N-Tartaric acid

The aqueous hydrazide solution is evaporated from a tared 2000 ml flask on an efficient rotary evaporator, using a bath temperature of 40° and an ice-cooled condenser the 3000 ml siphon flask assembly is used as storage for the vacuum feed. The weight of the crude hydrazide so obtained is determined, it is dissolved in about 170 ml 1 N tartaric acid, the aqueous solution washed with three 30 ml portions ether, made alkaline with 190 ml 1 N ammonium hydroxide, and exhaustively extracted with successive portions of chloroform, the first two portions being 100 ml each, the following 50 ml. 

Polonium tetrachloride is very soluble in 2 N tartaric acid, giving a colorless solution which slowly darkens owing to radiation decomposition. Electrolysis leads to deposition of about 12% of the polonium on the cathode and 65% on the anode (11). 

The 3-chloro-l-(4-indolyloxy)-2-propanol is dissolved in 50 ml of toluene and 50 ml of isopropylamine and heated to the boil for 45 h. Evaporation to dryness is effected in a vacuum, the residue is shaken out thrice between ethyl acetate and a 1 N tartaric acid solution and a 5 N sodium hydroxide solution is then added to the combined tartaric acid phases until an alkaline reaction is obtained. The alkaline solution is shaken out thrice with 50 ml of methylene chloride, the extracts are dried over magnesium sulfate and the solvent evaporated in vacuum. The residue is crystallized from ethyl acetate/ether to give the 4-(2-hydroxy-3-isopropylaminopropoxy)indole. 

Stirring is carried out first for 3 hours at room temperature and then for 2 hours at boiling temperature, it is then cooled and poured into 300 ml of ice-cold 20% ammonium chloride solution. It is then shaken out with methylene chloride, the methylene chloride solution washed with water and shaken 3 times with 30 ml portions of aqueous 2 N tartaric acid solution. The tartaric acid extract is rendered alkaline while cooling thoroughly and then extracted twice with methylene chloride. After washing with water, drying over potassium carbonate and reducing in volume by evaporation, the residue is recrystallized from ethanol. MP 197° to 199°C. 

XXII). The hydrolysis of XXI and subsequent oxidation of the products with calcium hypobromite produced in high yield n-tartaric acid... 

It is interesting that Nef assigned the correct configurations to the D-galactometasaccharinic acids, as well as to the D-glucometasaccharinic acids, on the basis of analogies between the optical rotations of n-tartaric acid, the 2,4-dihydroxyglutaric acids (obtained by oxidation of the five-carbon metasaccharinic acids), and the 2,3,5-trihydroxyadipic acids (obtained by oxidation of the six-carbon metasaccharinic acids). 

It is well known that catalytic amounts of aldehyde can induce racemization of a-amino acids through the reversible formation of Schiff bases [571. Combination of this technology with a classic resolution leads to an elegant asymmetric transformation of L-proline to n-proline (Scheme 8) [58,59]. When i.-proline is heated with one equivalent of o-tartaric acid and a catalytic amount of -butyral-dehyde in butyric acid, it first racemizes due to the reversible formation of the proline-butyraldehyde Schiff base. The newly generated o-prolinc fonns an insoluble salt with D-tartaric acid and precipitates out of the solution, while the soluble L-proline is continuously being racemized. The net effect is the continuous transformation of the soluble L-proline to the insoluble D-proline-n-tartaric acid complex, resulting in near complete conversion. Treatment of the n-proline-D-tartaric acid complex with concentrated ammonia in methanol liberates the d-proline (16) (99% ee, with 80-90% overall yield from L-proline). This is a typical example of a dynamic resolution in which L-proline is completely converted to D-proline with simultaneous in situ racemization. As far as the process is concerned, this is an ideal case because no extra step is required for recycle and racemization of the undesired enantiomer, and a 100% chemical yield is achievable. The only drawback of this process is tlie use of stoichiometric amount of... 

The purified commercial di-n-butyl d-tartrate, m.p. 22°, may be used. It may be prepared by using the procedure described under i o-propyl lactate (Section 111,102). Place a mixture of 75 g. of d-tartaric acid, 10 g. of Zeo-Karb 225/H, 110 g. (136 ml.) of redistilled n-butyl alcohol and 150 ml. of sodium-dried benzene in a 1-litre three-necked flask equipped with a mercury-sealed stirrer, a double surface condenser and an automatic water separator (see Fig. Ill, 126,1). Reflux the mixture with stirring for 10 hours about 21 ml. of water collect in the water separator. FUter off the ion-exchange resin at the pump and wash it with two 30-40 ml. portions of hot benzene. Wash the combined filtrate and washings with two 75 ml. portions of saturated sodium bicarbonate solution, followed by lOu ml. of water, and dry over anhydrous magnesium sulphate. Remove the benzene by distillation under reduced pressure (water pump) and finally distil the residue. Collect the di-n-butyl d-tartrate at 150°/1 5 mm. The yield is 90 g. 

