CN103508850B - Preparation method for 2,6-dihydroxytoluene - Google Patents
Preparation method for 2,6-dihydroxytoluene Download PDFInfo
- Publication number
- CN103508850B CN103508850B CN201310505791.9A CN201310505791A CN103508850B CN 103508850 B CN103508850 B CN 103508850B CN 201310505791 A CN201310505791 A CN 201310505791A CN 103508850 B CN103508850 B CN 103508850B
- Authority
- CN
- China
- Prior art keywords
- tert
- butyltoluene
- reaction
- weight ratio
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/045—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen
- C07C37/05—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen by substitution of a NH2 group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method for 2,6-dihydroxytoluene. The preparation method adopts p-tert-butyltoluene as a raw material which is subjected to nitration, reduction and hydrolytic tert-butyl elimination reactions to obtain 2,6-dihydroxytoluene. The preparation method has the characteristics of high selectivity and product purity, low cost, environmental friendliness and the like, and is a route with an industrialization prospect.
Description
Technical field
The present invention relates to a kind of preparation method of fragrant phenolic compound, especially relate to a kind of preparation method of 2,6-orcin.
Background technology
2,6-orcin, another name 2-methyl thunder lock sweet smell or 2-methylresorcinol, belong to fragrant phenolic compound, be a kind of important industrial chemicals, can be widely used in multiple fields such as pigment, dyestuff, hair dye, synthetic resins, medicine, agricultural chemicals.
The method for making of 2,6-orcin has had more research, and the preparation method of current 2,6-orcins mainly contains following several: (a) 2,6-diaminotoluene hydrolysis; B () take hydroresorcinol as raw material, pass through CH
3i or Mannich reaction introduces methyl dehydrogenation again at 2; C () Resorcinol is that raw material and methyl alcohol direct reaction obtain or Resorcinol first introduces the tertiary butyl in 4,6-positions, then slough the tertiary butyl etc. again by after 2 alkylations.
In aforesaid method, method (a) adopts 2,6-diaminotoluene to be hydrolyzed, and it can adopt diazonium to be hydrolyzed and high temperature and high pressure hydrolysis under acidic conditions, and the method step is short, needs to carry out under high-temperature and high-pressure conditions; But, which kind of hydrolysis method no matter is adopted all to have 2, the preparation of 6-diaminotoluene and separation problem, 2,6-diaminotoluene is generally reduced obtained by 2,6-dinitrotoluene (DNT), and 2 of known report, the preparation method of 6-dinitrotoluene (DNT) has trotyl reduction heavy nitrogen, tosic acid nitrify water solution, methylbenzene nitration mixture separation method three kinds of methods.Wherein trotyl solvent reduction, diazonium deamination method obtain 2,6-dinitrotoluene (DNT) yield about 45% through two-step reaction, and yield is on the low side, and raw material trotyl is too dangerous, there is larger potential safety hazard in production; Adopt the nitrated hydrolysis process of tosic acid to have the serious problem of temperature of reaction height equipment corrosion, nitrated temperature is 110 ~ 115 DEG C, and hydrolysis temperature is 170 DEG C, and technique is serious to equipment corrosion, and the security of production is poor, and the three wastes of generation are more; Methylbenzene nitration reduction can obtain the mixture of 2,4-dinitrotoluene (DNT) and 2,6-dinitrotoluene (DNT), because both character are close to having certain difficulty in separation; , all there is the problems such as separation difficulty, yield is low, the three wastes are large in the bibliographical information method of the separating-purifyings such as ethyl alcohol recrystallization, trieline recrystallization, dust technology recrystallization, vitriol oil recrystallization, complexing recrystallization.Thus on the source of 2,6-dinitrotoluene (DNT), there is larger difficulty.
Method (b) adopts 1, the hydroresorcinol dehydrogenation reaction that methylates prepares 2, the method of 6-orcin, its advantage is: raw material is simple and easy to get, reaction conditions is gentleer, be obtained by reacting the product of high level through 3 steps, preparation method has certain advantage, but the method needs through hydrogenation and dehydrogenation reaction, need to use a large amount of palladium-carbon catalysts, and reaction yield is low, the too high the method that causes of product cost cannot enter industrialization.
