CN111100090A - Benzoazacyclo derivative, preparation method and application thereof, and photoluminescent lubricating grease - Google Patents

Benzoazacyclo derivative, preparation method and application thereof, and photoluminescent lubricating grease Download PDF

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CN111100090A
CN111100090A CN201811267992.9A CN201811267992A CN111100090A CN 111100090 A CN111100090 A CN 111100090A CN 201811267992 A CN201811267992 A CN 201811267992A CN 111100090 A CN111100090 A CN 111100090A
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compound
derivative
integer
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CN111100090B (en
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刘欣阳
庄敏阳
郑会
何懿峰
刘中其
孙洪伟
段庆华
刘大军
刘伟
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C07D263/57—Aryl or substituted aryl radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/48—Heterocyclic nitrogen compounds the ring containing both nitrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
    • C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Lubricants (AREA)

Abstract

The invention provides a benzoazacyclo derivative, a preparation method and application thereof, and photoluminescent lubricating grease containing the benzoazacyclo derivative. The structure of the benzo nitrogen heterocyclic derivative is as follows:
Figure DDA0001845338870000011
wherein A is S, O or NR, R is hydrogen or C1～6An alkyl group; each RaRadical, each RbRadical, each RcThe radicals, equal to or different from each other, are each independently selected from C1～6A linear or branched alkyl group; x is an integer of 0 to 4, y is an integer of 0 to 3, and z is an integer of 0 to 4. The lubricating grease disclosed by the invention can emit orange yellow light under ultraviolet irradiation, has excellent photoluminescence performance and wear resistance, and can be used for related mechanical equipment in the electrical appliance industry, the metallurgical industry, the food industry, the paper industry, the automobile industry and the aircraft industry.

Description

Benzoazacyclo derivative, preparation method and application thereof, and photoluminescent lubricating grease
Technical Field
The invention relates to a benzoazacyclo derivative, in particular to a benzoazacyclo derivative with a luminescent property.
Background
Traditional organic chromophores generally have strong luminescence at low concentrations, and weak or even no luminescence at high concentrations or in solid states, exhibiting an aggregate fluorescence quenching effect. This is because in the aggregate state, the strong intermolecular interactions lead to an enhancement of the non-radiative decay process of the excited state, with a significant decrease in fluorescence quantum yield. In the practical application process, the practical application of the organic light-emitting material is limited to a great extent by the aggregate fluorescence quenching effect. In recent years, research shows that some compounds show the opposite properties to the traditional organic luminescent compounds, not only do not have aggregation fluorescence quenching effect, but also show Aggregation Induced Emission (AIE) properties, and the appearance of the aggregation induced emission compounds provides a new solution for the application of organic luminescent materials in a solid state or at high concentration. 2- (2' -hydroxyphenyl) benzothiazole is a typical AIE compound, and researchers have applied it to a plurality of research fields such as light-emitting devices, fluorescent probes, biological imaging and the like in recent decades.
The lubricating grease is a solid to semi-fluid product prepared by dispersing a thickening agent in a liquid lubricant, has the functions of lubrication, protection and sealing, and plays a vital role in industrial machinery, agricultural machinery, the transportation industry, the aerospace industry, the electronic information industry and various military equipment.
Under some dark working conditions, the monitoring of the lubricating grease has great difficulty, and the residual amount of the lubricating grease is difficult to directly observe by naked eyes in many cases.
Disclosure of Invention
The invention provides a benzoazacyclo derivative, a preparation method and application thereof, and photoluminescent lubricating grease containing the thiazole derivative.
The structure of the benzo nitrogen heterocyclic derivative is as follows:
Figure BDA0001845338860000011
wherein A is S, O or NR, R is hydrogen or C1～6An alkyl group; each RaRadical, each RbRadical, each RcThe radicals, equal to or different from each other, are each independently selected from C1～6Straight or branched alkyl (preferably C)1～4Straight or branched chain alkyl); x is an integer of 0 to 4 (preferably 0 or 1), y is an integer of 0 to 3 (preferably 0 or 1), and z is an integer of 0 to 4 (preferably 0 or 1).
