CN103936567A - Co-production method of preparing corresponding alcohol, ester, aldehyde and acid by oxidizing p-methoxyl methylbenzene by oxygen - Google Patents
Co-production method of preparing corresponding alcohol, ester, aldehyde and acid by oxidizing p-methoxyl methylbenzene by oxygen Download PDFInfo
- Publication number
- CN103936567A CN103936567A CN201410185353.3A CN201410185353A CN103936567A CN 103936567 A CN103936567 A CN 103936567A CN 201410185353 A CN201410185353 A CN 201410185353A CN 103936567 A CN103936567 A CN 103936567A
- Authority
- CN
- China
- Prior art keywords
- acid
- water
- acetate
- catalyst
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a co-production method for preparing corresponding alcohol, ester, aldehyde and acid by oxidizing p-methoxyl methylbenzene by oxygen. The method comprises the following steps: adding p-methoxyl methylbenzene, a catalyst I and a solvent into an oxidizing reaction kettle, and introducing oxygen to react; after oxidizing reaction, recovering the solvent and optionally selecting to apply mechanically, and then adding water to wash the catalyst I to obtain an organic phase I and an aqueous phase I; adding alkali into the organic phase I, decompressing and evaporating an organic phase II, after adding water to the bottom, adjusting the pH value by an acid, and filtering to obtain p-methoxybenzoic acid; distilling the water phase I to recover water, optionally selecting to apply mechanically, further adding the catalyst I and the solvent at the bottom, and optionally selecting to apply mechanically in oxidizing reaction; rectifying the organic phase II to obtain a product p-methoxybenzaldehyde and anisyl acetate; carrying out basic hydrolysis on anisyl acetate to obtain an anisic alcohol crude product; and rectifying to obtain an anisic alcohol pure product. The co-production method provided by the invention has the advantages of greenness and environment protection, mild reaction condition, low cost and less three waste, and is easy to industrially produce, and the obtained product is widely applied to the fields of foods, medicines and daily chemicals.
Description
Technical field
The present invention relates to a kind of preparation method of organic intermediate, in particular to the co-production preparation method of p-methoxybenzyl alcohol, cassie ketone, aubepine and anisic acid, belong to daily-use chemical industry technical field.
Background technology
Aubepine (Anisic aldehyde), is colourless to weak yellow liquid under normal temperature, has the smell of similar hawthorn.Density 1.123g/cm
3(20 DEG C).0 DEG C of fusing point.249.5 DEG C of boiling points.Specific refractory power 1.5731.Be insoluble in water, be soluble in ethanol, ether, acetone, chloroform.Can volatilize with water vapour.Be present in olium anisi, Sweet fennel oil, oleum anethi, acacia flos, vanilla medicinal extract at occurring in nature, obtain through oxidation separation and Extraction.As spices, preparation bouquet type composition, for food and makeup, perfumed soap etc.Pharmaceutically be used as the intermediate of antihistamine drug, as little being also used as such as antibiotic oxyammonia benzylpenicillin processed are electroplated optical brightener etc.
The synthetic method of aubepine comprises following several:
(1) methylated with methyl-sulfate by phenol, and then make (PCT2008023836 through the reaction such as chloromethylation, hydrolysis; CN01838173; Compt.Rend., 1934,198:2256-22588);
(2) by p-methyl phenol through methylating, reoxidize and obtain (CN1249362; Russ., 2043986; JP2011162489; CN1491930; JP2010202556; EP459729; Bull.Chem.Soc.Japan, 1988,61 (3): 967-971; EP228275; JP62108837; JP60233027; J.Mole.Catal., 1990,61 (1): 51-54; J.Org.Chem., 1997,62 (20): 6810-6813; JP102070382);
(3) methylate and obtain (Org.Process Res.Dev., 2005,9 (1): 70-79 by p-Hydroxybenzaldehyde; PCT2001009072; Chem.Res.Chin.Universities, 2013,29 (2): 319-323; JP10287608; CN102531860; CN101462933; NA9200968; CN1319581; JP63104937; CN1249298; CN1247851; Adv.Synth.Catal., 2004,346 (6): 633-638; EP577476).
P-methoxybenzyl alcohol, colourless or micro-yellow liquid.Fusing point 23-25.5 DEG C, 159 DEG C of boiling points, relative density 1.113 (15/15 DEG C), refractive index 1.5442.Be soluble in alcohol and ether, water-soluble hardly.There is slightly sweetish fennel fragrance, be usually used in preparing the essence such as jasmine, Syringa oblata Lindl., be suitable for allocating perfume.Gai Pinshi China GB2760-86 is defined as the flavouring agent that allows use.Mainly in order to prepare the essence such as vanilla, chocolate, cocoa, almond, peach.Also for organic synthesis with as solvent.
The method of synthetic p-methoxybenzyl alcohol mainly makes (CN102320939 by aubepine through reduction; J.Ind.Eng.Chem., 2007,13 (7): 1067-1075; J.Med.Chem., 2013,56 (20): 8201-8205; Angew.Chem.-Int.Edit., 2013,52 (45): 11871-11874; Angew.Chem.-Int.Edit., 2013,52 (19): 5120-5124; Organometallics, 2013,32 (16): 4501-4506; Chem.Commun., 2012,48 (66): 8276-8278; Angew.Chem.-Int.Edit., 2012,51 (48): 12102-12106; Catal.Lett., 2013,143 (1): 122-125; J.Mole.Catal.A:Chem., 2009,299 (1-2): 98-101; Eur.J. Org.Chem., 2009, (21): 3567-3572; Tetrahedron Lett., 2009,50 (32): 4624-4628; CN1994988; Tetrahedron Lett., 2006,47 (25): 4161-4165; PCT2003089395; Synth.Commun., 2001,31 (17): 2719-2725; Catal.Commun., 2012,28:147-151; Green Chem., 2012,14 (5): 1372-1375; J.Am.Chem.Soc., 2010,132 (34): 11978-11987; ACS Catal., 2013,3 (2): 182-185; Tetrahedron Lett., 2012,53 (2): 148-150; Daily chemical industry, 2008,38 (4): 242-244; JP2006088026).
