CN113735694B - Method for synthesizing 9-halogen-7H-benzo [ c ] fluorene-7-ketone - Google Patents
Method for synthesizing 9-halogen-7H-benzo [ c ] fluorene-7-ketone Download PDFInfo
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
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- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
The invention discloses a method for synthesizing 9-halogen-7H-benzo [ c ] fluorene-7-ketone (compound of formula I), wherein X is one of Cl and Br. The method comprises the following steps: 1-hydroxy-2-methyl naphthoate is taken as a raw material, and is etherified by trifluoro methane sulfonate to obtain a compound shown in a formula A; the compound of the formula A and 4-halogenated phenylboronic acid are subjected to Suzuki reaction to obtain a compound of the formula B; carrying out alkaline hydrolysis on the compound of the formula B to obtain a compound of the formula C; the compound of formula C is cyclized under acidic conditions to obtain the compound of formula I. The method solves the problems of large consumption of ring-closing reagent, large tar content, difficult purification, low yield and large wastewater content in the prior method, and is more beneficial to the subsequent amplified production process by improving the reaction method of the intermediate compound and the final product.
Description
Technical Field
The invention belongs to the technical field of organic electroluminescence (OLED), and particularly relates to a synthesis method of 9-halogen-7H-benzo [ c ] fluorene-7-ketone. The invention also provides a synthetic intermediate compound of the compound shown in the formula I and a preparation method thereof.
Background
Currently, fluorene compounds are widely used in organic optoelectronic devices, electrophotographic materials, solar cell materials, color liquid crystal materials, organic optical information recording materials, and the like. The spirobifluorene molecule has the characteristics of a non-planar space structure, higher glass transition temperature, proper HOMO (highest occupied molecular orbital) and LUMO (unoccupied electron lowest energy orbital) energy level and higher Eg orbit due to the unique structural characteristics, can be sublimated under the condition of no decomposition and no residue, can effectively improve the luminous performance and service life of an OLED device, and is suitable for phosphorescent and fluorescent (containing TADF) OLED devices. The compound of the formula I is an essential intermediate in the preparation process of spirobifluorene molecules, and is widely applied to various terminal compounds containing spirobifluorene structures.
Wherein X is one of Cl and Br.
The synthetic routes of the compounds of formula I disclosed in KR2014128879, KR2014128878, KR2015095545 and KR2016113488 preset the ketocarbonyl function on the benzene ring prior to the ring closure reaction, resulting in a large amount (20% to 50%) of the isomerised product as a result of the synthesis of the synthetic routes. The synthetic routes of the compounds of formula I disclosed in CN11592464 and CN105418357 use methyl 1-bromo-2-naphthoate as starting materials, and methyl 1-bromo-2-naphthoate is expensive, so that the cost problem exists in large-scale industrial production by adopting the synthetic routes. The synthetic route of the compound of formula I disclosed in JP5320722B2 solves the problem of higher product cost by replacing expensive methyl 1-bromo-2-naphthoate with inexpensive methyl 1-hydroxy-2-naphthoate, but the last step of the patent is actually a two-step reaction, namely hydrolysis reaction of carboxylate under acidic conditions and carboxylic acid ring closure reaction. Those skilled in the art will readily appreciate that acidic hydrolysis of carboxylic acid esters is a reversible reaction with limited yields. The two steps are combined into one step, so that the dosage of the ring-closing reagent is large, the tar amount of the system is large, and the yield of the last step is only 57%. Meanwhile, due to the use of a large amount of ring-closing reagents, the amount of wastewater is increased, and the environmental protection pressure is increased.
Although the above patents all propose synthetic routes to the compounds of formula I, the existence of these problems limits the subsequent commercial production of the compounds of formula I as an essential intermediate for compounds containing spirobifluorene structures. Therefore, it is necessary to study the optimization of the synthesis process of the compound of the formula I, and the guarantee is provided for the industrial production of the compound of the formula I.
Disclosure of Invention
The invention aims to solve the problems of large consumption of ring-closing reagent, large tar content, difficult purification, low yield and large wastewater content in the JP5320722B2 patent, and provides a synthetic method of a compound shown in a formula I suitable for industrial production.
Based on the above purposes, the invention provides a method for preparing the compound of the formula I by closing a ring under acidic conditions, has high yield of synthesis results, and improves the reaction method of the intermediate compound and the final product so as to be more beneficial to the subsequent amplified production process.
In one aspect, the invention relates to compounds of formula I:
Wherein X is one of Cl and Br.
