CN102417455A - Batch preparation method of 3,5-heptandiol dibenzoate - Google Patents
Batch preparation method of 3,5-heptandiol dibenzoate Download PDFInfo
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- CN102417455A CN102417455A CN2010102946109A CN201010294610A CN102417455A CN 102417455 A CN102417455 A CN 102417455A CN 2010102946109 A CN2010102946109 A CN 2010102946109A CN 201010294610 A CN201010294610 A CN 201010294610A CN 102417455 A CN102417455 A CN 102417455A
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Abstract
The invention discloses a batch preparation method of 3,5-heptandiol dibenzoate. The 3,5-heptandiol dibenzoate is 4-substituted 3,5-heptandiol dibenzoate or unsubstituted 3,5-heptandiol dibenzoate. The batch preparation method of the 3,5-heptandiol dibenzoate comprises the following steps that 1, in the presence of a solvent and a basic catalyst, ethyl propanoate and butanone undergo an acylation reaction to produce 3,5-heptanedione, and specially, after the acylation reaction is finished, the 3,5-heptanedione is processed into a 3,5-heptanedione product by a chelating purification method, 2, in the presence of a solvent and a basic catalyst, the 3,5-heptanedione product contacts and undergoes a 4-substitution reaction with a reagent to produce 4-substituted 3,5-heptanedione, and 3, in the presence of a solvent and a basic catalyst, the 4-substituted 3,5-heptanedione or unsubstituted 3,5-heptanedione is reduced into 3,5-heptandiol by a reducing agent under alkaline conditions, and 4, in the presence of a solvent, the reduced 3,5-heptandiol reacts with a carbonyl-containing compound under certain conditions to produce the 3,5-heptandiol dibenzoate. Through the batch preparation method, cheap raw materials as initiators can be prepared into needed heptandiol dibenzoate products at a high yield. Therefore, the batch preparation method can be utilized for mass preparation of the 3,5-heptandiol dibenzoate.
Description
Technical field
The present invention relates to the compound method of organic binary alcohol esters, refer in particular to 4 and replace or unsubstituted 3, the preparation method of 5-heptanediol diphenylmethyl acid esters.
Background technology
Replace or unsubstituted 3,5-heptanediol dibenzoic acid ester compound can be used for the catalyst component of olefinic polyreaction, thereby its compound method, and the method that is particularly useful for batch preparations has just had Practical significance.
The preparation method of this compounds that is used for polyolefin catalyst component is disclosed among the Chinese patent CN1454298A; Directly adopt 3; 5-heptadione or substituted 3, the 5-heptadione obtains final product as starting raw material through reduction and esterification and some treatment steps.This method has been used very expensive raw material, in the preparation process, has used the step such as higher costs such as " column chromatographies " simultaneously.Can judge that thus aforesaid method is a kind of laboratory compound method, should not be used for the preparation process with commercial significance of this compounds.
Though the disclosed compound method that is used for this compounds has used ethyl propionate and the more so inexpensive raw materials of butanone as initiator in Chinese patent CN1580034A; But still adopted the yield of very high treatment step of many costs and process also lower in the preparation process, can be judged as a kind of laboratory compound method equally and should not be used to have the batch preparations process of commercial significance.
Therefore develop a kind of practical approach that is applicable to batch preparations heptanediol dibenzoic acid ester compound highly significant.
Summary of the invention
The technical problem that the present invention will solve:
To the problem that exists in the prior art, the objective of the invention is to propose a kind of method that is applicable to the batch preparations heptanediol dibenzoic acid ester compound of commercial applications.
A kind ofly be used for 4 and replace or unsubstituted 3, the preparation method of 5-heptanediol diphenylmethyl acid esters comprises the steps:
The first step 3,5-heptadione synthetic
In the presence of solvent and basic catalyst, make ethyl propionate and butanone generation acylation reaction generate 3, the 5-heptadione is handled with the chelating purification process after stopped reaction especially and is obtained 3,5-heptadione product.
The temperature of said acylation reaction is 20-120 ℃, and solvent is non-proton type solvent, consumption (solvent: be 1 ethyl propionate): 1-10: 1 (mass ratio); The catalyzer add-on is (a catalyzer: be 0.5 ethyl propionate): 1-10: 1 (mol ratio); (ethyl propionate: be 0.3 butanone): 1-4: 1 (mol ratio), said basic catalyst are metal or nonmetallic hydrogenate to proportioning raw materials, like NaH; CaH, BF3 etc.
Said chelating purification process is to make reaction product 3,5-heptadione product and IB, and IIB, VIII family metal forms the inner complex solid.Solid is separated after acidification is 3 5-heptadione product from system.
