Method for preparing derivatives of 3-phenylsulfonylanthra-[1,9-cd]-isoxazole-6-one

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing derivatives of 3-phenylsulfonylanthra-[1,9-cd]-isoxazole-6-one of the general formula: wherein X means hydrogen, halogen atom or lower alkyl; Y means hydrogen atom or hydroxy-group. Method involves heating derivative of 2-phenylsulfonylanthraquinone in organic solvent wherein 1-(triazene-N-sulfonate)-2-phenylsulfonylanthraquinone of the general formula: wherein X and Y have above given values is used as derivative of 2-phenylsulfonylanthraquinone that is boiled in alkali alcoholic solution followed by neutralization with acetic acid. Invention provides simplifying technology of the process and expanding assortment of the end products.

EFFECT: improved preparing method.

2 tbl, 3 ex

 

The invention relates to the chemistry and technology of intermediates and organic dyes and can be used at the enterprises of the aniline dye industry to obtain antrahinonovye dyes.

Famous original substance to obtain 5,6-califonication-S,S-dioxides are the corresponding 5,6-fallprotection, which are oxidized by hydrogen peroxide in acetic acid (Patent 3519623. 1970. USA. S.A. V.73. A).

The disadvantage of this method is the use of explosive hydrogen peroxide, as well as the duration of the oxidation process.

The closest technological essence and the achieved result is a method of obtaining 3-phenolsulfonate[1,9-cd]isoxazol-6-ones, based on heating the corresponding 1-azido-2-vinylsulfonylacetamido in organic solvents (ermine L., levdansky, VA // Zhur.org.chem.. 1984. THH. VIP. S-2458).

The disadvantage of obtaining 1 azido-2-vinylsulfonylacetamido is the use of attestations acid or its alkali metal salts, which can form explosive mixtures with air (attestation acid)and in the presence of heavy metals (heavy metal azides are explosive), making it unsafe.

The problem solved by the invention is to create the AI a new method of obtaining derivatives of 3-phenolsulfonate[1,9-cd]isoxazol-6-it.

The technical result - the simplification of the process and expand the range of target products.

This technical is achieved by a new method of obtaining compounds of General formula I

who is that 1-(triazin-N-sulfonate)-2-vinylsulfonylacetamido General formula II

where X and Y have the above meanings, is boiled in alcoholic alkali solution, followed by neutralization with acetic acid.

The inventive product: derivatives of 3-phenolsulfonate[1,9-cd]isoxazol-6-it formula I

where X is hydrogen, halogen or lower alkyl, Y is hydrogen or a hydroxy-group.

Reagent: 1-(triazin-N-sulfonate)-2-vinylsulfonylacetamido formula II

Reaction conditions: boiling alcoholic solution of alkali.

The proposed method allows to obtain derivatives of 3-phenolsulfonate[1,9-cd]isoxazol-6-it is with high yield from previously unused for this purpose, 1-(triazin-N-sulfonate)-2-vinylsulfonylacetamido.

The composition and structure of the obtained 3-phenolsulfonate[1,9-cd]isoxazol-6-ones installed using elemental analysis and physical-chemical methods.

Example 1. 3-Phenolsulfonate[1,9-cd]isoxazol-6-he.

is 4.93 g (0.01 mol) 1-(Tr is Asen-N-sulfonate)-2-vinylsulfonylacetamido is boiled in a flask under reflux with stirring in 40 ml of ethanol, containing 0.4 g (0.01 mol) of sodium hydroxide for 30 minutes. The reaction mass is then cooled to 10-15°C, neutralized with acetic acid, diluted with 50-60 ml of water and the precipitated crystals filtered off, washed on the filter with 20-25 ml of water, dried at room temperature. The product yield was of 3.07 g (85%) TPL=183°C. Found, %: N 3,71, 4,00; S a total of 8.74, 9,06. C20H11NO4S. Calculated, %: N 3,88; S 8,86.

