CN1948250A - Synthesis method of adamantine alkylphenol - Google Patents
Synthesis method of adamantine alkylphenol Download PDFInfo
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- CN1948250A CN1948250A CN 200610123443 CN200610123443A CN1948250A CN 1948250 A CN1948250 A CN 1948250A CN 200610123443 CN200610123443 CN 200610123443 CN 200610123443 A CN200610123443 A CN 200610123443A CN 1948250 A CN1948250 A CN 1948250A
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- diamantane
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- biphenol
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Abstract
The present invention discloses a synthesis method of adamantalkylphenol. Said method includes the following steps: firstly, mixing the adamantane and liquid bromine according to mole ratio of 1:1-5, under the condition of 50-120 deg.C making reaction for 4-24 h to synthesize 1-bromoadamantane; then mixing the synthetic 1-bromoadamantane and metaphenylene diamine according to the mole ratio of 1:1-5, at the same time adding organic solvent, under the condition of 40-90 deg.C making reaction for 5-72 h so as to synthesize 4-(1-adamantalkyl)-1.3-diphenol. Its product yield can be up to 69.3%.
Description
Technical field
The present invention relates to adamantine alkylphenol, be specifically related to the synthetic method of adamantine alkylphenol.
Background technology
As shown in Figure 6, diamantane (three ring [3.3.1.1] decane) is a kind of straight symmetry, highly stable cage shape hydrocarbon, and by 10 carbon atoms and 16 ring-type tetrahedral carbon hydrogen compounds that hydrogen atom constitutes, its basic framework is similar to an adamantine lattice element.In its molecular weight ranges, diamantane is the hydrocarbon molecules of subglobular in the known molecular, its rigidity ring system and symmetry structures shape it have unique physical features and chemical property.
The chemical reactivity of diamantane is lower slightly than benzene, under usual conditions and reagent such as nitric acid, chromic acid, potassium permanganate do not have an effect, but under certain catalysts influence, can replace, reactions such as oxidation, rearrangement.Can form numerous adamantane derivatives by substitution reaction (halogenation, nitrated, sulfonation, alkylation etc.) as 4 bridgehead positions (1,3,5,7) of diamantane.Diamantane and derivative thereof are of many uses, are widely used in various fields such as medicine, functional polymer, lubricating oil, catalyzer, tensio-active agent, sensitive materials, agricultural chemicals, are called as fine chemical material of new generation.States such as America and Europe, Japan and Korea S are at the synthetic adamantyl functional polymer field quantity research that has high input that contains in recent years.Result of study shows: main chain or the side chain of the diamantane skeleton structure being introduced functional high-polymer polymkeric substance such as polyester, polycarbonate, polymeric amide, polysulfones, polyethers, urethane and polyimide, can significantly improve thermostability, chemical stability, the optical stability of polymkeric substance, improve its dielectric properties and mechanical property, thereby prepare a series of liquid crystal display material, semiconductor lithography glue material, holographic photochromics, separation membrane, intelligent plastics, contact lens and pharmaceutical carriers etc. with specific function.The diamantane polymkeric substance demonstrates wide application prospect at high-technology fields such as microelectronics, communication, aviation, opticinstrument, biomedicines.China relatively lags behind in the research in this field at present, does not see as yet so far to contain diamantane monomer and the synthetic aspect of polymkeric substance report.Adamantine alkylphenol is 4-(1-adamantyl)-1 just, and the 3-biphenol can be used as the monomer that synthesizes high heat resistance polyarylester, polyarylether and functional polymer polyarylsulphone etc., also can be used as other additive and uses.Have not yet to see the report of adamantine alkylphenol synthetic method.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, the synthetic method of a kind of simple and easy to do adamantine alkylphenol (4-(1-adamantyl)-1,3-biphenol) is provided.
Principle of the present invention is a starting raw material with the diamantane as shown in Figure 7, through bromination, carry out the reaction of nucleophilic substitution reaction two step with Resorcinol and synthesized 4-(1-adamantyl)-1,3-biphenol, yield 69.3%.
Purpose of the present invention is achieved through the following technical solutions:
A kind of synthetic method of adamantine alkylphenol comprises the steps:
(1) diamantane bromination: is 1 in molar ratio with diamantane with the liquid bromine: 1-5 mixes, and under 50-120 ℃ of temperature condition, reacts 4-24 hour, synthetic 1-bromine diamantane;
(2) be 1: 1～5 to mix in molar ratio with step (1) synthetic 1-bromine diamantane and Resorcinol, under 40-90 ℃ of temperature condition, reacted 5-72 hour, synthesized 4-(1-adamantyl)-1, the 3-biphenol.
