TW201319012A - Process for making hydrohalocarbons and selected compound - Google Patents

Abstract

A process is disclosed for producing addition compound CHCl2CHXCClYR, wherein X and Y are each independently selected from the group consisting of H, F, Cl and Br, and R = H or a perhalogenated alkyl group. The process involves a liquid phase reaction of CHCl3 with CHX=CYR in the presence of an addition catalyst. New compound disclosed is CHCl2CH2CHClCF3. It is useful as an intermediate for producing hydrofluorocarbons and hydrofluoroolefins.

Description

Process for making hydrogen halides and selected compounds

The present invention is generally directed to catalytic addition reactions of CHCl ₃ with monohydrohaloolefins and compounds made therefrom.

Halogenated alkanes, such as CFCs (chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons), have been used in a wide range of applications including push sprays, refrigerants, detergents, thermoplastics and thermoset foams. Expanding agent, heat transfer medium, gas dielectric, fire extinguishing agent and fire suppressant, power cycle working fluid, polymerization medium, particle removal fluid, carrier fluid, polishing abrasive and displacement desiccant. They can also be used as intermediates for more highly fluorinated compositions such as HFCs (hydrofluorocarbons) and HFOs (hydrofluoroolefins). HFCs have replaced CFCs and HCFCs in many applications, including as refrigerants or foam expanders, due to concerns that certain CFC and HCFC products can cause ozone depletion. HFOs have been seen as an excellent alternative to traditional CFCs, HCFCs and HFCs because they do not destroy the ozone layer and have low global warming potentials (GWPs).

The present invention provides a liquid phase process to produce a product mixture comprising the addition compound CHCl ₂ CHXCClYR wherein X and Y are each independently selected from the group consisting of H, F, Cl and Br, and R = H or A fully halogenated alkyl group. The process involves reacting CHCl ₃ with CHX = CYR in the presence of an addition catalyst.

The novel compound provided in accordance with the present invention is CHCl ₂ CH ₂ CHClCF ₃ . Which can be used as the production of hydrofluorocarbons and hydrofluoroolefins (e.g. CF ₃ CH = CHCF ₂ H) intermediates.

The above general description and the following detailed description are merely illustrative and illustrative, and are not limiting of the invention as defined by the appended claims. Other features and advantages of one or more of the embodiments will be apparent from the detailed description and appended claims.

The terms "comprising," "comprising," "having," For example, a process, method, article, or device that comprises a series of elements is not necessarily limited to the elements, but may include other elements not specifically listed or inherent to the process, method, article, or device. In addition, unless expressly stated to the contrary, "or" refers to an inclusive "or" rather than an exclusive "or". For example, any of the following conditions satisfies condition A or B: A is true (or exists) and B is false (or non-existent), A is false (or non-existent) and B is true ( Or existing), and A and B are both true (or exist).

Also, "a" or "an" is used to describe the elements and components described herein. This is for convenience only and provides a general sense of the scope of the invention. This description should be understood to include one or at least one, and the singular also includes the plural unless the

Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although methods or materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are still described below. All publications, patent applications, patents, and other references herein are hereby incorporated by reference in their entirety in their entirety herein In the event of a conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and are not intended to be limiting.

The present invention is a liquid phase process comprising reacting CHCl ₃ with CHX=CYR in the presence of an addition catalyst to form a product mixture comprising the addition compound CHCl ₂ CHXCClYR, wherein X and Y are each independently selected from a group consisting of H, F, Cl, and Br, and R = H or a perhalogenated alkyl group.

The starting materials for the addition reactions in the present invention, i.e., CHCl ₃ and CHX = CYR, can be combined by methods known in the art.

The term "alkyl" as used herein, alone or in the compound word, such as "perhalogenated alkyl", includes cyclic or acyclic and straight or branched alkyl groups such as methyl, ethyl, n-propyl. , isopropyl or its different isomers.

The term "perhalogenated alkyl" as used herein means a monoalkyl group wherein all of the hydrogen on the carbon atom is replaced by a halogen such as F, Cl, Br and I. Examples of perhalogenated alkyl groups include -CF ₃ and -CF ₂ CF ₃ .

