CN103086860A - One-step synthesis method of 1-benzoylpyrene - Google Patents
One-step synthesis method of 1-benzoylpyrene Download PDFInfo
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- CN103086860A CN103086860A CN2013100618974A CN201310061897A CN103086860A CN 103086860 A CN103086860 A CN 103086860A CN 2013100618974 A CN2013100618974 A CN 2013100618974A CN 201310061897 A CN201310061897 A CN 201310061897A CN 103086860 A CN103086860 A CN 103086860A
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- Prior art keywords
- pyrene
- alpw
- benzoyl
- catalyzer
- reaction
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- FGCOCPAQFSREBF-UHFFFAOYSA-N phenyl(pyren-1-yl)methanone Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1C(=O)C1=CC=CC=C1 FGCOCPAQFSREBF-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title 1
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 23
- 239000012074 organic phase Substances 0.000 claims description 22
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000004411 aluminium Substances 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 230000003252 repetitive effect Effects 0.000 claims description 7
- 238000005201 scrubbing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 238000004451 qualitative analysis Methods 0.000 claims description 2
- 238000004445 quantitative analysis Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000000975 dye Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 238000005917 acylation reaction Methods 0.000 description 15
- 238000006555 catalytic reaction Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000011964 heteropoly acid Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- -1 carboxylic acid halides Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 238000005618 Fries rearrangement reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 101100323029 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) alc-1 gene Proteins 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing an organic synthesis intermediate compound 1-benzoylpyrene having high yield and high selectivity through the catalytic Friedel-Crafts acylation reaction of condensed aromatic pyrene and benzoic anhydride by using cheap, accessible and hydrostable aluminum phosphotungstate and supported aluminum phosphotungstate as a catalyst and using non-polar solvent 1,2-dichloroethane as solvent. The 1-benzoylpyrene is widely used in multiple fields such as medicine, pesticide, dye and the like. The method is simple in reaction, convenient to operate, short in reaction time, low in reaction temperature, low in energy consumption and satisfactory in catalyst reusability, thus conforming to the requirements for greenness and environmental protection in the world at present.
Description
Technical field
The present invention relates to use the Friedel-Crafts acylation reaction, use respectively aluminium phosphotungstic acid, carried phospho-tungstic acid aluminium to make catalyzer, the method for synthetic 1-benzoyl pyrene.
Background technology
Aromatic ketone is as important organic synthesis intermediate, is widely used in medicine, agricultural chemicals, dyestuff, plastics, makeup synthetic; (as AlCl in Lewis acid
3, FeCl
3, TiCl
4Deng) or Brfnsted acid (HF, H
2SO
4, HCl etc.) under catalysis, obtained by acylting agent (being mainly carboxylic acid halides) and the Fries rearrangement reaction that Friedel-Crafts acylation reaction or aromatic ester occur aromatic hydrocarbons; Catalyzer is often excessive in traditional acylation reaction, causes producing comparatively serious " three wastes " problem in industrial aftertreatment, causes equipment corrosion serious in production process simultaneously; So seek low catalytic amount, environmental friendliness, cheapness, easy recovery, reusable green catalyst, replace carboxylic acid halides to make acylting agent with carboxylic acid or acid anhydrides, become the development trend of this reaction.
Heteropolyacid is as a kind of novel, the acid catalyst of environmental protection has strongly-acid, the advantages such as high reactivity, enjoy broad research person's concern, but be difficult to, specific surface area less (l-10m difficult with product separation in recovery, partial reaction due to heteropolyacid in homogeneous catalytic reaction
2/ the weak point such as g) has limited to a certain extent its application in acid catalyzed reaction, thereby has been difficult to better bring into play its catalytic performance; In nonhomogeneous system, use heteropolyacid salt or heteropolyacid is immobilized on porous support, can improve its catalytic performance, separate and reclaim catalyzer, reduce production costs.
