CN102174002A - Method for preparing 2-hydroxybenzonitrile from ammonium salicylate as raw material - Google Patents
Method for preparing 2-hydroxybenzonitrile from ammonium salicylate as raw material Download PDFInfo
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- CN102174002A CN102174002A CN2011100584678A CN201110058467A CN102174002A CN 102174002 A CN102174002 A CN 102174002A CN 2011100584678 A CN2011100584678 A CN 2011100584678A CN 201110058467 A CN201110058467 A CN 201110058467A CN 102174002 A CN102174002 A CN 102174002A
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Abstract
The invention discloses a method for preparing 2-hydroxybenzonitrile from ammonium salicylate as a raw material, comprising the following steps of: introducing ammonia gas or ammonia water to a salicylic acid slurry until the pH of the solution is 7.5-13.0, then evaporating to obtain ammonium salicylate solid; forming a mixture from the ammonium salicylate solid, urea, sulfamic acid, a catalyst and a solvent, wherein the catalyst is prepared from 0.0001-10 of magnesium oxide, 0.0001-5 of aluminum oxide, 0.0001-8 of calcium oxide, 0.0001-8 of silicon oxide and 0.0001-10 of artificial zeolite, and the solvent is prepared from 0.0001-10 of o-methyl phenol, 0.0001-6 of p-methyl phenol, 0.0001-8 of diethylene glycol, 0.0001-9 of methyl salicylate, 0.0001-10 of diphenyl oxide and 0.0001-12 of dichlorophenol; and after insulating at 150-180 DEG C for 0.5-10.0 hours and insulating at 190-260 DEG C for 0.5-10.0 hours, filtering or centrifuging the material, evaporating to remove the solvent, crystallizing, recrystallizing, and drying to obtain the 2-hydroxybenzonitrile product of which the mass percentage composition is greater than 90%.
Description
Technical field
Involved in the present invention a kind of be that the method for feedstock production salicylonitrile is the meticulous organic intermediate method of a kind of novel preparation phenolic hydroxy group virtue nitrile structure of field of fine chemical organic intermediate chemistry aspect with the Salicylate ammonium.
Background technology
Salicylonitrile has another name called salicylonitrile, 2-hydroxy-phenylformonitrile, o-hydroxy nitrile, 2-cyanophenol, willow nitrile, adjacent cyano group phenol, adjacent cyanophenol, and molecular formula is C
7H
5NO, molecular weight are 119.12, and the CAS registration number is 611-20-1.The fusing point of salicylonitrile general industry product is 95～98 ℃, and the fusing point of pure product is at 102～102.5 ℃, 149 ℃/1.9kPa of boiling point (14mmHg), have certain water-soluble, and to highly basic or strong oxidizer instability.As medicine intermediate, salicylonitrile can be used for treating the preparation of hypertension and angina drug bunitrolol; As pesticide intermediate, salicylonitrile can be used for the preparation of methoxy acrylic bactericide Azoxystrobin.In addition, salicylonitrile also can be used for the synthetic of multiple spices and liquid crystal material as important intermediate.
Salicylate ammonium has another name called the salicylic acid ammonium, is that the reaction of Whitfield's ointment and ammonia or ammoniacal liquor generates the organic acid ammonium salt, has well water-soluble.The different in kind of Salicylate ammonium is in Whitfield's ointment, and it does not have sublimability, and has certain high thermal resistance, does not resemble Whitfield's ointment and the decarboxylation decomposition at high temperature can take place and generate phenol.
The existing method that can be used for preparing adjacent oxybenzene formonitrile HCN has multiple, wherein relates generally to salicylic aldehyde and oxammonium hydrochloride to be the salicylaldoxime evaporation of raw material, to be the etherificate-catalytic ammoxidation method of raw material with the ortho-cresol, to be the direct evaporation of raw material with the salicylic amide, to be the displacement method of substitution etc. of raw material with the phenol o-iodine.
When preparing salicylonitrile by the salicylaldoxime evaporation; because of the price of the raw material salicylic aldehyde that uses and oxammonium hydrochloride all than higher; and in preparation process, also need a large amount of N-Methyl pyrrolidone, N of using; dinethylformamide high boiling point polar solvents such as (DMF); the product that generates need be separated out and causes a large amount of waste water to generate by thin up; not only production cost is higher when being equipped with salicylonitrile by this legal system thereby make, but also has the pressure of environment protection aspect.
