TW201223944A - Facile preparation of aromatic amines-based benzoxazines and naphthoxazines - Google Patents

Abstract

The present invention provides a facile approach for the synthesis of aromatic amines-based benzoxazine and naphthoxazine with high purity and yields from aromatic amine, aldehyde and phenol. The new route can solve the disadvantages of generation of gelation or high-molecular-weight insoluble products during the reaction.

Description

201223944 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for preparing a child-made preparation yj; a twisted milk-substituted nitrogen benzocyclohexane and an oxo-nitronaphthylcyclohexane. High-purity, high-yield oxo-nitrobenzoxanthene and oxo-naphthalene ring-halogenation from aromatic amines, formaldehyde and phenol, and can improve the condensed energy B in the reaction process. And the insoluble matter of the molecular ruthenium and the disadvantage of low yield. [Prior Art] Benzoxazine/naphthoxazine is a new type of phenol novolac, which is characterized by open-loop self-crossing after heating. Joint reaction. Oxygenated nitrogen benzocyclohexyl plant", Yang Lushu vinegar has high glass transition temperature (10), high modulus (: 〇dulus), low moisture absorption rate, good electrical properties, better flame resistance, door It is a char yleid, a catalyst that does not require acid strengthening during hardening, a product of hardening when it is produced, and a volume change rate of hardening is almost zero or less. Conventional oxo-nitrogen benzopyrene (Benz〇xazine) The manufacturing method is based on the reaction of biguanide and formaldehyde, and the common Bm and Ba are: The synthesis method is synthesized from bisphenol A with formaldehyde and methylamine [丨]. The B_a synthesis method is synthesized by double-test A with meto and aniline (1). The synthesis methods of ^ and ^ are as follows:

4CH20

152043.doc 201223944 However, if an aromatic difunctional amine is used as a starting material to synthesize furfural and monofunctional phenols, an aromatic diamine-based oxo-benzobenzoate (aromatic diamine-) Based benzoxazine) due to condensation between mercapto alcohol (N-CH2OH) and mercapto alcohol (N-CH2OH) in the Ar-(N-(CH2〇H)2)2 structure, formation of a trinitrogen-containing condensation Colloidal incorporation (gelation), the reaction can not be carried out smoothly [3]. The equation for the formation of the trinitrogen heterocycle is as follows.

In 2005, Matsushita Electric proposed to use kinetic control method to synthesize oxo-nitrobenzocyclohexane with 4,4'-diaminodiphenylmethane (DDM) as a solvent. Alkane [4]. The principle is to use the poor solubility of 4,4'-diaminodiphenylmethane in toluene, and let Ar-(N-(CH2OH)2)2 be in a low concentration state, resulting in methyl alcohol (N-CH2OH) and The mercapto alcohol (N-CH2OH) is not easily condensed, making the triazine structure difficult to form. However, the patent of Matsushita Electric Works can only be used to synthesize oxoazobenzocyclohexane with 4,4'-diaminodiphenyl decane as the substrate. If other diamines are used, there will still be a gel state. Insoluble matter is produced. Therefore, Lin et al. proposed a new process for oxo-nitrobenzoxane in 2008 [5], and the reaction is shown below. 152043.doc 201223944

NH2 2-hydroxybenzaldehyde DDM DMF R.T. w

DDM-HB-r

DDM-Bz uses the #香族双胺 to react with 2-hydroxylbenzide (2_hydroxybenzaidehyde) to form an imine (C=N) bond, followed by the reducing agent sodium borohydride (NaBH4) to C=N Double-bond reduction, arranging, adding a valeraldehyde heating ring to form an oxo-nitrobenzo benzohexanone with an aromatic bisamine as a matrix. This method can obtain high purity, high yield of oxoazobenzene:hexane, but the multi-step and the use of expensive reducing agent are its disadvantages; therefore, Lin et al. proposed a simple, environmentally friendly oxygen generation in 20H years. Nitrobenzocyclohexene-dicarbonation (10) is called the production method [6], and hydrogen is used to replace sodium hydrogen halide (10) as a reducing agent, and oxo-nitrobenzocyclohexanone is produced by a steel method. Although it simplifies the previous system, it is still a multi-step process and the raw material 2-hydroxybenzoic acid (2-hydr〇xybenzaldehyde) is more expensive than the auxiliaries. In addition, the use of hydrogen reduction also forms an Therefore, Maozhan is a low-cost, safe and suitable method for the production of oxo-nitrobenzo-cyclohexanes with different structures of aromatic amines 152043.doc 201223944, and can avoid condensation during the reaction. The production of gelled insolubles is an important research direction. [1] Nine X., Ishida HJ Polym. Sci. Part A: Polym. Chem. 1994, 32, 1121.

[2] Ishida H., Rodriguez Y. Polymer 1995, 36, 3151.

[3] Brunovska Z, Liu JP, Ishida H. Macromol Chem Phys 1999, 200, 1745.

[4] Koichi N., Masaaki O., Kenji O. (Matsushita Electric Works) JP Kokai 2005-213301, 2005.

[5] Lin C.H., Chang S.L., Hsieh C.W., Lee H.H. Polymer 2008, 49, 1220.

[6] Chang SL, Lin CHJ Polym. Sci. Part A: Polym. Chem. 2010, 48, 2430. SUMMARY OF THE INVENTION One object of the present invention is to provide an oxoazobenzocyclohexane or oxo generation. A method of nitronaphthylcyclohexane, which is prepared by reacting an aromatic amine, formaldehyde and phenol in a solvent containing an alcohol and/or an ether alcohol, and the general formula of the synthesis is as follows:

152043.doc 201223944 wherein η is 1, 2 or 3;

The RrRs are each independently selected from the group consisting of hydrogen, CVC6 alkyl, CVC6 alkoxy, hydroxy CVC6 alkyl, CF3, OCF3, phenyl, halogen, phenoxy and nitro;

