39110-21-9

Upstream product

• 2378-86-1 4-methylbenzyltriphenylphosphonium bromide 
• 1530-37-6 (4-methylbenzyl)triphenylphosphonium chloride 
• 104-81-4 4-Methylbenzyl bromide 
• 104-82-5 4-Methylbenzyl chloride 
• 603-35-0 triphenylphosphine 

Downstream Products

• 67162-63-4 6-(4-methylphenyl)-5-phenyl-1,2-dithiafulvene 
• 59625-63-7 2,3-Diphenyl-4-[1-p-tolyl-meth-(Z)-ylidene]-cyclobut-2-enone 
• 222547-17-3 1-Methyl-4-((Z)-3,3,3-trifluoro-2-hexylsulfanyl-propenyl)-benzene 
• 222547-26-4 1-Methyl-4-((Z)-3,3,4,4,4-pentafluoro-2-hexylsulfanyl-but-1-enyl)-benzene 
• 222547-04-8 1-Methyl-4-[(Z)-3,3,3-trifluoro-2-(hexane-1-sulfonyl)-propenyl]-benzene 
• 222547-14-0 1-Methyl-4-[(Z)-3,3,4,4,4-pentafluoro-2-(hexane-1-sulfonyl)-but-1-enyl]-benzene 
• 162779-96-6 (3R,4S)-1-Benzyl-3-hydroxy-4-(2-p-tolyl-ethyl)-azetidin-2-one 
• 162780-03-2 (S)-1-Benzyl-4-(2-p-tolyl-ethyl)-azetidine-2,3-dione 
• 162780-10-1 (S)-3-Benzyl-4-(2-p-tolyl-ethyl)-oxazolidine-2,5-dione 
• 603-35-0 triphenylphosphine 
• 791-28-6 Triphenylphosphine oxide 
• 127536-23-6 (E)-2-Ethoxy-3-p-tolyl-acrylic acid ethyl ester 
• 127536-15-6 (Z)-2-Ethoxy-3-p-tolyl-acrylic acid ethyl ester 
• 55088-80-7 1-(cyclopropylidenemethyl)-4-methylbenzene 

Relevant academic research and scientific papers

Substituted dienes prepared from betulinic acid – Synthesis, cytotoxicity, mechanism of action, and pharmacological parameters

A set of new substituted dienes were synthesized from betulinic acid by its oxidation to 30-oxobetulinic acid followed by the Wittig reaction. Cytotoxicity of all compounds was tested in vitro in eight cancer cell lines and two noncancer fibroblasts. Almost all dienes were more cytotoxic than betulinic acid. Compounds 4.22, 4.30, 4.33, 4.39 had IC50 below 5 μmol/L; 4.22 and 4.39 were selected for studies of the mechanism of action. Cell cycle analysis revealed an increase in the number of apoptotic cells at 5 × IC50 concentration, where activation of irreversible changes leading to cell death can be expected. Both 4.22 and 4.39 led to the accumulation of cells in the G0/G1 phase with partial inhibition of DNA/RNA synthesis at 1 × IC50 and almost complete inhibition at 5 × IC50. Interestingly, compound 4.39 at 5 × IC50 caused the accumulation of cells in the S phase. Higher concentrations of tested drugs probably inhibit more off-targets than lower concentrations. Mechanisms disrupting cellular metabolism can induce the accumulation of cells in the S phase. Both compounds 4.22 and 4.39 trigger selective apoptosis in cancer cells via intrinsic pathway, which we have demonstrated by changes in the expression of the crucial apoptosis-related protein. Pharmacological parameters of derivative 4.22 were superior to 4.39, therefore 4.22 was the finally selected candidate for the development of anticancer drug.

Direct and Scalable Electroreduction of Triphenylphosphine Oxide to Triphenylphosphine

The direct and scalable electroreduction of triphenylphosphine oxide (TPPO)-the stoichiometric byproduct of some of the most common synthetic organic reactions-to triphenylphosphine (TPP) remains an unmet challenge that would dramatically reduce the cost and waste associated with performing desirable reactions that are mediated by TPP on a large scale. This report details an electrochemical methodology for the single-step reduction of TPPO to TPP using an aluminum anode in combination with a supporting electrolyte that continuously regenerates a Lewis acid from the products of anodic oxidation. The resulting Lewis acid activates TPPO for reduction at mild potentials and promotes P-O over P-C bond cleavage to selectively form TPP over other byproducts. Finally, this robust methodology is applied to (i) the reduction of synthetically useful classes of phosphine oxides, (ii) the one-pot recycling of TPPO generated from a Wittig reaction, and (iii) the gram-scale reduction of TPPO at high concentration (1 M) with continuous product extraction and in flow at high current density.

Synthesis of aryl and heterocyclic polyenes and their activity in free radical scavenging

Aryl polyenes and heterocyclic polyenes with the same central C20 unit of β,β-carotene but different terminal groups were synthesised. Their free radical scavenging activity was measured by a 1,1-diphenyl-2-picrylhydrazinyl spectrophotometric method. The results indicated that all the new compounds have free radical scavenging activity.

