CN101318887A - Method for preparing indene compounds - Google Patents
Method for preparing indene compounds Download PDFInfo
- Publication number
- CN101318887A CN101318887A CNA2008100403581A CN200810040358A CN101318887A CN 101318887 A CN101318887 A CN 101318887A CN A2008100403581 A CNA2008100403581 A CN A2008100403581A CN 200810040358 A CN200810040358 A CN 200810040358A CN 101318887 A CN101318887 A CN 101318887A
- Authority
- CN
- China
- Prior art keywords
- formula
- acid
- compounds
- phenyl
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a method for preparing an indene compound, comprising the following steps that: a raw material of a substituted benzoic ether compound is converted into an indenone compound under the condition of cyclodehydration in the presence of a Lewis acid compounded organic acid or inorganic acid. The indenone compound is reduced to a hydroxyindane compound by a reducer; the hydroxyindane compound is converted to the indene compound through dehydration. The method of the invention uses the substituted benzoic ether compound which is common and easy to prepare to synthesize the indene compound, thereby simplifying the synthesis route and saving cost and allowing for mass production.
Description
Technical field
The present invention relates to the preparation method of organic compound, particularly a kind of preparation method of indene compounds.
Background technology
Indene compounds is the important intermediate of fine chemicals such as composite reactive drug component, liquid crystal, also is simultaneously the particularly important source material of the active ingredient of poly-alpha olefins usefulness metallocene catalyst of synthesis of polyolefins.
Indene compounds can be used for synthetic chirality ansa metallocene catalyst component with very important three-dimensional arrangement performance, and this catalyst component is formed with the transistion metal compound coordination with catalysis in olefine polymerization performance by indene compound or their derivative compound.
The variation of ligancy (as substituent variation on the part) can cause the change of metallocene catalyst performance, thereby causes the change of fluoropolymer resin performance, as improving the productive rate of polymkeric substance, three-dimensional regularity, molecular weight distribution, fusing point and rheological characteristics etc. reach the needed index of people.Particularly the metallocene compound of some bridging especially has alkyl on the position 2, and the metallocene compound that further has alkyl such as aromatic base on the position 4 can be formed the catalyst system of efficient and highly-solid selectively.Synthesizing of these effective catalysts, depend on the use of indene compounds.
In a sense, metallocene catalyst extensively promotes the use of the synthetic of the metallocene compound that depends on low synthetic cost.And the reduction of the synthetic cost of the indene compounds of the synthetic metallocene compound of conduct also becomes inevitable requirement.
In existing bibliographical information, the synthetic method of some indene compounds is disclosed, synthetic method comprising 2-alkyl-4-aryl indene compound, as EP 0576970A1, US4192888A1, US5770753, US5723640, US5789634 and Organometallics 2006,25,1217-1229.In these disclosed methods, the synthetic main carbonyl reduction of the indene compounds that replaces by corresponding indone compound, dehydration realizes then, wherein 4 aryl of 2-alkyl-4-aryl indene compound adopt the aryl-aryl coupling technology to realize that 2 alkyl is then by introducing by the presoma indanone compounds before constructing indene compounds.
As previously mentioned, in the literature method of synthetic preparation indene compounds, because the overwhelming majority all is the carbonyl reduction by indanone compounds, dehydration realizes then.Therefore prepare the key that the indone compound has become synthetic preparation indene compounds.
The main synthetic method of the indanone compounds of document (Organometallics 2006,25,1217-1229 and relevant document and support information, US2007/0135595A1 and US7038070B2) report has at present:
1, with the substituted aroma hydrocarbon is the synthetic method of starting raw material
This method is a starting raw material with the substituted aroma hydrocarbon, obtains by reactions steps such as chloride, cyclisation, hydrolysis, is shown below:
2, be the synthetic method of raw material to replace benzyl chloride
This method is that raw material synthesizes to replace benzyl chloride mainly, generates the phenylpropionic acid compound that replaces with the malonic ester reaction that replaces, and the synthetic indanone compounds of further then cyclisation is shown below:
3, with the phenyl aldehyde be the synthetic method of raw material
With the phenyl aldehyde that replaces is that raw material synthesizes indanone compounds through multistep, is shown below:
In the method that above-mentioned document provides, reaction scheme is via multistep, and is very long, too time-consuming, so the cost costliness.The synthetic method of developing indene compounds simple, with low cost becomes one of important goal of art technology worker.
Summary of the invention
Purpose of the present invention exactly in order to solve the problems referred to above that prior art exists, provides a kind of preparation method of indene compounds with low cost.
Technical scheme of the present invention is: a kind of preparation method of indene compounds may further comprise the steps:
A, be raw material, under the cyclodehydration condition that the acid of Lewis acid composite inorganic or organic acid participate in, be converted into the indanone compounds shown in the formula (IV) with the benzoate compounds of the replacement shown in the formula (III);
B, the indanone compounds shown in the formula (IV) is converted into the indanol compound shown in the formula V by reductive agent reduction;
C, the indanol compound shown in formula V dehydration is converted into the mixture of the arbitrary proportion of the indene compounds shown in indene compounds shown in the formula (I) or the formula (II) or above-mentioned two kinds of indene compounds;
Shown in above-mentioned formula (I), formula (II), formula (III), formula (IV) and the formula V in the compound, R
1, R
2, R
3, R
4, R
5And R
6Represent H, Cl, Br, I, F or C respectively independently
1-C
20Organic group.
