CN1931852A - Prepn process of polyalkyl hydroxyl benzodihydro pyran derivative - Google Patents
Prepn process of polyalkyl hydroxyl benzodihydro pyran derivative Download PDFInfo
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- CN1931852A CN1931852A CNA2006101136930A CN200610113693A CN1931852A CN 1931852 A CN1931852 A CN 1931852A CN A2006101136930 A CNA2006101136930 A CN A2006101136930A CN 200610113693 A CN200610113693 A CN 200610113693A CN 1931852 A CN1931852 A CN 1931852A
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Abstract
The preparation process of polyalkyl hydroxyl benzodihydro pyran derivative belongs to the field of organic compound preparing technology. Meta-polyhydric phenol is first dissolved in mixed solvent of ethanol and water in the weight ratio of 1to 5 and in the amount of 80-200 wt% of the meta-polyhydric phenol, ketone in the molar ratio to the meta-polyhydric phenol of 0.25 to 1 and acid as the catalyst and in the molar ratio to the meta-polyhydric phenol of 1/3 to 2/3 are then added to react at 30-60 deg.c for 5-12 hr, and through further water washing and decompression drying, polyalkyl hydroxyl benzodihydro pyran derivative is obtained. The preparation process has the advantages of high efficiency, high yield, high product purity, less pollution, etc.
Description
Affiliated field
The invention belongs to the organic compound preparation field, particularly the preparation of many alkyl hydroxies chroman derivatives.
Background technology
In 1997, P.Livant etc. adopt in the literature several different methods studies have shown that the reaction of Resorcinol and acetone product structure (referring to P.Livant, T.R.Webb, Weizheng Xu.Reaction of Resorcinolwith Acetone[J] .J.Org.Chem., 1997,62:737～742), think primary product that both react be 4-(3,3-dihydro-7-hydroxyl-2,4,4-trimethylammonium-2H-1-chromene-2-yl)-1, the 3-dihydroxy-benzene, structure is as follows:
This three-functionality-degree phenol generally is used to make agricultural chemicals, such as sterilant, remove the mite agent, remove Fungicide etc., because structurally belong to the polyhydroxy fragrant compound, and can also be as epoxy curing agent, or be used for organic synthesis as raw material.
The most common preparation method of such polyphenol is to be raw material with Resorcinol and acetone, and tetrahydrofuran (THF), methylene dichloride, ether, benzene, toluene etc. are solvent, react under the effect of acid catalyst.P.Livant etc. adopt methylene dichloride-ether mixed solvent, make catalyzer with 10% dilute hydrochloric acid and synthesize; But this method poor operability, the solvent toxicity of use is big, and is seriously polluted, the production cost height.Pieter etc. disclose a kind of preparation method in U.S. Pat 2947760, water is cooked solvent in the method, with strong inorganic acid (example hydrochloric acid, sulfuric acid, phosphoric acid) catalysis, generate the product overall yield and reach as high as 93%, but the reaction times of this method is relatively grown (48 hours).
Summary of the invention
The object of the present invention is to provide the preparation method that a kind of productive rate height, purity height, reaction efficiency height, technology are simple, workable, pollute little many alkyl hydroxies chroman derivatives.
The inventive method is as follows: a position polyphenol dissolves in ethanol/water mixed solvent between inciting somebody to action, the weight ratio of second alcohol and water is 5: 1～1: 1, preferred 7: 2～2: 1, described solvent load be between position polyphenol weight 80～200%, preferred 100～180%, add ketone and the acid of making catalyzer again, between the position polyphenol with acid mol ratio be 3: 1～3: 2, between the mol ratio of position polyphenol and ketone be 4: 1～1: 1, at 30～60 ℃, preferred 40～50 ℃, 5～12 hours reaction times, preferred 7～11 hours, afterwards through washing, the decompression oven dry, obtain the many alkyl hydroxies chroman derivatives shown in structural formula (I), wherein R is lower paraffin hydrocarbons or the naphthenic hydrocarbon that contains 1～4 carbon, and the value of n is 0～1.
Aforesaid position polyphenol is Resorcinol or Phloroglucinol.
