title: Organophosphorus chemistry of camphene

authors: Leach, Meto T.

abstract: Chapter one reviews the literature relating to terpene-phosphorus chemistry. Topics include a summary of the phosphorus chemistry of the monoterpenes and terpenoids camphor, menthol, camphene and pinene. A general discussion on terpene-phosphines and terpene-phosphonates is also included.
 
Chapter two of this thesis describes the chemistry of the camphene-derived phosphinic acids, 8-camphanylphosphinic acid [C₁₀H₁₇P(O)(H)(OH) 1] (2,2-dimethylbicyclo[2.2.1] hept-3-ylmethylphosphinic acid) and 8-camphanyl-(phenyl)phosphinic acid [C₁₀H₁₇P(O)(Ph)(OH) 3], which are formed by the radical-catalysed addition of hypophosphorous acid [H₃PO₂] and phenylphosphinic acid [PhPO₂H₂] to camphene. Reaction conditions which optimise the yield of 1 have been investigated along with the detailed characterisation by single crystal X-ray studies, ESMS and one- and two-dimensional NMR studies. The attempted preparation of chiral 1 starting from (R)-(+)-camphene yields only racemic material, the result of the acid-catalysed racemisation of camphene prior to the reaction with H₃PO₂. Methylation of the phosphinic acids 1 and 3 with diazomethane yields the methyl esters 6 [C₁₀H₁₇P(O)(H)(OMe)] and 7 [C₁₀H₁₇P(O)(Ph)(OMe)]. These methyl esters have been fully characterised by NMR and GCMS. 1 reacts with paraformaldehyde to form the hydroxymethylphosphinic acid 9 [C₁₀H₁₇P(O)(OH)(CH₂OH)] and with a formaldehyde/dimethylamine mixture to form 10 [(C₁₀H₁₇P(O)(OH)-(CH₂NHMe₂))Cl]. The oxidative chlorination of 1 and 3 with thionyl chloride [using a pyridine catalyst] yields the acid chlorides 11 [C₁₀H₁₇P(O)Cl₂] and 12 [C₁₀H₁₇P(O)(Ph)Cl]. 

The reaction of 1 with calcium nitrate and excess urea (for pH control) for 5 days yields polymeric calcium salt 13 [(Ca(C₁₀H₁₇PO₂H)₂(C₁₀H₁₇PO₂H₂)-(H₂O))ₙ] on the basis of a single crystal X-ray study. The dominance of the bulky camphanyl groups, which form a coherent, essentially ‘close-packed’ hydrocarbon sheath around the central hydrophilic inorganic Ca/O/P core give the appearance of individual chains resembling ‘insulated wire’. 

Chapter three describes the synthesis and subsequent derivatisation of the camphene-derived phosphonic acid 14 [C₁₀H₁₇P(O)(OH)₂]. The formation of 14 via both the oxidation of 1 and the hydrolysis of 11 [C₁₀H₁₇P(O)Cl₂] (in mild conditions), are investigated. 14 is characterised in detail by single crystal X-ray studies and one- and two-dimensional NMR studies. The treatment of 14 with diazomethane yields the methyl ester 15 [C₁₀H₁₇P(O)(OMe)₂]. 

Also included in Chapter 3 is the reaction of an excess of silver oxide with equimolar quantities of the platinum dichloride complexes cis-[PtCl₂L₂] [L=PPh₃, PPhMe₂; L₂=DPPE] {DPPE=1,2-bis(diphenylphosphane)ethane} and 14. The Pt(II) complexes 16, 17 and 18, [Pt{OP(O)(C₁₀H₁₇)O(L)₂} L=PPh₃, PPhMe₂; L₂=DPPE], which are formed in moderate yields, are characterised in detail by ³¹P, ¹H and ¹³C NMR spectroscopy. The analogous palladium chemistry of 14 is non-selective, forming a large number of unidentifiable products. 

