CN102875599A - Novel tridentate phosphine ligand and application of same to linear hydroformylation and similar reactions - Google Patents

Novel tridentate phosphine ligand and application of same to linear hydroformylation and similar reactions Download PDF

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CN102875599A
CN102875599A CN2012103742451A CN201210374245A CN102875599A CN 102875599 A CN102875599 A CN 102875599A CN 2012103742451 A CN2012103742451 A CN 2012103742451A CN 201210374245 A CN201210374245 A CN 201210374245A CN 102875599 A CN102875599 A CN 102875599A
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reaction
general formula
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hydroformylation
replacement
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CN102875599B (en
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张绪穆
陈才友
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Wuhan University WHU
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Abstract

The invention discloses a novel tridentate phosphine ligand and application of the same to linear hydroformylation and similar reactions. The tridentate phosphine ligand is applied to efficient high-selectivity hydroformylation for the first time at present and applicable to efficient high-selectivity isomerized hydroformylation, hydrocarboxylation, hydrocyanation, isomerized formylation, hydroaminomethylation and the similar reactions. During the linear hydroformylation, selectivity of the tridentate phosphine ligand is obviously higher than that of a corresponding bidentate phosphine ligand. Besides, compared with a corresponding quadridentate phosphine ligand, the tridentate phosphine ligand is approximate in selectivity, easier to synthesize and higher in yield and displays higher TON (turnover number). The novel tridentate phosphine ligand selectively converts 1-hexylene and 1-octylene into n-heptaldehyde (used for synthesis of orange essence and rose essence) and n-nonaldehyde (flavoring matter) and is of great significance to hydroformylation-based industrial production.

Description

New tridentate phosphine part and the application in linear hydroformylation and similar reaction thereof
Technical field
The present invention relates to series of new three tooth phosphine parts and the application in linear hydroformylation and similar reaction thereof.
Background technology
Hydroformylation reaction is that Otto Roelen teaches in discovery in 1938 [1], be widely used in subsequently in the industry, nowadays hydroformylation reaction has become homogeneous catalytic reaction largest in the industrial production.Every year, aldehydes and the alcohol compound by the hydroformylation reaction production of the metal catalytics such as Fe, Zn, Mn, Co, Cu, Ag, Ni, Pt, Pd, Rh, Ru and Ir now reached 1,000 ten thousand tons [2]
Industrial, take propylene as starting raw material, the linear hydroformylation reaction by Rh catalysis obtains the important intermediate butyraldehyde, reaches 3,000,000 tons through the annual plasticizer phthalic acid dioctyl ester (DEHP) of producing of subsequent reactions again, and reaction process is seen Fig. 1.Simultaneously; thereby reduce the toxicity of plastics with the infiltration that reduces plastics for the molecular weight that increases synthetic softening agent; at present industrially use cheap butylene instead and the mixture of iso-butylene is raw material; linear hydroformylation reaction by Rh catalysis obtains the intermediate valeraldehyde; pass through again the larger softening agent of subsequent reactions synthetic molecular weight; its toxicity reduces greatly, and reaction process is seen Fig. 1.Therefore, hydroformylation reaction is considerable in industry, and development has very important effect for the catalyzer of the efficient highly selective of hydroformylation reaction in order to optionally obtain linear product so.
Although the catalyzer that a lot of researchers relate to hydroformylation reaction has been done large quantity research, the present technical problem that has also that catalyst levels is high, speed of response is slow, selectivity is relatively poor etc. and need to be resolved hurrily.
The hydroformylation reaction of being found by Otto professor Roelen is with Co metal complex (HCo (CO) in early days 4) make catalyzer, but severe reaction conditions, the linear selectivity of reaction is also bad, in addition, the catalyst precursor Co that adopts in the reaction 2(CO) 8Toxicity is very large [3]After 20 century 70s, the Rh metal complex replaces the main catalyzer that the Co metal complex becomes hydroformylation reaction gradually.By the Pruett of Union Carbide and the Booth of Union Oil etc. [4]HRh (the CO) (PPh of development 3) 2Catalyzer is widely used in commercialization, but obtains the active catalytic species in order to ensure highly selective, has used the PPh with respect to 820 times of Rh catalyst levelss in the reaction 3Part, the linearity that obtains and the ratio of branched product reach 17:1.Need greatly excessive PPh 3The reason of part is Rh-P coordinate bond easy fracture, PPh 3Part is from active catalytic species A(HRh (CO) (PPh optionally 3) 2) on fall down after, just can form active high but catalytic species B and the C of poor selectivity, referring to Fig. 2.Increase PPh 3During equivalent, the direction of active catalytic species A moves the balance of active catalytic species to generating optionally, thereby can improve the selectivity of reaction.
For fear of a large amount of use PPh 3Part, and guarantee that highly selective, researcher have designed and synthesized the bidentate phosphine part, wherein the most representative three class parts are respectively Bisbi series part, Xantphos series part and have the Biphephos series part of large steric hindrance substituted radical [5], structure is seen Fig. 3.This three classes part has represented good selectivity in hydroformylation reaction, the consumption of part is reduced to 5 equivalents simultaneously.
