DE2436459A1 - PROCESS FOR THE PREPARATION OF 1,4 DIAMINO-5-NITROANTHRAQUINONE - Google Patents

Description

GIBA-GEIGY

CLBA-GEIGY AG, CH-4002 Basel
Case 1-8908 24 3 6 £ 45

Germany

DR. BERG DIPL.-ING. STAPF DIPL.-ING. SCHWABE DR. DR. SANDMAIR

PAT & NTANWÄLTE
6 MÖNCHEN 80 · MAU ER-KIRCHERSTR. 45

Lawyer File 25 107 July 29, 1974

Process for the production of l ^ -Diamino-S-nitroanthra-

chinone.

The present invention relates to a process for the preparation of 1,4-diamino-5-nitroanthraquinone by nitration of 1,4-diaminoanthraquinone with mixed acid via the intermediate stage of 1,9-4,10-anthraquinone disulfonimide

ORIGINAL INSPECTED

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CIBA-GEIGY AG

243645S

using sulfur trioxide as a masking reagent to form the 1,9-4,1O-anthraquinone disulfonimide in organic solvents which are inert to sulfur trioxide and mixed acid.

j The process runs according to the following reaction step scheme

away.

0 NH

so, SO ₀ / \ ² / \ ² 0 N 0 N

0 NH,

NO ₂ ; 0 H

SO ₀

NO ₂ 0

The 1,4-diamino-5-nitroanthraquinone is a valuable one purple dye.

The procedure according to the cited reaction level scheme is known and was, for example, in the BIOS Final Report No. 1484 p. 20.

In order to mask the amino groups of the 1,4-diaminoanthraquinone, oleum has hitherto been used.

[After the subsequent nitration with mixed acid the disulfonimide protective groups formed as intermediates are cleaved again by means of sulfuric acid '.'hydrolytically'.

] The nitration of 1,4-diaminoanthraquinone to '-1,4-diamino-5-Ni tr oanthraquinone according to this known

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ORIGINAL SNSrECTED

CIBA-GEIGY AG _ 3 ~

.: · '■■ 243645S

However, the process requires large amounts of sulfuric acid or oleum, partly as a reaction medium and partly as i masking reagent are used. !

; According to the BIOS Final Report, the following amounts of sulfuric acid or oleum are required for a batch of 100 kg of 1,4-diaminoanthraquinone.

a) As a solution medium for 1,4-diaminoanthraquinone and as a masking reagent for the formation of 1,9-4,10-anthraquinone disulfonimide 700.0 kg of oleum 657o ig. . j

. ■ · "■ · i

b) To dilute the reaction medium after the masking reaction: 293.0 kg of H ₂ SO ₄ 78% strength. ^v · '|

c) 86.5 kg H ₂ SO, 100% in the form of mixed nitration

j acid with 28% NHO ₃ content. . _;

'd) For washing the 5-nitro-1,9-4,10-anthraquinone disulfonimide 330.0 kg H ₂ SO ₄ 387o-ig. . 1

If the SO ₀ content of the oleum is converted into sulfuric acid, ι. 3 *

so on the above 100 kg batch for the first two • stages of the process 1'160.0 kg of sulfuric acid are required.

j borrowed. ' ^: j'

j Since this process sulfuric acid after completed Re-;

j i

, cycle of action only recycled in the most recent cases.

j should be barely, it represents a significant ecological problem. _v . .

In addition, for commercial reasons, the aim is to use

I I

^; basic media, which are absolutely necessary for a reaction, are small

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ORIGINAL INSPECTED

CIBA-GEIGYAG - 4 - "■

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III * *

<I ■

to keep.

It has now been found that when using liquid sulfur trioxide as a masking reagent for the 1,4-diaminoanthraquinone in inert organic solvents as

Reaction medium, surprisingly, considerably lower , Amounts of waste sulfuric acid are produced as known

Procedure.

, The effect is so severe that over 60% of the normal necessary sulfuric acid can be saved '.

