CN103421050A - Ferrocene dicarboxylate compounds and synthetic method thereof - Google Patents
Ferrocene dicarboxylate compounds and synthetic method thereof Download PDFInfo
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- CN103421050A CN103421050A CN201210154670XA CN201210154670A CN103421050A CN 103421050 A CN103421050 A CN 103421050A CN 201210154670X A CN201210154670X A CN 201210154670XA CN 201210154670 A CN201210154670 A CN 201210154670A CN 103421050 A CN103421050 A CN 103421050A
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Abstract
The invention discloses ferrocene dicarboxylate compounds and a preparation method thereof. The preparation method prepares ferrocene dicarboxylate (the carbon number of the carbon chain is 3, 4, 5, ...15) from dimethyl ferrocene dicarboxylate, etc. through an ester interchanging method; or prepares the ferrocene dicarboxylate by converting ferrocene dicarboxylic acid into ferrocene diacid halide, and then subjecting the ferrocene diacid halide to react with corresponding alcohol. At present, ferrocene dicarboxylate compounds with a carbon number of 3 to 15 have not been reported. The molecular structure of ferrocene dicarboxylate compounds meets the three main requirements on the molecular design of combustion catalysts: (1) the molecule must contain two big polarity functional groups; (2) the molecule must contain an alkyl group with a long chain; (3) the synthetic product is liquid. It has been proved by differential scanning calorimetry (DSC) analysis that dioctyl ferrocene dicarbonate has a very good catalytic effect on thermal cracking of ammonium perchlorate.
Description
Technical field
The invention discloses class novel ferrocene dicarboxylic ester compounds and a synthetic method thereof.
Background technology
The ferrocene analog derivative is the important organometallics of a class.Ferrocene and derivative thereof can the catalysis ammoniumper chlorate thermolysis, realize that the pyrolytic decomposition exothermic temperature of ammoniumper chlorate and fuming-off temperature descend, so ferrocene and derivative thereof are a kind of good positive burningrate catalysts.Ferrocene deriv has been widely used in usining in the many kinds of solids propelling agent and gasifier of ammoniumper chlorate as oxygenant at present.
In the solid propellant system, applied ferrocene catalyzer should have following three characteristics: under (1) room temperature, be preferably liquid; (2) should there is large polar functional group in molecular structure; (3) in molecular structure, chain alkyl functional group should be arranged.In document and patent, the report of ferrocene burningrate catalyst is more, but mostly is alkyl monokaryon ferrocene and alkyl biferrocene derivative.These ferrocene deriv can only meet one or two in three characteristics.This patent is designed and the synthetic carbon number obtained is 3 ~ 15 1, and l '-ferrocenedicarboxylic acid ester compound is showed no bibliographical information, after synthetic the evaluation, under the correct and room temperature of these ferrocene new compound structures, is liquid.
In sum, in designed synthetic its molecular structure of novel ferrocene carboxylic acid ester compound of the present invention, have: the ester group functional group of (1) two large polarity; (2) contain the different lengths alkyl chain; (3) product is liquid, has had three kinds of performances of designed molecule concurrently.
Summary of the invention
Purpose of the present invention is for providing a kind of novel ferrocene dicarboxylic ester compounds and synthetic method thereof.From ferrocene cheap and easy to get, through acetylize, oxidation, can obtain ferrocenedicarboxylic acid; The ferrocenedicarboxylic acid direct esterification can prepare ferrocenedicarboxylic acid dimethyl ester, diethyl ester and dipropyl easily.
The ferrocenedicarboxylic acid diester is take in the present invention, and as raw material can prepare by ester-interchange method the ferrocenedicarboxylic acid ester compound that has no bibliographical information, (carbon number of ester chain is 3,4,5,6 ... 15); Or first be converted into ferrocene two acetyl halide compounds with ferrocenedicarboxylic acid, then with corresponding alcohol, react the above-mentioned ferrocenedicarboxylic acid ester compound of preparation.The outstanding feature of this invention is designed and complete synthetic compound structure novelty; The synthesized compound to ammoniumper chlorate have that significant catalytic decomposition effect and synthetic operation are simple, convenient post-treatment and yield high.
