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Reactions with alkynes result in the formation of a mixture of regioisomeric divinyl sulfides. ... 1 : 2 system, the yield of the thiacyclane also increases but products of ... upon reaction of alkenes with thiobisamine–thionyl halide systems (Scheme ...

ISSN 00271314, Moscow University Chemistry Bulletin, 2014, Vol. 69, No. 6, pp. 254–265. © Allerton Press, Inc., 2014. Original Russian Text © N.V. Zyk, A.Yu. Gavrilova, M.A. Nechaev, O.B. Bondarenko, N.S. Zefirov, 2014, published in Vestnik Moskovskogo Universiteta. Khimiya, 2014, No. 6, pp. 337–350.

Reaction of Unsaturated Compounds with the Thiobisamine–SOHal2 System N. V. Zyk, A. Yu. Gavrilova, M. A. Nechaev, O. B. Bondarenko, and N. S. Zefirov Department of Chemistry, Moscow State University, Moscow, Russia email: [email protected] Received April 15, 2014

Abstract—A convenient method for the synthesis of di(βhaloalkyl)sulfides based on the reaction of unsat urated compounds with the thiobisamine–SOHal2 (Hal = Cl, Br) system was created. The reaction proceeds through an electrophilic mechanism with the formation of transaddition products. Reactions with alkynes result in the formation of a mixture of regioisomeric divinyl sulfides. Keywords: thiobisamines, thionyl halogenides, alkenes, dienes, alkynes, sulfenylation DOI: 10.3103/S002713141406008X

Di(βhaloalkyl)sulfides are potentially biologi cally active compounds [1] that may be used as intermediates in the synthesis of βsubstituted alkyl sulfides, sulfoxides, and sulfones. The main method for the preparation of di(βchloroalkyl)sulfides is based on electrophilic addition of sulfur dichloride (sulfoxylic acid dichloride) to olefins; however, this method is inconvenient from the preparative point of view due to the necessity of working with freshly prepared SCl2 [2]. The possibility of the synthesis of di(βbromoalkyl)sulfides by means of direct addi tion of SBr2 to olefins has not been studied because of the extremely low stability of sulfur dibromide. Recently, a new method for the synthesis of both di(βchloroalkyl)sulfides and di(βbromoalkyl)sul fides by reaction of alkenes with thiobisamines in the presence of phosphorus oxohalides was created [3, 4]. The possibility of using thionyl chloride as a coreagent in these reactions has been illustrated based on one example [5]. In our works devoted to studying the possibility of the activation of weak electrophiles with thionyl halides [6, 7], we studied reactions of alkenes, dienes, and alkynes with the following systems:

X

N S N

thiobismorpholine (TBM)–SOHal2 (Hal = Cl, Br) and thiobispiperidine (TBP)–SOHal2 (Hal = Cl, Br). It was found that cyclohexene, norbornene, cyclo hexadiene1,4, and cyclooctadiene1,5 react to form transdi(βhaloalkyl)sulfides (Scheme 1), with the best yields of sulfenhalogenation products being achieved when thionyl halides are added to a thio bisamine followed by addition of an alkene at a tem perature not higher than –40°C (Table 1). When using thionyl chloride as a coreagent, the optimal ratio of R2NSNR2 : SOCl2 is equal to 1 : 2, whereas equimolar amounts of thiobisamine and SOBr2 should be used in the case of thionyl bromide, due to the fact that use of an excess of thionyl bromide results in the formation of alkene bromination products. Therefore, at the first glance, sulfur dihalides (SHal2) that react with the olefinic C=C bond are gen erated in thiobisamine–SOHal2 systems. However, in some cases results that are inconsistent with this sup position were obtained. First, while addition of SCl2 to 1,4cyclohexadiene results in the formation of either 2,5bisendo7thiabicyclo[2.2.1]heptane or a poly mer product [8] depending on the reaction conditions, we isolated di(2halocyclohex4enyl)sulfides 3a,b independent of variation of the conditions (Table 1).

X + SOHal2 +

Hal

S

Hal

X = O, Hal = Cl, Br Scheme 1.

Second, it is known that upon reaction of sulfur dichloride with norbornadiene a single product from

the attack of an electrophile on the endoside of diene, namely thiacyclane 5a [9]. Upon reaction of norbor

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REACTION OF UNSATURATED COMPOUNDS

1 : 2 system, the yield of the thiacyclane also increases but products of norbornadiene bromination are formed as by products.

nadiene with thiobispiperidine in the presence of thio nyl chloride (TBP : SOCl2 = 1 : 2) and with thiobis morpholine in the presence of thionyl bromide (TBM : SOBr2 = 1 : 1), formation of products from exoattack on the C=C bond, namely disulfides 6a, 6b (Table 2), along with thiacyclanes 5a, 5b,was observed. In the reaction of norbornadiene with thiobispiperi dine in the presence of thionyl bromide (TBP : SOBr2 = 1 : 1), endo and exosulfenamides 7 and 8 were iso lated in addition to thiacyclane 5b, while carrying out the reaction at a higher dilution of the reaction mix ture resulting in increasing the yield of endosulfena mide 7 with simultaneous decreasing of the yield of the product 5b (Scheme 2). Vice versa, the use of a twofold excess of SOBr2 allows the yield of thiacyclane 5b to be increased due to the complete disappearance of endo sulfenamide 7 (Table 2). In the case of sulfenylation of norbornadiene with the thiobismorpholine : SOBr2 =

Hal

Taking the above facts into account, we do not exclude the possibility of in situ formation of sulfur dihalides. Nevertheless, we assume that sequential activation of one S–N bond of thiobisamine occurs upon reaction of alkenes with thiobisamine–thionyl halide systems (Scheme 3): when thiobisamine reacts with thionyl halide, aminosulfenhalide (I) is formed and it reacts with alkene to form sulfenamide (II). Subsequent reaction of sulfenamide (II) with thionyl halide or (R2N)2S(O)Hal (when Hal = Br) results in the formation of sulfenhalide (III), which may either react with an alkene to give sulfide (IV) or transform into disulfide (V) (the formation of disulfide should be facilitated by an increase in the reaction temperature).

Hal

(R2N)2S SOHal2

S +

Hal 6a, 6b

5a, 5b

R2N–S–Hal +

R2N

I

R

R + R2N–S–Hal R

P R Hal

SNR

SNR2 7

2

Hal 8

Scheme 2.

R2N–S–NR2 + SOHal2

R

Hal +

+

S Hal = Cl (5a, 6a), Br (5b, 6b); R = (–CH2)5, Hal = Br (7, 8)

255

R R Hal

S R R R R IV

O S

Hal

S NR2 R SOHal2 R R or R NS(O)Hal 2 R Hal II R

R

R

R

R R Hal

P R Hal

S Hal R R III

S S R R R R V

R R Hal

Scheme 3.

