Synthesis of Novel 2-(4-Oxo-3,4- Dihydroquinazolin-2-Ylsulfinylmethyl)-3H-Quinazolin-4-One

Abstract

Condensation of 2-mercapto-3H-quinazolin-4-one (1) with chloroacetic acid gave 4-oxo-3,4-dihydroquinazoline-2-yl-sulfanyl)-acetic acid (2) that with anthranilamide (3) gave 2-(4-oxo-3,4-dihydroquinazolin-2-ylsulfanylmethyl)-3H-quinazolin-4-one (4). Oxidation of 4 with sodium hypochlorite in alkaline medium gave the novel product, 2-(4-oxo-3,4- dihydroquinazolin-2-ylsulfinyl methyl)-3H -quinazolin-4-one) (5). The entire sequences of reactions in this work have been carried out using eco-friendly solvents and green conditions.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Ionic Liquid Promoted Efficient Three-Component Synthesis of 2-Thioxo-2H-Thiopyrans

Abstract

An efficient one-pot three-component method for the synthesis of a variety of 2-thioxo-2H-thiopyrans has been described. Fairly good yields are obtained by cyclization reactions of arylidenemalononitriles, derived in situ from ketones and malononitrile, with carbon disulfide in the presence of a base in the ionic liquid 1-butyl-3-methylimidazolium bromide as reaction medium.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Selected Data.]

GRAPHICAL ABSTRACT      

Über 3,6-Dihydro-2H-1,2-thiaphosphorin-2-sulfide

Zusammenfassung Dithiophosphonsäureanhydride (1) addieren sich an 1,3-Diene zu 3,6-Dihydro-2H-1,2-thiaphosphorin-sulfiden (2). Bei der Umsetzung mit unsymmetrischen 1,3-Dienen entspricht die Additionsrichtung einem Ablauf über das stabilste Diradikal. Metallierung der 3,6-Dihydro-2H-1,2-thiaphosphorin-sulfide führte unter Ringöffnung zu Salzen der Diendithiophosphinsäure (3), die mit Alkylierungsmitteln in die entsprechenden Dithiophosphinsäureester (4) übergeführt werden können.

---

3.6-Dihydro-2H-1.2-thiaphosphorin-2-sulfides

Addition of dithiophosphonic acid anhydrides (1) to 1.3-dienes affords 3.6-dihydro-2H-1.2-thiaphosphorin-2-sulfides (2). The course of this addition reaction in the case of unsymmetrical 1.3-dienes appears to be consistent with a mechanism involving the most stable biradical intermediate. Metallation of the resulting 3.6-dihydro-2H-1.2-thiaphosphorin-2-sulfides leads to ring opening forming salts of the diene-dithiophosphinic acid (3) which are converted via alkylation to the esters of the corresponding dithiophosphinic acid (4).

---

---

Mit 2 Abbildungen

---

Herrn Professor Dr.Erich Ziegler mit herzlichen Grüßen zum 60. Geburtstag gewidmet.

---

Korrespondenz an Ulrich Schmidt.     

4-Methylisocamphenilansäure und 4-(3,3,4-Trimethyl-2-exo-norbornyl)-3-buten-2-on

The synthesis of 4-methylisocamphenilanic acid (7) and of the unsaturated ketone 4-(3,3,4-trimethyl-2-exo-norbornyl)-3-buten-2-one (2), an analogue of -irone (1), are described. The preparation of2 has been accomplished by: catalyzedDiels—Alder reaction of methylcyclopentadiene and mesityl oxide, hydrogenation and isomerization of the resulting ketone mixture to theexo-ketone6, oxidation of6 to the acid7, reduction of7 to the corresponding aldehyde8 and aldol reaction of8 with acetone. The structure of the key intermediate6 was established by mass, 100 MHz¹H-NMR and¹³C-NMR spectra. The odour of2 is discussed briefly.

---

---

Teil der Diplomarbeit vonI. Schmidmayer.

---

9. Mitt.,G. Buchbauer undM. Wiltschko. J. Soc. Cosmet. Chem., im Druck.

---

8. Mitt.,G. Buchbauer undE. Klissenbauer, Mh. Chem.109, 499 (1978).     

Microwave-Assisted Preparation of 2-Substituted Benzothiazoles

Abstract

2-Substituted benzothiazoles ( 3a–h ) were prepared from the condensation reaction of 2-aminothiophenol 1 with aldehydes 2 in the presence of P-Ts-OH and graphite on the surface of solid mineral supports without using any oxidizing agent under microwave irradiation.     

