text: as for copper halides which are one of active ingredients of the catalyst , copper chloride , copper bromide and copper iodide are mentioned , and copper chloride may be used usually due to the cost and availability . as for tertiary organophosphorus compounds having phenyl group or alkyl group , alkylarylphosphines like triphenylphosphine , triphenylphosphite and dimethylphenylphosphine , trialkylphosphites like trimethylphosphite and triethylphosphite , and trialkylphosphates like triethylphosphate and trimethylphosphate are mentioned . the active ingredients may exist either in a form of a mixture of a copper halide and a tertiary organophosphorus compound having phenyl group or alkyl group , or in a form of a copper complex prepared by reacting a copper halide with a tertiary organophosphorus compound having phenyl group or alkyl group . the catalyst comprising a copper halide and a tertiary organophosphorus compound having phenyl group or alkyl group may either be carried or not carried on a porous carrier , however , that of carried on a porous carrier exhibits a higher yield of carbonic acid esters per unit weight of the active ingredient comprising a copper halide and a tertiary organophosphorus compound . as for porous carriers , those having surface areas of 30 m 2 / g or above are preferred , and active carbon , titanium oxide , zirconium oxide , niobium oxide , magnesium oxide , silica and alumina are exemplified , and active carbon is the most preferred . a copper halide and the above - mentioned tertiary organophosphorus compound may be carried on a carrier with a solvent at around the boiling point of the solvent . for example , it is conducted with ethanol solvent at 70 °- 80 ° c ., and preferably under an inert gas ( nitrogen , argon or helium ) stream saturated with ethanol . as a method of carrying a copper halide and a tertiary organophosphorus compound having phenyl group and alkyl group on a carrier , such manners are employable as the copper halide is carried firstly and then the tertiary organophosphorus compound is carried ; the tertiary organophosphorus compound is carried firstly and then the copper halide is carried ; and a copper complex prepared beforehand by reacting the copper halide with the tertiary organophosphorus compound is carried on a carrier . for example , in an ethanol solution of a copper halide is added a carrier so as the copper halide is carried , and then an ethanol solution of a tertiary organophosphorus compound is added to solidify copper halide - tertiary organophosphorus compound on the carrier . as another manner , an ethanol solution of a tertiary organophosphorus compound is firstly made contact with a carrier , and then an ethanol solution of a copper halide is made contact . amounts of the tertiary organophosphorus compound to be added are preferably 0 . 05 - 0 . 4 mol per copper atom mol in the copper halide . when the catalyst is carried on a carrier , contents of the copper halide in the catalyst is preferably around 2 - 10 wt . % per carrier as copper in the copper halide . after the copper halide - tertiary organophosphorus compound is fixed on a carrier , the solvent is removed . for example , removal of the solvent ethanol is performed by evaporation at 70 °- 80 ° c . under air or an inert gas atmosphere . in another manner , ethanol may be removed by applying vacuum at relatively low temperatures as 40 ° c . when a complex is prepared beforehand with a copper halide and a tertiary organophosphorus compound , then the complex is carried on a carrier , the copper halide is dissolved in a solvent like ethanol or methylene chloride , and to the solution is added under an inert gas atmosphere a tertiary organophosphorus compound dissolved in a solvent like ethanol or methylene chloride to cause a reaction , and then the solvent is removed to obtain the copper complex . the copper complex is carried on a carrier and fixed by dissolving thus obtained copper complex in such a solvent like chloroform , and the solution is applied on various porous carriers , or the complex is fixed on a carrier by mixing physically the complex wet with a solvent like a lower alcohol or in the absence of solvent , and then processing under an inert gas atmosphere ( nitrogen , argon or helium ) for