Ferrocene deriv of the present invention has following structural formula
R wherein
2C
3~ C
15Alkyl.Preferred R
2C
5~ C
10Alkyl.
The inventive method adopts following reaction:
R
1Methoxyl group, oxyethyl group, halogen R
2C
3~ C
15-alkyl
A acyl halogen process is 1. under-20 ℃ ~ reflux temperature of organic solvent neutralization, ferrocene dicarboxylic acid, within 0.5 ~ 48 hour, make two acetyl halide compounds with the carboxylic acid halides reagent react, described carboxylic acid halides reagent is thionyl chloride, oxalyl chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, tribromo oxygen phosphorus, phosphorus pentabromide; Described ferrocene dicarboxylic acid with the mol ratio of carboxylic acid halides reagent be 1: 0.5 ~ 10; Two acetyl halide compounds and the C that 2. under the catalysis of alkali, will make
3~ C
15Alcohol reaction, preferred R
2C
5~ C
10Alcohol.
By the reaction solution cancellation, use the organic solvent extraction reaction solution afterwards, the organic phase drying of merging, concentrated, column chromatography for separation or underpressure distillation obtain the purification of target product.Described reaction organic solvent is methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), chloroform, dioxane, benzene, toluene or acetonitrile; The mol ratio of described ferrocene dicarboxylic acid, carboxylic acid halides reagent and alkali is 1: 0.5 ~ 10: 0.5 ~ 50.
Under the catalysis of alkali and under-20 ℃ ~ reflux temperature, by above-mentioned two acetyl halide compounds and the C made
3~ C
15Alcohol reaction 0.5 ~ 48 hour; Described two acetyl halide compounds and C
3~ C
15The mol ratio of alcohol be 1: 1 ~ 20; Described alkali is triethylamine, pyridine, picoline, piperidines, salt of wormwood, sodium carbonate, cesium carbonate, sodium bicarbonate, saleratus, potassium alcoholate or sodium alkoxide.
The b ester-interchange method in organic solvent and under 40 ℃ ~ reflux temperature, the alcohol that the carbochain number is 3 ~ 15, the catalyzer such as acid or alkali, ferrocene dicarboxylic acid diester reaction 0.5 ~ 48 hour.
This reacts described organic solvent is methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), chloroform, benzene,toluene,xylene, mixed benzene, normal hexane, hexanaphthene, acetonitrile or their mixed solvent.This reacts described acid catalyst is hydrochloric acid, sulfuric acid, nitric acid, aluminum chloride and zinc chloride; Described alkaline catalysts comprises lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium ethylate, potassium ethylate, potassium methylate, sodium methylate, potassium tert.-butoxide and sodium tert-butoxide.Ferrocene dicarboxylic acid diester in this reaction, alcohol, catalyzer appropriate molar ratios be 1: 0.5 ~ 50: 0.1 ~ 10.Reaction product, can extract and separate by organic phase, drying, and concentrated, the methods such as column chromatography for separation or underpressure distillation obtain the target product of purifying.
The accompanying drawing explanation
Means of differential scanning calorimetry (DSC) the analytic curve figure of Fig. 1 ammoniumper chlorate (AP);
Fig. 2 adds means of differential scanning calorimetry (DSC) the analytic curve figure that 7% ferrocene dicarboxylic acid dioctyl ester mixes with ammoniumper chlorate (AP).
Wherein, AP ammoniumper chlorate; The DSC dsc.
Embodiment
［ embodiment 1 ］ 1, l '-diacetyl ferrocene synthetic
In the there-necked flask with reflux condensing tube (with drying tube), dropping funnel, substituted nitrogen, add 45g AlCl under nitrogen atmosphere
3, and the CH of 50mL drying
2Cl
2In, under stirring, drip the Acetyl Chloride 98Min. of 31mL and the CH of 60mL drying
2Cl
2Mixed solution.After dropwising, reflux until solid all dissolve.The 25g ferrocene is dissolved in to the dry CH of 80mL
2Cl
2In, move into dropping funnel, slowly be added dropwise in there-necked flask, reaction solution is in slight boiling condition (being that temperature is controlled at 40 ℃ of left and right) and become red-purple.After ferrocene dropwises, reaction at room temperature continues to stir, and TLC determines reaction end, and stopped reaction is slowly poured reaction solution on trash ice into and decomposed, and by the solution layering, separates organic phase.Water layer is used CHCl again
3After 3 * 50mL extraction, the organic phase obtained and the organic phase of front merge, and with separatory after saturated common salt washing once, the organic phase anhydrous sodium sulfate drying, after suction filtration is removed sodium sulfate crystal, revolve organic phase to steam to dry, obtains the red-brown solid.Recrystallization obtains red-brown crystal 31g, productive rate 85%, and HPLC purity is 98%.
