CN112517062B - Magnetic nanoparticle immobilized phosphoramidate catalyst, preparation method thereof and preparation method of gamma, delta-unsaturated ketone - Google Patents

Magnetic nanoparticle immobilized phosphoramidate catalyst, preparation method thereof and preparation method of gamma, delta-unsaturated ketone Download PDF

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CN112517062B
CN112517062B CN202011469456.4A CN202011469456A CN112517062B CN 112517062 B CN112517062 B CN 112517062B CN 202011469456 A CN202011469456 A CN 202011469456A CN 112517062 B CN112517062 B CN 112517062B
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phosphoramidate
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沈稳
王永军
黄文学
谢硕
张永振
黎源
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Wanhua Chemical Group Co Ltd
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Abstract

The invention discloses a magnetic nanoparticle immobilized phosphoramidate catalyst, a preparation method thereof and a preparation method of gamma, delta-unsaturated ketone. The catalyst has the structure of formula I or formula II:
Figure DDA0002832951580000011
wherein m is an integer of 1 to 5, n is an integer of 0 to 3, R is selected from C1 to C6 alkyl, phenyl and substituted phenyl, and X is selected from CH 2 NH, O or S. The method can realize the Saucy-Marbet reaction of allyl alcohol and 2-methoxypropene to generate gamma, delta-unsaturated ketone by using a catalyst with low cost. The catalyst has the advantages of high catalytic activity, high selectivity, low cost, simple preparation, repeated cyclic utilization, quick separation and recovery and the like, and overcomes the defects of low catalyst activity, long reaction time, high reaction temperature, expensive catalyst, low product selectivity and the like in the prior art.

Description

Magnetic nanoparticle immobilized phosphoramidate catalyst, preparation method thereof and preparation method of gamma, delta-unsaturated ketone
Technical Field
The invention belongs to the field of catalysts and organic synthesis, and particularly relates to a magnetic nanoparticle immobilized catalyst and application of the catalyst in synthesis of gamma, delta-unsaturated ketone.
Background
The gamma, delta-unsaturated ketone widely exists in natural products and fine chemicals, such as methyl heptenone, has fresh fruit fragrance, is edible essence which is allowed to be used by national standards, and simultaneously, the methyl heptenone is an important synthetic intermediate, and can be used for synthesizing fine chemicals with great economic values, such as linalool, linalyl acetate, vitamin A, vitamin E and the like. Furthermore, geranylacetone, farnesylacetone and the like are also typical γ, δ -unsaturated ketones, and have very important applications.
As early as 1967, Saucy et al found that gamma, delta-unsaturated ketones could be obtained by reacting allyl alcohol with 2-alkoxypropene at 120-200 ℃ for 12-16 hours in the presence of catalytic amounts of phosphoric acid; when the product was methylheptenone, the yield was only 41% (Helv. Chim. acta.1967,50, 2091-2095.). The pioneering work of Saucy et al provided a novel process for the preparation of gamma, delta-unsaturated ketones, and the reaction of allyl or propargyl alcohol with 2-alkoxypropene to form unsaturated ketones was named the Saucy-Marbet reaction, and it was later discovered that many other acidic catalysts can also catalyze this reaction.
Patent CN1914143A reports that hydrogenated tri (oxalic acid) phosphate or hydrogenated bis (oxalic acid) phosphate catalyzes the rearrangement reaction of 2-methyl-3-buten-2-ol and 2-alkoxy propylene, the amount of the catalyst is 0.15 mol% of 2-methyl-3-buten-2-ol, and the reaction can obtain a yield of more than 90% at 150 ℃ for 24 hours.
The patent CN102197014A adopts ammonium chloride, ammonium bromide or diammonium hydrogen phosphate to catalyze the reaction of allyl alcohol and 2-ethoxypropene, and has the advantages of high reaction yield, long reaction time and general requirement of 12-40 hours.
