CS196222B2 - Method of producing novel octahalogene-sulphophthaleine - Google Patents
Method of producing novel octahalogene-sulphophthaleine Download PDFInfo
- Publication number
- CS196222B2 CS196222B2 CS776442A CS644277A CS196222B2 CS 196222 B2 CS196222 B2 CS 196222B2 CS 776442 A CS776442 A CS 776442A CS 644277 A CS644277 A CS 644277A CS 196222 B2 CS196222 B2 CS 196222B2
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- acetic acid
- tetrachlorosulfophthalein
- glacial acetic
- sulphophthaleine
- octahalogene
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 47
- 229960000583 acetic acid Drugs 0.000 claims description 19
- 239000012362 glacial acetic acid Substances 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
Předmětem vynálezu je způsob výroby nových oktahalogensulfoftaleinů.It is an object of the present invention to provide novel octahalogen sulfophthaleins.
Tyto sloučeniny slouží v kombinaci s polypropylenglykoly jako indikátory bílkovin v tělesných tekutinách.These compounds, in combination with polypropylene glycols, serve as protein indicators in body fluids.
V daném případě jde zejména oIn the present case, it concerns in particular:
3‘,3“,5‘,5“-tetrabromfenol-3,4,5,6-tetrachlorsulfoftalem,3 ‘, 3,, 5‘, 5--tetrabromophenol-3,4,5,6-tetrachlorosulfophthal,
3‘,3“,5‘,5“-tetrachlorfenol-3,4,5,6-tetrabromsulfnftalein a 3‘,3“-dichlor-5‘,5“-dibromfenol-3,4,5,6-tetrachlorsulfoftalein.3 ‘, 3,, 5‘, 5--tetrachlorophenol-3,4,5,6-tetrabromosulfonaphthalein and 3 ‘, 3--dichloro-5‘, 5--dibromophenol-3,4,5,6-tetrachlorosulfophthalein.
Tyto sloučeniny se mohou vyrobit známými metodami, například reakcí známých tetrahalogenbenzensulfokarboanhydridů s fenoly nebo 2-halogenfenoly. v přítomnosti Lewisových kyselin, například chloridu cíničitého, a chloraci nebo bromací vzniklých fenolsulfoftaleinů v inertních rozpouštědlech, například chlorem nebo bromem v ledové kyselině octové.These compounds can be prepared by known methods, for example by reacting known tetrahalobenzenesulfocarboanhydrides with phenols or 2-halophenols. in the presence of Lewis acids such as tin (II) chloride and the chlorination or bromination of the phenolsulfophthalein formed in inert solvents such as chlorine or bromine in glacial acetic acid.
Jak již bylo výše uvedeno, tyto sloučeniny slouží jako indikátory, z nichž zejména výhodné jsou ty, které nesou v poloze 3‘,3“,5‘,5“ čtyři atomy chloru, protože ii nich je rušení dusíkatými bázemi ještě slabší než u odpovídajících hromovaných zástupců.As mentioned above, these compounds serve as indicators, of which particularly preferred are those which carry four chlorine atoms in the 3 ', 3', 5 ', 5' position, because even with them nitrogen interference is even weaker than the corresponding accumulated representatives.
Způsob výroby nových oktahalogensulfo196222 ftaleinů je spolu s jejich výtěžky á fyzikálními konstantami uveden v následujících příkladech.The process for the preparation of the novel octahalogensulfo196222 phthaleins, together with their yields and physical constants, is given in the following examples.
PřikladlHe did
3‘,3‘-dichlorfenol-3,4,5,6-tetrachlorsulfoftalein3 ‘, 3‘-dichlorophenol-3,4,5,6-tetrachlorosulfophthalein
25,7 g [0,2 molu) o-chlorfenolu se smísí se 45 g (0,14 molu) tetrachlor-o-sulfoanhydridu kyseliny benzoové, přidá se 9 ml (= = 20,4 g) chloridu cíničitého a 12 hodin se zahřívá za míchání na olejové lázni na 120 až 130 °C. Potom se přebytečný chlorfenol odstraní s vodní párou a zbytek se čistí vícenásobným rozpouštěním ve 4 N roztoku uhličitanu sodného a vysrážením kyselinou solnou a potom překrystalováním z ledové kyseliny octové. Získá se 5,3 g (=47%) růžově zbarveného 3‘,3“-dichlorfenol-3,4,5,6-tetrachlorsulfoftaleinu, který obsahuje 1 mol kyseliny octové, teplota tání 244 až 245 stupňů Celsia (molekulová hmotnost: C19H8CI6O5S. CzH4O2= 621,13).25.7 g (0.2 mol) of o-chlorophenol are mixed with 45 g (0.14 mol) of tetrachloro-o-sulfoanhydride benzoic acid, 9 ml (= 20.4 g) of tin (II) chloride are added and the mixture is stirred for 12 hours. with stirring in an oil bath at 120 to 130 ° C. The excess chlorophenol was then removed with water vapor and the residue purified by repeatedly dissolving in 4 N sodium carbonate solution and precipitating with hydrochloric acid and then recrystallizing from glacial acetic acid. 5.3 g (= 47%) of pink-colored 3 ', 3'-dichlorophenol-3,4,5,6-tetrachlorosulfophthalein are obtained, which contains 1 mol of acetic acid, m.p. (C2H4O2 = 621.13).
