JP6202492B2 - Method for producing dinitro compound - Google Patents

Description

  The present invention relates to a method for producing a dinitro compound from diaminophenol and nitrobenzoyl chloride.

  Semiconductors are making rapid progress in capacity, density, integration and surface mounting. With the progress, many problems have occurred in the manufacture of semiconductor devices. One problem is that heat or thermal stress is applied to the semiconductor chip as the sealing material becomes thinner. Therefore, it is necessary to protect fine semiconductor circuits from heat or thermal stress. On the other hand, in order to form a high-density and highly integrated circuit on a semiconductor, a multilayer wiring technique is indispensable. In order to achieve this, an interlayer dielectric having high heat resistance, high adhesiveness and low dielectric constant is required.

  It is known that the above problems can be solved by using aromatic polyimide or polybenzoxazole as a passivation film, buffer coat film or interlayer dielectric. Aromatic polyimides and polybenzoxazoles are polymers with excellent thermal stability, high mechanical properties, good electrical properties and excellent chemical resistance. Polybenzoxazole has a lower moisture uptake than polyimide, but has a problem that it has poor adhesion to a silicon wafer and is easily peeled off. In order to solve this problem, the adhesiveness can be improved by improving the polybenzoxazole-polyimide copolymer into which polyimide is introduced.

  As a specific example, as shown in the following formula, an example in which diamine and tetracarboxylic dianhydride are polymerized and poly (imide-benzoxazole) is obtained by heat treatment has been reported (see Patent Documents 1, 2, and 3). ).

  In this document, diamine is synthesized using propylene oxide as an acid scavenger in the reaction of nitrobenzoyl chloride and diaminophenol as shown in the following formula.

  However, since propylene oxide which is expensive and easily polymerized is used and reacts at a low temperature of -15 ° C, it is not suitable for mass production.

  In addition, as shown in the following formula, in the reaction of nitrobenzoyl chloride and diaminophenol, an example using triethylamine as an acid scavenger has been reported, but it was necessary to purify by recrystallization to isolate the target product ( (See Patent Document 4).

  The reason is that when triethylamine is used as an acid scavenger as shown in the following formula, a compound in which not only the amino group but also the phenol group is benzoylated is preferentially obtained, and the selectivity of the reaction is low. It is presumed that the purity of the product was low (see Patent Document 5).

  Moreover, although the case where the triethylamine is not used is reported in the above document, the selectivity is low and the problem is not improved. Therefore, good results have been obtained by adding lithium chloride and calcium chloride in order to achieve selectivity. However, in the case of electronic materials, it is preferable because trace amounts of metals such as lithium and calcium may cause a problem. Absent.

  As described above, there is a known method for obtaining a dinitro compound as a raw material of poly (imide-benzoxazole) used for electronic materials by reacting diaminophenol and nitrobenzoyl chloride at an industrial scale at a low cost. Absent.

JP-A-11-199557 JP 2009-62398 A JP 2001-235860 A JP 7-316294 A JP 2000-143806 A

  An object of the present invention is to provide a method for producing a highly pure dinitro compound by reacting diaminophenol and nitrobenzoyl chloride by a simple method.

  According to the present invention, a highly pure dinitro compound can be obtained in a high yield by a very simple method.

  By reducing the dinitro compound produced by the method of the present invention, a diamine is produced, which is polymerized with tetracarboxylic dianhydride and converted to poly (imide-benzoxazole) by heat treatment.

  The present invention provides a general formula

(Wherein R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.)
Nitrobenzoyl chloride represented by the general formula

(Wherein, A represents a single bond, or represents a C _{(CF 3) 2.)}
Is reacted in a nitrogen-containing organic solvent to give a general formula

(In the formula, A represents a single bond or C (CF ₃ ) ₂ , and R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.)
A dinitro compound represented by the formula:

  The present invention provides a general formula

(Wherein R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.)
Nitrobenzoyl chloride represented by the general formula

(Wherein, A represents a single bond, or represents a C _{(CF 3) 2.)}
Is reacted in a nitrogen-containing organic solvent to give a general formula

(In the formula, A represents a single bond or C (CF ₃ ) ₂ , and R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.)
A dinitro compound represented by the formula:

  General formula

In the nitrobenzoyl chloride represented by R ¹ , R ¹ is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a methoxy group or an ethoxy group, R ¹ is more preferably a hydrogen atom.