Chapter four describes the formation of the phosphines 20 [C₁₀H₁₇PH₂], 23 [C₁₀H₁₇P(CH₂OH)₂] and their derivatives. The reaction of phosphonic dichloride 11 [C₁₀H₁₇P(O)Cl₂] with lithium aluminium hydride does not afford the free phosphine but a metal-phosphine adduct of 8- camphanylphosphine. However when 1 is heated to 140°C under vacuum [0.5 mm Hg] 1 disproportionates to yield 8-camphanylphosphine 20 [C₁₀H₁₇PH₂] which, when treated with aqueous hydrochloric acid/formaldehyde, affords an air-stable tris(hydroxymethyl)phosphonium chloride 22 [(C₁₀H₁₇P(CH₂OH)₃)Cl]. 22 is the first tris(hydroxymethyl)phosphonium salt to date to be subjected to a crystallographic study.

The treatment of 22 with equimolar amounts of either potassium hydroxide or triethylamine affords the bis(hydroxymethyl)phosphine 23 [C₁₀H₁₇P(CH₂OH)₂]. The subsequent addition of an excess of sulfur or selenium yields the phosphine sulfide 24 [C₁₀H₁₇P(S)(CH₂OH)₂] and the phosphine selenide 25 [C₁₀H₁₇P(Se)(CH₂OH)₂]. The controlled oxidation of 23 with hydrogen peroxide gives the bis(hydroxymethyl)phosphine oxide 26 [C₁₀H₁₇P(O)(CH₂OH)₂]. 

The treatment of 23 with CODPtCl₂ {COD = 1, 5 cyclooctadiene} directly precipitates the platinum dichloride complex 27 [(C₁₀H₁₇P(CH₂OH)₂)₂PtCl₂) while the gold(I) chloride complex 28 [C₁₀H₁₇P(CH₂OH)₂AuCl] is precipitated by the action of tetrahydrothiophene gold(I) chloride upon 23. Hydroxymethylphosphine 23 and its derivatives [24-28] have been fully characterised by NMR spectroscopy and ESMS.

Included in Chapter four is an investigation of the gas phase decomposition of 20 by Berrigan and Russell at Auckland University. Aided by the use of I.R. Laser Powered Homogeneous Pyrolysis, results indicate that phosphine is firstly eliminated followed by the rearrangement and decomposition of camphene through two distinct pathways.

Chapter five describes the formation of uranyl nitrate complexes of the camphene-derived phosphorylic ligands 15, 7 and 29 [the synthesis of 29 [C₁₀H₁₇P(O)Ph₂] is also described therein]. The spontaneous evaporation of methanolic solutions containing uranyl(VI) nitrate and these monodentate ligands yield the uranyl(VI) nitrate complexes UO₂(NO₃)₂L₂ [30 L= C₁₀H₁₇P(O)(OMe)₂], [31 L= C₁₀H₁₇P(O)(Ph)(OMe)] and [32 L= C₁₀H₁₇P(O)Ph₂]. The uranyl(VI) nitrate complex [UO₂(NO₃)₂{C₁₀H₁₇P(O)(OMe)₂}₂] (30) has been subjected to a single crystal X-ray study. The structure determination was not straightforward, largely as a result of the combination of a dominant scattering atom (uranium) and substantial disorder of the camphanyl groups.

text: Organophosphorus chemistry of camphene Chapter one reviews the literature relating to terpene-phosphorus chemistry. Topics include a summary of the phosphorus chemistry of the monoterpenes and terpenoids camphor, menthol, camphene and pinene. A general discussion on terpene-phosphines and terpene-phosphonates is also included.
 
