CN106632229B - A kind of preparation method of cyclic acetal - Google Patents
A kind of preparation method of cyclic acetal Download PDFInfo
- Publication number
- CN106632229B CN106632229B CN201510740971.4A CN201510740971A CN106632229B CN 106632229 B CN106632229 B CN 106632229B CN 201510740971 A CN201510740971 A CN 201510740971A CN 106632229 B CN106632229 B CN 106632229B
- Authority
- CN
- China
- Prior art keywords
- compound
- long
- small molecule
- chain
- preparation
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—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
- C07D317/10—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 not condensed with other rings
- C07D317/12—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 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of cyclic acetal.This method is using long-chain polyols compound and small molecule aldehyde as substrate, and using long-chain low pole molecule as solvent, under the effect of the catalyst, the both ends hydroxyl condensation of aldehyde and long-chain polyols compound forms the cyclic acetal of intramolecular.It is compared to traditional acetal method, this method is using the difference on solvent and reactant and substrate properties, so that aldehydes is easy to react with two terminal hydroxy groups, the ratio of cyclic acetal is high in product.The conversion ratio of aldehyde compound reaches 80% or more, and the selectivity of cyclic acetal is up to 80% or more.
Description
Technical field
The present invention relates to chemical field, specifically a kind of preparation method of cyclic acetal.
Background technique
Cyclic acetal refers to such as 1,3- dioxolane, 1,4- butylene glycol formal, diethylene glycol formal, 4- hydroxyl
Base -1,3- dioxolane, 5,6- dihydroxy -1,3- Dioxepane etc..Cyclic acetal is usually as such as grease
Solvent, extractant, the intermediate of drug, raw material of resin material etc. use.
Cyclic formals are mainly obtained by the terminal hydroxy group of polyol and aldehydes condensation reaction.But polyhydroxy chemical combination
For object due to there is multiple hydroxyls, polyol can have multiple sites to be reacted, aldehyde when with the condensation such as formaldehyde
Class compound is easy to be condensed with neighbouring hydroxyl, forms the ethylidene ether structure of non-annularity, or formed with the hydroxyl of neighboring molecule
Intermolecular acetal.Cause the ratio of final cyclic acetal smaller, by taking erythrite as an example, molecule aldolactol has been possible to four
Kind, since two hydroxyls are closer in the acetal forming process of II and III, steric hindrance is smaller, thus in common acetal method
Under conditions of, the ratio of II and III in final product are higher, and the ratio of required cyclic acetal I is lower.If can
Method appropriate is taken, the erythrite of chain is existed when reaction with the conformation of annular, so that two end hydroxyls
Base approaches on space length, to improve the ratio of cyclic acetal in acetal product.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of cyclic acetal, this process employs long-chain low pole molecules to be
Solvent, since the polyol of long-chain is highly polar molecule, in the low pole molecular solvent of this long-chain, due to molten
The cage effect of agent exists, and polyol is forced mostly to exist with cyclic conformation so that in product cyclic acetal ratio
It is higher.Realize above-mentioned purpose.
The technical solution of the present invention is as follows:
According to the present invention, this method is weak with long-chain using long-chain polyols compound and small molecule aldehyde compound as substrate
Polar molecule is solvent, and under the effect of the catalyst, the both ends hydroxyl condensation of aldehyde and long-chain polyols compound forms intramolecular
Cyclic acetal.
According to the present invention, the long-chain polyols compound be ethylene glycol, propylene glycol, glycerine, 1,4-butanediol, two
Glycol, erythrite, xylitol, sorbierite, one of mannitol.
According to the present invention, the small molecule aldehyde compound is formaldehyde, acetaldehyde, one of benzaldehyde.
According to the present invention, the catalyst is Amberlyst-36, Amberlyst-15, Nafion-HNR-50, to first
Benzene sulfonic acid, benzene sulfonic acid, sulfuric acid, nitric acid, one of hydrochloric acid or two or more.
According to the present invention, the long-chain low pole molecular solvent be octadecane, octadecylene, oleic acid, oleyl alcohol, oleyl amine, ten
Eight alkanoic acids, octadecanol, one of octadecylamine.
