TW200934787A - Method for controlling precipitation of metal from transition metal complex - Google Patents

Abstract

A method by which a liquid reaction mixture resulting from a reaction conducted using a transition metal complex catalyst containing an organophosphorus ligand is inhibited from undergoing precipitation of the transition metal therein and the transition metal complex catalyst is efficiently taken out of the reaction system as a liquid containing the catalyst therein. The method is characterized in that a solution containing a complex which is a complex of a transition metal selected among transition metals of Groups 8 to 10 and has a ligand comprising a trivalent organophosphorus compound is brought into contact with an aromatic phosphite different from the trivalent organophosphorus compound to thereby inhibit the transition metal complex from causing metal precipitation in the solution.

Description

200934787 VI. Description of the Invention: [Technical Field] The present invention relates to a method for suppressing precipitation of a transition metal in a solution containing a transition metal having a transition metal and an organic ligand. In particular, the present invention relates to suppressing transition of a transition metal from a transition metal in a solution obtained by a hydrogenation reaction or an isomerization reaction using a transition metal-organophosphorus-containing ligand complex catalyst. The method of precipitation of the material. ❹[Prior Art] A complex catalyst containing a scaly ligand such as a transition metal and a phosphite ligand is used in many reaction processes as a reaction process, for example It is known that hydrogenation reaction, isomerization reaction of an unsaturated compound, hydroquinone reaction of an olefin, dimerization reaction of an olefin, and the like. Further, it is also known that when a hydroformylation reaction is carried out, "if a part of the sulfite ligand of the ruthenium-phosphite complex complex catalyst is formed, a by-product acid or hydrazine is produced. When the decomposition or the like is decomposed, the complex compound becomes unstable, and the metal of the complex catalyst is precipitated in the reaction solution. Therefore, the by-produced acidic compound must be removed (see Patent Document 1). The transition metal in the complex catalyst used in the reactions, for example, ruthenium (Group 8) or Group 10 (Group 10), is separated and recovered from the reaction solution after the reaction. However, in the actual reaction process, if the metal is precipitated from the complex catalyst during the reaction step, not only the catalyst metal loss but also a large cause of staining in the device is present. Problems with smooth operation such as a decrease in thermal conductivity. 097142815 200934787 When a metal is separated from a metal complex catalyst, a monodisperse distribution site of the metal complex catalyst decomposes due to oxidation or the like during the reaction or when the target product is separated or recovered, so that the complex does not become The stable situation is a major cause, so it is required to prevent the decomposition of the ligand in the complex catalyst to stabilize, inhibit the precipitation of metal in the process step, and touch the metal complex. The solution of the medium is discharged to the outside of the reaction system. [Patent Document 1] Japanese Patent Laid-Open No. 2000-501712 ❹ [Disclosure] The present invention provides a reaction after a reaction using a transition metal complex catalyst containing an organophosphorus ligand. A method of suppressing precipitation of a transition metal in a liquid and efficiently discharging the transition metal complex catalyst to the outside of the reaction system in the form of a solution containing the same. (Means for Solving the Problem) In order to prevent precipitation of a transition metal in a reaction liquid using a transition metal complex catalyst containing a sulfonate ligand or the like used in various reactions, the inventors of the present invention The state of the transition metal complex in the reaction liquid was studied intensively, and it was found that 'one of the major reasons is that the ligands such as the phosphite ligand of the transition metal complex catalyst are in the reaction. In the middle separation or recovery, it is decomposed by oxidation or the like, so that the complex compound becomes unstable, and the metal of the complex compound is easily precipitated. The present inventors have further found that the transition metal complex can be stabilized by the use of a phosphite as an antioxidant for the transition metal complex in the reaction solution to prevent the transition metal from being stabilized by the 097142815 4 200934787 process. Precipitate. The present invention has been completed based on this knowledge. That is, the gist of the present invention is as follows.方法. A method for inhibiting precipitation of a metal from a transition metal complex, characterized by transitioning a transition metal selected from transition metals of Groups 8 to 10 having a ligand composed of a trivalent organophosphorus compound The solution of the metal complex is contacted with an aromatic phosphite different from the trivalent organic phosphorus compound to inhibit precipitation of the metal from the transition metal complex in the solution. 2. The method for inhibiting precipitation of a metal from a transition metal complex according to the above item 1, wherein the aromatic phosphite has the following formula (丨): [Chemical Formula 1] P-(-0 - R}3 (1) [Formula In (I), 'three R' each independently represent a hydrocarbon group which may have a substituent, and at least one R is an aromatic group.

