CN103936568A - Method for preparing p-methoxybenzyl alcohol from p-methoxy toluene - Google Patents
Method for preparing p-methoxybenzyl alcohol from p-methoxy toluene Download PDFInfo
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Abstract
The invention relates to a method for preparing p-methoxybenzyl alcohol from p-methoxy toluene. The method comprises the following steps: adding p-methoxy toluene, a catalyst I and a solvent to an oxidation reaction kettle; charging oxygen; recovering the solvent after the oxidation reaction, and recycling optionally; washing with water to remove the catalyst I so as to obtain an organic phase I and a water phase I; adding aqueous alkali to the organic phase I; agitating; standing to separate out a water phase II for recycling optionally, so as to obtain an organic phase II; distilling the water phase I to recover water, and recycling optionally; supplementing the catalyst I and the solvent to distilling leaves, and recycling in oxidization reaction optionally; feeding the organic phase II to a hydrogenation kettle; adding a solvent and a catalyst II to hydrogenate until hydrogen is not absorbed; cooling; performing suction filtration to recover the catalyst II, and recycling optionally; recovering the solvent from the filtrate; then rectifying the filtrate to obtain p-methoxybenzyl alcohol. The novel method for preparing p-methoxybenzyl alcohol is mild in reaction condition and low in cost, produces few three wastes, and is easy for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of organic intermediate, in particular to the preparation method of p-methoxybenzyl alcohol, belong to daily-use chemical industry technical field.
Background technology
P-methoxybenzyl alcohol, also claims anisy alcohol, is colourless to micro-yellow liquid under normal temperature and pressure, 24 ℃ of fusing points, 259 ℃ of boiling points.P-methoxybenzyl alcohol has sweet fruital like peach fragrance, and fragrance is soft lasting, can be used for high-grade cigarette, the allotment of food flavor(ing).P-methoxybenzyl alcohol also has important application in field of fine chemical, is the essential raw material of producing another kind of senior spices acetic acid fennel ester; It is the raw material of preparing GCLE (synthetic important microbiotic raw material); It is the raw material for the synthesis of medicine, the important organic intermediate PARA METHOXY PHENYL ACETONITRILE of agricultural chemicals; Also be the raw material for the preparation of new polymers dielectric film.
The industrial p-methoxybenzyl alcohol of preparing mainly be take aubepine as raw material, through catalytic hydrogenation or through chemical reduction preparation (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; ).Catalytic hydrogenation needs high-tension apparatus, and investment is large, has potential safety hazard, through chemical reduction, needs to use the expensive original reagent of going back, and production cost is high.In addition, raw materials used aubepine is difficult for obtaining, complicated process of preparation, and serious three wastes, thereby expensive.
Take anisic acid and derivative thereof as raw material, through reduction reaction, prepare p-methoxybenzyl alcohol (Tetrahedron, 2001,57 (14): 2701-2710; Angew.Chem.-Int.Ed., 2012,51 (37): 9422-9424; US4585899; Synth.Commun., 2010,40 (19): 2897-2907; J.Org.Chem., 1996,61 (3): 826-830; Synth.Commun., 2005,35 (17): 2271-2276; Bull.Chem.Soc.J., 1988,61 (7): 2684-6; Synthesis, 1979, (11): 912; J.Chem.Res., 2003, (8): 522-525; J.Chin.Chem.Soc., 2006,53 (3): 643-645; Synthesis, 1987, (7): 647-648; J.Ind.Eng.Chem., 2007,13 (7): 1067-1075; Bull.Korean Chem.Soc., 2007,28 (11): 2034-2040), the method has green, economical, the advantage of environmental protection, but because used condition is comparatively harsh, as High Temperature High Pressure, or use the expensive original reagent of going back, make production cost very high, thus far away apart from suitability for industrialized production, also need further research.At present, whole world Jin You only a few producer has realized catalytic hydrogenation anisic acid and has prepared p-methoxybenzyl alcohol.
