CN115772094A - Oximation method of cyclododecanone - Google Patents
Oximation method of cyclododecanone Download PDFInfo
- Publication number
- CN115772094A CN115772094A CN202111049134.9A CN202111049134A CN115772094A CN 115772094 A CN115772094 A CN 115772094A CN 202111049134 A CN202111049134 A CN 202111049134A CN 115772094 A CN115772094 A CN 115772094A
- Authority
- CN
- China
- Prior art keywords
- cyclododecanone
- hexafluorophosphate
- oximation
- reaction
- hydroxylamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 238000006146 oximation reaction Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 32
- -1 alkyl glycoside Chemical class 0.000 claims abstract description 100
- SCRFXJBEIINMIC-UHFFFAOYSA-N n-cyclododecylidenehydroxylamine Chemical compound ON=C1CCCCCCCCCCC1 SCRFXJBEIINMIC-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229930182470 glycoside Natural products 0.000 claims abstract description 18
- 239000002608 ionic liquid Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 230000035484 reaction time Effects 0.000 claims abstract description 12
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 16
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 150000002443 hydroxylamines Chemical class 0.000 claims description 10
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims description 9
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 9
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Chemical compound CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000006073 displacement reaction Methods 0.000 claims description 8
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229940032094 squalane Drugs 0.000 claims description 6
- 230000008707 rearrangement Effects 0.000 claims description 5
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 claims description 4
- HYYHQASRTSDPOD-UHFFFAOYSA-N hydroxylamine;phosphoric acid Chemical compound ON.OP(O)(O)=O HYYHQASRTSDPOD-UHFFFAOYSA-N 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- SFVWPXMPRCIVOK-UHFFFAOYSA-N cyclododecanol Chemical compound OC1CCCCCCCCCCC1 SFVWPXMPRCIVOK-UHFFFAOYSA-N 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000005649 metathesis reaction Methods 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 1
- 229940043375 1,5-pentanediol Drugs 0.000 claims 1
- 229940051250 hexylene glycol Drugs 0.000 claims 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims 1
- 238000010626 work up procedure Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 238000006386 neutralization reaction Methods 0.000 description 11
- 238000004255 ion exchange chromatography Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000006462 rearrangement reaction Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 3
- 229920000299 Nylon 12 Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- PLUHAVSIMCXBEX-UHFFFAOYSA-N azane;dodecyl benzenesulfonate Chemical compound N.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 PLUHAVSIMCXBEX-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- DJESEHBVKKBTMM-UHFFFAOYSA-N cyclododecanimine Chemical compound N=C1CCCCCCCCCCC1 DJESEHBVKKBTMM-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Classifications
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an oximation method of cyclododecanone, which comprises the step of carrying out oximation reaction on the cyclododecanone and hydroxylamine under the condition of adding an ionic liquid catalyst and alkyl glycoside to generate the cyclododecanone oxime. By adopting the method, the oximation reaction time of the cyclododecanone can be reduced to be within 1h, and the selectivity of the cyclododecanone oxime can reach more than 99.5 percent.
Description
Technical Field
The invention relates to an oximation method, in particular to an oximation method of cyclododecanone, belonging to the technical field of organic synthesis.
Background
The nylon 12 material is widely applied to various fields of automobile fuel pipes, air brake hoses, submarine cables, 3D printing and the like, the main production process is an oximation method, and the technical barrier is high internationally. The oxidation oximation method for producing nylon 12 needs 7 steps of trimerization, catalytic hydrogenation, oxidation, ketonization, oximation, beckmann rearrangement, ring-opening polymerization and the like, and most of the manufacturers represented by winning companies adopt the process at present.
The invention relates to an oximation method of cyclododecanone, which uses cyclododecanone to react with hydroxylamine salt to generate cyclododecanone oxime, wherein the hydroxylamine salt is derived from sulfate, hydrochloride or phosphate of hydroxylamine. Because the water solubility of the cyclododecanone is poor, the reaction of the cyclododecanone and the hydroxylamine salt is an interfacial reaction, the reaction rate is low, the production efficiency is low, and the equipment investment is large; meanwhile, the low reaction rate causes free ammonia in the system to further react with cyclododecanone to generate cyclododecanimine, and the reaction selectivity is low.
