JPS6245563A - Production of bis(3-nitrophenoxy) compound - Google Patents

Abstract

PURPOSE:To obtain a bis(3-nitrophenoxy) compound in an extremely shortened reaction time in high purity in high yield while suppressing formation of by- products, by reacting a 4,4'-bisphenol with m-dinitrobenzene in the presence of a nitrogen-containing cyclic ether. CONSTITUTION:A 4,4'-bisphenol shown by the formula I [X is 1-10C bifunctional hydrocarbon or bifunctional group such as C(CF3)2, CO, S, SO, SO2 or O] is condensed with m-dinitrobenzene in the presence of a nitrogen- containing cyclic ether shown by the formula II (R is 1-4C alkyl; n is 1 or 2) as a phase transfer catalyst in an aprotic polar solvent in the presence of a base (e.g., potassium carbonate) at 100-240 deg.C for 5-30hr to give the aimed substance shown by the formula III. USE:An intermediate for synthesizing a diamine useful as a monomer for a high- resistant high polymer, especially a raw material for polyamide and polyimide.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a bis(3-nitrophenoxy) compound. More specifically, when producing a bis(3-nitrophenoxy) compound by condensing 4,4'-bisphenols and m-dinitrobenzene in an aprotic polar solvent in the presence of a base, the reaction is carried out using the general formula (
TII) N4CH2-CI-12-0-(CH2-CH2-0 No. R)3 (III) (wherein, R is 1 to 1
bis(3-nitrophenoxy) characterized in that the reaction is carried out in the presence of a phase transfer catalyst represented by an alkyl group having 1 or 2 carbon atoms, and n is an integer of 1 or 2.
Bis(3-nitrophenoxy) compound is an important compound as an intermediate for diamines, which are raw materials for heat-resistant polymers such as polyamide and polyimide. An adhesive having excellent heat resistance can be obtained from a polyimide whose diamine component is an ether diamine obtained by reduction.

(Prior Art) Many examples have been known regarding the reaction of replacing the nitro group activated by the electron-withdrawing group at the 0- or P-position with alcohols or phenols in aromatic nitro compounds. (e.g. journal op.
Polymer Science, Polymer Chemistry Bone Edition (J.

p, z, , , S c, , p, f, , , C6
m, Ed, ) 15.2441 (1977); Ji, 30
69 (1980); Journal of Organic Chemistry (J, 0.,.

cLtm, ) 39.1839 (1974), and tetrahedron (nmu αW--, ) 34.
There is a review article in 2057 (1978). )however,
Regarding reactions of unactivated nitro groups such as m-dinitrobenzene, some examples of substitution reactions using alcohols exclusively are known, but almost no examples of substitution reactions using phenols are known. That is, as a conventional technique for substitution reaction with phenols, 3-nitrodiphenyl ethers are produced by reacting m-dinitrobenzene with an alkali metal phenoxide in a polar tUa medium in the presence of a macrocyclic polyether. The method is only known (Japanese Unexamined Patent Publication No. 1983-39.030)
. However, in this case, it is necessary to use an expensive and toxic catalyst such as crown ether as a reaction promoter, and furthermore, there are no examples or yields described. On the other hand, in the process of investigating the condensation reaction between 4,4'-bisphenols and m-dinitrobenzene, the present inventor discovered that bis(3- He discovered that bis(3-aminophenoxy) compounds could be obtained in high yield and that bis(3-aminophenoxy) compounds could be easily produced by reduction, and he filed an earlier patent application (Patent Application 1983).
-32567.6O-32568). These diamines are used as monomers for heat-resistant polymers, but high-purity products are usually required in terms of quality. Therefore, it goes without saying that the higher the purity of the bis(3-nitrophenoxy) compound used as a raw material for diamines, the more desirable it is.

(Problems to be Solved by the Invention) The problems to be solved by the present invention are 4. ．． 1'-bisphenol i-
By providing an industrial method for producing highly pure bis(3-nitrophenoxy) compounds by greatly shortening the reaction time and suppressing the production of by-products in the condensation reaction with dinitrobenzene. be.

(Means for Solving the Problems) In order to solve the problems of the present invention, the present inventors have attempted to shorten the reaction time in the condensation reaction of 4,41-bisphenols and m-dinitrobenzene, which was previously filed. Various reaction accelerators, additives, catalysts, etc. have been intensively investigated to suppress the production of by-products. As a result, the condensation reaction can be expressed by the general formula (
By adding a nitrogen-containing chain ether represented by 1'II), the reaction time can be greatly shortened compared to the case without a catalyst, and the formation of by-products can also be suppressed. The present inventors have discovered that bis(3-nitrophenoxy) compounds are highly pure and can be produced industrially advantageously, leading to the completion of the present invention.

