A STUDY OF SOME UREA DERIVATIVES IN THE ALKANOLAMINE SERIES
RALPH W. CHARLTON, ALLAN R. DAY
J. Org. Chem
1937, 1 (6), pp 552–558
DOI: 10.1021/jo01235a004

.....here is a little something posted in the acetic anhydride thread......at sciencemadness.,.....java

http://www.sciencemadness.org/talk/viewthread.php?tid=9&page=4#pid55178

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stygian
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• posted on 27-11-2005 at 09:44 PM    Reply With Quote Report Post to Administrator

I'm going to assume that this was overlooked, otherwise I don't see why there'd be a continuing discussion on this.

Acetic Anhydride and Propionic Anhydride
Drone #342:

Here's what everyone's looking for. Some things are a little wierd about it, like the fact in the acetic anhydride synth they use a small quantity of acetic anhydride as a solvent. However, as one sees in propionic anhydride, such a solvent may not be necessary.

From "Chemistry & Industry", 1945, p. 382; "LABORATORY METHOD FOR THE PREPARATION OF ORGANIC ACID ANHYDRIDES" by Jehuda Orshansky and Eliahu Bograchov.

"...(1) Acetic anhydride. To 50 g. acetic anhydride in a round-bottomed flask of 1500 cc. capacity, placed in cold water, 440 g. of powdered sodium acetate (dried by fusion at 320 C) and at the same time a solution of 22. g of sulfur in 320 g. bromine is added while stirring. The operation takes about 30 minutes.

"The mixture is then stirred for a further 5 minutes, after which period the initially dark brownish-red colour has changed into pale yellow, and the anhydride is distilled off from a water bath under reduced pressure. The crude anhydrie (310 g) is redistilled under normal pressure, and the fraction boiling between 134-138 C is collected. Yield, 295 g. of 98% purity = 87.5%. The so purified anhydride contains neither bromine nor sulphur compounds and leaves no residue on evaporation..."

"(2) Propionic anhydride. To 40 g. fused and powdered sodium propionate in a flask of 250 cc. capacity a solution of 2 g. sulphur in 22 g. bromine was added while stirring. The temperature was kept at about 50 C. When the operation was completed, the anhydride was distilled off in vacuo. The crude product (25g.) was fractioned under normal pressure, and the fraction 155-156 C was collected. Yield, 23 g. propionic anhdride of 90% purity = 85%..."

The paper mentions that other alkali metals and alkali earth metals work just fine. Calcium propionate is a food preservative added to cheap white bread to keep it from molding. With these nuggets of information, the most closely watched reagent on the DEA's watched list, propionic anhydride, just turned OTC. I can almost see the fentanyl analogs clogging the opioid market already.

The one reason, and justafiably so, they poo-poo using chlorine (which does indeed work nicely) is that its a hassle to work with, especially considering the fact that they'd be adding a gas to a solid to make a liquid. I propose that perhaps with the use of chloroform as a solvent, chlorine could be bubbled in readily, and the reaction would go as previously stated. I assume they tried to avoid using extra solvents in hopes of staying away from azeotropes messing up their products' purity, so this may or may not work, depending on what you're trying to do.

Iudexk:

To 66.5g fused AcONa (made from AcOH + NaOH) was added a soln. of 3.3g S in 48.4g Br2 over 5mins, under manual stirring. Brown colour disappears rapidly on stirring to give slightly off-white mixture. Stirring continued for another 15mins. Mixture has v. strange consistancy; becomes almost liquid while stirring but as soon as one stops stirring it becomes solid again. Thus formed sludge was scooped up and dumped in a distillation flask (spilling much in the process - do this rxn in the same flask you're gonna distil from), and distilled.

Yield of Ac2O = 29.2g as a clear pungent liquid.

Note that basically all you need is NaOAc, S, and Br2. And some distilling equipment.

Conjugated nitroalkenes: versatile intermediates in organic synthesis
Anthony G. M. Barrett, Gregory G. Graboski
Chem. Rev.,
1986, 86 (5), pp 751–762
DOI: 10.1021/cr00075a002

Physical Properties of Eight High-Purity Nitroparaffins
Emory E. Troops, Jr
J. Phys. Chem.
1956, 60 (3), pp 304–306
DOI: 10.1021/j150537a012


Abstract
The boiling point, vapor pressure, freezing point, density and refractive index have been determined for the eight mononitroparaffins from nitromethane through the four isomeric nitrobutanes. The measurements were made on highly purified samples, characterized by both ebullioscopic and cryoscopic methods. The vapor pressure data have been fitted to the Antoine equation by the method of least squares

I'll ask for this one - it came up when I kept searching for Kolbe and nitroethane, it says on the front page that they made the nitroparaffins via synthesis as well as via purification and the Kolbe route is mentioned, fingers crossed:

Unless Murphy (or someone else) can translate the J.Prakt.Chem report of Kolbe himself, this might be the last-best bet we have for references for the nitropropionic acid decarboxylation.

