DE1048586B - - Google Patents
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- Publication number
- DE1048586B DE1048586B DENDAT1048586D DE1048586DA DE1048586B DE 1048586 B DE1048586 B DE 1048586B DE NDAT1048586 D DENDAT1048586 D DE NDAT1048586D DE 1048586D A DE1048586D A DE 1048586DA DE 1048586 B DE1048586 B DE 1048586B
- Authority
- DE
- Germany
- Prior art keywords
- hydrogen
- mol
- atm
- autoclave
- hours
- 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
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- -1 hydrocarbon radicals Chemical class 0.000 claims description 4
- 230000001603 reducing effect Effects 0.000 claims description 3
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000085 borane Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N N,N-Diethylethanamine Substances CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 7
- 239000000203 mixture Substances 0.000 claims 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 3
- 238000000354 decomposition reaction Methods 0.000 claims 3
- 150000002431 hydrogen Chemical class 0.000 claims 3
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 238000009835 boiling Methods 0.000 claims 2
- 150000001639 boron compounds Chemical class 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 2
- 239000001282 iso-butane Substances 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 2
- 239000001294 propane Substances 0.000 claims 2
- 101100231508 Caenorhabditis elegans ceh-5 gene Proteins 0.000 claims 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000007664 blowing Methods 0.000 claims 1
- HXNZTJULPKRNPR-UHFFFAOYSA-N borinine Chemical compound B1=CC=CC=C1 HXNZTJULPKRNPR-UHFFFAOYSA-N 0.000 claims 1
- 239000012043 crude product Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 claims 1
- 238000004868 gas analysis Methods 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- ORSUTASIQKBEFU-UHFFFAOYSA-N n,n-diethylbutan-1-amine Chemical compound CCCCN(CC)CC ORSUTASIQKBEFU-UHFFFAOYSA-N 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical class [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- FLLNLJJKHKZKMB-UHFFFAOYSA-N boron;tetramethylazanium Chemical group [B].C[N+](C)(C)C FLLNLJJKHKZKMB-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 208000001848 dysentery Diseases 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Description
DEUTSCHESGERMAN
C07fC07f
PATENTAMTPATENT OFFICE
V . Z5592IVb/12qV. Z5592IVb / 12q
BEKANNTMACHUNG DER ANMELDUNG UND AUSGABE DERNOTICE THE REGISTRATION AND ISSUE OF THE
Die Herstellung von N-substituierten Borazanen der allgemeinen Formel H3 B · NR'R"R"', in der R', R" und R'" einen aliphatischen, cycloaliphatischen und/oder aromatischen KohlenwasserstofTrest bedeuten, ist noch nicht befriedigend gelöst. Bisher ist lediglich das N-Trimiethylborazanbeschrieben worden. Für dessen Darstellung sind verschiedene Methoden bekannt. Zum Beispiel wird ein Borwasserstoff, beispielsweise das Diboran B2H6, mit Trimethykmin umgesetzt, wobei sich das N-Trimefhylborazani bildet (vgl. A. B.Burg, H. I. Schlesinger : Journal of American Society, 59, S. 780 bis 787 [1937]). Eine dieser Methoden verwandte Darstellungsart des N-Trimefihylborazans besteht in der Reaktion von Borin-Carbonyl H3B · CO mit Trimethylamin (vgl; H. I. Schlesinger, A.B.Burg: Chemical Reviews, 31, S. 19 [1942]).The preparation of N-substituted borazanes of the general formula H 3 B · NR'R "R"', in which R', R "and R '" denote an aliphatic, cycloaliphatic and / or aromatic hydrocarbon radical, has not yet been satisfactorily solved. Only N-trimiethylborazane has been described so far. Various methods are known for its representation. For example, a hydrogen boride, for example the diborane B 2 H 6 , is reacted with trimethylamine to form the N-trimefhylborazane (cf. ABBurg, HI Schlesinger: Journal of American Society, 59, pp. 780 to 787 [1937]). One type of representation of N-trimefihylborazane related to these methods consists in the reaction of borine carbonyl H 3 B · CO with trimethylamine (cf. HI Schlesinger, ABBurg: Chemical Reviews, 31, p. 19 [1942]).
