DE1940079A1 - New dioxazine derivatives, processes for their production and use - Google Patents

Description

DR. EULE DR. BERG DlPL.-ING-. STAPF

PATENTANWÄLTE 8 MÜNCHEN 2. H 1 LBLESTRASSE 2O

• Dr. Owl dr Berg Dipl.-Ing. Sfapf, 8 Munich 2, HilblestraÖe 20

Your reference - our reference date

"Aug. 6

Case 6543 / E
Germany

Attorney's file 18 625

CIBA Aktiengesellschaft, BASEL · / Switzerland.

New Bioxazine Derivatives, Process for Their Production and

Use,

The present invention "relates to valuable dioxazine derivatives and their preparation by reacting 1,4-Benzoquinones with aryl sulfamides, the hydroxy and amino groups Contain in neighboring position, to phenoxazones and reaction of the phenoxazones obtained with o-hydroxyarylamines ,,

British patent 411.132 mentions that the transfer of the condensation reaction of benzoquinones and especially halogenated benzoehinones with o-aminoaryl mercaptans to dyes of the thiazine series on o-amino

009809/1120

® (0311) 'S 16 20 81 Telegrams: PATENTEULE Manchen Bank: Bayerische Vereinsbank Munich 453 100 Postal check: Manchen 653

. ': ■ - ■. ■■ - 2 -. ■■ - ■ .. .- ■■: ■■■ '. ■■.;.

"^:; \ 1ΜΌ078

phenols and their halogen or alkyl derivatives are not included corresponding oxazine compounds.; ■ leads, since the quinort * ΐτΚ ■ "■ in this case only has an oxidizing effect. In. of the patent specification mentioned. A process is described, 'according to which, in contrast to the above finding, o-aminophenols, which contain a ■ nitro group, with eenzoquinones and halogenated benzoquinones can be condensed to form dyes of the oxazine series.

It has now been found that oxazine compounds

Surprisingly also by condensation of o-aminophanols, which contain a sulfamide group, available with!, ^ - quinoneη are. .

The inventive method consists in that compounds of the formula

(D

where X is a hydrogen atom or a removable substituent, ' In particular chlorine or bromine, and Y each a. -Water · - ' substance or halogen atom or a non-ionogenic substituent,

■ ■ ■ ■ ■ -. ■ - ^% ■

such as the cyano, amino, acylamino, acyloxy or. Alkoxy radical

means, with compounds of the formula H _p N, _v

HO
where R 1 is an aromatic radical which is a sulfamide group

0098097ΊΊ20

BATH

Λ 1940Q7S

and may contain further substituents, e.g. Halogen, alkyl, acyl (e.g. aroyl), aryl, acylamino, cyano, Nitro, cycloalkyl, and others, and to the HpN and HO groups in neighboring positions are bound to intermediate products of the

γ;. · "■ '■■. · ■■" · ■■'. ■. ■■■ - ■■ formula

wherein X, Y and R _{1 have} the meanings given above, and these with compounds of the formula

2. .- ■■ -.- ■ -.-. ■■ ■ -. ■■ -

where Rp is an aromatic radical containing substituents can, such as sulfamide, halogen, alkyl, acyl, aryl, Acylamino, nitro, cyano, cycloalkyl and others and to which the HgN- and the HO group are bonded in the adjacent position to form compounds of the formula

in which R *, K ₂ and Y have the meaning given above, are reacted.

