Preparation method of parylene series products and parylene series products

Abstract

The application provides a preparation method of a series of parylene products, comprising the following steps: S1. reacting compound 1, compound 2 and N,N,N',N'-tetramethyl-diaminomethane to obtain a double quaternary amine salt; S2. the double quaternary amine salt and a catalyst are subjected to an elimination reaction under alkaline conditions to obtain a general formula of the series of parylene products shown in formula I; the structural formula of compound 1, compound 2 and the double quaternary amine salt are general formulae shown in formula II, III and IV respectively; the double quaternary amine salt with a connecting arm is obtained by reacting various benzyl halides with N,N,N',N'-tetramethyl-diaminomethane; the double quaternary amine salt and the catalyst are subjected to an elimination reaction under alkaline conditions to release N,N,N',N'-tetramethyl-diaminomethane, and an intermediate state of para-quinque-methane is formed when intramolecular degradation occurs; due to the π-π conjugation of the two benzene rings of the intermediate state, the face-to-face ring closure reaction is more prone to occur, the head-to-tail linear polymerization side reaction of the intermediate state can be effectively avoided, the reaction yield is greatly improved, and the series of parylene products can be efficiently prepared.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic chemistry, and particularly relates to a preparation method of a parylene series product and the parylene series product. BACKGROUND

[0002] Parylene is a new type of coating material developed and applied in the 1970s, which is a polymer of p-xylene. The raw material used for parylene coating is cyclic p-xylene dimer. According to the different chemical structures of the cyclic p-xylene dimer, the parylene powder can be divided into parylene N powder, C powder, D powder, F powder and HT powder.

[0003] When the parylene powder is used, first, the above different series of cyclic p-xylene dimer powder is placed in an evaporation furnace of a coating equipment, and under the condition of vacuum 150 DEG C, the solid raw material is upgraded into a gaseous state, and then under the condition of pyrolysis of 650-700 DEG C, the gaseous raw material is cracked into a monomer with reactivity. The active monomer can form a straight-chain polymer under the condition of vacuum and temperature reduction, that is, a transparent insulating coating, which provides a complete high-quality protective coating for the element to resist the invasion of acid, alkali, salt mist, mold and various corrosive gases. At present, the parylene coating technology has been widely used in the fields of aerospace, new energy vehicles, circuit boards, magnetic materials, sensors, silicone rubber, sealing elements, medical devices, precious cultural relics and the like.

[0004] At present, the chemical synthesis methods of the parylene powder series mainly include photolysis desulfurization method, metal coupling method and Hofmann elimination method. These methods generally have many shortcomings such as expensive raw materials, low production efficiency and being not conducive to large-scale production.

[0005] Masaaki Iwata et al. used the photolysis desulfurization method to prepare parylene N powder derivatives by desulfurization of cyclic disulfide under the irradiation of a high-pressure mercury lamp, and the laboratory yield can reach more than 50%. However, the raw material cyclic disulfide needs to be prepared at an ultra-dilute concentration, and the production efficiency is extremely low, which is not suitable for large-scale production (Bull. Chem. Soc. Jpn., 58, 2502-2514).

[0006]

[0007] The United States Special Coating System Company has disclosed a method for preparing parylene HT powder by using the metal coupling method (WO1998041490A1), but seven fluorine impurities are generated, which are not easy to separate and purify.

[0008]

[0009] In 2018, Shanghai Qixin New Material Technology Co., Ltd. reported a method for preparing parylene F powder by zinc powder-mediated coupling reaction using 2,3,5,6-tetrafluoro-p-dichloromethylbenzene as raw material (CN109232168A). This method produces trimers and polymers, which are difficult to separate and purify, and the yield is not high.

[0010]

[0011] The above-mentioned method for preparing parylene powder material by metal coupling requires the use of intermediate raw materials 2,3,5,6-tetrafluoro-p-dichloromethylbenzene (TFC) and 1,4-bis(chlorodifluoromethyl) benzene (DCTF) with dibenzyl chloride structure. DCTF and TFC need to be prepared through multiple steps of harsh reactions, and the production cost is very high, which seriously restricts the industrial application of this technology.

[0012] Hak-Fun Chow et al. of Hong Kong University of Science and Technology published a method for preparing parylene N powder by Hofmann elimination reaction using quaternary ammonium salt of p-methyl chlorobenzyl as raw material, which has a yield of only 10-20%.

