Биоциклы, синтез и отделение

 UDC 547,288 + 546.221.1 + 547,711

 

SYNTHESIS AND SEPARATION stereoisomeric 2, 4, 6, 8-tetrasubstituted-3, 7-DITIA-1, 5-diazabicyclo [3.3.0] octane  

V.R. Ahmetova 1, N.N. Murzakova 1, G.R. Habibullina 1, T.V. Tyumkina 1, L.F. Korzhova 2, I.S. Bushmarinov 3, K.A. Lysenko 3  

1 Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,  
Russian Federation, 450075 Ufa, prosp. October, 141.  
Fax: (347 2) 31 2750. E-mail: ink@anrb.ru.  
2Bashkir Republic Research Centre of Ecology,  
450075 Ufa, prosp. October, 147. E-mail: ecocnt@diaspro.ru  
3Institute Organoelement Compounds. Named after A. N. Nesmeyanov, of  Russian Academy of Sciences,  
Russian Federation, 119991, Moscow, st. Vavilova 28.  
Fax: (495) 135 9271. E-mail: star@xray.ineos.ac.ru.  

Heterocyclization of hydrazine with aldehydes (R-CHO, where R = Me, Et, nPr, nBu, nPent, Ph, Ph-OCH3, 3-Py) and H2S synthesized and isolated stereoisomeric 2,4,6,8-tetrasubstituted-3, 7 ditia-1 ,5-diazabicyclo [3.3.0]-octanes. According to the XRD and 1H NMR and 13C inserted trans-transoid-trans conformation of 3,7-tetraalkilsubstituted ditia-1 ,5-diazabicyclo [3.3.0] octane.  

It is known that 1, 2, heterocycles of tiadiazolidinovogo series show a variety of biological activity. For the first time 3,7-ditia-1 ,5-diazabicyclo [3.3.0] octane, containing condensed tiadiazolidinovye cycles was obtained with yield 11% of the hydrazine and formaldehyde H2S3 at 0 ° C. Recently 4, 5 have proposed improved methods for its production with the yield of 76 and 80%. Conformational features of this bicyclane were investigated by us both in the crystal faze6 and in solution 4. In the crystal of molecule compounds adopt the cis-conformation with the conservation of symmetry of the second order С2ν. In solution (CDCl3) at room temperature (24.5 ° C) as a result of inversion of nitrogen atoms is observed conformational equilibrium of cis - 3,7-ditia-1 ,5-diazabicyclo[3.3.0]octane.  
        In order to develop effective methods of synthesis of alkyl-and aryl substituted 3,7-ditia-1 ,5-diazabicyclo [3.3.0] octane and study their structural characteristics, we investigated the reaction of tiomethylation of hydrazine with aliphatic and aromatic aldehydes and H2S.  
         Previously, we found that cyclometylation of hydrazine with formaldehyde and H2S depends on the ratio of initial reagents, temperature4 and PH5, and in the case of acetaldehyde and from the order of mixing the initial reagents.7 As a result, the synthesis of 2,4,6,8-tetramethyl- 3,7-ditia-1 ,5-diazabicyclo [3.3.0] octane 2 carried out with prior sparging acetaldehyde 1 with hydrogen sulfide and with subsequent dropping of hydrazine at a temperature below 0 ° C. Under these conditions, is formed exclusively bicyclo 2 with 64% yield as a mixture of stereoisomers 2a-d (Scheme 1, Table 1) according to 1H NMR, 13C, GC-MS. Application of this methodology in Heterocyclization of hydrazine with aliphatic aldehydes RCHO [R = Et (3), nPr (4), nBu (5), nPent (6)] and H2S similarly has a number of relevant 2,4,6,8-tetraalkyl-3 ,7-ditia-1 ,5-diazabicyclo [3.3.0] octane 7-10 as a mixture of stereoisomers. Condensation with aromatic aldehydes RCHO 11, 12 (Ph, 3-Py) led to a corresponding isomer 2,4,6,8-tetraaryl-3 ,7-ditia-1 ,5-diazabicyclo [3.3.0] octane 15, 16 and in case of aldehyde 13 (Ph-OCH3) of stereoisomeric 2,4,6,8-tetrakis (4'-methoxyphenyl) -3,7-ditia-1 ,5-diazabicyclo [3.3.0] octane 16.

Scheme 1

In the 1H NMR spectrum of the total stereoisomeric mixture of bicycle 2 at 20 ° C revealed two broadened signal corresponding to methyl and methine groups in the characteristic spectral regions, whereas in the 13C NMR spectrum in a relatively slabopolnoy narrow region of the spectrum 61.3-69.5 ppm observed seven signals of carbon atoms-CH-groups, as well as seven resonances of methyl groups. According GHMS 2,4,6,8-tetraalkyl-3 ,7-ditia-1 ,5-diazabicyclo [3.3.0] octane 2,7,8 are formed in the form of four, and 9.10 in the form of three isomers with different configuration of alkyl substituents. For the isomers 2b, c of bicyclooctane 2 GC-MS analysis determined retention indices – Kovach`s indices 8.  
        To isolate individual stereoisomeric bicyclo (2,7-10), we have developed conditions for separation by column chromatography (BCH) (Table 1) and made X-ray diffraction analysis of crystalline isomers, since the definition of the configuration of one of the isomers can be used to set the structure as the reference in the analysis of NMR 1H and 13C.  
          As adsorbents used activated carbon, Al2O3, SiO2, and SiO2, impregnated with AgNO3. The best results of separation of isomeric ditiadiazabicyclooctanes 2 were obtained from KX SiO2, impregnated AgNO3 (5%) 9.  
Table 1. Separation conditions KX, physical-chemical characteristics and yield stereoisomeric 2,4,6,8-tetraalkyl-3 ,7-ditia-1 ,5-diazabicyclo [3.3.0] octane 2,7-10  

