DK141601B - Process for chlorination in preferably para and / or ortho position of a phenolic compound by reaction with sulfuryl chloride using a catalyst. - Google Patents

Description

(11) PUBLICATION 141601 C 07 C 39/27 DENMARK (c. Intci.3 c 07 b 9/00 c 0; c «/«, C 07 C 59/70 t (21) Note 1 617/75 ( 22) Filed on 15 * aPr · 1975 (23) Running Dec 15 · Apr 1975

(44) The claim presented and R

the petition published on May 5, IUU

DIRECTORATE OF

PATENT AND TRADEMARKET SYSTEM (30) Prior Request from (71) THE DOW CHEMICAL COMPANY, 2050 Abbott Road, Midland, Michigan, US.

(72) Inventor: William David Watson, 5008 Spruce Street, Midland, Michi = gan, US.

(74) Plenipotentiary;

The company Chas. Hude.

(54) Process for chlorination in preferably para and / or ortho positioning of a phenolic compound by reaction with sulfuryl chloride using a catalyst.

The present invention relates to a process for chlorinating a phenolic compound.

From the specification to Danish Patent No. 83,955, it is known to chlorinate phenols with sulfuryl chloride alone and in the presence of a Friedel-Crafts catalyst such as AICI3, but long reaction times are required.

From the specification to Swedish Patent No. 301,155, chlorination of o-cresol using sulfuryl chloride is known in the presence of a metal = halide and Fuller soil. In the only exemplary embodiment, the reaction time is long, viz. 20 hours, the o-cresol conversion 63.2% and the 4-chloro-o-cresol yield, calculated on the o-cresol amount, approx. 58%.

According to the invention, there is provided a special process for chlorinating a phenolic compound of the general formula:

OR

The R 'wherein R is H, phenyl, alkyl or carboxyalkyl of 1-6 carbon atoms in the alkyl groups, R' is alkyl of 1-6 carbon atoms or halogen at the ortho or meta position, and n is 0-2, by reaction of the aromatic compound with sulfuryl chloride in the liquid phase and in the presence of a catalyst.

In the process of the invention, high yields of the desired compounds can be obtained at short reaction times.

The process according to the invention is characterized in that the catalyst consists of 0.1-10 wt. Of a metal salt and 0.02-10 wt. Of an organic divalent sulfur compound, calculated on the weight of the aromatic compound, wherein the metal salt is a halide of antimony, aluminum. , iron, tin, titanium or zinc or aluminum phenoxide, and wherein the sulfur compound is thiophene, p-dithian, diphenyl sulfide, thianthrene, dibenzyl sulfide, polyphenylene sulfide, diphenyl disulfide, thiophenol, dibenzothiophene, phenyl or halogen, or carbon disulfide, and the reaction temperature is 10-100 ° C.

The other reaction conditions are not critical and are usually worked in accordance with known methods and conditions for chlorination with sulfuryl chloride.

Metal halides derived from antimony, aluminum, iron and tin or aluminum phenoxide are preferred because of high selectivity. Catalysts derived from aluminum and iron are especially preferred because of their commercial availability and high selectivity. The halides of these metals, especially the chlorides, are of major importance in the reaction.

3 141601

Among the sulfur compounds, thiophene, p-dithian, diphenylsulfide, thianthrene, dibenzylsulfide, polyphenylene sulfide, diphenyl disulphide and thiophenol are preferred, and thiophene, p -dithian, diphenylsulfide and thian = threne are particularly preferred.

The organic divalent sulfur compounds may each contain substituents such as an alkyl or alkoxy of up to 10 carbon atoms, phenyl or halogen, which do not materially impair the efficiency of the reaction.

Preferred substituents on the sulfur cocatalysts are the hydrocarbon substituents with up to 6 carbon atoms. Representative examples of suitable substituted sulfur cocatalysts include: trichloro-thiophene, biphenylphenyl sulfide, polythiophene, bromophenylphenyl sulfide, methylthiophenol, di- similar compounds.

The concentration of the metal salt varies from 0.1 to 10% by weight of the aromatic compound. However, quantities greater than 5% provide little improvement. The concentration of the sulfur compound is from 0.02 to 10% by weight based on the aromatic compound and 0.05-2% by weight is preferred.

The aromatic chlorinated compound of the invention may conveniently be any compound of the general formula described previously. Phenol, diphenyl ether and alkyl phenols wherein the alkyl group contains 1-6 carbon atoms are particularly preferred and the dichlorination of phenol and the monochlorination of o-cresol are of particular interest.

The reaction conditions with respect to temperature and pressure can vary greatly when various aromatic compounds are chlorinated. The reaction is carried out in liquid phase at a temperature of 10-100 ° C. Although the rate of reaction increases as the temperature increases, the selectivity of the ice cream distribution tends to decrease when higher temperatures are used. For this reason, temperatures in the range from life to 60 °, 4 U1601 are particularly preferred when selectivity is important. The reaction is usually carried out at atmospheric pressure, but at higher temperatures it may be necessary to increase the pressure to maintain the liquid phase.

