CN113061149A - Preparation method of interchelated ligand, hydroformylation catalyst and dihydric alcohol - Google Patents

Preparation method of interchelated ligand, hydroformylation catalyst and dihydric alcohol Download PDF

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CN113061149A
CN113061149A CN202110332891.0A CN202110332891A CN113061149A CN 113061149 A CN113061149 A CN 113061149A CN 202110332891 A CN202110332891 A CN 202110332891A CN 113061149 A CN113061149 A CN 113061149A
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ligand
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hydroformylation
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rhodium
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CN113061149B (en
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许振成
刘超
黄少峰
任亚鹏
王加琦
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • 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
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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    • 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
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
    • C07C29/158—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof containing rhodium or compounds thereof
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom
    • 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
    • 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
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Abstract

The invention discloses a preparation method of an interchelated ligand, a hydroformylation catalyst and dihydric alcohol. The mutual matching typeLigand comprising ligand unit I
Figure DDA0002996163100000011
And ligand unit II

Description

Preparation method of interchelated ligand, hydroformylation catalyst and dihydric alcohol
Technical Field
The present invention relates to organophosphine ligands, and in particular to a complementary ligand for use in the hydroformylation of olefins and a process for the preparation of glycols.
Background
Hydroformylation is a common chemical process for the preparation of fatty aldehydes having one more carbon atom than the olefin used. Hydroformylation has become the largest homogeneous catalytic reaction on a commercial scale. Hydroformylation of olefins is an important method for industrially synthesizing aldehydes or alcohols, and the aldehydes, alcohols and derivatives thereof produced thereby are used in large quantities for producing plasticizers, solvents, pharmaceutical intermediates, perfumes, and the like.
The ligands commonly used in industry at present are phosphine ligands and phosphite ligands, wherein the phosphite ligands can show better catalytic activity and selectivity in the catalytic hydroformylation of Rh.
US5808168 uses a two-stage reaction system with a monodentate phosphine ligand as catalyst to produce alcohol by hydrogenation of the crude aldehyde, but this process has a lower catalyst selectivity and requires separation of the aldehyde from the product and further reaction with the production of a higher level of impurities. Patent US5922634 also uses a secondary reaction system, which also produces more impurities. Patent CN201280025530.0 mentions that the application of bisphosphine ligands to the hydroformylation for the preparation of 1, 4-butanediol produces a large amount of by-products, resulting in a low reaction yield.
A catalytic system for hydroformylation reaction with higher activity and selectivity is needed.
Disclosure of Invention
In order to overcome the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a ligand of the type which is complementary to a ligand of the type used in hydroformylation reactions and a hydroformylation catalyst. When the catalyst is used for catalyzing olefin to prepare dihydric alcohol, the catalyst has high reaction activity and linear selectivity.
A ligand of the interchelated type for hydroformylation reaction contains ligand unit
Figure BDA0002996163090000021
Figure BDA0002996163090000022
And a ligand unit
Figure BDA0002996163090000023
Wherein R is1、R2Independently from each other, selected from H, aryl or heterocyclic aromatic group, alkyl; is preferably C1-C4Alkyl, thienyl, phenyl, pyrrolyl.
In a preferred embodiment, the ligand unit I of the ligand of the invention is selected from the following compounds:
Figure BDA0002996163090000024
Figure BDA0002996163090000025
Figure BDA0002996163090000026
the ligand unit II is selected from the following compounds:
Figure BDA0002996163090000027
Figure BDA0002996163090000031
preferably, in the ligand of the invention, the molar ratio of the ligand unit I to the ligand unit II is 1.0 (1.0-1.5).
The preparation method of the ligand unit I comprises the following steps: (1) 5-bromo-2-aminopyrrole (III) with chlorophosphine R1R2PCl (IV) generates coupling reaction to generate an intermediate V; (2) and reacting the intermediate V with pyrrole-2-acetic acid (VI) to obtain a ligand unit I.
The specific reaction formula is shown as follows:
Figure BDA0002996163090000032
in the preparation method of the ligand unit I, the molar ratio of the 5-bromo-2-aminopyrrole to the chlorophosphine is 1 (1.0-3.0), preferably 1 (1.0-1.5).