Example 2. 3-Phenolsulfonate[1,9-cd]isoxazol-6-he.

is 4.93 g (0.01 mol) 1-(triazin-N-sulfonate)-2-vinylsulfonylacetamido, boiled in a flask under reflux with stirring in 40 ml of ethanol containing 0.4 g (0.01 mol) of potassium hydroxide for 30 minutes. The reaction mass is then cooled to 10-15°C, neutralized with acetic acid, diluted with 50-60 ml of water and the precipitated crystals filtered off, washed on the filter with 20-25 ml of water, dried at room temperature. The product yield was of 3.07 g (85%) TPL=183°C. Found, %: N 3,70, 4,01; S 8,75, 9,05. C20H11NO4S. Calculated, %: N 3,88; S 8,86.

The synthesis of the other 3-phenolsulfonate[1,9-cd]isoxazol-6-ones performed similarly, their characteristics are shown in table 1.

The original synthesis of 1-(triazin-N-sulfonate)-2-phenylsulfonyl-anthraquinones used to obtain 3-phenolsulfonate[1,9-cd]isoxazol-6-ones was carried out as follows.

P the emer 3. 1-(Triazin-N-sulfonate)-2-vinylsulfonylacetamido.

The solution 3,63 g (0.01 mol) of 1-amino-2-vinylsulfonylacetamido in 100 ml of acetic acid diasterous at 5-10°With solution nitrogylcerin acid prepared from 0,83 g (0.012 mol) of sodium nitrite and 10 ml of 95% sulfuric acid for 2 hours. Then the reaction mass is diluted with 10-15 ml water, add activated charcoal and filtered from impurities. Then the filtrate with stirring and cooling gain of 1.43 g (0.012 mol) of sodium salt of sulfamic acid and 0,098 g (0.012 mol) of sodium acetate. Stand 15-20 minutes with stirring, then the reaction mixture is diluted with 100 to 150 ml of cold water, the precipitated crystals of 1-(triazin-N-sulfonate)-2-vinylsulfonylacetamido filtered off, washed on the filter with cold water, dried at room temperature. The yield of product amounted to 4.14 g (84%) TPL=141°C. Found, %: N Scored 8.38, 8,65; S 12,81, of 13.05. C20H12N3O7S2Na. Calculated, %: N Charged 8.52; S 12,98. The synthesis of the remaining 1-(triazin-N-sulfonate)-2-vinylsulfonylacetamido is carried out in similar conditions. Characterization of the obtained compounds are shown in table 2.

Source 1-amino-2-vinylsulfonylacetamido obtained in a known manner in the interaction of 1-amino-2-chloroanthraquinone and 1-amino-2-chloro-4-hydroxyanthraquinone sodium salts vinylsulfonic KIS is from (Patent 1266902. 1968. The Federal Republic of Germany. S.A. V.69. 28600).

The obtained derivatives of 3-phenolsulfonate[1,9cd]isoxazol-6-it can be used mainly in organic synthesis for the preparation of derivatives of 5,6-califonication-S,S-dioxides used as dyes for polyester fibers.

Table 1

Features 3-phenolsulfonate[1,9-cd]isoxazol-6-ones
№ p/pDeputy*TPL°CFoundFormulaCalculatedOutput %
XYN %S %N %S %
1.HN1833,71; 4,00a total of 8.74; 9,06C20H11NO4S3,888,8685
2.HHE167to 3.58; 3,798,31; charged 8.52C20H11NO5S3,718,4983
3.CH3N221to 3.92; 3,758,43; 8,62C21H11NO4S to 3.738,5688
4.CH3HE1873,74; 3,518,12; at 8.36;C21H113NO5Sto 3.588,2184
5.Cln2133,42; 3,688,12; 8,27C20H10ClNO4S3,548,0986
6.Clhe1773,23; 3,477,65; to $ 7.91C20H10ClNO5S3,407,7887
7.Brhe1972,98; 3,176,89; 7,18C20H10BrNO5Sof 3.077,0282
* - shows the onset temperature of decomposition substances

