SU1131867A1 - Derivatives of 9,10-anthracene aldehydes as intermediate compounds for preparing anthracene-9,10-bis carbonylhydrazones or their derivatives having antimicrobial effect - Google Patents

Abstract

Novel anthracence-9,10-bis carbonyl hydrazones of formula: <IMG> (I) and the pharmaceutically aceptable acid addition salts thereof, useful as antibacterial agents, for inhibiting the growth of transplanted mouse tumors, and for inducing the rgression and/or palliation of leukemia and related cancers.

Description

The invention relates to new derivatives of 9,10-anthracenedialdehydes of the general formula KI J where the dotted link means that the position 9,10 of the core can be hydrogenated, R is the hydrogen; . R is hydrogen, fluorine is chlorine, R is hydrogen, chlorine, fluorine, methyl, ethyl, (lettoxy R. / - hydrogen, methyl, methoxy, or R and R, j, together with the adjacent carbon atoms to which they are attached, can to form phenyl irpynny, which are intermediates for producing anthraden-9,10-5-carbonyl hydrazones or its derivatives exhibiting antimicrobial activity. New anthracene-9, U-bis-carbonyl hydrazine of the general formula N-NC ICb Biv. l Z - (CH2) -C or -CH-CH-; 1,2,3, R-hydrogen, alkyl, Cj-C, cycloalkyl Cf-Cg, fensch or benzyl 45 R, R2, R ;, 1 have the indicated Rg is alkyp C | - Cg, Rg - hydrogen, alkyl C -. - Cd, phenyl or a fragment of the formula No. H2.r,; UII - CR tiflti - CY where m 2,3,4; 5G. R, - amino, anilino, hydrazino , a monohydroxyalkylamino-55 group, a carbon atom that is in alpha position to the nitrogen atom, according to a re act, a weedy ratio for the latter, or S may not have a hydroxy substituent, an alkylamino group containing up to 4 carbon atoms, a dialkylamino group in which each alkyl group contains up to 4 carbon atoms, a cycloalkylamino group containing 3-6 carbon atoms, benzylamino, (X-phenethylamino, - / -phenetyl ino, 2-furfurylamine, 3-furfurylamine of -tienilamino p -tienilamino about -piridilmetilamino, -piridilmetilamyno, y -piridilmetrshamino, indanyl o, pyrrolidino, piperidino, morpholino, thiomorpholino, K-methylpiperazino, alkoxy containing up to 4 carbon atoms carbon or alkylthio group containing up to -j4 carbon atoms, X oxo group, thioxo, imino group y-oxo, thio, or divalent group of the formula: N - Ryt, where R "is hydrogen, alkyl containing up to 4 carbon atoms, or monohydroxyl-kil containing 2-4 carbon atoms, and in which the carbon atom Finds schiys in the alpha position to the nitrogen atom can not be hydroxy substituent, Luciano izobteni of the novel compounds, are valuable timikrobialnye agents and possess wide spectrum of antibacterial i ivnosti stantnyh against a large number of laboratory microorganisms. - nG Their efficacy in comparison with iodine fluorouracil ij, used for the same purpose, is determined by a much smaller dosage. New compounds and their pharmaceutically applicable salts, and salts of quartic ammonium salts can be active against various cancers, especially blood diseases, such as leuke, when used in experiments on single dosages, are much more severe, than toxic. The aim of the invention is to provide new anthracene-9,10w C-carbonyl hydrazones or its derivatives, which show antimycro activity.

The goal is achieved by left derivatives of 9,10-anthracene aldehydes of the general formula.

New initial 9,10-anthracenedialdehyde can be obtained according to one of the above schemes.

According to one of the schemes, the anthracene derivative is suspended in dioxane and concentrated hydrochloric acid and saturated with HC1, after which the treatment with paraformaldehyde is carried out at a reflux temperature for 2-6.4, with the formation of 9.10-5 and C- (methyl chloride) anthracene derivative. This 9, U-BCS-Shllormethyl) anthracene is suspended in dry dimethyl sulfoxide of nitrogen at room temperature and then treated with sodium in ethanol to obtain 9,10-anthrisedicarboxaldehyde.