Shown in described formula (I), formula (II), formula (III), formula (IV) and the formula V in the compound, R
1And R
4Represent H, Cl, Br, I, F, hydroxyl, alkoxyl group, replacement or unsubstituted C respectively independently
6-C
18Aryl, described C
6-C
18Aryl comprises phenyl, 1-naphthyl, phenanthryl, 3-tert-butyl-phenyl, 4-tert-butyl-phenyl, 3,5-di-tert-butyl-phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 3,5-3,5-dimethylphenyl, 4,4 '-xenyl and 3,5-phenylbenzene phenyl.
Shown in described formula (I), formula (II), formula (III), formula (IV) and the formula V in the compound, R
5And R
6Represent H, C respectively independently
1-C
18The straight or branched alkyl, preferred H, C
1-C
10The straight or branched alkyl.
Shown in described formula (I), formula (II), formula (III), formula (IV) and the formula V in the compound, R
2And R
3Represent H, Cl, Br, I, F, hydroxyl, alkoxyl group, C respectively independently
1-C
18The straight or branched alkyl, preferred H, Cl, Br, I, F, hydroxyl, alkoxyl group, C
1-C
10The straight or branched alkyl.
Shown in described formula (I), formula (II), formula (III), formula (IV) and the formula V in the compound, R
1And R
2Perhaps R
2And R
3Perhaps R
3And R
4Between can be connected to C
3-C
12Cycloaliphatic ring or aromatic nucleus.
The temperature of reaction of the described conversion reaction of steps A is controlled between-30 ℃ to 200 ℃, and between preferred 50 ℃-130 ℃, described Lewis acid is selected from aluminum chloride, iron trichloride, zinc chloride or tin tetrachloride; Described mineral acid or organic acid are selected from phosphoric acid, two polyphosphoric acids, tripolyphosphate, polyphosphoric acid, the vitriol oil, trifluoromethanesulfonic acid or trifluoroacetic acid.
Preferred two polyphosphoric acids of described mineral acid or organic acid, tripolyphosphate, polyphosphoric acid, the vitriol oil or trifluoromethanesulfonic acid.
The preferred ethyl benzoate of the benzoate compounds of the replacement described in the steps A, isopropyl benzoate, 2-chloro-benzoic acid isopropyl ester, 2,3-dihydro-1H-indenes-5-carboxylic acid isopropyl, 3-methoxybenzoic acid ethyl ester, 4-isopropyl acid ethyl ester, 2-Phenylbenzoic acid isopropyl ester, 2-(4 '-tert-butyl-phenyl) isopropyl benzoate, phenylformic acid-2-polyhexamethylene or 2-(4 '-aminomethyl phenyl) isopropyl benzoate.
Among the present invention; the typical operating process of steps A is as follows: under exsiccant atmosphere such as nitrogen protection; the organic acid or the mineral acid that in churned mechanically reactor is housed, add 1-15 times of formula (III) compound mole number; be heated to 50 ℃ after 130 ℃ under stirring; the homogeneous solution that the aluminum trichloride (anhydrous) of adding formula (III) compound and 0.1-1.5 times of formula (III) compound mole number is made in reactor; after stirring reaction 0.2-5 hour; reaction mixture is cooled between 20 ℃-100 ℃; in reaction system, slowly add and be equivalent to organic acid or mineral acid quality 0.5-1.5 frozen water doubly; fully stir and when being cooled to 50 ℃-60 ℃; adding is equivalent to organic acid or mineral acid quality 0.1-1.0 nonpolar or weak polar solvent such as normal heptane doubly extracts mixture; leave standstill collected organic layer after the abundant layering; extremely alkaline with the saturated sodium bicarbonate solution washing; use desolventizing behind the anhydrous sodium sulfate drying organic layer then, obtain target product.
The described reductive agent of step B is selected from sodium borohydride, POTASSIUM BOROHYDRIDE, lithium aluminum hydride, diisobutyl aluminium hydride or two (dimethoxy oxyethyl group) sodium aluminum hydride.
The concrete reaction conversion process of step B also can be with reference to the organic chemistry document of classics, as " newly organized Synthetic Organic Chemistry " (2002, Chemical Industry Press).After selected appropriate reductant, can in polar solvent such as tetrahydrofuran (THF) or methyl alcohol or their mixture, reduce the indone compound, extract resultants with solvent such as ethyl acetate etc. then, can obtain the indanol compounds behind the precipitation.This process is familiar with (US 2007/0135595A1) by those skilled in the art.
Step C be reflected at and water generates in the azeotropic solvent (as benzene,toluene,xylene etc.) and carries out, with reflux dehydration under the catalysis of indanol compounds direct heating reflux dewatering or one or more mixtures in tosic acid, toluenesulphonic acids, sulfuric acid, trifluoromethanesulfonic acid or trifluoroacetic acid.This process also is familiar with (US 2007/0135595A1) by those skilled in the art.
