CN102167692B - Synthesis method of alkyl-substituted benzocrown ether - Google Patents
Synthesis method of alkyl-substituted benzocrown ether Download PDFInfo
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- CN102167692B CN102167692B CN201110050592.4A CN201110050592A CN102167692B CN 102167692 B CN102167692 B CN 102167692B CN 201110050592 A CN201110050592 A CN 201110050592A CN 102167692 B CN102167692 B CN 102167692B
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- hat
- ether
- benzocrown
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000001308 synthesis method Methods 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 28
- -1 crown ether compounds Chemical class 0.000 claims abstract description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 16
- 238000010189 synthetic method Methods 0.000 claims description 16
- 239000003929 acidic solution Substances 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 11
- 229960001701 chloroform Drugs 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- WFRBDWRZVBPBDO-UHFFFAOYSA-N 2-methyl-2-pentanol Chemical compound CCCC(C)(C)O WFRBDWRZVBPBDO-UHFFFAOYSA-N 0.000 claims description 6
- KRIMXCDMVRMCTC-UHFFFAOYSA-N 2-methylhexan-2-ol Chemical compound CCCCC(C)(C)O KRIMXCDMVRMCTC-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 14
- 238000007086 side reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 238000005804 alkylation reaction Methods 0.000 abstract description 3
- 150000002170 ethers Chemical class 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 30
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 22
- 239000012043 crude product Substances 0.000 description 20
- 238000001914 filtration Methods 0.000 description 20
- 238000010992 reflux Methods 0.000 description 20
- 125000000217 alkyl group Chemical group 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000000643 oven drying Methods 0.000 description 10
- 238000004886 process control Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000004949 mass spectrometry Methods 0.000 description 9
- 150000004996 alkyl benzenes Chemical class 0.000 description 7
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- 150000003983 crown ethers Chemical class 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 0 C1*c(cccc2)c2OCCOCCOc(cccc2)c2OCCOC1 Chemical compound C1*c(cccc2)c2OCCOCCOc(cccc2)c2OCCOC1 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002633 crown compound Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007336 electrophilic substitution reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DSFHXKRFDFROER-UHFFFAOYSA-N C1OCCOCCOc(cccc2)c2OCCOCCOC1 Chemical compound C1OCCOCCOc(cccc2)c2OCCOCCOC1 DSFHXKRFDFROER-UHFFFAOYSA-N 0.000 description 1
- CDVQWFXYOJACMS-UHFFFAOYSA-N CC(C)(C)c(cc1)cc2c1OCCOCCOCCOCCOCCO2 Chemical compound CC(C)(C)c(cc1)cc2c1OCCOCCOCCOCCOCCO2 CDVQWFXYOJACMS-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of alkyl-substituted benzocrown ether, belonging to the technical field of synthesis of crown ether compounds. The synthesis process comprises the following steps of: dissolving a specific benzocrown ether raw material in an appropriate solvent system; and reacting with an alcohol compound which is dissolved in the specific solvent in advance, at lower reaction temperature under the catalytic action of polyphosphoric acid to obtain a corresponding alkyl-substituted benzocrown ether product. By adopting the synthesis process, the problems of low alkylation reaction transformation ratio of the conventional benzocrown ether and alcohol compound, the presence of side reaction, difficulty in separating and purifying, difficulty in controlling reaction heat and the like can be solved; the synthesis method is suitable for the synthesis and enlarged production of various types of alkyl-substituted benzocrown ethers; and the product is easy and convenient to purify, and has very high purity and the yield of over 90 percent.
Description
Technical field
The invention belongs to the synthesis technical field of crown ether compound, be specifically related to a kind of synthetic method of alkyl-substituted benzocrown ether.
