CN105037125A - Method for preparing vitamin K3 - Google Patents
Method for preparing vitamin K3 Download PDFInfo
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- CN105037125A CN105037125A CN201510357088.7A CN201510357088A CN105037125A CN 105037125 A CN105037125 A CN 105037125A CN 201510357088 A CN201510357088 A CN 201510357088A CN 105037125 A CN105037125 A CN 105037125A
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- naphthoquinones
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- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 235000012711 vitamin K3 Nutrition 0.000 title claims abstract description 37
- 239000011652 vitamin K3 Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 29
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims abstract description 28
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 19
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 13
- 239000012046 mixed solvent Substances 0.000 claims abstract description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical class C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 23
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical group CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 20
- 230000001590 oxidative effect Effects 0.000 claims description 15
- 238000000967 suction filtration Methods 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 9
- -1 4-naphthoquinones sodium bisulfite Chemical class 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 8
- 238000007710 freezing Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- OHKRYVAKYCCYNX-UHFFFAOYSA-N 3-chloro-2,5-diethylpyrazine Chemical compound CCC1=CN=C(CC)C(Cl)=N1 OHKRYVAKYCCYNX-UHFFFAOYSA-N 0.000 abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 239000012065 filter cake Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 7
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 235000013343 vitamin Nutrition 0.000 description 4
- 239000011782 vitamin Substances 0.000 description 4
- 229940088594 vitamin Drugs 0.000 description 4
- 229930003231 vitamin Natural products 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 150000003722 vitamin derivatives Chemical class 0.000 description 3
- RYWSYCQQUDFMAU-UHFFFAOYSA-N Acetomenaphthone Chemical compound C1=CC=C2C(OC(=O)C)=CC(C)=C(OC(C)=O)C2=C1 RYWSYCQQUDFMAU-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229940041603 vitamin k 3 Drugs 0.000 description 2
- RZPFVRFSYMUDJO-UHFFFAOYSA-N 2h-naphthalen-1-one Chemical compound C1=CC=C2C(=O)CC=CC2=C1 RZPFVRFSYMUDJO-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010053567 Coagulopathies Diseases 0.000 description 1
- 208000031220 Hemophilia Diseases 0.000 description 1
- 208000009292 Hemophilia A Diseases 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- XTOIZCLIDNVTKL-UHFFFAOYSA-N S(=O)(O)O.N1=CC=CC2=CC=CC=C12 Chemical compound S(=O)(O)O.N1=CC=CC2=CC=CC=C12 XTOIZCLIDNVTKL-UHFFFAOYSA-N 0.000 description 1
- 108010064129 Thrombogen Proteins 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000023555 blood coagulation Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 230000035602 clotting Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- XDPFHGWVCTXHDX-UHFFFAOYSA-M menadione sodium sulfonate Chemical compound [Na+].C1=CC=C2C(=O)C(C)(S([O-])(=O)=O)CC(=O)C2=C1 XDPFHGWVCTXHDX-UHFFFAOYSA-M 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
- 235000005152 nicotinamide Nutrition 0.000 description 1
- 239000011570 nicotinamide Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003716 vitamin K3 derivatives Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/04—Preparation of quinones by oxidation giving rise to quinoid structures of unsubstituted ring carbon atoms in six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/10—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing vitamin K3, and relates to vitamin K3. The method for preparing vitamin K3 with the chemical name of 2-methyl-1,4-naphthoquinone includes the following steps: dissolving 2-methylnaphthalene into a hydrocarbon solvent; adding sodium dodecyl sulfate and chromium ion oxidation liquid for an oxidation reaction; after completion of the reaction, purifying the reaction solution to obtain vitamin K3 with the chemical name of 2-methyl-1,4-naphthoquinone. The method for preparing vitamin K3 with the chemical name of 2-methyl-1,4-naphthoquinone sodium bisulfate includes the following steps: dissolving 2-methyl-1,4-naphthoquinone into a mixed solvent of water and ethyl alcohol; then adding sodium bisulfite for a sulfonation reaction; after completion of the reaction, purifying the reaction solution to obtain vitamin K3 with the chemical name of 2-methyl-1,4-naphthoquinone sodium bisulfate. According to the invention, the method is high in reaction selectivity, mild in reaction conditions, short in operation steps, green and environment-friendly, and stable in process; the product purity is 97% or above, and the total yield is 79% or above.
Description
Technical field
The present invention relates to vitamin K3, specifically relate to a kind of preparation method of vitamin K3.