Org.Lett., 201214 (3): 938-941 has reported that take to methoxy toluene is raw material, adopt the method for anode electrolysis oxidation directly to obtain p-methoxybenzyl alcohol.Camaioni, the people such as Donald M. are at J.Org.Chem., 1984,49 (9): in 1607-1613, reported and take perchloric acid as oxygenant, cracking c h bond in acetonitrile solution, thereby produce 4-methoxy-benzyl free radical, this free radical and water effect obtain p-methoxybenzyl alcohol, but its yield is only 20%.The people such as Dalla Cort are at Synth.Commun., and 1988,18 (6):, in 613-616, reported that take to methoxy toluene is raw material, cupric nitrate is catalyzer, Sodium Persulfate and SODIUMNITRATE are oxygenant, in DMSO solvent, prepare p-methoxybenzyl alcohol.Other documents (Catal.Commun. for example, 2004,5 (1): 9-13; Bull.Chem.Soc.J., 1989,62 (11): 3567-3571; Science, 2011,331 (6014): 195-199) reported and take oxygen as oxygenant, adopt transition metal salt as catalyzer, under initiator exists, catalyzed oxidation is prepared p-methoxybenzyl alcohol to methoxy toluene, but its yield is less than 10%.Obviously, these methods, because energy consumption is high, it is large to pollute, have explosion hazard to be difficult to realize suitability for industrialized production.
Summary of the invention
The above-mentioned defect existing in order to overcome prior art, the object of the present invention is to provide a kind of method that can prepare high-quality p-methoxybenzyl alcohol, wherein do not using initiator, especially in halogen initiator situation, use cheap oxygen to carry out oxidizing reaction as oxygenant, avoid having used chemical oxidizing agent and other organic peroxide oxidant, hydrogenation conditions is gentle, selectivity is high, almost without over-hydrogenation reaction, occur, reaction mass and catalyzer are recyclable to be applied mechanically, reduced cost, reduced the generation of the three wastes, therefore economical, environmental protection and green high-efficient, 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, can obtain high-quality p-methoxybenzyl alcohol, and reactive chemistry formula is:
Methoxy toluene, through oxygen liquid phase catalytic oxidation, is mainly generated to aubepine, acetic acid fennel ester and a small amount of anisic acid.Optionally, after reclaiming solvent acetic acid and catalyzer, directly alkaline hydrolysis, obtains the mixture containing aubepine and p-methoxybenzyl alcohol through oily water separation, and a small amount of anisic acid that simultaneous oxidation produces is removed.Through shortening, make aubepine wherein change into p-methoxybenzyl alcohol again, finally by rectifying, obtain high-quality p-methoxybenzyl alcohol.
Therefore, the method for preparing p-methoxybenzyl alcohol according to the present invention 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 aqueous solution, stir, the phase II that anhydrates for standing minute, optionally for applying mechanically, obtains organic phase II; Water I Distillation recovery water, optionally for applying mechanically, heats up in a steamer the end and adds after catalyst I and solvent, optionally for oxidizing reaction, applies mechanically;
Step 4), organic phase II is put in hydrogenation still, add solvent, and add catalyst I I, carry out hydrogenation reaction, until while no longer absorbing hydrogen;
Step 5), cooling, suction filtration reclaims catalyst I I, and optionally for applying mechanically, filtrate is carried out rectifying after reclaiming solvent, obtains p-methoxybenzyl alcohol.
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 preferred 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.
Catalyst I is transition metal salt, preferred 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 that certain mol proportion forms, preferred cobaltous acetate, manganous acetate, chromium acetate, cerous acetate, acid chloride, ironic acetate, one of venus crystals etc., or they press the composite catalyst that certain mol proportion forms.
According to the present invention, select transition metal salt as the catalyzer of 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 ℃, and preferable reaction temperature is 80～120 ℃, more preferably 100～115 ℃.
Oxidation pressure is 0～2.0MPa, and preferred reaction pressure (gauge pressure) is 0～1.2MPa, more preferably normal pressure (being that gauge pressure is 0).
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, from oxidizing reaction system recovered solvent for example acetic acid preferably need to control certain moisture 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 separated, 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.During each washing, water is 0.1～40:1 with the mole dosage ratio to methoxy toluene, preferably 1～20:1, more preferably 2～10:1.
In step 3 of the present invention, to organic phase, I adds alkali aqueous solution, stirs, and the phase II that anhydrates for standing minute, optionally for applying mechanically, obtains organic phase II.
The alkali aqueous solution that step 3 of the present invention is used is the aqueous solution of basic metal inorganic acid salt or oxyhydroxide, be preferably the aqueous solution of sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide etc., more preferably the aqueous solution of sodium hydroxide, potassium hydroxide.
The mass percentage concentration of described alkali aqueous solution is 1～50%, preferably 5～30%.In alkali aqueous solution, alkali is 1～5:1 with the mole dosage ratio to methoxy toluene, preferably 1.2～3:1, more preferably 1.5～2:1.
The temperature of reaction of this hydrolysing step is 60～120 ℃, preferably 80～110 ℃; Reaction times is 0.2～10h, preferably 0.5～5h, more preferably 1.5～3.0h.
