DE1058661B - Process for the chlorination of cyclic compounds containing ring-shaped bonded carbonyl groups - Google Patents

Description

Many processes are already known which involve the introduction of halogen atoms into organic compounds allow. These known methods mostly use free halogen, e.g. chlorine or products like sulfuryl chloride, which behave like a mixture of sulfur dioxide and free chlorine however, in many cases considerable disadvantages, for example by the reaction on a large scale Scale progresses very slowly or by by the free halogen or by itself during the reaction evolving hydrogen halide a considerable attack on the equipment used takes place, in particular if the halogenation is only desired under relatively severe conditions Sense runs. In addition, because of the volatility of these common halogenating agents, it is an accurate one Dosing is associated with difficulties; in many cases the halogenation must be prolonged Control to be kept. The halogenation products from different approaches of the same The composition of the starting materials often differs from one another.

It has now been found that cyclic compounds containing ring-shaped carbonyl groups, which contain at most seven optionally condensed benzene nuclei, can advantageously be chlorinated if they are heated in an anhydrous chlorinating agent which, on the one hand, contains chlorides of the Friedel-Crafts type and, on the other hand, anhydrous sulfur trioxide Sulfuric acid or compounds of the general formula R — SO ₂ —halogen, in which R is one of the groups —OH, —O — metal or an organic radical.

The compounds to be subjected to chlorination and serving as starting materials for the present process should have a cyclic character and have carbonyl groups in the ring. Lots of these connections can be linked or have the character of a vat dye. Among the not Connectable compounds of this type are, for example, phthalic anhydride and its substitution products. As linkable connections that Benzoquinone, naphthoquinone, and anthraquinone can, for example, have no vat dye character and their substitution products, for example anthraquinone monosulfonic acids and the most diverse Anthraquinone disulfonic acids can be used; also oxyanthraquinones, nitroanthraquinones, Aminoanthraquinones and anthraquinone carboxylic acids and benzanthrone.

Among the actual vat dyes, pyrazole anthrones, Anthrapyrimidines, 1,2,5,6-Di- (2'-phenylthiazole) -anthraquinones, anthraquinone acridones, such as anthraquinone-l, 2-benzacridone or naphthacridone, Process for the chlorination of cyclic, ring-shaped carbonyl groups

containing compounds

Applicant: CIBA Aktiengesellschaft, Basel (Switzerland)

Representative: Dipl.-Ing. E. Splanemann, patent attorney, Hamburg 36, Neuer Wall 10

Claimed priority:

Switzerland from March 18, 1955

Dr. Armin Caliezi, Basel,

Dr. Walter Kern, Sissach,

and Dr. Theodor Holbro, Basel (Switzerland),

have been named as inventors

Dianthrimides and the carbazoles obtainable from them, condensation products of cyanuric chloride and aminoanthraquinones, Indanthrone, dibenzpyrenquinone, antanthrone, Flavanthrone, acedianthrone and the a, / S-bis (anthronylidene) ethane used as a starting material as well as derivatives of the abovementioned basic bodies are also mentioned. There are also vat dyes the indigo series such as indigo itself, thioindigo and their substitution products as well as bisl, 2, l ', 2'-naphthionaphthene indigo into consideration.

The chlorides of the Friedel-Crafts type are primarily the chlorides of iron and aluminum, e.g. aluminum chloride and iron (III) chloride can be considered.

For example, chlorosulfonic acid and fluorosulfonic acid and their metal salts, for example the sodium salts, can be used as compounds of the general formula R — SO _{2 —halogen.} Surprisingly, simple organic sulfonic acid chlorides which themselves cannot easily be chlorinated, in particular alkanesulfonic acid chlorides such as methanesulfonic acid chloride, act in a similar way. As a rule, sulfur trioxide or sulfur trioxide containing large amounts of sulfuric acid (oleum) or anhydrous sulfuric acid can also be used.

909 529/393

Acid can be used in the same way, especially when there is a possibility under the reaction conditions that compounds of the above formula R — SO ₂ —halogen are formed therefrom.

In many cases it is expedient to use the anhydrous chlorinating agent of the composition mentioned add substances that cause a lowering of the melting temperature, for example Sodium chloride, sodium fluoride, calcium chloride, potassium chloride, sulfur dioxide, sodium sulfite and Magnesium sulfate.