Nach dem Verfahren des USA.-Patents 2 678 949 wird, verglichen mit den vorstehend angeführten Verfahren, zwar die Verwendung von freiem gasförmigern Borwasserstoff bei der Herstellung von N-substituierten Borazanen vermieden, doch geht hier durch eine thermische Zersetzung von Tetramethylammoniumborhydrid (CH3)4NBH4 nach der Gleichung.According to the process of US Pat. No. 2,678,949, compared with the processes listed above, the use of free gaseous hydrogen boride in the production of N-substituted borazanes is avoided, but thermal decomposition of tetramethylammonium borohydride (CH 3 ) 4 NBH 4 according to the equation.
(CH3)4NBH4 -> H3B-N(CH3)3 + CH4 (CH 3) 4 NBH 4 -> H 3 BN (CH 3) 3 + CH 4
ein Viertel des bereits vorhandenen Borwasserstoffanteils verloren. Darüber hinaus ist die Herstellung der für das Verfahren notwendigen Ausgangsverbindungen mit besonderen Schwierigkeiten verbunden, da man für die Gewinnung von quartären Ammoniumborbydriden zunächst einmal ein Metallborhydrid herstellen muß.lost a quarter of the already existing hydrogen boride content. In addition, the manufacture the starting compounds necessary for the process are associated with particular difficulties, because for the production of quaternary ammonium borohydrides, first of all a metal borohydride must produce.
Es wurde gefunden, daß man ohne besondere Vorsichtsmaßregeln sämtliche Kohlenwasserstoffreste von Borkohlenwasserstoffen der allgemeinen Formel BR3, in der R einen Kohlenwasserstoffrest bedeutet, unmittelbar durch Wasserstoff ersetzen kann, wenn man die Borkohlenwasserstoffe in Gegenwart von tertiären Aminen der allgemeinen Formel NR'R"R"', in der R', R" und R'" einen Kohlenwasserstoffrest, insbesondere einen aliphatischen, cycloaliphatischen und/ oder aromatischen Kohlenwasserstoffrest, bedeuten, mit Wasserstoff unter Druck auf Temperaturen über 120° C erhitzt.It has been found that all hydrocarbon radicals of boron hydrocarbons of the general formula BR 3 , in which R denotes a hydrocarbon radical, can be replaced directly by hydrogen without special precautionary measures if the boron hydrocarbons are in the presence of tertiary amines of the general formula NR'R "R"', in which R', R "and R '" mean a hydrocarbon radical, in particular an aliphatic, cycloaliphatic and / or aromatic hydrocarbon radical, heated to temperatures above 120 ° C. with hydrogen under pressure.
Bei Temperaturen oberhalb 140° C werden dabei vorzugsweise in einer rasch verlaufenden Reaktion nach folgender allgemeiner Gleichung die N-trisubs'tituierten Borazane in nahezu quantitativer Ausbeute gebildet:At temperatures above 140 ° C., a rapid reaction is preferred according to the following general equation the N-trisubstituted borazanes in almost quantitative yield educated:
Verfahren zur Herstellung
von Kohlenwasserstoffreste,
Wasserstoff und Stickstoff enthaltenden
BorverbindungenMethod of manufacture
of hydrocarbon residues,
Containing hydrogen and nitrogen
Boron compounds
Anmelder:Applicant:
Studiengesellschaft Kohle m.b.H.,
Mülheim/Ruhr, Kais er-Wilhelm-Platz 2Study Society Coal mbH,
Mülheim / Ruhr, Kais er-Wilhelm-Platz 2
Dipl.-Chem. Dr. Roland Köster, Mülheim/Ruhr, ist als Erfinder genannt wordenDipl.-Chem. Dr. Roland Köster, Mülheim / Ruhr, has been named as the inventor
lose Flüssigkeiten, deren Geruch im allgemeinen weder die Anwesenheit von Amin noch die von Borwasserstoff erkennen läßt. Das einzige bisher in der Literatur beschriebene N-trisubstituierte Borazan, das N-Trimetbylborazan, ist dagegen eine gut kristallisierte, leicht, subliimierbare Verbindung. Die erfindungsgemäßen Reaktionsprodukte sind thermisch außerordentlich stabile Verbindungen. Sie sind luftunempfindlich und reagieren nicht ohne weiteres mit alkalischen oder neutralen wäßrigen Lösungsmitteln. Erst beim Ansäuern wird Wasserstoff als Gas frei.loose liquids, the odor of which generally reveals neither the presence of amine nor that of hydrogen boride. The only one so far in the N-trisubstituted borazane, N-trimethylborazane, is a well-crystallized, easy, sublimable connection. The reaction products of the invention are thermal extremely stable connections. They are insensitive to air and do not readily react with it alkaline or neutral aqueous solvents. Hydrogen is only released as a gas when acidified.