When n=3, W is selected from the following groups

152043.doc 201223944 When n=l, Q is a single bond, it is rated as σ-; is selected from hydrogen Cl_C6 alkyl, alkoxy, via Ci_C6, thiol, CF3, phenyl, _, benzene Sulfhydryl groups and nitrate groups; Y and z series are each independently selected from the group consisting of gas, CF η η wind Cl C6 pit base, 4-. 6 is a group consisting of an alkoxy group, a CF3 group, a group, an element, and a phenoxy group. Another object of the present invention is to provide a process for preparing an oxonitrobenzoxanone or oxonitronaphthacene which is obtained by reacting an alcohol and a solvent. A (4) In the above method of the present invention, the solvent used in & kg is a cosolvent, and a combination of a solvent and an alcohol and/or an ether alcohol is conventionally known. The brickwork is also a method of the invention mentioned above, and the six___he sword is preferably dioxane, dimethoprim, diterpenoid, N,N-dimethyl ketone. , dioxane, tri-gas N-methylpyrrole-. alkane, tetrahydrofuran, stupid, formazan s, o-xylene, m-dimethyl or p-xylene T and xylene, toluene and xylene good. In the above method of the present invention, a non-polar alcohol, alcohol, ethanol, propanol, isopropyl, ▲, a mixture, preferably a methyl pentyl alcohol, isoamyl alcohol, n- hexanol, ^ octaol , ethylene glycol, n-alcohol, 2-heptanol, n-octanol, alcohol, cyclohexanol, cyclopentanol, or isodecyl alcohol. Alcohol n-nonanol 'isodecyl alcohol, positive. In the above method of the present invention, rhodium is used as the second solvent, preferably 152043.doc 201223944 monodecyl ether, 2-methoxyethanol, 2-ethoxyethanol or 2, 2_Dimethoxyethanol. In the above method of the present invention, the alcohol and/or ether alcohol as the second solvent preferably has a volume ratio of 5% to 95% in the solvent containing the second solvent. In the above method of the present invention, the arylamine is unsubstituted or substituted with one or more substituents selected from the group consisting of an alkoxy group and a phenoxy group. For example, the substituted aromatic amine may be a difunctional amine or a hydrazine functional amine or the like, wherein the difunctional amine or the hydrazine functional amine may be selected from an aromatic amine group and an aromatic having an ether group. A group consisting of an amine group, an aromatic amine group having an ether group, a benzene ring/naphthylcycloamine group, and a substituent-containing aromatic amine group. In the above method of the present invention, the furfural refers to the reactant formaldehyde in the reaction, but the actual use is not limited to 100% formaldehyde, for example, about 37% formaldehyde solution or paraformaldehyde can provide furfural in the reaction. To complete the present invention. In the above method of the present invention, the test is selected from the group consisting of phenols substituted by aging, naphthalene and by a plurality of R, wherein the phenol substituted by one or more ruthenium is preferably 1 to 3 Heart substituted phenol, wherein Ri is as defined above. In the above method of the present invention, the temperature of the reaction is in the range of room temperature _15 〇 < 3 (:, the vehicle is preferably 60-13 0 C, and the reaction time of the reaction is in the range of 5 to 36 hours, preferably 10 to 26 hours. EXAMPLES The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the invention, and other aromatic amines (diamines, guanamines, guanamines), 152043.doc 201223944 may also undergo similar reactions. It is within the scope of the invention to obtain oxyazabenzene/naphthocyclohexane having a different structure. Any modifications and variations which are obtained without departing from the spirit of the invention are within the scope of the invention. Synthesis of 〇DA Bz using toluene/propylene glycol methyl ether as solvent. 10 g (0.05 mol) of 4,4-diaminodiphenyl ether (〇DA), 6 g (〇2 mol) of paraformaldehyde, 9.4 100 ml (volume ratio V/V = 3:1) of a bath of phenol and benzene/propylene glycol methyl ether of gram (〇.1 mol) was added to a three-neck reactor equipped with a condensing device, and the temperature was raised under a nitrogen atmosphere. After stirring for 12 hours at 1 °c, the solution was removed to give the product, and the product was washed with decyl alcohol. Filter and dry. Yield 83%. HR-MS (FAB+) m/z: 436.1781 for C28H25N2 〇3. H-NMR (DMSO-D6), 6=4.59 (4H), 5.38 (4H), 6.73 (2H ), 6.84 (4H), 6.86 (2H), 7.08 (2H), 7.09 (4H), 7_10 (2H). The product was identified as 〇DA-Bz by high-resolution mass spectrometry and 4 NMR.

Example 2 Synthesis of 〇da_Bz with toluene/2-ethoxyethanol as solvent: 10 g (0. 〇5 mol) of 4, 'diaminodiphenyl ether, 6 g (〇. 2 mol) Polyacetal, 9.4 g (0.1 mol) of phenol and diphenylbenzene/2-ethoxyethanol solvent 100 ml (v/v = 3:1 by volume) was added to a three-neck reactor equipped with a condensing unit. The temperature was raised to u under a nitrogen atmosphere. After stirring for 12 hours, the solution was extracted to obtain a product. The product was washed with methanol and then filtered and dried. The yield was 8 〇%. The product was identified by high-resolution mass spectrometry and 1H NMR. 152043.doc 201223944 ODA-Bz. Example 3 Synthesis of ODA-Bz with xylene/propylene glycol methyl ether as solvent. Take 10 g of 4,4-diaminodiphenyl ether, 6 g ((·〇5 mol). 0.2 moles of polyacetal, 9_4 g (0.1 mol) of phenol and xylene / propylene glycol methyl solvent 100 ml (volume ratio V / V = 3: l) was added to a three-neck reactor equipped with a condensing device In the nitrogen atmosphere, the temperature is raised to 1200 ° C and the reaction is stirred for 12 hours.