The chlorinating agent can be obtained in a simple manner by mixing the substances mentioned together, it being left open in individual cases to what extent a mutual reaction takes place between the mixing partners before the chlorination reaction occurs. In many cases it is expedient to add the compounds of the formula R — SO ₂ —- halogen (especially chlorosulfonic acid) or SO ₃ or oleum to the solid or molten chloride of the Friedel-Crafts type (eg aluminum chloride), as this is common in this way the stirrability of the melt is increased. In many cases it is also possible to introduce the compound to be chlorinated in a melt of a chloride of the Friedel-Crafts type, expediently prepared with the substances mentioned above, and _{to add the sulfur trioxide or the compounds of the formula R — SO 2} —halogen as the last component .

The chlorination should be carried out in an anhydrous medium. The temperatures to use generally depend on the temperature at which the chlorinating agent still has a forms stirrable melt. Temperatures of over 50 ° C. are advantageously used, the temperature as required up to significantly above 100 ° C., for example about 120 to 160 ° C., or individually Cases can also be increased above 200 ° C.

Surprisingly, the present process can be conducted in such a way that, despite the presence of strongly sulfonating compounds, practically no entry of sulfur or sulfonic acid groups into the molecule takes place. The fact that the sulfur trioxide or the compounds of the formula R-SO ₂ -halogen play an essential role in carrying out the chlorination reaction is evident from the fact that in general there is _{one chlorine atom per molecule of R-SO 2} -halogen in the compound to be chlorinated is introduced.

The reaction mechanism of the chlorination should be formulated via a complex salt formation according to equations (1) and (Z); however, the invention is in no way intended to be bound by any theory.

RSO ₂ Cl + AlCl ₃ - * - [AlCl ₃ · RSO ₂ ] ⁹ C1® (1)

[AlCl ₃ · RSO ₂ ] ³ Cl ³ + X - H - »-

- »- [AlCl ₃ · RS0 ₂ ] ^e H® + X-Cl, (2)

where R is one of the groups —OH, —O - metal or an organic radical and X —— H is the compound to be chlorinated. When using SO ₃ , the following primary reaction must be carried out

SO ₃ + Al Cl ₃ -

(3)

AICI ₂ OSO ₂ Cl,

the reaction scheme given then applies to the further stages.

The explanation for sulfuric acid is somewhat more difficult. It is assumed that some of the sulfuric acid in the aluminum chloride _{melt splits into SO 3} (+ H ₂ O), so that the SO _{3 released} would bring about the chlorination.

Since in the reaction carried out in anhydrous, liquid chlorinating agent, free chlorine is practical does not occur, the reaction can generally be carried out with considerable sparing of the apparatus will. It is also advantageous that in many cases the chlorination is completed in as little as 1 to 2 hours.

If the molecule of the substance to be halogenated according to the present process is such, that a z. B. intramolecular condensation or some other type of ring closure, e.g. B. a carbazolation is possible, such a condensation or such a ring closure can be carried out in addition to the halogenation reaction in many cases.

Some of the products obtainable by the present process are known or are isomeric with known ones Products. However, you can use the present method in a particularly simple and reliable Way, while sparing the reaction vessels and in a very often surprisingly short time will. Some of the new products obtainable according to the present process are valuable Intermediate products or stand out, provided they have colorant character have, through various favorable properties, in particular good fastness properties, e.g. B. Wet fastness or light fastness.

From the reports of the Deutsche Chemischen Gesellschaft Vol. 60 (1927), p. 577, it is known that AlCl _{3 has a} halogenating effect on perylene in the presence of oxidizing agents. However, this method has the following disadvantages compared to the one according to the invention:

a) Manganese dioxide must be removed from the reaction product by a special operation (reduction) .

b) During the chlorination, chlorine gas is released, which leads to increased corrosion of the equipment.

c) The chlorination is less effective than the claimed method because it is per mole of aluminum chloride less chlorine is introduced into the compound to be chlorinated.

In the following examples, unless otherwise stated, the parts mean parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

example 1

A mixture of 80 parts of anhydrous aluminum chloride, 13 parts of sodium chloride, 0.8 parts Sodium fluoride and 5 parts of chlorosulfonic acid are heated to 140 ° C. until a clear melt has formed is. The temperature of the melt is then lowered to 90 ° C. and 5 parts of the are carried through alkaline condensation from Bz-1-anthraquinonylamino-benzanthrone obtained dye. The mixture is stirred for 1 hour at 90 to 95 ° C. and the melt is carried on ice and water. The aqueous mixture is acidified with hydrochloric acid, heated for 1 hour and filtered. The neutral washed and dried dye stains cotton from the vat strong blue-green with very good fastness properties. Its chlorine content is 26.9%.