In recent years, the applicant designs and has synthesized four tooth phosphine parts on the Research foundation of bidentate phosphine part [6]The coordination mode of P atom and metal Rh has four kinds of forms shown in Figure 4 in the four tooth phosphine parts.Because four tooth phosphine parts have a plurality of chelatings site, have effectively suppressed the formation of low selective active catalytic species, the hydroformylation reaction take four tooth phosphine parts as catalyzer has obtained present best selectivity.
Although monodentate, bidentate and four tooth phosphine parts have been widely used in hydroformylation reaction, relatively high catalyzer equivalent, low reaction speed, relatively poor selectivity and narrower substrate scope remain problem demanding prompt solution in the linear hydroformylation reaction of selectivity.Given this, the design that is applicable to the efficient highly selective phosphine part of hydroformylation reaction remains present hot issue with synthetic.Simultaneously, have no the bibliographical information of any three tooth phosphine parts.
Relate to following reference in the literary composition:
[1]Chem?Abstr，1994，38-550;
[2]Adv.Synth.Catal.2009,351,537–540；
[3]Angew.Chem.Int.Ed.1994,33,2144；
[4]J.Org.Chem.1969,34,327；
[5]Chem.Abstr.,1988,108,7890；Acc.Chem.Res.2001,34,895；US?Patent,4769498,1988；
[6]J.Am.Chem.Soc.2006,128,16058-16061。
Summary of the invention
The present invention has proposed a series of three tooth phosphine parts, its synthetic method and the application in hydroformylation and similar reaction thereof take the efficient highly selective part that is applicable to linear hydroformylation reaction of Development of Novel as purpose.
In order to achieve the above object, the three tooth phosphine parts that the present invention proposes have the structure of general formula (I):
Figure BDA00002216830100021
In the general formula (I):
I, J, K, L, M, N, Q are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
Y is R, Ar, OR, OAr, pyrroles or substituted azole;
R is alkyl or substituted alkyl, and Ar is aryl.
Bridged linkage be can form between Q, the L replacement atom in the structure shown in the general formula (I) and five-ring or six-ring formed.
The first kind part of above-mentioned three tooth phosphine parts has the structure of general formula (II):
Figure BDA00002216830100031
In the general formula (II):
A, b, c, d, I, J, K, L, M, N, Q are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
R is alkyl or substituted alkyl, and Ar is aryl.
In the structure shown in the general formula (II), can form bridged linkage among a, b, c, d, I, J, K, L, M, N, the Q between any two adjacent replacement atoms and form five-ring or six-ring.
The Second Type part of above-mentioned three tooth phosphine parts has the structure of general formula (III):
Figure BDA00002216830100032
In the general formula (III):
A, b, c, d, E, F, G, I, J, K, L, M, N are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
R is alkyl or substituted alkyl, and Ar is aryl.
In the structure shown in the general formula (III), can form bridged linkage among a, b, c, d, E, F, G, I, J, K, L, M, the N between any two adjacent replacement atoms and form five-ring or six-ring.
The 3rd types of ligands of above-mentioned three tooth phosphine parts has the structure of general formula (IV):
Figure BDA00002216830100041
In the general formula (IV):
A, b, c, d, e, f, I, J, K, L, M, N, Q are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
R is alkyl or substituted alkyl, and Ar is aryl.
In the structure shown in the general formula (IV), can form bridged linkage among a, b, c, d, e, f, I, J, K, L, M, N, the Q between any two adjacent replacement atoms and form five-ring or six-ring.
The 4th types of ligands of above-mentioned three tooth phosphine parts has the structure of logical formula V:
Figure BDA00002216830100042
In the logical formula V:
A, b, c, d, e, I, J, K, L, M, N, Q are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
R is alkyl or substituted alkyl, and Ar is aryl.
In the structure shown in the logical formula V, can form bridged linkage among a, b, c, d, e, I, J, K, L, M, N, the Q between any two adjacent replacement atoms and form five-ring or six-ring.
The 5th types of ligands of above-mentioned three tooth phosphine parts has the structure of general formula (VI):
In the general formula (VI):
A, b, c, d, e, f, g, h, I, J, K, L, M, N, Q are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
Z is CH 2-CH 2, O, CH 2, NH or NR;
R is alkyl or substituted alkyl, and Ar is aryl.
In the structure shown in the general formula (VI), can form bridged linkage among a, b, c, d, e, f, g, h, I, J, K, L, M, N, the Q between any two adjacent replacement atoms and form five-ring or six-ring.
The 6th types of ligands of above-mentioned three tooth phosphine parts has the structure of general formula (VII):
Figure BDA00002216830100052
In the general formula (VII):
A, b, c, d, e, I, J, K, L, M, N, Q are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
R is alkyl or substituted alkyl, and Ar is aryl.
In the structure shown in the general formula (VI), can form bridged linkage among a, b, c, d, e, I, J, K, L, M, N, the Q between any two adjacent replacement atoms and form five-ring or six-ring.
The 7th type of part of above-mentioned three tooth phosphine parts has the structure of general formula (VIII):
Figure BDA00002216830100061
In the general formula (VIII):
A, b, c, d, e, f, g, h, I, J, K, L, M, N, Q are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
R is alkyl or substituted alkyl, and Ar is aryl.
