Prins-Reaktionen mit Arylaldehyden, 5. Mitt.: Zur Umsetzung mit 2-Buten und mit Cyclohexen

By reaction of 2-[(1RS, 2RS)-2-hydroxy-1-methyl-propyl]-2-phenyl-1,3-dithiane (1 a) withcis-2-butene oxide, subsequent reduction and acetalizationc-4,t-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 a) andt-4,c-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 b) were synthesized as model compounds. For the same purpose by aldol reaction of cyclohexanone and reduction (1RS, 2SR)-2[(RS)-hydroxy-(4-methoxyphenyl)methyl]cyclohexanol (7 a), (1RS, 2RS)-2[(SR)-hydroxy-(4-methoxyphenyl)methyl]cyclohexanol (8 a), and (1RS, 2RS)-2[(RS)-hydroxy-(4-nitrophenyl)methyl]cyclohexanol (8 b) and by acetalization (2 , 4 , 4 a, 8 a)-2,4-bis(4-methoxyphenyl)hexahydro-4H-1,3-benzodioxin (9 a) and (2 , 4 , 4 a, 8 a)-2,4-bis(4-nitrophenyl)hexahydro-4H-1,3-benzodioxin (10 b) were obtained. FromPrins reactions, starting with 2-butene3 a,c-4,c-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 c),r-4,t-5-dimethyl-c-6-phenyl-1,3,2-dioxathiane-2,2-dioxide (4), and (2Z, 4E)-1,5-diphenyl-4-methyl-2,4-pentadien-1-on (5), and starting with cyclohexene (E)-3-(4-methoxybenzylidene)cyclohexenyl-4-methoxyphenyl ketone (11) have been isolated in low yields.

4. Mitt.:Griengl, H., Nowak, P., Mh. Chem.109, 11 (1978).     

Prins-Reaktionen mit Arylaldehyden, 4. Mitt.: 2,4-Diphenylhexahydro-4H-1,3-benzodioxine

The four diastereomeric 2-(hydroxyphenylmethyl)cyclohexanols2a-2d are prepared. By reaction with benzaldehyde each2a-2c gives stereospecifically only one of the two possible configurationally correlated 2,4-diphenylhexahydro-4H-1,3-benzodioxins3a-3c. However, from (1RS, 2SR)-2 [(SR)-hydroxyphenylmethyl]cyclohexanol (2d) both dioxins3d and3e are obtained. The configurational assignments are based on¹H-NMR spectroscopy and synthetic correlations. Conformational aspects are discussed. As is shown by chromatography, inPrins reactions of cyclohexene with benzaldehyde only one dioxin3c is formed.     

Über 4,4,6-trisubstituierte 3,4-Dihydro-2(1H)-pyrimidinimine,Hexahydro-2(1H)-chinazolinimine bzw.-one bzw.-thione und Spiro[cycloalkan-1,4′(1′H)-cycloalkeno-pyrimidin]-2′ (3′H)-imine

The 2-alken-1-ones2 b, 2 c and3–8, which have very different structures, were reacted with guanidine to give cyclic compounds:2 b and2 c resp. are transformed by guanidine to the trisubstituted 3,4-dihydro-2(1H)-pyrimidinimines1 b and1 c resp., action of guanidine on the cyclo-hexylidenaceton (3) yields 4-methyl-1,3-diaza-4-spiro[5,5]-undecen-2-imine (11); isopropylidencyclohexanone4 and the isomeric (methylcyclohexenyl)ethanone5 condense with guanidine resp. urea resp. NH₄CNS to give 4,4-dimethyl-3,4,5,6,7,8-hexahydro-2(1H)-quinazolinimine (15), resp.-one (16), resp.-thione (17) and 4,8a-dimethyl-3,4,6,7,8,8a-hexahydro-2(1H)-quinazolinthione (19). With the cycloalkyliden-alkanones6–8 guanidine reacts to yield the spiro[cycloalkan-1,4(1H)-cycloalkenopyrimidin]-2(3H)-imines24–26. The structure of the compounds cited is derived from their NMR-and (partially) mass spectra; from most of the bases picrates were also synthesized.

