PRODUCTION OF C~~TELLURIPENTAXEDIONE DICHLOBLDES. 2611 CCCLIX-Production of cycloTelluripentuned~m Dichlorides. By GILBERT T. MORGAN. [With FREDERICK JAMES CORBY OLIVER CECIL ELVINS EVELINE JONES RICHARD EATOUGH KELLETT and CYRIL JAMES ALLAN TAYLOR. ] THE search for co-ordination derivatives of tellurium and the P-diketones led to the discovery of two new groups of cyclic tellurium compounds in which the diketone concerned furnishes a bivalent chelate group. These cyclic substances are not the sole products of the condensation of tellurium tetrachloride with P-diketones and certain of the diketones examined have not given them but as the result of numerous experiments it now becomes possible to predict with a fair degree of certainty which p-diketones are likely to furnish the chelate groups required to implicate tellurium in the six-membered rings.Certain constitutioml features must be present in a p-diketone in order that it may function in the desired sense and within the limits imposed by these structural requirements the reaction is a general one. T e a 0 /\ \/ R-YH yH,R’’ R-YH VHR,” (I.) oc co -3 oc co C \/ C /\ R’ R’ /\ R’ R’ Formula I represents any P-diketone which would condense with tellurium tetrachloride to produce a cyclic telluridichloride (11) provided that the substituents R R’ and R” are of the appropriate chemical type. Acetylacetone the simplest case where R = R’ = R” = H, gives as the main product cyclotelluripentane-3 Ei-dione 1 l-di-chloride (formula II). It has however also yielded two other products both of which are non-cyclic; the h t of these is the tellwitrichloride CH,*C( OEf):CH-CO*CH,-TeCl, obtained by the intervention of ethyl alcohol present in ordinary chloroform the second is a telluridichloride which is still enolic, { CH,*C( 0H):CHCO CH,) 2TeCI,.These by-products arise evidently from interaction between tellur-ium tetrachloride and acetylacetone in its monoenolic form induced 4 s 2612 MORCAN : by migration of hydrogen from the median carbon atom. It is, however highly probable that the main cyclic product is due to con-densation with a dienolic modification m C ( OH)-CH,-C(OH):CH,, developed by twofold enolisation from the two terminal hydro-carbon radicals. The process probably takes place in two stages, the tellurium tetrachloride fht combining additively with the dienolic m&cation of the 8-diketone giving rise to the hypo-thetical addition product (IV) which by subsequent loss of two molecules of hydrogen chloride passes into the stable cyclotelluri-dichloride (11) .TeCI, It is of general interest in connexion with dynamic isomerism that in these condensations the tetrachlorides of selenium and tellurium behave dissimilarly and evoke a different response from the reacting tautomeric diketone. Selenium tetrachloride attacks the monoenolic isomeride produced by median enolisation or its analogously constituted copper derivative. Tellurium tetrachloride links up the unsaturated ends of a five-membered chain arising from twofold terminal enolisation.This explanation of the mechanism of the tellurium condensation is supported by the following experimental evidence. So long as 2R’ in the foregoing formule represent two hydrogen atoms there is considerable tendency for one of these to migrate to an adjacent oxygen atom thus giving rise to median enolisation. The result of this dynamic change in the cme of acetylacetone has already been mentioned; it leads fo two non-cyclic products. Similar non-cyclic products have been noticed with propionylacetone dipropionylmethane di-n-butyryl-methane and hexoylacetone. The last two diketones exhibit the interesting case of an enolic non-cyclic telluritrichloride, (C,H,*CH,-C( OH):CH*COCH(C,H,) 1 TeC1 and 1. Hedian enolisation. (C,H,,*CH,*C( OH):CH-CO*CH,)TeCl,.It is probable that the three types of non-cyclic tellurium com-pounds (O-ethyl-trichloride and enolic trichloride and dichloride) may be present in other condensations with non-3-alkylated p-di-ketones but that owing to instability and great solubility these products have not been isolated the experimental f i c u l t i e s becoming greater as the number of carbon atoms in the chain increases PRODUWON OF C@ITELLURIPENTAXEDIONE DICHLORXDES. 