DE2644594A1 - FLUOR SUBSTITUTION IN 1,1,1-TRIHALOGENALKANES - Google Patents

Description

PATENT ADVOCATE DR. HANS-GÜNTHER EGGERT, DIPLOMA CHEMIST

5 COLOGNE Sl, OBERLÄNDER UFER 90 2644594

Cologne, October 1, 1976 No. 159

Halocarbon Products Corporation, 82 Barlews Court, Hackensack, New Jersey 761, USA ■, - "..". "

Fluorine substitution in 1,1,1 -Tr! Halogenalkaneη

The invention "relates to the substitution of other halogen atoms in organic compounds by fluorine.

Fluorine-containing alkanes and alkenes are generally "known" and are used in many ways. Fluoroalkanes are used in anesthesia and as intermediates for numerous chemical Reactions including the production of fluoroalkenes are used. The alkenes can be used to prepare fluorosilicones are silylated according to the "Belgian patent specification 647 975; these silicones are extremely stable chemically, i. inert, which is why they are "particularly suitable for the manufacture of resistant products such as seals, inserts and the like, if they are in the solid state, and for control fluids (functional fluids) when they are liquid.

With 1,1,1,3-Tetraehlorpropane (TCP) as starting material the representation of 1,1,1-trifluoropropene runs "for example as follows:

(I) CCl ₃ CH ₂ CH ₂ Gl + 3HP > CP ₃ CH ₂ CH ₂ Cl + 3HCl

(II) CP ₃ CH ₂ CH ₂ Ci + NaOH ^ CP ₃ CH = CH ₂ + NaCl + H ₃ O

However, the reaction with HP is difficult, slow and of low yield.

Various attempts are known, e.g. Henne JACS vol. (1951) 1042 and Haszeldine JCS (1953) 3371 ff, in particular 3374, reaction I under "Use of Antimony Halides

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e.g., antimony dichloro trifluoride and trifluoride, as fluorinating agents instead of HF to let it run.

However, these processes were also slow, not very productive, expensive and required the use of inert organic solvents to suspend and / or the antimony salts were difficult to rework.

It is therefore an object of the invention to provide a method for to create simple and effective substitution of other halogen atoms of a 1,1,1-trihalomethane by fluorine.

According to one embodiment of the invention, these and other objects and advantages are achieved by adding an at least approximately equimolar amount of antimony trihalide to 1,1,1-trihalomethane with liquid HP in the presence of a mixture of antimony pentahalide, whereby the 1-halogen atoms are selectively and " are gradually substituted by fluorine; here "means approximately equimolar 1: 1 · - ^approx · 1 ° $ · If the 1,1,1-trihalomethane also carries one or two other halogen atoms such as chlorine or bromine on the 3 or another carbon atom, the also carries at least one hydrogen atom, such other halogen atoms are not attacked, while the halogen atoms are substituted in the 1-position. With TCP as the 1 ₉ 1,1-trihalomethane as the starting material, the reactions can be shown schematically as follows:

q-h + 3 q-u + 5

(III) Cl ₃ C-CH ₂ -CH ₂ Cl + HP-FCl ₂ C-CH ₂ -CH ₂ Cl + HCl

(IV) FCl ₂ C-CH ₂ -CH ₂ Cl + HF - »F ₂ ClC-CH ₂ -CH ₂ Cl + HCl

(V) F ₂ ClC-CH ₂ -CH ₂ Cl + HF ■ - »F ₃ C-CH ₂ -CH ₂ Cl + HCl

The reaction can end before the last specified "enclosed step" and the product mixtures obtained can be fractionated to give each of the organic products from (III), (IV) and (V) to win.

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Preferred antimony pentahalides and trihalides are the fluorides and chlorofluorides. Fluorides and chlorofluorides can be formed in situ from the corresponding antimony chlorides, the hydrogen fluoride in sufficient quantity is used in order to obtain them advantageously in a slight excess. It is believed that the antimony pentahalide and trihalide form a 1: 1 complex "and this is possibly the active catalyst. The mixture from the complex and / or pentahalide plus excess trihalide can be obtained by adding only one component or "Both components in a ratio other than the desired one and transferring one component into the in situ others to establish the desired ratio may be formed. If only antimony pentahalide is added, a Reducing agents such as olefin (which itself could be formed in situ) or a metal can be used to produce a To convert part of the pentahalide into the trihalide and thereby to establish the desired ratio. Alternatively, if only trihalide is added, an oxidizing agent such as bromine or chlorine can be used to make less than half the trihalide in pentahalide to transfer, which in turn would achieve the desired ratio, and then HF are added.