The phase II that anhydrates for standing minute, preferably uses it for and applies mechanically.
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 4 of the present invention, the organic phase II obtaining is above put in hydrogenation still, add solvent, and add catalyst I I, carry out hydrogenation reaction, until while no longer absorbing hydrogen.
Hydrogenation solvent for use is alcoholic solvent, as methyl alcohol, ethanol, Virahol, the trimethyl carbinol, or varsol, as normal heptane, hexanaphthene, sherwood oil, or ether solvent, as n-butyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran etc., preferred alcohols kind solvent, as methyl alcohol, ethanol etc., particularly preferably methyl alcohol is as the solvent of hydrogenation reaction.
Hydrogenation solvent for use (as methyl alcohol) with to the weight ratio of methoxy toluene, be 1～10:1, preferably 2～5:1, more preferably 3～4:1.
Hydrogenation used catalyst II is skeleton nickel, palladium charcoal, ruthenium charcoal, rhodium charcoal, copper chromite etc., preferably skeleton nickel and palladium charcoal, particularly preferably skeleton nickel.
When hydrogenation feeds intake first, catalyzer (as skeleton nickel) with to the weight ratio of methoxy toluene, be 0.05～0.5:1, preferably 0.08～0.3:1, more preferably 0.1～0.2:1.
Hydrogenation reaction temperature is 25～100 ℃, preferably 30～95 ℃, and more preferably 50～90 ℃.
Hydrogenation reaction pressure is 0～1.5MPa, preferably 0.2～0.8MPa, more preferably 0.3～0.5MPa.
In the hydrogenation reaction of this step of the present invention, mild condition, selectivity is high, almost without over-hydrogenation reaction, occurs.
In step 5 of the present invention, cooling, suction filtration reclaims catalyst I I, and optionally for applying mechanically, filtrate is carried out rectifying after reclaiming solvent, obtains p-methoxybenzyl alcohol.
According to the present invention, after above-mentioned hydrogenation reaction finishes, cooling, preferably be cooled to 15～50 ℃, be more preferably cooled to 20～40 ℃, for example, be cooled to room temperature, the catalyst I I that suction filtration reclaims can be directly used in and apply mechanically, now need to add appropriate live catalyst, the additional amount of live catalyst be first catalyzer charging capacity 1～30%, preferably 2～15%.
Filtrate is reclaimed after solvent (particular methanol), for example, at 130-136 ℃ of still temperature with under pressure 3-5mmHg, carries out rectifying, obtains the finished product p-methoxybenzyl alcohol.
Beneficial effect of the present invention is mainly reflected in the following aspects:
(1), the oxidizing reaction stage, select transition metal salt as the catalyzer of oxidizing reaction, avoided the use of initiator, especially avoided the use of halogen initiator, for producing high-quality p-methoxybenzyl alcohol, provide a kind of good method, prepared product p-methoxybenzyl alcohol can be used for food, medicine and other fields.
(2), oxidizing reaction used 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), hydrogenation conditions is gentle, selectivity is high, almost without over-hydrogenation reaction, occurs.Catalyzer only needs simple filtration to get final product recovery, has realized the recycle of material, has reduced raw materials 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
By embodiment, further explain and describe content of the present invention below, but embodiment is not to be construed as limiting the scope of the invention.
embodiment 1
488.8Kg acetic acid (KF<1%), 30.2Kg cobaltous acetate, 13.2Kg manganous acetate and 122.2Kg are put in dry stainless steel oxidation still methoxy toluene, be warmed up to after 105-115 ℃, pass into oxygen, at pressure, be after insulation reaction 6.5h, to stop passing into oxygen under normal pressure (being that gauge pressure is 0MPa), GC is in sampling and HPLC detects, GC result is, to methoxy toluene 51.5365%, aubepine 16.8333%, p-methoxybenzyl alcohol 1.5437% and acetic acid fennel ester 28.9929%, HPLC detects aldehydic acid and compares 52.8:1.
Oxidizing reaction finishes, and reclaims acetic acid KF=4.87%, and acetic acid content 90.92% 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 I405.4Kg and oil phase I152Kg respectively.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 51.8266%, aubepine 16.6041%, p-methoxybenzyl alcohol 1.2122% and acetic acid fennel ester 29.6071%, HPLC detects aldehydic acid and compares 67:1.
