TW386075B - Process for the preparation of 5-formylvaleric acid and 5-formylvalerate ester - Google Patents

Description

Attachment: In the patent application No. 8312200: ¾ amendment to the specification f A7 __ B7 V. Description of the invention (1) The present invention relates to the preparation of 5-methylformylvaleric acid or the corresponding 5-methylformylvalerate The method is made by using a catalyst system including rhodium and phosphite ligands to perform hydrogenation reaction of 3-pentenoic acid or 3-pentenoate with carbon monoxide and hydrogen. The hydroformylation reaction herein refers to the reaction of an unsaturated hydrocarbon with carbon monoxide and hydrogen to produce an aldehyde compound in the presence of a catalyst. This method is disclosed in EP — A — 5 5 6 6 8 1. The method proposed in this patent specification is hydroformylation of methyl J-pentenoate to linear methyl 5-pentanovalerate. The catalyst used in this method contains rhodium and a bi-coordinated phosphite ligand such as formula (1), ---; --r ------ :, ^-(Please read the back first (Notes for filling in this page)

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs where + is the third butyl. According to EP-A-556681, the highest selectivity for methyl 5-methylamylvalerate can reach 76.7 mole%. Selectivity is calculated from the molar amount of a particular product relative to the molar amount of the 3-pentenoate (or acid) being converted. The disadvantages of the method described in E P — A — 5 5 6 6 8 1 are that the reaction tends to have low selectivity to 5-methylfluorenyl valerate, and that the organic phosphite ligands are generally difficult to prepare. It is an object of the present invention to provide a method in which 3-pentenoic acid or 3-pentenoate can be hydroformylated in the presence of a catalyst containing germanium and an easily prepared organic phosphite ligand. , Make straight chain 5—form paper size applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm)

Attachment: In the patent application No. 8312200: ¾ amendment to the specification f A7 __ B7 V. Description of the invention (1) The present invention relates to the preparation of 5-methylformylvaleric acid or the corresponding 5-methylformylvalerate The method is made by using a catalyst system including rhodium and phosphite ligands to perform hydrogenation reaction of 3-pentenoic acid or 3-pentenoate with carbon monoxide and hydrogen. The hydroformylation reaction herein refers to the reaction of an unsaturated hydrocarbon with carbon monoxide and hydrogen to produce an aldehyde compound in the presence of a catalyst. This method is disclosed in EP — A — 5 5 6 6 8 1. The method proposed in this patent specification is hydroformylation of methyl J-pentenoate to linear methyl 5-pentanovalerate. The catalyst used in this method contains rhodium and a bi-coordinated phosphite ligand such as formula (1), ---; --r ------ :, ^-(Please read the back first (Notes for filling in this page)

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs where + is the third butyl. According to EP-A-556681, the highest selectivity for methyl 5-methylamylvalerate can reach 76.7 mole%. Selectivity is calculated from the molar amount of a particular product relative to the molar amount of the 3-pentenoate (or acid) being converted. The disadvantages of the method described in E P — A — 5 5 6 6 8 1 are that the reaction tends to have low selectivity to 5-methylfluorenyl valerate, and that the organic phosphite ligands are generally difficult to prepare. It is an object of the present invention to provide a method in which 3-pentenoic acid or 3-pentenoate can be hydroformylated in the presence of a catalyst containing germanium and an easily prepared organic phosphite ligand. Straight chain 5—formamidine This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 ___B7 ___ V. Description of the invention (2) Valproic acid or 5-methylformylvalerate It can be obtained under high selectivity. This purpose is achieved because the phosphite ligand system is as shown by the following general formula (2):

