DE1670722B2 - 1- [4 '- (ß-AcylaminoäthylsulfonyO-phenyl] -3-aryl-A2 -pyrazoline, process for their preparation and use as optical brightening agent - Google Patents

Description

SO, —CH, -CH, -Ν — Η

in which R a hydrogen or chlorine atom, Y a -CO- or -SO ₂ -GrUpPe, Ri a hydrogen atom, an alkyl group with up to 18 carbon atoms, a phenyl group optionally substituted by a methyl, methoxy, ethoxy group or a chlorine atom or denotes the benzyl group, and R ₂ denotes a lower alkyl group, a phenyl group optionally substituted by a chlorine atom, a methyl, methoxy, ethoxy or phenyl group, a cyclohexyl group optionally substituted by a methyl group or a styryl group.

2. Process for the preparation of the compounds according to claim 1, characterized in that one Compounds of the formula

in which R and Ri have the meanings mentioned, with compounds of the formula

Cl-YR ₂

in which Y and R _{2 have} the meanings mentioned, in the presence of acid-binding agents at temperatures from 0 to 100 ⁰ C, or that one on compounds of the formula

SO, —CH, -CH, -N — SO, —R,

SO ₂ -CH = CH ₂

in which R and R _{2 have} the meanings mentioned, allowing alkylating agents to act, or compounds of the formula

Cl-CH ₂ -CH ₂ -CO

in which R has the meaning mentioned, with compounds of the formula

HNYR ₂

in which Y, Ri and R _{2 have} the meanings mentioned intimately mixed and in the presence of catalytic amounts of alkali briefly at temperatures

in which R has the meaning mentioned, with compounds of the formula

R.
H, N-NH- / ~ A- SO ₂ -CH ₂ -CH ₂ -NYR,

in which Y, Ri and R _{2 have} the meanings mentioned, condensed.

3. Use of the compounds according to claim 1 as optical brightening agents.

The Belgian patent 6 29 875 _{discloses 1,3-diphenyl-4 2} -pyrazoline-2 compounds in which the phenyl radical in the 1-position bears a substituted sulfone group in the para position. Among other things, this sulfonic group can be substituted by a j3-dimethylamino-ethyl group.

The invention relates to compounds of the formula (A)

IA)

CH = CH,

have, intimately mixed and in the presence of catalytic amounts of alkali, preferably sodium methylate, a short time to temperatures of 100-200 ° C, preferably 115- 14O ⁰ C, heated, or in that
b) compounds of formula (D)

(D)

R ₁

SO ₂ -CH ₂ -CH ₂ -NYR ₂

in which R is a hydrogen or chlorine atom, Y is a --CO or - SO ₂ group, Ri is a hydrogen atom, an alkyl group with up to 18 carbon atoms, an "optionally by a methyl, methoxy, ethoxy group or a chlorine atom-substituted phenyl group or the benzyl group, and R ₂ a lower alkyl group, a phenyl group optionally substituted by a chlorine atom, a methyl, methoxy, ethoxy or phenyl group, a cyclohexyl group optionally substituted by a methyl group or the sty ryl group.

The invention furthermore relates to processes for the preparation of the compounds of the formula (A) which are characterized in that one

a) compounds of formula (B) jo

(B)

40

SO, —CH, -CH, -Ν — Η

in which R and Ri have the meanings mentioned have, with compounds of formula (E)

Cl-Y-R,

(E)

in which Y and R _{2 have} the meanings mentioned, in the presence of acid-binding agents, e.g. B. pyridine bases, at temperatures from 0 to IDO ⁰ C, preferably at 0 to 45 ° C, is reacted, or that c) on compounds of the formula (F)

(F)

in which R has the meaning mentioned, with compounds of the formula (C)

SO ₂ -CH ₂ -CH ₂ -N-SO ₂ -R ₂

in which R and R _{2 have} the meanings mentioned, allows alkylating agents to act, or that one
d) compounds of formula (G)

R ₁

HNYR ₂

(C)

50

in which Y, Ri and R _{2 have} the meanings mentioned in which R has the meanings mentioned, with compounds of the formula (H)

H ₂ N-NH

R ₁
SO ₂ -CH ₂ -CH ₂ -NYR,

(H)

in which Y, R ₁ and R _{2 have} the meanings mentioned, condensed.

