Method for Preparing 2,3-Dichloro-1-Propanol and 3-Chloro-1-Propanol

Europaisches Patentamt 19 European Patent Office

Office europeen des brevets © Publication number : 0 579 362 A1

EUROPEAN PATENT APPLICATION

@ Date of filing : 19.05.93

© Priority: 13.07.92 JP 184910/92 @ Inventor: Watanabe, Hiroyoshi 18.12.92 JP 338584/92 3-4-1-141, Toriishi Takaishi-shi, Osaka-fu (JP) Inventor : Hayakawa, Fumie @) Date of publication of application : 4-7-3-342, Kamo 19.01.94 Bulletin 94/03 Takaishi-shi, Osaka-fu (JP)

© Designated Contracting States : © Representative : Stuart, Ian Alexander et al DE FR GB IT NL MEWBURN ELLIS 2 Cursitor Street London EC4A 1BQ (GB) © Applicant : MITSUI TOATSU CHEMICALS, Inc. 2-5 Kasumigaseki 3-chome Chiyoda-Ku Tokyo 100 (JP)

© A method for preparing 2,3-dichloro-l- propanol and 23-chloro-l-propanol is here dis- closed which comprises the step of reacting 1,2-dichloroethane with methanol by irradiation with light in the presence of at least one compound selected from europium compounds, samarium compounds and ytterbium compounds, and if necessary, in the additional presence of a zeolite.

CM CO CO o> ro- ta

LU Jouve, 18, rue Saint-Denis, 75001 PARIS 1 EP 0 579 362 A1 2

The present invention relates to a method for pre- As a method to solve these problems, the pres- paring 2,3-dichloro-1-propanol and 3-chloro-1- ent inventor have suggested a method for preparing propanol. 2,3-dichloro-1-propanol and 3-chloro-1-propanol by More specifically, the present invention relates to irradiating methanol and 1 ,2-dichloroethane as start- a method for preparing 2,3-dichloro-1-propanol and 5 ing materials with light in the presence of a peroxide 3-chloro-1-propanol by hydoxymethylating 1,2-di- and/or an azo compound (Japanese Patent Applica- chloroethane with methanol. These products are in- tion No. 325516/ 1990), and a method for preparing dustrially important in themselves or as intermediates 2,3-dichloro-1-propano and 3-chloro-1-propanol by of reactions. irradiating methanol and 1 ,2-dichloroethane as start- Since 2,3-dichloro-1-propanol can easily be con- 10 ing materials with light in the presence of a carbonyl verted into epichlorohydrin with a caustic alkali or milk compound (Japanese Patent Application No. of lime, it is useful as a precursor of epichlorohydrin 250700/1991). which is a raw material of an epoxy resin and a syn- These methods in which the reaction is caused to thetic rubber. On the other hand, 3-chloro-1-propanol occur by the light irradiation can remarkably simplify is also a useful substance and industrially important 15 the manufacturing process, as compared with a con- as an intermediate for a reaction. ventional method, but they have the following prob- Nowadays, 2,3-dichloro-1-propanol which is the lems to be solved. That is to say, according to knowl- precursor of epichlorohydrin can be industrially man- edge of the present inventors, in the method in which ufactured by a method which comprises chlorinating the light irradiation is done in the presence of the per- propylene at a high temperature to form allyl chloride, 20 oxide, the peroxide in an amount equimolar with me- and then treating allyl chloride with chlorine and water thanol is required to produce a hydromethyl radical to form a chlorohydrin, or a method which comprises from methanol, and besides danger attends the han- acetoxylating propylene with acetic acid in the pres- dling of the peroxide. On the other hand, in the meth- ence of a palladium catalyst to form allyl acetate, hy- od in which the light irradiation is done in the pres- drolyzing allyl acetate to form allyl alcohol, and then 25 ence of the azo compound and the method in which chlorinating it. In addition, Japanese Patent Applica- the light irradiation is done in the presence of the car- tion Laid-open No. 297333/1988 has suggested a bonyl compound, an improvement effect of activation method which comprises chlorinating acetone in the is much lower than in the case of using the peroxide. presence of an iodine chloride catalyst and a lithium The present inventors have intensively investi- chloride catalyst to form 1,3-dichloroacetone, and 30 gated to ameliorate such problems, and as a result, then reacting 1,3-dichloroacetone with isopropanol in they have found that when 1,2-dichloroethane is re- the presence of an aluminum isopropoxide catalyst. acted with methanol by the irradiation of light in the On the other hand, as methods for preparing 3- presence of at least one compound selected from eu- chloro-1-propanol, there are known a method in ropium compounds, samarium compounds and ytter- which a chloropropanol mixture obtained by treating 35 bium compounds, 1,2-dichloroethane is hydroxyme- 1 ,3-propanediol with hydrogen chloride is subjected thylated with methanol to produce 2,3-dichloro-1- to fractional distillation several times [Organic Syn- propanol and 3-chloro-1-propanol. In consequence, thesis Coll. Vol. 1 , 533-534 (1 964)], a method in which the present invention has now been completed. acrolein is reacted with hydrogen chloride in an alco- In addition, the present inventors have also found hol to produce an acetal of 3-chloropropionaldehyde, 40 that when the above-mentioned reaction is carried and this acetal is then reduced in the presence of a out in the presence of a zeolite, a reaction rate and ruthenium catalyst (Belgian Patent No. 634845), a yields of 2,3-dichloro-1-propanol and 3-chloro-1- method in which hydrogen chloride is added to acro- propanol are remarkably increased. lein to form 3-chloropropionaldehyde, and this is then That is to say, the present invention is directed to reduced with an alkali metal bonarate (Japanese Pa- 45 a method for preparing 2,3-dichloro-1-propanol and tent Publication No. 42769/1977), and a method in 3-chloro-1-propanol which comprises the step of re- which epichlorohydrin is reduced with zinc borohydr- acting 1,2-dichloroethane with methanol by the irra- ide supported on silica gel to obtain a mixture of 3- diation of light in the presence of at least one com- chloro-1-propanol and propylene chlorohydrin [yield pound selected from europium compounds, samari- of 3-chloro-1-propanol = 60%, J. C. S. Chem. Comm., 50 urn compounds and ytterbium compounds. p. 1334(1990)]. Furthermore, the present invention is also direct- However, in each of these methods, there are ed to a method for preparing 2,3-dichloro-1-propanol some problems such as the use of the prolonged and 3-chloro-1-propanol which comprises the step of manufacturing process because of requiring reac- reacting 1,2-dichloroethane with methanol by the ir- tions in the several steps, the use of the expensive 55 radiation of light in the presence of a zeolite and at catalysts and the consumption of a large amount of least one compound selected from europium com- chlorine for the chlorination of the raw material. Thus, pounds, samarium compounds and ytterbium com- a simple and economical method is desired. pounds. 2 3 EP 0 579 362 A1 4

