CN103936568B - A kind of method being prepared by methoxy toluene to p-methoxybenzyl alcohol - Google Patents
A kind of method being prepared by methoxy toluene to p-methoxybenzyl alcohol Download PDFInfo
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Abstract
The present invention relates to a kind of method being prepared by methoxy toluene to p-methoxybenzyl alcohol, comprising: add in oxidizing reactor methoxy toluene, catalyst I and solvent, pass into oxygen; Oxidizing reaction terminates rear recycling design, optionally for applying mechanically, then adding washing and going catalyst I, obtain organic phase I and aqueous phase I; In organic phase I, add alkali aqueous solution, stir, leaving standstill and divide the phase II that anhydrates, optionally for applying mechanically, obtaining organic phase II; Aqueous phase I Distillation recovery water, optionally for applying mechanically, heating up in a steamer after the end adds catalyst I and solvent, optionally applying mechanically for oxidizing reaction; Organic phase II is put in hydrogenation still, add solvent, and add catalyst I I and carry out hydrogenation reaction, till in time no longer absorbing hydrogen; Cooling, suction filtration reclaims catalyst I I, optionally for applying mechanically, carrying out rectifying, obtain p-methoxybenzyl alcohol after filtrate recycling design.The novel method reaction conditions preparing p-methoxybenzyl alcohol provided by the invention is gentle, cost is low, the three wastes are few, be easy to realize suitability for industrialized 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, fusing point 24 DEG C, boiling point 259 DEG C.P-methoxybenzyl alcohol has sweet fruital like peach fragrance, and fragrance is lastingly soft, 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 required raw material producing another kind of fine perfumery acetic acid fennel ester; It is the raw material preparing GCLE (synthesizing 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 novel polymer electrolyte film.
Industrial p-methoxybenzyl alcohol of preparing is mainly raw material with aubepine, 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; TetrahedronLett., 2009,50 (32): 4624-4628; CN1994988; TetrahedronLett., 2006,47 (25): 4161-4165; PCT2003089395; Synth.Commun., 2001,31 (17): 2719-2725; Catal.Commun., 2012,28:147-151; GreenChem., 2012,14 (5): 1372-1375; J.Am.Chem.Soc., 2010,132 (34): 11978-11987; ACSCatal., 2013,3 (2): 182-185; TetrahedronLett., 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, and then need to use through chemical reduction and expensive go back original reagent, production cost is high.In addition, raw materials used aubepine not easily obtains, complicated process of preparation, serious three wastes, thus expensive.
With anisic acid and derivative thereof for raw material, prepare p-methoxybenzyl alcohol (Tetrahedron, 2001,57 (14): 2701-2710 through reduction reaction; 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.KoreanChem.Soc., 2007,28 (11): 2034-2040), the method has green, economical, the advantage of environmental protection, but due to used condition comparatively harsh, as High Temperature High Pressure, or use and expensive go back original reagent, make production cost very high, thus distance suitability for industrialized production is comparatively far away, also needs further research.At present, whole world Jin You only a few producer achieves catalytic hydrogenation anisic acid and prepares p-methoxybenzyl alcohol.
Org.Lett., 201214 (3): 938-941 report with to methoxy toluene for raw material, adopt anode electrolysis oxidation method directly obtain p-methoxybenzyl alcohol.Camaioni, DonaldM. wait people at J.Org.Chem., 1984, report in 49 (9): 1607-1613 with perchloric acid is oxygenant, cracking c h bond in acetonitrile solution, thus producing 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 DallaCort at Synth.Commun., 1988,18 (6):, report in 613-616 with to methoxy toluene for raw material, cupric nitrate is catalyzer, and Sodium Persulfate and SODIUMNITRATE are oxygenant, in DMSO solvent, prepare p-methoxybenzyl alcohol.Other documents (such as Catal.Commun., 2004,5 (1): 9-13; Bull.Chem.Soc.J., 1989,62 (11): 3567-3571; Science, 2011,331 (6014): 195-199) then reporting with oxygen is oxygenant, adopt transition metal salt as catalyzer, under initiator exists, catalyzed oxidation prepares p-methoxybenzyl alcohol to methoxy toluene, but its yield is less than 10%.Obviously, these methods, because energy consumption is high, pollute large, have explosion hazard and be difficult to realize suitability for industrialized production.