In the structure shown in the general formula (VIII), any two adjacent substituted elements can form bridged linkage composition five-ring or six-ring among a, b, c, d, e, f, g, h, I, J, K, L, M, N, the Q.
The chelate ring of the active catalytic species that the bidentate phosphine part generates in the linear hydroformylation reaction of Rh catalysis is nonatomic ring.The sequestering power of nonatomic ring is significantly less than the sequestering power of corresponding five yuan and six-ring, therefore, under relatively high temperature, CO molecule with stronger coordination ability can replace the phosphorus atom that is sequestered in the Rh metal center get off relatively easily, see Fig. 5 (a), thereby but form the lower catalytic active species of active higher selectivity.
It is to increase part to the sequestering power of metal that the present invention designs one of purpose of three tooth phosphine parts, so that newly-generated active catalytic species have higher selectivity, thereby improves the selectivity of linear hydroformylation reaction.The active catalytic species that the present invention's three tooth phosphine parts and metal Rh form have two kinds of coordination modes, see Fig. 5 (b).Like this; dissociating of a phosphorus atom can be substituted by other the 3rd phosphorus atom in the three tooth phosphine parts; thereby the phosphorus concentration of Rh metal center increases greatly, thereby the active catalytic species that form have stronger sequestering power, will represent better selectivity in linear hydroformylation reaction.
Compare with existing four tooth phosphine parts, the selectivity of the present invention's three tooth phosphine parts is close to four tooth phosphine parts, but have advantages of be easy to synthetic and yield higher, the yield of the present invention's three tooth phosphine parts can reach 64%, but the yield of existing disclosed four tooth phosphine parts only has 32%.
Compared with prior art, the present invention has the following advantages and beneficial effect:
The present invention proposes a kind of novel, efficient highly selective three tooth phosphine parts, can be used as the catalyzer in linear hydroformylation and the similar reaction.Compare with four tooth phosphine parts, the selectivity of this three teeth phosphine part is suitable with four tooth phosphine parts, but more synthetic, and yield is higher.The present invention's three tooth phosphine parts can be converted into enanthaldehyde (being used for the synthetic of orange essence and rose compound) and n-nonyl aldehyde (food spice) with 1-hexene and 1-octene highly selective, and are therefore, significant to the industrial production based on hydroformylation reaction.
Description of drawings
Fig. 1 is the industrial reaction principle for preparing softening agent DEHP by the linear hydroformylation reaction of Rh catalysis;
Fig. 2 is the chemical equilibrium between active catalytic species A, B, the C, and wherein, A is the selective catalysis active specy, and B is active higher but catalytic species that selectivity is relatively poor, and C be that activity is the highest but catalytic species that selectivity is the poorest;
Fig. 3 is the structure iron of representative three class bidentate phosphine parts, and wherein, figure (a) be the structure iron of Bisbi series part, and figure (b) be the structure iron of Xantphos series part, schemes the structure iron that (c) is the serial part of Biphephos;
Fig. 4 be four tooth phosphine ligand structure figure and with four kinds of chelating patterns of metal Rh, wherein, figure (a) is four tooth phosphine ligand structure figure, figure (b) is four kinds of chelating patterns of four tooth phosphine parts and metal Rh; Fig. 5 is the coordination mode of bidentate phosphine part and three tooth phosphine parts and metal Rh, and wherein, figure (a) is the coordination mode of bidentate phosphine part and metal Rh, and figure (b) is the coordination mode of three tooth phosphine parts and metal Rh.
Embodiment
The part of the structure with general formula (I) that the present invention proposes according to the difference of X group, adopts different synthetic method preparations.
When X is O, adopt following synthetic method to prepare three tooth phosphine parts of the present invention:
Figure BDA00002216830100081
When X is CH 2The time, adopt following synthetic method to prepare three tooth phosphine parts of the present invention:
Figure BDA00002216830100082
When X is NH, adopt following synthetic method to prepare three tooth phosphine parts of the present invention:
Figure BDA00002216830100083
When X is NR, adopt following synthetic method to prepare three tooth phosphine parts of the present invention:
It is above,
I, J, K, L, M, N, Q are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
Y is R, Ar, OR, OAr, pyrroles or substituted azole;
R is alkyl or substituted alkyl, and Ar is aryl.
Bridged linkage be can form between Q, the L replacement atom in the general formula and five-ring or six-ring formed.
Below provide the specific examples (L1-L153) of the present invention's three tooth phosphine parts.
