Über Benzo‐polymethylen‐Verbindungen, VII.: Pharmakologische Analoga des ac .‐β‐Amino‐tetrahydro‐naphthalins

Abstract

400. Julius v. Braun, Heinrich Oruber und G e o r g Kir SJ c hb Bum: ober Benzo-polymethylen-Verbindungen, VII. : Pharmakologische Analogs des ac.-,8-Amino-tetrahydro-naphthalins. [Aus (I. Cliein. Institut d. Landwirtschaftl. IIochschule Bcrlin u. d. Chcm. Institut d. Universitjt Frankfurt a. M . ] (Eingegangen an1 13. Olitober 1912.)Die aliphatische, in @-Stellung zu einein aromatischen Kern gebundene A m i n o g r u p p e bedingf, allgemein gesprochen, eine crheblichc physiologische Wirksamkeit des Molekuls, die sich namentlich in der B l u t d r u c k -S t e i g e r u n g kundgiht: man findet diese JVirkung beim einfachstea ~-Aminoathyl-benzol (I.), bei seincn IIomologen, beiin (3-Amino-hydrinden (11.)1), beim l3-Airtino-(3-methylhydrinden (111.) 2) uiid endlich beim 0 -A m i n ot e t r ah y d r on a p h t 11 a 1 i n (IV.) wieder. y\,CHa I. LJ 'C&.NHzDiese letztere Base zeigt nun in physiologischer Bezieliung Eigentumlichkeiten sehr benierkenswerter Art, die sich wedcr bei I., iioch bei 11. oder 111. wiederfinden: sic wirkt, abgesehen davon, da13 sie BlutgefiiDe kontrahiert und daclurch den Blutdruclr steigert, auch noch n i y d r i a t i s c h und e r h i j h t s t a r k d i e K o rp e r t e m p e r a t u r s ) . Da diesc Wirkungen sich bei I., 11. und 111. nicht wiederfinden, so sind sic offenbar a n die g l e i c hz e i t i g e G e g e n w a r t d c s a r o r n a t i s c h e n u n d h y d r o -a r om a t i s c h e n R i n g e s gelinupft.Der Zweck der vorliegenden Untersuchung war, festzustellsn, ob fur das Znstandelrommen der eigenartigen physiologischen Wirkungen des ac.-(3-Ainiiio-tetralins g a n z e i n d e u t i g die strukturellcn Gedingungcn seines Afolekularbaues erfullt sein miissen, oder ob man, ohne diese Wirliungen zu vcrnichten oder mcnigstens weitgehend zu schwiichen, den aromatischen Kern, den hydro-1) K e n n e r und h l a t l i e w s , SOC. 105, 745 [1011]. -2) J. v. B r a u n , 0. K r u b e r und E. D a n z i g e r , R. 49, 2642 [1916]. 3 ) B. 21, 1115 [18S8].

Steric acceleration of lactonization reaction: an analysis of "stereopopulation control"

“…(29) (23) An unidentified peak was observed in the GLC analysis of the reaction (30) mixture from the thermolysis of 1-pentanesulfonyl azide in 2,4-dimethyl- (31) pentane. From its retention time we suspected It to be either the fiveor six-membered sultam formed by nitrene backbiting, but no attempt was (32) made to isolate the product.…”

Chemistry of carbanions. 31. Cyclization of the metal enolates from .omega.-bromo ketones

“…An authentic sample of the ketone 36 (Aldrich Chemical Co.) was recrystallized from hexane to separate the pure ketone 36 as colorless needles: mp 155-157 "C (sealed capillary) [lit.34 mp 151-152 "C]; IR (cc14) 1722 cm-* (C=O); NMR ( C c 4 ) 6 1.3-2.6 (m, aliphatic CH); mass spectrum m/e (re1 intensity) 138 (M+, loo), 82 (65),81 (41),68 (46), 67 (94), 54 (461, and 41 (46). I. Bromo Ketone 42 with i-PrzNLi.…”

“…(13 H, m, aliphatic CH); mass spectrum m/e (rel intensity) 220 (M+, <1), 218 (M+, <1), 139 (100), 138 (28), 111 (20), 110 (34), 109 (20), 98 (24), 95 (44), 81 (31), 69 (34), 67 (28), 55 (56), 41 (41), and 39 (23).…”

“…A 1.132-g aliquot was subjected to low-pressure liquid chromatography on silica gel with an Et20hexane eluent (2:3 v/v) to separate early fractions containing 244 mg of isomer 65a, n2Bo 1.4408, 542 mg of intermediate fractions containing (TLC) mixtures, and finally fractions containing 80 mg of isomer 65b, n25o 1.4466. The spectral properties of isomer 65a follow: IR (CCD 1722 (ester C=0), 1708 (C=0), and 1640 cm-1 (weak, C=C); UV (95% EtOH) end absorption with 16900 at 210 nm; NMR (CC14) 6.86 (1 H, q, J = 7 Hz, vinyl CH), 2.28 (3 H, s, COCH3), 1.88 (3 H, d, J = 7 Hz, CH3), and 1.52 (9 H, s, t-Bu); mass spectrum m/e (rel intensity) 169 (1), 128 (32), 111 (44), 69 (45), 57 (100), 43 (56), and The spectral properties of isomer 65b follow: IR (CCI4) 1725 (ester 0=0), 1700,1682 (0=0), 1645, and 1628 cm"1 (C=C); UV max (95% EtOH) 217 nm (e 8400); NMR (CCI4) 6.80 (1 H, q, J = 7 Hz, vinyl CH), 2.21 (3 H, s, CH3CO), 1.94 (3H,d,J = 7 Hz, CH3), and 1.54 (9 H, s, -Bul; mass spectrum rule (rel intensity), 169 (2), 129 (60), 128 (43), 113 (23), 111 (94), 74 (43), 69 (73), 57 (100), 43 (80), 41 group should be assigned structure 65b. Also based on the expectation that the group cis to the methyl group is more likely to be twisted away from coplanarity with the remainder of the system, it is reasonable to assume that the UV spectrum of isomer 65a will EtOH) 220 nm (e 10 800)25b].…”

“…The ketone 52 was obtained as a colorless liquid: n26n 1.4130 (lit. bp 113.5-114 °C,35 n20D 1.4 1 5036b); IR (CC14) 1781 cm"1 (C=0); NMR (CC14), 3.02 (2 H, t, J = 8.5 Hz, further partially resolved splitting apparent, CH2CO), 1.80 (2 H, t, J = 8.5 Hz, further partially resolved splitting apparent, CH2), and 1.18 (6 H, s, CH3); mass spectrum m/e (rel intensity) 98 (M+, 13), 70 (63), 56 (88), 55 (50), 42 (59), 41 (100), and 39 (35). These spectral features correspond to those previously reported38 for the ketone 52 and the NMR spectrum of our product clearly excludes the presence of any appreciable amount of the isomeric ketone 53.36b K. Bromo Ketone 50 with KOH in H20-DME.…”