TW200424154A - Isomerization of 2-methyl-3-butenenitrile to linear pentenenitrile - Google Patents

Abstract

Isomerization of 2-methyl-3-butenenitrile to linear pentenenitrile in the presence of a system comprising (a) Ni(0) (b) a trivalent phosphorus-containing compound which complexes Ni(0) as a ligand and c a Lewis acid, which comprises withdrawing a mixture comprising 2-methyl-3-butenenitrile and linear pentenenitrile from the reaction mixture during the isomerization.

Description

200424154 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for isomerizing 2-methylbutene to pentenenitrile in the following system, which includes a) Ni (〇) b ) A compound containing trivalent phosphorus, which is combined with Ni (0) to form a ligand, and c) a Lewis acid, which includes recovering fluorenyl butyronitrile and pentenenitrile from the reaction mixture during isomerization Of a mixture. [Previous technology] Methyl · 3_τenenitrile is formed in the presence of a catalyst, and is formed in a large amount by the hydrocyanation (hydrOCyanati) of dilute to dilute guess (for example, 3-pentenenitrile). by-product. Depending on the catalyst used, the molar ratio of 2-methyl-3_butene to pentenenitrile can be as high as 2: 1. 3__pentenenitrile can be converted into adiponitrile in a large amount in the health industry, and the month itself is an important raw material for preparing polyamides, especially in industrial quantities. Polyamine-6 (nylon · 6) and Polyamide 6,6 (nylon_6,6). : A sample of 2 · methyl_3_butenenitrile was used to prepare adiponitrile, and methyl-3-butenenitrile was isomerized to pentenenitrile (especially 3_pentene). : US Pat. No. 3,676,481, paragraph 52, lines 48-50, and examples, describe heating in the presence of memei 1 (), linolenic acid ligand, and some Lewis acids to perform batch isomerization of bis-nitrilenitrile. After isomerization, the product mixture delivered by the same heating is distilled out of the catalytic system. 0: 、 9_ll6.D〇c 200424154 The disadvantage of the husband is the long isomerization time, and the catalysis of 敎 sensitivity during the isomerization is 丨 古 古 #. Sexual beauty 冋, should be in the subsequent Distillation is sensitive to heat and the agent also has high thermal stress. The catalyst has a high content; the desired catalyst reduces the effect. 1. Stress, no ... [Summary of the invention] E: The purpose is to provide a technically simple and economical method capable of isomerizing 2-methyli-butenenitrile to 3-pentanonitrile. It has been found that this purpose can be achieved by the method originally defined. According to the invention, 2-methyl-3-butenenitrile isomerized. Known = a method of preparing 2-methyl-3-butenenitrile or containing 2-methyl "· butanezol and especially a mixture containing pentenenitrile additionally. In addition to the pure 2-methyl-3-butyronitrile compounds, they contain y memet = additional mixtures of daughter-in-law guessing 'can be used for: mentioned in the invention = in the context of the invention, the term 2-methyl 3_ Butenenitrile includes the pure compounds and their mixtures so far. It has been found that it is advantageous to reduce compounds other than 2-methyl_3_butylamine from these mixtures, for example, by distilling the roots-two [perspective methods] According to the present invention, the isomerization is in the The system includes the following steps: a) Ni (O) b) and Ni (0) to synthesize a ligand containing a trivalent phosphorus compound,

