CN103073399B - Preparation method of 3,5-dimethoxy phenylcarbinol - Google Patents
Preparation method of 3,5-dimethoxy phenylcarbinol Download PDFInfo
- Publication number
- CN103073399B CN103073399B CN201310031377.9A CN201310031377A CN103073399B CN 103073399 B CN103073399 B CN 103073399B CN 201310031377 A CN201310031377 A CN 201310031377A CN 103073399 B CN103073399 B CN 103073399B
- Authority
- CN
- China
- Prior art keywords
- dimethoxy
- hydrogen
- preparation
- methyl
- dimethoxybenzoic
- 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.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- AUDBREYGQOXIFT-UHFFFAOYSA-N (3,5-dimethoxyphenyl)methanol Chemical compound COC1=CC(CO)=CC(OC)=C1 AUDBREYGQOXIFT-UHFFFAOYSA-N 0.000 title abstract 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 60
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 60
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000010949 copper Substances 0.000 claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000005516 engineering process Methods 0.000 claims abstract description 18
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 66
- 239000007787 solid Substances 0.000 claims description 39
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- 239000004202 carbamide Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 150000001298 alcohols Chemical class 0.000 claims description 16
- 230000009467 reduction Effects 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 15
- 239000000428 dust Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 238000002525 ultrasonication Methods 0.000 claims description 9
- 206010013786 Dry skin Diseases 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 22
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- LUKBXSAWLPMMSZ-OWOJBTEDSA-N Trans-resveratrol Chemical compound C1=CC(O)=CC=C1\C=C\C1=CC(O)=CC(O)=C1 LUKBXSAWLPMMSZ-OWOJBTEDSA-N 0.000 description 11
- 238000001994 activation Methods 0.000 description 11
- 244000025254 Cannabis sativa Species 0.000 description 10
- 235000018991 trans-resveratrol Nutrition 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NGYYFWGABVVEPL-UHFFFAOYSA-N 5-(hydroxymethyl)benzene-1,3-diol Chemical compound OCC1=CC(O)=CC(O)=C1 NGYYFWGABVVEPL-UHFFFAOYSA-N 0.000 description 2
- 208000024172 Cardiovascular disease Diseases 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 244000153955 Reynoutria sachalinensis Species 0.000 description 2
- 235000003202 Reynoutria sachalinensis Nutrition 0.000 description 2
- 206010000496 acne Diseases 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940124443 chemopreventive agent Drugs 0.000 description 2
- 239000012627 chemopreventive agent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000000069 prophylactic effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 208000002874 Acne Vulgaris Diseases 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- 206010014759 Endometrial neoplasm Diseases 0.000 description 1
- 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 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 206010033128 Ovarian cancer Diseases 0.000 description 1
- 206010061535 Ovarian neoplasm Diseases 0.000 description 1
- 206010060862 Prostate cancer Diseases 0.000 description 1
- 208000000236 Prostatic Neoplasms Diseases 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 201000011529 cardiovascular cancer Diseases 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZZBBCSFCMKWYQR-UHFFFAOYSA-N copper;dioxido(oxo)silane Chemical compound [Cu+2].[O-][Si]([O-])=O ZZBBCSFCMKWYQR-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 201000003914 endometrial carcinoma Diseases 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 230000007365 immunoregulation Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 208000010110 spontaneous platelet aggregation Diseases 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the field of chemical synthetic technologies, and particularly relates to a preparation method of 3,5-dimethoxy phenylcarbinol. The preparation method solves the technical problem that the existing synthetic method is high in cost, complicated to operate and difficult to industrialize, and the amount of generated waste gas, waste water and waste residues is high. The preparation method of 3,5-dimethoxy phenylcarbinol comprises the following steps that a copper-bearing catalyst is prepared; 3,5-dimethoxy methyl benzoate reacts with hydrogen under the action of the copper-bearing catalyst; and 3,5-dimethoxy phenylcarbinol is prepared. A novel method which is simple, practicable, high in yield, low in cost, and more environment-friendly in technology and adopts no organic solvent during reaction is provided for preparing 3,5-dimethoxy phenylcarbinol industrially.
Description
Technical field
The invention belongs to chemical synthesis process field, be specifically related to the preparation method of 3,5-3,5-dimethoxybenzoic alcohol.
