CN100369874C - Prepn process of 1-fluoronaphthalene - Google Patents

Prepn process of 1-fluoronaphthalene Download PDF

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CN100369874C
CN100369874C CNB2006100284333A CN200610028433A CN100369874C CN 100369874 C CN100369874 C CN 100369874C CN B2006100284333 A CNB2006100284333 A CN B2006100284333A CN 200610028433 A CN200610028433 A CN 200610028433A CN 100369874 C CN100369874 C CN 100369874C
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salt
diazonium
fluoronaphthalene
acid
diazonium fluoride
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CN1887833A (en
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袁云龙
陈莹敏
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Shanghai Kangpeng Science and Technology Co., Ltd.
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SHANGHAI KANGPENG CHEMICAL CO Ltd
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Abstract

The preparation process of 1-fluoronaphthalene includes the following steps: (1) reacting 1-naphthylamine with nitrous acid, nitrous acid ester or nitrite in acid medium to obtain diazo salt; (2) reacting the diazo salt with fluoroboric acid or its salt or fluorophosphoric acid or its salt to obtain diazo fluoroborate or diazo fluorophosphate; and (3) heating the diazo fluoroborate or diazo fluorophosphate to decompose to obtain 1-fluoronaphthalene. The process has short synthesis path, less side products, mild reaction condition, easy control, relatively low cost, great production capacity, high product purity and other advantages, and the product is used as medicine intermediate.