Summary of the invention
In order to overcome the above-mentioned defect that prior art exists, the object of the present invention is to provide a kind of method can preparing high-quality p-methoxybenzyl alcohol, wherein do not using initiator, especially in halogen initiator situation, cheap oxygen is used to carry out oxidizing reaction as oxygenant, avoid employing chemical oxidizing agent and other organic peroxide oxidant, hydrogenation conditions is gentle, selectivity is high, almost occur without over-hydrogenation reaction, reaction mass and catalyzer is recyclable applies mechanically, reduce cost, decrease 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 present inventor is found by research, and by the synthesis technique comprised the steps, can obtain the p-methoxybenzyl alcohol of high-quality, reactive chemistry formula is:
To methoxy toluene through oxygen liquid phase catalytic oxidation, mainly generate aubepine, acetic acid fennel ester and a small amount of anisic acid.Optional after recycling design acetic acid and catalyzer, direct alkaline hydrolysis, obtain the mixture containing aubepine and p-methoxybenzyl alcohol through oily water separation, a small amount of anisic acid that simultaneous oxidation produces is removed.Again through shortening, make aubepine wherein change into p-methoxybenzyl alcohol, obtain the p-methoxybenzyl alcohol of high-quality finally by rectifying.
Therefore, the method preparing p-methoxybenzyl alcohol according to the present invention comprises the following steps:
Step 1), add in oxidizing reactor methoxy toluene, catalyst I and solvent, pass into oxygen at a certain temperature, stopped reaction after reaction certain hour;
Step 2), oxidizing reaction terminates, recycling design, optionally for applying mechanically, then adding washing and going catalyst I, obtain organic phase I and aqueous phase I;
Step 3), in organic phase I, add alkali aqueous solution, stir, leaving standstill and divide the phase II that anhydrates, optionally for applying mechanically, obtaining organic phase II; Aqueous phase I Distillation recovery water, optionally for applying mechanically, heating up in a steamer after the end adds catalyst I and solvent, optionally applying mechanically for oxidizing reaction;
Step 4), organic phase II is put in hydrogenation still, add solvent, and add catalyst I I, carry out hydrogenation reaction, till in time no longer absorbing hydrogen;
Step 5), cooling, suction filtration reclaims catalyst I I, optionally for applying mechanically, carrying out rectifying, obtain p-methoxybenzyl alcohol after filtrate recycling design.
The following specifically describes the present invention.
In step 1 of the present invention, add in oxidizing reactor methoxy toluene, catalyst I and solvent, pass into oxygen at a certain temperature, stopped reaction after reaction certain hour.
According to the present invention, the solvent used in step 1 is organic carboxyl acid class, and as formic acid, acetic acid, propionic acid, butyric acid, Mono Chloro Acetic Acid, trifluoroacetic acid etc., preferred acetic acid or propionic acid, particularly preferably acetic acid is the solvent of oxidizing reaction.
Solvent for use (such as acetic acid) be 1 ~ 50:1, preferably 3 ~ 30:1, more preferably 5 ~ 15:1 to the mole dosage ratio of methoxy toluene.
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 the composite catalyst of certain mol proportion composition pressed by several catalyzer wherein, preferred 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 transition metal salt as the catalyzer of oxidizing reaction, can avoid using initiator, especially not use halogen initiator, make not contain micro-initiator in the finished product p-methoxybenzyl alcohol, the safety requirements of food, medicine and other fields can be met completely.
Used catalyst I be 0.1 ~ 2.0:1 to the mole dosage ratio of 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 is 0 ~ 2.0MPa, and preferred reaction pressure (gauge pressure) is 0 ~ 1.2MPa, more preferably normal pressure (namely gauge pressure is 0).
Oxidation time is 0.1-20h, preferred 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 terminates, recycling design, optionally for applying mechanically, then adding washing and going catalyst I, obtain organic phase I and aqueous phase I.
According to the present invention, preferably need to control certain moisture from oxidizing reaction system recovered solvent such as acetic acid and just can apply mechanically, such as, control the moisture of acetic acid 0 ~ 50%, preferably control the moisture of acetic acid 3 ~ 30%.
After solvent recuperation terminates, need to add water and catalyst I is carried out washing separation, obtain organic phase I and aqueous phase I respectively.Washing times can be 1 ~ 10 time, and preferred washing times is 2 ~ 6 times, more preferably 3 ~ 5 times.During each washing water be 0.1 ~ 40:1, preferably 1 ~ 20:1, more preferably 2 ~ 10:1 to the mole dosage ratio of methoxy toluene.
In step 3 of the present invention, add alkali aqueous solution to organic phase I, stir, leaving standstill and divide the phase II that anhydrates, optionally for applying mechanically, obtaining organic phase II.