It is believed that the 1: 1 complex at an antimony trihalide: antimony pentahalide ratio of less than 1 still forms, but diluted with an excess of antimony pentahalide. Accordingly, to this extent he will ... those with the use of antimony pentahalide as Catalyst-connected compartment parts, namely replacement of hydrogen by halogen and corrosion.

The reaction temperature is not critical. Nevertheless, the reaction becomes a matter of course at higher temperatures accelerated. It is not recommended to implement it

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Carry out temperatures below room temperature, as this would require additional cooling. On the other hand, temperatures of more than 100 C generate unnecessarily high pressures. A temperature of about ο his 1oo ° C, preferably about ⁰ C 3o Ms 75, is thus suitable.

Since HCl boils at -85 ° C and KF at 19 ° C, it is desirable to carry out the process under pressure, e.g. at a

ο Overpressure of around 1.4 - 7, in particular around 2.8 - 5.6 kg / cm This enables HCl to be used at reasonable reflux temperatures to be removed by distillation during HF remains behind.

According to a "preferred embodiment of the invention, As stated above, TCP is used as the starting material and the reaction takes place gradually, adding one chlorine atom at a time is substituted, Ms to the end product 3-chloro-1,1,1-trifluoropropane (TPCP). In contrast, no reaction takes place if the same starting material with antimony trihalide in Absence of HF and antimony pentahalide is added. When HP is added, the reaction proceeds only slightly Scope. According to Gavlin et al, J. Org. Chem. 21 (1956) 1342-1347, antimony trifluoride is used together with antimony pentachloride Admittedly, part of the desired product is formed, but "., a. side reaction takes place that leads to the formation." of HCl leads in part to the following equation:

(VI) Cl ₃ C-CH ₂ -CH ₂ -Cl ^Sl3Cl 5 _> Cl ₂ C ^ CH-CH ₂ -Cl + HCl

The same result is obtained when antimony pentafluoride is used alone as the halogenating agent. The resulting Olefins form black, resinous polymers as a by-product and represent a considerable loss in yield Adding HF to antimony pentafluoride starts the reaction a little better, but it still creates one

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significant amount of resinous by-product. Highly serious is that antimony = pentafluoride or pentachloride together HF has an extremely corrosive effect on most metals and the complex device is quickly used up.

The antimony fluorides are very reactive, but you can use the antimony in the form of chlorides, whereby the hydrogen fluoride converts them into antimony fluoride and HCl gas. When the antimony fluoride reacts with the organic chlorides, the antimony salts are converted into the mixed chlorine-fluorine salts, which are still used as catalysts serve for the procedure. However, the chlorine-fluorine salts react repeatedly with the excess HF with renewed Formation of fluorides and HCl. If you leave the hydrogen fluoride content sink so that the antimony salts have a low fluorine content, so the catalytically decreases ^ Effect. As indicated earlier, pentavalent salts appear to be corroded eventually during the reaction of the metal vessel or by reaction with organic reducing agents. When that happens, diminishes the catalytic action and finally comes to a complete standstill. At this point in time, pentavalent antimony can then be used added, making the overall ratio of pentavalent too trivalent (including that formed by earlier reduction of the pentavalent) in the desired range is held.

At the beginning of a cycle, the antimony salts generally make up about 5-35 percent by weight, preferably 8-2o percent by weight, of the HF and the antimony salts. The proportion of antimony salt increases as the reaction progresses as a result of the consumption of HF and the addition of additional antimony salt.

The time to add the pentavalent antimony to the mixture to regenerate the catalytic effect is

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decisive. As the following example 10 shows, SbClc reacts violently with 1,1,3-trichloro-i-fluoropropane (MFCP) and TCP and as example 5 shows / the yield decreases by adding ShCl ₁ - and results in poorly converted mixtures, namely those called the reactions (IV) and. (V) have not expired sufficiently. The best way to avoid such difficulties is to monitor the extent of the reaction while limiting the addition of TCP or stopping it when the catalytic activity diminishes. It is useful to stop adding 5RCP when the remaining catalyst is available within a short period of time the total present in the mixture to about 9o TCP TPCP $ and $ 1o 1,3-dichloro-1,1-difluoropropane (DPCP) are reacted. A lower Eeaktionsumfang, wherein the mixture contains about 5% MI ¹ CP is from Far less recommendable for the reasons mentioned above.

