Thanks to you Sir

Synthesis and structure of soluble lithium alkoxides

T. V. Talalaeva, G. V. Tsareva, A. P. Simonov and K. A. Kocheshkov

Russian Chemical Bulletin
Volume 13, Number 4 / April, 1964
DOI: 10.1007/BF00845302

Abstract

The question of the structure and properties of lithium alkoxides RoLi has remained open until recently. Alkali-metal alkoxides, are usually regarded as ionic compounds. The properties of the simplest lithium alkoxides-lithium methoxide and ethoxide-correspond to this. They are white crystalline substances, involatile, insoluble in nonpolar organic solvents, and resistant to prolonged heating at high temperatures. According to recent data, lithium methoxide remains unchanged after being heated in a high vacuum for 18h at 360'. Under these conditiions aluminium and zirconium methoxides sublime. X-ray structural analysis of lithium methoxide also did not give a definate answer regarding the character ofthe bond in this compound.

Summary
 
1.    Methods for the synthesis of soluble lithium alkoxides of iso, secondary, and tertiary structure were developed.
2.    In their chemical properties the soluble lithium alkoxides do not fall out of line with the general series of alkoxide compounds, and the same general relationships hold.

Photocatalytic Oxidation of Alkanes with Dioxygen by Visible Light and Copper(II) and Iron(III) Chlorides: Preference Oxidation of Alkanes over Alcohols and Ketones
Ken Takaki, Jun Yamamoto, Kimihiro Komeyama, Tomonori Kawabata and Katsuomi Takehira
Bulletin of the Chemical Society of Japan Vol. 77 (2004) , No. 12 pp.2251-2255 doi:10.1246/bcsj.77.2251

Abstract

Visible light irradiation of alkanes in acetonitrile with CuCl2 and FeCl3 catalysts under atmospheric dioxygen gave the corresponding alcohols and ketones effectively; in these reactions, the total selectivity of the products did not decrease so much with increase of alkane conversion. For example, cyclohexanol and cyclohexanone were formed with ca. 70% selectivity at 50% conversion, because overoxidation of the products took place more slowly than cyclohexane oxidation. The relative reactivity values of cycloalkanes increased as their ring-sizes decreased. In the oxidation of hexane, the reactivity ratio of C1-/C2-/C3-H was found to be 1.0/1.4/1.8 with CuCl2 and 1.0/4.6/6.6 with FeCl3, respectively. Toluene and diphenylmethane were more reactive than cyclohexane with FeCl3, as expected, whereas the alkane was oxidized faster than the benzylic compounds in the separate reaction with CuCl2. Moreover, the alkane oxidation could be comparably performed by sunlight instead of an artificial lamp.

XXXIII.—The synthesis of 3--aminoethylindole
Arthur James Ewins
J. Chem. Soc., Trans., 1911, 99, 270 - 273 DOI: 10.1039/CT9119900270


Electrochemical synthesis of L-histidinol using solvated electrons
BELTRA A. P. ; BONETE P. ; GONZALEZ-GARCIA J. ; GARCIA-GARCIA V. ; MONTIEL V. ;
Journal of the Electrochemical Society (2005), 152(4), pp.65-68

Abstract

The feasibility of the preparation of L-histidinol (I) by reduction of L-histidine methyl ester (II) using an electrogenerated solvated electrons solution has been studied in a laboratory scale reactor. The solvated electrons solution was obtained by electrolysis of a solution of LiCI in EtNH2 that permits an easier handling than NH3or MeNH3. All components of the electrochemical setup have been optimized for the reaction conditions used. The influence of some reaction variables on the yield of (I) has been studied. Thus, increasing current intensity and temperature enhances the yield of L-histidinol. Nevertheless, the volatility of ethylamine limits the increase of the intensity current and the temperature. A fractionated feeding procedure of (II) was shown to be desirable. The work-up and isolation procedure of (I) has also been described. It includes an electrodialysis process that makes easier the isolation of (I), as well as the recovered LiCl could be recycled as supporting electrolyte.

