CN100582096C - Method for synthesizing pyrazoline derivatives capable of irradiating yellow green light - Google Patents
Method for synthesizing pyrazoline derivatives capable of irradiating yellow green light Download PDFInfo
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- CN100582096C CN100582096C CN200810054609A CN200810054609A CN100582096C CN 100582096 C CN100582096 C CN 100582096C CN 200810054609 A CN200810054609 A CN 200810054609A CN 200810054609 A CN200810054609 A CN 200810054609A CN 100582096 C CN100582096 C CN 100582096C
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Abstract
Disclosed is a synthesis method of pyrazoline derivatives emitting olivine light, in which the pyrazoline derivative, 1-phenyl-3-[4-(N-phenyl-1-naphthylamine)ethylene]-5-[4-(N-phenyl-1-naphthylamine)phenyl]-2-pyrazoline brown-green crystals are finally prepared through three-times intermediates, by selecting material, preparing sollution, chemical combination reaction, heating, mixing, water-circulation condensation, ice water washing, argon protection, column chromatography purification, recrystallization purification, vacuum filtering, evaporation and drying, the products are grain diamond-shaped, the color coordinate is that x=0.3257, y=0.5452, the maximal emission wavelength of photoluminescence spectrum is 523 nm and the full width at half maximum is 96 nm. The products have high purity, pure color, excellent irradiance performance, high irradiance intensity and high lighteness, the products are also capable of improving the stability, reliability and life time of organic electroluminescent devices, being used in the fields of advance electronic display and irradiance illumination technology, the method of the invention is strictness and reasonable.
Description
Technical field
The present invention relates to a kind of synthetic method of pyrazoline derivative of the green glow that turns to be yellow, belong to the application of electroluminescent organic material, the synthetic preparation method's of reaching technical field.
Background technology
Electroluminescent organic material---pyrazoline compounds has good hole transport function, has higher fluorescence quantum efficiency simultaneously, pyrazoline compounds is applied on organic electroluminescence device as blue light emitting material and hole mobile material, is usually used in technical fields such as organic light-guide, xerox.
The thermostability of pyrazoline compounds is relatively poor, also limited its range of application on organic electroluminescence device, in existing technology, synthetic, the preparation method of pyrazoline compounds also have a lot of drawbacks and deficiency, for example crystallinity problem, thermal stability problems, and product purity is lower, production yield rate is lower, has also limited the further development and the extendability of pyrazoline compounds and has used.
Summary of the invention
Goal of the invention
Purpose of the present invention is exactly at disadvantages of background technology, adopt a kind of new synthesis preparation method and technical process, adopt four kinds of solvents and three synthetic, purifications of intermediate product, finally make the pyrazoline derivative of highly purified jaundice green glow, to increase substantially the production yield rate of product, to improve the thermostability of its product, pyrazoline derivative is more widely used.
Technical scheme
The chemical substance that the present invention uses is: N-phenyl-1-naphthylamine, iodobenzene, potassium hydroxide, 18-hat-6, cuprous iodide, tetraline, aluminium sesquioxide, hexanaphthene, N, N '-dimethyl formamide, phosphorus oxychloride, calcium chloride, N, N '-phenylbenzene-naphthalidine, sodium hydroxide, 4-(N-phenyl-1-naphthylamine) phenyl aldehyde, acetone, dehydrated alcohol, ethylene glycol monoethyl ether, hydrochloric acid, phenylhydrazine, methylene dichloride, sherwood oil, benzene, ethyl acetate, argon gas, deionized water mixture of ice and water, quartz sand, absorbent cotton, its consumption is as follows: with gram, milliliter, centimetre
3Be measure unit
N-phenyl-1-naphthylamine: C
16H
13N 5.7g ± 0.05g
Iodobenzene: C
6H
5I 6ml ± 0.5ml
Potassium hydroxide: KOH 8.4g ± 0.05g
18-hat-6:C
20H
36O
60.5g ± 0.05g
Cuprous iodide: CuI 1.909g ± 0.05g
Aluminium sesquioxide: Al
2O
360g ± 5g
Hexanaphthene: C
6H
12150ml ± 10ml
N, N '-dimethyl formamide: C
3H
7NO 15ml ± 1ml
Phosphorus oxychloride: POCl
31.37ml ± 0.1ml
Calcium Chloride Powder Anhydrous: CaCl
25g ± 0.5g
N, N '-phenylbenzene-naphthalidine: C
22H
17N 1.475g ± 0.05g
Sodium hydroxide: NaOH 20% aqueous solution 10ml ± 0.5ml
Tetraline: C
10H
1260ml ± 2ml
4-(N-phenyl-1-naphthylamine) phenyl aldehyde: C
23H
17NO 0.978g ± 0.05g
Acetone: C
3H
6O 0.24ml ± 0.02ml
Dehydrated alcohol: C
2H
6O 70ml ± 2ml
Ethylene glycol monoethyl ether: C
4H
10O
220ml ± 1ml
Hydrochloric acid: HCl concentration 37.5% 0.2ml ± 0.05ml
Phenylhydrazine: C
6H
8N
20.05ml ± 0.01ml
Methylene dichloride: CH
2Cl
210ml ± 0.5ml
Sherwood oil: 30ml ± 2ml
Benzene: C
6H
620ml ± 1ml
Ethyl acetate: C
4H
8O
220ml ± 1ml
Argon gas: Ar 60000cm
3± 1200cm
3
Deionized water mixture of ice and water: H
2O 100ml ± 10ml
Quartz sand: SiO
20.5g ± 0.05g
Absorbent cotton: 0.1g ± 0.05g
Synthetic method is as follows:
(1) selected raw chemical material
To carry out selectedly to preparing required raw chemical material, and carry out precision, control of purity:
N-phenyl-1-naphthylamine: 95%
Iodobenzene: 98%
Potassium hydroxide: 〉=99%
18-hat-6:99%
Cuprous iodide: 〉=98%
Tetraline: 〉=97%