OQ 3. A method for inhibiting precipitation of a metal from a transition metal complex according to the above item 1 or 2, wherein at least one aromatic group in the 'aromatic phosphite system (1) has an ortho position in the ortho position thereof Substituent. 4. The method for inhibiting precipitation of a metal from a transition metal complex according to the above item 3, wherein at least one of the aromatic groups of the aromatic phosphite has a substituent at the ortho position. a substituent bonded by a 3 or 4 carbon atom. 5. The above-mentioned item 4 inhibits the precipitation of a metal from a transition metal complex. 097142815 5 200934787 In the formula (I) of the 'aromatic phosphite, three R systems are the same and have an adjacent position. A phenyl group substituted by a 3- or 4-stage carbon atom. The method for inhibiting precipitation of a metal from a transition metal compound according to any one of the above items 1 to 5 wherein the aromatic phosphite is a monodentate squamous acid vinegar. 7. The method for inhibiting precipitation of a metal from a transition metal complex according to any one of items 1 to 6 above, wherein the 'trivalent organic phosphorus compound is a phosphine, a decyl phosphite, and a phosphorous amine. At least one selected from the group consisting of: am idi te) 8. The method for inhibiting the precipitation of a metal from a transition metal complex according to any one of items 1 to 7 above, wherein the trivalent organic phosphorus compound It is at least one selected from the group consisting of a polydentate phosphine, a squarate, and a phosphite. 9. The method for inhibiting precipitation of a metal from a transition metal complex according to any one of items 1 to 8, wherein the transition metal of the 8th to 1st group is palladium or platinum. The method for inhibiting the precipitation of a metal from a transition metal complex according to any one of the above items 1 to 9, wherein the method comprises a ligand comprising a trivalent organic phosphorus compound and from the eighth to The solution of the transition metal complex of the transition metal selected from the group 10 transition metal is an isomerization reaction, a hydrogenation reaction, a hydroquinone reaction, a dehydrogenation reaction, and the transition metal complex as a catalyst. A solution after any reaction of a low polymerization 'reaction, metathesis reaction, coupling reaction or allylation reaction. 11. The method for inhibiting the precipitation of a metal from a transition metal complex according to the above item 10 097142815 6 200934787 The method 'where' contains a ligand composed of a trivalent organic phosphorus compound and a transition metal from the 8th to 10th groups The solution of the transition metal complex of the transition metal selected is a solution containing an allyl compound derivative different from the starting material after the isomerization reaction of the starting allyl compound derivative. 12. The method for inhibiting precipitation of a metal from a transition metal complex according to the above item 1 or item (wherein, comprising a ligand comprising a trivalent organic phosphorus compound and a transition from the 8th to 1st family) The transition metal selected as the transition metal in the metal is the skeptic material; the liquid solution is the reaction solution after the isomerization reaction of the ethoxylated propyl propyl compound. 13. The method for inhibiting precipitation of a metal from a transition metal complex according to the above item 12, wherein the ethoxylated allyl compound is obtained from a thixoethoxylated reaction silk scarf of butadiene. 4-Diethoxymethoxy-1-erene is contained as a main component. (Effect of the Invention) According to the method of the present invention, the reaction liquid towel after the reaction is carried out using a transition metal complex catalyst containing a chaperon ligand can suppress the precipitation of the transition metal and stabilize the complex, thereby reacting When metal loss does not occur in the system, the transition metal complex catalyst is efficiently discharged to the outside of the reaction system in the form of (4), and contamination in the apparatus, deterioration in thermal conductivity, and the like can be suppressed. [Embodiment] Hereinafter, the present invention will be described in more detail. The transition metal complex touch in the present invention comprises a transition metal complex containing a ligand composed of a trivalent organic phosphorus 097142815 200934787 compound and a transition metal selected from the group 8 to 10 transition metals. The ligand has a P-C bond, a p_0 bond, or a PN bond. Such transition metal complex catalysts are used, for example, for isomerization of allyl compound derivatives, hydrogenation of unsaturated compounds, hydroformylation of olefins, dehydrogenation, oligomerization of olefins, metathesis reactions, coupling The reaction is a known transition metal complex catalyst in a number of manufacturing processes such as hydrocyanation of a diene (deoxanylation of butene). © The transition metal complex catalyst of the present invention contains a ligand composed of a trivalent organic phosphorus compound, which is a compound having a PC bond, a P-Ο bond or a p_N bond, including a phosphine, a phosphite. And the single and multidentate ligands selected in the phosphorous amine. Examples of the phosphine include a trialkylphosphine, an alkyldiarylphosphine, a dialkylarylphosphine, a bicycloalkylarylphosphine, a cycloalkyldiarylphosphine, a triarylalkylphosphine, and a trivalent alkyl group. The phosphine, the diarylphosphine, and the like are represented, for example, by the following formula (i). • [Chemical 2] Ρ+R,) 3 (1) In the above formula (1), three R's are independent, and may be the same or different, and are substituted or unsubstituted alkyl or aromatic groups. The aryl group may, for example, be a phenyl group, a naphthyl group or a diphenyl group; and the alkyl group may be a group having a carbon number of 1 to 10, for example, an anthracenyl group, an ethyl group, a propyl group, a butyl group or a cyclohexyl group. Wait. Further, examples of the substituent which the group may have include an alkyl group, an alkoxy group, a decyl group, an amine group, a fluorenyl group, a carboxyl group, a dentate atom, a sulfonyl group, a sulfonic acid group, and a decene group of 097142815 8 200934787. Base, Sandun methyl and so on. Among these, an aryl group such as a phenyl group or a hetero group is preferable. Specific examples of the phosphine include triphenyl scale, ginseng (p-toluene phosphine, ginseng (p-methoxyphenyl) lin, ginseng (p-phenyl) phosphine, and ginseng (p-phenyl). Phosphine, ginseng (dimethylaminophenyl)phosphine, propyl diphenylphosphine, tert-butyldiphenylphosphine, n-butyldiphenylphosphine, n-hexyldiphenylphosphine, cyclohexyldiphenyl Ketone, dicyclohexylphenylphosphine, tricyclohexyl, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, etc. ❹ As the above-mentioned sub-genre, the following formula (1) and (2-1), the ligand of the single tooth and the double tooth. The above-mentioned phosphite is exemplified by the following formulas (1-2), (2-2), (2- 3), (2-4) and (2-5) the single and double tooth ligands.

(2-1) 097142815 200934787 [Chemical 4]

(1-2) (2*2) U-3> [Chemical 5]

In the above formula, Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8 and Y9 each independently represent a chain or a cyclic alkyl group, an aryl group or a heterocyclic group, and the groups may further have a substituent. . Further, Y2 and Y3, Y4 and Y5, Y6 and Y7, and Y8 and Y9 may be respectively interconnected to form a ring. η represents the length of the methylene chain (-CH2-), and η is 1 to 10, preferably 1 to 5, particularly preferably 2 to 4. m represents the length of the methylene chain, and m is from 1 to 5, preferably from 1 to 3. • R1 and R5 each independently represent a hydrogen atom, a secondary or tertiary hydrocarbon group having a carbon number of 3 to 20, and R2, R3, R6, R7, R9 and R1G each independently represent a carbon number which may have a substituent. a hydrocarbon group of 1 to 20 or a carbon number which may have a substituent of 097142815 10 200934787. The oxyl groups R and R8 each independently represent a hydrogen atom, a hydrocarbon group having a carbon number of 1 to 4, a cleavage or a carbon number of 1~ 4 alkoxy groups. The carbon number of the chain portion of the chain or ring-shaped filament and the alkoxy group is preferably from 1 to 20'. As specific examples thereof, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, pentyl, hexyl, octyl, decyl , cyclohexyl, cyclopentyl and the like. Further, examples of the substituent which the ruthenium group may have include an oxo group having a carbon number of 6 to 10, an amine group, a cyano group, and a carboxylic acid group having a carbon number of 2 to 1 Å. Base, halogen atom, etc. The carbon number of the above aromatic group is usually 6 to 2 G, preferably 6 to 14. Specific examples of the aromatic group include a phenyl group and a naphthyl group, and examples of the substituent which may be contained in the group include a hydrogen atom, a carbon group having a carbon number, and a carbon number of H? An oxy group, a cyclone having a carbon number of 3 to 20, an aromatic group having a carbon number of 6 to 2 fluorene, an aryloxy group having a carbon number of 6 to 20, a aryl group having a carbon number of 6 to 2 q, and a carbon number of 6 〜2〇=alkyl aryloxy group, aromatic base yarn having a carbon number of 6 to 2G, alkoxy group having a carbon number of 6 to 2 fluorene, a gas group, a g group, a hetero atom, a chlorine atom, a gas atom, etc. . In the case where Y1 to f are a base group which may have a substituent, specific examples thereof include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, and 2, 3_ 2 methylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethyl basic, 2-ethylphenyl, 2-isopropylphenyl 2_T-butylphenyl n-(t-butyl)phenyl, 2-chlorophenyl, 3-p-phenyl, 4-chlorophenyl n-dichlorophenyl, 2,4-dichlorobenzene Base, 2,5-dichlorophenyl, 3,4-diphenyl, to 097142815 200934787 dichlorophenyl, 4-trifluorodecylphenyl, 2-decyloxyphenyl, 3-oxo Phenylphenyl, 4-nonyloxyphenyl, 3,5-dimethoxyphenyl, 4-cyanophenyl, 4-nitrophenyl, trifluorodecylphenyl, pentafluorophenyl and under The basis of (C-1) to (C-8). [6] (C-1) (〇2)

Μ)) (Μ) (OT) (C-β) with the above formula (1-1), (1-2), (2-1), (2-2), (2-3), (2-4 The specificity of the ligand represented by φ and (2-5) φ is as follows. [化7] 097142815 12 200934787

(A-Ι»

(Α·β)

[化8] 13 097142815 200934787

System 2> (Mi)

«Μβ)

[Chemistry 9]

097142815

(Μ·)

(Ar24) 14 200934787 [Chem. 10]

200934787 [化11]

097142815 16 200934787 [Chemistry 12]