Anisic acid, colourless acicular crystal, fusing point 182-185 DEG C (lit.), 275 DEG C of boiling points, density 1.385, specific refractory power 1.571-1.576,185 DEG C of flash-points.Be dissolved in ethanol, ether, chloroform, be slightly soluble in hot water, be insoluble in cold water.As medicine intermediates such as eggplant La Xitan, ethamine sulphur skin ketone, also can be used for spices, sanitas etc.Can be raw material by P-hydroxybenzoic acid, react acquisition (Indian Pat.Appl., 2008MU01043 with methyl-sulfate; Indian Pat.Appl., 2006MU00718; ), can aubepine be also raw material, through oxidation preparation (Tetrahedron Lett., 2013,54 (46): 6222-6225; Synlett, 2013,24 (8): 963-966; Inorg.Chem., 2008,47 (13): 5821-5830; Indian Pat.Appl., 1999DE01492; PCT2011037542; PCT2004054956).
Acetic acid fennel ester, Anisyl acetate, density 1.014 (20 DEG C), 270 DEG C of boiling points, specific refractory power 1.5110~1.5160.Colourless to light yellow liquid, there are stronger Acacia fragrance and cassia bark fragrance, pleasantly sweet.Water insoluble, propylene glycol, glycerine, be dissolved in ethanol and most of non-volatile oils.The bouquet type compositions such as modulation cloves, silvery white Acacia, Acacia, violet, for makeup; The flavor essences such as modulation chocolate, cocoa, vanilla, berry, strawberry, for food.Taking anisy alcohol and acetic acid (acetic anhydride) as raw material, direct esterification makes (J.Flow Chem., 2012,2:47-51; Synthesis, 2011, (10): 1621-1625; J.Iran.Chem.Soc., 2009,6 (3): 523-532; Tetrahedron Lett., 2009,50 (4): 395-397; Catal.Commun., 2014,44:24-28; PCT2002038553).
Obviously, synthetic p-methoxybenzyl alcohol, anisic acid and acetic acid fennel ester, all need be taking aubepine as raw material, or through reduction, or through oxidation, or through esterification preparation, reaction process and aftertreatment are all loaded down with trivial details.And aubepine, at present mainly taking p-cresol as raw material, in alkaline medium, is prepared into p-Hydroxybenzaldehyde through dioxygen oxidation, obtain via methyl-sulfate etherificate.No matter be oxidation, or etherificate, all need to produce a large amount of three wastes, bring pressure to environmental protection and production.
Summary of the invention
The object of the present invention is to provide one can prepare high-quality p-methoxybenzyl alcohol simultaneously, cassie ketone, the co-production of aubepine and anisic acid, avoid use initiator in the oxidizing reaction stage, especially halogen initiator, use cheap oxygen as oxygenant, use chemical oxidizing agent and other organic peroxide oxidant are avoided, adopt gentle alkaline hydrolysis condition, adopt self-closing circulation to realize the circulation of material, therefore reduced the generation of manufacturing cost and the three wastes, alleviate environmental protection pressure, but also have easy, be easy to the feature of control and suitability for industrialized production.
The inventor finds by research, by the synthesis technique comprising the steps, taking to methoxy toluene as raw material, under the existence of Halogen catalyzer, generate p-methoxybenzyl alcohol, cassie ketone, aubepine and anisic acid through dioxygen oxidation, p-methoxybenzyl alcohol, cassie ketone, aubepine and the anisic acid that can obtain high-quality, reactive chemistry formula is:
Therefore the co-production that, dioxygen oxidation of the present invention is prepared corresponding p-methoxybenzyl alcohol, cassie ketone, aubepine and anisic acid to methoxy toluene comprises the following steps:
Step 1), in oxidizing reactor, add methoxy toluene, catalyst I and solvent, pass at a certain temperature oxygen, stopped reaction after reaction certain hour;
Step 2), oxidizing reaction finishes, and reclaims solvent, optionally for applying mechanically, then adds washing to go catalyst I, obtains organic phase I and water I;
Step 3), in organic phase I, add alkali, decompression steams organic phase II, heats up in a steamer the end and use sour adjust pH after adding water, and filtration obtains anisic acid;
Step 4), water I Distillation recovery water, optionally for applying mechanically, heats up in a steamer the end and adds after catalyst I and solvent, optionally applies mechanically for oxidizing reaction;
Step 5), organic phase II rectifying obtains finished product aubepine and cassie ketone;
Step 6), cassie ketone alkaline hydrolysis, obtains anisy alcohol crude product, obtains anisy alcohol sterling through rectifying.
The following specifically describes the present invention.
In step 1 of the present invention, in oxidizing reactor, add methoxy toluene, catalyst I and solvent, pass at a certain temperature oxygen, stopped reaction after reaction certain hour.
According to the present invention, the solvent using in step 1 is organic carboxyl acid class, as formic acid, acetic acid, propionic acid, butyric acid, Mono Chloro Acetic Acid, trifluoroacetic acid etc., and preferably acetic acid or propionic acid, the solvent that particularly preferably acetic acid is oxidizing reaction.
Solvent for use (for example acetic acid) is 1~50:1 with the mole dosage ratio to methoxy toluene, preferably 3~30:1, more preferably 5~15:1.
Used catalyst I is transition metal salt, preferably acetate, as cobaltous acetate, manganous acetate, nickelous acetate, cerous acetate, chromium acetate, zinc acetate, ironic acetate, crystal aerugo, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, manganous nitrate, nitric acid ketone, cobalt chloride, cobaltous bromide, acetylacetone cobalt, ferric acetyl acetonade, cobalt stearate, manganese stearate, cobalt naphthenate, acid chloride, one of Palladous chloride etc., or several catalyzer are wherein pressed the composite catalyst of certain mol proportion composition, preferably cobaltous acetate, manganous acetate, chromium acetate, cerous acetate, acid chloride, ironic acetate, one of venus crystals etc., or they press the composite catalyst of certain mol proportion composition.
