Synthesis and Herbicidal Activity of Novel Pyrimidinyl Derivatives Containing an α-Amino Phosphonate Moiety

In order to find novel pyrimidinyl carboxylic acid analogs with high activity and low toxicity, a series of novel pyrimidinyl derivatives containing an α-amino phosphonate moiety 5 was synthesized by the condensation of 4-(4,6-dimethoxypyrimidin-2-yloxy)phenoxyacetic 3a or propionic acids 3b with dialkyl α-amino substitutedbenzyl phosphonates 4. Their structures were characterized by spectroscopic data (IR, ¹H NMR, ³¹P NMR, MS) and elemental analyses. The results of preliminary herbicidal activities (in vitro) showed that most of these compounds exhibited higher herbicidal activities against dicotyledonous weeds (Brassica campestris L) than monocotyledonous weeds (Echinochloa crus-galli). Further bioassays (in vivo) indicated that some of compounds 5 possessed selective herbicidal activity against amaranth pigweed (A. retroflexus) in post-emergence treatment.

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.     

Synthesis and Herbicidal Activity of α-Hydroxy Phosphonate Derivatives Containing Pyrimidine Moiety

A series of α‐hydroxy phosphonate derivatives containing pyrimidine moiety were designed and synthesized. Their structures were characterized by IR, ¹H NMR, MS and elemental analysis. The results of preliminary herbicidal activities (in vitro) showed that some of the title compounds 2 exhibited moderate herbicidal activities against dicotyledonous weeds (Brassica campestris L), and most of compounds 2 showed better activity against dicotyledonous weeds than monocotyledonous weeds (Echinochloa crus‐galli). Further bioassays (in vivo) indicated that some of the title compounds 2 possessed good and selective herbicidal activity against amaranth pigweed (A. retroflexus) in both pre‐ and post‐emergence treatments at the dose of 1.5 kg/ha. For exmple, compounds 2a , 2b and 2e exhibited 100% inhibition against A. retroflexus in pre‐emergence treatment, and 91.7%, 98.8% and 99.5% inhibition in post‐emergence treatment at the dose of 1.5 kg/ha, respectively.     

Synthesis and Herbicidal Activity of Novel β-Methoxyacrylate Derivatives Containing a Substituted Phenylpyridine Moiety

In this paper, a series of new β-methoxyacrylate derivatives containing a substituted phenylpyridine moiety was synthesized and bioassayed. The structures of all compounds were confirmed by nuclear magnetic resonance(NMR) and high-resolution mass spectrometry(HRMS). Preliminary bioassays demonstrated that compound 8d showed more than 95% inhibition against Brassica juncea and Chenopodium serotinum at 37.5 g a.i./10⁴ m², when compared with the positive control halauxifen-methyl at 150 g a.i./10⁴ m². The present work demonstrated that compound 8d exhibited the more promising herbicidal activity and may serve as a new herbicidal agent for herbicide.     

Synthesis of New Purine Derivatives Containing α- and ω-Amino Acid Fragments

Russian Journal of Organic Chemistry - New conjugates of purine and 2-aminopurine with several α- and ω-amino acids have been synthesized following two approaches based on the...     

Soluble Polymer-Supported Synthesis of α-Amino Acid Derivatives

Due to the central role played by α-amino acid in chemistry and biology, the development of versatile and new methodology for the synthesis of natural and unnatural α-amino acid has emerged as an important and challenging synthetic endeavour for organic chemists.[1] Among the various methodologies reported for α-amino acid synthesis, [2,3] the solid-phase organic synthesis (SPOS) has served as an important approach. [4] However, inherent prob lems on solid supports are reactive site accessibility, site-site interaction and monitoring of the reaction.     