2613 2. Lengthening of the unbranched k i n . Providing that the tendency to terminal enolisation is not diminished by substitution of alkyl radicals for hydrogen in the reactive ferminal methylene groups R-WCO*C&-CO=mR' the lengthening of hydrogen chain R or R' does not prevent the formation of a cyelotelluri-pentanedione derivative and the general nature of the reaction has been demonstrated by condensing such higher ketones as n-octoyl-acetone n-nonoylacetone and n-duodecoylacetone (lauroylacetone) with tellurium tetrachloride.The last of these has yielded Z-n-hyZ-cycloteu.uripentune-3 5-dwne 1 l-didloride (VII) reducible to 2-n-decylcycloteUurope~m-3 5 - d i m (VIII). Sufficient examples have been selected to show that the pro-duction of cycZotelluripentanedione dichlorides and their reduction to cyclotelluropentane-3 5-diones are general reactions for all p-diketones having structural formula I when R and R" axe normal or unbranched hydrocarbon chains. 3. Alkylution of the median methylene group. When one B' is hydrogen and the other an alkyl group the tellurium condewation becomes simplified so that although many 3-alky1at.d fkliketones have been examined only one telluriferous product has been identified in each case.The 3-alkylacetylacetones react smoothly and give 4-alkylcyclotelluripentane-3 5-dione 1 1-dichlorides in good yield. The 3-lpropylprgmyi!acekmny~acetones (normal and iso) de-scribed below behave similarly and give rise to the two isomeric Z-~hy1-4-2wopyEcycloteuzcripentu~-~ & d i m 1 I-dichlorides (IT). 3-iso&tylacetylacetone also condenses smoothly with tellurium tetrachloride yielding only one product namely the cyclic telluri-dichloride (11). 4. Branched chzhs on the median carbon atom. 3-koBopyl-acetylac etone ( CH,) ,CH *CH (CO *CH,) and 3 - isopropylpropionyl-acetone (CH,),CHCHAc*CO*C,H, furnish interesting examples of the influence of chemical structure on median enolisation.They differ from their n-propyl isomerides in giving neither ferric nor cupric derivatives. 3-isoBut-ylacetylacetone, (CH,),CH*CH,*CH( CO-CH,),, in which a methylene group is interposed between the branched chain and the median carbon atom gives however both ferric and cupric derivatives just as readily as 3-n-butylacetyla~etone (J. 1924, 125 763). But although ordinary median enolisation is inhibited in the 3-isopropyl-P-diketones they react with tellurium tetra-chloride to give cyclic telluridichlorides. If enolisafion is an essential concomitant of the primary phase in this condensation, it is therefore more probably terminal than median. 5. 3 3-Didkyluted p - d i h e s .The fact that 3 3-dimethyl 2614 MOWAN : and 3 3-diethyl-acetylacetone both give cyclic telluridichlorides is conclusive evidence that any preliminary enolisation must be terminal since in these cases the possibility of median enohtion is absent (Morgan and Drew J. 1924,125 735 1601). In formula I the terminal chains are represented by the symbols R*CH,- and -CH2R” and it has been found that cyclic telluridichlorides are not produced unless both methylene groups ~ J X present. If cyclic condensation is prevented entirely by the conversion of one CH,R group into CHRR’ the p-diketones with one such branching chain give only non-cyclic telluritrichlorides and dichlorides. With two terminal branching chains as in diisobutyrylmethane, the formation of telluriferous products is reduced to a minimum, 90% of the tellurium is set free and the only telluriferous product is a non-cyclic telluritrichloride formed to a very slight extent (Morgan and Taylor this vol.p. 797). Benzoylacetone is incapable of twofold terminal enolisation and gives rise only to non-cyclic telluriferous compounds and for similar reitsons ill-defined products are obtainable from dibenzoylmethane. When present in the positions indicated by R R’ and R” phenyl radicals prevent completely the formation of cyclotelluridichlorides unless a methylene group is interposed. This intervention is effected at the median carbon atom by benzylating the sodium derivative of p-diketone as in 3-benzylprcvpionylacetone which condenses to form 4-benxyl-2-methylcyclotelluripentccne-3 5-dione 1 l-dichloride (VI).3-Benzyl- and 3 3-dibenzyl-acetylacetones have also been converted into cyclic telluridichlorides although condensation did not occur with 3 3-di-p-nitrobenzylacetylacetone (Morgan and Taylor la. cit.). A benzyl group waa introduced into terminal position R or R” (formula I) by operating with @-phenylpropionyZucetone which underwent condensation with tellurium tetrachloride in the normal way for although the cyclic telluridichloride was not isolated in a state of purity it was identified by conversion into its reduction product 2-benzyEcyclotellur~e~ne-3 5-dione (V). Te Te 6. Terminal branching c h i n s . 