The vinyl sulfonamides of the formula (B) can for example by the process of FR-PS 13 54 629 be won.

The carboxamides and sulfonamides of the formula (C) contain at least one hydrogen atom on the amide nitrogen wear, be z. B. named:

Acetamide, propionic acid amide,
n-butyric acid amide, isobutyric acid amide,
n-valeric acid amide, iso-valeric acid amide,
Approx. Pronic acid amide, diethyl acetic acid amide,
Hexahydro-benzamide,
4-methylhexahydrobenzamide, benzamide,
4-methyl-benzamide, 4-chloro-benzamide,
4-methoxy- and 4-ethoxy-benzamide,

Cinnamic acid amide, N-methylacetamide,

N-ethyl-acetamide,

N-n-propyl- and N-iso-propyl-acetamide,

N-n-Butylitcetamid, N-iso-Butyl-Acetamid,

N-dodecyl-acetamide, N-stearyl-acotamide,

N-methyl-hexahydro-benzamide,

N-methylbenzamide, N-methyl-cinnamic acid amide,

Acetanilide, 2-, 3- and 4-acetamidotoluene,

4-acetamido-anisole, 4-acetaminophenetol,

4-acetamino-chlorobenzene, N-benzyl-acetamide,

n-butyric anilide, hexahydro-benzanilide,

Benzanilide, cinnamic acid anilide,

Methanesulfonic acid amide, ethanesulfonic acid amide,

Benzenesulfonic acid amide,

Benzenesulfonic acid methylamide,

Benzenesulfonic acid ethylamide,

Toluene-4-sulfonic acid amide,

Toluene-4-sulfonic acid methylamide,

Toluene-4-sulfonic acid butylamide,

Toluene-4-sulfonic acid stearylamide,

Toluene-4-suJfonsäureanilid,

Toluene-4-sulfonic acid benzylamide.

Process b) starts with 1- [4 '- (0-amino-ethylsulfonyl) -phenyl] -3-aryl-42-pyrazolines of formula (D), which can be prepared, for example, by the process of Belgian patent 6 61 139.

Examples of carboxylic acid and sulfonic acid chlorides of the formula (E) are:

n-butyric acid chloride, iso-butyric acid chloride,

n-valeric acid chloride,

Hexahydrobenzoyl chloride,

4-methyl-hexahydrobenzoyl chloride,

Benzoyl chloride ^ -Methylbenzoyl chloride,

4-chloro-benzoyl chloride,

4-methoxy- and 4-ethoxy-benzoyl chloride,

Diphenyl-4-carboxylic acid chloride,

Cinnamic acid chloride, methanesulfonic acid chloride,

Ethanesulfonic acid chloride,

Benzenesulfonic acid chloride,

Toluene-4-sulfonic acid chloride.

The compounds of the present invention can also be obtained by the action of alkylating agents such as B. dimethyl or diethyl sulfate, to those compounds of the general formula (A) in which Ri is a hydrogen atom and Y is a - SO2 group mean.

The 42-pyrazoline compounds obtained by the process of the present invention of the general Formula (A) are almost colorless or pale yellow colored products that act as UV absorbers for reproduction materials, e.g. B. papers are extremely suitable. Furthermore, they can be excellent Use as an optical brightener.

The new compounds are characterized by excellent fluorescence properties and good lightfastness when lightening fiber materials made of cotton, polyacrylonitrile and their 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 very good fastness to hypochlorite and exhaust gas the end. The resistance to exhaust gases is particularly important in the case of lightening agents for cellulose and triacetate fibers are a very valuable property.

The lightening agents according to the invention can be used in a manner known per se, either in the form of solutions in organic solvents,

ι or in the form of aqueous dispersions, optionally with the aid of dispersants. The required quantities, which can fluctuate within wide limits, can be determined through preliminary tests.
The new connections can be commercially available

in detergents, even if they contain oxidative bleaching agents, such as B. contain perborate, are added to beautify the laundry. Furthermore, the new Vebrindungen also together with reductive chemical bleaching agents, e.g. B. sodium dithionite, sodium boron - "> hydride etc. are used.

