CN105713598B - Five substituted-tetrahydro pyrimidine derivatives are preparing the application in causing fluorescence off-color material with pressure - Google Patents

Abstract

The present invention provides an application of a five-substituted ectoine derivative in the preparation of a piezofluorescent material, the derivative having a structure as shown in formula (I): (I); the five-substituted ectoine compound with piezofluorescence characteristics of the present invention can be stimulated by grinding-solvent fumigation or grinding-heating external factors in the visible light region (400~500nm), and produce blue light and green light Mutual transformation, and repeated many times can not observe any attenuation and change of luminous wavelength. In addition, this kind of derivatives has self-healing piezofluorochromic properties in the visible light region (400-500nm), and has great application prospects in materials such as micro-stress sensing, trademark anti-counterfeiting, information storage, and environmentally friendly paper. .

Description

Five-substituted tetrahydropyrimidine derivatives in the preparation of piezofluorescent materials application

technical field

The invention belongs to the technical field of luminescent smart materials, and more specifically relates to the application of a penta-substituted ectoine derivative in the preparation of piezofluorescent materials.

Background technique

Piezofluorescence refers to the property that the luminescent color of a material changes under the stimulation of external factors (such as grinding, shearing, stretching, stress, etc.). Especially under the stimulation of external factors (such as solvent fumigation, heating, etc.), piezofluorochromic materials whose fluorescence properties can undergo reversible changes are widely used in micro-stress sensing, trademark anti-counterfeiting, information storage, light-emitting devices, environmentally friendly paper, fluorescent probes, etc. and other fields have great application prospects (Mechanochromic Fluorescent Materials Phenomena, Materials and Applications, 2013; Chem. Soc. Rev. 2012, 41, 3878-3896), which has attracted great attention from the scientific and industrial circles.

Aggregation-caused Quenching (ACQ) often occurs in ordinary organic fluorescent compounds, that is, the fluorescence is very strong in dilute solution, but the fluorescence is weakened or even quenched in concentrated solution or when aggregated. Since various devices are basically used in a solid state, the ACQ effect limits the use of fluorescent materials. In 2001, Tang Benzhong and others synthesized a compound that does not emit light in solution but emits light in its solid state. They called the observed special phenomenon aggregation-induced emission (Aggregation-induced emission, AIE) (Chem. Commun. 2001, 18, 1740-1741). In the short ten years since the discovery of the AIE phenomenon, the application research of AIE organic fluorescent compounds in various fields such as fluorescent probes, cell imaging, and light-emitting devices has shown its unique superior performance (Chem.Soc.Rev.2011, 40, 5361-5388; Adv. Mater. 2014, 26, 5429-5479; Mater. Today 2015, 18, 365-377). If a compound can have piezofluorescence and AIE effect at the same time, it will have great potential in practical application. At present, such organic molecules are still relatively few, and some of the compounds reported in the literature have a narrow range of fluorescence emission wavelengths (<30nm), are not sensitive to external stimuli, and their fluorescence changes are not obvious (see Figure 1 Compounds I, II, III, the fluorescence wavelengths before grinding are 455, 459, 520nm, respectively, and the fluorescence wavelengths after grinding are 465, 465, 540nm); some fluorescence changes have poor reversibility (see compound IV in Figure 1); some have complex synthesis methods, High preparation cost (see compound V, VI in Figure 1) (Chem.Eur.J.2014,20,8856-8861; J.Am.Chem.Soc.2014,136,7383-7394;Chem.Commun.,2014, 50, 9076-9078).

In addition, some piezofluorochromic compounds can gradually return to the color before grinding at room temperature with prolonged storage time after grinding, showing time-changing properties and self-healing ability. This kind of compound has its special application value, such as being used as automatic warning and self-repair of material damage, rewritable material, etc. However, such compounds reported in the literature are very rare (J.Am.Chem.Soc.2010,132,2160-2162; Adv.Mater.2011,23,3261-3265; J.Phys.Chem.C 2012,116,21967 -21972).

Therefore, it is very important to develop reversible piezofluorochromic AIE organic smart materials that are sensitive to external stimuli.

Contents of the invention

The object of the present invention is to provide the application of penta-substituted ectoine derivatives in the preparation of piezofluorochromic materials according to the deficiencies in the reversible piezofluorochromic materials in the prior art.

