TW200909411A - Method for isomerizing allyl compound - Google Patents

Abstract

Disclosed is a commercially advantageous method for isomerizing an allyl compound using a catalyst, which enables to obtain an isomer with high yield with use of a small amount of catalyst by suppressing deterioration of the catalyst. Specifically disclosed is a method for isomerizing a raw material allyl compound into a corresponding allyl compound in the presence of a catalyst. This isomerization method is characterized in that a liquid containing the raw material allyl compound is brought into contact with an organophosphorus compound before isomerization by the catalyst.

Description

200909411 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to an isomerization process for allyl compounds, and more particularly to an isomerization process characterized by isomerization, self 3-Ethyloxyallyl compound, which produces the corresponding compound of ethoxylated propyl compound. [Prior Art] Dilute propyl compounds are important starting materials for organic synthetic chemistry = should be converted into target products, especially diethyl ethoxylates. Because of their characteristic skeleton, *only The compound is also an important medium in which diols can be produced by hydrolysis. The development of the manufacturing process of the diethyl ethoxylated propyl compound. For example, 'Report has # used (4) A method for preparing a olefin by an ethoxylation reaction (Patent Document " for a bismuth== group: a total of two (10) oxygen;醯 醯 _ 丙基 化合物 化合物 ί 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在1 k city 酝 G 酝 二 二 酿 -2- -2- -2- -2- 丁 丁 , , , , , , , , , 4 Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ - B knows 1 milk base - a butene. Therefore, in the 11 - Ding process, the cost of butadiene in the raw material will increase. Therefore, it is developed to produce by-products = : a method for producing a U-oxydi-Sts milk-based (IV) compound. For example, a tool has been reported; sub-97117793 5 200909411: a complex complex catalyst of an acid ligand, converted from 3, 4_2 to U The isomerization reaction of diacetyloxyl I (patent Z also reported that in addition to the 18 complex catalyst and phosphite ligand, the patent is imported into the literature. And get the more active isomerization catalyst s surname +,, 丄, the medium of this specific ethoxy allylic compound. y, the alternative '", the member, and must use a large number of touch The cause of deterioration of the medium, the cut & θ ', 5 core is caused by the component of the bis-diethoxy allylic compound, and it is reported that the catalyst deteriorated component is removed by the solid experience. ^ Method (Patent Document 4). However, in this case, 'the solid experience is in addition to the secondary component of the catalyst, so it must have a large amount of solidity;: In addition to the knife, it also adsorbs several acids. Therefore, it is required to be able to remove the stagnation method in the palm of the hand. Patent Document 1 Patent Document 2 Patent Document 3 Patent Document 4 [Disclosure] (Problems to be Solved by the Invention) Method: The subject of Tian is to provide isomerization of an allyl compound to deteriorate , a method of isomerization of a decyl propyl compound, which can suppress the amount of catalyst used in the industry and the industry, and obtain an isomer in a high yield, 曰本专利特开平1 1-71327号In the inventors of the present invention, in order to solve the above problems, the inventors of the present invention have devoted themselves to research, and are now studying in detail in order to solve the above problems. The diterpenoid compound liquid can be removed by the sarcophagus compound; and the component which promotes the deterioration of the heterogeneous catalyst is apparently completed. : P, the present invention is intended to be the following [1]~[13] ', [1]-isomerization method, after contacting the allylate compound containing the starting material, in the presence of a catalyst, The method for isomerization of the above-mentioned compound [1], wherein the phosphorus compound is a compound having a compounding compound [5] as described in [3] or [4] above. The isomerization formula is triphenylphosphine. 〃, the above-mentioned organic phosphine [the same as the isomerization method of any one of [1] to [5], the amount of the phosphorus compound in contact with the liquid contained in the pot, i (1) is as the above-mentioned weight% Within the scope. The inclusion of a propyl group compound is a method of constitution, wherein the above is carried out. The night contact with the ruthenium compound is 60 t or more. [8] As in any of the above [1] to [7], there is a method of conjugated diene by dimethacene, wherein the method is further carried out. The reaction was carried out to obtain a solution containing the above-mentioned 97117793 200909411 allyl compound. [9] The isomerization method according to any one of [1] to [8] wherein the catalyst is a liquid phase homogeneous palladium catalyst and is a phosphorus compound having at least one P-0 bond. Bit-based catalyst. [10] The isomerization method of the above [9], wherein the above has a dip bond, , and . The debonding group is a bisphosphonate of a bidentate. [11] The isomerization method according to the above [9], wherein the above-mentioned bismuth bond: the % ligand is a bi-ligand phosphorous _ (phQsph., Λ, 12) as described above [1] The isomerization method according to any one of [11], wherein, the above, the ...-'-------------- a method for the isomerization of any one of the above [1] to [12] using the above allyl compound to produce a phase 3]-allyl compound, from the corresponding isomerization method The allyl compound of the invention. (Effect of the invention) The isomerization of the invention using the catalyst of the second a M , , , 〇® lactyl allyl compound can be used according to a small amount of catalyst. [Embodiment] An isomer is obtained in an intermediate yield. The present invention will be described in detail below. The constitution described below is an example of an embodiment of the present invention, and is not limited to May, and is also an alkene of the present invention. The propyl compound, :: the valence in the valley, and the isomerization of the stalk from the compound having a dilute propyl group by === propyl 97117793 200909411 The decyl group having a acetyl halide, a carboxylic acid or the like on the ally-position of the D-substance and the hexyl group is a rolling base. For example, 3, 4-diethyl-H is an image of its The compound is not specifically limited. In the present invention, the compound is subjected to isomerization to obtain a compound. The 1,4-diethyloxy allylation of human beings The method also includes converting a compound formed by the formation of an allyl group of :::::: to a compound having a core of the I:1 type to be a 3,4-di compound belonging to the allyl compound. 1 β isomerized by isomerization to produce the corresponding allyl group. The case of monoethoxylated allyl compound is taken as an example of the present invention = 3,4-diethyloxy fluorenyl propyl compound isoallyl A method for isomerizing a 3,4-compound of a raw material into a U-diethylene by a catalyst, characterized in that a liquid containing a 3,4-ipropylpropyl compound of a raw material is used (hereinafter referred to as 3,4-diacetateoxy:chemical & content-containing liquid), after contact with the compound, the isomerization of the 3/4-diethyloxyallyl compound in the presence of a catalyst Liquid f consists of:: compound ", with, 3, 4 - diethoxy allylic compound containing $ eight can be removed by phosphorus compound significantly promotes isomerization catalyst inferiority = compared to solid experience 'filled Since the compound is easy to process, it can be used to monitor the amount of &-ethoxylated allylic compound produced by isomerization, and the addition of inhibitor to the required amount of 97117793 200909411 Deterioration. In addition, because it is filled with a predetermined solid alkali before the start of operation, it is pre-processed in the process. In the case of (4) alkali, it can be used as a propyl propyl compound by isomerization. The method of the present invention may, for example, be a method of "U-diethyl oxypropylated compound: an allyl compound", "...diethylene and 1,4-diethoxypropenyl" Compound;; and q 4 w in the mixture is cut into a medium to contact 1 4-diethyl hydrazine m, - ^ milyl propyl compound isomerized to a lactyl allyl compound to enhance 丨 two = r:? Method"•“A mixture of alkoxy group and a group of U-diethoxy allylic compounds Indirectly, the U-diethoxy allylic compound in the mixture is isomerized to a 3,4-diethyloxyallyl compound to enhance the 3,4-dioxypropenyl compound. Method of concentration".