I'm sorry, but is that article really about using electrogenerated solvated electrons to reduce a fucking esterified amino acid to the alcohol? Using electricity, LiCl in Ethylamine? If so it is fucking HUGE.. I'm dancing here, that could be fucking tasty...

The Synthesis of Secondary and Tertiary Amines by Borohydride Reduction.
Shellenberg. K. A.
Journal of Organic Chemistry Vol. 28, Nov. 1963 pp. 3259-3261.



Abstract
This note concerns the generality of the synthesis of secondary and tertiary amines by the action of sodium borohydride at 0" on the neutral
aqueous solutions of amine salts and carbonyl compounds; reactions of this type were first reported for a special case (the preparation of dimethylamino acids)
by Biemann and co-~orkers.~T he process is advantageous, since it occurs rapidly without prior isolation of the Schiff bases, and even occurs in some instances
where the equilibrium for the formation of the Schiff base is too unfavorable to permit its ready isolation. This synthesis, unlike previous catalytic reductions of
Schiff bases formed in situ, may be used in the preparation of amines containing nitro or other groups sensitiveto catalytic hydrogenation







Reductive amination of phenylacetylcarbinols by sodium borohydride.
J. Weichet, J. Hodorova and L. Blaha
Coll. Czech. Chem. Commun. 26, 2040-2044 - CA 56, 5864c (1962)




Abstract
The technologically attractive NaBH4 is a suitable agent, since no extensive racemization occurred; however, the
course of the reaction was less stereospecific than in the catalytic process with colloidal Pt to yield a mixt. of
erythro and threo forms of the corresponding aminoales. in approx. 3-4:1 ratio. Thus, 7.5 g. pfluorophenylacetylcarbinol
(I)treated in 50 ml. MeOH at 0-5° with 15 ml. aq. 36% MeNH2, in 25 min. 1.5 g. NaBH4
added portionwise, the mixt. stirred 1 hr., 5 g. K2CO3 added, excess MeNH2 and MeOH distd. in vacuo, dild. with
20 ml. H2O, the product extd. with Et2O, the exts. dried, and satd. with HCl gave 7.1 g. crude HCl salt, m. 195
-205°, which yielded 1.5 g. p-fluoropseudoephedrine, m. 114° (H2O or cyclohexane); HCl salt m. 170° (Me2CO).
The mother liquors gave 4.5 g. p-fluoroephedrine-HCl, m. 234° (90% EtOH); free base m. 76°. Similarly were
obtained 5.5 g. ephedrine-HCl, m. 186-8° (base m. 76-8°) and 1.8 g. pseudoephedrine, m. 117° (HCl salt m.
164°), from 10 g. phenylacetylcarbinol (II) and 0.6 g. NaBH4, 15.6 g. optically active ephedrine-HCl, m. 216-17°,
[a]20D -34°, from 15 g. (-)-II, 6.8 g. m-hydroxyephedrine-HCl, m. 183-5°, from 8.3 g. mhydroxyphenylacetylcarbinol
(III), N-(b-hydroxyethyl)norephedrine, m. 110° (HCl salt m. 164-6°), from II and
HOCH2CH2NH2, and N-butylnorephedrine, m. 70° (HCl salt m. 219-20°), from II and BuNH2. m-
Hydroxyphenylethynylcarbinol, obtained by addn. of C2H2 to m-C6H4CHO in liquid NH3, decompn. of the mixt.
with ice, extn. with Et2O, and crystn. from C6H6 gave 74% crystals, m. 101-4°. Hydration of the ethynylcarbinols
according to the method of Hennion and Fleck (CA 50, 3203c) gave 77.5% I, b8 115-16°, n20 1.5095, 66.5% II,
b14 124-6°, n20 1.5330, and 90% III, m. 98° (C6H6).