Method (c) is that raw material is prepared 2,6-orcin and had two kinds of methods with Resorcinol: (1) Resorcinol and methyl alcohol 330 DEG C of direct reaction under catalysts conditions obtain product; (2) Resorcinol first introduces the tertiary butyl in 4,6-position, then sloughs the tertiary butyl with methyl alcohol or methyl iodide shortening again by after the alkylation of 2-position.Aforesaid method (1) not only needs to carry out under high temperature, condition of high voltage, and yield is low, the mixture separation of generation difficulty, unsuitable suitability for industrialized production; Method (2) is though can suitability for industrialized production, but methyl iodide is expensive, and product cost is high.
The cost had in these methods is above too high, and some actually operatings are more difficult, all can not meet the requirement of suitability for industrialized production.
Summary of the invention
In order to overcome the deficiency that prior art exists, the invention provides a kind of 2, the preparation method of 6-orcin, it take p-tert-butyltoluene as raw material, obtains 2 through nitrated, reduction, hydrolysis de-t-butylation, 6-orcin, have selectivity high, product purity is high, and cost is low, the features such as environmental friendliness are routes with industrial prospect.
A kind of preparation method of 2,6-orcin, comprises the steps:
(1) nitration reaction: be that raw material carries out mixed acid nitrification in organic solvent and obtains 2,6-dinitrobenzene-4-4-tert-butyltoluene with p-tert-butyltoluene;
(2) reduction and salt-forming reaction: in organic solvent, after carrying out hydro-reduction reaction under hydrogenation catalyst effect, acid adding obtains 2,6-diamino-4-4-tert-butyltoluene salt to 2,6-dinitrobenzene-4-4-tert-butyltoluene;
(3) hydrolysis and de-t-butylation: in aqueous, be hydrolyzed under catalyst action obtains 2,6-orcin with de-t-butylation to 2,6-diamino-4-4-tert-butyltoluene salt.
Preferably, in step (1), described nitration mixture comprise mass concentration be 95% nitric acid and mass concentration be the sulfuric acid of 98%; Nitration reaction temperature is 30 ~ 50 DEG C; Organic solvent is the one in tetracol phenixin, methylene dichloride, ethylene dichloride, benzene, toluene, DMF, and the weight ratio of described organic solvent and p-tert-butyltoluene is 2 ~ 6:1; The weight ratio of p-tert-butyltoluene, 95% nitric acid, 98% sulfuric acid is 1:0.8 ~ 1.2:0.6 ~ 3.
Preferably, in step (1), reaction solution is diluted in a certain amount of frozen water after having reacted, separatory, extraction, concentrated after, obtain 2,6-dinitrobenzene-4-4-tert-butyltoluene through recrystallization.
Preferably, in step (2), described reduction reaction temperature is 20 ~ 40 DEG C; Organic solvent is the one in methyl alcohol, ethanol, Virahol, ethyl acetate, toluene, and the weight ratio of described organic solvent and 2,6-dinitrobenzene-4-4-tert-butyltoluene is 4 ~ 10:1; Described hydrogenation catalyst is the one in palladium carbon, palladium aluminium, Raney's nickel, hydrogenation catalyst and 2,6-dinitrobenzene-4-4-tert-butyltoluene weight ratio be 0.01 ~ 0.05:1.
Preferably, in step (2), after reduction reaction completes, after filtration, acid adding salify, obtain 2,6-diamino-4-4-tert-butyltoluene salt; Wherein, described acid is the one in hydrochloric acid, sulfuric acid, phosphoric acid.
Preferably, in step (3), described hydrolysis and de-t-butylation temperature are 200 ~ 280 DEG C; Described catalyzer is the solid super-strong acid containing sulfate radical, and its carrier is one or more the arbitrary combination in ferric oxide, zirconium dioxide, titanium dioxide, and the weight ratio of catalyzer and 2,6-diamino-4-4-tert-butyltoluene salt is 0.1 ~ 0.8:1.
Preferably, in step (3), after having reacted through filtering, be washed to neutrality through organic solvent extraction, organic phase, steam organic solvent after, residual solid water recrystallization obtains 2,6-orcin; Wherein, the organic solvent that extraction is selected is the one in isopropyl ether, ether, methyl tertiary butyl ether, and the weight ratio of organic solvent and 2,6-diamino-4-4-tert-butyltoluene is 4 ~ 10:1; During recrystallization, the weight ratio of water and 2,6-diamino-4-4-tert-butyltoluene salt is 1.5 ~ 4:1.