The term "addition catalyst" as used herein means a catalyst which promotes the addition reaction.

In certain embodiments of the invention, X and Y are each independently selected from the group consisting of H, F, and Cl. In certain embodiments of the invention, CHX=CYR is selected from the group consisting of CH ₂ =CH ₂ , CH ₂ =CHCF ₃ , CH ₂ =CHCF ₂ CF ₃ , CH ₂ =CFCF ₃ and CHF=CHCF ₃ Group.

Examples of the addition compound CHCl ₂ CHXCClYR in the present invention include CHCl ₂ CH ₂ CH ₂ Cl, CHCl ₂ CH ₂ CHClCF ₃ , CHCl ₂ CH ₂ CHClCF ₂ CF ₃ , CHCl ₂ CH ₂ CClFCF ₃ and CHCl ₂ CHFCHClCF ₃ .

In certain embodiments of the invention, CHX=CYR is CH ₂ =CHCF ₃ and the resulting product CHCl ₂ CHXCClYR is CHCl ₂ CH ₂ CHClCF ₃ .

In certain embodiments of the invention, CHX=CYR is CH ₂ =CH ₂ and the resulting product CHCl ₂ CHXCClYR is CHCl ₂ CH ₂ CH ₂ Cl.

The addition reaction involving CHCl ₃ and CHX = CYR in the present invention is based on the stoichiometry of 1 mole of CHCl ₃ per mole of CHX = CYR. In fact, an excess of CHCl ₃ can be used as needed. Typically, the molar ratio of CHCl ₃ to CHX = CYR is from about 1:1 to about 10:1.

The addition reaction process of the present invention can be carried out by placing CHCl ₃ and CHX = CYR starting materials and addition catalyst in a reaction vessel, followed by heating and stirring the mixture. The process can be achieved by batch or continuous system.

At the end of the addition reaction, the desired product CHCl ₂ CHXCClYR can be recovered from the product mixture via conventional methods. In certain embodiments of the invention, the solid residue may be removed via decantation or filtration at the end of the addition reaction and the desired product may be purified or recovered via distillation of the resulting liquid product mixture.

Addition compounds comprising the products of the invention can be used as intermediates in the formation of hydrofluorocarbons and hydrofluoroolefins. An example of the use of the addition compound of the present invention to form a hydrofluoroolefin is disclosed in the Russian Patent Application No. 2010147004 [FL1372], which is incorporated herein by reference in its entirety herein in its entirety herein in its entirety in its entirety herein in The novel compound provided herein is CHCl ₂ CH ₂ CHClCF ₃ which can be prepared by reaction of CHCl ₃ with CH ₂ =CHCF ₃ as described in Example 1.

In certain embodiments of the invention, the addition catalyst is a copper catalyst comprising copper chloride and a suitable reducing agent.

The copper chloride used herein may be anhydrous (CuCl ₂ ) or hydrated (for example, CuCl ₂ ‧2H ₂ O). In certain embodiments of the invention, the amount of CuCl ₂ ‧2H ₂ O used in the addition reaction is from about 0.5 to about 10 weight percent based on the total weight of the starting materials (ie, CHCl ₃ and CHX=CYR) . In certain embodiments of the invention, the amount of CuCl ₂ ‧2H ₂ O used in the addition reaction is from about 1 to about 5 weight percent based on the total weight of the starting material. In certain embodiments of the invention, the amount of CuCl ₂ used in the addition reaction is from about 0.4 to about 8 weight percent based on the total weight of the starting material. In certain embodiments of the invention, the amount of CuCl ₂ used in the addition reaction is from about 0.8 to about 4 weight percent based on the total weight of the starting material.

A suitable reducing agent in the present invention is a compound which can reduce a Cu(II) compound (for example, CuCl ₂ ) to a Cu(I) compound (for example, CuCl) under the reaction conditions of the present invention, but does not react with the starting materials CHCl ₃ and CHX. = reducing agent for the CYR reaction. In certain embodiments of the invention, a stoichiometric amount of reducing agent is used in the addition reaction of the present invention. In certain embodiments of the invention, more than a stoichiometric amount of reducing agent is used in the addition reaction of the present invention.

