CN115215726A - Synthesis method of 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol - Google Patents
Synthesis method of 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol Download PDFInfo
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- CN115215726A CN115215726A CN202110418408.0A CN202110418408A CN115215726A CN 115215726 A CN115215726 A CN 115215726A CN 202110418408 A CN202110418408 A CN 202110418408A CN 115215726 A CN115215726 A CN 115215726A
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- tetrafluorobenzyl alcohol
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- halogenated methyl
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- PJCSTULKVNHEGW-UHFFFAOYSA-N (2,3,5,6-tetrafluoro-4-methylphenyl)methanol Chemical compound CC1=C(F)C(F)=C(CO)C(F)=C1F PJCSTULKVNHEGW-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000001308 synthesis method Methods 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000006227 byproduct Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000011049 filling Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000012454 non-polar solvent Substances 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000007868 Raney catalyst Substances 0.000 claims description 5
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000003799 water insoluble solvent Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- ADIJGVURNDURDC-UHFFFAOYSA-N [4-(bromomethyl)-2,3,5,6-tetrafluorophenyl]methanol Chemical compound OCC1=C(F)C(F)=C(CBr)C(F)=C1F ADIJGVURNDURDC-UHFFFAOYSA-N 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001924 cycloalkanes Chemical class 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZFHGXWPMULPQSE-SZGBIDFHSA-N (Z)-(1S)-cis-tefluthrin Chemical compound FC1=C(F)C(C)=C(F)C(F)=C1COC(=O)[C@@H]1C(C)(C)[C@@H]1\C=C(/Cl)C(F)(F)F ZFHGXWPMULPQSE-SZGBIDFHSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000005939 Tefluthrin Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- -1 4- (chloromethyl) -2,3,5, 6-tetrafluorobenzyl Chemical group 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- YFHZSPDQKWFAPH-UHFFFAOYSA-N [2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methanol Chemical compound COCC1=C(F)C(F)=C(CO)C(F)=C1F YFHZSPDQKWFAPH-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000004970 halomethyl group Chemical group 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 241001233061 earthworms Species 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- POCNHGFJLGYFIK-UHFFFAOYSA-N methylcyclooctane Chemical compound CC1CCCCCCC1 POCNHGFJLGYFIK-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol, which is obtained by reacting 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol with hydrogen under the conditions of a nonpolar water-insoluble solvent, deionized water, an alkaline substance and a nickel catalyst, wherein the conversion rate of the 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol reaches more than 99%, the maximum hydrogenation yield can reach 97%, the catalyst can be recycled for more than 50 times, and the synthesis process can produce inorganic salts as byproducts. The separation of the product, the catalyst and the byproduct salt can be conveniently realized by the post-treatment of the process, and the method has the characteristics of high product content, less impurities, simple process, small three-waste generation amount and the like, and meets the requirement of clean production.
Description
Technical Field
The invention relates to a method for synthesizing 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol, in particular to a method for synthesizing 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol by hydrogenating 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol.
Background
4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol is an important intermediate of tefluthrin. Tefluthrin is the first pyrethroid pesticide to be used as a soil pesticide, has lower acute toxicity than the commonly used organophosphorus and carbamate soil pesticides, and is safe to use especially under the recommended dosage. Has high toxicity to fish and aquatic invertebrates, but low toxicity to earthworms and low toxicity to birds. The tefluthrin is applied in the form of granules, soil spraying or seed treatment, has good volatility, can fully move in gas phase, and can control soil pests through steam.
