Mechanism of the Wacker Oxidation of Alkenes over Cu-Pd-Exchanged Y Zeolites
P. H. Espeel, G. De Peuter, M. C. Tielen, P. A. Jacobs
J. Phys. Chem. 1994, 98 (44), pp 11588–11596



Comments from Requestee
It appears to suggest that the oxygen that forms the Ketone in the wacker oxidation does not come from the external oxygen but is contained insitu from the water present in the process.

Here we go, hang on kiddies

A New Synthesis of Threonine

Mikio Sato, Kenji Okawa and Shiro Akabori

Bulletin of the Chemical Society of Japan
Vol.30 , No.9(1957)pp.937-938
   

Abstract:
     
A new method is described for the synthesis of threonine from acetaldehyde and copper glycinate. This method gives a mixture of allo-threonine and threonine in a high yield (64%).

The Direct Derivations of Some Amino Acids from Glycine
 
Akitsugu Nakahara,Shigeaki Nishikawa and Junji Mitani
Bulletin of the Chemical Society of Japan
Vol. 40 (1967) No. 9  pp.2212-2212

Abstract

Akabori and his co-workers have synthesized threonine from bis(glycinato)copper(II) and acetaldehyde in the presence of sodium carbonate, and have reasoned that the amino group would be protected by coordination, and sufficient activation of the methylene group would result from the polarizing effect of the metal atom. However, this method is not widely applicable for the derivation of many amino acids other than the b-hydroxy-a-amino acids, perhaps because of incomplete protection of the amino group or incomplete activation of the methylene group in the bis(glycinato)copper(II)

Introduction of Side Chains into Polyglycine Dispersed on Solid Surface. I

Shiro Akabori, Kenji Okawa and Mikio Sato
     

Abstract:

1) Polyglycine dispersed on the surface of kaolinite was prepared by the polycondensation of N-carboxylic anhydride or glycine ester on kaolinite.
2) It was concluded that a part of glycyl residues in polyglycine dispersed on kaolinite was easily converted to seryl or threonyl residues by the condensation with formaldehyde or acetaldehyde.
3) The condensation occurred not only at amino terminal glycyl residues but also at non-terminal glycyl residues.

Hmmmmmmmmmmmmmmm Got a sniff of 'something'.........
 

Synthesis of tropine-labeled atropine II. Prototype synthesis for the preparation of tropine-14C and atropine-14C from arabinose-14C
Gilbert C. Schmidt, Thomas E. Eling, John M. McOwen and John C. Drach
Journal of Pharmaceutical Sciences Volume 56 Issue 11, Pages 1453-1459, 1967


Abstract
Prototype methods for the synthesis of tropines-14C and tropine-labeled atropines are described. These compounds and the requisite labeled intermediates may be synthesized from arabinose-5-14C or arabinose-UL-14C. Yields for each step in the conversion of arabinose to succindialdehyde via 2, 5-diethoxytetrahydrofuran have been determined. Predicted yields of 27 per cent atropine, based on starting pentose, were confirmed by synthesis of the alkaloid from 2 mmole quantities of arabinose. This procedure is the first published method for labeling atropine in the carbon skeleton of the tropine moiety.

Synthesis of tropine-labeled atropine I. Micro methods for the synthesis of tropine and for its esterification with tropic acid
Gilbert C. Schmidt, Thomas E. Eling, John C. Drach
Journal of Pharmaceutical SciencesVolume 56 Issue 2, Pages 215-221, 1967


Abstract
Yields for each step in the esterification of tropine and tropic acid have been determined with micro and semimicro quantities of reactants. In a similar way, the Robinson condensation has been studied. Data are compared with the findings of other investigators. In the esterification of micro quantities of tropine and tropic acid, 70-75 per cent of theoretical atropine yields are obtained routinely. Based on any intermediate in the Robinson condensation, micro quantities of reactants routinely produce 67-72 per cent of theoretical tropine yields. Predicted yields of 47-54 per cent atropine from Robinson intermediates were confirmed by synthesis of atropine from each of the Robinson reactants. The procedures are designed for the synthesis of labeled tropine and tropine-labeled atropine from labeled arabinose


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Synthesis of tropine-labeled atropine III. Synthesis of N-methyl-14C-tropine and N-methyl-14C-atropine
Gilbert C. Schmidt, Thomas E. Eling, John M. McOwen
Journal of Pharmaceutical SciencesVolume 57 Issue 3, Pages 443 - 446, 1968


Abstract
Using a previously described modification of the Robinson condensation, N-methyl-14C-tropine, specific gravity 1 mc./mmole, was synthesized from methylamine-14C-HCl in 65 percent of theoretical yield. Subsequent esterification with unlabeled tropic acid gave N-methyl-14C-atropine, specific activity 1 mc./mmole, in 45 percent of theoretical yield, based on methylamine. Synthesis of these compounds validates previous studies and firmly establishes a general pathway for labeling the carbon skeleton of tropine with radioactive carbon.



