermined flow rate for a predetermined period of time using a plunger pump with a liquid-contacting part made of polytetrafluoroethylene. The tetrahydrofuran was cooled to 40°C using a heat exchanger. The packed tower 11, the liquid-passing section 12, the raw material adding section 13, and the heat exchanger were connected via ¼-inch PFA tubing. After the introduction of the raw material solution began, the temperatures at the inlet, midpoint, and outlet of the packed tower 11 were measured using K-type thermocouples. After the completion of the addition of the raw material solution, tetrahydrofuran was circulated for 20 minutes, and then the entire amount of circulated tetrahydrofuran was recovered in a buffer tank. Propylmagnesium bromide was quantified by gas chromatography analysis, and the conversion rate of 1-bromopropane was calculated.

[0073] Table 1 shows the evaluation results of the temperature of the packed column and the conversion rate of 1-bromopropane.

[0074] [Table 1]

[0075] From Table 1, it can be seen that in Examples 1-1 to 1-3, the temperature rise in the reaction system was suppressed and the conversion rate of 1-bromopropane was high.

[0076] [Examples 2-1 and 2-2] 1,3-Bis(dimethylchlorosilyl)propane was produced in the same manner as in Examples 1-1 to 1-3, except that a solution in which 1,3-dibromopropane (DBP) and dichlorodimethylsilane (CMS) were each dissolved in tetrahydrofuran at a concentration of 2.8 mol / L was used as the raw material solution, and the raw material solution was continuously added to the circulating tetrahydrofuran at a predetermined flow rate for a predetermined time.

[0077] In addition, 1 H-NMR analysis and 29 The product was identified by Si-NMR analysis. 1,3-bis(dimethylchlorosilyl)propane was quantified by the internal standard method (internal standard substance: toluene), and the conversion of 1,3-dibromopropane was calculated.

[0078] Table 2 shows the evaluation results of the temperature of the packed column and the conversion rate of 1,3-dibromopropane.

[0079] [Table 2]

[0080] From Table 2, it can be seen that in Examples 2-1 and 2-2, the temperature rise in the reaction system was suppressed and the conversion rate of 1,3-dibromopropane was high. [Explanation of symbols]

[0081] 10, 20 Organic compound manufacturing equipment 11, 21A, 21B, 21C packed tower 11a, 21a magnesium 12, 22 Liquid passage part 13, 23A, 23B, 23C Raw material addition section

Claims

1. The method includes a step of circulating a liquid containing an organic solvent through a packed column packed with magnesium, a raw material containing an organic halide and a ketone compound or a silane compound is continuously added to the circulating liquid at an upstream side of the packed tower; The method for producing an organic compound further comprises cooling the circulating liquid downstream of the packed tower.

2. The method for producing an organic compound according to claim 1 , wherein the liquid is circulated through a single packed column.

3. When the total amount of organic halide added to the circulating liquid is A [mol] and the amount of magnesium packed in the packed tower is B [mol], the following formula can be used: A / B x α (In the formula, α is 0.9 or more and 1.2 or less.) The method for producing an organic compound according to claim 2 , wherein the number of times of circulating the solution is determined by the following:

4. a packed tower filled with magnesium; a liquid passing section for circulating a liquid containing an organic solvent through the packed tower; a raw material adding section, located upstream of the packed tower, for continuously adding a raw material containing an organic halide and a ketone compound or a silane compound to the circulating liquid; a liquid cooling section downstream of the packed tower for cooling the circulating liquid.

5. The organic compound production apparatus according to claim 4 , wherein the liquid passing section circulates the liquid through the single packed tower.

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