stabilization . as for copper complexes prepared with a copper halide and a tertiary organophosphorus compound , those represented by the following formula are especially preferred ; cu ( pph 3 ) n x [ pph 3 = p ( c 6 h 5 ) 3 ; x = halogen ; n = 1 , 2 or 3 ]. the above - mentioned copper complex can be prepared with copper halides like cuprous chloride or cupric chloride and triphenylphosphine , ( refer to examples for preparing copper complexes ). contents of the copper complex in the catalyst are to be around 2 - 10 wt . % per carrier as copper in the copper complex . catalysts with such copper complexes carried on carriers exhibit higher activities than a copper complex by itself in the synthesis of carbonic acid esters by oxidation - carbonylation of alcohols . as to raw material alcohols , aliphatic alcohols having 1 - 4 carbon atoms , alicyclic alcohols and aromatic alcohols are employable . examples thereof are methanol , ethanol , propylalcohol , butanol , cyclohexanol and benzylalcohol , and primary alcohols like methanol and ethanol are preferred . reaction conditions for producing carbonic acid esters from alcohols , carbon monoxide and oxygen are preferably reaction temperature of 70 °- 200 ° c . and reaction pressure of from atmospheric pressure to 15 kg / cm 2 g for the vapor phase reaction , and reaction temperature of 80 °- 150 ° c . and reaction pressure of 5 - 30 kg / cm 2 g for the liquid phase reaction . molar ratios of carbon monoxide and oxygen to alcohols like methanol or ethanol are preferably around 1 . 2 - 0 . 5 and 0 . 55 - 0 . 01 respectively ( co / o 2 ratio = 1 / 1 - 100 / 1 ). the present invention will be explained concretely hereunder with examples , but the invention never be limited by the examples . a test was conducted for a known catalyst carrying copper halide on a porous carrier . into a 500 ml ( milliliter ) flask , 8 . 465 grams of cupric chloride ( cucl 2 ) and 150 ml of ethanol were charged to make a solution . then , 50 grams of an active carbon ( surface area : 1000 m 2 / g ; 4 - 16 mesh ) were added to the solution and stirred . ethanol was evaporated on a hot bath of 70 °- 80 ° c . to obtain catalyst b1 . for the purpose of measuring activity of catalyst b1 for dimethyl carbonate formation , a measurement was conducted using an ordinary atmospheric pressure fixed bed flow reactor under the following reaction conditions . into a stainless reactor tube having 10 mm inner diameter was packed 0 . 5 ml of catalyst b1 , and 6 ml / hr of methanol , 67 ml / min of carbon monoxide and 34 ml / min of oxygen were introduced into the tube under a vapor phase reaction conditions of 150 ° c . and atmospheric pressure to measure activity for dimethyl carbonate formation . the result is shown in table 1 . catalyst a1 - a7 mentioned hereunder were prepared , and their activities for dimethyl carbonate formation were measured under the same conditions with comparative example 1 , and the result are shown in table 1 . catalyst a1 : into a 500 ml flask equipped with a reflux condenser were charged 8 . 465 grams of cupric chloride ( cucl 2 ) and 150 ml of ethanol to make a solution , and 50 grams of an active carbon ( surface area : 1000 m 2 / g ; 4 - 16 mesh ) were added to the solution . the solution was maintained at 70 °- 80 ° c . under a stream of nitrogen gas saturated with ethanol , and a solution prepared by dissolving 1 . 94 grams of triphenylphosphine as the tertiary organophosphorus compound in 100 ml of hot ethanol was poured slowly into the flask through the reflux condenser . the mixture was stirred vigorously under reflux for 2 hours . after completion of the reflux , the reflux condenser was removed and ethanol was evaporated to obtain catalyst a1 . catalyst a2 : catalyst a2 was prepared in the same manner with catalyst a1 with the exception that 1 . 655 ml of triphenylphosphite was used as the tertiary organophosphorus compound in place of triphenylphosphine used for preparation of catalyst a1 . catalyst a3 : catalyst a3 was prepared in the same manner with catalyst a1 with the exception that 0 . 754 ml of trimethylphosphite was used as the tertiary organophosphorus compound in place of triphenylphosphine used for preparation of catalyst a1 . catalyst a4 : catalyst a4 was prepared in the same manner with catalyst a1 with the exception that 1 . 