Synthesis of Novel Ferrocenyl-containing Thiazole Derivatives

Ferrocenes and their derivatives have been used in material chemistry, electrochemistry and in nonlinear optics. Recently, increasing interests have been focused on their biological activity1. Ferrocifen is a ferrocene derivative of tamoxifen, will be sub…     

Synthesis,X-ray Crystallographic Analysis and Bioactivities of α-Aminophosphonates Featuring Pyrazole and Fluorine Moieties

A series of novel -aminophosphonates containing pyrazole and fluorine moieties was designed and synthesized through ultrasonic-assisted condensation and solvent-free addition reactions. Their structures were verified by IR, 1H NMR, 13 C NMR and elemental analysis. The crystal structure of diethyl[(4-cyano-1H-pyrazol-3-ylamino)(3,5-difluorophenyl)methyl]phosphonate(4a, C15H17F2N4O3P) was determined by single-crystal X-ray diffraction. Compound 4a crystallizes in the triclinic system, space group P1 with a = 8.381(3), b = 10.103(5), c = 11.268(3) , = 83.772(19), = 74.726(19), = 70.964(18), V = 869.9(6) 3, Mr = 370.30, Dc = 1.414 g/cm3, Z = 2, F(000) = 384, = 0.200 mm-1, Mo Ka radiation( = 0.71073 ), the final R = 0.0487 and w R = 0.0823 for 1582 observed reflections with I 2(I). X-ray diffraction analysis reveals that there are two planes in 4a, and the dihedral angle is 71.51. Two intermolecular hydrogen bonds and a face-to-face ··· stacking interaction are observed in the crystal structure. The compounds were evaluated for their antifungal, antiviral and antitumor activities, respectively. Among them, 4b, 4c, 4g and 4h exhibit good activities on Sclerotium rolfsii Sacc at 200 μg/m L, while 4b, 4c, 4f and 4g possess good anti-TMV activities at 500 μg/m L. Unfortunately, all of the compounds showed weak antitumor activities.     

Synthesis and Biological Activity of New Pyrethroid Acid Oxime－esters Containing Pyrazole Ring

A series of compounds containing oxime-ester linkage and pyrazole ring(in place of the ester linkage and the alcohol moiety in pyrethroid ester) was designed and synthesized. The structures of all the compounds prepared were confirmed by IH NMR and MS spectroscopy as well as elemental analyses. The binassay data of those compounds against tobacco mosaic virus (TMV), cucumber mosaic virus(CMV), potato virus X (PVX) and potato virus Y(PVY) were presented. Among them compound 6i was found to possess significant plant antiviral activities. But all the compounds showed low insecticidal and acaricidal activities.     

The Synthesis of Diphenyl Phosphonate Analogues of α-Amino Acids as Enzyme Inhibitors

Abstract

α-Aminoalkylphosphonic acids are analogues of natural aminoacids and as such have been the subject of much research effort over past years¹. The diphenyl esters of α- aminoalkylphosphonic acids are particularly potent and show high selectivity as irreversible inhibitors of serine proteinases. Thus far, α-aminoalkylphosphonic acid ester analogues of a number of aliphatic- and aromatic aminoacids have been prepared including valine, phenylalanine, tryptophan, and tyrosine², and the basic aminoacids ornithine, lysine. etc.³. We have now also prepared the a-diphenyl phosphonate analogues of the acidic aminoacids, aspartic and glutamic⁴. These have been examined as potential inactivators of serine proteinases exhibiting a P₁ specificity for aspartate and glutamate, e.g. S. aureus V8 protease and granzyme B.     

Enzymatic Synthesis of Noncanonical α-Amino Acids Containing γ-Tertiary Alcohols

Noncanonical amino acids (ncAAs) containing tertiary alcohols are valuable as precursors of natural products and active pharmaceutical ingredients. However, the assembly of such ncAA scaffolds from simple material by C−C bond formation remains a challenging task due to the presence of multiple stereocenters and large steric hindrance. In this study, we present a novel solution to this problem through highly selective enzymatic decarboxylative aldol addition. This method allows for the streamlined assembly of multifunctionalized ncAAs with γ-tertiary alcohols from readily available materials, such as _L-aspartatic acid and isatins, vicinal diones and keto esters. The modularity of electrophiles furnished four classes of ncAAs with decent efficiency as well as excellent site and stereocontrol. Computational modeling was employed to gain detailed insight into the catalytic mechanism and to provide a rationale for the observed selectivities. The method offers a single-step approach to producing multifunctionalized ncAAs, which can be directly utilized in peptide synthesis and bioactivity assessment.     

Synthesis and Antifungal Activity of Novel Chiral α-Aminophosphonates Containing Fluorine Moiety

Chiral α-aminophosphonates were synthesized using （R） or （S）-1-phenylethylamine in the presence of BF3·Et2O under microwave irradiation in moderate to good yields. The new compounds were identified by ^1H NMR, ^19F NMR, IR and elemental analysis. Their antifungal activities were evaluated and some compounds were found to exhibit excellent antifungal activities. To the best of our knowledge, this is the first report on antifungal activity of chiral α-aminophosphonates containing fluorine moiety.     