In order to improve the oximation reaction rate, in patent CN102906065A, carboxylic acid or carboxylate is used as a catalyst to improve the oximation reaction rate, the oximation reaction time is reduced from more than 15 hours to 4-7 hours, but the oximation reaction rate is still low; in patent CN1367166A, ammonium salt or substituted ammonium salt is used as a catalyst, so that the oximation reaction rate is improved and is still more than 2 h; patent CN1860098A reports that alkyl sulfonate is used as a phase transfer catalyst, but the oximation reaction time is still more than 8 h; patent CN108218742A uses azolyl anion functionalized ionic liquid as a catalyst to catalyze the reaction of ketone and hydroxylamine hydrochloride, the reaction time is 1.5-4.5h, but when the reaction time is shorter, the product yield is obviously reduced.
Therefore, the development of a catalyst system capable of further improving the oximation reaction rate and the cyclododecanone oxime selectivity has important significance for improving the whole process of nylon 12.
Disclosure of Invention
In order to solve the technical problems, the invention provides an oximation method of cyclododecanone, which has improved oximation reaction rate and cyclododecanone oxime selectivity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an oximation method of cyclododecanone is characterized in that the method is used for carrying out oximation reaction on the cyclododecanone and hydroxylamine under the condition of adding an ionic liquid catalyst and alkyl glycoside to generate the cyclododecanone oxime.
In the present invention, as a specific embodiment, the ionic liquid catalyst is a non-metal ionic liquid, preferably a hexafluorophosphate ionic liquid, more preferably tetraethylphosphonium hexafluorophosphate, N-butylpyridinium hexafluorophosphate, diphenyliodonium hexafluorophosphate, 1-methylpyridinium hexafluorophosphate, tri-p-tolylsulfonium hexafluorophosphate, chlorodipiperidinium hexafluorophosphate, 5-azoniaspiro [4.4] nonane hexafluorophosphate, tripyrrolidinyl phosphonium bromide hexafluorophosphate, chlorotriazolyl phosphonium hexafluorophosphate, 1-butyl-1-methylpyrrolidine hexafluorophosphate, 4-isobutylphenyl-4' -methylphenyliodiophosphate, N-hexylpyridinium hexafluorophosphate, tetrabutylphosphonium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3-methylimidazolium hexafluorophosphate, 2-fluoro-1, 3-dimethylimidazolium hexafluorophosphate, 1-vinyl-3-butylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium hexafluorophosphate, and still more preferably N-hexylphosphonium hexafluorophosphate.
In the present invention, as a specific embodiment, the alkyl glycoside has a saccharide polymerization degree of 1 to 3, preferably 1.2 to 2, an alkyl carbon number of 6 to 18, preferably 8 to 14; the alkyl glycoside is preferably one or more of Glucopon215UP, glucopon225DK, glucopon425N/HH, glucopon600CSUP, glucopon650EC, APG1214, APG0810 and APG0814, and more preferably APG1214 and Glucopon600CSUP.
In the present invention, as a specific embodiment, the hydroxylamine is obtained by neutralizing hydroxylamine salt aqueous solution with dropwise ammonia water; the hydroxylamine salt is one or more of hydroxylamine sulfate, hydroxylamine hydrochloride and hydroxylamine phosphate, and the hydroxylamine sulfate is preferred;
preferably, the concentration of the aqueous solution of hydroxylamine salt is 5-40%, preferably 10-30%; the concentration of the ammonia water is 10-50%, preferably 20-30%.
Preferably, the molar amount of the ammonia water is equal to the molar amount of the hydroxylamine radical ions in the hydroxylamine salt solution.
In the invention, as a specific embodiment, the addition amount of the ionic liquid catalyst is 0.01-1%, preferably 0.1-0.5% of the mass of the cyclododecanone; the addition amount of the alkyl glycoside is 0.05-1%, preferably 0.2-0.5% of the mass of the cyclododecanone.
In the present invention, as a specific embodiment, the molar ratio of hydroxylamine to cyclododecanone is (1.1-2.2): 1, preferably (1.3-1.5): 1.
In the present invention, as a specific embodiment, the reaction solvent of the oximation reaction is a saturated alcohol, preferably one or more of methanol, ethanol, n-propanol, isopropanol, propylene glycol, n-butanol, t-butanol, butanediol, pentanediol, pentanol, hexanediol, n-octanol, isooctanol, decanediol, cyclohexanol, and cyclododecanol, and more preferably isopropanol and t-butanol.
