CN114478241A - Preparation method of arylformyl formic ether - Google Patents
Preparation method of arylformyl formic ether Download PDFInfo
- Publication number
- CN114478241A CN114478241A CN202111682859.1A CN202111682859A CN114478241A CN 114478241 A CN114478241 A CN 114478241A CN 202111682859 A CN202111682859 A CN 202111682859A CN 114478241 A CN114478241 A CN 114478241A
- Authority
- CN
- China
- Prior art keywords
- aryl
- formate
- arylformyl
- reaction
- cyanide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 title description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 82
- -1 aryl formyl formate Chemical compound 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 29
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 28
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims abstract description 11
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 125000005251 aryl acyl group Chemical group 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000012527 feed solution Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 5
- 238000002347 injection Methods 0.000 abstract description 3
- 239000007924 injection Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000012295 chemical reaction liquid Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- TZIHFWKZFHZASV-UHFFFAOYSA-N anhydrous methyl formate Natural products COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 8
- 238000004064 recycling Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- SLVQLQSCRLIDRC-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]benzoyl cyanide Chemical compound CC1=CC=CC=C1OCC1=CC=CC=C1C(=O)C#N SLVQLQSCRLIDRC-UHFFFAOYSA-N 0.000 description 4
- WYXWANVHOUGOBI-UHFFFAOYSA-N 2-methylbenzoyl cyanide Chemical compound CC1=CC=CC=C1C(=O)C#N WYXWANVHOUGOBI-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- IZPOEGQHNRNBPO-UHFFFAOYSA-N CC1=CC=CC=C1.C(C1=CC=CC=C1)(=O)C#N Chemical compound CC1=CC=CC=C1.C(C1=CC=CC=C1)(=O)C#N IZPOEGQHNRNBPO-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- QKLCQKPAECHXCQ-UHFFFAOYSA-N ethyl phenylglyoxylate Chemical compound CCOC(=O)C(=O)C1=CC=CC=C1 QKLCQKPAECHXCQ-UHFFFAOYSA-N 0.000 description 3
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- YUCRNASRVPZKNQ-UHFFFAOYSA-N 2-chlorobenzoyl cyanide Chemical compound ClC1=CC=CC=C1C(=O)C#N YUCRNASRVPZKNQ-UHFFFAOYSA-N 0.000 description 2
- GJQBHOAJJGIPRH-UHFFFAOYSA-N benzoyl cyanide Chemical group N#CC(=O)C1=CC=CC=C1 GJQBHOAJJGIPRH-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- QUBYFEQCJJGPPA-UHFFFAOYSA-N 2-phenoxybenzoyl cyanide Chemical compound N#CC(=O)C1=CC=CC=C1OC1=CC=CC=C1 QUBYFEQCJJGPPA-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001264 acyl cyanides Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- CEIPQQODRKXDSB-UHFFFAOYSA-N ethyl 3-(6-hydroxynaphthalen-2-yl)-1H-indazole-5-carboximidate dihydrochloride Chemical compound Cl.Cl.C1=C(O)C=CC2=CC(C3=NNC4=CC=C(C=C43)C(=N)OCC)=CC=C21 CEIPQQODRKXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- NCLUHVGLCSDEKJ-UHFFFAOYSA-N tert-butyl 2-(2-methylphenyl)-2-oxoacetate Chemical compound C1(=C(C=CC=C1)C(C(=O)OC(C)(C)C)=O)C NCLUHVGLCSDEKJ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
- C07C257/04—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers
- C07C257/06—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers having carbon atoms of imino-carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms, or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/18—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of aryl formyl formate, which comprises the following steps: under the condition of acid gas, reacting a toluene solution of aryl cyanide with alcohol to obtain arylformyl imine hydrochloride, reacting in a jet reactor, hydrolyzing at low temperature to obtain arylformyl formate feed liquid, and desolventizing under negative pressure to obtain arylformyl formate; the acid gas is hydrogen chloride gas, the reaction temperature in the jet reactor is 50-100 ℃, and the pressure in the jet reactor is 0.02-0.05 MPa. The preparation method can effectively control the aryl formate impurities, greatly reduce the corrosivity to equipment, improve the environmental protection benefit, improve the gas-liquid mixing efficiency by utilizing the injection reactor, greatly shorten the reaction time, realize continuous reaction and have good stability.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of aryl formyl formate.