200Kg water and 60Kg sodium hydroxide are put in hydrolytic reaction pot, be warmed up to 80-85 ℃ after dissolving, drip oil phase I152Kg in 30min, drip off rear insulation 1.5-2h, after reaction finishes, stratification, obtains water II265.5Kg and oil phase II143Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 51.8215%, aubepine 16.7277%, p-methoxybenzyl alcohol 30.8563%, HPLC detects aldehydic acid and compares 2502:1.
Water I405.4Kg is proceeded in still kettle, open and stir, normal pressure, is warming up to 100-121 ℃, and recycle-water 352Kg is used for applying mechanically, and heats up in a steamer end catalyst I and applies mechanically for oxidizing reaction.
In autoclave, add oil phase II143Kg, 20Kg skeletal nickel catalyst (moisture 15%), 300Kg anhydrous methanol.By nitrogen purge 3 times, then use hydrogen emptying 3 times.Setting hydrogenation pressure is 0.3～0.4MPa, and setting temperature of reaction is 80～90 ℃.Continue to pass into hydrogen in hydrogenation still, till not when absorbing hydrogen.By still temperature drop to 30～40 ℃, hydrogen in emptying still, then use nitrogen purge 3 times.In still, for reclaiming catalyzer after pressing machine press filtration, applies mechanically for lower batch material, filtrate is reclaimed methyl alcohol and is applied mechanically for lower batch, under 131-137 ℃ of still temperature and 3-5mmHg pressure, carry out rectifying, obtain methoxy toluene 58.2Kg, GC purity 99.87%, p-methoxybenzyl alcohol 61.2Kg, GC purity 99.54%, yield 86.0%.
embodiment 2
488.8Kg acetic acid (KF<1%), 35.0Kg cobaltous acetate, 16.1Kg cerous acetate and 122.2Kg are put in dry stainless steel oxidation still methoxy toluene, be warmed up to after 105-115 ℃, pass into oxygen, at pressure, be after insulation reaction 7.0h, to stop passing into oxygen under normal pressure (being that gauge pressure is 0MPa), GC is in sampling and HPLC detects, GC result is, to methoxy toluene 46.3215%, aubepine 11.2277%, p-methoxybenzyl alcohol 1.6563% and acetic acid fennel ester 40.4488%, HPLC detects aldehydic acid and compares 72.4:1.
Oxidizing reaction finishes, and reclaims acetic acid KF=4.59%, and acetic acid content 90.31% 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 I413.1Kg and oil phase I163Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 46.2915%, aubepine 11.2385%, p-methoxybenzyl alcohol 1.2767% and acetic acid fennel ester 40.7267%, HPLC detects aldehydic acid and compares 73.8:1.
192Kg water and 48Kg sodium hydroxide are put in hydrolytic reaction pot, be warmed up to 65-75 ℃ after dissolving, drip oil phase I163Kg in 30min, drip off rear insulation 1.5-2h, after reaction finishes, stratification, obtains water II254.8Kg and oil phase II140.8Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 46.8186%, aubepine 11.2113%, p-methoxybenzyl alcohol 41.9827%, HPLC detects aldehydic acid and compares 2792:1.
Water I413.1Kg is proceeded in still kettle, open and stir, normal pressure, is warming up to 100-121 ℃, and recycle-water 352Kg is used for applying mechanically, and heats up in a steamer end catalyst I and applies mechanically for oxidizing reaction.
In autoclave, add oil phase II140.8Kg, 20Kg skeletal nickel catalyst (moisture 15%), 300Kg anhydrous methanol.By nitrogen purge 3 times, then use hydrogen emptying 3 times.Setting hydrogenation pressure is 0.3～0.4MPa, and setting temperature of reaction is 70～80 ℃.Continue to pass into hydrogen in hydrogenation still, till not when absorbing hydrogen.By still temperature drop to 30～40 ℃, hydrogen in emptying still, then use nitrogen purge 3 times.In still, for reclaiming catalyzer after pressing machine press filtration, applies mechanically for lower batch material, filtrate is reclaimed methyl alcohol and is applied mechanically for lower batch, under 130-138 ℃ of still temperature and 3-5mmHg pressure, carry out rectifying, obtain methoxy toluene 53.8Kg, GC purity 99.37%, p-methoxybenzyl alcohol 69.9Kg, GC purity 99.65%, yield 90.5%.
embodiment 3
488.8Kg acetic acid (KF<1%), 37.4Kg cobaltous acetate, 12.9Kg chromium acetate and 122.2Kg are put in dry stainless steel oxidation still methoxy toluene, be warmed up to after 105-115 ℃, pass into oxygen, at pressure, be after insulation reaction 6.5h, to stop passing into oxygen under normal pressure (being that gauge pressure is 0MPa), GC is in sampling and HPLC detects, GC result is, to methoxy toluene 41.4186%%, aubepine 14.7202%, p-methoxybenzyl alcohol 1.6113% and acetic acid fennel ester 41.4296%, HPLC detects aldehydic acid and compares 50:1.