Preferably, the preparation method of 2,6-orcin, comprises the steps:
(1) nitration reaction: be that raw material carries out mixed acid nitrification and obtains 2,6-dinitrobenzene-4-4-tert-butyltoluene in ethylene dichloride with p-tert-butyltoluene; Wherein, nitration reaction temperature is 40 DEG C, and the weight ratio of ethylene dichloride and p-tert-butyltoluene is 3.38:1; The weight ratio of p-tert-butyltoluene, 95% nitric acid, 98% sulfuric acid is 1:0.88:1.89; Nitration mixture time for adding is 3h, reaction times 3h;
(2) reduction and salt-forming reaction: 2,6-dinitrobenzene-4-4-tert-butyltoluene, in methyl alcohol, carries out after hydro-reduction obtains under 5% palladium-carbon catalyst effect, after filtration, add 98% sulfuric acid after obtain 2,6-diamino-4-4-tert-butyltoluene vitriol; Wherein, reduction reaction temperature is 30 DEG C, and the weight ratio of methyl alcohol and 2,6-dinitrobenzene-4-4-tert-butyltoluene is 5.25:1,5% palladium carbon and 2,6-dinitrobenzene-4-4-tert-butyltoluene weight ratio be 0.026:1; Reaction pressure 0.5MPa, reaction times 3h;
(3) hydrolysis and de-t-butylation: in aqueous, be hydrolyzed under the solid super-strong acid effect that carrier is zirconium dioxide obtains 2,6-orcin with de-t-butylation to 2,6-diamino-4-4-tert-butyltoluene vitriol; Wherein, temperature of reaction is 220 DEG C; The weight ratio of solid super-strong acid and 2,6-diamino-4-4-tert-butyltoluene vitriol is 0.53:1.
Compared with prior art, beneficial effect of the present invention is mainly reflected in: adopt method provided by the invention to prepare 2,6-orcin has good reaction selectivity, yield is high, by product is few, pollute the features such as little, efficiently solve existing 2,6-orcin preparation process Road line lengths, cost is high, condition is harsh, pollute large an etc. difficult problem.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this.
Embodiment 1
A kind of preparation method of 2,6-orcin, comprises the steps:
(1) nitration reaction: drop into a certain amount of p-tert-butyltoluene 148g in 1L four-hole bottle, ethylene dichloride 500g, stir, heating in water bath to 40 DEG C, the nitration mixture prepared (130g95% nitric acid and 280g98% sulfuric acid) is added drop-wise in the dichloroethane solution of p-tert-butyltoluene, nitration mixture is added dropwise to complete in 3h, be added dropwise to complete and continue stirring reaction 3h, sampling detection reacts completely to p-tert-butyltoluene, reaction solution is poured in the mixture of ice and water of 1kg, reaction solution layering, organic layer is separated, use 400g ethylene dichloride aqueous phase extracted again, layering, organic phase merges, wash once with 5% aqueous sodium hydroxide solution 200ml, wash twice with water again, each water 200ml, reclaim under reduced pressure ethylene dichloride, obtain 2, 6-dinitrobenzene-4-4-tert-butyltoluene crude product, add 500g methyl alcohol and be warming up to 50 DEG C of stirring 30min, be cooled to 0 DEG C again, suction filtration, dry, obtain product 219.2g(yield 92%), HPLC > 99%,
(2) reduction and salt-forming reaction: drop into 2, the 6-dinitrobenzene-4-4-tert-butyltoluenes that 95.3g step (1) obtains in 1L autoclave, methyl alcohol 500g, 5% palladium carbon 2.5g(moisture 50%), envelope still, is warming up to 30 DEG C, stirs, nitrogen replacement three times, hydrogen exchange three times, fills hydrogen to 0.5Mpa, samples after reaction 3h, react completely to raw material 2,6-dinitrobenzene-4-4-tert-butyltoluene; Reacting liquid filtering is removed catalyzer, directly adds 98% sulfuric acid acid out salify and obtain 2,6-diamino-4-4-tert-butyltoluene vitriol in reaction solution, oven dry obtains 2,6-diamino-4-4-tert-butyltoluene sulfate solid can be directly used in next step reaction;
(3) hydrolysis and de-t-butylation: drop into 2,6-diamino-4-4-tert-butyltoluene vitriol 37.4g in 500ml zirconium reactor, water 200ml, zirconium dioxide based solid super-strong acid (SO
4 2-/ ZrO
2) 20g, envelope still, be warming up to 220 DEG C, start reaction, 10h is sampled to raw material reaction and completes, be cooled to less than 40 DEG C, filter, removing solid acid, filtrate extracts 2 times with isopropyl ether, each use isopropyl ether 200ml, merge organic phase, organic phase washed with water 2 times, reclaim isopropyl ether and obtain crude product 2, 6-orcin, 60ml deionized water is added in crude product, be warming up to 60 DEG C, add gac 2g, vat powder 2g, stir 30min, suction filtration removing gac, be cooled to less than 10 DEG C, product white crystal is separated out, filter, 60 DEG C of vacuum dryings obtain 2, 6-orcin sterling 12.7g, yield 75.8%, HPLC>=99%.
