CN103562169B - The purification process of p-methylallyl pyrocatechol - Google Patents
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- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
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- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
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- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
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Abstract
The present invention relates to the method for purifying p-methylallyl pyrocatechol and prepared the method for spices and perfume compound by p-methylallyl pyrocatechol.
Description
Invention field
The present invention relates to the purification process of p-methylallyl pyrocatechol and prepared the method for spices and perfume compound by p-methylallyl pyrocatechol.
Background of invention
In preparation 2,3-dihydro-2,2-dimethyl-7-hydroxyl benzofuran (a kind of sterilant/nematocides---the intermediate of carbofuran) based in the method for pyrocatechol, pyrocatechol and methylallyl chloride react and produce 2-methyl allyloxyphenol and o-methylallyl pyrocatechol.Phenol/pyrocatechol mixture generation thermal rearrangement reaction also cyclisation forms 2,3-dihydro-2,2-dimethyl-7-hydroxyl benzofuran.The by product that this thermal rearrangement and cyclization process produce is p-methylallyl pyrocatechol, weight percent is about 25-30%, and it cyclisation can not form 2,3-dihydro-2,2-dimethyl-7-hydroxyl benzofuran, is dropped as waste material because not having commercial value.Preferably can find out and a kind ofly the business method of purifying is carried out to the p-methylallyl pyrocatechol from retort and uses it to prepare useful product.
Summary of the invention
The invention provides the application as the intermediate of some spices and perfume compound of the purification process of p-methylallyl pyrocatechol and p-methylallyl pyrocatechol.
Detailed Description Of The Invention
The invention provides the application as the intermediate of some spices and perfume compound of the purification process of p-methylallyl pyrocatechol and p-methylallyl pyrocatechol.
In preparation 2,3-dihydro-2,2-dimethyl-7-hydroxyl benzofuran (a kind of sterilant/nematocides---the intermediate of carbofuran) based in the method for pyrocatechol, pyrocatechol and methylallyl chloride react and produce 2-methyl allyloxyphenol (MOP) and o-methylallyl pyrocatechol (3-MAC), as shown in following step 1.Phenol/pyrocatechol mixture generation claisen (Clasien) thermal rearrangement cyclisation form 2,3-dihydro-2,2-dimethyl-7-hydroxyl benzofuran (7-hydroxyl), as shown in following step 2.The by product that this thermal rearrangement and cyclization process produce is p-methylallyl pyrocatechol (4-MAC), weight percent is about 25-30%, and it cyclisation can not form 2,3-dihydro-2,2-dimethyl-7-hydroxyl benzofuran, is dropped as waste material because not having commercial value.In step 2, the aluminum isopropylate of MOP, 3-MAC, dimethylbenzene and catalytic amount is placed in autoclave.By mixture heating about 4 hours, then cool autoclave, with aqueous sodium persulfate solution dilution and the stirred reaction mixture of 2%.Make demixing, take out organic phase.Underpressure distillation, to remove the dimethylbenzene in organic phase, leaves oiliness residue.Residue is distilled, collects the cut under 2.5-3 mmhg, 99 DEG C of-100 DEG C of conditions, i.e. 7-hydroxyl.Remaining residue (crude product 4-MAC) is usually used as waste disposal.
Step 1:
Step 2:
A kind of method being separated p-methylallyl pyrocatechol from remaining tarry residue after 7-hydroxyl removed by reaction mixture of present discovery.
The method of the p-methylallyl pyrocatechol of purifying of the present invention comprises:
A) residue that 2-methyl allyloxyphenol and o-methylallyl pyrocatechol generation claisen (Claisen) are reset and cyclisation obtains is heated, then removal 2 is distilled at reduced pressure conditions, 3-dihydro-2,2-dimethyl-7-hydroxyl benzofuran;
B) overhead product of under 1.2-1.5 mmhg pressure 110-120 DEG C is collected;
C) at elevated temperatures overhead product is dissolved in heptane;
D) cooling solution, makes the crystallization of p-methylallyl pyrocatechol;
E) the p-methylallyl pyrocatechol of collecting by filtration; With
F) dry p-methylallyl pyrocatechol.
The purity of the p-methylallyl pyrocatechol that the inventive method obtains is at least 95%.
In another embodiment, the invention provides the method using p-methylallyl pyrocatechol as some spices of Intermediate Preparation and perfume compound.
