WO2015166962A1 - Composition - Google Patents

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Publication number
WO2015166962A1
WO2015166962A1 PCT/JP2015/062879 JP2015062879W WO2015166962A1 WO 2015166962 A1 WO2015166962 A1 WO 2015166962A1 JP 2015062879 W JP2015062879 W JP 2015062879W WO 2015166962 A1 WO2015166962 A1 WO 2015166962A1
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WIPO (PCT)
Prior art keywords
compound
reaction
range
dibromoethylene
ppm
Prior art date
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PCT/JP2015/062879
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English (en)
Japanese (ja)
Inventor
淳 白井
寿美 石原
洋介 岸川
Original Assignee
ダイキン工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from JP2015012510A external-priority patent/JP5987926B2/ja
Application filed by ダイキン工業株式会社 filed Critical ダイキン工業株式会社
Priority to CN201580022827.5A priority Critical patent/CN106255675B/zh
Publication of WO2015166962A1 publication Critical patent/WO2015166962A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/204—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being a halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/075—Acyclic saturated compounds containing halogen atoms containing bromine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/14—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing bromine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a composition (in particular, a 1,1-dibromoethylene composition (that is, a composition containing 1,1-dibromoethylene as a main component)).
  • a composition in particular, a 1,1-dibromoethylene composition (that is, a composition containing 1,1-dibromoethylene as a main component)).
  • 1,1-Dibromoethylene is a synthetic intermediate for pharmaceuticals (for example, antibiotics), a synthetic intermediate for optical fiber sheath materials, a synthetic intermediate for coating materials, a synthetic intermediate for semiconductor resist materials, and a highly functional compound. This compound is useful as an intermediate for the synthesis of molecular monomers.
  • 1,1-dibromoethylene is obtained by dehydrobromination of 1,1,2-tribromoethane (Patent Document 1).
  • 1,1-Dibromoethylene has low stability, and even when stored in a light-shielded atmosphere under an inert gas atmosphere such as nitrogen, the purity is reduced in a short time and insoluble powder is precipitated. For this reason, even when used as a synthetic intermediate as described above, the handling thereof is not easy. Accordingly, an object of the present invention is to provide a means for stably maintaining 1,1-dibromoethylene.
  • the present invention includes the following aspects.
  • Item 1 [A] 1,1-dibromoethylene, [B] one or more amine compounds, and [C] (1) a compound having a hydroxyl group, (2) a compound having a sulfide bond, (3) a compound having a thiophenolic or thiol sulfur atom, (4) A composition containing one or more compounds selected from the group consisting of a sulfite compound and (5) a nitrite compound.
  • Item 2. The composition according to Item 1, wherein the one or more amine compounds are triethylamine.
  • 1,1-dibromoethylene [B] one or more amine compounds, and [C] (1) a compound having a hydroxyl group, (2) a compound having a sulfide bond, (3) A compound having a thiophenolic or thiol sulfur atom, and (4) a sulfite compound, and (5) one or more compounds selected from the group consisting of a nitrous acid compound. , 1,1-dibromoethylene stabilization method.
  • 1,1-dibromoethylene contained therein can be stably maintained.
  • the phrase “contains” includes the phrase “consisting essentially of” and the phrase “consisting of”.
  • composition of the present invention comprises: 1,1-dibromoethylene, One or more amine compounds, and (1) a compound having a hydroxyl group, (2) a compound having a sulfide bond, (3) a compound having a thiophenolic or thiol sulfur atom, It contains one or more compounds selected from the group consisting of (4) a sulfite compound and (5) a nitrite compound.
  • the composition of the present invention is a 1,1-dibromoethylene composition, that is, a composition containing 1,1-dibromoethylene as a main component.
  • the content of 1,1-dibromoethylene in the composition of the present invention is, for example, 50% (w / w) or more, 60% (w / w) or more, 70% (w / w) or more, 80% (w / w). w) or more, 90% (w / w) or more, 95% (w / w) or more, 96% (w / w) or more, 97% (w / w) or more, 98% (w / w) or more, or It can be 99% (w / w) or more.
  • composition of the present invention is stable. That is, in the composition of the present invention, 1,1-dibromoethylene has high stability.
  • an aliphatic primary amine an aliphatic secondary amine, an aliphatic tertiary amine, an alicyclic secondary amine, an alicyclic tertiary amine
  • examples include aromatic amines, heterocyclic amines, and polymer-supported amine compounds.
