DE1670722A1 - 1- [4 '- (ss-Acylaminoaethylsulfonyl) phenyl] -3-aryl-delta2-pyrazolines, process for their preparation and use as optical brightening agents - Google Patents

Description

From the Belgian patent specification 629 875 are 1, S- ^ Pyrazoline-g compounds are known in which the 1-position Phenyl radical located in the para position is a substituted Sul ~ fongruppe carries »Among other things, this sulfone group be substituted by a Q-dimethylamino'-ethyl group. j |

It has been found that one il ^ '- Cß'-phenyl7-5-' ^ar y ^{: L} ~ ^ g -pyrazoline of the general formula

(A)

in which R an optionally substituted aryl group, in particular a phenyl and preferably a f-chlorophenyl radical, Y a -GO- or -SO ^ argruppe »R ₁ hydrogen» an alkyl group of up to 20 carbon atoms, an optionally substituted phenyl radical Aralkyl radical and R ₂ mean a lower alkyl group »a cycloalkyl group, an optionally substituted aryl radical and the styryl group, can be produced» if one can use I ^ C ^ '- vinylsulfonylphenylJ-J-aryl-dg'-py ¹ * ⁵²⁰ ^^ * ¹ © » ^w ^ ^{0 &} ^ ^e can be obtained, for example, by the process of French patent 1,354,629, adding carboxamides and sulfonic acid amides which have at least one hydrogen atom on the amide nitrogen.

The reaction proceeds according to the following scheme _:

HN-Y-

O ₂ -CH = CH ₂ SO ₂ -CH ₂ -CH ₂ -NYR ₂

This addition occurs in the presence of a catalytic during brief heating an intimate mixture of vinyl sulfone compound with the carboxylic acid or sulfonic acid amide amounts of alkali, preferably in the presence of sodium methylate at temperatures of 100 ° -20Q ° C »$ preferably 11 ° -140 ⁰ C.

As carboxamides and sulfonic acid amides * - those on the amide nitrogen Carry at least one water stop »may be mentioned, for example ϊ

Acetamide, propionic acid amide, n-butyric acid amide »iso-butyric acid amide, n-valeric acid amide, iso-valeric acid amide, caproic acid amide, Diethyl acetic acid amide, hexahydrobenzamidj 4-methyl » hexahydrobenzamide, benzamide, 4-methylbenzemide, 4-chlorobenzamide », 4 »methoxy- and 4-ethoxy-benzamide, 2imtsäureamidj N-Metliylacfetamid, N-ethyl-acetamide, N-cn-propyl and N-iso-propyl

acetamide, N-n-butylacetamide »N-iso-butyl-aeetamide, N-bodecylacetamide, N-stearyl-aGetamide, N-methyl-hexahydro-benzamide, N-methylbenzömid, N-methyl-cinnamic acid amide, acetanilide 2-, 3- and 4-acetamino-toluene, 4-acetaminophenetole, 4-acetaminophenetole, 4-Acetaiaino-chlorobenzene, N-Benzyl-aeetamitl, n-Butyric anilide,

"I * hexahydro-benzanilide, benzanilide, lime-acid ani3.id, methanesulphonic acid amide, xthanesulphonic acid amide, benzenesulphonic acid amide Benzenesulphonic acid methylamide, benzenesulionic acid ethylamide, toluene-4-sulphonamide, toluene-4-sulphonamide, toluene-4-sulphonamide, toluene-4-sulfonamide ^{, toluene-4-sulfonamide, toluene-1-sulfonamide, toluene-1-sulfonamide, toluene-4-sulfonamide} -stearylamide, toluene-4-sulphonic acid anilide, toluene-4-sulphonic acid benzylamide »

20981W1662

Another method of making the inventive Compounds consists in the conversion of 1 ^ / 5 * - (ß-Ämino-ethylsulfonyl) -phenyl7-3-aryl - &> - pyrazolines, which still carry at least one hydrogen atom on the amine nitrogen and which can be produced, for example, by the process of Belgian patent 661 139, with carboxylic acid and sulfonic acid chlorides, according to the following reaction equation:

H ^ C '"■" "· C-" R

² II

+ CI-YR ₉ \ H ₉ CN. + HCl

SO ₂ -CH ₂ -CH ₂ -KH, -SOp ₁ -CH ₂ -CH ₂ -NYR ₂

This reaction is in the presence of acid-binding coat, preferably at 0-45 ⁰ C, carried out,

in the presence of pyridine bases, at temperatures of 0-1QO ⁰ C,

Examples of carboxylic acid and sulfonic acid chlorides are:

