CN116535303B - Method for synthesizing 4- (4-alkyl cyclohexyl) aryl ketone by replacing dichloroethane with methylcyclohexane - Google Patents
Method for synthesizing 4- (4-alkyl cyclohexyl) aryl ketone by replacing dichloroethane with methylcyclohexane Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 72
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- -1 aryl ketone Chemical class 0.000 title claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 152
- 238000003756 stirring Methods 0.000 claims abstract description 73
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 24
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 90
- 239000012074 organic phase Substances 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 30
- 238000005086 pumping Methods 0.000 claims description 29
- 239000012295 chemical reaction liquid Substances 0.000 claims description 22
- 239000005457 ice water Substances 0.000 claims description 21
- 238000006073 displacement reaction Methods 0.000 claims description 20
- 238000005191 phase separation Methods 0.000 claims description 19
- 230000007246 mechanism Effects 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 230000007062 hydrolysis Effects 0.000 claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 10
- 239000012346 acetyl chloride Substances 0.000 claims description 10
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 238000009434 installation Methods 0.000 claims description 7
- WMWOAQARUZYORF-UHFFFAOYSA-N (4-butylcyclohexyl)benzene Chemical compound C1CC(CCCC)CCC1C1=CC=CC=C1 WMWOAQARUZYORF-UHFFFAOYSA-N 0.000 claims description 6
- ZTKUBRNOEZWDJN-UHFFFAOYSA-N (4-ethylcyclohexyl)benzene Chemical compound C1CC(CC)CCC1C1=CC=CC=C1 ZTKUBRNOEZWDJN-UHFFFAOYSA-N 0.000 claims description 6
- FCAWXWGFZYRQJZ-UHFFFAOYSA-N (4-pentylcyclohexyl)benzene Chemical compound C1CC(CCCCC)CCC1C1=CC=CC=C1 FCAWXWGFZYRQJZ-UHFFFAOYSA-N 0.000 claims description 6
- PWGUTKLGUISGAE-UHFFFAOYSA-N (4-propylcyclohexyl)benzene Chemical compound C1CC(CCC)CCC1C1=CC=CC=C1 PWGUTKLGUISGAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000003507 refrigerant Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 3
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 30
- 238000001816 cooling Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 10
- 239000002912 waste gas Substances 0.000 description 7
- 150000002894 organic compounds Chemical class 0.000 description 6
- 239000012855 volatile organic compound Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000005917 acylation reaction Methods 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010170 biological method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000010815 organic waste Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- HXFNXEIKMAEASE-UHFFFAOYSA-N 4-(4-amino-3-chlorophenyl)-2-chloroaniline;hydrochloride Chemical compound Cl.C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HXFNXEIKMAEASE-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- BMFYCFSWWDXEPB-UHFFFAOYSA-N cyclohexyl(phenyl)methanone Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1 BMFYCFSWWDXEPB-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 231100000590 oncogenic Toxicity 0.000 description 1
- 230000002246 oncogenic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
- B01J4/007—Feed or outlet devices as such, e.g. feeding tubes provided with moving parts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
A method for synthesizing 4- (4-alkyl cyclohexyl) aryl ketone by replacing dichloroethane with methylcyclohexane belongs to the technical field of preparation of liquid crystal materials. According to the invention, methyl cyclohexane is used as a solvent for preparing 4- (4-alkyl cyclohexyl) aryl ketone, 4- (4-alkyl cyclohexyl) benzene and an acylating agent are used as raw materials, aluminum trichloride is used as a catalyst, and 4- (4-alkyl cyclohexyl) aryl ketone is synthesized by Friedel-crafts acylation reaction, and the total yield is more than 90%. According to the invention, the first reaction kettle is stirred and rotated by adopting the same motor, the movable disc is driven by the air cylinder to slide on the outer wall of the square block, and the switching operation is performed, so that the connecting column and the fixing frame are automatically fixed during stirring, the first reaction kettle is fixed, shaking during stirring is prevented, the stirring shaft position does not need to be moved out of the reaction kettle during pouring of the first reaction kettle, the operation is simplified, and the operation efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of preparation of liquid crystal materials, and particularly relates to a method for synthesizing 4- (4-alkyl cyclohexyl) aryl ketone by using methylcyclohexane instead of dichloroethane.
Background
Volatile organic compounds, also called VOCs, in China, generally refer to organic compounds with saturated vapor pressure of more than 70Pa and boiling point of less than 260 ℃ under normal pressure, or all organic compounds with vapor pressure of more than or equal to 10Pa and volatility at 20 ℃ and are classified into non-methane hydrocarbons (NMHCs for short), oxygen-containing organic compounds, halogenated hydrocarbons and the like. In addition, the standard of comprehensive emission of atmospheric pollutants (GB 16297-1996) in China also has an NMHC index, which is defined as a residual value after methane is subtracted from a total hydrocarbon measurement result, wherein the total hydrocarbon refers to the sum of gaseous organic matters which generate response on a gas chromatography hydrogen flame ionization detector under specified conditions.
The comprehensive emission standard of the atmospheric pollutants in China has clear regulation on the emission limit value of various volatile organic pollutants and NMHC. The maximum allowable emission concentration limit value of VOCs in the organic chemical industry is 50mg/cm 3 The maximum allowable discharge concentration limit of dichloroethane is only 1mg/cm 3 . The existing VOCs treatment process can be mainly divided into three categories, namely activated carbon adsorption, incineration and biological methods.
The burning method is also divided into a direct burning method and a catalytic burning method, and the destruction mechanism is through oxidation, thermal cracking and thermal decomposition, so as to achieve the purpose of treating VOCs. Direct combustion methods such as direct combustion (TO) and regenerative combustion (RTO) are catalytic combustion methods such as catalytic incinerator (CTO) which directly decompose high-concentration organic waste gas into harmless substances at high temperature by using fuel oil or gas as auxiliary fuel. The method has high energy consumption and increases the emission of carbon dioxide. On the other hand, the dichloroethane inevitably generates toxic dioxin in the high-temperature combustion process, and seriously pollutes the environment. The substance is an organic compound with stronger biological toxicity, the toxicity of the organic compound is 130 times of cyanide and 900 times of arsenic, and the organic compound has irreversible teratogenic, oncogenic and mutagenic toxicity and is regarded as one of the most dangerous chemical substances in the world. It is also called "century toxin" because it is difficult to degrade and eliminate naturally once it permeates into the environment.
Biological processes are also known as activated sludge processes. The core of the biological method is a biological filter bed, and microorganisms can grab organic matters in the organic waste gas as nutrients when the organic waste gas flows through the filter bed, so that the waste gas is purified. The process generally has high efficiency in removing VOCs and is effective in malodor, but is not suitable for halogenated organics and polymerized aromatics. The living requirements of the microorganisms are harsh to the temperature, humidity, pH value, components and other conditions of the waste gas, and the waste gas cannot contain toxic components, otherwise, the microorganisms are killed. The presence of dichloroethane clearly has a detrimental effect on biological treatment systems.