Aforesaid ketone is meant acetone, butanone, isopropylideneacetone or pimelinketone.
Aforesaid acid is meant hydrochloric acid, heteropolyacid or sulfuric acid.
Leach and contain a large amount of phenol and acid in the solvent, can add ketone in proportion and continue prepared in reaction polyfunctionality phenol.
Use method of the present invention, single step reaction obtains the finished product, and the product once through yield reaches 90～99%, and purity is higher than 92%, and reaction efficiency is very high, and the reaction times was much smaller than 48 hours of prior art.Owing in reaction process, use ethanol/water solution to make solvent, pollute little.
Embodiment
In order to further describe the present invention, provide following preferred embodiment, but specific implementation is not limited to these embodiment.
Embodiment 1:
With 330 parts of Resorcinols and 58 parts of acetone, 152 parts of concentration is that (mol ratio of phenol, ketone, acid is: phenol: ketone: acid=3: 1: 1.5) for 36% hydrochloric acid, 490 parts of dehydrated alcohol/water mixture (weight ratio of second alcohol and water is 2: 1) are at 40～50 ℃ of reactions, reaction times 7h.Product yield 96%, purity 94%, molecular weight distribution about 1.03.
Embodiment 2:
With 330 parts of Resorcinols and 116 parts of acetone, 152 parts of concentration is that (mol ratio of phenol, ketone, acid is: phenol: ketone: acid=3: 2: 1.5) for 36% hydrochloric acid, 490 parts of dehydrated alcohol/water mixture (weight ratio of second alcohol and water is 2: 1) are at 40～50 ℃ of reactions, reaction times 8h.Product yield 98%, purity 92%, molecular weight distribution about 1.03.
Embodiment 3:
With 220 parts of Resorcinols and 58 parts of acetone, 182 parts of concentration is that (mol ratio of phenol, ketone, acid is: phenol: ketone: acid=2: 1: 1) for 20% hydrochloric acid, 330 parts of dehydrated alcohol/water mixture (weight ratio of second alcohol and water is 2: 1) are at 40～50 ℃ of reactions, reaction times 9h.Product yield 92%, purity 92%, molecular weight distribution about 1.03.
Embodiment 4:
With 440 parts of Resorcinols and 98 parts of isopropylideneacetones, 132 parts of concentration is that (mol ratio of phenol, ketone, acid is: phenol: ketone: acid=4: 1: 1.4) for 36% hydrochloric acid, 750 parts of dehydrated alcohol/water mixture (weight ratio of second alcohol and water is 3: 1) are at 40～50 ℃ of reactions, reaction times 8h.Product yield 97%, purity 94%, molecular weight distribution about 1.03.
Embodiment 5:
With 330 parts of Resorcinols and 98 parts of isopropylideneacetones, 121 parts of concentration is that (mol ratio of phenol, ketone, acid is: phenol: ketone: acid=3: 1: 1) for 30% hydrochloric acid, 550 parts of dehydrated alcohol/water mixture (weight ratio of second alcohol and water is 7: 2) are at 40～50 ℃ of reactions, reaction times 9h.Product yield 98%, purity 92%, molecular weight distribution about 1.03.
Embodiment 6:
With 330 parts of Resorcinols and 58 parts of acetone, 102 parts of concentration is that (mol ratio of phenol, ketone, acid is: phenol: ketone: acid=3: 1: 1) for 96% sulfuric acid, 490 parts of dehydrated alcohol/water mixture (weight ratio of second alcohol and water is 2: 1) are at 40～50 ℃ of reactions, reaction times 9h.Product yield 94%, purity 94%, molecular weight distribution about 1.02.
Embodiment 7:
With 330 parts of Resorcinols and 116 parts of acetone, 102 concentration are 96% sulfuric acid (mol ratio of phenol, ketone, acid is: phenol: ketone: sour=3: 2: 1), 490 parts of dehydrated alcohol/water mixture (weight ratio of second alcohol and water is 2: 1) are at 40～50 ℃ of reactions, reaction times 8h.Product yield 97%, purity 93%, molecular weight distribution about 1.02.
