Nature chooses rings: Synthesis of silicon-containing macrocyclic peroxides

Article

pubs.acs.org/Organometallics

Nature Chooses Rings: Synthesis of Silicon-Containing Macrocyclic

Peroxides

Ashot V. Arzumanyan,^†Roman A. Novikov,^†Alexander O. Terent’ev,*^,†Maxim M. Platonov,^†

Valentin G. Lakhtin,^‡Dmitry E. Arkhipov,^§,∥Alexander A. Korlyukov,^§,∥Vladimir V. Chernyshev,^⊥,#

Andrew N. Fitch,^$Alexander T. Zdvizhkov,^†Igor B. Krylov,^†Yury V. Tomilov,^†and Gennady I. Nikishin^†

^†N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian

Federation

^‡State Research Institute for Chemistry and Technology of Organoelement Compounds, 38 shosse Entuziastov, Moscow 111123

Russian Federation

^§A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova ul, Moscow 119991 Russian

Federation

^∥Pirogov Russian National Research Medical University, Ostrovitianov str. 1, Moscow 117997 Russian Federation

^⊥Department of Chemistry, M. V. Lomonosov Moscow State University, 1-3 Leninskie Gory, Moscow 119991 Russian Federation

^#A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky prospect, Moscow

119071 Russian Federation

^$European Synchrotron Radiation Facility, B.P. 220, 38043 Grenoble Cedex, France

S

* Supporting Information

ABSTRACT: The reactions of 1,2-bis(dimethylchlorosilyl)-

ethane (1), 1,2-bis(dimethylchlorosilyl)ethene (6), and 1,2-

bis(dimethylchlorosilyl)ethyne (7) with gem-bis-

(hydroperoxides) 2a−h and 1,1′-bis(hydroperoxy)bis-

(cycloalkyl)peroxides 4a−c were found to proceed in an

unusual way. Thus, the reactions do not give the expected

polymeric peroxides; instead, they produce cyclic silicon-

containing peroxides containing 2, 4, or 6 silicon atoms in the

ring: 9- (3a−h), 12- (5a−c), 18- (8, 12), 24- (9, 10), 27- (13),

and 36-membered (11) compounds. The size of the rings

produced in the reactions increases in the series 1,2-bis(dimethylchlorosilyl)ethane < 1,2-bis(dimethylchlorosilyl)ethene < 1,2-

bis(dimethylchlorosilyl)ethyne. The resulting 9- and 12-membered cyclic peroxides are stable under ambient conditions. These

1

compounds were isolated by chromatography and characterized by H, ¹³C, and ²⁹Si NMR spectroscopy, X-ray diﬀraction,

elemental analysis, and high-resolution mass spectrometry. The yields vary from 77 to 95%. Structures of the larger-size rings

(18-, 24-, 27-, and 36-membered peroxides) were conﬁrmed by ¹H, ¹³C, and ²⁹Si NMR spectroscopy using 2D (COSY, HSQC,

1

and HMBC), 2D DOSY H, 3D H−²⁹Si HMBC-DOSY NMR experiments, and elemental analysis.

tetraoxepanes,¹²and 1,2,4,5-tetraoxanes.¹³Silicon-containing

INTRODUCTION

■

peroxides are produced as intermediates in the Fleming¹⁴and

Tamao−Kumada¹⁵oxidation. The fundamental aspects of the

structures, properties, and reactivities of heteroorganic

peroxides have drawn keen attention from researchers working

in this ﬁeld.¹⁶

Organic peroxides belong to a class of compounds that are in

considerable demand.¹For more than 50 years, these

compounds have been widely used in industry and scientiﬁc

research as oxidants, autoxidation products, polymerization

initiators, initiators in organic synthesis, cross-linking agents,

and building blocks. In the past decades, organic peroxides,

particularly those having a cyclic structure, have attracted

interest as pharmaceutically active compounds. For example,

some organic peroxides exhibit antimalarial,²antihelminthic,³

or antitumor activity.⁴Peroxides with the Si−O−O fragment

have similar applications and are used for the initiation of

polymerization,⁵hydroxylation of arenes,⁶peroxidation,⁷

thermal transformations,⁸and the synthesis of 1,2-dioxolanes,⁹

1,2-dioxanes,^9e,101,2,4-trioxanes,¹¹1,2-dioxepanes,^9e1,2,4,5-

On the whole, the chemistry of silicon-containing peroxides

is less well developed in comparison to the chemistry of

carbon-containing peroxides due, in part, to the shortage of

selective methods for their synthesis. There are a limited

number of routes to peroxides containing the Si−O−O

fragment. These methods are based on the reactions of silyl

Received: January 29, 2014

Published: April 21, 2014

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triﬂates or chlorosilanes with hydroperoxides in the presence of

bases,^7a,9a,b,17singlet oxygen with silyl enolates,¹⁸compounds

containing the Si−H bond with ozone,¹⁹hydroperoxides with

N,O-bis(trimethylsilyl)acetamide,²⁰and the Co(L)₂/O₂/Et₃SiH

system with unsaturated compounds.²¹

Advances in the chemistry of organosilicon peroxides have

been considered in detail in reviews by Brandes and

Blaschette,^22aAleksandrov,^22bTamao,^22cAndo,^22dRicci,^22e

and Davies^22fand in our review.^22g

Scheme 1. Synthesis of 9- and 12-Membered Peroxides 3a−h

and 5a−c by the Reactions of 1,2-

Bis(dimethylchlorosilyl)ethane (1) with gem-

Bis(hydroperoxides) 2a−h and 1,1′-

Bis(hydroperoxy)bis(cycloalkyl)peroxides 4a−c,

Respectively

Only a few publications have been devoted to investigations

on the chemistry of silicon-containing cyclic peroxides: in

particular, on their synthesis. Thus, structures containing the

endocyclic O−O−Si−O−O moiety were described: 3,3,6,6,9,9-

hexamethyl-1,2,4,5,7,8-hexaoxa-3,6,9-trisilonane,²³1,2,4,5,7,8-

hexaoxa-3-silonanes,²⁴and some other related com-

pounds.^22f,g,25The scarcity of data on Si-containing cyclic

peroxides is to a large extent associated with the fact that these

compounds are synthesized using two bifunctional reagents,

which easily form polymers. The synthesis of cyclic products of

a given composition rather than oligomeric and polymeric

products is a diﬃcult or even intractable problem.

In the present study, we succeeded in selectively synthesizing

9- (3a−h), 12- (5a−c), 18- (8, 12), 24- (9, 10), 27- (13), and

36-membered (11) peroxides by the reactions of the following

bifunctional reagents: gem-bis(hydroperoxides) 2a−h and 1,1′-

bis(hydroperoxy)bis(cycloalkyl)peroxides 4a−c with 1,2-bis-

(dimethylchlorosilyl)ethane (1), 1,2-bis(dimethylchlorosilyl)-

ethene (6), and 1,2-bis(dimethylchlorosilyl)ethyne (7). It

should be noted that 12-, 18-, 24-, 27-, and 36-membered

peroxides containing the SiOOC moiety have been previously

unknown. In organic chemistry, the approach to nine-

membered and particularly to larger-ring compounds is always

more diﬃcult in comparison to the synthesis of 5−7-membered

cyclic compounds. The synthesis of large-ring products is often

accompanied by the formation of oligomers and sometimes

requires special catalysts for the coupling of several molecules

or high-dilution cyclization methods.²⁶In addition, the

approach to cyclic peroxides is complicated by the instability

of the O−O group to some reagents used in organic synthesis.

often unsuitable for the synthesis of the latter compounds. In

many instances, the synthesis of such compounds is

accompanied by the formation of oligomers. It would be

quite reasonable to expect that the reaction of two bifunctional

reagents, geminal bis(hydroperoxides) 2a−h and dichlorodisi-

lane 1, in which the Si−Cl groups are separated by three bonds,

will lead to polycondensation. The latter process is observed in

similar reactions: for example, in the synthesis of polyesters,

polyamides, polycarbonates, polyurethanes, polyimides, and

poly(ether sulfones)²⁷(Scheme 2).

Scheme 2

RESULTS AND DISCUSSION

■

The present study consists of two parts. In the ﬁrst part, we

synthesized 9- and 12-membered peroxides and developed a

general experimental procedure. In the second part, we

synthesized 18-, 24-, 27-, and 36-membered peroxides.

Synthesis of Stable 9- and 12-Membered Peroxides.

In the framework of the general strategy of the synthesis of 9-

and 12-membered cyclic peroxides, we performed the reactions

of gem-bis(hydroperoxides) 2a−h and 1,1′-bis(hydroperoxy)-

b i s ( c y c l o a l k y l ) p e r o x i d e s 4 a − c w i t h 1 , 2 - b i s -

(dimethylchlorosilyl)ethane (1) (Scheme 1).

Earlier,²⁴we successfully synthesized cyclic peroxides but in a

more similar case. In dichlorosilanes used in our previous study,

two chlorine atoms acting as leaving groups were attached to

one silicon atom, whereas the large distance between chlorine

atoms in the present study should promote the formation of

polymers.²⁸

To optimize the reaction conditions, we varied the nature of

the base (amine) and the order of the addition of reagents in

the reaction of bis(hydroperoxide) 2d with dichlorodisilane 1.

We used aromatic and aliphatic bases, such as imidazole,

pyridine, 2,6-dimethylpyridine, 4-dimethylaminopyridine, qui-

noline, tetrahydroquinoline, diethylamine, triethylamine, and

DABCO. The yield of 1,2,7,8-tetraoxa-3,6-disilonane 3d can be

accurately determined due to a simple and reproducible

procedure for the isolation and puriﬁcation of this product

(Table 1).

The highest yield of peroxide 3d was obtained with the use of

aromatic nitrogen-containing bases: 95% yield in the presence

of imidazole (run 1) and somewhat lower yields (76, 65, and

64%) in the presence of 2,6-dimethylpyridine, DMAP, and

pyridine, respectively (runs 3, 4, and 2). The aliphatic amines

The work was performed in two stages. In the ﬁrst stage, we

examined the synthesis of 3-tert-butyl-9,9,12,12-tetramethyl-

7,8,13,14-tetraoxa-9,12-disilaspiro[5.8]tetradecane (3d) starting

from 1,2-bis(chlorodimethylsilyl)ethane (1) and 1,1-bis-

(hydroperoxy)-4-tert-butylcyclohexane (2d) and found the

optimum reaction conditions. Then other 9- and 12-membered

cyclic peroxides were synthesized, taking into account these

conditions.