Embodiment 2
A kind of preparation method of 2,6-orcin, comprises the steps:
(1) nitration reaction: drop into a certain amount of p-tert-butyltoluene 148g in 1L four-hole bottle, trichloromethane 390g, stir, heating in water bath to 50 DEG C, the nitration mixture prepared (120g95% nitric acid and 130g98% sulfuric acid) is added drop-wise in the chloroform soln of p-tert-butyltoluene, nitration mixture is added dropwise to complete in 2h, be added dropwise to complete and continue stirring reaction 3h, sampling detection reacts completely to p-tert-butyltoluene, reaction solution is poured in the mixture of ice and water of 1kg, reaction solution layering, organic layer is separated, use 400g chloroform extraction aqueous phase again, layering, organic phase merges, wash once with 5% aqueous sodium hydroxide solution 200ml, wash twice with water again, each water 200ml, reclaim under reduced pressure trichloromethane, obtain 2, 6-dinitrobenzene-4-4-tert-butyltoluene crude product, add 500g methyl alcohol in crude product and be warming up to 50 DEG C of stirring 30min, be cooled to 0 DEG C again and carry out recrystallization, suction filtration, dry, obtain product 223g(yield 93.6%), HPLC > 99%,
(2) reduction and salt-forming reaction: drop into 2, the 6-dinitrobenzene-4-4-tert-butyltoluenes that 100g step (1) obtains in 1L autoclave, ethyl acetate 450g, Raney's nickel 2.0g, envelope still, is warming up to 40 DEG C, stirs, nitrogen replacement three times, hydrogen exchange three times, fills hydrogen to 0.5Mpa, samples after reaction 3h, react completely to raw material 2,6-dinitrobenzene-4-4-tert-butyltoluene; Reacting liquid filtering is removed catalyzer, directly adds hydrochloric acid acid out salify and obtain 2,6-diamino-4-4-tert-butyltoluene hydrochloride in reaction solution, oven dry obtains 2,6-diamino-4-4-tert-butyltoluene HCl, solid can be directly used in next step reaction;
(3) hydrolysis and de-t-butylation: drop into 2,6-diamino-4-4-tert-butyltoluene hydrochloride 30g in 500ml zirconium reactor, water 200ml, titania-based solid super-strong acid (SO
4 2-/ TiO
2) 10g, envelope still, be warming up to 260 DEG C, start reaction, 10h is sampled to raw material reaction and completes, be cooled to less than 40 DEG C, filter, removing solid super-strong acid, filtrate extracts 2 times with methyl tertiary butyl ether, each use methyl tertiary butyl ether 200ml, merge organic phase, organic phase washed with water 2 times, reclaim methyl tertiary butyl ether and obtain crude product 2, 6-orcin, 60ml deionized water is added in crude product, be warming up to 60 DEG C, add gac 2g, vat powder 2g, stir 30min, suction filtration removing gac, be cooled to less than 10 DEG C, product white crystal is separated out, filter, 60 DEG C of vacuum dryings obtain 2, 6-orcin sterling 13.6g, yield 81.2%, HPLC>=99%.