DETAILED DESCRIPTION OF THE INVENTION An amount of the zeolite to be used may be in the range of from 0.01 to 100 parts by weight, preferably Examples of the europium compounds, samari- from 0.05 to 50 parts by weight based on 1000 parts um compounds and ytterbium compounds which can by weight of a mixture solution comprising at least one be used in a method of the present invention include 5 compound selected from the group consisting of eu- powders of these metals; trivalent oxides, trivalent hy- ropium compounds, samarium compounds and ytter- droxides, trivalent fluorides, divalent and trivalent bium compounds, 1,2-dichloroethane and methanol. chlorides, trivalent bromides and trivalent iodides of As the light for the light irradiation in the present these metals; salts of mineral acids such as trivalent invention, there can be used white light having a wide nitrates, trivalent sulfates and trivalent phosphates of 10 wave range of from ultraviolet light to visible light or these metals; salts of organic acids such as trivalent monochromatic light, but the preferable light is the acetates, trivalent propionates and trivalent oxalates light generated from a mercury vapor lamp or a flash- of these metals; alkoxides such as trivalent methox- lamp, or laser beams. With regard to the manner of ides, trivalent ethoxides, trivalent isopropoxides and the light irradiation, a light source may be disposed trivalent butoxides of these metals; chelate com- 15 outside or inside the reaction vessel, and a more ef- pounds such as tris(acetylacetonate) salts, fective manner may be selected. tris(heptafluorobutanoylpivaloylmethanate) salts and 1,2-dichloroethane which can be used as the tris(pivaloyltrifluoroacetonate) salts of these metals; starting material in the present invention can be inex- and trivalent carbonates, trivalent perchlorates and pensively manufactured usually as a raw material of trivalent tungstates of these metals. 20 vinyl chloride by the heat chlorination of ethylene or The europium compounds, samarium com- the oxy-chlorination of ethylene. With regard to the pounds and ytterbium compounds may be in the state purity of 1,2-dichloroethane usable in the present in- of anhydrides or hydrates. In particular, the salts of vention, a purity of 1,2-dichloroethane for use in the the mineral acids, the salts of the organic acids, the manufacture of usual vinyl chloride is enough. carbonates, the alkoxides and the chelate com- 25 The other starting material which can be used in pounds are preferable. the method of the present invention, i.e., methanol In the present invention, one compound or plural can be inexpensively manufactured from carbon mon- compounds selected from the group consisting of the oxide and hydrogen obtained by modifying a petro- europium compounds, samarium compounds and yt- leum gas or a natural gas. With regard to the purity terbium compounds can be used. 30 of methanol usable in the present invention, a purity In the method of the present invention, an of methanol containing about 0.1% by weight or less amount of the compound selected from the group of water for use in the manufacture of usual formalin consisting of the europium compounds, samarium is enough. compounds and ytterbium compounds and then used In the present invention, the molar ratio of 1 ,2-di- in the reaction may be in the range of from 0.01 to 35 chloroethane to methanol may be in the range of from 2000 milligram atoms, preferably from 0.1 to 1000 mil- 0.001 to 100, preferably from 0.01 to 50. If this molar ligram atoms in terms of the total metal atoms based ratio is less than 0.001 or more than 100, a sufficient on 1 liter of a liquid phase in the reactions system. reaction rate may not always be obtained. The zeolite which can be used in the method of Furthermore, in the method of the present inven- the present invention is a crystalline aluminosilicate, 40 tion, a production ratio between 2,3-dichloro-1-prop- and examples of the zeolite include shabasite, erion- anol and 3-chloro-1-propanol which are the products ite, offretite, A type zeolite, ferrierite, mordenite, L can be controlled by changing the molar ratio of 1,2- type zeolite, X type zeolite, Y type zeolite and ZSM- dichloroethane to methanol which are the starting 5 type zeolite made by Mobil Co., Ltd. All of Na+ type, materials. The molar ratio between the starting ma- NH4+ type and H+ type of these zeolites are also usa- 45 terials which can control the production ratio between ble. Particularly, preferable is the zeolite in which Na+ the products depends upon reacting conditions such is substituted with a polyvalent ion such as calcium, as a kind and an amount of catalyst to be used, an in- manganese or a rare earth element by an ion ex- tensity of the light source, a distance between the change method. light source and the reactor, and a material of the re- The zeolite may be placed in a reaction vessel 50 actor used in the case of the external irradiation, but without any pretreatment, and it may also be used in when the molar ratio of 1 ,2-dichloroethane to metha- the reaction under the light irradiation together with nol is about 2 or less, 3-chloro-1-propanol is the main one or more compounds selected from the group con- product, and when it is more than 2, 2,3-dichloro-1- sisting of the europium compounds, samarium com- propanol is obtained as the main component. pounds and ytterbium compounds. Alternatively, prior 55 In the method of the present invention, the reac- to the use in the reaction, Na+ in the zeolite may pre- tion can proceed, even if any reaction solvent is not viously be replaced with europium, samarium or ytter- used. However, the reaction can also be achieved in bium by the ion exchange method. the presence of the solvent. Any solvent can be used, 3 5 EP 0 579 362 A1 6 so long as it does not have a bad influence on the re- vessel which is provided with a nitrogen blowing ori- action. fice. In this case, the molar ratio of 1,2-dichloro- The reaction temperature may be in the range of ethane to methanol was 1, and the concentration of from -30 to 140°C, preferably from 0 to 100°C. If the europium was 5 milligram atoms/liter of a liquid reaction temperature is lower than -30°C, the reaction 5 phase. A nitrogen gas was introduced thereinto rate may be insufficient, and if it is higherthan 140°C, through the nitrogen blowing orifice to replace the at- the production of by-products increases. The reaction mosphere in the system with nitrogen, and afterward pressure may be atmospheric pressure or heightened the system was irradiated internally with a 300 W pressure. The reaction time depends upon the inten- high pressure mercury lamp at room temperature for sity of a light source for the light irradiation, the pos- 10 5 hours with stirring under the nitrogen atmosphere ition where the light source is disposed, an irradiation to carry out the reaction. distance, the amount of the starting materials for use After completion of the reaction, the reaction sol- in the reaction, the amount of the europium com- ution was quantitatively analyzed by gas chromatog- pound, samarium compound or ytterbium compound, raphy, and as a result, it was apparent that 9.53 mmol and the like, but it is usually in the range of from 10 15 of 2,3-dichloro-1-propanol (hereinafter abbreviated to minutes to 100 hours. If the reaction time is shorter "2,3-DCP"), 6.04 mmol of 3-chloro-1-propanol (here- than 1 0 minutes, a sufficient production cannot be ob- inafter abbreviated to "3-CP") and 11.32 mmol of tained, and if it is longer than 100 hours, much time ethylene glycol (hereinafter abbreviated to "EG") is taken for the reaction, which is not economical. were produced. The method of the present invention can be ach- 20 ieved by any of a batch process, a semi-batch process Example 2 and a continuous process. For example, in the case of the batch process, methanol, 1,2-dichloroethane, 2.5 g (0.078 mol) of methanol, 1.0 g (0.01 mol)of at least one compound selected from the group con- 1,2-dichloroethane and 0.015 g (0.041 mmol) of eu- sisting of europium compounds, samarium com- 25 ropium trichloride hexahydrate were placed in a 1 0 ml pounds and ytterbium compounds, and if necessary, Pyrex glass reaction tube having an internal diameter a zeolite and a reaction solvent are placed in an inter- of 8 mm and a height of 20 cm. In this case, the molar nal irradiation type light reaction device, and they are ratio of 1,2-dichloroethane to methanol was 0.128, then irradiated with light for a predetermined time, so and the concentration of europium was 10 milligram that the reaction proceeds. In the case of the contin- 30 atoms/liter of a liquid phase. Next, the atmosphere in uous process, methanol, 1,2-dichloroethane, at least the reaction tube was replaced with nitrogen, and the one compound selected from the group consisting of reaction tube was then sealed. After-ward, the reac- europium compounds, samarium compounds and yt- tion tube was rotated round a 300 W high- pressure terbium compounds, and if necessary, a zeolite and mercury vapor lamp in a thermostat tank at 20°C to a reaction solvent are continuously fed to one side of 35 carry out reaction. After completion of the reaction, the light reaction device, and a reaction mixture which the reaction solution was quantitatively analyzed by involves unreacted methanol and 1,2-dichloroethane gas chromatography, and as a result, it was apparent is continuously drawn from the other side of the de- that 0.02 mmol of 2,3-DCP, 0.07 mmol of 3-CP and vice, while the reaction is carried out. 0.05 mmol of EG were produced. According to the method of the present invention, 40 2,3-dichloro-1-propanol and 3-chloro-1-propanol can Example 3 be prepared from 1 ,2-dichloroethane and methanol in one step, and in particular, when the reaction is car- Reaction and quantitative analysis were carried ried out in the presence of the zeolite, reaction rate out by the same procedure as in Example 2 except and yield can be remarkably improved. Therefore, it 45 that the amount of methanol was 2.8 g (0.087 mol) is fair to say that the industrial value of the present in- and that of 1 ,2-dichloroethane was 0.5 g (0.005 mol). vention is extremely great. As a result, it was apparent that 0.01 mmol of 2,3- Now, the present invention will be described in DCP, 0.09 mmol of 3-CP and 0.24 mmol of EG were more detail in reference to examples. However, it is to produced. be noted that the scope of the present invention 50 should not be limited to these examples. Example 4