When proceeding to the synthesis of 9-membered peroxides,

one cannot be sure that the result will be positive because

structurally similar carbocycles are strained and, consequently,

general methods for the construction of cyclic structures are

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Table 1. Inﬂuence of the Nature of the Base and the Order of the Addition of Reagents on the Yield of Peroxide 3d in the

a

Reaction of Bis(hydroperoxide) 2d with Dichlorodisilane 1

a

General procedure of the synthesis of peroxide 3d: a solution of dichlorodisilane 1 (0.115 g, 0.535 mmol) in Et₂O (2 mL) was added with stirring

to a solution of bis(hydroperoxide) 2d (0.109 g, 0.535 mmol) and amine (0.076−0.150 g, 1.123 mmol, 2.1 mol/mol of 2d) in Et₂O (5 mL) at 20−

b

25 °C for 2−3 min. The mixture was stirred for 1.5 h. Yields of 3d are calculated as (mol of 3d)/(mol of 2d) × 100. The order of mixing of reagents

was changed: a solution of bis(hydroperoxide) 2d (0.109 g, 0.535 mmol) in Et₂O (2 mL) was added with stirring to a solution of dichlorodisilane 1

(0.115 g, 0.535 mmol) and amine (0.076−0.089 g, 1.123 mmol, 2.1 mol/mol of bis(hydroperoxide) 2d) in Et₂O (5 mL) at 20−25 °C for 2−3 min.

c

The mixture was stirred for 1.5 h. The order of mixing of reagents was changed: a solution of dichlorodisilane 1 (0.115 g, 0.535 mmol) and

bis(hydroperoxide) 2d (0.109 g, 0.535 mmol) in Et₂O (5 mL) was added with stirring to a solution of amine (0.076−0.089 g, 1.123 mmol, 2.1 mol/

d

mol of bis(hydroperoxide) 2d) in Et₂O (2 mL) at 20−25 °C for 2−3 min. The mixture was stirred for 1.5 h. Pyridine was used as the reaction

medium. Dichlorodisilane 1 (0.115 g, 0.535 mmol) was added with stirring to a solution of bis(hydroperoxide) 2d (0.109 g, 0.535 mmol) in pyridine

(5 mL) at 20−25 °C for 2−3 min. The mixture was stirred for 1.5 h.

(runs 5−8) Et₃N, Et₂NH, DABCO, and tetrahydroquinoline

are less eﬃcient than aromatic amines. In the absence of bases,

product 3d is not formed. The bases Et₂NH and

tetrahydroquinoline react with bis(dimethylchlorosilyl)ethane

and remove the latter from the reaction zone (runs 5 and 6).

In the presence of DABCO or Et₃N, a considerable amount

of bis(hydroperoxide) 2d decomposes to form 4-tert-

butylcyclohexanone (runs 7 and 8). This observation was

conﬁrmed by NMR spectroscopy. The ¹³C NMR spectrum

recorded 20 min after the addition of a 2-fold molar excess of

DABCO to a solution of bis(hydroperoxide) 2d in CDCl₃

showed a signal at δ 212.4 corresponding to the carbonyl

carbon atom of 4-tert-butylcyclohexanone.

was added to a solution of dichlorodisilane 1 and amine

according to footnote b (runs 1 and 2). In run 1, the yields

diﬀer by more than a factor of 6, whereas in run 2 the yields

remain unchanged. There is a substantial decrease in the yield

with a change in the order of the addition of reagents in the

reaction with imidazole (run 1), in contrast to the reactions

with the use of pyridine (run 2), in which the unchanged yield

is attributed to the formation of a complex stable to further

transformations in run 1^b. The existence of the latter complex

was conﬁrmed by NMR spectroscopy. In CDCl₃, the ¹³C and

²⁹Si NMR spectra of dichlorodisilane 1 were recorded, and then

the spectra of a mixture of 1 with imidazole (10−20 min after

mixing) taken in molar ratios of 1:1, 1:2, 1:4, and 1:6 were

measured. In the ¹³C NMR spectra, the signals of the SiCH₃

and SiCH₂groups, which are observed at δ 1.06 and 10.8,

respectively, for dichlorodisilane 1, are shifted to δ −0.128 and

9.7 (ratio 1:1), δ −1.203 and 8.667 (ratio 1:2), δ −3.042 and

7.055 (ratio 1:4), and δ −3.267 and 7.022 (ratio 1:6). In a

mixture of dichlorodisilane 1 with pyridine, no shifts of ¹³C

NMR signals are observed.

The TLC monitoring showed no conversion of bis-

(hydroperoxide) 2d and dichlorodisilane 1 in pyridine in run

2^d. Apparently, dichlorodisilane 1 and bis(hydroperoxide) 2d

are solvated with pyridine, which hinders the reaction between

the active centers of these reagents.

In the reaction, the base serves three main functions

responsible for the yield of peroxide 3d. First, the base

increases the nucleophilicity of hydroperoxide by accepting an

acidic proton. The second function is to react with chlorosilane.

For example, the formation of stable complexes of amines with

SiF₄was documented.²⁹In the present study, we observed a

substantial diﬀerence in the yield of peroxide 3d in the

reactions with the use of imidazole and pyridine carried out

according to two procedures, which are described in footnotes

a and b of Table 1 to runs 1 and 2 and which diﬀer in the order

of the addition of reagents. According to footnote a( general

procedure), dichlorodisilane 1 was added to a solution of 1,1-

bis(hydroperoxy)-4-tert-butylcyclohexane (2d) and amine,

whereas 1,1-bis(hydroperoxy)-4-tert-butylcyclohexane (2d)

In the ²⁹Si NMR spectrum of a mixture of dichlorodisilane 1

and imidazole, the signal of the silicon atom, which is observed

at δ 32.88 for the starting dichlorodisilane 1, is shifted to δ 28.1

(ratio 1:1), δ 24.6 (ratio 1:2), δ 18.85 (ratio 1:4), and δ 16.75

(ratio 1:6). The upﬁeld shifts of the signals in the ¹³C and ²⁹Si

NMR spectra are apparently due to the formation of the ﬁve-

coordinate complex in the reaction with the use of the reagents

in a ratio of 1:1 or 1:2 and the formation of a six-coordinate

complex with the use of a ratio of 1:4 or 1:6.^30a−cIt is also

possible to suggest the formation of trisubstituted silyl

imidazole in the case of 1:4 and 1:6 ratios on the basis of

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²⁹Si NMR spectral data.^30d−fIn the spectrum of a mixture of

dichlorodisilane 1 and pyridine, the position of the ²⁹Si NMR

signal remains virtually unchanged. In the reaction performed

according to footnote c of Table 1 (run 1), a solution of

dichlorodisilane 1 and bis(hydroperoxide) 2d was added to a

solution of amine, and peroxide 3d was obtained in a yield

equal to that obtained in the synthesis performed according to

the general procedure. The third main function of amine is to

bind hydrogen chloride that is eliminated and maintain a

weakly acidic medium, which is of great importance for the

reaction to proceed eﬃciently.

Table 2. Inﬂuence of the Reaction Time, the Reagent Ratio,

and the Nature of the Solvent on the Yield of Peroxide 3d in

the Reaction of Bis(hydroperoxide) 2d with

a

Dichlorodisilane 1 in the Presence of Imidazole as the Base

run

time, h

solvent

molar ratio imidazole:2d:1 yield of 3d, %

1

0.1

0.3

1.5

3

Et₂O

2.1:1:1

4:1:1

41

61

95

83

80

51

85

80

55

70

72

30

2

3

4

5

6:1:1

6

3.1:1:1.5

2.1:1:1

It was shown that the nature of the base is a key factor

determining selectivity of cycle formation. The general

cyclization mechanism was proposed on the basis of imidazole,

which is the best base (Scheme 3).

7

8

5

Et₂O

9

29

Et₂O

10

11

12

1.5

CH₃CN

CH₂Cl₂

THF

Scheme 3. Possible Mechanism of Cycle Formation from

Dichlorodisilanes and Dihydroperoxides with the Use of

Imidazole as a Base

a

General procedure of the synthesis of 3d: a solution of

dichlorodisilane 1 (0.115 or 0.173 g, 0.535 or 0.803 mmol) in Et₂O,

CH₃CN, CH₂Cl₂, or THF (2 mL) was added with stirring to a

solution of 2d (0.109 g, 0.535 mmol) and imidazole (0.076−0.218 g,

1.123−3.210 mmol, 2.1−6 mol/mol of peroxide 2d) in Et₂O, CH₃CN,

CH₂Cl₂, or THF (5 mL) at 20−25 °C for 2−3 min. The reaction

mixture was stirred for 0.1−29 h. Yields of 3d are calculated as (mol of

3d)/(mol of 2d) × 100.

(over 1−2 s rather than for 2−3 min) results in the formation

of an insoluble viscous white substance.

Peroxides 3a−h were synthesized in Et₂O in 80−95% yields

using a 2.1-fold molar excess of imidazole relative to

bis(hydroperoxides) 2a−h and dichlorodisilane 1 taken in

equimolar amounts (Table 3).

Depending on the reactivity of geminal bis(hydroperoxides)

2a−h, which decreases with increasing ring size, the reaction

time was varied from 1 to 20 h with the aim of synthesizing

3a−h in the highest yield. 1,1-Bis(hydroperoxy)-3,3,5-trime-

thylcyclohexane (2e) and 1,1-bis(hydroperoxy)cyclododecane

(2g) appeared to be the least reactive. Thus, the reactions

involving these compounds require 6.5 and 20 h, respectively,

to be completed as opposed to 1−1.5 h needed for

bis(hydroperoxides) 2a−d,f,h. The relatively low yield of

peroxide 3h is, apparently, due to the low stability of the

starting geminal bis(hydroperoxide) 2h under the reaction

conditions.

Determination of the Structures of 3a−h. The

structures of 3a−h were established on the basis of NMR

spectroscopic data, taking into account the elemental analysis

data. The ¹³C NMR spectra show characteristic signals at δ

105.03−121.22 corresponding to the OOCOO moiety in

related cyclic structures²⁴and signals for the CH₂CH₂(δ 4.61−

4.96) and CH₃(δ −3.5) groups. A signiﬁcant feature is the

change in the ²⁹Si NMR chemical shift, which is 32.9 ppm for

dichlorodisilane 1 and 26.25 and 26.76 ppm for cyclic peroxide

3d.