Nitro-toluol, n. nitrotoluene. -verbindung, /. nitro compound, -weinsaure, /. nitrotar-taric acid (tartaric acid dinitrate, also the mononitrate), -zelluloselack, m. nitrocellulose lacquer or dope. 

D,L-3-Hydroxy-N-methyl-morphinan Phenyl trimethyl ammonium chloride D-Tartaric acid... 

A mixture of 10.0 g of 3-methylsulfinyl phenothiazine (MP 193° to 195°C), 6.1 g of finely powdered sodium hydroxide and 125 cc of toluene is boiled for 1 hour under reflux with a water separator on an oil bath kept at a temperature of 150°C, while the mixture is stirred. Without interrupting the boil a solution of 7.0 g of 2-(N-methvl-piperidyl-2 )-1-chloroethane (BP 84°C/10 mm Hg) in 10 cc of toluene is added dropwise in the course of 1 hour, after which boiling is continued for another 3 hours. When the reaction mixture has cooled it is first washed with 25 cc of water three times and then extracted with 75 cc of a 15% aqueous tartaric acid solution. The tartaric acid extract is shaken out with 25 cc... 

After having been washed with 50 cc of water the benzene layer is dried over potassium carbonate, filtered, allowed to stand over 10 g of alumina for about VA hours for partial decolorization, filtered again and concentrated under reduced pressure. The oily base which remains as a residue is directly converted into the tartrate. A solution cooled to 0°C, of 6.50 g of the free base in 100 cc of acetic acid ethyl ester is thoroughly shaken and poured into an ice cold solution of 2.66 g of tartaric acid in 410 cc of acetic acid ethyl ester. The precipitated, analytically pure, tartrate of 3-methylsulfinyl-10-[2 -N-methyl-piperidyl-2")-ethyl-1 ]-phenothiazine melts at 115° to 120°C (foam formation) and sinters above B0°C. The base Is reacted with benzene sulfonic acid in a suitable solvent to give the besylate. 

Early examples of enantioselective extractions are the resolution of a-aminoalco-hol salts, such as norephedrine, with lipophilic anions (hexafluorophosphate ion) [184-186] by partition between aqueous and lipophilic phases containing esters of tartaric acid [184-188]. Alkyl derivatives of proline and hydroxyproline with cupric ions showed chiral discrimination abilities for the resolution of neutral amino acid enantiomers in n-butanol/water systems [121, 178, 189-192]. On the other hand, chiral crown ethers are classical selectors utilized for enantioseparations, due to their interesting recognition abilities [171, 178]. However, the large number of steps often required for their synthesis [182] and, consequently, their cost as well as their limited loadability makes them not very suitable for preparative purposes. Examples of ligand-exchange [193] or anion-exchange selectors [183] able to discriminate amino acid derivatives have also been described. 

The corrosion of tin by nitric acid and its inhibition by n-alkylamines has been reportedThe action of perchloric acid on tin has been studied " and sulphuric acid corrosion inhibition by aniline, pyridine and their derivatives as well as sulphones, sulphoxides and sulphides described. Attack of tin by oxalic, citric and tartaric acids was found to be under the anodic control of the Sn salts in solution in oxygen free conditions . In a study of tin contaminated by up to 1200 ppm Sb, it was demonstrated that the modified surface chemistry catalysed the hydrogen evolution reaction in deaerated citric acid solution. 

Similar results are found with the threose derivatives 11 and 13. Both aldehydes can be readily synthesized in either enantiomeric form from l- and D-tartaric acid. The open-chain aldehyde 11 with Grignard reagents affords predominantly the all-.v> n(xj/o)-diastereomer 12. The steric demand of the nucleophile apparently does not affect the diastereoselectivity, and the extremely high selectivity observed with [(l,3-dioxolan-2-yl)methyl]magnesium bromide is attributed to the presence of the dioxolane moiety, which is thought to stabilize the a-chelated transition state. 

Deacetylanisomycin (4) is synthesized using L-tartaric acid (1) as a precursor in 12% overall yield16. The key step is the diastereoselective addition of (4-methoxybenzyl)magnesium chloride to the C — N double bond of nitrone 2 at 0°C in the presence of 1 equivalent of ethylmagncsium-bromide diethyl ether complex in dichloromethane. This procedure affords a chromatograph-ically separable mixture of the hydroxylamines 3 a and 3 b in a diastereomeric ratio [(2R,35,4R)/ (25,35,47 )] 70 30 and 60% yield from 2. 

Enantiopure (R)- and (S)-nipecotic acid (Nip) derivatives 64 were obtained following classical resolution of ethyl nipecotate with either enantiomer of tartaric acid and successive recrystallization of the corresponding salts [153, 154, 156] or by resolution of racemic nipecotic acid with enantiomerically pure camphorsul-fonic acid [154]. N-Boc protected pyrrolidine-3-carboxylic acid (PCA) 65 for the synthesis of homo-ohgomers [155] was prepared by GeUman from trans-4-hydroxy-L-prohne according to a known procedure [157]. 

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