WO2018091623A1 and EP3323802A1 adopt organic phosphoric acid, such as 2-benzyloxy phosphoric acid, biphenol phosphoric acid and the like, to catalyze the rearrangement reaction of allyl alcohol and isopropenyl alkyl ether, the reaction temperature is 120-150 ℃, the reaction pressure is 8-12bar, and the gamma, delta-unsaturated ketone product is obtained with excellent yield, but the reaction time is long, the catalyst consumption is large, the catalyst cannot be recycled, the catalyst is expensive, and the catalyst is difficult to be applied to industrial production.
Patent CN106478514A reports that bronsted acid functionalized ionic liquid is used as catalyst to realize rearrangement reaction of allyl alcohol and 2-alkoxy propylene, and obtain better yield, but ionic liquid is expensive and not suitable for industrial application.
Patent CN108299171A reports that 2-methyl propylene and methyl butenol generate a Saucy-Marbet reaction to generate methyl heptenone under a critical state, a catalyst is not needed in the method, but the reaction temperature is up to 250-300 ℃, the energy consumption is high, and meanwhile, the safety risk exists.
In summary, although various catalysts have been used in the rearrangement of allyl alcohol and 2-alkoxy propylene, these catalysts generally have poor activity and require high reaction temperature and long reaction time to complete the reaction. Strong acid catalysts such as phosphoric acid and the like have good reaction activity, but the selectivity of the reaction is poor, and the raw material allyl alcohol is dehydrated to generate diene byproducts, which affects the separation. In addition, acid catalysts also affect the separation of 2-methoxypropene, requiring neutralization with a base.
In view of the importance of the gamma, delta-unsaturated ketone product, the development of a novel low-cost catalyst is needed at present, the catalyst has higher catalytic activity, the catalytic reaction can be completed in a shorter time under a milder reaction condition, the space-time yield of the device is improved, and the gamma, delta-unsaturated ketone product represented by the methyl heptenone is obtained more efficiently and quickly.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a magnetic nanoparticle immobilized phosphoramidate catalyst, a preparation method thereof and a preparation method of gamma, delta-unsaturated ketone. The catalyst has the advantages of high catalytic activity, high selectivity, low cost, simple preparation, repeated recycling, quick separation and recovery and the like, overcomes the defects of low catalyst activity, long reaction time, high reaction temperature, expensive catalyst, low product selectivity and the like in the prior art, and can realize the generation of gamma, delta-unsaturated ketone by the Saucy-Marbet reaction of allyl alcohol and 2-alkoxy propylene with the catalyst with low cost.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a magnetic nanoparticle-immobilized phosphoramidate catalyst is of a structure of formula I or formula II:
Figure BDA0002832951570000031
wherein m is an integer of 1 to 5, n is an integer of 0 to 3, R is selected from C1 to C6 alkyl, phenyl and substituted phenyl, and X is selected from CH 2 NH, O or S.
A method for preparing a magnetic nanoparticle immobilized phosphoramidate catalyst comprises the following steps:
(1) reacting dichlorophosphate with a silane coupling agent under the catalysis of organic base to obtain the silane coupling agent containing the phosphoramidate group;
(2) silane coupling agent containing phosphoramidate group and magnetic nano particle (SiO) coated by silicon dioxide 2 @Fe 3 O 4 ) And reacting to obtain the magnetic nanoparticle immobilized phosphoramidate catalyst.
The dichlorophosphate provided by the invention is selected from one or more of methyl dichlorophosphate, ethyl dichlorophosphate and phenyl dichlorophosphate, and phenyl dichlorophosphate is preferred.
The silane coupling agent is selected from one or more of 1- [3- (trimethoxysilyl) propyl ] Urea (UPTMS), (3-aminopropyl) trimethoxy silane (APTMS), (3-aminopropyl) triethoxy silane (APTES) and N- [3- (trimethoxysilyl) propyl ] Ethylenediamine (EDATMS), and 1- [3- (trimethoxysilyl) propyl ] urea is preferred.
