CN108610267A - A kind of pinacolone oxime synthetic method - Google Patents

A kind of pinacolone oxime synthetic method Download PDF

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Publication number
CN108610267A
CN108610267A CN201810619819.4A CN201810619819A CN108610267A CN 108610267 A CN108610267 A CN 108610267A CN 201810619819 A CN201810619819 A CN 201810619819A CN 108610267 A CN108610267 A CN 108610267A
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China
Prior art keywords
pinacolone
synthetic method
catalyst
kettle
oxime
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CN201810619819.4A
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Chinese (zh)
Inventor
王庆吉
王建青
王蕊
李进
王炳春
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Dalian Heterogeneous Catalyst Co Ltd
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Dalian Heterogeneous Catalyst Co Ltd
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Priority to CN201810619819.4A priority Critical patent/CN108610267A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a kind of pinacolone oxime synthetic methods, it is characterised in that puts into reaction kettle pinacolone, solvent and 1 catalyst of TS, is warming up in kettle 70 DEG C.20% ammonium hydroxide and 27.5%H is added dropwise into kettle simultaneously2O2Ammoxidation reaction is carried out, is added dropwise and was completed at 2 hours, 70 DEG C is kept the temperature and reacts 3 hours.Heat filtering obtains mother liquor cooling and solid is precipitated, then the product pinacolone oxime being filtered.The present invention controls H well2O2Decomposition, improve H2O2Effective rate of utilization, and raw material pinacolone oxime conversion ratio can be made to have reached 99.8% or more.And step is simple, and raw material is easy to get, and solvent for use and waste water can recycle, it is friendly to environment the features such as.