Background
Aryl formyl formic ether is an important intermediate of medicine and pesticide, the raw materials for synthesizing the compound are diversified, the industrialized process is that aryl acyl cyanide generates aryl formyl amide in the presence of strong acid, and further reacts with alcohol under the strong acid condition to generate aryl formyl formic ether, because the esterification step needs higher temperature and stronger acidity, a sulfuric acid and sodium bromide system is generally adopted, the reaction has the defects that the raw materials or intermediate state aryl formyl amide can generate aryl formyl carboxylic acid at high temperature in a strong acid aqueous solution, and the system needs to strictly control the water content and the temperature; aryl cyanide is easy to generate substitution reaction to generate aryl formate, the quality and yield of products are influenced, the proportion and concentration of alcohols are strictly controlled, other organic solvents are mostly adopted for dilution, the recovery and separation of mixed solvents are difficult, and the recycling effect is influenced; in addition, a gradient temperature rise and preservation mode is generally adopted for controlling impurities, so that the reaction period is long, the productivity is influenced, meanwhile, a strong acid water system is seriously corroded on equipment, the wastewater contains sulfur and bromine, the treatment cost is high, and the environmental benefit and the economic benefit are poor.
Disclosure of Invention
Aiming at the technical problems existing at present, the invention provides a preparation method of arylformyl formic ether, wherein a stage system for forming an intermediate imine hydrochloride by the method is anhydrous, aryl formic ether impurities can be effectively controlled, the corrosivity to equipment can be greatly reduced, hydrogen chloride is contained in wastewater and is used as acid water for neutralizing alkaline wastewater of an environment-friendly treatment station, the generation of sulfur-containing and bromine-containing wastewater in the traditional process is avoided, the environment-friendly benefit is improved, the reaction time is greatly shortened, the continuous reaction is realized, the stability is good, the product content is more than 98%, the yield is more than 95%, and the preparation method is suitable for industrial production.
The specific technical scheme of the invention is as follows:
a preparation method of aryl formyl formate comprises the following steps: under the condition of acid gas, reacting a toluene solution of aryl cyanide with alcohol to obtain arylformyl imine hydrochloride, reacting in a jet reactor, hydrolyzing at low temperature to obtain arylformyl formate feed liquid, and desolventizing under negative pressure to obtain arylformyl formate;
the acid gas is hydrogen chloride gas, the reaction temperature in the jet reactor is 50-100 ℃, and the pressure in the jet reactor is 0.02-0.05 MPa;
the reaction process is as follows:
R1-R5 are independently selected from hydrogen, alkyl, substituted alkyl, alkoxy, halogen, aryl, substituted aryl, aryloxy, benzyl or benzyloxy, and R6 is: methyl, ethyl or tert-butyl.
According to the method, aryl cyanide and alcohol are introduced with acid gas hydrogen chloride under an anhydrous condition to obtain an intermediate product, namely, arylformyl imine hydrochloride, and then, arylformyl formate is obtained through low-temperature hydrolysis. The advantage of this reaction is that it is anhydrous to form midbody imidate stage system, can effectively control aryl formic ester impurity, still greatly reduced the corrosivity to equipment, contain hydrogen chloride in the waste water, as acid water neutralization environmental protection processing station alkaline waste water, avoided traditional technology contain sulphur, bromine-containing waste water, promote environmental protection benefit, this technology combines the injection reactor, promote gas-liquid mixing efficiency, and utilize the system pressure-fired to further accelerate reaction rate, shorten reaction time greatly, realize the serialization reaction, good stability has, product content 98% is more than, yield 95% is more than, be applicable to the industrial production.
Preferably, the molar ratio of aryl cyanide to hydrogen chloride is 1: 1.1-1.5, the molar ratio of aryl cyanide to alcohol is 1: 1.1-1.3. If the ratio is over, raw materials are wasted, and if the ratio is not over, the reaction is incomplete, and acyl cyanide residues are large.