In the present invention, as a specific embodiment, the amount of the reaction solvent added is 3 to 10 times, preferably 4 to 6 times, the mass of cyclododecanone.
In the present invention, as a specific embodiment, the reaction conditions of the oximation reaction are: the reaction temperature is 90-100 ℃, and the reaction time is 0.5-1h.
The ionic liquid is used as an oximation reaction catalyst, the possible catalytic mechanism of the ionic liquid is shown as the following formula, the negative ions of the ionic liquid provide electrons for hydroxylamine, the positive ions attract the electrons on cyclododecanone oxygen atoms, and then nucleophilic reaction is promoted, and meanwhile, fluorine atoms have strong polarity, so that reaction dehydration can be promoted, and the oximation reaction is promoted. The alkyl glycoside has strong hydrophilic and lipophilic effects, can bring cyclododecanone into a water phase, and can bring hydroxylamine into an oil phase, thereby accelerating the oximation reaction speed; meanwhile, hydrogen atoms of a macrocyclic hydrophilic head of the alkyl glycoside and fluorine atoms of hexafluorophosphate radicals have hydrogen bonds, so that the oil solubility of hexafluorophosphate radicals ions can be improved, the combination of the hexafluorophosphate radicals with cyclododecanone and cyclododecanone oxime intermediates in an oil phase is improved, the dehydration efficiency is improved, the oximation reaction is promoted, the surface tension of a system can be synergistically reduced, and the reaction efficiency is improved.
In addition, saturated alcohol as polar solvent can raise oximation reaction rate in the present invention system, but sulfuric acid is used in the rearrangement step after oximation, and alcohol and sulfuric acid can produce serious carbonization reaction, so that the reaction liquid can not be directly fed into the rearrangement step for utilization. In order to directly apply the reaction solution to the rearrangement process, preferably, the method of the present invention further comprises the following post-reaction treatment processes:
separating oil from water after the reaction is finished; adding a displacement solvent into the oil phase, rectifying at normal pressure, extracting a reaction solvent from the top of the tower, obtaining a displacement solution containing cyclododecanone oxime from the bottom of the tower, and sending the displacement solution into a subsequent rearrangement process;
preferably, the metathesis solvent is one or more of methylcyclohexane, ethylcyclohexane, isopropylcyclohexane, dimethylcyclohexane, toluene, ethylbenzene, cumene, cyclododecane, decalin and squalane, preferably decalin, squalane;
preferably, the amount of the displacement solvent is 3 to 20 times, preferably 5 to 10 times, the mass of the cyclododecanone;
preferably, the atmospheric distillation conditions are 10-15 plates, reflux ratio of 0.5-2 and tower bottom temperature of 120-200 ℃.
The method can effectively improve the oximation reaction rate and the selectivity of the cyclododecanone oxime, can reduce the oximation reaction time of the cyclododecanone to be within 1h, and simultaneously can achieve the selectivity of the cyclododecanone oxime to be more than 99.5 percent.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The detection method adopted by the invention is as follows:
(1) Gas chromatography
The conversion rate and selectivity are determined by using gas chromatography area correction normalized analysis, and the chromatographic analysis conditions are as follows:
the instrument model is as follows: shimadzu GC2010; and (3) chromatographic column: DB-5 (30X 0.32X 0.25); column temperature: temperature programming (keeping at 60 ℃ for 5min, then raising the temperature to 100 ℃ at the temperature raising rate of 5 ℃/min, then raising the temperature to 300 ℃ at the temperature raising rate of 30 ℃/min, and keeping for 5 min); sample inlet temperature: 250 ℃; FID temperature: 300 ℃; n is a radical of 2 Flow rate: 1mL/min; h 2 Flow rate: 40mL/min; shock insulator purging (N) 2 ) Flow rate: 3mL/min; carrier gas (N) 2 ) Flow rate: 1mL/min; split-flow sample introduction, split-flow ratio: 50; sample injection amount: 0.05. Mu.L.
(2) Ion chromatography
The invention uses ion chromatography to analyze the distribution condition of hexafluorophosphate in two phases of oximated oil and water, and the ion chromatography type is as follows: swiss wangtong IC881, rinse: 0.001mol/L benzoic acid, flow rate of 1mL/min, and chromatographic column temperature of 40 ℃.