The above object of the present invention is achieved through the following technical solutions:

The present invention provides an application of a five-substituted ectoine derivative in the preparation of a piezofluorescent material. The derivative has a structure as shown in formula (I):

In the formula:

R ₁ is selected from C _1-8 straight chain or branched chain alkyl or substituted C _1-8 alkyl;

R ₂ and R ₄ are each independently selected from C _1-8 straight chain or branched chain alkyl, substituted C _1-8 alkyl, C _5-8 cycloalkyl, substituted C _5-8 cycloalkyl, C _{5 -6} aryl, substituted C _5-6 aryl, C _9-18 fused ring aryl, substituted C _9-18 fused ring aryl, C _5-6 heterocyclic, substituted C _5-6 heterocyclic Base, C _5-6 aromatic heterocyclic group or substituted C _5-6 aromatic heterocyclic group;

R ₃ is selected from C _5-6 aryl group, substituted C _5-6 aryl group, C _9-18 fused ring aryl group, substituted C _9-18 fused ring aryl group, C _5-6 aromatic heterocyclic group or substituted The C _5-6 aromatic heterocyclic group.

In 2011, we developed a highly efficient five-component reaction for the synthesis of pentasubstituted ectoine compounds, and found that this type of compound has strong AIE properties, that is, it does not emit light in various solutions, but the aggregated state fluorescence efficiency But as high as 93%. (Chem. Eur. J. 2013, 19, 1268-1280; Patent CN201110129857. X, 2013; Patent US8906927B2, 2014). We recently discovered that this class of compounds has sensitive piezofluorochromic properties. In the range of visible light (400-500nm), under the conditions of grinding-solvent fumigation or grinding-heating, sensitive and visible blue light and green light can be converted to each other, and repeated many times without any attenuation and luminous wavelength change. The change of emission wavelength of this kind of compound is as high as 75nm before and after grinding, which is more sensitive than most reported piezofluorochromic materials. In addition, we also found that several five-substituted ectochromic compounds have time-changing properties, and the ground samples gradually return to blue fluorescence with the prolongation of storage time at room temperature, that is, they have self-healing piezofluorochromic properties. Therefore, such fluorescent compounds have very good application prospects in the fields of micro-stress sensing, trademark anti-counterfeiting, self-healing fluorescent materials, information storage, light-emitting devices, environmentally friendly paper, and fluorescent probes.

Preferably, R ₁ is C _1-2 alkyl.

Preferably, R _is C _1-5 straight chain or branched chain alkyl, substituted C _1-5 alkyl, C _5-8 cycloalkyl, C _5-6 aryl or substituted C _5-6 aryl .

Preferably, R _is C _1-5 linear or branched alkyl, substituted C _1-5 alkyl, C _5-8 cycloalkyl, C _5-6 aryl or substituted C _5-6 aryl .

Preferably, the substituent is selected from the following groups: halogen, perhalogenated C _1-2 alkyl, halogenated C _1-4 alkyl, hydroxyl, C _1-6 linear or branched alkoxy, cyano Or C _1-3 straight chain or branched chain alkyl.

Preferably, _R is selected from methyl or ethyl;

_R is selected from phenyl, methylphenyl, fluorophenyl, chlorophenyl, bromophenyl, iodophenyl, trifluoromethylphenyl;

_R is selected from phenyl, bromophenyl, phenyl substituted with methoxyhydroxyl, trifluoromethylphenyl, naphthyl, thienyl, cyanophenyl;

_R4 is selected from phenyl, methylphenyl, fluorophenyl, chlorophenyl, bromophenyl, iodophenyl, trifluoromethylphenyl.

The present invention further provides the application of penta-substituted ectoine derivatives in the preparation of self-repairing piezofluorochromic materials, said derivatives having a structure as shown in formula (II):

In the formula:

R ₅ is C _1-2 alkyl; R ₆ and R ₈ are each independently selected from C _1-5 straight chain or branched chain alkyl, substituted C _1-5 alkyl, C _5-8 cycloalkyl, C _{5 -6} aryl or substituted C _5-6 aryl; R ₇ is C _1-5 straight or branched chain alkyl, substituted C _1-5 alkyl, C _5-8 cycloalkyl, C _5-6 Aryl or substituted C _5-6 aryl.

Preferably, the substituent is selected from the following groups: halogen, perhalogenated C _1-2 alkyl, halogenated C _1-4 alkyl, hydroxyl, C _1-6 linear or branched alkoxy, cyano Or C _1-3 straight chain or branched chain alkyl.

