WO2001038290A1

WO2001038290A1 - Process for producing 2,2-bis(3,4-diaminophenyl)hexafluoropropane

Info

Publication number: WO2001038290A1
Application number: PCT/JP2000/008196
Authority: WO
Inventors: Tsuyoshi Itagaki; Katsuhiko Iseki
Original assignee: Daikin Industries, Ltd.
Priority date: 1999-11-26
Filing date: 2000-11-21
Publication date: 2001-05-31

Abstract

A process for producing in high yield 2,2-bis(3,4-diaminophenyl)hexafluoropropane, which is useful as a crosslinking agent, from an inexpensive compound through a short reaction step. The process comprises catalytically reducing 2,2-bis[3-nitro-4-(substituted or unsubstituted benzylamino)phenyl]hexafluoropropane.

Description

Akira Itoda

2.2-Bis (3, 4-Jiaminofujinirile)

Manufacturing technology for hexafluoropropane

The present invention relates to a new method for manufacturing 2,2-bis (3,4-diaminophenyl) hexafluoropropane.

Also, the present invention relates to a novel compound, 2,2-bis (3--2-tro-4-tosyloxysulfenyl), which is a new compound. Regarding the low resolution.

In addition, the present invention is directed to the above-mentioned 2, 2-vis (3-nitro 4-tosyloxyifenil) from xafluoropropane. 2,2—Vis [3—Amino-4-1 (replaced or non-replaced phenylamine) phenyl] Kisa Fluoropropane On how to make it.冃 ', technology

2,2-bis (hexafluorophenol) hexafluoropropane is useful as a fluorine-based carrier, and Since,

(1) 2, 2-vis (4-aminophenyl) to be oxidized under normal conditions of cyclization. After that, the method of nitration, desealing, and rejuvenation under normal conditions (US Patent No. 3,310,573) (Details)

(2) The method described in (1) above, which is applied to 2, 2-bis (3-amino phenyl) from Kisa Fluoropropane 6-4 — 2 9 3 4 3

It has been known .

However, the starting material of these conventional methods, 2, 2-vis

(4—Amino Fe nil) Hexafluoropropane and

The synthesis of 2, 2-bis (3-aminophenyl) to hexafluorene can be done with 2, 2-bis (4-hydroxy) ) Hexafluoropropane (Bisphenol AF) is a known source of power (US Patent No. 4,

37 0, 501 No. Specifi cation, Japanese Patent Publication No. 0 3 1 1 0 2 8 Publication, Japanese Patent Publication 6 4-2 9 3 4 3 Publication All of these require multiple steps of synthesis (the final compound, 2,2—vis (3,4—diaminofeni) 7 to 8 processes are required to synthesize hexafluoropropane), and use low-yield, high-priced reagents. As a result, the result is a highly expensive substance.

The present invention is based on the excretion of 2,2-bis (4-hydroxyphenyl) to xafluoropropane (bisphenol AF). However, a new series of 2,2-bis (3,4-diaminophenyl) is a new type of xafluoropropane, which consists of a series of small reaction processes. The aim is to provide a specific synthesis method.

In addition, the present invention relates to a novel compound, 2,2-bis (3-nitro-4-tosyloxyfenyl), which is a new compound. It is intended to provide a lopron \ °.

In addition, the present invention is based on the above-mentioned 2, 2-bis (3-

4 _ 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _________________________ The purpose is to provide a new synthesis method for producing phenylaluminopropane) hexafluoropropane. Disclosure of the invention

The present invention is based on the new synthesis method described above, and is intended for use in 2, 2-bis (3, 4-diaminofenyl). 2, 2 -vis [3 -2tro-4-(replaced or unreplaced benzylamine) phenyl] which is the final process of the synthesis of The ability to retouch the saflo-prono \ ° to the 2,2—vis (3,4—diaminophenyl) This is related to the manufacturing method of Oropropane. In addition, 2, 2-vis [3-nitro-41 (replaced or non-replaced benzylamine) phenyl] \ ° is used to represent 2, 2 -vis [3-nitro-41- (benzylamine) phenyl] to xafluoropropane Let me explain.