Background technology
1967, Pedersen was synthetic and reported the polynary ether compound of large ring first, opened crown ether research prelude (Pedersen et al.J.Am.Chem.S.1967,89,7017-7036).The special property of crown ether is that it is to the cationic very strong coordination ability of alkalies and alkaline earth, and this coordination shows obvious selectivity along with the difference of ether ring hole size, heteroatomic kind and atom number to the special metal ion.As the motif compound of the numerous areas such as coordination chemistry, extraction chemistry, phase-transfer catalysis, ion selectivity carrier, crown ether has attracted increasing concern.In recent years, crown compound has represented application potential aspect the extracting and separating of high heat release radioelement again in the nuclear fuel reprocessing flow process.Such as, as extraction agent, extract radioactivity based on dicyclohexyl-18-crown-6 from high activity liquid waste
90sr
2+the extraction procedure of ion has been reported, and passed through hot experiment checking (Wang Jianchen, etc. atomic energy science and technology, 1998,32,57-62).
The difference of the substituted radical character on crown compound can affect complexation strength, selectivity and the solvability of itself and metal ion.Than unsubstituted crown ether, the lipophilicity of benzo-crown ether Yin Qigengjia and more concerned under study for action.But the latter's ungood solvability in low polar solvent, make it to be difficult to direct application.Recent research shows, on the aromatic ring of benzo-crown ether, introduces alkyl, especially the alkyl of large volume, effective way (the Sachleben et al.Tetrahedron that addresses the above problem, realizes the benzo-crown ether industrial application, 1997,53,13567-13582).
Realize the alkylation of benzo-crown ether, mainly contain two kinds of approach.One pyrocatechol that is based on corresponding alkyl replacement, as initial feed, obtains product by typical Williamson ethers building-up reactions; The 2nd, utilize alcohol under the protonic acid katalysis, directly corresponding alkyl by electrophilic substitution reaction and on keyed jointing on the aromatic ring of benzo-crown ether.The former is because the raw material of different substituents need to be controlled different reaction conditionss, and synthetic route is tediously long, and side reaction is often many, and yield is low, does not have the value of industrial application.Such as, the synthetic yield of the dibenzo that di-t-butyl that Pedersen reports replaces-18-hat-6 is only 17%, and indicate purifying process have difficulties (Pedersen et al.J.Am.Chem.S.1967,89,7017-7036).
More report is for a rear route of synthesis.Common synthetic method is that benzo-crown ether is added in excessive polyphosphoric acid (PPA) medium, the alcohol that adds again corresponding construction, under 60-70 ℃ of temperature condition, the reaction sufficiently long separates after the time and obtains product (Tashmukhamedova et al.Chem.Heterycl.Compd.1986,22,1178-1185).This reaction belongs to typical electrophilic substitution reaction mechanism, alcohol as reactant, especially the higher alcohols that there is the large volume alkyl, under the effect of protonic acid polyphosphoric acid, easily remove the hydroxyl in molecular structure, produce a large amount of carbonium ions, the phenyl ring of attack electronic cloud enrichment stably, thus realize the alkylation on phenyl ring.Yet, there is the shortcoming of following several respects in the synthesis technique of having reported at present: be at first that the reaction raw materials transformation efficiency is not good, substantially all can have side reaction product, and, because the character such as side reaction product structure, polarity are close with product, later separation purifying difficulty is larger.The synthetic method of having reported all needs to adopt the means such as post separation in purge process, and efficiency is not high, affects product yield simultaneously; Secondly, this reaction process very exothermic, and polyphosphoric acid reaction system viscosity is very large, and the benzo-crown ether raw material is directly mixed with it and is difficult to guarantee evenly.In reaction process, along with adding of alcohols, easily cause the too high and difficult heat radiation of local temperature, thereby increase the side reaction odds, and the control that also is unfavorable for amplifying temperature condition in synthesis technique; Again, because alkylating reagent is substantially all higher alcohols, its fusing point generally can be too not low, and what have exists with solid form at ambient temperature often, and in reinforced process, the control of reaction heat has difficulties, and very easily causes temperature in subrange to rise quickly.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of alkyl-substituted benzocrown ether, in the existing alkyl-substituted benzocrown ether synthetic method of solution, reaction conversion ratio is not good, and side reaction is more and separating-purifying is difficult, and reaction heat is difficult to the problems such as control.