According to the present invention, select the catalyzer of transition metal salt as oxidizing reaction, can avoid using initiator, especially do not use halogen initiator, make not contain micro-initiator in the finished product p-methoxybenzyl alcohol, can meet the safety requirements of food, medicine and other fields completely.
Used catalyst I is 0.1~2.0:1 with the mole dosage ratio to methoxy toluene, preferably 0.2~1.0.
The temperature of oxidizing reaction is 40~150 DEG C, and preferable reaction temperature is 80~120 DEG C, more preferably 100~115 DEG C.
Oxidation pressure (gauge pressure) is 0~2.0MPa, preferably 0~1.2MPa, and more preferably 0~0.5MPa wherein, carries out oxidizing reaction in the time that gauge pressure is 0 under normal pressure.
Oxidation time is 0.1-20h, preferably 1-10h, more preferably 2-8h.
By step 1 of the present invention, use cheap oxygen as oxygenant, to methoxy toluene catalyzed oxidation in liquid phase situation, avoid using chemical oxidizing agent and other organic peroxide oxidant, mainly generate aubepine, acetic acid fennel ester and a small amount of anisic acid.
In step 2 of the present invention, oxidizing reaction finishes, and reclaims solvent, optionally for applying mechanically, then adds washing to go catalyst I, obtains organic phase I and water I.
According to the present invention, preferably need to control certain moisture from for example acetic acid of oxidizing reaction system recovered solvent and just can apply mechanically, for example control the moisture of acetic acid 0~50%, preferably control the moisture of acetic acid 3~30%.
After solvent recuperation finishes, need to add water that catalyst I is washed to separation, obtain respectively organic phase I and water I.
Washing times can be 1~10 time, and preferably washing times is 2~6 times, more preferably 3~5 times.
When each washing, water is 0.1~40:1 with the mole dosage ratio to methoxy toluene, preferably 1~20:1, more preferably 3~5 times.
In step 3 of the present invention, in organic phase I, add alkali, decompression steams organic phase II, heats up in a steamer the end and use sour adjust pH after adding water, and filtration obtains anisic acid.
The alkali that step 3 of the present invention is used is basic metal inorganic acid salt or oxyhydroxide, is preferably sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide etc., more preferably sodium carbonate and salt of wormwood, particularly preferably sodium carbonate.
Described alkali adds with the form of solid, and alkali is 0.01~1:1 with the mole dosage ratio to methoxy toluene, preferably 0.05~0.5:1, more preferably 0.1~0.3:1.
Decompression steams organic phase II, heats up in a steamer the end to add after water with acid for adjusting pH value, can regulate pH value=1-5, preferably 2-3.Acid used is mineral acid example hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid etc., or organic acid is as formic acid, acetic acid, propionic acid, butyric acid etc., preferably sulfuric acid and acetic acid, particularly preferably sulfuric acid.
Taking sulfuric acid as example, its concentration is 5-85%, is preferably 72%; Temperature of reaction is 60~120 DEG C, preferably 80~110 DEG C.
In step 4 of the present invention, water I Distillation recovery water, optionally for applying mechanically, heats up in a steamer the end and adds after catalyst I and solvent, optionally applies mechanically for oxidizing reaction.
Water I Distillation recovery water, without any processing, can be directly used in washing in step 2 and apply mechanically, and heats up in a steamer the end and adds after appropriate catalyst I and solvent, is preferably directly used in oxidizing reaction and applies mechanically.
The above-mentioned amount of adding catalyzer be catalyzer first charging capacity 1~30%, preferably 1~10%.
Charging capacity is identical first with acetic acid to add the amount of solvent acetic acid.
In step 5 of the present invention, organic phase II rectifying obtains finished product aubepine and cassie ketone.
For example, at 124-130 DEG C of still temperature and under pressure 3-5mmHg, carry out rectifying and obtain aubepine, at 136-138 DEG C of still temperature and carry out rectifying under pressure 3-5mmHg, acquisition cassie ketone.
In step 6 of the present invention, cassie ketone alkaline hydrolysis, obtains anisy alcohol crude product, obtains anisy alcohol sterling through rectifying.
Alkaline hydrolysis alkali used is the aqueous solution of an alkali metal salt or oxyhydroxide, the preferably aqueous solution of sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide etc., the preferably aqueous solution of sodium hydroxide, potassium hydroxide etc.
The concentration of described alkali is 1~50%, preferably 5~30%.
Described alkali is 1~5:1 with the mole dosage ratio to methoxy toluene, preferably 1.2~3:1, more preferably 1.5~2:1.
Temperature of reaction is 60~120 DEG C, preferably 80~110 DEG C.
Reaction times is 0.5~5h, preferably 1.5~3.0h.
Then, the anisy alcohol crude product that hydrolysis reaction obtains for example at 130-136 DEG C of still temperature and pressure 3-5mmHg carry out rectifying, acquisition final product anisy alcohol.
Beneficial effect of the present invention is mainly reflected in the following aspects:
(1), the oxidizing reaction stage, select the catalyzer of transition metal salt as oxidizing reaction, avoid the use of initiator, especially avoided the use of halogen initiator, for p-methoxybenzyl alcohol, cassie ketone, aubepine and the anisic acid of production high-quality simultaneously provide a kind of good method, prepared product can be used for the fields such as food, medicine, detergents and cosmetic.
(2), oxidizing reaction uses cheap oxygen as oxygenant, avoided the use of chemical oxidizing agent and other organic peroxide oxidant, has the feature of economy, environmental protection, green high-efficient.
(3), a kind of convenient method that reclaims catalyzer is provided, and the catalyzer reclaiming applies mechanically repeatedly, do not find decay of activity.
(4), adopt gentle alkaline hydrolysis condition, cassie ketone can easily be changed into p-methoxybenzyl alcohol, reduced manufacturing cost.
(5), adopt self-closing circulation technology, realized the circulation of all materials, greatly reduce the generation of manufacturing cost and the three wastes, alleviated environmental protection pressure.
That the inventive method also has is easy, be easy to control and the feature of suitability for industrialized production.
