DE2103360B - - Google Patents

Description

at 20 to 25 ° 13 parts of anthraquinone, the mixture is heated to 45 ° and stirred for 6 hours. sales is 25% · The obtained 1-nitroanthracbinone contains only traces of dinitroanthraquinones.

Example 3

13 parts of anthraquinone are added to a mixture of 50 parts of 98% strength nitric acid at room temperature and 50 parts of 84% phosphoric acid entered. The mixture is heated slowly to 70 ° and stirred for 13 hours at this to Temperature. The anthraquinone dissolves completely in the reaction mixture during the reaction, however the 1-nitroanthraquinone crystallizes with a little dinitroanthraquinones, 2-nitroanthraquinone remains dissolved together with a large proportion of dinitroanthraquinone. The conversion is 50%. The isolated 1-nitroanthraquinone contains 3% anthraquinone and only traces of dinitroanthraquinones.

Example 4 _M

In a mixture of 22.4 parts of anthraquinone and 180 parts of 100% phosphoric acid are in the course 45 parts of 98% nitric acid were added over a period of 30 minutes. The mixture is heated to 45 ° for 16 hours After filtering through a G3 glass nutsche, as Washing with water and drying gives 20.5 parts of a product which is 90% 1-nitrcanthraquinone (70% of theory), 1% 2-nitrcanthraquinone,

1% anthraquinone

8% dinitroanthraquinones and

contains. _. . ,

example

22.4 parts of anthraquinone, 180 parts of 99.5% strength phosphoric acid and 36 parts of 98% strength nitric acid are used and heated 2? Hours at 45 ° according to the information in Example 4. The product obtained (17.2 parts) consists of 90% 1-nitroanthraquinone, 2% 2-nitroanthraquinone, 5% dinitroanthraquinones and 3% anthraquinone.

Example 6

The procedure is as indicated in Example 4, but 22.4 parts of anthraquinone and 180 parts 101.5% phosphoric acid and 36 parts 98% nitric acid heated to 45 ° for 18 hours. The yield is 22.6 parts of a product which, after drying, consists of 87% 1-nitroanthraquinone, 2.5% 2-nitroanthracbinone, 8% dinitroanthraquinones, 2% anthraquinone and 0.5% of other by-products

Example 7

The procedure is as indicated in Example 4, but 22.4 parts of anthraquinone and 180 parts are heated 99% phosphoric acid and 27 parts of 98% nitric acid for 16 hours at 45 °. After filtering and Drying, the yield is 18 parts of a product which is 90% 1-nitroanthraquinone, 8% dinitroanthraquinone and contains low levels of 2-nitroanthraquinone and anthraquinone.

The table below shows further examples of reaction conditions for the preparation according to the invention indicated by 1-nitroanthraquinone.

The yield given under (a) refers to that in a conventional manner by pouring Product obtained from ice that has more of / 3-nitro and dinitroanthraquinones is contaminated; the yield given under (b) relates to the significant purer product obtained by filtering the reacted mixture.

Teüe phosphoric acid Conc nitric acid Con Tempe time Molver Salts (a) sales volume (b) Anthra tration center rature in ratio Yield: Yield: ■ Rpi- chinone V tion hours Anthra Before Vt the DCl " 98 Vo chinone / theory theory game Parts 100 Parts 98 ⁰ C ENT, (Parts) 1-nitro V 1-nitro 20.8 101.5 98 45 16 anthra anthra 20.8 167 99.5 25th 98 45 16 1: 3.9 chinone chinone 8th 20.8 167 99.5 25th 98 45 18th 1: 3.9 46 40 9 20.8 167 100 33.4 98 45 18th 1: 5.3 60 50 10 20.8 167 100 20.8 98 45 18th 1: 3.3 74 71 11th 20.8 167 100 46 98 45 20th 1: 7.8 46 99 36 12th 20.8 167 101.5 41.8 98 45 16 1: 6.6 67 58 13th 20.8 167 100 41.8 98 45 20th 1: 6.6 (9) Well, SO < 70 50 62 14th 104 154 100 43.3 98 45 15th 1: 6.9 (9) NH ₄ NO ₃ 76 100 65 15th 104 836 100 210 98 45 16 1: 6.6 80 16 104 668 100 149 98 45 16 1: 4.72 75 65 65 17th 104 752 101.5 167 98 45 16 1: 5.3 56 48 18th 104 836 103.5 186 98 50 16 1: 5.9 68 63 19th 104 836 101.5 186 98 43 16 1: 5.9 69 63 20th 104 836 85 210 98 45 9 1: 6.6 75 65 21 104 836 101.5 210 98 45 11th 1: 6.6 75 66 22nd 13th 836 210 98 73 32 1: 6.6 73 40 66 23 52 50 75 60 20th 1: 6.6 (40) 73 95 68 24 418 74 1: 6.6 NH ₄ NO ₈ 25th 69 66

Claims (4)

