CN108129251A - A kind of synthesis technology of 2- ethyl styrenes - Google Patents
A kind of synthesis technology of 2- ethyl styrenes Download PDFInfo
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- CN108129251A CN108129251A CN201711404294.4A CN201711404294A CN108129251A CN 108129251 A CN108129251 A CN 108129251A CN 201711404294 A CN201711404294 A CN 201711404294A CN 108129251 A CN108129251 A CN 108129251A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/34—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen reacting phosphines with aldehydes or ketones, e.g. Wittig reaction
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Abstract
The invention discloses a kind of synthesis technologies of 2 ethyl styrene；It is as follows that 2 ethyl bromobenzenes are dissolved in dry polar organic solvent by (1), under cryogenic conditions, n-BuLi is added dropwise, time for adding is 14 hours, after being added dropwise, insulation reaction 16 hours under low temperature are subsequently added into anhydrous N, N dimethylformamides, 16 hours are kept the temperature after adding, adds and solvent quenching, washing is quenched, stratification, it is not purified separately after organic phase concentration, obtains intermediate, yield is 95 100%；(2) intermediate, inorganic base, trityl group phosphine and the solvent of drying are mixed, after mixing, under inert atmosphere, insulation reaction 2 10 hours under counterflow condition, post processing obtains pure target product, yield 80 90%.The product that the method for the present invention is produced is with high-quality, stable operation, high income, the three wastes are few, production cost is low.
Description
Technical field
The present invention relates to a kind of methods for preparing 2- ethyl styrenes, belong to organic synthesis technology field.
Background technology
Olefin-containing class compound is the important monomer of polymer, has reactivity, hydrogenation, halogenation, hydration, halogen can occur
The addition reactions such as hydrogenation, hypohalogenous acids, Sulfation, epoxidation, polymerization, the also oxidable fracture that double bond occurs, generation aldehyde, carboxylic
Acid etc., olefin-containing class compound are easy to carry out structural modification, it is convenient to introduce various functions base.2- ethyl styrenes are in chemistry
In be a kind of very wide link block of purposes, do not find related methods of synthesis in document；This patent is designed by with cheap and easy to get
2- ethyl bromobenzenes for raw material, 2- ethylo benzene formaldehyde is obtained after functional group converts, is then flowed back again with trityl group phosphine, alkali
Reaction, you can obtain target compound 2- ethyl styrenes.
Invention content
For the document for there are not synthesis 2- ethyl styrenes in the prior art, 2- ethylo benzenes are prepared the present invention provides a kind of
The synthesis route of ethylene, the product of production have that high-quality, stable operation, high income, the three wastes are few, production cost is low.
Technical scheme of the present invention is specifically described as follows.
A kind of synthesis technology of 2- ethyl styrenes, is as follows,
(1) 2- ethyl bromobenzenes are dissolved in dry polar organic solvent, under cryogenic conditions, n-BuLi, drop is added dropwise
It is 0.5-4 hours between added-time, after being added dropwise, insulation reaction 1-6 hours under low temperature, is subsequently added into anhydrous N, N- dimethyl formyls
Amine keeps the temperature 1-6 hours after adding, and adds and solvent quenching, washing is quenched, and stratification is not purified separately after organic phase concentration, obtained
To intermediate 2- ethylo benzene formaldehyde, it is directly used in step (2) reaction, yield 95-100%；
(2) intermediate 2- ethylo benzenes formaldehyde, inorganic base, trityl group phosphine and the solvent of drying are mixed, after mixing,
Under inert atmosphere, insulation reaction 2-10 hours under counterflow condition, after reaction, post processing obtains pure target product, yield
80-90%.
In the present invention, in step (1), low temperature is -60 DEG C -78 DEG C.
In the present invention, in step (1), dry polar organic solvent is dichloromethane or tetrahydrofuran.
In the present invention, in step (1), the molar ratio of 2- ethyl bromobenzenes, n-BuLi and n,N-Dimethylformamide is 1:
(1.1-2.0):The volume mass ratio of (1.2-2.0), dry polar organic solvent and 2- ethylo benzene formaldehyde is 10:1~20:
1mL/g。
In the present invention, in step (1), reagent is quenched as saturated ammonium chloride solution.
In the present invention, in step (1), time for adding is 0.5~1 hour, and 1~2 is kept the temperature under low temperature after dropwise addition n-BuLi
Hour, after adding n,N-Dimethylformamide, keep the temperature 1~2 hour.