To confirm the scheme we proposed, we studied the reaction of thionyl halides with a mixture of iso meric sulfenamides 9 and 10 (9 : 10 = 1 : 1) resulting from the reaction of norbornadiene with morpholi nosulfenbromide (Scheme 4). As a result, thiacy clane 5b and disulfide 6b (reaction with SOBr2), thi acyclanes 5a, 5c and disulfide 6b (reaction with SOCl2) were isolated. Obviously, thiacyclane 5c is formed from isomer 9, while disulfide 6b is a product of dimerization of sulfen halides 11a, 11b formed from isomer 10 (Scheme 5). MOSCOW UNIVERSITY CHEMISTRY BULLETIN

Thiacyclane 5a formed in the reaction of sulfena mides 9, 10 with thionyl chloride is a product of nucleophilic substitution of bromine by chlorine under the action of SOCl2. Thus, upon the reaction of a mixture of thiacyclanes 5c and 5a (5c : 5a = 2.9 : 1.0) with an excess of thionyl chloride, only compound 5a was isolated (Scheme 6). It was found that in the reaction of norbornadiene with the thiobismorpholine–SOCl2 (1 : 1) system, the main reaction product is sulfenamide 12, which is in agreement with the sequential activation of S–N bonds of thiobisamine (Scheme 7).

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Table 1. Products of reaction of cyclohexane, norbonene, cyclohexadiene1,4, and cyclooctadiene1,5 with thiobismor pholine (TBM) and thiobispiperidine (TBP) in the presence of SOHal2 Product formula

Alkene

SOHal2

Ratio of reagents C=C : (R2N)2S : SOHal2

SOCl2

2:1:2

TBM

1a

99a

2:1:2

TBP

1a

95a

2:1:1

TBM

1b

38a

2:1:1

TBP

1b

56a

2:1:2

TBM

2a

97b

2:1:2

TBP

2a

99b

2:1:1

TBM

2b

36c

2:1:1

TBP

2b

85c

2:1:2

TBM

3a

90d

2:1:2

TBP

3a

91d

2:1:1

TBM

3b

59d

2:1:1

TBP

3b

60d

1:1:2

TBM

4a

64

1:1:2

TBP

4a

99

1:1:1

TBM

4b

55

1:1:1

TBP

4b

65

S Hal

2

SOBr2

SOCl2

S SOBr2

Hal

2

SOCl2

S Hal

2

SOBr2

SOCl2

Hal

(R2N)2S

Product Yield, %

S SOBr2

Hal

The dl : meso ratio is (a) 5 : 4; (b) 3 : 2; (c) 5 : 3; (d) compounds 3a and 3b were obtained as dl and mesoisomers, however, we failed to determine their ratio due to proximity of proton signal values in the 1H NMR.

Table 2. Products of the reaction of norbornadiene with thiobismorpholine (TBM) and thiobispiperidine (TBP) in the presence of SOHal2 SOHal2

SOCl2

SOBr2

Thiobisamine

Products of endoattack

Products of exoattack

5

7

6

8

TBM

1:1:2

100







TBP

1:1:2

84



15



TBM

1:1:1

34



22



1:1:2

67a







1:1:1

56

3



31

1 : 1 : 1b

26

36



30

1:1:2

61



16

13

TBP

a

Ratio of reagents C=C : (R2N)2S : SOHal2

Products of norbornadiene bromination were isolated; b reaction was conducted at high dilution. MOSCOW UNIVERSITY CHEMISTRY BULLETIN

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O

Br

NSBr

SN 9

S

Br 6b, 43%

SN

9 + 10 = 98% 9 : 10 = 1 : 1

Br

O

10 SOCl2

Br

Br 6b, 8% +

Cl Cl + S 5c, 47%

S 5b, 39%

2

O

+

SOBr2

Br +

257

Cl S 5a, 16%

Scheme 4.

Br

Br

Br

SOBr2

S 5b

9

SN

SBr

11b

Br

Cl S 5c

O

SN

SOBr2

Br 2

SOCl2

SCl

O SOCl2 11a Br

10 Br

S Br 6b Scheme 5.

Br

Cl SOCl Cl S 5c Scheme 6.

bicyclic products (route B); rearrange [10, 11] (route C); and undergo an intramolecular AdE reaction to form isomers 15–19 (route D) (Scheme 8).

Cl

2

S 5a

To widen the model series and to determine the application limits of the sulfenylation method we pro posed, reactions of thiobisamines with cyclooctatet raene (COT) in the presence of SOCl2 were studied. We assumed that sulfenchloride 13 that forms in the reaction may participate in the following transforma tions depending on conditions: it may react intermo lecularly to form sulfides (route A); isomerize to form

O

N S N

2

It was found that the result of the reaction of cyclooctatetraene with thiobisamines in the presence of thionyl chloride depends significantly on reaction time. Thus, when conducting the reaction for 2 h we obtained a complex mixture of products. We failed to separate the obtained products by column chromatog raphy. An investigation of the reaction mixture by chromatography–mass spectrometry showed that there were three peaks in the chromatogram (one of them was broadened).

S

O

SN +

SOCl2

Cl 2a, 14%

2

Cl 12, 14%

Scheme 7.

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Table 3. Products of reaction of COT with thiobisamines in the presence of SOCl2* Reaction conditions Thio bisamine ratio C=C : (R2N)2S : time, h SOCl2 TBM

1:1:2 1:2:4 1:1:2 1:1:2 1:2:4 1:2:4

TBP

Yields of products, %

Ratio of products, % 14a, 14b

COT

48 24 2 48 2 48

14, 16, 19a

17.0 – 6.0 5.0 1.7 –

72 65 23 46 64 70

major

minor

– – 45 18 43 4

– – 13 8 11 2

16

19a

– – 6 2 11 4

100 100 36 72 35 90

* Yields and ratios of products were determined from 1H NMR spectroscopic data.

S

S S

Cl Cl

Cl Cl S A

SNR2

SCl

Cl

Cl

SCl

ClCl

Cl

S S

B

14 C

SCl

13

ClCl

Cl

D

Cl

Cl

S

Cl

S

Cl

Cl

S

S

Cl 15

16

17

Cl

Cl

S Cl

Cl

18

19a

Scheme 8.

Each peak has a corresponding mass spectrum that has the same scheme of fragmentation of the molecular ion, with the masses and ratios of the intensities of the molecular ion (206 [M]+) and isotopic ions (208 [M + 2]+, 210 [M + 4]+) corresponding to compounds with the empirical formula C8H8Cl2S [12]. An accurate analy sis of the 1H NMR spectra of reaction mixtures allowed us to distinguish four sets of signals. One of them consists of four multiplets and corresponds to the symmetrical structure of 19a [13]. There are eight multiplets of protons in each of the other three sets of signals and signals of three protons appear in the region of 3.5–4.9 ppm, which makes it possible to exclude trienes and symmetrical structures from con sideration. Therefore, we believe that thiacyclane 16 and bicyclic sulfenchloride 14 in the form of two iso

mers a and b (signals of 14a and 14b in the 1NMR spectrum have the same set of coupling constants that decrease concordantly upon addition of thionyl chlo ride) are formed as well as thiacyclane 19a (Table 3). Note that the structure of isomers 14a, 14b was not established definitively. On the one hand, it is not pos sible to determine the positions of substituents in cyclobutane from the set of coupling constants [14] and, on the other hand, the use of special methods of investigation (for example, NOE) for a mixture of four products is incorrect (Scheme 9). When conducting the reaction for 24–48 h we isolated a single product, namely thiacyclane 19a (Table 3). Cyclooctatetraene (COT) is less reactive in comparison to cyclooctadiene, so that the opti mal ratio of substrate and reagents in this reaction is

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Table 4. Products of the reaction of COT with thiobismorpholine in the presence of SOBr2a Yield of product, %b