The present invention has also found the preparation method of indanone compounds included among a kind of preparation method of indene compounds, this method is a raw material with the benzoate compounds of the replacement shown in the formula (III), under the cyclodehydration condition of acid of Lewis acid composite inorganic or organic acid participation, be converted into the indanone compounds shown in the formula (IV);
Shown in above-mentioned formula (III), the formula (IV) in the compound, R
1, R
2, R
3, R
4, R
5And R
6Represent H, Cl, Br, I, F or C respectively independently
1-C
20Organic group, wherein, R
1And R
4Represent H, Cl, Br, I, F, hydroxyl, alkoxyl group, replacement or unsubstituted C respectively independently
6-C
18Aryl, described C
6-C
18Aryl comprises phenyl, 1-naphthyl, phenanthryl, 3-tert-butyl-phenyl, 4-tert-butyl-phenyl, 3,5-di-tert-butyl-phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 3,5-3,5-dimethylphenyl, 4,4 '-xenyl and 3,5-phenylbenzene phenyl; R
5And R
6Represent H, C respectively independently
1-C
18The straight or branched alkyl, preferred H, C
1-C
10The straight or branched alkyl; R
2And R
3Represent H, Cl, Br, I, F, hydroxyl, alkoxyl group, C respectively independently
1-C
18The straight or branched alkyl, preferred H, Cl, Br, I, F, hydroxyl, alkoxyl group, C
1-C
10The straight or branched alkyl; R
1And R
2Perhaps R
2And R
3Perhaps R
3And R
4Between can be connected to C
3-C
12Cycloaliphatic ring or aromatic nucleus.
The benzoate compounds of the replacement shown in the formula (III) such as ethyl benzoate, isopropyl benzoate, 2-chloro-benzoic acid isopropyl ester and 2,3-dihydro-1H-indenes-5-carboxylic acid isopropyl can buy on market, perhaps can synthesize through esterification and obtain (" newly organized Synthetic Organic Chemistry " (2002, Chemical Industry Press)) by the phenylformic acid that method well-known to those skilled in the art such as acid catalysis replace.The phenylformic acid that replaces also can buy on market, perhaps synthesizes (" newly organized Synthetic Organic Chemistry " (2002, Chemical Industry Press)) by method well-known to those skilled in the art.
Compared with prior art, the characteristics of the inventive method maximum are exactly by adopting the conventional easily raw material of preparation---the benzoate compounds of replacement come the indene compounds shown in synthesis type (I) or the formula (II) or the two arbitrarily than mixture, simplified synthetic route, provide cost savings, be more suitable for mass production.
Embodiment
Below in conjunction with specific embodiment the present invention is described.Unless stated otherwise, the reagent that is adopted in the embodiment of the invention is directly buying on the market, does not pass through special processing.
Embodiment 1
2,3-bihydrogen-1-indenone synthetic:
Under nitrogen protection; in being housed, churned mechanically one liter round-bottomed flask adds two polyphosphoric acids, 85 grams; after being heated to 70 ℃; in reactor, add the homogeneous solution that is made into by ethyl benzoate 15 grams (0.1mol) and 2.7 gram (0.02mol) aluminum trichloride (anhydrous)s; stirring reaction is after half an hour; reaction mixture is cooled to below 20 ℃; in reaction system, slowly add frozen water 100 grams; fully stir and when being cooled to 50 ℃-60 ℃; add 100 milliliters of normal heptane extraction mixtures; leave standstill collected organic layer after the abundant layering, to alkalescence, use desolventizing behind the anhydrous sodium sulfate drying organic layer then with the saturated sodium bicarbonate solution washing; obtain organic product 10.1 grams; through gas Chromatographic Determination, wherein 2,3-bihydrogen-1-indenone content reaches 75%.Collect product after the rectification under vacuum, get 5.1 grams 2,3-bihydrogen-1-indenone, chromatographic purity＞98%.(
1H?NMR(300MHz，CDCl
3)：δ＝2.5-2.6(t，2H)，δ＝3.01-3.09(t，2H)，δ＝7.16-7.25(t，2H)，δ＝7.61-7.69(t，1H)，δ＝7.87-7.95(d，1H)。Repeat said process, prepare 2 of q.s, 3-bihydrogen-1-indenone product is standby.
Synthesizing of indenes:
Under nitrogen protection; 500 milliliters of mixed solvents that in 1 liter round-bottomed flask, add 1: 1 anhydrous tetrahydro furan and anhydrous methanol; add 2 then; 3-bihydrogen-1-indenone 66 grams (0.5mol); reaction mixture under agitation is cooled to below 5 ℃; slowly add sodium borohydride 1.5mol in batches; after finishing; reaction mixture slowly is warmed up to room temperature; and stir and spend the night; under agitation add 2M hydrochloric acid then to acid; reaction mixture 200ml * 2 ethyl acetate extractions; merge organic phase; desolventizing on another the 1 liter round-bottomed flask that backflow azeotropic dehydration device is housed; add toluene 200mL then; tosic acid 0.5 gram, heat temperature raising is to refluxing azeotropic dehydration; after not having moisture to steam; reaction mixture is cooled to below 50 ℃, and stirring down, a small amount of triethylamine of adding washs with saturated sodium bicarbonate solution then to remove the catalyzer tosic acid; organic layer is through being washed to neutrality; extremely anhydrous with anhydrous sodium sulfate drying then, distillation removes solvent toluene then, and the gained crude product obtains straight product 52 grams after rectifying; be a kind of indene compounds product of the present invention, gas-chromatography content 98.2%.(
1H?NMR(300MHz，CDCl
3)：δ＝3.21(d，2H)，δ＝6.33-6.43(m，1H)，δ＝6.58(d，1H)，δ＝6.58(d，1H)，δ＝6.95-7.05(m，2H)，δ＝7.20-7.30(m，2H)。
Embodiment 2
Change two polyphosphoric acids among the embodiment 1 into polyphosphoric acid, mass conservation, other condition is also constant, can obtain 2 after reaction, 3-bihydrogen-1-indenone 7.5 grams.Can be used for the synthetic of next step indene compounds.