A kind of synthetic method of alkyl-substituted benzocrown ether, is characterized in that, comprises the steps:
(1) benzo-crown ether is dissolved in solvent I, and adds polyphosphoric acid catalyzed dose, stir, make the acidic solution system of benzo-crown ether;
(2) alcohol compound is dissolved in solvent II, slowly joins in the acidic solution system of benzo-crown ether;
(3) controlling temperature of reaction system is 25-55 ℃, keeps stirring, and reacts more than 1 hour;
(4) while finishing reaction, the hydrolysis polyphosphoric acid is also isolated organic phase, and recrystallization after solvent evaporated, can obtain highly purified alkyl-substituted benzocrown ether product.
Described temperature of reaction system is 33-40 ℃, and the reaction times is 3-5 hour.
Described benzo-crown ether is phendioxin 2-hat-4, phendioxin 5-hat-5, phendioxin 8-hat-6, dibenzo-21-hat 7, dibenzo-12-crown-4, dibenzo-15-hat-5, dibenzo-18-hat-6, dibenzo-24-hat-8.
Described alcohol compound is Virahol, isopropylcarbinol, the trimethyl carbinol, benzylalcohol, tertiary amyl alcohol, 2-methyl-2-amylalcohol, 2-methyl-2-hexanol, 2,2,4-trimethylammonium-1-amylalcohol.
Described solvent I is methylene dichloride, trichloromethane, ethyl acetate, tetracol phenixin, ethylene dichloride, benzene, toluene, isopropyl benzene, o-Xylol, p-Xylol, m-xylene, chlorobenzene or orthodichlorobenzene.
Described solvent II is methylene dichloride, trichloromethane, ethyl acetate, tetracol phenixin, ethylene dichloride, benzene, toluene, isopropyl benzene, o-Xylol, p-Xylol, m-xylene, chlorobenzene, orthodichlorobenzene, ether, methyl alcohol or ethanol.
Add phenyl ring content in polyphosphoric acid catalyzer and benzo-crown ether mol ratio be 1: (1-20), preferred molar ratio is 1: (2-5).
Add phenyl ring content in alcohol compound and benzo-crown ether mol ratio be (1-30): 1, preferred molar ratio is (2-10): 1.
The mass ratio of the solubilizing agent II of institute and alcohol compound is (0.2-20): 1, and preferred mass is than being (2-5): 1.
Beneficial effect of the present invention: method of the present invention is dissolved in benzo-crown ether in suitable solvent in advance, the dispersion of having avoided benzo-crown ether and full-bodied polyphosphoric acid in existing method directly to mix participating in reaction to cause is uneven, heat radiation difficulty and follow the shortcoming such as side reaction generation, be beneficial to the control of amplifying temperature in production, also simplified the later separation purifying technique; Alcohol compound is also to be dissolved in advance in appropriate solvent, has both avoided the problem of its difficult feed under low room temperature condition, and the reaction heat that also allows fill process produce easily disperses, and can not bring because local temperature is too high side reaction.It is lower that method of the present invention is controlled temperature of reaction, and the side reactions such as ether ring cracking of having avoided hot conditions to bring, be beneficial to the finished product separation and purification; Reaction efficiency is high, and feedstock conversion is complete, and purifying process is simple, without column chromatography, also can guarantee product purity>90%, and productive rate is also more than 90%.
Embodiment
Below with different carbon chain lengths (Cn, wherein n means the substituted alkyl carbon atom quantity, n=3-7) the alkyl substituted diphenylamine also-18-hat-6 or different carbon chain lengths (Cn, wherein n means the substituted alkyl carbon atom quantity, n=3-7) alkyl substituted benzene also-18-hat-6 synthesize example, in conjunction with specific implementation method, the present invention is described.