Example 1 Reaction and quantitative analysis were carried out by the same procedure as in Example 2 except First, 107.3 g (3.35 mols) of methanol, 331.3 g 55 that the amount of methanol was 1.6 g (0.050 mol) (3.35 mols) of 1,2-dichloroethane and 0.697 g (1.9 and that of 1 ,2-dichloroethane was 2.5 g (0.025 mol). mmol) of europium trichloride hexahydrate were As a result, it was apparent that 0.05 mmol of 2,3- placed in a 400 ml inner source typed quartz reaction DCP, 0.08 mmol of 3-CP and 0.02 mmol of EG were 4 7 EP 0 579 362 A1 8 produced. Example 11

Example 5 Reaction and quantitative analysis were carried out by the same procedure as in Example 2 except Reaction and quantitative analysis were carried 5 that europium trichloride hexahydrate was replaced out by the same procedure as in Example 2 except with 0.002 g (0.010 mmol) of europium carbonate hy- that the amount of methanol was 1.0 g (0.031 mol) drate. As a result, it was apparent that 0.02 mmol of and that of 1 ,2-dichloroethane was 3.3 g (0.033 mol). 2,3-DCP, 0.07 mmol of 3-CP and 0.05 mmol of EG As a result, it was apparent that 0.05 mmol of 2,3- were produced. DCP, 0.05 mmol of 3-CP and 0.02 mmol of EG were 10 produced. Comparative Example 1