The prohengda patent CN01818042.6 and the Yangnong patent CN 1636949A mentioned in the examples that 4- (halogenated methyl) -2,3,5,6-tetrafluorobenzyl alcohol is hydrogenated under the conditions of methanol, 5% palladium carbon and magnesium oxide to obtain the product 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol, and the synthesis yield is 89.4%. However, in the process, because alcohols are used as solvents, the content of impurities such as ether alcohol, fluorine removal and the like in the synthesized product is high, and the synthesis yield is low.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for synthesizing 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol by hydrogenating 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol, the method effectively controls the generation of impurities such as 4-methoxymethyl-2, 3,5, 6-tetrafluorobenzyl alcohol and the like in the 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol, and simultaneously a hydrogenation catalyst can be recycled for more than 50 times, and inorganic salts are by-produced in the synthesis process; the method can conveniently realize the separation of the product, the catalyst and the byproduct salt, and has the advantages of high product content, less impurities, simple process, small three-waste generation amount and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol by hydrogenating 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol comprises the following steps:
4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol is adopted as a raw material, and the 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol and hydrogen are subjected to hydrogenation synthesis reaction in a non-water-soluble nonpolar solvent in the presence of deionized water, an alkaline substance and a nickel catalyst to obtain the 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol, wherein the reaction formula is shown as follows:
wherein: x represents Cl or Br.
In the above technical scheme, the non-water-soluble nonpolar solvent is any one of alkane, cycloalkane, and aromatic hydrocarbon, or a mixture of two or more thereof.
In the above technical solution, the alkane is preferably a C6 to C11 normal alkane and isomers thereof, and more preferably n-hexane, methylpentane, n-heptane, methylhexane, ethylpentane, n-octane, methylheptane, ethylheptane, nonane, undecane, or the like.
In the above-mentioned technical means, the cycloalkane is preferably a C6 to C11 cycloalkane and a cycloalkane isomer thereof, and more preferably cyclohexane, methylcyclohexane, methylcyclopentane, cyclooctane, methylcyclooctane, ethylcyclohexane or the like.
In the above technical solution, the aromatic hydrocarbon is preferably a C6 to C11 aromatic hydrocarbon and an aromatic hydrocarbon isomer thereof, and more preferably benzene, toluene, ethylbenzene, methylethylbenzene, xylene, trimethylbenzene, or the like.
In the above technical solution, the weight ratio of the 4- (halomethyl) -2,3,5, 6-tetrafluorobenzyl alcohol to the non-water-soluble nonpolar solvent is 1 to 50, preferably 1 to 10.
In the above technical scheme, the weight ratio of the 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol to the deionized water is 1. Quantitative water is added in the reaction process to dissolve salt generated by the reaction, so that the generated salt can be effectively prevented from covering the surface of the catalyst, and the reaction and the catalyst recovery are facilitated.
In the above technical scheme, the alkaline substance is any one of, or a mixture of two or more of oxides, hydroxides, carbonates and bicarbonates of alkali metals and alkaline earth metals. During the reaction, a certain amount of alkaline matter (or water solution of alkaline matter) is added to neutralize the hydrogen halide produced.
In the above technical solution, the alkaline substance is preferably any one of sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium hydroxide, potassium bicarbonate, potassium carbonate, calcium hydroxide, calcium oxide, magnesium hydroxide, and magnesium oxide, or a mixture of two or more of them.
In the above technical solution, the molar ratio of the 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol to the basic substance is 1:1.05-1.50.
In the technical scheme, the nickel-based catalyst is any one or a mixture of two of raney nickel and nickel-containing alloy; the nickel-containing alloy is preferably a nickel-aluminum alloy or a nickel-chromium alloy.
In the above technical solution, the weight ratio of the 4- (halomethyl) -2,3,5, 6-tetrafluorobenzyl alcohol to the nickel-based catalyst is 1.
In the above technical scheme, the hydrogenation synthesis reaction specifically comprises the following operations: adding 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol, a water-insoluble nonpolar solvent, deionized water, an alkaline substance and a nickel catalyst into a reaction kettle, replacing oxygen in a system by using nitrogen after the feeding is finished, and closing a feeding port when the oxygen content in the system is less than 1%; adding hydrogen into the system, stirring and heating, and hydrogenating 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol to synthesize 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol; after the reaction is finished, the separation of the product, the nickel catalyst and the byproduct salt is realized by filtering, standing and layering, the nickel catalyst can be recycled for more than 50 times, the oil layer is desolventized to obtain the 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol, and the byproduct inorganic salt can be obtained after the pH of the water layer is adjusted to be neutral.
