Phosphorous Oxychloride Research Articles

Energy transfer between ytterbium and erbium in phosphorous oxychloride

A study of energy transfer from ytterbium to erbium in POCl 3: ZrCl 4 was performed for wide range of donor and acceptor concentrations. The efficiences and the probabilities of energy transfer were calculated on the basis of experimental data and a theoretical model. The high values of transfer probabilities derived from experimental data were attributed to the formation of the large agglomerations of solvates rare earth ions.

Polymerisation of trioxane, 3. Kinetics of the reaction initiated by stannic chloride and phosphorous oxychloride

AbstractThe kinetics of polymerisation of 1,3,5‐trioxane initiated by stannic chloride and phosphorous oxychloride were investigated in the solvents chlorobenzene, o‐dichlorobenzene, trichloroethylene, and tetrachloroethylene. With pure reactants no induction periods were observed. The kinetic and equilibrium parameters were evaluated.

Reaktionen an Allencarotinoiden 2

AbstractThe conversion of the allenic end group 1 on HCl/CHCl3 treatment to the acetylenic 2 resp. to the chlorinated end group 3 previously reported has been confirmed using neoxanthin (4a) and its diacetate (4b). Analogous HBr treatment provided the corresponding brominated end group. Chemical and spectroscopical evidence for the position of the halogen atom at C(7) is given.Transformation to allenic anhydro products and acetylenic products on treatment of neoxanthin diacetate (4b) with phosphorous oxychloride in pyridine, as well as dehydration and chlorine substitution of neoxanthin (4a) are reported. These results are consistent with previous observations on related carotenoids.

Condensation Reactions of 2-Amino-N-acylphenethylamines and 2-Amino-β-acylaminostyrenes

Molecular sieves have been used to catalyze the condensation reaction of cis-β-(o-acetotoluidino)-2-aminostyrene (4) to yield 2-methyl-3-(o-tolyl)-3H-1,3-benzodiazepine (11). A second major product from the reaction was 2-(o-toluidino)-N-acetylindole (13), an example of the type of compound presumed to be an intermediate in the Fischer indole synthesis. The formation of N-acetylindole from 13 occurred on treatment of 13 with silica or alumina.The trans isomer, 5, and the reduced analog, 6, were unreactive with molecular sieves but 6 could be converted to 4,5-dihydro-2-methyl-3-(o-tolyl)-3H-1,3-benzodiazepine by reaction with phosphorous oxychloride.

Synthesis and properties of enamine derivatives of 1-methyl-2-phenyl-5-pyrrolone and 5-thiopyrrolone

The corresponding dimethylaminomethylene derivative, from which a number of similar compounds were synthesized by reaction with amines, was obtained by the reaction of 1-methyl-2-phenyl-2-hydroxy-5-oxotetrahydropyrrole with dimethylformamide in the presence of phosphorous oxychloride. The formyl derivatives of 1-methyl-2-phenyl-5-pyrrolone and 5-thiopyrrolone were obtained, and the UV and IR spectra of the enamines of these compounds were studied.

Studies on the Pyridazine Derivatives. XIV. Synthesis and Reaction of Pyrimido [4, 5-c] pyridazines

New pyrimido [4, 5-c] pyridazines were synthesized by cyclization of 3-amino-4-carbamoylpyridazines (IV, VII) and 3-chloro-4-ethoxycarbonylpyridazine (II). When 3-chloro-5-hydroxypyrimido [4, 5-c] pyridazine (XVI) was treated with phosphorous oxychloride and N, N-dimethylaniline, 1, 4-dihydro-3, 5-dichloro-4-(4'-N, N-dimethylaminophenyl) pyrimido-[4, 5-c] pyridazine (XX) was obtained, the structure was established by nuclear magnetic resonance spectra of dechlorination and hydrolysis products. Amination of XX affored 3-chloro-5-amino compounds.