1-[(E)-2-arylethenyl]-2,2-diphenylcyclopropanes: Kinetics and mechanism of rearrangement to cyclopentenes

Kinetic measurements for the thermal rearrangement of 2,2-diphenyl-1-[(E)- styryl]cyclopropane (22a) to 3,4,4-triphenylcyclopent-1-ene (23a) in decalin furnished ΔHρm{{-{isom}^{ne }}}$=31.0±1.2kcal mol-1 and ΔSρm{{-{isom}^{ne }}}$=-6. 0±2.6e.u. The lowering of ΔHa‰ by 20kcal mol-1, compared with the rearrangement of the vinylcyclopropane parent, is ascribed to the stabilization of a transition structure (TS) with allylic diradical character. The racemization of (+)-(S)-22a proceeds with ΔHρm{{-{rac}^{ne }}}$=28.2±0.8kcal mol -1 and ΔSρm{{-{rac}^{ne }}}$=-5±2e.u., and is at 150° 106 times faster than the rearrangement. Seven further 1-(2-arylethenyl)-2,2-diphenylcyclopropanes 22, (E)- and (Z)-isomers, were synthesized and characterized. The (E)-compounds showed only modest substituent influence in their krac (at 119.4°) and kisom (at 159.3°) values. The lack of solvent dependence of rate opposes charge separation in the TS, but a linear relation of log krac with log p.r.f., i.e., partial rate factors of radical phenylations of ArH, agrees with a diradical TS. The ring-opening of the preponderant s-trans-conformation of 22 gives rise to the 1-exo-phenylallyl radical 26 that bears the diphenylethyl radical in 3-exo-position, and is responsible for racemization. The 1-exo-3-endo-substituted allylic diradical 27 arises from the minor s-gauche-conformation of 22 and is capable of closing the three- or the five-membered ring, 22 or 23, respectively. The discussion centers on the question whether the allylic diradical is an intermediate or merely a TS. Quantum-chemical calculations by Houk etal. (1997) for the parent vinylcyclopropane reveal the lack of an intermediate. Can the conjugation of the allylic diradical with three Ph groups carve the well of an intermediate? Copyright

Untersuchungen im Wittig-System nach einem ordnenden Konzept auf der Basis alternativer Prinzipien

Our results show that the stereoselectivity of the Wittig-reaction can be controlled by the variation of substituents in accord with the ORDERING CONCEPT OF ALTERNATIV PRINCIPLES (individual pairs, known and unknown classes of alternatives).The "all-phenyl Wittig-system" having three phenyl groups on phosphorous two in ylid- and aldehyd-position was chosen as a standard for our investigations.Differentiation in ylid-position and compensation on phosphorous and aldehyd-position were observed by the comparison of "patterns".Consequently, most of the selectivity rules of Wittig-reactions can be explained by the differentiation through alternatives in the ylid-position.Inversion or conservation of the "patterns" of measured data points to the variation in structure of starting materials, reaction rates and selectivities.Amount-controls were also described in certain systems.

A Facile and New Route for the Synthesis of Substituted 1,2-Dithiafulvenes Using Phosphonium Ylides

A wide variety of 6-aryl-5-phenyl-1,2-dithiafulvenes and 6-aroyl-5-phenyl-1,2-dithiafulvenes (4) have been synthesized by the interaction of 5-phenyl-1,2-dithiol-3-one (3a) and phosphonium ylides (2).The synthesis of these dithiafulvenes has also been car

Reactions of the Cyclopropanone Hemiketal Magnesium Salt with Some Nucleophilic Reagents

Cyclopropanol (5), 1-(arylethynyl)cyclopropanol (7), 1-(3-hydroxypropyl)cyclopropanol derivative 10, 1-(2-propynyl)cyclopropanol (14), cyclopropanone cyanohydrin (19), 1-(aminomethyl)cyclopropanol (21) derivatives, benzylidenecyclopropanes 32, and ethyl cyclopropylideneacetate (38) have been prepared from the magnesium salt of cyclopropanone hemiketal 3. 3-Cyclopropylidene-1-propanol (12) and 3-cyclopropylidene-1-propyne (16) have been obtained from the cyclopropanols 10 and 14, respectively. Some reactions of this new synthon were specific. On the other hand, 3 did not undergo the nucleophilic addition of sulfur and nitrogen ylides; it underwent oxidizing ring opening with BrZnCH2COOEt and induced the decomposition of diazomethane.

3-(Substituted) vinyl cephalosporins

New 3-(substituted) vinyl cephalosporin compounds, e.g., 3-(2'-ethoxycarbonylvinyl)-7-phenoxyacetamido-3-cephem-4-carboxylic acid, which are useful as antibiotics, and 3-(substituted) vinyl cephalosporin compounds which are useful as intermediates in preparing antibiotic substances.