Figure BDA00002216830100092
Figure BDA00002216830100111
Figure BDA00002216830100121
Figure BDA00002216830100131
Figure BDA00002216830100141
Figure BDA00002216830100151
Figure BDA00002216830100161
Ar gets respectively following group in above-mentioned specific examples L37 ~ 56, L67 ~ 86, L126 ~ 145:
Figure BDA00002216830100171
Transition metal complex and any one three teeth phosphine part mixing afterreaction among the L1-L153 can be made catalyzer for linear hydroformylation reaction and similar reaction, and the similar reaction of linear hydroformylation reaction here refers to isomerization hydroformylation reaction, hydrocarboxylation reaction, the reaction of hydrogen cyano group, isomerization formyl reaction and hydroaminomethylation etc.The transition metal complex that is applicable among the present invention in linear hydroformylation and the similar reaction can be (Rh (COD) Cl) 2, (Rh (COD) 2) X, Rh (acac) are (CO) 2Or RuH (CO) 2(PPh 3) 2, wherein, COD is 1,5-cyclooctadiene, and acac is methyl ethyl diketone, and X is balance anion, can be BF 4, ClO 4, OTf, SbF 6, CF 3SO 3, B (C 6H 3(CF 3) 2) 4, Cl, Br or I.
In order to understand better the present invention, the present invention will be further described below in conjunction with example.
Embodiment 1
2,2 ', the preparation of 6-trimethoxy biphenyl (2,2 ', the preparation method of 6-trimethoxy biphenyl can be referring to document: Chem.Eur.J.2003, and 9,3209-3215), the building-up reactions formula is as follows:
Figure BDA00002216830100172
Two methyl-phenoxide 29.9g between adding in 500ml Shi Lunke (Schlenk) bottle that is full of nitrogen of drying; add 170mL anhydrous tetrahydro furan (THF) again and obtain mixing solutions under nitrogen protection, the hexane solution that at room temperature dropwise adds the n-Butyl Lithium of 136mL 1.6mol/L in this mixing solutions obtains reaction system.Behind the reaction 1h, dropwise add the THF solution of 69mL o-bromo-anisole in the reaction system, wherein, the quality of o-bromo-anisole is 18.7g, and is warming up to 60 ℃ of reaction 12h after at room temperature stirring 1h.After reaction finishes, reaction system is cooled to room temperature, adding the 200mL shrend goes out, separate organic phase, twice of extracted with diethyl ether of water, after the organic phase of gained merges with anhydrous sodium sulfate drying, filter, be spin-dried for, residuum is made eluent with sherwood oil and ethyl acetate and is separated through silica gel column chromatography and obtain target compound.The gained target compound is powdery white solid (7.56g, 31% productive rate).Rf=0.2(hexane/AcOEt=10:1); 1H?NMR(300MHz,CDCl 3):δ=3.63(s,6H;2OCH 3),3.66(s,3H;OCH 3),6.55-6.58(d, 3J(H,H)=8.3Hz,2H;3,5-H),6.89-7.12(m,3H;3,5,6-H),7.17-7.24ppm(m,2H;4-H); 13C?NMR(75MHz,CDCl 3):δ=55.8,56.0,104.2,111.2,120.3,123.6,128.6,128.8,132.2,157.5,158.1ppm.
Embodiment 2
2,2 ', the preparation of 6-trimethoxy biphenyl, the building-up reactions formula is as follows:
Figure BDA00002216830100181
Add 182mg 2 in Shi Lunke (Schlenk) pipe of drying, 6-dimethoxy phenylo boric acid adds the Pd (OAc) of 2.2mg again in mutually successively in gloves 2, the Xphos of 14.3mg, the anhydrous K of 318.5mg 3PO 4After the Schlenk pipe was replaced as nitrogen atmosphere, the o-bromo-anisole and the anhydrous THF of 3ml that add 0.5mmol obtained reaction system, and reaction system is reacted 24h under 60 ° of C.After reaction finishes, add the 3ml shrend and go out, with dichloromethane extraction 3 times, after the gained organic phase merges with anhydrous sodium sulfate drying, be spin-dried for, making the product that eluent obtains with sherwood oil and ethyl acetate behind silica gel column chromatography is white solid, productive rate 82%.Rf=0.2(hexane/AcOEt=10:1); 1H?NMR(300MHz,CDCl 3):δ=3.63(s,6H;2OCH 3),3.66(s,3H;OCH 3),6.55-6.58(d, 3J(H,H)=8.3Hz,2H;3,5-H),6.89-7.12(m,3H;3,5,6-H),7.17-7.24ppm(m,2H;4-H); 13C?NMR(75MHz?CDCl 3):δ=55.8,56.0,104.2,111.2,120.3,123.6,128.6,128.8,132.2,157.5,158.1ppm.
Embodiment 3
2,2 ', the preparation of 6-trihydroxy-biphenyl, the building-up reactions formula is as follows:
Figure BDA00002216830100182
In the 250mL of drying Schlenk bottle, add 2,2 of 2.44g ', 6-trimethoxy biphenyl, the Schlenk bottle is replaced as nitrogen atmosphere after, add the 100mL anhydrous methylene chloride and obtain mixing solutions.Under-78 ° of C, dropwise add the 4.4mL boron tribromide in the mixing solutions and obtain reaction system.Reaction system is risen to room temperature afterreaction 5h.After reaction finishes, reaction system is cooled to 0 ° of C, dropwise adding the 50ml shrend goes out, the separated and collected organic phase, water ethyl acetate extraction three times, each extraction 25mL ethyl acetate, merge organic phase and with filtering behind the anhydrous sodium sulfate drying, being spin-dried for, residuum is made eluent with sherwood oil and ethyl acetate, obtains powdery white solid (2.00g, 99% productive rate) after the silicagel column column chromatography for separation.Rf=0.5(AcOEt/hexane=1:1); 1H?NMR(300MHz,DMSO):δ=6.34-6.37(d, 3J(H,H)=7.8Hz,1H;2-OH),6.74-7.09(m,7H),8.81-8.84ppm(d, 3J(H,H)=10.8Hz,2H;2’,6-OH), 13C?NMR(75MHz,DMSO):δ=106.4,113.4,115.3,118.3,122.5,127.6,127.8,132.5,155.2,156.1ppm.