According to another scheme, dihydroxyanthraquinone is treated with trimethylsilyl chloride in dry tetrahydrofuran in the presence of triethylamine to form a trimethylsilyloxy derivative. The latter compound is then dissolved in tetrahydrofuran and treated with a solution of anhydrous diethyl ether and hexane containing about-lithium- (S, S-dimethylamino) methyldiphenylphosphine oxide at room temperature to form b-amine, which is hydrolyzed without isolation by adding 90% - formic acid solution with the formation of hydroxy-substituted 9,10-anthracenecarboxaldehyde.

According to one of the schemes, the anthracene derivative is heated with an excess of vnylene carbonate for 10-24 hours to form a cyclic carbonate. As a result of cyclic carbonate hydrolysis with water-ethanolic sodium hydroxide solution at 70-75 ° C for 1-4 hours, a diol is obtained, which in turn is treated with lead tetraacetate in acetic acid at 20-35 ° C for 10 minutes - 2 hours education 9,10-anthracenecarboxaldehyde.

According to another scheme, nitraquinone is treated with dimethylsulfonium methyliodide (fti and dimethyloxosulfonylmethyl iodide) in dimethyl sulphoxide at 10-40 ° C to form dispiroxyran-2.9 (1 OH) -antracene-10,2-oxirane. The latter compound is rearranged with lithium bromide (lithium perchlorate, boron trifluoride, magnesium bromide, trifluoroacetic acid, and metasulfonic acid) in an organic solvent medium to form 9-formyl-10-hydroxymethyl anthracene. Zatem9-formyl-10-gidroksimetilantratse oxidized on - chloranil or dihlortsiano-1, 4-benzoquinone, dimethyl sulfoxide, diethyl azodicarboxylate, lead tetraacetate, nickel peroxide, manganese oxide, chromium trioxide and selenium oxide, in an organic solvent at 20-100 C. the formation of 9,10-anthracenecarboxidedex.

In accordance with one of the schemes, anthraquinone is treated with dimethyl sulfoxide dianion at 10–40 ° C to form 9,10-DIHIDRO-9,10- (methane-methane) -antracenen-9, 10-DIOL-12-OKXI. The latter compound is treated with acetic anhydrite, then 88% formic acid, to form 9,10-anthracene-carboxaldehyde.

9,10-Dimethylanthracene in a solution of acetic acid, acetic anhydride and sulfuric acid is cooled to 0-10 ° C and treated with 2 mole equivalents of chromium trioxide to form tetraacetate, which is then hydrolyzed at 20-50 ° C with sodium carbonate solution to form dialdehyde.

Other oxidation agents can also be used for oxidation, such as selenium dioxide and mixed cerium and ammonium nitrate.

in accordance with another scheme: a mixture of anthracene and excess acetylene is heated in the absence of a solvent in an environment of an organic solvent such as xylene to 50-150 ° C for 2-20 hours with the formation of an adduct.