Embodiment 3
Change the gram of 85 among the embodiment 1 two polyphosphoric acids into 45 gram trifluoromethanesulfonic acids, temperature of reaction is brought up to 90 ℃, and other condition is constant, obtains 2 after reaction, 3-bihydrogen-1-indenone 5.8 grams.Can be used for the synthetic of next step indene compounds.
Embodiment 4
Change two polyphosphoric acids among the embodiment 1 into polyphosphoric acid, mass conservation, aluminum chloride make the Zinc Chloride Anhydrous of equimolar amount into, and temperature of reaction is brought up to 90 ℃ simultaneously, and other condition is constant, obtain 2 after reaction, 3-bihydrogen-1-indenone 4.8 grams.Can be used for the synthetic of next step indene compounds.
Embodiment 5
With the ethyl benzoate among the isopropyl benzoate replacement embodiment 1 of equimolar amount, other process is identical, obtains 9.8 gram 2-methyl-2,3-bihydrogen-1-indenone and 3-methyl-2, the mixture of 3-bihydrogen-1-indenone (mol ratio 7: 3).This mixture obtains 6.9 gram 2-methyl-2 respectively after separating, the 3-bihydrogen-1-indenone (
1H NMR (300MHz, CDCl
3): δ=1.29 (d, 3H), δ=2.55-2.75 (d, 2H), δ=3.35-3.45 (m, 1H), and δ=7.30-7.40 (t, 1H), δ=7.41-7.47 (t, 1H), δ=7.50-7.60 (t, 1H), δ=7.75-7.82 (t, 1H)) and 2.6 gram 3-methyl-2, the 3-bihydrogen-1-indenone (
1H NMR (300MHz, CDCl
3): δ=1.33 (d, 3H), δ=2.65-2.75 (m, 1H), δ=2.88-2.99 (m, 1H), δ=3.40-3.55 (m, 1H), δ=7.14-7.26 (m, 2H), δ=7.32-7.39 (t, 1H), δ=7.82-7.91 (d, 1H)).
Use 2-methyl-2 respectively, 3-bihydrogen-1-indenone and 3-methyl-2,3-bihydrogen-1-indenone are raw material, according to the synthetic method of indenes among the embodiment 1, respectively with 95% and 92% productive rate obtain 2-methyl indenes (
1H NMR (300MHz, CDCl
3): δ=2.15 (s, 3H), δ=3.25 (s, 2H), δ=6.45 (s, 1H), δ=7.00-7.10 (t, 1H), δ=7.15-7.27 (t, 2H), δ=7.32 (d, 1H)) and 3-methyl indenes/1-methyl indenes mixture.
Embodiment 6
With the ethyl benzoate among the 2-chloro-benzoic acid isopropyl ester replacement embodiment 1 of equimolar amount, other process is identical, obtains 10.7 gram 4-chloro-2-methyl-2,3-bihydrogen-1-indenone and 4-chloro-3-methyl-2, the mixture of 3-bihydrogen-1-indenone (mol ratio 8: 2).This mixture obtains 8.3 gram 4-chloro-2-methyl-2 respectively after separating, the 3-bihydrogen-1-indenone (
1H NMR (300MHz, CDCl
3): δ=1.30 (d, 3H), δ=2.60-2.80 (m, 2H), δ=3.30-3.41 (m, 1H), δ=7.3 (m, 1H), δ=7.52 (d, 1H), δ=7.65 (d, 1H)) and 1.7 gram 4-chloro-3-methyl-2, the 3-bihydrogen-1-indenone (
1H NMR (300MHz, CDCl
3): δ=1.31 (d, 3H), δ=2.65-2.85 (m, 2H), δ=3.45-3.55 (m, 1H), δ=7.2-7.6 (m, 3H), δ=7.65-7.75 (d, 1H)).
With 4-chloro-2-methyl-2, the 3-bihydrogen-1-indenone is the synthetic method of raw material according to indenes among the embodiment 1, the productive rate with 94% obtain 4-chloro-2-methyl indenes and 7-chloro-2-methyl indenes mixture (
1H NMR (300MHz, CDCl
3): δ=2.22 (s, 3H, CH
3), δ=3.30-3.40 (m, 2H, CH
2), δ=6.53-6.72 (m, 1H), δ=7.13-7.32 (m, 3H)).
