CN108623584A - Bis- (aryl ethane base) quinazolinones of 2,8- and its preparation method and application - Google Patents
Bis- (aryl ethane base) quinazolinones of 2,8- and its preparation method and application Download PDFInfo
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Abstract
The invention discloses one kind 2 as shown in formula (I), 8 bis- (aryl ethane base) quinazolinones, preparation method is using the dibromo pyridine of 5 bromo-isatin sums as raw material, 2, the 8 dibromo quinazolinones of reaction synthesis under the catalysis of Copper (II) reagent；2,8 dibromo quinazolinones are with substitutedphenylethynyl under Copper (I) reagents and the catalysis of Pd (IV) reagent, 2,8 bis- (aryl ethane base) quinazolinones shown in synthesis formula (I) are reacted in anhydrous organic amine.The advantages that preparation method raw material of the present invention is easy to get, is simple for process, route is short, reaction condition is mild, open up 2 simultaneously, 8 bis- applications of (aryl ethane base) quinazolinones as third order non-linear optical material have larger implementary value and good economic results in society.
Description
Technical field
The present invention relates to third order non-linear optical material fields, and in particular to bis- (aryl ethane base) quinazolines of 2,8- of one kind
Ketone compound and preparation method thereof and application as third order non-linear optical material.
Background technology
In the development of photoelectric technology, nonlinear optics (Nonlinera Optics, NLO) material be realize optical oomputing,
The important substance basis of the optical technologies such as optical communication and optical Limiting application.Although traditional Inorganic Nonlinear Optical Materials have larger
Non-linear susceptibility, but the nonlinear effect of such material is usually associated with resonance condition, thus, absorb and heat consumption compared with
Greatly, since response mechanism is distortion of lattice, cause the response time of material longer (ns magnitudes).Organic non linear optical material with
Inorganic material is compared, and has nonlinear optical coefficients are big, fast response time, optical damage threshold are high, direct current dielectric constant is low etc.
Notable advantage, therefore, by the scientific research personnel in each field of optical material it is long-term and persistent study.
As organic non linear optical material, there are the quinoxaline compounds and quinoline of similar structure to quinazolinones
Isoxazoline compound finds there is good optical property by research, has been widely used on optical material, such as anti-fake organic
Fluorescer, organic light-emitting etc..But research of the quianzolinones in optical property is less, it is non-thread in three ranks
The research of property optical property is almost nil.Quinazolinone has rigidity as charge transfer compound is conjugated in molecule
Coplanar structure and good by electronic capability, can reduce energy gap (Egap) and promote Intramolecular electron transfer process, by closing
Preferable optical property can be obtained after the modification of reason.
Quinazolinones have in photoelectric information, lead to due to its unique structure and electrochemistry and optical characteristics
The potential using value of the high-tech sectors such as news and integrated optics, has caused the broad interest of researcher.
Invention content
The present invention is intended to provide a kind of bis- (aryl ethane base)-quinazolinones of 2,8- and preparation method thereof and three
The application of rank nonlinear optical material, this method raw material is easy to get, is simple for process, route is short, reaction condition is mild, prepared chemical combination
Object has good organic third order non-linear optical property.
The technical solution adopted by the present invention is as follows：
Bis- (aryl ethane base) quinazolinones of 2,8- of one kind, as shown in formula (I)：
Wherein, R is hydrogen, the alkyl of C1~C5, C3~C6 naphthenic base, contains 1~2 selected from heteroatomic 3~6 yuan of N, O and S
Heterocycle, alkoxy, hydroxyl, halogen, nitro, CF3Or phenyl, in the phenyl 1~3 hydrogen can each independently by C1~
Alkyl, hydroxyl, phenyl, halogen, alkoxy, nitro or the CF of C43Substitution.
Bis- (aryl ethane base) quinazolinones of 2, the 8-, further preferably formula (I-1), (I-2), (I-
3), the compound of (I-4), (I-5), (I-6) structure：
The preparation method of bis- (aryl ethane base) quinazolinones of 2,8- of the present invention, includes the following steps：
Step (1)：Dibromo pyridine shown in 5-bromoisatin shown in formula (II) and formula (III) is dissolved in organic solvent a, is added
Enter inorganic salts and Copper (II) agent catalyst, reaction solution, which is warming up at 80~130 DEG C, to react 8~24 hours, and the reaction was complete
Afterwards, reaction solution obtains 2,8- dibromo quinazolinones shown in formula (IV) by post-processing A；
Step (2)：Under nitrogen protection, 2,8- dibromo quinazolinones shown in formula (IV) are dissolved in anhydrous organic
In amine, Copper (I) reagents and Pd (IV) agent catalyst is added, is stirred 0.5 hour~2 hours at 70 DEG C~90 DEG C, then drip
Add substitutedphenylethynyl shown in formula (V), reaction solution to be warming up to 90~120 DEG C, reacts 15~30 hours, after the reaction was complete, reaction
Liquid obtains bis- (aryl ethane base) quinazolinones of 2,8- shown in formula (I) by post-processing B；
Wherein, the R in the R and formula (I) in formula (V) has identical meanings.
