WO2004020376A1

WO2004020376A1 - Halogenated alcohol and process for producing the same

Info

Publication number: WO2004020376A1
Application number: PCT/JP2003/010729
Authority: WO
Inventors: Naoto Takada; Takeo Komata
Original assignee: Central Glass Company, Limited
Priority date: 2002-08-30
Filing date: 2003-08-26
Publication date: 2004-03-11
Also published as: JP2004091368A

Abstract

1,1-Dichloro-3,3,3-trifluoroacetone is contacted with hydrogen in the presence of water and a catalyst comprising platinum to obtain 1,1-dichloro-3,3,3-trifluoro-2-propanol. The reaction temperature is especially preferably 0 to 50°C. The 1,1-dichloro-3,3,3-trifluoro-2-propanol obtained has excellent performances when used as a solvent, detergent, etc. It is useful also as an intermediate for medicines or agricultural chemicals or a building block for organic compounds.

Description

BACKGROUND OF THE INVENTION

TECHNICAL FIELD The present invention relates to 1,1-dichloro-3,3,3-trifluoro-2-propanol and analogous compounds thereof, which are useful as a solvent, a solvent, an intermediate for pharmaceuticals / pesticides, and a reagent for introducing a fluorine-containing group.

1,1,1,3,3,3-hexafluoro-2-propanol (CF ₃ CH (OH) CF ₃ ) is used as a raw material for pharmaceuticals and agrochemicals, as a reagent for introducing a fluorine-containing group, and as a fluoropolymer. It is widely used as a solvent and a reaction solvent in organic synthesis. Also, 2,2,3,3-tetrafluoropropanol (CHF ₂ CF ₂ CH ₂ OH) is widely used as a dye solvent for optical storage media such as CD-R and DVD-R (W〇 2002/034841, JP-A-2002-53507).

1,1,1,3,3,3-hexafluoro-2-propanol and 2,2,3,3-tetrafluoropropanol mentioned above have their own solubility due to the effect of fluorine atoms in the molecule. Have. However, some solutes do not show sufficient solubility. For this reason, if an alcohol in which some of these fluorine atoms are substituted with chlorine atoms can be obtained, the solubility as a solvent will change appropriately, and a solubility different from that of the above-mentioned fluorine-containing alcohols will be developed. Expected.

Although 2,2,3,3-tetrafluoropropanol is flammable, a nonflammable or nonflammable solvent is required from the viewpoint of safety. Furthermore, 1,1,1,3,3,3_hexafluoro-2-propanol and 2,2,3,3-tetrafluoropropanol have boiling points of 59 ° C and 109, respectively. When used as a solvent for applying memory-active dyes to disks, if the boiling point is too low, the evaporation rate may be too high and uniform coating may be difficult. You. As the dye solvent, a compound that is flame-retardant or non-flammable, contains a fluorine atom and a chlorine atom, and has a boiling point of about 120 ° C is desired.

Applicants have found that reacting 1,1, dichloromouth—3,3,3—trifluoroacetone, which is industrially easily available, with zinc metal in the presence of a protic solvent gives 1,1,1,1 The fact that trifluoroacetone can be produced is disclosed in Japanese Patent Application Laid-Open No. 2000-226607. Furthermore, as an advantageous method of using a catalyst and reducing the waste load, 1,1-dichloro_3,3,3-trifluoroacetone is brought into contact with hydrogen in the gas phase in the presence of a catalyst containing palladium. Japanese Patent Application Laid-Open No. 2001-31632 discloses that 1,1,1-trifluoroacetone can be obtained in the same manner.

However, in the above methods, 1, 1 Jikuroro 3, 3, 3 - DOO Riffle O b dichloromethyl (one CHC 1 ₂₎ in acetone group or Torifuruorome chill (one CF ₃₎ group is subjected to reduction (hydrogenation) However, reduction of the carbonyl group was unlikely to occur, and it was extremely difficult to obtain alcohols. In fact, in the method of the above-mentioned literature, in addition to the main product 1,1,1-trifluoroacetone, 1,1-difluoroacetone, in which the trifluoromethyl group was further hydrogenated as a by-product, 1 1,1-Dichloroacetone—3,3,3—Trifluoroisopropanol and 1,1,1,1-trifluoro-2-, which are important substances as fluorinated alcohols, although small amounts of monofluoroacetone and acetone are produced. No propanol was obtained.

