JP7611076B2 - Phenothiazine derivative compounds and their production method - Google Patents

Description

The present invention relates to a phenothiazine derivative compound and a method for producing the same. More specifically, the present invention relates to a phenothiazine derivative compound having a polymerizable unsaturated group and a method for producing the same.

Emission regulations for carbon dioxide, NOx gas, and other gases emitted by internal combustion engines, such as automobile engines, are becoming increasingly strict. In response, automobile engines are required to have higher output, higher thermal efficiency, and reduced and harmless exhaust gases, and the temperature inside the engine compartment is on the rise. Accordingly, there is a demand for even greater heat resistance in the polymeric materials used around them, such as rubber and plastics.

As a specific example, vehicles equipped with turbocharger systems aimed at improving engine fuel efficiency are becoming more and more common. Because the air guided from this turbocharger to the intercooler and engine is at high temperature and pressure, the rubber hose material that transports this air must have high heat resistance.

As a result of the demand for higher temperatures and longer life for the polymeric materials used in automobile engines, it is common to add appropriate antioxidants to rubber product components to improve their heat resistance.

Here, phenol-based and amine-based antioxidants are used as antioxidants, and amine-based antioxidants are used especially for rubber components used in higher temperature environments.

For example, in the case of acrylic rubber, amine-based antioxidants, such as 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, are used as antioxidants (Patent Documents 1 to 6).

However, even the above amine-based antioxidants cannot fully satisfy today's heat resistance requirements.

As a countermeasure, efforts are being made to increase the molecular weight and melting point of amine-based antioxidants, but this raises problems such as reduced dispersibility in rubber and reduced migration within the rubber.

Y：化学的な単結合、－S(=O)-、-SO₂-
R^a、R^b：置換基を有してもよいC₁～C₃₀有機基
Z^a、Z^b：化学的な単結合、-SO₂-
X¹、X²：水素原子、ハロゲン原子、アルキル基、シアノ基、
ニトロ基、-OR¹、-O-CO-R¹、-CO-OR¹、-O-CO-OR¹、-NR²R³、
-NR²-CO-R¹、-CO-NR²R³、-O-CO-NR²R³
n、m：0～2、ただし、いずれか一方は0ではない Patent Document 7 describes a fused heterocyclic compound represented by the following general formula and an organic material composition containing the same, and states that it is possible to impart high processing stability, heat resistance, and long life to organic materials such as polymers that are susceptible to oxidative, thermal, or light-induced degradation.

Y: Chemical single bond, -S(=O)-, -SO ₂ -
R ^a , R ^b : C ₁ -C ₃₀ organic group which may have a substituent
Z ^a , Z ^b : Chemical single bond, -SO ₂ -
X ¹ , X ² : hydrogen atom, halogen atom, alkyl group, cyano group,
Nitro group, -OR ¹ , -O-CO-R ¹ , -CO-OR ¹ , -O-CO-OR ¹ , -NR ² R ³ ,
-NR ² -CO-R ¹ , -CO-NR ² R ³ , -O-CO-NR ² R ³
n, m: 0 to 2, but either one cannot be 0

R¹、R²：水素原子、芳香族環で置換されてもよい
C₁～C₈のアルキル基、
アルコキシ基、ハロゲン原子、シアノ基
R³：水素原子、C₁～C₆の鎖状または環状のアルキル基、
ビニル基、芳香族基
m、n：0～2
5位の硫黄原子が-SO₂-のフェノチアジン化合物も知られており、例えば特許文献８に記載されている。 In recent years, phenothiazine-based antioxidants have been considered to be effective as antioxidants for rubber materials. Patent Document 8 describes a rubber material that is excellent in vulcanization properties, mechanical properties, and heat aging properties and is particularly suitable for use as vibration-proof rubber, which contains (A) a diene rubber, (B) a bismaleimide compound, and (C) the following phenothiazine compound.

R ¹ , R ² : Hydrogen atom, optionally substituted with an aromatic ring
_C1 - _C8 alkyl groups,
Alkoxy group, halogen atom, cyano group
R ³ : a hydrogen atom, a C ₁ -C ₆ linear or cyclic alkyl group,
Vinyl group, aromatic group
m, n: 0 to 2
Phenothiazine compounds in which the sulfur atom at the 5-position is --SO ₂ -- are also known and are described in, for example, Patent Document 8.

In addition, antioxidants with polymerizable unsaturated groups have been marketed to prevent the evaporation of antioxidants and extend the life of rubber parts in high-temperature environments.

For example, Nocrac G-1 (Ouchi Shinko Chemical Industry Co., Ltd.) and APMA (Seiko Chemical Industry Co., Ltd.) are exemplified as such compounds (Non-Patent Documents 1 and 2).

However, the diphenylamino group of the above antioxidant inhibits radical polymerization, making it practically difficult to carry out radical copolymerization with a polymerizable unsaturated monomer (Patent Document 9).

In addition, several methods have been disclosed for introducing a diphenylamino structure into a polymer by a modification reaction of an elastomeric polymer. For example, a method of hydroformylating the side chain of an elastomer having an olefinic unsaturated group and then introducing a diphenylamino group (Patent Document 10) and a method of adding maleic anhydride to a diene copolymer in the presence of a free radical generator and then introducing a diphenylamino group (Patent Document 11) are known. However, these methods require an additional modification step of introducing a diphenylamino group after producing the base copolymer, and are not practical in terms of production costs.

Furthermore, a method is known in which acrylic rubber is crosslinked in the presence of 4-aminodiphenylamine (Patent Document 12). In this method, there is concern that 4-aminodiphenylamine may somewhat inhibit polyamine crosslinking.

Japanese Patent Application Publication No. 11-21411 WO 2007/005458 A1 JP 2010-254579 A WO 2006/001299 A1 JP 2011-032390 A WO 2011/58918 A1 WO 2011/093443 A1 JP 2015-227402 A JP 2009-209268 A Japanese Patent Application Publication No. 4-264106 Japanese Patent Application Publication No. 5-230132 WO 2020/158132 A1

Rubber Chem Technol., Vol. 46, p. 106(1973) Rubber Chem Technol., Vol. 52, p. 883 (1979)

The object of the present invention is to provide a novel phenothiazine derivative compound that can be easily copolymerized with a polymerizable unsaturated monomer, and a method for producing the same.

(ここで、R¹は炭素数1～20の一価の脂肪族炭化水素基または炭素数7～20のアラルキル基であり、R²は水素原子またはメチル基である)で表されるフェノチアジン誘導体化合物によって達成され、このフェノチアジン誘導体化合物は、一般式〔II〕

(ここで、R¹は炭素数1～20の一価の脂肪族炭化水素基または炭素数7～20のアラルキル基であり、R²は水素原子またはメチル基である)で表される化合物のカルボニル基をビニル基に変換することによって製造される。 The object of the present invention is to provide a compound represented by the general formula [I]

(wherein R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R ² is a hydrogen atom or a methyl group), and this phenothiazine derivative compound is represented by the general formula [II]:

(wherein ^R1 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and ^R2 is a hydrogen atom or a methyl group) by converting the carbonyl group of the compound represented by the formula (I) to a vinyl group.

Since the amino group ( _NHAr2 ) at the 10-position of the phenothiazine derivative compound of the present invention is alkylated, unlike conventional polymerizable amine-based antioxidants, it has the effect of suppressing the radical polymerization inhibitory effect and facilitating copolymerization with various polymerizable unsaturated monomers.

It is also presumed that during the processing stage (primary crosslinking, secondary crosslinking) or during actual use after processing, the alkyl group at the 10th position decomposes, liberating the amino group ( _HNAr2 ), which exerts an anti-thermal aging effect.

