2,3-dicarboxy-6,7-dimethylanthraquinone
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to 2,3-dicarboxy-6,7-dimethylanthraquinone of the formula (I):
that is characterized by melting point value Tm 207°C. This compound can be used as the parent substance in synthesis of metal complexes tetra(-di-6,7-carboxy)-anthraquinonoporphyrazine used as dyes and catalysts. Also, invention describes methods for synthesis and using compound of the formula (I).
EFFECT: value properties of compound and complexes.
4 dwg, 6 ex
The invention relates to the chemical industry, namely, to obtain a new derivative of 2,3-dicarboxaldehyde as starting compound for the synthesis of metal complexes of Tetra-(di-6,7-carboxy)-intrahemispheric that can be used as dyes, catalysts, and other fields of science and technology.
The level of technology
Known 2,3-dicarboxaldehyde, a structural analogue [K.Sakamoto, E.Ohno. Synthesis of Cobalt Phthalocyanine Derivatives and their Cyclic Voltammograms // Dyes and Pigments. 1997. Vol.35. N4. P.375-386].
However, when using this compound as the source can be obtained only tetranitroaniline that do not have coloring properties. Therefore, they cannot be used as a pigment or dye in the solutions.
The invention
Inventive task was to search for new compounds, which are derivatives of 2,3-dicarboxaldehyde that when using it as a source of product would give the opportunity to synthesize substituted tetranitroaniline possessing properties of dyes cotton and viscose materials, as well as catalysts of oxidation-reduction processes.
The problem is solved 2,3-dicarboxy-6,7-dimethylanthracene formula
The structure of this compound proved by data of elemental analysis and IR spectroscopy.
Thus, in the IR spectrum of the inventive compound (1) it is possible to allocate a number of common absorption bands with anthraquinone [.Pecile, .Lunelli Polarized Infrared Spectra of Single Crystals of 9,10-Anthraquinone and 9,10-Anthraquinone-ds// J.Chem.Phys. 1967. Vol.46. N6. P.2109-2118].
The invention provides the following advantages:
The use of 2,3-dicarboxy-6,7-dimethylanthracene gives you the ability to synthesize metal complexes of Tetra-(di-6,7-carboxy)intrahemispheric with the ability to paint in water-alkaline environments cotton and viscose materials, as well as the hair, when using them as an acid dye, exhibiting to the same catalytic activity in oxidation-reduction reactions.
Information confirming the possibility of carrying out the invention
The inventive compound can be obtained, for example, by the following method.
To implement the method using the following ingredients:
dianhydride pyromellitic acid - TU 6-14-786-72;
anhydrous aluminium chloride - OST 6-01-300-74;
concentrated sulphuric acid - GOST 4204-77;
o-xylene - GOST 9949-76
The method is implemented in two stages:
1. The acylation of o-xylene by dianhydride pyromellitic acid in the presence of anhydrous aluminum chloride with the EME
In a flask equipped with stirrer, thermometer and reflux condenser, was placed 10.0 g (0.046 mole) of the dianhydride pyromellitic acid, 20 ml of o-xylene and under vigorous stirring was added 18.4 g (0.138 mol) of anhydrous aluminum chloride. Slowly the reaction mixture is heated to 75-80°C and maintained at this temperature for 8 hours. After cooling, to the reaction mass is added 50 ml of water and after soaking for 30 minutes, add hot soda solution and separating the precipitated precipitate aluminum hydroxide. To the aqueous layer of the filtrate add hydrochloric acid to pH 3-4 and the precipitate is filtered intermediate product [5-(3,4-dimethyl)benzoyltartaric acid], which is washed with water until neutral environment and dried at a temperature of 75-80°C.
Obtained 5-(3,4-dimethyl)benzoylthiourea acid
2. Intramolecular cyclization by treatment of 5-(3,4-dimethyl)benzoyltartaric acid concentrated sulfuric acid (monohydrate) schema
In a flask with a volume of 200 ml equipped with a stirrer and thermometer, was placed 10 ml monohydrate and heated to 130°C. and Then for 15 minutes with vigorous stirring, add 5 g obtained in the first stage, 5-(3,4-dimethyl)benzoyltartaric acid, the temperature was raised to 150°With and the well is live in 5 hours. The mass after cooling with stirring, poured into 200 ml of water, filtered, washed with a large amount of ice-cold water, dissolve in soda solution and acidified with hydrochloric acid. The precipitate is filtered off and washed with water until the disappearance of the chloride ions. Such processing is repeated twice. Dried at 100°C.
