CH395988A - Process for the preparation of amino-diboron compounds - Google Patents
Process for the preparation of amino-diboron compoundsInfo
- Publication number
- CH395988A CH395988A CH365460A CH365460A CH395988A CH 395988 A CH395988 A CH 395988A CH 365460 A CH365460 A CH 365460A CH 365460 A CH365460 A CH 365460A CH 395988 A CH395988 A CH 395988A
- Authority
- CH
- Switzerland
- Prior art keywords
- amine
- formula
- compound
- boron
- diboron
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 24
- 150000001412 amines Chemical class 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 8
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 6
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- 125000004663 dialkyl amino group Chemical group 0.000 claims 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims 1
- -1 alkyl radical Chemical class 0.000 description 12
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000003141 primary amines Chemical group 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 238000005891 transamination reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 150000003840 hydrochlorides Chemical class 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- IIFFFBSAXDNJHX-UHFFFAOYSA-N 2-methyl-n,n-bis(2-methylpropyl)propan-1-amine Chemical compound CC(C)CN(CC(C)C)CC(C)C IIFFFBSAXDNJHX-UHFFFAOYSA-N 0.000 description 1
- WONYVCKUEUULQN-UHFFFAOYSA-N 2-methyl-n-(2-methylphenyl)aniline Chemical compound CC1=CC=CC=C1NC1=CC=CC=C1C WONYVCKUEUULQN-UHFFFAOYSA-N 0.000 description 1
- GELMWIVBBPAMIO-UHFFFAOYSA-N 2-methylbutan-2-amine Chemical compound CCC(C)(C)N GELMWIVBBPAMIO-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- OBYVIBDTOCAXSN-UHFFFAOYSA-N n-butan-2-ylbutan-2-amine Chemical compound CCC(C)NC(C)CC OBYVIBDTOCAXSN-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- IOXXVNYDGIXMIP-UHFFFAOYSA-N n-methylprop-2-en-1-amine Chemical compound CNCC=C IOXXVNYDGIXMIP-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation 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
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Description
Verfahren zur Herstellung von Amino-dibor-Verbindungen
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Organolor-Verbindungen der Formel (RffiN)2BB (NR'2)2 oder (R"HN)2B-B(NHR")2, worin R' einen einwertigen, aliphatischen oder cycloaliphatischen Rest mit mindestens einem Wasserstoff- atom an seinem a-Kohlenstoffatom, den Phenylrest oder einen substituierten Phenylrest darstellt, dessen ortho-Stellungen von Wasserstoffatomen besetzt sind, oder worin R'oN für die Piperidinogruppe steht und worin R" einen Alkylrest mit nicht mehr als 18 Kohlenstoffatomen, einen Cycloalkylrest oder einen Phenylrest bedeutet, welches dadurch gekennzeichnet ist,
dass man eine Verbindung der Formel B2(NR2)4, in der R einen einwertigen aliphatischen oder cycloaliphatischen Rest darstellt, der mindestens ein Wasser stoffatom an seinem a-Kohlenstoffatom aufweist, mit einer Verbindung der Formel R'2NH oder R"NH2 zur Reaktion bringt, wobei der Siedepunkt des Amins R2NH, das der Verbindung der Formel B2(NR2)4 entspricht, niedriger sein muss als der des Amins der Formel R'2NH oder R"NH2.
Gemäss der vorliegenden Erfindung findet eine Austauschreaktion statt, die eine Trans aminierung zwischen einer Tetra-amino-dibor-verbindung und einem Amin darstellt. Bei der Reaktion findet eine Spaltung von Stickstoff-Bor-Bindungen und Stickstoff-Wasserstoff-Bindungen statt, Während praktisch gleichzeitig neue Stickstoff-Bor-Bindungen und neue Stickstoff-Wasserstoff-Bindungen ausgebildet werden.