Embodiment 4
The preparation of two pyrroles's phosphorus chloride (2,2 ', the preparation method of 6-trimethoxy biphenyl can be referring to document: Organometallics, and 2002,21,3873-3883), the building-up reactions formula is as follows:
Figure BDA00002216830100191
Under nitrogen protection, add successively 8.7mL phosphorus trichloride and the anhydrous THF of 200mL in the 500mL Schlenk bottle of drying and obtain the THF solution of phosphorus trichloride; after the THF solution of phosphorus trichloride is cooled to 0 ℃; to contain 13.9mL pyrroles, 100mL(is excessive) the anhydrous THF mixed solution of 50mL of anhydrous triethylamine dropwise adds in the THF solution of phosphorus trichloride and obtains reaction system, NEt 3.HCl white precipitate is separated out at once.Reaction system is stirring reaction 12h under room temperature, and after reaction finished, the gained suspension liquid removed by filter NEt with the anhydrous THF dilution of 100mL 3.HCl.After filtrate is spin-dried for, and underpressure distillation (boiling point: 88 ℃, 2.7mmHg) collect target product, products therefrom is colourless transparent liquid, productive rate is 41%. 1H?NMR(300MHz,CDCl 3):δ=6.35(m,4H),7.04-7.05ppm(m,4H); 13C?NMR(75MHz,CDCl 3):δ=113.9,122.7ppm.
Embodiment 5
The preparation of three tooth phosphine ligand L 1, the building-up reactions formula is as follows:
In the 250mL of drying Schlenk bottle, under nitrogen protection, add respectively 8.7g two pyrroles's phosphorus chloride and the anhydrous THF of 50mL.Under room temperature, dropwise add successively 15mL(excessive) anhydrous triethylamine and 100mL 2,2 ', the THF solution of 6-trihydroxy-biphenyl obtains reaction system, NEt 3.HCl white precipitate is separated out at once, 2,2 ', in the THF solution of 6-trihydroxy-biphenyl 2,2 ', the quality of 6-trihydroxy-biphenyl is 2.02g.Reaction system is stirring reaction 6h under room temperature.Reaction removes by filter NEt after finishing 3.HCl white precipitate.After gained filtrate was spin-dried for, the gained mixture was at first made Fast Coarse by an alkali alumina chromatography column of carefully growing and is purified.After the leacheate that contains target product was spin-dried for, residuum recrystallization in methyl alcohol obtained white plates solid (4.26g), and productive rate is 64%.Rf=0.4(hexane/AcOEt=20:1); 1H?NMR(300MHz,CDCl 3):δ=6.21-6.23(d, 3J(H,H)=5.1Hz,12H),6.66-6.69(m,14H),6.83-6.85(d, 3J(H,H)=8.4Hz,1H),7.14-7.19(m,3H),7.29-7.34ppm(m,1H); 13C?NMR(75MHz,CDCl 3):δ=112.5,112.7,115.5,119.6,121.5,121.7,124.8,130.1,130.3,132.6ppm; 31P?NMR:δ=107.8ppm.
Embodiment 6
The hydroformylation reaction of simple terminal olefin
In being placed with the 5mL vial of magneton, adding 0.2mL is dissolved with the toluene solution of three tooth phosphine ligand L 1 of 0.8umol embodiment 5 preparations, 0.2mL be dissolved with (CO) 2 toluene solution of 0.2umol Rh metal complex Rh (acac), stirring at room 5min.Then add 2mmol terminal olefin and 0.1mL n-decane (as interior mark), adding toluene, to make the cumulative volume of reaction solution be 1mL again, and vial is transferred in the autoclave.Use N 2With the air displacement of autoclave three times, be filled with subsequently CO and H 2Each 5bar of gas.Adopt oil bath that autoclave is heated to 80 ℃, behind the reaction 2h, autoclave is positioned in the ice-water bath cools off.Discharge fully the gas in the autoclave is careful in stink cupboard, obtain the n:i value by gas-chromatography (GC) analyze reaction mixture at once, the n:i value is the linear product that generates behind the hydroformylation reaction and the ratio of the amount of substance of branched product.