Background technology
Vitamin K3 is not only a kind of important VITAMIN kind, and be the important intermediate of synthesis K system VITAMIN, such as can synthesise vitamins K1 (Beta-methyl-3-phytyl-l, 4-naphthalenone), multiprenylmenaquinone (Beta-methyl-3-difarnesyl-l, 4-naphthoquinones) etc.2-MNQ is the vitamin K3 that people adopt the earliest, active high, low price, but poor stability, not easily absorbs, and then people develop the vitamin K3 (sodium menadione sulfate) of novel easy absorption.The function of vitamin K3 promotes Blood clotting, in blood the level of thrombogen and the supply of vitamin K3 directly related.Be deficient in vitamin the animal of K3, and its clotting time can significant prolongation, and during famine, minor scratches will cause haemophilia and cause death.In order to promote growth of animal and preventing disease in aquatic products, livestock-raising, usually in feed, adding hormone and antibiotic, causing the shortage of animal vitamin K3.Therefore, in feed, usually add vitamin K3, with the content of vitamin K3 in supplementary animal body.
Vitamin K3 series products mainly contains vitamin k3 (MSB), vitamin k3 mixture (MSBC), vitamin k4 diformazan Kui Linpyrimido quinoline sulphite (MPB), vitamin k4 niacinamide sulphite (MNB) in the market.Modal formulation is vitamin k3 (94%), and its formal name used at school is 2-MNQ sodium bisulfite, and molecular formula is C
11h
8o
2naHSO
33H
2o is white or tawny crystalline powder, and odorless or micro-smelly, the easy moisture absorption, meets photolysis, soluble in water, is slightly soluble in ethanol.
Chinese patent CN101245038 discloses a kind of method of synthesise vitamins K3 (sodium menadione sulfate) in new solvent system.Its method is: 2-MNQ and sodium bisulfite add in solvent by (1), heated and stirred, carries out addition reaction; (2) reactant after addition reaction is refrigerated to less than 10 DEG C, centrifugation, obtains MSB crude product; (3) add ethanol, gac and sodium bisulfite, heating for dissolving, filtered while hot in MSB crude product, filtrate is refrigerated to less than 10 DEG C, centrifugation, crystallizing and drying, obtains MSB fine work.Wherein, the industrialization synthesis of 2-MNQ mainly contains two lines, and one is with 2-methylnaphthalene for raw material, under acetic acid exists, is oxidized obtains by chromic anhydride; Two is for raw material obtains through butadiene cyclization addition with toluene a kind of jade.Above-mentioned two lines all need to adopt chromium oxidation system, but current reaction system exists following shortcoming: poor selectivity, the productive rate of reaction are low, temperature of reaction is high, aftertreatment is complicated.
After in prior art, oxidizing reaction terminates, need by reaction solution stratification, the organic phase of then getting its upper strata concentrates, recrystallization purifying again, and the present invention only needs directly that reaction solution is freezing, suction filtration can obtain the product of higher degree and yield, simplifies operation steps.
4, environmental protection
The activated carbon treatment that can be passed through oxidized residual liquid of the present invention reclaims goes electrolytic regeneration to reuse, and therefore without discharging of waste liquid, is Green Chemistry.
5, process stabilizing
Experiment proves, present invention process condition maturity is stablized, and be applicable to suitability for industrialized production, obtained product purity is more than 97%, and total recovery is more than 79%.
Summary of the invention
In order to overcome the above-mentioned shortcoming that prior art exists, the first object of the present invention is to provide chemical name to be 2-methyl-l, the preparation method of the vitamin K3 of 4-naphthoquinones; The second object of the present invention is to provide chemical name to be the preparation method of the vitamin K3 of 2-MNQ sodium bisulfite.
Described chemical name is 2-methyl-l, the preparation method of the vitamin K3 of 4-naphthoquinones, and concrete steps are as follows:
Be dissolved in varsol by 2-methylnaphthalene, add sodium laurylsulfonate, chromium ion oxidation solution carries out oxidizing reaction, after reaction terminates, the purified chemical name that namely obtains of reaction solution is 2-methyl-l, the vitamin K3 of 4-naphthoquinones.