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Herrn Prof. Dr.H. Grubitsch zum 70. Geburtstag gewidmet.     

Prins-Reaktionen mit Arylaldehyden, 2. Mitt. Diene

By 1,4-addition of arylaldehydes to 2,3-dimethyl-1,3-butadiene in the presence of sulfuric acid 2-aryl-4,5-dimethyl-3,6-dihydro-2H-pyrans are obtained. From 1,3-butadiene and isoprene beside the corresponding 3,6-dihydro-2H-pyrans by reaction with two more molecules aldehydetrans-2,4,7-triphenyl-4a,7,8,8a-tetrahydro-4H,5H-pyrano[4,3-d-1,3-dioxines are formed. With 1,3-cyclohexadiene, however, 1,2-addition of benzaldehyde is observed to givecis-r-2,c-4-diphenyl-4a,5,6,8a-tetrahydro-1,3-benzodioxane.

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Herrn Prof. Dr.Anton v. Wacek, emerit. Vorstand des Instituts für Organische Chemie und Organisch-chemische Technologie der Technischen Universität Graz, in Verbundenheit zum 80. Geburtstag gewidmet.

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1. Mitt.:H. Griengl undK. P. Geppert, Mh. Chem.107, 421 (1976).     

1-[5-(1,3-二氧-4,5,6,7-四氢-1H-异吲哚-2-基)苯基]-3-取代脲衍生物的合成与除草活性研究

为了寻找高效低毒的原卟啉原氧化酶抑制剂(protox)类除草剂, 设计并合成了一系列1-[5-(1,3-二氧-4,5,6,7-四氢-1H-异吲哚-2-基)苯基]-3-取代脲类衍生物4a～4d和5a～5g. 化合物4a～4d经异氰酸酯法合成, 收率、纯度高; 化合物5a～5g利用固体光气一锅法合成, 反应时间短.所得化合物结构经¹H NMR, IR, 质谱和元素分析表征. 初步生物活性测试表明: 化合物4c, 5a, 5b, 5c在有效成分75 g/hm² 剂量下对苘麻、马刺苋、凹头苋等双子叶杂草表现出90%以上的防效.     

Reaktion von (Z,Z)-1,5-Cyclooctadien mit N-Bromsuccinimid in Gegenwart von Wasser oder Methanol

The action of N-bromosuccinimide (NBS) and water on (Z, Z)-1,5-cyclooctadiene (1) results in the formation ofendo,endo-2,5-dibromo-9-oxabicyclo [4.2.1]nonane (2),endo,endo-2,6-dibromo-9-oxabicyclo[3.3.1]nonane (3),trans-6-bromo-(Z)-cycloocten-5-ol (4a),endo-6-bromo-cis-bicyclo[3.3.0]octan-2-ol (5a), andtrans-5,6-dibromo-(Z)-cyclooctene (6).2 and3 are considered to be produced from intermediary4a via transanular participation of the hydroxyl group.5a is formed in a result of transanular double bond participation.The reaction of1 withNBS and methanol similarly produces2, 3,trans-6-bromo-5-methoxy-(Z)-cyclooctene (4b),endo-6-bromo-2-methoxy-cis-bicyclo-[3.3.0]octane (5b), and6.

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4. Mitt.:G. Haufe, M. Mühlstädt undJ. Graefe, Mh. Chem.108, 1431 (1977).

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2 Aus der Dissertation zur Promotion A vonG. Haufe, Karl Marx-Universität Leipzig, 1975.     