Reaction conditions COT : (R2N)2S : SOBr2

time, h

COT

19b

20

21

1:1:1

2

7

7

10



1:1:1

48

2

9

15



1:2:2

48

35

4

2



1:2:4

2



16



63

1:2:4

48



12



84

a Yields and ratios of products were determined from 1H NMR spectroscopic data; b in all cases, except the experiment where the ratio of reagent = 1 : 2 : 4 (reaction time was 48 h), unidentified products of bromination and aromatization are present.

tetraene : thiobisamine : SOCl2 = 1 : 2 : 4. A twofold excess of the reagents does not change the ratio of products; however, it allows 100% conversion of COT. When thionyl bromide is used as a coreagent, the formation of 9thia2,6bis(dibromo)bicycle[3,3,1]non H

H

SCl

(R2N)2S SOCl2

adiene2,6 thiacyclane 19b was detected in trace amounts in the 1H NMR spectrum. The main products (depending on the ratio of tetraene : reagents) are bro mides 20, 21 (Scheme 10) as well as their isomeric bro mides and aromatization products that we failed to isolate and identify (Table 4). SCl

+

H 14a

+

Cl

Cl + Cl

S

Cl

H 14b

Cl

16

Cl S

19a

Scheme 9. O

S

N

S

SOBr2

Br

Br

Br +

2

+

Br

Br 19b

Br

Br Br 21

20 Scheme 10.

Complete conversion of COT was achieved only at the ratio of tetraene : thiobisamine : SOBr2 = 1 : 2 : 4; however, in this case the main product is tetrabromide 21 (Table 4). It is obvious that formation of dibromide 20 is a result of bromination of COT, which was con firmed when conducting the reaction of this com pound with equimolar amount of bromine 21 (Scheme 11): H 1 8

Br2

6 7

H 20, 92%

Br H H Br

Scheme 11.

Transposition of bromine atoms in compound 20 was proven by conducting a NOE experiment. When MOSCOW UNIVERSITY CHEMISTRY BULLETIN

irradiating the signal H7CBr (δ 4.94 ppm), the Over hauser effect is observed for protons H1 and H6 (η = 1%). When irradiating the signal (δ 4.65 ppm), the Over hauser effect was not observed, which is in agreement with the above structure. Tetrabromide 21 is probably formed upon bromina tion of compound 20; however, a complex mixture of products was obtained upon reaction of COT with a two fold excess of bromine or with thionyl bromide [15, 16]. Therefore, reaction of COT with thiobismorpho line in the presence of thionyl halides may be consid ered as a preparative method for the synthesis of thia cyclane 19a only. Reactions of alkynes (heptyne1 and phenylacety lene) with thiobismorpholine in the presence of thio nyl chloride proceed smoothly with good yields. Divi nyl sulfides were isolated as resulting products. For mation of thiiranes was not detected, which is in

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agreement with the data on the addition of sulfur dichloride to alkynes [17]. When ascertaining the structure of the obtained compounds we took the fol lowing issues into consideration: first, at the first stage, addition of the electrophilic agent is possible either according to Markovnikov’s rule or contrary to it (with a ratio of addition products that depends on both the reaction conditions (for example, solvent) and the reagents [18]); second, formation of Z and Eisomers

O

S

N 2

R

SOCl2

R S

R

is possible. An analogous situation is also observed at the second stage of the addition of the already formed vinyl sulfide. On the whole, the number of possible isomers is equal to nine. However, it is known that electrophilic addition of sulfur chloride [17], amino sulfenchlorides [18–21], and sulfenhalides [18, 22] usually proceeds with the formation of transproducts, which allowed us to reduce the number of possible iso mers to three (22–24) (Scheme 12).

Cl

R

SNR2

+

R2SN

Cl H H

R Cl 22a, 22b

Cl H R TBM, SOCl2

H R TBM, SOCl2

R

Cl

H

Cl

S

H R

S

R R

H Cl 24a, 24b

H Cl 23a, 23b

R = C5H11 (22a, 23a) 22a + 23a = 52%, 22a : 23a = 2 : 1 R + Ph (22b, 23b) 22b + 23b = 93%, 22b : 23b = 1 : 1 Scheme 12.

Data on the values of chemical shifts of protons of vinyl chlorides and sulfides in the 1H NMR spectra are rather inconsistent [17, 19–22]. For this reason, to establish the structures of the obtained isomers, we used the data of 13C NMR spectroscopy. Thus, for compound 23a chemical shifts of carbon signals in SHC= and ClHC= are equal to 113.9 and 117.3 ppm, respectively, and those of carbon atoms in SRC= and ClRC= are 137.4 and 140.0 ppm, respectively, that is, signals of carbon atoms bonded with chlorine atom are shifted downfield. The signal of carbon in H2C–CCl= is also shifted downfield as compared to the signal of carbon in H2C–CS=. The structures of 22a and 24a have a symmetry axis; therefore, carbons at the double bond are equivalent and have equal chemical shifts. In this case, the chemical shift of carbon signals in XHC= and YRC= is equal to 118.6 ppm and 136.3 ppm, that is, comparison of values of the chemical shifts with anal ogous values for compound 23a allows one to con clude that X = Cl and Y = S, which is in agreement with the structure of 22a. The chemical shift of carbon signal for H2C–C= has also the value corresponding to the carbon signal for H2C–CS=. Therefore, in the 1H NMR spectrum of compounds 22a and 23a signals of protons in HCCl are shifted downfield as compared to the signal of the proton in HCS in compound 23a. Using the obtained results for compounds 22a and 23a, we assigned the proton and carbon signals for compounds 22b and 23b.

Therefore, reactions of alkenes, dienes and alkynes with thiobisamines in the presence of thionyl halides is a convenient method for the synthesis of di(βhaloalkyl)sulfides. MATERIALS AND METHODS and 13C NMR spectra were recorded on a Bruker Avance spectrometer (with working frequen cies of 400 and 100 MHz, respectively) at 28°C in CDCl3. Chemical shifts are given in the δ scale (ppm) relative to Me4Si as an internal standard. Mass spectra were recorded on a Finnigan MIAT TSQ 7000 chro mato–mass spectrometer at the energy of ionizing electrons of 70 eV. Monitoring of the reaction progress and individuality of compounds obtained was carried out by TLC on a fixed layer of silica gel (Silufol UV254). 1H

REACTION OF N,NTIOBISAMINES WITH ALKENES IN THE PRESENCE OF SOHal2 (GENERAL PROCEDURE) Thionyl chloride (or bromide) in absolute methyl ene chloride was slowly added to a solution of N,Ntiobisamines in absolute methylene chloride, with stirring at –40°C in a flow of dry argon and, after a second cooling of the reaction mixture to –40°C, a solution of the alkene in absolute methylene chloride

