WO2017130679A1 - チオカルボニル化合物の製造方法 - Google Patents
チオカルボニル化合物の製造方法 Download PDFInfo
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- WO2017130679A1 WO2017130679A1 PCT/JP2017/000423 JP2017000423W WO2017130679A1 WO 2017130679 A1 WO2017130679 A1 WO 2017130679A1 JP 2017000423 W JP2017000423 W JP 2017000423W WO 2017130679 A1 WO2017130679 A1 WO 2017130679A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C325/00—Thioaldehydes; Thioketones; Thioquinones; Oxides thereof
- C07C325/02—Thioketones; Oxides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/20—Esters of monothiocarboxylic acids
- C07C327/22—Esters of monothiocarboxylic acids having carbon atoms of esterified thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/20—Esters of monothiocarboxylic acids
- C07C327/26—Esters of monothiocarboxylic acids having carbon atoms of esterified thiocarboxyl groups bound to carbon atoms of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/36—Esters of dithiocarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/38—Amides of thiocarboxylic acids
- C07C327/40—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C327/42—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of a saturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/38—Amides of thiocarboxylic acids
- C07C327/48—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to carbon atoms of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
- C07D307/84—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
- C07D307/85—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 2
Definitions
- the present invention relates to a method for producing a thiocarbonyl compound.
- Non-patent Document 1 As a method for producing a thiocarbonyl compound from a carbonyl compound, for example, production of a thiocarbonyl compound using diphosphorus pentoxide (P 4 S 10 ) is disclosed (Non-patent Document 1). In addition, 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide (generic name, Lawson's reagent, hereinafter Lawson unless otherwise specified) A method for producing a thiocarbonyl compound using a reagent is described (Patent Document 1, and Non-Patent Documents 2 and 3).
- Non-Patent Document 1 since hydrogen sulfide or sulfur dioxide is used as a sulfiding agent, various problems may occur in implementation on an industrial scale.
- diphosphorus pentasulfide when used as a sulfiding agent, diphosphorus pentasulfide is solid but has high hygroscopicity, and when it absorbs moisture, it decomposes to generate hydrogen sulfide, and many by-products are generated, resulting in purification work. There was a problem such as becoming necessary.
- Non-Patent Documents 2 and 3 when Lawson's reagent is used as a sulfurizing agent, there is no problem as in the case of using the above-mentioned sulfurizing agent, and a very excellent sulfurizing agent. In recent years, it has been widely used. However, Lawesson's reagent always produces a thiophosphine compound as a by-product after the reaction. For this reason, in order to take out the target compound with high purity, it is generally necessary to use column chromatography in the purification step, and it has been difficult to carry out it on an industrial scale. In particular, Non-Patent Document 3 clearly describes problems caused by using Lawson's reagent.
- a high-purity thiocarbonyl compound can be obtained by using diphosphatane disulfide containing a Lawson reagent as a sulfurizing agent. I found it.
- the present invention provides the following [1] to [6].
- a process for producing a compound (B) comprising a structural unit (I-3) comprising, in this order, a step (2) of alkali treatment with an alkaline aqueous solution.
- A represents any of —C—, —O—, —S—, or —NR 1 —, and R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- R 2 and R 3 each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkylthio group having 1 to 6 carbon atoms.
- Ar represents an aryl group having 6 to 10 carbon atoms
- a 1 and A 2 each independently represents an alkyl group having 1 to 6 carbon atoms
- a halogen atom n 1 and n 2 represents each independently an integer of 0 to 4.
- A is the same as in (I-1).
- [2] The production method according to [1], wherein the alkali treatment is performed with an aqueous alkali solution having a concentration of 10 to 25% by weight.
- the alkali is sodium hydroxide, potassium hydroxide, or a mixture thereof.
- a high-purity thiocarbonyl compound can be obtained by a production method that can be industrialized by removing a by-product derived from a sulfurizing agent by a simple purification method after the reaction.
- the present invention includes a step (1) of obtaining a mixture by heating the compound (A) containing the structural unit (I-1), the compound (C), and the solvent (X), preferably with mixing, A step (2) of subjecting the obtained mixture to alkali treatment is included in this order.
- the step (1) will be described in detail.
- the compound (A) used in the step (1) has the following formula (I-1)
- the structural unit represented by is included.
- A represents —C—, —O—, —S—, or —NR 1 —
- R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. From the viewpoint of reducing side reactions, -C -, - O-, or -NR 1 - are preferable, -O -, - NR 1 - is preferred.
