AU4147897A - Preparation of tetraalkyl ammonium borohydrides - Google Patents
Preparation of tetraalkyl ammonium borohydrides Download PDFInfo
- Publication number
- AU4147897A AU4147897A AU41478/97A AU4147897A AU4147897A AU 4147897 A AU4147897 A AU 4147897A AU 41478/97 A AU41478/97 A AU 41478/97A AU 4147897 A AU4147897 A AU 4147897A AU 4147897 A AU4147897 A AU 4147897A
- Authority
- AU
- Australia
- Prior art keywords
- borohydride
- alkali metal
- ammonium hydroxide
- tetraethyl ammonium
- aqueous solution
- 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.)
- Abandoned
Links
- 125000005207 tetraalkylammonium group Chemical group 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 26
- 150000001340 alkali metals Chemical class 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 14
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 14
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 230000002452 interceptive effect Effects 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- -1 alkali metal alkoxide Chemical class 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- NQZKZGHOYUYCHU-UHFFFAOYSA-N boron;tetraethylazanium Chemical compound [B].CC[N+](CC)(CC)CC NQZKZGHOYUYCHU-UHFFFAOYSA-N 0.000 claims 7
- 238000004519 manufacturing process Methods 0.000 claims 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 2
- 239000000908 ammonium hydroxide Substances 0.000 claims 2
- 238000004090 dissolution Methods 0.000 claims 2
- 239000000047 product Substances 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring 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
WO 99/07712 PCT/US97/14084 -1 PREPARATION OF TETRAALKYL AMMONIUM BOROHYDRIDES FIELD OF THE INVENTION This invention is a method for the preparation of 5 tetraalkyl ammonium borohydrides. BACKGROUND OF THE INVENTION It is known to produce tetraalkyl ammonium borohydrides by exchange of the cation of an alkali metal borohydride with a tetraalkyl ammonium cation 0 exchange resin. See, Guillevic, et al., Bulletin de la Societe Chimique de France (1976), No. 7-8:1099-1100. See also, Mongeot, et al., Bulletin de la Societe Chimique de France (1986), No. 3:385-389. DETAILED DESCRIPTION OF THE INVENTION 5 Pursuant to the invention, a particulate solid alkali metal borohydride is added with agitation to a solution of tetraalkyl ammonium hydroxide in a non interfering solvent to produce the desired tetraalkyl ammonium borohydride. The reaction is illustrated by 0 the equation
OHN(R)
4 + MBH 4 > N(R)4+BN 4 + MOH (solution) (solid) (stir) 5 in which R is any straight or branched chain alkyl group, preferably an ethyl group, having one to ten carbon atoms, and M is any alkali metal, preferably sodium. The tetraalkyl ammonium hydroxide may be in 30 solution in any non-interfering solvent, such as water, or an alkanol, such as methanol or ethanol. Water is the preferred solvent. Any desired concentration, for example, any 40% to 60% by weight solution of tetraalkyl ammonium hydroxide WO 99/07712 PCT/US97/14084 -2 in a non-interfering solvent is useful in the practice of the invention. A commercially available 40% aqueous solution of tetraalkyl ammonium hydroxide may be utilized. The tetraalkyl ammonium hydroxide and alkali & metal borohydride may be reacted in any desired relative proportions. Stoichiometric amounts are preferred. The reaction may be conducted at any desired temperature. A preferred temperature range is 20°C. to ) 30'C. A specific embodiment of the invention entails addition of a particulate solid alkali metal borohydride to a 20% to 60% by weight aqueous tetraalkyl ammonium hydroxide solution. The addition 5 is accomplished with agitation to facilitate solution of said alkali metal borohydride in said aqueous tetraethyl ammonium hydroxide. An exothermic reaction occurs readily at room temperature. When the reaction is substantially complete, aqueous alkali metal ) hydroxide or aqueous alkali metal alkoxide is added in an amount sufficient to cause separation of the reaction mixture into a lower aqueous alkali metal hydroxide or alkoxide containing layer and an upper aqueous layer containing the desired tetraalkyl 5 borohydride as a hydrate, e.g., N(R)4+BH- 4 .5H 2 0. The upper layer is separated and dried by vacuum or heat to provide solid ammonium tetraalkyl borohydride hydrate. Drying by heat is undertaken with care to avoid the decomposition of the product which may occur at a 0 temperature of 260*C. The dried product is purified by recrystallization from an appropriate solvent, preferably an alkanol such as methanol, ethanol or 2-propanol.