The last method is activated carbon adsorption and is the only applicable treatment method for dichloroethane, but the adsorption capacity of the activated carbon is limited, regeneration is needed in the use process, and as the activated carbon is continuously used, the lower the adsorption capacity of the activated carbon is, and finally, the activated carbon becomes solid waste and must be treated as dangerous solid waste.
In view of the above, the current technology is either difficult to treat or costly to treat the dichloroethane-containing waste gas, and there is a strong need for disposal from the source.
4- (4-alkyl cyclohexyl) aryl ketone is an important intermediate for synthesizing liquid crystal materials, 4- (4-alkyl cyclohexyl) aryl ketone is prepared domestically and internationally at present, based on Lewis acid catalyst, acylation reagent is used for Friedel-crafts acylation reaction, but a large amount of dichloroethane is inevitably used as solvent in the method, such as an ethyl cyclohexyl phenyl alkyl ketone compound for display materials and a preparation method thereof disclosed in China patent No. CN201910769706, an anti-preparation method of trans-4, 4' -dicyclohexyl dicarboxylic acid disclosed in China patent No. CN201310713706 and the like, which are all used as reaction solvents, so that subsequent wastewater or waste gas treatment becomes a critical problem.
At present, as in the Chinese patent publication No. CN110294667, cyclohexane is used as a reaction solvent for synthesizing cyclohexyl phenyl ketone, and as in the Chinese patent publication No. CN108727199A, a method for producing 3,3 '-dichlorobenzidine hydrochloride by replacing toluene with methylcyclohexane is used for producing 3,3' -dichlorobenzidine hydrochloride, but no technical route for preparing 4- (4-alkyl cyclohexyl) aryl ketone by using methylcyclohexane is proposed. The methylcyclohexane is used as a low-toxicity solvent, is suitable for treating waste water or waste gas by a conventional treatment method, can be well treated by a biological method, and is an environment-friendly alternative solvent. In addition, compared with the traditional dichloroethane used as the solvent for the 4- (4-alkyl cyclohexyl) benzene acylation reaction, the solvent consumption of the required methylcyclohexane is 50% -60% of that of the traditional dichloroethane, the yield and the content of the product are not greatly changed, but the solvent consumption is obviously reduced, the cost can be greatly saved, the production efficiency is obviously improved, and the method has good application prospect in terms of solvent substitution.
In view of the above, the applicant has developed a method for synthesizing 4- (4-alkylcyclohexyl) aryl ketone by replacing dichloroethane with methylcyclohexane, which can realize the environment-friendly preparation of 4- (4-alkylcyclohexyl) aryl ketone, and the equipment used in the key reaction link is designed according to the new process technology, so that the production efficiency can be further improved, and the labor intensity and the labor cost can be reduced.
Disclosure of Invention
The invention aims at: in order to achieve the purposes of environmental protection and high efficiency in preparing 4- (4-alkyl cyclohexyl) aryl ketone and improving the synthesis efficiency of materials, the method for synthesizing the 4- (4-alkyl cyclohexyl) aryl ketone by using methyl cyclohexane to replace dichloroethane is provided.
In order to achieve the above purpose, the present invention provides the following technical solutions: the method for synthesizing the 4- (4-alkyl cyclohexyl) aryl ketone by replacing dichloroethane with methylcyclohexane is prepared by the following steps:
s1: adding methylcyclohexane into a first reaction kettle, starting stirring, and slowly adding aluminum trichloride, wherein the molar ratio of the aluminum trichloride to the methylcyclohexane is 1:2-3; stirring for 0.5-2 h at the temperature of 0-20 ℃ after the addition is finished;
s2: continuously stirring until the temperature of the mixture is reduced to-10-0 ℃, dropwise adding an acylating reagent, wherein the temperature is controlled to be not more than 20 ℃ in the dropwise adding process, and the dropwise adding is completed within about 2+/-0.5 hours;
s3: a compound of the formula:
，
wherein n=2 to 5;
controlling the temperature not to exceed 20 ℃ in the dripping process, and preserving the heat for 1-2 hours after finishing dripping within 2+/-0.5 hours;
s4: slowly stirring, and slowly pouring the reaction liquid obtained in the step S3 into a second reaction kettle containing ice water for hydrolysis, wherein the volume ratio of the reaction liquid to the ice water is 1:1; controlling the temperature not to exceed 20 ℃ in the hydrolysis process, standing and phase-separating after the hydrolysis is finished;
S5: standing for phase separation, extracting the organic phase with water above and water below until the organic phase is neutral;
s6: removing the solvent from the organic phase to obtain the 4- (4-alkyl cyclohexyl) aryl ketone, namely a compound shown in the following formula:
，
where n=2-5, m=1 or 2.
As still further aspects of the invention: in S2, the acylating agent used is one of acetyl chloride and propionyl chloride.
As still further aspects of the invention: in S2, the molar ratio of the acylating agent to the methylcyclohexane is 1:2-3.
As still further aspects of the invention: in S3, the compound is 4- (4-n-alkyl cyclohexyl) benzene, and the molar ratio of the 4- (4-n-alkyl cyclohexyl) benzene to the methylcyclohexane is 1:3 to 4.
As still further aspects of the invention: in S3, the compound is one of 4- (4-ethylcyclohexyl) benzene, 4- (4-propylcyclohexyl) benzene, 4- (4-butylcyclohexyl) benzene and 4- (4-pentylcyclohexyl) benzene.
As still further aspects of the invention: the first reaction kettle and the second reaction kettle are arranged on an installation seat, the top end of the installation seat is fixedly connected with two fixing frames, the first reaction kettle is subjected to stirring operation through a stirring mechanism, and the first reaction kettle is driven to rotate through a rotating mechanism;
The inner cavity of the second reaction kettle is provided with a second stirring shaft, the bottom end of the second reaction kettle is provided with a water pumping pipe, the outer wall of the water pumping pipe is provided with a water pumping valve, and the inner wall of the second reaction kettle is provided with a PH value detection sensor;
the inner walls of the first reaction kettle and the second reaction kettle are respectively provided with a hollow interlayer, and a circulating medium taking modified dihydric alcohol as a refrigerant is introduced into the hollow interlayer, so that the environment temperature in the first reaction kettle can be controlled, and the reaction heat generated in the first reaction kettle and the second reaction kettle can be circularly taken away;
the gas absorption device comprises a gas collecting hood arranged on a lifting bracket, the gas collecting hood is driven by the lifting bracket to descend to a lower limit, the lower end opening of the gas collecting hood can be sealed and buckled at the upper opening of the first reaction kettle and the second reaction kettle, the upper end of the gas collecting hood is connected with one end of a gas guide pipe, and a gas pump is arranged on the gas guide pipe; the other end of the air duct is inserted into a circulating water treatment box, a water inlet and a water outlet are formed in the circulating water treatment box, the water inlet is connected with a clean water source, and the water outlet is connected with a hydrochloric acid collecting box; control valves are arranged on the water inlet and the water outlet.