Described step (1) also comprises with saturated aqueous solution of sodium bisulfite reduces unreacted bromine, filters synthetic 1-bromine diamantane, is washed to neutrality, and recrystallizing methanol use in the vacuum drying oven oven dry, must 1-bromine diamantane xln.
Described step (2) also comprises synthetic 4-(1-adamantyl)-1,3-biphenol solution hot-water cure, make 4-(1-adamantyl)-1,3-biphenol precipitation, the unreacted Resorcinol of flush away simultaneously, suction filtration obtains 4-(1-adamantyl)-1,3-biphenol product after the vacuum drying oven drying, is used the toluene recrystallization then, get 4-(1-adamantyl)-1,3-biphenol xln.
For further realizing the object of the invention, the temperature of reaction of described step (1) is 70～110 ℃.The temperature of reaction of described step (2) is 60～90 ℃.
With respect to prior art, the present invention has following advantage:
1, novelty of the present invention a kind of preparation 4-(1-adamantyl)-1 with higher yields is provided, the method for 3-biphenol, product yield can reach 69.3%.
2, this method is a raw material with diamantane, liquid bromine and Resorcinol, and raw material is easy to get.
3, this method synthesis step is few, only through the diamantane bromination and with Resorcinol nucleophilic substitution two-step reaction, method is simple, products therefrom purity height.
Description of drawings
Fig. 1 is a 1-bromine diamantane infrared spectra;
Fig. 2 is 4-(1-adamantyl)-1,3-biphenol (ADRL) infrared spectrum;
Fig. 3 is 4-(1-adamantyl)-1,3-biphenol HNMR spectrogram;
Fig. 4 is 4-(1-adamantyl)-1,3-biphenol CNMR spectrogram;
Fig. 5 is the adamantine alkylphenol structural formula;
Fig. 6 is the adamantane structure formula;
Fig. 7 is 4-(1-adamantyl)-1,3-biphenol building-up reactions principle schematic.
Embodiment
The invention will be further described below in conjunction with embodiment; but be pointed out that; following examples can not be interpreted as limiting the scope of the invention, and those skilled in the art's foregoing according to the present invention still belongs to protection scope of the present invention to some nonessential improvement and the adjustment that the present invention makes.
Get in the reaction flask that 32g (0.235mol) diamantane, 0.235mol liquid bromine 12ml add the 100ml that the hydrogen bromide absorption unit is housed, be warming up to 50 ℃, react 0.5 hour, 90 ℃ were reacted 1.5 hours, and then at 120 ℃, reacted 2 hours.Placement is spent the night.Reduce unreacted bromine with saturated aqueous solution of sodium bisulfite, filter, be washed to neutrality, the vacuum drying oven oven dry.Use recrystallizing methanol, get light yellow crystallization, drying, yield 71.1%.
Get dried 1-bromine diamantane 10g (0.047mol), Resorcinol 5.2g (0.047mol), benzene 50ml (0.56mol) puts into the reaction flask that 100ml is connected to reflux.40 ℃ of reactions 6 hours, 60 ℃ of reactions 24 hours, 90 ℃ of back flow reaction 42 hours.The reacted solution hot-water cure makes 4-(1-adamantyl)-1,3-biphenol precipitation, and the unreacted Resorcinol of while flush away, suction filtration obtains product, and product is used the toluene recrystallization after the vacuum drying oven drying, get white product, yield 67.5%.Above-mentioned 4-(1-adamantyl)-1,3-biphenol synthetic reaction process as shown in Figure 7.
Get in the reaction flask that 32g (0.235mol) diamantane, 0.47mol liquid bromine 24ml add the 100ml that the hydrogen bromide absorption unit is housed, be warming up to 80 ℃ of reactions 6.5 hours,, reacted 3 hours then at 110 ℃.Placement is spent the night.Reduce unreacted bromine with saturated aqueous solution of sodium bisulfite, filter, be washed to neutrality, the vacuum drying oven oven dry.Use recrystallizing methanol, get light yellow crystallization, drying, yield 90.0%.
