CN104478645B - A kind of preparation method of 2-vinyl naphthalene compound - Google Patents
A kind of preparation method of 2-vinyl naphthalene compound Download PDFInfo
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- CN104478645B CN104478645B CN201410792869.4A CN201410792869A CN104478645B CN 104478645 B CN104478645 B CN 104478645B CN 201410792869 A CN201410792869 A CN 201410792869A CN 104478645 B CN104478645 B CN 104478645B
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Abstract
The present invention relates to the preparation method of a kind of 2 vinyl naphthalene compounds, described preparation method is with 2 acetyl group naphthalenes as raw material, and carbonyl reduction is hydroxyl in alcohols solvent by step (1), obtains intermediate；Step (2) hydroxyls dehydrate under polymerization inhibitor, catalysts conditions obtains vinyl.Dehydration is particularly as follows: by catalyst, step (1) gained intermediate, polymerization inhibitor mix homogeneously in pre-heat channel, add in reactor I and react, then continues reaction through reactor II.On condenser, gaseous product is condensed into liquid, obtains product from receiving tank, and vacuum maintains 0.1 ~ 2mmHg.Preparation method provided by the present invention, raw material is easy to get, yield high, and side reaction is few, and equipment needed thereby is simple, it is not necessary to high-temperature and high-pressure conditions.And, the present invention is suitable for the industrial amplification production of 2 vinyl naphthalene compounds.
Description
Technical field
The present invention relates to organic synthesis field, particularly relate to the preparation method of a kind of 2-vinyl naphthalene compound.
Background technology
Vinyl naphthalene (vinylnaphthalene) is the intermediate of synthesis of vinyl naphthalene polymer.Because it contains active vinyl, vinyl naphthalene extensively can should be used as medicine intermediate, dyestuff intermediate and optical element coating material etc..Various high molecular polymers can be given high heat-resisting by 2-vinyl naphthalene, low-k, low-dielectric loss, high index of refraction, the feature such as difficult combustion and agent of low hygroscopicity.As: polym.Eng.Sci., 33 (9), 549-58 (1993) and Macromolecules., discloses styrene and 2-vinyl naphthalene combined polymerization and Tg improves about 15 degree in 29 (10), 620-6245 (1996).
Patent publication No.:
CN101248391
Middle report vinyl naphthalene is possible to prevent anti-etching figure the subsiding after development of the granular with anti-etching figure as cellular construction gained coated substance.
The method of existing synthesis of vinyl naphthalene is as follows:
US5087769
Disclose
6-
Substituted
-2-
The synthetic method of vinyl naphthalene, its raw material is
2
The acyl-naphthaline that is replaced of position, its raw material has related to by catalytic hydrogenation, has restored dehydration and obtain
2-
The preparation method of vinyl naphthalene compound.Though can obtain product under this reaction condition, but its process conditions are harsh, technological requirement is complicated, operation easier is bigger.
US5191133Disclose and take under condition of high voltage, to carry out catalytic hydrogenation, again processed and obtain 2- The technique of vinyl naphthalene compound.
Unexamined Patent
06-138985
The reaction of ethylnaphthalene direct dehydrogenation is also obtained vinyl naphthalene by number publication.The method reaction raw materials and product are the most single, and to production Technology, catalyst activity requires the highest, is not suitable for general chemical enterprise.
And method most expensive starting materials post processing difficulty of some literature periodicals report, be more not suitable for production method.As:
Selective
Arylation and Vinylation at the
α
Position of Vinylarenes By Zou,yinjun te al from
Chemistry - A European Journal 19(10),3504-3511;2013
Report is used
2-
Bromonaphthalene with
F3BCH2CH2
Reaction preparation.The method expensive starting materials, post processing trouble is not suitable for commercial production；
Low pressure vinylation of aryl
and vinyl halides via Heck-Mizoroki reactions Using ethylene by smith ,Craig R and RajanBabu,T.V. From
Tetrahedron 66(5) 1102-1110;2010
With
2-
Bromonaphthalene with
CH2CH2
Reaction, this reaction selectivity is bad, and catalyst activity is required height.