That is, the present invention relates to the general formula (I) C, where X is a divalent hydrocarbon group having 1 to 10 carbon atoms, -C
(CF3) represents a divalent group of 2-, -CO-, -3-, -8O2- or -0-. In addition, 4,41-bisphenols represented by X may be directly bonded with a single bond) and m-dinitrobenzene are condensed in an aprotic solvent in the presence of a base, and n) (wherein, X has the same meaning as in general formula (I)), the reaction is carried out using the general formula GTI)N(-CH2-O
(2-o+CI-(2-CH,,-0+-R)3(II
I) In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and n is 1
or an integer of 2) is a method for producing a bis(3-nitrophenoxy) compound, characterized in that the process is carried out in the presence of a nitrogen-containing chain ether.

The raw materials used in the method of the present invention are m-dinitrobenzene and 4,41-bisphenols represented by the general formula (I). 4.41-Bisphenol specifically includes 4.4'-dihydroxybiphenyl; 4.
=4'-dihydroxydiphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(
4-hydroxyphenyl)-2-methylpentane, 2.
4-bis(4-hydroxyphenyl)-71-methyl-
1-pentene, 2.2-bis(4-hydroxyphenyl)-hexafluoropropane, 4.41-dihydroxybenzophenone, 4.4'-dihydroxydiphenyl sulfide, 4.41-dihydroxydiphenyl sulfoxide, 4.4'- Examples include dihydroxydiphenyl sulfone, 11.4'-dihydroxy/diphenyl ether, and the like.

The compound produced using these raw materials is a bis(3-nitrophenoxy) compound represented by the general formula (II). Specifically, 4,41-bis(3-nitrophenoxy)biphenyl, 4.4'-bis(3-nitrophenoxy)diphenylmethane, 2.2-bis(4-(
3-nitrophenoquine)phenyl]propane, 2.4-
Bis(4-(3-nitrophenoxy)phenylyo2-
Methylpentane, 2.4-bis(4-(3-nitrophenoxy)phenylcy4-methyl-1-pentene, 2.
2-bis(:4-(3-nitrophenoxy)phenyl)
-hexafluoropropane, 4,4'-bis(3-
nitrophenoxy)benzophenone, 4,4'-bis(
3-nitrophenoxy)diphenyl sulfide, 4
．． 41-His(3-nitrophenoxy) diphenyl sulfoxide, 4.41-bis(3-nitrophenoxy)
Examples include diphenyl sulfone, 4,4'-bis(3-nitrophenoxy) diphenyl ether, and the like.

In the method of the present invention, the amount of raw materials used is not particularly limited, but m-dinitrobenzene is usually used in 4.
It is used in an amount of 1.5 to 4.0 times the mole of 41-bisphenols.

The bases used are alkali metal oxides, hydroxides,
Carbonates, bicarbonates, hydrides or alkoxides.

Specifically, sodium oxide, lithium oxide, potassium hydroxide, sodium hydroxide), lithium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sulfur and lithium hydrogen carbonate, sodium hydride, potassium t- Butoxide, sodium methoxide, sodium ethoxide, etc. are used.

These may be used alone or in combination of two or more. The amount of the base to be used may be 1 to 5 times the molar amount, preferably 1.5 to 3 times the molar amount of the raw material bisphenols.

The nitrogen-containing chain ether used in the method of the present invention acts as a phase transfer catalyst, and has the general formula (rrI
).

Conventionally known products are easily available industrially (Japanese Patent Publication No. 57-37580, Japanese Patent Publication No. 58-34464-).

Specifically, tris(3-oxabutyl)amine [N (
CH2-CH2-0-CH3)s), Tris(3.6
-thioxaheptyl)amine (N (CH2-CH□-
0-CI2-Cl-12-〇-C13), Tris(3
・6,9-trioxadecyl)amine (N (CH2C
H2-0-Ct(2CH2-0-CH,,C)-12-
0-CH3)3: ], tris(3,6-thioxaoctyl)amine (N (Cl-12CI2-()-CH□
C1-12-〇-C21-1. )3':l, tris(3
・6,9-trioxaundecyl)amine [:N(CH
2C1-12-0-CH,, CH2-0-CI2C12
], tris(3,6-thiogysanonyl)amine [N(C
, I2CH2-m-CH2C! -12-0-C3H7)
,], Tris (:3,6φ9-trioxadodecyl)amine [N(C)I2CH2-0-CH2C1-
12-0-CH2CH2-0-C0H7)3: ],
Tris(3,6-dixadecyl)amine (N (CI,
.

CH2-0-CI-12CH2-0-C,I(,)3)
, l, lis(3,6,9-trioxaundecyl)amine [: N (CH,, Ct12-O-CH2C12-
0-CH2CH2-0-C41-1,)3], etc., and industrially, tris(drodioxaheptyl)
Amines are most commonly used.