- R 1 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- the compound (A) is preferably a compound represented by the following formula (I-2).
- M 1 and M 2 each independently represent any of a hydrogen atom, an aliphatic hydrocarbon group, an alkoxy group, an aromatic hydrocarbon group, or a heterocyclic group, and a combination thereof May have a substituent, may have a substituent, and M 1 and M 2 may be linked to each other to form a cyclic structure.
- M 1 and M 2 have at least one methylene group
- the methylene group is —O—, —S—, —CO—, —CS—, —COO—, CONR 4 —, and —NR 5 CO—. It may be substituted with any of them.
- R 4 and R 5 each independently represents an alkyl group having 1 to 10 carbon atoms, and may be linked to M 1 and / or M 2 to form a cyclic structure. Further, when M 1 and M 2 have a cyclic structure, the ring structure may be a condensed ring structure.
- A represents the same meaning as A in formula (I-1).
- the number of carbon atoms of M 1 and M 2 is not particularly limited, but is preferably 0 to 50 carbon atoms, more preferably 1 to 40 carbon atoms, still more preferably 2 to 30 carbon atoms, and most preferably 3 to 20 carbon atoms. is there. It is preferable for the carbon number of M 1 and M 2 to be in the above range since the solubility in the solvent (X) described later is good and the reactivity with the compound (C) is good.
- aliphatic hydrocarbon group examples include methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group, 1-butenyl group, 2 -Butenyl group and the like.
- aromatic hydrocarbon group examples include a phenyl group, a naphthyl group, a toluyl group, a xylyl group, and a mesityl group.
- the heterocyclic group refers to a group in which a heterocyclic structure is linked to the structural unit represented by the formula (I-1) via one linking group.
- Specific examples of the heterocyclic structure include pyrrolidine ring, pyrroline ring, pyrrole ring, piperidine ring, piperazine ring, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrazine ring, triazine ring, oxolane ring, oxane ring, Dioxane ring, furan ring, thiolane ring, thiophene ring, oxazole ring, thiazole ring, morpholine ring, indole ring, benzimidazole ring, benzofuran ring, benzothiazole ring, benzoxazole ring, quinoline ring, carbazole ring, porphyrin ring, etc. It is done.
- examples of the structure in which any of an aliphatic hydrocarbon group, an alkoxy group, an aromatic hydrocarbon group, and a heterocyclic group are combined include the following structures. (* Represents a bond.)
- substituents that M 1 and M 2 may have include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a thiol group, a sulfo group, an acryloyl group, a vinyl group, an amino group, and an azo group. And a formyl group.
- any of an aliphatic hydrocarbon group, an alkoxy group, an aromatic hydrocarbon group, and a heterocyclic group is preferable, and an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group are preferable.
- a cyclic group is more preferable.
- the substituent group of the M 1 and M 2 a halogen atom, a thiol group and an amino group, is preferable.
- Examples of the compound (A) include the following compounds.
- step (1) compound (C) is used as a sulfiding agent for compound (A).
- Compound (C) is represented by the following formula (II).
- Compound (C) is a diphosphatane disulfide compound such as Lawson's reagent.
- R 2 and R 3 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkylthio group having 1 to 6 carbon atoms.
- Ar represents an aryl group having 6 to 10 carbon atoms.
- the aryl group include a phenyl group (hereinafter abbreviated as Ph), a toluyl group, a xylyl group, and a naphthyl group.
- R 2 and R 3 may be appropriately selected according to the solubility of the compound (C) in the solvent (X) used in the reaction, but R 2 and R 3 are the same from the viewpoint of production of the compound (C).
- the structure is preferably a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or —O—Ph, and most preferably a methoxy group.
- a 1 and A 2 each independently represents an alkyl group having 1 to 6 carbon atoms or a halogen atom, and n 1 and n 2 each independently represents an integer of 0 to 4.
- a 1 and A 2 may be appropriately selected according to the solubility of the compound (C) in the solvent (X) used in the reaction, but A 1 and A 2 are the same from the viewpoint of production of the compound (C).
- Examples of the compound (C) include the following compounds.
- Compound (C) can be produced from diphosphorus pentoxide and a benzene derivative.
- the production method of Lawson reagent is described in, for example, non-patent literature (Organic Synthesis, Coll. Vol. 7, P372, 1990). Specifically, Lawesson's reagent can be produced by cooling the diphosphorus pentoxide in anisole after boiling, and filtering the precipitated crystals.