By etherificate-when the catalytic ammoxidation legal system is equipped with salicylonitrile, the phenolic hydroxyl group etherificate that needs earlier under certain conditions to make ortho-cresol with methyl-sulfate etc. as etherifying agent is in case its oxidation under hot conditions, and the product that generates after the simultaneous oxidation needs also that hydrolysis just can obtain product under alkaline condition; And the per pass conversion when being equipped with salicylonitrile by this legal system is low, for improving utilization ratio of raw materials, needs to use raw material and product separation middle device; In addition, the by product that produces in the catalytic oxidation process can make irreversibly inactivation of catalyzer in the short period of time, and requires the equipment can high pressure resistant and high temperature.Thereby etherificate-catalytic ammoxidation legal system is equipped with salicylonitrile and has complex technical process, invests big problem.
When preparing salicylonitrile by the direct evaporation of salicylic amide, need to use such as dewatering agents such as phosphorus oxychloride, phosphorus pentachloride, thiophosphoric anhydride, Vanadium Pentoxide in FLAKES, triphosgene, and the existence that the use of these dewatering agents has generates hazardous property gases such as hydrogenchloride, hydrogen sulfide, the problem that also has the generation phosphorus-containing wastewater that has, simultaneously employed raw material salicylic amide also needs to prepare by salicylic amidation, and these factors make the cost that is equipped with salicylonitrile by this legal system be difficult to satisfactory.
When preparing salicylonitrile by the displacement method of substitution, often need to use prussiates such as cupric cyanide as the primitive reaction raw material, and the existence of prussiates such as cupric cyanide is subjected to thermolability, and prussiate also can have been emitted very supervirulent prussic acid gas with the acid effect, and is very strict to the requirement of equipment and operation when this makes in the actual production and to be equipped with salicylonitrile by this legal system.
In addition, salicylonitrile can also be a raw material by wintergreen oil and ammonia, to be carried on phosphoric acid, borophosphoric acid on the silica gel, to be carried on borophosphoric acid, boron oxide-vanadium oxide-Vanadium Pentoxide in FLAKES or doping phosphoric acid boron carrier etc. on the aluminum oxide as catalyzer, and at first make its vaporization under the temperature of wintergreen oil being higher than, and enter the fluidized-bed reactor that is filled with catalyzer with ammonia, reaction and obtain salicylonitrile under 280～450 ℃ temperature.The deficiency that mainly has following several respects when preparing salicylonitrile by this method: the one, the regeneration of catalyzer, the 2nd, manufacturing specification request is bigger, and the 3rd, wintergreen oil high temperature decomposes the harm of the phenol of generation to the catalyzer existence down.
In a word; at the existing all multi-methods that are used for preparing salicylonitrile; or exist employed raw material height to cause the big problem of production cost; or the problem of " three wastes " that exist to generate environment protection aspect of bringing more; or the problem of the secure context that brings of the material toxicity height that exist to use; or having the problem of the aspects such as one-time investment height that employed production unit requirement height brings, the existence of these problems makes the production method of salicylonitrile improved and necessitates.