Aluminium sesquioxide: neutral fineness 200～300 orders 〉=98%
Hexanaphthene: 〉=99%
N, N '-dimethyl formamide: 〉=99%
Phosphorus trichloride: 〉=98%
Calcium Chloride Powder Anhydrous: 〉=96%
N, N '-phenylbenzene-naphthalidine: 97%
Sodium hydroxide: 〉=98%
4-(N-phenyl-1-naphthylamine) phenyl aldehyde: 95%
Acetone: 〉=99%
Dehydrated alcohol: 〉=99%
Methyl list ether: 〉=99%
Hydrochloric acid: concentration 37.5%
Phenylhydrazine: 98%
Methylene dichloride: 〉=99%
Sherwood oil: 60～90 ℃ of boiling points
Benzene: 〉=99%
Ethyl acetate: 〉=99%
Argon gas: 99.9%
Deionized water mixture of ice and water: 99.9%
Quartz sand: fineness 60～80 orders
Absorbent cotton: degreasing rate 98%
(2) preparation intermediate product I:N, N '-phenylbenzene-naphthalidine
1. in four-hole boiling flask, add:
N-phenyl-1-naphthylamine: 5.7g ± 0.05g
Iodobenzene: 6ml ± 0.5ml
18-hat-6:0.5g ± 0.05g
Potassium hydroxide: 8.4g ± 0.05g
Cuprous iodide: 1.909g ± 0.05g
Tetraline: 60ml ± 2ml
2. to four-hole boiling flask input protection gas: argon gas
Input speed: 40cm
3/ min
3. four-hole boiling flask is placed on the heating jacket;
4. heating jacket is placed on the magnetic stirring apparatus;
5. insert thermometer, dropping funnel, tunger tube, water cycle prolong on the four-hole boiling flask respectively;
6. open heating jacket, magnetic stirring apparatus, water condensation circulation tube, 200 ℃ ± 5 ℃ of Heating temperatures, the magnetic agitation frequency is 300r/min;
7. under heated condition, under the water cycle condensing state, under the argon shield, under the magnetic stirring apparatus vigorous stirring, stir, churning time 1440min ± 20min stirs the back and becomes mixing solutions;
8. cold filtration
Close argon gas, water condensation circulation, heating jacket, magnetic stirring apparatus, mixing solutions under static state naturally cools to 20 ℃ ± 3 ℃, pours into then in the funnel of the neutral qualitative filter paper of liner, filters and collect filtrate;
9. distillation
Beaker that filtrate is housed as on the Rotary Evaporators, is steamed excessive tetraline and iodobenzene, obtain crude product powder 4.45g ± 0.05g of intermediate product I;
10. the dry method column chromatography is purified:
Sorbent material: aluminium sesquioxide
Eluent: sherwood oil 30ml ± 2ml, benzene 20ml ± 1ml, sherwood oil: benzene=3: 2, hexanaphthene 150ml ± 10ml;
Carry out in the tubular type chromatography column, tubular type chromatography column top is placed with dropping funnel, and the bottom connects drain pipe, and by control valve control, the drain pipe bottom is provided with collection container;
The dress post: the absorbent cotton 0.1g ± 0.05g that packs in the cylinder bottom, place quartz sand 0.5g ± 0.05g on absorbent cotton; In post, slowly pour hexanaphthene 150ml ± 10ml then into, reinstall aluminium sesquioxide 60g ± 5g, beat shaft gently with the soft rubber rod simultaneously, make the aluminium sesquioxide even compact of packing into, no bubble produces, put crude product powder 4.45g ± 0.05g of intermediate product I to be purified on aluminium sesquioxide top, the eluent sherwood oil+benzene mixing solutions 50ml ± 3ml for preparing is poured in the dropping funnel, i.e. the chromatography column top;
Differentiate: after material to be separated is impregnated into aluminium sesquioxide fully, the colour band section of different colours will appear in shaft, use each color section of ultraviolet fluorescent light irradiation then, and each color section will produce luminous and not luminous section;
Wash-out: opening controlling valve, when powder to be purified is dissolved in hexanaphthene and is penetrated into aluminium sesquioxide fully, two colour bands appear in shaft, above a colour band be brown, below a colour band be light yellow, open dropping funnel, collect the solution of light yellow colour band, has collected closed control valve afterwards at liquid outlet;
Light yellow colour band solution with the Rotary Evaporators evaporate to dryness is collected gets intermediate product I white powder 3.95g ± 0.05g;
Recrystallization is purified
On the recrystallization equipment for purifying, carry out:
Beaker is placed on the magnetic stirring apparatus, in beaker, add dehydrated alcohol 15ml ± 1ml, intermediate product I powder 3.95g ± 0.05g, power-on, heated and stirred, temperature rise to 78 ℃ ± 0.5 ℃ of dehydrated alcohol boiling point, constant temperature boiling 0.5min, while hot solution is poured in the Glass Containers, placed the slowly volatilization of shady and cool place, recrystallization is purified and is repeated secondary, get intermediate product I:N, N '-phenylbenzene-naphthalidine white crystal 3.45g ± 0.05g;
(3) preparation intermediate product II:4-(N-phenyl-1-naphthylamine) phenyl aldehyde
1. preparation: N, N '-phenylbenzene-naphthalidine+N, N '-dimethyl formamide solution
In there-necked flask, with white crystal N, N '-phenylbenzene-naphthalidine 1.475g ± 0.05g and N, N '-dimethyl formamide 10ml ± 1ml mixes, and is stirred into solution;
2. stirrer is put into there-necked flask, there-necked flask is placed the beaker that fills mixture of ice and water, beaker is placed on the rotation magnetic force agitator;
3. in there-necked flask, add:
N, N '-dimethyl formamide 5ml ± 1ml, phosphorus oxychloride 1.37ml ± 0.1ml;
4. insert tunger tube at there-necked flask, input argon gas 40cm
3/ min;
5. insert drying tube and add siccative Calcium Chloride Powder Anhydrous 5g ± 0.5g at there-necked flask;