Zur Kenntnis organischerLewis-Säuren, 36.Cis—trans-Gleichgewichte und Konformationen von 2,(x)-Dialkyl-1-dicyanomethylencyclohexanen. Wahlweise einfache Darstellung dercis- odertrans-Formen

Knoevenagel condensation of malononitrile withcis- andtrans-2,5-dimethylcyclohexanone (1 c and1 t, respectively) leads to2 c and2 t, respectively, and withtrans-1-decalone to4 t. The equilibria2 c2 t and4 c4 t have been determined as well as, by means of 270-MHz-¹H-NMR, the conformations of these four compounds. The dicyanomethylene group is found to induce axial positions of neighbouring alkyl residues on the cyclohexane ring (or when this is impossible, as in the case of4 t, the twist form of the cyclohexane ring). This results in a strong predominance of thecis isomers in the equilibria2 c2 t and4 c4 t whereas thetrans isomers strongly predominate in the equilibria among the starting ketones. This situation allows the optional preparation of2 c or2 t, and of4 c or4 t, from the more stable starting ketone (or ketone mixture). The free conformational energy of the distorted twist form of4 t amounts to 17 kJ/mol.

Herrn Prof. Dr.E. Ziegler, Graz, zum 70. Geburtstag in aufrichtiger Verbundenheit gewidmet.     

Kondensierte Heterocyclen aus β-Isothiocyanatoketonen und Aminocarbonsäuren

On reaction of glycine, anthranilic acid and anthranilamide respectively with 4-isothiocyanato-4-methyl-2-pentanone (1), derivatives of condensed heterocycles (oxazolopyrimidine5, pyrimidobenzoxazine7 a, pyrimidobenzodiazine7 c) are formed. The same holds for the reaction of dithiocarbamates, prepared from glycine and CS₂ in aqueous NaOH, with 4-methyl-3-penten-2-one and cinnamaldehyde respectively (12 a, b). The reaction of hot dimethylformamide with7 a leads under initial aminolysis to pyrimidine-anthranildimethylamide2 i; this is subsequently transformed partly through methylpyrimidine-pyridine rearrangement into the N-4-pyridine-anthranil-N,N-dimethylamide10 d, partly under further aminolysis byDMF followed by rearrangement to the dimethylaminodihydro-2(1H)-pyridinethione10 c. 5 is converted to dihydro-4-methylamino-2(1H)-pyridinethione (10 a) in boiling hexanol and2 c to n-hexyl-3-(tetrahydrothioxo-pyridylamino)-propionate (10 b).     

Kondensierte Heterocyclen aus β-Isothiocyanatoketonen und Aminocarbons?uren

On reaction of glycine, anthranilic acid and anthranilamide respectively with 4-isothiocyanato-4-methyl-2-pentanone (1), derivatives of condensed heterocycles (oxazolopyrimidine5, pyrimidobenzoxazine7 a, pyrimidobenzodiazine7 c) are formed. The same holds for the reaction of dithiocarbamates, prepared from glycine and CS₂ in aqueous NaOH, with 4-methyl-3-penten-2-one and cinnamaldehyde respectively (12 a, b). The reaction of hot dimethylformamide with7 a leads under initial aminolysis to pyrimidine-anthranildimethylamide2 i; this is subsequently transformed partly through methylpyrimidine-pyridine rearrangement into the N-4-pyridine-anthranil-N,N-dimethylamide10 d, partly under further aminolysis byDMF followed by rearrangement to the dimethylaminodihydro-2(1H)-pyridinethione10 c. 5 is converted to dihydro-4-methylamino-2(1H)-pyridinethione (10 a) in boiling hexanol and2 c to n-hexyl-3-(tetrahydrothioxo-pyridylamino)-propionate (10 b).     

Über das Verhalten von Betainen gegenüber Phenylisocyanat

Zusammenfassung Pyridinbetain reagiert mit Phenylisocyanat unter Verlust von CO₂ und H₂ zum 2-Oxo-1,3-diphenyl-4-(1-pyridinio)-2,3-dihydro-imidazol-5-olat (1a), während sich Thetin mit dem genannten Reagens zum 2,4-Dioxo-1,3-diphenyl-5-(dimethylsulfonio)-1,2,3,4-tetrahydro-pyrimidin-6-olat (2a) umsetzt.