Description

A kind of pinacolone oxime synthetic method
Technical field
The invention belongs to fine chemistry industry synthetic methods, are related to the synthetic method of pinacolone oxime.
Background technology
Pinacolone oxime, also known as oxidation pinacolone, 3,3- dimethyl-2-butanone oximes, are white crystal under room temperature, fusing point, close Degree, boiling point be respectively 76-78 DEG C, 0.86g/cm3,172 DEG C.Ketoxime is a kind of important industrial chemicals, is the pass for producing amide Key intermediate, ketoxime can occur Beckmann rearrangement and obtain amide in acid condition, and pinacolone oxime is also rearrangeable to obtain N- methyl - 2,2- dimethylpropionamides.
Ammoximation reaction about ketone can usually select cyclic ketones class or straight chain ketone as reaction raw materials, patent It is all referred in US4410501, US4968842, US5227525, US5312987 and US6828459 oximes with the progress of cyclic ketones class Reaction.However, the related patents of the Ammoximation reaction about straight chain ketone are very few, patent CN1706818 and CN101318912 Middle introduction is a kind of to be aoxidized using TS-1 molecular sieve catalytics to prepare straight chain ketoxime, and still, the ketoxime yield of the patent is bad.
The preparation method of different types of ketoxime is reported at present, but there are no the synthesis sides of specific pinacolone oxime Method.
Invention content
The purpose of the present invention is to provide a kind of economical and effective, easy to operate, raw materials to be easy to get, wastewater flow rate is small, to environment friend The preparation method of kind, high yield high-purity pinacolone oxime.With overcome it is existing to prepare wastewater flow rate present in pinacolone oxime big, instead Answer the period is long and yield low-purity is low to wait technical barriers.
The present invention provides a kind of pinacolone oxime synthetic method, and pinacolone, solvent and TS-1 catalyst are put into reaction kettle, 70~75 DEG C are warming up in kettle.Ammonium hydroxide and H is added dropwise into kettle simultaneously2O2It is reacted, is added dropwise and was completed at 1~3 hour, heat preservation 70 ~75 DEG C are reacted 1~3 hour.Heat filtering separating catalyst recycles, and obtains mother liquor cooling and solid is precipitated, then be filtered drying Obtain product pinacolone oxime.
Pinacolone oxime prepares reaction equation：
Further, in the above-mentioned technical solutions, the solvent is acetonitrile.
Further, in the above-mentioned technical solutions, the TS-1 catalyst is Titanium Sieve Molecular Sieve, and catalyst charge is frequency 5~15%Wt of ketone；
Further, in the above-mentioned technical solutions, the ammonia concn is 20%Wt, H2O2A concentration of 27.5~50%Wt；
Further, in the above-mentioned technical solutions, the ratio is according to the molar ratio：Pinacolone：Ammonia：H2O2=1：1~2：1 ~1.5；
Further, in the above-mentioned technical solutions, the solvent is acetonitrile, and addition is：Acetonitrile：Pinacolone=3~5:1 (mass ratio)；
Further, in the above-mentioned technical solutions, the reaction temperature control is at 70~75 DEG C；
Further, in the above-mentioned technical solutions, H is controlled2O2And the time for adding of ammonium hydroxide was completed at 3 hours, when reaction Between at 1 hour；
Further, in the above-mentioned technical solutions, the heat filtering is controlled at 50~55 DEG C；
Further, in the above-mentioned technical solutions, solid is precipitated in the cooling, and control kettle temperature is at 0~5 DEG C；
Further, in the above-mentioned technical solutions, the drying temperature is 80 DEG C of ﹤.
The present invention controls H well2O2Decomposition, H2O2Effective rate of utilization reach 99.8, and raw material pinacolone can be made Oxime conversion ratio has reached 99.8% or more.
Description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure for the product that embodiment obtains.
Specific implementation mode
Embodiment 1
100.16g pinacolones, 300.5g acetonitriles and 5g TS-1 catalyst are put into reaction bulb, are warming up to 70 DEG C, simultaneously 102g20% ammonium hydroxide and 130.9g27.5%H is added dropwise2O2, it is added dropwise to complete within 2 hours, keeps that kettle temperature is constant is reacted 3 hours at 70 DEG C. Kettle temperature is dropped to 50~55 DEG C and filters out catalyst while hot, mother liquor is obtained and continues to cool to 0~5 DEG C, filtering, 80 DEG C of dryings must produce Object is confirmed as target product pinacolone oxime (see Fig. 1) by nucleus magnetic hydrogen spectrum, the results are shown in Table one.
Embodiment 2
100.16g pinacolones, 300.5g acetonitriles and 5g TS-1 catalyst are put into reaction bulb, are warming up to 70 DEG C, simultaneously 102g20% ammonium hydroxide and 130.9g27.5%H is added dropwise2O2, it is added dropwise to complete within 3 hours, keeps that kettle temperature is constant is reacted 3 hours at 75 DEG C. Kettle temperature is dropped to 50~55 DEG C and filters out catalyst while hot, mother liquor is obtained and continues to cool to 0~5 DEG C, filtering, 80 DEG C of dryings must produce Object pinacolone oxime, the results are shown in Table one.
Embodiment 3