Description

The preparation method of 1-fluoronaphthalene
Technical field
The present invention relates to the preparation method of 1-fluoronaphthalene.
Background technology
The 1-fluoronaphthalene is the pharmaceutical intermediate that a kind of development in recent years is got up.Hydrogen atom on the aromatic nucleus is replaced to fluorine atom, tend to the biological activity of compound is produced stronger and unexpected effect.In bioactive molecules, hydrogen atom is replaced to fluorine atom often can obtain having raising or improve bioactive similar compound.
In the prior art, fluoridize and to be undertaken by directly fluoridizing with fluorizating agent.Need use special reagent and equipment but directly fluoridize, and cost an arm and a leg, technology is immature, therefore is not suitable for industrial production.Fluoridize and to pass through halogen-fluorine permutoid reaction, carry out with the form of nucleophilic substitution.But this reaction often need be carried out comparatively high temps (generally being 150~300 ℃), often forms the degradation production and the tar of significant quantity easily.And this reaction often is attended by other side reaction, and the by product of formation is difficult to remove from product.
Reported a class naphthalene derivatives among the Chinese patent application CN99109523.5, the preparation method of such naphthalene derivatives is characterised in that alkyl lithiation reagent such as being to use magnesium or butyllithium, makes metal reagent, by the effect of fluorizating agent, finishes and fluoridizes.Though this method has overcome the temperature of reaction height of above-mentioned halogen-fluorine permutoid reaction, the shortcoming that by product is many, employed fluorizating agent and technology thereof, equipment are difficult to be realized, is difficult to suitability for industrialized production.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of 1-fluoronaphthalene, this method synthetic route is short, and mild condition easily realizes industrialization, and products obtained therefrom purity height and steady quality.
The invention provides a kind of method of the 1-of preparation fluoronaphthalene, this method may further comprise the steps:
(1) naphthalidine is obtained diazonium salt with nitrous acid, nitrous acid ester or nitrite reaction in acidic medium;
(2) diazonium salt that step (1) obtains and fluoroboric acid or its salt or hexafluorophosphoric acid or its salt are reacted, obtain diazonium fluoride borate or diazonium fluoride phosphoric acid salt;
(3) diazonium fluoride borate or the diazonium fluoride phosphoric acid salt that step (2) is obtained carries out thermal degradation, obtains the 1-fluoronaphthalene.
Preferably, described step (3) is carried out in nonpolar or polar organic solvent.More preferably, described step (3) is carried out in non-polar solvent.Described nonpolar or polar organic solvent preferably is selected from ethylene dichloride, trichloromethane, tetracol phenixin, chlorobenzene, bromobenzene, hexane, heptane, pentane, sherwood oil, hexanaphthene, benzene,toluene,xylene, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), N-Methyl pyrrolidone (NMP) or acetonitrile.Particularly preferred solvent is chlorobenzene or sherwood oil.
In aforesaid method, preferably, described step (1) forms the reaction of diazonium salt and described step (2) forms the diazonium fluoride borate or diazonium fluoride is phosphatic is reflected in-20 ℃~20 ℃ the temperature range and carries out.More preferably, described step (1) forms being reflected in-10 ℃~5 ℃ the temperature range of diazonium salt and carries out.More preferably, described step (2) forms the diazonium fluoride borate or diazonium fluoride is phosphatic is reflected in-5 ℃~5 ℃ the temperature range and carries out.
In aforesaid method, preferably, the thermal degradation temperature of described step (3) is controlled in 50~150 ℃ the scope.Be more preferably, the thermal degradation temperature of described step (3) is controlled in 70~120 ℃ the scope.
Preferably, the mol ratio of naphthalidine and described fluoroboric acid or its salt or hexafluorophosphoric acid or its salt is 1: 1~1: 4.Be more preferably, the mol ratio of naphthalidine and described fluoroboric acid or its salt or hexafluorophosphoric acid or its salt is 1: 1.2~1: 1.5.
Preferably, the mol ratio of naphthalidine and described nitrous acid, nitrous acid ester or nitrite is 1: 1.1~1: 3.
In aforesaid method, especially preferably, described acidic medium can be selected from HCl, H 2SO 4Or HBr; Described nitrite is NaNO 2Described fluoroborate is NaBF 4Described fluorophosphate is NaPF 6
Description of drawings
Fig. 1 is the mass spectrum of the 1-fluoronaphthalene for preparing of the embodiment of the invention 1.
Embodiment
The preparation method of 1-fluoronaphthalene of the present invention is raw material with the naphthalidine, passes through diazotization, forms diazonium fluoride borate or diazonium fluoride phosphoric acid salt again, carries out thermolysis then, forms 1-fluoronaphthalene product.
Specifically, the preparation method of 1-fluoronaphthalene may further comprise the steps:
(1) naphthalidine is obtained diazonium salt with nitrous acid, nitrous acid ester or nitrite reaction in acidic medium;
(2) diazonium salt that step (1) obtains and fluoroboric acid or its salt or hexafluorophosphoric acid or its salt are reacted, obtain diazonium fluoride borate or diazonium fluoride phosphoric acid salt;
(3) diazonium fluoride borate or the diazonium fluoride phosphoric acid salt that step (2) is obtained carries out thermal degradation, obtains the 1-fluoronaphthalene.
In step (1), acidic medium can be any medium that diazotization reaction provides sour environment that is well-suited for, and includes but not limited to: HCl, H 2SO 4Or HBr, particularly preferably be HCl.Nitrous acid ester can be any nitrous acid ester that diazotization reaction forms diazonium salt that is suitable for, and nitrite can be any nitrite that diazotization reaction forms diazonium salt that is suitable for.Particularly preferably be Sodium Nitrite (NaNO 2).
