CN117550961A - Method for synthesizing 1, 9-nonanal - Google Patents

Method for synthesizing 1, 9-nonanal Download PDF

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CN117550961A
CN117550961A CN202311512204.9A CN202311512204A CN117550961A CN 117550961 A CN117550961 A CN 117550961A CN 202311512204 A CN202311512204 A CN 202311512204A CN 117550961 A CN117550961 A CN 117550961A
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organic solvent
reaction
homogeneous catalyst
octenal
hydroxide
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刘传卓
李永刚
李志坚
汤易天
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Shanghai Zhonghua Technology Co ltd
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Shanghai Zhonghua Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
    • C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

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  • Organic Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention provides a method for synthesizing 1, 9-nonanediol, which comprises the following steps: (1) hydrolysis reaction: carrying out hydrolysis reaction on a compound of the formula I to prepare 7-octen-1-ol; (2) a selective oxidation reaction: carrying out selective oxidation reaction on 7-octen-1 alcohol to prepare 7-octenal; (3) hydroformylation reaction: carrying out hydroformylation on 7-octenal, hydrogen and carbon monoxide in the presence of a homogeneous catalyst to prepare 1, 9-nonanal; wherein the homogeneous catalyst consists of rhodium dicarbonyl acetylacetonate and 4, 6-bis (diphenylphosphine) phenazine. The method for synthesizing the 1, 9-nonanal has the advantages of high reaction efficiency, low cost, simple operation, high total yield of products and few byproducts.

Description

Method for synthesizing 1, 9-nonanal
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for synthesizing 1, 9-nonanal.
Background
Dialdehyde is a common intermediate of industrial chemicals, and can be subjected to oxidation, reduction, hydroamination and other reactions to obtain various important chemical raw materials, so that the synthesis of dialdehyde is always a hot spot for people to study.
1, 9-nonanediol is used as long-chain dialdehyde, and the oxidation product azelaic acid has the effects of inhibiting cell proliferation, reducing proliferation of propionibacteria, preventing synthesis of related proteins and the like, is commonly used for preparing external antibacterial products, and has antibacterial and anti-inflammatory effects; the reduction product nonanediol is an organic raw material with wider application, and is commonly used for producing perfumes, lubricating oil, printing ink, paint, cosmetics, plasticizer, various additives and the like; the reductive amination product, namely the nonanediamine, is a key intermediate of the high-temperature special nylon PA9T, and the high-temperature special nylon PA9T has the advantages of excellent formability, extremely low water absorption, high mechanical strength, toughness and dimensional stability, excellent chemical corrosion resistance, excellent electrical breakdown resistance, good colorability and the like, and has irreplaceable application in the fields of electronics, electrics, automobile industry and the like.
As early as 1961, walter et al (Justus Liebigs Annalen der Chemie,1961,640,111-26) reported a method for synthesizing 1, 9-nonanal by removing the imidazole ring from 1, 9-bis (3, 5-dimethyl-1H-pyrazol-1-yl) nonane-1, 9-dione, which is a raw material, but the synthesis method is complicated and the preparation cost is high.
In 2001, botteghi et al (J.mol. Catalyst. A: chem.2001,175, 17-25) reported the use of 1, 6-heptadiene as a starting material, rhodium tris (triphenylphosphine) carbonyl hydride (RhH (CO) (PPh) 3 ) 3 ) 4, 5-bis-diphenylphosphine-9, 9-dimethyl xanthene (Xantphos) is used as a catalyst to carry out hydroformylation reaction to prepare the 1, 9-nonanal. The reaction has high conversion rate but lower catalytic efficiency.
The colali company reports the reaction of obtaining 1, 9-nonanal from butadiene as a raw material through hydration dimerization, isomerization and hydroformylation reactions in sequence. US2009287032A1 discloses the hydration and dimerization of butadiene as starting material to 2, 7-octadien-1-ol using a catalyst composed of palladium/phosphorus ligands; US2012029229A1 discloses the isomerisation of 2, 7-octadien-1-ol to 7-octene 1-aldehyde under the catalysis of a copper catalyst; JP4183974B2, US7160835B2, JP2014189525A and US9464018B2 disclose H 2 And CO mixed gas is subjected to hydroformylation reaction under the action of catalysts consisting of rhodium dicarbonyl acetylacetonate and different organophosphorus complexes to obtain the 1, 9-nonanal. The method has the advantages of easily available raw materials and high reaction efficiency, but has higher requirements on reaction temperature and reaction process. The synthetic route of 1, 9-nonanediol reported by colali is as followsAs shown.
Therefore, development of a1, 9-nonanal synthesis method with low raw material cost, high reaction efficiency, high product yield, mild reaction conditions and simple operation is needed.
Disclosure of Invention
In order to solve the problems in the prior art, the invention develops a novel multi-step synthesis route of 1, 9-nonanediol. The method adopts a compound of the formula I as a starting material, and the 1, 9-nonanal is obtained through hydrolysis, selective oxidation and hydroformylation reactions in sequence. The method has the advantages of high reaction efficiency, low cost, simple operation, high total yield of products and few byproducts.
Specifically, the invention provides a method for synthesizing 1, 9-nonanediol, which comprises the following steps:
(1) Hydrolysis reaction: carrying out hydrolysis reaction on a compound of the formula I to prepare 7-octen-1-ol;
in the compound of the formula I, X is Cl, br, I, p-toluenesulfonyloxy, trifluoromethanesulfonyl, cyano or thiocyano;
(2) Selective oxidation reaction: carrying out selective oxidation reaction on 7-octen-1 alcohol to prepare 7-octenal;
(3) Hydroformylation reaction: carrying out hydroformylation on 7-octenal, hydrogen and carbon monoxide in the presence of a homogeneous catalyst to prepare 1, 9-nonanal;
wherein the homogeneous catalyst is formed by combining rhodium dicarbonyl acetylacetonate and 4, 6-bis (diphenylphosphine) phenazine.