Preferably, the mass concentration of the aryl cyanide in the toluene solution is 30-50%.
Preferably, the hydrolysis reaction temperature is 0-5 ℃, and impurities are easily generated at high hydrolysis temperature.
Preferably, the specific preparation method comprises the following steps:
adjusting the pressure and temperature in the jet reactor, introducing alcohol, hydrogen chloride gas and a toluene solution of aryl acyl cyanide into the jet reactor, reacting, detecting that the aryl acyl cyanide residue is less than or equal to 0.05% by a reaction solution, allowing the reaction solution to enter water, stirring for hydrolysis, stirring for 30min after the system does not release heat, separating and cutting water to obtain an organic-phase arylformyl formate feed solution, and removing toluene from the feed solution under negative pressure to obtain arylformyl formate.
Preferably, the flow rate of the hydrogen chloride gas is 5-12cm3/h。
According to the invention, a mode of esterification and hydrolysis is adopted, the imine hydrochloride intermediate is generated to replace an amide intermediate in the traditional process, no water is introduced in the esterification reaction process, the raw materials are prevented from being subjected to acidolysis to generate carboxylic acid, meanwhile, the raw materials are prevented from being subjected to nucleophilic substitution reaction to generate carboxylic ester, hydrogen chloride is used to replace a sulfuric acid and sodium bromide system, the acidity is reduced, the corrosivity of anhydrous conditions to reaction equipment is reduced, the generation of sulfur-containing and bromine-containing waste water is avoided, the environmental protection benefit is improved, and the jet reactor is used for preparing the arylformyl formic ester.
Drawings
FIG. 1 is a liquid chromatogram of a reaction solution of example 1;
FIG. 2 is a liquid chromatogram of the reaction solution of example 2;
FIG. 3 is a liquid chromatogram of the reaction solution of example 3;
FIG. 4 is a liquid chromatogram of the reaction solution of example 4;
FIG. 5 is a liquid chromatogram of the reaction solution of example 5;
FIG. 6 is a liquid chromatogram of the reaction solution of example 6;
FIG. 7 is a liquid chromatogram of the reaction solution of example 7;
FIG. 8 is a liquid chromatogram of the reaction solution of comparative example 1;
FIG. 9 is a schematic view of the structure of a spray reactor.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following percentages are by mass.
Example 1
A preparation method of methyl benzoylformate comprises the following specific steps:
preparing 100g (0.229mol) of 30% benzoyl cyanide toluene solution, adjusting the pressure of a jet reactor to be 0.02MPa and the temperature to be 65 ℃, introducing 8.06g (0.2519mol) of methanol, 9.19g (0.2519mol) of hydrogen chloride and 100g of benzoyl cyanide toluene solution into the jet reactor, and adjusting the flow rate of hydrogen chloride gas to be 8cm through a gas flow meter3And h, reacting for 1h, taking reaction liquid from an outlet of an injection reactor to detect that benzoyl cyanide residue is less than or equal to 0.05%, tracing a spectrogram as shown in figure 1, ensuring that the reaction is qualified, putting the reaction liquid into 100g of water, keeping stirring and hydrolyzing, wherein the hydrolysis temperature is not more than 10 ℃, stirring for 30min after the system does not release heat, separating and cutting the liquid to obtain organic phase methyl benzoylformate feed liquid, performing negative pressure desolventization on the feed liquid, removing toluene to obtain a product methyl benzoylformate 36.49g, the content of 98.2%, the yield of 95.3%, and recycling the recovered toluene.
Example 2
A preparation method of ethyl benzoylformate comprises the following specific steps:
preparing 100g (0.267mol) of 35% benzoyl cyanide toluene solution, adjusting the pressure of a jet reactor to be 0.02MPa, adjusting the temperature of the jet reactor to be 80 ℃, introducing 14.74g (0.32mol) of ethanol, 11.69g (0.32mol) of hydrogen chloride and 100g of benzoyl cyanide toluene solution into the jet reactor, and adjusting the flow rate of the hydrogen chloride gas to be 8.2cm by a gas flow meter3Reaction for 1.2h, taking reaction liquid from the outlet of the reactor to detect that the benzoyl cyanide residue is less than or equal to 0.05 percent, tracing spectrogram as shown in figure 2, and qualified reactionThe reaction solution is put into 100g of water, stirred and hydrolyzed at the temperature of 0-5 ℃, stirred for 30min and cut after the system does not release heat, organic phase ethyl benzoylformate feed liquid is obtained, the feed liquid is subjected to negative pressure desolventization, toluene is removed, 46.27g of ethyl benzoylformate is obtained, the content is 98.1%, the yield is 95.4%, and the toluene is recovered for recycling.
