CN102617301A - Synthesizing process for low rim tetra-benzyl substituted p-tert-butylcalix (4) arene derivative - Google Patents
Synthesizing process for low rim tetra-benzyl substituted p-tert-butylcalix (4) arene derivative Download PDFInfo
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Abstract
The invention discloses a synthesizing process for a low rim tetra-benzyl substituted p-tert-butylcalix (4) arene derivative. The process includes using p-tert-butylcalix (4) arene and benzyl halide compounds as raw materials, adding barium hydroxide and barium oxide in an organic solvent, subjecting the mixture to reaction at the temperature between 0 DEG C and 100 DEG C for 0.5 hour to 24 hours under the protection of nitrogen (N2), and obtaining the low rim tetra-benzyl substituted p-tert-butylcalix (4) arene derivative when the reaction liquid is subjected to post processing. According to the synthesizing process for the low rim tetra-benzyl substituted p-tert-butylcalix (4) arene derivative, the synthetic route is advanced, the synthetic condition is reasonable, the operation is simple and safe, the reaction yield is high, the selectivity is good, the purification is easy, the environment pollution is little, the atom economy is good, and the implementation value is high.
Description
(1) technical field
The present invention relates to a kind of lower edge tetrabenzyl and replace compound method tertiary butyl cup [4] arene derivatives.
(2) technical background
It is one type of important super molecular compound that the lower edge tetrabenzyl replaces tertiary butyl cup [4] arene derivatives; This analog derivative has unique cavity structure; Some metals ion, organic cation, negatively charged ion, neutral molecule etc. are all had high selectivity and affinity, important use is arranged in fields such as molecular recognition, chemical sensors.
The method that synthetic lower edge tetrabenzyl replaces tertiary butyl cup [4] arene derivatives in the prior art has: to be raw material to tertiary butyl cup [4] aromatic hydrocarbons and benzyl bromine, add NaH, THF and DMF are as mixed solvent, and 70 ℃ were reacted 1 hour, and obtained 5 through aftertreatment; 11,17,21-tetra-tert-25,26,27; 28-benzyloxy-4 cup [4] aromatic hydrocarbons (J.Org.Chem., 1991,56,4783); This method poor selectivity, the easy product that generates multiple configuration, not easy separation and easy purification, and raw material benzyl bromine consumption is more.
(3) summary of the invention
The lower edge tetrabenzyl that the technical problem that the present invention will solve provides that a kind of synthetic route is simple, easy to operate, reaction yield is high, selectivity good, is prone to purifying, environmental pollution is little, Atom economy is good replaces the compound method to tertiary butyl cup [4] arene derivatives.
The technical scheme that the present invention adopts is following:
A kind of suc as formula the compound method of the replacement of the lower edge tetrabenzyl shown in (I) to tertiary butyl cup [4] arene derivatives; Described method is: the benzyl halogen compounds to shown in tertiary butyl cup [4] aromatic hydrocarbons, the formula (III) with shown in the formula (II) is a raw material; Add hydrated barta and barium oxide, in organic solvent, N
2Protection down; Under 0～100 ℃ temperature of reaction; Reacted 0.5～24 hour, after reaction finished, reaction solution made suc as formula (I) described lower edge tetrabenzyl through aftertreatment and replaces tertiary butyl cup [4] arene derivatives; Said to tertiary butyl cup [4] aromatic hydrocarbons, benzyl halogen compounds, hydrated barta, barytic amount of substance ratio be 1: 4～15: 2～10: 2～10, be preferably 1: 4～6: 2～6: 2～6.
Reaction formula is following:
In the formula (III), X is Cl, Br or I;
In formula (I) or the formula (III), the H on the phenyl ring is substituted basic R replacement or is not substituted, and substituent R is I, methyl or ethyl.
Further, the benzyl halogen compounds shown in the preferred said formula (III) be benzyl chlorine, benzyl bromine, benzyl iodine, to iodine benzyl chlorine, an iodine benzyl bromine, adjacent iodine benzyl bromine, to iodine benzyl bromine, an iodine benzyl iodine, to iodine benzyl iodine, to methyl benzyl chlorine, adjacent methyl benzyl chlorine, a methyl benzyl chlorine, to methyl benzyl bromine, adjacent methyl benzyl bromine, a methyl benzyl bromine, to methyl benzyl iodine, adjacent methyl benzyl iodine, a methyl benzyl iodine, to the benzyl ethyl bromine or to benzyl ethyl chlorine.
