TW200530257A - Phosphinite phosphite - Google Patents

Abstract

The invention relates to phosphinite phosphites I of formula 1, 2, 3, 4, 5 or 6 and mixtures thereof, wherein R1, R2, R4 independently represent an alkyl or alkylene group with 1 to 8 carbon atoms, provided that at least one of the groups R1, R2, R4 is different from H; R5 to R22 independently represent H, an alkyl or alkylene group with 1 to 8 carbon atoms; R3 is H, methyl or ethyl; X is F, Cl or CF3, if n = 1 or 2 ; X is H, if n = 0.

Description

200530257 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a novel phosphinic acid phosphite (specifically, a chelated phosphinic acid phosphite) and a preparation method thereof. The present invention further provides its use as a ligand in a transition metal complex, a novel transition metal complex, and a suitable method for its preparation. In addition, the present invention relates to the use of the transition metal complex as a catalyst and a method in which the transition metal complex exists as a catalyst. [Prior art] I know that chelated phosphinic acid phosphite, nickel complexes with these phosphinic acid phosphite ligands, and the use of these complexes as catalysts. US 5,693,843 and 5,523,453 describe a method for hydrocyanating an unsaturated organic compound and isomerizing a nitrile compound in the presence of a complex having integrated linolenic acid and acetic acid as a ligand. There is a need to improve the stability of the chelating phosphinic acid ligands to increase the catalyst's time to production. There is also a need to improve the selectivity of catalysts (for example, 'selectivity to 3-pentenenitrile in chlorination of butane dichloride, or selectivity to adipate in hydrocyanation of 3-pentanonitrile) and Improve space-time yield. SUMMARY OF THE INVENTION An object of the present invention is to provide a phosphinic acid phosphite, which is capable and highly selective to hydrocyanate a technical organic compound. [Embodiment] Phosphonic acid phosphite, which is suitable as a catalyst to make unsaturated with high stability, high reaction, simple and economical way 96784.doc 200530257 I have found that via the following formula 1 or 2 or 3 Or 4 or 5 or 6 phosphinic acid phosphite I and mixtures thereof achieve this objective: Formula 1

R12 R13

formula

R12 R13 96784.doc -10- 200530257

Equation 5

formula

mt R10 in which R1, R2, and R4 are each independently an alkyl group or an alkylene group having 1 to 8 carbon atoms, and the restriction is that at least one of the groups R1, R2, and R4 is not H, and R5 to R22 are each independent Is fluorene, an alkyl or alkylene group having 1 to 8 carbon atoms, R3 is fluorene, methyl or ethyl, 96784.doc -11-200530257 When η is 1 or 2, χ is: ρ, CI * CF3, when η is 0, χ is η. According to the present invention, the R, R, and R 4 groups are each independently an alkyl group or an alkyl group having 2 to 8 carbon atoms, and the limitation is that at least one of the R 1, R 2 and R 4 groups is not Η . When R1 is 氲, R2 may be hydrogen and R4 is an alkyl group or an alkylene group having 1 to 8 carbon atoms, or R2 may be an alkyl group or an alkylene group having 1 to 8 carbon atoms and R4 is a lice Or R2AR4 may be each independently an alkyl group or an alkylene group having from 1 to ^ carbon atoms. When R1 is an alkyl group or an alkylene group having i to 8 carbon atoms, M and Y may each be hydrogen, or R2 (independent of R1) may be an alkyl group or an alkylene group having 1 to 8 carbon atoms. And R4 is hydrogen, or R2 may be hydrogen and Rule 4 (independent of R1) is an alkyl or alkylene group having 1 to 8 carbon atoms, or R2 and R4 may be each independent and independent of R1 as having Alkyl or alkylene groups of 1 to 8 carbon atoms. An alkyl group or an alkylene group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms (especially 1 to 4 carbon atoms), which is advantageously selected from the group consisting of: Fluorenyl, ethyl, n-propyl, isopropyl, n-butyl, first butyl, isobutyl, and third butyl, especially selected from fluorenyl, ethyl, n-propyl, isopropyl, and Tributyl group. According to the invention, R3 is hydrogen or methyl or ethyl. According to the present invention, a benzyl group bonded to a phosphorus atom may be unsubstituted or each phenyl group may independently carry 1 or 2 substituents, and thus 11 may have a value of 0, 1 or 2. The two phenyl groups bonded to the phosphorus atom may be the same or differently substituted, and under different substitution conditions, the difference between the two is related to the number of substituents and the type of the substituent 96784.doc -12-200530257. For the purposes of the present invention, formulae 1, 2 and 3 include the same and different substitutions of a phenyl group bonded to a scale atom. According to the invention, x is F, C1 or CF3, preferably F or CF3. If η is 2,

Then the two groups XI and χ2 can be independently ρ and C ^ cf3, that is,? And! 7, F and c, F and CF3, C1 and c, cmcF3, CF # CF3, preferably F and F, CF3 and CF3. In a preferred embodiment, if 11 is 1 and is 卩, It is useful to substitute a meta atom of a phosphorus atom bonded to a benzene ring in a benzene ring bonded to a phosphorus atom. In another preferred embodiment, if the former is tritium, it is useful to replace the para atom of the phosphorus atom bonded to the benzene ring in the benzene ring bonded to the dish atom. In a preferred embodiment, if 11 is 2 and both magic and 2 are F, it is useful = in the two-preferred embodiment of the disk atom bonded to the benzene ring in the benzene ring bonded to the disk atom, If 11 is 2 and both magic and 2 are CL, the substitution is located at two meta positions of the phosphorus 7 bonded to the benzene ring in the benzene ring bonded to the dish atom. ^ Particularly preferred phosphinates, as defined in Table 1 for Rl, R2. Phosphorous acid S is intended for the respective phosphorous acid phosphorous acid of formula ㈣, R3 and R4 groups, and R18 to R22 groups, respectively.