In the technical scheme, the system is stirred and filled with hydrogen and heated, the hydrogenation reaction pressure of the reaction system is maintained to be 0-10.0MPa, preferably 0-5MPa, the hydrogenation reaction temperature is 20-250 ℃, preferably 40-140 ℃, and hydrogen is continuously introduced for reaction for 5-20h.
In the method, 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol is adopted to carry out hydrogenation reaction in the presence of a non-polar non-water-soluble solvent, water, an alkaline substance and a nickel catalyst to obtain the 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol, and the conversion rate of the raw material 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol reaches 99 percent or more. The method effectively controls the generation of impurities such as 4-methoxymethyl-2, 3,5, 6-tetrafluorobenzyl alcohol and the like in the 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol, the content of the product 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol reaches more than 97.9 percent, and the yield reaches more than 97 percent; meanwhile, the hydrogenation catalyst can be recycled for more than 50 times, and the inorganic salt is a byproduct in the synthesis process. The method can conveniently realize the separation of the product, the catalyst and the byproduct salt, and has the advantages of high product content, less impurities, simple process, small three-waste generation amount and the like.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but the present invention is not limited to the following descriptions:
the invention will now be illustrated with reference to specific examples:
example 1:
a1000 ml autoclave equipped with a gas inlet probe and a draw probe (containing a built-in filter) was charged with 70g of 4- (bromomethyl) -2,3,5, 6-tetrafluorobenzyl alcohol, 300g of heptane, 150g of water, and 44.4g of 30% potassium hydroxide. And (5) after the feeding is finished, replacing the system with nitrogen until the oxygen content of the system is less than 1%. Under the protection of nitrogen, 10g of Raney nickel was charged into the autoclave, and the charging port was closed. The system is qualified by nitrogen replacement again. Stirring and filling hydrogen until the pressure is 1.0MPa, and heating. When the reaction temperature reaches 45 ℃, stopping heating, controlling the pressure reducing valve at the outlet of the hydrogen steel cylinder to be 4.5MPa, maintaining the temperature at 45-50 ℃ and the pressure at 4.5MPa, and continuously introducing hydrogen into the high-pressure kettle for reaction for 12 hours. After the reaction, standing, pressing the reaction liquid out of the probe tube by pressure, layering, desolventizing the oil layer to 100 ℃/5mmhg by negative pressure, collecting 47.3g of 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol, the content is 98.2 percent, and the yield is 93.3 percent.
Example 2:
a1000 ml autoclave equipped with a gas inlet probe and a draw probe (containing a built-in filter) was charged with 70g of 4- (bromomethyl) -2,3,5, 6-tetrafluorobenzyl alcohol, 280g of xylene, 150g of water, and 44.4g of 30% potassium hydroxide. And (5) after the feeding is finished, replacing the system with nitrogen until the oxygen content of the system is less than 1%. Under the protection of nitrogen, 15g of nickel-aluminum alloy (containing 60% of nickel) is put into the autoclave, and the feeding port is closed. The system is qualified by nitrogen replacement again. Stirring and filling hydrogen until the pressure is 1.0MPa, and heating. When the reaction temperature reaches 135 ℃, stopping heating, controlling the pressure reducing valve at the outlet of the hydrogen steel cylinder to be 4.0MPa, maintaining the temperature at 135-140 ℃ and the pressure at 4.0MPa, and continuously introducing hydrogen into the high-pressure kettle for reaction for 7 hours. After the reaction, standing, pressing the reaction liquid out of the probe tube by pressure, layering, desolventizing the oil layer to 120 ℃/5mmhg by negative pressure, collecting 48.2g of 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol, the content is 98.0 percent, and the yield is 94.8 percent.
