WO1992019586A1 - Process for the preparation of 1-amino-4-bromoanthraquinones - Google Patents
Process for the preparation of 1-amino-4-bromoanthraquinones Download PDFInfo
- Publication number
- WO1992019586A1 WO1992019586A1 PCT/US1992/003214 US9203214W WO9219586A1 WO 1992019586 A1 WO1992019586 A1 WO 1992019586A1 US 9203214 W US9203214 W US 9203214W WO 9219586 A1 WO9219586 A1 WO 9219586A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mixture
- anthraquinone
- bromine
- mole
- reactant
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- JOVRIPGYHSRFFR-UHFFFAOYSA-N 1-amino-4-bromoanthracene-9,10-dione Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C(Br)=CC=C2N JOVRIPGYHSRFFR-UHFFFAOYSA-N 0.000 title abstract description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 17
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 29
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 25
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 25
- 229910052794 bromium Inorganic materials 0.000 claims description 25
- 239000000376 reactant Substances 0.000 claims description 24
- 150000004056 anthraquinones Chemical class 0.000 claims description 22
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 11
- -1 anthraquinone compounds Chemical class 0.000 claims description 8
- 235000019260 propionic acid Nutrition 0.000 claims description 7
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 abstract description 13
- 230000031709 bromination Effects 0.000 abstract description 10
- 238000005893 bromination reaction Methods 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 2
- MVRDXWVWKOUPDO-UHFFFAOYSA-N 1-amino-2-bromoanthracene-9,10-dione Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C=CC(Br)=C2N MVRDXWVWKOUPDO-UHFFFAOYSA-N 0.000 abstract 1
- 235000011054 acetic acid Nutrition 0.000 description 9
- SVTDYSXXLJYUTM-UHFFFAOYSA-N disperse red 9 Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC SVTDYSXXLJYUTM-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZINRVIQBCHAZMM-UHFFFAOYSA-N 1-Amino-2,4-dibromoanthraquinone Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C(Br)=CC(Br)=C2N ZINRVIQBCHAZMM-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- IIPRUQZTMZETSL-UHFFFAOYSA-N 1-bromo-4-(methylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(Br)=CC=C2NC IIPRUQZTMZETSL-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- IQHSSYROJYPFDV-UHFFFAOYSA-N 2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC(Cl)=C(Br)C(Cl)=C1 IQHSSYROJYPFDV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- FJJMTRXALHEJFS-UHFFFAOYSA-N 2,4-dibromo-1-(methylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(Br)=CC(Br)=C2NC FJJMTRXALHEJFS-UHFFFAOYSA-N 0.000 description 1
- XPZRLOAGIQPVBC-UHFFFAOYSA-N 2-bromo-1-(methylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC(Br)=C2NC XPZRLOAGIQPVBC-UHFFFAOYSA-N 0.000 description 1
- 206010013647 Drowning Diseases 0.000 description 1
- 150000001243 acetic acids Chemical class 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000005236 alkanoylamino group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 150000004672 propanoic acids Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
- C07C225/26—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings
- C07C225/32—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings of condensed quinone ring systems formed by at least three rings
- C07C225/34—Amino anthraquinones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
Definitions
- This invention pertains to a novel process for the preparation of 1-amino-4-bromoanthraquinones by the bromination of the corresponding 1-aminoanthraquinone. More specifically, this invention pertains to the preparation of 1-amino-4-bromoanthraquinones by
- 1-Amino-4-bromoanthraquinones are used extensively in the manufacture of colorant and dye compounds.
- 1-methylamino-4-bromoanthraquinone may be reacted with various nucleophiles, e.g., amines, to produce red to blue disperse dyes used in the coloration of synthetic textile materials such as polyester fibers.
- the formation of the 2-isomer not only represents a loss in yield from the 1-aminoanthraquinone reactant but also can require purification of the bromination product depending, for example, on the use for which the 1-amino-4- bromoanthraquinone is intended.
