Synthesis of permethyldodecaborate and paramagnetic dodecaborate salt

Hawthorne, M Frederick; Peymann, Toralf

Title: Synthesis of permethyldodecaborate and paramagnetic dodecaborate salt

Abstract

The dodecamethyl closo-borane dianion [closo-B.sub.12 (CH.sub.3).sub.12 ].sup.2- and anion [closo-B.sub.12 (CH.sub.3).sub.12 ].sup.- were synthesized and characterized. Dodecamethyl-closo dodecaborate (2-) was produced from [closo-B.sub.12 H.sub.12 ].sup.2-, using trimethylaluminum, and methyl iodide and modified Friedel-Crafts reaction conditions. The anion was produced from the dianion by chemical oxidation using ceric (4) ammonium nitrate in acetonitrile. The anion and dianion were both characterized by .sup.1 H and .sup.11 B NMR spectroscopy, high-resolution fast atom bombardment (FAB) mass spectrometry, cyclic voltammetry, and single-crystal X-ray diffraction. The "camouflaged" polyhedral borane anion [closo-B.sub.12 (CH.sub.3).sub.12 ].sup.2-, can be used as a precursor to materials that offer a broad spectrum of novel applications ranging from drug applications and supramolecular chemistry to use as a weakly-coordinating dianion.

Inventors:

Hawthorne, M Frederick ^[1]; Peymann, Toralf ^[2]

Encino, CA
Los Angeles, CA

Issue Date:: 2002-01-01

Research Org.:: Univ. of California (United States)

OSTI Identifier:: 874276

Patent Number(s):: 6355840

Assignee:: The Regents of the University of California (Oakland, CA)

Patent Classifications (CPCs):: C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07F - ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM

Show more

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07F - ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
C07F5/05 - Cyclic compounds having at least one ring containing boron but no carbon in the ring

Show less

DOE Contract Number:: FG03-95ER61975

Resource Type:: Patent

Country of Publication:: United States

Language:: English

Subject:: synthesis; permethyldodecaborate; paramagnetic; dodecaborate; salt; dodecamethyl; closo-borane; dianion; closo-bsub12; chsub3sub12; sup2-; anion; sup-; synthesized; characterized; dodecamethyl-closo; 2-; produced; hsub12; trimethylaluminum; methyl; iodide; modified; friedel-crafts; reaction; conditions; chemical; oxidation; ceric; ammonium; nitrate; acetonitrile; sup1; sup11; nmr; spectroscopy; high-resolution; fast; atom; bombardment; fab; mass; spectrometry; cyclic; voltammetry; single-crystal; x-ray; diffraction; camouflaged; polyhedral; borane; precursor; materials; offer; broad; spectrum; novel; applications; ranging; drug; supramolecular; chemistry; weakly-coordinating; ammonium nitrate; /999/

Citation Formats


                    Hawthorne, M Frederick, and Peymann, Toralf. Synthesis of permethyldodecaborate and paramagnetic dodecaborate salt.  United States: N. p., 2002. 
        Web.

Copy to clipboard


                    Hawthorne, M Frederick, & Peymann, Toralf. Synthesis of permethyldodecaborate and paramagnetic dodecaborate salt.  United States.

Copy to clipboard


                    Hawthorne, M Frederick, and Peymann, Toralf. Tue .  
        "Synthesis of permethyldodecaborate and paramagnetic dodecaborate salt".  United States.  https://www.osti.gov/servlets/purl/874276.

Copy to clipboard


                    
@article{osti_874276,

  title        = {Synthesis of permethyldodecaborate and paramagnetic dodecaborate salt},

  author       = {Hawthorne, M Frederick and Peymann, Toralf},

  abstractNote = {The dodecamethyl closo-borane dianion [closo-B.sub.12 (CH.sub.3).sub.12 ].sup.2- and anion [closo-B.sub.12 (CH.sub.3).sub.12 ].sup.- were synthesized and characterized. Dodecamethyl-closo dodecaborate (2-) was produced from [closo-B.sub.12 H.sub.12 ].sup.2-, using trimethylaluminum, and methyl iodide and modified Friedel-Crafts reaction conditions. The anion was produced from the dianion by chemical oxidation using ceric (4) ammonium nitrate in acetonitrile. The anion and dianion were both characterized by .sup.1 H and .sup.11 B NMR spectroscopy, high-resolution fast atom bombardment (FAB) mass spectrometry, cyclic voltammetry, and single-crystal X-ray diffraction. The "camouflaged" polyhedral borane anion [closo-B.sub.12 (CH.sub.3).sub.12 ].sup.2-, can be used as a precursor to materials that offer a broad spectrum of novel applications ranging from drug applications and supramolecular chemistry to use as a weakly-coordinating dianion.},

  doi          = {},

  journal      = {},
number       = ,

  volume       = ,

  place        = {United States},

  year         = {2002},

  month        = {1}

}

Copy to clipboard

Patent:

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

An unpaired electron incarcerated within an icosahedral borane cage: synthesis and crystal structure of the blue, air-stable {[closo-B12(CH3)12]·}− radical
journal, January 1999