As still further aspects of the invention: the stirring mechanism comprises a rotating groove, the rotating groove is formed in the outer wall of the fixing frame, the connecting column is fixedly connected with the outer wall of the fixing frame, the connecting column is rotationally connected to the inner wall of the rotating groove, the connecting column is located below the connecting column, the outer wall of the fixing frame is fixedly connected with a mounting frame, a motor is installed on the outer wall of the mounting frame, the output end of the motor is connected with a connecting shaft, the connecting shaft extends into the connecting column, the outer wall of the connecting shaft is fixedly connected with a square block, a cylinder is installed on the outer wall of the fixing frame above the connecting column, the output end of the cylinder is connected with a movable plate, the bottom of the movable plate is fixedly connected with a movable frame, the bottom of the movable frame is rotationally connected with a movable plate, the movable plate is slidingly sleeved on the outer wall of the square block, the inner part of the connecting column is located at one end of the connecting shaft, the inner wall of the first reaction kettle is rotationally connected with a toothed ring, the outer wall of the toothed ring is meshed with the outer wall, and the stirring shaft is fixedly connected with a first stirring shaft of the toothed ring.
As still further aspects of the invention: the rotating mechanism comprises a displacement plate, the displacement plate is in sliding connection with the inside of the connecting shaft, a first inclined surface block and a first clamping block are fixedly connected with the top end of the displacement plate, the first inclined surface block and the first clamping block extend out of the top end of the connecting shaft, a second inclined surface block and a second clamping block are fixedly connected with the bottom end of the displacement plate, the second inclined surface block and the first inclined surface block are respectively located on the upper side and the lower side of the displacement plate, the first clamping block and the second clamping block are respectively located on the upper side and the lower side of the displacement plate, a slot for the connecting shaft to be inserted into is formed in the outer wall of the connecting column, a push rod is fixedly connected with the outer wall of the movable frame, a fixing groove is formed in the top end of the inner wall of the rotating groove, a slide rod extending out of the outer wall of the connecting column is slidingly connected with the inner end of the connecting column, a fixing block is arranged at one end of the connecting column in sliding connection with the fixing block, the fixing block extends out of the top end of the connecting column, and a spring is connected between the fixing block and the connecting column.
As still further aspects of the invention: an annular first inner gear ring is arranged in the inner cavity of the fluted disc, and one end of the first clamping block is clamped with the first inner gear ring;
The outer wall of the square block is attached to the inner wall of the movable disc, a T-shaped annular groove is formed in the outer wall of the movable disc, an arc block is fixedly connected to the bottom end of the movable frame, and the outer wall of the arc block is attached to the inner wall of the annular groove;
the inner wall of the rotating groove is attached to the outer wall of the connecting column, an annular second inner gear ring is arranged on the inner wall of the slot, and the second inner gear ring is clamped with one end of the second clamping block.
As still further aspects of the invention: the inner wall of the fixed slot is attached to the outer wall of the fixed block, an inclined plane is arranged at the bottom end of the fixed block, and the inclined plane is in contact with the sliding rod.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method is scientific and reasonable in design, and uses the methylcyclohexane to replace dichloroethane as a solvent for the 4- (4-alkyl cyclohexyl) benzene acylation reaction, and the methylcyclohexane is low in toxicity and has much lower solubility in water than the dichloroethane, so that the potential safety hazard and environmental protection hazards caused by using the dichloroethane are avoided, the difficulty of wastewater and waste gas treatment is greatly reduced, and the method is quite environment-friendly and is a clean synthesis process.
2. Compared with the traditional dichloroethane used as the solvent for the 4- (4-alkyl cyclohexyl) benzene acylation reaction, the invention has obviously reduced solvent consumption. The solvent consumption of the required methylcyclohexane is 50% -60% of the original dichloroethane solvent consumption, the yield and content of the product are not greatly changed, the cost can be saved, the production efficiency is obviously improved, and the method has good application prospect in terms of solvent substitution.
3. The invention designs reaction equipment aiming at the key link matching of the process, and the stirring mechanism and the rotating mechanism are arranged to drive the first reaction kettle to stir, rotate and tilt by adopting the same motor, and the cylinder drives the movable disc to slide along the outer wall of the square block to perform the switching operation of stirring, rotating and tilting; when stirring, the connecting column and the fixing frame are automatically fixed, so that the first reaction kettle is fixed, and shaking of the first reaction kettle during stirring is prevented; when the first reaction kettle is dumped, the stirring shaft is not required to be moved out of the reaction kettle, so that the operation is simplified, the labor intensity of workers is reduced, and the synthesis efficiency of materials is improved.
Drawings
FIG. 1 is a schematic diagram of the installation structure of a first reaction kettle and a second reaction kettle according to the invention;
FIG. 2 is a schematic diagram of the internal structure of a second reactor according to the present invention;
FIG. 3 is a schematic view of the installation structure of the first reaction kettle of the present invention;
FIG. 4 is a schematic view of the mounting structure of the fixed frame, the cylinder, the movable frame and the movable disk of the invention;
FIG. 5 is a schematic view of the installation structure of the connecting column, the connecting shaft and the first reaction kettle of the invention;
FIG. 6 is an enlarged view of FIG. 5A in accordance with the present invention;
fig. 7 is a schematic view of the internal structure of the connecting shaft of the present invention.
In the figure: 1. a mounting base; 2. a first reaction kettle; 3. a second reaction kettle; 4. a fixing frame; 5. a stirring mechanism; 501. a rotating groove; 502. a connecting column; 503. a mounting frame; 504. a motor; 505. a connecting shaft; 506. square blocks; 507. a cylinder; 508. a movable plate; 509. a movable frame; 510. a movable plate; 511. fluted disc; 512. a toothed ring; 513. a first stirring shaft; 514. an annular groove; 515. an arc-shaped block; 6. a rotating mechanism; 601. a displacement plate; 602. a first ramp block; 603. a second ramp block; 604. a first clamping block; 605. a second clamping block; 606. a slot; 607. a push rod; 608. a fixing groove; 609. a slide bar; 610. a fixed block; 611. a spring; 612. a first ring gear; 613. a second ring gear; 7. a second stirring shaft; 8. a water pumping pipe; 9. a water pumping valve; 10. a pH value detection sensor; 11. a gas collecting hood; 12. and an air duct.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
When the acylating agent is acetyl chloride and the compound is 4- (4-ethylcyclohexyl) benzene (65.3%), the product is 4- (4-ethylcyclohexyl) acetophenone.
S1: methyl cyclohexane is added into the first reaction kettle 2, 41.5g of aluminum trichloride is slowly added, and stirring is carried out for 0.5 to 2 hours at the temperature of between 0 and 20 ℃.
S2: and (3) continuously stirring and cooling to the temperature of between minus 10 and 0 ℃, adding 21.8g of acetyl chloride, controlling the temperature not to exceed 20 ℃ in the dripping process, and dripping for about 2 hours.
S3: after the dripping is completed, stirring and cooling to 0 ℃, dripping 40.5g of 4- (4-ethylcyclohexyl) benzene, wherein the temperature is controlled to be not more than 20 ℃ in the dripping process, and dripping is carried out for about 2 hours. After all the dripping is completed, preserving the heat for 1-2 h.