The main raw material information is as follows:
cyclododecanone: basf, CAS:830-13-7
N-hexylpyridinium hexafluorophosphate: west ann qiyue biotechnology limited, CAS:797789-00-5 tetrabutylphosphonium hexafluorophosphate: TCI, CAS:111928-21-3
1-butyl-3-methylimidazolium hexafluorophosphate: shanghai yu chemical limited, CAS:174501-64-5
Diphenyliodonium hexafluorophosphate: shanghai mairei chemical technology limited, CAS:58109-40-3
Tri-p-tolyl sulfonium hexafluorophosphate: shanghai xiandin Biotechnology Co., ltd., CAS:146062-15-9
Chlorotriazolylphosphonium hexafluorophosphate: TCI, CAS:133894-48-1
Glucopon600CSUP: alkyl glycoside, polymerization degree of 1.4, alkyl carbon number of 12-14, basf
APG1214: alkyl glycoside, polymerization degree of 1.4-1.8, alkyl carbon number of 12-14, morning share
Glucopon225DK: alkyl glycoside, polymerization degree of 1.7, alkyl carbon number of 8-10, basf
Glucopon215UP: alkyl glycoside, polymerization degree of 1.5, alkyl carbon number of 8-10, basf
APG0814: alkyl glycoside, polymerization degree of 1.4-1.8, alkyl carbon number of 8-14, morning share
APG0810: alkyl glycoside, polymerization degree of 1.4-1.8, alkyl carbon number of 8-10, morning share
Hydroxylamine sulfate: jiangsu Aikov science and technology, inc., CAS:10039-54-0
And (3) hydroxylamine hydrochloride: jiangsu Aikov science and technology, inc., CAS:5470-11-1
Hydroxylamine phosphate: hubei Yunw technologies, inc., CAS:20845-01-6
Tetrabutylphosphine benzotriazole salt: TCI, CAS:109348-55-2
Example 1
Adding 20g of cyclododecanone, 60g of isopropanol, 0.2g of N-hexylpyridine hexafluorophosphate and 0.01g of Glucopon600CSUP into a 0.5L reaction kettle, stirring and mixing, and heating to 90 ℃;
18.02g of hydroxylamine sulfate was dissolved in 27.03g of water, and the solution was neutralized with 37.36g of 10wt% aqueous ammonia, preheated to 70 ℃ after neutralization, and added to the reaction solution at once, and the reaction was started.
After the reaction is carried out for 0.5h, stopping stirring, carrying out oil-water separation, and testing the content of hexafluorophosphate ions in the oil phase to be 89.37% by ion chromatography; the oil phase was taken for gas phase analysis, the conversion of cyclododecanone was 99.87%, and the selectivity of cyclododecanone oxime was 99.92%.
Adding 60g of decalin into the oil phase, and carrying out normal pressure rectification under the following rectification conditions: the number of tower plates is 10, the reflux ratio is 1, and the tower bottom temperature is 180-200 ℃; the isopropanol is extracted from the tower top, and the decalin solution of cyclododecanone oxime is obtained from the tower bottom and used for the subsequent rearrangement reaction.
Example 2
Adding 20g of cyclododecanone, 200g of tert-butyl alcohol, 0.002g of tetrabutyl phosphonium hexafluorophosphate and 0.2g of APG1214 into a 1L reaction kettle, stirring and mixing, and heating to 100 ℃;
8.4g hydroxylamine hydrochloride dissolved in 159.62g water, using 4.11g concentration of 50wt% ammonia water neutralization, after neutralization preheating to 80 degrees C, once added to the reaction liquid, reaction start timing.
After the reaction is carried out for 0.9h, stopping stirring, carrying out oil-water separation, and testing the content of hexafluorophosphate ions in the oil phase to be 90.49% by ion chromatography; the oil phase was taken for gas phase analysis, the cyclododecanone conversion rate was 99.79%, and the cyclododecanone oxime selectivity was 99.89%.
Adding 400g of squalane into the oil phase, and carrying out normal pressure rectification under the following rectification conditions: 13 tower plates, the reflux ratio of 1.5 and the tower bottom temperature of 180-200 ℃; tertiary butanol is extracted from the tower top, and squalane solution of cyclododecanone oxime is obtained from the tower bottom and is used for the subsequent rearrangement reaction.