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Reaction of betaines with phenyl isocyanate (reactions with betaine, III)

(1-Pyridinio)acetate reacts with phenyl isocyanate under the loss of CO₂ and H₂ yielding 2-oxo-1.3-diphenyl-4-(1-pyridinio)-2.3-dihydro-imidazol-5-olate (1a). The reaction of thetine with phenyl isocyanate gives 2.4-dioxo-1.3-diphenyl-5-(dimethylsulfonio)-1.2.3.4-tetrahydro-pyrimidin-6-olate (2a).

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Auszugsweise vorgetragen anläßlich der Chemikertagung in Wien, September 1968.     

Acylgruppenwanderung in N-Acyl-2H-imidazol-4(3H)-thionen

On acylating 2H-imidazole-4(3H)-thiones the orange to violet crystalline N-1-acyl-2H-imidazole-4(3H)-thiones1 a–18 a are formed, the thermal stability of which depends on the acyl group and the substituents in the heterocyclic ring system. Thus the N-aroyl-2,2,5-trimethyl-2H-imidazole-4(3H)-thiones13 a–16 a are stable on being heated to the melting point, while1 a–12 a are converted quantitatively to the corresponding S-aroyl-2H-imidazole-4-thiols1–12. Rearrangement is faster when the heterocyclic ring bears bulky substituents. The aliphatic N-acyl compounds17 a and18 a are thermally unstable. This N S acyl group migration, described here for the first time, is shown to proceed by an intermolecular mechanism.

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Herrn Prof. Dr. Dr. h. c. mult.Hermann F. Mark zum 80. Geburtstag in Verehrung gewidmet.

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88. Mitt.:F. Asinger, A. Saus, H.-J. Gräber, E. Fichtner undW. Leuchtenberger, Mh. Chem.106, 1449 (1975).

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Teil der DissertationE. Fichtner, Techn. Hochschule Aachen, 1974.     

Zur Kenntnis der Reaktionsfähigkeit alkylsubstituierter Thiomorpholine, 1. Mitt.

Zusammenfassung Die Darstellung einigerMannichbasen (3 a-f) bzw.Mannich-basen-hydrochloride (2 a-f) und zahlreicher s-Triazin-Derivate (4 a-d, 5 a–m, 6 a–w, 7 a–e, 8 a–d, und9 a–l) auf Basis des unsubstituierten Thiomorpholins (1 a) sowie C-mono-[2-Methylthiomorpholin (1 b) und 2-Äthylthiomorpholin (1 c)] und C-dialkylierter Thiomorpholine [2-Methyl-3-äthylthiomorpholin (1 d)] wird beschrieben.

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Concomitant action of elementary sulfur and gaseous ammonia upon ketones, LXXIX: On the reactivity of alkyl substituted thiomorpholines, I

The preparation of someMannichbases (3 a-f) andMannich base hydrochlorides (2 a-f), resp., and numerous s-triazine derivatives (4 a-d, 5 a–m, 6 a–w, 7 a–e, 8 a–d, and9 a–l) based upon unsubstituted thiomorpholine (1 a) as well as C-mono-[2-methylthiomorpholine (1 b) and 2-ethylthio-morpholine (1 c)] and C-dialkylated thiomorpholines [2-methyl-3-ethylthiomorpholine (1 d)] is described.

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HerrE. Wilms dankt der Deutschen Texaco AG. für die Gewährung eines Stipendiums herzlichst.     

Stereoselektive Synthesen vons-Decahydropyrenen

Incomplete catalytic hydrogenation of [2.2]metacyclophane (1) or 5,13-dimethyl[2.2]metacyclophane (2) yields (1,2,3,3arH, 4,5,9,10,10acH, 10btH)-decahydropyrene (9) and the dimethylanalogue10, resp.via atransanular cyclisation between positions 8 and 16. Under the same reaction conditions catalytic deuteration (D₂, acetic acid-d₁) affords a selectively deuterated10 (10-d₅).9 is identical with as-decahydropyrene, obtained by high pressure hydrogenation of pyrene. The configurations of9 and10 were established by means of¹³C and¹H-NMR spectroscopy and by comparison with10-d₅.A compound formerly believed to be as-decahydropyrene isomer is shown to be (±)-(1,2,3,3a,4,5,9,10)-octahydropyrene (4).