Preferably, the silane Coupling agent containing phosphoramidate groups is one or more selected from Coupling-1 to Coupling-6, preferably Coupling-1, and has the following structural formula:
Figure BDA0002832951570000041
as a preferable scheme, the preparation method of the magnetic nanoparticle-supported phosphoramidate catalyst comprises the following steps:
(a) under the argon atmosphere, adding dichlorophosphate and organic alkali into anhydrous toluene, slowly dropwise adding a silane coupling agent at-10-0 ℃, reacting for 1-2 h at 0-30 ℃ after dropwise adding, then adding water, and reacting for 0.5-1.0 h at room temperature to obtain the silane coupling agent containing the phosphoramidate group;
(b) under the argon atmosphere, the magnetic nano particle SiO wrapped by the silicon dioxide 2 @Fe 3 O 4 Dispersing the mixture into anhydrous toluene, performing ultrasonic treatment for 1-2 h, adding a silane coupling agent containing phosphoramidate groups, reacting for 6h at 120 ℃, and performing magnetic field separation to obtain magnetic nanoparticle-immobilized phosphoramidate as a catalystWashing the agent with anhydrous toluene, drying in vacuum, and storing in argon atmosphere.
The preparation method of the magnetic nano-particles coated by the silicon dioxide refers to Green chem.2012 and 14,201.
The organic base is selected from one or more of Triethylamine (TEA), Diisopropylethylamine (DIPEA) and Pyridine (Pyridine), and Pyridine is preferred.
In the step (a), the molar ratio of the dichlorophosphate to the organic base is 1: 2-3, preferably 1: 2.2-2.5.
In the step (a) of the present invention, the molar ratio of water to the dichlorophosphate is 1.0-1.5: 1, preferably 1.1-1.2: 1.
In the step (a) of the present invention, the molar ratio of the silane coupling agent to the dichlorophosphate is 1.0-1.5: 1, preferably 1.1-1.2: 1.
In the step (b) of the present invention, SiO 2 @Fe 3 O 4 The mass ratio of the silane coupling agent to the silane coupling agent containing the phosphoramidate group is 1: 1-5, preferably 1: 2-3.
In another aspect, the present invention provides a method for preparing a γ, δ -unsaturated ketone, comprising the steps of: under the atmosphere of nitrogen, under the action of a phosphoramidate catalyst immobilized by magnetic nanoparticles, allyl alcohol and 2-methoxypropene undergo a Saucy-Marbet reaction to obtain gamma, delta-unsaturated ketone.
The allyl alcohol of the invention comprises one or more of 2-methyl-3-butylene-2-alcohol, linalool, nerolidol and the like.
In the preparation method of the gamma, delta-unsaturated ketone, the molar ratio of allyl alcohol to 2-methoxypropene is 1: 2-5, preferably 1: 2.5-3.5.
In the preparation method of the gamma, delta-unsaturated ketone, the dosage of the phosphoramidate catalyst immobilized on the magnetic nano particles is 0.01-0.05%, preferably 0.02-0.03%, based on the weight of allyl alcohol.
In the preparation method of the gamma, delta-unsaturated ketone, the reaction temperature is 80-130 ℃, and preferably 100-110 ℃; the reaction time is 2-6 h, preferably 3-4 h.
The structure of the prepared nanoparticle-immobilized phosphoramidate catalyst contains phosphoramide and phosphate ester groups, the preferable magnetic nanoparticle-immobilized phosphoramidate catalyst contains phenyl phosphate and phosphoryl urea structures, the phenyl phosphate improves the activity of the catalyst, the phosphoryl urea reduces the acidity of the surface of the catalyst and further improves the selectivity of a target product, the synergistic effect of the phenyl phosphate and the phosphoryl urea can improve the activity and the selectivity of the catalyst for catalyzing the Saucy-Marbet reaction, compared with the reported catalyst for the Saucy-Marbet reaction (such as dimethylphenyl phosphate), the catalyst can shorten the reaction time, remarkably improve the selectivity of the target product, and remarkably reduce diene byproducts generated by dehydrating allyl alcohol serving as a raw material.
By adopting the technical scheme, the invention has the following positive effects:
(1) the catalyst has the advantages of cheap and easily-obtained raw materials, simple preparation process, recyclability and great reduction of cost.
(2) The reaction condition is simple to operate, the catalyst activity is high, the selectivity and the yield of the target product are high, and meanwhile, the catalyst can be quickly separated without neutralization operation, so that the subsequent separation is not influenced.
Detailed Description
The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.