In the process for preparing ligand unit I according to the present invention, step (1) is preferably carried out in the presence of n-butyllithium added in an amount of 1.0 to 3.0 times, preferably 1.0 to 1.5 times, the molar amount of 5-bromo-2-aminopyrrole.
In the preparation method of the ligand unit I, the step (1) is preferably carried out in the presence of a solvent, and the solvent is preferably one or more of dichloromethane, toluene, chloroform and acetone.
In the preparation method of the ligand unit I, the reaction temperature in the step (1) is liquid nitrogen cooling bath temperature (-78 ℃ to-50 ℃).
In the preparation method of the ligand unit I, in the step (2), the feeding molar ratio of the intermediate V to the intermediate VI is 1 (1.0-10.0), preferably 1 (1.0-2.5).
In the preparation method of the ligand unit I, in the step (2), the adding amount of 4-Dimethylaminopyridine (DMAP) is 0.1-3.0 times, preferably 1.0-1.5 times of the molar amount of the intermediate IV.
In the preparation method of the ligand unit I, in the step (2), the addition amount of (N-N' diisopropylcarbodiimide) DIC is 0.1-3.0 times, preferably 1.0-1.5 times of the molar amount of the intermediate IV.
In the preparation method of the ligand unit I, the step (2) is preferably carried out in the presence of a solvent, wherein the solvent is one or more of n-hexane, chlorobenzene and dichloromethane.
In the preparation method of the ligand unit I, the reaction temperature in the step (2) is room temperature.
The preparation method of the ligand unit II comprises the following steps: (a) 5-Bromofuran-2-carboxylic acid (VI)I) With chlorophosphines R1R2PCl is subjected to coupling reaction to generate an intermediate IX; (b) and reacting the intermediate IX with 2-aminomethyl furan (X) to obtain the ligand II.
The specific reaction formula is shown as follows:
Figure BDA0002996163090000041
Figure BDA0002996163090000051
in the preparation method of the ligand unit II, the molar ratio of the 5-bromofuran-2-carboxylic acid to the chlorophosphine is 1 (1.0-3.0), preferably 1 (1.0-1.5).
In the process for preparing ligand unit II according to the present invention, step (a) is preferably carried out in the presence of n-butyllithium in an amount of 1.0 to 3.0 times, preferably 1.0 to 1.5 times, the molar amount of 5-bromofuran-2-carboxylic acid.
In the preparation method of the ligand unit II according to the present invention, the step (a) is preferably performed in the presence of a solvent, and the solvent is preferably one or more of dichloromethane, toluene, chloroform and acetone.
In the preparation method of the ligand unit II, the reaction temperature in the step (a) is the liquid nitrogen cooling bath temperature (-78 ℃ to-50 ℃).
In the preparation method of the ligand unit II, in the step (b), the molar ratio of the intermediate IX to the 2-aminomethyl furan (X) is 1 (1.0-10.0), preferably 1 (1.0-2.5).
In the process for preparing ligand unit II according to the present invention, 4-Dimethylaminopyridine (DMAP) is added in step (b) in an amount of 0.1 to 3.0 times, preferably 1.0 to 1.5 times, the molar amount of intermediate IX.
In the process for the preparation of ligand unit II according to the present invention, (N-N' diisopropylcarbodiimide) DIC is added in step (b) in an amount of 0.1 to 3.0 times, preferably 1.0 to 1.5 times the molar amount of intermediate IX.
In the preparation method of the ligand unit II, the step (b) is preferably carried out in the presence of a solvent, wherein the solvent is one or more of n-hexane, chlorobenzene and dichloromethane.
In the method for preparing the ligand unit II, the reaction temperature in the step (b) is room temperature.
The ligand of the invention can be used for preparing dihydric alcohol by hydroformylation of unsaturated fatty acid.
A hydroformylation catalyst comprising: the invention relates to a ligand and a transition metal compound.
The transition metal compound of the present invention may be one or more salts of transition metal central atoms such as Fe, Mn, Pt, Pd, Rh, Ru, Ir, Co, etc., preferably one or more salts of Co and Rh.