In the present invention, in step (2), inorganic base for potassium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate or
It is any in calcium hydroxide.
In the present invention, in step (2), the molar ratio of 2- ethylo benzenes formaldehyde, inorganic base and trityl group phosphine is 1:(1.1-
2.0):(1.1-2.5)。
In the present invention, in step (2), dry solvent is any in hexamethylene or Isosorbide-5-Nitrae-dioxane；Intermediate
The volume ratio of 2- ethylo benzenes formaldehyde and dry solvent is 1:8~1:15.
In the present invention, in step (2), the method for post processing is specific as follows：The solution after reaction was carried out first
Filter, obtained filtrate are washed successively, and ethyl acetate extraction, dry, concentration ethyl acetate add in petroleum ether after concentration, fills
Triphenylphosphine oxide is analyzed, filtering and concentrating obtains 2- ethyl styrenes again.
In the present invention, in step (2), kept the temperature under counterflow condition 7-8 hours anti-.
Compared to the prior art, the beneficial effects of the present invention are：
The present invention designs the synthesis route of a rational simple 2- ethyl styrene.The present invention is using cheap
The 2- ethyl bromobenzenes being easy to get are raw material, and 2- ethylamino benzonitriles are directly obtained by the reaction with DMF in dry solvent in the presence of low temperature
Aldehyde then with preparing 2- ethyl styrenes with trityl group phosphine back flow reaction in the environment of alkali, obtains crude product through washing, oil
The method purifying of ether washing filtering, you can the target product of high-purity is obtained, not using your reagent, complicated purifying hand
Section, this process route synthesis o-ethyl styrene process costs are low, easy to operate, and purity is high, high income, yield 80% with
On.
Specific embodiment
In conjunction with embodiment, the invention will be further described, but the implementation of the present invention is not limited to that.
Using the polar organic solvent in step (1) as DMF, the inorganic base in step (2) is for potassium carbonate, the present invention closes
Chemical equation into technique is as follows：
The synthesis technology of 1 2- ethyl styrenes of embodiment, its step are as follows：
First, the synthesis of 2- ethylo benzenes formaldehyde
2- ethyl bromobenzenes (6g, 32.4mmol) are dissolved in 100 milliliters dry of THF, are subsequently cooled to -78 DEG C,
Tert-butyl lithium cyclohexane solution 2.5mol/L (14.4ml) is added dropwise, time for adding is 0.5 hour, and temperature is controlled not during being added dropwise
More than -65 DEG C, after being added dropwise, reacted at -75 DEG C 1 hour, then add in 3mlDMF solution insulation reaction 1 hour, contact plate
Detection, saturated ammonium chloride solution quenching, washing, drying are concentrated under reduced pressure, can obtain colourless solution (4.3g, yield 98.8%).
2nd, the synthesis of 2- ethyl styrenes
2- ethylo benzenes formaldehyde (4.35g) is placed in single-necked flask, adds in 6.7g potassium carbonate and triphenylmethylphosphonium bromide
Phosphine 18g adds in 40 milliliters of dry Isosorbide-5-Nitrae-dioxane, under nitrogen protection, is warming to 110 DEG C of back flow reactions, reacts 6 hours
TLC plates detect, and are then cooled to room temperature, are filtered, washed again after petroleum ether, petroleum ether is added in after reduced pressure
Solid precipitation afterwards is filtered again, and collection liquid is mutually concentrated under reduced pressure, and can obtaining colourless liquid product 2- ethyl styrenes, (3.64g is received
Rate 85%).1H NMR(501MHz,CDCl3) δ 7.49 (dd, J=13.8,12.7Hz, 1H), 7.25-7.16 (m, 3H), 7.02
(dd, J=17.4,11.0Hz, 1H), 5.67 (dd, J=17.4,1.1Hz, 1H), 5.31 (dd, J=11.0,1.1Hz, 1H),
2.73 (q, J=7.6Hz, 2H), 1.22 (t, J=7.6Hz, 3H)
The synthesis technology of 2 2- ethyl styrenes of embodiment, its step are as follows：
First, the synthesis of 2- ethylo benzenes formaldehyde
2- ethyl bromobenzenes (6g, 32.4mmol) are dissolved in 100 milliliters dry of dichloromethane, be subsequently cooled to-
75 DEG C, tert-butyl lithium cyclohexane solution 2.5mol/L (18ml) is added dropwise, time for adding is 0.5 hour, and temperature is controlled during being added dropwise
Degree is no more than -65 DEG C, after being added dropwise, and is reacted at -75 DEG C 1 hour, it is small then to add in 3.7mlDMF solution insulation reaction 1
When, contact plate detection, saturated ammonium chloride solution quenching, washing, drying are concentrated under reduced pressure, can obtain colourless solution (4.27g, yield
99%).