Peymann, Toralf; Knobler, Carolyn B.; Frederick Hawthorne, M.
Chemical Communications, Issue 20
https://doi.org/10.1039/a905406e

Decakis(dichloromethyl)-1,12-dicarba-closo-dodecaborane(12): Camouflage of an Icosahedral Carborane by Using Bulky Functional Substituents
journal, November 1996

Jiang, Wei; Knobler, Carolyn B.; Hawthorne, M. Frederick
Angewandte Chemie International Edition in English, Vol. 35, Issue 21
https://doi.org/10.1002/anie.199625361

An Icosahedral Array of Methyl Groups Supported by an Aromatic Borane Scaffold: The [ c loso -B ₁₂ (CH ₃ ) ₁₂ ] ² ^- Ion
journal, June 1999

Peymann, Toralf; Knobler, Carolyn B.; Hawthorne, M. Frederick
Journal of the American Chemical Society, Vol. 121, Issue 23
https://doi.org/10.1021/ja990884q

Similar Records in DOE Patents and OSTI.GOV collections:

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

Patent Tierney, John W [Pittsburgh, PA]; Wender, Irving [Pittsburgh, PA]; Palekar, Vishwesh M [Pittsburgh, PA]

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amountmore » « less
Full Text Available
Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

Patent Tierney, John W [Pittsburgh, PA]; Wender, Irving [Pittsburgh, PA]; Palekar, Vishwesh M [Pittsburgh, PA]

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amountmore » « less
Full Text Available
Synthesis of perhydroxydodecaborate salts and related species

Patent Hawthorne, M Frederick [Encino, CA]; Peymann, Toralf [Los Angeles, CA]; Herzog, Axel Hans-Joachim [Los Angeles, CA]

New icosahedral borohydrates Cs.sub.2 [closo-B.sub.12 (OH).sub.12 ]; Cs[closo-1-H-1-CB.sub.11 (OH).sub.11 ]; and closo-1,12-H.sub.2 -1,12-C.sub.2 B.sub.10 (OH).sub.10 are disclosed. Also set forth are their preparation by refluxing the icosahedral boranes [closo-B.sub.12 H.sub.12 ].sup.2-, [closo-1-CB.sub.11 H.sub.12 ].sup.- and closo-1,12-(CH.sub.2 OH).sub.2 -1,12-C.sub.2 B.sub.10 H.sub.10 with a hydroxylating agent, preferably 30%.sub.w hydrogen peroxide.
Full Text Available
Synthesis of an acid addition salt of delta-aminolevulinic acid from 5-bromo levulinic acid esters

Patent Moens, Luc [Lakewood, CO]

A process of preparing an acid addition salt of delta-aminolevulinic acid comprising: dissolving a lower alkyl 5-bromolevulinate and an alkali metal diformylamide in an organic solvent selected from the group consisting of acetonitrile, methanol, tetrahydrofuran, 2-methyltetrahydrofuran and methylformate or mixtures thereof to form a suspension of an alkyl 5-(N,N-diformylamino) levulinate ester; and hydrolyzing said alkyl 5-(N,N-diformylamino) levulinate with an inorganic acid to form an acid addition salt of delta-amino levulinic acid.
Full Text Available
Methods for the synthesis of deuterated acrylate salts

Patent Yang, Jun; Bonnesen, Peter V.; Hong, Kunlun

A method for synthesizing a deuterated acrylate of the Formula (1), the method comprising: (i) deuterating a propiolate compound of Formula (2) to a methyne-deuterated propiolate compound of Formula (3) in the presence of a base and D.sub.2O: and (ii) reductively deuterating the methyne-deuterated propiolate compound of Formula (3) in a reaction solvent in the presence of deuterium gas and a palladium-containing catalyst to afford the deuterated acrylate of the Formula (1). The resulting deuterated acrylate compounds, derivatives thereof, and polymers derived therefrom are also described.
Full Text Available

Similar Records

Title: Synthesis of permethyldodecaborate and paramagnetic dodecaborate salt

Abstract

Citation Formats

An unpaired electron incarcerated within an icosahedral borane cage: synthesis and crystal structure of the blue, air-stable {[closo-B12(CH3)12]·}− radical journal, January 1999

Decakis(dichloromethyl)-1,12-dicarba-closo-dodecaborane(12): Camouflage of an Icosahedral Carborane by Using Bulky Functional Substituents journal, November 1996

An Icosahedral Array of Methyl Groups Supported by an Aromatic Borane Scaffold: The [ c loso -B 12 (CH 3 ) 12 ] 2 - Ion journal, June 1999

An unpaired electron incarcerated within an icosahedral borane cage: synthesis and crystal structure of the blue, air-stable {[closo-B12(CH3)12]·}− radical
journal, January 1999

Decakis(dichloromethyl)-1,12-dicarba-closo-dodecaborane(12): Camouflage of an Icosahedral Carborane by Using Bulky Functional Substituents
journal, November 1996

An Icosahedral Array of Methyl Groups Supported by an Aromatic Borane Scaffold: The [ c loso -B ₁₂ (CH ₃ ) ₁₂ ] ² ^- Ion
journal, June 1999