ORGANISCHE PHOSPHORVERBINDUNGEN 791 HERSTELLUNG UND EIGENSCHAFTEN VON α-AMINO-ω-CARBOXYALKYLPHOSPHON-UND-PHOSPHINSÄUREN

Abstract

The synthesis, chemical and spectral properties of α-amino-ω-carboxyalkylphosphonic acids, (HO)₂P(O)CH(NH₂)(CH₂) _x CO₂H, x = 2 to 6, and of α-amino-ω-carboxyalkyl-methylphosphinic acids CH₃(HO)P(O)CH(NH₂)(CH₂) _x CO₂H, x = 2 to 6 are described and the fungicidal activity of some of these derivatives is reported.     

Synthesis and Characterization of Monodisperse α,ω-Divinylpolydimethylsiloxane and ω-Vinylpolydimethylsiloxane

Abstract

ω-Vinylpolydimethylsiloxanes (ω-PDMS) and α,ω-divynilpolydimethylsiloxanes (α,ω-PDMS) have been synthesized by anionic polymerization of hexamethylcyclotrisiloxane (D3). The reactions were carried out in n-hexane and tetrahydrofuran (THF), respectively. The initiator was n-butyl-lithium (n-BuLi); tetrahydrofuran was used as an electron donor compound to promote the polymerization of D3. The synthesized polymers have been characterized by infrared (FTIR), proton nuclear magnetic resonance spectroscopy (NMR), light scattering (LALLS), and gel permeation chromatography (GPC). Molecular weights ranging from 20,000 to 100,000 were obtained with relatively narrow molecular weight distributions; Mw/Mn < 1.25.     

Synthesis and Mesomorphic Properties of Some ω′-Alkoxy-ω-benzoxypolyfluorotolane Compounds

Four homologue series of 4-cyano-nd 4-nitro-substituted benzoate-tolanes were synthesized and char-acterized by IR,NMR,MS spectra and elemental analysis.Their phase transition behaviors were investigated byDSC and polarized optical microscope.The effects on the mesomorphic properties of different positions of the per-fluorophenyl in the molecular core unit,the terminal cyano-substituted systems and the terminal nitro-substitutedones were discussed.     

N α,N ω-DIPHOSPHONO-, DIPHOSPHINO-METHYL-L-α,ω-DIAMINOCARBOXYLIC ACIDS

Abstract

Treatment of N-hydroxymethylated lactames 1,4-diamino-L-butanoic acid–1, L-ornithine–2, and L-lysine–3 is carried out with phosphorus trichloride to give the phosphonic acids 4, 5 and 6, and with methyldichlorophosphine to give the methylphosphinic acids 7, 8 and 9, which after alkaline hydrolysis liberate the carboxylic acids 10–15. Analogously, from the L-lysine derivative–16 and the aminomethylphosphonic acid derivative 18, the acids 15 and 19 are obtained after hydrolysis. The herbicidal activity of the lysine derivative 15 is established.     

ACTION DES CYANOARYLIDENES ACTIVES SUR LES β -CETO- δ -CARBETHOXYPHOSPHONATES ET PHOSPHINEOXYDES: SYNTHESE DE 2-AMINO-6-(PHOSPHONOMETHYL)-4H-PYRANES

The reaction of β-keto-δ-carbethoxyphosphonates and phosphineoxides 1 with active cyanoarylidenes 2 in basic conditions provides a convenient access to the new 2-amino-6-(phosphonomethyl)-4H-pyranes 3. The reaction is found to be highly regioselective. The structure of all obtained products is confirmed by NMR ( ¹ H, ³¹ P, ¹³ C), IR spectroscopy, and in some cases by mass spectrometry.     

Synthesis and properties of an ω,ω′-appended eighteen carbon chains hypericin derivative

Summary An ,-appended eighteen carbon chains hypercin derivative (2) was synthesized starting from emodin. The overall yield of the seven step synthesis was 12%. The¹H and¹³C NMR, absorption, and emission spectroscopic properties were measured;2 can be dissolved even in apolar solvents and polyethylene.

---

Synthese und Eigenschaften eines mit C₁₈-Ketten ,-substituierten Hypericinderivats

Zusammenfassung Ein in den Positionen , mit zwei C₁₈-Ketten substituiertes Derivat des Hypericins (2) wurde ausgehend von Emodin synthetisiert. Die Gesamtausbeute der siebenstufigen Synthese betrug 12%. Die¹H- und¹³C-NMR, absorptions- und emissionsspektroskopischen Eigenschaften wurden gemessen;2 kann sogar in apolaren Lösungsmitteln und Polyethylen gelöst werden.

     

SYNTIIESIS OF 2-AMINO-5-THIO-THIADIAZOLINE β-D-RIBOFURANOSIDES

ＳＹＮＴＩＩＥＳＩＳＯＦ２－ＡＭＩＮＯ－５－ＴＨＩＯ－ＴＨＩＡＤＩＡＺＯＬＩＮＥβ－Ｄ－ＲＩＢＯＦＵＲＡＮＯＳＩＤＥＳ￥ＹｕｎＹａｎＺＨＡＮＧ；ＹｕｎＤＩＮＧ；ＹｉＢｉｎｇＺＨＡＮＧ；ＹａｏＱｕａｎＣＨＥＮ￣＊（ＬａｂｏｒａｔｏｒｙｏｆＢｉｏ－ｏｒｇ...     