The elastomeric polymer material in which the phenothiazine derivative compound of the present invention is copolymerized can prevent the volatilization of anti-aging components due to heat or the extraction of anti-aging components by liquid media such as oils and oils or organic solvents, thereby enabling the rubber parts to have a longer life in a variety of deterioration environments.

1 is a graph showing the elongation at break of an acrylic rubber over time (solid line: Example 8, two-dot chain line: Comparative Example 2, long dashed line: Comparative Example 3). 1 is a graph showing the elongation at break of an acrylic rubber over time (solid line: Example 10, dashed dotted line: Comparative Example 4, dotted line: Example 9).

In the phenothiazine derivative compound represented by the general formula [I], R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.

Specific examples of the aliphatic hydrocarbon group include primary hydrocarbon groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-undecyl group, an n-pentadecyl group, and an n-heptadecyl group;
secondary hydrocarbon groups such as an isopropyl group, a 2-butyl group, a 2-pentyl group, a 3-pentyl group, a 2-hexyl group, a 3-hexyl group, a 2-heptyl group, a 3-heptyl group, a 4-heptyl group, a 2-octyl group, a 3-octyl group, and a 4-octyl group;
tertiary hydrocarbon groups such as a tertiary butyl group, a 1,1-dimethyl-1-propyl group, a 1,1-dimethyl-1-butyl group, a 1,1-dimethyl-1-pentyl group, a 1,1-dimethyl-1-hexyl group, a 3-methyl-3-pentyl group, a 3-ethyl-3-pentyl group, and a 3-methyl-3-hexyl group;
alicyclic hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 1-methyl-1-cyclopentyl group, and a 1-methyl-1-cyclohexyl group;
Examples of the alkyl group include aliphatic hydrocarbon groups having 1 to 20 carbon atoms, such as a 1-adamantyl group.
Examples of the aralkyl group include a benzyl group and a 1-phenylethyl group.

In the phenothiazine derivative compound represented by the general formula [I], ^R2 is a hydrogen atom or a methyl group.

There is no particular limitation on the method for producing the compound represented by the general formula [I]. When ^R2 is a hydrogen atom, the compound can be easily produced from inexpensive raw materials, for example, by the following method.

[Step 1] N-alkylation reaction of phenothiazine: (A) → (B)
In the N-alkylation of phenothiazine, an alkyl halide such as an alkyl chloride, alkyl bromide, or alkyl iodide is used as the alkylating agent.

The amount of alkyl halide used is in the range of about 1 to 2 moles per mole of phenothiazine.

The reaction is carried out by reacting phenothiazine with a base such as sodium amide, potassium tert-butoxide, sodium hydride, sodium hydroxide, or potassium hydroxide, and then reacting with an alkylating agent. Sodium amide, potassium tert-butoxide, or sodium hydride are used in the range of about 1 to 2 moles per mole of phenothiazine. Sodium hydroxide or potassium hydroxide is used as a highly concentrated aqueous solution, and the amount is in large excess relative to the phenothiazine. In this case, benzyltriethylammonium chloride or the like may be coexisted.

Reaction solvents that can be used include, for example, N,N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, etc.

The reaction of phenothiazine with a base occurs at approximately 0 to 10°C, while N-alkylation occurs at approximately 0 to 80°C.

[Step 2] Introduction of formyl group: (B) → (C)
There is no particular limitation on the method for introducing a formyl group into phenothiazine, but examples thereof include the Vilsmeire-Haack reaction.

Formylating agents that can be used include, for example, N-monoalkylformamide/phosphorus oxytrichloride, N,N-dialkylformamide/phosphorus oxytrichloride, N-methylformanilide/phosphorus oxytrichloride, etc., and N,N-dimethylformamide/phosphorus oxytrichloride is commonly used.

As the solvent, for example, a chlorine-containing hydrocarbon solvent such as metadichlorobenzene, chloroform, or 1,2-dichloroethane, or an aprotic polar solvent such as N,N-dimethylformamide, is used. These solvents can be used alone or in combination of two or more. The reaction is carried out at about 0 to 100°C.

[Step 3] Reduction of formyl group: (C) → (D)
The reduction reaction of the formyl group is carried out by a metal hydride or catalytic hydrogenation. Examples of metal hydrides include lithium aluminum hydride, sodium borohydride, lithium borohydride, magnesium borohydride, aluminum borohydride, calcium borohydride, and zinc borohydride. The metal hydride is used in a ratio of about 0.5 to 5 moles, preferably about 1 to 3 moles, per mole of (C). For catalytic hydrogenation, hydrogen/palladium, hydrogen/palladium carbon, hydrogen/platinum, etc. are used.

Solvents that can be used include, for example, methanol, ethanol, and tetrahydrofuran.

The reaction temperature is about 0 to 100°C, preferably about 0 to 60°C.

[Step 4] Oxidation of sulfur atom: (D) → (E)
The oxidizing agent used in the oxidation reaction is, for example, metachloroperbenzoic acid, peracetic acid, acetic acid/hydrogen peroxide, etc. The amount of the oxidizing agent used is about 2 to 6 moles per mole of compound (C).

Reaction solvents include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane and octane, chlorine-containing solvents such as dichloromethane and chlorobenzene, and acetic acid. These solvents can be used alone or in combination of two or more.

The reaction is carried out at a temperature ranging from about 0 to 150°C, preferably from about 20 to 100°C.

Oxidation of the sulfur atom can also be carried out on phenothiazine or its alkylated derivatives, followed by the introduction of a formyl group and its reduction in the same manner.

[Step 5] Conversion of hydroxymethyl group to formyl group: (E) → (F)
The conversion of a hydroxymethyl group to a formyl group can be carried out using mild oxidizing agents. For example, it can be carried out by Swern oxidation, PCC oxidation, PDC oxidation, TPAP oxidation, Dess-Martin oxidation, TEMPO oxidation, Mukaiyama oxidation, etc. In the case of Swern oxidation, oxalyl chloride/dimethyl sulfoxide is used as the oxidizing agent. Dichloromethane is used as the solvent, and the reaction is carried out at about -80 to -60°C, and then the conversion to a formyl group is achieved by the action of a basic nitrogen-containing compound that does not have an active hydrogen, such as triethylamine.

[Step 6] Conversion of formyl group to vinyl group: (F) → (G)
The conversion reaction of a formyl group to a vinyl group is not particularly limited, and can be carried out by the Wittig reaction, the Peterson reaction, or the like.

In the case of the Wittig reaction, compound (F) is reacted with a phosphorus ylide compound generated from 1 to 2 moles of a base such as potassium tert-butoxide and an alkyltriphenylphosphonium halide such as methyltriphenylphosphonium bromide per mole of compound (F) at about 0 to 60°C. Tetrahydrofuran or the like can be used as the reaction solvent.

When ^R2 is a methyl group, it can be easily produced from inexpensive raw materials, for example, by the following method.

[Step 1] Acetylation reaction of phenothiazine: (A) → (H)
Acetylation can be achieved using acetyl chloride in the presence of a Lewis acid catalyst, typically aluminum chloride.

[Step 2] Reduction of acetyl group: (H) → (I)
This can be carried out in the same manner as in the reduction of formyl group (C) → (D) above.

[Step 3] Acetylation of hydroxyl group: (I) → (J)
The reaction can be carried out using acetyl chloride in the presence of a basic compound, such as a nitrogen-containing compound having no active hydrogen, for example, pyridine, 4-N,N-dimethylaminopyridine, triethylamine, etc.