08 ml of triethylphosphite was used as the tertiary organophosphorus compound in place of triphenylphosphine used for preparation of catalyst a1 . catalyst a5 : catalyst a5 was prepared in the same manner with catalyst a1 with the exception that 1 . 08 ml of triethylphosphate was used as the tertiary organophosphorus compound in place of triphenylphosphine used for preparation of catalyst a1 . catalyst a6 : catalyst a6 was prepared in the same manner with catalyst a1 with the exception that 5 . 145 grams of triphenylphosphine was used as the tertiary organophosphorus compound . catalyst a7 : catalyst a7 was prepared in the same manner with catalyst a1 with the exception that 3 . 175 grams of cupric chloride and 1 . 94 grams of triphenylphosphine were used . as is shown clearly by the test results in table 1 , when an alcohol is reacted in a vapor phase with carbon monoxide and oxygen in the presence of a catalyst containing a copper halide and a tertiary organophosphorus compound having phenyl group or alkyl group , an enhanced activity of formation and selectivity for dimethyl carbonate are observed in comparison with the case of using the known catalyst b1 ( catalyst of international application publication w087 / 07601 ) carrying only a copper halide on a carrier . table 1__________________________________________________________________________catalyst dimethylcarbonate formationcu tertiary organo - mole ratio of activity of relative selec - relativecontent phosphorus organophosphorus formation activity of tivity selectiv - wt . % compound compound / cu mol / l - cat · h formation * 1 % ity * 2__________________________________________________________________________b1 8 none 0 0 . 70 1 . 0 32 1 . 0a1 8 triphenylphosphine 0 . 12 2 . 01 2 . 9 70 2 . 2a2 8 triphenylphosphite 0 . 10 1 . 39 2 . 0 55 1 . 7a3 8 trimethylphosphite 0 . 10 1 . 34 1 . 9 65 2 . 0a4 8 triethylphosphite 0 . 10 1 . 38 2 . 0 62 1 . 9a5 8 triethylphosphate 0 . 10 1 . 32 1 . 9 62 1 . 9a6 8 triphenylphosphine 0 . 31 1 . 64 2 . 3 56 1 . 8a7 3 triphenylphosphine 0 . 31 2 . 09 3 . 0 74 2 . 3__________________________________________________________________________ * 1 activity of formation relative to 1 . 0 of catalyst b1 * 2 selectivity relative to 1 . 0 of catalyst b1 catalyst b2 ( copper content 8 wt . %) was prepared in the same manner with comparative example 1 with the exception that an alumina ( surface area : 150 m 2 / g ) was used as a carrier . its activity of formation for dimethyl carbonate measured by the same method with comparative example 1 was 0 . 043 mol / l - cat . h . its selectivity for dimethyl carbonate was 18 %. catalyst a8 ( copper content 8 wt . %) mole ratio of organophosphorus compound / cu = 0 . 12 ) was prepared in the same manner with catalyst a1 of example 1 with the exception that an alumina ( surface area : 150 m 2 / g ) was used as a carrier . its activity of formation for dimethyl carbonate measured by the same method with comparative example 1 was 0 . 247 mol / l - cat . h , which was 5 . 7 times of the catalyst of comparative example 2 . its selectivity for dimethyl carbonate was 61 %, which was 3 . 4 times of the catalyst of comparative example 2 . catalyst b3 ( copper content 8 wt . %) was prepared in the same manner with comparative example 1 with the exception that titanium oxide ( surface area : 30 m 2 / g ) was used as a carrier . its activity of formation for dimethyl carbonate measured by the same method with comparative example 1 was 0 . 040 mol / l - cat . h . its selectivity for dimethyl carbonate was 16 %. catalyst a9 ( copper content 8 wt . %; mole ratio of organophosphorus compound / cu = 0 . 12 ) was prepared in the same manner with catalyst a1 of example 1 with the exception that titanium oxide ( surface area : 30 m 2 / g ) was used as a carrier . its activity of formation for dimethyl carbonate measured by the same method with comparative example 1 was 0 . 106 mol / l - cat . h , which was 2 . 7 times of the catalyst of comparative example 3 . its selectivity for dimethyl carbonate was 43 %, which was 2 . 