CN111848443A - Preparation method of salicylonitrile - Google Patents
Preparation method of salicylonitrile Download PDFInfo
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- CN111848443A CN111848443A CN201910357118.2A CN201910357118A CN111848443A CN 111848443 A CN111848443 A CN 111848443A CN 201910357118 A CN201910357118 A CN 201910357118A CN 111848443 A CN111848443 A CN 111848443A
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- salicylamide
- salicylonitrile
- thionyl chloride
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- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical compound OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 122
- SKZKKFZAGNVIMN-UHFFFAOYSA-N Salicilamide Chemical compound NC(=O)C1=CC=CC=C1O SKZKKFZAGNVIMN-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229960000581 salicylamide Drugs 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 29
- 239000008096 xylene Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000005070 sampling Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000010998 test method Methods 0.000 claims description 2
- 238000004811 liquid chromatography Methods 0.000 claims 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 abstract description 76
- 239000000047 product Substances 0.000 abstract description 47
- 239000006227 byproduct Substances 0.000 abstract description 7
- 239000012043 crude product Substances 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000010842 industrial wastewater Substances 0.000 abstract description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012024 dehydrating agents Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000005730 Azoxystrobin Substances 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- WFDXOXNFNRHQEC-GHRIWEEISA-N azoxystrobin Chemical compound CO\C=C(\C(=O)OC)C1=CC=CC=C1OC1=CC(OC=2C(=CC=CC=2)C#N)=NC=N1 WFDXOXNFNRHQEC-GHRIWEEISA-N 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KTZQTRPPVKQPFO-UHFFFAOYSA-N 1,2-benzoxazole Chemical compound C1=CC=C2C=NOC2=C1 KTZQTRPPVKQPFO-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910008159 Zr(SO4)2 Inorganic materials 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- BSDQITJYKQHXQR-UHFFFAOYSA-N methyl prop-2-eneperoxoate Chemical compound COOC(=O)C=C BSDQITJYKQHXQR-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- -1 thionyl chloride salicylaldehyde Chemical compound 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/20—Preparation of carboxylic acid nitriles by dehydration of carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
Abstract
The invention provides a preparation method of salicylonitrile, which comprises the following steps: (1) reacting thionyl chloride with a salicylamide solution to generate a crude salicylonitrile product; (2) and (3) adding thionyl chloride into the crude salicylonitrile product, and cooling and crystallizing to obtain the salicylonitrile. The preparation method provided by the invention has the advantages of simple process, high safety, easy control of the reaction process and less impurity byproducts generated in the reaction; particularly, the method for post-treating the crude product is simple and convenient, the separation and purification efficiency is high, the obtained salicylaldehyde is high in yield and purity, the mass percentage of the salicylamide in the salicylaldehyde product is effectively controlled to be lower than 0.5%, the purity of the salicylaldehyde product is up to more than 95%, a large amount of industrial wastewater cannot be generated, and the method is a green, environment-friendly, simple and efficient preparation process of the high-purity salicylaldehyde.
Description
Technical Field
The invention belongs to the technical field of organic compound preparation, and particularly relates to a preparation method of salicylonitrile.
Background
The salicylonitrile, namely the o-hydroxybenzonitrile, is an important chemical intermediate for synthesizing liquid crystal materials, perfumes, pesticides and the like, and particularly a key intermediate for synthesizing methoxy acrylate bactericides such as azoxystrobin, so that the salicylonitrile has wide application in the industrial fields of agrochemicals, medicinal chemicals, high molecular materials, dyes, organic synthesis and the like.
The preparation methods of the currently reported salicylaldehyde are mainly divided into two methods, one is to synthesize the salicylaldehyde by taking salicylaldehyde as a raw material, and the other is to dehydrate the salicylamide as a raw material to generate the salicylaldehyde. The preparation method using salicylaldehyde as a raw material comprises the steps of firstly reacting salicylaldehyde with hydroxylamine hydrochloride under an alkaline condition to obtain salicylaldoxime, and dehydrating the salicylaldoxime by using dehydrating agents such as acetic anhydride and concentrated sulfuric acid to generate salicylaldehyde; in the method, the reaction environment for preparing salicylaldoxime is alkaline, but the salicylaldehyde has poor stability under alkaline conditions, so that the byproducts are increased, and the separation and purification of the product are not facilitated; in addition, in the dehydration process of salicylaldoxime, if concentrated sulfuric acid and the like are used as dehydrating agents, 1, 2-benzisoxazole byproducts are easily generated, the dehydration is incomplete, the yield is low, if acid anhydride is used as the dehydrating agents, a hydrolysis process needs to be added, the post-treatment is relatively complicated, and a large amount of wastewater is generated. In contrast, the preparation method is more convenient and faster by taking salicylamide as a raw material and selecting a proper dehydrating agent to cyanize the amide group of the salicylamide to obtain the salicylaldehyde.