In step (1), in step (1), the organic solvent a is DMF (n,N-Dimethylformamide), DMSO (diformazans
Base sulfoxide), DMAC N,N' dimethyl acetamide, 2- methyltetrahydrofurans, one or more of dioxanes；The inorganic salts
For sodium bicarbonate or saleratus；Described Copper (II) reagent is Cu (OAc)2、Cu(OTf)2Or Cu (TFA)2；
The 5-bromoisatin (II)：Dibromo pyridine (III)：Inorganic salts：The amount of the substance that feeds intake of Copper (II) reagent
Than being 1.0：1.0~1.2：1.8~2.5：0.1~0.2；
The volumetric usage of the organic solvent a is calculated as 15~25mL/g with substrate 5-bromoisatin (II) quality；
The post-processing A is carried out as follows：After reaction solution cooling, it is poured into saturated salt solution, stirring and crystallizing waits for
Solid is precipitated completely, and filtering, filter cake is purified through column chromatography for separation, and eluant, eluent is volume ratio petroleum ether：CH2Cl2=1.5~2.5：
1, further preferably, eluant, eluent is volume ratio petroleum ether：CH2Cl2=2：1.
In step (2), the anhydrous organic amine be triethylamine, DBU (1,8- diazabicylo, 11 carbon -7- alkene),
DIPEA (N, N- diisopropylethylamine), N-methylmorpholine；Described Copper (I) reagent is CuCl, CuBr or CuI；Described
Pd (IV) reagent is Pd (PPh3)4、(MeCN)2PdCl2Or (PPh3)2PdCl2；
Further preferably, it stirs at 0.5 hour~2 hours, 80 DEG C and stirs 1 hour at 70 DEG C~90 DEG C.
The 2,8- dibromos quinazolinones (IV)：Substitutedphenylethynyl (V)：Copper (I) reagent：Pd (IV) is tried
The amount ratio of the substance that feeds intake of agent is 1.0：2.0~2.5：0.05~0.15：0.01~0.1；
The volumetric usage of the anhydrous organic amine is calculated as 20 with substrate 2,8- dibromos quinazolinones (IV) quality
~25mL/g；
The post-processing B is carried out as follows：After reaction solution cooling, evaporated under reduced pressure, solid is carried through column chromatography for separation
Pure, eluant, eluent is volume ratio petroleum ether：CH2Cl2=0.8~1.3：1, further preferably, eluant, eluent is volume ratio petroleum ether：
CH2Cl2=1：1.
It is of the present invention as to can be used as three ranks non-for bis- (aryl ethane base) quinazolinones of 2,8- shown in formula (I)
Linear optical material is tested using Z- scanning techniques；
With Nd：YAG laser (PL2143B, EKSPLA) is light source, and it is 532nm, arteries and veins to test laser pulse wavelength used
It is 190fs, repetition rate 10Hz to rush width；
Sample test：Sample is made into the CH of a concentration of 1.0mg/mL2Cl2Solution is placed in the sample cell that thickness is 2mm,
Incoming laser beam is focused on by focal length lenses in sample cell, and the hot spot waist radius of focal position is 30 μm, uses energy meter
(Laser Probe Corporation, Rj-7620) measures projectile energy and transmission energy；
Before test sample, solvent C H is under equal conditions tested2Cl2Nonlinear optical effect, as a result display can be with
Ignore influence of the nonlinear optical effect to test of solvent；
When sample there are a trepanning and closed pore curve when non-linear absorption, is done respectively, the data measured under closed pore are utilized
Divided by single nonlinear refraction property is obtained after trepanning data normalization；
The instantaneous light intensity of focal point laser is calculated by formula (1)：
The effective thickness L of sampleeff, it is calculated by formula (2)：
In formula (2), α0For the linear absorption of sample
The two-photon absorption factor beta of sample is calculated trepanning curve matching by formula (3)：
The nonlinear refractive index index n of sample2, it is calculated by formula (4)：
In formula (4), S is aperture linear transmittance, △ Tp-vFor sample peak-valley difference, n0For the linear refractive of solvent
Rate.
The third-order nonlinear susceptibility χ of sample(3)It is divided into real and imaginary parts, is calculated by following equation (5)：
Wherein, real part is calculated by formula (6)：
In formula (6), n0For the linear refractive index of solvent；
Imaginary part is calculated by formula (7)：
In formula (7), n0For the linear refractive index of solvent；ε0For permittivity of vacuum；ω is the angular frequency of light field；
The second hyperpolarizabilitieof γ of sample is calculated by formula (8)：
In formula (8), N is the molecular density of solute, N=NAC, c are the molar concentration of sample solution；F repaiies for local fields
Positive divisor, numerical value are equal to (n0 2+2)/3；
Third-order non-linear of the present invention such as bis- (aryl ethane base) quinazolinones of 2,8- shown in formula (I)
Optical property is tested using Z- scanning techniques, and test result is shown, with good performance, 2,8- bis- (aryl ethane bases)
Quinazolinones can be used as the application of third order non-linear optical material.