As a preferable embodiment, the transition metal compound according to the present invention includes one or more of rhodium acetate, rhodium octanoate, rhodium acetylacetonate carbonyl, rhodium dicarbonyl acetylacetonate, triphenylphosphine rhodium acetylacetonate, cobalt acetate, cobalt octanoate, cobalt acetylacetonate, and triphenylphosphine cobalt acetylacetonate, and preferably one or more of rhodium acetylacetonate, rhodium octanoate, and cobalt acetate.
A method for preparing dihydric alcohol comprises the following steps: in the presence of the hydroformylation catalyst, the olefin hydroformylation reaction is carried out to prepare the dihydric alcohol.
The olefin of the invention is C2-C20Linear or branched olefins, preferably one or more of ethylene, propylene, butene, pentene, hexene, butadiene, pentadiene.
Without being limited by any theory, the catalytic reaction of the ligand of the invention is that oxygen in furan group of ligand unit II, NH in pyrrole group of ligand unit I and amido are connected by hydrogen bond, and metal central atom forms a complex to form a bidentate phosphine ligand to catalyze the hydroformylation reaction of olefin in the first step; after hydroformylation is carried out to generate aldehyde, the pyrrole group in the ligand unit I and carbonyl oxygen bind aldehyde group hydrogen through hydrogen bonds, the reaction level of the carbonyl oxygen is reduced through the action of NH bond in the amide group and the carbonyl oxygen, and M-H bond in the catalyst is added into the aldehyde group to complete hydrogenation to generate alcohol, so that the alcohol is obtained.
The linear alcohol is obtained by using the hydroformylation catalyst in one step, so that the equipment investment is greatly reduced, the catalytic activity is high, the linear selectivity is good, the chelating capacity with metal is strong, the reaction activity is high, and the method is suitable for industrial large-scale production.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples.
The sources of the raw materials of the reagents used in the examples and comparative examples of the present invention are as follows:
n-butyllithium, 5-bromofuran-2-carboxylic acid, 5-bromo-2-aminopyrrole, chlorophosphine ligand, 2-aminomethylpyridine, 4-dimethylaminopyridine, N-N' -diisopropylcarbodiimide were all purchased from carbofuran reagents, Inc.; methylene chloride, n-hexane, commercially available from Shanghai national reagents, Inc.
The other raw materials of the reagents are all commercial products unless otherwise specified.
The above reagents were purchased and used directly.
The test methods used in the examples of the invention and the comparative examples are as follows:
the product structure was determined by an elemental analyzer, Vario EL cube Analyzer, Elementar, Germany.
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
Example 1
(1) Preparation of the catalyst
Ligand I: to CH of 5-bromo-2-aminopyrrole (67.94g, 0.422mol) at-78 ℃ under an argon atmosphere2Cl2To the (1.5L) solution was slowly added n-BuLi (29.75g, 0.4645 mol). The mixture was stirred for 30 minutes, then Ph was added2PCl (109.63g, 0.4965mol), after a further reaction at-78 ℃ for 1.5 hours, was warmed to room temperature and at this temperatureStirring at room temperature for an additional 2 hours to give intermediate V (106.5g, 0.4 mol); pyrrole-2-acetic acid (75.08g, 0.6mol), DMAP (48.9g, 0.4mol), DIC (75.72,0.6mol) were then added and reacted at room temperature for 4 hours to give the product (145.62g, 0.39 mol).
Figure BDA0002996163090000071
Elemental analysis: 70.79; h is 5.38; n is 11.23; o is 4.30; p is 8.30.
Ligand II: to CH of 5-bromofuran-2-carboxylic acid (80.59g, 0.422mol) under an argon atmosphere at-78 deg.C2Cl2To the (1.5L) solution was slowly added n-BuLi (29.75g, 0.4645 mol). The mixture was stirred for 30 minutes, then Ph was added2PCl (109.54g, 0.4965mol), after 1.5 hours at-78 ℃ and warming to room temperature and stirring at this temperature for a further 2 hours, gave intermediate IX (118.5g, 0.4 mol); 2-Aminomethylfuran (58.27g, 0.6mol), DMAP (48.9g, 0.4mol), DIC (75.72,0.6mol) were then added and reacted at room temperature for 4 hours to give the product (144.17g, 0.39 mol).
