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United States Patent (19) (11) 4,124,646 Kawamura Et Al

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United States Patent (19) (11) 4,124,646 Kawamura Et Al United States Patent (19) (11) 4,124,646 Kawamura et al. 45) Nov. 7, 1978 (54) PROCESS FOR PRODUCING THIOANISOLE 3,450,771 /1969 Dombro ............................. 260/609 3,470,257 /1969 Sparks ........... 260/609 75 Inventors: Masao Kawamura, Akashi; Masakazu Hatta, Kakogawa; Nobuhiro Koune, OTHER PUBLICATIONS Kobe; Nobuyuki Kitagishi, Takasago, Hansch et al., JACS, 72 (1950), 4810. all of Japan Vogel, JCS, (1948), 1820. 73 Assignee: Seitetsu Kagaku Co., Ltd., Japan Primary Examiner-Lewis Gotts 21 Appl. No.: 737,623 Assistant Examiner-Molly C. Eakin Attorney, Agent, or Firm-Pollock, Vande Sande & (22 Filed: Nov. 1, 1976 Priddy (30) Foreign Application Priority Data 57 ABSTRACT Nov. 5, 1975 JP Japan ................................ 50/133345 Industrially useful alkylphenyl sulfides are produced in Dec. 5, 1975 JP Japan ................................ 50/145280 high yield from phenyl mercaptan as a raw material by 51) Int. Cl.' ............................................ C07C 148/00 reaction of the phenyl mercaptan with an alkyl alcohol 52 U.S.C. ................................................. 260/609 E or dialkyl ether, or alkyl mercaptan or dialkyl sulfide 58) Field of Search .................................... 260/609 E having 1 to 4 carbon atoms as a novel alkylating agent (56) References Cited at an elevated temperature, for example, 150' to 600 C, U.S. PATENT DOCUMENTS in a gaseous phase. 2,745,878 /1956 Mavity ................................. 260/609 6 Claims, No Drawings 4,124,646 1 2 pyl alcohol, n-butyl alcohol, i-butyl alcohol, tert.butyl PROCESS FOR PRODUCING THIOANISOLE alcohol; dialkyl ethers such as dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, methylethyl ether, This invention relates to a novel process for produc ethylpropyl ether; alkyl mercaptan such as methylmer ing alkylphenyl sulfides. 5 captan, ethyl mercaptan, n-propyl mercaptan, n-butyl Alkylphenyl sulfides are industrially useful com mercaptan, tert.butyl mercaptan; dialkylsulfides such as pounds as raw materials for medicaments, agricultural dimethyl sulfide, diethyl sulfide, dipropyl sulfide, dibu chemicals, etc., and above all thioanisole is a very useful tyl sulfide, etc. compound having wide applications to herbicides, in In the present invention, the alkyl alcohols and the secticides and various solvents. 10 alkyl ethers can be used alone or in a mixture of at least Heretofore, the alkylphenyl sulfides have been usu two thereof, and the alkyl mercaptans and dialkyl sul ally produced by alkylating phenyl mercaptan with an fides can be used alone or in a mixture of at least two alkylating agent such as dialkyl sulfate, alkyl halide, thereof, as the alkylating agent. alkyl amine, etc., and above all the alkylation with dial In the case of dialkyl ether or dialkyl sulfide, the kyl sulfate has been regarded as preferable on account 15 process will be more simple, and its industrial practice of higher yield than those with other alkylating agents will be easier, when said R and R are identical with (A. I. Voger: JCS 1948 1820). However, these alkyla each other, as in the case of dimethyl ether, diethyl tions are all carried out in liquid phase, which requires ether, dimethyl sulfide, or diethyl sulfide. complicated steps for separating the reaction products, A mode of practising the present invention will be or the separated waste liquor or the like offers a prob- 20 described below. lem, when the prevention of environmental pollution is A molar ratio of the alkyl group of an alkylating taken into account. Especially, the process using dialkyl agent, R1OR2 or RSR2, to the phenyl group of phenyl sulfate is still not an advantageous one for industrial mercaptan, is in a range of 0.1 to 10, preferably 0.5 to application because the dialkyl sulfate is expensive, and 5. The molar ratio of more than 10 has no considerable because the dialkyl sulfate is so strongly irritating that 25 influence upon the yield, and a larger amount of the its handling is quite inconvenient, etc. alkylating agent must be uselessly handled, making the The present inventors have made an extensive study process uneconomical. Moreover, the larger amount of of a process for producing alkylphenyl sulfide by a the alkylating agent is liable to increase the steps of gaseous phase reaction that is advantageous in the in purification to remove the byproducts. On the other dustrial practice, and as a result have found that the 30 hand, the molar ratio of less than 0.1 naturally decreases alkylphenyl sulfides can be formed by reacting phenyl the yield, and a larger amount of phenyl mercaptan mercaptan with at least one of alkylating agents repre must be uselessly handled, making its industrial practice sented by the general formula, ROR2, wherein R is an unsuitable. Therefore, an appropriate molar ratio of the