[0013]

[0014] Since the 1970s, scientists around the world have found that during the research and development of the synthesis process of parylene powder material series, the traditional Hofmann elimination method for preparing parylene compounds is prone to the following head-to-tail linear polymerization reaction, and the main product becomes a polymer, which ultimately leads to a very low yield of the target product and an ineffective control of the cost.

[0015]

[0016] Therefore, there is an urgent need in the industry to develop a simple and low-cost method for preparing parylene series products. SUMMARY

[0017] In view of the deficiencies of the prior art, the purpose of the present application is to provide a preparation method for parylene series products, which is simple in process and can efficiently prepare parylene series products, thereby improving the reaction yield.

[0018] To achieve this purpose, the present application adopts the following technical solutions:

[0019] The first purpose of the present application is to provide a preparation method for parylene series products, comprising the following steps:

[0020] S1. Reacting compound 1, compound 2 and N,N,N',N'-tetramethyl-diaminomethane to obtain a bis-quaternary amine salt;

[0021] S2. The bis-quaternary ammonium salt and catalyst undergo an elimination reaction under alkaline conditions to obtain the Pyrelin series products of the general formula shown in Formula I;

[0022]

[0023] The structural formulas of compounds 1, 2, and the bisquaternary ammonium salt are the general formulas shown in formulas II, III, and IV, respectively:

[0024]

[0025] Among them, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from hydrogen atoms, halogens, amino groups, nitro groups, ester groups, aldehyde groups, methoxy groups, ethoxy groups, cyano groups, trifluoromethyl groups, ethynyl groups, vinyl groups, and saturated alkyl groups; X and Y are each independently selected from fluorine, chlorine, bromine, and iodine atoms.

[0026] Preferably, the saturated alkyl group has no more than 8 carbon atoms and includes at least one of the following: straight-chain or branched methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

[0027] The reaction process of this invention is as follows:

[0028]

[0029] Specifically, in step S2, the elimination reaction results in a p-quinone dimethane intermediate of the general formula shown in Formula V:

[0030]

[0031] The p-quinone dimethane intermediate undergoes a cyclization reaction to form the P-relin series products of the general formula shown in Formula I, wherein m is at least one of 1, 2, 3, and 4, and n is at least one of 5, 6, 7, and 8.

[0032] Specifically, in step S2, the catalyst is a quaternary ammonium salt and / or a quaternary phosphorus salt;

[0033] Preferably, the catalyst comprises at least one of the following quaternary phosphonium salts: triphenylmethylphosphonium bromide, tetraphenylphosphonium bromide, tetrabutylphosphonium hydroxide, benzyltriphenylphosphonium chloride, hexadecyltributylphosphonium chloride, hexadecyltrihexylphosphonium chloride, allyltriphenylphosphonium chloride, pentyltributylphosphonium chloride, benzyltributylphosphonium chloride, propyltriphenylphosphonium chloride, benzyltributylammonium chloride, tetrabutylammonium bromide, and tetrabutylammonium chloride.

[0034] Specifically, in step S1, compound 1 and compound 2 are each independently selected from at least one of the following structural formulas:

[0035]

[0036]

[0037] Specifically, the said series of products of pirellini is selected from at least one of the following structural formulae:

[0038]

[0039]

[0040] Specifically, the step S2 is to be carried out under alkaline conditions, and the alkali selected is a strong inorganic base.

[0041] Preferably, the said strong inorganic base is one selected from NaOH, KOH, LiOH, RbOH, CsOH, GrOH, Ca(OH)2, Sr(OH)2, Ba(OH)2and Ra(OH)2.

[0042] Specifically, in the step S1, the molar ratio of the said compound 1 and the said compound 2 is 1:1, and the molar ratio of the said compound 1 and the said N,N,N',N'-tetramethyl-diaminomethane is (0.9-1):1.

[0043] Preferably, the temperature of the said reaction is 10-50℃, and the time is 2-5h.

[0044] Specifically, in the step S2, the molar ratio of the total feeding of the said compound 1 and compound 2 to the said catalyst is 100:(0.1-1).

[0045] Preferably, the temperature of the said elimination reaction is 90-120℃, and the time is 18-30h.

[0046] Preferably, the molar ratio of the said compound 1 and the said N,N,N',N'-tetramethyl-diaminomethane can be 0.9:1, 0.91:1, 0.92:1, 0.93:1, 0.94:1, 0.95:1, 0.96:1, 0.97:1, 0.98:1, 0.99:1 or 1:1, etc.; more preferably, the temperature of the said reaction can be 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃ or 50℃, etc., and the time can be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h, etc., but is not limited to the above listed values, and other values not listed within the above range are also applicable.