Bis- (aryl ethane base) quinazolinones of 2,8- of one kind and preparation method of the present invention and it is non-in three ranks
Application in linear optics, advantageous effect are mainly reflected in：The preparation method raw material is easy to get, is simple for process, route is short, reaction item
The advantages that part is mild, while 2 have been opened up, bis- (aryl ethane base) quinazolinones the answering in third-order nonlinear optical of 8-
With with larger implementary value and good economic results in society.
Description of the drawings
Fig. 1 is to detect compound I-1~I-6, chemical combination obtained by the embodiment of the present invention 6 to embodiment 12 with Z- scanning techniques
Object QZ and solvent C H2Cl2Non-linear trepanning Z- scanning curves, wherein small circle be laboratory data, solid line be fitting number
According to.
Fig. 2 is to detect compound I-1~I-6, chemical combination obtained by the embodiment of the present invention 6 to embodiment 12 with Z- scanning techniques
Object QZ and solvent C H2Cl2Non-linear closed pore Z- scanning curves, wherein small circle be laboratory data, solid line be fitting number
According to.
Fig. 3 is to detect compound I-1~I-6 and change obtained by the embodiment of the present invention 6 to embodiment 12 with Z- scanning techniques
Close the non-linear trepanning Z- scanning curves of object QZ.
Specific implementation mode
Technical scheme of the present invention is described in more detail by following specific examples, but protection scope of the present invention is not
It is limited to this：
The synthesis of 2,8-, bis- bromo- 11H- pyridos [2,1-b] quinoline azoles -11- ketone, chemical equation shown in formula (IV)
It is as follows：
Embodiment 1
According to the amount of substance than 5-bromoisatin (II)：Dibromo pyridine (III)：Inorganic salts：Copper (II) reagent is 1.0：
1.0：1.8：0.2 feeds intake, wherein 5-bromoisatin (II) 2.26g, and dibromo pyridine (III) 2.37g, inorganic salts are sodium bicarbonate, throws
Material quality 1.51g, Copper (II) reagent is Cu (OAc)2, the quality that feeds intake 0.36g；Organic solvent a is DMF 35mL, volume
Dosage is 15 times (mL/g) of formula (II) quality；
In the there-necked flask of 100mL dried and cleans, dibromo shown in 5-bromoisatin, formula (III) shown in formula (II) is added
Pyridine, sodium bicarbonate, Cu (OAc)2With DMF (n,N-Dimethylformamide), 120 DEG C are heated to, it is anti-after reacting 10 hours
It should be complete；Reaction solution is cooled to room temperature 25 DEG C, is poured into the saturated salt solution of 3 times of amounts of reaction solution volume, stirring and crystallizing waits for solid
It is precipitated completely, filtering, through column chromatography for separation purification, (eluant, eluent is volume ratio petroleum ether to filter cake：CH2Cl2=2：1) 2,8- bis-, is obtained
Bromo- 11H- pyridos [2,1-b] quinoline azoles -11- ketone (compound IV) 3.0g, yield 84.7%；
Compound (IV) structural formula is as follows：
The characterize data of compound (IV) is as follows：
Fusing point：M.p.262-264℃.1H NMR(500MHz,CDCl3) δ 9.00 (dd, J=2.3,0.7Hz, 1H), 8.58
(d, J=2.3Hz, 1H), 7.96-7.87 (m, 1H), 7.67 (d, J=8.8Hz, 1H), 7.57 (dd, J=9.6,2.2Hz, 1H),
7.40 (dd, J=9.7,0.7Hz, 1H)
In conjunction with characterize data, show that the product that the present embodiment obtains is formula (IV) structure.
Embodiment 2
According to the amount of substance than 5-bromoisatin (II)：Dibromo pyridine (III)：Inorganic salts：Copper (II) reagent is 1.0：
1.1：2.0：0.15 feeds intake, wherein 5-bromoisatin (II) 2.26g, and dibromo pyridine (III) 2.61g, inorganic salts are sodium bicarbonate, throws
Material quality 1.68g, Copper (II) reagent is Cu (OAc)2, the quality that feeds intake 0.27g；Organic solvent a is DMSO 45mL, body
Product dosage is 20 times (mL/g) of formula (II) quality；
Wherein, reaction temperature is 130 DEG C, and the reaction time is 10 hours, other other operations obtain product with embodiment 1
2.85g, i.e. compound IV, yield 80.5%.