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REACTION OF UNSATURATED COMPOUNDS

was slowly added in drops. The reaction mixture was stirred for 1–2 h with a gradual increase in the temper ature to room temperature. The solution was passed through a columnfilter with silica gel or hydrolyzed followed by extraction. The solvent was evaporated in a vacuum. The reaction conditions and yields of the obtained products are given in Tables 1–4. The 1H NMR spec tra of the following compounds are in agreement with those published previously: 1, 2 [4], 4a [8], 5 [4], 12 [23], 19a [13, 24], and 21 [16]. The data on the 1H NMR spectra of compounds 7–10 are provided in Table 5. Di(2bromocyclohexyl)sulfide (dl : meso = 5 : 4) (1b). 13C NMR (CDCl3, δ, ppm): 23.07, 23.60, 29.71, 30.55, 31.00, 33.40, 34.02 (C of framework (dl and meso)), 50.63 (CS(dl)), 51.76 (CS(meso)), 56.87 (CBr(dl)), 58.13(CBr(meso)). Di(2chlorocyclohex4enyl)sulfide (dl and meso) (3a). Orange oily substance, Rf 0.78 (eluent: petro leum ether : ethyl acetate = 1 : 3). 1H NMR (CDCl3, δ, ppm, J/Hz): 2.21 m (1H, CHframework) 2.41 m (1H, CHframework), 2.85 m (2H, CHframework), 3.20 m (HCS), 4.25 m (1H, CHCl), 5.55 m (1H, HC=), 5.65 m (1H, HC=). 13C NMR (CDCl3, δ, ppm): 29.88, 30.03 (C5), 32.19, 32.59 (C2), 45.67, 46.18 (1H, HCS), 58.51, 59.58 (1H, HCCl), 122.99, 123.12 (1H, HC=), 124.03, 124.36 (1H, HC=). Found (%): C (54.80); H (6.41). C12H16Cl2S. Calcu lated (%): C (54.75); H (6.41). Di(2bromocyclohex4enyl)sulfide (dl and meso) (3b). White crystalline substance. Mp = 69.5°C. Rf = 0.87. (eluent: petroleum ether : ethyl acetate = 1 : 3). 1H NMR (CDCl , δ, ppm, J/Hz): 2.25 m (1H, CH 3 framework) 2.57 m (1H, CHframework), 2.93 m (1H, CHframework), 3.08 m (1H, CHframework), 3.28 m (1H, HCS), 4.39 m (1 H, CHCl), 5.57 m (1H, HC=), 5.65 m (1H, HC=). 13C NMR (CDCl3, δ, ppm): 29.88 (C5), 32.07 (C2), 45.68, 45.84 (HCS), 50.02, 50.69 (HCBr), 123.78 (HC=), 122.92, 122.99 (HC=). Found (%): C (40.77); H (4.73). C12H16Br2S. Calculated (%): C (40.92); H (4.55). 2,6Dichloro9thiabicyclo[3.3.1]nonane (4a). White crystalline substance. Mp = 100–103°C. Mp [25] = 101–102°C. 1H NMR (CDCl3, δ, ppm, J/Hz): 2.35– 1

5

8

2.17 m (6H, C H 2 , CH 2 , CH 2 ), 2.67 and 2.70 m (2H, 4

CH 2 ), 2.86 dt (HCS, J = 3.2, J = 4.1), 4.72 ddd (2H, CHCl, J = 3.6, J =7.4, J = 10.6). 13C NMR (CDCl3, δ, ppm): 28.30 (C4, C8), 32.60 (C1, C5), 37.30 (CS), 62.50 (CCl). 2,6Dibromo9thiabicyclo[3.3.1]nonane (4b). Lightyellow crystalline substance. Mp = 137–138°C. Mp [25] = 134.5–135.5°C. 1H NMR (CDCl3, δ, ppm, 4

8

J/Hz): 2.25–2.45 m (4H, CH 2 , CH 2 ), 2.56 m (4H, 1

5

C H 2 , CH 2 ), 2.97 m (HCS), 4.95 m (2H, CHBr). MOSCOW UNIVERSITY CHEMISTRY BULLETIN

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C NMR (CDCl3, δ, ppm): 30.50 (C4, C8), 33.60 (C1, C5), 37.70 (CS), 56.50 (CBr). Found (%): C (31.98), H (4.22). C8H12Br2S. Calculated (%): C (32.02), H (4.00). 2,6Diexochloro8thiatricyclo[2.2.1.13,5]heptane (5a). 13C NMR (CDCl3, δ, ppm): 35.9 (C7); 48.5 (CS); 50.4 (C1); 56.5 (C4); 64.3 (CCl). Mass spectrum, m/z (Irel, %): 198 (5) [M + 4]+, 196 (24) [M + 2]+, 194 (36) [M]+, 161 (36), 159 (100), 125 (24), 123 (18), 100 (40). 2,6Diexobromo8thiatricyclo[2,2,1,13,5]heptane (5b). 13C NMR (CDCl3, δ, ppm): 37.5 (C7); 48.0 (CS); 50.8 (C1); 54.6 (CBr); 57.0 (C4). Mass spectrum, m/z (Irel, %): 286 (25) [M + 4]+, 284 (34) [M + 2]+, 282 (26) [M]+, 205 (97), 203 (100), 171 (13), 169 (12), 124 (48), 123 (44). Di(endo3chlorobicyclo[2.2.1]hept5enexo2 yl)disulfide (6a). The compound was not isolated in individual state, its formation was detected from char acteristic signals of olefinic protons in the 1H NMR spectrum (CDCl3, δ, ppm, J/Hz): 6.21 dd (1H, HC=, J = 5.4, J = 2.9), 6.37 dd (1H, HC=, J = 5.4, J = 3.2) and data of mass spectrometry: Mass spectrum, m/z (Irel, %): 322 (0.7) [M + 4]+, 320 (2.8) [M + 2]+, 318 (3.6) [M]+, 285 (0.5), 283 (1.8), 159 (10.7), 127 (10.0), 91 (100). Di(endo3bromobicyclo[2.2.1]hept5enexo2 yl)disulfide (dl : meso mixture = 5 : 4) (6b). Rf = 0.70 (eluent: petroleum ether : ethyl acetate = 1 : 3). 1H NMR (CDCl , δ, ppm, J/Hz): 1.70 m (2H, anti 3 H7 (dl and meso)), 1.85 d (1H, synH7 (meso), J = 9.5), 1.88 d (1H, synH7 (dl), J = 9.4), 2.97 m (1H, H1 (dl)), 3.00 m (1H, H1 (meso)), 3.07 t (1H, H4 (meso), J = 3.0), 3.11 t (1H, H4 (dl), J = 3.0), 3.25 br. s (2H, (meso and dl)), 4.20 t (1H, HCBr (meso), J = 3.4), 4.30 t (1H, HCBr (dl), J = 3.4), 6.22 dd (2H, H5 (dl and meso), J = 5.7, J = 2.9), 6.39 dd (1H, H6 (dl), J = 5.7, J = 3.0), 6.40 dd (1H, H6 (meso), J = 5.7, J = 3.0). 13 C NMR (CDCl3, δ, ppm): 45.6 (C7), 48.5, 48.6 (C4), 49.9 (C1), 54.1, 54.5 (CS), 59.2, 59.5 (CBr), 136.7, 136.8, 136.9, 137.0 (C=C). Mass spectrum, m/z (Irel, %): 410 (6) [M + 4]+, 408 (10) [M + 2]+, 406 (6) [M]+, 329 (34), 327 (30), 205 (28), 203 (28), 173 (16), 171 (20), 124 (28), 123 (84), 91 (100). Mixture of N(endo3bromobicyclo[2.2.1]hept 5enexo2ylthio)piperidine (7) and N(exo3bromo bicyclo[2.2.1]hept5enendo2ylthio)piperidine (8). 13 C NMR (CDCl3, δ, ppm) for compound 7: 22.7, 26.7 (CH2 of piperidine), 45.8 (C7), 48.6, 49.3 (C4 and C1), 52.9 (CS), 55.8 (CBr), 58.6 (NCH2), 135.7, 137.0 (C=C). 13C NMR (CDCl3, δ, ppm) for compound 8: 23.1, 27.3 (CH2 of piperidine), 47.4 (C7), 48.1, 52.6 (C4 and C1), 54.1 (CS), 57.2 (CBr), 58.5 (NCH2), 134.8, 136.9 (C=C). Mass spectrum, m/z (Irel, %) for compound 7: 289 (24) [M + 2]+, 287 (24) [M]+, 223 (14). 221 (14), 208 (100), 142 (33), 123 (68), 90 (50). Mass spectrum, m/z (Irel, %) for compound 8: 289 (12) [M + 2]+, 287 (12) [M]+, 223 (24). 221 (24), 208 (100), 142 (38), 122 (44), 90 (34). 13