R1		Separation conditions		Rf	Physical  state	yield, %
		carrier	eluent
Me	2a	SiO2-AgNO3(5%)	C6H12:AcOEt:СHСl3 = 5:1:1	0.55	cristae	31
	2b			0.59	oil	18
	2c			0.61 0.63	oil	7 7
	2d
Et	7а	coal asset.  Brand AH-5	CH2Cl2 :hlf, 2:1	0.58 0.63 0.67 0.53	cristae  oil oil	42 21 8 8
	7b
	7c
	7d
Pr	8a	coal asset.  Brand AH-5	CH2Cl2 :hlf, 2:1	0.53 0.62 0.69 0.57	cristae oil oil	48 17 11 11
	8b
	8c
	8d
Bu	9b	SiO2-AgNO3(5%)	petr.ef-CH2Cl2, 5:3	0.56 0.66 0.78	oil oil oil	52 20 22
	9c
	9d
Pent	10b	SiO2-AgNO3(5%)	hexane: AcOEt:hlf, 5:1:1	0.57 0.68 0.75	oil oil oil	54 34 12
	10c
	10d

 

 

With the gradual evaporation of the eluent from the fraction with Rf 0.55 at room temperature, were obtained the crystals, which were investigated by XRD [7]. The structure is defined as trans-transoidny-trans (TTT) isomer of 2a.  

In the crystal structure of isomer 2a disordered positions have a population of 0,887 and 0.113 (CH group designated rooms with strokes) (Pict. 1). The atoms of nitrogen, sulfur and methyl groups are not disordered.

Pict.1. The molecular structure of the isomer TTT-2a.

Thus, the TTT configuration of methyl substituents relative to each other is determined. Conformation of the bicycle 2a in the crystal of cis with equatorial arrangement of the methyl groups.  
In the 13C NMR spectrum of the CH3 and CH groups in 2a appear in the form of four magnetically nonequivalent signals: two singlets, respectively, at δН 1.40 and 1.50 ppm and two unsplit singlet at δН 4.5 and 5.2 ppm In the 13C NMR spectrum also contained two signal in silnopolnoy and slabopolnoy regions of the spectrum at δс = 18.50, 26.40 ppm and δс = 64.76, 66.30 ppm respectively.  
         The second stereoisomer 2b (fraction with Rf 0.59), representing the oily product 1H NMR and 13C had two signals: at δH = 1.45 (J = 4Gts), δH = 4.52 ppm (3J = 4Gts) and δС = 29.8, 61.9 ppm respectively. Given the symmetry of the molecule two signals can be cis-cis-cissoid (TSTSTS) isomers of 2b with the equatorial or axial position of methyl groups.  
          There are three signal δс = 69.3, 67.3, 66.8 ppm In the 13C NMR spectrum of the third isomer (fractions with Rf 0.61),in the slabopolnoy spectrum region, corresponding to signals of carbon atoms of the cycle.  
           In the selected conditions in the individual form the fourth isomer 2d failed to allocate using the BCH, and therefore its corresponding signals obtained by subtracting the previously established signals of the three isomers 2a-c from the total spectrum of the reaction mixture of isomers. Thus,to the fourth stereoisomer classified signals 66.0 and 25.1 ppm in the 13C NMR spectrum, as well as 4.35 and 1.50 ppm – In the NMR 1H.  
           Thus, heterocyclization of hydrazine with acetaldehyde and H2S obtained four isomers of 2,4,6,8-tetramethyl-3 ,7-ditia-1 ,5-diazabicyclo [3.3.0] octane 2a-c in the cis conformation with different configurations of methyl groups, three of which are marked with KX in the individual form (Table 1).  
           When hydrazine interact with proponic acid (3), oil aldehydes(4) and H2S (Scheme 1), a similar pattern to obtain the four stereoisomeric 2,4,6,8-tetraethyl - and tetrapropilsubstituted bicyclane 7,8 which have been identified by the BCH on activated carbon grade K-5, is observed.  
            On the basis of the crystalline isomer of 2,4,6,8-tetrapropil-3 ,7-ditia-1 ,5-diazabicyclo [3.3.0] octane 8 was identified cis-conformation with TTT configuration propyl groups (Fig. 2). In the crystal structure of isomer 8 conformation of the articulated by link N (1)-N (2) five-membered [N2SC2] cycles is C (2) sofa and C (4) Sofa, respectively. Atoms C (2) and C (4) located in the top of sofas and deviate from the plane of the 4 other atoms, respectively on ... Å ... Å. The dihedral angle between mean planes of the cycles is about ... (Fig. 2). The spectra of four isomers of tetraethyl-7 and 8 tetrapropil bicyclane are similar to the spectra of configuration isomers for  tetrametilsubstituted bicyclane 2. The total yield stereoisomeric tetrametilsubstituted bicyclane 7-10 increased from 80-100% with increasing length of alkyl radical in the starting aldehyde.  