Example 3
A preparation method of o-chlorobenzoyl methyl formate comprises the following specific steps:
preparing 100g (0.2415mol) of toluene solution of 40% o-chlorobenzoyl cyanide, adjusting the pressure of a jet reactor to 0.03MPa, adjusting the temperature of the jet reactor to 65 ℃, introducing 10g (0.314mol) of methanol, 11.46g (0.314mol) of hydrogen chloride and 100g of o-chlorobenzoyl cyanide methanol solution into the jet reactor, and adjusting the flow rate of the hydrogen chloride gas to 8cm by a gas flow meter3And h, reacting for 1.2h, sampling from an outlet of a reactor to detect that the residue of o-chlorobenzoyl cyanide is less than or equal to 0.05 percent, tracking a spectrogram as shown in a figure 3, ensuring that the reaction is qualified, adding a reaction solution into 100g of water, stirring and hydrolyzing at 0-5 ℃, stirring for 30min after the system does not release heat, separating and cutting the solution to obtain organic adjacent chlorobenzoyl methyl formate feed liquid, performing negative pressure desolventization on the feed liquid, removing toluene to obtain a product of o-chlorobenzoyl methyl formate 46.47g, wherein the content is 98.5 percent, the yield is 95.4 percent, and recycling the toluene.
Example 4
A preparation method of o-methyl benzoyl methyl formate comprises the following specific steps:
preparing 100g (0.2754mol) of toluene solution of 40% o-methyl benzoyl cyanide, adjusting the pressure of a jet reactor to be 0.05MPa, adjusting the temperature of the jet reactor to be 65 ℃, introducing 10.58g (0.33mol) of methanol, 14g (0.3856mol) of hydrogen chloride and 100g of toluene solution of o-methyl benzoyl cyanide into the jet reactor after the parameters are stable, and adjusting the flow rate of hydrogen chloride gas to be 12cm by a gas flowmeter3Reaction for 1 hour, sampling from the outlet of the reactor to detect that the residue of o-methylbenzoyl cyanide is less than or equal to 0.05 percent, tracking a spectrogram as shown in figure 4, ensuring that the reaction is qualified, putting the reaction liquid into 100g of water, stirring and hydrolyzing at 0-5 ℃, stirring for 30min after the system does not release heat, cutting water to obtain organic phase o-methylbenzoyl methyl formate feed liquid, performing negative pressure desolventization on the feed liquid, and removing the solutionRemoving toluene to obtain the product methyl o-methylbenzoate 40.06g, the content is 98.3%, the yield is 95.2%, and the recovered toluene is recycled.
Example 5
A preparation method of o-phenoxy benzoyl methyl formate comprises the following specific steps:
preparing 100g (0.1569mol) of 35% o-phenoxybenzoyl cyanide toluene solution, adjusting the pressure of a spray reactor to 0.04MPa, adjusting the temperature of the spray reactor to 65 ℃, introducing 6.53g (0.2039mol) of methanol, 6.872g of hydrogen chloride and 100g of o-phenoxybenzoyl cyanide toluene solution into the spray reactor, and adjusting the flow rate of hydrogen chloride gas to 5.8cm by a gas flow meter3Reaction for 1 hour, sampling from the outlet of the reactor to detect that the residual o-phenoxy benzoyl cyanide is less than or equal to 0.05 percent, tracking a spectrogram as shown in figure 5, ensuring that the reaction is qualified, putting the reaction liquid into 100g of water, stirring and hydrolyzing at 0-5 ℃, stirring for 30min after the system does not release heat, cutting water to obtain organic adjacent phenoxy benzoyl methyl formate feed liquid, performing negative pressure desolventizing on the feed liquid, removing toluene to obtain 38.97g of o-phenoxy benzoyl methyl formate, ensuring the content to be 98.5 percent, ensuring the yield to be 95.5 percent, and recycling the toluene.
