DE2241015A1 - ALPHA-CYANOMETHANESULPHONEAMIDOBENZENE DERIVATIVES - Google Patents

Description

Patent registration
D 4533

cc-cyanomethanesulfonamidobenzene derivatives "

The invention relates to chemical compounds of the formula;

NH - SO ₂ - GH ₂ - CN

in which Y is hydrogen ₄ chlorine, bromine or an alkoxy group with 1-4 C atoms and Z is an NH _? - or. Mean OH group.

Examples of compounds of the type described are:

2-Amino-3- (a-cyano-methanesulfonamido) -l-nitro-benzoil, 2-amino-4- (α-cyano-methanesulfonamido) -l-nitro-benzene, l-amino-4- (a-cyano-methanesulfonamido) -2- nitro-benzene, 2-AmInO - ^ - ChIOr-l- (a-cyanmethanesulfonamido) -3-nitro-benzene _} l-amino-5- (a-cyanmethanesulfonamido) -4-methoxy-2-nitro-benzene, 2- Amino-3-chloro-4- (a-cyanomethanesulfonamido) -l-nitro-benzene, 1-amino-3 ~ (a-cyanmethanesulfonamido) -2-nitro-benzene, l-amino-2- (a-cyanomethanesulfonamido) - 4-nitro-benzene, 2-amino-l- (a-cyano-methanesulfonamido) -4-nitro-benzene, l-amino-5-bromo-2- (a-cyano-methanesulfonamido) -4-nitro-benzene, l-amino 2- (a-cyano-methanesulfonamido) -3-nitro-benzene, l-amino-3- (o-cyano-methanesulfonamido) -5-nitro-benzene,

409809 / 123A

Henkel & Cie GmbH u »· 2« "Potentonm« w _U n »d 4533

l-amino-2-chloro-3- (a-cyanmethanesulfonamido) -5-nitro-benzene, l-amino-2-butoxy - ^ - ( _a -cyanmethanesulfonamido) -5-nitro-ben2ol,

¹ I-Amino-2 - (<j-cyanmethanesulfonamido) -l-nitro-benzene,

^ -Amino-l-ethoxy-lJ-Ca-cyanmethanesul fonamido) -5 ~ nitro-benzene,

2- (α-Cyanmethanesulfonamido) - ^ - nitro-phenol, 2- ((χ-Cyanmethanesulfonamido) -6-nitro-phenol, ¹ l-chloro-2- ( _e -cyanmethanesulfonamido) -6-nitro-phenol _t 2 - (Q ^- -Cy anmet nansulfonamido) -3-methoxy- 6-nitro-phenol, 6-chloro-2- ( _a -cyanmethanesulfonamido) -4-nitro-phenol, 2- ( _a -cyanmethanesulfonamido) -5- nitro-phenol, 4-bromo-5- (a-cyano methanesulfonamido) -2-nitro-phenol, ¹ 4- ( _a- cyano-methanesulfonamido) -2-nitro-phenol, 3- (a-cyano-methanesulfonamido) -2-nitro-phenol , 2- (o-Cyanmethanesulfonamido) -5-nitro-phenol, 2- ( _a -cyanmethanesulfonamido) -3-methoxy-5-nitro-phenol, 5-chloro-2- (a-cyanmethanesulfonamido) - ii-nitro- phenol, 2- ( _a -cyanomethanesulfonamido) -3 ~ nitro-phenol, 5-butoxy-2- (o-cyanmethanesulfonamido) -3-nitro-pnenol, 3- (α-cyanmethanesulfonamido) -5-nitro-phenol, 2- BrOm- ¹ I- (a-cyano methanesulfonamido-3-nitro-phenol, 2-ethoxy-5 ~ (a-cy methanesulfonamido) -it-nit ro-phenol.

The compounds according to the invention can be prepared by reacting the corresponding optionally substituted ones Nitro-aminophenols or diamino-nitrobenzenes with the for Monosubstitution of an amino group stoichiometrically required Amount of chlorosulfonylacetonitrile. The implementation takes place advantageously in the presence of a solvent such as hydrocarbons, benzene, chlorobenzene, tetrahydrofuran in such a way that the chlorosulfonylacetonitrile dissolved in the respective solvent increases with ice cooling

409809/123

Henkel & Cie GmbH since. 3 mrPomntanmeidune d! 1533 '

added dropwise to the nitro-aminophenols or diamino-nitrobenzenes will. After the addition has ended, the reaction mixture is stirred for a few hours at room temperature held, then poured into water and separated off the reaction product obtained in the form of an oil or in solid form. Purification of the reaction product can be done by recrystallization from ethanol.

