CN113480394A - Green synthesis method of alkylene fluorene - Google Patents
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Abstract
The invention discloses a green synthesis method of alkylidene fluorene, which directly uses alcohol as an alkylidene reagent, uses water-soluble inorganic base as a catalyst and uses air as an oxidant to catalyze the direct oxidative condensation reaction of the alcohol and fluorene to synthesize an alkylidene fluorene compound; the reaction temperature is 80-140 ℃, and the reaction time is 12-48 hours. According to the technical scheme, no transition metal catalyst or ligand is used, the reaction does not need the protection of inert gas, the reaction can be directly carried out in the air, the conditions are relatively mild, the operation is simple, the water-soluble inorganic base can be conveniently washed and removed, and the product has no transition metal residue, so that the novel method for preparing the alkylidene fluorene is simple, efficient, mild, green, high in yield and high in selectivity. Due to the activity of an active alkenyl structure in the alkylene fluorene compound and the diversity of reactions, the invention has better synthesis value and application prospect in the aspect of synthesizing the mono-substituted fluorene or the functional group fluorene derivative.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a green synthesis method of alkylene fluorene.
Background
Fluorene and its derivatives are important organic synthetic raw materials, and are often used in the medical field to produce anticonvulsants, sedatives, analgesics, hypotensives, dyes, insecticides, herbicides, impact-resistant organic glass, fluorene-aldehyde resins, and the like. Fluorene and polymers substituting for fluorene are important organic polymer materials and important blue polymer luminescent materials with extremely high photoelectric activity, and are widely applied to the fields of polymer flat panel displays (PLEDs), solar cells, biological and chemical sensors and the like. In order to enhance the performance of the polyfluorene derivative polymer material, people make a lot of researches on modification of monomer fluorene.
Generally, the introduction of a substituent at the 9-position of fluorene can provide a corresponding polymer material with better solubility and processability. Currently, most methods for introducing a substituent at the 9-position of fluorene are performed by alkylation reaction. The alkylation reaction of fluorene needs to use n-butyl lithium (n-BuLi) and halohydrocarbon (RX), anhydrous, oxygen-free (inert gas protection such as nitrogen and argon), low temperature (-78 ℃), and other conditions; obviously, the method has harsh reaction conditions, and the use of n-butyllithium has high danger and cannot be used for large-scale synthesis. Some methods use caustic alkali (NaOH, KOH) and halogenated hydrocarbon to perform alkylation reaction on fluorene, but still need to use a large amount of alkali and excessive amount of highly active and highly toxic halogenated hydrocarbon (>3 equivalents), and need to use a phase transfer catalyst to effectively react, so that the method still has the disadvantages of more reaction waste, large pollution and the like. In addition, the above two methods can only obtain double alkylated products with two completely same substituents, so that it is difficult to control the reaction to stay in the single alkylation step, and the yield of the single alkylated product is generally low. In order to obtain the mono-substituted fluorene, the fluorene and aldehyde are condensed under alkaline conditions and then subjected to catalytic hydrogenation of transition metal to synthesize the mono-substituted fluorene by a literature method; however, the method needs to use active and unstable aldehyde which needs to be redistilled before use as a raw material; due to the large amount of alkali and the relatively active nature of aldehyde, the aldehyde is easy to generate Cannizzaro and other side reactions to generate byproducts, the reaction efficiency is reduced, and the atom economy is low.
It can be seen that the research of introducing alkylene into the 9 th position of fluorene by the method with high selectivity is very worthy of being carried out, and the development raw materials are easy to obtain, the toxicity is low, the method is simple and easy to implement, the reaction conditions are low, the reagent dosage is low, the generated waste is little, the pollution is low, and even no pollution is generated.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a green synthesis method of alkylene fluorene, which directly uses alcohol as an alkylidene reagent, water-soluble inorganic base as a catalyst and air as an oxidant to catalyze the direct oxidative condensation reaction of the alcohol and fluorene to synthesize the alkylene fluorene compound containing an active alkenyl structure without using a transition metal catalyst and a ligand.
