A review of the genetic effects of ethyl methanesulfonate
Gary A. Sega
Mutation Research/Reviews in Genetic Toxicology
1984, Volume 134, Issues 2-3, Pages 113-142
doi:10.1016/0165-1110(84)90007-1




Mutations induced by ethyl methanesulfonatenext term in maize
E. Amanoa and H.H. Smitha
Mutation Research/Fundamental and Molecular Mechanisms of Mutagenesis
1965, Volume 2, Issue 4, Pages 344-351
doi:10.1016/0027-5107(65)90070-9



Ethyl methanesulfonatenext term-induced mutations of the Sh1 protein in maize
Prem S. Chourey, and Drew Schwartza
Mutation Research/Fundamental and Molecular Mechanisms of Mutagenesis
1971, Volume 12, Issue 2,  Pages 151-157
doi:10.1016/0027-5107(71)90136-9

......Requested by no1uno


Recent contributions of kolbe electrolysis to organic synthesis
Hans-Jürgen Schäfer
Topics in Current Chemistry
1990, Volume 152/, Electrochemistry IV, pp. 91-151
DOI: 10.1007/BFb0034365

Abstract
Carboxylic acids can be decarboxylated by anodic oxidation to radicals (Kolbe-electrolysis) and/or carbocations (non-Kolbe electrolysis). The procedure and necessary equipment is simple, a scale-up easy, the choice of carboxylic acids wide, the selectivity towards radicals or carbocations can be controlled by reaction conditions and the structure of the carboxylic acid, the yields are in general good. The radical pathway can be used for the preparation of e.g. 1,n-diesters, pheromones, or rare fatty acids. Electrolysis in the presence of olefins affords additive dimers and monomers or by intramolecular addition five membered carbocycles and heterocycles. By non-Kolbe electrolysis carboxylic acids can be converted into ethers, acetals, olefins or acetamides. Rearrangements and fragmentations lead to stereospecifically substituted cyclopentanoids and one- or four-carbon ring extensions.

Requested by no1uno



Preparation of Substituted Acetoxy Silanes
Schuyten,H;Weaver,J;Reid,J
J. Am. Chem. Soc.
1947, Vol.69(9),  pp.2110–2112
DOI: 10.1021/ja01201a011


Abstract
The use of alkyl chlorosilanes, such as dimethyldichlorosilane, to impart water repellency to cotton textiles has been patented. Unfortunately, the hydrogen chloride produced during the reaction of the silane with adsorbed moisture or cellulosic hydroxyls may seriously weaken the cloth unless elaborate and efficient equipment is employed to avoid this difficulty



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Study of the oxidation of ethylenediaminetetra-acetic acid with lead dioxide suspension in sulphuric acid
Ito,Shinichi;Matsuda,Toshio;Nagai,Toyoshi
Talanta
1980, Vol.27(1),  pp.25-28
DOI: 10.1016/0039-9140(80)80006-3


Abstract
The stoichiometry of the reaction between lead dioxide suspension and EDTA was studied by derivative polarographic titration and determination of the products. Four moles of Pb(IV) are reduced per mole of EDTA with moderate speed at room temperature in sulphuric acid solutions. Four moles of carbon dioxide and 3 moles of formaldehyde are the products of the oxidation of 1 mole of EDTA. One mole of N-hydroxymethylethylenediamine is also thought to be produced. The overall reaction may be written as

4Pb(IV) + EDTA + 4H2O?4Pb(II) + 4CO2 + 3HCHO + H2NCH2CH2NHCH2OH + 8H+. Ethylenediamine is also partly produced if a large excess of lead dioxide is used.


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The oxidative decarboxylation of polyaminocarboxylic acids with lead dioxide suspension in neutral medium
El-Sayed,A;El-Shahat,M
Talanta
1983, Vol.30(12), pp.971-973
DOI: 10.1016/0039-9140(83)80225-2


Abstract
The reaction between a suspension of lead dioxide and polyaminocarboxylic adds in neutral medium at 80° has been examined titrimetrically and found to involve decarboxylation in which 3 moles of PbO2 oxidize 1 mole of the acid, the products being 3 moles of CO2, 3 moles of HCHO, 1 mole of ethylenediaminemonoacetic acid and 3 moles of Pb(II) followed by chelation of the 3 moles of Pb(II) by an additional 3 moles of EDTA.