The benzo nitrogen heterocyclic derivative comprises one or more of the following compounds:
Figure BDA0001845338860000021
the preparation method of the benzo nitrogen heterocyclic derivative comprises the step of reacting the benzo nitrogen heterocyclic compound shown in the general formula (II) with the alkyne compound shown in the general formula (III),
Figure BDA0001845338860000022
in the general formula (II), A is S, O or NR, R is hydrogen or C1～6An alkyl group; the group X is F, Cl, Br, I, OH (preferably Cl or Br); each RaRadical, each RbThe radicals, equal to or different from each other, are each independently selected from C1～6Straight or branched alkyl (preferably C)1～4Straight or branched chain alkyl); x is an integer of 0 to 4 (preferably 0 or 1), and y is an integer of 0 to 3 (preferably 0 or 1); in the general formula (III), each RcThe radicals, equal to or different from each other, are each independently selected from C1～6Straight or branched alkyl (preferably C)1～4Straight or branched chain alkyl); z is an integer of 0 to 4 (preferably 0 or 1).
Benzazepine compounds of the general formula (II) include:
Figure BDA0001845338860000023
Figure BDA0001845338860000031
the acetylene compounds represented by the general formula (III) include:
Figure BDA0001845338860000032
according to the production method of the present invention, in the reaction, the molar ratio between the thiazole compound represented by the general formula (II) and the alkyne compound represented by the general formula (III) is preferably 1 to 3: 1, most preferably 1 to 2: 1; the reaction temperature is 0-50 ℃, and preferably 15-35 ℃; the reaction time is preferably 12-96 h, and more preferably 24-72 h; the reaction is preferably carried out under an inert gas (preferably nitrogen) blanket.
According to the invention, a catalyst may or may not be added to the reaction. A catalyst is preferably added in the reaction. The catalyst is preferably one or more of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound, more preferably a mixture of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound, and the molar ratio of the three is preferably 1: 0.1-10: 0.1 to 10, more preferably 1: 0.2-5: 0.2 to 5.
According to the present invention, preferably, the metal phosphine complex has the structure
Figure BDA0001845338860000033
Wherein M is Pd, Ru or Rh, L is selected from PPh3Ph, F, Cl, Br, I. The metal phosphine complex can be one or more of tetrakis (triphenylphosphine) palladium, tris (triphenylphosphine) palladium chloride, bis (triphenylphosphine) palladium dichloride, (triphenylphosphine) palladium trichloride, tetrakis (triphenylphosphine) ruthenium, tris (triphenylphosphine) ruthenium chloride, bis (triphenylphosphine) ruthenium dichloride, (triphenylphosphine) ruthenium trichloride, tetrakis (triphenylphosphine) rhodium, tris (triphenylphosphine) rhodium chloride, bis (triphenylphosphine) rhodium dichloride and (triphenylphosphine) rhodium trichloride, and preferably one or more of tetrakis (triphenylphosphine) palladium, tris (triphenylphosphine) palladium chloride, bis (triphenylphosphine) palladium dichloride and (triphenylphosphine) palladium trichloride.
According to the present invention, preferably, the metal halide may be one or more of a copper halide, an iron halide and a zinc halide, for example, one or more of copper chloride, cuprous chloride, copper bromide, cuprous bromide, copper iodide, cuprous iodide, ferric chloride, ferrous chloride, ferric bromide, ferrous bromide, ferric iodide, ferrous iodide, zinc chloride, zinc bromide, zinc iodide and zinc iodide may be used, and more preferably one or more of copper chloride, cuprous chloride, copper bromide, cuprous bromide, copper iodide and cuprous iodide.
According to the present invention, preferably, the hydrocarbyl phosphine compound has the structure
Figure BDA0001845338860000041
Wherein each R is independently selected from C6～C10Aryl and C1～C6Wherein at least one R is C6～C10Aryl group of (1). Said C is6～C10The aryl group of (a) may be selected from phenyl, naphthyl; said C is1～C6The linear or branched alkyl group of (a) may be selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl or isohexyl. The hydrocarbyl phosphine compound can be selected from triphenylphosphine and diphenylbutylphosphine.
