CN106632222B - A kind of polyalcohol formal adds the method for hydrogen dehydroxylation - Google Patents
A kind of polyalcohol formal adds the method for hydrogen dehydroxylation Download PDFInfo
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- CN106632222B CN106632222B CN201510741143.2A CN201510741143A CN106632222B CN 106632222 B CN106632222 B CN 106632222B CN 201510741143 A CN201510741143 A CN 201510741143A CN 106632222 B CN106632222 B CN 106632222B
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
- C07D321/02—Seven-membered rings
- C07D321/04—Seven-membered rings not condensed with other rings
- C07D321/06—1,3-Dioxepines; Hydrogenated 1,3-dioxepines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
- C07D321/02—Seven-membered rings
- C07D321/04—Seven-membered rings not condensed with other rings
- C07D321/08—1,4-Dioxepines; Hydrogenated 1,4-dioxepines
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Abstract
The invention discloses a kind of methods that polyalcohol formal adds hydrogen dehydroxylation.This method is using polyol acetal as substrate, and using long-chain low pole molecule as solvent, under the effect of the catalyst, acetal adds hydrogen dehydroxylation to obtain oxa- cycloalkane and keeps ethylidene ether structure.Catalyst used can make Rh/C, Ru/C, Pd/C.This method selects special solvent, so that the ethylidene ether structure in hydrogenation process is maintained, the removal efficiency of hydroxyl is higher, and the conversion ratio of polyalcohol formal reaches 90% or more, and the selectivity of deshydroxy based products is up to 80% or more.
Description
Technical field
The present invention relates to chemical field, specifically a kind of polyalcohol formal adds the method for hydrogen dehydroxylation.
Background technique
Acetal compound it is widely used, can be used as such as fuel oil additive, solvent, extractant, the drug of grease
Intermediate, resin material raw material etc. use.Such as ethylene glycol acetal can be used as the solvent of low-boiling compound, and oil
Rouge, wax, dyestuff and fiber derivative extractant.
In recent years, with the exhaustion of petroleum resources, biomass-based resource is increasingly taken seriously, using biomass-based polynary
Alcohol is an important issue to produce acetal product.Biomass-based polyalcohol polyol due to there is multiple hydroxyls,
It is formed after acetal, often still has hydroxyl not react, and the presence of these hydroxyls can hinder it as solvent, extractant etc.
The application of aspect.Therefore, suitable method is selected, extra hydroxyl is removed, the structure of not hydroxyl is formed, just becomes one
Important proposition.The aldolisation of the substrate synthesis of acetals is a kind of reversible reaction, if using traditional hydrogenation and removing side
Method is removed, then acetals substrate is also easy to happen back reaction very much during adding hydrogen, so as to cause ethylidene ether structure
Destruction.Therefore, the hydrogenation process that can not destroy ethylidene ether structure is found, important project is just become.
The saturated alkane molecule of long-chain is the molecule of a kind of low pole, and polyalcohol formal is then highly polar molecule,
Due to the cage effect of solvent, the decomposition of acetal molecule can be hindered, to guarantee under hydroconversion condition, the integrality of ethylidene ether structure.
Summary of the invention
A kind of polyalcohol formal adds the method for hydrogen dehydroxylation, is solvent this process employs the saturated alkane of long-chain, long
The saturated alkane molecule of chain is the molecule of a kind of low pole, and polyalcohol formal is then highly polar molecule, due to solvent
Cage effect, can hinder the decomposition of acetal molecule, to guarantee under hydroconversion condition, the integrality of ethylidene ether structure.It realizes above-mentioned
Purpose.
The technical solution adopted by the present invention is：
Using polyalcohol formal as substrate, using long-chain low pole molecule as solvent, under the effect of the catalyst, acetal adds hydrogen
Dehydroxylation, and keep ethylidene ether structure.
The polyalcohol formal is 1,3- glycerol formal (5- hydroxyl -1,3- dioxane) (structural formula A),
1,2- glycerol formal (4- methylol -1,3- dioxolane) (structural formula B), Isosorbide-5-Nitrae-erythrite formal (5,6- dihydroxies
Base -1,3- Dioxepane) (structural formula C), 2,3- erythrite formals (5,6- dihydroxymethyl -1,3- Dioxepane)
(structural formula D), 1,3- erythrite formal (4- hydroxyl -5- methylol -1,3- dioxolane) (structural formula E), 5- hydroxyl -
One of 1,3- Dioxepane (structural formula F).
Catalyst used is Rh/C, Ru/C, one of Pd/C, wherein it is total to account for catalyst for metal component in catalyst
The mass percent of amount is 2-15wt%.
The long-chain low pole molecular solvent is one or more of C12-C24 saturated alkane, the long-chain
Low pole molecular solvent is specially dodecane, tridecane, the tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane,
Eicosane, heneicosane, docosane, tricosane, lignocerane.
The additional amount of catalyst is the 1-20% of polyalcohol formal quality, and the quality of preferably 4.5-5.5%, solvent are
1-20 times of quality of polyalcohol formal, preferably 4.5-5.5 times.
The reaction is suitable for batch tank reactor, and when reaction, long-chain polyols compound is added dropwise in solvent first,
Make its dispersion by being vigorously stirred, catalyst is then added, is filled with hydrogen to certain pressure, is warming up to relevant temperature, starts
Stirring, reaction is to terminating.
Reaction temperature is 60 to 220 DEG C, preferably 95-105oC, reaction time 0.5-10h, preferably 0.9-1.1h,
Hydrogen Vapor Pressure is 0.1-10MPa, preferably 1.8-2.2MPa.