Synthesis of [18O]thionyl chloride
Timothy W. Hepburn, Gordon Lowe
Journal of Labelled Compounds and Radiopharmaceuticals Volume 28 Issue 5, Pages 617 - 620, 2006


Abstract
A new synthesis of [18O]thionyl chloride has been developed which, for the first time, allows the product to be isolated in pure form

Cyanohydridoborate anion as a selective reducing agent
Borch, R. F.; Bernstein, M. D.; Durst, H. D.
J. Am. Chem. Soc. 1971, 93, 2897.


Abstract:
 Sodium cyanohydridoborate (NaBH3CN) reduces a wide variety of organic functional groups with
remarkable selectivity. The reduction of aldehydes and ketones is pH dependent, the reaction proceeding readily
at pH 3-4. Oximes are smoothly reduced to alkylhydroxylamines and enamines are reduced to amines under acid
catalysis. Reaction of an aldehyde or ketone with ammonia, primary amine, or secondary amine at pH -7 in the
presence of BHaCN- leads to primary, secondary, or tertiary amines, respectively, uia reductive amination of the
carbonyl group. Reaction of substituted pyruvic acids with ammonia and BH3CN- affords an excellent method
for the synthesis of amino acids; l5N labeling can be accomplished by using I5NH3. The hydrogens of BHICNcan
be readily exchanged for either deuterium or tritium, thus permitting the synthesis of deuterium- or tritiumlabeled
alcohols, amines, and amino acids.

Thanks very much Java!

An Improved Procedure for the Oxidation of Alkynols to Alkynoic Acids
B. C. Holland; N. W. Gilman
Synthetic Communications Volume 4, Issue 4 1974 , pages 203 - 210



Abstract
The chromic acid oxidation of alkynols I to the corresponding alkynoic acids II is a well known process.1 However, in most cases, the yield of the desired acid is poor to moderate (20-50%) due to the formation of the ester III as a by-product.

Versatile electrochemically based preparation of unusual Grignard reagents containing electrophilic substituents
Philippe Dauban, Robert H. Dodd
Tetrahedron Letters Volume 39, Issue 32, 6 August 1998, Pages 5739-5742


Abstract:
Upon electrochemical reduction of potassium perchlorate in dimethyl sulfoxide to potassium the strong dimsyl base (i.e. the conjugate base of dimethyl sulfoxide) is formed in the reaction of the alkali metal with the solvent. The electrolysis is performed in an undivided cell with a magnesium rod serving as sacrificial anode, thereby generating magnesium ions, which stabilize the generated dimsyl through ion-pair formation. In a second non-electrochemical step, Grignard type reagents R2Mg are obtained simply by letting the magnesium salt of dimsyl base deprotonate weakly acidic substrates (pKa < 26 in dimethyl sulfoxide) added to the solution. The advantage of generating these reagents through a deprotonation route rather than by reduction of halogen-substituted compounds as in the classical approach is that the substrates may contain electrophilic groups, such as halogen, carbonyl or cyano. The R2Mg reagents react with electrophiles akin to ordinary Grignard reagents as illustrated by the preparation of several substituted benzylidenefluorenes in nucleophilic addition reactions. The electrochemical properties of the products were investigated and a reasonable linear correlation of the first reduction potentials with the Hammett substituent coefficient ?? was found.

Keywords: Electrogenerated bases; Grignard type reagent; Sacrificial anode; Nucleophilic addition; Synthetic methods



Comment by requestee
This is an electrochemical synthesis of the Dimsyl ion which can be effectively condensed with Styrene and decomposed in heat to yeild Allylbenzene. It basicly boils down to it being the start of A simple high yeilding electro synthesis of Allylbenzene.

Efficient one pot synthesis of nitriles from aldehydes in solid state using peroxymonosulfate on alumina
D.Subhas Bose, A.Venkat Narsaiah
Tetrahedron Letters Volume 39, Issue 36, 3 September 1998, Pages 6533-6534


By chamula



Abstract
A simple and high yielding method for the synthesis of nitriles from aldehydes is described which occurs under mild and solvent-free conditions using microwave irradiation.