11,63; 11,89
Table 2

Features 1-(triazin-N-sulfonate)-2-vinylsulfonylacetamido
№ p/pDeputy*TPL°CFoundFormulaVicis the network Output %
XYN %S %N %S %
1.NN141scored 8.38; 8,6512,81; of 13.05C20H12N3O7S2Nacharged 8.5212,9884
2.HHE1388,53; 8,2112,79; 12,63C20H12N3O8S2Na8,2512,5787
3.CH3N1298,09; 7,9912,93; 12,80C21H14N3O7S2Na8,28br12.6283
4.CH3HE1277,79; 7,9912,47; 12,56C21H14N3O8S2Na8,0312,2486
5.ClN1528,12; 7,87up 11,86; 12,08C20H11ClN3O7S2Naof 7.9612,1388
6.ClHE1687,58; 7,84C20H11ClN3O8S2Na7,7311,7887
7.BrHE1756,99; 7,25br11.01; 10,75C20H11BrN3O8S2Na7,1410,8884
* - shows the onset temperature of decomposition substances

The method of obtaining derivatives of 3-phenolsulfonate[1,9-cd]isoxazol-6-it General formula

where X is hydrogen, halogen or lower alkyl;

Y is hydrogen or a hydroxy-group,

the heat derived 2-vinylsulfonylacetamido in an organic solvent, characterized in that as a derivative of 2-vinylsulfonylacetamido using 1-(triazin-N-sulfonate)-2-vinylsulfonylacetamido General formula

where X and Y are the specified values

which is boiled in alcoholic alkali solution, followed by neutralization with acetic acid.



 

Same patents:

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing derivatives of 3-phenylsulfonylanthra-[1,9-cd]-isoxazole-6-one of the general formula: wherein X means hydrogen, halogen atom or lower alkyl; Y means hydrogen atom or hydroxy-group. Method involves heating 1-substituted derivative of 2-phenylsulfonylanthraquinone in organic solvent wherein 1-hydroxytriazeno-2-phenylsulfonylanthraquinone of the general formula: wherein X and Y have above given values is used as 1-substituted derivative of 2-phenylsulfonylanthraquinone, and acetic anhydride is used as an organic solvent. Invention provides simplifying technology of the process and expanding assortment of the end products.

EFFECT: improved preparing method.

2 tbl, 5 ex

The invention relates to new biologically active compounds - substituted 3-methyl-4,5-dihydro-1,2-benzisoxazole formula I, where I

The invention relates to new substituted benzylamines formula I, each of R1and R2that may be the same or different, is chosen from the group comprising phenyl, phenyl-C1-alkyl in which the phenyl portion may be optionally substituted by a Deputy selected from C1-6-alkoxy, thiazolyl, 1,2-benzisoxazole, C1-6-alkylcarboxylic,2-4-heteroaryl-C1-6-alkyl; hydrogen, C1-6-alkyl, optionally substituted by a hydroxy-group, WITH2-6alkenyl; each of R3and R4that may be the same or different, is chosen from the group comprising phenyl which may be optionally substituted with halogen, phenyl - C1-6-alkyl, C2-4-heteroaryl-C1-6is alkyl, hydrogen, C1-6-alkyl, C3-6-cycloalkyl,4-6-cycloalkenyl,2-6alkenyl,2-6-quinil, halogen - C1-6alkenyl, cyano; or one of R3and R4together with one of R1and R2and N-atom to which they are attached, form a 5 - or 6-membered heterocycle; R5- halogen, hydrogen; R6Deputy ring of formula II, where the dotted line represents an optional bond; Y is - O-or-NR8, R8is hydrogen or C1-6-alkyl; R7- the