A 〇- P. (OR1) (OR2) (2) wherein R 1 and R 2 are the same or different monovalent aromatic organic groups, A is an η-valent group or an atom, and η is an integer of at least 2 and each I --- Γ ------ 蓼 i-(Please read the precautions on the back before filling out this page) -0-Ρ (0 R 1) (〇R) radicals can be the same or the same as each other Different radicals, and phosphites form che late-type complexes with germanium. We found that the hydroformylation of 3-pentene (or 3-valerate) in this case method can be highly selective If 5-methylformylvalerate is obtained, if 5-methylformylvalerate is the desired product, another advantage is that 4-methylformylvalerate is relative to 3-methylformylvalerate. The amount of valproic acid ester is lower than that produced by the method described in EP — a_5 5 6 6 8 1. The reason for its advantage is the boiling point of 4-formylvalerate and 5-formylvalerate The boiling points of the esters are almost the same, but when the amount of 4-methylamylvalerate is small, it is easier to separate the two by distillation. In addition, the 3-, 4-methylamylpentanyl produced in the method of the present invention The amount of esters is so small that 3-'4 a Distillation of 5-methylpentanovalerate is simpler. Another advantage is that the bi-coordinated phosphite ligands of formula (2) are available. This paper size is applicable to China National Standard (CNS) A4 specifications (210X 297 mm). ),? Τ Production cooperation of employees of the Central Bureau of Standards, Ministry of Economic Affairs, printed 5 A7 B7 V. Description of the invention (3) A simpler than the double-coordinated phosphite ligand exemplified by EP _A_ 5 5 6 6 8 1 In general, the ligand of formula (2) can be prepared by at least one step less than the synthetic step of the bi-coordinated phosphite ligand of EP-A-5 5 6 6 8 1, especially It is easier to prepare when the bi-coordinated phosphite ligands of formula (2) are symmetrical (the different _ (0 R 1) (◦ R 2) groups are the same). In addition, it does not need to be substituted. _ (bisphenol) to synthesize bi-coordinated phosphite ligands is also relatively easy to manufacture. The reason is that substituted bisphenols are generally not easy to obtain and must be synthesized separately. Bi-coordinated phosphite ligands of formula (1) Is an example of a compound made from two different substituted bisphenols. Furthermore, the bi-coordination of formula (1) Phosphate ligands are not symmetrical. A large number of synthetic steps required to prepare the ligands of formula (1) are disclosed in, for example, US-A-4748261. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (read first on the back) (Notes on this page, please fill in this page) Chelated complexes refer to a molecule containing a phosphite group (approximately) with at least two phosphorus P atoms and a germanium atom / ion forming a coordination bond. The non-chelated complex refers to that a molecule containing a phosphite group generally has only one phosphorus P atom system and a germanium atom / ion forming a coordination bond. The choice of the organic group A of the ligand of formula (2) determines whether the phosphite ligand forms a chelate complex with germanium. "A method similar to the catalyst system of the present case is used for hydroformylation. Revealed in EP — A — 5 1824 1. However, E P_A_ 5 1 8 2. 4 1 suggests that the catalyst system containing phosphites that form chelate complexes with germanium is suitable for the hydromethylation of terminally unsaturated olefins, and does not constitute chelate complexes ( Non-chelating) phosphite is suitable for the paper size. Applicable to China National Standard (CNS) A4 specification (210X297 mm) ^ ~ -6-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 __ 5. Description of the invention ( 4) It is used for the methylation of internally unsaturated olefins with branched chains into aldehydes with high selectivity. It was surprisingly found that when starting from an internally unsaturated 3-pentenoate and using a phosphite that forms a chelate complex with germanium, the reaction is highly selective towards 5-methylpentanoate. " The method of the present invention is performed in the presence of a catalyst, which contains a phosphite such as formula (2), wherein R 1 and R 2 are the same or different aromatic organic groups to have 6 -30 carbon atoms is preferred. Examples of suitable aromatic organic groups are: phenyl, fruit, M, or phenanthryl. Among them, phenyl and fluorenyl are preferred, because phosphorous acid esters having such groups are easily available. R1 and R2 are not connected to each other, but are connected only through a phosphorus atom P. Preferably, at least one carbon atom of the aromatic hydrocarbon group R 1 and / or R 2 which is immediately adjacent to the oxygen atom (from the 10_P — (— 〇—) 2 group) is replaced by a hydrogen atom. Group (hereinafter referred to as ortho-substituted). These phosphites are very stable. Both R1 and R2 are best when ortho-substituted. Generally speaking, the substituent is an organic group. Suitable organic groups that can be used as a substituent include: Ci-c2. Alkyl, c6-c2. Aryl and c5-c2. Cycloalkyl. Examples of such substituents are straight-chain or branched-chain alkyl groups, Such as methyl, ethyl, propyl, butyl, tertiary butyl, pentyl, and linear nonyl. Other suitable organic groups are alkoxy 'such as methoxy and ethoxy; alkoxycarbonyl such as Methoxycarbonyl and ethoxycarbonyl; and phenyl, etc .. Particularly suitable are alkyl groups (large groups) capable of generating steric hindrances. For example, isoalkyl groups such as isopropyl, third butyl, and new Amyl. However, other substituents, such as anion, are also acceptable, such as halogen paper standard (CNS) 8 4 (21GX29 7mm): -7-(Please read the notes on the back before filling this page)-Binding Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ____B7 _ V. Invention Description (5) Base (One C5, One Br , A F, -1), Ci-Ce alkyl ester groups such as methyl esters, third butyl ester groups, and C5-C 2. Aryl ester groups such as phenyl esters; eyes; keto groups; and Shuo .. R 1 and R 2 may also contain non-positively substituted substituents, and these substituents may be the ones described above. A in formula (2) may be an η-valent group or an atom, and a suitable atom is selected from the element periodic system. (The Periodic System of Elements) (CAS version 'Chemical and Engineering News, 63 (5), 27, 1 9 8 5) IV A, IV B, m A, IE B and lanthanides, such as S i, B, A Ai, and T i (n is equal to the valence of the atom). The n valence base of the present invention is any that can be combined with two or more [_ 0 — P (0 R 1) ( 0 R 2)] group, this group may be an organic group or an inorganic group. Η in the polymer is infinite and organic groups in the macromolecule η-generally 8 or more are suitable as the η valence group A. Suitable In formation Examples of polymers with an η-valent group A are polyvinyl alcohol and carbohydrates. The A group may also be an inorganic compound in which A represents, for example, a carrier for a heterogeneous catalyst. Suitable inorganic A groups may be silica and zeolite. 2) In A, an η-valent organic group having 1 to 30 carbon atoms and η is 2 to 8 are preferred. Examples of such ligands include the following ligands (1) to (8), Wherein t—Bu is a third butyl group, Me is a methyl group, n CgH19 is a straight bond nonyl group, and Me is a methoxy group. This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297mm) ---- Γ .----- installation-(please read the precautions on the back before filling this page), βτ ~ 8- A7 B7 V. Description of Invention (6)

