DE109933C - - Google Patents
Info
- Publication number
- DE109933C DE109933C DENDAT109933D DE109933DA DE109933C DE 109933 C DE109933 C DE 109933C DE NDAT109933 D DENDAT109933 D DE NDAT109933D DE 109933D A DE109933D A DE 109933DA DE 109933 C DE109933 C DE 109933C
- Authority
- DE
- Germany
- Prior art keywords
- pyridine
- dissolved
- yellow
- chlorine
- bases
- 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.)
- Active
Links
- 239000000460 chlorine Substances 0.000 claims description 24
- 150000003222 pyridines Chemical class 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- HCUYBXPSSCRKRF-UHFFFAOYSA-N Diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-Methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N Phosphorus pentoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000004651 carbonic acid esters Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- QFFVPLLCYGOFPU-UHFFFAOYSA-N Barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N Dichlorine monoxide Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
KLASSE 12: Chemische Verfahren und Apparate.CLASS 12: Chemical processes and apparatus.
Patentirt im Deutschen Reiche vom 27. Mai 1898 ab.Patented in the German Empire on May 27, 1898.
Perchlormethylformiat ,Cl Perchloromethyl formate , Cl
COCO
Cl O — Cf^-Cl Cl O - Cf ^ -Cl
Cl sowie Hexachlordimethylcarbonat Cl and hexachlorodimethyl carbonate
ClCl
Cf-Cl ClCf-Cl Cl
,Cl -Cl, Cl -Cl
-Cl-Cl
CO:CO:
0— C0- C
und Eohlenoxychlorid C O Cl2 verbinden sich mit den Basen der Pyridinreihe zu bisher noch nicht beschriebenen Derivaten, und zwar entsteht '— gleichgültig, welchen der drei genannten Chlorkörper man mit der Base in Wechselwirkung treten läfst — stets dasselbe Product.and carbon oxychloride CO Cl 2 combine with the bases of the pyridine series to form derivatives not yet described, and the result is always the same product, regardless of which of the three above-mentioned chlorine compounds is allowed to interact with the base.
Beispielsweise bildet sich das Pyridinderivat in quantitativer Ausbeute, wenn man wasserfreies Pyridin, in trocknem, alkoholfreiem Aether gelöst, mit einer ätherischen Lösung von Hexachlordimethylcarbonat versetzt. Diese neue Verbindung stellt —· frisch bereitet — ein citronengelbes, mikrokrystallinisches Pulver dar, welchem die Formel zukommt:For example, the pyridine derivative is formed in quantitative yield when anhydrous Pyridine, dissolved in dry, alcohol-free ether, with an ethereal solution of hexachlorodimethyl carbonate offset. This new compound is - freshly prepared - a lemon-yellow, microcrystalline powder, to which the formula applies:
Analyse: Berechnet: Gefunden:
Chlor 27,63 pCt. 27,24 pCt.Analysis: Calculated: Found:
Chlorine 27.63 pCt. 27.24 pCt.
Folgende drei Gleichungen erläutern den Bildungsprocefs des Pyridinderivates:The following three equations explain the formation process of the pyridine derivative:
ClCl
Cl C: O -f 2 (C5 H5 N) = C: Cl C : O -f 2 (C 5 H 5 N) = C:
NC5H5 NC 5 H 5
ClCl
,Cl, Cl
C: OC: O
/Cl O — Cf- Cl/ Cl O - Cf - Cl
A(C5H5N) = 2 C : A (C 5 H 5 N) = 2 C:
ClCl
,ei,egg
O — Cf-ClO - Cf-Cl
C:0 + 6(C5H5N)C: 0 + 6 (C 5 H 5 N)
\ /Cl\ / Cl
O — Cf-ClO - Cf-Cl
ClCl
= 3= 3
C: O ^NCHC: O ^ NCH
C/C /
Gleichfalls in der Form gelber Pulver werden solche Chlorkörper von den Homologen des Pyridins erhalten. Die neuen Verbindungen werden als Chlorcarbonyle bezeichnet.Such chlorine bodies are also in the form of yellow powders from the homologues obtained from pyridine. The new compounds are called chlorocarbonyls.
Beispiel I.Example I.
Zu 316 g absolut wasserfreiem, reinem Pyridin, welche in 500 g Benzol gelöst sind, fügt man unter Umrühren und Abkühlen eine Lösung, bestehend aus 198 g Perchlormethylformiat und 500 g Benzol. Sofort fällt in quantitativer Ausbeute das citronengelbe Pyridinchlorcarbonyl aus, welches auf trockenen porösen Thonplatten ausgebreitet und unter peinlichster Fernhaltung von Wasser im Vacuum über Phosphorpentoxyd getrocknet wird.Add to 316 g of absolutely anhydrous, pure pyridine, which are dissolved in 500 g of benzene a solution consisting of 198 g of perchloromethyl formate is added with stirring and cooling and 500 g of benzene. The lemon-yellow pyridine chlorocarbonyl falls immediately in quantitative yield from, which is spread out on dry, porous clay slabs and carefully kept away from water in a vacuum is dried over phosphorus pentoxide.
Beispiel II.Example II.
Man vereinigt unter Umrühren und starkem Abkühlen 558 g a-Picolin558 g of a-picoline are combined with stirring and vigorous cooling
CHCH / %./%. CH CHCH CH
Il IIl I
CH C- CHCH C- CH
gelöst in 1500 g absolutem alkoholfreiem Aether, mit 297 g Hexachlordimethylcarbonat, gleichfalls gelöst in der genügenden Menge Aether.dissolved in 1500 g of absolute alcohol-free ether, with 297 g of hexachlorodimethyl carbonate, likewise dissolved in a sufficient quantity of ether.
Alsbald scheidet sich das neue a-Picolinderivat als gelber Niederschlag aus. Er kann wie in Beispiel I angegeben isolirt werden.The new a-picoline derivative soon separated as a yellow precipitate. It can be isolated as indicated in Example I.
Beispiel III.Example III.
Man leitet in 214g a-Lutidin
CH One passes a-lutidine into 214 g
CH
CH CHCH CH
J IlJ Il
C · CH% C' CH$C · CH% C 'CH $
gelöst in 500 g Toluol (oder Xylol), 99 g Köhlenoxychlorid ein, oder giebt dazu eine Phosgenlösung, welche 99 g C O Cl2 enthält. Für starkes Abkühlen mufs Sorge getragen werden. Auch hier findet sogleich die Abscheidung des gelben a-Lutidinchlorcarbonyls statt.dissolved in 500 g of toluene (or xylene), 99 g of coal oxychloride, or added a phosgene solution which contains 99 g of CO Cl 2 . Care must be taken to ensure that it cools down considerably. Here, too, the yellow a-lutidine chlorocarbonyl is immediately deposited.
Bei Verwendung anderer Homologen des Pyridins verläuft die Reaction in gleicher Weise.If other homologues of pyridine are used, the reaction proceeds in the same way.
Haltbar sind die neuen Producte nur, wenn man jede Spur Wasser von ihnen fern hält. Für die praktische Verwendung suspendirt man sie in einem trockenen, indifferenten Liquidum. Mit Wasser zersetzen sie sich unter lebhafter Reaction. Bei Verwendung des Pyridinderivates verläuft diese Zersetzung nach folgender Gleichung:The new products are only durable if you keep every trace of water away from them. For practical use, they are suspended in a dry, indifferent liquid. With water they decompose with vigorous reaction. When using the pyridine derivative this decomposition proceeds according to the following equation:
ClCl
C: O + H2O= 2 (C5H5N-H Cl) + C O2. C: O + H 2 O = 2 (C 5 H 5 NH Cl) + C O 2 .
}nc5h5 } nc 5 h 5
ClCl
Mit Alkoholen, Phenolen und phenolartigen Körpern tritt Umsetzung nach folgendem Schema ein:With alcohols, phenols and phenol-like bodies, reaction occurs according to the following Scheme a:
C/C /
^N^ N C: OC: O
ClCl
HO —RHO —R
+ = 2(C5H5N-HCl) + C: Ό + = 2 (C 5 H 5 N-HCl) + C: Ό
HO —RHO —R
O—RO-R
O— RO— R
Es werden dabei also Kohlensäureester der Alkohole oder Phenole gebildet.In the process, carbonic acid esters of alcohols or phenols are formed.
Die beschriebenen neuen Producte sollen zur Darstellung solcher Kohlensäureester und als wasserabspaltende Agentien (z. B. zur Anhydridbildung) Verwendung finden.The new products described are intended to represent such carbonic acid esters and as Find water-releasing agents (e.g. for anhydride formation) use.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE109933C true DE109933C (en) |
Family
ID=379784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT109933D Active DE109933C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE109933C (en) |
-
0
- DE DENDAT109933D patent/DE109933C/de active Active
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