title: Regioisomeric preferences in the orthomanganation of meta-substituted acetophenones and isopropyl benzoates, and application of iodo-demanganation with iodine chloride to the synthesis of 2-iodo-3-O-substituted and other ortho-iodo arylcarbonyl compounds

authors: Cooney, Janine M.

subjects: Manganese

abstract: Synthesis is reported of regioisomeric ortho-[Mn(CO)4] derivatives of aryl ketones (2-chlorothioxanthen-9-one and 3′,4′-methylenedioxyacetophenone) and esters (isopropyl 3-methoxy- and 3-acetoxy-benzoate), as well as of the single ortho-[Mn(CO)4] products from methyl 4-methoxy- and 3,5-dimethoxy-benzoate. Factors influencing the preference for manganation at the crowded positions ortho to the C=O in meta-substituted aryl ketones and esters are considered. The frequency of the lowest energy metal carbonyl stretching mode is useful in the structural assignment of the regioisomers. Isopropyl 2-iodo-3-methoxy- and 2-iodo-3-acetoxy-benzoates are obtained by reaction of iodine chloride to replace the Mn(CO)4 group at the crowded 2-position of the corresponding orthomanganated 3-O-substituted benzoate esters. ortho-Iodoacetophenones were prepared likewise, without α-iodination, some with iodine in crowded positions (2′-iodo-3′-methoxy-, -3′,4′-methylenedioxy- and -3′,4′,5′-trimethoxy-acetophenone), others with O-protected 2′-hydroxy groups (2′-benzyloxy- and 2′-t-butyldimethylsilyloxy-3′,4′-dimethoxy-6′-iodobenzene and 2′-t-butyldimethylsiloxy-6′-iodobenzene). Potential general synthetic routes to derivatives of 2-iodo-3-hydroxy-, 2-iodo-3,4-dihydroxy-, and 2-iodo-6-hydroxy-aryl carbonyl compounds are indicated. The corresponding routes to 3-iodo-4-acetyl-2,5-dimethylthiophene and 3-iodo-2-acetylthiophene are also reported.

text: Regioisomeric preferences in the orthomanganation of meta-substituted acetophenones and isopropyl benzoates, and application of iodo-demanganation with iodine chloride to the synthesis of 2-iodo-3-O-substituted and other ortho-iodo arylcarbonyl compounds Synthesis is reported of regioisomeric ortho-[Mn(CO)4] derivatives of aryl ketones (2-chlorothioxanthen-9-one and 3′,4′-methylenedioxyacetophenone) and esters (isopropyl 3-methoxy- and 3-acetoxy-benzoate), as well as of the single ortho-[Mn(CO)4] products from methyl 4-methoxy- and 3,5-dimethoxy-benzoate. Factors influencing the preference for manganation at the crowded positions ortho to the C=O in meta-substituted aryl ketones and esters are considered. The frequency of the lowest energy metal carbonyl stretching mode is useful in the structural assignment of the regioisomers. Isopropyl 2-iodo-3-methoxy- and 2-iodo-3-acetoxy-benzoates are obtained by reaction of iodine chloride to replace the Mn(CO)4 group at the crowded 2-position of the corresponding orthomanganated 3-O-substituted benzoate esters. ortho-Iodoacetophenones were prepared likewise, without α-iodination, some with iodine in crowded positions (2′-iodo-3′-methoxy-, -3′,4′-methylenedioxy- and -3′,4′,5′-trimethoxy-acetophenone), others with O-protected 2′-hydroxy groups (2′-benzyloxy- and 2′-t-butyldimethylsilyloxy-3′,4′-dimethoxy-6′-iodobenzene and 2′-t-butyldimethylsiloxy-6′-iodobenzene). Potential general synthetic routes to derivatives of 2-iodo-3-hydroxy-, 2-iodo-3,4-dihydroxy-, and 2-iodo-6-hydroxy-aryl carbonyl compounds are indicated. The corresponding routes to 3-iodo-4-acetyl-2,5-dimethylthiophene and 3-iodo-2-acetylthiophene are also reported.

