AFM, SPM
CH 2 W 2 NaH, THF
A. S. Pankova
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
3. Advanced Methods of Organic Synthesis: Poster presentation P-69 SYNTHESIS OF HYDROXYSULFIDES BASED ON
3,5,8-TRIOXABICYCLO[5.1.0]OCTANES 1 - A.M. Butlerov Chemical Institute, Kazan Federal University, Kazan, Russia
2 - Chemistry Department, Kazan State Medical University, Kazan, Russia
R.S. Pavelyev1 S.G. Gnevashev1
R.M. Vafina1 L.E. Nikitina2 Yu.G. Shtyrlin1
E.N. Klimovitskii1 pavelev.r.s@rambler.ru
Thiolysis of 3,5,8-trioxabicyclo[5.1.0]octanes I-IV by thiophenol was found to be рН-dependent and leads to the 5-7 – membered cyclic acetals. Only the seven-membered products (a) were formed under the basic conditions. In the acidic medium 1,3-dioxepane I- III (a) is isomerized to the less-membered cyclic acetals I-II (c) and III (b). This approach is very suitable for the preparation of five- and six-membered cycles. Unsubstituted at C2 dioxepane IV (a) was established to remain intact in the presence of acid.
O O O
R1
R2 O
O R1
R2 HO
PhS PhSH, K2CO3
R1= R2= CH3(I); R1= R2= -(CH2)5- (II); R1= H, R2= Ph (exo, endo) (III); R1= R2= H (IV) solvent-free, toC
I-IV I-IV (a)
O O R1
R2 HO
PhS
R1= R2= CH3(I); R1= R2= -(CH2)5- (II); R1= H, R2= Ph (III).
CHCl3,H+
O O R1
R2 HO
PhS
O
O R1
R2 OH
PhS O
O R1
R2 SPh
HO
(a) (b) (c)
(a)
Equilibrium
I and II: 9 : < 1 : 90
III: < 7 : 85 : <7
Hydroxysulfides including there acetates was oxidized to the corresponding sulfones.
The product structure was confirmed by 1D, 2D NMR, chromato-mass spectrometry and single crystal X-ray diffraction.
3. Advanced Methods of Organic Synthesis: Poster presentation P-70 ALKYLATION OF 1,4-DIHYDROXYNAPHTHALENE WITH TERTIARY ALCOHOLS AND SYNTHESIS OF
NITROGEN-CONTAINING DERIVATIVES OF 2-(ADAMANTHYL-1)-TETRALIN-1,4-DIONE 1 - Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia
2 - Siberian Federal University, Krasnoyarsk, Russia I.V. Peterson1
W.A. Sokolenko1 N.M. Svirskaya1
A.I. Rubailo2 Defender200385@mail.ru
Conversion 1,4-dyhydroxynaphthalene into its tautomer 1,2,3,4-tetrahydro-naphthalene-1,4- dione and chemistry of it derivatives was studied by the authors [1].
We studied 1,4-dyhydroxynaphthalene (1) alkylation with adamantanol-1, tert-butyl and tert- amyl alcohols in trifluoroacetic acid. We found that compound 1 C-alkylation occurred in the position 2 with simultaneous keto-enol tautomerization and corresponding 1,4- dyhydroxynaphthalenes were formed in diketone form. Diketones 2-4 were stable in usual conditions. Dienol form, 2-(adamanthyl-1)-1,4-dyhydroxynaphthalene (5), was received at 2- (adamanthyl-1)-tetralin-1,4-dione (2) by interaction with morpholine under an argon atmosphere in the sealed NMR tube. After loss of sealing of NMR-tube, 5 quickly oxidized into 2-(adamanthyl-1)- 1,4-naphthoquinone (6).