The character of Keggin type heteropolyacid salt depends on cationic type, the smaller category-A salt of positively charged ion has the character similar to the body heteropolyacid: soluble in water, lower specific surface area is arranged, on the contrary, the category-B salt that positively charged ion is larger is not soluble in water, and larger specific surface area and relatively high thermostability are arranged; Given this, it is comparatively extensive that the category-B salt that positively charged ion is larger is studied, be applied in multiple catalyzed reaction, and the research of category-A salt is less, the people (Tetrahedron Letters 44 (2003) 5343-5345) such as Habib Firouzabadi have studied under the trifluoroacetic anhydride existence condition, the acylation reaction of aluminium phosphotungstic acid catalyzing aromatic hydrocarbon and carboxylic acid, has the reaction conditions gentleness, reaction times is shorter, the characteristics that the yield of product is higher, but this process has added more expensive reagent trifluoroacetic anhydride to remove the water that produces in reaction process; In addition, the acylation reaction of aluminium phosphotungstic acid catalyzing aromatic hydrocarbon and carboxylic acid has also been studied by this subject study group, although the yield of product is higher, temperature of reaction is high, and power consumption is large (Tetrahedron 60 (2004) 10843-10850); But because aluminium phosphotungstic acid belongs to category-A salt, have similar character to the body phospho-wolframic acid, will inevitably exist certain defective in the number acid catalyzed reaction; There is the investigator to study aluminium phosphotungstic acid is loaded on and improves its catalytic performance on porous support, Ch. the people (Journal of Molecular Catalysis A:Chemical 350 (2011) 83-90) such as Ramesh Kumar has studied the benzyl reaction of titanium dichloride load aluminium phosphotungstic acid catalysis methyl-phenoxide and phenylcarbinol, experimental result shows that catalyzer has showed good catalytic effect, and does not occur the leaching problem of active ingredient in reaction process.
The at present research for the Friedel-Crafts acylation reaction of aromatic hydrocarbons mainly concentrates on benzene and naphthalene and derivative thereof, and for the condensed-nuclei aromatics anthracene, phenanthrene, pyrene etc. also have a small amount of bibliographical information, but for aluminium phosphotungstic acid (AlPW
12O
40) and the synthetic 1-benzoyl pyrene of the acylation reaction of carried phospho-tungstic acid aluminium catalysis pyrene and benzoyl oxide, through By consulting literatures, report is not arranged both at home and abroad at present.
Summary of the invention
The object of the present invention is to provide a kind ofly to be easy to get with cheaply the AlPW of hydrostable Keggin type
12O
40, charge capacity is the 40 silicon dioxide carried AlPW of %
12O
40(40 % AlPW
12O
40/ SiO
2) or charge capacity be 40 % titanium dichloride load AlPW
12O
40(40 % AlPW
12O
40/ TiO
2) make catalyzer, high yield, highly selective catalyze and synthesize the method for 1-benzoyl pyrene under the condition of gentleness.
The one-step method for synthesizing of the 1-benzoyl pyrene described in the present invention is described below:
1) to catalyzer and non-polar solvent 1,2-ethylene dichloride (CH
2Cl
2-CH
2Cl
2) in the mixing solutions that forms, slowly add while stirring the acylting agent benzoyl oxide, mix and form mixing solutions 1,
VSolvent:
n(pyrene)=15:0.25,
n(catalyzer):
n(pyrene)=0.04 ~ 0.1.
2) the condensed-nuclei aromatics pyrene is slowly joined in mixing solutions 1,
n(pyrene):
n(benzoyl oxide)=1:1 ~ 1:7; 60 ~ 90
οWater bath with thermostatic control back flow reaction 10 ~ 120 min under C form reaction soln 2, stir in reaction process, make reaction soln 2 be down to room temperature after reaction.
3) reaction soln 2 is filtered, use CH
2Cl
2-CH
2Cl
2To filter residue repetitive scrubbing 2-3 time, and recycling; Filtrate is through GC-MS, and GC detects, and wherein material is carried out quantitative and qualitative analysis;
4) filtrate after step 3 filtration is extracted, extract organic phase, it is neutral that repetitive scrubbing to organic phase is;
5) organic phase is carried out drying after, the solvent in organic phase is removed in underpressure distillation, gets the yellow solid crude product, with crude product washing and recrystallization, gets yellow tabular crystal, and this material is carried out FT-IR,
1H NMR phenetic analysis is finished product 1-benzoyl pyrene.
In above-mentioned preparation method, the stirring in step 1 neutralization procedure 2 is magnetic agitation.
In above-mentioned preparation method, go out organic phase with extracted with diethyl ether successively in step 4, with the mixed solution (volume ratio is 1:10) of 36 % hydrochloric acid and frozen water to organic phase repetitive scrubbing 3-4 time, then standing demix in separating funnel, with chloroform extraction upper strata water 3-4 time, extraction liquid and lower floor's organic phase of chloroform extraction upper strata water are mixed, use saturated Na
2CO
3Repeatedly be washed till neutrality.