Piperonylaldehyde is being commonly called as of 1,3-benzodioxole-5-formaldehyde, is a kind ofly to have the aromatic aldehyde being usually described as the fragrance of a flower being similar to Vanillin and cherry.Use in spices and perfume.As illustrated in scheme 1 below, p-methylallyl pyrocatechol can be used as raw material to prepare piperonylaldehyde.
Scheme 1:
Steps A
Step B
step C
In scheme 1, steps A, in the presence of base, 4-MAC and methylene dichloride react in a solvent and produce 5-(2-methyl-2-propylene-1-base)-1,3-benzodioxole, compound 1.In this step, alkali can be water-based or non-water oxyhydroxide, such as potassium hydroxide or sodium hydroxide, or organic bases, such as 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene.Solvent can be methyl-sulphoxide, triethylamine, alcohol if butanols, Isosorbide-5-Nitrae-diox, water or ether are as two (2-methoxy ethyl) ether, depend on alkali used.
In stepb, under the existence of glycol, heating compound 1 and alkali, form 5-(2-methyl-1-propylene-1-base)-1,3-benzodioxole, compound 2.In this step, alkali is preferably oxyhydroxide, such as potassium hydroxide.Preferably, glycol is polyoxyethylene glycol (PEG300), for catalytic cpd 1, isomerization occurs and forms compound 2.Solvent can be there is as water or alcohol, such as, can propyl carbinol be used.
In step C, under the existence of acid-soluble dose, compound 2 is oxidized and produces piperonylaldehyde.Preferably, oxygenant is potassiumchromate, and acid-soluble dose is sulfuric acid.
The another kind application of p-methylallyl pyrocatechol is the raw material as helional, helional is Alpha-Methyl-1, the popular name of 3-benzodioxole-5-propionic aldehyde, helional has the fragrance of a flower being usually described as similar new mown hay and the aromatic aldehyde used in perfume.Scheme 2 describes the method preparing helional.
Scheme 2:
Steps A
Step B
In scheme 2, steps A, prepares 3-(1,3-benzodioxole-5-base-methyl)-3-methyl-2-oxyethane, compound 3 with oxidizer treatment compound 1 in a solvent.Oxygenant is preferably 3-chlorine peroxybenzoic acid, and preferred solvent is methylene dichloride.
In stepb, agitate compounds 3 and catalyzer in a solvent, produces helional.Preferred catalyst/solvent combination is zinc chloride/Isosorbide-5-Nitrae-diox; Boron trifluoride diethyl etherate/Isosorbide-5-Nitrae-diox; Tetrafluoroboric acid copper (II)/methylene dichloride; Indium chloride (III)/tetrahydrofuran (THF); With 1,1,1-trifluoromethayl sulfonic acid bismuth (III)/methylene dichloride.
In addition, p-methylallyl pyrocatechol is used can to prepare other spices and perfume compound as raw material.This comprises rancinamycin IV, rancinamycin IV is 3, the popular name of 4-Dihydroxy benzaldehyde, it is a kind of phenolic aldehyde, a kind of compound be discharged into by cork stopper in grape wine, can be used as the precursor synthesizing following material: Vanillin (3-methoxy-4-hydroxybenzaldehyde), vanillal (4-hydroxyl-3-ethoxy-benzaldehyde), veratryl aldehyde (3,4-dimethoxy benzaldehyde), veratryl alcohol (3,4-dimethoxy-benzyl alcohol) and veratric acid (3,4-dimethoxybenzoic acid).P-methylallyl pyrocatechol also can be used for preparing some drugs as raw material, such as suprarenin, Dopamine HCL and L-DOPA.
Unless be otherwise noted in embodiment, envrionment temperature represents the temperature of about 15-20 DEG C.Following examples are only used to set forth the present invention, and should not be construed as restrictive, because the further improvement of described invention is apparent to those skilled in the art.Think that all these improve to drop in scope of the present invention that claims limit.
