WO1997006097A1 - Procede d'elaboration d'hydrure de lithium et d'aluminium dans des solvants etheres - Google Patents

Procede d'elaboration d'hydrure de lithium et d'aluminium dans des solvants etheres Download PDF

Info

Publication number
WO1997006097A1
WO1997006097A1 PCT/US1996/012889 US9612889W WO9706097A1 WO 1997006097 A1 WO1997006097 A1 WO 1997006097A1 US 9612889 W US9612889 W US 9612889W WO 9706097 A1 WO9706097 A1 WO 9706097A1
Authority
WO
WIPO (PCT)
Prior art keywords
aluminum hydride
lithium
tetrahydrofuran
reaction
lithium chloride
Prior art date
Application number
PCT/US1996/012889
Other languages
English (en)
Inventor
Terry L. Rathman
James A. Schwindeman
Eric J. Granger
Sharon B. Smith
Original Assignee
Fmc Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fmc Corporation filed Critical Fmc Corporation
Priority to EP96928089A priority Critical patent/EP0843645A1/fr
Priority to AU67683/96A priority patent/AU6768396A/en
Publication of WO1997006097A1 publication Critical patent/WO1997006097A1/fr

Links

Classifications

    • 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
    • C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
    • C01B6/243—Hydrides containing at least two metals; Addition complexes thereof containing only hydrogen, aluminium and alkali metals, e.g. Li(AlH4)

Definitions

  • This invention concerns a process for the preparation of lithium aluminum hydride in ethereal solvents by metathesis of sodium aluminum hydride with lithium chloride.
  • Lithium aluminum hydride (LiAIH 4 ) is a powerful reducing agent, soluble in organic solvents. This reagent has found wide utility in organic synthesis, due to its reducing power. A wide variety of functional groups are reduced with this reagent, including aldehydes, ketones, esters, amides, epoxides, and nitrites.
  • a common synthetic method for the commercial preparation of lithium aluminum hydride involves the metathesis of sodium aluminum hydride (NaAIH 4 ) with lithium chloride to form lithium aluminum hydride and sodium chloride (equation 1).
  • the first method involves preparing a solution of sodium aluminum hydride in the desired solvent system first, before carrying out the metathesis reaction. This procedure involves a separate reactor and reaction step, slow filtration, and analysis prior to using the sodium aluminum hydride solution in the metathesis reaction. The metathesis reaction is then typically run with an appreciable amount of toluene as a co ⁇ solvent and a few mole percent of lithium aluminum hydride to catalyze the reaction.
  • the second method typically involves a one step process in which sodium aluminum hydride and lithium chloride are reacted together in one reactor along with toluene as a co-solvent and a few mole percent of lithium aluminum hydride to catalyze the reaction.
  • the reaction mixture is filtered to remove the sodium chloride by-product.
  • lithium aluminum hydride can be prepared via metathesis in one step in an ethereal solvent such as tetrahydrofuran without any co-solvent, catalyst, or prior preparation of sodium aluminum hydride in solution.
  • Solid sodium aluminum hydride is added to lithium chloride which is generally present in a slight excess, for example, 1.1 equivalents, based on the sodium aluminum hydride, in an ethereal solvent at room temperature.
  • the reaction is heated to a temperature between 25 °C to the reflux temperature of the solvent until the reaction is complete, about six hours at the reflux temperature of tetrahydrofuran, cooled, and filtered to remove excess lithium chloride and sodium chloride by-product.
  • Solvents useful in the practice of this invention include but are not limited to the ethereal solvents selected from the group consisting of tetrahydrofuran, t-butyl methyl ether, 2-methyl-tetrahydrofuran, 1 ,2- dimethoxyethane, diethoxymethane, and mixtures thereof.
  • the amount of lithium chloride can be varied from 0.9 equivalents to up to 5.0 equivalents, based on the sodium aluminum hydride charged.
  • the process is conducted in an inert atmosphere, preferably under a noble gas atmosphere, most preferably under argon.
  • the temperature can vary between 25 °C and the reflux temperature of the solvent.
  • the amount of time required to complete the reaction varies with the temperature and with the solvent selected. When using tetrahydrofuran at its reflux temperature about 6 hours is generally sufficient to complete the reaction.
  • the following examples further illustrate the invention. Unless noted otherwise, all temperatures are in degrees Centigrade, all reactions were conducted in an inert argon atmosphere and weights are in grams.
  • a 2 liter, 3-neck round bottom flask was equipped with a mechanical stirrer and a Claisen adapter with a teflon coated temperature probe and a dry ice condenser. This apparatus was dried in an oven at 125 °C overnight, assembled hot, and allowed to cool to room temperature in a stream of argon. Lithium chloride (46.8g, 1.1 mole, 1.1 equivalent) was weighed out into the flask in a glove box. Tetrahydrofuran (750 ml) was added. The slurry was stirred at room temperature (20-25 °C) for 145 min.
  • Sodium aluminum hydride (62.4g, 1.0 mole, 1.0 equivalent, Albemarle, 86.5%) was weighed out into a separate flask in a glove box, then added to the reaction flask via a transfer tube over 10 min. The flask was rinsed with tetrahydrofuran (250 ml). The reaction mixture was heated to reflux (67-68 °C) for 6 hours, then cooled to room temperature with stirring overnight. The reaction was transferred to a 1 liter sintered glass pressure filter (medium frit). The product solution was filtered with 3- 4 psi argon pressure. In two hours, 737.3 grams (840 ml) of filtrate was collected. The filtrate was a clear, colorless solution and contained no visible solids.
  • the slurry was stirred at room temperature (20-25 °C) for 45 min.
  • Sodium aluminum hydride (120.5g, 2.0 mole, 1 equivalent, Aldrich, 90%) was weighed out into a separate flask in a glove box, then added to the reaction flask via a transfer tube.
  • the flask was rinsed with tetrahydrofuran (250 ml).
  • the reaction mixture was heated to reflux (67-68 °C) for 6 hours, then cooled to room temperature with stirring overnight. Then reaction was transferred to a 1 liter sintered glass pressure filter (coarse frit).
  • the product solution was filtered with 3-4 psi argon pressure.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)