It can be proposed without getting into speciﬁcs that one Si−

O bond is formed on the ﬁrst stage. Then imidazole

coordinates with a silicon atom and successively via a hydrogen

atom with an oxygen atom of another peroxide group. This

coordination envelops the molecule. Finally the second Si−O

bond is formed with preparation of the peroxide cycle.

Then, to optimize the reaction conditions, we studied the

inﬂuence of the nature of the solvent, the reaction time, and the

imidazole:peroxide 2d:dichlorodisilane 1 molar ratio on the

yield of cyclic peroxide 3d (Table 2).

Diethyl ether is the solvent of choice. Thus, in the time

period from 0.1 to 29 h, the yield of peroxide 3d varied in the

range 41−95% (Table 2, runs 1−9); in runs 1 and 2 the

reaction was not brought to completion, and in run 9 the target

product was largely decomposed.

An excess amount of the base has little eﬀect on the

formation of peroxide 3d. The reactions with the use of 2.1-, 4-,

and 6-fold molar excesses of imidazole relative to bis-

(hydroperoxide) 2d and dichlorodisilane 1 gave the target

product in 95, 83, and 80% yields, respectively (Table 2, runs

3−5). The use of a 1.5-fold molar excess of dichlorodisilane 1

relative to bis(hydroperoxide) 2d (run 6) led to a decrease in

the yield of peroxide 3d to 51%.

Solvents such as CH₃CN (Table 2, run 10) and CH₂Cl₂(run

11) also proved to be eﬃcient in this reaction; the reactions in

THF gave the target product in lower yield (run 12).

It should be emphasized that the result depends on the rate

of the addition of dichlorodisilane 1 to a mixture of

bis(hydroperoxide) 2d and imidazole. Thus, the rapid addition

Since 1,2,4,5-tetraoxadisilonanes have been previously

unknown, the formation of 18-membered peroxides as

condensation products of four (2 + 2 coupling) rather than 2

molecules of the starting reagents cannot be ruled out. We

studied the structures of 3d (Figure 1) and 3g by X-ray

diﬀraction analysis and showed that these peroxides have a 9-

membered cyclic structure.

Peroxides 3a−h are stable during storage at 0 °C and can be

puriﬁed by chromatography on silica gel. Peroxides 3a−c,e,f,h

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Table 3. Structures, Yields, and the Time of the Synthesis of 1,2,7,8-Tetraoxa-3,6-disilonanes 3a−h from gem-

a

Bis(hydroperoxides) 2a−h and 1,2-Bis(dimethylchlorosilyl)ethane (1)

a

General procedure of the synthesis of 1,2,7,8-tetraoxa-3,6-disilonanes 3a−h: a solution of dichlorodisilane 1 (0.115 g, 0.535 mmol) in Et₂O (2 mL)

was added with stirring to a solution of bis(hydroperoxides) 2a−h (0.148−0.200 g, 0.535 mmol) and imidazole (0.076 g, 1.123 mmol, 2.1 mol/mol

of 2a−h) in Et₂O (5 mL) at 20−25 °C for 2−3 min. The solution was stirred for 1−20 h.

oligomers or polymers.^27,28However, we obtained 12-

membered cyclic peroxides 5a−c with good selectivity (Scheme

4).

Scheme 4. Synthesis of 1,2,7,8,10,11-Hexaoxa-3,6-

disilacyclododecanes 5a−c from 1,1′-

Bis(hydroperoxy)bis(cycloalkyl)peroxides 4a−c and 1,2-

Bis(dimethylchlorosilyl)ethane (1)

Peroxides 5a−c were synthesized in diethyl ether using a 2.1-

Figure 1. General view of molecule 3d presented in ADP ellipsoids at

fold molar excess of imidazole (Table 4).

The ring size (ﬁve-, six-, and seven-membered rings) in the

starting dihydroperoxyperoxides 4a−c has little eﬀect on the

results of the synthesis. Thus, peroxides 5a−c were synthesized

in 77−90% yields. Attempts to prepare 1,2,7,8,10,11-hexaoxa-

3,6-disilacyclododecane using 1,1′-bis(hydroperoxy)bis-

(cyclododecyl)peroxide containing sterically hindered reaction

centers failed even when the reaction time was increased to 24

h.

50% probability. Hydrogen atoms are omitted for clarity.

are oily liquids, and peroxides 3d,g are solids with melting

points of 87−89 and 110−112 °C (without decomposition),

respectively.

Synthesis of 12-Membered Cyclic Peroxides 5a−c

from 1,1′-Bis(hydroperoxy)bis(cycloalkyl)peroxides 4a−

c and 1,2-Bis(dimethylchlorosilyl)ethane (1). Twelve-

membered cyclic compounds are diﬃcult to synthesize, and

they are poorly known in comparison to ﬁve- to seven-

membered and even nine-membered cyclic compounds.

Twelve-membered rings involving the SiOOC moiety are

unknown, and only a few cyclic compounds containing the

COOC moiety in such rings were described.²⁴

When proceeding to the synthesis of 12-membered peroxides

with the use of two bifunctional reagents, such as bis-

(hydroperoxy)bis(cycloalkyl)peroxides 4a−c and dichlorodisi-

lane 1, in which the reaction centers are distant from each

other, one would expect the predominant formation of

1,2,7,8,10,11-Hexaoxa-3,6-disilacyclododecanes 5a−c show

no clear evidence of decomposition during storage for 1

month at 0 °C. These compounds can be recrystallized from

anhydrous solvents (MeOH and MeCN). Peroxides 5b,c were

found to have high melting points (113−116 and 124−126 °C

(without decomposition), respectively).The structures of 5a−c

were determined by NMR spectroscopy, elemental analysis,

and high-resolution mass spectrometry. The characteristic

NMR signals at δ 109.1−121.0 correspond to the OOCOO

moiety in related cyclic structures.²⁴It is indicative that the ¹³

C

NMR chemical shifts change on going from dichlorodisilane 1

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Synthesis and Analysis of 18- (8, 12), 24- (9, 10), 27-

(13), and 36-Membered (11) Peroxides, Reaction

Products of 1,2-Bis(dimethylchlorosilyl)ethene (6) and

1,2-Bis(dimethylchlorosilyl)ethyne (7) with gem-Bis-

(hydroperoxide) 2d and 1,1′-Bis(hydroperoxy)peroxide

4c. Compounds containing 18-, 24-, 27-, or 36-membered rings

are exceptionally rare among organic synthesis products

because polymerization is often an insurmountable obstacle

to their formation. In this part of the work, we performed the

reactions of diperoxides 2d and 4c with the use of

dichlorodisilanes³¹6 and 7 having a double bond in the E

conﬁguration and a triple bond to synthesize silicon-containing

macrocycles. The structural rigidity of dichlorodisilanes 6 and 7

should evidently preclude the ring formation by the coupling of

two molecules; in this case the formation of oligomers seemed

to be more likely. Instead, the reaction of 2d or 4c with 1,2-

bis(dimethylchlorosilyl)ethene (6) gave cyclic peroxides 8 and

9 of a dimeric (2 + 2) composition, whereas the reaction with

1,2-bis(dimethylchlorosilyl)ethyne (7) produced cyclic per-

oxides 10 and 12 of a dimeric (2 + 2) composition and 11 and

13 of a trimeric (3 + 3) composition.

The structures of cyclic peroxides 8−13 were determined by

¹H, ¹³C, and ²⁹Si NMR spectroscopy using the 2D correlation

techniques COSY, HSQC, and HMBC and by diﬀusion-

ordered spectroscopy (DOSY), which allowed us to estimate

the molecular weight and, as a consequence, the number of

bis(hydroperoxide) and dichlorodisilane moieties in cyclic

peroxides.

Diﬀusion-ordered spectroscopy is a very eﬃcient tool for

analyzing mixtures of compounds without their separation.³²

The diﬀusion coeﬃcient for the molecule represented as a hard

sphere is inversely proportional to six hydrodynamic radii of

this sphere according to the Stokes−Einstein equation. On the

assumption that there are no interactions between molecules of

the dissolved compound and the solvent, the diﬀusion of

molecules depends only on their molecular weight; con-

sequently, diﬀusion coeﬃcient measurements provide fairly

accurate estimates of the molecular weights of dissolved

compounds.³²

Table 4. Structures, Yields, and the Times of the Synthesis of

1,2,7,8,10,11-Hexaoxa-3,6-disilacyclododecanes 5a−c from

1,1′-Bis(hydroperoxy)bis(cycloalkyl)peroxides 4a−c and

c

1,2-Bis(dimethylchlorosilyl)ethane (1)

a

b

Isolated by column chromatography. Isolated by crystallization from

c

MeOH. General procedure of the synthesis of 5a−c: a solution of

dichlorodisilane 1 (0.150 g, 0.698 mmol) in Et₂O (1.5 mL) was added

with stirring to a mixture of bis(hydroperoxy)peroxides 4a−c (0.163−

0.202 g, 0.698 mmol) and imidazole (0.1 g, 1.465 mmol, 2.1 mol/mol

of peroxide 4a−c) in Et₂O (3.5−4 mL) at 20−25 °C for 3−4 min. The

reaction mixture was stirred for 3 h.

to 1,2,7,8,10,11-hexaoxa-3,6-disilacyclododecanes 5a−c from

1.06 to −3.73 to −3.62 ppm for CH₃and from 10.80 to 5.68−

5.73 ppm for CH₂. The ²⁹Si NMR spectrum of dichlorodisilane

1 shows a signal at δ 32.88, whereas the corresponding signal in

the spectrum of cyclic peroxide 5c is observed at δ 27.5.

Since 1,2,7,8,10,11-hexaoxa-3,6-disilacyclododecanes have

been previously unknown, the formation of 24-membered

peroxides as condensation products of four (2 + 2 coupling)

rather than two molecules of the starting reagents cannot be

ruled out. It seemed to be important to directly conﬁrm the

structures of these compounds by X-ray diﬀraction analysis. For

this purpose, we studied compound 5c by X-ray diﬀraction

(Figure 2).

The 11-membered ring adopts a crownlike conformation. It

is worth noting that the presence of three peroxide groups does

not lead to substantial changes in the bond lengths and bond

angles in 5c in comparison with those in 3d,g.