Ligand (1) CCH2-〇—P- / tBu \ \

-aCyH}

-t.Bu

Me, c · ch2-o ~ p-

Me / t.Bu 1 \

Ligand (2)

Ligand (3) (Please read the notes on the back before filling out this page) • Binding-Order Printed by the Staff Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs / 2 /

Ligand (4) This paper size applies to Chinese national standards (CNS> A4 size (210X297mm) 1 W4 _ A7 B7 V. Description of invention (7) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

I --- „---------- Install-C Please read the notes on the back before filling out this page) The size of the paper is applicable to the Chinese National Standard (CNS) A4 (2IOX297 mm) 10 -Printed by A7 B7, Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs 5. Description of the Invention (8) Phosphites used as ligands can be prepared by a two-step synthesis method. This synthesis process can be performed in a single container (middle The product has not been purified). Phosphorous halides such as phosphorus trichloride are reacted with a hydroxy hydrocarbon compound represented by the general formulas of RiOH and R2OH. The reaction is in a solvent (such as toluene) with a hydrogen halide receptor (receptor). In the case of an amine, an intermediate product having the general formula CJ? — P (OR1) (OR2) is prepared. The phosphite of the present invention is obtained in the second step by using the intermediate product with formula A — (0H.) N is prepared by the reaction of hydroxy hydrocarbons. The preparation method of such a phosphite compound is also described in the aforementioned EP-A-5 1 8 2 4 1. As mentioned above, the present invention prepares the phosphorous acid The ester starts with an inorganic hydrocarbon having n hydroxyl groups (η of Formula 2). Advantageous. This compound forms the basis of the n-valent group A, and the position of the hydroxyl group in the organic compound determines whether a phosphite capable of forming a chelate complex is prepared. An appropriate phosphite that forms a chelate complex In the preparation, it can start from the following hydrocarbon compounds containing hydroxyl groups: 2,2-biphenyldiol, 2,2-dihydroxydiphenyl methylamine, catechol, .1, 2-cyclohexane. Alcohol, cis-1,2-cyclododecanediol, ethylene glycol, 1,3-propanediol, isopentaerythritol, 1,1 thiobis (2-a certain hydrazone), 1, 1 / -dihydrophenol, 2,3 -dihydroxyfluorene and 1,8-dihydroxyfluorene. Formula (2) It is preferred that A is a C — (CH2 —) 4 group and η is 4, and such a phosphite is used as a ligand. The compound can be made from easily available isopentyl alcohol, and the resulting compound has a low cost and is extremely advantageous. When a small number of ligands are decomposed in the reaction, it is necessary to supply fresh ligands to this paper. Chinese national standards apply (CNS) Α4 size (210 X 297 mm) (Please read the precautions on the back before filling this page) • Installation.