It turns out that the decomposition of MPCP and TCP does not occurs after SbClc has been added to the mixture and one

it will react with HP and the trivalent antimony present Purposeful

leaves. A process sequence - as shown below by way of example - comprised the following steps;

1. The total amount of HP is placed in a steel reaction vessel given.

2. SbCIr- and SbCl-> are in a molar ratio

5 3

1: 1 premixed and in the form of a melt in the Given reaction vessel.

3. TCP is added in such an amount that it

is converted into approx. 9o $ TPCP and 1o $ DPCP (see example 14).

4. Then another batch of SbCl ₁ - and an additional amount of TCP are added.

5. Measures 3 and 4 are repeated until the Mixture contains approx. 2 - 8 percent by weight of HP.

6. The mixture is separated to obtain the TPCP product.

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In practice, the last chlorine atom of a trichloromethane is the most difficult to substitute for fluorine. If a reaction product contains a mixture of different compounds, but a substantial proportion of 1,1,1 _{T is} trifluorinated, this is an indication that the reaction has ended too early because the system is apparently capable of producing the desired Product to "form." Likewise, you can quickly check the feasibility and reaction conditions with 1-chloro-1,1-difluoromethyl as the starting material. If it is easily converted into the corresponding 1,1,1-trifluoromethyl, this is an indication that the reaction would also proceed easily using the corresponding 1,1,1-trichloromethyl.

The invention is explained in more detail by the following examples, whereby all information is given in weight percent, if nothing else is expressly stated.

example 1

14.98 kg of HF were placed in a double-walled 37.58 l monel autoclave, which is provided with a column with a coolant-cooled condenser, a stirrer and lines for adding and checking the contents of the vessel. The hydrogen fluoride was heated to 50 ⁰ C and then $ 3.95 kg of a 91 Mo 1 .. ". SbCl ;, and $ 9 moles SbCl ^ melt containing added. It was an immediate increase a slight pressure, of the fluorination at the antimony salts and the formation of HCl based. 8.63 kg of an equal amounts TFCP and DFCP- containing mixture was added rapidly while the mixture one hour was then held at 50 ⁰ C and two hours at 70-80 ° C. during this time of the hydrogen chloride was distilled out immediately upon formation. the distillation was continued while reducing the pressure to atmospheric pressure until the head tempera door in the range of 10-20 ⁰ C was, which indicated that a mixture of the organic product and the HF flowed back.

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The raw product is also suitable without further purification directly for the reaction with a lye according to equation II shown above.

As stated earlier, the response is general to Trihalomethane applicable, after also on precursors of the same, although some compounds respond better than others. The starting material can include, for example, 1,1,1-trihaloalkane or 1,1,1-trihalomethyl benzene, e.g. cter;! lrihalomethyl radical or a corresponding residue of hydrogen (trihalomethane), halogen (tetra carbon), an alkyl residue, in particular a lower alkyl radical with up to 4 carbon atoms, ζ.B. Ethyl (1,1,1-trihalopropane) or methyl (1,1,1-trihaloethane), a halogen substituted one Alkyl radical, in particular a lower alkyl radical with "to to 4 carbon atoms and one or more chlorine, bromine and / or fluorine atoms, e.g. chloromethyl- (2-chloro-i, 1,1-trifluoroethane) or 2-chloroethyl- (1,1,1,3-tetrachloropropane), a aromatic radical, especially one with 6-10 carbon atoms such as phenyl (benzotrichloride) or phenylene (hexachlorxyloi), halogen-substituted products of the same i.a. be bound.

This can also be applied to precursors such as trichlorethylene, which in this case forms 1,1,2-trichloro-1-fluoroethane with the HF. For certain reasons that cannot be fully explained, certain other substituents on the molecule have a certain inhibitory effect such that longer times are required or lower yields are achieved, e.g. two fluorine atoms on a carbon adjacent to the trihalomethyl group as in CFpBrCFpCHpCHpBr. Likewise, for example, CCI ^ CH ₂ CH ₂ Ch ₂ CH ₂ CI is somewhat less reactive than TCP.