With 4-chloro-3-methyl-2, the 3-bihydrogen-1-indenone is a raw material, according to the synthetic method of indenes among the embodiment 1, the productive rate with 93% obtain 4-chloro-3-methyl indenes and 4-chloro-1-methyl indenes mixture (
1HNMR (300MHz, CDCl
3): δ=1.65 (d ,～2.1H, CH
3), δ=2.24 (s ,～0.9H, CH
3), δ=3.32 (s ,～0.6H, CH
2), δ=3.75 (s ,～0.7H, CH), δ=6.3-6.50 (m, 1H), δ=7.30-7.65 (m, 3H)).
Embodiment 7
With 2 of equimolar amount, 3-dihydro-1H-indenes-5-carboxylic acid isopropyl replaces the ethyl benzoate among the embodiment 1, and other process is identical, obtains 11.2 gram 2-methyl-2,3,6,7-tetrahydrochysene-s-indacene-1 (5H)-ketone (
1H NMR (300MHz, CDCl
3): δ=1.26 (d, 3H, CH
3), δ=2.11 (m, 2H), δ=2.64 (m, 2H), δ=2.87 (m, 4H), δ=3.24 (m, 1H), δ=7.20 (s, 1H), δ=7.52 (s, 1H)).Synthetic method according to indenes among the embodiment 1 obtains the 6-methyl isophthalic acid with 96% productive rate, and 2,3,5-tetrahydrochysene-s-indacene compound (
1H NMR (300MHz, CDCl
3): δ=2.24 (m, 5H, CH
2And CH
3), δ=3.00 (t, 4H, 2 * CH
2), δ=3.31 (s, 2H, CH
2), δ=6.52 (s, 1H), δ=7.21 (s, 1H), δ=7.33 (s, 1H)).
Embodiment 8
With the ethyl benzoate among the 3-methoxybenzoic acid ethyl substituted embodiment 1 of equimolar amount, two polyphosphoric acids are added in the mixture of 3-methoxybenzoic acid ethyl ester and aluminum chloride, other reaction conditions and process are constant, after reaction, obtain 6-methoxyl group-2,3-bihydrogen-1-indenone and 4-methoxyl group-2, mixture 11.9 grams of 3-bihydrogen-1-indenone.This mixture obtains 7.14 gram 6-methoxyl groups-2 after separating, 3-bihydrogen-1-indenone and 4.76 gram 4-methoxyl groups-2,3-bihydrogen-1-indenone.Be directly used in the synthetic of next step indene compounds.
With synthetic 6-methoxyl group-2,3-bihydrogen-1-indenone and 4-methoxyl group-2,3-bihydrogen-1-indenone are the synthetic method of raw material according to indenes among the embodiment 1, adopt lithium aluminum hydride as reductive agent, respectively with 95% and 93% productive rate obtain 5-methoxyl group indenes (
1H NMR (300MHz, CDCl
3): δ=3.25 (d, 2H), δ=3.75 (s, 3H), δ=6.40-7.02 (m, 5H)) and 7-methoxyl group indenes (
1H NMR (300MHz, CDCl
3): δ=3.26 (d, 2H), δ=3.73 (s, 3H), δ=6.40-6.62 (m, 4H), δ=7.00-7.10 (d, 1H)).
Embodiment 9
With the ethyl benzoate among the 4-isopropyl acid ethyl substituted embodiment 1 of equimolar amount, the polyphosphoric acid of quality such as use to replace two polyphosphoric acids among the embodiment 1, other condition is constant, obtains 12.6 gram 5-sec.-propyls-2 after reaction, the 3-bihydrogen-1-indenone.Directly with synthetic 5-sec.-propyl-2, the 3-bihydrogen-1-indenone is a raw material, and according to the synthetic method of indenes among the embodiment 1, the employing POTASSIUM BOROHYDRIDE is a reductive agent, the productive rate with 94% obtain 5-sec.-propyl indenes (
1H NMR (300MHz, CDCl
3): δ=1.24 (d, 6H), δ=2.86 (m, 1H), δ=3.22-3.33 (m, 2H), δ=6.41-6.62 (m, 2H), δ=6.89-7.10 (m, 3H)).