Example 6 Reaction and quantitative analysis were carried out by the same procedure as in Example 2 except Reaction and quantitative analysis were carried 15 that europium trichloride hexahydrate was not used. out by the same procedure as in Example 2 except As a result, any product was not detected. that the amount of europium trichloride hexahydrate was 0.075 g (0.20 mmol). As a result, it was apparent Comparative Example 2 that 0.01 mmol of 2,3-DCP, 0.02 mmol of 3-CP and 0.11 mmol of EG were produced. 20 Reaction and quantitative analysis were carried out by the same procedure as in Example 2 except Example 7 that light irradiation was not given. As a result, any product was not detected. Reaction and quantitative analysis were carried out by the same procedure as in Example 2 except 25 Comparative Example 3 that the amount of europium trichloride hexahydrate was changed to 0.004 g (0.011 mmol). As a result, it Reaction and quantitative analysis were carried was apparent that 0.01 mmol of 2,3-DCP, 0.03 mmol out by the same procedure as in Example 2 except of 3-CP and 0.10 mmol of EG were produced. that 1,2-dichloroethane was not used. As a result, 30 0.24 mmol of EG was only produced. Example 8 Example 12 Reaction and quantitative analysis were carried out by the same procedure as in Example 2 except Reaction was carried out by the same procedure that a Pyrex glass reaction tube was replaced with a 35 as in Example 1 except that europium trichloride hex- quartz reaction tube. As a result, it was apparent that ahydrate was replaced with 0.693 g (1.9 mmol) of sa- 0.10 mmol of 2,3-DCP, 0.65 mmol of 3-CP and 1.96 marium chloride hexahydrate. mmol of EG were produced. After completion of the reaction, the reaction solution was quantitatively analyzed by gas chromatog- Example 9 40 raphy, and as a result, it was apparent that 9.53 mmol of 2,3-DCP, 11 .32 mmol of 3-CP and 6.04 mmol of EG Reaction and quantitative analysis were carried were produced. out by the same procedure as in Example 2 except that europium trichloride hexahydrate was replaced Example 13 with 0.003 g (0.010 mmol) of europium acetate hy- 45 drate. As a result, it was apparent that 0.02 mmol of 1.6 g (0.050 mol) of methanol, 3.8 g (0.038 mol) 2,3-DCP, 0.05 mmol of 3-CP and 0.04 mmol of EG of 1 ,2-dichloroethane and 0.01 8 g (0.05 mmol) of sa- were produced. marium chloride hexahydrate were placed in a 1 0 ml quartz reaction tube having an internal diameter of 8 Example 10 so mm and a height of 20 cm. In this case, the molar ratio of 1 ,2-dichloroethane to methanol was 0.76, and the Reaction and quantitative analysis were carried concentration of samarium was 10 milligram out by the same procedure as in Example 2 except atoms/liter of a liquid phase. Next, the atmosphere in that europium trichloride hexahydrate was replaced the reaction tube was replaced with nitrogen, and the with 0.005 g (0.014 mmol) of europium perchlorate 55 reaction tube was then sealed. Afterward, the reac- hexahydrate. As a result, it was apparent that 0.01 tion tube was rotated round a 300 W high- pressure mmol of 2,3-DCP, 0.06 mmol of 3-CP and 0.07 mmol mercury vapor lamp in a thermostat tank at 20°C to of EG were produced. carry out reaction for 5 hours. 5 g EP 0 579 362 A1 10

After completion of the reaction, the reaction sol- chloride hexahydrate was changed to 0.004 g (0.010 ution was quantitatively analyzed by gas chromatog- mmol). raphy, and as a result, it was apparent that 0.03 mmol After completion of the reaction, the reaction sol- of 2,3-DCP, 0.11 mmol of 3-CP and 0.02 mmol of EG ution was quantitatively analyzed by gas chromatog- were produced. 5 raphy, and as a result, it was apparent that 0.01 mmol of 2,3-DCP, 0.04 mmol of 3-CP and 0.01 mmol of EG Example 14 were produced.