Example 6
A preparation method of o-methyl benzoyl formic acid tert-butyl ester comprises the following specific steps:
preparing 100g (0.3443mol) of 50% o-methylbenzoyl cyanide toluene solution, adjusting the pressure of a jet reactor to 0.05MPa, adjusting the temperature of the jet reactor to 84 ℃, introducing 33.18g (0.4477mol) of tert-butyl alcohol into the jet reactor, introducing 18.85g (0.5164mol) of hydrogen chloride and 100g of o-methylbenzoyl cyanide toluene solution, adjusting the flow rate of hydrogen chloride gas to 11cm by a gas flow meter, and adjusting the flow rate of hydrogen chloride gas to 11cm by a gas flow meter3And h, reacting for 1.5h, taking reaction liquid from an outlet of the reactor to detect that the residual o-methylbenzoyl cyanide is less than or equal to 0.05 percent, tracking a spectrogram as shown in figure 6, ensuring that the reaction is qualified, adding the reaction liquid into 100g of water, stirring and hydrolyzing at 0-5 ℃, stirring for 30min after the system does not release heat, cutting water to obtain o-methylbenzoyl tert-butyl formate feed liquid, performing negative pressure desolventization on the feed liquid, removing methylbenzene to obtain a product, namely, the o-methylbenzoyl tert-butyl formate 83.93g, the content is 98.2 percent, the yield is 95.3 percent, and recycling the methylbenzene.
Example 7
A preparation method of 2- (2-methylphenoxymethyl) methyl benzoylformate comprises the following steps:
preparing 100g (0.12mol) of 30% toluene solution of 2- (2-methylphenoxymethyl) benzoyl cyanide, adjusting the pressure of a jet reactor to be 0.05MPa, adjusting the temperature of the jet reactor to be 65 ℃, introducing 4.22g (0.132mol) of methanol, 6.57g (0.18mol) of hydrogen chloride and 100g of toluene solution of 2- (2-methylphenoxymethyl) benzoyl cyanide into the jet reactor, reacting for 1h, taking reaction liquid from an outlet of the reactor, detecting that the residue of the 2- (2-methylphenoxymethyl) benzoyl cyanide is less than or equal to 0.05 percent, tracking a spectrogram as shown in a figure 7, ensuring that the reaction is qualified, introducing the reaction liquid into 100g of water, stirring and hydrolyzing at 0-5 ℃, stirring for 30min and cutting water after the system does not release heat any more to obtain organic phase methyl 2- (2-methylphenoxymethyl) benzoyl formate feed liquid, carrying out negative pressure desolvention the feed liquid, wherein the pressure is-0.096 MPa, removing until no fraction flows out, and obtaining the product of methyl 2- (2-methylphenoxymethyl) benzoyl formate 33.1g with the content of 98.4 percent and the yield of 95.5 percent at the system temperature of 98 ℃, and recycling the recovered toluene.
Comparative example 1
The method adopts a kettle type reaction to prepare the 2- (2-methylphenoxymethyl) benzoyl methyl formate, and comprises the following specific steps:
adding 100g (0.12mol) of 30% 2- (2-methylphenoxymethyl) benzoyl cyanide toluene solution into a reaction bottle, cooling to 10 ℃, adding 4.22g (0.132mol) of methanol and 90g of hydrochloric acid, heating to 40 ℃, carrying out heat preservation reaction for 8 hours, taking reaction liquid for detection, detecting the normalized content of 2- (2-methylphenoxymethyl) benzoyl cyanide by liquid phase tracking, wherein the tracking spectrogram is shown in figure 8;
carrying out negative pressure desolventizing on the reaction liquid under the pressure of-0.096 MPa until no fraction flows out, and obtaining 31.08g of methyl 2- (2-methylphenoxymethyl) benzoylformate at the system temperature of 98 ℃, and calculating the content by an external standard method through HPLC detection: 90% and yield 82%.
