DE2036136B - Process for the production of kationi see dyes of the naphthoylenebenzimid azole series - Google Patents

Description

where the core H is metin 1- by chlorine or bromine atoms. O- Y -. Nitrite or Trilluormethv, I groups can be substituted and R is an optionally substituted alkyl group or aralkyl group is. condensed.

French patent specification 1,440,053 discloses lationic ones derived from naphthylene benzimidazole Dyes known by the following allf cmcine formula can be represented:

(I)

NNR

Ii <■

the Naphlhalin nucleus A by one ocier several (chlorine or bromine atoms, one or two one or two O Y groups, where Y is cine alkyl. Aralkyl or aryl group, preferably is the methyl or ethyl group. can be substituted.

de. Benzene ring B by chlorine or bromine atoms, Methyl-, O · -Y, where Y has the same meanings as above, nitrile or trifluoromelhyl groups can be substituted,

at least one of the nuclei A or B is substituted.

R cine alkyl or aralkyl groups and

X is a monovalent Anton or its equivalent. The I ¹ UrI) SIoITe of the formula (I) are converted to the formula by Ouai · ternization of the naphthoylenhenzimidazole Dci Uau

Il

wherein the cores A and B have the same rJedeuiunycn as in formula (I), with HiHc an alk \ iating agent, possibly in the presence of οι ganischem Solvent.

The dyes of the formula (H) are generally prepared in a manner known per se by that one naphthalene anhydride or his - 25 substituted derivatives with o-l'henylenediamine oiic; condensed its substituted derivatives, is is in in the same way known that in the case of substituted derivatives this condensation in general a mixture of isomers ran, Fs form two isomers if only one of the nuclei A or Ii is substituted, and there are theoretically four isomers possible if the two nuclei A and B are substituted are, and the case of a pair-wise symmetrical polysubstitution of the nucleus A or B are identical Substitution arises in the case of correctly substituted derivatives.

An attempt has been made to determine the number of Is> meicn au! i or 2 can be traced back by a selective synthesis. why one the position of the Si: bstituenlen of the core B fixed. This can be achieved through this. dall one of the formula (II) corresponding Fainstoff the quartering subjugates, whereby dic-ei has been established thereby. that one uses the naphalic anhydride or its substituted 1 derivatives

4s condensed with a substituted o-nitroaniline, you Reduced nitro group and cyclized. being the two the latter implementations can be demonstrated at the same time. This production method is off <iei /iisat/-pa!cn!.%chrifi 90 779 to the French !; ! 'ate !!!' .'- '!! · iü

so I. + 4O 053 known.

Although this preparation is easy in F.iboralorien is to be made. leads them in industrial I mlans; always to trouble. The condensation of a substituted o-nitroaniline with naphthalic acid oil

5S hydride is used without a solvent in a mixture of the reaction parallels duiehg-led reaction only takes place at about 240 C, 111 H
If larger quantities are used, the (ii-L Ii

the reaction finally with explosive evidence

fo goes through. On the other hand, the quartz rune; of the dyes of the formula (II). which is relatively easy . when it comes to stirring a methyl radical on the nitrogen. difficult, not to say impossible, if the alkyl radical is too large or substituted

■ '5 is tuated.

It has now been a new process for the manufacture of the dyes of the form! (I) found that it makes it possible to customize these compounds

2 036! 36

© line isomers / ii er
<| cr shape!

iah.cn. for which purpose I) KiIi cm anhydride

Jwnin any Suhslituenlen of the core Λ the same | ledciiiimg as stated above, in (iegen- | \ ari of acetic acid or one of its higher homologues and around fish with an o-nilraniline of the allgelncineii formula

NO,

St.

NIIR

(IV

wherein any Siibsliluenten of the core B the same ! Have the meaning given above and K either an alkyl base. which optionally, for example, by hydroxy. Alkoxy or nitrile groups is substituted isl or an aralky! group. condensed. The acid used is preferably acidic acid. The new process selectively delivers a quai lei nary dye in a single operation ι he general form!