According to the present invention, when reaction, long-chain polyols compound should be added dropwise in solvent first, be made by being vigorously stirred
It disperses, and catalyst and small molecule aldehyde compound is then added, and is warming up to relevant temperature, confined reaction system, reaction to knot
Beam.
According to the present invention, the molar ratio of small molecule aldehyde compound and long-chain polyols compound is 1:1-1:1.5, preferably
For 1:1.09-1:1.11.The additional amount of catalyst is the 1- of small molecule aldehyde compound and long-chain polyols compound gross mass
20%, preferably 4.5-5.5%.The quality of solvent is small molecule aldehyde compound and long-chain polyols compound gross mass 1-20
Times, preferably 4.9-5.1 times.
According to the present invention, the reactor used that reacts is autoclave stirred reactor.
According to the present invention, reaction temperature is 60 to 220 DEG C, preferably 95-105 DEG C, reaction time 0.5-10h, preferably
For 0.9-1.1h.The conversion ratio of aldehyde compound reaches 80% or more, and the selectivity of cyclic acetal is up to 80% or more.
The invention has the advantages that
Compared to traditional catalysis process, it is solvent that this method, which selects special long-chain low pole molecular organic compound,
Have many advantages, such as that high conversion rate, cyclic acetal ratio are high.
Detailed description of the invention
Fig. 1 is the mass spectrogram of product in resulting embodiment 1；Wherein top is products obtained therefrom spectrogram, lower section 1,3-
The standard spectrogram of glycerol formal.
Specific embodiment
Method provided by the invention is described in detail below with reference to embodiment, but the invention is not limited in any way.
Embodiment 1
40g octadecylene is added into reaction kettle, 3g glycerine is added dropwise to by heating stirring under conditions of being vigorously stirred
In octadecylene, after the two is stirred evenly, 0.3g catalyst Amberlyst-15 is added, is added dropwise to 0.9g formaldehyde, is warming up to
100 DEG C, 1h being reacted, is examined by chromatography, the conversion ratio of formaldehyde is 95%, in products therefrom, cyclic acetal 1,3- glycerol acetonide first
Aldehyde (5- hydroxyl -1,3- dioxane) selectively reaches 80%.
Equation is as follows:
Embodiment 2-5
The reaction process of embodiment 1 is repeated, the difference is that reaction condition is different from used solvent, catalyst.Each reality
It applies the specific reaction condition of example and the results are shown in Table 1.
Table 1, the specific reaction condition of embodiment 2-5
Embodiment 6
Octadecane 30g is added into reaction kettle, 2.5g glycerine is added dropwise under conditions of being vigorously stirred for heating stirring
Enter in octadecane, after the two is stirred evenly, catalyst Amberlyst-360.3g is added, is added dropwise to formaldehyde 0.8g, heat up
To 120 DEG C, 1.2h being reacted, is examined by chromatography, the conversion ratio of formaldehyde is 95%, in products therefrom, cyclic acetal 1,3- glycerol
Formal selectively reaches 80%.
Embodiment 7-10
The reaction process of embodiment 6 is repeated, the difference is that the substrate used is different.The specific substrate of each embodiment is listed in table
In 2.
Table 2, the specific reaction condition of embodiment 7-10
Embodiment 11
Oleyl amine 30g is added into reaction kettle, 2.2g ethylene glycol is added dropwise to by heating stirring under conditions of being vigorously stirred
In oleyl amine, after the two is stirred evenly, catalyst Amberlyst-150.2g is added, is added dropwise to acetaldehyde 0.6g, is warming up to 150
DEG C, 0.8h is reacted, is examined by chromatography, the conversion ratio of acetaldehyde is 93%, in products therefrom, the choosing of cyclic acetal glycol ethylidene-acetal
Selecting property reaches 82%.
Reaction equation is as follows:
Embodiment 12
Oleyl alcohol 40g is added into reaction kettle, 3g ethylene glycol is added dropwise to oil under conditions of being vigorously stirred by heating stirring
In amine, after the two is stirred evenly, catalyst sulfuric acid 0.2g is added, is added dropwise to benzaldehyde 0.9g, is warming up to 180 DEG C, reaction
2h is examined by chromatography, and the conversion ratio of benzaldehyde is 83%, in products therefrom, cyclic acetal ethylene glycol condensing benzaldehyde selectivity
Reach 80%.