7. InJluence of aromatic groups. ,. \/ CHR R = n- or iso-C,H or CH2Ph PRODUC!L'ION OF CydQTELLlJRIPENTANEDIONE DICHLORIDES.2615 8. Reduction of cycloikUu~pentunedkme dkhhidtv to cyclo-teuuropentadiones. Apart from the chemical significance attach-ing to the new group of cyclic tellmidichlorides these derivatives are of interest from the point of view of chemical bacteriology, because each member of the group is readily reducible to a cyclo-telluropentanedione (V and VI) the reaction being a general one. Many of these cyclic telluro-derivatives are sufiiciently soluble in cold water to impart to the aqueous soluttions outstanding germicidal properties. The most powerful bacfericide of the series is 2 6-dimethylcycEotelluropntane-3 5-dione (from dipropionyl-methane) but as this derivative is difficult to produce in large amount the next most efficient members have been most exten-sively employed in bacteriological tests.These substances are 2-methylcyclotelluropentane-3 5-dione (from propionylacetone) and its 3-alkylated homologues. The methyl and ethyl derivatives have already been prepared whereas the n- and iso-propyl compounds and the benzyl derivatives all symbolised by the general formula VI, are described in the experimental part of this communication. The chemical con-stitution ascribed to cyclotelluropentane-3 5-diones (V and VI) as the result of the preceding experimental proofs is confirmed by the oximation of these substances. In general both monoximes and dioximes are obtainable, although it is evident that the progress of this reaction is affected by steric hindrance.2-Methylcyclotelluropentane-3 5-dione resembles syclotelluro-pentane-3 5-dione the simplest member of the series in yieldmg chiefly the dioxime whereas 2 -methyl- 4- e t hylc yclotellur opentane-3 5-dione yields both mono- and di-oximes and the monoxime is never entirely absent even when drastic oximation is employed. These examples and the earlier cases (Morgan and Drew Morgan and Taylor h. cit.) demonstrate the presence of two ketonic carbonyl groups in the cyclotelluropentane-3 5-diones. 9. Oximes of cyclotelluropentane-3 5-dimes. E x P E R I M E N T A L. [With FREDERICK JAMES CORBY.] 1. 2-Methyl-4-~~yEcycloteuur~entane-3 5-dione (VI). Sodium propionylacetone (23 g.) made from the diketone in dry ether wils heated for 8 hours with 80 g.of n-propyl iodide; reaction commenced a t 115" the temperature was maintained at 130" for 2 hours and finally raised to 150". The cooled mixture wm added to water the aqueous layer extracted with ether and the et,hereal extract added to the organic layer. The latter o 2616 MORGAN : fractionation furnished n-propglprophylacetone b. p. 210"/750 mm. with slight decomposition. This n-propyl diketone gave an intense bluish-purple coloration with ferric chloride quite distinct from the blood-red tints obtained with the non-3-alkylated diketones. The new diketone had a pleasant terpenoid odour and yielded with ammoniacal cupric acetate a greenish-grey voluminous precipitate of copper 3-n-propyZpropionylacetone readily soluble in acetone, methyl and ethyl alcohols and crystallising from benzene in greenish-grey silvery needles melting and decomposing a t 178" (Found Cu 16.8.2-Methyl-4-n-propylcyclotdluripentane-3 5-ddone 1 1 -Diclhloride, Cl,HMO,Cu requires Cu 17.0y0). COCH - CH,'[CH,120CH<C0.CH(CH3)>Tec1~. -After heating under reflux for 1* hours a mixture of 6 g. of 3-n-propylpropionylacetone 5-7 g. of tellurium tetrachloride and 50 C.C. of chloroform the orange filtrate from tellurium wm concentrated in a vacuum over calcium chloride until crystals of the telluri-dichIoride separated. The mother-liquor after extraction with light petroleum to remove unchanged diketone was again con-centrated and the