CN109569730B - Catalyst and application thereof - Google Patents

Catalyst and application thereof Download PDF

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CN109569730B
CN109569730B CN201811426351.3A CN201811426351A CN109569730B CN 109569730 B CN109569730 B CN 109569730B CN 201811426351 A CN201811426351 A CN 201811426351A CN 109569730 B CN109569730 B CN 109569730B
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catalyst
bmim
tfsi
ionic liquid
alcl
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CN109569730A (en
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张永伟
张刚
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Jiangsu Normal University
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    • 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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
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  • Materials Engineering (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a catalyst and application thereof, wherein the catalyst is a homogeneous composite catalyst[bmim][TFSI]/AlCl3The catalyst avoids the corrosion of equipment, the reaction condition is easy to control, the yield is high, and the product is easy to purify.

Description

Catalyst and application thereof
Technical Field
The invention relates to a catalyst and application thereof, belonging to the field of chemical synthesis.
Background
5-Bromoindanone (5-Bromoidanone) CAS: 34598-49-7 is an important organic synthesis intermediate, has various biological activities such as smooth muscle relaxation activity, cyclooxygenase inhibition activity and the like, and the compound separated from marine cyanobacteria shows the activity of inhibiting the growth of vascular endothelial factors of human beings, and has application prospect in the aspect of tumor angiogenesis regulation. In the prior art, 3-bromobenzaldehyde is used as a raw material, and 5-bromoindanone is prepared by condensation, ester protecting group removal, deacidification, catalytic hydrogenation and Friedel-Crafts reaction; the synthesis method has many steps, resulting in low comprehensive yield. The reaction raw material 3-chlorobenzaldehyde has high market price and is not suitable for storage, the hydrogenation cost of the palladium catalyst is high, the reaction process is not easy to control, and the reaction conditions are harsh, so that the method is not beneficial to large-scale industrial production. Therefore, the development of a preparation method which can reduce the cost and improve the production benefit is of great significance.
Disclosure of Invention
The invention aims to provide a catalyst which has a good catalytic effect on the synthesis of 5-bromoindanone.
The catalyst is homogeneous composite catalyst [ bmim][TFSI]/AlCl3-LiCl。
The homogeneous composite catalyst [ bmim][TFSI]/AlCl3-LiCl is prepared as follows:
step 1, firstly, slowly heating 20ml of ionic liquid 1-butyl 3-methylimidazolium bromide to 80 ℃, then slowly adding isovolumetric bis (trifluoromethylsulfonyl) imide into the ionic liquid, and stirring for 24 hours under the condition of nitrogen;
step 2, dissolving the obtained mixture with an ethyl acetate solvent, taking the filtrate and evaporating to dryness to obtain an ionic liquid [ bmim ] [ TFSI ];
step 3, heating the ionic liquid [ bmim ] [ TFSI ] to 80 ℃, slowly adding 3.2g of aluminum chloride and 1.6g of lithium chloride into the ionic liquid under the condition of nitrogen, and stirring for 6 hours at 80 ℃ until the solid is completely dissolved;
step 4, centrifuging and standing the mixture, and then obtaining the homogeneous composite catalyst [ bmim][TFSI]/AlCl3-LiCl。
The catalyst is applied to the synthesis of 5-bromoindanone.
Has the advantages that: the invention provides a homogeneous composite catalyst [ bmim][TFSI]/AlCl3-LiCl is used for catalytic synthesis of 5-bromoindanone, bromobenzene and 3-bromopropionyl chloride in homogeneous composite catalyst [ bmim][TFSI]/AlCl3Under the action of LiClAnd carrying out Friedel-Crafts acylation and Friedel-Crafts alkylation reaction to obtain the 5-bromoindanone intermediate. Bromobenzene can react with 3-bromopropionyl chloride under the action of a catalyst to obtain aryl ketone with higher purity. The active component of the catalyst is complexed with acyl chloride to promote the generation of positive ions of acyl, and compared with acyl chloride which is used as an acylation reagent, the byproduct organic acid generated by acid anhydride consumes more triflic acid with the same amount; the consumption of the trifluoromethanesulfonic acid is increased, the price is expensive, and the industrial production is not facilitated. The use of the compounded catalyst avoids the corrosion of equipment, the reaction condition is easy to control, the yield is high, and the product is easy to purify.
