Title of Invention	PROCESS FOR PRODUCING ANTHRACENE DIETHER
Abstract	An industrially advantageous process is presented wheraby a high purity anthracene diether can be produced in good yield. 5 An aqueous medium containing an alkali salt of 9,10- anthracenediol is added to an organic solvent containing an etherifying agent in the presence or absence of a quaternary ammonium compound or a quaternary phosphonium compound, to carry out the etheritying reaction to 10 produce the anthracene diether.

Title of Invention

PROCESS FOR PRODUCING ANTHRACENE DIETHER

Abstract

An industrially advantageous process is presented wheraby a high purity anthracene diether can be produced in good yield. 5 An aqueous medium containing an alkali salt of 9,10- anthracenediol is added to an organic solvent containing an etherifying agent in the presence or absence of a quaternary ammonium compound or a quaternary phosphonium compound, to carry out the etheritying reaction to 10 produce the anthracene diether.

Full Text	I/We, (1) Kawasaki Kasei Chemicals Ltd. of (2) 12-1. Ekimaeoncho, Kawasaki-ku., Kawasaki-shi, Kanagawa 210-0007 Japan a/an (3) Japanese do hereby certify that the attached document is a complete and faithful English translation of - * the Specification comrprising of the description, the claims as filed, text matter of drawings (if any) and the Abstract ■—the Claimo as amended under PCT Article No. 19 ■—the Statement as filed under PCT Article No. 19 ■—the amendments—to—the deseription,—the claime,the- text ---matter of the drawings that are annexed to the- ---International preliminary Examination Report in respect of the International Application No. PCT/JP02/13314 filed on December 19, 2002 at Japan (Receiving Office) , Dated this l7th day of may 2005 (4) Signature Name (in block letters) ______Takamori Miyazaki____________ Designation Board Director, General Manager of Research and_Devilopment Center (1) Name of the Applicant in India. (2) Address of the Applicant, (3) Nationality (state of incorporation for corporate bodies) of the applicant in India. (4) Signature of the applicant "Note: Please use separate verification formats for each. document while striking out the inapplicable portions for the respective verifications. 1 DESCRIPTION PROCESS FOR PRODUCING ANTHRACENE DIETHER 5 TECHNICAL FIELD The present invention relates to a process for producing an anthracene diether. More particularly, it relates to a process for producing a dialkoxyanthracene useful as a sensitizer for a photocurable composition 10 employing energy rays such as ultraviolet rays as the light source, particularly a dialkoxyanthracene such as 9 , 10-dipropoxyanthracene or 9,10-dibutoxyanthracene, or a diaryloxyanthracene such as 5,10-diphenoxyanthracene. 15 BACKGROUND ART Heretofore, as a process for producing a 9,10- dialkoxyanthracene, a process is, for example, known wherein an anthracenedione compound is reduced and alkylated as disclosed in u. Seitz at al., Synthesis, 20 686-688 (1986) . The process disclosed in this publication is a process wherein in a two phase solvent system having water and methylene chloride mixed, hydrosulfite is used as a reducing agent, and methyl iodide is used as an alkylating agent. However, the 25 process disclosed in this publication has a problem of environmental pollution by methylene chloride, and further it can hardly be regarded as an industrially 2 advantageous process, as an expensive alkylating agent is employed. Further, JP-A-2000-119208 discloses a process wherein an anthracenedione compound is reduced and 5 alkylated in an alcohol medium by using hydrosulfite as a reducing agent and diethyl acetate as an alkylating agent. However, according to the test conducted by the present inventors, if dipropyl sulfate or propyl bromide was used as an alky1asting agent when dipropoxy anthracene 10 was prepared by the process disclosed in this publication, by-products were substantial, and the desired dipropoxyanthracene was not obtained. Further, in a case where butyl bromide was used as an alkylating agent, dinutoxyan thracene could not be obtained. 15 Under such a circumstance, the present inventors have conducted an extensive study for the purpose of providing a process for producing, industrially advantageously in good yield, a dialkoxyanthracene, particularly a high purity anthracene diether such as 20 9,lO-dipropoxyanthracene or 9,10-dibutoxyanthracene, and as a result, the present invention has been accomplished. DISCLOSURE OF THE INVENTION To solve the above-mentioned problems, the present 25 inventors have conducted an extensive study and as a result, have arrived at the present invention having the following constructions.+ (1) A process for producing an anthracene diether represented by the following formula (1): (wherein R is an alkyl group, an allyl group, an aryl group, a benzylgroup, a hydroxyalkyl group or an 5 alkoxyalkyl group, each of R5 and R6 is a substituent inert to etherification, and each of m and n is an integer of from 0 to 4), which comprises reacting an etherifying agent and an alkali salt of a 9,10- anthracenediol compound to produce the anthracene diether, 10 characterized in that an aqueous medium containing the alkali salt of a 9,10-arrthracenediol compound, is added to an organic solvent containing the etherifying agent to carry out the reaction, (2) The process for producing an anthracene diether 15 according to the above (1), wherein the etherifying agent is one selected from dialkyl sulfates, alkyl hales, aryl halides or allyl halides. (3) The process for producing an anthracene diether according to the above (1) or (2), wherein the organic 20 solvent is one selected from polar solvents, (4) The process for producing an anthracene diether according to the above (3), wherein the polar solvents are those selected from aprotic polar solvents. 4 (5) A process for producing an anthracene diether represented by the following formula (1) : (wherein R is an alkyl group, an allyl group, an aryl 5 group, a benzyl group, a hydroxyalkyl group or an alkoxyalkyl group, each of R5 and R6 is a substituent inert to etherification, and each of m and n is an integer of from 0 to 4), which comprises reacting an echerifying agent and an alkali salt of a 9,10- 10 anthracenediol compound to produce the anthracene diether, characterized in that an aqueous medium containing the alkali salt of a 9,10-anthracenediol compound and an organic solvent containing the etherifying agent are mixed in the presence of a quaternary ammonium compound 15 or a quaternary phosphonium compound to carry out the reaction. (6) The process for producing an anthracene diether according to the above (5), wherein the aqueous medium containing the alkali salt of a 9,10-anthracenediol 20 compound is added to the organic solvent containing the etherifying agent to carry out the reaction. (71 A process for producing an anthracene diether 5 represented by the following formula (1) : (wherein R is an alkyl group, an allyl group, an aryl group, a benzyl group, a hydroxyalkyl group or an 5 alkoxyalkyl group, each of R5 and R6 is a substituent inert to etherification, and each of m and n is an integer of from 0 to 4), which comprises reacting an etherifying agent and an alkali salt of a 9,10- anthracenediol compound co produce the anthracene diether, 10 characterized in that an aqueous medium containing the alkali salt of a 9,10-anthracenediol compound is added to an alkyl halide in the presence of a quaternary ammonium compound or a quaternary phosphonium compound to carry out the reaction- 15 (8) The process according to the above (5), (6) or (7), wherein as the quaternary ammonium compound or the quaternary phosphonium compound, a quaternary ammonium compound or a quaternary phosphonium compound represented by the following formula (4): 20 R1 (wherein each of Rl to R4 which are independent of one another, is a low molecular weight or high molecular weight organic group, particularly a substituted, or 5 unsubstituted alkyl, cycloalkyl or aryl group, Y is a nitrogen atom or a phosphorus atom, and An- is an anian) is used. EMBODIMENTS OF THE INVENTION 10 The first embodiment of the present invention is a process wherein an aqueous medium containing an alkali salt of a 9,10-anthracenediol compound is added to an organic solvent containing an etherifying agent to carry out the reaction. 15 The 9,10-anthracenediol compound is represented by the following formula (2) : (wherein like in the above formula (1), each of R5 and R6 7 is a substituent inert to etherification, and each of in and n is an integer of from 0 to 4)and can be obtained. by reducing the corresponding 9,10-anthracenedione compound. 5 Each of substituents R5 and R6 is a substituent inert to the etherification reaction in the process of the present invention. Specifically, a C1-10 alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkylamino group, an alkylsulfonyl group, an 10 alkoxycarbony1 group or a halogen group, may, for example, be mentioned. Each of m and n represents the number of substituents bonded to the aromatic ring and is an integer of from 0 to 4, preferably an integer of from 0 to 2 . 