CN110105165A - A kind of preparation method of high-purity 1,4- dibromine naphthalene - Google Patents
A kind of preparation method of high-purity 1,4- dibromine naphthalene Download PDFInfo
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- CN110105165A CN110105165A CN201910506024.7A CN201910506024A CN110105165A CN 110105165 A CN110105165 A CN 110105165A CN 201910506024 A CN201910506024 A CN 201910506024A CN 110105165 A CN110105165 A CN 110105165A
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- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
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Abstract
The present invention relates to a kind of preparation methods of high-purity Isosorbide-5-Nitrae-dibromine naphthalene, belong to technical field of organic synthesis.To solve in the prior art 1; the preparation method of 4- dibromine naphthalene is complicated; reaction condition requires high; the problem of product purity is low, and yield is low and unstable product quality, the present invention provides a kind of high-purities 1; the preparation method of 4- dibromine naphthalene; four steps are purified including one kettle way acetylation protection and selective bromination process, hydrolysis deprotection process, diazo coupling reaction process and recrystallization method, obtain high-purity Isosorbide-5-Nitrae-dibromine naphthalene.Preparation method provided by the invention has synthetic route short, and reaction condition is mild, easily controllable, the low advantage of production cost.Organic synthesis site of the present invention is single, and selectivity is high, and product purity is up to 99.0%, and total recovery is up to 71.7%.The present invention is easily industrialized production, can effectively meet Isosorbide-5-Nitrae-dibromine naphthalene large-scale production needs, have broad application prospects.
Description
Technical field
The invention belongs to technical field of organic synthesis more particularly to a kind of high-purity Isosorbide-5-Nitrae-dibromine naphthalene preparation methods.
Background technique
It is the halogenated naphthalene compound of representative and its derivative in organic synthesis, chemical development, microorganism using 1,4- dibromine naphthalene
Chemistry, medicine, dyeing industry and agricultural etc. are multi-field to have extensive use and in the hot spot for increasingly becoming research and development in recent years.
The halogenated naphthalene derivatives such as Isosorbide-5-Nitrae-dibromine naphthalene are that the triple Fluorescent receptors of synthesis are blue due to its distinctive Electroluminescence Properties
The intermediate of color phosphor material is widely used in the synthesis of electroluminescent organic material, it has also become organic electronic in recent years
The research hotspot in and photoelectric information field.
It can be used for synthesizing the precursor of other naphthalene substitutive derivatives, such as phenol using Isosorbide-5-Nitrae-dibromine naphthalene as the halogenated naphthalene compound of representative
The naphthalenes substitutive derivative such as class, amine, ethers and metallo-organic compound is very wide in organic synthesis field application.
1,4- dibromine naphthalene can be used as medicine intermediate applied in the research and development and production of a variety of drugs.Such as synthetic drug Ah reaching
The bromo- 2- 2-methyl naphthoate of the intermediate 6- of pa woods, 6- [3- (1- adamantyl) -4- methoxyphenyl] -2- 2-methyl naphthoate etc..
Halogenated naphthalene derivatives are important dyestuff intermediate, the synthesis applied to various dyestuffs.It is blue such as to prepare direct mantoquita
Intermediate Neville acids of dyestuffs such as BR, direct mantoquita indigo plant 2R, Acid Red B, acidic intermedium bordeaux B etc..
Prior art preparation Isosorbide-5-Nitrae-dibromine naphthalene is mainly the synthetic method by direct halogenation, and principle is as follows:
Parental materials etc. occur at a certain temperature with halide reagent for the above method anti-using naphthalene or naphthalene derivatives as raw material
It should be synthesized, but contain a certain amount of isomer in product, it is difficult to be separated.
Summary of the invention
Low, the low problem of yield for the existing Isosorbide-5-Nitrae-dibromine naphthalene preparation method products obtained therefrom purity of solution, the present invention provides
A kind of preparation method of high-purity 1,4- dibromine naphthalene.