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■. - 4 - Pw 5140

• Acetic acid chloride, propionic acid chloride, η-butt er acid chloride, '' ;. ■ Isobutyric acid chloride, n-valeric acid chloride, hexahydroegradyl chloride, 4-methyl-hexahydrobenzoyl chloride, benzoyl chloride, 4-Kethylben3oylchlorid, 4-Chloro-b2nzQyl-Chlorid, 4-Kethoxy- and 4-a'tho'xy-benzoyl chloride, diphenyl-4-carbon

acid chloride, cinnamic acid chloride, kethanesulfonic acid β chloride, - _k -

. Ithanesulfonic acid chloride, benzenesulfonic acid chloride, toluene-4-sulf onic acid chi orid. . -

As 1- (4'-vinylsulfonyl-phenyl) -3-aryl-A ₂ -pyrazolines are '- ■ 1 - [[4' - (β-Aminoethylsulfonyl) -phenyl]] - 3-aryl-A g-pyrazolines ^ are, for example, the lists in which the Arylr.eat a phenyl or an alkylated alkoxyliertcn, halogenated or a Acylasiinogruppe bearing Phonylrest represents, for example, 4-methylphenyl, 4-methoxy-phenyl, ^{4-Acetaminophenyl-;} 4-iithoxyphenyl-, 4-briaphenyl- and "3,4-dichlorophenyl. Of particular interest are in general those compounds" in which the aryl radical (R) denotes a phenyl or a p "chlorophenyl radical." .- '·. -

The compounds according to the invention can also receive are caused by the action of alkylating agents such as · ζ »Β. . Dimethyl or diethyl sulfate, on such compounds of the

general formula A), in which R _{1 is} a hydrogen atom. r. and Y- represent a -SOg group.

Also the condensation of optionally substituted UM3hlor-. .. propiophenones with phenylhydrazines, which _{carry the ■ -SO 2} CH ₂ CH ₂ -KYR ₂ radical in the p-position, leads to Ag-Pyrazöiinen der

^έ ι -. \. ■ ■ '". ■'

general formula A)

The listed substituents R> E ^ # Rg and Y have the meaning given in the gas, X stands for chlorine.

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5140

1870722

obtained by the method of the present invention ■ Δg-jyrasoline-y compounds of the general formula A) are • almost colorless or «slightly yellow colored products, dio •. as UV absorbers for reproduction materials, E.g. papers are extremely suitable * "· · '.

B. It was also found that almost colorless or pale yellow colored, fluorescent Ä ₂ pyrazolines. that of the general formula. . ·. . ·.

SO ₂ CH ₂ CH ₂ -NYR ₂

v.

. excellent as an optical brightening element. let use. . ^: . · ■

! Di © new connections are characterized by an excellent Fluorescence power and good lightfastness when lightening of fiber materials made of construction wool, polyacrylonitrile and its copolymers, but mainly made of cellulose two-and-a-half and triacetate, polyamide and wool.

The compounds according to the invention are also distinguished by a very good hypochlorite and exhaust gas fastness from .. The Resistance to exhaust gases is particularly important in the case of lightening ■ agents for cellulose two-and-a-half and triacetate fibers one very valuable property.

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■ / ■ 167Ö722

.. - 6 -

The lightening agents according to the present invention can be used in be used in a manner known per se, either in the form of lozenges in organic solvents, or in the form of aqueous Dispersions, optionally with the aid of dispersants. The required quantities, which vary within wide limits can be determined through preliminary tests «

The new compounds can be used with commercially available detergents, even if they contain oxidative bleaching agents such as perborate, can be added to beautify the laundry. Furthermore, the new compounds can also be used together with reductive chemical Bleaching agents, e.g. sodium dithionite "sodium brhydride etc. can be used. .

The new substances can be combined with suitable textile finishing agents such as antistatic agents, softeners, water repellants, etc. ' can be used in combination, which results in very good lightening and finishing effects in one operation. Another one These bodies are used in dye baths. The result is lively, bright colors that are special are desirable for pastel tones. Furthermore, they can also spinning and casting compounds, for example from polymerization products of vinyl chloride, vinylidene chloride, polyethylene, polypropylene, among other things, are added, which are used for the production of artificial fibers, threads, films, foils, Bauer and other moldings,

The new compounds are the closest comparable constitution to the pyrazolines known from Belgian patent specification 629 875 especially due to their better healing capacity of cellulose acetate and polyamide fiber materials.