  Specific compounds of nitrobenzoyl chloride include 3-nitrobenzoyl chloride, 4-nitrobenzoyl chloride, and 2-nitrobenzoyl chloride, and 3-nitrobenzoyl chloride and 4-nitrobenzoyl chloride are particularly preferable.

  General formula

A in in represented by diaminophenol single bond, or, to display the C _{(CF 3) 2.}

Specific compounds of diaminophenol include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3′-dihydroxybenzidine, 3,3′-diamino-4, 4′-dihydroxy. etc. biphenylene, Le, and the like. Diaminophenol is preferably 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3'-dihydroxy Ben Jiji down.

  General formula produced by the method of the present invention

Specific examples of the dinitro compound represented by the formula include those having the following structures.

  General formula

The nitrobenzoyl chloride represented by is preferably used in an amount of 2.0 to 3.0 moles, more preferably 2.0 to 2.5 moles, relative to diaminophenol.

  In the production method of the present invention, a nitrogen-containing organic solvent is used for the reaction. Specifically, the nitrogen-containing organic solvent is N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl- 3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, N-methylcaprolactam, hexamethylphosphoric triamide, tetramethylurea, etc. are preferred, N-methyl-2-pyrrolidone (NMP), or N, N-dimethylacetamide (DMAC) is more preferred. A nitrogen-containing organic solvent may be used independently and may be used in combination of multiple types.

  The amount of nitrogen-containing organic solvent used is the general formula

The compound is preferably used in an amount of 1 to 40 times by weight, more preferably 2 to 20 times by weight based on the above compound.

  In the production method of the present invention, since a nitrogen-containing organic solvent as a solvent is used as an acid scavenger, usually no base is added. This production method has an advantage that the production cost is reduced because the amino group of diaminophenol selectively reacts with nitrobenzoyl chloride, does not use a base, and requires only a small amount of solvent.

  In the production method of the present invention, it is preferable to first dissolve diaminophenol in a nitrogen-containing organic solvent and then add nitrobenzoyl chloride. When added in this order, the diaminophenol always becomes excessive in the reaction solution, so that the amino group of the diaminophenol reacts selectively.

  Nitrobenzoyl chloride may be added in the form of a solid, or may be added after being heated and dissolved at a temperature higher than the melting point. A solution dissolved in a solvent that does not react with nitrobenzoyl chloride may be added.

  Examples of the solvent that does not react with nitrobenzoyl chloride include nitrogen-containing organic solvents, aromatic hydrocarbons, ethers, and the like. The nitrogen-containing organic solvent is preferably a nitrogen-containing organic solvent used in the reaction, more preferably N-methyl-2-pyrrolidone (NMP) or N, N-dimethylacetamide (DMAC). The aromatic hydrocarbon is preferably benzene, toluene or xylene, more preferably toluene. The ether is preferably tetrahydrofuran. The amount of the solvent for dissolving nitrobenzoyl chloride is preferably 0.1 to 5 times by weight, more preferably 0.2 to 1 times by weight based on nitrobenzoyl chloride.

  The reaction temperature is preferably in the range of −10 to 100 ° C., more preferably in the range of 10 to 50 ° C. The reaction time is preferably 1 hour to 1 week, more preferably 2 hours to 1 day. As the reaction atmosphere, an inert gas atmosphere such as nitrogen or argon is preferable.

  In the method for producing a dinitro compound of the present invention, after completion of the reaction, the target compound can be isolated and purified by a method such as extraction, concentration, crystallization, or filtration. The target dinitro compound can be obtained by filtering the target product in which precipitation has occurred.

  In the method for producing a dinitro compound of the present invention, after completion of the reaction, at least one solvent selected from water and alcohols is added, or the reaction solution is dropped into at least one solvent selected from water and alcohols. The desired dinitro compound can be obtained by filtering the resulting precipitate.

  The filtered precipitate is preferably washed with at least one solvent selected from water and alcohols. The use amount of at least one solvent selected from water and alcohols is preferably 0.1 to 20 times by weight, more preferably 1 to 10 times by weight, based on nitrobenzoyl chloride. As alcohols, methanol, ethanol, isopropanol and the like are preferable. At least one solvent selected from water and alcohol used for addition and washing after completion of the reaction may be used singly or in combination.