The new substances can be treated with suitable textile finishing agents such as antistatic agents, plasticizers, Water repellants etc. can be used in combination, which results in very good results in one operation

2Ii lightening and finishing effects achieved. Another area of application for these bodies is the use of dye baths. The result is lively, bright colors that are particularly desirable for pastel shades. You can also use spinning and casting compounds,

2Ί for example from polymerization products of vinyl chloride, Vinylidene chloride, polyethylene, polypropylene, among others, are added to the production artificial fibers, threads, films, foils, tapes and other shaped bodies are used.

example 1

41.6 parts by weight of the 1- (4'-vinylsulfonyl-phenyl) -3- (p-chlorophenyl) - ^ 2-pyrazoline are with 12 weight

r, share acetamide and 2 parts by weight of sodium methylate intimately mixed and heated for 10 minutes 135-140 ⁰ C. The melt that has formed soon solidifies. After cooling, the crystals are crushed, boiled with 200 parts by volume of methanol, the undissolved

4 (i separated and with 200 parts by volume of cold methanol rewashed. The compound VI (see table) shows after repeated recrystallization from glacial acetic acid Melting point of 211 - 212 ° C.

Example 2

9.36 parts by weight of the 1- (4'-vinylsulfonyl-phenyl) -3-phenyl- / d2-pyrazoline are with 2.95 parts by weight of acetamide and 0.5 parts by weight of sodium methylate

■■) (i intimately mixed and heated for 10 minutes 115-120 ⁰ C. The melt formed solidifies upon cooling. The crystals are crushed and extracted with 40 volumes of cold methanol. The compound of formula I (s obtained. Table) after multiple recrystallization from methanol has a melting point of 147-148 ⁰ C.

Example 3

Bo 13.6 parts by weight of 1- [4 '- (j3-benzylamino-ethylsulfonyl) -phenyl] -3- (p-chlorophenyl) -Zl2-pyrazoline are suspended in 40 parts by volume of pyridine. At 0-5 ⁰ C is allowed to 6 parts by weight of 4-methoxy-benzoylchIorid zuiropfen and then stirred for l '/ 2 hours at

tv> room temperature after. The reaction mixture is with About 100 parts by volume of methanol are added, the mixture is cooled in an ice bath, and the acylation product which has precipitated is added suctioned off and washed with methanol. The resulting-

ne compound XV (see table) shows, after repeated recrystallization from benzene, a melting point of 122-124 ° C.

B e i s ρ i e I 4>

12.57 parts by weight of 1- [4 '- (j3-Benzylamino-ethylsulfonyl) -phenyl] -3-phenyl-z12-pyrazoline are added to 40 parts by volume of pyridine and at 0-10 ° C with stirring with 5.0 parts by weight of methanesulfochloin rid dropwise added. Then it is warmed to 40-45 ° C and held at this temperature for one hour. cools down again to room temperature, sucks the precipitate and washes with methanol. That Sulfonamide V (see table) melts after repeated π recrystallization from chlorobenzene at 175-176 ° C.

Example 5

10.4 parts by weight of 1- (4'-vinyisulfonylphenyl) -3- 2i> (p-chlorophenyl) -Zl2-pyrazoline are intimately mixed with 9 parts by weight of toluene-4-sulfonamide and 1 part by weight of sodium methylate and heated to 160- 18O ⁰ C heated. After cooling, the melt formed is rubbed with 60 parts by volume of methanol, with crystallization occurring. It is filtered off with suction and washed with methanol. The compound XIX obtained (see table) has a melting point of 200-202 ° C. after repeated recrystallization from chlorobenzene.

Example 6

13.6 parts by weight of 1- [4 '- (j9-Benzylamino-ethylsulfonyl) -phenyl] -3- (p-chlorophenyl) -42-pyrazoline are dissolved in 40 parts by volume of pyridine and kept at 0-5 ° C 7.5 parts by weight of acetyl chloride are added dropwise to stirring. The mixture is then stirred for about 1 hour 40-45 ° C., the mixture is poured onto ice and the acetylation product formed sucks after it has solidified and wash off copiously with water. The resulting compound IX (see table) melts again repeated dissolving from methanol at 159-160 ° C.