96784.doc -13 · 200530257

96784.doc 14- 200530257 In this equation, the R1, R2, R3, and R4 groups and the R18 to R22 groups are each defined as follows:

Formula Rl, R18, R19 R2, R16, R21 R3, R15, R22 R4, R17, R20 Ial, Ibl, Icl, Idl, Iel, If 1, Igl, Ihl, Iil5 Ijl Me Me HH Ia2, Ib2, Ic2, Id2 , Ie2, If2, Ig2, Ih2, Ii2, Ij2 Et t-Bu HH Ia3, Ib3, Ic3, Id3, Ie3, Ιβ, Ig3, Ih3, li3, Ij3 i-Pr H Me H Ia4, Ib4, Ic4, Id4, Ie4, If4, Ig4, Ih4, li4, Ij4 t-Bu t-Bu HH Ia5, Ib5, Ic5, Id5, Ie5, If5, Ig5, Ih5, Ii5, Ij5 Et Me HH Ia6, Ib6, Ic6, Id6, Ie6, If6, Ig6, Ih6, Ii6, Ij6 n-Pr Me HH Ia7, Ib7, Ic7, Id7, Ie7, If7, Ig7, Ih7, li7, Ij7 t-Bu Me HH Ia8, Ib8, Ic8, Id8, Ie8, IfB, Ig8, Ih8, Ii8, Ij8 Me H Me Me Ia9, Ib9, Ic9, Id9, Ie9, If9, Ig9, Ih9, Ii9, Ij9 Me t-Bu HH Table 1 Other particularly preferred phosphorous acid phosphites are theirs The formula of phosphinic acid is shown in the formula Ik-Io. Ik