The compounds according to the invention are valuable hair dyes. They can be used as substantive dyes that result in differently nuanced yellow tones. Compared to the starting substances used for their production, which are known as direct pullers, they are characterized by better mounting and fastness properties and also give significantly different color nuances.

The compounds according to the invention can also be used as yellow Couplers are used in oxidation dyes in combination with customary developer substances, the achievable The color tones of the developer components and the intensity of the oxidation vary from different yellow tones to brown can be.

The invention accordingly further relates to the use of compounds of the general formula

NH - SO ₂ - CH ₂ - CN.

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Henkel & Cie GmbH s «i> e l \ mr patent application D

in which Y is hydrogen, chlorine, bromine or an alkoxy group with 1-4 C atoms and Z is an NHp or OH group, in preparations for coloring hair.

A particular embodiment of this subject of the invention relates to the use of compounds of above formula in combination with customary developer substances in preparations for the oxidative coloring of Hair.

In this case, the compounds usually used for this purpose come into consideration as developing substances. Examples of this are primarily primary aromatic amines with a further functional group in the p-position name, e.g. B. p-phenylenediamine, p-tolylenediamine, p-dimethylaminoaniline, p-aminopheriol, p-diaminoanisole or other compounds of the type mentioned, which also have one or more functional groups in the form of OH-, NHp-, NHR-, NRp- (R = lower alkyl or hydroxyalkyl radical with 1-4 carbon atoms). Other suitable developer substances are Diaminopyridine derivatives, heterocyclic hydrazone derivatives and, in particular, 4-amino-pyrazolone derivatives according to Austrian Patent Specification 277,465.

The coupler components according to the invention are expediently used in approximately molar amounts based on the developer substances used used. However, it is generally not disadvantageous if the color coupler component to a certain extent Excess or deficit is present.

Both the color coupler components and the developer substances mixtures of compounds of the above

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Henkel & Cie GmbH page 5 for patent application O llK. ~ 2nd ~ Z.

called kind.

The oxidative coupling, i.e. H. the development of color, can in principle, as with other oxidation dyes, be carried out using atmospheric oxygen. Appropriately however, chemical oxidizing agents are used. Hydrogen peroxide, in particular, is used as the chemical oxidizing agent or its addition products with urea, melamine and sodium borate and mixtures of such hydrogen peroxide addition products with potassium peroxydisulfate.

For the abovementioned uses, the compounds according to the invention can be in the form of aqueous solutions. Such solutions should contain the dyes or the dye combinations of coupler and developer components in amounts of 0.2-5> in particular 2 % by weight.

The compounds according to the invention can also be used in the form of creams or emulsions. To this end you can the dyes or dye mixtures are mixed with the components usually present in such preparations will. Such components include any wetting agents or detergents of the anionic or nonionic type, e.g. Alkyl benzene sulfonates, fatty alcohol sulfates, alkyl sulfonates, fatty acid ethanolamides, Addition products of ethylene oxide with fatty acids and fatty alcohols .. Furthermore, such preparations Thickening agents such as methyl cellulose, starch and higher fatty alcohols, paraffin oil and fatty acids and perfume oils or Hair care products, such as pantothenic acid and cholesterol, contain.

-S-

409809/1234

Henkel & Cie GmbH Since 6 lor patent application D 1 | 53 Λ

The additives are used in the amounts customary for this purpose. In this context, amounts of 0.5-30% in particular come into consideration as wetting agent additives and amounts of 0.1-25 % as thickener additives, each based on the total composition. The concentration of the dyes or dye combinations in such agents, which are present in cream or emulsion forms, is likewise up to 5 %, preferably 0.1-2 %, based on the total composition, depending on the intended use.

The coloration can take place at temperatures between 15 and 40 C im weakly acidic, neutral and preferably alkaline medium.

The dyeings obtained have good lightfastness, washfastness and rubfastness properties and can easily be removed again with reducing agents.

409809/123 /.