O: \ 91 \ 91116.DOC 200424154 0—Lewis acid The damage prevention of the catalytic system containing N1 (0) is known per se, and the object of the present invention can be achieved by methods known per se. Furthermore, the system also contains a compound that is suitable as a Ni (0) ligand and contains at least one trivalent europium, bovine atom, or a mixture of these compounds. In a preferred embodiment, the compound suitable for use as a ligand in +, & A, h J may be a compound of the formula p (x1R1) (xV) (X3R3). In the context of the present invention, the compound It is a single compound or a mixture of different compounds described by the following formula. X1, X2, and X3 may be each independently an oxygen or a single bond. When all the X1, X2, and X3 groups are single bonds, the compound ⑴ is a phosphine of formula P (R R2R3), and R1, R2, and R3 have the definitions as described in the specification. When two groups in X, X, and χ are single bonds and one group is oxygen, compound (I) has the formula ^ OrWr2) ^ 3) or p (Rl) (〇R2) (R3) or P ( R) (R) (OR) is a monobasic phosphonic acid (PhoSphinite), R1, R2 and R3 have the definition as described in the description. When one of X1, X2, and X3 is a single bond and two groups are oxygen, the compound ⑴ is of formula P (〇R1) (〇R2) (R3) or p (r1) (〇r2) (〇 r3) or P (〇Ι ^) (Ι12) (ΟΚ3) phosphonic acid, R1, R2 and R3 have the definition as described in the description. In yet another preferred embodiment, all the X1, X2, and X3 groups should be oxygen, and the compound (I) is advantageously of formula? (〇1 ^) (〇112) (〇113) phosphorous acid, its Ri, O: \ 9l \ 9iiig Doc 200424154 R and R3 have the definition as described in the description. According to the present invention, RUR2 is independently the same or different organic group. R and R are each independently an alkyl group, preferably having from 1 to W carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl Tertiary butyl, aryl groups such as phenyl, o-methylbenzyl, m-tolyl, p-tolyl, 1-naphthyl, 2-naphthyl or hydrocarbyl, preferably having 1 to 20 carbon atoms , Such as u, -diphenol and u, -dinaphthol. R, R, and R may be bonded directly (ie, not individually) via a central phosphorus atom. The R, R and R3 groups are preferably not directly bonded together. In a preferred embodiment, Ri, & 2 and R3 are selected from the group consisting of benzyl, o-tolyl, m-tolyl and p-tolyl. In a particularly preferred embodiment, at most two R1, R2 & R3 groups should be phenyl. In another preferred embodiment, at most two R1, R2 and R3 groups should be o-tolyl. Particularly preferred compounds that can be used are compounds of the formula (o-tolyl-〇) w (m-tolyl-0) x (p-tolyl-0) y (phenyl_0) Z ?, where w, x , Y, z are natural numbers, W + X + y + z = 3 and W, Z are less than or equal to 2, for example (p-tolyl-0) (phenyl) 2P, (m-phenylphenyl_〇) (Phenyl) 2p, (o-tolyl_〇) (phenyl) 2P, (m-tolyl-0) 2 (phenyl) P, (o-tolyl_〇) 2 (phenyl) p, (m-fluorene) Phenyl-0) (p-phenylphenyl) p, (o-tolyl_〇K p-tolyl-〇) (phenyl) P, (o-tolyl_〇) (m-tolyl-〇octaphenyl) ) Ρ, (p-phenylphenyl-0) 3P, (m-phenylphenyl-0) (p-tolyl-0) 2ρ, (o-tolyl-0) O: \ 91 \ 91116.DOC -10- 200424154 (p-phenylphenyl-0) 2 P, (m-phenylphenyl-〇) 2 (p-phenylphenyl-〇) p, (o-tolyl'〇) 2 (p-phenylphenyl- 0) P, ( O-fphenyl-〇) (m-phenylphenyl_〇) (p-tolyl-0) p, (m-tolyl-0) 3P, (o-tolyl_〇) (m-tolyl_〇) 21 >, (O-tolyl-〇) 2 (m-tolyl-〇) P or a mixture of these compounds, for example, containing (m-tolyl_0) 3 p, (M-tolyl is called (p-tolyl_0) p (m-tolyl-0) (p-tolyl_0) 2? And (p-tolyl_〇) 3 P 'mixture can be obtained from crude oil The mixture processed by the branch can be obtained by reacting the mixture containing meta-parallax and para-pan (especially 2: 1), and tridentate (H_trihalide). §Hai Si compound and its preparation are already in themselves In another preferred embodiment, the compound of human A, I 6 as a Ni (0) ligand may be a compound of the formula R11-X11 R12-X12 X21-R21 /

ρ · X13-Y-X23. P f X22 R22 where X11, X12, X13, X21, X22 23

Rll and r12 are independently oxygen or single bond, each independently is the same or different, individual or bridged organic group, R2 > R22 are each independently the same or different, individual or bridged organic group, Υ , Is a bridging group.

