FR2642751A1 - PROCESS FOR THE PREPARATION OF BIS (TRIFLUOROMETHOXYPHENYL) CARBONATE AND ITS DERIVATIVES - Google Patents

Abstract

According to the invention, the bis (methoxyphenyl) carbonate is first reacted with chlorine gas in an organic solvent and then the bis (trichloromethoxyphenyl) carbonate formed in the first reaction is reacted with anhydrous hydrogen fluoride in a solvent organic; bis (trifluoromethoxyphenyl) -carbonate derivatives having a halogen, perfluoroalkyl or perfluoroalkoxyl substituent in each phenyl group can also be prepared, by the same method, using the bis (methoxyphenyl) carbonate derivatives having a halogen, perhaloalkyl or perhaloalkoxyl substituent in each phenyl group. The invention applies in particular to the preparation of intermediates for the manufacture of bactericides, herbicides or medicaments.

Description

The present invention relates to a process for the preparation of

  bis (trifluoromethoxyphenyl) carbonate and its derivatives, which are useful as intermediates for bactericides, herbicides or medicaments, from bis (methoxyphenyl) carbonate or its derivatives.

  It is known to prepare bis (trifluoromethoxyphenyl)

  carbonate by first reacting the hydroquinone with carbonyl difluoride and then fluorinating the reaction product with sulfur tetrafluoride

CO F2; (O) F4

COF3O 0 =

(CF - <- C = O

J. Org. Chem., 2 (1J), 1 (1964).

  However, this method is not favorable in industrial practice because COF and SF are 2-4 both very difficult to handle and also because the yield of bis (trifluoromethoxyphenyl) carbonate

is weak.

  The subject of the present invention is a process

  easy preparation of bis (trifluoromethoxyphenyl) -

  carbonate or its derivatives (with substitution in

  each phenyl group) at a high yield.

  It has been discovered that bis (trifluoromethoxy-

  phenyl) carbonate was obtained at a fairly high yield by first chlorinating bis (methoxyphenyl) carbonate followed by fluorinating the chlorinated intermediate, and derivatives of bis (trifluoromethoxyphenyl) carbonate having a halogen substituent, perfluoroalkyl or in perfluoroalkoxyle

(IIi?) = -

  t axxoieoleqad adnoj2 a no alIoleq.ad adnoa2 a 'euefoleqp amoae a' 8ueoJpiPp amoU4E a 4se r.o lx (i T) = O 3O - - _, C: (III) 9iE.1uS inm t o e $. _e_, uasgadca -, sodwoo umn aeiaoj 2Rod @ nbTu-eao uuAios a suep xnGze aaolqo np oeAe IiI 8ei2u9a alunmlou oi sed resles ofJ 0I 9sodmoo an iT5a al! sJ () P dapede4gl 9 apgo-d eldxoiTeoJonlJJad Gdnoj2 a no oiiosnlaid adno .2 '8u2oleq4 p Imose a' lua2ojpX4q p * SL3 -um his X No. I r) fo = D0 () igeoU @ 'nJ; j el-ed 94ues8adaJ 9soduoz a p ap uoTdeaedead Gpgoojd a ajjo S uoTsueAUT auesead eI ';! emu aTInoTzed SNRD - (. ilXupqd xoqupum) STQ ap seA TJP September aTnIed u apgooid eamGi el jed saxedaid a @ eAnod that aiXuGgd -rnca enbleqo 3- o X!' is as defined above with respect to the general formula (II), and (b) reacting the compound represented by the general formula (III) with anhydrous hydrogen fluoride in an organic solvent. For this process, the starting compound, bis (methoxyphenyl) carbonate or its derivative of the general formula (II) can easily be prepared by reaction of methoxyphenol or its derivative with carbonyl dichloride and can therefore be obtained at a price relatively low. In this process, both the reaction of the first stage of chlorination and the reaction of the second stage of fluorination can easily be carried out in industrial manners and the compound

  desired is obtained at a sufficiently high yield.