  • Examples of the aliphatic primary amine include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, and ethylenediamine.
  • Examples of the aliphatic secondary amine include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, and dicyclohexylamine.
  • Examples of the aliphatic tertiary amine include trimethylamine, triethylamine, diisopropylethylamine, tributylamine, and N, N, N ′, N′-tetramethylethylenediamine.
  • Examples of the alicyclic secondary amine include piperidine, piperazine, pyrrolidine, and morpholine.
  • Examples of the alicyclic tertiary amine include N-methylpiperazine, N-methylpyrrolidine, 5-diazabicyclo [4.3.0] nonane-5-ene, and 1,4-diazabicyclo [2.2.2]. ] Octane is mentioned.
  • Examples of the aromatic amine include aniline, methylaniline, dimethylaniline, N, N-dimethylaniline, haloaniline, and nitroaniline.
  • Heterocyclic amines include, for example, pyridine, melamine, pyrimidine, piperazine, quinoline, and imidazole.
  • Examples of the polymer-supported amine compound include polyallylamine and polyvinyl pyridine.
  • the amine compound may be used alone or in combination of two or more.
  • the amine compound is preferably a compound containing neither an oxygen atom nor a sulfur atom.
  • the amine compound is preferably one or more amine compounds selected from pyridine, melamine, diisopropylethylamine, tributylamine, triethylamine, and the like.
  • the amine compound is more preferably one or more amine compounds selected from pyridine, melamine, triethylamine, and the like.
  • the amount of the one or more amine compounds in the composition of the present invention is preferably in the range of 100 to 50,000 ppm (w / w), more preferably 100 to 10,000 ppm, relative to 1,1-dibromoethylene. (W / w), more preferably within a range of 100 to 3000 ppm (w / w), even more preferably within a range of 100 to 2000 ppm (w / w), and particularly preferably within a range of 100 to 1500 ppm ( w / w).
  • the composition of the present invention comprises: (1) a compound having a hydroxyl group, (2) a compound having a sulfide bond, (3) a compound having a thiophenolic or thiol sulfur atom, One or more compounds selected from the group consisting of (4) a sulfite compound and (5) a nitrite compound (in this specification, the group may be referred to as a compound group (C))
  • the compound may be referred to as compound (C).) Containing.
  • the compound (C) is preferably a stabilizer.
  • the “stabilizer” can be a “polymerization inhibitor”, a “decomposition inhibitor”, or a “polymerization inhibitor” and a “decomposition inhibitor”.
  • the said compound (C) may be used individually by 1 type, or may be used in combination of 2 or more type.
  • Examples of the “(1) hydroxyl group-containing compound” include, for example, a formula such as methanol, ethanol, isopropyl alcohol, and t-butanol: R—OH (wherein R is, for example, an alkyl having 1 to 6 carbon atoms) An alcohol represented by a group); and phenol, hydroquinone, 4-methoxyphenol, 2,5-di-tert-butylhydroquinone, methylhydroquinone, tert-butylhydroquinone (TBH), p-benzoquinone, methyl-p -Substituted with one or more hydroxyl groups such as benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenyl-p-benzoquinone, and 2,6-di-tert-butyl-4-methylphenol (BHT)
  • the number of carbon atoms in the compound is preferably a 6-20.
  • the compound may be simply referred to as phenolic compounds.
  • the “(2) compound having a sulfide bond” include, for example, a dialkyl sulfide (the two “alkyl” have the same or different carbon number, preferably 1 to 6), and a diphenyl sulfide structure.
  • compounds having a phenyl sulfide structure and having a sulfide bond having 6 to 20 carbon atoms, such as diphenyl sulfide and phenothiazine such as diphenyl sulfide and phenothiazine.
  • Examples of the “(3) compound having a thiophenolic or thiol sulfur atom” include R (—SH) such as thiophenol, benzenedithiol, 1,2-ethanedithiol, and 1,3-propanedithiol.
  • R represents, for example, an alkane having 1 to 6 carbon atoms or an aromatic carbocyclic ring having 6 to 12 carbon atoms (eg, benzene, diphenyl); and n represents, for example, 1 or 2 Represents an integer.
  • R represents, for example, an alkane having 1 to 6 carbon atoms or an aromatic carbocyclic ring having 6 to 12 carbon atoms (eg, benzene, diphenyl); and n represents, for example, 1 or 2 Represents an integer.
  • the compound represented by this is mentioned.