According to the invention, the amount of the catalyst added is preferably 1% to 20% of the amount of the silole compound represented by formula (IV).
According to the preparation method of the present invention, a solvent may or may not be added in the reaction, and preferably a solvent is added. The solvent is preferably furan or C1～6Chlorinated alkane of (C)1～6Alkyl amine (more preferably furan, C)1～4Chlorinated alkane of (C)1～4The alkylamine of (b) may be selected, for example, from one or more of tetrahydrofuran, chloroform, methylene chloride, methyl chloride, trimethylamine, triethylamine and tripropylamine.
According to the production method of the present invention, it is preferable to subject the product of the reaction to a purification treatment. The purification treatment is preferably a recrystallization method and/or a column chromatography method. The recrystallization method is to separate and purify the product by using a solvent through a recrystallization method; the solvent is preferably one or more of benzene, toluene, xylene and hexane (more preferably a mixed solvent of toluene and n-hexane, and the mass ratio of the toluene to the n-hexane is 1: 0.1-10). The column chromatography method is to separate and purify a product by using an eluant through column chromatography; the eluent is preferably C1～6Chlorinated alkane of (C)1～6The alcohol(s) (more preferably a mixed solution of dichloromethane and methanol, in a volume ratio of 1: 0.05-10).
According to the production method of the present invention, preferably, the method for producing a benzazepine compound represented by the general formula (II) comprises a step of reacting a compound represented by the general formula (IV) with a compound represented by the general formula (V),
Figure BDA0001845338860000051
in the general formula (IV), A is S, O or NR, R is hydrogen or C1～6An alkyl group; each RaThe radicals, equal to or different from each other, are each independently selected from C1～6Straight or branched alkyl (preferably C)1～4Straight or branched chain alkyl); x is an integer between 0 and 4 (preferably 0 or 1); in formula (V), the group X is F, Cl, Br, I, OH (preferably Cl or Br); each RbThe radicals, equal to or different from each other, are each independently selected from C1～6Straight or branched alkyl (preferably C)1～4Straight or branched chain alkyl); y is an integer of 0 to 3 (preferably 0 or 1).
According to the production method of the present invention, preferably, in the production method of the benzazepine compound represented by the general formula (II), the molar ratio between the compound represented by the general formula (IV) and the compound represented by the general formula (V) is preferably 0.5 to 2: 1, most preferably 0.9 to 1.1: 1. the temperature for the reaction of the compound represented by the general formula (IV) and the compound represented by the general formula (V) is 80-240 ℃ (preferably 140-180 ℃); the reaction time is preferably 2-24 h (more preferably 4-12 h); the reaction is preferably carried out under protection of an inert gas, preferably nitrogen. A solvent is preferably added in the reaction, and the solvent is preferably one or more of polyphosphoric acid, dimethyl sulfoxide, dimethylformamide and 1, 4-dioxane (more preferably polyphosphoric acid).
The benzo nitrogen heterocyclic ring derivative has excellent photoluminescence performance, can emit orange yellow light under ultraviolet irradiation, and can be applied to light-emitting parts and devices, fluorescent probes, biological imaging, lubricating oil and lubricating grease.
The invention also provides lubricating grease which comprises the benzo nitrogen heterocycle derivative, a thickening agent and lubricating base oil. The benzoazacyclo derivative accounts for 0.0005 to 5 percent of the total mass of the lubricating grease, and preferably 0.001 to 1 percent; the thickening agent accounts for 5-30%, preferably 10-20% of the total mass of the lubricating grease; the lubricating base oil constitutes the main component of the grease.
The thickening agent comprises one or more of a polyurea thickening agent, a lithium-based thickening agent, a composite lithium-based thickening agent, a calcium-based thickening agent and a composite aluminum-based thickening agent, preferably the polyurea thickening agent, the lithium-based thickening agent, the composite lithium-based thickening agent and the composite aluminum-based thickening agent, and most preferably the lithium-based thickening agent.
The base oil may be one or more of mineral oil, vegetable oil and synthetic oil, preferably mineral oil and synthetic oil.