Tabel

CH, C-R

I "Il

CH, N

// R ₁

SO ₂ -CH ₂ CH ₂ -NYR,

R ₁

M.p.
(in ° Celsius) 148 147 132 130 179 178 201 199 176 175 212 211 177 175 161
160 160
159

- CO— —H

-CH ₂ C ₁ H ₅

- CO -

IV J
' X - \ -Cl - SO ₂ V _J 3 -Cl - SO ₂ Vl "Xs "X - Cl - co VII ~ \ > C! - co VIII ../ X, - co IX co

OCH.,

Y-

OCH., -CH,

-CH,

-CH,

-CH,

-CH,

-CH,

CH,

CH,

CH ₂ C ₁₁ H,

continuation

Cl —CO— —H

Cl —CO— —Η

Cl —CO— -CH,

XlII Y. > CI - co XIV _ / ~ > ■ Cl - co XV Y CI - co XVI > CI - co XVII > Y> Cl - co XVIII > Y Cl -SO ₂ XIX Y> -f Cl -SO ₂ XX Y > Cl -SO ₂ XXI Cl -SO ₂ XXiI Y Cl -SO ₂ XXIIl _J ~ Cl -SO ₂

LJ

"CH ₃

-CH ₂ C ₆ H ₅

-CH ₃

-CH ₃

-CH ₂ C ₆ H ₅

-CH ₃ -C ₄ H ₉ (n) -C ₁₈ H ₃₇ (Ii)

CI -SO ₂ - - H

example

10

CH ₂ CH ₂ CH ₃ CH, CH,

Y "Y

-CH CH,

Y Y

CH ₂ CH,

CH, CH,

CH CH,

Y Y '

CH ₂ CH ₂

OCH ₃

OCH ₃

- CH = CH

CH ₃

CH ₃

CH ₃

CH ₁

-CH ₃

M.p.

(in ° Celsius)

205 207

272-274

166-167

270-272 108-109 122-124 166-168 198-200 210-211 200-202 181-183 161-162 126-127 183-185 186-187

A conventionally pre-bleached fabric from Whiteness measurement, carried out with the Zeiss-El-Cellulose two-and-a-half acetate, results in a liquor ratio repho device at a wavelength of 460 μm

an increase of 20% over the _non-r brightened tissue.

^bJ To prepare the aqueous dispersion, 0.15 g of compound VI was added to 7.5 ml of dimethylformamide

Cellulose two and a half ace

1:20 with an aqueous dispersion per liter

0.15 g of compound VI (table) and 1 ml of formic acid (85%) contains

dissolved and this solution in 1 l of hot water that ^{treated 0.38 g at a temperature of 80 0} C for 30 minutes. of the oxethylation product from nonylphenol and 23

Moles of ethylene oxide contained, poured.

A cellulose triacetate fabric bleached in the same way shows an improvement in the degree of whiteness at 15%.

Example 8

A woolen fabric bleached in the usual way is treated in a liquor ^{ratio of 1:20 at 60 °} C. for 45 id minutes with an aqueous dispersion containing a liter

0.3 g of compound I (table),

1.2 g sodium dithionite and r,

0.8 g sodium pyrophosphate

contains.

This treatment resulted in an 11% increase in whiteness.

The aqueous dispersion was prepared in the manner indicated in Example 7.

20th

Example 9

A bleached fabric made of wool is in long FIoUs (1:20) 45 minutes at 60 ° C with an aqueous Dispersion treats that per liter

0.2 g of compound XV (table), 1.2 g of sodium dithionite and 0.8 g of sodium pyrophosphate

contains. This treatment results in an increase in the degree of whiteness of 10% compared to the non-lightened fabric.

The aqueous dispersion was prepared in the manner indicated in Example 7.

JO 0.15 g of compound XlX (table) and 1 g of sodium carbonate

contains Compared to the non-lightened fabric, the result is an increase in whiteness of 10%.

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

10% brightening is also achieved when using the same amount of compound VI and using it of 1 ml of formic acid instead of the 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 that 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) compound of formula I (table)

b) Compound XXV of the formula (BE-PS 6 29 875)

40

Example 10

A fabric consisting of at least 85% polyacrylonitrile is used in a liquor ratio of 1:20 for 30 minutes treated at 98 ° C with an aqueous dispersion that in liter

0.2 g of compound I (table), r _{) 0}

1 ml of formic acid (85%) and 1 g of alkylaryl polyglycol ether

contained. The improvement in the whiteness effect compared to the original fabric is 10%.