& Cie GmbH Page for patent application D

Examples

example 1
l-Amino-2- (q-cyanomethanesulfonamido) -4-nitro-benzene

To a solution of 15.3 g (0.1 mol) of 1.2-diamino- ⁱ l-nitro-benzene in 200 ml of absolute tetrahydrofuran, a solution of I ¹ g (0.1 mol) of chlorosulfonyl acetonitrile in 50 ml of absolute tetrahydrofuran were slowly added dropwise. The mixture is then stirred for a further six hours at room temperature. It is filtered off with suction and the piltrate is poured into water, an oil separating out and being separated off from the aqueous phase. After a while this oil solidifies to a crystal pulp. It is suctioned off and recrystallized three times from ethanol.

M.p. 185 - 187 ° C.

Analysis calculated for CnHoNj.0 ^ .3

Calc .: C 37.50 H 3.12 N 21.88 found: C 37.72 H 2.86 N 22.07

Example 2

^ -Amino-2 - ((x-cyanmethanesulfonamido) - 1-nitro-benzpl

15> 3 g (0.1 mol) 1,3-diamino-4-nitro-benzene, in 100 ml absolute Dissolved tetrahydrofuran, and 14 g (0.1 mol) 'in 50 ml of absolute Tetrahydrofuran dissolved chlorosulfonylacetonitrile, are like

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Hang! & CiC GmbH S.it. 8 for Potent Registration D ^

in Example 1 described implemented. The precipitate is recrystallized twice from ethanol.

Mp. 216-217 ° C.

Analysis calculated for CgHgN ^ S

Calcd .: C 37.50 H 3.12 N 21.88 found: C 37.7 H 2.82 N 22.32

Example 3

l-Amino-4- (a-cyanomethanesulfonamidp) -2-nitro-ben2: pl

15> 3 g (0.1 mol) of 1. A-diamino-2-nitro-benzene, dissolved in 2.O ₁ Qpil of absolute tetrahydrofuran, and I ^ g (0.1 mol) of chlorosulfonyl acetonitrile, in 50 ml dissolved in absolute tetrahydrofuran are reacted as described in Example 1. The reaction product is recrystallized once from ethanol, the precipitate which has been sucked off is washed with a little ether and then recrystallized again from water.

M.p. 157-162 ° C.

Analysis calculated for CgHgN ^ OnS

Calc .: C 37.50 H 3.12 N 21.88 found: C 37.51 H 2.79 N 22.07

Example k

H - chlorine-2- (α-cyanomethanesulfonamido) -6-nitro-phenol

18.8 g (0.1 mol) of 2-amino-4-chloro-6-nitro-phenol, in 100 ml of absolute Slurried tetrahydrofuran, and 1 ^ .0 g (0.1 mol)

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Henkel & Cie GmbH ■ Page 9 for Paiont registration O 4533

Chlorosulfonylacetonitrile, in 50 ml of absolute tetrahydrofuran dissolved, are implemented as described in Example 1. The precipitate is recrystallized twice from ethanol.

M.p. "74 - 177 ° C

Analysis calculated for CqH-TN ₇ O ₁ -SCI

ö 6 3 5

calc .: C 32.93 H 2.19 N 14.41 found : C -33.51 H 2.06 Nl4.53 Example 5
6 "chloro -2- (a -cyanomethanesulfonamido) -4-nitro-phenol

18.8 g (0.1 mol) of 2-amino-6-chloro-4-nitro-phenol, slurried in 100 ml of absolute terahydrofuran, and 14.0 g (0.1 mol) of chlorosulfonylacetonitrile, dissolved in 50 ml of absolute tetrahydrofuran _f are implemented as described in Example 1. The precipitate is recrystallized twice from ethanol.

Mp. 182-184 ° C.

Analysis calculated for CnH ^ N ₇ O ₁ -SCl

ö 6 3 5

calc .: C 32.93 H 2.19 S 10.94 found: C 33.08 H 1.72 S 10.60

Example 6
2- (q-Cyanmethanesulfonamido) -4-nitro-phenol

15.4 g (0.1 mol) of 2-amino-4-nitro-phenol, dissolved in 100 ml of absolute tetrahydrofuran, and 14.0 g (0.1 mol) of chlorosulfonyl

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Henkel & Cie GmbH S * i «· 10 » ι Pat * nlanm «ldun _B D 4533

acetonitrile, dissolved in 50 ml of absolute tetrahydrofuran implemented as described in Example 1. The reaction product is recrystallized twice from ethanol and once from water.