Example 3
Adding 20g cyclododecanone, 100g n-butanol, 0.1g 1-butyl-3-methylimidazolium hexafluorophosphate and 0.08g Glucopon225DK into a 0.5L reaction kettle, stirring and mixing, and heating to 95 ℃;
13.52g hydroxylamine sulfate dissolved in 31.54g water, using 11.21g concentration of 25wt% ammonia water neutralization, after neutralization preheating to 75 degrees C, once added to the reaction liquid, the reaction start timing.
After reacting for 0.8h, stopping stirring for oil-water separation, and testing the content of hexafluorophosphate ions in an oil phase to be 87.65% by ion chromatography; and (3) taking an oil phase for gas phase analysis, wherein the conversion rate of the cyclododecanone is 99.61 percent, and the selectivity of the cyclododecanone oxime is 99.74 percent.
Adding 200g of decalin into the oil phase, and carrying out normal pressure rectification under the following rectification conditions: the number of tower plates is 15, the reflux ratio is 1.5, and the tower bottom temperature is 180-200 ℃; n-butanol is extracted from the tower top, and the decalin solution of cyclododecanone oxime is obtained from the tower bottom and used for the subsequent rearrangement reaction.
Example 4
Adding 20g of cyclododecanone, 120g of n-propanol, 0.02g of diphenyliodonium hexafluorophosphate and 0.04g of glucopon215UP into a 0.5L reaction kettle, stirring and mixing, and heating to 97 ℃;
9.38g of hydroxylamine phosphate dissolved in 37.52g of water, using 12.14g concentration for 20wt% ammonia water neutralization, after neutralization preheating to 73 degrees C, once added to the reaction liquid, reaction start timing.
After the reaction is carried out for 0.7h, stopping stirring, carrying out oil-water separation, and testing the content of hexafluorophosphate ions in the oil phase to be 87.93% by ion chromatography; the oil phase was taken for gas phase analysis, the conversion of cyclododecanone was 99.68%, and the selectivity of cyclododecanone oxime was 99.69%.
Adding 360g of ethyl cyclohexane into the oil phase, and carrying out normal pressure rectification under the following rectification conditions: 11 tower plates, a reflux ratio of 0.5 and a tower bottom temperature of 120-150 ℃; n-propanol is extracted from the top of the tower, and the ethyl cyclohexane solution of cyclododecanone oxime is obtained from the bottom of the tower and is used for the subsequent rearrangement reaction.
Example 5
Adding 20g of cyclododecanone, 140g of n-propanol, 0.06g of tri-p-tolyl sulfonium hexafluorophosphate and 0.06g of APG0814 into a 0.5L reaction kettle, stirring and mixing, and heating to 92 ℃;
12.62g hydroxylamine sulfate dissolved in 113.54g water, using 6.54g concentration for 40wt% ammonia water neutralization, after neutralization preheating to 78 degrees C, once added to the reaction liquid, reaction start timing.
After the reaction is carried out for 0.6h, stopping stirring, carrying out oil-water separation, and testing the content of hexafluorophosphate ions in the oil phase to be 88.64% by ion chromatography; the oil phase was taken for gas phase analysis, the conversion of cyclododecanone was 99.71%, and the selectivity of cyclododecanone oxime was 99.64%.
Adding 100g of cyclododecane into the oil phase, and carrying out normal pressure rectification under the following rectification conditions: the number of tower plates is 10, the reflux ratio is 1, and the tower bottom temperature is 180-200 ℃; n-propanol is extracted from the top of the tower, and cyclododecane solution of cyclododecanone oxime is obtained from the bottom of the tower and is used for the subsequent rearrangement reaction.
Example 6
Adding 20g of cyclododecanone, 80g of tert-butyl alcohol, 0.2g of chlorotriazolylphosphonium hexafluorophosphate and 0.016g of APG0810 into a 0.5L reaction kettle, stirring and mixing, and heating to 96 ℃;
10.81g hydroxylamine sulfate dissolved in 20.08g water, using 7.47g concentration 30wt% ammonia water neutralization, after neutralization after preheating to 71 degrees C, once added to the reaction liquid, the reaction is started timing.
After the reaction is carried out for 0.8h, stopping stirring, carrying out oil-water separation, and testing the content of hexafluorophosphate ions in the oil phase to be 89.47% by ion chromatography; the oil phase was taken for gas phase analysis, the cyclododecanone conversion rate was 99.69%, and the cyclododecanone oxime selectivity was 99.78%.