Most preferred, the benzyl halogen compounds shown in the said formula (III) is benzyl chlorine, benzyl bromine, to iodine benzyl bromine, to iodine benzyl iodine or to methyl benzyl bromine, more preferably benzyl chlorine, benzyl bromine or to methyl benzyl bromine.
In the formula (I), the H on the said phenyl ring preferably is not substituted or by to methyl substituted.
Organic solvent of the present invention is one of following: THF, 2-methyltetrahydrofuran, chloroform, methylene dichloride, 1; 2-methylene dichloride, N; Dinethylformamide, N; N-N,N-DIMETHYLACETAMIDE, acetone, acetonitrile, benzene or toluene are preferably one of following: THF, N, dinethylformamide, acetonitrile or toluene.
Said volume of organic solvent consumption is to count 30～80mL/g, preferred 45～65mL/g to the quality of tertiary butyl cup [4] aromatic hydrocarbons.
Temperature of reaction of the present invention is preferably 20～50 ℃, and the preferred reaction time is 1～8h.
In the inventive method; Described reaction solution post-treating method is: pour in the frozen water behind the reaction solution concentrating under reduced pressure; Separate out solid after the stirring; Suction filtration, filter cake, obtain the lower edge tetrabenzyl and replace tertiary butyl cup [4] arene derivatives with volume ratio 1: 1～3 blended mixed solvent recrystallizations with methylene dichloride and methyl alcohol.
More specifically, the method for the invention is carried out according to following steps: according to being 1: 4～6: 2～6: 2～6 to feed intake to tertiary butyl cup [4] aromatic hydrocarbons, benzyl halogen compounds, hydrated barta, barytic amount of substance, add in the organic solvent N
2Protection down; In 20～50 ℃ the reaction 1～8 hour after; Pour in the frozen water behind the reaction solution concentrating under reduced pressure, separate out solid, suction filtration after the stirring; Filter cake, obtains replacing tertiary butyl cup [4] arene derivatives suc as formula the lower edge tetrabenzyl shown in (I) with volume ratio 1: 1～3 blended mixed solvent recrystallizations with methylene dichloride and methyl alcohol; Said benzyl halogen compounds is benzyl chlorine, benzyl bromine, to iodine benzyl bromine, to iodine benzyl iodine or to methyl benzyl bromine; Described organic solvent is one of following: THF, N, dinethylformamide, acetonitrile or toluene.
The present invention compared with prior art, its advantage is:
(1) reaction conditions is gentle, and the reaction times is short, and synthetic route is simple, and operational safety is reliable, and environmental pollution is little.
(2) good reaction selectivity, aftertreatment is simple, is prone to purifying, and Atom economy is good, and reaction yield is high, has implementary value preferably.
(4) embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1.1
5,11,17,21-tetra-tert-25,26,27,28-benzyloxy-4 cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 1.012g (8mmol) benzyl chlorine, 3.150g (10mmol) barium hydroxide, 1.531g (10mmol) barium oxide, 40ml toluene; Nitrogen protection, 100 ℃ of magnetic agitation 1 hour are poured frozen water into behind the reaction solution concentrating under reduced pressure, separate out a large amount of white precipitates; Suction filtration, filter cake with the mixed solvent recrystallization of 17ml methylene dichloride and 26ml methyl alcohol after suction filtration get white 5,11,17; 21-tetra-tert-25,26,27,28-benzyloxy-4 cup [4] aromatic hydrocarbons 0.81g; Yield 80.4%, fusing point are 237.7-239.9 ℃, HPLC purity 99.1%
1H NMR (400MHz, CDCl
3) δ 7.14-7.30 (m, 20H, ArH), 6.68 (s, 8H, ArH), 4.84 (s, 8H, OCH
2Ar), 4.15 (d, J=12.4Hz, 4H, ArCH
2Ar), 2.83 (d, J=12.4Hz, 4H, ArCH
2Ar), 1.05 (s, 36H, C (CH
3)
3).