(A-«3) [Chem. 13]

097142815 17 200934787 [Chem. 14]

(B»7)

(B-4)

(Β-β)

097142815 18 200934787 [Chem. 15]

097142815 19 200934787 [Chem. 16]

(B-17)

(Β·20) [Chem. 17]

097142815 20 (&28) 200934787 [Chem. 18]

(B-30)

[Chem. 19]

(B-32)

(B-33)

(B-34)

097142815 21 200934787 [Chem. 20]

(B-42) The transition metal of Group 8 to 1 in the transition metal complex catalyst in the present invention is preferably ruthenium, rhodium "nickel, palladium, platinum or the like, and particularly preferably palladium. The transition metal genus is supplied in the form of a compound, and specific examples thereof include acetate, sulfate, nitrate, halide salt, organic salt, inorganic salt, acetophenone _ compound, and rare hydrocarbon coordination. A compound, an amine complex, a pyridinium complex, a carbon monoxide complex, a phosphine complex, a phosphite complex, and the like. Specific examples of the palladium compound include palladium metal, palladium acetate, trifluoroacetic acid r, sulfuric acid, nitric acid, chlorination, bromination, genomic, bis(acetonitrile)palladium, cyclooctane. Diene palladium dichloride, bis(triphenylphosphine) dipalladium palladium, ruthenium (triphenylphosphine), bis(dibenzylidene propyl), four gas decommissioning, four gas sodium , 097142815 22 200934787 bis(nickel nitrile) palladium dichloride, bis(acetonitrile) dipalladium dichloride and other carboxylate compounds, olefin-containing compounds, organophosphine-containing compounds, allyl palladium chloride dimers Wait. In particular, acetic acid, palladium trifluoroacetate, bis(acetonitrile)palladium, ruthenium (triphenylphosphine)palladium or the like is suitably used in terms of price and ease of handling. The amount of the above ligand added in the transition metal complex of the present invention is preferably such that the molar ratio of the phosphorus atom in the ligand to the transition metal i mole in the transition metal complex is 0. 1~1000, more preferably 1~100, especially good 1~1〇. ❹ and 'as a ligand' may contain one or several ligands. The preparation method of the transition metal complex is not particularly limited. For example, when the reaction is carried out using the complex as a catalyst, the desired ratio of the transition metal compound and the ligand compound can be obtained by heating. The reaction is carried out in a solvent to prepare a catalyst-containing liquid. In the present invention, a solution containing a transition metal complex comprising the above-mentioned ligand composed of a trivalent organic phosphorus compound and a transition metal of Group 8 to 10 is contacted with an aromatic squarate. The family linoleate is not the same as the trivalent® organic tank compound as a ligand. One of the major reasons for the metal to precipitate from the transition metal complex catalyst is that the phosphite ligand of the metal complex catalyst is oxidized during the reaction or during the separation and recovery process to change the complex. It is unstable. Therefore, the aromatic phosphite which is in contact therewith has a function as a component which is oxidized as long as it has a ligand which prevents oxidation of a ligand composed of a trivalent organic scaly compound which is possessed by the above-mentioned metal complex catalyst. The aromatic cleavage vinegar represented by the following formula (丨) may be mentioned. 097142815 23 200934787 P-f-O-R), (i) In the above formula (1), '3 R' stands for a hydrocarbon group having a silk taken off, and at least one R is an aromatic group. The nicotyl group in formula (I) is selected from the group consisting of an alkyl group or a peryl group. The carbon number of the base is usually 20, preferably a money or a branched alkyl group or a cyclic alkyl group. Specific alkyl groups include methyl, ethyl, n-propylamine, and isopropylidene. Base, n-butyl, isobutyl, t-butyl, tert-butyl, pentyl, hexyl octyl, decyl, cyclohexyl, cyclopentyl and the like. Further, examples of the substituent which the calcining group may have include an alkoxy group having a carbon number of 1 to 10, an aromatic group having a carbon number of 6 to 1 fluorene, an amine group, a cyano group, and a carbon number of 2 to 10. A vinegar group, a thiol group, a dentate atom, and the like. The carbon number of the aromatic group is usually from 6 to 20, preferably from 6 to 14. Specific examples of the aromatic meaning include a phenyl group and a naphthyl group. Examples of the substituent base which the base group may have include a hydrogen atom, a base having a carbon number of 2, a oxy group having a carbon number of 3 Å, a ring wire having a carbon number of 3 to 20, and carbon. An aromatic group having a number of 6 to 1 fluorene, an aryloxy group having 6 to 20 carbon atoms, a aryl group having 6 to 2 carbon atoms, a carbon number of 6 to = aryloxy group, carbon number It is an aromatic nucleus of 6 to 2Q, a aryloxy group having a carbon number of 6 to 2 fluorene, a cyano group, a vine group, a thiol group, and a dentate atom such as chlorine or fluorine. As the wire, isopropyl group, isobutyl group, second butyl group, and third group are preferable. Cyclohexyl, etc., particularly preferably a third butyl group. Preferably, the earthy aromatic propylene has a substituent in the formula (1) having a substituent at the position (position 2 or 6), and preferably having a substitution at the ortho position 097142815 24 200934787 A substituent bonded to an aromatic group by a carbon atom of a 3 or 4 stage. Particularly suitable aromatic phosphites are those in which all three r in the formula (I) are the same and have a substituent bonded by a 3 or 4 carbon atom in the ortho position. Further, the aromatic phosphite is preferably a phosphite of a single tooth. Particularly preferred is a single-dentate farnic acid ester having a phenyl group of a third butyl group in the ortho position. ❹ ❹ As the aromatic phosphite, specific examples include phenyl phosphite, phosphite (o-tolyl) ester, phosphite (o-isopropylphenyl) ester, and phosphorous phosphite (2_ third) Butyl phenyl) ester, bis(isobutylphenyl) phosphite, bis(isopropylphenyl) phosphite, sub-acid ginseng (2,4-di(t-butyl)phenyl ) ester, sub-acid acid ginseng (2, 5 - (second butyl) phenyl) ester, phthalic acid ginseng (tertiary butyl) phenyl) fluorene w acid (2, 3- bis ( Tertiary butyl) phenyl) vinegar, phosphite ginseng (2 bis (isopropyl) phenyl) vinegar, bismuth citrate (2,5-di(isopropyl)phenyl) vinegar, phthalic acid Reference (2,6-di(isopropyl)phenyl)§|, phosphite (2,3-di(isopropyl)phenyl)', propipropyl bis(2_t-butylphenyl) Ester, butyl bisphosphonate (2-tert-butylphenyl) vinegar, n-butyl bis(2-tert-butylphenyl) phthalate, n-hexyl diphenyl phosphite, sub Tert-butylbis(2,4-t-butylphenyl)phosphate, n-butylbis(2,first butyl-based) phosphite, phosphorous Two, / Λ tributylphenyl) cyclohexyl acetate, Yawei reference (2-tert-butyl cyclohexyl) a 9 acid (2-tert-butyl cyclohexyl) phenyl ester. The phosphorous acid ginseng (2-: r: its lean dragon, this Ψ 1 ^ _ (isopropyl = phosphite ginseng (isobutyl phenyl) vinegar, sub-fox ginseng such as basic fine, vassin (2, ester) , phosphite ginseng (2 4 - Γ笸-butan, spear one) storm 丞 丞 gt; > (second butyl) phenyl) vinegar, etc., wait for the phosphite 097142815 25 200934787 (2, 4 - bis(t-butyl)phenyl) ester. Specifically, the transition metal containing a ligand composed of a trivalent organophosphorus compound and a transition metal of Group 8 to 1 () is contained in the present invention. A solution obtained by reacting a liquid system with the transition metal catalyst. The reaction of the conjugated metal complex (IV) includes, for example, the isomerization of the allyl compound 'derivative Hydrogenation of an unsaturated compound, hydroformylation of an olefin, dehydrogenation of an olefin, oligomerization, metathesis, coupling, dilute hydrocyanation (dinitrification of dimethoate), etc. In the present invention, it is preferred that the transition metal complex is used as a catalyst and (10) the propyl compound is derivatized by a purely isomerization reaction. The ethoxylated propyl compound obtained by the oxidation of the acetylation reaction, ie, 3 4_diethyl sulfhydryl + butadiene, constitutes the heterogeneity of 1,4-diethoxycarbonyl-2-butene In the method of the present invention, the reaction liquid obtained by the reaction using the transition metal catalyst is brought into contact with an aromatic phosphite, and as a reaction liquid, the reaction can be directly