Thus, there has been a demand for a means of efficiently synthesizing alcohols containing both a fluorine atom and a chlorine atom using readily available compounds as raw materials.

Summary of the Invention

An object of the present invention is to provide alcohols which are useful as an intermediate for a solvent, a solvent, a pharmaceutical or agrochemical, or as a reagent for introducing a fluorine-containing group, and contain both a fluorine atom and a chlorine atom.

Still another object of the present invention is to provide a method for efficiently producing the alcohols by using a readily available compound as a raw material. In view of the above problems, the present inventors have made intensive studies on the synthesis of alcohols containing both a fluorine atom and a chlorine atom. As a result, they have found that the above-mentioned problems can be solved by reacting 1,1-dichloro-3,3,3-trifluoromethylacetone, which is easily available, with hydrogen gas under specific conditions.

That is, the present inventors have found that 1,1-dichloro-3,3,3-trifluoromethylethylacetone is a novel compound when brought into contact with hydrogen gas in the presence of water and in the presence of a catalyst containing at least platinum and in the presence of water. It was found that 1,1-dichloro-3,3,3-trifluoromethyl-2-propanol was produced mildly. The present invention is common to the inventions of JP-A-2000-226057 and JP-A-2001-316322 in that 1,1-dichloro-3,3,3-trifluoromethylacetone is subjected to reduction treatment. The site of occurrence is completely different from these. That is, heretofore the 2-position of the carbonyl group which has been considered difficult with reduction extremely receives preferential reduction in those compounds, dichloro Romechiru (one CHC 1 ₂₎ group or a triflate Ruo Russia methyl group are preserved Gave the surprising result. Furthermore, when the above reaction is carried out in a temperature range of -10 ° C to 150 ° C, 1,1-dichloro-3,3,3-trifluoromethyl-2-propanol may be formed with particularly high selectivity. found.

The 1,1-dichloro-3,3,3-trifluoromethyl-12-propanol obtained in this way has a boiling point of 123 ° C and not only has an appropriate boiling point as a solvent for dissolving the dye, but also However, it was found that there was no flash point, and that the alcohol was particularly safe in handling. It was also found that it has high solubility in organic compounds and functions well as a detergent. This compound has three fluorine atoms, two chlorine atoms and a hydroxyl group, and is also useful as a new building block in the synthesis of fluorinating agents and pharmaceuticals. The present inventors have further found that when 1,1-dichloro-3,3,3-trifluoromethyl-2-propanol is synthesized by the above-mentioned method, 1,1,1-trifluoro-2-propanol is used as a by-product. In particular, when the reaction is carried out at a temperature of 50 ° C or more in the presence of excess water, 1,1,1-trifluoro- It was found that the amount of 2-propanol produced increased. This 1,1,1-trifluoro-2-propanol cannot be produced by the methods described in JP-A-2000-226057 and JP-A-2001-316322, and also as a fluorine-introducing agent. It is a useful compound.

The production method of 1,1,1-trifluoro-2-propanol is described in Ange wand te Chemie, Internati on al Edition (1999), 38 (13/1), P.2052-2054. A method for applying 3,3,3_trifluoro-1-propene to hydroporation has been disclosed. However, compared with the method of the literature, the present invention is easy to obtain raw materials industrially, and is a catalyst reaction, and can use harmless hydrogen gas as a reducing agent. Are better.

Thus, the present inventors have proposed a novel compound, 1,1-dichloro-3,3,3.

3-Trifluoromethyl-2-propanol was obtained, and a new use of this compound was found. Furthermore, they found a new synthetic means for efficiently synthesizing 1,1-dichloro-3,3,3-trifluoromethyl-2-propanol and its related substance 1,1,1-trifluoro-2-propanol. The present invention has been completed.

That is, the present invention provides a novel compound, 1,1 dichloromouth-3,3,3-trifluoro-2-propanol.

The present invention is also characterized in that 1,1-dichloro-3,3,3-trifluoroacetone is brought into contact with hydrogen gas in the presence of water and a catalyst containing at least platinum. Disclosed is a method for producing 2,3,3-trifluoro-2-propanol. In this case, the amount of water may be 3 mol or more per mol of 1,1-dichloro-3,3,3-trifluoroacetone.

Further, the present invention comprises contacting 1,1-dichloro-3,3,3-trifluoroacetone with hydrogen gas in the presence of water and a catalyst containing at least platinum. 2_ How to make propanol provide. In this case, the amount of water may be 10 mol or more per 1 mol of 1,1-dichloro-3,3,3-trifluoroacetone.