2‐Phenyl‐5‐(trichloromethyl)‐1,3,4‐oxadiazoles, A new class of antimalarial substances

AbstractAn investigation of hybrids of 2,5‐dimethyl‐1,3,4‐oxadiazole (I) and α,α,α,α',α',α'‐hexachloro‐p‐xylene (Hetol®) (II) as potential antimalarial agents led to the synthesis of representative 2‐phenyI‐5‐(trichloromethyl)‐1,3,4‐oxadiazoles (VIa‐f, VIII‐X) and related trichloromethyl 1,2,4‐oxadiazole, 1,3,4‐oxadiazoles, and 1,3,4‐thiadiazole (VII, XIII‐XV). Treatment of the appropriately substituted benzoic: acid hydrazides (IVa‐f) with trichloroacetic anhydride afforded the intermediate 1‐benzoyl‐2‐(triehloroacetyl)hydrazines (Va‐f) which were cyclized to the desired 5‐(chlorophenyl, tolyl, or α,α,α‐trifluorotolyl)‐2‐(trichloromethyl)‐1,3,4‐oxadiazoles (VIa‐f) (44–66%) in situ utilizing phosphorous oxychloride. Chlorination of the 5‐tolyl‐2‐(trichloromethyl)‐1,3,4‐oxadiazoles (VId‐f) afforded 2‐(trichloromethyl)‐5‐(α,α,α‐trichloro‐m‐ and p‐tolyl)‐1,3,4‐oxadiazole (VIII and IX) and 2‐(α,α,α,α',α',α'‐hexachloro‐3,5‐xylyl)‐5‐(trichloromethyl)‐1,3,4‐oxadiazole (X) in 23–56% yield. Each of the 2‐phenyl‐5‐(trichloromethyl)‐1,3,4‐oxadiazoles (VIa‐f, VIII‐X) was active against Plasmodium berghei in mice when administered in single 160 or 640 mg./kg. subcutaneous doses or given orally by drug‐diet for 6 days at doses of 29–336 mg./kg./day. The 2‐(trichloromethyl)‐5‐(α,α,α‐trichlorotolyl)‐1,3,4‐oxadiazoles (VIII‐X) were the most active compounds prepared and exhibited activity against P. berghei comparable with Hetol®. Structure‐activity relationships are discussed.

The Analysis of some Pyrazolone Dyes

Usually azo compounds are identified by cleavage of azo group by reduction, followed by identification of produced. amines This method, however, can not be successfully applied to azo dyes with pyrazolone component, because the resulting amino-pyrazolones are unstable and change rapidly into very complex rubazonic acids. On the other hand, when the hydroxyl group at 5-position of pyrazolone was substituted by chlorine with phosphorous oxychloride, the resultant amino pyrazole derivatives were stable. By this way identification of pyrazolone component can be accomplished.

Synthesis of Some Substituted Benzoxazole [3,4-b] imidazoles

In this paper the synthesis of 4-substituted benzoxazole [3,4-b] imidazole (9,10) and 4-aryl hexahydrobenzoxazole [3,4-b] imidazole (13,14) is reported. Glycine was treated with benzoyl chloride or p-nitrobenzoyl chloride to give N-aroyl glycine (1,2), the reaction of N-aroyl glycine with thionyl chloride followed by treatment the product (3,4) with ammonium hydroxide to give N-aroyl glycine amide (5,6). Treatment of the amide with 1-bromocyclohexanone gave N-methylene-2-hexahydrobenzoxazole) aryl amide (7,8), cyclization of this gave product (9,10), whereas the compounds (13,14) was synthesized from o-aminophenol and the acid chlorides to give N-methylene (2-benzoxazole) aryl amide (11,12) which cyclized with phosphorous oxychloride to give the products (13,14). The structure of all synthesized compounds were confirmed by physical and spectral data.