Background technology
3,5-3,5-dimethoxybenzoic alcohol is the important intermediate preparing trans-resveratrol.Trans-resveratrol is a kind of biological very strong natural polyphenol class material, be also called resvertrol, it is the chemopreventive agent of tumour, also be to reduction platelet aggregation, the chemopreventive agent of prevention and therapy atherosclerosis, cardiovascular and cerebrovascular diseases, the verified beneficial effect had cardiovascular disorder and cancer of the experimental study of trans-resveratrol.Trans-resveratrol has obvious prophylactic effect to hormone-dependent tumor (comprising mammary cancer, prostate cancer, carcinoma of endometrium and ovarian cancer etc.).Also can there is prophylactic effect to osteoporosis, acne (comedo) and senile dementia, there is antiviral and immunoregulation effect.At present, trans-resveratrol uses in a large number as healthcare products, makeup and foodstuff additive etc., and market demand is very large.
Trans-resveratrol
At present, the preparation of trans-resveratrol mainly contains following several approach: (1), from the plant containing trans-resveratrol as extracted grape, giant knotweed, because the content of trans-resveratrol in plant is very low, and plant resources is limited, the method is difficult to prepare highly purified product, and cost is high, throughput is little; (2) biological fermentation, as extracted trans-resveratrol with yeast solid anaerobic digestion giant knotweed, the method production cycle is long, process is complicated; (3) chemical synthesis, is reduced into 3,5-3,5-dimethoxybenzoic alcohol by 3,5-dimethoxy p-methyl, and 3,5-3,5-dimethoxybenzoic alcohol, after halogenation, makes Wittig reagent, then reacts with anisyl aldehyde, finally sloughs three methyl and is prepared from.Its reaction formula is:
And in above-mentioned chemical synthesis, when preparation 3,5-3,5-dimethoxybenzoic alcohol, need to use a large amount of sodium borohydrides and tetrahydrofuran (THF).The maximum problem of the method is: 1) can produce a large amount of waste gas when reacting; 2) a large amount of inorganic salt can be produced during aftertreatment; 3) need to use a large amount of organic solvents; 4) loaded down with trivial details, the complicated operation of this technique process, is unfavorable for industrialization.Therefore this technique " three wastes " generation is large, production cost is high, is not easy to industrialization.
Tetrahedron Letters, reports the existing route of synthesis of another outer synthesis 3,5-dihydroxy-benzyl alcohol in 1996,37,1191 – 1194.Its reaction formula is:
The shortcoming of this route is: LiAlH
4(Lithium Aluminium Hydride) is too expensive, produces a large amount of hydrogen in reaction process, production is difficult to control, use of large-scale production danger close.
Summary of the invention
Technical problem to be solved by this invention is that existing synthetic method " three wastes " generation is large, cost is high, complicated operation, is difficult to industrialization.
The technical scheme that the present invention solves the problems of the technologies described above is to provide a kind of preparation method of 3,5-3,5-dimethoxybenzoic alcohol, comprises the steps: first to prepare copper containing catalyst; Again 3,5-dimethoxy p-methyl is reacted with hydrogen under the effect of copper containing catalyst, obtained 3,5-3,5-dimethoxybenzoic alcohol.
Wherein, in the preparation method of above-mentioned 3,5-3,5-dimethoxybenzoic alcohols, the preparation of described copper containing catalyst comprises the following steps:
A, by after silicon sol acidifying through ultrasonication 5 ~ 60 minutes, obtain modified silicasol carrier;
B, the modified silicasol carrier that step a is obtained, join in the aqueous solution of urea and cupric nitrate, stir 1 ~ 10 hour, then system stirred 10 ~ 28 hours at 50 ~ 98 DEG C, filtered while hot goes out solid, deionized water wash solid;
C, by step b washing after solid drying after roasting;
D, the solid hydrogen reducing after step c roasting to be activated, obtained described copper containing catalyst.
Wherein, in the preparation method of above-mentioned 3,5-3,5-dimethoxybenzoic alcohols, described copper containing catalyst is with copper for main activeconstituents, and its carrier is silicon-dioxide; Wherein, copper content is 10% ~ 40% of vehicle weight, and carrier specific surface area is 150 ~ 450m
2/ g.Preferably, copper content is 25% ~ 35% of vehicle weight, and carrier specific surface area is 250 ~ 400m
2/ g.
Wherein, in aforesaid method, dust technology acidifying is used in the acidifying in described step a, and the concentration of dust technology is 0.001 ~ 0.05mol/L.
Preferably, the concentration of described dust technology is 0.005 ~ 0.01mol/L.
Wherein, the ultrasonic treatment time described in aforesaid method step a is preferred 20 ~ 40min.