Embodiment 1.2
5,11,17,21-tetra-tert-25,26,27,28-benzyloxy-4 cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 0.759g (6mmol) benzyl chlorine, 1.890g (6mmol) barium hydroxide, 0.918g (6mmol) barium oxide; The 30ml acetonitrile, nitrogen protection, 70 ℃ of magnetic agitation 8 hours are poured frozen water into behind the reaction solution concentrating under reduced pressure; Separate out a large amount of white precipitates, suction filtration, filter cake with the mixed solvent recrystallization of 18ml methylene dichloride and 24ml methyl alcohol after suction filtration get white 5,11; 17,21-tetra-tert-25,26,27; 28-benzyloxy-4 cup [4] aromatic hydrocarbons 0.84g, yield 83.3%, fusing point are 237.7-239.9 ℃, HPLC purity 98.3%.
Embodiment 1.3
5,11,17,21-tetra-tert-25,26,27,28-benzyloxy-4 cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 0.855g (5mmol) benzyl bromine, 0.787g (2.5mmol) barium hydroxide, 0.383g (2.5mmol) barium oxide, 30ml N; Dinethylformamide, nitrogen protection, 20 ℃ of magnetic agitation 2 hours are poured frozen water into behind the reaction solution concentrating under reduced pressure; Separate out a large amount of white precipitates, suction filtration, filter cake with the mixed solvent recrystallization of 17ml methylene dichloride and 25ml methyl alcohol after suction filtration get white 5,11; 17,21-tetra-tert-25,26,27; 28-benzyloxy-4 cup [4] aromatic hydrocarbons 0.83g, yield 82.3%, fusing point are 237.7-239.9 ℃, HPLC purity 98.6%.
Embodiment 1.4
5,11,17,21-tetra-tert-25,26,27,28-benzyloxy-4 cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 1.026g (6mmol) benzyl bromine, 2.520g (8mmol) barium hydroxide, 1.224g (8mmol) barium oxide; The 35ml THF, nitrogen protection, 50 ℃ of magnetic agitation 15 hours are poured frozen water into behind the reaction solution concentrating under reduced pressure; Separate out a large amount of white precipitates, suction filtration, filter cake with the mixed solvent recrystallization of 18ml methylene dichloride and 26ml methyl alcohol after suction filtration get white 5,11; 17,21-tetra-tert-25,26,27; 28-benzyloxy-4 cup [4] aromatic hydrocarbons 0.81g, yield 80.4%, fusing point are 237.7-239.9 ℃, HPLC purity 98.2%.
Embodiment 1.5
5,11,17,21-tetra-tert-25,26,27,28-benzyloxy-4 cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 3.270g (15mmol) benzyl iodine, 1.261g (4mmol) barium hydroxide, 0.612g (4mmol) barium oxide; The 40ml chloroform, nitrogen protection, 30 ℃ of magnetic agitation 10 hours are poured frozen water into behind the reaction solution concentrating under reduced pressure; Separate out a large amount of white precipitates, suction filtration, filter cake with the mixed solvent recrystallization of 15ml methylene dichloride and 29ml methyl alcohol after suction filtration get white 5,11; 17,21-tetra-tert-25,26,27; 28-benzyloxy-4 cup [4] aromatic hydrocarbons 0.67g, yield 66.5%, fusing point are 237.7-239.9 ℃, HPLC purity 98.8%.
Embodiment 1.6
5,11,17,21-tetra-tert-25,26,27,28-benzyloxy-4 cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 0.872g (4mmol) benzyl iodine, 0.63g (2mmol) barium hydroxide, 0.306g (2mmol) barium oxide; The 30ml methylene dichloride, nitrogen protection, 0 ℃ of magnetic agitation 6 hours is poured frozen water into behind the reaction solution concentrating under reduced pressure; Separate out a large amount of white precipitates, suction filtration, filter cake with the mixed solvent recrystallization of 15ml methylene dichloride and 20ml methyl alcohol after suction filtration get white 5,11; 17,21-tetra-tert-25,26,27; 28-benzyloxy-4 cup [4] aromatic hydrocarbons 0.59g, yield 58.5%, fusing point are 237.7-239.9 ℃, HPLC purity 98.9%.