Preferably, _R is selected from methyl or ethyl;

R ₂ is selected from phenyl or trifluoromethylphenyl;

_R is selected from phenyl or trifluoromethylphenyl;

_R4 is selected from phenyl or trifluoromethylphenyl.

The present invention also provides a penta-substituted ectoine derivative, which has piezofluorescent color-changing properties, and the derivative has a structure as shown in formula (III):

In the formula:

_R9 is selected from methyl or ethyl;

_R is selected from phenyl, fluorophenyl, chlorophenyl, bromophenyl, iodophenyl, trifluoromethylphenyl;

R ₁₁ is selected from phenyl, bromophenyl, phenyl substituted with methoxyhydroxyl, trifluoromethylphenyl, cyanophenyl;

R ₁₂ is the same or different from R ₁₀ , and R ₁₂ is selected from phenyl, fluorophenyl, chlorophenyl, bromophenyl, iodophenyl, trifluoromethylphenyl.

Preferably, when said R ₉ is methyl, R ₁₁ is phenyl, trifluoromethylphenyl, cyanophenyl, bromophenyl;

R ₁₀ is phenyl, fluorophenyl, chlorophenyl, bromophenyl, trifluoromethylphenyl; R ₁₂ is the same as R ₁₀ .

When said R ₉ is ethyl, R ₁₁ is phenyl, trifluoromethylphenyl, phenyl substituted by methoxyl hydroxyl;

R ₁₀ is phenyl, iodophenyl, chlorophenyl, bromophenyl; R ₁₂ is the same as R ₁₀ .

The present invention also provides a penta-substituted ectoine derivative, which has self-repairing piezofluorochromic properties, and the derivative has a structure as shown in formula (IV):

In the formula:

R ₁₃ is selected from methyl or ethyl;

R ₁₄ is selected from trifluoromethyl or phenyl;

R ₁₅ is selected from trifluoromethyl or phenyl;

R ₁₄ is the same or different from R ₁₆ , and R ₁₆ is selected from trifluoromethyl or phenyl.

Preferably, R ₁₃ is methyl; R ₁₄ is trifluoromethyl; R ₁₅ is trifluoromethyl; R ₁₆ is trifluoromethyl.

On the basis of previous research, the present invention synthesized the above-mentioned class of new compounds. Through subsequent performance research, it was found that this class of new compounds exhibited piezofluorescent discoloration with self-repairing properties, and were used in micro-stress sensing and trademark anti-counterfeiting. , information storage or environmentally friendly paper fields, has potential application prospects.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

The piezofluorescent compound provided by the present invention is simple to prepare, sensitive to external stimuli, good in fluorescence change and reversibility, and has a wide range of fluorescence emission wavelength. Solvent fumigation or grinding-heating is stimulated by external factors, and the mutual conversion of blue light and green light occurs, and no attenuation and change of luminescent wavelength can be observed after repeated times. In addition, the present invention also provides piezofluorochromic derivatives with self-healing properties. Such derivatives have self-healing piezofluorescent discoloration properties in the visible light region (400-500nm), and have great application prospects in materials in the fields of micro-stress sensing, trademark anti-counterfeiting, information storage, and environmentally friendly paper.

Description of drawings

Figure 1 is an example of compounds with both piezofluorescence and AIE properties reported in the literature;

Fig. 2 is a photograph of three homogeneous polycrystalline crystals and an amorphous form of compound 1 in Example 1 with different fluorescence at λ = 365 nm. Among them, crystal A emits blue-violet fluorescence (425nm), crystal B emits blue fluorescence (445nm), crystal C emits blue-green fluorescence (468nm), and amorphous form D emits green fluorescence (485nm);

Figure 3 is a photograph of the reversible change in fluorescence of compound 1 crystal A under the action of grinding and solvent fumigation;

Fig. 4 is the fluorescence spectrum (a) and the maximum emission wavelength (b) of five grinding and fumigation cycles of crystal A of compound 1.

Figure 5 shows that crystal A of compound 1 is ground into powder and applied on a filter paper sheet to prepare rewritable fluorescent paper;

Fig. 6 is a photograph of self-healing properties of the fully ground green powder of compound 18 crystals placed at room temperature (at 365 nm).

Detailed ways

The present invention will be further described below in conjunction with specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.

Unless otherwise specified, the reagents and materials used in the present invention are commercially available.