Stejným způsobem se získá při použití 0-bromfenolu 3‘,3“-dibromfenol-3,4,5,6-tetrachlorsulfoftalein, který po překrystalování z ledové kyseliny octové krystaluje rovněž s 1 molem kyseliny octové, teplota tání 172 až 173 °C.In the same way, 3 ‘, 3'-dibromophenol-3,4,5,6-tetrachlorosulfophthalein, which, after recrystallization from glacial acetic acid, also crystallizes with 1 mole of acetic acid, melts at 172-173 ° C, using O-bromophenol.
Příklad 2Example 2
3‘,3“-dibromfenol-3,4,5,6-tetrachlo'rsulf oftalein3 ‘, 3'-dibromophenol-3,4,5,6-tetrachlorosulfphthalein
4,9 g (0,01 molu) fenol-3,4,5,6-tetrachlbrsulfoftaleinu se rozpustí v 50 ml ledové kyseliny octové a při 20 °C se za míchání prikape roztok 1,1 ml (=3,37 g) bromu (0,04 gramatomu) v 50 ml ledové kyseliny octové. Míchá se ještě 3 hodiny, vzniklé krystaly se odsají a překrystalují z ledové kyseliny octové. Získá se 3,9 g (=55%) 3‘,3“-dibromfenol-3,4,5,6-tetrachlorsulfoftaleinu, teplota tání 173 až 174 °C. Sloučenina obsahuje 1 mol krystalické kyseliny octové (molekulová hmotnost: CisHsBrzCUOsS. C2H4O2= = 710,05).4.9 g (0.01 mole) of phenol-3,4,5,6-tetrachlorosulfophthalein are dissolved in 50 ml of glacial acetic acid and a solution of 1.1 ml (= 3.37 g) is added dropwise with stirring at 20 ° C. bromine (0.04 gram) in 50 ml glacial acetic acid. Stirring is continued for 3 hours, the crystals formed are filtered off with suction and recrystallized from glacial acetic acid. 3.9 g (= 55%) of 3 ‘, 3'-dibromophenol-3,4,5,6-tetrachlorosulfophthalein are obtained, m.p. 173-174 ° C. The compound contains 1 mole of crystalline acetic acid (molecular weight: C 18 H 18 Br 2 CuO 5 S. C 2 H 4 O 2 = = 710.05).
Příklad 3Example 3
3‘,3“-dibrom-5‘,5“-dichlorfenol-3,4,5,6-terachlorsulfoftalein3 ‘, 3--dibromo-5‘, 5--dichlorophenol-3,4,5,6-terachlorosulfophthalein
3,55 g (0,005 molu) 3‘,3“-dibromfenol-3,4,5,6-tetrachlorsulfoftalelnu se suspenduje v 50 ml ledové kyseliny octové. K tomu se přidává pomalu za míchání roztok 0,94 g (0,025 gramatomu) chloru v 50 ml ledové kyseliny octové. Po vícehodinovém míchání se získá 3,8 g ( = 90,5%) bezbarvých krystalů 3‘,3“-dibrom-5‘,5“-dichlorfenol-3,4,5,6-tetrachlorsulfoftaleinu, teplota tání 265 až 268 °C. Sloučenina krystaluje se 2 moly kyseliny octové (molekulová hmotnost) Ci9H6Br2Cl6O5S. . 2 C2H4O2=839,01).3.55 g (0.005 mol) of 3 ‘, 3'-dibromophenol-3,4,5,6-tetrachlorosulfophthalelin are suspended in 50 ml of glacial acetic acid. To this is added slowly with stirring a solution of 0.94 g (0.025 gram) of chlorine in 50 ml of glacial acetic acid. After stirring for several hours, 3.8 g (= 90.5%) of colorless crystals of 3 ', 3'-dibromo-5', 5'-dichlorophenol-3,4,5,6-tetrachlorosulfophthalein, m.p. 265-268 °, are obtained. C. The compound crystallizes with 2 moles of acetic acid (molecular weight) of C 19 H 6 Br 2 Cl 6 O 5 S. . 2 (C2H4O2 = 839.01).