Adding 300g of isopropyl cyclohexane into the oil phase, and carrying out normal pressure rectification under the following rectification conditions: the number of tower plates is 15, the reflux ratio is 1.5, and the tower bottom temperature is 150-170 ℃; tertiary butanol is extracted from the top of the tower, and the isopropyl cyclohexane solution of cyclododecanone oxime is obtained from the bottom of the tower and is used for the subsequent rearrangement reaction.
Comparative example 1
Cyclododecanone oxime was prepared under the same conditions as in example 1 except that: glucopon600CSUP was not added. After the reaction is carried out for 0.5h, stopping stirring, carrying out oil-water separation, and testing the content of hexafluorophosphate ions in the oil phase to be 12.14% by using an ion chromatography; the oil phase was taken for gas phase analysis, the cyclododecanone conversion rate was 83.97%, and the cyclododecanone oxime selectivity was 97.12%.
Comparative example 2
Cyclododecanone oxime was prepared under the same conditions as in example 1 except that: no N-hexylpyridinium hexafluorophosphate was added. After the reaction is carried out for 0.5h, oil-water separation is carried out, and gas phase analysis confirms that the conversion rate of the cyclododecanone is 65.79 percent and the selectivity of the cyclododecanone oxime is 96.65 percent.
Comparative example 3
Cyclododecanone oxime was prepared under the same conditions as in example 1 except that: n-hexylpyridinium hexafluorophosphate and Glucopon600CSUP were not added. After 0.5h of reaction, oil-water separation is carried out, and gas phase analysis confirms that the conversion rate of the cyclododecanone is 20.75 percent and the selectivity of the cyclododecanone oxime is 93.05 percent.
Comparative example 4
Cyclododecanone oxime was prepared under the same conditions as in example 1 except that ammonium dodecylbenzenesulfonate was used as a catalyst in place of N-hexylpyridinium hexafluorophosphate, while Glucopon600CSUP was not added. After the reaction time of 0.5h, the stirring was stopped and oil-water separation was carried out, and gas phase analysis confirmed that the cyclododecanone conversion was 30.69% and the cyclododecanone oxime selectivity was 95.43%.
Comparative example 5
Cyclododecanone oxime was prepared under the same conditions as in example 1 except that: tetrabutyl phosphine benzotriazole salt is used as a catalyst instead of N-hexyl pyridine hexafluorophosphate. After the reaction time of 0.5h, the stirring was stopped and oil-water separation was carried out, and gas phase analysis confirmed that the cyclododecanone conversion was 67.99% and the cyclododecanone oxime selectivity was 97.03%.
Comparative example 6
Cyclododecanone oxime was prepared under the same conditions as in example 1 except that: tetrabutylphosphine benzotriazole salt was used as a catalyst instead of N-hexylpyridine hexafluorophosphate salt, while Glucopon600CSUP was not added. After the reaction time of 0.5h, the stirring was stopped and oil-water separation was carried out, and gas phase analysis confirmed that the conversion of cyclododecanone was 44.19% and the selectivity of cyclododecanone oxime was 97.11%.
According to the test results, the hexafluorophosphate ionic liquid is used as an oximation reaction catalyst, the alkyl glycoside is used as an oximation reaction surfactant, the oximation reaction rate and the cyclododecanone oxime selectivity can be effectively improved, the synergistic effect of the oximation reaction rate and the cyclododecanone oxime selectivity is obvious, by adopting the method, the oximation reaction time of the cyclododecanone can be reduced to within 1 hour, and the cyclododecanone oxime selectivity can reach more than 99.5%.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (10)
1. An oximation method of cyclododecanone is characterized in that cyclododecanone and hydroxylamine are subjected to oximation reaction under the condition of adding an ionic liquid catalyst and alkyl glycoside to generate cyclododecanone oxime.
2. The process for oximation of cyclododecanone according to claim 1, wherein the ionic liquid catalyst is a non-metal type ionic liquid, preferably a hexafluorophosphate type ionic liquid, further preferably tetraethylphosphonium hexafluorophosphate, N-butylpyridinium hexafluorophosphate, diphenyliodonium hexafluorophosphate, 1-methylpyridinium hexafluorophosphate, tri-p-tolylsulfonium hexafluorophosphate, chlorodipiperidinium hexafluorophosphate, 5-azoniaspiro [4.4] nonane hexafluorophosphate, tripyrrolidinyl phosphonium bromide hexafluorophosphate, chlorotriazolyl phosphonium hexafluorophosphate, 1-butyl-1-methylpyrrolidine hexafluorophosphate, 4-isobutylphenyl-4' -methylphenyliodiophosphate, N-hexylpyridinehexafluorophosphate, tetrabutylphosphonium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3-methylimidazolium hexafluorophosphate, 2-fluoro-1, 3-dimethylimidazolium hexafluorophosphate, 1-vinyl-3-butylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium hexafluorophosphate, one or more preferably tetrahexyl hexafluorophosphate.
