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Les facteurs électroniques dans la réaction de formylation des hydrocarbures aromatiques condensés
Abstracts
CHEMISTRY THE ISOLATION
of some accepted
Tetrahedroo
papers
29
OF THE PODOCARPACEAE-II
OF GENISTEIN
FROM PODOCARPUS
AND THE CONSTITUTION
SPICATUS
OF PODOSPICATIN
L. H. BRIGGSand T. P. CEBAU) Dept. of Chemistry, University of Auckland, New Zealand (Received 10 Novmbm Abstract-Genistein has been isolated from the heartwood. the constitution 5:5’:7-trihydroxy-2’:~6-dimethoxyisoflavone.
1958) Podospicatin has be811shown to have
SUR LA SYNTHl-?SE DU DIBENZO[A,I]PYRENE, DU TRIBENZO[A,EI]PYR&NE, ET DE NOUVEAUX HOMOLOGUES DU NAPHT0[2,3-AIPYRENE et DENISE LAVIT lnstitut du Radium, Universiti de Paris
N. P. Buu-Hoi
(kceiued 6 November 1958)
R&mm&--Ledibcnzo[a,i)pyr&ne (I) a CtCsynthttist &partir du benzo[alpyrene par condensation
avec I’anhydride succinique en position 1, reduction de I’acide Cctonique obtenu en acide y-l-benzo[a]pyrbnyl-butyrique, cyclisation en 4-c&o-l :2:3 :44etrahydrodibenz~a,i&yrene, reduction de cette c&one en 1:2:3:4-tttrahydro-dibenzo[a,i]pyrene, et d&hydrogenation. D’autre part, la synthese du tribenzo[a,e,i]pyrene a partir de l’octahydroanthra&ne symetrique a et& r&xamin&, et celle de deux nouveaux homologues du naphto[2,3-a]pyr&ne est d&rite. Abstract-The synthesis of dibenzo[a,i]pyrene is reported, starting from benzo[alpyrene. obtained by condensation of succinic anhydride in position 1, followed by reduction of the resulting keto acid to y-I-benzo[a]pyrenylbutyric acid, and cyclisation to 4-keto-I :2:3 :4-tetrahydrodibenzo[a,ilpyrene; the latter ketone was reduced to 1:2:3 :4-tetrahydrodiber&a,ibyrene, which was then dehydrogenated. Further, the preparation of symmetrical octahydroanthracene has been re-examined, and the synthesis of two new homologues of naphtho[2,3-alpyrene is described.
LEE FACTEURS BLECTR~NIQUES DANS LA ~~A~ION DE FORMYLATION DES HYDROCARBURES AROMATIQUES CONDENS& N. P. Buu-Hoi, DENISE LAVIT et 0. CHALVFJT Institut du Radium, Universite
de Paris
(Received6 Nimember1958) R&m&-On montre, par Nude
de la formylation
de plusieurs hydrocarbures
aromatiques condens&
30
Abstracts of some accepted Tetrahedroo papers
qu’8 l’intcrieur dcchaque classe dCtcrminCe d’hydrocarburcs. la facilitC de formylation cst unc fonction croissantc de I’indice de valence librc sur le sommet qui entrc en reaction. Cette r&gle permet de prevoir, outrc la reactivite des hydrocarburcs eux-mimes, egalcment celle dcs divcrses positions 1 l’int&itur de chacunc de ces mol&ules. On applique ces observations ,& l’ttude du tribenzo[a,cJ]naphtadnc et du phCnanthro[2,3-alpyrtne, qui donncnt chacun un seul aldthydc, conformemmt &la thCorie, laquclle indiquc. comme positions priviEgi&s, le sommct I7 dans le premier cas, et lc sommet 6 dans lc second cas. Abstract-A study of the formylation of several condensed aromatic hydrocarbons shows that within each class of such hydrocarbons, the reactivity increases with the free valence. index of the position to be substituted. This rule makes it possible to predict not only the behaviour of the hydrocarbons themselves, but also that of the various positions inside each molecule. These considerations arc applied to tribcnzo[a,c,j]naphtacene and phcnanthro[2.3-alpyrcnc, each of which gave a single aldchydc, in accordance with the theory, the formylation site predicted being position 17 in the first case, and position 6 in the second.
SYNTHESE DU 1:6-ANHYDRO-GALACTOSE A. FERNEZet P. J. ST&FVN Universit6 Libre de Bruxellcs, Facult6 des Sciences, Service de Chimie Organique (Received 6 November 1958) Abstract-1 :6-anhydro+D-galactopyranose has been synthesised from galactoae in a 70 per cent yield. Purification of intermediate derivatives was made unnecessary. R6wm6-La synthase du 1:6-anhydro-/I-D-galactopyranose a CtC r&is& avec un rendcmcnt global de 70% g partir de galactose et sans isolemcnt des produits interm6diaires.
ETUDES CINETIQUES DES REACSIONS DE SOLVOLYSE DE CHLORURES D’a-PHENYLETHYLE SUBSTITUES EQUATIONS
DE HAMMETT, WINSTEIN-GRUNWALD C. MBCHJSLYNCK-DAVID
et
ET TOMMILA
P. J. C. FIERENS
(Rreeiocd 6 Noocnrbcr 1958) Ab&act-The kinetic study of the solvolysis of m-CH,, p_CH,, m-OCH*, pc1, mc1 and pF substituted a-phcnylethyl chlorides has been carried out in the following media: water 20.5% dioxane 795% dioxane 50.7% water 493% dioxane 33.33 % water 6666% formic acid 69.7% dioxane 25.8 % water 5.3% formic acid 54.1% dioxanc 39.8 % water 6.1% formic acid 34.0% dioxane m2% water 5.8 ‘A Correlation of solvolysis rates has b&n made with the equations of Hammett, Wiusteinawaid and Tommila.
