CH470334A - Process for the preparation of polycyclic quinoid compounds - Google Patents

Description

  

  



  Process for the preparation of polycyclic quinoid compounds
The present invention relates to a process for the preparation of polycyclic quinoid compounds of the formula
EMI1.1
 in which Z denotes the atoms necessary to form an optionally substituted, unsaturated, mononuclear or polynuclear, carbocyclic or heterocyclic ring and the nucleus A is optionally substituted.



   The process is characterized in that a 1,3 diene, which consists of the atoms of Z, is attached to a dienophilic compound of the formula
EMI1.2
 added in 2,3-position according to Diels-Alder.



   The addition is expediently carried out at temperatures of 50 to 250.degree. C., preferably in the temperature range from 800 to 180.degree. C., in solution or suspension.



   The solvent or suspension medium used is water or inert, i.e. organic solvents which do not react with any of the reactants under the reaction conditions, e.g. aliphatic, optionally halogen atoms, hydroxyl groups, alkoxy groups or nitro groups, such as straight-chain or branched alkanes with about 6 to 12 carbon atoms (n-hexane, n-octane, n-decane, n-dodecane) or their mixtures, carbon tetrachloride, tetrachloroethane, n- or iso-amyl chloride, n-hexyl chloride, n- or iso-octyl chloride, alcohols (ethanol, n- and iso-propanol, n-, iso- and sec. butanol, n-, iso- and sec.



  Pentanol, n-hexanol, n- and iso-octanol, manufactured using the oxo process. Ullmann encyclopedia of techn.



  Chemie Vol. 3 p. 290 (1953) Kirk. Othmer Encyclopedie of Chem. Techn. Vol. 1 page 528 (1963), oxo-nonanol n- and oxo-decanol), alkoxyalkanes (di-iso-propyl ether, di-n-butyl ether, di-n- or -isoamyl ether , l-methoxypentane), nitro-alkanes (nitromethane, nitroethane, 1 or 2-nitro-propane), also alicyclic or arylaliphatic compounds (cyclohexane, methylcyclohexane, cyclohexanol, benzyl alcohol) and aromatic hydrocarbons, optionally containing halogen atoms, alkyl groups, alkoxy groups or nitro groups (Benzene, toluene, xylenes, trimethylbenzenes, ethylbenzene, isopropylbenzene, n-butyl-, iso-butyl- or tert-butylbenzene, tert.

   Amylbenzene, chloro-, dichloro-, trichlorobenzenes, fluorobenzene, bromobenzene, ethoxybenzene, methoxybenzene, tetrahydronaphthalene, decahydronaphthalene, cw- and ss-methylnaphthalene, and ss-chloronaphthalene, ar- and ss-methoxy, or diphenyl, diphenaphthalene as well as nitrobenzene, nitro-toluenes, etc.). Mixtures of solvents with one another or with water are of course also possible.



   When using water or alcohols or nitrated hydrocarbons as solvents or suspending agents, it is advisable to carry out the reaction at a maximum of 120 ° C., since water and the alcohols cause the chlorine atom to be split off at temperatures above 120 ° C., while the nitrated hydrocarbons also cause dehydrogenation and can cause amination.



   The solvent or suspending agent can also be partially or wholly replaced by an excess of the compound containing at least two conjugated double bonds capable of addition. The nucleus A can be used as a substituent e.g. Halogen atoms (chlorine, bromine, fluorine), low molecular weight, optionally substituted alkyl groups, (methyl, ethyl, isopropyl, isoamyl, n amyl, ß-hydroxyethyl) hydroxyl or carboxy groups carry.



   Suitable 1,3-dienes are e.g. from the aliphatic series:
1,3-butadiene and its alkyl, aryl, halogen, hydroxy, alkoxy, aryloxy and alkanoyloxy derivatives, such as 2-methyl-1, 3-butadiene, 1-methyl-1, 3-butadiene (2,4-pentadiene), 1,4-dimethyl-1,3-butadiene (2,4-hexadiene), 1,3, or 2,3-dimethyl-1,3-butadiene, 2-chloro or 2-bromo-1 , 3-butadiene, 2,3-dichloro- or 2,3-dibromo-1,3-butadiene, 1-phenyl-1,3-butadiene, 1-hydroxy1,3-butadiene, 1-methoxy or 1-ethoxy 1,3-butadiene, 2,3-dimethoxy-1,3-butadiene, 1- or 2-acetoxy-1,3butadiene, 1,3,5-hexatriene; from the carbocyclic series:

   Cyclopentadiene, cyclohexadiene, hexachlorocyclopentadiene, diemthoxycyclopentadienes, tetrachlorodimethoxycyclopentadienes, hexachlorocyclohexadienone, anthracene, methylene-anthrone, and from the heterocyclic series: a-pyrones, furans, such as halo-pyrones, thorfanes, and thiophanes, as well as halo-methyl-furans, tetrofurophanes, and trofuranophanes, o-methyl-furanes, and halofurophanes with fused aryl cores.