process repeated so that three crops of crystals were obtained (yield 62%). Recrystallised from chloroform the dichloride separated in colourless prisms darkening a t 145" blacken-ing a t 150" (Found Cl 20.2; Te 35.9.CgHl,02C&Te requires C1 20.2; Te 36.15%). When suspended in ice-cold water and treated with potassium metabisulphite the dichloride was readily reduced to 2-methyl-4-n-propylc yclotelluropen tane-3 &dime (VI) with slight deposition of tellurium. The product was soluble in water but less soluble than its 3-methyl analogue ; it was recovered from aqueous solution by benzene. It was obtained from methyl alcohol in golden-yellow crystals m. p. 102" with slight decomposition (Found: C 38.3 ; H 5.1 ; Te 44.9. CgHl,O,Te requires C 38.4; H 5.0 ; Te 45*20/). 2. 2-iMethyZ-4-isopropylcyclotelluropentu,~ze-3 5-dime (VI). Sodium propionylacetone (23 g.) was heated with 120 g.of isopropyl iodide for 8 hours at 130". The cooled mixture was poured into water and the two layers were worked up as in t'he case of the n-propyl isomeride. 3-isoPrqyZpopionyZacelacetone CH3-CH,COCH(CHMe,)*CO*CH,, boiled at 195"/750 mm. with slight decomposition; it differed from 3-n-propylpropionylacetone in not developing any ferric coloration and in not giving a copper derivative with ammoniacal cupric acetate -Ten g. of the preceding diketone 9 g. of tellurium tetrachloride, and 80 C.C. of purified chloroform were heated under reflus for 2 hours and the orange filtrate waa concentrated to the cptallising point. The subsequent procedure was the =me as in the case of the n-propyl isomeride and the telluridichloride crysh- in colourless glistening prisms darkening at 168" and blackening at 173' (Found Cl 20.1; Te 35-8.C,H1,O,&Te requires C1, 20.2; Te 36.17%). Reduction in the normal way led with liberation of free tellurium, to 2-~~yZ-4-isopropylcycloteuur~ntu.~e-3 5-dione (VI) ; this pro-duct cqmtallised from methyl alcohol in light yellow needles, m. p. 127" ; it was much less soluble in water than the corresponding n-propyl compound (Found C 38.5; H 5.05; Te 44-85. C&€,,O,Te requires C 38.4; H 5.0; Te 45-10/,). An attempt was now made to prepre a third isomeride of the foregoing isomeric propyltelluro-derivatives. 3-Methylpropionyl-acetone prepared by the method formerly described (J. 1924, 125 7459 was dissolved in dry ether and converted info sodium salt.The latter was heated with 3 parts of ethyl iodide in an autoclave for 6 hours at 180" the pressure.being 10 atmospheres. The dialkylated diketone was extracted from the mixture by the procedure adopted for the two propylated diketones. On fraction-ation 3-methyl-3-ethyZprqpimylizcetone distilled at llSo/10 mm. (yield 25%). The diketone which had a fragrant odour gave neither coloration with ferric chloride nor precipitate with am-moniacd cupric acetate. In the condensation with tellurium tetrachloride and 3-methyl-3-ethylpropionylacetone tellurium was deposited and a consider-able amount of tar was produced; the telluridichloride was not isolated although it was probably present in the brown tarry chloroform solution since $his changed to bright yellow on treat-ment with aqueous metabisulphite.3. 4-BenzyZ-2-methylcyclotdluropentu.ne-3 5-dime (VI). 3-Benzylpropionylac~.-Sodium propionylacetone (34 g.) was heated under reflux with 13 g. of rectified benzyl chloride for 8 hours at 140" the product being worked up as in the caae of the propylated diketones. The benzylated diketone which dis-tilled at 185"/20 mm. waa a colourless liquid with fragrant odour; it developed an intense reddish-violet coloration with ferric chloride and with ammoniacal cupric acetate it yielded a wppm derivative 4 s 2618 MOMAN : readily soluble in alcohol acetnne or benzene to dark olive-green solutions. Copper 3- b e n z g l p ~ * m ~ ~ crystallised from these solvents in pale grey silvery needles m. p. 182" (Found Cu, 13.4. C,,H,O,Cu requires (31 1305%).4-Benzyl-2-mthyEcycloteUuripentane-3 5-dime 1 l-DkMoride, -The orange solution obtained by heating 8.5 g. of 3-benzyl-propionylacetone 5.8 g. of tellurium tetrachloride and 50 C.C. of dry chloroform for 2 hours was decanted from tellurium and con-centrated in a vacuum to the crystallising point. The mother-liquor was treated as in the caae of