ω-Hydroxy and ω-Amino-carboxylic Acid Derivatives for the Preparation of Ester and Amide Crown Ethers

An oxymercuration reaction between methyl acrylate and the monobenzyl ethers (3) of mono-, di-, and triethylene glycol, followed by reduction with sodium borohydride, gives the expected polyether esters (4). These are converted by standard procedures into various derivatives of the ω-hydroxy and ω-amino acids (1) and (2) respectively.     

ω,ω′-Diphospholylalkanes

Abstract

The reaction of compounds (1) with lithium or sodium can lead to different results depending on the length of the exocyclic chain : when n=1,2 or 4, we observe cleavage of both exocyclic P-C bonds, giving pure phospholyllithium or sodium.     

SYNTHESE DE SPIROPHOSPHORANES CONTENANT UNE LIAISON P–C

Abstract

Les réactions des oxa et oxazaspirophosphoranes à liaison P–H (1)–(4) avec les doubles liaisons activées C?C conduisent aux spirophosphoranes à liaison P_VC (9)-(20). Nous considérons les composés (9)-(20) comme des précurseurs de phosphonates. Le mécanisme de ces réactions a été examiné.

The reaction of oxa and oxazaspirophosphoranes containing P–H bond (1)-(4) with C?C activated double bond lead to spirophosphoranes containing P_V-C bond (9)-(20). We consider compounds (9)-(20) as phosphonates precursors. The mechanism of these reactions has been examined.     

Synthesis and Biological Activities of ω-Heterocyclyl-ω-(1H-1,2,4-triazol-1-yl) Acetophenones

Inrecentyears,agreatvarietyofheterocycliccompoundsbearing1H-l,2,4-triazoleringhavebeensynthesizedduetotheirbroadspectrumbiologicalactivitiesincludingantiinflammatory.insecticidal,antiviralandantiturnoractivities'-',someofwhichhavebeendevelopedintocommerciallyantifungalagentssuchastriadimefon.triadimenolanddiniconazele.Wepreviouslysynthesizedmanykindsofheterocycliccompoundssuchasl,3,4-oxadiazole,l,2,4-triazole,l,3.4-thiadiazoleandl,2.3-triazolederivativeswhichexhibitedantibacterial,antitubercul…     

Type I and type II photochemical reaction of ω-isobutyryl-ω-methyl-2,3-benzocycloalk-2-en-1-ones

ω-Isobutyryl-ω-methyl-2,3-benzocycloalk-2-en-l-ones. (6a-c) undergo both type I and type II photoreactions. The type I/type II product ratio depends on the ring size; the six-membered ketone 6a is subject to type II reaction and the eight-membered ketone 6c is subject to type I reaction predominantly. The cyclization/elimination ratio of the type II reaction of 6 also depends on the ring size; the ratio decreases with increasing ring size.     

The synthesis of ω-thienylalkane acids from ω-chloroalkane acids

Summary We have worked out a preparative method for the synthesis of -thienylalkane acids by acylation of thiophene with -chloroalkane acid chlorides followed by conversion of the resulting -chloroalkyl(2-thienyl)ketones into the corresponding acids by reaction with sodium malonic ester or potassium cyanide, and reduction of the resulting products with their simultaneous hydrolysis.Here and later we mean -(2-thienyl)alkne acids.We take this opportunity to thank R. Kh. Freidlina, A. A. Beér, and M. A. Besprozvannii for giving us enough -chloroalkane acids.     

[1,3]-CARBANIONISCHE UMLAGERUNGEN—SYNTHESE VON 1,3-BENZOXASILOLENEN

Abstract

2-Bromoaryloxy-chloromethyldiorganosilanes react with sodium in a one-pot-reaction via metallation, [1,3]-carbanionic rearrangement and cyclization to give diorgano-1,3-benzoxasilolenes. The title compounds have been characterized by n.m.r. spectroscopic data and an alternative independent synthesis.     

1-AMINO-1-ARYL- AND 1-AMINO-1-HETEROARYL-METHANEPHOSPHONIC ACIDS AND THEIR N-BENZHYDRYL–PROTECTED DIETHYL ESTERS: PREPARATION AND CHARACTERIZATION

n-Benzhydryl-protected diethyl[3.3pc] esters of 1-amino-1-aryl- (phenyl, cumyl, p-dimethylaminophenyl, piperonyl, 1′-naphthyl, 9′-anthryl, 1′-pyrenyl) and 1-amino-1-heteroaryl- (furyl, 2′-thienyl, 3′-thienyl, 2′-pyrrolyl)-methanephosphonic acids, prepared by the addition of diethyl phosphite to the corresponding benzhydryl imines, have been isolated, purified, and characterized. The presence of chiral α -carbon and prochiral phosphorus in these esters gives rise to complicated features in their NMR spectra, which are discussed. Hydrolysis of the crude 1-aryl compounds in situ gave modest yields of the corresponding aminophosphonic acids (except for 1′-pyrenyl). Of the 1-heteroaryl derivatives, only the 2′-thienyl compound gave the expected aminophosphonic acid; in other cases, alternative[-18pc] modes of decomposition may occur under hydrolytic conditions. NMR and mass spectral data are given for all products.     

FACILE SYNTHESIS OF 4-AMINO-4-DEOXY-4''''-DEMETHYLEPIPODOPHYLLOTOXIN

4-Amino-4-deoxy-4′-demethylepipodophyllotoxin has beendirectly synthesized from 4′-demethylepipodophyllotoxin and HN_3in the presence of BF3·Et_2O,followed by hydrogenation withpalladium on charcoal as catalyst.