In the present invention, a 3,4-diethyloxyallyl compound (including "3, a mixture of a diethylene ethoxyallyl compound and a fluorene, a 4-diethoxy allylic compound") It is not particularly limited, and it can be produced by a total of one ethylene-based ethoxylation reaction in the presence of a catalyst. The dimerization of a total of a diene of a ethoxylated allyl compound can be carried out by various methods. Most commonly in the presence of a catalyst, the reaction of butyl hydrazine, acetic acid and oxygen is carried out, and 1,4-diethoxycarbonyl-2-butene which is a diethyl ethoxyallyl compound is obtained. 3,4-Diethyl 醢 9717793 10 200909411 Oxygen + Ding. Further, it is also combined to form a hydrolyzate belonging to such a base compound, which is a hydrolyzate of the above-mentioned base compound, and is formed by a hydrolyzate of the above-mentioned base compound. A conjugated diene which can be used as the present invention: butyl: special. Two: dilute. 2,3-dimethyl [two-hearted bismuth " heteropolar pentane dichloride, U-cycloheptadiene, U-cyclooctadiene ^, 1,3-1,3-hexadiene 2,4_hexadiene, etc., preferably, pentylene, f U-cyclohexane, 丨'3-ring 戍 two return, especially good for D::,, = two women's such as Ding Erjiao , gentleman - to, q 4 - postal, different bismuth. The highest reactivity, so a small number of common diene, as shown as a common vehicle, a dilute of the second brewing, with the ability to replace the common two with the second I brewing oxygen Catalysts can be used in any soil compound: ^_, especially good for _ body touch:: body = family