  If necessary, the dinitro compound of the present invention can be purified by a method such as recrystallization, reprecipitation, column chromatography or the like. In the case of recrystallization, solvents that do not react with the target product can be used alone or in combination of two or more.

  By reducing the dinitro compound thus obtained, a general formula

(In the formula, A represents a single bond or C (CF ₃ ) ₂ , and R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.)
The diamine represented by this can be obtained.

  Reduction methods include a method in which hydrogen gas is allowed to act in the presence of a metal catalyst such as palladium / carbon, Raney nickel, a method in which ammonium formate is allowed to act in the presence of a metal catalyst such as palladium / carbon, Raney nickel, and stannous chloride. A method using hydrochloric acid, a method using iron and hydrochloric acid, a method using hydrazine, and the like can be used.

  Poly (imide-benzoxazole) can be obtained by polymerizing the obtained diamine as a monomer.

  Below, based on an Example, this invention is demonstrated in detail.

  In the following examples, the following apparatus was used for the measurement, and general reagents purchased from reagent manufacturers (Tokyo Chemical Industry, Wako Pure Chemical Industries, Nacalai Tesque) were used as raw materials.

IR measurement
Shimadzu IR Prestige-21 was used. It measured by ATR method using KBr.

HPLC measurement LC-10AVP series manufactured by Shimadzu Corporation was used. As the column, Inertsil ODS 80A manufactured by Gaschrom Industries was used, and the purity was calculated with an area of 100%.

Melting | fusing point measurement The trace amount melting | fusing point measuring apparatus MP-J3 made from Yanaco apparatus research laboratory was used.

Example 1
2,2-bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoropropane

  A 100 mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer was charged with 10.2 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 37 g of NMP. After dissolving by stirring, it was cooled to 30 ° C. or lower. A solution prepared by dissolving 10.3 g of 3-nitrobenzoyl chloride in 5 g of toluene was added dropwise at a temperature of 25-30 ° C. over 30 minutes, and then stirred at 25-30 ° C. for 3.5 hours. A part of the sample was taken and subjected to HPLC analysis by adding methanol and triethylamine. As a result, 0.5% of 3-nitrobenzoic acid, 2,2-bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoro Propane was 99.1%.

  A 300 mL four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 150 g of methanol and heated to 45 ° C. under a nitrogen stream. The previous reaction solution was added dropwise at a temperature of 40 to 45 ° C. over 30 minutes. After cooling to room temperature in 1 hour, the deposited precipitate was filtered, washed with 26 g of methanol and dried to obtain 18 g of 2,2-bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoropropane. It was. As a result of HPLC analysis, the purity was 99.8%.

IR (ATR) cm ⁻¹ : 3414, 3181, 1655, 1537, 1352, 1252
mp: 300 ° C. or higher.

Example 2
2,2 -bis (3-amino-4) was added to a 300 mL four-necked flask equipped with 2,2-bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoropropane stirrer, dropping funnel and thermometer. -Hydroxyphenyl) hexafluoropropane 10.1 g and NMP 45 g were charged and dissolved by stirring at 40 ° C. in a nitrogen stream. A solution prepared by dissolving 10.4 g of 3-nitrobenzoyl chloride in 5 g of NMP was added dropwise at 40 ° C. over 30 minutes, and then stirred at 40 ° C. for 3 hours. A part of the sample was taken and subjected to HPLC analysis with methanol and triethylamine added. As a result, 0.8% 3-nitrobenzoic acid, 2,2-bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoro Propane was 98.9%.

  The reaction solution was heated to 60 ° C., 100 g of methanol was added dropwise over 1 hour, and after cooling to room temperature, the deposited precipitate was filtered, washed with 18 g of methanol, dried, and 2,2-bis [3- (3 16.2 g of (nitrobenzamido) -4-hydroxyphenyl] hexafluoropropane was obtained. As a result of HPLC analysis, the purity was 99.6%.

Example 3
2,2-bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoropropane In Example 1, except that isopropanol was used instead of methanol, 2,2-bis [3- (3-Nitrobenzamido) -4-hydroxyphenyl] hexafluoropropane was obtained. As a result of HPLC analysis, the purity was 99.6%.

