bluuebunny/crossref_metadata_2025_split huggingface dataset:
Transannular hemi‐acetal formation from 6‐hydroxycyclodecanone
Authors: Mijs W. J. , de Vries K. S. , Westra J. G. , Gaur H. A. Angad , Smidt J. , Vriend J. 
Published: September 2010

AbstractThe existence of a temperature and solvent dependent equilibrium between the oxo form (Ia) and the hemi‐acetal form (Ib) of 6‐hydroxycyclodecanone (I) has been proved by chemical methods and by infrared and nuclear magnetic resonance spectroscopy.
The structure of davanone a new sesquiterpene from davana: (Artemisia pallens, Wall.)
Authors: Sipma G. , van der Wal B. 
Published: September 2010

AbstractStructure I, based on chemical and spectroscopic evidence, is proposed for a new sesquiterpenoid ketone, davanone, isolated from the essential oil of Artemisia pallens, Wall., known as davana oil.
Electronic and steric effects in the hydrogenation of alkyl aryl ketones on palladium
Authors: van Bekkum H. , Kieboom A.P.G. , van De Putte K.J.G. 
Published: September 2010

AbstractThe hydrogenation of some forty aromatic ketones to the corresponding alcohols has been studied in ethanol using carbon‐supported palladium as the catalyst. Zero order kinetics with respect to ketone is observed. For acetophenones electronic substituent effects may be expressed in terms of a Hammett‐Yukawa relationship with ρ = 0.7. 2‐Alkylacetophenones react very slowly. With alkyl phenyl ketones increase of size of the alkyl group causes increasing rate of hydrogenation. The adsorbed state is discussed on the basis of competition experiments.
The bromodecarboxylation of thiophenecarboxylic acids
Authors: Zwanenburg D. J. , Wynberg Hans 
Published: September 2010

AbstractBromodecarboxylation of the disodium salt of 3,4‐dimethylthiophene‐2,5‐dicarboxylate with bromine in water gave 2,5‐dibromo‐3,4‐dimethylthiophene. This bromodecarboxylation reaction, first mentioned by Melles and Backer (1953), has interesting synthetic aspects and a number of other examples are given.
Protonation of azo‐compounds. Part II: The structure of the conjugate acid of trans‐azobenzene
Authors: Hoefnagel M. A. , van Veen A. , Wepster B. M. 
Published: September 2010

AbstractThe basic strengths of trans‐azobenzene and its 2‐methyl and 2,2′‐dimethyl derivatives strongly favour the “classic” view that protonation of these compounds takes place with formation of an NH σ‐bond. This is further confirmed by the rates of oxidation by perbenzoic acid of these compounds and of the corresponding trans‐stilbenes.A few remarks are made on the arguments which led to the assumption that the azo‐group acts as a “single basic center”.
Rearrangements of substituted propargyl vinyl sulfides: Formation of allenic dithioesters and their conversion into derivatives of 2H‐thiopyran and thiopene
Authors: Schuijl P. J. W. , Bos H. J. T. , Brandsma L. 
Published: September 2010

AbstractCompounds of the general formula R1CH=C(SC2H5)S‐CH2C2≡CR2 (II) (with R1=H, alkyl or aryl and R2=H or CH3) prepared by metallation of dithioesters R1CH2C(=S)SC2H5 (I) with potassium amide in liquid ammonia and subsequent reaction with R2C≡CCH2Br, rearrange at elevated temperatures. The first product is the allenic dithioester CH2=C=C(R2)‐CH(R1)C(=S)SC2H5 (III), which can undergo cyclisation either to a 2 H‐thiopyran derivative (IV, see reaction scheme) or to a substituted thiophene (V, see scheme I). The thiopyran formation is strongly accelerated by triethylamine, whereas (traces of) acids favour the cyclisation to thiophenes.Energies of activation for the conversion of II to III have been determined.
C17‐substituted 5‐ and 5(10)‐estrenes and their 7α‐methyl homologues
Authors: Bolt C. C. , de Jongh H. P. , Siegmann C. M. , van Vliet N. P. , Zeelen F. J. 
Published: September 2010