  In the first stage of a process according to

  According to the invention, the starting compound is a bis (methoxy

  phenyl carbonate or its derivative (II). In each case, the starting compound is solid at normal temperature. For the reaction with chlorine gas, the starting compound is dissolved in an organic solvent. With regard to bis (methoxyphenyl) carbonate (II) derivatives, practical significance is attached to derivatives having Cl, CCl3 or CCl30 as the substituent X '. It is desirable to use an organic solvent which dissolves both the

  starting compound and bis (trichloromethoxyphenyl) -

  carbonate or its derivative (III) formed by the chlorination reaction, which is inactive under the conditions of the chlorination reaction and which is not polar. of the

  examples of very suitable solvents are the -

  carbon tetrachloride, dichloromethane,

  trichloromethane, chlorobenzene and dichlorobenzene.

  If the chlorination reaction is carried out in the presence of metal ions or water, it is likely that the benzene nucleus of the starting compound will be chlorinated because the benzene ring is activated by the methoxyl group. Therefore, care should be taken to avoid the presence of metal ions or water in the chlorination reaction system. If necessary, the organic solvent is refined by filtration to remove a trace of suspended metal material by adding, for example, a urea compound to convert the metal ions to metal complexes by distillation to remove the water or by

  treatment with a desiccant such as a zeolite.

  Since the chlorination reaction in this process is a free radical reaction, it is favorable to improve the reaction rate by irradiating the reaction liquid with light at appropriate wavelengths or by using a general agent: r free radicals such as a peroxide

  organic or an organic azo compound.

  It is appropriate to carry out the chlorination reaction at a temperature between 30 and 150 ° C. that an optimum temperature depends on the other conditions of the reaction. When the temperature of the reaction is lower than 30 C, its pace is too slow. When the temperature of the reaction is above C, the yield of the desired compound is low because of

  of the favored decomposition of the starting compound.

  By contacting the bis (methoxyphenyl) carbonate or its derivative (II) with gaseous chlorine, the methoxy grope of this compound is preferably chlorinated so bis (trichloromethoxyphenyl) carbonate or its derivative (III)

  is formed at a high selectivity.

  The second stage of the process is the fluorination of bis (trichlorometoxyphenyl) carbonate or its derivative (III) formed by the chlorination reaction described above with anhydrous hydrogen fluoride. The fluorination reaction or halogen exchange reaction between chlorine and fluorine is carried out in an organic solvent which dissolves the starting compound. Examples of suitable solvents are carbon tetrachloride, dichloromethane, trichloromethane, chlorobenzene and dichloromethane. The solvent for the fluorination reaction may differ from that used in the above chlorination reaction. However, for the simplification of the operations and the reduction of the production price, it is favorable to carry out the fluoridation reaction in the solvent used in the chlorination reaction. In this case, the fluorination reaction begins after removal of the chlorine and hydrogen chloride from the solution of the product of the chlorination reaction by blowing an inactive gas such as nitrogen

or helium in the solution.

  The fluorination or halogen exchange reaction proceeds at a sufficiently high rate under the temperature and pressure conditions described below and therefore it is not necessary to use a catalyst for this reaction. However, in the case of the fluorination of a bis (trichloromethoxyphenyl) carbonate (III-) derivative having the substituent X 'halogen, perhaloalkyl or perhaloalkoxyl, the reaction rate is relatively slow and the reaction can be promoted using a suitable catalyst such as antimony pentachloride, antimony trichloride or antimony pentafluoride. By using such a catalyst, the appropriate amount of the catalyst is

  0.1 to 10 mol% of the starting chlorinated compound.

  It is appropriate to use 6.0-6.6 moles of anhydrous hydrogen fluoride per mole of bis (trichloromethoxyphenyl) carbonate. If less than 6 moles of hydrogen fluoride are used, the desired fluorination reaction remains incomplete and the use of more than 6.6 moles of hydrogen fluoride has little effect on the yield of the desired compound and is economically unfavorable. In the case of

  the reaction of a derivative of bis (trichloromethoxyphenyl) -

  carbonate o the substituent X 'is a perchloroalkyl group or a perchloroalkoxyl group, the substituent group is also fluorinated to a perfluoroalkyl group or a perfluoroalkoxyl group. Therefore, in such a case, one uses in the reaction

  an increased amount of hydrogen fluoride.