Example 4
2,2-bis [3- (4-nitrobenzamido) -4-hydroxyphenyl] hexafluoropropane

In Example 1, 2,2-bis [3- (4-nitrobenzamido) -4-hydroxy was used in the same manner as in Example 1, except that 4-nitrobenzoyl chloride was used instead of 3-nitrobenzoyl chloride. Phenyl] hexafluoropropane was obtained. As a result of HPLC analysis, the purity was 99.5%.
Example 5
2,2 -bis (3-amino-4) was added to a 100 mL three-necked flask equipped with a 2,2-bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoropropane stirrer, a dropping funnel and a thermometer. -Hydroxyphenyl) hexafluoropropane (12.5 g) and DMAC (37.6 g) were charged, stirred at 30 ° C. in a nitrogen stream, and a solution of 3-nitrobenzoyl chloride (12.7 g) dissolved in DMAC (3.8 g) was added dropwise over 30 minutes. Then, the mixture was stirred at 30 ° C. for 2 hours. A part of the sample was taken and subjected to HPLC analysis with methanol and triethylamine added. As a result, 0.8% 3-nitrobenzoic acid, 2,2-bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoro Propane was 98.8%. To this, 12.3 g of methanol was added, and the resulting precipitate was dissolved.

  A 300 mL four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was charged with 125 g of methanol and heated to 30 ° C. under a nitrogen stream. The previous reaction solution was added dropwise from the dropping funnel over 30 minutes. Cool in an ice-water bath and cool to 10 ° C. or lower. The deposited precipitate is filtered, washed with 25 g of methanol and dried to give 2,2-bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoropropane. 21.5 g was obtained. As a result of HPLC analysis, the purity was 99.9%.

Example 6
2,2 -bis (3-amino-4) was added to a 100 mL three-necked flask equipped with a 2,2-bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoropropane stirrer, a dropping funnel and a thermometer. -Hydroxyphenyl) hexafluoropropane 7.9 g and DMAC 21.4 g were charged, stirred at 35 ° C. under a nitrogen stream, and a solution of 8.0 g of 3-nitrobenzoyl chloride dissolved in 5.3 g of THF was added dropwise over 15 minutes. Then, the mixture was stirred at 30-35 ° C. for 2 hours. A part of the sample was taken and subjected to HPLC analysis with methanol and triethylamine added. As a result, 1.0% of 3-nitrobenzoic acid, 2,2-bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoro Propane was 98.8%. To this, 8.0 g of methanol was added, and the resulting precipitate was dissolved.

  A 300 mL four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was charged with 73 g of methanol and stirred at room temperature under a nitrogen stream. The previous reaction solution was added dropwise over 15 minutes. The mixture was stirred at room temperature for 1 hour, and the deposited precipitate was filtered, washed with 33 g of methanol and dried to obtain 13.9 g of 2,2-bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoropropane. It was. As a result of HPLC analysis, the purity was 99.6%.

Example 7
4,4'-bis (4-nitrobenzamide) -3,3'-dihydroxybiphenyl

In the same manner as in Example 1 except that 3,3′-dihydroxybenzidine was used instead of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane in Example 1, 4,4 '-Bis (4-nitrobenzamide) -3,3'-dihydroxybiphenyl was obtained. As a result of HPLC analysis, the purity was 99.0% IR (ATR) cm ⁻¹ : 3320, 1650, 1520
Reference example 1
The 2,2-bis [3- (3-aminobenzamido) -4-hydroxyphenyl] hexafluoropropane stirrer, reflux condenser and thermometer equipped with 2,2-bis [3- (3-aminobenzamido) -4-hydroxyphenyl] -Bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoropropane 17.2 g, N, N-dimethylformamide 144 g, and isopropanol 17 g were charged with nitrogen, and 5% palladium / carbon 0.69 g was added. And stirred vigorously. Hydrogen was introduced here with a balloon, and the mixture was stirred at 70 ° C. for 5 hours, and it was confirmed that the balloon no longer deflated. A part of the sample was taken and analyzed by HPLC. As a result, 3-aminobenzoic acid was 0.1% and 2,2-bis [3- (3-aminobenzamido) -4-hydroxyphenyl] hexafluoropropane was 97.3%. there were. After cooling, the catalyst was filtered and the filtrate was concentrated to obtain 31 g of a concentrated solution.