Abstract17α‐Alkylated derivatives of 5‐estren‐17β‐ol and their 7α‐methyl homologues have been prepared (Chart I). The key step in these syntheses is the reduction of the 3β‐chloro‐5‐estrenes (IV) with lithium in liquid ammonia.Similar derivatives of the 5(10)‐estrenes have been synthesised (Chart II). The preparation and the reduction of the dithio‐acetals VIII are discussed. 5(10)‐Estren‐17‐one has been obtained together with other double bond isomers by isomerisation of 4‐estren‐17‐one.
Complexes with ligands containing S = O. Part VIII. Metal solvates with the ligand 1,4‐dithiane monosulfoxide
Authors: Reedijk J. , Fleur A. H. M. , Groeneveld W. L. 
Published: September 2010

AbstractThe ligand properties of 1,4‐dithiane monosulfoxide (DTMSO) have been studied by preparing a number of coordination compounds of formula M(DTMSO)6(anion)n, and by investigating their structure and properties by means of physical measurements.The ligand is shown, by means of infrared spectroscopy to coordinate via the oxygen lone pair electrons to the metal ions investigated.Both infrared and ligand‐field spectra showed the presence of octahedral ions M(DTMSO)6n+ in the compounds M(DTMSO)6(ClO4)n and M(DTMSO)6(BF4)n. In the case of M = Cu2+ these ions are distorted from regular octahedral, as is shown by infrared spectroscopy and by paramagnetic resonance spectroscopy.The ligand DTMSO has been placed in the spectrochemical and nephelauxetic series with respect to the metal ions Ni(II) and Co(II). The spectrochemical series appears to be DMSO < DTMSO < TOSO < PMSO, and the nephelauxetic series has the reversed order (DMSO = dimethyl sulfoxide, TOSO = 1,4‐thioxane sulfoxide, PMSO = pentamethylene sulfoxide).
Spectra of some tetrathiometallates and tetraselenometallates
Authors: Omloo W. P. F. A. M. , Jellinek F. 
Published: September 2010

AbstractThe electronic absorption spectra of (NH4)2MoS4 and K3VS4 have been studied and discussed in terms of Viste and Gray's MO scheme of tetrahedral tetroxometallate anions. Diffuse reflection spectra of the compounds Cu3MVX4 and Tl3MVX4 (MV = V, Nb, Ta; X = S, Se) show that the energies of the absorption edges and absorption maxima increase in the sequence MV = V → → Nb → Ta and decrease in the order X = O → S → Se. The infrared spectra of the sulfides were also investigated.
Chemistry of acetylenic ethers 94: Addition of carbonyl dichloride to 1‐alkynyl sulfides and 1‐alkynyl ethers
Authors: van den Bosch G. , Bos H. J. T. , Arens J. F. 
Published: September 2010

Abstract1‐Alkynyl sulfides and 1‐alkynyl ethers of the type R‐CC‐Y‐R′ (R = H or alkyl, R′ = alkyl and Y = O or S) were converted into β‐alkyl‐thio‐ and β‐alkoxy‐β‐chloro‐acrylic chlorides R′Y‐CClCR‐CO‐Cl by addition of carbonyl dichloride (phosgene).Thecis‐isomers are formed initially [Cl and (COCl)cis], but partial isomerization occurs during work‐up. Configurations were determined by comparison of the NMR data with those of several derivatives of acrylic acid.Relative addition rates have been determined in competition experiments. The mechanism of the reaction is discussed.
The synthesis and spectra of some heterocyclic conjugated spiranes
Authors: Wynberg Hans , Heeres G. J. , Jordens P. , Sinnige H. J. M. 
Published: September 2010

AbstractFour spiro[cyclopentabithiophene]fluorenes have been synthesized. A distinct bathochromic shift due to spiroconjugation is found in their UV spectra, as predicted by SimmonsH. E. Simmons and T. Fukunaga, J. Am. Chem. Soc. 89, 5208 (1967).
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Réactivité des trialcoylalcoxy‐ et dialcoylalcoxychlorogermanes et de leurs isologues soufrés vis à vis des aldéhydes et des cétones
Authors: Dousse M. M. Gabriel , Satgé Jacques 
Published: September 2010

AbstractAldehydes and ketones add onto the germanium‐oxygen bond of triethylmethoxy‐ and diethylmethoxy‐chlorogermanes with formation of the corresponding germanium acetals, the stability, the mode of thermal decomposition and certain properties of which have been investigated.The germanium acetals of hexafluoroacetone are stable. β‐Elimination reactions are observed from germanium acetals of chloral and hexachloroacetone. The decomposition of the germanium acetals of the aldehydes and ketones takes place, in the presence of H2PtCl6, to give the corresponding acetals of the starting carbonyl compounds and trialkylgermanium oxides.Additions and decompositions of the same type are observed in the action of the aliphatic aldehydes on the trialkyl(alkylthio)‐ and dialkyl(alkylthio)‐chlorogermanes. Chloral gives a reversible insertion reaction, however, at 90°, besides the β‐elimination reaction, a chlorine‐methylthio exchange reaction is also observed with formation of tri(methylthio)acetaldehyde and triethyl‐germanium chloride.The influence of the inductive effects of the substituents on the germanium or on the carbonyl group in the course of these reactions as well as the catalytic action of the chloroplatinic acid or of zinc chloride seem to confirm the addition mechanism considered.
Pyrazoles and imidazoles as ligands. Part IX: Some adducts formed between Cu(II) salts and substituted pyrazoles
Authors: Reedijk J. , Windhorst J.C.A. , van Ham N.H.M. , Groeneveld W.L. 
Published: September 2010

AbstractA number of adducts of general formula Cu(PZ)x2+(anion)2− is reported. In this formula PZ stands for: pyrazole. N‐methyl pyrazole. 3(5)‐methylpyrazole. 3,5‐dimethylpyrazole. 4‐chloropyrazole, 4‐bromopyrazole and 4‐nitropyrazole; the anions are ClO4−, BF4−, NO3−. Br− and Cl−. The value of x varies from 2–4 for the several ligands and anions.The compounds are synthesized from the hydrated Cu(II) salts and the stoichiometric amounts of pyrazoles in ethanol or acetone solutions, with the addition of triethyl orthoformate for dehydration.The adducts were characterized and identified by chemical analyses, infrared spectra, ligand‐field spectra and paramagnetic measurements. In all compounds the Cu2+ ions were found to be in a six‐coordinate, distorted octahedral environment. In contrast with other divalent metal ions, solvates containing the unit Cu(PZ)62+ could not be prepared.
Complexes with ligands containing nitrile groups. Part XIII: Metal(II) solvates containing substituted benzonitriles as ligands
Authors: van Driel C.A.A. , Groeneveld W.L. 
Published: September 2010

AbstractA number of solvates having the general formula M(R‐BN)n2+(anion−)2 is reported. The cations M are the divalent ions: Mg, Mn, Fe, Co, Ni, Cu, Zn and Cd. The substituted benzonitriles R‐BN are: 4‐Cl‐BN, 3‐Cl‐BN, 2‐Cl‐BN, 4‐CH3O‐BN, 2,6‐diCl‐BN, 3,4‐di(CH3O)‐BN and 2,5‐di(CH3)‐BN; n is usually 6 except for Cu2+ where n is found to be 6,5 or 4. One complex of Zn2+ is prepared where n is 4. The anions used are SbCl6−, FeCl4− and InCl4−.The infrared nitrile absorptions are examined and compared with those of the free nitrile. Metal‐nitrogen vibrations are obtained from far‐infrared spectra. Ligand‐field spectra parameters have been calculated.
Optimization, mechanism, and kinetics of the hydrogenation of skipped polyynoic acids to all‐cis skipped polyenoic acids
Authors: Steenhoek A. , van Wijngaarden B. H. , Pabon H. J. J. 
Published: September 2010

AbstractHydrogenation of skipped polyynoic acids and esters over Lindlar's catalyst in the presence of quinoline proceeds with optimum results in light petroleum, ethyl acetate, or acetone at room temperature, yielding the corresponding all‐cis polyenoic compounds in purities of 90‐99%, depending on the number of triple bonds.For hydrogenations of this type mechanistic schemes are presented, including the formation of ene‐ynoic intermediates. Using Langmuir adsorption and Hinshelwood kinetics, analogue computer simulation showed a simultaneous uptake of more than one H2 molecule to be an important step in the reaction route.The formation of trans‐double bonds occurs only via isomerization of cis‐double bonds.
Nitrogen fixation by reduced transition metal complexes: I. ESR measurements on a nitrogen‐binding vanadium complex
Authors: Beelen T. P. M. , van Erk W. 
Published: September 2010