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (9) This is especially true in the case of catalyst systems to maintain a reasonable response rate and / or selectivity. The method of the present invention can start with 3-pentenoic acid to prepare 5-methylpentenovaleric acid or start from 3-pentenoate to produce 5-methylpentanovalerate in a process. This ester compound will be described further below, and the reaction conditions described below also apply to the acid. 3-Pentenoate can be represented by the following general formula: CH3-CH = CH-CH2-C-〇-R (3)

II 〇 wherein R represents a (cyclo) alkyl group having 1 to 8 carbon atoms or an aryl group or aralkyl group having 6 to 12 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, cyclohexyl, fluorenyl, and phenyl. Among them, methyl ester and ethyl ester are preferred. These ester compounds can be prepared from butadiene with methanol or ethanol in a simple manner with high selectivity. The 3-pentenoate can be hydroformylated in a pure matrix state or in a mixture state with other isomeric pentenoates. The other pentenoates refer to 4-pentenoates and 2-pentenoates. This process should preferably start with a pentenoate mixture because such a mixture is easy to prepare. For example, 'the mixture is made by the carbonylation of butadiene with carbon monoxide and an alcohol. This alcohol will correspond to the ester group R of formula (3), and it is the same as R — OH. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling in this. Page), ίτ -12-Α7 Β7 5. Description of the invention (10). The method of carbonylation of butadiene is described in US-A-3 1 6 1 6 7 2 'US-A-3253018 and EP-a-301450. The preparation method of the pentenoic acid mixture is described in EP-A-284170 and EP-A ~ 45〇577. Generally speaking, the content of 3-pentenoate (or acid) in such a mixture is higher than 50%. In addition, when 3-pentenoate is used in a continuous process (wherein The pentenoate is recovered and sent to the hydroformylation zone for further reaction.) During the reaction, the reaction mixture usually contains a small amount of 2-pentenoate and 4-pentenoate. The linear 5-formamylvalerate (or acid) prepared by the method of the present invention can be used as adipic acid (a raw material of nylon-6, 6) and e-caprolactam (a nylon A 6 of the raw materials) of the raw materials. Ε-caprolactam can be prepared by the method disclosed in US-A-47.3 3 0 0 4 1 using 5-methylmethylvalerate; and e-caprolactam is prepared by 5-methylmethylvaleric acid The method is disclosed in EP — A — 24 2 5 0 5. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs ---- ^ ----------(Please read the notes on the back before filling this page) The temperature of the hydroformylation reaction is usually between 3 The temperature is preferably between 0 and 150 ° C, preferably 50 and 120 ° C; the pressure may be between 0.1 and 20 MPa, and more preferably 0.2 and 5 OMPa. Usually the amount of the bi-coordinated phosphite compound relative to the amount of money during the hydroformylation reaction is an excess of the 'bi-coordinated phosphite compound to germanium ratio (L / Rh, expressed as mo 芡 / mo 芡)-general system Between 1: 1 to 100: 1 'is preferably between .1 to 15.0: 1. Η2. The CO mole ratio may be between 1: 10 ~ 10: 1, and preferably between 1: 2 ~ 5: 1. This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm). Printed by A7 B7, consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs. Ⅴ. Description of Invention (η) Germanium can be used in various forms, and rhodium is sent into The method used in the reaction mixture is not important. Generally speaking, germanium precursors such as Rh (CO) 2 (acac) (_a cac = ethyl pyruvate) 'R h 2 0 3' R h 4 (C 0)! 2 'R h 6 (C 0) χ e' Rh (N03) 2, Rh (OAc) 2 (0Ac = acetate) and substituted triphenylphosphine-based catalytically active complexes are produced in the reaction mixture of. Among them, Rh (C〇) 2 (acac) or Rh (OAc) 2 is preferable because it is easy to obtain. The 5-formamylvalerate in the reaction mixture can be recovered by distillation. The bi-coordinated phosphite compound will remain in the liquid phase due to its high molecular weight and high stability, so it will not be easily degraded due to the high distillation temperature. As a result, 5-methylformylvalerate can be separated from the reaction mixture and catalyst in a simple manner. The hydroformylation reaction is usually carried out in the presence of a solvent, but it may also be carried out in the absence of a solvent. Suitable solvents are inert organic solvents or solvents that do not interfere with the reaction. For example, it may be a starting compound, a process product, and a compound related to a product to be formed, such as a by-product, especially a condensation product, which may be generated during hydroformylation. Other suitable solvents are saturated hydrocarbon compounds such as petroleum + naphthas kerosine, mineral oil, and cyclohexane with aromatic compounds, ethers, ketones, and nitriles, such as toluene, benzene, Xylene, .texanol® (Union Carbide), diphenyl ether, tetrahydrofuran, cyclohexanone and benzonitrile. The present invention will be further explained through the following examples, but these examples only apply this paper to the Chinese National Standard (CNS) A4 specification (210X297 mm): ": -14----- Γ .-- r- --Ά Install 11 r I (Please read the precautions on the back before writing this page with 4V) Order A7 B7 V. Description of the invention (12) It is for the purpose of illustration and not to limit the invention.