the propylated dichlorides and 5 g. of telluriferous product were obtained. Recrystallised from acetone the telluridichhide separated in colourless glistening prisms m. p. 168" (Found C1 17-7; Te 31.8. C,,H,,O,~Te requires Cl 17-75; Te 31.7%). Suspended in water and reduced with potassium metabisulphite, the dichloride yielded 4-benzyl-2-methylcyclotellur~entane-3 5-dione with very slight elimination of tellurium.This telluro-derivative crystallised from methyl alcohol in yellow needles m. p. 124" with decomposition. The crystals did not sublime in a vacuum and were only slightly soluble in water (Found C 47-5 ; H 4.4 ; ,Te, 38.4. CI3H,,O2Te requires C 47.3 ; H 4-3 ; Te 3843%). [With EVELINE JONES.] 1. 3-isoButylmetylacetone ( CH3),CH*CH2*CH(C0 *CH3)2. Rectified isobutyl iodide (b. p. 117-120") was obtained in 60% yield by Blaise's method (Bull. Soc. chim. 1911 9 1). A mixture of 161 g. of this iodide and 52 g. of sodium acetylacetone con-tained in a stoppered glass bottle was heated gradually in a rotating autoclave to 170" and was maintained at this temperature for an hour (pressure 150 lb. per sq. inch). The liquid contents of the bottle were drained from sodium iodide and unchanged sodium acetylacetone and the latter solids were extracted with ether.The oil and ethereal extracts were distilled together up to 124" to remove solvent and isobutyl iodide and the residue was fractionated under reduced pressure; the fraction distilling at 93-94"/10 mm. consisted of 3-isobutylacetylacetone which developed a bluish-purple coloration with ferric chloride and was purified by con-version .into its copper derivative by interaction with ammoniacal cupric acetate. Copper isobutyhtylacetone crystallised from petro-leum (b. p. 60-80") in well-defined steel-grey needles m. p. 158" (Found Cu 16-9. C,,HmO,Cu requires Cu 17-070) PRODUCTION OF C~C~!ELLURIPENTANEDIONE DICHLOIUDES. 2619 4-isoBzctylcycldeUur~~ne-3 ; 5 - d i m 1 I-&*-, -A mixture of 5.8 g.of isobutylacetylacehne and 5 g. of tellurium tetraddoride in 40 C.C. of purified dry chloroform was heated on the water-bath for 1-2 hours. The filtrate from a small deposit of tellurium ww concentrated at the ordinary temperature until acicdar crystals separated. R e c r y s t d . k d from acetone or chloro-form the dichibide separated in well-defined colourless need-, m. p. 142" (yield 2 g.) (Found Cl 20.3; Te 36-4. C&O,Te(& requires Cl 20-1; Te 36.2%). 4-isoButylcycloteUuropentane-3 Li-dione, -The foregoing dichloride when reduced with aqueous potassium metabisulphite yielded a yellow solid sparingly soluble in water. Recrystallised from benzene the tellnro-derivative separated in yellow leaflets m.p. 150" (Found C 38.4; H 5.0. C&Il4O2Te requires C 38.4 ; H 5.0%). 2. $- Phen ylpropion ylacetone C,H5*CH2*CH2CO*CH,-C0.CH,. Ethyl P-phenylpropionate prepared by boding 209 g. of P-phenyl-propionic acid for 2 hours with 900 C.C. of absolute alcohol con-taining 30 g. of hydrogen chloride was fractionated until boiling a t 244-245". The Claisen condensation was carried out with acetone and sodium in calculated quantities and ethyl p-phenyl-propionate (3 mols.) the acetone being diluted with six tima its volume of dry benzene. After 12 hours the mixture was heated on the water-bath cooled and poured on to ice the aqueous layer being treated successively with acetic acid and cupric acetate. The precipitate consisted of a mixture of copper a-phenylpropionate and copper P-phenylpropionylucetone which were separated by fractional crystallisation from benzene the latter compound being the more soluble.When purified it had a greyish-blue colour and melted a t 158" (Found Cu 14-4. C,,H,60,Cu requires Cu, 14.4%). 2-Benzylcyclotellurilientane-3 5 - d i m 1 l-Dic&&.-Hydrogen chloride was evolved with a slight deposition of tellurium when 5 g. of tellurium tetrachloride 5-3 g. of p-phenylpropionylacetone and 40 C.C. of purified chloroform were heated on the water-bath for 2 hours. The solution was concentrated in a vacuum desiccator to a dark brown jelly and stirred with light petroleum but the semi-solid maas showed no tendency to crystallise and accordingly it wm reduced with aqueous potassium metabbulphite when a 4 s* 2620 MORGAN : yellow solid sepamted mixed with tarry matter and tellurium.After extraction with hot alcohol the golden-yellow filtrate yielded 2-benzylcycloteUuropentane-3 5-dione (V) in small yellow crystals decomposing at 159" (Found C 46.8; H 3.9; Te 41.0. C1,Hl,O,Te requires C 46.6 ; H 3.8 ; Te 40.4%). [With CYRIL JAMES ALLAN TAYLOR.] 