Wherein, in aforesaid method, in the urea in described step b and the aqueous solution of cupric nitrate, the concentration of urea is 0.05 ~ 1.5mol/L, and the concentration of cupric nitrate is 0.01 ~ 0.5mol/L.
Preferably, in the aqueous solution of described urea and cupric nitrate, the concentration of urea is 0.1 ~ 1.0mol/L, and the concentration of cupric nitrate is 0.05 ~ 0.4mol/L.
Wherein, in aforesaid method, the solid in described step c was 90 ~ 120 DEG C of dryings 6 ~ 12 hours, then roasting 2 ~ 6 hours at 200 ~ 400 DEG C.
Further, described solid was 100 ~ 110 DEG C of dryings 8 ~ 12 hours, then roasting 2 ~ 6 hours at 300 ~ 350 DEG C.
Wherein, in aforesaid method, the reduction activation in described steps d, under referring to normal pressure, activation temperature is 150 ~ 300 DEG C, is the hydrogen stream reduction activation of 60 ~ 150mL/min with flow.
Preferably, the flow of described hydrogen stream is 80 ~ 120mL/min, and activation temperature is 180 ~ 250 DEG C.
Wherein, in aforesaid method, described 3,5-dimethoxy p-methyl reacts with hydrogen under the effect of copper containing catalyst, and concrete operations comprise: gasified by 3,5-dimethoxy p-methyl in atmosphere of hydrogen, make hydrogen and 3, the gas mixture of 5-dimethoxy p-methyl, by copper containing catalyst, obtains product 3,5-3,5-dimethoxybenzoic alcohol; Wherein, the mol ratio of hydrogen and 3,5-dimethoxy p-methyl is 100 ~ 200 ︰ 1, and temperature of reaction is 250 ~ 400 DEG C, and the volume space velocity of 3,5-dimethoxy p-methyl is 0.01 ~ 0.8h
-1, hydrogen pressure is 5 ~ 30atm.
Further, the mol ratio of described hydrogen and 3,5-dimethoxy p-methyl is 70 ~ 150 ︰ 1, and temperature of reaction is 300 ~ 350 DEG C, and the volume space velocity of 3,5-dimethoxy p-methyl is 0.05 ~ 0.6h
-1, hydrogen pressure is 10 ~ 20atm.
Wherein, the concrete operation step of the preparation method of above-mentioned 3,5-3,5-dimethoxybenzoic alcohols comprises:
A, by silicon sol with after dust technology acidifying, through ultrasonication 5 ~ 60 minutes, obtain modified silicasol carrier;
B, the modified silicasol carrier obtained by step a, join urea and cupric nitrate is mixed with in the aqueous solution, and stir 1 ~ 10 hour, be then warming up to 50 ~ 98 DEG C, stir 10 ~ 28 hours, filtered while hot goes out solid, deionized water wash solid;
C, by solid obtained in step b 90 ~ 120 DEG C of dryings 6 ~ 12 hours, then roasting 2 ~ 6 hours at 200 ~ 400 DEG C;
D, by the solid after step c roasting at normal pressure 150 ~ 300 DEG C, be the hydrogen stream reduction activation of 60 ~ 150mL/min with flow, obtained described copper containing catalyst;
E, in atmosphere of hydrogen, 3,5-dimethoxy p-methyl to be gasified, then copper containing catalyst to be fixed on hydrogenation bed, make hydrogen and 3, the gas mixture of 5-dimethoxy p-methyl passes through the bed of catalyzer, and product 3,5-3,5-dimethoxybenzoic alcohol is drawn by reactor bottom; Wherein, the mol ratio of hydrogen and 3,5-dimethoxy p-methyl is 100 ~ 200 ︰ 1, and temperature of reaction is 250 ~ 400 DEG C, and the volume space velocity of 3,5-dimethoxy p-methyl is 0.01 ~ 0.8h
-1, hydrogen pressure is 5 ~ 30atm.
Beneficial effect of the present invention is: technical scheme provided by the invention is the reaction of copper containing catalyst hydrogen catalyzed reduction 3, the 5-dimethoxy p-methyl utilizing preparation.Copper containing catalyst is with copper for main activeconstituents, and be prepared from by precipitation sedimentation, its carrier is silicon-dioxide; Wherein, copper content is 10% ~ 40% of vehicle weight; Carrier specific surface area is 150 ~ 450m
2/ g.This catalyzer has very high reactive behavior in the reaction of hydrogen catalyzed reduction 3,5-dimethoxy p-methyl, and reactivity worth is steady, does not use any organic solvent, achieves the application of green chemistry process, make this novel process environment more friendly.This process costs is low, workable, is easy to suitability for industrialized production.