Diazotization reaction should be carried out at low temperatures, preferably carries out in-20 ℃~20 ℃ temperature range, preferably carries out in-10 ℃~5 ℃ temperature range especially.
Step (1) preferably is dissolved in naphthalidine in the acidic medium (for example hydrochloric acid soln), and then adding nitrous acid, nitrous acid ester or nitrite carry out diazotization reaction.If desired, can naphthalidine be dissolved in the acidic medium by heating a little, heating and temperature control is not only helping dissolving but also can not produce in the dysgenic scope reaction, and preferably 40~120 ℃, especially preferably 50~80 ℃.
In step (2), used reagent can be fluoroboric acid or fluoroborate, also can use hexafluorophosphoric acid or fluorophosphate.Particularly preferably be Sodium tetrafluoroborate or Sodium phosphorofluoridate.
The reaction of step (2) should be carried out at low temperatures, preferably carries out in-20 ℃~20 ℃ temperature range, preferably carries out in-5 ℃~5 ℃ temperature range especially.
In step (3), the diazonium fluoride borate or the diazonium fluoride phosphoric acid salt that step (2) are obtained by heating decompose, and obtain 1-fluoronaphthalene product.The pyrolysated temperature preferably is controlled in 50 ℃~150 ℃ the scope, is more preferably in 70 ℃~120 ℃ scope.
Particularly preferably be, in step (3), diazonium fluoride borate or diazonium fluoride phosphoric acid salt that step (2) is obtained carry out thermolysis in solvent.Described solvent comprises such as but not limited to ethylene dichloride, trichloromethane, tetracol phenixin, chlorobenzene, bromobenzene, hexane, heptane, pentane, sherwood oil, hexanaphthene, benzene,toluene,xylene, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), N-Methyl pyrrolidone (NMP) or acetonitrile.Preferred solvent is chlorobenzene or sherwood oil.
Above-mentioned preparation method's synthesis path for example can be represented with following reaction formula.
In above reaction formula, adopt HCl as acidic medium, adopt Sodium Nitrite as diazo reagent, adopt the reagent of fluoroboric acid as step (2).As can be known, used reagent is an example to those skilled in the art in the above reaction formula, does not limit the scope of the invention after having read this specification sheets.When using other reagent to carry out preparation method of the present invention, also can represent synthesis path with corresponding reaction formula.
Major advantage of the present invention is as follows.The preparation method of 1-fluoronaphthalene of the present invention compares with prior art, and synthetic route is short, and by product is few, and reaction conditions is gentle and easy to control, cost is lower, easily realizes industrialization, and throughput is big, products obtained therefrom purity height, steady quality, and meet service requirements fully as pharmaceutical intermediate.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, or carries out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are molar part, and all per-cent is molar percentage.
Embodiment 1
In the four-hole bottle of 2000ml, add 143 gram (being equivalent to 1 mole) naphthalidine and 400ml hydrochloric acid solns, keeping temperature is 50~60 ℃ of stir about half an hour, then reacting liquid temperature is cooled to-3 ℃, drip 40% sodium nitrite in aqueous solution 250ml (being equivalent to 1.1 moles of Sodium Nitrites), dropwised in lasting about 2 hours, and be incubated about half an hour.Then, drip 40% fluoborate aqueous solution 308ml (being equivalent to 1.4 moles of fluoroboric acid), generate tiny solid immediately, dropping continues to finish half an hour approximately, after stirring 1 hour, and suction filtration, washing obtains diazonium fluoride borate solid 222.8 grams after the oven dry.
The 1000ml four-hole bottle is heated, temperature is controlled to be 70~75 ℃, drop into the diazonium fluoride borate solid that as above obtains in batches, make it carry out thermolysis, after decomposition finishes, with the organic phase rectifying that obtains, receive to such an extent that product 76.5 restrains, described product is a colourless liquid, records with area normalization method by gas-chromatography, and 1-fluoronaphthalene weight percentage wherein is 99.5%.The mass spectrum of product 1-fluoronaphthalene as shown in Figure 1.Measure with rectificating method, the boiling point of gained 1-fluoronaphthalene product is 88 ℃ (20mmHg).
Embodiment 2
In the four-hole bottle of 2000ml, add 143 gram (being equivalent to 1 mole) naphthalidine and 450ml sulphuric acid solns, keeping temperature is 60~70 ℃ of stir about half an hour, reacting liquid temperature is cooled to 5 ℃ then, drip 40% sodium nitrite in aqueous solution 680ml (being equivalent to 3.0 moles of Sodium Nitrites), dropwised in lasting about 2 hours, and be incubated about half an hour.Then, drip 40% Sodium tetrafluoroborate aqueous solution 270ml (being equivalent to 1.2 moles of Sodium tetrafluoroborates), generate tiny solid immediately, dropping continues to finish half an hour approximately, after stirring 1 hour, and suction filtration, washing obtains diazonium fluoride borate solid 232 grams after the oven dry.
The 1000ml four-hole bottle is heated, temperature is controlled to be 140-150 ℃, drop into the diazonium fluoride borate solid that as above obtains in batches, make it carry out thermolysis, after decomposition finishes, with the organic phase rectifying that obtains, receive to such an extent that product 82.1 restrains, described product is a colourless liquid, records with area normalization method by gas-chromatography, and 1-fluoronaphthalene weight percentage wherein is 99.3%.Measure with rectificating method, the boiling point of gained 1-fluoronaphthalene product is 88 ℃ (20mmHg).
Embodiment 3
In the four-hole bottle of 2000ml, add 143 gram (being equivalent to 1 mole) naphthalidine and 400ml hydrochloric acid solns, keeping temperature is 70-80 ℃ of stir about half an hour, then reacting liquid temperature is cooled to-5 ℃, drip 40% sodium nitrite in aqueous solution 340ml (being equivalent to 1.5 moles of Sodium Nitrites), dropwised in lasting about 2 hours, and be incubated about half an hour.Then, drip 40% hexafluorophosphoric acid aqueous solution 150ml (being equivalent to 1 mole of hexafluorophosphoric acid), generate tiny solid immediately, dropping continues to finish half an hour approximately, after stirring 1 hour, and suction filtration, washing obtains diazonium fluoride phosphoric acid salt solid 235 grams after the oven dry.
The 1000ml four-hole bottle is heated, temperature is controlled to be 120-130 ℃, drop into the diazonium fluoride phosphoric acid salt solid that as above obtains in batches, make it carry out thermolysis, after decomposition finishes, with the organic phase rectifying that obtains, receive to such an extent that product 84 restrains, described product is a colourless liquid, records with area normalization method by gas-chromatography, and 1-fluoronaphthalene weight percentage wherein is 99.4%.Measure with rectificating method, the boiling point of gained 1-fluoronaphthalene product is 88 ℃ (20mmHg).
Embodiment 4
In the four-hole bottle of 2000ml, add 143 gram (being equivalent to 1 mole) naphthalidine and 400ml hydrochloric acid solns, keeping temperature is 50~60 ℃ of stir about half an hour, then reacting liquid temperature is cooled to-10 ℃, drip 40% sodium nitrite in aqueous solution 450ml (being equivalent to 2 moles of Sodium Nitrites), dropwised in lasting about 2 hours, and be incubated about half an hour.Then, drip 40% Sodium phosphorofluoridate aqueous solution 480ml (being equivalent to 3.2 moles of Sodium phosphorofluoridates), generate tiny solid immediately, dropping continues to finish half an hour approximately, after stirring 1 hour, and suction filtration, washing obtains diazonium fluoride phosphoric acid salt solid 228 grams after the oven dry.
The 1000ml four-hole bottle is heated, temperature is controlled to be 55-60 ℃, drop into the diazonium fluoride phosphoric acid salt solid that as above obtains in batches, make it carry out thermolysis, after decomposition finishes, with the organic phase rectifying that obtains, receive to such an extent that product 91.2 restrains, described product is a colourless liquid, records with area normalization method by gas-chromatography, and 1-fluoronaphthalene weight percentage wherein is 99.2%.Measure with rectificating method, the boiling point of gained 1-fluoronaphthalene product is 88 ℃ (20mmHg).
Embodiment 5
Undertaken by embodiment 1 identical method, different is to make after the diazonium fluoride borate solid, add 360 milliliters of chlorobenzenes in the 1000ml four-hole bottle, temperature is controlled to be 70~75 ℃, drops into the diazonium fluoride borate solid that as above obtains in batches, make it carry out thermolysis, after decomposition finished, chlorobenzene was removed in distillation, carries out rectifying again, receive to such an extent that product colourless liquid 96.5 restrains, described product is a colourless liquid, records with area normalization method by gas-chromatography, and 1-fluoronaphthalene weight percentage wherein is 99.5%.Measure with rectificating method, the boiling point of gained 1-fluoronaphthalene product is 88 ℃ (20mmHg).
Embodiment 6
Undertaken by embodiment 2 identical methods, different is, make after the diazonium fluoride borate solid, in the 1000ml four-hole bottle, add 350 milliliters of sherwood oils, temperature is controlled to be 100-120 ℃, drop into the diazonium fluoride borate solid that as above obtains in batches, make it carry out thermolysis, after decomposition finished, sherwood oil was removed in distillation, carries out rectifying again, receive to such an extent that product colourless liquid 103.4 restrains, described product is a colourless liquid, records with area normalization method by gas-chromatography, and 1-fluoronaphthalene weight percentage wherein is 99.2%.Measure with rectificating method, the boiling point of gained 1-fluoronaphthalene product is 88 ℃ (20mmHg).
Embodiment 7
Undertaken by embodiment 3 identical methods, different is, make after the diazonium fluoride phosphoric acid salt solid, in the 1000ml four-hole bottle, add 380 ml n-hexanes, temperature is controlled to be 80-100 ℃, drop into the diazonium fluoride phosphoric acid salt solid that as above obtains in batches, make it carry out thermolysis, after decomposition finished, normal hexane was removed in distillation, carries out rectifying again, receive to such an extent that product colourless liquid 111.2 restrains, described product is a colourless liquid, records with area normalization method by gas-chromatography, and 1-fluoronaphthalene weight percentage wherein is 99.1%.Measure with rectificating method, the boiling point of gained 1-fluoronaphthalene product is 88 ℃ (20mmHg).
Embodiment 8
Undertaken by embodiment 4 identical methods, different is, make after the diazonium fluoride phosphoric acid salt solid, in the 1000ml four-hole bottle, add 400 milliliters of tetracol phenixin, temperature is controlled to be 55-60 ℃, drop into the diazonium fluoride phosphoric acid salt solid that as above obtains in batches, make it carry out thermolysis, after decomposition finished, tetracol phenixin was removed in distillation, carries out rectifying again, receive to such an extent that product colourless liquid 98.5 restrains, described product is a colourless liquid, records with area normalization method by gas-chromatography, and 1-fluoronaphthalene weight percentage wherein is 99.3%.Measure with rectificating method, the boiling point of gained 1-fluoronaphthalene product is 88 ℃ (20mmHg).
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.