Embodiment 10
Replace ethyl benzoate among the embodiment 1 with the 2-Phenylbenzoic acid isopropyl ester of equimolar amount, the polyphosphoric acid of quality such as use to replace two polyphosphoric acids among the embodiment 1, other condition is constant, obtains 11.8 gram 4-phenyl-2-methyl-2,3-bihydrogen-1-indenone after reaction.Directly with synthetic 4-phenyl-2-methyl-2, the 3-bihydrogen-1-indenone is a raw material, and according to the synthetic method of indenes among the embodiment 1, the productive rate with 95% obtains 2-methyl-7-phenyl-1H-indenes.(
1HNMR(300MHz，CDCl
3)：7.46-7.50(m，2H)，7.35-7.41(m，2H)，7.30(m，1H)，7.27(d，1H)，7.21(dd，1H)，7.10(dd，1H)，6.51(hex，1H)，3.32(m，2H)，2.07(m，3H))。
Embodiment 11
With the ethyl benzoate among 2-(4 '-tert-butyl-phenyl) the isopropyl benzoate replacement embodiment 1 of equimolar amount, with etc. the polyphosphoric acid of quality replace two polyphosphoric acids among the embodiment 1, other condition is constant, after reaction, obtain 13.9 gram 4-(4 '-tert-butyl-phenyl)-2-methyl-2, the 3-bihydrogen-1-indenone.Directly with synthetic 4-(4 '-tert-butyl-phenyl)-2-methyl-2, the 3-bihydrogen-1-indenone is a raw material, according to the synthetic method of indenes among the embodiment 1, the productive rate with 92% obtain 2-methyl-7-(4 '-tert-butyl-phenyl)-1H-indenes (
1H MR (300MHz, CDCl
3): 7.40-7.48 (m, 4H), 7.28 (d, 1H), 7.22 (dd, 1H), 7.14 (dd, 1H), 6.51 (hex, 1H), 3.38 (m, 2H), 2.11 (m, 3H), 1.38 (s, 9H)).
Embodiment 12
With the ethyl benzoate among 2-(4 '-aminomethyl phenyl) the isopropyl benzoate replacement embodiment 1 of equimolar amount, with etc. the polyphosphoric acid of quality replace two polyphosphoric acids among the embodiment 1, other condition is constant, after reaction, obtain 10.8 gram 4-(4 '-aminomethyl phenyl)-2-methyl-2, the 3-bihydrogen-1-indenone.Directly with synthetic 4-(4 '-aminomethyl phenyl)-2-methyl-2, the 3-bihydrogen-1-indenone is a raw material, according to the synthetic method of indenes among the embodiment 1, the productive rate with 91% obtain 2-methyl-7-(4 '-aminomethyl phenyl)-1H-indenes (
1H NMR (300MHz, CDCl
3): 7.18-7.29 (m, 6H), 6.93 (dd, 1H), 6.52 (hex, 1H), 3.04 (s, 2H), 2.11 (s, 3H), 2.08 (m, 3H).
Embodiment 13
Replace ethyl benzoate among the embodiment 1 with the phenylformic acid of equimolar amount-2-polyhexamethylene, the polyphosphoric acid of quality such as use to replace two polyphosphoric acids among the embodiment 1, other condition is constant, obtains 5.3 gram 2-butyl-2,3-bihydrogen-1-indenone after reaction.Directly with synthetic 2-butyl-2, the 3-bihydrogen-1-indenone is a raw material, according to the synthetic method of indenes among the embodiment 1, the productive rate with 89% obtain 2-butyl-1H-indenes (
1H NMR (300MHz, CDCl
3): δ=0.97 (t, 3H), δ=1.32 (m, 4H), δ=2.05 (s, 2H), δ=3.22 (s, 2H), δ=6.46 (s, 1H), δ=7.01-7.10 (t, 1H), δ=7.14-7.25 (t, 2H), δ=7.32 (d, 1H)).
Claims (10)
1. the preparation method of an indene compounds is characterized in that, may further comprise the steps:
A, be raw material, under the cyclodehydration condition that the acid of Lewis acid composite inorganic or organic acid participate in, be converted into the indanone compounds shown in the formula (IV) with the benzoate compounds of the replacement shown in the formula (III);
B, the indanone compounds shown in the formula (IV) is converted into the indanol compound shown in the formula V by reductive agent reduction;
C, the indanol compound shown in formula V dehydration is converted into the mixture of the arbitrary proportion of the indene compounds shown in indene compounds shown in the formula (I) or the formula (II) or above-mentioned two kinds of indene compounds;
Shown in above-mentioned formula (I), formula (II), formula (III), formula (IV) and the formula V in the compound, R
1, R
2, R
3, R
4, R
5And R
6Represent H, Cl, Br, I, F or C respectively independently
1-C
20Organic group.
2. the preparation method of indene compounds as claimed in claim 1 is characterized in that: shown in described formula (I), formula (II), formula (III), formula (IV) and the formula V in the compound, and R
1And R
4Represent H, Cl, Br, I, F, hydroxyl, alkoxyl group, replacement or unsubstituted C respectively independently
6-C
18Aryl, described C
6-C
18Aryl comprises phenyl, 1-naphthyl, phenanthryl, 3-tert-butyl-phenyl, 4-tert-butyl-phenyl, 3,5-di-tert-butyl-phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 3,5-3,5-dimethylphenyl, 4,4 '-xenyl and 3,5-phenylbenzene phenyl.
3. the preparation method of indene compounds as claimed in claim 1 is characterized in that: shown in described formula (I), formula (II), formula (III), formula (IV) and the formula V in the compound, and R
5And R
6Represent H, C respectively independently
1-C
18The straight or branched alkyl, preferred H, C
1-C
10The straight or branched alkyl.
4. the preparation method of indene compounds as claimed in claim 1 is characterized in that: shown in described formula (I), formula (II), formula (III), formula (IV) and the formula V in the compound, and R
2And R
3Represent H, Cl, Br, I, F, hydroxyl, alkoxyl group, C respectively independently
1-C
18The straight or branched alkyl, preferred H, Cl, Br, I, F, hydroxyl, alkoxyl group, C
1-C
10The straight or branched alkyl.