Embodiment 7
The hydroformylation reaction of simple internal olefin:
In being placed with the 5mL vial of magneton, adding 0.2mL is dissolved with the toluene solution of three tooth phosphine ligand L 1 of 0.8umol embodiment 5 preparations, 0.2mL be dissolved with (CO) 2 toluene solution of 0.2umol Rh metal complex Rh (acac), stirring at room 5min.Then add 2mmol internal olefin and 0.1mL n-decane (as interior mark), adding toluene, to make the cumulative volume of reaction solution be 1mL again, and vial is transferred in the autoclave.Use N 2With the air displacement in the autoclave three times, be filled with subsequently CO and H 2Each 5bar of gas.Adopt oil bath that autoclave is heated to 100 ℃, behind the reaction 1h, autoclave is positioned in the ice-water bath cools off.In stink cupboard that the air release in the autoclave is complete, obtain the n:i value by gas-chromatography (GC) analyze reaction mixture at once, the n:i value is the linear product that generates behind the hydroformylation reaction ratio with the amount of substance of branched product.
Embodiment 8
Cinnamic hydroformylation reaction:
In being placed with the 5mL vial of magneton, add the toluene solution that 0.1mL is dissolved with three tooth phosphine ligand L 1 of 2umol embodiment 5 preparations, 0.1mL is dissolved with (CO) 2 toluene solution of 1umol Rh metal complex Rh (acac), stirring at room 5min.Then add 1mmol vinylbenzene and 0.1mL n-decane (as interior mark), adding toluene, to make the cumulative volume of reaction solution be 1mL again, and vial is transferred in the autoclave.Use N 2With the air displacement in the autoclave three times, be filled with subsequently CO and H 2Each 5bar of gas.Adopt oil bath that autoclave is heated to 80 ℃, behind the reaction 1h, autoclave is positioned in the ice-water bath cools off.In stink cupboard that the air release in the autoclave is complete, obtain the n:i value by gas-chromatography (GC) analyze reaction mixture at once, the n:i value is the linear product that generates behind the hydroformylation reaction ratio with the amount of substance of branched product.
The present invention's three conditional filtering and the application of tooth phosphine part in linear hydroformylation reaction
Table 1 will be illustrated reactive behavior and the selectivity of three tooth phosphine ligand L 1 in linear hydroformylation reaction synthetic among the present invention.Also the reactive behavior of bidentate and four tooth phosphine parts and selectivity and three tooth phosphine parts are compared among the present invention.For this reason, selecting 1-octene and 1-hexene is substrate, respectively three tooth phosphine ligand L 1, bidentate phosphine part, four tooth phosphine parts is used for linear hydroformylation reaction; the hydroformylation reaction condition is: S/C=10; 000, Rh concentration [Rh]=0.2mmol/L, part and Rh (acac) are (CO) 2Mol ratio be that 3:1(three tooth phosphine parts are 4:1), make solvent with toluene, mark in doing with positive flow silane, reaction 1h is detected by gas-chromatography (GC) and to obtain the n:i value, duplicate detection is averaged for twice, the results are shown in Table 1; Selection vinylbenzene is substrate, respectively three tooth phosphine ligand L 1, bidentate phosphine part, four tooth phosphine parts is used for hydroformylation reaction, and the hydroformylation reaction condition is: S/C=1000, and Rh concentration [Rh]=1mmol/L, part and Rh (acac) are (CO) 2Mol ratio be 2:1, make solvent with toluene, mark in doing with positive flow silane, reaction 30min is detected by gas-chromatography (GC) and to obtain the n:i value, duplicate detection is averaged for three times, the results are shown in Table 1.Data in the table 1 best n:i value that to be three kinds of phosphine parts obtain under optimal conditions separately.Result from table can find out, the selectivity of three tooth phosphine ligand L 1 in linear hydroformylation reaction be significantly better than the bidentate phosphine part, approaches with four tooth phosphine parts.
Table 1 bidentate, three teeth, four tooth phosphine parts optionally compare in linear hydroformylation reaction
Figure BDA00002216830100211
In order further to contrast reactive behavior and the selectivity of above-mentioned three kinds of phosphine parts, select 2-octene, 1-hexene and vinylbenzene substrate to test selectivity and the reactive behavior of three tooth phosphine ligand L 1 under the differential responses condition, the reaction conditions that adopts is: S/C=10,000, Rh concentration [Rh]=0.2mmol/L, three tooth phosphine ligand L 1 and Rh (acac) are (CO) 2Mol ratio be 4:1, bidentate phosphine ligand L 2 and Rh (acac) are (CO) 2Mol ratio be 3:1, four tooth phosphine ligand L 3 and Rh (acac) are (CO) 2Mol ratio be 3:1, make solvent with toluene, mark in doing with positive flow silane is detected by gas-chromatography (GC) and to obtain the n:i value, duplicate detection is averaged for twice, the results are shown in Table 2, reaction formula is as follows:
Figure BDA00002216830100221
Data from table 2 also can find out, the selectivity of three tooth phosphine ligand L 1 in hydroformylation reaction is significantly better than the bidentate phosphine part, simultaneously close to four tooth phosphine parts.The TON value is the molecule number of a part catalyzer conversion of substrate in the table 2.
The hydroformylation reaction result of table 2 1-hexene and 2-octene
Figure BDA00002216830100222
The cinnamic hydroformylation reaction result of table 3.