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• Λ-,

Part of the refluxing condensate was allowed to form layers, the lower organic layer was removed and the upper HF layer passed back into the column. $ 98 of the organic material was obtained and the yield was the theoretical yield.

Example 2

10.90 kg of TCP were added to the HP and the antimony salts, which remained in the autoclave according to Example 1, in 12 hours, the temperature of the reaction vessel being kept at 50 ° C. and the hydrogen chloride being removed as it was formed. The reaction vessel was then held at 50 ° C. for a further hour and heated to 75-80 ° C. for a further four hours; a distillation and separation carried out according to Example 1 then gave a mixture of 28 $ Ti ¹ CP and 72 $ DPCP with 87 $ of the theoretical yield. This shows the decreasing effect of the catalyst, which is probably due to the reduction of the pentavalent antimony content as the reaction progresses.

Example 3

To the mixture remaining in the reaction _{vessel according to Example 2, 0.45 kg of SbCl 1} - was added and the organic product according to Example 2 was then returned to the vessel. The hydrogen chloride was distilled off and the distillation separation was carried out, with a product of 99.7 $ TPCP at 93 $ of theory. It can therefore be seen that the activity of the catalyst also increases when the proportion of pentavalent antimony is increased compared to the amount present at the end of Example 2.

Example 4

Using the vessel and the procedure according to Example 1, the following compounds and amounts were mixed: 13 »50 kg HP,

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1.14 kg of 46 moles of trivalent and 54 moles of fatty antimony chloride, 11.35 kg of 11GT. After 17,5stündiger reaction "at 5O ⁰ C component, the separated organic material to 90 $ of Ti ¹ CP and $ 10 from DPGP" theoretical almost -Full yield. It follows from this that slight deviations from the minimum equimolar ratio of trivalent to pentavalent antimony are permissible.

Example 5

The mixture remaining in the reaction vessel according to Example 4 was added within 5.6 hours to 9.53 kg of TCP "at 50 ° C. Insufficient amount of HCl developed, which indicates incomplete fluorination. Antimony pentachloride (0.284 kg) became and led to an extremely rapid evolution of HCl. A further 90 o8 kg of TCP were then added, which caused insufficient HCl formation. ShCIc (0.68 kg) was added again and resulted in immediate evolution of HCl Analysis of the contents of the reaction vessel indicated that a large amount of non-volatile residue and only a small amount of TS ¹ CP and DI ¹ CP had been detected.

Example 6

9, o8 kg HP and 0.9I kg of a mixture of 57 mol $ ShCl o and 43 moles of $ ShCl, - were mixed as in Example 1.

Then 2.72 kg of TCP were added at 5o C and the hydrogen chloride was removed when it was formed. After that, about 0.45 kg of SfcClc and then 4.54 kg of TCP were added. o27) Amounts of ShCl c followed by the addition of TCP in amounts of 2.27-4.54 kg were repeated "until a total amount of 25.42 kg of TCP had been added. The distillation separation resulted in a mixture of $ 74 TPCP, $ 18 DPCP, 8 $ MPCP and traces of TCP in $ 98 of theory.

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Example 7

In an experiment similar to Example 6, the final product was un. HP together from the reaction mixture without separation distilled. The distillate was then placed in a dry ice trichlorethylene bath chilled and the layers separated. Each layer was only with small amounts of the other layer contaminated.

Example 8

The same vessel as in Example 1 was used. 4.99 kg of SfcClc were added to 19.98 kg of HF at approx. 23 ° C. Then 3 kg of TGP were added, the temperature being kept between 23-35 ° C. The hydrogen fluoride was removed and recovered the organic product by distillation and separation. The organic yield was 99 $ pure TPCP, but only $ 34 of theory. This showed that a to high ratio (initially infinite with reduction during the reaction) of the pentavalent to the trivalent Antimony leads to a low yield.

Example 9

The residue remaining in the reaction vessel was used; 15.21 kg of TCP were added to this. The reaction and distillation were carried out so that the temperature does usually at 2o C, but always within the range from 18 to 38 ⁰ C was. The result of the distillation and separation was $ 99.6 TPCP in $ 95 of theory. This indicates that the bulk ratio of pentavalent to trivalent antimony at the end of Example 8 had been reduced to a level at which the conversions were essentially complete and quantitative.