Embodiment 3
A kind of preparation method of 2,6-orcin, comprises the steps:
(1) nitration reaction: drop into a certain amount of p-tert-butyltoluene 148g in 1L four-hole bottle, toluene 600g, stir, heating in water bath to 35 DEG C, the nitration mixture prepared (170g95% nitric acid and 400g98% sulfuric acid) is added drop-wise in p-tert-butyltoluene solution, nitration mixture is added dropwise to complete in 4h, be added dropwise to complete and continue stirring reaction 5h, sampling detection reacts completely to p-tert-butyltoluene, reaction solution is poured in the mixture of ice and water of 1.2kg, reaction solution layering, organic layer is separated, use 500g toluene aqueous phase extracted again, layering, organic phase merges, wash once with 5% aqueous sodium hydroxide solution 300ml, wash twice with water again, each water 300ml, reclaim under reduced pressure toluene, obtain 2, 6-dinitrobenzene-4-4-tert-butyltoluene crude product, add 500g methyl alcohol and be warming up to 50 DEG C of stirring 30min, be cooled to 0 DEG C again, suction filtration, dry, obtain product 217.3g(yield 91.2%), HPLC > 99%,
(2) reduction and salt-forming reaction: drop into 2, the 6-dinitrobenzene-4-4-tert-butyltoluenes that 90g step (1) obtains in 1L autoclave, Virahol 600g, palladium Al catalysts 4.0g, envelope still, is warming up to 30 DEG C, stirs, nitrogen replacement three times, hydrogen exchange three times, fills hydrogen to 0.5Mpa, samples after reaction 3h, react completely to raw material 2,6-dinitrobenzene-4-4-tert-butyltoluene; Reacting liquid filtering is removed catalyzer, directly adds 98% sulfuric acid acid out salify and obtain 2,6-diamino-4-4-tert-butyltoluene vitriol in reaction solution, oven dry obtains 2,6-diamino-4-4-tert-butyltoluene sulfate solid can be directly used in next step reaction;
(3) hydrolysis and de-t-butylation: drop into 2,6-diamino-4-4-tert-butyltoluene vitriol 37.4g in 500ml zirconium reactor, water 200ml, carrier is the solid super-strong acid (SO of ferric oxide, zirconium dioxide combination
4 2-/ ZrO
2-Fe
2o
3) 15g, envelope still, be warming up to 220 DEG C, start reaction, 10h is sampled to raw material reaction and completes, be cooled to less than 40 DEG C, filter, removing solid super-strong acid, filtrate is by extracted with diethyl ether 2 times, each use ether 200ml, merge organic phase, organic phase washed with water 2 times, reclaim ether and obtain crude product 2, 6-orcin, 60ml deionized water is added in crude product, be warming up to 60 DEG C, add gac 2g, vat powder 2g, stir 30min, suction filtration removing gac, be cooled to less than 10 DEG C, product white crystal is separated out, filter, 60 DEG C of vacuum dryings obtain 2, 6-orcin sterling 13.2g, yield 75.8%, HPLC>=99%.
Claims (6)
1. the preparation method of an orcin, is characterized in that comprising the steps:
(1) nitration reaction: be that raw material carries out mixed acid nitrification in organic solvent and obtains 2,6-dinitrobenzene-4-4-tert-butyltoluene with p-tert-butyltoluene;
(2) reduction and salt-forming reaction: in organic solvent, after carrying out hydro-reduction reaction under hydrogenation catalyst effect, acid adding obtains 2,6-diamino-4-4-tert-butyltoluene salt to 2,6-dinitrobenzene-4-4-tert-butyltoluene;
(3) hydrolysis and de-t-butylation: in aqueous, be hydrolyzed under catalyst action obtains 2,6-orcin with de-t-butylation to 2,6-diamino-4-4-tert-butyltoluene salt;
In step (3), described hydrolysis and de-t-butylation temperature are 200 ~ 280 DEG C; Described catalyzer is the solid super-strong acid containing sulfate radical, its carrier is one or more the arbitrary combination in ferric oxide, zirconium dioxide, titanium dioxide, the weight ratio of catalyzer and 2,6-diamino-4-4-tert-butyltoluene salt is 0.1 ~ 0.8: 1;
After in step (3), being washed to neutrality after having reacted through filtration, organic solvent extraction, organic phase, steaming organic solvent, residual solid water recrystallization obtains 2,6-orcin; Wherein, the organic solvent that extraction is selected is the one in isopropyl ether, ether, methyl tertiary butyl ether, and the weight ratio of organic solvent and 2,6-diamino-4-4-tert-butyltoluene is 4 ~ 10: 1; During recrystallization, the weight ratio of water and 2,6-diamino-4-4-tert-butyltoluene salt is 1.5 ~ 4: 1.
