Betylates. 1. Synthesis and reactions of an isolable [0]betylate, N,N-dimethyl-N-(phenoxysulfonyl)methanaminium fluorosulfate

1981 ◽  
Vol 59 (2) ◽  
pp. 356-361 ◽  
Author(s):  
James Frederick King ◽  
Teresa Mee-Ling Lee
Keyword(s):  
Methyl Carbon ◽  
Phenyl Cation ◽  
Satisfactory Method

Phenyl [0]betylate fluorosulfate (2), the first example of a "[0]betylate" (trialkylammoniosulfate ester), has been prepared by methylation of phenyl N,N-dimethylsulfamate with methyl fluorosulfate. Nucleophiles react with 2 either by attack on the sulfur or methyl carbon atoms, but with no sign of any products derived from benzyne or the phenyl cation. A synthesis of enol N,N-dimethylsulfamates has been devised using a reagent, [Formula: see text], prepared from tetramethylsulfamide and methyl fluorosulfate, but no satisfactory method was found for converting the sulfamic ester to the [0]betylate. Evidence is presented that phenyl chlorosulfate reacts with trimethylamine to give the phenyl [0]betylate which then undergoes further reaction.

Effects of Ultrasounds on Neat nitrobenzene

2019 ◽  
Vol 70 (8) ◽  
pp. 3085-3088
Author(s):  
Carmen Eugenia Stavarache ◽  
Yasuaki Maeda ◽  
Mircea Vinatoru
Keyword(s):  
Nitro Group ◽  
Radical Cation ◽  
Reaction Mechanisms ◽  
Diphenyl Ether ◽  
Argon Atmosphere ◽  
Phenyl Radical ◽  
Dissolved Gas ◽  
Decomposition Products ◽  
Oxygenated Compounds ◽  
Phenyl Cation

Neat nitrobenzene was continuously irradiated at two ultrasonic frequencies: 40 and 200 kHz, under air and argon atmosphere, respectively. Samples taken at intervals of 1, 5, 10 and 24 h were analyzed by GC-MS and decomposition products were identified. Possible reaction mechanisms are discussed. Presence of air as dissolved gas leads to oxygenated compounds such as 1,4-benzoquinone, 2,4-dinitrophenol, m-dinitrobenzene while argon inhibits the decomposition of nitrobenzene, especially at sonication times under 5 h. Based on the nature of the compounds identified we advanced a mechanism, involving a divergent splitting of unstable radical cation of NB in air and argon respectively. Thus, under air, the phenyl cation formation is preferred leading to 1,4-benzoquinone nitro-biphenyls and dinitrobenzene, while under argon, the phenyl radical formation seems to be favored, leading to phenol and diphenyl ether. The oxygenated compounds detected under argon clearly are a consequence of the nitro group splitting.

scholarly journals IR photofragmentation of the phenyl cation: spectroscopy and fragmentation pathways

2021 ◽  
Vol 23 (7) ◽  
pp. 4334-4343
Author(s):  
Sandra D. Wiersma ◽  
Alessandra Candian ◽  
Joost M. Bakker ◽  
Giel Berden ◽  
John R. Eyler ◽  
...  
Keyword(s):  
Gas Phase ◽  
Spectral Range ◽  
Infrared Spectra ◽  
Fragmentation Pathways ◽  
Phenyl Cation

We present the gas-phase infrared spectra of the phenyl cation, phenylium, in its perprotio (C6H5+) and perdeutero (C6D5+) forms, in the 260–1925 cm−1 (5.2–38 μm) spectral range, and investigate the observed photofragmentation.

The ground state (1A1) and the lowest triplet state (3B1) of the phenyl cation C6H5+ revisited

1997 ◽  
Vol 106 (18) ◽  
pp. 7541-7549 ◽  
Author(s):  
Jan Hrušák ◽  
Detlef Schröder ◽  
Suehiro Iwata
Keyword(s):  
Triplet State ◽  
Ground State ◽  
Phenyl Cation

Communist International Front Organizations: Their Nature and Function

1956 ◽  
Vol 9 (1) ◽  
pp. 76-87 ◽  
Author(s):  
Bernard S. Morris
Keyword(s):  
Psychological Warfare ◽  
Satisfactory Method ◽  
And Function ◽  
Positive Results

IT was once suggested that the basic trait of psychological warfare—and, incidentally, the greatest asset to those that practice it—is its lack of known positive results.1 No satisfactory method has yet been developed to measure the effects of a propaganda campaign on its chosen audience. This characteristic is at once the greatest weakness of propaganda and psychological warfare (how does the operator know whether his effort was well spent or not?) and their greatest strength (if there is no reliable evaluation of the effort, it had better be continued, or even intensified, lest ground be lost).

scholarly journals How Suitable is Quantile Mapping For Postprocessing GCM Precipitation Forecasts?