S4: slowly pouring the reaction liquid in the first reaction kettle 2 into a second reaction kettle 3 containing ice water for hydrolysis, wherein the volume ratio of the reaction liquid to the ice water is 1:1, after stirring fully, standing and phase-separating in a second reaction kettle 3.
S5: after the phase separation is observed (light yellow transparent organic phase is positioned above and water is positioned below) through a vertical strip-shaped transparent observation window arranged on the outer wall of the second reaction kettle 3, a water pumping valve 9 on a bottom water pumping pipe 8 is opened, and the water below the phase separation is discharged. The organic phase in the second reactor 3 was washed with water to neutrality.
S6: the washed organic phase was discharged from the second reactor 3, and the solvent was removed by vacuum evacuation to obtain 45.0g of 4- (4-ethylcyclohexyl) acetophenone, with a yield of 90.9% and a content of 58.3%.
The structures of the first reaction kettle and the second reaction kettle used in the process are shown in fig. 1-7.
Referring to fig. 2, a second stirring shaft 7 is disposed in an inner cavity of the second reaction kettle 3, a water pumping pipe 8 is disposed at a bottom end of the second reaction kettle 3, a water pumping valve 9 is mounted on an outer wall of the water pumping pipe 8, a PH value detecting sensor 10 is mounted on an inner wall of the second reaction kettle 3, and the PH value detecting sensor 10 is used for detecting whether a PH value of an organic phase in the second reaction kettle reaches neutrality after washing.
In this embodiment: s1 to S3 are carried out in a first reaction kettle 2, the first reaction kettle 2 is driven in S4 to pour the prepared product in the step S3 into a second reaction kettle 3 containing ice water at a very slow speed, and both reaction kettles have a stirring function.
Since the reaction requires control of the reaction temperature and a large amount of heat generation during the reaction, it is necessary to provide cooling devices in both the first reaction tank 2 and the second reaction tank 3, specifically: the inner walls of the first reaction kettle 2 and the second reaction kettle 3 are respectively provided with a hollow interlayer, and a circulating medium taking modified dihydric alcohol as a refrigerant is introduced into the hollow interlayer, so that the environment temperature in the first reaction kettle 2 can be controlled, and the reaction heat generated in the first reaction kettle 2 and the second reaction kettle 3 can be circularly taken away.
Since hydrogen chloride gas is generated during the reaction in both the first reaction tank 2 and the second reaction tank 3, it is also necessary to specially provide an absorption device for the hydrogen chloride gas, specifically: the gas absorption devices are respectively arranged above the first reaction kettle 2 and the second reaction kettle 3, each gas absorption device comprises a gas collecting hood 11 arranged on a lifting bracket, the gas collecting hoods 11 which are driven by the lifting bracket to descend to a lower limit can be tightly buckled at the upper opening of the first reaction kettle 2 and the second reaction kettle 3, the upper ends of the gas collecting hoods 11 are connected with one end of a gas guide pipe 12, and a gas pump is arranged on the gas guide pipe 12; the other end of the air duct 12 is inserted into a circulating water treatment box, a water inlet and a water outlet are formed in the circulating water treatment box, the water inlet is connected with a clean water source, and the water outlet is connected with a hydrochloric acid collecting box; control valves are arranged on the water inlet and the water outlet. The gas absorbing device operates as follows: when the first reaction kettle 2 or the second reaction kettle 3 carries out chemical combination reaction, the gas collecting hood 11 which is driven by the lifting bracket to descend to the lower limit is tightly buckled above the first reaction kettle 2 or the second reaction kettle 3, the gas pump is started, so that the hydrogen chloride gas generated by the reaction is led into the circulating water treatment box through the gas guide pipe 12, hydrochloric acid is produced by the water reaction in the circulating water treatment box, and the hydrochloric acid product can be collected into the hydrochloric acid collection box through the water outlet. After the reaction is finished, the lifting support can drive the gas collecting hood 11 to move upwards, so that the dumping operation of the first reaction kettle 2 or the cleaning operation of the two reaction kettles cannot be influenced. The arrangement of the gas absorption device can effectively avoid the pollution of hydrogen chloride gas generated in the reaction process to the environment.
The second reaction kettle 3 needs to pump the water after the internal phase separation through a water pumping pipe 8 and a water pumping valve 9, and the PH value of the organic phase is automatically sampled and tested through a PH value detection sensor 10. For accurate temperature control, the reaction steps of S1-S3 cannot be performed in an oversized container, and the center temperature of the oversized container has a larger temperature difference compared with the temperature close to the side wall; in addition, the reaction liquid generated in the step S3 has viscous oiliness, so that the flow guiding and speed regulating are not suitable for being carried out through a pipeline and a control valve arranged in the pipeline, and reactants for multiple operations remain in the pipeline wall after long-term use, and the pipeline and a valve body are not easy to clean, so that the quality of a product is affected, and therefore, the reaction liquid is led into the second reaction kettle 3 by adopting a dumping mode through the first reaction kettle 2.
Referring to fig. 2-7, a first reaction kettle 2 and a second reaction kettle 3 are disposed on a mounting seat 1, two fixing frames 4 are fixedly connected to the top end of the mounting seat 1, the first reaction kettle 2 is stirred by a stirring mechanism 5, and the first reaction kettle 2 is driven to rotate by a rotating mechanism 6. The stirring mechanism 5 comprises a rotating groove 501, the rotating groove 501 is arranged on the outer wall of a fixed frame 4, a connecting column 502 is fixedly connected to the outer wall of the fixed frame 4, the connecting column 502 is rotationally connected to the inner wall of the rotating groove 501, the outer wall of the fixed frame 4 is fixedly connected with a mounting frame 503 below the connecting column 502, a motor 504 is arranged on the outer wall of the mounting frame 503, the output end of the motor 504 is connected with a connecting shaft 505, the connecting shaft 505 extends into the connecting column 502, the outer wall of the connecting shaft 505 is fixedly connected with a square block 506, an air cylinder 507 is arranged above the connecting column 502, the output end of the air cylinder 507 is connected with a movable plate 508, the bottom end of the movable plate 508 is fixedly connected with a movable frame 509, the bottom end of the movable frame 509 is rotationally connected with a movable disc 510 which is sleeved on the outer wall of the square block 506 in a sliding manner, one end of the connecting column 502 is rotationally connected with a fluted disc 511, the inner wall of the first reaction kettle 2 is rotationally connected with a toothed ring 512, the outer wall of the toothed ring 512 is contacted with the outer wall of a fluted disc 511, the bottom end of the toothed ring 512 is fixedly connected with a first stirring shaft 513, the rotating mechanism 6 comprises a displacement plate 601, the displacement plate 601 is slidingly connected inside a connecting shaft 505, the top end of the displacement plate 601 is fixedly connected with a first inclined surface block 602 and a first clamping block 604, the first inclined surface block 602 and the first clamping block 604 extend out of the top end of the connecting shaft 505, the bottom end of the displacement plate 601 is fixedly connected with a second inclined surface block 603 and a second clamping block 605, the second inclined surface block 603 and the first inclined surface block 602 are respectively positioned on the upper side and the lower side of the displacement plate 601, the first clamping block 604 and the second clamping block 605 are respectively positioned on the upper side and the lower side of the displacement plate 601, the outer wall of the connecting column 502 is provided with a slot 606 for the connecting shaft 505 to be inserted, the outer wall of the movable frame 509 is fixedly connected with a push rod 607, the fixed slot 608 is arranged at the top end of the inner wall of the rotary slot 501, the sliding rod 609 extending out of the outer wall of the connecting column 502 is connected inside the connecting column 502 in a sliding manner, the fixed block 610 is connected at one end of the sliding rod 609 inside the connecting column 502 in a sliding manner, the fixed block 610 extends out of the top end of the connecting column 502, and the spring 611 is connected between the fixed block 610 and the connecting column 502.