[0047] Preferably, in step S2, the molar ratio of the total feed of compound 1 and compound 2 to the feed of the catalyst is 100:0.1, 100:0.2, 100:0.3, 100:0.4, 100:0.5, 100:0.6, 100:0.7, 100:0.8, 100:0.9 or 100:1, etc. More preferably, the temperature of the elimination reaction can be 90℃, 95℃, 100℃, 105℃, 110℃, 115℃ or 120℃, and the time can be 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h or 30h, etc. However, the above-mentioned values are not limited, and other values within the above-mentioned range are also applicable.

[0048] Specifically, the first solvent in step S1 is selected from dichloromethane, methanol, ethanol, isopropanol, tetrahydrofuran, toluene, 1,4-dioxane, and N,N-dimethylformamide. In step S2, a second solvent with a boiling point greater than 85℃ is also included, and the second solvent is selected from at least two of xylene, dimethyl sulfoxide, toluene, anisole, 1,4-dioxane, mesitylene, and chlorobenzene.

[0049] The second object of the present application is to provide a series of pirellini products prepared by the above-mentioned preparation method, wherein the series of pirellini products are selected from at least one of the following structural formulae:

[0050]

[0051]

[0052]

[0053] Compared with the prior art, the present application has the following beneficial effects:

[0054] The present application provides a preparation method of a series of pirellini products and a series of pirellini products. Various benzyl halides are reacted with N,N,N',N'-tetramethyl-diaminomethane to prepare a double quaternary ammonium salt with a connecting arm. In the presence of a catalyst and an alkaline condition, intramolecular degradation occurs through an elimination reaction, releasing N,N,N',N'-tetramethyl-diaminomethane while forming a p-quinodimethane intermediate. Due to the π-π conjugation of the two benzene rings of the p-quinodimethane intermediate, a face-to-face ring closure reaction is more likely to occur, which can effectively avoid the head-to-tail linear polymerization side reaction of the p-quinodimethane intermediate, greatly improving the reaction yield and efficiently preparing pirellini N powder, C powder, D powder, F powder, halogen-free C powder and other pirellini series products. DETAILED DESCRIPTION

[0055] The technical solutions of the present application are further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations of the present application.

[0056] Embodiment 1

[0057] The present embodiment provides a preparation method of a series of parylene products (parylene N powder) and the series of parylene products, and the reaction equation is as follows:

[0058]

[0059] Specifically includes the following steps:

[0060] S1. In dichloromethane (500 ml), 4-(chloromethyl)-1-methylbenzene (1.1 mol), N, N, N', N'-tetramethyl-diaminomethane (0.5 mol) were added in sequence, and the reaction was stirred at 20°C for 5 hours. After detecting the end of the reaction, the solvent was removed under reduced pressure to obtain a solid crude product, which was slurried with methyl tert-butyl ether (200 ml) to obtain a double quaternary ammonium salt JA-1 (0.45 mol) with a yield of 90%;

[0061] S2. A reaction bottle was added with a 51% KOH (6.09 mol) aqueous solution (669 g), xylene (1000 ml), dimethyl sulfoxide (430 ml), and benzyl triphenyl phosphonium chloride (0.004 mol). Under stirring, an aqueous solution containing 0.4 mol of double quaternary ammonium salt JA-1 (500 ml) was added dropwise at 90°C, and the dropping was completed in 4 hours. The reaction was maintained at 90°C for 24 hours. The reaction liquid was allowed to stand and separate into layers, and the upper xylene phase was taken. After washing with water and decolorizing with activated carbon, the filtrate was concentrated to 750 ml by distillation, and white crystals were obtained by cooling and crystallization. After vacuum drying at 50°C, 58.3 grams of parylene N powder (0.28 mol) was obtained with a yield of 70%.

[0062] The nuclear magnetic resonance characterization data are as follows: 1 HNMR (400 MHz, CDCl3): δ 3.09 (s, 8H, ArCH2), 6.50 (s, 8H, ArH).