Figure BDA00002216830100223
The data that table 3 is listed be vinylbenzene in hydroformylation reaction, three tooth phosphine parts and metal catalyst Rh (acac) are (CO) 2Reactive behavior under different ratios and selectivity, reaction conditions is: S/C=1000, Rh concentration [Rh]=1mmol/L, make solvent with toluene, mark in doing with positive flow silane obtains the n:i value by gas-chromatography (GC) detection, duplicate detection is averaged for three times, the results are shown in Table 3, the molecule number of the substrate that the TOF value transforms within the unit time for a part catalyzer in the table 3, reaction formula is as follows:
Figure BDA00002216830100231
The principal element that affects hydroformylation reaction has: the ratio of part and metal catalyst, temperature of reaction, CO and H 2The pressure of gas, reaction times and other, such as catalyzer to the consumption of substrate and reaction solvent etc.The below will be take the 1-octene as substrate, main ratio, temperature of reaction, CO and H from part and metal Rh reagent 2Reactive behavior and the selectivity of three tooth phosphine ligand L 1 in linear hydroformylation studied in these four aspects of the pressure of gas and reaction times.What table 4-table 7 provided is reactive behavior and the selectivity that the 1-octene utilizes three tooth phosphine ligand L 1 to obtain under different reaction conditionss in linear hydroformylation reaction.
The selection of the ratio of part and metal reagent is very large on the impact of reaction result such as selectivity and transformation efficiency etc., and what table 4 was listed is that selection 1-octene is the template reaction substrate, and part and Rh (acac) are (CO) 2Mol ratio change to the response data that 8:1 obtains by 1:1, draw under the reaction conditions that adopts: take the 1-octene as substrate, the metal complex of employing be Rh (acac) (CO) 2, S/C=10,000, make solvent with toluene, mark in doing with positive flow silane; 80 ℃ of temperature of reaction, reaction times 1h, CO and H 2The pressure of gas is 10bar; After reaction finishes, obtain the n:i value by gas-chromatography (GC) detection, duplicate detection is averaged for twice, the results are shown in Table 4, and reaction formula is as follows:
The ratio of table 4 part and metal catalyst is on the impact of 1-octene hydroformylation reaction
Figure BDA00002216830100233
In linear hydroformylation reaction, temperature of reaction has very large impact to selectivity, transformation efficiency and the TON value of reaction.Take the 1-octene as substrate, the response data that obtains under the differential responses temperature is as shown in table 5.Reaction conditions in the table 5 is as follows: adopt metal catalyst Rh (acac) (CO) 2Complex compound and three tooth phosphine ligand L 1, S/C=10,000, Rh concentration [Rh]=0.2mmol/L, ligand L 1 and metal catalyst Rh (acac) are (CO) 2Mol ratio see Table 5, make solvent with toluene, mark in doing with positive flow silane, reaction times 1h, CO and H 2The pressure of gas is 10bar; After reaction finishes, obtain the n:i value by gas-chromatography (GC) detection, duplicate detection is averaged for twice, the results are shown in Table 5, and reaction formula is as follows:
Figure BDA00002216830100234
Table 5. temperature of reaction is on the impact of 1-octene hydroformylation reaction
Figure BDA00002216830100241
For hydroformylation reaction, CO and H 2Gaseous tension affects speed, selectivity, TON value of reaction etc.Take the 1-octene as substrate, different CO and H 2The response data that obtains under the gaseous tension is as shown in table 6.Reaction conditions in the table 6 is as follows: adopt Rh (acac) (CO) 2Complex compound and three tooth phosphine ligand L 1, S/C=10,000, Rh concentration [Rh]=0.2mmol/L, ligand L 1 and metal catalyst Rh (acac) are (CO) 2Mol ratio and CO and H 2Air pressure sees Table 6, makes solvent with toluene, mark in doing with positive flow silane, reaction times 1h, 80 ℃ of temperature of reaction; After reaction finishes, obtain the n:i value by gas-chromatography (GC) detection, duplicate detection is averaged for twice, the results are shown in Table 6, and reaction formula is as follows:
Table 6.CO and H 2Gaseous tension is on the impact of 1-octene hydroformylation reaction
Figure BDA00002216830100243
In hydroformylation reaction, the reaction times affects transformation efficiency and the yield of reaction.Take the 1-octene as substrate, the response data that obtains under the differential responses time is as shown in table 7.The reaction conditions of table 7 is as follows: adopt Rh (acac) (CO) 2Complex compound and three tooth phosphine ligand L 1, S/C=10,000, Rh concentration [Rh]=0.2mmol/L, ligand L 1 and metal catalyst Rh (acac) are (CO) 2Mol ratio see Table 7, make solvent with toluene, mark in doing with positive flow silane, 80 ℃ of temperature of reaction, CO and H 2The pressure of gas is 5bar; After reaction finishes, obtain the n:i value by gas-chromatography (GC) detection, duplicate detection is averaged for twice, the results are shown in Table 7, and reaction formula is as follows:
Figure BDA00002216830100251
Table 7 reaction times is on the impact of the linear hydroformylation reaction of 1-octene
Figure BDA00002216830100252

Claims (13)

1. three tooth phosphine parts is characterized in that having the structure of general formula (I):
In the general formula (I):
I, J, K, L, M, N, Q are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
Y is R, Ar, OR, OAr, pyrroles or substituted azole;
R is alkyl or substituted alkyl, and Ar is aryl;
Described Q, L replace can form bridged linkage composition five-ring or six-ring between the atom.