The preferred reason for L is that the catalyst 2 is 碲. The combination of exemption and deuterium is the choice of the propyl propyl compound W ′ and the obtained diethoxy ethoxylate as the active ingredient (4). Therefore, it is preferable to carry it in a preferred manner, and it is preferably carried on a carrier which is not particularly limited to activated carbon or graphite, such as titanium oxide, titanium oxide, or cerium oxide. The physical properties of the carrier are preferably 'excellently preferred as the dioxins having superior strength. In the carrier with the carrier, the ratio of the porous genus of the shell is usually 2 ). I. Relative to the catalyst of the catalyst as a whole. 垔 垔 preferably 1 to 10% by weight, again, phase 97117793 200909411 The ratio of other auxiliary catalyst metals in the whole media is selected from the range of U1 to 30%, and if the value is too small, the cost competitiveness is low, and if the value is too The competitiveness of the catalyst is reduced due to over-consumption of the cost of the catalyst. The above-mentioned diethyl ethoxylation reaction is preferably carried out in air or an oxidized empty milk, air or oxygen diluted with an inert gas such as nitrogen. The oxygen concentration may be in the range of H00voi%, more preferably 2 to 5, and the secret is preferably 3 to 4 vol%. The higher the agricultural degree, the higher the reaction rate, and the lower the oxygen concentration. The explosion occurs, and the process of the people's fire temple is less dangerous. - The ethoxylation reaction can be carried out according to any of the gas phase and the liquid phase. The reaction temperature f is 0 to 30 (the range of TC, preferably 10~) 25 (rc, better 3 ◦ ~ 2 〇〇ς range. The higher the reaction temperature, the higher the reaction speed, the better the efficiency of J generation On the other hand, the lower the reaction temperature, the less the risk of explosion and fire. The reaction pressure is preferably a dry circumference of atmospheric pressure ~ 5 GMPa, preferably atmospheric pressure ~ 30 MPa, particularly preferably 1 to 20 MPa. In the case of carrying out the diethyl ethoxylation reaction, the solvent used for the reaction is not particularly limited as long as it dissolves the reaction raw material, and is preferably a carboxylic acid such as water or a squab, or a butadiene. The conjugated diene itself, or the diethyl ethoxyallyl compound itself, which belongs to the product, can also be used as a hydrocarbon solvent such as hexane, Gengxuan, and xinzhu; An ether such as ethyl ether or triglyme; an ester such as ethyl acetate or butyl butyrate; 1,4-butanediol such as acetone or methyl isobutyl ketone; Alcohols, etc. ' 97117793 12 200909411 The weight of the conjugated diene and the catalyst to be used as a raw material is preferably in the range of 1 to ιοο, οοο, οοο, more preferably in the range of 1 〇 to 5 〇〇〇〇〇〇〇. , especially good for 100~20, 000,000. The smaller the weight ratio, the higher the reaction speed, and it is easy to rely on short time. Further, the larger the weight ratio, the less the catalyst cost can be achieved. In addition, the "3,4-diethyl oxyallyl compound-containing liquid" in the present invention means 3, There is no particular limitation on the 4-diethoxymethoxyallyl compound or a liquid containing a mixture of a 3,4-ethyleneoxyallyl compound and a fluorene, 4-diethoxy allylic compound. Preferably, any one of the following is referred to as a "3,4-diethyloxyallyl compound-containing solution": (1) a 3,4-diethyloxyallyl compound-containing solution and Before the phosphorus compound is contacted, a step of diacetylating the conjugated diene by the above catalyst is provided, and the reaction obtained by the reaction forms the stream itself; (7) the stream is formed from the reaction by the steaming A compound which is lighter in weight than a diethylene oxyallyl compound (hereinafter, a compound having a lower boiling point than a diethyl ethoxyallyl compound is simply referred to as a light-boiling compound) / :- Part or all; (3) from the reaction to generate a stream, by the remainder, etc. = the boiling formed by by-products a compound of the 3,4-diethyloxy propyl sulfonate (hereinafter, a compound having a higher boiling point than the 3,4-diethoxy oxonium compound is simply referred to as a high-boiling compound) The king's (4) generates a stream from the reaction, and removes either or both of the light-boiling compound and the high-boiling compound of the by-product by steaming or the like. Among them, it is particularly preferable to produce (1) a reaction obtained by the reaction of a catalyst and an ethylene-oxyl ethoxylation reaction. 97117793 13 200909411 The body is 3, 4- 7 years old - Gan, One, 4-ethyl allyl allyl compound containing liquid". In the "3,4_-based terpene:f compound-containing liquid", L is produced from the reaction obtained by the ethoxylation reaction of the catalyst by the above-mentioned catalyst, and the corresponding one exists in the contained liquid. , 4-diethyl ethoxylate = propyl = compound... "3, monooxyl propyl compound = 3, 4: two genus two! 'i: hydrolyzed propyl propyl allylic compound Compound/, and U-based ethoxylated propyl propyl compound of the compound and/or 3,4-di-based allylic propyl compound ft, and /, used "3 , [Diethyl ethoxyallyl compound containing thiodifluoride will contain 3'4-diethoxy allylic compound, U-diethyl liquid allylic compound, low boiling point compound and high boiling point Compound 1 4-- In the column, a liquid containing a high-fossil compound and a di(tetra) I: group compound is extracted from the bottom of the column, and a 3,4- : mercaptopropyl compound-containing liquid is distilled from the upper portion of the column to obtain Base: The compound-containing liquid can also be extracted from the top of the column and lightly boiling from the top of the column, and is extracted from the side stream, and the light-boiling compound is taken from the top of the tower. The ... is widely extracted from the bottom of the tower, but a small amount and 3, The 4-diethyloxy allyl compound-containing liquid is extracted from the upper or side stream of the column. Further, the pressure of the distillation column can be set to any, but from the viewpoint of the energy cost of the torrefaction Buddha. In order to make the temperature of the bottom of the tower; low 97117793 14 200909411 is preferably set to the top waste force of 1 to 76OmmHg. Further, the preferred top force is 5~200_Hg, particularly preferably 10~l〇〇_Hg. If the top of the tower is too low, it will cost too much to maintain the pressure. In addition, the steaming tower itself will become larger, which will increase the construction cost. Moreover, the pressure in the dome is too high. The temperature at the bottom of the distillation column becomes higher and the cost of steam increases. The top of the column is generally 〇20 (rc, preferably 2 (M60t, more preferably 4〇~14〇.^). If the temperature is at the top of the tower If it is too low, a special device such as a cooler is required to deteriorate the cost. Moreover, if the temperature is too high, the temperature at the bottom of the column also becomes a temperature, so that the steam cost is increased. The reflux ratio can be 1 〇〇, preferably 5 = If the ratio is too small, it will cause the deterioration of the separation ability. If the reflux ratio is too high, the addition of m will become the cause of the deterioration of the cost. Take care of the base material: the product containing 3 s of ethylene ethoxy allylate, 4 - ethoxylated allyl compound, low boiling point compound and liquid compound to the boiling point compound轫 戥 戥 & & & & ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The liquid, and the self-side (4) of the 3,4_diethyl-oxo-dot-point compound in the light-bulk allylate-containing two-introducing liquid from the top of the tower crane, so that the light bottom of the introduction liquid is extracted and contains the right Contains, and is known to be distilled from the top of the column. The liquid of the compound from the distillation column, = compound and 1,4-diethoxydecyl dimethyl ethoxy allylate contains low boiling point compounds. Class 3, 4, the case of the second thing per unit time, the material balance of the steaming tower is set to 100 when the weight of the overhead product is set to 100, the car father per unit time is 5~3 0 . At this time, from the bottom of the tower each 9711793 200909411 compound::: effluent f compound and 丨 '4-diethoxy allyl in the self-steaming tower SI!: preferably 5 ° ~ 99, Better 7〇,. Further, the ethoxylated propyl group is compounded with a W compound and a U-diethyl group, and is distilled from a side stream; 4 one liquid 't is a light boiling point compound from the top of the column, and 16—Ethylene oxyallyl compound contains liquid ^, and the weight of the introduced flow rate is set to 100 00, and the flow rate is. .". More than one, the best is 0.9~5. , more pieces:; The amount of the propyl compound-containing liquid is higher than that of the species and 1 4 - π soil 〇. Further, the liquid per unit time of the liquid containing the high-boiling point-injected caronate compound from the bottom of the column is preferably from 20 to 99, more preferably from 50 to 97. = from the top of the tower, the content of the compound _ compound 3 士二二二: ΐ 丙 : :: compound containing liquid 'can be distilled by distillation to remove the light boiling point distillation tower from the top of the crane to light-boiling compounds, and by Including η: extraction 3, [diethoxy allyl compound containing liquid. "'The pressure of the steaming tower can be set to any, but the energy cost of the steaming tower is good, ', ° is better to be bound... β 4 to lower the temperature of the bottom, ',, The force of 1 is set to 760_Hg. Further, the pressure of the top of the tower is 5~400_Hg, and the range of 1~2〇〇mmHg is particularly good. If the top pressure is used, it will cost too much to maintain the pressure. This ^ has also become larger 'and increased process construction costs. Moreover, in the case of the same pressure at the top of the tower, the temperature at the bottom of the steaming tower tower becomes higher, and the steam cost increases. The temperature at the top of the tower is generally 0~2〇 (rc, preferably 2〇~16 (rc, better 4〇~14〇97117793 16 200909411 = circumference. If the temperature at the top of the tower is too low), it needs cooling. ί costs deteriorate. Also, if the temperature is too high, it is due to the bottom of the tower. The temperature can also be W, the cost of reflux can be 1~100, preferably 〖~1n right back & too small, it will cause the separation ability to deteriorate, if the required heat increases, into A Zhitai A After the confinement, the A is the cause of the deterioration of the cost. In the tower of the tower, the farm is good for the introduction of the base of the steamed crane tower. The liquid-liquidity measurement of the low-boiling compound is taken into consideration. Further, the base of the compound of the base material is extracted from the bottom of the column including the side stream, and In the case of the top-cutting point compound, the distillation column material balance is obtained by introducing a weight of HV°°° per unit time, and the flow rate per unit time is 1 to 50, 杈# 5 to 45. At this time, the amount of the liquid containing the 3,4-diethyloxyl-propyl compound per unit time including the bottom of the side stream is preferably from 50 to 99, more preferably from 55 to 95. The present invention is characterized in that the 3,4-diethyleneoxyallyl compound-containing liquid is contacted with a phosphorus compound, but is obtained by a diethylation reaction step of a conjugated diene by a catalyst. When the reaction product is a "3' 4-diethoxy allyl compound-containing liquid", the reaction product stream may be supplied to the phosphine before being subjected to distillation separation; or the conjugated The reaction product formed by the diethyl ethoxylation reaction of the alkene is subjected to distillation separation, and then 3 is distilled off from the top of the column. The 4-diethoxy allyl compound-containing solution is contacted with a phosphine; and the 3,4-diethyloxyallyl compound distilled from the side stream may also be contacted with a phosphine. The amount of phosphorus compound can be exerted in a small amount, and it is preferable to make the phosphorus compound in contact with the top of the column. The liquid distilled from the side stream is used as a distillation tower which can be used. Etc., preferably a plate column. Let = two:: for example, a packed column, a plate column with liquid and 14--B, an ethyl decyl allyl compound, and a 4-ethoxylated allyl compound The Ta's f-segment is set to be more than 3 segments, and the special section is inserted into the ^"^. The economics of the steaming crane tower construction, the difficulty of operation, and the touch and the right segment are too small to be classified. The 3,4-diethoxylated propyl compound used in the isomerization reaction of the present invention is specifically 3,4-diethyloxy_丨-butene, 3,4 Diethyl methoxy- 2-methyl-1-butene, 3, 4-diethoxycarbonyl-methyl-butene, 3,4-diethyloxy-2,3-dimethyl- Butene, 3,4_two醯oxy-1-cyclohexene, 3,4-diethyloxy-p-cyclopentene, 3-decyloxy-1-cycloheptene, 3,4-diethyloxy Bicyclooctene, more preferably 3, 4-diethoxycarbonyl-butene, 3,4-diethyloxy-2-methyl-butadiene, 3,4-ethoxycarbonyl 3 methyl-1-butene, 4 -diethyloxy-b-cyclohexene, 3,4-diethyloxy-p-cyclopentanyl, especially preferably convertible to 1,4-butane The intermediate of the alcohol is 1,4-diethoxycarbonyl-2-indene 3,4-diethyloxy-1-butene. Further, in the hydrolyzate belonging to 3,4-diethyloxy-1-butene, 3-hydroxy-4-ethenyloxy-butene, 4-hydroxy-3-acetoxy-1-butane The isomerization method of the present invention is also applicable to the isomerization reaction of the olefin. In addition, in the present invention, the 1,4-diethyloxyallyl allylated 3,4-diethyloxy group obtained by the composition of the 3,4-diethyloxyallyl compound is 97117793 18 200909411. The allylic compound corresponds to the 1,4-diethyloxy ene complex of the isomer. Preferably, it is 1,4-diethoxycarbonyl-2-butene, 4, <RTI ID=0.0>>>>> U-diethoxycarbonyl-2,3-dimethyl emulsion-diethoxycarbonyl-2-cyclohexene, U-diethyloxy::,-diethoxycarbonyl-2-cycloheptane Alkene, U-diacetateoxy + ring is 1,4-diethoxycarbonyl-1 - butyl, oxime oxime / butene, 1,4-diethoxycarbonyl-3-methyl + butyl Alkene, u_ soil: 1 its own cyclohexene, 1,4-diethoxycarbonyl-; [W field of [_if decyl-butanol, especially good for the intermediate of j-private intermediates, 4, 4 - Diethyl methoxy 丨 丁烯 - butene. When the reaction of the 3,4-diethoxymethoxypropyl compound is carried out, various solvents can be used. The solvent is not used and can be used: formic acid, acetic acid, propionic acid, octaethanol, propanol, butanol, pentanol, ?r, decanoic acid; methanol, a r M Cob, sub-know, g Alcohols such as alcohols and octanols; - ethers of Ethyl, Tetra-, Di-, and Tri-glycol; benzene, toluene, dimethyl, temple, simmer, simmer, and sesame: An organic solvent such as a hydrocarbon, a hydrocarbon, or the like. Comparison: 2: hexyl, cycline, etc., 乂 乂 马 f f f, acetic acid, propionic acid, butyric acid, etc. = class is particularly good for the acetic acid to increase the isomerization rate of the ethoxylated oxygen. The reason why the father of vinegar is good is that it helps to increase the rate of isomerization, so that the concentration of acetoxy group, that is, the concentration of acetic acid becomes higher. The addition amount of the medium is relative to the diethyl ethoxyallyl compound, and the weight of the hexanyl group is 0 to 10, 000% by weight, preferably 〇U〇〇wt%, and particularly good 97117793 19 200909411 1 20 The smaller the amount of addition, the more the reactor capacity can be added, and the catalyst degradation rate tends to decrease as the overnight. For example, the catalyst used in the isomerization of 3,4-di-ethoxy allylic compound in the month has the ability to make the 3,4-diethyloxyallyl compound isoindole ..., 1, 4 - the ability of the ethoxylated allylic compound is not particularly limited: it can be a liquid phase homozygous compound touch 豸 'better 8th ~ workers 过 / / degree metal of the sentence is wrong The material catalyst is particularly preferably a liquid phase homogeneous palladium complex catalyst which exhibits an extremely high activity for the isomerization rate of ethoxylation. The liquid phase homogeneous chelating catalyst can be adjusted from various transition metals, and specific examples thereof include acetate, acetylated acetic acid compound, chloride, desert salt, salt, sulfate, nitrate, organic salt, There are no coordination compounds, carbon oxide coordination compounds, phosphine coordination compounds, phosphorous acid coordination compounds, and the like. I. Liquid phase homogeneous complex catalyst, preferably palladium metal 'Palladium acetate, = chemical! ε, dichlorocyclohexane, two women, 肆 (triphenyl lin), double (two sub-soil acetone)! Ba-fluoroacetic acid, acetamidine propionate, acetic acid, dicyclooctane:: nickel gas = molybdenum cyclooctadiene, etc. 'Specially cheap _: vinegar t: - palladium fluoroacetate. In the present invention, the above-mentioned metal compound and Γ :: ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... For example, if it is a phosphine, an acid, or a dish, it is used. This % coordination = (tetra) (iv) ligand " can be used without any particular limitation. The ligand may be a mono- or poly-ligand. As the ligand, 97117793 20 200909411 is preferably a compound having a p-o bond, particularly preferably a phosphorous acid or a squamous amine, particularly preferably a bi-ligand phosphorous acid or a phosphite. The reason is that in the isomerization reaction of the fluorene-allyl intermediate, since the ligand having a lower electron density promotes an increase in the reaction rate, it is preferred to have a P-Ο bond having a lower electron density. Phosphorus compound. Further, in the present invention, generally, one type of ligand is used, but two or more kinds of phosphorus ligands may be used in combination. Further, other ligands may be used in combination as long as the effects of the present invention are not significantly impaired. In the present invention, in the case of using a phosphorus compound having a p_〇 bond as a ligand, for example, the following general formulas (1) to (5) and formula (6_υ~(6-7) are not mentioned. Further, in the present invention, generally, a ligand of a ruthenium species is used, but two or more kinds of phosphorus ligands may be used in combination. Further, if necessary, it may be used in a range that does not significantly impair the effects of the present invention. Bit. ' 97117793 21 200909411 [Chemical 1] f (3) X'-H) x,, (5) (X1) ~〇-P(OR1)(OR2) (Y1) (X2) ~op(or3) <nr4r5) (Y2) (X3) ~OP(NR6R7)(NR8R9) (X4) R10 —NP(OR11)(OR12) (Y3) (X5) R13 ~-NP(OR14)(NR15R16) (Y1) — 〇-pC〇7a1 (Y2) -〇-p-°>2 d20