In above-mentioned preparation method, use anhydrous MgSO in step 5
4Organic phase is carried out drying; Use sherwood oil that crude product is washed and recrystallization in acetone.
In above-mentioned preparation method, the catalyzer in step 1 is AlPW
12O
40Or charge capacity is the 40 silicon dioxide carried AlPW of %
12O
40(40 % AlPW
12O
40/ SiO
2) or charge capacity be 40 % titanium dichloride load AlPW
12O
40(40 % AlPW
12O
40/ TiO
2).
In above-mentioned preparation method, charge capacity is the 40 silicon dioxide carried AlPW of %
12O
40The calculating of the charge capacity of catalyzer:
In formula:
ωCharge capacity for catalyzer;
m 1Be the quality of active ingredient aluminium phosphotungstic acid, g;
m 2Be the quality of carrier, g.
Explain: for example in this patent (
ω) AlPW
12O
40/ SiO
2The expression charge capacity is
ωSiO
2Load AlPW
12O
40Catalyzer.
The reaction equation that the present invention relates to is as follows:
Innovative point of the present invention is to use the AlPW of environmental protection
12O
40, 40 % AlPW
12O
40/ SiO
2With 40 % AlPW
12O
40/ TiO
2Catalysis condensed-nuclei aromatics pyrene and benzoyl oxide Friedel-Crafts acylation reaction; by the optimization to experiment conditions such as proportioning raw materials, catalyst levels, temperature of reaction, reaction times; the yield of the target product 1-benzoyl pyrene that obtains is higher; selectivity is good, has the reaction times short, and temperature of reaction is more suitable; the advantages such as catalyzer more easily reclaims, and reusability is good.Catalyzer is after three repeated experiments, and the yield of product and selectivity do not have great decline; The by product phenylformic acid, the more easily separated recovery of unreacted raw material pyrene has reduced " pollutions of the three wastes ", has realized the requirement of environmental protection.
Embodiment
Case study on implementation 1The preparation of titania support
Compound concentration is the Ti (SO of 1mol/L, 2mol/L respectively
4)
2Then solution and NaOH solution dropwise are added drop-wise to Ti (SO with the NaOH solution for preparing
4)
2In solution, dropwise rear continuation and stir 2-4 h, hold over night, the centrifugal SO that removes
4 2-Ion (is used BaCl
2Detect SO
4 2-Whether ion eliminates), gained solution is poured out tetrafluoroethylene reactor, 180
οReaction 24 h under C migrate out liquid in still, 80 after reaction finishes
οThe C oven dry is ground.
Case study on implementation 2AlPW
12O
40The preparation of catalyzer
Reference: Chen Min, fine chemistry industry, 25(112), 2005,1245-1248
10 g phospho-wolframic acids and 0.75 g aluminum nitrate are made into respectively the certain density aqueous solution, while stirring aluminum nitrate aqueous solution slowly are added drop-wise in phosphotungstic acid aqueous solution under room temperature, finish, continue to stir 30 min, in standing 2 h of room temperature, 80
οC is evaporated to moisture dried, in 100
οThe oven dry of C left and right, 300
οC roasting 3 h namely make dry A1PW
12O
40, it is standby that catalyzer is placed in moisture eliminator.
Case study on implementation 3 40 %Silicon dioxide carried aluminium phosphotungstic acid (40 % AlPW
12O
40/ SiO
2) preparation of catalyzer
Get a certain amount of nano silicon (buying in Aladdin company) carrier with the salt acid dipping of 5 % 2-3 days, use distilled water wash, centrifugal to neutral, dry a few hours under infrared lamp are at last 500
οStandby after roasting 3 h in the C retort furnace, 4 g cases are implemented the AlPW for preparing in 2
12O
40Catalyst dissolution slowly is added drop-wise in the beaker of the silicon-dioxide that the 10 above-mentioned processing of g are housed in 20 mL distilled water, and constantly stirs, and dropwises, and stirs 12 h, more standing 3h, and unnecessary moisture is by 80
οEvaporate to dryness under C, then 100
οThe lower oven dry in C left and right is at last 300
οRoasting 3 h under C make the AlPW that charge capacity is 40 %
12O
40/ SiO
2Catalyzer, it is standby that catalyzer is placed in moisture eliminator.