A similar product is obtained if the chlorosulfonic acid in the above example is replaced by fluorosulfonic acid is replaced.

Example 2

To a melt of 80 parts of aluminum chloride, 13 parts of sodium chloride and 0.8 parts of sodium

fluoride are given at 90 ° C 5 parts of the example 1 dye used and then slowly dropwise 2 parts of methanesulfonic acid chloride. Man The mixture is stirred at 90 to 92 ° C. for 1 hour and worked up as indicated in Example 1. One he S holds a sulfur-free dye with a chlorine content of 11.5%. He dyes on cotton from the Vat a strong dark olive with very good fastness properties.

Example 3

To a liquid melt of 100 parts of aluminum chloride, 20 parts of sodium chloride and 17.5 parts of chlorosulfonic acid carry 10.4 parts of anthraquinone at 120 ° C a. Then the mixture is heated to 200 ° C within 2 hours and one hour at stirred at this temperature. After the usual work-up, a sulfur-free product is obtained which contains about 24% chlorine.

Example 4

90 parts of aluminum chloride, 13 parts of sodium chloride, 0.9 parts of sodium fluoride and 19 parts of chlorosulfonic acid are heated together to 150 ° C until a clear melt has formed. Then one lets the temperature of the melt drop to 125 ° C. and enter 11.9 parts of 1,4-diaminoanthraquinone. the Melt is stirred for a further 1 hour at 125 to 130 ° C and then, as indicated in Example 1, worked up. A sulfur-free product with a chlorine content of about 31% is obtained.

Example 5

11.3 parts of α-aminoanthraquinone are added at 130 ° C. to a melt used as in Example 4 and then the mixture is stirred for 1 hour at 130 to 135 ° C. After work-up, it is obtained one 12.2 parts of a chlorine-containing product that does not contain sulfur.

Example 6

A mixture of 80 parts of aluminum chloride, 13 parts of sodium chloride, 0.8 part of sodium fluoride and 7.5 parts of chlorosulfonic acid are heated to 140 ° C until a clear melt has formed. This is cooled to 110 ° C and 5 parts of acedianthrone are entered. The mixture is stirred at 110 to 115 ° C. for 1 hour and works up the reaction mixture as usual. The sulfur-free product obtained has a Chlorine content of around 20%.

Sodium fluoride and 3.68 parts of chlorosulfonic acid are added to 5 parts of the dye of the formula at 80.degree

Example 7

To a liquid melt of 80 parts of aluminum chloride, 13 parts of sodium chloride, 0.8 parts Sodium fluoride and 5 parts of chlorosulfonic acid are added at 90 ° C. to 5 parts of 2,2'-dichloro-dianthrone-ethane (Condensation product of 2 moles of 2-chloro-anthrone (9) and 1 mole of glyoxal sulfate) and then stirred 1 hour at 90 to 95 ° C. After the usual work-up, a sulfur-free, strong, red-brown vat dye of the acedianthron type with a chlorine content of about 21%.

55

60

and stir the whole thing for 4 hours at 80 ° C. It is then heated to 120 ° C. in the course of 2 hours and then worked up as in Example 1. The strong yellow coloring of cotton has a Chlorine content of around 12%.

Example 9

To a melt prepared from 200 parts of aluminum chloride, 40 parts of sodium chloride, 2 parts of sodium fluoride and 40 parts of chlorosulfonic acid, 10 parts of N-dihydro-1,2,2 ', 1'-anthraquinone azine are added ^{at 140 ° C.} The mixture is stirred for 2 hours at 140.degree. C., then for 2 hours at 160.degree. C. and a further hour at 180.degree. C. The product is worked up as in Example 1. The moist suction filter is then stirred with 1000 parts of water, 6 parts of sodium hydroxide and 10 parts of sodium hydrosulfite for 20 hours at 20.degree. After isolation and drying, the dye has a chlorine content of about 32%.

Example 10

Into a melt of 125 parts of aluminum chloride, 25 parts of sodium chloride, 1.25 parts sodium fluoride, and 5.25 parts of chlorosulfonic acid are added at ^90: C. 5 parts of 3,4,8,9-dibenzpyrenequinone-5, 10, and stirred for 2V2 hours. at 90 ° C. and for a further 2½ hours at 120 ° C. After the usual work-up, a yellow vat dye with a chlorine content of about 15% is obtained.