The adduct in the medium of such a solvent as ether or dioxane, is treated with osmium tetroxide in the presence of pyridine at 10-60 ° C for 12 hours and 2 days and then with mainitis to form UitiC-glycol. Then this compound is treated with lead tetraacetate in an acetic acid medium at 20–60 ° C for 1–5 h with the formation of dicarbonylanthracene. In the case when R is fcoOH, the compound is heated to quinoline or pyridine at 100-180 ° C to form 9,10-anthracene dicarboaldehyde. The use of the compounds of the invention is that they are reacted with a hydrazine of the formula: / RI where R. has the indicated values, or -C (SR) NR2, provided that if Z is C-CHO, then H; cn is c-d II NH where R has the indicated values, and if necessary, when R and the compound of the formula are hydrogen. H CSR, where Krt has the indicated meanings, and if Rn - C {SR) -NR is reacted with a suitable amine to obtain a compound of the formula (It), R or -C —Y where R (1.1 M-CCH-z ) where X, Y, K, and p have the indicated meanings, and if necessary, pharmacologically acceptable addition salts with an acid or quaternary ammonium salts are obtained. Example 1 2-Chloro-9,10-anthraredicarboxaldehyde. A solution of 15.0 g of 2-hlorantracene in 60.8 g of vinylene carbonate is heated under reflux for 20 hours. Ex. 4 vinylene carbonate is removed by vacuum distillation. The residue, a brown solid, is recrystallized from chlor. methylene methanol to form 2-chloro-9,10-dihydro-3, 10-ethane anthracene-11,12-diol cyclic carbonate, so pl. 200-230 ° C. Calculated,%: C 68.3, H 3.7. C ,, H, C10 Found,%: C 67.9, H 3.9. A mixture consisting of 12.0 g of such cyclic carbonate and 9, potassium hydroxide in 100 ml of water and 12 ml of ethanol, is heated at 75 ° C for 2 hours. The resulting mixture is evaporated under reduced pressure for a volume of 50 ml and then treated with 7,400 ml of water. The crystalline product is collected and recrystallized from toluene to form 2-CHLOR-9,10-DIHIDRO-9,10-ethananthracene-11, 12-diol, mp. 195-210 0. Calculated,%: C 70.5, H 4.8, C1 19.0, Cyy. C 10/7 Found,%: C 70.4, H 4.9, C1 12 , 7 To a suspension containing 2.73 g of such a diol in 70 ml of acetic acid, at 35 ° C, 8.8 g of lead tetraacetate are added over 5 minutes. The reaction mixture is stirred at 39 ° C for a further 2 hours to form 1, 5 g of an orange crystalline compound; An additional 0.5 g of compound is obtained by evaporation of the mother liquor. Both parts are combined and recrystallized from 50 ml of toluene to form 2-chloro-9, 1O-anthracene dicarbodealdehyde, so pl. 193-196 0. Calculated,%: C, 70.3, H, 3.5, C1, 13.0. Found,% C 70.6, H 3.7, C1 12.6. PRI mme R 2. 2-Methyl-9,10-anthracenecarboxaldehyde. 13 g of 2-methylanthracene are converted to 2-methyl-9,10-anthracenecarboxaldehyde by the three-step process described for the 2-chloro analog in Example 1, mp. 162-164 ° C, yield 76%. Calculated,%: C 82.2, H 4.9. Found,%: C 82.6, H 5.2. Example 11 1-Chloro-9,10-anthracene dicarboxaldehyde .. 15 g of 1-chloro-anthracene are converted to 1-chloro-9,10-anthracene dicarboxaldehyde according to the three-step method described in Example 1, mp 189 C , yield 36%. 71.5, H 3.4, Calculated,%: C C1 13.2. C, gH, C102 Found: C 71.9, H 3.5, C1 13.1. PRI me R 4. 2-Ethyl-9,10-anthracenecarboxaldehyde. 