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4.07 t (J = 3.4) 3.02e

2.80 m 3.18 m

3.18b m

H(6)

antiH(1)

synH(1)

1.40 m (2H), 1.60d m (4H) 3.00cm (4H, H2CN)

NR2

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2.83 br.s 3.02j br.s 5.93 dd (J = 5.3, 6.13k J = 3.1)

2.01 d (J = 9.1) 1.66 dd (J = 9.0, J = 1.4)

(a) CDCl3 as a solvent; (b) signals are overlapped; (c) signals are overlapped; (d) signals are overlapped; (e) signals are overlapped; (f) CDCl3 : C6D6 = 3 : 2 as a solvent; (g) signals are in the region of 2.94–3.07 ppm and overlapped with the signal of NCH2 group; (h) signals are overlapped; (i) C6D6 as a solvent; (j) signals are overlapped; (k) signals are overlapped; (l) signals are overlapped.

10i 3.69 t (J = 2.9) 3.52l

4.00 t (J = 3.3) 2.99 t (J = 2.7) 2.69 br.s 3.02j br.s 6.13k dd (J = 5.5, 6.24 dd (J = 5.5, 1.56 d (J = 9.3) 1.49 dd (J = 9.3, J = 1.6) 2.91 m J = 3.1) (4H, NCH2) 3.55 l t J = 2.6) (4H, NCH2, J = 4.5)

2.05 d (J = 9.1) 1.58 dq (J = 9.1, J = 1.4)

9i

5.72 dd (J = 5.2, 6.153h J = 3.2)

g

3.81 t (J = 3.1) 3.63 t (J = 2.3) 2.75 br.s

1.55 d (J = 9.2) 1.40 dq (J = 9.2, J = 2.1) 1.21 m (2H), 1.47 m (4H) 3.01 m (4H, H2CN)

8f

6.15h m

g

4.07 t (J = 3.4) 3.16 t (J = 3.0) 2.68 br.s

6.12 dd (J = 5.7, 6.22 dd (J = 5.7, 2.08 d (J = 9.2) 1.78 ddd (J = 9.2, J = 3.2) J = 2.1) J = 2.1, J = 1.8)

6.19 dd (J = 5.7, 6.37 dd (J = 5.7, 1.67 d (J = 9.3) 1.61 ddd (J = 9.3, J = 2.5, 3.00e m (4H, NCH2) J = 2.1) J = 3.0) J = 1.9) 3.67 m (4H, NCH2)

6.10 dd (J = 5.7, 6.24 dd (J = 5.7, 2.07 d (J = 9.0) 1.76 dq (J = 9.0, J = 1.9) J = 3.2) J = 2.1)

6.19 dd (J = 5.7, 6.37 dd (J = 5.7, 1.67 d (J = 9.3) 1.62d J = 2.9) J = 3.1)

H(5)

7f

10a 3.75 t (J = 3.1) 3.59 t (J = 2.7) 3.02 m 3.16 m

9a

3.75 t (J = 3.1) 3.60 t (J = 2.5) 3.00 d

H(4)

2.80 br.s 3.00c

H(1)

8a

HCS

4.10 t (J = 3.4) 3.18b br.s

HCHal

7a

Pro duct

Table 5. 1H NMR spectra of products 7–10

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REACTION OF UNSATURATED COMPOUNDS

8Chlorobicyclo[4.2.0]octa2,4dien7sulfenchlo ride (14). Detected in a mixture with thiacyclane 16 by NMR spectroscopy as two isomers. 1H NMR (CDCl3, δ, ppm, J/Hz) of the major isomer: 3.62 dddd (1H, HC1 or HC6, J = 8.7, J = 7.6, J = 3.1, J = 1.1), 4.03 m (1H, HC1 or HC6), 4.72 t (1H, HCS, J = 4.5), 5.60 ddd (1H, HC=, J = 11.0, J = 4.4, J = 1.8), 5.77 dd (1H, HCCl, J = 3.5, J = 0.8), 5.97 ddd (1H, HC=, J = 11.0, J = 8.6, J = 1.0), 6.43 t (1H, HC=, J = 8.4), 6.56 dd (1H, HC=, J = 8.8, J = 8.0). 1H NMR (CDCl3, δ, ppm, J/Hz) of the minor isomer: 3.55 (1H, HC1 or HC6, overlapped with the signal of the major isomer), 3.95 m (1H, HC1 or HC6), 4.92 td (1H, HCS, J = 5.3, J = 1.0), 5.45 d (1H, HCCl, J = 4.1), 5.79 ddd (1H, HC=, J = 11.2, J = 4.4, J = 1.9), 6.05 ddd (1H, HC=, J = 11.5, J = 8.1, J = 1.7), 6.33 ddd (1H, HC=, J = 8.9, J = 7.3, J = 0.8), 6.43 ddd (1H, HC=, J = 9.0, J = 8.3, J = 1.1). 13C NMR (CDCl3, δ, ppm) of the major isomer: 42.3, 43.6 (C1 and C6), 59.0 (CS), 68.6 (CCl), 127.6, 128.6, 130.9, 135.2 (C=C). 13C NMR (CDCl3, δ, ppm) of the minor isomer: 41.7, 44.8 (C1 and C6), 67.4 (CCl), 129.1, 130.7, 136.4 (C=C), the signal of CS and signal of one carbon at double bond are over lapped with signal of compounds 14 (the major iso mer) and 16. Mass spectrum, m/z (Irel, %): 210 (1.0) [M + 4]+, 208 (5.7) [M + 2]+, 206 (8.1) [M]+, 173 (13.3), 171 (33.2), 135 (38.9), 125 (14.4), 91 (100). 2,9Dichloro8thiabicyclo[5.1.1]nona3,5diene (16). Isolated in a mixture with compound 19a. 1H NMR (CDCl , δ, ppm, J/Hz) of compound 16: 3.95 m 3 (2H), 4.39 ddd (1H, J = 4.8, J = 1.2, J = 0.9) (signals of HCS and HCCl), 5.06 d.q (1H, HC2Cl, J = 4.9, J = 1.8), 5.76 dd (1H, HC3 or HC6, J = 10.5, J = 2), 6.02 dd (1H, HC3 or HC6, J = 10.5, J = 4.9), 6.43 ddd (1H, HC4 or HC5, J = 10.4, J = 6.5, J = 2.0), 6.32 ddd (1H, HC4 or HC5, J = 10.5, J = 6.7, J = 1.2). Mass spectrum, m/z (Irel, %): 210 (2.2) [M + 4]+, 208 (13.0) [M + 2]+, 206 (19.1) [M]+, 173 (37.6), 171 (100), 135 (76.1), 97 (31.0), 91 (63.2). 2,6Dichloro9thiabicyclo[3.3.1]nonadiene3,7 (19a). 1H NMR (CDCl , δ, ppm, J/Hz): 3.50 t (2H, HCS, 3 J = 5.7), 5.15 m (2H, HCCl), 5.92 d (2H, HC3, HC7, J = 10.9), 6.25 ddd (2H, HC4, HC8, J = 10.9, J = 6.0, J = 1.8). 13C NMR (CDCl3, δ, ppm): 35.91 (CS), 58.89 (CCl), 127.92 (C3, C7), 130.79 (C4, C8). Mass spectrum, m/z (Irel, %): 210 (2.5) [M + 4]+, 208 (13.8) [M + 2]+, 206 (19.9) [M]+, 173 (28.6), 171 (75.1), 135 (79.7), 97 (100), 91 (59.4). 2,6Dibromo9thiabicyclo[3.3.1]nonadiene3,7 (19b). 1H NMR (CDCl , δ, ppm, J/Hz): 3.53 t (2H, HCS, 3 J = 5.7), 5.28 m (2H, HCBr), 6.07 dd (2H, HC3, HC7, J = 10.5, J = 1.1), 6.27 ddd (2H, HC4, HC8, J = 10.5, J = 6.1, J = 1.8). 13C NMR (CDCl3, δ, ppm): 35.90 (CS), 49.61 (CBr), 129.01 (C3, C7), 131.01 (C4, C8). Mass spectrum, m/z (Irel, %): 298 (4.6) [M + 4]+, 296 (9.0) [M + 2]+, 294 (4.6) [M]+, 217 (51.8), 215 (52.2), 136 (57.3), 135 (100), 97 (33.0), 91 (64.1). Trans7,8dibromobicyclo[4.2.0]octa2,4diene (20). 1H NMR (CDCl , δ, ppm, J/Hz): 3.20 dddd (1H, 3 MOSCOW UNIVERSITY CHEMISTRY BULLETIN