2nd, the synthesis of 2- ethyl styrenes
2- ethylo benzenes formaldehyde (4.35g) is placed in single-necked flask, adds in 7.8g sodium carbonate and trityl group phosphine
13.5g adds in 40 milliliters of dry Isosorbide-5-Nitrae-dioxane, under nitrogen protection, is warming to 110 DEG C of back flow reactions, reacts 8 hours
TLC plates detect, and are then cooled to room temperature, are filtered, washed again after petroleum ether, petroleum ether is added in after reduced pressure
Solid precipitation afterwards is filtered again, is collected liquid phase concentration, can be obtained colourless liquid product 2- ethyl styrene (3.5g, yield
81.7%).
The synthesis technology of 3 2- ethyl styrenes of embodiment, its step are as follows：
First, the synthesis of 2- ethylo benzenes formaldehyde
2- ethyl bromobenzenes (6g, 32.4mmol) are dissolved in 100 milliliters dry of tetrahydrofuran, be subsequently cooled to-
78 DEG C, tert-butyl lithium cyclohexane solution 2.5mol/L (25ml) is added dropwise, time for adding is 0.5 hour, and temperature is controlled during being added dropwise
Degree is no more than -65 DEG C, after being added dropwise, and is reacted at -78 DEG C 1 hour, it is small then to add in 3.7mlDMF solution insulation reaction 1
When, contact plate detection, saturated ammonium chloride solution quenching, washing, drying concentrate, can obtain colourless solution (4.2g, yield 96.5%).
2nd, the synthesis of 2- ethyl styrenes
2- ethylo benzenes formaldehyde (4.35g) is placed in single-necked flask, adds in 1.95g sodium hydroxides and trityl group phosphine
15.7g adds in 40 milliliters of dry Isosorbide-5-Nitrae-dioxane, under nitrogen protection, is heated to back flow reaction, reacts 7 hours TLC plates
Detection, after being cooled to room temperature, is filtered, is washed again after petroleum ether, and solid after petroleum ether is added in after reduced pressure
Precipitation is filtered again, collects liquid phase, and concentration can obtain colourless liquid product 2- ethyl styrene (3.55g, yield
82.9%).
The synthesis technology of 4 2- ethyl styrenes of embodiment, its step are as follows：
First, the synthesis of 2- ethylo benzenes formaldehyde
2- ethyl bromobenzenes (6g, 32.4mmol) are dissolved in 100 milliliters dry of dichloromethane, be subsequently cooled to-
70 DEG C, tert-butyl lithium cyclohexane solution 2.5mol/L (22.7ml) is added dropwise, time for adding is 0.5 hour, is controlled during being added dropwise
Temperature is no more than -65 DEG C, after being added dropwise, and is reacted at -70 DEG C 1 hour, it is small then to add in 3.7mlDMF solution insulation reaction 1
When, contact plate detection, saturated ammonium chloride solution quenching, washing, drying concentrate, can obtain colourless solution (4.21g, yield 96.8%).
2nd, the synthesis of 2- ethyl styrenes
2- ethylo benzenes formaldehyde (4.35g) is placed in single-necked flask, adds in 1.95g potassium hydroxide and trityl group phosphine
15.7g adds in 40 milliliters of dry hexamethylenes, under nitrogen protection, is heated to back flow reaction, reacts TLC plates detection in 6 hours,
Then it carries out decompression and screws out out hexamethylene, after decompression, filtered, washed again after petroleum ether, be concentrated under reduced pressure
Solid precipitation is filtered again after adding in petroleum ether afterwards, is collected liquid phase concentration, can be obtained colourless liquid product 2- ethyl styrenes
(3.4g, yield 85.1%).
The synthesis technology of 5 2- ethyl styrenes of embodiment, its step are as follows：
First, the synthesis of 2- ethylo benzenes formaldehyde
2- ethyl bromobenzenes (6g, 32.4mmol) are dissolved in 100 milliliters dry of tetrahydrofuran, be subsequently cooled to-
75 DEG C, tert-butyl lithium cyclohexane solution 2.5mol/L (25.8ml) is added dropwise, time for adding is 0.5 hour, is controlled during being added dropwise
Temperature is no more than -65 DEG C, after being added dropwise, and is reacted at -75 DEG C 1 hour, it is small then to add in 3.7mlDMF solution insulation reaction 1
When, contact plate detection, saturated ammonium chloride solution quenching, washing, drying are concentrated under reduced pressure, can obtain colourless solution (4.25g, yield
97.7%).