  • Examples of the “(4) sulfite compound” include potassium sulfite, calcium sulfite, sodium hydrogen sulfite, sodium sulfite, barium sulfite, magnesium sulfite, dimethyl sulfite, diethyl sulfite, diamyl sulfite, dipropyl sulfite, and diisopropyl sulfite.
  • Examples of the “(5) nitrite compound” include potassium nitrite, sodium nitrite, Mention may be made of methyl nitrite, ethyl nitrite, amyl nitrite, propyl nitrite and isopropyl nitrite.
  • the compound (C) is preferably the “(1) hydroxyl group-containing compound”, and more preferably a phenol compound.
  • the compound (C) include hydroquinone, 4-methoxyphenol, 2,5-di-tert-butylhydroquinone, methylhydroquinone, tert-butylhydroquinone (TBH), p-benzoquinone, methyl-p -Benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,6-di-tert-butyl-4-methylphenol (BHT), and phenothiazine.
  • the compound (C) is preferably one or more compounds selected from 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol (BHT), phenothiazine, and the like.
  • the compound (C) is particularly preferably 2,6-di-tert-butyl-4-methylphenol (BHT).
  • the composition of the present invention comprises: [1] one or more of such suitable compounds (C), and optionally, [2] Other than the “one or more suitable compounds (C)” (1) a compound having a hydroxyl group, (2) a compound having a sulfide bond, (3) a compound having a thiophenolic or thiol sulfur atom, It can be a composition containing one or more compounds selected from the group consisting of (4) a sulfite compound and (5) a nitrite compound. That is, a preferred composition of the present invention is, for example, a composition in which one of the “one or more compounds (C)” is 2,6-di-tert-butyl-4-methylphenol (BHT). The composition is a composition containing one or more compounds (C) other than 2,6-di-tert-butyl-4-methylphenol (BHT), if desired.
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • the content of the compound (C) in the composition of the present invention is preferably in the range of 100 to 50000 ppm (w / w), more preferably 100 to 10000 ppm (with respect to 1,1-dibromoethylene).
  • w / w more preferably in the range of 100 to 3000 ppm (w / w), even more preferably in the range of 100 to 2000 ppm (w / w), particularly preferably in the range of 100 to 1500 ppm (w / W).
  • the content of the one or more amine compounds is preferably in the range of 100 to 50,000 ppm (w / w), more preferably 100 to 50,000, based on 1,1-dibromoethylene.
  • the content of the one or more compounds (C) is preferably in the range of 100 to 50000 ppm (w / w) with respect to 1,1-dibromoethylene.
  • the total content of one or more amine compounds and the total content of the one or more compounds (C) is preferably 200 to 100,000 ppm with respect to 1,1-dibromoethylene.
  • the range of (w / w) more preferably within the range of 200 to 20000 ppm (w / w), and even more preferably within the range of 200 to 6000 ppm (w / w).
  • composition of the present invention can be produced, for example, by the production method described below.
  • 1,1,2-tribromoethane and / or 1,1,1-tribromoethane is dehydrobrominated using a base, Step B to obtain 1-dibromoethylene is included.
  • Step B At any point with respect to Step B, that is, at any time before, during, and after the reaction in Step B, (1) one or more amine compounds and ( 2)
  • the composition of the present invention can be produced by adding each of the one or more compounds (C).
  • (1) one or more amine compounds and (2) one or more compounds (C) may be added as follows: A mode in which both are added from the beginning of step B (this includes “before the reaction of step B”), A mode in which one is added from the beginning of the step B and the other is added after the start of the reaction in the step B (this includes “after the reaction in the step B”), A mode in which one is added from the beginning of the step B and both are added after the start of the reaction in the step B (that is, a mode in which the “one” is further added), A mode in which both are added after completion of the reaction without adding them at the beginning of the step B, An example of adding both at the same time during the reaction without adding them at the beginning of Step B and an example of adding them separately during the reaction without adding them at the beginning of Step B are exemplified.
  • the reaction without adding them at the beginning of Step B is exemplified.
  • the amount of the one or more amine compounds used in the method for producing the composition of the present invention, and the amount of the one or more compounds (C) depends on the desired amount of these in the composition of the present invention. Just decide.
  • the one or more amine compounds can function as the base in Step B when added to the reaction system before and during the reaction in Step B.
  • the one or more amine compounds can also function as a stabilizer described later.
  • 1,1,2-Tribromoethane and 1,1,1-tribromoethane can be produced by a known method or a method analogous thereto, respectively.