Technical solution of the present invention:
The reaction principle of high-purity 1,4- dibromine naphthalene preparation method of the present invention is as follows:
A kind of preparation method of high-purity Isosorbide-5-Nitrae-dibromine naphthalene, includes the following steps:
Step 1: one kettle way acetylation protection and selective bromination process:
Naphthalidine is mixed with acetic anhydride by certain mol proportion, takes water as a solvent and reacts at a certain temperature, reaction is completed
After be cooled to room temperature, it is sub- that bromo succinyl is added into reaction system by the molar ratio of certain naphthalidine and bromo-succinimide
Amine, the reaction was continued at a certain temperature, and filtration drying obtains the bromo- 1- acetylamino naphthalene of 4-, and structural formula is as follows:
Step 2: hydrolysis deprotection process:
The bromo- 1- acetylamino naphthalene of 4- obtained by step 1 is dissolved in ethyl alcohol, is added anti-at a certain temperature after concentrated hydrochloric acid
It answers, filtration drying obtains the bromo- naphthalidine of 4-, and structural formula is as follows:
Step 3: diazo coupling reaction process:
Hydrobromic acid is added into the bromo- naphthalidine of 4- obtained by step 2 by the molar ratio of the bromo- naphthalidine of certain 4- and hydrobromic acid
Solution, heat treatment cool down after a certain period of time, and acetonitrile is added；By the molar ratio of the bromo- naphthalidine of certain 4- and sodium nitrite to anti-
Answer and sodium nitrite solution be added dropwise in system dropwise, then by the bromo- naphthalidine of certain 4- and sodium fluoborate molar ratio to reaction system
In sodium fluoborate solution is added dropwise dropwise, be stirred to react under certain reaction temperature after a certain period of time, by the bromo- naphthalidine of certain 4- with
The molar ratio of cuprous bromide gained reaction system is added in the dilute hydrobromic acid solution of cuprous bromide, stirs at a certain temperature
To Isosorbide-5-Nitrae-dibromine naphthalene, gained reaction system is post-processed to obtain Isosorbide-5-Nitrae-dibromine naphthalene crude product；
Step 4: purification purification process:
Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is purified with recrystallization method, obtains high-purity Isosorbide-5-Nitrae-dibromine naphthalene.
Further, the molar ratio of naphthalidine and acetic anhydride described in step 1 is 1.0:(1.1~1.3)；The naphthalidine
With bromo-succinimide molar ratio 1.0:(1.1~1.3).
Further, reaction temperature described in step 1 is 90~100 DEG C, the reaction time of the naphthalidine and acetic anhydride
For 9~10h, the reaction time after bromo-succinimide is added is 6~8h.
Further, the mass fraction of concentrated hydrochloric acid described in step 2 is 37%, and the reaction temperature is 80 DEG C, the reaction time
For 6h.
Further, the molar ratio of the bromo- naphthalidine of 4- described in step 3 and hydrobromic acid is 1.0:(2.0~4.0), the hydrogen
The mass fraction of bromic acid is 35~40%, and the heat treatment is to heat 1h at 50 DEG C.
Further, the molar ratio of the bromo- naphthalidine of 4- described in step 3 and sodium nitrite is 1.0:(1.02~1.1), institute
The mass fraction for stating sodium nitrite solution is 30%.
Further, the bromo- naphthalidine of 4- described in step 3 and sodium fluoborate molar ratio are 1.0:(1.1~1.3), the fluorine
The mass fraction of dobell's solution is 30%.
Further, molar ratio 1.0:(1.1~1.3 of the bromo- naphthalidine of 4- described in step 3 and cuprous bromide), the bromine
The mass fraction for changing cuprous bromide in cuprous dilute hydrobromic acid solution is 30%, and the reaction temperature is -10~5 DEG C, described
Reaction time is 0.5~1h.
Further, the step of post-processing described in step 3 is: isometric toluene being added into reaction system, uses sulfurous
Acid sodium aqueous solution washes twice, and is washed with water to neutrality, liquid separation, and magnesium sulfate is added and is dried, and revolving removal solvent obtains
1,4- dibromine naphthalene crude product.
Further, the step of recrystallization method described in step 4 purifies is: Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is complete
Fully dissolved is in ethyl alcohol, then successively carries out cooling down, crystallize, filter and being dried.
Beneficial effects of the present invention:
The preparation method of high-purity Isosorbide-5-Nitrae-dibromine naphthalene provided by the invention has synthetic route short, and reaction condition is mild, easily
In control, the low advantage of production cost.Organic synthesis site of the present invention is single, and selectivity is high, and product purity is up to
99.0%, total recovery is up to 71.7%.The present invention is easily industrialized production, and it is extensive can effectively to meet Isosorbide-5-Nitrae-dibromine naphthalene
The needs of production, have broad application prospects.
Specific embodiment
Below with reference to embodiment, the following further describes the technical solution of the present invention, and however, it is not limited to this, all right
Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be contained
Lid is within the protection scope of the present invention.