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Example 1o

A few grams of MFCP were added to a small amount of SbCl, - in a test tube. This led to an immediate evolution of HCl and the mixture turned black and viscous. TCP responded similarly. SbCIc and SbCl ^ mixtures showed this same result.

Example 11

A number of metal test strips were placed in the autoclave described in Example 1 for a series of at 50.degree performed TCP fluorinations in which the original

+5 + λ
Sb: Sb molar ratio was 43:57, then pure SbClc was added several times, but the molar Sb ⁺ concentration in the mixture, consisting of the added and formed, was always above the molar concentration of the Sb. Weighing and surface loss calculation show the following corrosion values in mils per year:

Inconel boo 2.9 Nickel 2oo 5.9 stainless steel 316 3.3 Monel 4oo 13th C-2ο Cb3 1.4

From this it can be seen that the preferred ratio of pentavalent to trivalent antimony is the metals that make up Reaction vessels are generally made, not unduly corroded.

Example 12

The following corrosion tests were carried out in polytetrafluoroethylene bottles carried out at 2o ° C:

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/ f.

added
salt Salt in
based Weight ^ metal
on Hi ¹ Corrosion in
Mil / year SbCl ₅ 25th 316 stainless steel no longer
measurable Il Il Carbon steel Il Il Il Carpenter 2o Il Il i Io lead Il Il Il silver Il SbP ₃ 10 Monel 6.7 C! TVIP / Dt » Il Carpenter 2o 6.9 O ΙΛΕ - \ f .DL r ~%
(5/1 wt.) 12th Monel 7th Il Il Carpenter 2o 6th SbCl ₅ 3 Monel 289 Il Il Carpenter 2o 132 SbcWSbCl. 1p Monel 1.8 (5o / 5o molar) Il Il Carpenter 2o 1.1

The investigation shows that pentavalent antimony salts as such were significantly more corrosive than trivalent salts and that the equimolar mixture was only slightly corrosive. Aluminum is relative to all of these mixtures inert.

Example 13

166 g of TCP became a mixture of 13.2 g of SbP-. and 4.5 g SbClc in 68o g hydrogen fluoride at 16-19 C in a poly te met luoräthylenf las before given. After 18 hours, the mixture was partially converted into fluorinated chloropropanes, the yield being $ 99.4.

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/fa.

Example 14

In an experiment similar to Example 6, "the original amount of HF was 13.96 kg xuid 1.27 kg ShCl3 / S1) Cl ₅ in a molar ratio of 57/43. This mixture was" at 50 ° C. 9.08 kg TCP added, then 0.11 kg of SlDCl ₅ and then 4.54 kg of TOP. The following S "bCl, - / TCP quantities (in kg) were added in stages every two hours:

0.11 / 7.38
0.23 / 2.72
0.23 / 4.54
0.23 / 6.81

There was an essentially quantitative yield of organic material from 88.4 $ TI ¹ CP, 8.5 $ DPCP and 3 $ MPCP.

Example 15

This example shows that fluorination with antimony pentachloride without antimony trichloride "considerable amounts of undesirable By-products can arise, it "causes namely the Substitution of hydrogen by chlorine.

3.63 kg of HF were placed in a 16.05 liter Teflon-coated autoclave, which is provided with a coolant-cooled condenser, a Teflon-coated stirrer, and lines for adding and checking the contents of the vessel. 1.16 kg (0.085 mol) S1) Cl ₅ "was added at room temperature. The vessel temperature was "kept at 35 C and the hydrogen chloride evolved by the fluorination of the ShCl ^ salts was removed by distillation. Over a period of one hour 1.26 kg (0.0228 mol) of trichlorethylene were added while the mixture" was kept at 3o - 35C. The temperature was then set between 21 and 42 ^° C. for 24 hours, during which time the hydrogen chloride was "distilled out" as it was formed.

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Then 2, chloro-1,1,1-trifluoroethane was through Distillation removed from the vessel and 1.87 kg HP of the HF and antimony salts remaining in the reaction vessel admitted. 1.45 kg (0.0243 moles) of trichlorethylene were added over a period of 15 minutes. The temperature was kept between 23 and 47 ° C for a period of 4 hours while the hydrogen chloride was removed by distillation became. A sample of the organic phase in the vessel resulted in known substances in gas-liquid chromatography the following values in percent:

Cl $ 49.2

CP ₂ ClCH ₂ Cl $ 16.6

CP ₂ ClCHCl ₂ $ 16.1

CPCl ₂ CHCl ₉ 9.4 $

C.

