DE2050798C3 - Process for the production of anthraquinone - Google Patents

Description

in which the individual radicals R ₄ , R ₅ and R _{6 can be} identical or different and each represent a hydrogen atom or an aliphatic radical, and the two radicals R ₅ and / or the two radicals R _{6 can} each together designate an oxo group , and / or R ₄ and a radical R ₆ together for an optionally substituted alkylene radical with 2 to 8 carbon atoms or for a substituted methylene radical or, if the radicals R _{5 is} an oxo group and a radical R _{6 is} a hydrogen atom, for an unsubstituted one Methylene radical or both radicals R ₅ and one radical R ₆ or one radical R ₅ and both radicals R ₆ or both radicals R ₅ and both radicals R _{6 can} each together also mean an aliphatic radical, oxidized as starting materials.

The subject of the main patent 1 934 063 and the additional patent 2028 424 is a process / i-r production of anthraquinone by oxydauon of indanes of the general formula

in which R ₁ , R ₂ , R _{3 can be} identical or different and each represent an alkyl radical, R ₁ and / or R ₃ can also each denote a hydrogen atom, with oxygen in the gas phase in the presence of vanadium pentoxide and / or vanadates of elements of groups IVa, IVb, Vb, VIIa and VIII of the periodic table, optionally in a mixture with oxides of elements of groups IV to VI, a and b, VIIa and / or VIII of the periodic table, the reaction also in the presence of Vanadium-V compounds and additionally of compounds of potassium, boron, thallium and / or antimony, whereby the combination of vanadium (V) and antimony according to patent 1934063 is excluded, can be carried out according to patent 1934063 and patent 2028424, characterized that instead of the starting materials I diphenylimethane derivatives of the general formula

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in which R ₁ , R ₂ , R _{3 can be the} same or different and each represent an alkyl radical, R ₁ and / or R ₃ can also each denote a hydrogen atom, with oxygen in the gas phase in the presence of vanadium pentoxide and / or vanadates of elements of groups IVa, IVb, Vb, VIIa and VIII of the periodic table, optionally in a mixture with oxides of elements of groups IV to VI, a and b, VIIa and / or VIII of the periodic table, the reaction also in the presence of Vanadium V compounds and also compounds of potassium, boron, thallium and / or antimony, with the exception of the combination of vanadium (V) and antimony according to Patent 1934 063, can be carried out.

It has been found that the process of the main patent or the additional patent develop further if one uses instead of the starting materials I diphenylmethane derivatives of the general formula

R ₄

(H)

in which the individual radicals R ₄ , R ₅ and R _{6 can be} identical or different and each represent a hydrogen atom or an aliphatic radical, and the two radicals R ₅ and / or the two radicals R _{6 can} each together designate an oxo group , and / or R ₄ and a radical R «, together for an optionally substituted alkylene radical with 2 to 8 carbon atoms or for a substituted methylene radical or, if the radicals R _{5 is} an oxo group and a radical R _{6 is} a hydrogen

atom mean, can stand for an unsubstituted methylene _{radical or both radicals R 5} and one radical R ₆ or one radical R ₅ and both radicals R ₆ or both radicals R ₅ and both radicals R _{6 can} each together also mean an aliphatic radical, as starting materials oxidized.

Preferred starting materials il are those of the general formula II, in which the individual radicals R ₄ , R ₅ and R _{6 can be} identical or different and are each a hydrogen atom or an alkyl radical with 1 to 8, preferably 1 to 4, optionally substituted by chlorine atoms or bromine atoms Mean carbon atoms, in addition, the two radicals R ₅ and / or the two radicals R _{6 can} each together denote an oxo group, and / or R ₄ and one radical R ₆ together represent a group consisting of chlorine atoms, bromine atoms or an alkyl group with 1 to 3 Carbon atoms substituted methylene radical or an alkylene radical optionally substituted by chlorine atoms or bromine atoms with 2 to 8, or, if the radicals R _{5 is} an oxo group and one radical R _{6 is} a hydrogen atom, an unsubstituted methylene radical.