The present invention also provides a method using 1,1-dichloro-3,3,3-trifluoro-2-propanol as a solvent and a cleaning agent.

Further, the present invention provides a method for dissolving a dye in 1,1-dichloro-3,3,3-trifluoro-2-propanol.

BRIEF DESCRIPTION OF THE FIGURES

1, 1 obtained in Example 2, 1 Jikuroro 3, 3 is a chart of ^l H- NMR in CDC 1 ₃ in a solvent 3-triethoxysilylpropyl Furuoro 2-propanol (purity 99% or more) (use Equipment: JEOL 400MHz FT-NMR (-400)).

2 Example 1 was obtained by 2, 1 Jikuroro 3, 3, 3-triflate Ruoro 2-propanol (purity 99% or higher) Chiya is one city of ¹⁹ F- NMR in CD C 1 ₃ in a solvent (Used equipment: JEOL 400MHz FT-NMR (α-400)).

3 1 obtained in Example 2, 1 Jikuroro 3, 3, a Chiya one capital of ¹³ C-NMR in CD C 1 ₃ in a solvent 3-triflate Ruoro 2-propanol (purity 99%) ( Equipment used: JEOL 400MHz FT-NMR (-400).

Description of the preferred embodiment

The scheme of the reaction according to the present invention is shown below.

1,1, 1-Trifle Thread 2-F. The present invention will be described in more detail below. First, a method for synthesizing 1,1-dichloro-3,3,3-trifluoro-2-propanol will be described.

This reaction can be carried out in a gas phase system or a liquid phase system. Here, the gas phase method refers to a method in which a mixture containing raw materials is vaporized to perform a reaction. In this method, a mixture containing the raw material compound 1,1-dichloro-3,3,3-trifluoroacetone is vaporized, then mixed with hydrogen gas, and introduced into a reaction group at a predetermined temperature containing a catalyst. Can be reached. On the other hand, the liquid phase method refers to a method in which a mixture containing raw materials is kept in a liquid phase and is brought into contact with hydrogen gas to cause a reaction. In this method, a mixture (liquid) containing 1,1 dichloro-3,3,3-trifluoromethylacetone as a raw material is introduced into a reaction group, hydrogen gas is introduced in the presence of a catalyst, and the mixture is stirred at a predetermined temperature. Can be achieved by

In the case of the gas phase method, it is necessary to vaporize the raw material before introducing it into the reactive group, but the boiling point of the raw material compound 1, 1-dichloro-3,3,3-trifluoroacetone is 75 ° C at normal pressure Therefore, in order to carry out the reaction in a particularly preferable temperature range (50 ° C. or lower) shown below, it is necessary to reduce the pressure in the reaction system, and the operation becomes complicated. On the other hand, in the case of the liquid phase system, the reaction can be carried out under normal pressure or pressurized conditions, so that the reaction can usually be carried out more easily than in the gas phase system. That is, in the present invention, the liquid phase method is recommended from the viewpoint of operation. The temperature in the system at the time of carrying out this reaction is preferably in the range of 110 ° C. to + 10 ° C., and particularly preferably in the range of 0 ° C. to + 50 ° C. In this reaction, 1,1,1-tritrifluoromethyl-2-propanol is by-produced in addition to the target product 1,1-dichloro-1,3,3,3-trifluoro-2-propanol. However, in the temperature range below 50 ° C, the formation of the latter is suppressed to a small extent, and 1,1 dichloro-1,3,3,3-trifluoro-2-propanol can be obtained as the main component. In particular, when the reaction is carried out at room temperature (25 ° C) or lower, the selectivity of 1,1-dichloro mouth—3,3,3-trifluoro-2-propanol is particularly high, so that 1,1-dichloro-3,3,3 This is particularly effective when only 3-trifluoro-2-propanol is the target substance.

If the reaction temperature is higher than 100 ° C, the amount of 1,1,1-trifluoromethyl-2-propanol increases, so the desired 1,1-dichloro-3,3,3-trifluoro- 2- The selectivity of propanol decreases. Conversely, when the temperature is lower than 110 ° C., it is not preferable because not only the reaction rate is reduced but also the raw material may be solidified.