Example I Rh (CO) 2 (aCac) (1.15 X 1 0 _5m oj?), A phosphite corresponding to the ligand (1) [ligand / error (L / Rh) ) = 5mo j? / Mo cross) and 40 in β toluene were charged into a 150 m 殳 Hasta_lloy-C steel autoclave (Pa rr), then the autoclave was sealed and filled with nitrogen. The autoclave was then heated to 90 ° C over a period of about 30 minutes and the pressure was brought to IMP a 'with carbon monoxide / hydrogen (1: 1 mol / mol). Thereafter, a matrix mixture (3.3 g of methyl 3-pentenoate and 1.0 g of nonane and toluene was added to 10 mj?) Was injected into the autoclave. The composition of the reaction mixture was analyzed by gas chromatography, and the results are shown in Table 1. (Please read the notes on the reverse side before filling out this page)-Installed, * τ Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -15 -A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (l3) Table 1 Example 3-MP / Rh time / hour conv. /% 4—mp cis + trans -2-mp mv 3-fv 4- fv 5-fv I 1950 7 13.5 8.9 7.5 6.0 5.3 2.3 69.6 1950 25.5 45.3 2.0 6.7 7.0 4.5 2.1 77.5 Π 15820 6.5 15.8 15.6 11.7 5.6 4.3 1.9 61.0 15820 27 54.2 1.2 5.7 5.4 5.2 2.0 80.4 (Please read the note on the back first Please fill in this page again for details). The size of this paper is applicable to Chinese National Standard (CNS) A4 (210X297 mm). Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. A7 ____B7 ___ 5. Description of the invention (14) c ο η v. = converted 3-methyl- and 5-pentenoic acid methyl ester (%) 4-mp = yield of 4-pentenoic acid methyl ester / c ο η ν (mol% ) c i_s + tr ans — 2. — m. ρ = 2—cis_ valeric acid. vinegar and 2 —transpentenoate Yield / conv. (Mol%) mv = yield of methyl valerate./conv. (% Of Wuer) 4-fv = 4-Yield of methylformylvalerate / c 〇nv · ( Molar%) 5-fV = 5-methylmethylvalerate yield / conv. (Mol%)

Example H The procedure of Example 1 was repeated with 20 mj of toluene (instead of 40 m ^ toluene) and 27.lg of methyl 3-pentenoate. The results from Table 1 show that the selectivity to methyl 5-formamylvalerate (80.4 mol%) is clearly better than that of the prior art (Ugliao Yi Wan-55668 1 .: 76.7 mol%). In addition, the ratio of methyl 5-methylformylvalerate to methyl 3-formylvalerate to methyl 4-formylvalerate (92: 8 to 85:15) is better. This result, and the fact that the undesired isoformyl methyl ester is roughly composed of methyl 3-formylvalerate, helped to convert the desired 5.-methylformylvalerate from the unwanted isomer ( 3-fv and 4-fv) were separated by distillation. This paper size applies to China National Standard (CNS) A · 4 specifications. (210 '乂 297 mm) (read the precautions on the back and then fill out this page), ιτ 17 — A7 _ ^^ _ B7 ___ five Explanation of the invention (15) Comparative experiment B The procedure of Example I was repeated t.Bu t.Bu with a phosphite of the following formula (the phosphite ester No. 2 used in EP — A — 5 1 8 24 1).