In order to achieve the purpose, the invention provides the following technical scheme: a green synthesis method of alkylidene fluorene is characterized in that an alcohol is directly used as an alkylidene reagent, a water-soluble inorganic base is used as a catalyst, and air is used as an oxidant to catalyze the direct oxidative condensation reaction of the alcohol and fluorene to synthesize an alkylidene fluorene compound; the reaction temperature is 80-140 ℃, the reaction time is 12-48 hours, and the reaction formula is as follows:
wherein R is1Is a substituent group which is methyl, methoxy, halogen or trifluoromethyl; r2Is phenyl, phenyl substituted at the 2-, 3-, 4-positions, aryl, substituted aryl, heteroaryl, substituted heteroaryl, straight chain alkyl or various substituted branched alkyl groups.
Preferably, the synthesis of the alkylenefluorene compound does not use any transition metal catalyst and ligand, and does not require inert gas shielding.
Preferably, the molar ratio of the raw material fluorene or substituted fluorene to the alcohol is 1:1 to 1: 3.
Preferably, the water-soluble inorganic base used is LiOH, NaOH, KOH, CsOH, t-BuOK, t-BuONa, Mg (OH)2Or Ca (OH)2。
Preferably, the water-soluble inorganic base catalyst is used in an amount of 10 to 200 mol%.
Preferably, an organic solvent is used in the reaction, and the organic solvent is toluene, xylene, benzene, DMSO, DMF, acetonitrile, or dioxane.
Preferably, the reaction is carried out directly under air, oxygen or an oxidizing agent.
Preferably, the reaction time is 24 hours when the reaction temperature is 100 ℃.
The invention has the advantages that: the invention directly uses alcohol as an alkylidene reagent, water-soluble inorganic base as a catalyst and air as an oxidant to catalyze the direct oxidative condensation reaction of the alcohol and the fluorene to synthesize the alkylidene fluorene compound containing the active alkenyl structure without using a transition metal catalyst and a ligand.
Due to the activity of an active alkenyl structure in the alkylene fluorene compound and the diversity of reactions, the invention has better synthesis value and application prospect in the aspect of synthesizing the mono-substituted fluorene or the functional group fluorene derivative.
The present invention will be further described with reference to the following specific examples.
Detailed Description
The invention discloses a green synthesis method of alkylidene fluorene, which directly uses alcohol as an alkylidene reagent, water-soluble inorganic base as a catalyst and air as an oxidant to catalyze the direct oxidative condensation reaction of the alcohol and fluorene to synthesize an alkylidene fluorene compound; the reaction temperature is 80-140 ℃, the reaction time is 12-48 hours, and the reaction formula is as follows:
wherein R is1Is a substituent group which is methyl, methoxy, halogen or trifluoromethyl; r2Is phenyl, phenyl substituted at the 2-, 3-, 4-positions, aryl, substituted aryl, heteroaryl, substituted heteroaryl, straight chain alkyl or various substituted branched alkyl groups.
Preferably, the synthesis of the alkylenefluorene compound does not use any transition metal catalyst and ligand, and does not require inert gas shielding.
Preferably, the molar ratio of the raw material fluorene or substituted fluorene to the alcohol is 1:1 to 1: 3. Among them, the molar ratio of the raw material fluorene or substituted fluorene to the alcohol is preferably 1: 1.5.
Preferably, the water-soluble inorganic base used is LiOH, NaOH, KOH, CsOH, t-BuOK, t-BuONa, Mg (OH)2Or Ca (OH)2. Among them, NaOH is preferably used as the water-soluble inorganic base.
Preferably, the water-soluble inorganic base catalyst is used in an amount of 10 to 200 mol%. Among them, the amount of the water-soluble inorganic base catalyst is preferably 20 mol%.
Preferably, an organic solvent is used in the reaction, and the organic solvent is toluene, xylene, benzene, DMSO, DMF, acetonitrile, or dioxane. Among them, toluene is preferable as the organic solvent.
Preferably, the reaction is carried out directly under air, oxygen or an oxidizing agent. Among them, the reaction is preferably carried out under air.
Preferably, the reaction time is 24 hours when the reaction temperature is 100 ℃.
The following examples will help to understand the present invention, but are not limited to the contents of the present invention.