M.p. 166 - 168 ° C.

Analysis calculated for C ₀ H ₁₇ N-JD ₁ -S

calc .: C 37.36 H 2.74 N 16.3 ¹ J found: C 37.11 H 2.62 N 16.43

Example 7

4 - («- Cyanmethanesulfonarnido) - 2-nitro-phenol

15.4 g (0.1 mol) of 4-amino-2-nitro-phenol, in 100 ml of absolute Dissolved tetrahydrofuran, and 14.0 g (0.1 mol) of chlorosulfonylacetonitrile in 50 ml of absolute tetrahydrofuran are dissolved implemented as described in Example 1. The precipitate is recrystallized from ethanol.

M.p. 150-155 ° C.

Analysis calculated for C _O H ₇ N, O _C S

0 7 3 5

Calcd .: C 37.36 H 2.74 · N 16.34 Found: C 37.71 H 2.74 M 16.29

Example 8

in a cream base of the composition

10 parts by weight of fatty alcohols C ₃ ^ -C

10 parts by weight of petalcohol sulfate

(technical mixture

75 parts by weight of water

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Henkel & Cie GmbH

Selto J. J. for patent application D ^ IS 3 "5

were "■ - ■

2 parts by weight of l-amino-2- (a-cyanmethanesulfonaroido) -4-nitro-benzoi

incorporated and the pH of the mixture by adding Ammonia adjusted to 9 »5. This emulsion was made with Water made up to 100 parts by weight. The coloring cream thus obtained was applied to naturally graying human hair and left to act for 30 minutes at room temperature. The hair was then washed and dried. The result was a strong deep yellow coloring of the hair.

Examples 9-14

With otherwise the same procedure as indicated in Example 8, but using those listed in the table below Dye components from Examples 2-7 give the hair colorations indicated in the same line;

Example no.

Dye component

hair coloring obtained

4-Amino-2- (a.-cyano methanesulfonamido) 1-nitro-benzene

l-Amino-4- (a ~ cyanomethanesulfonamido) -2-nitro-benzene

4-chloro-2- (a-cyanomethanesulfonamido) -6-nitro-phenol

6-chloro-2- (α-cyanomethanesulfonamido) -4-nitro-phenol

2- (cc-cyano methanesulfonamido J-JJ-phenol

^ - (α-Cyanmethanesulfonamido) -2-nitrophenol

olive yellow topaz yellow

pompe janish yellow

honey yellow

- olive yellow

ivory

409 ^ 0 W T2 34

Henkel & Cie GmbH SU 12 iur Potenlanmeldunü D ^ 533

Example 15

In a cream base, as described in Example 8, equimolar amounts of ^ -amino-1-phenyl-3-carbamoylpyrazolon-5 as developer component and l-amino-2 (a-cyanmethanesulfonamido) - ^ - nitro-benzene as coupler component emulsified. The molar concentrations are calculated so that in the subsequent oxidative coupling reaction, 100% conversion provided that 2 g of dye in 100 g of cream (corresponding to a 2 # dye concentration) are located. The emulsion is adjusted to a pH of 9.5 by adding ammonia and then it is made up with water to 100 parts by weight. The coloring cream obtained in this way colors by acting the oxygen in the air or a lozenge or nine Hydrogen peroxide solution human hair within 30 Minutes mustard-brown to yellow-brown, depending on the oxidizing agents used (or their different Concentrations) different shades of color can be obtained.

Examples 16-52

With otherwise the same procedure as in Example 15, but using the developers and couplers listed in the table below as dye components a) and b), naturally gray human hair was dyed and the colorations indicated in the last column were obtained (with atmospheric oxygen as well as with aqueous solution and 9% H _? Op solution). The dye components were used in equimolar amounts. The total amount of the dye to be formed was

- 13 -

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Henkel & Cie GmbH ropes 13 for patent application D 4533

in 100 g cream base 2 g each, the duration of action Minutes at room temperature.