2. according to the preparation method of 2,6-orcins described in claim 1, it is characterized in that: in step (1), described nitration mixture comprise mass concentration be 95% nitric acid and mass concentration be the sulfuric acid of 98%; Nitration reaction temperature is 30 ~ 50 DEG C; Organic solvent is the one in tetracol phenixin, methylene dichloride, ethylene dichloride, benzene, toluene, and the weight ratio of described organic solvent and p-tert-butyltoluene is 2 ~ 6: 1; The weight ratio of p-tert-butyltoluene, 95% nitric acid, 98% sulfuric acid is 1: 0.8 ~ 1.2: 0.6 ~ 3.
3. according to the preparation method of 2,6-orcins described in claim 2, it is characterized in that: in step (1), reaction solution is diluted in a certain amount of frozen water after having reacted, separatory, extraction, concentrated after, obtain 2,4-dinitrobenzene-4-4-tert-butyltoluene through recrystallization.
4. according to the preparation method of 2,6-orcins described in claim 1, it is characterized in that: in step (2), described reduction reaction temperature is 20 ~ 40 DEG C; Organic solvent is the one in methyl alcohol, ethanol, Virahol, ethyl acetate, toluene, and the weight ratio of described organic solvent and 2,6-dinitrobenzene-4-4-tert-butyltoluene is 4 ~ 10: 1; Described hydrogenation catalyst is the one in palladium carbon, palladium aluminium, Raney's nickel, hydrogenation catalyst and 2,6-dinitrobenzene-4-4-tert-butyltoluene weight ratio be 0.01 ~ 0.05: 1.
5. according to the preparation method of 2,6-orcins described in claim 4, it is characterized in that: in step (2), after reduction reaction completes, after filtration, acid adding salify, obtain 2,6-diamino-4-4-tert-butyltoluene salt; Wherein, described acid is the one in hydrochloric acid, sulfuric acid, phosphoric acid.
6., according to the preparation method of 2,6-orcins described in claim 1, it is characterized in that comprising the steps:
(1) nitration reaction: be that raw material carries out mixed acid nitrification and obtains 2,6-dinitrobenzene-4-4-tert-butyltoluene in ethylene dichloride with p-tert-butyltoluene; Wherein, nitration reaction temperature is 40 DEG C, and the weight ratio of ethylene dichloride and p-tert-butyltoluene is 3.38: 1; The weight ratio of p-tert-butyltoluene, 95% nitric acid, 98% sulfuric acid is 1: 0.88: 1.89; Nitration mixture time for adding is 3h, reaction times 3h;
(2) reduction and salt-forming reaction: 2,6-dinitrobenzene-4-4-tert-butyltoluene, in methyl alcohol, carries out after hydro-reduction obtains under 5% palladium-carbon catalyst effect, after filtration, add 98% sulfuric acid after obtain 2,6-diamino-4-4-tert-butyltoluene vitriol; Wherein, reduction reaction temperature is 30 DEG C, and the weight ratio of methyl alcohol and 2,6-dinitrobenzene-4-4-tert-butyltoluene is 5.25:1,5% palladium carbon and 2,6-dinitrobenzene-4-4-tert-butyltoluene weight ratio be 0.026: 1; Reaction pressure 0.5MPa, reaction times 3h;
(3) hydrolysis and de-t-butylation: in aqueous, be hydrolyzed under the solid super-strong acid effect that carrier is zirconium dioxide obtains 2,6-orcin with de-t-butylation to 2,6-diamino-4-4-tert-butyltoluene vitriol; Wherein, temperature of reaction is 220 DEG C; The weight ratio of solid super-strong acid and 2,6-diamino-4-4-tert-butyltoluene vitriol is 0.53: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310505791.9A CN103508850B (en) | 2013-10-24 | 2013-10-24 | Preparation method for 2,6-dihydroxytoluene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310505791.9A CN103508850B (en) | 2013-10-24 | 2013-10-24 | Preparation method for 2,6-dihydroxytoluene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103508850A CN103508850A (en) | 2014-01-15 |
| CN103508850B true CN103508850B (en) | 2015-05-13 |
Family