Example 1
Preparation of 9-benzylidene fluorene by reaction of fluorene and benzyl alcohol
Fluorene (1mmol), benzyl alcohol (1.5mmol,1.5equiv.), NaOH (20 mol%), 0.5mL toluene were added to a 100mL reaction tube in sequence, directly under airSealing and heating to 100 ℃ for reaction for 24h, concentrating the reaction mixture, and separating and purifying by using column chromatography to obtain the product with the separation yield of 93%.1H NMR(500MHz,CDCl3):δ7.77,(d,J＝7.5Hz,1H),7.71-6.68(m,3H),7.58-7.54(m,3H),7.45-7.42(m,2H),7.39-7.35(m,2H),7.33-7.27(m,2H),7.06-7.02(m,1H).13C NMR(125.4MHz,CDCl3):δ141.2,139.5,139.2,136.9,136.5,136.47,129.2,128.5,128.2,128.0,127.2,126.9,126.6,124.4,120.2,119.7,119.6.MS(EI):m/z(％)113(13),125(11),126(23),250(23),251(8),252(58),253(100),254(82,M+)。
Example 2
Reaction of fluorene and 4-methylbenzyl alcohol to prepare 9- (4-methylbenzylidene) fluorene
Fluorene (1mmol), 4-methylbenzyl alcohol (1.5mmol,1.5equiv.), NaOH (40 mol%) and 0.5mL of toluene are sequentially added into a 100mL reaction tube, the reaction is directly sealed and heated to 100 ℃ under air for 24 hours, a reaction mixture is concentrated and then separated and purified by column chromatography, and the separation yield of the product is 94%.1H NMR(300MHz,CDCl3):δ7.82(d,J＝7.5Hz,1H),7.77-7.71(m,4H),7.53(d,J＝7.5Hz,2H),7.43-7.26(m,5H),7.14-7.09(m,1H),2.47(s,3H).13C NMR(125.4MHz,CDCl3):δ141.1,139.6,139.0,138.0,136.6,135.9,133.8,129.24,129.18,128.4,128.0,127.5,126.9,126.6,124.3,120.1,119.6,119.5,21.4.MS(EI):m/z(％)126(23),133(13),250(13),252(76),253(94),254(19),263(11),265(13),267(41),268(100),269(41)。
Example 3
Reaction of fluorene and 4-methoxy benzyl alcohol to prepare 9- (4-methoxy benzylidene) fluorene
Fluorene (1mmol), 4-methoxybenzyl alcohol (1.5mmol,1.5equiv.), NaOH (20 mol%) and 0.5mL of toluene were sequentially added to a 100mL reaction tube, and the reaction tube was directly sealed and heated in the airReacting at 100 ℃ for 24h, concentrating the reaction mixture, and separating and purifying by column chromatography to obtain the product with the separation yield of 86%.1H NMR(300MHz,CDCl3):δ7.80-7.71(m,4H),7.67(s,1H),7.56(dd,J＝0.6Hz,J＝9.0Hz,2H),7.41-7.30(m,3H),7.13-7.08(m,1H),7.03-6.98(m,2H),3.90(s,3H).13C NMR(125.4MHz,CDCl3):δ159.5,141.1,139.7,138.9,136.6,135.4,130.8,129.1,128.3,127.9,127.3,126.9,126.6,124.2,120.1,119.7,119.5,113.9,55.3.MS(EI):m/z(％)120(18),239(51),240(24),241(18),253(30),269(16),283(22),284(100),285(23)。
Example 4
Reaction of fluorene and 3-methoxy benzyl alcohol to prepare 9- (3-methoxy benzylidene) fluorene
Fluorene (1mmol), 3-methoxybenzyl alcohol (1.5mmol,1.5equiv.), NaOH (20 mol%) and 0.5mL of toluene are sequentially added into a 100mL reaction tube, the reaction is directly sealed and heated to 100 ℃ under air for 24 hours, the reaction mixture is concentrated and then separated and purified by column chromatography, and the separation yield of the product is 87%.1H NMR(300MHz,CDCl3):δ7.82-7.79(m,1H),7.76-7.72(m,2H),7.69(s,1H),7.64(d,J＝7.8Hz,1H),7.43-7.31(m,4H),7.22-7.15(m,2H),7.13-7.07(dt,J＝0.9Hz,J＝7.5Hz,1H),6.97(dd,J＝2.4Hz,J＝8.1Hz,1H),3.86(s,3H).13C NMR(125.4MHz,CDCl3):δ159.6,141.2,139.4,139.2,138.2,136.6,136.5,129.6,128.5,128.2,127.0,126.9,126.6,124.6,121.6,120.2,119.7,119.5,114.2,114.0,55.3.MS(EI):m/z(％)120(27),252(43),253(79),268(29),269(19),283(40),284(100),285(21)。
