Reaction of polysulfide anions with α, β, unsaturated isoprenoid aldehydes in aquatic media:: simulation of oceanic conditions

被引:41
作者
Amrani, A [1 ]
Aizenshtat, Z [1 ]
机构
[1] Hebrew Univ Jerusalem, Casali Inst Appl Chem, Dept Organ Chem, IL-91904 Jerusalem, Israel
关键词
D O I
10.1016/j.orggeochem.2004.04.002
中图分类号
P3 [地球物理学]; P59 [地球化学];
学科分类号
0708 ; 070902 ;
摘要
Polysulfide anions react with alpha, beta unsaturated aldehydes in aquatic media. Michael addition mechanisms control the first step, which follows the same pathway as in phase transfer catalysis (PTC) systems. The end products are polysulfide cross-linked oligo-polymers. The kinetic profiles, measured by H-1 NMR and elemental analysis, changed dramatically with the length of the carbon skeleton. The reaction rates are controlled by the concentration of both polysulfides and the substrate. A comparative study revealed the importance of the cation (e.g., sodium or ammonium) and pH conditions, as controlling factors. The mechanism proposed is further elucidated by the detailed study of MeLi/MeI degradation products release from the oligo-polymers formed. These results are important in increasing our understanding the role of polysulfides in sulfur enrichment of organic matter in marine environments. (C) 2004 Elsevier Ltd. All rights reserved.
引用
收藏
页码:909 / 921
页数:13
相关论文
共 36 条
[1]   Clues to early diagenetic sulfurization processes from mild chemical cleavage of labile sulfur-rich geomacromolecules [J].
Adam, P ;
Schneckenburger, P ;
Schaeffer, P ;
Albrecht, P .
GEOCHIMICA ET COSMOCHIMICA ACTA, 2000, 64 (20) :3485-3503
[2]  
Aizenshtat, 1983, ADV ORGANIC GEOCHEMI
[3]   Photosensitized oxidation of naturally occurring isoprenoid allyl alcohols as a possible pathway for their transformation to thiophenes in sulfur rich depositional environments [J].
Amrani, A ;
Aizenshtat, Z .
ORGANIC GEOCHEMISTRY, 2004, 35 (06) :693-712
[4]  
ASINGER F, 1959, LIEBIGS ANN CHEM, V627, P195
[5]   ISOPRENOID THIOPHENES - NOVEL PRODUCTS OF SEDIMENT DIAGENESIS [J].
BRASSELL, SC ;
LEWIS, CA ;
DELEEUW, JW ;
DELANGE, F ;
DAMSTE, JSS .
NATURE, 1986, 320 (6058) :160-162
[6]   LABORATORY SIMULATION OF NATURAL SULFURIZATION .1. FORMATION OF MONOMERIC AND OLIGOMERIC ISOPRENOID POLYSULFIDES BY LOW-TEMPERATURE REACTIONS OF INORGANIC POLYSULFIDES WITH PHYTOL AND PHYTADIENES [J].
DEGRAAF, W ;
DAMSTE, JSS ;
DELEEUW, JW .
GEOCHIMICA ET COSMOCHIMICA ACTA, 1992, 56 (12) :4321-4328
[7]   THE DISTRIBUTION AND ISOTOPIC COMPOSITION OF SULFUR IN ORGANIC-RICH SEDIMENTARY-ROCKS [J].
DINUR, D ;
SPIRO, B ;
AIZENSHTAT, Z .
CHEMICAL GEOLOGY, 1980, 31 (1-2) :37-51
[8]   ENDOCYCLIC VS EXOCYCLIC ATTACK IN NUCLEOPHILIC DISPLACEMENT-REACTIONS ON 5-MEMBERED AND 6-MEMBERED CYCLIC ONIUM SALTS [J].
ELIEL, EL ;
HUTCHINS, RO ;
MEBANE, R ;
WILLER, RL .
JOURNAL OF ORGANIC CHEMISTRY, 1976, 41 (06) :1052-1057
[9]   Biogeochemical controls on reaction of sedimentary organic matter and aqueous sulfides in holocene sediments of Mud Lake, Florida [J].
Filley, TR ;
Freeman, KH ;
Wilkin, RT ;
Hatcher, PG .
GEOCHIMICA ET COSMOCHIMICA ACTA, 2002, 66 (06) :937-954