The compounds used as starting materials. of formula (1) can conveniently be obtained by Condensation from a hol of a halogenate or nitrated one

009809/1120

p-Benzoquinones 2.B.2,5-dinitro- (or 2, 5-dihalogen-) 1,4-benzoquinone or 2j3 * 5,6-tetrachloro- (or tetrabromo-) benzoquinone (1/4) with compounds, which contain hydrogen or easily exchangeable substituents, such as ammonia, amines, alcohols, ethers or the like, in the presence of an acid-binding agent such as sodium acetate or magnesium oxide. Tetra'chlor-l, 4-benzoquinone (chloranil) is used, which can be prepared by one of the usual processes, e.g. by chlorination of phenol or o-chlorophenol, or by chlorination of aniline in sulfuric acid at 110 C. The starting materials of the formula ( 2) are for

for the most part known and can be obtained by known processes, e.g. by implementing the appropriate

jo ^ Nitrochlorobenzene-sulfochlpride with ammonia, primary .._.._ "._

Replacement. "Of" halogen by "_djie_Hydroxy 1 group and reduction. To amine, or secondary amines, '; As starting materials of the formula (2)

are for example mentioned:

l-Hydroxy-2-aminobenzene-4-sulfonic acid-N-methylamide, i-Hydroxy-2-aminobenzene-5 "-sulfonic acid-N-methylamide, l-Hydroxy ^ -aminobenzene- ^ sulfonic acid amide,

l-Hydroxy-2-aminobenzene-4-sulfonic acid-N-ethylamide, ν

l-hydroxy-2-aminoberizole-5-sulfonic acid-N-propylamide, l-Hydroxy-2-aminobenzene-4 --- sulfonic acid -N- isopropoxypropylamide,

i-Hydroxy-2-aminobenzene-5-sulfonic acid-N-i.Ξopropylamide, l-hydroxy-2-aminobenzene-4-sulfonic acid-N-cyclohexylamide,

009809/1120 '; bad original

l-Hydroxy-2-amino-4 ■ -chlarbenz.ol - ^ - sulfonic acid-N-ethyiamide, l-hydroxy-2-amino- ⁱ | -chlorobenzene-'5 ⁱ -suironic acid-N-methyiam ± d , l-Hydroxy ^ -amino - ^ - chlorobenzene-S-sulphonic acid-N-butylamide, l-hydroxy-2-amino-4-bromobenzal-5-sulphonic acid-li ~ isopropylamide, l-hydroxy ^ -amino - ^ - methoxybenzene -S-sulfonic acid-N-isopropylamide, l-hydroxy-2-amino- ⁱ l-phenylbenzene-5-sulfonamide, l-hydroxy-2-amino- ^ - methylbenzene-5-sulfonic acid-N-isopropoxyp'ropylamide,

2-hydroxy-3-aminonaphthalene-6-sulfonic acid amide, l-Hydroxy-2-afinonaphthalene-5-sulfonic acid-N-me thy! amide, 2-Hydroxy-1-aminonaphthalene- ^ - sulfonic acid-N-isopropoxypropylamide.

The starting materials of the formula (2) continue to exist o-Hydroxyaminoär! sulfonic acid amides into consideration, other Amide nitrogen atom- the following radicals are bonded: ß-hydroxyethyl, ß-cyanoethyl, Ύ-methoxypropyl, β, γ-dihydroxypropyl, 'j' ^ - hydroxypropyl, ß-methoxyethyl, ß-ethoxyethyl, γ-ethoxyprjopyl, Y-phenoxypropyl, phenyl, benzyl, 2-naphthyl, Piperidyl, morpholyl and others.

As starting materials of the formula (2), ^{according to US 1} Se rdemaromatic o-hydroxyamino compounds come into consideration, which contain N-disubstituted sulfonic acid amide groups. Such N-disubstituted sulfonic acid amide groups are named: sulfonic acid-N-dialkylamid groups-such as sulfonic acid-M-dimethy 1-, -N-diethyl'-, -N-dipropyl-j -W-dibutyl-y -W-di- (ß-hydroxyethyl) -, -N-di ^ -ß, γ-dihydroxypropylamide group or the sulfonic acid group ^ N-methy 1-N-ß-hydroxyethyl amide group _s SuIforic acid-N-dieycloalky 1-

'· 0-Ö9ÖQ 37 11-20 * '"'■■""" ■■. *

BATH ORIGINAL

amide groups vile the sulfonic acid-N-dicycloxylamide group, Sulfonic acid M-diaralkylamide groups, such as the sulfonic acid ^ N-dibenzylamide group, Sulfonic acid-N-alkyl-N-cycloalkylamide groups, like the sulfonic acid-N-methyl-N-cyclohexyl amide group, sulfon- - ■ acid-N-alkyl-N-aralkylamide groups, such as the sulfonic acid-N- ' methyl-N-benzyl-amide group or sulfonic acid-N-alkyl-N-arylamide groups, like sulfonic acid-N-methy1-N-phenyl- or -N-ethyl-N-phenylamide group.