100.16g pinacolones, 300.5g acetonitriles and 5g TS-1 catalyst are put into reaction bulb, are warming up to 70 DEG C, simultaneously 102g20% ammonium hydroxide and 130.9g27.5%H is added dropwise2O2, it is added dropwise to complete within 2 hours, keeps that kettle temperature is constant is reacted 3 hours at 60 DEG C. Kettle temperature is dropped to 50~55 DEG C and filters out catalyst while hot, mother liquor is obtained and continues to cool to 0~5 DEG C, filtering, 80 DEG C of dryings must produce Object pinacolone oxime, the results are shown in Table one.
Embodiment 4
100.16g pinacolones, 300.5g acetonitriles and 5g TS-1 catalyst are put into reaction bulb, are warming up to 80 DEG C, simultaneously 102g20% ammonium hydroxide and 130.9g27.5%H is added dropwise2O2, it is added dropwise to complete within 2 hours, keeps that kettle temperature is constant is reacted 3 hours at 80 DEG C. Kettle temperature is dropped to 50~55 DEG C and filters out catalyst while hot, mother liquor is obtained and continues to cool to 0~5 DEG C, filtering, 80 DEG C of dryings must produce Object pinacolone oxime, the results are shown in Table one.
Embodiment 5
100.16g pinacolones, 300.5g acetonitriles and 5g TS-1 catalyst are put into reaction bulb, are warming up to 70 DEG C, simultaneously 102g20% ammonium hydroxide and 133.5g27.5%H is added dropwise2O2, it is added dropwise to complete within 2 hours, keeps that kettle temperature is constant is reacted 3 hours at 70 DEG C. Kettle temperature is dropped to 50~55 DEG C and filters out catalyst while hot, mother liquor is obtained and continues to cool to 0~5 DEG C, filtering, 80 DEG C of dryings must produce Object pinacolone oxime, the results are shown in Table one.
Embodiment 6
100.16g pinacolones, 300.5g acetonitriles and 5g TS-1 catalyst are put into reaction bulb, are warming up to 70 DEG C, simultaneously 85g20% ammonium hydroxide and 130.9g27.5%H is added dropwise2O2, it is added dropwise to complete within 2 hours, keeps that kettle temperature is constant is reacted 3 hours at 70 DEG C.It will Kettle temperature drops to 50~55 DEG C and filters out catalyst while hot, obtains mother liquor and continues to cool to 0~5 DEG C, filtering, 80 DEG C of dryings obtain product Pinacolone oxime, the results are shown in Table one；The present embodiment is comparative example, and the tripping in amount of ammonia is less.
Embodiment 7
100.16g pinacolones, 300.5g acetonitriles and 5g TS-1 catalyst are put into reaction bulb, are warming up to 70 DEG C, simultaneously 102g20% ammonium hydroxide and 72g50%H is added dropwise2O2, it is added dropwise to complete within 2 hours, keeps that kettle temperature is constant is reacted 3 hours at 70 DEG C.By kettle temperature It drops to 50~55 DEG C and filters out catalyst while hot, obtain mother liquor and continue to cool to 0~5 DEG C, filtering, 80 DEG C of dryings obtain product frequency Ketoxime the results are shown in Table one.
Embodiment 8
100.16g pinacolones, 300.5g acetonitriles and 5g TS-1 catalyst are put into reaction bulb, are warming up to 70 DEG C, simultaneously 127.5g20% ammonium hydroxide and 130.9g27.5%H is added dropwise2O2, it is added dropwise to complete within 2 hours, keeps the constant reaction 3 at 70 DEG C of kettle temperature small When.Kettle temperature is dropped to 50~55 DEG C and filters out catalyst while hot, mother liquor is obtained and continues to cool to 0~5 DEG C, filtering, 80 DEG C of dryings obtain Product pinacolone oxime, the results are shown in Table one.
Embodiment 9
100.16g pinacolones, 200.3g acetonitriles and 5g TS-1 catalyst are put into reaction bulb, are warming up to 70 DEG C, simultaneously 102g20% ammonium hydroxide and 130.9g27.5%H is added dropwise2O2, it is added dropwise to complete within 2 hours, keeps kettle temperature is constant to be reacted 3 hours 70.It will Kettle temperature drops to 50~55 DEG C and filters out catalyst while hot, obtains mother liquor and continues to cool to 0~5 DEG C, filtering, 80 DEG C of dryings obtain product Pinacolone oxime, the results are shown in Table one.
Embodiment 10
100.16g pinacolones, 500.8g acetonitriles and 5g TS-1 catalyst are put into reaction bulb, are warming up to 70 DEG C, simultaneously 102g20% ammonium hydroxide and 130.9g27.5%H is added dropwise2O2, it is added dropwise to complete within 2 hours, keeps that kettle temperature is constant is reacted 3 hours at 70 DEG C. Kettle temperature is dropped to 50~55 DEG C and filters out catalyst while hot, mother liquor is obtained and continues to cool to 0~5 DEG C, filtering, 80 DEG C of dryings must produce Object pinacolone oxime, the results are shown in Table one.
Embodiment 11
100.16g pinacolones, 300.5g acetonitriles and 5g TS-1 catalyst are put into reaction bulb, are warming up to 70 DEG C, simultaneously 102g20% ammonium hydroxide and 130.9g27.5%H is added dropwise2O2, it is added dropwise to complete within 1 hour, keeps that kettle temperature is constant is reacted 3 hours at 70 DEG C. Kettle temperature is dropped to 50~55 DEG C and filters out catalyst while hot, mother liquor is obtained and continues to cool to 0~5 DEG C, filtering, 80 DEG C of dryings must produce Object pinacolone oxime, the results are shown in Table one.
Embodiment 12
100.16g pinacolones, 300.5g acetonitriles and 5g TS-1 catalyst are put into reaction bulb, are warming up to 70 DEG C, simultaneously 102g20% ammonium hydroxide and 130.9g27.5%H is added dropwise2O2, it is added dropwise to complete within 3 hours, keeps that kettle temperature is constant is reacted 3 hours at 70 DEG C. Kettle temperature is dropped to 50~55 DEG C and filters out catalyst while hot, mother liquor is obtained and continues to cool to 0~5 DEG C, filtering, 80 DEG C of dryings must produce Object pinacolone oxime, the results are shown in Table one.
Table one：