The lubricating grease disclosed by the invention can emit orange yellow light under ultraviolet irradiation, and has excellent photoluminescence performance and wear resistance.
The preparation method of the lubricating grease comprises the following steps: mixing lubricating base oil, thickener and benzoazacyclo derivative, refining, and grinding into grease. The refining operation temperature is 160-240 ℃, and preferably 180-220 ℃; the refining operation time is 10-240 min, preferably 20-60 min. All the lubricating base oil, the benzoazacyclo derivative and the thickening agent can be mixed and refined together, or part of the lubricating base oil, part of the benzoazacyclo derivative and the thickening agent can be mixed and refined and then mixed with the rest of the lubricating base oil and the rest of the benzoazacyclo derivative. The benzoazacyclo derivative is preferably dissolved in a solvent and then mixed with lubricating base oil and a thickening agent for refining, wherein the solvent is preferably an aromatic hydrocarbon solvent, such as toluene and xylene.
The thickener can be a soap-based thickener or a non-soap-based thickener. The soap-based thickener is preferably a metal soap, and can be a single metal soap or a composite metal soap, and the metal can be one or more of lithium, sodium, calcium, aluminum, zinc, potassium, barium, lead and manganese. The non-soap-based grease thickener is preferably one or more of graphite, carbon black, asbestos, polyurea group, bentonite and organic clay.
The preparation method of the polyurea lubricating grease comprises the following steps: mixing part of lubricating base oil, the thiazole derivative, the amine and the isocyanate, reacting at 65-95 ℃ for 10-60min, continuously heating to 190-220 ℃ after complete reaction, refining at high temperature, adding the rest base oil, cooling to 60-120 ℃, and grinding into grease. The amine is C2-C20 alkylamine and/or C6-C20 aromatic amine, and can be one or more of octadecylamine, cyclohexylamine and aniline; the isocyanate is C2-C20 isocyanate, and can be one or more of Toluene Diisocyanate (TDI) and 4, 4' -diphenylmethane diisocyanate (MDI).
The preparation method of the lithium-based lubricating grease comprises the following steps: mixing and heating part of lubricating base oil and fatty acid in a reaction kettle, heating to 40-90 ℃, adding the aqueous solution of the benzo nitrogen heterocycle derivative and the lithium hydroxide, heating to remove water, continuously heating to 190-220 ℃ for high-temperature refining, adding the rest lubricating base oil, cooling to 60-120 ℃, and grinding into grease. The fatty acid is C12-C20 fatty acid and/or C12-C20 hydroxy fatty acid, and can be one or more of lauric acid, palmitic acid, stearic acid and 12-hydroxystearic acid.
The preparation method of the composite aluminum-based lubricating grease comprises the following steps: mixing and heating part of base oil, fatty acid and micromolecular acid in a reaction kettle, heating to 40-90 ℃, adding the benzo nitrogen heterocycle derivative, mixing and heating the other part of lubricating base oil and an aluminum alkoxide compound to 40-100 ℃, adding the mixture into the reaction kettle after the aluminum alkoxide compound is completely dissolved, continuously heating to 190-220 ℃ for high-temperature refining, adding the rest of lubricating base oil, cooling to 60-120 ℃, and grinding into grease. The fatty acid is C12-C20 fatty acid and/or C12-C20 hydroxy fatty acid, and can be one or more of lauric acid, palmitic acid, stearic acid and 12-hydroxystearic acid; the micromolecular acid is C2-C11 organic acid, and can be one or more of acetic acid, propionic acid, oxalic acid, adipic acid, azelaic acid, sebacic acid and terephthalic acid; the aluminium alkoxide compound is preferably selected from aluminium isopropoxide, aluminium isopropoxide dimer, aluminium isopropoxide trimer.
The lubricating grease disclosed by the invention can emit orange yellow light under ultraviolet irradiation, has excellent photoluminescence performance and wear resistance, and can be used for related mechanical equipment in the electrical appliance industry, the metallurgical industry, the food industry, the paper industry, the automobile industry and the aircraft industry.