Abstract

Procédé d'élaboration d'hydrure de lithium et d'aluminium dans un solvant éthéré par métathèse d'hydrure d'aluminium et de sodium et de chlorure de lithium selon une réaction à une seule étape consistant à porter ensemble l'hydrure d'aluminium et de sodium et le chlorure de lithium à une température comprise entre 25 °C et la température de reflux du solvant jusqu'à achèvement de la réaction.
PCT/US1996/012889 1995-08-09 1996-08-08 Procede d'elaboration d'hydrure de lithium et d'aluminium dans des solvants etheres WO1997006097A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP96928089A EP0843645A1 (fr) 1995-08-09 1996-08-08 Procede d'elaboration d'hydrure de lithium et d'aluminium dans des solvants etheres
AU67683/96A AU6768396A (en) 1995-08-09 1996-08-08 Process for the preparation of lithium aliminum hydride in ethereal solvents

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US205895P 1995-08-09 1995-08-09
US60/002,058 1995-08-09
US3569696P 1996-02-12 1996-02-12
US08/600,356 1996-02-12

Publications (1)

Publication Number Publication Date
WO1997006097A1 true WO1997006097A1 (fr) 1997-02-20

Family

ID=26669863

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/012889 WO1997006097A1 (fr) 1995-08-09 1996-08-08 Procede d'elaboration d'hydrure de lithium et d'aluminium dans des solvants etheres

Country Status (1)

Country Link
WO (1) WO1997006097A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998013319A1 (fr) * 1996-09-24 1998-04-02 Fmc Corporation Nouvelles compositions de reduction et leurs procedes de fabrication
US6444190B2 (en) 1995-08-03 2002-09-03 Fmc Corporation Reduction compositions and processes for making the same
DE10237441A1 (de) * 2002-08-16 2004-02-26 Chemetall Gmbh Verfahren zur Herstellung von Lithiumaluminiumhydridlösungen
WO2007026018A1 (fr) * 2005-09-01 2007-03-08 Chemetall Gmbh Solutions d'hydrure d'aluminium et de lithium

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB820513A (en) * 1956-12-21 1959-09-23 Ici Ltd Improvements in and relating to the production of lithium aluminium hydride
GB905985A (en) * 1959-02-24 1962-09-19 Ethyl Corp Preparing metal-alumino hydrides
US3180700A (en) * 1961-09-26 1965-04-27 Ethyl Corp Process for preparing lithium aluminum hydride
US3387947A (en) * 1961-11-29 1968-06-11 Ethyl Corp Process for preparing lithium aluminum hydride