96784.doc 15 200530257 formula to

formula

In Table 1, the abbreviations are defined as follows: Η: hydrogen Me: methyl Et: ethyl n-Pr: n-propyl t-Bu: tertiary butyl In order to prepare phosphinic acid phosphites, the procedure can be in accordance with the United States Patent Nos. 5,523,453 and 5,693,843 and WO 03/62171 for the preparation methods for the phosphorus chelate ligands described therein, for example, by making (Xη · phenyl) (Xn -Phenyl) phosphine chloride reacts with a diol having R1, R2, R + 3, and R4 groups and R15 to R22 groups, and then with phenoxy) (Rn-phenoxy) phosphine chloride . The preparation is efficiently and economically successful from readily available reagents. 96784.doc -16- 200530257 Diphenylphosphine chloride used as a starting compound and its preparation itself are known to us, for example from H. Schindlbauer, Monatshefte Chemie, vol. 96, 1965, pages 1936-1942 . (Χη • phenylphenyl) phosphine chloride can be prepared in a similar manner by the method for preparing fluorophenyl dichlorophosphine described therein. The optimum preparation parameters for a specific (xη-phenyl) (χη-phenyl) phosphine chloride can be easily determined by a few simple preliminary experiments. Phosphite phosphite I can be used as a ligand in transition metal complexes. Beneficial transition metals in this context are metals of the transition groups 丨 to 2 and 6 to 8 of the periodic table, preferably metal elements of transition group 8 of the periodic table, more preferably iron, cobalt and nickel, especially nickel. ^ When nickel is used, it can exhibit different valences, such as 0, +1, +2, +3. In this paper, nickel (0) and nickel (+2) are preferred, especially nickel (〇). In order to prepare a transition metal complex, a compound containing a transition metal or a preferred transition metal can be reacted with a phosphinite phosphite, and the phosphinite phosphite I used can be a separate phosphite Ester "is a mixture of several phosphinic acid phosphites I. Transition metals can be obtained from the appropriate compounds before the reaction, for example by reduction with a test metal (eg, zinc) from a salt such as a chloride. When used When a compound containing a transition metal is used to prepare a transition metal complex, advantageous compounds for this purpose are salts such as gaseous, bromide, acetamylpyruvate, sulfate, and nitrate salts (for example, nickel chloride) (Π)), or a state (0) complex such as bis (1,5-cyclooctadiene) Ni (0). In a compound containing a transition metal or a transition metal and phosphinous acid phosphite After the I reaction, a suitable oxidizing or reducing agent (for example, non-precious metal such as 96784.doc 17 200530257 of zinc, or hydrogen or molecular form of chemically bonded form such as sodium borohydride) can be used, or electrochemically modified The valence of the transition metal in the complex. In a particularly preferred embodiment, the useful reaction is to provide an organic monophosphine, monophosphite, monophosphine, etc. according to the method described in German Patent Application No. 10136488.1. Ni (〇) complex of acid diester or monophosphite ligand reacts with phosphite I. In the transition metal complex, the transition metal and phosphite phosphite The ratio may be in the range of 1 to 6, preferably 2 to 5, especially 2, 3 or 4. In addition to phosphinic acid phosphite I, the transition metal complex may not contain other ligands. Except for phosphines In addition to acid phosphites, transition metal complexes may contain other ligands, for example: nitriles, such as acetonitrile, adipoxie, 3-pentamidine, 4-pentamidine, 2-methyl-3-butane Enenitrile; olefins, such as butadiene; or phosphorus compounds, such as organic monophosphines, monophosphinic acid vinegars, monophosphinic acid diacetates, or carboxylic acids. In principle, the preparation of these transition metal complexes can be As described in the literature (for example, in DE-A-2 237 703, US | 3 85〇973, US A 3 766 237 or US-A-3,903,120), Tris-o-methylbenzyl phosphite, tri-m-phenylene phosphite or tri-p-tolyl phosphite transition metal complexes by using the phosphinic acid of the present invention Phosphite 1 can be partially or completely substituted for these phosphinates. The transition metal complex of the present invention can be used as a catalyst, especially as a homogeneous catalyst. We have found that in the addition of hydrocyanic acid To olefinic double bonds (especially those conjugated with other double bonds of 96784.doc 200530257, such as butadiene) to obtain 2-methylpentenenitrile mixtures using transition metal complexes as contacts It is advantageous to use a certain dagger. It is also advantageous to add hydrocyanic acid to a dilute double bond unrelated to the other f (for example, 3-pentenenitrile or 4 · acetonitrile or a mixture thereof, = 3-pentanenitrile) In order to obtain adipic acid or 3. valeric acid vinegar or (3-pentenyl ester), thereby obtaining 5-cyanovalerate as a catalyst. We have also found that organic nitriles (especially those organic nitriles in which the guess group is not conjugated with an olefinic double bond, such as 2-methyl_3 • butenenitrile) are detailed: The use of the transition metal complex of the present invention as a catalyst is particularly advantageous in enenitrile. It is also advantageous to use it as a catalyst in the isomerization of organic nitriles in which a guess group and a dilute double bond are common. In principle, The method of adding hydrocyanic acid to a dilute double bond or isomerizing cyanonitrile can be carried out by using the phosphinic acid phosphite scale of the present invention, for example, as described in WQ 99 / 丨 3983 or Thoroughfat. This is accomplished by partially or completely replacing the phosphite described therein with the acid motif I. The present invention further provides a method for the preparation by hydrocyanation of a hydrocarbon mixture containing 1,3 · butadiene in the presence of a catalyst A method of a mixture of mono-diluted C5-mononitrile with non-co-c = c and CN bonds, in which hydrocyanation is achieved in the presence of at least one of the aforementioned inventive systems. In order to prepare mono-diluted by the method according to the invention c "single guess, it is preferred to use at least 10% by volume, preferably at least 25% by volume, It has a hydrocarbon mixture with a 1,3-butadiene content of at least 40% by volume. For the preparation of, for example, 3-pentenenitrile and 2-methyl · 3 · butanthyl and is suitable for 96784.doc -19- 200530257 Mixtures of mono-Cy-mononitrile as intermediates for further processing into hexadiene, either pure butadiene or hydrocarbon mixtures containing i, 3-butadiene can be used. 1,3-butadiene mixtures can be used on an industrial scale For example, in the treatment of mineral oil by radon steam cracking naphtha, a hydrocarbon mixture called a C4 fraction and having a high total olefin fraction is obtained, in which 3-butadiene accounts for about 40%, The remainder of I is monoene, polyunsaturated hydrocarbons, and alkanes. These streams also always contain a small portion, usually up to 5%, of fast hydrocarbons, W-diene, and ethylene blocks. Pure 1,3-butane The olefins can be separated from industrially available hydrocarbon mixtures by, for example, extractive distillation. The C4 fraction is optionally substantially free of alkynes (e.g., propyne or butyne), 2-dienes (e.g., propane) Diene) and alkenyl alkynes (for example, vinyl acetylene) In addition, in some cases, where c = c double bond with CsN Production of Bonded Vehicles ^ 〇 " Applied Homogeneous Catalysis with Organometalic Compounds ,,, Volume 丄, VCH Weinheim, page 479 reveals the isomerization of fluorenylmethyl-3-butenenitrile and 3.valeronitrile The formed co-red pentapropene acts as a reaction inhibitor for the sub-addition of hydrogen cyanide to adiponitrile. We have found that the aforementioned conjugated nitriles obtained in the hydrocyanation of 0 fractions without pretreatment also Acts as a catalyst poison in the first reaction step (ie, a single addition of hydrogen cyanide) in the preparation of adipic acid. Therefore, they are partially or completely removed from the hydrocarbon mixture, as appropriate, in the catalytic hydrocyanation process. Components of toxicants, especially alkynes, 2-dienes and mixtures thereof. In order to remove these components', it is preferred to subject the catalyst to a catalytic partial hydrogenation prior to the addition of the atmosphere. This partial hydrogenation system is achieved in the presence of hydrogenation catalysts. &Amp; In addition to other diolefins and monoolefins, the hydrogenation catalyst group 96784.doc -20- 200530257 could selectively make alkynes and Olefins are hydrogenated. A suitable heterogeneous catalyst system usually contains a transition metal compound on an inert support. Suitable inorganic support systems are based on oxides (especially silica and alumina), aluminosilicates, zeolites, carbides, nitrides, etc., and mixtures thereof which are customary for this purpose. The support used is preferably Al203, Si02 & y, this a substance. It is in particular the heterogeneous catalysts used in US-A-4,587,369, US-A-4,704,492 and US-A-4,493,906, all of which are incorporated herein by reference. Other suitable copper-based catalyst systems are sold as KLP catalysts by Dow Chemical. The addition of hydrogen cyanide to 1,3-butadiene or a hydrocarbon mixture containing 1,3-butadiene (e.g., pretreated, partially hydrogenated C4 fraction) can be achieved continuously, semi-continuously, or batchwise. In a suitable variant of the method according to the invention, the addition of hydrogen cyanide is effected continuously. Appropriate reactors for continuous reactions are known to those skilled in the art and are used in, for example, ullmanns Enzyklpadie der