Embodiment 3
According to the amount of substance than 5-bromoisatin (II)：Dibromo pyridine (III)：Inorganic salts：Copper (II) reagent is 1.0：
1.2：2.5：0.10 feeds intake, wherein 5-bromoisatin (II) 2.26g, and dibromo pyridine (III) 2.84g, inorganic salts are sodium bicarbonate, throws
Material quality 2.10g, Copper (II) reagent is Cu (OTf)2, the quality that feeds intake 0.36g；Organic solvent a is N, N- dimethylacetamides
Amine 55mL, volumetric usage are 25 times (mL/g) of formula (II) quality；
Wherein, reaction temperature is 120 DEG C, and the reaction time is 10 hours, other other operations obtain product with embodiment 1
3.10g, i.e. compound IV, yield 87.6%.
Embodiment 4
According to the amount of substance than 5-bromoisatin (II)：Dibromo pyridine (III)：Inorganic salts：Copper (II) reagent is 1.0：
1.1：2.0：0.10 feeds intake, wherein 5-bromoisatin (II) 2.26g, and dibromo pyridine (III) 2.61g, inorganic salts are saleratus, throws
Material quality 2.00g, Copper (II) reagent is Cu (OTf)2, the quality that feeds intake 0.36g；Organic solvent a is 2- methyltetrahydrofurans
45mL, volumetric usage are 20 times (mL/g) of formula (II) quality；
Wherein, reaction temperature is 80 DEG C, and the reaction time is 24 hours, other other operations obtain product with embodiment 1
2.92g, i.e. compound IV, yield 82.5%.
Embodiment 5
According to the amount of substance than 5-bromoisatin (II)：Dibromo pyridine (III)：Inorganic salts：Copper (II) reagent is 1.0：
1.2：2.3：0.15 feeds intake, wherein 5-bromoisatin (II) 2.26g, and dibromo pyridine (III) 2.84g, inorganic salts are saleratus, throws
Material quality 2.30g, Copper (II) reagent is Cu (TFA)2, the quality that feeds intake 0.43g；Organic solvent a is dioxanes 55mL, body
Product dosage is 25 times (mL/g) of formula (II) quality；
Wherein, reaction temperature is 100 DEG C, and the reaction time is 18 hours, other other operations obtain product with embodiment 1
3.01g, i.e. compound IV, yield 85.0%.
The synthesis of bis- (aryl ethane base) quinazolinones of 2,8- shown in formula (I), chemical equation are as follows：
Embodiment 6
The preparation of bis- (phenylacetylene base) -11H- pyridos [2,1-b] quinoline azoles -11- ketone (compound abbreviation I-1) of 2,8-：It presses
According to the amount ratio 2,8- dibromos quinazolinones (IV) of substance：Substitutedphenylethynyl (V)：Copper (I) reagent：Pd (IV) reagent
It is 1.0：2.0：0.15：0.1 feeds intake, wherein 2,8- dibromo quinazolinones (IV) 1.06g, substitutedphenylethynyl (V) are benzene
Acetylene, the quality that feeds intake 0.61g, Copper (I) reagent are CuCl, and the quality that feeds intake 0.045g, Pd (IV) reagent is Pd (PPh3)4, throw
Expect quality 0.35g；Anhydrous organic amine is triethylamine 25mL, and volumetric usage is 25 times (mL/g) of formula (IV) quality
In the there-necked flask of 100mL dried and cleans, 2,8- dibromos quinazolinones, three second shown in formula (IV) are added
Amine, CuCl and Pd (PPh3)4, lead to nitrogen protection, be heated to 80 DEG C, stir 1 hour, phenylacetylene is added dropwise, reaction solution is warming up to
90 DEG C, the reaction was complete after 30 hours for reaction, and after the cooling of reaction solution reaction solution, evaporated under reduced pressure, solid is purified through column chromatography for separation, is washed
De- agent is volume ratio petroleum ether：CH2Cl2=1：1, obtain product 0.97g, as compound (I-1), yield 81.6%.
Compound (I-1) structural formula is as follows：
The characterize data of compound (I-1) is as follows：
Fusing point：M.p.211-212℃.1H NMR(500MHz,CDCl3) δ 9.09 (dd, J=1.9,0.8Hz, 1H), 8.64
(dd, J=2.0,0.5Hz, 1H), 7.95 (dd, J=8.6,2.0Hz, 1H), 7.77 (dd, J=8.6,0.6Hz, 1H), 7.58
(dddd, J=7.3,5.7,4.1,2.4Hz, 5H), 7.50 (dd, J=9.4,0.8Hz, 1H), 7.43-7.36 (m, 6H)
HRMS(ESI)m/z calcd for C28H17N2O+[M+H]+397.13,found 397.13.
In conjunction with characterize data, show that the product that the present embodiment obtains is formula (I-1) structure.