Reaction equation is as follows:
Claims (7)
1. a kind of preparation method of cyclic acetal, it is characterised in that: with long-chain polyols compound and small molecule aldehyde compound
For substrate, using long-chain low pole molecular organic compound as solvent, under the effect of the catalyst, small molecule aldehyde compound and length
The both ends hydroxyl condensation of chain polyol forms the cyclic acetal of intramolecular；
The long-chain polyols compound is glycerine；The small molecule aldehyde compound is formaldehyde, acetaldehyde, one in benzaldehyde
Kind；The catalyst is Amberlyst-36, Amberlyst-15, Nafion-HNR-50, p-methyl benzenesulfonic acid, benzene sulfonic acid, sulphur
Acid, nitric acid, one of hydrochloric acid or two or more；The long-chain low pole molecular organic compound be octadecane, octadecylene,
Oleic acid, oleyl alcohol, oleyl amine, octadecanoid acid, octadecanol, one of octadecylamine.
2. preparation method described in accordance with the claim 1, it is characterised in that: when reaction, long-chain polyols compound is dripped first
It is added in solvent, makes its dispersion by being vigorously stirred, catalyst and small molecule aldehyde compound is then added, is warming up to corresponding temperature
Degree, confined reaction system, reaction is to terminating.
3. preparation method according to claim 1 or 2, it is characterised in that: small molecule aldehyde compound and long-chain polyols
The molar ratio of compound is 1:1-1:1.5；The additional amount of catalyst is small molecule aldehyde compound and long-chain polyols compound
The 1-20% of gross mass；The quality of solvent is small molecule aldehyde compound and 1-20 times of gross mass of long-chain polyols compound.
4. preparation method according to claim 1 or 2, it is characterised in that: small molecule aldehyde compound and long-chain polyols
The molar ratio of compound is 1:1.09-1:1.11；The additional amount of catalyst is small molecule aldehyde compound and long-chain polyols
Close the 4.5-5.5% of object gross mass；The quality of solvent is small molecule aldehyde compound and long-chain polyols compound gross mass
4.9-5.1 again.
5. preparation method described in accordance with the claim 1, it is characterised in that: reaction temperature is 60 to 220 DEG C, and the reaction time is
0.5-10h。
6. preparation method described in accordance with the claim 1, it is characterised in that: reaction temperature is 95-105 DEG C, and the reaction time is
0.9-1.1h。
7. preparation method described in accordance with the claim 1, it is characterised in that: the reactor used that reacts is that autoclave stirring is anti-
Answer device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510740971.4A CN106632229B (en) | 2015-11-04 | 2015-11-04 | A kind of preparation method of cyclic acetal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510740971.4A CN106632229B (en) | 2015-11-04 | 2015-11-04 | A kind of preparation method of cyclic acetal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106632229A CN106632229A (en) | 2017-05-10 |
| CN106632229B true CN106632229B (en) | 2019-04-05 |
Family
ID=58851208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510740971.4A Active CN106632229B (en) | 2015-11-04 | 2015-11-04 | A kind of preparation method of cyclic acetal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106632229B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721582B (en) * | 2017-10-30 | 2020-11-13 | 中国石油化工股份有限公司 | Preparation method of 1, 3-oxacycloalkane |
| CN107935832A (en) * | 2017-12-30 | 2018-04-20 | 郑州智谷工业技术有限公司 | A kind of method using fabricated by dehydrogenating alcohol for aldehyde or hemiacetal |
| CN110156744A (en) * | 2019-04-29 | 2019-08-23 | 南京点元环境科技有限公司 | A kind of preparation method of hexa-atomic glycerine acetal |
| CN110339861A (en) * | 2019-07-22 | 2019-10-18 | 苏州大学 | The superpower catalysis synthetic method for solid acid of diamino diarylmethanes class compound |