stejná látka se dá vyrobit také bromací 3‘,3‘-dichlorfenol-3,4,5,6-tetrachlorsulfoítaleinu (získaného chloraci fenol-3,4,5,6-tetrachlorsulfoftaleinu, výtěžek 60%). Příklad 4the same substance can also be produced by bromination of 3 ‘, 3‘-dichlorophenol-3,4,5,6-tetrachlorosulfothalealein (obtained by chlorination of phenol-3,4,5,6-tetrachlorosulfophthalein, yield 60%). Example 4
3‘,3“,5‘,5“-tetrachlorfenol-3,4,5,6-tetrabromsulf oftalein3 ‘, 3,, 5‘, 5--tetrachlorophenol-3,4,5,6-tetrabromsulf ofthalein
13,8 g (0,02 molu) fenol-3,4,5,6-tetrabrpmsulfoftaleinu se suspenduje ve 100 ml ledové kyseliny octové a za míchání se při teplotě místnosti přikape roztok 3,6 g chloru (~0,l gramatomu) ve 30 ml ledové kyseliny octové. Poté se smíchá více hodin a vzniklé zbarvené krystaly se odsají. Po překrystalování ze směsi kyseliny octové a vody 9:1 se získá 11 g ( = 58,3 %) 3‘,3“,5‘,5“-tetrachlorfenol-3,4,5,6-tetrabromsulfoftaleinu, bezbarvé krystaly, teplota tání 203 až 204 °C (rozklad).13.8 g (0.02 mol) of phenol-3,4,5,6-tetrabrpmsulfophthalein are suspended in 100 ml of glacial acetic acid and a solution of 3.6 g of chlorine (~ 0.1 gram) is added dropwise with stirring at room temperature. in 30 ml of glacial acetic acid. It is then mixed for several hours and the resulting colored crystals are aspirated. Recrystallization from 9: 1 acetic acid and water gave 11 g (= 58.3%) of 3 ', 3', 5 ', 5' -tetrachlorophenol-3,4,5,6-tetrabromosulfophthalein, colorless crystals, temperature mp 203-204 ° C (dec.).
Sloučenina krystaluje se 2 molekulami kyseliny octové s 1 molekulou vody) molekulová hmotnost: Ci9H6Br4Cl4O5S . 2 CH3COOH . . H2O = 945,9).The compound crystallizes with 2 molecules of acetic acid with 1 molecule of water) molecular weight: C 19 H 6 Br 4 Cl 4 O 5 S. 2 CH3COOH. . H 2 O = 945.9).
Analogickým způsobem se získá z fenol-3,4,5,6-tetrachlorsulfoftaleinu chloraci v ledové kyselině octové 3‘,3“,5‘,5“-tetrachlorfenol-3,4,5,6-tetrachlorsulf oftalein, teplota tání 277 až 278 l0C. Sloučeniny krystalují s 1 molekulou kyseliny octové (molekulová hmotnost: C19H6CI8O5S . C2H4O2 = 690).In an analogous manner, chlorination in glacial acetic acid 3 ', 3', 5 ', 5' -tetrachlorophenol-3,4,5,6-tetrachlorosulfophthalein, m.p. l0 278 C. compounds crystallized with 1 molecule of acetic acid (molecular weight: C19H6CI8O5S. C2H4O2 = 690).
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS776442A CS196222B2 (en) | 1975-03-12 | 1977-10-05 | Method of producing novel octahalogene-sulphophthaleine |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2510633A DE2510633C3 (en) | 1975-03-12 | 1975-03-12 | Diagnostic agent for the detection of protein in body fluids and indicator dyes suitable therefor |
| CS761458A CS190526B2 (en) | 1975-03-12 | 1976-03-05 | Diagnostic means for detecting the protein in the bodily fluids |
| CS776442A CS196222B2 (en) | 1975-03-12 | 1977-10-05 | Method of producing novel octahalogene-sulphophthaleine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS196222B2 true CS196222B2 (en) | 1980-03-31 |
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ID=25745432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS776442A CS196222B2 (en) | 1975-03-12 | 1977-10-05 | Method of producing novel octahalogene-sulphophthaleine |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS196222B2 (en) |
-
1977
- 1977-10-05 CS CS776442A patent/CS196222B2/en unknown
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