In prior art, the facile syntheesis technique of vinyl naphthalene lacks, and existing process conditions are harsh, technological requirement is complicated, and products obtained therefrom also exists impurity content compared with the shortcoming such as big, product yield is low, product content is low.Therefore, the improvement of the synthesis technique of vinyl naphthalene is significant.
Summary of the invention
For problems of the prior art, it is an object of the invention to provide one 2- Vinyl naphthalene compound is mainly 2- The preparation method of vinyl naphthalene.Described preparation method raw material is easy to get, technique is simple, easy and simple to handle, and there is low cost and the high advantage of productivity。
The present invention provides a kind of
2-
The preparation method of vinyl naphthalene compound, the method comprises the following steps: by
2-
Acetyl group naphthalene is raw material, is hydroxyl by carbonyl reduction, then by hydroxyls dehydrate, to obtain final product.
Concrete, said method comprising the steps of
:
(
1
) with
2-
Acetyl group naphthalene is raw material, is dissolved in alcoholic solvent, adds reducing agent, carries out reduction reaction；Add acid regulation reactant liquor
pH
Extremely
6-8
Separate out solid, obtain product intermediate；
(
2
) by step (
1
Products obtained therefrom intermediate in), with catalyst, polymerization inhibitor mixing preheating, carries out dehydration and obtains product；
(
3
) to step (
2
) gained crude product carries out recrystallization.
In said method:
Described step
1
In):
Alcohol
The consumption of solvent is raw material weight
3.33
Times；
Described reducing agent is sodium borohydride, potassium borohydride or lithium aluminium hydride reduction, and described reducing agent with the mol ratio of raw material is
1:0.25-1:0.45
；
The temperature of described reduction reaction is
10-40
DEG C, the response time is
2-3 h
；
Described addition acid regulation reactant liquor
pH
Value, described acid is hydrochloric acid, and described aqueous acid mass fraction is
5-15%
；
Described step (
1
) and (
2
Through post processing purification operations before): it is it that products obtained therefrom intermediate joins quality
2
Toluene again dissolves, stands
30min
Layering takes upper organic phase, then concentrates and (keeps temperature
70
Spending concentrating under reduced pressure carried out above, concentrated to obtain the product intermediate of molten, concentrating under reduced pressure improves efficiency) organic phase solution, then crystallisation by cooling.
Described step (
2
In):
In pre-heat channel, intermediate adds heat fusing completely, and the temperature of heating is not less than
120
Degree, adds polymerization inhibitor, catalyst after thawing；
Described polymerization inhibitor is 4- Methoxyphenol, hydroquinone, polymerization inhibitor 168 , copper sulfate, described polymerization inhibitor with the mass ratio of product intermediate is10-5 :1-0.01:1 。
Described catalyst is potassium acid sulfate, and described catalyst with the mol ratio of product intermediate is
0.05:1-0.1:1
。
The dehydration time is
1-5 h
, by controlling the joining day adjusting reaction time of material.In course of reaction, vacuum maintains
0.1~2mmHg
。
Described step (
3
In):
Ethanol consumption is crude product weight
2.5
Times.