In this embodiment: before stirring objects in the first reaction kettle 2, at this time, the push rod 607 is in contact with the slide rod 609, the slide rod 609 extrudes the fixed block 610 into the fixed groove 608, the spring 611 is extruded, the connecting column 502 and the fixed frame 4 are fixed, and the first reaction kettle 2 is prevented from shaking; meanwhile, the inner wall of the movable disc 510 is contacted with the second inclined surface block 603, and the first clamping block 604 is clamped with the inner wall of the fluted disc 511; when stirring objects in the first reaction kettle 2, the motor 504 is started, the motor 504 runs to drive the connecting shaft 505 to rotate, the connecting shaft 505 drives the fluted disc 511 to synchronously rotate through the first clamping block 604, the fluted disc 511 rotates to drive the toothed ring 512 to rotate, the toothed ring 512 rotates to drive the first stirring shaft 513 to rotate, and materials in the first reaction kettle are stirred. It should be noted that fig. 5 is only a reference schematic diagram of the structure of the apparatus of the present patent, and in practical application, a sealing ring capable of rotating along with the inner sidewall of the toothed ring 512 is further disposed to prevent the reactant from entering into the space of the rotary motion of the toothed ring 512.
When the first reaction kettle 2 is subjected to dumping operation, the air cylinder 507 is started to drive the movable plate 508 to move, the movable plate 508 moves to drive the movable plate 510 to move through the movable frame 509, the movable plate 510 slides on the outer wall of the square block 506, the movable plate 510 is separated from the second inclined block 603 and then moves continuously to be in contact with the first inclined block 602, the first inclined block 602 is pushed to move, the first inclined block 602 is shifted to drive the shift plate 601 to shift, the shift plate 601 is shifted to drive the first clamping block 604 to be separated from the inner wall of the fluted disc 511, the connecting shaft 505 is separated from the fluted disc 511, and meanwhile, the second clamping block 605 is clamped with the inner wall of the connecting column 502, so that the connecting shaft 505 is fixed with the connecting column 502; meanwhile, the movable frame 509 is moved to drive the push rod 607 to be moved to be separated from the slide rod 609, the fixed block 610 is moved out of the fixed groove 608 under the action of the elastic force of the spring 611, the fixation of the connecting column 502 is canceled, the starting motor 504 drives the connecting shaft 505 to rotate, and the connecting shaft 505 rotates to drive the first reaction kettle 2 to rotate through the connecting column 502. The motor 504 is a servo motor, and can realize fixed-angle rotation, so as to control the rotation angle of the first reaction kettle 2 and then control the dumping flow rate of the liquid material in the first reaction kettle.
Referring to fig. 5 and 7, an annular first ring gear 612 is disposed in an inner cavity of the fluted disc 511, one end of the first clamping block 604 is engaged with the first ring gear 612, and the fluted disc 511 is meshed with the toothed ring 512.
In this embodiment: the motor 504 operates to drive the connecting shaft 505 to rotate, the connecting shaft 505 drives the fluted disc 511 to synchronously rotate through the first clamping block 604, the fluted disc 511 rotates to drive the toothed ring 512 to rotate, and the toothed ring 512 rotates to drive the first stirring shaft 513 to rotate so as to stir materials.
Referring to fig. 3-5, the outer wall of the square block 506 is attached to the inner wall of the movable disk 510, the outer wall of the movable disk 510 is provided with a T-shaped annular groove 514, the bottom end of the movable frame 509 is fixedly connected with an arc block 515, and the outer wall of the arc block 515 is attached to the inner wall of the annular groove 514.
In this embodiment: the movable disk 510 can slide on the outer wall of the square block 506; when the motor 504 operates to drive the connecting shaft 505 to rotate, the connecting shaft 505 rotates to drive the square block 506 to rotate, the square block 506 rotates to drive the movable disc 510 to rotate at the bottom end of the movable frame 509, and at the moment, the arc-shaped block 515 slides in the annular groove 514.
Referring to fig. 3, 6 and 7, the inner wall of the rotating groove 501 is attached to the outer wall of the connecting post 502, the inner wall of the slot 606 is provided with a second annular ring gear 613, and the second ring gear 613 is engaged with one end of the second clamping block 605.
In this embodiment: the starting cylinder 507 drives the movable plate 508 to move, the movable plate 508 moves to drive the movable plate 510 to move through the movable frame 509, the movable plate 510 slides on the outer wall of the square block 506, the movable plate 510 is separated from the second inclined surface block 603 and then moves continuously to be in contact with the first inclined surface block 602, the first inclined surface block 602 is pushed to move, the first inclined surface block 602 is shifted to drive the shifting plate 601 to shift, the shifting plate 601 is shifted to drive the first clamping block 604 to be separated from the fluted disc 511, the connecting shaft 505 is separated from the fluted disc 511, meanwhile, the second clamping block 605 is clamped with the connecting column 502, the connecting shaft 505 is fixed with the connecting column 502, the starting motor 504 drives the connecting shaft 505 to rotate, and the connecting shaft 505 rotates to drive the first reaction kettle 2 through the connecting column 502.
Referring to fig. 4-7, the inner wall of the fixing groove 608 is attached to the outer wall of the fixing block 610, and an inclined surface is disposed at the bottom end of the fixing block 610 and contacts the sliding rod 609.
In this embodiment: the movable frame 509 is displaced to drive the push rod 607 to be displaced and separated from the slide rod 609, the fixed block 610 is displaced out of the fixed groove 608 under the action of the elastic force of the spring 611, and the fixation of the connecting column 502 is canceled.
Example 2
When the acylating agent is acetyl chloride and the compound is 4- (4-propylcyclohexyl) benzene (75.1% content), the product is 4- (4-propylcyclohexyl) acetophenone.
S1: methyl cyclohexane is added into the first reaction kettle 2, 37.5g of aluminum trichloride is slowly added, and stirring is carried out for 0.5 to 2 hours at the temperature of between 0 and 20 ℃.
S2: and (3) continuously stirring and cooling to the temperature of between minus 10 and 0 ℃, adding 22.5g of acetyl chloride, controlling the temperature not to exceed 20 ℃ in the dripping process, and dripping for about 2 hours.