• There is another major advantage of the new procedure

• in that the masked nitration product is insoluble in the reaction medium. This brings reaction kinetic advantages and enables an exact separation of the product from the reactants without having to use any phase-changing auxiliary, such as water. This will easily way directly pro- receive domestic product and also the regeneration of the _reaction: media much easier.

i The new process for the production of 1,4-di-

i '

j amino-5-nitroanthraquinone from 1,4-diaminoanthraquinone

j by nitration with HNO ₃ / H ₂ SO, mixed acid whereby before the

i nitration masking the two amino groups

I 1,9-4,10-anthraquinone disulfoniraid takes place, which after which is hydrolytically decomposed again by nitration

509808/109 1 original inspected

CIBA-GEIGYAG - 5 -

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characterized in that the masking of the 1,4-diaminoanthraquinone zum! ^^, IQ-anthraquinone disulfonimide Carries out with liquid sulfur trioxide and as a reaction medium for carrying out the entire nitration process liquid solvents used against the re-

; actands are inert.
The raw material can be both pure and technical

• 1,4-diaminoanthraquinone can be used.

Inert organic solvents which come into consideration as the reaction medium are those which are used in the

! applied reaction temperatures are liquid, or by the cryoscopic temperature decrease in the reaction

: mass become liquid and do not enter into any chemical reaction with sulfur trioxide and mixed acid.

Preferred liquid, inert solvents are those which have at least one -SO ^ group in the molecule, such as dimethyl sulfate, sulfolane, dimethyl sulfone, diethyl sulfone, tetramethylene sulfone, hexamethylene

i sulfone, methylethyl sulfon etc.

The method j according to the invention is advantageously carried out as follows.

The solvent is placed in the reaction vessel, using amounts which are 4 to 8 times greater in volume than the 1,4-diaminoanthraquinone to be nitrated. Then liquid sulfur trioxide is poured into the solution

' medium dosed. ~ - -

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ORIGINAL INSPECTED

CIBA-GEIGYAG - 6 -

The amount of sulfur trioxide must be at least 4 moles based on one mole of 1,4-diarainoanthraquinone and should not exceed 8 moles. During this operation the temperature rises adiabatically to 30-40 ° C, which is not critical; represents value. The temperature may also rise to 60-65 ° C, for example. Subsequently, the 1,4-diaminoanthraquinone is introduced in portions with stirring so that the temperature does not exceed 80 ⁰ C.

Temperatures between 50 and 65 ⁰ C. Advantageously, the reaction mass is then stirred for some time depending on the batch size of between 2 to 8 hours ^ at said temperatures and then cooled to about 20 ⁰ C.

The subsequent nitration takes place with so-called "mixed acid ¹¹ as used in technology for nitriding

, rungsreaktion is used. A mixed acid with 50% HNO ₃ and 50% H ₂ SO ₄ content and an HNO excess to the theoretically required amount of 25-50% is common and advantageous. ■.

Other mixed acids can also be used, for example with HNO ^ contents between 20 and 80%. at j low HNOo concentrations, the nitration

I ■. * ■

j action, however, falls too slowly, too stormy if it is too high.

The mixed acid is added continuously at such a rate that the reaction temperature is 25.degree ; does not exceed, possibly being cooled

tv.

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■. ORIGINAL INSPECTED

CIBA-GEIGYAG

After the addition of mixed acids has ended, stirring is continued for some time, usually between 2 to 8 hours.

The 5-nitro anthraquinone-1,9-4,10-disulfonimide formed during the reaction is insoluble in the reaction medium and crystallizes out.

It is separated from the reaction medium by suction filtration or other separation processes, with water washed neutral and dried.

The 1,4-diamino-5-nitroanthraquinone is converted from the 5-nitroanthraquinone-l, 9-4,10-disulfonimide using a known method, e.g. by saponification with 96% sulfuric acid

. 120 ⁰ C won.

The yields are between 70 and 80%. ·

The following table comparison of the implementation

. steps up to 5-nitro-l, 9-4,10-anthraquinone disulfonimide illustrates the difference between known processes and the process according to the invention in relation to the process to be used or the sulfuric acid solution, where S0 ~ values were in each case converted to H ₂ SO. It is here-

j for a batch with 100 kg of 1,4-diaminoanthra

chinone. . ;