- the amount of compound (C) used in step (1) is usually 0.50 ⁇ Z to 5.0 ⁇ Z mol, preferably 0.50 ⁇ Z, relative to 1 mol of compound (A) used. It is in the range of ⁇ 2.0 ⁇ Z mol, more preferably 0.50 ⁇ Z to 1.0 ⁇ Z mol.
- Z represents the number of carbonyl groups that the compound (A) has in one molecule. If the usage-amount of a compound (C) is in the said range, it is preferable from a viewpoint of suppression of the side reaction resulting from a compound (C), and the ease of a refinement
- Compound (C) may be used alone, or a plurality of different compounds may be used.
- the solvent (X) to be used does not react with the compound (A) and compound (C) to be used, or the by-product resulting from the compound (B) and compound (C) produced by the reaction. If a thing is used, it will not specifically limit.
- the solvent (X) include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and mesitylene; hetero molecules in molecules such as anisole and thioanisole.
- Aromatic solvents having atoms aromatic heterocyclic solvents such as pyridine and pyrazine; ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane and 1,4-dioxane; and chlorination such as dichloromethane, chloroform, chlorobenzene and bromobenzene
- a hydrocarbon solvent is mentioned.
- toluene, xylene, mesitylene, and chlorobenzene are preferable.
- solvent (X) a plurality of solvents may be used in combination.
- the temperature at which the step (1) is carried out is preferably in the range of 30 ° C. to 160 ° C., more preferably in the range of 50 ° C. to 130 ° C., and most preferably 60 to 120 ° C. If the temperature which implements a process (1) is in the said range, it is preferable from a viewpoint of the solubility of a compound (A) and a compound (C), and side reaction suppression.
- the pressure in the reaction vessel for carrying out step (1) is usually atmospheric pressure. However, from the viewpoint of solubility of the compound (A) or the compound (C), when a solvent having a boiling point of 80 ° C. or lower is used as the solvent (X), it may be carried out under a pressurized condition. In this case, the pressure in the reaction vessel is usually in the range of 2 kPa to 1 MPa.
- step (1) compound (B) containing a structural unit represented by the following formula (I-3) is obtained by reaction between compound (A) and compound (C).
- a in formula (I-3) represents the same meaning as A in formula (I-1).
- compound (A) is a compound represented by formula (I-2)
- compound (B) obtained in step (1) is a compound represented by formula (I-4) below.
- a in the formula (I-4), M 1 , and M 2 represents A, M 1, and the same meaning as M 2 in the formula (I-2).
- Examples of the compound (B) include the following compounds.
- the present invention includes a step (2) of subjecting the obtained mixture to an alkali treatment.
- step (2) will be described.
- compound (C) is converted to a compound represented by the following formula (III-1) and formula (III-2).
- R 2 , R 3 , A 1 , A 2 , n 1 and n 2 in formula (III-1) and formula (III-2) each have the same meaning as in formula (II).
- the compounds represented by formula (III-1) and formula (III-2) are generally oxidizing.
- the compound represented by the formula (III-1) and the formula (III-2) is mixed in the compound (B).
- the compounds represented by the formulas (III-1) and (III-2) cause a side reaction.
- the compounds represented by the formulas (III-1) and (III-2) react with the oxidizing agent to inhibit the target reaction. Therefore, it is preferable to separate the compound (B) from the compound represented by the formula (III-1) and the formula (III-2).
- the compounds represented by the formulas (III-1) and (III-2) are converted into the compounds represented by the following formulas (IV-1) and (IV-2). It can be easily removed by converting to a water-soluble compound.
- R 2 , R 3 , A 1 , A 2 , n 1 , and n 2 in formula (IV-1) and formula (IV-2) have the same meaning as in formula (II).
- the alkali treatment carried out in the step (2) means that the compounds represented by the formula (III-1) and the formula (III-2) are converted into the formula (IV-1) and the formula (IV-2) using a basic compound. ).
- the basic compound used for the alkali treatment may be an organic compound base (hereinafter abbreviated as an organic base) or an inorganic compound base (hereinafter abbreviated as an inorganic base).
- organic base include triethylamine, pyridine, piperidine, imidazole, ethylenediamine, N, N-dimethyl-4-aminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5- And diazabicyclo [4.3.0] -5-nonene, 1,4-diazabicyclo [2.2.2] octane, and the like.
