Note sur la préparation du monoester (triméthylammonio-4-butyl)-sulfurique

4-Trimethylammoniobutyl hydrogensulfate, heated at 185°C under reduced pressure, yields 4-trimethylammoniobutylsulfuric monoester. The rate of scission of this ester in alkaline medium grows with the concentration of the OH^? ions.     

Recherches sur la formation et la transformation des esters LXXI Sur la préparation des acides ω-(phénylthiocarbamylamino)-alcoylphosphoriques et sur leur scission à divers pH

Sodium ω-phenylthiocarbamylaminoalkyl phosphates C₆H₅NHCSNH–(CH₂)_n–OPO₃Na₂ have been obtained by reacting phenylisothiocyanate with the corresponding aminoalkyl phosphoric monoester in the presence of 2 eq. of NaOH.     

Recherches sur la formation et la transformation des esters LXXIII Sur la préparation d'acides ω-[aryl (ou aralcoyl ou alcoyl) carbamylamino]-alcoylphosphoriques et sur leur vitesse de scission à divers pH

N-Aryl(or aralkyl or alkyl)carbamoyl-aminoalkyl phosphoric monoesters have been prepared by the reaction of isocyanates R′-N?C?O on the corresponding amino-alkylphosphoric monoesters H₂N? R? OPO₃H₂ in the presence of 2 equivalents of NaOH. The rates of scission of the phosphoric monoester group and occasionally of the phenylcarbamoylamino group of these monoesters have been studied at 100°, in solutions 0.1M in ester and at various pH.     

Synthèse de la diméthyl-4,4-dihydrofuranedione-2,3

4,4-Dimethyl-dihydro-2,3-furanedione ( 4 ), an intermediate in the synthesis of (+)-D -pantothenic acid, is obtained in good yield from readily available substances such as isopropyl chloride, diethyl oxalate and formaldehyde, without oxidative conditions.     

Recherches sur la formation et la transformation des esters LXXXI [1]. Sur la réaction d'isothiocyanates avec l'acide hydrazinoéthylphosphorique,et de l'isocyanate de phényle avec l'acide colaminephosphoreux

Hydrazinoethyl phosphoric monoester has been prepared by reacting hydrazinoethanol with polyphosphoric acid, and isolated as di-sodium salt. Sodium hydrazinoethyl phosphate reacts with phenylisothiocyanate (in H₂O+ethanol) to yield mainly the derivative thiocarbamoylated at the substituted nitrogen atom. This derivative, heated for one night at 100° in 0.5 N HCl, is cyclized to 3-amino-2-phenylimino-thiazolidine in 62% yield. Sodium hydrazinoethyl phosphate reacts with o-methoxycarbonylphenyl isothiocyanate (in H₂O+dioxane) at the unsubstituted nitrogen atom to yield mainly the corresponding quinazoline derivative (IV, X = OPO₃Na₂). This derivative, heated for one night at 100° in 0.5 N HCl, is cyclized to 2-o-carboxyphenylamino-dihydro-δ²-1, 3, 4-thiadiazine (Va) in 55% yield (hydrolysis of the lactamic function as well). Aminoethyl phosphorous monoester (colaminephosphorous acid) reacted with phenylisocyanate (in H₂0+dioxane) in slightly alkaline medium (one equivalent of NaOH) yields sodium N-phenylcarbamoylaminoethyl phosphite. Refluxed for 20 minutes in 1N NaOH, this carbamoyl derivative is not cyclized but only hydrolyzed to the open-chained N-phenyl-N′-hydroxyethylurea (VII).     

Recherches sur la formation et la transformation des esters LXVII. Note sur la scission des acides ω-(N-phénylthiocarbamylamino)-alcoyl-sulfuriques à divers pH

In aqueous solutions at 100°C varying from HCl 2N to NaOH 2N , N-phenylthiocarbamoyl derivatives of aminoalkylsulfuric monoesters C₆H₅NH? CS? R? OSO₃H are split in the following ways:

• (a) With R = ? CH₂? CH(CH₃)? or ? (CH₂)₃? the scission of the monoester group is very rapid in the hole pH-range studied, especially in alkaline medium; the resulting cyclic products, 5-methyl-2-phenylamino-thiazoline and 2-phenylimino-tetrahydrothiazine respectively, formed by nucleophilic attack of an unshared pair of the S atom on the C bearing the monoester group, have been isolated and identified.
• (b) With R = ? (CH₂)₄? , the rate of the scission in alkaline or neutral medium is very much higher than that of an alkylsulfuric monoester; in these media a cyclic product is also formed (this time by nucleophilic attack of the unshared pair of the thiocarbamoylated N atom on the C bearing the monoester function) which has been isolated after alcaline scission, and identified as N-phenylcarbomoyl-pyrrolidine. In acid medium, no special influence of the phenylthiocarbamoyl group is observed.
• (c) With R = ? (CH₂)₅? or ? (CH₂)₆? , the rate of the scission in alkaline medium is 30 to 1000 times lower than in the previous cases; no pure organic scission products have been isolated. In acid or neutral medium, these two esters behave like usual alkylsulfuric acids.