Oxidizing reaction finishes, and reclaims acetic acid KF=5.32%, and acetic acid content 88.07% 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 I412.3Kg and oil phase I156.8Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 41.2031%, aubepine 14.7714%, p-methoxybenzyl alcohol 1.2053% and acetic acid fennel ester 41.8369%, HPLC detects aldehydic acid and compares 49.8:1.
200Kg water and 60Kg sodium hydroxide are put in hydrolytic reaction pot, be warmed up to 65-75 ℃ after dissolving, drip oil phase I156.8Kg in 30min, drip off rear insulation 1.5-2h, after reaction finishes, stratification, obtains water II270.8Kg and oil phase II141.6Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 41.2213%, aubepine 15.0727%, p-methoxybenzyl alcohol 42.8422%, HPLC detects aldehydic acid and compares 2717:1.
Water I412.3Kg is proceeded in still kettle, open and stir, normal pressure, is warming up to 100-121 ℃, and recycle-water 354Kg is used for applying mechanically, and heats up in a steamer end catalyst I and applies mechanically for oxidizing reaction.
In autoclave, add oil phase II141.6Kg, 20Kg skeletal nickel catalyst (moisture 15%), 300Kg anhydrous methanol.By nitrogen purge 3 times, then use hydrogen emptying 3 times.Setting hydrogenation pressure is 0.4～0.5MPa, and setting temperature of reaction is 70～80 ℃.Continue to pass into hydrogen in hydrogenation still, till not when absorbing hydrogen.By still temperature drop to 30～40 ℃, hydrogen in emptying still, then use nitrogen purge 3 times.In still, for reclaiming catalyzer after pressing machine press filtration, applies mechanically for lower batch material, filtrate is reclaimed methyl alcohol and is applied mechanically for lower batch, under 130-138 ℃ of still temperature and 3-5mmHg pressure, carry out rectifying, obtain methoxy toluene 48.6Kg, GC purity 99.562%, p-methoxybenzyl alcohol 75.7Kg, GC purity 99.49%, yield 91.1%.
embodiment 4
488.8Kg acetic acid (KF<1%), 46Kg cobaltous acetate and 122.2Kg are put in dry stainless steel oxidation still methoxy toluene, be warmed up to after 105-115 ℃, pass into oxygen, at pressure, be after insulation reaction 4.0h, to stop passing into oxygen under normal pressure (being that gauge pressure is 0MPa), GC is in sampling and HPLC detects, GC result is, to methoxy toluene 63.6926%, aubepine 23.5696%, p-methoxybenzyl alcohol 6.7011% and acetic acid fennel ester 2.1628%, HPLC detects aldehydic acid and compares 3.8:1.
Oxidizing reaction finishes, and reclaims acetic acid KF=7.16%, and acetic acid content 98.97% 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 I435.6Kg and oil phase I136.4Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 63.6327%, aubepine 23.5046%, p-methoxybenzyl alcohol 6.2017% and acetic acid fennel ester 2.7008%, HPLC detects aldehydic acid and compares 4.2:1.
100Kg water and 10Kg sodium hydroxide are put in hydrolytic reaction pot, be warmed up to 65-75 ℃ after dissolving, drip oil phase I136.4Kg in 30min, drip off rear insulation 1.5-2h, after reaction finishes, stratification, obtains water II109Kg and oil phase II137.1Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 63.6698%, aubepine 23.7772%, p-methoxybenzyl alcohol 8.5563%, HPLC detects aldehydic acid and compares 2562:1.
Water I435.6Kg is proceeded in still kettle, open and stir, normal pressure, is warming up to 100-121 ℃, and recycle-water 359.6Kg is used for applying mechanically, and heats up in a steamer end catalyst I and applies mechanically for oxidizing reaction.