6. add the N for preparing at the there-necked flask liquid adding hole, N '-phenylbenzene-naphthalidine+N, N '-dimethyl formamide solution stirs 60min ± 10min under the ice-water bath state;
7. there-necked flask is placed in the heating jacket, heating jacket places on the rotation magnetic force agitator, removes drying tube, changes the water condensation circulation tube, opens heating jacket, is warming up to 60 ℃ ± 5 ℃, and constant temperature keeps 360min ± 10min, and mixing solutions carries out combination reaction;
8. after reaction finishes, reaction soln in the there-necked flask is poured in the beaker of the deionized water mixture of ice and water that fills 100ml ± 10ml, mix the back and a large amount of yellow-green colour flosss occur, add sodium hydroxide solution 10ml ± 0.5ml, the limit drips, stir on the limit, treats pH=6～8 o'clock, solution meta-alkalescence, stop to drip, continue to stir 60min ± 10min then;
9. suction filtration: mixing solutions is poured in the B of the three layers of middling speed qualitative filter paper of liner on the vacuum filtration bottle, is used the vacuum pump suction filtration rapidly, the khaki color solid product;
10. dry: as to get intermediate product II, i.e. 4-(N-phenyl-1-naphthylamine) phenyl aldehyde powder after the seasoning;
Column chromatography is purified
Intermediate product II:4-(N-phenyl-1-naphthylamine) phenyl aldehyde that makes is placed the column chromatography equipment for purifying, carrying out column chromatography with aforesaid method of purification purifies, eluent is the mixing solutions 40ml ± 2ml of ethyl acetate+sherwood oil, ethyl acetate: sherwood oil=1: 1, collect luminous colour band, obtain intermediate product II solution;
Evaporate to dryness product solution
With Rotary Evaporators evaporate to dryness intermediate product II solution, obtain intermediate product II yellow powder, that is: 4-(N-phenyl-1-naphthylamine) phenyl aldehyde 1.184g ± 0.1g;
(4) preparation intermediate product III:4,4 '-two (N, N '-phenylbenzene-naphthalidine)-pentadiene ketone
1. in there-necked flask, add: 4-(N-phenyl-1-naphthylamine) phenyl aldehyde 0.978g ± 0.05g, acetone 0.24ml ± 0.02ml, dehydrated alcohol 40ml ± 2ml;
2. dropping sodium+ethanolic soln in there-necked flask: 15ml ± 0.5ml, the speed of splashing into is 15/min, control pH=7～9, meta-alkalescence;
3. stirring reaction 1440min ± 30min under 20 ℃ ± 3 ℃ temperature of normal temperature stirs back solution and is safran, generates yellow floss;
4. suction filtration
The safran solution that will contain yellow floss places the B of vacuum filtration bottle, with three layers of middling speed qualitative filter paper suction filtration, stays the product filter cake;
5. seasoning: will get intermediate product III yellow powder, i.e. 4,4 '-two (N, N '-phenylbenzene-naphthalidine)-pentadiene ketone 0.57g ± 0.05g after the filter cake seasoning;
(5) the synthetic final product of preparation: pyrazoline derivative---1-phenyl-3-[4-(N-phenyl-1-naphthylamine)-phenyl vinyl]-5-[4-(N-phenyl-1-naphthylamine) phenyl]-the 2-pyrazoline
1. in there-necked flask, add: 4,4 '-two (N, N '-phenylbenzene-naphthalidine)-pentadiene ketone 0.32g ± 0.05g, ethylene glycol monoethyl ether 20ml ± 1ml;
2. drip concentrated hydrochloric acid 0.2ml ± 0.05ml in there-necked flask, solution becomes light green;
3. in there-necked flask, drip phenylhydrazine 0.05ml ± 0.01ml, there-necked flask is placed on the heating jacket heat then, 100 ℃ ± 5 ℃ of Heating temperatures, time 180min ± 10min, solution becomes sorrel;
4. in there-necked flask, add methylene dichloride 10ml ± 0.5ml, the solution layering, the upper strata is a dichloromethane solution, lower floor is an ethylene glycol monoethyl ether solution, collects upper strata brown-green liquid;
5. evaporimeter drying
With Rotary Evaporators desciccate solution, get final product powder 0.215g ± 0.05g;
6. recrystallization is purified
In beaker, add dehydrated alcohol 10ml ± 0.5ml, 0.215g ± 0.05g puts into beaker with the final product powder, power-on, heated and stirred, temperature rise to 78 ℃ ± 0.5 ℃ of dehydrated alcohol boiling point, constant temperature boiling 0.5min, while hot solution is poured in the Glass Containers, place the slowly volatilization of place, cool place, recrystallization is purified and is repeated secondary, gets the brown-green final product;
7. seasoning
The final product of purifying through secondary recrystallization carries out seasoning in cleaning place, time 120min ± 10min, get high purity final product crystal, i.e. brown-green pyrazoline derivative: 1-phenyl-3-[4-(N-phenyl-1-naphthylamine)-phenyl vinyl]-5-[4-(N-phenyl-1-naphthylamine) phenyl]-the 2-pyrazoline;
(6) detect, analyze, characterize
Synthetic pyrazoline derivative product is detected, analyzes and characterizes:
1. recording the product crystal morphology for 100 times with the scanning electron microscope amplification is the particulate state rhombus;
2. use determination of infrared spectroscopy product molecular structure;
3. measure the photoluminescence spectrum and the chromaticity coordinates of product with fluorescence spectrophotometer;
4. carry out ultraviolet absorption spectroscopy with ultraviolet spectrometer;
(7) store
The turn to be yellow pyrazoline derivative product of green glow of synthetic is placed brown transparent Glass Containers, airtight keeping in Dark Place, be stored in cool place, drying, the clean environment, waterproof, protection against the tide, fire prevention, sun-proof, anti-acid and alkali corrosion, storing temp is 20 ℃ ± 3 ℃, relative humidity≤30%.