Solvents may optionally be used. Suitable solvents include those described by Campbell and Shield in Tetrahedron 21 (2) 221 (1965), but it is preferred to carry out the reaction without the presence of a solvent.

The invention is illustrated by the following examples.

Examples 1-3 * 1 and Comparative Examples A-E

The reaction of 1 gram of o-cresol with 1 gram of sulfuryl chloride was conducted in parallel experiments to determine the effect of various cocatalysts on the rate and selectivity of the chlorination.

The o-cresol was placed in a reaction vessel maintained at the temperature indicated in the tables, and sulfuryl chloride was continuously added at that temperature during the time shown in the tables. After the addition, the reaction mixture was heated to remove dissolved gas and the product obtained was analyzed by vapor phase chromatography. In each example, the reaction was carried out in the presence of 1 gram of the organic sulfur catalyst and 1 gram of metal catalyst.

Table 1 shows comparative examples of o-cresol and sulfuryl chloride or chlorine in the presence or absence of catalysts. Table 2 shows the reaction of o-cresol and sulfuryl chloride in the presence of dihydric sulfur catalysts and AlCl 3 of the present invention. Table 3 shows the reaction of o-cresol and sulfuryl chloride in the presence of various metal salt catalysts and diphenyl sulfide. Table shows the effect of substituents on diphenyl sulfide in the reaction of sulfuryl chloride with o-cresol. Table 5 shows the reaction of various substituted phenols. Table 6 shows the chlorination of different ethers. In all the tables, the product analysis heading kCl / eci is the amount of the monochlorine product which is para-substituted divided by the amount of the monochlorine product which is ortho-substituted.

In the tables, 0 means phenyl.

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Table 5

Chlorination of 1 mole of differently substituted phenols with sulfuryl chloride in the presence of 0.1 g of PeCl 2 and 0.2 g of diphenyl sulfide at 15-20 ° C for 2 hours

Substituted -ProduMaualysis, ... ^ -

Ex. phenol unreacted 4C1 / 601 Dichloro 2 5 m-methyl 2.3 7.5 5.1 26 o-ethyl 0.5 16.23 1.5 27 on-propyl 1.3 15.4 0.9 28 o-ethyl isopropyl 0.4 8.7 2.7 29 o-sec-butyl 1.3 14.2 0.4 30 ot-butyl 0.3 5.4 3.0 31 o-cyclohexyl 2.4 6.65 l , 9

Table 6

Chlorination of 1 mole of different ethers with sulphuryl chloride in the presence of 0.2 g EeCl 2 and 0.1 g di = phenylsulfide at 15-20 ° 0 1 2 hours

Product Analysis, Weight # _

Ex. Ether unreacted 401/601 Dichloro 32 anisole 2.6 8.1 0.3 33 o-methylanisole 1.4 26.3 0 34 diphenyl ether 13.0 10.1 11.7 In the following Table 7,% conversion and% are summarized yield obtained in Examples 1-34.

10 141601

Table 7% yield of 4-C1 calculated on added%% yield, theoretical amount of phenolic

Example Conversion 4-Cl 6-C1 Dichloro Compound 1 96.2 95.1 4.4 0.5 91.5 2 97.5 94.9 4.6 0.5 92.4 3 99.96 91.4 4 , 8 3.8 91.3 4 94.5 86.6 4.8 8.6 81.9 5 86.4 93.4 5.9 0.7 80.6 6 99.9 89.7 7.8 2.5 89.6 7 95.9 91.9 7.9 0.2 88.5 8 96.6 91.0 8.2 0.8 87.9 9 89.6 90.6 8.3 1, 1 81.1 10 93.2 90.1 9.1 0.8 83.9 11 77.9 90.4 9.6 0.0 70.4 12 94.1 94.9 4.9 0.2 89 , 3 13 100 90.3 4.2 5.5 14 95.1 94.6 5.1 0.3 89.9 15 95.9 93.5 5.1 1.4 89.7 16 96.3 93 , 9 5.4 0.7 90.4 17 97.2 92.5 5.9 1.6 89.9 18 93.6 90.3 7.9 1.8 84.5 19 .94.5 90, 5 8.4 1.1 85.5 20 93.4 93.3 5.0 1.7 87.2 21 86.1 85.2 4.7 10.1 73.4 22 83.8 93.7 5 , 8 0.5 78.5 23 95.7 91.5 6.7 1.8 87.6 24 95.6 90.4 8.8 0.8 86.4 25 97.0 85.9 11.4 2.6 83.4 26 99.3 92.9 5.8 1.3 92.2 27 98.4 93.2 6.0 0.8 91.7 28 99.5 87.4 7.2 5, 4 86.9 29 98.4 93.1 6.5 0.4 91.6 30 99.6 75.3 22.1 2.6 75.0 31 97.1 85.5 12.8 1.7 83 , 0 32 96.6 88.8 10.9 0.3 85.8 33 98.2 96.3 3.7 0 94.6 34 84.5 80.4 7.9 11.7 67.9