2. three tooth phosphine parts claimed in claim 1 is characterized in that having the structure of general formula (II):
Figure FDA00002216830000012
In the general formula (II):
A, b, c, d, I, J, K, L, M, N, Q are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
R is alkyl or substituted alkyl, and Ar is aryl.
Bridged linkage be can form among described a, b, c, d, I, J, K, L, M, N, the Q between any two adjacent replacement atoms and five-ring or six-ring formed.
3. three tooth phosphine parts claimed in claim 1 is characterized in that having the structure of general formula (III):
In the general formula (III):
A, b, c, d, E, F, G, I, J, K, L, M, N are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
R is alkyl or substituted alkyl, and Ar is aryl.
Bridged linkage be can form among described a, b, c, d, E, F, G, I, J, K, L, M, the N between any two adjacent replacement atoms and five-ring or six-ring formed.
4. three tooth phosphine parts claimed in claim 1 is characterized in that having the structure of general formula (IV):
Figure FDA00002216830000022
In the general formula (IV):
A, b, c, d, e, f, I, J, K, L, M, N, Q are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
R is alkyl or substituted alkyl, and Ar is aryl.
Bridged linkage be can form among described a, b, c, d, e, f, I, J, K, L, M, N, the Q between any two adjacent replacement atoms and five-ring or six-ring formed.
5. three tooth phosphine parts claimed in claim 1 is characterized in that having the structure of logical formula V:
Figure FDA00002216830000031
In the logical formula V:
A, b, c, d, e, I, J, K, L, M, N, Q are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
R is alkyl or substituted alkyl, and Ar is aryl.
Bridged linkage be can form among described a, b, c, d, e, I, J, K, L, M, N, the Q between any two adjacent replacement atoms and five-ring or six-ring formed.
6. three tooth phosphine parts claimed in claim 1 is characterized in that having the structure of general formula (VI):
Figure FDA00002216830000032
In the general formula (VI):
A, b, c, d, e, f, g, h, I, J, K, L, M, N, Q are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
Z is CH 2-CH 2, O, CH 2, NH or NR;
R is alkyl or substituted alkyl, and Ar is aryl.
Bridged linkage be can form among described a, b, c, d, e, f, g, h, I, J, K, L, M, N, the Q between any two adjacent replacement atoms and five-ring or six-ring formed.
7. three tooth phosphine parts claimed in claim 1 is characterized in that having the structure of general formula (VII):
Figure FDA00002216830000041
In the general formula (VII):
A, b, c, d, e, I, J, K, L, M, N, Q are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
R is alkyl or substituted alkyl, and Ar is aryl.
Bridged linkage be can form among described a, b, c, d, e, I, J, K, L, M, N, the Q between any two adjacent replacement atoms and five-ring or six-ring formed.
8. three tooth phosphine parts claimed in claim 1 is characterized in that having the structure of general formula (VIII):
Figure FDA00002216830000042
In the general formula (VIII):
A, b, c, d, e, f, g, h, I, J, K, L, M, N, Q are H, R, Ar, replacement Ar, OR, OAr, COOEt, halogen, SO 2R, SO 3H, SO 2NHR or NR 2
X is O, CH 2, NH or NR;
R is alkyl or substituted alkyl, and Ar is aryl.
Any two adjacent substituted elements can form bridged linkage composition five-ring or six-ring among described a, b, c, d, e, f, g, h, I, J, K, L, M, N, the Q.
9. can make after each described three tooth phosphine parts and the transition metal complex hybrid reaction among the claim 1-8 as the catalyzer in hydroformylation, isomerization hydroformylation reaction, hydrocarboxylation reaction, the reaction of hydrogen cyano group, isomerization formyl reaction and the hydroaminomethylation.
10. catalyzer that is used for hydroformylation reaction is characterized in that:
Described catalyzer is prepared by each described three tooth phosphine parts and transition metal complex hybrid reaction among the claim 1-8.
11. the described catalyzer for hydroformylation reaction of claim 10 is characterized in that:
Atoms metal in the described transition metal complex is Fe, Zn, Mn, Co, Cu, Ag, Ni, Pt, Pd, Rh, Ru or Ir.
12. claim 10 or 11 described catalyzer for hydroformylation reaction is characterized in that:
Described transition metal complex is (Rh (COD) Cl) 2, (Rh (COD) 2) X, Rh (acac) are (CO) 2Or RuH (CO) 2(PPh 3) 2, wherein, X is balance anion.
13. the described catalyzer for hydroformylation reaction of claim 12 is characterized in that:
Described X is BF 4, ClO 4, OTf, SbF 6, CF 3SO 3, B (C 6H 3(CF 3) 2) 4, Cl, Br or I.
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CN103804413B (en) * 2014-01-27 2017-03-15 武汉大学 Three Phosphine ligands preparation method of biphenyl and progressively replace PPh in hydroformylation3Application
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WO2023206791A1 (en) 2022-04-26 2023-11-02 浙江新和成股份有限公司 Method for preparing phosphorus-containing ligand

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