The viscosity of the solvent CDCl₃is insuﬃcient to obtain

high-quality interpretable DOSY NMR spectra. However, it was

impossible to perform the reaction and record DOSY NMR

spectra in commonly used, more viscous DMSO or D₂O

because the peroxides in question are unstable in these solvents.

To increase the viscosity of solutions in CDCl₃, we developed a

method for recording DOSY NMR spectra by the addition of

dry chemically inert nanosized silica gel (silica fume, powder,

14 nm particle size) to the solution under study in an amount

of 1 wt %. It appeared that even small amounts of silica gel

substantially increase the viscosity of the solution by converting

it to gel, the spectral resolution remaining virtually unchanged.

As a consequence, in the DOSY NMR spectra measured in the

thickened solvent CDCl₃, individual components of the mixture

are easily separated on the basis of the diﬀering translation

diﬀusion coeﬃcients. In addition, the diﬀusion coeﬃcients

showed a logarithmic dependence on the molecular weight,

thus providing a fairly accurate estimate of the molecular

weights of the compounds in question.

1

The diﬀusion coeﬃcients were measured by 2D DOSY H

NMR spectroscopy using the BPP-LED pulse sequence³³in the

presence of dibenzo-18-crown-6, pyridine, hexaoxononane

(8,9,22,23,36,37-hexaoxatrispiro[6.2.11¹⁰.2.11²⁴.2⁷]-

heptatriacontane),³⁴and peroxides 3d and 5c, which are similar

Figure 2. General view of molecule 5c presented in ADP ellipsoids at

50% probability. Hydrogen atoms are omitted for clarity.

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in the structure and polarity to the macrocyclic peroxides in

question, as internal calibrants of known molecular masses.

Since the chemical nature of these calibrants is similar to that of

the compounds under study, their diﬀusion coeﬃcients have a

logarithmic dependence on the molecular weight, which was

unambiguously established for the test specimen containing

dibenzo-18-crown-6, hexaoxononane (8,9,22,23,36,37-

hexaoxatrispiro[6.2.11¹⁰.2.11²⁴.2⁷]heptatriacontane), pyridine,

and peroxides 3d and 5c with established structures.

Synthesis of 18-Membered Peroxide 8 from 1,2-

Bis(dimethylchlorosilyl)ethene (6) and gem-Bis-

(hydroperoxide) 2d. The synthesis of 18-membered peroxide

8 from 1,2-bis(dimethylchlorosilyl)ethene (6) and gem-bis-

(hydroperoxide) 2d was performed on a preparative scale in the

presence of imidazole in Et₂O. The NMR spectra were

measured in the presence of pyridine in CDCl₃or CDCl₃

using silica fume for 2D DOSY ¹H NMR. Under these

conditions, the reaction aﬀords peroxide 8 as the major product

along with trace amounts of nine-membered peroxide 8′

(Scheme 5).

the molecular weight of peroxide 8 is higher than that of the

crown ether. The diﬀusion coeﬃcient of the monomeric

compound 8′ should be larger than that of dibenzo-18-crown-6,

which is unambiguously conﬁrmed by the fact that the diﬀusion

coeﬃcient of the monomeric analogue 3d is larger than that of

dibenzo-18-crown-6 (Figure 4). The structure of 3d has been

established by X-ray diﬀraction analysis (vide supra). We

1

recorded two 2D DOSY H NMR spectra (Figures 3 and 4),

which diﬀer in that peroxide 3d was added as the calibrant to

the second sample (Figure 4), to avoid possible errors in the

determination of the diﬀusion coeﬃcients.

After the determination of the structure of the main

compound 8, the reaction mixture was analyzed by 3D

¹H−²⁹Si-HMBC-DOSY NMR spectroscopy for the presence

1

of monomeric (8′) and trimeric peroxides. The 3D H−²⁹Si-

HMBC-DOSY spectrum was acquired using a new pulse

sequence developed by us. In this approach, silicon is detected

in the inverse mode, which substantially enhances the

1

sensitivity of the method. On the basis of the 3D H−²⁹Si-

HMBC-DOSY NMR spectroscopic data (see the Supporting

Information), it can be concluded that the mixture contains, in

addition to the major dimeric peroxide 8, a minor amount of

the low-molecular-weight component, the monomeric peroxide

8′.

Scheme 5. Synthesis of 8 from 1,2-

Bis(dimethylchlorosilyl)ethene (6) and gem-

Bis(hydroperoxide) 2d

Synthesis of 24-Membered Peroxide 9 from 1,2-

Bis(dimethylchlorosilyl)ethene (6) and 1,1′-Bis-

(hydroperoxy)bis(cycloheptyl)peroxide (4c). The prepa-

rative synthesis of 24-membered peroxide 9 was performed

starting from 1,2-bis(dimethylchlorosilyl)ethene (6) and 1,1′-

bis(hydroperoxy)bis(cycloheptyl)peroxide (4c) in the presence

of imidazole in Et₂O. The NMR experiments were carried out

in the presence of pyridine in CDCl₃and CDCl₃with silica

1

fume for 2D DOSY H NMR (Scheme 6).

This reaction aﬀords peroxide 9 in 80% yield. The 24-

membered dimeric structure of this compound was established

by analogy with peroxide 8 on the basis of the ¹H, ¹³C, and ²⁹Si

NMR spectroscopic data using 2D correlation techniques

(COSY, HSQC, and HMBC) and DOSY NMR spectra

(Supporting Information).

Synthesis of 24- (10) and 36-Membered (11)

Peroxides from 1,2-Bis(dimethylchlorosilyl)ethyne (7)

and 1,1′-Bis(hydroperoxy)bis(cycloheptyl)peroxide (4c).

The reaction of bis(dimethylchlorosilyl)ethyne (7) with 1,1′-

bis(hydroperoxy)bis(cycloheptyl)peroxide (4c), giving a mix-

ture of products, was carried out in the presence of imidazole in

Et₂O. This reaction gives two macrocyclic peroxides: 24-

membered dimeric peroxide 10 (30%) and 36-membered

trimeric peroxide 11 (50%), as well as trace amounts (5%) of

monomeric peroxide 10′. The structure of 10′ was determined

by X-ray diﬀraction (Scheme 7).

What is surprising is the fact that this reaction aﬀords cyclic

peroxides, which can be isolated from the reaction mixture,

because the direct triple bond is an unsuitable fragment for the

ring formation. Peroxides 10 and 11 are poorly stable. These

compounds are less stable than 18-membered peroxide 8 and

undergo spontaneous decomposition during storage in the

reaction mixture in an NMR tube for 1−2 days, even at

temperatures below 0 °C.

Peroxide 8 was isolated in nearly quantitative yield (90%). In

CDCl₃and CDCl₃with silica fume, peroxide 8 is stable for

several days at temperatures below 0 °C.

The structure of peroxide 8 was unambiguously established

by ¹H, ¹³C, and ²⁹Si NMR spectroscopy using the 2D

correlation techniques COSY, HSQC, and HMBC and by

diﬀusion-ordered spectroscopy (DOSY). A combination of 1D

and 2D NMR techniques enabled us to determine the cyclic

skeleton of the molecule, and the DOSY NMR data provided

an estimate of its molecular weight and, consequently, the

number of residual fragments of bis(peroxide) 2d and

dichlorodisilane 6 in molecule 8.

On the basis of two 2D DOSY ¹H NMR spectra, it was found

that peroxide 8 is a (2 + 2) dimer rather than the possible (1 +

1) monomer 8′ (Figures 3 and 4).

The structures of dimeric and trimeric peroxides 10 and 11

were established by ¹H, ¹³C, and ²⁹Si NMR spectroscopy using

2D correlation techniques (COSY, HSQC, and HMBC) and

As can be seen from the 2D DOSY NMR spectrum (Figure

3), the diﬀusion coeﬃcient of dimer 8 is smaller than the

diﬀusion coeﬃcient of dibenzo-18-crown-6 and, consequently,

1

DOSY NMR spectroscopy, including the 3D H−²⁹Si-HMBC-

DOSY NMR spectra. The diﬀusion coeﬃcients of these

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35

1

Figure 3. 2D DOSY H NMR spectrum processed with the SCORE algorithm for peroxide 8 using dibenzo-18-crown-6 as the calibrant.

1

Figure 4. 2D DOSY H NMR spectrum processed with the SCORE algorithm for peroxide 8 using dibenzo-18-crown-6 and 3d as the calibrants.

compounds showed a logarithmic dependence on the

molecular weight (Figure 5 and the Supporting Information).

The 2D DOSY ¹H NMR spectrum (Figure 5) shows that the

diﬀusion coeﬃcient of peroxide 10 is smaller than that of the

crown ether (consequently, its molecular weight is higher than

that of the crown ether), which is consistent with the molecular

weight of dimeric peroxide. The smaller diﬀusion coeﬃcient of

peroxide 11 in comparison with that of peroxide 10 is evidence

for the trimeric structure of 11. Peaks of higher-molecular-

weight oligomeric peroxides with the assumed diﬀusion

coeﬃcients (a brown dashed rectangle) are not observed.

Since dimeric and trimeric peroxides 10 and 11 have

1

complex structures, we used 3D H−²⁹Si-HMBC-DOSY NMR

spectroscopy with the pulse sequence developed by us (see

Figure 6; for more detail, see the Supporting Information) to

exclude the possible error. According to this procedure, ²⁹Si

atoms are detected in the inverse mode on the basis of protons,

which substantially enhances the sensitivity of the method. The

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and HMBC) and DOSY NMR spectroscopy, including 3D

¹H−²⁹Si-HMBC-DOSY NMR spectra.

Scheme 6. Synthesis of Peroxide 9 from 1,2-

Bis(dimethylchlorosilyl)ethene (6) and 1,1′-

Bis(hydroperoxy)bis(cycloheptyl)peroxide (4c)

Analysis of Peroxides 3d, 5c, and 8−13 on the Basis of

²⁹Si NMR Data. Along with DOSY NMR spectroscopy, the

analysis of the chemical shifts in the ²⁹Si NMR spectra is a key

point in the determination of the structures. These chemical

shifts vary over a wide range and are strongly sensitive to the

environment of the silicon atom, due to which the Si−O−O

group can be ultimately identiﬁed in the molecular structure.

To identify silicon-containing peroxides 8−13, we used ²⁹Si

NMR data. The chemical shifts in the ²⁹Si NMR spectra of 3d

and 5c proved to be suitable as the reference values, because

the structures of these compounds were determined by X-ray

diﬀraction. The chemical shifts in the ²⁹Si NMR spectra of

compounds 3d, 5c, and 8−13, which were synthesized in the

present study, and in the spectra of dichlorodisilanes 1, 6, and 7

and their hydrolysis products (siloxanes) are given in Table 5.

