Β-diketone Derivatives Research Articles

Arene molybdenum chemistry: arene(π-allyl)molybdenum derivatives containing carboxylate, aminocarboxylate, and related ligands

The carboxylato-compounds benzene Mo(π-C3H5)L, where L = O2CH, O2CMe, O2CPh, O2CCH2[Fe(CO)2[π-(π-C5H5)], and related derivatives are described. The complexes where L = NH2CH2CO2 or NH2[CH2]2S have been prepared. The latter reacts with methyl iodide forming the cation {C6H6Mo(π-C3H5)(MeS[CH2]2NH2)}+. β-Diketone derivatives where L = MeCOCHCOMe or MeCOCHCO(OEt) have also been isolated.

Thallium(I) derivatives of β-diketones, phenols and carboxylic acids

A number of thallium(I) derivatives of β-diketones, phenols, and carboxylic acids have been prepared. The u.v. spectra in a variety of aprotic and protic solvents have been observed and interpreted. The results suggest that the thallium–oxygen bond in these derivatives has considerably more covalent character than the analogous alkali-metal–oxygen bonds. The mass spectra have been recorded, and dimeric species observed. Attempts to prepare complexes of these derivatives are reported.

Thio derivatives of β-diketones and their metal chelates. XII. Dipole moments of the nickel(II), palladium(II), and platinum(II) chelates of 3-Mercapto-1,3-diphenylprop-2-en-1-one

Thio derivatives of β-diketones and their metal chelates. XII. Dipole moments of the nickel(II), palladium(II), and platinum(II) chelates of 3-Mercapto-1,3-diphenylprop-2-en-1-one

Boron difluoride chelates as catalysts for curing epoxy resins

AbstractBF2‐chelates are powerful polymerisation catalysts for epoxy resins; derivatives of β‐diketones and of β‐ketoamides are especially interesting as ‘latent’ hardeners. Comparison of these metal halide chelates with BF3‐amine complexes in various epoxy systems has shown the chelates to be superior in several respects. Particular advantages are the ease with which reactivity can be varied by choice of chelate structure and by addition of moderators, and the reduced sensitivity to atmospheric moisture during cure. Use of BF2‐Chelates also gives cured products with better electrical properties, and in many cases better mechanical properties, than with BF3‐amine complexes.

Thio derivatives of β-diketones and their metal chelates. X. The anomalous paramagnetism of some iron(III) chelates of monothio-β-diketones

The magnetic susceptibilities of the iron(111) chelates Fe(R1CS=CHCOR2)3 (R1 = Ph, p-MeC6H4, p-MeOC6H4, p-BrC6H4, 2-thienyl, 2-furyl, R2 = CF3; R1 = Ph, R2 = Ph, OEt) have been investigated over a temperature range. The iron(111) complex of ethyl thiobenzoylacetate (R1 = Ph, R2 = OEt) is of the high-spin type and obeys the Curie-Weiss law with θ =-8�k. The moments of the other complexes vary between 2.31 and 6.61 B.M. at room temperature and are temperature-dependent, ranging from 1.86 to 4.07 B.M. at 80�k, depending on the nature of R1 and R2 This behaviour is postulated to be due to a thermal equilibrium between the nearly equi-energetic spin-paired (t5/2g) and spin-free (t3/2ge2/g) configurations of the iron atom, resulting from the approximately equal magnitudes of the ligand field (Δ) and the pairing energy (π) in these complexes. The ligand field and consequently the magnetic behaviour are sensitive to the nature of R1 and R2: electron-withdrawing groups appear to be the most effective in increasing the population of the spin-paired configuration.

Thio derivatives of β-diketones and their metal chelates. VIII. Adducts of metal chelates of fluorinated monothio-β-diketones

Complexes of l,l,l-trifluoro-4-mercapto-4-phenylbut-3-en-2-one, PhC(SH)= CHCOCF3, with cobalt(111), nicke1(11), palladium(11), platinum(11), copper(11), zinc(11), cadmium(11), and mercury(11) have been prepared and characterized. Their infrared spectra and the spectra of metal complexes of two other fluorinated monothio-β-diketones are discussed. Adducts of nickel (11) palladium(11), platinum(11), zinc(11), cadmium(11), mercury(11), and lead(11) complexes of the fluorinated monothio-β-diketones, RC(SH)=CHCOCF3 (R = Ph, α-thienyl, or Me), with pyridine, α-picoline, γ-picoline, 2,2'-bipyridyl, 1,l0-phenanthroline, 2,9-dimethyl-1,l0-phenanthroline, 2,2',2"-terpyridyl, or triphenylphosphine are described. Molecular weight and visible spectral measurements on PdL2(PPh3)2 (L = C4H3SC(SH)=CHCOCF3) show that in nitro- benzene and toluene solution one phosphine moiety is lost. Similarly, ZnL2 pic2 (pic = α- or γ-picoline) loses one molecule of picoline in nitrobenzene solution. The infrared data indicate that in the adducts nickel, zinc, and probably cadmium are six-coordinate and palladium, platinum, mercury, and lead are four-coordinate, while zinc is five-coordinate in the mono-adducts ZnL2 pic.