alkyl group having 1 to 4 carbon atoms, and R2 is a alkylating agent to phenyl mercaptan should be selected hydrogen atom, or an alkyl group having 1 to 4 carbon 35 in said range. For example, in the case of using phenyl atoms, or at least one of alkylating agents represented mercaptan, and methanol, dimethyl ether, methyl mer by the general formula, RSR, wherein R represents captain or dimethyl sulfide as the alkylating agent, the an alkyl group having 1 to 4 carbon atoms, and R2 yield of the desired product thioanisole reaches a maxi represents a hydrogen atom or an alkyl group having 1 mum, that is, 96% or more, based on the fed phenyl to 4 carbon atoms at an elevated temperature condition 40 mercaptan, when the molar ratio of the alkyl group of in a gaseous phase. When there is a catalyst, for exam the alkylating agent to the phenyl group of phenylmer ple, activated alumina, in the reaction system, it has captan of 1.0 to 2.0 is selected in view of the above been found that said reaction is considerably promoted, considerations. and the present invention has been established based on Reaction temperature for carrying out the alkylation the foregoing findings. 45 of the present invention must be high enough to main An object of the present invention is to provide a tain said two raw materials in a gaseous phase, but not novel process for producing alkylphenyl sulfides in so high as to decompose the raw materials and the reac good yield with industrial advantages, using phenyl tion product, and is usually in a range of 150 to 600 C., mercaptan and a low cost alkylating agent. The present preferably 200 to 500° C. In most cases, the alkylation invention is characterized by using an alkylating agent 50 is carried out under the atmospheric pressure, but, if represented by the general formula, ROR2 or RSR2 desired, can be carried out under an increased or re wherein R represents an alkyl group having 1 to 4 duced pressure. To obtain a good contact of the two carbon atoms, and R represents a hydrogen atom or an raw materials, heat-resistant materials, such as porcelain alkyl group having 1 to 4 carbon atoms, which has been rings, can be filled in a reactor before the alkylation, if so far unknown as the alkylating agent for phenylmer- 55 desired. captan, and conducting the alkylation reaction in a It is desirable to conduct the alkylation of the present gaseous phase. More particularly, the characteristics of invention in the presence of a catalyst, which is very the present invention are that the present alkylating effective for promotion of the reaction. Examples of the agent is cheap, by-products are hardly produced, yields catalyst include activated alumina, silica, silica-alumina, of alkyl phenylsulfides are high, and the process is very 60 activated acid clay, zeolite, diatomaceous earth, other simple and thus is very economically advantageous, as silica-alumina compositions, activated carbon, etc. Usu compared with the conventional process, ally the shape of the catalyst is granular, and its sizes are The alkylating agent represented by the general for in a range of 2 mm to 10 mm. These catalysts can be mula, ROR, or RSR2, where R represents an alkyl used alone or in a mixture of at least two thereof, or group having 1 to 4 carbon atoms, and R2 represents a 65 together with an additive of improving the strength or hydrogen atom or an alkyl group having 1 to 4 carbon activity of the catalyst, atoms include, for example, alkyl alcohols such as The catalytic reaction in the gaseous phase of the methyl alcohol, ethyl alcohol, n-propyl alcohol, i-pro present invention is carried out at said reaction tempera 4,124,646 3 4. ture usually in a tubular reactor at a space velocity of 20 methyl alcohol and/or dimethyl ether as an alkylating to 2000 hrt, though depending upon the selected reac agent. The thioanisole yield based on phenyl mercaptan tion temperature. can reach 96% or more by selecting appropriate reac At the elevated temperature as in the present inven tion conditions, and the reaction product can be readily tion, especially in the presence of the catalyst dialkyl separated into an aqueous layer and an oil layer by ether and water are formed from alkyl alcohol, and cooling the reaction product. The oil layer contains a reversibly alkyl alcohol from dialkyl ether and water. small amount of the unreacted raw materials, but more In the case of alkyl mercaptan and dialkyl sulfide, than 95% by weight of the oil layer is thioanisole, and di-alkyl sulfide and hydrogen sulfide are similarly the thioanisole yield, based on the reacted phenyl mer formed from alkyl mercaptan, and reversibly alkyl mer 10 captan, reaches a surprisingly high value such as 99%. captan from dialkyl sulfide and hydrogen sulfide. By distilling the oil layer, a fraction of unreacted phenyl Therefore, even if, for example, methyl alcohol, or mercaptan and successively a fraction of thioanisole can dimethyl ether, or a mixture thereof is used to react be obtained.
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