Tartranilide.
 H. Polikier
Ber.
1918, 2959-2962
doi. 10.1002/cber.189102402125


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Synthesis of indole from tartaric acid and aniline (Ueber eine Indolsynthese aus Weinsa?ure und Anilin)
H. Poliker
Ber.
1918, 2954-2959
doi. 10.1002/cber.189102402124

The Synthesis of Chloramphenicol Analogs
Charles F. Huebner, Caesar R. Scholz
J. Am. Chem. Soc.
1951, 73 (5), pp 2089–2094
DOI: 10.1021/ja01149a054

The Fluorosulfuric Acid Solvent System. I. Electrical Conductivities, Transport Numbers, and Densities
J. Barr, R. J. Gillespie, R. C. Thompson
Inorg. Chem.
1964, 3 (, pp 1149–1156
DOI: 10.1021/ic50018a019



Abstract
The results of measurements of the conductivities and transport numbers of solutions of some alkali and alkaline earth metal fluorosulfates in fluorosulfuric acid are reported. It is concluded that fluorosulfate ion conducts mainly by a proton-transfer process. Conductometric studies of a number of other bases are reported. Dissociation constants are calculated for several weak bases. Densities of solutions of a number of solutes have been measured.


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The Fluorosulfuric Acid Solvent System. II. Solutions of Antimony Pentafluoride, Antimony Tetrafluoride Monofluorosulfate, and Antimony Pentafluoride-Sulfur Trioxide Mixtures
R. C. Thompson, J. Barr, R. J. Gillespie, J. B. Milne & R. A. Rothenbury
Inorg. Chem.
1965, 4 (11), pp 1641–1649
DOI: 10.1021/ic50033a024



Abstract
Conductometric, cryoscopic, and nuclear magnetic resonance studies on solutions of SbF3, SbF4SO2F and SbF3-SO2 mixtures in flourosulfuric acid show that there exists a series of acids with the general formula H[SbF3n(SO2F)n] where n=0,1,2, and 3 which increase in strength with increasing values of n. The acid H[SbF2(SO3F)4] is a strong acid of the fluorosulfuric acid solvent system. Dimeric and probably higher polymeric forms of these acids are also present in the solutions and n.m.r. studies show that polymerization occurs through fluorosulfate bridges. The fluorosulfuric acidium ion, H2SO3F, has been shown to have abnormally high conductivity in this solvent and it is concluded that it conducts by proton transfer


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Fluorosulfuric Acid Solvent System. III. Cryoscopic Measurements
R. J. Gillespie, J. B. Milne & R. C. Thompson
Inorg. Chem.
1966, 5 (3), pp 468–473
DOI: 10.1021/ic50037a030




Abstract
The apparatus and technique for making cryoscopic measurements in fluorosulfuric acid is described. The cryoscopic constant was determined from the freezing-point depressions produced by some nonelectrolytes and it was found to have the value 3.93 +/-0.05 deg mole-1 kg. The freezing points of the system HF-SO3 in the region of the composition HSO3F have been studied. The freezing point of HSO3F was found to be -88.93'C. The extent of self-dissociation into SO3 and HF at the maximum freezing point was found to be very small, but the freshly distilled acid generally contains a very small excess of SO3. The self-dissociation equilibrium constant K = [SO3][HF] probably has a value less than 3 x 10(-7). Both SO3 and HF are shown to behave as nonelectrolytes in solution in HSO3F. Metal fluorosulfates and benzoic acid were found to behave as simple binary electrolytes. The extent of ionization of some nitro compounds has been determined from their freezing-point depressions.


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The Fluorosulfuric Acid Solvent System. IV. The Solutes Water and Potassium Nitrate
R. J. Gillespie, J. B. Milne & J. B. Senior
Inorg. Chem.
1966, 5 (7), pp 1233–1235
DOI: 10.1021/ic50041a034




Abstract
It is shown that solutions of water in fluorosulfuric acid protonation and partial hydrolysis occur, and the following equilibrium is set up: H2O + SO3F <==> HF H2SO4. Values for the equilibrium constant of this reaction have been obtained at 25, 0, and at -78.5'C. Potassium Nitrate ionizes according to the equation: KNO3 + 3HSO3F = K + NO2 + H2O and 3SO3F. A general method is outlined for interpreting the results of conductivity measurements on complex electrolytes such as potassium nitrate that ionize to produce water. A technique is described for the measurement of conductivities at -78.5'C.



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The Fluorosulfuric Acid Solvent System. V. Iodine Trifluorosulfate
R. J. Gillespie & J. B. Milne
Inorg. Chem.
1966, 5 (7), pp 1236–1238
DOI: 10.1021/ic50041a035



Abstract
The results of nmr, freezing point, and conductivity measurements in 1:7 and 1:3 I2-S2O6F2 solutions in fluorosulfuric acid are reported. They show that iodine trifluorosulfate is highest fluorosulfate formed in solution in fluorosulfuric acid. Iodine trifluorosulfate behaves as an apholyte in fluorosulfuric acid and reacts with water at low temperatures to give iodosyl fluorosulfate, IOSO2F. Acid and base ionization constants have been determined.