Embodiment 2.1
5,11,17,21-tetra-tert-25,26,27,28-four (4-iodine benzyloxy) cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 3.783g (15mmol) is to iodine benzyl chlorine, 1.891g (6mmol) barium hydroxide, 0.918g (6mmol) barium oxide, 30ml benzene; Nitrogen protection, 80 ℃ of magnetic agitation 3 hours are poured frozen water into behind the reaction solution concentrating under reduced pressure, separate out a large amount of white precipitates; Suction filtration, filter cake with the mixed solvent recrystallization of 15ml methylene dichloride and 28ml methyl alcohol after suction filtration get white 5,11,17; 21-tetra-tert-25,26,27,28-four (4-iodine benzyloxy) cup [4] aromatic hydrocarbons 0.98g; Yield 64.8%, fusing point are 224.0-225.8 ℃, HPLC purity 98.2%
1H NMR (400MHz, CDCl
3) δ 7.50 (d, J=8.0Hz, 8H, ArH), 6.93 (d, J=7.6Hz, 8H, ArH), 6.71 (s, 8H, ArH), 4.72 (s, 8H, OCH
2Ar), 4.08 (d, J=12.8Hz, 4H, ArCH
2Ar), 2.88 (d, J=12.4Hz, 4H, ArCH
2Ar), 1.06 (s, 36H, C (CH
3)
3).
Embodiment 2.2
5,11,17,21-tetra-tert-25,26,27,28-four (4-iodine benzyloxy) cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 1.515g (6mmol) is to iodine benzyl chlorine, 1.575g (5mmol) barium hydroxide, 0.765g (5mmol) barium oxide; The 30ml DMAC N,N, nitrogen protection, 40 ℃ of magnetic agitation 18 hours; Pour frozen water into behind the reaction solution concentrating under reduced pressure, separate out a large amount of white precipitates, suction filtration, filter cake with the mixed solvent recrystallization of 14ml methylene dichloride and 25ml methyl alcohol after suction filtration get white 5; 11,17,21-tetra-tert-25,26; 27,28-four (4-iodine benzyloxy) cup [4] aromatic hydrocarbons 0.92g, yield 60.8%, fusing point are 224.0-225.8 ℃.
Embodiment 2.3
5,11,17,21-tetra-tert-25,26,27,28-four (4-iodine benzyloxy) cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 2.376g (8mmol) is to iodine benzyl bromine, 2.522g (8mmol) barium hydroxide, 1.224g (8mmol) barium oxide; 30ml 2-methyltetrahydrofuran, nitrogen protection, 10 ℃ of magnetic agitation 24 hours are poured frozen water into behind the reaction solution concentrating under reduced pressure; Separate out a large amount of white precipitates, suction filtration, filter cake with the mixed solvent recrystallization of 16ml methylene dichloride and 26ml methyl alcohol after suction filtration get white 5; 11,17,21-tetra-tert-25; 26,27,28-four (4-iodine benzyloxy) cup [4] aromatic hydrocarbons 1.15g; Yield 76.1%, fusing point are 224.0-225.8 ℃, HPLC purity 98.8%.
Embodiment 2.4
5,11,17,21-tetra-tert-25,26,27,28-four (4-iodine benzyloxy) cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 1.485g (5mmol) is to iodine benzyl bromine, 0.631g (2mmol) barium hydroxide, 0.306g (2mmol) barium oxide; 30ml N, dinethylformamide, nitrogen protection, 30 ℃ of magnetic agitation 5 hours; Pour frozen water into behind the reaction solution concentrating under reduced pressure, separate out a large amount of white precipitates, suction filtration, filter cake with the mixed solvent recrystallization of 16ml methylene dichloride and 26ml methyl alcohol after suction filtration get white 5; 11,17,21-tetra-tert-25; 26,27,28-four (4-iodine benzyloxy) cup [4] aromatic hydrocarbons 1.22g; Yield 80.7%, fusing point are 224.0-225.8 ℃, HPLC purity 98.3%.