If, instead of the compound I, the compound V is used in the same amount and works in the same way Way, you also get a lightening of 10%.

The aqueous dispersion was prepared as described in Example 7. bo

Example 11

A bleached in a conventional manner Polycaprolaetamge- _b5 weave is a liquor ratio of 1: 30 minutes treated for 20 seconds with an aqueous dispersion at 60 "C containing per liter

SO, —CH, -CH, -N

CH,

CH ₃

The whiteness measurement resulted in the following values:

Raw fabric 83.0%

Tissue lightened with compound I 105.5% Tissue lightened with compound XXV 99.2%

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

Tissue lightened with compound I: 5

Tissue lightened with compound XXV: 4

The analogous lightening of polyamide 6 fabric resulted in the following degrees of whiteness:

Raw fabric 86.0%

Tissue lightened with compound I 104.5% Tissue lightened with compound XXV 99.2%

Example 13 The following compounds were compared:

SO, -CH, -CH, -X

XXIV
XXV

-NH-CO - CH.,

-NH-SO ₂ -CH.,
-N (CH.,) ;, (BE-PS 6 29 875)

A. Loosen the optical brighteners

Brightener

WciWgrad

in front of me

Authenticity test.

grade

XIV 167.0 163.0 5 XXlV 159.0 154.0 5 XXV 155.2 132.8 4th

C. Optical brightening of polyamide 6

Polyamide-6 raw material was made according to the above Regulation lightened, the following results were obtained:

Brightener at Whiteness 73.3 VI 159.5 XIl 157.3 XIV 159.8 XXlV 140.9 XXV 110.7 game 14

With equimolar amounts of the compounds XXlI j "(table) and XXVI

100 mg each of the optical brighteners mentioned Clearly dissolved in 5 ml of dimethylformamide by heating and, after adding 5 ml of an emulsifier (based on of a nonylphenol polyglycol ether with an average of 23 moles of ethylene oxide, 87%) in 100 ml of distilled Water dispersed.

B. Optical brightening of cellulose-2 ^1/2-acetate

A bleached gray fabric of cellulose 2 ^1/2 acetate was at a liquor ratio 1: 0.3%, based on weight, of the optical brighteners referred to below contained in a Aufhellungsbad, which was adjusted with sulfuric acid to pH 2 and 20, Treated for 30 minutes at boiling temperature. The goods were then rinsed and dried in the usual way.

The whiteness of the tissue samples was measured using the ELREPHO reflectance photometer from Zeiss (Standard illuminant C, FM filter) and from the values obtained in this way, the degree of whiteness according to the formula of B e r g e r (The color 8 [1959] 187-202)

W = Y + 3 (Z - X)

calculated.

The hypochlorite fastness of the brightening was carried out in accordance with DIN 54 034 and on those treated in this way The whiteness of the samples was then determined again. The results are shown in the following table:

-C = N

H, C -CH,

> —SO, —NH,

(XXVl)

a soft polyvinyl chloride preparation of the 4 (i following composition was added and on a Laboratory test mill processed into plates:

75 grams of emulsion polyvinyl chloride

25 grams of dioctyl phthalate

4-, 2 g titanium dioxide (rutile)

1.5 g commercially available barium-cadmium

stabilizer

0.2 g polyethylene wax

0.2mmol brightener

The whiteness of the samples obtained in this way was measured with the ZEISS-ELREPHO device and after Formula calculated by B e r g e r. The following table shows the degrees of whiteness obtained:

Brightener

Whiteness

Lightening cell

Brightener

Whiteness

before after

Iichthcilsprül'ung

Nolc XXII
XXVI

89.4%
118.9%
117.5%

29.5% 28.1%

- 77.5 - 5 Vl 174.6 168.0 5 XII 165.9 160.0

With the compound XXII a lightening effect is thus improved by 1.4 absolute% or 5 relative% achieved. In addition, the pattern lightened with Compound XXII shows a more "neutral" white.

Claims (1)

1. Compounds of the formula Patent claims: heated from 100-200 ⁰ C, or that one compound R ₁ SO ₂ -CH ₂ -CH ₂ -NYR ₂ gene of the formula