14 g of 2-methylanthracene are converted to 2-EHYL-9,10 anthracenecarboxaldehyde by the three-step method described in Example 1, mp. 99-100 0,. yield 25%. Calculated,% C 82.4, H 5.4, Found,%: C 81.9, H 5.6. Example 5, 2-Methyl-9,10-anthracene dicarboxaldehyde. A mixture of 2-isomers of 2-methyl-11,12-di-hydroxy-9,10-ethanoanthracene weighing 2.1 is dissolved in 45 ml of glacial acetic acid and treated at a commercial temperature of 7.45 g of lead tetraacetate to a positive reaction to starch. .. After 2-3 hours the reaction at room temperature, followed by cooling, precipitates orange crystals, which are collected by filtration. And recrystallize from the mixture methylene chloride and thiol to form 1.1 g of orange crystals with mp. 162-164C. Calculated,%: C 82.2, H 4.9 17% 2 Found,%: C 82.6, H 5.2. PRI me R 6. 1,4-Dimethoxy-9, 10-anthracenecarboxaldehyde. A mixture of isomers of 1,4-dimethoxy-11, 12-DIHYDROXI-9,10-ethanol-anthra, weighing 10 g, is dissolved in 150 ml of glacial acetic acid at 50 ° C and treated with portions of 30 g of lead tetraacetate. After 2 hours at 50, the solution is filtered to remove insoluble substances and cooled to form orange crystals, which are filtered, washed with glacial acetic acid and dried, mp. 208-212 ° C, yield 5%. Calculated,%: C, 72.3; H, 4.9. C, gH ,, 25..H20 Found,% 72.6, H 4.8. Example 7. 2,6-Difluoro-9,10-anthracene dicarboxaldehyde. 15 g of 2,6-difluoroanthracene are converted to the 2,6-difluoro-9,10-anthracenecarboxaldehyde by the three-step method described in Example 1, mp. 240-242 ° C, yield 32%. Calculated,%: C 64.7, H 3.9, F 12.8. Found,%: C 64.8, H 3.7, F 11.7. : Example 8. 2,3-Dimethyl-9, 10-anthracene dicarboxaldehyde. 14 g of 2,3-dimethylanthracene are converted to 2,3-dimethyl-9,10-anthracene box aldehyde by a three-step process described in example 1, mp. 203204 ° C, yield 47%. Calculated,%: C 82.4, H 5.4. Found,%: C 82.4, H 5.4. PRI me R 9. 2,6-Dichloro 79,10-anthracenecarboxaldehyde. 13 g of 2,6-dichlorantracene are converted to the 2,6-dichloro-9,1 p-anthracenecarboxaldehyde by the three-step process described in Example 1. Example 10. 1,4-Dimethyl-9, 10-anthracene dicarboxaldehyde. 16 g of 1,4-dimethylanthracene are converted into 1,4-dimesh1-9,10-anthra. Cenedicarboxaldehyde by a three-step method described in Example 1, mp. 158-162 ° C, yield 10%. Calculated,%: C 78.5, H 5.6. .0.75 HgO Found,%: C 78.6 N 5.5. Example 11. 9,10-Dihydro-. -9,10-anthracene. Dicarboxaldehyde. A mixture of 21.3 g of vinyl vinyl carbonate (twice distilled to obtain a colorless liquid with a boiling point of 71-73 C, 28 mm) and 4.4 g of dry anthracene are heated under reflux (165-170 ° C) under nitrogen atmosphere for 20 h and then subjected to vacuum distortion (62-64 ° C, 17 mm) with the formation of 10.2 cu residue. This residue is taken up in 100 ml of methylene chloride, treated with charcoal and filtered. The obtained filtrate is treated with 100 ml of methanol and cooled to form colorless crystals 1.0c -9910-dihydro-9, 10-ethanoanthracene-11,12-diol cyclic carbonate (mp 260-262 ° C). A mixture of cyclic carbonate Tschs-9,10-dig1-shch-9,1O-ethanoanthracec-11, 12-diol (5.6 g), 4.9 g of potassium hydroxide, 6.4 ml of water and 53 ml of ethanol is stirred at 70 75 ° C for 2 hours. The resulting bilayer is filtered. The filtrate is diluted with a double volume of water and cooled to form colorless crystals of cis-9, 10-dihydro-9, 10-ethanoanthracene-11, 12-diol (mp 202204 0. Mixture 2, 10-dihydro-9, 10 -Stanoanthracene-11, 12-diol in 40 ml of glacial acetic acid at room temperature is treated in portions of 4.8 g of lead tetraacetate with stirring for 10 minutes, the mixture is cooled to and, 9 the resulting solid is collected by filtration, washed