15 In an aqueous medium containing an alkaline active agent, the 9,10-anthracenediol compound is dissolved in the form of an alkali salt of a 9,10-anthracenediol compound represented by the formula (3): 20 (wherein R5, R6, m and n have the same meanings as in the above formula (2) , and M is an alkali metal) . As such an alkaline active agent, sodium hydroxide or potassium 8 hydroxide may, for example, be mentioned, and it is used in an amount of preferably at least 2 times by mol, more preferably from 2.2 to 3 times by mol, relative to the 9, 10-anthracenediol compound. The aqueous medium means, 5 in addition to water, a lower alcohol such as methyl alcohol, ethyl alcohol or isopropyl alcohol or a mixed medium of such a lower alcohol with water, or a water, soluble ether such as tetrahydrofuran or dioxane or a raixjed medium of such a. water-soluble lower ether with 10 water. The solubility of the alkali salt of a 9,10- anthracenediol compound varies depending upon the types of the substituents, but in the case of an aqueous solution, a solution having a. concentration of from about 5 to 30 wt% is preferably selected. 15 As the method for reducing the 9,10-anthracenedione compound, (1) a method of carrying out hydrogen reduction in a solvent such as an alcohol in the presence of a hydrogenation catalyst, or (2) a method of carrying out reduction in an aqueous mediuma by means of hydrosulfite, 20 may, for example, be mentioned. The above method (2) is preferred, since by the reduction in the presence of an alkaline compound such as sodium hydroxide, an alkali salt of a 9,10-anthracenediol compound can directly be obtained. Further, (3)a method for producing an alkali 25 salt of anthracenediol which comprises reducing 9,10- anthracenedione with a solution of an alkaline compound of 1,4-dihydro-9,10-dihydroxyanthracene (JP-A-9-16982) 9 may, for example, be mentioned, This method (3) is preferred, since 1,4-dihydro-9,10-dihydroxyanthracene used for the reduction, becomes anthracene diol, whereby there will be no necessity to remove the reducing agent 5 after use. The etherification agent in the present invention may, for example, be an alkylating agent, an aryl- modifying agent or art allyl-modifying agent, which will be described below. Namely, the alkylating agent may, 10 for example, be a dialkyl sulfate such as diethyl sulfate or dipropyl sulfate, or an alkyl halide such as ethyl bromide, propyl bromide or butyl bromide. The aryl- modifying agent may, for example, be an aryl halide such as bromobensene, chlorobenzene, p-chlorotoluene, p- 15 bromotoluene, m-bromotoluene, m-chlorotoluene, a chloronaphtha1ene, a -bromonaphthalene,b- chloronaphthalene or b-bromonaplithalene. Further, the allyl-modifying agent may, for example, be an allyl halide such as allyl bromide, allyl chloride or methallyl 20 chloride. As other etherifying agents, 2-bromoethanol may be mentioned for hydroxyethylation, and 2- bromoethylmethyl ether may be mentioned for methoxyethyllation. Among these etherifying agents, from the viewpoint 25 of the reactivity, etc.. preferred is a dialkyl sulfate, an alkyl halide, an aryl halide or an allyl halide, and particularly preferred is an alkyl halide such as propyl 10 bromide or butyl bromide. Such an etherifying agent is used in an amount of at least 2 times by mol, particularly preferably within a range of from 2 to 5 times by mol, relative to the alkali metal of a 9,10- 5 anthracenediol compound as the material. If it is less than 2 times by mol, an unreacted case will increase, and if it exceeds 5 times by mol, side reactions will increase, such being undesirable. In the present invention, the organic solvent to 10 contain such an etherification agent may be any solvent, so long as it is a, solvent capable of constantly dissolving the etherification agent, but a polar solvent is particularly preferred. The polar solvent may be an aprotic polar solvent or a protic polar solvent, but an 15 aprotic polar solvent is more preferred. as the aprotic polar solvent, the following may be mentioned. Namely, an N, H-di-C1-2-alky 1 amide of a C1-3- carboxylic acid, such as N,N-dimethylformamide, N,N- diethylformamide, N,N-dipropylformamide, N,N- 30 dimethylacetamide, N,N-diethylacetamide, N,N- dipropylacetamide or N,N-dimethylproprionic amide; a cyclic N-alkyl carboxylic amide such as N- methylpyrrolidone; a cyclic N-forinyl compound such as N- formylpholine or N-formylpiperidine; a 25 hexaalkylphosphoric triaraide such as hexaiftethyl phosphoric triamide; a suit oxide such as climethylsulfoxide or tetramethylene sulfoxide; a 11 tetraalkylurea such as tetramethylurea; a. cyclic ether such as tetrahydrofuran, 1,4-dioxane or trioxane; an acetal such as 1,2-dimethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol 5 diethyl ether or diethylene glycol dibutyl ether; a ketone such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2- heptanone, 4-heptanone, diisobutyl ketone or acetonitrile acetone; or an ether such as diethyl ether, dipropyl 10 ether, diisopropyl ether or dibutyl ether, may be mentioned. On the other hand, as the protic polar solvent, the following may be mentioned. Namely, an alcohol such as methanol, ethanol, 1-propano1, 2-propanol, 1 -butane 1, 2- 15 butanol or tert-butyl alcohol; or a glycol such as ethylene glycol, propylene glycol, trimethylene glycol, 1, 2-butandiol, 1,3-butandiol or 1,4-butandiol, may be mentioned. among these polar solvents, particularly preferred 20 is an aprotic polar solvent having a boiling point of at least 60°C, such as N-methylpyrrolidone, N- dimethyl formanide, methyl ethyl ketone or methyl isobutyl ketone. Such an organic solvent is used usually in an amount 25 of from 1.5 to 10 times by weight relative to the alkali salt of a 9,10-anthracenediol compound as the material. In the first embodiment for producing an anthracene 12 diether of the present invention, an aqueous medium containing the alkali salt of a 9,10-anthraceriediol compound is added to the organic solvent containing the etherifying agent to carry out the etherifying reaction 5 to obtain the anthracene diether as the desired substance. In order to let the etherification reaction proceed efficiently, the order of addition of these materials is important. Namely, if the order of addition is changed, and the organic solvent containing the 10 etherifying agent is added to the aqueous solution of the alkali salt of a 9, 10-anthracenediol compound, side leactions tend to proceed, whereby the yield of the desired anthracene diether will decrease, such being undesirable, 15 The temperature for the etherification reaction in the present invention is preferably at least 0°C where the aqueous solution of the alkali salt of a 9,10- anthracenediol compound will not freeze and not higher than the boiling point of the etheritying agent dissolved 20 in the solvent, under atmospheric pressure. If the temperature is lower than 20°C, the etherification reaction tends to hardly proceed, and if it exceeds 80°C, side reactions tend to proceed. Accordingly, it is preferred to select the temperature within a range of 25 from 20 to 80°C. The second embodiment for producing an anthracene diether of the present invention is a process wherein an 13 aqueous medium containing the alkali salt of a 9,10- anthracenediol compound and an organic solvent containing the etherifying agent are mixed to carry out the reaction, and wherein the reaction is carried out in the 5 presence of a quaternary ammonium compound or a quaternary phosphoniuin compound. The quaternary ammonium compound or the quaternary phosplvonium compound pisfened for this reaction is a quaternary ammonium compound or a quaternary phosphonium 10 compound represented by the following formula (4): (wherein each of R1 to R4 which are independent of one another, is a low molecular weight or high molecular weight organic group, particularly a substituted or 15 unsubstituted alkyl, cycloalkyl or aryl group, Y is a nitrogen atom or a phosphorus atom, and An' is an anion). A particularly preterred compound is a quaternary ammonium compound of the above formula wherein Y=N, and each of R1, R2 and R3 which are independent of one 20 another, is a C1-18 alkyl group and R4 is a C1-18 alkyl group or a phenyl group. A suitable alkyl group may, for example, be a C1-18 14 alkyl group such as a methyl group, an ethyl group, a propyl group, a n-butyl group, a hexyl group, an octyl group, a dodecyl group or an octadecyl group, or a C1-18 alkyl group substituted by a hydroxyl group, a cyano 5 group or at phenyl group, such as a 2 -hydroxyethyl group, a 2-hydroxypropyl group, a 2-cyanoethyl group or a 2- phenylathy 1 group- A suitable cycloalkyl group for each, of R1 to R4 may, for example, be a C5_6 cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, and a 10 phenyl group substituted by a C1_4 alkyl group. The anion An- may preferably be a halogen ion, particularly a chlorine ion or a bromine ion, or a hydrogen sulfate ion. As the quaternary ammonium compound which may be used in the present invention, the following may, for 15 example, be mentioned. Tetrabutylammonium bromide or chloride dodecyltrimethylammonium chloride, n- hexadecyltributylammonium chloride, tetrapropylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium bromide, benzyltrihexylammonium 20 bromide, benzyltrioctylammonium bromide, tetrabutylammonium iodide, trioctylmethylammonium chloride, N-dodecylpyridinium bromide, cyclohexyl trie thy lammonium bromide, n- dodecyl triethylammonium bromide, n-Octyltributylammonium 25 bromide, n-hexadecyltrimethylammonium bromide, n- hexadecyltriethylammonium bromide, n- hexadecyltripropyl ammonium bromide, n-dodecyl-bis (b - 15 hydroxyethy1)-benzylammonium chloride and n - hexadecyl - tri (b-hydroxeyethyl) -ammonium chloride. A suitable phosphonium salt may, for example, be n- hexadecy1tributy1phosphonium bromide, 5 tetrabutylphosphonium chloride, tetraphenylphosphonium bromide or trioctylethylphosphonium bromide. Among them, particularly preferred is tetrabutylammonium bromide or tetrbutylammonium chlorida, n-hexadecyltributylammonium chloride, tetrapropylammonium chloride, 10 benzyltributylainmonium bromide or chloride, or trioctylmethylammonium bromide or chloride. The amount of the quarternary ammonium compound or the quaternary phosphorium compound to be used in the present invention may be varied within a wide range, but 15 it is preferably from 0.001 to 10 tinted by mol, particularly preferably from 0.01 to 1 time by mol, per mol of the alkali salt of a 9,l0-anthracenediol compound. It is undesirable to use it excessively, since such is economically disadvantageous. 