Embodiment 1:C7 alkyl substituted diphenylamine also-18-hat-6 synthetic
Take dibenzo-18-hat-6 and 2-methyl-2-hexanol is raw material, in the dichloromethane solvent system synthetic C7 alkyl substituted diphenylamine also-reaction equation of 18-hat-6 is as follows:
5.4g dibenzo-18-hat-6 (DB18C6) are dissolved in to the 75mL methylene dichloride, then add 50g polyphosphoric acid (PPA), guarantee system stirs.Get 16g 2-methyl-2-hexanol and be dissolved in the 30mL methylene dichloride, and this mixing solutions slowly is added dropwise in the acidic solution system of aforementioned DB18C6, drip the process control system temperature and be no more than 30 ℃.After dropwising, keep stirring, 38 ℃ of reactions 3 hours
Reaction adds deionized water after finishing in system, hydrolysis PPA.Isolate organic phase, be washed to neutrality.Add anhydrous magnesium sulfate drying toward organic phase, after filtration, revolve to steam and remove CH
2cl
2obtain crude product.The gained crude product is dissolved in the 50mL normal heptane, refluxes half an hour, add the gac of 5wt%, then after refluxing 20 minutes, heat filtering, filtrate is standing cooling, separates out white crystal.Filter and obtain the finished product in 60 ℃ of vacuum drying oven dryings, productive rate is 91%.The gas-chromatography test result shows that the purity of product is 94%.Mass spectroscopy: 556.25 (calculated value is 556.77).6.88(CH，2H，s)，6.83(CH，2H，d)，6.79(CH，2H，d)，4.08(CH
2，8H，d)，3.79(CH
2，8H，m)，1.54(CH
2，4H，t)，1.18(CH
3，12H，s)，0.97(CH
2，8H，m)，0.79(CH
3，6H，t)。
Embodiment 2:C6 alkyl substituted diphenylamine also-18-hat-6 synthetic
Take dibenzo-18-hat-6 and 2-methyl-2-amylalcohol is raw material, in the trichloromethane solvent system synthetic C6 alkyl substituted diphenylamine also-reaction equation of 18-hat-6 is as follows:
5.4g dibenzo-18-hat-6 (DB18C6) are dissolved in to the 60mL trichloromethane, then add 40g polyphosphoric acid (PPA), guarantee system stirs.Get 15g 2-methyl-2-amylalcohol and be dissolved in the 20mL trichloromethane, and this mixing solutions slowly is added dropwise in the acidic solution system of aforementioned DB18C6, drip the process control system temperature and be no more than 30 ℃.After dropwising, keep stirring, 35 ℃ of reactions 4 hours
Reaction adds deionized water after finishing in system, hydrolysis PPA.Isolate organic phase, be washed to neutrality.Add anhydrous magnesium sulfate drying toward organic phase, after filtration, revolve to steam and remove CH
2cl
3obtain crude product.The gained crude product is dissolved in the 50mL normal heptane, refluxes half an hour, add the gac of 5wt%, then after refluxing 20 minutes, heat filtering, filtrate is standing cooling, separates out white crystal.Filter and obtain the finished product in 60 ℃ of vacuum drying oven dryings, productive rate is 90%.The gas-chromatography test result shows that the purity of product is 93%.Mass spectroscopy: 528.31 (calculated value is 528.72).Proton nmr spectra (chemical shift δ/ppm, solvent is DMSO-d6): 6.85 (CH, 2H, s), 6.82 (CH, 2H, d), 6.78 (CH, 2H, d), 4.05 (CH
2, 8H, d), 3.83 (CH
2, 8H, m), 1.51 (CH
2, 4H, t), 1.20 (CH
3, 12H, s), 0.99 (CH
2, 4H, m), 0.77 (CH
3, 6H, t).Experimental data shows to meet the target product structure.