1. Copper duodecoylacetone prepared by the Claisen condens-ation from methyl undecyl ketone (Morgan and Holmea J . Xoc. Chem. Id. 1925 44 108~) was decomposed with sulphuric acid in presence of ether. The free P-diketone obtained from the ethereal layer melted at 31-32' and had the characteristic pro-perties of it8 series. 2-n-DecylcycloteUurientane-3 5-&one 1 I - D i c W (VII). (VII.) ~lo%*p*Te%*p2 C l P 2 1*(p-Te-p2 ( VI I I.) OC-CH,-CO OCLCH,-CO -Four g.of tellurium tetrachloride and 5 g. (1.6 mols.) of duo-decoylacetone were heated in chloroform solution for 3 hours. The dark brown oil obtained on evaporation was extracted repeatedly with petroleum (b. p. 40-60") to remove unchanged diketone and then left for 1 month in a vacuum desiccator. Crystallisation set in and the solid product was stirred successively with carbon tetrachloride and petroleum. The warm benzene extract of this producf was diluted with excess of petroleum when silvery-white flakes separated (yield 21%) (Found C1 16.4; Te 29.4. C,,H,,O,&Te requires C1 16.3; Te 29.2y0). 2-n-Decylcyclotelluripentane-3 5-dione 1 l-dichloride was readily soluble in cold benzene chloroform or acetone less soluble in carbon tetrachloride and dissolved only sparingly in petroleum; it melted a t 89'.2-n-D~~~ycloteUuropentane-3 5-dione (VIII) obtained by the reduction of the preceding substance with alkali bisulphite crystal-lised from aqueous alcohol in pale yellow woolly masses m. p. 98-99' (decomp.) (Found C 49.1 ; H 7.1. C,,H,,O,Te requires C 49.25; H 7.1%). This telluropentanedione derivative was readily soluble in cold benzene or alcohol insoluble in water but dissolved in dilute aqueous caustic soda especially on warming; on prolonged boiling, tellurium was deposited. 2. Tellurium Tetrachloride and 3-Phe.lzylpropionyt~n~. Four g . of tellurium tetrachloride were added to 6.0 g. (2 mols.) of 3-phenylpropionylaetone (Ber. 1925 58 340) in 25 C.C.of chloroform and the solution was boiled for 1-2 hours. Afte PRODUCTION OF CZJ~QTELLURTPENTANEDIONE DICHLORIDES. 2621 evaporating off the solvent the tarry residue waa extracted twice with light petroleum and digested with carbon tetrachloride and the solution in this solvent concentrated when crydalbation set in. The product which was much discoloured separated from carbon tetrachloride in colourless lamella! m. p. 64-68". It gave the enolic reaction with ferric chloride and was very sensitive to moisture; it did not evolve the earthy odour of an 0-ethyl P-diketone with cold alkali. The condensation was varied by changing the proportion of di-ketone but the products were similar and contained about 19-40/; of chlorine with C 27.1 ; H 2.6%.These numbers did not corre-spond with the values calculated for a cyclic dichloride X"TeC.&, or for di- and tri-chlorides of the type X'TeG and X'2TeC14. The reduction product with alkali bisulphite was unstable. It was therefore evident that the condensation of 3-phenylpropionyl-acetone with tellurium tetrachloride did not lead to a derivative of the cyclotelluripentanedione dichloride series. [With RICHARD EATOUGH KELLETT.] 1. 2-blethyEcyclote1lu~~opentane-3 5-dione Dioxhe, CH,.FH-Te-piH* NOH:C-CH, -Two g. of hydroxylamine sulphate in 30 C.C. of water were added to 0.7 g. of 2-methylcyclotelluropentane-3 5-dione (J. 1923 123, 450) in 50 C.C. of water ; the solution was neutralised with sodium hydroxide and warmed on the water-bath. The crude oxime separated on cooling in minute yellow crystals.Extraction of this precipitate with boiling benzene gave a small amount of soluble product probably monoxime blackening at 135-150". The residue dissolved in warm alcohol and separated in greykh-yellow crystals darkening at 153" and melting sharply at 161.5" (Found N 10-4; Te 47.0. C,H,,0~2Te requires N 10-4; Te, 47 -3 Yo). The dioxime was insoluble in hot water or benzene. 