Chemie, Volume 1, Third Edition, 1951, page 743 ff. First, a stirred tank set or a tubular reactor is used to carry out a continuous variant of the method according to the invention. / In a preferred variant of the method according to the invention, the addition of hydrogen cyanide to I,) · butadiene or a hydrocarbon mixture with 1,3-butadiene is carried out semi-continuously. The semi-continuous method includes: a) feeding a hydrocarbon mixture (including a part of hydrogen cyanide as appropriate and the hydrocyanation catalyst of the present invention optionally generated as%) and optionally a solvent into a reactor, 96784.doc -21 -200530257 b) At high temperature and pressure, the mixture is reacted by feeding hydrogen cyanide in semi-continuous mode according to its consumption, c) The reaction is completed by continuing the reaction and then processing it. Suitable constant pressure reactors are known to those skilled in the art and are described in, for example, Ullmanns Enzyklop Sdiedertechnischen Chemie, Volume 1, Third Edition, 1951, pages 769 ff. An autoclave is usually used to carry out the method according to the invention, which can be equipped with a stirring device and an internal bushing if necessary. For the above steps, the following steps should preferably be considered: Step a): Before the reaction begins, feed partially hydrogenated C4 fraction or butadiene, cyanide gas, hydrocyanation catalyst, and optionally solvent into the Pressure reactor. Suitable solvents are the aforementioned preferred aromatic hydrocarbons used to prepare the catalysts of the present invention, such as toluene and xylene, or tetrahydrofuran. Step b): The conversion of the mixture is usually achieved under high temperature and pressure. The reaction temperature is usually in the range of about 0 to 20 ° C., preferably about 50 to 150 ° C. The pressure is usually in the range of about 1 to 200 bar, preferably about 1 to 100 bar, especially 1 to 100 bar. 50 bar, especially from 1 to 20 bar. During the reaction, hydrogen cyanide is fed in according to its consumption, during which the pressure in the autoclave is kept substantially constant. The reaction time is about 30 minutes to 5 hours. Steps c): For the conversion, the reaction time which can continue from 0 minutes to about 5 hours after the reaction time is preferably about 1 hour to 3.5 hours, during which time hydrogen cyanide is no longer fed into the autoclave Medium. At this time, the temperature is kept substantially constant at the reaction temperature set in advance 96784.doc 200530257. Treatment is carried out by ordinary methods, including: removal of untransformed 1 3 -ding-, go beta soil & spear Take it and hydrogen cyanide, for example, by washing or recovering the remaining reaction mixture to remove valuable products and recover catalysts that are still active. In another method of the invention In a suitable variant, the addition of aerated ammonia to a hydrocarbon mixture containing butane-desulfurization is achieved in batches. Roughly The reaction conditions described in the semi-continuous method were retained, as in step "in step b) no additional cyanide lice were fed and instead they were all fed in initially. By adding 2 moles Equivalent hydrogen cyanide can be divided into three steps from a mixed adiponitrile containing τ dilute: 1. Preparation of a nitrile-functional C5 monoolefin mixture. 2. The 2-methylbutane present in these mixtures. The enenitrile isomerizes to 3 · pentanenitrile, and the 3-pentanenitrile formed in this way and already present in the mixture from step jade isomerizes to different n-pyrene. This should form a very A high proportion of 3-pentanenitrile and / or 4-pentanenitrile and a small portion of conjugated 2-pentenenitrile and 2-methyl-2-butanenitrile which are catalytically toxic in certain conditions. 3. Adiponitrile is prepared by adding hydrogen cyanide to 3-pentenenitrile which has been previously isomerized to 4-pentenenitrile formed in step 2. The product of Tian 1J appears as (for example ) From hydrogen cyanide to 4-pentenenitrile, or turbid hydrogenation to 3-pentamyl, and vice versa] yjark〇vnik〇v addition of 2. methylglutaronitrile, and from hydrogen cyanide to 3 _Pentenenitrile 2Mar k〇vnik〇v ethyl succinonitrile in the addition. The catalyst of the invention based on a phosphinate ligand is also advantageously suitable for the position in step 2 and the double bond isomerization and / or step 3 Secondary addition of hydrogen cyanide 96784.doc -23- 200530257 Advantageously, the catalyst used in accordance with the present invention not only exhibits the same results obtained in the hydrocyanation of a hydrocarbon mixture containing 1,3-butadiene The high selectivity associated with the mono-addition product of Alkali, and it can also be mixed with excess hydrogen cyanide in hydrocyanation without causing significant deposition of