Embodiment 7
2,8- bis- (p-methoxyphenyl acetenyls) -11H- pyridos [2,1-b] quinoline azoles -11- ketone (compound abbreviation I-2)
Preparation：According to the amount ratio 2,8- dibromos quinazolinones (IV) of substance：Substitutedphenylethynyl (V)：Copper (I) reagent：
Pd (IV) reagent is 1.0：2.3：0.10：0.05 feeds intake, wherein 2,8- dibromo quinazolinones (IV) 1.06g, substituted benzene
Acetylene (V) is to Methoxy-phenylacetylene, and the quality that feeds intake 0.91g, Copper (I) reagent is CuBr, the quality that feeds intake 0.043g, Pd
(IV) reagent is (MeCN)2PdCl2, the quality that feeds intake 0.038g；Anhydrous organic amine is DBU 20mL, and volumetric usage is formula (IV)
20 times (mL/g) of quality
Wherein, reaction temperature is 120 DEG C, and the reaction time is 15 hours, other other operations obtain product with embodiment 6
1.08g, i.e. compound (I-2), yield 78.9%.
Compound (I-2) structural formula is as follows：
The characterize data of compound (I-2) is as follows：
Fusing point：M.p.252-253℃.1H NMR(500MHz,CDCl3) δ 9.04 (dd, J=2.0,0.8Hz, 1H), 8.59
(d, J=1.9Hz, 1H), 7.92 (dd, J=8.6,2.0Hz, 1H), 7.74 (d, J=8.6Hz, 1H), 7.55-7.47 (m, 6H),
6.96-6.87 (m, 4H), 3.86 (d, J=1.1Hz, 7H)
HRMS(ESI)m/z calcd for C30H21N2O3 +[M+H]+457.15,found 457.15.
In conjunction with characterize data, show that the product that the present embodiment obtains is formula (I-2) structure.
Embodiment 8
The system of 2,8- bis- (to chlorobenzene acetenyls) -11H- pyridos [2,1-b] quinoline azoles -11- ketone (compound abbreviation I-3)
It is standby：According to the amount ratio 2,8- dibromos quinazolinones (IV) of substance：Substitutedphenylethynyl (V)：Copper (I) reagent：Pd
(IV) reagent is 1.0：2.5：0.05：0.01 feeds intake, wherein 2,8- dibromo quinazolinones (IV) 1.06g, substituted benzene second
Alkynes (V) is to chlorobenzene acetylene, and the quality that feeds intake 1.02g, Copper (I) reagent is CuI, the quality that feeds intake 0.029g, Pd (IV) reagent
For (PPh3)2PdCl2, the quality that feeds intake 0.021g；Anhydrous organic amine is DIPEA 20mL, and volumetric usage is formula (IV) quality
20 times (mL/g)
Wherein, reaction temperature is 120 DEG C, and the reaction time is 15 hours, other other operations obtain product with embodiment 6
0.96g, i.e. compound (I-3), yield 68.8%.
Compound (I-3) structural formula is as follows：
The characterize data of compound (I-3) is as follows：
Fusing point：M.p.285-286℃.1H NMR(500MHz,CDCl3) δ 9.08 (dd, J=2.0,0.8Hz, 1H), 8.63
(d, J=1.9Hz, 1H), 7.94 (dd, J=8.6,2.0Hz, 1H), 7.77 (d, J=8.6Hz, 1H), 7.57 (dd, J=9.4,
1.9Hz,1H),7.53–7.47(m,6H),7.41–7.35(m,5H),7.28(s,4H).
HRMS(ESI)m/z calcd for C28H15N2OCl2 +[M+H]+465.05,found 465.05.
In conjunction with characterize data, show that the product that the present embodiment obtains is formula (I-3) structure.
Embodiment 9
The system of 2,8- bis- (to methyl phenylacetylene bases) -11H- pyridos [2,1-b] quinoline azoles -11- ketone (compound abbreviation I-4)
It is standby：According to the amount ratio 2,8- dibromos quinazolinones (IV) of substance：Substitutedphenylethynyl (V)：Copper (I) reagent：Pd
(IV) reagent is 1.0：2.3：0.10：0.10 feeds intake, wherein 2,8- dibromo quinazolinones (IV) 1.06g, substituted benzene second
Alkynes (V) is to methyl phenylacetylene, and the quality that feeds intake 0.80g, Copper (I) reagent is CuI, the quality that feeds intake 0.057g, Pd (IV) examination
Agent is Pd (PPh3)4, the quality that feeds intake 0.35g；Anhydrous organic amine is N-methylmorpholine 25mL, and volumetric usage is formula (IV) quality
25 times (mL/g)
Wherein, reaction temperature is 110 DEG C, and the reaction time is 20 hours, other other operations obtain product with embodiment 6
1.02g, i.e. compound (I-4), yield 80.1%.
Compound (I-4) structural formula is as follows：
The characterize data of compound (I-4) is as follows：
Fusing point：M.p.271-272℃.1H NMR(500MHz,CDCl3) δ 9.04 (d, J=10.2Hz, 1H), 8.69-8.51
(m, 1H), 7.98-7.85 (m, 1H), 7.74 (d, J=8.6Hz, 1H), 7.55 (d, J=8.6Hz, 1H), 7.46 (t, J=
8.8Hz, 5H), 7.19 (dd, J=7.9,3.4Hz, 4H), 2.40 (s, 6H)
HRMS(ESI)m/z calcd for C30H21N2O+[M+H]+425.16,found 425.16.