For this reaction, it is essential that water coexist in the system. If there is no water in the system, the target product 1,1-dichloro-3,3,3-trifluoromethyl-2-propanol cannot be obtained. There is no lower limit for the amount of water, but to obtain the desired product in sufficient yield, 3 moles per 1 mole of the raw material 1,1-dichloro-3,3,3-trifluoromethylacetone It is preferably from 30 to 30 mol, more preferably from 5 to 20 mol. If the added amount of water is less than 3 mol, the deterioration of the catalyst, the reduction of the reaction rate, the reduction of the selectivity of the desired product, etc. occur with the progress of the reaction, which is not preferred. There is no upper limit to the amount of water, but no significant improvement in reactivity is observed even when 50 mol or more is added to 1 mol of 1,1-dichloro-3,3,3-trifluoromethylacetone. This is not preferred because it is only disadvantageous for the public. For this reaction, it is essential that a catalyst containing at least platinum is present in the system. Although there is no particular limitation on the form of this catalyst, a solid phase catalyst in which a compound containing platinum is supported on a carrier such as activated carbon, silica, or alumina is preferred.

The target reaction proceeds even if palladium, ruthenium, iridium, or rhodium is present as a catalyst other than platinum as a metal. In the case of the solid phase catalyst described above, a solid phase catalyst in which these metals are supported on a carrier together with platinum corresponds to this. However, unlike platinum, these metals have the effect of hydrogenating the 1,1-dichlorofluoromethyl group and increase the by-products such as 1,1,1-trifluoromethyl 2-propanol. The higher the number, the lower the yield of the desired 1,1-dichloro mouth—3,3,3-trifluoromethylacetone. Therefore, when only 1,1-dichloro-3,3,3-trifluoromethylacetone is intended, it is particularly preferable to use a catalyst containing no metal other than platinum.

When these metals are supported on a solid support, a known method may be used. That is, an aqueous solution of a metal compound (for example, hexacloplatinum (IV) acid hexahydrate (H ₂ [PtCl ₆ ] · 6H ₂₀ ) or palladium nitrate) is added to a carrier such as activated carbon, silica, or alumina. The solid phase catalyst can be prepared by means of dipping and spraying, drying, and heating to about 150 to 350 ° C while flowing hydrogen gas or the like. Alternatively, a commercially available solid phase catalyst can be used.

The supported amount of the metal is preferably in the range of 0.01 wt% to 20 wt% (amount converted into metal atoms) with respect to the carrier, and the supported amount of 0.51;% to 51;% is particularly preferable.

The catalyst prepared in this way can be used as a dry product that does not contain moisture or as a wet product that has been conditioned in advance. However, the dry product may ignite in the air, so handling with care is required. Since the present invention is characterized by adding water to the system, a wet product is recommended from the viewpoint of safety. The amount of the catalyst to be added in carrying out the reaction of the present invention is not necessarily limited, but the weight of the solid catalyst prepared as described above, excluding water, is 1,1-dichloro-1,3,3,3. -It is appropriate to be in the range of 0.5 wt% to 30 wt% based on trifluoroacetone. If the amount of catalyst added is less than this, the reaction time may be extremely long, or the reaction may be stopped halfway. Conversely, when a large amount of the catalyst is used, no particularly useful effect on the reactivity is observed, which is economically disadvantageous. In addition, since these catalysts are solid phase catalysts, they can be easily recovered and reused after the completion of the reaction.

When a halogen-containing compound is reduced with hydrogen in the presence of a catalyst, a basic compound (eg, NaOH, KOH, LOH) is added to the system in order to neutralize the by-produced hydrogen halide and prevent poisoning of the catalyst. _{_{i OH, Na 2 C0 3,}} N aHC0 3, K 2 C_〇 _3, Toryechiruamin, pyridine, etc., a material solution pH of 8 or more when dissolve in a concentration of 1 mo 1 · dm- ³ in water ) Are commonly made to coexist (for example, JP-A-63-280035). However, the raw material compound for this reaction, 1,1-dichloro-3,3,3-trifluoroacetone, undergoes hydrolysis upon contact with a basic compound and is converted to an aldehyde (J. Org. Chem. , 1988, 53, p. 5088-5092), which leads to a decrease in yield and a decrease in purity, and therefore, in the present invention, addition of a base is not preferred. In the present invention, with the progress of the reaction of interest, as a side reaction, dichloromethyl (one CHC 1 ₂₎ 1 occurs hydrogenation group, 1, 1 one triflumizole Ruoro 2-propanol as a byproduct, At this time, hydrogen chloride is generated. Although there is a concern that this hydrogen chloride lowers the activity of the catalyst, in the present invention, as described above, the water added into the system absorbs and detoxifies hydrochloric acid produced as a by-product, and the function of the catalyst is reduced. It has been found that little happens.