In one or more embodiments, in step (1), the compound of formula I, a basic material, tetrabutylammonium iodide, an organic solvent, and water are mixed and subjected to a hydrolysis reaction to provide 7-octen-1-ol.
In one or more embodiments, in step (1), the alkaline substance is selected from one or more of a metal oxide selected from one or more of calcium oxide, magnesium oxide, barium oxide, aluminum oxide, and ferric oxide, a metal hydroxide selected from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, neodymium hydroxide, and cesium hydroxide, a metal carbonate selected from one or more of sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, barium carbonate, rubidium carbonate, and cesium carbonate, and a metal bicarbonate selected from one or more of sodium bicarbonate, potassium bicarbonate, and calcium bicarbonate.
In one or more embodiments, in step (1), the organic solvent is selected from one or more of aprotic polar solvents selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, 1, 4-dioxane, tetrahydrofuran, and dichloromethane, and protic polar solvents selected from one or more of alcohol compounds; preferably, the alcohol compound is selected from one or two of methanol and ethanol.
In one or more embodiments, in step (1), the basic substance and the compound of formula I are fed in a molar ratio of from 0.01:1 to 50:1, preferably from 0.2:1 to 5:1.
In one or more embodiments, in step (1), the feed molar ratio of tetrabutylammonium iodide to the compound of formula I is from 0.001:1 to 50:1, preferably from 0.05:1 to 0.5:1.
In one or more embodiments, in step (1), 0.01 to 5L, preferably 0.02 to 2L, of the organic solvent is used per mole of the compound of formula I.
In one or more embodiments, in step (1), the volume ratio of water to organic solvent is from 0.1:1 to 5:1, preferably from 0.3:1 to 1:1.
In one or more embodiments, in step (1), the temperature of the hydrolysis reaction is from 80 to 110 ℃, preferably from 90 to 110 ℃.
In one or more embodiments, in step (2), 7-octen-1-ol, an oxidant, and an organic solvent are mixed and subjected to a selective oxidation reaction to obtain 7-octenal.
In one or more embodiments, in step (2), the oxidizing agent is selected from one or both of dess-martin reagent and 2-iodoxybenzoic acid.
In one or more embodiments, in step (2), the organic solvent is selected from one or more of aprotic polar solvents selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, 1, 4-dioxane, tetrahydrofuran, and dichloromethane, and protic polar solvents selected from one or more of alcohol compounds; preferably, the alcohol compound is selected from one or two of methanol and ethanol.
In one or more embodiments, in step (2), the oxidant and 7-octen-1-ol are fed in a molar ratio of from 0.5:1 to 10:1, preferably from 0.6:1 to 1.5:1.
In one or more embodiments, in step (2), 1 to 10L, preferably 1 to 5L, of the organic solvent is used per mole of 7-octen-1-ol.
In one or more embodiments, in step (2), the temperature of the selective oxidation reaction is from-10 to 40 ℃.
In one or more embodiments, step (3) comprises: rhodium dicarbonyl acetylacetonate and 4, 6-bis (diphenylphosphine) phenazine are mixed in an organic solvent under anhydrous and anaerobic conditions to obtain a homogeneous catalyst solution.
In one or more embodiments, rhodium dicarbonyl acetylacetonate and 4, 6-bis (diphenylphosphine) phenazine are mixed at a temperature of 10 to 40 ℃ in the preparation of a homogeneous catalyst solution.
In one or more embodiments, the organic solvent is selected from one or more of a non-polar solvent selected from one or more of benzene, toluene, xylene, and ethylbenzene, and a polar solvent selected from one or more of dimethyl sulfoxide, N-methylpyrrolidone, sulfolane, N-dimethylformamide, N-dimethylacetamide, 1, 4-dioxane, and tetrahydrofuran in the homogeneous catalyst solution; preferably, the organic solvent is selected from one or more of non-polar solvents.
In one or more embodiments, the molar ratio of rhodium dicarbonyl acetylacetonate to 4, 6-bis (diphenylphosphine) phenazine in the homogeneous catalyst is in the range of from 1:1 to 1:20, preferably in the range of from 1:2 to 1:6.
In one or more embodiments, 100 to 5000L, preferably 500 to 2000L, of the organic solvent is used per mole of rhodium dicarbonyl acetylacetonate in the homogeneous catalyst solution.
In one or more embodiments, in step (3), the organic solvent, the homogeneous catalyst and 7-octenal are mixed, hydrogen and carbon monoxide are introduced, and hydroformylation reaction is performed to obtain 1, 9-nonanal.
In one or more embodiments, in step (3), the organic solvent is selected from one or more of a non-polar solvent selected from one or more of benzene, toluene, xylene, and ethylbenzene, and a polar solvent selected from one or more of dimethyl sulfoxide, N-methylpyrrolidone, sulfolane, N-dimethylformamide, N-dimethylacetamide, 1, 4-dioxane, and tetrahydrofuran; preferably, the organic solvent is selected from one or more of non-polar solvents.
In one or more embodiments, in step (3), the 7-octenal and rhodium dicarbonyl acetylacetonate in the homogeneous catalyst are fed in a molar ratio of from 10:1 to 10 6 1, preferably 10 4 :1～10 5 :1。
In one or more embodiments, in step (3), the molar ratio of hydrogen to carbon monoxide is from 0.1:1 to 10:1, preferably from 0.5:1 to 2:1.
In one or more embodiments, in step (3), 0.01 to 10L, preferably 0.02 to 5L, of the organic solvent is used per mole of 7-octenal.