  • Examples of the base used in Step B include inorganic bases such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide; inorganic basic salts such as sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, and sodium bicarbonate. And organic bases such as amine compounds.
  • the example of the said amine compound is the same as the example of the amine compound which the composition of this invention demonstrated above contains.
  • Preferable examples of the base include sodium hydroxide, potassium hydroxide, ammonia and triethylamine.
  • the said base may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the combination may be, for example, a combination of an inorganic base and an amine compound exemplified as a stabilizer described later.
  • the base may be used in the form of an aqueous solution (eg, sodium hydroxide aqueous solution, aqueous ammonia).
  • the water of the aqueous solution can function as a reaction solvent.
  • the amount of the base is preferably in the range of 0.9 equivalent to 2.0 equivalents relative to the total amount of 1,1,2-tribromoethane and 1,1,1-tribromoethane, and more Preferably, it is in the range of 1.0 equivalent to 1.5 equivalent, more preferably in the range of 1.0 equivalent to 1.2 equivalent.
  • the amount of the base including the amine compound is preferably such an amount.
  • the upper limit of the reaction temperature in Step B is preferably 100 ° C, more preferably 80 ° C, and still more preferably 60 ° C.
  • the lower limit of the reaction temperature in Step B is preferably 0 ° C, more preferably 5 ° C, and still more preferably 10 ° C.
  • the reaction temperature in Step B is preferably in the range of 0 ° C. to 100 ° C., more preferably in the range of 5 ° C. to 80 ° C., still more preferably in the range of 10 ° C. to 60 ° C.
  • the reaction time of step B is usually in the range of 0.5 to 40 hours.
  • Step B can be performed preferably in the presence of a stabilizer.
  • the stabilizer can be added to the reaction system before the reaction in Step B and at any time during the reaction.
  • the stability of 1,1-dibromoethylene, which is the product of Step B can be improved.
  • Part or all of the stabilizer is a component contained in the composition of the present invention.
  • the one or more amine compounds and / or the one or more compounds (C) can be a stabilizer.
  • the stabilizer is preferably the “(1) hydroxyl group-containing compound”, and more preferably a phenol compound. In the production method, a stabilizer other than the stabilizer may also be used.
  • the stabilizer used in the production method is preferably diisopropylethylamine, tributylamine, triethylamine, 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol (BHT), phenothiazine and the like. Can be mentioned.
  • the said stabilizer may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the amount is preferably 100 to 50,000 ppm (w / w) relative to the total amount of 1,1,2-tribromoethane and 1,1,1-tribromoethane.
  • range of 100 to 1500 ppm (w / w) is particularly preferable.
  • the amine compound as the stabilizer can also function as the base.
  • the stabilizer preferably an inorganic base as the base and a stable It is preferable to use in combination with an amine compound as an agent.
  • the amine compound as a stabilizer may function as a base here, while the amine compound as a base may function as a stabilizer.
  • the reaction of step B is preferably carried out in the presence of a reaction solvent.
  • the reaction solvent include a water-soluble solvent, water, and a mixed solvent of two or more thereof.
  • the reaction solvent is preferably a water-soluble solvent or a mixed solvent of a water-soluble solvent and water.
  • the mixed solvent of water-soluble solvent and water is a mixed solvent containing a water-soluble solvent and water, and may contain a solvent other than these, but preferably consists essentially of a water-soluble solvent and water, More preferably, it consists only of a water-soluble solvent and water.
  • water may be derived from an aqueous base solution as described above.
  • reaction solvent or the water-soluble solvent in the reaction solvent for example, Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butyl alcohol; Ketones such as acetone and methyl ethyl ketone (MEK); And ethers such as diethyl ether and tetrahydrofuran (THF); and acetic acid, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), and 1-methyl-2-pyrrolidone (NMP).
  • the water-soluble solvent is preferably methanol, DMF, THF, or NMP.
  • the amount of the reaction solvent is usually in the range of 0 to 20 parts by weight, preferably 1 part by weight of the total amount of 1,1,2-tribromoethane and 1,1,1-tribromoethane, preferably It is in the range of 0.1 to 15 parts by weight, more preferably in the range of 0.1 to 10 parts by weight.
  • Step B is performed in the presence of water and in the absence of a water-soluble organic solvent, it is preferable to use a phase transfer catalyst.
  • the water can be water as the “reaction solvent” or water of an aqueous solution of the base.