R R N R 18 19

(6-1) r-〇-p»〇r24 (6-2) RWp»Nr27rM (6-3) 33 /531 R 〇-w. # R30 R32 (6-4) r3S rWk»〇r39 R36 (6-5) R«〇_pC〇>.tA^〇r43 R40 (6-6) R45 ...«P, Nr, 49 R44 (6- 7) RS1 r53r52«x r5〇U (Υ4) -Ν_ρφΑ4 R21 (Y5) _N_p-〇-A5 N 〇22 In the above formulas (1) to (5), x~x", Υ^Υ,,5άΓ I (y] \ rv,., from any of () (X5), U1) (Y5) is optional. The above (Χ1)~(Χ5), (Υ1)~(Υ5) and (6-1) )~(6-7), r, r 22 97117793 200909411 Oxygen t independently means that oxygen, alkoxy, cycloalkyl, aryloxy, anthracene and amine or f' group can also have a substituent which is a substituent having an alkyl skeleton in R' aryloxygen (for example, a methyl group, a car: preferably: 14. butyl, different) Butyl, second butyl, first butyl methacrylate: /, isopropyl, n-eight dibutyl, pentyl, hexyl, octyl, :::, ., and 'alkyl or alkyl backbone moiety Further, it may further have a substituent, and the substituent may, for example, be an alkoxy group having a carbon number, an aryl group having a carbon number of 1 ft, a ft group, a carboxylic acid group having a carbon number of 2 to 1 Å, a thiol group, and a dentate group. original When RR and R to R are an aryl group, or a substituent having an aryl skeleton, the carbon number is usually 6 to 2 Å, preferably 6 to u. The aryl or aryl bone T portion may further have The substituent may, for example, be a hydrogen atom, an alkyl group of a carbon number, an alkoxy group of a carbon number 1 (a), a cycloalkyl group having a carbon number of 3 to 20, and a carbon number of 6 to 20. An aryl group, an aryloxy group having 6 to 2 carbon atoms, an alkylaryl group having 6 to 20 fluorene, an alkylaryloxy group having 6 to 2 carbon atoms, an arylalkyl group having 6 to 20 carbon atoms, The arylalkoxy group, the cyano group, the ester group, the ester group, the hydroxyl group and the halogen atom having 6 to 2 carbon atoms. Specific examples of the case where R, R' and R1 to R54 are an aryl group include a phenyl group. , 1-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethyl basic 2,4-.monomethylphenyl, 2,5-dimethylphenyl , 2,6-dimethylphenyl, 2~~ethylphenyl, 2-isopropylphenyl, 1-tert-butylphenyl, 2 di-dibutylpropyl, 2-benzene benzene Base, 3-chlorophenyl, 4-phenylphenyl, 2,3~dichlorophenyl, 2,4-diphenyl, 2,5-dichlorophenyl, 3,4-diphenyl, 3, 5-gas phenyl, 4-trifluoromethylphenyl, 2-methoxyphenyl, 3-methoxy 97117793 23 200909411 phenyl, 4-methoxyphenyl, 3,5-dimethoxyphenyl, 4-cyano Phenyl, 4-nitrophenyl, trifluoromethyl, pentafluoroethyl, pentafluorophenyl and the following groups (Cl) to (C-8). [Chemical 2]

(C-1)

(C-2)

(C-3)

(C-4) ΒιΛ

(C-6)

Buf

(C-7)

(C-8) In the formulas (1) to (5) and (Yl) to (Y5), 'A~A, and 'A5, respectively, are not: an alkyl group having a carbon number of a substituent, It can have a carbon number of 611717 24 200909411 and a carbon number of 6~30. It can be used in the middle and right--"the square base can also be positive in Af-QW", and there is a <Bei key knot base. Its "Li Shi, Li Qiang has introduced the gentleman's commentary base (where Ar*1 and Ar2 respectively can not have the carbon number of the substituent 6~18 formula (6-1)~(6_"φ, Τ1 τ7 v #方基) A, 1 y y knife independently represents a carbon atom, an alkane four basic four base, or may have a τ8-(〇2) τ9 private-valence group, τ8 and r respectively The fourth substituent of the substituent "μ R π Residue 1~1 (3 of the trifluorocarbon group, and the === benzenetriyl group may also have a substituent trivalent group. Q1 and W are independently represented - CR55r56. - - -ο-, -S-, -C0-, η are P55aD56 VIII, s/R and R each independently represent a hydrogen atom, an aryl group of 6 to 20 of Shilutong, and may have a substituent. Soil, or carbon number J ” when A~A, and Π5 are extensible bases, for example, four*two one f base extension Further, when A to A, and A1 to A5 are those which may have a j-stretched wire, the substituent may, for example, be an aryl group or an amine group having a carbon number of 10 W and a carbon number of 6 to 2 Å. a cyano group, a stilbene group, a trifluoro group; and, in addition, A to A, and A1 to A5 are exoaryl groups which may have a substituent, such as a phenyl group or a naphthyl group. The base may, for example, be an alkoxy group of a meal 10, a aryl group having a carbon number of 6 to 20, an amine group, an alkyl group = a number group, a trifluoromethyl group, etc. Sik amines, in A to A" and A When it is a di-aryl group which may have a divalent bond group in Arl_(Ql)n_Ar2, Arl and Ar2 are each independently a substituted aryl group having a carbon number of 6 to 18 which has a substituent, and the aryl group The product has 6 to 24, more preferably 6 to 16. As a specific example of a preferred substituent, = is an alkyl group having a carbon number of 1 to 10, an alkoxy group having a carbon number of 10, and a carbon number of 6 to 22 cases. ^, amide, cyano, decylamino, trifluoromethyl, etc. 97117793 25 200909411 Further, specific examples of A to A'' and A1 to A5 include -(CH2)2-, _(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -CH(CH3)-CH(CH3)-, -CH(CH3)CH2CH(CH3)- , -(CH3)2-C(CH3)2-, -C(CH3)2-CH2-C(CH3)2-, and the following groups (A-1) to (A-4).