The contact element is a metal belonging to Group VIII of the periodic system according to Maya Mendelev (for example, white gold, palladium, iron, nickel, etc.). ), But due to the high reaction speed and the high reaction speed, the presence of the hydroxylated palladium catalyst is not sufficient. It is better to do it at

The above 2 and 2-vis [3-nitro-41 (benzylamino) phenyl] hexafluoropropane are 2 and 2-vis (3—2 Troll 4—Tosyloxyfenyl) can also be obtained by converting benzofluoropropane to benzylamine. Okay, or to the 2 and 2—vis (3—Nitro 4—Tri-fluorene) Benzyl Aminification of Propane May Be Beneficial

The benzylamine is placed in an organic solvent such as ethyl acetate, butyrate acetate, tetrahydrofuran, etc. under heated reflux. A substituted or non-replaced benzylamine compound, for example, benzylamine, p-methoxybenzylylamine or p-cloth It is preferable to do this by reacting the mouth venjireamin.

Any organic solvent can be used as the organic solvent, but non-solvents such as ethyl acetate, acetyl acetate, tetrahydrofuran, etc. may be used. Protonic solvents are preferred, and especially, butyl acetate. Further, it is preferable that the temperature during the heating and returning is set to 25 ° C or more.

2, 2-vis (3-2 tro 4-tosyloxyphenyl) described above The hexafluoropropane is a new compound.

This invention is based on the above-mentioned 2, 2-vis (3-2 tro 4-tosyloxyfeni), which has been replaced with xafluoropropane. Reacting a non-replaced phenylamine compound with a 2,2—vis [3—nitro—4— (replaced or non-replaced phenylamine ) 2, 2-vis [3-amino 1 4, which produces hexafluoropropane, which can be used for contact reduction — (Replaced or non-replaced phenyl amino) phenyl] Related to the manufacturing method of hexafluoropropane.

First, the best form for carrying out the invention is the 2,2—vis (4–hydroxy phenyl). (2,2-bis) (3,4-diaminophenol) consisting of a series of small reaction processes, using phenol (AF) as the starting material A brief description of the whole new synthesis of hexafluoropropane is provided. This synthesis method consists of the following reaction processes (1) to (4). However, the reaction conditions (1) to (3) are merely illustrative. (1) Nitro conversion of 2,2 — bis (4-hydroxy phenyl) to hexafluoropropane (bis phenol AF) Reaction process

2.2 — Bis (4-hydroxyphenyl) hexafluoroproponone (bisphenol AF) is converted to acetic acid or methanol Dissolved in water, and nitric acid is added to the solution [] to form a two-port (50 ° C, 4 hours), and a 2,2-bis (3-two-trough 4-hydr) To obtain a hexafluoropropane.

(2 A) 2, 2-Vis (3-Nitroguchi 1 4-Hydroxyphenyl) Toxylation of xafluoropropane

2,2—vis (3—nitro-4-hydrofuran) to p-fluorobenzene and p-toluenesuronic Dissolve the light in an organic solvent such as dichloromethan, cool it, add triethylamine, stir (about 1 hour) ), Then stir at room temperature and react (about 3 hours), and go to 2,2-bis (3-nitro-14-trisyloxyfenyl) Obtain a propeller outlet propane.

(2 B) 2, 2-bis (3-nitro 4-hydroxyphenyl) to the trifluorometer of the xafluoropropane Sulfonylation reaction process

2,2—Vis (3—Nitro 14—Hydroxy phenyl), Fluoroprono, Chromometer for ° C and Pyridine The difluoromethan solution of trifluormethan sulphonic anhydride was added to the solution at -78 ° C, and the temperature was reduced to 1 at that temperature. Stir for an hour, then react at room temperature for 3 hours, and use 2,2-bis (3-nitro 4-trifluorene) To obtain a fluoropropane.

(3 A) 2 '2-VIS (3-2 TRO Hexafluoropropene Benzilla Aminoidi reaction process

To the 2,2—vis (3—Nitro 4—Tosyloxyfenyl) synthesized in the reaction process (2A) Is dissolved in butyrate acetate, and benzylamine is dropped under the heat return flow of calo to give 2,2—vis [3—2-tro-41-1 (benzyl) (Amino) phenyl] to obtain hexafluoropropane (about 4 hours).