Example 3:
a1000 ml autoclave equipped with a gas inlet probe and a withdrawal probe (containing a built-in filter) was charged with 70g of 4- (bromomethyl) -2,3,5, 6-tetrafluorobenzyl alcohol, 400g of cyclohexane, 140g of water, and 7.0g of magnesium oxide. And (5) after the feeding is finished, replacing the system with nitrogen until the oxygen content of the system is less than 1%. Under the protection of nitrogen, 14g of nickel-chromium alloy (75% nickel) was charged into the autoclave, and the charging port was closed. The system is qualified by nitrogen replacement again. Stirring and filling hydrogen until the pressure is 1.0MPa, and heating. When the reaction temperature reaches 80 ℃, stopping heating, controlling the pressure reducing valve at the outlet of the hydrogen steel cylinder to be 3.0MPa, maintaining the temperature to be 75-80 ℃ and the pressure to be 3.0MPa, and continuously introducing hydrogen into the high-pressure kettle for reaction for 6 hours. After the reaction, standing, pressing the reaction liquid out of the probe tube by pressure, layering, desolventizing the oil layer to 100 ℃/5mmhg by negative pressure, collecting 49.1g of 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol, the content is 98.2 percent, and the yield is 97.0 percent.
Example 4:
70g of 4- (bromomethyl) -2,3,5, 6-tetrafluorobenzyl alcohol, 350g of methylcyclohexane, 140g of water, and 12.0g of magnesium hydroxide were charged into a 1000ml autoclave equipped with a gas inlet probe and a draw probe (including built-in filtration). And (5) after the feeding is finished, replacing the system with nitrogen until the oxygen content of the system is less than 1%. Under the protection of nitrogen, 8.4g of Raney nickel was charged into the autoclave, and the charging port was closed. The system is qualified by nitrogen replacement again. Stirring and filling hydrogen until the pressure is 1.0MPa, and heating. When the reaction temperature reaches 100 ℃, stopping heating, controlling the pressure reducing valve at the outlet of the hydrogen steel cylinder to be 2.5MPa, maintaining the temperature to be 100-105 ℃ and the pressure to be 2.5MPa, and continuously introducing hydrogen into the high-pressure kettle for reaction for 6 hours. After the reaction, standing, pressing the reaction liquid out of the probe tube by pressure, layering, desolventizing the oil layer to 110 ℃/5mmhg by negative pressure, collecting 47.4g of 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol, wherein the content is 97.5 percent, and the yield is 93.0 percent.
Example 5:
70g of 4- (bromomethyl) -2,3,5, 6-tetrafluorobenzyl alcohol, 400g of cyclohexane, 200g of water and 32.6g of sodium carbonate are put into a 1000ml autoclave with an air inlet probe and a drawing probe (containing built-in filtration). And (5) after the feeding is finished, replacing the system with nitrogen until the oxygen content of the system is less than 1%. Under the protection of nitrogen, 15g of nickel-aluminum alloy (containing 60% of nickel) is put into the autoclave, and the feeding port is closed. The system is qualified by nitrogen replacement again. Stirring and filling hydrogen until the pressure is 1.0MPa, and heating. When the reaction temperature reaches 85 ℃, stopping heating, controlling the pressure reducing valve at the outlet of the hydrogen steel cylinder to be 3.5MPa, maintaining the temperature to be 85-90 ℃ and the pressure to be 3.5MPa, and continuously introducing hydrogen into the high-pressure kettle for reaction for 12 hours. After the reaction, the mixture is stood, reaction liquid is extruded out from a probe tube through pressure, layering is carried out, an oil layer is desolventized to 100 ℃/5mmhg through negative pressure, 47.7g of 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol is collected, the content is 97.9 percent, and the yield is 95.3 percent.