Chapter two of this thesis describes the chemistry of the camphene-derived phosphinic acids, 8-camphanylphosphinic acid [C₁₀H₁₇P(O)(H)(OH) 1] (2,2-dimethylbicyclo[2.2.1] hept-3-ylmethylphosphinic acid) and 8-camphanyl-(phenyl)phosphinic acid [C₁₀H₁₇P(O)(Ph)(OH) 3], which are formed by the radical-catalysed addition of hypophosphorous acid [H₃PO₂] and phenylphosphinic acid [PhPO₂H₂] to camphene. Reaction conditions which optimise the yield of 1 have been investigated along with the detailed characterisation by single crystal X-ray studies, ESMS and one- and two-dimensional NMR studies. The attempted preparation of chiral 1 starting from (R)-(+)-camphene yields only racemic material, the result of the acid-catalysed racemisation of camphene prior to the reaction with H₃PO₂. Methylation of the phosphinic acids 1 and 3 with diazomethane yields the methyl esters 6 [C₁₀H₁₇P(O)(H)(OMe)] and 7 [C₁₀H₁₇P(O)(Ph)(OMe)]. These methyl esters have been fully characterised by NMR and GCMS. 1 reacts with paraformaldehyde to form the hydroxymethylphosphinic acid 9 [C₁₀H₁₇P(O)(OH)(CH₂OH)] and with a formaldehyde/dimethylamine mixture to form 10 [(C₁₀H₁₇P(O)(OH)-(CH₂NHMe₂))Cl]. The oxidative chlorination of 1 and 3 with thionyl chloride [using a pyridine catalyst] yields the acid chlorides 11 [C₁₀H₁₇P(O)Cl₂] and 12 [C₁₀H₁₇P(O)(Ph)Cl]. 

The reaction of 1 with calcium nitrate and excess urea (for pH control) for 5 days yields polymeric calcium salt 13 [(Ca(C₁₀H₁₇PO₂H)₂(C₁₀H₁₇PO₂H₂)-(H₂O))ₙ] on the basis of a single crystal X-ray study. The dominance of the bulky camphanyl groups, which form a coherent, essentially ‘close-packed’ hydrocarbon sheath around the central hydrophilic inorganic Ca/O/P core give the appearance of individual chains resembling ‘insulated wire’. 

Chapter three describes the synthesis and subsequent derivatisation of the camphene-derived phosphonic acid 14 [C₁₀H₁₇P(O)(OH)₂]. The formation of 14 via both the oxidation of 1 and the hydrolysis of 11 [C₁₀H₁₇P(O)Cl₂] (in mild conditions), are investigated. 14 is characterised in detail by single crystal X-ray studies and one- and two-dimensional NMR studies. The treatment of 14 with diazomethane yields the methyl ester 15 [C₁₀H₁₇P(O)(OMe)₂]. 

Also included in Chapter 3 is the reaction of an excess of silver oxide with equimolar quantities of the platinum dichloride complexes cis-[PtCl₂L₂] [L=PPh₃, PPhMe₂; L₂=DPPE] {DPPE=1,2-bis(diphenylphosphane)ethane} and 14. The Pt(II) complexes 16, 17 and 18, [Pt{OP(O)(C₁₀H₁₇)O(L)₂} L=PPh₃, PPhMe₂; L₂=DPPE], which are formed in moderate yields, are characterised in detail by ³¹P, ¹H and ¹³C NMR spectroscopy. The analogous palladium chemistry of 14 is non-selective, forming a large number of unidentifiable products. 

Chapter four describes the formation of the phosphines 20 [C₁₀H₁₇PH₂], 23 [C₁₀H₁₇P(CH₂OH)₂] and their derivatives. The reaction of phosphonic dichloride 11 [C₁₀H₁₇P(O)Cl₂] with lithium aluminium hydride does not afford the free phosphine but a metal-phosphine adduct of 8- camphanylphosphine. However when 1 is heated to 140°C under vacuum [0.5 mm Hg] 1 disproportionates to yield 8-camphanylphosphine 20 [C₁₀H₁₇PH₂] which, when treated with aqueous hydrochloric acid/formaldehyde, affords an air-stable tris(hydroxymethyl)phosphonium chloride 22 [(C₁₀H₁₇P(CH₂OH)₃)Cl]. 22 is the first tris(hydroxymethyl)phosphonium salt to date to be subjected to a crystallographic study.