The developer components under a) are abbreviated in the table as follows;

^ -Amino-1-phenyl - ^ - carbamoyl-pyrazolone-S = A

4-amino-1-phenyl-3-ethoxycarbonyl-pyrazolone-5 ⁼ B

4-Amino-1H-3-ethoxycarbonyl-pyrazolone-5 = C

p-tolylenediamine. = D

l-methyl-pyridone-2-hydrazone = E

l-methyl-quinolone-4-hydrazone - = F.

4Q9809 / U34

example

No.

Dye components

a) developer b) coupler

Nuance of the colored hair

by air oxidation

16

17 18 19

O 2O (O

00 21 O
(O

22nd 23

24 25 26 27

28 29 30

C D E F A

C D

E F A

B C D

1% HO solution
« 2t

x) with 4% HO solution ^ 2

HO solution
2 2

l-amino-2- (a -cyanmethane
sulfonamido) -4-nitro-benzene olive brown brass yellow reddish yellow dto. linoleum brown olive brown creamy yellow dto. olive brown nut brown hazel brown dto. olive olive dto. brownish yellow brownish yellow light brown 4 -A mino -2 - (a -cyanmethane -
sulfonamido) -1 -nitro-benzene olive brown olive olive dto. olive brown honey yellow blond dto.
dto. olive brown
olive brown olive yellow
dark brown olive yellow
linoleum brown dto. olive yellow olive green Ό
olive brown dto. olive yellow olive brown ³ O
golden yellow 1 -A mino -4 -fa -cyanmethane -
sulfonamido) -2-nitro-benzene
dto. rust brown
duct brown cocoa brown
light brown titian red
autumn gold dto. Brown duct brown autumn gold dto. autumn gold dark brown red-brown

Example no,

31

32 33

-JN 34 O

<O 35 CO
IO 36 to

£ ^ 37 38 39

40

41 42 43 44

45

Dye components

a) developer b) coupler

Nuance of the colored hair

Q A

B C D E F A

B C

D E A

by air oxidation

single HO solution

dto.

khaki

9% HO solution

Ct Cj

1 -A rrnno -4 - (α -cyanmethane -
sulfonamido) -2-nitro-benzene cognac brown dark brown dark brown dto. terra di Siena hazel brown dark brown 2- (a-cyanomethanesulfone
a mido) -4-chloro-6-nitro-phenol somali brown fawn titian red dto. brick red terra di Siena brown orange dto. titian red autumn gold Red gold dto. brick red beaver brown umbra dto. brick red somali brown dark brown dto. Red gold Red gold X)
autumn gold 2 - (cfcyanomethanesulfone -
amido) -6-chloro -4 -nitro -phenol bronze brown bronze brown yellow-brown dto.
dto. olive brown
yellow-brown olive brown
olive brown deep yellow
deep yellow dto. olive brown, soot brown yellow-brown dto. deep yellow yellow 2- {cx-Cyanmethanesulfon-
amido) -4 ^: nitro-phenol olive brown ■ · brown bronze brown

x)

χ)

X)

grey yellow

JS-VJI VyY Vyy

x) with 4 <7o

-Solution

example
Kr. Dye components b) coupler Nuance of colored hair 9 <70 HO solution
ti ti O 46 a) developer 2- (ct-cyano methanesulfone- by air oxidation l ^ ige HO solution
Ci £ t honey yellow icle C. amido) -4 -nitro-phenol clay colored honey yellow fr 47 dto. linoleum brown O
S " 48 D. dto. golden yellow soot brown ι GmbH 49 F. 4 - (a-cyano methanesulfone - ocher yellow golden brown grey Red A. amido) -2-nitro-phenol brown-gray brown-gray 5O dto. beaver brown O 61 D. dto. nougat brown nutriabrown X)
purple brown Ϊ <£>
09 52 E. dto. olive brown purple brown Brown 09 / F. pompeian yellow Brown

χ) m-t 4% iser HO solution

2 2

JS-

Claims (3)

Henkel & Cie GmbH S.It. 17 * ur Palontonmetduns D ^ 533 claims 1. Chemical compounds of the formula Y-fO-f-NH - SO ₂ - CH ₂ - CN NO, in which Y is hydrogen, chlorine, bromine or an alkoxy group with 1-4 C atoms and Z is an NH ₂ or OH group. 2. Use of compounds according to claim 1 in preparations for coloring hair. 3. Use of compounds according to claim 1 in combination with customary developer substances in preparations for oxidative purposes Coloring of hair. 409809/1234