(3 B) 2, 2-VIS (3-2 TRO 4-TRI FLUOROMETERS LE HONIL ROXIFENIL) Pan Benzyl Aminogenization Reaction Process

2,2-bis (3-2-4-trifluoro-ure-sul-ho-n-loxy-fenil) synthesized in the reaction process (2B) Hexafluoropropane is dissolved in tetrahydrofuran, and benzylamine is dropped under the heat return stream to give 2,2-bis [ 3—Nitro 4— (Benzylamino) phenyl] Hexafluoropropane is obtained.

(4) 2, 2-Vis [3-Nitro-41 (benzylamino) phenyl] Contact reaction of xafluoropropane Process (method of the present invention)

2,2-vis obtained in the reaction process (3A) or (3B)

[3—Nitro-41- (benzylamino) phenyl] hexafluoropropane in organic solvent to hydrogen in the presence of catalyst The reduction of the nitro group and the elimination of the N-benzyl group were carried out at the same time, and the 2,2-bis (3,4-di To obtain the hexafluoropropane.

The organic solvent to be used is, for example, alcohol, such as methanol, ethanol, or isopropanol. Can be used. 2, 2-VIS [3-2 TRO 4-(BANGELAMINO) FENYL] EXA FLOOR PROPRONON is MENU, ETANO Is a poorly soluble compound, but it is a target compound, 2,2-bis (3,4-diaminofurenyl). Since ropane dissolves, it is useful for separation of a target compound.

As the catalyst, for example, palladium-carbon, hydroxylated palladium-carbon, white gold, iron, nickel, etc. are used. However, it is easy to remove the benzyl group, and the yield and purity are high and the price is low. In particular, 5 to 40% of hydroxylated sodium hydroxide is preferable, and especially, 20% of hydroxylated sodium is preferably used. . When 20% hydroxylated no-radium carbon is used, the target compound can be obtained with a high yield of 80 to 90%. The amount of catalyst to be added is the raw material (2,2—vis [3—2-tro 41- (benzylamino) phenyl] hexafluoropropane) 1 to 20% by weight, and preferably 3 to 8% by weight.

Other reaction conditions include a reaction temperature of 10 to 70 ° C, preferably 20 to 30 ° C, and a hydrogen pressure of 0.1 to 10 IMP a ( 1 to 100 atm), preferably 0. IMPa (1 atm) is employed.

In addition, 2, 2 -vis [3-nitro 1-4-(benzylamino), which is the starting material of the production method (reaction process (4)) of the present invention. ) [Fenyl] hexafluoropropane is synthesized by the method (2A)-(3A) as described above. 2 B) One (3 B) process can be used, and in both cases, 2,2-vis [3-2-1-4-1 (benzilamino) fu Niru] Hexafluoropropane is a new manufacturing method. Mekkun in the flow at the same time

However, the method (3A) via the tosilation process (2A) is cheaper without the use of high-priced water-free trifluorene sulfonic acid. The method using the trifluorene-inlet-sulfonylation process (2B) in that p-toluenesulfonate is used (3

B) It is more profitable. Hereinafter, this manufacturing method (3A) will be described.

Organic solvents to be used include, for example, ethyl acetate, vinegar acetate, tetrahydrofuran, acetonitrile, darimum, and the like. It is preferable to use butyrate acetate butter power, which has high power such as black mouth hologram, high yield power and short reaction time.

The bezelamine compound is a compound described in the description of the preferred benzilamine force, ρ-metoxybenzamine, i-b. Replacement benzyl realm compounds such as benzene amide are also acceptable. When using a substituted benzene compound, the corresponding 2, 2 -vis [3-nitro-41 (replaced benzene amino) [Fenyl] Hexafluoropropane is obtained. Replaced or non-replaced benzylamine compounds are 2,

2-bis (3-nitro 4-tosyloxyphenyl) to 2 to 10 equivalents of xafluoropropane, preferably 5 to 6 Use this. The reaction temperature is preferably 25 ° C or higher, and the ability to carry out heat reduction is preferable.