Provided by the present invention
2-
The preparation method of vinyl naphthalene compound has the advantage that
1
, raw material is easy to get, technique is simple, easy and simple to handle, and it is high to have low cost and productivity, the advantage that products obtained therefrom purity is high；
2
, with prior art present in compared with preparation method, preparation method of the present invention is without using the harsh process conditions such as high pressure, and products obtained therefrom productivity is high and impurity content is few, can conveniently and effectively be applied to
2-
In the production of vinyl naphthalene compound.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
The present invention provides a kind of
2-
The preparation method of vinyl naphthalene compound, by
2-
Acetyl group naphthalene is raw material, by being hydroxyl by carbonyl reduction, then is obtained the method for vinyl by hydroxyls dehydrate and prepares
2-
Vinyl naphthalene compound
:
Wherein, described preparation method comprises the following steps
:
(
1
) with
2-
Acetyl group naphthalene is raw material, is dissolved in alcoholic solvent, adds reducing agent,
10
~
40
Reduction reaction is carried out at DEG C
2
~
3 h
.Described reducing agent is sodium borohydride, potassium borohydride or lithium aluminium hydride reduction, and described reducing agent with the mol ratio of raw material is
1:0.25
~
1:0.45
；Described alcoholic solvent is methanol, ethanol water.After reaction, by adding aqueous acid, regulate reactant liquor
pH
Extremely
6-8
Separating out solid, obtain product intermediate, it is it that products obtained therefrom intermediate adds quality
2
Toluene again dissolves, and stratification takes upper organic phase, concentrates organic phase solution, crystallisation by cooling.Wherein said aqueous acid mass fraction is
5
~
15%
；The preferred hydrochloric acid of described acid；
( 2 ) by step ( 1 In), products obtained therefrom intermediate adds heat fusing and adds polymerization inhibitor and catalyst the most afterwards, is preheated to 120 ~ 130 DEG C pass through reaction unit I,II Carrying out dehydration, in reaction, water byproduct is directly removed by vacuum, departs from reaction system, and the dehydration time is 1 ~ 5 h .Described polymerization inhibitor is 4- Methoxyphenol, hydroquinone, polymerization inhibitor 168 , copper sulfate, described polymerization inhibitor with the mass ratio of product intermediate is10-5: 1～10-2:1；Described catalyst is potassium acid sulfate, and described catalyst with the mol ratio of product intermediate is 0.1:1 ~ 0.05:1 ；
(
3
) by step (
2
In), products obtained therefrom carries out recrystallization, and it is crude product that solvent adds quality amount
2.5
Times.
Embodiment
1
Will
10 kg
Methanol joins in the reactor with cold cooling unit, adds to it
3 kg
's
2-
Acetyl group naphthalene, opens stirring and makes it dissolve, until it dissolves completely.Reacting liquid temperature is down to
10
DEG C, add sodium borohydride
2.67 kg
Reduce, keep reaction temperature
10
React about DEG C
2 h
.With
TLC
Monitoring reactant liquor in real time, determine wherein without stopped reaction after starting material left, adding mass fraction in still is
10%
Hydrochloric acid solution, regulation system
pH
Extremely
7
, separate out solid, be centrifuged to obtain product intermediate
2-
Hydroxyethyl naphthalene crude product.It is it by products obtained therefrom crude intermediate quality
2
Toluene heating for dissolving again, stratification, separatory is removed aqueous phase, is existed by gained organic phase solution
70
Concentrate at DEG C, after completing, molten product is placed in pallet and cools down to obtain product intermediate.By parts by weight it is again
7200
The product intermediate of part adds in the pre-heat channel with heating and stirring device and adds heat fusing, and rear melted addition parts by weight are
20
Part
4-
Methoxyphenol and parts by weight are
56
The potassium acid sulfate of part.Enter speed by regulation, made material exist
1h
In reacted by reactor.Reactor
I
Temperature is set
135
Degree, temperature of reactor is arranged
120
Degree, condensate temperature
70
Degree.Obtaining yield after reaction is
88%
Product crude product, wherein
2-
Vinyl naphthalene content is
95%
.Directly add in the reception tank of function to be heated
2.5
Anhydrous alcohol solution again, recrystallization.Finally obtaining product, total recovery is
79%
, product
GC
Purity reaches
99.1%
。
Embodiment
2
Will
11 kg95%
Ethanol joins in cold cooling unit reactor to be had, and adds to it
3kg
's
2-
Acetyl group naphthalene, opens stirring and makes it dissolve, until it dissolves completely.Reacting liquid temperature is down to
10
Within DEG C, add potassium borohydride
1.483 kg
Reduce, keep reaction temperature
10
Reaction is continued within DEG C
3 h
.With
TLC
Monitoring reactant liquor in real time, determine wherein without stopped reaction after starting material left, adding mass fraction in still is
10%
Hydrochloric acid solution, regulation system