Acylderivate von 2-Amino-p-pyrrolinen

Zusammenfassung Die Acylierung von 2-Amino-3.3-diphenyl-5-methyl-1-pyrrolin (1) und 2-Amino-3.3-diphenyl-1-pyrrolin (2) erfolgt in den hier untersuchten Fällen am N-2-(exo)-Stickstoff. Die Umsetzung der cyclischen Amidine1 und2 mit BrCN gibt jedoch neben den N-2-(exo)-auch die N-1-(endo)-Cyanamidine. Diese werden in die entsprechenden Carbamoyl- und Thiocarbamoylamidine umgewandelt.

---

Acylderivatives of 2-amino-1-pyrrolines

Acylations of 2-amino-3.3-diphenyl-5-methyl-1-pyrroline (1) and 2-amino-3.3-diphenyl-1-pyrroline (2) occur at the N-2-(exo)-nitrogen. However, reaction of1 and2 with BrCN yields not only the N-2-(exo)-cyanoamidines but also the N-1-(endo)-isomers. Either is converted into the corresponding carbamoyl and thiocarbamoyl amidines.

---

---

3. Mitt.:W. Klötzer undB. Schmidt, Mh. Chem.102, 180 (1971).

---

Teile dieser Arbeit sind Gegenstand von Patentanmeldungen.     

Thalidomid-Analoga, 2. Mitt.

Zusammenfassung Unter Hinweis auf die Notwendigkeit der Suche nach neuen Sedativa werden die Vorzüge und unerwünschten Nebenwirkungen des bekannten Schlafmittels Thalidomid (1) kurz dargelegt und einige Ergebnisse früherer Untersuchungen über die Struktur—Wirkungs-Beziehungen bei verschiedenen,1 strukturell nahestehenden Verbindungen diskutiert. In Fortführung dieser Arbeiten wurden weitere Thalidomid-Analoga mit Brücken-Ringsystemen für die pharmakologische Untersuchung systhetisiert.

---

Pointing out the necessity of the search for new sedative drugs the advantages and unfavourable side effects of the wellknown hypnotic thalidomide (1) are set forth briefly and some results from previous investigations on the structure-activity relationships in several compounds structurally related to1 are discussed. In continuation of this work further thalidomide analogues with bridged ring systems have been synthesized for the pharmacological evaluation.

---

---

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

---

1. Mitt.:H. Koch undJ. Kotlan, Mh. Chem.97, 1648 (1966).     

The Synthesis of the 2- and 2′-Monodeoxygenated Analogues of β-Maltosyl-(1→4)-Trehalose 1

Abstract

Two derivatives of β-maltosyl-(1→4)-trehalose monodeoxygenated at C-2 or C-2′ have been synthesized in [2+2] block syntheses. N-Iodosuccinimide-mediated coupling of tetra-O-benzyl-glucose to tri-O-acetyl-D-glucal followed by O-acetylation furnished 3,4,6-tri-O-acetyl-2-deoxy-2-iodo-α-D-mannopyranosyl 2,3,4,6-tetra-O-benzyl-α-D-glucopyranoside (7), which was used as a starting material for both tetrasaccharides. For the preparation of the 2′-monodeoxygenated saccharide the deoxyiodo pyranose moiety of 7 was further elaborated by de-O-acetylation, O-benzylidenation, O-benzylation, and selective reductive opening of the benzylidene acetal to give glycosyl acceptor 10. Glycosylation with hepta-O-acetylmaltosyl bromide and deprotection including removal of the iodo substituent afforded the 2′-deoxymaltosyl-(1→4)-trehalose 14. On the other hand, the non-iodinated pyranose moiety of 7 was transformed to a glycosyl acceptor. The removal of the benzyl groups of 7 necessitated also the reduction of the iodo group at this early stage. The resulting 3,4,6-tri-O-acetyl-2-deoxy-α-D-arabino-hexopyranosyl α-D-glucopyranoside was subjected to a similar reaction sequence as above to finally result in the 2-deoxymaltosyl-(1→4)-trehalose 22.

     

3-(5-Substituted 2-Methoxyphenyl)-4-Nitro-2-Phenyl-5-Thiophene-2-yl-Isoxazolidines - Synthesis and Conformational Studies

Abstract

The synthesis of a new set of 2,3,4,5-substituted isoxazolidines having a sulfur containing heterocyclic moiety has been described. The structural features of the compounds have been analyzed by ¹H and ¹³C NMR spectroscopy as well as by single crystal X-ray studies.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: .cif file.]     

Zur Reaktion von 4-Hydroxy-2-chinolon mit reaktiven Malonsäurederivaten

The reaction of 4-hydroxy-2-quinolone (1) with malonyl chlorides2 in the presence of N,N-dimethylaniline yields the linear pyrono-quinolones4. These are thermically rearranged to angular derivatives5, which can also be obtained by direct condensation of1 with trichlorophenyl malonates3. The reaction of 4-benzyloxy-2-quinolone with2a gives the mesoionic 1,3-oxazine derivative8.

