DE1058478B - Process for the production of hydrogen compounds of boron or aluminum - Google Patents
Process for the production of hydrogen compounds of boron or aluminumInfo
- Publication number
- DE1058478B DE1058478B DEK35676A DEK0035676A DE1058478B DE 1058478 B DE1058478 B DE 1058478B DE K35676 A DEK35676 A DE K35676A DE K0035676 A DEK0035676 A DE K0035676A DE 1058478 B DE1058478 B DE 1058478B
- Authority
- DE
- Germany
- Prior art keywords
- boron
- aluminum
- sodium hydride
- weight
- parts
- 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
- 229910052796 boron Inorganic materials 0.000 title claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims description 9
- 229910052782 aluminium Inorganic materials 0.000 title claims description 8
- 238000000034 method Methods 0.000 title claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 5
- 150000002483 hydrogen compounds Chemical class 0.000 title claims description 3
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 14
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000012312 sodium hydride Substances 0.000 claims description 10
- 239000012190 activator Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 150000004045 organic chlorine compounds Chemical class 0.000 claims description 2
- 239000000375 suspending agent Substances 0.000 claims description 2
- 150000002366 halogen compounds Chemical class 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- -1 boron halides Chemical class 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- PRJQLUNGZQZONS-UHFFFAOYSA-N chloro(diethyl)borane Chemical compound CCB(Cl)CC PRJQLUNGZQZONS-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 2
- 229910000103 lithium hydride Inorganic materials 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 2
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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 Wasserstoffverbindungen des Bors oder Aluminiums Die Erfindung betrifft ein Verfahren zur Herstellung verschiedener Hydride von Bor und Aluminium, welches durch die Umsetzung der Chloride bzw. Organochloride dieser Elemente mit durch Boralkyle oder Aluminiumalkyle aktiviertem Natriumhydrid gekennzeichnet ist.Process for the production of hydrogen compounds of boron or Aluminum The invention relates to a process for the preparation of various hydrides of boron and aluminum, which is caused by the conversion of the chlorides or organochlorides of these elements with sodium hydride activated by boron alkyls or aluminum alkyls is marked.
Die Umsetzung von Alkalihydriden mit Borhalogeniden und Borsäureestern ist bisher nur bei Anwendung hoher Temperaturen, meist außerdem unter höherem Druck, bekannt. Dabei werden nur geringe Ausbeuten an Alkaliborhydriden erzielt. Allein mit Lithiumhydrid lassen sich auch drucklose Reaktionen bei niederen Temperaturen mit Borhalogeniden durchführen, doch steht einer technischen Verwendung von Lithiumhydrid dessen hoher Preis entgegen. Hinzu kommt, daB zur Ingangsetzung der Reaktion die Verwendung eines sogenannten Promotors, meist in Form des erstrebten Reaktionsproduktes, erforderlich ist. Die Anwendung von Natriumhydrid zur drucklosen Hydrierung bei niederen Temperaturen ist bisher nur als Natriumhydrid-Borsäureester-Komplex gelungen, wobei Bortrifluorid zum Natriumborhydrid umgesetzt wird. Die gleiche Reduktion ist mit Kaliumhydrid durchführbar.The implementation of alkali hydrides with boron halides and boric acid esters has so far only been used when high temperatures are used, usually also under higher pressure, known. Only low yields of alkali borohydrides are achieved. Alone With lithium hydride, pressureless reactions can also be carried out at low temperatures perform with boron halides, but there is an industrial use of lithium hydride contrary to its high price. In addition, to initiate the reaction, the Use of a so-called promoter, usually in the form of the desired reaction product, is required. The use of sodium hydride for pressureless hydrogenation so far only a sodium hydride-boric acid ester complex has been successful at lower temperatures, whereby boron trifluoride is converted to sodium borohydride. The same reduction is feasible with potassium hydride.
Es wurde nun gefunden, daB sich die Reaktion Natriumhydrid mit Bor- oder Aluminiumchloriden zu den entsprechenden Bor- oder Aluminiumhydriden einfach ohne Anwendung von Druck bei Temperaturen unter 200° C herbeiführen läBt, wenn sie in Gegenwart sogenannter Aktivatoren eingeleitet wird. Unter solchen Aktivatoren werden Bor- oder Aluminiumalkyle verstanden, ihre eingesetzte Menge beträgt vorzugsweise zwischen 0,1 und 30°/a, bezogen auf das I%Tatriumhydrid. Die zu reduzierenden Ausgangsverbindungen Bor- oder Aluminiumchloride können sowohl die Trichloride sein als auch Chloride mit ein- oder zweifach substituiertem organischem Rest. Bei Verwendung von Bor- oder Aluminiumchlorid entsteht das komplexe Natriumborhydrid bzw. Natriumaluminiumhydrid.It has now been found that the reaction of sodium hydride with boron or aluminum chlorides to the corresponding boron or aluminum hydrides without the application of pressure at temperatures below 200 ° C, if it is initiated in the presence of so-called activators. Among such activators boron or aluminum alkyls are understood, their amount used is preferably between 0.1 and 30 ° / a, based on the I% sodium hydride. The starting compounds to be reduced Boron or aluminum chlorides can be both the trichlorides and the chlorides with one or two times substituted organic radical. When using boron or aluminum chloride forms the complex sodium borohydride or sodium aluminum hydride.