^Λ i .ν

N N R

The I! Introduction del Aniliiiderivale dei I oimchlYi ni known and made possible! it. slightly .'ic ait dr-. i'Cstc ¹ . R m very extended i <ireiizen to choose Xiidereiscit- condenser! the resulting Λ mm "group, which arises from the reduction of the Nitrogriippi in dci mass, slightly mil ilei Xnhvdi idtü uppc

I) it '-, e implementation also runs with Naphthalu ^ äinC " iiihvdi idcn the l'orniel

R, R.

(YIl

O ^u O

away. wherein the radical K _{1 is} an alkyl group. which is optionally substituted by alkoxy, NiUiI or Trilluoimethylreslcn and R _{2 is} an alkyl group. the alkoxy can also be used. Nitrile or I rilluoimethyhesien subsiiiuieri or a riienylgnippe isl, which optionally subsiiiuieri isl by halogen atoms or alkyl, alkoxy, siluormelhyl- or Nilrilgiuppen and the radicals R ₁ and R> with the nitrogen atom with which they are connected, a llelerocycliis, how to form a piperidyl oiler moipholinyl ring. So applied, made possible! the eilindur.gsgcmülk 'process of producing the larbslollc known from the French Ralenlschnfi 1 472 179 in a different way.

The isetic acid, which is used as a conversion agent must enthalieii water. Your 1 ilei can be between 4 (1 and 9Sl ", ι. preferably between 9 (1 and 95" i .. ausvälill will.

The l-iseii. in a linen IHiKeis. can in . Ls is always advantageous to use the amount at the end of the I iin.sci / ιιημ leads to a basic l.i.scnaceiat that is sparingly soluble in the aqueous liquid.

The implementation is running at different levels Temperature :! Ah. They are routed between two 90 C and the boiling point of the solvent.

In order to isolate the dye, it is sufficient, for example, the mixture is mixed with boiling water to dilute the basic Fiscnacelal Schlamni abzulillriereii and variable amounts of sodium chloride to add to the nitrate to make the Farhstoll (chloride from / '. i cases.

In the following examples, Mch adjust the parts and percentages as (iewehtsemheiten) unless otherwise stated.

Example !

1! Classification reads 5'-Mellioxy-N-melh \ Inaphthov lenhenzimidazolium-cl'.lorids

30 leite 4 - N - Melhslainino - 3 - niiroaiiiMil and 3.ΐ Ί hurry Naphlhalinsiiureai'l.ydiid graze in 20Oi hurry '' 5 ".. ige I ssigsäuie registered. One hurries aiii 9 (1 '. And gives in the course \ The temperature is exothermic, and the temperature is kept at 100 (. The heating is continued for a period of 100 to 105 ( lil-Ii leil, to alvuiicnnen the unli'isüehe.basic 1 isenacelate. You rinse and add 50'IeUe 'sodium chloride to the nitrate. rs krisUiü' ^ 'C!' d: is> -Mcthow-N - nietlu I - naphthov lenbeiiziniidazoliuni-chloi id. It is enveloped and taken up with IU (M) '! hurry M> (warm water. The obtained I öMing 2 I hurry revealing charcoal is added. nilii 1 IU minutes I.iir. :. liltiici! and gii'i dem 1 illral 50 Ί hurry Naiiiiim-ι him id. Let aiii / immeilempei, hui cool, nitrate, wash with a 5 "i> igen N, ill mi iiu. ti 1 <· Ϊ́ 'idless iing. then with a little water. qiii-is; hl and dries at hU to 'M) <'. In this way one obtains 52 parts of very pure substance with a yield of 9%.

For analysis one recrystallizes from water. for the gross formcl

(,,,! 1 ,, (IN ₂ O _2. Il, ()
One keeps the following notes:

I-.rrcthnct:
(05.2. H 4.07. N7.60. (I 9.d4. H ₂ O4.4%:

found:

(64.7. 114.42. N 7.44. (19.50. H ₂ O 5.00 ";,.