Be equipped with by the Salicylate ammonium legal system in the research process of salicylonitrile, contacted the technical information that much prepares and utilize the aspect about fragrant formonitrile HCN compounds, wherein have mainly comprising of certain reference value: " 3, synthesizing of 5-dihalo-4-hydroxy-phenylformonitrile " (East China University of Science's journal, 1997, Vol.23, No.4), " the synthetic para hydroxybenzene formonitrile HCN research of oxidation proceses of ammonia " (Wuhan University's journal, 2003, Vol.49, No.4), " the synthetic and STUDY ON CORROSION INHIBITION of cyanobenzene series compound " (Speciality Petrochemicals, 1997, No.2), " synthesizing of cloth Lip river Neil " (medicine industry, 1987, Vol.18, No.8), " to the study on the synthesis of oxybenzene formonitrile HCN " (fine chemistry industry, 1994, Vol.11, No.2), " improvement of para hydroxybenzene formonitrile HCN synthetic method " (chemical reagent, 2005, Vol.27, No.3), " about by the carboxylic acid one-step synthetising nitrile " (Beijing University of Technology's journal, 1989, Vol.15, No.1), " Efficient one-pot preparation of nitriles from aldehydesusing N-methylpyrrolidone " (Synthesis, 1999, No.4), " theoretical investigation of adjacent cyanophenol and benzoxazole isomerization reaction " (Chinese Journal of Chemical Physics, 1995, Vol.8, No.6), " synthesizing of Azoxystrobin " (fine-chemical intermediate, 2007, Vol.37, No.2), " the application of methoxy acrylic bactericide, exploitation present situation and prospect " (pesticide science and management, 2003,2 Vol.24, No.12), " salicylic aldehyde single stage method synthesizing o-hydroxy formonitrile HCN " (pesticide research and application, 2007, Vol.11, No.2), " Method for the preparation of 2 hydroxybenzonitrile " (US 5637750,1997-06-10), " about by the carboxylic acid one-step synthetising nitrile " (Beijing University of Technology's journal, 1989, Vol.15, No.1), " method for preparing amino or hydroxy-phenylformonitrile " (CN 1146452A, 1997-04-02) with " salicylic amide single stage method synthesizing o-hydroxy formonitrile HCN " (Shanxi chemical industry, 2009, Vol.29, No.1) etc.
Summary of the invention
A kind of is the invention of feedstock production salicylonitrile method with the Salicylate ammonium, mainly be that the reactions steps that exists in existing salicylonitrile preparation method and the technology is many in order to solve, technology is comparatively complicated, conversion of raw material is not high, facility investment big or product in the problem of the not high aspects of bringing such as product application performance of salicylonitrile content.
Contain in the mixture of Whitfield's ointment and water by ammonia is fed, or Whitfield's ointment is directly joined in the ammoniacal liquor, and at room temperature to stir until what form homogeneous and contain the bigcatkin willow acid ammonium solution; The aqueous solution that will contain Salicylate ammonium obtains the Salicylate ammonium solid at normal pressure or reduced pressure through evaporation; By Salicylate ammonium in organic solvent and urea reaction in the presence of the catalyzer generate contain the mixture of salicylonitrile after, then after filtration or centrifugation, underpressure distillation, crystallization or recrystallization obtain the Minute Organic Synthesis intermediate neighbour oxybenzene formonitrile HCN that can be widely used in a plurality of fields such as medicine, agricultural chemicals, spices, liquid crystal materials.When preparing salicylonitrile by this method, not only can reduce and produce salicylonitrile the requirement of equipment and the production cost of salicylonitrile, and can improve the salicylic utilization ratio of raw material, " three wastes " quantity discharged that exists when reducing, the quality that improves product by existing prepared salicylonitrile.
In the invention related a kind of be the method for feedstock production salicylonitrile with the Salicylate ammonium, its characteristics show as: direct reaction in the presence of catalyzer prepares salicylonitrile by Salicylate ammonium and urea, make the operation of reaction more simple, the equipment requirements of preparation salicylonitrile is reduced; By the use of high boiling solvent, the stirring that makes material in the reaction is more prone to mixing, and makes also that reaction mass is easier to be separated with byproduct with catalyzer; By the use of catalyzed by amino sulfonic acid agent, make " three wastes " that produce in the adjacent oxybenzene formonitrile HCN production technique still less, utilization ratio of raw materials is higher; The content height of salicylonitrile in the product; The Whitfield's ointment distillation that has existed when having avoided preparing salicylonitrile for the raw material single stage method and decomposing by Whitfield's ointment.
By the method in the invention, can be implemented on the simpler equipment with the adjacent oxybenzene formonitrile HCN of the explained hereafter of more late operation, and make raw material generate the salicylonitrile product, and the content of salicylonitrile is higher than 90% in the product with higher transformation efficiency.
Description of drawings
Fig. 1 is the structural formula figure of salicylonitrile, and Fig. 2 is the FT-IR figure of salicylonitrile product.