The main raw material information is as follows:
nano ferroferric oxide dispersion liquid (10-50 nm, 20% in H) 2 O), purchased from alatin reagent;
tetraethyl orthosilicate, 99% GC, from alatin reagent;
phenyl dichlorophosphate, methyl dichlorophosphate and ethyl dichlorophosphate with the purity of 98-99% are purchased from an alladin reagent;
chlorosulfonic acid, purchased from carbofuran reagent, purity 99%;
silane coupling agents such as UPTMS, APTMS, APTES and EDATMS, the purity of which is 95-98%, and the silane coupling agents are purchased from an Aladdin reagent;
TEA, DIPEA, Pyridine, etc., 98% pure, purchased from alatin reagent;
toluene, AR, from alatin reagent, was distilled under reduced pressure to remove water with sodium metal/benzophenone before use;
2-methoxypropene, purity 99%, Anhui Hua Yongguan;
2-methyl-3-buten-2-ol, nerolidol and linalool with purity of 97-98% are purchased from an alatin reagent;
ditolyl phosphate, 99% purity, purchased from alatin reagent;
the gas chromatography test conditions of the invention are as follows:
the instrument model is as follows: agilent GC; a chromatographic column: agilent HP-INNOwax 19091N-213I; column temperature: the initial temperature is 40 ℃, the temperature is kept for 5min, the temperature is raised to 70 ℃ at the speed of 3 ℃/min, then the temperature is raised to 100 ℃ at the speed of 10 ℃/min, and finally the temperature is raised to 240 ℃ at the speed of 12 ℃/min, and the temperature is kept for 5 min; sample inlet temperature: 240 ℃; FID detector temperature: 240 ℃; split-flow sample injection with a split-flow ratio of 30: 1; sample introduction amount: 0.5 mu L; h 2 Flow rate: 40 mL/min; air flow rate: 400 mL/min.
Example 1: SiO 2 2 @Fe 3 O 4 Preparation of
Taking nano ferroferric oxide dispersion liquid (10-50 nm, 20 wt% in H) under argon atmosphere 2 O)100mL, 300mL ethanol, 2mL ammonia (25%) and 2mL oleic acid were added. Performing ultrasonic treatment for 0.5-1.0 h, dropwise adding 40g of ethyl orthosilicate ethanol solution (0.5g/mL), stirring at normal temperature for 12h, and applying magnetic field to separate SiO 2 @Fe 3 O 4 And washing with ethanol for three times, and storing under an argon atmosphere.
Example 2: preparation of silane Coupling agent Coupling-1 containing phosphoramidate group
Figure BDA0002832951570000081
Under an argon atmosphere, a 250ml Schlenk flask was charged with anhydrous toluene (105.49g), pyridine (8.71g, 0.11mol) and phenyl dichlorophosphate (10.55g, 0.05mol), stirred, placed in an ice-salt mixture at-10 ℃ and the temperature of the mixed solution in the flask was lowered to-10 ℃. Slowly dripping a silane coupling agent UPTMS (13.34g, 0.06mol) by using a constant-pressure dropping funnel (the dripping time is about 30min), and controlling the temperature of the reaction solution in a Schlenk bottle to be between-10 and 0 ℃ in the dripping process. After the completion of the dropwise addition, the reaction was carried out at 30 ℃ for 1 hour, deionized water (1.08g, 0.06mol) was added thereto, and the reaction was terminated after 0.5 hour at room temperature. The reaction mixture was filtered, the filtrate was distilled under reduced pressure to give a crude product as a pale yellow oil, which was washed with anhydrous toluene and dried in a vacuum oven (150 ℃ C., 10Pa) for 24 hours to give a pale yellow oil (17.5g, yield 92.5%, based on phenyl dichlorophosphate).