Example 5
Reaction of fluorene and 2-methoxy benzyl alcohol to prepare 9- (2-methoxy benzylidene) fluorene
Fluorene (1mmol) and 2-methoxybenzyl alcohol (1.5 m) were sequentially added to a 100mL reaction tubemol,1.5equiv.), NaOH (20mol percent), 0.5mL toluene, sealing and heating to 100 ℃ under the air directly for reacting for 24 hours, concentrating the reaction mixture, and separating and purifying by column chromatography, wherein the separation yield of the product is 85 percent.1H NMR(300MHz,CDCl3):δ7.86-7.83(m,1H),7.74-7.71(m,3H),7.68-7.62(m,2H),7.44-7.26(m,4H),7.10-7.00(m,3H),3.88(s,3H).13C NMR(125.4MHz,CDCl3):δ157.7,141.4,139.6,139.0,136.8,136.1,131.2,129.9,128.2,127.9,126.9,126.5,125.5,124.3,123.9,120.5,120.3,119.6,119.4,110.8,55.5.MS(EI):m/z(％)120(11),178(100),179(15),239(20),284(34),285(8)。
Example 6
Reaction of fluorene and 4-fluorobenzyl alcohol to prepare 9- (4-fluorobenzylidene) fluorene
Fluorene (1mmol), 4-fluorobenzyl alcohol (1.5mmol,1.5equiv.), NaOH (40 mol%) and 0.5mL of toluene are sequentially added into a 100mL reaction tube, the reaction is directly sealed and heated to 100 ℃ under air for 24 hours, the reaction mixture is concentrated and then separated and purified by column chromatography, and the separation yield of the product is 63%.1H NMR(300MHz,CDCl3):δ7.77(d,J＝7.2Hz,1H),7.71(d,J＝7.5Hz,2H),7.62(s,1H),7.57-7.49(m,3H),7.41-7.29(m,3H),7.17-7.12(m,2H),7.09-7.04(m,1H).13C NMR(125.4MHz,CDCl3):δ162.4(d,J＝247.2Hz),141.3,139.2(d,J＝18.2Hz),136.5(d,J＝45.1Hz),132.8,131.1,131.0,128.6,128.3,127.0,126.7,126.0,124.2,120.2,119.8,119.6,115.7,115.6.MS(EI):m/z(％)122(9),125(9),126(11),135(19),268(15),270(55),271(100),272(92),273(18)。
Example 7
Preparation of 9- (4-chlorobenzylidene) fluorene by reaction of fluorene and 4-chlorobenzyl alcohol
Fluorene (1mmol), 4-chlorobenzyl alcohol (1.5mmol,1.5equiv.), and NaOH (20 mol%) were sequentially added to a 100mL reaction tube0.5mL of toluene, directly sealing and heating to 100 ℃ under the air, reacting for 24h, concentrating the reaction mixture, and separating and purifying by using a column chromatography, wherein the separation yield of the product is 82%.1H NMR(300MHz,CDCl3):δ7.81-7.78(m,1H),7.76-7.73(m,2H),7.62(s,1H),7.57-7.54(m,3H),7.48-7.45(m,2H),7.42-7.33(m,3H),7.11(dt,J＝0.9Hz,J＝7.8Hz,1H).13C NMR(125.4MHz,CDCl3):δ141.4,139.23,139.21,137.1,136.3,135.3,133.8,130.6,128.8,128.4,127.0,126.7,125.6,124.3,120.2,119.8,119.6.MS(EI):m/z(％)113(22),125(26),126(40),250(32),252(95),253(100),254(19),288(62),289(17),290(21)。
Example 8
Preparation of 9- (3-chlorobenzylidene) fluorene by reaction of fluorene and 3-chlorobenzyl alcohol
Fluorene (1mmol), 3-chlorobenzyl alcohol (1.5mmol,1.5equiv.), NaOH (20 mol%) and 0.5mL of toluene are sequentially added into a 100mL reaction tube, the reaction is directly sealed and heated to 100 ℃ under the air for 24 hours, the reaction mixture is concentrated and then separated and purified by column chromatography, and the separation yield of the product is 80%.1H NMR(300MHz,CDCl3):δ7.81-7.77(m,2H),7.75(s,1H),7.53-7.36(m,6H),7.17-7.12(m,1H).13C NMR(125.4MHz,CDCl3):δ141.4,139.3,139.1,138.7,137.4,136.1,134.4,129.7,129.1,128.8,128.5,128.0,127.4,127.0,126.8,125.2,124.3,120.3,119.8,119.6.MS(EI):m/z(％)113(19),125(22),126(33),250(32),252(91),253(100),254(20),288(55),289(15),290(19)。