[0063] Embodiment 2

[0064] The embodiment provides a preparation method of a series of pirellin products (pirlin N powder) and the series of pirellin products, and comprises the following steps which are basically the same as those in the embodiment 1, except that in the step S1, the selected benzyl halide is 4-(bromomethyl)-1-methylbenzene (1.1 mol), and a double quaternary ammonium salt JA-9 (0.46 mol) is obtained, with a yield of 92%; and in the step S2, the aqueous solution (500 ml) containing 0.4 mol of the double quaternary ammonium salt JA-0 is added dropwise at 90 DEG C, and finally 56.2 grams of the pirellin N powder (0.27 mol) is obtained, with a yield of 68%.

[0065] Embodiment 3

[0066] The embodiment provides a preparation method of a series of pirellin products (pirlin M powder) and the series of pirellin products, and the reaction equation is as follows:

[0067]

[0068] Specifically, the steps include the following steps:

[0069] S1. 1-(chloromethyl)-1,3,4-trimethylbenzene (1.1 mol) and N,N,N',N'-tetramethyl-diaminomethane (0.5 mol) are sequentially added into ethanol (500 ml), and then the mixture is stirred at 40 DEG C for 4 hours; after the reaction is detected to be completed, the solvent is removed under reduced pressure to obtain a solid crude product, which is beaten with methyl tert-butyl ether (200 ml) to obtain a double quaternary ammonium salt JA-5 (0.44 mol), with a yield of 88%;

[0070] S2. A reaction bottle is added with a 51% KOH (6.09 mol) aqueous solution (669 g), xylene (1000 ml), dimethyl sulfoxide (430 ml) and benzyl tributyl ammonium chloride (0.004 mol), and then an aqueous solution (500 ml) containing 0.4 mol of the double quaternary ammonium salt JA-5 is added dropwise under stirring at 100 DEG C; after the dropping is completed for 4 hours, the internal temperature is kept at 100 DEG C for 20 hours of reaction. The reaction liquid is allowed to stand and separate into layers, the upper xylene phase is taken, washed with water, decolorized with activated carbon, and the filtrate is concentrated to 750 ml by distillation, and then cooled to crystallize white crystals; the white crystals are dried at 50 DEG C under vacuum to obtain 58.2 grams of the pirellin M powder (0.22 mol), with a yield of 55%.

[0071] The nuclear magnetic resonance characterization data are as follows: 1 HNMR (400MHz, CDCl3): δ 2.24 (s, 12H, CH3), 2.73 (m, 4H, CH2), 3.16 (m, 4H, CH2) 6.40 (s, 4H, ArH).

[0072] Embodiment 4

[0073] The embodiment provides a preparation method of a series of perrylene products (perrylene B powder) and the series of perrylene products, and a reaction equation is as follows:

[0074]

[0075] The embodiment comprises the following steps:

[0076] S1. N, N, N', N'-tetramethyl-diaminomethane (0.5 mol) is added into dichloromethane (300 ml), a dichloromethane solution containing 0.5 mol of 4-(chloromethyl)-1-methylbenzene is added dropwise at 20 DEG C, stirring is carried out for 3 hours, then a dichloromethane solution containing 0.5 mol of 2-bromo-4-(chloromethyl)-1-methylbenzene is added dropwise, stirring is carried out for 3 hours, the solvent is removed under reduced pressure to obtain a solid crude product, and the crude product is slurried in methyl tert-butyl ether (200 ml) to obtain a double quaternary ammonium salt JA-7 (0.42 mol), and the yield is 84%.

[0077] S2. A 51% KOH aqueous solution (669 g) is added into a reaction bottle, toluene (1000 ml) and dimethyl sulfoxide (430 ml) are added, and benzyl triphenyl phosphonium chloride (0.004 mol) is added; a double quaternary ammonium salt JA-7 aqueous solution (500 ml) containing 0.4 mol of the double quaternary ammonium salt JA-7 is added dropwise under stirring at 100 DEG C, dropwise addition is completed in 4 hours, and the reaction is carried out for 22 hours while keeping the internal temperature at 100 DEG C. The reaction liquid is allowed to stand to separate into two layers, the upper toluene phase is taken, washed with water, decolorized with activated carbon, the filtrate is concentrated to 500 ml by distillation, and white crystals are obtained by cooling and crystallization; and 54.6 grams of perrylene B powder (0.19 mol) is obtained by vacuum drying at 50 DEG C, and the yield is 48%.

[0078] NMR characterization data are as follows: 1 HNMR (400 MHz, CDCl3): δ 2.76-2.88 (m, 8H), 6.93 (dd, 1H, ArH), 7.06-7.11 (m, 5H, ArH), 7.17 (d, 1H, ArH).