97117793 26 200909411 [Chemical 3]

97117793 27 200909411 [Chemical 4]

(A-13) (A-14) H2〇—CHj H2C—ch2

(A-15)

97117793 28 200909411 [Chemical 5]

(A-36) 97117793 29 200909411 [Chem. 6]

(A-37)

(A-42)

s

(A-44)

97117793 30 200909411 A preferred specific example of the compound of the formula (1) to (5) and the formula (6-1) to (6-7) which represents a ligand of the present invention can be exemplified by the following monodentate group ( Specific examples of L-1) to (L-16) and multi-ligand (L-17) to (L-44) '(L-17) to (L_36) can be exemplified. [化7] /

(L-8) 97117793 31 200909411 [Chem. 8]

MeO

97117793 32 200909411 [Chemistry 9]

/ (L-18) lBu /Bu

(L-19)

97117793 33 200909411 [化 ίο]

97 97117793 34 200909411 [化11]

35 97117793 200909411

97117793 36 200909411 [Chem. 13]

(L-42)

In the specific examples of the phosphorous acid and the phosphite, it is preferably L20 to L44 and particularly preferably 1 L3G. The reason for these reasons is that the thermal stability of the ligand is higher, and the loss of the active species of the coal is less. The amount of the homogeneous tyrosine catalyst used for the isomerization of the diethoxylated bromopropyl compound in the present month is the metal in the liquid of the 3, 4-diethoxy allylic compound. The amount of the solution is preferably 〇·〇(Π~10〇〇wtppm, more preferably 0. 0b lOOwtppm, particularly good 卜·lOwtppm, relative to the 3,4-diethoxy allyl compound-containing liquid. If the amount of the catalyst is larger, the reaction rate is higher, the size of the reactor can be reduced, and the equipment cost can be reduced. In addition, if the amount of the catalyst is less, the cost of the ligand can be reduced. 97117793 37 200909411 The molar ratio of the phosphorus atom in the ligand of the ligand of the ligand is preferably 〇1 to 1〇〇〇, more preferably 1 to 100, and more preferably 1 to the transition metal in the complex catalyst. ~10. The more the amount of the ligand, the higher the reaction rate. On the other hand, the smaller the amount of the ligand, the lower the catalyst cost. The reaction temperature at the time of the isomerization reaction is preferably 4 〇~2〇{rc, f 8 (M8(TC, Tejia 1{)) (M6 (rc. The higher the reaction temperature, the more the anti-shore f degree rises) and the reactor can be reduced, so it can be reduced Equipment cost. Another f touch 2 The lower the reaction temperature, the slower the deterioration of the catalyst is, so it can be reduced. In addition to the upper ligand, other phosphorus compounds can also be used as an auxiliary catalyst, thereby enhancing the touch. The stability of the medium or the reaction rate. The phosphorus compound used herein is not particularly limited as long as it is bonded to the phosphorus atom. Preferably, it is triphenylphosphine or tris(2). a triarylphosphine such as a phosphine, a tris(4-methylphenyl)phosphine, a tris(2-methoxyphenyl) lin or a tris(4-f oxyphenyl)phosphine; M-lin, diphenylethylphosphine, phenylpropylphosphine, etc. m-phosphine; dimethyldiphosphine: diphenylphosphine, etc., dialkylarylphosphine, trioctylphosphine, dibutyl a trialkylphosphine of a diphosphine or the like; more preferably a triphenylphosphine, a trisphosphine, a phenyl group, a tris(2-methoxybenzene:) scale A = a methyl group), a base, a base) a triarylphosphine such as a phosphine; particularly preferably a triphenyl phenyl group. The amount of other phosphorus compound other than the auxiliary catalyst other than the ligand is a molar ratio of the molar ratio of the compound to the compound ^ The amount of metal to be transferred is H0 , _, compared to ... just, especially good 5 〇: = too little amount of phosphorus compound, the reaction speed is reduced 'too much to increase the cost. 97117793 38 200909411 If this range is ', then you can use a combination of multiple disc compounds. The chemical substance's can be mixed with the shape used in the reaction of the isomerization reaction in the month of the moon, and the like is the same as the tube type reactor, the trough type reaction and the multi-stage: :: in use. The special tank type reactor is a reactor. It is preferably a multi-stage tank type in which an open-disc tray is provided. In the present invention, the q1 medium is isomerized to 4' ethoxylated allylate. The base compound is contacted with the dish compound by the contact of the ^,4-diethyloxyallyl compound. Squamous: "," organic " ^ compound, the organophosphorus compound, more preferably the right (four) acid, organic sulfonamide, organic phosphine, particularly preferred are:: class. The organic phosphine can be The mono-ligand, the double-coordination: preferably the above-mentioned organophosphine, preferably a mono-coordinated phosphine having two or more aryl groups. These are not particularly limited, and the use of the city:: a phosphine, a dipyridyl ketone, a tributyl linyl, a triamyl hexyl hexanyl; a diheptylphosphine, a trioctylphosphine, a tricyclopentylphosphine, a tricyclic ring; a phosphine; or a triphenyl group; Phosphine, diphenyl: A: base stray: # phosphine, diphenylbutylphosphine, dimethylphenylphosphine, dimo-butylphenylphosphine, cis (tolyl) phosphine, 1,2-bis (diyl) ) phenyl phosphine, etc.; more preferably phenyl phosphine, the special material: fluorene toluene diphenylmethylphosphine, diphenylethylphosphine 'diphenyl butyl bis (methyl) phosphine, take It is preferably triphenylphosphine. A compound of one kind of dish is used. However, two or more types may be used in combination: and: 97117793 39 200909411 may be used in combination with other compounds as long as it does not significantly impair the effects of the present invention. The temperature at which the 3,4-diethoxy allylic compound is contacted with the phosphorus compound before isomerization to the 1,4-diethoxy allylic compound by a catalyst, usually 60. The above is preferably 80 〇C or more, and particularly preferably 1 〇{rc or more. On the other hand, the temperature at which the phosphorus compound is normally contacted is generally two or less. The higher the temperature, the higher the inhibitory effect of the catalyst degradation component of the scaly compound. Further, the lower the temperature, the lower the energy cost for heating the phosphorus compound. Further, the contact time is preferably 丨 minute to 1 〇〇 hour, ～10 hour, and particularly preferably 30 minutes to 5 hours. The more complete the removal of the contact time, the more the components can be removed. Moreover, the operational efficiency of contact = becomes high. Table column::; dish ί system relative to Μdiethyl ethoxy allylate

The substance 3 has a liquid, and may be used in a weight % of 0 000 H I, more preferably 0.0001 to 1% by weight. The target range of the / η ηηι Λ / / ° is particularly preferably 0·001 to 0.1% by weight. The more the phosphating δ is used, the more it can be obtained. Another artifact + removes the effects of catalyst degradation. On the other hand, the cost of using the phosphorus compound is the cost. Use less in the right and right to reduce the wall. In the present invention, as a 3 r female ώ mu &, a fluorenylallyl compound by a catalyst, is a diacetoxy allylic compound Previously, a method of contacting a base compound with a phosphorus compound, and a propyl compound and a scale compound were placed in (4). The ruthenium 3,4-diethyloxy group was diluted into a trough, and the mixture was stirred and mixed 97117793. 200909411 method; (2) additionally preparing a solution containing a compound compound of a phosphorus compound, and 3,4-diethyloxy group of 3,4-diethylenedi-=oxypropylate compound In the method of mixing and mixing, the solution of the container solution is separately prepared as a flowing liquid, and each of the methods is prepared by bubbling and mixing the mixture with a solution. Also == integrated into one pipe. Hunting is carried out by the above required temperature and time. From the point, r, preferably a continuous process, as a method of contacting, the 3,4-diethyloxyallyl compound can be contained in the (3) diethyl ethoxyallyl compound solution. Divided into: D, 3, 4, a pipeline (pipe) integrated into a variety of phosphorus compounds and 3,4-diacetate oxygen m / /, contact this combination. It can be either divided or continuous, and the contact method of the soil compound is continuous flow. Weaving: In terms of matter, it is particularly good, different =: after the bundle, and the composition of the catalyst is two. From the diethylene glycol minus the propyl compound, the dish compound can be recovered by the steaming u- / knife, but - From this, outside the system. Further, it is discharged as a waste liquid to the reaction liquid which is produced by the isomerization reaction, and in addition to the unreacted reaction of the diethyl compound, there is a separation of the compound by steaming or the like. The reaction liquid U-B-based gas-based propyl compound contains 97117793 200909411 ί, system:: the pressure of the tower can be arbitrarily set 'but in order to reduce the temperature of the bottom of the tower, the top pressure of the tower is set to be 76 〇 pressure is 5 , 0_g, especially good 1 (Μ - more == = over two: Τ maintain pressure requires a large cost, and two = large, and θ plus process construction costs. In addition, the bottom temperature of the tower top pressure distillation tower Change the ancient α ^ 5 Λ η η ηη〇Γ ά back and increase the rolling cost. The temperature at the top of the tower is usually 〇 ~ 200 C, preferably 2 〇 ~ 16 〇 t, better 4 〇 ~ i4 (rc 2 top f If the degree is low, a special device such as a cooler is required, so that the cost is deteriorated and the I:::over direction is applied. Since the temperature at the bottom of the column also becomes a higher temperature, the steaming is increased. The reflux ratio may be (10), preferably.卜1〇. If the amount of return: force: lead to deterioration 'if the reflux ratio is too high' then the required thermal conductivity 22 = cause. The amount of the top of the tower, preferably tied to B: In the liquid of the ethoxylated allyl compound, the 1,4- 虱 decylallyl compound, and the low-boiling substance, the compound is made up of 3 4_1, (4) by: negative and... People call for; "quote propyl compound and light boiling point oxymethene: if, in the case of self-flowing 3,4-diethyl guanidine, it is better to introduce the liquid into the liquid: =:=The content of the species, from the sidestream crane, so that: liquid; == the content of the species from the tower of the 1 point