Example 9
Preparation of 9- (2-chlorobenzylidene) fluorene by reaction of fluorene and 2-chlorobenzyl alcohol
Fluorene (1mmol), 2-chlorobenzyl alcohol (1.5mmol,1.5equiv.), NaOH (20 mol%) and 0.5mL toluene are sequentially added into a 100mL reaction tube, sealed and heated to 100 ℃ under the air directly for reaction for 24h,the reaction mixture was concentrated and purified by column chromatography, and the isolated yield of the product was 91%.1H NMR(300MHz,CDCl3):δ7.89-7.86(m,1H),7.77-7.70(m,3H),7.66(s,1H),7.59-7.56(m,1H),7.47-7.33(m,6H),7.09(dt,J＝1.2Hz,J＝7.5Hz,1H).13C NMR(125.4MHz,CDCl3):δ141.4,139.4,139.1,137.5,136.3,135.4,134.0,131.4,129.7,129.5,128.8,128.5,127.1,126.7,126.6,124.4,123.9,120.6,119.8,119.6.MS(EI):m/z(％)113(19),125(21),126(33),250(31),252(81),253(100),254(20),288(54),289(13),290(18).T。
Example 10
Preparation of 9- (4-bromobenzylidene) fluorene by reaction of fluorene and 4-bromobenzyl alcohol
Fluorene (1mmol), 4-bromobenzyl alcohol (1.5mmol,1.5equiv.), NaOH (80 mol%) and 0.5mL of toluene are sequentially added into a 100mL reaction tube, the reaction is directly sealed and heated to 100 ℃ under the air for 24 hours, the reaction mixture is concentrated and then separated and purified by column chromatography, and the separation yield of the product is 71%.1H NMR(500MHz,CDCl3):δ7.71(d,J＝7.5Hz,1H),7.67(d,J＝7.5Hz,2H),7.55-7.53(m,2H),7.51-7.49(m,2H),7.40(d,J＝8.0Hz,2H),7.35(dt,J＝1.0Hz,J＝7.5Hz,1H),7.29(dt,J＝1.0Hz,J＝7.5Hz,2H),7.05(dt,J＝1.0Hz,J＝7.5Hz,2H).13C NMR(125.4MHz,CDCl3):δ141.3,139.21,139.19,137.0,136.2,135.7,131.7,130.9,128.8,128.4,127.0,126.7,125.6,124.3,122.0,120.2,119.8,119.6.MS(EI):m/z(％)113(21),125(24),126(44),250(34),252(100),253(99),254(21),332(46),333(14),334(45)。
Example 11
Preparation of 9- (3-bromobenzylidene) fluorene by reaction of fluorene and 3-bromobenzyl alcohol
To a 100mL reaction tube were added fluorene (1mmol), 3-bromobenzyl alcohol (1.5mmol,1.5equiv.), NaOH (80 mol%), 0.5mL of toluene, sealing and heating to 100 ℃ under the air directly for reacting for 24 hours, concentrating the reaction mixture, and separating and purifying by using a column chromatography, wherein the separation yield of the product is 79%.1H NMR(500MHz,CDCl3):δ7.72-7.67(m,4H),7.52(s,1H),7.51-7.42(m,3H),7.36(t,J＝7.5Hz,1H),7.31-7.27(m,3H),7.07-7.04(m,1H).13C NMR(125.4MHz,CDCl3):δ141.4,139.3,139.1,139.0,137.5,136.2,132.0,130.9,130.0,128.9,128.5,127.8,127.1,126.8,125.1,124.4,122.6,120.3,119.8,119.6.MS(EI):m/z(％)113(20),125(23),126(42),207(15),221(15),250(31),252(84),253(100),254(20),332(43),334(45)。
Example 12
Reaction of fluorene and 2-pyridinemethanol to prepare 9- (2-pyridinemethylene) fluorene
Fluorene (1mmol), 2-pyridine benzyl alcohol (1.5mmol,1.5equiv.), NaOH (20 mol%) and 0.5mL toluene are sequentially added into a 100mL reaction tube, the reaction is directly sealed and heated to 100 ℃ under the air for 24 hours, the reaction mixture is concentrated and then separated and purified by column chromatography, and the separation yield of the product is 55%.1H NMR(300MHz,CDCl3):δ8.80(d,J＝4.8Hz,1H),8.33(d,J＝7.8Hz,1H),7.81-7.69(m,4H),7.64(d,J＝7.8Hz,1H),7.59(s,1H),7.40-7.25(m,4H),7.20-7.15(m,1H).13C NMR(125.4MHz,CDCl3):δ155.6,149.7,141.7,139.9,138.8,136.2,129.2,128.7,127.04,127.00,126.3,125.7,125.6,122.4,120.5,119.59,119.56.MS(EI):m/z(％)113(7),126(6),127(15),226(8),253(9),254(100),255(27)。