Es ist bekannt, dass viele Reaktionen von Bor-Bor Bindungen enthaltenden Verbindungen eine Spaltung der Bor-Bor-Bindung verursachen, aber es wurde bis her nicht gefunden, dass Amino-dibor-Verbindungen (die zu dieser Gruppe von Verbindungen gehören) eine Transaminierung unter Bildung von neuen Verbindungen ohne Aufspaltung der Bor-Bor-Bindung eingehen können.
Insbesondere werden nach dem erfindungsgemä Ben Verfahren die folgenden Verbindungen hergestellt: Tetra-(n-hexylamino)dibor, Tetra-(diphenyl amino)-dibor, Tetra-anilino-dlibor.
Wie oben beschrieben, leiten sich die in dem er findungsgemässen Verfahren als Reaktionspartner verwendeten Bor enthaltenden Verbindungen von sekundären Aminen ab, deren aliphatischen oder cycloaliphatischen Reste an den a-Kohlenstoffatomen mindestens ein Wasserstoffatom aufweisen, wodurch also die tertiären Reste ausgeschlossen sind.
Ist das als Reaktionspartner verwendete Amin ein sekundäres aliphatischs oder cycloaliphatisches Amin (R'2NH), ist es offensichtlich, dass tertiäre Gruppen hier ebenfalls ausgeschlossen sind, und ist das Amin ein sekundäres, substituiertes Phenylamin (R'2NH), dann müssen die substituierten Phenylkerne in den ortho-Stellungen Wasserstoff enthalten. Es wurde gefunden, dass diese Einschränkungen für den Reaktionsablauf von Bedeutung sind, denn in beiden Fällen treten dureh tertiäre Reste bzw. Substituenten in ortho-Stellung Effekte der sterischen Hinderung auf, die die Trans aminierung verhindern. Dadurch werden jedoch die Verbindungen, die verschiedene Reste R' in der Aminogruppe aufweisen, nicht von der Anwendung ausgeschlossen.
In dem Fall, in dem das als Reaktionspartner verwendete Amin ein primäres Amin ist, ist es offensichtlich, dass die oben beschriebenen Einschränkungen nicht in Erscheinung treten, da gefunden wurde, dass eine sterische Hinderung hier nicht auftritt.
Das erfindungsgemässe Verfahren kann durch die folgenden Gleichungen dargestellt werden:
EMI2.1
Als Reaktionspartner, die durch die Formel B2(NR2)4 dargestellt werden, können die Verbindungen verwendet werden, in denen R den Methyl¯, Äthyl-, n-Propyl-, Isopropyl-, nButyl-, n-Pentyl und n-Hexylrest bedeutet. Aus Gründen des Preises und der leichten ZUgänglichkeit werden vorzugsweise die Tetra - dialkylamino - dibor-verbindungen verwendet, deren Alkylreste 1 bis 3 Kohlenstoffatome enthalten; insbesondere ist für das erfindungsgemässe Verfahren die Verwendung von Tetra-(dimethylamino)-dibor zu empfehlen.
Als sekundäre Amine können beispielsweise die folgenden Verbindungen verwendet werden: Dimethylamin, Diäthylamin, Di-n-propyiamin, Diisopropylamin, Di-n-butylamin, Di-sek.-butylamin, Dicyclohexylamin, Di-nohexylamin, Piperidin, Diphenyl amin und Di-tolylamin.
Als primäre Amine können die folgenden Verbindungen verwendet werden: Methylamin, Äthyl- amin, n-Propylamin, Isopropylamin, n-Butylamin, sek.-Butylamin, tert.-Butylamin, Cyclohexylamin, Cyclopentylamin, Anilin und p-Toluidin.
Es werden zweckmässigerweise 4 Mol Amin pro Mol der Verbindung B2(NR2)4 verwendet.
Die erfindungsgemäss ausgeführten Reaktionen können durch Ammoniumchlorid, Ammoniumbromid oder Ammoniumsulfat oder Salze einer starken Säure mit einem Amin, z. B. die Hydrochloride, Hydrobromide, Sulfate, Trifluoracetate, katalysiert werden.