In one or more embodiments, in step (3), the hydroformylation reaction is carried out at a temperature of from 60 to 150 ℃, preferably from 85 to 140 ℃.
In one or more embodiments, in step (3), the pressure of the hydroformylation reaction is from 0.1 to 10MPa, preferably from 0.5 to 5MPa.
The invention also provides a method for synthesizing 1, 9-nonanediol, which comprises step (3) of the method.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present invention, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
Herein, "comprising," "including," "containing," and similar terms are intended to cover the meaning of "consisting essentially of … …" and "consisting of … …," e.g., "a consisting essentially of B and C" and "a consisting of B and C" should be considered to have been disclosed herein when "a comprises B and C" is disclosed herein.
In this document, all features such as values, amounts, and concentrations that are defined as ranges of values or percentages are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise specified, percentages refer to mass percentages, and proportions refer to mass ratios.
Herein, when embodiments or examples are described, it should be understood that they are not intended to limit the invention to these embodiments or examples. On the contrary, all alternatives, modifications, and equivalents of the methods and materials described herein are intended to be included within the scope of the invention as defined by the appended claims.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
The invention provides a method for synthesizing 1, 9-nonanediol, which comprises the following steps:
(1) Hydrolysis reaction: carrying out hydrolysis reaction on a compound of the formula I to prepare 7-octen-1-ol;
in the compound of the formula I, X is Cl, br, I, p-toluenesulfonyloxy (-OTs), trifluoromethanesulfonyl-oxy (-OTf), cyano (-CN) or thiocyano (-SCN);
(2) Selective oxidation reaction: carrying out selective oxidation reaction on 7-octen-1 alcohol to prepare 7-octenal;
(3) Hydroformylation reaction: carrying out hydroformylation on 7-octenal, hydrogen and carbon monoxide in the presence of a homogeneous catalyst to prepare 1, 9-nonanal;
wherein the homogeneous catalyst consists of rhodium dicarbonyl acetylacetonate (chemical formula is Rh (acac) (CO)) 2 ) Combined with 4, 6-di (diphenyl phosphine) phenazine (Ni-Xantphos for short).
In the invention, the X group in the compound of the formula I is easy to leave, so that the required reaction condition is mild, the hydrolysis reaction is easy to occur, the generation efficiency of the hydrolysis product 7-octen-1-ol is improved, and the whole reaction efficiency is further improved. In some embodiments, the compound of formula I is 8-bromo-1-octene, which is inexpensive and readily available.
In the invention, the catalyst for the hydroformylation reaction is a homogeneous catalyst formed by combining rhodium metal and Ni-Xantphos, and has the advantages of high raw material conversion rate, extremely high product selectivity, high catalyst conversion number and the like, and has excellent catalytic performance.
In some embodiments, 8-bromo-1-octene is used as a raw material to prepare 1, 9-nonanediol through hydrolysis, selective oxidation and hydroformylation in sequence.
The hydrolysis reaction of step (1) is carried out under alkaline conditions.
In some embodiments, in step (1), the compound of formula I, a basic material, tetrabutylammonium iodide (TBAI), an organic solvent, and water are mixed to perform a hydrolysis reaction to provide 7-octen-1-ol. The hydrolyzed product 7-octene-1-alcohol in the step can be used for the next step through simple extraction, and the reaction is efficient and the operation is simple.
In the step (1), the alkaline substance may be selected from one or more of metal oxides, metal hydroxides, metal carbonates and metal hydrogencarbonates, the metal oxides may be selected from one or more of calcium oxide, magnesium oxide, barium oxide, aluminum oxide and ferric oxide, the metal hydroxides may be selected from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, neodymium hydroxide and cesium hydroxide, the metal carbonates may be selected from one or more of sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, barium carbonate, rubidium carbonate and cesium carbonate, and the metal hydrogencarbonates may be selected from one or more of sodium hydrogencarbonates, potassium hydrogencarbonates and calcium hydrogencarbonates. In some preferred embodiments, the alkaline material is selected from one or more of sodium hydroxide, potassium hydroxide, cesium carbonate, potassium carbonate and sodium carbonate, more preferably from one or both of cesium carbonate and potassium carbonate, which facilitates improved reaction conversion and 7-octen-1-ol yield in the product.
In the step (1), the organic solvent may be selected from one or more of aprotic polar solvents and protic polar solvents. The aprotic polar solvent may be selected from one or more of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DME), N-methylpyrrolidone, dimethylsulfoxide (DMSO), sulfolane, 1, 4-dioxane, tetrahydrofuran and dichloromethane. The protic polar solvent may be selected from one or more of the alcohol compounds. Preferably, the alcohol compound may be selected from one or both of methanol and ethanol. In some preferred embodiments, the organic solvent used in step (1) is DMF, which is advantageous in increasing the conversion of the reaction and the yield of 7-octen-1-ol in the product.
In step (1), the molar ratio of basic substance to compound of formula I may be in the range of from 0.01:1 to 50:1, preferably from 0.2:1 to 5:1, for example 0.5:1, 1.5:1, 2.5:1, 3.5:1, 4.5:1. In the invention, the feeding ratio is adjusted within the range, which is beneficial to improving the reaction yield and the reaction efficiency.
In step (1), the molar ratio of tetrabutylammonium iodide to the compound of formula I may be in the range from 0.001:1 to 50:1, preferably from 0.05:1 to 0.5:1, for example 0.1:1, 0.2:1, 0.3:1, 0.4:1. In the invention, the feeding ratio is adjusted within the range, which is beneficial to improving the reaction yield and the reaction efficiency.
In step (1), 0.01 to 5L, preferably 0.02 to 2L, for example 0.01L, 0.02L, 0.05L, 0.1L, 0.2L, 0.5L, 0.7L, 0.9L, 1.1L, 1.3L, 1.5L, 1.7L, 1.9L of organic solvent may be used per mole of the compound of formula I.