     

Sur le mécanisme de la réaction de meth-cohn-tarnowski de préparation des thiocoumarines

Reaction of 2-t-butylthiobenzaldehyde with N-(2-dialkylaminoethyl)-cyanacetamides followed by heating of the resulting 3-(2-t-butylthiophenyl)-2-cyanoacrylamides in polyphosphoric acid leads to the formation of 3-carboxamido-2-imino-2H-benzo[b][l]thiopyrann intermediates which afford thiocoumarins on hydrolysis. The authors postulate the intermediate formation of a thiophenate ion by an electronic mechanism involving six centers.     

Recherches sur la formation et la transformation des esters LXXIV [1] etude à l'aide de H2[18O] de la scission de quelques monoesters N-phénylthiocarbamyl(ou N-phénylcarbamyl)- aminoalcoylphosphoriques et de l'acide dibromo-2,3-allyl-phosphorique

The scission of some N-phenylthiocarbamoyl(or phenylcarbamoyl)-aminoalkyl phosphoric monoesters and of 2,3-dibromoallyl phosphoric monoester is studied in H₂[¹⁸O], at 100°C and at various pH.     

Etude de l'oxydation de tétrahydroisoquinoléinols-4 diméthoxylés en 6,7 ou 7,8, et sur la réactivité du carbonyle de la tétrahydroisoquinolone-4 diméthoxylée en 6,7

Preparation of the tetrahydroisoquinolin-4-ols indicated in the title and their oxidation by different reagents (chromic anhydride, NBA, dimethylsulfoxide, Oppenauer oxidation) is reported. Only the last reaction led to the title compounds, while the other reagents (except NBA) yielded 1,2,3-trioxotetrahydroisoquinoline. Furthermore, the reactivity of 6,7-dimethoxytetrahydroisoquinolin-4-one was examined towards different carbonyl reagents.     

Quaternarisation de diméthyl-5,6 pyrazolidino[4,3-d )isoxazolines-2

We have determined the quaternization site of bicyclic molecules such as dimethyl-5,6 pyrazolidino[4,3-d]isoxazolines-2 containing two vicinal sp³ nitrogen atoms in a cycle and one sp² nitrogen atome in the other by spectral methods and by degradation of their corresponding iodomethylates. The quaternization takes place on one of the two sp³ nitrogen atoms and is controlled by steric effects.     

Recherches sur la formation et la transformation des esters LXXVII [1]. Etude à l'aide de H2[18O] de la scission de quelques monoesters phosphoreux et de l'acide propargyl-benzènephosphonique

(1) Monopotassium phosphite KH₂PO₃ heated at 300°C with CO[¹⁸O] exchanges one atom of oxygen after 3 hours, one to two atoms after 6 hours, and its three O atoms after 12 hours; the probable mecanism of this exchange is discussed. When the same treatment is carried out in the presence of o-phenylene diamine hydrochloride, the exchange is total (three O) after 3 hours at 300°C. Treated by this last procedure, benzenephosphonic acid C₆H₅PO(OH)₂ undergoes equally a total exchange of its O atoms in 3 hours.     

Action d'organolithiens sur la méthyl-2 quinoxaline. Etude de la réactivité des adduits

The action of organolithium reagents such as phenyllithium or n-bulyllithium on 2-methylquinoxaline gave lithiation of the methyl group which upon reaction with electtropholesphiles produce side chain alkenyl derivatives. On the other hand organolithium reagents react with the quinoxaline azomethine bond to give I-lithio-2-alkyl)or ary-1)-3 methylquinoxalines which can be further loithiated on the methyl group to give 2-alkyl(or aryl)-3-alkenylquinoxaline derivatives. The adducts can be condensed with clectrophiles such as benzonitrile or methlyl benzoate but only methyl benzoate leads to N condensed derivatives. Furthermore substituted 1,2,3,4-terahydroqinoxalines are available via the above lithio intermediates.