DE1419329B1 - 1,3-diaryl-delta-pyrazoline compounds and their use as whitening agents - Google Patents

Description

From the Swiss patent specification 288,169 it is known that man u for the fluorescent whitening of fiber materials, films, or the like. Successfully fluorescent 1,3-diaryl- and 1,3,5-triaryl l may use ² -pyrazolinverbindungen. This 1 ² -Pyrazolinverbindungen preferably have sulfonic acid groups in addition to the diverse other substituents. However, these compounds fluoresce in the long-wave blue to green spectral range and therefore result in a strong green-tinged brightening.

The invention relates to 1,3-diaryl ² -pyrazoline compounds of the general formula I

H ₂ C
H ₇ C

C- <

SO ₂ -X

in which R is a hydrogen or chlorine atom and X is the vinyl radical or a group of the general formula

- CH ₂ - CH ₂ - SO ₃ Me *

means, where Me ' ^{5 represents} a cation, and their use as a lightening agent.

These compounds are characterized by an excellent fluorescence capacity in the short-wave blue Area and are therefore ideal as optical brightening agents. When lightening Fiber materials, especially made of polyamide, wool and acetylated cellulose, give them a neutral white to slightly purple-tinged lightening.

The pyrazolines of the general formula I can be prepared in many ways, for example by reacting / i-Halogenäthylphenylketonen with hydrazinophenyl - ^ - hydroxyethyl sulfone or hydrazinophenyl - ^ - sulfoethyl sulfone. With the hydrazinophenyl-ff-hydroxyethyl sulfones obtained Pyrazolines

(Formula I: X = - CH ₂ - CH ₂ - OH)

are converted into their sulfuric acid esters by esterification with concentrated sulfuric acid and these isolated in the form of their alkali salts. The neutral sulfuric acid ester salts thus obtained

(Formula I: X = - CH ₂ - CH ₂ - OSO ₃ Me *)

become alkaline in aqueous solution upon exposure to it acting agent in the very reactive vinylsulfonyl compounds

(Formula I: X = -CH = CH ₂ )

transformed.

If you take the action of alkaline agents on the sulfuric acid esters mentioned in the presence of salts of sulphurous acid, e.g. B. sodium sulfite, and optionally at elevated temperature before, the salts of the // - suifoethylsulfonyl compounds are also obtained in this way

(Formula I: X = -CH ₂ -CH ₂ -SO ₃ Me ¹ ).

Suitable / ί-haloethylphenyl ketones are: , / - chloroethylphenyl ketone and / i-chloroethyl-p-chlorophenyl ketone.

The compounds with a / j-sulfoäthylgriinpe

(Formula I: X = - CH ₂ - CH ₂ - SO ₃ Me)

are characterized by their permanent water solubility, ie they are water-soluble in the acidic as well as in the neutral and alkaline range. You ίο can therefore be used both in acidic baths, e.g. B. bleach or dye baths, as well as in alkaline, z. B. in washing liquors, easy to use.
The compounds with a vinyl group

(Formula I: X = - CH = CH,)

are characterized by their reactivity towards substrates with reactive hydrogen atoms, for example Cellulose or polyamide. This is how you achieve with them even with delicate washing conditions (40 C) a high degree of whiteness.

The pyrazoline compounds can be used as lightening agents in the customary manner. If the whitening agents are soluble in water, they are expediently used in the form of an aqueous solution and if they are insoluble in water, they can ^; In the form of aqueous dispersions, if appropriate with the aid of dispersants, can be used. The quantities required for the lightening tests, which can vary within wide limits, can easily be determined by preliminary tests.

It is particularly advantageous that the pyrazoline compounds according to the invention can be used in a wide variety of bleaching baths can be used, so that an additional operation is omitted. Also in combination With the usual detergents, the whitening agents according to the invention are excellent White effects achieved. The compounds can continue to improve the beauty of white and colored soaps can be used.

Another area of application for these bodies is use in dye baths. It results here lively, bright colors that are particularly desirable for pastel shades.