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Synthesis of tropine-labeled atropine IV. Labeling of the 2, 3, and 4 positions of atropine from citric-14C acid
Thomas E. Eling, John M. McOwen, Gilbert C. Schmidt
Journal of Pharmaceutical SciencesVolume 57 Issue 8, Pages 1357-1360, 1968




Abstract
Using a modification of the Robinson condensation, citric-3-14C acid, citric-2,4-14C acid, and citric-2,3,4-14C acid were converted into correspondingly labeled tropine and atropine. The specific activities of the products varied from 0.62 to 1.0 depending on the labeled compound. This is the first reported syntheses of tropine or atropine labeled with 14C in positions other than the endo-methyl group.

The Three-Dimensional Structures of the Cocaines. II. Racemic Allococaine and Racemic Allopseudococaine
STEPHEN P. FINDLAY
J. Org. Chem., 1959, 24 (10), pp 1540–1550


Abstract
Catalytic hydrogenation of racemic 2-carbomethoxy-tropinone in acetic acid yields racemic alloecgonine methyl ester, which can be transformed to the racemates of alloecgonine, allococaine, allopseduoecgonine, allopseudoecgonine methyl ester, and allopseudococaine. Some limitations of a generalization concerning the course of catalytic hydrogenation of cyclic ketones as it applies to certain keto derivatives of the tropane and morphine alkaloids are noted. The three-dimensional structures of the new cocaines are tentatively assigned. The possible utility of molecular rotation data in ascertaining the absolute configuration of transformation products of the 2-carbomethoxy derivatives of both tropinone and N-methyl-granatonine is indicated. Some other possible methods of synthesizing the new cocaine isomers and the drawbacks thereof are mentioned.



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Fmoc-protected tropane-based amino acids for peptide structure-function studies
Philip E. Thompson and Milton T. W. Hearn
Tetrahedron Letters Volume 38, Issue 16, 21 April 1997, Pages 2907-2910


Abstract
Cyclic amino acids derived from the tropane alkaloid nucleus have been prepared and incorporated into synthetic peptides. These conformationally constrained ?-amino acids hold considerable potential for use in the development of novel, synthetic analogues of biologically active peptides.

The Three-dimensional Structure of the Cocaines. Part I. Cocaine and Pseudococaine
Stephen P. Findlay
J. Am. Chem. Soc. 1954, 76 (11), pp 2855–2862


Abstract
Published experimental data on the chemistry of cocaine and its simpler derivatives are interpreted as indicating that this base is 2B-carbomethoxy-3B-benzoxytropane and pseudococaine 2a-carbomethoxy-3B-benzoxytropane. Pertinent data in the literature have been verified or corrected. Cocaine is readily transformed by sodium methoxide in methanol to pseudoecgoninine methyl ester. Willstatter's ecgonine methylbetaine is in fact the pseudo isomer. O-Benzolnorecgonine is convertible in the presence of base to the previously unknown N-benzoyl isomer. Names and structures for the other two possible cocaines are proposed.

Alkaloids of the sorghum ergot pathogen (Claviceps africana): assay methods for grain and feed and variation between sclerotia/sphacelia

B. J. Blaney, R. Maryam, S-A. Murray and M. J. Ryley

Australian Journal of Agricultural Research 54(2) 167 - 175
DOI:10.1071/AR02095

Abstract

Assay methods for the alkaloids of sorghum ergot (Claviceps africana) are described and compared. Sorghum ergot bodies (sclerotia/sphacelia) from various regions of Queensland and New South Wales were collected in 1997 and 2001 and assayed by spectrophotometry, thin layer chromatography, or high performance liquid chromatography (HPLC). All contained dihydroergosine (DHES) as the main alkaloid component (about 80%), with smaller amounts of dihydroelymoclavine and festuclavine. The preferred method of assay for infected sorghum and mixed feeds involved extraction into dichloromethane:methanol:ethyl acetate:ammonium hydroxide (50:5:25:1) using an ultrasonic bath. After solvent removal, the extract was dissolved in diethyl ether and partitioned into 0.5 M hydrochloric acid. After adjusting the pH to 8–10 with ammonium hydroxide, the alkaloids were extracted into dichloromethane, the solvent evaporated, and the residue dissolved in methanol. HPLC separation was on a C18 column, 150 × 3.9 mm, run isocratically at 40°C, with acetonitrile:0.1% ammonium acetate:methanol (31:50:20) as the mobile phase. Detection was either by UV at 280 nm or by fluorescence with excitation at 235 nm and absorbance at 340 nm. Levels of quantitation for DHES in sorghum approached 0.1 mg/kg (UV) and 0.01 mg/kg (fluorescence). Method recoveries for DHES in the range of 0.025–7 mg/kg averaged 75%. The total alkaloid content of ergot bodies (sclerotia/sphacelia) from different batches of grain varied from 100 to 7900 mg/kg (0.79%). Within batches, there was much less variation in the alkaloid content of ergot bodies, but larger ergots tended to contain more alkaloid than smaller ergots, and those infected with Cerebella species contained even less; this probably related to the ratio of sclerotial/sphacelial tissue present. Honeydew also contained DHES (1–10 mg/kg) and might contaminate clean grain at significant levels. Tests on 4 farms showed that substantial amounts of ergot bodies and alkaloids were removed during grain harvesting.