Pict. 2. Molecular structure of 2,4,6,8-tetrapropil-3 ,7-ditia-1 ,5-diazabicyclo [3.3.0]octane8.  
          Note that in the case of valerian (5) and nylon (6) aldehydes were formed only three isomers of 9,10. Isomeric bicyclane have also been identified by us in the individual form BCH. And all three stereoisomeric fractions of tetrabutyl-and tetrapentylsubstituted bicyclane are oily liquids. Obviously, bulky substituents (nBu, nPent) all of transcancelled 9 stresses do not form crystalline TTT 2,4,6,8-tetrabutyl-,-tetrapentil-3 ,7-ditia-1 ,5-diazabicyclo [3.3.0] octanes.  
          Just found that in the reaction of hydrazine and H2S with aromatic aldehydes in the case of benzaldehyde 11 and pyridine-3-il-aldehyde 12, stereoselective formation of the corresponding 2,4,6,8-tetraarilzameschennye-3 ,7-ditia-1, 5 - diazoniabicyclo [3.3.0] octanes 14, 15 formed. While the reaction with aniseed aldehyde 13 passes with the formation of stereoisomeric bicyclooctane 16 in the ratio 1:2:1 (data 1H NMR and 13C, HSQC and HPLC). In addition, due to the reduction reaction activity of aromatic aldehydes (conversion 40%) compared with aliphatic aldehydes (conversion 100%) total yield of 2,4,6,8-tetraarylsubstituted-3 ,7-ditia-1 ,5-diazoniabicyclo [3.3. 0] octane 14-16 does not exceed 30%.  
                                    Experimental part 
           Analysis of the reaction products of tiomethylation performed by GLC on chromatograph "Chrom-5" with flame ionization detector, stationary phase "SE-30" (5%) on the carrier Chromaton N-AW-HMDS (packed steel column 2400 • 3-mm, programming temperature 50-270 ° C, 8°/min., carrier gas helium). 1H NMR spectra of compounds are registered on the spectrometer "Bruker AM-400 with an operating frequency of 400 MHz and 13C NMR spectra - on spectometre Jeol FX 90 Q "with the operating frequency of 22.50 MHz, solvent - CDCl3. IR spectra were measured on a spectrophotometer "Specord 75 IR" in suspension in liquid paraffin with KBr. Chromato-mass spectral analysis of compound 2 was performed on the device "Finigan", model 4021 (glass capillary column 50000h0.25mm, stationary phase HP-5, carrier gas-helium, temperature programming from 50 to 300° C 5 deg/min speed, temperature evaporator 280 ° C, the temperature of the ion source 250 ° C, 70eV), compound 3 on the device SHIMADZU LCMS-2010EV. Elemental analysis of samples performed on elemental analyzer firm Karlo Erba, model number 1106. For column chromatography using silica gel grade KSKG impregnated AgNO3.14. TLC was performed on plates of Silufol W-254, showed pairs of J2.  
          The general methodology cyclomethylation N2H4 · H2O by aldehydes RCHO [R = Me, Et, nPr, nBu, nPent, Ph, Ph-OCH3, 3-Py]. Aldehyde (0.2 mol) at a given temperature (-70, or -10, 0 ° C) saturated with hydrogen sulfide (0.2 mol) for 15 minutes, then dripped (0.05 mol) of hydrazine. The mixture was stirred for 3 hours at a given temperature, then extracted with chloroform (3 × 50 ml), evaporated on a rotary evaporator,get products of 2-16, which was purified by column chromatography.  
           X-ray analysis of compounds 2a [7] and 8 made on the diffractometer «Enraf * Nonius CAD4» (Mo-Кα radiation, graphite monochromator, θ/2θ scan, 2θmax = 54 º)  
           Colorless crystals of 8 (C20H40N2S2), obtained by recrystallization from a mixture of methylene chloride-chloroform (2:1) are orthorhombic: a = 8.560 (7), b = 14.204 (1), c = 16.715 (1) Å, V = 2032.1 (3) Å3, dvych. = 1,336 g/cm-3, space group Pbca, Z = 8. After averaging equivalent reflections 22494 obtained in 2656 (R (int) = 0.0242) independent reflections, which are used in further calculations. The structure was solved by direct methods and refined by full-matrix anisotropic-isotropic approximation of F2. All hydrogen atoms were placed in calculated positions and refined in a model "rider”. Final divergence factors: wR2 = 0.0767 (calculated at Fhkl for 2506 reflections with I> 2σ (I)), GOF = 1.021, 146 refined parameters.  