The invention relates to compounds of the formula I, their pharmaceutically acceptable salts and stereoisomeric forms, where R is hydrogen or C1-6-alkyl; R2is hydrogen; C1-6-alkyl; trihalomethanes; C1-6-alkyl, substituted carboxyla,1-6-alkylcarboxylic,1-6-allyloxycarbonyl, or R1and R2taken together with the nitrogen atom to which they are attached, may form a ring morpholinyl or optionally substituted heterocyclic radical; R3- R10each independently represents hydrogen; R8, R9independently represent hydrogen or halogen; R11and R12is hydrogen; n= 1, 2, 3, 4, 5 or 6; X Is O, S, S(=O)

The invention relates to a method for 3-{ 2-[4-(6-toranzo[d]isoxazol-3-yl) piperidine-1-yl] ethyl} -2-methyl-6,7,8,9-tetrahydro-4H-pyrido-[1,2-a] pyrimidine-4-it (I) interaction of 3-(2-amino-ethyl)-2-methyl-6,7,8,9-tetrahydro-4H-pyrido[1,2-a] pyrimidine-4-it (II) isoxazol derivative of the formula (III)where Y and Z represent the deleted group, such as halogen or alkyl - or arylsulfonate, in the presence of a suitable solvent and base

The invention relates to 9-amino-1,2,3,4-tetrahydropyridines and related compounds of the formula I

< / BR>
in which Y is C= O or CHOH; R1is hydrogen or lower alkyl; R2is hydrogen, lower alkyl or phenyl-lower alkyl; R3is hydrogen, OR4in which R4is hydrogen, COR5in which R5is lower alkyl, X is hydrogen, lower alkyl, halogen, lower alkoxy-, hydroxy-group or trifluoromethyl, their geometric or optical isomers, N-oxides, or their pharmaceutically acceptable salts and accessions acids (acid additive salts), which are useful in reducing dysfunction in memory and are thus indicative for the treatment of disease Allgamer

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing derivatives of 3-phenylsulfonylanthra-[1,9-cd]-isoxazole-6-one of the general formula: wherein X means hydrogen, halogen atom or lower alkyl; Y means hydrogen atom or hydroxy-group. Method involves heating 1-substituted derivative of 2-phenylsulfonylanthraquinone in organic solvent wherein 1-hydroxytriazeno-2-phenylsulfonylanthraquinone of the general formula: wherein X and Y have above given values is used as 1-substituted derivative of 2-phenylsulfonylanthraquinone, and acetic anhydride is used as an organic solvent. Invention provides simplifying technology of the process and expanding assortment of the end products.

EFFECT: improved preparing method.

2 tbl, 5 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing derivatives of 3-phenylsulfonylanthra-[1,9-cd]-isoxazole-6-one of the general formula: wherein X means hydrogen, halogen atom or lower alkyl; Y means hydrogen atom or hydroxy-group. Method involves heating derivative of 2-phenylsulfonylanthraquinone in organic solvent wherein 1-(triazene-N-sulfonate)-2-phenylsulfonylanthraquinone of the general formula: wherein X and Y have above given values is used as derivative of 2-phenylsulfonylanthraquinone that is boiled in alkali alcoholic solution followed by neutralization with acetic acid. Invention provides simplifying technology of the process and expanding assortment of the end products.

EFFECT: improved preparing method.

2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the method of obtaining the derivatives of 3-aroilantra(1,9-cd)isoxazol-6-one with the general formula of where X - hydrogen, halogen or the lowest alkyl, which are used as intermediate products in synthesis of derivatives 7,8-phthalylclaridone, used as dyes for the polyester fibres. The essence of the method lies in heating 1-hydroxytriazone-2-aroilantraquinone in acetic anhydride.

EFFECT: simpler technology and safer process.

1 cl, 2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the method of obtaining the derivatives 3-aroilanra-(1,9-cd)isoxazole-6-one of the general formula where X - hydrogen, halogen or the lowest alkyl, which are used as intermediate products in synthesis of derivatives 7,8-phthalylclaridone used as dyes for various polymeric materials and polyester fibres. The essence of the method lies in boiling 1(triazene-N-sulfonate)-2-aroihtranquonine in spirit solution of alkali with the subsequent neutralisation by acetic acid.