Embodiment 8:
With 220 parts of Resorcinols and 58 parts of acetone, 98 parts of concentration is that (mol ratio of phenol, ketone, acid is: phenol: ketone: acid=2: 1: 0.7) for 60% sulfuric acid, 330 parts of dehydrated alcohol/water mixture (weight ratio of second alcohol and water is 2: 1) are at 40～50 ℃ of reactions, reaction times 8h.Product yield 94%, purity 93%, molecular weight distribution about 1.02.
Embodiment 9:
With 440 parts of Resorcinols and 98 parts of isopropylideneacetones, 160 parts of concentration is that (mol ratio of phenol, ketone, acid is: phenol: ketone: acid=4: 1: 1.4) for 80% sulfuric acid, 760 parts of dehydrated alcohol/water mixture (weight ratio of second alcohol and water is 3: 1) are at 40～50 ℃ of reactions, reaction times 10h.Product yield 96%, purity 93%, molecular weight distribution about 1.02.
Embodiment 10:
With 330 parts of Resorcinols and 98 parts of isopropylideneacetones, 245 parts of concentration is that (mol ratio of phenol, ketone, acid is: phenol: ketone: acid=3: 1: 1) for 40% sulfuric acid, 560 parts of dehydrated alcohol/water mixture (weight ratio of second alcohol and water is 7: 2) are at 40～50 ℃ of reactions, reaction times 11h.Product yield 98%, purity 92%, molecular weight distribution about 1.02.
Can find out that from above embodiment method of the present invention has realized goal of the invention fully.
Claims (8)
1. the preparation method of alkyl hydroxy chroman derivatives more than a kind, it is characterized in that: a position polyphenol dissolves in ethanol/water mixed solvent between inciting somebody to action, the weight ratio of second alcohol and water is 5: 1～1: 1, described solvent load be between position polyphenol weight 80～200%, add ketone and the acid of making catalyzer again, between the position polyphenol with acid mol ratio be 3: 1～3: 2, between the mol ratio of position polyphenol and ketone be 4: 1～1: 1, at 30～60 ℃, 5～12 hours reaction times, afterwards through washing, the decompression oven dry, obtain the many alkyl hydroxies chroman derivatives shown in structural formula (I), wherein R is lower paraffin hydrocarbons or the naphthenic hydrocarbon that contains 1～4 carbon, and the value of n is 0～1.
2. preparation method according to claim 1 is characterized in that: described position polyphenol is Resorcinol or Phloroglucinol.
3. preparation method according to claim 1 and 2 is characterized in that: the weight ratio of second alcohol and water is 7: 2～2: 1.
4. according to the described preparation method of claim 1～3, it is characterized in that: described solvent load be between position polyphenol weight 100～180%.
5. according to the described preparation method of claim 1～4, it is characterized in that: described ketone is acetone, butanone, isopropylideneacetone or pimelinketone.
6. according to the described preparation method of claim 1～5, it is characterized in that: described acid is hydrochloric acid, heteropolyacid or sulfuric acid.
7. according to the described preparation method of claim 1～6, it is characterized in that: the reaction times is 7～11 hours.
8. according to the described preparation method of claim 1～7, it is characterized in that: temperature of reaction is 40～50 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9868683B2 (en) | 2013-06-13 | 2018-01-16 | Empire Technology Development Llc | Multi-functional phenolic resins |
| US9890130B2 (en) | 2013-02-15 | 2018-02-13 | Empire Technology Development Llc | Phenolic epoxy compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE557525A (en) * | 1956-05-17 | |||
| JPS565476A (en) * | 1979-06-27 | 1981-01-20 | Mitsui Petrochem Ind Ltd | Polyalkyl-2- 2,4-dihydroxyphenyl -7-hydroxychroman and its preparation |
| JPH0231073B2 (en) * | 1984-07-18 | 1990-07-11 | Mitsui Petrochemical Ind | OKISHIFURABANKAGOBUTSUNOSEIZOHO |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9890130B2 (en) | 2013-02-15 | 2018-02-13 | Empire Technology Development Llc | Phenolic epoxy compounds |
| US9868683B2 (en) | 2013-06-13 | 2018-01-16 | Empire Technology Development Llc | Multi-functional phenolic resins |
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