Dichlorodisilanes 1, 6, and 7, peroxides 3d, 5c, and 8−13,

and hydrolysis products of 1, 6, and 7^28d(siloxanes) have

diﬀerent chemical shifts in the ²⁹Si NMR spectra. In the series

of each class of compounds, the signals are shifted upﬁeld on

going from the C−C to CC bond. Upﬁeld shifts are

observed also in the series chlorosilane−peroxysilane−siloxane.

Scheme 7. Synthesis of Peroxides 10′, 10, and 11 from 1,2-

Bis(dimethylchlorosilyl)ethyne (7) and 1,1′-

Bis(hydroperoxy)bis(cycloheptyl)peroxide (4c)

CONCLUSIONS

■

We found a new phenomenon in the reactions of bifunctional

chlorosilanes with diperoxide compounds, in which the

cyclization dominates over polymerization. The nature of the

base and the reaction conditions have a considerable eﬀect on

the selectivity of the ring formation.

The reactions of 1,2-bis(dimethylchlorosilyl)ethane (1) with

gem-bis(hydroperoxides) 2a−h and 1,1′-bis(hydroperoxy)bis-

(cycloalkyl)peroxides 4a−c in the presence of bases produced

the previously unknown classes of cyclic peroxides containing

two silicon atoms in the ring: 9-membered 1,2,7,8-tetraoxa-3,6-

disilonanes 3a−h and 1,2,7,8,10,11-hexaoxa-3,6-disilacyclodo-

decanes 5a−c containing a 12-membered ring, which are

uncommon in the chemistry of peroxides. Peroxides 3a−h and

5a−c are stable at 0 to −5 °C during storage for 3 months.

These compounds were isolated by chromatography and

recrystallization and were then characterized by NMR spec-

troscopy, mass spectrometry, X-ray diﬀraction, and elemental

analysis. The yields of these products vary from 77 to 95%

depending on the structural features.

The reactions of 1,2-bis(dimethylchlorosilyl)ethene and 1,2-

bis(dimethylchlorosilyl)ethyne with gem-bis(hydroperoxide) 2d

and 1,1′-dihydroperoxyperoxide 4c in the presence of bases

aﬀord the previously unknown 18- (8, 12), 24- (9, 10), 27-

(13), and 36-membered (11) peroxides, whereas the expected

polymeric peroxides are virtually not formed at all. The DOSY

NMR spectroscopy proved to be a key method for structural

investigations of silicon-containing peroxides. Peroxides 8−13

are stable at 0 to −5 °C during storage for 2 weeks.

addition of the third dimension in comparison with 2D spectra

enables the separation of overlapping signals. The 3D ¹H−²⁹Si-

HMBC-DOSY NMR spectrum was recorded over 10−30 min.

The applicability of the 3D ¹H−²⁹Si-HMBC-DOSY NMR

techniques for the purposes of the present study was examined

using a test sample composed of silicon-containing peroxides

3d and 5c with established structures. The 3D ²⁹Si DOSY

spectrum (Figure 6) ultimately conﬁrms the structures of the

peroxides. Thus, this spectrum shows two components with

diﬀerent diﬀusion coeﬃcients corresponding to dimeric

peroxide 10 and trimeric peroxide 11.

Synthesis of 18- (12) and 27-Membered (13)

Peroxides from 1,2-Bis(dimethylchlorosilyl)ethyne (7)

and gem-Bis(hydroperoxide) 2d. The reaction of 1,2-

bis(dimethylchlorosilyl)ethyne (7) with gem-bis-

(hydroperoxide) 2d aﬀorded a mixture of 9- (12′), 18- (12),

and 27-membered (13) peroxides in 7, 32, and 40% yields,

respectively (Scheme 8).

The reactions of 1,2-bis(dimethylchlorosilyl)ethane, 1,2-

b i s ( d i m e t h y l c h l o r o s i l y l ) e t h e n e , a n d 1 , 2 - b i s -

(dimethylchlorosilyl)ethyne give cyclic peroxides by the

coupling of two, four, or six molecules, respectively. A decrease

in the degree of freedom in chlorosilanes in going from 1,2-

bis(dimethylchlorosilyl)ethane to 1,2-bis(dimethylchlorosilyl)-

ethyne directs the reaction to the formation of larger-size rings.

The structures of peroxides 12 and 13 were established by

1

analogy with peroxides 10 and 11 by H, ¹³C, and ²⁹Si NMR

spectroscopy using 2D correlation techniques (COSY, HSQC,

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1

Figure 5. 2D DOSY H NMR spectrum processed by the monoexponential ﬁtting for peroxides 10 and 11 using dibenzo-18-crown-6 as the

calibrant.

ms, and J_SiH= 6 Hz. The total experimental time varied from 10 to 30

EXPERIMENTAL SECTION

■

min depending on the sample used. The 3D DOSY NMR spectra were

General Experimental Details. Caution! We have encountered

processed by the monoexponential ﬁtting of cross-peak volumes using

explosions in working with peroxides: precautions, such as the use of

the Bruker TopSpin software. Peroxides 3d and 5c, which were added

shields and fume hoods and the avoidance of transition-metal salts,

to the studied substances in a ∼1:1 molar ratio, served as the internal

heating, and shaking, should be taken whenever possible.

and external calibrants of known molecular masses in the DOSY NMR

spectra.

1

The H and ¹³C NMR spectra were recorded on 400 MHz (400.1

and 100.6 MHz, respectively) and 300 MHz spectrometers (300.1 and

MeCN (HPLC grade) for ESI-HRMS experiments was ordered

75.5 MHz, respectively) in CDCl₃containing 0.05% Me₄Si as the

from Merck and used as supplied. All samples for ESI-HRMS

internal standard. The assignments of H and ¹³C NMR signals were

made with the aid of 2D COSY, HSQC, and HMBC spectra where

1

experiments were prepared in 1.5 mL Eppendorf tubes. All plastic

necessary. The ²⁹Si NMR spectra were recorded on a 300 MHz

disposables (Eppendorf tubes and tips) used in sample preparation

1

were washed with MeCN before use.

spectrometer (59.6 MHz; 300.1 MHz for H) in CDCl₃using the

INEPT pulse sequence and Me₄Si as the standard. The assignments of

High-resolution mass spectra were recorded on a Bruker maXis

²⁹Si NMR signals were made with the aid of 2D HMBC spectra where

instrument equipped with an electrospray ionization (ESI) ion

source.³⁶All measurements were performed in a positive (+MS) ion

necessary. Since it was impossible to directly detect some chemical

shifts in the ²⁹Si NMR spectra, their values were taken from the

corresponding 2D spectra. The reactions were monitored in NMR

tubes in CDCl₃solution containing 0.05% Me₄Si as the internal

standard. The diﬀusion coeﬃcients were measured using 2D DOSY

¹H NMR spectroscopy (diﬀusion ordered spectroscopy)³²in CDCl₃

mode (interface capillary voltage 4500 V) with scan range m/z 50−

3000. External calibration of the mass spectrometer was performed

with Electrospray Calibrant Solution (Fluka). A direct syringe

injection was used for the all analyzed solutions in MeCN (ﬂow rate

3 μL/min). Nitrogen was used as nebulizer gas (0.4 bar) and dry gas

(4.0 L/min); the interface temperature was set at 180 °C. All spectra

were processed by using the Bruker DataAnalysis 4.0 software package.

The TLC analysis was carried out on standard silica gel

chromatography plates. The melting points were determined on a

Koﬂer hot-stage apparatus. Chromatography was performed on silica

gel (63−200 mesh and 5−40 μm).

CH₂Cl₂, Et₂O, petroleum ether (PE; 40/70), MeCN, THF, ethyl

acetate, H₂O₂(37% aqueous solution), cyclopentanone, cyclo-

hexanone, 4-methylcyclohexanone, 4-tert-butylcyclohexanone, cyclo-

heptanone, cyclododecanone, 4-methyl-2-pentanone, imidazole, pyr-

idine, DMAP, 2,6-lutidine, tetrahydroquinoline, diethylamine, triethyl-

1

solution on a 300 MHz spectrometer (300.1 MHz for H). The BPP-

LED pulse sequence was used with Δ = 100 ms and T_e= 5 ms. The

2D DOSY NMR spectra were processed by the monoexponential

ﬁtting and SCORE algorithm using the Bruker TopSpin and

DOSYToolbox software.³³Dibenzo-18-crown-6 and peroxides 3d

and 5c, which were added to the studied substances in a ∼1:1 molar

ratio, served as the internal and external calibrants of known molecular

masses in the DOSY NMR spectra. The 3D H−²⁹Si HMBC-DOSY

1

NMR spectra were acquired in CDCl₃on a 300 MHz spectrometer

1

(300.1 MHz for H). The novel pulse sequence composed of BBP-

LED and HMBC pulse sequences was used with Δ = 100 ms, T_e= 5

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1

Figure 6. 3D H−²⁹Si-HMBC-DOSY NMR spectrum processed by the monoexponential ﬁtting of cross-peak volumes for peroxides 10 and 11.

amine, and DABCO were purchased from Acros. Silica fume (particle

size 0.007 mm, S5130) was purchased from Sigma. A solution of H₂O₂

in Et₂O (5.8 wt %) was prepared by extraction with Et₂O (5 × 100

mL) from a 37% aqueous solution (100 mL) followed by drying over

MgSO₄.

gem-Bis(hydroperoxides) 2a−h. These compounds were

synthesized according to known procedures.³⁸

1,1-Bis(hydroperoxy)cyclopentane (2a).³⁸Oil. H NMR (250.13

1

MHz, CDCl₃): δ 1.582.-2.05 (m, 8H), 9.80−10.05 (br s, 2H). ¹³C

NMR (62.9 MHz, CDCl₃): δ 24.4, 33.0, 122.1.

Crystal structure data have been deposited at the Cambridge

Crystallographic Data Centre: CCDC 992998 (3d), 992999 (3g),

993000 (5c), 993001 (10′).

1,1-Bis(hydroperoxy)cyclohexane (2b).³⁸Colorless crystals. Mp:

48−50 °C (Et₂O) (lit.³⁸mp 48−49 °C). H NMR (250.13 MHz,

1

CDCl₃): δ 1.32−1.61 (m, 6H), 1.72−1.91 (m, 4H), 9.45−9.65 (br s,

2H). ¹³C NMR (62.9 MHz, CDCl₃): δ 22.3, 25.2, 29.4, 111.1.