S3: after the dripping is completed, continuously stirring and cooling to 0 ℃, dripping 44.5g of 4- (4-propyl cyclohexyl) benzene, wherein the temperature is controlled to be not more than 20 ℃ in the dripping process, and dripping is carried out for about 2 hours. After all the dripping is completed, preserving the heat for 1-2 h.
S4: slowly pouring the reaction liquid in the first reaction kettle 2 into a second reaction kettle 3 containing ice water for hydrolysis, wherein the volume ratio of the reaction liquid to the ice water is 1:1, after stirring fully, standing and phase-separating in a second reaction kettle 3.
S5: after the phase separation is observed (light yellow transparent organic phase is positioned above and water is positioned below) through a vertical strip-shaped transparent observation window arranged on the outer wall of the second reaction kettle 3, a water pumping valve 9 on a bottom water pumping pipe 8 is opened, and the water below the phase separation is discharged. The organic phase in the second reactor 3 was washed with water to neutrality.
S6: the washed organic phase was discharged from the second reactor 3, and the solvent was removed by vacuum evacuation to obtain 48.5g of 4- (4-propylcyclohexyl) acetophenone, with a yield of 92.4% and a content of 70.6%.
The rest of implementation methods, device structures and use methods of this embodiment are the same as those of the first embodiment, and will not be described again.
Example 3
When the acylating agent is acetyl chloride and the compound is 4- (4-butylcyclohexyl) benzene (99.53%), the product is 4- (4-butylcyclohexyl) acetophenone.
S1: methyl cyclohexane is added into the first reaction kettle 2, 38.5g of aluminum trichloride is slowly added, and stirring is carried out for 0.5 to 2 hours at the temperature of between 0 and 20 ℃.
S2: and (3) continuously stirring and cooling to the temperature of between minus 10 and 0 ℃, adding 23.0g of acetyl chloride, controlling the temperature not to exceed 20 ℃ in the dripping process, and dripping for about 2 hours.
S3: after the dripping is completed, stirring and cooling to 0 ℃, dripping 48.5g of 4- (4-butylcyclohexyl) benzene, wherein the temperature is controlled to be not more than 20 ℃ in the dripping process, and dripping is carried out for about 2 hours. After all the dripping is completed, preserving the heat for 1-2 h.
S4: slowly pouring the reaction liquid in the first reaction kettle 2 into a second reaction kettle 3 containing ice water for hydrolysis, wherein the volume ratio of the reaction liquid to the ice water is 1:1, after stirring fully, standing and phase-separating in a second reaction kettle 3.
S5: after the phase separation is observed (light yellow transparent organic phase is positioned above and water is positioned below) through a vertical strip-shaped transparent observation window arranged on the outer wall of the second reaction kettle 3, a water pumping valve 9 on a bottom water pumping pipe 8 is opened, and the water below the phase separation is discharged. The organic phase in the second reactor 3 was washed with water to neutrality.
S6: the washed organic phase was discharged from the second reactor 3, and the solvent was removed by vacuum evacuation to obtain 52.8g of n-4- (4-butylcyclohexyl) acetophenone, with a yield of 95.2% and a content of 92.0%.
The rest of implementation methods, device structures and use methods of this embodiment are the same as those of the first embodiment, and will not be described again.
Example 4
When the acylating agent is acetyl chloride and the compound is 4- (4-pentylcyclohexyl) benzene (68.0%), the product is 4- (4-pentylcyclohexyl) acetophenone.
S1: methyl cyclohexane is added into the first reaction kettle 2, 39.0g of aluminum trichloride is slowly added, and stirring is carried out for 0.5 to 2 hours at the temperature of between 0 and 20 ℃.
S2: and (3) continuously stirring and cooling to the temperature of between minus 10 and 0 ℃, adding 25.7g of acetyl chloride, controlling the temperature not to exceed 20 ℃ in the dripping process, and dripping for about 2 hours.
S3: after the dripping is completed, stirring and cooling to 0 ℃, and dripping 53.5g of 4- (4-amyl cyclohexyl) benzene, wherein the temperature is controlled to be not more than 20 ℃ in the dripping process, and the dripping is carried out for about 2 hours. After all the dripping is completed, preserving the heat for 1-2 h.
S4: slowly pouring the reaction liquid in the first reaction kettle 2 into a second reaction kettle 3 containing ice water for hydrolysis, wherein the volume ratio of the reaction liquid to the ice water is 1:1, after stirring fully, standing and phase-separating in a second reaction kettle 3.
S5: after the phase separation is observed (light yellow transparent organic phase is positioned above and water is positioned below) through a vertical strip-shaped transparent observation window arranged on the outer wall of the second reaction kettle 3, a water pumping valve 9 on a bottom water pumping pipe 8 is opened, and the water below the phase separation is discharged. The organic phase in the second reactor 3 was washed with water to neutrality.
S6: the washed organic phase was discharged from the second reactor 3, and the solvent was removed by vacuum evacuation to obtain 54.1g of n-4- (4-pentylcyclohexyl) acetophenone, with a yield of 92.5% and a content of 51.6%.
The rest of implementation methods, device structures and use methods of this embodiment are the same as those of the first embodiment, and will not be described again.
Example 5
When the acylating agent is propionyl chloride and the compound is 4- (4-ethylcyclohexyl) benzene (65.3%), the product is 4- (4-ethylcyclohexyl) propiophenone.
S1: methyl cyclohexane is added into the first reaction kettle 2, 39.5g of aluminum trichloride is slowly added, and stirring is carried out for 0.5 to 2 hours at the temperature of between 0 and 20 ℃.
S2: and (3) continuously stirring and cooling to the temperature of between minus 10 and 0 ℃, adding 25.7g of propionyl chloride, controlling the temperature not to exceed 20 ℃ in the dripping process, and dripping for about 2 hours.
S3: after the dripping is completed, stirring and cooling to 0 ℃, dripping 45.5g of 4- (4-ethylcyclohexyl) benzene, wherein the temperature is controlled to be not more than 20 ℃ in the dripping process, and dripping is carried out for about 2 hours. After all the dripping is completed, preserving the heat for 1-2 h.
S4: slowly pouring the reaction liquid in the first reaction kettle 2 into a second reaction kettle 3 containing ice water for hydrolysis, wherein the volume ratio of the reaction liquid to the ice water is 1:1, after stirring fully, standing and phase-separating in a second reaction kettle 3.
S5: after the phase separation is observed (light yellow transparent organic phase is positioned above and water is positioned below) through a vertical strip-shaped transparent observation window arranged on the outer wall of the second reaction kettle 3, a water pumping valve 9 on a bottom water pumping pipe 8 is opened, and the water below the phase separation is discharged. The organic phase in the second reactor 3 was washed with water to neutrality.
S6: the washed organic phase was discharged from the second reactor 3, and the solvent was removed by vacuum evacuation to obtain 48.2g of 4- (4-ethylcyclohexyl) propiophenone, with a yield of 91.8% and a content of 60.1%.
The rest of implementation methods, device structures and use methods of this embodiment are the same as those of the first embodiment, and will not be described again.