---

---

4. Mitt.:G. Schindler, D. Furtunopulos undTh. Kappe, Z. Naturforsch.31 b, 500 (1976).

---

Aus der DissertationG. Nöhammer, Graz 1971.     

Über die Umsetzung von 2-Methyl-2,5-diphenyl-imidazolin-4-thion und 2-Methyl-2,5-diphenyl-4-chlor-2H-imidazol mit aliphatischen und aromatischen Aminen,Alkoholen und Phenolen

Zusammenfassung Aliphatische Amine bzw. Alkohole reagiren (in Gegenwart von PbO) mit 2-Methyl-2,5-diphenyl-imidazolin-4-thion (1) glatt zu 4-Alkylamino-2H-imidazolen (2 a-f, 7) bzw. 4-Alkoxy-2H-imidazolen (9 a-g). Die Darstellung von 4-Arylamino-2H-imidazolen (4 a-j) bzw. 4-Aroxy-2H-imidazolen (10 a-t) gelingt in guten Ausbeuten durch Umsetzung von 2-Methyl-2,5-diphenyl-4-chlor-2H-imidazol (3) mit aromatischen Aminen in siedenden Lösungsmitteln (Petroläther, Aceton) bzw. mit Phenolen in siedendem Aceton in Gegenwart von HCl-Acceptoren (K₂CO₃, Dabco). Die Umsetzung von3 mit Anthranilsäure liefert in 83proz. Ausbeute 1-Methyl-1,3-diphenyl-1H, 9H-imidazo[5,1-b]chinazolin-9-on (6). Aus3 und Thiophenol erhält man glatt 2-Methyl-2,5-diphenyl-4-phenylthio-2H-imidazol (11).

---

On the reaction of 2-Methyl-2,5-diphenyl-imidazoline-4-thione and 2-Methyl-2,5-diphenyl-4-chloro-2H-imidazole with aliphatic and aromatic amines, alcohols and phenols (joint action of elemental sulfur and gaseous ammonia upon ketones, LXXVI

Aliphatic amines and alcohols (in the presence of PbO) easily react with 2-methyl-2.5-diphenyl-imidazoline-4-thione (1) to 4-alkylamino-2H-imidazoles (2 a-f, 7) and 4-alkoxy-2H-imidazoles (9 a-g), resp. 4-arylamino-2H-imidazoles (4 a-j) are prepared in good yields by the reaction of 2-methyl-2.5-diphenyl-4-chloro-2H-imidazole (3) with aromatic amines under reflux in light naphtha or acetone; in the same manner 4-aroxy-2H-imidazoles (10 a-t) are obtained from3 and phenols in boiling acetone in the presence of HCl-acceptors (K₂CO₃, Dabco). Reaction of3 with anthranilic acid leads to1-methyl-1.3-diphenyl-1H.9H-imidazo[5.1-b]chinazoline-9-one (6) in 83% yield. By reaction of thiophenol with3 2-methyl-2.5-diphenyl-4-phenylthio-2H-imidazole (11) is easily obtained.

---

---

Herrn Prof. Dipl.-Ing., Dr. techn., Dr. e. h.Otto Kratky zum 70. Geburtstag herzlichst gewidmet.

---

Teil der DiplomarbeitJ. Gräber, Techn. Hochschule Aachen, 1970.

---

Teil der DiplomarbeitU. Lames, Techn. Hochschule Aachen, 1971.     

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.

---

---

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

---

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

---

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

Syntheses of 2,6-Anhydro-3-Deoxy-D-Glycero-D-Galacto-Non-2-Enonic Acid (Kdn2En) and Its Hydrogenation Products 1

Abstract

Methyl 4,5,7,8,9-penta-O-acetyl-2,6-anhydro-3-deoxy-D-glycero-D-galacto-enonate (5) was synthesized from KDN methyl ester 2 with a catalytic amount of concentrated sulfuric acid in acetic anhydride, or from 2-chloro-KDN methyl ester 4 with DBU in good yield. Hydrogenation of 4 and 5 with 10% Pd-C gave 2-deoxy-2-H_ax-KDN 8 and 2-deoxy-2-H_eq-KDN derivative 11 in high yield, respectively. The structures of these compounds were elucidated from the MS, elemental analysis, ¹H NMR and ¹³C NMR data.

     

Synthesis of Protein Conjugates of 2-Carboxy-L-Arabinitol 5-Phosphate and 2-Carboxy-L-Ribitol 5-Phosphate

Abstract

The synthesis of 5-O-[5-(pentanoic acid)]-phosphono-L-erythro-pent-2-ulose 2 was successfully achieved by coupling benzyl 5-hydroxypentanoate 9b and 1-O-benzyl-L-erythro-pent-2-ulose ethane- 1,2-diyl dithioacetal 13 with the enediol pyrophosphate 18. Compound 2 was coupled to carrier proteins, porcine thyroglobuline and bovine serum albumin and the conjugates were treated with KCN to give conjugates of the hapten 1, designed to raise catalytic antibodies.     

Synthesis and Antimicrobial Activity of Some New 5-(3-Chloro-1-Benzothiophen-2-YL)-1,3,4-Oxadiazole-2-Thiol and Their Derivatives

Abstract

3-Chloro-1-benzothiophene-2-carbonylchloride 1 was made to reacts with hydrazine hydrate afforded 3-chloro-1-benothiophene-2-carbohydrazide 2 in good yield. 5-(3-chloro-1-benzothiophen-2-yl)-1,3,4-oxadiazole-2-thiol 4 was synthesized from 3-chloro-1-benzothiophene-2-carbohydrazide 2. Mannich bases, alkyl halide, and acid chlorides derivatives were then prepared. Compound 4 on condensation with chloroacetone in the presence of NaOH as base and ethanol as solvent gave 1-{[5-(3-chloro-1-benzo[b]thiophen-2-yl)-1,3,4-oxadiazol-2-yl]sulfanyl}propan-2-on 6. Condensation of compound 6 with various aromatic aldehydes afforded a series of chalcones 7a–h. The structures of all the synthesized compounds were confirmed by spectral data and have been screened for antibacterial activity.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

GRAPHICAL ABSTRACT      

trans-Tetradec-2-enoic Acid in Impatiens glandulifera

Purification of the hydrophobic extracts of the flowers and seed pods of Impatiens glandulifera(Himilayan balsam) yielded 2-methoxy-[1,4]-naphthoquinone 1, 1-hydroxyeicosan-3-one 16, and an unusual unsaturated fatty acid, trans-tetradec-2-enoic acid 6. Mass spectrometry and nuclear magnetic resonance spectroscopy indicated that the latter compound (6) was isolated as a mixture with linolenic acid 8 and saturated acids 7, 9, and 10 (chain lengths C-16, 18, and 20). Its structure was subsequently proven by independent chemical synthesis.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

An Efficient Route for the Synthesis of 3-(4-Bromophenyl)-2-Phenyl-3,4-Dihydro-2H-Benzo[E][,32,]Oxazaphosphinine,its P-Chalcogenides and Metal Complexes

Abstract

2-[(4-bromophenylamino)-methyl]-phenol (1) gave substantially pure 3-(4-bromophenyl)-2-phenyl-3,4-dihydro-2H-benzo[e][1,3,2]- oxazaphosphinine (2) on cyclization with phenyldichlorophosphine in toluene at 0 °C. Reaction of 2 with H₂O₂ in dichloromethane gave selectively 3. P-chalcogenides (4 and 5) were prepared by reacting 2 with elemental S and Se powder in toluene, whereas the tungsten pentacarbonyl complex 6 was prepared by reacting 2 with [W(CO)₅(CH₃CN)] in tetrahydrofuran at 25 °C.

Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures.     

Chemoselective Aza-Michael addition of indoles with 2-arylidenemalononitriles

Abstract

The selective aza-Michael addition at N1-position of indoles to 2-arylidenemalononitriles in the presence of potassium hydroxide is described. The salient features of this protocol are no transition-metal catalysts, mild conditions, high chemoselectivity, high atom economy, high yield and simple work-up procedures.     

Synthesis of 3-Fluoro-2-(Diethoxyphosphoryl) Imidazo[1,2-A]Pyrimidine

Abstract

The first representative of 3-fluoro-2-(dialkoxyphosphoryl)imidazo[1,2-a]pyrimidi nes has been synthesized by the reaction of N-(pyrimidin-2-yl)-2,2,2-trifluoroacetimidoyl chloride with triethyl phosphite.

[Supplemental materials are available for this article. Go to the publisher's online edition ofPhosphorus, Sulfur, and Silicon and the Related Elements to view the following free supplemental file: Figures]     

Das Schwingungsspektrum von Sr2V2O7 und die Schwingungseigenschaften des Divanadat-Ions

The infrared and laser-Raman spectra of Sr₂V₂O₇ are reported and discussed by means of a Site Symmetry analysis. The principal force constants as well as the mean amplitudes of vibration for the V₂O₇ ^4– ion have been calculated using a simplified molecular model. Some aspects of the vibrational behaviour of the V–O–V bridge in this ion are also discussed.

---

---

Mit 1 Abbildungen

---

22. Mitt. der Reihe Orthovanadate und verwandte Verbindungen. 21. Mitt.:M. E. Escobar undE. J. Baran, Z. Naturforsch.B32, 349 (1977); 20. Mitt.:E. J. Baran undI. L. Botto, Mh. Chem.,108, 311 (1977); 19. Mitt.:E. J. Baran, Z. anorg. allgem. Chem.427, 131 (1976).