glacial acetic acid, then thoroughly washed with water to form the desired product as a colorless Grain seeds, mp 144-146 C, yield 94%. Calcined,%: C 81.3, H 5.1. Found,%: C 80.9, H 5.1. Example 12.U, t4C -1,4-Dimetok si-9,10-dihydro 9, U-anthracenecarboxydehyde, 1 g of 1,4-dimethoxy-9,10-dihydro-9, 10-ethanoanthracene-11,12-diol suspendruyruot of 30 ml an aqueous solution containing 0.77 g of periodate potassium and 1 ml of ethanol is then stirred at room temperature for 24 hours, the insoluble material is removed by filtration, washed well with water and dried to form a yellowish product, so pl. 129-132 0, -. Yield 28%. Calculated,%: C 73.0, H 5.4. TSVN, b04 Found,%: C 13.0, H 5.7. Example 13. Bis (2-imidazolin -2-ylhydrazone) -9,10-dihydro 9; 10-anthracenecarboxaldehyde. A mixture of 2.36 g of 9,10-dihydro-9,10-anthracene dicarboxaldehyde and 3.46 2-hydrazinoimidazole dihydrochloride in 200 ml of H-propanol is boiled for 1 1/2 hours, bringing the solution to a volume of 100 ml. The resulting mixture is cooled and allowed to stand overnight, to form a solid, which is collected by filtration, washed with H-propanol and dried, 0.4 g of this solid is recrystallized from water to form dihydrochloride in the form of colorless flakes, mp. 258-262 pp and then vacuum distilled. The resulting residue is crystallized from a mixture of methylene-methanol chloride to form isis-2-chloro-9, 10-DIHIDRO-9,10-ethanoanthracene-11, 12 diol of cyclic carbonate in the form of gray crystals, so pl. 200-230s. A mixture consisting of 12.8 g of cyclic cis-2-chloro-9,1067 carbonate 10-dihydro-9,10-ethanoanthracene-11,12-diol, 9.2 g of potassium hydroxide, 12 ml of water and 100 ml the ethanol is heated for 2 hours and then evaporated in vacuo to a volume of 50 ml. The concentrate is diluted with 400 ml of water and the resulting solid is collected by filtration. This solid is recrystallized from toluene, discolored with a small amount of charcoal to form colorless crystals of cis -2-chloro-9,10-dihydro-9, 1O-ethanoanthracene-11, 12-diol, so pl. 195-210 ° C. To a solution of 2.7 gt wc-2-chloro-9,10-dihydro-9, 1O-ethanoanthracene-11,12-diol in 20 ml of acetic acid at a natural temperature was added 5.0 g lead tetraacetate containing 10% acetic acid. The resulting mixture is stirred for 10 minutes, cooled in an ice-water bath, the resulting crystals are collected by filtration and washed with cold acetic acid to form the product as white crystals, mp. 113--115 ° C, yield 33%. Calculated,%: C 70.0, H 4.2, C1 12.9. C | j ,, 2.0.25 Found: C 70.0, H 4.1, C1 12.6. Example 15. 1-chloro-9,10-dihydro-9, 10-anthracenecarboxaldehyde. A mixture of 29.5 g of 1-chloroanthracene and 126 g of vinyl carbonate react as described in Example 4 to form t5ac -1-chloro-9, 10-ethanoanthracene-1i, 12-diol, cyclic carbonate crystals, mp. 242-250 ° C. (Reaction mixture containing 27.9 G ;; 1 C-1-Chlor-9, 10-DIHYDRO-9, 10-ethanoanthracene-11, 12-diol, cyclic carbonate, 21.4 g of potassium hydroxide 28 ml of water and 230 ml of ethanol are heated at 75 ° C for 2 hours and then evaporated in vacuo to a volume of 30 ml. The residue is dissolved in 500 ml of chloroform. The chloroform solution is washed with three portions of 70 ml of each water and provided with activated carbon. The chloroform is removed and the yellow residue is dissolved in 150 ml of toluene. After cooling, the reaction product-e "C-1-chloro-9, 10-dihydro-9, 10-ethano-anthracene-11,12-diol is collected as white colored crystals, m.p. 180-182 ° C.