inactive nickel (Π) compounds (eg, nickel (11)) Unlike known hydrocyanation catalysts based on non-complexed phosphine and phosphinate ligands, phosphine-containing phosphite catalysts are therefore not only suitable for applications in which hydrogen cyanide excess is usually effectively avoided in the reaction mixture. Continuous hydrocyanation processes, which are also suitable for semi-continuous and batch processes where high hydrogen cyanide excess is usually present. Therefore, the catalyst used in the present invention and the hydrocyanation method based thereon generally have a higher catalyst recycling rate and a longer catalyst production time than the existing methods. In addition to better economic feasibility, it is also beneficial from a morphological point of view, because nickel cyanide formed from active catalysts and oxidized chlorine is highly toxic and must be processed or disposed of at high cost. Except for the hydrocyanation of a hydrocarbon mixture containing 1,3-butadiene, the system of the present invention is generally applicable to all common hydrocyanation processes. This includes, among other things, the hydrocyanation of unactivated dilute hydrocarbons (e.g., styrene and% pentenenitrile). It can be advantageously performed in the presence of one or more Lewis acids that affect the activity of the catalyst system of the present invention. The addition (especially the addition of people :) Ge in ^ or to 3 · pentenenitrile, 4 · cyanonitrile or a mixture of pentene guess) or in the invention of the catalyst system (especially will ... Ding The isomerization of branched nitriles is the helmet and the right K soil, "structured to 3-pentenenitrile." Useful accelerators are non-mechanical and organic compounds. Among them, Fei, Ti mi f consists of the following ions , Zinc, Cobalt, Steel, Ci, Boron, Aluminum, 96784.doc -24 · 200530257 Yttrium, Zirconium, Niobium, Molybdenum, Cadmium, Baht, and Tin. As generally described in US 6,171,996 B1, examples include ZnBr2 , Z11I2, ZnCI〗, ZnS〇4, C11CI2, CuCl, Cu (03SCF3) 2, CoCl2, CoI2, Fel2, FeCl3, FeCl2, FeCl2 (THF) 2, TiCl4 (THF) 2, TiCl4, TiCl3, ClTi (0- Iso-Pr) 3, MnCl2, ScCl3, A1C13, (C2H5) A1C12, (C2H5) 2A1C1, (C2H5) 3A12C13, (C8H17) A1C12, (C8H17) 2A1C1, (Iso-C4H9) 2A1CM, Ph2AlC2Ph l5, ZrCl4, ZrCl2, NbCl5, VC13, CrCl2, MoC15, YC13, CdCl2, LaCl3, Er (03SCF3) 3, Yb (02CCF3) 3, SmCl3, B (C6H5) 3, TaCl5. The preferred accelerators are also in US 3,496,217 , US 3,496,218 and 1 ^ 4,774,3 53. It includes metal salts such as 211 (:: 12, (:: 〇12 and SnCh) and such as RA1C12, R3Sn03SCF3 and R3B (wherein R is alkyl or aryl Organometallic compounds.) US 4,874,884 describes how to choose a synergistic combination of promoters to increase the catalytic activity of the catalyst system. Preferred promoters include Cdcl2, FeCl2, ZnCl2, B (C6H5) 3 and (C6H6) 3SnZ 'Among them 2 is cf3S〇3, CH3C6h4S〇3 or (C6H5) 3BcN. Molar ratio of promoter and nickel in the catalyst system can be between 1:16 and 50' 丨. Another advantageous embodiment of structuring can be obtained from us MM 772. The content of the case is incorporated by reference in its entirety. The use of the invention system or a mixture of these systems instead of the patent Catalyst specified in the manual. d L and another advantageous embodiment of isomerization can be obtained from US 6,127,567 in the oral case. The content of this application is incorporated by reference in its entirety. The condition of the application is the use of an inventive system or a mixture of these systems. Replaces the bracelet medium specified in this patent 96784.doc 200530257 § children's book. Ammonia cyanation is another-advantageous embodiments can be obtained by reference in its entirety and incorporated into this text: 93: 3, the invention system or these systems are used in this case. Catalyst .... The alternatives to the cyanidation in the patent specification can be obtained from the present invention by using the internal reference method, and the application is limited to the following conditions: Ming system or a mixture of these systems instead of the catalyst specified in this patent specification. The invention is described in detail with reference to the following non-limiting examples. Example yield is determined by gas chromatography (column: 30mHp_50; Temperature program · Isothermal at 40C for n minutes, then heated to 280 C at a rate of 100 c / minute; gas chromatograph: Hewlett Packard HP 589). All male cases were performed under an argon protective atmosphere. Favorable specifications of the starting materials, HCN, 3PN and 2M3BN are available from wo 03/045552. The abbreviation nickel (0) (m-phosphite / p-tolyl ester) means a mixture which contains 2.35% by weight of O ( ), 19% by weight of 3-pentenenitrile and 78.65% by weight with 2: 1 / Comparison meta / p-tolyl phosphite. The chelating ligands used are: 96784.doc -26- 200530257