Example 11

5 parts of thioindigo are added at 80 ° C. to a melt of 100 parts of aluminum chloride, 20 parts of sodium chloride and 7.9 parts of chlorosulfonic acid. The mixture is allowed to stir for 2 hours at 85.degree. C., 2 hours at 100.degree. C., 1 hour at 110.degree. C., V for ₂ hours at 120.degree. ^{C. and 1 1/2 hour at 140.degree.} After working up, a red-violet powder is obtained which has about 29% chlorine.

Example 12

200 parts of aluminum chloride, 40 parts of sodium chloride and 23 parts of chlorosulfonic acid are heated to 140.degree heated until a clear melt has formed. The melt is then cooled to 100 ° C. and 7.5 parts are added Dichloranthanthrone too. In the course of 2/2 hours, the temperature is increased to 140 ° C. and work is carried out as in example 1. The chlorine content of the product thus obtained is about 36%.

Example 13

Example 8 I ^ne i ^ne melt of 80 parts of iron (III) chloride,

20 parts of sodium chloride and 5 parts of chlorosulfone

7 parts of that in Example 1 are added at 160 ° C. to a melt prepared from 125 parts of aluminum acid minium chloride, 25 parts sodium chloride, 1.25 parts 70 of the dye used. The melt will

Stirred for 30 minutes at 160 ° C. and then poured into 500 parts of hot water. Once all the iron salt is in Solution is gone, the dye is filtered off. It contains about 23% chlorine.

5 Example 14

In a melt of 120 parts of anhydrous aluminum chloride, 25 parts of sodium chloride and 4.5 parts Sulfur trioxide 5 parts of the dye used in Example 1 are introduced at 100.degree. Man stirred for 1 hour at 95 ° to 105 ° C. and worked up as in Example 1. A dye, cotton, is obtained colors similar to that of Example 1 and contains about 25% chlorine.

Example 15

80 parts of aluminum chloride, 13 parts of sodium chloride and 6 parts of sulfuric acid are heated to 140.degree heated until a clear melt has formed. Then cool to 120 ° C and wear 5 parts of the example 1 dye used. The whole is stirred for 1 hour at 120 ° C and then as in Example 1 worked up. The product contains 10.6% chlorine.

Example 16

80 parts of aluminum chloride, 10 parts of sodium chloride and 7.15 parts of the sodium salt of chlorosulfonic acid are heated to 120 ° C until a liquid melt has formed. Then you admit this melt 5 parts of the dye used in Example 1 and heated the whole thing for 1 hour 120 ° C. Work up as in Example 1. The product contains 22.3% chlorine.

Claims (10)

Claims: 40 1. Process for the chlorination of cyclic, ring-shaped carbonyl groups containing Compounds which contain a maximum of seven optionally condensed benzene nuclei, characterized in that this is heated in an anhydrous chlorinating agent, which on the one hand Chlorides of the Friedel-Crafts type and on the other hand sulfur trioxide, anhydrous sulfuric acid or compounds of the general formula R-SO ₂ halogen contains, in which R is one of the groups —OH, —O— metal or an organic radical. 2. The method according to claim 1, characterized by the use of anhydrous aluminum chloride as a connection of the Friedel-Crafts type. 3. The method according to any one of claims 1 or 2, characterized by the use of Chlorosulfonic acid. 4. The method according to any one of claims 1 to 3, characterized in that one is in the presence Melting point depressants, especially inorganic melting point depressants Means, works. 5. The method according to any one of claims 1 to 4, characterized in that 1 mol Chlorosulfonic acid used at least 1 mole of aluminum halide. 6. The method according to any one of claims 1 to 5, characterized in that at temperatures of at least 50i ° C works. 7. The method according to claim 1 to 6, characterized in that such compounds chlorinated, which in addition to at least one aromatic nucleus have at least one heterocyclic ring. 8. The method according to any one of claims 1 to 7, characterized in that such Chlorinated compounds which have the character of a vat dye. 9. The method according to claim 8, characterized in that indigoid vat dyes subject to chlorination. 10. The method according to claim 8, characterized in that one anthraquinone vat dyes subject to chlorination. Considered publications:
Reports of the German Chemical Society, Vol. 60 (1927), p. 577. When the application was announced, a test report and a coloring table were displayed. © 909 529/393 5.59