CHEMISTRY THE ISOLATION
of some accepted
Tetrahedroo
papers
29
OF THE PODOCARPACEAE-II
OF GENISTEIN
FROM PODOCARPUS
AND THE CONSTITUTION
SPICATUS
OF PODOSPICATIN
L. H. BRIGGSand T. P. CEBAU) Dept. of Chemistry, University of Auckland, New Zealand (Received 10 Novmbm Abstract-Genistein has been isolated from the heartwood. the constitution 5:5’:7-trihydroxy-2’:~6-dimethoxyisoflavone.
1958) Podospicatin has be811shown to have
SUR LA SYNTHl-?SE DU DIBENZO[A,I]PYRENE, DU TRIBENZO[A,EI]PYR&NE, ET DE NOUVEAUX HOMOLOGUES DU NAPHT0[2,3-AIPYRENE et DENISE LAVIT lnstitut du Radium, Universiti de Paris
N. P. Buu-Hoi
(kceiued 6 November 1958)
R&mm&--Ledibcnzo[a,i)pyr&ne (I) a CtCsynthttist &partir du benzo[alpyrene par condensation
avec I’anhydride succinique en position 1, reduction de I’acide Cctonique obtenu en acide y-l-benzo[a]pyrbnyl-butyrique, cyclisation en 4-c&o-l :2:3 :44etrahydrodibenz~a,i&yrene, reduction de cette c&one en 1:2:3:4-tttrahydro-dibenzo[a,i]pyrene, et d&hydrogenation. D’autre part, la synthese du tribenzo[a,e,i]pyrene a partir de l’octahydroanthra&ne symetrique a et& r&xamin&, et celle de deux nouveaux homologues du naphto[2,3-a]pyr&ne est d&rite. Abstract-The synthesis of dibenzo[a,i]pyrene is reported, starting from benzo[alpyrene. obtained by condensation of succinic anhydride in position 1, followed by reduction of the resulting keto acid to y-I-benzo[a]pyrenylbutyric acid, and cyclisation to 4-keto-I :2:3 :4-tetrahydrodibenzo[a,ilpyrene; the latter ketone was reduced to 1:2:3 :4-tetrahydrodiber&a,ibyrene, which was then dehydrogenated. Further, the preparation of symmetrical octahydroanthracene has been re-examined, and the synthesis of two new homologues of naphtho[2,3-alpyrene is described.
LEE FACTEURS BLECTR~NIQUES DANS LA ~~A~ION DE FORMYLATION DES HYDROCARBURES AROMATIQUES CONDENS& N. P. Buu-Hoi, DENISE LAVIT et 0. CHALVFJT Institut du Radium, Universite
de Paris
(Received6 Nimember1958) R&m&-On montre, par Nude
de la formylation
de plusieurs hydrocarbures
aromatiques condens&
30
Abstracts of some accepted Tetrahedroo papers
qu’8 l’intcrieur dcchaque classe dCtcrminCe d’hydrocarburcs. la facilitC de formylation cst unc fonction croissantc de I’indice de valence librc sur le sommet qui entrc en reaction. Cette r&gle permet de prevoir, outrc la reactivite des hydrocarburcs eux-mimes, egalcment celle dcs divcrses positions 1 l’int&itur de chacunc de ces mol&ules. On applique ces observations ,& l’ttude du tribenzo[a,cJ]naphtadnc et du phCnanthro[2,3-alpyrtne, qui donncnt chacun un seul aldthydc, conformemmt &la thCorie, laquclle indiquc. comme positions priviEgi&s, le sommct I7 dans le premier cas, et lc sommet 6 dans lc second cas. Abstract-A study of the formylation of several condensed aromatic hydrocarbons shows that within each class of such hydrocarbons, the reactivity increases with the free valence. index of the position to be substituted. This rule makes it possible to predict not only the behaviour of the hydrocarbons themselves, but also that of the various positions inside each molecule. These considerations arc applied to tribcnzo[a,c,j]naphtacene and phcnanthro[2.3-alpyrcnc, each of which gave a single aldchydc, in accordance with the theory, the formylation site predicted being position 17 in the first case, and position 6 in the second.
SYNTHESE DU 1:6-ANHYDRO-GALACTOSE A. FERNEZet P. J. ST&FVN Universit6 Libre de Bruxellcs, Facult6 des Sciences, Service de Chimie Organique (Received 6 November 1958) Abstract-1 :6-anhydro+D-galactopyranose has been synthesised from galactoae in a 70 per cent yield. Purification of intermediate derivatives was made unnecessary. R6wm6-La synthase du 1:6-anhydro-/I-D-galactopyranose a CtC r&is& avec un rendcmcnt global de 70% g partir de galactose et sans isolemcnt des produits interm6diaires.
ETUDES CINETIQUES DES REACSIONS DE SOLVOLYSE DE CHLORURES D’a-PHENYLETHYLE SUBSTITUES EQUATIONS
DE HAMMETT, WINSTEIN-GRUNWALD C. MBCHJSLYNCK-DAVID
et
ET TOMMILA
P. J. C. FIERENS
(Rreeiocd 6 Noocnrbcr 1958) Ab&act-The kinetic study of the solvolysis of m-CH,, p_CH,, m-OCH*, pc1, mc1 and pF substituted a-phcnylethyl chlorides has been carried out in the following media: water 20.5% dioxane 795% dioxane 50.7% water 493% dioxane 33.33 % water 6666% formic acid 69.7% dioxane 25.8 % water 5.3% formic acid 54.1% dioxanc 39.8 % water 6.1% formic acid 34.0% dioxane m2% water 5.8 ‘A Correlation of solvolysis rates has b&n made with the equations of Hammett, Wiusteinawaid and Tommila.