Ni (COD) 2 represents Ni (O) -bis- (1,4-cyclooctadiene); 2M3BN represents 2-fluorenyl-2-butenenitrile; t2M2BN represents trans-2-methyl-2-butene Nitrile; C2M2BN means cis-2-methyl-2-butenenitrile; t2PN means trans-2-pentenenitrile; 4PN means 4-pentenenitrile; t3PN means trans-3-pentenenitrile; c3PN means cis-3 -Pentenenitrile; MGN means methylglutaronitrile; 3PN means the sum of t3PN and c3PN; BD means 1,3-butadiene; HCN means hydrocyanic acid; ADN means adiponitrile; and THF means tetrazole Mum. Example 1-3: Hydrocyanation of BD to 2M3BN / 3PN, followed by 2M3BN isomerization Example 1 (control): (0.51 mmol Ni (0)) 96784.doc -27- 200530257

In THF, 1 equivalent of Ni (COD) 2 and 3 equivalents of ligand 1 were stirred for 20 minutes. This solution was mixed with 797 equivalents of BD, fed into glass high pressure flea at 25 ° C, and heated to 90 ° C. After 60 minutes, 465 equivalents of HCN in THF were dosed immediately, and stirring was continued for another 75 minutes at 90 ° C. After 135 minutes, the 2M3BN / 3PN ratio (GC area percentage) was measured by GC. The 2M3BN / 3PN ratio is 1.9 / 1. Subsequently, the entire mixture was heated to 115 ° C for 60 minutes to directly isomerize 2M3BN to 3PN. The conversion rate of HCN to 2M3BN / 3PN is greater than 95% (GC area percentage; internal standard: ethylbenzene). The 2M3BN / 3PN ratio is 1.8 / 1. Example 2 (invention): (0.5 · 3 mmol Ni (0))

Ligand 2 96784.doc -28- 200530257 Ligand synthesis: In an argon atmosphere at -15 ° C, initially 40 mmol of 2,2'-dihydroxy-3,3 ', 5,5'- Tetramethyldiphenol and 160 mmol of triethylamine were fed to 120 ml of toluene in a 500 ml flask. At this temperature, 44 mmol of diphenylphosphine dissolved in 40 ml of toluene was added dropwise over 40 minutes. The mixture was stirred at -15 ° C for another 6 hours. At -15 ° C, 40 mmol of di-o-tolyl chlorophosphite dissolved in 40 ml of toluene was added dropwise to the mixture. The mixture was allowed to reach room temperature and stirred for another 15 hours. The mixture was filtered, and the filtrate was concentrated sufficiently. 25.3 g of product were obtained. 31P NMR (C6D6): 133.5 ppm and 112.8 ppm; Bisphosphonic acid S impurity: 112.5 ppm. 1 equivalent of Ni (COD) 2 and 3 equivalents of ligand 2 were stirred in THF for 20 minutes. This solution was mixed with 740 equivalents of BD, fed into a high-pressure glass at 25 t, and heated to 80 ° C. After 100 minutes, 465 equivalents of HCN in THF were metered out immediately, and stirred for another 20 minutes at 80 ° C. After 120 minutes, the 2M3BN / 3PN ratio (% of GC area) was determined by gas phase GC. The 2M3BN / 3PN ratio is 1.5 / 1. Subsequently, the entire batch mixture was heated to 115 ° C for 60 minutes to directly isomerize 2M3BN to 3PN. The conversion rate from HCN to 2M3BN / 3PN is greater than 95% (GC area percentage; internal standard: ethylbenzene). The 2M3BN / 3PN ratio is 1 / 4.6. Example 3 (Invention): (0.76 mmol Ni (0)) 96784.doc -29- 200530257

Ligand Synthesis: In an argon atmosphere at -15 ° C, 40 mmol of 2,2f-dihydroxy-hexamethyldiphenol and 160 mmol of triethylamine were initially fed to 120 ml of toluene in a 500 ml flask. in. At this temperature, 44 mmol of diphenylchlorophosphine dissolved in 40 ml of toluene was added dropwise over 40 minutes. The mixture was stirred at -15 ° C for another 6 hours. 40 mmol of di-o-tolyl chlorophosphite dissolved in 40 ml of toluene was added dropwise to the mixture at -15 ° C. The mixture was allowed to reach room temperature and stirred for another 15 hours. The mixture was filtered, and the filtrate was concentrated sufficiently. 21.5 g of product were obtained. 31P NMR (C6D6): 134.7 ppm and 110.6 ppm. 1 equivalent of Ni (COD) 2 and 3 equivalents of ligand 3 were stirred in THF for 20 minutes. This solution was mixed with 770 equivalents of BD, fed into a glass autoclave at 25 ° C, and heated to 80 ° C. After 60 minutes, 465 equivalents of HCN in THF were dosed immediately and stirred at 80 ° C for another 40 minutes. After 100 minutes, the 2M3BN / 3PN ratio (% of GC area) was measured by GC. The 2M3BN / 3PN ratio is 2.5 / 1. Subsequently, the entire batch was heated to 115 ° C for 60 minutes to directly isomerize 2M3BN to 3PN. 96784.doc -30- 200530257 The conversion rate of HCN to 2M3BN / 3PN is greater than 95% (GC area percentage; internal standard: ethylbenzene). The 2M3BN / 3PN ratio is 1 / 2.6. Example 4-8: Isomerization of 2M3BN to 3PN Example 4 (control): (0.5 mmol Ni (0)) 1 equivalent of nickel (〇) (m- / p-tolyl phosphite) 5.7 and 465 equivalents of 2M3BN Mix and heat to 115 ° C. After 90 minutes and 180 minutes, take a GC sample from the reaction mixture and analyze it by GC (% of GC area). Time 2M3BN t2M2BN C2M2BN t2PN 4PN / t3PN / c3PN 3PN / 2M3BN 90 minutes 84.5 1.3 0.3 0 13.0 0.15 180 minutes 72.4 1.5 0.5 0 24.4 0.34 Example 5 (control): (0.5 · 1 mmol Ni (0)) 1 equivalent of Ni (COD) 2 was mixed with 3 equivalents of ligands 1 and 465 equivalents of 2M3BN and stirred at 25 ° C 1 hour and heated to 115 ° C. After 0, 1 hour, and 3 hours, GC samples were taken from the reaction mixture and analyzed by GC (GC area percentage). Time 2M3BN c, t-2M2BN c, t-2PN 4PN c, t-3PN 3PN / 2M3BN 0 hours 94.8 4.96 0 0 0 1 hour 86.04 5.98 0 0 6.85 0.08 3 hours 79.67 7.09 0 0 11.28 0.14 Example 6 (Invention) : (0.4 mmol Ni (0))