[0079] Embodiment 5

[0080] The embodiment provides a preparation method of a series of perrylene products (perrylene C powder) and the series of perrylene products, and a reaction equation is as follows:

[0081]

[0082] The embodiment comprises the following steps:

[0083] S1. In toluene (500 ml) 3-chloro-4-methyl chlorobenzyl (1.1 mol), N, N, N', N'-tetramethyl diamino methane (0.5 mol) were added in turn, and the reaction was stirred at 50°C for 4 hours. After the reaction was detected to be completed, the solvent was removed under reduced pressure to obtain a solid crude product. The product was slurried with methyl tert-butyl ether (200 ml) to obtain a double quaternary ammonium salt JA-2 (0.46 mol) with a yield of 93%.

[0084] S2. A 51% KOH aqueous solution (669 g) (6.09 mol), xylene (1000 ml), dimethyl sulfoxide (430 ml), and tetrabutylammonium bromide (0.004 mol) were added to a reaction bottle. An aqueous solution (500 ml) containing 0.4 mol of double quaternary ammonium salt JA-2 was added dropwise under stirring at 90°C. After 4 hours of dropping, the internal temperature was kept at 90°C for 24 hours of reaction. The reaction liquid was allowed to stand and separate into layers. The upper xylene phase was taken, washed with water, decolorized with activated carbon, and the filtrate was concentrated by distillation to 300 ml. White crystals were obtained by cooling and crystallization. After vacuum drying at 50°C, 63.8 grams of a parilin C powder (0.23 mol) was obtained with a yield of 58%.

[0085] NMR characterization data are as follows: 1 HNMR (400 MHz, CDCl3): δ 2.80-2.84 (m, 2H, CH2), 2.95-2.99 (m, 2H, CH2), 3.13-3.20 (m, 2H, CH2), 3.51-3.57 (m, 2H, CH2), 6.31 (d, 2H, ArH), 6.47 (d, 2H, ArH), 7.06 (dd, 2H, ArH).

[0086] Example 6

[0087] The present embodiment provides a preparation method of a parilin series product (parilin F powder) and the parilin series product. The reaction equation is as follows:

[0088]

[0089] Specifically includes the following steps:

[0090] S1. In dichloromethane (500 ml) 1,2,4,5-tetrafluorobromobenzyl (1.1 mol), N, N, N', N'-tetramethyl diamino methane (0.5 mol) were added in turn, and the reaction was stirred at 20°C for 5 hours. After the reaction was detected to be completed, the solvent was removed under reduced pressure to obtain a solid crude product. The product was slurried with methyl tert-butyl ether (200 ml) to obtain a double quaternary ammonium salt JA-4 (0.46 mol) with a yield of 92%.

[0091] S2. To the reaction flask was added 51% KOH (6.09 mol) aqueous solution (669 g), xylene (1000 ml), dimethyl sulfoxide (430 ml), tetrabutylammonium bromide (0.004 mol), and an aqueous solution (500 ml) containing 0.4 mol of the bis-quaternary ammonium salt JA-4 was added dropwise with stirring at 110°C. After 4 hours of dropwise addition, the internal temperature was maintained at 110°C for 18 hours. The reaction solution was allowed to stand and separate into layers, and the upper xylene phase was removed, washed with water, decolorized with activated carbon, and the filtrate was concentrated by distillation to 350 ml. White crystals were obtained by cooling and crystallization, and the product was dried under vacuum at 50°C to obtain 101.4 g of the parvulin F powder (0.29 mol), with a yield of 73%.

[0092] NMR characterization data are as follows: 1 HNMR (400 MHz, CDC13): δ 3.30 (s, 8H, CH2).