Der glatte Ablauf der Reaktion läBt sich durch die Tatsache erklären, daB das in allen gebräuchlichen Lösungsmitteln unlösliche Natriumhydrid unmittelbar vor der Reaktion durch den Aktivator in den reaktionsfähigen gelösten Zustand versetzt wird. Je nach der Art des Ausgangsprodukts variiert die Menge des einzusetzenden Aktivators. Die Umsetzung wird meist in Gegenwart eines Lösungs- oder Suspensionsmittels durchgeführt, wobei sich die Verwendung von hochsiedendem Mineralöl besonders bewährt hat. Jedoch auch Kohlenwasserstoffe, wie Octan, eignen sich für diesen Zweck. Beispiel 1 In eine Suspension von 50 Gewichtsteilen feinteiligem Natriumhydrid in 220 Gewichtsteilen eines Mineralöls vom Kp.i=180 bis 190°C wurden unter Rühren zunächst 5 Gewichtsteile Bortriäthyl eingetragen, sodann wurden bei einer Temperatur von 105° C insgesamt 65 Gewichtsteile Bortrichlorid in schnellem Strom eingeleitet.The smooth course of the reaction can be explained by the fact that sodium hydride, which is insoluble in all common solvents, is immediate prior to the reaction by the activator in the reactive dissolved state will. The amount to be used varies depending on the type of starting product Activator. The reaction is usually carried out in the presence of a solvent or suspending agent carried out, whereby the use of high-boiling mineral oil has proven particularly successful Has. However, hydrocarbons such as octane are also suitable for this purpose. example 1 In a suspension of 50 parts by weight of finely divided sodium hydride in 220 parts by weight of a mineral oil with a boiling point of 180 to 190 ° C were initially 5 parts by weight with stirring Boron triethyl entered, then were at a temperature of 105 ° C in total 65 parts by weight of boron trichloride introduced in a fast stream.
Nach Abkühlen und Verdünnung mit Benzol wurde abzentrifugiert, der Rückstand mit Benzol gewaschen und im Vakuum eingedampft. Erhalten wurden 120 Gewichtsteile eines Gemisches von Natriumchlorid und Natriumborhydrid mit einem Gehalt von 16'°/a Na B H4. Das eingeleitete Bortrichlorid wurde quantitativ umgesetzt.After cooling and dilution with benzene, the Washed residue with benzene and evaporated in vacuo. 120 parts by weight were obtained a mixture of sodium chloride and sodium borohydride with a content of 16 ° / a Na B H4. The boron trichloride introduced was converted quantitatively.
Beispiel 2 Eine Suspension von 25 Gewichtsteilen feinteiligem NaH in 250 Gewichtsteilen Octan wurde bei 70 bis 95° C zunächst mit 15 Gewichtsteilen Bortriäthyl versetzt, worauf unter Rühren 104 Gewichtsteile Diäthylchlorid zugesetzt wurden. Sofortiges Einsetzen der Reaktion unter Abscheidung von Na Cl. Die Reaktionstemperatur wurde mit der Diäthylborchlorid-Zugabe reguliert und auf 80 bis 100° C gehalten.Example 2 A suspension of 25 parts by weight of finely divided NaH in 250 parts by weight of octane was initially at 70 to 95 ° C with 15 parts by weight Boron triethyl is added, whereupon 104 parts by weight of diethyl chloride are added with stirring became. Immediate start of the reaction with separation of Na Cl. The reaction temperature was regulated with the addition of diethylboron chloride and kept at 80 to 100.degree.
Nach Abkühlen wurde das ausgeschiedene Na Cl abzentrifugiert, das Diäthylborchlorid wurde beinahe quantitativ in Diäthylborhydrid, gelöst in Octan, übergeführt. Das entstandene Na Cl reagierte .icht mit Wasser, ein Beweis - dafür, daß das eingeetzte NaH zu 1001% umgesetzt wurde. Ausbeute ;08 Gewichtsteile einer Lösung von Diäthylboriydrid in Octan.After cooling, the precipitated Na Cl was centrifuged off, the Diethyl boron chloride was almost quantitatively dissolved in diethyl borohydride in octane, convicted. The resulting Na Cl reacted .not with water, a Proof - that 1001% of the NaH used was converted. Yield; 08 parts by weight a solution of diethyl borohydride in octane.