It is also easily possible to use the compounds mentioned in a wide variety of finishing processes, such as finishing and softening. It should be emphasized that some of these pyrazolines are even used in high refinement can be used with some condensable resins without losing their lightening effect. The new compounds are the whitening agents known from Swiss patent specification 288 169 by their fluorescence intensity and by the favorable position of their fluorescence maximum /, " in the neutral white to slightly violet-tinged area from about 430 to about 445 m; x consider how from the following comparison results:

H, C

No. R ¹ Cl R- ' P-NO ₂ C. Vi nVi In the.') 1 H Cl P-NH ₂ 189 344 - 2 H Cl p-NH - CO CH ₃ 184 400 - - 3 H Cl p-NH - CO - C ₀ H ₅ 242 373 477 26.3 4th H Cl m-NO ₂ 263 313 513 1.3 5 H Cl o-NO, 146 ³ ) - - 6th H H P-NO ₂ 173 ³ ) - - 7th QH ₅ H p-NH, 181 309 - 8th QH ₅ H P-NH-CO-CH ₃ 186 383 - 9 C ₆ H ₅ H p-NH - CO - C _h H ₅ 203 362 472 24.6 10 QH ₅ H m-NO ₂ 257 375 - 11th QH ₅ H m-NH - CO C ₁₁ H ₅ 121 ³ ) - 12th QH ₅ H o-NO,; 225 363 463 15th 13th QH ₅ H o-NH-CO-CH ₃ 172 ³ ) - 14th QH ₅ H o-NH - CO Q ₁ H ₅ 216 363 - 15th C ₆ H ₅ H P-SO ₃ H 188 336 - - 16 H Cl P-SO ₃ H 363 468 69.3 17th H Cl P-SO ₂ - CH ₂ - CH ₂ - SO ₃ Na ⁴ ) - 375 480 57.8 18th H Cl P-SO ₂ - CH ₂ - CH ₂ - SO ₃ Ca 2 368 442 54.0 19th H Cl P-SO ₂ - CH ₂ - CH ₂ - SO ₃ Al .V) 369 439 75.7 20th H Cl P-SO ₂ - CH = CH ₂ 368 438 86.7 21 H ¹ I in dimethylformamide solution.
^:) Fluorescence intensity against L ran \ lglass standard = HK)
■ ') Not determined.
⁴ I 35 ”attitude.
- " ¹ I In Dimeuiylformamid Was» er (3: 2i. 192 372 441 82.0

The following examples are intended to demonstrate the wide range of possible applications demonstrate.

example 1

A fabric made of polycaprolactam is treated for 20 minutes at 60 C with a solution containing 1 "" formic acid (85 ° ₍₎ ig) and 0.4 "" of the compound of the following constitution (II)

H, C

H, C

I:
N

, · - ei

(II)

SO ₂ CH ₂ CH ₂ SO ₃ Na =

60

contains. The fabric shows an excellent degree of whiteness that can be achieved without the use of an optical Brightener cannot be achieved.

The white measurements were made with a Zeiss-Elrepho device carried out and compared against magnesium oxide as a standard at one wavelength of 460 ma, a value of 81 ",, (unbrightened Goods: 71%).

The above compound II can be produced in the following way:

43.2 parts by weight of 4-hydrazinophenyl -, - oxyeth \ lsulfon and 40.8 parts by weight of - chloroethyl-p-chlorophenyl ketone are added in 400 parts by volume of methanol to which 40 parts by volume of pyridine have been added. Boiled under reflux for 1 hour. The reaction mixture is then cooled to 0 to 5 ° C., held at this temperature for 2 hours and the 1- (4 '-, - oxyethylsulfonylphenyl) -3- (4 "-chlorophenyl) -l ² -pyrazoline with a melting point of 222 ° C. is suctioned off away.

^{For esterification, 25 parts by weight of the aforementioned dry I 2} -pyrazoline in 150 parts by weight of concentrated sulfuric acid are introduced at room temperature and the mixture is stirred for a further 15 hours. The solution is poured onto 750 parts by volume of ice water and stirred in the cold for 1 hour; the precipitated acidic acid ester is filtered off with suction and ground for several hours in a ball mill with a saturated methanolic potassium acetate solution. The potassium salt of the sulfuric acid ester is filtered off with suction, washed free of sulfate ions with ice water and dried at 60 ° C. in a vacuum.