In described chromium ion oxidation solution, chromium ion concentration can be 2.75mol/L; Described 2-methylnaphthalene can be 1mol with the molecular volume ratio of chromium ion oxidation solution: (2 ~ 5) L, preferred 1mol: 3.3L; The mass ratio of described 2-methylnaphthalene and sodium laurylsulfonate can be 10: (0.5 ~ 2.0), and preferably 10: 1; Described varsol can be selected from least one in normal hexane, hexanaphthene, normal heptane, toluene etc., and the mass volume ratio of described 2-methylnaphthalene and varsol can be 1kg: (1 ~ 8) L, and preferred 1kg: 2L; The temperature of described oxidizing reaction can be 15 ~ 45 DEG C, and the time of oxidizing reaction can be 1 ~ 12h; The temperature of described oxidizing reaction preferably 30 DEG C, the time preferably 1 ~ 5h of oxidizing reaction.
After oxidizing reaction terminates, the method for described purifying can be: by reaction solution at-25 ~-10 DEG C, and preferably suction filtration after crystallization 6h at-18 DEG C, washes with water, and obtaining the chemical name that purity is greater than 97% is 2-methyl-l, the vitamin K3 of 4-naphthoquinones.
Described chemical name is 2-methyl isophthalic acid, the concrete steps of the preparation method of the vitamin K3 of 4-naphthoquinones sodium bisulfite are as follows: by 2-methyl isophthalic acid, 4-naphthoquinones is dissolved in the mixed solvent of water and ethanol, add sodium bisulfite again and carry out sulfonation reaction, after reaction terminates, namely reaction solution is purified obtains the vitamin K3 that chemical name is 2-MNQ sodium bisulfite.
Described 2-methyl isophthalic acid, the mass ratio of 4-naphthoquinones and sodium bisulfite can be 1: (1 ~ 2.4), preferably 1: 1.2, described 2-methyl isophthalic acid, the mass volume ratio of 4-naphthoquinones and water can be 1kg: (1 ~ 1.5) L, and preferred 1kg: 1.5L, described 2-methyl isophthalic acid, the mass volume ratio of 4-naphthoquinones and ethanol can be 1kg: (3 ~ 10) L, preferred 1kg: 5L; The temperature of described sulfonation reaction can be 35 ~ 70 DEG C, and the time of sulfonation reaction can be 2 ~ 12h; The temperature of described sulfonation reaction preferably 50 DEG C, the time preferred 4h of sulfonation reaction.
After sulfonation reaction terminates, the method for described purifying can be: in reaction solution, add the dissolution of solid that water makes precipitation, then add ethanol and gac, after absorption, suction filtration, filtrate freezing and crystallizing, filter and obtain the vitamin K3 that chemical name is 2-MNQ sodium bisulfite.
The add-on of described gac can be 1.5% of 2-MNQ by mass percentage; Through magnetic resonance detection, obtained chemical name is the yield of the vitamin K3 of 2-MNQ sodium bisulfite is 79%, and purity is 98.9%.
Compared with the preparation method of existing vitamin K3, the present invention has following outstanding technique effect:
1, reaction preference is high
The present invention, owing to adding a small amount of sodium laurylsulfonate tensio-active agent (SDS), therefore effectively can suppress distillation and the side reaction of raw material 2-methylnaphthalene, improves the selectivity of reaction, also improves the transformation efficiency of raw material.
2, reaction conditions is gentle
Carry out oxidizing reaction owing to adding a small amount of sodium laurylsulfonate tensio-active agent, therefore effectively can increase the contact surface of two phase reaction, make the reaction conditions of oxidizing reaction more gentle, the reaction times is shorter.
3, operation steps is brief
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the 2-MNQ that the embodiment of the present invention 1 prepares;
Fig. 2 is the carbon-13 nmr spectra figure of the 2-MNQ that the embodiment of the present invention 1 prepares;
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of the 2-MNQ sodium bisulfite that the embodiment of the present invention 4 prepares;
Fig. 4 is the carbon-13 nmr spectra figure of the 2-MNQ sodium bisulfite that the embodiment of the present invention 4 prepares.
Embodiment
The compound method of following examples 1 ~ 3 chromium ion oxidation solution is as follows: join in the water of 0.55L by the chromium trioxide of 0.275kg, add the sulfuric acid that 0.175kg massfraction is 17.5% after stirring and dissolving again, obtained chromium ion concentration is the chromium ion oxidation solution of 2.75mol/L.
Embodiment 12-methyl isophthalic acid, the preparation of 4-naphthoquinones
At 15 DEG C, after 2-methylnaphthalene (1kg) is dissolved in normal hexane (2L), add the chromium ion oxidation solution (35L) of sodium laurylsulfonate (0.1Kg), 2.75mol/L again, mechanical stirring, after reaction 3h, reaction solution is put into refrigerator freezing (-18 DEG C) crystallization 6h, suction filtration, wash with water, obtain filter cake, filter cake is through magnetic resonance detection, confirm as 2-methyl isophthalic acid, 4-naphthoquinones, weighs after dry, yield 84.5%, employing high performance liquid chromatography detects, and purity is 97%.