used. The reaction liquid may also be a reaction liquid containing a catalyst removed from the reaction liquid or a catalyst-containing reaction liquid separated from the catalyst, and particularly preferably in contact with the reaction liquid phase after the reaction. Contact of the reaction liquid with the aromatic phosphite. Specifically, the reaction is carried out by adding a solution containing an aromatic linoleic acid vinegar to the reaction solution, and the phase is contacted. The aromatic phosphite may be a solid itself or a solution, but when added In terms of the contact efficiency with the reaction liquid, it is preferred to uniformly dissolve it in advance. Thus, the 'transition metal complex catalyst and the aromatic phosphite in the reaction liquid after the reaction step are in the form of a homogeneous solution. In the piping in the step, steaming 09914 2815 26 200934787 It is transferred inside the device, such as Guta, so that it is possible to suppress metal loss due to precipitation of catalytic metal in the piping and in the steaming tower, and to cause contamination in the step system. The catalyst metal is discharged in the form of a liquid: to the outside of the system, the solution discharged is delivered to the catalyst treatment (catalyst recovery or disposal). In the catalyst treatment step, the discharged solution is directly incinerated, or The metal is recovered and the discharged solution is transferred to another place, or the metal ash or the like is recovered by using a water burning device or the like provided in the factory. The heat treatment temperature is required to heat the mixture of the reaction liquid and the material group. Usually 2 (rc~20 (rc, preferably 8 generations to 18 generations). When the treatment is carried out at a high temperature exceeding this range, the aromatic hydrazine is thermally decomposed by itself, and if the temperature is too low, the solubility of the aromatic acetal in the reaction liquid is lowered, and the precipitation of the metal is suppressed. The effect is reduced. As a basis for selecting an aromatic phosphite, in order to maximize the function of preventing oxidation of the phosphite, it is necessary to avoid a solution caused by factors other than oxygen, and specifically, § is not suitable for use. A phosphite that thermally decomposes or chemically decomposes. Therefore, it is preferred to thermally stabilize the aromatic phosphite, and in addition to 'improve chemical stability', it is necessary to prevent the p-o bond from being broken due to reaction with other chemical components, so it is preferred that the aromatic ring is relative to A phosphite having a bulky substituent at the ortho position of the p_〇 bond. Further, in general, the price of a single-disc azimuth is lower than that of a multi-toothed yoghurt, and it is preferably an aromatic phosphite of a single tooth from the viewpoint of function and cost. When an aromatic phosphite is added to a reaction liquid obtained by a reaction using a transition metal catalyst and 097142815 27 200934787, the ratio of the aromatic phosphorous is relative to the ruthenium according to the reaction The axis, amount, and the like of the transition metal contact are different, and generally the amount of metal 1 mol relative to the transition metal catalyst is 1 time mA ~ 100 G times the molar amount, preferably 2 times the molar amount ~ 5 G times the Mo The amount of the ear is more than the amount of the ray, and the effect is suppressed. (4) On the one hand, even if the amount of addition is too large, the effect corresponding to the added amount cannot be obtained', so that the cost is not good. The concentration of the aromatic phosphite added to the mash is different depending on the type of the aromatic amide, and is usually 5 Gwt 〜 1 wt%, preferably 10 MPa ppm to 5 〇〇〇 wt ppm. The method is as follows. It is known to make a reaction between the counter-examination of the ethoxylated propyloxy compound by using a transition metal complex catalyst and the aromatic phosphorous. The diene and the like a plurality of dienes are subjected to an oxidative diethoxylation reaction to produce a diethoxylated butadiene and/or 1,4-diethoxy ethoxylate as an ethoxylated allyl compound. Base 2 - butene method. In the presence of the most common domain catalyst, the reaction of butadiene, acetic acid and oxygen is carried out, and k 1 '4-diethoxycarbonyl | butene and 3 4 -diethoxycarbonyl + butene The liquid usually also contains 2 ethoxy oxime I butyl, 3 - secret + ethoxylated + butadiene, 4 hydroxy ~ 3 ~ ethoxylated - which are hydrolyzed by the bis- butyl ketone. 1-butene and the like. As a raw material, 3, 4-di(tetra)oxy+τ 097142815 r14-?»ic 28 200934787 olefin is supplied to the thixotropic reaction. In addition to the pure product, the above butadiene is also subjected to the diethoxylation reaction. After the reaction liquid itself; or by steaming the scale, the acetic acid, water, etc., are at least partially removed from the substance of the diethylidene oxide + butene or by the steaming scale a part or all of the by-products of B-base-butene; furthermore, part or all of the low-boiling by-products and the high-fossil by-products are removed. In the method of the present invention, "3 4_ Diethoxy olefin as a cut for the city" ❹. In general, the "containing liquid of 3,4_diethyl oxime + as a domain" used in the present invention also contains U-diethoxycarbonyl_2_丁妇" 3-Hydroxy-4-buteneoxy-1-butene, 4-hydroxy-3-ethenyloxy-butene, which may contain a hydrolyzate of 3,4-diethyloxy+butene And/or 3, 4_dihydroxybutadiene, which in turn may also contain a hydrolyzate of #1,4-diethyloxyl butadiene and a ethoxy-4-hydroxy-2-butene and/or丨 '4-dihydroxy-2-butene. a transition metal complex used as a catalyst in the isomerization reaction of the above ethoxylated allylic compound, etc., the tether is preferably linoleic acid or sub-hetero, particularly preferably squamous amine The resulting complex is catalystd. The transition metal complex is used in an amount of 醯. wt. A range of 100 wtppm. The temperature at which the isomerization reaction is carried out is usually 20 to 2 Torr (TC, preferably 8 Torr to 18 Torr °C), particularly preferably 100 to 16 (rC. If the reaction temperature is too high, the transition metal complex catalyst) It will be deteriorated by metallization, resulting in the disappearance of activity. If the reaction temperature is lower than 097142815 29 200934787, the reaction rate will decrease. A long and large reactor is required. The pressure for performing the isomerization reaction is usually 1 atm. Depressurization, preferably from 1 atmosphere to 10 atmospheres, particularly preferably from atmospheric pressure to 3 atmospheres. If the reaction pressure is too low, the catalytic activity decreases as the reaction temperature decreases, and if the reaction pressure is too high, The cost of the reactor is increased. The isomerization reaction is usually carried out in a liquid phase, and the isomerization reaction can be carried out in the presence or absence of a solvent. In the case of using a solvent, as a preferred solvent, It is not particularly limited as long as it can dissolve the catalyst and the raw material compound, and specific examples of the solvent include diethylene glycol dimethyl ether, diphenyl ether, dibenzyl ether, and Allyl ether, tetrahydrofuran (τ, te Trahydrofuran), two, and other ethers such as N-methyl-2-pyrrolidone, n, 'dimethylamine amine, N,N-dimethyletheneamine and other guanamines; Other classes; vinegar such as n-butyl vinegar, butane vinegar, bismuth acid (n-octyl) vinegar; aromatic hydrocarbons such as toluene, xylene and dodecylbenzene; n-pentane, n-hexane, positive An aliphatic cigarette such as heptane or n-morphic; a by-product formed by the isomerization reaction; an allyl compound derivative belonging to the raw material itself; an allyl compound belonging to the product itself 'from the original (tetra)propyl compound The compound of Naji's sister, etc. As a particularly preferable solvent, the allylic compound itself which is a raw material, the propyl compound itself which is a product, etc. are used. However, since the isomerization reaction proceeds mainly in response, it is desirable to carry out the reaction in an amount less than the previous solvent. Usually, the total weight of the allyl compound derivative as a raw material is 097142815 30 200934787. 