P—O

t.Bu t.Bu The conversion rate of employees' cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs after printing for 1 hour was 56.9%, and the following products were obtained: 4-pentenoic acid methyl ester 19 mol% 2-pentenoic acid methyl Esters 3 0 5 Mole% Methyl valerate 3 8 Mole% 3 — Methylmethylvalerate 1 2 5 Mole% 4 — Methyl as *? Methylvalerate 2 7 7 Mole% 5-Methylformylvalerate 2 3 6 Mole% 1 9 Conversion rate after 9 hours is 99.9% 9 The following products are obtained 2- Methylvalerate 0 2 Mole% Methylvalerate 1 8 9 Mole% 3 — Methylformylvalerate 1 6 • 7 Mole% 4 — Methylformylvalerate 3 5 • 2 Mole% 5 — Methylformylvalerate 2 9 • 0 The above Mohr results show that the formation of non-chelated ligands such as 4C, C, as used in the present m) is not suitable for the highly selective preparation of 5-formamylpentyl (read first Note the surface to fill out this page) • This paper stapled scale applicable Chinese National Standard (CNS) A4 size (210X297 mm) -18 -. A7 B7 V. Description (16 invention)

Comparative experiment C uses the phosphite ester of the following formula (equivalent to EP-A-N ester 1 acid for phosphorus rate conversion after conversion. 1 hour 2 8 small table 6 6 0 6, refer to 5 steps 5 steps ο 3 Choice of 6 1 The actual production of the selected examples is heavy. X% 0

C \\

£ JC 〇 ο

(Please read the precautions on the back before filling out this page.) _ Order printed by the Central Standards Bureau of the Ministry of Economic Affairs, printed by the employee consumer cooperatives. The paper size applies to Chinese National Standard (CNS) A4 (210X297 mm). 1 19 — 386075 Α7 Β7 V. Description of the invention (Π) Table 2 Time 6 hours 2 6 hours Conversion rate 13.6 48.3 2 Methylpentenoate 12.0 10.4 4 Methyl monopentenoate 4.6 1 · 3 Methyl pentanoate 3.5 1 3-methyl valerate 17.1 9. 5 4-methylmethylvalerate 19.9 2 1.9 —methylmethylvalerate --------, ...'... ............. 4 2.7 5 2.0 Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Example m Uses such as the ligand ( 2) Phosphite repeat example I. Its L / R h is 4.9. The concentration of R h is the same as in Example I. After 47 hours, the conversion rate was 26.7%, and the selectivity to methyl 5-methylfluorenylvalerate was 63.4 mole%, and the n / b ratio was 2.8 (n / b is applicable to the paper size China National Standard (CNS) A4 specification (210X297 mm): -20-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 386075 A7 B7 V. Description of the invention (18) Linear 5-Methylmethylvalerate The ratio of the branched chain of 3-methylamylvalerate and 4-methylamylvalerate).

Example IV The procedure of Example I was repeated using a phosphite such as the ligand (3). The concentration of R h was the same as in Example I, L / R h was 4 · 9 and the conversion rate after 3 1 1 hours was 35.7%. The selectivity for methyl 5-formamylvalerate is 75.8 mol% and the n / b ratio is 6.1.

Example V The procedure of Example 1 was repeated using a phosphite such as the ligand (4), the concentration of R h was the same as that of Example I, L / Rh was 5, and the conversion rate was 26.8% after 28 hours. The selectivity to methyl 5-methylformylvalerate is 65.8 mole% and the n / b ratio is 4.4.

Example VI The procedure of Example I was repeated using a phosphite such as the ligand (5), the concentration of R h was the same as that of Example I, L / R h was 5, and the conversion was 43.9% after 44.5 hours. The selectivity to methyl 5-formamylvalerate was 62.4 mol% and the n / b ratio was 3.3.