The q 4_ - 7 X liquid obtained by distillation separation is introduced into the lyophile-based propyl compound containing .# /, and the unreacted 3 4_-

The ethylenyl allylate compound is isomerized to a u-divinyl comb I compound. Recycled to the 3,4-diethyloxypropyl propyl group of this reactor; 97137793 42 200909411 =11: The temperature or the like at the time of separation by the steaming crane is maintained, depending on the degree, but no recycling At the same time, the temperature and pressure are subjected to isomerization to a u-diethyloxypropylpropyl compound. Again, the condition of this neck s. The isomerization reaction condition of τ may be the same system m!:: 1,4-diethyl fluorenyl propyl compound, in the presence of =, step by step steaming, etc., after purification, in transition metal catalyst Save, enter the ” line" can also be replaced with a substituent, 4_ diethoxy butyl butyl compound. This is the commercial hydrogenation catalyst, the household is into the right 4 bucket" and metal touch The medium may be a catalyst of generally 3 precious metals such as palladium or rhodium, =. : In the presence of such a hydrogenation catalyst, the contact at time two is usually (four) (four); = I is that the catalyst deteriorates rapidly, and if the reaction: the degree: the inverse 5 ==== is too low, the reaction rate is lowered. If the pressure is too high, it will be expensive. The diethyl hydrazine obtained by the hydrogenation reaction is used as a catalyst, which is preferably a solid acid catalyst, and the use of the W sub-parent for the resin is used, because the hydrolysis rate is faster, and the furan-like by-product is less, so Suitable for. Specifically, in order to use a copolymer of stupid ethylene::vinylidene as a precursor, the sulfonic acid type is replaced by a resin, and may be a gel type or a porous type - and a sub-parent 30 to 11 ( The temperature L reaction of TC, preferably 40~赃 is usually 卞13,000 yoke. If the temperature is too low, 97117793 43 200909411 (4) The solution speed is reduced, requiring an expensive and bulky reactor. If the temperature is too south, then the four humming When the by-products are increased, the yield of 1>4-butanediol is lowered. The water-based group is usually 2 to 100 moles, preferably 4 to 50 moles, relative to u-diethyloxybutanol. The amount of the range of the ear. If the amount of water is too small, the reaction rate is lowered, and an expensive and bulky reactor is required. Moreover, if the amount of water is hydrolyzed and the water is removed from the U-butanediol, the energy required is increased. (Embodiment) The present invention will be described in more detail by way of Y', but without departing from the present invention, it is not limited to the following examples. One of the following examples, 3, Analysis of 4-diethyloxy-1-butene and 1,4--ethoxy-2-butene by internal standard method The bulk acoustic analysis method was carried out. Dodecane was used as the internal standard material. "Multiple test cases 1 · Ding Yi diacetate ethoxylation reaction step in the presence of Pd Te catalyst ikg to make butadiene oxime. 21kg /hr, oxalic acid 2.94kg/hr, 6v〇_/94v〇1% nitrogen mixed gas 〇 is /^ 二内丨! Through '*8rc, 6MPa conditions for acetic acid oxylation one μ in 丨J 3 L-diethoxycarbonyl-2-butene 81% by weight, 3 4 diethoxy nonoxybutene 9 wt%, 3-hydroxy-4-ethenyloxy+1: alkenyl 2, acetic acid 3 wt% And a mixture of other light-boiling compounds, 3% by weight, and Nanfo point compound, 2% by weight. Multi-test 2. 3, 4-diethyloxy-1 - butene-containing liquid separation from test example 1 The mixed liquid 11L is separated by continuous steaming to separate the 3 4 - ethyl hydrazine-based 4-butene-containing liquid. Further, in the distillation, the 20-stage 97117793 44 200909411 is used.

Oldershaw steamed the tower. Maintain a temperature range of 2〇_Hg at the top of the column, a reflux ratio of 3, a top temperature of 95 C, and a bottom temperature of 151 °C. Continuously at the position of the first stage from the bottom of the tower at a flow rate of 150 cc/hr. The introduction was carried out continuously from the top of the column at 27 cc/hr, and continuously withdrawn from the bottom of the column at i23 cc/hr. By this continuous distillation, a liquid containing hydrazine, 4-diethoxycarbonyl-2-butene is obtained as a bottom liquid from the bottom of the column, and 3,4-diethyloxy-1-butene is obtained from the top of the column. The liquid is contained as a distillate. The obtained 3,4-diethoxymethoxy-butene-containing liquid system contains 3,4-diethyloxy-indene-butene 45 wt%, 3-hydroxy-4-ethenyloxy-1. Butene n% by weight, acetic acid & wt%, other components having a lower boiling point than 3,4-diacetoxyoxy-butene, 2% by weight, and a higher boiling point than 3,4-ethyloxy-butene A mixture of 2% by weight of the ingredients. Further, the content of the 3,4-diethyloxy+butene-containing liquid is preferably 1% by weight or less.

The purified 3,4-oxyl-1-butene-containing liquid is more than a portion of the light-boiling compound. x, in steaming, use 4 stages of ldershaw steaming (four). Material lOOmmHg, reflux ratio!, topping, θ sore king is 1〇η / tower top brewing 95C, tower bottom temperature 148χ: 2 / The degree of the dish is continuously introduced from the bottom of the tower according to the flow rate of 100Cc/hr, and is connected at the top of the tower at 41cc/hr.