Reaction was carried out by the same procedure Example 19 as in Example 13 except that the amount of methanol 10 was 2.8 g (0.087 mol) and that of 1,2-dichloroethane Reaction was carried out by the same procedure was 0.5 g (0.005 mol). as in Example 13 except that a quartz reaction tube After completion of the reaction, the reaction sol- was replaced with a Pyrex glass reaction tube. ution was quantitatively analyzed by gas chromatog- After completion of the reaction, the reaction soi- raphy, and as a result, it was apparent that 0.02 mmol ls ution was quantitatively analyzed by gas chromatog- of 2,3-DCP, 0.27 mmol of 3-CP and 0.61 mmol of EG raphy, and as a result, it was apparent that 0.02 mmol were produced. of 2,3-DCP, 0.06 mmol of 3-CP and 0.01 mmol of EG were produced. Example 15 20 Example 20 Reaction was carried out by the same procedure as in Example 13 except that the amount of methanol Reaction was carried out by the same procedure was 1.6 g (0.050 mol) and that of 1,2-dichloroethane as in Example 13 except that samarium chloride hex- was 2.5 g (0,025 mol). ahydrate was replaced with 0.003 g (0.010 mmol) of After completion of the reaction, the reaction sol- 25 samarium acetate (III) hydrate. ution was quantitatively analyzed by gas chromatog- After completion of the reaction, the reaction sol- raphy, and as a result, it was apparent that 0.03 mmol ution was quantitatively analyzed by gas chromatog- of 2,3-DCP, 0.21 mmol of 3-CP and 0.25 mmol of EG raphy, and as a result, it was apparent that 0.02 mmol were produced. of 2,3-DCP, 0.05 mmol of 3-CP and 0.04 mmol of EG 30 were produced. Example 16 Example 21 Reaction was carried out by the same procedure as in Example 13 except that the amount of methanol Reaction was carried out by the same procedure was 1.0 g (0.031 mol) and that of 1,2-dichloroethane 35 as in Example 13 except that samarium chloride hex- was 3.3 g (0,033 mol). ahydrate was replaced with 0.004 g (0.010 mmol) of After completion of the reaction, the reaction sol- samarium perchlorate (III) hexahydrate. ution was quantitatively analyzed by gas chromatog- After completion of the reaction, the reaction sol- raphy, and as a result, it was apparent that 0.04 mmol ution was quantitatively analyzed by gas chromatog- of 2,3-DCP, 0.06 mmol of 3-CP and 0.01 mmol of EG 40 raphy, and as a result, it was apparent that 0.01 mmol were produced. of 2,3-DCP, 0.06 mmol of 3-CP and 0.07 mmol of EG were produced. Example 17 Example 22 Reaction was carried out by the same procedure 45 as in Example 13 except that the amount of samarium Reaction was carried out by the same procedure chloride hexahydrate was changed to 0.037 g (0.10 as in Example 13 except that samarium chloride hex- mmol). ahydrate was replaced with 0.005 g (0.010 mmol) of After completion of the reaction, the reaction sol- samarium carbonate (III) hydrate. ution was quantitatively analyzed by gas chromatog- so After completion of the reaction, the reaction sol- raphy, and as a result, it was apparent that 0.02 mmol ution was quantitatively analyzed by gas chromatog- of 2,3-DCP, 0.09 mmol of 3-CP and 0.01 mmol of EG raphy, and as a result, it was apparent that 0.02 mmol were produced. of 2,3-DCP, 0.07 mmol of 3-CP and 0.05 mmol of EG were produced. Example 18 55 Comparative Example 4 Reaction was carried out by the same procedure as in Example 13 except that the amount of samarium Reaction was carried out by the same procedure 6 11 EP 0 579 362 A1 12 as in Example 1 3 except that samarium chloride hex- were produced. ahydrate was not used. After completion of the reaction, the reaction sol- Example 25 ution was quantitatively analyzed by gas chromatography, and as a result, it was apparent that any prod- 5 Reaction was carried out by the same procedure uct was not detected. as in Example 23 except that the amount of methanol was 1.6 g (0.050 mol) and that of 1,2-dichloroethane Comparative Example 5 was 2.5 g (0.025 mol). After completion of the reaction, the reaction sol- Reaction was carried out by the same procedure 10 ution was quantitatively analyzed by gas chromatog- as in Example 13 except that light irradiation was not raphy, and as a result, it was apparent that 0.03 mmol given. of 2,3-DCP, 0.27 mmol of 3-CP and 0.09 mmol of EG After completion of the reaction, the reaction sol- were produced. ution was quantitatively analyzed by gas chromatography, and as a result, it was apparent that any prod- 15 Example 26 uct was not detected. Reaction was carried out by the same procedure Comparative Example 6 as in Example 23 except that the amount of methanol was 1.0 g (0.031 mol) and that of 1,2-dichloroethane Reaction was carried out by the same procedure 20 was 3.3 g (0.033 mol). as in Example 13 except that 1,2-dichloroethane was After completion of the reaction, the reaction sol- not used. ution was quantitatively analyzed by gas chromatog- After completion of the reaction, the reaction sol- raphy, and as a result, it was apparent that 0.06 mmol ution was quantitatively analyzed by gas chromatog- of 2,3-DCP, 0.07 mmol of 3-CP and 0.01 mmol of EG raphy, and as a result, it was apparent that 0.24 mmol 25 were produced. of EG was only produced. Example 27 Example 23 Reaction was carried out by the same procedure 1.6 g (0.050 mol) of methanol, 3.8 g (0.038 mol) 30 as in Example 23 except that the amount of ytterbium of 1 ,2-dichloroethane and 0.019 g (0.050 mmol) of yt- chloride hexahydrate was changed to 0.039 g (0.100 terbium chloride hexahydrate were placed in a 10 ml mmol). quartz reaction tube having an internal diameter of 8 After completion of the reaction, the reaction sol- mm and a height of 20 cm. In this case, the molar ratio ution was quantitatively analyzed by gas chromatog- of 1 ,2-dichloroethane to methanol was 0.76, and the 35 raphy, and as a result, it was apparent that 0.05 mmol concentration of ytterbium was 10 milligram of 2,3-DCP, 0.14 mmol of 3-CP and 0.02 mmol of EG atoms/liter of a liquid phase. Next, the atmosphere in were produced. the reaction tube was replaced with nitrogen, and the reaction tube was then sealed. Afterward, the reac- Example 28 tion tube was rotated round a 300 W high-pressure 40 mercury vapor lamp in a thermostat tank at 20°C to Reaction was carried out by the same procedure carry out reaction for 5 hours. as in Example 23 except that the amount of ytterbium After completion of the reaction, the reaction sol- chloride hexahydrate was changed to 0.004 g (0.010 ution was quantitatively analyzed by gas chromatog- mmol). raphy, and as a result, it was apparent that 0.04 mmol 45 After completion of the reaction, the reaction sol- of 2,3-DCP, 0.13 mmol of 3-CP and 0.02 mmol of EG ution was quantitatively analyzed by gas chromatog- were produced. raphy, and as a result, it was apparent that 0.02 mmol of 2,3-DCP, 0.05 mmol of 3-CP and 0.01 mmol of EG Example 24 were produced. 50 Reaction was carried out by the same procedure Example 29 as in Example 23 except that the amount of methanol was 2.8 g (0.087 mol) and that of 1,2-dichloroethane Reaction was carried out by the same procedure was 0.5 g (0.005 mol). as in Example 23 except that a quartz reaction tube After completion of the reaction, the reaction sol- 55 was replaced with a Pyrex glass reaction tube. ution was quantitatively analyzed by gas chromatog- After completion of the reaction, the reaction sol- raphy, and as a result, it was apparent that 0.02 mmol ution was quantitatively analyzed by gas chromatog- of 2,3-DCP, 0.63 mmol of 3-CP and 0.16 mmol of EG raphy, and as a result, it was apparent that 0.03 mmol 7 13 EP 0 579 362 A1 14 of 2,3-DCP, 0.06 mmol of 3-CP and 0.01 mmol of EG tion was quantitatively analyzed by gas chromatogra- were produced. phy. As a result, it was apparent that 0.07 mmol of 2,3- DCP, 0.06 mmol of 3-CP and 0.01 mmol of EG were Example 30 produced. 5 Reaction was carried out by the same procedure Example 34 as in Example 23 except that ytterbium chloride hexahydrate was replaced with 0.004 g (0.010 mmol) of Reaction was carried out by the same procedure ytterbium acetate (III) hydrate. as in Example 33 except that TSZ-841 was replaced After completion of the reaction, the reaction sol- 10 with 30 mg of a Y type zeolite. ution was quantitatively analyzed by gas chromatog- After completion of the reaction, the zeolite pow- raphy, and as a result, it was apparent that 0.02 mmol der was removed by filtration, and the reaction solu- of 2,3-DCP, 0.05 mmol of 3-CP and 0.02 mmol of EG tion was quantitatively analyzed by gas chromatogra- were produced. phy. As a result, it was apparent that 0.06 mmol of 2,3- 15 DCP, 0.05 mmol of 3-CP and 0.01 mmol of EG were Example 31 produced.