7 times of the catalyst of comparative example 3 . as is shown clearly by the above test results , when an alcohol is reacted in a vapor phase with carbon monoxide and oxygen in the presence of a catalyst containing a copper halide and a tertiary organophosphorous compound having phenyl group or alkyl group , an enhanced activity of formation and selectivity for dimethyl carbonate are observed in comparison with a known catalyst composed of only a copper halide . synthesis tests for dimethyl carbonate were conducted using a high pressure fixed bed reactor . into a stainless reactor tube having 12 mm inner diameter was packed respectively 7 ml of catalysts a10 - a19 mentioned below . to the tube were introduced 5 g / hr of methanol , 57 . 8 ml / min of carbon monoxide and 3 . 6 ml / min of oxygen under vapor phase reaction conditions of 6 kg / cm 2 g and 150 ° c . to measure activities for dimethyl carbonate ( dmc ) formation . the results after 5 hours from the start of reaction are shown in table 2 . catalyst a10 : into a 500 ml flask equipped with a reflux condenser were charged 13 . 44 grams of cupric chloride and 150 ml of ethanol to make a solution . the solution was maintained at 70 °- 80 ° c . under an inert gas ( nitrogen ) stream . then , 39 . 35 grams of triphenylphosphine [ p ( c 6 h 5 ) 3 abbreviated as pph 3 ] dissolved in 300 ml of ethanol were poured slowly and stirred for 2 hours under reflux . after completion of the reflux , the reaction product washed well with hot ethanol and filtered to obtain a complex represented by a formula cu ( pph 3 ) cl as catalyst a10 . catalyst a11 : to 3 . 751 grams of a complex obtained in the same manner with catalyst a10 were added 20 grams of an active carbon ( surface area : 1000 m 2 / g ; 4 - 16 mesh ) and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was treated under an inert gas stream at 250 ° c . for 3 hours to obtain catalyst a11 . catalyst a12 : to 3 . 751 grams of a complex obtained in the same manner with catalyst a10 were added 20 grams of the active carbon used in catalyst a11 and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was treated under an inert gas stream at 300 ° c . for 3 hours to obtain catalyst a12 . catalyst a13 : to 1 . 705 grams of a complex obtained in the same manner with catalyst a10 were added 20 grams of the active carbon used in catalyst a11 and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was treated under an inert gas stream at 250 ° c . for 3 hours to obtain catalyst a13 . catalyst a14 : to 5 . 114 grams of a complex obtained in the same manner with catalyst a10 were added 20 grams of the active carbon used in catalyst a11 and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was treated under an inert gas stream at 250 ° c . for 3 hours to obtain catalyst a14 . catalyst a15 : to 6 . 820 grams of a complex obtained in the same manner with catalyst a10 were added 20 grams of the active carbon used in catalyst a11 and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was treated under an inert gas stream at 250 ° c . for 3 hours to obtain catalyst a15 . catalyst a16 : to 3 . 751 grams of a complex obtained in the same manner with catalyst a10 were added 20 grams of titanium oxide and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was molded and treated under an inert gas stream at 250 ° c . for 3 hours to obtain catalyst a16 . catalyst a17 : to 6 . 252 grams of a complex obtained in the same manner with catalyst a10 were added 20 grams of zirconium oxide and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was molded and treated under an inert gas stream at 250 ° c . for 3 hours to obtain catalyst a17 . catalyst a18 : to 6 . 252 grams of a complex obtained in the same manner with catalyst a10 were added 20 grams of niobium oxide and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was molded and treated under an inert gas stream at 250 ° c . for 3 hours to obtain catalyst a18 . catalyst a19 : to 3 . 751 grams of a complex obtained in the same manner with catalyst a10 were added 20 grams of silica and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was molded and treated under an inert gas stream at 250 ° c . for 3 hours to obtain catalyst a19 : by using 3 . 