SU339549A1 - - Google Patents

Description

METHOD FOR PRODUCING PENOTIAZINE DERIVATIVES The invention relates to the field of production of new phenothiazine derivatives, which can be used as stabilizers for polymeric materials. There is a well-known literature in the literature for the preparation of phenothiazines by reacting diarylamine with sulfur in the presence of iodine at a temperature of about 160 ° C. The products are isolated in a known manner. Describes a known reaction method for the preparation of phenothiazine derivatives of the general formula 0-K-0-R where R is phenylaminophenyl, phenylaminonaphthyl, 2-phenothiazinyl, 2- (6,7-benzofenthiazinyl) residue, X - 2-hydroxypropyl, ethoxyethyl, Ag - phenyl, substituted phenyl, naphthyl. The method consists in that the bisamine of the general formula where X and Ar have the values indicated above, is reacted with sulfur in the presence of iodine. The process is preferably carried out at a temperature higher than 100 ° C, better than 180-190 ° C. Products are isolated in a known manner. Example 1. Preparation of 2-hydroxy-1- (2-fentiazinoxy) -3-fekylaminophenoxypropane. A 10.66 g (0.025 g mol) 2-hydroxy-1,3-di- (p-phenylaminophenoxy) propane, 1.6 g (1.6 ml) was charged to a three-necked flask with a capacity of 0.15 l, equipped with a baffle, thermometer, and gas venting tube. 0.06 g mol) sulfur and 0.106 g iodine. The reaction mass is heated in an air bath. At a temperature of 145 ° C, the reaction mass melts, and hydrogen sulfide begins to precipitate, which is taken up with a solution of potassium hydroxide. Then the reaction mass is heated up to 160-175 ° C and maintained at this temperature until the release of hydrogen sulfide (sample on lead paper). The reaction mass is hot poured into a mortar and ground well into powder.

The resulting powder was washed with ethanol until the iodine disappeared. A light gray powder is obtained with mp. 182-183 ° C.

2-Oxy-1- (2-: fenitiazinoxy) -) - phenylaminophenoxypropane is highly soluble in dimethylformamide and dimethyl sulfoxide, when heated it is soluble in acetone, partly in chlorobenzene and ethyl acetate.

Calculated,% |: C 71.03; And 5.09; N 6.14; S 7.02.

S27P24 250z.

Found,% :: C 71,14; H 5.39; ; N 6.10; S 7.16.

Example 2. Preparation of 2-hydroxy-1- 2-6,7-benzofenthiazinoxy-3 - ha - (/ naphthylamino) phenoxy-propane.

The system for synthesis is collected, as in the previous experiment. In a flask with a capacity of 0.15 l, 10.53 g (0.02 g tol 2-oxy1, 3-di-n- (D-naphthylamino) phenoxy-propane, 1.28 g (0.04 g mol) sulfur and 0.105 g of iodine.

The reaction mass is heated in an air bath. At a temperature of 165 ° C, the reaction mass melts, and hydrogen sulfide begins to precipitate, which is inhaled, filled with caustic potassium solution. Then the reaction mass is heated to 200 ° C and kept at this temperature until the release of hydrogen sulfide (sample on lead paper) stops.

The reaction mass is hot poured into a mortar and ground well into powder.

11.2 g of 2-hydroxy-1- 2- (b, 7-benzofenthiazinoxy) (UZ - naphthylamino) -phenoxy propane are obtained, the yield is quantitative, counting on 2-hydroxy-1,3-di- - (; naphthylamino) - fepoxy propane.

The resulting powder was washed with ethanol until the iodine disappeared. Get the green powder with m. PL. 218-218,5 ° C.

2-Oxy-1- 2- (6, 7-benzofentiazinoksi) (; 5-naphthylamino) -phepoxy-propane is highly soluble in dimethylformamide and dimethyl sulfoxide, when heated, partially soluble in acetone, chlorobenzene and ethyl acetate.

Calculated,%: C 75.51; H 5.07; N 5.03; S 5.76.