1,1-Bis(hydroperoxy)-4-methylcyclohexane (2c).³⁸Colorless crys-

1,2-Bis(chlorodimethylsilyl)ethane (1). This compound was

1

purchased from Acros Organics. The H and ¹³C NMR spectroscopic

data are similar to those reported in the study.³⁷¹H NMR (300.13

MHz, CDCl₃): δ 0.42 (s, 12H), 0.81 (s, 4H). ¹³C NMR (75.48 MHz,

CDCl₃): δ 0.96, 10.70. ²⁹Si NMR (59.62 MHz, CDCl₃): δ 33.02.

tals. Mp: 54−56 °C (Et₂O) (lit.³⁸mp 53−55 °C). H NMR (250.13

1

MHz, CDCl₃): δ 0.92 (m, 3H), 1.1−1.71 (m, 7H), 2.11−2.29 (m,

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1,1-Bis(hydroperoxy)cyclododecane (2g).³⁸Colorless crystals. Mp:

138−140 °C (Et₂O) (lit.³⁸mp 138−140 °C). ¹H NMR (250.13 MHz,

CDCl₃): δ 1.21−1.82 (m, 22H), 9.98−10.04 (br s, 2H). ¹³C NMR

(62.9 MHz, CDCl₃): δ 20.0, 22.2, 22.5, 26.4, 26.5, 27.4, 113.

2,2-Bis(hydroperoxy)-4-methylpentane (2h).³⁸Oil. ¹H NMR

(250.13 MHz, CDCl₃): δ 0.96 (d, 6H, CH₃, J = 6.7 Hz), 1.42 (s,

3H, CH₃), 1.65−1.90 (m, 3H, CH₂, CH), 9.20−9.45 (br s, 2H,

OOH). ¹³C NMR (62.9 MHz, CDCl₃): δ 17.9 (CH), 23.7, 24.2

(CH₃), 41.3 (CH₂), 112.7 (C).

Scheme 8. Synthesis of Peroxides 12′, 12, and 13 from 1,2-

Bis(dimethylchlorosilyl)ethyne (7) and gem-

Bis(hydroperoxide) 2d

1,1′-Bis(hydroperoxy)bis(cycloalkyl)peroxides 4a−c. These

compounds were synthesized as has been described previously for

4a,³⁹4b,³⁹4c,³⁹and 1,1′-bis(hydroperoxy)bis(cyclododecyl)-

peroxide.³⁹

1,1′-Bis(hydroperoxy)bis(cyclopentyl)peroxide (4a). Colorless

crystals. Mp: 60−62 °C (H₂O) (lit.^24amp 60−63 °C). ¹H NMR

(250.13 MHz, CDCl₃): δ 1.53−1.80 (m, 8H), 1.81−2.11 (m, 8H),

9.82−9.98 (br s, 2H). ¹³C NMR (62.9 MHz, CDCl₃). δ: 23.5, 33.1,

122.1.

1,1′-Bis(hydroperoxy)bis(cyclohexyl)peroxide (4b). Colorless crys-

tals. Mp: 80−82 °C (H₂O) (lit.^24amp 80−81 °C). H NMR (250.13

1

MHz, CDCl₃): δ 1.43−1.67 (m, 12H), 1.79−1.93 (m, 8H), 9.40−9.62

(br s, 2H). ¹³C NMR (62.9 MHz, CDCl₃): δ 22.8, 25.4, 29.9, 111.2.

1,1′-Bis(hydroperoxy)bis(cycloheptyl)peroxide (4c). Colorless

crystals. Mp: 71−73 °C (H₂O) (lit.^24amp 71−72 °C). ¹H NMR

(250.13 MHz, CDCl₃): δ 1.51−1.71 (m, 16H), 1.93−2.04 (m, 8H),

9.57−9.65(s, 2H). ¹³C NMR (62.9 MHz, CDCl₃): δ 22.5, 29.8, 33.0,

116.2.

Table 5. ²⁹Si NMR Chemical Shifts (δ, ppm) for

1,1′-Bis(hydroperoxy)bis(cyclododecyl)peroxide. Colorless crys-

tals. Mp: 154−155 °C (Et₂O) (lit.^24amp 154−155.5 °C). H NMR

1

Dichlorodisilanes 1, 6, and 7, Si-Containing Peroxides 3d,

5c, and 8−13, and Siloxanes Synthesized by the Hydrolysis

(300.13 MHz, CDCl₃): δ 1.21−1.82 (m, 44H), 9.78 (br s, 2H). ¹³C

NMR (75.47 MHz, CDCl₃): δ 19.4, 21.9, 22.1, 25.9, 26.2, 26.4, 115.4.

Experiment Referred to Table 1: Synthesis of 3-tert-Butyl-

9,9,12,12-tetramethyl-7,8,13,14-tetraoxa-9,12-disilaspiro[5.8]-

tetradecane (3d). Footnote a. A solution of dichlorodisilane 1

(0.115 g, 0.535 mmol) in Et₂O (2 mL) was added with vigorous

stirring at 20−25 °C for 2−3 min to a solution of 1,1-

bis(hydroperoxy)-4-tert-butylcyclohexane (2d; 0.109 g, 0.535 mmol)

and, in runs 1−8, the corresponding amine: imidazole, pyridine, 2,6-

dimethylpyridine, 4-dimethylaminopyridine, quinoline, tetrahydroqui-

noline, diethylamine, triethylamine, or DABCO (0.076−0.150 g, 1.123

mmol, 2.1 mol/mol of 2d) in Et₂O (5 mL); in run 9, amine was not

added. The mixture was stirred for 1.5 h. Petroleum ether (30 mL) was

added to the reaction mixture, and the mixture was ﬁltered through a

short layer (1.5−2 cm) of silica gel (5−40 μm) using a water-jet

vacuum pump. Then the solvent was evaporated using a water-jet

vacuum pump.

a

of 1, 6, and 7

Footnote b. A solution of 1,1-bis(hydroperoxy)-4-tert-butylcyclo-

hexane (2d; 0.109 g, 0.535 mmol) in Et₂O (2 mL) was added with

vigorous stirring at 20−25 °C for 2−3 min to a solution of

dichlorodisilane 1 (0.115 g, 0.535 mmol) and amine (imidazole in

run 1 and pyridine in run 2; 0.076−0.089 g, 1.123 mmol, 2.1 mol/mol

of peroxide 2d) in Et₂O (5 mL). The mixture was stirred for 1.5 h.

Compound 3d was isolated as described in footnote a.

a

The ²⁹Si NMR spectra were recorded using the INEPT pulse

sequence and 2D HMBC techniques.

Footnote c, Run 2. Dichlorodisilane 1 (0.115 g, 0.535 mmol) was

added with vigorous stirring at 20−25 °C for 2−3 min to a solution of

1,1-bis(hydroperoxy)-4-tert-butylcyclohexane (2d; 0.109 g, 0.535

mmol) in pyridine (5 mL). The mixture was stirred for 1.5 h. The

TLC data and ¹H and ¹³C NMR spectra showed no conversion of the

starting reagents.

Footnote d. A solution of amine (0.076−0.089 g, 1.123 mmol, 2.1

mol/mol of peroxide 2d) in Et₂O (2 mL) was added with stirring at

20−25 °C for 2−3 min to a solution of dichlorodisilane 1 (0.115 g,

0.535 mmol) and 1,1-bis(hydroperoxy)-4-tert-butylcyclohexane (2d;

0.109 g, 0.535 mmol) in Et₂O (5 mL). The mixture was stirred for 1.5

h. Compound 3d was isolated as described in footnote a.

2H), 8.90−9.50 (br s, 2H). ¹³C NMR (62.9 MHz, CDCl₃): δ 21.3,

29.0, 30.0, 31.5, 110.9.

1,1-Bis(hydroperoxy)-4-tert-butylcyclohexane (2d).³⁸Colorless

crystals. Mp: 81−83 °C (Et₂O) (lit.³⁸mp 81−82.5 °C). H NMR

1

(250.13 MHz, CDCl₃): δ 0.85 (s, 9H), 0.98−1.78 (m, 7H), 2.24−2.35

(m, 2H), 9.25−9.40 (br s, 2H). ¹³C NMR (62.9 MHz, CDCl₃): δ 23.4,

27.6, 29.8, 32.3, 47.5, 110.7.

1,1-Bis(hydroperoxy)-3,3,5-trimethylcyclohexane (2e).³⁸Colorless

crystals. Mp: 55−57 °C (Et₂O) (lit.³⁸mp 55.5−57 °C). H NMR

1

(250.13 MHz, CDCl₃): δ 0.76−2.4 (m, 16H), 9.3−9.7 (br s, 2H). ¹³

C

NMR (62.9 MHz, CDCl₃): δ 21.95, 25.3, 26.2, 31.39, 33.5, 37.5, 40.5,

48.1, 112.0.

NMR Experiment on the Decomposition of 2d with DABCO

and Et₃N. 1,1-Bis(hydroperoxy)-4-tert-butylcyclohexane (2d; 0.025 g,

0.123 mmol) and DABCO (0.029 g, 0.257 mmol) or Et₃N (0.026 g,

0.123 mmol) were dissolved in CDCl₃(0.6 mL) in an NMR tube.

1,1-Bis(hydroperoxy)cycloheptane (2f).³⁸Colorless crystals. Mp:

20−21 °C (Et₂O) (lit.³⁸mp 19−21 °C). H NMR (250.13 MHz,

1

CDCl₃): δ 1.28−1.65 (m, 8H), 1.70−2.03 (m, 4H), 9.60−9.80 (br s,

1

2H). ¹³C NMR (62.9 MHz, CDCl₃): δ 22.6, 29.7, 32.7, 115.7.

After storage for 20 min, H and ¹³C NMR spectra were recorded. In

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the ¹³C NMR spectrum, a signal corresponding to the carbonyl carbon

atom of 4-tert-butylcyclohexanone appeared at δ 212.4. The TLC data

for the reaction mixture also conﬁrmed the formation of 4-tert-

butylcyclohexanone.