Described high purity pyrazoline derivative---1-phenyl-3-[4-(N-phenyl-1-naphthylamine)-phenyl vinyl]-5-[4-(N-phenyl-1-naphthylamine) phenyl]-2-pyrazoline jaundice green glow, its chromaticity coordinates x=0.3257, y=0.5452, photoluminescence spectra maximum emission wavelength are that 523nm, halfwidth are 96nm.
The pyrazoline derivative product crystal of described jaundice green glow, its pattern are brown-green particulate state rhombus.
The molecular structure of the pyrazoline derivative product of described jaundice green glow is:
Beneficial effect
The present invention compares with background technology has tangible advance; make the pyrazoline derivative of preparation high purity jaundice green glow become possibility; by intermediate product I; II; the preparation of III; prepare through final product; through picking of raw material; obtain solution; combination reaction; heating; stir; the water cycle condensation; ice-water bath; argon shield; column chromatography is purified; recrystallization is purified; distillation is purified; vacuum filtration; evaporation drying; finally make: pyrazoline derivative---1-phenyl-3-[4-(N-phenyl-1-naphthylamine) vinyl]-5-[4-(N-phenyl-1-naphthylamine) phenyl]-2-pyrazoline brown-green product crystal; the product pattern is a brown-green particulate state rhombus; its chromaticity coordinates x=0.3257; y=0.5452; the photoluminescence spectra maximum emission wavelength is 523nm; halfwidth is 96nm; be the photic emission of yellow green light; the product purity height; color is pure; luminescent properties is good; the luminous intensity height; brightness is big; can increase substantially the stability of organic electroluminescence device; reliability and life-span; can be used for fields such as advanced electronic demonstration and luminouslighting technology; this preparation synthetic method craft is tight; rationally; well arranged clear, be the method that ideal prepares the electroluminescent organic material pyrazoline derivative.
Description of drawings
Fig. 1 is preparation technology's schema
Fig. 2 prepares state graph for intermediate product I four-hole boiling flask
Fig. 3 is intermediate product I column chromatography purification state graph
Fig. 4 is intermediate product II there-necked flask ice-water bath synthetic state figure
Fig. 5 is intermediate product II there-necked flask synthetic state figure
Fig. 6 amplifies 100 times of shape appearance figures for product crystal grain
Fig. 7 is the product infrared spectrogram
Fig. 8 is the molecular structure of product
Fig. 9 is product fluorescence spectrum figure
Figure 10 is the chromaticity coordinates figure of product
Figure 11 is the product uv absorption spectra
Shown in the figure, list of numerals is as follows:
1, electric mantle, 2, four-hole boiling flask, 3, tunger tube, 4, dropping funnel, 5, the water condensation circulation tube, 6, rising pipe, 7, water inlet pipe, 8, the air outlet, 9, control valve, 10, thermometer, 11, argon bottle, 12, inlet pipe, 13, the argon gas valve, 14, N-phenyl-1-naphthylamine+iodobenzene+18-hat-6+ cuprous iodide+tetraline mixing solutions, 15, magnetic stirring apparatus 16, stirrer, 17, shaft, 18, dropping funnel, 19, the intermediate product powder, 20, aluminium sesquioxide, 21, quartz sand, 22, absorbent cotton, 23, drain pipe, 24, control valve, 25, container, 26, luminous product solution, 27, support, 28, the fluorescence chromatic discrimination device, 29, eluent sherwood oil+benzene, 30, the rotation magnetic force agitator, 31, stirrer, 32, there-necked flask, 33, large beaker, 34, mixture of ice and water, 35, argon bottle, 36, inlet pipe, 37, variable valve, 38, dropping funnel, 39, drying tube, 40, N, N '-dimethyl formamide+phosphorus trichloride solution, 41, Calcium Chloride Powder Anhydrous, 42, N, N '-phenylbenzene-naphthalidine+N, N '-dimethyl formamide solution, 43, the rotation magnetic force agitator, 44, heating jacket, 45, stirrer, 46, N, N '-phenylbenzene-naphthalidine+N, N '-dimethyl formamide+phosphorus trichloride solution, 47, there-necked flask, 48, thermometer, 49, rising pipe, 50, the water cycle prolong, 51, water inlet pipe, 52, the air outlet, 53, inlet pipe, 54, control valve, 55, argon bottle.
Embodiment
The present invention will be further described below in conjunction with accompanying drawing:
Shown in Figure 1, be preparation technology's schema, carry out in strict accordance with processing parameter, according to the order of sequence operation.
Required raw chemical material is to determine in the numerical range that sets in advance in the preparation synthetic product, with gram, milliliter, centimetre
3, minute be measure unit, when carrying out industrialization and produce, with kilogram, liter, rice
3, minute be measure unit.
Want strict selected to preparing required raw chemical material and subsidiary material, and carry out control of purity, must not have impurity to get involved, prevent to generate by product, influence product purity and luminescent properties.
It is clean that the four-hole boiling flask that uses in preparation process, there-necked flask, beaker, filter flask, chromatography column, water cycle prolong, B, stirrer, dropping funnel, thermometer, qualitative filter paper, container, magnetic stirring apparatus, heating jacket etc. will keep, in order to avoid normal reaction of influence and generation by product.