When the reaction is performed in a liquid phase system, the pressure in the reaction system is not particularly limited, but is preferably in the range of normal pressure (0.IMPa) to 5 MPa, particularly in the range of 0.5 MPa to 3 MPa. preferable. The higher the reaction pressure, the more advantageous in terms of chemical equilibrium. In addition, it is preferable because the solubility of hydrogen in the liquid phase is high, but a reactor with high pressure resistance is required.

A reactor coated with polytetrafluoroethylene or the like as a material inside the reaction group of the liquid phase type is recommended in terms of corrosion resistance. On the other hand, materials such as stainless steel and glass are susceptible to corrosion, and therefore, it is not preferable to use them as materials inside the reaction group.

Although a specific embodiment of the liquid phase system is not particularly limited, an example of a preferable embodiment will be described below. That is, the raw materials 1,1-dichloro-3,3,3-trifluoroacetone, water, and the catalyst are charged in predetermined amounts into a reaction group capable of withstanding the pressurized condition. Next, the container is sealed, and stirring in the container is started. Connect to a hydrogen gas cylinder and pressurize with hydrogen gas. Thereafter, hydrogen gas may be supplied continuously or intermittently so that the inside of the reactor is maintained at a predetermined pressure at a predetermined temperature. During the reaction, analysis of the reaction mixture may be appropriately analyzed by means such as gas chromatography, and the reaction may be continued until the raw materials are sufficiently consumed. The reaction time is not particularly limited and varies depending on the conditions, but if the reaction is continued for a long time after the raw materials have been sufficiently consumed, the generated 1,1-dichloro-3,3,3-trifluoro-2-propanol is further increased. Hydrogenation is not preferred because the yield of the desired product may be rather reduced.

Next, the method for producing 1,1,1-trifluoro-2-propanol from 1,1-dichloro-3,3,3-trifluoroacetone will be described. As mentioned earlier, 1,1 dichloro-mouth 3,3,3-trifluoroacetone is used as a raw material, and this is brought into contact with hydrogen gas in the presence of water and in the presence of a catalyst containing at least platinum. By the means, 1,1-dichloro-3,3,3-trifluoro-2-propanol and 1,1,1-trifluoro-2-propanol are produced simultaneously. Therefore, the production methods of both compounds are basically common. However, there are differences in the conditions for the production of 1,1-dichloro-3,3,3-trifluoro-2-propanol and 1,1,1-trifluoro-2-propanol. There is a need to. First, in the production of 1,1-dichloro-1,3,3,3-trifluoro-2-propanol, a catalyst containing platinum alone as a metal element was most suitable as a catalyst. When R2-propanol is used as the target substance, not only a platinum-only catalyst, but also a metal such as palladium, ruthenium, iridium or rhodium (which is added to ) Is more preferable because the hydrogenation of the dichloromethyl group in the raw material is promoted and the selectivity of 1,1,1,1-trifluoro-2-propanol is increased. There is no particular limitation on the weight ratio of platinum to the added metal, but if the amount of platinum is too small, the reduction of the carbonyl group of the raw material compound will not proceed easily, so the amount of 1,1,1-trifluoromethylacetone produced Results in an increase in the selectivity of the target product. Therefore, when 1,1,1-trifluoro-2-propanol is the target substance, the number of moles of the added metal relative to 1 mole of platinum is preferably within 2 and more preferably within 1.5. . It is an example of a particularly preferred embodiment that the molar ratio of platinum to the additional metal is set to around 1: 1.

Next, regarding the reaction temperature, in the production of 1,1-dichloro-3,3,3-trifluoro-2-propanol, the range of 0 ° C. to 5 Ot was particularly suitable. In the case of producing monotrifluoro-2-propanol, the temperature is preferably from 50: 150 ° C, more preferably from 80 ° C to 150 ° C. When the temperature is lower than 50, the production of 1,1-dichloro-3,3,3-trifluoro-2-propanol becomes relatively large. In this case, the formed 1,1-dichloro-3,3,3-trifluoro-2-propanol can be further reduced and converted to the desired 1,1,1,1-trifluoro-2-propanol, It is not preferable because it takes a long time. Although the target reaction proceeds even at a temperature higher than 150 ° C., it is not preferable because hydrogenation of a trifluoromethyl group and by-product of hydrofluoric acid accompanying the hydrogenation are likely to occur. In this reaction, the addition of water is essential. However, when producing 1,1,1 trifluoro-2-propanol, the production of 1,1, dichloro-3,3,3—trifluoro mouth—2-propanol is higher than that of producing 2-propanol. It is preferred to add more water. Specifically, it is preferable to add water in a range of 10 to 40 moles to 1 mole of 1,1-dichloro-3,3,3-trifluoroacetone, and more preferably from 20 to 40 moles. It is further preferred to add 30 times the molar amount of water. By the addition of this water, hydrogen chloride produced as a by-product of the reaction is detoxified, and a decrease in the activity of the catalyst accompanying the reaction is suppressed, so that the reaction can be continued in a stable state.