In conjunction with characterize data, show that the product that the present embodiment obtains is formula (I-4) structure.
Embodiment 10
2,8- bis- (to n-propylbenzene acetenyls) -11H- pyridos [2,1-b] quinoline azoles -11- ketone (compound abbreviation I-5)
It prepares：According to the amount ratio 2,8- dibromos quinazolinones (IV) of substance：Substitutedphenylethynyl (V)：Copper (I) reagent：Pd
(IV) reagent is 1.0：2.0：0.10：0.05 feeds intake, wherein 2,8- dibromo quinazolinones (IV) 1.06g, substituted benzene second
Alkynes (V) is to n-propylbenzene acetylene, and the quality that feeds intake 0.87g, Copper (I) reagent is CuI, the quality that feeds intake 0.057g, Pd (IV)
Reagent is Pd (PPh3)4, the quality that feeds intake 0.17g；Anhydrous organic amine is triethylamine 25mL, and volumetric usage is formula (IV) quality
25 times (mL/g)
Wherein, reaction temperature is 90 DEG C, and the reaction time is 30 hours, other other operations obtain product with embodiment 6
1.07g, i.e. compound (I-5), yield 74.2%.
Compound (I-5) structural formula is as follows：
The characterize data of compound (I-5) is as follows：
Fusing point：M.p.222-223℃.1H NMR(500MHz,CDCl3) δ 9.03 (dd, J=2.0,0.8Hz, 1H), 8.58
(d, J=2.0Hz, 1H), 7.90 (dd, J=8.6,2.0Hz, 1H), 7.72 (d, J=8.6Hz, 1H), 7.60-7.36 (m, 6H),
7.19 (dd, J=8.1,3.1Hz, 4H), 2.62 (dd, J=8.4,6.8Hz, 4H), 1.66 (dtd, J=14.8,7.4,1.3Hz,
4H), 0.97 (t, J=7.3Hz, 6H)
HRMS(ESI)m/z calcd for C34H29N2O+[M+H]+481.22,found 481.22.
In conjunction with characterize data, show that the product that the present embodiment obtains is formula (I-5) structure.
Embodiment 11
2,8- bis- (to n-butylbenzene acetenyls) -11H- pyridos [2,1-b] quinoline azoles -11- ketone (compound abbreviation I-6)
It prepares：According to the amount ratio 2,8- dibromos quinazolinones (IV) of substance：Substitutedphenylethynyl (V)：Copper (I) reagent：Pd
(IV) reagent is 1.0：2.5：0.15：0.01 feeds intake, wherein 2,8- dibromo quinazolinones (IV) 1.06g, substituted benzene second
Alkynes (V) is to n-butylbenzene acetylene, and the quality that feeds intake 1.19g, Copper (I) reagent is CuBr, the quality that feeds intake 0.065g, Pd (IV)
Reagent is (MeCN)2PdCl2, the quality that feeds intake 0.01g；Anhydrous organic amine is N-methylmorpholine 25mL, and volumetric usage is formula (IV)
25 times (mL/g) of quality
Wherein, reaction temperature is 110 DEG C, and the reaction time is 20 hours, other other operations obtain product with embodiment 6
1.11g, i.e. compound (I-6), yield 72.7%.
Compound (I-6) structural formula is as follows：
The characterize data of compound (I-6) is as follows：
Fusing point：M.p.201-202℃.1H NMR(500MHz,CDCl3) δ 9.03 (dd, J=2.0,0.8Hz, 1H), 8.58
(d, J=1.9Hz, 1H), 7.90 (dd, J=8.6,2.0Hz, 1H), 7.72 (d, J=8.6Hz, 1H), 7.53 (dd, J=9.4,
1.9Hz, 1H), 7.49-7.44 (m, 5H), 7.19 (dd, J=8.1,3.1Hz, 5H), 2.74-2.56 (m, 4H), 1.63 (pd, J
=7.6,1.6Hz, 4H), 1.38 (hd, J=7.4,1.2Hz, 4H), 0.96 (t, J=7.4Hz, 6H)
HRMS(ESI)m/z calcd for C36H33N2O+[M+H]+509.25,found 509.25.
In conjunction with characterize data, show that the product that the present embodiment obtains is formula (I-6) structure.