[0093] Example 7

[0094] This example provides a method for preparing a parvulin product (parvulin D powder) and the parvulin product, and the reaction equation is as follows:

[0095]

[0096] The method comprises the following steps:

[0097] S1. 2,4-dichloro-4-methyl chlorobenzene (1.1 mol) and N,N,N',N'-tetramethyl-diaminomethane (0.5 mol) were sequentially added to toluene (500 ml) and stirred at 50°C for 5 hours. After the reaction was completed, the solvent was removed under reduced pressure to obtain a solid crude product, which was slurried in methyl tert-butyl ether (200 ml) to obtain the bis-quaternary ammonium salt JA-3 (0.45 mol) with a yield of 90%;

[0098] S2. To the reaction flask was added 51% KOH (6.09 mol) aqueous solution (669 g), xylene (1000 ml), dimethyl sulfoxide (430 ml), tetrabutylammonium bromide (0.004 mol), and an aqueous solution (500 ml) containing 0.4 mol of the bis-quaternary ammonium salt JA-3 was added dropwise with stirring at 90°C. After 4 hours of dropwise addition, the internal temperature was maintained at 90°C for 24 hours. The reaction solution was allowed to stand and separate into layers, and the upper xylene phase was removed, washed with water, decolorized with activated carbon, and the filtrate was concentrated by distillation to 300 ml. White crystals were obtained by cooling and crystallization, and the product was dried under vacuum at 50°C to obtain 96.9 g of the parvulin D powder (0.28 mol), with a yield of 70%.

[0099] NMR characterization data are as follows: 1HNMR (400 MHz, CDC13): δ 7.20 (s, 4H, Ar-H), 3.29-3.18 (m, 4H, CH2), 3.04-2.93 (m, 4H, CH2).

[0100] Example 8

[0101] The present example provides a preparation method of a series of parylene products (parylene P-5 powder) and the series of parylene products, and the reaction equation is as follows:

[0102]

[0103] Specifically comprising the following steps:

[0104] S1. 2,4-dibromo-4-methylbenzyl bromide (1.1 mol), N,N,N',N'-tetramethyl-diaminomethane (0.5 mol) were sequentially added in dichloromethane (500 ml), and stirred at 20°C for 5 hours. After detecting the end of the reaction, the solvent was removed under reduced pressure to obtain a solid crude product, which was slurried with methyl tert-butyl ether (200 ml) to obtain a double quaternary ammonium salt JA-18 (0.47 mol) with a yield of 94%;

[0105] S2. A 51% KOH aqueous solution (669 g) (6.09 mol), toluene (1000 ml), dimethyl sulfoxide (430 ml), and benzyl tributyl ammonium bromide (0.004 mol) were added to a reaction bottle, and an aqueous solution (500 ml) containing 0.4 mol of double quaternary ammonium salt JA-18 was added dropwise at 90°C with stirring. After 4 hours of dropping, the internal temperature was kept at 90°C for 28 hours of reaction. The reaction liquid was allowed to stand and separate into layers, and the upper toluene phase was taken, washed with water, decolorized with activated carbon, and the filtrate was concentrated to 300 ml by distillation, and then cooled to crystallize white crystals; vacuum drying at 50°C yielded 152 grams of parylene P-5 powder (0.29 mol) with a yield of 72.5%.

[0106] The nuclear magnetic resonance characterization data are as follows: 1 HNMR (400 MHz, CDC13): δ 7.20 (s, 4H, Ar-H), 3.29-3.18 (m, 4H, CH2), 3.04-2.93 (m, 4H, CH2).

[0107] Example 9

[0108] The present example provides a preparation method of a series of parylene products (parylene P-5 powder) and the series of parylene products, and the reaction equation is as follows:

[0109]

[0110] Specifically comprising the following steps:

[0111] S1. In tetrahydrofuran (500 ml), 2-ethyl-4-methylbenzyl bromide (1.1 mol) and N, N, N', N'-tetramethyl-diaminomethane (0.5 mol) were sequentially added, and the reaction was stirred at 40°C for 3 hours. After the reaction was detected to be completed, the solvent was removed under reduced pressure to obtain a solid crude product. The product was slurried with methyl tert-butyl ether (200 ml) to obtain a double quaternary ammonium salt JA-12 (0.46 mol) with a yield of 92%.

[0112] S2. A 51% KOH aqueous solution (669 g) was added to a reaction bottle, followed by the addition of xylene (1000 ml), dimethyl sulfoxide (430 ml), and benzyl tributyl ammonium bromide (0.004 mol). An aqueous solution (500 ml) containing 0.4 mol of the double quaternary ammonium salt JA-12 was added dropwise under stirring at 90°C. After 4 hours of dropping, the internal temperature was maintained at 90°C for 30 hours. The reaction liquid was allowed to stand to separate into layers, and the upper xylene phase was taken. The xylene phase was washed with water, decolorized with activated carbon, and concentrated to 300 ml by distillation. The product was crystallized by cooling, and 66 g of a white crystal of parirelin E powder (0.25 mol) was obtained with a yield of 62.5%.