The following examples are intended to demonstrate the wide range of possible applications show without, however, being restricted to it

C. Example 1

41.6 parts by weight of 1- (4 ^l -Vinylsulfonylphenyl) -3- (p-chlorophenylJ - ^ - pyrazoline are intimately mixed with 12 parts by weight of acetamide and 2 parts by weight of sodium methylate and

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- 7 - Sw 51

Heated to 135-140 ⁰ O for 10 minutes. The melt formed soon solidifies. After cooling, the crystals are comminuted, boiled with 200 parts by volume of methanol, the undissolved particles are separated off and washed with 200 parts by volume of cold methanol. The acetamide-Additionsproaukt VI (s. Table) shows after repeated recrystallization from glacial acetic acid a Schmäzpunkt 211-212 ⁰ C. * '".."

Example 2 , ""

9.36 parts by weight of 1- (4 ^l -Vinylsulfonyl-pheayl) -3-pheayl-. Δ p-pyrazoline will share with 2.95 6ewic) iteteilen acetamide and 0.5 weight Uatriumiaethylat intimately mixed and 10 minutes at 115 - 120 ⁰ C heated. The formed Schinelza solidifies when it cools down, - The crystals are crushed and. Extracted with 40 parts by volume of cold ethanol. The resulting addition product of the formulaΊ. (s · table) zeigt.nach more-. compartments recrystallization from methanol has a melting point of 147 - '148 ⁰ C. - ■. . /

13 | 6 parts by weight dee! - [^ '- (B-Benzylamino-ethylsulfonyl) -

are in 40 VoIu-

mentally puffed up pyridine. At 0 - 5 ⁰ C can be nan 6 Gewiohtsteile 4-methoxy-benzoyl chloride are added dropwise and stirred anschliei3end 1 1/2 hours at room temperature. About 100 parts by volume of methanol are added to the reaction mixture, it is cooled in an ice bath and the acylation product which has precipitated is filtered off with suction and washed with methanol. The compound XV formed (see table) has a melting point of 122-124 after repeated recrystallization from benzene ⁰ C,

Example 4

12.57 parts by weight of the 1-t4 ^r - (ß-Bensylamino-ethylsulfonyl) -phenyl ~} ~ 3-phenyl-Ä2-pyrasoline are added to 40 parts by volume of pyridine and at 0 - 10 ⁰ C while stirring with '

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■■ // Τ- .: ', \ - ■■ - ■: ._ ..- · "'"■; 1670722

5 * 0 parts by weight of kethanesulfonyl chloride are added dropwise. Is then heated to 40 - 45 ⁰ C, holding for one hour at this temperature, again cooled on tree temperature from * the precipitate is suctioned from und.wäscht with methanol. The Sui fonaraid V (see Table) "melts after repeated recrystallization from chlorobenzene at 175 -.176 ⁰ C. ...

10.4 parts by weight of 1- (4'-vinylsulfonylphenyl) -5- (p-chlorophenyl) - ^ 2-py3? Azoline were intimately mixed with 9 parts by weight of 5-ol and heated to ^{160-180 0} O for 5 minutes. The formed enamel © is rubbed with 60 parts by volume of methanol after the srlcold, during which crystallization occurs

washes with Methanoi. The obtained compound XIX (s, iabelle) aeigt after repeated recrystallization from chlorobenzene a melting point 200-202 ⁰ O, ..., ..,

Example 6 ^; '; * -Y ^ / · ^: [. ;>'R .- / - yV j ... - ■: _..':, .χ '' .- _ ■■: _ ■■ '"■'

13> 6 ßev / lichtsteile & es "1-

g 4 / Yo "Pyriata gelHftt and 0 - vereetzt .5 ⁰ C under HOhrung 7.5 Stwichtsteilen Acetylehlorid dropwise · is then stirred for about 1 hour at 40 - 45 ⁰ C after, the mixture is added to ice ,, sucks off the acetylation product formed after it has solidified and washes copiously with it. Water after. The resulting compound IX (s. Table) melts after repeated reprecipitation from methanol at 159-160 C. ^Q

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Mr. ·

'.'..- Ϊ -a toe 1 1 e

² I i! ^Eg \ /

■.?