20 As the method of carrying out the reaction in the presence of the quaternary ammonium compound or the quaternary phosphonium compound, a method may, for exsumple, be meritioned wherein the quaternary ammonium compound or the quaternary phosphonium compound is added 25 to the organic solvent containing the etherifying agent and then mixed with the aqueous medium wherein, the alkali salt of a 9,10-anthracenediol compound is dissolved to 16 carry out the reaction. The order of mixing the respective reactants in the present invention may be any order, but a method is preferred wherein the quaternary ammonium compound or the quaternary phospbonium compound 5 is added in a prescribed amount to the organic solvent containing the etherifying agent, and then, the aqueous medium wherein the alkali salt of a 9,lO-anthracenediol compound, is dissolved, is added. By this method of employing the quaternary ammonium compound or the 10 quaternary phosphonium compound, a preferred effect may be obtained such that the etherification reaction proceeds quickly, and formation of by-products can be suppressed. Especially in a case where an organic solvent poor in miscibility with water is used, if the 15 etherification reaction is carried out in the presence of a phase transfer catalyst such as tetrabutylamtfionium bromide, the etherification reaction product will be extracted in the organic solvent, whereby separation of the reaction product will be easy, and such may be 20 regarded as an industrially preferred method. Such an organic solvent poor in miscibility with water may, for example, be an aliphatic hydrocarbon type organic solvent such as n-hexane or cyclohexne, an aromatic hydrocarbon type organic solvent such as benaene, toluene or xylene, 25 or a halogenated hydrocarbon type organic solvent such as chloroform or dichloromethane. Further, as the third embodiment for producing an 17 anthracene diether of the present invention, a method may be mentioned wherein in a case where a certain specific etherification agent is employed, the reaction is carried out without using any organic solvent. Namely, it is a 5 process for producing an anthracene diether wherein an alkyl halide or the like is used as the etherifying agent, and the etherifying reaction is carried out by adding an aqueous medium containing the alkali salt of a 9,1O-anthracenediol compound to the alkyl halide in the 10 presence of the quaternary ammonium compound or the quaternary phosphonium compound without using any organic solvent. For example, a process may be mentioned wherein using an alkyl bromide such as butyl bromide in excess, an aqueous medium containing the alkali salt of a 9,10- 15 anthracenediol compound, is added in the presence of the quaternary ammonium compound or the quaternary phosphonium compound, to carry out the reaction. According to the process of the present invention, an anthracene diether can be obtained which is 20 represented by the following formula. (wherein R is an alkyl group, an allyl group, an aryl 18 group, a benzyl group, a hydroxyalkyl group or an alkoxyalkyl group, and each of R5 and R6 is a substituent inert to etherification, and each of in and n is an integer of from 0 to 4). The alkyl group for subtituent 5 R may be a C1-5 alkyl group, preferably a C1-4 alkyl group. specifically, a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, an i-butyl group, a t-butyl group, a n-pentyl group or an i-pentyl group may, for example, be mentioned. The allyl group 10 may, for example, be allyl or 2-methylallyl, The aryl group may, for example, be a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a naphthyl group or a biphenyl group. The hydroxyalkyl group may, for example, be a 2- 15 hydroxyethyl group, a 3-hydroxypropyl group, a 2-methyl- 2-hydroxyethyl group or a 2-ethyl-2-hydroxyethyl group. The alkoxyalkyl group may, for example, be a 2- methoxyethyl group, a 3-methoxypropyl group, a 2- ethoxyethyl group or a 3-ethoxypropyl group. 20 Each of substituents R5 and R6 is a substituent inert to the etherification reaction in the process of the present invention, and specifically, a C1-10 alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkylamino group, an alkylsulfonyl group, an 25 alkoxycarbonyl group or a halogen atom, may, for example, be mentioned. A specific example of the anthracene diether 19 represented by the above formula (1) to be produced in the present invention may, for example, be a dialkoxyanthracene such as 9,10-dimethoxyanthracene, 9 , 10-diethoxyanthracene, 9,l0-dipropoxyanthracene, 9,10- 5 dibutoxyanthracene, 2-ethyl-9 , 10-diethoxyanthracene, 2- (4-methylpenty 1) -9 ,10-diethoityanthracene, 2- (4-methyl-3- pentenyl)-9,lO-diethoxyanthracene or 2,3-diethyl-9,10- diethoxyanthracene; a diaryloxyanthracene such as 9,10- diphen oxyanthracene, 9, 10 - di (p -toly1oxy) anthraocene or 10 9,10-dinaphthy1oxyanthracene; a diallyloxyanthracene such as 9 ,10-diaryloxyanthracene or 9,10-di(2- methylallyloxy)anthracene; (9-10-di(2 - hydroxyethoxy)anthracene; or 9,10-di(2- methoxyethoxy) anthracene . 15 The anthracene diether represented by the above formula (1) , particularly a dialkoxyanthiracene, obtained by the process of the present invention, is useful as a sensitizer for a photocurable composition employing energy rays such as ultraviolet rays as the light source, 20 EXAMPLES Now, the present invention will be described in detail with, reference to Examples. However, it should be understood that the present invention is by no means restricted by the following Examples. In the following 25 Examples, "%" means "wt%" unless otherwise specified. EXAMPLE 1 A three necked flask having a capacity of 300 ml and 20 equipped with a stirrer, a thermometer, a heating jacket and a charge inlet, 32 g of 30% sodium hydroxide aqueous solution and 57 g of water were charged, and with stirring, 25 g of 9,10-anthraeenedione was charged and 5 suspended, whereupon air in the flask was substituted by nitrogen. While stirring the content in this flask, 130 g of an aqueous solution of a sodium salt of 1,4-dihydro- 9 , 10-dihydroxyanthracene (22% as the concetration of anthracenedione) was added, and the mixture was 10 maintained at an internal temperature within a range of from 85 to 900C for 4 hours to obtain an agueous solution of a sodium salt of 9,10-anthracenediol. into an autoclave having a capacity of 1 L and equipped with a stirrer, a thermometer, a heating jacket 15 and a charge inlet, a solution having 92 g of propyl bromide (1-bromopropane, the same applies hereinafter) dissolved in 300 g of dimethylformamide, was charged, and the internal temperature was raised to 65°C and maintained at that level. To this autoclave, the aqueous 20 solution of the sodium salt of 9,10-anthracenediol prepared by the above method, was added over a period of one hour with stirring. After completion of the addition of the aqueous solution of the sodium salt of 9,10- anthracenediol, the internal temperature was raised to 25 and maintained at 700C for one hour, Then, the internal temperature was lowered to 30°C to have crystals of the product precipitated. The crystals were collected by 21 filtration, washed with 100 ml of methanol and dried to obtain a product. The product had a melting point of 930C and was confirmed to be 9,10-dipropoxyanthracene by the NMR spectrum. The amount of the product was 48 g, 5 and the yield based on the sodium salt of 9,10- anthracenediol thereinatter referred to simply as the yieldl was 60 mol%. COMPARATIVE EXAMPLE 1 Firstly, by the method disclosed in Example 1, an 10 agueous solution of the sodium salt of 9,10- anthracenediol was prepared. Then, into the autoclave used in the method disclosed in Example 1, this aqueous solution of the sodium salt of 9,10-anthxacenediol was charged, and the internal temperature was raised to and 15 maintained at 650C with stirring. A solution having 92 g of, propyl bromide dissolved in 300 g of dimethylformamide, was added over a period of one hour. After completion of the addition of propyl bromide, the internal temperature was further raised to and maintained 20 at 70°C for one hour. Then, the internal temperature was lowered to 300C to have crystals precipitated, followed by filtration and drying in the same manner as in Example 1 to obtain a product. However, in the NMR spectrum, the product could not be corfirmed to be 9, 10- 25 dipropoxyanthracene, end the melting point was also 1710C. The structure assumed from the NMR was 9-hydro-9- oxo-10-hydroxy-10-propylamthracene. 