Embodiment 3:C5 alkyl substituted diphenylamine also-18-hat-6 synthetic
Take dibenzo-18-hat-6 and tertiary amyl alcohol is raw material, in the toluene solvant system synthetic C5 alkyl substituted diphenylamine also-reaction equation of 18-hat-6 is as follows:
5.4g dibenzo-18-hat-6 (DB18C6) are dissolved in 100mL toluene, then add 60g polyphosphoric acid (PPA), guarantee system stirs.Get the 13.5g tertiary amyl alcohol and be dissolved in 30mL toluene, and this mixing solutions slowly is added dropwise in the acidic solution system of aforementioned DB18C6, drip the process control system temperature and be no more than 30 ℃.After dropwising, keep stirring, 40 ℃ of reactions 4 hours.
Reaction adds deionized water after finishing in system, hydrolysis PPA.Isolate organic phase, be washed to neutrality.Add anhydrous magnesium sulfate drying toward organic phase, after filtration, revolve to steam and remove toluene and obtain crude product.The gained crude product is dissolved in the 50mL normal heptane, refluxes half an hour, add the gac of 5wt%, then after refluxing 20 minutes, heat filtering, filtrate is standing cooling, separates out white crystal.Filter and obtain the finished product in 60 ℃ of vacuum drying oven dryings, productive rate is 92%.The gas-chromatography test result shows that the purity of product is 97%.Mass spectroscopy: 500.29 (calculated value is 500.67).Proton nmr spectra (chemical shift δ/ppm, solvent is DMSO-d6): 6.84 (CH, 2H, s), 6.83 (CH, 2H, d), 6.77 (CH, 2H, d), 4.07 (CH
2, 8H, d), 3.82 (CH
2, 8H, m), 1.57 (CH
2, 4H, t), 1.24 (CH
3, 12H, s), 0.60 (CH
3, 6H, t).Experimental data shows to meet the target product structure.
Embodiment 4:C4 alkyl substituted diphenylamine also-18-hat-6 synthetic
Take dibenzo-18-hat-6 and the trimethyl carbinol is raw material, in the xylene solvent system synthetic C4 alkyl substituted diphenylamine also-reaction equation of 18-hat-6 is as follows:
5.4g dibenzo-18-hat-6 (DB18C6) are dissolved in 75mL dimethylbenzene, then add 54g polyphosphoric acid (PPA), guarantee system stirs.Get the 12g trimethyl carbinol and be dissolved in 10mL dimethylbenzene, and this mixing solutions slowly is added dropwise in the acidic solution system of aforementioned DB18C6, drip the process control system temperature and be no more than 30 ℃.After dropwising, keep stirring, 38 ℃ of reactions 3.5 hours.
Reaction adds deionized water after finishing in system, hydrolysis PPA.Isolate organic phase, be washed to neutrality.Add anhydrous magnesium sulfate drying toward organic phase, after filtration, revolve steaming and obtain crude product except removal xylene.The gained crude product is dissolved in the 50mL normal heptane, refluxes half an hour, add the gac of 5wt%, then after refluxing 20 minutes, heat filtering, filtrate is standing cooling, separates out white crystal.Filter and obtain the finished product in 60 ℃ of vacuum drying oven dryings, productive rate is 90%.The gas-chromatography test result shows that the purity of product is 95%.Mass spectroscopy: 472.24 (calculated value is 472.61).Proton nmr spectra (chemical shift δ/ppm, solvent is DMSO-d6): 6.92 (CH, 2H, s), 6.84 (CH, 4H, t), 4.06 (CH
2, 8H, d), 3.83 (CH
2, 8H, m), 1.25 (CH
3, 18H, s).Experimental data shows to meet the target product structure.
