DE2020297A1 - Hexachloro dipyrimidyl by trichloropyrimidine chlorination and use as - andpigment intermediate - Google Patents
Hexachloro dipyrimidyl by trichloropyrimidine chlorination and use as - andpigment intermediateInfo
- Publication number
- DE2020297A1 DE2020297A1 DE19702020297 DE2020297A DE2020297A1 DE 2020297 A1 DE2020297 A1 DE 2020297A1 DE 19702020297 DE19702020297 DE 19702020297 DE 2020297 A DE2020297 A DE 2020297A DE 2020297 A1 DE2020297 A1 DE 2020297A1
- Authority
- DE
- Germany
- Prior art keywords
- trichloropyrimidine
- dipyrimidyl
- hexachloro
- chlorination
- andpigment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005660 chlorination reaction Methods 0.000 title description 2
- GIKMWFAAEIACRF-UHFFFAOYSA-N 2,4,5-trichloropyrimidine Chemical compound ClC1=NC=C(Cl)C(Cl)=N1 GIKMWFAAEIACRF-UHFFFAOYSA-N 0.000 title 1
- AUWPHGWEYHEAIG-UHFFFAOYSA-N 4,5,6-trichloropyrimidine Chemical compound ClC1=NC=NC(Cl)=C1Cl AUWPHGWEYHEAIG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract description 2
- 239000001000 anthraquinone dye Substances 0.000 abstract description 2
- 239000000975 dye Substances 0.000 abstract description 2
- 230000000855 fungicidal effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 239000001052 yellow pigment Substances 0.000 abstract 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 1
- 241000228452 Venturia inaequalis Species 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- GVBHCMNXRKOJRH-UHFFFAOYSA-N 2,4,5,6-tetrachloropyrimidine Chemical compound ClC1=NC(Cl)=C(Cl)C(Cl)=N1 GVBHCMNXRKOJRH-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- UNCQVRBWJWWJBF-UHFFFAOYSA-N 2-chloropyrimidine Chemical compound ClC1=NC=CC=N1 UNCQVRBWJWWJBF-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/30—Halogen atoms or nitro radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
Hexachloridpyrimidyl Gegenstand der Erfindung ist 4, 4 ,5,5-'-6,61-Hexachlor-2,2'-dipyrimidyl- der Formel Gegenstand der Erfindung ist desweiteren ein Verfahren zur Herstellung von 4,4', 5,5', 6,6'-Hexachlor-2,2'-dipyrimidyl der Formel (I), das dadurch gekennzeichnet ist, daß man 4,5,6-Trichlor-pyrimidin bei Temperaturen von etwa 1500 C bis etwa 2500 C unter W-Bestrahlung mit überschüssigem gasförmigem Chlor umsetzt.Hexachloridpyrimidyl The invention relates to 4, 4, 5,5 -'- 6,61-hexachloro-2,2'-dipyrimidyl- of the formula The invention also relates to a process for the preparation of 4,4 ', 5,5', 6,6'-hexachloro-2,2'-dipyrimidyl of the formula (I), which is characterized in that 4,5, 6-Trichloropyrimidine is reacted with excess gaseous chlorine at temperatures of about 1500 C to about 2500 C under UV irradiation.
Chloriert man 4,5,6-Trichlor-pyrimidin gemäß den Angaben der Belgischen Patentschrift Nr. 706 760, so erhält man überraschenderweise neben dem dort beschriebenen Tetrachlorpyrimidin die Verbindung der Formel (I) in Ausbeuten vor etwa 5 - 15 ° der Theorie.If 4,5,6-trichloropyrimidine is chlorinated according to the instructions of the Belgische Patent No. 706 760 is surprisingly obtained in addition to that described there Tetrachloropyrimidine the compound of the formula (I) in yields of about 5-15 ° the theory.
bas erfindungsgemäße Verfahren wird so durchgeführt, daß man in eine schmelze von 4,5,6-Trichlor-pyrimidin (Pp. 51 bis 520 C) bei Temperaturen zwischen 1500 C und 2500 C, bevorzugt bei 200 bis 220O C, überschüssiges ChLorgas einleitet, wobei vori außen und/oder innen (Tauchbrenner) mit UV-Licht bestrahlt wird. Unter "überschüssigem Chlorgas" ist hierbei zu verstehen, daß in den Reaktionsabgasen noch deutlich die grüne Farbe des Chlors erkennbar ist. Zur Erhöhung der Effektivität der W-Bestrahlung ist es vorteilhaft, möglichst wasserhelle, von gefärbten Verunreinigungen freie Schmelzen von 4,5,6-Trichlor-pyrimidin zu verwenden. Die Chlorierung unter Uv-Bestrahlung wird so lange fortgesetzt, bis kein weiteres Hexachlordipyrimidyl der Formel (I) mehr gebildet wird.bas process according to the invention is carried out so that one in a melt 4,5,6-trichloropyrimidine (pp. 51 to 520 C) at temperatures between 1500 C and 2500 C, preferably at 200 to 220 ° C, introduces excess chlorine gas, being irradiated with UV light in front of the outside and / or inside (immersion burner). Under "Excess chlorine gas" is to be understood here as being in the reaction exhaust gases the green color of the chlorine can still be clearly seen. To increase the effectiveness With UV irradiation, it is advantageous to remove colored impurities as light as possible to use free melts of 4,5,6-trichloropyrimidine. The chlorination under UV irradiation is continued until no further hexachlorodipyrimidyl of formula (I) is formed more.
Die Abtrennung des erfindungsgemäßen Hexachlor-dipyrimidyls der Formel (I) vom gleichzeitig entstandenen Tetrachlorpyrimidin und gegebenenfalls Resten unumgesetztem 4,5,6-Trichlorpyrimidin erfolgt in sehr einfacher Weise aufgrund seiner wesentlich geringeren Flüchtigkeit durch Abdestillieren von etrachlor- (und gegebenenfalls Trichlor-) pyrimidin, oder aufgrund seiner wesentlich geringeren Löslichkeit: Man versetzt das Reaktionsgemisch bei gewöhnlicher Temperatur mit einem lösungsmittel, das Tetra- bzw. 4,5,6-Trichlorpyrimidin vollständig, hingegen das Dipyrimidyl der Formel (I) praktisch nicht löst und isoliert letzteres durch einfache Filtration. Lösungsmittel, die hierfür geeignet sind, sind beispielsweise Methylenchlorid, Chloroform oder Petroläther.The separation of the hexachlorodipyrimidyl according to the invention of the formula (I) from the tetrachloropyrimidine formed at the same time and optionally residues unreacted 4,5,6-trichloropyrimidine takes place in a very simple manner because of it significantly lower volatility due to distilling off etrachloro (and possibly Trichloro-) pyrimidine, or due to its much lower solubility: Man adds a solvent to the reaction mixture at normal temperature, the tetra- or 4,5,6-trichloropyrimidine completely, however the dipyrimidyl the Formula (I) practically does not dissolve and isolates the latter by simple filtration. Solvents that are suitable for this are, for example, methylene chloride and chloroform or petroleum ether.
Man kann die beiden erwähnten rennungsverfahren auch kombiniert anwenden, indem man destillativ zunächst die Hauptmenge des etra(Tri)chlor-pyrimidine entfernt (etwa bis zum Kp.You can also use the two mentioned separation processes in combination, by first removing most of the etra (tri) chloropyrimidine by distillation (up to about Kp.
.1100/12 Torr) und anschließend den DastillationsrUckstand mit einem Lösungsmittel digeriert. Selbstverständlich können bei kleineren Raktionsansätzen auch säulen- oder dünnschichtchromatographische Trenmethoden angewandt werden. Das erfindungsgemäße Hexachlor-dipyrimidyl (I) kann aus organischen Lösungsmitteln, insbesondere Kohlenwasserstoffen wie z. B..1100 / 12 Torr) and then the distillation residue with a Solvent digested. Of course you can with smaller ones Reaction approaches also column or thin-layer chromatographic separation methods are used will. The hexachlorodipyrimidyl (I) according to the invention can be prepared from organic solvents, in particular hydrocarbons such as. B.
Waschbenzin (Siedebereich 100 - 1400 C) oder Benzol umkristallisiert erden.Recrystallized benzene (boiling range 100 - 1400 C) or benzene earth.
Das Dipyrimidyl (I) kann beispielsweise als Zwischenprodukt zur Herstellung wertvoller neuer Pig.ientfarbstoffe Verwendung finden. So erhält man durch dreistündiges Erhitzen von 1 Mol (I) mit 2,5 Mol 1-Aminoantnraehinon in Nitrobenzol bei 2000 C in Gegenwart einer Spur wasserfreiem FeCl3 den Anthrachinonfarbstoff (II) Analyse des Rohprodukts (bei 1000 C aus dem Nitrobenzol abgesaugt): C36H16Cl4N6O4 (738,4) Ber.: C: 58,5 % H: 2,2 % Cl: 19,2 % N: 11,4 % 0: 8,7 % Gef.: C: 58,3 % H: 2,3 % Cl: 18,6 % N: 11,4 % 0: 9t0 y ))er neue rotatichig gelbe Pigmentfarbstoff zeigt sehr gute Licht-, Migrations- und Überlackierechtheit.The dipyrimidyl (I) can be used, for example, as an intermediate for the production of valuable new pigment dyes. By heating 1 mole (I) with 2.5 moles of 1-aminoantnraehinone in nitrobenzene at 2000 C in the presence of a trace of anhydrous FeCl3, the anthraquinone dye (II) is obtained for three hours. Analysis of the crude product (sucked out of the nitrobenzene at 1000 C): C36H16Cl4N6O4 (738.4) Calc .: C: 58.5% H: 2.2% Cl: 19.2% N: 11.4% 0: 8, 7% found: C: 58.3% H: 2.3% Cl: 18.6% N: 11.4% 0: 9t0 y)) he new rotatichig yellow pigment shows very good fastness to light, migration and overcoating .
Darüberhinaus zeigt das Dipyrimidyl (I) selbst fungizide Eigenschaften, insbesondere gegen Susicladium dendriticum.In addition, the dipyrimidyl (I) itself shows fungicidal properties, especially against Susicladium dendriticum.
Beispiel In einem Dreihals-Glasgefäß, das mit Chloreinleitungsrohr, Rückflußkühler, Thermometer und einer Hochdruck-UV-Tauchlampe (Marke Hanau, 81 Watt) versehen ist, werden 290 g (1,58 Mol) 4,5,6-Trichlorpyrimidin 5 Stunden bei 200 - 2100 C unter UV-Bestrahlung mit einem so starken Chlorstrom behandelt, daß in den Abgasen noch die grüne Farbe überschüssigen Chlors erkennbar ist. Nach Durchblasen eines Stickstoffstroms und Abkühlen auf Raumtemperatur wird das Reaktionsgemisch in etwa 1 Liter Methylenchlorid gegeben, 10 Minuten gerührt, abgesaugt, mit Methylenchlorid nach gewaschen und getrocknet.Example In a three-necked glass vessel fitted with a chlorine inlet tube, Reflux condenser, thermometer and a high pressure UV diving lamp (brand Hanau, 81 watts) is provided, 290 g (1.58 mol) of 4,5,6-trichloropyrimidine are 5 hours at 200 - Treated 2100 C under UV radiation with such a strong stream of chlorine that in The green color of excess chlorine can still be seen in the exhaust gases. After blowing through a stream of nitrogen and cooling to room temperature, the reaction mixture given in about 1 liter of methylene chloride, stirred for 10 minutes, filtered off with suction, with methylene chloride after washed and dried.
Ausbeute 27 g (9,3 % der Theorie) Reachlor-dipyrimidyl der Formel (I). Schmelzpunkt nach dem Umkristallisieren aus Benzol 289 - 2900 C.Yield 27 g (9.3% of theory) of reachlorodipyrimidyl of the formula (I). Melting point after recrystallization from benzene 289 - 2900 C.
Analyse: C8Cl6N4 t364,8) Ber.: C 26,3 % Cl: 58,3 % N: 15,4 % Gef.: C 26,7 % Cl: 58,1 % N: 15,3 %Analysis: C8Cl6N4 t364.8) Calc .: C 26.3% Cl: 58.3% N: 15.4% Found: C 26.7% Cl: 58.1% N: 15.3%
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19702020297 DE2020297A1 (en) | 1970-04-25 | 1970-04-25 | Hexachloro dipyrimidyl by trichloropyrimidine chlorination and use as - andpigment intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19702020297 DE2020297A1 (en) | 1970-04-25 | 1970-04-25 | Hexachloro dipyrimidyl by trichloropyrimidine chlorination and use as - andpigment intermediate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2020297A1 true DE2020297A1 (en) | 1971-11-11 |
Family
ID=5769374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19702020297 Pending DE2020297A1 (en) | 1970-04-25 | 1970-04-25 | Hexachloro dipyrimidyl by trichloropyrimidine chlorination and use as - andpigment intermediate |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2020297A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0109930A1 (en) * | 1982-10-25 | 1984-05-30 | Ciba-Geigy Ag | Chromogenic bis-quinazoline compounds, method of preparing them and their use as chromogenes in pressure-sensitive or heat-sensitive recording materials |
-
1970
- 1970-04-25 DE DE19702020297 patent/DE2020297A1/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0109930A1 (en) * | 1982-10-25 | 1984-05-30 | Ciba-Geigy Ag | Chromogenic bis-quinazoline compounds, method of preparing them and their use as chromogenes in pressure-sensitive or heat-sensitive recording materials |
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