Get dried 1-bromine diamantane 10g (0.047mol), Resorcinol 10.4g (0.094mol), benzene 70ml (0.79mol) puts into the reaction flask that 100ml is connected to reflux, 60 ℃ of reactions 8 hours, 90 ℃ of back flow reaction 40 hours.The reacted solution hot-water cure makes 4-(1-adamantyl)-1,3-biphenol precipitation, and the unreacted Resorcinol of while flush away, suction filtration obtains product, and product is used the toluene recrystallization after the vacuum drying oven drying, get white product, yield 69.3%.Above-mentioned 4-(1-adamantyl)-1,3-biphenol synthetic reaction process as shown in Figure 7.
Get in the reaction flask that 32g (0.235mol) diamantane, 1.175mol liquid bromine 60ml add the 250ml that the hydrogen bromide absorption unit is housed, be warming up to 60 ℃, react 8 hours, 80 ℃ were reacted 10 hours, and then at 115 ℃, reacted 6 hours.Placement is spent the night.Steam unreacted liquid bromine 30-50ml, with the unreacted bromine of saturated aqueous solution of sodium bisulfite reduction residue, filter then, be washed to neutrality, the vacuum drying oven oven dry.Use recrystallizing methanol, get light yellow crystallization, drying, yield 94.0%.
Get dried 1-bromine diamantane 10g (0.047mol), Resorcinol 26g (0.235mol), benzene 150ml (1.69mol) puts into the reaction flask that 250ml is connected to reflux, 90 ℃ of back flow reaction 5 hours.The reacted solution hot-water cure makes 4-(1-adamantyl)-1,3-biphenol precipitation, and the unreacted Resorcinol of while flush away, suction filtration obtains product, and product is used the toluene recrystallization after the vacuum drying oven drying, get white product, yield 45.0%.Above-mentioned 4-(1-adamantyl)-1,3-biphenol synthetic reaction process as shown in Figure 7.
Analyze embodiment
(1) infrared analysis
Products therefrom prepares sample and carries out infrared spectroscopy (FTIR) and analyze among the embodiment 1.The preparation of KBr pressed disc method is adopted in specimen preparation, and sample is analyzed on NICOLET 760 type infrared spectrophotometers.Specifically be, sample was dried 10 hours down for 50 ℃ in vacuum drying oven through the toluene secondary recrystallization, and the sample that takes a morsel KBr compressing tablet is analyzed through infrared spectroscopy (FTIR), gets the IR spectrogram.
As shown in Figure 1, be positioned at 673cm in 1-bromine diamantane (ADBr) spectrogram
-1What locate is C-Br (by force) absorption peak, disappears with this peak behind the resorcin reaction.As shown in Figure 2, at 4-(1-adamantyl)-1,3-biphenol (ADRL) infrared spectrum as seen, products therefrom is then respectively at 3486cm
-1And 3396cm
-1The absorption peak that two phenolic hydroxyl groups occur is with 3420cm in the Resorcinol infrared spectrum
-1An absorption peak difference only appears (owing to the symmetry of phenolic hydroxyl group in the Resorcinol, an absorption peak only appears in spectrogram), this is owing on the phenyl ring substitution reaction has taken place, and has destroyed original symmetry, and variation has taken place the phenolic hydroxyl group absorption peak that is under the varying environment.By Fig. 1 and Fig. 2 analytical results as can be known, reaction has taken place with Resorcinol in 1-bromine diamantane really, has formed adamantine alkylphenol.Can confirm further that below by nmr analysis reaction product is 4-(1-adamantyl)-1, the 3-biphenol.
(2) nmr analysis: prepare sample with embodiment 1 products therefrom, adopt Bruker 400MHz nuclear magnetic resonance analyser, solvent is DMSO.Specifically be, sample was dried 10 hours down for 50 ℃ in vacuum drying oven through the toluene secondary recrystallization, and the sample that takes a morsel is dissolved in deuterium among the DMSO, carries out nmr analysis, and its analytical results is shown in Fig. 3,4.
Fig. 3 is 4-(1-adamantyl)-1, the 3-biphenol
1The HNMR spectrogram; Fig. 4 is 4-(1-adamantyl)-1, the 3-biphenol
13The CNMR spectrogram; Shown in Fig. 3,4, each is composed the peak and belongs to as follows:
1HNMR:8.99 (1H), 8.89 (1H) are the phenolic hydroxyl group proton signal, 6.79 (1H), 6.21 (1H), 6.10 (1H) they are hydrogen absorption peak on the phenyl ring, 1.98 (9H), 1.68 (6H) they are diamantane skeleton hydrogen absorption peak.