In autoclave, add oil phase II137.1Kg, 25Kg skeletal nickel catalyst (moisture 15%), 300Kg anhydrous methanol.By nitrogen purge 3 times, then use hydrogen emptying 3 times.Setting hydrogenation pressure is 0.1～0.3MPa, and setting temperature of reaction is 70～80 ℃.Continue to pass into hydrogen in hydrogenation still, till not when absorbing hydrogen.By still temperature drop to 30～40 ℃, hydrogen in emptying still, then use nitrogen purge 3 times.In still, for reclaiming catalyzer after pressing machine press filtration, applies mechanically for lower batch material, filtrate is reclaimed methyl alcohol and is applied mechanically for lower batch, under 129-136 ℃ of still temperature and 3-5mmHg pressure, carry out rectifying, obtain methoxy toluene 71.6Kg, GC purity 99.93%, p-methoxybenzyl alcohol 42.4Kg, GC purity 99.54%, yield 74.5%.
embodiment 5
By 488.8Kg acetic acid (KF<1%), 24.2Kg 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 ℃, pass into oxygen, at pressure, be after insulation reaction 1.5h, to stop passing into oxygen under normal pressure (being that gauge pressure is 0MPa), GC is in sampling and HPLC detects, GC result is, to methoxy toluene 47.2913%, aubepine 11.0735%, p-methoxybenzyl alcohol 1.2312% and acetic acid fennel ester 40.0429%, HPLC detects aldehydic acid and compares 10.9:1.
Oxidizing reaction finishes, and reclaims acetic acid KF=3.26%, and acetic acid content 84.62% 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 I410.4Kg and oil phase I156.9Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 47.2365%, aubepine 10.9783%, p-methoxybenzyl alcohol 0.9347% and acetic acid fennel ester 40.2075%, HPLC detects aldehydic acid and compares 11.2:1.
200Kg water and 60Kg sodium hydroxide are put in hydrolytic reaction pot, be warmed up to 65-75 ℃ after dissolving, drip oil phase I156.9Kg in 30min, drip off rear insulation 1.5-2h, after reaction finishes, stratification, obtains water II265.5Kg and oil phase II151.4Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 47.1987%, aubepine 11.7928%, p-methoxybenzyl alcohol 40.7085%, HPLC detects aldehydic acid and compares 2813:1.
Water I410.4Kg is proceeded in still kettle, open and stir, normal pressure, is warming up to 100-121 ℃, and recycle-water 356.2Kg is used for applying mechanically, and heats up in a steamer end catalyst I and applies mechanically for oxidizing reaction.
In autoclave, add oil phase II151.4Kg, 25Kg skeletal nickel catalyst (moisture 15%), 300Kg anhydrous methanol.By nitrogen purge 3 times, then use hydrogen emptying 3 times.Setting hydrogenation pressure is 0.3～0.4MPa, and setting temperature of reaction is 70～80 ℃.Continue to pass into hydrogen in hydrogenation still, till not when absorbing hydrogen.By still temperature drop to 30～40 ℃, hydrogen in emptying still, then use nitrogen purge 3 times.In still, for reclaiming catalyzer after pressing machine press filtration, applies mechanically for lower batch material, filtrate is reclaimed methyl alcohol and is applied mechanically for lower batch, under 130-136 ℃ of still temperature and 3-5mmHg pressure, carry out rectifying, obtain methoxy toluene 54.9Kg, GC purity 99.35%, p-methoxybenzyl alcohol 68.6Kg, GC purity 99.72%, yield 90.3%.
embodiment 6
By 488.8Kg acetic acid (KF<1%), 24.2Kg cobaltous acetate, chromium acetate 14.3Kg cerous acetate 10.0Kg and 122.2Kg put in dry stainless high-pressure oxidizing kettle methoxy toluene, be warmed up to after 105-115 ℃, setting oxygen pressure is 0.14-0.18MPa, continue to pass into oxygen, after pressure (gauge pressure) is for insulation reaction 2.0h under 0.20MPa, stop passing into oxygen, GC is in sampling and HPLC detects, GC result is, to methoxy toluene 53.1552%, aubepine 30.6235%, p-methoxybenzyl alcohol 1.9814% and acetic acid fennel ester 13.4165%, HPLC detects aldehydic acid and compares 11.8:1.
Oxidizing reaction finishes, and reclaims acetic acid KF=3.43%, and acetic acid content 90.10% 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 I414.2Kg and oil phase I152.7Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 53.1265%, aubepine 30.6738%, p-methoxybenzyl alcohol 1.6842% and acetic acid fennel ester 13.7175%, HPLC detects aldehydic acid and compares 11.6:1.
200Kg water and 60Kg sodium hydroxide are put in hydrolytic reaction pot, be warmed up to 65-75 ℃ after dissolving, drip oil phase I152.7Kg in 30min, drip off rear insulation 1.5-2h, after reaction finishes, stratification, obtains water II267.2Kg and oil phase II153.5Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 53.1879%, aubepine 30.5928%, p-methoxybenzyl alcohol 15.4266%, HPLC detects aldehydic acid and compares 2075:1.