- the mole ratio of hydrobromic acid:anthraquinone reactant is at least 0.5:1 at the commencement of the bromine addition;
- R 1 is hydrogen or an alkyl or cycloalkyl radical
- R 2 is an alkyl radical, a cycloalkyl radical, halogen or -NH-R 1 ;
- n 0, 1 or 2.
- the bromination process provided by the invention occurs in a heterogeneous system wherein a substantial amount of the anthraquinone reactant exists as a slurry or dispersion in the carboxylic acid.
- the lower carboxylic acid employed as the reaction medium may be selected from aliphatic carboxylic acids having 2 to 4 carbon atoms, especially acetic acid, propionic acid or a mixture thereof. Since the freezing point of acetic acid is 16.6°C, when the process is carried out within the preferred temperature range, acetic acid must be used in combination with one or more other carboxylic acids.
- the preferred reaction medium or diluent may be selected from aliphatic carboxylic acids having 2 to 4 carbon atoms, especially acetic acid, propionic acid or a mixture thereof. Since the freezing point of acetic acid is 16.6°C, when the process is carried out within the preferred temperature range, acetic acid must be used in combination with one or more other carboxylic acids.
- carboxylic acid comprises a mixture of acetic and propionic acids, e.g., in acetic:propionic weight ratios of 4:1 to 1:1.
- the amount of carboxylic acid used is not critical and can be varied substantially, e.g., amounts which give carboxylic acid:anthraquinone reactant weight ratios in the range of 9:1 to 25:1.
- the carboxylic acid:-anthraquinone reactant weight ratio normally is in the range of 10:1 to 12:1.
- the hydrogen bromide may be provided to the process in the form of an aqueous solution, e.g, hydrobromic acid having a HBr concentration of 30 to 65, preferably 40 to 50 weight percent.
- an aqueous solution e.g, hydrobromic acid having a HBr concentration of 30 to 65, preferably 40 to 50 weight percent.
- the amount of hydrogen bromide initially present preferably gives a hydrogen bromide:anthraquinone mole ratio of 0.5:1 to 1.5:1.
- the amount of elemental bromine added over the course of the reaction in accordance with my novel process normally is 1.0 to 1.2 mole Br 2 per mole of anthraquinone reactant.
- the use of lesser amounts of bromine results in an unsatisfactory degree of reactant conversion whereas larger amounts causes the formation of excessive amounts of dibrominated by-product, i.e., 1-amino-2,4-dibromoanthraquinones.
- the elemental bromine may be added as essentially pure bromine or as a mixture with an inert diluent such as one or more of the carboxylic acids described above. Typically, the bromine is added to a vigorously agitated, cooled mixture of the anthraquinone reactant, the hydrogen bromide and the carboxylic acid (or mixture of
- the bromine addition usually is completed within 45 to 60 minutes although the rate of addition may be faster or slower depending upon the particular operating procedure and equipment used and the efficiency of the heat
- the bromination process is performed at
- the alkyl and cycloalkyl groups represented by R 1 and R 2 in formulas (I) and (II) may be unsubstituted or substituted alkyl of up to 12 carbon atoms or unsubstituted or substituted cycloalkyl containing 5 to 7 ring carbon atoms.
- substituents which may be present on the substituted alkyl groups include alkoxy of up to 4 carbon atoms, e.g., methoxy, ethoxy and butoxy; alkanoyloxy of up to 4 carbon atoms, e.g., acetoxy; hydroxy; cyano; alkanoylamino, e.g., acetylamino (acetamido); and the like.
- the -NH-R 1 groups which R 2 may represent may be the same as or different from the -NH-R 1 at the 1-position of the anthraquinone nucleus.
- R 1 is an a lkyl or cycloalkyl radical, preferably unsubstituted alkyl of up to 6 carbon atoms such as methyl ethyl, propyl, isopropyl, butyl, isobutyl, hexyl and the like.
- a vigorously agitated mixture of acetic acid (135.8 parts), propionic acid (74.5 parts), 48% hydrobromic acid (12.8 parts, 0.076 mole) and 1-methylaminoanthraquinone (18.0 parts, 0.076 mole) is cooled to 0 to 5°C.
- Bromine (13.3 parts, 0.083 mole) is added to the mixture over a period of about 1 hour at a rate of 2.2 to 2.5 parts per 10 minutes while maintaining the temperature of the mixture at 0 to 5°C.
- the product also contained about 0.3% total of 1-amino-4-bromoanthraquinone and 1-amino-2,4-dibromoanthraquinone.
- the 1-methylaminoanthraquinone reactant contained some 1-aminoanthraquinone resulting in the presence of minor amounts of 1-amino-4-bromoanthraquinone and 1-amino-2,4-dibromoanthraquinone in the final reaction mixture.
- the 1-methylaminoanthraquinone reactant contained some 1-aminoanthraquinone resulting in the presence of minor amounts of 1-amino-4-bromoanthraquinone and 1-amino-2,4- dibromoanthraquinone in the final reaction mixture.
- the 1-methylaminoanthraquinone reactant contained some 1-aminoanthraquinone resulting in the presence of minor amounts of 1-amino-4-bromoanthraquinone and 1-amino-2,4-dibromoanthraquinone in the final reaction mixture.
- 1,X-diaminoanthraquinone impurity A mixture (20 mL) of acetic acid and bromine (8.75 parts, 0.0547 mole) is added to the mixture over a period of about 1 hour while maintaining the temperature of the mixture at 0 to 5°C. Samples of the reaction mixture were taken (1) after 2 mL of the bromine-containing mixture had been added, (2) after 10 mL of the bromine-containing mixture had been added and (3) 5 minutes after 20 mL of the bromine-containing mixture had been added. Water (120 mL) was added to the mixture to precipitate the product which was collected by filtration, washed first with water and then with isopropanol and dried. The crude product weighed 12.92 g. The three samples of the reaction mixture and the crude product were analyzed by liquid chromatography. The results of the analyses, reported in area percent, are shown below wherein AQ means anthraquinone.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4511866A JPH06507409A (ja) | 1991-05-02 | 1992-04-20 | １−アミノ−４−ブロモアントラキノン類の製造方法 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/694,612 US5117014A (en) | 1991-05-02 | 1991-05-02 | Process for the preparation of 1-amino-4-bromoanthraquinones |
| US694,612 | 1991-05-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1992019586A1 true WO1992019586A1 (en) | 1992-11-12 |
Family
ID=24789565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1992/003214 WO1992019586A1 (en) | 1991-05-02 | 1992-04-20 | Process for the preparation of 1-amino-4-bromoanthraquinones |
Country Status (6)
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105369A (zh) * | 2019-12-12 | 2021-07-13 | 林齐坤 | 溶剂法制备溴氨酸的磺化方法 |
| CN111116425A (zh) * | 2019-12-30 | 2020-05-08 | 江苏亚邦染料股份有限公司 | 一种溴氨酸钠盐溴化工艺 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE164791C (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * | ||||
| DE146691C (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * | 1900-10-15 | |||
| GB1239778A (en) * | 1968-10-03 | 1971-07-21 | Ici Ltd | Halogenation process |
-
1991
- 1991-05-02 US US07/694,612 patent/US5117014A/en not_active Expired - Fee Related
-
1992
- 1992-03-17 TW TW081101986A patent/TW216416B/zh active
- 1992-04-08 CA CA002065695A patent/CA2065695A1/en not_active Abandoned
- 1992-04-20 EP EP92913607A patent/EP0585395A1/en not_active Withdrawn
- 1992-04-20 WO PCT/US1992/003214 patent/WO1992019586A1/en not_active Application Discontinuation
- 1992-04-20 JP JP4511866A patent/JPH06507409A/ja active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE164791C (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * | ||||
| DE146691C (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * | 1900-10-15 | |||
| GB1239778A (en) * | 1968-10-03 | 1971-07-21 | Ici Ltd | Halogenation process |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0585395A1 (en) | 1994-03-09 |
| JPH06507409A (ja) | 1994-08-25 |
| TW216416B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1993-11-21 |
| US5117014A (en) | 1992-05-26 |
| CA2065695A1 (en) | 1992-11-03 |
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