To prepare compound II, 24.2 parts by weight of the potassium salt of the sulfuric acid ester are boiled in 350 parts by volume of water with 25.2 parts by weight of crystallized sodium sulfite for 2 ¹ ₂ hours under reflux cooling until a sample taken ⁽ due to the addition of dilute sodium hydroxide solution) no longer shows any precipitation low

Claims (1)

impurities sucked off; 37.5 parts by weight of sodium chloride are added to the clear solution, and compound II is isolated after the solution has cooled. It is washed free of sulfate ions with 10 ° sodium chloride solution and dried at 60 ° C. in a vacuum. Example 2 In a liquid mild detergent with the following composition: 10% alkylarylsulfonal, 4% oleylmethyltauride sodium salt, 6% p-toluenesulfonate, 12% potassium pyrophosphate, 67.7% water are 0.3 ° 0 of the optical brightener of the following constitution (III) % Liquor uptake squeezed off and dried. In addition to the desired finish effect, the fabric has a beautiful white. Example 5 To achieve a soft, supple handle, a polycaprolactam knitted fabric is treated with a solution containing 2% of a mixture of fatty acid sarcosides for 20 minutes at 60 ° C. on the reel skid, with the bath 0.4%, based on the weight of the goods, an aqueous dispersion of the following compound IV H1C H, C 20 (IV) (HD SO2CH2CH2SO3Na- incorporated. After a single treatment for 15 minutes at 50 ° C. and a flow ratio of 1:30 with the use of 5 g of 1 of the aforementioned detergent, knitted polycaprolactam fabrics show a Brilliant brightening. Even after repeated washing there were no signs of accumulation. The compound III can be prepared using the methylphenyl ketone as described in Example 1. B eis ρ ie I 3 A wool flannel is for 3 hours at 45 C with a 400O hydrogen peroxide (35%). 4 ° I, sodium pyrophosphate and 2 "" solution containing ammonia (25%) bleached Acidification with 2% acetic acid (HH) "" ig) for 15 minutes in the cold takes place in a reductive bleaching with a solution which contains 4% sodium dithionite and 0.4% of the compound II per liter. The bleaching time is 1.5 hours at 50 ° C. It is then acidified again. The wool fabric treated in this way shows a brilliant white. The result is an increase in whiteness from 69 "" (unbleached goods) to 78%. For 1 4 6s Bleached polycaprolactam juice is finished with a 20 "polyvinyl acetate dispersion. the 0.1 "" of the compound III "contains. SO2 - CH = CH, can be added. The result is an increase in whiteness from 71.3 ″ (raw knitted fabric) to 80.9 ″ and a pleasant, supple handle. To prepare the vinylsulfonyl compound IV, 9.7 parts by weight of the potassium salt of the sulfuric acid ester mentioned in Example 1 are dissolved in 200 parts by volume of water at 80 ° C., the solution is allowed to cool to 20 ° C. and then made alkaline with about 25 parts by volume of 2N sodium hydroxide solution against triazene paper. The mixture is subsequently stirred at 20 ° C. for 1 hour, the product which has precipitated is filtered off with suction, washed neutral with water and dried at 60 ° C. in vacuo. The vinylsulfonyl compound IV has a melting point of 192 C. after a single dissolution from butanol. 4S claims: 1. 1,3-Diaryl- I ² -pyrazolines of the general formula I H, C - R SO ₂ X in which R is a hydrogen or chlorine atom and X is the vinyl radical or a group of the general formula -CH ₂ -CH ₂ -SO ₃ Me- means. where Mc ^{1 represents} a cation. 7 8 2. Use of 1,3-diaryl l ² -pyrazolines in which R is a hydrogen or chlorine atom and X is the general formula I denotes the vinyl radical or a group of the general H ₂ C COR ^FOrmCl _HiC ν 5 CH ₂ -CH ₂ -SO ₃ Me- • N (D 1 means, where Me represents a cation, as ! , Lightening agents. 1, ¹ I ίο so, x 9O9 583'18f