5 wide continuous extraction. By this continuous distillation, (iv) top; two-phase compounds as (four) liquid. The amount of the 3,4-diethyl-K phase of the I-diethylene-oxyl+butadiene 16 H(10)59 heavy distillation column is 15 weight (10), 97117793 45 200909411 ^, which is introduced into the amount of the steam-ethyl lactyl (tetra)-based compound. / = Compared with 3, 4_-ethoxycarbonyl - I-butene low composition 39. 4 weight 'transfer f'j from the bottom of the liquid containing 3,4_diethyloxy + butyl, — 72% by weight, 3-hydroxy_4_ethyloxy_丨-butene μ% by weight, other euthanasia/Focus compound 6% by weight, high-boiling compound 4% by weight of 3, 4-diethyl醯oxy-丨-butene containing liquid. Reference Example 4: The catalyst was prepared under a nitrogen atmosphere, and 10.5 mg of palladium acetate was used in a glass Schlenk flask, and the phosphite ligand represented by the above L21 was 96.31 Å, diphenylphosphine 49.8. The hydrazine was added to the 3,4-diethyloxy-1-butene-containing liquid 41.3 § obtained in Reference Example 3. The mixture was heated for 1 hour to obtain a completely dissolved catalyst solution.邺 三 邺 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 56 Add to 13.13 g of toluene. 5mg,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, 8 mg of the ligand represented by the above L30 and triphenylphosphine 25.10 mg were added to 12.19 g of toluene. The mixture was heated at uot: for 2 minutes to obtain a completely dissolved catalyst liquid. Example 1) 3,4-diethyloxy-1-butene-containing liquid obtained by the above-mentioned Reference Example 3 "Purification distillation of 3,4 -ethyloxy-1-butane-containing liquid" (3) , 4-二97117793 46 200909411 Li Dingfu 72% by weight, 3-ionyl- 4-ethyl oxy-butane + hexanthene; V he has a boiling point of 3, [diethyl decyloxy + butene low component b罝%,; 佛点轻q羞-, a ethoxylated butene high component 4 weight / purified 3,4 ~ diacetyl children 7 , lactyl butene) 1 · 5cc, three Phenylphosphine. 〇; (10) (relative to 3,4 diethyl ethoxylate + butene is 73 weight / made a phenyl shame concentration 〇 · 86% acetic acid solution 18 # L and added, to 15CTC The temperature was stirred for 3 hours. Secondly, 15 cc of acetic acid was added. The mixture was mixed into a Schlenk apparatus and heated to 13 (TC) by an oil bath. Here, the catalyst liquid 26 / L prepared in Reference Example 4 was added under a nitrogen atmosphere, and heated at 13 CTC for 3 hours (reaction liquid The palladium concentration in the medium is 1.0 wtppm. The liquid after the isomerization reaction is analyzed by the gas layer-analysis method, and the result is 1,4-diethoxycarbonyl-2-butene (the total of the cis-form and the trans-form) And the weight ratio of 3, 4-diethoxymethoxy-indene-butene is 45: 55. Further, dodecane is used as an internal standard substance. The result (Example 2) is in Example 1, except The addition was carried out in the same manner as in Example 1 except that the amount of triphenylphosphine added was changed to 332332 mg (147% by weight based on 3,4-diethyloxy-1-butene). After the isomerization reaction, the liquid I was analyzed by gas chromatography, and the result was 1,4-diacetoxy 2 -butyral (complex, trans-complex) and 3, 4-diethyloxy- The weight ratio of 丨-丁妇 was 44: 56. Further, dodecane was used as the internal standard substance. = The results are shown in Table 1. '(Example 3) In Example 1, except that the three stupid bases were added After the phosphine is disturbed at 15〇 97117793 47 200909411 The reaction was carried out in the same manner as in Example 1 except that the temperature was C for 1 hour. The liquid after the isomerization reaction was analyzed by gas chromatography, and the result was 1,4-diethoxycarbonyl-2. The weight ratio of butene (total of cis, trans isomer) to 3,4-diethyloxyl-1-butene was 44: 56. Further, dodecane was used as an internal standard substance. The results are shown in Table 1. (Example 4) In Example 1, except that 166 mg of triphenylphosphine was added (0.0073% by weight based on 3,4-diethyloxy-1-butene) at 30 ° C The stirring was carried out for 5 hours at the same temperature, and the rest was carried out in the same manner as in Example 1. The liquid after the reaction was analyzed by gas chromatography, and the result was 1,4-diethoxycarbonyl-2-butene (the total of the cis, trans, and 3,4-diethyloxy-1). The weight ratio of butene is 40:6〇. Also, dodecane was used as an internal standard substance. The results are shown in Table 1. (Example 5) In the first embodiment, except that triphenylphosphine was changed to triphenylphosphoric acid, the amount of triphenylphosphoric acid added was changed to 〇166 mg (relative to 3 4 diethoxymethoxy group). The same procedure as in the Example was carried out except that 1-butene was hydrazine and 0073% by weight. The liquid after the isomerization reaction was analyzed by gas chromatography, and as a result, 1,4-diacetoxy 2 -butylene (the total of the cis, trans, and 3,4-diethyleneoxy)- The weight ratio of butene is %: ^. Also, dodecane was used as an internal standard substance. The results are shown in Table ^. (Example 6) Pure 3'4-ethyleneoxy-oxime-butene-containing liquid of the 3,3,2-diethoxymethoxy-1-butene-containing liquid obtained by the above-mentioned reference exemplified distillation 3, 4 - 2 9717793 48 200909411 Ethyloxy-1-butene 72% by weight, 3-hydroxy-4-ethenyloxy-1-butene 18 heavy!_/, other boiling points are more than 3, 4 - two Ethyloxy_ι_ butene low content of 6 wt%, a higher boiling point than 3,4-diethyloxy-indene-butene, 4 parts by weight of 0/〇, purified 3,4-diethoxycarbonyl -1-butene) 2.94 (^, the triphenylphosphine 0.1511^ (relative to 3,4-diethyloxy-1-butene is 〇.〇〇5〇% by weight) as diphenylphosphine After the concentration of 0 86% acetic acid solution was added, the mixture was stirred at a temperature of 1501 for 3 hours. Next, 0.06 cc of acetic acid was added and mixed into a Schlenk apparatus, and the temperature was raised to 130 C by an oil bath. Here, in a nitrogen atmosphere. The contact prepared in Reference Example 5 was added, and the liquid was 18//L, and the mixture was heated and stirred at 130 ° C for 3 hours (palladium in the reaction liquid) 1 Owtppm. The liquid after the isomerization reaction was passed through the gas layer. Analysis by analysis, the result is 1,4-diethoxyoxybutene (cis, trans) The weight ratio of the total) to 3,4-diethyloxy-ι-butene was 49: 53. Further, dodecane was used as the internal standard material. The results are shown in Table 2. (Example 7) Example 3 "3,4-diethyl gfoxy-p-alkene-containing purified 瘵 stuffing" 3, 4-diethoxy-anthracene-butene-containing solution (3,4-diethyl hydrazine) 72% by weight of oxy+butene, 18% by weight of 3-carbyl+ethenyloxy+butene, 6 parts% by weight of other components of m4_diethoxycarbonyl+butene, and a boiling point of 3, 4 1-2 ethoxylated butyl butyl sulphate high content 4% by weight of purified 3,4_diethoxycarbonyl + butene) 2 94cc, triphenyl sulfonium. 15mg (^ mesh for 3, 4 - Diethyloxyl + butene is 〇〇〇 5 〇 by weight) 8" of an acetic acid solution having a triphenylphosphine concentration of 8686% is added and then stirred at 15 (TC temperature for 3 hours). 97117793 49 200909411 Next, the acetic acid 0. 06cc was added and mixed into the Schlenk, and the temperature was raised to 130 ° C by the oil bath. Here, the catalyst liquid prepared in Reference Example 6 was added at a rate of 18 // L under a nitrogen atmosphere. Heated at 13 0 °C for 4 hours (in the reaction solution Palladium concentration 1. Owtppm). The liquid after isomerization reaction was analyzed by gas chromatography, and the result was 1,4-diethoxycarbonyl-2-butene (cis, trans-comp. § 10) The weight ratio to 3,4-diethyloxy-1-butene was 52: 48. Further, dodecane was used as an internal standard material. The results are shown in Table 2. (Comparative Example 1) In addition to the substitution of triphenylphosphine, an anion exchange resin (Diaion, WA20) 7.8 mg (relative to 3,4-diethyloxy-1-butene) is 0. The 50% by weight of '% is equivalent to the two bases. The Q2% by weight of the amine exchange capacity) was carried out in the same manner as in Example 1 except that the mixture was stirred at a temperature of 30 ° C for 1 hour. The liquid after the reaction was analyzed by gas chromatography, and as a result, 1,4-diethoxycarbonyl-2-butene (complex of cis, trans, and 3, 4-diethyloxyl-1) The weight ratio of butene is: 7〇. Also, dodecane was used as an internal standard substance. The results are shown in Table 1. (Comparative Example 2) In Example 1, an anion exchange resin (Diaion, WA20) was added in addition to the substitution of triphenylphosphine (38. 9 mg (relative to 3, 4-diethyloxy-butene). The weight %' corresponds to the amine exchange capacity of 1% by weight of triphenylphosphine ruthenium), and the same as in Example 1 except that the mixture was stirred for 1 hour at a temperature of 30 ° C. The liquid after the reaction was borrowed. Analysis by gas chromatography, the result is a weight ratio of 1,4-diethoxycarbonyl-2-butene (complex of cis, trans) to 3,4-diethyloxy-1-butene 33: 67. Further, the use of 9717793 50 200909411 was used as the internal standard substance. The results are shown in Table 1. (Comparative Example 3) = Reference Example 3 above, "3, 4-diethyloxy-1-butene 3, 4-diethyloxy-1-butane-containing solution (3,4-diethyloxyl-1-butene 72% by weight, 3-hydroxy-4) obtained by purifying and purifying the olefin-containing liquid _Ethyloxy-I-butene 18% by weight, other components having a lower boiling point than hexamethyleneoxy-butene, 6 wt%, and a boiling point lower than 3,4-diethoxycarbonyl- 1-butene high component 4% by weight, '屯化3,4~ In the 0cc, the acetic acid wide 0_06cc was added and mixed into the Schlenk apparatus, and the temperature was raised to 13〇 by the oil bath. Here, the reference example 5 was added under a nitrogen atmosphere. The prepared catalyst liquid 18 / L, ' 〇 ^ was heated and mixed for 3 hours (concentration of 1. Owtppm in the reaction liquid). The liquid after the isomerization reaction was analyzed by gas chromatography, and the result was 1. The weight ratio of 4-diethoxycarbonyl_2_butene (the total of cis, trans isomer) to 3,4-ethoxycarbonyl-indene-butene is. In addition, eleven-burning is used as the internal standard substance. The results are shown in Table 2. (Comparative Example 4) V = the above-mentioned Reference Example 3 "Purified Lamb of 3,4-Diethyloxy-1-butene-containing liquid," known as 3, 4 to 2醯oxy-butene-containing liquid (3,4_bis' oxo 1 butene 72% by weight, 3-hydroxy-4-ethenyloxy-1-butene. 18 heavy denier %, other boiling point car 3,4-diethyloxy+butene low component 6 wt%, Buddha point 3 / comparative 4~diethoxy-1-butene high component 4 weight•% purification 3 4 - 2 7 μ & 'air-based-1-butene» 3. 〇cc, add 0 cc ^ of acetic acid to the Schlenk The temperature was raised to 13 passages by the oil bath. The catalyst liquid prepared in Reference Example 6 was added under the conditions of 虱 rolling. 18// L·, 97117793 51 200909411 Heating and stirring at 130 ° C for 3 hours (palladium in the reaction liquid) Concentration i · Owtppm). The liquid after isomerization was analyzed by gas chromatography. 'Results 1,4-diethoxycarbonyl_2_butene (cis, trans total) 3 + The weight ratio of butene is 40: 6〇. Also, the element is an internal standard substance. The results are shown in Table 2 〇97117793 52 200909411 (i than fortunate example 2 anionic cross-fat 38.9 LO 1 hour | 2,2' -Bis[bis(l-na phtoxy)phosph i nyΙο xy]-3,3' ,5,5' -di -tert-butyl-6, &-dimethyl-1, Γ -bip henyl 33: 67 CO Comparative Example 1 Anionic cross-fat: LO CZJ 1 hour 2, 2' -Bis [bis(l-na phtoxy)phosphinylo xy]-3,3',5,5' ~di -tert-butyl-6,6* -dimethyl-1, Γ -bip henyl 30:70 CO LO Example 5 Benzene 0.166 0.0073 g T-丨 - 3 hours 2,2' -Bis[bis〇-na phtoxy)phosphinylo xy]-3,3,,5,5' -tert-butyl-6, & ~ dimethyl-1 , Γ -bip henyl CO to CO 3253 Example 4 Triphenyl fine 0.166 0.0073 Another 5 minutes 2,2' -Bis[bis(l-na phtoxy )phos^ i ny 1 o xy]-3,3',5, 5' >di -tert-butyl-6,6* -dimethyl-1, Γ -bip henyl § 3614 Example 3 Triphenylphosphine 0.166 0. 0073 S 1 1 1 hour 2,2' -Bis[bis( L-na phtoxy)phosphinylo xy]-3,3',5,5' ji -tert-butyl-6,6* -dimethyl-1, Γ -bip henyl 45:55 4066 Example 2 Triphenyl fine: 0.332 0.0147 1_ S Ϊ-^ 3 hours 2,2' -Bis [bis(l-na phtoxy)phosphinylo xy]-3,3',5,5' -tert-butyl-6,-dimethyl-1, Γ -bip henyl ~7\ Mh9\ <L.21J 44:56 1988 丨 - - - - - - - - - - - - - - - - - - -3 45 : 55 4066 Adding force /-"N 1 relative to 3,4-DABE(*l) The amount of σ (wt%) contact temperature (ΐ: contact time isomerization reaction Catalyst ligand base lean S'Capacity ※乇趄S驷^ g >w βQ d ^ ^ bond him CO" relative to additive. 1,4-DABE weight ratio (after isomerization) (4 *S3 , sl0f-l—33-^i : 3ϋ Window) Ib-Ι-315ιο“-κε: 39ναΛίο(Ι8 KU6 200909411 'ft Comparative Example 4 1 1 1 1 I Nl, N3-Dimethyl-Nl, N3- Bis[2,4,8,10-tetrakis(l,l-dimethylethyl)-l, 11-dimethyldibenzo[d, f ][1.3.2]dioxa ftosphepin-6-yl]-l, 3-propanediami ne (L -30) 40:60 1 Comparative Example 3 1 1 ! 1 1 Nl, N3-Dimethyl-Nl, N3-bis[4,8-bis( 1, l-dimethylethyl)-2,10-dimethoxy dibenzo[d, f ][1.3.2]dioxaphosphepi n-6-yl]-l, 3-propanediamine Me° QX )3⁄4 MeO OMe (L-29) 1 Example 7 Triphenyl fine LO CZ5 0.005 S τ-^ 3 hours Nl, N3-Dimethyl-Nl, N3-bis[2,4,8,10-tetrakis(l,l-dimethylethyl)-l, 11-dimethyldibenzo[ d, f][l. 3. 2]dioxa iiiosphepin-6-yl]-l, 3-propanediami ne (La〇) 52: 48 9173 Example 6 Triphenyl fine αα C3 0.005 S 3 hours Nl, N3-Dimethyl -Nl, N3-bis[4,8-bis( 1,1-dimethylethy 1)-2,10-dimethoxy dibenzo[d, f][l. 3.2]dioxaiiiosiiiepi n-6-yl]-l, 3-propanediamine MeO^Xs^ Jy 〇, px /3⁄4 MeO OMe (L-29) 49 : 53 8644 Addition W φΗ 1 is Write surface 53⁄4 $| 要 Contact temperature rc contact time isomerization reaction catalyst ligand +※玉_ $辋'τ' W d ^ ^ Λ 重量 The weight ratio of 1,4-DABE relative to the additive (after isomerization) (+ts3 , -sfi.h—T3«N3?rI — i (st-h-lw^lsto-r-too: 39va-Kco(i) inch $ S6PIU6 200909411 二上,! It can be seen that if the examples and comparative examples are compared, the weight is added to the additive, or For the exchange capacity of the phosphorus and nitrogen atoms in the crowning process, the results of the isomerization reaction were all improved. (Industrial Applicability) t July is a method for isomerization of a propyl compound which inhibits catalyst degradation and obtains an isomer according to a small amount of catalyst usage. on. The specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2007-132184, filed on May 17, 2007, the entire contents of