ID=49892338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310505791.9A Active CN103508850B (en) | 2013-10-24 | 2013-10-24 | Preparation method for 2,6-dihydroxytoluene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103508850B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152870A (en) * | 2015-08-27 | 2015-12-16 | 河南黑马动物药业有限公司 | Method for preparing pyroline by means of water re-crystallization |
| CN107473943A (en) * | 2017-08-22 | 2017-12-15 | 江苏鼎烨药业有限公司 | A kind of preparation method of 2,6 orcin |
| CN114315526A (en) * | 2020-09-27 | 2022-04-12 | 中石化南京化工研究院有限公司 | Preparation method of resorcinol |
| CN113698276B (en) * | 2021-09-01 | 2023-10-03 | 南京杰运医药科技有限公司 | Synthesis method of 2, 6-dihydroxytoluene |
| CN115784846B (en) * | 2022-11-28 | 2024-01-16 | 安徽英特美科技有限公司 | Preparation method of 2,6-dihydroxytoluene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245010A (en) * | 2008-03-08 | 2008-08-20 | 西北师范大学 | Method for producing civil dinitrotoluene |
-
2013
- 2013-10-24 CN CN201310505791.9A patent/CN103508850B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245010A (en) * | 2008-03-08 | 2008-08-20 | 西北师范大学 | Method for producing civil dinitrotoluene |
Non-Patent Citations (1)
| Title |
|---|
| 2,6-二羟基甲苯合成工艺研究;杜彬斌;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20100915(第9期);第6页1.2.5部分；第12页第2段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103508850A (en) | 2014-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103508850B (en) | Preparation method for 2,6-dihydroxytoluene | |
| CN107746380A (en) | A kind of industrialized preparing process of the acetyl-anisidine of 2 amino 4 | |
| CN103012074B (en) | Prepare the method for aromatic methyl ether compound | |
| CN109336769A (en) | A kind of preparation method of p-phenylenediamine | |
| CN101591224A (en) | A kind of method for preparing the 2-tertiary butyl-4-methylphenol | |
| CN103508908B (en) | Preparation method for 4-amino-3-methylphenol | |
| CN104557640A (en) | Method for preparing 2-nitro-4-methylsulfuryl benzoic acid by molecular oxygen catalytic oxidation | |
| CN102336633B (en) | Preparation method of 2,4-dicumyl phenol | |
| CN103508881B (en) | Alkyl salicylic acid synthesis method | |
| CN113024385B (en) | Preparation method of 2,2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl | |
| CN104177447B (en) | A kind of method that phenols chemicals is prepared in carbon-based solid acid Catalytic lignin degraded | |
| CN108358783B (en) | 3-substituted glutaric diester and preparation method of glutaconic diester | |
| CN102603547B (en) | New synthesis process of 1-amino-2-acetylanthraquinone and derivatives thereof | |
| CN103193660B (en) | Synthetic method of 4-alkoxy phenylamine compound | |
| CN101747156A (en) | New method for preparing 2,4-ditert-pentyl-phenol | |
| CN107935837A (en) | A kind of method of metacresol catalysis oxidation synthesis m-hydroxybenzoic acid | |
| CN106631991B (en) | Simple synthesis method of N-butyl-2, 2,6, 6-tetramethyl-4-piperidylamine | |
| CN103787908A (en) | Preparation method of para aminoacet anilide | |
| CN205635425U (en) | Hydrolysis production system of p toluidine preparation paracresol of catalysis | |
| CN103086898A (en) | Preparation method of diphenylamine or ring-substituted derivative thereof | |
| CN106631651A (en) | Preparation method of benzyl methylbenzene | |
| CN104529790A (en) | Method for coproducing menthane diamine and pseudothiohydantoin | |
| CN106866378B (en) | Synthetic process of phloroglucinol | |
| CN105418358A (en) | Method for preparing o-chlorotoluene | |
| CN101811945B (en) | Process for preparing alkyl diphenyl ether from fatty alcohol and diphenyl ether |
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 | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 311228 Linjiang Industrial Park, Xiaoshan District, Zhejiang, Hangzhou Patentee after: Zhejiang DINGLONG Technology Co.,Ltd. Address before: 311228 Linjiang Industrial Park, Xiaoshan District, Zhejiang, Hangzhou Patentee before: ZHEJIANG DINGLONG TECHNOLOGY Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |