Needs and gaps in optical underwater technologies and methods for the investigation of marine animal forest 3D-structural complexity

Marine animal forests are benthic communities dominated by sessile suspension feeders (such as sponges, corals, and bivalves) able to generate three-dimensional (3D) frameworks with high structural complexity. The biodiversity and functioning of marine animal forests are strictly related to their 3D complexity. The present paper aims at providing new perspectives in underwater optical surveys. Starting from the current gaps in data collection and analysis that critically limit the study and conservation of marine animal forests, we discuss the main technological and methodological needs for the investigation of their 3D structural complexity at different spatial and temporal scales. Despite recent technological advances, it seems that several issues in data acquisition and processing need to be solved, to properly map the different benthic habitats in which marine animal forests are present, their health status and to measure structural complexity. Proper precision and accuracy should be chosen and assured in relation to the biological and ecological processes investigated. Besides, standardized methods and protocols are strictly necessary to meet the FAIR (findability, accessibility, interoperability, and reusability) data principles for the stewardship of habitat mapping and biodiversity, biomass, and growth data

The trifluoromethoxy group:- a long-range electron-withdrawing substituent

Judged by its capacity to promote a hydrogen/metal permutation at an ortho position, the trifluoromethoxy group is superior to both the methoxy and trifluoromethyl groups. Moreover, like CF3 and unlike OCH3, OCF3 exerts a long-range effect that still considerably lowers the basicity of arylmetal compds. when located in a more remote meta or even para position. As a consequence, 4-(trifluoromethoxy)anisole is deprotonated by sec-butyllithium mainly, and by tert-butyllithium exclusively, at a position adjacent to the OCH3 group rather than next to the strongly electron-withdrawing CF3O group. 1,3-Benzodioxole undergoes ortho lithiation only six times faster than anisole, whereas 2,2-difluoro-1,3-benzodioxole reacts about 5000 times faster, as evidenced by competition expts. The structure and distance dependence of substituent effects can be rationalized by assuming superposing s- and p-polarizing interactions. [on SciFinder (R)]LSCOCAN 137:5886 22-12 Physical Organic Chemistry Institut de Chimie Organique Ecole Polytechnique Federale de Lausanne,Lausanne,Switz. Journal 0947-6539 written in English. 274-09-9 (1,3-Benzodioxole); 710-18-9 (4-(Trifluoromethoxy)anisole); 1583-59-1 (1,3-Benzodioxole, 2,2-difluoro-); 2216-69-5 (1-Methoxynaphthalene); 403646-52-6 (Naphthalene, 1-(trifluoromethoxy)-) Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), RCT (Reactant), PROC (Process), RACT (Reactant or reagent) (trifluoromethoxy group as long-range electron-withdrawing substituent); 142738-94-1P (Benzene, 1-methoxy-3-(Trifluoromethoxy)-); 261952-22-1P (Benzene, 1-methoxy-2-(Trifluoromethoxy)-) Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), PROC (Process), RACT (Reactant or reagent) (trifluoromethoxy group as long-range electron-withdrawing substituent); 827-99-6 (Phenol, 3-(trifluoromethoxy)-); 32858-93-8 (Phenol, 2-(trifluoromethoxy)-) Role: RCT (Reactant), RACT (Reactant or reagent) (trifluoromethoxy group as long-range electron-withdrawing substituent); 594-19-4 (tert-Butyllithium); 598-30-1 (sec-Butyllithium) Role: RGT (Reagent), RACT (Reactant or reagent) (trifluoromethoxy group as long-range electron-withdrawing substituent); 883-21-6P (2-Naphthoic acid, 1-methoxy); 5768-39-8P (1,3-Benzodioxole-4-carboxylic acid); 191604-88-3P (Benzoic acid, 2-methoxy-5-(trifluoromethoxy)-); 433330-69-9P; 433330-70-2P; 433330-71-3P; 433330-72-4P; 433330-73-5P Role: SPN (Synthetic preparation), PREP (Preparation) (trifluoromethoxy group as long-range electron-withdrawing substituent

The metalation of 1- and 2-(trifluoromethyl)naphthalenes: Noteworthy site selectivities

This article provides insight into the various factors by which electroneg. substituents affect the kinetic acidity of arenes and, more specifically, naphthalenes. Both 1- and 2-(trifluoromethyl)naphthalenes were consecutively treated with an organometallic or lithium dialkylamide-type base and carbon dioxide. Due to single electron-transfer triggered side reactions, the yields of (trifluoromethyl)naphthoic acids were moderate to poor. 1-(Trifluoromethyl)naphthalene was exclusively attacked at the 2-position as expected. The 2-isomer reacted with tert-butyllithium in the presence of potassium tert-butoxide solely at the 1-position, but with sec-butyllithium in the presence of N,N,N',N'-tetramethylethylenediamine concomitantly at the 3- and 4-positions. Authentic samples of the key acids were prepd. based on independent, unambiguous methods. [on SciFinder (R)

A homologous series of O- and N-functionalized 2,2-difluoro-1,3-benzodioxoles: An exercise in organometallic methodology

The conversion of 2,2-difluoro-1,3-benzodioxole, an exceptionally acidic arene, via a 4-lithiated intermediate into more than three dozen new derivs. was conceived as a case study. The lithiated species was trapped by C0-electrophiles (4-toluenesulfonyl azide, fluorodimethoxyborane, iodine), C1-electrophiles (carbon dioxide, N,N-dimethylformamide, formaldehyde, di-Me sulfate), C2-electrophiles (oxalic acid diesters, oxirane), C3-electrophiles (oxetane), and higher alkyl iodides. The resulting carboxylic acid 2,2-difluoro-1,3-benzodioxole-4-carboxylic acid may be treated with organolithium compds. to afford ketones and the aldehyde 2,2-difluoro-1,3-benzodioxole-4-carboxaldehyde may be condensed with nitromethane or acetic anhydride under basic conditions. If not oxidized with chromium trioxide to the corresponding carboxylic acids, the alcs., e.g., 4-(3-hydroxypropyl)-2,2-difluoro-1,3-benzodioxole can be transformed into the corresponding bromides or sulfonates. Their condensation with nitrogen-contg. C0-nucleophiles (hydroxylamine, sodium azide, potassium phthalimide), C1-nucleophiles (potassium cyanide), and C2-nucleophiles (acetonitrile) opens a convenient access to amines. Other reactions gave, despite a proven track record in other areas, only moderate yields. [on SciFinder (R)

Trifluoromethoxy Substituted Anilines: Metalation as the Key Step for Structural Elaboration

Trifluoromethoxy-substituted anilines undergo hydrogen/lithium permutation (\"metalation\") with optional site selectivity depending on the N-protective group employed. N-tert-Butoxycarbonyl-2- and -4-(trifluoromethoxy)aniline react with tert-BuLi at the nitrogen-adjacent 6- and 2-position affording, after electrophilic trapping, the corresponding substituted anilines I (R1 = F3CO, R2 = H, R3 = HO2C; R1 = H, R2 = F3CO, R3 = Me, CHO, HO2C, HOCH2CH2). In contrast, deprotonation of the N,N-bis(trimethylsilyl)-substituted 4-(trifluoromethoxy)aniline occurs at the oxygen-neighboring 3-position. Sec-BuLi attacks 3-trifluoromethoxy-N-(trimethylsilyl)aniline at the 2-position, but 3-trifluoromethoxy-N,N-bis(trimethylsilyl)aniline at the 4-position to provide the corresponding acids II (R4 = HO2C, R5 = H; R4 = H, R5 = HO2C), resp., after carboxylation. The synthesis of two new benzodiazepines III (R6 = F3CO, R7 = H, R8 = F; R6 = Cl, R7 = HO, R8 = F3CO) illustrates the preparative potential of the aniline functionalization mediated by organometallic reagents. [on SciFinder (R)]LSCOCAN 139:117169 25-4 Benzene, Its Derivatives, and Condensed Benzenoid Compounds Institut de Chimie moleculaire et biologique,Ecole Polytechnique Federale,Lausanne,Switz. Journal 0022-3263 written in English. 403646-45-7P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (amidation; prepn. of functionalized anilines, aminobenzoic acids and benzodiazepinones via regioselective metalation/electrophilic substitution of trifluoromethoxy-substituted anilines); 561304-53-8P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (azidation; prepn. of functionalized anilines, aminobenzoic acids and benzodiazepinones via regioselective metalation/electrophilic substitution of trifluoromethoxy-substituted anilines); 94651-33-9 (2-(Trifluoromethoxy)benzaldehyde) Role: RCT (Reactant), RACT (Reactant or reagent) (electrophile; prepn. of functionalized anilines, aminobenzoic acids and benzodiazepinones via regioselective metalation/electrophilic substitution of anilines); 446-52-6 (2-Fluorobenzaldehyde) Role: RCT (Reactant), RACT (Reactant or reagent) (electrophile; prepn. of functionalized anilines, aminobenzoic acids and benzodiazepinones via regioselective metalation/electrophilic substitution of trifluoromethoxy-substituted anilines); 561304-52-7P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (intramol. heterocyclization; prepn. of functionalized anilines, aminobenzoic acids and benzodiazepinones via regioselective metalation/electrophilic substitution of trifluoromethoxy-substituted anilines); 18437-66-6 Role: RCT (Reactant), RACT (Reactant or reagent) (prepn. of functionalized anilines, aminobenzoic acids and benzodiazepinones via regioselective metalation/electrophilic substitution of anilines); 561304-62-9P; 561304-63-0P; 561304-64-1P; 561304-65-2P; 561304-66-3P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of functionalized anilines, aminobenzoic acids and benzodiazepinones via regioselective metalation/electrophilic substitution of anilines); 561304-67-4P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of functionalized anilines, aminobenzoic acids and benzodiazepinones via regioselective metalation/electrophilic substitution of anilines); 124-68-5 (2-Amino-2-methyl-1-propanol); 461-82-5 (4-(Trifluoromethoxy)aniline); 1535-73-5 (3-(Trifluoromethoxyaniline); 1535-75-7 (2-(Trifluoromethoxy)aniline) Role: RCT (Reactant), RACT (Reactant or reagent) (prepn. of functionalized anilines, aminobenzoic acids and benzodiazepinones via regioselective metalation/electrophilic substitution of trifluoromethoxy-substituted anilines); 212696-37-2P; 220107-35-7P; 561304-39-0P; 561304-40-3P; 561304-42-5P; 561304-47-0P; 561304-49-2P; 561304-51-6P; 561304-55-0P; 561304-57-2P; 561304-58-3P; 561304-59-4P; 561304-60-7P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of functionalized anilines, aminobenzoic acids and benzodiazepinones via regioselective metalation/electrophilic substitution of trifluoromethoxy-substituted anilines); 83265-56-9P; 220107-38-0P; 307989-56-6P; 505084-60-6P; 561304-41-4P; 561304-43-6P; 561304-44-7P; 561304-45-8P; 561304-46-9P; 561304-48-1P; 561304-50-5P; 561304-56-1P; 561304-61-8P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of functionalized anilines, aminobenzoic acids and benzodiazepinones via regioselective metalation/electrophilic substitution of trifluoromethoxy-substituted anilines); 561304-54-9P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (redn.; prepn. of functionalized anilines, aminobenzoic acids and benzodiazepinones via regioselective metalation/electrophilic substitution of trifluoromethoxy-substituted anilines

Metalation of 2-Heterosubstituted Naphthalenes at the 1- or 3-Position: Factors That May Determine the Regiochemistry

Upon metalation and subsequent electrophilic trapping, 2-fluoronaphthalene inevitably gives rise to regioisomeric mixtures in varying proportions, whereas 2-(trifluoromethyl) naphthalene undergoes deprotonation either at the 1- or the 3-position, depending on the choice of the reagent. On the other hand, 2-(trifluoromethoxy) naphthalene and 2-methoxynaphthalene react exclusively at the 3-position when, respectively, sec-butyllithium and superbasic reagents are employed. Steric repulsion by the peri hydrogen in combination with crowding due to coordination of the lithium atom with the methoxy group disfavors attack at the 1-position