In step (1), the volume ratio of water to organic solvent may be from 0.1:1 to 5:1, preferably from 0.3:1 to 1:1, for example 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1.
In the step (1), the temperature of the hydrolysis reaction may be 80 to 110℃such as 85℃and 90℃and 95℃and 100℃and 105 ℃. In some preferred embodiments, the temperature of the hydrolysis reaction is between 90 and 110 ℃, which is advantageous in increasing the conversion of the reaction and the yield of 7-octen-1-ol in the product.
In some embodiments, the product produced in step (1) may be isolated and purified by: an aqueous electrolyte solution (e.g., saturated sodium chloride solution) is added to the reacted mixture, extracted with an extractant, dried, filtered, and the solvent is removed under reduced pressure to obtain 7-octen-1-ol. The separation and purification operation of the step is simple, and the reaction can be used for the next reaction after extraction.
In the process of separating and purifying the product in the step (1), the extractant can be selected from one or more of methyl ether, diethyl ether, propyl ether, methyl tertiary butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethyl acetate and dichloromethane.
In the process of separating and purifying the product in the step (1), anhydrous sodium sulfate can be added for drying.
The reaction of step (2) is carried out in the presence of an oxidizing agent.
In some embodiments, in step (2), 7-octen-1 alcohol, an oxidizing agent, and an organic solvent are mixed and subjected to a selective oxidation reaction to obtain 7-octenal.
In the step (2), the oxidizing agent may be Dess-Martin reagent, 2-iodoxybenzoic acid (IBX), or the like, and is preferably Dess-Martin reagent. The structure of Dess-Martin reagent isThe Dess-Martin reagent is used as an oxidant, so that the yield and the selectivity of the oxidation reaction are improved.
In the step (2), the organic solvent may be selected from one or more of aprotic polar solvents and protic polar solvents. The aprotic polar solvent may be selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, 1, 4-dioxane, tetrahydrofuran and dichloromethane. The protic polar solvent may be selected from one or more of the alcohol compounds. Preferably, the alcohol compound may be selected from one or both of methanol and ethanol.
In step (2), the molar ratio of oxidant to 7-octen-1 alcohol may be in the range of 0.5:1 to 10:1, preferably 0.6:1 to 1.5:1, for example 0.6:1, 0.8:1, 1.0:1, 1.1:1, 1.3:1, 1.5:1. In the invention, the feeding ratio is adjusted within the range, which is beneficial to improving the reaction yield and the reaction efficiency.
In the step (2), 1 to 10L, preferably 1 to 5L, for example, 1.2L, 1.5L, 1.7L, 2L, 3L, 4L of the organic solvent may be used per mole of 7-octen-1 alcohol.
In step (2), the temperature of the selective oxidation reaction may be-10 to 40 ℃, for example-5 ℃,0 ℃,5 ℃,10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃. In some embodiments, the temperature of the selective oxidation reaction is from 10 to 40 ℃, such as from 20 to 30 ℃. In the invention, the reaction is carried out at the temperature in the range of the interval, the reaction is mild, and the operation is simple.
In some embodiments, the product produced in step (2) may be isolated and purified by: quenching the reaction, adjusting pH to 6-8, filtering to remove insoluble substances, separating, extracting the water phase, mixing the organic phases, drying, filtering, and distilling under reduced pressure.
In the process of separating and purifying the product in the step (2), the product can be quenched by using an alkaline saturated solution.
In the process of separating and purifying the product in the step (2), the alkaline saturated solution can be one or more selected from saturated sodium hydroxide solution, saturated potassium hydroxide solution, saturated sodium carbonate solution, saturated potassium carbonate solution, saturated sodium bicarbonate solution and saturated potassium carbonate solution.
In the process of separating and purifying the product in the step (2), the extractant can be selected from one or more of methyl ether, diethyl ether, propyl ether, methyl tertiary butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, ethyl acetate and dichloromethane.
In the process of separating and purifying the product in the step (2), anhydrous sodium sulfate can be used for drying.
In the separation and purification of the product of step (2), the temperature of reduced pressure distillation may be 50 to 200℃and preferably 100 to 160℃such as 110℃120℃130℃140℃150 ℃.
In the process of separating and purifying the product of the step (2), the pressure of reduced pressure distillation may be 1 to 10000Pa, preferably 50 to 2000Pa, for example 100Pa, 400Pa, 700Pa, 1000Pa, 1300Pa, 1600Pa, 1900Pa.
In some embodiments, the homogeneous catalyst is prepared by: mixing rhodium dicarbonyl acetylacetonate with Ni-Xantphos in organic solvent under anhydrous and anaerobic condition to obtain homogeneous catalyst solution. Rhodium dicarbonyl acetylacetonate and Ni-Xantphos may be mixed at 10-40℃ (e.g., 20℃, 25℃, 30℃). The homogeneous catalyst can be directly added into the reaction system of the step (3) and mixed with 7-octenal in the form of a homogeneous catalyst solution for hydroformylation.
In the present invention, the organic solvent used in preparing the homogeneous catalyst may be selected from one or more of a nonpolar solvent and a polar solvent. The non-polar solvent may be selected from one or more of benzene, toluene, xylene and ethylbenzene. The polar solvent may be selected from one or more of dimethylsulfoxide, N-methylpyrrolidone, sulfolane, N-dimethylformamide, N-dimethylacetamide, 1, 4-dioxane and tetrahydrofuran. Preferably, the organic solvent may be selected from one or more of non-polar solvents.
In the present invention, the molar ratio of rhodium dicarbonyl acetylacetonate to Ni-Xantphos in the homogeneous catalyst may be in the range of 1:1 to 1:20, preferably 1:2 to 1:6, for example 1:2, 1:3, 1:4, 1:5, 1:6.