Example 1

Compound 1 was synthesized according to our reported method (Chem.Eur.J.2013,19,1268-1280; PatentCN201110129857.X,2013;Patent US8906927B2,2014). Its homogeneous polycrystalline crystals A, B, and C (see Figure 2) were prepared according to our reported literature (Chem. Sci. 2015, 6, 4690-4697). Dissolve the solid product in dichloromethane, add distilled water (leave a small hole on the water surface), and let the dichloromethane evaporate gradually at room temperature. After 2 to 3 hours, the green fluorescent amorphous form D can be obtained (Fig. 2D).

The above-mentioned blue-purple fluorescent crystal A (maximum emission wavelength is 425nm) is fully ground with an agate mortar, and the ground powder is observed to turn green under an ultraviolet lamp (365nm) (see Figure 3), and its fluorescence spectrum is tested, and it is found that The emission wavelength is significantly red-shifted (the maximum emission wavelength is 490nm). Fumigate it with organic solvents such as dichloromethane, observe that the green powder turns back to blue under ultraviolet light, measure its emission spectrum with fluorescence spectroscopy, and the maximum emission wavelength is 425nm. Such grinding and fumigation cycle can be repeated many times without any attenuation and change of luminescent wavelength observed (see Figure 4). Apply the ground powder on the filter paper, fumigate it to blue, and write on it with a pen. It can be observed that the color of the writing changes to a clear green, while the background color is still blue; fumigate it with an organic solvent, It can be observed that the color of the handwriting changes from green to blue, consistent with the background color, and the handwriting disappears (see Figure 5). Such writing and erasing can be repeated many times without observing any decay.

Example 2-17

Penta-substituted ectoine compound 2-17 (see Table 3 for the structural formula) was ground and solvent (dichloromethane) fumigated cycle experimental procedure was the same as that of Example 1, and its fluorescence wavelength changes are shown in Table 1.

Table 1 Fluorescence wavelength changes of five-substituted ectoine compounds 1-20 after grinding and solvent fumigation

Example 18

Compound 18 was synthesized according to our reported method (Chem.Eur.J.2013,19,1268-1280; PatentCN201110129857.X,2013;Patent US8906927B2,2014). details as follows:

(1) Add 1 mmol (142 mg) of dimethyl butyndioate and 1 mmol (161 mg) of m-trifluoromethylaniline into 3 mL of methanol in sequence, and stir at room temperature for 30 min.

(2) Add 1.5 mmol (242 mg) of m-trifluoromethylaniline, 1.2 mmol (96 mg) of 30% formaldehyde, and 5 mmol (300 mg) of acetic acid into 5 mL of methanol, and stir at room temperature for 10 min.

(3) Mix the reaction solutions of (1) and (2), add 1.5mmol (261mg) m-trifluoromethylbenzaldehyde at room temperature, react for 36h, add 20mL saturated aqueous sodium chloride solution, and dichloromethane Methane 20mL extraction, repeated three times, the combined dichloromethane solution, and then 20mL saturated sodium chloride solution, repeated three times, the obtained dichloromethane solution was dried with magnesium sulfate, and the solvent was distilled off under reduced pressure, and then used to prepare a thin chromatography plate The product was purified, the developing solvent was n-hexane+ethyl acetate (10:1), the eluent was ethyl acetate, and the solvent was removed by vacuum rotary evaporation to obtain compound 18.

The initial crystals were fully ground, and then stood at room temperature. Under the ultraviolet light, it can be observed that the ground green powder gradually returns to blue fluorescence as the storage time prolongs (see Figure 6), and the fluorescence emission wavelength also appears corresponding Blue shift (see the following table 2 for the fluorescence spectrum test data). This result suggests that such materials can be used as self-healing piezofluorochromic materials.

Example 19-20

For penta-substituted ectoine compounds 19-20, the synthesis steps refer to Example 18 (see Table 3 for the structural formula). The experimental procedures for piezofluorescent discoloration and self-recovery are the same as in Example 18. The fluorescence wavelength changes are shown in Tables 1 and 2.

Table 2 Five-substituted ectoine compound 18-20 self-healing fluorescence wavelength changes with time

Table 3 is the molecular structure of the compounds in Examples 1-20. Some of the compounds in the examples have been disclosed in 201110129857.X and 201510212629.7. For the compounds not specifically disclosed in 201110129857.X, we give the corresponding structural characteristic data.