The aqueous solution that the alkali aqueous solution that step 3 of the present invention uses is 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., the more preferably 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 be 1 ~ 5:1, preferably 1.2 ~ 3:1, more preferably 1.5 ~ 2:1 to the mole dosage ratio of methoxy toluene.
The temperature of reaction of this hydrolysing step is 60 ~ 120 DEG C, preferably 80 ~ 110 DEG C; Reaction times is 0.2 ~ 10h, preferably 0.5 ~ 5h, more preferably 1.5 ~ 3.0h.
Leave standstill and divide the phase II that anhydrates, preferably use it for and apply mechanically.
Aqueous phase I Distillation recovery water, without the need to any process, can be directly used in step 2 washing and to apply mechanically, and heats up in a steamer after the end adds appropriate catalyst I and solvent, is preferably directly used in oxidizing reaction and applies mechanically.
The above-mentioned amount 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 obtained above is put in hydrogenation still, adds solvent, and add catalyst I I, carry out hydrogenation reaction, till in time 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) be 1 ~ 10:1, preferably 2 ~ 5:1, more preferably 3 ~ 4:1 to the weight ratio of methoxy toluene.
Hydrogenation used catalyst II is skeleton nickel, palladium charcoal, ruthenium charcoal, rhodium charcoal, copper chromite etc., preferred skeleton nickel and palladium charcoal, particularly preferably skeleton nickel.
When hydrogenation feeds intake first, catalyzer (as skeleton nickel) be 0.05 ~ 0.5:1, preferably 0.08 ~ 0.3:1, more preferably 0.1 ~ 0.2:1 to the weight ratio of methoxy toluene.
Hydrogenation reaction temperature is 25 ~ 100 DEG C, preferably 30 ~ 95 DEG C, more preferably 50 ~ 90 DEG C.
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 occurs without over-hydrogenation reaction.
In step 5 of the present invention, cooling, suction filtration reclaims catalyst I I, optionally for applying mechanically, carrying out rectifying, obtain p-methoxybenzyl alcohol after filtrate recycling design.
According to the present invention, after above-mentioned hydrogenation reaction terminates, cooling, preferably be cooled to 15 ~ 50 DEG C, be more preferably cooled to 20 ~ 40 DEG C, such as, 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 is 1 ~ 30% of catalyzer charging capacity first, preferably 2 ~ 15%.
After filtrate recycling design (particular methanol), such as, at still temperature 130-136 DEG C He under pressure 3-5mmHg, carry out rectifying, obtain 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, avoid the use of initiator, particular avoid the use of halogen initiator, p-methoxybenzyl alcohol for production high-quality provides a kind of good method, and obtained product p-methoxybenzyl alcohol can be used for food, medicine and other fields.
(2), oxidizing reaction uses cheap oxygen as oxygenant, avoids the use of chemical oxidizing agent and other organic peroxide oxidant, has the feature of economy, environmental protection, green high-efficient.
(3), provide a kind of convenient method reclaiming catalyzer, and the catalyzer reclaimed is applied mechanically repeatedly, does not find decay of activity.
(4), hydrogenation conditions is gentle, and selectivity is high, almost without over-hydrogenation reaction generation.Catalyzer only needs simple filtration to get final product recovery, achieves the recycle of material, reduces raw materials cost.
(5), adopt self-closing circulation technology, achieve the circulation of all materials, greatly reduce the generation of manufacturing cost and the three wastes, alleviate environmental protection pressure.
The inventive method also has easy, to be easy to control and suitability for industrialized production feature.
Embodiment
Further explain and describe content of the present invention below by way of embodiment, 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 to methoxy toluene, after being warmed up to 105-115 DEG C, pass into oxygen, stop after insulation reaction 6.5h passing into oxygen under pressure is normal pressure (namely gauge pressure is 0MPa), sampling is GC and HPLC and is detected, GC result is, aldehydic acid is detected to methoxy toluene 51.5365%, aubepine 16.8333%, p-methoxybenzyl alcohol 1.5437% and acetic acid fennel ester 28.9929%, HPLC and compares 52.8:1.