The purpose compound of the present invention, 2,2-bis (3,4-diaminophenyl), is as described above. It is useful as a cross-linking agent. In addition, it can also be expected to be used as a monomer for polymer synthesis such as polyimidazole.

Finally, a new compound, 2,2 -vis (3 -2 to 14 tol oxy phenyl), is a dimensional fluoropropane. Is the starting material, and the 2,3-bis [3-amino-41- (replaced or non-replaced phenylamine) phenyl] The whole of the new synthesis method of the olopropane is briefly described (this explanation. The synthesis reaction is shown in the following two (5) and (6)) It consists of a reaction process, a 2, 2-[3-2 □ □ 1 4 1

(Replaced or non-replaced phenylamine) phenyl) to the 2,3-bis [ Row 4 — (phenylamino) phenyl] The explanation is given on behalf of a hexfluoropropane.

(5) 2, 2-bis (3-2-4-4----------------------------------------------------------------------------------------/ / / / /////// Application

To the 2,2-bis (3-2-1-4-tosyloxy phenyl) synthesized in the reaction process (2 A). Is dissolved in an organic solvent, and a phenylamine compound is dropped under the heated reflux to obtain a 2,2-bis [3-difluoro-41- (phenyl). Lumino) phenyl] Get hexafluoropropane

(About 30 hours).

Organic solvents to be used include, for example, ethyl acetate, butyrate acetate, tetrahydrofuran, acetate nitrile, and glassy acetate. Butyl acetate is preferred because of its ability to excite, such as rubbers and porcelain horns, yield power, and short reaction time.

Examples of phenylamine compounds include phenylamine, 0-chloroaniline, o-methoxyaniline, etc. The compound may be a substituted phenylamine compound. When using a substituted phenylamine compound, the corresponding 2, 2-vis

[3—Nitro 4— (Replacement Fenirile Amino) Fenirile] Hexafluoropropane is obtained. Replacement or non-replacement The phenylamine compound is 2, 2-bis (3-nitro- 4-1-phenyl phenyl) to the fluoramine compound. 2 to 20 equivalents, preferably 8 to 10 equivalents. The reaction temperature is preferably 25 ° C or higher, and it is preferable that the reaction be performed under heated reflux.

(6) 2, 2-vis [3-2 tro 4-(phenylamino) phenyl] hexafluoropropane Process

2,2-bis obtained in the reaction step (5) [3-2-tro 41 (phenylamino) phenyl] Kisafluoropropane In the organic solvent, the reduction of the nitro group is carried out by hydrogen in the presence of the catalyst in the presence of the catalyst, and the 2,2—vis [3—amino 4 — (Feni Luamino) phenyl] hexafluoropropane.

Organic solvents to be used include, for example, alcohols such as methanol, ethanol, and isoprozol. Can be used. 2, 2 — VIS [3 — NITRO 4 — (FUNILAMINO) FUENIL] EXA FLUOROPLOPAN is a mezzanine, ethanol 2,2-bis [3-amino 1-41 (phenylamino) phenyl, which is a poorly soluble but highly soluble product, but is a reaction product. Hexafluoropropane dissolves, which is advantageous for the separation of reaction products.

Catalysts include, for example, sodium-radiocarbon—hydroxide, hydroxylated, “radical-carbon, platinum, iron, nickel, etc. Can be used, but the ease of post-processing, the high yield and purity, and the low cost of palladium-carbon, especially 5 ~ 20% \\ ° Radium per cylinder, especially 10% Palladium per carbon is preferred.10% Palladium per cylinder When using a boron, the target compound can be obtained with a high yield of 80%. . The amount of catalyst added is the amount of raw material (2, 2-bis [3-2-tro 41 (phenylamino) phenyl)]. ) Is 0.1 to 10% by weight, preferably 0.5 to 2% by weight. Other reaction conditions include a reaction temperature of 10 to 70 ° C, preferably 20 to 30 ° C, and a hydrogen pressure of 0.1 to: L 0. a (1 to 100 atm), preferably 0.; to 2.03 MPa (1 to 20 atm), especially 1. OMPa (10 atm) Used.