1 H-NMR(400MHz,DMSO-d6):δ7.18～7.28(m,5H),5.28(s,H),5.13(s,H),3.51(s,9H),3.10(t,J＝7.3Hz 2H),1.58(m,2H),0.56(t,J＝7.1Hz 2H)；ESI-MS:C 13 H 23 N 2 O 7 P Si([M-H])377.10。
Example 3: preparation of silane Coupling agent Coupling-2 containing phosphoramidate group
Figure BDA0002832951570000091
Under an argon atmosphere, a 250ml Schlenk flask was charged with anhydrous toluene (105.49g), pyridine (9.89g, 0.13mol) and phenyl dichlorophosphate (10.55g, 0.05mol), stirred, placed in an ice-salt mixture at-10 ℃ and the temperature of the mixed solution in the flask was lowered to-10 ℃. Slowly dripping a silane coupling agent APTMS (11.65g, 0.065mol) by using a constant-pressure dropping funnel (the dripping time is about 30min), and controlling the temperature of a reaction solution in a Schlenk bottle to be between-10 and 0 ℃ in the dripping process. After the completion of the dropwise addition, the reaction was carried out at 30 ℃ for 1 hour, deionized water (1.35g, 0.075mol) was added thereto, and the reaction was terminated after 0.5 hour at room temperature. The reaction mixture was filtered, the filtrate was distilled under reduced pressure to give a crude product as a pale yellow oil, which was washed with anhydrous toluene and dried in a vacuum oven (150 ℃ C., 10Pa) for 24 hours to give a pale yellow oil (15.0g, yield 89.5%, based on phenyl dichlorophosphate).
1 H-NMR(400MHz,DMSO-d6):δ7.19～7.34(m,5H),5.18(s,H),3.54(s,9H),2.7(t,J＝7.1Hz 2H),1.51(m,2H),0.54(t,J＝7.2Hz 2H)；ESI-MS:C 12 H 22 NO 6 P Si([M-H])334.10。
Example 4: preparation of silane Coupling agent Coupling-3 containing phosphoramidate group
Figure BDA0002832951570000092
Under an argon atmosphere, a 250ml Schlenk flask was charged with anhydrous toluene (105.49g), pyridine (8.71g, 0.11mol) and phenyl dichlorophosphate (10.55g, 0.05mol), stirred with stirring, the Schlenk flask was placed in an ice-salt mixture at-10 ℃ and the temperature of the mixed solution in the flask was lowered to-10 ℃. Slowly dripping silane coupling agent APTES (13.28g, 0.06mol) by using a constant-pressure dropping funnel (the dripping time is about 30min), and controlling the temperature of the reaction liquid in a Schlenk bottle to be between-10 and 0 ℃ in the dripping process. After the addition, the reaction was carried out at 30 ℃ for 1 hour, deionized water (0.9g, 0.05mol) was added, and the reaction was terminated at room temperature for 0.5 hour. The reaction mixture was filtered, the filtrate was distilled under reduced pressure to give a crude product as a pale yellow oil, which was washed with anhydrous toluene and dried in a vacuum oven (150 ℃ C., 10Pa) for 24 hours to give a pale yellow oil (17.1g, yield 90.6%, based on phenyl dichlorophosphate).
1 H-NMR(400MHz,DMSO-d6):δ7.21～7.36(m,5H),5.15(s,H),3.83(m,6H),2.75(t,J＝6.9Hz 2H),1.50(m,2H),1.24(t,J＝7.3Hz 9H),0.56(t,J＝7.2Hz 2H)；ESI-MS:C 15 H 28 NO 6 PSi([M-H])376.14。
Example 5: preparation of silane Coupling agent Coupling-4 containing phosphoramidate group
Figure BDA0002832951570000101
Under an argon atmosphere, a 250ml Schlenk flask was charged with anhydrous toluene (105.49g), pyridine (8.71g, 0.11mol) and phenyl dichlorophosphate (10.55g, 0.05mol), stirred, placed in an ice-salt mixture at-10 ℃ and the temperature of the mixed solution in the flask was lowered to-10 ℃. Slowly dripping a silane coupling agent EDATMS (12.23g, 0.055mol) by using a constant-pressure dropping funnel (the dripping time is about 30min), and controlling the temperature of a reaction solution in a Schlenk bottle to be-10-0 ℃ in the dripping process. After the completion of the dropwise addition, the reaction was carried out at 30 ℃ for 1 hour, deionized water (1.08g, 0.05mol) was added thereto, and the reaction was terminated after 0.5 hour at room temperature. The reaction mixture was filtered, the filtrate was distilled under reduced pressure to give a crude product as a pale yellow oil, which was washed with anhydrous toluene and dried in a vacuum oven (150 ℃ C., 10Pa) for 24 hours to give a pale yellow oil (16.7g, yield 88.3%, based on phenyl dichlorophosphate).