The solution was stripped to give the product. The product was washed with ethanol and then filtered and dried. The yield was 85%. The product was identified as ODA-Bz by high-resolution mass spectrometry and H NMR. Example 4 Synthesis of ODA-Bz with Stupid/Propanediol Methyl Ether as Solvent 10 g (0·〇5 mol) of 4,4-diaminodiphenyl ether and 6 g (0.2 mol) of poly-furfural 9.4 g (0.1 mol) of phenol and benzene/propylene glycol methyl ether solvent i〇〇 ml (volume ratio V/V=3:l) was added to a three-neck reactor equipped with a condensing device, and the temperature was raised under a nitrogen atmosphere. After 8 hours of rc stirring reaction, the solution was added dropwise to % hexane to obtain a product. The yield was 76%. The product was identified as 〇DA_Bz by high-resolution mass spectrometer and 4 NMR. Example 5 7 methanol as a solvent to synthesize ODA-Bz Take 1 g (0.05 mol) of 4,4-diaminodiphenyl ether, 6 g (〇2 mol), 9.4 g (0.1 mol) of benzene Hope that the solvent of toluene/methanol solvent (volume ratio V/V=3:2) is added to the three-neck reactor equipped with a condensing device, and the temperature is raised to 7 under nitrogen atmosphere (the solution is dripped after 24 hours of rc mixing reaction). Ring 152043.doc 201223944 The product was isolated in hexanes. The yield was 83%. The product was identified as odA-Bz by high-resolution mass spectrometry and 1H NMR. Example 6 Synthesis with a toluene/methanol solvent ODA-Bz takes 10 g (0.05 mol) of 4,4-diaminodicholine, 6 g (〇·2 mol) of poly-furfural, 9.4 g (0.1 mol) of phenol and xylene 1 mM solvent (volume ratio V/V = 4:1) was added to a three-necked reactor equipped with a condensing device, and the temperature was raised to 70 under a nitrogen atmosphere. After stirring for 24 hours, the solution was dropped into the ring. The yield of the product obtained by calcination was 85%. The product was identified as 〇dA-Bz by high-resolution mass spectrometer and H NMR. Example 7 Synthesis of ODA-Bz with toluene/ethanol as solvent 10 g (0.05 Mo 4,4-diaminodiphenyl ether, 6 g (02 mol), 9.4 g (0.1 mol) of benzene and benzene/ethanol solvent 1 〇〇 ml (volume The ratio of V/V=3:l) was added to a three-necked reactor equipped with a condensing device, and the temperature was raised to 85 eC under a nitrogen atmosphere for 24 hours. After the solution was removed, the solution was washed away with decyl alcohol. The yield was 84. 〇/0. The product was identified as oda-Bz by high-resolution mass spectrometer and ι NMR. Example 8 Synthesis of ODA-Bz with toluene/isopropanol as solvent 10 g (0.05 mol) of 4,4-di Aminodiphenyl ether克(0.2 mol) polypolycarboxylic acid, 9.4 g (0.1 mol) phenol and toluene/isopropanol solvent ι〇〇 ml (volume ratio V/V=3:l) were added to the three condensing device In the neck reactor, the temperature was raised to 9 ° C in a nitrogen atmosphere, and the reaction was stirred for 24 hours, and then the solution was dropped into 152043.doc -12-201223944 to obtain a product. The yield was 83%. The product was confirmed to be 〇da_Bz by high-resolution mass spectrometry and 1H NMR. Example 9 Synthesis of 〇DA_NBz using toluene/propylene glycol methyl ether as a solvent. Take 10 g (0.05 mol) of 4,4-diaminodiphenyl ether and 6 g (〇2 mol) of the town of polyfurfural. ' 14.4 g ((U Moer) 2_naphthol and toluene / propylene glycol methyl ether solvent 100 ml (volume ratio ν / ν = 4:1) was added to a three-neck reactor equipped with a condensing device in a nitrogen atmosphere The temperature was raised to 115. After stirring the reaction for 12 hours, the solution was removed to give the product, which was washed with decyl alcohol and then filtered and dried. The yield was 81% 〇HR-MS (FAB+) m/z; 537.2106 for C36H28N2〇3. - NMR (DMSO-D6) 5 6=4.25 (4H), 5.30 (4H), 6.72 (4H), 6.83 (4H), 6.92 (2H), 7.41 (2H), 7.54 (2H), 7.65 (2H), 8.02 (2H)' 8.11 (2H). The product was identified as ODA-NBz by high-resolution mass spectrometer and lH ^^. ODA-NBz Example 10 Synthesis of ODA-NBz with toluene/ethanol as solvent 10 g (0.05 4,4-diaminodiphenyl ether of Mohr), paraformaldehyde of 6 g (〇·2 mol), 2·naphthol of 14·4 g (〇.丨莫耳), and 曱/ethanol 100 ml of solvent (volume ratio V/V = 3:1) was added to a three-neck reactor equipped with a condensing unit, under nitrogen The temperature was raised to 85 «c. After stirring for 24 hours, the solution was removed and the product was washed with methanol. The yield was 84%. The product was identified by high-resolution mass spectrometer 152043.doc •13·201223944 and 1H NMR. -NBz » Example 11 Synthesis of ODA-NBz using xylene/n-pentanol as solvent 10 g (0.05 mol) of 4,4-diaminodiphenyl ether and 6 g (0.2 mol) of polyfluorene Aldehyde, 9.4 g (〇.1 mol) of 2-naphthol and diphenylbenzene / n-pentanol solvent 100 ml (volume ratio V / V = 4:1) was added to a three-neck reactor equipped with a condensing device 'The temperature was raised to U5〇c under nitrogen atmosphere. After stirring for 12 hours, the solution was added dropwise to cyclohexane to obtain a product. The yield was 82%. The product was confirmed to be odA-NBz by high-resolution mass spectrometer and 1H NMRJ. Example 12 Synthesis of p_Bz using toluene/propylene glycol methyl ether as a solvent 10 g (0.093 mol) of p-phenylenediamine (p_PD), un*(〇37 mol) paraformaldehyde, 17.49 g (0.1) 86 ml of phenol and toluene / propylene glycol oxime ether bath 100 ml (volume ratio ν / ν = 3: 丨) into a three-neck reactor equipped with a condensing device, in a nitrogen atmosphere Heating iU〇t: the reaction was stirred for 12 hours / valley agent pumping and the product was washed with methanol. The yield was 84 D/❶. HR _ _ _ _ _ (4H). The product was confirmed to be ρ-Βζ via a high-resolution mass spectrometer and a brilliant recording. ,

Example 13 152043.doc -14- 201223944 Synthesis of p_Bz using benzene/propylene glycol methyl ether as a solvent Take 10 g (0.093 mol) of p-phenylenediamine, U11 g (0·37 mol) of poly-branched, I7 .49 g (〇.ι86 mol) of phenol and benzene/propylene glycol methyl ether solvent 100 ml (volume ratio V / V = 3: l) was added to a three-neck reactor equipped with a condensing device to 'heat up under nitrogen atmosphere To 85. After stirring for 24 hours, the solution was added dropwise to cyclohexane to obtain a product. The yield was 85%. The product was confirmed to be p_Bz by high-resolution mass spectrometry and 1H NMR. Example 14