Figure BDA0002996163090000081
Elemental analysis: 70.38; h is 4.86; n is 3.75; o is 12.81; p is 8.20.
(2) Preparation of n-propanol by hydroformylation of ethylene
Benzene 300g, Rh (acac) (CO)20.2g of ligand I2 g and ligand II 2g are added into an autoclave with a stirrer and a thermometer, and H is used in the autoclave2The synthesis gas with 1:1 of CO is replaced for 3 times, then the ethylene is added to 1.0MPaG, and then the volume ratio H is added2: the synthesis gas with CO 1:1 is heated to the pressure of 3.2MPaG, the temperature is raised to 90 ℃, the stirring speed is 900rpm, the reaction is carried out for 2 hours, the liquid product is taken out, and the liquid product is kept stand and layered, so that the product of n-propanol is obtained (the conversion rate is 97%, and the selectivity is 98.6).
Example 2
(1) Preparation of the catalyst
Ligand I: preparation ofThe procedure is as in example 1, except that Ph in example 1 is used2Change of PCl (109.54g, 0.4965mol) to C8H8S2PCl (115.53g, 0.4965 mol). The product was finally obtained (180.73g, 0.4 mol).
Figure BDA0002996163090000091
Elemental analysis: c, 58.59; n is 10.28; h is 3.92; 15.62 parts of S; o is 3.92; p: 7.67.
ligand II: the procedure is as in example 1 except that Ph in example 1 is2Change of PCl (109.54g, 0.4965mol) to C8H8S2PCl (115.53g, 0.4965 mol). The product was finally obtained (151.09g, 0.39 mol).
Figure BDA0002996163090000092
Elemental analysis: 55.79; n is 3.65; h is 3.62; 12.41 parts of O; p is 8.02; s: 16.51.
(2) preparation of n-butanol by hydroformylation of propylene
300g of benzene, 0.2g of rhodium octoate, 2g of ligand I and 2.42g of ligand II are added into an autoclave with a stirrer and a thermometer, and H is used in the autoclave2Replacing 3 times with 1:1 CO for synthetic gas, adding propylene to 1.5MPaG, and adding H in volume ratio2: the synthesis gas with CO being 1:1 is heated to the pressure of 4.7MPaG, the temperature is raised to 100 ℃, the stirring speed is 900rpm, the reaction is carried out for 1.5 hours, the liquid product is taken out, and the liquid product is kept stand and layered, so that the product n-butanol is obtained (the conversion rate is 98.6%, and the selectivity is 97.1%).
Example 3
(1) Preparation of the catalyst
Ligand I: the procedure is as in example 1 except that Ph in example 1 is2Change of PCl (109.54g, 0.4965mol) to C8H8N2PCl (110.22, 0.4965 mol). The final product was 137.02g (0.39 mol).
Figure BDA0002996163090000101
Elemental analysis: c, 61.50; n is 19.92; h is 5.14; o is 4.55; p: 8.89.
ligand II: the procedure is as in example 1 except that Ph in example 1 is2Change of PCl (109.54g, 0.4965mol) to C8H6S2PCl (115.53g, 0.4965 mol). The product was finally obtained (151.09g, 0.39 mol).
Figure BDA0002996163090000102
Elemental analysis: 55.79; n is 3.65; h is 3.62; 12.41 parts of O; p is 8.02; s: 16.51.
(2) preparation of 1, 6-hexanediol by hydroformylation of 1, 3-butadiene
300g of benzene, 0.2g of cobalt acetate, 2g of ligand I and 3.3g of ligand II are added into an autoclave with a stirrer and a thermometer, and H is used in the autoclave2The synthesis gas with 1:1 of CO is replaced 3 times, 1, 3-butadiene is added to 2MPaG, and then H is added in volume ratio2: the synthesis gas with CO being 1:1 is heated to the pressure of 5.0MPaG, the temperature is increased to 105 ℃, the stirring speed is 900rpm, the reaction is carried out for 3 hours, the liquid product is taken out, and the liquid product is kept stand and layered, so that the product 1, 6-hexanediol (the conversion rate is 97.6%, and the selectivity is 96.8%) is obtained.