10 times or less by weight, preferably 0 times by weight or more and 5 parts by weight When the amount is less than or equal to 1 part by weight or less, the reaction rate is lowered when the amount of the solvent is too large. • As a reaction method for performing the isomerization reaction, a stirring type fully mixed reactor or a plug type can be used. The reactor is carried out in any one of a continuous mode, a semi-continuous mode or a batch mode, and the gas phase portion in the reactor is free from vapors such as a solvent, a raw material compound, a reaction product, a reaction by-product, a catalytic decomposition product, and the like. , ® is ideally formed by an inert gas such as argon or nitrogen. In particular, the incorporation of oxygen into the air can cause deterioration of the catalyst, that is, the oxidation of the phosphorus compound disappears. Therefore, it is desirable to reduce the air as much as possible. The amount of the aromatic phosphite solution is injected into the reaction liquid continuously flowing out from the isomerization reactor from the supply port provided on the pipe near the outlet of the reactor. The aromatic phosphite solution may be injected in any of a continuous mode or a batch mode, preferably continuously. The reaction solution supplied with the aromatic phosphite is transferred to a product obtained by isomerization of *3,4-diethoxy-1-butene (1,4-diethyloxy) 2-butadiene) The separation step (steaming tower) separated from the isomerization reaction liquid was carried out to perform steam strip separation. Separation of the product can be carried out by a conventional separation operation. Specifically, in addition to simple steaming, vacuum distillation, thin film steaming, steam steaming (four) steaming, gas liquid separation and evaporation can also be mentioned (evapomiorO, Separation operation such as stripping, gas absorption, extraction, etc. Separation steps can be carried out in separate steps, and two or more components can be separated at the same time. Further, the product can be separated, and the raw material is diluted with a propyl compound. 097142815 31 200934787 The residual liquid after separation is delivered to the above-mentioned catalyst treatment. As a reaction to the isomerization of the above-mentioned isomerization, the reaction of the olefin is usually carried out. By using a metal complex catalyst comprising a transition metal (eg, Rh, Pd, etc.) and a ligand composed of an organophosphorus compound, the olefin and water gas (carbon monoxide) are present in the presence or absence of a solvent. 2摩尔%。 The amount of the catalyst is 0. 2mol% or more. Take The reaction temperature is usually -20 ° c to 15 (TC, preferably (TC ~ 10 (rc, reaction pressure is usually 0.01 MPa ~ 30 MPa ' is preferred) In addition, as another reaction example, a hydrogenation reaction of an olefin, a carbonyl compound, an imine compound or the like using the transition metal complex catalyst may be mentioned. In the hydrogenation reaction, the catalyst is used. The amount of use is usually 〇丨ppm mole or more, preferably 1 ppm molar or more, and is 〇. 2 mol% or less, preferably 0 〇. 1 mol% or less, relative to the reaction substrate. The reaction temperature is usually -20. (: 〜15 〇. (:, preferably 〇〇c~1〇〇 °C 'The hydrogen partial pressure is usually o.ool MPa~3〇MPa, preferably 〇〇1 Μρ&amp 〜20 MPa. The method of the present invention is applied to the reaction liquid obtained by the above reaction example, whereby the transition metal-containing solution can be smoothly taken out from the reaction liquid. [Examples] Hereinafter, examples and comparisons are made. EXAMPLES The method of the present invention will be described in more detail, but the present invention is not limited to the examples. 097142815 32 200934787 [ Example 1] In the presence of 1 kg of Pd-Te catalyst, the butadiene was made up of 21 kg/hf, acetic acid at 2.94 kg/hr, and 6 vol% oxygen/94 vol% nitrogen. The existing gas is circulated at 34 kg/hr, and the ethoxylation reaction is carried out at 8 (TC, 6 MPa) to obtain 81 wt% of 1,4-diethoxycarbonyl-2-butene. * Diethyleneoxy-1-butene 9 wt%, 3-hydroxy-4-ethoxycarbonyl_ι__butyl 2% by weight, acetic acid 3wt%, other than boiling point below 3,4__ Ethyloxy 4 is a mixture of 3 wt% of a component of butene and 2 wt% of a component having a boiling point higher than that of 3,4-diethyloxybutene. [Reference Example 2] 分离 By the continuous distillation, the mixed liquid u L obtained in Reference Example 1 was separated into a 3 'diethyl decyloxy-1-butene-containing liquid and diethyl ethoxylated 2-butene-containing liquid. liquid. In addition, the steaming system uses the 40-segment 〇idershaw steaming tower. In the continuous steaming, the top pressure was maintained at 20 mmHg, the reflux ratio was maintained at 3, and the overhead production was maintained at 95. (: 'The bottom temperature is kept at 15 rc, then the 5 cc/hr 'dimer solution is continuously introduced into the 2Q segment from the bottom of the tower to be connected from the top of the tower, 'from the bottom of the tower at 123 cc / hr Continuous discharge. Borrowed continuous steaming 'U-diethyl-based + butene containing liquid from the tower as: the bottom liquid, from the tower, 3,4-diethyl oxime oxime + τ ene containing Wei as a The obtained 3' 4-:(tetra)oxy-containing liquid system contains ^diethoxycarbonyl +1^45 wt%, 3_cheng + (tetra)oxy + lysine, and acetic acid 22 Wt% 'except which The point of the Buddha is less than 3, 4-diethyloxy + 097142815 33 200934787 The composition of 20 w is a mixture of 2 wt% of the component with a boiling point higher than 3, 4_diethoxydecene. The content of 1,4-diethyloxy-2-butane in the 4-diethoxy-i-butene-containing liquid is 1 wt% or less. [Reference Example 3] The obtained in Reference Example 2 The 3,4-diethoxy-anthracene-butene containing liquid is continuously distilled, thereby separating most of the components having a boiling point lower than 3,4-diethyloxy+butene. The steam filling station is filled with a 5 m regular filling cartridge TM-700M (MC PACK) packed tower (HETP140 mm/N) TP). In continuous distillation, the pressure at the top of the column is maintained at 100 mmHg, the reflux ratio is maintained at 3, the temperature at the top of the column is maintained at 77 C. The temperature at the bottom of the column is maintained at 144 ° C, and the flow rate at 2 〇 kg / hr is 3, 300 kg of 4-diethyloxy-1-butane containing liquid was continuously introduced to a distance of 2610 mm from the bottom of the column, and continuously distilled from the top of the column at 7.6 kg/hr, from a distance of 580 mm from the bottom of the column. In the form of side stream, at 11 4 kg / hr and continuous discharge from the bottom of the tower at 1 kg / hr. With the continuous steaming hall, the point from the top of the tower is less than 3, 4-diethyloxy The component of 1-butene is used as the co-exit. The coke solution contains 71% by weight of acetic acid and 0.18% by weight of 3,4-diethyloxy-l-butylene (equivalent to 3 in the steaming tower). The amount of the 4-diethoxy methoxyl compound is 0.17% by weight, and the content of the component having a boiling point lower than that of the 3,4-diethyloxy 丨 丁 butyl sulphate is 21 wt%. The liquid discharged from the bottom of the column contains 70 wt% of 3,4-diethyloxy-1-butene, and 3-glycosyl-4-ethenyloxy-1 to butylene 9 wt%, and contains The boiling point is lower than that of 3, 4-diethyloxy butyl butyl group, 3 wt%, and the boiling point is about 3, 4-diethyl hydrazine. The composition of the base-1-butadiene is 18 wt%. In addition, from the effluent of the side stream 097142815 34 200934787, 3,4-diethyloxy-1-butanyl 69 is obtained with 1:%, 3 _ group -4-Ethyloxy-1-butene 15 wt%', in addition to the content of 4 wt% lower than the 3,4-diethyloxy-1-butene, and the Buddha point higher than 3, The composition of 4-diethoxymethoxy-1-butene is 12 wt% of purified 3,4-diethyloxy-1-butene. [Example 1] 31.2 mg of a ligand represented by the following formula (1), which is represented by the above formula (B-3), was added to a glass flask under a nitrogen atmosphere. The β-position is 2 times the molar amount relative to the palladium metal) and the 3,4-diethyloxy-1-butene containing liquid 75 g from the side stream in Reference Example 3 is heated at 80 ° C. The mixture was stirred for 1 hour to be dissolved to prepare a palladium catalyst solution. Inductively coupled plasma mass spectrometry (ICP-MS ' Inductively Coupled Plasma Mass