In the present invention, 100 to 5000L, preferably 500 to 2000L, for example 8000L, 1000L, 1200L, 1500L, of organic solvent may be used per mol of rhodium dicarbonyl acetylacetonate in the homogeneous catalyst solution. In the step (3), the organic solvent, the homogeneous catalyst and 7-octenal are mixed, hydrogen and carbon monoxide are introduced, and hydroformylation reaction is carried out, so that 1, 9-nonanal is obtained.
In some embodiments, in step (3), the organic solvent, the homogeneous catalyst, and the 7-octenal are mixed, hydrogen and carbon monoxide are introduced, and hydroformylation is performed to obtain 1, 9-nonylaldehyde.
In the step (3), the organic solvent may be selected from one or more of a nonpolar solvent and a polar solvent. The non-polar solvent may be selected from one or more of benzene, toluene, xylene and ethylbenzene. The polar solvent may be selected from one or more of dimethylsulfoxide, N-methylpyrrolidone, sulfolane, N-dimethylformamide, N-dimethylacetamide, 1, 4-dioxane and tetrahydrofuran. Preferably, the organic solvent may be selected from one or more of non-polar solvents.
In the step (3), the feeding mole ratio of the 7-octenal to the rhodium dicarbonyl acetylacetonate in the homogeneous catalyst can be 10:1-10 6 1, preferably 10 4 :1～10 5 1, for example 10000:1, 20000:1, 30000:1, 40000:1, 50000:1, 60000:1, 70000:1, 80000:1, 90000:1, 100000:1. In the invention, the feeding ratio is adjusted within the range, which is beneficial to improving the reaction yield and the reaction efficiency.
In step (3), the molar ratio of hydrogen to carbon monoxide may be from 0.1:1 to 10:1, preferably from 0.5:1 to 2:1, for example 0.7:1, 0.9:1, 1.1:1, 1.3:1, 1.5:1, 1.7:1, 1.9:1. In the invention, the proportion of the mixed gas is adjusted within the range, which is beneficial to improving the reaction yield and the reaction efficiency.
In the step (3), 0.01 to 10L, preferably 0.02 to 5L, for example, 0.03L, 0.04L, 0.05L, 0.06L, 0.08L, 0.1L, 0.2L, 0.5L, 1L, 2L, 3L, 4L of an organic solvent may be used per mole of 7-octenal. In the invention, the dosage of the organic solvent is adjusted within the range, which is beneficial to improving the reaction yield and the reaction efficiency.
In step (3), the hydroformylation reaction may be carried out at a temperature of 60 to 150℃and preferably 85 to 140℃such as 90℃95℃105℃115℃100℃125℃135 ℃. In some preferred embodiments, the hydroformylation reaction is carried out at a temperature of from 90 to 140 ℃, e.g., from 100 to 140 ℃, from 100 to 120 ℃, from 110 to 120 ℃, which facilitates good conversion while using less catalyst.
In step (3), the pressure of the hydroformylation reaction may be from 0.1 to 10MPa, preferably from 0.5 to 5MPa, for example 1MPa, 2MPa, 3MPa, 4MPa.
In some embodiments, the product produced in step (3) may be isolated and purified by: cooling, deflating, concentrating to remove the solvent, and distilling under reduced pressure to obtain 1, 9-nonanal.
In the process of separating and purifying the product in the step (3), the cooling temperature can be 20-30 ℃, such as 25 ℃.
In the process of separating and purifying the product of the step (3), the temperature of reduced pressure distillation may be 80 to 250 ℃, preferably 120 to 180 ℃, such as 130 ℃, 140 ℃, 150 ℃, 160 ℃ and 170 ℃.
In the process of separating and purifying the product of the step (3), the pressure of reduced pressure distillation may be 1 to 20000Pa, preferably 1000 to 10000Pa, for example 2000Pa, 3000Pa, 4000Pa, 5000Pa, 6000Pa, 7000Pa, 8000Pa, 9000Pa.
The invention also provides a method for synthesizing 1, 9-nonanediol comprising the step (3) of the invention.
Compared with the prior art, the invention has the following beneficial effects:
(1) The reaction scale of the hydrolysis reaction and the selective oxidation reaction is large, the yield is high, and the scale of the selective oxidation reaction is enlarged to 500g level, so that the reaction yield and purity are not reduced;
(2) The method has mild reaction conditions, the intermediate product generated by the hydrolysis reaction does not need to be separated, and the selective oxidation step uses reduced pressure distillation for separation, so that the method has low cost, and is convenient and efficient;
(3) The invention uses the homogeneous catalyst composed of rhodium metal and Ni-Xantphos for 7-octenal hydroformylation for the first time through the hydroformylation reaction step, the highest raw material conversion rate can reach more than 99%, the normal-to-iso ratio can reach more than 44.0, the catalyst conversion number (TON) can reach 499550, and the catalytic performance is excellent.
The invention will be illustrated by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the invention. The methods, reagents and materials used in the examples are those conventional in the art unless otherwise indicated. The starting compounds in the examples are all commercially available.
Example 1
Hydrolysis of 8-bromo-1-octene:
experiment 1: sequentially adding K into a reaction bottle 2 CO 3 (55.3 mg,0.4 mmol), TBAI (147.9 mg,0.4 mmol), DMF (1 mL), water (0.5 mL) and 8-bromo-1-octene (382.2 mg,2 mmol) and stirred at 100℃for 16h to give 7-octen-1-ol.
Experiment 2: other conditions are the same as in experiment 1, and only the alkaline substance is changed from K 2 CO 3 Replacement by Cs 2 CO 3 。
Experiment 3: other conditions are the same as in experiment 1, and only the alkaline substance is changed from K 2 CO 3 Replaced by Na 2 CO 3 。
Experiment 4: other conditions are the same as in experiment 1, and only the alkaline substance is changed from K 2 CO 3 And replaced with NaOH.