175 grams of cupric chloride in comparative example 1 and in the same manner with comparative example 1 , catalyst b4 was obtained . its activity of formation for dimethyl carbonate was measured in the same manner with example 4 . result obtained after 5 hours from the start of reaction is shown in table 2 . table 2__________________________________________________________________________catalyst amount of yield of dmc content complex yield of per unit amount of cu charged dmc of complexcarrier % * 1 g % * 2 %/ g__________________________________________________________________________b4 active carbon 3 . 0 -- 1 . 8 -- a10 none -- 4 . 1 10 . 7 2 . 6a11 active carbon 3 . 3 0 . 584 9 . 6 16 . 4a12 active carbon 3 . 3 0 . 584 9 . 2 15 . 8a13 active carbon 1 . 5 0 . 291 4 . 5 15 . 5a14 active carbon 4 . 5 0 . 753 10 . 6 14 . 1a15 active carbon 6 . 0 0 . 992 10 . 5 10 . 6a16 titanium oxide 3 . 3 1 . 026 11 . 4 11 . 1a17 zirconium oxide 5 . 5 1 . 858 9 . 8 5 . 27a18 niobium oxide 5 . 5 1 . 858 16 . 6 8 . 93a19 silica 3 . 3 0 . 426 4 . 1 9 . 62__________________________________________________________________________ * 1 : weight ratio of cu per carrier ## str1 ## dmc is obtained more effectively by using a catalyst containing a complex represented by the formula cu ( pph 3 ) cl when compared with the case using a known catalyst b4 ( catalyst in international application publication wo87 / 07601 ) carrying only cucl 2 on a carrier . though a high yield of dmc is obtained when catalyst a10 composed only of a complex represented by the formula cu ( pph 3 ) cl , however , catalysts carried on carriers are superior from the viewpoints of yield of dmc per unit amount of the complex . synthesis tests for dimethyl carbonate were conducted with catalysts a20 - a36 mentioned below using a high pressure fixed bed reactor . into a stainless reactor tube having 12 mm inner diameter was packed 7 ml of respective catalyst . to the tube were introduced 5 g / hr of methanol , 57 . 8 ml / min of carbon monoxide and 3 . 6 ml / min of oxygen under vapor phase reaction conditions of 6 kg / cm 2 g and 150 ° c . to measure activities for dimethyl carbonate formation . yields of dimethyl carbonate after 5 hours from the start of reaction are shown in table 3 . catalyst a20 : into a flask equipped with a reflux condenser were charged 4 . 90 grams of cuprous chloride ( cucl ) and 100 ml of methylene chloride to make a solution , and the solution was maintained at around 10 ° c . under an inert gas ( nitrogen ) stream . then , 26 . 2 grams of triphenylphosphine ( pph 3 ) dissolved in 100 ml of methylene chloride were poured slowly into the solution and the reaction was continued under agitation for 2 hours . after the reaction was completed , the reaction product was washed with hot ethanol and 5 % aqueous ammonia , then filtered to obtain a complex represented by a formula cu ( pph 3 ) 2 cl as catalyst a20 . catalyst a21 : to 5 . 89 grams of the complex cu ( pph 3 ) 2 cl obtained in the same manner with catalyst a20 were added 20 grams of an active carbon ( surface area 1000 m 2 / g ; 4 - 16 mesh ) and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was treated under an inert gas stream at 250 ° c . for 3 hours to obtain catalyst a21 . catalyst a22 : to 5 . 89 grams of the complex cu ( pph 3 ) 2 cl obtained in the same manner with catalyst a20 were added 20 grams of the active carbon used in catalyst a21 and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was treated under an inert gas stream at 330 ° c . for 3 hours to obtain catalyst a22 . catalyst a23 : to 5 . 89 grams of the complex cu ( pph 3 ) 2 cl obtained in the same manner with catalyst a20 were added 20 grams of the active carbon used in catalyst a21 and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was treated under an inert gas stream at 390 ° c . for 3 hours to obtain catalyst a23 . catalyst a24 : to 9 . 82 grams of the complex cu ( pph 3 ) 2 cl obtained in the same manner with catalyst a20 were added 20 grams of the active carbon used in catalyst a21 and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was treated under an inert gas stream at 250 ° c . for 3 hours to obtain catalyst a24 . catalyst a25 : into a flask equipped with a reflux condenser were charged 4 . 90 grams of cuprous chloride ( cucl ) and 100 ml of methylene chloride to make a solution , and the solution was maintained at around 40 ° c . under an inert gas ( nitrogen ) stream . then , 39 . 