  It is appropriate to carry out the fluorination reaction at a temperature of from about 0 ° C to about 200 ° C at a pressure of about 0 bar to about 100 bar. At temperatures below 0 ° C, the reaction rate is too slow. When the reaction temperature is above 200 ° C., the hydrogen fluoride vapor pressure becomes too high for easy construction and operation of the reaction apparatus and it is likely that a tar-like substance will be formed by following the decrease in the yield of the target compound. Preferably, the reaction is carried out at a temperature of between 0 and 800 ° C. under a pressure of between 20 bars and 20 bars. Examples of compounds which can be prepared by the process according to the invention are given below:

  bis (4-trifluoromethoxyphenyl) carbonate, bis (3-trifluoro-

  methoxyphenyl) carbonate, bis (3-chloro-4-trifluoro-

  methoxyphenyl) carbonate, bis (2-chloro-4-trifluoro-

  methoxyphenyl) carbonate, bis (2-chloro-5-trifluoro-

  methoxyphenyl) carbonate, bis (4-chloro-5-trifluoro-

  methoxyphenyl) carbonate, bis (3-trifluromethyl-4-

  trifluoromethoxyphenyl) carbonate, bis (2-trifluoromethyl)

  4-trifluoromethoxyphenyl) carbonate, bis (2-trifluoro-

  methyl-5-trifluoromethoxyphenyl) carbonate, bis (4-

  trifluoromethyl-5-trifluoromethoxyphenyl) carbonate,

  bis (3-trifluoromethoxy-4-trifluoromethoxyphenyl) -

  carbonate, bis (2-trifluoromethoxy-4-trifluoromethoxy)

  phenyl) carbonate, bis (2-trifluoromethoxy-5-trifluoro-

  methoxyphenyl) carbonate and bis (4-trifluoromethoxy-5-trifluoromethoxyphenyl) carbonate. The invention will be better illustrated by the

  non-limiting examples that follow.

EXAMPLE 1

  A 300 ml three-necked glass flask was charged with 50 g of bis (4-methoxyphenyl) carbonate and g of carbon tetrachloride. To remove moisture from the reaction system, the temperature was raised while nitrogen gas was blown into the flask until 30 grams of carbon tetrachloride were distilled from the flask. Then, as a free radical generating agent, 1.0 g of azobisisobutyronitrile (AIBN) was placed in the flask. Then, the chlorination reaction was carried out by continuously blowing chlorine gas into the flask while the temperature of the liquid therein was maintained between 65 and 70 C. The reaction was continued for 8 hours. During the 8 hour reaction, AIBN was added several times, each time at 1.0 g, to compensate for the decrease in

  reaction. As a result, his (4-trichloromethoxyphenyl)

  carbonate formed at a selectivity of 79.6%.

  Then were added 20 g of bis (4-trichlorométboxyphényl) carbonate obtained by the above reaction in a stainless steel autoclave of 100 ml together with 10 g of dichloromethane and 24 g of anhydrous hydrogen fluoride and Fluoridation reaction was carried out for 9 hours at a temperature of 130 C under a pressure of 25 bar. After the reaction, the reaction liquid was washed with water and then with a 5% aqueous solution of sodium carbonate and then the dichloromethane was removed using an evaporator. 11 g of bis (4-trifluoromethoxyphenyl) carbonate were then obtained. In the fluorination reaction, the selectivity for the target compound

was 68.2% /.

EXAMPLE 2

  First of all, 50 g of bis (2-chloro-5-

  methoxyphenyl) carbonate by substantially repeating the chlorination reaction of Example 1. The product was

  closed with 62 g of bis (2-chloro-5-trichloromethoxyphenyl) -

  carbonate. The selectivity of the reaction for this compound

was 70%.

  After the chlorination reaction, nitrogen gas was blown into the flask to disperse the chlorine from the reaction liquid and the flask. Then, the reaction liquid was transferred to a stainless steel autoclave and 90 grams of anhydrous hydrogen fluoride was added. In the autoclave, the fluorination reaction was carried out under the same conditions as those of Example 1. As a result, 38 g of bis (2-chloro-5-trifluoromethoxyphenyl) carbonate were obtained. The selectivity of the reaction for this compound was 3%.