As examples of starting materials of the formula (A) are mentioned:

l-Hydroxy-2-arnino-Amethy! benzene,
l-Hydroxy-S-amino - ^ - or -5-chlorobenzene, l · -Hydroxy-2-arnino- ² 1-chlorobenzene-5-sulfonic acid-M-methylamide /. l-Hydroxy-2- ^amino-1 ! - or -5-nitrobenzene, l-hydroxy-S-amino-A ^ o-dichlorobenzene.,
l-Hydroxy-2-amino- ⁱ ) - prior-5-n-trobenzene,. l-Hydroxy-2-amino - A-nitro-6-chlorobenzene,: _,,. _; ,

1-hydroxy-2-amino- ' ⁱ {-acetaminobenzene, 1-hydroxy-2-amino- ^ ~ phenylberizole _J
l-Hydroxy.-2-amino ~ 4- (2, '-methylpheny! benzene,

l-Hydroxy-2-aminonaphthaliri-4-sulinoic acid amide-

2-Hydroxy-J-amlno-ö-methpxy naphthalene.

009809/112 ©

. "- ■■■. - ■ _.-_- ν

BATH ORIGINAL

Of particular interest are dioxazine derivatives that are obtained when the starting materials are chosen so that R- and Rp in the given formula of the end product represent the same aromatic radicals, in particular benzene radicals »Starting materials of the formula (2) which have a substituent of the formula - SOo-NHg or a sulfonic acid amide group containing a low molecular weight alkyl or alkoxyalkyl radical are particularly suitable for the process according to the invention because of the condensation reaction which proceeds very smoothly and in high yield with them. If the same starting materials of the formula (2) and (4) are used, the finished compound contains a sulfamide group _{in both radicals R and R 2.} In this case, if the intermediate product is not isolated, the preparation leads in one step to the end product of the formula (-5). However, the possibility of preparing dioxazine derivatives with asymmetric molecules, as described in Examples 2, 5 and others, is particularly important are·

It is according to the method according to the invention

also possible to get to oxazine thi azo compounds by instead of a starting material of the formula (4) one of the formula

R ₂

S:

is used, in which R _{2 has} the meaning given in the explanation of the formula (4).

009809/1120

The reactions according to the invention take place expediently in an organic medium, e.g. in alcohols such as ethyl or amyl alcohol, or in esters such as ethyl acetate, in methyl ethyl ketone, carbon tetrachloride, N-methylpyrrolidone, Dimethylformamide, mono- or dichlorobenzene, nitrobenzene and the like, optionally with heating of the reaction mixture, which is preferably also an acid-binding agent, in particular potassium or sodium acetate, optionally also contains a ring-closing agent.

The dioxazine derivatives obtained according to the invention of the formula (5), in which Y is halogen, can subsequently with suitable compounds, ζ · B. with potassium cyanide, Ammonia, amines such as methylamine or aniline, organic acids such as acetic acid, formic acid or benzoic acid, if appropriate in the form of their salts, alcohols such as methyl or isopropyl alcohol, or phenols or organic acid amides such as Acetamide, nicotinic acid amide or benzamide are reacted, the halogen atoms Y being replaced by other radicals,

The according to the inventive method

intermediate products and dioxazine derivatives obtained are new " The intermediate products are valuable starting materials for the production of dyes. They are easily available and can be isolated in pure form without difficulty.

The dioxazine derivatives obtained are valuable, mostly red or yellow dyes, which are e.g.