C35H28N2SO3.

Found,%: C 75.63; H 5.25; N 4.89; S 5.56.

Example 3. Getting / 5- (2-feniazinoksi) - - (p-phenylaminophenoxy) -diethyl ether.

The system for synthesis is collected as in the previous experiment. In a flask with a capacity of 0.25 l load 22,02 g (0.05 g mol) 2,2di- (tt-phenylaminophenoxy) -diethyl ether, 3.2 g (0.1 g mol) of sulfur and 0.22 g of iodine .

The reaction mass is heated in an air bath. At a temperature of 100 ° C, the reaction mass melts, and hydrogen sulfide begins to precipitate, which is taken up with a solution of potassium hydroxide.

stopping the release of hydrogen sulfide (lead paper test).

The reaction mass is hot poured into a mortar and ground to a fine powder.

12.32 g of y5- (2-fentiazinoxy) -y5 (l-phenylaminoxy) diethyl ether is obtained, which is 87.4%, calculated as 2,2-di- (p-phenylaminopheno: xi) -diethyl ether.

The resulting powder was washed with ethanol until the iodine disappeared. A light gray powder is obtained with mp. 137-138 ° C. The product is well pounded and washed with ethyl alcohol, has so pl. 142-143.2 ° C.

 (2-Fenthiazinoxy) - UZ- (l-phenylaminophenoxy) -diethyl ether is well soluble in 3 dimethylformamide, dimethyl sulfoxide, soluble in acetone, chlorobenzene and ethyl acetate.

Calculated,% :: C 71,46; H 5.57; N 5.95; S 6,81.

C28H26N2SO3.

Found,%: C 71.61; H 5.80; N 6.16; S 6.93.

Example 4. Obtaining (6,7-benzofeniazinoxy) -y5- "-C - naphthylamino) -phenoxy diethyl ether.

Synthesis systems are collected as in the previous experiment. In a flask with a capacity of 0.25 l load 16.62 g (0.03 g-mol) 2,2 di-: l- (/ -naphtylamino) -phenoxy-diethyl ether, 1.92 g (0.06 g mol) of sulfur and 0.162 g of iodine.

The reaction mass is heated in an air bath. At a temperature of 130 ° C, the reaction mass melts, and in this process hydrogen sulfide begins to be released, which is taken up with a solution of caustic potash. Then the reaction mass is heated to 160-180 ° C and maintained at this temperature until the release of hydrogen sulfide (sample on lead paper).

The reaction mass is hot poured into a mortar and ground to a fine powder.

9.62 g of (6,7-benzofenthiazinoxy) (D-, naphthylamino) -fvnoxy-diethyl ether are obtained, which is 84.4%, calculated as 2.2-di- - (/ 3-naphthylamino) -phenoxy - diethyl ether.

The resulting powder was washed with ethanol until the iodine disappeared. A dark green powder is obtained with mp. 152-153 ° C.

(6,7-Ba Б zofeniazinoxy) (/ 3-naphthylamino) -phenoxy-diethyl ether is highly soluble in dimethylformamide, dimethyl sulfoxide, when heated, partially soluble in acetone, chlorobenzene and ethyl acetate.

Calculated ° C ° 75.76; H 5.29; N 4.91; S 5.62.

SzbNZoMgZOZ.

Found,%: C 75.51; H 5.15; N 4.80; S 5.59.

Example 5. Stage I Preparation of 2,2-di (p-phenylaminophenoxy) diethyl ether.

Once in a vacuum / g-oxydiphenylamine and 250 ml of n-butanol (toluene or isopropanol).

The reaction mass is brought to a boil; 21.43 g (0.555 g mol) of caustic soda is charged, kept at the boil for

10 min and load 35.8 g (0.25 g mol) of 2,2 dichlorodiethyl ether in 20 ml of n-butanol (toluene, isopropanol).