"IL-

1S7Ö722

-CO-

II -

VI.

VIII - ^ ^N Vci -CO-

-CO-. -H '. -CH

-H

-Cl -CO-

-H -OH

-CH

-OCH ₃ -CH ₃

IX. '-

-co- -CH ₂ C ₆ H ₅

-CO- -H

-CH,

-147-148 °; 130-152 °

, 178-179 °. 199-201 °

■■ - "'* Ä *

,; 175-176 °

; 211-212 °

175-177 °

. 160 * 161 °

159-160 °

-CH ₂ CH ₂ CH ₃ 205-207 *

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- ~ 10 -

'-CO- -H

-CH CH
/

-CO- -OH-

-CH

XIII XIV XV XVI: XVII XVIII

ci -co-

-CO- -

-dO- -OH ₂ CgH ₅

-CO-

-CO- '-CH ^

-CH,

-SO ₂ - -H

-SO ₂ -

-CH ₃

-SO ₉ - -C, H _Q (n)

XXII. -f V-Ci -SO ₂ - -C ₁₆ H ₃₇ Cn) -rj

XIIXI " -f \ -Cl -SO,

-SO ₂ -. -H -CH,

1 / 16S2L "'-Fw 5140

272-274

166-167 ° "

270-272 '

108-10S *

122-124 °

166-168 ° 198-200 °. 210-211 °. . 200-202 ° 181-183 ° 161-162 ° 126-127 ° 183-185 ° 186-187 °

- 11 - -. · Υ4ΡΒΓ 5HO

167Q722

Example 7

A conventionally pre-bleached fabric of cellulose two and a half acetate is in the fleet ratio is20 with a aqueous dispersion, which per liter ■ -

0.15 g of compound VI (table) and

1 ml of formic acid (85%) contains'

30 minutes at a temperature of 80 ⁰ G treated. The degree of whiteness, carried out with the Zeiss Elrepho device "at a wavelength of 460/1 m, shows an increase of. ■. ■ 20 ^ compared to the non-lightened tissue"

Vrarde for preparing the dispersion vmßrigen 0.15 g of compound VI in 7 »5 ml Dimethylformaiaid dissolved and this © solution in 1 1 of hot v / ater, the 0.38 g of the Ozäthylierunge-" product from Iiony! _# Phenol and 23 mol Ethylene oxide dissolved • contained, .poured. * - .. * · '·,' ■

An equally bleached tissue made from sellulo triacetate tends to improve the whiteness by 15 S ^. · ... - ·.

A woolen fabric bleached in the usual way is treated in a liquor ratio of 1.20 at 6O ⁰ G for 45 minutes with a watery. Dispersion treated, the im. Liter

0.3 g of compound I (table),

1.2 g sodium dithionite as well 0.8 g Hatriua pyrophosphate

contains. , -.

This treatment can increase the whiteness by 11 5 » established v / earth.

200811 /

The aqueous dispersion was given in Example 7 Way .made. *

Example 9

■ 'A bleached fabric aus.Wolle .wird.ig long Plot with plot (1 * 20) treated for 45 minutes at 60 ⁰ C with an aqueous dispersion, in -the liter'. . ·.

0.2 g of compound XV (table), '

1.2 g Hatriua dithionite and

0.8 g liatrium pyrophosphate L _ ·.

™ contains. This treatment results in a degree of whiteness. "£ 10 increase over non-lightened tissue".

The aqueous dispersion is used in the example; 7 specified. Art manufactured. - ·. . . .

Example 10

A fabric * consisting of at least $ 85> polyacrylonitrile is treated in a liquor ratio of Ίί20'30 minutes at 98 ⁰ O with an aqueous dispersion, which is in the liter

0.2 g of compound I (table),

* 1 .ml formic acid (85 ^ ig) and, "". .

.1 g of alkylaryl polyglycol ether

contained. The improvement of the whiteness correct compared to the Starting tissue is 10 ^.

If, instead of the compound I, the compound V is used in the same amount and works in the same way, one obtains 'Also a lightening of $ 10.