Detailed Description
The main raw materials used are as follows:
chemical reagents such as polyphosphoric acid, o-aminothiophenol, sodium hydroxide bromosalicylate, sodium carbonate, 4- (dicyanovinyl) phenylacetylene, cuprous iodide, triphenylphosphine, palladium tetratriphenylphosphine, 1, 4-dioxane, octadecylamine, MDI, 12-hydroxystearic acid, lithium hydroxide monohydrate, stearic acid, benzoic acid, aluminum isopropoxide trimer, tetrahydrofuran, triethylamine, dichloromethane, methanol, toluene and the like are from the company Bailingwei reagent, the company Inoka reagent or the company Sigma reagent, and are analytically pure;
the PAO10 base oil was obtained from Exxon Mobil.
Example 1
200mL of polyphosphoric acid (PPA), 0.2mol of o-aminosulfol and 0.2mol of p-bromosalicylic acid are added into a 500mL three-neck flask, and the mixture is stirred and reacted for 6 hours at 160 ℃ under the protection of nitrogen. After the reactant is cooled, a large amount of ice water is used for diluting, 10% sodium hydroxide solution and saturated sodium carbonate solution are used for adjusting the reactant to be neutral, a large amount of solids are separated out, and a crude product is obtained by filtration. Dissolving the crude product with 1, 4-dioxane, filtering to remove insoluble impurities, adding appropriate amount of water into the filtrate, collecting the precipitated solid, and drying at 60 deg.C with vacuum oven to obtain 2- (2' -hydroxy-4-bromophenyl) benzothiazole with a yield of 54%. The nuclear magnetic results are:1H NMR(400MHz,DMSO-d6),δ(TMS,ppm):11.71(s,1H),8.02(d,1H),7.88(d,1H),7.62(d,1H),7.45(m,1H),7.33(m,1H),6.24(d,1H),6.15(d,1H,),5.95(s,2H).MS(ESI-TOF):304.95([M+H]+)。
the reaction formula of example 1 is as follows:
Figure BDA0001845338860000071
example 2
A100 mL Schlenk flask was charged with 10mmol of 2- (2' -hydroxy-4-bromophenyl) benzothiazole, 30mmol of 4- (dicyanovinyl) phenylacetylene, 1mmol of cuprous iodide, and 1mmol of triphenylphosphine. 0.2mmol of tetratriphenylphosphine palladium, 50mL of tetrahydrofuran/triethylamine (2/1, v/v) were added under nitrogen, and the mixture was reacted at room temperature for 48 hours. After the reaction is finished, filtering, drying the filtrate in a spinning mode, and separating and purifying the product by using a column chromatography method by using a dichloromethane/methanol (20/1, v/v) mixed solvent as an eluent to obtain the productThe product was a yellow solid in 57% yield. The nuclear magnetic results are:1H NMR(400MHz,CDCl3),δ(TMS,ppm):11.71(s,1H),8.02(d,1H),7.98(d,1H),7.78(s,1H),7.62(d,2H),7.58(d,1H),7.45(m,1H),7.35(d,2H),7.33(m,1H),6.24(d,1H),6.15(d,1H,).MS(MALDI-TOF):m/z calcd:403.1[M]+,found:403.1。
the reaction formula of example 2 is as follows:
Figure BDA0001845338860000081
example 3
Mixing 145 g of PAO10 base oil and 44.39 g of octadecylamine in a reaction kettle, heating to 60 ℃, dissolving 2.5 g of 2- (2 '-hydroxy-4' -dicyanovinylphenyl alkynyl) benzothiazole in 5 g of toluene, adding into the reaction kettle, mixing 145 g of PAO10 base oil and 20.61 g of MDI, heating to 60 ℃, adding into the reaction kettle after the MDI is completely dissolved, heating to 80 ℃, reacting for 30min, continuously heating to 210 ℃, adding 145 g of PAO10 base oil, cooling to about 100 ℃, and grinding.
Comparative example 1
Mixing 145 g of PAO10 base oil and 44.39 g of octadecylamine in a reaction kettle, heating to 60 ℃, mixing 145 g of PAO10 base oil and 20.61 g of MDI, heating to 60 ℃, adding the mixture into the reaction kettle after the MDI is completely dissolved, heating to 80 ℃, reacting for 30min, continuously heating to 210 ℃, adding 145 g of PAO10 base oil, cooling to about 100 ℃, and grinding.