In the preferred starting materials, both radicals R ₅ and one radical R ₆ or one radical R ₅ and both radicals R _{6 can} each together be an alkylidene radical optionally substituted by chlorine atoms or bromine atoms and having 1 to 8, preferably 1 to 4 carbon atoms, which is linked to one of the two adjacent carbon atoms is connected via a double bond, or both radicals R ₅ and both radicals R ₆ together can also be an alkylidene radical optionally substituted by chlorine atoms or bromine atoms with 2 to 8, preferably 2 to 4 carbon atoms, which is connected to both adjacent carbon atoms a double bond is linked, denote. The radicals mentioned can be straight-chain or branched. If both radicals R _{5 are} alkyl radicals, R ₄ denotes in particular a hydrogen atom. If one radical R _{6 is} an alkyl radical, the other radical R _{6 is} preferably a hydrogen atom. The aforementioned radicals can also be replaced by groups and / or atoms which are inert under the reaction conditions, e.g. B. oxo groups, alkoxy groups, alkyl groups each having 1 to 3 carbon atoms may be substituted.

For example, the following compounds are suitable as starting materials II: 2-formyl, 2-isopropyl, 2-ethyl- and preferably 2-methyl-benzophenone; 2-isopropyl-, 2-ethyl-, 2-formyl- and preferably 2-methyl-diphenylmethane and corresponding ones on the methylene member by a methyl or propyl group substituted homologues; 2-chloro, 2-methoxy, 2-methoxyethyl, 2-ethyl-1-oxo-3-phenylindane and preferably the unsubstituted I - oxo - 3 - phenylindane, 2-methyl- or 2-bromo-1-oxo-3-phenylindane; 2-methyl, 3-methyl, 2-isopropyl and preferably l-methyl-3-phenylindene; 2-ethyl, 2,3-diethyl, 4-methyl, 4-propyl, 2,3-dimethyl, 2,4 - dimethyl, 3 - methyl - 4 - ethyl -1 - phenyltetralin and preferably 1-phenyltetralin; 1-phenylnaplithalin and its 2-chloro, 2,3-dimethyl, 4-ethyl derivatives; l-Phenylindene- (l) and its 3-methyl, 2-methyl compounds.

The starting materials II can be prepared in a known manner, for. B. 2-benzyltoluene by reaction of benzyl chloride and toluene (Ber. 6 [1873], 906), l-oxo-3-phenylindane by reaction of trans-cinnamic acid and benzene (J. Amer. Chem. Soc. 65 [1943], 59), 1-phenyltetralin from styrene by thermal dimerization (J. Amer. Chem. Soc. 90 [1968], 1289), 2-methylbenzophenone by reaction of benzene and o-toluic acid chloride (Ber. 24 [1891], 2805), l-oxo-2-methyl-3-phenylindene by reaction of 2-methyl-3,3-diphenyl acrylic acid (J. Amer. Chem. Soc. 67 [1945], 430), l-oxo-2-bromo-3-phenylindane by bromination of l-oxo-3-phenylindane (Monthly. 48 [1927], 342), 2-MethyI-1-phenylindene from / i-Methy] -} '- phenyl-cinnamon alcohol (Ber. 55 [1922], 3414). The homologues of the starting materials mentioned can be obtained in an analogous manner.

Otherwise, the process is under the conditions of the process according to the main patent or of the additional patent carried out, in particular with regard to the conduct of the reaction, catalyst preparation and -Composition and beneficial use of

ίο Catalysts containing vanadium pentoxide spherical carriers by a flame spraying or plasma spraying process, e.g. B. after in the German patent application P 20 25 430.2 described method.

The parts listed in the examples mean Parts by weight. They relate to parts of volume like kilograms to liters.