Embodiment
The preparation method of 3,5-3,5-dimethoxybenzoic alcohol, comprises the steps:
A, by silicon sol with after dust technology acidifying, through ultrasonication 5 ~ 60 minutes, obtain modified silicasol carrier.
B, the modified silicasol carrier obtained by step a, join urea and cupric nitrate is mixed with in the aqueous solution, and stir 1 ~ 10 hour, be then warming up to 50 ~ 98 DEG C, stir 10 ~ 28 hours, filtered while hot goes out solid, deionized water wash solid.
C, by solid obtained in step b 90 ~ 120 DEG C of dryings 6 ~ 12 hours, then roasting 2 ~ 6 hours at 200 ~ 400 DEG C, obtains grass green solid.
D, by grass green solid obtained for step c at normal pressure 150 ~ 300 DEG C, be the hydrogen stream of 60 ~ 150mL/min with flow, carry out the online reduction activation of catalyzer, obtained described copper containing catalyst; The catalyzer of oxidation state does not have catalytic activity, has to pass through reduction activation process before using.
E, in atmosphere of hydrogen, 3,5-dimethoxy p-methyl to be gasified, then copper containing catalyst to be fixed on hydrogenation bed, make hydrogen and 3, the gas mixture of 5-dimethoxy p-methyl passes through the bed of catalyzer, and product 3,5-3,5-dimethoxybenzoic alcohol is drawn by reactor bottom; Wherein, the mol ratio of hydrogen and 3,5-dimethoxy p-methyl is 100 ~ 200 ︰ 1, and temperature of reaction is 250 ~ 400 DEG C, and the volume space velocity of 3,5-dimethoxy p-methyl is 0.01 ~ 0.8h
-1, hydrogen pressure is 5 ~ 30atm.
Wherein, in the preparation method of above-mentioned 3,5-3,5-dimethoxybenzoic alcohols, described copper containing catalyst is with copper for main activeconstituents, and its carrier is silicon-dioxide; Wherein, copper content is 10% ~ 40% of vehicle weight, and carrier specific surface area is 150 ~ 450m
2/ g.Described copper containing catalyst is also referred to as cupric silicate catalysts in the art.The above-mentioned copper containing catalyst prepared is grass green amorphous powder, and its outer appearnce of this grass green amorphous powder is similar to chrysocolla.
Wherein, in the step a of aforesaid method, the concentration of described dust technology is 0.001 ~ 0.05mol/L.
As preferred version of the present invention, described dust technology concentration is 0.005 ~ 0.01mol/L.
As preferred version of the present invention, ultrasonic treatment time is 20 ~ 40min.The object of ultrasonication be silicon sol acidifying is obtained evenly, obtain through the acidified modified silicon sol carrier of nitric acid.
Wherein, in the step b of aforesaid method, in the aqueous solution that described urea and cupric nitrate are mixed with, the concentration of urea is 0.05 ~ 1.5mol/L, and the concentration of cupric nitrate is 0.01 ~ 0.5mol/L.
As preferred version of the present invention, the concentration of urea is 0.1 ~ 1.0mol/L, and the concentration of cupric nitrate is 0.05 ~ 0.4mol/L.
As preferred version of the present invention, in step c, described solid was 100 ~ 110 DEG C of dryings 8 ~ 12 hours, then roasting 2 ~ 6 hours at 300 ~ 350 DEG C.
As preferred version of the present invention, in steps d, the flow of hydrogen stream is 80 ~ 120mL/min, and temperature control, at 180 ~ 250 DEG C, carries out the reduction activation of catalyzer.
As preferred version of the present invention, in step e, the mol ratio of described hydrogen and 3,5-dimethoxy p-methyl is 70 ~ 150 ︰ 1, and temperature of reaction is 300 ~ 350 DEG C, and the volume space velocity of 3,5-dimethoxy p-methyl is 0.05 ~ 0.6h
-1, hydrogen pressure is 10 ~ 20atm.
Specific embodiment is below provided to be described further technical scheme of the present invention.
Embodiment 1
A, by silicon sol 60 grams, join 150 milliliters, in the dust technology of 0.01mol/L, by ultrasonication 40 minutes.