Experiment 5: other conditions were the same as in experiment 1, only TBAI was not added.
Experiment 6: other conditions were the same as in experiment 1, except that the organic solvent was replaced with DMSO instead of DMF only.
After the reaction is finished, the residual raw material content and the content of each product in the reaction liquid in the test experiments 1-6 are analyzed by a gas chromatograph, and the raw material conversion rate, the 7-octene-1-alcohol yield and the octadiene yield are obtained through calculation by an area normalization method. The specific experimental conditions and results of experiments 1-6 are shown in Table 1. Table 1: experimental conditions and results of experiments 1-6 for synthesizing 7-octen-1-ol by hydrolysis of 8-bromo-1-octene in example 1
Example 2
Hydrolysis of 8-bromo-1-octene:
experiment 1: sequentially adding K into eggplant-shaped bottle 2 CO 3 (1.382 g,10 mmol), TBAI (3.694 g,10 mmol), DMF (25 mL), water (12.5 mL) and 8-bromo-1-octene (9.552 g,50 mmol) were stirred at 80℃for 16h to give 7-octen-1-ol.
Experiment 2: other conditions were the same as in experiment 1, and the temperature was adjusted to 100℃only.
Experiment 3: other conditions were the same as in experiment 1, and the temperature was adjusted to 110℃only.
Experiment 4: other conditions were the same as in experiment 1, the temperature was adjusted to 100℃only, K 2 CO 3 The amount of (C) was adjusted to 25mmol.
After the reaction, the raw material conversion rate, the 7-octene-1-ol yield and the octadiene yield in the reaction liquid of the test experiments 1-4 are analyzed and tested by a gas chromatograph. The specific experimental conditions and results of experiments 1-4 are shown in Table 2.
Table 2: experimental conditions and results of experiments 1-4 for synthesizing 7-octen-1-ol by hydrolysis of 8-bromo-1-octene in example 2
Example 3
Hydrolysis of 8-bromo-1-octene: sequentially adding K into 100mL eggplant-shaped bottle 2 CO 3 (1.38 g,10 mmol), TBAI (3.694 g,10 mmol), DMF (25 mL), water (12.5 mL) and 8-bromo-1-octene (9.56 g,50 mmol) were stirred at 100deg.C for 16h. After the reaction, a saturated sodium chloride solution (400 mL) was added, the mixture was extracted 3 times with ethyl acetate (400 mL), the extracted organic phases were combined, and ethyl acetate and anhydrous Na were removed under reduced pressure 2 SO 4 Drying, filtering and decompressing to remove the solvent to obtain the crude 7-octen-1-ol.
Selective oxidation of 7-octen-1-ol: dichloromethane (60 mL) was added to the crude 7-octen-1-ol obtained in the previous step in an ice-water bath, dess-Martin reagent (21.2 g,50 mmol) was added in several portions and stirred at room temperature (25 ℃) overnight. After the reaction was completed, GC-MS was performed. After confirming that the basic reaction of the raw materials is complete, saturated NaHCO 3 The solution was quenched and the pH was adjusted to 7. Insoluble materials were filtered off, the solution was separated, and the aqueous phase was extracted with dichloromethane (3 x 2 l). The organic phases were combined, na 2 SO 4 And (5) drying. Filtering, removing the solvent under reduced pressure, and decompressing the residueThe colorless liquid 7-octenal 4.29g was obtained by distillation and separation, the total yield of the two steps was 68%, and the purity was 96.4%.
Example 4
Hydrolysis of 8-bromo-1-octene: according to the hydrolysis reaction of 8-bromo-1-octene in example 3, 500g (2615 mmol) of 8-bromo-1-octene was used as a raw material to prepare crude 7-octen-1-ol in several portions.
Selective oxidation of 7-octen-1-ol: dichloromethane (4.5L) was added to the crude 7-octen-1-ol obtained in the previous step in an ice-water bath, dess-Martin reagent (1.11 kg,2615 mmol) was added in several portions and stirred at room temperature (25 ℃) overnight. GC-MS detection. After confirming that the basic reaction of the raw materials is complete, saturated NaHCO 3 The solution was quenched and the pH was adjusted to 7. Insoluble materials were filtered off, the solution was separated, and the aqueous phase was extracted with dichloromethane (3 x 2 l). The organic phases were combined, most of the dichloromethane was removed under reduced pressure, and saturated NaHCO was used again 3 The solution was washed until no gas was generated to remove acetic acid as much as possible. Separating the organic phase from the aqueous phase with Na 2 SO 4 And (5) drying. The solvent was removed by filtration under reduced pressure, and the residue was separated by distillation under reduced pressure to give 244.56g of 7-octenal as a colorless liquid, with a total yield of 74% in two steps and a purity of 98%.
Example 5
Preparation of homogeneous catalyst solution: under anhydrous and anaerobic conditions, rh (acac) (CO) is added into a reaction bottle 2 (2.58 mg,0.01 mmol) and Ni-Xantphos (17.2 mg,0.03 mmol) were added 10mL of toluene and stirred at room temperature (25 ℃ C.) for 5 minutes to prepare a homogeneous catalyst solution having a concentration of 0.001mol/L.
Hydroformylation of 7-octenal:
experiment 1: toluene (3 mL), a preformed homogeneous catalyst solution (1 mL,0.001 mmol), and 7-octenal (0.15 mL,1 mmol) were added sequentially to a hydrogenation flask and transferred to a 100mL autoclave. Replacing hydrogen three times, sequentially charging hydrogen with the pressure of 1.0MPa and carbon monoxide with the pressure of 1.0MPa, and reacting at the temperature of 85 ℃ for 16h. After stopping the reaction, the autoclave was cooled to room temperature (25 ℃) and the gas was vented.