Embodiment 1
The present embodiment provides a kind of preparation methods of high-purity Isosorbide-5-Nitrae-dibromine naphthalene, include the following steps:
Step 1: one kettle way acetylation protection and selective bromination process:
Naphthalidine is mixed with acetic anhydride by certain mol proportion, takes water as a solvent and reacts at a certain temperature, reaction is completed
After be cooled to room temperature, it is sub- that bromo succinyl is added into reaction system by the molar ratio of certain naphthalidine and bromo-succinimide
Amine, the reaction was continued at a certain temperature, and filtration drying obtains the bromo- 1- acetylamino naphthalene of 4-, and structural formula is as follows:
Step 2: hydrolysis deprotection process:
The bromo- 1- acetylamino naphthalene of 4- obtained by step 1 is dissolved in ethyl alcohol, is added anti-at a certain temperature after concentrated hydrochloric acid
It answers, filtration drying obtains the bromo- naphthalidine of 4-, and structural formula is as follows:
Step 3: diazo coupling reaction process:
Hydrobromic acid is added into the bromo- naphthalidine of 4- obtained by step 2 by the molar ratio of the bromo- naphthalidine of certain 4- and hydrobromic acid
Solution, heat treatment cool down after a certain period of time, and acetonitrile is added；By the molar ratio of the bromo- naphthalidine of certain 4- and sodium nitrite to anti-
Answer and sodium nitrite solution be added dropwise in system dropwise, then by the bromo- naphthalidine of certain 4- and sodium fluoborate molar ratio to reaction system
In sodium fluoborate solution is added dropwise dropwise, be stirred to react under certain reaction temperature after a certain period of time, by the bromo- naphthalidine of certain 4- with
The molar ratio of cuprous bromide gained reaction system is added in the dilute hydrobromic acid solution of cuprous bromide, stirs at a certain temperature
To Isosorbide-5-Nitrae-dibromine naphthalene, gained reaction system is post-processed to obtain Isosorbide-5-Nitrae-dibromine naphthalene crude product；
Step 4: purification purification process:
Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is purified with recrystallization method, obtains high-purity Isosorbide-5-Nitrae-dibromine naphthalene.
Embodiment 2
The present embodiment provides a kind of preparation methods of high-purity Isosorbide-5-Nitrae-dibromine naphthalene, include the following steps:
Step 1: one kettle way acetylation protection and selective bromination process:
By naphthalidine and acetic anhydride 1.0:(1.1~1.3 in molar ratio) it mixes, the water of 1~3 times of volume is added, 90~
9~10h is reacted at a temperature of 100 DEG C, is cooled to room temperature after the reaction was completed, by the molar ratio of naphthalidine and bromo-succinimide
1.0:(1.1~1.3) bromo-succinimide is added into reaction system, 6~8h, filtering are reacted at a temperature of 90~100 DEG C
It is dried to obtain the bromo- 1- acetylamino naphthalene of 4-；
Step 2: hydrolysis deprotection process:
The bromo- 1- acetylamino naphthalene of 4- obtained by step 1 is dissolved in ethyl alcohol, is added anti-at a certain temperature after concentrated hydrochloric acid
It answers, filtration drying obtains the bromo- naphthalidine of 4-；
Step 3: diazo coupling reaction process:
Hydrobromic acid is added into the bromo- naphthalidine of 4- obtained by step 2 by the molar ratio of the bromo- naphthalidine of certain 4- and hydrobromic acid
Solution, heat treatment cool down after a certain period of time, and acetonitrile is added；By the molar ratio of the bromo- naphthalidine of certain 4- and sodium nitrite to anti-
Answer and sodium nitrite solution be added dropwise in system dropwise, then by the bromo- naphthalidine of certain 4- and sodium fluoborate molar ratio to reaction system
In sodium fluoborate solution is added dropwise dropwise, be stirred to react under certain reaction temperature after a certain period of time, by the bromo- naphthalidine of certain 4- with
The molar ratio of cuprous bromide gained reaction system is added in the dilute hydrobromic acid solution of cuprous bromide, stirs at a certain temperature
To Isosorbide-5-Nitrae-dibromine naphthalene, gained reaction system is post-processed to obtain Isosorbide-5-Nitrae-dibromine naphthalene crude product；
Step 4: purification purification process:
Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is purified with recrystallization method, obtains high-purity Isosorbide-5-Nitrae-dibromine naphthalene.
Embodiment 3
The present embodiment provides a kind of preparation methods of high-purity Isosorbide-5-Nitrae-dibromine naphthalene, include the following steps:
Step 1: one kettle way acetylation protection and selective bromination process:
By naphthalidine and acetic anhydride 1.0:(1.1~1.3 in molar ratio) it mixes, the water of 1~3 times of volume is added, 90~
9~10h is reacted at a temperature of 100 DEG C, is cooled to room temperature after the reaction was completed, by the molar ratio of naphthalidine and bromo-succinimide
1.0:(1.1~1.3) bromo-succinimide is added into reaction system, 6~8h, filtering are reacted at a temperature of 90~100 DEG C
It is dried to obtain the bromo- 1- acetylamino naphthalene of 4-；
Step 2: hydrolysis deprotection process:
The bromo- 1- acetylamino naphthalene of 4- obtained by step 1 is dissolved in 100mL95% ethyl alcohol, 4- in gained mixed solution
The mass concentration of bromo- 1- acetylamino naphthalene is 30~60%, and the concentrated hydrochloric acid that mass concentration is 37% is added into mixed solution
6h is reacted after 50mL at a temperature of 80 DEG C, filtration drying obtains the bromo- naphthalidine of 4-；
Step 3: diazo coupling reaction process:
Hydrobromic acid is added into the bromo- naphthalidine of 4- obtained by step 2 by the molar ratio of the bromo- naphthalidine of certain 4- and hydrobromic acid
Solution, heat treatment cool down after a certain period of time, and acetonitrile is added；By the molar ratio of the bromo- naphthalidine of certain 4- and sodium nitrite to anti-
Answer and sodium nitrite solution be added dropwise in system dropwise, then by the bromo- naphthalidine of certain 4- and sodium fluoborate molar ratio to reaction system
In sodium fluoborate solution is added dropwise dropwise, be stirred to react under certain reaction temperature after a certain period of time, by the bromo- naphthalidine of certain 4- with
The molar ratio of cuprous bromide gained reaction system is added in the dilute hydrobromic acid solution of cuprous bromide, stirs at a certain temperature
To Isosorbide-5-Nitrae-dibromine naphthalene, gained reaction system is post-processed to obtain Isosorbide-5-Nitrae-dibromine naphthalene crude product；
Step 4: purification purification process:
Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is purified with recrystallization method, obtains high-purity Isosorbide-5-Nitrae-dibromine naphthalene.
