CN102718806A - Novel method for synthesizing ferroceneboronic acid ester - Google Patents
Novel method for synthesizing ferroceneboronic acid ester Download PDFInfo
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- CN102718806A CN102718806A CN2012101047665A CN201210104766A CN102718806A CN 102718806 A CN102718806 A CN 102718806A CN 2012101047665 A CN2012101047665 A CN 2012101047665A CN 201210104766 A CN201210104766 A CN 201210104766A CN 102718806 A CN102718806 A CN 102718806A
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- ferrocene
- boric acid
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- acid ester
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Abstract
The present invention relates to a synthetic method of ferroceneboronic acid ester. A novel synthetic method of ferroceneboronic acid ester comprises steps of: a) synthesis of ferroceneboronic acid ester: reacting a raw material of ferroceneboronic acid ester in an anhydrous ether solvent with n-butyllithium at 0-40 DEG C to obtain ferrocene lithium salt; b) synthesis of ferroceneboronic acid: adding B(OR)3 (R represents alkyl) into the ferrocene lithium salt solution at -50 DEG C, cooling naturally to room temperature, stirring for 2-5 hours, adding alkaline aqueous solution to quench unreacted n-butyllithium, separating liquid, washing an organic phase with an aqueous alkali solution for one time, adjusting a pH of an aqueous phase to 6-7, separating out a ferroceneboronic acid crude product, and carrying out suction filtration and washing with water for two times; and c) synthesis of ferroceneboronic acid ester: adding the crude product into an aromatic hydrocarbon solvent, then adding the pinacol, heating, returning and diverting water for 6-12 h, evaporating the solvent, and carrying out column chromatography separation to obtain two products. The invention has the advantages of simple operation, uniform solvent used, direct acquisition of boric acid without synthesis of brominated compound, no usage of TMEDA and other amino compounds, no usage of ultralow temperature reaction, and simple synthesis and separation.
Description
Technical field
The invention belongs to organic cpds synthetic field, the particularly chemical synthesis process of ferrocene boric acid ester.
Background technology
Ferrocene because it is not had an effect with acid, alkali, UV-lamp, has thermostability, chemicalstability and the radiation resistance of height as a kind of organo-transition metal compound with aromatic series character.Especially its verivate all has application widely in industries such as industry, agricultural, medicine, space flight, energy-saving and environmental protection.
Ferrocene boric acid is synthetic ferrocene deriv important material through the Suzuki coupling method.Cendrine Patoux study group is through the synthetic intramolecularly transfer transport module that obtains multiple novelty of ferrocene boric acid, and this supramolecule research for research transfer transport and molecular switch has important effect.(reference: Cendrine Patoux; Inorganic Chemistry, 1997,36,22).
Ferrocene boric acid and pinacol ester thereof are as one of synthetic ferrocene deriv important source material, yet its compound method is reported seldom at present.The synthetic earlier ferrocene bromo-derivative that obtains of Harold shechter study group, reaction obtains ferrocene boric acid with n-Butyl Lithium then; With and process Grignard reagent with the ferrocene bromo-derivative, obtain ferrocene boric acid at last.(reference: Harold shechter; J. Org. Chem., 1961,26,1034) this method troublesome poeration, and be difficult to separate and obtain than straight product, synthesis step is long, and cost is higher.A kind of in addition compound method is exactly that Ralf Knapp study group uses n-Butyl Lithium, TMEDA and ferrocene direct reaction to produce the ferrocene lithium salts, and reaction obtains ferrocene boric acid with tributyl borate then.(reference: Ralf Knapp; Journal of Organometallic Chemistry, 1993,452,235-240).This method complicated operation, and separation is difficult to obtain purity than high product.
Summary of the invention
The invention solves the problems referred to above, a kind of novel method of synthetic ferrocene boric acid ester is provided, simple to operate; Use the homogeneous solvent, and need not synthesize bromo-derivative and directly obtain boric acid, need not use aminocompounds such as TMEDA; Do not use the very low temperature reaction, the synthetic separation than being easier to.