Example 6:
a1000 ml autoclave equipped with a gas inlet probe and a draw probe (containing a built-in filter) was charged with 58.0g of 4- (chloromethyl) -2,3,5, 6-tetrafluorobenzyl alcohol, 300g of methylcyclohexane, 400g of water, and 52g of sodium hydrogencarbonate. And (5) after the feeding is finished, replacing the system with nitrogen until the oxygen content of the system is less than 1%. Under the protection of nitrogen, 8.4g of Raney nickel was charged into the autoclave, and the charging port was closed. The system is qualified by nitrogen replacement again. Stirring and filling hydrogen until the pressure is 1.0MPa, and heating. When the reaction temperature reaches 90 ℃, stopping heating, controlling the pressure reducing valve at the outlet of the hydrogen steel cylinder to be 3.5MPa, maintaining the temperature to be 100-105 ℃ and the pressure to be 3.5MPa, and continuously introducing hydrogen into the high-pressure kettle for reaction for 8 hours. After the reaction, standing, pressing the reaction solution out of the probe tube by pressure, layering, desolventizing the oil layer to 110 ℃/5mmhg under negative pressure, recovering 47.3g of 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol, the content is 97.6 percent, and the yield is 93.8 percent.
Example 6: (comparative example)
A1000 ml autoclave equipped with an air inlet probe and a draw probe (containing a built-in filter) was charged with 70.0g of 4- (bromomethyl) -2,3,5, 6-tetrafluorobenzyl alcohol, 266g of methanol, 4.4g of water, and 13.4g of magnesium oxide. And (5) after the feeding is finished, replacing the system with nitrogen until the oxygen content of the system is less than 1%. Under nitrogen protection, 0.6g of 5% palladium on carbon (type 58, 100% by weight) was charged into the autoclave, and the charging port was closed. The system is qualified by nitrogen replacement again. Stirring and filling hydrogen until the pressure is 0.25MPa, and raising the temperature. When the reaction temperature reaches 45 ℃, stopping heating, controlling the pressure reducing valve at the outlet of the hydrogen steel cylinder to be 0.25MPa, maintaining the temperature to be 48-50 ℃ and the pressure to be 0.25MPa, and continuously introducing hydrogen into the high-pressure kettle until the reaction does not basically absorb hydrogen (about 2 hours). After the reaction is finished, standing, pressing the reaction liquid out of the probe tube through pressure, layering, taking out the materials, washing the kettle with 30g of methanol, taking out, and filtering; washing the filter cake with methanol (2 x 30g), mixing the filtrates, desolventizing at a negative pressure of 100 ℃/5mmhg, and recovering 46.8g of 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol, with a content of 95.2% and a yield of 89.6%.
Example 7: (comparative example)
A1000 ml autoclave equipped with a gas inlet probe and a withdrawal probe (including a built-in filter) was charged with 58.0g of 4- (chloromethyl) -2,3,5, 6-tetrafluorobenzyl alcohol, 266g of methanol, 4.4g of water, and 13.4g of magnesium oxide. And (5) after the feeding is finished, replacing the system with nitrogen until the oxygen content of the system is less than 1%. Under nitrogen protection, 0.6g of 5% palladium on carbon (type 58, 100% by weight) was charged into the autoclave, and the charging port was closed. The system is qualified by nitrogen replacement again. Stirring and filling hydrogen until the pressure is 0.25MPa, and raising the temperature. When the reaction temperature reaches 65 ℃, stopping heating, controlling the pressure reducing valve at the outlet of the hydrogen cylinder to be 0.25MPa, maintaining the temperature at 68-70 ℃ and the pressure at 0.25MPa, and continuously introducing hydrogen into the high-pressure kettle until the reaction does not basically absorb hydrogen (about 3-4 hours). After the reaction is finished, releasing the pressure, replacing hydrogen by nitrogen to be less than 1 percent, taking out the material, washing the kettle by 30g of methanol, taking out the material, and filtering; washing the filter cake with methanol (2 × 30g), mixing filtrates, desolventizing at negative pressure to 100 deg.C/5 mmhg, and recovering 46.5g of 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol with content of 93.9% and yield of 88.6%.