Second step replaced 3,5-heptadione synthetic
In the presence of solvent and basic catalyst, enable with 3, the reagent that the 4-substitution reaction takes place the 5-heptadione contacts with it, and it is substituted 3 to obtain 4-, the 5-heptadione.
The C1-C20 that solvent comprises straight or branched contains or does not contain the alkane of other atoms except that hydrocarbon atom, aromatic hydrocarbons, alcohol, ketone, ether, ester, sulfoxide, phenols.Catalyzer comprises the compound of first or second main group metal.Mentioned reagent comprises containing of C1-C20 straight or branched or does not contain other halogenated organic matters except that hydrocarbon halogen atom.
The temperature of above-mentioned reaction is not less than 10 ℃, and preferred 20-100 ℃, proportion of raw materials (alkylating reagent: 3, the 5-heptadione) be not less than 0.5: 1 at least (mol ratio), preferably be not less than 0.8: 1 (mol ratio).Catalyzer with 3, the proportioning of 5-heptadione is not less than 0.3: 1 (mol ratio), preferably is not less than 0.7: 1 (mol ratio).
As preparing unsubstitutedly 3,5-heptanediol ester then can omit this step.
Synthesizing of the 3rd step heptanediol
Under solvent or solvent-free situation, use the reductive agent reduction to replace in the alkaline condition or unsubstituted 3, the 5-heptadione obtains 3, the 5-heptanediol.
Reductive agent is selected from hydrogen, the borine of metal hydride compounds and C1-C5.The C1-C20 that solvent comprises straight or branched comprises or does not comprise the alkane of other atoms except that hydrocarbon atom, aromatic hydrocarbons, alcohol, ketone, ether, ester, sulfoxide, phenols.Dropping and temperature of reaction are not less than-20 ℃ at least, preferably are not less than-5 ℃, and the proportioning of reductive agent and diketone is 0.2: 1-4: 1 (mol ratio).
Synthesizing of the 4th step heptanediol dibenzoate
With reduzate 3, the 5-heptanediol reacts under certain condition with the compound that contains carbonyl and obtains product heptanediol dibenzoate in the solvent.
The C1-C20 that solvent comprises straight or branched comprises or does not comprise the alkane of other atoms except that hydrocarbon atom, aromatic hydrocarbons, alcohol, ketone, ether, ester, sulfoxide, phenols.The compound that contains carboxylic acid comprises phenylformic acid, Benzoyl chloride 99min., benzoic ether, benzoyl oxide.
Temperature of reaction is not less than 20 ℃ at least, preferably is not less than 30 ℃.The raw material part (3,5-heptanediol: be 1 carboxylated compound): 1-1: 5 (mol ratios).
The invention has the beneficial effects as follows:
Technical scheme according to the present invention proposes can use inexpensive raw material to obtain required heptanediol dibenzoate product with high yield as initiator; The preparation process adopts and is suitable for synthetic means of cell operation in enormous quantities, prepares process so can be used for the commercialization of this compounds.
Embodiment
Embodiment 1
4-ethyl-3, the preparation of 5-heptanediol dibenzoate
(1) in reaction kettle, adds the solvent THF of NaH 107.5kg and 310kg, mix, take by weighing butanone 107.9kg and ethyl propionate 153.7kg mixes, within 20h, join in the tetrahydrofuran solution of NaH, add a spot of ethanol initiation reaction.The reinforced back that finishes keeps reaction system backflow (55 ℃) reaction to stop heating, cooling after 2 hours.
Acetic acid 172.7kg is added in the 500kg frozen water, and the formation solution that stirs adds the frozen water solution of Glacial acetic acid min. 99.5 with reaction solution, static layering, and water layer extracts with ETHYLE ACETATE 120*2kg.Underpressure distillation obtains 3,5-heptadione bullion.
(2) the saturated neutralized verdigris solution of preparation.Get above obtain 3, the 5-heptadione adds saturated neutralized verdigris solution 1736.15kg (solubleness is 7.2g/100g) after adding 95% alcohol dilution of 513.25kg, obtains deposition; Filter; Filter cake washs with 60% ethanol 501.38kg, uses the 600kg water washing again, finally obtains the chelating solid.
The chelating solid is dissolved in the methylene dichloride of 300kg, adds dilute sulphuric acid (32%) 398.25kg and carry out acidifying, layering, water layer is used the 50kg dichloromethane extraction.Organic phase is through after removing water treatment, and evaporating solvent obtains 3, and the pure article of 5-heptadione, yield are 51.8%.