Example W The procedure of Example I was repeated using a phosphite such as the ligand (6). The concentration of Rh was the same as that of Example I, and the L / Rh was 5. After 66 hours, the paper size was adapted to the Chinese National Standard (CNS). A4 specification (210X297mm) (Please read the precautions on the back before filling this page) -β

-21-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 386075 A7 B7 V. Description of the invention (19) The chemical conversion rate is 50.2%, and the selectivity to methyl 5-formamylvalerate is 71_1 mole%, n / The b ratio is 6.4. (谙 Please read the precautions on the back before filling this page) Binding This paper size is applicable to China National Standard (CNS) A4 (210X297mm) -22-

Claims (1)

6. Annex 1 to the scope of patent application Patent application No. 8 3 1 1 2 2 0 0 Chinese patent application amendment Amendment of the Republic of China 88 February 1 Amendment 1. A use of carbon monoxide and hydrogen in the presence of germanium and phosphite In the case of a catalyst system for a seat, a method of preparing 3-pentylenoic acid or 3-pentenoic acid ester by hydroformylation to prepare 5-methylpentanoic acid or the corresponding 5-methylpentanoyl ester, It is characterized in that the phosphite ligand is represented by the following formula: nnn ^ Ί · nnn -nn 1 κ I · · 1 · 1 (Please read the precautions on the back before filling this page) Wherein R1 and R2 are the same or different monovalent aromatic hydrocarbon groups containing 6 to 30 carbon atoms, which may be substituted at the ortho position by an alkoxy group or an alkyl group, and A is an η valence having 1 to 30 carbon atoms. Hydrocarbyl, η is an integer from 2 to 8, and each [—O — PCOR1) (OR2)] group may be the same or different from each other, R1 and R2 are not connected to each other, and only pass through the phosphorus atom P is connected, and the phosphite and germanium form a chelate complex. 2. The method according to item 1 of the patent application, wherein the hydrocarbon groups Ri and R2 are substituted with a branched alkyl group having 3 to 6 carbon atoms. Method, wherein R1 and R2 are independently phenyl or / 3-fluorenyl. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)-line Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs. Printed by Consumer Cooperatives 6. Annex 1 to the scope of patent application Patent application No. 8 3 1 1 2 2 0 0 Chinese patent application amendment Amendment of the Republic of China 88 February 1 Amendment 1. A use of carbon monoxide and hydrogen in the presence of germanium and phosphite In the case of a catalyst system for a seat, a method of preparing 3-pentylenoic acid or 3-pentenoic acid ester by hydroformylation to prepare 5-methylmethylpentanoic acid or the corresponding 5-methylpentanoyl ester, It is characterized in that the phosphite ligand is represented by the following formula: nnn ^ Ί · nnn -nn 1 κ I · · 1 · 1 (Please read the precautions on the back before filling this page) Wherein R1 and R2 are the same or different monovalent aromatic hydrocarbon groups containing 6 to 30 carbon atoms, which may be substituted at the ortho position by an alkoxy group or an alkyl group, and A is an η valence having 1 to 30 carbon atoms. Hydrocarbyl, η is an integer from 2 to 8, and each [—O — PCOR1) (OR2)] group may be the same or different from each other, R1 and R2 are not connected to each other, and only pass through the phosphorus atom P is connected, and the phosphite and germanium form a chelate complex. 2. The method according to item 1 of the patent application, wherein the hydrocarbon groups Ri and R2 are substituted with a branched alkyl group having 3 to 6 carbon atoms. Method, wherein R1 and R2 are independently phenyl or / 3-fluorenyl. This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm)-employees of the Bureau of Intellectual Property of the Ministry of Economic Affairs. Printed by Consumer Cooperatives A8 B8 C8 D8 386075 t, patent application scope 4. If the scope of patent application is the first Or 2 methods, where A is C — (CH2—) 4. 5. The method of claim 1 or 2, wherein the 3-pentenoate is represented by the following general formula (2), CH3-CH-CH-CH2-COR II 〇. Where R is having 1 (cyclo) alkyl of 8 carbon atoms. Or aryl or aralkyl having 6-12 carbon atoms. 6. The method according to item 1 or 2 of the scope of patent application, in addition to 3-pentenoates, there are also 4-pentene 'esters and 2-pentenoates' and 3-pentenoates The concentration is higher than 50%. -------, ----- ί-Strike .------- Order · -------- Line (Please read the notes on the back before filling this page) Ministry of Economy The paper size printed by the Intellectual Property Bureau employee consumer cooperative is applicable to China National Standard (CNS) A4 (210 X 297 mm) -2-