Embodiment 1
Present embodiment describes the method for preparation and the p-methylallyl pyrocatechol of purifying
Steps A
90.0 grams of pyrocatechols, 38.4 grams of salt of wormwood, 79.1 grams of methylallyl chlorides and methyl iso-butyl ketone (MIBK) of 319.0 grams of 1:1 and the mixture of water are added in 1000 milliliters of stainless steel autoclaves.Reactor sealing is also heated to 130 DEG C while stirring.After 2 hours, reactor is cooled to envrionment temperature.Reactor is vented, and opens, and is poured in 1000 ml flasks by content.While stirring, the aqueous sodium persulfate solution (140.0 grams) of 2% is added in flask.Mixture is heated to 70 DEG C, with dilute hydrochloric acid, the pH value of mixture is adjusted to 3-4.After 30 minutes, stop stirring, each phase layering.Be separated organic phase, with the aqueous sodium persulfate solution dilution of 215.0 gram 2%, mixture carries out component distillation to remove the material distilled at 140 mmhg, 40-48 DEG C.Add in retort residue by dimethylbenzene (250 grams), mixture stirs 30 minutes at the temperature of 30-40 DEG C.Stop stirring, be respectively separated.Take out organic phase, with dimethylbenzene dilution until gross weight is 387 grams.The organic phase aqueous sodium persulfate solution of 2% extracts four times, at every turn with 118.3 grams of aqueous sodium persulfate solutions.Remaining water is removed by component distillation under the pressure of 55 mmhg, leaves the xylene solution that 338 grams comprise 2-methyl allyloxyphenol (MOP) and o-methylallyl pyrocatechol (3-MAC).
Step B
MOP and 3-MAC mixture and 0.34 gram of aluminum isopropylate that 338 grams of dimethylbenzene, steps A obtain is added in 1000 milliliters of stainless steel autoclaves.Reactor sealing is also heated to 180 DEG C while stirring.After about 4 hours, reactor is made to be cooled to envrionment temperature with water coolant.Reactor is vented, and opens, and is poured in 1000 ml flasks by content.The organic mixture aqueous sodium persulfate solution of 2% extracts three times, each aqueous sodium persulfate solution using 118.3 gram 2%.Added by trioctylphosphine amine (0.34 gram) in the organic mixture of washing, dimethylbenzene is removed in underpressure distillation, leaves residue.Residue carries out scraped film type distillation, collects the overhead product (7-hydroxyl) under 1 mmhg, 99-100 DEG C condition.Residue carries out fractionation, collects the overhead product (7-hydroxyl) under 1 mmhg, 99-100 DEG C condition.The retort residue that scraped film type distillation and fractionation obtain is for step C.
Step C
The retort residue prepared 7-hydroxyl and obtain is operated, totally 1450 grams by carrying out several times according to above steps A and B.This material is placed in 3 liters of round-bottomed flasks, carries out vacuum distilling, collect the cut of under 1.2-1.5 mmhg pressure 110-120 DEG C.751 grams of overhead products, comprise the p-methylallyl pyrocatechol of 60.2 % by weight.A part of overhead product (250 grams) is placed in the three neck round-bottomed flasks of 3 liters being equipped with high-performance mechanical agitator and thermometer, adds 2500 milliliters of skellysolve Ds wherein.The temperature of the mixture stirred is increased to 55 DEG C, forms settled solution.This solution is cooled to envrionment temperature, stir about 18 hours.Form solid, solid collected by filtration.Filter cake 300 milliliters of skellysolve D drip washing, then drying under reduced pressure, obtain the p-methylallyl pyrocatechol of 116 grams of pale solid forms, fusing point 63-65 DEG C, and gas-chromatography area percent shows that purity is 96.3%.Mass spectroscopy: 164 (M
+), 149 (M
+,-methyl), 123 (M
+-CH (CH
3)=CH
2).HNMR(CDCl3，300MHz)：1.63(s，CH
3，3H)，3.17(S，CH
2，2H)，4.69(s，=CH
2，1H)，4.77(s，=CH
2，1H)，5.59(s，OH，2H)，6.59～6.78(m，Ph，3H)。
IR(KBr)：3253，1618，1604，1518，1446，1369，1349，1280，1259，1212，1187，1109，950，901。
Embodiment 2
Piperonylaldehyde is prepared by p-methylallyl pyrocatechol