O: \ 91 \ 91116.DOC -11-200424154 = In the text, the compound is a single compound or a mixture of different compounds described by the following formula. In a preferred embodiment, χΐΐ

X

X, X21, χ22, and χ23 may each be oxygen. In this case, the bridging group is bonded to the phosphite group. In another preferred embodiment, χ and χ12 may each be oxygen and χΐ3 is a single bond, or X " and X13 are oxygen and _ u ',, and are early bonds, so they are surrounded by X11, χ12, and χ13. The stilbene atom is a ν22 2λ family fluorene atom in phosphonic acid. In this case, χ21, may be oxygen 'or χ21, χ22 may each be oxygen and X, a single bond, two X and m are oxygen and χ22 is a single bond, or χ23 may be oxygen and χ2ΐ and m ,, Or χ21 may be oxygen and χ22 and χ23 are each-single bonds, 3 χ and χ may be single bonds, so the phosphorogen + surrounded by X21, X22, and X23 may be phosphorous acid, phosphonic acid, and -monophosphine The central atom of the acid or phosphine is preferably a phosphonic acid. In another preferred embodiment, 'X13 may be oxygen and each is a single bond, may be oxygen and χ12 and χ13 are each a single bond, so the phosphorus atom surrounded by ^, X12 and X13' is a phosphine Central atom of acid. In this case, X, X, and X23 may each be oxygen, or 乂 23 may be oxygen and χ2ι, χυ are a single bond, or X21 is oxygen and X22 and X23 are each a single bond, or X23 may be oxygen and X21 and X22 are each a single bond, or are oxygen and X22 and X23 are each a single bond, or X21, X22, and X23 can each be a single bond, so the phosphorus atom surrounded by X2, X22, and X can be The central atom of phosphorous acid, monophosphonic acid or phosphine is preferably monophosphonic acid. In another preferred embodiment, χΠ, χ12 & χ13 may each be a single bond, so the filling atom surrounded by X " is the central atom of Lin.

O: \ 91 \ 91116.DOC -12- 200424154 In this case, X22 and X23 can each be oxygen or χ11, X22 and X23 can each be a single bond, and therefore are phosphorus atoms surrounded by X2, X22 and X23 , Can be the central atom of phosphinic acid or phosphine, preferably phosphine. The bridging group Υ is preferably a substituted aryl group, for example, substituted by a q_C4-alkyl picture element (such as fluorine, chlorine, molybdenum), a halogenated alkyl group (such as tridecylfluorenyl), and an aryl group (such as aryl). 'Or an unsubstituted aryl group, preferably an aromatic group having from 6 to 10 carbon atoms, especially catechol (Cyclobutadiene, Bipan, or Dinaphthyl. The 11 and R groups may be independent of each other Are the same or different organic radicals. Advantageous K and K radicals are square radicals, preferably unsubstituted, mono- or poly-substituted with 6 to 1 () carbon atoms, especially via C1_C4_alkyl , Pixels (such as fluorine, gas, bromine), dentified alkyl (such as trifluoromethyl), aryl (such as phenyl), or unsubstituted aryl groups. ^ 21 and R22 groups can each μ Shu Li is the same or different organic groups. Advantageous R21 and R22 groups are aryl groups, preferably unsubstituted, mono- or poly-substituted with ... box carbon atoms, especially via C1_C4_ Element (such as appearance, chlorine, bromine), alkylated (such as trifluoromethyl), aryl (such as benzene unsubstituted aryl group. / R11 and R12 groups can be separated or bridged separately. R21 And R22 groups can be separated or bridged.

R

The methods of R, R21 and R22 based closable cord numbers can be separated separately, two can be separated and two bridges can be connected, or all four bridges can be connected. In a particularly preferred embodiment, the AA people,

The compounds used are those described in US 5,723,64i], ","!, And ...

O: \ 91 \ 91116.DOC -13- 200424154 In the 4-inch example, the compounds used are those described in still 5,512,696, especially the formulas used in Examples 1 to 31. , IV, V, VI and VII compounds.