(3) in reaction kettle, add 3 successively, the pure article 81.2kg of 5-heptadione, iodoethane 99.16kg acetone 243.6kg and Anhydrous potassium carbonate 142kg; Heat temperature raising is to refluxing, and reaction 19h filters; Filtrating obtains 4-ethyl-3,5-heptadione, yield 95% through underpressure distillation.
(4) NaOH of adding 0.5kg in reaction kettle, the Peng Qinghuana of 23kg and the water of 390L are cooled to after the dissolving below 0 ℃; Beginning slowly adds 4-ethyl-3, the ethanolic soln of the pure article 105kg of 5-heptadione (the alcoholic acid quality is a 4-ethyl 3, the pure article of 5-heptadione 2.4 times); Add the back holding temperature at 0 ℃ of 2h; Be warming up to room temperature reaction 15h afterwards, reaction finishes the back adds 390L in reaction kettle water and 156kg*3 chloroform extraction, and the organic phase distillation obtains 4-ethyl-3 after removing and desolvating; The 5-heptanediol, yield 96%.
(5) the 4-ethyl-3 after adding is dewatered in reaction kettle successively, 5-heptanediol 136.9kg, the toluene of dehydration pyridine 159.4kg and 432kg; Slowly add Benzoyl chloride 99min. 202.45kg, control reaction temperature is reacted 8h about 50 ℃; Filter,, remove impurity through distillation with toluene 56.2kg washing leaching cake; Obtain 4-ethyl-3,5-heptadione dibenzoate, yield 96%.
Embodiment 2
3, the preparation of 5-heptanediol benzoic ether
(1) NaOH of adding 0.372kg in reaction kettle, the Peng Qinghuana of 21.36kg and the water of 254L are cooled to after the dissolving below 0 ℃; Beginning slowly adds 3, the ethanolic soln of the pure article of 5-heptadione (embodiment 1 second step product) 84.65kg (the alcoholic acid quality is 3, the pure article of 5-heptadione 2.4 times); Add the back holding temperature at 0 ℃ of 2h; Be warming up to room temperature reaction 15h afterwards, reaction finishes the back adds 508L in reaction kettle water and 125.3*3kg chloroform extraction, and the organic phase distillation obtains 3 after removing and desolvating; The 5-heptanediol, yield 96.87%.
(2) 3 after the adding dehydration in reaction kettle successively, 5-heptanediol 85kg, the toluene of dehydration pyridine 122.25kg and 358kg; Slowly add Benzoyl chloride 99min. 159.27kg, the control dropping temperature is warming up to about 70 ℃ of reaction 3h afterwards about 50 ℃; Filter,, remove impurity through distillation with toluene 45.2kg washing leaching cake; Obtain 3,5-heptanediol dibenzoate, yield 95%.
Claims (10)
- One kind be used for 4 substituted 3, the preparation method of 5-heptanediol diphenylmethyl acid esters comprises the steps:The first step, in the presence of solvent and basic catalyst, make ethyl propionate and butanone generation acylation reaction generate 3, the 5-heptadione is handled with the chelating purification process after stopped reaction especially and is obtained 3,5-heptadione product;Second step, in the presence of solvent and basic catalyst, enable with 3, the reagent that the 4-substitution reaction takes place the 5-heptadione contacts with it, it is substituted 3 to obtain 4-, the 5-heptadione;The 3rd step, under solvent or solvent-free situation, it is substituted 3 to use reductive agent to reduce in the alkaline condition, the 5-heptadione obtains 3, the 5-heptanediol;With reduzate 3, the 5-heptanediol reacts under certain condition with the compound that contains carbonyl and obtains product heptanediol dibenzoate in the 4th step, the solvent.
- 2. according to claim 1 a kind of be used for 4 substituted 3, the preparation method of 5-heptanediol diphenylmethyl acid esters, the temperature that it is characterized in that the first step acylation reaction is 20-120 ℃; Solvent is non-proton type solvent; Consumption (solvent: be 1 ethyl propionate): 1-10: 1 (mass ratio), the catalyzer add-on is (a catalyzer: be 0.5 ethyl propionate): 1-10: 1 (mol ratio), proportioning raw materials (ethyl propionate: be 0.3 butanone): 1-4: 1 (mol ratio); Said basic catalyst is metal or nonmetallic hydrogenate; Like NaH, CaH, BF3 etc.
- 3. according to claim 1 a kind of be used for 4 substituted 3, the preparation method of 5-heptanediol diphenylmethyl acid esters is characterized in that the chelating purification process is to make reaction product 3,5-heptadione product and IB, IIB, VIII family metal forms the inner complex solid.