CN106083648A discloses a method for synthesizing salicylamide with high yield, which comprises the steps of mixing salicylamide with a solvent xylene, introducing phosgene at 170-175 ℃ for phosgenation reaction, introducing nitrogen for removing gas after the reaction is finished, and further rectifying to obtain a product; the method accelerates the synthesis rate of the salicylonitrile by heating, reduces the generation of byproducts, and simultaneously recycles and reuses the solvent and the redundant phosgene to reduce the consumption of raw materials.
CN109433230A discloses a preparation method of a solid acid-base bifunctional catalyst for preparing salicylaldehyde by dehydrating salicylamide, wherein the solid catalyst comprises Zr (NO)3)4·5H2O and montmorillonite, in which Zr (NO)3)4·5H2O and montmorillonite carrier after acid treatment are compounded, impregnated and roasted to form catalyst SO4 2-/Zr(SO4)2Montmorillonite with strong Bronsted acid center and weak Bronsted base center, and can reduce the activation energy of reaction in the course of catalytic amide dehydration, so that the reaction can be carried out at lower temperature; the catalyst can catalyze salicylamide at 1The salicylonitrile is generated by the reaction at 10 ℃, and the catalyst is easy to separate and recycle after the reaction is finished.
CN102516122A discloses an environment-friendly method for preparing a DMF solution of o-hydroxybenzonitrile, the DMF solution of o-hydroxybenzonitrile and application thereof, wherein triphosgene and salicylamide are respectively added into DMF for full reaction to obtain more than 98% of o-hydroxybenzonitrile (with solvent being subtracted), the chemical conversion rate and the selectivity are both more than 98%, no polluting waste gas and waste water are discharged in the production process, and residues can be recycled, so that the method is an environment-friendly production process.
However, in the existing technology for preparing the salicylaldehyde, the dehydrating agent phosgene is a highly toxic gas although the reaction activity is high, so that the danger is high in production and the operation difficulty is high; and phosgene has active chemical property, is easy to generate side reactions such as carbonylation, cyclized condensation and the like with nucleophilic reagent containing C, N, O atoms, and has higher requirements on reaction conditions. Although the preparation method adopting the solid catalyst avoids a highly toxic dehydrating agent, the post-reaction treatment needs to use a large amount of organic solvents such as benzene and the like for crystallization and recrystallization, thereby causing higher waste liquid treatment cost. Triphosgene is a solid-phase substitute of phosgene and can react with salicylamide to generate salicylamide, but the residual amount of the salicylamide in the product obtained by the method is high and can reach 3 percent, thereby seriously influencing the subsequent use of the salicylamide, and particularly influencing the product yield and purity when the salicylamide is used for preparing azoxystrobin; the method of repeatedly washing with acid liquor and alkali liquor is commonly used in industry to remove salicylamide in salicylaldehyde, but the method can generate a large amount of industrial waste liquor which is difficult to treat, and causes environmental pollution.
Therefore, the development of a preparation method of high-purity salicylaldehyde which is environment-friendly, has high yield and can effectively control the content of salicylamide is a research focus in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of salicylaldehyde, which is simple in process, does not generate a large amount of industrial three wastes, can ensure that the product salicylaldehyde has higher purity and yield, can control the mass percentage content of salicylamide in the product to be lower than 0.5 percent, has the salicylaldehyde content of more than 95 percent, and is a green, environment-friendly, simple and efficient preparation process of high-purity salicylaldehyde.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of salicylonitrile, which comprises the following steps:
(1) reacting thionyl chloride with a salicylamide solution to generate a crude salicylonitrile product, wherein the reaction formula is as follows:
(2) and (2) adding thionyl chloride into the crude salicylonitrile product obtained in the step (1), and cooling and crystallizing to obtain the salicylonitrile.