Embodiment 2.5
5,11,17,21-tetra-tert-25,26,27,28-four (4-iodine benzyloxy) cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 1.376g (4mmol) is to iodine benzyl iodine, 1.890g (6mmol) barium hydroxide, 0.918g (6mmol) barium oxide; 30ml toluene, nitrogen protection, 20 ℃ of magnetic agitation 0.5 hour are poured frozen water into behind the reaction solution concentrating under reduced pressure; Separate out a large amount of white precipitates, suction filtration, filter cake with the mixed solvent recrystallization of 18ml methylene dichloride and 24ml methyl alcohol after suction filtration get white 5,11; 17,21-tetra-tert-25,26,27; 28-four (4-iodine benzyloxy) cup [4] aromatic hydrocarbons 1.23g, yield 81.3%, fusing point are 224.0-225.8 ℃, HPLC purity 99.0%.
Embodiment 2.6
5,11,17,21-tetra-tert-25,26,27,28-four (4-iodo-benzyloxy) cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 4.128g (12mmol) is to iodine benzyl iodine, 2.521g (8mmol) barium hydroxide, 1.224g (8mmol) barium oxide; 40ml 1,2-methylene dichloride, nitrogen protection, 60 ℃ of magnetic agitation 8 hours; Pour frozen water into behind the reaction solution concentrating under reduced pressure, separate out a large amount of white precipitates, suction filtration, filter cake with the mixed solvent recrystallization of 18ml methylene dichloride and 28ml methyl alcohol after suction filtration get white 5; 11,17,21-tetra-tert-25; 26,27,28-four (4-iodine benzyloxy) cup [4] aromatic hydrocarbons 1.16g; Yield 76.7%, fusing point are 224.0-225.8 ℃, HPLC purity 98.4%.
Embodiment 3.1
5,11,17,21-tetra-tert-25,26,27,28-four (4-methyl benzyloxy) cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 0.562g (4mmol) is to methyl benzyl chlorine, 1.260g (4mmol) barium hydroxide, 0.612g (4mmol) barium oxide, 30ml acetone; Nitrogen protection, 30 ℃ of magnetic agitation 8 hours are poured frozen water into behind the reaction solution concentrating under reduced pressure, separate out a large amount of white precipitates; Suction filtration, filter cake with the mixed solvent recrystallization of 15ml methylene dichloride and 36ml methyl alcohol after suction filtration get white 5,11,17; 21-tetra-tert-25,26,27,28-four (4-methyl benzyloxy) cup [4] aromatic hydrocarbons 0.68g; Yield 63.9%, fusing point are 199.6-201.2 ℃, HPLC purity 99.2%
1H NMR (400MHz, CDCl
3) δ 7.12 (d, J=7.6Hz, 8H, ArH), 6.98 (d, J=7.6Hz, 8H, ArH), 6.67 (s, 8H, ArH), 4.79 (s, 8H, OCH
2Ar), 4.16 (d, J=12.4Hz, 4H, ArCH
2Ar), 2.83 (d, J=12.8Hz, 4H, ArCH
2Ar), 2.32 (s, 12H, CH
3), 1.05 (s, 36H, C (CH
3)
3).
Embodiment 3.2
5,11,17,21-tetra-tert-25,26,27,28-four (4-methyl benzyloxy) cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 1.405g (10mmol) is to methyl benzyl chlorine, 2.520g (8mmol) barium hydroxide, 1.224g (8mmol) barium oxide; 30ml N, dinethylformamide, nitrogen protection, 50 ℃ of magnetic agitation 4 hours; Pour frozen water into behind the reaction solution concentrating under reduced pressure, separate out a large amount of white precipitates, suction filtration, filter cake with the mixed solvent recrystallization of 16ml methylene dichloride and 39ml methyl alcohol after suction filtration get white 5; 11,17,21-tetra-tert-25,26; 27,28-four (4-methyl benzyloxy) cup [4] aromatic hydrocarbons 0.72g, yield 67.7%, fusing point are 199.6-201.2 ℃.