Embodiment
Further explain and describe content of the present invention by embodiment below, but embodiment is not to be construed as limiting the scope of the invention.
embodiment 1
488.8Kg acetic acid (KF<1%), 25.2Kg cobaltous acetate, 12.5Kg manganous acetate and 122.2Kg are put in dry stainless steel oxidation still methoxy toluene, be warmed up to after 105-115 DEG C, pass into oxygen, after pressure (gauge pressure) is for insulation reaction 6.5h under 0.10MPa, stop passing into oxygen, GC is in sampling and HPLC detects, GC result is, to methoxy toluene 51.5699%, aubepine 25.9841%, p-methoxybenzyl alcohol 1.1660% and acetic acid fennel ester 20.5117%, HPLC detects aldehydic acid and compares 13.2:1.
Oxidizing reaction finishes, and reclaims acetic acid KF=5.42%, and acetic acid content 89.29% is directly used in down batch oxidizing reaction and applies mechanically.Acetic acid reclaims and finishes, and under nitrogen protection, with 200Kg, 100Kg and the clean tap water washing of 50Kg, stratification after stirring 30min, obtains water I399.3Kg and oil phase I150.5Kg respectively.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 51.5072%, aubepine 25.8914%, p-methoxybenzyl alcohol 0.9629% and acetic acid fennel ester 20.9071%, HPLC detects aldehydic acid and compares 13.5:1.
Under nitrogen protection, the oil phase I150.5Kg of washing gained is added in still kettle, add anhydrous sodium carbonate 5Kg, underpressure distillation obtains organic phase II137Kg.Heating up in a steamer the end adds 100Kg water, is neutralized to pH=2-3 with 72% sulfuric acid, filters, and obtains anisic acid 4.5Kg.
Organic phase II137Kg rectifying under 110-124 DEG C of still temperature and 6-8mmHg pressure obtains methoxy toluene 57.9Kg, GC purity 99.87%, under 124-130 DEG C of still temperature and 3-5mmHg pressure, rectifying obtains aubepine 33.7Kg, GC purity 99.27%, obtain cassie ketone 35.1Kg, GC purity 99.93% with rectifying under 136-138 DEG C of still temperature and 3-5mmHg pressure.
Water I405.4Kg is proceeded in still kettle, open and stir, normal pressure, is warming up to 100-121 DEG C, and recycle-water 352Kg is used for applying mechanically, and heats up in a steamer end catalyst I and applies mechanically for oxidizing reaction.
192Kg water and 48Kg sodium hydroxide are put in hydrolytic reaction pot, after dissolving, be warmed up to 65-75 DEG C, in 30min, drip cassie ketone 35.1Kg, drip off rear insulation 1.5-2h, after reaction finishes, stratification, obtains water II248.1Kg and p-methoxybenzyl alcohol crude product 28.1Kg, GC purity 99.19%.Then under 130-136 DEG C of still temperature and 3-5mmHg pressure, carry out rectifying, obtain finished product p-methoxybenzyl alcohol 25.6Kg, GC purity 99.85%.
embodiment 2
488.8Kg acetic acid (KF<1%), 25.6Kg cobaltous acetate, 19.9Kg cerous acetate and 122.2Kg are put in dry stainless steel oxidation still methoxy toluene, be warmed up to after 105-115 DEG C, pass into oxygen, be after insulation reaction 5.0h, to stop passing into oxygen under normal pressure (being that gauge pressure is 0MPa) at pressure, GC is in sampling and HPLC detects, GC result is, to methoxy toluene 54.4636%, aubepine 15.2655%, p-methoxybenzyl alcohol 0.6895% and acetic acid fennel ester 27.8973%, HPLC detects aldehydic acid and compares 39.4:1.
Oxidizing reaction finishes, and reclaims acetic acid KF=5.24%, and acetic acid content 88.89% is directly used in down batch oxidizing reaction and applies mechanically.Acetic acid reclaims and finishes, and under nitrogen protection, with 200Kg, 100Kg and the clean tap water washing of 50Kg, stratification after stirring 30min, obtains water I407.3Kg and oil phase I149.6Kg respectively.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 54.3072%, aubepine 15.3044%, p-methoxybenzyl alcohol 0.4785% and acetic acid fennel ester 28.1905%, HPLC detects aldehydic acid and compares 40.2:1.
Under nitrogen protection, the oil phase I149.6Kg of washing gained is added in still kettle, add anhydrous sodium carbonate 5Kg, underpressure distillation obtains organic phase II138.5Kg.Heating up in a steamer the end adds 100Kg water, is neutralized to pH=2-3 with 72% sulfuric acid, filters, and obtains anisic acid 5.2Kg.
Organic phase II138.5Kg rectifying under 109-125 DEG C of still temperature and 6-8mmHg pressure obtains methoxy toluene 63.2Kg, GC purity 99.72%, under 125-132 DEG C of still temperature and 3-5mmHg pressure, rectifying obtains aubepine 19.8Kg, GC purity 99.53%, obtain cassie ketone 48.2Kg, GC purity 99.92% with rectifying under 135-138 DEG C of still temperature and 3-5mmHg pressure.
Water I407.3Kg is proceeded in still kettle, open and stir, normal pressure, is warming up to 100-121 DEG C, and recycle-water 349Kg is used for applying mechanically, and heats up in a steamer end catalyst I and applies mechanically for oxidizing reaction.
200Kg water and 60Kg sodium hydroxide are put in hydrolytic reaction pot, after dissolving, be warmed up to 65-75 DEG C, in 30min, drip cassie ketone 48.2Kg, drip off rear insulation 1.5-2h, after reaction finishes, stratification, obtains water II270.5Kg and p-methoxybenzyl alcohol crude product 37.3Kg, GC purity 99.15%.Then under 129-137 DEG C of still temperature and 3-5mmHg pressure, carry out rectifying, obtain finished product p-methoxybenzyl alcohol 35.2Kg, GC purity 99.73%.
embodiment 3
488.8Kg acetic acid (KF<1%), 23.4Kg cobaltous acetate, 14.3Kg chromium acetate and 122.2Kg are put in dry stainless steel oxidation still methoxy toluene, be warmed up to after 105-115 DEG C, pass into oxygen, after pressure (gauge pressure) is for insulation reaction 2.5h under 0.09MPa, stop passing into oxygen, GC is in sampling and HPLC detects, GC result is, to methoxy toluene 41.1563%, aubepine 29.5622%, p-methoxybenzyl alcohol 2.2164% and acetic acid fennel ester 26.2614%, HPLC detects aldehydic acid and compares 13.0:1.