Embodiment 12
The preparation of bis- bromo- 11H- pyridos [2,1-b] quinoline azoles -11- ketone (compound abbreviation QZ) of quinazolinone parent nucleus 2,8-：
In the there-necked flask of 100mL dried and cleans, isatin (0.73g, 5mmol), a bromopyridine (0.79mg, 5mmol), bicarbonate is added
Sodium (0.84g, 10mmol), Cu (OAc)2(0.18mg, 1mmol) and DMF 20mL are heated to 120 DEG C, react 15 hours
The reaction was complete afterwards；Reaction solution is cooled to room temperature, and is poured into the saturated salt solution of 150mL, stirring and crystallizing, waits for that solid is precipitated completely,
Filtering, through column chromatography for separation purification, (eluant, eluent is petroleum ether to filter cake：CH2Cl2=2：1) compound (QZ) 0.83g, yield, are obtained
85.0%；
Compound (QZ) structural formula is as follows：
The characterize data of compound (QZ) is as follows：
Fusing point：M.p.210-211℃.1H NMR(500MHz,CDCl3) δ 8.89 (dt, J=7.4,1.3Hz, 1H), 8.66-
8.33 (m, 1H), 7.85 (ddd, J=8.4,6.9,1.6Hz, 1H), 7.79 (dt, J=8.3,0.9Hz, 1H), 7.55-7.43
(m, 3H), 6.88 (ddd, J=7.6,5.0,2.8Hz, 1H)
In conjunction with characterize data, show that the product that the present embodiment obtains is formula (QZ) structure.
Embodiment 13
Third order non-linear optical property detects：
Third-order non-linear of the present invention such as bis- (aryl ethane base) quinazolinones of 2,8- shown in formula (I)
Optical property is tested using Z- scanning techniques；
With Nd：YAG laser (PL2143B, EKSPLA) is light source, and it is 532nm, arteries and veins to test laser pulse wavelength used
It is 190fs, repetition rate 10Hz to rush width；
Sample test：Sample is made into the CH of a concentration of 1.0mg/mL2Cl2Solution is placed in the sample cell that thickness is 2mm,
Incoming laser beam is focused on by focal length lenses in sample cell, and the hot spot waist radius of focal position is 30 μm, uses energy meter
(Laser Probe Corporation, Rj-7620) measures projectile energy and transmission energy；
Before test sample, solvent C H is under equal conditions tested2Cl2Nonlinear optical effect, as a result display can be with
Ignore influence of the nonlinear optical effect to test of solvent；
When sample there are a trepanning and closed pore curve when non-linear absorption, is done respectively, the data measured under closed pore are utilized
Divided by single nonlinear refraction property is obtained after trepanning data normalization；
The instantaneous light intensity of focal point laser is calculated by formula (1)：
The effective thickness L of sampleeff, it is calculated by formula (2)：
In formula (2), α0For the linear absorption of sample
The two-photon absorption factor beta of sample is calculated trepanning curve matching by formula (3)：
The nonlinear refractive index index n of sample2, it is calculated by formula (4)：
In formula (4), S is aperture linear transmittance, △ Tp-vFor sample peak-valley difference, n0For the linear refractive of solvent
Rate.
The third-order nonlinear susceptibility χ of sample(3)It is divided into real and imaginary parts, is calculated by following equation (5)：
Wherein, real part is calculated by formula (6)：
In formula (6), n0For the linear refractive index of solvent；
Imaginary part is calculated by formula (7)：
In formula (7), n0For the linear refractive index of solvent；ε0For permittivity of vacuum；ω is the angular frequency of light field；
The second hyperpolarizabilitieof γ of sample is calculated by formula (8)：
In formula (8), N is the molecular density of solute, N=NAC, c are the molar concentration of sample solution；F repaiies for local fields
Positive divisor, numerical value are equal to (n0 2+2)/3；
Test result is as shown in table 1, from third-order nonlinear susceptibility χ(3)With second hyperpolarizabilitieof γ as it can be seen that compared to quinoline
Oxazoline ketone parent nucleus compound QZ, the non-linear absorption coefficient of compound I-1~I-6 is significantly higher, has excellent performance, wherein I-2's
Performance is best, third-order nonlinear susceptibility χ(3)It is three times of quinazolinone parent nucleus compound QZ；
The structure-activity relationship of analysis and control compounds is it is found that 2,8 in quinazolinone mother nucleus structure introduce substituted benzene second
After ethynylene group, the steric hindrance of the both sides quinazolinone parent QZ can be increased, reduce intermolecular pi-pi accumulation, and by phenylacetylene
The push-pull configuration that group and quinazolinone skeleton are formed reduces the band gap Egap of molecule, to obtain better nonlinear optical
Learn response；
Compound I-2 is responded with better third-order nonlinear optical, and main there are two reasons：(1) due to methoxyl group
Good electron donability matter so that intramolecular charge mobility is more preferable, and the charge delocalization of molecule is also improved；(2) first
It is pi-conjugated that the lone pair electrons of oxygroup oxygen atom and the pi-electron of double bond form effective p-.
Bis- (aryl ethane base) the quinazolinones third order non-linear optical property parameters of 1 2,8- of table
Claims (10)
1. one kind 2, bis- (aryl ethane base) quinazolinones of 8-, which is characterized in that as shown in formula (I)：
Wherein, R be hydrogen, it is the alkyl of C1~C5, C3~C6 naphthenic base, miscellaneous selected from heteroatomic 3~6 yuan of N, O and S containing 1~2
Ring, alkoxy, hydroxyl, halogen, nitro, CF3Or phenyl, 1~3 hydrogen can be each independently by C1~C4's in the phenyl
Alkyl, hydroxyl, phenyl, halogen, alkoxy, nitro or CF3Substitution.