Reaction was carried out by the same procedure Example 35 as in Example 23 except that ytterbium chloride hexahydrate was replaced with 0.005 g (0.010 mmol) of 20 Reaction was carried out by the same procedure ytterbium perchlorate (III) hexahydrate. as in Example 33 except that TSZ-841 was replaced After completion of the reaction, the reaction sol- with 30 mg of a mordenite powder. ution was quantitatively analyzed by gas chromatog- After completion of the reaction, the zeolite pow- raphy, and as a result, it was apparent that 0.02 mmol der was removed by filtration, and the reaction solu- of 2,3-DCP, 0.04 mmol of 3-CP and 0.07 mmol of EG 25 tion was quantitatively analyzed by gas chromatogra- were produced. phy. As a result, it was apparent that 0.06 mmol of 2,3- DCP, 0.05 mmol of 3-CP and 0.01 mmol of EG were Example 32 produced.

Reaction was carried out by the same procedure 30 Example 36 as in Example 23 except that ytterbium chloride hexahydrate was replaced with 0.004 g (0.010 mmol) of Reaction was carried out by the same procedure ytterbium nitrate (III) hydrate. as in Example 33 except that TSZ-841 was replaced After completion of the reaction, the reaction sol- with 30 mg of a molecular sieves 13X powder. ution was quantitatively analyzed by gas chromatog- 35 After completion of the reaction, the zeolite pow- raphy, and as a result, it was apparent that 0.02 mmol der was removed by filtration, and the reaction solu- of 2,3-DCP, 0.07 mmol of 3-CP and 0.04 mmol of EG tion was quantitatively analyzed by gas chromatogra- were produced. phy. As a result, it was apparent that 0.04 mmol of 2,3- DCP and 0.04 mmol of 3-CP were produced. Example 33 40 Example 37 0.01 8 g (0.050 mmol) of europium trichloride hexahydrate were placed in a 10 ml quartz reaction tube Reaction was carried out by the same procedure having an internal diameter of 8 mm and a height of as in Example 33 except that europium trichloride 20 cm, and then dissolved in 2.0 g (0.062 mol) of me- 45 hexahydrate was replaced with 0.01 5 g (0.041 mmol) thanol. After-ward, 30 mg of a ZSM-5 type zeolite of samarium trichloride hexahydrate. (TSZ-841) powder made by Toso Co., Ltd. which had After completion of the reaction, the zeolite pow- been dried at 200°C for 10 hours were added thereto der was removed by filtration, and the reaction solu- and then sufficiently dispersed therein by ultrasonic tion was quantitatively analyzed by gas chromatogra- wave. Next, 1.0 g (0.010 mol) of 1,2-dichloroethane 50 phy. As a result, itwasapparentthat0.07mmolof2,3- was added thereto, and the atmosphere in the reac- DCP, 0.12 mmol of 3-CP and 0.01 mmol of EG were tion tube was replaced with nitrogen and the reaction produced. tube was then sealed. Afterward, the reaction tube was rotated round a 300 W high-pressure mercury va- Example 38 por lamp in a thermostat tank at 20°C to carry out re- 55 action for 5 hours. Reaction was carried out by the same procedure After completion of the reaction, the zeolite pow- as in Example 34 except that europium trichloride der was removed by filtration, and the reaction solu- hexahydrate was replaced with 0.01 5 g (0.041 mmol) 8 15 EP 0 579 362 A1 16 of samarium trichloride hexahydrate. solution inlet and a solution outlet, and a pump, the After completion of the reaction, the zeolite pow- vessel (A), the bottle (B) and the pump being connect- der was removed by filtration, and the reaction solu- ed to each other by Teflon tubes. The solution outlet tion was quantitatively analyzed by gas chromatogra- of the wide mouth bottle (B) was connected to the sol- phy. As a result, it was apparent that 0.06 mmol of 2,3- 5 ution inlet of the glass reaction vessel (A) via the DCP and 0.10 mmol of 3-CP were produced. pump, and the solution outlet of the glass reaction vessel (A) was connected to the solution outlet of the Example 39 wide mouth bottle (B). After the atmosphere in the system was replaced with a nitrogen gas, a material Reaction was carried out by the same procedure 10 mixture solution comprising 93.40 g (2.92 mol) of me- as in Example 35 except that europium trichloride thanol, 239.26 g (2.42 mol) of 1 ,2-dichloroethane and hexahydrate was replaced with 0.016 g (0.041 mmol) 1 .541 g (4.22 mmol) of europium trichloride hexahy- of ytterbium trichloride hexahydrate. drate was placed in the wide mouth bottle (B). In this After completion of the reaction, the zeolite pow- case, the molar ratio of 1 ,2-dichloroethane to metha- der was removed by filtration, and the reaction solu- 15 nol was 0.83, and the concentration of europium was tion was quantitatively analyzed by gas chromatogra- 10 milligram atoms/liter of a liquid phase. Next, the phy. As a result, it was apparent that 0.05 mmol of 2,3- material mixture