The raw material, namely the toluene solution of aryl acyl cyanide, can enter from the middle part of the jet reactor, the alcohol can enter from the upper part of the jet reactor, the acid gas, namely the hydrogen chloride, can enter from the lower part of the jet reactor, and the introduction position can be changed according to the situation in the actual operation process.
As can be seen from examples 1-7 and comparative examples, the most obvious advantages of the invention are shortened reaction time, increased product content and increased reaction yield after the jet reactor is used. Compared with the kettle type reaction, the reaction time of the invention can be shortened by 5 times, the product content is improved to more than 98 percent, and the reaction yield is improved to more than 95 percent.
Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention.
Claims (6)
1. A preparation method of aryl formyl formate is characterized by comprising the following steps: under the condition of acid gas, reacting a toluene solution of aryl cyanide with alcohol to obtain arylformyl imine hydrochloride, reacting in a jet reactor, hydrolyzing at low temperature to obtain arylformyl formate feed liquid, and desolventizing under negative pressure to obtain arylformyl formate;
the acid gas is hydrogen chloride gas, the reaction temperature in the jet reactor is 50-100 ℃, and the pressure in the jet reactor is 0.02-0.05 MPa;
the reaction process is as follows:
R1-R5 are independently selected from hydrogen, alkyl, substituted alkyl, alkoxy, halogen, aryl, substituted aryl, aryloxy, benzyl or benzyloxy, and R6 is: methyl, ethyl or tert-butyl.
2. The method of claim 1, wherein the molar ratio of aryl cyanide to hydrogen chloride is 1: 1.1-1.5, the molar ratio of aryl cyanide to alcohol is 1: 1.1-1.3.
3. The method of claim 1, wherein the mass concentration of the aryl cyanide in toluene is 30-50%.
4. The process of claim 1, wherein the hydrolysis temperature is 0-5 ℃.
5. The preparation method of the aryl formyl formate according to claim 1, which comprises the following steps:
adjusting the pressure and temperature in the jet reactor, introducing alcohol, hydrogen chloride gas and a toluene solution of aryl acyl cyanide into the jet reactor, reacting, detecting that the aryl acyl cyanide residue is less than or equal to 0.05% by a reaction solution, allowing the reaction solution to enter water, stirring for hydrolysis, stirring for 30min after the system does not release heat, separating and cutting water to obtain an organic-phase arylformyl formate feed solution, and removing toluene from the feed solution under negative pressure to obtain arylformyl formate.
6. The method of claim 5, wherein the flow rate of hydrogen chloride gas is 5-12cm3/h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111682859.1A CN114478241A (en) | 2021-12-31 | 2021-12-31 | Preparation method of arylformyl formic ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111682859.1A CN114478241A (en) | 2021-12-31 | 2021-12-31 | Preparation method of arylformyl formic ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114478241A true CN114478241A (en) | 2022-05-13 |
Family
ID=81510859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111682859.1A Pending CN114478241A (en) | 2021-12-31 | 2021-12-31 | Preparation method of arylformyl formic ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114478241A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773193A (en) * | 2022-05-17 | 2022-07-22 | 荆州瑞东医药科技有限公司 | Preparation method of 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetic acid methyl ester |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4596885A (en) * | 1977-02-25 | 1986-06-24 | Bayer Aktiengesellschaft | Process for the preparation of phenylglyoxylic acid esters |
| US5221762A (en) * | 1990-12-31 | 1993-06-22 | Basf Aktiengesellschaft | Preparation of e-oxime ethers of phenylglyoxylic esters |
| CN101139308A (en) * | 2007-08-21 | 2008-03-12 | 江苏耕耘化学有限公司 | Method for preparing bactericidal agent intermediate (E)-2-(2'-chloromethyl)phenyl-2-methoxy imino methyl acetate |