Alkaloid production by isolates of the sorghum ergot pathogen (Claviceps africana) from Australia and other countries

Barry Blaney, Sukumar Chakraborty, Sally-Ann Murray

Australian Journal of Agricultural Research, Vol. 57 No. 9 Pages 1023 - 1028
doi:10.1071/AR05334

Abstract

Isolates of Claviceps africana from Australia, Africa, Asia, and America were tested for the production of dihydroergosine (DHES), and its biogenic precursors dihydroelymoclavine (DHEL) and festuclavine (FEST), in culture. Several growth media were evaluated to optimise alkaloid production with little success. The best of these involved 2-stage culturing on high-sucrose substrate. Australian C. africana isolates varied widely and inconsistently in alkaloid production, with DHES concentrations in mycelium ranging from: <0.1 to 9 mg DHES/kg; <0.1 to 1.6 mg DHEL/kg; and <0.1 to 0.4 mg FEST/kg. In a separate experiment using similar culturing techniques, DHES was produced by 2 of 3 Australian isolates, 1 of 3 USA isolates, 1 of 4 Indian isolates, the sole Puerto Rican isolate, the sole Japanese isolate, but not the sole South African isolate. In this experiment, DHES concentrations detected in mycelium of Australian isolates (0.1–1.0 mg DHES/kg) were of similar magnitude to isolates from other countries (0.2–1.8 mg DHES/kg). Three C. africana isolates, including one that produced only traces of alkaloid in culture after 8 weeks, were inoculated onto panicles of sterile male sorghum plants. After 8 weeks, all 3 isolates produced 10–19 mg DHES/kg in the panicles, demonstrating that the growing plant favoured more consistent alkaloid production than culture medium.

FUNGAL NEUROTOXINS

W.L. BRYDEN
14th Annual Conference. Nutrition Society of Australia; (1989)
Proceedings of the Nutrition Society of Australia, Murdoch WA, 1989. pp. 45-53

Summary

The fungal neurotoxins are briefly reviewed, especially where they have known involvement in human and animal disease. The neurological effects of ergot alkaloids and the tremorgens have been studied in detail as these groups of toxins have often been associated with mycotoxicoses. Other neurotoxic mycotoxins are briefly discussed, but, in most instances, very little research has been carried out on these compounds. Further detailed study of fungal neurotoxins will determine their likely occurence in the food chain, assist in the delineation of neurological function and may provide a source of compounds with medical application.

Ergot: A New Disease threat to Sorghum in the Americas and Australia

R. Bandiopadhyay, D.E. Frederickson, N.W. McLaren, G.N. Odvody and M.J. Ryley
Plant Disease (1998) Volume 82(4), pp. 356-367
DOI: 10.1094/PDIS.1998.82.4.356

Abstract

Sorghum, Sorghum bicolor (L.) Moench, is the world's fifth most important cereal crop, cultivated on about 45 million hectares for food, feed, beverage, and fodder. The most significant technological change since the 1960's has been the development and use of F1 hybrid seed, which has led to a dramatic improvement in the crops productivity. Sorghum cultivation in intensive, commercialized systems where yields average 3 to 5 t ha-1 relies almost entirely on hybrid seed. In contrast, yields vary widely and average less than 1 t ha-1 in low-input production systems.

Sorghum Ergot: Distinguishing Sphacelia and Sclerotia of Claviceps africanus in Seed

Debra E. Frederickson and Gary N. Odvody. Assisted by Thomas Isakeit*

Texas Agricultural Extension Service
The Texas A&M University System (L-5315/6-99)

Abstract

The field symptoms of sorghum ergot are familiar to anyone involved in sorghum production, but it is more difficult to identify the fungal pathogen in seed. This is because there is a lack of understanding about the structure and function of sphacelia and sclerotia and because immature, cracked and moldy seed and other foreign objects are frequently misidentified as ergot fungal bodies.

Effect of climate variability on event frequency of sorghum ergot in Australia

Wang, E. and Ryley, M. and Meinke, H.

Australian Journal of Agricultural Research, 54(6) (2003), pp. 599-611.

Abstract

The significant effect of ergot, caused by Claviceps africana, on the Australian sorghum industry, has led to considerable research on the identification of resistant genotypes and on the climatic conditions that are conducive to ergot outbreaks. Here we show that the potential number of monthly ergot events differs strongly from year to year in accordance with ENSO (El Niño–Southern Oscillation)-related climate variability. The analysis is based on long-term weather records from 50 locations throughout the sorghum-growing areas of Australia and predicts the potential number of monthly ergot events based on phases of the Southern Oscillation Index (SOI). For a given location, we found a significant difference in the number of potential ergot events based on SOI phases in the preceding month, with a consistently positive SOI phase providing the greatest risk for the occurrence of ergot for most months and locations. This analysis provides a relative risk assessment for ergot outbreaks based on location and prevailing climatic conditions, thereby assisting in responsive decision-making to reduce the negative effect of sorghum ergot.