Claims (10)

1. a kind of pinacolone oxime synthetic method, it is characterised in that put into reaction kettle pinacolone, solvent and TS-1 catalyst, rise 70~75 DEG C in temperature to kettle；Ammonium hydroxide and H is added dropwise into kettle simultaneously2O2It is reacted, keeps the temperature 70~75 DEG C and react 1~3 hour；Heat It is separated by filtration catalyst circulation use, mother liquor cooling is obtained and solid is precipitated, then be filtered and dry to obtain product pinacolone oxime.
2. a kind of synthetic method of pinacolone oxime according to claim 1, which is characterized in that the TS-1 catalyst is titanium Si molecular sieves, catalyst charge are 5~15%Wt of pinacolone.
3. a kind of synthetic method of pinacolone oxime according to claim 1, which is characterized in that the ammonia concn is 20% Wt, H2O2A concentration of 27.5~50%Wt.
4. a kind of synthetic method of pinacolone oxime according to claim 1, which is characterized in that the ratio is in molar ratio Meter：Pinacolone：Ammonia：H2O2=1：1~2：1~1.5.
5. a kind of synthetic method of pinacolone oxime according to claim 1, which is characterized in that the solvent is acetonitrile, is added Entering amount mass ratio is：Acetonitrile：Pinacolone=3~5:1.
6. a kind of synthetic method of pinacolone oxime according to claim 1, which is characterized in that the reaction temperature control exists 70~75 DEG C.
7. a kind of synthetic method of pinacolone oxime according to claim 1, which is characterized in that control H2O2And the drop of ammonium hydroxide It was completed at 1~3 hour between added-time.
8. a kind of synthetic method of pinacolone oxime according to claim 1, which is characterized in that the heat filtering, control exist 50~55 DEG C.
9. a kind of synthetic method of pinacolone oxime according to claim 1, which is characterized in that solid is precipitated in the cooling, Kettle temperature is controlled at 0~5 DEG C.
10. a kind of synthetic method of hydroxylamine hydrochloride according to claim 1, which is characterized in that the drying temperature is ﹤ 80 ℃。
CN201810619819.4A 2018-06-15 2018-06-15 A kind of pinacolone oxime synthetic method Pending CN108610267A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85101577A (en) * 1984-05-17 1987-01-10 拜尔股份公司 The biologically active agent and the manufacture method thereof that contain isoxazolidine
WO2006064340A2 (en) * 2004-12-13 2006-06-22 Pfizer Limited Process for the preparation of n-acyl beta-aminoaldehydes
CN101143839A (en) * 2007-08-16 2008-03-19 华东师范大学 Synthesizing method for oxime
CN205562490U (en) * 2016-01-18 2016-09-07 中触媒新材料股份有限公司 Device of cyclohexanone oxime ization reaction evaluation catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85101577A (en) * 1984-05-17 1987-01-10 拜尔股份公司 The biologically active agent and the manufacture method thereof that contain isoxazolidine
WO2006064340A2 (en) * 2004-12-13 2006-06-22 Pfizer Limited Process for the preparation of n-acyl beta-aminoaldehydes
CN101143839A (en) * 2007-08-16 2008-03-19 华东师范大学 Synthesizing method for oxime
CN205562490U (en) * 2016-01-18 2016-09-07 中触媒新材料股份有限公司 Device of cyclohexanone oxime ization reaction evaluation catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
卢福军等: "肟的合成及其水解制备盐酸羟胺的新工艺", 《中国优秀硕士学位论文全文数据库 工程科技第I辑》 *

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