00 9 809/1120

as pigments and can be used for a wide variety of pigment applications, e.g. in finely divided form for dyeing rayon and rayon or _; Cellulose ethers esters und. or super polyamides or _o Super polyurethanes or polyesters in the dope, as well as for the production of colored lacquers or ^ paint agents, solutions and products of acetyl cellulose, nitrocellulose, natural resins or synthetic resins such as polymerization resins or condensation resins, ζ, Ε, aminoplasts , Alkyd resins, phenoplasts, polyolefins such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, rubber, casein, silicone and silicone resins ", they can also be used advantageously in the manufacture of colored pencils, cosmetic preparations or laminating plates"

The compounds obtained according to the invention, which are soluble in organic solvents such as esters and especially in alcohol and acetone, can be used for dyeing natural or synthetic resins, waxes, lacquers and plastic materials, e.g. from cellulose ethers or esters, for example for dyeing Acetate silk as well as for dyeing natural or synthetic. Polymers or condensation products are used _e

With the compounds according to the invention leaves see e.g. acetate rayon after the spin dyeing method in dye clear, over-dyeing, chlorine- and exhaust-gas-resistant shades *

- LO -

1940Ö7

The colorations obtained are in general very migration-proof and excellent wet-fast. The fastness to dyeing of the acetate silk dyeings is also remarkable. What is particularly striking is the astonishingly high color strength, the purity of the nuances and the liveliness of the new dyes.

In the following examples, the mean Parts / unless otherwise stated, parts by weight, the percentages are percentages by weight, and the temperatures "are in Degrees Celsius.

ORIGINAL BATHROOM

1 12 QP

-. Example 1 » '

29 parts of S-amino-l-hydroxybenzor - ^ - sulfone-

acid-N-isopropoxypropylamide, 25 parts of chloranil and 8.5 parts Anhydrous sodium acetate is mixed with 20Q parts of ethyl alcohol Stirred for hours at room temperature. One filters off, washes with ethyl alcohol and water and dries. The condensation product of the formula

Cl

Cl 0 <_> _{-S0 2} NH (CH ₂ ) ₅ OCH (CH ₃ ) ₂

falls in orange-red crystals with a melting point. It is made in acetone and using aromatic solvents orange-yellow color soluble. In concentrated sulfuric acid, the condensation product dissolves with a green color.

:. ■ Using the same method, the in Manufacture the products listed in the table below. In column I is the constitution of the product obtained, in Column II shows the melting points and column III shows the solution color in sulfuric acid. \

0098097112 0. .

BATH ORIGINAL

Cl Cl

Cl

II

282-283

273 ^υ . ; Decomposition III green

olive

00 9 80 97 1 12 0

Example 2. ,

24 parts of that obtained in Example 1

1 _f 3 »4-trichloro-6-sulfonic acid-N- (isopropoxypropyl) amidophenoxazon-2 and 12.5 parts of 4-chloro-2-amino-1-hydroxybenzene in the form of the dry sodium enolate are stirred in 200 parts of dimethylformamide . Condensation sets in with self-heating. After stirring for one hour, the mixture is heated to 120-125 and held at this temperature for a further 60 minutes. After cooling, the reaction mixture formed is poured into 2000 parts of a 2 strength sodium chloride solution and the precipitated compound or dye is separated off by filtration and washed with water. Pas dried condensation product of the formula

represents a brown powder, which dissolves in acetone with an orange color and acetate silk spinning mass in strong colors reddish-yellow tones. The compound or the dye dissolves in concentrated sulfuric acid pure blue color.

09809/1120

Example ^ »

24 parts of 1,3,4-triehlor-6-sulfon3 acid-N- (isopropoxypropyl) amido-phenoxazone-2, 18 parts of 4-chloro-2-araino-loxybenzene-5-N-methyl-sulfaiaide and 6.5 parts of anhydrous sodium acetate are suspended in 200 parts of chlorobenzene and kept stirring at 120-125 for several hours. The solvent is then distilled off with steam, the residue is filtered off and washed with methyl alcohol and water washed. The dried condensate product of the formula

is a brown powder that dissolves in acetone with orange color dissolves and acetate silk in shining orange tones. In concentrated sulfuric acid 8ioh dissolves the compound or the dye with a pure blue color,

00980 9 / 112Ö

Example 4.