Embodiment 5:C3 alkyl substituted diphenylamine also-18-hat-6 synthetic
Take dibenzo-18-hat-6 and Virahol is raw material, in the ethyl acetate solvent system synthetic C3 alkyl substituted diphenylamine also-reaction equation of 18-hat-6 is as follows:
5.4g dibenzo-18-hat-6 (DB18C6) are dissolved in the 75mL ethyl acetate, then add 60g polyphosphoric acid (PPA), guarantee system stirs.Get the 10g Virahol and be dissolved in the 15mL ethyl acetate, and this mixing solutions slowly is added dropwise in the acidic solution system of aforementioned DB18C6, drip the process control system temperature and be no more than 30 ℃.After dropwising, keep stirring, 40 ℃ of reactions 5 hours.
Reaction adds deionized water after finishing in system, hydrolysis PPA.Isolate organic phase, be washed to neutrality.Add anhydrous magnesium sulfate drying toward organic phase, after filtration, revolve to steam and remove ethyl acetate and obtain crude product.The gained crude product is dissolved in the 50mL normal heptane, refluxes half an hour, add the gac of 5wt%, then after refluxing 20 minutes, heat filtering, filtrate is standing cooling, separates out white crystal.Filter and obtain the finished product in 60 ℃ of vacuum drying oven dryings, productive rate is 91%.It is correct that gas-chromatography test result display-object product goes out peak position.
Embodiment 6:C7 alkyl substituted benzene also-18-hat-6 synthetic
The phendioxin 8-of take hat-6 and 2-methyl-2-hexanol are raw material, in the dichloromethane solvent system synthetic C7 alkyl substituted benzene also-reaction equation of 18-hat-6 is as follows:
4.7g phendioxin 8-hat-6 (B18C6) are dissolved in to the 70mL methylene dichloride, then add 45g polyphosphoric acid (PPA), guarantee system stirs.Get 16g 2-methyl-2-hexanol and be dissolved in the 30mL methylene dichloride, and this mixing solutions slowly is added dropwise in the acidic solution system of aforementioned B18C6, drip the process control system temperature and be no more than 30 ℃.After dropwising, keep stirring, after 38 ℃ of reactions reaction in 3 hours finishes, in system, add deionized water, hydrolysis PPA.Isolate organic phase, be washed to neutrality.Add anhydrous magnesium sulfate drying toward organic phase, after filtration, revolve to steam and remove CH
2cl
2obtain crude product.The gained crude product is dissolved in the 50mL normal heptane, refluxes half an hour, add the gac of 5wt%, then after refluxing 20 minutes, heat filtering, filtrate is standing cooling, separates out white crystal.Filter and obtain the finished product in 60 ℃ of vacuum drying oven dryings, productive rate is 95%.The gas-chromatography test result shows that the purity of product is 97%.Mass spectroscopy: 410.35 (calculated value is 410.54).
Embodiment 7:C6 alkyl substituted benzene also-18-hat-6 synthetic
The phendioxin 8-of take hat-6 and 2-methyl-2-amylalcohol are raw material, in the dichloromethane solvent system synthetic C6 alkyl substituted benzene also-reaction equation of 18-hat-6 is as follows:
4.7g phendioxin 8-hat-6 (B18C6) are dissolved in to the 70mL methylene dichloride, then add 45g polyphosphoric acid (PPA), guarantee system stirs.Get 15g 2-methyl-2-amylalcohol and be dissolved in the 30mL methylene dichloride, and this mixing solutions slowly is added dropwise in the acidic solution system of aforementioned B18C6, drip the process control system temperature and be no more than 30 ℃.After dropwising, keep stirring, 38 ℃ of reactions 3.5 hours
Reaction adds deionized water after finishing in system, hydrolysis PPA.Isolate organic phase, be washed to neutrality.Add anhydrous magnesium sulfate drying toward organic phase, after filtration, revolve to steam and remove CH
2cl
2obtain crude product.The gained crude product is dissolved in the 50mL normal heptane, refluxes half an hour, add the gac of 5wt%, then after refluxing 20 minutes, heat filtering, filtrate is standing cooling, separates out white crystal.Filter and obtain the finished product in 60 ℃ of vacuum drying oven dryings, productive rate is 93%.The gas-chromatography test result shows that the purity of product is 92%.Mass spectroscopy: 396.29 (calculated value is 396.52).