AbstractMolecular nitrogen has been bonded on vanadium trichloride, after reduction with lithium naphthalide. During these reduction and fixation reactions several ESR‐signals appeared. By measurements of signal intensities in the presence and absence of N2it was shown that these signals did not correspond with a vanadium‐nitrogen complex. They do indicate, however, the degree of reduction of the system and therefore provide information on the state of reduction of the complex (not ESR‐active in itself) that binds N2.
Chemistry of small ring compounds. Part 16: Kinetics and mechanism of the isomerization of some 1,1‐cyclopropanedicarboxylic acids in water and in aqueous sulfuric acid
Authors: Bus J. , Steinberg H. , de Boer Th. J. 
Published: September 2010

AbstractThe kinetics of the isomerization of 1,1‐cyclopropanedicarboxylic acid 1a to αcarboxy‐γ‐butyrolactone 3a in D2O and in aqueous D2SO4 (up to 56%) has been studied at temperatures up to 160°C.The pseudo first‐order reaction is progressively accelerated by increasing sulfuric acid concentrations and according to Bunnett's w, w* and ψ‐values, the rate‐limiting step is probably the nucleophilic attack of water on a cyclopropyl ring carbon atom of the protonated substrate.2‐Methyl‐1,1‐cyclopropanedicarboxylic acid 1b and 2,2‐dimethyl‐ 1,1‐cyclopropanedicarboxylic acid 1c isomerize faster than 1a by a factor of 31 and 80,000 respectively. The tremendous, rate‐enhancement of 1c can be explained by a rate‐limiting dissociation of a ring carbon‐carbon bond of the protonated substrate (SN1‐reaction).
Epoxidation of olefins by alkylperoxy radicals
Authors: Koelewijn P. 
Published: September 2010

AbstractWe have studied the reactions of alkylperoxy radicals with olefins in an inert solvent and atmosphere. The peroxy radicals react by addition to the double bond, mainly leading to epoxide formation, and by abstraction of allylic hydrogen, followed by termination between allyl and peroxy radicals. Relative and absolute rate constants at 120°C have been determined of the reactions of tert‐butylperoxy radicals with 2,3‐dimethyl‐2‐butene, 1‐hexene, α‐methylstyrene, propene, 3,3‐dimethyl‐1‐butene and styrene, and of α‐cumylperoxy radicals with 3,3‐dimethyl‐1‐butene.We have found that for olefins having allylic hydrogen the abstraction/addition ratio determines the efficiency as well as the rate of epoxide formation, whereas substantial epoxide formation from olefins lacking easily abstractable hydrogen atoms can be expected only if the double bond is sufficiently reactive to suppress the reactions between the peroxy radicals.
Reactions of hydroxycarbonium ions in strong acids VI: Interconversion of trimethyltetrahydrofuryl ions via dicarbonium ions. Relative acidities of superacids
Authors: Brouwer D. M. , van Doorn J. A. 
Published: September 2010

AbstractThe rearrangement of 5‐ethyl‐2‐methyltetrahydrofuryl ion (2) to the 2,5,5‐trimethyltetrahydrofuryl ion (4) is proceeded by a much more rapid equilibration of 2 with the 2,4,5‐trimethyl isomers (3, cis and trans). These reactions are both acid catalysed and only take place in superacids (HF‐SbF5 and FSO3H‐SbF5). They involve skeleton rearrangements in intermediate dications (C,O‐diprotonated alkenones), the most stable one of which has been observed directly in 1:1 HF‐SbF5.From the rates of the above and other, similar reactions the relative acidities of 1:1 HF‐SbF5, 9:1 HF‐SbF5, 1:1 FSO3H‐SbF5 and 5:1 FSO3H‐SbF5 have been estimated as > 500:1:10−1:10−5.From the fact that 2 isomerizes much faster to 3 than to 4 it is concluded that in branching rearrangements of alkylcarbonium ions (e.g. linear to mono‐branched ions) the ring opening of the intermediate protonated 1,2‐dialkyl‐cyclopropane to the branched structure goes first to a secondary branched ion as a distinct intermediate.
Ring transformations in reactions of heterocyclic halogeno compounds with nucleophiles (XXV): On the mechanism of the conversion of chloropyrazine into aminopyrazine and of 2‐chloroquinoxaline into 2‐aminoquinoxaline with potassium amide in liquid ammonia
Authors: Lont P. J. , van der Plas H. C. , Verbeek A. J. 
Published: September 2010

