CN107721974A - A kind of synthetic method of hexatomic ring list sulfocarbonate - Google Patents
A kind of synthetic method of hexatomic ring list sulfocarbonate Download PDFInfo
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- CN107721974A CN107721974A CN201710874357.6A CN201710874357A CN107721974A CN 107721974 A CN107721974 A CN 107721974A CN 201710874357 A CN201710874357 A CN 201710874357A CN 107721974 A CN107721974 A CN 107721974A
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- propane diols
- glycol
- synthetic method
- zinc oxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
- C07D327/06—Six-membered rings
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Abstract
The invention discloses a kind of method for synthesizing hexatomic ring list sulfocarbonate, using carbonyl sulfide and glycol compound as raw material, using acetonitrile as solvent and deicer, is reacted in the presence of catalyst and obtains hexatomic ring list sulfocarbonate；Catalyst is selected from zinc oxide, zinc hydroxide, zinc salt or alkali metals modified zinc oxide.The mol ratio of acetonitrile and glycol compound is 0.5~50:1, the mass ratio of catalyst and glycol compound is 0.5~50:100, the mol ratio of carbonyl sulfide and glycol compound is 0.1~50:1, reaction temperature is 50~200 DEG C, and the reaction time is 1~24 hour.The present invention have raw material it is cheap and easy to get, by the use of acetonitrile as dehydrating agent improve glycol compound conversion ratio and hexatomic ring list sulfocarbonate yield the advantages of.
Description
Technical field
The present invention relates to compound elegant synthetic methods preparation field, and more particularly to one kind is by carbonyl sulfide and glycols
The method of compound synthesis hexatomic ring list sulfocarbonate.
Background technology
Ring list sulfocarbonate is potential polar non-solute, drug synthesis intermediate, and prepares high refractive power and refer to
Monomer of number resin Polythiocarbonate etc..Therefore the synthesis of research ring list sulfocarbonate has important value.
Carbonyl sulfide is atmosphere pollution, and is industrial waste gas, but is also a kind of important chemical synthesis raw material simultaneously,
Ring list sulfocarbonate is prepared using carbonyl sulfide and glycol compound reaction, on the one hand can effectively utilize carbonyl sulfide
Synthesize valuable Organic chemical products；On the other hand this reaction has very high Atom economy, meets Green Chemistry original
Then.
If hexatomic ring list sulfocarbonate can be synthesized using carbonyl sulfide and glycol compound reaction, due to
Glycol compound is lower compared to epoxyalkane price, then party's rule has more IP prospecting and meaning, simultaneously
This is also another new friendly process for synthesizing hexatomic ring list sulfocarbonate.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of synthetic method of hexatomic ring list sulfocarbonate.
In order to solve the above technical problems, a kind of technical scheme provided by the invention is a kind of hexatomic ring list sulfocarbonate
Synthetic method, using carbonyl sulfide and glycol compound as raw material, under the conditions of existing for catalyst and acetonitrile, coupling is de-
Hexatomic ring list sulfocarbonate is obtained after water reaction；Its reactional equation is as follows：
R1, R2, R3 are any combination in hydrogen atom, alkyl, vinyl, phenyl, cyclohexyl, cyclopenta, are to hereafter
Described in glycol compound signal, when R1 is identical with R3, product only have one kind.
Preferably, described glycol compound be selected from 1,3-PD, 2- methyl isophthalic acids, ammediol, 2- ethyl -1,
Ammediol, 2- n-propyl -1,3- propane diols, 2- isopropyl -1,3- propane diols, 2,2- dimethyl -1,3- propane diols, 2- second
Base -2- methyl-1,3-propanediols, 2- phenyl -1,3- propane diols, the chloro- 1,3- propane diols of 2-, the bromo- 1,3- propane diols of 2-, 2- first
Ester group -1,3- propane diols, 2- ethoxycarbonyl -1,3- propane diols, 2- methoxyl group -1,3- propane diols, 2- benzyl -1,3- propane diols, 2-
Phenoxy group -1,3- propane diols, 1,3 butylene glycol, (R)-(-) -1,3 butylene glycol, (S)-(+) -1,3 butylene glycol, 1,3- fourths two
Alcohol, 1,3- pentanediols, 2,4- pentanediols, 1,3- hexylene glycols, 2,4- hexylene glycols, 1,3- heptandiols, 2,4- heptandiols, 1,3- are pungent
At least one of glycol, more preferably 1,3-PD, 2- methyl isophthalic acids, ammediol, 2,2- dimethyl -1,3- third
Glycol, 2- phenyl -1,3- propane diols, the chloro- 1,3- propane diols of 2-, 2- methoxyl group -1,3- propane diols, 2- phenoxy groups -1,3- the third two
At least one of alcohol, 1,3 butylene glycol.