[0113] The nuclear magnetic resonance characterization data are as follows: 1 HNMR (400 MHz, CDCl3): δ 6.60-6.56 (m, 2H, ArH), 6.31-6.29 (m, 2H, ArH), 6.14 (bs, 2H, ArH), 3.38-3.30 (m, 2H, CH2), 3.06-2.96 (m, 4H, CH2), 2.83-2.72 (m, 2H, CH2), 2.32-2.22 (m, 4H, CH2-CH3), 1.18-1.38 (m, 6H, CH3).

[0114] Example 10

[0115] The present embodiment provides a preparation method of a parirelin series product (parirelin P-3 powder) and the parirelin series product. The reaction equation is as follows:

[0116]

[0117] Specifically, the method comprises the following steps:

[0118] S1. In dichloromethane (500 ml), 3-bromo-4-methylbenzyl bromide (1.1 mol) and N, N, N', N'-tetramethyl-diaminomethane (0.5 mol) were sequentially added, and the reaction was stirred at 20°C for 5 hours. After the reaction was detected to be completed, the solvent was removed under reduced pressure to obtain a solid crude product. The product was slurried with methyl tert-butyl ether (200 ml) to obtain a double quaternary ammonium salt JA-6 (0.45 mol) with a yield of 91%.

[0119] S2. To the reaction bottle, 51% KOH (6.09 mol) aqueous solution (669 g), xylene (1000 ml), dimethyl sulfoxide (430 ml), tetrabutylammonium bromide (0.004 mol) were added, and an aqueous solution (500 ml) containing 0.4 mol of bis-quaternary ammonium salt JA-6 was added dropwise under stirring at 90°C. After 4 hours of dropwise addition, the internal temperature was maintained at 90°C for 24 hours. The reaction solution was allowed to stand and separate into layers, and the upper xylene phase was taken, washed with water, decolorized with activated carbon, and the filtrate was concentrated by distillation to 300 ml. Crystallization was performed by cooling, and white crystals were obtained. After vacuum drying at 50°C, 102.5 grams of parvulin P-3 powder (0.28 mol) was obtained, with a yield of 70%.

[0120] NMR characterization data are as follows: 1 HNMR (400 MHz, CDCl3): δ = 7.17 (d, 2H), 6.60 (d, 2H), 6.47 (dd, 2H), 3.36-3.25 (m, 2H), 3.11-3.01 (m, 4H), 2.93-2.83 (m, 2H).

[0121] Example 11

[0122] This example provides a preparation method of a parvulin series product (parvulin P-8 powder) and the parvulin series product, and the reaction equation is as follows:

[0123]

[0124] Specifically includes the following steps:

[0125] S1. In dichloromethane (500 ml), 3-trifluoromethyl-4-methylbenzyl bromide (0.5 mol) and N,N,N',N'-tetramethyl-diaminomethane (0.5 mol) were added in sequence, and stirring was performed at 20°C for 3 hours. Then, an aqueous solution (100 ml) containing 0.5 mol of 4-(bromomethyl)-1-methylbenzene in dichloromethane was added dropwise, and stirring was performed for 3 hours. After detection of the end of the reaction, the solvent was removed under reduced pressure to obtain a solid crude product, which was slurried with methyl tert-butyl ether (200 ml) to obtain bis-quaternary ammonium salt JA-11 (0.45 mol), with a yield of 91%;

[0126] S2. To the reaction flask was added 51% KOH (6.09 mol) aqueous solution (669 g), xylene (1000 ml), dimethyl sulfoxide (430 ml), tetrabutylammonium bromide (0.004 mol), and an aqueous solution (500 ml) containing 0.4 mol of the bisquaternary ammonium salt JA-11 was added dropwise with stirring at 90°C. After the dropwise addition was completed, the internal temperature was maintained at 90°C for 24 hours. The reaction solution was allowed to stand and separate into layers, and the upper xylene layer was removed. The xylene layer was washed with water, decolorized with activated carbon, and the filtrate was concentrated by distillation to 300 ml. The solution was cooled to induce crystallization, and white crystals were obtained. The crystals were dried in a vacuum at 50°C to obtain 71.84 g of the product (0.26 mol) as a white powder, which was identified as Perylins P-8. The yield was 65%.

