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The rearrangement of allylarylethers (allylphenylether, crotyl-4-methylphenylether) in trifluoracetic acid to the corresponding 2-allylphenols according to Svanholm & Parker [1] is shown to be of the charge-induced [3s, 3s]-type [3]. Because of the subsequent formation of cyclic ethers and other sideproducts, yields are low.

3, 4-Diphenyl-sydnone (1a) and 3-p-tolyl-4-phenyl-sydnone (1b) on irradiation with a mercury high-pressure lamp in pyrex vessels yield 2,4,5-triphenyl- (3a) and 2-p-tolyl-4,5-diphenyl-1,2,3-triazole (3b), respectively. Irradiation of 1a and 1b in the presence of dimethyl acetylene-dicarboxylate or indene leads to the formation of the pyrazoles 4a and 4b and the Δ2-pyrazolines 5a and 5b, respectively. Reactive intermediates of the photoreaction of 1a and 1b seem to be the diazirines 2a and 2b, which open to give the 1,3-dipolar structures 8a and 8b.

Asterigerina, Asterigerinoides, Asterigerinata, Eoeponidella and Amphistegina all have similar test construction and bilamellar walls, differ in chamber shape, apertures, pores and ornamentation

The stereochemistry of the transition state in the CLAISEN rearrangement of crotyl propenyl ethers (2) has been established. By heating trans, cis-, cis, cis- and trans, trans-crotyl propenyl ether at 142,5°, erythro and threo 2, 3-dimethylpent-4-en-1-al (3 and 4) were obtained. From the ratio 3/4 it was shown that the rearrangement of the three ethers largely involves (97–98%) a chair-like transition state.

The knowledge of the stereochemical course of Cope and Claisen rearrangements is important both for mechanistic and synthetic reasons. In the first part an analysis of the possible transition state geometries (cf Table 1) for these reactions is given and methods which allow to distinguish between the various geometries are discussed (cf Schemes 1 and 2). In the second part known examples are analyzed. Generally, in Cope and Claisen rearrangements of acyclic systems a chair-like transition state (C) is favoured above a boat-like (B). Steric effects may alter this preference.

The metallurgical significance of the magnetic hardness test is a matter that will require considerably more study and development before the facts are better known and better understood. At this stage of development, however, the magnetic hardness characteristics appear definitely to be related to one of the properties in the steel, at least, which contributes to the physical hardness, and there are indications that correlations also exist with other properties of the steel.

2-(1′-cis,3′-cis-)- and 2-(1′-cis,3′-trans-Penta-1′,3′-dienyl)-phenol (cis, cis-4 and cis, trans-4, cf. scheme 1) rearrange thermally at 85–110° via [1,7 a] hydrogen shifts to yield the o-quinomethide 2 (R CH3) which rapidly cyclises to give 2-ethyl-2H-chromene (7). The trans formation of cis, cis- and cis, trans-4 into 7 is accompanied by a thermal cis, trans isomerisation of the 3′ double bond in 4. The isomerisation indicates that [1,7 a] hydrogen shifts in 2 compete with the electrocyclic ring closure of 2. The isomeric phenols, trans, trans- and trans, cis-4, are stable at 85–110° but at 190° rearrange also to form 7. This rearrangement is induced by a thermal cis, trans isomerisation of the 1′ double bond which occurs via [1, 5s] hydrogen shifts. Deuterium labelling experiments show that the chromene 7 is in equilibrium with the o-quinomethide 2 (R CH3), at 210°. Thus, when 2-benzyl-2H-chromene (9) or 2-(1′-trans,3′-trans,-4′-phenyl-buta1′,3′-dienyl)-phenol (trans, trans-6) is heated in diglyme solution at >200°, an equilibrium mixture of both compounds (∼ 55% 9 and 45% 6) is obtained.

Indazoles and anthranils on irradiation with a mercury high-pressure lamp in acidic solution (H2SO4/H2O or H2SO4/CH3OH) yield 2-amino-5-hydroxy(or methoxy)-benzaldehydes (acetophenones, respectively) as major products and 2-amino-3-hydroxy (or methoxy)-benzaldehydes (acetophenones, respectively) as minor products. Photolysis of benzisoxazoles in conc. sulfuric acid results in the formation of 2,5-and 2, 3-dihydroxybenzaldehydes (acetophenones, respectively). 5-Methylindazoles form on irradiation in diluted sulfuric acid 2-amino-5-methyl-benzaldehydes.

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2-(1′-Arylallyl)-phenols (9, 10, 11, 12, 13, 14, 15, 16) are transformed on heating in N, N-diethylaniline at 225° into trans-2-aryl-3-methyl-coumarans (26, 29, 32, 34, 36, 38, 40, 42) in excellent yields. The corresponding cis-coumarans are minor products. Similar thermal behaviour is shown by 2-(1′-vinylallyl)-phenols (7, 8) which are thermally converted into trans-3-methyl-2-vinyl-coumarans (24, 19) and 5-methyl-2,5-dihydro-(1-benzoxepins) (25, 18). The latter compounds are thermally unstable and rearrange to give approximatively 3:1 mixtures of trans- and cis-3-methyl-2-vinyl-coumarans (24, 19). Reaction mechanisms for these new thermal rearrangements are discussed in schemes 2, 3 and 4. The 2-(1′-arylallyl)-phenols 9, 12 and 14 yield under acidic conditions (HBr/HOAc) the expected 3-aryl-2-methyl-coumarans 28, 35, 39 along with 2-aryl-3-methyl-coumarans 26, 34, 38 and 2-aryl-2-methyl-coumarans 44, 45, 46. The intervention of phenonium ions is discussed for these reactions (cf. scheme 5). When the 2-(1′-arylallyl)-phenols 12 and 14 were irradiated in benzene solution with a mercury high pressure lamp, the main products obtained were 3-aryl-2-methyl-coumarans 35 and 39 which were formed rapidly. 2-Aryl-3-methyl-coumarans yield also 3-aryl-2-methyl-coumarans, when irradiated in benzene solution.

Irradiation of 3-phenyl-(4), 2-methyl-3-phenyl-(8), and 2,3-diphenyl-2H-azirine (10), in benzene solution in the presence of aldehydes, yields the corresponding aryl-3-oxazolines. Photochemical reaction of 4 and 10 with carbon dioxide leads to the formation of 4-phenyl- (15) and 2,4-diphenyl-3-oxazolin-5-one (16), respectively.

Anthranils 1a, b, 4 und 5 yield on irradiation in cone. sulfuric acid 2-amino-5 hydroxy-acylbenzenes 2a, b, 6 and 7 which are isolated mainly as their acetates. Small amounts of 2-amino-3-hydroxy-acylbenzenes 3a and 3b are formed as by-products (cf. tables 1 and 2). Simila results were obtained when the corresponding 2-azido-acylbenzenes were decomposed thermally i cone. sulfuric acid (cf. tables 1 and 2). 3,5-Dimethylanthranil (8) forms, on irradiation in sulfuric acid and subsequent acetylation, 2-acetamino-5-acetoxy-6-methylacetophenone (6) and 2-acetamino-5-acetoxymethyl-acetophenone (10). The same compounds were obtained from the thermaldecomposition of 2-azido-5-methyl-acetophenone (19) in sulfuric acid.

(1961). Uptake of S35 in the Intervertebral Discs after Injection of S35-Sulphate. An Autoradiographic Study. Acta Orthopaedica Scandinavica: Vol. 30, No. 1-4, pp. 84-90.

Irradiation of 3-phenyl-2H-azirine (2) in benzene solution with a high-pressure mercury lamp yields 4,5-diphenyl-1,3-diazabicyclo[3,1,0]hex-3-ene (4) and not 3-phenylimino-4-phenyl-1-azabicyclo[2,1,0]pentane (1), as had been reported previously by others [2]. 2-Methyl-3-phenyl-2H-azirine (3) yields on irradiation a 2:1 mixture of 2-exo, 6-exo- and 2-exdo, 6-exo-dimethyl-4,5-diphenyl-1,3-diazabicyclo[3,1,0]hex-3-ene (2-exo,6-exo- and 2-endo, 6-exo-5). Irradiation of 2,3-diphenyl-2H-azirine (8) leads to the formation of 2,4,5-triphenyl-imidazole (9) and tetra-phenylpyrazine (10). The suggested reaction path for the generation of 9 and 10 is shown in Scheme 2.

The irradiation of N-acylated 11-methyl-1,2,3,4,10,11-hexahydrocarbazoles (compounds 6–10) and of the 8-methoxy derivatives 11–13 in hexane solution, with 254 nm light, in the presence of air, leads to 11-methyl-2,3,4,11-tetrahydro-1 H-carbazole (2) (table 1) and its 8-methoxy derivative 21, respectively (scheme 2). Furthermore the 8-acylated products. 14, 15, 16, 18, are formed in minor amounts by a “photoanilide” rearrangement. Irradiation of the N-acetyl-8-methoxy-indoline 12 gives in addition (by elimination of the 8-methoxy group) the 8-acetyl-indoline 14 and, by coupling, the dimeric compound 23 (schemes 2 and 4). Irradiation of the N-formyl-indoline 6 yields, besides the indolenine 2 the indoline 1 (table 1). The mechanism of the anaerobic part of these photoreactions were investigated by CIDNP experiments. It is possible to convert directly indoline 1 to the indolenine 2, in 33% yield, by irradiation at 60° in the presence of oxygen.

The possible transition state conformations (chair (S), boat (W), and twist (T), respectively cross (K) forms) and methods for their determination in the thermal ortho-CLAISEN rearrangement of allyl aryl ethers are discussed. Crotyl 3,5-dimethylphenyl ether (11) gives a mixture of 2-(α-methylallyl)-3,5-dimethyl-phenol (12) and 4-crotyl-3,5-dimethyl-phenol (13) on heating in N, N-diethylaniline. Values of 3 and 31 were obtained for the ratio of 12/13 for trans-11 and cis-11, respectively. It therefore follows that both ethers rearrange steroselectively ( > 90%) by the S or W forms of the activated complex. αMethylallyl 6-alkylphenyl ethers rearrange on heating in various solvents to a mixture of trans-and cis-2-crotyl-6-alkyl-phenols. The amount of the cis-phenols in the rearrangement products decreases with the increasing bulk of the 6-alkyl substituent. This result is only obvious if the chair form of the transition state during the rearrangement of these ethers is highly favoured. trans-Crotyl 2,6-dimethylphenyl ether (trans-33) rearranges highly steroselectively (94%) on heating to trans-4-crotyl-2,6-dimethyl-phenol (trans-34). In the case of the corresponding cis ether 33, the rapid cis trans isomerisation of this ether and the cis/trans ratio of the phenol 34 indicate that the reverse rearrangement of the intermediate ortho-dienone to the ether 33 and the further rearrangement to 4-crotyl-2,6-dimethyl-phenol (34) has little stereoselective character.

In the present study of 253 patients with chronic pain syndrome we have made a multidimensional approach. All patients have been included in the study independent of coexisting states of anxiety or depression. We included criteria for diagnosis, duration, generability and intensity of pain, anxiety and depression, psychosocial stressors and social functioning. Using this system we have evaluated the antipain effectiveness of clomipramine and mianserin in a double-blind, placebo-controlled trial. By use of the Melancholia Scale 16 patients (6%) had a major depression, and by use of the Hamilton Anxiety Scale, 72 patients (28%) had a generalized anxiety disorder. The results showed no statistically significant difference between the three treatments, when using a visual analogue scale (VAS 10 cm with cut-off score 2 cm) for severity of pains as outcome criteria or the results of VAS and Global Clinical Impression Scale using the criteria of reduction of 50% or more between the pretreatment and posttreatment scores. By use of all the assessments it is possible to make an improvement curve for each patient expressed by the area under the curve, and not even there we found a difference between the three treatments. Clomipramine and mianserin were significantly superior to placebo in the topographical pain subgroup with headache using area under the improvement curves as criteria (p less than 0.05). When the 60-item General Health Questionnaire was used to identify minor psychiatric morbidity 44% was found. We can use this as a measure of quality of life. Our results have indicated that placebo-controlled studies are still needed in this field of research.

Irradiation of 2-methyl- (1a), 2,2-dimethyl- (1b) and 2,3-diphenyl-2H-azirine (1c) in the presence of diethyl mesoxalate yields the corresponding 4-phenyl-5,5-diethoxycarbonyl-3- oxazolines 3a–c. Similar cycloadducts are observed (cf. 6) by irradiation of 1b and 1c in the presence of trifluoroacetophenone. When ethyl cyanoformate is used as trapping agent photolysis of 1b or 1c leads to cycloadducts with the carbonyl and nitrile group, respectively which are present in the cyanoformate.

Irradiation of 2-methyl- (1c) and 2,2-dimethyl-3-phenyl-2H-azirine (1d) in benzene solution in the presence of carbon dioxide yields 2-methyl-4-phenyl- (3c) and 2,2-dimethyl-4-phenyl-3-oxazolin-5-one (3d), respectively. Similar cycloadducts are observed (see table) when 2,3-diphenyl-2H-azirine (1b) and 1d are irradiated in the presence of phenylisocyanate, o-tolylisocyanate, phenylisothiocyanate or di-o-tolyl-carbodiimide.

Correlated auroral and VLF emissions have been identified at L = 4 during simultaneous recordings of TV auroral images and broadband VLF. Pulsation frequencies of 1.3 ± 0.4 Hz and 3.0 ± 0.4 Hz are prominent in the power spectra of both the VLF and the optical intensity variations. These are shown to be consistent with an external oscillator source driving at a frequency of about 3 Hz. The external source induces wave growth and strong pitch angle scattering via the cyclotron resonance interaction when the electron pitch angle distribution function is such that the flux levels exceed the trapping limit.

Six patients (two females and four males in one family) with hemiplegic migraine are described. The age of onset was between six and eighteen years. Hemiplegic attacks were usually accompanied by transient neurological disturbances referable to the territory of the vertebrobasilar arterial tree. Brain-stem involvement and vertebrobasilar dysfunction in the reported family was supported by angiography in one case, revealing a marked and prolonged spasm of the basilar artery. Despite its dramatic character and occasionally prolonged deficits the course was essentially benign. Hemiplegic attacks disappeared during adolescence in five of the six patients. No permanent neurological residual phenomena were encountered during a mean follow-up of 14 years. The possibility is raised of a genetically determined susceptibility to periodic vasoconstriction in a particular vascular area as the basis of the syndrome.

Acute mesenterial ischemia resulting from thrombosis of atherosclerotic mesenterial arteries still carries a very high mortality, even when revascularization is undertaken early. Four patients are presented in whom acute revascularization of the superior mesenteric artery with minor intestinal resections were performed. Three of the patients had previous histories of abdominal angina; one of these died postoperatively. Of the surviving three patients, two were free of gastrointestinal symptoms 13 and 19 months after the operation respectively, while the last was still hospitalized three months postoperatively with frequent bouts of diarrhea and feeding problems. Since approximately 50 per cent of patients with acute intestinal ischemia develop abdominal angina prior to the acute exacerbation, it is of utmost importance to diagnose this condition before onset of the acute episode, as an elective operation has a low mortality and a good long-term prognosis. A dramatic improvement in the operative results of the acute episode are not to be expected, but revascularization as soon as possible after the onset of the acute episode combined with localized intestinal resection as required can improve the prognosis, especially in younger patients free from complicating cardiac disease.

Plasma CEA levels have been determined in 92 normal women and 768 women with benign or malignant breast diseases. Only one of 92 normal women had a CEA level above 5 ng/ml. Of 253 women with benign breast diseases (gross cystic disease, adenofibroma, fibrosis, etc.) only one had a CEA level above 5 ng/ml. Ninety-four percent of the above two groups of women had CEA levels below 3 ng/ml. Of 164 women operated upon for Columbia Clinical Classification Stage A or B breast carcinoma, preoperative CEA levels were above 5 ng/ml in seven (4%). Patients with a preoperative CEA level above 3 ng/ml seemed to have an increased incidence of tumor recurrence. Elevated CEA levels (greater than 10 ng/ml) in our postmastectomy population of 288 patients have correlated with development of metastases in 14 of 46 subjects. Of 216 patients under treatment for metastatic breast carcinoma, CEA levels above 10 ng/ml have been detected in 15 percent of patients with soft tissue metastases, 38% of patients with visceral metastases and 50% of patients with osseous metastases. Of metastatic breast carcinoma patients with CEA levels above 10 ng/ml serial measurements have correlated with the patients response to therapy, progressively increasing in treatment failures and decreasing in treatment responders.

The advent of immunoperoxidase histochemistry techniques has allowed the more convenient visualization by light microscopy of antigenic cellular constituents. Application of the unlabeled and labeled antibody enzyme methods to the localization of carcinoembryonic antigen in conventionally prepared tissue specimens has revealed the feasibility of using immunoperoxidase techniques in routine diagnostic pathology. The methods involved are well defined and once antibody specificity and antigen stability are determined, they are adaptable to the identification of other immunological markers that may appear in malignant tissue specimens.

We have previously reported that human anti-mouse IgG antibody (HAMA) can cause false-positive and false-negative results in "sandwich"-type monoclonal antibody (MAb) assays. To eliminate HAMA interference in "sandwich"-type MAb assays, we investigated the use of MAb on solid-phase, vinylidene fluoride floccules, which we have previously used as a solid-phase second antibody for RIA. The simple procedure effectively removes greater than 95% of HAMA from the most positive serum we have obtained from patients hyperimmunized to murine MAb, and it allows for accurate quantification of carcinoembryonic antigen. The solid-phase complex, added to blood, effectively removes HAMA and (or) "HAMA-type" heterophilic antibody from the sera or plasma.