Other conditions and methods for the production of 1,1,1-trifluoro-2-propanol from 1,1-dichloro-3,3,3-trifluoroacetone are the same as those described above for 1,1-dichloro-3. Same as for the production of, 3,3-trifluoro-2-propanol.

For the production of 1,1-dichloro-3,3,3-trifluoro-2-propanol and for the production of 1,1,1-trifluoro-2-propanol, isolation of the target compound from the reaction mixture after completion of the reaction The method may be a known method for organic compounds, and is not particularly limited. To illustrate a specific method, first, the reaction mixture is distilled to distill and remove only water and impurities having a low boiling point, and then a dehydrating agent such as concentrated sulfuric acid, zeolite, calcium chloride, and magnesium sulfate is added to remain. Remove moisture. As a dehydrating agent, concentrated sulfuric acid is particularly recommended. By subsequent precision distillation, high-purity 1,1-dichloro-3,3,3-trifluoro-2-propanol or 1,1,1-trifluoro-2-propanol can be isolated.

For 1,1, dichloro-3,3,3-trifluoro-2-propanol, the flash point was measured by the method specified by the Fire Service Law. As a result, no flash point was obtained. Solvents, cleaning agents, draining agents, etc. Excellent in safety when used in applications. It is also possible to add methanol, ethanol, isopropyl alcohol, etc. to control the cleaning and draining properties. The addition amount of these alcohols is optional, but 1,1-dichloro-3,3,3-trif The content is preferably from lwt% to 30 wt%, more preferably from 5 to 15 wt%, based on Luoro 2-propanol.

The surface tension of 1,1-dichloro-3,3,3-trifluoro-2-propanol was measured and found to be 26.4 mN / m, which is 2,2,3,3-tetrafluoropropanol (currently used). The result was almost the same as CHF ₂ CF ₂ CH ₂ 〇H, 26.5 mN / m), so it can be used as a substitute for nonflammable solvents.

Optical storage media such as CD-R and DVD-R use dyes such as cyanine, phthalocyanine, and azo dyes dissolved in a solvent and apply the dye to the base. Since 3,3,3-trifluoro-2-propanol has a fluorine atom and a hydroxyl group, it can be used as a solvent for the dye, and shows good solubility in these.

In addition, 1,1-dichloro-3,3,3-trifluoro-2-propanol and 1,1,1-trifluoro-2-propanol have hydroxyl groups, so they contain fluorine-containing building blocks for pharmaceuticals, agricultural chemicals, etc. It is very promising.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples.

[Comparative Example 1]

Into a 2 liter glass-lined reactor, add 576 g of water, 384 1,1-dichloro-3,3,3,3-trifluoroacetone and 19 g of 5% palladium on activated carbon catalyst (50% water content) Then, stirring was started. After replacing the inside of the system with nitrogen and hydrogen gas, the temperature of the reactor was raised with warm water. Then, hydrogen gas was continuously supplied so that the pressure in the reactor was maintained at 1.0 MPa. The reactor was heated and reacted at an internal temperature of 80 to 90 ° C for about 8 hours. After confirming that hydrogen consumption had ceased, the reaction was terminated. Analysis of the organic components in the reaction mixture by gas chromatography revealed that 1,1,1 trifluoroacetone was 97.8%, 1,1 difluoroacetone was 0.03%, Black mouth one 1, 1,2% difluoroacetone, 1,1 1-Trifluoro2-propanol, trace amount, 1,1 dichloro-mouth, 3,3 3 1

Nol was not detected.