The hydrogen nuclear magnetic resonance spectrogram of the 2-MNQ that embodiment 1 prepares is see Fig. 1, and the carbon-13 nmr spectra figure of the 2-MNQ that embodiment 1 prepares is see Fig. 2.
Embodiment 22-methyl isophthalic acid, the preparation of 4-naphthoquinones
At 45 DEG C, after 2-methylnaphthalene (1kg) is dissolved in normal hexane (2L), add the chromium ion oxidation solution (14L) of sodium laurylsulfonate (0.1kg), 2.75mol/L again, mechanical stirring, after reaction 3h, reaction solution is put into refrigerator freezing (-18 DEG C) crystallization 6h, suction filtration, wash with water, obtain filter cake, filter cake is through magnetic resonance detection, confirm as 2-methyl isophthalic acid, 4-naphthoquinones, weighs after dry, yield 89.1%, employing high performance liquid chromatography detects, and purity is 98.5%.
Embodiment 32-methyl isophthalic acid, the preparation of 4-naphthoquinones
At 45 DEG C, after 2-methylnaphthalene (1kg) is dissolved in normal hexane (2L), then add the chromium ion oxidation solution (14L) of sodium laurylsulfonate (0.2kg), 2.75mol/L, mechanical stirring, reaction 3h after by reaction solution at-25 DEG C of crystallization 6h, suction filtration, wash with water, obtain filter cake, filter cake is through magnetic resonance detection, confirm as 2-methyl isophthalic acid, 4-naphthoquinones, weighs after dry, yield 82.5%, employing high performance liquid chromatography detects, and purity is 99.1%.
Embodiment 42-methyl isophthalic acid, the preparation of 4-naphthoquinones sodium bisulfite
At 50 DEG C, toward the 2-methyl isophthalic acid that embodiment 1 prepares, water (1.5L) is added in 4-naphthoquinones (1.02kg), ethanol (5L), after stirring and dissolving, add sodium bisulfite (1.2kg), after reaction 4h, separate out solid, the water that past reaction solution adds 500mL makes the dissolution of solid of precipitation, add 500mL ethanol again, adding quality is 2-methyl isophthalic acid, the gac of 4-naphthoquinones 1.5%, 15min is adsorbed at 50 DEG C, suction filtration while hot, filtrate is freezing and crystallizing at-18 DEG C, filter, filter cake is through magnetic resonance detection, confirm 2-methyl isophthalic acid, 4-naphthoquinones sodium bisulfite, yield 79%, high performance liquid phase purity is 98.9%.
The hydrogen nuclear magnetic resonance spectrogram of the 2-MNQ sodium bisulfite that embodiment 4 prepares is see Fig. 3; The carbon-13 nmr spectra figure of the 2-MNQ sodium bisulfite that embodiment 4 prepares is see Fig. 4.
Embodiment 52-methyl isophthalic acid, the preparation of 4-naphthoquinones sodium bisulfite
At 50 DEG C, toward the 2-methyl isophthalic acid that embodiment 1 prepares, water (3L) is added in 4-naphthoquinones (1.02kg), ethanol (10L), after stirring and dissolving, add sodium bisulfite (1.2kg), after reaction 4h, separate out solid, the water that past reaction solution adds 500mL makes the dissolution of solid of precipitation, add 500mL ethanol again, adding quality is 2-methyl isophthalic acid, the gac of 4-naphthoquinones 1.5%, 15min is adsorbed at 50 DEG C, suction filtration while hot, filtrate is freezing and crystallizing at-18 DEG C, filter, filter cake is through magnetic resonance detection, confirm 2-methyl isophthalic acid, 4-naphthoquinones sodium bisulfite, yield 82%, high performance liquid phase purity is 97.9%.