B, the urea of the cupric nitrate of 20 grams and 20 grams is joined in the reaction flask of 1 liter, rethink in bottle the deionized water adding 300 milliliters, after stirring and dissolving clarification, modified silicasol obtained in step (a) is joined in the mixing solutions of cupric nitrate and the urea prepared, in stirred at ambient temperature after 4 hours, this reaction flask is heated to 90 DEG C, and stirs 14 hours at this temperature; Filtered while hot, and wash solids by 200 ml deionized water.
C, by solid obtained in step (b) at 100 DEG C, dry 8 hours, then roasting 3 hours in 300 DEG C of retort furnaces, obtain grass green solid.
D, by grass green solid obtained for step (c) at ambient pressure, flow is the hydrogen stream of 100mL/min, and temperature control, at 230 DEG C, carries out the online reduction activation of catalyzer, the active catalyst that just can obtain.
E, by 100 grams 3,5-dimethoxy p-methyl is preheated to 300 DEG C of gasifications in hydrogen, again copper containing catalyst obtained in step (d) is placed in pipeline reactor, be fixed on hydrogenation bed, make hydrogen and 3, the gas mixture of 5-dimethoxy p-methyl passes through the bed of catalyzer, and product 3,5-3,5-dimethoxybenzoic alcohol is drawn by reactor bottom; The mol ratio of hydrogen and 3,5-dimethoxy p-methyl is 150:1, and temperature is at 300 DEG C, and volume space velocity when 3,5-dimethoxy p-methyl is liquid is 0.6h
-1, react under the hydrogen pressure of 20atm, after 1 hour, collect 3, the 5-3,5-dimethoxybenzoic alcohols of 84 grams, productive rate is 98.0%.
Embodiment 2
A, by silicon sol 60 grams, join 150 milliliters, in the dust technology of 0.005mol/L, by ultrasonication 30 minutes.
B, the urea of the cupric nitrate of 15 grams and 15 grams is joined in the reaction flask of 1 liter, rethink in bottle the deionized water adding 250 milliliters, after stirring and dissolving clarification, modified silicasol obtained in step (a) is joined in the mixing solutions of cupric nitrate and the urea prepared, in stirred at ambient temperature after 4 hours, this reaction flask is heated to 70 DEG C, and stirs 14 hours at this temperature; Filtered while hot, and wash solids by 200 ml deionized water.
C, by solid obtained in step (b) at 110 DEG C, dry 6 hours, then roasting 2 hours in 350 DEG C of retort furnaces, obtain grass green solid.
D, by grass green solid obtained for step (c) at ambient pressure, flow is the hydrogen stream of 90mL/min, and temperature control, at 180 DEG C, carries out the online reduction activation of catalyzer, the active catalyst that just can obtain.
E, by 120 grams 3,5-dimethoxy p-methyl is preheated to 300 DEG C of gasifications in hydrogen, again copper containing catalyst obtained in step (d) is placed in pipeline reactor, be fixed on hydrogenation bed, make hydrogen and 3, the gas mixture of 5-dimethoxy p-methyl passes through the bed of catalyzer, and product 3,5-3,5-dimethoxybenzoic alcohol is drawn by reactor bottom; The mol ratio of hydrogen and 3,5-dimethoxy p-methyl is 80:1, and temperature is at 350 DEG C, and volume space velocity when 3,5-dimethoxy p-methyl is liquid is 0.4h
-1, react under the hydrogen pressure of 15atm, after 2 hours, collect 3, the 5-3,5-dimethoxybenzoic alcohols of 100 grams, productive rate is 97.2%.
Embodiment 3
A, by silicon sol 80 grams, join 200 milliliters, in the dust technology of 0.008mol/L, by ultrasonication 30 minutes.
B, the urea of the cupric nitrate of 30 grams and 30 grams is joined in the reaction flask of 1 liter, rethink in bottle the deionized water adding 320 milliliters, after stirring and dissolving clarification, modified silicasol obtained in step (a) is joined in the mixing solutions of cupric nitrate and the urea prepared, in stirred at ambient temperature after 4 hours, this reaction flask is heated to 90 DEG C, and stirs 14 hours at this temperature; Filtered while hot, and wash solids by 250 ml deionized water.
C, by solid obtained in step (b) at 90 DEG C, dry 9 hours, then roasting 5 hours in 330 DEG C of retort furnaces, obtain grass green solid.
D, by grass green solid obtained for step (c) at ambient pressure, flow is the hydrogen stream of 120mL/min, and temperature control, at 250 DEG C, carries out the online reduction activation of catalyzer, the active catalyst that just can obtain.