The molecular structure of the compound in table 3 embodiment 1～20

Among them, compounds THP-1, THP-3, THP-5, THP-8, THP-9, THP-11, THP-14, THP-16, THP-20 are disclosed in the aforementioned patents; compound THP-2 , THP-4, THP-6, THP-7, THP-10, THP-12, THP-13, THP-15, THP-17～19 are new compounds, and its synthesis method can refer to the prior art, select the The raw materials of the corresponding substituents can be used, and the structural characteristic data are as follows:

THP-2:

¹ H NMR (400MHz, CDCl ₃ ) δ8.50–6.50 (m, 14H), 6.15 (s, 1H), 4.33 (d, J=17.9Hz, 1H), 4.20–4.07 (m, 4H), 3.56 ( d, J=18.0Hz, 2H), 1.26(t, J=6.8Hz, 3H), 1.07(t, J=7.2Hz, 3H) ppm. ¹³ C NMR(101MHz, CDCl ₃ ) δ165.14, 163.99, 149.19, 144.51, 144.15, 129.38, 129.17, 127.48, 126.19, 126.06, 124.18, 121.78, 118.94, 102.29, 79.34, 61.71, 60.27, 42.77ppm.

THP-4:

¹ H NMR (400MHz, CDCl ₃ ) δ=7.78(m,4H),7.27–7.18(m,4H),7.01–6.84(m,4H),6.02(s,1H),4.22–4.10(m,4H ), 3.53 (d, J=18Hz, 1H), 1.19 (m, 6H) ppm; ¹³ C NMR (101MHz, CDCl ₃ ) δ=164.86, 163.73, 147.72, 143.86, 142.67, 141.69, 131.88, 129.41, 127.32, 127.06, 126.25, 125.17, 120.41, 103.12, 79.80, 61.98, 60.51, 42.71, 14.08, 13.59ppm.

THP-6:

¹ H NMR (400MHz, CDCl ₃ ) δ7.99–6.64 (m, 12H), 5.92 (s, 1H), 4.18 (d, J=18.2Hz, 1H), 3.69 (d, J=8.9Hz, 6H) ,3.53(d,J＝18.2Hz,1H)ppm. ¹³ C NMR(101MHz,CDCl ₃ )δ165.48,144.89,127.38,126.28,126.19,121.55,121.47,116.26,116.13,116.03,115.91,101.485,8 ,51.57,42.53ppm.

THP-7:

¹ H NMR (400 MHz, CDCl ₃ ) δ=7.77(m,4H),7.28–7.18(m,4H),7.03–6.80(m,4H),6.03(s,1H),4.22(d,J= 1.2 Hz, 1H), 3.71(d, J＝4.8 Hz, 6H), 3.54(d, J＝18.4Hz, 1H) ppm; ¹³ C NMR (101 MHz, CDCl ₃ ) δ＝165.26, 164.34, 147.63, 143.95 ,142.55,131.96,129.56,129.43,127.30,127.19,126.28,124.87,120.45,102.93,79.91,52.80,51.67,42.64 ppm.

THP-10:

¹ H NMR (400 MHz, CDCl ₃ ) δ7.81–6.74 (m, 12H), 5.92 (s, 1H), 4.16 (d, J＝18.0Hz, 1H), 3.68 (d, J＝9.9 Hz, 6H ), 3.58 (d, J=17.9 Hz, 1H) ppm. ¹³ C NMR (101 MHz, CDCl ₃ ) δ165.73, 164.55, 161.97, 159.52, 159.38, 156.98, 145.85, 145.28, 140.17, 137.80, 129.15, 128.5 ,126.49,126.40,121.47,121.39,116.09,116.00,115.86,115.77,100.39,52.58,51.44,42.30 ppm.

THP-12:

¹ H NMR (400 MHz, CDCl ₃ ) δ7.81–6.86 (m, 13H), 6.30 (s, 1H), 4.41 (d, J=17.9Hz, 1H), 4.26–4.07 (m, 4H), 3.68 (d, J=18.0 Hz, 1H), 1.26(t, J=7.1 Hz, 3H), 1.15(t, J=7.1Hz, 3H) ppm. ¹³ C NMR (101 MHz, CDCl ₃ ) δ164.99, 163.89, 149.03, 144.09, 143.81, 138.26, 138.17, 137.57, 129.69, 129.19, 128.95, 128.60, 126.70, 125.63, 120.77, 102.85, 90.31, 83.77, 79.27, 61.858, 420.5pm

THP-13:

¹ H NMR (400 MHz, CDCl ₃ ) δ7.96–6.80 (m, 14H), 6.14 (s, 1H), 4.32 (d, J＝18.0Hz, 1H), 3.69 (d, J＝6.3 Hz, 6H ), 3.53 (d, J=18.0 Hz, 1H) ppm. ¹³ C NMR (101MHz, CDCl ₃ ) δ165.43, 164.59, 148.95, 144.43, 143.93, 143.55, 132.99, 129.45, 129.36, 127.88, 126.34, 122.03 118.93, 118.49, 112.48, 102.63, 79.36, 52.65, 51.57, 42.77 ppm.