WO 99/07712 PCT/US97/14084 -3 EXAMPLE 1 1838 grams of 40% aqueous tetraalkyl ammonium hydroxide was charged to a reaction vessel. 193.5 grams of particulate solid sodium borohydride was added, and the reaction mixture stirred at 25 0 C for 30 minutes until the reaction was substantially complete. The aqueous sodium hydroxide was separated. The upper product was an aqueous solution of tetraalkyl ammonium borohydride hydrate N(C 2
H
5 )4- BH4--5H 2 0. )The upper layer was separated and dried by vacuum distillation. The resulting dry N(C 2
H
5 )4-.BH 4- product was recrystallized from 2-propanol. Yield 645 grams, 89% yield. It will be apparent to the skilled individual that 5 alkali metal borohydride in solution in a non interfering solvent may be combined with the tetraalkyl ammonium hydroxide solution. The use of a solid alkali metal borohydride is cost effective and is preferred for other practical reasons. For example, a 20% to 40% 0 by weight aqueous alkali metal borohydride solution may be used in lieu of particulate solid alkali metal borohydride.
Claims (10)
1. A method for producing a tetraalkyl ammonium borohydride which comprises reacting a tetraalkyl ammonium hydroxide with an alkali metal borohydride, 5 wherein a tetraalkyl ammonium borohydride reaction product is produced.
2. A method for producing a tetraalkyl ammonium borohydride which comprises combining a solution of tetraalkyl ammonium hydroxide in a non-interfering 3 solvent for reaction with a solid alkali metal borohydride, wherein a reaction mixture is formed which contains said tetraalkyl ammonium borohydride in solution in said non-interfering solvent.
3. The claim 2 method in which said tetraalkyl 5 ammonium hydroxide is tetraethyl ammonium hydroxide and in which said solid alkali metal borohydride is sodium borohydride and wherein said reaction mixture that is formed contains an aqueous solution of tetraethyl ammonium borohydride hydrate. 0
4. A method for producing tetraethyl ammonium borohydride which comprises: (i) providing an aqueous solution of tetraethyl ammonium hydroxide; (ii) adding a solid alkali metal borohydride to 5 said aqueous solution of tetraethyl ammonium hydroxide, wherein said addition is accomplished with agitation to facilitate dissolution of said alkali metal borohydride in said aqueous solution of tetraethyl ammonium hydroxide, 0 and wherein said tetraethyl ammonium hydroxide of step (i) and said alkali metal borohydride of step (ii) react to form a WO 99/07712 PCT/US97/14084 -5 reaction mixture containing said tetraethyl ammonium borohydride; and (iii) separating said tetraethyl ammonium hydroxide from said reaction mixture.
5 5. The claim 4 method further comprising a step (iv) recrystallizing said tetraethyl ammonium borohydride separated in step (iii) from an alkanol solution thereof.
6. The claim 4 or claim 5 method wherein said 0 solid alkali metal borohydride added in step (ii) is sodium borohydride.
7. The claim 4 or claim 5 method in which said aqueous solution of tetraethyl ammonium hydroxide provided in step (i) is a 40% to 60% by weight aqueous 5 solution. WO 99/07712 - 6 - PCT/US97/14084 AMENDED CLAIMS [received by the International Bureau on 15 April 1998 (15.04.98); original claim 4 amended; original claims 1-3 cancelled; new claims 8-10 added; remaning claims unchanged ( 3 pages)] 1. [CANCELLED] 5 2. [CANCELLED] 10 3. [CANCELLED] 15 20 4. A method for producing tetraethyl ammonium borohydride which comprises: (i) providing an aqueous solution of tetraethyl ammonium hydroxide; (ii) adding a particulate solid alkali metal 25 borohydride to said aqueous solution of tetraethyl ammonium hydroxide, wherein said addition is accomplished with agitation to facilitate dissolution of said alkali metal borohydride in said aqueous 30 solution of tetraethyl ammonium hydroxide, and wherein said tetraethyl ammonium hydroxide of step (i) and said alkali metal borohydride of step (ii) react to form a WO 99/07712 PCT/US97/14084 - 7 reaction mixture containing said tetraethyl ammonium borohydride; and (iii) separating said tetraethyl ammonium 5 hydroxide from said reaction mixture. 5. The claim 4 method further comprising a step (iv) recrystallizing said tetraethyl ammonium borohydride separated in step (iii) from an alkanol solution thereof. 10 6. The claim 4 or claim 5 method wherein said solid alkali metal borohydride added in step (ii) is sodium borohydride. 7. The claim 4 or claim 5 method in which said aqueous solution of tetraethyl ammonium hydroxide 15 provided in step (i) is a 40% to 60% by weight aqueous solution.