Embodiment 62-methyl isophthalic acid, the preparation of 4-naphthoquinones sodium bisulfite
At 50 DEG C, toward the 2-methyl isophthalic acid that embodiment 1 prepares, water (3L) is added in 4-naphthoquinones (1.02kg), ethanol (10L), after stirring and dissolving, add sodium bisulfite (2.4kg), after reaction 4h, separate out solid, the water that past reaction solution adds 500mL makes the dissolution of solid of precipitation, add 500mL ethanol again, adding quality is 2-methyl isophthalic acid, the gac of 4-naphthoquinones 1.5%, 15min is adsorbed at 50 DEG C, suction filtration while hot, filtrate is freezing and crystallizing at-18 DEG C, filter, filter cake is through magnetic resonance detection, confirm 2-methyl isophthalic acid, 4-naphthoquinones sodium bisulfite, yield 85%, high performance liquid phase purity is 99.1%.
Claims (10)
1. chemical name is 2-methyl-l, and the preparation method of the vitamin K3 of 4-naphthoquinones is characterized in that its concrete steps are as follows:
Be dissolved in varsol by 2-methylnaphthalene, add sodium laurylsulfonate, chromium ion oxidation solution carries out oxidizing reaction, after reaction terminates, the purified chemical name that namely obtains of reaction solution is 2-methyl-l, the vitamin K3 of 4-naphthoquinones.
2. preparation method as claimed in claim 1, is characterized in that in described chromium ion oxidation solution, chromium ion concentration is 2.75mol/L; Described 2-methylnaphthalene is 1mol: (2 ~ 5) L, preferred 1mol: 3.3L with the molecular volume ratio of chromium ion oxidation solution.
3. preparation method as claimed in claim 1, is characterized in that the mass ratio of described 2-methylnaphthalene and sodium laurylsulfonate is 10: (0.5 ~ 2.0), preferably 10: 1.
4. preparation method as claimed in claim 1, is characterized in that described varsol is selected from least one in normal hexane, hexanaphthene, normal heptane, toluene; The mass volume ratio of described 2-methylnaphthalene and varsol can be 1kg: (1 ~ 8) L, preferred 1kg: 2L; The temperature of described oxidizing reaction can be 15 ~ 45 DEG C, and the time of oxidizing reaction can be 1 ~ 12h; The temperature of described oxidizing reaction preferably 30 DEG C, the time preferably 1 ~ 5h of oxidizing reaction.
5. preparation method as claimed in claim 1, after it is characterized in that oxidizing reaction terminates, the method for described purifying is: by reaction solution at-25 ~-10 DEG C, preferably suction filtration after crystallization 6h at-18 DEG C, wash with water, obtaining chemical name is 2-methyl-l, the vitamin K3 of 4-naphthoquinones.
6. chemical name is 2-methyl isophthalic acid, the preparation method of the vitamin K3 of 4-naphthoquinones sodium bisulfite, it is characterized in that its concrete steps are as follows: by 2-methyl isophthalic acid, 4-naphthoquinones is dissolved in the mixed solvent of water and ethanol, add sodium bisulfite again and carry out sulfonation reaction, after reaction terminates, namely reaction solution is purified obtains the vitamin K3 that chemical name is 2-MNQ sodium bisulfite.
7. preparation method as claimed in claim 6, it is characterized in that described 2-methyl isophthalic acid, the mass ratio of 4-naphthoquinones and sodium bisulfite is 1: (1 ~ 2.4), preferably 1: 1.2, the mass volume ratio of described 2-MNQ and water can be 1kg: (1 ~ 1.5) L, preferred 1kg: 1.5L, the mass volume ratio of described 2-MNQ and ethanol can be 1kg: (3 ~ 10) L, preferred 1kg: 5L.
8. preparation method as claimed in claim 6, it is characterized in that the temperature of described sulfonation reaction is 35 ~ 70 DEG C, the time of sulfonation reaction is 2 ~ 12h; The temperature of described sulfonation reaction preferably 50 DEG C, the time preferred 4h of sulfonation reaction.
9. preparation method as claimed in claim 6, after it is characterized in that sulfonation reaction terminates, the method of described purifying is: in reaction solution, add the dissolution of solid that water makes precipitation, add ethanol and gac again, after absorption, suction filtration, filtrate freezing and crystallizing, filter and obtain the vitamin K3 that chemical name is 2-MNQ sodium bisulfite.
10. preparation method as claimed in claim 9, is characterized in that the add-on of described gac is 1.5% of 2-MNQ by mass percentage.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108558775A (en) * | 2018-06-07 | 2018-09-21 | 山东华升化工科技有限公司 | A kind of preparation method of dimethyl pyrimidine alcohol sulfurous acid menadione |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108558775A (en) * | 2018-06-07 | 2018-09-21 | 山东华升化工科技有限公司 | A kind of preparation method of dimethyl pyrimidine alcohol sulfurous acid menadione |
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