Described catalyst is selected from zinc oxide, zinc hydroxide, zinc salt and alkali metals modified zinc oxide.Zinc salt, which is selected from, to be had
Machine acid zinc salt (such as acetate, stearate), inorganic zinc salt (such as chloride, sulfate, nitrate, phosphate, carbonate,
Subcarbonate and bicarbonate etc.)；More preferably zinc oxide, zinc hydroxide, zinc acetate, zinc chloride, zinc nitrate be wherein
At least one.
Described alkali metal includes lithium, sodium, potassium, caesium wherein at least one.
Described alkali metals modified zinc oxide is lithium carbonate/zinc oxide, sodium carbonate/zinc oxide, potassium carbonate/zinc oxide, carbon
At least one of sour caesium/zinc oxide, is prepared by infusion process.
Preferably, the mol ratio of carbonyl sulfide and glycol compound is 0.1~50：1；Preferably 1~10：1.
Preferably, the mass ratio of acetonitrile and glycol compound is 0.5~50:1；Preferably 1~10：1.
Preferably, the mass ratio of catalyst and glycol compound is 0.5~50:100；Preferably 1~20： 100.
Preferably, reaction temperature is 30~300 DEG C, and the reaction time is 1~24 hour.
The present invention is used as catalyst using zinc oxide, zinc hydroxide, zinc salt and alkali metals modified zinc oxide etc., in second
Under the conditions of nitrile is existing, hexatomic ring list sulfocarbonate is effectively synthesized by carbonyl sulfide and glycol compound, passes through acetonitrile
Hydrolysis can remove a part of water generated in course of reaction, improve the conversion ratio and hexatomic ring list sulphur of glycol compound
For the yield of carbonic ester.Acetonitrile is not only solvent in the reaction system, while it also acts the effect of dehydration, promotes
The progress of reaction.
Because carbonyl sulfide has asymmetrical chemical constitution, when the glycol reacted with carbonyl sulfide is also with asymmetric
During structure (as above shown in reaction equation, i.e. when group R1 and R3 are differed), reaction can generate different hexa-atomic of two kinds of structures
Ring list sulfocarbonate (as above shown in reaction equation), the selectivity (ratio i.e. in the product) of two kinds of products are not urged
The influence of agent, it is only relevant with the structure of glycol.
Advantages of the present invention is as follows:
1) for by carbonyl sulfide and glycol compound reaction synthesize hexatomic ring list sulfocarbonate provide one newly
Thinking；
2) reaction raw materials are cheap and easy to get, and synthesis technique cost is relatively low；
3) conversion ratio and the thio carbon of hexatomic ring list of glycol compound are drastically increased by the use of acetonitrile as dehydrating agent
The yield of acid esters.
Embodiment
Such scheme is described further below in conjunction with specific embodiment.It should be understood that these embodiments are to be used to illustrate
The present invention and be not limited to limit the scope of the present invention.The implementation condition used in embodiment can be according to the condition of specific producer
Further adjustment is done, unreceipted implementation condition is usually the condition in normal experiment.
Introduce and summarize
The present invention by way of example rather than provides the mode of limitation to illustrate.It should be noted that in present disclosure
Described " one " or " one kind " embodiment is not necessarily referring to same embodiment, and refers at least a kind of.