Embodiment 8:C5 alkyl substituted benzene also-18-hat-6 synthetic
The phendioxin 8-of take hat-6 and tertiary amyl alcohol are raw material, in the dichloromethane solvent system synthetic C5 alkyl substituted benzene also-reaction equation of 18-hat-6 is as follows:
4.7g phendioxin 8-hat-6 (B18C6) are dissolved in to the 70mL methylene dichloride, then add 45g polyphosphoric acid (PPA), guarantee system stirs.Get the 13.5g tertiary amyl alcohol and be dissolved in the 30mL methylene dichloride, and this mixing solutions slowly is added dropwise in the acidic solution system of aforementioned B18C6, drip the process control system temperature and be no more than 30 ℃.After dropwising, keep stirring, 40 ℃ of reactions 4 hours
Reaction adds deionized water after finishing in system, hydrolysis PPA.Isolate organic phase, be washed to neutrality.Add anhydrous magnesium sulfate drying toward organic phase, after filtration, revolve to steam and remove CH
2cl
2obtain crude product.The gained crude product is dissolved in the 50mL normal heptane, refluxes half an hour, add the gac of 5wt%, then after refluxing 20 minutes, heat filtering, filtrate is standing cooling, separates out white crystal.Filter and obtain the finished product in 60 ℃ of vacuum drying oven dryings, productive rate is 91%.The gas-chromatography test result shows that the purity of product is 94%.Mass spectroscopy: 382.37 (calculated value is 382.49).
Embodiment 9:C4 alkyl substituted benzene also-18-hat-6 synthetic
The phendioxin 8-of take hat-6 and tertiary amyl alcohol are raw material, in the trichloromethane solvent system synthetic C4 alkyl substituted benzene also-reaction equation of 18-hat-6 is as follows:
4.7g phendioxin 8-hat-6 (B18C6) are dissolved in to the 80mL trichloromethane, then add 45g polyphosphoric acid (PPA), guarantee system stirs.Get the 12g trimethyl carbinol and be dissolved in the 15mL trichloromethane, and this mixing solutions slowly is added dropwise in the acidic solution system of aforementioned B18C6, drip the process control system temperature and be no more than 30 ℃.After dropwising, keep stirring, 38 ℃ of reactions 3 hours
Reaction adds deionized water after finishing in system, hydrolysis PPA.Isolate organic phase, be washed to neutrality.Add anhydrous magnesium sulfate drying toward organic phase, after filtration, revolve to steam and remove trichloromethane and obtain crude product.The gained crude product is dissolved in the 50mL normal heptane, refluxes half an hour, add the gac of 5wt%, then after refluxing 20 minutes, heat filtering, filtrate is standing cooling, separates out white crystal.Filter and obtain the finished product in 60 ℃ of vacuum drying oven dryings, productive rate is 96%.The gas-chromatography test result shows that the purity of product is 97%.Mass spectroscopy: 368.24 (calculated value is 368.46).
Embodiment 10:C3 alkyl substituted benzene also-18-hat-6 synthetic
The phendioxin 8-of take hat-6 and tertiary amyl alcohol are raw material, in the toluene solvant system synthetic C3 alkyl substituted benzene also-reaction equation of 18-hat-6 is as follows:
4.7g phendioxin 8-hat-6 (B18C6) are dissolved in to 100mL toluene, then add 45g polyphosphoric acid (PPA), guarantee system stirs.Get the 15g Virahol and be dissolved in 30mL toluene, and this mixing solutions slowly is added dropwise in the acidic solution system of aforementioned B18C6, drip the process control system temperature and be no more than 30 ℃.After dropwising, keep stirring, 40 ℃ of reactions 4 hours
Reaction adds deionized water after finishing in system, hydrolysis PPA.Isolate organic phase, be washed to neutrality.Add anhydrous magnesium sulfate drying toward organic phase, after filtration, revolve to steam and remove toluene and obtain crude product.The gained crude product is dissolved in the 50mL normal heptane, refluxes half an hour, add the gac of 5wt%, then after refluxing 20 minutes, heat filtering, filtrate is standing cooling, separates out white crystal.Filter and obtain the finished product in 60 ℃ of vacuum drying oven dryings, productive rate is 92%.The gas-chromatography test result shows that the purity of product is 91%.Mass spectroscopy: 354.19 (calculated value is 354.44).