Embodiment
What relate in the invention is the method for feedstock production salicylonitrile with the Salicylate ammonium, and its process mainly comprises following components: (1) Whitfield's ointment is scattered in the water of certain mass and stirs and forms the Whitfield's ointment slip; (2) feed ammonia or add ammoniacal liquor to the Whitfield's ointment slip, and at room temperature continue stirring until the aqueous solution that contains Salicylate ammonium that forms homogeneous; (3) the solution evaporation concentration under normal pressure or reduced pressure that contains Salicylate ammonium obtains the Salicylate ammonium solid; (4) Salicylate ammonium solid and urea are joined in the reactor by the certain mass ratio, and by certain mass than add thionamic acid and by magnesium oxide, aluminum oxide, calcium oxide, silicon oxide and permutite by certain mass than the catalyzer that constitutes, obtain containing the solid mixture material of Salicylate ammonium, urea and thionamic acid and catalyzer after the stirring; (5) by certain mass than in the solid mixture material that contains Salicylate ammonium, urea and thionamic acid and catalyzer, adding by ortho-methyl phenol, p-methyl phenol, a condensed ethandiol, wintergreen oil, phenyl ether and chlorophenesic acid by certain mass than the organic solvent that constitutes, and stir the formation mixture; (6) mixture that forms in (5) is heated, and behind insulation certain hour under 150～180 ℃, continue to be warming up to 190～260 ℃ of insulation certain hours down again, obtain containing the mixture of salicylonitrile; (7) contain the mixture filtered while hot or the centrifugation of salicylonitrile, and with hot solvent washing solid filter residue, merging filtrate or centrifugate obtain containing the solution of adjacent oxybenzene formonitrile HCN; (8) solution that contains salicylonitrile carries out rectifying again and obtains the salicylonitrile crude product after the reduced pressure steaming desolventizes under reduced pressure; Or the solution that contains salicylonitrile reduced pressure steam remove most of solvent after, crystallization under room temperature or cold condition again, and after filtration or centrifugation obtain the salicylonitrile crude product; (9) the salicylonitrile crude product double solvents recrystallization that constitutes by chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF), ethanol, methyl alcohol, ethylene dichloride; (7) material behind the recrystallization is again through cooling, crystallization, centrifugal or filter and obtain the salicylonitrile wet stock; (10) the salicylonitrile wet stock can obtain the salicylonitrile product through normal pressure or vacuum-drying.
Relate in the invention a kind of be the method for feedstock production salicylonitrile with the Salicylate ammonium, the processing parameter of the adjacent oxybenzene formonitrile HCN of its related preparation is as follows: the mass ratio of Whitfield's ointment and water is 0.01～10 during (1) preparation Whitfield's ointment slip, after feeding ammonia or add ammoniacal liquor in the Whitfield's ointment slip, the pH that finally makes solution is 7.5～13.0; (2) mass ratio of Salicylate ammonium and urea is 0.1～6.0, with the mass ratio of thionamic acid be 0.2～5.0; (3) mass ratio of catalyzer and Salicylate ammonium is 0.00001～1.0, and wherein catalyzer is pressed m by magnesium oxide, aluminum oxide, calcium oxide, silicon oxide and permutite
Magnesium oxide: m
Oxygen Change aluminium: m
Calcium oxide: m
Silicon oxide: m
PermutiteConstitute at=0.0001～10: 0.0001～5: 0.0001～8: 0.0001～8: 0.0001～10; (4) mass ratio of Salicylate ammonium and solvent is 0.01～10.0, and wherein solvent is pressed m by ortho-methyl phenol, p-methyl phenol, a condensed ethandiol, wintergreen oil, phenyl ether and chlorophenesic acid
Ortho-methyl phenol: m
P-methyl phenol: m
One condensed ethandiol: m
Wintergreen oil: m
Phenyl ether: m
Chlorophenesic acidConstitute at=0.0001～10: 0.0001～6: 0.0001～8: 0.0001～9: 0.0001～10: 0.0001～12; (5) contain the mixture heating of Salicylate ammonium, urea and thionamic acid and organic solvent after, the soaking time under 150～180 ℃ is 0.5～10.0 hour, the soaking time under 190～260 ℃ is 0.5～10.0 hour; (6) solvent that is used for salicylonitrile crude product recrystallization by chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF), ethanol, methyl alcohol, ethylene dichloride by mass ratio 0.01～10: constitute at 0.001～12: 0.1～10: 0.001～16: 0.001～18: 0.001～5: 0.001～6: 0.001～8; (7) during recrystallization, the mass ratio of double solvents and salicylonitrile crude product is 1.0～20.0; (8) vacuum tightness of salicylonitrile wet stock when carrying out vacuum-drying is that 0.01～0.1MPa, temperature are 10～120 ℃; (9) the vacuum drying time is 1.0～48.0 hours; (10) in the product after the vacuum-drying salicylonitrile quality percentage composition greater than 90%.