5. the preparation method of indene compounds as claimed in claim 1 is characterized in that: shown in described formula (I), formula (II), formula (III), formula (IV) and the formula V in the compound, and R
1And R
2Perhaps R
2And R
3Perhaps R
3And R
4Between can be connected to C
3-C
12Cycloaliphatic ring or aromatic nucleus.
6. the preparation method of indene compounds as claimed in claim 1, it is characterized in that: the temperature of reaction of the described conversion reaction of steps A is controlled between-30 ℃ to 200 ℃, between preferred 50 ℃-130 ℃, described Lewis acid is selected from aluminum chloride, iron trichloride, zinc chloride or tin tetrachloride; Described mineral acid or organic acid are selected from phosphoric acid, two polyphosphoric acids, tripolyphosphate, polyphosphoric acid, the vitriol oil, trifluoromethanesulfonic acid or trifluoroacetic acid.
7. the preparation method of indene compounds as claimed in claim 6 is characterized in that: preferred two polyphosphoric acids of described mineral acid or organic acid, tripolyphosphate, polyphosphoric acid, the vitriol oil or trifluoromethanesulfonic acid.
8. the preparation method of indene compounds as claimed in claim 1, it is characterized in that: the preferred ethyl benzoate of the benzoate compounds of the replacement described in the steps A, isopropyl benzoate, 2-chloro-benzoic acid isopropyl ester, 2,3-dihydro-1H-indenes-5-carboxylic acid isopropyl, 3-methoxybenzoic acid ethyl ester, 4-isopropyl acid ethyl ester, 2-Phenylbenzoic acid isopropyl ester, 2-(4 '-tert-butyl-phenyl) isopropyl benzoate, phenylformic acid-2-polyhexamethylene or 2-(4 '-aminomethyl phenyl) isopropyl benzoate.
9. the preparation method of indene compounds as claimed in claim 1, it is characterized in that: the described reductive agent of step B is selected from sodium borohydride, POTASSIUM BOROHYDRIDE, lithium aluminum hydride, diisobutyl aluminium hydride or two (dimethoxy oxyethyl group) sodium aluminum hydride; Be reflected at and the water of step C form in the azeotropic solvent and carry out, with reflux dewatering under the catalysis of indanol compounds direct heating reflux dewatering or one or more mixtures in tosic acid, toluenesulphonic acids, sulfuric acid, trifluoromethanesulfonic acid or trifluoroacetic acid.
10. the preparation method of the included indanone compounds of the preparation method of a kind of indene compounds as claimed in claim 1 is characterized in that:
Benzoate compounds with the replacement shown in the formula (III) is a raw material, under the cyclodehydration condition of acid of Lewis acid composite inorganic or organic acid participation, is converted into the indanone compounds shown in the formula (IV);
Shown in above-mentioned formula (III), the formula (IV) in the compound, R
1, R
2, R
3, R
4, R
5And R
6Represent H, Cl, Br, I, F or C respectively independently
1-C
20Organic group, wherein, R
1And R
4Represent H, Cl, Br, I, F, hydroxyl, alkoxyl group, replacement or unsubstituted C respectively independently
6-C
18Aryl, described C
6-C
18Aryl comprises phenyl, 1-naphthyl, phenanthryl, 3-tert-butyl-phenyl, 4-tert-butyl-phenyl, 3,5-di-tert-butyl-phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 3,5-3,5-dimethylphenyl, 4,4 '-xenyl and 3,5-phenylbenzene phenyl; R
5And R
6Represent H, C respectively independently
1-C
18The straight or branched alkyl, preferred H, C
1-C
10The straight or branched alkyl; R
2And R
3Represent H, Cl, Br, I, F, hydroxyl, alkoxyl group, C respectively independently
1-C
18The straight or branched alkyl, preferred H, Cl, Br, I, F, hydroxyl, alkoxyl group, C
1-C
10The straight or branched alkyl; R
1And R
2Perhaps R
2And R
3Perhaps R
3And R
4Between can be connected to C
3-C
12Cycloaliphatic ring or aromatic nucleus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100403581A CN101318887B (en) | 2008-07-08 | 2008-07-08 | Method for preparing indene compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100403581A CN101318887B (en) | 2008-07-08 | 2008-07-08 | Method for preparing indene compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101318887A true CN101318887A (en) | 2008-12-10 |
| CN101318887B CN101318887B (en) | 2011-03-23 |
Family
ID=40179194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100403581A Active CN101318887B (en) | 2008-07-08 | 2008-07-08 | Method for preparing indene compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101318887B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491886A (en) * | 2011-12-01 | 2012-06-13 | 上海化工研究院 | Method for synthetizing indanone compound |
| CN103086834A (en) * | 2013-01-08 | 2013-05-08 | 上海化工研究院 | Preparation method of biaryl indene compounds |