1H?NMR(300MHz,CDCl
3):2.34(s,6H)，4.50(s,4H)，4.76(s,4H).
［ embodiment 2 ］ 1, l '-ferrocene dicarboxylic acid synthetic
10L with churned mechanically reaction flask in, add 367g1, l '-diacetyl ferrocene, the 4000mL10% aqueous sodium hypochlorite solution also stirs.The system heating, in controlling, temperature, between 46 ~ 50 ℃, after stirring 2h, drips the 600mL10% aqueous sodium hypochlorite solution every 1h in system, and 20min dropwises, and in the hierarchy of control, temperature, between 46 ~ 50 ℃, is added 5 times altogether.Insulated and stirred 1h again after dropwising for 5 times.Filtered while hot, filter cake generates without yellow solid to sampling acidifying filtrate with hot wash.Filtrate is carried out acidifying with concentrated hydrochloric acid and is obtained yellow solid, controls souring temperature not higher than 40 ℃.Filtration obtains yellow filter cake, by distilled water wash filter cake to filtrate pH value, is neutral.Filter cake is dried and is obtained 357g1,1 '-ferrocene dicarboxylic acid, productive rate 96%.
1H?NMR(300MHz,d
6-DMSO):4.46(d,4H)，4.69(d,4H)，12.30(br,2H).
［ embodiment 3 ］ 1, l '-ferrocene dicarboxylic acid dimethyl ester
In with reflux condensing tube, churned mechanically 3L there-necked flask, add 200g1,1 '-ferrocene dicarboxylic acid, 2200mL methyl alcohol, open stirring.Under vigorous stirring, drip the 15.5mL vitriol oil in system, open heating, control 85 ℃ of oil baths.TLC Analysis deterrmination reaction end.After reaction solution is cooling, with core, filter, obtain brown needle-like crystals, with 400mL * 2 distilled water washs, filtrate merges distilled water wash to neutral, drains, and the combining solid recrystallization obtains the 197.5g brown needle-like crystals, productive rate 90%.
1H?NMR(300MHz,CDCl
3):3.82(s,6H)，4.40(s,4H)，4.82(s,4H).
［ embodiment 4 ］ 1, l '-ferrocene dicarboxylic acid diethyl ester
Add 241mg(0.88mmol in reaction tubes) 1,1 '-ferrocene dicarboxylic acid and 4mL ethanol, add 0.04mL(0.7mmol under vigorous stirring) vitriol oil, reflux, reaction 24h.Reaction solution is spin-dried for, and with methylene dichloride, dissolves, with 30mL10% solution of potassium carbonate washing organic phase, stratification.Separate organic phase, water 10mL dichloromethane extraction 2 times.Merge organic phase, use 10mL distilled water wash 2 times, use anhydrous magnesium sulfate drying 2h.The filtration organic phase is spin-dried for, and the plate layer chromatography separation obtains the 74mg product, salmon liquid, productive rate 30%.
1H?NMR(300MHz,CDCl
3):1.34(t,6H)，4.25(t,4H)，4.41(s,4H)，4.83(s,4H).
［ embodiment 5 ］ 1, l '-ferrocene dicarboxylic acid dipropyl
1, l '-ferrocene dicarboxylic acid dipropyl with 1,1 '-method preparation that the ferrocene dicarboxylic acid diethyl ester is identical, productive rate is 10.4%.
1H?NMR(300MHz,CDCl
3):1.00(t,6H),1.72(q,4H),4.16(t,4H),4.39(t,4H),4.82(t,4H).