This color shade dyes acrylonitrile in a gulb-green, lively, strong shade • very good real health sciences in particular opposite light.

Example 2>

Production of the 4'-melhoxy-N-melhylnaphlhoylenhcn / i cn iduzoli u in-chloride

In Example I, the 4-N-melhylamino-3-nitroanisol is replaced an equal amount of its isomer ig S-N-methylamino ^ -nitroanisole is obtained under the 4'-methoxy isomer of the dye described in Example I under the same conditions. It dyes polyacrylic fibers in a shade corresponding to that of the dye of Example I.

Example 3

Production of 5'-methoxy-4- or 5-bromo-N-methylnaphthoylenebenzimidazolium

chloride, ₀

This connection is obtained by one in Example I the 33 parts of naphthalic anhydride were replaced by 56 parts of 4-bromonaphthalic anhydride. The material to be implemented is considered to be orange-bonded Needles. ο

Results of the analysis after recrystallization in water:

Gross formula: C ₂₀ H ₁₄ ClBrN ₂ O ₂ + 7.50% H ₂ O.

Calculated:

C 54.4, H 3.05, N 6.10, Cl + Br (in mol) 2.00%;

found:
C 54.0. H 3.0S, N 6.30, Cl + Br (in moles) 1.92%.

B e i s ρ i c 1 4

Preparation of S'-methoxy-N-benzylnaphthoylenebenzimidazolium chloride

The procedure is as in Example 1 with the following amounts: 37 parts of naphthalic anhydride, 43 parts of 4c 4-N - Benzylamino-3-nitroanisole. 300 parts 95% Acetic acid and 23 parts iron powder. The raw dye is taken up in 1500 parts of boiling water, to which 3 parts of decolorizing carbon were added. The filtrate is precipitated by adding 200 parts by volume of concentrated hydrochloric acid. The crystallized Dye is filtered, with a 5% sodium chloride solution, then washed with very little ice water. The weight obtained after drying is about 50 parts; Yield about 70%.

Line in water iinikristallisk rle sample lieierl du the following analytical events:

Step formula C, "l I ,,, CIN, 1) ,, 3 ILO.

Calculated:
C 64.9, 115.20, N 5.82, Cl 7.28, ILOI2.fi ",.;

found:

C 65.1, 114.59, N 5.75, Cl 7.46, 1LOI0.6 ',,.

This dye dyes acrylic fiber !! in a yellow-green, very lively, strong color tint with very good fastness properties, especially in relation to it Light.

Example! 5

Production of 5'-methoxy-N -, .'- cyanoäthylna phi hoy len benzimidazolium chloride

This dye is obtained if, as in Example 1, with 12 parts of 4-N- / i'-Cyanoüthylamino-3-nitroanisole, 13 parts No. _ 'ithalic anhydride, 66 parts by volume 95% acetic acid and 7.6 parts iron is working.

The dye dyes acrylic fibers in a yellow-green, remarkably lively shade with good fastness properties, especially towards light.

The 4-N- / i-cyanoethylamino-3-nitroanisole used can be prepared in the following manner: 16.8 parts of 2-nitro-4-methoxyaniline are dissolved in 50 parts by volume Dioxane. 5 parts by volume of a 10% strength methanolic solution of ammonium tetrabutyl hydroxide are added and then, gradually, at 40 C 30 parts by volume of acrylonitrile.

The mixture is stirred for 3 hours at 40 ° C. After allowing it to stand for 16 hours at room temperature, the mixture is distilled under Vacuum approximately two thirds of the solvent. It is cooled to IOC, filtered, squeezed off and washed the strong red, crystalline appearance with alcohol.

After drying, 1 5.5 parts are obtained.

For analysis, the product is crystallized in dichloroethane in a ratio of 1 part to 5 parts of solvent around. The product obtained has a melting point of 105 C.