It is well known that many nitrogen-containing adamantine derivatives are used in pharmacology (Rimantadine, Amantadine, Dopamantine, Bemantane and etc.) [2]. We studied diketone 2 reactions with the following nitrogen-containing compounds: hydroxylamine (R1), 2,4- dinitrophenylhydrazine (R2), semicarbazide (R3) and thiosemicarbazide (R4). The new synthesized compounds 7-10 could be interesting as compounds with potential biological activities and as the starting material for further organic synthesis.
General synthesis compounds 2-10 scheme is presented on figure 1. Physical data of compounds 2-6 and their synthesis methods are described in article [3].
References:
1. a). Pearson M. S., Jensky B.J. J. Org. Chem. 1978. V.43. P.4617-4622. b). Laatsch H. Liebigs Ann. Chem.
1980. V.1. P.140-157. c). Kundig E. P., Garcia A. E. Angew. Chem. Int. Ed. 2006. V.45. P.98-101.
2. Morozov, I.S. Pharmacology of adamantanes. 2001. Volgograd. – 320 p.
3. Peterson I.V., Sokolenko W.A., Svirskaya N.M., Rubailo A.I. Journal of Siberian Federal University.
Chemistry. 2010, V.3, №3, p. 253-259.
3. Advanced Methods of Organic Synthesis: Poster presentation P-71 THIONILANILINES AS DIENE STRUCTURES IN
DIELS-ALDER REACTIONS
1 - Immanuel Kant Baltic Federal University, Kaliningrad, Russia 2 - A.E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences, Kazan, Russia
V.V. Plemenkov1 Ya.V. Veremeychik1
D.N. Shurpik1 I.A. Litvinov2 O.A. Lodochnikova2
D.B. Krivolapov2 plem-kant@yandex.ru
On basement of reactivity of aromatic N-sulfinilamines as heteroatom dienes in Dieal-Alder reactions, adducts of substituted thionilanilines with norbornene and norbornodiene was obtained. Their molecular structure was determined using methods of X- ray diffraction, IR and NMR spectroscopy and considered to be benzo-ortho-thiazine. We clarified that addition of diene component to bicyclo[2.2.1]heptene structure in all cases is performing from the side of methilene bridge of last. Configuration of sulfoxide group corresponds to both endo-orientation of addens in case of Z-configuration of parent thionilanilines or exo-orientation in case of E-configuration of thionilanilines.
N S
O
R
N S
O
R
N S
O
H
R
N S H
R H
O
H
R = H, CH3, OCH3, NO2
Reactions of meta-substituted thionilanilines lead to formation of two isomers (A and B). Proportion of isomers depends on the type of substitute and thermal conditions of reaction: with R = NO2 and t = 20 °C ratio of A:B is 1:1 and with growing of temperature the part of isomer B significantly increases.
N S
R O
N S H
O
H H R
N S H
O
H H R
R = CH3, NO2 (A) (B)
3. Advanced Methods of Organic Synthesis: Poster presentation P-72 CHEMICAL MODIFICATION OF MONOTERPENES
BY DIELS-ALDER REACTIONS
1 - Immanuel Kant Baltic Federal University, Kaliningrad, Russia 2 - A.E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences, Kazan, Russia
3 - Kaliningrad State Technical University, Kaliningrad, Russia M.S. Dzyurkevich1
V.V. Plemenkov1 O.A. Lodochnikova2
D.B. Krivolapov2 I.A. Litvinov2
O.V. Kazimirchenko3 plem-kant@yandex.ru
By interaction of myrcene and alloocimene with maleic and citraconic anhydrides adducts of Diels-Alder reaction which is anhydrides of dicarboxylic acids of sesquiterpene class were obtained. By further modification of adducts using morpholine, piperazine and N-substituted piperazines corresponding mono- and bis- amides were obtained. The disclosure of cyclic anhydride fragment takes place preferably to one of two carbonyl groups as it shown in scheme.