Oxidizing reaction terminates, and reclaims acetic acid KF=4.87%, acetic acid content 90.92%, is directly used in down batch oxidizing reaction and applies mechanically.Acetic acid reclaims and terminates, and under nitrogen protection, respectively with the clean tap water washing of 200Kg, 100Kg and 50Kg, stratification after stirring 30min, obtains aqueous phase I405.4Kg and oil phase I152Kg.Get oil phase and do GC and HPLC detection, GC result is, detects aldehydic acid compare 67:1 to methoxy toluene 51.8266%, aubepine 16.6041%, p-methoxybenzyl alcohol 1.2122% and acetic acid fennel ester 29.6071%, HPLC.
Put in hydrolytic reaction pot by 200Kg water and 60Kg sodium hydroxide, be warmed up to 80-85 DEG C after dissolving, drip oil phase I152Kg in 30min, drip off rear insulation 1.5-2h, after reaction terminates, stratification, obtains aqueous phase II265.5Kg and oil phase II143Kg.Get oil phase and do GC and HPLC detection, GC result is, methoxy toluene 51.8215%, aubepine 16.7277%, p-methoxybenzyl alcohol 30.8563%, HPLC are detected to aldehydic acid and compare 2502:1.
Proceed in still kettle by aqueous phase I405.4Kg, 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.
Oil phase II143Kg is added, 20Kg skeletal nickel catalyst (moisture 15%), 300Kg anhydrous methanol in autoclave.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 DEG C.Continue to pass into hydrogen in hydrogenation still, to not when absorbing hydrogen.By still temperature drop to 30 ~ 40 DEG C, hydrogen in emptying still, then use nitrogen purge 3 times.Apply mechanically for material reclaims catalyzer for lower batch after pressing machine press filtration in still, filtrate is reclaimed methyl alcohol and is applied mechanically for lower batch, rectifying is carried out under still temperature 131-137 DEG C and 3-5mmHg pressure, 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 to methoxy toluene, after being warmed up to 105-115 DEG C, pass into oxygen, stop after insulation reaction 7.0h passing into oxygen under pressure is normal pressure (namely gauge pressure is 0MPa), sampling is GC and HPLC and is detected, GC result is, aldehydic acid is detected to methoxy toluene 46.3215%, aubepine 11.2277%, p-methoxybenzyl alcohol 1.6563% and acetic acid fennel ester 40.4488%, HPLC and compares 72.4:1.
Oxidizing reaction terminates, and reclaims acetic acid KF=4.59%, acetic acid content 90.31%, is directly used in down batch oxidizing reaction and applies mechanically.Acetic acid reclaims and terminates, and under nitrogen protection, uses the clean tap water of 200Kg, 100Kg and 50Kg respectively, and stratification after stirring 30min, obtains aqueous phase I413.1Kg and oil phase I163Kg.Get oil phase and do GC and HPLC detection, GC result is, detects aldehydic acid compare 73.8:1 to methoxy toluene 46.2915%, aubepine 11.2385%, p-methoxybenzyl alcohol 1.2767% and acetic acid fennel ester 40.7267%, HPLC.
Put in hydrolytic reaction pot by 192Kg water and 48Kg sodium hydroxide, be warmed up to 65-75 DEG C after dissolving, drip oil phase I163Kg in 30min, drip off rear insulation 1.5-2h, after reaction terminates, stratification, obtains aqueous phase II254.8Kg and oil phase II140.8Kg.Get oil phase and do GC and HPLC detection, GC result is, methoxy toluene 46.8186%, aubepine 11.2113%, p-methoxybenzyl alcohol 41.9827%, HPLC are detected to aldehydic acid and compare 2792:1.
Proceed in still kettle by aqueous phase I413.1Kg, 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.
Oil phase II140.8Kg is added, 20Kg skeletal nickel catalyst (moisture 15%), 300Kg anhydrous methanol in autoclave.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 DEG C.Continue to pass into hydrogen in hydrogenation still, to not when absorbing hydrogen.By still temperature drop to 30 ~ 40 DEG C, hydrogen in emptying still, then use nitrogen purge 3 times.Apply mechanically for material reclaims catalyzer for lower batch after pressing machine press filtration in still, filtrate is reclaimed methyl alcohol and is applied mechanically for lower batch, rectifying is carried out under still temperature 130-138 DEG C and 3-5mmHg pressure, 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 to methoxy toluene, after being warmed up to 105-115 DEG C, pass into oxygen, stop after insulation reaction 6.5h passing into oxygen under pressure is normal pressure (namely gauge pressure is 0MPa), sampling is GC and HPLC and is detected, GC result is, aldehydic acid is detected to methoxy toluene 41.4186%%, aubepine 14.7202%, p-methoxybenzyl alcohol 1.6113% and acetic acid fennel ester 41.4296%, HPLC and compares 50:1.