The preparation method provided by the invention takes salicylamide as a raw material, takes thionyl chloride as a dehydrating agent, and reacts with the salicylamide to obtain the salicylaldehyde. Compared with the prior art which takes phosgene as a dehydrating agent, the chemical property of thionyl chloride is more stable than that of phosgene, so the reaction process is easy to control, and impurity byproducts generated in the reaction are less; the liquid thionyl chloride is more convenient to operate in production than phosgene, the toxicity is lower, the uncontrollable property of phosgene reaction can be avoided, the side reaction generated by the phosgene reaction can be avoided due to the strong dehydration capacity of the thionyl chloride, the reaction yield is higher, and the leakage risk generated by the highly toxic phosgene is avoided; therefore, the reaction of thionyl chloride and salicylamide is a preparation process which is obviously superior to a phosgene method in safety and operability.
In order to remove salicylamide and obtain high-purity salicylaldehyde by the preparation method, the following steps are surprisingly found: the method of directly adding a proper amount of thionyl chloride into the mixed solution after the reaction for preparing the salicylaldehyde is finished, cooling, crystallizing, filtering and drying is adopted to obtain the high-purity salicylaldehyde which has the salicylamide mass percentage of less than 0.5% and meets the requirement of industrial production.
The preparation method of the high-purity salicylonitrile provided by the invention is simple in process, washing liquor does not need to be added in the post-treatment process for washing for multiple times (such as acid washing, alkali washing and the like), a large amount of cyanide-containing industrial wastewater is avoided, and the preparation method is an environment-friendly preparation process.
The preparation method has the advantages that the yield of the thionyl chloride salicylaldehyde is high, the impurities are few, and the hydrogen chloride and the sulfur dioxide which are the reaction by-products can be recovered through simple purification treatment.
Preferably, the salicylamide solution in the step (1) is a mixed solution of salicylamide and an organic solvent.
Preferably, the organic solvent is selected from any one of xylene, toluene, benzene or chlorobenzene or a combination of at least two of the xylene, and is further preferably xylene.
Preferably, the mass ratio of the salicylamide to the organic solvent is 1 (1-20), such as 1:1.5, 1:2, 1:3, 1:5, 1:7, 1:9, 1:10, 1:12, 1:14, 1:15, 1:17, 1:19 or 1: 20.
Preferably, the molar ratio of thionyl chloride to salicylamide in step (1) is (1-1.5): 1, for example 1.05:1, 1.1:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1, 1.35:1, 1.4:1, 1.45:1 or 1.5: 1.
Preferably, the reaction temperature in step (1) is 100-145 ℃, such as 103 ℃, 105 ℃, 108 ℃, 110 ℃, 113 ℃, 115 ℃, 118 ℃, 120 ℃, 122 ℃, 125 ℃, 128 ℃, 130 ℃, 132 ℃, 135 ℃, 137 ℃, 140 ℃, 143 ℃ or 145 ℃, and the specific values between the above values are limited to the space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the reaction time in step (1) is 1 to 20 hours, such as 1.5 hours, 2 hours, 3 hours, 4 hours, 5 hours, 7 hours, 9 hours, 10 hours, 12 hours, 14 hours, 15 hours, 17 hours, 19 hours or 20 hours, and the specific values between the above values are not exhaustive, and the invention is not limited to the specific values included in the range for brevity and conciseness.
Preferably, the reaction of step (1) is carried out under stirring conditions.
Preferably, the thionyl chloride in the step (1) is added dropwise.
Preferably, the dropping time is 1 to 15 hours, such as 1.5 hours, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or 15 hours, and the specific values between the above values are limited by space and for the sake of brevity, the invention is not exhaustive to list the specific values included in the range.
Preferably, the molar amount of the supplementary thionyl chloride in step (2) is 0.1 to 5% of the molar amount of the salicylamide in step (1), such as 0.1%, 0.3%, 0.5%, 1.7%, 1.9%, 2%, 2.3%, 2.5%, 2.7%, 2.9%, 3%, 3.3%, 3.5%, 3.7%, 4%, 4.2%, 4.5%, 4.7% or 4.9%, and specific values therebetween, limited by space and for brevity, the invention is not exhaustive of the specific values included in the ranges.
The preparation method provided by the invention provides an efficient and simple post-treatment method for the crude product, and the crude product of the salicylaldehyde is purified by adding a small amount of thionyl chloride and cooling and crystallizing.