1 equivalent of Ni (COD) 2 was mixed with 3 equivalents of ligand 2 and 465 equivalents of 2M3BN, stirred at 25 ° C for 1 hour, and heated to 115 ° C. After 0, 5 and 25 minutes, GC samples were taken from the reaction mixture and analyzed by GC (GC 96784.doc -31-200530257 area percentage). Time 2M3BN 2M2BN] 2PN 3PN + 4PN 3PN / 2M3BN 0 minutes 85.5 4.1 0 8.4 0.1 5 minutes 51.4 4.1 0 42.3 1.2 25 minutes 4.8 4.0 0 89.1 18.6 Example 7 (invention): (0.3 8 mmol Ni (0)) 1 equivalent Ni (COD) 2 was mixed with 3 equivalents of ligand 3 and 465 equivalents of 2M3BN, stirred at 25 ° C for 1 hour, and heated to 115 ° C. After 0, 5 and 25 minutes, GC samples were taken from the reaction mixture and analyzed by GC (GC area percentage). Time 2M3BN 2M2BN 2PN 3PN + 4PN 3PN / 2M3BN 0 minutes 91.1 4.5 0 2.9 0.03 5 minutes 68.1 4.4 0 25.3 0.38 25 minutes 4.8 4.4 0.1 88.4 18.4 Example 8 (Invention): (0.35 mmol Ni (0))

Ligand Synthesis: In an argon atmosphere at -15 ° C, 40 mmol 2,2 ^ dihydroxy- 96784.doc -32- 200530257 3,3'-diisopropyl-6,6'- Dimethyldiphenol and 44 mmol of diphenylchlorophosphine were fed into 120 ml of toluene in a 500 ml flask. At this temperature, 160 mmol of triethylamine dissolved in 40 ml of toluene was added dropwise over 40 minutes. The mixture was stirred at -15 ° C for another 6 hours. At -15 ° C, 40 mmol of di-o-o-tolyl chlorosulfinic acid dissolved in 40 ml of toluene was added dropwise to the mixture. The mixture was allowed to reach room temperature and stirred for an additional 15 hours. The mixture was filtered, and the filtrate was concentrated sufficiently. 21.5 g of product were obtained. 31PNMR (C6D6): 132.5 ppm and 113.5 ppm ○ 1 equivalent of Ni (COD) 2 was mixed with 3 equivalents of ligand 4 and 465 equivalents of 2M3BN, stirred at 25 ° C for 1 hour, and heated to 115 ° C. After 0, 5 and 25 minutes, GC samples were taken from the reaction mixture and analyzed by GC (GC area percentage). Time 2M3BN 2M2BN 2PN 3PN + 4PN 3PN / 2M3BN 0 minutes 89.1 4.8 0 4.2 0.05 5 minutes 78.8 4.6 0 14.9 0.19 25 minutes 41.5 4.4 0 52.5 1.27