24 parts of 1,3,4-trichloro-6-sulfonic ^ äure-N- (i3opropoxypropyl) amidophenoxazon-2, 11.5 parts of 5-nitro-2-araino- '■' _ 1-hydroxybenzene and 6T5 parts of anhydrous Natriuin- acetate are stirred in 300 parts of nitrobenzene for three hours at 120-125 °. The solvent is then distilled off with steam, the residue is separated off by filtration and washed with a mixture of ether and petroleum ether. The condensation product of the formula that has finally been boiled with water and dried

^) ₃ OCH (OH ₃ ).

represents a dark brown powder "which dissolves in acetone with an orange color and dyes acetate silk spinning mass in bright orange tones. The compound or the dye with a pure blue color dissolves in concentrated sulfuric acid ·

0Q9809 /

Well the one given in Examples 2-4 Procedures can be derived from those mentioned in the table below Manufacture of starting materials other dioxazine derivatives. In column I is the trichlorophenoxazone used for condensation, the o-aminophenol indicated in column II; Column III contains the solution color of the compound formed (color toffee) in acetate silk spinning pulp. In the formulas given, R denotes the isopropoxypropyl-NH radical.

. I.
f """■" ■ ' Il egg - II Cl t
♦ - "·." * ■ - ' HN 01 Cl II> S0 ₂ R
-: - - H0 <~> -S0 »NIJ
- ■ ^ j. HN Cl Cl - ^ VSO ₂ NH, Cl
01 . V -> - S0 ₂ R H (HC ^ -0H- "" XIy "^ ^ r vvfl« » HO-C ^ -Cl-
ι, '

reddish yellow

eoharlaoh

009809/1120

! MSPEGTED

I. _> S0 ₂ R II H N III Cl = £ / H ₂ JT
HO-0-so> jir (o.Ho) _?
w_. T ί / ^ - Scarlet fever /
Cl I> S0 ₂ R . η. orange Cl
co / Eq reddish
yellow

009809/1120

'"■' \ Example 5. -

29 parts of 2-amino-1-hydro: / cybenzene-4-sulfonic acid-N-isopropoxypropylamide in the form of dry sodium phenolate are dissolved in 200 parts of dimethylformamide and a total of 12 parts of chloranil are added in portions to the solution with stirring. Condensation occurs under self-heating. To the The reaction is ended and the mixture is stirred at 120-125 ° for some time. Then the reaction mixture is divided into 2000 parts of a 5% sodium chloride solution discharged. The dye is

separated by filtration and washed with water. He can be redissolved from methylbenzene for cleaning. The condensation product of the formula thus obtained

represents an orange powder which dissolves in acetone with orange color dissolves and acetate silk spinning mass in bright, reddish yellow tones.

- 18a -

0 0 9 8 0 9/1 12 JD

$ 1

Dlacetylamihodichior-benzoquinone is used instead of chloranil used as a starting material / a dye of the following formula is obtained:

(CH _x ) _o CH0 (CH _0. )

NHCOCH

CH "C0HN ·

If you replace the chloranil in the above example by 2-, 5-Dlbroin-benzoquinone-Ι, Λ ", 'then one obtains the Dye of the formula

009809/1120

η - 40

which has similar properties.

Following the same procedure; one obtains from Chloranil and those mentioned in column I of the table below o-aminophenols further symmetrical triphendioxazine dyes, in column II is the color of the corresponding Dioxazine derivative given in acetate silk spinning mass

, -. '■ ι - -. . · Red -. -, ■ ■; ':' ■■■. - ,. reddish yellow Scarlet fever .-
bluish red. NH ₂ D ^: SO ₂ NHCH (GH, -. -, ·. . . '> ■ ■ ■■ ■
- ^H0 "lL -r / 1120 HO-A ", ·
U-OCH ₅ ' SO ₂ R, 00 9 80 ■ '.- ■. * .- ■, -. ■ ■

IWSPECTED.