The treatment of 22 with equimolar amounts of either potassium hydroxide or triethylamine affords the bis(hydroxymethyl)phosphine 23 [C₁₀H₁₇P(CH₂OH)₂]. The subsequent addition of an excess of sulfur or selenium yields the phosphine sulfide 24 [C₁₀H₁₇P(S)(CH₂OH)₂] and the phosphine selenide 25 [C₁₀H₁₇P(Se)(CH₂OH)₂]. The controlled oxidation of 23 with hydrogen peroxide gives the bis(hydroxymethyl)phosphine oxide 26 [C₁₀H₁₇P(O)(CH₂OH)₂]. 

The treatment of 23 with CODPtCl₂ {COD = 1, 5 cyclooctadiene} directly precipitates the platinum dichloride complex 27 [(C₁₀H₁₇P(CH₂OH)₂)₂PtCl₂) while the gold(I) chloride complex 28 [C₁₀H₁₇P(CH₂OH)₂AuCl] is precipitated by the action of tetrahydrothiophene gold(I) chloride upon 23. Hydroxymethylphosphine 23 and its derivatives [24-28] have been fully characterised by NMR spectroscopy and ESMS.

Included in Chapter four is an investigation of the gas phase decomposition of 20 by Berrigan and Russell at Auckland University. Aided by the use of I.R. Laser Powered Homogeneous Pyrolysis, results indicate that phosphine is firstly eliminated followed by the rearrangement and decomposition of camphene through two distinct pathways.

Chapter five describes the formation of uranyl nitrate complexes of the camphene-derived phosphorylic ligands 15, 7 and 29 [the synthesis of 29 [C₁₀H₁₇P(O)Ph₂] is also described therein]. The spontaneous evaporation of methanolic solutions containing uranyl(VI) nitrate and these monodentate ligands yield the uranyl(VI) nitrate complexes UO₂(NO₃)₂L₂ [30 L= C₁₀H₁₇P(O)(OMe)₂], [31 L= C₁₀H₁₇P(O)(Ph)(OMe)] and [32 L= C₁₀H₁₇P(O)Ph₂]. The uranyl(VI) nitrate complex [UO₂(NO₃)₂{C₁₀H₁₇P(O)(OMe)₂}₂] (30) has been subjected to a single crystal X-ray study. The structure determination was not straightforward, largely as a result of the combination of a dominant scattering atom (uranium) and substantial disorder of the camphanyl groups.

year: 1999

title: Preliminary impacts of a new seasonal work program on rural household incomes in the Pacific

authors: Gibson, John

subjects: propensity score matching

abstract: Seasonal work programs are increasingly advocated by international aid agencies as a way of enabling both developed and developing countries to benefit from migration. They are argued to provide workers with new skills and allow them to send remittances home, without the receiving country having to worry about long-term assimilation and the source country worrying about permanent loss of skills. However, formal evidence as to the development impact of seasonal worker programs is non-existent. This paper provides the first such evaluation, studying New Zealand's new Recognized Seasonal Employer (RSE) program which allows Pacific Island migrants to work in horticulture and viticulture in New Zealand for up to seven months per year. We use baseline and follow-up waves of surveys we are carrying out in Tonga to form difference-in-difference and propensity score matching estimates of short-term impacts on household income and consumption.

text: Preliminary impacts of a new seasonal work program on rural household incomes in the Pacific Seasonal work programs are increasingly advocated by international aid agencies as a way of enabling both developed and developing countries to benefit from migration. They are argued to provide workers with new skills and allow them to send remittances home, without the receiving country having to worry about long-term assimilation and the source country worrying about permanent loss of skills. However, formal evidence as to the development impact of seasonal worker programs is non-existent. This paper provides the first such evaluation, studying New Zealand's new Recognized Seasonal Employer (RSE) program which allows Pacific Island migrants to work in horticulture and viticulture in New Zealand for up to seven months per year. We use baseline and follow-up waves of surveys we are carrying out in Tonga to form difference-in-difference and propensity score matching estimates of short-term impacts on household income and consumption.