The reaction mass is maintained at boiling for 6-9 hours, while during the aging the reaction mass thickens due to precipitation. Then the reaction mass is cooled to room temperature and the precipitated precipitate is filtered off, which is a mixture of the target product and the sodium chloride formed. The filter cake is washed with 150-250 ml of n-butanol (toluene or isopropanol).

The precipitate is transferred to a beaker, 300-400 ml of water is added, triturated thoroughly, heated to 60 ° C and filtered, washing on a filter with water until chlorine is gone, and then 20-30 ml of isopropanol.

94.1 g of 2,2-di- ("- 1-phenylamine-phenoxy) -diethyl ether are obtained, which is 85.4%, calculated as p-oxydiphenylamine. White or white with a pinkish tinge crystalline powder with m. Pl. 101 - 102 ° C (from toluene).

11Stadi. Getting / 5, D-di- (2-fentiazin) xi) -diethyl ether.

In a three-necked flask with a capacity of 0.15 l, equipped with a stirrer, a thermometer and a venting tube, 26.4 g (0.06 g mol) of 2.2-di- (p - phenylaminophenoxy) - diethyl ether, 7.68 g (6 0.24 g-mol) sulfur and 0.26 g iodine.

The reaction mass is heated in an air bath. At a temperature of 100 ° C, the reaction mass dissolves, and hydrogen sulfide begins to be released, which is absorbed with a solution of caustic potash. Then the reaction mass is heated to 170-180 ° C and maintained at this temperature until the release of hydrogen sulfide (sample on lead paper).

The reaction mass is hot poured into a mortar and ground well into powder.

27.2 g of (g) di (2-fentiazinoxy) diethyl ether are obtained, which is 90.2%, calculated on 2,2-di (g-phenylaminophenoxy) diethyl ether.

The resulting powder was washed with ethanol until the iodine disappeared. A gray powder is obtained with mp. 166.8-167.6 ° C.

/ 5, / -di- (2-fentiazinoksi) -diethyl ether is very soluble in dimethylformamide and dimethyl sulfoxide, when heated, soluble in chlorobenzene and acetone, partially soluble when heated in acetic acid, ethyl acetate and benzene.

Example 6. Stage I Preparation of 2,2-di "- (/ 5-naphthylamino) phenoxy-diethyl ether.

In a three-necked flask with a capacity of 0.5 l, equipped with a reflux condenser, a stirrer, a thermometer, and a gas supplying tube, 70.59 g (0.3 g mol) of l-oxyphenyl- / 3-naphthylamine and 200-250 ml of vacuum distilled in vacuum are charged. -butanol (toluene or isopropanol), pre-forced air from the flask with nitrogen.

The reaction mass is brought to a boil, 12.85 g (0.321 g-mol) of caustic soda are charged in a stream of nitrogen, kept at the boil for 10 min, and 21.45 g (0.15 g

mol) 2,2-1Dichlorodiethyl ether (hlorex) in 20 ml of n-butanol (toluene or isopropanol).

The reaction mass at boiling for 6–9 hours, the precipitate precipitates during the aging. Then, the reaction mass is cooled to room temperature in a stream of nitrogen and the precipitated precipitate is filtered off, which is a mixture of the target product and the sodium chloride formed. The precipitate on the filter is washed with 200-250 ml of n-butanol (toluene or isopropanol).

The precipitate is transferred to a beaker, 300 ml of water is added, triturated thoroughly, heated to 60 ° C and filtered, washed on a filter with water until the chlorine ion disappears.

53.6 g of 2,2-di- / g - (- naphthylamino) -phenoxy-diethyl ether are obtained, which is 66.2%, based on g-hydroxyphenyl-) y-naphthylamine. Light brown or light gray crystalline powder with m. Pl. 128-129 ° C. m.p. recrystallized from acetic acid or chlorobenzene 131-132 ° C (light gray plates). The recrystallization yield of 90.7%.

And the stage. Getting / 5, / 3-day- 2- (6,7-benzofentiazinoksi) -diethyl ether.