Examples of suitable reducing agents include hydrazine (N ₂ H ₄ ) and its derivatives (for example, monomethyl hydrazine (CH ₃ (NH) NH ₂ ) and 1,1-dimethyl hydrazine ((CH ₃ ) ₂ ) NNH ₂ ), etc.), disulfites (eg Na ₂ S ₂ O ₄ , K ₂ S ₂ O ₄ and (NH ₄ ) ₂ S ₂ O _{4 ,} etc.), copper (zero valence, eg copper powder) And magnesium (zero price), and iron (zero price, such as iron powder). In certain embodiments of the invention, low molecular weight nitriles can also be used as a suitable reducing agent, such as acetonitrile and propionitrile.

Generally, a solvent is used with the copper catalyst in the present invention. In certain embodiments of the invention, the solvent is a low molecular weight nitrile such as acetonitrile and propionitrile. In certain embodiments of the invention, the solvent is a guanamine selected from the group consisting of dimethylformamide (DMF), dimethylacetamide, and N-methylpyrrolidone.

A total of the catalyst may be used together with the copper catalyst in the addition reaction of the present invention, as needed. Suitable cocatalysts are those which form a coordination compound with Cu(I) or Cu(II). Examples of co-catalysts suitable for the copper catalyst system include bis ([or oxime] oxazoline), 2,2-bipyridine and derivatives thereof.

When the addition reaction of the present invention is carried out in the presence of a copper catalyst, the temperature used is usually in the range of from about 60 ° C to about 240 ° C. In certain embodiments of the invention, the temperature used in such addition reactions is in the range of from about 130 °C to about 190 °C. The pressure used in the addition reaction is not critical. Usually, the addition reaction is carried out under autogenous pressure.

In certain embodiments of the invention, the addition catalyst is an iron catalyst comprising iron and ferric chloride.

The ferric chloride used herein may be anhydrous (FeCl ₃ ) or hydrated (e.g., FeCl ₃ ‧6H ₂ O). The iron used herein is a metal iron having zero valence. In certain embodiments of the invention, iron powder is used in the addition reaction. Generally, the molar ratio of iron to ferric chloride used in the addition reaction of the present invention is from about 1:1 to about 10:1. In certain embodiments of the present invention, the total amount of the addition reaction of iron and FeCl ₃ in CHCl ₃ as a reference amount of from about 5 to about 30 weight percent.

Generally, a total of catalysts can be used with the iron catalyst in the addition reaction of the present invention. In some embodiments of the invention, the cocatalyst is an alkyl phosphate or an aryl phosphate, such as: triethyl phosphate, tributyl phosphate, diethyl phenyl phosphate, diethyl phosphate, dibutyl phosphate Esters, phenyl phosphate, butyl phosphate and the like. Typically, the molar ratio of iron catalyst to phosphate cocatalyst is from about 2:1 to about 20:1. In certain embodiments of the invention, the molar ratio of the iron catalyst to the phosphate cocatalyst is from about 5:1 to about 10:1.

A solvent may be used together with the iron catalyst in the present invention, as needed. In certain embodiments of the invention, the starting material CHCl ₃ can also be used as a solvent. In certain embodiments of the invention, the solvent is an inert compound that does not react with other compounds or catalysts during the reaction. If such an inert solvent is used, it should be boiled at a temperature such that it can be separated from the unconverted starting materials CHCl ₃ and CHX=CYR and the product CHCl ₂ CHXCClYR.

When the addition reaction of the present invention is carried out in the presence of an iron catalyst, the temperature used is usually in the range of from about 60 ° C to about 240 ° C. In certain embodiments of the invention, the temperature used in the addition reaction is in the range of from about 130 °C to about 190 °C. The pressure used in this addition reaction is not critical. Usually, the addition reaction is carried out under autogenous pressure.