THP-15:

¹ H NMR (400 MHz, CDCl ₃ ) δ7.51–6.69(m,11H),5.98(s,1H),5.70(s,1H),4.37–4.02(m,5H),3.92(s,3H) , 3.63(d, J=18.0 Hz, 1H), 1.25(t, J=7.0 Hz, 3H), 1.14(t, J=7.0Hz, 3H) ppm. ¹³ C NMR(101 MHz, CDCl ₃ ) δ165. 03, 147.96, 146.95, 145.72, 143.81, 142.94, 129.30, 129.25, 126.53, 124.76, 120.28, 119.70, 114.95, 109.22, 103.02, 79.72, 61.83, 60.33, 425.698 ppm,

THP-17:

1H NMR (400 MHz, CDCl3) δ=7.56-7.35(m,8H),6.99–6.73(m,4H),5.96(s,1H),4.22(d,J=18 Hz,1H),3.71(s ,3H),3.70(s,3H),3.56(d,J=18 Hz,1H)ppm; ¹³ C NMR(101MHz,CDCl3)δ=165.28,164.38,148.10,143.80,143.11,136.51,132.49,132.44, 132.31, 128.55, 125.05, 122.87, 120.67, 119.65, 114.36, 102.90, 79.48, 52.78, 51.64, 42.55 ppm.

THP-18:

¹ H NMR (400 MHz, CDCl ₃ ) δ8.06–7.01 (m, 12H), 6.19 (s, 1H), 4.37 (d, J＝18.4Hz, 1H), 3.72 (d, J＝7.3 Hz, 6H ), 3.65 (d, J=18.4 Hz, 1H) ppm. ¹³ C NMR (101 MHz, CDCl ₃ ) δ164.95, 164.25, 149.31, 144.58, 143.07, 138.30, 130.29, 130.09, 125.80, 122.13, 119.74, 115.7 , 105.38, 78.85, 52.76, 51.81, 43.44 ppm.

THP-19::

¹ H NMR (400 MHz, CDCl ₃ ) δ7.86–6.90 (m, 12H), 6.29 (s, 1H), 4.39 (d, J＝18.2Hz, 1H), 3.71 (d, J＝14.7 Hz, 6H ), 3.62 (d, J=18.2 Hz, 1H) ppm. ¹³ C NMR (101MHz, CDCl ₃ ) δ164.86, 164.23, 151.13, 146.98, 142.58, 140.89, 127.14, 126.88, 126.52, 122.37, 117.25, 1035.009 51.89,43.01 ppm.

Claims (4)

1. five substituted-tetrahydro pyrimidine derivatives are preparing the application in causing fluorescence off-color material with pressure, it is characterised in that

The derivative has the structure as shown in formula (I)：

In formula：

R₁Selected from methyl or ethyl；

R₂Selected from phenyl, aminomethyl phenyl, fluorophenyl, chlorphenyl, bromophenyl, iodophenyl, trifluoromethyl；

R₃Selected from phenyl, bromophenyl, the phenyl of methoxyl group hydroxyl substitution, trifluoromethyl, naphthyl, thienyl, cyano-phenyl；

R₄Selected from phenyl, aminomethyl phenyl, fluorophenyl, chlorphenyl, bromophenyl, iodophenyl, trifluoromethyl.

2. application according to claim 1, it is characterised in that the derivative be applied to microstress sensing, trademark anti-counterfeit, Information stores or environmentally friendly paper domains.

3. application of the five substituted-tetrahydro pyrimidine derivatives in preparing the pressure with self-regeneration and causing fluorescence off-color material, its feature It is, the derivative has the structure as shown in formula (II)：

In formula：

R₅Selected from methyl or ethyl；

R₆Selected from phenyl or trifluoromethyl；

R₇Selected from phenyl or trifluoromethyl；

R₈Selected from phenyl or trifluoromethyl.

4. a kind of five substituted-tetrahydro pyrimidine derivatives, it is characterised in that the derivative has structure as shown below：