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Fluorosulfuric acid solvent system. VI. Solutions of phosphorus, arsenic, bismuth, and niobium pentafluorides and titanium tetrafluoride
Ronald J. Gillespie, Kenichi Ouchi & Guido P. Pez
Inorg. Chem.
1969, 8 (1), pp 63–65
DOI: 10.1021/ic50071a015



Abstract
Conductivity measurements on solutions of PF5, AsF5, NbF5, PF5-SO3, NbF-SO3, and AsF5-SO3 are reported. Condumetric titrations ahve been carried out on solutions of AsF6, BiF5, and AsF5.SO3. The results are compared with those obtained previously for SbF5 and SbF5-SO3. It is concluded that acid strength increases in the order: PF5~NbF5<TiF4~AsF6<BiF3<AsF4(SO2F)<SbF5<AsF2(SO3F)3<SbF2(SO3F)3.


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Fluorosulfuric acid solvent system. VII. The behavior of some extremely weak bases in the superacid system fluorosulfuric acid- antimony pentafluoride-sulfur trioxide
Ronald J. Gillespie & Guido P. Pez
Inorg. Chem.
1969, 8 (6), pp 1233–1235
DOI: 10.1021/ic50076a006



Abstract
Nitrogen, oxygen, neon, xenon, hydrogen, nitrogen trifluoride, and carbon monoxide all have very small solubility in the HSO3F-SbF3-SO3 system and do not appear to be protonated. Carbon dioxide has moderate solubility and sulfur dioxide has a high solubility in this superacid solvent but neither is protonated to any significant extent. The very weak base 1,3,5-trinitrobenzene appears to be completely protonated.



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Chemistry in super acids. I. Hydrogen exchange and polycondensation of methane and alkanes in FSO3H-SbF5 ("magic acid") solution. Protonation of alkanes and the intermediacy of CH5+ and related hydrocarbon ions. The high chemical reactivity of "paraffins" in ionic solution reactions
George A. Olah & Richard H. Schlosberg
J. Am. Chem. Soc.
1968, 90 (10), pp 2726–2727
DOI: 10.1021/ja01012a066


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Chemistry in super acids. II. Nuclear magnetic resonance and laser Raman spectroscopic study of the antimony pentafluoride-fluorosulfuric acid (sulfur dioxide) solvent system (magic acid). The effect of added halides, water, alcohols, and carboxylic acids. Study of the hydronium ion
Auguste Commeyras & George A. Olah
J. Am. Chem. Soc.
1969, 91 (11), pp 2929–2942
DOI: 10.1021/ja01039a019



Abstract
Proton 19F nmr, and Raman spectroscopic studies on solutions of SbF5-HSO3F show the existence of equilibria 1-6. When SO2 is used as a solvent the acidity of the system decreases. The equimolecular complex SbF5-SO2 is formed shifting the equilibria 5 and 6 and consequently 4 to the left. Equilibrium 3 is shifted to the right. In all cases equilibrium 3 shifts to the right when the acidity of the system decreases and to the left when the acidity increases. When any base is protonated, the anion [Sb2F10SO2F] is formed. Upon dehydration of alcohols or carboxylic acid, to for R+ or RCO+, the water formed is immediately quenched (protonated) by excess acid, to form [H2O]+ which is in equilibrium with [H2OHoH2]+. On formation of cations from haloorganic precursors (RX, RCOX), the anions [Sb2F11]- and [SbF6]- are in equilibrium.



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Additions and Corrections - Chemistry in Super Acids. III. Protonation of Alkanes and the Intermediacy of Alkanonium Ions, Pentacoordinated Carbon Cations of the CH5+ Type. Hydrogen Exchange, Protolytic Cleavage, Hydrogen Abstraction, and Polycondensation of Methane, Ethane, 2,2-Dimethylpropane (Neopentane), and 2,2,3,3-Tetramethylbutane in FSO3H-SbF5 ("Magic Acid") Solution
George Olah, Gilles Klopman & Richard Schlosberg
J. Am. Chem. Soc.
1970, 92 (4), p 1107
DOI: 10.1021/ja00707a603

Über einige Derivate des Äthyl-brenzcatechins
H. Pauly, K. Neukam
Berichte der deutschen chemischen Gesellschaft
1918, Volume 41, Issue 3 , Pages4151 - 4161
DOI: 10.1002/cber.190804103124[/color]

Preparation of N-Chloroamides Using Trichloroisocyanuric Acid
Gene A. Hiegel;  Tyrone J. Hogenauer; Justin C. Lewis
Synthetic Communications
2005,  Volume 35, Issue 15, pages 2099 -2105
DOI: 10.1081/SCC-200066703