Example 13
Reaction of fluorene and 2-furancarbinol to prepare 9- (2-furanmethylene) fluorene
Fluorene (1mmol), 2-thiophenemethanol (1.5mmol,1.5equiv.), NaOH (40 mol%) and 0.5mL of toluene were sequentially added to a 100mL reaction tube, and the reaction tube was directly sealed and heated in the airReacting for 24 hours at 100 ℃, concentrating the reaction mixture, and separating and purifying by column chromatography to obtain the product with the separation yield of 85%.1H NMR(300MHz,CDCl3):δ8.81(d,J＝7.5Hz,1H),7.79-7.72(m,4H),7.45-7.30(m,5H),6.79(d,J＝3.0Hz,1H),6.61(s,1H).13C NMR(125.4MHz,CDCl3):δ152.1,143.8,141.0,140.2,138.9,136.1,132.7,128.4,127.8,127.1,126.8,125.6,119.8,119.54,119.51,115.5,112.6,112.4.MS(EI):m/z(％)95(13),107(11),189(12),213(20),215(100),216(20),243(21),244(74),245(14)。
Example 14
Reaction of fluorene and 2-thiophenemethanol for preparing 9- (2-thiophenemethylene) fluorene
Fluorene (1mmol), 2-thiophenemethanol (1.5mmol,1.5equiv.), NaOH (40 mol%) and 0.5mL of toluene are sequentially added into a 100mL reaction tube, the reaction is directly sealed and heated to 100 ℃ under air for 24 hours, the reaction mixture is concentrated and then separated and purified by column chromatography, and the separation yield of the product is 88%.1H NMR(300MHz,CDCl3):δ8.15(d,J＝7.8Hz,1H),7.78-7.72(m,3H),7.64(s,1H),7.49-7.46(m,2H),7.41-7.31(m,3H),7.23-7.16(m,2H).13C NMR(125.4MHz,CDCl3):δ141.2,139.5,139.1,138.9,136.6,136.1,129.3,128.7,128.2,127.6,127.3,127.0,126.8,124.4,120.2,119.8,119.6,119.0.MS(EI):m/z(％)129(20),213(12),215(16),226(12),227(12),258(42),259(100),260(87),261(20)。
Example 15
Preparation of 9- (2-naphthylmethylene) fluorene by reaction of fluorene and 2-naphthylmethanol
Sequentially adding fluorene (1mmol), 2-naphthylmethanol (1.5mmol,1.5equiv.), NaOH (80 mol%) and 0.5mL of toluene into a 100mL reaction tube, directly sealing and heating to 100 ℃ under air for reaction for 24 hours, concentrating the reaction mixture, separating and purifying by using a column chromatography, and obtaining a product with the separation yield of 74%。1H NMR(300MHz,CDCl3):δ8.06(s,1H),7.92-7.81(m,5H),7.73-7.68(m,3H),7.61(d,J＝7.8Hz,1H),7.54-7.51(m,2H),7.41-7.28(m,3H),7.03-6.98(m,1H).13C NMR(125.4MHz,CDCl3):δ141.3,139.5,139.2,136.7,136.5,134.3,133.3,132.9,128.6,128.5,128.2,128.1,128.06,127.8,127.3,127.2,127.0,126.7,126.4,126.39,124.4,120.3,119.7,119.6.MS(EI):m/z(％)73(16),145(11),150(20),151(32),207(26),281(18),300(24),302(58),303(94),304(100),305(24)。
Example 16
Reaction of fluorene and 1-naphthylcarbinol to prepare 9- (1-naphthylmethylene) fluorene
Fluorene (1mmol), 1-naphthylmethanol (1.5mmol,1.5equiv.), NaOH (20 mol%) and 0.5mL of toluene are sequentially added into a 100mL reaction tube, the reaction is directly sealed and heated to 100 ℃ under the air for 24 hours, the reaction mixture is concentrated and then separated and purified by column chromatography, and the separation yield of the product is 86%.1H NMR(300MHz,CDCl3):δ8.09(d,J＝8.4Hz,2H),7.98-7.93(m,3H),7.79-7.72(m,3H),.7.60-7.41(m,5H),7.31-7.25(m,1H),7.13(d,J＝7.8Hz,1H),6.93(t,J＝7.5Hz,1H).13C NMR(125.4MHz,CDCl3):δ141.1,139.4,139.1,137.9,136.7,134.2,133.6,131.6,128.5,128.47,128.44,128.3,127.1,127.0,126.7,126.3,126.2,125.4,125.3,125.1,124.7,120.4,119.64,119.60.MS(EI):m/z(％)145(15),150(27),151(36),207(20),281(15),300(24),302(60),303(96),304(100),305(25)。