Claims (1)

200909411 V X. Patent application scope: 1. An isomerization method in which the allylic compound is subjected to isomerization in the presence of a catalyst after contacting the allylic compound of the starting material with the lining compound. % 2. The isomerization method of claim 1, wherein the compound is an organophosphorus compound. 3. For the isomerization process of claim 2, the organophosphorus compound is an organophosphine. 4. The isomerization method of the third aspect of the patent application, the organophosphine system has two or more aryl groups. And the method of isomerization of claim 3 or 4, wherein the above organophosphine is a triphenylphosphine. The secretory method of claim 1, wherein the amount of the scaly compound in contact with the liquid of the compound of the compound is in the range of 〇. In the method of isomerization of the i-th aspect of the patent range, wherein the contact system of the compound containing the compound and the phosphorus compound is ☆ above, the method of isomerization of the item: a step-by-step propyl compound containing a liquid; a step B-based reaction to obtain an upper (four) medium i = 1 of the enthalpy 'where the above-mentioned touch-disc ligand; ^ catalyst, and contains at least - ρ ο 上述 上述 上述 上述 上述 上述 上述 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 971 The group is a bisphosphonate of the bidentate. 11. The isomerization method according to claim 9, wherein the phosphorus ligand having a P-fluorene bond is a bis-coordinate group of Phosphoramidite. 12. The method for isomerization according to the scope of claim 2, wherein the /V allyl compound is a 3,4-diethyloxyallyl compound, which is formed by isomerization and is olefinic The 1,4-diethoxymethoxyallyl compound of the corresponding compound of the base compound. A method for producing a allylic compound, which is a method for isomerization of a compound of the invention, which is an isomerized compound. U 97117793 57 200909411 VII. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. : without 97117793 4