The limited scope of azabicyclohexane synthesis from δ,ε-unsaturated amines

1978 ◽  
Vol 31 (10) ◽  
pp. 2247 ◽  
Author(s):  
DSC Black ◽  
JE Doyle
Keyword(s):  
Sodium Hydride ◽  
Similar Treatment ◽  
Limited Scope

The reported synthesis of 1-azabicyclo[3,1,0]hexanes from β,β-diphenyl δ,ε-unsaturated alkylamines has been verified and extended. However, similar treatment of alkyl-substituted δ,ε-unsaturated alkylamines with bromine and sodium hydride fails to afford azabicyclohexanes and unsaturated acyclic products are formed. It is concluded that satisfactory synthesis of azabicyclohexanes from δ,ε-unsaturated amines is contingent on the presence of suitable bulky substituents.

Nucleophilic and acid-catalyzed cleavage of the cyclopropane rings of β,γ-unsaturated α-spirocyclopropyl ketones

1983 ◽  
Vol 61 (1) ◽  
pp. 78-85 ◽  
Author(s):  
Peter Yates ◽  
Patrick Hugh Helferty ◽  
Paul Mahler
Keyword(s):  
Nucleophilic Addition ◽  
Cyclopropane Ring ◽  
Sodium Hydride ◽  
Ring Cleavage ◽  
Similar Treatment ◽  
Torsional Strain ◽  
Rate Of Reaction ◽  
Saturated Compound ◽  
Acid Catalyzed ◽  
Rapid Protonation

Treatment of isophorone (8) with sodium amide and 1,2-dibromomethane gives 6,6-dimethyl-8-methylenespiro[2.5]octan-4-one (9) and 6,6,8-trimethylspiro[2.5]oct-7-en-4-one (10); similar treatment of 3-methylcyclohex-2-en-1-one (5) gives analogous spiro compounds 6 and 7 together with 8-methylenedispiro[2.1.2.3]decan-4-one (11) and 8-methyldispiro[2.1.2.3]dec-8-en-4-one (12). The spiro ketones 6, 7, 9, and 10 undergo homoconjugate nucleophilic addition on being heated in morpholine with cleavage of the cyclopropane rings to give 2-[2-(4-morpholinyl)ethyl]cyclohex-2-en-1-ones. The rates of reaction are much greater for the exo methylene compounds 6 and 9 than for their endo isomers 7 and 10, but the rate of reaction of 10 is only slightly greater than that of the corresponding saturated compound, 6,6,8-trimethylspiro[2.5]octan-4-one (15). A corresponding rate differential between 9 and 10 is observed in their reactions with isophorone (8) and sodium hydride to give 2,2′-(ethanediyl)bis[3,5,5-trimethylcyclohex-2-en-1-one] (18). The acceleration in the cases of 6 and 9 relative to that of 15 is attributed to spiroactivation by both the carbonyl and exocyclic ethylenic groups; the much smaller effect of the endocyclic ethylenic groups in the cases of 7 and 10 is ascribed to torsional strain in the transition states for ring opening. The spiro ketones 6, 7, 9, and 10 also undergo acid-catalyzed cyclopropane ring cleavage in ethanol, giving 2-(2-ethoxyethyl)cyclohex-2-en-1-ones. Again the exo methylene compounds 6 and 9 react much more rapidly than their endo isomers 7 and 10; this is considered to be due to factors analogous to those operative in the nucleophilic addition reactions and/or the more rapid protonation of the exo methylene compounds.

Filled with Spirit and Power: Protestant Clergy in Politics. By Laura R. Olson. Albany: State University of New York Press, 2000. 174p. $57.50 cloth, $18.95 paper.

2001 ◽  
Vol 95 (4) ◽  
pp. 1005-1006
Author(s):  
Paul J. Weber
Keyword(s):  
New York ◽  
African American ◽  
Family Values ◽  
State University ◽  
Protestant Clergy ◽  
African American Pastors ◽  
The Family ◽  
Limited Scope

Laura Olson is one of a small but energetic and influential group of Christian political scientists determined to bring the debate politically legitimate called it either racist or sexist. Yet, somewhat surprisingly, African American pastors held the most consistently conservative views on family values, although they also saw the connections among crime, violence, and the deterioration of the family. Within the authorÕs intentionally limited scope, this is an excellent study, but one should be cautious about generalizing.