22 EXAMPLE 2 Firstly, by the method disclosed in Example 1, an agueous solution of the sodium salt of 9,10- anthracenediol was prepared. Then, into the autoclave 5 used in the method disclosed in Example 1, a solution having 108 g of butyl bromide (1-bromobutane, the same applies hereinafter) dissolved in 300 g of dimethylformamide, was charged, and the internal temperature was raised to and maintained at 650C. To 10 this autoclave, the aqueous solution of the sodium, salt of 9,10-anthracenediol prepared by the method disclosed in Example 1, was added over a period of one hour with stirring. After adding the agueous solution of the sodium salt of 9,10-anthracenediel, the internal 15 temperature was further raised to and maintained at 70°C for one hour with stirring. Then, the internal temperature was lowered to 30°C to have crystals of the product precipitated. The crystals were collected by filtration, washed with methanol and dried to obtain a 20 product, the product had a melting point of 107°c, and was confirmed to be 9,10-dibutoxyanthracene by the NMR spectrum. The amount of the product was 53 g, and the yield was 70 mol% . COMPARATIVE EXAMPLE 2 25 Firstly, by the method disclosed in Example 1, an aqueous solution of the sodium salt of 9,10- anthracenediol was prepared. Then, into the autoclave 23 used in the method, disclosed in Example 1, this aqueous solution of the sodium salt of 9, 10-anthracenediol was charged, and the internal temperature was raised to and maintained at 65°C with stirring. A solution having 108 5 g of butyl bromide dissolved in 300 g of dimethylformamide, was added over a period of one hour. After completion of the addition of butyl bromide, the internal temperature was further raised to and maintained at 700C for one hour. Then, the incerna1 temperature was 10 lowered to 30°C to have crystals precipitated, followed by filtration and drying in the same manner as in Example 1 to obtain a product. However, the product was a mixture of 9 , lO-dibutoxyanthracene, 9,10-anthracenedione and 9-hydro-9-oxo-10-butylanthacene having the structure 15 assumed by NMR. The purity of 9,10-dibutoxyanthracene in the product was calculated, whereby the yield was 9 mol%. IN a three necked flask having a capacity of 500 ml and equipped, with a stirrer, a thermometer, a heating 20 jacket and a charge inlet, 16 g of sodium hydroxide was dissolved in 80 g of water, and 40 g of 9,10- anthracenedione was charged and suspended with stirring, whereupon air in the flask was substituted by nitrogen. While stirring the content in this flask, 209 g of an 25 aqueous solution of a sodium salt of 1, 4-dihydro-9 ,10- dihydroxyanthracene (22% as the concentration of anthracenedione) was added, and the internal temperature 24 was maintained within a range of from 95 to 970C for 4 hours to obtain an aqueous solution of the sodium salt of 9,10-anthracenediol. Into an autoclave having a capacity of 300 ml and 5 equipped with a stirrer, a thermometer, a heating jacket and a charge inlet, a solution having 40 g of butyl bromide and 1.9 g of tetrabutylammoniun bromide dissolved in 70 g of methyl ethyl ketone, was charged, and the internal temperature was raised to and maintained at 10 65°C. To this autoclave, 100 g of the agueous solution of the sodium salt of 9,10-anthracenediol prepared by the above-mentioned method, was added over a period of 3 hours with stirring. After completion of the addition of the aqueous solution of the sodium salt of 9,10- 15 anthracenediol, the internal temperature was further raised to and maintained at 70°C for one hour. Then, the internal temperature was lowered to 30°C, and 50 ml of methanol was added to the autoclave to have crystals of the product precipitated. The crystals were collected by 20 filtration, washed with 100 ml of methanol and dried to obtain a product. The amount of the product was 33 g, the yield of 9, lO-dilobutoxyanthracene was 90 mol%- COMPARATIVE EXAMPLE 3 The same operation was carried out by the Method 25 disclosed in Example 3 except that no tetrabutylammonium bromide was added, whereby the yield of 9,10- dibutoxyanthracene was 14 mol%, 25 EXAMPLE 4 As an addition method reverse to the method disclosed in Example 3, the same operation was carried out except that a solution having 40 g of butyl bromide 5 dissolved in 70 g of methyl ethyl ketone, was added over a period of three hours to the aqueous solution of the sodium salt of 9, 10-anthrsceriediol having tetrabutylammonium bromide added, whereby the yield of 9, 10-dibutoxyanthracene was 70 mol%. 10 EXAMPLE 5 The same operation was carried out by the method disclosed in Example 3 except that diethyl sulfate was used instead of butyl bromide, thereby the yield of 9,10- diethoxyanthracene was 87 mol%. 15 EXAMPLE 6 The same operation was carried out by the method, disclosed in Example 3 except that propyl bromide was used instead of butyl bromide, whereby the yield of 9,10- dipropoxyanthracene WAS 89 mol%, 20 EXAMPLE 7 The same operation was carried out by the method disclosed in Example 3 except that instead of using methyl ethyl ketone as an organic solvent, butyl bromide was increased to 57 g, whereby the yield of 9,10- 25 dibutoxyanthracene was 85 mol%, EXAMPLE 8 The same operation was carried out by the method 25 disclosed in Example 3 except that methyl isobutyl ketone was used instead of methyl ethyl ketone, whereby the yield of 9,lO-dibutoxyantbracene was 82 mel%. COMPARATIVE EXAMPLE 4 5 The same operation was carried out by the method disclosed in Example 3 except that isopropyl alcohol was used instead of methyl ethyl ketone, whereby the yield of 9,10-dibutoxyanthracene was 50 mol%. COMPARATIVE EXAMPLE 5 10 The same operation, was carried out by the method disclosed in Example 3 except that o-xylene was used instead of methyl ethyl ketone, whereby the yieid of 9 , 10-dibutoxyanthracene was 43 mol% , The process of the present invention provides the following especially advantageous effects, and thus its industrial value is extremely high. 1, The desired anthracene diether can be produced 20 industrially advantageously by using not only a dialkyl sulfate but also an industrially inexpensive alkyl halide, as an etherifying agent. 2 . As compared with conventiona1 production processes, a high purity anthracene diether can be 25 produced in a high yield. 3. Further, by tarrying out the reaction in the presence of a quaternary ammonium compound or a 27 quaternary phosphonium compound, preferred effects can be obtained such that the etherification reaction proceeds quickly, and formation of by-products can be suppressed. Further, in the case of an alkyl halide such as butyl 5 bromide, the reaction can be carried out without using an organic solvent . 28 CLAIMS 1. A process for producing an anthracene diether represented by the following formula (1): Wherein R is an alkyl group, an allyl group, an aryl 5 group, a benzyl group, a hydroxyalkyl group or an alkoxyalkyl group, each of R5 and R6 is a substituent- inert to etherification, and eacli of m and n is an integer of from 0 to 4), which comprises reacting an etheritying agent and an alkali salt of a 9,10- 10 anthracenediol compound to produce the anthracene diether, characterized in that an aqueous medium containing the alkali salt of a 9, 10-anthracenediol compound is added to an organic solvent containing the etherifying agent to carry out the reaction, 15 2. The process for producing an anthracene diether according to Claim 1, wherein the etherifying agent is one selected from dialkyl sulfates, alkyl halides, aryl halides or allyl halides. 3. The process for producing an anthracene diether 20 according to Claim 1 or 2, wherein the organic solvent is one selected from polar solvents. 4- The process for producing an anthracene diether according to Claim 3, wherein the polar solvents are 29 those selected from aptotic polar solvents. 5. A process for producing an anthracene diether represented by the following formula (1): 5 (wherein R is an alkyl group, an allyl group, an aryl group, a benzyl group, a hydroxyalkyl group or an alkoxyal group, each of R5 and R6 is a substituent inert to etherification, and each of m and n is an integer of from 0 to 4), which comprises reacting an 10 etherifying agent and an alkali salt of a 9.10- anthracenediol compound to produce the anthracene diether, characterized in that an aqueous medium containing the alkali salt of a 9, lO-anthracenediol compound and an organic solvent containing the etherifying agent are 15 mixed in the presence of a quaternary ammonium compound or a quaternary phosphonium compound to carry out the reaction. 6 . The process for producing an anthracene diether according co Claim 5, wherein the aqueous medium 20 containing the alkali salt of a 9, 10-anthracenediol compound is added to the organic solvent containing the etherifying agent to carry out the reaction. 30 7. A process for producing an anthracene diether represented by the following formula (1): (wherein R is an alkyl group, an allyl group, an aryl group, a benzyl group, a hydroxyalkyl group or an 5 alkoxyalkyl group, each of R5 and R6 is a substituent inert to etherification, and each of m and n is an integer of from 0 to 4), which comprises reacting an etherifying agent and an alkali salt of a 9,10- authracetiediol compound to produce the anthracene diether, 10 characterized in that an aqueous medium containing the alkali salt of a 9,10-anthracenediol compound is added to an alkyl halide in the presence of a quaternary ammonium copound or a guaternary phosphonium compound to carry out the reaction. 15 B. The process according to Claim 5, 6 or 7, wherein as the quaternary ammonium compound or the quaternary phosphonium compound,a quaternary ammonium compound or a quaternary phosphonium compound represented by the following formula (4): (wherein each of R1 to R4 which are independent of one another, is a low molecular weight or high molecular weight organic group, particularly a substituted or 5 unsubstituted alkyl, cycloalkyl or aryl group, y is a nitrogen atom or a phosphorus atom, and An is an anion) is used. 32 An industrially advantageous process is presented wheraby a high purity anthracene diether can be produced in good yield. 5 An aqueous medium containing an alkali salt of 9,10- anthracenediol is added to an organic solvent containing an etherifying agent in the presence or absence of a quaternary ammonium compound or a quaternary phosphonium compound, to carry out the etheritying reaction to 10 produce the anthracene diether.