2. bis- (aryl ethane base) quinazolinones of 2,8- according to claim 1, which is characterized in that be formula (I-
1), the compound of (I-2), (I-3), (I-4), (I-5), (I-6) structure：
3. the preparation method of bis- (aryl ethane base) quinazolinones of 2,8- according to claim 1 or 2, feature
It is, includes the following steps：
Step (1)：Dibromo pyridine shown in 5-bromoisatin shown in formula (II) and formula (III) is dissolved in organic solvent a, nothing is added
Machine salt and Copper (II) agent catalyst, reaction solution, which is warming up at 80~130 DEG C, reacts 8~24 hours, after the reaction was complete, instead
Liquid is answered to obtain 2,8- dibromo quinazolinones shown in formula (IV) by post-processing A；
Step (2)：Under nitrogen protection, 2,8- dibromo quinazolinones shown in formula (IV) are dissolved in anhydrous organic amine
In, Copper (I) reagents and Pd (IV) agent catalyst is added, is stirred 0.5 hour~2 hours at 70 DEG C~90 DEG C, then be added dropwise
Substitutedphenylethynyl shown in formula (V), reaction solution are warming up to 90~120 DEG C, react 15~30 hours, after the reaction was complete, reaction solution
Bis- (aryl ethane base) quinazolinones of 2,8- shown in formula (I) are obtained by post-processing B；
Wherein, the R in the R and formula (I) in formula (V) has identical meanings.
4. preparation method according to claim 3, which is characterized in that in step (1), the organic solvent a is N, N-
One or both of dimethylformamide, dimethyl sulfoxide (DMSO), DMAC N,N' dimethyl acetamide, 2- methyltetrahydrofurans, dioxanes
More than；
The inorganic salts are sodium bicarbonate or saleratus；
Described Copper (II) reagent is Cu (OAc)2、Cu(OTf)2Or Cu (TFA)2。
5. preparation method according to claim 3, which is characterized in that in step (1), the 5-bromoisatin：Dibromo pyrrole
Pyridine：Inorganic salts：The amount ratio of the substance that feeds intake of Copper (II) reagent is 1.0：1.0~1.2：1.8~2.5：0.1~0.2；
The volumetric usage of the organic solvent a is calculated as 15~25mL/g with 5-bromoisatin quality.
6. preparation method according to claim 3, which is characterized in that in step (1), the post-processing A is by following step
It is rapid to carry out：It after reaction solution cooling, is poured into saturated salt solution, stirring and crystallizing, waits for that solid is precipitated completely, filter, filter cake is through column layer
Separating-purifying is analysed, eluant, eluent is volume ratio petroleum ether：CH2Cl2=1.5~2.5：1.
7. preparation method according to claim 3, which is characterized in that in step (2), the anhydrous organic amine is three second
Amine, DBU, DIPEA or N-methylmorpholine；
Described Copper (I) reagent is CuCl, CuBr or CuI；
Described Pd (IV) reagent is Pd (PPh3)4、(MeCN)2PdCl2Or (PPh3)2PdCl2。
8. preparation method according to claim 3, which is characterized in that in step (2), 2, the 8- dibromo quinazolinones
Compound：Substitutedphenylethynyl：Copper (I) reagent：The amount ratio of the substance that feeds intake of Pd (IV) reagent is 1.0：2.0~2.5：0.05
~0.15：0.01~0.1.
The volumetric usage of the anhydrous organic amine is calculated as 20~25mL/g with substrate 2,8- dibromo quinazolinones quality.
9. preparation method according to claim 3, which is characterized in that in step (2), the post-processing B is by following step
It is rapid to carry out：After reaction solution cooling, evaporated under reduced pressure, solid is purified through column chromatography for separation, and eluant, eluent is volume ratio petroleum ether：CH2Cl2
=0.8~1.3：1.
10. bis- (aryl ethane base) quinazolinones of 2,8- according to claim 1 or 2 are as third-order non-linear light
Learn the application of material.
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| CN1884281A (en) * | 2006-07-05 | 2006-12-27 | 浙江工业大学 | 3,7-diaryldibenzofuran-2,6-diketone third order nonlinear optical material |
| CN107936013A (en) * | 2017-11-13 | 2018-04-20 | 浙江工业大学 | A kind of D π A π D type quinazolinone third order non-linear optical materials and its preparation method and application |
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| CN107936013A (en) * | 2017-11-13 | 2018-04-20 | 浙江工业大学 | A kind of D π A π D type quinazolinone third order non-linear optical materials and its preparation method and application |
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| CN107936013B (en) * | 2017-11-13 | 2020-01-14 | 浙江工业大学 | D-pi-A-pi-D type quinazolinone three-order nonlinear optical material and preparation method and application thereof |
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