Case study on implementation 4 40 %Titanium dichloride load aluminium phosphotungstic acid (40 % AlPW
12O
40/ SiO
2) preparation of catalyzer
With the AlPW for preparing in 4 g cases enforcements 2
12O
40Catalyzer is dissolved in the mixing solutions of isopyknic water and methyl alcohol, then is added dropwise to case and implements 1 10 gTiO that prepare
2In the mixed system of water, ultrasonic 1h at room temperature, dipping 12 h, 150
οDry under C, at last 300
οRoasting 3 h under C, it is standby that catalyzer is placed in moisture eliminator.
Case study on implementation 5 ~ 7AlPW
12O
40, 40 % AlPW
12O
40/ SiO
2With 40 % AlPW
12O
40/ TiO
2The catalytic activity experiment of catalyzer to the acylation reaction of pyrene and benzoyl oxide
The AlPW that case study on implementation 2 ~ 4 is prepared
12O
40, 40 % AlPW
12O
40/ SiO
2With 40 % AlPW
12O
40/ TiO
2Catalyzer is estimated it as follows to the catalytic activity of the acylation reaction of pyrene and benzoyl oxide.
7 mol % catalyzer are joined fill CH
2Cl
2-CH
2Cl
2In the 50 mL three-necked flasks with spherical reflux condensing tube of (10 mL), slowly add benzoyl oxide (1 mmol) under magnetic agitation, be stirred to AlC1
3Dissolving and mixing; Again 0.05 g pyrene (0.25 mmol) is dissolved in 5 mL CH
2Cl
2-CH
2Cl
2, and it is slowly splashed in three-necked flask, then three-necked flask is placed on 75
οIn the C thermostat water bath, open magnetic agitation, stop after anti-40 min stirring, flask is taken out, make reaction system be down to room temperature; Filter, use CH
2Cl
2-CH
2Cl
2Filter residue is washed 2-3 time, and 120
οIn the C baking oven, dry 3 h are standby; Pour filtrate in separating funnel standing demix, take out organic phase, go out organic phase with extracted with diethyl ether successively, with the mixed solution (volume ratio is 1:10) of 36 % hydrochloric acid and frozen water to organic phase repetitive scrubbing 3-4 time, then standing demix in separating funnel, with chloroform extraction upper strata water 3-4 time, chloroform extraction liquid and lower floor's organic phase are mixed, use saturated Na
2CO
3Repeatedly be washed till neutrality; Use anhydrous MgSO
4Organic phase is carried out drying; The solvent in organic phase is removed in underpressure distillation, gets yellow solid, with its with petroleum ether and in acetone recrystallization, get yellow tabular crystal, amount and the catalytic activity of different catalysts see Table 1.
The catalytic activity of the various catalyzer of table 1 to the acylation reaction of pyrene and benzoyl oxide
| The case study on implementation title | 5 | 6 | 7 |
| Used catalyst | AlPW 12O 40 | 40 % AlPW 12O 40/SiO 2 | 40 % AlPW 12O 40/TiO 2 |
| 1-benzoyl pyrene yield % | 54.09 % | 86.23 % | 80.83 % |
| 1-benzoyl pyrene selectivity % | 100 % | 100 % | 100 % |
By as seen from Table 1, under identical experiment condition, 40 % AlPW
12O
40/ SiO
2Catalyzer is best to the catalytic activity effect of the acylation reaction of benzene and benzoyl oxide, and can find out significantly that the catalyst of aluminium phosphotungstic acid of load shows better catalytic effect than simple catalyst of aluminium phosphotungstic acid in the acylation reaction of pyrene and benzoyl oxide.
Case study on implementation 840 % AlPW
12O
40/ SiO
2The repeat performance research of catalyzer
After case is implemented 6 reaction end, filter, use CH
2Cl
2-CH
2Cl
2To filter residue (40 % AlPW
12O
40/ SiO
2) wash 2-3 time, and 120
οDry 3 h in the C baking oven, the acylation reaction of catalysis pyrene and benzoyl oxide again, reaction conditions implements 6 with case, the results are shown in table 2.
Case study on implementation 9
After case 8 reactions to be performed finish, filter, use CH
2Cl
2-CH
2Cl
2To filter residue (40 % AlPW
12O
40/ SiO
2) wash 2-3 time, and 120
οDry 3 h in the C baking oven, the acylation reaction of catalysis pyrene and benzoyl oxide again, reaction conditions implements 6 with case, the results are shown in table 2.