In another aspect, the present invention relates to a method of synthesizing a compound of formula i comprising the steps of:
Closing ring of the compound of formula C under acidic condition to obtain the compound of formula I:
Wherein X is one of Cl and Br.
In another aspect, the present invention relates to a method of synthesizing a compound of formula C, comprising the steps of:
alkaline hydrolysis of the compound of formula B to give a compound of formula C:
Wherein X is one of Cl and Br.
In another aspect, the present invention relates to a method of synthesizing a compound of formula B comprising the steps of:
The compound of the formula A and 4-halogenated phenylboronic acid are subjected to Suzuki reaction to obtain a compound of the formula B:
Wherein X is one of Cl and Br.
In another aspect, the present invention relates to a method of synthesizing a compound of formula a comprising the steps of:
1-hydroxy-2-methyl naphthoate is used as a raw material, and is etherified by trifluoromethane sulfonate to obtain a compound of a formula A:
in another aspect, the present invention provides the following reaction scheme for compounds of formula i:
specifically, the compound of formula a is prepared by:
dissolving raw material 1-hydroxy-2-methyl naphthoate in a solvent I, wherein the volume mass ratio of the solvent to the raw material 1-bromo-2-methyl naphthoate is 2:1-10:1, adding an acid-binding agent, the mol ratio of the acid-binding agent to the raw material 1-bromo-2-methyl naphthoate is 1:1-3:1, dropwise adding trifluoromethanesulfonic anhydride at the temperature of-20-40 ℃, adding the mol ratio of the trifluoromethanesulfonic anhydride to the raw material 1-hydroxy-2-methyl naphthoate is 0.9:1-1.5:1, reacting for 1-6 h at the temperature of-20-40 ℃ after the dropwise adding, acidifying, extracting, washing and concentrating to obtain the compound shown in the formula A.
In some embodiments, wherein the method is performed in the presence of a solvent; preferably, the solvent I is selected from dichloromethane, dichloroethane, chloroform, toluene, methylcyclohexane; preferably, the reaction solvent I is one of dichloromethane and toluene.
In some embodiments, wherein the method is performed in the presence of an acid binding agent; preferably, the acid binding agent used is selected from triethylamine, pyridine, dimethylethylenediamine or 4-dimethylaminopyridine; preferably, the acid binding agent is one of triethylamine and pyridine.
Specifically, the compound of formula B is prepared by the steps of:
Under the action of a catalyst, the mol ratio of the catalyst to the compound of the formula A is 0.0001:1-0.01:1, the compound of the formula A, 4-halogeno phenylboronic acid and alkali are uniformly mixed in a solvent II, the mol ratio of the compound of the formula A to the 4-halogeno phenylboronic acid is 1:0.9-1:1.5, the volume mass ratio of the solvent II to the compound of the formula A is 5:1-15:1, the mol ratio of the alkali to the compound of the formula A is 0.5:1-3:1, the Suzuki reaction is carried out for 2-25 h at the temperature of 60-120 ℃, and the compound of the formula B is prepared by extraction, water washing and concentration.
In some embodiments, wherein the process is performed in the presence of a catalyst; preferably, the catalyst used is selected from Pd (Pph 3)4、PdCl2(Pph3)2, pd-132).
In some embodiments, wherein the method is performed in the presence of a solvent; preferably, the solvent II is one, two or three of ethanol, toluene, dioxane, tetrahydrofuran and water; preferably, the solvent II is a mixed solvent of toluene and water; preferably, the solvent II is toluene.
In some embodiments, wherein the method is performed in a basic environment; preferably, the reaction base is selected from K2CO3、Na2CO3、KHCO3、NaHCO3、CH3COOK、CH3COONa;, preferably, the reaction base is selected from K 2CO3、Na2CO3、KHCO3.
Specifically, the compound of formula C is prepared by the steps of:
Mixing a compound of a formula B and an alkaline hydrolysis reagent, carrying out reflux reaction on the mixture and a solvent III for 1 to 10 hours at a temperature of between 70 and 100 ℃, enabling the molar ratio of the alkaline hydrolysis reagent to the compound of the formula B to be 1.5:1 to 5:1, enabling the volume mass ratio of the solvent III to the compound of the formula B to be 3:1 to 10:1, and carrying out acidification, extraction, water washing and material drying to obtain a compound of the formula C;
in some embodiments, wherein the method is performed in the presence of an alkaline hydrolysis reagent; preferably, the alkaline hydrolysis reagent used is selected from potassium hydroxide, sodium hydroxide.