Full Text

I/We, (1) Kawasaki Kasei Chemicals Ltd. of (2) 12-1.
Ekimaeoncho, Kawasaki-ku., Kawasaki-shi, Kanagawa 210-0007
Japan a/an (3) Japanese do hereby certify that the attached
document is a complete and faithful English translation of -
* the Specification comrprising of the description, the claims as
filed, text matter of drawings (if any) and the Abstract
■*—the Claimo as amended under PCT Article No. 19
■*—the Statement as filed under PCT Article No. 19
■*—the amendments—to—the deseription,—the claime,the- text
---matter of the drawings that are annexed to the-
---International preliminary Examination Report
in respect of the International Application No. PCT/JP02/13314
filed on December 19, 2002 at Japan (Receiving Office) ,
Dated this l7th day of may 2005
(4) Signature
Name (in block letters)
______Takamori Miyazaki____________
Designation Board Director, General
Manager of Research and_Devilopment Center
(1) Name of the Applicant in India.
(2) Address of the Applicant,
(3) Nationality (state of incorporation for corporate bodies)
of the applicant in India.
(4) Signature of the applicant
*"Note: Please use separate verification formats for each.
document while striking out the inapplicable portions
for the respective verifications.

1
DESCRIPTION
PROCESS FOR PRODUCING ANTHRACENE DIETHER
5 TECHNICAL FIELD
The present invention relates to a process for
producing an anthracene diether. More particularly, it
relates to a process for producing a dialkoxyanthracene
useful as a sensitizer for a photocurable composition
10 employing energy rays such as ultraviolet rays as the
light source, particularly a dialkoxyanthracene such as
9 , 10-dipropoxyanthracene or 9,10-dibutoxyanthracene, or a
diaryloxyanthracene such as 5,10-diphenoxyanthracene.
15 BACKGROUND ART
Heretofore, as a process for producing a 9,10-
dialkoxyanthracene, a process is, for example, known
wherein an anthracenedione compound is reduced and
alkylated as disclosed in u. Seitz at al., Synthesis,
20 686-688 (1986) . The process disclosed in this
publication is a process wherein in a two phase solvent
system having water and methylene chloride mixed,
hydrosulfite is used as a reducing agent, and methyl
iodide is used as an alkylating agent. However, the
25 process disclosed in this publication has a problem of
environmental pollution by methylene chloride, and
further it can hardly be regarded as an industrially

2
advantageous process, as an expensive alkylating agent is
employed.
Further, JP-A-2000-119208 discloses a process
wherein an anthracenedione compound is reduced and
5 alkylated in an alcohol medium by using hydrosulfite as a
reducing agent and diethyl acetate as an alkylating
agent. However, according to the test conducted by the
present inventors, if dipropyl sulfate or propyl bromide
was used as an alky1asting agent when dipropoxy anthracene
10 was prepared by the process disclosed in this
publication, by-products were substantial, and the
desired dipropoxyanthracene was not obtained. Further,
in a case where butyl bromide was used as an alkylating
agent, dinutoxyan thracene could not be obtained.
15 Under such a circumstance, the present inventors
have conducted an extensive study for the purpose of
providing a process for producing, industrially
advantageously in good yield, a dialkoxyanthracene,
particularly a high purity anthracene diether such as
20 9,lO-dipropoxyanthracene or 9,10-dibutoxyanthracene, and
as a result, the present invention has been accomplished.
DISCLOSURE OF THE INVENTION
To solve the above-mentioned problems, the present
25 inventors have conducted an extensive study and as a
result, have arrived at the present invention having the
following constructions.+

(1) A process for producing an anthracene diether
represented by the following formula (1):

(wherein R is an alkyl group, an allyl group, an aryl
group, a benzylgroup, a hydroxyalkyl group or an
5 alkoxyalkyl group, each of R5 and R6 is a substituent
inert to etherification, and each of m and n is an
integer of from 0 to 4), which comprises reacting an
etherifying agent and an alkali salt of a 9,10-
anthracenediol compound to produce the anthracene diether,
10 characterized in that an aqueous medium containing the
alkali salt of a 9,10-arrthracenediol compound, is added to
an organic solvent containing the etherifying agent to
carry out the reaction,
(2) The process for producing an anthracene diether
15 according to the above (1), wherein the etherifying agent
is one selected from dialkyl sulfates, alkyl hales,
aryl halides or allyl halides.
(3) The process for producing an anthracene diether
according to the above (1) or (2), wherein the organic
20 solvent is one selected from polar solvents,
(4) The process for producing an anthracene diether
according to the above (3), wherein the polar solvents
are those selected from aprotic polar solvents.

4
(5) A process for producing an anthracene diether
represented by the following formula (1) :

(wherein R is an alkyl group, an allyl group, an aryl
5 group, a benzyl group, a hydroxyalkyl group or an
alkoxyalkyl group, each of R5 and R6 is a substituent
inert to etherification, and each of m and n is an
integer of from 0 to 4), which comprises reacting an
echerifying agent and an alkali salt of a 9,10-
10 anthracenediol compound to produce the anthracene diether,
characterized in that an aqueous medium containing the
alkali salt of a 9,10-anthracenediol compound and an
organic solvent containing the etherifying agent are
mixed in the presence of a quaternary ammonium compound
15 or a quaternary phosphonium compound to carry out the
reaction.
(6) The process for producing an anthracene diether
according to the above (5), wherein the aqueous medium
containing the alkali salt of a 9,10-anthracenediol
20 compound is added to the organic solvent containing the
etherifying agent to carry out the reaction.
(71 A process for producing an anthracene diether

5
represented by the following formula (1) :

(wherein R is an alkyl group, an allyl group, an aryl
group, a benzyl group, a hydroxyalkyl group or an
5 alkoxyalkyl group, each of R5 and R6 is a substituent
inert to etherification, and each of m and n is an
integer of from 0 to 4), which comprises reacting an
etherifying agent and an alkali salt of a 9,10-
anthracenediol compound co produce the anthracene diether,
10 characterized in that an aqueous medium containing the
alkali salt of a 9,10-anthracenediol compound is added to
an alkyl halide in the presence of a quaternary ammonium
compound or a quaternary phosphonium compound to carry
out the reaction-
15 (8) The process according to the above (5), (6) or (7),
wherein as the quaternary ammonium compound or the
quaternary phosphonium compound, a quaternary ammonium
compound or a quaternary phosphonium compound represented
by the following formula (4):
20

R1
(wherein each of Rl to R4 which are independent of one
another, is a low molecular weight or high molecular
weight organic group, particularly a substituted, or
5 unsubstituted alkyl, cycloalkyl or aryl group, Y is a
nitrogen atom or a phosphorus atom, and An- is an anian)
is used.
EMBODIMENTS OF THE INVENTION
10 The first embodiment of the present invention is a
process wherein an aqueous medium containing an alkali
salt of a 9,10-anthracenediol compound is added to an
organic solvent containing an etherifying agent to carry
out the reaction.
15 The 9,10-anthracenediol compound is represented by
the following formula (2) :

(wherein like in the above formula (1), each of R5 and R6

7
is a substituent inert to etherification, and each of in
and n is an integer of from 0 to 4)and can be obtained.
by reducing the corresponding 9,10-anthracenedione
compound.
5 Each of substituents R5 and R6 is a substituent inert
to the etherification reaction in the process of the
present invention. Specifically, a C1-10 alkyl group, an
alkenyl group, an alkoxy group, an amino group, an
alkylamino group, an alkylsulfonyl group, an
10 alkoxycarbony1 group or a halogen group, may, for
example, be mentioned. Each of m and n represents the
number of substituents bonded to the aromatic ring and is
an integer of from 0 to 4, preferably an integer of from
0 to 2 .
15 In an aqueous medium containing an alkaline active
agent, the 9,10-anthracenediol compound is dissolved in
the form of an alkali salt of a 9,10-anthracenediol
compound represented by the formula (3):

20 (wherein R5, R6, m and n have the same meanings as in the
above formula (2) , and M is an alkali metal) . As such an
alkaline active agent, sodium hydroxide or potassium

8
hydroxide may, for example, be mentioned, and it is used
in an amount of preferably at least 2 times by mol, more
preferably from 2.2 to 3 times by mol, relative to the
9, 10-anthracenediol compound. The aqueous medium means,
5 in addition to water, a lower alcohol such as methyl
alcohol, ethyl alcohol or isopropyl alcohol or a mixed
medium of such a lower alcohol with water, or a water,
soluble ether such as tetrahydrofuran or dioxane or a
raixjed medium of such a. water-soluble lower ether with
10 water. The solubility of the alkali salt of a 9,10-
anthracenediol compound varies depending upon the types
of the substituents, but in the case of an aqueous
solution, a solution having a. concentration of from about
5 to 30 wt% is preferably selected.
15 As the method for reducing the 9,10-anthracenedione
compound, (1) a method of carrying out hydrogen reduction
in a solvent such as an alcohol in the presence of a
hydrogenation catalyst, or (2) a method of carrying out
reduction in an aqueous mediuma by means of hydrosulfite,
20 may, for example, be mentioned. The above method (2) is
preferred, since by the reduction in the presence of an
alkaline compound such as sodium hydroxide, an alkali
salt of a 9,10-anthracenediol compound can directly be
obtained. Further, (3)a method for producing an alkali
25 salt of anthracenediol which comprises reducing 9,10-
anthracenedione with a solution of an alkaline compound
of 1,4-dihydro-9,10-dihydroxyanthracene (JP-A-9-16982)

9
may, for example, be mentioned, This method (3) is
preferred, since 1,4-dihydro-9,10-dihydroxyanthracene
used for the reduction, becomes anthracene diol, whereby
there will be no necessity to remove the reducing agent
5 after use.
The etherification agent in the present invention
may, for example, be an alkylating agent, an aryl-
modifying agent or art allyl-modifying agent, which will
be described below. Namely, the alkylating agent may,
10 for example, be a dialkyl sulfate such as diethyl sulfate
or dipropyl sulfate, or an alkyl halide such as ethyl
bromide, propyl bromide or butyl bromide. The aryl-
modifying agent may, for example, be an aryl halide such
as bromobensene, chlorobenzene, p-chlorotoluene, p-
15 bromotoluene, m-bromotoluene, m-chlorotoluene, a
chloronaphtha1ene, a -bromonaphthalene,b-
chloronaphthalene or b-bromonaplithalene. Further, the
allyl-modifying agent may, for example, be an allyl
halide such as allyl bromide, allyl chloride or methallyl
20 chloride. As other etherifying agents, 2-bromoethanol
may be mentioned for hydroxyethylation, and 2-
bromoethylmethyl ether may be mentioned for
methoxyethyllation.
Among these etherifying agents, from the viewpoint
25 of the reactivity, etc.. preferred is a dialkyl sulfate,
an alkyl halide, an aryl halide or an allyl halide, and
particularly preferred is an alkyl halide such as propyl