- the inorganic base include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, barium hydroxide and the like.
- the basic compound used is preferably an inorganic base, more preferably sodium hydroxide or potassium hydroxide. From the viewpoint of not reacting with the compound (B) obtained in the step (1) and economical efficiency.
- a basic compound may be used independently, respectively, and a plurality of different compounds may be used.
- the inorganic base may be used as it is, but it is preferably used as an aqueous solution having a predetermined concentration.
- an inorganic base is used as an aqueous solution, the compounds represented by formula (IV-1) and formula (IV-2) produced by alkali treatment can be extracted into the aqueous solution, and the compound (B) obtained in step (1) It is preferable because it can be easily separated.
- the concentration of the inorganic base is preferably in the range of 10 to 25% by weight, more preferably in the range of 15 to 23% by weight, and 18 to 22%. Most preferred is a weight percent range.
- the compounds represented by formula (III-1) and formula (III-2) are efficiently represented by formula (IV-1) and formula (IV-2). This is preferable because it can be converted into a compound and mass property deterioration can be prevented.
- the mass mentioned here means a liquid composition comprising the compound (A), the compound (B), the compound (C), the solvent (X) and the basic compound obtained in the step (1).
- Deterioration of mass properties means, for example, that the compounds represented by formula (III-1) and formula (III-2) and / or formula (IV-1) and formula (IV-2) are in a massive high viscosity state. It means that it becomes non-uniform property.
- a liquid separation improver may be used to improve the liquid separation property. Separation improver means that the difference in specific gravity between the organic layer and the aqueous layer is small during the separation operation, and it works to eliminate emulsions and precipitation that occur when low-solubility components and amphiphilic components are mixed.
- liquid separation improver examples include inorganic salt compounds such as lithium chloride, sodium chloride, potassium chloride, calcium chloride, and barium chloride; methanol, ethanol, 2-propanol, tetrahydrofuran, 1,4-dioxane, acetonitrile And amphiphilic solvents such as acetone and 2-butanone. A plurality of these liquid separation improvers may be used in combination.
- a solvent may be newly added to dissolve the compound (B).
- the solvent that can be used in this case include methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, di-ethylene, in addition to the solvent (X) described above.
- Alcohol solvents such as acetone alcohol; ketone solvents such as acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether, ethyl lactate and ⁇ -butyrolactone; N And aprotic polar solvents such as N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and the like. These solvents may be used in combination.
- the amount of the basic compound used for the alkali treatment is usually 2.0 / E to 20 / E mol, preferably 2.2 / E with respect to 1 mol of the compound (C) used in the step (1).
- E represents the valence of the basic compound.
- the compound represented by the formula (IV-1) and the formula (IV-2) can be efficiently converted into the aqueous solution. It is preferable because it can be extracted.
- the pH of the aqueous solution is preferably in the range of 12.0 to 13.9, and more preferably in the range of 13.0 to 13.9. It is preferable that the pH of the aqueous solution be within the above range because the compounds represented by the formula (III-1) and the formula (III-2) can be efficiently converted into the compound represented by the formula (IV).
- the temperature at which the alkali treatment is carried out is usually in the range of 40 to 90 ° C., preferably 50 to 85 ° C., more preferably 60 to 83 ° C. It is preferable that the temperature is within this temperature range because the compound represented by formula (III) can be efficiently converted into the compounds represented by formula (IV-1) and formula (IV-2).
- the mixture was cooled to an internal temperature of 80 ° C., 40 g of 20% aqueous sodium hydroxide solution was dropped into the system over 30 minutes using a dropping funnel, and then kept at an internal temperature of 80 ° C. for 12 hours or more.
- a 500 mL-jacketable separable flask having a two-way cock at the bottom was prepared separately, and a stirrer, a Dimroth condenser, and a thermometer were installed.
- a 60 ° C. heating medium was circulated through the jacket using a constant temperature circulator, and the temperature inside was adjusted to 60 ° C.