Experiment 2: to a 100 mL-volume autoclave, toluene (20 mL), a preformed homogeneous catalyst solution (1 mL,0.001 mmol) and 7-octenal (1.5 mL,10 mmol) were sequentially added, hydrogen was replaced three times, hydrogen gas of 1.0MPa and carbon monoxide of 1.0MPa were sequentially charged, and the reaction was carried out at 85℃for 16 hours. After stopping the reaction, the autoclave was cooled to room temperature (25 ℃) and the gas was vented.
Experiment 3: other conditions were the same as in experiment 2, except that the temperature was adjusted to 120℃and the amount of 7-octenal was adjusted to 10mmol.
Experiment 4: otherwise, the conditions were the same as in experiment 2, and the amount of 7-octenal was adjusted to 20mmol and the temperature was adjusted to 120 ℃.
Experiment 5: other conditions were the same as in experiment 2, except that the amount of 7-octenal was adjusted to 50mmol, the temperature was adjusted to 120℃and the hydrogen pressure was adjusted to 1.5MPa, and the carbon monoxide pressure was adjusted to 1.5MPa.
After the reaction is finished, the residual raw materials and the contents of all products in the reaction liquid in the test experiments 1-5 are analyzed by a gas chromatograph, and the raw material conversion rate, the aldehyde product normal-to-iso ratio and the product yield are calculated by an area normalization method. The specific experimental conditions and results of experiments 1-5 are shown in Table 3. Herein, S/C is 7-octenal and Rh (acac) (CO) 2 N-iso ratio = linear aldehyde yield/branched aldehyde yield. Then, toluene was removed by concentration, and the resultant was distilled under reduced pressure to obtain the objective 1, 9-nonanediol.
Table 3: experimental conditions and results for experiments 1-5 of Rh (I)/Ni-Xantphos catalyzed hydroformylation of 7-octenal in example 5
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Comparative example 1
Preparation of homogeneous catalyst solution: anhydrous anaerobic conditionNext, rh (acac) (CO) was added to the reaction flask 2 (2.58 mg,0.01 mmol) and Ni-Xantphos (17.2 mg,0.03 mmol) were added 10mL of toluene and stirred at room temperature (25 ℃ C.) for 5 minutes to prepare a homogeneous catalyst solution having a concentration of 0.001mol/L.
Hydroformylation of 7-octenal:
experiment 1: to a 100 mL-volume autoclave, toluene (20 mL), a preformed homogeneous catalyst solution (1 mL,0.001 mmol) and 7-octenal (1.5 mL,10 mmol) were sequentially added, hydrogen was replaced three times, hydrogen gas of 1.0MPa and carbon monoxide of 1.0MPa were sequentially charged, and the reaction was carried out at 85℃for 16 hours. After stopping the reaction, the autoclave was cooled to room temperature (25 ℃) and the gas was vented.
Experiment 2: other conditions were the same as in experiment 1, and the temperature was adjusted to 100℃only.
Experiment 3: other conditions were the same as in experiment 1, and the temperature was adjusted to 120℃only.
Experiment 4: otherwise, the conditions were the same as in experiment 1, except that the amount of 7-octenal was adjusted to 20mmol and the temperature was adjusted to 120 ℃.
Experiment 5: other conditions were the same as in experiment 1, except that the amount of 7-octenal was adjusted to 50mmol, the temperature was adjusted to 120℃and the hydrogen pressure was adjusted to 1.5MPa, and the carbon monoxide pressure was adjusted to 1.5MPa.
After the reaction is finished, a gas chromatograph is adopted to analyze and test the conversion rate of raw materials, the positive-to-negative ratio of aldehyde products and the yield of each product in the reaction liquid of the experiment 1-5. The specific experimental conditions and results of experiments 1-5 are shown in Table 4. Then, toluene was removed by concentration, and the resultant was distilled under reduced pressure to obtain the objective 1, 9-nonanediol.
Table 4: experimental conditions and results of experiments 1-5 of Rh (I)/Xantphos-catalyzed 7-octenal hydroformylation in comparative example 1
As can be seen from tables 3 and 4, the reaction has a higher normal-to-iso ratio and fewer hydrogenation byproducts than when using Xantphos and using Ni-Xantphos ligand, exhibiting excellent reaction effect of Rh (I)/Ni-Xantphos catalyst in catalyzing the hydroformylation of 7-octenal.

Claims (10)

1. A method of synthesizing 1, 9-nonanediol, the method comprising the steps of:
(1) Hydrolysis reaction: carrying out hydrolysis reaction on a compound of the formula I to prepare 7-octen-1-ol;
in the compound of the formula I, X is Cl, br, I, p-toluenesulfonyloxy, trifluoromethanesulfonyl, cyano or thiocyano;
(2) Selective oxidation reaction: carrying out selective oxidation reaction on 7-octen-1 alcohol to prepare 7-octenal;
(3) Hydroformylation reaction: carrying out hydroformylation on 7-octenal, hydrogen and carbon monoxide in the presence of a homogeneous catalyst to prepare 1, 9-nonanal;
wherein the homogeneous catalyst is formed by combining rhodium dicarbonyl acetylacetonate and 4, 6-bis (diphenylphosphine) phenazine.
2. The process according to claim 1, wherein in step (1), the compound of formula I, an alkaline substance, tetrabutylammonium iodide, an organic solvent and water are mixed and subjected to hydrolysis to obtain 7-octen-1-ol.