The preparation method limits the molar quantity of the supplemented thionyl chloride to be 1-5% of the molar quantity of the salicylamide in the step (1), if the thionyl chloride addition is lower than 1%, the salicylamide and the salicylanitrile product cannot be separated, and the content of the salicylamide in the product cannot be reduced to be lower than 0.5%; if the thionyl chloride make-up is above 5%, the yield of the product, salicylonitrile, will also decrease.
Preferably, the temperature of the temperature-reducing crystallization in step (2) is 0 to 10 ℃, for example, 1 ℃, 2 ℃, 3 ℃, 4 ℃, 5 ℃, 6 ℃, 7 ℃, 8 ℃, 9 ℃ or 10 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the reaction of step (1) is terminated at 1.5-3% by mass of salicylamide in the reaction system, such as 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9% or 3%, and the specific values therebetween are limited by space and for brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the test method of the mass percentage content of the salicylamide in the reaction system is as follows: sampling from the reaction system, and determining the mass percent of the salicylamide in the sampling by gas chromatography.
The preparation method can control the mass percentage of the salicylamide in the salicylonitrile product to be lower than 0.5%, so that the purity of the salicylonitrile is up to more than 95%.
Preferably, the preparation method further comprises a filtering and drying step.
Preferably, the preparation method comprises the following steps:
(1) mixing salicylamide and xylene according to a mass ratio of 1 (1-20) to obtain a mixed solution, and dropwise adding thionyl chloride into the mixed solution at 100-145 ℃ under a stirring condition for 1-15 hours; wherein the molar ratio of the thionyl chloride to the salicylamide is (1-1.5) to 1; continuing the reaction for 1-20 h after the dropwise addition is finished, and reaching the reaction end point when the mass percentage of the salicylamide in the reaction system is 1.5-3% to obtain a crude salicylonitrile product;
(2) Adding thionyl chloride into the crude salicylonitrile product obtained in the step (1), and cooling to 0-10 ℃ to obtain crystals; filtering and drying the crystals to obtain a product, namely the salicylonitrile; wherein the molar weight of the supplemented thionyl chloride is 1-5% of the molar weight of the salicylamide in the step (1).
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the salicylamide, the salicylamide and the thionyl chloride react to generate a crude product of the salicylamide, and then the salicylamide is separated and purified by supplementing the thionyl chloride to the crude product and cooling and crystallizing to obtain a high-purity salicylamide product, wherein the mass percentage of the salicylamide in the salicylamide product is effectively controlled to be lower than 0.5%, and the purity of the salicylamide is up to more than 95%.
The preparation method has the advantages of simple process, high safety, easy control of the reaction process and less impurity by-products generated in the reaction; in particular, the method for post-treating the crude product is simple and convenient, the separation and purification efficiency is high, the obtained salicylaldehyde is high in yield and purity, a large amount of industrial wastewater cannot be generated, and the method is a green, environment-friendly, simple and efficient preparation process of the high-purity salicylaldehyde.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of salicylonitrile, which specifically comprises the following steps:
(1) adding 20g of salicylamide and 200g of xylene into a four-neck flask, and stirring and heating to an internal temperature of 105 ℃; then slowly dropwise adding thionyl chloride into the four-neck flask under the stirring condition, wherein the dropwise adding time is 5 hours, and the dropwise adding amount of the thionyl chloride is 20.67 g; after the dropwise addition, continuously preserving the heat at 105 ℃ for 2 hours, sampling and measuring about 2% of residual salicylamide in the reaction system to obtain a reaction end point, and obtaining salicylonitrile xylene solution;
(2) adding 0.21g of thionyl chloride into the salicylonitrile xylene solution obtained in the step (1), cooling to 5 ℃, and crystallizing and separating out the salicylonitrile; the crystals were filtered and dried to obtain 16.33g of the product, salicylaronitrile content 97%, salicylamide residue 0.08%, salicylaronitrile yield 92.1%.
Example 2
The embodiment provides a preparation method of salicylonitrile, which specifically comprises the following steps:
(1) adding 20g of salicylamide and 100g of xylene into a four-neck flask, and stirring and heating to an internal temperature of 125 ℃; then slowly dripping thionyl chloride into the four-neck flask under the stirring condition, wherein the dripping time is 10 hours, and the dripping amount of the thionyl chloride is 24.67 g; after the dropwise addition, continuously preserving the heat at 125 ℃ for 2 hours, sampling and measuring about 2% of residual salicylamide in the reaction system to obtain a reaction end point, and obtaining salicylonitrile xylene solution;
(2) Adding 0.3g of thionyl chloride into the salicylonitrile xylene solution obtained in the step (1), cooling to 8 ℃, and crystallizing and separating out the salicylonitrile; the crystals were filtered and dried to obtain 17.01g of the product salicylaronitrile, with a salicylaronitrile content of 97%, salicylamide residue of 0.11%, and a yield of 95.9%.