Example la

100 parts of powdered vanadium pentoxide are mixed with a solution of 7.85 parts of antimony trichloride mixed homogeneously in 0.5 parts of concentrated hydrochloric acid, neutral with concentrated ammonia solution placed and evaporated to dryness. Then smoke is taken with concentrated nitric acid to avoid the Drive off ammonia as ammonium nitrate. After smoking, the mass is melted and powdered. From the powdered mass, 10.0 parts to 90 parts of silicon carbide balls are made using a flame spray device applied from 4 to 6 mm in diameter.

Example Ib

48 parts of the catalyst prepared according to Example 1 a are placed in a tubular reactor (21 mm inner Pipe diameter). Now a mixture of 147,000 vol. To divide air and 5.6 parts l-methyl-3-phenylindene every hour through the catalyst directed. The tube wall temperature is 375 ° C., the temperature inside the catalyst layer 424 "C. The gaseous reaction mixture leaving the reactor is cooled to 50 ° C., with the end product and the unreacted 1-methyl-3-phenylindene condense. The uncondensed portion is washed with water. After evaporation of the wash water, the remaining residue is combined with the condensate.

The following results are obtained:
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Starting material l-methyl-3-phenylindene 9.8 parts

Exhaust gas quantity 264,000 parts by volume

Content of the exhaust gas
Carbon mono and

-dioxide 2.2 percent by volume
Raw end product 7.8 parts

In the raw end product, the following are determined by UV absorption:

69 percent by weight

Anthraquinone = 5.38 parts.
20 percent by weight

Phthalic anhydride = 1.56 parts.

(corresponds to an anthraquinone yield, based on the starting material used, of 55% of theory).

Example 2

48 parts of the catalyst prepared according to Example 1 a are placed in a tubular reactor (21 mm inner Pipe diameter). Now there is a mixture of 109,000 parts by volume of air and 5.1 parts l-oxo-3-phenylindane every hour through the catalyst directed. The pipe wall temperature is 418 C. the temperature inside the catalyst layer 445 "C. The gaseous state leaving the reactor The reaction mixture is cooled to 50 ° C., the end product and the unreacted i-oxo-3-phenylindane condense. The uncondensed portion is washed with water. After evaporation of the wash water, the remaining residue is combined with the condensate.

The following results are obtained:

Starting material 1-oxo-

3-phenylindane 10.2 parts

Exhaust gas quantity 218,000 volumetric parts

Content of the exhaust gas of carbon mono- and

-dioxide 2.8 volume-

Raw end product.

percentage
8.1 parts

In the raw end product, the following are determined by UV absorption:

50.4 percent by weight
Anthraquinone = 4.08 parts.

25 percent by weight

Phthalic anhydride = 2.02 parts.

(corresponds to an anthraquinone yield, based on the starting material used, of 40% of theory).

Example 3

48 T ^ iIe of the catalyst prepared according to Example 1 a are filled into a tube reactor (21 mm tube diameter). Now it becomes a mixture of 148 0 (X) parts by volume of air and 5.5 parts of 1-phenyl-naphthalene passed hourly through the catalyst. The pipe wall temperature is 4 (X) C. die Temperature inside the catalyst layer 450 ° C. The gaseous reaction mixture leaving the reactor is cooled to 50 ° C., with the end product and condense the unreacted l-phenyl-naphtha! in. The uncondensed portion will washed with water. After the washing water has evaporated, the residue that remains is with the condensate combined.

The following results will be obtained:

Starting material 1-phenyl-

naphthalene 11 parts

Exhaust gas quantity 296 (X) O parts by volume

Content of the exhaust gas

Carbon mono and

-dioxide 3.S volume percent
Raw end product 7.0 parts

In the raw end product, the following are determined by UV absorption:

40 percent by weight

Anthraquinone = 2.8 parts.
31 percent by weight

Phthalic anhydride = 2.17 parts.

(corresponds to an anthraquinone yield, based on the starting material used, of 25% of theory).

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Claims (1)

Claim: Further embodiment of the process for the production of anthraquinone by oxidation of Indanes of the general formula (Π) 45