10
bromide or butyl bromide. Such an etherifying agent is
used in an amount of at least 2 times by mol,
particularly preferably within a range of from 2 to 5
times by mol, relative to the alkali metal of a 9,10-
5 anthracenediol compound as the material. If it is less
than 2 times by mol, an unreacted case will increase, and
if it exceeds 5 times by mol, side reactions will
increase, such being undesirable.
In the present invention, the organic solvent to
10 contain such an etherification agent may be any solvent,
so long as it is a, solvent capable of constantly
dissolving the etherification agent, but a polar solvent
is particularly preferred. The polar solvent may be an
aprotic polar solvent or a protic polar solvent, but an
15 aprotic polar solvent is more preferred.
as the aprotic polar solvent, the following may be
mentioned. Namely, an N, H-di-C1-2-alky 1 amide of a C1-3-
carboxylic acid, such as N,N-dimethylformamide, N,N-
diethylformamide, N,N-dipropylformamide, N,N-
30 dimethylacetamide, N,N-diethylacetamide, N,N-
dipropylacetamide or N,N-dimethylproprionic amide; a
cyclic N-alkyl carboxylic amide such as N-
methylpyrrolidone; a cyclic N-forinyl compound such as N-
formylpholine or N-formylpiperidine; a
25 hexaalkylphosphoric triaraide such as hexaiftethyl
phosphoric triamide; a suit oxide such as
climethylsulfoxide or tetramethylene sulfoxide; a

11
tetraalkylurea such as tetramethylurea; a. cyclic ether
such as tetrahydrofuran, 1,4-dioxane or trioxane; an
acetal such as 1,2-dimethoxyethane, 1,2-dibutoxyethane,
diethylene glycol dimethyl ether, diethylene glycol
5 diethyl ether or diethylene glycol dibutyl ether; a
ketone such as acetone, methyl ethyl ketone, 2-pentanone,
3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-
heptanone, 4-heptanone, diisobutyl ketone or acetonitrile
acetone; or an ether such as diethyl ether, dipropyl
10 ether, diisopropyl ether or dibutyl ether, may be
mentioned.
On the other hand, as the protic polar solvent, the
following may be mentioned. Namely, an alcohol such as
methanol, ethanol, 1-propano1, 2-propanol, 1 -butane 1, 2-
15 butanol or tert-butyl alcohol; or a glycol such as
ethylene glycol, propylene glycol, trimethylene glycol,
1, 2-butandiol, 1,3-butandiol or 1,4-butandiol, may be
mentioned.
among these polar solvents, particularly preferred
20 is an aprotic polar solvent having a boiling point of at
least 60°C, such as N-methylpyrrolidone, N-
dimethyl formanide, methyl ethyl ketone or methyl isobutyl
ketone.
Such an organic solvent is used usually in an amount
25 of from 1.5 to 10 times by weight relative to the alkali
salt of a 9,10-anthracenediol compound as the material.
In the first embodiment for producing an anthracene

12
diether of the present invention, an aqueous medium
containing the alkali salt of a 9,10-anthraceriediol
compound is added to the organic solvent containing the
etherifying agent to carry out the etherifying reaction
5 to obtain the anthracene diether as the desired
substance. In order to let the etherification reaction
proceed efficiently, the order of addition of these
materials is important. Namely, if the order of addition
is changed, and the organic solvent containing the
10 etherifying agent is added to the aqueous solution of the
alkali salt of a 9, 10-anthracenediol compound, side
leactions tend to proceed, whereby the yield of the
desired anthracene diether will decrease, such being
undesirable,
15 The temperature for the etherification reaction in
the present invention is preferably at least 0°C where
the aqueous solution of the alkali salt of a 9,10-
anthracenediol compound will not freeze and not higher
than the boiling point of the etheritying agent dissolved
20 in the solvent, under atmospheric pressure. If the
temperature is lower than 20°C, the etherification
reaction tends to hardly proceed, and if it exceeds 80°C,
side reactions tend to proceed. Accordingly, it is
preferred to select the temperature within a range of
25 from 20 to 80°C.
The second embodiment for producing an anthracene
diether of the present invention is a process wherein an

13
aqueous medium containing the alkali salt of a 9,10-
anthracenediol compound and an organic solvent containing
the etherifying agent are mixed to carry out the
reaction, and wherein the reaction is carried out in the
5 presence of a quaternary ammonium compound or a
quaternary phosphoniuin compound.
The quaternary ammonium compound or the quaternary
phosplvonium compound pisfened for this reaction is a
quaternary ammonium compound or a quaternary phosphonium
10 compound represented by the following formula (4):

(wherein each of R1 to R4 which are independent of one
another, is a low molecular weight or high molecular
weight organic group, particularly a substituted or
15 unsubstituted alkyl, cycloalkyl or aryl group, Y is a
nitrogen atom or a phosphorus atom, and An' is an anion).
A particularly preterred compound is a quaternary
ammonium compound of the above formula wherein Y=N, and
each of R1, R2 and R3 which are independent of one
20 another, is a C1-18 alkyl group and R4 is a C1-18 alkyl
group or a phenyl group.
A suitable alkyl group may, for example, be a C1-18

14
alkyl group such as a methyl group, an ethyl group, a
propyl group, a n-butyl group, a hexyl group, an octyl
group, a dodecyl group or an octadecyl group, or a C1-18
alkyl group substituted by a hydroxyl group, a cyano
5 group or at phenyl group, such as a 2 -hydroxyethyl group,
a 2-hydroxypropyl group, a 2-cyanoethyl group or a 2-
phenylathy 1 group- A suitable cycloalkyl group for each,
of R1 to R4 may, for example, be a C5_6 cycloalkyl group
such as a cyclopentyl group or a cyclohexyl group, and a
10 phenyl group substituted by a C1_4 alkyl group. The anion
An- may preferably be a halogen ion, particularly a
chlorine ion or a bromine ion, or a hydrogen sulfate ion.
As the quaternary ammonium compound which may be
used in the present invention, the following may, for
15 example, be mentioned. Tetrabutylammonium bromide or
chloride dodecyltrimethylammonium chloride, n-
hexadecyltributylammonium chloride, tetrapropylammonium
chloride, benzyltriethylammonium chloride,
benzyltributylammonium bromide, benzyltrihexylammonium
20 bromide, benzyltrioctylammonium bromide,
tetrabutylammonium iodide, trioctylmethylammonium
chloride, N-dodecylpyridinium bromide,
cyclohexyl trie thy lammonium bromide, n-
dodecyl triethylammonium bromide, n-Octyltributylammonium
25 bromide, n-hexadecyltrimethylammonium bromide, n-
hexadecyltriethylammonium bromide, n-
hexadecyltripropyl ammonium bromide, n-dodecyl-bis (b -

15
hydroxyethy1)-benzylammonium chloride and n - hexadecyl -
tri (b-hydroxeyethyl) -ammonium chloride. A suitable
phosphonium salt may, for example, be n-
hexadecy1tributy1phosphonium bromide,
5 tetrabutylphosphonium chloride, tetraphenylphosphonium
bromide or trioctylethylphosphonium bromide. Among them,
particularly preferred is tetrabutylammonium bromide or
tetrbutylammonium chlorida, n-hexadecyltributylammonium
chloride, tetrapropylammonium chloride,
10 benzyltributylainmonium bromide or chloride, or
trioctylmethylammonium bromide or chloride.
The amount of the quarternary ammonium compound or
the quaternary phosphorium compound to be used in the
present invention may be varied within a wide range, but
15 it is preferably from 0.001 to 10 tinted by mol,
particularly preferably from 0.01 to 1 time by mol, per
mol of the alkali salt of a 9,l0-anthracenediol compound.
It is undesirable to use it excessively, since such is
economically disadvantageous.
20 As the method of carrying out the reaction in the
presence of the quaternary ammonium compound or the
quaternary phosphonium compound, a method may, for
exsumple, be meritioned wherein the quaternary ammonium
compound or the quaternary phosphonium compound is added
25 to the organic solvent containing the etherifying agent
and then mixed with the aqueous medium wherein, the alkali
salt of a 9,10-anthracenediol compound is dissolved to

16
carry out the reaction. The order of mixing the
respective reactants in the present invention may be any
order, but a method is preferred wherein the quaternary
ammonium compound or the quaternary phospbonium compound
5 is added in a prescribed amount to the organic solvent
containing the etherifying agent, and then, the aqueous
medium wherein the alkali salt of a 9,lO-anthracenediol
compound, is dissolved, is added. By this method of
employing the quaternary ammonium compound or the
10 quaternary phosphonium compound, a preferred effect may
be obtained such that the etherification reaction
proceeds quickly, and formation of by-products can be
suppressed. Especially in a case where an organic
solvent poor in miscibility with water is used, if the
15 etherification reaction is carried out in the presence of
a phase transfer catalyst such as tetrabutylamtfionium
bromide, the etherification reaction product will be
extracted in the organic solvent, whereby separation of
the reaction product will be easy, and such may be
20 regarded as an industrially preferred method. Such an
organic solvent poor in miscibility with water may, for
example, be an aliphatic hydrocarbon type organic solvent
such as n-hexane or cyclohexne, an aromatic hydrocarbon
type organic solvent such as benaene, toluene or xylene,
25 or a halogenated hydrocarbon type organic solvent such as
chloroform or dichloromethane.
Further, as the third embodiment for producing an

17
anthracene diether of the present invention, a method may
be mentioned wherein in a case where a certain specific
etherification agent is employed, the reaction is carried
out without using any organic solvent. Namely, it is a
5 process for producing an anthracene diether wherein an
alkyl halide or the like is used as the etherifying
agent, and the etherifying reaction is carried out by
adding an aqueous medium containing the alkali salt of a
9,1O-anthracenediol compound to the alkyl halide in the
10 presence of the quaternary ammonium compound or the
quaternary phosphonium compound without using any organic
solvent. For example, a process may be mentioned wherein
using an alkyl bromide such as butyl bromide in excess,
an aqueous medium containing the alkali salt of a 9,10-
15 anthracenediol compound, is added in the presence of the
quaternary ammonium compound or the quaternary
phosphonium compound, to carry out the reaction.
According to the process of the present invention,
an anthracene diether can be obtained which is
20 represented by the following formula.