The reactor, distillation column and its combined supply pipe, effluent pipe and related units used in the process of the embodiment of the invention may be constructed of corrosion-resistant materials. Typical materials of construction include glass and Teflon ^TM. Typical constituent materials also include stainless steel (austenite type especially those), known high nickel alloys (Monel ^TM e.g. nickel-copper alloy, Hastelloy ^TM nickel-based alloys and Inconel ^TM nickel-chromium alloy), and copper-clad steel.

The various aspects and embodiments described above are illustrative only and not limiting. After reading this specification, those skilled in the art will appreciate that other aspects and embodiments may be possible without departing from the scope of the invention.

Instance

The concepts described herein are further illustrated by the following examples, which do not limit the scope of the invention described in the claims.

Example 1

Example 1 illustrates the addition reaction of CHCl ₃ with CF ₃ CH=CH ₂ in the presence of an iron catalyst to form the addition compound CHCl ₂ CH ₂ CHClCF ₃ .

The tributyl 7.5 g of iron powder, 7.35 g phosphoric acid 4 g FeCl ₃ and 144 g (1.2 mole) CHCl ₃ Hastelloy ^TM tube was charged in 400 ml. The tube was cooled, evacuated and fed 57.6 g (0.6 mole) CF ₃ CH = CH _2. The reaction mixture was heated to 185 ° C and maintained at this temperature for 3 hours. The product mixture was distilled to obtain 87 g of the desired product CHCl ₂ CH ₂ CHClCF ₃ (bp 122 to 124 ° C / atmospheric pressure) in a yield of 67.7%. The product CHCl ₂ CH ₂ CHClCF _{3 was} further characterized by mass spectrometry and NMR:

MS: 179 [M-Cl], 159 [M-Cl-HF], 143 [CHCl ₂ CH ₂ Cl], 117 [CF ₃ CHClCH ₂ ], 109 [CHCl ₂ CH ₂ CH], 83 [CHCl ₂ ], 69[CF ₃ ].

¹ H NMR (CDCl ₃ ): (CCl ₂ H ^a CH ₂ ^b CH ^c ClCF ₃ ) 1H ^a 5.93 ppm d (9.9 Hz) d (3.2 Hz), 2H ^b 2.75 ppm mult, 1H ^c 4.37 ppm mult.

¹⁹ F NMR (CDCl ₃ ): -75.1 ppm d (6.5 Hz).

Example 2

Example 2 illustrates the addition reaction of CHCl ₃ with CF ₃ CH=CH ₂ in the presence of a copper catalyst to form the addition compound CHCl ₂ CH ₂ CHClCF ₃ .

21.25 g of CuCl ₂ ‧2H ₂ O, 13.5 g of phenyl hydrazine, 75 ml of acetonitrile and 360 g (3 moles) of CHCl _{3 were} charged into a 1 L Hastelloy ^TM autoclave. The autoclave was cooled, evacuated and fed with 120 g of CF ₃ CH=CH ₂ . The reaction mixture was heated to 185 ° C and maintained at this temperature for 20 hours. The yield of CF ₃ CCl ₂ CH ₂ CHClCF ₃ was 30%.

Example 3

Example 3 illustrates the addition reaction of CHCl ₃ with CH ₂ =CH ₂ in the presence of an iron catalyst to form the addition compound CHCl ₂ CH ₂ CH ₂ Cl.

The tributyl 7.5 g of iron powder, 4.35 g phosphoric acid, 4 g FeCl ₃ and 144 g (1.2 mole) CHCl ₃ was charged to a 400 ml Hastelloy ^TM tube. The tube was cooled, evacuated and fed 22.4 g (0.8 mole) CH ₂ = CH _2. The reaction mixture was heated to 150 ° C and maintained at this temperature for 3 hours. The product mixture was distilled to give the desired product CHCl ₂ CH ₂ CH ₂ Cl (bp 88 ° C / 150 mm Hg), yield 54%.

Example 4

Example 4 illustrates the addition reaction of CHCl ₃ with CF ₃ CH=CH ₂ in the presence of a copper catalyst to form the addition compound CHCl ₂ CH ₂ CHClCF ₃ .