O R2
R3
R4
R5 R1 O
O O
O
O R1
O O
O R1
HN X X = O, NH, N SO2 Ar
R2 R3
R4
R5 R1
COOH O
N X
R2 R3
R4
R5 R1 O
N X
O
N X
Molecular structures of all compounds were determined using methods of X-ray diffraction, IR and NMR spectroscopy
The amides obtained were tested for biological activity. It was shown that number of compounds is demonstrating moderate and high activity against Escherichia coli, Staphylococcus sp. and Aspergillus niger.
3. Advanced Methods of Organic Synthesis: Poster presentation P-73 DIAZIRIDINE RING EXPANSION IN
6-ARYL-1,5-DIAZABICYCLO[3.1.0]HEXANES UNDER THE ACTION OF ACRYLONITRILE AT BORON TRIFLUORIDE ETHERATE CATALYSIS N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences (ZIOC RAS), Moscow, Russia
M.I. Pleshchev V. Yu. Petukhova
V.V. Kuznetsov
N.N. Makhova michele-chem@yandex.ru
Diaziridine ring expansion reactions in mono- and bicyclic diaziridines under the action of different dipolarophiles were widely studied in ZIOC RAS, in particular the [3+2]-cycloaddition reactions of CS2, activated nitriles, 1,3-diphenylpropen-2-one, β-nitrosterenes to azomethine imines 1, generated from 6-aryl-1,5- diazabicyclo[3.1.0]hexanes 2 in ionic liquids (ILs) at BF3·Et2O catalysis.1,2 These reactions proceeded with high both regio- and stereoselectivity resulting in new methods for the synthesis of tetrahydro-1H,5H-pyrazoles annelated by 1,3,4-thiazolidine, 1,2,4-triazoline, pyrazolidine heterocycles.
In this work diaziridine ring expansion reactions in 6-aryl-1,5- diazabicyclo[3.1.0]hexanes 2a-h were performed with acrylonitrile both in ionic liquids ([bmim][BF4] and [bmpyrr][NTf2]) and in MeCN at BF3·Et2O catalysis. In both kinds of solvents reactions proceeded regiospecifically contrary to the Michael addition mechanism and with high diastereoselectivity resulting in the mixture of diasteremers 3-aryltetrahydro- 1H,5H-pyrazolo[1,2-a]pyrazoles 3a-h and 3′a-h with predominamce of diastermers 3a-h (1H NMR) in ratio 2.5-4:1. Diastereomers 3b and 3’b were separated by column chromatography on SiO2. The total yields of compounds synthesized were moderate. The best results (39%) were obtained in IL [bmpyrr][NTf2] in excess of acrylonitrile.
Ar N N
2a-h
N N Ar
1a-h
CN
N N H
Ar CN
H N
N H
Ar H
CN +
3a-h 3'a-h
Ar = 4-MeOC6H4 (a), 4-EtOC6H4 (b), 4-MeC6H4 (d), 3,4-(Methylenedioxy)phenyl (c), Ph (e), 2-MeOC6H4 (f), 3-MeOC6H4 (g), 2,4-(MeO)2C6H3 (h)
BF3 Et2O ILs
(MeCN, acrylonitrile);
40 to 60oC; 2 d
References:
1. Yu.S. Syroeshkina, V.V. Kuznetsov, K.A. Lyssenko, N.N. Makhova, Mendeleev Commun., 2008, 18, 42-44, 207-208; 2009, 19, 276-278.
2. Yu.S. Syroeshkina, V.V. Kuznetsov, L.L. Fershtat, N.N. Makhova, Russ. Chem. Bull, Int Ed., 2009, 58, 366-379; 2010, 59, 1621-1630.
3. Advanced Methods of Organic Synthesis: Poster presentation P-74 METATHESIS OF CARBONYL COMPOUNDS IN
REACTION OF 6-ARYL-1,5-DIAZA-
BICYCLO[3.1.0]HEXANES WITH ISATINS AT BORON TRIFLUORIDE ETHERATE CATALYSIS N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
M.I. Pleshchev V.Yu. Petukhova
L.L. Fershtat