E, by 150 grams 3,5-dimethoxy p-methyl is preheated to 300 DEG C of gasifications in hydrogen, again copper containing catalyst obtained in step (d) is placed in pipeline reactor, be fixed on hydrogenation bed, make hydrogen and 3, the gas mixture of 5-dimethoxy p-methyl passes through the bed of catalyzer, and product 3,5-3,5-dimethoxybenzoic alcohol is drawn by reactor bottom; The mol ratio of hydrogen and 3,5-dimethoxy p-methyl is 120:1, and temperature is at 300 DEG C, and volume space velocity when 3,5-dimethoxy p-methyl is liquid is 0.2h
-1, react under the hydrogen pressure of 18atm, after 4 hours, collect 3, the 5-3,5-dimethoxybenzoic alcohols of 124 grams, productive rate is 96.4%.
More than experiment shows, technical scheme provided by the invention is the hydrogen catalyzed reduction of copper containing catalyst utilizing preparation, the reaction of 5-dimethoxy p-methyl, in this reaction, copper containing catalyst has very high reactive behavior, reactivity worth is steady, do not use any organic solvent, achieve the application of green chemistry process, make this novel process environment more friendly.This process costs is low, workable, is easy to suitability for industrialized production.
Claims (12)
- The preparation method of 1.3,5-3,5-dimethoxybenzoic alcohol, is characterized in that: first prepare copper containing catalyst; Again 3,5-dimethoxy p-methyl is reacted with hydrogen under the effect of copper containing catalyst, obtained 3,5-3,5-dimethoxybenzoic alcohol; The preparation of described copper containing catalyst comprises the following steps:A, by after silicon sol acidifying through ultrasonication 5 ~ 60 minutes, obtain modified silicasol carrier; Dust technology acidifying is used in described acidifying, and the concentration of dust technology is 0.001 ~ 0.05mol/L;B, the modified silicasol carrier that step a is obtained, join in the aqueous solution of urea and cupric nitrate, stir 1 ~ 10 hour, then system stirred 10 ~ 28 hours at 50 ~ 98 DEG C, filtered while hot goes out solid, deionized water wash solid;C, by step b washing after solid drying after roasting;D, the solid hydrogen reducing after step c roasting to be activated, obtained described copper containing catalyst.
- 2. the preparation method of 3,5-3,5-dimethoxybenzoic alcohols according to claim 1, is characterized in that: the concentration of described dust technology is 0.005 ~ 0.01mol/L.
- 3. the preparation method of 3,5-3,5-dimethoxybenzoic alcohols according to claim 1, is characterized in that: the ultrasonic treatment time in described step a is 20 ~ 40min.
- 4. the preparation method of 3,5-3,5-dimethoxybenzoic alcohols according to claim 1, is characterized in that: in the urea in described step b and the aqueous solution of cupric nitrate, the concentration of urea is 0.05 ~ 1.5mol/L, and the concentration of cupric nitrate is 0.01 ~ 0.5mol/L.
- 5. the preparation method of 3,5-3,5-dimethoxybenzoic alcohols according to claim 4, is characterized in that: in described urea and the aqueous solution of cupric nitrate, the concentration of urea is 0.1 ~ 1.0mol/L, and the concentration of cupric nitrate is 0.05 ~ 0.4mol/L.
- 6. the preparation method of 3,5-3,5-dimethoxybenzoic alcohols according to claim 1, is characterized in that: the solid in described step c was 90 ~ 120 DEG C of dryings 6 ~ 12 hours, then roasting 2 ~ 6 hours at 200 ~ 400 DEG C.
- 7. the preparation method of 3,5-3,5-dimethoxybenzoic alcohols according to claim 6, is characterized in that: described solid was 100 ~ 110 DEG C of dryings 8 ~ 12 hours, then roasting 2 ~ 6 hours at 300 ~ 350 DEG C.
- 8. the preparation method of 3,5-3,5-dimethoxybenzoic alcohols according to claim 1, is characterized in that: the reduction activation in described steps d, and under referring to normal pressure, activation temperature is 150 ~ 300 DEG C, is the hydrogen stream reduction activation of 60 ~ 150mL/min with flow.
- 9. the preparation method of 3,5-3,5-dimethoxybenzoic alcohols according to claim 8, is characterized in that: the flow of described hydrogen stream is 80 ~ 120mL/min, and activation temperature is 180 ~ 250 DEG C.
- 10. according to claim 13, the preparation method of 5-3,5-dimethoxybenzoic alcohol, it is characterized in that: described 3,5-dimethoxy p-methyl reacts with hydrogen under the effect of copper containing catalyst, and operation comprises: gasified by 3,5-dimethoxy p-methyl in atmosphere of hydrogen, make hydrogen and 3, the gas mixture of 5-dimethoxy p-methyl, by copper containing catalyst, obtains product 3,5-3,5-dimethoxybenzoic alcohol; Wherein, the mol ratio of hydrogen and 3,5-dimethoxy p-methyl is 100 ~ 200 ︰ 1, and temperature of reaction is 250 ~ 400 DEG C, and the volume space velocity of 3,5-dimethoxy p-methyl is 0.01 ~ 0.8h -1, hydrogen pressure is 5 ~ 30atm.
- 11. according to claim 10 3, the preparation method of 5-3,5-dimethoxybenzoic alcohol, it is characterized in that: described hydrogen and 3, the mol ratio of 5-dimethoxy p-methyl is 70 ~ 150 ︰ 1, temperature of reaction is 300 ~ 350 DEG C, the volume space velocity of 3,5-dimethoxy p-methyl is 0.05 ~ 0.6h -1, hydrogen pressure is 10 ~ 20atm.
- The preparation method of 12. 3,5-3,5-dimethoxybenzoic alcohols according to claim 1, is characterized in that: comprise following operation steps:A, by silicon sol with after dust technology acidifying, through ultrasonication 5 ~ 60 minutes, obtain modified silicasol carrier;B, the modified silicasol carrier obtained by step a, join urea and cupric nitrate is mixed with in the aqueous solution, and stir 1 ~ 10 hour, be then warming up to 50 ~ 98 DEG C, stir 10 ~ 28 hours, filtered while hot goes out solid, deionized water wash solid;C, by solid obtained in step b 90 ~ 120 DEG C of dryings 6 ~ 12 hours, then roasting 2 ~ 6 hours at 200 ~ 400 DEG C;D, by the solid after step c roasting at normal pressure 150 ~ 300 DEG C, be the hydrogen stream reduction activation of 60 ~ 150mL/min with flow, obtained described copper containing catalyst;E, in atmosphere of hydrogen, 3,5-dimethoxy p-methyl to be gasified, then copper containing catalyst to be fixed on hydrogenation bed, make hydrogen and 3, the gas mixture of 5-dimethoxy p-methyl passes through the bed of catalyzer, and product 3,5-3,5-dimethoxybenzoic alcohol is drawn by reactor bottom; Wherein, the mol ratio of hydrogen and 3,5-dimethoxy p-methyl is 100 ~ 200 ︰ 1, and temperature of reaction is 250 ~ 400 DEG C, and the volume space velocity of 3,5-dimethoxy p-methyl is 0.01 ~ 0.8h -1, hydrogen pressure is 5 ~ 30atm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310031377.9A CN103073399B (en) | 2013-01-28 | 2013-01-28 | Preparation method of 3,5-dimethoxy phenylcarbinol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310031377.9A CN103073399B (en) | 2013-01-28 | 2013-01-28 | Preparation method of 3,5-dimethoxy phenylcarbinol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103073399A CN103073399A (en) | 2013-05-01 |
| CN103073399B true CN103073399B (en) | 2015-04-22 |
Family
ID=48150123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310031377.9A Active CN103073399B (en) | 2013-01-28 | 2013-01-28 | Preparation method of 3,5-dimethoxy phenylcarbinol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103073399B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5328777B2 (en) * | 2008-04-30 | 2013-10-30 | 三井化学株式会社 | Propylene glycol production method |
| CN101544591B (en) * | 2009-05-06 | 2013-07-10 | 河北科技大学 | (E)-substituted styrene compound and preparation method thereof |
| CN102125843B (en) * | 2010-12-07 | 2013-04-10 | 浙江大学 | Method for preparing catalyst for hydrogenation reaction of dimethyl oxalate and product |
| CN102380381B (en) * | 2011-09-09 | 2013-05-01 | 久泰能源科技有限公司 | Nanometer ultrafine glycol copper silicon catalyst and preparation method thereof |
-
2013
- 2013-01-28 CN CN201310031377.9A patent/CN103073399B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103073399A (en) | 2013-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104069883B (en) | A kind of cobalt-base catalyst for alcohol oxidation generation ester and preparation method thereof and application | |
| CN104069891B (en) | The preparation method of the immobilized HP catalyst of a kind of polymer microballoon | |
| CN103121987B (en) | Method for preparing alkylene carbonate | |