Claims (9)
1. the synthetic method of an alkyl-substituted benzocrown ether, is characterized in that, comprises the steps:
(1) benzo-crown ether is dissolved in the solvent I, and adds polyphosphoric acid catalyzed dose, stir, make the acidic solution system of benzo-crown ether;
(2) alcohol compound is dissolved in the solvent II, slowly joins in the acidic solution system of benzo-crown ether;
(3) controlling temperature of reaction system is 25-55 ℃, keeps stirring, and reacts more than 1 hour;
(4) while finishing reaction, the hydrolysis polyphosphoric acid is also isolated organic phase, and recrystallization after solvent evaporated, can obtain highly purified alkyl-substituted benzocrown ether product;
Described high purity is that purity is greater than 90%;
Described solvent I is methylene dichloride, trichloromethane, ethyl acetate, tetracol phenixin, ethylene dichloride, benzene, toluene, isopropyl benzene, o-Xylol, p-Xylol, m-xylene, chlorobenzene or orthodichlorobenzene;
Described solvent II is methylene dichloride, trichloromethane, ethyl acetate, tetracol phenixin, ethylene dichloride, benzene, toluene, isopropyl benzene, o-Xylol, p-Xylol, m-xylene, chlorobenzene, orthodichlorobenzene, ether, methyl alcohol or ethanol:
Described alcohol compound is Virahol, isopropylcarbinol, the trimethyl carbinol, benzylalcohol, tertiary amyl alcohol, 2-methyl-2-amylalcohol, 2-methyl-2-hexanol, 2,2,4-trimethylammonium-1-amylalcohol.
2. a kind of synthetic method of alkyl-substituted benzocrown ether according to claim 1, is characterized in that, described temperature of reaction system is 33-40 ℃, and the reaction times is 3-5 hour.
3. a kind of synthetic method of alkyl-substituted benzocrown ether according to claim 1, it is characterized in that, described benzo-crown ether is phendioxin 2-hat-4, phendioxin 5-hat-5, phendioxin 8-hat-6, dibenzo-21-hat 7, dibenzo-12-crown-4, dibenzo-15-hat-5, dibenzo-18-hat-6, dibenzo-24-hat-8.
4. a kind of synthetic method of alkyl-substituted benzocrown ether according to claim 1, is characterized in that, add phenyl ring content in polyphosphoric acid catalyzer and benzo-crown ether mol ratio be 1:(1-20).
5. a kind of synthetic method of alkyl-substituted benzocrown ether according to claim 1, is characterized in that, add phenyl ring content in polyphosphoric acid catalyzer and benzo-crown ether mol ratio be 1:(2-5).
6. a kind of synthetic method of alkyl-substituted benzocrown ether according to claim 1, is characterized in that, add phenyl ring content in alcohol compound and benzo-crown ether mol ratio be (1-30): 1,
7. a kind of synthetic method of alkyl-substituted benzocrown ether according to claim 1, is characterized in that, add phenyl ring content in alcohol compound and benzo-crown ether mol ratio be (2-10): 1.
8. a kind of synthetic method of alkyl-substituted benzocrown ether according to claim 1, is characterized in that, the mass ratio of institute's solubilizing agent II and alcohol compound is (0.2-20): 1.
9. a kind of synthetic method of alkyl-substituted benzocrown ether according to claim 1, is characterized in that, the mass ratio of institute's solubilizing agent II and alcohol compound is (2-5): 1.
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