pH
Extremely
7
, separate out product, be centrifuged to obtain product intermediate
2-
Hydroxyethyl naphthalene crude product.It is it by products obtained therefrom crude intermediate quality
2
Toluene heating for dissolving again, stratification, separatory is removed aqueous phase, is existed by gained organic phase solution
70
Concentrate at DEG C, after completing, molten product is placed in pallet and cools down to obtain product intermediate.By parts by weight it is again
7200
Adding heat fusing in the reactor of the product intermediate addition band heated and stirred of part, rear melted addition parts by weight are
18
Hydroquinone and the parts by weight of part are
32
The potassium acid sulfate of part.Enter speed by regulation, made material exist
1h
In reacted by reactor.Reactor
I
Temperature is set
140
Degree, temperature of reactor is arranged
125
Degree, condensate temperature
70
Degree.Obtaining yield after reaction is
86%
Product crude product, wherein
2-
Vinyl naphthalene content is
94.5%
.Directly add in the reception tank of function to be heated
2.5
Anhydrous alcohol solution again, recrystallization.Finally obtaining product, total recovery is
77%
, product
GC
Purity reaches
99.0%
。
Embodiment
3
Will
10 kg
Methanol joins in the reactor with cold cooling unit, adds to it
3 kg
's
2-
Acetyl group naphthalene, opens stirring and makes it dissolve, until it dissolves completely.Reacting liquid temperature is adjusted to
40
DEG C, add sodium borohydride
1.483 kg
Reduce, keep reaction temperature
40
React about DEG C
3 h
.With
TLC
Monitoring reactant liquor in real time, determine wherein without stopped reaction after starting material left, adding mass fraction in still is
10%
Hydrochloric acid solution, regulation system
pH
Extremely
7
, separate out solid, be centrifuged to obtain product intermediate
2-
Hydroxyethyl naphthalene crude product.It is it by products obtained therefrom crude intermediate quality
2
Toluene heating for dissolving again, stratification, separatory is removed aqueous phase, is existed by gained organic phase solution
70
Concentrate at DEG C, after completing, molten product is placed in pallet and cools down to obtain product intermediate.By parts by weight it is again
7200
The product intermediate of part adds in the reactor with heating and stirring device and adds heat fusing, and rear melted addition parts by weight are
0.072
The polymerization inhibitor of part
168
With parts by weight it is
428
The potassium acid sulfate of part.Enter speed by regulation, made material exist
1h
In reacted by reactor.Reactor
I
Temperature is set
130
Degree, temperature of reactor is arranged
120
Degree, condensate temperature
70
Degree.Obtaining yield after reaction is
84%
Product crude product, wherein
2-
Vinyl naphthalene content is
95.5%
.Directly add in the reception tank of function to be heated
2.5
Anhydrous alcohol solution again, recrystallization.Finally obtaining product, total recovery is
78%
, product
GC
Purity reaches
99.2%
。
Embodiment
4
Will
60 kg
Methanol joins in the reactor with cold cooling unit, adds to it
18 kg
's
2-
Acetyl group naphthalene, opens stirring and makes it dissolve, until it dissolves completely.Reacting liquid temperature is adjusted to
40
DEG C, add sodium borohydride
12.72 kg
Reduce, keep reaction temperature
40
React about DEG C
3 h
.With
TLC
Monitoring reactant liquor in real time, determine wherein without stopped reaction after starting material left, adding mass fraction in still is
10%
Hydrochloric acid solution, regulation system
pH
Extremely
7
, separate out solid, be centrifuged to obtain product intermediate
2-
Hydroxyethyl naphthalene crude product.It is it by products obtained therefrom crude intermediate quality
2
Toluene heating for dissolving again, stratification, separatory is removed aqueous phase, is existed by gained organic phase solution
70
Concentrate at DEG C, after completing, molten product is placed in pallet and cools down to obtain product intermediate.By parts by weight it is again
10800
The product intermediate of part adds in the reactor with heating and stirring device and adds heat fusing, and rear melted addition parts by weight are
0.12
The polymerization inhibitor of part
168
With parts by weight it is
60
The potassium acid sulfate of part.Enter speed by regulation, made material exist
4h
In reacted by reactor.Reactor
I
Temperature is set
135
Degree, temperature of reactor is arranged
125
Degree, condensate temperature
70
Degree.Obtaining yield after reaction is
89%
Product crude product, wherein
2-
Vinyl naphthalene content is
95.3%
.Directly add in the reception tank of function to be heated
2.5
Anhydrous alcohol solution again, recrystallization.Finally obtaining product, total recovery is
80%
, product
GC
Purity reaches
99.1%
。
Although, use general explanation, detailed description of the invention and test, the present invention is described in detail, but on the basis of the present invention, can make some modifications or improvements it, and this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention.
