AFM, SPM
CH 2 W 2 NaH, THF
R. Shamilov I.D. Nizamov
R.A. Cherkasov isnizamov@mail.ru
There is a considerable interest in tetracoordinated phosphorus organic acids and thioacids and their derivatives due to their great variety of useful applications. These substances may be prepared on the basis of petrochemical and renewable wood raw materials. Thus, industrial fractions С16-С18, С20-С26 and С28-С40 are waste materials of olygomerization of ethylene, where as natural isoprenoides as aldehydes and alcohols in pyrophosphate forms seem to be renewable wood raw materials for phosphorylation. Hyperbranched aliphatic polyols have found an expanding application as additives thermoplastic resins and crosslinked thermosetting resins, rheology modifers for thermoplastics, resins for coatings etc.
The reactions of higher monoolefins of industrial fractions С16-С18, С20-С26 and С28-С40 with dialkyl phosphites in the presence of benzoyl peroxide were studied. On the basis of these studies, the technological method of synthesizing o,o-dialkyl esters of mixed long-chain alkylphosphonic acids was developed. O,O-Dialkyl alkylphosphonates obtained were used as intermediates for the synthesis of corresponding higher alkylphosphonic acids and their potassium salts. Higher alkylphosphonous and dialkylphosphinic acids were obtained by the reactions of water solution of hypophosphorous acid with olefins of fractions С16-С18, С20-С26 and С28-С40 in the presence of benzoyl peroxide and sulfuric acid. Addition reactions of O,O-dialkyl dithiophosphoric and bisaryldithiophosphonic acids with olefins of industrial fractions of С16-С18 and С20-С26 were performed in the presence of anhydrous of ZnCl2 with the formation of the mixture of adducts. The model reactions of O,O-diethyl dithiophosphoric acid with individual octene-1, hexadecane-1 and octadecene-1 as α-olefins of linear structure and with 2-methylpentene-1 as an isomeric vinylidene α-olefin results in the formation of adducts in accordance with Markovnikow’s rule. Long chain alkylphosphonic, alkylphosphonous and dialkylphosphinic acids, their esters and salts, S-alkyl esters and diesters of dithiophosphoric and bisdithiophosphonic acids possess high anticorrosion activities toward steel hand-make goods in the condition of aggressive carbonaceous medium.
Substitution reactions of geraniol, nerol and racemic linalool with amido- and chloro- phosphites, Kabachnik-Fields reaction of citral with dialkyl phosphites in the presence alkyl amines, imine formation reaction of E,Z-citral, R,S-citronellal and (R)-(–)-myrtenal with primary amines and Pudovik reactions of prenyl imines obtained with dialkyl phosphites or with O,O-dialkyl trimethylsilylphosphites were studied. On the basis of these studies, new dienyl diprenoid phosphite esters, unsaturated prenyl imines and α-aminophosphonates were prepared.
We have developed convenient method for the thiophosphorylation of aliphatic polyesters of Boltorn H20, H30 and H40 containing 16, 32 and 64 hydroxyl groups respectively by the reactions with 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides to give oligomeric dithiophosphonic acids. Their ammonium salts were also obtained. The reactions of hyperbranched polyols with cyclic amidophosphites were performed with the formation of the corresponding phosphite derivatives and the elimination of diethylamine. The hyperbranched polyols were found to react with pyrocatechol chlorophosphite in the presence of triethylamine to give 1,3,2-dioxaphospholane derivatives. Dialkyl phosphate derivatives of Boltorn H20, H30 and H40 were prepared by use of ultrasonic irradiation in the substitution reactions of the polyesterpolyols with dialkyl chlorophosphates. Unsaturated polyacrylates obtained by the reactions of Boltorn H20, H30 and H40 with acryloyl and methacryloyl chlorides reacts with O,O-dialkyl dithiophosphoric acids to form the corresponding dithiophosphates.
3. Advanced Methods of Organic Synthesis: Poster presentation P-65 INVESTIGATION OF CHEMICAL MODIFICATION OF
2-AMINO-4-DIETHYLPHOSPHONOTHIAZOLE Academician E.A. Buketov Karaganda State University, Faculty of Chemistry, Department of Organic Chemistry and Polymers, Karaganda, Kazakhstan
L.K. Salkeyeva M.T. Nurmaganbetova
Y.V. Minayeva A.K. Shibayeva
E.K. Tayshibekova ritunur@mail.ru
Interest in organophosphorous compounds was defined by their variety and unique set of features making these substances valuable objects of theoretical research and significant for practical use.
Previously, we developed a convenient method for the synthesis of phosphorylated thiazole (I) according to the scheme of classical Hantzsch reaction based on diethylketophosphonate and thiourea [1].
Chemical modification of the synthesized phosphorus-containing amino-thiazole (I) can be implemented with the participation of the free amino group, which has a sufficiently high nucleophilicity. Using this feature of the structure allows receiving a variety of derivatives based on nucleophilic substitution reactions. We carried out the reaction of 2- amino-4-diethylphosphonothiazole (I) with diethylphosphite in the presence of base, as a result of which 2 - (N-diethylphosphonamino)-4-diethylphosphonothiazole (II) was obtained.
N S (EtO)2P
NH2 O
+ P
Cl O
(EtO)2 Et3N
-Et3N*HCl
N S (EtO)2P
NH O
P O
(OEt)2
(I) (II)
In our opinion, easily accessible and reactive 2.4-dinitrochlorobenzene is interesting nucleophilic agent in chemical modification reactions of the (I). The reaction of 2-amino-4- diethylphosphonothiazole (I) with 2.4 - dinitrochlorobenzene was carried out in the presence of triethylamine in benzene.
N S (EtO)2P
NH2
O
+ + Et3N N
S (EtO)2P
NH O
Cl O2N
NO2
бензол O2N
NO2 - Et3N*HCl
(I)
(III)
The resulting 2 - (N-2 .4-dinitrophenylamino)-4-diethylphosphonothiazole (III) is a valuable reagent for further chemical modifications.
References:
1. Salkeyeva L.K., Minayeva, E.V., Mantel, A.I., Nurmaganbetova M.T. Synthesis and chemical modification of the phosphorus-containing derivatives of 2-aminothiazole /Proceedings of the 6th Beremzhanov’s Congress on Chemistry and Chemical Engineering. Karaganda: Karaganda State University, 2008. - P. 365-368.
3. Advanced Methods of Organic Synthesis: Poster presentation P-66 PYRIDINIUM YLIDES IN THE SYNTHESIS OF
2-ACYL-SUBSTITUTED CONDENSED DIHYDROFURANS
Samara State Technical University, Organic Chemistry, Samara, Russia
V.A. Osyanin D.V. Osipov
Y.N. Klimochkin vosyanin@mail.ru
Arene ring-fused dihydrofurans have attracted widespread interest in view of their presence in natural products, and their pharmacological activities. Extended arenofurans have potential applications as fluorescent dyes, organic light-emitting diodes, two-photon absorption materials etc.
We have developed a simple, general route to the condensed dihydrofurans (1a-d), substituted in position 2 by an acyl group, starting from phenolic Mannich bases (2,3), salicylic alcohol (4), ortho-triethylammoniomethylphenolate (5) and the carbonyl-stabilised pyridinium ylides (6):
N OH
N N
O O
R OH
OH
O O
R
O O
O2N R
O
N(C2H5)3
NO2 + _
R O
_ +N
OH N(CH3)2 R1
O R
O R
1
R = 1-Ad, C(CH3)3, cyclopropyl, Ar R1= H, Ar
1a
1b
1c
1d 2
3 4
5
6
The reaction proceeds readily in acetonitrile at reflux temperature and usually affords the desired products in good yields. The formation of condensed dihydrofurans can be rationalized in terms of a Michael addition of the ylides generated in situ from pyridinium salts and DBU to ortho- quinone methides (A). Resulting phenolate (B) undergoes a five membered ring O-cyclization to give (1a-d). In case of 1,2-disubstituted 1,2-dihydronaphtho[2,1-b]furans (1d) the trans-structure is clearly assigned by the analysis of the vicinal coupling constant of the two methine protons (J = 5 Hz). In this reaction, no cyclopropanes (C) derived from a three-membered ring C-cyclization could be found.
R O
N Br
OH OH
- H2O
O O
N
COR - Py
O O
- R
O
COR - Py
- + +
6 DBU
A B
C
Some of the prepared products may be useful intermediates for the preparation of highly functionalized arenofurans.
This work was supported by the Council on Grants of the President of the Russian Federation (the program of state support of young Russian scientists, grant MK-3368.2011.3) and using the equipment CCU "Investigation of physical and chemical properties of substances and materials".
3. Advanced Methods of Organic Synthesis: Poster presentation P-67 SYNTHESIS OF OXAZOLIDINES BASIS ON VICINAL AMINO ALCOHOL SULFOLANE SERIES 1 - Dnepropetrovsk National University
2 - Scientific Center "AKSO" NAS of Ukraine V.A. Palchikov1
I.S. Prishlyak1 S.V. Tretyakov1
P.G. Dulnev2 palchikoff@mail.ru
Compounds including vicinal amino alcohol and sulfolane fragments as well as substances containing naturally widespread oxazolidine cycle possess distinct and various biological activities. Since few compounds containing both fused sulfolane and oxazolidine fragments are currently described, we have developed the appropriate synthesis route.
It was considered the possibility of formation novel heterocycles from amino alcohol (1) and aldehydes (2-7, R = p-NO2С6Н4 (2), p-BrС6Н4 (3), p-FС6Н4 (4), H (5), Ph (6), C3H7
(7)) having different electronic pattern of sustituents. The reactions were carried out by refluxing equimolar quantities of precursors in benzene with p-toluenesulphoacid (5-10 mol.%) using a Dean-Stark trap.
All the reactions gave desired heterocycles in moderate yields (30-65%) except for the interaction involving electron-enriched aromatic aldehyde.
SO2
H2N OH R=2-5
RCHO
R=6, 7 SO2 O HN
R
1
In addition, cis-amino alcohol (8) containing both norbornene and sulfolane fragments turned out to be inactive towards aromatic aldehydes but it easily underwent heterocyclization when treating with formaldehyde (5).
SO2
NH OH
R=5
RCHO R=6, 7
SO2 O N
8
The structures of the products were proven by NMR 1H and IR methods.
3. Advanced Methods of Organic Synthesis: Poster presentation P-68 TRANSFORMATION OF
BIS(TRIMETHYLSILYL)ACETYLENE TO ALKYNYL SUBSTITUTED NITROGEN HETEROCYCLES Saint-Petersburg State University, Chemistry Department, Saint-Petersburg, Russia