Embodiment 4
The present embodiment provides a kind of preparation methods of high-purity Isosorbide-5-Nitrae-dibromine naphthalene, include the following steps:
Step 1: one kettle way acetylation protection and selective bromination process:
By naphthalidine and acetic anhydride 1.0:(1.1~1.3 in molar ratio) it mixes, the water of 1~3 times of volume is added, 90~
9~10h is reacted at a temperature of 100 DEG C, is cooled to room temperature after the reaction was completed, by the molar ratio of naphthalidine and bromo-succinimide
1.0:(1.1~1.3) bromo-succinimide is added into reaction system, 6~8h, filtering are reacted at a temperature of 90~100 DEG C
It is dried to obtain the bromo- 1- acetylamino naphthalene of 4-；
Step 2: hydrolysis deprotection process:
The bromo- 1- acetylamino naphthalene of 4- obtained by step 1 is dissolved in 100mL95% ethyl alcohol, 4- in gained mixed solution
The mass concentration of bromo- 1- acetylamino naphthalene is 30~60%, and the concentrated hydrochloric acid that mass concentration is 37% is added into mixed solution
6h is reacted after 50mL at a temperature of 80 DEG C, filtration drying obtains the bromo- naphthalidine of 4-；
Step 3: diazo coupling reaction process:
By molar ratio 1.0:(2.0~4.0 of the bromo- naphthalidine of 4- and hydrobromic acid) into the bromo- naphthalidine of 4- obtained by step 2
Addition mass fraction is 35~40% hydrobromic acid solutions, and cooling, 0.5~2 times of volumes of acetonitrile of addition after 1h is heated at 50 DEG C；By 4-
Molar ratio 1.0:(1.02~1.1 of bromo- 1- naphthylamines and sodium nitrite) be added dropwise dropwise into reaction system mass fraction be 30%
Sodium nitrite solution, then press the bromo- naphthalidine of 4- and sodium fluoborate molar ratio 1.0:(1.1~1.3) into reaction system dropwise
Dropwise addition mass fraction is 30% sodium fluoborate solution, after stirring 0.5~1h under -10~5 DEG C of reaction temperatures, by the bromo- 1- naphthalene of 4-
Molar ratio 1.0:(1.1~1.3 of amine and cuprous bromide) gained reaction system is slowly added to cuprous bromide dilute hydrobromic acid it is molten
In liquid, the mass fraction of cuprous bromide is 30% in the dilute hydrobromic acid solution of cuprous bromide, is stirred under -10~5 DEG C of reaction temperatures
After mixing 0.5~1h, isometric toluene is added into reaction system, is washed twice with sodium sulfite aqueous solution, be washed with water to
Neutrality, liquid separation are added magnesium sulfate and are dried, and revolving removal solvent obtains Isosorbide-5-Nitrae-dibromine naphthalene crude product；
Step 4: purification purification process:
Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is purified with recrystallization method, obtains high-purity Isosorbide-5-Nitrae-dibromine naphthalene.