One CHCl ₃ (78 g, 0.661 mol), CF ₃ CH=CH ₂ (12.6 g, 0.131 mol), CH ₃ CN (10 ml) and CuCl ₂ ‧2H ₂ O (2.2 g, 13 at 170 ° C) The mixture of millimolar was shaken in a 100 ml steel autoclave for 18 hours. The resulting product mixture was distilled to obtain 0.3 g of CF ₃ CH=CH ₂ , 68.1 g of fraction I containing 95 mol % CHCl ₃ and 5 mol % (3.4 g) CHCl ₂ CH ₂ CHClCF ₃ (bp 55 to 95 ° C / atmospheric pressure Force) and 18.9 g of Fraction II (35-108 ° C / 35 mm Hg) containing 80% (15.1 g) of CHCl ₂ CH ₂ CHClCF ₃ . The conversion of CF ₃ CH=CH ₂ was about 97%, and the yield of CHCl ₂ CH ₂ CHClCF ₃ was 68.7. Further distillation yielded an analytical sample having a boiling point of 127-128 ° C at atmospheric pressure.

Example 5

Example 5 illustrates the addition reaction of CHCl ₃ with CF ₃ CH=CH ₂ in the presence of a copper catalyst to form the addition compound CHCl ₂ CH ₂ CHClCF ₃ .

One CHCl ₃ (77.5 g, 0.651 mol), CF ₃ CH=CH ₂ (13.4 g, 0.139 mol), CH ₃ CN (10 ml), CuCl ₂ ‧2H ₂ O (2.2 g, 13 at 170 ° C A mixture of millimolar and 0.83 g of copper powder (13 mmol) was shaken in a 100 ml steel autoclave for 18 hours. The resulting product mixture was distilled to obtain 2 g of CF ₃ CH=CH ₂ , 71 g of fraction I containing 96.3 mol % CHCl ₃ and 3.7 mol % CHCl ₂ CH ₂ CHClCF ₃ (bp 55 to 98 ° C / atmospheric pressure) and 17 g Fraction II (38 to 120°/38 to 40 mm Hg) containing 68.6% CHCl ₂ CH ₂ CHClCF ₃ . The conversion of CF ₃ CH=CH ₂ was about 85%, while the yield of CHCl ₂ CH ₂ CHClCF ₃ was 56%.

Example 6

Example 6 illustrates the addition reaction of CHCl ₃ with CH ₂ =CH ₂ in the presence of a copper catalyst to form the addition compound CHCl ₂ CH ₂ CH ₂ Cl.

One CHCl ₃ (80 g, 0.678 mol), CH ₃ CN (10 ml), CuCl ₂ ‧2 H ₂ O (2.2 g, 13 mmol), 0.8 g copper powder (13 mmol) at 170 ° C A mixture of 2,2'-bipyridyl (2.8 g, 14 mmol) and 3.4 g of CH ₂ =CH ₂ was shaken in a 100 ml steel autoclave for 11 hours. The resulting product mixture is distilled to obtain a fraction having a boiling point of 125 to 150 ° C at atmospheric pressure. The fraction was further distilled to obtain 19 g (96% purity) of CHCl ₂ CH ₂ CH ₂ Cl (bp 69-71° / 65 mm Hg).

It should be noted that not all of the acts described in the general description or examples above are necessary, and one of the specific actions may not be necessary, and one or more other actions may be performed in addition to the actions described. Moreover, the order of the actions listed is not necessarily the order in which the steps are performed.

In the above description, the concept of a particular embodiment has been described. However, it will be understood by those skilled in the art that various modifications and changes can be made without departing from the scope of the invention. Accordingly, the description is to be considered as illustrative and not restrictive.

Benefits, other advantages, and solutions to problems with respect to particular embodiments have been described above. However, benefits, advantages, problem solutions, and any features that would make these benefits, advantages, or problem solutions more prominent are not to be construed as critical, essential, or essential features of any or all of the patent applications.