［ embodiment 6 ］ 1, l '-ferrocene dicarboxylic acid dibutylester
N
2Add successively 500mg1 under protection, l '-ferrocene dicarboxylic acid dimethyl ester 22.35mg sodium methylate, 9ml toluene, finally add the 0.613g propyl carbinol, opens stirring, and oil bath is heated to 125 ℃ of reactions 12 hours.Reaction solution is poured cancellation in 20mL water into, the standing organic phase that separates, 20mL for water * 3 ether extraction.Merge organic phase, 50mL saturated common salt water washing for organic phase.Organic phase is spin-dried for, obtains brown oily liquids.Column chromatography for separation obtain red-brown oily 1,1 '-ferrocene dicarboxylic acid dibutylester liquid, yield 71%.
1H NMR (300MHz, CDCl
3): 0.99 (t, 6H), 1.40-1.53 (m, 4H), 1.63-1.76 (m, 4H), 4.22 (t, 4H), 4.39 (t, 4H), (4.82 t, 4H) .IR(KBr compressing tablet): 3110,2960,2931,2873,1716,1463,1374,1277,1139,1027,963,837,775. ultimate analysis, theoretical value: C 62.19%, H 6.78%. measured value: C62.81%, H 7.08%.
［ embodiment 7 ］ 1, l '-ferrocene dicarboxylic acid di-isooctyl
Add successively 500mg1 under the N2 protection, l '-ferrocene dicarboxylic acid dimethyl ester, 22.35mg sodium methylate, 9ml toluene, finally add 1.3mL(1.08g, 8.28mmol) isooctyl alcohol, open stirring, oil bath is heated to 125 ℃ of reactions 15 hours.Reaction solution is poured cancellation in 20mL water into, the standing organic phase that separates, 20mL for water * 3 ether extraction.Merge organic phase, 50mL saturated common salt water washing for organic phase.Organic phase is spin-dried for, obtains brown oily liquids.Column chromatography for separation obtain red-brown oily 1,1 '-ferrocene dicarboxylic acid di-isooctyl liquid, yield 60%.
1H NMR (300MHz, CDCl
3): 0.88-0.99 (m, 12H), 1.25-1.55 (m, 20H), 1.67 (q, 2H), 4.15 (t, 4H), 4.38 (t, 4H), 4.84 (t, 4H) .IR(KBr films): 3096,2959,2930,2860,1719,1460,1380,1274,1140,1027,962,836,775,727. ultimate analysis, theoretical value C67.47%, H 8.49%. measured value: C 67.14%, H 8.65%.
［ embodiment 8 ］ 1, l '-ferrocene dicarboxylic acid dioctyl ester
In with water trap, reflux condensing tube, churned mechanically 3L four-hole boiling flask, N
2Add successively the 94mL n-Octanol under protection,, open stirring, then add the 33.8g sodium methylate, finally add 90g1, l '-ferrocene dicarboxylic acid dimethyl ester, 2250mL toluene, oil bath is heated to 125 ℃.TLC Analysis deterrmination reaction end.Reaction solution is poured cancellation in 800mL water into, the standing organic phase that separates, 100mL for water * 3 ether extraction.Merge organic phase, 100mL for organic phase * 4 saturated common salt water washings.Organic phase is spin-dried for, obtains brown oily liquids.Through column chromatography for separation obtain red-brown oily 1,1 '-ferrocene dicarboxylic acid dioctyl ester liquid, yield 65%.
1H NMR (300MHz, CDCl
3): 0.86 (d, 6H), 1.28-1.42 (m, 20H), 1.67 (q; 4H), 4.18 (t, 4H), 4.38 (s, 4H); 4.82 (s, 4H) .IR(KBr films): 3106,2958,2928,2856; 1717,1463,1375,1275; 1142,1027,958,825; 775,723. ultimate analyses, theoretical value C 67.47%, and H 8.49%; Measured value: C67.82%, H 8.31%.