Detailed Description
Example 1
Homogeneous composite catalyst [ bmim][TFSI]/AlCl3-LiCl is prepared as follows:
step 1, firstly, slowly heating 20ml of ionic liquid 1-butyl 3-methylimidazolium bromide to 80 ℃, then slowly adding isovolumetric bis (trifluoromethylsulfonyl) imide into the ionic liquid, and stirring for 24 hours under the condition of nitrogen;
step 2, dissolving the obtained mixture with an ethyl acetate solvent, taking the filtrate and evaporating to dryness to obtain an ionic liquid [ bmim ] [ TFSI ];
step 3, heating the ionic liquid [ bmim ] [ TFSI ] to 80 ℃, slowly adding 3.2g of aluminum chloride and 1.6g of lithium chloride into the ionic liquid under the condition of nitrogen, and stirring for 6 hours at 80 ℃ until the solid is completely dissolved;
step 4, centrifuging and standing the mixture, and then obtaining the homogeneous composite catalyst [ bmim][TFSI]/AlCl3-LiCl。
The method for synthesizing 5-bromoindanone is characterized by comprising the following steps:
step 1, adding 5.5ml bromobenzene into a 100ml flask to be dissolved in 45ml dichloromethane, keeping the temperature in the flask at 5 ℃ under an ice salt bath, and adding 8g of homogeneous phase composite catalyst [ bmim ] into the flask in two times][TFSI]/AlCl3-LiCl, stirring at low temperature for 30 min;
step 2, controlling the temperature in the bottle to be lower than 5 ℃, slowly dripping 4.5ml of 3-bromopropionyl chloride, and reacting at room temperature for 16 hours after dripping;
step 3, slowly dripping 4.5ml of trifluoromethanesulfonic acid into the system, uniformly mixing, stirring and heating to 90 ℃, and carrying out TCL tracking monitoring reaction for 4 hours;
step 4, cooling to room temperature after complete reaction, slowly adding a mixture of 4g of concentrated hydrochloric acid and 12g of ice under an ice salt bath, and cooling;
step 5, adding dichloroethane of 45m1 for extraction after all the solids are dissolved, transferring the mixture into a separating funnel, adjusting the pH of the water phase to be =5 by using a NaOH solution with the concentration of 20%, standing and separating, and extracting the water phase by using the dichloroethane for three times;
step 6, after extraction, combining ice water washing and saturated salt water washing with the same volume, and washing with anhydrous MgSO4Drying the organic phase, removing the extractant by rotary evaporation to obtain a crude product, purifying the crude product by a silica gel column, and removing the solvent by rotary evaporation to obtain the faint yellow 5-bromoindanone.
Example 2
Step 1, adding 5.0ml bromobenzene into a 100ml flask to be dissolved in 45ml dichloromethane, keeping the temperature in the flask at 5 ℃ under an ice salt bath, and adding 8g of homogeneous phase composite catalyst [ bmim ] into the flask in two times][TFSI]/AlCl3-LiCl, stirring at low temperature for 30 min; the rest of the procedure was the same as in example 1.
Example 3
Step 1, adding 4.5ml bromobenzene into a 100ml flask to be dissolved in 45ml dichloromethane, keeping the temperature in the flask at 5 ℃ under an ice salt bath, and adding 8g of homogeneous phase composite catalyst [ bmim ] into the flask in two times][TFSI]/AlCl3-LiCl, stirring at low temperature for 30 min; the rest of the procedure was the same as in example 1.