A 300 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 105 g of water and heated to 45 ° C. under a nitrogen stream. The concentrated solution was dropped from the dropping funnel in 30 minutes and cooled to room temperature, and then the resulting precipitate was filtered, washed with water and dried, and 2,2-bis [3- (3-aminobenzamide) -4 7.9 g of -hydroxyphenyl] hexafluoropropane was obtained. As a result of HPLC analysis, the purity was 99.4%.
mp: 300 ° C. or higher Comparative Example 1
Example of using organic base imidazole as acid scavenger
2,2-Bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoropropane thermometer, stirrer, and dropping funnel were added to a 100 mL three-necked flask with 2,2-bis (3-amino- 4-hydroxyphenyl) hexafluoropropane (6.0 g), NMP (24 g), and imidazole (2.6 g) were charged, and a mixed solution of NMP (10 g) and 3-nitrobenzoyl chloride (6.2 g) was added dropwise over 1 hour at 60 ° C. in a nitrogen stream. Thereafter, aging was performed at 60 ° C. for 4 hours. A part of the sample was taken, and methanol / triethylamine was added to unesterify 3-nitrobenzoyl chloride to be methyl esterified and analyzed by HPLC. As a result, 1.3-nitrobenzoic acid 1.3%, methyl 3-nitrobenzoate 7 4%, 2- [3- (3-nitrobenzamido) -4-hydroxyphenyl] -2- (3-amino-4-hydroxyphenyl) hexafluoropropane 11.8%, 2,2-bis [3- (3-Nitrobenzamide) -4-hydroxyphenyl] hexafluoropropane was 77.1%, and the reaction was incomplete.

Comparative Example 2
Example using tetrahydrofuran as solvent and imidazole organic base as acid scavenger
2,2-Bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoropropane thermometer, stirrer, and dropping funnel were added to a 100 mL three-necked flask with 2,2-bis (3-amino- 4-hydroxyphenyl) hexafluoropropane (6.0 g), tetrahydrofuran (47 g), and imidazole (2.5 g) were charged, and the mixture was stirred in a water bath under a nitrogen stream. A mixed solution of 13 g of THF and 6.0 g of 3-nitrobenzoyl chloride was added dropwise at 10-15 ° C. over 1 hour, followed by stirring overnight at room temperature. A part of the sample was taken, and methanol / triethylamine was added to unesterify 3-nitrobenzoyl chloride to methyl ester. As a result of HPLC analysis, 2,2-bis [3- (3-nitrobenzamide) -4- The purity of hydroxyphenyl] hexafluoropropane was 26.3%. In addition, a number of peaks such as compounds substituted with one nitrobenzoyl chloride, compounds substituted with three, compounds substituted with four, 3-nitrobenzoic acid, methyl 3-nitrobenzoate were detected, and there was no selectivity in the reaction. It was.

Comparative Example 3
Example using acetone as solvent and imidazole organic base as acid scavenger
In 2,2-bis [3- (3-nitrobenzamido) -4-hydroxyphenyl] hexafluoropropane Comparative Example 2, the reaction was performed in the same manner as Comparative Example 2 except that acetone was used instead of THF as a solvent. A part of the sample was taken, and methanol / triethylamine was added to unesterify 3-nitrobenzoyl chloride to methyl ester. As a result of HPLC analysis, 2,2-bis [3- (3-nitrobenzamide) -4- The purity of hydroxyphenyl] hexafluoropropane was 14.0%. In addition, a number of peaks such as compounds substituted with one nitrobenzoyl chloride, compounds substituted with three, compounds substituted with four, 3-nitrobenzoic acid, methyl 3-nitrobenzoate were detected, and there was no selectivity in the reaction. It was.

Claims (4)

General formula

(In the formula, R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.)
Nitrobenzoyl chloride represented by the general formula

(Wherein, A represents a single bond, or represents a C _{(CF 3) 2.)}
Is reacted in a nitrogen-containing organic solvent to give a general formula

(In the formula, A represents a single bond or C (CF ₃ ) ₂ , and R 1 represents a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.)
A method for producing a dinitro compound represented by the formula: The method for producing a dinitro compound according to claim ¹ , wherein R ¹ is a hydrogen atom. The method for producing a dinitro compound according to claim 1 or 2 , wherein the nitrogen-containing organic solvent is N-methyl-2-pyrrolidone or N, N-dimethylacetamide. The manufacturing method of the dinitro compound in any one of Claims 1-3 which does not add a base.