Oxidizing reaction finishes, and reclaims acetic acid KF=3.43%, and acetic acid content 90.1% is directly used in down batch oxidizing reaction and applies mechanically.Acetic acid reclaims and finishes, and under nitrogen protection, with 200Kg, 100Kg and the clean tap water washing of 50Kg, stratification after stirring 30min, obtains water I399.3Kg and oil phase I154.8Kg respectively.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 41.1236%, aubepine 29.6537%, p-methoxybenzyl alcohol 2.0289% and acetic acid fennel ester 26.4344%, HPLC detects aldehydic acid and compares 12.9:1.
Under nitrogen protection, the oil phase I154.8Kg of washing gained is added in still kettle, add anhydrous sodium carbonate 6.2Kg, underpressure distillation obtains organic phase II145.6Kg.Heating up in a steamer the end adds 100Kg water, is neutralized to pH=2-3 with 72% sulfuric acid, filters, and obtains anisic acid 6.0Kg.
Organic phase II145.6Kg rectifying under 108-122 DEG C of still temperature and 6-8mmHg pressure obtains methoxy toluene 53.6Kg, GC purity 99.81%, under 124-129 DEG C of still temperature and 3-5mmHg pressure, rectifying obtains aubepine 38.8Kg, GC purity 99.26%, obtain cassie ketone 44.9Kg, GC purity 99.91% with rectifying under 136-139 DEG C of still temperature and 3-5mmHg pressure.
Water I399.3Kg is proceeded in still kettle, open and stir, normal pressure, is warming up to 100-121 DEG C, and recycle-water 341.5Kg is used for applying mechanically, and heats up in a steamer end catalyst I and applies mechanically for oxidizing reaction.
200Kg water and 60Kg sodium hydroxide are put in hydrolytic reaction pot, after dissolving, be warmed up to 65-75 DEG C, in 30min, drip cassie ketone 44.9Kg, drip off rear insulation 1.5-2h, after reaction finishes, stratification, obtains water II268.9Kg and p-methoxybenzyl alcohol crude product 35.7Kg, GC purity 99.32%.Then under 132-138 DEG C of still temperature and 3-5mmHg pressure, carry out rectifying, obtain finished product p-methoxybenzyl alcohol 32.7Kg, GC purity 99.90%.
embodiment 4
By 488.8Kg acetic acid (KF<1%), 23.3Kg cobaltous acetate, chromium acetate 14.3Kg cerous acetate 10.0Kg and 122.2Kg put in dry stainless steel oxidation still methoxy toluene, be warmed up to after 105-115 DEG C, pass into oxygen, be after insulation reaction 1.5h, to stop passing into oxygen under normal pressure (being that gauge pressure is 0MPa) at pressure, GC is in sampling and HPLC detects, GC result is, to methoxy toluene 55.6059%, aubepine 12.0937%, p-methoxybenzyl alcohol 0.6513% and acetic acid fennel ester 30.395%, HPLC detects aldehydic acid and compares 50.4:1.
Oxidizing reaction finishes, and reclaims acetic acid KF=5.27%, and acetic acid content 89.92% is directly used in down batch oxidizing reaction and applies mechanically.Acetic acid reclaims and finishes, and under nitrogen protection, uses respectively the clean tap water of 200Kg, 100Kg and 50Kg, and stratification after stirring 30min, obtains water I409.5Kg and oil phase I147.0Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 55.6129%, aubepine 12.0737%, p-methoxybenzyl alcohol 0.5574% and acetic acid fennel ester 30.7071%, HPLC detects aldehydic acid and compares 51.0:1.
Under nitrogen protection, the oil phase I147.0Kg of washing gained is added in still kettle, add anhydrous sodium carbonate 5Kg, underpressure distillation obtains organic phase II140.0Kg.Heating up in a steamer the end adds 100Kg water, is neutralized to pH=2-3 with 72% sulfuric acid, filters, and obtains anisic acid 4.3Kg.
Organic phase II140.0Kg rectifying under 108-126 DEG C of still temperature and 6-8mmHg pressure obtains methoxy toluene 64.5Kg, GC purity 99.93%, under 123-128 DEG C of still temperature and 3-5mmHg pressure, rectifying obtains aubepine 15.6Kg, GC purity 99.39%, obtain cassie ketone 52.0Kg, GC purity 99.85% with rectifying under 137-142 DEG C of still temperature and 3-5mmHg pressure.
Water I409.5Kg is proceeded in still kettle, open and stir, normal pressure, is warming up to 100-121 DEG C, and recycle-water 356.9Kg is used for applying mechanically, and heats up in a steamer end catalyst I and applies mechanically for oxidizing reaction.
200Kg water and 60Kg sodium hydroxide are put in hydrolytic reaction pot, after dissolving, be warmed up to 65-75 DEG C, in 30min, drip cassie ketone 52.0Kg, drip off rear insulation 1.5-2h, after reaction finishes, stratification, obtains water II267.4Kg and p-methoxybenzyl alcohol crude product 42.6Kg, GC purity 99.12%.Then under 136-139 DEG C of still temperature and 3-5mmHg pressure, carry out rectifying, obtain finished product p-methoxybenzyl alcohol 39.8Kg, GC purity 99.54%.
embodiment 5
By 488.8Kg acetic acid (KF<1%), 23.3Kg cobaltous acetate, chromium acetate 14.3Kg cerous acetate 10.0Kg and 122.2Kg put in dry stainless steel high-pressure oxidizing kettle methoxy toluene, be warmed up to after 105-115 DEG C, setting oxygen pressure is 0.14-0.18MPa, continue to pass into oxygen, after pressure (gauge pressure) is for insulation reaction 1.5h under 0.3MPa, stop passing into oxygen, GC is in sampling and HPLC detects, GC result is, to methoxy toluene 41.1018%, aubepine 45.3527%, p-methoxybenzyl alcohol 0.2268% and acetic acid fennel ester 13.1939%, HPLC detects aldehydic acid and compares 8.0:1.