[Step 4] N-alkylation reaction of phenothiazine: (J) → (K)
This can be done in the same manner as above (A) → (B).

[Step 5] Oxidation of sulfur atom: (K) → (L)
This can be done in the same manner as above (D) → (E).

[Step 6] Ester hydrolysis: (L) → (M)
The reaction can be carried out using an alkali metal hydroxide, and a mixed solvent of water/methanol can be used as the solvent.

[Step 7] Oxidation of 1-hydroxyethyl group to acetyl group: (M) → (N)
This can be done in the same manner as above (E) → (F).

[Step 8] Conversion of carbonyl group to olefin: (N) → (O)
This can be done in the same manner as above (F) → (G).

When copolymerizing another polymerizable unsaturated monomer with the phenothiazine derivative compound [I] of the present invention, the compound [I] is used in an amount of about 0.1 to 5 parts by weight, preferably about 0.3 to 3 parts by weight, per 100 parts by weight of the other polymerizable unsaturated monomer. If the amount is less than this, a sufficient anti-aging effect cannot be expected. On the other hand, if more than this is used, no improvement in the anti-aging effect can be expected, and it is uneconomical.

The scope of application of the above-mentioned phenothiazine derivative compound [I] is not particularly limited as long as it is an elastomeric polymer material produced by radical polymerization.

Acrylic copolymers are produced by the general copolymerization method for acrylic rubber. The copolymerization reaction can be carried out by any method, such as emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization, but it is preferable to use emulsion polymerization or suspension polymerization, and the reaction is carried out at a temperature of about -10 to 100°C, preferably about 5 to 80°C.

Polymerization initiators for the reaction include organic peroxides or hydroperoxides such as benzoyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide, and p-methylene hydroperoxide, diazo compounds such as azobisisobutyronitrile and azobisisobutylamidine, and peroxide salts such as ammonium salts, sodium salts, and potassium salts, which are used alone or as redox systems.

Emulsifiers that are particularly preferred for use in emulsion polymerization methods include anionic or nonionic surfactants, which are used as aqueous solutions, with the pH adjusted with an acid or base as necessary, and buffered with an inorganic salt.

The polymerization reaction is continued until the conversion rate of the monomer mixture reaches 90% or more. The obtained aqueous latex is coagulated by a salt-acid coagulation method, a method using a salt such as calcium chloride, magnesium sulfate, sodium sulfate, or ammonium sulfate, a method using a boron compound such as boric acid or borax, a heat coagulation method, or a freeze coagulation method, and the obtained copolymer is thoroughly washed with water and dried. This acrylic rubber has a Mooney viscosity PML ₁₊₄ (100°C) of about 5 to 100, preferably about 20 to 80.

Other examples of elastomeric copolymers include styrene-butadiene rubber (SBR), chloroprene rubber (CR), ethylene-vinyl acetate rubber (EVA), nitrile rubber (NBR), hydrogenated nitrile rubber (H-NBR), ethylene-methyl acrylate rubber (AEM), etc.

Next, the present invention will be explained using examples.

化合物(g)は、下記の方法により製造した。

Example 1
Preparation of compound (g)

Compound (g) was produced by the following method.

¹H NMR(400MHz、Acetone-d6)δ ppm (TMS)：
3.39 (s、3H、N-CH ₃)
6.91-6.98 (m、4H、Ar)
7.14 (dd、J=7.6Hz、J=1.6Hz、2H、Ar)
7.21 (td、J=7.6Hz、J=1.6Hz、2H、Ar) [First step] (a) → (b):
In a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, a dropping funnel, and a nitrogen gas inlet/outlet, 40.0 g (201 mmol) of phenothiazine and 200 ml of N,N-dimethylformamide were placed and the flask was heated under a nitrogen atmosphere. The temperature in the system was cooled to 5°C or less. While keeping the temperature in the system at 10°C or less, 7.2g (300mmol) of sodium hydride was added and reacted for 1 hour. The temperature in the system was cooled to 20°C or less. While maintaining the temperature, 34.2 g (241 mmol) of methyl iodide was added dropwise and the reaction was continued for another hour. After the reaction was completed, the reaction mixture was added to a saturated aqueous solution of sodium chloride. The colorless solid that precipitated was filtered and dissolved in acetic acid. The organic layer was washed with a saturated aqueous solution of sodium chloride, and then dried over anhydrous magnesium sulfate. Insoluble matter was then filtered off. Volatile components were removed from the filtrate under reduced pressure to obtain a crude product. The product was obtained in an amount of 45.9 g (crude yield 107%). Recrystallization from ethanol gave 40.5 g (yield 94%) of 10-methyl-10H-phenothiazine (b) as colorless needle crystals.

^1H NMR (400MHz, Acetone-d6) δ ppm (TMS):
3.39 (s, 3H, NC H ₃ )
6.91-6.98 (m, 4H, Ar)
7.14 (dd, J=7.6Hz, J=1.6Hz, 2H, Ar)
7.21 (td, J=7.6Hz, J=1.6Hz, 2H, Ar)

¹H NMR(400MHz、Acetone d6)δ ppm (TMS)：
3.49 (s、3H、N-CH ₃)
7.00-7.06 (m、2H、Ar)
7.10 (d、J=8.4Hz、1H 、Ar)
7.15-7.19 (m、1H、Ar)
7.22-7.28 (m、1H、Ar)
7.61 (d、J=1.6Hz、1H、Ar)
7.75 (dd、J=8.4Hz、J=1.6Hz、1H、Ar)
9.85 (s、1H、-CHO) [Step 2] (b) → (c):
210 ml of N,N-dimethylformamide was placed in a 500 ml four-neck flask equipped with a magnetic stirrer, a dropping funnel, a thermometer, a gas inlet/outlet, and a reflux condenser. Under a nitrogen atmosphere, 129.4 g (844 mmol) of phosphorus oxytrichloride was added dropwise while maintaining the internal temperature of the system below 10°C, and the reaction was continued for another 30 minutes. Next, 30 g (141 mmol) of compound (b) obtained in the first step was added, and the reaction was continued at 60°C for 24 hours. After the reaction was completed, the contents were poured into an aqueous sodium acetate solution, and sodium bicarbonate was added for neutralization. The product was extracted from the resulting aqueous solution using ethyl acetate, and the organic layer was washed once with a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate, and insoluble matter was filtered off, and then volatile components were distilled off from the filtrate under reduced pressure to obtain 33.5 g of crude product (crude yield 98%) as a red oily substance. The low Rf components were removed by column chromatography (carrier: Wakogel C300) using ethyl acetate as an eluent to obtain 33.2 g (98% yield) of the crude product as a yellow solid. Further recrystallization using ethyl acetate gave 30.1 g (88% yield) of 10-methyl-10H-phenothiazine-3-carbaldehyde (c) as a yellow crystal.