Steps A: preparation 5-(2-methyl-2-propylene-1-base)-1,3-benzodioxole
16 grams of solid potassium hydroxide, 215 grams of methyl-sulphoxides and 15 grams of water are added in the three neck round-bottomed flasks being equipped with 1 of stirrer, thermometer, dropping funnel and condenser liter.Mixture is stirred and is heated to 92 DEG C.Slowly add the solution of 20 grams of p-methylallyl pyrocatechols in 25 grams of methyl-sulphoxides and 30 grams of methylene dichloride, after having added, mixture is stirred 3 hours at 95 DEG C.Mixture cools and uses 500 grams of water dilutions.With dichloromethane extraction mixture three times, use 100 grams of methylene dichloride at every turn.Merge extract, with the aqueous sodium hydroxide solution washing of 100 gram 1%, then wash three times with water, each use 25 grams of water.Extract through washing also uses silica gel chromatography through concentrating under reduced pressure, obtains 21 grams of oily 5-(2-methyl-2-propylene-1-base)-1,3-benzodioxole.NMR is consistent with described structure.HNMR(CDCl
3，300MHz)：1.66(s，CH3，3H)，3.22(s，CH2，2H)，4.73～4.79(d，CH2，2H)，5.92(s，CH2，2H)，6.61～6.74(m，Ph，3H)。
Step B: preparation 5-(2-methyl-1-propylene-1-base)-1,3-benzodioxole
The mixture of 35 grams of 5-(2-methyl-2-propylene-1-base)-1,3-benzodioxole, 3.5 grams of potassium hydroxide and 3.5 grams of polyoxyethylene glycol (PEG300) is heated to 120 DEG C under agitation and keeps 2.5 hours.Mixture underpressure distillation, collects the cut under 2.0 mmhg pressures, 90 DEG C of conditions, purifying on silica gel column chromatography, obtains 30 grams of oily 5-(2-methyl-1-propylene-1-base)-1,3-benzodioxole.NMR is consistent with described structure.HNMR(CDCl
3，300MHz)：1.83(s，CH3，3H)，1.87(s，CH3，3H)，5.92(s，CH2，2H)，6.17(s，CH，1H)，6.62～6.78(m，Ph，3H)。Gas chromatographic analysis (area %) shows that purity is 90%.
Step C: prepare piperonylaldehyde
Under agitation, in the mixture of 3.8 grams of 5-(2-methyl-1-propylene-1-base)-1,3-benzodioxole, 18.0 grams of sulfuric acid and 1.0 grams of ammonium sulfate, add 6.0 grams of potassiumchromates in batches, maintain temperature of reaction lower than 60 DEG C simultaneously.After having added, mixture is stirred 1 hour at 45 DEG C, adds 1.0 grams of potassiumchromates.Mixture stirs 40 minutes at 45 DEG C, cooling, with 100 ml water dilutions.Mixture 50 milliliters of dichloromethane extractions.Organic extract washes with water, then concentrating under reduced pressure, obtains 0.5 gram of oily matter.Carry out gas chromatographic analysis to oily matter to show to comprise 65 % by weight piperonylaldehydes and 15 % by weight 5-(2-methyl-1-propylene-1-base)-1,3-benzodioxole.GC-MS analyzes and the display of main peak analytical results, and EI-MS ((M-1) 149,121,91,63) is consistent with piperonylaldehyde standard diagram.Other impurity peaks display EI – MS (M176) is 5-(2-methyl-1-propylene-1-base)-1,3-benzodioxole.
Find, to 5-(2-methyl-2-propylene-1-base)-1, adding a small amount of polyoxyethylene glycol (PEG300 or PEG800) or polyethylene glycol monomethyl ether (PEG300DM) in the reaction mixture of 3-benzodioxole, (2-propylene isomer) and alkali can isoversion reaction, form 5-(2-methyl-1-propylene-1-base)-1,3-benzodioxole, (1-propylene isomer).When adding glycol, this reaction is carried out faster.Following table 1 summarizes containing glycol with not containing the experimental result of glycol, and wherein area % is the gas-chromatography area % of the reaction mixture sample obtained in the shown time.
Table 1
The isomerization of 2-propylene isomer forms 1-propylene isomer
* contrast the continuation of 1 experiment, 170 DEG C kept after 4 hours, and temperature of reaction is reduced to 130 DEG C, adds 0.3 gram of PEG-300.
The continuation of * 2A, after 2 hours, adds 0.2 gram of PEG-300DM.
From the data of table 1, slowly can form 1-propylene isomer with alkaline purification 2-propylene isomer, but add glycol, after especially adding PEG-300, speed of response significantly improves.