| CN104262120B (en) | A kind of vanillin food grade,1000.000000ine mesh catalytic hydrodeoxygenation prepares the method for 4-methyl guaiacol and 4 | |
| CN106495105A (en) | A kind of method of synthesis nanometer selenium material | |
| CN113385171A (en) | Metal-based catalyst protected by few-layer carbon and application thereof in ethylene oxide carbonylation | |
| CN111097416A (en) | Preparation of carbon-supported cobalt heterogeneous catalyst and application of carbon-supported cobalt heterogeneous catalyst in catalyzing hydroformylation reaction of olefin | |
| CN103864549B (en) | Method for preparing diphenyl ketone compound | |
| CN109926056A (en) | It is a kind of using carbon nanotube as the catalyst of carrier, preparation method and application | |
| CN102295524A (en) | Method for preparing cyclohexanol and cyclohexanone by selective oxidation of cyclohexane | |
| CN103145545A (en) | Method of preparing propanoldiacid through catalytic oxidation of glycerol | |
| CN105964306B (en) | It is a kind of based on poly ion liquid magnetic nano-particle, preparation method and its application in three component reactions | |
| CN104815657A (en) | Preparation method of catalyst for producing catechol and hydroquinone through hydroxylation of phenol | |
| CN105772000A (en) | Graphene oxide promoted copper-based methanol synthesis catalyst and preparation method thereof | |
| CN109772326A (en) | A kind of catalyst and its preparation method and application synthesizing Fluorenone | |
| CN103012079B (en) | The method of solid base catalyst catalytically synthesizing glycol propenyl ether | |
| CN102407160A (en) | Preparation method of core-shell structure CeO2@SiO2 load metalloporphyrin catalyst prepared by double wrapping method | |
| CN102464633B (en) | Synthetic method for (methyl) glycidyl acrylate | |
| CN103073399B (en) | Preparation method of 3,5-dimethoxy phenylcarbinol | |
| JP5914615B1 (en) | Heterogeneous catalyst for producing 3-hydroxypropionic acid from allyl alcohol, and method for producing 3-hydroxypropionic acid from allyl alcohol using the same | |
| CN103709010B (en) | A kind of by tetrahydrobenzene, carboxylic acid and water Reactive Synthesis hexalin method | |
| CN105906484A (en) | Method for preparing phenol by directly oxidizing benzene | |
| CN110256230A (en) | Efficient catalytic glycerol prepares catalyst of glyceric acid and preparation method thereof under the conditions of a kind of alkali-free | |
| CN101898156A (en) | Preparation method for CeO2 doped organosilicon nanometer microsphere metal cobalt loaded (ii) porphyrin catalyst | |
| CN104311404A (en) | Method for producing cinnamyl aldehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20150922 Address after: Wenjiang District 611130 of Sichuan city of Chengdu province Chengdu Strait science and Technology Industry Development Park No. 488 West Ke Lin Lu Patentee after: ASTATECH (CHENGDU) PHARM. CO., LTD. Address before: Gaopeng Avenue, Chengdu hi tech Development Zone 611137 Sichuan province No. 5 students Pioneering Park East (Chengdu) Medical Technology Co Ltd Patentee before: AstaTech (Chengdu) Pharmaceutical Co., Ltd. |
|
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: Wenjiang District 610000 of Sichuan city of Chengdu province Chengdu Strait science and Technology Industry Development Park No. 488 West Ke Lin Lu Patentee after: Astatech (Chengdu) biological pharmaceutical Limited by Share Ltd Address before: Wenjiang District 611130 of Sichuan city of Chengdu province Chengdu Strait science and Technology Industry Development Park No. 488 West Ke Lin Lu Patentee before: ASTATECH (CHENGDU) PHARM. CO., LTD. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method and equipment for prepn. of 1,2,3-pentaerythritol Effective date of registration: 20170822 Granted publication date: 20150422 Pledgee: Chengdu SME financing Company Limited by Guarantee Pledgor: Astatech (Chengdu) biological pharmaceutical Limited by Share Ltd Registration number: 2017510000052 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20180801 Granted publication date: 20150422 Pledgee: Chengdu SME financing Company Limited by Guarantee Pledgor: Astatech (Chengdu) biological pharmaceutical Limited by Share Ltd Registration number: 2017510000052 |