2. The O x i m of 2 - M e t h y l - 4 - e t ~ y ~ y c ~ o ~ ~ ~ ~ ~ - 3 5-dione. -Two g. of hydroxylamine sulphate in 50 C.C. of water were addd to 0.7 g. of 2-methyl-4-ethylcycluropentane-3 5-&one (J., 1924 125 758) in 50 C.C. of warm alcohol. Sodium acetate was added with sufficient water to bring the reagents into solution when heated on the water-bath.Some tellurium separated and after 10 minutes the cooled solution deposited a voluminous mass-of yellow crystals; the greater part of this dissolved readily in warm benzene but the nitrogen content of the crystalbed product waa 7-7 that is intermediate between 5-0 and 9-4 required fo 2622 MORGAN : the mono- and di-osimes respectively. The mixture ww extracted with either boiling water or a small amount of benzene. After repeated crystallisation the more soluble momxime was isolated in bright yellow crystah blackening at 135" and melting at 157" (Pound N 5.1 ; Te 45-1. C,H,,O;NTe requires N 5-0; Te, 45- 1 yo). 2 - ~ e t ~ y l - 4 - e t h y l c y c l o t e l l u r ~ e ~ ~ - ~ $dime wwrwxime (IX) was only sparingly soluble in hot water and decomposed slightly in aqueous solution.(IX.) 08-CHEt-C:NOH NOH%CHEzzOH (x') CH,. H-Te-YH CH,* H-T 2-~ethy~-4-ethyZcycloteZZu~opentane-3 5 - d i m Dioxime (X).-Oximation to the dioxime was never complete even on carrying out the condensation in solutions rendered alkaline with sodium hydroxide either by direct treatment of the diketone or by the further action of hydroxyla,mine on the monoxime. The mixed products from either of these operations were extracted with boiling benzene to remove monoxime and the residues crystallised from boiling alcohol in which they dissolved without decomposi-tion. The dioxime separated as a greyish-yellow cryst,alline powder blackening at 170" and decomposing at 182" (Found N 9-7 ; Te 42.7. The dioxime is practically insoluble in hot water or cold benzene, more soluble in the latter on boiling and dissolves with slight decomposition in warm acetylacetone.C,H,,O,N,Te requires N 9.4; Te 42.85%). [With OLIVER CECIL ELvrnTs.1 1. 4-sec.-Butylcyclotelluri(pentane-3 5-dione Bichloride. sa.-Butyl alcohol synthesised by Wood and Scarf's process ( J . Soc. Chem. Ind. 1923 42 1 3 ~ ) (74 g.) was converted into sec.-butyl iodide by treating with red phosphorus (20 g . ) and iodine (128 g.), the latter reagent being added in small quantities. After warming the mixture the iodide was distilled off washed with aqueous sodium carbonate dried and fractionated (b. p. 117-118"). 3 - sec .-But yZucet ylacetone (CH,-CO) ,CH- CH ( C2H 5 ) =CH was o b -tained by heating in a rotating autoclave at 14&160" for 2 hours (pressure 120 lb.per sq. inch) 35 g. of sodium acetylacetone and 10 g. of 8s.-butyl iodide. The resulting mixture was filtered the sodium iodide washed with ether and the combined filtrates were distilled first under the ordinary and then under reduced pressure. The fraction boiling at 110-113"/13 mm. was again rectified until it ceased to give the red coloration with ferric chloride. Th PEODUCIXON OF C ~ % T E . L L ~ E ~ A N E D I O N E DICHLOBXDIES. 2623 final product boiled at 109-111°/13 mm. but the yield was only 9% of theory. 3-sec.-Butylacetylacetone gave no copper derivative with am-moniacal copper acetate but underwent condensation with tellurium tetrachloride. A chloroform solution (30 c.c.) of the latter reagent (2-9 g.) and diketone (2-5 g.) evolved hydrogen chloride on boiling and 0-2 g.of tellurium was set free. The fltrate concentrated in a vacuum to a brown tar solidikd on treatment with light petroleum. The solid product c r y s m from benzene in lustrous, colourless prismatic peedles darkening at 162" and melting at 168-169" (yield 370/,) (Found Cl 20.0. C,H,,02C4Te requires 4-sec.-Butylcyclotripentane-3 5-dione 1 1-dichloride (XI) wa8 reduced with aqueous sodium bisulphite and the insoluble reduction product was extracted with benzene and c r y s m from alcohol. EEI,-Te%?H CH2-Te3H2 (XI.) 0-YH-CO b V H - C O (XTJ-1 CH3*CH*C2H5 CH3*CH-C2H c1 20.1y0). 4-sec.-ButyZcyclotelluropentane-3 5-dione (XI) was obtained in C 38.2; H 5.3. primrose-yellow needles m.p. 145" (Found : C,H,,O,Te requires C 38.45; H 540/b). 2. 4-sec.-dl-Amylcyclotelluripentune-3 5 - d i m 1 l-Dichloride. (m.1 CO- FH-60 CO-H-ZO (m-1 -An intimate mixture of 52 g. of dl-amyl iodide and 20 g of sodium acetylacetone was maintained at 130" for 2 hours in the rotating autoclave (100 lb. per sq. inch) and fhally at 160" for 30 minutes. The oily product and the sodium iodide were treated as in the preceding preparation (p. 2622). dl-sec.-Am?/lacetylacetone wit8 obtained as an oil b. p. 116"/15 mm. (yield 36%). In alcoholic solution this 3-alkylated diketone developed a purple coloration with ferric chloride the liquid becoming blue on addition of water. With ammoniacal cupric acetate the copper derivative was obtained ; it crystallised from methyl alcohol in greenish-grey needles m.p. 120" and was very soluble in chloroform benzene or petroleum (b. p. 80-100") but dissolved only slightly in light petroleum (b. p. 40-60") (Found Cu 16-2. C&€=04Cu requires Cu, 15.9y0). Condensation of the diketone and telIurium tetrachloride was effected in purified chloroform and the cyclic &chloride extracted aa in the preceding preparation (p. 2623) the yield being 35%. FQ-TeC&*H2 p2-Te- Hz CqCHMeEt CQCHMeE 2624 PRODUCTION OF CY~OTEUURIPENTANEDIONE DICHLOBIDES. 4-sec.-Amylcyclotelluri~en~~-3 5-dime dichbride (XIII) crys-tallised from benzene in colourless lustrous prismatic needles darkening at 136" and melting at 162" (Found CI 19.6; Te 34.5. Clo13,60,C&Te requires Cl 19.3 ; Te 34-8:4,).4-sec.-AmylcycloteUuro-pentane-3 5-dim (XIV) obtained from the preceding dichloride by reduction with bisulphite c r y a a from benzene or dilute alcohol in pale yellow leaflets dissolving sparingly in hot water and soluble in benzene but insoluble in petroleum (b. p.-40-60"); m. p. 138-139" (Found C 40.9; H 5.7. C,oH,,02Te requires C 40-6; H 5.45%). Although the two foregoing telluriferous compounds containing sec.-amyl groups were obtained as crystalline products the con-densation of tellurium tetrachloride with 3-sec.-amyZdipropionyl-methane resulted in oily products. This 3-akylated diketone was obtained without using the autoclave by heating under reflux 20 g. of sec.-amyl iodide and 5 g. of sodium dipropionylmethane for 1 hour at 140-145"; sodium iodide separated slowly and the oily product on distillation yielded 2.5 g.of the diketone b. p. 137"/15-17 mm. which developed a purple coloration with ferric chloride. Copper 3 -sec . -amyl&ipropion ylmethune was slowly formed on shaking the diketone with ammoniacal cupric acetate. Crystalljsed from petroleum b. p. 60-SO" it separated as a greenish-grey meal m. p. 105"; it was very soluble in benzene or chloroform (Found Cu 14-5. Addendum.-In addition to the copper derivatives obtained as above from the open-chain diketones the following metallic deriv-atives from the cyclic acetylmethylcyclohexanone (Leser Bull. Soc. chim. 1900,23 370; 1901,25 196) were examined. The diketone employed had D:T 1-024 and [a]& + 105.8". Its copper deriv-ative was examined for the presence of isomerides by fractional crysta,llisation from alcohol but no change in the melting point (186") was noticed.A benzene solution was too deeply coloured for determination of its rotation. Beryllium Acetylmethylcyclohmanone Be( C,Hl,02)2.-On shaking together a concentrated solution of beryllium acetate containing sodium acetate and 1.5 g. of acetylmethylcyclohexanone in 30 C.C. of alcohol a white precipitate of the beryllium derivative was obtained in quantitative yield. This producf was very soluble in benzene or chloroform; evaporation of the latter solution led to a glass which became crystalline on rubbing. Minute crystals obtained from petroleum (b. p. 80-100") melted at 159-160". Four crops of crystals obtained by fractionation from petroleum were examined at 17" in the polarimeter (0-5 g. in 10 C.C. of benzene ; 1 = 1). The rotations and melting points remained constant : C,H,,O,Cu requires Cu 13.9%) INTEB~CTIONS OF TELLURIUM TETB~CHM;BIDE ETC. 2625 a 2*66" 2-67" 2-66" 2-68' ; m. p. 160" 159-5" 160' 1596" ; whence [ a g + 106-4" or [MI + 335" (Found Be 2-95. C,,H&,Be requires Be 3.0%). The authors desire to express their thanks to the Advisory Council of the Department of Scientific and Industrial m h , to the Government Grant Committee of the Royal Society and fo the Research Committee of the University of Birmingham for grants which have helped to defray the expense of this investigation. UNIVEBSITY OF BIEWINGHAM, EDGBASTON. [Received October 2 4 1925.