Embodiment 1:
138 gram Whitfield's ointments are after water are made into slip with 400 grams, make its formation uniform solution to wherein feeding ammonia or add ammoniacal liquor, stirring again, are 8.0 and obtain containing the aqueous solution of Salicylate ammonium until the pH of solution; Contain Salicylate ammonium solid transfer that the aqueous solution of Salicylate ammonium obtains after evaporation concentration, crystallization, filtration or centrifugation behind reactor, add again 90 gram urea, 97 gram thionamic acids and 1 gram by magnesium oxide, aluminum oxide, calcium oxide, silicon oxide, permutite by m
Magnesium oxide: m
Aluminum oxide: m
Calcium oxide: m
Silicon oxide: m
Permutite=0.0001: 0.005: 0.8: 0.08: 1.0 catalyzer that constitute and 120 grams are pressed m ortho-methyl phenol: m by ortho-methyl phenol, p-methyl phenol, a condensed ethandiol, wintergreen oil, phenyl ether and chlorophenesic acid
P-methyl phenol: m
One condensed ethandiol: m
Wintergreen oil: m
Phenyl ether: m
Two Chlorophenol=0.0001: 0.006: 0.0008: 9: the solvent that constitutes at 0.01: 0.12, stir and form mixture; The heated mixt material make its temperature rise to 150 ℃ and be incubated 0.5 hour after, continue heating again and make material rise to 190 ℃ and be incubated 0.5 hour, obtain containing the mixture of salicylonitrile; Contain the mixture filtered while hot or the centrifugation of salicylonitrile, and with identical hot solvent washing solid filter residue, merging filtrate or centrifugate obtain containing the solution of adjacent oxybenzene formonitrile HCN; The solution that contains salicylonitrile carries out rectifying again and obtains the salicylonitrile crude product after the reduced pressure steaming desolventizes under reduced pressure; The salicylonitrile crude product with 50 the gram press mass ratio 0.01: 2: 3 by chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF), ethanol, methyl alcohol, ethylene dichloride: 0.001: 0.18: 5: 0.6: 2 the formation the double solvents recrystallization, and after filtration or centrifugation obtain the salicylonitrile wet stock; Salicylonitrile wet stock 0.01Mpa vacuum tightness and 50 ℃ of dryings 1.0 hours obtain the quality percentage composition and are 90.5% salicylonitrile product.
Embodiment 2:
138 gram Whitfield's ointments are after water are made into slip with 200 grams, make its formation uniform solution to wherein feeding ammonia or add ammoniacal liquor, stirring again, are 9.0 and obtain containing the aqueous solution of Salicylate ammonium until the pH of solution; Contain Salicylate ammonium solid transfer that the aqueous solution of Salicylate ammonium obtains after evaporation concentration, crystallization, filtration or centrifugation behind reactor, add again 105 gram urea, 146 gram thionamic acids and 2 grams by magnesium oxide, aluminum oxide, calcium oxide, silicon oxide, permutite by m
Magnesium oxide: m
Aluminum oxide: m
Calcium oxide: m
Oxygen Change silicon: m
Permutite=0.001: 0.05: 1.8: 0.8: 2.0 catalyzer that constitute and 160 grams are pressed m ortho-methyl phenol: m by ortho-methyl phenol, p-methyl phenol, a condensed ethandiol, wintergreen oil, phenyl ether and chlorophenesic acid
P-methyl phenol: m
One condensed ethandiol: m
Wintergreen oil: m
Two Phenylate: m
Chlorophenesic acid=1.0: 0.6: 0.8: 3: the solvent that constitutes at 2.0: 6, stir and form mixture; The heated mixt material make its temperature rise to 170 ℃ and be incubated 2.5 hours after, continue heating again and make material rise to 190 ℃ and be incubated 1.5 hours, obtain containing the mixture of salicylonitrile; Contain the mixture filtered while hot or the centrifugation of salicylonitrile, and with identical hot solvent washing solid filter residue, merging filtrate or centrifugate obtain containing the solution of adjacent oxybenzene formonitrile HCN; The solution that contains salicylonitrile carries out rectifying again and obtains the salicylonitrile crude product after the reduced pressure steaming desolventizes under reduced pressure; The salicylonitrile crude product with 50 the gram press mass ratio 10: 5: 1 by chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF), ethanol, methyl alcohol, ethylene dichloride: 6: 3: 1: 3: 2 the formation the double solvents recrystallization, and after filtration or centrifugation obtain the salicylonitrile wet stock; Salicylonitrile wet stock 0.03Mpa vacuum tightness and 60 ℃ of dryings 3.0 hours obtain the quality percentage composition and are 91.5% salicylonitrile product.