1 H-NMR(400MHz,DMSO-d6):δ7.19～7.35(m,5H),5.14(s,H),3.54(s,9H),2.84(m,2H),2.56～2.65(m,4H),2.18(s,1H),1.37(m 2H),0.58(t,J＝7.2Hz 2H)；ESI-MS:C 14 H 27 N 2 O 6 PSi([M-H])377.14。
Example 6: preparation of silane Coupling agent Coupling-5 containing phosphoramidate group
Figure BDA0002832951570000111
Under an argon atmosphere, a 250ml Schlenk flask was charged with anhydrous toluene (111.68g), pyridine (8.71g, 0.11mol) and methyl dichlorophosphate (7.45g, 0.05mol), stirred, placed in an ice-salt mixture at-10 ℃ and the temperature of the mixed solution in the flask was lowered to-10 ℃. Slowly dripping a silane coupling agent UPTMS (12.23g, 0.055mol) by using a constant-pressure dropping funnel (the dripping time is about 30min), and controlling the temperature of a reaction solution in a Schlenk bottle to be-10-0 ℃ in the dripping process. After the completion of the dropwise addition, the reaction was carried out at 30 ℃ for 1.0h, deionized water (1.08g, 0.05mol) was added thereto, and the reaction was terminated after 0.5h at room temperature. The reaction mixture was filtered, the filtrate was distilled under reduced pressure to give a crude product as a yellow oil, which was washed with anhydrous toluene and dried in a vacuum oven (150 ℃ C., 10Pa) for 24 hours to give a yellow oil (13.6g, yield 86.0% based on methyl dichlorophosphate).
1 H-NMR(400MHz,DMSO-d6):δ5.58(s,H),5.33(s,H),3.78(s,3H),3.56(s,9H),3.16(t,J＝7.2Hz 2H),1.51(m,2H),0.58(t,J＝7.1Hz 2H)；ESI-MS:C 8 H 21 N 2 O 7 P Si([M-H])315.09。
Example 7: preparation of silane Coupling agent Coupling-6 containing phosphoramidate group
Figure BDA0002832951570000121
Under an argon atmosphere, a 250ml Schlenk flask was charged with anhydrous toluene (122.21g), pyridine (8.71g, 0.11mol) and ethyl dichlorophosphate (8.15g, 0.05mol), the stirring was turned on, the Schlenk flask was placed in an ice-salt mixture at-10 ℃ and the temperature of the mixed solution in the flask was lowered to-10 ℃. Slowly dripping a silane coupling agent UPTMS (12.23g, 0.055mol) by using a constant-pressure dropping funnel (the dripping time is about 30min), and controlling the temperature of a reaction solution in a Schlenk bottle to be-10-0 ℃ in the dripping process. After the completion of the dropwise addition, the reaction was carried out at 30 ℃ for 1.0 hour, deionized water (1.08g, 0.05mol) was added thereto, and the reaction was terminated after 0.5 hour at room temperature. The reaction solution was filtered, and the filtrate was distilled under reduced pressure to give a crude product as a yellow oil, which was washed with anhydrous toluene and dried in a vacuum oven (150 ℃ C., 10Pa) for 24 hours to give a yellow oil (14.0g, yield 84.8%, based on ethyl dichlorophosphate).