Es ist selbstverständlich, dass diese Verbindungen sich nicht an der Reaktion beteiligen (in dem Sinne, dass sie verbraucht werden), aber sie können in katalytischen Mengen angewendet werden, um die Reaktion zu beschleunigen. So kann das Salz eines jeden primären, sekundären oder tertiären Amins mit einer starken Säure als Katalysator bei den Reaktionen des erfindungsgemässen Verfahrens verwendet werden'.
Beispielsweise können die Hydrochloride, Hydrobromide, Sulfate, Trifluoracetate der folgenden Amine als Katalysatoren verwendet werden: Methylamin, Äthylamin, n-Propylamin, Isopropylamin, nrsek.- und tert.-Butylamin, n- und tert.-Amylamin, Hexylamin, Pyrrol, Anilin, Aminopyridin, Thiophenylamin, Dimethylamin, Diäthylamin, Di-n-butylamin, Di-isopropylamin, Allylmethylamin, N-Methylanilin, Diphenylamin, Trimethylamin, Triäthylamin, Tri-n-propylamin, Tri-iso-butylamin, Trihexylamin, Triphenylamin und Pyridin.
Die vorliegende Erfindung erlaubt eine praktische und wirtschaftliche Methode zur Herstellung einer Amino-dibor-verbindung aus einer anderen derartigen Verbindung.
Beispiel 1
4,00 g (0,0202 Mol) Tetra-(dimethylamino)ibor und 8,17 g (0,0808 Mol) nHexylamin werden von 241150 C ungefähr 3 Stunden lang erhitzt. Das entstehende Dimethylamin wird mit Hilfe eines trockenen Stickstoffstromes entfernt und in eine wässrige HCl-Lösung eingeleitet. Der erhaltene Rückstand ist Tetra-(n-hexylamino)-dibor, eine farblose, nichtflüchtige Flüssigkeit mit dem Brechungsindex n D25 1,4606.
Die Ausbeute beträgt 91 %. Laut Analyse enthält die Verbindung 5,20 % Bor, berechnet für Q4H56N4B2: 5,11% Bor.
Beispiel 2
Eine Lösung aus 5,0 g (0,025 Mol) Tetra-(dimethylamino)-dibor und 13,04 g (0,101 Mol) Di-n- butylamin in 25 cm3 Hexan wird bei 741740 C etwa 21 Stunden lang in einer Stickstoffatmosphäre am Rückfluss erhitzt. Das entweichende Dimethylamin wird in eine standardisierte wässrige HCl-Lösung geleitet. Das Lösungsmittel und die umgesetzten, Ausgangsmaterialien werden durch Destillation bei 0,1 bis 0,5 mm Hg entfernt. Man erhält 93,4% Tetra (di-n-butylamino)-dibor, Kp: 170-183 C bei 0,55 mm, n D25 1,4667.
Analyse: C32H72N4B2:
Berechnet: B 4,05 N 10,48 % Molgewicht: 534
Gefunden: B 4,30 N 10,35 % Molgewicht: 557 (krysoskopisch ermittelt in C6H6)
Beispiel 3
Eine Lösung aus 10,3 g (0,0607 Mol) Diphenylamin und 3,0 g (0,0152 Mol) Tetra-(dimethylamino)- dibor in 25 cm3 Toluol und einer katalytischen Menge Methylamin-hydtochlorid wird 100 Stunden lang auf 1000 C erhitzt (der Katalysator erhöht die Reaktion geschwindigkeit mindestens um das Doppelte). Das Dimethylamin wird mit Hilfe eines Stickstoffstromes in standardisierte Säurelösung eingeleitet.
Das Toluol wird durch Vakuumdestillation entfernt, und man erhält das Tetra-(diphenylamino)-dibor in 100% iger Ausbeute als eine grüne, viskose Flüssigkeit, die laut Analyse 3,10% Bor enthält (berechnet für Tetra diphenylamino-dibor: 3,12 B). Dieses Produkt ist ih Benzol und Chloroform löslich, unlöslich in n Hexan, Bromoform und kaltem Aceton.