Die N-Trialkylborazane sind in der anorganischen und insbesondere der organischen Chemie ähnlichThe N-trialkylborazanes are similar in inorganic and especially organic chemistry
R3B· + NR3 + 3H, =R 3 B + NR 3 + 3H, =
H3BH 3 B
NR3 + 3HR.NR 3 + 3HR.
Die nach dem erfindungsgemäßen Verfahren hergestellten Verbindungen sind fast ausnahmslos farbwie die Metallborhydride zu Reduktionszwecken geeignet. Gegenüber Alkali- und Erdalkaliboranaten weisen sie den Vorteil auf, nicht so stark alkalisch zu reagieren, wenn die Reduktionswirkung eingesetzt hat. Trotzdem ist ihre Reduktionskraft, verglichen mit der von komplexen Metallborhydriden, kaum verändert. Diesen gegenüber weisen sie den weiteren Vorteil auf, daß sie in vielen organischen Lösungsmitteln weitaus besser löslich sind.Almost without exception, the compounds produced by the process according to the invention have the same color the metal borohydrides are suitable for reduction purposes. Compared to alkali and alkaline earth boranates they have the advantage of not reacting as strongly alkaline when the reducing effect is used Has. Nevertheless, their reducing power is hardly changed compared to that of complex metal borohydrides. Compared to these, they have the further advantage that they can be used in many organic solvents are much more soluble.
Die erfindungsgemäß hergestellten Borazane lassen sich in einfacher Weise reinigen und werden im allgemeinen durch Umkristallisieren aus Kohlenwasserstoffen, vorzugsweise jedoch durch Destillation bzw. Sublimation, in völlig reiner Form erhalten. Im großen und ganzen sind die erfindungsgemäß hergestellten Verbindungen jedoch unmittelbar so rein, daß derartige Reinigungsverfahren nicht nötig sind.The borazanes prepared according to the invention can be cleaned in a simple manner and are generally used by recrystallization from hydrocarbons, but preferably by distillation or Sublimation, preserved in a completely pure form. By and large are those made in accordance with the invention However, compounds are immediately so pure that such cleaning processes are not necessary.
809 729i'285809 729i'285
Claims (1)
Publications (1)
Publication Number | Publication Date |
---|---|
DE1048586B true DE1048586B (en) | 1959-01-15 |
Family
ID=589744
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DENDAT1048586D Pending DE1048586B (en) |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE1048586B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3013016A (en) * | 1957-05-24 | 1961-12-12 | Bayer Ag | Trialkylamine boranes and their preparation |
US3362995A (en) * | 1962-12-21 | 1968-01-09 | Nat D Etudes Et De Rech S Off | Benzidene boron complex and process for preparing the same |
-
0
- DE DENDAT1048586D patent/DE1048586B/de active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3013016A (en) * | 1957-05-24 | 1961-12-12 | Bayer Ag | Trialkylamine boranes and their preparation |
US3362995A (en) * | 1962-12-21 | 1968-01-09 | Nat D Etudes Et De Rech S Off | Benzidene boron complex and process for preparing the same |
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