[Example 1]

A piece of ice is added little by little to 1,1 dichloro mouth, 33,3 trifluoroacetone (purity: 99.5%), which has been dehydrated with sulfuric acid in advance, and 1,1 dichloro-3,3,3-trifluoro An aqueous solution having a molar ratio of loacetone to water of 1:20 was prepared. 50 g of this aqueous solution into a pressure-resistant glass container with an internal volume of 100 Om 1 and 5 wt% PtZC powder manufactured by Degussa Japan Co., Ltd. 50% water-containing product (100 g of activated carbon, 5 g of white gold (In terms of metal atoms) 1.7 g of a supported catalyst (humidified so that the water content was 50% by weight) was added. After closing the vessel, the air was replaced several times with hydrogen through a blowing tube, and then hydrogen was introduced so that the pressure became IMPa. The reaction solution was gradually heated to 100 ° C. while sufficiently stirring with a magnetic mixer. Since the hydrogen pressure decreased during the reaction, hydrogen gas was additionally introduced sequentially so that the pressure of 1 MPa was maintained. After 5 hours from the start of the reaction, the stirring was stopped. After cooling naturally to room temperature, the mixture was further cooled in an ice bath and purged with hydrogen. As a result of analyzing the contents by gas chromatography, 1,1-dichloro-1,3,3,3-trifluoroacetone (raw material): trace amount, 1,1-chloro-3,3,3-trifluoroacetone: Trace amount, 1, 1, 1-trifluoroacetone: 3.4%, 1,1,1-trifluoro-2-propanol: 53.6%, 1,1-dichloro-3,3,3-trifluoro-2-propanol : 41.2%.

[Example 2]

Ice chips (270 g) were added little by little to 1,1-dichloro-3,3,3-trifluoroacetone (purity: 99.5%, 180 g), which had been previously dehydrated with sulfuric acid. An aqueous solution of 1-dichloro-3,3,3-trifluoroacetone was prepared. To a 1.5 liter polytetrafluoroethylene-lined autoclave, add this aqueous solution (450 g) and Degussa Japan Co., Ltd. 5 wt% PtZC powder 50% water-containing product (catalyst in which 5 g of platinum in terms of metal atoms is supported per 100 g of activated carbon, and moisture is adjusted so that the water content becomes 50 wt%) 18 g I charged. After cooling with a refrigerator and replacing the air several times with hydrogen through a blowing tube, hydrogen was introduced so that the pressure became 2 MPa. The temperature of the reaction solution was controlled to be 0 to 2 ° C while sufficiently stirring with a stirring blade (cradle type + propeller). Since the hydrogen pressure dropped during the reaction, hydrogen was additionally introduced sequentially to maintain the pressure at 2 MPa. The stirring was stopped 16 hours after the start of the reaction, and hydrogen was purged. As a result of analyzing the contents by gas chromatography, 1,1-dichloro-3,3,3-trifluoroacetone (raw material): 16.4%, 1-chloro mouth-3,3,3-trifluoroacetone: 0 1%, 1,1,1-trifluoroacetone: 9.4%, 1,1,1-trifluoro-2-propanol: 4.8%, 1,1-dichloro-3,3,3-trifluoro- 2-propanol: 68.3%. After the reaction solution and the catalyst were separated by filtration, vacuum distillation was performed to remove water and low-boiling compounds. Then, after dehydration by the action of sulfuric acid, precision distillation was performed under normal pressure using a distillation column having 30 theoretical plates. The fraction at an overhead temperature of 122 ° C to 124 ° C was recovered as the main fraction. When the obtained main fraction was analyzed by gas chromatography, the purity of 1,1 dichloro-opening-3,3,3-trifluoro-2-propanol was 99% or more. The main fraction the CD C 1 ₃ in a solvent NMR (JEOL 400 MHz FT-NMR (shed - 400)) was analyzed, the following results were obtained.

NMR result: ¹ H—NMR (reference material: TMS = 0 ppm)

δpm: 4.1 (s, 1H), 4.5 (s, 1H), 6.0 (d, 1H)

^{, 9} F-NMR (reference material: CFC 1 ₃ = 0ppm)

δ p pm: -75.4 (d, 3F, CF ₃ )

1 ³ C-NMR (standard substance: CDC l ₃ = 77.0ppm)

δ p pm: 68.5 (d, CHC1 2), 74.7 (m, CH (OH)), 122.4 (dq, CF 3) Further, in FIGS. 1-3 shows a chart of the NMR.