The present invention for realizing the technical scheme that above-mentioned purpose adopted is: a kind of novel method of synthetic ferrocene boric acid ester, and concrete steps are following:
A) the ferrocene lithium salts is synthetic: with the ferrocene is raw material, in the anhydrous ether kind solvent, reacts the lithium salts that obtains ferrocene at the 0-40 degree with n-Butyl Lithium;
B) ferrocene boric acid is synthetic: spend B (OR)-78～-50
3Join in the lithium salt solution of ferrocene a), wherein R is an alkyl, adds the back that finishes and is warmed up to room temperature naturally; Stirred 2-15 hour, and added the intact n-Butyl Lithium of alkaline aqueous solution cancellation unreacted then, separatory; Organic phase is washed once with alkaline aqueous solution, and water is transferred PH=6-7 with acid, separates out ferrocene boric acid bullion; Suction filtration obtains 1-ferrocene one boric acid and 1, the diborated mixture of 1 '-ferrocene twice with washing;
C) the ferrocene boric acid ester is synthetic; The ferrocene mebor that obtains is added in the aromatic solvent, add tetramethyl ethylene ketone again, reflux was divided water 6-12 hour, and solvent evaporated, column chromatography for separation obtain 1-ferrocene one boric acid pinacol ester and 1,1 '-ferrocene hypoboric acid, two pinacol esters respectively.
Synthesizing of said a) ferrocene lithium salts: ferrocene and n-Butyl Lithium be 1:2-1:5 in molar ratio, in the anhydrous ether kind solvent, and 0-40 degree reaction 6-18 hour, the ether solvent of generation ferrocene lithium salts;
B) ferrocene boric acid is synthetic: ferrocene and B (OR)
3Mol ratio 1:2-1:5, wherein R is an alkyl, spends B (OR)-50
3Join in the lithium salt solution of the ferrocene that a) obtains, add the back that finishes and be warmed up to room temperature naturally, stirred 2-15 hour; Obtain ferrocene boric acid ester lithium salt complex, add the intact n-Butyl Lithium of alkaline aqueous solution cancellation unreacted then, and decompose the complex compound that it obtains; Separatory, organic phase is washed once with alkaline aqueous solution, and water is transferred PH=6-7 with acid; Separate out ferrocene boric acid bullion, suction filtration obtains 1-ferrocene one boric acid and 1 for twice, the diborated mixture of 1 '-ferrocene with the washing bullion;
C) the ferrocene boric acid ester is synthetic; With b) the ferrocene mebor that obtains adds in the aromatic solvent; Press ferrocene and tetramethyl ethylene ketone mol ratio 1:1.5-1:2.5 again; Add tetramethyl ethylene ketone, reflux was divided water 6-12 hour, solvent evaporated; Column chromatography for separation obtains product 1-ferrocene one boric acid pinacol ester and 1,1 '-ferrocene hypoboric acid, two pinacol esters respectively.
Synthetic route of the present invention is following:
R is an alkyl in the formula, comprises methyl, ethyl sec.-propyl, normal-butyl or isobutyl-etc.
Said b) in ferrocene boric acid synthetic, raw material B (OR)
3, R is methyl, ethyl, sec.-propyl, normal-butyl or isobutyl-.
In said a) ferrocene lithium salts synthetic, the anhydrous ether kind solvent is ether, isopropyl ether, MTBE, glycol dimethyl ether or THF.
Said c) during the ferrocene boric acid ester synthesized, the aromatic solvent that uses was toluene, benzene or YLENE.
Said b) in ferrocene boric acid synthetic, it is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or acetic acid that employed acid is transferred in acid.
Said b) in ferrocene boric acid synthetic, use the alkaline aqueous solution of cancellation to be aqueous sodium hydroxide solution or potassium hydroxide aqueous solution.
Said b) in ferrocene boric acid synthetic, after the alkaline aqueous solution cancellation, separatory; Use MTBE (MTBE) aqueous phase extracted once, use the alkaline aqueous solution extracted organic phase once, suction filtration is transferred in acid; Obtain 1-ferrocene one boric acid and 1 after the washing, 1 '-ferrocene hypoboric acid mixture.
Synthetic and the b of said a) ferrocene lithium salts) synthetic two reaction process of ferrocene boric acid are carried out under protections such as rare gas element such as argon gas, nitrogen.
Chemical synthesis process highway route design of the present invention is reasonable, and processing condition are gentle, uses the homogeneous solvent; And need not synthesize bromo-derivative and directly obtain boric acid, need not use aminocompounds such as TMEDA, not use the very low temperature reaction; Simple to operate being easy to controlled, and synthetic the separation than being easier to.Can industry amplify acquisition than straight product, cost is lower, satisfies the application demand of industries such as industry, agricultural, medicine, space flight, energy-saving and environmental protection.
Embodiment:
Below in conjunction with specific embodiment the present invention is described in further detail, but the present invention is not limited to specific embodiment, all belong to the scheme of the present invention's design all in protection domain of the present invention.