Synthesis and Magnetic Properties of Polyamide Complex Containing Bithiazole Moieties

A new polyamide containing bithiazole moieties （PTA） was synthesized by the polycondensation of 2, 2＇-diamino-4, 4＇-bithiazole （DABT） and oxalyl chloride. The polymer complex was prepared from PTA and NdC13 in DMSO. They were characterized through IR and elemental analysis. The preliminary magnetic properties of the complex PTA-Nd^3＋ was investigated, it was found that the material is a ferromagnet at low temperature.     

Synthesis and Herbicidal Activity of 3-Subsituted Amino-6-(substituted phenoxyl)pyridazine Derivatives

In recent years, many pyridazine derivatives have shown highly biological activities, such as fungicides, insecticides and herbicides. Especially, the researches of 3-(substituted phenoxyl)pyridazine derivatives have become the focus of pesticidal chemistry.     

Synthesis of New Germanium Compounds Containing α-Amino AcidEster or α-Phosphonate Groups

Bothaminoacidsanda-aminophosphonicacidshavebioachvihes-e.g.antibacteria['l.anhtUmori=],etc.ReCentStudiesshowthatthecombinahonofandnoacidsandgennaSeSquiokidesleadstohigheranhtUInorachvitythanoriginalcompoundsl'-'].Theresearchworkintroducinga-andnophoSPhonatesintoorganogewiumcompogndshaveboncAnedoubyourresearhgrouP-andthebioachvitiesoftheproductsarebeinginveshgated.AspartofthisworkwerePOrtthepreparationofthesekindsofcomPOundsinthispaPer.L1-Trichlorogermylpropionylchloridswereallowedtoreac…     

Synthesis and Pharmacological Activity of Annelated Pyrimidine Derivatives

A series of 1-glycosyl-2-glycosylthiopyrimidine (4), annelated pyrimidine derivatives, pyrazolo[3,4-d]-pyrimidine (8), ditetrazolo[1,5-a;1‘,5‘-c]pyrimidine (9), 2,9a,10-triazaanthracene (12), thieno[2,3-d]pyrimidine (14),9-thia-1,3,5,7-tetraazafluorene-8-one (15), 7-oxa-9-thia-1,3,5-triazafluorene-8-one (16), 5-oxa-9-thia-1,3-diaza-fluorene (21a and 21b) derivatives have been synthesized via a sequence of heterocyclization reactions of suitably functionalized 6-[5-(4-bromophenyl)oxazol-4-yl]-1，2，3，4-tetrahydro-2-thioxo-4-oxopyrimidine-5-carbonitrile (2) with different electrophiles and nucleophiles. The new compounds were prepared with the objective to study their pharmacological properties.     

Direct Synthesis of α-Amino Acid Derivatives by Hydrative Amination of Alkynes

α-Amino acid derivatives are key components of the molecules of life. The synthesis of α-amino carbonyl/carboxyl compounds is a contemporary challenge in organic synthesis. Herein, we report a practical method for the preparation of α-amino acid derivatives via direct hydrative amination of activated alkynes under mild conditions, relying on sulfinamides as the nitrogen source. Computational studies suggest that the reaction is enabled by a new type of sulfonium [2,3]-sigmatropic rearrangement.     

Synthesis and Antitumor Activity of New Derivatives of Podophyllotoxin

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New Method for the Synthesis of α-Amino Substituted Benzyl Phosphonic Acids and their Derivatives

Abstract

A new method for the synthesis of α-amino-substituted benzyl-phosphonic or phosphinic acid (5) was descrided. By reaction of phosphoramides (1) with substituted benzaldehydes (2) and phosphite (3) in the presence of BF₃, α-(N-phosphorylamino)-substituted benzylphosphonates or phosphinates (4) was obtained in moderate to good yield. This method distinguished itself by the simple manipulation and higher purity of the product resulted in both steps of the reaction sequences. Meanwhile, aminophosphonic esters are useful intermediated in the phosphorus peptide synthesis. The influence of variation in structure of 1, 2 and 3 on the yield of 5 was evaluated on the basis of sturcture-reactivity studies.