Oxidizing reaction terminates, and reclaims acetic acid KF=5.32%, acetic acid content 88.07%, is directly used in down batch oxidizing reaction and applies mechanically.Acetic acid reclaims and terminates, and under nitrogen protection, uses the clean tap water of 200Kg, 100Kg and 50Kg respectively, and stratification after stirring 30min, obtains aqueous phase I412.3Kg and oil phase I156.8Kg.Get oil phase and do GC and HPLC detection, GC result is, detects aldehydic acid compare 49.8:1 to methoxy toluene 41.2031%, aubepine 14.7714%, p-methoxybenzyl alcohol 1.2053% and acetic acid fennel ester 41.8369%, HPLC.
Put in hydrolytic reaction pot by 200Kg water and 60Kg sodium hydroxide, be warmed up to 65-75 DEG C after dissolving, drip oil phase I156.8Kg in 30min, drip off rear insulation 1.5-2h, after reaction terminates, stratification, obtains aqueous phase II270.8Kg and oil phase II141.6Kg.Get oil phase and do GC and HPLC detection, GC result is, methoxy toluene 41.2213%, aubepine 15.0727%, p-methoxybenzyl alcohol 42.8422%, HPLC are detected to aldehydic acid and compare 2717:1.
Proceed in still kettle by aqueous phase I412.3Kg, open and stir, normal pressure, is warming up to 100-121 DEG C, and recycle-water 354Kg is used for applying mechanically, and heats up in a steamer end catalyst I and applies mechanically for oxidizing reaction.
Oil phase II141.6Kg is added, 20Kg skeletal nickel catalyst (moisture 15%), 300Kg anhydrous methanol in autoclave.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 DEG C.Continue to pass into hydrogen in hydrogenation still, to not when absorbing hydrogen.By still temperature drop to 30 ~ 40 DEG C, hydrogen in emptying still, then use nitrogen purge 3 times.Apply mechanically for material reclaims catalyzer for lower batch after pressing machine press filtration in still, filtrate is reclaimed methyl alcohol and is applied mechanically for lower batch, rectifying is carried out under still temperature 130-138 DEG C and 3-5mmHg pressure, 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 to methoxy toluene, after being warmed up to 105-115 DEG C, pass into oxygen, stop after insulation reaction 4.0h passing into oxygen under pressure is normal pressure (namely gauge pressure is 0MPa), sampling is GC and HPLC and is detected, GC result is, aldehydic acid is detected to methoxy toluene 63.6926%, aubepine 23.5696%, p-methoxybenzyl alcohol 6.7011% and acetic acid fennel ester 2.1628%, HPLC and compares 3.8:1.
Oxidizing reaction terminates, and reclaims acetic acid KF=7.16%, acetic acid content 98.97%, is directly used in down batch oxidizing reaction and applies mechanically.Acetic acid reclaims and terminates, and under nitrogen protection, uses the clean tap water of 200Kg, 100Kg and 50Kg respectively, and stratification after stirring 30min, obtains aqueous phase I435.6Kg and oil phase I136.4Kg.Get oil phase and do GC and HPLC detection, GC result is, detects aldehydic acid compare 4.2:1 to methoxy toluene 63.6327%, aubepine 23.5046%, p-methoxybenzyl alcohol 6.2017% and acetic acid fennel ester 2.7008%, HPLC.
Put in hydrolytic reaction pot by 100Kg water and 10Kg sodium hydroxide, be warmed up to 65-75 DEG C after dissolving, drip oil phase I136.4Kg in 30min, drip off rear insulation 1.5-2h, after reaction terminates, stratification, obtains aqueous phase II109Kg and oil phase II137.1Kg.Get oil phase and do GC and HPLC detection, GC result is, methoxy toluene 63.6698%, aubepine 23.7772%, p-methoxybenzyl alcohol 8.5563%, HPLC are detected to aldehydic acid and compare 2562:1.
Proceed in still kettle by aqueous phase I435.6Kg, open and stir, normal pressure, is warming up to 100-121 DEG C, 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.