The preparation building-up process divided for four steps carried out:
The first step; preparation intermediate product I:N; N '-phenylbenzene-naphthalidine; adding N-phenyl-1-naphthylamine+iodobenzene+18-hat-6+ cuprous iodide+tetraline earlier in four-hole boiling flask blendes together solution, under argon shield, under the water cycle condensation, under the heated condition, under the magnetic stirring apparatus vigorous stirring, makes mixing solutions; purify through column chromatography purification, dehydrated alcohol recrystallization again; obtain white crystal,, get white intermediate product I through seasoning.
Second step; preparation intermediate product II:4-(N-phenyl-1-naphthylamine) phenyl aldehyde; earlier intermediate product I and N; N '-dimethyl formamide is mixed with into mixing solutions; in there-necked flask, add N; N '-dimethyl formamide+phosphorus trichloride solution; under argon shield; in ice-water bath, stir 60min ± 10min, be heated to 60 ℃ ± 5 ℃ then; be poured in the 100ml frozen water behind reaction 360min ± 10min; drip NaOH solution to pH=6～8, after filtration; drying gets khaki color intermediate product powder; purify through column chromatography again; evaporate to dryness makes yellow intermediate product II.
The 3rd step, preparation intermediate product III:4,4 '-two (N, N '-phenylbenzene-naphthalidine)-and pentadiene ketone, in there-necked flask, add 4-(N-phenyl-1-naphthylamine) phenyl aldehyde+acetone+ethanolic soln, dropping sodium then, through vacuum filtration, drying, get safran intermediate product III.
The 4th step, preparation final product: pyrazoline derivative---1-phenyl-3-[4-(N-phenyl-1-naphthylamine)-phenyl vinyl]-5-[4-(N-phenyl-1-naphthylamine) phenyl]-the 2-pyrazoline, in there-necked flask, add: 4,4 '-two (N, N '-phenylbenzene-naphthalidine)-pentadiene ketone+ethylene glycol monoethyl ether solution, dripping hydrochloric acid, phenylhydrazine, add methylene dichloride and get brown-green solution, through evaporation drying, purify through the dehydrated alcohol recrystallization, dry, get brown-green final product crystal, i.e. 1-phenyl-3-[4-(N-phenyl-1-naphthylamine)-phenyl vinyl]-5-[4-(N-phenyl-1-naphthylamine) phenyl]-2-pyrazoline crystal.
Shown in Figure 2, for four-hole boiling flask prepares intermediate product I state graph, the bottom is a magnetic stirring apparatus 15, magnetic stirring apparatus 15 tops are heating jackets 1, heating jacket 1 top is four-hole boiling flask 2, four-hole boiling flask 2 tops are provided with temperature agent 10 side by side, dropping funnel 4, tunger tube 3, water cycle prolong 5, dropping funnel 4 is by control valve 9 controls, tunger tube 3 is by 13 controls of argon gas valve and connect inlet pipe 12 and argon bottle 11, water cycle prolong 5 is connected external water source by water inlet pipe 7 with rising pipe 6, and water cycle prolong 5 tops are air outlet 8, is N-phenyl-1-naphthylamine+iodobenzene+18-hat-6+ cuprous iodide+tetraline mixing solutions 14 in the four-hole boiling flask 2.
Shown in Figure 3, column chromatography purification state graph, dropping funnel 18 is put on shaft 17 tops, the bottom connects drain pipe 23, and by control valve 24 controls, drain pipe 23 bottoms are provided with collection container 25, and the dress post is in proper order: absorbent cotton 22, quartz sand 21, aluminium sesquioxide 20, N, put eluent sherwood oil+benzene in N '-phenylbenzene-naphthalidine powder dropping funnel 18, fluorescence is differentiated sidepiece and the irradiation of instrument at shaft.
Shown in Figure 4, be intermediate product II there-necked flask ice-water bath synthetic state figure, the bottom is a rotation magnetic force agitator 30, put large beaker 33 on the magnetic stirring apparatus 30, mixture of ice and water 34 is housed in the large beaker 33, in large beaker 33, put into there-necked flask 32, inlet pipe 36 is inserted on there-necked flask 32 tops side by side, dropping funnel 38, drying tube 39, inlet pipe 36 connects variable valve 37, argon bottle 35, in the there-necked flask 32 is N, and N '-dimethyl formamide+phosphorus trichloride solution 40 is equipped with N in the dropping funnel 38, N '-phenylbenzene-naphthalidine+N, N '-dimethyl formamide mixing solutions 42.
Shown in Figure 5, be intermediate product II there-necked flask synthetic state figure, the bottom is a rotation magnetic force agitator 43, be placed with heating jacket 44 on the rotation magnetic force agitator 43, be placed with there-necked flask 47 in the heating jacket 44, be placed with stirrer 45 in the there-necked flask 47, N, N '-phenylbenzene-naphthalidine+N, N '-dimethyl formamide+phosphorus trichloride solution 46, there-necked flask 47 from left to right is inserted with inlet pipe 53, thermometer 48, water cycle prolong 50 successively, inlet pipe 53 is by control valve 54 controls and connect argon bottle 55, and water-in 51 is arranged on the water cycle prolong 50, water outlet 49, air outlet 52.
Fig. 6 is that product crystal grain amplifies 100 times of shape appearance figures, among the figure as can be known: the product pattern is the particulate state rhombus, is irregular alignment, and ruler units is um.
Fig. 7 is the product infrared spectrogram, and ordinate zou is a relative intensity, and X-coordinate is wavelength cm
-1, among the figure as can be known: occurring C-H stretching vibration peak on the phenyl ring near 3056.83, near 1589.53, having the flexible vibrations of strong C=N peak, showing to have the C=N key in the product molecule, illustrating to have formed the pyrazoline ring; Near the stretching vibration peak that C=C 1623.48, occurred, this peak belongs to the two keys on 3 on the pyrazoline ring, 1273.17 and 1227.12C belongs to C-N stretching vibration in the C-N stretching vibration and naphthalene nucleus on the phenyl ring respectively, 741.21 and 727.14 belong to C-H flexural vibration in the C-H flexural vibration and phenyl ring on the naphthalene nucleus respectively, wherein C is a carbon atom, and N is a nitrogen-atoms, and H is a hydrogen atom, C=N is a carbon-to-nitrogen double bon, and C=C is a carbon-carbon double bond.