   After the reaction has ended, the compounds of the formula (1) can be isolated after one of the basic operations, such as filtration, evaporation to a small volume, if appropriate under reduced pressure, steam distillation of the solvent, precipitation with a suitable agent.



   The polycyclic quinoid compounds of the formula (I) can be used as intermediates for the preparation of amino dyes by reacting them with ammonia or an amine which reacts with the Cl atom. Such amino compounds are suitable as disperse dyes. If the compound of the formula (I) has reacted with arylamines, these can be sulfonated and water-soluble dyes for natural and synthetic polyamide fibers can be obtained (cf. Ja Posstowski and L.N. Goldyrew-Central-Blatt 1942, page 1875).



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



   example 1
1 part of 10-chloro-1-hydroxy-4,9-antrachinone is heated to 100 ° in a pressure vessel with 5 parts of 1,3-butadiene for 5 hours. Then the excess 1,3-butadiene is distilled off. The residue consists of 1.15 parts (= 95% of theory) of 10-chloro-1-hydroxy-4,9-anthraquinone-butadiene adduct and melts at 162-169 ".



   A sample recrystallized from benzene melts at 176.



   The analysis of the pipe product gives: found: 69.20 / 0 C 4.5 0/0 H 15.0% 0 11.3% C1 calc: 69.1% C 4.2% H 15.40 / 0 0 11 , 3% C1
Example 2
If the 5 parts of 1,3-butadiene are replaced in Example 1 by 3 parts of 2-methyl-1,3-butadiene (isoprene) and the procedure is the same, 1.24 parts are obtained (= 98% of theory) 10-chloro-1-hydroxy-4,9-anthraquinone isoprene adduct. It melts at 162-166 ". A sample recrystallized from benzene melts at 175.



   The analysis of the adduct shows: found: 70.0 0/0 C 4.6 0 / o H 14.5% 0 10.6% Cl ber: 69.9% C 4.6% H 14.7% O 10 , 9% Cl.



   Example 3
1 part of 10-chloro-1-hydroxy-4,9-anthraquinone is suspended with 2 parts of 2-methyl-1,3-butadiene (isoprene) in 10 parts of water and heated to 100 in a pressure vessel for 8 hours.



   The excess isoprene is then distilled off, the aqueous suspension is filtered off and the residue is dried at 70 °. It consists of 1.24 parts of 10-chloro-1 hydroxy-4, 9 -anthraquinone-isoprene adduct and melts at 160-1650. A sample recrystallized from benzene melts at 175. Analysis of the product gives: found: 69.40 / o C 4.20 / o H 15.20 / o 0 10.6% Cl ber: 69.9% C 4.6% H 14.7 o / o 0 10.9% C1.



   Example 4
1 part of 10-chloro -1-hydroxy-4,9-anthraquinone is heated to 900 for 12 hours with 5 parts of 2-chloro-1,3-butadiene (chloroprene). Then the excess chloroprene is distilled off. The residue consists of crude 10-chloro-1-hydroxy-4, 9-anthraquinone-chloroprene adduct. A sample recrystallized from benzene melts at 155.



   Example 5
1 part of 10-chloro -1-hydroxy-4,9 -anthraquinone is refluxed at 1600 in 5 parts of hexachlorocyclopentadiene for 14 hours. Then the excess hexachlorocyclopentadiene is distilled off and the residue is dried at 80 in a vacuum.



   The yield is 1.9 parts = 92% of theory. The crude product melts at 2022060, after recrystallization from benzene petroleum ether at 210.



   The analysis shows. found: 43.2% C 1.3% H 9.5% O 46.6% Cl. ber: 42.9% C 1.3% H 9.0% O 46.8% Cl. Table of the starting and end products of the reactions described in the examples, Example 1
EMI3.1
 Example 2
EMI3.2
 Example 5
EMI3.3
 Example 4
EMI3.4
  Example 5
EMI4.1


 

Claims (1)

PATENT CLAIM Process for the preparation of polycyclic quinoid compounds of the formula EMI4.2 EMI4.3 added in 2,3-position according to Diels-Adler. where Z denotes the atoms necessary for the formation of an optionally substituted, unsaturated mononuclear or polynuclear, carbocyclic or heterocyclic ring and the nucleus A is optionally substituted, characterized in that a 1,3-diene which is composed of the atoms of Z exists, to a dienophilic compound of the formula UNTIIR CLAIMS 1. The method according to claim, characterized in that the reaction is carried out at temperatures of 50-250 "C. 2. The method according to claim, characterized in that the reaction is carried out in solution. 3. The method according to claim, characterized in that the reaction is carried out in suspension.