Example 4
Step 1, adding 4.0ml bromobenzene into a 100ml flask to be dissolved in 45ml dichloromethane, keeping the temperature in the flask at 5 ℃ under an ice salt bath, and adding 8g of homogeneous phase composite catalyst [ bmim ] into the flask in two times][TFSI]/AlCl3-LiCl, stirring at low temperature for 30 min; the rest of the procedure was the same as in example 1.
Example 5
Step 1, adding 3.5ml bromobenzene into a 100ml flask to be dissolved in 45ml dichloromethane, keeping the temperature in the flask at 5 ℃ under an ice salt bath, and adding 8g of homogeneous phase composite catalyst [ bmim ] into the flask in two times][TFSI]/AlCl3-LiCl, stirring at low temperature for 30 min; the rest of the procedure was the same as in example 1.
Example 6
Step 1, adding 3.0ml bromobenzene into a 100ml flask to be dissolved in 45ml dichloromethane, keeping the temperature in the flask at 5 ℃ under an ice salt bath, and adding 8g of homogeneous phase composite catalyst [ bmim ] into the flask in two times][TFSI]/AlCl3-LiCl, stirring at low temperature for 30 min; the rest of the procedure was the same as in example 1.
Example 7
Step 2, controlling the temperature in the bottle to be lower than 5 ℃, slowly dripping 4.0ml of 3-bromopropionyl chloride, and reacting at room temperature for 16 hours after dripping; the rest of the procedure was the same as in example 1.
Example 8
Step 2, controlling the temperature in the bottle to be lower than 5 ℃, slowly dripping 3.5ml of 3-bromopropionyl chloride, and reacting at room temperature for 16 hours after finishing dripping; the rest of the procedure was the same as in example 1.
Example 9
Step 2, controlling the temperature in the bottle to be lower than 5 ℃, slowly dripping 3.0ml of 3-bromopropionyl chloride, and reacting at room temperature for 16 hours after finishing dripping; the rest of the procedure was the same as in example 1.
Example 10
Step 2, controlling the temperature in the bottle to be lower than 5 ℃, slowly dripping 2.5ml of 3-bromopropionyl chloride, and reacting at room temperature for 16 hours after finishing dripping; the rest of the procedure was the same as in example 1.
Comparative example 1
The difference from embodiment 1 is that: synthesis of intermediates step 1, the same amount of [ bmim ] [ TFSI ] was used as catalyst and the rest of the procedure was exactly the same as in example 1.
Comparative example 2
The difference from embodiment 1 is that: in the synthesis step 1 of the intermediate, the homogeneous composite catalyst is not added any more, and the rest steps are completely the same as those in example 1.
Comparative example 3
The difference from embodiment 1 is that: synthesis of catalyst in step 1, the volume ratio of 1-butyl 3-methylimidazolium bromide to bis (trifluoromethylsulfonyl) imide is 1:2, and the rest of the procedure is exactly the same as in example 1.
Comparative example 4
The difference from embodiment 1 is that: synthesis of catalyst in step 1, the volume ratio of 1-butyl 3-methylimidazolium bromide to bis (trifluoromethylsulfonyl) imide is 2:1, and the rest of the procedure is exactly the same as in example 1.
Comparative example 5
The difference from embodiment 1 is that: synthesis of catalyst in step 1, bis (trifluoromethanesulfonyl) imide was substituted with the same amount of bis (chlorosulfonyl) imide, and the rest of the procedure was exactly the same as in example 1.
Comparative example 6
The difference from embodiment 1 is that: synthesis of catalyst in step 1, bis (trifluoromethylsulfonyl) imide was substituted with the same amount of bis (perfluorohexylsulfonyl) imide, and the rest of the procedure was exactly the same as in example 1.
Comparative example 7
The difference from embodiment 1 is that: in the step 3 of synthesizing the catalyst, no aluminum chloride is added; the rest of the procedure was exactly the same as in example 1.