Synthetic route of the present invention is following:
Embodiment 1:
A kind of novel method of synthetic ferrocene boric acid ester, concrete composition of raw materials and step are following:
A) the ferrocene lithium salts is synthetic: ferrocene (0.9mol) is added among the THF (1L), cool to 20 ± 2 degree under the argon shield, drip n-Butyl Lithium (2.7mol), temperature drips off stirred overnight at room temperature less than 40 degree in keeping;
B) cool to about-50 degree and drip B (Oi-Pr)
3(2mol), drip off nature and be warmed up to stirred overnight at room temperature, with 2N aqueous sodium hydroxide solution (1L) cancellation; Water is washed once with MTBE (500ml); Organic phase is washed once with 2N aqueous sodium hydroxide solution (0.5L), and water is transferred PH=6-7 with sulfuric acid, and suction filtration obtains yellow solid; The water making beating is washed and is obtained 1-ferrocene one boric acid and 1 for twice, the diborated mixture of 1 '-ferrocene;
C) said mixture solution is joined in the toluene, and the adding tetramethyl ethylene ketone (PNC, 1.6mol); Reflux is divided water, and TLC identifies no boric acid residue, evaporate to dryness toluene; Column chromatography (EA:Hex=1:20) obtains 1-ferrocene one boric acid pinacol ester and 1,1 '-ferrocene hypoboric acid, two pinacol esters.Performance liquid chromatography (HPLC) Han Liang>97%, proton nmr spectra (
1HNMR) consistent with literature value.
Embodiment 2:
A kind of novel method of synthetic ferrocene boric acid ester, concrete composition of raw materials and step are following:
A) the ferrocene lithium salts is synthetic: ferrocene (0.9mol) is added among the THF (1L), cool to the 0-40 degree under the argon shield, drip n-Butyl Lithium (2.7mol), temperature drips off stirred overnight at room temperature less than 40 degree in keeping;
B) cool to about-50 degree and drip B (OMe)
3(2mol), drip off nature and be warmed up to stirred overnight at room temperature, with 2N aqueous sodium hydroxide solution (1L) cancellation; Water is washed once with MTBE (500ml); Organic phase is washed once with 2N aqueous sodium hydroxide solution (0.5L), and water is transferred PH=6-7 with sulfuric acid, and suction filtration obtains yellow solid; The water making beating is washed and is obtained 1-ferrocene one boric acid and 1 for twice, the diborated mixture of 1 '-ferrocene;
C) said mixture solution is joined in the toluene, add PNC (1.6mol), reflux is divided water; TLC identifies no boric acid residue; Evaporate to dryness toluene, column chromatography (EA:Hex=1:20) obtain 1-ferrocene one boric acid pinacol ester and 1,1 '-ferrocene hypoboric acid, two pinacol esters.HPLC Han Liang>97%,
1HNMR is consistent with literature value.
Embodiment 3:
A kind of novel method of synthetic ferrocene boric acid ester, concrete composition of raw materials and step are following:
A) the ferrocene lithium salts is synthetic: ferrocene (0.9mol) is added among the THF (1L), cool to the 0-40 degree under the argon shield, drip n-Butyl Lithium (2.7mol), temperature drips off stirred overnight at room temperature less than 40 degree in keeping.
B) cool to about-50 degree and drip B (Oi-Bu)
3(2mol), drip off nature and be warmed up to stirred overnight at room temperature.With 2N aqueous sodium hydroxide solution (1L) cancellation; Water is washed once with MTBE (500ml); Organic phase is washed once with 2N aqueous sodium hydroxide solution (0.5L), and water is transferred PH=6-7 with sulfuric acid, and suction filtration obtains yellow solid; The water making beating is washed and is obtained 1-ferrocene one boric acid and 1 for twice, the diborated mixture of 1 '-ferrocene;
C) said mixture solution is joined in the toluene, add PNC (1.6mol), reflux is divided water; TLC identifies no boric acid residue; Evaporate to dryness toluene, column chromatography (EA:Hex=1:20) obtain 1-ferrocene one boric acid pinacol ester and 1,1 '-ferrocene hypoboric acid, two pinacol esters.HPLC Han Liang>97%,
1HNMR is consistent with literature value.
Embodiment 4:
A kind of novel method of synthetic ferrocene boric acid ester, concrete composition of raw materials and step are following:
A) the ferrocene lithium salts is synthetic: ferrocene (0.9mol) is added among the THF (1L), cool to the 0-40 degree under the argon shield, drip n-Butyl Lithium (2.7mol), temperature drips off stirred overnight at room temperature less than 40 degree in keeping.