Embodiment 3:
138 gram Whitfield's ointments are after water are made into slip with 500 grams, make its formation uniform solution to wherein feeding ammonia or add ammoniacal liquor, stirring again, are 10.0 and obtain containing the aqueous solution of Salicylate ammonium until the pH of solution; Contain Salicylate ammonium solid transfer that the aqueous solution of Salicylate ammonium obtains after evaporation concentration, crystallization, filtration or centrifugation behind reactor, add again 120 gram urea, 194 gram thionamic acids and 5 grams by magnesium oxide, aluminum oxide, calcium oxide, silicon oxide, permutite by m
Magnesium oxide: m
Aluminum oxide: m
Calcium oxide: m
Silicon oxide: m
Permutite=0.01: 0.5: 8: 8: 1.0 catalyzer that constitute and 180 grams are pressed m ortho-methyl phenol: m by ortho-methyl phenol, p-methyl phenol, a condensed ethandiol, wintergreen oil, phenyl ether and chlorophenesic acid
P-methyl phenol: m
One condensed ethandiol: m
Wintergreen oil: m
Two stupid ethers: m
Chlorophenesic acid=2.0: 0.6: 1.5: 1.9: the solvent that constitutes at 5.0: 3.0, stir and form mixture; The heated mixt material make its temperature rise to 175 ℃ and be incubated 1.5 hours after, continue heating again and make material rise to 200 ℃ and be incubated 2.0 hours, obtain containing the mixture of salicylonitrile; Contain the mixture filtered while hot or the centrifugation of salicylonitrile, and with identical hot solvent washing solid filter residue, merging filtrate or centrifugate obtain containing the solution of adjacent oxybenzene formonitrile HCN; The solution that contains salicylonitrile carries out rectifying again and obtains the salicylonitrile crude product after the reduced pressure steaming desolventizes under reduced pressure; The salicylonitrile crude product with 80 the gram press mass ratio 5.0: 1.2: 10 by chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF), ethanol, methyl alcohol, ethylene dichloride: 8: 8: 5: 0.6: 8 the formation the double solvents recrystallization, and after filtration or centrifugation obtain the salicylonitrile wet stock; Salicylonitrile wet stock 0.05Mpa vacuum tightness and 60 ℃ of dryings 13.0 hours obtain the quality percentage composition and are 92.5% salicylonitrile product.
Embodiment 4:
138 gram Whitfield's ointments are after water are made into slip with 300 grams, make its formation uniform solution to wherein feeding ammonia or add ammoniacal liquor, stirring again, are 11.0 and obtain containing the aqueous solution of Salicylate ammonium until the pH of solution; Contain Salicylate ammonium solid transfer that the aqueous solution of Salicylate ammonium obtains after evaporation concentration, crystallization, filtration or centrifugation behind reactor, add again 120 gram urea, 194 gram thionamic acids and 10 grams by magnesium oxide, aluminum oxide, calcium oxide, silicon oxide, permutite by m
Magnesium oxide: m
Aluminum oxide: m
Calcium oxide: m
Silicon oxide: m
Permutite=1.0: 0.5: 0.8: 0.8: 5.0 catalyzer that constitute and 200 grams are pressed m ortho-methyl phenol: m by ortho-methyl phenol, p-methyl phenol, a condensed ethandiol, wintergreen oil, phenyl ether and chlorophenesic acid
P-methyl phenol: m
One condensed ethandiol: m
Wintergreen oil: m
Two Phenylate: m
Chlorophenesic acid=2.0: 0.6: 1.5: 1.9: the solvent that constitutes at 5.0: 3.0, stir and form mixture; The heated mixt material make its temperature rise to 175 ℃ and be incubated 5.5 hours after, continue heating again and make material rise to 240 ℃ and be incubated 6.0 hours, obtain containing the mixture of salicylonitrile; Contain the mixture filtered while hot or the centrifugation of salicylonitrile, and with identical hot solvent washing solid filter residue, merging filtrate or centrifugate obtain containing the solution of adjacent oxybenzene formonitrile HCN; The solution that contains salicylonitrile reduced pressure steam remove most of solvent after, crystallization under room temperature or cold condition again, and after filtration or centrifugation obtain the salicylonitrile crude product; The salicylonitrile crude product with 100 the gram press mass ratio 5.0: 2.0: 6.0 by chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF), ethanol, methyl alcohol, ethylene dichloride: 8.0: 8.0: 5.0: 0.6: 4.0 the formation the double solvents recrystallization, and after filtration or centrifugation obtain the salicylonitrile wet stock; Salicylonitrile wet stock 0.07Mpa vacuum tightness and 90 ℃ of dryings 16.0 hours obtain the quality percentage composition and are 95.5% salicylonitrile product.