Various aspects of the invention are described below.However, as will be readily apparent to one of skill in the art,
The present invention can be implemented according to the only some or all of aspects of the present invention.For purposes of illustration, specific numbering, material are provided herein
Material and configuration, enable one to thoroughly understand the present invention.However, it will be evident for those of skill in the art
, it is of the invention to implement without concrete details.In other examples, not make the present invention is obscure to be omitted or simplified
Well-known feature.
Various operations are described successively as multiple discrete steps, and with most helpful in the understanding present invention's
Mode illustrates；However, in-order description should not be construed as to imply that these operations are necessarily dependent on order.
Reactant according to type species is illustrated to various embodiments.It will show for those of skill in the art
And be clear to, any number of different types of reactant can be used to implement for the present invention, and be more than those to illustrate mesh
And the reactant that provides herein.In addition, also it is evident that, the invention is not limited in any specific mixing
Example.
Embodiment 1
If the 1,3-PD of dry mass is added into the autoclave of 10ml capacity successively, acetonitrile, catalyst oxidation
The mass ratio of zinc, catalyst and glycol is 0.5:100, the mass ratio of acetonitrile and glycol is 0.5:1.Then reactor is closed,
Carbonyl sulfide gas is passed through to specified pressure, the mol ratio of carbonyl sulfide and glycol is 0.1:1, reactor is placed in 30 DEG C of oil
Reacted 1 hour under self-generated pressure in bath.Reaction is cooled to room temperature, emptying gas after terminating, sampling is calculated by nucleus magnetic hydrogen spectrum
Yield, test result are shown in Table 1.
Embodiment 2
If the 1,3-PD of dry mass, acetonitrile, catalyst hydrogen-oxygen are added into the autoclave of 10ml capacity successively
The mass ratio of change zinc, catalyst and glycol is 1:100, the mass ratio of acetonitrile and glycol is 1:1.Then reactor is closed, led to
Enter carbonyl sulfide gas to specified pressure, the mol ratio of carbonyl sulfide and glycol is 0.5:1, reactor is placed in 50 DEG C of oil baths
In reacted 2 hours under self-generated pressure.Reaction is cooled to room temperature, emptying gas after terminating, sampling is calculated by nucleus magnetic hydrogen spectrum and produced
Rate, test result are shown in Table 1.
Embodiment 3
If adding the 2- methyl isophthalic acids of dry mass into the autoclave of 10ml capacity successively, ammediol, acetonitrile, urge
The mass ratio of agent zinc acetate, catalyst and glycol is 2:100, the mass ratio of acetonitrile and glycol is 2:1.Then by reactor
Closing, carbonyl sulfide gas is passed through to specified pressure, the mol ratio of carbonyl sulfide and glycol is 1:1, reactor is placed in 80 DEG C
Reacted 5 hours under self-generated pressure in oil bath.Reaction is cooled to room temperature, emptying gas after terminating, sampling passes through nucleus magnetic hydrogen spectrum meter
Yield is calculated, test result is shown in Table 1.
Embodiment 4
If the NPG of dry mass, second are added into the autoclave of 10ml capacity successively
The mass ratio of nitrile, catalyst zinc chloride, catalyst and glycol is 5:100, the mass ratio of acetonitrile and glycol is 5:1.Then will be anti-
Answer kettle to close, be passed through carbonyl sulfide gas to specified pressure, the mol ratio of carbonyl sulfide and glycol is 2:1, reactor is placed in
Reacted 8 hours under self-generated pressure in 100 DEG C of oil baths.Reaction is cooled to room temperature, emptying gas after terminating, sampling passes through nuclear-magnetism
Hydrogen spectrum calculates yield, and test result is shown in Table 1.
Embodiment 5
If adding the PPD of dry mass into the autoclave of 10ml capacity successively, acetonitrile, urge
The mass ratio of agent zinc nitrate, catalyst and glycol is 8:100, the mass ratio of acetonitrile and glycol is 8:1.Then by reactor
Closing, carbonyl sulfide gas is passed through to specified pressure, the mol ratio of carbonyl sulfide and glycol is 5:1, reactor is placed in 120
Reacted 10 hours under self-generated pressure in DEG C oil bath.Reaction is cooled to room temperature, emptying gas after terminating, sampling passes through nuclear-magnetism hydrogen
Spectrum calculates yield, and test result is shown in Table 1.