Water I414.2Kg is proceeded in still kettle, open and stir, normal pressure, is warming up to 100-121 ℃, and recycle-water 349.2Kg is used for applying mechanically, and heats up in a steamer end catalyst I and applies mechanically for oxidizing reaction.
In autoclave, add oil phase II152.7Kg, 25Kg skeletal nickel catalyst (moisture 15%), 300Kg anhydrous methanol.By nitrogen purge 3 times, then use hydrogen emptying 3 times.Setting hydrogenation pressure is 0.3～0.4MPa, and setting temperature of reaction is 70～80 ℃.Continue to pass into hydrogen in hydrogenation still, till not when absorbing hydrogen.By still temperature drop to 30～40 ℃, hydrogen in emptying still, then use nitrogen purge 3 times.In still, for reclaiming catalyzer after pressing machine press filtration, applies mechanically for lower batch material, filtrate is reclaimed methyl alcohol and is applied mechanically for lower batch, under 132-137 ℃ of still temperature and 3-5mmHg pressure, carry out rectifying, obtain methoxy toluene 61.7Kg, GC purity 99.55%, p-methoxybenzyl alcohol 60.3Kg, GC purity 99.72%, yield 88.3%.
embodiment 7
Various recovered material to embodiment 3 are applied mechanically.
To reclaim acetic acid 478.2Kg acetic acid (KF=5.32%, acetic acid content 88.07%, to methoxy toluene 6.61%), new acetic acid 67.6Kg (KF<1%), reclaim catalyzer, fresh cobaltous acetate 0.5Kg, fresh chromium acetate 0.3Kg and 90.6Kg put in dry stainless steel oxidation still methoxy toluene, be warmed up to after 105-115 ℃, pass into oxygen, at pressure, be after insulation reaction 6.5h, to stop passing into oxygen under normal pressure (being that gauge pressure is 0MPa), GC is in sampling and HPLC detects, GC result is, to methoxy toluene 42.5812%, aubepine 13.2537%, p-methoxybenzyl alcohol 1.5345% and acetic acid fennel ester 41.7962%, HPLC detects aldehydic acid and compares 48.6:1.
Oxidizing reaction finishes, and reclaims acetic acid KF=9.94%, and acetic acid content 84.82% 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 I421.5Kg and oil phase I168.8Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 42.5717%, aubepine 12.9291%, p-methoxybenzyl alcohol 1.0953% and acetic acid fennel ester 42.5863%, HPLC detects aldehydic acid and compares 47.5:1.
200Kg water and 60Kg sodium hydroxide are put in hydrolytic reaction pot, be warmed up to 65-75 ℃ after dissolving, drip oil phase I168.8Kg in 30min, drip off rear insulation 1.5-2h, after reaction finishes, stratification, obtains water II269.3Kg and oil phase II140.2Kg.Get oil phase and do GC and HPLC detection, GC result is that, to methoxy toluene 42.5413%, aubepine 13.2271%, p-methoxybenzyl alcohol 43.5417%, HPLC detects aldehydic acid and compares 1950:1.
Water I421.5Kg is proceeded in still kettle, open and stir, normal pressure, is warming up to 100-121 ℃, and recycle-water 358.4Kg is used for applying mechanically, and heats up in a steamer end catalyst I and applies mechanically for oxidizing reaction.
In autoclave, add oil phase II140.2Kg, reclaim skeletal nickel catalyst, fresh skeletal nickel catalyst 2.0Kg skeletal nickel catalyst (moisture 15%), 300Kg reclaims methyl alcohol.By nitrogen purge 3 times, then use hydrogen emptying 3 times.Setting hydrogenation pressure is 0.4～0.5MPa, and setting temperature of reaction is 70～80 ℃.Continue to pass into hydrogen in hydrogenation still, till not when absorbing hydrogen.By still temperature drop to 30～40 ℃, hydrogen in emptying still, then use nitrogen purge 3 times.In still, for reclaiming catalyzer after pressing machine press filtration, applies mechanically for lower batch material, filtrate is reclaimed methyl alcohol and is applied mechanically for lower batch, under 131-136 ℃ of still temperature and 3-5mmHg pressure, carry out rectifying, obtain methoxy toluene 49.4Kg, GC purity 99.89%, p-methoxybenzyl alcohol 74.2Kg, GC purity 99.65%, yield 90.27%.
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, based on explanation herein, can farthest utilize the present invention, and can within not departing from claim scope of the present invention or spirit, carry out multiple modification or modification.Each reference that the application quotes, which is hereby incorporated by reference.