Beispiel 4
1 Teil Tetra-(dimethylamino)-dibor wird mit 4 Teilen Anilin erhitzt. Die Reaktion wird auf die in Beispiel 1 beschriebene Weise durchgeführt, und das entstehende Produkt, das Tetraanillno-dibor, wird in 95 % iger Ausbeute erhalten.
Process for the preparation of amino-diboron compounds
The present invention relates to a process for the preparation of organoloric compounds of the formula (RffiN) 2BB (NR'2) 2 or (R "HN) 2B-B (NHR") 2, in which R 'is a monovalent, aliphatic or cycloaliphatic radical represents at least one hydrogen atom on its a-carbon atom, the phenyl radical or a substituted phenyl radical whose ortho positions are occupied by hydrogen atoms, or in which R'oN stands for the piperidino group and in which R "is an alkyl radical with not more than 18 carbon atoms, denotes a cycloalkyl radical or a phenyl radical, which is characterized by
that a compound of the formula B2 (NR2) 4, in which R is a monovalent aliphatic or cycloaliphatic radical which has at least one hydrogen atom on its a-carbon atom, is reacted with a compound of the formula R'2NH or R "NH2 , the boiling point of the amine R2NH, which corresponds to the compound of the formula B2 (NR2) 4, must be lower than that of the amine of the formula R'2NH or R "NH2.
According to the present invention, an exchange reaction takes place which represents a trans amination between a tetra-amino-diboron compound and an amine. During the reaction, nitrogen-boron bonds and nitrogen-hydrogen bonds are split, while new nitrogen-boron bonds and new nitrogen-hydrogen bonds are formed practically at the same time.
It is known that many reactions of compounds containing boron-boron bonds cause cleavage of the boron-boron bond, but it has not yet been found that amino-diboron compounds (belonging to this group of compounds) undergo transamination Formation of new compounds without breaking the boron-boron bond.
In particular, the following compounds are produced by the process according to the invention: tetra- (n-hexylamino) diboron, tetra- (diphenylamino) -diboron, tetra-anilino-diboron.
As described above, the boron-containing compounds used as reactants in the process according to the invention are derived from secondary amines, the aliphatic or cycloaliphatic radicals of which have at least one hydrogen atom on the a-carbon atoms, so that the tertiary radicals are excluded.
If the amine used as the reactant is a secondary aliphatic or cycloaliphatic amine (R'2NH), it is obvious that tertiary groups are also excluded here, and if the amine is a secondary, substituted phenylamine (R'2NH), then the substituted phenyl nuclei must contain hydrogen in the ortho positions. It has been found that these restrictions are important for the course of the reaction, because in both cases effects of steric hindrance occur due to tertiary radicals or substituents in the ortho position, which prevent the trans amination. However, this does not exclude the compounds which have different radicals R 'in the amino group from use.
In the case where the amine used as the reactant is a primary amine, it is obvious that the limitations described above do not appear, since it has been found that steric hindrance does not occur here.
The method according to the invention can be represented by the following equations:
EMI2.1
The compounds in which R denotes the methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl and n-hexyl radicals can be used as reactants represented by the formula B2 (NR2) 4 . For reasons of price and ease of access, the tetra-dialkylamino-diboron compounds are preferably used, the alkyl radicals of which contain 1 to 3 carbon atoms; In particular, the use of tetra (dimethylamino) diboron is recommended for the process according to the invention.
The following compounds, for example, can be used as secondary amines: dimethylamine, diethylamine, di-n-propyiamine, diisopropylamine, di-n-butylamine, di-sec-butylamine, dicyclohexylamine, di-nohexylamine, piperidine, diphenylamine and di-tolylamine .
The following compounds can be used as primary amines: methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, cyclohexylamine, cyclopentylamine, aniline and p-toluidine.
It is expedient to use 4 moles of amine per mole of compound B2 (NR2) 4.
The reactions carried out according to the invention can be carried out by ammonium chloride, ammonium bromide or ammonium sulfate or salts of a strong acid with an amine, e.g. B. the hydrochlorides, hydrobromides, sulfates, trifluoroacetates, are catalyzed.