           2,4,6,8-tetramethyl-3 ,7-ditia-1 ,5-diazabicyclo [3.3.0] octanes  
          2a. Colorless crystals, yield 31%, Tm. 65-66 ° C. Rf 0.55, SiO2-AgNO3. Eluent hexane-ethyl , ppm, J, Hz, 20 ° C): 1.40 (q, 6H,dacetate-chloroform, 5:1:1 1H NMR spectrum ( SH3 (9, 12); J = 4); 1.50 (d, 6H, SH3 (10, 11); J = 4), 4.50 (ush. s, 2H, CH (2,4) W1 / 2 = 60 Hz), 5.20 (ush. s, 2H, CH ( 6,8) W1 / 2 = 60 Hz). , ppm): 16.90d13C NMR spectrum ( (a, C (10, 11)), 26.40 (a, C (9, 12)), 64.76 (q, C (4, 6)), 66.30 ( d, C (2, 8)). Mass spectrum, m / z (Iotn (%)): 204 [M] + (90), 119 [N2H3CH (CH3) SC (CH3)] + (98), 74 [NCH (CH3) S] + (8 ), 57 [N2CH (CH3)] + (97). Found (%): C 47.50, H, 7.52; N, 13.63; S, 30.98. Calculated for S8N16N2S2 (%): C 47.02, H, 7.89; N, 13.71; S, 31.38.  
         2b. Oil light - yellow, yield 18%. Rf 0.59, SiO2-AgNO3. Eluent hexane-ethyl acetate-chloroform, 5:1:1. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 1.45 (d, 12N, SH3 (9,10,11,12)), 4.52 (s, 4H, CH (2,4, 6,8)). , ppm): 29.80d13C NMR spectrum ( (a, C (9,10,11,12)); 61.90 (a, C (2,4,6,8)). IK = 1550. Mass spectrum, m / z (Iotn (%)): 204 [M] + (90), 119 [N2H3CH (CH3) SC (CH3)] + (98), 74 [NCH (CH3) S] + (8 ), 57 [N2CH (CH3)] + (97) Found (%): C 47.50, H, 7.52; N, 13.63; S, 30.98. Calculated for S8N16N2S2 (%): C 47.02, H, 7.89; N, 13.71; S, 31.38.  
         2c. Oil light - yellow, yield 7%. Rf 0.61, SiO2-AgNO3. Eluent hexane-ethyl acetate-chloroform, 5:1:1. , ppm, J, Hz,d1H NMR spectrum ( 20 C °): 1.41 (m, 3H, SH3 (10)), 1.48 (c, 3H, SH3 (9)), 1.41 (c, 3H, SH3 (11)), 1.66 (s, 3H, SH3 (12)), 4.38 (ush. s, 1H, CH (2)), 4.38 (ush. s, 2H, CH (6,8)), 5.34 ( ush. s, 1H, CH (4)). , ppm): 17.6d13C NMR spectrum ( (a, C (9)), 23.4 (a, C (10)) 25.8.6 (a, C (11)), 28.1 (a, C ( 12)), 61.80 (q, C (2)), 67.30 (q, C (4)), 69.30 (q, C (6,8)). IK = 1530. Mass spectrum, m / z (Iotn (%)): 204 [M] + (90), 119 [N2H3CH (CH3) SC (CH3)] + (98), 74 [NCH (CH3) S] + (8 ), 57 [N2CH (CH3)] + (97). Found (%): C 47.50, H, 7.52; N, 13.63; S, 30.98. Calculated for S8N16N2S2 (%): C 47.02, H, 7.89; N, 13.71; S, 31.38.  
        2d. Oil light - yellow, yield 7%. Rf 0.63, SiO2-AgNO3. Eluent hexane-ethyl acetate-chloroform, 5:1:1. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 1.50 (d, 12N, SH3 (9,10,11,12)), 4.35 (s, 4H, CH (2,4, 6,8)). , ppm): 25.10d13C NMR spectrum ( (a, C (9,10,11,12)); 66.00 (a, C (2,4,6,8)). Mass spectrum, m / z (Iotn (%)): 204 [M] + (90), 119 [N2H3CH (CH3) SC (CH3)] + (98), 74 [NCH (CH3) S] + (8 ), 57 [N2CH (CH3)] + (97). Found (%): C 47.50, H, 7.52; N, 13.63; S, 30.98. Calculated for S8N16N2S2 (%): C 47.02, H, 7.89; N, 13.71; S, 31.38.  
               2,4,6,8-tetraethyl-3 ,7-ditia-1 ,5-diazabicyclo [3.3.0] octanes  
         7a. Colorless crystals, yield 42%. Tm. 58-59 ° C. Rf 0.58, Sakt (AH-5). Eluent CH2Cl2: hlf = 2:1. 1H NMR spectrum (d, ppm, CDCl3, J / Hz): 0.95 (d, 12N, 3SH3 (10,12,14,16) J = 6.09 Hz), 1.56 (m, 8H, SH3 (9, 11,13,15) J = 6.58 Hz), 4.79 (ush.s., 4H, CH (2,4,6,8), W1 / 2 = 18 Hz). 13C NMR spectrum (d, ppm): 11.39 (C, CH3 (12,14)), 11.75 (C, CH3 (10,16)), 25.54 (t, CH2 (11,13)), 31.44 ( m, CH2 (15,9)), 69.71 (q, C (4,6)), 72.41 (q, C (2,8)). Found (%): C 55.27, H, 9.18; N, 10.63; S, 24.54. Calculated for S12N24N2S2 (%): C 55.34, H, 9.29; N, 10.76; S, 24.68.  