Claims (1)
1. the preparation method of a 2-vinyl naphthalene compound, it is characterised in that with 2 acetyl naphthalene as raw material, by being hydroxyl by carbonyl reduction, prepared 2-vinyl naphthalene compound by the method for hydroxyls dehydrate again；Reaction equation:
Wherein, described preparation method comprises the following steps:
(1) with 2 acetyl naphthalene as raw material, it is dissolved in alcoholic solvent, adds reducing agent, at 40 DEG C, carry out reduction reaction 2～3 h；Described reducing agent is sodium borohydride, potassium borohydride, and described reducing agent is 1:0.25～1:0.45 with the mol ratio of raw material；Described alcoholic solvent is methanol, 95% ethanol water；After reaction, by adding aqueous acid, regulation reactant liquor pH to 6-8 separates out solid, obtaining product intermediate, it is that its toluene of 2 times dissolves that products obtained therefrom intermediate adds quality, and stratification takes upper organic phase, concentrating organic phase solution, crystallisation by cooling obtains intermediate；Wherein said aqueous acid mass fraction is 5～15%；Described acid is hydrochloric acid；
(2) products obtained therefrom intermediate in step (1) is added heat fusing and add polymerization inhibitor and catalyst the most afterwards, it is preheated to 120～130 DEG C by reactor I, II carries out dehydration, reactor I temperature is 130 ~ 140 degree, reactor II temperature is 120 ~ 125 degree, and in course of reaction, vacuum maintains 0.1 ~ 2mmHg, and in reaction, water byproduct is directly removed by vacuum, departing from reaction system, the dehydration time is 1～5 h；Described polymerization inhibitor is 4-methoxyphenol, hydroquinone；Described catalyst is potassium acid sulfate, and described catalyst is 0.1:1～0.05:1 with the mol ratio of product intermediate；
(3) products obtained therefrom in step (2) carrying out recrystallization, solvent adds 2.5 times that quality is crude product, and wherein solvent is ethanol.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747162A (en) * | 2009-12-25 | 2010-06-23 | 南京工业大学 | Synthetic technology of p-methoxystyrene |
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2014
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747162A (en) * | 2009-12-25 | 2010-06-23 | 南京工业大学 | Synthetic technology of p-methoxystyrene |
Non-Patent Citations (2)
| Title |
|---|
| SYNTHESIS AND POLYMERIZATION OF 2-VINYLQUINOLINE AND 2-VINYLNAPHTHALENE WITH A1Et3-VCI3: INFLUENCE OF PYRIDINE AS DONOR LIGAND;Y. BENITO et al.,;《Eur. Polym. J.》;19901231;第26卷(第6期);第690页左栏第2和3段 * |
| 对氟苯乙烯的合成;何明阳等;《石油化工》;20011231;第30卷(第5期);第381页1.3.3 * |
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