In some embodiments, wherein the method is performed in the presence of a solvent; preferably, the solvent III is one or a mixture of two of methanol, ethanol and water.
Specifically, the compound of formula I is prepared by the following steps:
Dissolving a compound of a formula C in a solvent IV, wherein the volume mass ratio of the solvent IV to the compound of the formula C is 4:1-10:1, then adding a ring closing reagent, wherein the mass ratio of the ring closing reagent to the compound of the formula C is 5:1-10:1, reacting at 40-140 ℃ for 4-15 hours, extracting, washing, concentrating and recrystallizing to obtain the compound of the formula I;
In some embodiments, wherein the method is performed in the presence of a ring-closing reagent; preferably, the ring-closing reagent used is selected from PPA, methylsulfonic acid.
In some embodiments, wherein the method is performed in the presence of a solvent; preferably, the solvent used is selected from dichloromethane, dichloroethane, toluene or xylene.
Compared with the prior art, the invention has the following beneficial effects or advantages:
(1) The invention disassembles the ring closing reaction of the prepared compound of the formula I into two steps of alkaline hydrolysis and ring closing reaction, replaces acidolysis with carboxylic ester classical alkaline hydrolysis, avoids the occurrence of reversible reaction, has the yield of more than 90% in the two steps of reaction, and is more beneficial to large-scale industrial production;
(2) The invention selects the compound of the formula C as a precursor for synthesizing the compound of the formula I, and carboxyl in the compound of the formula C is easy to carry out substitution reaction to prepare the compound of the formula I, thereby ensuring the yield of the step;
(3) The invention has low consumption of the ring-closing reagent, avoids the generation of tar in the reaction system, ensures that the purification of the final product is simpler, and reduces the consumption of wastewater.
Detailed Description
The methods of the present invention can be carried out using the methods disclosed herein and conventional modifications thereof, which modifications will be apparent from the disclosure herein and from methods well known in the art. Conventional and well known synthetic methods may be used in addition to those taught herein. The synthesis of typical compounds described herein (e.g., compounds of formula i) can be accomplished as described in the examples below.
Example 1
The present examples provide the preparation and synthesis of compounds of formula A, formula B, formula C, and formula I.
(1) Preparation of Compounds of formula A
600Ml of toluene, 202.2g of 1-hydroxy-2-naphthoic acid methyl ester and 101.2g of triethylamine are sequentially added into a 3L three-port bottle under the protection of nitrogen, the system is cooled to-20 ℃, 253.9g of trifluoromethanesulfonic anhydride is dropwise added, the temperature is controlled to-20 ℃ to-10 ℃, and the reaction is stopped after the addition is completed for 6 hours. The reaction system was poured into 2000ml of 7% diluted hydrochloric acid, stirred, extracted with 2000ml of toluene, the combined organic phases were washed to neutrality, concentrated under reduced pressure until no solvent was evolved, yielding 300.0g of the compound of formula A.
Wherein GC (gas phase purity) >96%, Y (yield) =90%.
(2) Preparation of Compounds of formula B
To a 5L three-necked flask, 300.0g of the compound of formula A, 1500ml of toluene, 126.3g of 4-chlorophenylboronic acid, 61.9g of potassium carbonate and 0.06g of catalyst Pd-132 were successively introduced under nitrogen atmosphere. Heating, refluxing at 114-118 deg.c for 1 hr, cooling to room temperature, extracting the reaction system with 2000ml water once with 500ml toluene, merging organic phases, water washing to neutrality, and decompression concentrating to no solvent flow out to obtain reddish brown viscous concentrate 240.0g compound of the formula B.
Wherein LC (liquid phase purity) >98%, y=90%.
(3) Preparation of Compounds of formula C
240.0G of the compound of formula B obtained in the step (2), 67.9g of potassium hydroxide and 720g of water are added into a 5L three-necked flask, the mixture is heated to 100 ℃, stirred and reacted until the system is clear (about 4 hours), the reaction solution is cooled to room temperature, the pH of the system is regulated to be less than 4 by concentrated hydrochloric acid, the mixture is filtered, the obtained white solid is leached to be neutral by water, and the mixture is baked to be constant weight at 100 ℃ to obtain 228.6g of the compound of formula C.
Wherein LC >99%, y=100%.