| CN104326892A (en) * | 2014-09-18 | 2015-02-04 | 沈阳药科大学 | Synthetic method of indanone by gold-catalysis |
| CN108329197A (en) * | 2017-12-18 | 2018-07-27 | 滨海康杰化学有限公司 | A kind of preparation method of indanone compounds |
| CN109180449A (en) * | 2018-09-04 | 2019-01-11 | 南通雅本化学有限公司 | The preparation method of one kind 2,6- dimethyl -2,3- bihydrogen-1-indenone |
| CN112939780A (en) * | 2020-09-15 | 2021-06-11 | 浙江大学 | Synthetic method of indanone derivatives |
| CN112939753A (en) * | 2020-09-15 | 2021-06-11 | 浙江大学 | Synthesis method of 1-indanone compound |
| CN113248356A (en) * | 2021-05-13 | 2021-08-13 | 宣城菁科生物科技有限公司 | Industrial production method of 4-hydroxy-1-indanone |
-
2008
- 2008-07-08 CN CN2008100403581A patent/CN101318887B/en active Active
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491886A (en) * | 2011-12-01 | 2012-06-13 | 上海化工研究院 | Method for synthetizing indanone compound |
| CN102491886B (en) * | 2011-12-01 | 2014-10-01 | 上海化工研究院 | Method for synthetizing indanone compound |
| CN103086834A (en) * | 2013-01-08 | 2013-05-08 | 上海化工研究院 | Preparation method of biaryl indene compounds |
| CN104326892A (en) * | 2014-09-18 | 2015-02-04 | 沈阳药科大学 | Synthetic method of indanone by gold-catalysis |
| CN108329197A (en) * | 2017-12-18 | 2018-07-27 | 滨海康杰化学有限公司 | A kind of preparation method of indanone compounds |
| CN109180449A (en) * | 2018-09-04 | 2019-01-11 | 南通雅本化学有限公司 | The preparation method of one kind 2,6- dimethyl -2,3- bihydrogen-1-indenone |
| CN112939780A (en) * | 2020-09-15 | 2021-06-11 | 浙江大学 | Synthetic method of indanone derivatives |
| CN112939753A (en) * | 2020-09-15 | 2021-06-11 | 浙江大学 | Synthesis method of 1-indanone compound |
| CN112939753B (en) * | 2020-09-15 | 2022-04-05 | 浙江大学 | Synthesis method of 1-indanone compound |
| CN113248356A (en) * | 2021-05-13 | 2021-08-13 | 宣城菁科生物科技有限公司 | Industrial production method of 4-hydroxy-1-indanone |
| CN113248356B (en) * | 2021-05-13 | 2023-04-04 | 宣城菁科生物科技有限公司 | Industrial production method of 4-hydroxy-1-indanone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101318887B (en) | 2011-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101318887B (en) | Method for preparing indene compounds | |
| CN101337874B (en) | Method for preparing indanone compounds | |
| CN101570550B (en) | Method for synthesizing chiral ferrocene diphosphine ligand | |
| CN108329197A (en) | A kind of preparation method of indanone compounds | |
| Dong et al. | Heterogeneous asymmetric addition of diethylzinc to aromatic aldehydes catalyzed by Ti (IV)/imine bridged poly (R)-binaphthol | |
| CN112979402A (en) | Industrial production method of benzo [ a ] anthracene | |
| CN114560802B (en) | Method for constructing carbon-nitrogen axis chiral indole-naphthol biaryl compound | |
| CN114805013B (en) | Synthesis method of halogenated biaryl compound | |
| CN106748752A (en) | A kind of preparation method of 2,3 naphthalenedicarboxylic acid | |
| Huo et al. | Highly Efficient Bulky α‐Diimine Palladium Complexes for Suzuki‐Miyaura Cross‐Coupling Reaction | |
| CN102491886A (en) | Method for synthetizing indanone compound | |
| CN105820111A (en) | Preparation method of catalyst and method for preparing 2,2-dipyridyl through catalysis by virtue of catalyst | |
| CN111484436A (en) | Method for introducing isopentenyl group to C3 position of indole | |
| CN111807954B (en) | Preparation method of simmond intermediate | |
| CN108047243A (en) | A kind of five butterfly alkene tetracarboxylic acid dianhydride compounds of 2,3,6,7- and its synthetic method | |
| CN107814757A (en) | A kind of method for synthesizing polysubstituted pyrrole derivative | |
| CN105801553B (en) | A kind of preparation method of Benzochromene derivatives | |
| CN103086834B (en) | Preparation method of biaryl indene compounds | |
| CN110304989A (en) | A kind of synthesis technology of 9,9- dialkyl fluorene derivative | |
| CN111747879A (en) | Large-process synthesis method of erexib | |
| CN104496899B (en) | The synthetic method of the intermediate of Menglusitena | |
| CN109796372B (en) | Method for preparing polysubstituted alkenyl amidine | |
| CN113173842B (en) | Synthesis method of 2-alkyl terephthalquinone compound | |
| CN1332930C (en) | Method for preparing precursor of cycloprothrin | |
| CN116410126A (en) | Ligand, ruthenium complex, preparation method thereof and application of ligand and ruthenium complex in catalyzing alkyne semi-hydrogenation reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 200062 Shanghai city Putuo District Yunling Road No. 345 Patentee after: Shanghai Chemical Research Institute Co., Ltd. Address before: 200062 Shanghai city Putuo District Yunling Road No. 345 Patentee before: Shanghai Research Institute of Chemical Industry |