Fig. 8 is the product molecular structure, among the figure as can be known: N is a nitrogen-atoms.
Fig. 9 is product fluorescence spectrum figure, and ordinate zou is a relative intensity, and X-coordinate is wavelength nm, among the figure as can be known: the photoluminescence spectra maximum emission wavelength is that 523nm, halfwidth are 96nm.
Figure 10 is product chromaticity coordinates figure, among the figure as can be known: chromaticity coordinates x=0.3257, y=0.5452, the jaundice green glow.
Figure 11 is the product uv absorption spectra, and ordinate zou is a relative intensity, and X-coordinate is wavelength nm, and two absorption peaks appear in uv-absorbing, are respectively the π → π that is positioned at the 349nm place
*Transition absorption peak and the n → π that is positioned at the 420nm place
*The transition absorption peak; π → π
*Transition: the more easy excitated π that transits to of π-electronics
*Track, π
*Track is an antibonding(molecular)orbital, and the corresponding wavelength scope is longer, absorbs generally greater than 200nm; N → π
*Transition: occur in carbon atom or other atom and have in the π key compound that heteroatoms of Cheng Jian does not form n → π
*Transition institute energy requirement is lower, and the corresponding wavelength scope is near ultraviolet region 190～400nm.
Claims (3)
1, a kind of synthetic method of pyrazoline derivative of the green glow that turns to be yellow, it is characterized in that: the chemical substance that preparation is used is: the N-phenyl-1-naphthylamine, iodobenzene, potassium hydroxide, 18-hat-6, cuprous iodide, tetraline, aluminium sesquioxide, hexanaphthene, N, N '-dimethyl formamide, phosphorus oxychloride, Calcium Chloride Powder Anhydrous, N, N '-phenylbenzene-naphthalidine, sodium hydroxide, 4-(N-phenyl-1-naphthylamine) phenyl aldehyde, acetone, dehydrated alcohol, ethylene glycol monoethyl ether, hydrochloric acid, phenylhydrazine, methylene dichloride, sherwood oil, benzene, ethyl acetate, argon gas, the deionized water mixture of ice and water, quartz sand, absorbent cotton, its consumption is as follows: with gram, milliliter, centimetre
3Be measure unit
N-phenyl-1-naphthylamine: C
16H
13N 5.7g ± 0.05g
Iodobenzene: C
6H
5I 6ml ± 0.5ml
Potassium hydroxide: KOH 8.4g ± 0.05g
18-hat-6:C
20H
36O
60.5g ± 0.05g
Cuprous iodide: CuI 1.909g ± 0.05g
Aluminium sesquioxide: Al
2O
360g ± 5g
Hexanaphthene: C
6H
12150ml ± 10ml
Phosphorus oxychloride: POCl
31.37ml ± 0.1ml
Calcium Chloride Powder Anhydrous: CaCl
25g ± 0.5g
N, N '-phenylbenzene-naphthalidine: C
22H
17N 1.475g ± 0.05g
Sodium hydroxide: NaOH 20% aqueous solution 10ml ± 0.5ml
NaOH 15% ethanolic soln 15ml ± 0.5ml
Tetraline: C
10H
1260ml ± 2ml
4-(N-phenyl-1-naphthylamine) phenyl aldehyde: C
23H
17NO 0.978g ± 0.05g
Acetone: C
3H
6O 0.24ml ± 0.02ml
Ethylene glycol monoethyl ether: C
4H
10O
220ml ± 1ml
Hydrochloric acid: HCl concentration 37.5% 0.2ml ± 0.05ml
Phenylhydrazine: C
6H
8N
20.05ml ± 0.01ml
Methylene dichloride: CH
2Cl
210ml ± 0.5ml
Benzene: C
6H
620ml ± 1ml
Ethyl acetate: C
4H
8O
220ml ± 1ml
Argon gas: Ar 60000cm
3± 1200cm
3
Deionized water mixture of ice and water: H
2O 100ml ± 10ml
Quartz sand: SiO
20.5g ± 0.05g
Absorbent cotton: 0.1g ± 0.05g
Synthetic method is as follows:
(1) selected raw chemical material
To carry out selectedly to preparing required raw chemical material, and carry out precision, control of purity:
N-phenyl-1-naphthylamine: 95%
Iodobenzene: 98%
Potassium hydroxide: 〉=99%
18-hat-6:99%
Cuprous iodide: 〉=98%
Tetraline: 〉=97%
Aluminium sesquioxide: neutral fineness 200～300 orders 〉=98%
Hexanaphthene: 〉=99%
N, N '-dimethyl formamide: 〉=99%
Phosphorus trichloride: 〉=98%
Calcium Chloride Powder Anhydrous: 〉=96%
N, N '-phenylbenzene-naphthalidine: 97%
Sodium hydroxide: 〉=98%
4-(N-phenyl-1-naphthylamine) phenyl aldehyde: 95%
Acetone: 〉=99%
Dehydrated alcohol: 〉=99%
Ethylene glycol monoethyl ether: 〉=99%
Hydrochloric acid: concentration 37.5%
Phenylhydrazine: 98%
Methylene dichloride: 〉=99%
Sherwood oil: 60～90 ℃ of boiling points
Benzene: 〉=99%
Ethyl acetate: 〉=99%
Argon gas: 99.9%
Deionized water mixture of ice and water: 99.9%
Quartz sand: fineness 60～80 orders
Absorbent cotton: degreasing rate 98%
(2) preparation intermediate product I:N, N '-phenylbenzene-naphthalidine
1. in four-hole boiling flask, add:
N-phenyl-1-naphthylamine: 5.7g ± 0.05g
Iodobenzene: 6ml ± 0.5ml
18-hat-6:0.5g ± 0.05g
Potassium hydroxide: 8.4g ± 0.05g
Cuprous iodide: 1.909g ± 0.05g
Tetraline: 60ml ± 2ml
2. to four-hole boiling flask input protection gas: argon gas
Input speed: 40cm
3/ min
3. four-hole boiling flask is placed on the heating jacket;
4. heating jacket is placed on the magnetic stirring apparatus;
5. insert thermometer, dropping funnel, tunger tube, water cycle prolong on the four-hole boiling flask respectively;
6. open heating jacket, magnetic stirring apparatus, water condensation circulation tube, 200 ℃ ± 5 ℃ of Heating temperatures, the magnetic agitation frequency is 300r/min;
7. under heated condition, under the water cycle condensing state, under the argon shield, under the magnetic stirring apparatus vigorous stirring, stir, churning time 1440min ± 20min stirs the back and becomes mixing solutions;