Advantage of the present invention：
Add hydrogen dehydroxylation catalysis process compared to traditional, this method selects the saturated alkane of long-chain as solvent, adds hydrogen
Ethylidene ether structure in the process is maintained, and the removal efficiency of hydroxyl is higher, and the conversion ratio of polyalcohol formal reaches 90% or more, takes off
The selectivity of hydroxy product is up to 80% or more.
Detailed description of the invention
Fig. 1 is products obtained therefrom in embodiment 11H-NMR spectrum.
Fig. 2 is products obtained therefrom in embodiment 113C-NMR spectrogram.
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 octadecane is added into reaction kettle, heating stirring, by 3g 1,3- glycerol formal is in the condition being vigorously stirred
Under, it is added drop-wise in the middle of octadecane, after stirring evenly, 0.1g Ru/C catalyst is added, be flushed with hydrogen atmospheric pressure to 2.0MPa, rise
Temperature is reacted 4h, is examined by chromatography to 140 DEG C, and the conversion ratio of 1,3- glycerol formal is 90%, product 1,3- dioxa hexamethylene
Alkane selectively reaches 85%.
Embodiment 2~9：The reaction process of embodiment 1 is repeated, the difference is that reaction condition and used solvent, catalysis
Agent is different.The specific reaction condition of each embodiment and the results are shown in Table 1.
Table 1, the specific reaction condition of embodiment 2~9
Embodiment 10：
Hexadecane 50g, heating stirring, by 3.5g 5- hydroxyl -1,3- dioxane violent are added into reaction kettle
It under conditions of stirring, is added drop-wise in the middle of oleyl alcohol, after stirring evenly, catalyst is added to Pd/C 0.2g.It is flushed with hydrogen gas extremely
4MPa is warming up to 120oC reacts 4h, examines by chromatography, and the conversion ratio of 1,3- glycerol formal is 95%, product 1,3- third
Glycol formaldehyde selectively reaches 85%.
Embodiment 11~14：The reaction process of embodiment 10 is repeated, the difference is that the substrate used is different.Each embodiment
Specific substrate is listed in Table 2 below.
Table 2, the specific reaction condition of embodiment 11~14
Claims (5)
1. a kind of polyalcohol formal adds the method for hydrogen dehydroxylation, it is characterised in that：This method using polyalcohol formal as substrate,
Using long-chain low pole molecule as solvent, under the effect of the catalyst, acetal adds hydrogen dehydroxylation, and keeps ethylidene ether structure；It is described
Long-chain low pole molecule be one or more of C12-C24 saturated alkane；
The polyalcohol formal is 1,3- glycerol formal, and 1,2- glycerol formal, Isosorbide-5-Nitrae-erythrite formal, 2,3- is red
Moss alcohol formal, 1,3- erythrite formal, one of 5- hydroxyl -1,3- Dioxepane.
2. according to the method for claim 1, it is characterised in that：Catalyst used is Rh/C, one in Ru/C, Pd/C
Kind, wherein it is 2-15 wt% that metal component, which accounts for the mass percent of catalyst total amount, in catalyst.
3. according to the method for claim 1, it is characterised in that：The additional amount of catalyst is the 1- of polyalcohol formal quality
20 %, the quality of solvent are 1-20 times of quality of polyalcohol formal.
4. according to the method for claim 1, it is characterised in that：The reaction is suitable for batch tank reactor, first when reaction
First long-chain polyols compound is added dropwise in solvent, makes its dispersion by being vigorously stirred, catalyst is then added, is filled with hydrogen
To certain pressure, it is warming up to relevant temperature, starting stirring, reaction is to terminating.
5. according to the method for claim 1, it is characterised in that：Reaction temperature is 60 to 220 DEG C, reaction time 0.5-10
H, Hydrogen Vapor Pressure are 0.1-10 MPa.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6294666B1 (en) * | 1999-10-01 | 2001-09-25 | Academia Sinica | Methods of preparing optically pure sugars |
| CN103864737A (en) * | 2012-12-17 | 2014-06-18 | 天津药物研究院 | Phenyl C-glucoside derivative containing deoxyglucose structure as well as preparation method and application thereof |
-
2015
- 2015-11-04 CN CN201510741143.2A patent/CN106632222B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6294666B1 (en) * | 1999-10-01 | 2001-09-25 | Academia Sinica | Methods of preparing optically pure sugars |
| CN103864737A (en) * | 2012-12-17 | 2014-06-18 | 天津药物研究院 | Phenyl C-glucoside derivative containing deoxyglucose structure as well as preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Complete Structure of the Mycolactones;Steve Fidanze;《J. Am. Chem. Soc.》;20010727;第123卷;Supporting Info.第1页化合物1a-d的合成 * |
| Doubly carbon-branched pentoses: synthesis of both enantiomers of 2,4-di-C-methyl arabinose and 2-deoxy-2,4-di-C-methyl arabinose using only acetonide protection;K. Victoria Booth;《Tetrahedron Letters》;20090625;第50卷;第5090页式5 * |
| K. Victoria Booth.Doubly carbon-branched pentoses: synthesis of both enantiomers of 2,4-di-C-methyl arabinose and 2-deoxy-2,4-di-C-methyl arabinose using only acetonide protection.《Tetrahedron Letters》.2009,第50卷第5088-5093页. * |
| Rodney A. Fernandes.A Chiron Approach to the Total Synthesis of (−)-Juglomycin A, (+)-Kalafungin, (+)-Frenolicin B, and (+)-Deoxyfrenolicin.《J. Org. Chem.》.2012,第77卷第10455-10460页. * |
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