solution was forwarded to the glass DCP and 0.09 mmol of 3-CP were produced. reaction vessel (A) by means of the tube pump, and the space between the inside cylinder and the out- Comparative Example 7 20 side cylinder was filled with the material mixture solution. The overflow from the glass reaction vessel (A) Reaction was carried out by the same procedure was introduced into the wide mouth bottle (B), and as in Example 33 except that TSZ-841 was not used. the reaction temperature in the glass reaction vessel After completion of the reaction, the reaction sol- (A) was maintained at 7°C in a thermostat tank and ution was quantitatively analyzed by gas chromatog- 25 the reaction solution was irradiated with light for 3 raphy, and as a result, it was apparent that 0.03 mmol hours to carry out reaction, while the reaction solution of 2,3-DCP, 0.03 mmol of 3-CP and 0.01 mmol of EG was circulated through the above-mentioned route by were produced. means of the pump. After completion of the reaction, the reaction sol- Comparative Example 8 30 ution was quantitatively analyzed by gas chromatography, and as a result, it was apparent that 7.62 mmol Reaction was carried out by the same procedure of 2,3-DCP, 12.82 mmol of 3-CP and 6.48 mmol of EG as in Example 37 except that TSZ-841 was not used. were produced. After completion of the reaction, the reaction solution was quantitatively analyzed by gas chromatog- 35 Example 41 raphy, and as a result, it was apparent that 0.03 mmol of 2,3-DCP, 0.06 mmol of 3-CP and 0.02 mmol of EG Reaction was carried out by the same procedure were produced. as in Example 40 except that the amount of methanol was 67.98 g (2.12 mol) and that of 1 ,2-dichloroethane Comparative Example 9 40 was 430.38 g (4.35 mol). In this case, the molar ratio of 1 ,2-dichloroethane to methanol was 2.05, and the Reaction was carried out by the same procedure concentration of europium was 10 milligram as in Example 39 except that any mordenite powder atoms/liter of a liquid phase. was not used. After completion of the reaction, the reaction sol- After completion of the reaction, the reaction sol- 45 ution was quantitatively analyzed by gas chromatog- ution was quantitatively analyzed by gas chromatography, and as a result, it was apparent that 7.78 mmol raphy, and as a result, it was apparent that 0.03 mmol of 2,3-DCP, 8.69 mmol of 3-CP and 1 0.89 mmol of EG of 2,3-DCP, 0.08 mmol of 3-CP and 0.02 mmol of EG were produced. were produced. 50 Example 42 Example 40 Reaction was carried out by the same procedure There was prepared a device comprising a 1 90 ml as in Example 40 except that the amount of methanol reaction vessel (A) in which a 300 W high-pressure was 30.87 g (0.96 mol) and that of 1 ,2-dichloroethane mercury vapor lamp (having a quartz protective tube) 55 was 477.29 g (4.82 mol). In this case, the molar ratio as a light source was inserted into a glass vessel pro- of 1 ,2-dichloroethane to methanol was 5.02, and the vided with a solution inlet and a solution outlet, a 150 concentration of europium was 10 milligram ml wide mouth bottle (B) equipped with a lid having a atoms/liter of a liquid phase. 9 17 EP 0 579 362 A1 18

After completion of the reaction, the reaction sol- Example 46 ution was quantitatively analyzed by gas chromatography, and as a result, it was apparent that 6.30 mmol Reaction was carried out by the same procedure of 2,3-DCP, 3.34 mmol of 3-CP and 3.24 mmol of EG as in Example 44 except that 0.015 g (0.04 mmol) of were produced. 5 europium trichloride hexahydrate and 0.016 g (0.04 mmol) of ytterbium trichloride hexahydrate were used Example 43 as catalysts. After completion of the reaction, the reaction sol- Reaction was carried out by the same procedure ution was quantitatively analyzed by gas chromatog- as in Example 40 except that the amount of methanol 10 raphy, and as a result, it was apparent that 0.16 mmol was 25.82 g (0.81 mol) and that of 1 ,2-dichloroethane of 2,3-DCP, 0.51 mmol of 3-CP and 0.21 mmol of EG was 490.39 g (4.96 mol). In this case, the molar ratio were produced. of 1 ,2-dichloroethane to methanol was 6.12, and the concentration of europium was 10 milligram Comparative Example 10 atoms/liter of a liquid phase. 15 After completion of the reaction, the reaction sol- Reaction was carried out by the same procedure ution was quantitatively analyzed by gas chromatog- as in Example 40 except that europium trichloride raphy, and as a result, it was apparent that 13.29 hexahydrate was not used. mmol of 2,3-DCP, 2.31 mmol of 3-CP and 2.64 mmol After completion of the reaction, the reaction sol- of EG were produced. 20 ution was quantitatively analyzed by gas chromatography, and as a result, it was apparent that any prod- Example 44 uct was not detected.

