DE1080983B - Process for the production of alkaline earth borohydrides - Google Patents
Process for the production of alkaline earth borohydridesInfo
- Publication number
- DE1080983B DE1080983B DEST12303A DEST012303A DE1080983B DE 1080983 B DE1080983 B DE 1080983B DE ST12303 A DEST12303 A DE ST12303A DE ST012303 A DEST012303 A DE ST012303A DE 1080983 B DE1080983 B DE 1080983B
- Authority
- DE
- Germany
- Prior art keywords
- alkaline earth
- borohydrides
- hydrocarbon radical
- production
- compounds
- 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 8
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000002904 solvent Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 150000001639 boron compounds Chemical class 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- -1 hydrocarbon radical Chemical group 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 101100219382 Caenorhabditis elegans cah-2 gene Proteins 0.000 description 1
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Chemical compound CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZGLFRTJDWWKIAK-UHFFFAOYSA-M [2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]-triphenylphosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC(=O)OC(C)(C)C)C1=CC=CC=C1 ZGLFRTJDWWKIAK-UHFFFAOYSA-M 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 229910000095 alkaline earth hydride Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008096 xylene Substances 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
Description
Verfahren zur Herstellung von Erdalkaliborhydriden Zusatz zum Patent 1 227 Gegenstand des Hauptpatents 1 227 ist ein Verfahren zur Herstellung von Alkaliborhydriden durch Behandlung von Komplexverbindungen der Formel Me (BH,~,R,), in der Me ein Alkalimetall, R einen Kohlenwasserstoffrest und X eine Zahl von 1 bis 3 bedeutet, mit überschüssigen Borverbindungen der allgemeinen Formel BHRR', in der R einen gesättigten aliphatischen Kohlenwasserstoffrest und R' einen gesättigten aliphatischen Kohlenwasserstoffrest oder Wasserstoff bedeutet.Process for the production of alkaline earth borohydrides 1 227 The subject of the main patent 1 227 is a process for the preparation of alkali borohydrides by treating complex compounds of the formula Me (BH, ~, R,), in the Me a Alkali metal, R is a hydrocarbon radical and X is a number from 1 to 3, with excess boron compounds of the general formula BHRR ', in which R is a saturated aliphatic hydrocarbon radical and R 'is a saturated aliphatic Means hydrocarbon radical or hydrogen.
Die Komplexverbindungen der allgemeinen Formel Me (B H,~,Rn) erhält man durch Anlagerung von Alkalihydriden an Borverbindungen der allgemeinen Formel BRR'2. The complex compounds of the general formula Me (B H, ~, Rn) are obtained by adding alkali metal hydrides to boron compounds of the general formula BRR'2.
Es wurde nun gefunden, daß auch Erdalkalihydride die erwähnte Spaltungsreaktion der teilweise alkylierten Borwasserstoffe ermöglichen. Dabei werden als einzige feste Verbindungen Erdalkaliborhydride der allgemeinen Formel Me (B H4)2, in der Me Erdalkalimetall bedeutet, gewonnen. Die Umsetzung verläuft dabei z. B. gemäß der Gleichung MeH2 +3B2H2R4 =Me(BH4)2 +4ER3. It has now been found that alkaline earth metal hydrides also cause the above-mentioned cleavage reaction of the partially alkylated boron hydrocarbons. Be the only one solid compounds alkaline earth borohydrides of the general formula Me (B H4) 2, in which Me alkaline earth metal means extracted. The implementation proceeds z. B. according to the equation MeH2 + 3B2H2R4 = Me (BH4) 2 + 4ER3.
Grundsätzlich kann man wie beim Hauptpatent 1 227 von freiem Metall ausgehen. Da im Gegensatz zu den Alkalimetallen die Erdalkalimetalle jedoch einen sehr hohen Schmelzpunkt haben, wird das Arbeiten mit den feinverteilten Hydriden fast immer vorteilhafter sein. In principle, as in the case of the main patent 1,227 of free metal go out. Since, in contrast to the alkali metals, the alkaline earth metals have one have a very high melting point, working with the finely divided hydrides almost always be more beneficial.
Zweckmäßig arbeitet man mit einem Überschuß an Alkyldiboran. Das erfindungsgemäße Verfahren kann daher unter Verwendung von teilweise alkylierten Borwasserstoffen der allgemeinen Formel B2Ha;R6-Zx in der x eine Zahl von 2 bis 5 bedeutet, als Lösungsmittel durchgeführt werden. Weitere geeignete Lösungsmittel sind vor allem gesättigte aliphatische und aromatische Kohlenwasserstoffe sowie Äther. Bei höheren Temperaturen, insbesondere bei Temperaturen über 1600 C, arbeitet man zweckmäßig in Gegenwart von tertiären Aminen. It is expedient to work with an excess of alkyldiborane. That The inventive method can therefore using partially alkylated Boron hydrogen of the general formula B2Ha; R6-Zx in which x is a number from 2 to 5 means to be carried out as a solvent. Other suitable solvents are mainly saturated aliphatic and aromatic hydrocarbons as well Ether. At higher temperatures, especially at temperatures above 1600 C, works one expediently in the presence of tertiary amines.
Bei Verwendung bestimmter Äther als Lösungsmittel, wie z. B. Tetrahydrofuran, Diglykoldimethyläther, Triglykoltrimethyläther usw., erhält man die Erdalkaliborhydride, insbesondere die des Magnesiums, Calciums und Strontiums zunächst in Lösung als Ätherate, aus denen sie in bekannter Weise in reiner Form isoliert werden können. Bei einer solchen Arbeitsweise vermeidet man das Umkristallisieren, das sonst erforderlich wird, wenn die eingesetzten Erdalkalihydride nicht rein waren.When using certain ethers as solvents, such as. B. tetrahydrofuran, Diglycol dimethyl ether, triglycol trimethyl ether, etc., one obtains the alkaline earth borohydrides, especially those of magnesium, calcium and strontium initially in solution as Etherates from which they can be isolated in a known manner in pure form. Such a procedure avoids recrystallization, which would otherwise be necessary if the alkaline earth hydrides used were not pure.