EFFECT: simpler technology and safer process.

1 cl, 2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention can be applied in medicine and concerns inhibitors of MaR-kinase p38 of formula where W represents N or O, when Y represents C, and W represents C, when Y represents N; U represents CH or N; V represents C-E or N; X represents O, S, SO, SO2, NH, C=O,-C=NOR1 or CHOR1; B represents H or NH2; R1, E and A stands for H or various alkyl, heteroalkyl, aromatic and heteroaromatic substitutes.

EFFECT: production of new biologically active compounds.

48 cl, 138 ex, 54 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to novel hexafluoroisopropanol-substituted ether derivatives of formula (I) to their pharmaceutically acceptable salts and to esters which are capable of bonding with LXR-alpha and/or LXR-beta, as well as to pharmaceutical compositions based on said compounds. In formula (I) R1 is hydrogen, lower alkyl or halogen, one of groups R2 and R3 is hydrogen, lower alkyl or halogen, and the second of groups R2 and R3 is -O-CHR4-(CH2)m-(CHR5)n-R6. Values of R4, R5, R6 m and n are given in the formula of invention.

EFFECT: novel compounds have useful biological properties.

22 cl, 4 dwg, 102 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel compounds of formula IA and their pharmaceutically acceptable salts. Claimed compounds have inhibitory effect on DAAO. In formula IA , A denotes hydrogen; Z denotes O; R1 is selected from a hydrogen atom, hydroxy or methoxy; R2 is selected from a hydrogen atom, F, Cl, hydroxy, methoxy and methyl; or R1 is selected from a hydrogen atom, F, hydroxy and methoxy; and R2 is selected from a hydrogen atom, Cl, hydroxy, methoxy and methyl; R3 is selected from C1-C6alkyl, hydroxy, methoxy, halogen, cyano, CH2-CH2-phenyl and OCH2-phenyl; R4a is selected from C1-C6alkyl, hydroxy, methoxy and halogen. The invention also relates to use of compounds in which R3a denotes hydrogen, C1-C6alkyl, hydroxy, methoxy, halogen, cyano, CH2-CH2-phenyl, O-CH2-phenyl, NH-CO-O-CH2-phenyl, R4a denotes H, C1-C6alkyl, hydroxy, methoxy, halogen, NH-CO-O-CH2-phenyl, for making a medicinal agent.

EFFECT: wider field of use of the compounds.

14 cl, 4 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to compounds of structural formula I and their pharmaceutically acceptable salts. In structural formula I , X is oxygen; Y is oxygen; Y1 Y2, R7 and R4 represent H; X1 and X2 are independently selected from a group consisting of hydrogen, an alkyl group containing 1 to 5 carbon atoms, in which one or more hydrogen atoms of the alkyl group can be substituted with a halogen, aryl group containing 6 to 10 carbon atoms or a cycloalkyl group containing 3 to 9 carbon atoms, or a 5-9-member heterocyclic group with 2 heteroatoms selected from N and O, or a cycloalkyl group containing 5 to 9 carbon atoms; values of the rest of the radicals are given in the formula of invention. The invention also pertains to a pharmaceutical composition having properties of selective inhibitors of type IV phosphodiesterase, containing a therapeutically effective amount of the invented compound.

EFFECT: increased effectiveness of the compounds.