8. cold filtration
Close argon gas, water condensation circulation, heating jacket, magnetic stirring apparatus, mixing solutions under static state naturally cools to 20 ℃ ± 3 ℃, pours into then in the funnel of the neutral qualitative filter paper of liner, filters and collect filtrate;
9. distillation
Beaker that filtrate is housed as on the Rotary Evaporators, is steamed excessive tetraline and iodobenzene, obtain crude product powder 4.45g ± 0.05g of intermediate product I;
10. the dry method column chromatography is purified:
Sorbent material: aluminium sesquioxide
Eluent: sherwood oil 30ml ± 2ml, benzene 20ml ± 1ml, sherwood oil: benzene=3: 2, hexanaphthene 150ml ± 10ml;
Carry out in the tubular type chromatography column, tubular type chromatography column top is placed with dropping funnel, and the bottom connects drain pipe, and by control valve control, the drain pipe bottom is provided with collection container;
The dress post: the absorbent cotton 0.1g ± 0.05g that packs in the cylinder bottom, place quartz sand 0.5g ± 0.05g on absorbent cotton;
In post, slowly pour hexanaphthene 150ml ± 10ml then into, reinstall aluminium sesquioxide 60g ± 5g, beat shaft gently with the soft rubber rod simultaneously, make the aluminium sesquioxide even compact of packing into, no bubble produces, put crude product powder 4.45g ± 0.05g of intermediate product I to be purified on aluminium sesquioxide top, the eluent sherwood oil+benzene mixing solutions 50ml ± 3ml for preparing is poured in the dropping funnel, i.e. the chromatography column top;
Differentiate: after material to be separated is impregnated into aluminium sesquioxide fully, the colour band section of different colours will appear in shaft, use each color section of ultraviolet fluorescent light irradiation then, and each color section will produce luminous and not luminous section;
Wash-out: opening controlling valve, when powder to be purified is dissolved in hexanaphthene and is penetrated into aluminium sesquioxide fully, two colour bands appear in shaft, above a colour band be brown, below a colour band be light yellow, open dropping funnel, collect the solution of light yellow colour band, has collected closed control valve afterwards at liquid outlet;
Light yellow colour band solution with the Rotary Evaporators evaporate to dryness is collected gets intermediate product I white powder 3.95g ± 0.05g;
On the recrystallization equipment for purifying, carry out:
Beaker is placed on the magnetic stirring apparatus, in beaker, add dehydrated alcohol 15ml ± 1ml, intermediate product I powder 3.95g ± 0.05g, power-on, heated and stirred, temperature rise to 78 ℃ ± 0.5 ℃ of dehydrated alcohol boiling point, constant temperature boiling 0.5min, while hot solution is poured in the Glass Containers, placed the slowly volatilization of shady and cool place, recrystallization is purified and is repeated secondary, get intermediate product I:N, N '-phenylbenzene-naphthalidine white crystal 3.45g ± 0.05g;
(3) preparation intermediate product II:4-(N-phenyl-1-naphthylamine) phenyl aldehyde
1. preparation: N, N '-phenylbenzene-naphthalidine+N, N '-dimethyl formamide solution
In there-necked flask, with white crystal N, N '-phenylbenzene-naphthalidine 1.475g ± 0.05g and N, N '-dimethyl formamide 10ml ± 1ml mixes, and is stirred into solution;
2. stirrer is put into there-necked flask, there-necked flask is placed the beaker that fills mixture of ice and water, beaker is placed on the rotation magnetic force agitator;
3. in there-necked flask, add:
N, N '-dimethyl formamide 5ml ± 1ml, phosphorus oxychloride 1.37ml ± 0.1ml;
4. insert tunger tube at there-necked flask, input argon gas 40cm
3/ min;
5. insert drying tube and add siccative Calcium Chloride Powder Anhydrous 5g ± 0.5g at there-necked flask;
6. add the N for preparing at the there-necked flask liquid adding hole, N '-phenylbenzene-naphthalidine+N, N '-dimethyl formamide solution stirs 60min ± 10min under the ice-water bath state;
7. there-necked flask is placed in the heating jacket, heating jacket places on the rotation magnetic force agitator, removes drying tube, changes the water condensation circulation tube, opens heating jacket, is warming up to 60 ℃ ± 5 ℃, and constant temperature keeps 360min ± 10min, and mixing solutions carries out combination reaction;
8. after reaction finishes, reaction soln in the there-necked flask is poured in the beaker of the deionized water mixture of ice and water that fills 100ml ± 10ml, mix the back and a large amount of yellow-green colour flosss occur, add sodium hydroxide 20% aqueous solution 10ml ± 0.5ml, the limit drips, stir on the limit, treats pH=6～8 o'clock, solution meta-alkalescence, stop to drip, continue to stir 60min ± 10min then;
9. suction filtration: mixing solutions is poured in the B of the three layers of middling speed qualitative filter paper of liner on the vacuum filtration bottle, is used the vacuum pump suction filtration rapidly, the khaki color solid product;
10. dry: as to get intermediate product II, i.e. 4-(N-phenyl-1-naphthylamine) phenyl aldehyde powder after the seasoning;