Accordingly, at 25.5 $ of the product, hydrogen was substituted by chlorine on the 2-carbon atom.

Example 16

14.98 kg HP were placed in a double-walled 37.58 l monel autoclave, which is provided with a column with a coolant-cooled condenser, a stirrer and lines for adding and checking the contents of the vessel. The hydrogen fluoride was heated to 30 ° C. and then 4.99 kg (o.i0368 "MdI) _- USTjCIp- were added over the course of half an hour. The vessel was heated and the hydrogen chloride developed was drawn off by distillation. 13.62 kg (o , 228 mol) of trichlorethylene added to the reaction vessel, the mixture being kept at 5o ° C and hydrogen chloride

was distilled out immediately as it was formed. The product was distilled out of the jar and the test by gas-liquid chromatography showed 36.3 moles of Cl with 100 conversion and 78.0 moles of yield.

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The analysis of a sample of the dark gray, from the heating vessel recovered residue yielded $ 91.3 Sb, $ 1.89 Cu and $ 6.81 Ni. Accordingly, in the absence of SbCl ^ reaction carried out corrosion of the reaction vessel, for the presence of copper and nickel in the residue is due to this.

Example 17

22.1 g of a SbCl ^ -SbCl ^ mixture in a ratio of 50-5o mole was placed in a 180 ml 316 stainless steel bomb fitted with a Teflon-coated magnetic stirrer, water-cooled condenser and manometer. The reaction vessel was then charged with 150 g (7.5 mol) of HP. Then 36o g (2.57 moles) were added over a period of two and a half hours. The temperature was maintained between 4-2 and 49 ° C and the evolved gases passed through an aqueous KOH solution and a trap containing dry ice. The hydrogen chloride was eye in the ^ collected and the volatile organic compounds in the IUF safety gear: - 326 '; gr (- 2 _r 4'1 "Jffol.) J 53 ° C added a second time soon after...?. 12.9 g (0.043 mol) of SbClc were added for 23 hours at a temperature between 56 and 70 ° C. The mixture was then kept at a temperature of 40 ° -60 ° C. for 24 hours ° C with 131.5 g (1 mol oo) COl charged ₂ = CClH, and after 1.6 h with an additional 131.5 g CCl ₂ = CClH. ^e ine temperature of 5o-6o ° C was stirred for 21 in the Maintain reaction vessel.

The total yield of organic compounds including those remaining in the bomb was:

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-W-

MoI

CP ₃ CH ₂ Cl 4.34

CP ₂ ClCH ₂ Cl o.99

CPCl ₂ CH ₂ Cl 1.57

CCl ₂ = CHCl ο, ο72

6,972

which means an almost quantitative extraction of material. The hydrogen fluoride made up only $ 0.96 of the total weight of the organic compounds. From the high proportion of CPoCH ₂ Cl it can be seen that an even higher yield would have been achieved if the reaction had been continued, because the intermediates were on their way to the end product with only minimal hydrogen substitution.

Example 18

In a vessel as described in Example 17, 14.4 g of an SbP -, - SbCl, - mixture with 50 mol% each were placed. Then, 2o6,5 g (1o, 33 mol) of HP added and, after heating the bomb at 58 ⁰ C was added over 2.5 h 3.19 mol CCloCHpCl. When the HCl formed was drained off, an additional 41.4 g (0.138 mol) of SbCl ^ were added to the apparatus, the mixture was heated to 50 ° C. and kept at this temperature for 7 hours. The organic product obtained was 94.3 mol $ and the theoretical yield of CP ^ CHpCl 31.1 $ and of CP ₂ ClCH ₂ Cl 57.9 $. Again it was found that had the reaction continued, the yield of the desired end product would have been higher.