It is to be understood that some of the features of the various embodiments described herein may be combined in a separate embodiment for the purpose of clarity. Conversely, for the sake of brevity, many of the features described herein are in the same embodiment, which may also be provided separately or in any sub-combination. Further, the relevant numerical values described in the range include each and every value within the range.

Figures 1 - 1 are diagrams of a CHCl ₂ CH ₂ CHClCF ₃ mass spectrum.

2A-2A are diagrams showing the ¹ H NMR spectrum of a CHCl ₂ CH ₂ CHClCF ₃ .

2B-2B are detailed diagrams of a ¹ H NMR spectrum of CHCl ₂ CH ₂ CHClCF ₃ at around 5.9 ppm.

2C-2C are detailed diagrams of a ¹ H NMR spectrum of CHCl ₂ CH ₂ CHClCF ₃ around 4.4 ppm.

2D-2D are detailed views of a ¹ H NMR spectrum of a CHCl ₂ CH ₂ CHClCF ₃ at around 2.8 ppm.

3A-3A are diagrams of a ¹⁹ F NMR spectrum of CHCl ₂ CH ₂ CHClCF ₃ .

3B-3B are detailed diagrams of a ¹⁹ F NMR spectrum of CHCl ₂ CH ₂ CHClCF ₃ around -75 ppm.

Claims (17)

A liquid phase process comprising reacting CHCl ₃ with CHX=CYR in the presence of an addition catalyst to form a product mixture comprising an addition compound CHCl ₂ CHXCClYR wherein X and Y are each independently selected from H, F, a group consisting of Cl and Br, and R = H or a perhalogenated alkyl group. The liquid phase process of claim 1, wherein the addition catalyst is a copper catalyst comprising copper chloride and a suitable reducing agent. The liquid phase process of claim 2, wherein the suitable reducing agent is selected from the group consisting of hydrazines and derivatives thereof, dithionite, copper, magnesium, and iron. The liquid phase process of claim 2, wherein a solvent is used with the copper catalyst. The liquid phase process of claim 4, wherein the solvent is selected from the group consisting of acetonitrile, propionitrile, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. . The liquid phase process of claim 2 wherein the reaction is carried out at a temperature of from about 60 ° C to about 240 ° C. The liquid phase process of claim 1, wherein the addition catalyst is an iron catalyst comprising iron and ferric chloride. The liquid phase process of claim 7, wherein the ferric chloride is FeCl ₃ . The liquid phase process of claim 7, wherein a cocatalyst is used with the iron catalyst, and wherein the cocatalyst is an alkyl phosphate or an aryl phosphate. The liquid phase process of claim 9, wherein the cocatalyst is selected from the group consisting of triethyl phosphate, tributyl phosphate, diethyl phenyl phosphate, diethyl phosphate, dibutyl phosphate, and phenyl phosphate. And a group consisting of butyl phosphate. The liquid phase process of claim 7, wherein the reaction is carried out at a temperature of from about 60 ° C to about 240 ° C. The liquid phase process of claim 1, wherein the CHX=CYR is selected from the group consisting of CH ₂ =CH ₂ , CH ₂ =CHCF ₃ , CH ₂ =CHCF ₂ CF ₃ , CH ₂ =CFCF ₃ and CHF=CHCF ₃ groups of groups. The liquid phase process of claim 1, wherein the CHX=CYR is CH ₂ =CHCF ₃ and the addition compound CHCl ₂ CHXCClYR is CHCl ₂ CH ₂ CHClCF ₃ . The liquid phase process of claim 1, wherein the CHX=CYR is CH ₂ =CH ₂ and the addition compound CHCl ₂ CHXCClYR is CHCl ₂ CH ₂ CH ₂ Cl. The liquid phase process of claim 1 further comprising recovering the addition compound CHCl ₂ CHXCClYR from the product mixture. The liquid phase process of claim 15 wherein the addition compound CHCl ₂ CHXCClYR is recovered from the product mixture via distillation. A compound of the formula CHCl ₂ CH ₂ CHClCF ₃ .