Example 6
When the acylating agent is propionyl chloride and the compound is 4- (4-propylcyclohexyl) benzene (75.1% content), the product is 4- (4-propylcyclohexyl) propiophenone.
S1: methyl cyclohexane is added into the first reaction kettle 2, 40.0g of aluminum trichloride is slowly added, and stirring is carried out for 0.5-2 h at the temperature of 0-20 ℃.
S2: and (3) continuously stirring and cooling to the temperature of between minus 10 and 0 ℃, adding 26.0g of propionyl chloride, controlling the temperature not to exceed 20 ℃ in the dripping process, and dripping for about 2 hours.
S3: after the dripping is completed, stirring and cooling to 0 ℃, dripping 47.5g of 4- (4-propyl cyclohexyl) benzene, wherein the temperature is controlled to be not more than 20 ℃ in the dripping process, and dripping is carried out for about 2 hours. After all the dripping is completed, preserving the heat for 1-2 h.
S4: slowly pouring the reaction liquid in the first reaction kettle 2 into a second reaction kettle 3 containing ice water for hydrolysis, wherein the volume ratio of the reaction liquid to the ice water is 1:1, after stirring fully, standing and phase-separating in a second reaction kettle 3.
S5: after the phase separation is observed (light yellow transparent organic phase is positioned above and water is positioned below) through a vertical strip-shaped transparent observation window arranged on the outer wall of the second reaction kettle 3, a water pumping valve 9 on a bottom water pumping pipe 8 is opened, and the water below the phase separation is discharged. The organic phase in the second reactor 3 was washed with water to neutrality.
S6: the washed organic phase was discharged from the second reactor 3, and the solvent was removed by vacuum evacuation to obtain 51.0g of 4- (4-propylcyclohexyl) propiophenone, with a yield of 91.9% and a content of 67.7%.
The rest of implementation methods, device structures and use methods of this embodiment are the same as those of the first embodiment, and will not be described again.
Example 7
When the acylating agent is propionyl chloride and the compound is 4- (4-butylcyclohexyl) benzene (99.53%), the product is 4- (4-butylcyclohexyl) propiophenone.
S1: methyl cyclohexane is added into the first reaction kettle 2, 40.5g of aluminum trichloride is slowly added, and stirring is carried out for 0.5 to 2 hours at the temperature of between 0 and 20 ℃.
S2: and (3) continuously stirring and cooling to the temperature of between minus 10 and 0 ℃, adding 26.7g of propionyl chloride, controlling the temperature not to exceed 20 ℃ in the dripping process, and dripping for about 2 hours.
S3: after the dripping is completed, stirring and cooling to 0 ℃, dripping 48.5g of 4- (4-butylcyclohexyl) benzene, wherein the temperature is controlled to be not more than 20 ℃ in the dripping process, and dripping is carried out for about 2 hours. After all the dripping is completed, preserving the heat for 1-2 h.
S4: slowly pouring the reaction liquid in the first reaction kettle 2 into a second reaction kettle 3 containing ice water for hydrolysis, wherein the volume ratio of the reaction liquid to the ice water is 1:1, after stirring fully, standing and phase-separating in a second reaction kettle 3.
S5: after the phase separation is observed (light yellow transparent organic phase is positioned above and water is positioned below) through a vertical strip-shaped transparent observation window arranged on the outer wall of the second reaction kettle 3, a water pumping valve 9 on a bottom water pumping pipe 8 is opened, and the water below the phase separation is discharged. The organic phase in the second reactor 3 was washed with water to neutrality.
S6: the washed organic phase was discharged from the second reactor 3, and the solvent was removed by vacuum evacuation to obtain 56.0g of 4- (4-butylcyclohexyl) propiophenone, with a yield of 95.8% and a content of 95.4%.
The rest of implementation methods, device structures and use methods of this embodiment are the same as those of the first embodiment, and will not be described again.
Example 8
When the acylating agent is propionyl chloride and the compound is 4- (4-pentylcyclohexyl) benzene ((content 68.0%), the product is 4- (4-pentylcyclohexyl) propiophenone.
S1: methyl cyclohexane is added into the first reaction kettle 2, 41.0g of aluminum trichloride is slowly added, and stirring is carried out for 0.5 to 2 hours at the temperature of between 0 and 20 ℃.
S2: and (3) continuously stirring and cooling to the temperature of between minus 10 and 0 ℃, adding 27.5g of propionyl chloride, controlling the temperature not to exceed 20 ℃ in the dripping process, and dripping for about 2 hours.
S3: after the dripping is completed, stirring and cooling to 0 ℃, dripping 55.5g of 4- (4-amyl cyclohexyl) benzene, wherein the temperature is controlled to be not more than 20 ℃ in the dripping process, and dripping is carried out for about 2 hours. After all the dripping is completed, preserving the heat for 1-2 h.
S4: slowly pouring the reaction liquid in the first reaction kettle 2 into a second reaction kettle 3 containing ice water for hydrolysis, wherein the volume ratio of the reaction liquid to the ice water is 1:1, after stirring fully, standing and phase-separating in a second reaction kettle 3.
S5: after the phase separation is observed (light yellow transparent organic phase is positioned above and water is positioned below) through a vertical strip-shaped transparent observation window arranged on the outer wall of the second reaction kettle 3, a water pumping valve 9 on a bottom water pumping pipe 8 is opened, and the water below the phase separation is discharged. The organic phase in the second reactor 3 was washed with water to neutrality.
S6: the washed organic phase was discharged from the second reactor 3, and the solvent was removed by vacuum evacuation to obtain 57.0g of 4- (4-pentylcyclohexyl) propiophenone, with a yield of 92.7% and a content of 65.3%.
The rest of implementation methods, device structures and use methods of this embodiment are the same as those of the first embodiment, and will not be described again.