［ embodiment 9 ］ ferrocene dicarboxylic acid dihexyl
In the 50mL reaction tubes, add and roll to pulverous ferrocene dicarboxylic acid 1g (3.65mmol, 1eq), substitute nitrogen.Adding 15mL newly to steam methylene dichloride stirs.Slowly drip oxalyl chloride 3.5mL (36.5mmol, 10eq), stirred overnight at room temperature.Reaction solution is concentrated, nitrogen protection, stand-by.Build reaction unit, the 50ml reaction flask, substitute nitrogen three times.Add successively n-hexyl alcohol 4.57mL (36.5mmol, 10eq), methylene dichloride 5mL, triethylamine 1.02mL (7.3mmol, 2eq), stir.Above-mentioned concentrated ferrocene dimethyl chloride is dissolved in to the 10mL methylene dichloride, slowly drops in reaction flask, emit a large amount of white smoke, stirring at room 2hr.Reaction solution is poured into water, the water dichloromethane extraction, the organic phase of merging is used 5% aqueous sodium carbonate successively, saturated aqueous common salt, distilled water is respectively washed once.Column chromatography for separation obtains target product, is yellow oil, and yield is 84.43%.
1H NMR (300MHz, CDCl
3): 0.91 (t, 6H), 1.32-1.45 (m, 20H), 1.67-1.74 (m, 4H), 4.21 (t, 4H), 4.38 (s, 4H), 4.82 (s, 4H) .IR(KBr films): 3110,2929.3,2858,1716,1463,1374,1271,1137,1053,1026,980,927,907,836,774,726,489. ultimate analyses, theoretical value, C 65.16%H 7.7%; Measured value, C 65.25%, and H 7.73%.
The catalyticing decomposition action of ［ embodiment 10 ］ ferrocene dicarboxylic acid dioctyl ester to AP.
Use the differential scanning calorimetric analysis method, pure ammoniumper chlorate (AP) and the heat decomposition temperature of AP that adds the ferrocene dicarboxylic acid dioctyl ester of 7% embodiment 8 preparations are analyzed.
Figure 1A P is most widely used oxygenant in composite solidpropellant now.AP is at room temperature more stable, and its temperature, at 244 ℃, crystal phase transition occurs, and after surpassing 280 ℃, thermolysis occurs AP.From pure AP heat decomposition curve, can find out: AP low-temperature decomposition temperature is 298 ℃ (290 ℃-320 ℃ of data in literature) left and right, high-temperature decomposition temperature is 356 ℃ (document is more than 350 ℃), decomposes fully or claims that fuming-off temperature is 436 ℃ (440 ℃ of data in literature) left and right.(the data in literature reference: the burning of solid propellant and catalysis, Zhang Ren writes, P15-16, press of the National University of Defense technology, 1992).
Fig. 2 surveys and tests the number a tree name and show by add after 7% ferrocene dicarboxylic acid dioctyl ester institute in AP, and interpolation ferrocene dicarboxylic acid dioctyl ester does not affect the crystal conversion temperature of AP, and the low-temperature decomposition temperature is delayed to 300 ℃ by 298 ℃; And as most important index pyrolytic decomposition peak and the fuming-off temperature of catalysis, significant reduction is all arranged, wherein the pyrolytic decomposition peak is 10 ℃ in advance, at 346 ℃, starts to decompose; And fuming-off temperature shifts to an earlier date 50 ℃ to 386 ℃.The ferrocene dicarboxylic acid dioctyl ester has significant catalytic effect to the thermolysis of AP as can be seen here.
Claims (4)
1. a class ferrocenedicarboxylic acid ester compound, is characterized in that described ferrocene deriv has following structural formula
R wherein
2C
3~ C
15Alkyl.
2. according to ferrocenedicarboxylic acid ester compound claimed in claim 1, it is characterized in that described R
2C
3~ C
15Alkyl.