Oxidizing reaction finishes, and reclaims acetic acid KF=6.31%, and acetic acid content 88.48% is directly used in down batch oxidizing reaction and applies mechanically.Acetic acid reclaims and finishes, and under nitrogen protection, uses respectively the clean tap water of 200Kg, 100Kg and 50Kg, and stratification after stirring 30min, obtains water I413.5Kg and oil phase I142.7Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 41.1029%, aubepine 45.1617%, p-methoxybenzyl alcohol 0.1684% and acetic acid fennel ester 13.2977%, HPLC detects aldehydic acid and compares 9.9:1.
Under nitrogen protection, the oil phase I142.7Kg of washing gained is added in still kettle, add anhydrous sodium carbonate 5Kg, underpressure distillation obtains organic phase II136.9Kg.Heating up in a steamer the end adds 100Kg water, is neutralized to pH=2-3 with 72% sulfuric acid, filters, and obtains anisic acid 5.2Kg.
Organic phase II136.9Kg rectifying under 109-123 DEG C of still temperature and 6-8mmHg pressure obtains methoxy toluene 47.7Kg, GC purity 99.57%, under 125-130 DEG C of still temperature and 3-5mmHg pressure, rectifying obtains aubepine 58.6Kg, GC purity 99.82%, obtain cassie ketone 22.6Kg, GC purity 99.95% with rectifying under 136-140 DEG C of still temperature and 3-5mmHg pressure.
Water I413.5Kg is proceeded in still kettle, open and stir, normal pressure, is warming up to 100-121 DEG C, and recycle-water 353.6Kg is used for applying mechanically, and heats up in a steamer end catalyst I and applies mechanically for oxidizing reaction.
192Kg water and 48Kg sodium hydroxide are put in hydrolytic reaction pot, after dissolving, be warmed up to 65-75 DEG C, in 30min, drip cassie ketone 22.6Kg, drip off rear insulation 1.5-2h, after reaction finishes, stratification, obtains water II240.2Kg and p-methoxybenzyl alcohol crude product 19.3Kg, GC purity 99.22%.Then under 130-135 DEG C of still temperature and 3-5mmHg pressure, carry out rectifying, obtain finished product p-methoxybenzyl alcohol 17.3Kg, GC purity 99.76%.
embodiment 6
Various recovered material to embodiment 5 are applied mechanically.
To reclaim acetic acid 468.9Kg acetic acid (KF=6.31%, acetic acid content 88.48%, to methoxy toluene 6.61%), new acetic acid 73.9Kg (KF<1%), reclaim catalyzer, fresh cobaltous acetate 0.5Kg, fresh chromium acetate 0.3Kg and 97.8Kg put in dry stainless steel high-pressure oxidizing kettle methoxy toluene, be warmed up to after 105-115 DEG C, setting oxygen pressure is 0.14-0.18MPa, continue to pass into oxygen, after pressure (gauge pressure) is for insulation reaction 1.5h under 0.25MPa, stop passing into oxygen, GC is in sampling and HPLC detects, GC result is, to methoxy toluene 39.4319%, aubepine 43.1831%, p-methoxybenzyl alcohol 0.1000% and acetic acid fennel ester 15.7635%, HPLC detects aldehydic acid and compares 7.8:1.
Oxidizing reaction finishes, and reclaims acetic acid KF=9.49%, and acetic acid content 84.28% is directly used in down batch oxidizing reaction and applies mechanically.Acetic acid reclaims and finishes, and under nitrogen protection, uses respectively the clean tap water of 200Kg, 100Kg and 50Kg, and stratification after stirring 30min, obtains water I410.5Kg and oil phase I149.0Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 39.4233%, aubepine 43.1812%, p-methoxybenzyl alcohol 0.0591% and acetic acid fennel ester 15.8286%, HPLC detects aldehydic acid and compares 8.4:1.
Under nitrogen protection, the oil phase I149.0Kg of washing gained is added in still kettle, add anhydrous sodium carbonate 5Kg, underpressure distillation obtains organic phase II139.5Kg.Heating up in a steamer the end adds 100Kg water, is neutralized to pH=2-3 with 72% sulfuric acid, filters, and obtains anisic acid 5.7Kg.
Organic phase II139.5Kg rectifying under 111-122 DEG C of still temperature and 6-8mmHg pressure obtains methoxy toluene 45.8Kg, GC purity 99.87%, under 124-128 DEG C of still temperature and 3-5mmHg pressure, rectifying obtains aubepine 55.8Kg, GC purity 99.37%, obtain cassie ketone 27.0Kg, GC purity 99.59% with rectifying under 135-139 DEG C of still temperature and 3-5mmHg pressure.
Water I410.5Kg is proceeded in still kettle, open and stir, normal pressure, is warming up to 100-121 DEG C, and recycle-water 352.1Kg is used for applying mechanically, and heats up in a steamer end catalyst I and applies mechanically for oxidizing reaction.
192Kg water and 48Kg sodium hydroxide are put in hydrolytic reaction pot, after dissolving, be warmed up to 65-75 DEG C, in 30min, drip cassie ketone 27.0Kg, drip off rear insulation 1.5-2h, after reaction finishes, stratification, obtains water II241.4Kg and p-methoxybenzyl alcohol crude product 22.8Kg, GC purity 99.36%.Then under 130-137 DEG C of still temperature and 3-5mmHg pressure, carry out rectifying, obtain finished product p-methoxybenzyl alcohol 20.7Kg, GC purity 99.65%.
Should be appreciated that, although the present invention has been described in detail in conjunction with example, above-mentioned explanation is intended to illustrate, and limits never in any form its summary of the invention.Concerning art technology people, the explanation based on herein can farthest utilize the present invention, and can carry out multiple amendment or modification not departing from claim scope of the present invention or spirit.Each reference that the application quotes, which is hereby incorporated by reference.