In a particularly preferred embodiment, the compounds used are those described in US 5,821,378, in particular the formulae 1, 11, 111, IV, V, VI, νπ, VIII used in Examples 1 to 73 , IX, XV compounds. X, XI, XΠ, XIII, XIV and in a particularly preferred embodiment, the compounds used are those described in US 5,512,695, especially the formulae used in Examples 1 to 6; [, π, Π, IV, V and VI compounds. In particularly preferred embodiments, the compounds used are those described in Still 5,981,772, and in particular Formula 1 used in Examples 1 to 66 thereof] [1, 111, IV, V, VI, VII , Vm, Ιχ, χ, χι, χπ, Gamma, and Liao compounds. In a particularly preferred embodiment, the compounds used are those described in still 6,127,567, and used in Examples 1 to 29 thereof. In a particularly preferred embodiment, the compounds used are those described in 6,002,516, in particular the formulae 1, 11, 111, IV, V, VI used in Examples 1 to 33 , VII, VIII, Ιχ & χ compounds. In a particularly preferred embodiment, the compounds used are those described in US 5,959,135, and the compounds used in its examples. In a particularly preferred embodiment, the compounds used are those compounds of formula I, IIIAII described in still 5,847,191. These are described in US, 5, 6, 7, 8, 9, and in a particularly preferred embodiment, the compound 5,523,453 'is used, especially one of formulas 1, 2, 3, 4

O: \ 91 \ 91116.DOC -14- 200424154 10 11 12, 13, 14, 15, 16, 17, 18, 19, 20 and 21 compounds. In the special μ conjugate example, the compounds used are those described in WO 01/14392, preferably among the formulas v, VI, m, νιι, X,

XVI1, XXI, XXII, XXIII XI, XII, XIII, XIV, XV, XVI, compounds. In particularly preferred embodiments, the compounds used are those described in WO 98/27054. In a particularly preferred embodiment, the compounds used are those described in Che 99/13983. The compounds used in the particularly preferred embodiments are those described in Touch 99/64155. The compounds used in a particularly preferred embodiment are those described in German Patent Publication DE 1003 8037. In a particularly preferred embodiment, the compounds used are those described in German Published Specification DE 104 0625. These compounds and their preparation are known per se. In another preferred embodiment, mixtures suitable for use as Ni (0) ligands and containing one or more of the following compounds, and suitable for use as Ni (〇) ligands and containing two phosphorus atoms can be applied. One or more compounds. … In the implementation of the Xiajia, the system used is described in the international patent application PCT / EP02 / 07888 and contains Ni (〇) and the mixed character D. In addition, the system contains a Lewis acid. In the context of the present invention, the Lewis acid may be a single Lewis acid or a mixture of multiple Lewis acids, such as two, three or four Lewis acids.

O: \ 91 \ 91116.DOC -15- 200424154 The Lewis acid used may be an inorganic or organometallic compound, wherein the cation is selected from the group consisting of sharp, titanium, vanadium, chromium, magnesium, iron, cobalt, copper, zinc, boron, A group consisting of aluminum, metals, rhenium, niobium, molybdenum, cadmium, baht, and tin. For example, as described in US 6,127,567, US 6,1 71,996, and US 6,380,421,