Oil phase II137.1Kg is added, 25Kg skeletal nickel catalyst (moisture 15%), 300Kg anhydrous methanol in autoclave.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 DEG C.Continue to pass into hydrogen in hydrogenation still, to not when absorbing hydrogen.By still temperature drop to 30 ~ 40 DEG C, hydrogen in emptying still, then use nitrogen purge 3 times.Apply mechanically for material reclaims catalyzer for lower batch after pressing machine press filtration in still, filtrate is reclaimed methyl alcohol and is applied mechanically for lower batch, rectifying is carried out under still temperature 129-136 DEG C and 3-5mmHg pressure, 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 puts in dry stainless steel oxidation still to methoxy toluene, after being warmed up to 105-115 DEG C, pass into oxygen, stop after insulation reaction 1.5h passing into oxygen under pressure is normal pressure (namely gauge pressure is 0MPa), sampling is GC and HPLC and is detected, 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 terminates, and reclaims acetic acid KF=3.26%, acetic acid content 84.62%, is directly used in down batch oxidizing reaction and applies mechanically.Acetic acid reclaims and terminates, and under nitrogen protection, uses the clean tap water of 200Kg, 100Kg and 50Kg respectively, and stratification after stirring 30min, obtains aqueous phase I410.4Kg and oil phase I156.9Kg.Get oil phase and do GC and HPLC detection, GC result is, detects aldehydic acid compare 11.2:1 to methoxy toluene 47.2365%, aubepine 10.9783%, p-methoxybenzyl alcohol 0.9347% and acetic acid fennel ester 40.2075%, HPLC.
Put in hydrolytic reaction pot by 200Kg water and 60Kg sodium hydroxide, be warmed up to 65-75 DEG C after dissolving, drip oil phase I156.9Kg in 30min, drip off rear insulation 1.5-2h, after reaction terminates, stratification, obtains aqueous phase II265.5Kg and oil phase II151.4Kg.Get oil phase and do GC and HPLC detection, GC result is, methoxy toluene 47.1987%, aubepine 11.7928%, p-methoxybenzyl alcohol 40.7085%, HPLC are detected to aldehydic acid and compare 2813:1.
Proceed in still kettle by aqueous phase I410.4Kg, open and stir, normal pressure, is warming up to 100-121 DEG C, 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.
Oil phase II151.4Kg is added, 25Kg skeletal nickel catalyst (moisture 15%), 300Kg anhydrous methanol in autoclave.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 DEG C.Continue to pass into hydrogen in hydrogenation still, to not when absorbing hydrogen.By still temperature drop to 30 ~ 40 DEG C, hydrogen in emptying still, then use nitrogen purge 3 times.Apply mechanically for material reclaims catalyzer for lower batch after pressing machine press filtration in still, filtrate is reclaimed methyl alcohol and is applied mechanically for lower batch, rectifying is carried out under still temperature 130-136 DEG C and 3-5mmHg pressure, 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 puts in dry stainless high-pressure oxidizing kettle to methoxy toluene, after being warmed up to 105-115 DEG C, setting oxygen pressure is 0.14-0.18MPa, continue to pass into oxygen, stop passing into oxygen after pressure (gauge pressure) is for insulation reaction 2.0h under 0.20MPa, sampling is GC and HPLC and is detected, 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 terminates, and reclaims acetic acid KF=3.43%, acetic acid content 90.10%, is directly used in down batch oxidizing reaction and applies mechanically.Acetic acid reclaims and terminates, and under nitrogen protection, uses the clean tap water of 200Kg, 100Kg and 50Kg respectively, and stratification after stirring 30min, obtains aqueous phase I414.2Kg and oil phase I152.7Kg.Get oil phase and do GC and HPLC detection, GC result is, detects aldehydic acid compare 11.6:1 to methoxy toluene 53.1265%, aubepine 30.6738%, p-methoxybenzyl alcohol 1.6842% and acetic acid fennel ester 13.7175%, HPLC.
Put in hydrolytic reaction pot by 200Kg water and 60Kg sodium hydroxide, be warmed up to 65-75 DEG C after dissolving, drip oil phase I152.7Kg in 30min, drip off rear insulation 1.5-2h, after reaction terminates, stratification, obtains aqueous phase II267.2Kg and oil phase II153.5Kg.Get oil phase and do GC and HPLC detection, GC result is, methoxy toluene 53.1879%, aubepine 30.5928%, p-methoxybenzyl alcohol 15.4266%, HPLC are detected to aldehydic acid and compare 2075:1.
Proceed in still kettle by aqueous phase I414.2Kg, open and stir, normal pressure, is warming up to 100-121 DEG C, 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.