- 4. according to claim 1 a kind of be used for 4 substituted 3, the preparation method of 5-heptanediol diphenylmethyl acid esters is characterized in that the inner complex solid that the chelating purification process forms separates after acidification is 3 5-heptadione product from system.
- 5. according to claim 1 a kind of be used for 4 substituted 3, the preparation method of 5-heptanediol diphenylmethyl acid esters, the C1-C20 that the solvent that it is characterized in that for second step comprises straight or branched contains or does not contain the alkane of other atoms except that hydrocarbon atom; Aromatic hydrocarbons, alcohol, ketone; Ether; Ester, sulfoxide, phenols; Catalyzer comprises the compound of first or second main group metal; Reagent comprises containing of C1-C20 straight or branched or does not contain other halogenated organic matters except that hydrocarbon halogen atom.
- 6. according to claim 1ly a kind ofly be used for 4 substituted 3; The preparation method of 5-heptanediol diphenylmethyl acid esters; The temperature that it is characterized in that the reaction of second step is not less than 10 ℃, and preferred 20-100 ℃, proportion of raw materials (alkylating reagent: 3; The 5-heptadione) is not less than 0.5: 1 at least (mol ratio), preferably is not less than 0.8: 1 (mol ratio).Catalyzer and 3, the proportioning of 5-heptadione are not less than 0.3: 1 (mol ratio), preferably are not less than 0.7: 1 (mol ratio).
- 7. according to claim 1 a kind of be used for 4 substituted 3, the preparation method of 5-heptanediol diphenylmethyl acid esters is characterized in that the 3rd step reductive agent is selected from hydrogen, the borine of metal hydride compounds and C1-C5; The C1-C20 that solvent comprises straight or branched comprises or does not comprise the alkane of other atoms except that hydrocarbon atom, aromatic hydrocarbons, alcohol, ketone, ether, ester, sulfoxide, phenols; Dropping and temperature of reaction are not less than-20 ℃ at least, preferably are not less than-5 ℃, and the proportioning of reductive agent and diketone is 0.2: 1-4: 1 (mol ratio).
- 8. according to claim 1 a kind of be used for 4 substituted 3, the preparation method of 5-heptanediol diphenylmethyl acid esters is characterized in that C1-C20 that the 4th step solvent comprises straight or branched comprises or do not comprise the alkane of other atoms except that hydrocarbon atom, aromatic hydrocarbons; Alcohol, ketone, ether; Ester, sulfoxide, phenols; The compound that contains carboxylic acid comprises phenylformic acid, Benzoyl chloride 99min., benzoic ether, benzoyl oxide.
- 9. according to claim 1 a kind of be used for 4 substituted 3, the preparation method of 5-heptanediol diphenylmethyl acid esters is characterized in that the four-step reaction temperature is not less than 20 ℃ at least, preferably is not less than 30 ℃; The raw material part (3,5-heptanediol: be 1 carboxylated compound): 1-1: 5 (mol ratios).
- 10. one kind is used for unsubstitutedly 3, and the preparation method of 5-heptanediol diphenylmethyl acid esters comprises the steps:The first step, in the presence of solvent and basic catalyst, make ethyl propionate and butanone generation acylation reaction generate 3, the 5-heptadione is handled with the chelating purification process after stopped reaction especially and is obtained 3,5-heptadione product;Second step, under solvent or solvent-free situation, it is unsubstituted 3 to use reductive agent to reduce in the alkaline condition, the 5-heptadione obtains 3, the 5-heptanediol;With reduzate 3, the 5-heptanediol reacts under certain condition with the compound that contains carbonyl and obtains product heptanediol dibenzoate in the 3rd step, the solvent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541554A (en) * | 2014-11-04 | 2016-05-04 | 中国石油化工股份有限公司 | Method for preparing beta-diol from beta-diketone |
| CN105622346A (en) * | 2014-11-04 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparation of beta-diol from beta-diketone by fixed bed hydrogenation |
| CN105622345A (en) * | 2014-11-04 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparation of beta-diol |
| CN117447323A (en) * | 2023-10-25 | 2024-01-26 | 岳阳聚成化工有限公司 | Preparation method of 3, 5-heptanediol dibenzoate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541554A (en) * | 2014-11-04 | 2016-05-04 | 中国石油化工股份有限公司 | Method for preparing beta-diol from beta-diketone |
| CN105622346A (en) * | 2014-11-04 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparation of beta-diol from beta-diketone by fixed bed hydrogenation |
| CN105622345A (en) * | 2014-11-04 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparation of beta-diol |
| CN117447323A (en) * | 2023-10-25 | 2024-01-26 | 岳阳聚成化工有限公司 | Preparation method of 3, 5-heptanediol dibenzoate |
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Application publication date: 20120418 |