B) cool to about-50 degree and drip B (On-Bu)
3(2mol), drip off nature and be warmed up to stirred overnight at room temperature.With 2N aqueous sodium hydroxide solution (1L) cancellation; Water is washed once with MTBE (500ml); Organic phase is washed once with 2N aqueous sodium hydroxide solution (0.5L), and water is transferred PH=6-7 with sulfuric acid, and suction filtration obtains yellow solid; The water making beating is washed and is obtained 1-ferrocene one boric acid and 1 for twice, the diborated mixture of 1 '-ferrocene;
C) said mixture solution is joined in the toluene, add PNC (1.6mol), reflux is divided water; TLC identifies no boric acid residue; Evaporate to dryness toluene, column chromatography (EA:Hex=1:20) obtain 1-ferrocene one boric acid pinacol ester and 1,1 '-ferrocene hypoboric acid, two pinacol esters.HPLC Han Liang>97%,
1HNMR is consistent with literature value.
Embodiment 5
A kind of novel method of synthetic ferrocene boric acid ester, concrete raw material and process step are identical with embodiment 1, and different is that the proportioning raw materials consumption is following:
Ferrocene 0.9mol; N-Butyl Lithium 1.8 mol; B (Oi-Pr)
32mol; PNC 1.5mol.Obtain 1-ferrocene one boric acid pinacol ester and 1,1 '-ferrocene hypoboric acid, two pinacol esters.HPLC Han Liang>97%,
1HNMR is consistent with literature value.
Embodiment 6
A kind of novel method of synthetic ferrocene boric acid ester, concrete raw material and process step are identical with embodiment 2, and different is that the proportioning raw materials consumption is following:
Ferrocene 0.9mol; N-Butyl Lithium 2 mol; B (OMe)
32.2mol; PNC 2 mol.Obtain 1-ferrocene one boric acid pinacol ester and 1,1 '-ferrocene hypoboric acid, two pinacol esters.HPLC Han Liang>97%,
1HNMR is consistent with literature value.
Embodiment 7
A kind of novel method of synthetic ferrocene boric acid ester, concrete raw material and process step are identical with embodiment 3, and different is that the proportioning raw materials consumption is following:
Ferrocene 0.9mol; N-Butyl Lithium 2.2 mol; B (Oi-Bu)
32.4 mol; PNC 2 mol.Obtain 1-ferrocene one boric acid pinacol ester and 1,1 '-ferrocene hypoboric acid, two pinacol esters.HPLC Han Liang>97%,
1HNMR is consistent with literature value.
Embodiment 8
A kind of novel method of synthetic ferrocene boric acid ester, concrete raw material and process step are identical with embodiment 4, and different is that the proportioning raw materials consumption is following:
Ferrocene 0.9mol; N-Butyl Lithium 2.4mol; B (Oi-Pr)
32.6mol; PNC 2.2mol.Obtain 1-ferrocene one boric acid pinacol ester and 1,1 '-ferrocene hypoboric acid, two pinacol esters.HPLC Han Liang>97%,
1HNMR is consistent with literature value.
Claims (9)
1. the novel method of a synthetic ferrocene boric acid ester, it is characterized in that: concrete steps are following:
A) the ferrocene lithium salts is synthetic: with the ferrocene is raw material, in the anhydrous ether kind solvent, reacts the lithium salts that obtains ferrocene at the 0-40 degree with n-Butyl Lithium;
B) ferrocene boric acid is synthetic: spend B (OR)-78～-50
3Join in the lithium salt solution of ferrocene a), wherein R is an alkyl, adds the back that finishes and is warmed up to room temperature naturally; Stirred 2-15 hour, and added the intact n-Butyl Lithium of alkaline aqueous solution cancellation unreacted then, separatory; Organic phase is washed once with alkaline aqueous solution, and water is transferred PH=6-7 with acid, separates out ferrocene boric acid bullion; Suction filtration obtains 1-ferrocene one boric acid and 1, the diborated mixture of 1 '-ferrocene twice with washing;
C) the ferrocene boric acid ester is synthetic; The ferrocene mebor that obtains is added in the aromatic solvent, add tetramethyl ethylene ketone again, reflux was divided water 6-12 hour, and solvent evaporated, column chromatography for separation obtain 1-ferrocene one boric acid pinacol ester and 1,1 '-ferrocene hypoboric acid, two pinacol esters respectively.