| CN113024360B (en) * | 2021-03-30 | 2022-07-08 | 国药集团化学试剂有限公司 | Synthesis method of m-methoxy benzyl alcohol |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962377A (en) * | 2009-07-23 | 2011-02-02 | 中国科学院兰州化学物理研究所 | Method for catalysis synthesis of glycerol formal by gemini dication acidic ion liquid |
| CN102405204A (en) * | 2009-04-21 | 2012-04-04 | 弗门尼舍有限公司 | Acetals as perfuming ingredients |
| CN103619830A (en) * | 2011-06-24 | 2014-03-05 | 伊士曼化工公司 | Production of cyclic acetals or ketals using liquid-phase acid catalysts |
| CN103619829A (en) * | 2011-06-24 | 2014-03-05 | 伊士曼化工公司 | Production of cyclic acetals or ketals using solid acid catalysts |
| CN104262319A (en) * | 2014-08-14 | 2015-01-07 | 江西农业大学 | Nopylaldehyde hydride cyclic acetal compound and synthesis method thereof |
-
2015
- 2015-11-04 CN CN201510740971.4A patent/CN106632229B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102405204A (en) * | 2009-04-21 | 2012-04-04 | 弗门尼舍有限公司 | Acetals as perfuming ingredients |
| CN101962377A (en) * | 2009-07-23 | 2011-02-02 | 中国科学院兰州化学物理研究所 | Method for catalysis synthesis of glycerol formal by gemini dication acidic ion liquid |
| CN103619830A (en) * | 2011-06-24 | 2014-03-05 | 伊士曼化工公司 | Production of cyclic acetals or ketals using liquid-phase acid catalysts |
| CN103619829A (en) * | 2011-06-24 | 2014-03-05 | 伊士曼化工公司 | Production of cyclic acetals or ketals using solid acid catalysts |
| CN104262319A (en) * | 2014-08-14 | 2015-01-07 | 江西农业大学 | Nopylaldehyde hydride cyclic acetal compound and synthesis method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106632229A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106632229B (en) | A kind of preparation method of cyclic acetal | |
| Oprescu et al. | Synthesis and testing of glycerol ketals as components for diesel fuel | |
| JP4886283B2 (en) | Method for producing α, β-unsaturated aldehyde compound | |
| Pandiangan et al. | Transesterification of coconut oil using dimethyl carbonate and TiO2/SiO2 heterogeneous catalyst | |
| Sharma et al. | Microencapsulated cardanol derived benzoxazines for self-healing applications | |
| Lewicki et al. | On the synthesis and structure of resorcinol-formaldehyde polymeric networks–precursors to 3D-carbon macroassemblies | |
| DE102006009079A1 (en) | New carbonylhydrogenated ketone-aldehyde resin useful in lacquer industries, coating materials and for weathering | |
| CN107406652A (en) | Modified polyvinyl acetal resin composition | |
| Nowicki et al. | Novel basic ionic liquids from cyclic guanidines and amidines–new catalysts for transesterification of oleochemicals | |
| WO2016094859A1 (en) | Polyols from protein biomass | |
| Pryde et al. | Ozonization of soybean oil. The preparation and some properties of aldehyde oils | |
| JP2012500287A (en) | Method for producing glycerol formal | |
| TWI235149B (en) | A process for preparing straight-chain aliphatic carboxylic acids from aldehydes | |
| Arnold et al. | Amine-catalyzed aldol condensation in the presence of lithium perchlorate | |
| JPH06100665A (en) | Epoxy resin composition | |
| TWI650304B (en) | Method for producing cyclobutane tetracarboxylic acid derivative | |
| WO2017093473A1 (en) | Guerbet condensation reaction | |
| Berrouane et al. | Sustainable synthesis of a novel bio-based low temperature curable benzoxazine monomer from quercetin: Synthesis, curing reaction and thermal properties | |
| CN105885044A (en) | Synthesis method of crude phenol-based benzoxazines resin prepolymers | |
| Podgorski et al. | Bismuth Compounds in Organic Synthesis: Synthesis of Dioxanes, Dioxepines, and Dioxolanes Catalyzed by Bismuth (III) Triflate | |
| CN114341096A (en) | Method for producing dialdehydes | |
| Fareghi-Alamdari et al. | An efficient synthetic approach to substituted trisphenols (phloroglucide analogues) using tungstosilicic acid in water | |
| US2538884A (en) | Acetone-formaldehyde resins | |
| DE102006026758A1 (en) | Formaldehyde-free, carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde with low OH functionality and a process for their preparation | |
| RU2634902C1 (en) | Method of producing dibutylkarbitolformal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |