Absolute configuration of ro-phenyl-2-alkylamines Ia -Ic (R = H) and their N-methyl derivatives la-Ie (R = CH 3 ) has been determined by the method of the asymmetric transformation and analysis of ORD curves. In the case of the amine Ic (R = H) also the chemical corr.elation has been used.In connection with the use of the asymmetric transformation in determining the absolute configuration of organic compounds 1 -3, the absolute configuration of co-phenyl-2-alkylamines la-Ie (R = H) and their N-methyl derivatives la-Ie (R = CH 3 ) has been determined. In molecules of these amines, the aromatic ring is separated in a various distance from the asymmetric carbon atom by a saturated chain. It was therefore of interest to measure the 0 RD curves of these compounds and to determine the influence of the aromatic chromophore on the shape and sign of the Cotton effect while the absolute configuration is equal.

The availability of [¹²⁵I]-16α-iodo-3,17β-estradiol ([¹²⁵I]-E₂) with binding characteristics similar to estrogen receptor (ER) enabled us to establish a double-labeling assay for the simultaneous determination of ER and progesterone receptors (PgR) using ¹²⁵I-E₂ and [³H]-R5020. The criteria for the establishment of such a double-labeling assay are described. 150 human mammary tumor cytosols have been investigated with the standard routine receptor assay for ER as well as PgR and the results were compared to those obtained by the double-labeling assay. ER: a coefficient of correlation of 0.691 was obtained, the parameters of the regression line were Y = 1.025 x X-0.036. When referring to the standard assay, 3 determinations were false-positive and 4 false-negative. PgR: a correlation coefficient of 0.984 was found, the parameters of the regression line were Y = 0.960 × X + 12.16. One value was false-negative and 1 false-positive. An equivalence of the two methods could be demonstrated. This new assay reduces by half the amount of tissue necessary for a valid 4-to 6-point saturation analysis, the time required for performing the assay and its cost.

Summary:A radioimmunoassay for extracted, N-acetylated human serum serotonin (5-hydroxytryptamine) is described. Antisera were raised in rabbits against a conjugate of bovine serum albumin with serotonin hemisuccinamide. Polyethylene glycol in combination with anti-rabbit immunoglobulins was used to separate bound and unbound ns \-Bolton Hunter-strolonin conjugate. Ethanol precipitation of serum proteins was used to extract serotonin, which was subsequently acetylated with acetic anhydride to N-acetyl serotonin. The average recovery was 66%. The minimal detectable concentration of N-acetyl serotonin was 0.012 μηιοΐ/ΐ serum (25 fmol per tube). The intra-assay precision (CV) was 6.8% (n = 20) at a level of 0.9 ± 0.06 μιηοΐ/ΐ. The inter-assay CV was 10% at a level of 0.49 ± 0.049 μπιοΐ/ΐ, and 25% (n = 10) at a level of 2.16 ± 0.53. Analytical recovery of serotonin, corrected for losses during extraction and acetylation, was 99 ± 13%. The only substance cross-reacting with the antibody was endogenous N-acetyl serotonin. This was detectable when the acetylation Step was omitted, and it can be removed by extraction before the acetylation. The observed r nge for the concentration of serotonin in serum was for 59 women 0.45 -3.46 (mean + SD: 1.37 ± 0.63 μπιοΐ/ΐ) aiid for 59 men 0.19 -2.8 (mean ± SD: 1.18 ± 0.56 μιηοΐ/ΐ). All values are corrected for endogenous N-acetyl serotonin: observed r nge 0 -0.18 (mean ± SD: 0.03 ± 0.03 μηιοΐ/ΐ). Radioimmunologische Bestimmung des Serotonins in HumanserumZusammenfassung: Wir beschreiben die radioimmunologische Bestimmung des extrahierten und N-acetylierten Serotoni s (5-Hydroxytryptamin) im Serum des Menschen. Antiseren wurden gegen das an Rinderserumalbumin gebundene Bernsteins uremonoamid-Derivat des Serotonins bei Kaninchen erzeugt. Polyethylenglycol und anti-Kaninchen Immimglobulin wurden zur Trennung des freien und gebundenen 125 I-markierten Serotonins verwendet. Serotonin wurde durch Ethanolfallung der Serumproteine extrahiert und anschlie end mit Essigs ureanhydrid zum N-Acetylserotonin acetyliert. Gesamtausbeute: 66%. Die Nachweisgrenze f r N-Acetylserotonin betr gt 0,012 μπιοΐ/ΐ Serum (25 fmol pro Assayr hrchen). Der Intra-Assay-Variationskoeffizient (VK> bei einer Serotoninkonzentrati n von 0,9 ± 0,06 μιηοΐ/ΐ betr gt 6,8% (n = 20), die InterAssay VK bei 0,49 ± 0,049 und 2,16 + 0,53 μηιοΐ/ΐ betragen 10 bzw. 25% (n = .10). K nstlich erh hte Serotoninkonzentrationen werden nach der Korrektur auf Extraktions-und Acetylierungsverluste zu 99 ± 13% wiedergefunden. Nur endogenes N-Acetylserotonin zeigt eine Kreuzreaktion mit dem Antik rper und kann durch Extraktion ohne Acetylierung nachgewiesen werden.

Allyl-aryl-sulfone, Allyl-diphenyl-phosphinoxid, Allylphosphonsiiure-diathylester, Allyltriphenyl-phosphoniumbromid und Allyl-triphenyl-arsoniumbromid lagern sich an basischem A1203 in die entsprechenden I-Propenyl-Verbindungen um. Allyl-diphenyl-phosphin und Diallyl-phenyl-phosphin isomerisieren sich unter Mitwirkung von Natriumathylat zu den cntsprechenden 1 -Propenyl-Verbindungen. Die Allyl-und 1 -Propenyl-Verbindungen werden IR-und NMR-spektroskopisch sowie polarographisch charakterisiert. -Bei der kathodischen Spaltung von 1-Propenyl-triphenyl-phosphoniumbromid entstehen 92% Triphenylphosphin und Propen. 1 -Propenyl-phenyl-sulfon wird elektrochemisch in Propen und Benzolsulfinsliure aufgespalten.Organic Phosphorus Compounds, 643) Allyl-Propenyl RearrangementsThe Electrochemical Behaviour of some Propenyl Compounds4) Allyl aryl suffones, allyldiphenylphosphine oxide, diethyl allylphosphonate, allyltriphenylphosphonium bromide and allyltriphenylarsonium bromide undergo rearrangement on basic A1203 (the last-named allyl compound only to a limited extent) to give the corresponding 1 -propenyl compounds. Allyldiphenylphosphine and diallylphenylphosphine also rearrange on treatment with sodium ethoxide to give the corresponding I-propenyl compounds. The allyl and I-propenyl compounds are characterised by i.r. and n.m.r. spectroscopy as well as polarographically.Cathodic cleavage of (1-propcny1)triphenylphosphonium bromide, affords triphenylphosphine and propene in 92% yield. 1-Propenyl phenyl sulfone is cleaved electrochemically to propene and benzenesulfinic acid.Es ist lange bekannt, daR sich Allyl-aryl-Verbindungen unter dem EinfluR von Basen in 1-Propenyl-aryl-Verbindungen urnlagern. Diese Isomerisierung verlauft besonders leicht, wenn das nach Deprotonierung entstehende Allyl-Anion durch elektrophile Gruppen stabili-1 ) Auszug aus der Diplomarbeit I. Ertel, Univ. Mainz 1968.

Summary:The behaviour of the antifertilizing synthetic steroid RU 38486 towards human uterine progestin receptor was investigated. RU 38486 competed in the same order of magnitude äs progesterone for the [ 3 H]R 5020 binding site of progestin receptor, whereas R 5020 was unable to compete against [ 3 H]RU 38486. This apparent contradiction could be explained by means of HPLC-chroniatography. HPLC-chromatography with an anion exchange column (MonoQ, Pharmacia, Uppsala, Sweden) showed that [ 3 H]RU 38486 forms at least two stable complexes with uterine cytosol, on one hand with serum albumin, which presents almost 90% of bound radioactivity, and on the other hand with the two native progestin receptor forms, corresponding to 4 S and 8 S receptor forms in sucrose density gradient analysis.Whether reduced binding of salt-activated RU 38486 receptor complexes to DNA-cellulose is due to reduced activation is still uncertain and remains to be further investigated. H-Markiertes RU38486: Charakterisierung der Bindungseigenschaften in Cytosol aus Introductionprogesterone in vivo, a property that is manifested "~~ ~^ , , ^ . ,~ intheinterruptionofthelutealphaseofthemenstrual RU 38486 (structure see scheine 1) is the first cycle of ^y pregnancy in women . synthetic steroid possessmg a greater afnnity for the progestin receptor in different animal target tissues There are some indications that the potent antagonist than progesterone, but without exhibiting any agonist effect of RÜ 38486 is related to the essential bioprogestin activity (1-3). Moreover, at large doses chemical Steps following progestin receptor this steroid is capable of antagonizing the effects of occupancy which leäd to the biological response i. e.