Embodiment 5
The present embodiment provides a kind of preparation methods of high-purity Isosorbide-5-Nitrae-dibromine naphthalene, include the following steps:
Step 1: one kettle way acetylation protection and selective bromination process:
By naphthalidine and acetic anhydride 1.0:(1.1~1.3 in molar ratio) it mixes, the water of 1~3 times of volume is added, 90~
9~10h is reacted at a temperature of 100 DEG C, is cooled to room temperature after the reaction was completed, by the molar ratio of naphthalidine and bromo-succinimide
1.0:(1.1~1.3) bromo-succinimide is added into reaction system, 6~8h, filtering are reacted at a temperature of 90~100 DEG C
It is dried to obtain the bromo- 1- acetylamino naphthalene of 4-；
Step 2: hydrolysis deprotection process:
The bromo- 1- acetylamino naphthalene of 4- obtained by step 1 is dissolved in 100mL95% ethyl alcohol, 4- in gained mixed solution
The mass concentration of bromo- 1- acetylamino naphthalene is 30~60%, and the concentrated hydrochloric acid that mass concentration is 37% is added into mixed solution
6h is reacted after 50mL at a temperature of 80 DEG C, filtration drying obtains the bromo- naphthalidine of 4-；
Step 3: diazo coupling reaction process:
By molar ratio 1.0:(2.0~4.0 of the bromo- naphthalidine of 4- and hydrobromic acid) into the bromo- naphthalidine of 4- obtained by step 2
Addition mass fraction is 35~40% hydrobromic acid solutions, and cooling, 0.5~2 times of volumes of acetonitrile of addition after 1h is heated at 50 DEG C；By 4-
Molar ratio 1.0:(1.02~1.1 of bromo- 1- naphthylamines and sodium nitrite) be added dropwise dropwise into reaction system mass fraction be 30%
Sodium nitrite solution, then press the bromo- naphthalidine of 4- and sodium fluoborate molar ratio 1.0:(1.1~1.3) into reaction system dropwise
Dropwise addition mass fraction is 30% sodium fluoborate solution, after stirring 0.5~1h under -10~5 DEG C of reaction temperatures, by the bromo- 1- naphthalene of 4-
Molar ratio 1.0:(1.1~1.3 of amine and cuprous bromide) gained reaction system is slowly added to cuprous bromide dilute hydrobromic acid it is molten
In liquid, the mass fraction of cuprous bromide is 30% in the dilute hydrobromic acid solution of cuprous bromide, is stirred under -10~5 DEG C of reaction temperatures
After mixing 0.5~1h, isometric toluene is added into reaction system, is washed twice with sodium sulfite aqueous solution, be washed with water to
Neutrality, liquid separation are added magnesium sulfate and are dried, and revolving removal solvent obtains Isosorbide-5-Nitrae-dibromine naphthalene crude product；
Step 4: purification purification process:
Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is purified with recrystallization method, Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is complete
Fully dissolved is in 95% ethyl alcohol, then successively carries out cooling down, crystallize, filter and being dried, and obtains high-purity Isosorbide-5-Nitrae-dibromine naphthalene.
The preparation method of high-purity Isosorbide-5-Nitrae-dibromine naphthalene provided in this embodiment has synthetic route short, and reaction condition is mild,
Easily controllable, the low advantage of production cost, the present embodiment organic synthesis site is single, and reaction selectivity is high, product purity
Up to 99.0%, total recovery is up to 71.7%.
Embodiment 6
The present embodiment provides a kind of preparation methods of high-purity Isosorbide-5-Nitrae-dibromine naphthalene, include the following steps:
Step 1: one kettle way acetylation protection and selective bromination process:
By naphthalidine, 1.0:1.2 is mixed in molar ratio with acetic anhydride, and the water of 1 times of volume is added, reacts at a temperature of 100 DEG C
9h is cooled to room temperature after the reaction was completed, is added by the molar ratio 1.0:1.1 of naphthalidine and bromo-succinimide into reaction system
Enter bromo-succinimide, 6h is reacted at a temperature of 100 DEG C, filtration drying obtains the bromo- 1- acetylamino naphthalene of 4-；
Step 2: hydrolysis deprotection process:
The bromo- 1- acetylamino naphthalene of 4- obtained by step 1 is dissolved in 100mL95% ethyl alcohol, 4- in gained mixed solution
The mass concentration of bromo- 1- acetylamino naphthalene is 30%, after the concentrated hydrochloric acid 50mL that mass concentration is 37% is added into mixed solution
6h is reacted at a temperature of 80 DEG C, filtration drying obtains the bromo- naphthalidine of 4-；
Step 3: diazo coupling reaction process:
Quality is added into the bromo- naphthalidine of 4- obtained by step 2 by the molar ratio 1.0:2.5 of the bromo- naphthalidine of 4- and hydrobromic acid
Number is 40% hydrobromic acid solution, and cooling after 1h is heated at 50 DEG C, 0.5 times of volumes of acetonitrile is added；By the bromo- naphthalidine of 4- and Asia
It is 30% sodium nitrite solution that mass fraction is added dropwise into reaction system dropwise by the molar ratio 1.0:1.05 of sodium nitrate, then presses 4-
It is 30% sodium fluoborate that mass fraction is added dropwise into reaction system dropwise by the molar ratio 1.0:1.2 of bromo- 1- naphthylamines and sodium fluoborate
Solution, after stirring 0.5h under -5 DEG C of reaction temperatures, by the molar ratio 1.0:1.2 of the bromo- naphthalidine of 4- and cuprous bromide by gained
Reaction system is slowly added in the dilute hydrobromic acid solution of cuprous bromide, the matter of cuprous bromide in the dilute hydrobromic acid solution of cuprous bromide
Measuring number is 30%, after stirring 0.5h under -5 DEG C of reaction temperatures, isometric toluene is added into reaction system, uses sulfurous acid
Sodium water solution washes twice, and is washed with water to neutrality, liquid separation, and magnesium sulfate is added and is dried, and revolving removal solvent obtains 1,
4- dibromine naphthalene crude product；
Step 4: purification purification process:
Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is purified with recrystallization method, Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is complete
Fully dissolved is in 95% ethyl alcohol, then successively carries out cooling down, crystallize, filter and being dried, and obtains high-purity Isosorbide-5-Nitrae-dibromine naphthalene.
Isosorbide-5-Nitrae manufactured in the present embodiment-dibromine naphthalene product purity is 99.0%, total recovery 71.7%.
Embodiment 7
The present embodiment provides a kind of preparation methods of high-purity Isosorbide-5-Nitrae-dibromine naphthalene, include the following steps:
Step 1: one kettle way acetylation protection and selective bromination process:
By naphthalidine, 1.0:1.3 is mixed in molar ratio with acetic anhydride, and the water of 2 times of volumes is added, reacts at a temperature of 100 DEG C
10h is cooled to room temperature after the reaction was completed, by the molar ratio 1.0:1.2 of naphthalidine and bromo-succinimide into reaction system
Bromo-succinimide is added, 8h is reacted at a temperature of 100 DEG C, filtration drying obtains the bromo- 1- acetylamino naphthalene of 4-；
Step 2: hydrolysis deprotection process:
The bromo- 1- acetylamino naphthalene of 4- obtained by step 1 is dissolved in 100mL95% ethyl alcohol, 4- in gained mixed solution
The mass concentration of bromo- 1- acetylamino naphthalene is 40%, after the concentrated hydrochloric acid 50mL that mass concentration is 37% is added into mixed solution
6h is reacted at a temperature of 80 DEG C, filtration drying obtains the bromo- naphthalidine of 4-；
Step 3: diazo coupling reaction process:
Quality is added into the bromo- naphthalidine of 4- obtained by step 2 by the molar ratio 1.0:4.0 of the bromo- naphthalidine of 4- and hydrobromic acid
Number is 40% hydrobromic acid solution, and cooling after 1h is heated at 50 DEG C, 1 times of volumes of acetonitrile is added；By the bromo- naphthalidine of 4- and nitrous
It is 30% sodium nitrite solution that mass fraction is added dropwise into reaction system dropwise by the molar ratio 1.0:1.1 of sour sodium, then presses the bromo- 1- of 4-
It is 30% sodium fluoborate solution that mass fraction is added dropwise into reaction system dropwise by the molar ratio 1.0:1.3 of naphthylamines and sodium fluoborate,
After stirring 1h under 0 DEG C of reaction temperature, by the molar ratio 1.0:1.3 of the bromo- naphthalidine of 4- and cuprous bromide by gained reaction system
It is slowly added in the dilute hydrobromic acid solution of cuprous bromide, the mass fraction of cuprous bromide is in the dilute hydrobromic acid solution of cuprous bromide
30%, after stirring 1h under 0 DEG C of reaction temperature, isometric toluene is added into reaction system, is washed with sodium sulfite aqueous solution
It washs twice, is washed with water to neutrality, liquid separation, magnesium sulfate is added and is dried, it is thick to obtain Isosorbide-5-Nitrae-dibromine naphthalene for revolving removal solvent
Product；
Step 4: purification purification process:
Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is purified with recrystallization method, Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is complete
Fully dissolved is in 95% ethyl alcohol, then successively carries out cooling down, crystallize, filter and being dried, and obtains high-purity Isosorbide-5-Nitrae-dibromine naphthalene.
Isosorbide-5-Nitrae manufactured in the present embodiment-dibromine naphthalene product purity is 99.0%, total recovery 71.1%.
Embodiment 8
The present embodiment provides a kind of preparation methods of high-purity Isosorbide-5-Nitrae-dibromine naphthalene, include the following steps:
Step 1: one kettle way acetylation protection and selective bromination process:
By naphthalidine, 1.0:1.1 is mixed in molar ratio with acetic anhydride, and the water of 3 times of volumes is added, reacts at a temperature of 95 DEG C
9.5h is cooled to room temperature after the reaction was completed, by the molar ratio 1.0:1.1 of naphthalidine and bromo-succinimide into reaction system
Bromo-succinimide is added, 7h is reacted at a temperature of 95 DEG C, filtration drying obtains the bromo- 1- acetylamino naphthalene of 4-；
Step 2: hydrolysis deprotection process:
The bromo- 1- acetylamino naphthalene of 4- obtained by step 1 is dissolved in 100mL95% ethyl alcohol, 4- in gained mixed solution
The mass concentration of bromo- 1- acetylamino naphthalene is 50%, after the concentrated hydrochloric acid 50mL that mass concentration is 37% is added into mixed solution
6h is reacted at a temperature of 80 DEG C, filtration drying obtains the bromo- naphthalidine of 4-；
Step 3: diazo coupling reaction process:
Quality is added into the bromo- naphthalidine of 4- obtained by step 2 by the molar ratio 1.0:3.0 of the bromo- naphthalidine of 4- and hydrobromic acid
Number is 37% hydrobromic acid solution, and cooling after 1h is heated at 50 DEG C, 1.5 times of volumes of acetonitrile are added；By the bromo- naphthalidine of 4- and Asia
It is 30% sodium nitrite solution that mass fraction is added dropwise into reaction system dropwise by the molar ratio 1.0:1.02 of sodium nitrate, then presses 4-
It is 30% sodium fluoborate that mass fraction is added dropwise into reaction system dropwise by the molar ratio 1.0:1.1 of bromo- 1- naphthylamines and sodium fluoborate
Solution is reacted gained with the molar ratio 1.0:1.1 of cuprous bromide by the bromo- naphthalidine of 4- after stirring 1h under 5 DEG C of reaction temperatures
System is slowly added in the dilute hydrobromic acid solution of cuprous bromide, the mass parts of cuprous bromide in the dilute hydrobromic acid solution of cuprous bromide
Number is 30%, and after stirring 1h under 5 DEG C of reaction temperatures, isometric toluene is added into reaction system, water-soluble with sodium sulfite
Liquid washes twice, and is washed with water to neutrality, liquid separation, and magnesium sulfate is added and is dried, and revolving removal solvent obtains Isosorbide-5-Nitrae-dibromo
Naphthalene crude product；
Step 4: purification purification process:
Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is purified with recrystallization method, Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is complete
Fully dissolved is in 95% ethyl alcohol, then successively carries out cooling down, crystallize, filter and being dried, and obtains high-purity Isosorbide-5-Nitrae-dibromine naphthalene.