Example 3
The embodiment provides a preparation method of salicylonitrile, which specifically comprises the following steps:
(1) adding 20g of salicylamide and 140g of xylene into a four-neck flask, and stirring and heating to an internal temperature of 115 ℃; then slowly dropwise adding thionyl chloride into the four-neck flask under the stirring condition, wherein the dropwise adding time is 4 hours, and the dropwise adding amount of the thionyl chloride is 20.67 g; continuing to keep the temperature at 115 ℃ for 2 hours after the dropwise addition is finished, sampling and measuring about 2% of residual salicylamide in the reaction system to obtain a reaction end point, and obtaining salicylonitrile xylene solution;
(2) adding 0.4g of thionyl chloride into the salicylonitrile xylene solution obtained in the step (1), cooling to 0 ℃, and crystallizing and separating out the salicylonitrile; the crystals were filtered and dried to obtain 16.8g of the product salicylaronitrile, with a salicylaronitrile content of 97.1%, salicylamide residue of 0.21%, yield 94.7%.
Example 4
(1) Adding 20g of salicylamide and 80g of xylene into a four-neck flask, and stirring and heating to an internal temperature of 135 ℃; then slowly dripping thionyl chloride into the four-neck flask under the stirring condition, wherein the dripping time is 8 hours, and the dripping amount of the thionyl chloride is 22.67 g; after the dropwise addition, continuously preserving the heat at 135 ℃ for 2 hours, sampling and measuring about 2% of residual salicylamide in the reaction system to obtain a reaction end point, and obtaining salicylonitrile xylene solution;
(2) Adding 0.5g of thionyl chloride into the salicylonitrile xylene solution obtained in the step (1), cooling to 0 ℃, and crystallizing and separating out the salicylonitrile; the crystals were filtered and dried to obtain 17.24g of the product, salicylaronitrile content 96.8%, salicylamide residue 0.32%, salicylaronitrile yield 97.2%.
Example 5
(1) Adding 20g of salicylamide and 400g of toluene into a four-neck flask, and stirring and heating to an internal temperature of 100 ℃; then slowly dripping thionyl chloride into the four-neck flask under the stirring condition, wherein the dripping time is 10 hours, and the dripping amount of the thionyl chloride is 26.06 g; after the dropwise addition, continuously preserving the heat for 2 hours at 100 ℃, sampling and measuring about 2% of residual salicylamide in the reaction system as a reaction end point to obtain salicylonitrile xylene liquid;
(2) adding 0.17g of thionyl chloride into the salicylonitrile xylene liquid product obtained in the step (1), cooling to 5 ℃, and crystallizing and separating out the salicylonitrile; the crystals were filtered and dried to obtain 17.1g of the product salicylaronitrile, with a salicylaronitrile content of 97.5%, salicylamide residue of 0.3%, and a salicylaronitrile yield of 97.1%.
Example 6
(1) Adding 20g of salicylamide and 200g of chlorobenzene into a four-neck flask, and stirring and heating to an internal temperature of 130 ℃; then slowly dropwise adding thionyl chloride into the four-neck flask under the stirring condition, wherein the dropwise adding time is 20 hours, and the dropwise adding amount of the thionyl chloride is 20.67 g; continuing to keep the temperature at 130 ℃ for 2 hours after the dropwise addition is finished, sampling and measuring about 2% of residual salicylamide in the reaction system to obtain a reaction end point, and obtaining salicylonitrile xylene solution;
(2) Adding 0.52g of thionyl chloride into the salicylonitrile xylene solution obtained in the step (1), cooling to 10 ℃, and crystallizing and separating out the salicylonitrile; the crystals were filtered and dried to obtain 16.7g of the product salicylaronitrile, with a salicylaronitrile content of 97.5%, salicylamide residue of 0.2%, and a salicylaronitrile yield of 94.8%.