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Mit 4 Abbildungen

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Herrn Prof. Dr.F. Hecht zum 70. Geburtstag gewidmet.

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Auszugsweise vorgetragen bei der Tagung des Vereins Österreichischer Chemiker in Linz am 27. September 1973.     

三苯基咪唑类化合物的合成及其紫外、荧光性质研究

设计合成了四种三苯基咪唑类化合物:4,5-二苯基-2-对甲酰基苯基咪唑(2a),4,5-二(2-硝基苯基)-2-对甲酰基苯基咪唑(2b),N-苄基-4,5-二苯基-2-对甲酰基苯基咪唑(2c)和N-苄基-4,5-二(2-硝基苯基)-2-对甲酰基苯基咪唑(2d),并用FT-IR,NMR和MS进行结构表征.在乙酸乙酯-石油醚溶液中获得了2c的单晶,用X射线单晶衍射法测定了其晶体结构,晶体属于三斜晶系,空间群P1,晶胞参数a=0.73796(15)nm,b=0.90136(18)nm,c=1.6644(3)nm,α=86.87(3)°,β=78.25(3)°,γ=89.94(3)°,V=1.0822(4)nm3,Dc=1.272g/cm3,Z=2,F(000)=436,μ=0.077mm-1,R1=0.0459,wR2=0.1303.研究了四种化合物的紫外与荧光性质,发现官能团硝基与苄基的引入,对其吸收峰和发射峰均有不同程度的影响:在紫外光谱中两种官能团均使吸收峰蓝移;在荧光光谱中苄基使发射峰蓝移而硝基使发射峰红移.测定了2a和2c在不同溶剂中的荧光寿命,其中2a在DMSO中寿命最长,为3.18ns.这些光谱性质为研究其双光子吸收、双光子荧光和非线性光学性质奠定了理论和实验基础.     

A study of the Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one derivatives

Summary The Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 a) gave 7-hydroxy-8-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (3 a) and 2,3-dihydro-2,6-diphenyl-3-methyl-(7H)furo[2,3-h]-1-benzopyran-7-one (7 a). 2-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 b) afforded4 b and7 b. 8-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (12) gave only the alkali soluble product 7-hydroxy-8-methyl-6-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (13).3 a,4 b, and13 were further cyclized in acidic medium to9 a,10 b, and14 followed by dehydrogenation.This paper is dedicated to Dr. F. M. Dean, Department of Organic Chemistry, Robert Robinson Laboratories, University of Liverpool, Liverpool, U. K., on his retirement     

Gemeinsame Einwirkung von elementarem Schwefel und Äthylenimin auf Ketone, 2. Mitt.

Zusammenfassung Bei der gemeinsamen Einwirkung von Schwefel und Äthylenimin auf 4-Heptanon, Cyclopentanon, Cyclohexanon und Cyclooctanon bilden sich in glatter Reaktion 5,6-Dihydro-4H-1,4-thiazine (3–6). Als Nebenprodukte von3, 4 und5 fallen die dem jeweiligen Keton zugrunde liegenden 2,2-dialkylierten Thiazolidine (7–9) an. Bei Einsatz von Phenylisopropylketon in diese Reaktion wird dagegen das 2-Isopropyl-2-phenylthiazolidin (12) zum Hauptprodukt, während das entsprechende 5,6-Dihydro-2H-1,4-thiazin (11) nur in untergeordnetem Maße entsteht.Die Reaktionsmechanismen sowohl der 5,6-Dihydro-1,4-thiazin-als auch der Thiazolidin-Bildung werden diskutiert.Die Umsetzung der 5,6-Dihydro-1,4-thiazine (1, 3–5, 11) mit überschüss. Ameisensäure führt zu N-Formylthiomorpholinen (13–17), die sich mit verd. HCl glatt zu den entsprechenden Thiomorpholinen (18–22) verseifen lassen.