[Example 3] The flash point of 1,1-dichloro-3,3,3-trifluoro-2-propanol (purity: 99% or more) obtained in Example 2 was measured by the method specified by the Fire Service Law. In other words, the flash point from 20 ° C to 80 ° C was measured using the closed tag type, but no flash phenomenon was observed. Next, the flash point from 20 ° C to 123 was measured by the Cleveland method. No flash phenomenon was observed up to 123 ° C. At around 123 ° C, 1,1-dichloro-3,3,3- The trifluoro-2-propanol boiled and the test flame extinguished. Based on the above, it was determined that there was no flash point. The environment of the measurement room at this time was room temperature 20 ° (:, atmospheric pressure 1024 hPa, relative humidity 39%).

[Example 4]

The surface tension of 1,1-dichloro_3,3,3-trifluoro-2-propanol (purity of 99% or more) obtained in Example 2 was measured using an automatic surface tension measurement device (CBVP-A3 manufactured by Kyowa Kaimen Kagaku Co., Ltd.). (Type). Measured at 23 ° C after calibration with benzene, pure water, HC FC_141 b. As a result, the surface tension of 1,1-dichloro-3,3,3-trifluoro-2-propanol was 26.4 mN / m.

[Example 5]

Dye (copper (II) 1,2,3,4,8,9,10,11,15,16,17,18) in 100 g of 1,3 dichloro-1,3-, 3-trifluoro-2-propanol , 22, 23, 24, 25-hexadecidium fluoro-29H, 31H-monophthalocyanine) was added, and the mixture was heated and stirred at 50 ° C. After standing at room temperature for 24 hours, it was found to be well dissolved by visual observation.

[Example 6]

0.1 g of the dye (nickel (II) phthalocyanine) was added to 100 g of 1,3-dichloro-1,3-, 3-trifluoro-2-propanol, and the mixture was heated and stirred at 50 ° C. After standing at room temperature for 24 hours, it was visually dissolved and found to be well dissolved. .

[Example 7] 1.0952 g of flux for solder was applied to a glass plate and heated at 120 ° C for 10 minutes. This glass plate was placed in a mixed solution of 500 g of 1,1-dichloro-3,3,3-trifluoro-2-propanol and 50 g of 2-propanol, and washed with an ultrasonic cleaner for 5 minutes. After taking out the glass plate and draining the solution, put the glass plate into a new solution of 1,1-dichloro-3,3,3-trifluoro-2-propanol and finish ultrasonic cleaning for 1 minute. went. As a result of measuring the weight of the dried glass plate, no increase in the mass of the glass plate was observed. This indicates that the flux was successfully removed.

[Example 8]

In order to evaluate the performance as a drainer, water droplets were added to a solution of 500 g of 1,1-dichloro-3,3,3,1-trifluoro-2-propanol in 50 g of methanol by washing with ultrapure water. The attached spectacle lens was inserted. After ultrasonic cleaning for 2 minutes, it was dried with hot air at 120 ° C. Visual inspection revealed no spots.

[Example 9]

Put a stainless steel nut with mechanical oil on it into a solution of 100 g of 1,3 dichloro-1,3-, 3-trifluoro-2-propanol and 10 g of ethanol, and perform ultrasonic cleaning for 5 minutes. And dried at 120 ^ for 10 minutes. Upon visual inspection, the surface was clean.

Claims

The scope of the claims

1. 1,1-dichloro-1,3,3,3-trifluoro-2-propanol.

2. 1,1-Dichloro-1,3,3-trifluoroacetone is brought into contact with hydrogen gas in the presence of water and a catalyst containing at least platinum. 1,1,1-Dichloro-1,3 , 3-Trifluo P—Method for producing 2-propanol.

3. The 1,1,1-dichloro-3,3,3,3,3,3,3,3 according to claim 2, characterized in that the amount of water is at least 3 mol per 1 mol of 1,1-dichloro-3,3,3-trifluoroacetone. Method for producing 3-trifluoro-2-propanol.

4. 1,1,1-trifluoroacetone characterized by contacting 1,1,1-chloro-1,3-trifluoroacetone with hydrogen gas in the presence of water and a catalyst containing at least platinum. Rho 2—Propanol production method.

5. The 1,1,1-trifluoro-2- according to claim 4, wherein the amount of water is at least 10 moles per mole of 1,1-dichloro-3,3,3-trifluoroacetone. Method for producing propanol.

6. A method using 1,1-dichloro-3,3,3-trifluoro-2-propanol as a solvent or cleaning agent.

7. A method in which the dye is dissolved in 1,1,1-dichloro-1,3,3,3-trifluoro-2-propanol.