AbstractIt has been found that 2‐chloropyrazine, containing an excess of 15N in position 1, by treatment with potassium amide in liquid ammonia at −65° yields 2‐aminopyrazine, in which the exocyclic nitrogen contains all the excess of 15N. An A(ddition)‐N(ucleophilic)‐R(ing)‐O(pening)‐R(ing)‐C(losure) mechanism is proposed. The corresponding animation of 2‐chloro[1(4)‐15N]quinoxaline at −33° leads to 2‐amino[1(4)‐15N]quinoxaline. In the last‐mentioned conversion an A(ddition)‐E(limination) mechanism is operative.
Reactions of hydroxycarbonium ions in strong acids. VII: Rearrangement of the 2,5,5‐trimethyldihydrofuryl ion, a heteroaromatic carbonium‐ion rearrangement
Authors: Brouwer D. M. , van Doorn J. A. , Kiffen A. A. 
Published: September 2010

AbstractThe rearrangement of 2,5,5‐ to 2,4,5‐trimethyldihydrofuryl ion, a heteroaromatic rearrangement via 1,2‐methyl and hydride shifts, is reported. The half‐life of the reaction is about 25 minutes at 100°.
Reduction and reductive alkylation of cycloheptatriene with alkali metals in liquid ammonia
Authors: Dirkzwager H. , Nieuwstad Th. J. , van Wijk A. M. , van Bekkum H. 
Published: September 2010

AbstractWhen treated with alkali metals in liquid ammonia at −70° cycloheptatriene adopts two electrons and a proton yielding the cycloheptadienyl anion. Protonation of this anion yields 1,3‐ and 1,4‐cycloheptadiene in a ratio which depends rather strongly on the proton donor used. Decreasing acid strength of the proton donor favours 1,3‐cycloheptadiene formation. The selectivity of protonation also depends on the alkali metal used and on the concentration. At −33° ammonia protonates the cycloheptadienyl anion yielding 1,3‐cycloheptadiene. This enables one step reduction of cycloheptatriene to cycloheptene. Reduction of 7‐deuterocycloheptatriene shows the first proton addition to cycloheptatriene to be irreversible.Alkylation of the cycloheptadienyl anion yields mixtures of 3‐alkyl‐1,4‐cycloheptadiene and 5‐alkyl‐1,3‐cycloheptadiene in which the former compound invariably predominates.
The selective monobromination of methane with mixtures of bromine and chlorine
Authors: van Drumpt J. D. 
Published: September 2010

AbstractThe reaction between methane and mixtures of bromine and chlorine was investigated.Maximum conversions of bromine into methyl bromide of 63% were obtained; this yield can be improved by further increasing the methane: halogen ratio.When ethane was used instead of methane, higher yields (up to 75%) and a higher selectivity towards monobromination were found.The results strongly suggest a branched free radical chain reaction. The rate determining step is the attack of a chlorine radical on the hydrocarbon.These conclusions are supported by approximate calculations, based upon the proposed reaction mechanism.
Aromatic lead(IV) compounds IV The plumbylation of halogen‐ and alkyl‐substituted aromatic ethers
Authors: de Vos D. , Boschman F. E. H. , Wolters J. , van der Gen A. 
Published: September 2010

AbstractThe preparation and some physical properties of aryllead triacetates in which the nucleus bears an alkoxy and a halogen or alkyl substituent, are reported.
Preparation of 5‐cyano‐2H‐thiopyrans and 4‐cyano‐2‐methylthiophenes by thermal rearrangement of the adducts from 2‐propynethiol and cyanoalkynes
Authors: van Der Welle R. A. , Brandsma L. 
Published: September 2010

Abstract5‐Cyano‐2H‐thiopyran and a number of derivatives have been obtained in fair to good yields by heating compounds with the system CCCSCCCN in silicon oil; 4‐cyano‐2‐methylthiophenes are formed by heating these systems in dimethylsulfoxide in the presence of diisopropylamine. The starting systems were prepared by nucleophilic addition of 2‐propynethiol, HCCCH2SH, to cyanoalkynes RCCCN (R  H or alkyl).
Mechanism of the antioxidant action of dialkyl sulfoxides II. Aspects of the antioxidant and pro‐oxidant actions of sulfoxides
Authors: Koelewijn P. , Berger H. 
Published: September 2010