Requested by Quantum Dude



Facile Oxidation of Aldehydes to Acids and Esters with Oxone
Benjamin R. Travis, Meenakshi Sivakumar, G. Olatunji Hollist, and Babak Borhan
Org. Lett.
2003, 5 (7), pp 1031–1034
DOI: 10.1021/ol0340078


Abstract
A highly efficient, mild, and simple protocol is presented for the oxidation of aldehydes to carboxylic acids utilizing Oxone as the sole oxidant. Direct conversion of aldehydes in alcoholic solvents to their corresponding ester products is also reported. These reactions may prove to be valuable alternatives to traditional metal-mediated oxidations.

@ no1uno



Selective reductions. 26. Lithium triethylborohydride as an exceptionally powerful and selective reducing agent in organic synthesis. Exploration of the reactions with selected organic compounds containing representative functional groups[/u]

Brown,Herbert;Kim,S;Krishnamurthy,S

J. Org. Chem.
Vol.45(1) 1980 pp.1-12
DOI: 10.1021/jo01289a001
http://pubs.acs.org/doi/abs/10.1021/jo01289a001

Abstract

The approximate rates, stoichiometry, and products of the reaction of lithium triethylborohydride (Li(Et3)BH) with selected organic compounds containing representative functional groups under standard conditions (tetrahydrofuran, 0'C) were examined in order to explore the reducing characteristics of this reagent, and to establish the utility of the reagent as a selective reducing agent. Primary and secondary alcohols, phenols and thiols evolve hydrogen rapidly and quantitatively, whereas the reaction with 3-ethyl-3-pentanol is slow. n-Hexylamine is inert to this reagent. Aldehydes and Ketones are reduced rapidly and quantitatively to the corresponding alcohols. Even the highly hindered ketone, 2,2,4,4-tetramethyl-3-pentanone is reduced within 30 minutes. The stereoselectivities achieved with this reagent in the reduciton of mono- and bicyclic ketones are better than those realized with lithium aluminium hydride, lithium alkoxyaluminohydrides and lithium borohydride; thus norcamphor is reduced to 1% exo- and 99% endo-2-norbonanol. The reagent rapidly reduces cinnamaldehdye to the cinnamyl alcohol stage, with further addition to the double bond being sluggish. Anthraquinone is cleanly reduced to 9,10-dihydro-9,10-dihydroxyanthracene. The diol was isolated in 77% yield Carboxoylic acids evolve hydrogen gas rapidly and quantitatively (1 eqiv); further reduction is very slow. Acyclic anhydrides utilize 2 equiv of hydride to give an equimolar mix of acid and alcohol after hydrolysis. Utilizing this procedure, we converted phthalic anhydride to phthalide in 90% yield. Acid chlorides, esters, and lactones are rapidly and quantitatively reduced to the corresponding carbinols. Epoxides undergo rapid reduction with the uptake of 1 equiv. of hydrogen. In the case of of unsymmetrical epoxides, exclusive Markovnikov ring opening was observed. Acetals, ketals, and ortho esters are inert to this reagent. Primary amides evolve 1 equiv. of hydrogen rapidly, further reduction of caproamide is slow, whereas benzamide is not reduced. Tertiary amides are rapidly and quantitatively reduced by LiEt3BH exclusively to the corresponding alcohols. Such a clean transformation has not been observed with any other hydride reagent currently available. Benzonitrile rapidly utilizes 2 equiv of hydride to go to the amine stage, whereas capronitrile only takes 1 equiv. Hydrolysis of the latter mixture did not give the expected caproaldehyde, but n-hexylamine and the starting materials were recovered in equal amounts. It appears possible that to selectively reduce tertiary amides and aromatic nitriles to aldehydes in excellent yields by using stoichiometric quantities of the reagent. 1-Nitropropane utilizes only 1 equiv of hdyride for hydrogen evolution without any reduction. Nitrobenzene, azobenzene, and azoxybenzene are rapidly reduced. Cyclohexanone oxime rapidly evolves hydrogen but no reduction is observed. Phenyl isocyanate readily consumes 1 equiv of hydrogen in going to the formanilide stage. Pyridine is rapidly reduced to the tetrahydropyridine stage, followed by furhter, slow reduction. Pyridine N-Oxide, also undergoes rapid reaction with this reagent. Disulfides are rapidly reduced to the thiol stage, whereas sulfoxide, sulfonic acid and sulfides are practically inert to this reagent. Cyclohexyl Tosylate is slowly reduced to give a mixture of cyclohexane (80%) and cyclohexene (20%). Diphenyl sulfone slowly reacts to give an unexpected product, ethylbenzene in excellent yield. The nature of the intermediates of representative reactions were also studied. Products of the reaction of the reagent with simple primary and secondary alcohols, tert-butyl alcohol, and most ketones exist as weak triethylborane complexes, whereas those of 3-ethyl-pentanol, phenols, carboxylic acids, thiols, and 1-nitropropane exist as their lithium salts without coordinating with the triethylboron formed.