^1H NMR (400MHz, Acetone d6) δ ppm (TMS):
3.49 (s, 3H, NC H ₃ )
7.00-7.06 (m, 2H, Ar)
7.10 (d, J=8.4Hz, 1H, Ar)
7.15-7.19 (m, 1H, Ar)
7.22-7.28 (m, 1H, Ar)
7.61 (d, J=1.6Hz, 1H, Ar)
7.75 (dd, J=8.4Hz, J=1.6Hz, 1H, Ar)
9.85 (s, 1H, -CHO )

¹H NMR(400MHz、Acetone d6)δ ppm (TMS)：
3.38 (s、3H、N-CH ₃)
4.08 (t、J=6.0Hz、1H、-CH₂OH)
4.53 (d、J=6.0Hz、2H、-CH ₂OH)
6.87-6.98 (m、3H、Ar)
7.10-7.23 (m、4H、Ar) [3rd step] (c) → (d):
Into a 2000 ml four-neck flask equipped with a magnetic stirrer, a thermometer, a gas outlet and a reflux condenser, 30 g (124 mmol) of the compound (c) obtained in the second step and 1200 ml of methanol were placed. While keeping the temperature below 30°C, 4.7 g (124 mmol) of sodium borohydride was slowly added and the reaction was continued for another hour. Methanol was distilled off under reduced pressure, and the residue was dissolved in methyl isobutyl ketone. The organic layer was washed once with a saturated aqueous solution of sodium chloride, and then the organic layer was dried over anhydrous magnesium sulfate, after which the insoluble matter was filtered off. The volatile components were removed from the filtrate under reduced pressure to obtain a crude product as a pale yellow solid. The product was obtained in an amount of 29.4 g (crude yield 97%). Recrystallization was carried out using ethyl acetate to obtain 28.2 g (yield) of 3-hydroxymethyl-10-methyl-10H-phenothiazine (d) as a pale yellow solid. The success rate was 93%.

^1H NMR (400MHz, Acetone d6) δ ppm (TMS):
3.38 (s, 3H, NC H ₃ )
4.08 (t, J=6.0Hz, 1H, -CH ₂ O H )
4.53 (d, J=6.0Hz, 2H, -C H ₂ OH)
6.87-6.98 (m, 3H, Ar)
7.10-7.23 (m, 4H, Ar)

¹H NMR(400MHz、Acetone d6)δ ppm (TMS)：
3.80 (s、3H、-N-CH ₃)
4.43 (t、J=6.0Hz、1H、-CH₂OH)
4.75 (d、J=6.0Hz、2H、-CH ₂OH)
7.35 (t、J=7.6Hz、1H、Ar)
7.56 (t、J=8.4Hz、2H、Ar)
7.68-7.76 (m、2H、Ar)
8.00-8.05 (m、2H、Ar) [Step 4] (d) → (e):
Into a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, and a reflux condenser, 17.0 g (70 mmol) of the compound (d) obtained in the third step, 150 ml of acetic acid, and 19.0 g (168 mmol) of 30% hydrogen peroxide were added and reacted at 60° C. for 1 hour and at 80° C. for 1 hour. Acetic acid was distilled off from the reaction mixture under reduced pressure, and the residue was recrystallized using methanol to obtain 17.8 g (yield 92%) of 3-hydroxymethyl-10-methyl-10H-phenothiazine-5,5-dioxide (e) as a pale yellow solid.

^1H NMR (400MHz, Acetone d6) δ ppm (TMS):
3.80 (s, 3H, -NCH3 ₎
4.43 (t, J=6.0Hz, 1H, -CH ₂ O H )
4.75 (d, J=6.0Hz, 2H, -C H ₂ OH)
7.35 (t, J=7.6Hz, 1H, Ar)
7.56 (t, J=8.4Hz, 2H, Ar)
7.68-7.76 (m, 2H, Ar)
8.00-8.05 (m, 2H, Ar)

¹H NMR(400MHz、Chlorofolm-d)δ ppm (TMS)：
3.79 (s、3H、N-CH ₃)
7.35-7.45 (m、3H、Ar)
7.66-7.73 (m、1H、Ar)
8.11-8.16 (m、2H、Ar)
8.58 (d、J=1.6Hz、1H、Ar)
10.00 (s、1H、-CHO) [Step 5] (e) → (f):
In a 500-mL four-neck flask equipped with a magnetic stirrer, thermometer, dropping funnel, and gas inlet/outlet, add 15.3 g (121 mmol) of oxalyl chloride and 225 mL of dichloromethane.
The mixture was cooled to -80 to -70°C under a nitrogen atmosphere. 14.1g (181mmol) of dimethylsulfoxide was slowly added dropwise, and the mixture was allowed to react for another 30 minutes. 16.5g (60mmol) of compound (e) dissolved in 8g of dimethylsulfoxide was added dropwise, and the mixture was allowed to react for another 2 hours at -80 to -70°C. Next, 36.6g of triethylamine was added, and the mixture was allowed to rise to room temperature. A saturated aqueous solution of sodium chloride was added to the reaction mixture, and the product was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. The volatile components were removed from the filtrate under reduced pressure to obtain 28.0g of crude product (94% yield). Column chromatography (carrier: Wakogel C300) using dichloromethane as an eluent was performed, and 15.4g (94% yield) of compound (f) was obtained as a pale yellow solid.

^1H NMR (400MHz, Chloroform-d) δ ppm (TMS):
3.79 (s, 3H, NC H ₃ )
7.35-7.45 (m, 3H, Ar)
7.66-7.73 (m, 1H, Ar)
8.11-8.16 (m, 2H, Ar)
8.58 (d, J=1.6Hz, 1H, Ar)
10.00 (s, 1H, -CHO )

¹H NMR(400MHz、Chlorofolm-d)δ ppm (TMS)：
3.71 (s、3H、N-CH ₃)
5.31 (d、J=11.2Hz、1H、Arに対してtrans-CH ₂=CH-Ph)
5.79 (d、J=17.6Hz、1H、Arに対してcis-CH ₂=CH-Ph)
6.74 (dd、J=11.2Hz、17.6Hz、1H、CH₂=CH-Ph)
7.23-7.34 (m、3H、Ar)
7.59-7.69 (m、2H、Ar)
8.09-8.15 (m、2H、Ar) [Step 6] (f) → (g):
250 ml of tetrahydrofuran was placed in a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, and a gas inlet/outlet, and the inside temperature was cooled to 10°C or less while replacing the inside of the reaction vessel with nitrogen. 11.2 g (99.7 mmol) of potassium tert-butoxide was added, followed by 35.6 g (99.7 mmol) of methyltriphenylphosphonium bromide, and the reaction was carried out for 30 minutes. 22.7 g (83.1 mmol) of compound (f) obtained in the fifth step above was added to this, and the reaction was carried out for 2 hours at 10 to 30°C. The resulting reaction mixture was added to a saturated aqueous sodium chloride solution, and the product was extracted with dichloromethane. After drying with anhydrous magnesium sulfate, insoluble matter was filtered off, and volatile components were distilled off from the filtrate under reduced pressure, obtaining 47.5 g of residue. Column chromatography (carrier: Wakogel C300) was performed using dichloromethane as an eluent to remove triphenylphosphine oxide, and then recrystallization was performed using acetone to obtain 8.8 g (yield 39%) of compound (g) as a colorless solid.

^1H NMR (400MHz, Chloroform-d) δ ppm (TMS):
3.71 (s, 3H, NC H ₃ )
5.31 (d, J=11.2Hz, 1H, trans- CH2 =CH- _Ph for Ar)
5.79 (d, J=17.6Hz, 1H, cis _- CH2 =CH-Ph for Ar)
6.74 (dd, J=11.2Hz, 17.6Hz, 1H, CH ₂ =C H -Ph)
7.23-7.34 (m, 3H, Ar)
7.59-7.69 (m, 2H, Ar)
8.09-8.15 (m, 2H, Ar)

化合物(n)は下記の方法により製造した。

Example 2
Preparation of compound (n)

Compound (n) was prepared by the following method.