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HC1, J1,6 = 10.7, J1,8 = 8.4, J1,2 = 5.9, J = 1.5), 3.66 m (1H, HC6), 4.65 td (1H, HC8, J8,1 ≈ J8,7 = 8.4, J8,6 = 1.2), 4.94 t (1H, HC7, J7,6 ≈ J7,8 = 8.4), 5.66–5.73 m (2H, HC2, HC5), 5.91 dd (1H, HC3, J3,2 = 9.3, J3,4 = 5.6), 6.05 dddd (1H, HC4, J4,5 = 10.3, J4,3 = 5.6, J4,6 = 2.0, J = 1.0). 1H NMR (C6D6, δ, ppm, J/Hz): 2.66 ddd (1H, HC1, J = 11.0, J = 8.4, J = 5.7), 2.94 m (1H, HC6), 4.50 t (1H, HC7, J = 8.5), 4.5 td (1H, HC8, J = 8.4, J = 1.0), 5.32 ddd (1H, HC3, J = 9.7, J = 5.6, J = 1.0), 5.49–5.56 m (2H, HC2, HC5), 5.70 ddd (1H, HC4, J = 10.2, J = 5.9, J = 2.0). 13C NMR (CDCl3, δ, ppm): 42.64, 40.36 (C1, C6), 55.17, 58.40 (CBr), 122.26, 123.79, 124.46, 125.58 (C=C). Mass spec trum, m/z (Irel, %): 266 (0.4) [M + 4]+, 264 (0.9) [M + 2]+, 262 (0.5) [M]+, 185 (7.5), 183 (7.4), 104 (40.3), 103 (19.1), 78 (100), 77 (16.0). Found (%): C 36.20; H 3.25. C8H8Br2. Calculated (%): C 36.40; H 3.05. 4,5,7,8Tetrabromobicyclo[4.2.0]octa2en (21). 1H NMR (CDCl , δ, ppm, J/Hz): 3.27 tddd (1H, 3 HC6, J6,1 = J6,7 = 9.0, J6,5 = 2.6, J = 1.6, J = 0.9), 3.48 m (1H, HC1), 4.66 dd (1H, HC8, J8,1 = 8.5, J8,7 = 8.3), 4.85 dd (1H, HC5, J5,6 = 2.6, J = 1.3), 5.09 m (1H, HC4), 5.15 ddd (1H, HC7, J7,6 = 9.0, J7,8 = 8.3, J = 1.0), 6.05 dd (1H, HC2, J2,3 = 10.3, J2,1 = 3.8), 6.16 ddt (1H, HC3, J3,2 = 10.3, J3,4 = 5.0, J = 1.3). 13C NMR (CDCl3, δ, ppm): 36.28, 43.67, 44.06, 48.10, 48.80, 49.87 (C1, C4, C5, C6, C7, C8), 125.48, 128.24 (C=C). Mass spectrum, m/z (Irel, %): 347 (3.6) [M + 6 – Br]+, 345 (11.3) [M + 4 – Br]+, 343 (11.9) [M + 2 – Br]+, 341 (3.7) [M – Br]+, 265 (37.2), 263 (71.9), 261 (39.3), 184 (60.2), 182 (59.8), 159 (32.8), 157 (35.5), 104 (57.5), 103 (55.4), 78 (100), 77 (83.5). Mixture of di((E)1chlorohept1en2yl)sulfide (22a) and ((E)1chlorohept1en2yi)((E)2chlorohept 1en2yl)sulfide (23a). As a result of reaction of 0.53 g (2.6 mmol) N,Nthiobismorpholine, 0.62 g (5.2 mmol) thionyl chloride and 0.50 g (5.2 mmol) of heptyn1, a mixture of 22a and 23a (22a : 23a = 2 : 1) as a yellow liquid (0.40 g (52%)) was obtained after column chro matography (ethyl acetate–petroleum ether 1 : 10). Rf = 0.94. 1H NMR (CDCl3, δ, ppm, J/Hz) of the 1

mixture of compounds 22a and 23a : 0.94 m (6H, CH3 (isomer 22a) + 6H, CH3 (isomers 23a)), 1.35 m (8H, 4H4, 4H5 (isomer 22a) + 8H, 4H4, 4H5 (isomer 23a)), 1.50–1.65 m (4H, 4H3 (isomer 22a) + 4H, 4H3 (iso mer 23a)), 2.35 t (4H, CH2CS (isomer 22a), J = 7.6), 2.41 t (2H, CH2CS (isomer 23a), J = 7.6), 2.56 t (2H, CH2CCl, (isomer 23a), J = 7.4), 5.98 s (1H, HCS (isomer 23a)), 6.11 s (1H, HCCl (isomer 23a)), 6.23 s (2H, HCCl (isomer 22a)). 13C NMR (CDCl3, δ, ppm): 14.01 (CH3 (isomers 22a, 23a)), 22.45 (C6 (iso mers 22a, 23a)), 26.79 (C5 (radical R–CCl= of isomer 23a)), 26.87 (C5 (radical R–S= of isomers 22a, 23a)), 30.76 (C4 (radical R–CCl= of isomer 23a)), 31.10 (C4 (radical R–CS= of isomers 22a, 23a)), 31.20 (CH2CS 1 Integral intensities are given separately for compounds 22a and 23a.