Found, %: C - 66.1; H - 3.8; C18H12O6.
Calculated, %: 66.7; H - 3.7.
Yield: 6.7 g (33%). The melting point of 207°C.
The obtained target product - 2,3-dicarboxy-6,7-dimethylanthracene - solid white, soluble in aqueous-alkaline solutions, hot water, DMF.
Example 1. The use of 2,3-dicarboxy-6,7-dimethylanthracene as a starting compound for the synthesis of copper complex of Tetra-(di-6,7-carboxy)intrahemispheric.
The method is carried out in two stages:
1 stage. In a test tube made of quartz glass place the pounded mixture of 0.2 g (0.6 mmol) of 2,3-dicarboxy-6,7-dimethylanthracene, 0.24 g (4.0 mmol) of urea, 0.036 g (0.18 mmol) of copper acetate, 0.02 g (0.4 mmol) of ammonium chloride and 0.002 g (0.01 mmol) of ammonium molybdate. The mass is slowly heated to 180°C for one hour and incubated for 3 hours. Purification of the target product consistently washing with 5%hydrochloric acid, acetone and presidenial of sulphuric acid.
The output of Tetra-(di-6,7-methyl)intrahemispheric 0.06 g (30%)
Dark blue substance has a solubility in concentrated sulfuric acid.
Found, %: C - 70.9; H - 3.4; N - 9.6. C72H40N8O8Cu.
Calculated, %: C - 71.6; H - 3.3; N - 9.3.
stage 2. In dvuhhodovoy flask containing 10 ml of water, add a solution of 0.2 g of Tetra-(di-6,7-methyl)intrahemispheric copper in 3 ml of concentrated sulfuric acid. Heated to 55-60°and with stirring, add 0.3 g of potassium permanganate in units of 0.05 g as the disappearance of its color. Adding lead to the emergence of sustainable staining solution. The hot suspension is filtered. The precipitate is washed with hot sodium hydroxide solution and after cooling, acidified with hydrochloric acid to pH 3-4. The precipitation Tetra-(di-6,7-carboxy)intrahemispheric copper is filtered off, washed with water until neutral. Then the product is dissolved in soda solution and acidified with hydrochloric acid. The precipitate is filtered off and washed with water until the disappearance of the chloride ions. Such processing is repeated twice. Dried at 75-80°C.
The output of Tetra-(di-6,7-carboxy)intrahemispheric copper 0.1 g (48%).
Dark blue substance has a solubility in aqueous-alkaline solutions, DMF, concentrated sulfuric acid.
ESP in aqueous-alkaline solution, λmaxnm: 681 (figure 2).
Neid is but %- 58.9; H - 1.8; N - 8.0. C72N8H24O24Cu.
Calculated, %: C - 59.7; H - 1.7; N - 7.7.
Example 2. The use of 2,3-dicarboxy-6,7-dimethylanthracene as a starting compound for the synthesis of cobalt complex of Tetra-(di-6,7-carboxy)intrahemispheric.
Synthesis is carried out analogously to example 1. In the first stage instead of copper acetate is used 0.038 g (0.18 mmol) of cobalt acetate.
The output of Tetra-(di-6,7-methyl)intrahemispheric cobalt: 0.11 g (54%).
Dark blue substance has a solubility in concentrated sulfuric acid.
Found, %: C - 58.8; H - 1.6; N - 8.0. C72N8H24O24Co.
Calculated, %: 59.9; H - 1.7; N - 7.8.
In the second stage instead of the Tetra-(di-6,7-methyl)intrahemispheric copper using 0.2 g of Tetra-(di-6,7-methyl)intrahemispheric cobalt.
The output of Tetra-(di-6,7-carboxy)intrahemispheric cobalt: 0.09 g (43%).
Dark blue substance has a solubility in aqueous-alkaline solutions, DMF, concentrated sulfuric acid.
ESP in aqueous-alkaline solution, λmaxnm: 676 (figure 3).