| CN104529818A (en) * | 2014-12-16 | 2015-04-22 | 江苏耕耘化学有限公司 | Method for preparing (E)-2-(2-substituted phenyl)-2-methoxyimino acetic acid derivative |
| CN107473971A (en) * | 2017-09-21 | 2017-12-15 | 湖北沙隆达股份有限公司 | Benzoyl cyanide synthesizes the new technology of methyl benzoylformate |
| CN109912417A (en) * | 2018-12-29 | 2019-06-21 | 京博农化科技有限公司 | A kind of 2-(2- methylenedioxy phenoxy methyl)-methyl benzoylformate synthetic method |
-
2021
- 2021-12-31 CN CN202111682859.1A patent/CN114478241A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4596885A (en) * | 1977-02-25 | 1986-06-24 | Bayer Aktiengesellschaft | Process for the preparation of phenylglyoxylic acid esters |
| US5221762A (en) * | 1990-12-31 | 1993-06-22 | Basf Aktiengesellschaft | Preparation of e-oxime ethers of phenylglyoxylic esters |
| CN101139308A (en) * | 2007-08-21 | 2008-03-12 | 江苏耕耘化学有限公司 | Method for preparing bactericidal agent intermediate (E)-2-(2'-chloromethyl)phenyl-2-methoxy imino methyl acetate |
| CN104529818A (en) * | 2014-12-16 | 2015-04-22 | 江苏耕耘化学有限公司 | Method for preparing (E)-2-(2-substituted phenyl)-2-methoxyimino acetic acid derivative |
| CN107473971A (en) * | 2017-09-21 | 2017-12-15 | 湖北沙隆达股份有限公司 | Benzoyl cyanide synthesizes the new technology of methyl benzoylformate |
| CN109912417A (en) * | 2018-12-29 | 2019-06-21 | 京博农化科技有限公司 | A kind of 2-(2- methylenedioxy phenoxy methyl)-methyl benzoylformate synthetic method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773193A (en) * | 2022-05-17 | 2022-07-22 | 荆州瑞东医药科技有限公司 | Preparation method of 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetic acid methyl ester |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7176331B2 (en) | Method of making fluorinated vinyl ethers | |
| CN106748712B (en) | The preparation method of hyptafluorobutyric acid and its derivative | |
| CN109721545A (en) | A kind of preparation method of azoxystrobin intermediate | |
| CN111689908B (en) | Post-treatment method for synthesizing 4, 6-dihydroxypyrimidine | |
| CN111470939A (en) | Production device and method for continuously producing 2-bromo-3, 3, 3-trifluoropropene | |
| CN106458809B (en) | Process for preparing 2, 5-dihalophenols | |
| CN109503418A (en) | A kind of preparation process of methyl hydrazine | |
| CN102659650B (en) | Device and method for preparing DL-methionine salt | |
| CN114478241A (en) | Preparation method of arylformyl formic ether | |
| WO2022088306A1 (en) | Method for preparing intermediate 4,4-dimethylisoxazol-3-one | |
| CN110183358A (en) | Hydrazine hydrochloride is as the purposes of production aminoguanidine carbonate and the combine production method of aminoguanidine carbonate and ammonium chloride | |
| CN112592285A (en) | Continuous ammoniation production method of aminoacetic acid | |
| CN107118073A (en) | The method that two alcohol catalysis prepare dichloro alkyl halide | |
| CN108586243B (en) | Method for indirectly synthesizing organic carbonate from carbon dioxide and organic amine | |
| CN113072449B (en) | Synthesis method of 4,4, 4-trifluoroacetylacetic acid ethyl ester | |
| CN106478422B (en) | A kind of preparation method of paranitrophenylacetic acid | |
| CN109232508B (en) | Preparation method of 1, 1-cyclohexyl diacetic anhydride | |
| CN114436966A (en) | Continuous synthesis method of N-vinyl imidazole | |
| CN113387329A (en) | Low-cost high-efficiency preparation method of iodine monochloride and obtained iodine monochloride | |
| CN111004184A (en) | Synthesis process of 4, 6-dichloropyrimidine | |
| CN219559579U (en) | Closed loop production system of trifluoroethanol | |
| US9061978B1 (en) | Process for the production of ethionic acid | |
| CN115703722B (en) | Preparation method of N, N-dimethyl trifluoromethyl sulfonamide | |
| CN113979854B (en) | Method for electrochemically preparing 2-phenylpropionic acid | |
| CN111362798B (en) | Safe production process of butyl acrylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220513 |
|
| RJ01 | Rejection of invention patent application after publication |