Including ZnBr2, Znl2, ZnCl2, ZnSO4, CuCl2, CuC, Cu (03SCF3) 2, CoC12, CoI2, Fel2, FeCl3, FeCl2, FeCl2 (THF) 2, TiCl4 (THF) 2, TiCl4, TiCl3, ClTi (〇 -Isopropyl) 3, MnCl2, ScCl3, A1C13, (C8H17) A1C12, (C8H17) 2A1C1, (iso-C4H9) 2A1C1, (C6H5) 2A1C1, (C6H5) A1C12, ReCl5, ZrCl4, NbCl5, VC13, CrCl2, MoCl5, YC13, CdCl2, LaCl3, Er (03SCF3) 3, Yb (02CCF3) 3, SmCl3, B (C6H5) 3, TaCl5. For example, as described in US 3,496,217, US 3,496,218 and US 4,774,353, metal salts such as CoI2, SnCl2 & organometallic compounds such as raic12, R2A1C1, RSnOsSCF3 and I ^ B, where R is an alkyl group or an aryl group Group. According to us 3,773,809 'promoter used may be a metal in cationic form' is selected from the group consisting of rhetoric, edible, beryllium, aluminum, gallium, indium, indium, titanium, tungsten, thallium, thallium, germanium, Tin, vanadium, niobium, rhenium, chromium, molybdenum, tungsten, magnesium, rhenium, palladium, rhenium, iron, and cobalt, preferably cadmium, titanium, tin, chromium, iron, and cobalt, compounds The anionic group may be selected from halides (such as fluoride, chloride, bromide, and iodide), low-carbon fatty acid anions having 2 to 7 carbon atoms, HPOf, h3P〇2-, CF3CO-, C Hi5〇s〇2 · or s〇 ^ each group of composition. In addition, suitable promoters disclosed in us 3,773,809 are borohydrides, organic borohydrides, and boroesters of the formula RsB and B (〇R) 3, where R is selected from hydrogen and has 6 to 18 carbon atoms. Aryl, via

O: \ 91 \ 91116.DOC -16- 200424154 aromatic groups substituted with alkyl groups of carbon atoms and aryl groups substituted with alkyl groups substituted with cyano groups having from 1 to 7 carbon atoms, advantageous Is triphenyl boron. Furthermore, as described in US 4,874,884, synergistic activities f, 'and 5 of Lewis acids can be used to increase the activity of the catalytic system. Suitable promoters can be selected from the group consisting of cdCl2, FeCl2, ZnCl2, b (C6h5) a (C6H5) 3SnX, wherein X = cF3S03, called ㈣⑽3 or _5) 3. The ratio of electrons to nickel is from about 1:16 to about 50: 1. In the context of the present invention, the term Lewis acid also includes the promoters described in US 3,496,218. US 3,496,218 US 4,774,353. US 4,874,884 US 6,127,567, US 6,171,996 and US 6,38M21. Among the mentioned Lewis acids, particularly preferred are metal salts, and more preferred metal functional compounds 'such as fluorides, chlorides, deserts, iodides, especially chlorides', among which the most preferred are chlorides, chlorides Iron hafnium and iron chloride (HI). According to the invention, isomerization produces pentenenitrile. In the context of the present invention, the term pentenenitrile refers to a single isomer thereof or a mixture of 2 to 4 or 5 different isomers. §Phenenenitrile may be cis-2-pentenenitrile :: 3 transpentenenitrile, 4-pentenenitrile, or a mixture thereof 'preferably cis: dilute :, trans 4-pentamonitrile or a mixture thereof' In particular, the cis-3.pentene compound, Lin or its aging products, whose towels are used as a mixture in the text refers to 3-pentenenitrile. Two crops: Γ = in the presence of a release agent, (such as (e.g. Ethyl, tetra'dimethylcyclohexyl, benzene), such as clams, monolactone, glyme, anisole

O: \ 91 \ 91116.DOC -17- 200424154 (amsole)), for example, esters (such as _r — acetonitrile, acetocyanate) or for example, nitrile canine (such as acetonitrile, benzonitrile (benzonitri) Or a mixture of 5 Haisi dilute swords. In a preferred embodiment, the first use of 哕 hian η is performed without liquid diluent B. It is found that the isomerization is more effective in a non-oxidizing environment. For example, under a protective gas environment of lice or a pure gas (such as argon). According to the present invention, during the isomerization, 2-fyl-3-butenenitrile and pentenenitrile will be contained. The mixture was recovered from the reaction mixture. Not in the-preferred embodiment, a stream containing 2_methyl_3_butyronitrile and pentylene (preferably, from 2 · methyl_3_butenenitrile and pentylene The composition of enenitrile is continuous or quasi ~ (qUasi_eGntinuc) usly). It is relatively continuous when it is used. Dagger 2 Methyl-3-butanenitrile is a continuous or quasi-continuous feed, preferably In a preferred embodiment, the feed stream may have a methyl-3-butenenitrile content ranging from 10 to 100% by weight, It is preferably from 80% to ι00% by weight. In a preferred embodiment, the withdrawal stream may have a 2-methyl-3_butenenitrile content ranging from $ to 80% by weight. It is preferably from 20% to 60% by weight, and the content of pentenenitrile ranges from 20 to 95% by weight, preferably from 40% to 80% by weight, and the additional condition is 2-formaldehyde. The total content of butylenenitrile and pentenenitrile is at most 100% by weight. Advantageously, recovery can be performed by distillation. The steaming device can use conventional devices suitable for this purpose, such as described in Kirk-Othmer, Encyclopedia of Chemical Technology, Article =