3. according to the preparation method of the said ferrocenedicarboxylic acid ester compound of claim 1, it is characterized in that obtaining by ester-interchange method or two kinds of methods of carboxylic acid halidesization:
R
1Methoxyl group, oxyethyl group, halogen R
2C
3~ C
15-alkyl,
1) ester-interchange method
In organic solvent and under 40 ℃ ~ reflux temperature, C
3~ C
15Alcohol, acid or alkaline catalysts and ferrocene dicarboxylic acid diester reaction 0.5 ~ 48 hour; The mol ratio of described ferrocene dicarboxylic acid diester, alcohol or alkali, catalyzer is 1: 0.5 ~ 50: 0.1 ~ 10; Described acid catalyst is hydrochloric acid, sulfuric acid, nitric acid, aluminum chloride and zinc chloride; Described alkaline catalysts is lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium methoxide, lithium ethoxide, sodium ethylate, potassium ethylate, potassium methylate, sodium methylate, potassium tert.-butoxide and sodium tert-butoxide; Described organic solvent is methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), chloroform, benzene,toluene,xylene, normal hexane, hexanaphthene, acetonitrile or their mixed solvent;
2) acyl halogen process
Under-20 ℃ ~ reflux temperature of organic solvent neutralization, ferrocene dicarboxylic acid with within 0.5 ~ 48 hour, make two acetyl halide compounds with the carboxylic acid halides reagent react; Described ferrocene dicarboxylic acid with the mol ratio of carboxylic acid halides reagent be 1: 0.5 ~ 10; Described carboxylic acid halides reagent is thionyl chloride, oxalyl chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, tribromo oxygen phosphorus or phosphorus pentabromide;
Under the catalysis of alkali and under-20 ℃ ~ reflux temperature, by above-mentioned two acetyl halide compounds and the C made
3~ C
15Alcohol reaction 0.5 ~ 48 hour; Described two acetyl halide compounds, C
3~ C
15Alcohol and the mol ratio of alkali be 1: 1 ~ 20: 0.5 ~ 50; Described alkali is triethylamine, pyridine, picoline, piperidines, salt of wormwood, sodium carbonate, cesium carbonate, sodium bicarbonate, saleratus, potassium alcoholate or sodium alkoxide;
Described organic solvent is methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), chloroform, dioxane, benzene, toluene or acetonitrile.
4. according to the preparation method of the said ferrocenedicarboxylic acid ester compound of claim 3, it is characterized in that step 1) or 2) reaction product, carry out purifying with organic solvent extraction separation and purification, drying, concentrated, column chromatography for separation or underpressure distillation.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103739875A (en) * | 2013-12-30 | 2014-04-23 | 上海葆硕磁性材料有限公司 | Aliphatic chain ester metal complex modified material for macromolecule injection molding magnetic material |
| CN104402916A (en) * | 2014-11-19 | 2015-03-11 | 西南科技大学 | Cerium trimesic acid complex for catalyzing thermal decomposition of AP (ammonium perchlorate) and preparation method of cerium trimesic acid complex |
| CN108329360A (en) * | 2018-04-16 | 2018-07-27 | 陕西师范大学 | Fragrant cyclopentadienyl iron picrate ionic compound and preparation method thereof |
| CN110305174A (en) * | 2019-05-28 | 2019-10-08 | 黎明化工研究设计院有限责任公司 | A method of preparing ferrocenedicarboxylic acid dihydroxyalkyl ester |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739875A (en) * | 2013-12-30 | 2014-04-23 | 上海葆硕磁性材料有限公司 | Aliphatic chain ester metal complex modified material for macromolecule injection molding magnetic material |
| CN104402916A (en) * | 2014-11-19 | 2015-03-11 | 西南科技大学 | Cerium trimesic acid complex for catalyzing thermal decomposition of AP (ammonium perchlorate) and preparation method of cerium trimesic acid complex |
| CN108329360A (en) * | 2018-04-16 | 2018-07-27 | 陕西师范大学 | Fragrant cyclopentadienyl iron picrate ionic compound and preparation method thereof |
| CN108329360B (en) * | 2018-04-16 | 2020-10-13 | 陕西师范大学 | Ferrocene picrate ionic compound and preparation method thereof |
| CN110305174A (en) * | 2019-05-28 | 2019-10-08 | 黎明化工研究设计院有限责任公司 | A method of preparing ferrocenedicarboxylic acid dihydroxyalkyl ester |
| CN110305174B (en) * | 2019-05-28 | 2023-03-24 | 黎明化工研究设计院有限责任公司 | Method for preparing ferrocene dicarboxylic acid dihydroxy alkyl ester |
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Application publication date: 20131204 |