Oil phase II152.7Kg is added, 25Kg skeletal nickel catalyst (moisture 15%), 300Kg anhydrous methanol in autoclave.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 DEG C.Continue to pass into hydrogen in hydrogenation still, to not when absorbing hydrogen.By still temperature drop to 30 ~ 40 DEG C, hydrogen in emptying still, then use nitrogen purge 3 times.Apply mechanically for material reclaims catalyzer for lower batch after pressing machine press filtration in still, filtrate is reclaimed methyl alcohol and is applied mechanically for lower batch, rectifying is carried out under still temperature 132-137 DEG C and 3-5mmHg pressure, obtain methoxy toluene 61.7Kg, GC purity 99.55%, p-methoxybenzyl alcohol 60.3Kg, GC purity 99.72%, yield 88.3%.
embodiment 7
The various recovered material of embodiment 3 are applied mechanically.
Acetic acid 478.2Kg acetic acid (KF=5.32% will be reclaimed, acetic acid content 88.07%, to methoxy toluene 6.61%), new acetic acid 67.6Kg (KF<1%), reclaim catalyzer, fresh acetic acid cobalt 0.5Kg, fresh acetic acid chromium 0.3Kg and 90.6Kg puts in dry stainless steel oxidation still to methoxy toluene, after being warmed up to 105-115 DEG C, pass into oxygen, stop after insulation reaction 6.5h passing into oxygen under pressure is normal pressure (namely gauge pressure is 0MPa), sampling is GC and HPLC and is detected, 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 terminates, and reclaims acetic acid KF=9.94%, acetic acid content 84.82%, is directly used in down batch oxidizing reaction and applies mechanically.Acetic acid reclaims and terminates, and under nitrogen protection, uses the clean tap water of 200Kg, 100Kg and 50Kg respectively, and stratification after stirring 30min, obtains aqueous phase I421.5Kg and oil phase I168.8Kg.Get oil phase and do GC and HPLC detection, GC result is, detects aldehydic acid compare 47.5:1 to methoxy toluene 42.5717%, aubepine 12.9291%, p-methoxybenzyl alcohol 1.0953% and acetic acid fennel ester 42.5863%, HPLC.
Put in hydrolytic reaction pot by 200Kg water and 60Kg sodium hydroxide, be warmed up to 65-75 DEG C after dissolving, drip oil phase I168.8Kg in 30min, drip off rear insulation 1.5-2h, after reaction terminates, stratification, obtains aqueous phase II269.3Kg and oil phase II140.2Kg.Get oil phase and do GC and HPLC detection, GC result is, methoxy toluene 42.5413%, aubepine 13.2271%, p-methoxybenzyl alcohol 43.5417%, HPLC are detected to aldehydic acid and compare 1950:1.
Proceed in still kettle by aqueous phase I421.5Kg, open and stir, normal pressure, is warming up to 100-121 DEG C, 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 DEG C.Continue to pass into hydrogen in hydrogenation still, to not when absorbing hydrogen.By still temperature drop to 30 ~ 40 DEG C, hydrogen in emptying still, then use nitrogen purge 3 times.Apply mechanically for material reclaims catalyzer for lower batch after pressing machine press filtration in still, filtrate is reclaimed methyl alcohol and is applied mechanically for lower batch, rectifying is carried out under still temperature 131-136 DEG C and 3-5mmHg pressure, 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 has been intended to illustrate, and limits its summary of the invention never in any form.Concerning art technology people, farthest can utilize the present invention based on explanation herein, and multiple amendment or modification can be carried out not departing from right of the present invention or spirit.Each reference that the application quotes, which is hereby incorporated by reference.
Claims (12)
1. prepared by methoxy toluene to a method for p-methoxybenzyl alcohol, it is characterized in that, comprise the following steps:
Step 1), add methoxy toluene, catalyst I and solvent acetic acid in oxidizing reactor, catalyst I is transition metal salt, acetic acid be 1 ~ 50:1 to the mole dosage ratio of methoxy toluene, pass into oxygen at a certain temperature, stopped reaction after reaction certain hour;
Step 2), oxidizing reaction terminates, recycling design acetic acid, and recovered solvent acetic acid controls its moisture 0 ~ 50%, for applying mechanically, then adding washing and going catalyst I, obtain organic phase I and aqueous phase I;
Step 3), in organic phase I, add alkali aqueous solution, alkali aqueous solution used is the aqueous solution of basic metal inorganic acid salt or alkali metal hydroxide, stirs, and leaving standstill and divides the phase II that anhydrates, for applying mechanically, obtaining organic phase II; Aqueous phase I Distillation recovery water, for applying mechanically, heating up in a steamer after the end adds catalyst I and solvent, applying mechanically for oxidizing reaction;
Step 4), organic phase II is put in hydrogenation still, adds solvent, hydrogenation solvent for use be 2 ~ 5:1 to the weight ratio of methoxy toluene, and add catalyst I I, carry out hydrogenation reaction, till in time no longer absorbing hydrogen;
Step 5), be cooled to 15 ~ 50 DEG C, suction filtration reclaims catalyst I I, for applying mechanically, carrying out rectifying, obtain p-methoxybenzyl alcohol after filtrate recycling design.