¹H NMR(400MHz、Acetone-d6)δ ppm (TMS)：
0.98 (t, J=7.2Hz, 3H, -CH₂CH₂CH ₃)
1.79 (sext, J=7.2Hz, 2H, -CH₂CH ₂CH₃)
3.90 (t, J=7.2Hz, 2H, -CH ₂CH₂CH₃)
6.93 (td, J=7.6, 1.2Hz, 2H,Ar)
7.00 (d, J=8.0Hz, 2H, Ar)
7.13 (dd, J=7.6Hz, 1.6Hz, 2H, Ar)
7.16-7.22 (m, 2H, Ar) [First step] (h) → (i):
Using 38.7 g (194 mmol) of phenothiazine, 7.0 g (292 mmol) of sodium hydride, 28.6 g (233 mmol) of 1-bromopropane, and 200 ml of N,N-dimethylformamide, the reaction was carried out in the same manner as in the first step of Example 1. The resulting crude product was recrystallized using ethanol to obtain 42.1 g (yield 90%) of compound (i) as a colorless solid.

^1H NMR (400MHz, Acetone-d6) δ ppm (TMS):
0.98 (t, J=7.2Hz, 3H, -CH ₂ CH ₂ C H ₃ )
1.79 (sext, J=7.2Hz, 2H, -CH ₂ CH ₂ CH ₃ )
3.90 (t, J=7.2Hz, _{2H, -CH 2 CH 2} CH _{3 )}
6.93 (td, J=7.6, 1.2Hz, 2H,Ar)
7.00 (d, J=8.0Hz, 2H, Ar)
7.13 (dd, J=7.6Hz, 1.6Hz, 2H, Ar)
7.16-7.22 (m, 2H, Ar)

¹H NMR (400MHz, Acetone-d6) δppm (TMS)：
1.01 (t, J=7.2Hz, 3H, NCH₂CH₂CH ₃）
1.83 (sext, J=7.2Hz, 2H, NCH₂CH ₂CH₃）
3.99 (t, J=7.2Hz, 2H, NCH ₂CH₂CH₃）
7.01 (td, J=8.0Hz, 1.2Hz, 1H, Ar)
7.08 (d, J=7.6Hz, 1H, Ar)
7.12-7.18 (m, 2H, Ar)
7.20-7.26 (m, 1H, Ar)
7.60 (d, J=2.4Hz, 1H, Ar)
7.73 (dd, J=8.4Hz,2.0Hz, 1H, Ar)
9.83 (s, 1H, -CHO) [Second step] (i) → (j):
Compound (i) 34 g (141 mmol), phosphorus oxytrichloride 129.4 g (844 mmol), and N,N-dimethylformamide 210 ml were used to carry out a reaction in the same manner as in the second step of Example 1 to obtain compound (j). 35.8 g (yield 94%) was obtained.

^1H NMR (400MHz, Acetone-d6) δppm (TMS):
1.01 (t, J=7.2Hz, 3H, NCH ₂ CH ₂ CH ₃ )
1.83 (sext, J=7.2Hz, 2H, NCH ₂ CH ₂ CH ₃ )
3.99 (t, J=7.2Hz, 2H, NC H ₂ CH ₂ CH ₃ )
7.01 (td, J=8.0Hz, 1.2Hz, 1H, Ar)
7.08 (d, J=7.6Hz, 1H, Ar)
7.12-7.18 (m, 2H, Ar)
7.20-7.26 (m, 1H, Ar)
7.60 (d, J=2.4Hz, 1H, Ar)
7.73 (dd, J=8.4Hz,2.0Hz, 1H, Ar)
9.83 (s, 1H, -CHO )

[3rd step] (j) → (k):
In the same manner as in the third step of Example 1, 35.8 g (133 mmol) of compound (j), 5.0 g (133 mmol) of sodium borohydride, and 400 ml of tetrahydrofuran were used and reacted at 60° C. for 2 hours to obtain compound (k ) was obtained in an amount of 36.1 g (yield 100%).

[4th step] (k) → (l):
In the same manner as in the fourth step of Example 1, a reaction was carried out using 36.1 g (133 mmol) of compound (k), 45.6 g (402 mmol) of a 30% aqueous hydrogen peroxide solution, and 200 ml of acetic acid to obtain 40.6 g of compound (l). g (yield 100%) was obtained.

[5th step] (l) → (m):
In the same manner as in the fifth step of Example 1, a solution of 40.6 g (134 mmol) of compound (l) dissolved in 50 g of dimethyl sulfoxide, 33.9 g (268 mmol) of oxalyl chloride, 31.4 g (402 mmol) of dimethyl sulfoxide, and dichloromethane were mixed. The reaction was carried out using 300 ml of water and 81.2 g (804 mmol) of triethylamine to obtain 40.6 g (yield 97%) of compound (m).

¹H NMR (400MHz, Chloroform-d) δppm (TMS)：
1.07 (t, J=7.6Hz, 3H, NCH₂CH₂CH ₃)
1.95 (sext, J=7.6Hz, 2H, NCH₂CH ₂CH₃)
4.11 (t, J=7.6Hz, 2H, NCH ₂CH₂CH₃)
5.30 (d, J=11.2Hz, 1H, Arに対してtrans-CH ₂=CH-Ph)
5.78 (d, J=17.6Hz, 1H, Arに対してcis-CH ₂=CH-Ph)
6.73 (dd, J=11.2Hz, 17.6Hz, 1H, CH₂=CH-Ph)
7.23-7.35 (m, 3H, Ar)
7.58-7.68 (m, 2H, Ar)
8.10-8.16 (m, 2H, Ar)
[6th step] (m) → (n):
In the same manner as in Step 6 of Example 1, 39.2 g (130 mmol) of compound (m), 17.5 g (156 mmol) of potassium tert-butoxide, 55.7 g (156 mmol) of methyltriphenylphosphonium bromide, and 350 ml of tetrahydrofuran were used. The reaction yielded 73.9 g of a crude product. Triphenylphosphine oxide was removed by column chromatography (carrier: Wakogel C300) using dichloromethane as an eluent to obtain 18.0 g of compound (n) as a yellow solid. g (yield 46%) was obtained. By further recrystallization using ethyl acetate, 16.3 g (yield 42%) of compound (n) was obtained.

^1H NMR (400MHz, Chloroform-d) δppm (TMS):
1.07 (t, J=7.6Hz, 3H, NCH ₂ CH ₂ C H ₃ )
1.95 (sext, J=7.6Hz, 2H, NCH ₂ CH ₂ CH ₃ )
4.11 (t, J=7.6Hz, 2H, NC H ₂ CH ₂ CH ₃ )
5.30 (d, J=11.2Hz, 1H, trans- CH2 =CH- _Ph for Ar)
5.78 (d, J=17.6Hz, 1H, cis _- CH2 =CH-Ph for Ar)
6.73 (dd, J=11.2Hz, 17.6Hz, 1H, CH ₂ =C H -Ph)
7.23-7.35 (m, 3H, Ar)
7.58-7.68 (m, 2H, Ar)
8.10-8.16 (m, 2H, Ar)

化合物(v)は下記の方法により製造した。

Example 3
Preparation of compound (v)

Compound (v) was prepared by the following method.

[First step] (o) → (p):
Into a 2000 ml four-neck flask equipped with a magnetic stirrer, a thermometer, a gas outlet and a reflux condenser, 25.0 g (104 mmol) of 2-acetylphenothiazine (p) (a product of Tokyo Chemical Industry Co., Ltd.) and 1000 ml of methanol were placed. While maintaining the internal temperature at 45 to 55° C., 19.6 g (518 mmol) of sodium borohydride was slowly added and the reaction was continued for another hour. Methanol was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate. The organic layer was washed once with a saturated aqueous solution of sodium chloride, then dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. The volatile components were removed from the filtrate under reduced pressure to obtain the crude product as a pale yellow solid. Recrystallization was carried out using 85% by weight ethanol to obtain 23.6 g (yield 94%) of 2-(1-hydroxyethyl)-10H-phenothiazine (p) as a pale yellow solid.