The greases of example 3 and comparative example 1 were evaluated for performance according to GB/T3498, GB/T269, SH/T0202, SH/T0204, and SH/T0324, and the evaluation results are shown in Table 1.
TABLE 1 evaluation results
Figure BDA0001845338860000091
Example 4
Mixing 300 g of PAO10 base oil and 39.21 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, dissolving 2.5 g of 2- (2 '-hydroxy-4' -dicyanovinylphenyl alkynyl) benzothiazole in 5 g of toluene, adding the toluene into the reaction kettle, mixing 6.06 g of lithium hydroxide monohydrate and 40 g of distilled water, heating to 95 ℃, adding the lithium hydroxide into the reaction kettle after the lithium hydroxide is completely dissolved, heating to 210 ℃ after water is removed, adding 160 g of PAO10 base oil, cooling and grinding.
Comparative example 2
Mixing 300 g of PAO10 base oil and 39.21 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 6.06 g of lithium hydroxide monohydrate and 40 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, heating to 210 ℃ after dehydration by heating, adding 160 g of PAO10 base oil, cooling and grinding.
The greases of example 4 and comparative example 2 were evaluated for performance according to GB/T3498, GB/T269, SH/T0202, SH/T0204, and SH/T0324, and the evaluation results are shown in Table 2.
TABLE 2 evaluation results
Figure BDA0001845338860000101
Example 5
Mixing 200 g of PAO10 base oil, 32.5 g of stearic acid and 14 g of benzoic acid in a reaction kettle, heating to 90 ℃, dissolving 2.5 g of 2- (2 '-hydroxy-4' -dicyanovinylphenyl alkynyl) benzothiazole in 5 g of toluene, adding the toluene into the reaction kettle, mixing and heating 100 g of PAO10 base oil and 32 g of aluminum isopropoxide trimer, adding the mixture into the reaction kettle after the aluminum isopropoxide trimer is completely dissolved, continuously heating to 210 ℃, reacting for 30 minutes, adding 150 g of PAO10 base oil, cooling and grinding.
Comparative example 3
Mixing 200 g of PAO10 base oil, 32.5 g of stearic acid and 14 g of benzoic acid in a reaction kettle, heating to 90 ℃, mixing and heating 100 g of PAO10 base oil and 32 g of aluminum isopropoxide trimer, adding the mixture into the reaction kettle after the aluminum isopropoxide trimer is completely dissolved, continuously heating to 210 ℃ for reaction for 30 minutes, adding 150 g of PAO10 base oil, cooling and grinding.
The greases of example 5 and comparative example 3 were evaluated for performance according to GB/T3498, GB/T269, SH/T0202, SH/T0204, and SH/T0324, and the evaluation results are shown in Table 3. TABLE 3 analytical results
Figure BDA0001845338860000111

Claims (11)

1. A benzazepine derivative having the structure:
Figure FDA0001845338850000011
wherein A is S, O or NR, R is hydrogen or C1～6An alkyl group; each RaRadical, each RbRadical, each RcThe radicals, equal to or different from each other, are each independently selected from C1～6Straight or branched alkyl (preferably C)1～4Straight or branched chain alkyl); x is an integer of 0 to 4 (preferably 0 or 1), y is an integer of 0 to 3 (preferably 0 or 1), and z is an integer of 0 to 4 (preferably 0 or 1).
2. Benzacyclo derivative according to claim 1, wherein the Benzacyclo derivative comprises one or more of the following compounds:
Figure FDA0001845338850000012
3. a process for producing a benzazepine derivative, comprising the step of reacting a benzazepine compound represented by the general formula (II) with an acetylene compound represented by the general formula (III),
Figure FDA0001845338850000013
in the general formula (II), the A group is S, O or NR, R isHydrogen or C1～6An alkyl group; the group X is F, Cl, Br, I, OH (preferably Cl or Br); each RaRadical, each RbThe radicals, equal to or different from each other, are each independently selected from C1～6Straight or branched alkyl (preferably C)1～4Straight or branched chain alkyl); x is an integer of 0 to 4 (preferably 0 or 1), and y is an integer of 0 to 3 (preferably 0 or 1); in the general formula (III), each RcThe radicals, equal to or different from each other, are each independently selected from C1～6Straight or branched alkyl (preferably C)1～4Straight or branched chain alkyl); z is an integer of 0 to 4 (preferably 0 or 1).