2017 ◽  
Vol 30 (9) ◽  
pp. 3185-3196 ◽  
Author(s):  
Tongtiegang Zhao ◽  
James C. Bennett ◽  
Q. J. Wang ◽  
Andrew Schepen ◽  
Andrew W. Wood ◽  
...  
Keyword(s):  
Joint Probability ◽  
Ensemble Model ◽  
Ensemble Spread ◽  
Quantile Mapping ◽  
Ensemble Forecasts ◽  
Probability Modeling ◽  
Satisfactory Method ◽  
Coherent Forecasts ◽  
Ensemble Model Output Statistics ◽  
Model Output Statistics

GCMs are used by many national weather services to produce seasonal outlooks of atmospheric and oceanic conditions and fluxes. Postprocessing is often a necessary step before GCM forecasts can be applied in practice. Quantile mapping (QM) is rapidly becoming the method of choice by operational agencies to postprocess raw GCM outputs. The authors investigate whether QM is appropriate for this task. Ensemble forecast postprocessing methods should aim to 1) correct bias, 2) ensure forecasts are reliable in ensemble spread, and 3) guarantee forecasts are at least as skillful as climatology, a property called “coherence.” This study evaluates the effectiveness of QM in achieving these aims by applying it to precipitation forecasts from the POAMA model. It is shown that while QM is highly effective in correcting bias, it cannot ensure reliability in forecast ensemble spread or guarantee coherence. This is because QM ignores the correlation between raw ensemble forecasts and observations. When raw forecasts are not significantly positively correlated with observations, QM tends to produce negatively skillful forecasts. Even when there is significant positive correlation, QM cannot ensure reliability and coherence for postprocessed forecasts. Therefore, QM is not a fully satisfactory method for postprocessing forecasts where the issues of bias, reliability, and coherence pre-exist. Alternative postprocessing methods based on ensemble model output statistics (EMOS) are available that achieve not only unbiased but also reliable and coherent forecasts. This is shown with one such alternative, the Bayesian joint probability modeling approach.

Speech Differences along the Ontario United States Border

1956 ◽  
Vol 2 (2) ◽  
pp. 41-59 ◽  
Author(s):  
Walter S. Avis ◽  
R. M. C. Kingston
Keyword(s):  
United States ◽  
Multiple Choice ◽  
Level Of Education ◽  
Field Worker ◽  
Satisfactory Method ◽  
Multiple Choice Questionnaire

The most satisfactory method of collecting data concerning speech habits demands that a trained fieldworker conduct personal interviews with representative informants. Since, however, the time and money required for carrying out such interviews are seldom available, the investigator must often turn to less satisfactory but more practicable methods; one of these is the multiple-choice questionnaire of the type used to gather the information for this limited survey of Ontario speech habits. The fundamental weakness of the circulated questionnaire is self-evident: the informant must substitute for the trained field worker and observe his own usage. His success in making reliable observations will depend on his native intelligence and level of education, his understanding of the significance of the survey, and his conscientiousness with regard to answering the questions.

scholarly journals The action of radium and certain other salts on gelatin

1906 ◽  
Vol 78 (525) ◽  
pp. 380-384
Keyword(s):  
Cambridge Philosophical Society ◽  
Satisfactory Method ◽  
Active Substances

The action of radio-active substances on gelatin media has recently attracted attention. In 'Nature’ there appears a letter by J. B. Burke, in which the writer states that certain “bacterial-like” cells are obtained as the result of the action, the cells grow up to a certain stage and subdivide, they contain a nucleus, and appear to be highly organised bodies. The author has made numerous experiments on this subject, and has made several communications to ‘Nature’ and to the Cambridge Philosophical Society. The present paper deals chiefly with the results obtained by the aid of photography, which obviously is a much more satisfactory method of recording than mere drawing.

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