2, 2-bis [3-amino-4-(phenylamino) phenyl], a reaction product of the present invention. Nonyl is useful as a cross-linking agent. In addition, it can also be expected to be used as a monomer for polymer synthesis such as polyimidazole.

Next, the present invention will be described based on embodiments, but the present invention is not limited to only such embodiments. All reactions were performed in a nitrogen atmosphere, and the reagents and solvents used were dehydrated.

Example 1

(1) 2, 2 — Vis (4-hydroxy phenyl) to hexa-reflex port Propan (bis phenol AF) Nitro reaction Process

2, 2-bis (4-hydroxy phenyl) hexafluoroprone (bisphenol AF) 5 g (14.9 mi Was dissolved in 20 ml of acetic acid, and the solution was kept at 50 ° C under stirring. A solution prepared by dissolving 2.3 ml (35.766 millimol) of 70% nitric acid in 20 ml of acetic acid was added thereto for 1 hour, and the solution was dropped. After dropping, stir at 50 ° C for 4 hours. Continued. As the reaction progressed, yellow crystals began to precipitate. After confirming the disappearance of the raw material by thin-layer chromatography (TLC), the solution was poured into cold water (150 ml) and the precipitated yellow crystals were collected by filtration. After washing thoroughly with water, depressurize and dry to reduce the pressure to 2,2—vis (312 tro 4—hydroxifene). 5 g of pan was obtained (yield: 95%).

(2 A) 2, 2-Vis (3-2 tro 4-Hydroxyphenyl) Toxyl fluoropropane tosylation reaction process

2,2—Vis (3—Nitro 14-hydroxy phenyl) Hexafluoropropane 4.6 23 g (10.85 mm ) And p-toluenesulfonyl chloride 4.96 3 g (26.03 milimol) dissolved in 50 ml of dichloromethane Then, the mixture was cooled, and then 6.05 ml of triethylamine was dropped. After completion of the dropping, stirring was continued at 0 ° C. for 1 hour, and then the mixture was reacted at room temperature for 3 hours. The reaction solution was poured into 30 ml of diluted hydrochloric acid, the organic layer was taken out, and the aqueous layer was extracted twice with 50 ml of dichloromethane. The extract is added to the above organic layer, washed with dilute hydrochloric acid and water, dried with anhydrous sulfuric acid magnesium, and then dried with magnesium sulfate. The um was filtered off and the solvent was depressurized and distilled off. This was recrystallized from a mixture of hexane and tetrahydrofuran to form a 2,2-vis (3-2 tro-4 -1 toloxy sulfide). 7.3 g of hexafluoropronoone was obtained (yield: 92%).

The physical properties of this material were examined.

Melting point: 20.5 to 21.7 ° C

^{1 H - NMR (DMF - d} 7):.. <5 (ppm) - 7 6 0 ~ 8 1 8 (1 4 H, m, aromatic ring), 2 · 4 9 (6 Η, s, C Η 3 ) ^{IR (KB r) cm 1 =} 1 5 3 6 1 3 5 2 ( Shea turbocharger one-flops be sampled and Russia in _{g, N 0 9), 1 2} 7 0 ~ 1 1 4 0 ( blanking □ one de, vinegar Bok Russia Ring CF 3)

M m 'z = 7 3 4 (m +)

HRMSC _{2 9} H ₂ 0 F ₆ N ₂ 0 S (m +)

Calculated value = 7 3 4 .0 4 5

Measured value = 7 3 4 .0 4 4

(3A) 2,2—vis (3—Nitro 4—Tosyloxyphenyl) Benzylumination of xafluoropropane Reaction process

To the 2,2—vis (312 □ □ 14 卜シシキエエ) synthesized in the reaction process (2 A) Dissolve 300 mg (0.408 milliliter) in 25 ml of butyric acetate and apply it to a gentle and powerful heat-return stream.

0.44 m1 (4.08 millimoles) was dropped, and heating and refluxing were continued at the same temperature for 4 hours. After confirming the disappearance of the raw material with TLC (hexane / ethyl acetate = 3/1), the reaction solution was added.