- - ORIGINAL INSPECTED

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cn

co

OO O

OO

co

I NAOHi? «- ^. E! CHTJ

BIOS - 1Λ-diamino
anthraohinone procedure 100 kg 500 kg SO kg 175 .0 kg Inventor procedure - with SO ¹ SO ₃ kg H SO ₁
2 4 kg 200 kg 325.O kg 70 .0 kg c) mix. 50Ji 100 kg 99.3 kg 184.1 a) Oleum 65 # 293 kg 130.0 228 .5 kg d) washing acid & Q% 218.0 120 kg 86 .5 kg a) oleum 65 % - Bound SO 283.5 kg kg b) H ₂ SO ^ 785 « 330 kg 125 .5 kg SO (as disulfone) 218.0 kg 36.8 kg c) mix. 28 # ENT kg kg I27.I d) washing acid 38 # -67.O Total sulfuric acid 73.6 kg -67.O - Bound SO kg. - ^ 75 .0 kg 211.8 kg kg = kg (as disulfone) 388.O 1160 .0 kg 250.3 = 303.0 kg 65I.O • Total sulfuric acid

oc

ω m 3

CO co

cn co

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After the separation of the 5-nitro-l, 9-4,10-anthraquinone disulfonimide the mother liquor can be worked up by distillation. Fractions of nitric acid are obtained, the solvent used and a residue of predominantly sulfuric acid and impure by-products contains and which can be processed ecologically harmless. The regenerated solvent can be used without further be reused.

In the examples below, the parts mean, unless otherwise stated, parts by weight, the Percentages by weight and temperatures are given in degrees Celsius. Between weight and volume ; divide is the same ratio as between grams and cubic centimeters.

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ORIGINAL INSPECTED

CIBA-GEIGYAG - IC - example 1

60 g of sulfur trioxide are added dropwise in 150 g of sulfolane within 15 minutes. The temperature is am Final 30-40 °. 23.8 g of 1,4-diaminoanthraquinone are added with stirring closed, holds 4 hours at 60-65 ° and then cools down to 20-25 °. At this temperature, 16.5 g of mixed acid are obtained a 50% added within 2 hours and stirred for a further 4 hours. The precipitated crystallized 5-nitro-1,9-4,10-anthraquinone disulfonimide is filtered off, washed with water and dried. The yield is 74.5% the theory. The 1,4-diamino-5-nitroanthraquinone is made from the nitroanthraquinone disulfonimide according to a known method, e.g. by saponification with 96% sulfuric acid at 120 °, won.

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ORIGINAL INSPECTED

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Example 2 ^;

* Add 60 g of liquid to 100 g of dimethyl sulfone Add dropwise SO- at 40-50 °. Little by little one emerges tangible mixture. 23.8 g of 1,4-diaminoanthraquinone are added with stirring, holds for 4 hours at 60-65 ° and then cools the reaction mixture down to 20 °. Then, within 2 hours, 27.5 g of mixed acid with 307% HNO ^ content are added dropwise. The nitration is done through 4 hours of stirring at 20-25 ° completed. That 5-nitro-1,9-4,10-anthraquinone disulfonimide formed and precipitated in crystalline form is then suctioned off with water

Washed neutral and dried. The yield is 78% of theory.

The 1,4-diamino-5-nitroanthraquinone is known Method by hydrolysis of the disulfonimide groups in 96% -. iger sulfuric acid obtained.

; Example 3

ι · —————————. ,

ι ■ ■:

j Used instead of sulfolane or dimethyli sulfone "corresponding amounts of dimethyl sulfate as organic

! ULTRASONIC solvent and the procedure is otherwise as described in the \ Examples 1 and 2, there are likewise obtained

ι ·

a very pure product in 80% yield.

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ORIGINAL INSPECTED

Claims (3)

Claims 1. Process for the preparation of 1,4-diamino-5-nitroanthraquinone from 1,4-dianiinoanthraquinone by nitration with HNO- / H ^ SO, mixed acid before nitration a masking of the two amino groups to 1. 9-4.10 ~ anthraquinone disulfonimide takes place, which is hydrolytically split again after the nitration, thereby marked, that the masking of 1,4-diaminoanthraquinone to 1,9-4,10-anthraquinone disulfonimide with liquid Performs sulfur trioxide and liquid as the reaction medium for carrying out the entire nitration process Solvents used which are inert to the reactants. 2. The method according to claim 1, characterized gekennzeich-.net that such inert, liquid, organic solvents are used, which in the molecule at least one -S0 _? - Have group. ; 3. The method according to claim 1 and 2, characterized I draws that one is considered an inert, liquid, organic solvent Dimethyl sulfate, sulfolane, dimethyl sulfon, Methyl ethyl sulfone, diethyl sulfone, tetramethylene sulfone, Hexamethylene sulfone is used. 509808/1091