2. the novel method of a kind of synthetic ferrocene boric acid ester according to claim 1 is characterized in that: concrete steps are following:
A) the ferrocene lithium salts is synthetic: ferrocene and n-Butyl Lithium be 1:2-1:5 in molar ratio, in the anhydrous ether kind solvent, and 0-40 degree reaction 6-18 hour, the ether solvent of generation ferrocene lithium salts;
B) ferrocene boric acid is synthetic: ferrocene and B (OR)
3Mol ratio 1:2-1:5, wherein R is an alkyl, spends B (OR)-50
3Join in the lithium salt solution of the ferrocene that a) obtains, add the back that finishes and be warmed up to room temperature naturally, stirred 2-15 hour; Obtain ferrocene boric acid ester lithium salt complex, add the intact n-Butyl Lithium of alkaline aqueous solution cancellation unreacted then, and decompose the complex compound that it obtains; Separatory, organic phase is washed once with alkaline aqueous solution, and water is transferred PH=6-7 with acid; Separate out ferrocene boric acid bullion, suction filtration obtains 1-ferrocene one boric acid and 1 for twice, the diborated mixture of 1 '-ferrocene with the washing bullion;
C) the ferrocene boric acid ester is synthetic; With b) the ferrocene mebor that obtains adds in the aromatic solvent; Press ferrocene and tetramethyl ethylene ketone mol ratio 1:1.5-1:2.5 again; Add tetramethyl ethylene ketone, reflux was divided water 6-12 hour, solvent evaporated; Column chromatography for separation obtains product 1-ferrocene one boric acid pinacol ester and 1,1 '-ferrocene hypoboric acid, two pinacol esters respectively.
3. the novel method of a kind of synthetic ferrocene boric acid ester according to claim 1 and 2 is characterized in that: b) in ferrocene boric acid synthetic, and raw material B (OR)
3, R is methyl, ethyl, sec.-propyl, normal-butyl or isobutyl-.
4. the novel method of a kind of synthetic ferrocene boric acid ester according to claim 1 and 2 is characterized in that: a) in ferrocene lithium salts synthetic, the anhydrous ether kind solvent is ether, isopropyl ether, MTBE, glycol dimethyl ether or THF.
5. the novel method of a kind of synthetic ferrocene boric acid ester according to claim 1 and 2 is characterized in that: during c) the ferrocene boric acid ester synthesized, the aromatic solvent that uses was toluene, benzene or YLENE.
6. the novel method of a kind of synthetic ferrocene boric acid ester according to claim 1 and 2 is characterized in that: b) in ferrocene boric acid synthetic, it is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or acetic acid that employed acid is transferred in acid.
7. the novel method of a kind of synthetic ferrocene boric acid ester according to claim 1 and 2 is characterized in that: b) in ferrocene boric acid synthetic, use the alkaline aqueous solution of cancellation to be aqueous sodium hydroxide solution or potassium hydroxide aqueous solution.
8. the novel method of a kind of synthetic ferrocene boric acid ester according to claim 1 and 2 is characterized in that: b) in ferrocene boric acid synthetic, after the alkaline aqueous solution cancellation; Separatory; Use the MTBE aqueous phase extracted once, use the alkaline aqueous solution extracted organic phase once, suction filtration is transferred in acid; Obtain 1-ferrocene one boric acid and 1 after the washing, 1 '-ferrocene hypoboric acid mixture.
9. the novel method of a kind of synthetic ferrocene boric acid ester according to claim 1 and 2 is characterized in that: a) the synthetic and b of ferrocene lithium salts) synthetic two reaction process of ferrocene boric acid are carried out under protections such as rare gas element such as argon gas, nitrogen.
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| CN105817571A (en) * | 2016-05-27 | 2016-08-03 | 马鞍山市兴隆铸造有限公司 | Anti-sagging modified quartz-based mica powder full mold paint and preparation method thereof |
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| WO2008055942A1 (en) * | 2006-11-10 | 2008-05-15 | Solvias Ag | Preparation of optically pure ferrocenediphosphines |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2008055942A1 (en) * | 2006-11-10 | 2008-05-15 | Solvias Ag | Preparation of optically pure ferrocenediphosphines |
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| CN105817571A (en) * | 2016-05-27 | 2016-08-03 | 马鞍山市兴隆铸造有限公司 | Anti-sagging modified quartz-based mica powder full mold paint and preparation method thereof |
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Application publication date: 20121010 |