Found, %: C - 61.0; H - 1.8; N - 7.6. C72N8H24O24Co.
Calculated, %: 59.9; H - 1.7; N - 7.8.
Example 3. The use of Tetra-(di-6,7-carboxy)intrahemispheric copper as a dye cotton fabrics. Dyeing conducted according to the methodology [Laboratory is atorny workshop on the application of dyes, Ed. Melnikov B.N. M.: Chemistry, 1972. 342 S.]
A sample of cotton fabric weighing 1 g moisten within 0.5 min, squeezed to 100% gain and is placed in a dye bath composition, g/l:
Tetra-(di-6,7-carboxy)intrahemispheric copper | 2 |
Sulfacid - 31 | 0.5 |
Sodium chloride | 5 |
Module baths | 50 |
Within 15-30 min heat the bath to the boil and maintain for 1 hour. The sample was then drained, washed thoroughly with warm, then cold water, and dried.
Example 4. The use of Tetra-(di-6,7-carboxy)intrahemispheric copper as a dye viscose fabrics. Dyeing conducted according to the methodology [Laboratory workshop on the application of dyes, Ed. Melnikov B.N. M.: Chemistry, 1972. 342 S.].
Sample viscose fabric weighing 1 g was soaked in a period of 0.5 minutes at a temperature of 40°C, press up to 100% of body weight and placed in a dye bath composition, g/l:
Tetra-(di-6,7-carboxy)intrahemispheric copper | 2 |
Sulfacid - 31 | 0.5 |
Sodium chloride | 10 |
Sodium carbonate | 0.5 |
Module baths |
Within 15-30 min heat the bath to boiling and maintained at this temperature for 40 minutes and 20 minutes in the cooling up to 30°With tub. The sample was then drained, washed thoroughly with warm, then cold water, and dried.
Example 5. The use of Tetra-(di-6,7-carboxy)intrahemispheric copper as an acid dye.
A sample of wool (fiber) mass of 1 g is placed in a dye bath composition, g/l:
Tetra-(di-6,7-carboxy)intrahemispheric copper | 6 |
Glauber's salt | 40 |
Module baths | 50 |
Within 15-30 min heat the tub up to 60°C and maintained at this temperature for 40 minutes and 20 minutes in the cooling up to 30°With tub.
The sample was then drained, washed thoroughly with warm, then cold water and treated with a solution of sulfuric acid composition, ml:
sulfuric acid | 1 |
water | 50 |
The sample is drained, washed thoroughly with warm, then cold water, and dried.
Samples of the color charts according to examples 3, 4, 5 shown in figure 4.
Example 6. The use of Tetra-(di-6,7-carboxy)intrahemispheric cobalt as a catalyst in the reaction liquid phase OK the comprehension of cysteine. Catalytic activity was determined by the method of [Shikova YEAR Study of the effect of chemical modification of the phthalocyanine ligand on the catalytic properties of metal complexes. Dis.... Kida. chem. Sciences. Ivanovo, 1999. 156 S.]
The experiments were carried out in the liquid phase in the reaction vessel, mounted on a high-speed shaker (350 qual/min), temperature-controlled with an accuracy of ±0,2°C. the reaction Rate was measured volumetric, accuracy of measurement ±of 0.05 ml. Processes were carried out at 298 K. the reaction vessel connected to a Gasometer, was loaded with 10 ml of substrate solution and an accurately weighed sample of the catalyst placed in the boat. The kinetic experiments were carried out in the field, when the reaction rate is observed linear dependence on the number of swings.
The activity of Tetra-(di-6,7-carboxy)intrahemispheric cobalt (A) in the reaction liquid-phase oxidation of cysteine was
A=126 g-mol O2×(g-mol cat-RA)-1×min-1.
2,3-dicarboxy-6,7-dimethylanthracene formula
FIELD: organic chemistry, medicine, oncology.
SUBSTANCE: sensitizing agent for photodynamic disruption of malignant neoplasm cells represents a new compound - 18-hydroxy-substituted cycloimide of chlorine p6 or 7,8-dihydroxybacteriochlorine of the formula (I):
. Compounds of the formula (I) are used as an agent in treatment of malignant neoplasm. Invention expands assortment of sensitizing agents used in carrying out the photodynamic therapy.
EFFECT: valuable medicinal properties of agent.
6 cl, 1 dwg
FIELD: chemistry of metalloorganic compounds.
SUBSTANCE: invention relates to new derivatives of metalloporphyrazines of the general formula (I):
wherein M means Cu, Co. These compounds can be used as dyes, catalysts of different processes and material for sensitive members of gas pickups.
EFFECT: valuable properties of complexes.
4 fig, 1 dwg, 5 ex
FIELD: microbiology.
SUBSTANCE: invention relates to method for production of porphyrinopeptides satisfying the formula I , wherein R1 and R2 independently from one another represent amino acids or peptides comprising 2-15 of amino acid residues, wherein α-carboxylic groups of amino acids or peptides may be modified by C1-C8-alkyl ester and side functional groups of amino acids or peptides may be protected; in particular R1 is ArgOMe; R2 is -OH (III); R1 is LeuHisOMe; R2 is -OH (IV); R1 is LeuLeuValPheOMe; R2 is -OH (V); porphyrin carboxylic group may be modified by methyl or other C1-C9-ester or pharmaceutically acceptable salt; Y- represents Cl-; Me represents Zn, Cu, Fe, Mn. Claimed method includes activation of porphyrin carboxylic group with N-oxy-5-norbornene-2,3-dicarboxyimede in molar ratio of 1:1 in presence of N,N'-dicyclohexylcarbodiinide; or with diphenylphosphorylazide (DPPA) in equimolar ratio of porphyrin/DPPA in presence of base. Then porphyrin with activated carboxylic group is brought into reaction with amino component (amino acid or peptide) in form of mineral acid salt, which is neutralized with base. Also disclosed are methods for application of compounds (I) as nucleotic agents.
EFFECT: new nucleotic agents.
4 cl, 7 ex, 1 tbl
FIELD: biochemistry.
SUBSTANCE: invention relates to method for production of synthetic chlorophyll (Chl) or bacteriochlorophyll (Bchl) derivatives of general formula I , wherein X is O;. Claimed method includes interaction under anaerobic conditions of Chl, Bchl derivatives containing COOCH3-group in C-132-position and COOR3-group in C-172-position in presence of tetraethyl orthotitanate. Further compounds of formula I wherein R1 and R2 are different radicals are obtained in aproton solvent such as peroxide-free tetrahydrofurane and dimethyl formamide, and compounds of formula I wherein R1 and R2 are the same ones are produced by using R1OH as a solvent. Derivatives of present invention are useful as stabilizers, linkage/spacer for binding another acceptable molecules to Chl/Bchl macrocycle.
EFFECT: simplified method for production of various chlorophyll or bacteriochlorophyll derivatives.
13 cl, 3 ex, 2 tbl, 8 dwg
FIELD: organic chemistry.
SUBSTANCE: invention relates to new derivatives of metalloporphyrazine of the general formula (I): wherein M means Cu, Co. These compounds can be used as dyes, catalysts in different processes and materials of sensitive members of gas sensor.
EFFECT: valuable properties of compounds.
2 cl, 6 sch, 1 dwg, 5 ex
where R1and R2- substituents, which may represent amino acids, derivatives of amino acids, peptides, consisting of 1-15 amino acid residues, derived peptides consisting of 1-15 amino acid residues, and-carboxyl group of amino acids or peptides and side groups of amino acids or peptides can be modified, and it is possible that R1=R2or R1
R2=OH; carboxyl group of the porphyrin can be modified methyl or other C2-C8-ester or a physiologically acceptable salt; Y-represents Cl-CH3SOO-; Me represents Fe, with the exception of compounds where
Me=Fe3+, Y-=Cl-,
R1=-LeuLeuValPheOMe, R2=-OH; R1=-ValPheOMe, R2=-OH; R1=-LeuHisOMe,
R2=-OH; R1=-LeuHisAlaOMe, R2=-OH; R1=-LeuHisNHC10H20COOMe, R22=-LeuHisNHC10H20COOMe; R1=-Lys(Tfa)AlaAlaOMe, R2=-OH;
R1=-ValPheOMe, R2=-LeuHisOMe; R1=-LeuLeuValPheOMe, R2=-LeuHisOMe;
R1=-LeuLys(Tfa)LeuOMe, R2=-OH; R1=-LeuLys(Tfa)LeuOMe, R2=-LeuHisOMe;
R1=-Lys(Tfa)AlaAlaOMe, R2=-AlaHisLys(Cbz)LeuOMe; R1=-GlyOBzl,
R2=-GlyOBzl; R1=-HisOMe, R2=-HisOMe; R1=-LeuHisOMe, R2=-LeuHisOMe;
R1=-LeuHisLeuGlyCys(Bzl)OBzl, R2=-LeuHisLeuGlyCys(Bzl)OBzl;
R1=-LeuHisOMe, R2=-OEt; R1=-LeuHisLeuGlyCys(Bzl)OBzl, R2=-OEt; R1=-OBzl,
R2=-OBzl; R1=-OBzl, R2=-OH; R1=-AlaOMe, R2=-OBzl; R1=-HisOMe, R2=-OBzl;
R1=-LeuHisOMe, R2=-OBzl; R1=-LeuHisLeuGlyCys(Bzl)OBzl, R2=-OBzl;
R1=-LeuHisAlaLys(Cbz)GlyCys(Bzl)OBzl, R2=-OBzl; R1=-LeuHisLys(Cbz)OMe,
R2=-OH; R1=-LeuHis(Bzl)Lys(Cbz)OMe, R2=-OH; R1=-LeuHisOMe, R2=-OMe;
R1=-LeuHis(Bzl)Lys(Cbz)OMe, R2=-OMe; R1=-AlaLeuAlaPheAlaCys(Bzl)OMe,
R2=-LeuHis(Bzl)Lys(Cbz)OMe; R1=-AlaLeuAlaPheAlaCys(Bzl)OBzl,
R2=-LeuHis(Bzl)Lys(Cbz)OMe; R1=-LeuHisAlaLys(Cbz)Cys(Bzl)OBzl,
R2=-LeuHis(Bzl)Lys(Cbz)OMe; R1=-LeuHisOMe, R2=-OMe;
R1=-GlyProArgGlyGlyOMe, R2=-OH;
R1=-ArgProProGlyPheSer(Bzl)PheArgGlyGlyOMe, R2=-OH,
two ways to get hemin derivatives of General formula I, hemin derivatives of the formula I, formerly known above, as inhibitors of proteolytic enzymes: the HIV protease, pepsin, trypsin, chymotrypsin
with antitumor activity and low toxicity, which can be used in boron neutron capture therapy had cancer







FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to 2,3-dicarboxy-6,7-dimethylanthraquinone of the formula (I):
that is characterized by melting point value Tm 207°C. This compound can be used as the parent substance in synthesis of metal complexes tetra(-di-6,7-carboxy)-anthraquinonoporphyrazine used as dyes and catalysts. Also, invention describes methods for synthesis and using compound of the formula (I).
EFFECT: value properties of compound and complexes.
4 dwg, 6 ex
FIELD: organic chemistry.
SUBSTANCE: invention relates to 2,3-dicarboxy-5,6,8-trimethylanthraquinone of the formula (I):
. This compound can be used in synthesis of metal complexes of tetra-(tri-5,6,8-carboxy)-anthraquinonoporphyrazine used as dyes and catalysts. Compound of the formula (I) is characterized by melting point value (Tm) 207°C. Also, invention describes methods for synthesis and using compound of the formula (I).
EFFECT: valuable properties of compound.
4 cl, 6 ex
FIELD: chemistry.
SUBSTANCE: present invention refers to the method for preparation of aloe-emodin, and rein or diacerein used for treatment of the diseases concerned with anomalous dystrophy of connective tissues. The method for preparation of aloe-emodin includes oxidation of aloin dissolved in the polyatomic alcohol with oxygen-containing gas in the presence of acid. The method for preparation of rein or diacerein includes the following stages: a) oxidation of aloin dissolved in the polyatomic alcohol with oxygen-containing gas in the presence of acid to aloe-emodin; b) oxidation of aloe-emodin with chrome-free oxidising media to rein; c) purification of the rein obtained on the stage b) and d) optional acetylation of the rein obtained on the stage c) with acetylation agent to diacerein. The claimed method allows obtaining of aloe-emodin with good yield and purity level without using of toxic or harmful substances and complicated purification methods.
EFFECT: claimed method allows also diacerein obtaining without using of hexavalent; chrome as oxidiser and without complicated purification methods.
17 cl, 1 tbl, 5 ex
FIELD: organic chemistry.
SUBSTANCE: invention relates to new derivatives of metalloporphyrazine of the general formula (I): wherein M means Cu, Co. These compounds can be used as dyes, catalysts in different processes and materials of sensitive members of gas sensor.
EFFECT: valuable properties of compounds.
2 cl, 6 sch, 1 dwg, 5 ex
FIELD: biochemistry.
SUBSTANCE: invention relates to method for production of synthetic chlorophyll (Chl) or bacteriochlorophyll (Bchl) derivatives of general formula I , wherein X is O;. Claimed method includes interaction under anaerobic conditions of Chl, Bchl derivatives containing COOCH3-group in C-132-position and COOR3-group in C-172-position in presence of tetraethyl orthotitanate. Further compounds of formula I wherein R1 and R2 are different radicals are obtained in aproton solvent such as peroxide-free tetrahydrofurane and dimethyl formamide, and compounds of formula I wherein R1 and R2 are the same ones are produced by using R1OH as a solvent. Derivatives of present invention are useful as stabilizers, linkage/spacer for binding another acceptable molecules to Chl/Bchl macrocycle.
EFFECT: simplified method for production of various chlorophyll or bacteriochlorophyll derivatives.
13 cl, 3 ex, 2 tbl, 8 dwg
FIELD: microbiology.
SUBSTANCE: invention relates to method for production of porphyrinopeptides satisfying the formula I , wherein R1 and R2 independently from one another represent amino acids or peptides comprising 2-15 of amino acid residues, wherein α-carboxylic groups of amino acids or peptides may be modified by C1-C8-alkyl ester and side functional groups of amino acids or peptides may be protected; in particular R1 is ArgOMe; R2 is -OH (III); R1 is LeuHisOMe; R2 is -OH (IV); R1 is LeuLeuValPheOMe; R2 is -OH (V); porphyrin carboxylic group may be modified by methyl or other C1-C9-ester or pharmaceutically acceptable salt; Y- represents Cl-; Me represents Zn, Cu, Fe, Mn. Claimed method includes activation of porphyrin carboxylic group with N-oxy-5-norbornene-2,3-dicarboxyimede in molar ratio of 1:1 in presence of N,N'-dicyclohexylcarbodiinide; or with diphenylphosphorylazide (DPPA) in equimolar ratio of porphyrin/DPPA in presence of base. Then porphyrin with activated carboxylic group is brought into reaction with amino component (amino acid or peptide) in form of mineral acid salt, which is neutralized with base. Also disclosed are methods for application of compounds (I) as nucleotic agents.
EFFECT: new nucleotic agents.
4 cl, 7 ex, 1 tbl
FIELD: chemistry of metalloorganic compounds.
SUBSTANCE: invention relates to new derivatives of metalloporphyrazines of the general formula (I):
wherein M means Cu, Co. These compounds can be used as dyes, catalysts of different processes and material for sensitive members of gas pickups.
EFFECT: valuable properties of complexes.
4 fig, 1 dwg, 5 ex
FIELD: organic chemistry, medicine, oncology.
SUBSTANCE: sensitizing agent for photodynamic disruption of malignant neoplasm cells represents a new compound - 18-hydroxy-substituted cycloimide of chlorine p6 or 7,8-dihydroxybacteriochlorine of the formula (I):
. Compounds of the formula (I) are used as an agent in treatment of malignant neoplasm. Invention expands assortment of sensitizing agents used in carrying out the photodynamic therapy.
EFFECT: valuable medicinal properties of agent.
6 cl, 1 dwg
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to 2,3-dicarboxy-6,7-dimethylanthraquinone of the formula (I):
that is characterized by melting point value Tm 207°C. This compound can be used as the parent substance in synthesis of metal complexes tetra(-di-6,7-carboxy)-anthraquinonoporphyrazine used as dyes and catalysts. Also, invention describes methods for synthesis and using compound of the formula (I).
EFFECT: value properties of compound and complexes.
4 dwg, 6 ex