6 cl, 23 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to novel compounds, which possess qualities to estrogen modulators, of general formula (1) or its pharmaceutically acceptable salt, where R1 represents hydrogen atom or (C1-C6)alkyl, -SO2NR7R8, phenyl (C1-C3)alkyl or (C1-C3)alkyl, substituted with 5-8-member heterocyclic radical, containing nitrogen atom; R2 and R3 each independently represents hydrogen atom or hydroxyl, halogen atom or (C1-C6)alkoxy; X represents O, S, SO, SO2 or NR4; R4 represents hydrogen atom or (C1-C6)alkyl, phenyl, phenyl(C1-C3)alkyl, (C1-C3)alkyl, substituted with 5-8-member saturated heterocyclic radical, containing one nitrogen atom, or group -COR7, -CO2R7 or -SO2NR7R8, where phenyl is not substituted or is substituted with at least one substituent, selected from group which includes hydroxyl, halogen atom or phenyl(C1-C3)alkoxy; Y represents direct bond, -(CR10R11)n- or -R10C=CR11-; R7 and R8 each independently represents hydrogen atom or (C1-C6)alkyl group; R10 and R11 each independently represent hydrogen atom or cyano, or group CONR7R8; n equals 1 or 2; A represents (C3-C12)cycloalkyl or phenyl, where phenyl is not substituted or is substituted with at least one substituent, selected from group which includes hydroxyl, halogen atom, (C1-C3)alkyl, (C1-C3)alkoxy; when X represents NR4, Y and R2 together with containing them indazole cycle can also form 1H-pyrano[4,3,2-cd)indazole; on condition that: 1) when X represents O, S or NR4, R1 represents hydrogen atom or (C1-C6)alkyl, and Y stands for direct bond, then A is not optionally substituted phenyl; 2) when X represents O, R1O represents 6-OH or 6-OCH3, Y represents direct bond and A represents cyclopeptyl, then (R2, R3) or (R3, R2) are different from (H, CI) in position 4, 5; 3) when X stands for O, R1O represents 6-OH, R2 and R3 represent H, and Y represents CH=CH, then A is not phenyl or methoxyphenyl; 4) when X represents SO2, A represents phenyl and R1O represents 5-or 6-OCH3, then (R2, R3) or (R3, R2) are different from (H, OCH3) in position 6- or 5-, compound not being one of the following: 3-phenyl-5-(phenylmethoxy)-1H-indazole; n-hydroxy-3-phenylmethyl-7-(n-propyl)-benz[4,5]isoxazole; 3-(4-chlorphenylmethyl)-6-hydroxy-7-(n-propyl)-benz[4,5]isoxazole; 6-hydroxy-3-(2-phenylethyl)-7(n-propyl)-benz[4,5]isoxazole; 3-cyclopropyl-6-hydroxy-3-phenylmethyl-7-(n-propyl)-benz[4,5|isoxazole; 3-cyclohexylmethyl-6-hydroxy-3-phenylmethyl-7-propyl-benz[4,5]isoxazole. Invention also relates to pharmaceutical composition, application and method of prevention and treatment of disease, where modulation of estrogen receptors is required.

EFFECT: obtaining novel compounds, which possess qualities of estrogen receptors modulators.

18 cl, 7 dwg, 8 tbl, 97 ex

FIELD: chemistry.

SUBSTANCE: invention relates to azole derivatives of formula I , where: A denotes S, O; W denotes -(C=O)-; X are identical or different and denote =C(-R)- or =N-; Y denotes -O- or -NR1-; R denotes hydrogen, halogen, (C1-C6)-alkyl, nitro; R1 denotes hydrogen; R2 denotes (C5-C16)-alkyl, (C1-C4)alkyl-phenyl, where phenyl can be optionally mono- or poly-substituted with (C1-C6)-alkyl; R3 denotes hydrogen; or R2 and R3 together with the nitrogen atom bearing them can form a monocyclic saturated 6-member ring system, where separate members of this ring system can be substituted with 1 group selected from the following: -CHR5-, -NR5-; R5 denotes (C1-C6)-alkyl, trifluoromethyl; and physiologically acceptable salts thereof. The invention also pertains to methods of producing said compounds and a medicinal agent based on said compounds.

EFFECT: novel compounds and a medicinal agent based on said compounds are obtained, which can be used as hormone-sensitive lipase (HSL) or endothelial lipase (EL) inhibitors.

12 cl, 11 ex

Up!