The amount of these nitrogen-containing chain ethers used is not limited, but usually a catalytic amount is sufficient, and is 0.1 to 10 mol%, preferably 0.5 to 2 mol%, based on the raw material bisphenols. . The effect of promoting the reaction depends on the amount of catalyst used and the type of compound, but if it is used in an amount of 1 mol % based on the bisphenols as raw materials, the reaction time can be shortened to 1/2 to 1/10.

In general, phase transfer catalysts are known to be effective in improving yields and selectivity in various reactions. The most commonly used catalyst to achieve this effect is a tetraalkylammonium salt, but this catalyst is said to have low thermal stability, and in fact, when applied to this reaction,
No effect was observed compared to the case without catalyst. In addition, phosphonium salts and polyethylene glycol are also known, but only a slight effect was observed in this reaction. Furthermore, crown ethers and cryptates are also known, but they are highly toxic and expensive, so they cannot be used industrially; however, even when applied to this reaction, they have little effect. I was not able to admit. On the other hand, the nitrogen-containing chain ether represented by the general formula (ITI) used in the method of the present invention has the effect of greatly shortening the reaction rate as described above.

This indicates that the effects of various phase transfer catalysts vary greatly depending on the type of reaction, and that it is not easy to select one that exhibits the optimal catalytic effect for a particular reaction.

As the reaction solvent, an aprotic polar solvent is used. Specifically, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, dimethylsulfone, sulfolane,
1-methyl-2-hyrolidinone, 1,3-dimethyl-2
-imidazolidinone, N, N, N+, N+-tetramethylurea, hexamethylphosphotriamide, 1,3-dimethyl-3,4,5,6-titrahydro-2(IH)-
Examples include pyrimidine. The amount of these solvents used is not particularly limited, but usually 1 to 10 times the weight of the raw materials is sufficient.

When implementing the method of the present invention, there are no particular limitations on the charging method of raw materials, but for example, (1) a predetermined amount of bisphenols, a base, and a solvent are charged to prepare an alkali metal salt of bisphenols in advance. There are two methods: (1) adding nitrogen-containing chain ether and m-dinitrobenzene and reacting, or (2) charging all raw materials containing m-dinitrobenzene from the beginning and allowing the reaction to proceed as is. The reaction proceeds also by the method described above, and is not particularly limited.

Water generated in the reaction system using an alkali metal oxide, hydroxide, etc. as a base can be gradually removed from the system during the reaction by, for example, bubbling nitrogen gas, or benzene, toluene, xylene, A method is used in which chlorobenzene or the like is used to remove it from the system as an azeotrope. On the other hand, when using carbonates, hydrogen carbonates, etc., dehydration operations are particularly required.

The reaction temperature is usually 100 to 240°C, preferably 12
The temperature ranges from 0 to 180°C, and the reaction time ranges from 5 to 30 hours. The end point of the reaction can be determined by thin layer chromatography, high performance liquid chromatography, and the like.

After the reaction is complete, the desired crude product can be obtained by distilling off the solvent or by directly discharging the reaction solution into water. Although this crude product can be further purified by recrystallization or the like, its purity is as high as 95% or more and can usually be used as is.

(Functions and Effects) According to the method of the present invention, the condensation reaction between bisphenols and m-dinitrobenzene is significantly accelerated by the presence of a nitrogen-containing chain ether in the reaction system, and relatively easily produces high purity and Various bis(3-nitrophenoxy) compounds can be produced in high yields.Therefore, it is an extremely excellent method from an industrial perspective.

(Example) Hereinafter, the present invention will be described in more detail by comparing the present invention with examples and comparative examples.

Example 1 4.41-Dihydrokibiphenyl 186!7 (1.0 mol), m-dinitrobenzene 403 (2.4 mol), potassium carbonate 331 (2.4 mol), tris (3.6-
3.2 g (0.01 mol) of thioxaheptyl)amine and 21 N,N-dimethylformamide and 14
React at 5-150°C for 2 hours. After the reaction is complete, cool
After filtering and removing the solvent of the solution by vacuum distillation, 65
Cool to °C, charge 11 methanol and stir for 1 hour. After washing the crystals with methanol and drying them, the crystals were washed with 4.4I-
Yellowish brown crystals of bis(3-nitrophenoxy)biphenyl were obtained. The yield was 4269C (yield 99.5%), and the purity by liquid chromatography was 97.5%. The crude crystals were recrystallized with dimethyl sulfoxide to obtain a pure product.