Example 35 11 141601

Chlorination of phenol with EeCl 2 -diphenyl sulfide In the same way as shown above, 5 moles of phenol were reacted with 10.5 moles of sulfuryl chloride in the presence of 1 g diphenyl sulfide and 1.5 g EeCl 2. The sulfuryl chloride was added continuously at a temperature of about 25 ° C over 15/4 hours. After 5/4 hours, a sample showed that the product distribution by weight% was: 1.7% phenol, 8.5% 2-chloro = phenol, 89.5% 4-chlorophenol and 0.5% 2,4-dichlorophenol for a 4- to 2-isomer ratio of 10.5. After 15/4 hour at 25 ° C, the reaction mixture was heated to ca. 85 ° C for 1/4 hour and 819.9 g of product were recovered and found by analysis to contain: 97j3% 2,4-dichloro = phenol, 0.4% 2,6-dichlorophenol and 2.0% 2 , 4,6-trichlorophenol for a 2.4- to 2.6-isomer ratio of over 200. In a comparison experiment using direct chlorination of phenol with chlorine in the presence of an Eriedel-Craft catalyst, 2.4- to 2, 6-isomer ratio 11.5. In the absence of a sulfur activator, only 4% dichlorophenol was obtained with 2.1 moles of sulfuryl chloride in the presence of 2% FeCl 2 for 24 hours at 40-45 ° C.

Example 56

Chlorination of o-chlorophenol In the same way as shown above, 1 mole of 2-chlorophenol was chlorinated with 1 mole of sulfuryl chloride in the presence of 0.2 g of diphenyl sulfide and 0.5 g of EeCly Sulfuryl chloride was added over 2 1/2 hours at 35 ° C, and after heating to 85 ° C for 1 hour, 163.2 g of product were isolated which, by analysis, were found to contain: 1.6% 2-ehloro = phenol, 94.0% 2,4-dichlorophenol, 4 , 2% 2,6-dichlorophenol and 0.2% 2,4,6-trichlorophenol for a 2.4 to 2.6 isomer ratio of 22.4.

Example 37

Chlorination of diphenyl ether In a similar manner as described above, 0.2 moles of diphenyl ether were reacted with 0.4 moles of sulfuryl chloride in the presence of 1 g of diphenyl sulfide and 1 g of AlCl 2. The sulfuryl chloride was continuously added to the diphenyl ether over 45 minutes at a temperature of 22-30 ° C. The mixture was then kept at 70 ° C for 1 hour and 45 g of product were recovered which, by analysis, were found to contain: 3% monochlorodiphenyl ether, 19.8% 2,4'-dichlorodiphenyl ether and 11.2% 4 , 4'-dichlorodiphenyl = ether for a 4,4 'to 2,4' isomer ratio of 3.9.

Claims (2)

Example 38 Ohloration of 3,5-xylenol In a similar manner to the above examples, a reaction vessel was provided with 490 g (4.0 mole) of 3,5-xylenol, 4.0 g of diphenyl = sulfide and 4.0 g EeClj. To this reaction mixture was added slowly over 2 1/2 hours 540 g (4.0 moles) of sulfuryl chloride. The final product, by analysis, was found to contain 1.9 wt $ 3,5-xylenol, 2.4 $ 2-chloro-3,5-xylenol and 89.9 $ 4-chloro-3,5-xylenol. Example 39 Oloration of 2-methylphenoxyacetic acid. In a similar manner to the above examples, 20.8 g (0.125 mole) of 2-methylphenoxyacetic acid in 60 g of glacial acetic acid, 5 drops of diphenyl sulfide and 0.1 g of EeCl 2 were added to a reaction vessel. To this reaction mixture was slowly added 16.9 g (0.125 mol) of sulfuryl chloride over 1 hour and 20 minutes. The product obtained weighed 25.8 g and had a melting point of 111-113 ° C. An analysis of the product showed that this contained 2.5% by weight of $ 2-methylphenoxyacetic acid, 90.8% by weight 4-chloro-2-methylphenoxyacetic acid, 5.8% by weight 6-chloro-2-methyl = phenoxyacetic acid, and 0.2% by weight % 4,6-dichloro-2-methylphenoxyacetic acid. The 4-chloro to 6-chloro ratio was 15.6. Claims. A process for ohlorination in preferably para and / or ortho position of a phenolic compound of the formula: OR (o) - wherein R is H, phenyl, alkyl or carboxyalkyl of 1-6 carbon atoms in the alkyl groups, R 'is alkyl having 1-6 carbon atoms or halogen at the ortho or meta position, and n is 0-2, by reacting the aromatic compound with sulfuryl chloride in the liquid phase and in the presence of a catalyst, characterized in that the catalyst consists of 0.1 -10% by weight of a metal salt and 0.02-10% by weight of an organic