Cool to the dish, add 20 ml of dilute hydrochloric acid, and add acetic acid ethyl acetate.

The extract was extracted twice, and the extract was washed with dilute hydrochloric acid, aqueous solution of sodium hydrogen carbonate, and saturated saline solution. After the obtained organic layer was dried with anhydrous magnesium sulfate, the magnesium sulfate was filtered off, and the solvent was distilled off under reduced pressure. The obtained residue ¾r The short-circuiting ram (silicone force, hexane Z ethyl acetate 2-1Z1) was used to remove impurities near the origin of TLC. After removal, water / water pressure, re-opened, said, 2,21-vis [3212- □□ 14- (Benzylamino) Hue [Nil] hexafluoropropane) (215 mg) was obtained (yield 83%).

We examined the physical properties of the material. Melting point: 1 3 1 1 3 2 ° C

^!... H - NMR (in _{CDC 1 3): δ (ppm} ) = 6 8 2 8 2 9 (1 6 H, m, Fang incense ring), 4 5 7 (4 H , d, CH 2) 8 . 5 2 (2 H, t, NH)

^{1 9} F - NMR (in _{CDC 1 3):. (5} (ppm) - 6 4 9 (s CF 3)

IR (KB r): cm - 1 1 5 3 5 1 3 5 4 ( sheet catcher-loop, vinegar collected by filtration in g, N 〇 ₉₎ 1 2 7 0 1 1 4 0 (blanking Russia over pass to collected by filtration down G CF

M S m 6 0 4 (m +)

HRMS: C29H22F , _; N, O (m +)

Calculated value = 6 0 4. 1 5 5

Measured value = 6 0 4 .1 5 6

(4) 2 2-Vis [3-Nitro-4-(Benzyl Amino) Fenil] Hex Refrigerant Port Propane Touching Source Reaction About

2 2-Vis [3-2-Tro 4-(Benzylamino) phenyl] Hexafluoropronone 1g (1.65 4S Remote ) Is dispersed in 20 ml of methanol, and then 50 mg of 20% hydroxylamine per degree of boron is added and 50 mg of boron is added, and then replaced with hydrogen. After that, the mixture was vigorously stirred for 24 hours at a hydrogen pressure of 0. IMPa (1 atm) at room temperature. The raw material, 2,2-vis [3—2-nitro-4— (benzylamine) phenyl] is a meta-propane. As the reaction proceeded, the solution gradually dissolved, and the solution became colorless as well. After confirming the disappearance of the raw material by TLC, the reaction solution was filtered off the catalyst with cerite and the methanol was distilled off under reduced pressure. The residue contains 20 m1 of degassed water, and 15% hydrochloric acid The mixture was adjusted to pH 1 by heating, heated to 70 to 80 ° C with a force D, added with 200 mg of activated carbon, and stirred at the same temperature for 15 minutes. After the temperature was lowered to room temperature, activated charcoal was removed by filtration through Celite. Nitrogen gas was blown into the obtained colorless filtrate, and then adjusted to pH 7 with 28% ammonia water at 0 to 20 ° C and settled. You got a gift. The precipitate is collected by filtration, washed thoroughly with degassed water, dried at 35 ° C under reduced pressure until the weight becomes constant, and white-colored. 500 mg of solid 2,2-bis (3,4-diaminophenyl) hexafluoroprone was obtained (yield 83%). . Melting point 218 to 220. C.

In addition, 2,2-bis (3,4-diaminophenyl) hexafluoropropane is unstable to light, heat, and oxygen. Avoid exposure to oxygen as much as possible (hydrochloric acid salts are stable). If recrystallization is required, it may be recrystallized from a mixture of Hexane Z and ethyl acetate.

Example 2

The xafluoropropane was added to the 2,2—vis (3—2-troll-41-hydroxyl) prepared in Example 1 (1). Reactions that convert to trifluorene (3B) and their products are converted to benzylamines (3B) An example of all the synthesis is shown. The obtained 2,2—vis [3—2 □□ 141 (benzylamine) phenyl] hexafluoropropane is the same as in Example 1. It is possible to produce the target compound according to the step (4).