Pale yellow crystal mp 134-136°C*) Elemental analysis Calculated value (%) 67.30 3,74
6.54 analysis value C%) 67.34 3.70
6.48*) MS as C2j-LaN20a: 428 (M+) IR (KBrd'); 1520.1350 (No2 group); 1240 (ether bond) Comparative example 1 4.41-dihydroxybiphenyl 186 g (1.0 mol) , m-dinitrobenzene 438 (2,6 mol) potassium carbonate 363! ;l (2,6 mol) and N, N-
Dimethylformamide 21 was charged and the reaction was carried out at 145-150°C for 16 hours without using a phase transfer catalyst. The same post-treatment as in Example I was carried out to obtain brown crystals of 4,41-bis(3-nitrophenoxy)biphenyl. Yield 4
269 (Yield 99.5%) The purity of the product by liquid chromatography was 91.0%.

Example 2 2.2-bis(4-hydroxyphenyl)propane 34
3 g (1.5 mol), m-dinitrobenzene 605 g (
3,6 mol), potassium carbonate 4989 (3,6 mol),
Tris(3,6-dioxahebutyl)amine 4.85(
0,015 mol), DMF'3.4 # was charged, 1
React for 4 hours at 45-150°C. After the reaction was completed, it was cooled and filtered, and the solvent of the solution was distilled off under reduced pressure.
Cool to 5°C, add 1.81 g of methanol and stir for 1 hour. 2. The crystals are washed door to door with methanol and then dried.
Yellowish brown crystals of 2-bis(4-(3-nitrophenoxy)phenyl)propane were obtained. 705.4 g (yield: 9
9.8%) The purity of the product by liquid chromatography was 98%. The crude crystals were recrystallized with methyl cellosolve to obtain a pure product.

Elemental analysis Calculated value (%) bread) 68,93 4.71
5.96 Analysis value (%) 69.05 4.65
5.94*) MS as C27N2□N206: 470 (M+), 455 (~f-CH3)
+IR (KBr, L:i'): 1520hi 1:34
0 (No2 group); 1240 (ether bond) Comparative example 2 2.2-bis(4-hydroxyphenyl)furopane 83
．． 6 (0,375 mol), m-dinitrobenzene 15
1.2 mol (0.9 mol), potassium carbonate 124.6 mol (
0.9 mol), and N,N-dimethylformamide 6
60- and 145-1 without using a phase transfer catalyst.
The reaction was carried out at 50°C for 10 hours. The same post-treatment as in Example 2 was carried out to obtain !?4B colored crystals of 2,2-bis(-1-(3-nitrophenoxy)phenyl)furopane.

Yield: 165 g (yield: 93.5%). Purity of the product by liquid chromatography was 93%.

Note that the yield of the above-mentioned target product was 61% by liquid chromatography after 4 hours of reaction.

Example 3 218 g of 4.4'-dihydroxydiphenyl sulfide
(1 mol), m-dinitrobenzene 40:3!7 (2=
, 1 mol) Potassium carbonate 331 mm (2.4 mol), )'
Js(3,6-dioxahebutyl)amine 3.237(
0.01 mol) O, J: and D ~ IF2.5e are charged,
React at 1/15 to 150'C for 5 hours. After the reaction is complete,
Cool, filter through 2, and remove the solvent of the P solution by distillation under reduced pressure.

After cooling to 65°C, charge 800ml of methanol and
Stir for an hour. The crystals were separated from P, washed with methanol, dried, and mulled to obtain yellowish brown crystals of s,,i'-bis(3-nitrophenoxy)diphenyl sulfide. Yield 45
The purity of the product was 95% by liquid chromatography (yield: 98.5%). The crude crystals were recrystallized from methyl cellosolve to obtain a pure product.

Pale yellow crystal mp 97-b HNS elemental analysis calculated value (%) 62.603.476.0
96.96 Analysis value (%) 62.873.296.
026.77 Comparative Example 3 A reaction was carried out at 145 to 150°C for 200 hours in the same manner as in Example 3, except that no phase transfer catalyst was used. A similar post-treatment was performed to obtain dark brown crystals of 4,41-bis(3-nitrophenoxy)diphenyl sulfide. Yield: 429 yen (yield: 93.2%) The purity of the product by liquid chromatography was 85%.

Claims (1)

[Claims] 1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X is a divalent hydrocarbon group having 1 to 10 carbon atoms, -C
(CF_3)_2-, -CO-, -S-, -SO-, -
Indicates a divalent group of SO_2- or -O-. Also, X may be directly bonded with a single bond)
'-Bisphenols and m-dinitrobenzene are condensed in an aprotic polar solvent in the presence of a base to form the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (wherein, X is the general formula ( I) has the same meaning as in case of
In producing the bis(3-nitrophenoxy) compound represented by the general formula (III) N-(CH_2
-CH_2-O-(CH_2-CH_2-O)-_nR
)_3 (III) (wherein, R represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or 2). A method for producing a bis(3-nitrophenoxy) compound.