Comparative example 8
The difference from embodiment 1 is that: in the step 3 of synthesizing the catalyst, lithium chloride is not added; the rest of the procedure was exactly the same as in example 1.
Comparative example 9
The difference from embodiment 1 is that: in the step 3 of synthesizing the catalyst, the mass ratio of aluminum chloride to lithium chloride is 1: 1, the rest of the procedure is exactly the same as in example 1.
Comparative example 10
The difference from embodiment 1 is that: in the step 3 of synthesizing the catalyst, the mass ratio of aluminum chloride to lithium chloride is 1:2, the rest of the procedure was exactly the same as in example 1.
The results of the reactions under different conditions in the examples and the comparative examples are shown in the table
Figure 627300DEST_PATH_IMAGE001
The experimental result shows that the catalyst has good catalytic effect on the acylation reaction after the substitution of bromobenzene and 3-bromopropionyl chloride, and when the reaction condition is fixed, the higher the intermediate yield is, the better the catalytic performance is, otherwise, the worse the intermediate yield is; the volume ratio of bromobenzene to 3-bromopropionyl chloride is 11: 9, other ingredients are fixed, the synthesis effect is best, and the difference from the example 1 is that the yield is not as high as that of the example 1 although the main raw materials of bromobenzene and 3-bromopropionyl chloride are respectively changed from the example 2 to the example 10, and the yield is higher than that of the example 1 although the effect is certain; the homogeneous phase composite catalyst is not added any more and is replaced by the same amount of [ bmim ] [ TFSI ] in comparison examples 1 to 2, and other steps are completely the same, so that the product yield is obviously reduced, and the effect of the homogeneous phase composite catalyst is very good; comparative examples 3 to 6, in which the volume ratio of 1-butyl 3-methylimidazolium bromide to bis (trifluoromethylsulfonyl) imide was changed and bis (chlorosulfonyl) imide and bis (perfluorohexylsulfonyl) imide were used for substitution, the effect was still poor, indicating that either the mixture ratio or the composition of bis (trifluoromethylsulfonyl) imide was very suitable for the reaction system; comparative examples 7 to 10 do not contain aluminum chloride and lithium chloride, and the reaction effect is still poor by changing the ratio of the aluminum chloride to the lithium chloride, which shows that the synergistic catalysis effect of the aluminum chloride and the lithium chloride is better than that of single-component catalysis; therefore, the catalyst has excellent catalytic effect on the synthesis reaction of the intermediate 5-bromoindanone.

Claims (2)

1. The catalyst is characterized in that the catalyst is a homogeneous composite catalyst [ bmim][TFSI]/AlCl3-LiCl; the homogeneous composite catalyst [ bmim][TFSI]/AlCl3-LiCl is prepared as follows: step 1, firstly, slowly heating 20ml of ionic liquid 1-butyl 3-methylimidazolium bromide to 80 ℃, then slowly adding isovolumetric bis (trifluoromethylsulfonyl) imide into the ionic liquid, and stirring for 24 hours under the condition of nitrogen; step 2, dissolving the obtained mixture with ethyl acetate solvent, taking filtrate and evaporating to dryness to obtain ionic liquid [ bmim][TFSI](ii) a Step 3, mixing the ionic liquid [ bmim][TFSI]Heating to 80 ℃, slowly adding 3.2g of aluminum chloride and 1.6g of lithium chloride into the ionic liquid under the condition of nitrogen, and stirring for 6 hours while keeping the temperature of 80 ℃ until the solid is completely dissolved; step 4, centrifuging and standing the mixture, and then obtaining the homogeneous composite catalyst [ bmim][TFSI]/AlCl3-LiCl。
2. The use of the catalyst of claim 1 in the synthesis of 5-bromoindanone.
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CN104418700A (en) * 2013-08-23 2015-03-18 无锡昱天生物医药有限公司 Synthetic method for 7-bromoindene
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