year: 2001-09-01

title: Rapid carbon accumulation in a peatland following Late Holocene tephra deposition, New Zealand

authors: Ratcliffe, Joshua Lee

abstract: Contemporary measurements of carbon (C) accumulation rates in peatlands around the world often show the C sink to be stronger on average than at times in the past. Alteration of global nutrient cycles could be contributing to elevated carbon accumulation in the present day. Here we examine the effect of volcanic inputs of nutrients on peatland C accumulation in Moanatuatua Bog, New Zealand, by examining a high-resolution Late Holocene C accumulation record during which powerful volcanic eruptions occurred, depositing two visible rhyolitic tephra layers (Taupo, 232 ± 10 CE; Kaharoa, 1314 ± 12 CE). Carbon accumulation rates since c. 50 CE, well before any human presence, increased from a background rate of 23 g C m−2 yr−1 up to 110 g C m−2 yr−1 following the deposition of the Taupo Tephra, and 84 g C m−2 yr−1 following the deposition of the Kaharoa Tephra. Smaller but nevertheless marked increases in C accumulation additionally occurred in association with the deposition of three andesitic-dacitic cryptotephras (each ≤ ∼1 mm thick) of the Tufa Trig Formation between the Taupo and Kaharoa events. These five periods of elevated C uptake, especially those associated with the relatively thick Taupo and Kaharoa tephras, were accompanied by shifts in nutrient stoichiometry, indicating that there was greater availability of phosphorus (P) relative to nitrogen (N) and C during the period of high C uptake. Such P was almost certainly derived from volcanic sources, with P being present in the volcanic glass at Moanatuatua, and many of the eruptions described being associated with the local deposition of the P rich mineral apatite. We found peatland C accumulation to be tightly coupled to N and P accumulation, suggesting nutrient inputs exert a strong control on rates of peat accumulation. Nutrient stoichiometry indicated a strong ability to recover P within the ecosystem, with C:P ratios being higher than most other peatlands in the literature. We conclude that nutrient inputs, deriving from volcanic eruptions, have been very important for C accumulation rates in the past. Therefore, the elevated nutrient inputs occurring in the present day could offer a more plausible explanation, as opposed to a climatic component, for observed high contemporary C accumulation in New Zealand peatlands.

text: Rapid carbon accumulation in a peatland following Late Holocene tephra deposition, New Zealand Contemporary measurements of carbon (C) accumulation rates in peatlands around the world often show the C sink to be stronger on average than at times in the past. Alteration of global nutrient cycles could be contributing to elevated carbon accumulation in the present day. Here we examine the effect of volcanic inputs of nutrients on peatland C accumulation in Moanatuatua Bog, New Zealand, by examining a high-resolution Late Holocene C accumulation record during which powerful volcanic eruptions occurred, depositing two visible rhyolitic tephra layers (Taupo, 232 ± 10 CE; Kaharoa, 1314 ± 12 CE). Carbon accumulation rates since c. 50 CE, well before any human presence, increased from a background rate of 23 g C m−2 yr−1 up to 110 g C m−2 yr−1 following the deposition of the Taupo Tephra, and 84 g C m−2 yr−1 following the deposition of the Kaharoa Tephra. Smaller but nevertheless marked increases in C accumulation additionally occurred in association with the deposition of three andesitic-dacitic cryptotephras (each ≤ ∼1 mm thick) of the Tufa Trig Formation between the Taupo and Kaharoa events. These five periods of elevated C uptake, especially those associated with the relatively thick Taupo and Kaharoa tephras, were accompanied by shifts in nutrient stoichiometry, indicating that there was greater availability of phosphorus (P) relative to nitrogen (N) and C during the period of high C uptake. Such P was almost certainly derived from volcanic sources, with P being present in the volcanic glass at Moanatuatua, and many of the eruptions described being associated with the local deposition of the P rich mineral apatite. We found peatland C accumulation to be tightly coupled to N and P accumulation, suggesting nutrient inputs exert a strong control on rates of peat accumulation. Nutrient stoichiometry indicated a strong ability to recover P within the ecosystem, with C:P ratios being higher than most other peatlands in the literature. We conclude that nutrient inputs, deriving from volcanic eruptions, have been very important for C accumulation rates in the past. Therefore, the elevated nutrient inputs occurring in the present day could offer a more plausible explanation, as opposed to a climatic component, for observed high contemporary C accumulation in New Zealand peatlands.

year: 2020

title: Exploring te ao Māori: The role of museums

authors: Clarkin-Phillips, Jeanette

subjects: museum

abstract: Museums offer many opportunities for developing knowledge of the bicultural heritage of Aotearoa New Zealand. This article reports on research involving a kindergarten located in a national museum. It discusses children’s growing understanding of te ao Māori (the world of Māori) through their regular visits to the collections and exhibits in the museum and suggests teachers in early childhood centres may find connecting with their local museum a valuable resource for enhancing bicultural practice.

text: Exploring te ao Māori: The role of museums Museums offer many opportunities for developing knowledge of the bicultural heritage of Aotearoa New Zealand. This article reports on research involving a kindergarten located in a national museum. It discusses children’s growing understanding of te ao Māori (the world of Māori) through their regular visits to the collections and exhibits in the museum and suggests teachers in early childhood centres may find connecting with their local museum a valuable resource for enhancing bicultural practice.

year: 2012