Claims (9)
1. dioxygen oxidation is prepared a co-production for correspondent alcohol, ester, aldehyde and acid to methoxy toluene, it is characterized in that, comprises the following steps:
Step 1), in oxidizing reactor, add methoxy toluene, catalyst I and solvent, pass at a certain temperature oxygen, stopped reaction after reaction certain hour;
Step 2), oxidizing reaction finishes, and reclaims solvent, optionally for applying mechanically, then adds washing to go catalyst I, obtains organic phase I and water I;
Step 3), in organic phase I, add alkali, decompression steams organic phase II, heats up in a steamer the end and use sour adjust pH after adding water, and filtration obtains anisic acid;
Step 4), water I Distillation recovery water, optionally for applying mechanically, heats up in a steamer the end and adds after catalyst I and solvent, optionally applies mechanically for oxidizing reaction;
Step 5), organic phase II rectifying obtains finished product aubepine and cassie ketone;
Step 6), cassie ketone alkaline hydrolysis, obtains anisy alcohol crude product, obtains anisy alcohol sterling through rectifying.
2. preparation method according to claim 1, is characterized in that,
In step 1,
Solvent is organic carboxyl acid class, as formic acid, acetic acid, propionic acid, butyric acid, Mono Chloro Acetic Acid, trifluoroacetic acid etc., and preferably acetic acid or propionic acid, particularly preferably acetic acid,
Solvent for use (for example acetic acid) is 1~50:1 with the mole dosage ratio to methoxy toluene, preferably 3~30:1, more preferably 5~15:1.
3. preparation method according to claim 1 and 2, is characterized in that,
In step 1,
Catalyst I is transition metal salt, preferably acetate, as cobaltous acetate, manganous acetate, nickelous acetate, cerous acetate, chromium acetate, zinc acetate, ironic acetate, crystal aerugo, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, manganous nitrate, nitric acid ketone, cobalt chloride, cobaltous bromide, acetylacetone cobalt, ferric acetyl acetonade, one of cobalt stearate, manganese stearate, cobalt naphthenate, acid chloride, Palladous chloride etc., or the composite catalyst of several catalyzer compositions wherein, preferably one of cobaltous acetate, manganous acetate, chromium acetate, cerous acetate, acid chloride, ironic acetate, venus crystals etc., or the composite catalyst of their compositions;
Used catalyst I is 0.1~2.0:1 with the mole dosage ratio to methoxy toluene, preferably 0.2~1.0.
4. according to the preparation method one of claims 1 to 3 Suo Shu, it is characterized in that,
In step 1,
The temperature of oxidizing reaction is 40~150 DEG C, and preferable reaction temperature is 80~120 DEG C, more preferably 100~115 DEG C;
Oxidation pressure (gauge pressure) is 0~2.0MPa, preferably 0~1.2MPa, more preferably 0~0.5MPa.
5. according to the preparation method one of claim 1 to 4 Suo Shu, it is characterized in that,
In step 2,
Reclaim such as acetic acid of solvent, control its moisture 0~50%, preferably 0~30%.
6. according to the preparation method one of claim 1 to 5 Suo Shu, it is characterized in that,
In step 2,
After solvent recuperation finishes, add water that catalyst I washing is separated, washing times is 1~10 time, preferably 2~6 times, and more preferably 3~5 times.
7. according to the preparation method one of claim 1 to 6 Suo Shu, it is characterized in that,
In step 3,
Alkali used is basic metal inorganic acid salt or oxyhydroxide, is preferably sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide etc., more preferably sodium carbonate and salt of wormwood, particularly preferably sodium carbonate;
Alkali adds with the form of solid, and alkali is 0.01~1:1 with the mole dosage ratio to methoxy toluene, preferably 0.05~0.5:1, more preferably 0.1~0.3:1;
Decompression steams organic phase II, heats up in a steamer the end to add after water with acid for adjusting pH value, regulates pH value=1-5, preferably 2-3.
8. according to the preparation method one of claim 1 to 7 Suo Shu, it is characterized in that,
In step 4,
Water I Distillation recovery water, without any processing, is directly used in washing in step 2 and applies mechanically, and heats up in a steamer the end and adds after appropriate catalyst I and solvent, is preferably directly used in oxidizing reaction and applies mechanically;
The amount of adding catalyzer be catalyzer first charging capacity 1~30%, preferably 1~10%;
Charging capacity is identical first with acetic acid to add the amount of solvent acetic acid.
