DE1009190B - Process for the preparation of reaction products of chlorotriazines - Google Patents
Process for the preparation of reaction products of chlorotriazinesInfo
- Publication number
- DE1009190B DE1009190B DED22163A DED0022163A DE1009190B DE 1009190 B DE1009190 B DE 1009190B DE D22163 A DED22163 A DE D22163A DE D0022163 A DED0022163 A DE D0022163A DE 1009190 B DE1009190 B DE 1009190B
- Authority
- DE
- Germany
- Prior art keywords
- chlorotriazines
- preparation
- reaction products
- water
- chloride
- 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
- 238000000034 method Methods 0.000 title claims description 7
- RTNUTCOTGVKVBR-UHFFFAOYSA-N 4-chlorotriazine Chemical class ClC1=CC=NN=N1 RTNUTCOTGVKVBR-UHFFFAOYSA-N 0.000 title claims description 6
- 239000007795 chemical reaction product Substances 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- GGUFVZFOCZNPEG-UHFFFAOYSA-N 4,5,6-triphenyltriazine Chemical compound C1=CC=CC=C1C1=NN=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 GGUFVZFOCZNPEG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Verf ahren zur HersteHung von Umsetzungsprodukten von Chlortriazinen In der deutschen Patentschrift 959 096 ist ein Verfahren zur Herstellung von Umsetzungsprodukten von Chl#ortriazinen, vorzugsweise Cyanurchlorid, mit aromatischen Kohlenwasserstoffen oder ihren Substitutionsprodukten unter Bildung von Kohlenstoff-, Kohlenstoffbindungen am Triazinring beschrieben. Das Verfahren ist dadürch gekennzeichnet, daß die Chlortriazine mit Benzol, seinen Homologen oder seinen Substitutionsprodukten, die keine labilen H-Atome enthalten, in Gegenwart von etwa 1 bis 3 Mol Friedel-Crafts-Katalysatoren, insbesondere Aluminiurn,chlorid, und in Gegenwart solcher Mengen von Halogenwasserstoff, daß das Reaktionsgemisch mit diesem gesättigt ist, umgesetzt werden. Vorzugsweise verfährt man hierbei so, daß der Katalysator oder das Chlortriazin allmählich in das Reaktionsgetnisch eingetragen werden.Process for the preparation of reaction products of chlorotriazines In the German patent specification 959 096 a process for the preparation of reaction products of chlorotriazines, preferably cyanuric chloride, with aromatic hydrocarbons or their substitution products with the formation of carbon, carbon bonds on the triazine ring is described. The process is characterized in that the chlorotriazines with benzene, its homologues or its substitution products which contain no labile H atoms, in the presence of about 1 to 3 mol Friedel-Crafts catalysts, in particular aluminum, chloride, and in the presence of such amounts of hydrogen halide so that the reaction mixture is saturated with this, can be reacted. The procedure here is preferably such that the catalyst or the chlorotriazine are gradually introduced into the reaction table.
Nach der USA.-Patentschrift 1734 029 ist es bereits bekannt, Tr#iphenyltriazin durch Urnsetzung von Cyan,urchlorid mit Benzol in Gegenwart von wasserfreiem Aluminiumchlorid in hoher Ausbeute herzustellen. Im Gegensatz zu den Angaben der genannten Patentschrift hat es sich gezeigt, daß nur dann gute Ausbeuten erhalten werden und die Umsetzung sich einwandfrei durchführen läßt, wenn das Reaktionsgemisch mit Halogenwasserstoff gesättigt ist.After USA. Patent 1,734,029 it is already known, Tr # iphenyltriazin by Urnsetzung of cyan, produce urchlorid with benzene in the presence of anhydrous aluminum chloride in high yield. In contrast to the information in the cited patent, it has been found that good yields can only be obtained and the reaction can only be carried out properly if the reaction mixture is saturated with hydrogen halide.
Bei der weiteren Entwicklung dieses Verfahrens wurde überraschenderweise festgestellt, daß es nicht erforderlich ist, von vornherein in Gegenwart größerer Mengen von Chlorwasserstoff zu arbeiten, daß man aber den gewünschten Erfolg erreicht, wenn man dem Gemisch des Chlortriazins mit dem aromatischen Kohlenwasserstoff und dem Katalysator geringe Mengen von Wasser zusetzt. Unter diesen Umständen setzt die Umsetzung auch ohne Zusatz von freiem Chlorwasserstoff sofort ein und läßt sich ohne Schwierigkeit bis zum Ende durchführen.In the further development of this process, surprisingly found that it is not necessary a priori in the presence of larger ones To work quantities of hydrogen chloride, but that one achieves the desired result, if you mix the chlorotriazine with the aromatic hydrocarbon and adds small amounts of water to the catalyst. In these circumstances continues the reaction starts immediately even without the addition of free hydrogen chloride and can be Carry out to the end without difficulty.
Erfindungsgemäß werden demnach Umsetzungsprodukte von Chlortriazinen dadurch hergestellt, da-ß Cyanurchlorid mit Benzol oder seinen Hornologen in Gegenwart von etwa 1 bis 3 Mol Aluminiumehlorid und in Gegenwart geringer Mengen von Wasser umgesetzt wird. Beispiel 1 In einen 3-Tubus-Kolben werden 60 ccm Benzol, 15 g Cyanurchlorid und 35 g wasserfreies Aluminiumchlorid unter Rühren am Rückflußkühler erhitzt. Bei Zugabe von 0,5 ccm Wasser setzt eine reichliche Chlorwasserstoffentwicklung ein. Es wird weiter 8 Stunden am Rückflußkühler unter Rühren gekocht.According to the invention, reaction products of chlorotriazines are accordingly prepared by reacting cyanuric chloride with benzene or its hornologues in the presence of about 1 to 3 mol of aluminum chloride and in the presence of small amounts of water. EXAMPLE 1 60 cc of benzene, 15 g of cyanuric chloride and 35 g of anhydrous aluminum chloride are heated in a 3-tube flask with stirring on a reflux condenser. When 0.5 cc of water is added, an abundant evolution of hydrogen chloride begins. It is boiled for a further 8 hours on the reflux condenser with stirring.
Nach dem Erkalten ist das Reaktionsgemisch fast vollständig erstarrt. Zur Aufarbeitung wird es mit Wasser zersetzt und der Rückstand durch mehrmaliges Aufkochen mit Wasser und Abnutschen säurefrei gewaschen. Nach dem Trocknen im Trockenschrank bei 130 bis 1401 werden 22,7 g (90,4% der Theorie) hellbraunes Triphenyltriazin mit einem Schmelzpunkt von 228 bis 2301 erhalten.After cooling, the reaction mixture is almost completely solidified. For work-up, it is decomposed with water and the residue is washed free of acid by boiling it up several times with water and filtering off with suction. After drying in a drying cabinet at 130 to 1401, 22.7 g (90.4% of theory) of light brown triphenyltriazine with a melting point of 228 to 2301 are obtained.
Wird der Versuch unter sonst gleichen Bedingungen, aber ohne Zusatz von 0,5 ccin Wasser d.urchgeführt, so wird bei Sstündigern Kochen am Rückflußkühler eine dunkle Flüssigkeit mit einer festen schwarzen Masse erhalten, die überhaupt kein Triphenyltriazin enthält. Beispiel 2 In einem 3-Tubus-Kolben werden 90 cem Toluol, 15 g Cyanurchlorid und 35 #g wass-erfreies Aluminiumchlorid, sowie 0,5 ccm Wasser unter Rühren am Rückflußkühler auf einem Heizbad mit allmählich steigender BadtemPeratur erhitzt. Bei 70' Innentemperatur -,verden nochmals 0,5 ccm Wasser nachgegeben, worauf bei 80' Innentemperatur eine mittelstarke Chlorwasserstoffentwicklung einsetzt. Man läßt die Badtemperatur allmählich bis auf 145' steigen, wobei, eine Innentemperatur von 112' erreicht wird, die Gesamtreaktionszeit beträgt 8 Stunden.If the experiment is carried out under otherwise identical conditions, but without the addition of 0.5 cc of water, a dark liquid with a solid black mass which does not contain any triphenyltriazine is obtained when boiling for half an hour on the reflux condenser. Example 2 In a 3-tube flask, 90 cem toluene, 15 g cyanuric chloride and 35 μg water-free aluminum chloride and 0.5 ccm water are heated with stirring on a reflux condenser on a heating bath with gradually increasing bath temperature. At an internal temperature of 70 ' , another 0.5 cc of water was added, whereupon, at an internal temperature of 80', a moderate evolution of hydrogen chloride began. The bath temperature is allowed to rise gradually to 145 ', an internal temperature of 112' being reached, the total reaction time being 8 hours.
Nach dem Erkalten besteht das Reaktionsprodukt aus einer in der toluolisch-en Lösung verteilten festen Masse. Zur Aufarbeitung wird das Toluol im Vakuum abdestilliert und das zurückbleibende Produkt durch mehrmaliges Auskochen mit verdünnter Salzsäure zersetzt und zuletzt mit Wasser säufrefrei gewaschen. Naeh dem Trocknen im Trockensch-rank bei 130' werden 19,2 g Tritolyltriazin erhalt-en. Das Produkt besteht aus einem Gemisch der p- und o-Verbindung und schmilzt zwischen 205 und 235'. After cooling, the reaction product consists of a solid mass distributed in the toluene solution. For work-up, the toluene is distilled off in vacuo and the remaining product is decomposed by boiling it out several times with dilute hydrochloric acid and finally washed with water until free from acid. After drying in the drying cabinet at 130 ' , 19.2 g of tritolyltriazine are obtained. The product consists of a mixture of the p- and o-compounds and melts between 205 and 235 '.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED22163A DE1009190B (en) | 1956-01-21 | 1956-01-21 | Process for the preparation of reaction products of chlorotriazines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED22163A DE1009190B (en) | 1956-01-21 | 1956-01-21 | Process for the preparation of reaction products of chlorotriazines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1009190B true DE1009190B (en) | 1957-05-29 |
Family
ID=7037357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED22163A Pending DE1009190B (en) | 1956-01-21 | 1956-01-21 | Process for the preparation of reaction products of chlorotriazines |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1009190B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1734029A (en) * | 1926-03-08 | 1929-11-05 | American Cyanamid Co | Process of producing benzoic acid |
-
1956
- 1956-01-21 DE DED22163A patent/DE1009190B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1734029A (en) * | 1926-03-08 | 1929-11-05 | American Cyanamid Co | Process of producing benzoic acid |
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