Comment: Concerning the Paper of R. P. Mariella and K. H. Brown "A Novel SN1 Displacement: The Reaction of Tertiary Amines with Acetic Anhydride"

1973 ◽  
Vol 51 (13) ◽  
pp. 2174-2176 ◽  
Author(s):  
Ya. L. Gol'dfarb ◽  
L. I. Belen'kii

The remarks on the paper of Mariella and Brown (1) concern three points: (1) some similar data from the literature were not mentioned; (2) the mechanism proposed does not take into account the possibility of catalysis of the reaction; and (3) the interpretation of the process as SN1 displacement is not compatible with known data.

1971 ◽  
Vol 49 (20) ◽  
pp. 3348-3351 ◽  
Author(s):  
R. P. Mariella ◽  
K. H. Brown

The action of actic anhydride on tertiary amines at reflux may cause the displacement of one of the R groups from the amine. The groups which are displaced are benzyl, t-butyl, benzhydryl, trityl, and cinnamyl; the groups which are not displaced are methyl, ethyl, n-butyl, phenyl, α-naphthyl, iso-propyl, allyl, and propargyl. An SN1 mechanism with special steric requirements is consistent with the experimental results.


1973 ◽  
Vol 51 (13) ◽  
pp. 2177-2179 ◽  
Author(s):  
R. P. Mariella ◽  
K. H. Brown

The failure of methyl-substituted tertiary amines to yield methyl acetate on cleavage by acetic anhydride indicates that the mechanism proposed by Gol'dfarb and Belen'kii cannot be correct. The results of cleavage of cinnamyldimethylamine are offered as support for the mechanism proposed by Mariella and Brown. Catalysis by acetic acid is not considered to be important.


Author(s):  
R.L. Pinto ◽  
R.M. Woollacott

The basal body and its associated rootlet are the organelles responsible for anchoring the flagellum or cilium in the cytoplasm. Structurally, the common denominators of the basal apparatus are the basal body, a basal foot from which microtubules or microfilaments emanate, and a striated rootlet. A study of the basal apparatus from cells of the epidermis of a sponge larva was initiated to provide a comparison with similar data on adult sponges.Sexually mature colonies of Aplysillasp were collected from Keehi Lagoon Marina, Honolulu, Hawaii. Larvae were fixed in 2.5% glutaraldehyde and 0.14 M NaCl in 0.2 M Millonig’s phosphate buffer (pH 7.4). Specimens were postfixed in 1% OsO4 in 1.25% sodium bicarbonate (pH 7.2) and embedded in epoxy resin. The larva ofAplysilla sp was previously described (as Dendrilla cactus) based on live observations and SEM by Woollacott and Hadfield.


2019 ◽  
Vol 4 (5) ◽  
pp. 814-824 ◽  
Author(s):  
Bonnie E. Smith ◽  
Ruth Huntley Bahr ◽  
Hector N. Hernandez

Purpose The purpose of this study was to determine the attendance and success rates for seniors in voice therapy, identify any contributing patient-related factors, and compare results to existing findings for younger patients. Method This retrospective study included information from the voice records of 50 seniors seen by the same speech-language pathologist in a private practice. Analysis of attendance and outcome data divided participants into 6 groups. Outcomes for Groups 1–3 (64% of patients) were considered successful (positive voice change), while outcomes for Groups 4–6 (36% of patients) were considered unsuccessful. These data were compared to similar data collected for younger adults in a previous study. Results The attendance and success rates for seniors in this study were higher than those previously reported for younger patients. Further consideration of patient factors revealed that reports of increased stress, Reflux Symptom Index scores > 13, and higher Voice Handicap Index functional subscale scores were significant in distinguishing between patients in the successful and unsuccessful treatment outcome groups. Conclusions The relatively high attendance and success rates among this sample of seniors suggest the desire to achieve voice improvement does not diminish with age, and chances for success in voice therapy among nonfrail seniors may be greater than for younger patients.


2020 ◽  
Vol 17 (1) ◽  
pp. 319-328
Author(s):  
Ade Muchlis Maulana Anwar ◽  
Prihastuti Harsani ◽  
Aries Maesya

Population Data is individual data or aggregate data that is structured as a result of Population Registration and Civil Registration activities. Birth Certificate is a Civil Registration Deed as a result of recording the birth event of a baby whose birth is reported to be registered on the Family Card and given a Population Identification Number (NIK) as a basis for obtaining other community services. From the total number of integrated birth certificate reporting for the 2018 Population Administration Information System (SIAK) totaling 570,637 there were 503,946 reported late and only 66,691 were reported publicly. Clustering is a method used to classify data that is similar to others in one group or similar data to other groups. K-Nearest Neighbor is a method for classifying objects based on learning data that is the closest distance to the test data. k-means is a method used to divide a number of objects into groups based on existing categories by looking at the midpoint. In data mining preprocesses, data is cleaned by filling in the blank data with the most dominating data, and selecting attributes using the information gain method. Based on the k-nearest neighbor method to predict delays in reporting and the k-means method to classify priority areas of service with 10,000 birth certificate data on birth certificates in 2019 that have good enough performance to produce predictions with an accuracy of 74.00% and with K = 2 on k-means produces a index davies bouldin of 1,179.


1969 ◽  
Vol 61 (1_Suppl) ◽  
pp. S12 ◽  
Author(s):  
V. H. T. James ◽  
A. E. Rippon ◽  
M. L. Arnold

2019 ◽  
Author(s):  
Christopher J. Legacy ◽  
Frederick T. Greenaway ◽  
Marion Emmert

We report detailed mechanistic investigations of an iron-based catalyst system, which allows the α-C-H oxidation of a wide variety of amines, including acyclic tertiary aliphatic amines, to afford dealkylated or amide products. In contrast to other catalysts that affect α-C-H oxidations of tertiary amines, the system under investigation employs exclusively peroxy esters as oxidants. More common oxidants (e.g. tBuOOH) previously reported to affect amine oxidations via free radical pathways do not provide amine α-C-H oxidation products in combination with the herein described catalyst system. Motivated by this difference in reactivity to more common free radical systems, the investigations described herein employ initial rate kinetics, kinetic profiling, Eyring studies, kinetic isotope effect studies, Hammett studies, ligand coordination studies, and EPR studies to shed light on the Fe catalyst system. The obtained data suggest that the catalytic mechanism proceeds through C-H abstraction at a coordinated substrate molecule. This rate-determining step occurs either at an Fe(IV) oxo pathway or a 2-electron pathway at a Fe(II) intermediate with bound oxidant. We further show via kinetic profiling and EPR studies that catalyst activation follows a radical pathway, which is initiated by hydrolysis of PhCO3 tBu to tBuOOH in the reaction mixture. Overall, the obtained mechanistic data support a non-classical, Fe catalyzed pathway that requires substrate binding, thus inducing selectivity for α-C-H functionalization.<br>


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