Embodiment 5:
138 gram Whitfield's ointments are after water are made into slip with 600 grams, make its formation uniform solution to wherein feeding ammonia or add ammoniacal liquor, stirring again, are 12.0 and obtain containing the aqueous solution of Salicylate ammonium until the pH of solution; Contain Salicylate ammonium solid transfer that the aqueous solution of Salicylate ammonium obtains after evaporation concentration, crystallization, filtration or centrifugation behind reactor, add again 180 gram urea, 281 gram thionamic acids and 16 grams by magnesium oxide, aluminum oxide, calcium oxide, silicon oxide, permutite by m
Magnesium oxide: m
Aluminum oxide: m
Calcium oxide: m
Silicon oxide: m
Permutite=0.1: 0.5: 0.8: 0.8: 1.0 catalyzer that constitute and 300 grams are pressed m ortho-methyl phenol: m by ortho-methyl phenol, p-methyl phenol, a condensed ethandiol, wintergreen oil, phenyl ether and chlorophenesic acid
P-methyl phenol: m
One condensed ethandiol: m
Wintergreen oil: m
Two Phenylate: m
Chlorophenesic acid=2.0: 0.6: 1.5: 1.9: the solvent that constitutes at 5.0: 3.0, stir and form mixture; The heated mixt material make its temperature rise to 180 ℃ and be incubated 5.0 hours after, continue heating again and make material rise to 260 ℃ and be incubated 6.0 hours, obtain containing the mixture of salicylonitrile; Contain the mixture filtered while hot or the centrifugation of salicylonitrile, and with identical hot solvent washing solid filter residue, merging filtrate or centrifugate obtain containing the solution of adjacent oxybenzene formonitrile HCN; The solution that contains salicylonitrile reduced pressure steam remove most of solvent after, crystallization under room temperature or cold condition again, and after filtration or centrifugation obtain the salicylonitrile crude product; The salicylonitrile crude product with 150 the gram press mass ratio 5.0: 2.0: 6.0 by chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF), ethanol, methyl alcohol, ethylene dichloride: 6.0: 6.0: 5.0: 0.6: 2.0 the formation the double solvents recrystallization, and after filtration or centrifugation obtain the salicylonitrile wet stock; Salicylonitrile wet stock 0.09Mpa vacuum tightness and 90 ℃ of dryings 20.0 hours obtain the quality percentage composition and are 96.5% salicylonitrile product.
Claims (9)
1. one kind is the method for feedstock production salicylonitrile with the Salicylate ammonium, it is characterized in that: Whitfield's ointment is scattered in the Whitfield's ointment slip that forms in the water and feeds ammonia or add ammoniacal liquor, and the aqueous solution that contains Salicylate ammonium that at room temperature forms obtains the Salicylate ammonium solid through evaporation concentration under normal pressure or reduced pressure; In organic solvent, Salicylate ammonium solid and urea, thionamic acid and catalyzer are joined in the reactor by the certain mass ratio, behind insulation certain hour under 150～180 ℃, continue to be warming up to 190～260 ℃ of insulation certain hours down again, obtain containing the mixture of salicylonitrile; Contain the mixture filtered while hot or the centrifugation of salicylonitrile, and wash the solid filter residue, obtain containing the solution of adjacent oxybenzene formonitrile HCN with hot solvent; The solution that contains salicylonitrile steams in reduced pressure and carries out rectifying again after desolventizing under reduced pressure and obtain the salicylonitrile crude product, or reduced pressure steam remove most of solvent after again under room temperature or cold condition crystallization obtain the salicylonitrile crude product; Salicylonitrile crude product double solvents recrystallization through cooling, crystallization, centrifugal or filtration, normal pressure or vacuum-drying, obtains the salicylonitrile product again.