(wherein R is an alkyl group, an allyl group, an aryl

18
group, a benzyl group, a hydroxyalkyl group or an
alkoxyalkyl group, and each of R5 and R6 is a substituent
inert to etherification, and each of in and n is an
integer of from 0 to 4). The alkyl group for subtituent
5 R may be a C1-5 alkyl group, preferably a C1-4 alkyl group.
specifically, a methyl group, an ethyl group, a n-propyl
group, an i-propyl group, a n-butyl group, an i-butyl
group, a t-butyl group, a n-pentyl group or an i-pentyl
group may, for example, be mentioned. The allyl group
10 may, for example, be allyl or 2-methylallyl, The aryl
group may, for example, be a phenyl group, an o-tolyl
group, a m-tolyl group, a p-tolyl group, a naphthyl group
or a biphenyl group.
The hydroxyalkyl group may, for example, be a 2-
15 hydroxyethyl group, a 3-hydroxypropyl group, a 2-methyl-
2-hydroxyethyl group or a 2-ethyl-2-hydroxyethyl group.
The alkoxyalkyl group may, for example, be a 2-
methoxyethyl group, a 3-methoxypropyl group, a 2-
ethoxyethyl group or a 3-ethoxypropyl group.
20 Each of substituents R5 and R6 is a substituent inert
to the etherification reaction in the process of the
present invention, and specifically, a C1-10 alkyl group,
an alkenyl group, an alkoxy group, an amino group, an
alkylamino group, an alkylsulfonyl group, an
25 alkoxycarbonyl group or a halogen atom, may, for example,
be mentioned.
A specific example of the anthracene diether

19
represented by the above formula (1) to be produced in
the present invention may, for example, be a
dialkoxyanthracene such as 9,10-dimethoxyanthracene,
9 , 10-diethoxyanthracene, 9,l0-dipropoxyanthracene, 9,10-
5 dibutoxyanthracene, 2-ethyl-9 , 10-diethoxyanthracene, 2-
(4-methylpenty 1) -9 ,10-diethoityanthracene, 2- (4-methyl-3-
pentenyl)-9,lO-diethoxyanthracene or 2,3-diethyl-9,10-
diethoxyanthracene; a diaryloxyanthracene such as 9,10-
diphen oxyanthracene, 9, 10 - di (p -toly1oxy) anthraocene or
10 9,10-dinaphthy1oxyanthracene; a diallyloxyanthracene such
as 9 ,10-diaryloxyanthracene or 9,10-di(2-
methylallyloxy)anthracene; (9-10-di(2 -
hydroxyethoxy)anthracene; or 9,10-di(2-
methoxyethoxy) anthracene .
15 The anthracene diether represented by the above
formula (1) , particularly a dialkoxyanthiracene, obtained
by the process of the present invention, is useful as a
sensitizer for a photocurable composition employing
energy rays such as ultraviolet rays as the light source,
20 EXAMPLES
Now, the present invention will be described in
detail with, reference to Examples. However, it should be
understood that the present invention is by no means
restricted by the following Examples. In the following
25 Examples, "%" means "wt%" unless otherwise specified.
EXAMPLE 1
A three necked flask having a capacity of 300 ml and

20
equipped with a stirrer, a thermometer, a heating jacket
and a charge inlet, 32 g of 30% sodium hydroxide
aqueous solution and 57 g of water were charged, and with
stirring, 25 g of 9,10-anthraeenedione was charged and
5 suspended, whereupon air in the flask was substituted by
nitrogen. While stirring the content in this flask, 130
g of an aqueous solution of a sodium salt of 1,4-dihydro-
9 , 10-dihydroxyanthracene (22% as the concetration of
anthracenedione) was added, and the mixture was
10 maintained at an internal temperature within a range of
from 85 to 900C for 4 hours to obtain an agueous solution
of a sodium salt of 9,10-anthracenediol.
into an autoclave having a capacity of 1 L and
equipped with a stirrer, a thermometer, a heating jacket
15 and a charge inlet, a solution having 92 g of propyl
bromide (1-bromopropane, the same applies hereinafter)
dissolved in 300 g of dimethylformamide, was charged, and
the internal temperature was raised to 65°C and
maintained at that level. To this autoclave, the aqueous
20 solution of the sodium salt of 9,10-anthracenediol
prepared by the above method, was added over a period of
one hour with stirring. After completion of the addition
of the aqueous solution of the sodium salt of 9,10-
anthracenediol, the internal temperature was raised to
25 and maintained at 700C for one hour, Then, the internal
temperature was lowered to 30°C to have crystals of the
product precipitated. The crystals were collected by

21
filtration, washed with 100 ml of methanol and dried to
obtain a product. The product had a melting point of
930C and was confirmed to be 9,10-dipropoxyanthracene by
the NMR spectrum. The amount of the product was 48 g,
5 and the yield based on the sodium salt of 9,10-
anthracenediol thereinatter referred to simply as the
yieldl was 60 mol%.
COMPARATIVE EXAMPLE 1
Firstly, by the method disclosed in Example 1, an
10 agueous solution of the sodium salt of 9,10-
anthracenediol was prepared. Then, into the autoclave
used in the method disclosed in Example 1, this aqueous
solution of the sodium salt of 9,10-anthxacenediol was
charged, and the internal temperature was raised to and
15 maintained at 650C with stirring. A solution having 92 g
of, propyl bromide dissolved in 300 g of
dimethylformamide, was added over a period of one hour.
After completion of the addition of propyl bromide, the
internal temperature was further raised to and maintained
20 at 70°C for one hour. Then, the internal temperature was
lowered to 300C to have crystals precipitated, followed
by filtration and drying in the same manner as in Example
1 to obtain a product. However, in the NMR spectrum, the
product could not be corfirmed to be 9, 10-
25 dipropoxyanthracene, end the melting point was also
1710C. The structure assumed from the NMR was 9-hydro-9-
oxo-10-hydroxy-10-propylamthracene.

22
EXAMPLE 2
Firstly, by the method disclosed in Example 1, an
agueous solution of the sodium salt of 9,10-
anthracenediol was prepared. Then, into the autoclave
5 used in the method disclosed in Example 1, a solution
having 108 g of butyl bromide (1-bromobutane, the same
applies hereinafter) dissolved in 300 g of
dimethylformamide, was charged, and the internal
temperature was raised to and maintained at 650C. To
10 this autoclave, the aqueous solution of the sodium, salt
of 9,10-anthracenediol prepared by the method disclosed
in Example 1, was added over a period of one hour with
stirring. After adding the agueous solution of the
sodium salt of 9,10-anthracenediel, the internal
15 temperature was further raised to and maintained at 70°C
for one hour with stirring. Then, the internal
temperature was lowered to 30°C to have crystals of the
product precipitated. The crystals were collected by
filtration, washed with methanol and dried to obtain a
20 product, the product had a melting point of 107°c, and
was confirmed to be 9,10-dibutoxyanthracene by the NMR
spectrum. The amount of the product was 53 g, and the
yield was 70 mol% .
COMPARATIVE EXAMPLE 2
25 Firstly, by the method disclosed in Example 1, an
aqueous solution of the sodium salt of 9,10-
anthracenediol was prepared. Then, into the autoclave

23
used in the method, disclosed in Example 1, this aqueous
solution of the sodium salt of 9, 10-anthracenediol was
charged, and the internal temperature was raised to and
maintained at 65°C with stirring. A solution having 108
5 g of butyl bromide dissolved in 300 g of
dimethylformamide, was added over a period of one hour.
After completion of the addition of butyl bromide, the
internal temperature was further raised to and maintained
at 700C for one hour. Then, the incerna1 temperature was
10 lowered to 30°C to have crystals precipitated, followed
by filtration and drying in the same manner as in Example
1 to obtain a product. However, the product was a
mixture of 9 , lO-dibutoxyanthracene, 9,10-anthracenedione
and 9-hydro-9-oxo-10-butylanthacene having the structure
15 assumed by NMR. The purity of 9,10-dibutoxyanthracene in
the product was calculated, whereby the yield was 9 mol%.
IN a three necked flask having a capacity of 500 ml
and equipped, with a stirrer, a thermometer, a heating
20 jacket and a charge inlet, 16 g of sodium hydroxide was
dissolved in 80 g of water, and 40 g of 9,10-
anthracenedione was charged and suspended with stirring,
whereupon air in the flask was substituted by nitrogen.
While stirring the content in this flask, 209 g of an
25 aqueous solution of a sodium salt of 1, 4-dihydro-9 ,10-
dihydroxyanthracene (22% as the concentration of
anthracenedione) was added, and the internal temperature