Embodiment 3.3
5,11,17,21-tetra-tert-25,26,27,28-four (4-methyl benzyloxy) cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 1.480g (8mmol) is to methyl benzyl bromine, 0.630g (2mmol) barium hydroxide, 0.306g (2mmol) barium oxide; The 30ml acetonitrile, nitrogen protection, 70 ℃ of magnetic agitation 6 hours are poured frozen water into behind the reaction solution concentrating under reduced pressure; Separate out a large amount of white precipitates, suction filtration, filter cake with the mixed solvent recrystallization of 20ml methylene dichloride and 41ml methyl alcohol after suction filtration get white 5,11; 17,21-tetra-tert-25,26,27; 28-four (4-methyl benzyloxy) cup [4] aromatic hydrocarbons 0.91g, yield 85.5%, fusing point are 199.6-201.2 ℃, HPLC purity 98.8%.
Embodiment 3.4
5,11,17,21-tetra-tert-25,26,27,28-four (4-methyl benzyloxy) cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 0.925g (5mmol) is to methyl benzyl bromine, 0.945g (3mmol) barium hydroxide, 0.459g (3mmol) barium oxide; 30ml N, dinethylformamide, nitrogen protection, 25 ℃ of magnetic agitation 2 hours; Pour frozen water into behind the reaction solution concentrating under reduced pressure, separate out a large amount of white precipitates, suction filtration, filter cake with the mixed solvent recrystallization of 20ml methylene dichloride and 42ml methyl alcohol after suction filtration get white 5; 11,17,21-tetra-tert-25,26; 27,28-four (4-methyl benzyloxy) cup [4] aromatic hydrocarbons 0.92g, yield 86.5%, fusing point are 199.6-201.2 ℃.
Embodiment 3.5
5,11,17,21-tetra-tert-25,26,27,28-four (4-methyl benzyloxy) cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 1.392g (6mmol) is to methyl benzyl iodine, 2.521g (8mmol) barium hydroxide, 1.224g (8mmol) barium oxide; The 30ml chloroform, nitrogen protection, 0 ℃ of magnetic agitation 12 hours is poured frozen water into behind the reaction solution concentrating under reduced pressure; Separate out a large amount of white precipitates, suction filtration, filter cake with the mixed solvent recrystallization of 16ml methylene dichloride and 37ml methyl alcohol after suction filtration get white 5,11; 17,21-tetra-tert-25,26,27; 28-four (4-methyl benzyloxy) cup [4] aromatic hydrocarbons 0.76g, yield 71.4%, fusing point are 199.6-201.2 ℃, HPLC purity 98.5%.
Embodiment 3.6
5,11,17,21-tetra-tert-25,26,27,28-four (4-methyl benzyloxy) cup [4] aromatic hydrocarbons synthetic:
In two mouthfuls of flasks of the 100ml that TM, reflux condensing tube are housed, add 0.648g (1mmol) to tertiary butyl cup [4] aromatic hydrocarbons, 1.624g (7mmol) is to methyl benzyl iodine, 0.787g (2.5mmol) barium hydroxide, 0.383g (2.5mmol) barium oxide; 30ml toluene, nitrogen protection, 80 ℃ of magnetic agitation 3 hours are poured frozen water into behind the reaction solution concentrating under reduced pressure; Separate out a large amount of white precipitates, suction filtration, filter cake with the mixed solvent recrystallization of 18ml methylene dichloride and 38ml methyl alcohol after suction filtration get white 5,11; 17,21-tetra-tert-25,26,27; 28-four (4-methyl benzyloxy) cup [4] aromatic hydrocarbons 0.84g, yield 78.9%, fusing point are 199.6-201.2 ℃, HPLC purity 99.1%.
Claims (10)
1. one kind replaces the compound method to tertiary butyl cup [4] arene derivatives suc as formula the lower edge tetrabenzyl shown in (I); It is characterized in that described method is: the benzyl halogen compounds to shown in tertiary butyl cup [4] aromatic hydrocarbons, the formula (III) with shown in the formula (II) is a raw material; Add hydrated barta and barium oxide; In organic solvent, N
2Protection down; Under 0～100 ℃ temperature of reaction; Reacted 0.5～24 hour; After reaction finished, reaction solution made suc as formula (I) described lower edge tetrabenzyl through aftertreatment and replaces tertiary butyl cup [4] arene derivatives, said to tertiary butyl cup [4] aromatic hydrocarbons, benzyl halogen compounds, hydrated barta, barytic amount of substance ratio be 1: 4～15: 2～10: 2～10;
In the formula (III), X is Cl, Br or I;
In formula (I) or the formula (III), the H on the phenyl ring is substituted basic R replacement or is not substituted, and substituent R is I, methyl or ethyl.