(2 B) 2, 2-bis (3-2-4-hydroxyphenyl) to hexafluoropropane trifluorometer Sulfurization reaction process

2, 2 1 vis (3-2 tro 4-Hydroxif enil) Hexafluoropropane 5 1 g (0.12 mol.) And pyridin 2 16 ml (0.27 mol.) Were added to dichloromethane. m1 and cooled to 178 ° C, a mixture of 74 g (0.26 mol) of water-free trifluoromethanthrylephonic acid was obtained. The solution was dropped into the rolometane solution (130 ml) over a period of 3.75 hours without stirring. After the dropping was completed, IS stirring was continued at the same temperature for 1 hour, and then the reaction was performed by stirring at room temperature for 4 hours. The reaction solution was poured into 100 ml of diluted hydrochloric acid, the organic layer was removed, and the aqueous layer was extracted twice with 100 ml of dichloromethane. The extract is added to the organic layer described above, washed with water with 100 ml of dilute hydrochloric acid, dried with anhydrous sulfuric acid magnesium, and then dried with anhydrous sulfuric acid. The gum was filtered off and the solvent was distilled off under reduced pressure. This was recrystallized from a mixture of Hexane Z and ethyl acetate to give 2 '2 -vis (3-2-tro-4--fluoro- 78.6 g (yield 95%) of melting point of 130.1 to 131X were obtained.

(3 B) 2, 2-VIS (3-PORT-4-TRIFLUOROMETERS LE HONILILLE OXIFENIL) Nozzle Benzilla Minorization Reaction Process

2, 2-bis (3-2 to 4) synthesized by the reaction process (2B) ) Hexafluoropropane (3 g, 0.435 mm) is dissolved in tetrahydrofuran (100 m1), followed by gentle addition. Under the heat return flow, 4.46 m 1 (40.8 millimol) of benzylamine was dropped, and the heat return flow was continued for 3 hours at the same temperature. The reaction solution was poured into 100 ml of diluted hydrochloric acid, 200 ml of ethyl acetate was added, the organic layer was removed, and the aqueous layer was extracted with 10 ml of ethyl acetate. It was extracted twice at 0 m1. The extracted liquid is applied to the above-mentioned screw layer, and diluted salt is added. Wash with water using a single 50 m acid, dry with anhydrous magnesium sulfate, filter off magnesium anhydride, and reduce the pressure of the solvent. I left. This is recrystallized from a mixed solution of water and Z ethanol, and is transferred to 2,2—vis [3—two-row 4 _ (benzylamine) phenyl]. 2.42 g of kisafluoroprone was obtained (yield: 93%). Melting point 13 1 to 13 2 ° (:.

Example 3

To the 2,2-bis (3-nitro 4-1-octyloxy phenyl) synthesized in Example 1 (2A). Here is an example of a reaction (5) that converts a phenylamine into a phenylamine, and a reaction (6) that involves contacting the product.

(5) 2, 2-bis (3-nitro-4-tosyloxyphenyl) to phenylapropanol phenylamine Process

To the 2,2—vis (3—Nitro 4—Tosyloxyfenyl) synthesized in the reaction process (2A) Dissolve 300 mg (0.408 millimol) of butylamine in 25 ml of butyric acetate, and apply mild heat to phenylamine 0.372 ml (4.08 milliliters) was dropped, and the heating and recirculation were continued at the same temperature for 30 hours. After confirming the disappearance of the raw material by TLC (hexano acetic acid ethyl ester = 3/1), the reaction solution was cooled to room temperature and 20 ml of diluted hydrochloric acid was added. In addition, extraction was performed twice with ethyl acetate, and the extracted liquid was washed with dilute hydrochloric acid, aqueous solution of sodium hydrogen carbonate and saturated aqueous solution of sodium chloride. After the obtained organic layer was dried with magnesium sulfate free, magnesium sulfate free was filtered off, and the solvent was distilled off under reduced pressure. The obtained residue is applied to a short column (silica, hexane Z ethyl acetate = 1/1) to remove impurities near the origin of TLC. After removing it, Recrystallized from water Z ethanol to 2,2—vis [3_2-nitro4— (phenylamino) phenyl] 181 mg of propane were obtained (yield 77%).