The invention directly uses alcohol as an alkylidene reagent, water-soluble inorganic base as a catalyst and air as an oxidant to catalyze the direct oxidative condensation reaction of the alcohol and the fluorene to synthesize the alkylidene fluorene compound containing the active alkenyl structure without using a transition metal catalyst and a ligand.
Due to the activity of an active alkenyl structure in the alkylene fluorene compound and the diversity of reactions, the invention has better synthesis value and application prospect in the aspect of synthesizing the mono-substituted fluorene or the functional group fluorene derivative.
The above embodiments are described in detail for the purpose of further illustrating the present invention and should not be construed as limiting the scope of the present invention, and the skilled engineer can make insubstantial modifications and variations of the present invention based on the above disclosure.
Claims (8)
1. A green synthesis method of alkylene fluorene is characterized in that: directly using alcohol as an alkylidene reagent, using water-soluble inorganic base as a catalyst and using air as an oxidant to catalyze the direct oxidative condensation reaction of the alcohol and fluorene to synthesize an alkylidene fluorene compound; the reaction temperature is 80-140 ℃, the reaction time is 12-48 hours, and the reaction formula is as follows:
wherein R is1Is a substituent group which is methyl, methoxy, halogen or trifluoromethyl; r2Is phenyl, phenyl substituted at the 2-, 3-, 4-positions, aryl, substituted aryl, heteroaryl, substituted heteroaryl, straight chain alkyl or various substituted branched alkyl groups.
2. A green synthesis method of an alkylenefluorene according to claim 1, wherein: the synthesis of the alkylidene fluorene compound does not use any transition metal catalyst and ligand, and does not need inert gas protection.
3. A green synthesis method of an alkylenefluorene according to claim 1, wherein: the molar ratio of the raw material fluorene or substituted fluorene to the alcohol is 1: 1-1: 3.
4. A green synthesis method of an alkylenefluorene according to claim 1, wherein: the water-soluble inorganic base is LiOH, NaOH, KOH, CsOH, t-BuOK, t-BuONa, Mg (OH)2Or Ca (OH)2。
5. A green synthesis method of an alkylenefluorene according to claim 1, wherein: the dosage of the water-soluble inorganic base catalyst is 10-200 mol%.
6. A green synthesis method of an alkylenefluorene according to claim 1, wherein: the reaction uses organic solvent which is toluene, xylene, benzene, DMSO, DMF, acetonitrile or dioxane.
7. A green synthesis method of an alkylenefluorene according to claim 1, wherein: the reaction is directly carried out under the condition of air, oxygen or oxidant.
8. A green synthesis method of an alkylenefluorene according to claim 1, wherein: the reaction time was 24 hours when the reaction temperature was 100 ℃.
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