Ii

II

-NH,

"V-

NH,

Red

Red

SO ₂ R

In the formulas given, R denotes the isopropoxypropyl-NH radical and - <fir "> the cyclohexyl radical.

009809/1 IIP

Claims (1)

Claims, ^; . Iy Process for the preparation of Moxazia & derivatives, characterized in that compounds of the formula Y '
X
(V) where X is a hydrogen atom or a split-cleavable substituent and Y each represents a hydrogen or halogen atom or a nonionic substituent means «with compounds H ₂ N the formula (2) N1 wherein R ^ is an aromatic radical which is a sulfamide group contains, and to which the HpN and the HG groups in Waehbarst separation are bound to intermediate products of the formula (3) ■ ■ - · ■■ γ -: r ... ■ ■: ■■■ - ■ -.... ·; ■■■ - .. where X, Y and R-, half the meaning given above, and these with compounds of the formula (4) R ₂ OH NH ₂ wherein R _{2 is} an aromatic radical, on the äi @ E ₂ H- and the 009809/1120 ^ _{ORSQINÄL! NWE} GT _E D HO-Gruppe in Neighborhood are bound to compounds the ... formula where R- ,, Rg and Y have the meaning given above, implemented. 2. The method according to claim 1, characterized in that the starting materials of the formulas (2) and (4) are the same. 3. The method according to claim 1 and 2, characterized in that the radicals R ₁ and R _{2 represent} benzene radicals * 4. The method according to claims 1 to 3 thereby characterized in that X and Y are chlorine or bromine. 5. The method according to claims 1 to 4, characterized characterized that R-, a -SOoNHp group, a sulfonic acid-N-alkyl- or If-CÄlkoxyalkyl) amidgruppe contains. 6. The method according to claims 1 to 5, characterized characterized in that the reactions are carried out in the presence of dehydrating agents and optionally ring-closing agents be performed. 7. Process according to Claims 1 to 6, characterized in that the reactions are carried out in organic solvents be performed. · 00 980 9/1: 1.10 194007S θ * method according to claims 1 to 7 »characterized in that the reactions are carried out at 120 to 125 ° to _p end." 9. The method according to claims 2 to 6, characterized in that the preparation of the dioxazine derivatives is carried out without isolating the intermediate product. 10. Process for the preparation of dioxazine derivatives according to claim 1, according to the examples given. 11. The obtained according to claim 1 according to the examples given Di oxazinderi vat e. 12 · DioxesiBderivate of the formula wherein
to have" and Y has the meaning given in claim 1 13 · DioxaBinäerivate according to claim 12, wherein R ^ and R _{2 represent the} same radicals, 14. Di oxazinderivatβ according to claims 12 and 13, wherein R 1 and R _{2 are} benzene radicals. 15. Dioxazine derivatives according to claims 12 to H, where Y means chlorine or broa * 16. Dioxazine derivatives according to claims 12 to 15, wherein R ^ represents an aromatic radical which contains a group ier formula -SO ₂ NH ₂ or an N-alkyl or an N-alkoxyalkyl sulfamide group. 0 0 9 8 0 9/1120 17. The dioxazine derivatives mentioned in the examples given. 18.. The according to claims. 1 to 9 obtained Dioxazine derivatives. 19. Compounds of the formula wherein X, Y and R have the meaning given in claim 1 to have. 20. Use of the oxazine derivatives according to claims 12 to 19 for coloring and printing. 21. Use of the oxazine derivatives according to claims 12 to 19 as pigments. 22. Use of oxazine derivatives according to claims 12 to 19 for dyeing acetate silk spinning mass 23 ·. The material dyed or printed according to claims 20 to 22. 009809/1