Example 4
(1) Preparation of the catalyst
Ligand I: the procedure is as in example 1 except that Ph in example 1 is2PCl (109.54g, 0.4965mol) was changed to di-n-butyl phosphine chloride C8H18PCl (89.70g, 0.4965 mol). The final product was 130.03g (0.39 mol).
Figure BDA0002996163090000111
Elemental analysis: c, 64.83; n is 12.57; h is 8.48; p: 9.31, respectively; o is 4.81.
Ligand II: the procedure is as in example 1 except that Ph in example 1 is2PCl (109.54g, 0.4965mol) was changed to di-n-butyl phosphine chloride C8H18PCl (89.70g, 0.4965 mol). The product was finally obtained (130.79g, 0.39 mol).
Figure BDA0002996163090000112
Elemental analysis: 64.48; n is 4.21; h is 7.83; 14.29 parts of O; p is 9.19.
(2) Preparation of n-heptanol by hydroformylation of hexene
300g of benzene, 0.2g of cobalt acetate, 2g of ligand I and 2g of ligand II are added into an autoclave with a stirrer and a thermometer, and H is used in the autoclave2The CO is replaced by 1:1 synthetic gas for 3 times, then the hexene is added to 2MPaG, and then the volume ratio H is added2: the synthesis gas with CO 1:1 is heated to the pressure of 5.5MPaG, the temperature is increased to 102 ℃, the stirring speed is 900rpm, the reaction is carried out for 2.5 hours, the liquid product is taken out, and the liquid product is kept stand and layered, so that the product n-heptanol (the conversion rate is 97.5 percent, and the selectivity is 97.9 percent) is obtained.
Example 5: preparation of n-butanol by hydroformylation of propylene
300g of benzene, 0.2g of rhodium octanoate, 2g of ligand I prepared in example 2 and 0.5g of ligand II were placed in an autoclave equipped with a stirrer and a thermometer, and H was used in the autoclave2Replacing 3 times with 1:1 CO for synthetic gas, adding propylene to 1.5MPaG, and adding H in volume ratio2: the synthesis gas with CO 1:1 is heated to the pressure of 4.7MPaG, the temperature is raised to 100 ℃, the stirring speed is 900rpm, the reaction is carried out for 1.5 hours, the liquid product is taken out, and the liquid product is kept stand and layered to obtain the product n-butanol (the conversion rate is 95.5 percent, and the selectivity is 96.7 percent).
Example 6: preparation of n-butanol by hydroformylation of propylene
300g of benzene, 0.2g of rhodium octanoate, 2g of ligand I prepared in example 2, and 0.8g of ligand II were charged into an autoclave equipped with a stirrer and a thermometer, and the inside of the autoclave was purged with H2Replacing 3 times with 1:1 CO for synthetic gas, adding propylene to 1.5MPaG, and adding H in volume ratio2: synthesis gas with CO 1:1 to 4.7MPaG pressure, raising temperature to 100 deg.C and stirring speedThe reaction is carried out at the speed of 900rpm for 1.5 hours, and a liquid product is taken out and is kept stand for layering to obtain a product of n-butanol (the conversion rate is 84.2.3 percent, and the selectivity is 82.3 percent).
Comparative example 1: preparation of n-propanol by hydroformylation of ethylene
Benzene 300g, Rh (acac) (CO)20.2g of ligand I2 g of example 1 are placed in an autoclave equipped with a stirrer and a thermometer and the autoclave is purged with H2The synthesis gas with 1:1 of CO is replaced for 3 times, then the ethylene is added to 1.0MPaG, and then the volume ratio H is added2: the synthesis gas with CO 1:1 is heated to the pressure of 3.2MPaG, the temperature is raised to 90 ℃, the stirring speed is 900rpm, the reaction is carried out for 2 hours, the liquid product is taken out, and the liquid product is kept stand and layered, so that the product, namely the n-propanol, is obtained (the conversion rate is 81.2%, and the selectivity is 75.4%).