Case study on implementation 10
After case 9 reactions to be performed finish, filter, use CH
2Cl
2-CH
2Cl
2To filter residue (40 % AlPW
12O
40/ SiO
2) wash 2-3 time, and 120
οDry 3 h in the C baking oven, the acylation reaction of catalysis pyrene and benzoyl oxide again, reaction conditions implements 6 with case, the results are shown in table 2.
Table 2 40 % AlPW
12O
40/ SiO
2Catalyzer repeats catalytic performance
| The case study on implementation title | 6 | 8 | 9 | 10 |
| Multiplicity | 0 | 1 | 2 | 3 |
| 1-benzoyl pyrene yield % | 86.23 % | 85.98 % | 85.64 % | 84.12 % |
| 1-benzoyl pyrene selectivity % | 100 % | 100 % | 100 % | 100 % |
As shown in Table 2, through three repeated experiments, 40 % AlPW
12O
40/ SiO
2The catalytic activity of catalyzer does not significantly reduce, and more than still remaining on 84 %, and the selectivity of product still remains on 100 %.
Case study on implementation 1140 % AlPW
12O
40/ TiO
2The repeat performance research of catalyzer
After case 7 reactions to be performed finish, filter, use CH
2Cl
2-CH
2Cl
2To filter residue (40 % AlPW
12O
40/ SiO
2) wash 2-3 time, and 120
οDry 3 h in the C baking oven, the acylation reaction of catalysis pyrene and benzoyl oxide again, reaction conditions implements 7 with case, the results are shown in table 3.
Case study on implementation 12
After case 11 reactions to be performed finish, filter, use CH
2Cl
2-CH
2Cl
2To filter residue (40 % AlPW
12O
40/ SiO
2) wash 2-3 time, and 120
οDry 3 h in the C baking oven, the acylation reaction of catalysis pyrene and benzoyl oxide again, reaction conditions implements 7 with case, the results are shown in table 3.
Case study on implementation 13
After case 12 reactions to be performed finish, filter, use CH
2Cl
2-CH
2Cl
2To filter residue (40 % AlPW
12O
40/ SiO
2) wash 2-3 time, and 120
οDry 3 h in the C baking oven, the acylation reaction of catalysis pyrene and benzoyl oxide again, reaction conditions implements 7 with case, the results are shown in table 3.
Table 3 40 % AlPW
12O
40/ TiO
2Catalyzer repeats catalytic performance
| The case study on implementation title | 7 | 11 | 12 | 13 |
| Multiplicity | 0 | 1 | 2 | 3 |
| 1-benzoyl pyrene yield % | 80.83 % | 78.98 % | 77.35 % | 76.64 % |
| 1-benzoyl pyrene selectivity % | 100 % | 100 % | 100 % | 100 % |
As shown in Table 3, through three repeated experiments, 40 % AlPW
12O
40/ TiO
2The catalytic activity of catalyzer does not significantly reduce, and more than still remaining on 76 %, and the selectivity of product still remains on 100 %.
Claims (8)
1.1-the one-step method for synthesizing of benzoyl pyrene is characterized in that comprising the steps:
(1) to catalyzer and non-polar solvent 1,2-ethylene dichloride (CH
2Cl
2-CH
2Cl
2) in the mixing solutions that forms, add while stirring the acylting agent benzoyl oxide, mix and form mixing solutions 1;
(2) the condensed-nuclei aromatics pyrene is slowly joined in mixing solutions 1,
VSolvent:
n(pyrene)=15:0.25,
n(catalyzer):
n(pyrene)=0.04 ~ 0.1,
n(pyrene):
n(benzoyl oxide)=1:1 ~ 1:7; 60 ~ 90
οWater bath with thermostatic control back flow reaction 10 ~ 120 min under C form reaction soln 2, stir in reaction process, make reaction soln 2 be down to room temperature after reaction;
(3) reaction soln 2 is filtered, use CH
2Cl
2-CH
2Cl
2To filter residue repetitive scrubbing 2-3 time, and recycling; Filtrate is through GC-MS, and GC detects, and wherein material is carried out quantitative and qualitative analysis;
(4) filtrate after step 3 filtration is extracted, extract organic phase, it is neutral that repetitive scrubbing to organic phase is;
(5) organic phase is carried out drying after, the solvent in organic phase is removed in underpressure distillation, gets the yellow solid crude product, with crude product washing and recrystallization, gets yellow tabular crystal, and this material is carried out FT-IR,
1H NMR phenetic analysis is finished product 1-benzoyl pyrene.