  • the phase transfer catalyst include quaternary ammonium such as tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium sulfate, and trioctylmethylammonium chloride. Salts; quaternary phosphonium salts such as tetrabutylphosphonium chloride; pyridinium compounds such as dodecylpyridinium chloride; and crown ethers.
  • tetramethylammonium chloride or tetrabutylammonium bromide is preferable.
  • the amount thereof is preferably in the range of 0.01 equivalent to 1 equivalent with respect to the total amount of 1,1,2-tribromoethane and 1,1,1-tribromoethane. More preferably, it is in the range of 0.01 equivalents to 0.5 equivalents, more preferably in the range of 0.01 equivalents to 0.1 equivalents.
  • Step B 1,1,2-tribromoethane and / or 1,1,1-tribromoethane, reaction solvent, and stabilizer placed in a reactor And a method of adding a reaction solvent solution of a base.
  • the 1,1-dibromoethylene obtained by the production method can be isolated or purified by a conventional method, if necessary.
  • the method is preferably a method in which the one or more amine compounds and the one or more compounds (C) are not removed or are not easily removed, such as by adding water to separate the liquid.
  • a stabilizer may be added to the product.
  • “After the reaction of Step B” can be after isolation or purification of 1,1-dibromoethylene.
  • the storage stability of the product can be improved by adding a stabilizer to the product after the reaction in Step B.
  • the stabilizer include the same stabilizers used before and after the reaction in Step B and at any time during the reaction (that is, during the reaction in Step B).
  • the stabilizer added to the product after the reaction of Step B is the same as the stabilizer used during the reaction of Step B. May be different.
  • the stabilizer used after the reaction in the step B is preferably different from the stabilizer used in the reaction in the step B.
  • at least one of the two or more stabilizers used after the reaction in Step B is different from the stabilizer used in the reaction in Step B. It is also preferable.
  • one or more amine compounds are added to the reaction system before or during the reaction of Step B, and 1 More than one kind of compound (C) (preferably “(1) a compound having a hydroxyl group”, more preferably a phenol compound, particularly preferably BHT) is added after the reaction in Step B (preferably 1,1- Add to product after isolation or purification of dibromoethylene).
  • the amount of stabilizer added to the product after the reaction of Step B is preferably in the range of 100-50000 ppm (w / w), more preferably 100-10000 ppm, relative to 1,1-dibromoethylene.
  • the one or more amine compounds and the one kind are included in the reaction system before the reaction in Step B and at any time during the reaction (that is, during the reaction in Step B).
  • the composition of the present invention can be obtained by adding the above compound (C) (preferably, the “(1) hydroxyl group-containing compound”, more preferably a phenol compound, and particularly preferably BHT).
  • the one or more amine compounds and the one or more compounds (C) preferably the “(1) hydroxyl group-containing compound”, more preferably a phenolic compound, particularly preferably the reaction system of Step B. Is preferably added before the reaction in Step B.
  • the amount of the one or more amine compounds added to the reaction system during the reaction in Step B is preferably 100 to 50,000 ppm relative to 1,1-dibromoethylene ( w / w), more preferably within the range of 100 to 10,000 ppm (w / w), even more preferably within the range of 100 to 3000 ppm (w / w), even more preferably between 100 and 2000 ppm (w / W), particularly preferably in the range of 100 to 1500 ppm (w / w).
  • the one or more compounds (C) (preferably the “(1) hydroxyl group-containing compound”, more preferably, added to the reaction system during the reaction of the step B (preferably before the reaction of the step B),
  • the amount of phenolic compound, particularly preferably BHT is preferably in the range from 100 to 50,000 ppm (w / w), more preferably from 100 to 10,000 ppm (w / w), relative to 1,1-dibromoethylene. In the range of 100 to 3000 ppm (w / w), more preferably in the range of 100 to 2000 ppm (w / w), particularly preferably in the range of 100 to 1500 ppm (w / w). Within range.
  • the one or more amine compounds are added to the reaction system before the reaction in Step B and at any time during the reaction (that is, during the reaction in Step B).
  • the one or more compounds (C) preferably, “(1) a compound having a hydroxyl group”, more preferably a phenol compound, particularly preferably BHT” is added to the product.
  • the amine compound is added to the reaction system in Step B before the reaction in Step B.