O: \ 91 \ 91116.DOC -18- 200424154 edition, Book VII, John Wiley & Sons, New York, 1979, pages 870-881, such as sieve-tray columns, blister plates I-bubble-cap tray columns, distillation columns with structured packing or distillation packing with random packing. Can be recovered directly from the reactor without the need for a stage. The composition of the recycle stream 'the molar ratio of 2-methyl-3-butanenitrile and valeronitrile is determined by the composition of the feed stream, and it can be subjected to the effects of steaming crane temperature, pressure and reflux ratio Adjust in a technically simple way. In the case of using a distillation device as a reaction vessel, the temperature of the isomerization zone (area of the bottom layer) is more preferably at least 0 °, more preferably at least 60 ° C, and preferably at least 1 °. 〇〇. 〇, particularly preferably at least U (rc. In the case of using a distillation device as a reaction vessel, the temperature of the isomerization zone (area of the bottom layer) is more preferably at most 2000, and more favorable It is at most 15CTC, preferably at most 14 °. (:, Particularly preferably at most 13 (Γ (:. In the case of a steam room device as a reaction vessel, the isomerization zone (the area of the bottom layer)) Regional pressure is more preferably at least 5 mbar, more preferably at least 200 mbar, more preferably at least 500 mbar, and particularly preferably at least 600 mbar ( mbar). In the case of using a distillation device as a reaction vessel, the regional pressure of the isomerization zone (the area at the bottom layer) is more preferably up to 10⑻ mbar, and even more preferably up to 95. Millibar (mba0, preferably up to 9㈧ G (mbar) 'Extremely preferably up to 1000 mbar (mbar). The specific pressure can also be passed by passing inert gas such as nitrogen or gas (degassing) Partial pressure of the nitrile stream with stnpping effect).

O: \ 91 \ 91116.DOC -19- 200424154 The stream containing 2-methyl-3-butenenitrile and pentenenitrile recovered from the isomerization can be favorably separated into 2_methyl_ The first stream of 3-butenenitrile, the weight ratio of 2-methyl_3-butenenitrile in this stream should be higher than the heavy summer proportion in the output stream, and the second stream containing pentenenitrile, The weight ratio of pentenenitrile in this stream should be higher than the weight ratio in this recycle stream. The separation action of 30% can be carried out by a separation method known per se, such as distillation, extraction, and crystallization. Distillation is more advantageous. The retort device used may be a conventional device suitable for this purpose, for example, described in Kirk-Othmer, Encyclopedia of Chemical Technology, seventh edition of the younger brother 'john Wiley & Sons, New York, 1979, 87th. On page 881, such as a sieve-tray column, bubble-cap tray coumiums, a steaming column with a normalized packing called ㈣ Ping, or a bulk packing ( random packing). Regarding the weight ratio of 2-methylbutenenitrile of the first stream composition to the weight ratio of pentenenitrile of the mth compound # 1, it depends on the composition of the feed material, which can be obtained through distillation. The temperature, pressure and reflux ratios are adjusted in a technically simple way. In a preferred embodiment, the weight ratio of 2-methyl-3 · butenenitrile in the first stream should be at least 50% by weight, preferably at least weight & and particularly preferably 90% by weight. In the embodiment of the vehicle, the first stream can be fed into the constructive effect of the method according to the present invention, and particularly into the method according to the present invention. The purpose of the invention according to the method of the present invention is astonishing, because the boiling point of 2-methyme _3_butyro-dihydrocarbon is 124 ° C (atmospheric pressure) than the boiling of 3-pentenenitrile