To a solution of 0.54 g of tJiuC-1-xnop-9, 10-dihydro-9, 10-ethanoanthracene-11,12-diol in 5 ml of acetic acid was added 1.0 g of lead tetraacetate. The resulting mixture is stirred for 10 minutes, cooled in an ice-water bath, and the crystals formed are collected by filtration and washed with cold acetic acid to form the product as colorless crystals, mp. 144-146 ° C, yield 34%.

Calculated,%: C 70.0, H 4.2, C1 12.9.C, bN „C1 020.25

Found,%: C 70.4., H 4.0, C1 12,

PRI me R 16. 2-Methyl 9,10-dihydro-9, 10-anthracenecarboxaldehyde

10 g of 2-methylanthracene in 50 ml of vinylene carbonate is heated under reflux in a nitrogen atmosphere for 20 h. Excess vinylene carbonate is removed by vacuum distillation (55 ° C, 11-12 mm) and the residue is taken up in 100 ml of methylene chloride,

filtered and treated with a triple volume of methanol. The reaction product, cyclic carbonate if, iic -2-methyl-9, 10-DIHYDRO-9,10-ethane-trans-cene-11, 12-diol, is regenerated in syn. And anti-forms as cream crystals (mp. 225-227 s and 183-185s).

2.8 g of one of the anti-or synform of the cyclic carbonate Cys -2-meTSh1-8, 1O-dihydro-9,1 0-ethanoanthracene-11, 12-diol (so pl. 225-227 ° C) in mixture si with 2.5 g of potassium carbonate, 2.3 ml of water and 27 ml of ethanol are stirred at 70 ° C for 2 hours. The mixture is treated with three times the volume of water to form the corresponding blue forms of the cis-2-methyl-9,10-dihydro antiform -9, 10-ethanoanthracene-11,12-diol in the form of light yellow crystals (mp. 227-228 0.

7.4 g of syn- or anti-forms of cyclic tjuc -2-metsh1-9 carbonate, 1O-dihydro-9,10-ethanoanthracene-11, 12-diol m.p. 183-185 ° C) in a mixture of 6.15 g of potassium hydroxide and 8.1 ml of water and 70 ml of ethanol are reacted as described with the formation of a corresponding syn or antiform 1 | C 1c-2-methyl-9510-DIHYDRO-9, 10 ethanol, 11, 12-diol in the form of a cream solid (so pl. 153-156 C).

Calculated,%: C, 81.6, H 5.6.

Found,%: C 81.6, H 6.0.

2.5-1 (IC-2-Methyl-9,10-dihydro-9, 10-ethanoanthracene-11,12-diol (mp. 227-228 C) are suspended in 100 MP of an aqueous solution containing 2.14 g periodate sodium and 1 ml of ethanol. This mixture is stirred at room temperature for 2 hours, the resulting solid is collected by filtration, washed with water and dried to form the product as a light yellow solid, m, 125-126 °, yield 96%

Example 17. 2,3-Dimethyl-9, 1O-dihydro-9,10-anthracene dicarbox aldehyde.

A mixture of 35.4 g of vinylene carbonate and 8.5 g of 2,3-dimethyl anthracene is heated under reflux under nitrogen for 20 hours. The cooled solution is treated with 100 ml of methanol, heated, decolorized with charcoal, filtered and cooled with forming 7.1 g of colorless crystals (mp. 207-212 ° C) of 2,3-dimethyl-9,10-dihydro-9, 10-ethanoanthracene-11,12-diol, cyclic carbonate.

A mixture consisting of 6.4 g of 2,3-dimethyl-9, 1O-dihydro-9,10-ethanoanthracene-11, 12-diol, cyclic carbonate, 5 g of potassium hydroxide, 6.6 ml of water and 60 ml of ethanol stirred at room temperature for 56 hours. The precipitate formed is filtered, dissolved in glacial acetic acid and precipitated with excess waterN to form-4, 0 g of colorless 2,3-dimetry-9, 1O-dihydro-9,10-ethanoanthrace-11 , 12-diol (mp. 240-245 ° C).