2. the one-step method for synthesizing of 1-benzoyl pyrene as claimed in claim 1, it is characterized in that: the stirring in step 1 neutralization procedure 2 is magnetic agitation.
3. the one-step method for synthesizing of 1-benzoyl pyrene as claimed in claim 1, it is characterized in that: go out organic phase with extracted with diethyl ether successively in step 4, be that the mixed solution of the 36 % hydrochloric acid of 1:10 and frozen water is to organic phase repetitive scrubbing 3-4 time with volume ratio, then standing demix in separating funnel, with chloroform extraction upper strata water 3-4 time, extraction liquid and lower floor's organic phase of chloroform extraction upper strata water are mixed, use saturated Na
2CO
3Repeatedly be washed till neutrality.
4. the one-step method for synthesizing of 1-benzoyl pyrene as claimed in claim 1, is characterized in that: use anhydrous MgSO in step 5
4Organic phase is carried out drying; Use sherwood oil that crude product is washed and recrystallization in acetone.
5. the one-step method for synthesizing of 1-benzoyl pyrene as claimed in claim 1, it is characterized in that: the catalyzer in step 1 is AlPW
12O
40Or charge capacity is the 40 silicon dioxide carried AlPW of %
12O
40(40 % AlPW
12O
40/ SiO
2) or charge capacity be 40 % titanium dichloride load AlPW
12O
40(40 % AlPW
12O
40/ TiO
2).
6. the one-step method for synthesizing of 1-benzoyl pyrene as claimed in claim 5, it is characterized in that: charge capacity is 40 %
Silicon dioxide carried AlPW
12O
40The calculating of the charge capacity of catalyzer:
In formula:
ωCharge capacity for catalyzer;
m 1Be the quality of active ingredient aluminium phosphotungstic acid, g;
m 2Be the quality of carrier, g.
7. the one-step method for synthesizing of 1-benzoyl pyrene as claimed in claim 5, it is characterized in that: charge capacity is 40 %
Titanium dichloride load AlPW
12O
40The calculating of the charge capacity of catalyzer:
In formula:
ωCharge capacity for catalyzer;
m 1Be the quality of active ingredient aluminium phosphotungstic acid, g;
m 2Be the quality of carrier, g.
8. the one-step method for synthesizing of 1-benzoyl pyrene as claimed in claim 5, it is characterized in that: the catalyzer in step 1 is AlPW
12O
40Or charge capacity is the 40 silicon dioxide carried AlPW of %
12O
40(40 % AlPW
12O
40/ SiO
2).
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6376726B1 (en) * | 1997-10-14 | 2002-04-23 | Council Of Scientific & Industrial Research | Process for the production of nitroaromatic compounds from aromatic hydrocarbons using modified clay catalysts |
| CN102173992A (en) * | 2011-03-21 | 2011-09-07 | 南通大学 | Preparation method of nitrophenol compounds |
-
2013
- 2013-02-28 CN CN201310061897.4A patent/CN103086860B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6376726B1 (en) * | 1997-10-14 | 2002-04-23 | Council Of Scientific & Industrial Research | Process for the production of nitroaromatic compounds from aromatic hydrocarbons using modified clay catalysts |
| CN102173992A (en) * | 2011-03-21 | 2011-09-07 | 南通大学 | Preparation method of nitrophenol compounds |
Non-Patent Citations (4)
| Title |
|---|
| CHRISTOPHE LE ROUX等: "BiCl3-catalyzed Friedel–Crafts acylation reactions: bismuth(III) oxychloride as a water insensitive and recyclable procatalyst", 《TETRAHEDRON LETTERS》 * |
| HABIB FIROUZABADI等: "Aluminum dodecatungstophosphate (AlPW12O40) as a non-hygroscopic Lewis acid catalyst for the efficient Friedel–Crafts acylation of aromatic compounds under solvent-less conditions", 《TETRAHEDRON》 * |
| MIN CHEN等: "Synthesis of 1-benzoylpyrene using silica-supported phosphotungstic heteropoly acid as an efficient and reusable catalyst", 《KOREAN J. CHEM. ENG.》 * |
| 胡玉华等: "杂多酸催化剂在有机合成中的应用", 《化工进展》 * |
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