EXAMPLE 3

  First of all, 50 g of bis (3-chloro-4-

  methoxyphenyl) carbonate by substantially repeating the chlorination reaction of Example 1. The product was

  formed of 62 g of bis (3-chloro-4-trichloromethoxyphenyl) -

  carbonate. The selectivity for this compound was

72.0%.

  Then, 20 g of bis (3-chloro-4-trichloromethoxyphenyl) carbonate were reacted with anhydrous hydrogen fluoride under the same conditions as in the fluorination reaction of Example 1.

  12 g of bis (3-chloro-4-trifluoro-

  méthoxypbényl) carbonate. The selectivity for this compound

was 68.5%.

EXAMPLE z

  First, 50 g of bis (2-chloro)

  4-methoxyphenyl) -carbonate substantially repeating the fluorination reaction of Example 1. This product was

  formed of 60 g of bis (2-chloro-4-tricbloromethoxyphenyl) -

  carbonate. The selectivity for this compound was 67.2%.

  Then, 20 g of bis (2-

  chloro-4-trichloromethoxyphenyl) carbonate with anhydrous hydrogen fluoride under the same conditions as in the fluorination reaction of Example 1.

  10 g of bis (2-chloro-4-trifluoro-

  methoxyphenyl) carbonate. The selectivity for this compound has

was 66.3%.

EXAMPLE 5

  First of all, 50 g of bis (3-tricylic acid) were

  romethyl-4-methoxyphenyl) carbonate by repeating

  substantially the blinding reaction of Example 1.

  The product consisted of 59 g of bis (3-trichloromethyl)

  4-trichlorométhoxyphényl) carbonate. Selectivity for

this compound was 69.3%.

  Then, 20 g of bis (3-

  tricbhloromethyl-4-trichloromethoxyphenyl) carbonate with anhydrous hydrogen fluoride under the same conditions as the fluorination reaction of Example 1. By

  subsequently, 9 g of bis (3-trifluoromethyl-4-

  trifluoromréthoxyphényl) carbonate. The selectivity for this

compound was 67.0%.

(III) .O = D

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(II) 0 = 3- OJ)

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ILS L Z 7 9O

  X 'is as defined above with respect to the general formula (II), and (b) reacting the compound represented by the general formula (III) with anhydrous hydrogen fluoride in an organic solvent. 2. Method according to claim 1, characterized in that the reaction in step (a) is carried out at a temperature between about 30 0C

and 150 C.

  3. Method according to claim 1, characterized in that the organic solvent of step (a)

is a non-polar solvent.

  4. Process according to claim 1, characterized in that the organic solvent of step (a) is selected from the group consisting of carbon tetraehloride, dichloromethane, trichloromethane and chlorobenzene.

and dichlorobenzene.

  5. Method according to claim 1, characterized in that the reaction in step (a) is carried out in the presence of a free radical generating agent selected from the group consisting of peroxides

  organic and organic azo compounds.

  6. Process according to claim 1, characterized in that the reaction in step (b) is carried out at a temperature of between approximately 0 ° C. and approximately 2000 ° C. at a pressure of between approximately 1 ° C.

bar and about 100 bars.

  7. Method according to claim 6, characterized in that the above temperature is between 0 and 80 C and the above pressure is

between 5 and 20 bar.

  8. Process according to claim 1, characterized in that the organic solvent in step (b) is selected from the group consisting of carbon tetrachloride, dichloromethane, trichloromethane, chlorobenzene and dichlorobenzene. 9. Process according to claim 1, characterized in that the reaction in step (b) is carried out in the presence of a catalyst which is a

antimony halide.

  10. Process according to claim 1, characterized in that X 'in the general formulas (II) and (III) is a chlorine atom, a trichloromethyl group or a trichloromethoxy group and X in the general formula (I) is a atom of chlorine, a group

  trifluoromethyl or a trifluoromethoxyl group.