2. according to claim 1 a kind of be the method for feedstock production salicylonitrile with the Salicylate ammonium, it is characterized in that: the organic solvent that in the solid mixture material that contains Salicylate ammonium, urea and thionamic acid and catalyzer, adds by ortho-methyl phenol, p-methyl phenol, a condensed ethandiol, wintergreen oil, phenyl ether and chlorophenesic acid by m
Ortho-methyl phenol: m
P-methyl phenol: m
One condensed ethandiol: m
Bigcatkin willow The acid methyl esters: m
Phenyl ether: m
Chlorophenesic acidConstitute at=0.0001～10: 0.0001～6: 0.0001～8: 0.0001～9: 0.0001～10: 0.0001～12.
3. according to claim 1 a kind of be the method for feedstock production salicylonitrile with the Salicylate ammonium, it is characterized in that: the solid mixture that contains Salicylate ammonium, urea and thionamic acid and catalyzer is added the mixture heating that organic solvent forms, and after being incubated 0.5～10.0 hour under 150～180 ℃, continuing to be warming up to 190～260 ℃ again and be incubated 0.5～10.0 hour down.
4. according to claim 1 a kind of be the method for feedstock production salicylonitrile with the Salicylate ammonium, it is characterized in that: the solvent that is used for salicylonitrile crude product recrystallization by chloroform, ethyl acetate, ether, dioxane, tetrahydrofuran (THF), ethanol, methyl alcohol, ethylene dichloride by mass ratio 0.01～10: constitute at 0.001～12: 0.1～10: 0.001～16: 0.001～18: 0.001～5: 0.001～6: 0.001～8.
5. according to claim 1 a kind of be the method for feedstock production salicylonitrile with the Salicylate ammonium, it is characterized in that: the mass ratio of Salicylate ammonium and urea is 0.1～6.0, the mass ratio of Salicylate ammonium and thionamic acid is 0.2～5.0, the mass ratio of Salicylate ammonium and solvent is 0.01～10.0, the mass ratio of Salicylate ammonium and solvent is 0.01～10.0, and the mass ratio of catalyzer and Salicylate ammonium is 0.00001～1.0.
6. according to claim 1 a kind of be the method for feedstock production salicylonitrile with the Salicylate ammonium, it is characterized in that: the mass ratio of Whitfield's ointment and water is 0.01～10 during preparation Whitfield's ointment slip, after feeding ammonia or add ammoniacal liquor in the Whitfield's ointment slip, the pH that finally makes solution is 7.5～13.0.
7. according to claim 1 a kind of be the method for feedstock production salicylonitrile with the Salicylate ammonium, it is characterized in that: during recrystallization, the mass ratio of double solvents and salicylonitrile crude product is 1.0～20.0; The vacuum tightness of salicylonitrile wet stock when carrying out vacuum-drying is that 0.01～0.1MPa, temperature are 10～120 ℃.
8. according to claim 1 a kind of be the method for feedstock production salicylonitrile with the Salicylate ammonium, it is characterized in that: salicylonitrile quality percentage composition is greater than 90% in the dried product.
9. according to claim 1 a kind of be the method for feedstock production salicylonitrile with the Salicylate ammonium, it is characterized in that: catalyzer is pressed m by magnesium oxide, aluminum oxide, calcium oxide, silicon oxide and permutite
Magnesium oxide: m
Aluminum oxide: m
Calcium oxide: m
Silicon oxide: m
Artificial ZeoliteConstitute at=0.0001～10: 0.0001～5: 0.0001～8: 0.0001～8: 0.0001～10.
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| CN103864644A (en) * | 2014-04-04 | 2014-06-18 | 武汉大学 | Method for preparing cyanobenzene by ammonifying benzoic acid gaseous phase |
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