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(isomer 22a)), 31.69 (CH2CS (isomers 23a)), 34.84 (CH2CCl (isomer 23a)), 113.87 (CHS, (isomers 23a)), 117.34 (CHCl (isomers 23a)), 118.61 (CHCl (isomer 22a)), 136.26 (=C–S (isomer 22a)), 137.42 (RCS (isomer 23a)), 139.77 (RCCl (isomer 23a)). Found (%): C 56.75; H 8.26. C16H12Cl2S. Calculated (%): C 56.93; H 8.13. Mass spectrum, m/z (Irel, %): 296 (12.9) [M]+, 261 (46.2) [M + 2 – Cl]+, 260 (29.0) [M + 1 – Cl]+, 259 (100) [M – Cl]+, 223 (6.4) [M – 2Cl], 203 (34.4), 95 (61.3), 71 (79.6). Mass spectrum, m/z (Irel, %): 296 (9.7) [M]+, 259 (46.2) [M – Cl]+, 223 (7.5) [M – 2Cl]+, 203 (215), 95 (38.7), 71 (100). Mixture of di((E)2chloro1phenylethynyl)sulfide (22b) and ((E)2chloro1phenylethynyl)((E)2 chloro2phenylethynyl)sulfide (23b). As a result of the reaction of 0.51 g (2.5 mmol) N,Nthiobismorpho line, 0.58 g (4.9 mmol) thionyl chloride and 0.50 g (4.9 mmol) of phenylacetylene, a mixture of 22b and 23b (22b : 23b = 1 : 1) as a lightbrown liquid (0.70 g (93%)) was obtained after column chromatography (ethyl acetate–petroleum ether 1 : 10). Rf = 0.89. 1H NMR (CDCl , δ, ppm, J/Hz) of the mixture of 3 compounds 22b and 23b: 6.33 s (1H, HCS (compound 23b)); 6.55 s (1H, HCCl (compounds 23b)), 6.56 m (2H, HCCl (compound 22b)) 7.22–7.54 (24H, arom.). 13C NMR (CDCl , δ, ppm): 116.66 (CS in com 3 pound 23b), 118.72, 120.98 (CHCl (in compounds 22b and 23b)), 122.03, 128.25, 128.42, 128.50, 128.66, 128.72, 128.81, 128.88, 129.35, 129.46, 129.75, 129.90 (C arom.), 134.55, 134.66, 135.91, 136.04, 136.12, 136.66 (C2Cl (in compound 23b), C arom. (C1), C2S (in compounds 22b and 23b)). Found (%): C (62.47); H (4.03). C16H12Cl2S. Calculated (%): C (65.52); H (3.91). The chromato–mass spectrum contains four peaks. The major compounds: mass spectrum, m/z (Irel, %): 273 (26.9) [M + 2 – Cl]+, 272 (18.3) [M + 1 – Cl]+, 271 (79.6) [M – Cl]+, 236 (100) [M – 2Cl], 203 (5.4) [M – 2Cl – SH), 134 (23.7), 121 (18.3), 102 (82.8); mass spectrum, m/z (Irel, %): 308 (3.9) [M + 2]+, 307 (2.2) [M + 1]+, 306 (4.3) [M]+, 273 (16.1) [M + 2 – Cl]+, 272 (7.5) [M + 1 – Cl]+, 271 (41.9) [M – Cl]+, 236 (26.9) [M – 2Cl], 203 (3.2) [M – 2Cl – SH), 134 (18.3), 121 (100), 102 (43.0). The minor products: mass spectrum, m/z (Irel, %): 273 (8.6) [M + 2 – Cl]+, 272 (7.5) [M + 1 – Cl]+, 271 (25.8) [M – Cl]+, 236 (24.7) [M – 2Cl], 203 (4.3) [M – 2Cl – SH), 134 (46.2), 121 (100), 102 (60.2); mass spectrum, m/z (Irel, %): 308 (29.0) [M + 2]+, 307 (11.8) [M + 1]+, 306 (36.6) [M]+, 271 (100) [M – Cl]+, 236 (73.1) [M – 2Cl], 203 (18.3) [M – 2Cl – SH2), 134 (93.5), 121 (62.4), 102 (68.8). Reaction of norbornadiene with morpholinesulfen bromide. To a solution of 0.38 g (1.6 mmol) of dithio bismorpholine in 10 mL of CHCl3, a solution of 0.26 g (1.6 mmol) of bromine in 8 mL of CHCl3 was added at –20°C in a flow of argon. Stirring was carried out at this temperature for 10 min; the temperature then was raised to 0°C for an additional 10 min. The reaction

mixture was cooled to –25°C and a solution of 0.32 g (3.5 mmol) of norbornadiene in 5 mL of CHCl3 was added. Stirring was carried out at this temperature for 10 min. The temperature was increased to room temper ature and the solvent was evaporated to afford 0.93 g (98%) of a mixture of endo3bromobicyclo[2,2,1]hept 5enexo2yl sulfenmorpholide (9) and exo3bro mobicyclo[2.2.1]hept5enendo2yl sulfenmor pholide (10) (9 : 10 = 1 : 1) as a colorless liquid with strong odor. Rf = 0.69 (eluent: petroleum ether : ethyl acetate = 1 : 3). 13C NMR (CDCl3, δ, ppm) for com pound 9: 45.8 (C7), 48.5, 49.3 (C4 and C1), 53.4 (CS), 55.2 (CBr), 57.1 (NCH2), 67.6 (OCH2), 135.9, 136.9 (C=C). 13C NMR (CDCl3, δ, ppm) for compound 10: 47.3 (C7), 48.0, 52.5 (C4 and C1), 54.8 (CS), 56.7 (CBr), 57.0 (NCH2), 67.6 (HCH2), 135.1, 136.6 (C=C). Mass spectrum, m/z (Irel, %) for compound 9: 291 (16) [M + 2]+, 289 (16) [M]+, 225 (15), 223 (15), 210 (100), 123 (62), 91 (59). Mass spectrum, m/z (Irel, %) for compound 10: 291 (11) [M + 2]+, 289 (11) [M]+, 225 (22), 223 (22), 210 (100), 123 (52), 91 (39). Found (%): C (45.39); H (5.13); N (4.70). C11H16BrNOS. Calculated (%): C (45.52); H (5.22); N (4.83). Reaction of mixture of compounds 9 and 10 with thionyl bromide. To a solution of 0.19 g (0.655 mmol) of mixture of sulfenamides 9 and 10 (1 : 1) in 15 mL of chloroform, a solution of 0.68 g (0.37 mmol) SOBr2 in 5 mL of chloroform was added by drops at –40°C by drops in a flow of argon. Stirring was conducted at this temperature for 20 min, the temperature was slowly raised to room temperature and stirring was continued for additional 1 h. The reaction mixture was passed through a columnfilter packed with silica gel (h = 5 cm). The solvent was evaporated to give 0.13 g of a mixture of 2,6diexobromo8thiatricyclo[2.2.1.13,5]heptane (5b) (39%) and di(endo3bromobicyclo[2.2.1]hept5en exo2yl)disulfide (dl : meso mixture = 5 : 4) (6b) (43%). Reaction of mixture of compounds 9 and 10 with thionyl chloride. To a solution of 0.47 g (1.62 mmol) of mixture of sulfenamides 9 and 10 (1 : 1) in 20 mL of chloroform, a solution of 0.3 g (2.5 mmol) SOCl2 in 10 mL of chloroform was added by drops at –40°C by drops in a flow of argon. Stirring was conducted at this temperature for 20 min, the temperature was slowly raised to room temperature and stirring was continued for 24 h. The reaction mixture was passed through a columnfilter packed with silica gel (h = 5 cm). The solvent was evaporated to give 0.26 g of a mixture of 2,6diexochloro8thiatricyclo[2.2.1.13,5]heptane (5a) (16%), 2exobromo6exochloro8thiatricy clo[2.2.1.13,5]heptane (5c) (47%) and di(endo3bro mobicyclo[2.2.1]hept5enexo2yl)disulfide (6b) (8%). After additional chromatographic purification (eluent: petroleum ether : ethyl acetate = 10 : 1), 0.18 g of a mix ture of 2,6diexochloro8thiatricyclo[2.2.1.13,5]hep tane (5a) (14%) and 2exobromo6exochloro8 thiatricyclo[2.2.1.13,5]heptane (5c) (35%). 1H NMR (CDCl3, δ, ppm, J/Hz) of compound 5c: 2.15 dq (1H,