Wenn sämtliche bei der Reaktion eingesetzten oder gebildeten festen Stoffe in dem verwendeten Lösungsmittel unlöslich sind, arbeitet man vorteilhaft in einer Kugelmühle. If all of the solid used or formed in the reaction Substances are insoluble in the solvent used, it is advantageous to work in a ball mill.
Die Ausbeuten an Erdalkaliborhydriden bei dem erfindungsgemäßen Verfahren sind praktisch quantitativ. Die Erdalkaliborhydride sind insbesondere als selektive Reduktionsmittel in der präparativen Chemie und zur Herstellung von Diboran B2 H6 geeignet. The yields of alkaline earth borohydrides in the process according to the invention are practically quantitative. The alkaline earth borohydrides are particularly selective Reducing agents in preparative chemistry and for the production of diborane B2 H6 suitable.
Beispiel 1 CaH2 + 3B2H2(C3H7)4 = Ca (B H4)a + 4B(QH7)3 8,4 g (0,2 Mol) Calciumhydrid werden in 200 ccm Xylol zusammen mit einem Überschuß (etwa 150 g) Tetran-propyldiboran (etwa 0,76 Mol) in einer heizbaren Kugelschwingmühle unter Stickstoff während 3 bis 4 Stunden am Rückfluß auf 140 bis 150"C erhitzt. Man erhält anschließend nach Ab destillieren des Lösungsmittels und des entstandenen Bortri-n-propyls zusammen mit dem unverbrauchten Tetra-n-propyldiboran als Rückstand 13,5 g Calciumborhydrid. Falls unreines Calciumhydrid verwendet wurde, wird das Calciumborhydrid aus Tetrahydrofuran umkristallisiert. Die Ausbeute ist annähernd quantitativ. Example 1 CaH2 + 3B2H2 (C3H7) 4 = Ca (B H4) a + 4B (QH7) 3 8.4 g (0.2 Mol) calcium hydride are in 200 ccm xylene together with an excess (about 150 g) Tetran-propyldiborane (about 0.76 mol) in a heatable vibrating ball mill Nitrogen heated under reflux to 140 to 150 ° C. for 3 to 4 hours. This gives then after distilling off the solvent and the resulting boron tri-n-propyl together with the unused tetra-n-propyldiborane as residue 13.5 g calcium borohydride. If impure calcium hydride was used, the calcium borohydride recrystallized from tetrahydrofuran. The yield is almost quantitative.
Beispiel 2 BaH2 + 2B2H3(C2Hs)3 = Ba(BH4)2 + 2B(C2H5)3 Wie im Beispiel 1 erhält man aus 69,5 g (0,5 Mol) Bariumhydrid in 400 ccm Perhydrocumol und 120 g (1,07 Mol) Triäthyldiboran insgesamt 75 g (= 90 0/, Ausbeute) Bariumborhydrid. Example 2 BaH2 + 2B2H3 (C2Hs) 3 = Ba (BH4) 2 + 2B (C2H5) 3 As in the example 1 is obtained from 69.5 g (0.5 mol) of barium hydride in 400 cc of perhydrocumene and 120 g (1.07 mol) of triethyldiborane, a total of 75 g (= 90%, yield) of barium borohydride.
PATENTANSPR8CHE 1. Abänderung des Verfahrens zur Herstellung von Metallborhydriden nach Patent 1 062227, dadurch gekennzeichnet, daß man zur Herstellung von Erd- PATENT CLAIMS 1. Modification of the process for making Metal borohydrides according to Patent 1,062,227, characterized in that for the production of terrestrial
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEST11020A DE1062227B (en) | 1956-03-28 | 1956-03-28 | Process for the preparation of alkali borohydrides |
| DEST12303A DE1080983B (en) | 1956-03-28 | 1957-03-06 | Process for the production of alkaline earth borohydrides |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEST11020A DE1062227B (en) | 1956-03-28 | 1956-03-28 | Process for the preparation of alkali borohydrides |
| DEST12303A DE1080983B (en) | 1956-03-28 | 1957-03-06 | Process for the production of alkaline earth borohydrides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1080983B true DE1080983B (en) | 1960-05-05 |
Family
ID=33030691
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEST11020A Pending DE1062227B (en) | 1956-03-28 | 1956-03-28 | Process for the preparation of alkali borohydrides |
| DEST12303A Pending DE1080983B (en) | 1956-03-28 | 1957-03-06 | Process for the production of alkaline earth borohydrides |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEST11020A Pending DE1062227B (en) | 1956-03-28 | 1956-03-28 | Process for the preparation of alkali borohydrides |
Country Status (1)
| Country | Link |
|---|---|
| DE (2) | DE1062227B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH129294A (en) * | 1926-08-23 | 1928-12-01 | Degussa | Process for the production of alkali hydride. |
| US2729540A (en) * | 1945-09-24 | 1956-01-03 | Du Pont | Process of preparing alkali metal and alkaline earth metal borohydrides |
-
1956
- 1956-03-28 DE DEST11020A patent/DE1062227B/en active Pending
-
1957
- 1957-03-06 DE DEST12303A patent/DE1080983B/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE1062227B (en) | 1959-07-30 |
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