It goes without saying that these compounds do not take part in the reaction (in the sense that they are consumed), but they can be used in catalytic amounts to speed up the reaction. Thus, the salt of any primary, secondary or tertiary amine with a strong acid can be used as a catalyst in the reactions of the process according to the invention.
For example, the hydrochlorides, hydrobromides, sulfates, trifluoroacetates of the following amines can be used as catalysts: methylamine, ethylamine, n-propylamine, isopropylamine, nr-sec.- and tert-butylamine, n- and tert-amylamine, hexylamine, pyrrole, aniline , Aminopyridine, thiophenylamine, dimethylamine, diethylamine, di-n-butylamine, di-isopropylamine, allylmethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, tri-n-propylamine, tri-iso-butylamine, trihexylamine, triphenylamine and pyridine.
The present invention provides a convenient and economical method of making an amino-diboron compound from another such compound.
example 1
4.00 g (0.0202 mol) of tetra (dimethylamino) ibor and 8.17 g (0.0808 mol) of n-hexylamine are heated at 241150 ° C. for about 3 hours. The dimethylamine formed is removed with the aid of a stream of dry nitrogen and introduced into an aqueous HCl solution. The residue obtained is tetra (n-hexylamino) diboron, a colorless, non-volatile liquid with the refractive index n D25 1.4606.
The yield is 91%. According to analysis, the compound contains 5.20% boron, calculated for Q4H56N4B2: 5.11% boron.
Example 2
A solution of 5.0 g (0.025 mol) of tetra (dimethylamino) diboron and 13.04 g (0.101 mol) of di-n-butylamine in 25 cm3 of hexane is refluxed at 741740 C for about 21 hours in a nitrogen atmosphere . The dimethylamine that escapes is passed into a standardized aqueous HCl solution. The solvent and the reacted starting materials are removed by distillation at 0.1 to 0.5 mm Hg. 93.4% of tetra (di-n-butylamino) diboron are obtained, b.p .: 170-183 ° C. at 0.55 mm, n D25 1.4667.
Analysis: C32H72N4B2:
Calculated: B 4.05 N 10.48% molecular weight: 534
Found: B 4.30 N 10.35% molar weight: 557 (determined crysoscopically in C6H6)
Example 3
A solution of 10.3 g (0.0607 mol) of diphenylamine and 3.0 g (0.0152 mol) of tetra (dimethylamino) diboron in 25 cm3 of toluene and a catalytic amount of methylamine hydrochloride is heated to 1000 ° C. for 100 hours heated (the catalyst increases the reaction speed at least twice). The dimethylamine is introduced into standardized acid solution with the aid of a stream of nitrogen.
The toluene is removed by vacuum distillation, and the tetra- (diphenylamino) diboron is obtained in 100% yield as a green, viscous liquid which, according to analysis, contains 3.10% boron (calculated for tetrahiphenylamino-diboron: 3.12 B). This product is soluble in benzene and chloroform, insoluble in hexane, bromoform and cold acetone.
Example 4
1 part of tetra (dimethylamino) diboron is heated with 4 parts of aniline. The reaction is carried out in the manner described in Example 1 and the resulting product, tetraanillodiboron, is obtained in 95% yield.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US81672659A | 1959-05-29 | 1959-05-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH395988A true CH395988A (en) | 1965-07-31 |
Family
ID=25221454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH365460A CH395988A (en) | 1959-05-29 | 1960-04-01 | Process for the preparation of amino-diboron compounds |
Country Status (3)
| Country | Link |
|---|---|
| BE (1) | BE588759A (en) |
| CH (1) | CH395988A (en) |
| SE (1) | SE303761B (en) |
-
1960
- 1960-03-17 BE BE588759A patent/BE588759A/en unknown
- 1960-04-01 SE SE324160A patent/SE303761B/xx unknown
- 1960-04-01 CH CH365460A patent/CH395988A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BE588759A (en) | 1960-07-18 |
| SE303761B (en) | 1968-09-09 |
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