Claims (10)
1. prepared by methoxy toluene to a method for p-methoxybenzyl alcohol, it is characterized in that, comprise 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 aqueous solution, stir, the phase II that anhydrates for standing minute, optionally for applying mechanically, obtains organic phase II; Water I Distillation recovery water, optionally for applying mechanically, heats up in a steamer the end and adds after catalyst I and solvent, optionally for oxidizing reaction, applies mechanically;
Step 4), organic phase II is put in hydrogenation still, add solvent, and add catalyst I I, carry out hydrogenation reaction, until while no longer absorbing hydrogen;
Step 5), cooling, suction filtration reclaims catalyst I I, and optionally for applying mechanically, filtrate is carried out rectifying after reclaiming solvent, obtains p-methoxybenzyl alcohol.
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, acetic acid particularly preferably, and/or
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, preferred 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 that certain mol proportion forms, preferred cobaltous acetate, manganous acetate, chromium acetate, cerous acetate, acid chloride, ironic acetate, one of venus crystals etc., or the composite catalyst that they form, and/or
The temperature of oxidizing reaction is 40～150 ℃, preferably 80～120 ℃;
Oxidation pressure is 0～2.0MPa, and preferred reaction pressure (gauge pressure) is 0～1.2MPa, more preferably normal pressure;
Oxidation time is 0.1-20h, preferably 1-10h.
4. according to the preparation method one of claims 1 to 3 Suo Shu, it is characterized in that,
In step 2, recovered solvent for example acetic acid is controlled its moisture 0～50%, and preferably 3～30%, after solvent recuperation finishes, add water that catalyst I is washed separated, obtain respectively organic phase I and water I.
5. according to the preparation method one of claim 1 to 4 Suo Shu, it is characterized in that,
In step 3,
Alkali aqueous solution used is the aqueous solution of basic metal inorganic acid salt or oxyhydroxide, is preferably the aqueous solution of sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide etc., more preferably the aqueous solution of sodium hydroxide, potassium hydroxide etc.;
The mass percentage concentration of alkali aqueous solution is 1～50%, preferably 5～30%;
In alkali aqueous solution, alkali is 1～5:1 with the mole dosage ratio to methoxy toluene, preferably 1.2～3:1, more preferably 1.5～2:1;
The temperature of reaction of this hydrolysing step is 60～120 ℃, preferably 80～110 ℃;
Water I Distillation recovery, without any processing, is directly used in washing in step 2 and applies mechanically; Heating up in a steamer the end adds and is directly used in oxidizing reaction after catalyst I and solvent and applies mechanically.
6. according to the preparation method one of claim 1 to 5 Suo Shu, it is characterized in that,
In step 4, hydrogenation solvent for use is alcoholic solvent, as methyl alcohol, ethanol, Virahol, the trimethyl carbinol, or varsol, as normal heptane, hexanaphthene, sherwood oil, or ether solvent, as n-butyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran etc., preferred alcohols kind solvent, as methyl alcohol, ethanol etc., particularly preferably methyl alcohol.
7. according to the preparation method one of claim 1 to 6 Suo Shu, it is characterized in that,
In step 4, hydrogenation solvent for use (as methyl alcohol) with to the weight ratio of methoxy toluene, be 1～10:1, preferably 2～5:1, more preferably 3～4:1.
8. according to the preparation method one of claim 1 to 7 Suo Shu, it is characterized in that,
In step 4, hydrogenation used catalyst II is skeleton nickel, palladium charcoal, ruthenium charcoal, rhodium charcoal, copper chromite etc., preferably skeleton nickel and palladium charcoal, particularly preferably skeleton nickel.
9. according to the preparation method one of claim 1 to 8 Suo Shu, it is characterized in that,
In step 4,
Hydrogenation reaction temperature is 25～100 ℃, preferably 30～95 ℃, and more preferably 50～90 ℃;
Hydrogenation reaction pressure is 0～1.5MPa, preferably 0.2～0.8MPa, more preferably 0.3～0.5MPa.
10. according to the preparation method one of claim 1 to 9 Suo Shu, it is characterized in that,
In step 5, after hydrogenation reaction finishes, be cooled to 15～50 ℃, preferably be cooled to 20～40 ℃, for example be cooled to room temperature, suction filtration recovery catalyst I I is directly used in and applies mechanically, and now adds appropriate live catalyst, the additional amount of live catalyst be first catalyzer charging capacity 1～30%, preferably 2～15%.
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