Isosorbide-5-Nitrae manufactured in the present embodiment-dibromine naphthalene product purity is 99.0%, total recovery 70.2%.
Embodiment 9
The present embodiment provides a kind of preparation methods of high-purity Isosorbide-5-Nitrae-dibromine naphthalene, include the following steps:
Step 1: one kettle way acetylation protection and selective bromination process:
By naphthalidine, 1.0:1.3 is mixed in molar ratio with acetic anhydride, and the water of 1.5 times of volumes is added, anti-at a temperature of 100 DEG C
9h is answered, is cooled to room temperature after the reaction was completed, by the molar ratio 1.0:1.3 of naphthalidine and bromo-succinimide to reaction system
Middle addition bromo-succinimide, reacts 6h at a temperature of 100 DEG C, and filtration drying obtains the bromo- 1- acetylamino naphthalene of 4-；
Step 2: hydrolysis deprotection process:
The bromo- 1- acetylamino naphthalene of 4- obtained by step 1 is dissolved in 100mL95% ethyl alcohol, 4- in gained mixed solution
The mass concentration of bromo- 1- acetylamino naphthalene is 60%, after the concentrated hydrochloric acid 50mL that mass concentration is 37% is added into mixed solution
6h is reacted at a temperature of 80 DEG C, filtration drying obtains the bromo- naphthalidine of 4-；
Step 3: diazo coupling reaction process:
Quality is added into the bromo- naphthalidine of 4- obtained by step 2 by the molar ratio 1.0:3.0 of the bromo- naphthalidine of 4- and hydrobromic acid
Number is 40% hydrobromic acid solution, and cooling after 1h is heated at 50 DEG C, 2 times of volumes of acetonitrile are added；By the bromo- naphthalidine of 4- and nitrous
It is 30% sodium nitrite solution that mass fraction is added dropwise into reaction system dropwise by the molar ratio 1.0:1.08 of sour sodium, then bromo- by 4-
It is that 30% sodium fluoborate is molten that mass fraction is added dropwise into reaction system dropwise by the molar ratio 1.0:1.3 of naphthalidine and sodium fluoborate
Liquid, after stirring 1h under -10 DEG C of reaction temperatures, the molar ratio 1.0:1.3 by the bromo- naphthalidine of 4- and cuprous bromide is anti-by gained
System is answered to be slowly added in the dilute hydrobromic acid solution of cuprous bromide, the quality of cuprous bromide in the dilute hydrobromic acid solution of cuprous bromide
Number is 30%, after stirring 1h under -10 DEG C of reaction temperatures, isometric toluene is added into reaction system, uses sodium sulfite
Aqueous solution washes twice, and is washed with water to neutrality, liquid separation, and magnesium sulfate is added and is dried, and revolving removal solvent obtains Isosorbide-5-Nitrae-
Dibromine naphthalene crude product；
Step 4: purification purification process:
Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is purified with recrystallization method, Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is complete
Fully dissolved is in 95% ethyl alcohol, then successively carries out cooling down, crystallize, filter and being dried, and obtains high-purity Isosorbide-5-Nitrae-dibromine naphthalene.
Isosorbide-5-Nitrae manufactured in the present embodiment-dibromine naphthalene product purity is 99.0%, total recovery 71.2%.