Embodiment 6
If adding the PPD of dry mass into the autoclave of 10ml capacity successively, acetonitrile, urge
The mass ratio of agent lithium carbonate/zinc oxide, catalyst and glycol is 10:100, the mass ratio of acetonitrile and glycol is 10:1.Then
Reactor is closed, is passed through carbonyl sulfide gas to specified pressure, the mol ratio of carbonyl sulfide and glycol is 8:1, by reactor
It is placed in 150 DEG C of oil baths and is reacted 12 hours under self-generated pressure.Reaction is cooled to room temperature, emptying gas after terminating, and sampling passes through
Nucleus magnetic hydrogen spectrum calculates yield, and test result is shown in Table 1.
Embodiment 7
If 2- methoxyl groups -1,3-PD of dry mass is added into the autoclave of 10ml capacity successively, acetonitrile,
The mass ratio of catalyst sodium carbonate/zinc oxide, catalyst and glycol is 20:100, the mass ratio of acetonitrile and glycol is 20:1.So
Reactor is closed afterwards, is passed through carbonyl sulfide gas to specified pressure, the mol ratio of carbonyl sulfide and glycol is 10:1, will be anti-
Answer kettle to be placed in 200 DEG C of oil baths to react 16 hours under self-generated pressure.Reaction is cooled to room temperature, emptying gas, sampling after terminating
Yield is calculated by nucleus magnetic hydrogen spectrum, test result is shown in Table 1.
Embodiment 8
If 2- phenoxy groups -1,3-PD of dry mass is added into the autoclave of 10ml capacity successively, acetonitrile,
The mass ratio of catalyst potassium carbonate/zinc oxide, catalyst and glycol is 30:100, the mass ratio of acetonitrile and glycol is 30:1.So
Reactor is closed afterwards, is passed through carbonyl sulfide gas to specified pressure, the mol ratio of carbonyl sulfide and glycol is 30:1, will be anti-
Answer kettle to be placed in 250 DEG C of oil baths to react 20 hours under self-generated pressure.Reaction is cooled to room temperature, emptying gas, sampling after terminating
Yield is calculated by nucleus magnetic hydrogen spectrum, test result is shown in Table 1.
Embodiment 9
If the 1,3-BDO of dry mass, acetonitrile, catalyst carbonic acid are added into the autoclave of 10ml capacity successively
The mass ratio of caesium/zinc oxide, catalyst and glycol is 50:100, the mass ratio of acetonitrile and glycol is 50:1.Then by reactor
Closing, carbonyl sulfide gas is passed through to specified pressure, the mol ratio of carbonyl sulfide and glycol is 50:1, reactor is placed in 300
Reacted 24 hours under self-generated pressure in DEG C oil bath.Reaction is cooled to room temperature, emptying gas after terminating, sampling passes through nuclear-magnetism hydrogen
Spectrum calculates yield, and test result is shown in Table 1.
When R1 is identical with R3, product only has one kind, such as embodiment 1~8 in table.When R1 is with R3 differences, R1 pairs in product
The substituent that molecular weight is larger is answered, product 1 and product 2 are distinguished with this.
The test result of the reaction product of the embodiment 1~9 of table 1.
1Yield：Determined by nucleus magnetic hydrogen spectrum, product 1 and product 2 in yield 1 and the difference counterparty's formula of yield 2.
Specific embodiment described above is only the preferred embodiment of the present invention, it is noted that for the art
For those of ordinary skill, under the premise without departing from the principles of the invention, some improvement or replacement can also be made, these change
Enter or replace to should also be as being considered as protection scope of the present invention.
Claims (8)
- A kind of 1. synthetic method of hexatomic ring list sulfocarbonate, it is characterised in that using carbonyl sulfide and glycol compound as Raw material, under the conditions of existing for catalyst and acetonitrile, hexatomic ring list sulfocarbonate is obtained after coupling dehydration.