2. preparation method according to claim 1, is characterized in that,
In step 1, acetic acid be 3 ~ 30:1 to the mole dosage ratio of methoxy toluene.
3. preparation method according to claim 1, is characterized in that,
In step 1,
Catalyst I is cobaltous acetate, manganous acetate, nickelous acetate, cerous acetate, chromium acetate, zinc acetate, ironic acetate, venus crystals, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, manganous nitrate, cupric nitrate, cobalt chloride, cobaltous bromide, acetylacetone cobalt, ferric acetyl acetonade, one of cobalt stearate, manganese stearate, cobalt naphthenate, acid chloride, Palladous chloride, or the composite catalyst of certain mol proportion composition pressed by several catalyzer wherein, and/or
The temperature of oxidizing reaction is 40 ~ 150 DEG C;
Oxidation pressure is 0 ~ 2.0MPa;
Oxidation time is 0.1-20h.
4. preparation method according to claim 3, is characterized in that,
In step 1,
Catalyst I is one of cobaltous acetate, manganous acetate, chromium acetate, cerous acetate, acid chloride, ironic acetate, venus crystals, or the composite catalyst of their compositions, and/or
The temperature of oxidizing reaction is 80 ~ 120 DEG C;
Oxidation pressure is normal pressure;
Oxidation time is 1-10h.
5. preparation method according to claim 1, is characterized in that,
In step 2, recovered solvent acetic acid controls its moisture 3 ~ 30%, after solvent recuperation terminates, adds water and catalyst I is carried out washing separation, obtain organic phase I and aqueous phase I respectively.
6., according to the preparation method one of claim 1 to 5 Suo Shu, it is characterized in that,
In step 3,
Alkali aqueous solution used is the aqueous solution of sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide;
The mass percentage concentration of alkali aqueous solution is 1 ~ 50%;
In alkali aqueous solution alkali be 1 ~ 5:1 to the mole dosage ratio of methoxy toluene;
The temperature of reaction of this hydrolysing step is 60 ~ 120 DEG C;
Aqueous phase I Distillation recovery, without the need to any process, is directly used in washing in step 2 and applies mechanically; Heat up in a steamer the end add catalyst I and solvent after be directly used in oxidizing reaction and apply mechanically.
7., 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, or varsol, or ether solvent.
8. preparation method according to claim 7, is characterized in that,
In step 4, hydrogenation solvent for use is methyl alcohol, ethanol, Virahol, the trimethyl carbinol, normal heptane, hexanaphthene, sherwood oil, n-butyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran.
9., 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 be 3 ~ 4:1 to the weight ratio of methoxy toluene.
10., according to the preparation method one of claim 1 to 5 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.
11., according to the preparation method one of claim 1 to 5 Suo Shu, is characterized in that,
In step 4, hydrogenation reaction temperature is 25 ~ 100 DEG C; Hydrogenation reaction pressure is 0 ~ 1.5MPa.
12., according to the preparation method one of claim 1 to 5 Suo Shu, is characterized in that,
In step 5, after hydrogenation reaction terminates, be cooled to 20 ~ 40 DEG C, suction filtration recovery catalyst I I is directly used in and applies mechanically, and now add appropriate live catalyst, the additional amount of live catalyst is 1 ~ 30% of catalyzer charging capacity first.
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| US5354919A (en) * | 1992-06-29 | 1994-10-11 | Rhone-Poulenc Chimie | Oxidation of aromatic compounds substituted by oxidizable alkyl moieties |
| CN101774946A (en) * | 2009-12-15 | 2010-07-14 | 华东理工大学 | Method for preparing para methoxy phenyl acetonitrile |
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| US5354919A (en) * | 1992-06-29 | 1994-10-11 | Rhone-Poulenc Chimie | Oxidation of aromatic compounds substituted by oxidizable alkyl moieties |
| CN101774946A (en) * | 2009-12-15 | 2010-07-14 | 华东理工大学 | Method for preparing para methoxy phenyl acetonitrile |
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