Embodiment 3
Helional is prepared by p-methylallyl pyrocatechol
Steps A: preparation 3-(1,3-benzodioxole-5-base-methyl)-3-methyl-2-oxyethane
Under the condition stirred, to 9.0 grams of 5-(2-methyl-2-propylene-1-base)-1,3-benzodioxole (embodiment 2, prepared by steps A) add 12.0 grams of m-chlorine peroxybenzoic acid in solution in 100 grams of methylene dichloride in batches, maintain temperature of reaction simultaneously and be about 35 DEG C.After having added, mixture stirs 2 hours at 35 DEG C.Reaction mixture filters, filter cake 10 milliliters of eluent methylene chlorides.The filtrate merged, with the aqueous sodium persulfate solution extraction of two parts each 100 grams 5%, then extracts with two parts of each water of 50 milliliters.Organic phase concentrating under reduced pressure, residue silica gel chromatography, obtains 9.0 grams of oily 3-(1,3-benzodioxole-5-base-methyl)-3-methyl-2-oxyethane.HNMR(CDCl
3，300MHz)：1.27(s，CH3，3H)，2.60～2.65(m，CH2，2H)，2.72～2.83(m，CH2，2H)，5.94(s，CH2，2H)，6.64～6.76(m，Ph，3H)。
Step B: prepare helional
The mixture of 1.0 grams of 3-(1,3-benzodioxole-5-base-methyl)-3-methyl-2-oxyethane, 0.004 gram of 1,1,1-Bismuth triflate (III) and 10 grams of methylene dichloride is stirred 2 hours at 20-25 DEG C.Reaction mixture water extracting twice.Organic phase, by gas chromatographic analysis, shows to comprise the methylene dichloride of 48% and the helional of 45%.Organic phase reduction vaporization, residue, by purification by column chromatography, obtains oily helional, HNMR (CDCl
3, 300MHz): 1.07 ~ 1.10 (d, CH3,3H), 2.50 ~ 2.65 (m, CH2,2H), 2.97 ~ 3.03 (m, CH, 1H), 5.93 (s, CH2,2H), 6.60 ~ 6.75 (m, Ph, 3H), 9.70 (s, CHO, 1H);
CNMR(CDCl
3，300MHz)：204.3，147.7，146.1，132.4，121.9，109.3，108.2，100.9，48.2，36.4，13.1)。
Although emphasize that preferred implementation describes the present invention, it will be understood by those skilled in the art that can use the variant of preferred equipment and method and the present invention can specifically describe herein outside mode implement.Therefore, present invention resides in changing of containing in spirit and scope that appended claims limits.
Claims (3)
1. prepared the method for helional by 5-(2-methyl-2-propylene-1-base)-1,3-benzodioxole for one kind, the method comprises:
A) with oxidizing 5-(2-methyl-2-propylene-1-base)-1,3-benzodioxole to form 3-(1,3-benzodioxole-5-base-methyl)-3-methyl-2-oxyethane;
B) use catalyst treatment 3-(1,3-benzodioxole-5-base-methyl)-3-methyl-2-oxyethane to form helional.
2. the method for claim 1, it is characterized in that, described oxygenant is m-chlorine peroxybenzoic acid, and described catalyzer is selected from zinc chloride, boron trifluoride, indium chloride (III), 1,1,1-Bismuth triflate (III) and Tetrafluoroboric acid copper (II).
3. compound 3-(1,3-benzodioxole-5-base-methyl)-3-methyl-2-oxyethane.
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| PCT/US2012/041032 WO2012173842A2 (en) | 2011-06-13 | 2012-06-06 | Purification process for para-methallylpyrocatechol |
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|---|---|---|---|---|
| US3008968A (en) * | 1958-02-11 | 1961-11-14 | Int Flavors & Fragrances Inc | Process for making 2-methyl-3-(3'-4'-methylenedioxyphenyl)-propanal |
| FR2470768A1 (en) * | 1979-12-07 | 1981-06-12 | Rhone Poulenc Agrochimie | PROCESS FOR THE PREPARATION OF BENZOFURAN DERIVATIVES |
| US4380654A (en) * | 1982-02-18 | 1983-04-19 | Fmc Corporation | Process for preparation of 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran |
| PH26101A (en) * | 1987-03-04 | 1992-02-06 | Eisai Co Ltd | Benzodioxole derivatives |
| CN1024098C (en) * | 1988-06-15 | 1994-03-30 | 北京燕山石油化工公司京蒸化工技术开发公司 | Process of para-tertiary butyl catechol recovery |
-
2012
- 2012-06-06 CN CN201280010957.3A patent/CN103562169B/en not_active Expired - Fee Related
- 2012-06-06 WO PCT/US2012/041032 patent/WO2012173842A2/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012173842A2 (en) | 2012-12-20 |
| WO2012173842A3 (en) | 2013-02-28 |
| CN103562169A (en) | 2014-02-05 |
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