Synthesis of pBz with toluene / 2-methoxyethanol as solvent 10 g (0.093 mol) of p-phenylenediamine, U11 g (0.37 mol) of paraformaldehyde, 17_49 g (0.186 mol) of phenol and toluene /2-methoxyethanol solvent 100 ml (volume ratio v / v = 4j) was added to a three-neck reactor equipped with a condensing device. 'The temperature was raised to 12 ° C under nitrogen atmosphere. After stirring for 12 hours, the solvent was pumped. The product was washed with methanol. The yield was 79%. The product was confirmed to be p_Bz by high-resolution mass spectrometry and 1H NMR. Example 15 Synthesis of p_Bz using toluene/ethanol as a solvent 10 g (0.093 mol) of p-phenylenediamine, molar polydequalal, 17.49 g (0.186 mol) of phenol and toluene/ethanol solvent 1 〇〇 ml (volume ratio V/V = 3:1) was placed in a three-necked reactor equipped with a condensing device, and the temperature was raised to 85 ° C under a nitrogen atmosphere. After stirring for 12 hours, the solvent was removed and the product was washed with methanol. . The yield was 82%. The product was confirmed to be p_Bz by high-resolution mass spectrometry and 1H NMR. Example 16 152043.doc -15- 201223944 Synthesis of p_Bz using xylene/n-butanol as solvent 10 g (0.093 mol) of p-phenylenediamine, 11.11 g (0.37 mol) of paraformaldehyde, 17.49 g ( 100 ml of a solvent of 0.1 86 moles of phenol and diphenylbenzene/n-butanol (volume ratio V/V=4:1) was added to a three-necked back-twist equipped with a condensing device and heated to 110 in a nitrogen atmosphere. After stirring the reaction for 12 hours at ° C, the solution was dropped into a % hexane to give a product. The yield was 75 %. The product was confirmed to be p_Bz by high-resolution mass spectrometry and 1H NMR. Example 17 Synthesis of p_NBz using toluene/propanol as a solvent 10 g (0.093 mol) of p-phenylenediamine, 1111 g (〇37 mol) of poly-methane, 26.79 g (0.186 mol) 100 ml of a solvent of 2-naphthoquinone and anthraquinone/propylene glycol methyl ether (volume ratio V/V=4:1) was added to a three-neck reactor equipped with a condensing device to raise the temperature to 1 〇〇 °c under a nitrogen atmosphere. After the reaction was stirred for 24 hours, the solution was added dropwise to cyclohexane to precipitate. The yield was 830 /. . HR-MS (FAB + ) m/z: 445.1834 for C3()H24N2〇2. </ RTI> <RTIgt; 〇 2 (2H), 8.11 (2H). The product was identified as ρ_ΝΒζ by high-resolution mass spectrometry and 1H NMR.

Example 18 Synthesis of ρ_Βζ with xylene/2-methoxyethanol as solvent 152043.doc •16- 201223944 Take 10 g (0.093 mol) of p-phenylenediamine, Ull g (〇37 mol) poly poly Road, 26.79 g (〇.186 mol) of 2-naphthol and xylene / 2 - methoxyethanol / gluten 1 vol (volume ratio ν / ν Μ)) added to the neck with a condensing device In the reactor, the temperature was raised to π〇β under a nitrogen atmosphere (after stirring the reaction for 12%, the solution was dropped into cyclohexane to precipitate. The yield was 76%. The product was confirmed by high-resolution mass spectrometer and 1H NMR. p_NBz. Example 19 Synthesis of p NBz with a solution of a stupid/isobutanol. 10 g (0.093 mol) of p-phenylenediamine, u-gram (3) molars of paraformaldehyde, 26.79 g (〇. 186 moles of 2_naphthol and diphenylbenzene / isobutanol solvent 1 〇〇 ml (volume ratio V / V = 3:1) added to the three-necked reaction Is with a condensing device, under nitrogen The temperature was raised to 10 (the solution was added dropwise to cyclohexane after 12 hours of stirring reaction, and the yield was 81%. The product was confirmed to be p_NBz by a high-resolution mass spectrometer and H NMR. Example 20 /methanol as solvent to synthesize p_NBz 10 g (0.093 mol) of p-phenylenediamine, uu* (〇37 mol) poly-furfural, 26.79 g (0.186 mol) of 2-naphthol and toluene/methanol A solvent of 100 ml (volume ratio V/V = 3:1) was placed in a three-necked reactor equipped with a condensing device, and the temperature was raised to 80 t under a nitrogen atmosphere: after stirring for 24 hours, the solution was dropped into cyclohexane to precipitate. The yield was 82%. The product was identified as p_NBz by high-resolution mass spectrometry and 1 h NMR. Example 21 Synthesis of baPP_Bz with toluene/propylene glycol methyl ether as a solvent 152043.doc -17· 201223944 Take 10 g (0.024 mol) 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 2.94 g (0.098 mol) of paraformaldehyde, 4.51 g (0.048 mol) of phenol and toluene/ 100 ml of a solvent of propylene glycol oxime ether (volume ratio V/V = 3:1) was placed in a three-necked reactor equipped with a condensing device, and the temperature was raised to 100 ° C under a nitrogen atmosphere. After stirring for 12 hours, the solution was dropped into the ring. The product was isolated from the alkane. Yield: 88%. HR-MS (FAB+) m/z: 647.2917, C43H3904N2. 1H NMR (DMSO-D6), δ=1_57 (6H), 4.61 (4H), 5.39 (4H) , 6.73 (2H), 6.79 (4H), 6.86 (2H), 6.90 (4H), 7.08 (2H), 7.09 (2H), 7.12 (4H), 7.13 (4H). The product was confirmed to be baPP-Bz by high-resolution mass spectrometry and 1H NMR.

Example 22 Synthesis of BAPP-Bz using xylene/2-methoxyethanol as a solvent 10 g (0.024 mol) of 2,2-bis[4-(4-aminophenyloxy)phenyl]propane, 2.94 g (0.098 mol) of poly-furfural, 4_51 g (〇〇48 mol) of phenol and diphenylbenzene/2-methoxyethanol solvent 1 〇〇 ml (volume ratio V/V = 3: 2) Adding to a three-neck reactor equipped with a condensing device to raise the temperature to 12 under a nitrogen atmosphere (the solution was dropped into cyclohexane after 12 hours of TC stirring reaction to obtain a product. The yield was 77%. Using high resolution The mass spectrometer and 1hnmr identified the product as BAPP-Bz. Example 23 152043.doc 201223944 Synthesis of BAPP-Bz with xylene/n-butanol as solvent 10 g (0.024 mol) of 2,2-bis[4-( 4-aminophenoxy)phenyl]propane, 2.94 g (0.098 mol) of paraformaldehyde, 4.51 g (0.048 mol) of phenol and xylene/n-butanol solvent 1 〇〇 ml (volume ratio V/V=4: l) In a three-necked reactor equipped with a condensing device, the temperature was raised to 1 l〇°C under a nitrogen atmosphere, and the reaction was stirred for 12 hours, and then the solution was dropped into cyclohexane to obtain a product. For 70./ Using high-resolution mass spectrometry and identified iH NMR confirmed the product as BAPP-Bz.

Example 24 Synthesis of BAPP-Bz using toluene/methanol as a solvent 10 g (0.024 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2.94 g (0.098 mol) More than one ear of polyether A '4.51 g (0.048 mol) phenol and toluene / methanol solvent 1 〇〇 ml (volume ratio V / V = 2: l) was added to a three-neck reactor equipped with a condensing device, The temperature was raised to 7 under a nitrogen atmosphere (the mixture was removed after 24 hours of rc reaction, and the product was washed with ethanol. The yield was 72%. The product was identified as BAPP-Bz by high-resolution mass spectrometry and iH NMR. 25 Synthesis of BAB-Bz with toluene/propylene glycol methyl ether as a solvent Take 10 g (0.034 mol) of 1,4-bis(4-aminophenoxy)benzene (bab), 4.08 g (0.136 mol) Phenylaldehyde, 6 39 g (〇〇68 mol) of phenol and toluene / propylene glycol methyl ether solvent 1 〇〇 ml (volume ratio v / v = 4:1) was added to a three-neck reactor equipped with a condensing device 'The temperature is raised to } under nitrogen atmosphere. 〇 (12 hours after the rc reaction was mixed, the solution was dropped into cyclohexane and the product was precipitated. The yield was 152043.doc 19 201223944. The rate was 85%. HR-MS (FAB + ) m/z : 529.2129 for C34H3〇04N2. H NMR (DMSO-d6), 5=4.61 (4H), 5.39 (4H), 6.72 (2H), 6.86 (2H)} 6.89 (4H), 6.91 (4H), 7.08 (2H), 7.09 (2H), 7.12 (4H). The product was confirmed to be BAB-Bz by high-resolution mass spectrometer and iH nmr.

Example 26 Synthesis of BAB_Bz using toluene/2-ethoxyethanol as a solvent 10 g (0.034 mol) of i, 4_bis(4-aminophenoxy)benzene, 4 g 8 g (0.136 mol) Polyacetal, 6 39 g (〇〇68 mol) of phenol and toluene/2-ethoxyethanol solvent 100 ml (volume ratio ν / ν = 4: ι) was added to the two-neck reaction with a condensing device The temperature was raised to 丨1 in a nitrogen atmosphere, and the reaction was stirred for 12 hours, and then the solution was poured into a cyclohexane to obtain a product. The yield was 72/. The product was identified as ΒΑΒ-Βζ ° by means of an inter-resolution mass spectrometer and 1H NMR. Example 27 Synthesis of ΒΑΒ-Βζ using toluene/ethanol as a solvent 1 gram (0.034 mole)! , 4-bis(4-aminophenoxy)benzene, 4 〇 8 g (〇·136 mol) polypolymethyl disk, 6.39 g (0.068 mol) of benzene and toluene /: alcohol solvent U) 〇ml (volume ratio v/v=3:l) was added to the reactor with a condensing device to react 3 towels' under nitrogen atmosphere to the thief reaction % hour J52043.doc -20- 201223944 and then the solution was dropped into cyclohexane The product was precipitated. The yield was 74%. The product was confirmed to be B AB_Bz by high-resolution mass spectrometry and 1H NMR. Example 28 Synthesis of BAB-Bz using this /isopropanol as solvent 10 g (0.034 mol) of 1,4-bis(4-aminophenoxy)benzene, 4.08 g

(0.136 mol) of polyacetal, 6.39 g (0 068 mol) of phenol and benzene / isopropanol solvent 100 ml (volume ratio V / V = 3:1) added to the two necks with a condensing device In the reactor, the temperature was raised to 8 Torr under a nitrogen atmosphere. After the reaction was stirred for 2 hours, the solution was added dropwise to cyclohexane to obtain a product. The yield was 78 〇/〇. The product was identified as baB-Bz by high-resolution mass spectrometry and 1H NMR. Example 29 Synthesis of DDS-Bz using xylene/propylene glycol methyl ether as a solvent 10 g (0_04 mol) of diamine diphenyl hydrazine (1) 1) 8), 4 - 84 g (0.16 mol) of poly-furfural , 7.52 g (0.08 mol) of phenol and diphenylbenzene/propylene glycol methyl ether solvent 100 ml (volume ratio v/v = 4:1) was added to a three-neck reactor equipped with a condensing device in a nitrogen atmosphere The mixture was heated to i 2 〇〇C and stirred for 24 hours, and then the solution was added dropwise to cyclohexane to obtain a product. The yield was 82%.

HR-MS (FAB+) m/z: 485.1545 for C28H2604N2S. H NMR (DMS0-d6), 6=4.71 (4H), 5.47 (4H), 6.74 (2H), 6.88 (2H), 7.08 (2H), 7·11 (2H), 7.23 (4H), 7.71 ( 4H). The product was confirmed to be DDS-Bz by high-resolution mass spectrometry and 1H NMR.

152043.doc •21· 201223944 Example 30 Synthesis of ddS-Bz with xylene/2-ethoxyethanol as solvent 10 g (〇·〇4 mol) of diamine disulfolane, 48 g (〇16) More than acetal, 7.52 g of phenol and xylene/2·ethoxyethanol 100 ml (volume ratio V/V=4:1) were added to the three condensers. In the neck reaction, the temperature was raised to 12 Torr in a nitrogen atmosphere. (After stirring for 12 hours, the solution was added dropwise to a hexanes to give a product. The yield was 8 〇%. The product was identified as DDS-Bz by high-resolution mass spectrometry and 1H NMR. Example 31 Toluene/methanol For the solvent synthesis DDS-Bz take 10 grams (0. 04 moles) of diamine diphenyl hydrazine, 4.8 grams (0.16 moles) of polycarboxylic acid, 7.52 grams (〇. 〇 8 moles) of phenol and stupid / 1 mM of methanol solvent (volume ratio V/V = 3:1) was placed in a three-neck reactor equipped with a condensing device, and the temperature was raised to 70 ° C under a nitrogen atmosphere. After stirring for 24 hours, the solution was removed. The yield was 74%. The product was identified as DDS-Bz by high-resolution mass spectrometer and iH NMR. Example 32 Synthesis of DDS-Bz with xylene/ethylene glycol as solvent 10 g (0·04 mol) Diamine diphenyl sulfone, 4.8 g (0.16 mol) of poly-capric acid, 7.52 g of phenol and xylene/ethylene glycol solvent 100 ml (volume ratio V/V) =3:2) In a three-necked reactor equipped with a condensing device, the temperature was raised to 13 Torr under a nitrogen atmosphere, and after stirring for 12 hours, the solution was removed to obtain a product. 71%. The product was identified as ddS-Bz by high resolution mass spectrometer and ι NMR. 152043.doc • 22· 201223944 Example 33 Synthesis of BAP F-Bz using a toluene/propanol methyl bond as solvent

Take 10 g (0.029 mmol) of 9 '9-bis(4-aminophenyl)fluorene' 9.32 g (0.16 mol) of poly-furfural, 5.40 g (〇·〇8 mol) of phenol and 100 ml of a solvent of diphenylbenzene / propylene glycol oxime ether (volume ratio V / V = 3:1) was placed in a three-necked reactor equipped with a condensing device to raise the temperature to u 氮气 under a nitrogen atmosphere. After stirring for 2 hours, the solution was added dropwise to cyclohexane to obtain a product. The yield was 69%. The 1H NMR spectrum of BAPF-Bz is shown in Figure 1. The product was identified as BAPF-Bz by high-resolution mass spectrometry and 1H NMR. Example 34 Synthesis of BAPF-Bz with Toluene/Ethanol as Solvent 10 g (0.029 mmol) of 9,9-bis(4-aminophenyl)fluorene, 9.32 g (0.16 mol) of poly-purine route, 5·4() g (4) 8 m) Benzene and Benzene/Ethanol 1001⁄4 liter (volume ratio v/v=3:2) is added to a three-neck reactor equipped with a condensing unit under nitrogen atmosphere After heating to 9 Torr for 12 hours, the solution was dropped into cyclohexane to obtain a product. The yield was 63%. The product was confirmed to be BApFBz by high-resolution mass spectrometry and 1H NMR. Example 3 5 Synthesis of BApF Bz with toluene/isopropanol as solvent (〇·(tetra)mole) 9,9_2 (4_aminobenzene (tetra), 9 32 g (〇·16 mol) Polyfluorene, 5.4G grams (G.G8 Moer) benzene and toluene / propylene glycol solvent (10) ml (volume ratio: 1) added to the reaction with a condensing device 4 'heated under nitrogen atmosphere After stirring for 9 hours in the 9th generation, the solution was added dropwise to cyclohexane to obtain a product. The yield was (10). The product was identified as BAPF-Bz by high resolution 152043.doc -23· 201223944 析 mass spectrometer and 4 NMR. 1 Synthesis of ODA-Bz with toluene as solvent 10 g (0.05 mol) of 4,4-diaminodiphenyl ether, 6 g (0.2 mol) of poly-furfural, 9.4 g (0.2 mol) 1 〇〇ml of phenol and toluene was added to a three-necked reactor equipped with a condensing device, and the temperature was raised to 1 Torr under a nitrogen atmosphere (the rc was stirred in the reaction process. During the reaction, insoluble matter gradually precipitated in the reactor, and finally agglomerated in the reactor. The bottom of the reactor was not analyzed by the expected structure. This result showed that ODA-Bz could not be obtained smoothly with terpene as a solvent. Comparative Example 2 Dissolved in xylene Synthesis of ODA-Bz Take 10 g (0.55 mol) of 4,4-diaminodiphenyl ether, 6 g (〇·2 mol) of poly-furfural, 9.4 g (0.2 mol) of phenol And adding 1 liter of diphenylbenzene to a three-necked reactor equipped with a condensing device, 'heating under nitrogen to l2 〇 (&gt;c, mixing reaction), gradually insoluble matter is precipitated in the reactor during the reaction, and finally The product was not analyzed at the bottom of the reactor. The results showed that the ODA-Bz could not be obtained smoothly with diphenylbenzene. Comparative Example 3 Synthesis of ODA-Bz with benzene as solvent 10 g (0.05 m) 4,4-diaminodiphenyl, 6 g (0.2 mol) polypyruic acid, 9.4 g (0.2 mol) of phenylhydrazine and stupid ml were added to a three-neck reactor equipped with a condensing device In a nitrogen atmosphere, the temperature is raised to 9 〇β (: search reaction) during the reaction, gradually insoluble matter is precipitated in the reactor, and finally agglomerates at the bottom of the reactor, and the product is not analyzed by the expected structure. .doc -24- 201223944 It is not possible to obtain 〇DA-Bz smoothly with benzene as solvent. Comparative Example 4 Synthesis of ODA-N with mono-toluene as solvent Bz