Furannes et pyrroles disubstitués en 2,3—IX : Nouvelle methode de synthèse des aza-5 indoles

N-methyl 2-formyl 3-carbethoxy pyrroles react with nitromethan in alcoholic sodium ethoxide solution to give the corresponding 1-[2′-(3′-carbethoxypyrryl)] 2-nitroethanols which are reduced to pyrrylethanolamines by catalytic hydrogenation. These compounds were isolated as acetate salts and cyclized in basic medium to produce 1-methyl-4,5,6,7-tetrahydro-4-oxo-7-hydroxy-5-azaindoles. After deshydratation by heating above their m.p., phosphorous oxychloride transformed the compounds into 1-methyl-4-ch]oro-5-azaindoles, the chlorine atom of which was replaced by nucleophilic agents such as amines, thiourea and hydrazine to give the corresponding alkylamino, dialkylamino, mercapto and hydrazino derivatives.

Isolation and characterization of 4-chloro-3,4′;3′,4″-tercoumarin

The products from the reaction of 4-hydroxycoumarin with phosphorous oxychloride are the reported 4-chlorocoumarin and an additional compound of high molecular weight. This latter compound was characterized by substitution, degradation, and deuteration reactions as 4-chloro-3,4′;3′,4″-tercoumarin, a trimer corresponding to condensations between three coumarin molecules.

Synthesis of 2-aminomethyl-1,1-diphenylbut-1-ene (studies on the synthesis of heterocyclic compounds. CCXXXIX)

Ethyl α-ethyl-β-hydroxy-β, β-diphenylpropionate (IV) was obtained in 71% yield from Reformatsky reaction between ethyl α-bromo-n-butyrate (III) and benzophenone. After the dehydration of IV with phosphorous oxychloride, the resulting ethyl α-ethyl-β, β-diphenylacrylate (VII) was hydrolized to give α-ethyl-β, β-diphenylacrylic acid (VIII), which was reacted to acid chloride with thionyl chloride in pyridine, and it was treated with ammonia giving α-ethyl-β, β-diphenylacrylamide (IX). IX was reduced with lithium aluminium hydride in dehydrated tetrahydrofuran to give 2-aminomethyl-1, 1-diphenylbut-1-ene (I), which was confirmed as its hydrochloride. On the other hand, as abnormal products, 1, 1-diphenylbut-1-ene (V), 2-ethyl-3-phenyliden-1-one (XIII) and XI were produced and they were confirmed by the elemental analyses and spectral data.

Sydnones—III: Some reactions of lithium phenylsydnone with acid and non-metallic chlorides

The reactions of lithium phenylsydnone with the acid chloride of 3-phenylsydnonyl 4-carboxylic acid, as well as with acetyl, valerianyl, benzoyl, oxalyl chlorides and with phosphorous trichloride, phosphorous oxychloride, sulphur monochloride and thionyl chloride, are described.

The carotenoids of blue-green algae—III. : A comparative study of mutatochrome and flavacin

Flavacin, obtained in small quantity from Aphanizomenon flos-aquae and Oscillatoria agardhii has been directly compared with mutatochrome (III), synthesized by monoperphthalic acid oxidation of β-carotene (I) to β-carotene-monoepoxide (II) and subsequent acid rearrangement. The results favour identity, although the available evidence does not rule out stereochemical differences. Complex metal hydride reduction of mutatochrome (III) (and flavacin) resulted in hydrogenolytic opening of the oxide ring. The main product 5-hydroxy-5,6-dihydro-β-carotene (IV) was dehydrated by phosphorous oxychloride to α-carotene (V).

五酸化リンよりオキシ塩化リンの生成反応

五酸化リンよりオキシ塩化リンの生成反応

Synthesis of 4-hydroxy-, 4-chloro-, 4-amino- and 4-substituted aminoisoxazolo [5.4-d] pyrimidines

Treatment of 4-hydroxyisoxazolo [5.4-d] pyrimidines (II) with phosphorous oxychloride furnishes the 4-chloro analogues (III) which react readily with ammonia, primary and secondary amines yielding the corresponding 4-amino, 4-mono and 4-disubstituted amino derivatives (IV) respectively.