Example 19

38.2 g of an SbClo-SbCl ^ mixture of 50 mol $ each were introduced into the apparatus described in Example 17. Then 9.2o mol of HP were added and then within 9 hours 3.82 mol of CCl ^ CH ₂ Cl at 3o-40 ° C. during the development

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Hydrogen chloride through, a dilute aqueous KDH solution is withdrawn and the low-boiling product in one TroekeneisabfangvorrichtuÄg is condensed. The mixture was then held at 45-5 ° C. for 3/4 hour. The overall yield of the organic compounds obtained give the following quantitative ratio:

Mole

GP ₃ CH ₂ Cl 1.31

CP ₂ ClCH ₂ Cl 1.95

CP ₂ ClCHCl ₂ lane

CPCl ₂ CH ₂ Cl o, 31

CCl ₂ = CHCl o, o5

CPCl ₂ CHCl ₂ o, o1

CCl ₃ CH ₂ Cl 0.04

CCl ₃ CHCl ₂ lane

other o, o1

0.68 (yield -96.3 $)

It follows that compounds with only one hydrogen atom, i.e. those "where chlorination rather than just the chlorine has been substituted by fluorine, can only be obtained in small quantities.

A 316 stainless steel solder strip showed after the loss of 17 mils / year over the entire process flow, i.e. minimal corrosion.

Example 2o

In a similar experiment to Example 19, except that it ran out of trichlorethylene, was obtained after about 47 h "at 25 - ⁰ 5o C a quantitative yield of organic compounds of the following composition:

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CP ₂ ClCH ₂ Cl
CPCl ₂ CH ₂ Cl
CCl ₃ CH ₂ Cl

Here, too, the chlorine deficiency was extremely low. A corrosion test strip of Carpenter 20 steel showed a loss of 3.8 mils / year and 316 stainless steel a loss of 1.7 Mil / year, i.e. minimal corrosion.

Example 21

In an Eeaktion similar to Example 2o, in which the However, the temperature was kept below 3o C, was the Implementation after 4.5 hours similar to that in Example 2o.

Example 22

In a similar experiment to Example 21, "in which, however, an SbCl, -SbCl ^ mixture - was used at a molar ratio of 67-33 has been" a low conversion in the product mixture after 24 h "at about 25 ⁰ C , but after a further day "at 5o C a reaction similar to Example 2o" was observed.

Example 23

In the apparatus described in Example 17 ″, 1.11 mol of CHClPp were fluorinated using 2o.6 g of a 50 molar SbCl, -SbCl ₅ mixture in 7.7 mol of HP at about 25 ° C. in 47 h At this point, $ 52.8 of the starting material had been converted to CHP-3
easily fluorinated.

transferred to CHP-j. CCl. can be done in a similar way

Example 24

The antimony salts and HP remaining according to Example 23 were used for the fluorination of 180 g of benzotrichloride. To

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The contents of the reaction vessel were separated for about 15 minutes and 119 g of a substance obtained from benzotrifluoride for $ 98.4 duration.

Example 25

_{3 g of a 50 mol SbCl ^ -SbCl 1} mixture and 97 g of hydrogen fluoride were placed in a 113.4 g Teflon bottle with a .teflon-coated magnetic stirrer. 13.5 g of hexachlorometaxylene, which had been dissolved in 35.6 g of dichlorotetrafluoroethane, were added over the course of 45 minutes. After a further 2.25 hours at room temperature, all of the hexachlorometaxylene had been converted into hexafluorometaxylene.

Example 26

26.9 g of a 50 molar SbCl ^ -SbCl ^ -G mixture were placed in the reaction vessel according to Example 17, and 200 g of HF were added. Then 295 g of 1,1,1-trichloropropane were added over the course of 2 hours, the temperature being kept below 32 ^° C. After a total of 24 hours, a yield of 81% 1,1,1-trifluoropropane was obtained.

The invention is to be understood that by the Description and examples are merely illustrative and illustrative is in no way restricted, and it is also possible through a variety of modifications and changes can be modified without "however thereby deviating from the general inventive concept and the Leaves the scope of the invention.

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Claims (1)