Spectrometry) The concentration of the dissolved palladium metal in the palladium catalyst solution was measured, and as a result, the metal was 20 wtppm. To the 2 cc of the catalyst liquid, DBP0 [2,4-di(t-butyl)phenyl) phosphite represented by the following formula (2)] is added to the cc. 20 times the molar amount) 'heated at atmospheric pressure, i75 ° c for 27 hours. The heated catalyst solution was filtered through a filter having a pore size of 8 m. The concentration of palladium remaining in the filtrate was measured by ICP-MS. As a result, the residual palladium metal concentration after heating and filtration was 2 〇 wtppm. The dissolution residual ratio of the palladium metal was calculated from the initial concentration before heating and the residual dissolved concentration. As a result, the dissolution residual ratio of the metal was 100%, and the Pd metal precipitation rate was 〇%. Dissolution residual ratio (%) == residual dissolved concentration / initial concentration Pd metallization amount (wtPpm) = initial concentration - residual dissolved concentration 097142815 35 200934787

Pd metal precipitation rate (8) = [Pd metallization amount] / [initial concentration] [Chem. 22]

[Comparative Example 1] (Control test) φ The operation was carried out in the same manner as in Example 1 except that DBP0' was not added to the palladium catalyst solution and heated at normal pressure and 1 WC. As a result, the concentration of the palladium metal remaining after heating and filtration was 6 wtppm, and the Pd metal precipitation rate was 70%. [Comparative Example 2] (Comparative effect of DBPO with triphenylphosphine), except that DBP was not added to the palladium catalyst solution, and instead, 3 mg (4 times molar relative to palladium metal) was added. The operation was carried out in the same manner as in the above Example 1 except that it was heated under normal pressure and 175 art. 097142815 36 200934787. As a result, the concentration of the palladium metal dissolved in the remaining after heating and filtration was 2 wtppm', and the Pd metal precipitation rate was 90%. [Example 2] (Conditions of triphenylphosphine 1 〇〇〇 wt ppm) Under a nitrogen atmosphere, acetic acid was added to a glass flask to give 7.8, and the ligand represented by the formula (1) was 78.8 mg ( 2 times the molar amount relative to the palladium metal), 76.5 mg of β-triphenylphosphine (the concentration of triphenylphosphine in the catalyst solution is 1 〇〇〇 wt ppm), and 3 obtained from the side stream in Reference Example 3 , 4 g of diethyleneoxyl-butene was contained, and the solution was dissolved by heating at 80 ° C for a few hours to prepare a palladium catalyst solution. The concentration of the palladium metal dissolved in the palladium catalyst solution was measured by ICP-MS, and as a result, the metal palladium concentration was 54 wtppm. To the palladium catalyst liquid 2, DBPO [phosphoric acid phosphite (2,4-di(t-butyl)phenyl) ester] represented by the above formula (2) was added to 12.6 mg (2 相对 relative to palladium metal). Moum), heated at atmospheric pressure, ® 175 ° C for 10 hours. The heated catalyst solution was filtered through a filter having a pore size of 8 Am, and the concentration of palladium remaining in the filtrate was measured by ICP-MS. As a result, the residual palladium metal concentration after heating and filtration was 52 wtppm. The dissolution residual ratio of the palladium metal was calculated from the initial concentration and the residual concentration before heating. As a result, the dissolution residual ratio of palladium metal was 96%, and the pd metal deposition rate was 4%. [Example 3] The operation was carried out in the same manner as in the above Example 2, except that the amount of DBPO added was adjusted to 6.3 mg (relative to the amount of metal 097142815 37 200934787). As a result, the residual palladium metal concentration after heating and filtration was 50 wtppm, and the Pd metal precipitation rate was 7%. [Example 4] In addition to adding triphenylphosphine [P(〇Ph)3]5 /U to a palladium catalyst solution (relative to the amount of metal 4 times the molar amount) instead of DBP0' under normal pressure, Π5Ϊ The operation was carried out in the same manner as in the above Example 2 except that heating was performed. As a result, the residual concentration after heating and filtration was 23 wtppm, and the Pd metal precipitation rate was 57%. [Example 5] In a nitrogen atmosphere, 'palladium acetate 5.0 was added to a glass flask, 48.4 mg of the ligand represented by the above formula (1) (2 times the molar amount relative to the palladium metal), and triphenyl group. 12.4 mg of phosphine (concentration of triphenylphosphine in a catalyst solution of 5 〇〇 wtppm) and 3,4-diethyloxy-p-butyl sulphide 24 g obtained from the side stream in Reference Example 3, Dissolving at 80 ° C for 1 hour to prepare a solution of the catalyst. Adding DBPO [phosphorous acid phosphite (2) represented by the above formula (2) to 3 cc of the palladium catalyst solution , 4-di(t-butyl) stupid) vinegar] L 3,4-diethyloxy-butene-containing liquid 1.8 § (relative to the metal 2 • • mole amount). The concentration of the metal concentration in the Jingjing solution was determined by ICP-MS to be 59 wtppm. The shaft catalyst solution was heated at 175 C for 10 hours under normal pressure. Use a filter with a pore size of 8 to secrete the heated catalyst solution, _ ICP-MS to remove the residue in the solution. 097142815 38 200934787 Concentration. As a result, the concentration of the dissolved palladium metal remaining after filtration is 55 wtppm. The residual rate of dissolution is taken before the heating 39. The fine fruit is called the concentration concentration in the concentration domain, and the precipitation rate of the metal is calculated. ♦ The residual rate of metal dissolution is 93%, and the genus of genus [Comparative Example 3] is not added to the method of reading the catalyst (10), and the application of Example 2 is the same as 0 dan', ° fruit, and remains after heating and filtering. The dissolved palladium metal concentration was 4 mm, and the Pd metal precipitation rate was coffee. [Comparative Example 4] In addition to the catalyst-free medium, the sub-filled n-butyl acrylate [P(On-Bu) 3] 5el (relatively single metal) was added to the liquid. The operation was carried out in the same manner as in the above Example 2 except that DBp was replaced by 4 times the molar amount. As a result, the residual dissolved metal concentration after heating and filtration was 2 wtppra, and the Pd metal precipitation rate was 96%. The results of the above Examples 1 to 5 and Comparative Examples 1 to 4 are collectively shown in Table lc> 097 097142815 39 200934787 Example 5 03 m DBPO/ Pd=20 PPh3 : 500 wtppm o to ΙΛ CO 03⁄4 卜 Comparative Example 4 LO P(0n-Bu)3/ Pd=4 PPh3 : 1000 wtppm LO oi 03 inch CD 05 Comparative Example 3 Inch LO 1 PPh3 : 1000 wtppm LO寸卜CO 05 Example 4 Inch 1〇P(0Ph)3/ Pd=4 PPh3 : 1000 wtppm L〇t—H o CO CO Example 3 Inch LO DBPO/ Pd=10 PPh3 : 1000 wtppm LO rH o p&quot Brick s CO 05 Example 2 LO DBPO/ Pd=20 PPh3 : 1000 wtppm rH CD CNJ in CO 05 inch Comparative Example 2 Ο 03 PPh3/ Pd=4 1 Lrt r.丨丨H C<1 ο § Comparison Example 1 S 1 1 LO CO Ο Example 1 DBPO/ Pd=20 1 LO Bu c^ag 溶解 Dissolved Pd concentration of raw material liquid (wtppm) Molar ratio additive of additive 1 and Pd metal 2 (wtppm) Temperature (° c) Time (h) Dissolved Pd concentration after heating and filtration (wtppm) Dissolved Pd residual rate (%) 1 Pd metal precipitation rate (%)