4. A production method according to claim 3,
benzazepine compounds of the general formula (II) include:
Figure FDA0001845338850000021
the acetylene compounds represented by the general formula (III) include:
Figure FDA0001845338850000022
5. the process according to claim 3, wherein the molar ratio of the benzoazacyclic compound of formula (II) to the alkyne compound of formula (III) in the reaction is 1 to 3: 1 (preferably 1-2: 1); the reaction temperature is 0-50 ℃ (preferably 15-35 ℃); the reaction time is 12-96 h (preferably 24-72 h); the reaction is carried out under the protection of an inert gas, preferably nitrogen.
6. The process according to claim 3, wherein a catalyst is added to the reaction (the catalyst is preferably one or more of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound, more preferably a mixture of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound, and the molar ratio of the three is preferably 1: 0.1 to 10, more preferably 1: 0.2 to 5).
7. A process according to claim 3, characterized in that the process for the preparation of the benzazepine compound of the formula (II) comprises the step of reacting a compound of the formula (IV) with a compound of the formula (V),
Figure FDA0001845338850000031
in the general formula (IV), A is S, O or NR, R is hydrogen or C1～6An alkyl group; each RaThe radicals, equal to or different from each other, are each independently selected from C1～6Straight or branched alkyl (preferably C)1～4Straight or branched chain alkyl); x is an integer between 0 and 4 (preferably 0 or 1); in formula (V), the group X is F, Cl, Br, I, OH (preferably Cl or Br); each RbThe radicals, equal to or different from each other, are each independently selected from C1～6Straight or branched alkyl (preferably C)1～4Straight or branched chain alkyl); y is an integer of 0 to 3 (preferably 0 or 1).
8. The process according to claim 7, wherein the molar ratio of the compound of formula (IV) to the compound of formula (V) in the process for preparing the benzazepine compound of formula (II) is 0.5 to 2: 1 (preferably 0.9-1.1: 1); the temperature for the reaction of the compound represented by the general formula (IV) and the compound represented by the general formula (V) is 80-240 ℃ (preferably 140-180 ℃); the reaction time is 2-24 h (preferably 4-12 h); the reaction is carried out under the protection of an inert gas, preferably nitrogen.
9. Use of the benzazepine derivative of claim 1 or 2 or prepared according to the method of any one of claims 3 to 8 in light emitting components and devices, fluorescent probes, bio-imaging, lubricating oils and greases.
10. A grease comprising the benzazepine derivative of claim 1 or 2 or the benzazepine derivative produced by the method according to any one of claims 3 to 8, a thickener, and a lubricating base oil.
11. A method of preparing a grease of claim 10, comprising: mixing lubricating base oil, thickener and benzoazacyclo derivative, refining, and grinding into grease.
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JP2008115237A (en) * 2006-11-02 2008-05-22 Chugoku Electric Power Co Inc:The Corrosion resistant grease composition and corrosion resistant overhead wire
CN103214428A (en) * 2013-04-16 2013-07-24 浙江大学 Benzothiazole-cyanophenyl compound serving as hydrazine fluorescence probe as well as preparation method and application method of benzothiazole-cyanophenyl compound

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Publication number Priority date Publication date Assignee Title
JP2008115237A (en) * 2006-11-02 2008-05-22 Chugoku Electric Power Co Inc:The Corrosion resistant grease composition and corrosion resistant overhead wire
CN103214428A (en) * 2013-04-16 2013-07-24 浙江大学 Benzothiazole-cyanophenyl compound serving as hydrazine fluorescence probe as well as preparation method and application method of benzothiazole-cyanophenyl compound

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