Example 7
(1) Adding 20g of salicylamide and 20g of benzene into a four-neck flask, and stirring and heating to an internal temperature of 100 ℃; then slowly dripping thionyl chloride into the four-neck flask under the stirring condition, wherein the dripping time is 1 hour, and the dripping amount of the thionyl chloride is 19.1 g; after the dropwise addition, keeping the temperature at 100 ℃ for 1 hour, sampling and measuring about 2% of residual salicylamide in the reaction system to obtain a reaction end point, and obtaining a salicylonitrile xylene solution;
(2) adding 0.43g of thionyl chloride into the salicylonitrile xylene solution obtained in the step (1), cooling to 5 ℃, and crystallizing and separating out the salicylonitrile; the crystals were filtered and dried to obtain 16.4g of the product salicylaronitrile, with a salicylaronitrile content of 97.6%, salicylamide residue of 0.23%, and a salicylaronitrile yield of 93.2%.
Example 8
This example differs from example 1 in that the amount of thionyl chloride added in step (2) was 0.1g and the other preparation conditions were chosen in the same manner as in example 1 to give 17.3g of the product salicylaronitrile with a content of salicylaronitrile of 97.1%, residual salicylamide of 0.4% and a yield of salicylaronitrile of 97.8%.
Example 9
This example differs from example 1 in that the amount of thionyl chloride added in step (2) was 0.22g and the other preparation conditions were chosen in the same manner as in example 1 to give 17.2g of the product salicylaronitrile with a content of salicylaronitrile of 97.5%, a residual salicylamide of 0.25% and a yield of salicylaronitrile of 97.6%.
Comparative example 1
The difference between the comparative example and the example 1 is that thionyl chloride is not supplemented in the step (2), and direct cooling and crystallization are carried out to obtain 17.2g of the product, the content of the salicylaldehyde is 95.4%, the residual salicylamide is 1.6%, and the yield of the salicylaldehyde is 95.6%.
Comparative example 2
The comparative example provides a preparation method of salicylaldehyde, which specifically comprises the following steps:
(1) adding 20g of salicylamide and 200g of xylene into a four-neck flask, and stirring and heating to an internal temperature of 105 ℃; then slowly dropwise adding thionyl chloride into the four-neck flask under the stirring condition, wherein the dropwise adding time is 5 hours, and the dropwise adding amount of the thionyl chloride is 20.67 g; after the dropwise addition, continuously preserving the heat at 105 ℃ for 2 hours, sampling and measuring about 1.7 percent of residual salicylamide in the reaction system to obtain a reaction end point, and obtaining a salicylonitrile xylene solution;
(2) introducing nitrogen into the reaction system to blow out acid gas, cooling to 5 ℃, and separating out crystals of the salicylonitrile; the crystals were filtered and dried to obtain 17.05g of the product, salicylaronitrile content 95%, salicylamide residue 1.5%, salicylaronitrile yield 94.2%.
Comparative example 3
The comparative example provides a preparation method of salicylaldehyde, which specifically comprises the following steps:
(1) adding 20g of salicylamide and 80g of xylene into a four-neck flask, and stirring and heating to an internal temperature of 135 ℃; then, dropwise adding a toluene solution of solid phosgene into a four-neck flask under the stirring condition, wherein the dropwise adding time is 5 hours, and the dropwise adding amount of the solid phosgene is 18.79 g; after the dropwise addition, continuously preserving the heat at 135 ℃ for 2 hours, sampling and measuring about 2% of residual salicylamide in the reaction system as a reaction end point to obtain a crude salicylonitrile product;
(2) introducing nitrogen into the reaction system to blow out acid gas, cooling to 5 ℃, and separating out crystals of the salicylonitrile; the crystals were filtered and dried to obtain 16.57g of the product salicylaronitrile, with a salicylaronitrile content of 93.5%, salicylamide residue of 2.5%, and a salicylaronitrile yield of 90.2%.
The quality of the salicylaldehyde products prepared in the embodiments 1 to 10 and the comparative examples 1 to 3, the content of the salicylaldehyde in the products, the residual amount of the salicylamide in the products and the yield are specifically tested by the following steps:
(1) the method for testing the content of the salicylonitrile comprises the following steps: liquid phase external standard method, shimadzu LC-20AT high performance liquid chromatography, mobile phase acetonitrile: water 30: 70.
(2) The method for testing the residual quantity of the salicylamide in the product comprises the following steps: liquid phase external standard method, shimadzu LC-20AT high performance liquid chromatography, mobile phase acetonitrile: water 30: 70.