¹ DIo aqueous dispersion was, as described in Example 7,. divided. , · '. _

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JJ70722

Example 11 ■

A bleached in a conventional manner Polycaprolactamgewebe is treated at a liquor ratio of 1:20 at 6O ⁰ C for 30 minutes with an aqueous dispersion containing, per liter,

Q, 15gder. Compound XIX (table) and. 1 g sodium carbonate

contains. The result is compared to the tissue that has not been lightened an increase in whiteness of 10%,

The aqueous dispersion was prepared in the manner indicated in Example 7. When using the same amount of compound I instead of XIX, the increase in remission is 12 %, when using compound IX 10 % _m

10% brightening is also achieved when using the same Amount of compound VI and use of 1 ml formic acid instead of sodium carbonate under otherwise identical conditions »

Example 12 '-

A bleached raw fabric made of cellulose two-and-a-half acetate was in a liquor ratio of 1:20 in a whitening bath which was adjusted to pH 2 with sulfuric acid and which contained 0.3%, based on the weight of the goods, of optical brightener for 30 minutes at 60 ° C treated. The goods were rinsed and dried in the usual way.

The following brighteners were used;

a J compound of formula I b) compound of formula XXV

O ₂ -CH ₂ -CH ₂ -N

The whiteness measurement resulted in the following value ■ Raw fabric 83ι0 %

tissue lightened with compound I 105.5 % tissue lightened with compound XXV 99 »2 %

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CH, CH,

The lightened fabrics showed the following hypochlorite fastness according to DIN 54 034 on:

Tissue lightened with Compound I: 5 tissue lightened with compound XXV: 4

The lightening of polyamide 6 fabric carried out in the same way gave the following degrees of whiteness:

Raw fabric 86.0 %

Tissue lightened with Compound I 104.5 %

"Tissue lightened with compound XXV 99.2 %

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Claims (2)

P 5140 Pat r- η t. a η s ρ r ü c Ii e 1) Process for the production of almost colorless or 1- £ 4 '- (β-acylaaino-ethyl3ulfonyl) -p} ienyl] -3-aryl-Ag-pyrasoline compounds pale yellow of the general formula ·. H ₂ OOE in which R is an optionally substituted aryl group, in particular a phenyl group and preferably a p-chlorophenyl group, Y is a -CO- or -SOg group, E ^ is hydrogen, an alkyl group of up to 20 carbon atoms, an optionally substituted phenyl group, an aralkyl group and Rg denotes a lower AljQrlgruppe, a cycloalkyl group, an optionally substituted aryl radical and the ■ styryl group, characterized in that 1- (4'-vinylaulfonyl-phenyl) ~ 3-aryX-A g-pyrazoline with carboxylic acid with carboxylic acid and sulfonic acid aides which carry at least one hydrogen atom on Amidst iciest off, intimately mixed and in the presence of catalytic amounts of alkali, preferably in the presence of Batriuicaiethylat, briefly heated to temperatures of 100-20O ⁰ C, preferably 115 - HO ⁰ C or that one 1-C4 '- ■ (3-Amino-ethy-sulfonyl) -phenyl-j-3-aryl-A g-pyrazoline Compound, the ara Aminstiekatoff at least one hydrogen atom wear, with carbonic and sulfonic acid chlorides in 209811/1662 _ _Λ iAri.7ilAbs.2Ur.1SaU3 * »AndwunBii« .v.4 t Pw 5HO- The presence of acid-binding agents, at temperatures of 0 - ICO ⁰ C, preferably 0 - 45 ⁰ C, or that one on compounds of the general formula A), in which R-a Hydrogen at cai and Y mean a -SOg group,. Alkylating agents, or that one substituted W-chloro-propiophenoneG with phenylhydrazines, which carry the -SO ₂ CH ₂ CH ₂ -Ii-YR ₀ radical in the p-position, where the radicals Y, R ₁ and R ₂ , which have the meaning given above, condensed to the compounds of the general formula A). ·. . · · 2) Use of almost colorless or pale yellow, fluorescent A ₂ pyrazolines of the general Porsiel H ₉ C-GS. ² I Ij ':' ^R 1 in which R is an optionally substituted aryl radical, especially a phenyl and. vorau ^ sv.'eise a p-chlorine— phenyl radical, Y a -CO- or -SOg group, R- hydrogen, an alkyl group up to 20 carbon atoms, one optionally substituted phenyl radical, an AralJcylreat and Rp is a lower alkyl group, a cycloalkyl group, denote an optionally substituted aryl group and the styryl group as optical brightening agents. 209811/1662