  • the amount of the one or more amine compounds added to the reaction system during the reaction in Step B is preferably 100 to 50,000 ppm relative to 1,1-dibromoethylene ( w / w), more preferably within the range of 100 to 10,000 ppm (w / w), even more preferably within the range of 100 to 3000 ppm (w / w), even more preferably between 100 and 2000 ppm (w / W), particularly preferably in the range of 100 to 1500 ppm (w / w).
  • the amount of the one or more compounds (C) (preferably “(1) a compound having a hydroxyl group”, more preferably a phenol compound, particularly preferably BHT) added to the product after the reaction in Step B is preferably in the range of 100 to 50,000 ppm (w / w), more preferably in the range of 100 to 10000 ppm (w / w), still more preferably in the range of 100 to 3000 ppm, relative to 1,1-dibromoethylene.
  • one or more amine compounds are added to the reaction system during the reaction of Step B, and one or more additional amines are added to the product after the reaction of Step B.
  • a compound and one or more compounds (C) preferably, the “(1) hydroxyl group-containing compound”, more preferably a phenol compound, and particularly preferably BHT) are added.
  • the addition of the “one or more amine compounds” to the reaction system of Step B is preferably before the reaction of Step B.
  • the amount of the one or more amine compounds added to the reaction system during the reaction in Step B is preferably 100 to 50,000 ppm relative to 1,1-dibromoethylene ( w / w), more preferably within the range of 100 to 10,000 ppm (w / w), even more preferably within the range of 100 to 3000 ppm (w / w), even more preferably between 100 and 2000 ppm (w / W), particularly preferably in the range of 100 to 1500 ppm (w / w).
  • the amount of the one or more additional amine compounds added to the product after the reaction of Step B is preferably in the range of 100 to 50000 ppm (w / w) relative to 1,1-dibromoethylene, more Preferably, within the range of 100 to 10,000 ppm (w / w), more preferably within the range of 100 to 3000 ppm ppm (w / w), even more preferably within the range of 100 to 2000 ppm (w / w), particularly preferably Is in the range of 100-1500 ppm (w / w).
  • the amount of the one or more compounds (C) (preferably “(1) a compound having a hydroxyl group”, more preferably a phenol compound, particularly preferably BHT) added to the product after the reaction in Step B is preferably in the range of 100 to 50,000 ppm (w / w), more preferably in the range of 100 to 10000 ppm (w / w), still more preferably in the range of 100 to 3000 ppm, relative to 1,1-dibromoethylene.
  • the method for stabilizing 1,1-dibromoethylene of the present invention comprises: 1,1-dibromoethylene, 1 or more types of amine compounds and 1 or more types of compounds (C) (preferably said "(1) the compound which has a hydroxyl group", More preferably, it is a phenol compound, Most preferably, it is BHT) It is characterized by coexisting with.
  • the coexistence can be performed, for example, in the same manner as in the method for producing the composition of the present invention described above.
  • compositions of the invention can be used in conventional 1,1-dibromoethylene applications. Furthermore, since 1,1-dibromoethylene contained therein is stably maintained, the composition can be used for applications where it has not been easy to use 1,1-dibromoethylene.
  • the composition of the present invention includes, for example, 1,1-dibromo-1-fluoroethane, which includes step 2A of reacting 1,1-dibromoethylene with hydrogen fluoride to obtain 1,1-dibromo-1-fluoroethane. It can use for the manufacturing method of. [Step 2A] In step 2A, 1,1-dibromoethylene is reacted with hydrogen fluoride to give 1,1-dibromo-1-fluoroethane. The 1,1-dibromoethylene is 1,1-dibromoethylene in the composition of the present invention.
  • the composition of the present invention is composed of the one or more amine compounds and the one or more compounds (C) (preferably the “(1) hydroxyl group-containing compound”, more preferably a phenol compound, particularly preferably Can be suitably used in the production method of 1,1-dibromo-1-fluoroethane as it is without removing BHT).
  • the reaction of step 2A can be a liquid phase reaction or a gas phase reaction.
  • the reaction in step 2A is preferably a liquid phase reaction.
  • the reaction of step 2A can be carried out in the absence or presence of a solvent.
  • the reaction of step 2A is preferably carried out in the absence of a solvent.
  • examples of the solvent are: Alcohol solvents (eg, methanol, ethanol, n-propanol, isopropanol, and n-BuOH); Ketone solvents (eg, acetone and methyl ethyl ketone (MEK)); Ether solvents (eg, diethyl ether, tetrahydrofuran (THF), and 1-methoxy-2- (2-methoxyethoxy) ethane (Diglyme)); Halogen-containing solvents (eg: Methylene chloride, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, and Hydrochlorofluoroalkanes such as
  • Step 2A is preferably carried out using an autoclave as the reaction vessel.