The physical properties of this material were examined.

Melting point: 16 1 ° C

'H - NMR (in _{CDC 1 3):...} Δ (ppm) = 7 1 5 ~ 8 3 2 (8 H, m, Fang aromatic), 9 6 3 (2 H , S, - NH)

^{1 9} F - NMR (in _{CDC 1 3):. Δ (} ρ ρ πι) = - 6 4 9 (s, CF 3)

IR (KBr): cm- ¹ = 1 5 3 5, 1 3 5 4 (Sharp, Strong, N 0 ₂ ), 1 2 7 0 to 1 1 4 0 (Broad , Strong, CF ₃ )

M S m / z = 5 7 6 (m +)

HRMS ^ 27 H 18 NO ₄ F _fi (m +)

Calculated value = 5 7 6. 1 2 2 8

Measured value = 5 7 6 .1 2 3 0

(6) 2, 2-Vis [3-Nitroguchi 1-41 (phenylamino) phenyl] Reversing source reaction of Kisafluoropropane Process

2, 2-bis [3-dibutylamino] phenyl] hexafluoropropane 200 mg (0.347 mirimo) ) Is dispersed in 4 ml of ethanol, then 10% paradigm-2 mg of carbon is added to the mixture, replaced with hydrogen and brought to room temperature. The stirring was continued violently for 24 hours at a hydrogen pressure of 1 MPa (10 atm). The raw material 2,2—vis [3-2-tro 4— (phenylamino) phenyl] It is difficult to dissolve in the reed, and the reaction is proceeding.

in □ Dimension M

Claims

Scope of claim 2, 2-vis [3-Nitro 1-4 (substituted or non-substituted benzyl relay mino) phenyl] 2,2—vis (3,4,1-diaminophenyl) to contact and restore the propane to the xafluoropropane Manufacturing method.

The process described in Paragraph 1 of the scope of the request to be made in the presence of the contacted S-hydroxylated palladium catalyst.

To the above mentioned 2, 21 [3-Nitro 1-4 (replaced or non-replaced benzylamine) phenyl] To a 2,2—vis (3—Nitro-141-oxy-phenyl), replace or unreplace the xafluoropropane. The scope of the claim that can be obtained by conversion to an enzyme. The manufacturing method described in Paragraph 1 or Paragraph 2.

_Λ . / ■

Description 2, 2-vis [3-nitro-4-1 (substituted or non-substituted benzylamine) phenyl] To the 2,2 1-vis (3-Nitro 4-tri-fluoro mouth) The production method described in Paragraph 1 or Paragraph 2 in which the scope is obtained by replacing or non-replacement benzyl amino.

刖 Replaced or unreplaced benzylamine is replaced by nonreplaceable benzylamine under a heated reflux in an organic solvent. The scope of the claim to be made by reacting the product. The manufacturing method described in Paragraph 3 or 4.

The substituted or unsubstituted benzylamine compound is benzylamine, P-methoxybenzene amide or p. 口第第の製製.

7. Claims in which the organic solvent is a non-protonic solvent and the heating temperature is 25 ° C or more Scope of Claim 5 or 6 The manufacturing method described above.

8. The at least one organic solvent is selected from the group consisting of ethyl acetate, butyrate acetate and tetrahydrofuran. The manufacturing method according to claim 5 or claim 6, wherein the heating temperature is 25 ° C or higher.

9.2, 2—Visions (3—2 to 14-to-one-to-one).

0.2, 2—Vis (3—Nitro-41-silicon phenyl) Replaced or non-replaced with hexafluoropropane Reacting Nilamine compound to react 2,2—vis [3—Nitro—4— (replaced or non-replaced phenylamine) phenyl ] To manufacture a hexafluoropropane, and then to retouch it, use the 2,2—vis [3—amino 4 Replacement or non-replacement phenylamino) phenyl] manufacturing method of hexafluoropropane.