8. A method which comprises: (i) providing a 20 to 60% by weight aqueous solution of a tetraalkyl ammonium hydroxide; 20 (ii) adding a particulate solid alkali metal borohydride wherein said addition is accomplished with agitation, wherein said alkali metal borohydride 25 described in said step (i) aqueous solution reacts with said tetraalkyl ammonium hydroxide, and wherein a reaction mixture which is an aqueous solution of a tetraalkyl ammonium borohydride and an alkali metal hydroxide is 30 formed; AMENDED SHEET (ARTICLE 19) WO 99/07712 PCT/US97/14084 - 8 (iii) upon substantial completion of said reaction, adding aqueous ammonium hydroxide and aqueous metal alkoxide to said step (ii) reaction mixture, 5 wherein said step (ii) reaction mixture separates into a lower aqueous alkali metal hydroxide or alkali metal alkoxide containing layer and an upper layer containing an ammonium tetraalkyl borohydride hydrate; 10 (iv) separating said step (iii) upper and lower layers; and (v) drying and separating said upper layer, wherein a solid ammonium tetraalkyl borohydride product is obtained. 15
9. The claim 8 method further comprising: (vi) recrystallizing said step (v) product from an alkanol.
10. The claim 8 or claim 9 method wherein, said step (i) aqueous solution of a tetraalkyl ammonium 20 hydroxide is a 40% to 60% by weight aqueous solution of tetraethyl ammonium hydroxide, said step (ii) particulate solid alkali metal borohydride is sodium borohydride, said step (iii) is conducted at a temperature of 200 to 25 30 0 C, and said drying step (v) is accomplished by vacuum distillation. AMENDED SHEET (ARTICLE 19)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1997/014084 WO1999007712A1 (en) | 1997-08-12 | 1997-08-12 | Preparation of tetraalkyl ammonium borohydrides |
Publications (1)
Publication Number | Publication Date |
---|---|
AU4147897A true AU4147897A (en) | 1999-03-01 |
Family
ID=22261427
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU41478/97A Abandoned AU4147897A (en) | 1997-08-12 | 1997-08-12 | Preparation of tetraalkyl ammonium borohydrides |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0937086A1 (en) |
JP (1) | JP2001518120A (en) |
AU (1) | AU4147897A (en) |
CA (1) | CA2267979A1 (en) |
WO (1) | WO1999007712A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009040677A (en) * | 2007-07-26 | 2009-02-26 | Rohm & Haas Co | Preparation of hydrogen source for fuel cell |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2756259A (en) * | 1954-05-17 | 1956-07-24 | Metal Hydrides Inc | Method for preparing quaternary ammonium borohydrides |
US4216168A (en) * | 1978-10-16 | 1980-08-05 | Allied Chemical Corporation | Preparation of high purity tetrahydrocarbylammonium tetrahydridoborates |
-
1997
- 1997-08-12 JP JP51207199A patent/JP2001518120A/en active Pending
- 1997-08-12 WO PCT/US1997/014084 patent/WO1999007712A1/en not_active Application Discontinuation
- 1997-08-12 CA CA002267979A patent/CA2267979A1/en not_active Abandoned
- 1997-08-12 AU AU41478/97A patent/AU4147897A/en not_active Abandoned
- 1997-08-12 EP EP97939377A patent/EP0937086A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
CA2267979A1 (en) | 1999-02-18 |
JP2001518120A (en) | 2001-10-09 |
WO1999007712A1 (en) | 1999-02-18 |
EP0937086A1 (en) | 1999-08-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5336765A (en) | Process of preparing N-substituted aldobionamides | |
CA2459087A1 (en) | Synthesis of ester linked long chain alkyl moieties | |
US4709083A (en) | Method of making boron analogues | |
TW503233B (en) | Process for the preparation of hydroxy methylthiobutyric acid esters | |
IE52602B1 (en) | Process for the synthesis of isosorbide mononitrates | |
AU4147897A (en) | Preparation of tetraalkyl ammonium borohydrides | |
US20050203287A1 (en) | Process for the preparation of sulfamate derivatives | |
US4517122A (en) | Cyclic peptides | |
US4390732A (en) | Process for the production of guaiacol glycerine ether | |
US5808070A (en) | Process for preparing alkaline aminoborohydrides and alkaline aminoborohydride complexes | |
US4297509A (en) | Process for preparing alkali metal salts 3-amino-2, 5-dichlorobenzoic acid | |
EP0052819B1 (en) | Process for preparing amidinecarboxylic acids | |
US4301129A (en) | Synthesis of NaBH3 CN and related compounds | |
US4380631A (en) | Preparation of caffeine | |
US4632988A (en) | Process for preparing N-polythiodimorpholines | |
EP0288495B1 (en) | Synthesis of n-epoxypropyl lactams | |
ES8403124A1 (en) | Process for the preparation of vincaminic acid esters | |
GB2160204A (en) | Preparation of N-methyl-1-alkylthio-2-nitroethenamines | |
JPS6372661A (en) | Production of alkylhydrazines | |
Easton et al. | α-Benzoyloxy-and α-Methoxy-Substituted Glycine Derivatives as Atypical Substrates for Free-Radical Reactions With Stannanes | |
US6121490A (en) | Production of solid tertiary amine oxides | |
JPS5711938A (en) | Preparation of 1,1-dialkoxy-3-alkynes | |
US5227509A (en) | Process for manufacture of organic esters of strong acids | |
JPS565499A (en) | Preparation of thymine derivative | |
US5290532A (en) | Preparation of hydridomagnesium chloride |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MK1 | Application lapsed section 142(2)(a) - no request for examination in relevant period |