Beispiel 3 Zu einer gut gerührten Suspension von 100 Gevichtsteilen feinteiligem NaH in 700 Gewichtsteilen )ctan wurden bei 120 bis 130° C zunächst 12 Gevichtsteile Aluminiumtriäthyl zugetropft, sodann die Cemperatur des Reaktionsgerilisches auf 80 bis 75° C esenkt. 480 Gewichtsteile Diäthylaluminiumchlorid vurden daraufhin kontinuierlich zugesetzt, wobei die teaktion, die sofort ansprang, mit der Zugabegechwindigkeit des Diäthylaluminiumchlorids reguiert wurde.Example 3 For a well-stirred suspension of 100 parts by weight finely divided NaH in 700 parts by weight) ctan were initially at 120 to 130 ° C 12 parts by weight of aluminum triethyl was added dropwise, then the temperature of the reaction mixture lowered to 80 to 75 ° C. 480 parts by weight of diethyl aluminum chloride were then added continuously added, the action, which started immediately, with the rate of addition of diethyl aluminum chloride was regulated.
Nach Abzentrifugieren vom entstandenen Kochalz wurde eine Lösung von Diäthylaluminiumhydrid n Octan erhalten (992 Gewichtsteile). Die Um-,etzung, bezogen auf eingesetztes NaH und Diäthyl-Juminiumchlorid, war quantitativ. Das als Lösungsnittel benutzte Octan konnte vom Diäthylaluminiumiydrid durch Vakuumdestillation entfernt werden.After centrifuging off the resulting common salt, a solution of Obtained diethyl aluminum hydride n octane (992 parts by weight). The implementation, related on NaH and diethyl aluminum chloride used, was quantitative. That as a solvent the octane used could be removed from the diethylaluminum hydride by vacuum distillation will.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEK35676A DE1058478B (en) | 1956-12-15 | 1956-12-15 | Process for the production of hydrogen compounds of boron or aluminum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEK35676A DE1058478B (en) | 1956-12-15 | 1956-12-15 | Process for the production of hydrogen compounds of boron or aluminum |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1058478B true DE1058478B (en) | 1959-06-04 |
Family
ID=7220431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEK35676A Pending DE1058478B (en) | 1956-12-15 | 1956-12-15 | Process for the production of hydrogen compounds of boron or aluminum |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1058478B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1085857B (en) | 1957-12-24 | 1960-07-28 | Kali Chemie Ag | Process for the reduction of organic or inorganic halides |
| DE1136314B (en) | 1958-10-29 | 1962-09-13 | Bayer Ag | Process for the preparation of sodium borate by reacting sodium hydride with boron halides in the presence of catalysts |
| US3222121A (en) * | 1959-10-30 | 1965-12-07 | Kali Chemie Ag | Preparation of sodium borohydrides |
| US6524542B2 (en) | 2001-04-12 | 2003-02-25 | Millennium Cell, Inc. | Processes for synthesizing borohydride compounds |
| US6670444B2 (en) | 2000-11-08 | 2003-12-30 | Millennium Cell, Inc. | Processes for synthesizing borohydride compounds |
| US7019105B2 (en) | 2000-11-08 | 2006-03-28 | Millennium Cell, Inc. | Compositions and processes for synthesizing borohydride compounds |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1120200A (en) * | 1955-01-19 | 1956-07-02 | Callery Chemical Co | Improvements relating to alkali metal borohydrides |
-
1956
- 1956-12-15 DE DEK35676A patent/DE1058478B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1120200A (en) * | 1955-01-19 | 1956-07-02 | Callery Chemical Co | Improvements relating to alkali metal borohydrides |
Non-Patent Citations (1)
| Title |
|---|
| DE D19629 (Bekanntgemacht am 05.07.1956) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1085857B (en) | 1957-12-24 | 1960-07-28 | Kali Chemie Ag | Process for the reduction of organic or inorganic halides |
| DE1136314B (en) | 1958-10-29 | 1962-09-13 | Bayer Ag | Process for the preparation of sodium borate by reacting sodium hydride with boron halides in the presence of catalysts |
| US3222121A (en) * | 1959-10-30 | 1965-12-07 | Kali Chemie Ag | Preparation of sodium borohydrides |
| US6670444B2 (en) | 2000-11-08 | 2003-12-30 | Millennium Cell, Inc. | Processes for synthesizing borohydride compounds |
| US7019105B2 (en) | 2000-11-08 | 2006-03-28 | Millennium Cell, Inc. | Compositions and processes for synthesizing borohydride compounds |
| US6524542B2 (en) | 2001-04-12 | 2003-02-25 | Millennium Cell, Inc. | Processes for synthesizing borohydride compounds |
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