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Concomitant action of elementary sulfur and gaseous ammonia upon ketones, LXXI. Concomitant action of elementary sulfur and ethylenimine upon ketones, II

The interaction of sulfur and ethylenimine with 4-heptanone, cyclopentanone, cyclohexanone, and cyclooctanone leads to 5.6-dihydro-4H-1.4-thiazines (3–6) in good yields. As byproducts of3, 4 and5 2.2-dialkylated thiazolidines (7–9, resp.) are isolated. When this reaction is carried out with phenyl isopropyl ketone, however, the main product is 2-isopropyl-2-phenylthiazolidine (12), the corresponding 5.6-dihydro-2H-1.4-thiazine (11) is but formed in a small quantity.The mechanisms of the formation of 5.6-dihydro-1.4-thiazines, as well as the formation of the thiazolidines are discussed.Reaction of 5.6-dihydro-1.4-thiazines (1, 3–5, 11) with excess formic acid leads to N-formylthiomorpholines (13–17) which can be easily saponified with dil. HCl to the corresponding thiomorpholines (18–22).

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Herrn Prof. Dr.O. Hromatka mit herzlichen Grüßen zum 65. Geburtstag gewidmet

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70. Mitt.:F. Asinger, H. Offermanns, D. Neuray undF. Abo Dagga, Mh. Chem.101, 500 (1970)

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Teil der DissertationK. H. Lim, Techn. Hochschule Aachen, 1969.

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Teil der DissertationD. Neuray, Techn. Hochschule Aachen, 1969

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1. Mitt.:F. Asinger, H. Offermanns, W. Pürschel, K. H. Lim undD. Neuray, Mh. Chem.99, 2090 (1968).     

Mechanistic and Synthetic Studies on the Formation of 1,2,4-Trioxanes Related to Arteannuin. Photooxygenation of a bicyclic dihydropyran

The photooxygenation of (4R,4aS,7R)-4,4a,5,6,7,8-hexahydro-4,7-dimethyl-3H-2-benzopyran ( 16 ) was performed in (i) MeOH, (ii) acetaldehyde, and (iii) acetone at ?78°. The products obtained respectively were (i) (2R)-2-[(1S,4R)-4-methyl-2-oxocyclohexyl]propyl formate ( 17 ; 72% yield), (ii) 17 (54.5%), (1R,4R,4aS,7R)-3,4,4a,5,6,7-hexahydro-4,7-dimethyl-1H-2-benzopyran-2-yl hydroperoxide ( 19 ; 16.7%), a 12:1 ratio of (3R,4aR,7R,7aS,10R,11aR)-7,7a,8,9,10,11-hexahydro-3,7,10-trimethyl-6H-[2]benzopyrano[1,8a-e]-1,2,4-trioxane ( 20 ) and its C(3)-epimer 21 (17%), together with evidence for the 1,2-dioxetane ( 22 ) originating from the addition of dioxygen to the re-re face of the double bond of 16 , and iii) unidentified products and traces of 22 . Addition of trimethylsilyl trifluoromethanesulfonate (Me₃SiOTf) to the acetone solution of 16 after photooxygenation afforded (4aR,7R,7aS,10R,11aR)-7,7a,8,9,10,11-hexahydro-3,3,7,10-tetramethyl-6H-[2]benzopyrano[1,8a-e]-1,2,4,-trioxane ( 23 , 40%). The photooxygenation of 16 in CH₂Cl₂ at ?78° followed by addition of acetone and Me₃SiOTf afforded 17 (11%), 23 (59%), and (4aR,7R,7aS,10R,11aR)-7,7a,8,9,10,11-hexahydro-3,3,7,10-tetramethyl-6H-[2]benzopyrano[8a,1-e]-1,2,4-trioxane ( 24 ; 5%. Repetition of the last experiment, but replacing acetone by cyclopentanone, gave 17 (16%), (4′aR,7′R,7′aS,10′R,11′aR)-7′,7′a,8′,9′,10′,11′-hexahydro-7′,10′-dimethylspiro[cyclopentane-1,3′-6′H-[2]benzopyrano[1,8a-e]-1,2,4-trixane] ( 25 ; 61%), and (4′aR,7′R,7′aS,10′R,11′aR)-7′,7′a,8′,9′,10′,11′-hexahydro-7′,10′-dimethylspiro[cyclopentane-1,3′-6′H-[2]benzopyrano[8a,1-e]-1,2,4-trixane] ( 26 , 4%). The X-ray analysis of 23 was performed, which together with the NMR data, established the structure of the trioxanes 20, 21, 24, 25 , and 26 . Mechanistic and synthesis aspects of these reactions were discussed in relation to the construction of the 1,2,4-trioxane ring in arteannuin and similar molecules.     