[Second step] (p) → (q):
In a 500 ml four-neck flask equipped with a magnetic stirrer and a thermometer, 21.4 g (87.9 mmol) of compound (p), 48.7 g (615 mmol) of pyridine, and 200 ml of dichloromethane were placed. The internal temperature was kept below 15°C. While the reaction mixture was being stirred, 34.5 g (440 mmol) of acetyl chloride was added dropwise and the reaction was continued for another hour. The reaction mixture was added to a saturated aqueous solution of sodium chloride, and the product was extracted with dichloromethane. The product was then dried over anhydrous magnesium sulfate and the insoluble matter was extracted with dichloromethane. The volatile components were distilled off from the filtrate under reduced pressure to obtain 23.7 g (yield 94%) of 2-(1-acetoxyethyl)-10H-phenothiazine (q).

[3rd step] (q) → (r):
In a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, and a gas inlet/outlet, 23.7 g (83.0 mmol) of compound (q) and 170 ml of N,N-dimethylformamide were placed under a nitrogen atmosphere. While keeping the internal temperature below 5°C, 3.0g (125mmol) of sodium hydride was added and reacted for 1 hour. Furthermore, 14.7g (116mmol) of benzyl chloride was added and reacted at 60°C for 1 hour. The reaction mixture was added to a saturated aqueous solution of sodium chloride, and the product was extracted with ethyl acetate. The mixture was then dried over anhydrous magnesium sulfate, and the insoluble matter was filtered off. The volatile components were removed from the filtrate by distillation under reduced pressure. As a result, 34.9 g of crude 2-(1-acetoxyethyl)-10-benzyl-10H-phenothiazine (r) was obtained.

¹H NMR (400MHz, Acetone-d6) δppm (TMS)：
1.31 (d, J=6.8Hz, 3H, CH ₃CH(OCOCH₃)-Ar)
1.85 (s, 3H, CH₃CH(OCOCH ₃)-Ar )
5.66 (s, 2H, Ar-CH ₂)
5.78 (q, J=6.8Hz, 1H, CH₃CH(OCOCH₃)-Ar)
7.23-7.42 (m, 9H, Ar)
7.62 (t, J=8.4Hz, 1H, Ar)
8.04 (d, J=8.4Hz, 1H, Ar)
8.06 (dd, J=8.4Hz, 1H, Ar) [4th step] (r) → (s):
Into a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, and a reflux condenser, 34.9 g (about 83.0 mmol) of the crude compound (r) obtained in the third step, 50 g of acetic acid, and 56 g of 30% hydrogen peroxide were added. (494 mmol) and 300 ml of toluene were added. The reaction was carried out at 50°C, 60°C, and 70°C for 1 hour each, and then at 80°C for 2 hours. The upper layer of the reaction mixture was taken out, and the volatile components were distilled under reduced pressure. The crude product was recrystallized from a toluene/ethanol mixed solvent (v/v=1/1) to give 2-(1-acetoxyethyl)-10-benzyl-10H-phenothiazine. 27.3 g (81% yield from compound (q)) of 5,5-dioxide (s) was obtained.

^1H NMR (400MHz, Acetone-d6) δppm (TMS):
1.31 (d, J=6.8Hz, 3H, C H ₃ CH(OCOCH ₃ )-Ar)
1.85 (s, 3H, CH ₃ CH(OCOC H ₃ )-Ar )
5.66 (s, 2H, Ar- CH2 ₎
5.78 (q, J=6.8Hz, 1H, CH ₃ C H (OCOCH ₃ )-Ar)
7.23-7.42 (m, 9H, Ar)
7.62 (t, J=8.4Hz, 1H, Ar)
8.04 (d, J=8.4Hz, 1H, Ar)
8.06 (dd, J=8.4Hz, 1H, Ar)

¹H NMR (400MHz, Acetone-d6) δppm (TMS)：
1.31 (d, J=6.8Hz, 3H, CH ₃CH(OH)-Ar)
4.40 (d, J=４.0Hz, 1H, CH₃CH(OH)-Ar)
4.86 (quint, J=6.0Hz, 1H, CH₃CH(OH)-Ar)
5.63 (s, 2H, Ar-CH ₂)
7.24-7.45 (m, 9H, Ar)
7.57-7.63 (m, 1H, Ar)
8.01 (d, J=8.0Hz, 1H, Ar)
8.07 (dd, J=8.4Hz, 2.0Hz, 1H, Ar) [5th step] (s) → (t):
In a 1000 ml four-neck flask equipped with a magnetic stirrer, a thermometer, and a reflux condenser, 26.9 g (66.0 mmol) of compound (s), 18.5 g (330 mmol) of potassium hydroxide, 500 ml of methanol, and 150 ml of water were placed. The reaction was carried out at 70°C for 2 hours. After the reaction was completed, the volatile components were distilled off under reduced pressure, water was added to the residue, and the product was extracted with dichloromethane. Then, the mixture was dried over anhydrous magnesium sulfate. The insoluble matter was then filtered off. Volatile components were removed from the filtrate under reduced pressure to obtain 23.4 g of a crude product. The product was recrystallized from methanol to give 2-(1-hydroxyethyl)- 22.2 g (yield 92%) of 10-benzyl-10H-phenothiazine-5,5-dioxide (t) was obtained as a pale yellow solid.

^1H NMR (400MHz, Acetone-d6) δppm (TMS):
1.31 (d, J=6.8Hz _{, 3H, CH3CH} ( OH)-Ar)
4.40 (d, J=4.0Hz, 1H, CH ₃ CH( OH )-Ar)
4.86 (quint, J=6.0Hz, 1H, CH ₃ CH (OH)-Ar)
5.63 (s, 2H, Ar- CH2 ₎
7.24-7.45 (m, 9H, Ar)
7.57-7.63 (m, 1H, Ar)
8.01 (d, J=8.0Hz, 1H, Ar)
8.07 (dd, J=8.4Hz, 2.0Hz, 1H, Ar)

¹H NMR (400MHz, Chloroform-d) δppm (TMS)：
2.50 (s, 3H, CH ₃(C=O)-Ar)
5.48 (s, 2H, Ar-CH ₂)
7.19 (d, J=8.8Hz, 3H, Ar)
7.28-7.40 (m, 4H, Ar)
7.52 (t,J=7.6Hz, 1H, Ar)
7.73 (s, 1H, Ar)
7.78 (d, J=8.4Hz, 1H, Ar)
8.15 (d, J=9.2Hz, 1H, Ar)
8.23 (d, J=8.4Hz, 1H, Ar) [6th step] (t) → (u):
330 ml of dichloromethane and 14.4 g (113 mmol) of oxalyl chloride were placed in a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, and a gas inlet and outlet. The temperature in the reaction vessel was adjusted to - After cooling to 70 to -80°C, 13.3g (170mmol) of dimethylsulfoxide was slowly added dropwise and the temperature was maintained for 1 hour. After the addition, the reaction was carried out at the same temperature for 2 hours. After adding 34 g (337 mmol) of triethylamine, the temperature was slowly raised to room temperature, and the reaction mixture was added to a saturated aqueous solution of sodium chloride. The product was extracted with dichloromethane, After drying over anhydrous magnesium sulfate, the insoluble matter was filtered off, and the volatile components were distilled off from the filtrate under reduced pressure to obtain 29.2 g of a crude product. Column chromatography using dichloromethane as an eluent gave 17.8 g (yield 86%) of 2-acetyl-10-benzyl-10H-phenothiazine-5,5-dioxide (u) as a pale yellow solid.