10:1). ¹H NMR (300.13 MHz, CDCl₃): δ 0.10−0.20 (m, 12H), 0.66−

2.36 (m, 20H). ¹³C NMR (75.48 MHz, CDCl₃): δ −3.86, −3.17, 4.61,

4.79, 22.09, 25.42, 26.35, 31.42, 33.68, 48.50, 110.74. ²⁹Si NMR (59.6

MHz, CDCl₃): δ 25.9, 26.5. Anal. Calcd for C₁₅H₃₂O₄Si₂: C, 54.17; H,

9.70; Si, 16.89. Found: C, 54.16; H, 9.43; Si, 16.92.

10,10,13,13-Tetramethyl-8,9,14,15-tetraoxa-10,13-disilaspiro-

[6.8]pentadecane (3f). Oil. R_f= 0.77 (TLC, hexane−ethyl acetate,

10:1). ¹H NMR (300.13 MHz, CDCl₃): δ 0.15 (s, 12H), 0.78 (s, 4H),

1.51−2.02 (m, 12H). ¹³C NMR (75.48 MHz, CDCl₃): δ −3.48, 4.92,

23.09, 30.17, 33.19, 105.03. ²⁹Si NMR (59.6 MHz, CDCl₃): δ 24.8,

26.2. Anal. Calcd for C₁₃H₂₈O₄Si₂: C, 51.27; H, 9.27; Si, 18.45. Found:

C, 51.40; H, 9.14; Si, 18.63.

NMR Monitoring of the Reaction of 1,2-Bis-

(dimethylchlorosilyl)ethane (1) with Imidazole in Diﬀerent

Ratios. Dichlorodisilane 1 (0.046 g, 0.214 mmol) and imidazole taken

in molar ratios of 1:1 (0.0146 g, 0.214 mmol), 1:2 (0.029 g, 0.428

mmol), 1:4 (0.058 g, 0.856 mmol), and 1:6 (0.087 g, 1.284 mmol)

were dissolved in CDCl₃(0.6 mL) in an NMR tube. After storage for

1

20 min, the H, ¹³C, and ²⁹Si NMR spectra were recorded. At the

ratios 1:imidazole = 1:1 and 1:2, the ²⁹Si NMR spectra were recorded

also 24 h after mixing.

3,3,6,6-Tetramethyl-1,2,7,8-tetraoxa-3,6-disilaspiro[8.11]-

eicosane (3g). White crystals. Mp = 110−112 °C (MeOH). R_f= 0.9

Experiment Referred to Table 2: Inﬂuence of the Reaction

Time, the Reagent Ratio, and the Nature of the Solvent on the

Synthesis of 3d from 2d in the Presence of Imidazole as the

Base. General Procedure of the Synthesis of 3d. A solution of

dichlorodisilane 1 (0.115 or 0.173 g, 0.535 or 0.803 mmol) in Et₂O,

CH₃CN, CH₂Cl₂, or THF (2 mL) was added with vigorous stirring at

20−25 °C for 2−3 min to a solution of 1,1-bis(hydroperoxy)-4-tert-

butylcyclohexane (2d; 0.109 g, 0.535 mmol) and imidazole (0.076−

0.218 g, 1.123−3.210 mmol, 2.1−6 mol/mol of peroxide 2d) in Et₂O,

CH₃CN, CH₂Cl₂, or THF (5 mL). The mixture was stirred for 0.1−29

h.

The isolation was performed as described for 3d (Table 1).

Experiment on the Eﬀect of the Rate of the Addition of

Bis(dimethylchlorosilyl)ethane (1) to a Mixture of 2d and

Imidazole on the Synthesis of 3d. A solution of dichlorodisilane 1

(0.115 g, 0.535 mmol) in Et₂O (2 mL) was added with vigorous

stirring at 20−25 °C for 1−2 s to a solution of 1,1-bis(hydroperoxy)-4-

tert-butylcyclohexane (2d; 0.109 g, 0.535 mmol) and imidazole (0.076

g, 1.123 mmol, 2.1 mol/mol of peroxide 2d) in Et₂O (5 mL). An

insoluble white viscous mixture was obtained.

1

(TLC, hexane−ethyl acetate, 10:1). H NMR (300.13 MHz, CDCl₃):

δ 0.14 (s, 12H), 0.78 (s, 4H), 1.3−1.74 (m, 22H). ¹³C NMR (75.48

MHz, CDCl₃): δ −3.48, 4.77, 19.56, 21.97, 22.32, 26.15, 26.70, 113.91.

²⁹Si NMR (59.6 MHz, CDCl₃): δ 25.9. Anal. Calcd for C₁₈H₃₈O₄Si₂:

C, 57.70; H, 10.22; Si, 14.99. Found: C, 57.92; H, 10.12; Si, 15.14.

9-Isobutyl-3,3,6,6,9-pentamethyl-1,2,7,8,3,6-tetraoxadisilonane

1

(3h). Oil. R_f= 0.84 (TLC, hexane−ethyl acetate, 10:1). H NMR

(300.13 MHz, CDCl₃): δ 0.14 (s, 12H), 0.78 (s, 4H), 091−1.86(m,

12H). ¹³C NMR (75.48 MHz, CDCl₃): δ −3.52, 4.81, 18.44, 23.84,

24.40, 42.47, 111.36. ²⁹Si NMR (59.6 MHz, CDCl₃): δ 26.4. Anal.

Calcd for C₁₂H₂₈O₄Si₂: C, 49.27; H, 9.65; Si, 19.20. Found: C, 49.36;

H, 9.70; Si, 16.32.

Experiment Referred to Table 4: Synthesis of 1,2,7,8,10,11-

Hexaoxa-3,6-disilacyclododecanes 5a−c. General Procedure

of the Synthesis of 5a−c. a solution of dichlorodisilane 1 (0.150 g,

0.698 mmol) in Et₂O (1.5 mL) was added with vigorous stirring at

20−25 °C for 3−4 min to a mixture of 1,1′-bis(hydroperoxy)bis-

(cycloalkyl)peroxides 4a−c (0.163−0.202 g, 0.698 mmol) and a base

(0.1 g, 1.465 mmol) in Et₂O (3.5−4 mL). The mixture was stirred for

3 h.

Footnote a. Petroleum ether (30 mL) was added to the reaction

mixture, and the mixture was ﬁltered through a short layer (1.5−2 cm)

of silica gel (5−40 μm) using a water-jet vacuum pump. Then the

solvent was evaporated using a water-jet vacuum pump.

Experiment Referred to Table 3. Synthesis of 1,2,7,8-

Tetraoxa-3,6-disilonanes 3a−h. A solution of dichlorodisilane 1

(0.115 g, 0.535 mmol) in Et₂O (2 mL) was added with vigorous

stirring at 20−25 °C for 2−3 min to a solution of 2a−h (0.148−0.200

g, 0.535 mmol) and imidazole (0.076 g, 1.123 mmol, 2.1 mol/mol of

2a−h) in Et₂O (5 mL). The mixture was stirred for 1−20 h. The

isolation was performed as described for 3d (Table 1).

Footnote b. Petroleum ether (30 mL) was added, and the mixture

was successively washed with a 5% NaOH solution (2 × 10 mL) and

water (2 × 10 mL). The organic phase was separated and dried over

MgSO₄. The solvent was evaporated using a water-jet vacuum pump.

Products 5a−c were isolated by crystallization from MeOH.

15,15,18,18-Tetramethyl-6,7,13,14,19,20-hexaoxa-15,18-

disiladispiro[4.2.4.8]eicosane (5a). White crystals. Mp = 85−88 °C

(MeOH). R_f= 0.7 (TLC, hexane−ethyl acetate, 10:1). ¹H NMR

(300.13 MHz, CDCl₃): δ 0.14 (s, 12H), 0.85 (br s, 4H), 1.52−2.21

(m, 16H). ¹³C NMR (75.48 MHz, CDCl₃): δ −3.73, 5.68, 24.92,

33.97, 120.98. Anal. Calcd for C₁₆H₃₂O₆Si₂: C, 51.03; H, 8.56; Si,

14.92. Found: C, 50.83; H, 8.31; Si, 15.00. HRMS (ESI) m/z [M +

Na]⁺: calcd for [C₁₆H₃₂NaO₆Si₂]⁺, 399.1630; found, 399.1629.

17,17,20,20-Tetramethyl-7,8,15,16,21,22-hexaoxa-17,20-

disiladispiro[5.2.5.8]docosane (5b). White crystals. Mp = 113−116

8,8,11,11-Tetramethyl-6,7,12,13-tetraoxa-8,11-disilaspiro[4.8]-

1

tridecane (3a). Oil. R_f= 0.57 (TLC, hexane−ethyl acetate, 10:1). H

NMR (300.13 MHz, CDCl₃): δ 0.15 (s, 12H), 0.80 (s, 4H), 1.22−2.07

(m, 8H). ¹³C NMR (75.48 MHz, CDCl₃): δ −3.48, 4.96, 24.83, 33.42,

121.22. ²⁹Si NMR (59.6 MHz, CDCl₃): δ 26.7. Anal. Calcd for

C₁₁H₂₄O₄Si₂: C, 47.79; H, 8.75; Si, 20.32. Found: C, 47.56; H, 8.74; Si,

20.45.

9,9,12,12-Tetramethyl-7,8,13,14-tetraoxa-9,12-disilaspiro[5.8]-

tetradecane (3b). Oil. R_f= 0.79 (TLC, hexane−ethyl acetate, 10:1).

¹H NMR (300.13 MHz, CDCl₃): δ 0.14 (s, 12H), 0.78 (s, 4H), 1.23−

1.86 (m, 10H). ¹³C NMR (75.48 MHz, CDCl₃): δ −3.48, 4.80, 22.76,

25.61, 30.07, 109.54. ²⁹Si NMR (59.6 MHz, CDCl₃): δ 26.4. Anal.

Calcd for C₁₂H₂₆O₄Si₂: C, 49.61; H, 9.02; Si, 19.34. Found: C, 49.55;

H, 9.10; Si, 19.48.

1

°C (MeOH). R_f= 0.7 (TLC, hexane−ethyl acetate, 10:1). H NMR

3,9,9,12,12-Pentamethyl-7,8,13,14-tetraoxa-9,12-disilaspiro[5.8]-

tetradecane (3c). Oil. R_f= 0.68 (TLC, hexane−ethyl acetate, 10:1).