Suspension consisting of 0.3 g

2,3, -dimethyl-9,10-dihydro-9, 10-ethanoanthracene-11, 12-diol in 10 ml of water and 0.1 ml of ethanol are treated with 0.243 g of periodate sodium and stirred at 20 ° C for 2.5 hours The solid that was formed was filtered, washed with water and dried to form 2,3-dimethyl-9,10-dihydro-9, 10-anthracene-carboxaldehyde (mp 113-117 ° C), yield 0.2 g. Calculated,%: C 81.8, H 6.1.

Found,%: С 81.0 Н 6.2.

Example 18. 1,4-Yaimethyl-9,10-dihydro-9, 10-anthracene dicarboxaldehyde. A mixture of 4.12 g of a 1,4-dimethyl anthramine and 17.2 g of vinylene carbonate is heated under reflux under nitrogen for 18 hours, cooled, treated with four volumes of methanol, stirred, and cooled. The crystals formed are filtered, washed with methanol and dried to give 5.45 g of pure 1,4-dimethyl-9,1O-dihydro-9,10-ethanoanthracene-11,12-diol, cyclic carbonate (mp. 225-245 A mixture of 4,4 g 1,4-dimethyl-9, 1O-dihydro-9,10-ethanoanthracene.-11,12-diol, cyclic carbonate, 3.45 g of potassium hydroxide, 4.5 water and 40 ml of ethanol are stirred at 20 With 16 h. The two-layer mixture is filtered through a zeolite and treated with four times the volume of water to form 3.8 g of colorless 1,4-dimethyl-9,10-dihydro-9,10-ethane anthracene-11, 12-diol (t. pl, 158160 ° C.). Calculated.%: C 81.8, H 6.1. C, sH, 02 On deno%: C 81.5, H 6.3. A mixture of 1.5 g of 1,4-dimethyl-9, 1. O-dihydro-9,10-ethanoanthracene-11, 12-diol and 1.22 g periodate on ri 50 ml of water and 1 ml of ethanol are stirred for 2 hours at 20 ° C. The solid formed is filtered off, washed with water and dried to give 1.45 g of 1,4-dimethyl-9, 1O-dihydro 9,10-anthracene carboxaldehyde (m.p. 159-160 C) Example 19. 4-Dimetic Si-9,1O-dihydro-9,10-ethanoanthracene-11, 12-diode, acyclic carbonate, syn- and antiisomers. 14 g of 1,4-dimethoxyanthracene are heated under reflux in a nitrogen atmosphere in 55 g of vinylene carbonate for 16 h. Excess vinylene carbonate is removed under vacuum (55 ° C, 12 mm), the resulting residue is treated with chloroform and a filter to form 13 g of a mixture of yellow and colorless crystals. When this mixture is boiled with methylene chloride and after filtration I get 10.5 g of colorless crystals, so pl. C, in viD syn or anti-isomeric forms. Calculated,%: C 69.3, H 5.0. C, aH, 050.25 HgO Found: C 69.1, H 5.0 Another syn or anti-isomer is obtained from the chloroform filtrate by precipitation with methanol and recrystallization from a mixture of methylene chloride and methanol to form 5 g of colorless crystals, tons. square 255-260 C. Both isomers have the same IR spectra and exhibit a lower mixed melting point (238-245 s). Calculated,%: C 68.5, H 5.1. С „Н, б050,25 Found, С 69,2, Н 5,3. Example 20. CCs -1,4-dime.tok-; Si-9,1O-dihydro-9,10-ethanoanthracene-11,. 12-diol., Syn- and anti-isomers. A mixture of 10.5 g of CP with -1,4-dimethoxy-9, 1O-dihydro-9,10-ethanoanthracene-11, 12-diol, cyclic carbonate (mp 283-285 ° C) and 8.5 g of potassium hydroxide, 12 ml of water and 85 ml of ethanol are stirred at room temperature for 16 hours. The solid formed is filtered, washed and dried to give 5.0 g of one of the isomers of the product, so pl. 187-188 C. Calculated,%: C, 72.4; H, 6.1. C (gH | gO Found,%: C 72.0, H 6.3. Another syn / anti isomer is obtained in the same manner from 4.0 g of the corresponding cyclic carbonate, mp 238-245 ° C in an amount of 2, 1 g of product, mp 183-185 C. Both isomeric diols have the same IR spectra and exhibit a lower mixed melting point, mp 155-158 ° C. Calculated,%: C 71.3, H 6, 1. C, gH | g04.0.25 HgO Found: C 71.7, H 6.3, Example 21. 5,12-Dihydro-5, 12-benz (c) anthracenecarboxaldehyde. , A mixture of 7.0 g of benz (s) anthracene and 26 g of vinylene carbonate is heated under reflux in a nitrogen atmosphere for 20 h. Excess vinyl The carbonate is removed by vacuum distillation (mm) and the residue is taken up in 25 ml of methylene chloride and filtered. The filtrate is treated with a double volume of methanol and then cooled to form a gummy solid and a mother liquor, which is saved. The resulting solid is recrystallized from 60 ml 1,2-dichloromethane, collected