9. according to the preparation method one of claim 1 to 8 Suo Shu, it is characterized in that,
In step 6,
Alkaline hydrolysis alkali used is the aqueous solution of an alkali metal salt or oxyhydroxide, the preferably aqueous solution of sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide etc., the preferably aqueous solution of sodium hydroxide, potassium hydroxide etc.;
Temperature of reaction is 60~120 DEG C, preferably 80~110 DEG C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410185353.3A CN103936567B (en) | 2014-05-04 | 2014-05-04 | Co-production method of preparing corresponding alcohol, ester, aldehyde and acid by oxidizing p-methoxyl methylbenzene by oxygen |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410185353.3A CN103936567B (en) | 2014-05-04 | 2014-05-04 | Co-production method of preparing corresponding alcohol, ester, aldehyde and acid by oxidizing p-methoxyl methylbenzene by oxygen |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103936567A true CN103936567A (en) | 2014-07-23 |
CN103936567B CN103936567B (en) | 2015-04-15 |
Family
ID=51184489
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410185353.3A Active CN103936567B (en) | 2014-05-04 | 2014-05-04 | Co-production method of preparing corresponding alcohol, ester, aldehyde and acid by oxidizing p-methoxyl methylbenzene by oxygen |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103936567B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105237317A (en) * | 2015-10-28 | 2016-01-13 | 衢州群颖化学科技有限公司 | Combined production method for substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid |
CN105601473A (en) * | 2015-10-28 | 2016-05-25 | 衢州群颖化学科技有限公司 | Method for combined production of benzyl alcohol, benzaldehyde and benzoic acid through oxidizing toluene |
CN106608817A (en) * | 2015-11-09 | 2017-05-03 | 宁夏际华环境安全科技有限公司 | Production technology of p-methoxybenzoic acid |
CN106673985A (en) * | 2015-11-09 | 2017-05-17 | 宁夏际华环境安全科技有限公司 | Production process of p-methoxybenzyl alcohol |
CN112778107A (en) * | 2019-11-06 | 2021-05-11 | 复旦大学 | Method for synthesizing acetophenone or benzoic acid compound by oxidizing toluene compound |
CN113527074A (en) * | 2021-09-01 | 2021-10-22 | 湖北师范大学 | Method for preparing anisic aldehyde by continuously catalyzing and oxidizing p-methyl anisole through micro-channel |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5354919A (en) * | 1992-06-29 | 1994-10-11 | Rhone-Poulenc Chimie | Oxidation of aromatic compounds substituted by oxidizable alkyl moieties |
CN102219662A (en) * | 2011-04-27 | 2011-10-19 | 武汉万园寺药业有限公司 | Method for preparing benzaldehyde, benzyl alcohol and benzyl benzoate through air catalytic oxidation of methylbenzene |
-
2014
- 2014-05-04 CN CN201410185353.3A patent/CN103936567B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5354919A (en) * | 1992-06-29 | 1994-10-11 | Rhone-Poulenc Chimie | Oxidation of aromatic compounds substituted by oxidizable alkyl moieties |
CN102219662A (en) * | 2011-04-27 | 2011-10-19 | 武汉万园寺药业有限公司 | Method for preparing benzaldehyde, benzyl alcohol and benzyl benzoate through air catalytic oxidation of methylbenzene |
Non-Patent Citations (1)
Title |
---|
YASUO FUTAMI,ET.AL,: "reaction of alkylarenes benzyl alcohols, sulfides,and phosphine with manganese (III) acetate-chloride ions", 《BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN》, vol. 62, no. 11, 1989, pages 3567 - 3571, XP001189402 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105237317A (en) * | 2015-10-28 | 2016-01-13 | 衢州群颖化学科技有限公司 | Combined production method for substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid |
CN105601473A (en) * | 2015-10-28 | 2016-05-25 | 衢州群颖化学科技有限公司 | Method for combined production of benzyl alcohol, benzaldehyde and benzoic acid through oxidizing toluene |
CN106608817A (en) * | 2015-11-09 | 2017-05-03 | 宁夏际华环境安全科技有限公司 | Production technology of p-methoxybenzoic acid |
CN106673985A (en) * | 2015-11-09 | 2017-05-17 | 宁夏际华环境安全科技有限公司 | Production process of p-methoxybenzyl alcohol |
CN112778107A (en) * | 2019-11-06 | 2021-05-11 | 复旦大学 | Method for synthesizing acetophenone or benzoic acid compound by oxidizing toluene compound |
CN112778107B (en) * | 2019-11-06 | 2022-06-10 | 复旦大学 | Method for synthesizing acetophenone or benzoic acid compound by oxidizing toluene compound |
CN113527074A (en) * | 2021-09-01 | 2021-10-22 | 湖北师范大学 | Method for preparing anisic aldehyde by continuously catalyzing and oxidizing p-methyl anisole through micro-channel |
CN113527074B (en) * | 2021-09-01 | 2022-11-04 | 湖北师范大学 | Method for preparing anisic aldehyde by continuously catalyzing and oxidizing p-methyl anisole through micro-channel |
Also Published As
Publication number | Publication date |
---|---|
CN103936567B (en) | 2015-04-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103936567B (en) | Co-production method of preparing corresponding alcohol, ester, aldehyde and acid by oxidizing p-methoxyl methylbenzene by oxygen | |
Miles et al. | Aroylations at the Methyl Group of Benzoylacetone and Related β-Diketones with Esters to Form 1, 3, 5-Triketones by Sodium Hydride. Other Terminal Condensations1 | |
CN108484545A (en) | A kind of method and system of continuous synthesis furandicarboxylic acid | |
CN103965045B (en) | Preparation process and device for glycerol triacetate | |
CN106866366B (en) | Method for removing dihydric alcohol or polyhydric alcohol impurities in ethylene glycol and increasing yield of ethylene glycol | |
CN102115444B (en) | Process and device for continuously producing glyceryl triacetate | |
CN109651128A (en) | A kind of continuous production method of milk lactone synthetic perfume | |
CN109678699A (en) | A kind of milk lactone spice is continuously synthesizing to method | |
CN106631783A (en) | Preparation method for n-butyl acetate | |
CN101831198A (en) | Preparation method of capsanthin | |
CN103739486A (en) | Production method for ethyl acetate crude product | |
CN103936568B (en) | A kind of method being prepared by methoxy toluene to p-methoxybenzyl alcohol | |
CN109748900A (en) | A kind of production method of ε-decalactone synthetic perfume | |
CN101508645B (en) | Method of preparing diacetyl rhein | |
CN106083540B (en) | A method of preparing natural benzaldehyde using phase transfer catalyst | |
CN105254480B (en) | A kind of preparation method of anisic aldehyde | |
JPH0748346A (en) | Integrated production of di-tert-butyl peroxide | |
CN108218686A (en) | A kind of method that Anderson heteropoly acid catalysis oxidation prepares Pyromellitic Acid | |
CN107746370A (en) | A kind of preparation method of laurine | |
CN109694311B (en) | Method for synthesizing isoliquiritigenin | |
CN103553891B (en) | Method for preparing levonorgestrel intermediate condensation compound | |
CN102660378B (en) | Method for extracting natural coenzyme Q10 by using palm residue | |
CN111362784A (en) | Method for preparing ethyl vanillin from sassafras oil | |
CN105198840A (en) | Method for preparing 2,5-dihydro-2,5-dimethoxyfuran by using fixed bed method | |
CN209722082U (en) | A kind of process units of ε-decalactone synthetic perfume |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |