WO2014069674A1 - Procédé de production d'acide 6-bromo-2-naphtoïque - Google Patents

Procédé de production d'acide 6-bromo-2-naphtoïque Download PDF

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Publication number
WO2014069674A1
WO2014069674A1 PCT/JP2013/080361 JP2013080361W WO2014069674A1 WO 2014069674 A1 WO2014069674 A1 WO 2014069674A1 JP 2013080361 W JP2013080361 W JP 2013080361W WO 2014069674 A1 WO2014069674 A1 WO 2014069674A1
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WIPO (PCT)
Prior art keywords
naphthoic acid
bromo
acid
reaction
amino
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PCT/JP2013/080361
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English (en)
Japanese (ja)
Inventor
健治 峯山
聡志 立花
幸司 宮城
充浩 西野
寿秀 駿河
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スガイ化学工業株式会社
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Publication of WO2014069674A1 publication Critical patent/WO2014069674A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms

Definitions

  • the present invention relates to a method for producing 6-bromo-2-naphthoic acid (6-bromo-2-naphthalenecarboxylic acid).
  • the target compound of the present invention 6-bromo-2-naphthoic acid (CAS number: 5773-80-8), is a known substance, and is a useful compound as a synthetic intermediate in the production of pharmaceuticals, agricultural chemicals and the like. Therefore, establishment of an inexpensive and industrial production method is strongly desired.
  • 6-hydroxy-2-methylnaphthalene is brominated with a triphenylphosphine-bromine complex to give 6-bromo-2-methylnaphthalene in an organic solvent, and the compound is converted to acetic acid or the like.
  • Patent Document 1 In the method described in Patent Document 1, it is necessary to use relatively expensive raw materials and reaction reagents. Moreover, since an organic solvent is used, there is a problem that the cost including the recovery cost increases. Furthermore, the total yield is about 60%, and there is a problem that a heavy metal catalyst is used. Therefore, the method described in Patent Document 1 is not appropriate as a method for producing 6-bromo-2-naphthoic acid easily and inexpensively. Further, in the method described in Patent Document 2, 2-bromonaphthalene is acetylated by Friedel-Crafts reaction, the impurities increase, and it is difficult to obtain high-purity 6-bromo-2-acetylnaphthalene in high yield. .
  • Patent Document 2 the yield of 6-bromo-2-acetylnaphthalene after recrystallization is 21%, and it is difficult to obtain 6-bromo-2-naphthoic acid, which is the final target product, in high yield.
  • a large amount of fuming anhydrous aluminum chloride is used, there are problems in the working environment and wastewater treatment.
  • Patent Document 2 since an organic solvent is used in Patent Document 2, there is also a problem of an increase in cost.
  • the conventional method for producing 6-bromo-2-naphthoic acid has various problems, and an industrially established method for producing 6-bromo-2-naphthoic acid is not known.
  • the present inventors examined an industrial production method of 6-bromo-2-naphthoic acid.
  • a hydroxyl group of 6-hydroxy-2-naphthoic acid was converted to an amino group by a Bucherer reaction.
  • 6-amino-2-naphthoic acid is converted to a group, and the obtained 6-amino-2-naphthoic acid is subjected to a diazotization reaction to form a diazotized product, which is then reacted with copper bromide to give 6
  • -bromo-2-naphthoic acid was obtained in high yield.
  • This invention is based on the knowledge which concerns, and this invention provides the industrial manufacturing method of 6-bromo- 2-naphthoic acid.
  • the raw materials and the reaction reagent are inexpensive, and the production cost can be reduced.
  • any reaction proceeds using water as a solvent, an increase in cost due to the use of an organic solvent can be avoided.
  • the reaction position is specified, there are few side reactions and the target product can be obtained with high purity. Therefore, according to the production method of the present invention, there is an effect that 6-bromo-2-naphthoic acid can be produced industrially and inexpensively.
  • the present invention comprises the above-described configuration.
  • 6-hydroxy-2-naphthoic acid is obtained by reacting 6-hydroxy-2-naphthoic acid with ammonia in the presence of sulfite or bisulfite. Is converted to an amino group to obtain 6-amino-2-naphthoic acid, and this reaction is known as a Bucherer reaction. In this reaction, sulfite or bisulfite is used as a catalyst, and both may be used in combination.
  • sulfite used examples include alkali metal salts of sulfite (for example, sodium salt, potassium salt, etc.), ammonium salts, and the like, and bisulfite salts are also exemplified by similar salts.
  • bisulfite is preferably used, and ammonium bisulfite is particularly preferably used from the viewpoint of yield.
  • the amount of sulfite or bisulfite used is in the range of 0.1 to 1.5 molar ratio, preferably 0.2 to 1.0 molar ratio, relative to 6-hydroxy-2-naphthoic acid.
  • the molar ratio is less than 0.1, it is difficult to proceed with the reaction, and if it exceeds 1.5, there is no particular problem, but it is sufficient if it is less than 1.5.
  • ammonia ammonia gas, ammonia water (for example, 28% ammonia water) or the like is used.
  • the amount of ammonia used is in the range of 2 to 12 molar ratio, preferably 3 to 7 molar ratio with respect to 6-hydroxy-2-naphthoic acid. If the molar ratio is less than 2, the progress of the reaction is difficult, and if it exceeds 12, the yield may decrease.
  • This reaction is usually carried out in a solvent, and any solvent can be used as long as the solvent does not adversely influence the reaction, but an aqueous solvent is usually used.
  • the reaction temperature is 80 to 150 ° C, preferably 110 to 130 ° C. As a preferred embodiment, it is carried out under pressure and heating conditions using a pressure vessel such as an autoclave.
  • the pressure is 0.2 to 1.0 MPa, preferably 0.3 to 0.7 MPa, and the reaction temperature is 110 to 150 ° C.
  • the reaction time is 5 to 15 hours, usually 8 to 12 hours.
  • 6-amino-2-naphthoic acid is produced from 6-hydroxy-2-naphthoic acid.
  • 6-amino-2-naphthoic acid obtained above is subjected to a diazotization reaction to give a diazotized product, and then reacted with copper bromide to give 6-bromo-2-naphthoic acid. It is the process of obtaining.
  • the diazotization reaction is a reaction well known to those skilled in the art, and a normal method can be used for the synthesis of the diazotized product.
  • the diazotization reaction can be carried out by subjecting 6-amino-2-naphthoic acid to diazotization with a nitroso source under acidic conditions in an aqueous solvent according to a conventional method.
  • nitroso source used in the diazotization reaction examples include nitrous acid, nitrite (for example, sodium nitrite), isoamyl nitrite and the like.
  • the amount of the nitroso source used is in the range of 1 to 10 molar ratio, preferably 1 to 5 molar ratio with respect to 6-amino-2-naphthoic acid. If the molar ratio is less than 1, the reaction does not proceed sufficiently. On the other hand, if it exceeds 10, there is no problem, but the amount up to that point is sufficient.
  • inorganic acid such as hydrochloric acid, sulfuric acid, hydrogen halide solution (for example, hydrobromic acid solution, hydroiodic acid solution, etc.) and organic acid such as acetic acid are used.
  • the reaction is carried out for cooling (about 0 to 5 ° C.), and the reaction is completed within 30 minutes to 3 hours, usually about 1 to 2 hours, and a diazotized product is formed.
  • the diazotide obtained above can be used in the next step as it is, and 6-bromo-2-naphthoic acid is produced by reacting with copper (I) bromide. This reaction is well known as the Sandmeyer reaction.
  • This reaction is usually performed in an aqueous solvent in the presence of an acid, and examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, and a hydrogen halide solution. Among them, a hydrogen halide solution is preferable, and particularly hydrobromic acid.
  • a liquid is preferably used.
  • the amount of copper (I) bromide to be used is in the range of 0.5 to 5 molar ratio, preferably 1 to 4 molar ratio with respect to the diazotized product. When the molar ratio is less than 0.5, the reaction does not proceed sufficiently. On the other hand, when the molar ratio exceeds 5, there is no problem, but the reaction proceeds sufficiently with the previous amount.
  • the reaction temperature is 5 to 80 ° C, preferably room temperature to 70 ° C.
  • the reaction time is 1 to 20 hours, usually 10 to 16 hours.
  • 6-bromo-2-naphthoic acid is precipitated from the reaction system by this process, and can be obtained by filtering the precipitate. If necessary, purification is performed by a conventional method such as recrystallization.
  • Example 1 To an autoclave of 6- amino-2-naphthoic acid 2 L, 188.2 g (1.0 mol) of 6-hydroxy-2-naphthoic acid, 500 mL of water, 99.3 g (0.74 mol) of ammonium sulfite, 219% aqueous ammonia 219 .2 g (3.61 mol) was charged, and the autoclave was sealed. The temperature was raised to 130 ° C. with stirring. After the temperature increase, the reaction was conducted at 0.6 MPa for 11 hours at the same temperature. After cooling to 5 ° C.
  • Example 2 In Example 1, it reacted similarly except using ammonium hydrogensulfite instead of ammonium sulfite, and 6-amino- 2-naphthoic acid was obtained (purity: 98%, yield: 93%).
  • Example 3 In Example 1, instead of ammonium sulfite, ammonium bisulfite (1.0 molar ratio with respect to 6-hydroxy-2-naphthoic acid) was used in the same manner except that ammonium bisulfite was used.
  • Example 4 In Example 1, instead of ammonium sulfite, the reaction was carried out in the same manner except that ammonium hydrogen sulfite (0.2 molar ratio with respect to 6-hydroxy-2-naphthoic acid) was used. The acid was obtained (yield 92%).
  • Example 5 In Example 1, 6-amino-2-naphthoic acid was obtained in the same manner as in Example 1 except that sodium hydrogen sulfite was used instead of ammonium sulfite and the pressure was 0.4 MPa (yield 92%).
  • Example 6 In a 3 L flask of 6- bromo -2-naphthoic acid, 71.8 g (0.376 mol) of 6-amino-2-naphthoic acid, 972.6 g of water, 262.3 g of 47% hydrobromic acid (4.05 mol ratio) ), And cooled to 5 ° C. or lower. 146.2% sodium nitrite aqueous solution 206.2g (1.1 molar ratio) was dripped at 5 degrees C or less, and it stirred for 2 hours, and obtained the diazotization liquid.
  • Example 7 In the Sandmeyer reaction step of Example 6, the reaction was carried out in the same manner except that the amount of copper (I) bromide used was 2.66 molar ratio to obtain 6-bromo-2-naphthoic acid (yield 78%). ).
  • 6-bromo-2-naphthoic acid which is useful as a raw material for pharmaceuticals, agricultural chemicals and the like, can be produced industrially and inexpensively.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de production d'acide 6-bromo-2-naphtoïque qui est utilisé en tant que matière première dans des produits pharmaceutiques, des produits agrochimiques, etc. Ledit procédé de production d'acide 6-bromo-2-naphtoïque comprend les étapes consistant à faire réagir de l'acide 6-hydroxy-2-naphtoïque avec de l'ammoniac en présence de sulfite ou de bisulfite afin d'obtenir de l'acide 6-amino-2-naphtoïque, à soumettre l'acide 6-amino-2-naphtoïque obtenu à une réaction de diazotisation afin d'obtenir un composé diazotisé, puis à faire réagir ledit composé diazotisé avec du bromure de cuivre en présence d'un acide. La présente invention permet de produire de l'acide 6-bromo-2-naphtoïque d'une grande pureté avec un bon rendement et pour un faible coût.
PCT/JP2013/080361 2012-11-01 2013-10-31 Procédé de production d'acide 6-bromo-2-naphtoïque WO2014069674A1 (fr)

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JP2012-242257 2012-11-01

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110590541A (zh) * 2019-10-16 2019-12-20 吕东 一种5-溴-2-氯苯甲酸的制备方法
CN112778116A (zh) * 2020-12-30 2021-05-11 湖北鸿鑫化工有限公司 一种1，4-萘二甲酸的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60500815A (ja) * 1983-03-03 1985-05-30 エス・ア−ル・アイ・インタ−ナシヨナル ナフチルまたはテトラヒドロナフチル置換されたナフトエ酸および誘導体
JPH05502469A (ja) * 1989-12-29 1993-04-28 ヘキスト・アクチェンゲゼルシャフト アゾ化合物、その製法及び染料としての該化合物の用途

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60500815A (ja) * 1983-03-03 1985-05-30 エス・ア−ル・アイ・インタ−ナシヨナル ナフチルまたはテトラヒドロナフチル置換されたナフトエ酸および誘導体
JPH05502469A (ja) * 1989-12-29 1993-04-28 ヘキスト・アクチェンゲゼルシャフト アゾ化合物、その製法及び染料としての該化合物の用途

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
EDITED BY CSJ: "The Chemical Society of Japan, Kagaku Benran Kiso-hen, revised 5th edition", KAGAKU BENRAN KISO-HEN, REVISED 5TH EDITION,UZEN CO., LTD, 20 February 2004 (2004-02-20), pages II-423 *
EDITED BY CSJ: "The Chemical Society of Japan, Shin Jikken Kagaku Koza 14", SHIN JIKKEN KAGAKU KOZA, MARUZEN CO., LTD, vol. 14, 20 February 1978 (1978-02-20), pages 1356 - 1357 *
KARISHIN, A. P.: "Halo-8-nitro-1-naphthoic acids", ZHURNAL OBSHCHEI KHIMII, vol. 33, no. 7, 1963, pages 2247 - 2250 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110590541A (zh) * 2019-10-16 2019-12-20 吕东 一种5-溴-2-氯苯甲酸的制备方法
CN112778116A (zh) * 2020-12-30 2021-05-11 湖北鸿鑫化工有限公司 一种1，4-萘二甲酸的制备方法

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