Take 10 g (0.05 mol) of 4,4-diaminodiphenyl ether, 6 g (〇2 mol) of paraformaldehyde, 14.4 g (〇"mol) of 2-naphthol and xylene 1 〇〇ml was added to a three-necked reactor equipped with a condensing device, and the reaction was stirred under a nitrogen atmosphere to 120 ° C. After the reaction was completed, the solution was dropped into cyclohexane to precipitate, and the yield was 32%. The analysis results show that the synthesis of 〇DA NBz with xylene as a solvent has a low yield. Comparative Example 5 Synthesis of p-Bz using toluene as a solvent. 10 g (O.O93 mol) of p-phenylenediamine, uu* (〇37 mol) of paraformaldehyde, 17_49 g (0.186 mol) of phenol and 100 ml of toluene was added to a two-necked reactor equipped with a condensing device. The temperature was raised to 1 t under a nitrogen atmosphere. The reaction was stirred during the reaction. During the reaction, insoluble matter gradually precipitated in the reactor, and finally the solution was dropped into cyclohexane to precipitate. The yield was 8〇/0. The analysis results showed that the synthesis of p-Bz with toluene as a solvent was low in yield and poor in purity. Comparative Example 6 Synthesis of p_Bz using xylene as solvent 10 g (O.O93 mol) of p-phenylenediamine, U11 g (〇37 mol) of paraformaldehyde, 17.49 g (0.186 mol) of phenol and 1 〇〇ml of xylene was added to a three-necked reactor equipped with a condensing device. The temperature was raised to 120 ° C in a nitrogen atmosphere to stir the reaction. During the reaction, insoluble matter gradually precipitated in the reactor, and finally the solution was dropped into the ring. The alkane precipitated in a yield of 11%. Analytical Results 152043.doc -25- 201223944 The results show that the synthesis of P_Bz with a solvent is low and the purity is poor. Comparative Example 7 Synthesis of p-NBz using mono-toluene as a solvent Take 10 g (0.093 mol) of p-phenylenediamine, iMog (〇37 mol) of paraformaldehyde, 26_79 g (0.186 mol) of 2_ Add 1 ml of naphthol and diphenylbenzene to a three-neck reactor equipped with a condensing device, and raise the temperature to 120 ° C under a nitrogen atmosphere to stir the reaction. Finally, the solution was dropped into cyclohexane to precipitate 36%. . The analysis results show that the synthesis of diphenylbenzene is a low yield. Comparative Example 8 Synthesis of BAPP-Bz from benzene as solvent 10 g (0.034 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4.08 g (0.136 mol) POM, 6S9g (〇〇68mol) phenol and benzene 100ml were added to a three-neck reactor equipped with a condensing device to raise the temperature to 9CTC in a nitrogen atmosphere, and finally agglomerate at the bottom of the reactor, and the product was analyzed. Not the expected structure. This result shows that BAPP-Bz cannot be obtained smoothly with benzene as a solvent. Comparative Example 9 Synthesis of BAPP-Bz using toluene as a solvent 10 g (0.024 mol) of 2,2-bis[4(4aminophenoxy)phenyl]propane, 2.94 g (0.098 mol) of polypolymer Furfural, 4 51 g (〇〇48 mol) of benzene and 100 ml of toluene were placed in a three-neck reactor equipped with a condensing device, and the temperature was raised to 丨〇 under the turbulence of nitrogen (rc stirring reaction finally caked) At the bottom of the reactor, the product was not analyzed to the expected structure. This result showed that bapp_bz could not be obtained smoothly with a solvent. 152043.doc 201223944 Comparative Example 1 ο Synthesis of ΒΑΒ-Βζ with toluene as solvent 10 g (0.034 mol) ) Μ _ bis (4 - aminophenoxy) benzene, 4 〇 8 gram of Mo) poly poly A, 6.39 g (0. 068 m) of benzene age and f benzene _ ml add people with condensation In the three-neck reactor of the apparatus, the temperature is raised to 100 C (d) in a nitrogen atmosphere, and the process t is gelled, and finally agglomerates at the bottom. The product was analyzed and was not the expected structure. This result shows that BAB-Bz cannot be obtained smoothly with toluene as a solvent. Comparative Example 11 Synthesis of BAB-Bz using xylene as a solvent 1 gram (0.034 mole) of bis(cardamosylphenoxy)benzene, 4 〇 8 g (0.136 mol) of poly-ply, 6 39克(四)68莫耳) benzene and dimethyl (tetra) 〇 ml plus a three-neck reactor with condensation t set, stirring under the atmosphere ring / dish to 120 C, the reaction is gelatinized The phenomenon produces 'final agglomeration at the bottom. The product was analyzed and was not the expected structure. This result shows that bab_Bz cannot be obtained smoothly with xylene as a solvent. Comparative Example 12 Synthesis of Fluorene-Bz with a solvent of 10 gram (0.029 mmol) of 9,9-bis(4-aminophenyl) seedling, 9 32 g (0.16 mol) of poly-branched, 5 4 (^ (g g8 Moer) silk and benzene benzene life d 100 ml into a three-neck reactor with a condensing device in the nitrogen f brother down m 11 〇 c search reaction 'the process is coagulation The gelation phenomenon resulted in 'final agglomeration at the bottom. The product was not analyzed by the expected structure. This result shows that Fiu〇rene_Bz could not be obtained smoothly with a solvent. 152043.doc •27· 201223944 Comparative Example 13 Using xylene as a solvent Synthesis of BAPF-Bz 10 g (0.029 mmol) of 9,9-bis(4-aminophenyl)phosphonium, 9.32 g (0.16 mol) of paraformaldehyde, 5.40 g (0.08 mol) of phenol and 100 ml of a solvent of xylene was placed in a three-necked reactor equipped with a condensing device, and the temperature was raised to 120 ° C under a nitrogen atmosphere to stir the reaction, and gelation occurred during the process, and finally the cake was agglomerated at the bottom. The expected structure. This result shows that BAPF-Bz cannot be obtained smoothly with toluene as a solvent. The experimental results of the comparative examples are summarized in the following Table 1: Table 1 Aromatic amine phenolic solvent type Solvent ratio Reaction temperature (0 〇 time (h) Result (volume ratio V/V) (yield (%)) Example 1 ODA phenol toluene / propylene glycol methyl 03:01 100 12 83 Example 2 ODA benzene xylene / 2 - ethoxyethanol 03:01 110 12 80 Example 3 ODA phenol xylene / propylene glycol methyl ether 03:01 120 12 85 Example 4 ODA Phenol/propylene glycol methyl ether 03:01 80 24 76 Example 5 ODA Benzene/Methanol 03:02 70 24 83 Example 6 ODA Phenol Dimethyl/Methanol 04:01 70 24 85 Implementation Example 7 ODA Phenolphthalein/Ethanol 03:01 85 24 84 Example 8 ODA Phenol Toluene/Isopropanol 03:01 90 24 83 Example 9 ODA 2-naphtholtoluene/propylene glycol oxime 04:01 115 12 81 Example 10 ODA 2-naphthol toluene/ethanol 03:01 85 24 84 Example 11 ODA 2-naphthol xylene/n-pentanol 04:01 115 12 82 Example 12 p-PD Phenol toluene/propylene glycol methyl 03:01 110 12 84 -28- 152043.doc 201223944