3 grams of triphenylphosphine ( pph 3 ) dissolved in 100 ml of methylene chloride were poured slowly into the solution , and the reflux was continued under agitation for 2 hours . after the reflux was completed , the reaction product was washed with hot ethanol and 5 % aqueous ammonia , then filtered to obtain a complex having a structure of cu ( pph 3 ) 3 cl as catalyst a25 . catalyst a26 : to 8 . 36 grams of the complex cu ( pph 3 ) 3 cl obtained in the same manner with catalyst a25 were added 20 grams of the active carbon used in catalyst a21 and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was treated under an inert gas stream at 330 ° c . for 3 hours to obtain catalyst a26 . catalyst a27 : into a flask equipped with a reflux condenser were charged 11 . 2 grams of cupric bromide ( cubr 2 ) and 100 ml of ethanol to make a solution , and the solution was maintained at 70 °- 80 ° c . under an inert gas stream . then , 20 . 0 grams of triphenylphosphine ( pph 3 ) dissolved in 100 ml of hot ethanol were poured slowly into the solution , and refluxed for 2 hours under agitation . after completion of the reflux , the reaction product was washed with hot ethanol , then filtered to obtain a complex represented by a formula cu ( pph 3 ) br as catalyst a27 . catalyst a28 : to 3 . 83 grams of the complex cu ( pph 3 ) br obtained in the same manner with catalyst a27 were added 20 grams of the active carbon used in catalyst a21 and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was treated under an inert gas stream at 330 ° c . for 3 hours to obtain catalyst a28 . catalyst a29 : into a flask equipped with a reflux condenser were charged 7 . 00 grams of cuprous bromide ( cubr ) and 100 ml of methylene chloride to make a solution and the solution was maintained at around 10 ° c . under an inert gas stream . then , 26 . 2 grams of triphenylphosphine ( pph 3 ) dissolved in 100 ml of methylene chloride were poured slowly into the solution and the reaction was continued for 2 hours under agitation . after completion of the reaction , the reaction product was washed with hot ethanol and 5 % aqueous ammonia , then filtered to obtain a complex having a structure of cu ( pph 3 ) 2 br as catalyst a29 . catalyst a30 : to 6 . 31 grams of the complex cu ( pph 3 ) 2 br obtained in the same manner with catalyst a29 were added 20 grams of the active carbon used in catalyst a21 and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was treated under an inert gas stream at 250 ° c . for 3 hours to obtain catalyst a30 . catalyst a31 : to 6 . 31 grams of the complex cu ( pph 3 ) 2 br obtained in the same manner with catalyst a29 were added 20 grams of the active carbon used in catalyst a21 and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was treated under an inert gas stream 340 ° c . for 3 hours to obtain catalyst a31 . catalyst a32 : to 10 . 5 grams of the complex cu ( pph 3 ) 2 br obtained in the same manner with catalyst a29 were added 20 grams of the active carbon use in catalyst a21 and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was treated under inert gas stream at 340 ° c . for 3 hours to obtain catalyst a32 . catalyst a33 : into a flask equipped with a reflux condenser were charged 7 . 00 grams of cuprous bromide and 100 ml of methylene chloride to make a solution , and the solution was maintained at around 40 ° c . under an inert gas stream . then , 39 . 3 grams of triphenylphosphine ( pph 3 ) dissolved in 100 ml of methylene chloride were poured slowly into the solution and the solution was refluxed for 2 hours under agitation . after completion of the reflux , the reaction product was washed with hot ethanol and 5 % aqueous ammonia , then filtered to obtain a complex represented by a formula cu ( pph 3 ) 3 br as catalyst a33 . catalyst a34 : to 8 . 79 grams of the complex cu ( pph 3 ) 3 br obtained in the same manner with catalyst a33 were added 20 grams of the active carbon used in catalyst a21 and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was treated under an inert gas stream at 340 ° c . for 3 hours to obtain catalyst a34 . catalyst a35 : into a flask equipped with a reflux condenser were charged 6 . 