Claims (12)

1. method for preparing the 1-fluoronaphthalene, this method may further comprise the steps:
(1) naphthalidine is obtained diazonium salt with nitrous acid, nitrous acid ester or nitrite reaction in acidic medium;
(2) diazonium salt that step (1) obtains and fluoroboric acid or its salt or hexafluorophosphoric acid or its salt are reacted, obtain diazonium fluoride borate or diazonium fluoride phosphoric acid salt;
(3) diazonium fluoride borate or the diazonium fluoride phosphoric acid salt that step (2) is obtained carries out thermal degradation, obtains the 1-fluoronaphthalene.
2. the method for claim 1 is characterized in that, described step (3) is carried out in nonpolar or polar organic solvent.
3. method as claimed in claim 2, it is characterized in that described solvent is selected from ethylene dichloride, trichloromethane, tetracol phenixin, chlorobenzene, bromobenzene, hexane, heptane, pentane, sherwood oil, hexanaphthene, benzene,toluene,xylene, dimethyl formamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone or acetonitrile.
4. method as claimed in claim 3 is characterized in that described solvent is selected from chlorobenzene or sherwood oil.
5. the method for claim 1 is characterized in that, described step (1) forms the reaction of diazonium salt and described step (2) forms the diazonium fluoride borate or diazonium fluoride is phosphatic is reflected in-20 ℃~20 ℃ the temperature range and carries out.
6. as each described method among the claim 1-4, it is characterized in that the thermal degradation temperature of described step (3) is controlled in 50~150 ℃ the scope.
7. method as claimed in claim 6 is characterized in that, the thermal degradation temperature of described step (3) is controlled in 70~120 ℃ the scope.
8. the method for claim 1 is characterized in that, the mol ratio of naphthalidine and described fluoroboric acid or its salt or hexafluorophosphoric acid or its salt is 1: 1~1: 4.
9. the method for claim 1 is characterized in that, the mol ratio of naphthalidine and described nitrous acid, nitrous acid ester or nitrite is 1: 1.1~1: 3.
10. the method for claim 1 is characterized in that, described acidic medium is selected from HCl, H 2SO 4Or HBr.
11. the method for claim 1 is characterized in that, described nitrite is NaNO 2
12. the method for claim 1 is characterized in that, described fluoroborate is NaBF 4Described fluorophosphate is NaPF 6
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CN101870636B (en) * 2010-04-01 2013-01-23 大唐(杭州)医药化工有限公司 Preparation method of 2-bromo-6-fluoronaphthalene
CN102557865B (en) * 2011-12-27 2014-03-12 浙江永太科技股份有限公司 Method for preparing 1-fluoronaphthalene
CN102643160A (en) * 2012-04-19 2012-08-22 江苏施美康药业有限公司 Preparation method of 1,2,4-trifluorobenzene
CN103664512B (en) * 2013-09-22 2015-02-11 荆楚理工学院 Method for preparing 1-fluoronaphthalene of 99.9% in purity
CN104447189A (en) * 2014-11-17 2015-03-25 武汉瑞阳化工有限公司 New method for synthesizing naphthaline-series fluorine-containing intermediate 1-fluoronaphthalene
CN105753631B (en) * 2014-12-15 2018-11-02 沈阳化工研究院有限公司 A kind of synthetic method of aromatic fluorine compound
CN106866350B (en) * 2017-04-01 2019-06-11 宁夏中星显示材料有限公司 A kind of preparation method of high-purity 2- bromine fluorenes
CN109180416A (en) * 2018-09-06 2019-01-11 武汉瑞阳化工有限公司 The synthetic method of naphthalene system fluoro-containing intermediate 1- fluoronaphthalene
CN112778075A (en) * 2021-02-01 2021-05-11 李佰卫 Preparation method of 1-fluoronaphthalene

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1246469A (en) * 1998-04-22 2000-03-08 大日本油墨化学工业株式会社 Naphthacridine derivative and liquid crystal composite containing it

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1246469A (en) * 1998-04-22 2000-03-08 大日本油墨化学工业株式会社 Naphthacridine derivative and liquid crystal composite containing it

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