Claims (10)
1. a kind of preparation method of high-purity Isosorbide-5-Nitrae-dibromine naphthalene, which comprises the steps of:
Step 1: one kettle way acetylation protection and selective bromination process:
Naphthalidine is mixed with acetic anhydride by certain mol proportion, takes water as a solvent and reacts at a certain temperature, it is cold after the reaction was completed
But to room temperature, bromo-succinimide is added into reaction system by the molar ratio of certain naphthalidine and bromo-succinimide,
The reaction was continued at a certain temperature, and filtration drying obtains the bromo- 1- acetylamino naphthalene of 4-, and structural formula is as follows:
Step 2: hydrolysis deprotection process:
The bromo- 1- acetylamino naphthalene of 4- obtained by step 1 is dissolved in ethyl alcohol, is reacted at a certain temperature after concentrated hydrochloric acid is added, mistake
Filter is dried to obtain the bromo- naphthalidine of 4-, and structural formula is as follows:
Step 3: diazo coupling reaction process:
Hydrobromic acid solution is added into the bromo- naphthalidine of 4- obtained by step 2 by the molar ratio of the bromo- naphthalidine of certain 4- and hydrobromic acid,
Heat treatment cools down after a certain period of time, and acetonitrile is added；By the molar ratio of the bromo- naphthalidine of certain 4- and sodium nitrite to reaction system
In be added dropwise sodium nitrite solution dropwise, then by the molar ratio of the bromo- naphthalidine of certain 4- and sodium fluoborate into reaction system dropwise
Sodium fluoborate solution is added dropwise, is stirred to react under certain reaction temperature after a certain period of time, by the bromo- naphthalidine of certain 4- and protobromide
The molar ratio of copper gained reaction system is added in the dilute hydrobromic acid solution of cuprous bromide, stirs to get Isosorbide-5-Nitrae-at a certain temperature
Dibromine naphthalene post-processes gained reaction system to obtain Isosorbide-5-Nitrae-dibromine naphthalene crude product；
Step 4: purification purification process:
Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 is purified with recrystallization method, obtains high-purity Isosorbide-5-Nitrae-dibromine naphthalene.
2. a kind of preparation method of high-purity Isosorbide-5-Nitrae-dibromine naphthalene according to claim 1, which is characterized in that 1- described in step 1
The molar ratio of naphthylamines and acetic anhydride is 1.0:(1.1~1.3)；The naphthalidine and bromo-succinimide molar ratio 1.0:(1.1
~1.3).
3. a kind of preparation method of high-purity Isosorbide-5-Nitrae-dibromine naphthalene according to claim 1 or claim 2, which is characterized in that step 1 institute
Stating reaction temperature is 90~100 DEG C, and the reaction time of the naphthalidine and acetic anhydride is 9~10h, and it is sub- that bromo succinyl is added
Reaction time after amine is 6~8h.
4. a kind of preparation method of high-purity Isosorbide-5-Nitrae-dibromine naphthalene according to claim 3, which is characterized in that dense described in step 2
The mass fraction of hydrochloric acid is 37%, and the reaction temperature is 80 DEG C, reaction time 6h.
5. a kind of preparation method of high-purity Isosorbide-5-Nitrae-dibromine naphthalene according to claim 4, which is characterized in that 4- described in step 3
The molar ratio of bromo- naphthalidine and hydrobromic acid is 1.0:(2.0~4.0), the mass fraction of the hydrobromic acid is 35~40%, described
Heat treatment is to heat 1h at 50 DEG C.
6. a kind of preparation method of high-purity Isosorbide-5-Nitrae-dibromine naphthalene according to claim 5, which is characterized in that 4- described in step 3
The molar ratio of bromo- naphthalidine and sodium nitrite is 1.0:(1.02~1.1), the mass fraction of the sodium nitrite solution is
30%.
7. a kind of preparation method of high-purity Isosorbide-5-Nitrae-dibromine naphthalene according to claim 6, which is characterized in that 4- described in step 3
Bromo- naphthalidine and sodium fluoborate molar ratio are 1.0:(1.1~1.3), the mass fraction of the sodium fluoborate solution is 30%.
8. a kind of preparation method of high-purity Isosorbide-5-Nitrae-dibromine naphthalene according to claim 7, which is characterized in that 4- described in step 3
Molar ratio 1.0:(1.1~1.3 of bromo- naphthalidine and cuprous bromide), protobromide in the dilute hydrobromic acid solution of the cuprous bromide
The mass fraction of copper is 30%, and the reaction temperature is -10~5 DEG C, and the reaction time is 0.5~1h.
9. a kind of preparation method of high-purity Isosorbide-5-Nitrae-dibromine naphthalene according to claim 8, which is characterized in that after described in step 3
The step of processing, is: isometric toluene is added into reaction system, is washed twice with sodium sulfite aqueous solution, be washed with water to
Neutrality, liquid separation are added magnesium sulfate and are dried, and revolving removal solvent obtains Isosorbide-5-Nitrae-dibromine naphthalene crude product.
10. a kind of preparation method of high-purity Isosorbide-5-Nitrae-dibromine naphthalene according to claim 9, which is characterized in that described in step 4
The step of recrystallization method purifies is: Isosorbide-5-Nitrae-dibromine naphthalene crude product obtained by step 3 being dissolved completely in ethyl alcohol, then is successively carried out cold
But, crystallize, filter and be dried.
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