0 inch-SH&O 200934787 [Chem. 24]

(3) @ [Example 6] Under a nitrogen atmosphere, acetic acid was added to a glass flask to give 2. 5 ffig, (3) the ligand represented by 19.5 mg (relative to metal = 2 times molar = And in Reference Example 3, 20 g of the 3,4-bis(10)oxy+-containing liquid was obtained from the towel, and it was heated at 8 Gt for 1 hour to dissolve to prepare a butterfly solution. The catalyst solution was determined by ICP-MS. The concentration of the metal was as follows, and the metal palladium concentration was 42 wtppm. To the palladium catalyst solution, DBP0 [2,4-di(t-butyl) represented by the above formula (2) 添加 was added to 3 cc of the palladium catalyst solution. Phenyl) ester] 19 mg (20 times molar amount relative to palladium metal), heated at 175 ° C under normal pressure for 1 hour. The heated catalyst solution was filtered with a pore size of 8 filter. The concentration of palladium remaining in the filtrate was measured by ICP-MS. As a result, the residual metal concentration after heating and filtration was 41 wtppm. The initial concentration and residual degree before heating were used to calculate the metal. When the residual ratio β was dissolved, the residual ratio of palladium metal was 98%, and the precipitation rate of Pd metal was 2%. [Comparative Example 5] 097142815 41 20093478 7 The operation was carried out in the same manner as in the above Example 6 except that DBP0 was not added to the catalyst solution. As a result, the residual concentration after heating and filtration was 0 wtppm, and the Pd metal precipitation rate was 1〇〇. [Example 7] In a nitrogen atmosphere, a palladium acetate was added to a glass flask, 2. 2 mg, and a ligand represented by the formula (3) was 19.5 mg (2 times compared to the palladium metal). Ear amount), triphenylphosphine 20 mg (triphenylphosphine concentration in the catalyst solution is 1 〇〇〇 wtppm), © and 3,4-diethyl methoxy group obtained from the side stream in Reference Example 3. -Bubutylene containing 20 g, and heating and stirring at 80 ° C for 1 hour to dissolve, to prepare a palladium catalyst solution. The concentration of dissolved palladium metal in the palladium catalyst solution was determined by ICP-MS. To the palladium catalyst liquid 2 Cc, DBP0 [2, 4-di(t-butyl)phenyl) phosphite represented by the above formula (2)] 19 mg (relative to palladium metal) For 20 times the molar amount, it is heated at normal pressure and 175 ° for 1 hour. The heated catalyst solution is filtered by a filter with a pore size of 8, using ICP- The concentration of palladium dissolved in the filtrate was measured by MS. As a result, the concentration of the dissolved palladium metal remaining after heating and filtration was 40 wtppm. The residual concentration of palladium metal was calculated from the initial concentration and residual concentration before heating. The palladium metal dissolution rate was 96%, and the Pd metal precipitation rate was 4%. * [Comparative Example 6] Operations were carried out in the same manner as in Example 7 except that DBP0 was not added to the palladium catalyst solution. . As a result, the residual solution after heating and filtration had a metal concentration of 0 wtppm' Pd metal deposition rate of 1%. 097142815 42 200934787 [Example 8] In a nitrogen atmosphere, 'palladium acetate 5.1 mg was added to a glass flask, and the ligand represented by the above formula (3) was 46.2 mg (relative to the metal being 2 times the molar amount). ), 12.7 mg of triphenylphosphine (concentration of triphenylphosphine in the catalyst solution: 5 〇〇 wt ppm) and 丄昝 醯 醯 醯 — 卜 含有 含有 24 参考 参考 参考 参考 参考 参考 参考 参考The mixture was stirred at 80 ° C for 1 hour to dissolve, and a saturated catalyst solution was prepared. To the 3 cc of the catalyst liquid, 3, 4-, DBP0 [2,4-di(t-butyl)phenyl) phosphite represented by the above formula (2) is added. The diethyl ethoxy-1-butene contained 1.8 g (2 〇 moles relative to the palladium metal). The dissolved palladium metal concentration in the palladium catalyst solution was measured by ICP-MS, and as a result, the metal palladium concentration was 58 wtppm. The palladium catalyst solution was heated under normal pressure at 175X: for 10 hours. The heated catalyst solution was filtered using a filter having a pore size of 8 " m, and the concentration of palladium remaining in the filtrate was measured by ICP-MS. As a result, the residual palladium metal concentration after heating and filtration was 卯"1. The initial concentration and residual concentration before heating were used to calculate the dissolution of the palladium metal. As a result, the residual solubility of the metal was 97%, and the precipitation rate of the pd metal was 3%. The results of the above Examples 6 to 8 and Comparative Examples 5 to 6 are collectively shown in Table 2. 097142815 43 200934787 [Table 2] Example 6 Comparative Example 5 Example 7 Comparative Example 6 Example 8 Dissolution of raw material liquid Pd concentration (wtppm) 42 42 42 42 58 Molar ratio of additive 1 to Pd metal DBP0 / Pd = 20 - DBP0/ Pd=20 - DBPO/ Pd=20 Additive 2 (wtppm) - - PPh3 : 1000 wtppm PPh3 : 1000 wtppn PPh3 : 500 wtppm Temperature 175 175 175 175 175 175 Time (h) 10 10 10 10 10 After heating and filtering Dissolved Pd concentration (wtppm) 41 0 40 0 56 Dissolved Pd residual rate (%) 98 0 96 0 97 Pd metal precipitation rate (%) 2 100 4 100 3 [Example 9]