70 grams of cupric chloride , 15 grams of sodium iodide and 100 ml of ethanol to make a solution , and the solution was maintained at 70 °- 80 ° c . under an inert gas ( nitrogen ) stream . then , 20 grams of triphenylphosphine ( pph 3 ) dissolved in 100 ml of ethanol were poured slowly into the solution and refluxed for 2 hours under agitation . after completion of the reflux , the reaction product was washed with hot alcohol , then filtered to obtain a complex represented by a formula cu ( pph 3 ) i as catalyst a35 . table 3__________________________________________________________________________catalyst yield of dmcorgano - carrier : content amount of yield per unitphosphorus treatment of cu complex charged of dmc amount of complexcompound temperature % * 1 g % * 2 %/ g__________________________________________________________________________a20 cu ( pph . sub . 3 ). sub . 2 cl none -- 4 . 2 1 . 8 0 . 43a21 cu ( pph . sub . 3 ). sub . 2 cl active carbon 3 . 0 0 . 911 4 . 0 4 . 39 250 ° c . a22 cu ( pph . sub . 3 ). sub . 2 cl active carbon 3 . 0 0 . 911 6 . 5 7 . 14 330 ° c . a23 cu ( pph . sub . 3 ). sub . 2 cl active carbon 3 . 0 0 . 911 6 . 0 6 . 59 390 ° c . a24 cu ( pph . sub . 3 ). sub . 2 cl active carbon 5 . 0 1 . 480 7 . 2 4 . 86 250 ° c . a25 cu ( pph . sub . 3 ). sub . 3 cl none -- 4 . 6 1 . 2 0 . 26a26 cu ( pph . sub . 3 ). sub . 3 cl active carbon 3 . 0 1 . 179 5 . 6 4 . 39 330 ° c . a27 cu ( pph . sub . 3 ) br none -- 4 . 3 10 . 9 2 . 52a28 cu ( pph . sub . 3 ) br active carbon 3 . 0 0 . 611 8 . 0 13 . 1 330 ° c . a29 cu ( pph . sub . 3 ). sub . 2 br none -- 4 . 7 1 . 6 0 . 34a30 cu ( pph . sub . 3 ). sub . 2 br active carbon 3 . 0 0 . 936 5 . 0 5 . 34 250 ° c . a31 cu ( pph . sub . 3 ). sub . 2 br active carbon 3 . 0 0 . 936 7 . 5 8 . 01 340 ° c . a32 cu ( pph . sub . 3 ). sub . 2 br active carbon 5 . 0 1 . 520 8 . 2 5 . 39 340 ° c . a33 cu ( pph . sub . 3 ). sub . 3 br none -- 4 . 9 1 . 2 0 . 24a34 cu ( pph . sub . 3 ). sub . 3 br active carbon 3 . 0 1 . 179 4 . 5 3 . 82 340 ° c . a35 cu ( pph . sub . 3 ) i none -- 4 . 3 2 . 3 0 . 53a36 cu ( pph . sub . 3 ) i active carbon 3 . 0 0 . 652 4 . 0 6 . 13 380 ° c . a37 cu ( pph . sub . 3 ). sub . 2 cl tio . sub . 2 : 250 ° c . 3 . 0 1 . 802 2 . 0 1 . 11a38 cu ( pph . sub . 3 ). sub . 2 cl zro . sub . 2 : 250 ° c . 3 . 0 3 . 240 4 . 1 1 . 26a39 cu ( pph . sub . 3 ). sub . 2 cl nb . sub . 2 o . sub . 5 : 250 ° c . 3 . 0 3 . 230 4 . 8 1 . 49__________________________________________________________________________ * 1 : weight ratio of cu per carrier ## str2 ## catalyst a36 : to 4 . 28 grams the complex cu ( pph 3 ) i obtained in the sam manner with catalyst a35 were added 20 grams of the active carbon used in catalyst a21 and a small amount of ethanol as a solvent and mixed . after drying , the mixture was treated under an inert gas stream at 380 ° c . for 3 hours to obtain catalyst a36 . catalyst a37 : to 5 . 89 grams of the complex obtained in the same manner with catalyst a20 were added 20 grams of titanium oxide and a small amount of ethanol , and mixed . after drying , the mixture was molded and treated under an inert gas stream at 250 ° c . for 3 hours to obtain catalyst a37 . catalyst a38 : to 5 . 80 grams of the complex obtained in the same manner with catalyst a20 were added 20 grams of zirconium oxide and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was molded and treated under an inert gas stream at 250 ° c . for 3 hours to obtain catalyst a38 . catalyst a39 : to 5 . 89 grams of the complex obtained in the same manner with catalyst a20 were added 20 grams of niobium oxide and a small amount of ethanol as a solvent , and mixed . after drying , the mixture was molded and treated under an inert gas stream at 250 ° c . for 3 hours to obtain catalyst a39 . it is noticed from table 3 that copper complexes represented by the formula cu ( pph 3 ) n x [ pph 3 is p ( c 6 h 5 ) 3 ; x = halogen ; n = 1 , 2 or 3 ] are effective for production of carbonic acid esters , and especially that the yield per unit amount of copper complex increases remarkably for complexes carried on carriers . using catalyst a7 which carried firstly a copper chloride and then triphenylphosphine and catalyst a11 which carried a complex prepared beforehand by the reaction of a copper chloride and triphenylphosphine , activities for dimethyl carbonate ( dmc ) formation were investigated after 2 hours and 40 hours from the start of vapor phase reactions by the same method with example 4 , and the result are shown in table 4 . table 4______________________________________catalyst yield of dmc (%) * 2content of cu 2 hours after 40 hours afterwt . % * 1 start of reaction start of reaction______________________________________a11 3 . 