Claims · Process for the substitution of other halogen atoms on the ^v - 1 carbon atom of a 1,1,1-trihalomethane by fluorine, characterized in that the 1,1,1-trihalomethane with liquid hydrogen fluoride in the presence of a mixture of antimony pentahalide and an at least approximately equimolar Amount of antimony trihalide added. 2 '. Process according to Claim 1, characterized in that the reaction is carried out in a steel reaction vessel. 3. The method according to claim 1, characterized in that the halogen substituted by fluorine is chlorine and the reaction is carried out at such a temperature and pressure that the; .. formed Hydrogen chloride distilled and hydrogen fluoride borne back. 4. The method according to claim 1, characterized in that the mixture of antimony pentahalide and antimony trihalide in situ by mixing liquid hydrogen fluoride with antimony pentachloride and antimony trichloride is formed. 5. The method according to claim 1, characterized in that the starting material is added 1,1,1-trihalomethane and when the reaction slows down, more antimony pentachloride is added and then more Source material. 709815/1199 -WF- 6. The method according to claim 1, characterized in that the mixture used in the fluorination of antimony pentahalide and antimony trihalide is prepared in situ by mixing from a mixture with a higher content of pentahalide than is used in the subsequent fluorination and part of the pentahalide reduced to form the desired mixture. 7. The method according to claim 1, characterized in that the mixture used in the fluorination of antimony pentahalide and antimony trihalide is prepared in situ by mixing from a mixture with a higher content goes out of antimony trihalide than in the following : Fluorination is used and part of the trihalide oxidized to form the desired mixture. 8. The method according to claim 1, characterized in that the reaction mixture is distilled to a distillate of To separate hydrogen fluoride and organic material from remaining antimony salts, the distillate for separation cools into a lower organic layer and an upper hydrogen fluoride layer and separates the layers from one another. 9. The method according to claim 1, characterized in that the reaction mixture is distilled under reflux and that backflowing condensate can form a lower organic layer and an upper hydrogen fluoride layer, which The lower organic layer is removed and the upper hydrogen fluoride layer is returned to the reaction mixture. 0o. Method according to claim 1, characterized in that the hydrogen fluoride is present in at least about three times the molar amount of the 1,1,1-trihalomethane. 709815/1199 11. The method according to claim 1, characterized in that the mixture of antimony pentahalide and trihalide is formed in situ by adding the corresponding mixture of antimony pentachloride and the liquid hydrogen fluoride -trichloride is added. 12. The method according to claim 11, characterized in that 1,1,1-trihalomethane is added and, if the reaction becomes slower, further antimony pentachloride is added and then further 1,1,1-trihalomethane. .13. Process according to Claim 1, characterized in that the reaction mass is distilled to produce a hydrogen fluoride distillate and to separate organic material from residual antimony salts, the distillate for separation into a lower organic layer and an upper hydrogen fluoride layer and cools the layers apart separates. 14. The method according to claim 1, characterized in that 1,1,1-trihalomethane, 1,1,1-trihaloalkane or is a 1,1,1-trihalomethyl benzene. 15. The method according to claim 1, characterized in that the 1,1,1-trihalomethane is 1,1,1,3-tetrachloropropane and the reaction to the formation of 3-chloro-1,1,1-trifluoropropane is continued. 16. The method according to claim 1, characterized in that the 1,1,1-trihalomethane 1,2-dichloro-1,1-dif luoroethane and the reaction to the formation of 2-chloro-1,1,1-trifluoroethane is continued. 709815/1 199 17. Process according to Claim 1, characterized in that 1,1,1-trihalomethane is obtained in situ from 1,1,2-trichlorethylene is formed and the reaction "continues until 2-chloro-1,1,1-trifluoroethane is formed. 18. The method according to claim 1, characterized in that the 1,1,1-trihalomethane is chlorodifluoromethane and the reaction Ms continued to form trifluoromethane will. 19 «Method according to claim 1, characterized in that the 1,1,1-trihalomethane is tetracarbon. 2o. Process according to claim 1, characterized in that the 1,1,1-trihalomethane is benzotrichloride and the Reaction Ms to form benzotrifluoride continues. 21 · Process according to claim 1, characterized in that the 1,1,1-trihalomethane is hexachlorometaxylene and the reaction "until the formation of hexafluorometaxylene is continued. 22. Process for the production of 3,3 »3-trifluoropropene, where 1,1,1,3-tetrachloropropane to 3-chloro-1,1,1-trifluoropropane is fluorinated, which is then reacted with an alkali, characterized in that the fluorination with liquid hydrogen fluoride in the presence of one of antimony pentachloride and one at least equimolar Amount of antimony trichloride molten catalyst carried out the organic constituents from the hydrogen chloride formed, via final hydrogen fluoride and solid antimony salts and the organic components are subjected to a reaction with an alkali. 709815/1 199 • cT 23. Method for storing a mixture of hydrogen fluoride and antimony pentahalide in a vessel which is normally corroded by the mixture, characterized in that that the mixture antimony trihalide in at least one about 'equimolar amount' based on the, pentahalide clogs, whereby the corrosion of the vessel is avoided. 70981 5/1199