The easy hydrolysis of hexacyanocyclopropane, ethyl 1,2,2,3,3-pentacyanocyclopropane-1-carboxylate, 1,2,2,3,3-pentacyanocyclopropane-1-carboxamide, andN,N-dimethyl-1,2,2,3,3-pentacyanocyclopropane-1-carboxamide tor-1,c-2,c-3-tricyanocyclopropane-t-carboxamide

Hydrolysis of hexacyanocyclopropane (1a), ethyl 1,2,2,3,3-pentacyanocyclopropane-1-carboxylate (1b), 1,2,2,3,3-pentacyanocylopropane-1-carboxamide (1c), andN,N-dimethyl-1,2,2,3,3-pentacyanocylopropane-1-carboxamide (1d) in 95% acetic acid yieldsr-1,c-2,c-3-tricyanocyclopropane-t-1-carboxamide (3). The structure of3 was proved by X-ray diffraction analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 454–456, March, 1998.     

Darstellung von 4 t -Brom-1 c , 10 c -decalol und 4 t -Brom-1 c -methoxy-9 c , 10 c -decalin

The reaction of (Z, E)-1,5-cyclodecadiene with N-bromosuccinimide in the presence of water or methanol leads to transannular cyclizations producing 4 ^t -bromo-1 ^c , 9 ^c , 10 ^c -decalol, and 4 ^t -bromo-1 ^c -methoxy-9 ^c , 10 ^c -decalin, resp., in high yields. The stereochemistry of the products has been established by chemical methods, and NMR-techniques.

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Mit 1 Abbildung

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2. Mitt.:J. Graefe, G. Haufe undM. Mühlstädt, Z. Chem.16 180 (1976).

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Aus der Dissertation zur PromotionA. G. Haufe, Universität Leipzig, 1975.     

Stereoselective epoxidation of 2-arylidene-1-indanones and 2-arylidene-1-benzosuberones

Summary Oxidation of the (E) and (Z) isomers of 2-arylidene-1-indanones (1) and 2-arylidene-1-benzosuberones (4) by alkaline hydrogen peroxide (methodi) afforded the spiroepoxidestrans-2a–g andtrans-5a–g from both isomers as sole products in high yields. On the other hand, dimethyldioxirane epoxidation(methodii) of the (E) isomers1a–g and4a–g gave the correspondingtrans spiroepoxides in good yields, whereas the (Z) isomers1a,c,e and4a,c,e led to thecis spiroepoxides in moderate yields. Dimethyldioxirane oxidation (methodii) of (Z)-1c and (Z)-4c,e gave diones3c and6c,e as by-products as well. Epoxidation of (Z)-1a,c,e and (Z)-4a,c,e bym-chloroperoxybenzoic acid (methodiii) resulted inca. 6:1 mixtures ofcis-2a,c,e andtrans-2a,c,e orcis-5a,c,e andtrans-5a,c,e spiroepoxides.Dedicated to Prof.W. Fleischhacker on the occasion of his 65^th birthday