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HC7, J7,7 = 12.3, J = 1.1), 2.22 dq (1H, HC7, J7,7 = 12.3, J = 1.1), 3.27 td (1H, HCS, J = 4.2, J = 1.1), 3.29 br.s (1 H, HC1) 3.42 td (2H, HCS, J = 4.4, J = 1.1), 4.02 m (1H, HC4), 4.66 s (1H, HCCl), 4.71 s (1H, HCBr). 13C NMR (CDCl3, δ, ppm): 36.71 (C7); 48.23, 48.31 (CS); 50.57 (C1); 54.73 (CBr); 56.76 (C4), 64.27 (CCl). Mass spectrum, m/z (Irel, %) of com pound 5c: 242 (7.9) [M + 4]+, 240 (24) [M + 2]+, 238 (21.7) [M]+, 205 (4.1), 203 (3.9), 161 (36.6), 159 (100), 125 (26.9), 123 (36.1), 97 (17.3), 79 (22.8), 65 (26.7). Reaction of mixture of compounds 5a and 5c with thionyl chloride. A solution of 0.18 g of a mixture of thiacyclanes 5a and 5c (1.0 : 2.9) (0.04 g of 5a and 0.14 g of 5c, respectively) and 0.3 g of SOCl2 in 10 mL of chloroform was stirred at room temperature for 48 h. The reaction mixture was passed through a column filter packed with silica gel (h = 5 cm). The solvent was evaporated to yield 0.14 g 2,6diexochloro8thia tricyclo[2.2.1.13,5]heptane (5a) (yield in reaction of transformation of 5c into 5a is 88%). Reaction of cyclooctatetraene with bromine. To a solution of 0.4 g (3.8 mmol) of cyclooctatetraene in 15 mL of CHCl3 at –30°C, a solution of 0.6 g (3.8 mmol) of bromine in 15 mL of CHCl3 was added. The reaction mixture was stirred for 10 min, then the temperature was raised to room temperature and stirring was con tinued for 1–2 h. The mixture was then washed with a sodium sulfite solution until the disappearance of bro mine coloration. The organic layer was separated, the aqueous phase was extracted three times with chloro form, and organic extracts were combined and dried over sodium sulfate. The solution was passed through a column–filter. The solvent was removed in vacuum to yield 0.936 g (92%) of dibromide 20. ACKNOWLEDGMENTS The work was supported by the Russian Founda tion for Basic Research (project no. 110300707a) and by the Presidium of the Russian Academy of Sci ences (the Elaboration of methods for the preparation of chemical substances and development of novel materials program of basic research). REFERENCES 1. Mashkovskii, M.D., Lekarstvennye sredstva (Medical Drugs), Kharkov, 1998, vol. 1. 2. Tolstikov, G.A., Sulfur Rep., 1983, vol. 3, p. 39. 3. Zyk, N.V., Vatsadze, S.Z., Beloglazkina, E.K., Dubin skaya, Yu.A., Titanyuk, I.D., and Zefirov, N.S., Dokl. Chem., 1997, vol. 357, nos. 1–3, p. 263.

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4. Zyk, N.V., Beloglazkina, E.K., Vatsadze, S.Z., Tit anyuk, I.D., and Dubinskaya, Yu.A., Russ. J. Org. Chem., 2000, vol. 36, no. 6, p. 794. 5. Zyk, N.V., Beloglazkina, E.K., Vatsadze, S.Z., and Tit anyuk, I.D., Russ. Chem. Bull., 1998, vol. 47, no. 12, p. 2434. 6. Zyk, N.V., Gavrilova, A.Y., Mukhina, O.A., Bond arenko, O.B., and Zefirov, N.S., Russ. Chem. Bull., 2008, vol. 57, no. 12, p. 2572. 7. Bondarenko, O.B., Gavrilova, A.Yu., Tikhanushkina, V.N., and Zyk, N.V., Russ. Chem. Bull., 2005, vol. 54, no. 9, p. 2133. 8. Corey, E.J. and Block, E., J. Org. Chem., 1966, vol. 31, p. 1663. 9. Lautenschlaeger, F., J. Org. Chem., 1966, vol. 31, p. 1679. 10. Eberson, L., Nyberg, K., Finkelstein, M., Petersen, R.C., Ross, S.D., and Uebel, J.J., J. Org. Chem., 1967, vol. 32, p. 16. 11. Connors, G., Wu, X., and Fry, A.J., Org. Lett., 2007, vol. 9, p. 1671. 12. Pretsch, E., Buhlmann, P., and Affolter, C., Structure Determination of Organic Compounds, Berlin: Springer Verlag, 2000. 13. Lautenschlaeger, F., J. Org. Chem., 1968, vol. 33, p. 2627. 14. Georgian, V., Georgian, L., and Robertson, A.V., Tet rahedron, 1968, vol. 19, p. 1219. 15. Huisgen, R. and Boche, G., Tetrahedron Lett., 1965, vol. 6, p. 1769. 16. Boche, G. and Huisgen, R., Tetrahedron Lett., 1965, vol. 6, p. 1775. 17. Barton, T.J. and Zika, R.G., J. Org. Chem., 1970, vol. 35, p. 1729. 18. Zyk, N.V., Beloglazkina, E.K., Belova, M.A., and Dubinina, N.S., Usp. Khim., 2003, vol. 72, p. 864. 19. Mueller, W.H. and Butler, P.E., J. Org. Chem., 1968, vol. 33, p. 2111. 20. Denisenko, O.V., Cand. Sci. (Khim.) Dissertation, Mos cow, 1991. 21. Zyk, N.V., Beloglazkina, E.K., Belova, M.A., Dubin ina, N.S., and Kleva, I.A., Russ. Chem. Bull., 2003, vol. 52, no. 7, p. 1425. 22. Zyk, N.V., Beloglazkina, E.K., Belova, M.A., and Zefirov, N.S., Russ. Chem. Bull., 2000, vol. 49, no. 11, p. 1846. 23. Zyk, N.V., Gavrilova, A.Yu., Nechaev, M.A., Mukhina, O.A., Bondarenko, O.B., and Zefirov, N.S., Izv. Akad. Nauk, Khim., 2009, p. 2435. 24. Blanc, P.Y., Diehl, P., Fritz, H., and Schlapfer, P., Experienta, 1967, vol. 23, p. 896. 25. Weil, E.D., Smith, K.J., and Gruber, R.J., J. Org. Chem., 1966, vol. 31, p. 1669.

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Translated by M. Makarov

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2014

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