THE AFRICAN WIFE OF SOLOMON (1 KINGS 3:1; 9:16; 7:8; 11:1)

2017 ◽  
Vol 23 (1) ◽  
Author(s):  
David Tuesday Adamo
Keyword(s):  
African Woman ◽  
Archaeological Record ◽  
Not Given ◽  
Similar Treatment ◽  
Ancient Israel ◽  
1 Kings

Both the Deuteronomist and the Chronicler repeatedly testify that Solomon married an African woman who was the daughter of Pharaoh. The fact that Pharaoh‟s daughter was singled out in this manner is significant as similar treatment was not given to his many other wives and concubines. In the African polygamous system, the first wife exercises enormous power over the husband and other wives. In keeping with the tradition, as chief wife Pharaoh‟s daughter would have had immense influence over Solomon. This pervasive influence can be seen in the economic, political, and administrative policies of the day, as well as in the prohibition on Solomon marrying an Israelite woman. Although Solomon‟s African wife is nameless in the biblical record, and both Solomon and his wife are unattested in the archaeological record, the marriage represents an aspect of African influence on and contribution to ancient Israel.

Polyunsaturated fatty acids are less effective to reduce methanogenesis in rumen inoculum from calves exposed to a similar treatment early in life

2017 ◽  
Vol 0 (0) ◽  
pp. 0
Author(s):  
A. Ruiz-González ◽  
S. Debruyne ◽  
J. Jeyanathan ◽  
L. Vandaele ◽  
S. De Campeneere ◽  
...  
Keyword(s):  
Fatty Acids ◽  
Polyunsaturated Fatty Acids ◽  
Similar Treatment

The Cornucopia in the Minefield

2020 ◽  
Vol 54 (1-3) ◽  
pp. 253-279
Author(s):  
Jennifer B. Spock
Keyword(s):  
Soviet Union ◽  
Individual Characteristics ◽  
Social Classes ◽  
Material Objects ◽  
Daily Lives ◽  
Building Projects ◽  
Holy Trinity ◽  
Spiritual Path ◽  
The Soviet Union ◽  
Limited Scope

Abstract The study of monasticism in Russia has found new acolytes since the dissolution of the Soviet Union. With the separation of the Soviet republics, religion became, and continues to become, a vibrant subfield of Russian studies. This article examines the problems inherent in attempting to grasp the day-to-day life of monks and monasteries given their individual characteristics, social classes, roles, and the wide variety, yet often limited scope, of various texts and material objects that can be used as sources. The vast source base is an embarrassment of riches in one sense, but problematic in another as prescriptive and normative texts must be understood in context. One important element that has not been directly addressed is the cacophony of sound, the interruptions, and the distractions of the constant activity of expanding cloisters in the sixteenth and seventeenth centuries. How did monks maintain their spiritual path and pious duties when on service expeditions outside the monastery: when engaged in salt-production, fishing, trade, rent-collecting, or other activities outside its walls? How intrusive were building projects, which abounded in the period, or even efforts to adorn the churches? How strict was oversight, or how weak? Such questions still need answers and can only be fully understood by integrating diverse source bases. This article uses Solovki, Holy Trinity, and Kirillov monasteries to exemplify the problems that remain in understanding the daily lives of monastics and their adherents within and without the confines of the cloister.

Bio-efficacy of post emergence herbicides in boro rice nursery as well as main field and their residual effects on non-target microorganisms

2020 ◽  
Vol 57 (3) ◽  
pp. 199-210
Author(s):  
Rajib Kundu ◽  
Mousumi Mondal ◽  
Sourav Garai ◽  
Ramyajit Mondal ◽  
Ratneswar Poddar
Keyword(s):  
Weed Control ◽  
Weed Management ◽  
Field Experiments ◽  
Block Design ◽  
Resistance Index ◽  
Residual Effects ◽  
Cost Ratio ◽  
Main Field ◽  
Weed Species ◽  
Similar Treatment

Field experiments were conducted at research farm of Bidhan Chandra Krishi Viswavidyalaya, Kalyani, West Bengal, India (22°97' N latitude and 88°44' E longitude, 9.75 m above mean sea level) under natural weed infestations in boro season rice (nursery bed as well as main field) during 2017-18 and 2018-19 to evaluate the herbicidal effects on weed floras, yield, non-target soil organisms to optimize the herbicide use for sustainable rice-production. Seven weed control treatments including three doses of bispyribac-sodium 10% SC (150,200, and 250 ml ha-1), two doses of fenoxaprop-p-ethyl 9.3% EC (500 and 625 ml ha-1), one weed free and weedy check were laid out in a randomized complete block design, replicated thrice. Among the tested herbicides, bispyribac-sodium with its highest dose (250 ml ha-1) resulted in maximum weed control efficiency, treatment efficiency index and crop resistance index irrespective of weed species and dates of observation in both nursery as well as main field. Similar treatment also revealed maximum grain yield (5.20 t ha-1), which was 38.38% higher than control, closely followed by Fenoxaprop-p-ethyl (625 ml ha-1) had high efficacy against grasses, sedge and broadleaf weed flora. Maximum net return (Rs. 48765 ha-1) and benefit cost ratio (1.72) were obtained from the treatment which received bispyribac-sodium @ 250 ml ha-1. Based on overall performance, the bispyribac-sodium (250 ml ha-1) may be considered as the best herbicide treatment for weed management in transplanted rice as well as nursery bed.

Macropolyhedral Boron-Containing Cluster Chemistry. A Metallathiaborane from S2B17H17: Isolation and Characterisation of [(PMe2Ph)2PtS2B16H16]; A neo-arachno Ten-Vertex Cluster Shape, and the Constitution of the [arachno-B10H15]- Anion

2005 ◽  
Vol 70 (4) ◽  
pp. 430-440 ◽  
Author(s):  
Michael J. Carr ◽  
Michael G. S. Londesborough ◽  
Jonathan Bould ◽  
Ivana Císařová ◽  
Bohumil Štíbr ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Sodium Hydride ◽  
Hydrogen Atoms ◽  
Subsequent Reaction ◽  
Cluster Chemistry ◽  
Cluster Shape ◽  
Open Face

The deprotonation of S2B17H17 with sodium hydride and subsequent reaction with [PtCl2(PMe2Ph)2] gives the new macropolyhedral metallathiaborane [(PMe2Ph)2PtS2B16H16], of which the cluster consists of a conventional eleven-vertex nido {SB10} unit, fused, with two boron atoms in common, with a {PtSB8} unit of unique ten-vertex neo-arachno constitution and geometry. The latter geometry suggests a configuration for the previously structurally uncharacterised [B10H15]- anion; starting from this configuration, DFT calculations of structure and thence of boron nuclear shieldings, which are found very closely to mimic those found experimentally, thence support a fluxional structure for [B10H15]- with three {BHB(bridging)} and two {BH(endo)} hydrogen atoms around a six-membered open face.

scholarly journals A cross-dehydrogenative C(sp3)−H heteroarylation via photo-induced catalytic chlorine radical generation

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Chia-Yu Huang ◽  
Jianbin Li ◽  
Chao-Jun Li
Keyword(s):  
Hydrogen Atom ◽  
Hydrogen Evolution ◽  
Alkyl Radical ◽  
Cobalt Catalyst ◽  
Alkylation Reaction ◽  
Hydrogen Atom Abstraction ◽  
Dehydrogenative Coupling ◽  
Radical Generation ◽  
Limited Scope

AbstractHydrogen atom abstraction (HAT) from C(sp3)–H bonds of naturally abundant alkanes for alkyl radical generation represents a promising yet underexplored strategy in the alkylation reaction designs since involving stoichiometric oxidants, excessive alkane loading, and limited scope are common drawbacks. Here we report a photo-induced and chemical oxidant-free cross-dehydrogenative coupling (CDC) between alkanes and heteroarenes using catalytic chloride and cobalt catalyst. Couplings of strong C(sp3)–H bond-containing substrates and complex heteroarenes, have been achieved with satisfactory yields. This dual catalytic platform features the in situ engendered chlorine radical for alkyl radical generation and exploits the cobaloxime catalyst to enable the hydrogen evolution for catalytic turnover. The practical value of this protocol was demonstrated by the gram-scale synthesis of alkylated heteroarene with merely 3 equiv. alkane loading.