year: 2008-12

title: Ko wai tō ingoa? The transformative potential of Māori names

authors: Seed-Pihama, Joeliee Elizabeth

subjects: Māori names

abstract: Ingoa tangata (personal names) are an expression of te reo Māori, Māori identity, and tino rangatiratanga (self-determination). Nevertheless, our names are still mispronounced, marginalised and demeaned by individuals and institutions, such as schools, the health system, politics and media. This thesis argues that the gift of a Māori name and the assertion of that name over one’s lifetime is simultaneously a political act of resistance and an act of normalisation – an act of just being Māori. In particular, the thesis reveals how whānau naming practices endure and are important for whānau identity and belonging.

A Kaupapa Māori theoretical approach is used to highlight the mana of our ingoa tangata within te ao Māori (the Māori world). I analyse the experiences of six generations of one whānau and the ways in which they have resisted, reclaimed and regenerated our ingoa tangata and associated practices. Kaupapa Māori theory provides a much-needed theoretical framework that privileges te reo Māori and mātauranga Māori throughout this research. This theory also supports Māori researchers to critique and disrupt Western power dynamics within research as well as maintaining the political imperative of decolonisation and resurgence agendas within the research of Indigenous communities.

This thesis foregrounds Pūrākau as a research method to tell the kōrero ingoa (naming stories) of six generations of one whānau, totalling twenty-six different stories. I explore the possibilities of pūrākau as a method and ako (to teach/ learn) as a powerful component in the building and sharing of stories, as writing tools for the (re)presentation of that material and in expressing the researcher’s positionality. Pūrākau as method also enables the utilisation of our cosmogonies as important sources of mātauranga Māori and therefore as crucial to an analysis of our naming motivations and notions of belonging. Furthermore, I critically analyse the disruptions and interruptions to ingoa tangata caused by institutions of colonialism such as religion, law and education. This research argues for the transformative potential of our ingoa tangata and their associated kōrero ingoa in terms of enhancing identity, embedding whakapapa kōrero and keeping Māori values alive within whānau, and beyond.

text: Ko wai tō ingoa? The transformative potential of Māori names Ingoa tangata (personal names) are an expression of te reo Māori, Māori identity, and tino rangatiratanga (self-determination). Nevertheless, our names are still mispronounced, marginalised and demeaned by individuals and institutions, such as schools, the health system, politics and media. This thesis argues that the gift of a Māori name and the assertion of that name over one’s lifetime is simultaneously a political act of resistance and an act of normalisation – an act of just being Māori. In particular, the thesis reveals how whānau naming practices endure and are important for whānau identity and belonging.

A Kaupapa Māori theoretical approach is used to highlight the mana of our ingoa tangata within te ao Māori (the Māori world). I analyse the experiences of six generations of one whānau and the ways in which they have resisted, reclaimed and regenerated our ingoa tangata and associated practices. Kaupapa Māori theory provides a much-needed theoretical framework that privileges te reo Māori and mātauranga Māori throughout this research. This theory also supports Māori researchers to critique and disrupt Western power dynamics within research as well as maintaining the political imperative of decolonisation and resurgence agendas within the research of Indigenous communities.

This thesis foregrounds Pūrākau as a research method to tell the kōrero ingoa (naming stories) of six generations of one whānau, totalling twenty-six different stories. I explore the possibilities of pūrākau as a method and ako (to teach/ learn) as a powerful component in the building and sharing of stories, as writing tools for the (re)presentation of that material and in expressing the researcher’s positionality. Pūrākau as method also enables the utilisation of our cosmogonies as important sources of mātauranga Māori and therefore as crucial to an analysis of our naming motivations and notions of belonging. Furthermore, I critically analyse the disruptions and interruptions to ingoa tangata caused by institutions of colonialism such as religion, law and education. This research argues for the transformative potential of our ingoa tangata and their associated kōrero ingoa in terms of enhancing identity, embedding whakapapa kōrero and keeping Māori values alive within whānau, and beyond.

year: 2017