3. The method of oximation of cyclododecanone according to claim 2, wherein the alkyl glycoside has a saccharide polymerization degree of 1 to 3, preferably 1.2 to 2, an alkyl carbon number of 6 to 18, preferably 8 to 14; the alkyl glycoside is preferably one or more of Glucopon215UP, glucopon225DK, glucopon425N/HH, glucopon600CSUP, glucopon650EC, APG1214, APG0810 and APG0814, and more preferably APG1214 and Glucopon600CSUP.
4. The method for oximation of cyclododecanone according to claim 3, wherein the hydroxylamine is obtained by neutralizing an aqueous solution of hydroxylamine salt with dropwise addition of aqueous ammonia; the hydroxylamine salt is one or more of hydroxylamine sulfate, hydroxylamine hydrochloride and hydroxylamine phosphate, and the hydroxylamine sulfate is preferred;
preferably, the concentration of the aqueous solution of hydroxylamine salt is 5-40%, preferably 10-30%; the concentration of the ammonia water is 10-50%, preferably 20-30%.
5. The process for the oximation of cyclododecanone according to any one of claims 1 to 4, wherein the ionic liquid catalyst is added in an amount of 0.01 to 1%, preferably 0.1 to 0.5% by mass of cyclododecanone; the addition amount of the alkyl glycoside is 0.05-1%, preferably 0.2-0.5% of the mass of the cyclododecanone.
6. The method of oximation of cyclododecanone according to claim 5, wherein the molar ratio of hydroxylamine to cyclododecanone is (1.1-2.2): 1, preferably (1.3-1.5): 1.
7. The method for oximation of cyclododecanone according to claim 6, wherein the reaction solvent for oximation reaction is a saturated alcohol, preferably one or more of methanol, ethanol, n-propanol, isopropanol, propylene glycol, n-butanol, t-butanol, butylene glycol, pentylene glycol, pentanol, hexylene glycol, n-octanol, isooctanol, decanediol, cyclohexanol, cyclododecanol, more preferably isopropanol, t-butanol.
8. The method of oximation of cyclododecanone according to claim 7, wherein the amount of the reaction solvent added is 3 to 10 times, preferably 4 to 6 times, the mass of the cyclododecanone.
9. The method for oximation of cyclododecanone according to any one of claims 1 to 8, wherein the reaction conditions of the oximation reaction are: the reaction temperature is 90-100 ℃, and the reaction time is 0.5-1h.
10. The method of oximation of cyclododecanone according to any of claims 1 to 9, characterized in that it further comprises the following post-reaction work-up procedures:
after the reaction is finished, oil-water separation is carried out; adding a displacement solvent into the oil phase, rectifying at normal pressure, extracting a reaction solvent from the top of the tower, obtaining a displacement solution containing cyclododecanone oxime from the bottom of the tower, and sending the displacement solution into a subsequent rearrangement process;
preferably, the metathesis solvent is one or more of methylcyclohexane, ethylcyclohexane, isopropylcyclohexane, dimethylcyclohexane, toluene, ethylbenzene, cumene, cyclododecane, decalin and squalane, preferably decalin, squalane;
preferably, the amount of the displacement solvent is 3 to 20 times, preferably 5 to 10 times, the mass of the cyclododecanone;
preferably, the atmospheric distillation conditions are 10-15 plates, reflux ratio of 0.5-2 and tower bottom temperature of 120-200 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111049134.9A CN115772094B (en) | 2021-09-08 | 2021-09-08 | Cyclododecanone is to be oximated |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111049134.9A CN115772094B (en) | 2021-09-08 | 2021-09-08 | Cyclododecanone is to be oximated |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115772094A true CN115772094A (en) | 2023-03-10 |
| CN115772094B CN115772094B (en) | 2024-09-10 |
Family