1 H-NMR(400MHz,DMSO-d6):δ5.38(s,H),5.16(s,H),4.48(m,2H),3.56(s,9H),3.15(t,J＝7.4Hz,2H),1.51(m,2H),1.31(t,J＝7.1Hz 2H),0.57(t,J＝7.1Hz 2H)；ESI-MS:C 9 H 23 N 2 O 7 P Si([M-H])329.10。
Comparative example 1: silane Coupling agent Coupling-SO containing sulfonic acid group 2 Preparation of OH
Figure BDA0002832951570000122
Under an argon atmosphere, a 250ml Schlenk flask was charged with anhydrous toluene (87.15g), pyridine (8.71g, 0.11mol) and chlorosulfonic acid (5.81g, 0.05mol), stirred, the Schlenk flask was placed in an ice-salt mixture at-10 ℃ and the temperature of the mixed solution in the flask was lowered to-10 ℃. Slowly dropwise adding a silane coupling agent UPTMS (12.23g, 0.055mol) by using a constant-pressure dropping funnel (the dropwise adding time is about 30min), and controlling the temperature of a reaction solution in a Schlenk bottle to be-10-0 ℃ in the dropwise adding process. After the completion of the dropwise addition, the reaction was carried out at 30 ℃ for 1.5 hours, deionized water (1.08g, 0.05mol) was added thereto, and the reaction was terminated after 0.5 hour at room temperature. The reaction solution was filtered, and the filtrate was distilled under reduced pressure to give a tan-colored crude product, which was washed with anhydrous toluene and dried in a vacuum oven (150 ℃ C., 10Pa) for 24 hours to give a yellow oily product (14.3g, yield 94.6%).
1 H-NMR(400MHz,DMSO-d6):δ8.39(s,H),6.56(s,H),5.48(s,H),3.55(s,9H),3.16(m,2H),1.49(m,2H),0.57(t,J＝7.1Hz 2H)；ESI-MS:C 7 H 18 N 2 O 7 SSi([M-H])301.06。
Examples 8-13, comparative example 2: preparation of nano particle supported catalyst
200g of anhydrous toluene was added to a 500mL Schlenk flask under an argon atmosphere, and the prepared SiO 2 @Fe 3 O 4 (2g) Dispersing into the anhydrous toluene, performing ultrasonic treatment for 1h, adding the silane coupling agent of the embodiment or the comparative example, reacting for 6h at 120 ℃, performing magnetic field separation to obtain the magnetic nanoparticle supported catalyst, washing with the anhydrous toluene, performing vacuum drying, and storing under argon atmosphere.
The preparation process of the nanoparticle-supported catalysts of the examples and comparative examples is shown in table 2:
TABLE 2 preparation of nanoparticle-immobilized phosphoramidate catalysts
Figure BDA0002832951570000131
Figure BDA0002832951570000141
Examples 14 to 19, comparative examples 3 to 4: synthesis of 6-methyl-5-hepten-2-one
A1000 mL high-pressure reaction kettle is added with a magnetic nanoparticle immobilized phosphoramidate catalyst, 2-methyl-3-buten-2-ol (172.26g, 2mol) and 2-methoxypropene (432.66g, 6mol), the reaction kettle is closed, and nitrogen is replaced for three times. Starting the reaction kettle, heating and stirring, keeping the temperature for reaction after the temperature is raised to the specified temperature, and stopping the reaction after the conversion rate of the 2-methyl-3-butene-2-alcohol is more than 99 percent by GC monitoring. After the reaction solution is cooled to room temperature, a magnetic field is applied to rapidly separate the phosphoramidate catalyst immobilized by the magnetic nanoparticles, the reaction solution is discharged, and the conversion rate of 2-methyl-3-butene-2-, the selectivity of the product 6-methyl-5-hepten-2-one (methylheptene) and the selectivity of the byproduct isoprene are sampled and analyzed, wherein the results are shown in Table 3:
TABLE 36 Synthesis of methyl-5-hepten-2-one
Figure BDA0002832951570000142
Example 20: synthesis of geranylacetone
A100 mL autoclave was charged with 0.046g of the nanoparticle-immobilized phosphoramidate catalyst prepared in example 8, linalool (154.26g, 1mol), and 2-methoxypropene (216.33g, 3mol), closed, and purged with nitrogen three times. Starting the reaction kettle, heating and stirring, keeping the temperature for reaction for 3 hours after the temperature is raised to 110 ℃, monitoring the conversion rate of linalool by GC to be more than 99%, and stopping the reaction. After the reaction liquid is cooled to room temperature, a magnetic field is added to rapidly separate the phosphoramidate catalyst immobilized by the magnetic nanoparticles, the reaction liquid is discharged, sampling analysis is carried out, the conversion rate of linalool is 99.4%, the selectivity of geranylacetone is 97.1%, and the selectivity of an olefin byproduct generated by dehydration of linalool is 1.7%.