- the liquid separation solution was transferred to the separable flask, and the liquid separation lower layer (water layer) was removed from the lower two-way cock at an internal temperature of 60 ° C. 50 g of pure water was added to the remaining toluene container, stirred for 30 minutes at an internal temperature of 60 ° C., and then allowed to stand to remove the lower layer (aqueous layer). Separation washing with pure water was performed three times in total so that the drainage pH was ⁇ 9. The separated organic layer was concentrated under reduced pressure to adjust the concentration of Compound 2 to 25% and cooled to 25 ° C. The precipitated crystals were filtered using a Nutsche, and the obtained wet crystals were washed with 10 g of methanol and then dried at 60 ° C. with a vacuum dryer to obtain 9.44 g of dried crystals of Compound 2. Yield 90%.
- the mixture was cooled to an internal temperature of 80 ° C., and 57 g of a 20% sodium hydroxide aqueous solution was dropped into the system over 30 minutes using a dropping funnel, and then kept at an internal temperature of 80 ° C. for 12 hours or more.
- a 500 mL-jacketable separable flask having a two-way cock at the bottom was prepared separately, and a stirrer, a Dimroth condenser, and a thermometer were installed.
- a 60 ° C. heating medium was circulated through the jacket using a constant temperature circulator, and the temperature inside was adjusted to 60 ° C.
- the liquid separation solution was transferred to the separable flask, and the liquid separation lower layer (water layer) was removed from the lower two-way cock at an internal temperature of 60 ° C. 50 g of pure water was added to the remaining toluene container, stirred for 30 minutes at an internal temperature of 60 ° C., and then allowed to stand to remove the lower layer (aqueous layer). Separation washing with pure water was performed three times in total so that the drainage pH was ⁇ 9. The separated organic layer was concentrated under reduced pressure to adjust the concentration of Compound 3 to 25% and cooled to 25 ° C. The precipitated crystals were filtered using a Nutsche, and the obtained wet crystals were washed with 10 g of methanol and then dried at 60 ° C. in a vacuum dryer to obtain 8.89 g of Compound 3 as dry crystals. Yield 83%.
- Example 3 All were carried out in the same manner as in Example 1 except that the internal temperature at which the temperature was kept for 12 hours or more with a 20% aqueous sodium hydroxide solution was changed to 70 ° C. Using an ICP emission spectrometer ICPS-7510 (manufactured by Shimadzu Corporation), the amount of residual phosphorus in the dried crystals of Compound 2 obtained was quantified and found to be 88 ppm.
- Example 4 All were carried out in the same manner as in Example 1 except that the internal temperature at which the temperature was kept for 12 hours or more with a 20% aqueous sodium hydroxide solution was changed to 60 ° C. after the reaction. Using an ICP emission spectrometer ICPS-7510 (manufactured by Shimadzu Corporation), the amount of residual phosphorus in the dried crystals of Compound 2 obtained was quantified and found to be 1300 ppm.