The above examples are only for illustrating the technical concept and features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (10)
1. A method for synthesizing 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol by hydrogenating 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol is characterized by comprising the following steps of:
4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol is adopted as a raw material, and the 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol and hydrogen are subjected to hydrogenation synthesis reaction in a non-water-soluble nonpolar solvent in the presence of deionized water, an alkaline substance and a nickel catalyst to obtain the 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol, wherein the reaction formula is shown as follows:
wherein: x represents Cl or Br.
2. The method of claim 1, wherein: the non-water-soluble nonpolar solvent is any one of alkane, cyclane and arene, or a mixture of two or more of the alkane, the cyclane and the arene.
3. The method of claim 1, wherein: the weight ratio of the 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol to the non-water-soluble nonpolar solvent is 1-50.
4. The method of claim 1, wherein: the weight ratio of the 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol to the deionized water is 1.
5. The method of claim 1, wherein: the alkaline substance is any one of oxide, hydroxide, carbonate and bicarbonate of alkali metal and alkaline earth metal, or a mixture of two or more of the alkali metal and the alkaline earth metal.
6. The method of claim 1, wherein: the molar ratio of the 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol to the alkaline substance is 1.
7. The method of claim 1, wherein: the nickel catalyst is any one or a mixture of two of Raney nickel and nickel-containing alloy.
8. The method of claim 1, wherein: the weight ratio of the 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol to the nickel catalyst is 1.
9. The method of claim 1, wherein: the hydrogenation synthesis reaction comprises the following specific operations: adding 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol, a water-insoluble nonpolar solvent, deionized water, an alkaline substance and a nickel catalyst into a reaction kettle, replacing oxygen in a system by using nitrogen after the feeding is finished, and closing a feeding port when the oxygen content in the system is less than 1%; adding hydrogen into the system while stirring, heating, and hydrogenating 4- (halogenated methyl) -2,3,5, 6-tetrafluorobenzyl alcohol to synthesize 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol; after the reaction is finished, the separation of the product, the nickel catalyst and the byproduct salt is realized by filtering, standing and layering, the nickel catalyst can be recycled for more than 50 times, the oil layer is desolventized to obtain the 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol, and the byproduct inorganic salt can be obtained after the pH of the water layer is adjusted to be neutral.
10. The method of claim 9, wherein: and (3) stirring and filling hydrogen into the system, heating, maintaining the hydrogenation reaction pressure of the reaction system at 0-10.0MPa and the hydrogenation reaction temperature at 20-250 ℃, and continuously introducing hydrogen for reaction for 5-20 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1438209A (en) * | 2003-03-21 | 2003-08-27 | 江苏省农用激素工程技术研究中心 | Method for preparing 4-methyl-tetrafluoro-benzil-alcohol |
| CN1458137A (en) * | 2003-06-06 | 2003-11-26 | 天津大学 | Process for preparing 2,3,5,6-Tetrafluoro-para-xylyl alcohol |
| CN103917510A (en) * | 2011-11-10 | 2014-07-09 | 住友化学株式会社 | Method for producing 4-hydroxymethyl-2,3,5,6-tetrafluorotoluene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438209A (en) * | 2003-03-21 | 2003-08-27 | 江苏省农用激素工程技术研究中心 | Method for preparing 4-methyl-tetrafluoro-benzil-alcohol |
| CN1458137A (en) * | 2003-06-06 | 2003-11-26 | 天津大学 | Process for preparing 2,3,5,6-Tetrafluoro-para-xylyl alcohol |
| CN103917510A (en) * | 2011-11-10 | 2014-07-09 | 住友化学株式会社 | Method for producing 4-hydroxymethyl-2,3,5,6-tetrafluorotoluene |
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| Title |
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| 何明阳等: ""4-甲基-2, 3, 5, 6-四氟苯甲醇的合成"", 《化工进展》, vol. 25, no. 7, pages 811 - 814 * |
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