3 9 . 6 9 . 6a7 3 . 0 12 . 0 3 . 4______________________________________ * 1 : weight ratio of cu per carrier ## str3 ## it is noticed that catalyst a11 carrying on a porous carrier a complex prepared beforehand by reacting cupric chloride with triphenylphosphine possesses time a stable capability for a longer period of in comparison with catalyst a7 which carried firstly copper chloride and then triphenylphosphine . into an autoclave were charged 50 ml of methanol , 0 . 07 mol of oxygen , 0 . 149 mol of carbon monoxide , 0 . 078 mol of n 2 and 0 . 01 mol ( 3 . 61 g ) of a complex ( catalyst a10 ) represented by the formula cu ( pph 3 ) cl , and a reaction was conducted under agitation for 6 . 5 hours under liquid phase reaction conditions of 13 kg / cm 2 g and 120 ° c . to obtain a dmc formation rate of 5 . 05 mol / l - meoh . g - mol complex . h . on the other hand , a reaction was conducted in the same manner with the above using 0 . 01 mol ( 1 . 344 g ) of a conventional cucl 2 catalyst to obtain a dmc formation rate of 2 . 5 ml - l / l - meoh . g - mol catalyst . h . from these results , it is noticed that catalyst a10 is two times as active as cucl 2 . the complex cu ( pph 3 ) cl prepared in example 7 was carried on an active carbon ( surface area : 1000 m 2 / g ; 4 - 16 mesh ) to prepare a catalyst ( cu content 3 wt . %), and 10 grams of the catalyst was used to conduct a reaction under the same conditions with example 7 . the amount of complex carried on the catalyst was 0 . 004 mol ( 1 . 46 g ). as the result , a dmc formation rate of 24 . 2 mol / l - meoh . g - mol complex . h was obtained , which was about 5 times of the case of example 7 using singly a complex cu ( pph 3 ) cl . under the same reaction conditions with example 7 , a reaction was conducted using 0 . 01 mol ( 6 . 23 g ) of catalyst a20 [ cu ( pph 3 ) 2 cl ; no carrier ]. as the result , a dmc formation rate of 1 . 03 mol / l - meoh . g - mol complex . h was obtained . under the same reaction conditions with example 7 , a reaction was conducted using 10 grams of catalyst a22 [ cu ( pph 3 ) 2 cl ; carried on active carbon ]. the amount of complex carried on the catalyst was 0 . 0036 mol ( 2 . 27 g ). as the result , a dmc formation rate of 7 . 20 mol / l - meoh . g - mol complex . h was obtained , which was about 7 times of the case of example 9 using catalyst a20 [ cu ( pph 3 ) 2 cl ; no carrier ]. under the same reaction conditions with example 7 , a reaction was conducted using 0 . 01 mol ( 9 . 30 g ) of catalyst a33 [ cu ( pph 3 ) 3 br ; no carrier ]. as the result , a dmc formation rate of 0 . 85 mol / l - meoh . g - mol complex . h was obtained . under the same reaction conditions with example 7 , a reaction was conducted using 10 grams of catalyst a34 [ cu ( pph 3 ) 3 br ; carried on active carbon ]. the amount of complex carried on the catalyst was 0 . 0033 mol ( 3 . 05 g ). as the result , a dmc formation rate of 5 . 10 mol / l - meoh . g - mol complex . h was obtained , which was 6 times of the case of example 11 using catalyst a33 [ cu ( pph 3 ) 3 br ; no carrier ]. under the same reaction conditions with example 7 , a reaction was conducted using 0 . 01 mol ( 4 . 06 g ) of catalyst a27 [ cu ( pph 3 ) br ; no carrier ]. as the result , a dmc formation rate of 5 . 28 mol / l - meoh . g - mol complex . h was obtained . under the same reaction conditions with example 7 , a reaction was conducted using 10 grams of catalyst a28 [ cu ( pph 3 ) br ; carried on active carbon ] ( cu content 3 wt . %). the amount of complex carried on the catalyst was 0 . 004 mol ( 1 . 61 g ). as the result , a dmc formation rate of 31 . 9 mol / l - meoh . g - mol complex . h was obtained , which was about 6 times of the case of example 13 using catalyst a27 [ cu ( pph 3 ) br ; no carrier ]. it is noticed that a copper complex comprising a copper halide and a tertiary organophosphorus compound is effective for the liquid phase production of carbonic acid esters , and especially that a complex carried on a porous carrier is remarkably active .