Selective reductions. 31. Lithium triethylborohydride as an exceptionally powerful nucleophile. A new and remarkably rapid methodology for the hydrogenolysis of alkyl halides under mild conditions[/u]

Krishnamurthy,S;Brown,Herbert

J. Org. Chem
Vol.48(18) 1983 pp.3085–3091
DOI: 10.1021/jo00166a031
http://pubs.acs.org/doi/abs/10.1021/jo00166a031


Abstract

Lithium triethylborohydride exhibits enormous nucleophilic power in SN displacement reactions with alkyl halides, far more powerful than the other common nucleophiles, such as n-butyl mercaptide (14 times), thiophenoxide (20 times), borohydride (104 times), and nitrate (107 times). The reaction follows second-order kinetics and exhibits typical characteristics of a nucleophilic substitution of the SN type. In addition to being the best nucleophile, it is the most powerful nucleophilic reducing agent available for the reduction of alkyl halides, far more powerful and cleaner than lithium aluminium hydride and lithium borohydride. Even hindered alkyl halides, like cyclohexyl bromide, neopentyl bromide, and exo-norbornyl bromide, undergo facile reduction to the corresponding alkanes in >96% yield with this reagent. Consequently, the new reagent provides a highly useful and simple means as a probe for studying SN displacement reactions and also for the facile dehalogenation of hindered alkyl halides where this is required in synthetic transformations. The corresponding deuterated derivative, lithium triethylborodeuteride, conveniently synthesized from lithium deuteride and triethylborane, is useful for the stereospecific introduction of deuterium in the molecule.

Requested by no1uno

The second group of requests are included because (1) they may include an alternative route and (2) there is apparently preliminary pharmacological study on the N-(2-methoxybenzyl)Phenethylamine(s). I've yet to see any real reports on that.

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The Reaction of Lewis Acids of Boron with Sodium Hydride and Borohydride

Brown,Herbert;Tierney,Paul

J. Am. Chem. Soc.
1958, Vol.80(7),  pp.1552-1558
DOI: 10.1021/ja01540a011

Abstract

In the presence of diglyme, sodium hydride absorbs diborane to form sodium borohydride. In the presence of excess diborane, additional diborane is absorbed to yield NaBH₄.BH₃. In diglyme solution boron trifluoride readily reacts with sodium hydride to form diborane. Diglyme solutions of sodium borohydride react readily with boron trifluoride in either stoichiometric or excess amounts to liberate diborane quantitatively. Boron trichloride can also be used in stoichiometric amount; however, excess boron trichloride reacts with diborane to form chloroborane etherates, resulting in reduced yields of diborane. Dimethoxyboron chloride reacts with sodium borohydride in diglyme to give diborane and methyl borate. Methyl chloride is reduced to methane by sodium borohydride in diglyme.

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Syntheses based on?-phenylethylamines. I. Preparation of substituted ?-phenylethylamines
Vinogradova,V;Yunusov,M;Kuchin,A;Tolstikov,G;Sagandykov,R;Khalmuratov,Kh;Alimov,A
Chemistry of Natural Compounds
1990, Vol.26(1), pp.57-59
DOI: 10.1007/BF00605201

Abstract

A comparative study has been made of methods of synthesizing substituted beta-phenylethylamines via the corresponding nitriles and via nitrostyrenes, and a superiority of the latter method has been established. The possibility has been shown for the first time of reducing nitrostyrenes to saturated amines with diisobutylaluminum hydride (DIBAH). The use of DIBAH as reducing agent enables amines to be obtained in high yields.