ID=85387994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111049134.9A Active CN115772094B (en) | 2021-09-08 | 2021-09-08 | Cyclododecanone is to be oximated |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115772094B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100063274A1 (en) * | 2008-09-11 | 2010-03-11 | CHINA PETROCHEMICAL DEVELOPMENT CORPORATION, Taipei(Taiwan) | Method for preparing amide |
| US20110105793A1 (en) * | 2009-10-30 | 2011-05-05 | China Petrochemical Development Corporation | Method for separating amide from amino acid ionic liquid |
| CN109761854A (en) * | 2019-02-21 | 2019-05-17 | 中南大学 | The synthetic method of hydroximic acid compound |
| CN109867616A (en) * | 2017-12-05 | 2019-06-11 | 万华化学集团股份有限公司 | A kind of production method of lauric lactam |
-
2021
- 2021-09-08 CN CN202111049134.9A patent/CN115772094B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100063274A1 (en) * | 2008-09-11 | 2010-03-11 | CHINA PETROCHEMICAL DEVELOPMENT CORPORATION, Taipei(Taiwan) | Method for preparing amide |
| US20110105793A1 (en) * | 2009-10-30 | 2011-05-05 | China Petrochemical Development Corporation | Method for separating amide from amino acid ionic liquid |
| CN109867616A (en) * | 2017-12-05 | 2019-06-11 | 万华化学集团股份有限公司 | A kind of production method of lauric lactam |
| CN109761854A (en) * | 2019-02-21 | 2019-05-17 | 中南大学 | The synthetic method of hydroximic acid compound |
Non-Patent Citations (1)
| Title |
|---|
| YOSHIRO FURUYA ET AL.: "Cyanuric Chloride as a Mild and Active Beckmann Rearrangement Catalyst", 《J. AM. CHEM. SOC.》, vol. 127, no. 32, 23 July 2005 (2005-07-23), pages 11240 - 11241, XP002441494, DOI: 10.1021/ja053441x * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115772094B (en) | 2024-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107001236B (en) | Purification method of 1, 5-pentanediamine and 1, 5-pentanediamine | |
| US8816069B2 (en) | Method for producing amide compound | |
| EP1794110B1 (en) | Method for purifying and concentrating dinitrogen monoxide | |
| US20060205939A1 (en) | Process for producing cyclohexanone oxime | |
| WO2007033582A1 (en) | A method for preparing amides by heterogeneous oximation and rearrangement | |
| EP2551261B1 (en) | Method for producing oxime | |
| CN115772094A (en) | Oximation method of cyclododecanone | |
| ES2417180T3 (en) | Purification of cyclododecanone by heat treatment | |
| CN109134172B (en) | Ligand-regulated method for selectively synthesizing Z-and E-olefin by catalyzing alcohol hydrogen-donating iridium | |
| CA1108193A (en) | Method of producing alcohols with 2 - 4 c atoms by catalytic hydration of olefins | |
| CN109678754B (en) | Preparation method of 11-cyanoundecanoic acid | |
| CN110498748A (en) | L-arginine and its derivative are used to prepare the purposes and a kind of method for preparing cyclododecanone oxime of cyclododecanone oxime | |
| US20110065913A1 (en) | Process for producing laurolactam | |
| US6245907B1 (en) | Process for producing a high purity caprolactam | |
| CN107540520A (en) | A kind of method that Pyromellitic Acid or trimellitic acid are prepared by pinacol | |
| CN109251125B (en) | Method for preparing cyclohexanol by oxidizing cyclohexane | |
| CN113548980A (en) | Method for preparing cyclododecanone oxime | |
| CN109092375B (en) | Free radical stabilizer for preparing adipic acid by direct oxidation of cyclohexane | |
| US8962861B2 (en) | Catalyst composition and method for preparing amide | |
| CN115770615B (en) | Preparation method of rare earth doped titanium-silicon molecular sieve catalyst and ammoximation method of cyclododecanone | |
| CN114471699B (en) | Catalyst composition for cyclododecanone ammoximation reaction and application thereof | |
| CN115536527B (en) | Preparation method of isobutyl (methyl) acrylate | |
| KR20190080596A (en) | Method for manufacturing cyclododecanone and apparatus for manufacturing the same | |
| CN112661619B (en) | Method for preparing cyclopentanone | |
| US3173964A (en) | Reduction of 1, 5, 9-cyclododecatriene to cyclododecene with lithium metal in ethyl aine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |