DE306316C - - Google Patents
Info
- Publication number
- DE306316C DE306316C DENDAT306316D DE306316DA DE306316C DE 306316 C DE306316 C DE 306316C DE NDAT306316 D DENDAT306316 D DE NDAT306316D DE 306316D A DE306316D A DE 306316DA DE 306316 C DE306316 C DE 306316C
- Authority
- DE
- Germany
- Prior art keywords
- diphenylamine
- urethane
- mole
- solution
- hydrochloric acid
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 125000005266 diarylamine group Chemical group 0.000 claims description 5
- -1 chloroformic acid ester Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000003673 urethanes Chemical class 0.000 claims description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N Diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- HKTSLDUAGCAISP-UHFFFAOYSA-N ethyl N,N-diphenylcarbamate Chemical compound C=1C=CC=CC=1N(C(=O)OCC)C1=CC=CC=C1 HKTSLDUAGCAISP-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JEFJSEIUEJBMSR-UHFFFAOYSA-N hydron;N-phenylaniline;chloride Chemical compound Cl.C=1C=CC=CC=1NC1=CC=CC=C1 JEFJSEIUEJBMSR-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N Chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N Chloroformic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 230000036826 Excretion Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-M carbonochloridate Chemical compound [O-]C(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-M 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- DDKMFOUTRRODRE-UHFFFAOYSA-N chloromethanone Chemical compound Cl[C]=O DDKMFOUTRRODRE-UHFFFAOYSA-N 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- VYWQTJWGWLKBQA-UHFFFAOYSA-M urea;chloride Chemical class [Cl-].NC(N)=O VYWQTJWGWLKBQA-UHFFFAOYSA-M 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
Description
Zur Darstellung von Diphenylurethan ließ man bisher auf 2 MbI. Diphenylamin 1 Mol. Chlorameisensäureest^r einwirken (B. d. D. eh. G. XVIII, 2574), wobei .Diphenylurethan und Diphenylaminchlorhydrat entstehen nach der Gleichung:For the representation of diphenyl urethane one left to 2 MbI. Diphenylamine 1 mole. Chloroformic acid esters act (B. d. D. eh. G. XVIII, 2574), where. Diphenyl urethane and Diphenylamine chlorohydrate is formed according to the equation:
2 (C6H5)2NH+ ClCO2C2H5 .
= (C6H5)2 N - CO2C2H5 + (C6-Et5J8 — N H · H Cl.2 (C 6 H 5 ) 2 NH + ClCO 2 C 2 H 5 .
= (C 6 H 5 ) 2 N - CO 2 C 2 H 5 + (C 6 -Et 5 J 8 - NH · H Cl.
Zur Trennung wurde das Urethan in Benzol gelöst und von dem salzsauren Diphenylamin durch Abnutschen befreit. Dieses Verfahren leidet an dem Übelstande, daß durch die konzentrierten Lösungen der Diarylmethane in Kohlenwasserstoffen nicht unerhebliche Mengen Diarylaminchlorhydrate in Lösung gehalten werden, was bei der Abscheidung der. Urethane störend empfunden wird. Es hat sich nun' gezeigt, daß dieser Mißstand vermieden wird, wenn.man statt 2 Mol. nur 1 Mol. Diphenylamin anwendet und darauf 1 Mol. oder mehr .Chlorameisensäureester in der Wärme einwirken läßt. Es tritt dabei unter Chlorwasserstoffabspaltung eine völlige Um-Wandlung des Diphenylamine in Urethan ein. Dieser Reaktionsverlauf war nicht vorauszusehen. To separate the urethane was dissolved in benzene and from the hydrochloric acid diphenylamine freed by suction. This method suffers from the drawback that by the concentrated solutions of diarylmethanes in hydrocarbons are not insignificant Amounts of diarylamine chlorohydrates are kept in solution, which occurs during the deposition of the. Urethane is bothersome. It has now been shown that this deficiency has been avoided if.man instead of 2 moles. only 1 mole. Diphenylamine is used and then 1 mole. or more .chloroformate in the Lets warmth act. A complete conversion occurs with elimination of hydrogen chloride of diphenylamine in urethane. This course of the reaction could not be foreseen.
In der Patentschrift 285134 ist zwar ein Verfahren beschrieben, das die Herstellung von Diarylhärnstoffchloriden aus Diarylaminen ■und Phosgen auf ähnlichem Wege zum Gegenstand hat, die Ähnlichkeit des neuen Verfahrens mit dem bekannten ist aber nur eine scheinbare; denn bei der bekannten ungünstigen Einwirkung, die freier Chlorwasserstoff bei der Darstellung des Chlprameisensäureesters auf diesen ausübt, und bei der Neigung des Esters, auf .geringen Anstoß hin, z. B. in Gegenwart von Metallhologeniden, sich in Äthylchlorid und Kohlensäure zu zersetzen, konnte die glatte Bildung von Urethanen auf dem angegebenen Wege nicht vorausgesehen werden (vgl. Beilstein, Handbuch der organischen Chemie 1893, Bd. 1, S. 466, Abs. 4). In the patent 285134 is a Process described that the production of diaryl urea chlorides from diarylamines ■ and phosgene in a similar way has the similarity of the new process with the known, however, there is only an apparent one; because with the known unfavorable Exposure to the free hydrogen chloride in the preparation of the chloroprformic acid ester exerts on this, and with the tendency of the ester to. Am Presence of metal halides to decompose into ethyl chloride and carbonic acid, could not foresee the smooth formation of urethanes in the indicated way (cf. Beilstein, Handbuch derorganischen Chemie 1893, Vol. 1, p. 466, Paragraph 4).
Die Vorteile des Verfahrens, d. h.. Ersparnis an Rohstoffen (Diphenylamin, Soda), Raum und Arbeitshandlung, gewünschtenfalls Gewinnung eines verwertbaren Nebenproduktes (Salzsäure), Reinheit und damit leichte Isolierung des Endproduktes, sind einleuchtend. Wie Diphenylamin verhalten sich auch andere Diarylamine; statt der freien Basen können auch deren Chlorhydrate verwandt werden.The advantages of the process, i. h .. Saving of raw materials (diphenylamine, soda), space and Work activity, if desired, extraction of a usable by-product (hydrochloric acid), Purity and thus easy isolation of the end product are evident. Like diphenylamine also behave other diarylamines; Instead of the free bases, their chlorohydrates can also be used.
170 kg Diphenylamin werden mit einer Lösung von 120. kg Chlorameisensäureester in 200 kg Solventnaphta I unter Rühren langsam zum Sieden erhitzt. Bald tritt Ausscheidung von salzsaurem Diphenylamin ein, das aber dann bei weiterem Erhitzen unter allmählicher Steigerung der. Temperatur von 95 ° auf 115 bis 120° unter Chlorwasserstoffentwicklung in Lösung geht. Wenn alles Chlorhydrat gelöst ist, und die Chlorwasserstoffentwicklung nachgelassen hat, was nach 4- bis 5-stüridigem Erhitzen der Fall ist, ist die Reaktion zu Ende. Aus der nötigenfalls durch Sodalösung von Spuren Salzsäure befreiten Diphenylurethanlösung kann das Urethan durch Kristallisation170 kg of diphenylamine are mixed with a solution of 120 kg of chloroformic acid ester in 200 kg of solvent naphtha I slowly heated to boiling while stirring. Excretion soon occurs of hydrochloric acid diphenylamine, but this gradually increases with further heating Increase in. Temperature from 95 ° to 115 goes up to 120 ° with evolution of hydrogen chloride in solution. When all the chlorohydrate is dissolved is, and the evolution of hydrogen chloride has subsided, which after 4 to 5 hours of heating is the case, the reaction is over. If necessary, by soda solution of Diphenyl urethane solution freed from traces of hydrochloric acid can cause the urethane to crystallize
oder Vakuumdestillation gewonnen werden. Die Ausbeute ist nahezu quantitativ.or vacuum distillation. The yield is almost quantitative.
■ -·■ ^ f. A■ - · ■ ^ f. A
:,' v Beispiel 2.:, 'v Example 2.
100 l^ifeälzsaures DiprieMyiamin werden zusammen mit einer Lösung von 60 kg Chlorameisensäureester in Xylol am Rückfluß unter Rühren bis zur Beendigung der Chlorwasserstoff entwicklung erhitzt. Die erhaltene Diphenylurethanlösung wird analog Beispiel 1 weiter bearbeitet.100 l ^ ifeälzsaures DiprieMyiamin are combined with a solution of 60 kg of chloroformic acid ester in xylene under reflux with stirring until the hydrogen chloride has ceased development heated. The diphenyl urethane solution obtained is analogous to Example 1 further edited.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE306316C true DE306316C (en) |
Family
ID=559756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT306316D Active DE306316C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE306316C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050175390A1 (en) * | 2004-01-20 | 2005-08-11 | Meadwestvaco Corporation | Erasable writing system |
| US20050226675A1 (en) * | 2004-04-07 | 2005-10-13 | Sanford L.P. | Single- or double-ended multi-section nib marker |
-
0
- DE DENDAT306316D patent/DE306316C/de active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050175390A1 (en) * | 2004-01-20 | 2005-08-11 | Meadwestvaco Corporation | Erasable writing system |
| US20050226675A1 (en) * | 2004-04-07 | 2005-10-13 | Sanford L.P. | Single- or double-ended multi-section nib marker |
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