  • the amount of hydrogen fluoride is usually within the range of 0.5 to 60 mol, preferably within the range of 3 to 50 mol, more preferably with respect to 1 mol of 1,1-dibromoethylene in the composition of the present invention. Within the range of 5 to 40 moles.
  • Step 2A is usually performed at a temperature in the range of 0 to 200 ° C, preferably in the range of 5 to 80 ° C, more preferably in the range of 5 to 70 ° C.
  • the temperature can be adjusted, for example, by adjusting the external temperature of the reaction vessel to a predetermined temperature. It can be considered that the internal temperature in the reaction vessel is substantially the same as the external temperature.
  • the reaction time in Step 2A is usually within the range of 1 to 40 hours, preferably within the range of 1 to 24 hours, and more preferably within the range of 1 to 20 hours. 1,1-dibromo-1-fluoroethane can be obtained after the reaction time has elapsed, for example, by cooling the temperature of the reaction system by cooling, adding water to the reaction solution, and then separating the solution it can.
  • the hydrogen fluoride layer and the 1,1-dibromo-1-fluoroethane layer are separated by a liquid separation operation to obtain 1,1-dibromo-1-fluoro. While obtaining ethane, hydrogen fluoride can also be recovered.
  • hydrogen fluoride is distilled off under reduced pressure to obtain 1,1-dibromo-1-fluoroethane, and hydrogen fluoride may be recovered. It can.
  • the cooling method can be, for example, cooling by leaving at room temperature, cooling with ice water, cooling with a chiller, or cooling with dry ice.
  • the obtained 1,1-dibromo-1-fluoroethane can be further purified by known purification methods such as solvent extraction, drying, filtration, distillation, concentration, and combinations thereof, if desired.
  • the hydrogen fluoride used in Step 2A is commercially available.
  • the hydrogen fluoride used in Step 2A can be, for example, in the form of anhydrous hydrogen fluoride (that is, anhydrous hydrofluoric acid) or hydrofluoric acid (that is, aqueous hydrogen fluoride solution, hydrofluoric acid).
  • the hydrogen fluoride used in step 2A may be in the form of a gas.
  • the gaseous hydrogen fluoride can be a mixture of HF (hydrogen fluoride) and a polymer of HF.
  • step 2A is preferably performed in the presence of an amine compound.
  • Part or all of the amine compound can be derived from the composition of the present invention.
  • part or all of the hydrogen fluoride may form a complex with the amine compound.
  • the example of the said amine compound added by process 2A can be the same as the example of the amine compound which the composition of this invention contains.
  • the amine compound is preferably the same as the amine compound contained in the composition of the present invention.
  • the amount of the amine compound in step 2A is preferably in the range of 1 to 100% (w / w), more preferably in the range of 1 to 50% (w / w), and more preferably relative to hydrogen fluoride. Preferably, it is in the range of 1 to 30% (w / w), more preferably 3 to 30% (w / w).
  • Hydrogen fluoride may be added to the composition of the present invention
  • a mixture of an amine compound and hydrogen fluoride may be added to the composition of the present invention
  • Hydrogen fluoride and an amine compound may be added to the composition of the present invention, respectively
  • a mixture of an amine compound and hydrogen fluoride and hydrogen fluoride may be added to the composition of the present invention, respectively.
  • the mixture of amine compound and hydrogen fluoride can be a complex of amine compound and hydrogen fluoride.
  • composition of the present invention is now made up of the one or more amine compounds and the one or more compounds (C) (preferably the “(1) a compound having a hydroxyl group”, more preferably a phenol compound, particularly preferably Is used as it is in the method for producing 1,1-dibromo-1-fluoroethane without removing BHT), in the method for producing 1,1-dibromo-1-fluoroethane including the step 2A, 1,1-dibromo-1-fluoroethane,
  • the one or more amine compounds and the one or more compounds (C) preferably, the “(1) hydroxyl group-containing compound”, more preferably a phenol compound, and particularly preferably BHT).
  • a composition containing is obtained.
  • 1,1 obtained by a process for producing 1,1-dibromo-1-fluoroethane which comprises step 2A of reacting 1,1-dibromoethylene with hydrogen fluoride to obtain 1,1-dibromo-1-fluoroethane
  • 1-Bromo-1-fluoroethylene can be synthesized from -dibromo-1-fluoroethane by a known method (for example, the method described in JP-A-5-331083).