15

by filtration, washed with methanolBm and maintained. The mother liquor is concentrated to form a viscous solid, which is recrystallized from methylene chloride-methanol to form a gray solid, which is combined with the obtained solid and recrystallized from ethyl acetate, and after treatment with charcoal, 5,12-dihydro-5,12 is obtained - ethanobenz (c) anthracene-13,14-diol, cyclic carbonate in the form of colorless rods.

A mixture consisting of 1.3 g of cyclic carbonate, 1.05 g of potassium hydroxide, 1 ml of water and 15 ml of ethanol is stirred at 60-65 ° C for 2 hours. The mixture is diluted with 1-2 volumes of water, filtered and the solid is washed with water and dried to form cis-5,12-dihydro-5, 12-ethanobenz (c) anthracene-13,14-diol as a colorless solid. Ethanobenz (c) anthracene-13, 14-diolav 400 ml of glacial acetic acid at 2CP are added to a solution of 2.6 hzx-5,12-digi {pho-5, 12 - ethanobenz (c) of 4.4 tetraacetate of lead. The contents of the reaction mass is stirred for 45 minutes The light purple solid is filtered off.

6716

washed with glacial acetic acid and water, then dried to form 1.0 g (mp. 170-172 0 5,12-dihydro-5, 12-benz (in) anthrac of dicarboxaldehyde.

PRI me R 22. 7; 12-Venz (a) anthracene dicarboxaldehyde.

The mixture of isomers of 7,12-dihydro-7,12-benz (a) -transuccinol dehydrate was suspended in 75 ml of glacial acetic acid, treated with 6 g of iron chloride hexahydrate and stirred at room temperature for 3 hours. The remaining yellow solid was filtered, washed with iron chloride and washed at room temperature for 3 hours. The remaining yellow solid was filtered, washed with iron chloride and washed at room temperature for 3 hours. and water to obtain a yellow product, so pl. 197-198 ° C.

Etc. and mera 23. 5,12-Benz (c) antarcénabarbobokaldegid.

A solution of 5 g of 13,14-dioxy-5,12-ethanobenz (c) anthracene in 110 ml of glacial acetic acid is treated with 15.4 g of tetraacetate and stirred at 30-40 ° C for 3 hours. The resulting violet solid is filtered, washed acetic acid and then water, dried, recrystallized from methylene chloride-methanol and get connection with so pl. 215, yield 20%.

Calculated,%: C 84.5, H 4.3.

C oHjjO

Found,%: C 84, -6, H 4.3.

Claims (1)

PRI me R 23. 5,12-Benz (c) anthracenecarboxaldehyde. A solution of 5 g of 13,14-dioxy-5,12-ethanobenz (c) anthracene in 110 ml of glacial acetic acid is treated with 15.4 g of tetraacetate and stirred at 30-40 ° C for 3 hours. The resulting violet solid is filtered, washed acetic acid and then water, dried, recrystallized from methylene chloride-methanol and get connection with so pl. 215 "" 217 ° C, yield 20%. Calculated,%: C 84.5, H 4.3. Found,%: C 84, -6, H 4.3.