^1H NMR (400MHz, Chloroform-d) δppm (TMS):
2.50 (s, 3H, C H ₃ (C=O)-Ar)
5.48 (s, 2H, Ar- CH2 ₎
7.19 (d, J=8.8Hz, 3H, Ar)
7.28-7.40 (m, 4H, Ar)
7.52 (t,J=7.6Hz, 1H, Ar)
7.73 (s, 1H, Ar)
7.78 (d, J=8.4Hz, 1H, Ar)
8.15 (d, J=9.2Hz, 1H, Ar)
8.23 (d, J=8.4Hz, 1H, Ar)

¹H NMR (400MHz, Chloroform-d) δppm (TMS)：
1.96 (s, 3H, CH₂=CH(CH ₃)-Ar)
5.10 (s, 1H, Arに対してtrans-CH ₂=C(CH₃)-Ar)
5.22 (s, 1H, Arに対してcis-CH ₂=C(CH₃)-Ar)
5.43 (s, 2H, Ar-CH ₂-)
7.12-7.42 (m, 9H, Ar)
7.49 (t, J=8.8Hz, 1H, Ar)
8.08 (d, J=8.4Hz, 1H, Ar)
8.15 (d, J=7.6Hz, 1H, Ar) [Step 7] (u) → (v):
200 ml of tetrahydrofuran was placed in a 500 ml four-neck flask equipped with a magnetic stirrer, a thermometer, and a gas inlet and outlet, and the temperature inside the vessel was cooled to 0°C or lower under a nitrogen atmosphere. Potassium tert-butoxide 8.2 g (73.5 mmol) of compound (u) was added and the mixture was kept at the same temperature for 10 minutes, and then 26.3 g (73.5 mmol) of methyltriphenylphosphonium bromide was added and the mixture was kept at the same temperature for 30 minutes. The reaction mixture was added to a saturated aqueous solution of sodium chloride, and the product was extracted with dichloromethane. The product was then dried over anhydrous magnesium sulfate, and insoluble matter was filtered off. Volatile components were removed from the filtrate under reduced pressure to obtain a crude product. 2-(1-methylethenyl)-10-benzyl-10H-phenothiazine-5,5-dioxide (v ) was obtained as a colorless solid (8.4 g, 47% yield).

^1H NMR (400MHz, Chloroform-d) δppm (TMS):
1.96 (s, 3H, CH ₂ =CH( CH ₃ )-Ar)
5.10 (s, 1H, trans-C H ₂ =C(CH ₃ )-Ar for Ar)
5.22 (cis- CH2 =C( _CH3 )-Ar for s, _1H , Ar)
_5.43 (s, 2H, Ar- CH2- )
7.12-7.42 (m, 9H, Ar)
7.49 (t, J=8.8Hz, 1H, Ar)
8.08 (d, J=8.4Hz, 1H, Ar)
8.15 (d, J=7.6Hz, 1H, Ar)

Example 4
In a separable flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube, and a Dimroth condenser,
Water 187 parts by weight
Sodium lauryl sulfate 2 〃
Polyoxyethylene lauryl ether 2 Same
Charged monomer mixture
Ethyl acrylate [EA] 97.9 〃
Mono-n-butyl fumarate [MBF] 1.6 〃
Compound (g) of Example 1 0.5 〃
After thoroughly removing oxygen from the system by replacing the chamber gas,
Sodium formaldehyde sulfoxylate 0.008 parts by weight
(Fujifilm Wako Pure Chemical products Rongalit)
Tertiary butyl hydroperoxide 0.0047 〃
(NOF Products Perbutyl H-69)
The polymerization reaction was started at room temperature and continued until the polymerization conversion reached 90% or more. The resulting aqueous latex was coagulated with a 10% by weight aqueous solution of sodium sulfate, washed with water and dried to obtain acrylic rubber A. The Mooney viscosity _PML1+4 (100°C) of the resulting acrylic rubber A was 36.

The molar fraction composition was calculated from the following formula using ¹ H-NMR (400 MHz, Acetone d6, δ ppm), and was found to be compound (g): 0.19 mol %, EA + MBF: 99.81 mol %.
α: integral value of signal from 7.0 to 8.2 ppm
β: integral value of signals from 3.2 to 5.0 ppm Compound (g) (mol%) = 200 × α / (2α + 7β)
EA+MBF(mol%)=100-compound (g)(mol%)
The approximate weight fraction composition was calculated from the following formula: Compound (g): 0.5% by weight;
EA+MBF: 99.5% by weight.
Compound (g) (wt%) = (Compound (g) (mol%) × 271.34 × 100) /
[Compound (g) (mol%) x 271.34 + (EA + MBF (mol%)) x 100.8)]
EA + MBF (weight%) = 100-compound (g) (weight%)

Example 5
An acrylic rubber B was obtained by carrying out a copolymerization reaction in the same manner as in Example 4, except that the following monomer mixture was used.
Charged monomer mixture
Ethyl acrylate [EA] 97.4 〃
Mono-n-butyl fumarate [MBF] 1.6 〃
Compound (g) of Example 1 1.0

The Mooney viscosity PML ₁₊₄ (100° C.) of the obtained acrylic rubber B was 27.
The molar fraction composition was compound (g): 0.34 mol %, and EA+MBF: 99.66 mol %.
The approximate weight fraction composition is compound (g): 1.0% by weight, EA+MBF: 99.0% by weight.
It was.

Example 6
Except for using the following charged monomer mixture, copolymerization reaction was carried out in the same manner as in Example 4 to obtain Acrylic Rubber C. The Mooney viscosity PML ₁₊₄ (100° C.) of the obtained Acrylic Rubber C was 31.
Charged monomer mixture
Ethyl acrylate [EA] 97.4 〃
Mono-n-butyl fumarate [MBF] 1.6 〃
Compound (n) of Example 2 1.0

The molar fraction composition was calculated from the following formula using ¹ H-NMR (400 MHz, Acetone d6, δ ppm), and was found to be compound (n): 0.34 mol %, EA+MBF: 99.66 mol %.
α: integral value of signal from 7.0 to 8.2 ppm
β: integral value of signals from 3.2 to 5.0 ppm Compound (n) (mol%) = 200 × α/ (2α + 7β)
EA+MBF(mol%)=100-compound (n)(mol%)
The approximate weight fraction composition was calculated from the following formula: Compound (n): 1.0% by weight;
EA+MBF: 99.0% by weight.
Compound (n) (wt%) = (Compound (n) (mol%) × 299.39 × 100) /
[Compound (n) (mol%) × 299.39 + (EA + MBF (mol%)) × 100.8)]
EA+MBF (wt%) = 100-compound (n) (wt%)

Example 7
Except for using the following charged monomer mixture, copolymerization reaction was carried out in the same manner as in Example 4 to obtain Acrylic Rubber D. The Mooney viscosity PML ₁₊₄ (100° C.) of the obtained Acrylic Rubber D was 25.
Charged monomer mixture
Ethyl acrylate [EA] 97.9 〃
Mono-n-butyl fumarate [MBF] 1.6 〃
Compound (v) of Example 3 0.5 〃

The molar fraction composition was calculated from the following formula using ¹ H-NMR (400 MHz, Acetone d6, δ ppm), and was found to be compound (v): 0.14 mol %, EA+MBF: 99.86 mol %.
α: integral value of signal from 7.0 to 8.2 ppm
β: integral value of signals from 3.2 to 5.0 ppm Compound (v) (mol%) = 100 × α / (α + 6β)
EA+MBF(mol%)=100-compound (v)(mol%)
The approximate weight fraction composition was calculated from the following formula, and was found to be compound (v): 0.5% by weight, and EA+MBF: 99.5% by weight.
Compound (v) (wt%) = (Compound (v) (mol%) × 361.34 × 100) /
[Compound (v) (mol%) x 361.34 + (EA + MBF (mol%)) x 100.8)]
EA + MBF (wt%) = 100-compound (v) (wt%)