           7b. Oil light - yellow, yield 21%. Rf 0.63, Sakt (AH-5). Eluent CH2Cl2: hlf = 2:1. 1H NMR Spectrum (d, ppm, CDCl3, J / Hz): 0.79 (m, 12N, 3SH3 (10,12,14,16) J = 3.90 Hz), 1.52 (m, 8H, SH3 (9, 11,13,15) J = 7.07 Hz), 4.00 (s, H, CH (2)), 4.78 (s, H, CH (4)), 4.9 (s, H, CH (6,8)). 13C NMR spectrum (d, ppm): 15.03 (C, CH3 (10)), 15.46 (C, CH3 (12)), 16.60 (C, CH3 (14,16)), 29.26 (t, CH2 ( 9)), 33.82 (t, CH2 (11)), 35.13 (t, CH2 (15,13)), 70.84 (q, C (2)), 73.29 (q, C (4)), 76.02 (q, C (6,8)). Found (%): C 55.27, H, 9.18; N, 10.63; S, 24.54. Calculated for S12N24N2S2 (%): C 55.34, H, 9.29; N, 10.76; S, 24.68.  
           7c. Oil light - yellow, yield 8%. Rf 0.67, Sakt (AH-5). Eluent CH2Cl2: hlf = 2:1. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 0.94 (m, 12N, SH3 (10, 12, 14, 16), J = 7.2); 1.72 - 1.67 (m, 4H, SN1 (9,11,13,15)), 4.57 (c, 4H, CH (2, 4, 6, 8), J = 5.8 Hz). , ppm): 13.99dSpectrum 13C NMR ( (a, C (10, 12 and 14, 16)), 28.52 (t, C (9,11,13,15)), 72.80 (q, C (2, 4, 6, 8)). Found (%): C 55.27, H, 9.18; N, 10.63; S, 24.54. Calculated for S12N24N2S2 (%): C 55.34, H, 9.29; N, 10.76; S, 24.68.  
           7d. Oil light - yellow, yield 8%. Rf 0.53, Sakt (AH-5). Eluent CH2Cl2: hlf = 2:1. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 1.04 (m, 12N, SH3 (10, 12, 14, 16), J = 7.2); 1.72 - 1.67 (m, 4H, SN1 (9,11,13,15)), 4.50 (c, 4H, CH (2, 4, 6, 8), J = 5.8 Hz). , ppm): 12.99d13C NMR spectrum ( (a, C (10, 12, 14, 16)), 27,50 (t, C (9,11,13,15)), 72.80 (d, C (2, 4 and 6, 8)). Found (%): C 55.27, H, 9.18; N, 10.63; S, 24.54. Calculated for S12N24N2S2 (%): C 55.34, H, 9.29; N, 10.76; S, 24.68.  
                2,4,6,8-tetrapropil-3 ,7-ditia-1 ,5-diazabicyclo [3.3.0] octanes  
            8a. Colorless crystals, yield 48%, Tm. 61-62 ° C. Rf 0.53, Sakt (AH-5). Eluent CH2Cl2: hlf = 2:1. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 0.83 (k, 12N, SH3 (11, 14, 17, 20)), 1.41 (m, 8H, SH2 (10, 13, 16, 19)), 2.25 (c, 8H, SH2 (9, 15, 12, 18)), 4.17 (c, 2H, CH (2,8) J = 4.8 Hz J = 8.4 Hz), 4.74 (m, 2H, CH (4,6) J = 4.8). , ppm): 13.93d13C NMR spectrum ( (a, C (11, 14, 17, 20)), 21.38 (t, C (13, 16)), 21.94 (t, C (10, 19) ), 41.54 (t, C (12, 15)), 42.91 (t, C (, 9 18)), 72.77 (d, C (4, 6)). Found (%): C 60.27, H, 10.15; N, 8.53; S, 20.24. Calculated for S20N40N2S2 (%): C 60.70, H, 10.19; N, 8.85; S, 20.26.  
           8b. Oil light - green, yield 17%. Rf 0.62, Sakt (AH-5). Eluent CH2Cl2: hlf = 2:1. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 0.96 (m, 12N, SH3 (11, 14, 17, 20)), 4.83 (d, 4H, CH (2, 4, 6, 8)). , ppm): 13.80d13C NMR spectrum ( (a, C (11, 14, 17, 20)), 20.83 (t, C (10, 13, 16, 19)), 41.18 (t, C ( 9, 12, 15, 18)), 71.04 (q, C (2, 4, 6, 8)), 73.71 (q, C (2,8)). Found (%): C 60.27, H, 10.15; N, 8.53; S, 20.24. Calculated for S20N40N2S2 (%): C 60.70, H, 10.19; N, 8.85; S, 20.26.  
           8c. Oil light - green, yield 11%. Rf 0.69, Sakt (AH-5). Eluent CH2Cl2: hlf = 2:1. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 0.96 (m, 12N, SH3 (11, 14, 17, 20)), 4.83 (d, 4H, CH (2, 4, 6, 8)). , ppm): 13.80d13C NMR spectrum ( (a, C (11, 14, 17, 20)), 20.83 (t, C (10, 13, 16, 19)), 41.18 (t, C ( 9, 12, 15, 18)), 71.04 (q, C (2, 4, 6, 8)). Found (%): C 60.27, H, 10.15; N, 8.53; S, 20.24. Calculated for S20N40N2S2 (%): C 60.70, H, 10.19; N, 8.85; S, 20.26. IR spectrum (cm-1): 670, 740, 880, 1120, 1450, 2972.  
           8d. Oil light - green, yield 11%. Rf 0.57, Sakt (AH-5). Eluent CH2Cl2: hlf = 2:1. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 0.84 (m, 12N, SH3 (11, 14, 17, 20)), 4.53 (d, 4H, CH (2, 4, 6, 8)). , ppm): 13.80d13C NMR spectrum ( (a, C (11, 14, 17, 20)), 23.80 (t, C (10, 13, 16, 19)), 42.01 (t, C ( 9, 12, 15, 18)), 72.04 (q, C (2, 4, 6, 8)). Found (%): C 60.27, H, 10.15; N, 8.53; S, 20.24. Calculated for S20N40N2S2 (%): C 60.70, H, 10.19; N, 8.85; S, 20.26. IR spectrum (cm-1): 670, 740, 880, 1120, 1450, 2972.  
                2,4,6,8-tetrabutyl-3 ,7-ditia-1 ,5-diazabicyclo [3.3.0] octane  
        9d. Oil red yield 52%. Rf 0.56, SiO2-AgNO3. Eluent Peter effect: CH2Cl2 = 5:3. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 0.81 (s, 6H, SH3 (12, 24)), 0.82 (s, 6H, SH3 (16, 20)), 1.31 ( ush. pp., 24N, SH3 (9, 10, 11, 13, 14, 15, 17, 18, 19, 21, 22, 23) W1 / 2 = 90 Hz), 4.42 (s, 2H, CH (2, 8)), 4.80 (c, 2H, CH (2,8)). , ppm): 13.67d13C NMR spectrum ( (a, C (16,20)); 13.76 (R, C (12, 24)), 22.16 (t, C (19, 15)), 22.26 ( m, C (11, 23)), 26.82 (t, C (14, 18)), 28.02 (t, C (10, 22)), 34.47 (t, C (13, 17)), 35.45 (t, C (9, 21)), 72.86 (q, C (4, 6)), 73.74 (q, C (2, 8)). Found (%): C 64.27, H, 10.28; N, 7.50; S, 17.19. Calculated for S20N40N2S2 (%): C 64.46, H, 10.82; N, 7.52; S, 17.24. IR spectrum (cm-1): 670, 740, 880, 1120, 1450, 2972.  
         9c. Oil red output of 20%. Rf 0.66, SiO2-AgNO3. Eluent Peter effect: CH2Cl2 = 5:3. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 0.74 (c, 3H, SH3 (12)), 0.88 (a, 3H, SH3 (16) J = 5.61 Hz), 0.74 ( to, 3H, SH3 (12)); 0.94 (s, 6H, SH3 (20.24)) 1.22 (s, 2H, SH2 (11)), 1.51 (s, 2H, SH2 (15)), 1.88 ( s, 4H, SH2 (19,23)), 2.25 (ush.s, 16N, SH2 (9,10,17,18,13,14,21,22)), 4.67 (s, 1H CH (2)), , 4.76 (m, 1H CH (4) J = 5.13 Hz), 4.87 (s, 2H, CH (6,8)). , ppm): 13.69d13C NMR spectrum ( (a, C (20,24)); 13.70 (R, C (16)), 13.73 (C, C (12)), 22.17 (t, C ( 19, 23)), 22.19 (t, C (15)), 22.26 (t, C (11)), 25.45 (t, C (18,22)), 25.54 (t, C (14)), 25.71 ( t, C (10)) 33.36 (t, C (17,21)), 33.67 (t, C (13)), 33.95 (t, C (9)), 68.17 (q, C (6,8) ), 71.11 (q, C (4)), 72.37 (q, C (4)). Found (%): C 64.27, H, 10.28; N, 7.50; S, 17.19 .. Calculated for S20N40N2S2 (%): C 64.46, H, 10.82; N, 7.52; S, 17.24. IR spectrum (cm-1): 670, 740, 880, 1120, 1450, 2972.  
        9d. The oil is dark - orange, yield 22%. Rf 0.78, SiO2-AgNO3.Elyuent hexane-ethyl acetate-chloroform, 5:1:1. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 0.84 (ush.s, 12N, SH3 (13, 18, 23,28)), 1.29 (ush.s, 32N, SH2 ( 9,10,11,12,14,15,16,17,19,20,21,22,24,25,26,27)), 4.23 (ush.s, 3H, CH (4,6,8) ) 5.15 (s, 1H, CH (2)). , ppm): 13.67d13C NMR spectrum ( (a, C (13,18,23,28)); 22.36 (t, C (12,17,22,27)), 26.66 (t, C ( 21,26)), 27.08 (t, C (16)), 27.63 (t, C (11)), 31.12 (t, C (20,25)), 31.41 (t, C (15)), 31.40 ( t, C (10)) 37.76 (t, C (19,24)), 38.50 (t, C (14)), 38.80 (t, C (9)), 68.17 (q, C (6,8) ), 71.10 (q, C (4)), 72.37 (q, C (2)). Found (%): C 67.16, H, 11.22; N, 6.52; S, 14.24. Calculated for S24N48N2S2 (%): C 67.23, H, 11.28; N, 6.53; S, 14.96. IR spectrum (cm-1): 670, 740, 880, 1120, 1450, 2972.  
                  2,4,6,8-tetrapentil-3 ,7-ditia-1 ,5-diazabicyclo [3.3.0] octane  
          10b. Oil is dark - orange, yield 54%. Rf 0.57, SiO2-AgNO3 .. Eluent hexane-ethyl acetate-chloroform, 5:1:1. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 0.84 (k, 12N, SH3 (13, 18, 23, 28)), 1.10 - 1.50 (m, 16N, SH2 (11, 12, 16, 17, 21, 22, 26, 27)), 1.50 - 2.00 (m, 16N, SH2 (9, 10, 14, 15, 19, 20, 25, 24)), 4,24 (ush. pp., 4H, CH (2, 4, 6, 8)). , ppm): 13.80d13C NMR spectrum ( (a, C (13, 18, 23, 28)), 22.43 (t, C (12, 17, 22, 27)), 27.22 (t, C ( 11, 16, 21, 26)), 31.51 (t, C (10, 15, 20, 25)), 38.91 (t, C (9, 14, 19, 24)), 71.21 (q, C (2, 4, 6, 8)). Found (%): C 67.16, H, 11.22; N, 6.52; S, 14.24. Calculated for S24N48N2S2 (%): C 67.23, H, 11.28; N, 6.53; S, 14.96.  
          10c. The oil is dark - orange, yield 34%. Rf 0.68, SiO2-AgNO3. Eluent hexane-ethyl acetate-chloroform, 5:1:1. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 0.84 (ush.s, 12N, SH3 (13, 18, 23,28)), 1.29 (ush.s, 32N, SH2 ( 9,10,11,12,14,15,16,17,19,20,21,22,24,25,26,27)), 4.23 (ush.s, 3H, CH (4,6,8) ), 5.15 (s, 1H, CH (2)). , ppm): 13.67d13C NMR spectrum ( (a, C (13,18,23,28)); 22.36 (t, C (12,17,22,27)), 26.66 (t, C ( 21,26)), 27.08 (t, C (16)), 27.63 (t, C (11)), 31.12 (t, C (20,25)), 31.41 (t, C (15)), 31.40 ( t, C (10)) 37.76 (t, C (19,24)), 38.50 (t, C (14)), 38.80 (t, C (9)), 68.17 (q, C (6,8) ), 71.10 (q, C (4)), 72.37 (q, C (2)). Found (%): C 67.16, H, 11.22; N, 6.52; S, 14.24. Calculated for S24N48N2S2 (%): C 67.23, H, 11.28; N, 6.53; S, 14.96.  
          10d. The oil is dark - orange, yield 12%. Rf 0.75, SiO2-AgNO3.Elyuent , ppm, J, Hz, 20 ° C):dhexane-ethyl acetate-chloroform, 5:1:1 1H NMR spectrum ( 0.84 (k, 12N, SH3 (13, 18, 23, 28)), 1.10 - 1.50 (m, 16N, SH2 (11, 12, 16, 17, 21, 22, 26, 27)), 1.50 - 2.00 (m, 16N, SH2 (9, 10, 14, 15, 19, 20, 25, 24)), 4,24 (ush.s., 4H, CH (2, 4, 6, 8)). , ppm): 13.80d13C NMR spectrum ( (a, C (13, 18, 23, 28)), 22.43 (t, C (12, 17, 22, 27)), 27.22 (t, C ( 11, 16, 21, 26)), 31.51 (t, C (10, 15, 20, 25)), 38.91 (t, C (9, 14, 19, 24)), 71.21 (q, C (2, 4, 6, 8)). Found (%): C 67.16, H, 11.22; N, 6.52; S, 14.24 .. Calculated for S24N48N2S2 (%): C 67.23, H, 11.28; N, 6.53; S, 14.96.  
2,4,6,8-tetrafenil-3 ,7-ditia-1 ,5-diazabicyclo [3.3.0] octane (14). Orange kritally, the yield of 19%. Tm 88 ° C. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 4.79 (ush.s, 4H, CH (2,4,6,8) W1 / 2 = 17.9), 7.51 (d, 4H , CH (12, 18, 24,30) J = 2,29 Hz), 7.90 (s, 12N, CH (11, 17, 29, 23, 10, 16, 28,22,14,20,32,26 )). , ppm): 53.39d13C NMR spectrum ( (q, C (2,4,6,8)); 128.09 (q, C (12,18,30, 24)), 128.41 (q, C ( 10, 16, 22, 28)), 128.74 (q, C (11, 13,17,19,23,25,29,31)), 131.18 (q, C (14,20,26,32)); 140.00 (s, C (9,15,21,27)). Found (%): C 74.14, H, 5.21; N, 6.05; S, 14.10. Calculated for S28N24N2S2 (%): C 74.30, H, 5.34; N, 6.19; S, 14.17.  