γ-Butyrolactoneの利用研究 (第10報)

2, 5-Dimethoxyaniline and α-acetyl-γ-butyrolactone were reacted to 2-[1-(2, 5-dimethoxyphenylimino) ethyl]-γ-butyrolactone (I), which was later treated with phosphorous oxychloride to give 2-methyl-3-(2-chloroethyl)-4-chloro-5, 8-dimethoxyquinoline (II). Treatment of (II) with either acetic acid or thiourea afforded the corresponding 4-methyl-6, 9-dimethoxy-2, 3-dihydrofuro [3, 2-c]-quinoline (III) and 4-methyl-6, 9-dimethoxy-2, 3-dihydrothieno [3, 2-c] quinoline (VI), respectively. (III) and (VI) were treated with 47% hydrobromic acid to give 4-methyl-2, 3-dihydrofuro [3, 2-c] quinoline-6, 9-diol hydrobromide (IV) and 4-methyl-2, 3-dihydrothieno [3, 2-c] quinoline-6, 9-diol hydrobromide (VI) which were converted to 4-methyl-2, 3-dihydrofuro [3, 2-c] quinoline-6, 9-dione (V) and 4-methyl-2, 3-dihydrothieno [3, 2-c] quinoline-6, 9-dione (VIII) respectively by the oxidation of potassium permanganate in sulfuric acid.

Formation of different esterphosphates in the reaction of dehydroepiandrosterone with phosphorous oxychloride

Studying the reaction of dehydroepiandrosterone (DHEA) with phosphorous oxychloride in ether/pyridine, we obtained the monophosphate (I), pyrophosphate (II) and diesterphosphate (III) of DHEA. The three esterphosphates may be separated on the basis of their different solubility and also by column chromatography on alumina. Several forms of I are obtained, differing in their contents of crystal water and alcohol respectively.

Dibenzo‐azepine, ‐diazepine, ‐Oxazepine und ‐thiazepine. 3. Mitteilung über siebengliedrige Heterocyclen

AbstractAn examination of the BISCHLER‐NAPIERALSKI reaction starting with 2‐acylamino‐diphenyl‐amines, ‐sulfides, ‐methanes, and ethers, resp., is reported. Using phosphorous oxychloride or polyphosphoric acid, the products are azomethine derivatives of 5H‐dibenzo[b, e]‐1,4‐diazepines, dibenzo[b, f]‐l,4‐thiazepines, llH‐dibenzo[b, e]‐azepines resp. dibenzo[b, f]‐l, 4‐oxazepines having the general formula III. The azomethine bridge in III can be hydrogenated catalytically or reduced with LiAlH4, to give derivatives of the general formula VI. Using several dialkylaminoalkyl chlorides in the presence of Na‐amide, these derivatives are alkylated to VII. The basic strengths of several derivatives of III and VI are reported and the correlation between the basicity and the heteroatom in III and VI is discussed. The thiazepine derivatives show a noticeably lowered basicity, which we could not explain either by the inductive or by mesomeric effects of the sulfur bridge‐atom.

A Synthesis of l-Proline from l-Glutamine

Abstract 1. Novel syntheses of optically active proline and ornithine from optically active glutamine are described. 2. Carbobenzoxy-l-glutamine esters were dehydrated to γ-cyano-α-l-carbobenzoxyaminobutyric acid esters with p-toluenesulfonyl chloride, phosphorous oxychloride or thionyl chloride. 3. Hydrogenation of γ-cyano-α-l-carbobenzoxyaminobutyric acid esters in aqueous solvent systems were effected by silk-palladium catalyst to yield mainly l-proline. 4. By hydrogenation in the presence of Raney nickel in non-aqueous solvent, l-ornithine was obtained.