AbstractThis paper analyses several complicating factors which can play a role in the inhibition of autoxidation by dialkyl sulfoxides, the uncomplicated case having been dealt with in the first paper1. It was found that in those cases where the autoxidation proceeds via tertiary peroxy radicals, sulfoxides yielding tertiary (or, possibly, also secondary) alkylsulfenic acids show poor antioxidant activity. This is attributed to the generation of radicals from the sulfinic acid perester formed by the reaction of peroxy radicals with the sulfinic radicals produced in the inhibition reaction.A type of inhibition of autoxidation which does not involve radical scavenging arises from the ionic decomposition of hydroperoxides by strong acids formed from sulfoxides; this type of inhibition is most effective with those sulfoxides which are also active as inhibitors via the formation of sulfenic acid.Sulfoxides also display a pro‐oxidant action, which is explained as a catalysis of the radical decomposition of hydroperoxides via the formation of a compound or complex from hydroperoxide and sulfoxide.
Reaction of 2‐halogeno‐4‐phenylpyrimidines with potassium amide in liquid ammonia. On the possible occurrence of two SN(ANRORC)‐mechanisms
Authors: Kroon A. P. , van der Plas H. C. 
Published: September 2010

AbstractOn amination of 2‐X‐4‐phenylpyrimidine (X=F, Cl, 1) with potassium amide in liquid ammonia at −75°. 2‐amino‐4‐phenylpyrimidine is obtained as main product, together with some 3‐amino‐3‐phenylacrylonitrile. It was proved using 2‐halogeno‐4‐phenyl‐[1,3‐15N]‐pyrimidines that the displacement reaction occurs for the greater partviaan SN(ANRORC)‐mechanism (82% for X=F, 88% for X=Cl and 73% for X=1). It was further found that the 3‐amino‐3‐phenylacrylonitrile, obtained from the15N‐labelled pyrimidines.does not contain15N. This very unexpected result is discussed.
The chemistry of small ring compounds. Part 27. Heterocyclic condensation products from cyclopropanone and methylamine
Authors: van Tilborg W. J. M. , Steinberg H. , de Boer Th. J. 
Published: September 2010

AbstractThe adduct 2 of methylamine with two molecules of cyclopropanone gives, on mild heating, a variety of six‐ and eight‐membered heterocycles (with hetero‐atoms NNN, NON, ONO, NONO or ONOO) and three or four unruptured (spiro‐)cyclopropyl groups attached to the ring. The cyclisation mechanism involves in all cases an initial rapid dimerisation of 2.The aniline‐cyclopropanone adduct 10 on heating gives only the related six‐membered cyclo‐condensation products.
Nucleophilic additions on sulfonyl cyanides. Formation of C‐(arylsulfonyl)‐ and C‐(alkylsulfonyl)formamidrazones and their conversion to 1,2,4‐triazoles
Authors: Jagt J.C. , van Leusen A.M. 
Published: September 2010

AbstractC‐Sulfonylformamidrazones are formed as isolable adducts from sulfonyl cyanides and the α‐effect nucleophiles hydrazine and phenylhydrazine. The adducts react with triethyl orthoformate or orthoacetate to give 1,2,4‐triazoles.
Base‐catalysed cyclisation of trans‐enyne alcohols to derivatives of furan
Authors: Schreurs P.H.M. , Galesloot W.G. , Brandsma L. 
Published: September 2010

Abstracttrans‐Enyne alcohols of the type R1C≡CCHCHCR2R3OH (R2 and R3 = H or alkyl) undergo cyclisation to substituted furans or dihydrofurans with potassium tert‐butoxide in dimethyl sulfoxide at 100° (if R1 = H) or at 25° (if R1 = CH3S or Ph).
Electrophilic alkylation of thiocamphorS‐oxide
Authors: Veenstra G.E. , Zwanenburg B. 
Published: September 2010

AbstractTreatment of thiocamphorS‐oxide2with thallium(I) ethoxide gives a thallium(I) vinyl‐sulfenate which alkylates at sulfur with the alkyl halides CH3I, C6H5CH2Br, CH2CHCH2Br, EtOOCCH2Br, NCCH2Cl, CH3COCH2Cl andp‐BrC6H4COCH2Br to the α,β‐unsaturated sulfoxides3. These products were converted into the corresponding sulfones which were prepared by an alternative route from thiocamphor by treatment with LiN(iPr)2,S‐alkylation to vinyl sulfides5and subsequent oxidation.