Example 21: synthesis of geranylacetone
0.066g of the nanoparticle-immobilized phosphoramidate catalyst prepared in example 8, nerolidol (222.37g, 1mol), and 2-methoxypropene (216.33g, 3mol) were charged into a 100mL autoclave, which was closed and purged with nitrogen three times. Starting the reaction kettle, heating and stirring, keeping the temperature for reaction for 3 hours after the temperature is raised to 110 ℃, monitoring the conversion rate of the nerolidol by GC to be more than 99%, and stopping the reaction. After the reaction liquid is cooled to room temperature, a magnetic field is added to rapidly separate the phosphoramidate catalyst immobilized by the magnetic nanoparticles, the reaction liquid is discharged, and sampling analysis is carried out, wherein the conversion rate of nerolidol is 99.6%, the selectivity of the product farnesyl acetone is 96.6%, and the selectivity of an olefin byproduct generated by dehydration of nerolidol is 2.1%.
Finally, it should be noted that the above-mentioned embodiments only illustrate the preferred embodiments of the present invention, and do not limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications can be made by modifying the technical solution of the present invention or equivalent substitutions within the scope of the present invention defined by the claims.

Claims (12)

1. A method for preparing a gamma, delta-unsaturated ketone, comprising the steps of: under the atmosphere of nitrogen, under the action of a phosphoramidate catalyst immobilized by magnetic nanoparticles, allyl alcohol and 2-methoxypropene undergo a Saucy-Marbet reaction to obtain gamma, delta-unsaturated ketone; the magnetic nanoparticle immobilized phosphoramidate catalyst has a structure of formula I or formula II:
Figure FDA0003593536900000011
wherein m is an integer of 1 to 5, n is an integer of 0 to 3, R is selected from C1 to C6 alkyl, phenyl and substituted phenyl, and X is selected from CH 2 NH, O or S.
2. The method according to claim 1, wherein the preparation method of the magnetic nanoparticle-supported phosphoramidate catalyst comprises the following steps:
(1) reacting dichlorophosphate with a silane coupling agent under the catalysis of organic base to obtain the silane coupling agent containing the phosphoramidate group;
(2) and reacting the silane coupling agent containing the phosphoramidate group with the magnetic nano particles coated by the silicon dioxide to obtain the phosphoramidate catalyst immobilized on the magnetic nano particles.
3. The method according to claim 2, wherein the dichlorophosphate is selected from one or more of methyl dichlorophosphate, ethyl dichlorophosphate and phenyl dichlorophosphate.
4. The method according to claim 2, wherein the silane coupling agent is selected from one or more of 1- [3- (trimethoxysilyl) propyl ] urea, (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, and N- [3- (trimethoxysilyl) propyl ] ethylenediamine.
5. The method of claim 2, wherein the phosphoramidate group-containing silane Coupling agent is one or more selected from Coupling-1 to Coupling-6, and has the following structural formula:
Figure FDA0003593536900000021
6. the method according to claim 2, wherein the mass ratio of the silica-coated magnetic nanoparticles to the silane coupling agent containing the phosphoramidate group is 1: 1-5.
7. The method according to claim 2, wherein the mass ratio of the silica-coated magnetic nanoparticles to the silane coupling agent containing the phosphoramidate group is 1: 2-3.
8. The method of claim 1, wherein the allylic alcohol comprises one or more of 2-methyl-3-buten-2-ol, linalool, and nerolidol.
9. The method of claim 1, wherein the amount of the magnetic nanoparticle-immobilized phosphoramidate catalyst is from 0.01% to 0.05% based on the weight of allylic alcohol.
10. The method of claim 1, wherein the amount of the magnetic nanoparticle-supported phosphoramidate catalyst is 0.02 to 0.03% based on the weight of the allylic alcohol.
11. The method according to claim 1, wherein the reaction temperature is 80 to 130 ℃; the reaction time is 2-6 h.
12. The method according to claim 1, wherein the reaction temperature is 100 to 110 ℃; the reaction time is 3-4 h.
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