The foregoing description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical solution of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (5)
1. The method for synthesizing the 4- (4-alkyl cyclohexyl) aryl ketone by replacing dichloroethane with methylcyclohexane is characterized by comprising the following steps of:
s1: adding methylcyclohexane into a first reaction kettle (2), starting stirring, and slowly adding aluminum trichloride, wherein the molar ratio of the aluminum trichloride to the methylcyclohexane is 1:2-3; stirring for 0.5-2 h at the temperature of 0-20 ℃ after the addition is finished;
S2: continuously stirring until the temperature of the mixture is reduced to-10-0 ℃, dropwise adding an acylating reagent, wherein the temperature is controlled to be not more than 20 ℃ in the dropwise adding process, and the dropwise adding is completed within about 2+/-0.5 hours;
s3: a compound of the formula:
，
wherein n=2 to 5;
controlling the temperature not to exceed 20 ℃ in the dripping process, and preserving the heat for 1-2 hours after finishing dripping within 2+/-0.5 hours;
s4: slowly stirring, and slowly pouring the reaction liquid obtained in the step S3 into a second reaction kettle (3) containing ice water for hydrolysis, wherein the volume ratio of the reaction liquid to the ice water is 1:1; controlling the temperature not to exceed 20 ℃ in the hydrolysis process, standing and phase-separating after the hydrolysis is finished;
s5: standing for phase separation, extracting the organic phase with water above and water below until the organic phase is neutral;
s6: removing the solvent from the organic phase to obtain the 4- (4-alkyl cyclohexyl) aryl ketone, namely a compound shown in the following formula:
，
wherein n=2-5, m=1 or 2;
the first reaction kettle (2) and the second reaction kettle (3) are arranged on an installation seat (1), two fixing frames (4) are fixedly connected to the top end of the installation seat (1), the first reaction kettle (2) is subjected to stirring operation through a stirring mechanism (5), and the first reaction kettle (2) is driven to rotate through a rotating mechanism (6);
The inner cavity of the second reaction kettle (3) is provided with a second stirring shaft (7), the bottom end of the second reaction kettle (3) is provided with a water pumping pipe (8), the outer wall of the water pumping pipe (8) is provided with a water pumping valve (9), and the inner wall of the second reaction kettle (3) is provided with a PH value detection sensor (10);
the inner walls of the first reaction kettle (2) and the second reaction kettle (3) are respectively provided with a hollow interlayer, and a circulating medium taking modified dihydric alcohol as a refrigerant is introduced into the hollow interlayer, so that the environment temperature in the first reaction kettle (2) can be controlled, and the heat generated by the reaction in the first reaction kettle (2) and the second reaction kettle (3) can be circularly taken away;
the gas absorption device is arranged above the first reaction kettle (2) and the second reaction kettle (3) respectively, the gas absorption device comprises a gas collecting hood (11) arranged on a lifting support, the gas collecting hood (11) which is driven by the lifting support to descend to a lower limit can be tightly buckled at the upper opening of the first reaction kettle (2) and the second reaction kettle (3), the upper end of the gas collecting hood (11) is connected with one end of a gas guide pipe (12), and a gas pump is arranged on the gas guide pipe (12); the other end of the air duct (12) is inserted into a circulating water treatment box, a water inlet and a water outlet are formed in the circulating water treatment box, the water inlet is connected with a clean water source, and the water outlet is connected with a hydrochloric acid collecting box; control valves are arranged on the water inlet and the water outlet;
The stirring mechanism (5) comprises a rotating groove (501), the rotating groove (501) is formed in the outer wall of the fixing frame (4), a connecting column (502) is fixedly connected to the outer wall of the fixing frame (4), the connecting column (502) is rotatably connected to the inner wall of the rotating groove (501), a mounting frame (503) is fixedly connected to the outer wall of the fixing frame (4) below the connecting column (502), a motor (504) is mounted on the outer wall of the mounting frame (503), a connecting shaft (505) is connected to the output end of the motor (504), the connecting shaft (505) extends into the connecting column (502), a square block (506) is fixedly connected to the outer wall of the connecting shaft (505), an air cylinder (507) is mounted on the outer wall of the fixing frame (4) above the connecting column (502), a movable plate (508) is connected to the output end of the air cylinder (507), a movable frame (509) is fixedly connected to the bottom end of the movable plate (509), a square fluted disc (510) is connected to the inner side of the rotating disc (510), the inner wall of the first reaction kettle (2) is rotationally connected with a toothed ring (512), the outer wall of the toothed ring (512) is meshed with the outer wall of the fluted disc (511), and the bottom end of the toothed ring (512) is fixedly connected with a first stirring shaft (513);
The rotating mechanism (6) comprises a displacement plate (601), the displacement plate (601) is slidably connected to the inside of the connecting shaft (505), a first inclined surface block (602) and a first clamping block (604) are fixedly connected to the top end of the displacement plate (601), the first inclined surface block (602) and the first clamping block (604) extend out of the top end of the connecting shaft (505), a second inclined surface block (603) and a second clamping block (605) are fixedly connected to the bottom end of the displacement plate (601), the second inclined surface block (603) and the first inclined surface block (602) are respectively positioned on the upper side and the lower side of the displacement plate (601), the first clamping block (604) and the second clamping block (605) are respectively positioned on the upper side and the lower side of the displacement plate (601), a slot (606) for the connecting shaft (505) to be inserted into is formed in the outer wall of the connecting column (502), a push rod (509) is fixedly connected to the outer wall of the movable frame (509), a fixed groove (607) is formed in the top end of the inner wall of the displacement plate (601), a fixed groove (608) is formed in the inner wall of the rotating groove (603), a fixed groove (502) is formed in the inner wall, a sliding block (609) is connected to the inner wall (502), one end (610) of the connecting column (502) is fixedly connected with the sliding column (610), a spring (611) is connected between the fixed block (610) and the connecting column (502);
An annular first inner gear ring (612) is arranged in the inner cavity of the fluted disc (511), and one end of the first clamping block (604) is clamped with the first inner gear ring (612); the outer wall of the square block (506) is attached to the inner wall of the movable disc (510), a T-shaped annular groove (514) is formed in the outer wall of the movable disc (510), an arc block (515) is fixedly connected to the bottom end of the movable frame (509), and the outer wall of the arc block (515) is attached to the inner wall of the annular groove (514); the inner wall of the rotating groove (501) is attached to the outer wall of the connecting column (502), an annular second inner gear ring (613) is arranged on the inner wall of the slot (606), and the second inner gear ring (613) is clamped with one end of the second clamping block (605);
the inner wall of the fixed groove (608) is attached to the outer wall of the fixed block (610), an inclined plane is arranged at the bottom end of the fixed block (610), and the inclined plane is in contact with the sliding rod (609).
2. The method for synthesizing 4- (4-alkyl cyclohexyl) aryl ketone by replacing dichloroethane according to claim 1, wherein the method comprises the following steps of: in S2, the acylating agent used is one of acetyl chloride and propionyl chloride.
3. The method for synthesizing 4- (4-alkyl cyclohexyl) aryl ketone by replacing dichloroethane according to claim 1, wherein the method comprises the following steps of: in S2, the molar ratio of the acylating agent to the methylcyclohexane is 1:2-3.
4. The method for synthesizing 4- (4-alkyl cyclohexyl) aryl ketone by replacing dichloroethane according to claim 1, wherein the method comprises the following steps of: in S3, the compound is 4- (4-n-alkyl cyclohexyl) benzene, and the molar ratio of the 4- (4-n-alkyl cyclohexyl) benzene to the methylcyclohexane is 1:3 to 4.
5. The method for synthesizing 4- (4-alkyl cyclohexyl) aryl ketone by replacing dichloroethane according to claim 1, wherein the method comprises the following steps of: in S3, the compound is one of 4- (4-ethylcyclohexyl) benzene, 4- (4-propylcyclohexyl) benzene, 4- (4-butylcyclohexyl) benzene and 4- (4-pentylcyclohexyl) benzene.
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| US4818429A (en) * | 1986-09-11 | 1989-04-04 | Chisso Corporation | Cyclohexylphenylpyridazines |
| US5430015A (en) * | 1992-03-16 | 1995-07-04 | Unilever Patent Holdings, Bv | Acylation of tetralins |
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