  • the composition containing 1-bromo-1-fluoroethylene can contain one or more solvents selected from the group consisting of methanol and amide. When the composition contains such a solvent, 1-bromo-1-fluoroethylene in the composition can have high stability.
  • gas chromatography was performed according to the following GC conditions. ⁇ GC conditions> GC equipment; SHIMADZU GC-2010 Column: J & W DB-5MS (0.25 ⁇ m, 60 m, 0.25 mm ID) Column oven: 40 ° C. (4 minutes) ⁇ Temperature rise (10 ° C./min) ⁇ 300° C. (0 minute) Vaporization chamber temperature: 200 ° C
  • Examples 1,1-dibromoethylene test compositions 1-4 containing the stabilizers of Table 1 were prepared. The content of the stabilizer was measured by a calibration curve method using GC.
  • Test compositions 1 to 4 of Examples and 1,1-dibromoethylene of Reference Example were each stored in a nitrogen atmosphere at 20 ° C., protected from light.
  • insoluble powder did not precipitate after one week, but the purity in 1 H-NMR measurement was reduced by 30%.
  • Test Compositions 2 and 3 there was almost no decrease in purity in 1 H-NMR measurement after 4 weeks, and no insoluble powder was deposited.
  • test composition 4 1,1-dibromoethylene, an insoluble powder precipitated in a few minutes.

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Abstract

　La présente invention concerne : une composition contenant [A] du 1,1-dibromoéthylène, [B] un ou plusieurs composés amine et [C] un ou plusieurs composés choisis dans le groupe comprenant (1) des composés ayant un groupe hydroxyle, (2) des composés ayant une liaison sulfure, (3) des composés ayant un atome de soufre thiophénolique ou thiolique, (4) des composés d'acide sulfureux et (5) des composés d'acide nitreux, ainsi qu'un procédé de stabilisation du 1,1-dibromoéthylène au moyen de cette composition.
PCT/JP2015/062879 2014-04-28 2015-04-28 Composition WO2015166962A1 (fr)

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Citations (5)

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JPS5052006A (fr) * 1973-09-13 1975-05-09
US3957892A (en) * 1973-05-23 1976-05-18 Ethyl Corporation Stabilized vinylidene halide
JPH1072383A (ja) * 1996-09-03 1998-03-17 Tosoh Corp 臭化アリルの安定化方法、及び安定化された臭化アリル組成物
JP2010116330A (ja) * 2008-11-11 2010-05-27 National Institute Of Advanced Industrial Science & Technology フッ化シクロブタン化合物の製造方法
WO2013008509A1 (fr) * 2011-07-13 2013-01-17 東ソー有機化学株式会社 Procédé pour la stabilisation d'un composé de bromure d'allyle et composition de composé de bromure d'allyle stabilisée

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US1891415A (en) * 1930-04-09 1932-12-20 Dow Chemical Co Preparation of brominated hydrocarbons
US4418232A (en) * 1982-11-29 1983-11-29 E. I. Du Pont De Nemours & Co. Dehydrohalogenation process
JPS6456637A (en) * 1987-08-25 1989-03-03 Toso Yuki Kagaku Kk Production of 3-bromobenzaldehyde
WO2011102538A2 (fr) * 2010-02-19 2011-08-25 Daikin Industries, Ltd. Procédé pour la production de 2-chloro-3,3,3-trifluoropropène
JP5743014B2 (ja) * 2013-09-03 2015-07-01 ダイキン工業株式会社 １，１−ジブロモ−１−フルオロエタンの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957892A (en) * 1973-05-23 1976-05-18 Ethyl Corporation Stabilized vinylidene halide
JPS5052006A (fr) * 1973-09-13 1975-05-09
JPH1072383A (ja) * 1996-09-03 1998-03-17 Tosoh Corp 臭化アリルの安定化方法、及び安定化された臭化アリル組成物
JP2010116330A (ja) * 2008-11-11 2010-05-27 National Institute Of Advanced Industrial Science & Technology フッ化シクロブタン化合物の製造方法
WO2013008509A1 (fr) * 2011-07-13 2013-01-17 東ソー有機化学株式会社 Procédé pour la stabilisation d'un composé de bromure d'allyle et composition de composé de bromure d'allyle stabilisée

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