In a three-necked flask with a capacity of 0.15 l equipped with a stirrer, a thermometer, and a venting tube, 10.82 g (0.02 g

mol) 2,2-di-p - (/ 3-naphthylamino) phenoxy-diethyl ether, 2.56 g (0.08 g mol) of sulfur and 0.108 g of iodine.

The reaction mass is heated in an air bath. At a temperature of 130 ° C, the reaction mass melts, and hydrogen sulfide begins to precipitate, which is absorbed by a solution of caustic potash. The reaction mass is then heated to 160-165 ° C and maintained at this temperature until the evolution of hydrogen sulfide is stopped (sample on lead paper). The reaction mass is hot poured into a mortar and ground well into powder.

11.5 g of α-di-2 (6.7 benzofenthiazinoxy) diethyl ether are obtained, which is 95% yield, calculated on 2,2-di- (α-naphthylamino) phenoxy-diethyl ether.

/ 3,; 3-di- 2- (6,7-benzofentiazinoksi) -diethyl ether is well soluble in dimethylformamide and dimethyl sulfoxide, partially soluble when heated in chlorobenzene, acetic acid, acetone, benzene and ethyl acetate.

Calculated,%: C 71.58; H 4.69; N 4.66; S 10.67.

SzbNgvMaZgOzNadno,%: C 72.06; H 4.51; N 4.34; S 11.07.

Example 7. 1 stddy. Preparation of 2-oxI1, 3-di - (“- phenylaminophenoxy) -propaNa.

92.62 g (0.5 g mol) of p-oxydiphenylamine distilled in yakum and 250 ml of isopropanol (or c-butanol), preliminarily loaded into a three-necked 0.5 L flask equipped with a reflux condenser, a stirrer, a thermometer, and a gas supply tube. displacing air from the flask with nitrogen.

The reaction mass is brought to a boil, 21.43 g (0.535 g mol) of sodium hydroxide are charged in a stream of nitrogen, boiled for 10 minutes, and 32.3 g (0.25 g mol of 20 ml isoprstpanol (or butanol).

The reaction mass is maintained at boiling for 5-7 hours, and during this exposure, the reaction mass thickens greatly due to precipitation. The reaction Riatcy in TdKe is then cooled to room temperature with a filter cake, which is a mixture of the desired product and the sodium chloride formed. The filter cake is washed with 150-200 ml of isopropanol (or butanol).

The precipitate is transferred to a beaker, 300-400 ml of water is added, crushed thoroughly, heated to 60 ° C and filtered, washed on the filter with water until chlorine disappears, and then 20-30 ml of iso-tanol.

86.37 g of 2-oxy-1,3-dy - ("- FeNyla Shfenbksi) -propane are obtained, which is 81%. counting on p-oxydiphenylamine, white or white with a pinkish tinge crystalline powder with m. pl. 144-145 ° C. P st-hey Preparation of 2-hydroxy-1,3-di- (2-fentiazinoxy) propane.

In a three-necked flask with a capacity of 0.15 ug, equipped with a stirrer, a thermometer and a gas tube with a tube, load 17.04 g (0, 04 gmol) 2-hydroxy-1,3-; di- (p-phenylaminophenoxy) propane , 5.12 g (OIb g mole of sulfur and 0.17 g iodine.

The reaction mass is heated in an air bath. At a temperature of 140 ° C, the reaction mass melts, and hydrogen sulfide begins to be released, which is filled with caustic potassium solution. Then the reaction mass is heated to 180–1900 ° C and maintained at this temperature until the release of hydrogen sulfide (sample on lead paper) is stopped.

19.07 g of 2-hydroxy-1,3-di- (2-phenthazyloxane) propane are obtained, which is 97.9%, based on 2-hydroxy-1,3-di - (/ g-phenylaminophenoxy) propane .

5 The resulting powder is washed with ethanol until the iodine disappears. Get .powder gray-green color with m. PL. 209-210 ° C. 2-hydroxy-1,3-di - (2-fentiazinoksi) -propane is well soluble in dimethylformamide and dimethyl sulfoxide, partially soluble in acetone.