24
was maintained within a range of from 95 to 970C for 4
hours to obtain an aqueous solution of the sodium salt of
9,10-anthracenediol.
Into an autoclave having a capacity of 300 ml and
5 equipped with a stirrer, a thermometer, a heating jacket
and a charge inlet, a solution having 40 g of butyl
bromide and 1.9 g of tetrabutylammoniun bromide dissolved
in 70 g of methyl ethyl ketone, was charged, and the
internal temperature was raised to and maintained at
10 65°C. To this autoclave, 100 g of the agueous solution
of the sodium salt of 9,10-anthracenediol prepared by the
above-mentioned method, was added over a period of 3
hours with stirring. After completion of the addition of
the aqueous solution of the sodium salt of 9,10-
15 anthracenediol, the internal temperature was further
raised to and maintained at 70°C for one hour. Then, the
internal temperature was lowered to 30°C, and 50 ml of
methanol was added to the autoclave to have crystals of
the product precipitated. The crystals were collected by
20 filtration, washed with 100 ml of methanol and dried to
obtain a product. The amount of the product was 33 g,
the yield of 9, lO-dilobutoxyanthracene was 90 mol%-
COMPARATIVE EXAMPLE 3
The same operation was carried out by the Method
25 disclosed in Example 3 except that no tetrabutylammonium
bromide was added, whereby the yield of 9,10-
dibutoxyanthracene was 14 mol%,

25
EXAMPLE 4
As an addition method reverse to the method
disclosed in Example 3, the same operation was carried
out except that a solution having 40 g of butyl bromide
5 dissolved in 70 g of methyl ethyl ketone, was added over
a period of three hours to the aqueous solution of the
sodium salt of 9, 10-anthrsceriediol having
tetrabutylammonium bromide added, whereby the yield of
9, 10-dibutoxyanthracene was 70 mol%.
10 EXAMPLE 5
The same operation was carried out by the method
disclosed in Example 3 except that diethyl sulfate was
used instead of butyl bromide, thereby the yield of 9,10-
diethoxyanthracene was 87 mol%.
15 EXAMPLE 6
The same operation was carried out by the method,
disclosed in Example 3 except that propyl bromide was
used instead of butyl bromide, whereby the yield of 9,10-
dipropoxyanthracene WAS 89 mol%,
20 EXAMPLE 7
The same operation was carried out by the method
disclosed in Example 3 except that instead of using
methyl ethyl ketone as an organic solvent, butyl bromide
was increased to 57 g, whereby the yield of 9,10-
25 dibutoxyanthracene was 85 mol%,
EXAMPLE 8
The same operation was carried out by the method

25
disclosed in Example 3 except that methyl isobutyl ketone
was used instead of methyl ethyl ketone, whereby the
yield of 9,lO-dibutoxyantbracene was 82 mel%.
COMPARATIVE EXAMPLE 4
5 The same operation was carried out by the method
disclosed in Example 3 except that isopropyl alcohol was
used instead of methyl ethyl ketone, whereby the yield of
9,10-dibutoxyanthracene was 50 mol%.
COMPARATIVE EXAMPLE 5
10 The same operation, was carried out by the method
disclosed in Example 3 except that o-xylene was used
instead of methyl ethyl ketone, whereby the yieid of
9 , 10-dibutoxyanthracene was 43 mol% ,
The process of the present invention provides the
following especially advantageous effects, and thus its
industrial value is extremely high.
1, The desired anthracene diether can be produced
20 industrially advantageously by using not only a dialkyl
sulfate but also an industrially inexpensive alkyl
halide, as an etherifying agent.
2 . As compared with conventiona1 production
processes, a high purity anthracene diether can be
25 produced in a high yield.
3. Further, by tarrying out the reaction in the
presence of a quaternary ammonium compound or a

27
quaternary phosphonium compound, preferred effects can be
obtained such that the etherification reaction proceeds
quickly, and formation of by-products can be suppressed.
Further, in the case of an alkyl halide such as butyl
5 bromide, the reaction can be carried out without using an
organic solvent .

28
CLAIMS
1. A process for producing an anthracene diether
represented by the following formula (1):

Wherein R is an alkyl group, an allyl group, an aryl
5 group, a benzyl group, a hydroxyalkyl group or an
alkoxyalkyl group, each of R5 and R6 is a substituent-
inert to etherification, and eacli of m and n is an
integer of from 0 to 4), which comprises reacting an
etheritying agent and an alkali salt of a 9,10-
10 anthracenediol compound to produce the anthracene diether,
characterized in that an aqueous medium containing the
alkali salt of a 9, 10-anthracenediol compound is added to
an organic solvent containing the etherifying agent to
carry out the reaction,
15 2. The process for producing an anthracene diether
according to Claim 1, wherein the etherifying agent is
one selected from dialkyl sulfates, alkyl halides, aryl
halides or allyl halides.
3. The process for producing an anthracene diether
20 according to Claim 1 or 2, wherein the organic solvent is
one selected from polar solvents.
4- The process for producing an anthracene diether
according to Claim 3, wherein the polar solvents are

29
those selected from aptotic polar solvents.
5. A process for producing an anthracene diether
represented by the following formula (1):

5 (wherein R is an alkyl group, an allyl group, an aryl
group, a benzyl group, a hydroxyalkyl group or an
alkoxyal group, each of R5 and R6 is a substituent
inert to etherification, and each of m and n is an
integer of from 0 to 4), which comprises reacting an
10 etherifying agent and an alkali salt of a 9.10-
anthracenediol compound to produce the anthracene diether,
characterized in that an aqueous medium containing the
alkali salt of a 9, lO-anthracenediol compound and an
organic solvent containing the etherifying agent are
15 mixed in the presence of a quaternary ammonium compound
or a quaternary phosphonium compound to carry out the
reaction.
6 . The process for producing an anthracene diether
according co Claim 5, wherein the aqueous medium
20 containing the alkali salt of a 9, 10-anthracenediol
compound is added to the organic solvent containing the
etherifying agent to carry out the reaction.

30
7. A process for producing an anthracene diether
represented by the following formula (1):

(wherein R is an alkyl group, an allyl group, an aryl
group, a benzyl group, a hydroxyalkyl group or an
5 alkoxyalkyl group, each of R5 and R6 is a substituent
inert to etherification, and each of m and n is an
integer of from 0 to 4), which comprises reacting an
etherifying agent and an alkali salt of a 9,10-
authracetiediol compound to produce the anthracene diether,
10 characterized in that an aqueous medium containing the
alkali salt of a 9,10-anthracenediol compound is added to
an alkyl halide in the presence of a quaternary ammonium
copound or a guaternary phosphonium compound to carry
out the reaction.
15 B. The process according to Claim 5, 6 or 7, wherein as
the quaternary ammonium compound or the quaternary
phosphonium compound,a quaternary ammonium compound or a
quaternary phosphonium compound represented by the
following formula (4):

(wherein each of R1 to R4 which are independent of one
another, is a low molecular weight or high molecular
weight organic group, particularly a substituted or
5 unsubstituted alkyl, cycloalkyl or aryl group, y is a
nitrogen atom or a phosphorus atom, and An is an anion)
is used.

32

An industrially advantageous process is presented
wheraby a high purity anthracene diether can be produced
in good yield.
5 An aqueous medium containing an alkali salt of 9,10-
anthracenediol is added to an organic solvent containing
an etherifying agent in the presence or absence of a
quaternary ammonium compound or a quaternary phosphonium
compound, to carry out the etheritying reaction to
10 produce the anthracene diether.

Documents:

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Patent Number

216306

Indian Patent Application Number

01136/KOLNP/2005

PG Journal Number

11/2008

Publication Date

14-Mar-2008

Grant Date

12-Mar-2008

Date of Filing

14-Jun-2005

Name of Patentee

KAWASAKI KASEI CHEMICALS LTD.

Applicant Address

12-1,EKIMAEHONCHO, KAWASAKI-KU KAWASAKI-SHI, KANAGAWA 210-0007, JAPAN

Inventors:

#	Inventor's Name	Inventor's Address
1	HONDA, HIROYUKI	C/O KAWASAKI KASEI CHEMICALS LTD., 10-1, SHIOHAMA 3-CHOME, KAWASAKI-KU, KAWASAKI-SHI,KANAGAWA 210-0826 JAPAN.
2	NAKANO, HIROKI	C/O KAWASAKI KASEI CHIMICALS LTD.,10-1,SHIOHAMA 3-CHOME, KAWASAKI-KU KAWASAKI-SHI, KANAGAWA 210-0826 JAPAN
3	NUMATA, SHIGEAKI	C/O KAWASAKI KASEI CHEMICALS LTD., 10-1, SHIOHAMA 3-CHOME, KAWASAKI-KU, KAWASAKI-SHI, KANAGAWA 210-0826 JAPAN.

PCT International Classification Number

C07C 41/16

PCT International Application Number

PCT/JP2002/013314

PCT International Filing date

2002-12-19

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	PCT/JP2002/013314	2002-12-19	Japan