[0127] NMR characterization data are as follows: 1 HNMR (400 MHz, CDCl3): δ = 2.90-3.30 (m, 6H, CH2), 3.41-3.57 (m, 2H, CH2), 6.36-6.94 (m, 7H, ArH).

[0128] The applicant states that the present application is illustrated by the above examples, which are a preparation method of a product of the Perylins series of the present application, but the present application is not limited to the above examples, i.e., it does not mean that the present application must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc., all fall within the protection scope and disclosure scope of the present application.

Claims

1. A process for the preparation of a parylene series product, characterized in that, Comprising the following steps: S1. Compound 1, compound 2 and N,N,N',N'-tetramethyl-diaminomethane are reacted to obtain a bis-quaternary amine salt; S2. The bis-quaternary amine salt and a catalyst are subjected to an elimination reaction under alkaline conditions to obtain a parylene series product of the general formula of formula I; Formula I The structural formulas of compound 1, compound 2 and bis-quaternary amine salt are respectively the general formulas of formula II, III and IV: 、 、 Formula II Formula III Formula IV Wherein, R1, R2, R3, R4, R5, R6, R7, R8 are each independently selected from hydrogen atom, halogen, amino, nitro, ester group, aldehyde group, methoxy, ethoxy, cyano, trifluoromethyl, ethynyl, vinyl, saturated alkyl; X, Y are each independently selected from fluorine, chlorine, bromine and iodine atom.

2. The method of claim 1, wherein, In step S2, the elimination reaction forms a p-quinodimethane intermediate of the general formula of formula V: Formula V The p-quinodimethane intermediate undergoes ring closure reaction to form a parylene series product of the general formula of formula I, wherein m is at least one of 1, 2, 3, 4, and n is at least one of 5, 6, 7, 8.

3. The method of claim 1 or 2, wherein the method further comprises, In step S2, the catalyst is a quaternary ammonium salt and / or a quaternary phosphonium salt.

4. The preparation method according to claim 3, characterized in that, The catalyst includes at least one of triphenylmethyl phosphonium bromide, tetraphenyl phosphonium bromide, tetrabutylphosphonium hydroxide, benzyltriphenylphosphonium chloride, hexadecyltributylphosphonium chloride, hexadecyltrihexylphosphonium chloride, allyltriphenylphosphonium chloride, pentyltributylphosphonium chloride, benzyltributylphosphonium chloride, propyltriphenylphosphonium chloride, benzyltributylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride.

5. The method of claim 1 or 2, wherein the step of preparing the mixture is performed at a temperature of 20 to 30°C. In step S1, compound 1 and compound 2 are each independently selected from at least one of the following structural formulas:

6. The method of claim 1 or 2, wherein the step of preparing the mixture is performed at a temperature of 20°C to 30°C. The parylene series product is selected from at least one of the following structural formulas:

7. The method of claim 1 or 2, wherein the method is carried out at a temperature of from 20°C to 30°C. Step S2 is carried out under alkaline conditions, and a strong inorganic base is selected.

8. The preparation method according to claim 7, characterized in that, The strong inorganic base is selected from one of NaOH, KOH, LiOH, RbOH, CsOH, GrOH, Ca(OH)2, Sr(OH)2, Ba(OH)2 and Ra(OH)2.

9. The method of claim 1 or 2, wherein the method is carried out at a temperature of from 20°C to 30°C. In step S1, the molar ratio of the compound 1 to the compound 2 is 1:1, and the molar ratio of the compound 1 to the N,N,N',N'-tetramethyl-diaminomethane is (0.9-1):

1.

10. The preparation method according to claim 9, characterized in that, The reaction temperature is 10-50℃, and the reaction time is 2-5h.

11. The method of claim 1 or 2, wherein, In step S2, the molar ratio of the total dosage of compound 1 and compound 2 to the catalyst is 100:(0.1-1).

12. The preparation method according to claim 11, characterized in that, The elimination reaction temperature is 90-120℃, and the reaction time is 18-30h.

13. The method of claim 1 or 2, wherein the method is carried out at a temperature of from 20°C to 30°C. In step S1, a first solvent is further included, and the first solvent is selected from dichloromethane, methanol, ethanol, isopropanol, tetrahydrofuran, toluene, 1,4-dioxane, N,N-dimethylformamide; In step S2, a second solvent with a boiling point greater than 85℃ is further included, and the second solvent is selected from at least two of xylene, dimethyl sulfoxide, toluene, anisole, 1,4-dioxane, mesitylene, chlorobenzene.

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