Thio derivatives of β-diketones and their metal chelates. IX. Nickel and copper complexes of some new fluorinated monothio-β-diketones

Four new fluorinated monothio-β-diketones of general formula RC(SH)=CH- COCF3 have been prepared; they are: l,l,l-trifluoro-4-mercapto-4-(4-methylphenyl)but-3-en-2-one (R = p-methylphenyl), 1,1,1-trifluoro-4-mercapto-4- (4-methoxyphenyl)but-3-en-2-one (R = p-methoxyphenyl), 4-(4-bromophenyl)-l,l,l- trifluoro-4-mercaptobut-3-en-2-one (R = p-bromophenyl), and l,l,l-trifluoro-4- (2-furyl)-4-mercaptobut-3-en-2-one (R = 2-furyl). Their nickel complexes, which are brown and diamagnetic, yield stable high-spin bis-pyridine adducts. When R = p-MeC6H4, p-MeOC6H4, or p-BrC6H4 the ligand yields both copper(1) and copper(11) complexes but when R = 2-furyl only a copper(11) complex is obtained. Infrared data indicate that in the copper(1) complexes the ligand is coordinated through the sulphur atom only.

Thio derivatives of β-diketones and their metal chelates. VII. The visible-ultraviolet spectra of some monothio-b-diketones and their metal chelates

The electronic spectra of 3-mercapto-1,3-diphenylprop-2-en-1-one, PhC(SH)=CHCOPh, and its zinc(II), silver(I), cadmium(II), mercury(II), and S-methyl derivatives are given and some provisional assignments of the bands are made. The spectra indicate that the oxygen atom of the ligand is weakly coordinated in the silver and cadmium complexes and that in the mercury complex the ligand is coordinated through the sulphur atom only. The spectra of two other monothio-β-diketones, R1C(SH)=CHCOR2 (R1 = R2 = Me, But), are also given. The spectra of the nickel(II) chelates of seven monothio-β- diketones are discussed and the bands are assigned as metal d-d, metal- to-ligand, ligand-to-metal, and ligand-to-ligand transitions.

Thio derivatives of β-diketones and their metal chelates. VI. Metal chelates of 3-Mercapto-1,3-diphenylprop-2-en-1-one and their infrared spectra

Complexes of 3-mercapto-1,3-diphenylprop-2-en-1-one, PhC(SH)=CHCOPh, with iron(III), cobalt(III), rhodium(III), nickel(II), palladium(II), platinum(II), copper(II), silver(I), zinc(II), cadmium(II), and mercury(II) have been prepared and characterized. Complexes of 4- mercaptopent-3-en-2-one, MeC(SH)=CHCOMe, with cobalt(III) and cadmium(II) and of ethyl thioacetoacetate, MeC(SH)=CHCOOEt, with cobalt(III) and copper(I) are also reported. The infrared spectra of the complexes of 3-mercapto-1,3- diphenylprop-2-en-1-one are discussed. The similarity of the spectra of the silver(I), cadmium(II), and mercury(II) complexes to those of the free ligand and its S-methyl derivative, PhC(SMe)=CHCOPh, indicate that in these three complexes the carbonyl oxygen of the ligand is not, or is at most weakly, coordinated to the metal ion. The assignments of the principal bands in the other metal complexes of this ligand are: 1550- 1525 cm-1, v(C-C); 1480-1458 cm-1, v(C=O); 1438-1412 cm-1, v(C=O)+δ(C-H); 1270-1260 cm-1, v(C--S); 498-437 cm-1, v(M-O); 399-376 cm-1, v(M-S).

Thio derivatives of β-diketones and their metal chelates. V. Acid dissociation constants of some Monothio-β-diektones and stability constants of anickel(II) and a copper(II) chelate

The acid dissociation constants (PKD) of the monothio derivatives of acetyl-acetone, dibenzoylmethane, and 3,3,3-trifluoro-1-(2- thenoyl)acetone, viz. 4-mercap-topent-3-en-2-one (I), 3-mercapto-1,3- diphenylprop-2-en-1-one (II), and 1,1,1-trifluoro-4-mercapto-4-(2- thienyl)but-3-en-2-one (III), were determined in dioxan/water solutions with varying mole fraction (n2) of dioxan. Over a range of n2 from 0.18 to 0.44 the values of pKD were found to vary linearly with n2 as given by the equations: (I) pKD = 5.7+12.0n2; (II) pKD = 7.0+10.9n2; (III) pKD = 3.55 + 9.2n2. The thio derivatives (I), (II), and (III) have pKD values 2.0-2.7 log units lower than their oxygen analogues. The logarithm of the stability constants (log β2) for the nickel(II) and copper(II) complexes of (II) were found to be 21.7 and 22.2, respectively. For both complexes K2 > K1. Comparison with the stability constants of the dibenzoylmethane complexes shows that for nickel(II) the complex of the monothio-β-diketone is more stable than that of the β-diketone while the converse is true for copper(II).

Thio derivatives of β-Diketones and their metal chelates. III. Metal chelates of some fluorinated Monothio-β-diketones

Metal chelates of 1,1,1-trifluoro-4-mercapto-4-(2-thienyl)but-3-en-2 one, C4H3SC(SH)=CHCOCF3 (TTMBH), and 1,1,1-trifluoro-4-mercaptopent-3-en-2-one, MeC(SH)=CHCOCF3 (TMPH) have been prepared. Inner complexes of both TTMBH and TMPH were obtained with cobalt(III), nicke1(II), palladium(11), platinum(II), zinc(II), cadmium(11), mercury(11), and lead(II); they are readily soluble in organic solvents. TTMBH gives the spin-free complex Fe(TTMB)3, the copper(II) complex Cu(TTMB)2, and the μ-dioxo-bridgedvanadium(1V) compound V2O2(TTMB)4. Iron(III) and copper(II) oxidize TMPH to the disulphide (TMP)2; however, a polymeric copper(I) complex Cu(TMP) was isolated. The complexing ability of TMPH appears to be weaker than that of TTNBH.

Thio derivatives of β-diketones and their metal chelates. I. Some Monothio-β-diketones and their nickel(II) chelates

Monothio-β-diketones of general formula RC(SH)=CHCOR? (R = Me, R* = Me, Ph, OEt; R = Ph, R' = Ph, OEt; R = α-thienyl, R' = CF3; and 12 = R' = CMe,) have been prepared in order to study their metal complexes. Five of these thio derivatives are new and were prepared by treatment of a dilute solution of the corresponding β-diketone in alcohol with hydrogen sulphide at low temperature. Mass spectrometric examination has established the structures of MeC(SH)=CHCOPh and RC(SH)=CHCOCF, (R = α-thienyl). The red compounds PhC(SH)=CHCOPh (VI) and MeC(SH)=CHCOPh (V) can be oxidized to yellow products. The structure of the yellow compound (XV) obtained from (VI) was established by mass and n.m.r. spectroscopy as the disulphide PhCOCH=C(Ph)SSC(Ph)=CHCOPh. The molecular ion of (XV) undergoes novel rearrangement reactions involving, inter alia, elimination of H2S to produce a thiophene ion. The nickel chelates Ni(RCS=CHCOR')2 are brown, diamagnetic, and soluble in organic solvents. Unstable paramagnetic bis-pyridine adducts, derived from two of the nickel chelates, were isolated. The infrared spectra of the monothio-β-diketones and their nickel chelates are reported. The spectra of the monothio-β-diketones show no SH band at c. 2570 cm-1 ; this indicates strong chelation of the thiol hydrogen between the sulphur and oxygen atoms. The monothio-β-diketones display four characteristic bands which are assigned as follows : 1670-1590 cm-1, v(C--O) ; 1638-1530 cm-1, v(C=C) ; 1267-1190 cm-1, v(C=S) ; 837-805 cm-1, provisionally assigned as v(C=S) + δ(C-H). The nickel chelates exhibit five characteristic bands: 1590-1535 cm-1, V(C=C); 1542-1477 cm-1, v(C-0); 1261-1220 cm-1, v(C--S); 817-800 cm-1, provisionally assigned to v(C-S)+ δ(C-H); 499-451 cm-1, v(Ni-O). No band corresponding to v(Ni-S) was detected above 250 cm-1. However, the metal-sulphur stretching frequency was observed as a peak of medium intensity within the range 360-308 cm-1 in the spectra of bis(o-methylthiobenzenethiolo)-nickel(II) and the diethyl dithiophosphate complexes of nicke1(II), palladium(II), chromium(III), and cobalt(III).

Thio derivatives of β-diketones and their metal chelates. II. α-Substituted Monothio-β-diketones as ligands

The α-methyl substituted monothio-β-diketones, 4-mercapto-3-methylpent-3-en-2-one, MeC(SH)=C(Me)COMe, and 3-mercapto-2-methyl-1,3-diphenylprop-2-en-1-one, PhC(SH)=C(;Me)COPh, were prepared; the former was not obtained pure. The complexing ability of these ligands appears to be weaker than that of other monothio-β-diketones; this can be partly explained on the basis of steric hindrance caused by the methyl group attached to the central carbon atom. The diamagnetic complexes, Ni(MeCS=CMeCOMe)2, Co(MeCS=CMeCOMe)3, and Ni(PhCS=CMeCOPh)2 were obtained but attempts to prepare other metal complexes of these ligands were unsuccessful. The infrared spectra of the three metal chelates display four characteristic bands for which assignments are given: 1570-1540 cm-1, v(C--C); 1525-1500 cm-1, v(C-0); 1230-1223 cm-1, v(C--8); 497-458 cm-1, v(M-0).

オルト及びパラ置換フェノール誘導体の合成並びに抗菌作用

Phenol derivatives possessing a long-chain alkyl or -COR group in the ortho or para position of phenol, β-diketone derivatives having -COCH2COR group, and monoketo acid derivatives possessing -CO(CH2)nCOOR group were synthesized and their antibacterial activity against Staphylococcus aureus and antifungal activity against Trychophyton were examined.

Studies of co-ordination.—Part II. absorption spectra of metallic derivatives of benzoylcamphor

In the preceding paper of the present series on “Absorption Spectra and Co-ordination of some Cupric Compounds” observations were recorded of the absorption spectra, in the infra-red, visible and ultra-violet regions, of a series of metallic derivatives of copper, ranging from typical metallic salts, such as the blue aqueous sulphate and nitrate, through the blue-green acetate and its homologues, to the violet, yellow or brown derivatives of various β-diketones. In spite of the wide differences of colour in these compounds, the variations were found to be due to a mere displacement of a single absorption band, e. g ., from 9600 Å. U. in K 2 CuCl 4 to 6000 Å. U. in [Cu. 4NH 3 SO 4 , and the conclusion was drawn that the cupric ion in all these compounds exhibits a fourfold co-ordination, either with the anions of the salt or with molecules of the solvent. In the present paper analogous methods have been applied to the study of the metallic derivatives of benzoylcamphor. The investigation had its origin in a suggested correlation between the phenomena of dynamic isomerism in prototropic compounds and of co-ordination in their metallic derivatives. The former phenomenon was attributed, on the basis of an extended definition of acids and bases,† to the possibility of separating a proton from two alternative positions in the molecule, giving rise to two isomeric anions, which could be converted into one another through an intermediate multipolar ion, e. g ., HO.C=C─⇌ - O─C─C-⇌ - O─ + | | | | Enol. Enolic anion. C─ - C─⇌O=C─ - C─⇌O=C─C─ | | | | | | Multipolar ion. Ketonic anion. Ketone. H

XLV.—Researches on residual affinity and co-ordination. Part XVII. Stannic derivatives of β-diketones

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The Bactericidal Action of Tellurium Derivatives of certain Aliphatic β-Diketones

Research Article| January 01 1923 The Bactericidal Action of Tellurium Derivatives of certain Aliphatic β-Diketones Gilbert Thomas Morgan; Gilbert Thomas Morgan 1The Chemical Department, University of Birmingham, Edgbaston Search for other works by this author on: This Site PubMed Google Scholar Evelyn Ashley Cooper; Evelyn Ashley Cooper 1The Chemical Department, University of Birmingham, Edgbaston Search for other works by this author on: This Site PubMed Google Scholar Arnold Wigham Burtt Arnold Wigham Burtt 1The Chemical Department, University of Birmingham, Edgbaston Search for other works by this author on: This Site PubMed Google Scholar Biochem J (1923) 17 (1): 30–33. https://doi.org/10.1042/bj0170030 Views Icon Views Article contents Figures & tables Video Audio Supplementary Data Peer Review Share Icon Share Facebook Twitter LinkedIn MailTo Cite Icon Cite Get Permissions Citation Gilbert Thomas Morgan, Evelyn Ashley Cooper, Arnold Wigham Burtt; The Bactericidal Action of Tellurium Derivatives of certain Aliphatic β-Diketones. Biochem J 1 January 1923; 17 (1): 30–33. doi: https://doi.org/10.1042/bj0170030 Download citation file: Ris (Zotero) Reference Manager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex toolbar search Search Dropdown Menu toolbar search search input Search input auto suggest filter your search All ContentAll JournalsBiochemical Journal Search Advanced Search This content is only available as a PDF. © 1923 CAMBRIDGE UNIVERSITY PRESS1923 Article PDF first page preview Close Modal You do not currently have access to this content.