scholarly journals OP0162 ETANERCEPT RESPONSE CLUSTERS IN JUVENILE IDIOPATHIC ARTHRITIS

2021 ◽  
Vol 80 (Suppl 1) ◽  
pp. 97.1-98
Author(s):  
S. Shoop-Worrall ◽  
K. Hyrich ◽  
L. Wedderburn ◽  
W. Thomson ◽  
N. Geifman
Keyword(s):  
Young People ◽  
Disease Activity ◽  
Treatment Response ◽  
Similar Response ◽  
Response Patterns ◽  
Active Joint ◽  
Research Support ◽  
Similar Treatment ◽  
Children And Young People ◽  
Multiple Drugs

Background:In children and young people (CYP) with JIA, we have previously identified clusters with different patterns of disease impact following methotrexate (MTX) initiation. It is unclear whether clusters of treatment response following etanercept (ETN) therapy exist and whether, in a group of CYP who have responded inadequately to or had adverse events on methotrexate, similar treatment response patterns exist. Novel response patterns would aid stratified treatment approaches through better understanding and potential forecasting of more specific response patterns across multiple domains of disease.Objectives:To identify and characterise trajectories of juvenile arthritis disease activity score (JADAS) components following ETN initiation for JIA.Methods:ETN-naïve CYP with non-systemic JIA were selected if enrolled prior to January 2019 in at least one of four CLUSTER consortium studies: BSPAR-ETN, BCRD, CAPS and CHARMS, at point of starting ETN as their first biological therapy. JADAS components (active joint count, physician’s global assessment (0-10cm), parental global evaluation (0-10cm) and standardised ESR (0-10) were collected at ETN initiation and during the following year.Multivariate group-based trajectory models, that identify clusters of CYP with similar patterns of change over time, were used to explore ETN response clusters across the different JADAS components. Censored-normal (global scores, ESR) and zero-inflated Poisson (active joint count) models were used, adjusting for year of ETN initiation. Optimal models were selected based on a combination of model fit (BIC), parsimony, and clinical plausibility.Results:Of the 1003 CYP included, the majority were female (70%) and of white ethnicity (90%), with rheumatoid factor-negative JIA the most common disease category (39%).The optimal model identified five trajectory clusters of disease activity following initiation of ETN (Figure 1). Clusters following ETN were similar and covered similar proportions of CYP to those previously identified following MTX: Fast (Group 1: 13%) and Slow (Group 2: 10%) response, active joint count improves but either physician (Group 3: 6%) or parent global scores (Group 4: 34%) remain persistently raised and a group with persistent raised scores across all JADAS components (Group 5: 36%). Compared to the persistent disease cluster, those with greater improvement had lower age and higher functional ability at ETN initiation and those with persistent raised parent global scores had lower ESR levels and were less likely to be RF-positive at ETN initiation.Figure 1.Clusters identified following ETN initiation in children and young people recruited to the UK BSPAR-ETN, BCRD, CAPS and CHARMS studies.Conclusion:This study has identified that within CYP initiating ETN, similar response clusters are evident to those previously identified following MTX. This commonality suggests a new framework for understanding treatment response, beyond a simple responder/non-responder analysis at a set point, which applies across multiple drugs despite different mechanisms of action and previous unfavourable treatment outcomes. Understanding both clinical factors associated with, and biological mechanisms underpinning, these clusters would aid stratified medicine in JIA.Acknowledgements:We thank the children, young people and families involved in CLUSTER, as well as clinical staff, administrators and data management teams. Funding for CLUSTER has been provided by generous grants from the MRC, Versus Arthritis, GOSH children’s charity, Olivia’s vision and the NIHR Manchester and GOSH BRC schemes.Disclosure of Interests:Stephanie Shoop-Worrall: None declared, Kimme Hyrich Speakers bureau: Abbvie, Grant/research support from: BMS, UCB, Pfizer, Lucy Wedderburn Speakers bureau: Pfizer, Grant/research support from: Abbvie, Sobi, Wendy Thomson Grant/research support from: Abbvie, Sobi, Nophar Geifman Grant/research support from: Abbvie, Sobi

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