Calculated,% ;: C 66,64; H 4.56; N 5.75; S 13.15.

C27H22N2S2O3.

5 Found,%: C 66.70; H 4.63; , N 5.75; S 13.41.

Example 8. I stage. Preparation of 2-hydroxy, 3-di-n - ((v-naphthylamino) feioxy-propane).

Into a three-necked flask with a capacity of 0.5 l, equipped with a reflux condenser, a stirrer, a thermometer, and a gas supplying tube, 94.12 g (0.4 g-mol of p-hydroxyphenyl-ultrasonic naphthylamine and 250 ml of isopropanol (or -butanol), pre-displacing the air from the flask with nitrogen.The reaction mass is brought to a boil, in a stream of nitrogen load 17.13 g (0.428 g mole of sodium hydroxide, incubate at boiling for 10 min and load 25.8 g (Q, 2 g mol of 1,3-dichlorohydrin glycerol in 20 ml of isopropanol (or n-butanol).

The reaction mass is maintained at boiling for 5-7 hours, while in the course of g aging the reaction mass thickens strongly due to the precipitated precipitate. Then, the reaction mass in a stream of nitrogen is cooled to a room temperature and the precipitated precipitate, which is a mixture of

d of the desired product and the resulting sodium chloride. The filter cake is washed with 150-200 ml of isopropanol (or n-butanol). The precipitate is transferred to a beaker, 300-400 ml of water is added, triturated thoroughly, heated to 60 ° C and filtered, washing on a filter with water until chlorine is gone, and then 20-30 ml of isopropanol.

94 g of 2-hydroxy-1, ((3-naphthylamino) phenoxy propane, which is 89%, calculated on p-hydroxyphenyl-naphthylamine, are obtained. Crystalline powder of gray or light brown color with m. Il. 162.4- 163.2 ° C. Stage II. Preparation of 2-hydroxy-1,3-di- 2- {6 75 benz6fenthiazinoxy) -pr6pan.

In a three-necked flask with a capacity of 0.15 l, equipped with a stirrer, a thermometer, and a gas-venting tube, 10.53 g (0.02 g mol 2-OXY-1,3-di-l-naphthylamino-phenoxy-propane) are charged. , 2.56 g (0.08 g-mol of sulfur and 0.105 g of iodine.

the mass is heated to 190 ° C and kept at this temperature until cessation of hydrogen sulfide release (lead paper test).

The reaction mass is hot poured into a mortar and ground well into powder. 11.16 g of 2-hydroxy-1,3-di-2- (6,7-benzofenthiazinoxy) propane is obtained, which is 95.1%, calculated as 2-hydroxy-1,3-: di- / g - (D-, naphthylamino) phenoxy-propane.

The resulting powder was washed with ethanol until the iodine disappeared. Get the green powder with m. PL. 226-227.5 ° C.

2-Oxy-1,3-di-2 - (6, 7 - benzofeniazinoxy-propane is highly soluble in dimethylformamide and dimethyl sulfoxide, partly in acetone and chlorobenzene.

Calculated,%: C 71.64; H 4.46; N 4.77; S 10.93.

Sz5N2bM252Oz.

Found%:

C, 71.53; H 4.43; N 4.80; S 11.14.

The subject matter of the invention is 1. A method for producing phenothiazine derivatives of the formula

Vv

Ag | I r -X-O-R

where R is phenylaminophenyl, phenylaminonaphthyl, 2-fentiazinil, 2- (6,7-benzofeniazinil) - residue;

X - 2-o "sipropil, ethoxyethyl;

Ar - phenyl, substituted phenyl, naphthyl. characterized in that the bisamine of the general formula

-NH-Ar

-0-XO

Ag-MH where X and Ar have the above-mentioned values, are reacted with sulfur in the presence of iodine, at a temperature above 100 ° C, followed by isolation of the products in a known manner.

2. A method according to claim 1, characterized in that the process is carried out at a temperature of 180-190 C.