Ether Example 13 p-PD phenol benzene/propylene glycol methyl ether 03:01 85 24 85 Example 14 p-PD phenol toluene/2-methoxyethanol 04:01 120 12 79 Example 15 p-PD phenol toluene/ethanol 03:01 85 12 82 Example 16 p-PD Phenylene xylene/n-butanol 04:01 110 12 75 Example 17 p-PD 2-naphtholphthalein/propylene glycol oxime ether 04:01 110 24 83 Example 18 p-PD 2-Nylidene/2-methoxyethanol 04:01 120 12 76 Example 19 p-PD 2-naphthol xylene/isobutanol 03:01 100 12 81 Example 20 p-PD 2-naphthol toluene/methanol 03:01 70 24 82 Example 21 BAPP Phenol toluene/propylene glycol oxime ether 03:01 100 12 88 Example 22 BAPP Phenol diphenylbenzene/2-methoxy. Ethyl alcohol 03:02 120 12实施 Example 23 BAPP phenol xylene/n-butanol 04:01 110 12 70 Example 24 BAPP phenolphthalein/methanol 02:01 70 24 72 Example 25 BAB phenol toluene/propylene glycol oxime ether 04:01 100 12 85 Implementation Example 26 BAB phenol toluene/2-ethoxyethanol 04:01 110 12 72 Example 27 BAB phenol toluene/ethanol 03:01 80 24 74 Example 28 BAB phenol benzene/isopropanol 03:01 80 24 78 Example 29 DDS Phenolphthalein/propylene glycol methyl ether 04:01 120 24 82 Example 30 DDS Phenolphthalein/2-ethoxyethanol 04:01 120 12 80 Example 31 DDS Benzene Benzene/Decanol 03: 01 70 24 74 Example 32 DDS Phenylene xylene/ethylene glycol 03:02 130 12 71 Example 33 BAPF Phenylene xylene/propylene glycol oxime ether 03:01 110 12 69 Example 34 BAPF Phenol toluene/ethanol 03:02 90 12 63 Example 35 BAPF Phenol Toluene/Isopropanol 02:01 90 24 66 152043.doc -29- 201223944 Comparative Example 1 ODA Phenol toluene - 100 - Insoluble matter production Comparative Example 2 ODA Phenyl diphenylbenzene - 120 - insoluble matter Production Example 3 ODA Phenol Benzene-90 - Insoluble Production Comparative Example 4 ODA 2-naphthol xylene-120 12 32 Comparative Example 5 p-PD phenolphthalein Benzene - 100 12 8 Comparative Example 6 p-PD Phenol Dimethyl Stupid - 120 12 11 Comparative Example 7 p-PD 2-naphthol xylene-120 12 36 Comparative Example 8 苯酚 Phenol Benzene - 90 - Insoluble matter Production Comparative Example 9 笨 Streptophenol toluene - 100 Insoluble matter Production Comparative Example 10 苯酚 Phenol Benzene-100 - insoluble matter production Comparative Example 11 苯酚 Phenol dimethyl - 120 - Insoluble matter production Comparative Example 12 BAPF Phenol toluene - 110 - Insoluble matter production Comparative Example 13 BAPF Phenylene xylene - 120 - Insoluble matter generation [Simplified illustration] Fig. 1 is a BAPF-Bz synthesized in Example 33. 1 H NMR spectrum. 152043.doc •30·

Claims (1)

201223944 VII. Scope of application for patents: 1. A method for preparing oxo-nitrogen, 1 system is: reacting in a ring-opened or oxo-nitronaphthylcyclohexane, which is amine, methyl and hope to contain alcohol and / or solvent of the key alcohol, the formula of 0 is as follows: / η w~fQ-nh2 ) + 4 again Η Where η is 1, 2 or 3; Each is independently selected from the group consisting of hydrogen, C丨-C6 alkyl, C "C6 alkoxy, hydroxy CVC6 alkyl, CF3, hydrazine CF3, phenyl, halogen, phenoxy and nitro; Q is a single Key, - Hyper, -. 4, Office. 4 When n=2, the W system is selected from the group consisting of: 152043.doc 201223944 When n=3, W is selected from the following group A or when n=1, Q is a single bond, and W is T is selected from the group consisting of gas, Ci_c6 alkyl 'c'c alkyl group, carboxyl group, CF3, benzoquinone. 70 gas base, hydroxyl group (group; * base, hydroxyl, stupidoxy and thiol and oxime are each independently selected from a hydrogen group, a U6 alkyl group, a C, a C6;隽氡: a group of M, 'prime, stupid oxy. &gt; Stupid and cyclohexane or oxo-naphthalene 152043.doc • 2 · 201223944 Method of the method, which is obtained by reacting in a solvent of an arylamine ether alcohol. 3. The method according to claim 1 or 2, wherein the dimethyl carbamide, the dimethyl sulphide N- fluorenyl group is 0 to 0 ketone, the dichloro hydrazine benzene and the diterpene benzene, the o- dimethyl stupid group. The paraformaldehyde and the phenol are contained in the alcohol and/or the solvent is selected from the group consisting of dioxane, N,N-dimercaptoacetamide, gas benzene, dioxane, tetrahydrofuran, benzene, and The composition of the toluene or the dimethyl benzoate. The alcohol of the claim 1 or 2, wherein the alcohol is used as the second solvent, which is used for one by one, and is selected from the group consisting of methanol, ethanol, propanol, and Propion, n-butanol, isobutanol ethylene glycol cyclopentanol isodecyl alcohol disolvent-based ethanol n-pentanol, isoamyl alcohol, n-hexanol, 2-hexanol, cyclohexanol, n-heptanol, /_g a group consisting of an alcohol, n-octanol, isooctanol, n-nonanol, n-nonanol or isodecyl alcohol; the alcohol is selected from the group consisting of propylene glycol, 2-methoxyethanol, m 2, 2 a group consisting of dimethoxyethanol. 5. The method of claim 1 or 2, wherein: ♦ Xuan Zuo 笛, 々 丨 、, τ is the first solvent alcohol of the hummer and/or ether alcohol in the solvent containing the second solvent The volume ratio is 5% to 95%. 6. The method of claim 2, wherein the arylamine is unsubstituted or substituted with - or a plurality of substituents selected from the group consisting of alkoxy groups and phenoxy groups. The method of claim 1 or 2, wherein the phenol is selected from the group consisting of phenols, naphthols, and phenols substituted with 1 to 3, wherein R] is as defined in the requesting work. . 8. The method of claim 1 or 2, wherein the temperature of the reaction ranges from room temperature to 150 ° C. 9. The method of claim 8, wherein the temperature of the reaction ranges from 6 to 13 Torr. Hey. 152043.doc 201223944 The method of claim (4), which is the method of the formula (4), which is a compound of the formula k, which is a compound having the formula k, which is a compound of the formula η is 1, 2 or 3; H3 is each independently selected from the group consisting of hydrogen, .Ci_c6 alkyl, c丨·c6 alkoxy, hydroxyCl-C6, CF3, 〇CF3 'phenyl, halogen, phenoxy and a group of nitro groups; When n=2, you are selected from the following groups: 152043.doc .4 201223944 h—'hch OMSMO OMC CH3-C-ICH3 CH3—ilCH3 CICIC ο -3 CIC 3 1 3 F I F CICIC 6 When n=3, W is selected from the following groups T is selected from the group consisting of hydrogen, CVC6 alkyl, CVC6 alkoxy, CVC6 alcohol, carboxyl, CF3, phenyl, halogen, phenoxy and nitro; γ and Z are each independently selected from hydrogen, hydrazine :,-(Group of 36 alkyl, CVC6 alkoxy, CF3, phenyl, _, phenoxy). 152043.doc