OA91 \ 91116.DOC -20-200424154 point (144 ° C, atmospheric pressure) is low, and in addition, the 3-pentenenitrile obtained in the isomerization can be removed from the mixture by gas phase distillation Of it. Example A 97 g (m / p-tolyl)-(o-isopropylphenyl) nickel phosphite catalyst was charged in a stirred tank. 80 g / h of liquid 2-methyl-3-butenenitrile was continuously added to the catalyst placed in a reactor at a temperature of 130 ° C. Use a vacuum pump to fix the pressure at 750-800 mbar. Using butane = 143, its temperature controller supplies enough energy to remove the 2-fluorenyl-3-butenenitrile ('' 2M3BN '') and 3-pentenenitrile (`` 3PN '') in the gas phase. 80 g / h of nitrile mixture (the relationship between composition and time is shown in Figure 1). The capacity of the reactor was fixed at 225 m. The nitrile was then separated into 2-methyl-3-butenenitrile (upper layer) at atmospheric pressure and 3-pentenenitrile (bottom layer). The mixed composition is depicted in Figure 1. Figure 1 120 η 2M3BN conversion and 3PN selectivity 100 8060400 \ o ^ sf ί + conversion selectivity 20-〇--1 ii ί 1 1 〇50 100 150 200 250 300 Action time (hours) O: \ 91 \ 91116.DOC -21-

Claims (1)

200424154 Patent application ... 1. A method for isomerizing 2-methyl-3 -butenenitrile to pentenyl in the presence of the following system 'This system includes a) Ni (〇) b ) A compound containing trivalent phosphorus, which is co-synthesized with Ni (0) as a ligand, and c) a Lewis acid, which includes the reaction mixture from the reaction mixture during isomerization, which will contain 2-methyl-3 · butene A mixture of nitrile and pentenenitrile is recovered. 2. The method according to item 丨 of the patent application, wherein the isomerization is from 10 to 200. (: Temperature range. 3. The method according to item 丨 of the patent application range, wherein the isomerization is performed at a temperature range from 100 to 150 ° c. 4. A method as described in the patent application range 1 to A method according to any one of 3 items, wherein the isomerization is performed under a pressure range from 5 to 10,000 mbar (mbarw々 pressure). 5. A method as described in any one of claims 1 to 3 A method wherein, during isomerization, a stream containing 2-methyl-3-enenenitrile is added to the reaction mixture, and a stream containing pentenenitrile is recovered from the reaction mixture, and the recycle stream is It has a lower weight ratio of 2_methyl_3_ butyronitrile than the feed stream. 6. A method as in any one of the claims 1 to 3 of the patent application scope, which contains 2_fluorenyl · 3 · τenenitrile and pentenenitrile recovery streams are then separated into the first stream containing 2-methyl-3-butenenitrile. The weight ratio of 2_methyl_3_butyronitrile in this stream should be higher than that in The weight ratio of the output stream, and O: \ 91 \ 91116.DOC 200424154 package, the second stream of valeronitrile, pentenenitrile The weight ratio in this logistics should be higher than the weight ratio in the recycled logistics. 7. If the method of the scope of patent application No. 6 is adopted, where the-logistics system is involved in isomerization. The method according to any one of items i to 3, wherein the obtained pentenenitrile is cis-2 · pentanenitrile, trans-1pentenenitrile, cis_3-pentenenitrile, transpentenenitrile, 4-pentenenitrile Or a mixture thereof. ~ The method according to any of claims 1 to 3 of the patent claim, wherein the pentenenitrile is cis-pentenenitrile, trans-3-pentenenitrile, 4-pentenenitrile or Mixtures: 10. The methods such as = any one of items 1 to 3 in the patent scope, wherein, and hexanitrile are cis-3_pentamonitrile, trans-3-pentenenitrile, or a mixture thereof O: \ 91 \ 91116.DOC 200424154 柒. Designated representative map: (1) The designated representative map in this case is: (none). (II) Brief description of the representative symbols of the components in this map: 捌, if there is a chemical formula in this case, Please disclose the chemical formula that best characterizes the invention: (none) O: \ 91 \ 91116.DOC