2. the method for claim 1, it is characterized in that the benzyl halogen compounds shown in the said formula (III) be benzyl chlorine, benzyl bromine, benzyl iodine, to iodine benzyl chlorine, an iodine benzyl bromine, adjacent iodine benzyl bromine, to iodine benzyl bromine, an iodine benzyl iodine, to iodine benzyl iodine, to methyl benzyl chlorine, adjacent methyl benzyl chlorine, a methyl benzyl chlorine, to methyl benzyl bromine, adjacent methyl benzyl bromine, a methyl benzyl bromine, to methyl benzyl iodine, adjacent methyl benzyl iodine, a methyl benzyl iodine, to the benzyl ethyl bromine or to benzyl ethyl chlorine.
3. the method for claim 1, it is characterized in that the benzyl halogen compounds shown in the said formula (III) be benzyl chlorine, benzyl bromine, to iodine benzyl bromine, to iodine benzyl iodine or to methyl benzyl bromine.
4. the method for claim 1; It is characterized in that described organic solvent is one of following: THF, 2-methyltetrahydrofuran, chloroform, methylene dichloride, 1; 2-methylene dichloride, N, dinethylformamide, DMAC N,N, acetone, acetonitrile, benzene or toluene.
5. method as claimed in claim 4 is characterized in that described organic solvent is one of following: THF, N, dinethylformamide, acetonitrile or toluene.
6. the method for claim 1 is characterized in that said volume of organic solvent consumption is to count 30～80mL/g to the quality of tertiary butyl cup [4] aromatic hydrocarbons.
7. the method for claim 1 is characterized in that described temperature of reaction is 20～50 ℃, and the reaction times is 1～8h.
8. the method for claim 1; It is characterized in that described reaction solution post-treating method is: pour in the frozen water behind the reaction solution concentrating under reduced pressure; Separate out solid after the stirring; Suction filtration, filter cake, obtain the lower edge tetrabenzyl and replace tertiary butyl cup [4] arene derivatives with volume ratio 1: 1～3 blended mixed solvent recrystallizations with methylene dichloride and methyl alcohol.
9. the method for claim 1, it is characterized in that said to tertiary butyl cup [4] aromatic hydrocarbons, benzyl halogen compounds, hydrated barta, barytic amount of substance ratio be 1: 4～6: 2～6: 2～6.
10. the method for claim 1; It is characterized in that said method carries out according to following steps: according to being 1: 4～6: 2～6: 2～6 to feed intake to tertiary butyl cup [4] aromatic hydrocarbons, benzyl halogen compounds, hydrated barta, barytic amount of substance; Add in the organic solvent N
2Protection down; In 20～50 ℃ the reaction 1～8 hour after; Pour in the frozen water behind the reaction solution concentrating under reduced pressure, separate out solid, suction filtration after the stirring; Filter cake, obtains replacing tertiary butyl cup [4] arene derivatives suc as formula the lower edge tetrabenzyl shown in (I) with volume ratio 1: 1～3 blended mixed solvent recrystallizations with methylene dichloride and methyl alcohol; Said benzyl halogen compounds is benzyl chlorine, benzyl bromine, to iodine benzyl bromine, to iodine benzyl iodine or to methyl benzyl bromine; Described organic solvent is one of following: THF, N, dinethylformamide, acetonitrile or toluene.
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| CN1821203A (en) * | 2006-03-24 | 2006-08-23 | 中国科学院上海有机化学研究所 | Synthetic method for preparing 2-acyl 4-allcyl phenol |
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| CN1821203A (en) * | 2006-03-24 | 2006-08-23 | 中国科学院上海有机化学研究所 | Synthetic method for preparing 2-acyl 4-allcyl phenol |
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| CN112774736A (en) * | 2020-12-19 | 2021-05-11 | 贵州大学 | Q8/SC 6A supermolecule self-assembly body and its application |
| CN112774736B (en) * | 2020-12-19 | 2022-11-01 | 贵州大学 | Q8/SC 6A supermolecule self-assembly and its application |
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