3. The method of claim 2, wherein the method has one or more of the following features:
in the step (1), the alkaline substance is selected from one or more of metal oxides, metal hydroxides, metal carbonates and metal bicarbonates, the metal oxides are selected from one or more of calcium oxide, magnesium oxide, barium oxide, aluminum oxide and ferric oxide, the metal hydroxides are selected from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, neodymium hydroxide and cesium hydroxide, the metal carbonates are selected from one or more of sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, barium carbonate, rubidium carbonate and cesium carbonate, and the metal bicarbonates are selected from one or more of sodium bicarbonate, potassium bicarbonate and calcium bicarbonate;
in the step (1), the organic solvent is selected from one or more of aprotic polar solvents and protic polar solvents, the aprotic polar solvents are selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, 1, 4-dioxane, tetrahydrofuran and dichloromethane, and the protic polar solvents are selected from one or more of alcohol compounds; preferably, the alcohol compound is selected from one or two of methanol and ethanol;
in the step (1), the feeding mole ratio of the alkaline substance to the compound of the formula I is 0.01:1-50:1, preferably 0.2:1-5:1;
in the step (1), the feeding mole ratio of the tetrabutylammonium iodide to the compound of the formula I is 0.001:1-50:1, preferably 0.05:1-0.5:1;
in step (1), 0.01 to 5L, preferably 0.02 to 2L, of the organic solvent is used per mole of the compound of formula I;
in the step (1), the volume ratio of the water to the organic solvent is 0.1:1-5:1, preferably 0.3:1-1:1;
in the step (1), the temperature of the hydrolysis reaction is 80 to 110 ℃, preferably 90 to 110 ℃.
4. The process according to claim 1, wherein in the step (2), 7-octen-1-ol, an oxidizing agent and an organic solvent are mixed and subjected to a selective oxidation reaction to obtain 7-octenal.
5. The method of claim 4, wherein the method has one or more of the following features:
in the step (2), the oxidant is selected from one or two of dess-martin reagent and 2-iodized benzoic acid;
in the step (2), the organic solvent is selected from one or more of aprotic polar solvents and protic polar solvents, the aprotic polar solvents are selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, 1, 4-dioxane, tetrahydrofuran and dichloromethane, and the protic polar solvents are selected from one or more of alcohol compounds; preferably, the alcohol compound is selected from one or two of methanol and ethanol;
in the step (2), the feeding mole ratio of the oxidant to the 7-octene-1-alcohol is 0.5:1-10:1, preferably 0.6:1-1.5:1;
in the step (2), 1 to 10L, preferably 1 to 5L of the organic solvent is used per mole of 7-octen-1-ol;
in the step (2), the temperature of the selective oxidation reaction is-10-40 ℃.
6. The method of claim 1, wherein step (3) comprises: rhodium dicarbonyl acetylacetonate and 4, 6-bis (diphenylphosphine) phenazine are mixed in an organic solvent under anhydrous and anaerobic conditions to obtain a homogeneous catalyst solution.
7. The method of claim 6, wherein the method has one or more of the following features:
when preparing a homogeneous catalyst solution, mixing rhodium dicarbonyl acetylacetonate and 4, 6-bis (diphenylphosphine) phenazine at the temperature of 10-40 ℃;
the organic solvent is selected from one or more of a nonpolar solvent and a polar solvent, the nonpolar solvent is selected from one or more of benzene, toluene, xylene and ethylbenzene, and the polar solvent is selected from one or more of dimethyl sulfoxide, N-methylpyrrolidone, sulfolane, N-dimethylformamide, N-dimethylacetamide, 1, 4-dioxane and tetrahydrofuran; preferably, the organic solvent is selected from one or more of non-polar solvents;
in the homogeneous catalyst, the molar ratio of rhodium dicarbonyl acetylacetonate to 4, 6-bis (diphenylphosphine) phenazine is 1:1-1:20, preferably 1:2-1:6;
in the homogeneous catalyst solution, 100 to 5000L, preferably 500 to 2000L of the organic solvent is used per mol of rhodium dicarbonyl acetylacetonate.
8. The method of claim 1, wherein in step (3), the organic solvent, the homogeneous catalyst and 7-octenal are mixed, hydrogen and carbon monoxide are introduced, and hydroformylation reaction is performed to obtain 1, 9-nonanal.
9. The method of claim 8, wherein the method has one or more of the following features:
in the step (3), the organic solvent is selected from one or more of a nonpolar solvent selected from one or more of benzene, toluene, xylene and ethylbenzene, and a polar solvent selected from one or more of dimethyl sulfoxide, N-methylpyrrolidone, sulfolane, N-dimethylformamide, N-dimethylacetamide, 1, 4-dioxane and tetrahydrofuran; preferably, the organic solvent is selected from one or more of non-polar solvents;
in the step (3), the feeding mole ratio of the 7-octenal to the rhodium dicarbonyl acetylacetonate in the homogeneous catalyst is 10:1-10 6 1, preferably 10 4 :1～10 5 :1；
In the step (3), the molar ratio of rhodium dicarbonyl acetylacetonate to 4, 6-bis (diphenylphosphine) phenazine in the homogeneous catalyst is 1:1-1:20, preferably 1:2-1:6;
in the step (3), the molar ratio of the hydrogen to the carbon monoxide is 0.1:1-10:1, preferably 0.5:1-2:1;
in the step (3), 0.01 to 10L, preferably 0.02 to 5L of the organic solvent is used per mole of 7-octenal;
in the step (3), the temperature of the hydroformylation reaction is 60-150 ℃, preferably 85-140 ℃;
in the step (3), the pressure of the hydroformylation reaction is 0.1-10 MPa, preferably 0.5-5 MPa.
10. A method of synthesizing 1, 9-nonanediol, comprising step (3) of the method of claim 1.
CN202311512204.9A 2023-11-14 2023-11-14 Method for synthesizing 1, 9-nonanal Pending CN117550961A (en)

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