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB820513A (en) * 1956-12-21 1959-09-23 Ici Ltd Improvements in and relating to the production of lithium aluminium hydride
GB905985A (en) * 1959-02-24 1962-09-19 Ethyl Corp Preparing metal-alumino hydrides
US3180700A (en) * 1961-09-26 1965-04-27 Ethyl Corp Process for preparing lithium aluminum hydride
US3387947A (en) * 1961-11-29 1968-06-11 Ethyl Corp Process for preparing lithium aluminum hydride

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6444190B2 (en) 1995-08-03 2002-09-03 Fmc Corporation Reduction compositions and processes for making the same
WO1998013319A1 (fr) * 1996-09-24 1998-04-02 Fmc Corporation Nouvelles compositions de reduction et leurs procedes de fabrication
DE10237441A1 (de) * 2002-08-16 2004-02-26 Chemetall Gmbh Verfahren zur Herstellung von Lithiumaluminiumhydridlösungen
WO2007026018A1 (fr) * 2005-09-01 2007-03-08 Chemetall Gmbh Solutions d'hydrure d'aluminium et de lithium
US8840805B2 (en) 2005-09-01 2014-09-23 Chemetall Gmbh Solutions of lithium aluminum hydride

Similar Documents

Publication Publication Date Title
CA1135480A (fr) Procede d'obtention d'hydrures de magnesium
US5730952A (en) Process for the preparation of lithium aluminum hydride in etheral solvents
Semmelhack et al. Preparation of acylpentacarbonylchromate salts and alkoxycarbene pentacarbonyl complexes of chromium employing the pentacarbonylchromate dianion ([Cr (CO) 5] 2-)
CN112979400A (zh) 一种在碱金属氢化物作用下制备2-碘代芳醚的方法
JPH0233643B2 (fr)
Weckhuysen et al. Spectroscopy of the formation of microporous transition metal ion containing aluminophosphates under hydrothermal conditions
WO1997006097A1 (fr) Procede d'elaboration d'hydrure de lithium et d'aluminium dans des solvants etheres
Deacon et al. Organolanthanoids. III. Preparations and properties of some Di (alkynyl) lanthanoids
US5886229A (en) Method of synthesis of alkali metal trisubstituted borohydride reagents
Brown et al. Addition compounds of alkali-metal hydrides. 23. Preparation of potassium triisopropoxyborohydride in improved purity
JP2001500834A (ja) ＬｉＰＦ▲下６▼製造方法
US4778908A (en) Process for preparing disilylmethanes
CA2108512C (fr) Procede d'obtention du ph3c[b(c6f5)4]
US20090112027A1 (en) Activated Alkaline Earth Metal, In Particular Magnesium, For The Preparation Of Organoalkaline Earth Metal Compounds
JPS58217426A (ja) ホウ水素化ナトリウムと置換アルミニウム水素化物との同時製造法
US5808070A (en) Process for preparing alkaline aminoborohydrides and alkaline aminoborohydride complexes
CA1140561A (fr) Procede de synthese de derives alcoxyles d'hydrures mixtes d'aluminium et de metaux alcalino-terreux
JP3570835B2 (ja) アルキルリチウムの製造方法
EP1273554B1 (fr) Procédé de production d'hydrure de lithium-aluminium à partir d'hydrure de sodium-aluminium
Ossola et al. Synthesis and characterization of tricyclopentadienyluranium tetrahydroaluminate
JPH0240603B2 (ja) Suisokaarukarikinzokusakukagobutsunoseizoho
US4278611A (en) Process for synthesizing alkoxyalanates of alkaline earth metals
JP2001106693A (ja) 有機置換アルカリ金属・アルミニウム水素化物の製造方法
WO2022188012A1 (fr) Utilisation d'un composé de terre rare silylamino dans la catalyse de la réaction d'un composé d'isatine et d'un composé de cyclopropénone
US5290532A (en) Preparation of hydridomagnesium chloride

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IL IS JP KE KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1996928089

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1996928089

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWW Wipo information: withdrawn in national office

Ref document number: 1996928089

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: CA