- 2. synthetic method according to claim 1, it is characterised in that the glycol compound be selected from 1,3-PD, 2- methyl-1,3-propanediols, 2- ethyl -1,3- propane diols, 2- n-propyl -1,3- propane diols, 2- isopropyl -1,3- propane diols, 2,2- dimethyl -1,3- propane diols, 2- Ethyl-2-Methyl -1,3- propane diols, 2- phenyl -1,3- propane diols, the chloro- 1,3- third of 2- The bromo- 1,3- propane diols of glycol, 2-, 2- carbomethoxy -1,3- propane diols, 2- ethoxycarbonyl -1,3- propane diols, 2- methoxyl groups -1,3- third Glycol, 2- benzyl -1,3- propane diols, 2- phenoxy group -1,3- propane diols, 1,3 butylene glycol, (R)-(-) -1,3 butylene glycol, (S) - (+) -1,3-BDO, 1,3-BDO, 1,3- pentanediols, 2,4- pentanediols, 1,3- hexylene glycols, 2,4- hexylene glycols, 1,3- heptan At least one of glycol, 2,4- heptandiols, 1,3- ethohexadiols, more preferably 1,3-PD, 2- methyl isophthalic acids, 3- the third two Alcohol, 2,2- dimethyl -1,3- propane diols, 2- phenyl -1,3- propane diols, the chloro- 1,3- propane diols of 2-, 2- methoxyl groups -1,3- the third two At least one of alcohol, 2- phenoxy group -1,3- propane diols, 1,3 butylene glycol.
- 3. synthetic method according to claim 1, it is characterised in that the catalyst is selected from zinc oxide, zinc hydroxide, zinc Salt and alkali metals modified zinc oxide.
- 4. synthetic method according to claim 3, it is characterised in that the alkali metals modified zinc oxide is lithium carbonate/oxygen Change at least one of zinc, sodium carbonate/zinc oxide, potassium carbonate/zinc oxide, cesium carbonate/zinc oxide.
- 5. synthetic method according to claim 1, it is characterised in that the mol ratio of carbonyl sulfide and glycol compound is 0.1~50：1.
- 6. synthetic method according to claim 1, it is characterised in that the mass ratio of acetonitrile and glycol compound is 0.5 ~50:1.
- 7. synthetic method according to claim 1, it is characterised in that the mass ratio of catalyst and glycol compound is 0.5~50:100.
- 8. synthetic method according to claim 1, it is characterised in that reaction temperature is 30~300 DEG C, the reaction time 1 ~24 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358886A (en) * | 2018-04-04 | 2018-08-03 | 常熟理工学院 | A method of preparing trimethylene list sulfocarbonate with ionic liquid-catalyzed |
| CN108530417A (en) * | 2018-05-10 | 2018-09-14 | 杭州普力材料科技有限公司 | A kind of preparation method of trimethylene list sulfocarbonate |
| CN115925673A (en) * | 2022-11-10 | 2023-04-07 | 浙江大学杭州国际科创中心 | Preparation method of six-membered ring monothiocarbonate |
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| CN101029039A (en) * | 2007-04-13 | 2007-09-05 | 中国科学院山西煤炭化学研究所 | Method for synthesizing five-membered ring carbonate ester |
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- 2017-09-25 CN CN201710874357.6A patent/CN107721974A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101029039A (en) * | 2007-04-13 | 2007-09-05 | 中国科学院山西煤炭化学研究所 | Method for synthesizing five-membered ring carbonate ester |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358886A (en) * | 2018-04-04 | 2018-08-03 | 常熟理工学院 | A method of preparing trimethylene list sulfocarbonate with ionic liquid-catalyzed |
| CN108530417A (en) * | 2018-05-10 | 2018-09-14 | 杭州普力材料科技有限公司 | A kind of preparation method of trimethylene list sulfocarbonate |
| CN115925673A (en) * | 2022-11-10 | 2023-04-07 | 浙江大学杭州国际科创中心 | Preparation method of six-membered ring monothiocarbonate |
| CN115925673B (en) * | 2022-11-10 | 2024-06-11 | 浙江大学杭州国际科创中心 | Preparation method of six-membered ring monothiocarbonate |
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