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Syntheses based on B-phenylethylamines. II. Preparation of N-(2-methoxybenzyl)-3,4-dimethoxyphenethylamine

Golodnyuk,T;Vinogradova,V;Yunusov,M

Chemistry of Natural Compounds
1990, Vol.26(2),  pp.232-233
DOI: 10.1007/BF00607561

Abstract

The possibility has been previously shown of using a 2-hydroxybenzyl protection of an N-H bond and the subsequent ready elimination of the protective group on thermolysis. The thermal decomposition of N-(2-hydroxybenzyl)-3,4-dimethoxyphenethylamine [1] gives homoveratrylamine [2] with 80% yield. The ease of a retrodiene breakdown of a substamce of the type of [1] is connected with the formation of the o-quinone methide.

For no1uno.


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Preparation and Properties of Some Trialkylboranes

Rosenblum,Louis

J. Org. Chem.
Vol.25(9) 1960 pp.1652-1655
DOI: 10.1021/jo01079a043


Abstract

Triethyl-, tri-n-propyl-, and tri-n-butylborane were prepared and fractionated under an inert atmosphere to prevent oxidation. Triethylborane and tri-n-propylborane were obtained in purities of 99.8 and 99.7 mole percent, respectively, while tri-n-butylborane underwent thermal decomposition during distillation. The following physical and thermodynamic properties of triethylborane and tri-n-propylborane were determined: freezing point, boiling point, refractive index, density, dielectric constant, and heat of combustion.

Triethylborane (Et3B)
O'Mahony,Gavin
Synlett
Vol.3 2004 pp.572-573  
DOI: 10.1055/s-2004-815434
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The Synthesis and Infra-Red Spectrum of Carbon-Deuterated Ethylenediamine Dihydrobromide
Gaver,R;Mumann,R

J.Inorganic and Nuclear Chemistry
Vol.26(5) 1964 pp.881-885
DOI: 10.1016/0022-1902(64)80335-3


Abstract

Ethylenediamine-C-d4 · 2HBr is produced in 80–90 per cent yield by the reaction of anhydrous NH3 with 1,2-dibromoethane-d4 in a sealed tube at 55°. An estimation of the level of C---H impurity is made from a comparison of the Infrared Spectra of normal and carbon-deuterated ethylenediamine dihydrobromide and verified by the Nuclear Magnetic Resonance Spectra of the free amines. Little or no hydrogen exchange on the carbon atoms occurs during the reaction and subsequent purification. On the basis of simplicity, high yield, relative freedom from side reactions, and lack of isotopic exchange, this method is suggested for the preparation of carbon and hydrogen isotopically substituted ethylenediamine.

requested by no1uno






Addition Compounds of Alkali Metal Hydrides. Sodium Trimethoxyborohydride and Related Compounds
Brown,Herbert;Schlesinger,H;Sheft,Irving;Ritter,D
J.Am. Chem. Soc.
1953, Vol.75(1), pp.192–195
DOI: 10.1021/ja01097a051



Abstract
Sodium hydride reacts readily at moderate temperatures with borate esters such as methyl, ethyl, and n-butyl borate to form acid-base addition complexes. These new substances Na[BH(OR)[size=-2]3[/size]][size=-2]3[/size], are stable white solids with strong reducing properties. The reactions of sodium trimethoxyborohydride with water, alcohol, hydrogen chloride, boron fluoride and carbon dioxide are described. With boron fluoride etherate, diborane is obtained by a convenient reaction. Qualitative observations on the reducing properties of the compound in aqueous solution are noted. The corresponding reaction of methyl borate with lithium hydride does not proceed as smoothly because the addition compound appears to undergo decomposition and disproportionation fairly readily. Addition of other compounds of trivalent boron, eg. alkyl borons to alkali metal hydrides is described.




[/quote]

Requested by lugh


The sommelet reaction. Part II. The ortho-effect
S. J. Angyal, (Miss) P. J. Morris, R. C. Rassack and (Miss) J. A. Waterer
J. Chem. Soc.,
1949, 2704 - 2706,
DOI: 10.1039/JR9490002704[/color]