Comparative example 2: preparation of n-propanol by hydroformylation of ethylene
Benzene 300g, Rh (acac) (CO)20.2g of ligand II from example 1 was charged into an autoclave equipped with a stirrer and a thermometer and charged with H2The synthesis gas with 1:1 of CO is replaced for 3 times, then the ethylene is added to 1.0MPaG, and then the volume ratio H is added2: the synthesis gas with CO 1:1 is heated to the pressure of 3.2MPaG, the temperature is raised to 90 ℃, the stirring speed is 900rpm, the reaction is carried out for 2 hours, the liquid product is taken out, and the liquid product is kept stand and layered, so that the product, namely the n-propanol, is obtained (the conversion rate is 78.3%, and the selectivity is 74.1%).
Comparative example 3
(1) Preparation of n-heptanol by hydroformylation of hexene
300g of toluene, 0.2g of cobalt acetate and 2.8g of ligand Xantphos (4, 5-bis-diphenylphosphino-9, 9-dimethylxanthene) were placed in an autoclave equipped with a stirrer and a thermometer, and the autoclave was purged with H2The CO is replaced by 1:1 synthetic gas for 3 times, then the hexene is added to 2MPaG, and then the volume ratio H is added2: the synthesis gas with CO 1:1 is heated to the pressure of 12.5MPaG, the temperature is raised to 130 ℃, the stirring speed is 900rpm, the reaction is carried out for 4 hours, the liquid product is taken out, and the liquid product is kept stand and layered, so that the product n-heptanol (the conversion rate is 92.1 percent, and the selectivity is 85.4 percent) is obtained.

Claims (10)

1. A ligand of the interworking type for hydroformylation reactions, comprising a ligand unit I
Figure FDA0002996163080000011
And ligand unit II
Figure FDA0002996163080000012
Wherein R is1、R2Independently from each other, selected from H, aryl or heterocyclic aromatic group, alkyl; is preferably C1-C4Alkyl, thienyl, phenyl, pyrrolyl.
2. The ligand of claim 1, wherein the ligand unit I is selected from one or more of the following compounds:
Figure FDA0002996163080000013
Figure FDA0002996163080000014
3. the ligand of claim 1, wherein the ligand unit II is selected from one or more of the following compounds:
Figure FDA0002996163080000015
Figure FDA0002996163080000021
4. the ligand of claim 1, wherein the molar ratio of ligand unit I to ligand unit II is 1.0 (1.0-1.5).
5. The ligand of claim 1 or 2, wherein the ligand unit I is prepared by a process comprising the steps of: (1) 5-bromo-2-aminopyrrole with chlorophosphine R1R2PCl is subjected to coupling reaction to generate an intermediate V
Figure FDA0002996163080000022
(2) And reacting the intermediate V with pyrrole-2-acetic acid to obtain a ligand unit I.
6. The ligand of claim 1 or 3, wherein the ligand unit II is prepared by a process comprising the steps of: (a) 5-bromofuran-2-carboxylic acid with chlorophosphine R1R2PCl is subjected to coupling reaction to generate an intermediate IX
Figure FDA0002996163080000023
(b) And reacting the intermediate IX with 2-aminomethyl furan to obtain a ligand unit II.
7. A hydroformylation catalyst comprising a ligand of any one of claims 1 to 6 in a mutually coordinating form and a transition metal compound.
8. The hydroformylation catalyst according to claim 7, wherein the transition metal compound comprises one or more of rhodium acetate, rhodium octanoate, rhodium acetylacetonate, dicarbonyl acetylacetonate, triphenylphosphine rhodium acetylacetonate, cobalt acetate, cobalt octanoate, cobalt acetylacetonate, and triphenylphosphine cobalt acetylacetonate, preferably one or more of rhodium acetylacetonate, rhodium octanoate, and cobalt acetate.
9. A method for preparing dihydric alcohol comprises the following steps: the hydroformylation of olefins to produce glycols in the presence of the hydroformylation catalyst of claim 7.
10. The process of claim 9 wherein the olefin is C2-C20Linear or branched olefins, preferably one or more of ethylene, propylene, butene, pentene, hexene, butadiene, pentadiene.
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