- Example 5 The same procedure as in Example 1 was performed except that the caustic soda aqueous solution used after the reaction was changed to 100 g of an 8% aqueous solution. Using an ICP emission spectrometer ICPS-7510 (manufactured by Shimadzu Corporation), the amount of residual phosphorus in the dried crystals of Compound 2 obtained was quantified and found to be 2900 ppm.
Abstract
Description
(式(I-3)中、Aは(I-1)中と同様である。)
[2]10~25重量%濃度のアルカリ水溶液でアルカリ処理する[1]に記載の製造方法。
[3]アルカリが、水酸化ナトリウム、水酸化カリウム、又はこれらの混合物である[1]または[2]に記載の製造方法。
[4]60℃以上90℃以下でアルカリ処理する[1]~[3]のいずれかに記載の製造方法。
[5]溶媒(X)が、炭化水素溶媒である[1]~[4]のいずれかに記載の製造方法。
[6]混合しながら加熱する[1]~[5]のいずれかに記載の製造方法。
式(I-2)中、M1およびM2は、それぞれ独立に、水素原子、脂肪族炭化水素基、アルコキシ基、芳香族炭化水素基、または複素環基のいずれかを表し、これらを組み合わせた構造であってもよく、置換基を有していてもよく、また、M1とM2が互いに連結して環状構造を形成していてもよい。M1およびM2が少なくとも1つのメチレン基を有する場合、該メチレン基は-O-、-S-、-CO-、-CS-、-COO-、CONR4-、および-NR5CO-のうちのいずれかで置換されていてもよい。ここでR4、およびR5は、それぞれ独立に、炭素数1~10のアルキル基を表し、M1および又はM2と連結して環状構造を形成してもよい。また、M1およびM2が環状構造を有する場合、該環構造は縮環構造であってもよい。Aは、式(I-1)中のAと同じ意味を表す。
下部に二方コックを有する500mL-ジャケット付セパラブルフラスコを別途準備し、攪拌機、ジムロート冷却管、温度計を設置した。恒温循環装置を用いてジャケットに60℃熱媒を循環させ、内部を60℃に温調した。上記分液溶液を該セパラブルフラスコに移し、内温60℃にて分液下層(水層)を下部二方コックより取り除いた。残ったトルエン容器に純水50gを加え、内温60度にて30分間撹拌し、その後静置して下層(水層)を除去した。排水pHが<9になるよう、純水による分液洗浄を計3回実施した。分液後の有機層を減圧濃縮し、化合物2の濃度を25%に調整し、25℃まで冷却した。析出した結晶をヌッチェを用いて濾過し、得られた湿晶をメタノール10gで洗浄した後、減圧乾燥器で60℃にて乾燥し、化合物2の乾燥結晶9.44gを得た。収率90%。
下部に二方コックを有する500mL-ジャケット付セパラブルフラスコを別途準備し、攪拌機、ジムロート冷却管、温度計を設置した。恒温循環装置を用いてジャケットに60℃熱媒を循環させ、内部を60℃に温調した。上記分液溶液を該セパラブルフラスコに移し、内温60℃にて分液下層(水層)を下部二方コックより取り除いた。残ったトルエン容器に純水50gを加えて、内温60度にて30分間撹拌し、その後静置して下層(水層)を除去した。排水pHが<9になるよう、純水による分液洗浄を計3回実施した。分液後の有機層を減圧濃縮し、化合物3濃度を25%に調整し、25℃まで冷却した。析出した結晶をヌッチェを用いて濾過し、得られた湿晶をメタノール10gで洗浄した後、減圧乾燥器で60℃にて乾燥し、化合物3の乾燥結晶8.89gを得た。収率83%。
反応後に20%苛性ソーダ水溶液で12時間以上保温する内温を70℃に変更した以外、全て実施例1と同様に実施した。ICP発光分析装置ICPS-7510((株)島津製作所製)を用いて、得られた化合物2の乾燥結晶中の残存リン量を定量した結果、88ppmであった。
反応後に20%苛性ソーダ水溶液で12時間以上保温する内温を60℃に変更した以外、全て実施例1と同様に実施した。ICP発光分析装置ICPS-7510((株)島津製作所製)を用いて、得られた化合物2の乾燥結晶中の残存リン量を定量した結果、1300ppmであった。
反応後に使用する苛性ソーダ水溶液として、8%水溶液100gに変更した以外は全て実施例1と同様に実施した。ICP発光分析装置ICPS-7510((株)島津製作所製)を用いて、得られた化合物2の乾燥結晶中の残存リン量を定量した結果、2900ppmであった。
反応後に使用する苛性ソーダ水溶液として30%水溶液27gに変更したところ、滴下中に茶色の塊状不溶物が発生し、均一な撹拌が困難となった。
Claims (6)
- 構造単位(I-1)を含む化合物(A)、化合物(C)および溶媒(X)を加熱して混合物を得る工程(1)、および得られた混合物を25重量%以下の濃度のアルカリ水溶液でアルカリ処理する工程(2)をこの順に含む構造単位(I-3)を含む化合物(B)の製造方法。
(式(I-1)中、Aは、-C-、-O-、-S-、または-NR1-のいずれかを表し、R1は水素原子または炭素数1~10のアルキル基を表す。)
(化合物(C)中、R2およびR3は、それぞれ独立に水素原子、水酸基、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、炭素数1~6のアルキルチオ基、または-O-Arを表し、Arは炭素数6~10のアリール基を表し、A1およびA2は、それぞれ独立に炭素数1~6のアルキル基、ハロゲン原子を表し、n1およびn2は、それぞれ独立に0~4の整数を表す。)
(式(I-3)中、Aは(I-1)中と同様である。) - 10~25重量%濃度のアルカリ水溶液でアルカリ処理する請求項1に記載の製造方法。
- アルカリが、水酸化ナトリウム、水酸化カリウム、又はこれらの混合物である請求項1または2に記載の製造方法。
- 60℃以上90℃以下でアルカリ処理する請求項1~3のいずれかに記載の製造方法。
- 溶媒(X)が、炭化水素溶媒である請求項1~4のいずれかに記載の製造方法。
- 混合しながら加熱する請求項1~5のいずれかに記載の製造方法。
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