2 103 380 1 2 Claims: The reaction temperature can be wide 1. Process for the preparation of 1-nitro range can be chosen. Thus between about 0 ° C anthraquinone by nitrating anthraquinone and the boiling point of the reaction mixture with nitric acid, marked under normal pressure and at higher temperatures that one ratures in the presence of phosphoric acid 5, for example up to 125 ° C, nitrating under increased pressure and the water content of the reaction can be nitrated. Anthraquinone is preferably at most 16% from 30 to 90 ^° C. and in particular from 40 to 70 ^° C. in the case of a mixture at the start of the reaction. 1-nitroanthraquinone converted. Since in the course of the 2. The method according to claim 1, characterized in that reaction water is formed, the reaction can indicates that the reaction mixture is no longer ok by adding more nitric acid, phosphoric acid, contains more than 5 percent by weight of water. Polyphosphoric acids and / or phosphorus pentoxide 3. The method according to claim 1, characterized in that they are accelerated. draws that at temperatures between 30. The reaction mixture can be heated as long as and 9O ⁰ C nitrided. until a complete or almost complete 4. The method according to claim 1, characterized in that the anthraquinone is set, but it is also draws that per mole of anthraquinone min- in some cases advantageous to undermine the reaction Break 1 mole and preferably 10 to 40 moles, e.g. if 50 to 90% of the used Phosphoric acid and at least 1 mole and preferred anthraquinone have reacted. In the latter wise 3 to 13 moles of nitric acid are used. In the case, the 1-nitroanthraquinone obtained is separated so off and use the filtrate for a new approach, possibly after the original consignment It is known to restore 1-nitroanthraquinone by nitration centering on nitric acid and phosphoric acid of anthraquinone with nitric acid. Made in. The presence of sulfuric acid results in larger quantities. The reaction product can be iso- Amounts of by-products, mainly dinitroanthra- »5 are lated, z. B. by filtering off after cooling quinone in addition to 2-nitroanthraquinone. In addition, the reaction mixture remains. If so desired, it can a certain amount of anthraquinone not reacted can be washed with water and dried. It back. The purification of the 1-nitro thus obtained consists predominantly of 1-nitroanthraquinone and Anthraquinone is cumbersome and makes it more expensive. Contains at most small amounts of the starting product drive. 30 and by-products. It has now been found that 1-nitroanthra- It was not to be expected that the addition of phosphorus quinone in particular purity and in particular in phosphoric acid in the nitration of anthraquinone would lead to useful results in an economical way by nitrating anthracite, since in K i r k- quinone can be made with nitric acid if one o t h m e r, Encyclopedia of Chemical Technology 9, nitrated in the presence of phosphoric acid and the 35 p. 317, the addition of phosphoric acid generally not Water content of the reaction mixture is recommended for reaction start is a maximum of 16%. Those obtained in U.S. Patent 2,874,168 The phosphoric acid is particularly useful in results could not be confirmed by the inventor Amounts of at least 1 mole and preferably of. This is in line with H ο u b e n- 10 to 40 mol, based on 1 mol of the 40 W e y 1 to be nitrated, "Methods of Organic Chemistry", Vol. X / l Anthraquinones, used. It preferably contains (1971), p. 614. more than 61% PsO ₈ (whereby the acid content of the Phos- The parts mentioned in the examples are weight phosphoric acid is calculated as P ₂ O ₅ content), in particular parts and percentages percentages by weight. The tempe- more than 70% P ₂ O ₅ . (Percent is given here and in temperatures are in degrees Celsius, understood the following weight percent.) You can 45. thus also polyphosphoric acids and phosphorus pea oxide Example 1 use. 13 parts of anthraquinone and 100 parts of crystallized, Nitric acid, 98% phosphoric acid, is preferably used as the nitrating agent and is heated together to 45 ° in amounts of at least 1 mol, particularly advantageously. At this temperature, 20 parts of 98% strength nitric acid and 8 moles, based on 1 mole of anthraquinone, are used within from 3 to 13 moles and in particular from 4 to 50 30 minutes. 0.5 part of sulfur trioxide was added. After 24 hours of stirring at 40 to 45 °, it is particularly advantageous to use thin-layer chromatography, in particular 95 to 98 percent nitric acid, to graphically demonstrate that the conversion to 1-nitro is used. Also 40 to 90 percent nitric acid anthraquinone is made to about 50%. This can be used, but if the reaction mixture is used in this case to cool to 25 °, the highly concentrated phosphoric acid or P ₂ O _{5 is} sucked off. To divorced product, wash it with water until place of nitric acid can also be water-soluble, the filtrate is neutral, and dry it. It contains nitrates, e.g. B. ammonium nitrate, used as nitrating agent 96% 1-nitroanthraquinone and 4% anthraquinone. be turned. The yield is 7 parts. The filtrate contains Furthermore, the reaction mixture can contain sulfuric acid 60 anthraquinone in addition to a little 1-nitroanthraquinone. It contain. This can be used as such or in the form of can be reused after going through SO ₃ or alkali metal sulfates, for example Na ₈ SO ₄ , addition of polyphosphoric acid with a P ₂ O ₅ -Ciie- in amounts of about 0.01 to 0.1 mol and in particular from 83 to 84%, the water content is kept to the low from 0.03 to 0.05 mol, based on 1 mol of anthracite, has brought the initial value. quinone, may be added. SO ₃ can also be used as a di- 65. . methylformamide-SO ₃ complex are added. Example 2 At the start of the reaction, the reaction mixture contains a mixture of 100 parts of 98% phosphorus preferably no more than 5% water. acid and 30 parts of 98% nitric acid carry niian