(3) Yield calculation of the salicylanitrile product: (weight of salicylaronitrile/molecular weight of salicylaronitrile)/(weight of salicylamide/molecular weight of salicylamide).
As can be seen from the comparison of examples 1-9 and comparative examples 1-3, salicylamide and thionyl chloride react to generate a crude salicylaldehyde product, and thionyl chloride is supplemented into the crude salicylaldehyde product to realize separation and purification of the product, so that the residual quantity of salicylamide impurities in the product is lower than 0.5%, and the purity of the salicylaldehyde is as high as more than 95%. If the addition amount of the salicylamide in the crude product exceeds the range defined by the invention, the residual amount of the salicylamide impurity in the product is increased, and the purity of the salicylaldehyde is reduced; if thionyl chloride is not supplemented in the crude salicylonitrile product and direct temperature reduction and crystallization are carried out, the residual quantity of salicylamide in the product is higher than 1%, the purity of the salicylonitrile is lower than 95%, and adverse effects are brought to subsequent use of the salicylonitrile.
The applicant states that the present invention is illustrated by the above examples to provide a method for preparing salicylanitrile, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must rely on the above examples to practice the present invention. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of salicylonitrile is characterized by comprising the following steps:
(1) reacting thionyl chloride with a salicylamide solution to generate a crude salicylonitrile product, wherein the reaction formula is as follows:
(2) and (3) adding thionyl chloride into the crude salicylonitrile product obtained in the step (1), and cooling and crystallizing to obtain a salicylonitrile product.
2. The method according to claim 1, wherein the salicylamide solution in the step (1) is a mixed solution of salicylamide and an organic solvent;
preferably, the organic solvent is selected from any one or a combination of at least two of xylene, toluene, benzene or chlorobenzene, and is further preferably xylene;
preferably, the mass ratio of the salicylamide to the organic solvent is 1 (1-20).
3. The preparation method according to claim 1 or 2, wherein the molar ratio of the thionyl chloride to the salicylamide in the step (1) is (1-1.5): 1.
4. The method according to any one of claims 1 to 3, wherein the reaction temperature in step (1) is 100 to 145 ℃;
preferably, the reaction time in the step (1) is 1-20 h;
preferably, the reaction of step (1) is carried out under stirring conditions.
5. The process according to any one of claims 1 to 4, wherein the thionyl chloride in the step (1) is added dropwise;
preferably, the dripping time is 1-15 h.
6. The method according to any one of claims 1 to 5, wherein the molar amount of the additional thionyl chloride in the step (2) is 0.1 to 5% of the molar amount of the salicylamide in the step (1).
7. The preparation method according to any one of claims 1 to 6, wherein the temperature of the temperature-reducing crystallization in the step (2) is 0 to 10 ℃.
8. The preparation method according to any one of claims 1 to 7, wherein the end point of the reaction in the step (1) is that the mass percentage of the salicylamide in the reaction system is 1.5 to 3%;
preferably, the test method of the mass percentage content of the salicylamide in the reaction system is as follows: sampling from the reaction system after the reaction in the step (1), and determining the mass percentage of the salicylamide in the sample by liquid chromatography;
preferably, the preparation method further comprises a filtering and drying step after the temperature reduction and crystallization in the step (2).
9. The preparation method according to any one of claims 1 to 8, wherein the mass percentage of salicylamide in the salicylaronitrile product is less than 0.5%.
10. The method according to any one of claims 1 to 9, characterized by comprising the steps of:
(1) mixing salicylamide and xylene according to a mass ratio of 1 (1-20) to obtain a mixed solution, and dropwise adding thionyl chloride into the mixed solution at 100-145 ℃ under a stirring condition for 1-15 hours; wherein the molar ratio of the thionyl chloride to the salicylamide is (1-1.5) to 1; continuing the reaction for 1-20 h after the dropwise addition is finished, and reaching the reaction end point when the mass percentage of the salicylamide in the reaction system is 1.5-3% to obtain a crude salicylonitrile product;
(2) adding thionyl chloride into the crude salicylonitrile product obtained in the step (1), and cooling to 0-10 ℃ to obtain crystals; filtering and drying the crystals to obtain a product, namely the salicylonitrile; wherein the molar weight of the supplemented thionyl chloride is 1-5% of the molar weight of the salicylamide in the step (1).
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| CN112521308A (en) * | 2020-12-01 | 2021-03-19 | 山东国邦药业有限公司 | Synthesis method of dichloroacetonitrile |
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