13CNMR:a:155.8, c: δ 156.6; B: δ 103.6, d: δ 105.5; E, f: δ 126.6,126.4 is a carbon signal on the phenyl ring.Each peak of δ 28.5-40.43 is a carbon signal on the diamantane, each peak ownership situation: C1: δ 40.4; C2, C8, C9: δ 36.7; C3, C5, C7:35.4; C4, C6, C10: δ 28.5, numbering as shown in Figure 6.
By
1HNMR and
13The CNMR spectrum analysis is the result can see, Resorcinol
1Has only a phenolic hydroxyl group peak in the HNMR spectrogram, observe visible two the phenolic hydroxyl group peaks of Fig. 3, lay respectively at 8.99 (1H) and δ 8.89 (1H), substitution reaction has taken place on the bimodal appearance explanation phenyl ring, and be asymmetric replacement, the deducibility replacement can only occur in f shown in Figure 5 position in view of the above, and can not occur in b or e position.Occur the chemical shift peak of hydrogen on three phenyl ring between the δ 6-7, further specifying product is structure shown in Figure 5.Observe Fig. 4
13CNMR spectrogram, δ 100-160 are the chemical shift of benzene, with Resorcinol
13The CNMR spectrogram is compared, because asymmetric substitution reaction has taken place on phenyl ring, phenyl ring no longer has symmetry in the product, thereby represents the spectral line number of carbon on the phenyl ring also to increase to 6 by 4.In sum, can determine that the synthetic product is 4-(1-adamantyl)-1,3-biphenol, structure are shown in Figure 5.
Claims (5)
1, a kind of synthetic method of adamantine alkylphenol is characterized in that comprising the steps:
(1) diamantane bromination: with diamantane and liquid bromine is 1: 1～5 to mix in molar ratio, under 50-120 ℃ of temperature condition, reacts 4-24 hour, synthetic 1-bromine diamantane;
(2) be 1: 1～5 to mix in molar ratio with step (1) synthetic 1-bromine diamantane and Resorcinol, add organic solvent simultaneously, the add-on of described organic solvent and the mol ratio of Resorcinol are 7～12: 1; Under 40-90 ℃ of temperature condition, reacted 5-72 hour, synthesized 4-(1-adamantyl)-1, the 3-biphenol.
2, according to the synthetic method of the described adamantine alkylphenol of claim 1, the temperature of reaction that it is characterized in that described step (1) is 70～110 ℃.
3, according to the synthetic method of the described adamantine alkylphenol of claim 1, it is characterized in that, described step (1) also comprises with saturated aqueous solution of sodium bisulfite reduces unreacted bromine, filter synthetic 1-bromine diamantane, be washed to neutrality, recrystallizing methanol is used in the vacuum drying oven oven dry, gets 1-bromine diamantane xln.
According to the synthetic method of claim 1 or 3 described adamantine alkylphenols, it is characterized in that 4, described step (2) also comprises synthetic 4-(1-adamantyl)-1,3-biphenol solution hot-water cure, make 4-(1-adamantyl)-1,3-biphenol precipitation, the unreacted Resorcinol of flush away simultaneously, suction filtration obtains 4-(1-adamantyl)-1,3-biphenol product after the vacuum drying oven drying, is used the toluene recrystallization then, get 4-(1-adamantyl)-1,3-biphenol xln.
5, according to the synthetic method of the described adamantine alkylphenol of claim 1, the temperature of reaction that it is characterized in that described step (2) is 60～90 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429095B (en) * | 2008-11-17 | 2011-08-17 | 庞明 | Process for producing bromoadamantane |
| CN114573801A (en) * | 2022-01-26 | 2022-06-03 | 安徽理工大学 | Preparation method of phenol red type polyarylate material |
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2006
- 2006-11-10 CN CN 200610123443 patent/CN1948250A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429095B (en) * | 2008-11-17 | 2011-08-17 | 庞明 | Process for producing bromoadamantane |
| CN114573801A (en) * | 2022-01-26 | 2022-06-03 | 安徽理工大学 | Preparation method of phenol red type polyarylate material |
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