(4) Preparation of the target product of the compound of formula I
To a dry 3L three-necked flask, 2280ml of xylene, 228.6g of the compound of formula C, 1143g of PPA were sequentially added, and the mixture was heated to 140℃to reflux and reacted for 15 hours. The reaction system was cooled to room temperature, poured into 3000ml of water, extracted with 2280ml of toluene, the organic phases were combined, washed with water to neutrality, concentrated under reduced pressure until no solvent was evolved, and the resulting orange solid was recrystallized from dichloroethane and dried at 100℃to give 193.0g of the compound of formula I (9-chloro-7H-benzo [ c ] fluoren-7-one).
Wherein LC >99.9%, y=90%.
Example 2
(1) Preparation of Compounds of formula A
2000Ml of dichloromethane, 202.2g of 1-hydroxy-2-naphthoic acid methyl ester, 237.0g of pyridine are sequentially added into a 3L three-port bottle under the protection of nitrogen, the system is cooled to 10 ℃, 564.3g of trifluoromethanesulfonic anhydride is dropwise added, the temperature is controlled to 10-20 ℃, and the reaction is stopped after the addition is completed for 1 hour. Pouring the reaction system into 2000ml of 7% diluted hydrochloric acid, stirring, adding 2000ml of toluene for extraction, combining organic phases, washing with water to be neutral, and concentrating under reduced pressure until no solvent flows out to obtain 327.6g of a compound of formula A.
Wherein GC >96%, y=98%.
(2) Preparation of Compounds of formula B
To a 10L three-necked flask, 327.6g of the compound of formula A, 3270ml of toluene, 655ml of ethanol, 295.23g of 4-bromophenylboric acid, 246.97g of sodium hydrogencarbonate, 655ml of water and 6.87g of bis (triphenylphosphine) palladium dichloride were successively added under nitrogen. After the mixing is finished, heating to a reaction temperature of 70-74 ℃, carrying out reflux reaction for 25h, cooling to room temperature, adding 2000ml of water into a reaction system, separating liquid, extracting once with 500ml of toluene, combining organic phases, washing to be neutral, concentrating under reduced pressure until no solvent flows out to obtain 282.1g of reddish brown viscous concentrate of the compound of the formula B.
Wherein LC >98%, y=97%.
(3) Preparation of Compounds of formula C
To a 5L three-necked flask were added 282.1g of the compound of formula B obtained in example 2, 190.1g of sodium hydroxide, 1400ml of water, 1400ml of methanol, heated to 70℃to 75℃and stirred to react until the system became clear (about 10 hours), the reaction solution was cooled to room temperature, pH of the system was adjusted to <4 with concentrated hydrochloric acid, filtered, the obtained white solid was rinsed to neutrality with water and baked to constant weight at 100℃to obtain 268.76g of the compound of formula C.
Wherein LC >99%, y=100%.
(4) Preparation of the target product of the compound of formula I
To a dry 3L three-necked flask, 920ml of methylene chloride, 228.6g of the compound of formula C and 2286g of methanesulfonic acid were successively added, and the mixture was heated to 40℃to reflux and reacted for 4 hours. The reaction system was cooled to room temperature, poured into 3000ml of water, extracted with 920ml of dichloromethane, the combined organic phases were washed with water to neutrality, concentrated under reduced pressure until no solvent was evolved, the resulting orange solid was recrystallized from dichloroethane and dried at 100℃to give 200.0g of the compound of formula I (9-chloro-7H-benzo [ c ] fluoren-7-one).
Wherein LC >99.9%, y=93.5%.
(5) Atlas detection of Compounds of formula I
The resulting compound of formula I (9-chloro-7H-benzo [ c ] fluoren-7-one) was analyzed using a gas chromatograph-mass spectrometer (GC-MS) and the profile detection data were as follows:
Mass spectrum of target compound (GC-MS): m=264.
1H-NMR of the target compound (500 MHz, CDCl 3): δ=8.40 (1H); δ=7.85 to 7.95 (1H); δ=7.60 (1H); δ=7.60 to 7.65 (3H); δ=7.48 (1H), whereby successful synthesis of the compound can be demonstrated.
The present invention may be better implemented as described above, and the above examples are merely illustrative of preferred embodiments of the present invention and not intended to limit the scope of the present invention, and various changes and modifications made by those skilled in the art to the technical solution of the present invention should fall within the scope of protection defined by the present invention without departing from the spirit of the design of the present invention.