(Inhibition of metal precipitation of palladium metal by DBP0 under reduced pressure) In a nitrogen atmosphere, a glass flask was charged with 21 mg of palladium acetate and 200 mg of a complex represented by the formula (1) (relative to palladium metal). 2 times the molar amount), triphenylphosphine 49 mg (the concentration of triphenylphosphine in the catalyst solution is 1 〇 wtppm) & and Reference Example 3, 3, 4_ diacetamidine obtained from the side stream The oxy-indole-butene contains 4 cc of cc, and is heated and stirred at 8 C for 1 hour to prepare a catalyst solution to obtain a reaction liquid containing a metal palladium concentration of 50 wtppm. The obtained reaction liquid and the formula ( 2) DBP0 (1.22 g, 2 〇 moles relative to palladium metal) is placed in the container, sealed, and then heated to 165 C under reduced pressure (300~380 torr). Maintaining the same temperature, starting from the time point when the temperature reaches i65 〇C ('me 〇), the concentration of the reaction solution in the reaction solution is measured at a predetermined time, and the change over time is observed. The results are shown in Fig. 1. The concentration was measured by IPC-MS. Further, the dissolution residual ratio (8) 097142815 44 200934787 was proportional to the initial concentration in the reaction solution. Comparative Example 7 The change in the palladium concentration over time was observed in the same manner as in Example 9 except that DBp was not added. The results are shown in Fig. 1 (industrially available) The method of the present invention is carried out in an industrial reaction such as an isomerization reaction or a hydrogenation reaction which is carried out by using a transitional gold lip complex as a catalyst, and can be suppressed in a device such as a pipe or a steam tower. The metal loss caused by the precipitation of the catalyst metal and the generation of contamination due to the catalytic metal in the treatment system, and further, the catalyst metal can be efficiently discharged to the outside of the system in the form of dissolving the contained liquid. It is very useful in the industry. In addition, the specification, patent application scope, drawings and abstracts of the patent application No. 2007-288508, filed on the sig. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing changes with time in the Pd dissolution residual ratio in Examples 9 and Comparative Example 7. The vertical axis indicates the Pd dissolution residual ratio (%). , The horizontal axis represents time (8), and DBPO refers to bisphosphite (2,4-di(t-butyl)phenyl) ester. 097142815 45

Claims (1)

200934787, 'VII. Patent application scope: 1. A method for inhibiting the precipitation of a metal from a transition metal complex, characterized in that it comprises a ligand having a complex composed of a trivalent organic compound from the eighth to tenth The solution of the transition metal complex of the transition metal selected from the group transition metal is contacted with an aromatic phosphite different from the trivalent organic dish compound, thereby inhibiting the metal from the transition metal in the solution. The compound precipitated. ❹ 2· For example, the method of precipitating the metal from the transition metal complex in the first item of the towel material 'where' the aromatic phosphite is represented by the following formula (I): [Chemical 1] PH-0-R)t ( I) [In the formula (I), three R's each independently represent a hydrocarbon group which may have a substituent, and at least one R is an aryl group. 3. A method for inhibiting precipitation of a metal from a transition metal complex according to claim 1 or 2, wherein at least one aromatic group of the aromatic phosphite in the formula (I) has an ortho position in the ortho position thereof Substituent. 4. A method for inhibiting precipitation of a metal from a transition metal complex according to the third aspect of the patent application, wherein at least one aromatic group in the formula of the aromatic phosphite has a substituent in the ortho position, A substituent bonded to a '3 or 4 carbon atom'. 5. The method for inhibiting the precipitation of a metal from a transition metal complex as in the fourth aspect of the patent application, wherein three of the 'aromatic phosphite systems are the same, and the 097142815 46 200934787 has a level of 3 in the ortho position. Or a phenyl group of a substituent bonded to a 4-stage carbon atom. 6. The method of inhibiting precipitation of a metal from a transition metal complex according to any one of claims 1 to 5, wherein the aromatic phosphite is a monodentate phosphite. 7. The method for inhibiting precipitation of a metal from a transition metal complex according to any one of claims 1 to 6, wherein the trivalent organophosphorus compound is derived from a phosphine, a phosphite, and a phosphoramide One of the groups consisting of idi te ) is selected to be less than one. 8. The method for inhibiting precipitation of a metal from a transition metal complex according to any one of claims 1 to 7, wherein the trivalent organophosphorus compound is a polydentate phosphine, a phosphite, and a phosphite. At least one of the selected groups. The method of inhibiting precipitation of a metal from a transition metal complex according to any one of claims 1 to 8, wherein the '8th to 1st' group transition metal is palladium or platinum. 10. The method for inhibiting precipitation of a metal from a transition metal-based complex according to any one of claims 1 to 9, wherein 'containing a ligand comprising a trivalent organic phosphorus compound and from the eighth to A solution of a transition metal complex of a transition metal selected from a group 10 transition metal, wherein the transition metal complex is used as a catalyst for isomerization, hydrogenation, hydroquinone, dehydrogenation, and low A solution after any one of a polymerization reaction, a metathesis reaction, a coupling reaction, or an allylation reaction. 11. The method for inhibiting the precipitation of a metal from a transition metal complex according to claim 10 of the patent application, wherein the composition comprises a 097142815 47 200934787 seat composed of a trivalent organophosphorus compound and a transition metal from the 8th to the 0th group A solution of the transition metal complex of the transition metal selected is a solution containing an allyl compound derivative different from the starting material after the isomerization reaction of the starting allyl compound derivative. 12. A method for inhibiting precipitation of a metal from a transition metal complex according to the first or second aspect of the patent application, wherein the method comprises a ligand comprising a trivalent organophosphorus compound and a transition from the 帛8 to 1 〇 family The solution of the transition metal complex of the transition metal selected in the metal is the reaction liquid after the isomerization reaction of the ethoxylated allyl compound. 13. For example, the method for suppressing the precipitation of a metal from a transition metal complex by the 12th item of the application, in which the 'ethoxylated propyl compound is a ethoxylated oxylation reaction product from butadiene. The liquid containing 3 4_diethyloxy+din was obtained as a main component. 097142815 48