Example 9-13: 3PN hydrocyanation to ADN Example 9 (control) · (0.6 mmol Ni (0)) 1 equivalent of nickel (〇) (m- / p-tolyl phosphite) 5-7 and 3 65 equivalents of 3PN mixed, stirred at 25 ° C for one hour, and heated to 70 ° C. 1 equivalent of ZnCl2 was added to the mixture and stirred for another 5 minutes. In an argon carrier gas stream, 94 equivalents of HCN / h * Ni were injected immediately. After 30 minutes, 60 minutes, and 150 minutes, GC samples were taken from the reaction mixture and analyzed by GC (GC area percentage; internal standard: ethylbenzene). 96784.doc -33- 200530257 Time MGN ADN ADN selection rate (%) 30 minutes 3.35 10.75 76.2 60 minutes 6.87 26.39 79.3 150 minutes 7.11 27.82 79.6 Example 10 (control) · (0 · 45 mmol Ni (0)) will be 1 Equivalent Ni (COD) 2 was mixed with 3 equivalents of ligand 1 and 365 equivalents of 3PN, stirred at 25 ° C for one hour, and heated to 70 ° C. 1 equivalent of ZnCl2 was added to the mixture and stirred for another 5 minutes. In an argon carrier gas stream, immediately inject 286 equivalents of HCN / h * Ni. After 60 minutes, a GC sample was taken from the reaction mixture and analyzed by GC (GC area percentage; internal standard: ethylbenzene). Time MGN ADN ADN selectivity (%) 60 minutes 1.4 8.4 86.0 Example 11 (invention): (0.3 7 mmol Ni (0)) Mix 1 equivalent of Ni (COD) 2 with 3 equivalents of ligand 2 and 3 65 equivalents of 3PN , Stir for one hour at 25 ° C, and heat to 40 ° C. 1 equivalent of ZnCl2 was added to the mixture and stirred for another 5 minutes. In an argon carrier gas stream, immediately inject 3 09 equivalents of 11 €! ^ / 11 * chuan. After 88 minutes, take 10 (: sample from the reaction mixture and analyze by GC (GC area percentage; internal standard: ethylbenzene). Time MGN ADN ADN selectivity (%) 88 minutes 6.5 68.3 91.3 Example 12 ( Invention): (0.3 6 mmol Ni (0)) 96784.doc -34- 200530257 Mix 1 equivalent of Ni (COD) 2 with 3 equivalents of ligand 3 and 365 equivalents of 3PN, stir at 25 ° C for one hour, and Heat to 40 ° C. Add 1 equivalent of ZnCl2 to the mixture and stir for 5 minutes. In an argon carrier gas stream, immediately inject 3 02 equivalents of 1 ^ ~ 11 *. After 80 minutes, take 0 from the reaction mixture. (: Samples and analysis by GC (GC area percentage; internal standard: ethylbenzene). Time MGN ADN ADN selectivity (%) 80 minutes 7.2 62.4 89.7 Example 13 (invention) · (0.39 mmol Ni (0 )) Mix 1 equivalent of Ni (COD) 2 with 3 equivalents of ligands 4 and 3 65 equivalents 3 卩 1 ^, stir at 25 ° C for one hour, and heat to 40 ° C. Add 1 equivalent of ZnCl2 to the The mixture was stirred for another 5 minutes. In an argon carrier gas stream, 289 equivalents of HCN / h * Ni were injected immediately. After 82 minutes, the reaction mixture was removed from the reaction mixture. A GC sample, and analyzed by GC (GC area percentage; internal standard: ethylbenzene) Time MGN ADN ADN selectivity (%) 82 minutes 5.4 59.2 91.7 96784.doc 35-.

Claims (1)

200530257 10. Scope of patent application: 1. A phosphinic acid phosphite I and its mixture of the following formula 1 or 2 or 3 or 4 or 5 or 6: Formula 1 2 3 R1R1 R12 R13 R2 96784.doc 200530257 type B11 R10 R11 R10 wherein R1, R2, and R4 are each independently an alkyl or alkyl group having 1 to 8 carbon atoms, and the restriction is that at least one of the groups R1, R2, and R4 is not fluorene, and R5 to R22 are each independent Is fluorene, an alkyl group or alkynyl group having 1 to 8 carbon atoms, 96784.doc 200530257 R3 is fluorene, methyl or ethyl, when η is 1 or 2, X is F, Cl or CF3, and when η When it is 0, X is η. 2. The phosphinic acid phosphite I according to claim 1, wherein ri, r2, R4, R5, R7, R8, R10, R12, R13 are each independently selected from the group consisting of the following groups: Η, 曱Methyl, ethyl, n-propyl, isopropyl and tert-butyl. 3. The use of phosphinic acid phosphatidic acid I as described in item 1 or 2 as a ligand in a transition metal complex. 4. A transition metal complex containing a phosphinite as claimed in claim 1 or 2 as a ligand. 5. The transition metal complex of claim 4, wherein the transition metal used is brocade;. 6. A method for preparing a transition metal complex as claimed in claim 4 or 5, in which an elemental transition metal or a compound containing a transition metal and a sub-formula of the formula as described in item 1 or 2 are clarified Phosphonic acid phosphite I reacts. 7_ A use of a transition metal complex as claimed in item 4 or 5 as a catalyst. 8. The use of item 7 as a catalyst for adding hydrocyanic acid to a diene double bond. The purpose of claim 7 is as a medium for isomerizing organic nitriles. 10. A method for adding hydrocyanic acid to an ene double bond in the presence of a catalyst, wherein the catalyst used is a transition metal complex as claimed in claim 4 or 5.口 11. The method of claim 10, wherein hydrocyanic acid is added to butadiene to obtain 96784.doc 200530257. A method selected from the group consisting of 2, methyl-3-butenenitrile, and% pentenenitrile. The compound of the group 12. 13. 14. Method of penteneΜ: M wherein hydrocyanic acid is added to pentenenitrile, 4-pentenenitrile, or a mixture thereof to obtain adiponitrile. A method for isomerizing an organic nitrile in the presence of a catalyst, wherein the catalyst used is a transition metal complex as claimed in claim 4 or 5. The method of claim 13, wherein 2-methyl-3-butenenitrile is isomerized to 3-pentenenitrile. 96784.doc 200530257 7. Designated Representative Map: (1) The designated representative map of this case is: (none) (2) The component symbols of this representative map are simply explained: 8. If there is a chemical formula in this case, please disclose the one that can best show the characteristics of the invention. Chemical formula: Formula 1 R12 R13 96784.doc 200530257 Equation 5 formula R11 R10 96784.doc