2,4,6,8-tetrakis (4-methoxyphenyl) -3,7-ditia-1 ,5-diazabicyclo [3.3.0] octanes (15).  
          15a. Orange crystals, yield 22%. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 3.85 (s, 12N, SH3 (33,36,38,40)), 5.69 (ush.s, 4H, CH (2, 4,6,8)), 6.85 (d, 4H, CH (13,19,25,31) J = 7,2 Hz), 7.27 (s, 4H, CH (10,16,22,28)), 7.78 (s, 4H, CH (14,20,26,32)). , ppm): 52.73d13C NMR spectrum ( (a, C (34,36,38,40)); 55.56 (q, C (2,4,6,8)); 114.30 (q, C ( 11,13,17,19,23,25,29,31)), 129.19 (q, C (10,16,22,28)), 130.46 (q, C (9,15,21,27)), 131.99 (q, C (14,20,26,32)), 162.14 (q, C (12,18,24,30)). Found (%): C 67.06, H, 5.12; N, 4.30; S, 11.01. Calculated for S32N32N2O4S2 (%): C 67.11, H, 5.63; N, 4.89; S, 11.20; O, 11.17.  
            15b. Orange crystals, yield 22%. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 3.83 (s, 12N, SH3 (33,36,38,40)), 5.99 (ush.s, 4H, CH (2, 4,6,8)), 6.95 (d, 4H, CH (13,19,25,31) J = 8,8 Hz), 7.36 (s, 4H, CH (10,16,22,28)); 7.81 (s, 4H, CH (14,20,26,32)). , ppm): 52.73d13C NMR spectrum ( (a, C (34,36,38,40)); 51.0 (d, C (2,4,6,8)); 114.25 (d, C ( 11,13,17,19,23,25,29,31)), 129.50 (q, C (10,16,22,28)), 130.3 (q, C (9,15,21,27)); 132.3 (d, C (14,20,26,32)), 161.12 (d, C (12,18,24,30)). Found (%): C 67.06, H, 5.12; N, 4.30; S, 11.01. Calculated for S32N32N2O4S2 (%): C 67.11, H, 5.63; N, 4.89; S, 11.20; O, 11.17.  
              15C. Orange crystals, yield 22%. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 3.76 (s, 12N, SH3 (33,36,38,40)), 5.31 (ush.s, 4H, CH (2, 4,6,8)), 6.99 (d, 4H, CH (13,19,25,31) J = 7,81 Hz), 7.38 (s, 4H, CH (10,16,22,28)), 7.83 (s, 4H, CH (14,20,26,32)). , ppm): 52.73d13C NMR spectrum ( (a, C (34,36,38,40)); 58.41 (q, C (2,4,6,8)); 116.25 (q, C ( 11,13,17,19,23,25,29,31)), 126.19 (q, C (10,16,22,28)), 130.20 (q, C (9,15,21,27)); 132.0 (d, C (14,20,26,32)), 159.86 (d, C (12,18,24,30)). Found (%): C 67.06, H, 5.12; N, 4.30; S, 11.01. Calculated for S32N32N2O4S2 (%): C 67.11, H, 5.63; N, 4.89; S, 11.20; O, 11.17.  
2,4,6,8-tetrapiridin - 3 - yl - 3,7-ditia-1 ,5-diazabicyclo [3.3.0] octane (16) Orange crystals, yield 24%. Tm 79 ° C. , ppm, J, Hz,d1H NMR spectrum ( 20 ° C): 4.55 (ush.s, 4H, CH (2,4,6,8) W1 / 2 = 17.9), 7.12 (ush.s , 2H, CH (13, 23)), 7.30 (d, 4H, CH (14,16,32,22)), 8.42 (ush.s, 2H, CH (10,26)), 8.58 (s, 4H , CH (12,18,24,30)). , ppm): 51.17d13C NMR spectrum ( (q, C (2,4,6,8)); 123.78 (q, C (13,17,23,31)), 129.65 (q, C ( 9,15,21, 27)), 134.88 (q, C (14,16,22,32)), 150.30 (q, C (10,20,26,28)), 151.91 (q, C (12, 18,24,30)). Found (%): C, 63.06, H, 4. 12; N, 18.30; S, 14.01. Calculated for S24N20N6S2 (%): C 63.13, H, 4.42; N, 18.41; S, 14.05.  
            We are grateful to Corresponding Member. Sciences Prof. WM Dzhemilev and Prof. LM Khalilov for participation in the discussion of results.  

 

 

 

 

 

 

 

 

 

 

 

 

 

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