Claims (4)
1. A method of synthesizing a compound of formula i:
wherein X is one of Cl and Br;
the method comprises the following steps:
Etherification is carried out on 1-hydroxy-2-naphthoic acid methyl ester to form a compound of a formula A; the compound of the formula A is subjected to Suzuki reaction to form a compound of the formula B; carrying out alkaline hydrolysis on the compound of the formula B to obtain a compound of the formula C; converting the compound of formula C into a compound of formula I,
The compound of formula a is:
the compound of formula B is:
The compound of formula C is:
The preparation method of the compound of the formula A comprises the steps of dissolving raw material 1-hydroxy-2-methyl naphthoate in a solvent I, adding an acid binding agent, dropwise adding trifluoro methanesulfonic anhydride at the reaction temperature of-20-40 ℃, reacting for 1-6 h at the temperature of-20-40 ℃ after the dropwise adding, and obtaining the compound of the formula A through acidification, extraction, water washing and concentration;
The preparation method of the compound of the formula B comprises the steps of uniformly mixing the compound of the formula A, 4-halogenated phenylboronic acid and alkali in a solvent II under the action of a catalyst, carrying out Suzuki reaction for 2-25 h at 60-120 ℃, extracting, washing with water, and concentrating to obtain the compound of the formula B;
The step of preparing the compound of the formula C is that the compound of the formula B and an alkaline hydrolysis reagent are mixed and then are subjected to reflux reaction with a solvent III for 1 to 10 hours at the temperature of between 70 and 100 ℃, and the compound of the formula C is obtained through acidification, extraction, water washing and material drying;
The step of converting the compound of the formula C into the compound of the formula I comprises the steps of dissolving the compound of the formula C in a solvent IV, adding a ring-closing reagent, reacting for 4-15 hours at the reaction temperature of 40-140 ℃, extracting, washing, concentrating and recrystallizing to obtain the compound of the formula I;
The molar ratio of the alkaline hydrolysis reagent to the compound of formula B is 1.5:1-5:1; the mass ratio of the solvent III to the compound of the formula B is 3:1-10:1; the alkaline hydrolysis reagent is one of potassium hydroxide and sodium hydroxide; the solvent III is one or two of methanol, ethanol and water;
The mass ratio of the ring-closing reagent to the compound of the formula C is 5:1-20:1, and the mass ratio of the solvent IV to the compound of the formula C is 4:1-10:1; the ring closing reagent is one of PPA and methylsulfonic acid; the solvent IV is one of dichloromethane, dichloroethane, toluene and xylene.
2. The process for preparing a compound of the formula I according to claim 1, characterized in that the molar ratio of trifluoromethanesulfonic anhydride to methyl 1-hydroxy-2-naphthoate is from 0.9:1 to 1.5:1, the volumetric mass ratio of solvent I to methyl 1-bromo-2-naphthoate is from 2:1 to 10:1; the solvent I is one of dichloromethane, dichloroethane, chloroform, toluene and methylcyclohexane; the acid binding agent is one of triethylamine and pyridine.
3. The process for preparing a compound of formula I according to claim 1, wherein the molar ratio of the compound of formula A to the 4-halogenophenylboronic acid is from 1:0.9 to 1:1.5 and the molar ratio of the catalyst to the compound of formula A is from 0.0001:1 to 0.01:1, based on the molar mass; the catalyst is Pd (Pph 3)4、PdCl2(Pph3)2 or Pd-132), the solvent II is one or a mixture of two or three of ethanol, toluene, dioxane, tetrahydrofuran and water, and the alkali is one of K2CO3、Na2CO3、KHCO3、NaHCO3、CH3COOK、CH3COONa.
4. Use of a process according to any one of claims 1 to 3 for the synthesis of 9-halo-7H-benzo [ c ] fluoren-7-one.
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| JP2009114114A (en) * | 2007-11-06 | 2009-05-28 | Tosoh Corp | Benzofluorenone derivative and method for producing the same |
| CN110832657A (en) * | 2017-07-11 | 2020-02-21 | Sfc株式会社 | Organic Light Emitting Elements with High Efficiency |
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| KR102030354B1 (en) * | 2014-05-13 | 2019-10-10 | 에스에프씨주식회사 | Heterocyclic compound comprising aromatic amine group and organic light-emitting diode including the same |
| WO2018160003A1 (en) * | 2017-02-28 | 2018-09-07 | 주식회사 엘지화학 | Heterocyclic compound and organic light-emitting device comprising same |
| CN111592464A (en) * | 2019-02-20 | 2020-08-28 | 常州强力电子新材料股份有限公司 | Organic Compounds Containing Spirobifluorene Structure and Their Applications |
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| JP2009114114A (en) * | 2007-11-06 | 2009-05-28 | Tosoh Corp | Benzofluorenone derivative and method for producing the same |
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