Analysis for the gross formula C ₁₁₁ H _n N ₁ O,:

Calculated ... C 54.28, H 4.97, N 19.01%;
found .... C 54.6, H 5.62. N 18.8%.

The table below gives further examples of dyes which were prepared as in Example 1.

table example

6th 7th 8th 9 IO

methyl

methyl

ethyl

methyl

methyl

Suhsliluent from Λ

5- or 4-Methoxy Siibsliuienl from M

5-chlorine

5'-methyl

5'-methyl

5'-bromine

5'-methoxy

Shades of color ιΐιιΓ '' (ilyiimlfii

Pale yellow
Pale yellow
Pale yellow
aia yellow
Intense yellow-green

Il

example

Preparation of 5- or 4-morpholino-5'-methoxy-N-methylnaphthoylenebenzimidazolum chloride

A mixture of 60 parts of 4-morpholinonaphthalene uric anhydride is heated under gentle reflux, 36 parts of 4-N-methylamino-3-nitroanisole and 700 parts of 95% acetic acid. One leads in small surcharges in about 1 hour 27 parts iron powder. The mixture is heated under for a further 2 hours Reflux, 2500 parts of warm water are added and the mixture is filtered at the boiling point. 150 parts are added to the filtrate

36

Add sodium chloride and allow to cool. The precipitated one Dye is filtered with a 5% sodium chloride solution rinsed, squeezed and dried. In this way, 85 parts of the dye are obtained Polyacrylic fibers in a strong, extremely luminous, vermilion tint stains.

For analysis, it is crystallized in hydrochloric acid Water, then twice in ethanol.

Analysis for the gross form C ₂₄ H ₂₂ CIN ₁ O ₁ , 2H ₂ O: Calculated ... C 61.1, H 5.51, N 8.91. Cl 7.53%; found .... C 61.1, H 6.26, N 8.87, Cl 8.26%.

4-Morpholinonaphthalic anhydride can be prepared in the following way: 83.1 parts of 4-bromonaphthalic anhydride and 103.2 parts of morpholine are heated ^{to 150 ° C. for 2 hours.} After cooling to 90 ^° C., 450 parts of water are added, the mixture is heated for a few moments, filtered in the heat in order to separate off the insoluble traces and the filtrate is acidified by adding 75 parts by volume of concentrated hydrochloric acid. The precipitate is filtered, washed with water until the bromine ions in the filtrate are removed, squeezed and dried. 84.7 parts of reaction material are obtained, which are recrystallized from acetic acid anhydride. The product thus obtained melts at 228 to 229 "C (above the Maquenne block).

Analysis for the gross formula C ₁₆ H ₁ , NO ₄ :
Calculated ... C 67.85, H 4.59, N 4.94%;
found .... C 67.8, H 4.22. N 4.79%.

The following table explains further examples of dyes which are produced by the method of Bei game 11 were made.

Table 2 example

12th 13th 14th 15th

16

17th

methyl
methyl
methyl
methyl

methyl
methyl

Siibstitucnt from Λ Substilucnt of B

5- or 4-morpholino 5- or 4-morpholino 5- or 4-morpholino (2,6-dimethyl) -5- or

4-morpholino 5- or 4-morpholino (2,6-dimethyl) -5- or

4-morpholino 5'-bromo
5'-Ch I or
5'-methyl
5'-methoxy

4'-methoxy
4'-Mcthoxv

Shades
on acrvlfiisers

vivid scarlet fever
lively cinnabar ■
lively coral
lively cinnabar

vivid scarlet fever
vivid scarlet fever

Claims (1)

Claim: Process for the preparation of canonical dyes of the Naphlhoylenhenzimidazol-Rcihe, S da lI u ι cli geke η η ζ eic Ii η c ι, dal or two hydroxyl groups, by one or two OY groups, where Y is an alkyl, aralkyl or aryl group, or is substituted by a tertiary amino group, in the presence of acetic acid or one of its higher homologues and \ on iron with one secondary amine of the general formula NO ₁ NHR