Comparative Example 1
Except for using the following charged monomer mixture, copolymerization reaction was carried out in the same manner as in Example 4 to obtain Acrylic Rubber E. The Mooney viscosity PML ₁₊₄ (100° C.) of the obtained Acrylic Rubber E was 33.
Charged monomer mixture
Ethyl acrylate [EA] 98.4 parts by weight
Mono-n-butyl fumarate [MBF] 1.6 〃

Example 8
Acrylic rubber A 100 parts by weight
FEF Carbon Black (Tokai Carbon Products Seast GS0) 60 〃
Stearic acid (Miyoshi Oil Products TST)
Polyoxyethylene stearyl ether phosphate 0.5 〃
(Toho Chemical Industry Co., Ltd. Phosphanol RL-210)
Crosslinking accelerator (Vulcofac ACT55, Safic-Alcan) 1 Same
Hexamethylenediamine carbamate 0.6 〃
(Unimatec product Cheminox AC6F)
Among the above components, acrylic rubber A, FEF carbon black, stearic acid and polyoxyethylene stearyl ether phosphate were mixed in a bumper mixer. The remaining components were mixed with the resulting mixture in an open roll to obtain an acrylic rubber composition.

This was subjected to primary crosslinking at 180°C for 8 minutes using a 100-ton press molding machine and oven crosslinking (secondary crosslinking) at 175°C for 4 hours, yielding a sheet-like crosslinked product with a thickness of approximately 2 mm and a cylindrical crosslinked product with a diameter of approximately 29 mm and a height of approximately 12.5 mm.
The crosslinking characteristics of the acrylic rubber composition and the physical properties of the crosslinked product were measured as follows.
Mooney scorch test: JIS K6300 compliant (125℃)
Using a Mooney Viscometer AM-3 manufactured by Toyo Seiki Seisakusho,
Measure Mooney viscosity (MLmin) and scorch time (t5) Crosslinking test: JIS K6300-2 compliant (180℃, 12 minutes)
Using a rotorless rheometer RLR-3 manufactured by Toyo Seiki Seisakusho, ML, MH,
Measure the values of tc(10) and tc(90)
ML: Minimum torque
MH: Maximum torque
tc(10): Time required for the cross-linking torque to reach ML+(MH-ML)×0.1
tc(90): Time required for crosslinking torque to reach ML+(MH-ML)×0.9 Normal state physical properties: Compliant with JIS K6251 and JIS K6253 Air heating aging test: Compliant with JIS K6257
(190℃: 100 hours, 200 hours, 300 hours, 400 hours, 500 hours)
Compression set: JIS K6262 compliant (175°C: 70 hours)

Example 9
In Example 8, acrylic rubber B was used instead of acrylic rubber A.

Example 10
In Example 8, Acrylic Rubber C was used in place of Acrylic Rubber A.

Comparative Example 2
In Example 8, Acrylic Rubber E was used in place of Acrylic Rubber A.

Comparative Example 3
In Comparative Example 2, 0.5 parts by weight of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Nocrac CD, a product of Ouchi Shinko Chemical Industry Co., Ltd.) was further added.

Comparative Example 4
In Comparative Example 2, 1.0 part by weight of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Nocrac CD, a product of Ouchi Shinko Chemical Industry Co., Ltd.) was further added.

The results obtained in the above Examples 8 to 10 and Comparative Examples 2 to 4 are shown in the following table.

table
Measurement results Actual 8 Actual 9 Actual 10 Ratio 2 Ratio 3 Ratio 4
Mooney scorch test (125℃)
ML min (pts) 66 69 62 71 69 68
t5 (min) 2.7 3.3 2.6 2.6 3.1 3.1

Cross-linking test (180℃)
tc(10) (min) 0.50 0.53 0.51 0.49 0.49 0.48
tc(90) (min) 5.15 5.07 5.10 4.77 4.82 4.81
ML (N・m) 0.29 0.30 0.30 0.27 0.29 0.28
MH (N・m) 1.00 1.02 1.00 1.04 1.05 1.03

Normal physical properties Hardness (Duro A) 68 68 69 68 67 68
100% Modulus (MPa) 5.5 6.0 5.6 5.6 6.0 5.2
Breaking strength (MPa) 18.3 17.4 17.8 17.2 17.4 17.5
Elongation at break (%) 254 245 264 242 236 241

Heat aging test (190℃, 100 hours)
Hardness change (Duro A) 72 76 76 71 71 72
100% Modulus (MPa) 3.3 4.1 3.7 3.0 3.6 3.7
Breaking strength (MPa) 7.5 8.6 8.5 7.4 10.1 10.9
Elongation at break (%) 301 268 294 297 293 296
Heat aging test (190℃, 200 hours)
Hardness change (Duro A) 79 82 80 82 78 77
100% Modulus (MPa) 3.4 3.8 3.5 3.9 3.0 2.9
Breaking strength (MPa) 5.4 6.0 5.7 5.7 5.8 6.3
Elongation at break (%) 275 264 284 200 293 309
Heat aging test (190℃, 300 hours)
Hardness change (Duro A) 88 88 88 92 87 82
100% Modulus (MPa) 5.0 5.2 4.5 5.3 4.2
Breaking strength (MPa) 5.4 5.8 5.3 6.9 5.4 5.3
Elongation at break (%) 135 157 181 51 111 184
Heat aging test (190℃, 400 hours)
Hardness change (Duro A) 90 90 89 94 92 88
100% Modulus (MPa) 6.3 5.8 5.3
Breaking strength (MPa) 6.6 6.3 6.0 8.8 6.4 5.4
Elongation at break (%) 82 103 125 23 62 103
Heat aging test (190℃, 500 hours)
Hardness change (Duro A) 96 95 94 96 93 90
100% Modulus (MPa)
Breaking strength (MPa) 10.0 8.5 8.1 9.3 10.6 8.2
Elongation at break (%) 29 40 45 1 17 36

Compression set
175℃, 70 hours (%) 16 16 16 16 15 15

From the above results, the following can be concluded:
(1) The thianothiazine derivative compound of the present invention can be easily copolymerized with a polymerizable unsaturated monomer.
(2) During processing or during actual use after processing, the alkyl or aralkyl group at the 10-position decomposes to release an amino group, thereby exerting an anti-thermal aging effect.
(3) The elastomeric polymer material in which the phenothiazine derivative compound of the present invention is copolymerized has excellent heat aging resistance in terms of various properties of the elastomeric polymer material, particularly in terms of elongation at break which indicates elastomeric properties.

Claims (6)

General formula [I]

(wherein R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R ² is a hydrogen atom or a methyl group). General formula [II]

(wherein ^R1 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and ^R2 is a hydrogen atom or a methyl group) is converted into a vinyl group. The method for producing a phenothiazine derivative compound according to claim 2, wherein the vinylation reaction is carried out in the presence of an alkyltriphenylphosphonium halide. The phenothiazine derivative compound according to claim 1, which is used as a polymerizable unsaturated monomer for an elastomeric copolymer. The phenothiazine derivative compound according to claim 4, wherein the phenothiazine derivative compound is used in a ratio of 0.1 to 5 parts by weight per 100 parts by weight of the other polymerizable unsaturated monomer. The phenothiazine derivative compound according to claim 4 or 5, wherein the elastomer copolymer is an acrylic elastomer copolymer.

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