Intermediate product II:4-(N-phenyl-1-naphthylamine) phenyl aldehyde that makes is placed the column chromatography equipment for purifying, carrying out column chromatography with aforesaid method of purification purifies, eluent is the mixing solutions 40ml ± 2ml of ethyl acetate+sherwood oil, ethyl acetate: sherwood oil=1: 1, collect luminous colour band, obtain intermediate product II solution;
With Rotary Evaporators evaporate to dryness intermediate product II solution, obtain intermediate product II yellow powder, that is: 4-(N-phenyl-1-naphthylamine) phenyl aldehyde 1.184g ± 0.1g;
(4) preparation intermediate product III:4,4 '-two (N, N '-phenylbenzene-naphthalidine)-pentadiene ketone
1. in there-necked flask, add: 4-(N-phenyl-1-naphthylamine) phenyl aldehyde 0.978g ± 0.05g, acetone 0.24ml ± 0.02ml, dehydrated alcohol 40ml ± 2ml;
2. 15% ethanolic soln of dropping sodium: 15ml ± 0.5ml in there-necked flask, the speed of splashing into is 15/min, control pH=7～9, meta-alkalescence;
3. stirring reaction 1440min ± 30min under 20 ℃ ± 3 ℃ temperature of normal temperature stirs back solution and is safran, generates yellow floss;
4. suction filtration
The safran solution that will contain yellow floss places the B of vacuum filtration bottle, with three layers of middling speed qualitative filter paper suction filtration, stays the product filter cake;
5. seasoning: will get intermediate product III yellow powder, i.e. 4,4 '-two (N, N '-phenylbenzene-naphthalidine)-pentadiene ketone 0.57g ± 0.05g after the filter cake seasoning;
(5) the synthetic final product of preparation: pyrazoline derivative---1-phenyl-3-[4-(N-phenyl-1-naphthylamine)-phenyl vinyl]-5-[4-(N-phenyl-1-naphthylamine) phenyl]-the 2-pyrazoline
1. in there-necked flask, add: 4,4 '-two (N, N '-phenylbenzene-naphthalidine)-pentadiene ketone 0.32g ± 0.05g, ethylene glycol monoethyl ether 20ml ± 1ml;
2. drip concentrated hydrochloric acid 0.2ml ± 0.05ml in there-necked flask, solution becomes light green;
3. in there-necked flask, drip phenylhydrazine 0.05ml ± 0.01ml, there-necked flask is placed on the heating jacket heat then, 100 ℃ ± 5 ℃ of Heating temperatures, time 180min ± 10min, solution becomes sorrel;
4. in there-necked flask, add methylene dichloride 10ml ± 0.5ml, the solution layering, the upper strata is a dichloromethane solution, lower floor is an ethylene glycol monoethyl ether solution, collects upper strata brown-green liquid;
5. evaporimeter drying
With Rotary Evaporators desciccate solution, get final product powder 0.215g ± 0.05g;
6. recrystallization is purified
In beaker, add dehydrated alcohol 10ml ± 0.5ml, 0.215g ± 0.05g puts into beaker with the final product powder, power-on, heated and stirred, temperature rise to 78 ℃ ± 0.5 ℃ of dehydrated alcohol boiling point, constant temperature boiling 0.5min, while hot solution is poured in the Glass Containers, place the slowly volatilization of place, cool place, recrystallization is purified and is repeated secondary, gets the brown-green final product;
7. seasoning
The final product of purifying through secondary recrystallization carries out seasoning in cleaning place, time 120min ± 10min, get high purity final product crystal, be the brown-green pyrazoline derivative: 1-phenyl-3-[4-(N-phenyl-1-naphthylamine)-phenyl vinyl]-5-[4-(N-phenyl-1-naphthylamine) phenyl]-the 2-pyrazoline, described product structure is as follows:
(6) detect, analyze, characterize
Synthetic pyrazoline derivative product is detected, analyzes and characterizes:
1. recording the product crystal morphology for 100 times with the scanning electron microscope amplification is the particulate state rhombus;
2. use determination of infrared spectroscopy product molecular structure;
3. measure the photoluminescence spectrum and the chromaticity coordinates of product with fluorescence spectrophotometer;
4. carry out ultraviolet absorption spectroscopy with ultraviolet spectrometer;
(7) store
The turn to be yellow pyrazoline derivative product of green glow of synthetic is placed brown transparent Glass Containers, airtight keeping in Dark Place, be stored in cool place, drying, the clean environment, waterproof, protection against the tide, fire prevention, sun-proof, anti-acid and alkali corrosion, storing temp is 20 ℃ ± 3 ℃, relative humidity≤30%.
2, the synthetic method of the pyrazoline derivative of a kind of green glow that turns to be yellow according to claim 1, it is characterized in that: described high purity pyrazoline derivative---1-phenyl-3-[4-(N-phenyl-1-naphthylamine)-phenyl vinyl]-5-[4-(N-phenyl-1-naphthylamine) phenyl]-2-pyrazoline jaundice green glow, its chromaticity coordinates x=0.3257, y=0.5452, photoluminescence spectra maximum emission wavelength are that 523nm, halfwidth are 96nm.
3, the synthetic method of the pyrazoline derivative of a kind of green glow that turns to be yellow according to claim 1 is characterized in that: the pyrazoline derivative product crystal of described jaundice green glow, its pattern are brown-green particulate state rhombus.
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