title: Deamination and hydrolysis of tertiary systems

authors: Van Der Beeke, Paul Gerard Johan

abstract: This thesis reports the aqueous nitrous acid deamination of two tertiary carbinamines; 2-amino-2-methylpropane and 3-amino-3-methylpentane (at 80°C, pH4). The hydrolysis (at 80°C, pH4) of the two corresponding alkyldimethyl sulphonium salts; dimethyl-(2-methyl-2-propyl) sulphonium perchlorate and dimethyl-(3-methyl-3-pentyl) sulphonium perchlorate, is also reported. A comparison of the two types of reaction (deamination and hydrolysis) shows small but definite differences. Both deaminations produced a greater proportion of elimination than the corresponding hydrolyses. The deamination of 3-amino-3-methylpentane produced lower 2-ene/1-ene and trans/cis ratios than the corresponding hydrolysis. 
It is suggested that the deamination carbocations are short-lived and shielding by the departing nitrogen prevents complete loss of the “excess” energy acquired from the irreversible decomposition of the diazonium ions. The “excess” energy of the deamination product precursors relative to the hydrolysis analogs makes the higher energy product-forming pathways more favourable in deamination than hydrolysis.

text: Deamination and hydrolysis of tertiary systems This thesis reports the aqueous nitrous acid deamination of two tertiary carbinamines; 2-amino-2-methylpropane and 3-amino-3-methylpentane (at 80°C, pH4). The hydrolysis (at 80°C, pH4) of the two corresponding alkyldimethyl sulphonium salts; dimethyl-(2-methyl-2-propyl) sulphonium perchlorate and dimethyl-(3-methyl-3-pentyl) sulphonium perchlorate, is also reported. A comparison of the two types of reaction (deamination and hydrolysis) shows small but definite differences. Both deaminations produced a greater proportion of elimination than the corresponding hydrolyses. The deamination of 3-amino-3-methylpentane produced lower 2-ene/1-ene and trans/cis ratios than the corresponding hydrolysis. 
It is suggested that the deamination carbocations are short-lived and shielding by the departing nitrogen prevents complete loss of the “excess” energy acquired from the irreversible decomposition of the diazonium ions. The “excess” energy of the deamination product precursors relative to the hydrolysis analogs makes the higher energy product-forming pathways more favourable in deamination than hydrolysis.

year: 1980

title: On the CUSP of innovation: From CUSP to CUSP2

authors: Cooper, Bronwen

abstract: The Collaborative University-School Partnership project (CUSP) documents the experiences of a New Zealand university and seven schools as they collaborated on the development and introduction of a reframed practicum programme in the first year of a three-year undergraduate primary initial teacher education (ITE) programme. The CUSP programme was designed to enhance teacher, university lecturer, and student-teacher experience of the school-based components of the ITE programme by weaving the university and school-based components into a more coherent and seamless whole to which each community contributed and benefited. In the co-constructed and reconceptualised school-based programme, lecturers and teachers became jointly responsible for student-teacher development.

text: On the CUSP of innovation: From CUSP to CUSP2 The Collaborative University-School Partnership project (CUSP) documents the experiences of a New Zealand university and seven schools as they collaborated on the development and introduction of a reframed practicum programme in the first year of a three-year undergraduate primary initial teacher education (ITE) programme. The CUSP programme was designed to enhance teacher, university lecturer, and student-teacher experience of the school-based components of the ITE programme by weaving the university and school-based components into a more coherent and seamless whole to which each community contributed and benefited. In the co-constructed and reconceptualised school-based programme, lecturers and teachers became jointly responsible for student-teacher development.

year: 2019

title: Mā Te Wai - Ka Piki Ake Te Hauora

authors: Rollo, Te Manaaroha Pirihira

abstract: This paper researched traditional Māori forms of music therapy focusing on waiata¹ and taonga pūoro² . Linking cultures: collaborative partnerships in music therapy and related disciplines is the main objective of this research. In support, this paper examined past and current Māori practices that aim to heal and promote ‘well-being’ amongst people, thus resulting in linking the Māori culture and therapeutic values and practices in contemporary New Zealand

text: Mā Te Wai - Ka Piki Ake Te Hauora This paper researched traditional Māori forms of music therapy focusing on waiata¹ and taonga pūoro² . Linking cultures: collaborative partnerships in music therapy and related disciplines is the main objective of this research. In support, this paper examined past and current Māori practices that aim to heal and promote ‘well-being’ amongst people, thus resulting in linking the Māori culture and therapeutic values and practices in contemporary New Zealand

year: 2013-11-23