2nd, the synthesis of 2- ethyl styrenes
2- ethylo benzenes formaldehyde (4.35g) is placed in single-necked flask, adds in 3.6g potassium hydroxide and trityl group phosphine
22.5g adds in 40 milliliters of dry hexamethylenes, under nitrogen protection, is heated to back flow reaction, reacts TLC plates detection in 6 hours,
Then it carries out decompression and screws out out hexamethylene, after decompression, room temperature is cooled to after distillation, is filtered, petroleum ether
It is washed again afterwards, solid precipitation is filtered again after addition petroleum ether after reduced pressure, is collected liquid phase concentration, can be obtained colourless
Fluid product 2- ethyl styrenes (3.9g, yield 91.1%).
Basic principle, main feature and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.
Claims (10)
1. a kind of synthesis technology of 2- ethyl styrenes, which is characterized in that it is as follows,
(1) 2- ethyl bromobenzenes are dissolved in dry polar organic solvent, under cryogenic conditions, n-BuLi are added dropwise, during dropwise addition
Between for 0.5-4 hours, after being added dropwise, insulation reaction 1-6 hours under low temperature, be subsequently added into anhydrous n,N-Dimethylformamide,
1-6 hours are kept the temperature after adding, adds and reagent quenching, washing is quenched, stratification is not purified separately after organic phase concentration, obtained
Intermediate 2- ethylo benzene formaldehyde is directly used in step (2) reaction, yield 95-100%；
(2) intermediate 2- ethylo benzenes formaldehyde, inorganic base, trityl group phosphine and the solvent of drying are mixed, after mixing, inertia
Under atmosphere, insulation reaction 2-10 hours under counterflow condition, after reaction, post processing obtains pure target product, yield 80-
90%.
2. synthesis technology according to claim 1, it is characterised in that：In step (1), low temperature is -60 DEG C -78 DEG C.
3. synthesis technology according to claim 1, it is characterised in that：In step (1), dry polar organic solvent is two
Chloromethanes or tetrahydrofuran.
4. synthesis technology according to claim 1, it is characterised in that：In step (1), 2- ethyl bromobenzenes, n-BuLi and
The molar ratio of N,N-dimethylformamide is 1:(1.1-2.0):(1.2-2.0), dry polar organic solvent and 2- ethylo benzenes
The volume mass ratio of formaldehyde is 10:1~20:1mL/g.
5. synthesis technology according to claim 1, which is characterized in that in step (1), it is molten for saturated ammonium chloride that reagent is quenched
Liquid.
6. synthesis technology according to claim 1, which is characterized in that in step (1), time for adding is 0.5~1 hour,
1~2 hour is kept the temperature under low temperature after dropwise addition n-BuLi, after adding n,N-Dimethylformamide, keeps the temperature 1~2 hour.
7. synthesis technology according to claim 1, it is characterised in that：In step (2), inorganic base is potassium hydroxide, hydrogen-oxygen
Change any in sodium, sodium carbonate, sodium bicarbonate, potassium carbonate or calcium hydroxide；In step (2), 2- ethylo benzenes formaldehyde, inorganic base and
The molar ratio of trityl group phosphine is 1:(1.1-2.0):(1.1-2.5).
8. synthesis technology according to claim 1, it is characterised in that：In step (2), dry solvent be selected from hexamethylene or
It is any in 1,4- dioxane；The volume ratio of intermediate 2- ethylo benzenes formaldehyde and dry solvent is 1:8~1:15.
9. synthesis technology according to claim 1, it is characterised in that：In step (2), the method for post processing is specific as follows：
The solution after reaction is filtered first, obtained filtrate is washed successively, ethyl acetate extraction, dry, concentration
Ethyl acetate adds in petroleum ether after concentration, triphenylphosphine oxide is fully precipitated, and filtering and concentrating obtains 2- ethyl styrenes again.
10. synthesis technology according to claim 1, which is characterized in that in step (2), it is small that anti-7-8 is kept the temperature under counterflow condition
When.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111056927A (en) * | 2019-12-10 | 2020-04-24 | 清华大学 | Method for synthesizing monosubstituted styrene |
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Application publication date: 20180608 |