1.27 g (0.04 mol) of methanol, 3.01 g (0.03 mol) Comparative Example 11 of 1,2-dichloroethane, 0.015 g (0.04 mmol) of euro- 25 pium trichloride hexahydrate and 0.009 g (0.04 mmol) Reaction was carried out by the same procedure of europium dichloride hydrate as catalysts were as in Example 40 except that light irradiation was not placed in a 10 ml quartz reaction tube having an in- given. ternal diameter of 8 mm and a height of 20 cm. In this After completion of the reaction, the reaction sol- case, the molar ratio of 1 ,2-dichloroethane to metha- 30 ution was quantitatively analyzed by gas chromatog- nol was 0.75, and the concentration of europium was raphy, and as a result, it was apparent that any prod- 20 milligram atoms/I iter of a liquid phase. Next, the at- uct was not detected. mosphere in the reaction tube was replaced with nitrogen, and the reaction tube was then sealed. After- Comparative Example 12 ward, the reaction tube was rotated round a 300 W 35 high-pressure mercury vapor lamp in a thermostat Reaction was carried out by the same procedure tank at 20°C to carry out reaction for 5 hours. as in Example 40 except that 1 ,2-dichloroethane was After completion of the reaction, the reaction sol- not used. ution was quantitatively analyzed by gas chromatog- After completion of the reaction, the reaction sol- raphy, and as a result, it was apparent that 0.23 mmol 40 ution was quantitatively analyzed by gas chromatog- of 2,3-DCP, 0.58 mmol of 3-CP and 0.23 mmol of EG raphy, and as a result, it was apparent that 106.21 were produced. mmol of EG was only produced.

Example 45 45 Claims Reaction was carried out by the same procedure as in Example 44 except that 0.015 g (0.04 mmol) of 1. A method for preparing 2,3-dichloro-1-propanol europium trichloride hexahydrate and 0.015 g (0.04 and 3-chloro-1-propanol which comprises the mmol) of samarium trichloride hexahydrate were used step of reacting 1,2-dichloroethane with metha- as catalysts. 50 nol by irradiation with light in the presence of at After completion of the reaction, the reaction sol- least one compound selected from europium ution was quantitatively analyzed by gas chromatog- compounds, samarium compounds and ytter- raphy, and as a result, it was apparent that 0.18 mmol bium compounds. of 2,3-DCP, 0.46 mmol of 3-CP and 0.25 mmol of EG were produced. 55 2. A method for preparing 2,3-dichloro-1-propanol and 3-chloro-1-propanol which comprises the step of reacting 1,2-dichloroethane with methanol by irradiation with light in the present of a zeo- 10 19 EP 0 579 362 A1 20

lite and at least one compound selected from europium compounds, samarium compounds and ytterbium compounds.

3. The method according to claim 1 or 2 wherein a 5 production ratio between 2,3-dichloro-1-propanol and 2-chloro-1-propanol is controlled by changing a molar ratio between 1,2-dichloroethane and methanol. 10

11 EP 0 579 362 A1

European Patent Application Number J EUROPEAN SEARCH REPORT Office

DOCUMENTS CONSIDERED TO BE RELEVANT EP 93303893.7 Citation of document with indication, where appropriate, Relevant CLASSIFICATION OF THE Category of relevant passages to claim APPLICATION (Int. a.5) US - A 5 104 504 1,2 C 07 C 31/36 ( MAS ATO TANKAKA ET AL.) C 07 C 29/32 * Claim 1 *

US A - 4 788 351 1,2 ( SADAO TAKAKUWA ET AL . ) * Abstract *

PATENT ABSTRACTS OF JAPAN, 1,2 unexamined applications , C field, vol. 8, no. 251, November 16, 1984 THE PATENT OFFICE JAPANESE GOVERNMENT page 12 C 252 * No. 59-128 340 (SHOWA DENKO)

PATENT ABSTRACTS OF JAPAN, 1,2 unexamined applications , C field, vol. 8, no. 251, TECHNICAL FIELDS November 16, 1984 SEARCHED (Int. CI.5) THE PATENT OFFICE JAPANESE GOVERNMENT C 07 C 29/00 page 12 C 252 C 07 C 31/00 * No. 59-128 341 (SHOWA DENKO) *

GB 2 129 794 1,2 (THE LUMMUS COMPANY) * Abstract *

PATENT ABSTRACTS OF JAPAN, 1,2 unexamined applications, C section, vol. 2, no. 67, May 20, 1978 THE PATENT OFFICE JAPANESE GOVERNMENT page 542 C 78 * No. 53-21 111 (KOGYO

The present search report has been drawn up for all claims Place of search Dale of completion of the search Examiner VIENNA 07-10-1993 REIF

CATEGORY OF CITED DOCUMENTS theory or principle underlying the invention earlier patent document, but published on. or X : particularly relevant if taken alone after the filing date V : particularly relevant if combined with another : document cited in the application document of the same category document cited for other reasons A : technological background O : non-written disclosure & : member of the same patent family, corresponding P : intermediate document document

12 :P 0 579 362 A1

Patent i ...... -~. European EUROPEAN SEAKCH KtfUKi iyVtf~mm,i )fficc

)OCUMENTS CONSIDERED TO BE KLLEVAfN 1 2P 93303893.7 station or document with indication, wnere appropriate, :ateg«ry claim APPLICATION Qnt. Q.5) of relevant passages __ o GIJUTSUIN) *

3E - A - 2 115 327 (DEUTSCHE GOLD- UND SILBER-] * Claim 1 *

iEARCHED (In«- CI.5)

The present search report has been drawn up for all claims Hace O! searcn IMC u i x.uni|jrc»uii Wl »--~ »•»■ VIENNA REIF

CATEGORY OF CITED DOOJMEMb i : tneory or principle unuenymg me lunamun E : earlier patent document, but published on, or \ : particularly relevant if taken alone after the filing date Y : particularly relevant if combined with another D : document cited in the application document of the same category L : document cited for other reasons A : technological background O : non-written disclosure & : member of the same patent family, corresponding P : intermediate document document