¹H NMR (300.13 MHz, CDCl₃): δ 0.15 (s, 12H), 0.78 (s, 4H), 0.87−

(300.13 MHz, CDCl₃): δ 0.14 (s, 12H), 0.85 (br s, 4H), 1.14−2.23

(m, 20H). ¹³C NMR (75.48 MHz, CDCl₃): δ −3.62, 5.75, 22.70,

25.58, 30.60, 109.01. Anal. Calcd for C₁₈H₃₆O₆Si₂: C, 53.43; H, 8.97;

Si, 13.88. Found: C, 53.18; H, 8.86; Si, 14.02. HRMS (ESI) m/z [M +

Na]⁺: calcd for [C₁₈HH₃₆NaO₆Si₂]⁺, 427.1943; found, 427.1943.

19,19,22,22-Tetramethyl-8,9,17,18,23,24-hexaoxa-19,22-

disiladispiro[6.2.6.8]tetracosane (5c). White crystals. Mp = 124−126

2.41 (m, 12H). ¹³C NMR (75.48 MHz, CDCl₃): δ −3.49, 4.79, 21.52,

29.56, 31.04, 31.80, 109.50. ²⁹Si NMR (59.6 MHz, CDCl₃): δ 26.3,

26.7. Anal. Calcd for C₁₃H₂₈O₄Si₂: C, 51.27; H, 9.27; Si, 18.45. Found:

C, 51.40; H, 9.28; Si, 18.62.

1

3-tert-Butyl-9,9,12,12-tetramethyl-7,8,13,14-tetraoxa-9,12-

°C (MeOH). R_f= 0.75 (TLC, hexane−ethyl acetate, 10:1). H NMR

disilaspiro[5.8]tetradecane (3d). White crystals. Mp = 78−81 °C

(300.13 MHz, CDCl₃): δ 0.13 (s, 12H), 0.85 (br s, 4H), 1.46−2.10

(m, 24H). ¹³C NMR (75.48 MHz, CDCl₃): δ −3.67, 5.73, 23.39,

31.07, 34.46, 115.04. Anal. Calcd for C₂₀H₄₀O₆Si₂: C, 55.52; H, 9.32;

Si, 12.98. Found: C, 55.45; H, 9.23; Si, 12.83. HRMS (ESI) m/z [M +

Na]⁺: calcd for [C₂₀H₄₀NaO₆Si₂]⁺, 455.2256; found, 455.2269.

Synthesis and Analysis of 18-Membered Peroxide 3,18-Di-

t e r t - b u t y l - 9 , 9 , 1 2 , 1 2 , 2 3 , 2 3 , 2 6 , 2 6 - o c t a m e t h y l -

7,8,13,14,21,22,27,28-octaoxa-9,12,23,26-tetrasiladispiro-

[5.8.5.8]octacosa-10,24-diene (8) from 1,2-Bis-

1

(MeOH). R_f= 0.81 (TLC, hexane−ethyl acetate, 10:1). H NMR

(300.13 MHz, CDCl₃): δ 0.14 (s, 12H), 0.78 (s, 4H), 0.84 (s, 9H),

0.89−2.4 (m, 9H). ¹³C NMR (75.48 MHz, CDCl₃): δ −3.48, 4.86,

23.64, 27.63, 30.25, 32.30, 47.51, 109.42. ²⁹Si NMR (59.6 MHz,

CDCl₃): δ 26.25, 26.8. Anal. Calcd for C₁₆H₃₄O₄Si₂: C, 55.44; H, 9.89;

Si, 16.21. Found: C, 55.46; H, 9.77; Si, 16.35.

2,2,4,9,9,12,12-Heptamethyl-7,8,13,14-tetraoxa-9,12-disilaspiro-

[5.8]tetradecane (3e). Oil. R_f= 0.57 (TLC, hexane−ethyl acetate,

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(dimethylchlorosilyl)ethene (6) and gem-Bis(hydroperoxide)

2d. A solution of dichlorodisilane 6 (0.114 g, 0.535 mmol) in Et₂O (2

mL) was added with vigorous stirring under argon at 20−25 °C for 2−

3 min to a solution of 1,1-bis(hydroperoxy)-4-tert-butylcyclohexane

(2d; 0.109 g, 0.535 mmol) and imidazole (0.076 g, 1.123 mmol, 2.1

mol/mol of 2d) in Et₂O (5 mL). The mixture was stirred for 1.5 h.

Petroleum ether (30 mL) was added to the reaction mixture, and the

mixture was ﬁltered through a short layer (1.5−2 cm) of silica gel (5−

40 μm) using a water-jet vacuum pump. Then the solvent was

evaporated using a water-jet vacuum pump. A mixture of peroxides 8

and 8′ was obtained in a total amount of 0.175 g. The yields of

peroxides 8 and 8′ were approximately 90 and 5%, respectively

was ﬁltered through a short layer (1.5−2 cm) of silica gel (5−40 μm)

using a water-jet vacuum pump. Then the solvent was evaporated

using a water-jet vacuum pump. Product 9 was synthesized in 80%

yield (0.184 g, 0.214 mmol).

Reaction of 1,2-Bis(dimethylchlorosilyl)ethene (6) with 1,1′-

Bis(hydroperoxy)bis(cycloheptyl)peroxide (4c). Analysis of the

Products on the Basis of ¹H, ¹³C, ²⁹Si, COSY, HSQC, and HMBC

NMR Data. 1,1′-Bis(hydroperoxy)bis(cycloheptyl)peroxide (4c; 0.05

g, 0.1724 mmol) and pyridine (0.0286 g, 0.362 mmol) taken in a

molar ratio of 1:2.1 were dissolved in CDCl₃(0.6 mL) in an NMR

tube. The tube was purged with argon, and then bis-

(chlorodimethylsilyl)ethylene (6; 0.0367 g, 0.1724 mmol) was

1

added. After storage for 1 h, H, ¹³C, and ²⁹Si NMR spectra were

1

(estimated from the 2D DOSY H NMR spectrum).

recorded using 2D correlation techniques COSY, HSQC, and HMBC.

Reaction of 1,2-Bis(dimethylchlorosilyl)ethene (6) with 1,1′-

Bis(hydroperoxy)bis(cycloheptyl)peroxide (4c) in the Presence

of Dibenzo-18-crown-6 as the Calibrant. Analysis of the

Reaction of 1,2-Bis(dimethylchlorosilyl)ethene (6) with gem-

Bis(hydroperoxide) 2d. Analysis of the Products on the Basis

of ¹H, ¹³C, ²⁹Si, COSY, HSQC, and HMBC NMR Data. 1,1-

Bis(hydroperoxy)-4-tert-butylcyclohexane (2d; 0.0352 g, 0.1724

mmol) and pyridine (0.0286 g, 0.362 mmol) taken in a molar ratio

of 1:2.1 were dissolved in CDCl₃(0.6 mL) in an NMR tube. The tube

was purged with argon and then bis(chlorodimethylsilyl)ethene (6;

1

Products on the Basis of 2D DOSY H NMR Data. The reaction

was performed as described above. After 1 h, dibenzo-18-crown-6

(0.0250 g, 0.0694 mmol) was added as the calibrant. Then silica fume

(1 wt %) was added to the NMR tube, and the mixture was shaken.

1

0.0367 g, 0.1724 mmol) was added. After 1 h, the H, ¹³C, and ²⁹Si

1

The 2D DOSY H NMR spectrum was recorded.

NMR spectra of 8 and 8′ were recorded using 2D correlation

1 9 , 1 9 , 2 2 , 2 2 , 4 3 , 4 3 , 4 6 , 4 6 - O c t a m e t h y l -

8,9,17,18,23,24,32,33,41,42,47,48-dodecaoxa-19,22,43,46-

tetrasilatetraspiro[6.2.6¹⁰.8.6²⁵.2.6³⁴.8⁷]octatetraconta-20,44-diene

techniques COSY, HSQC, and HMBC.

Reaction of 1,2-Bis(dimethylchlorosilyl)ethene (6) with gem-

Bis(hydroperoxide) 2d in the Presence of Dibenzo-18-crown-6

as the Calibrant. Analysis of the Products on the Basis of 2D

1

(9). R_f= 0.7 (TLC, hexane−ethyl acetate, 10:1). H NMR (400.1

1

MHz, CDCl₃): δ 0.1−0.6 (m, 24H), 1.3−2.2 (m, 48H), 6.7−6.8 (m,

4H). ¹³C NMR (100.6 MHz, CDCl₃): δ −3.5 (br), 23.1, 30.8, 34.4,

115.5, 148.6. ²⁹Si NMR (59.6 MHz, CDCl₃): δ 11.6, 12.65. Anal.

Calcd for C₄₀H₇₆O₁₂Si₄: C, 55.78; H, 8.89; Si, 13.04. Found: C, 54.23;

H, 9.01; Si, 12.36.

DOSY H NMR Data (Figure 3). The reaction was carried out as

described above. After 1 h, dibenzo-18-crown-6 (0.0250 g, 0.0694

mmol) was added as the calibrant. Then silica fume (1 wt %) was

added to the NMR tube, and the mixture was shaken. The 2D DOSY

¹H NMR spectrum was recorded. Conditions: CDCl₃, 8 0.3 mol/L, 1

Synthesis and Analysis of 24- and 36-Membered Peroxides

1 9 , 1 9 , 2 2 , 2 2 , 4 3 , 4 3 , 4 6 , 4 6 - O c t a m e t h y l -

8,9,17,18,23,24,32,33,41,42,47,48-dodecaoxa-19,22,43,46-

tetrasilatetraspiro[6.2.6¹⁰.8.6²⁵.2.6³⁴.8⁷]octatetraconta-20,44-

diyne (10) and 19,19,22,22,43,43,46,46,67,67,70,70-dodeca-

methyl-8,9,17,18,23,24,32,33,41,42,47,48,56,57,65,66,71,72-

octadecaoxa-19,22,43,46,67,70-hexasilahexaspiro-

[6.2.6¹⁰.8.6²⁵.2.6³⁴.8.6⁴⁹.2.6⁵⁸.8⁷]doheptaconta-20,44,68-triyne

(11) from 1,2-Bis(dimethylchlorosilyl)ethyne (7) and 1,1′-

Bis(hydroperoxy)bis(cycloheptyl)peroxide (4c). A solution of

dichlorodisilane 7 (0.113 g, 0.535 mmol) in Et₂O (2 mL) was added

with vigorous stirring under argon at 20−25 °C for 2−3 min to a

solution of 1,1′-bis(hydroperoxy)bis(cycloheptyl)peroxide (4c; 0.155

g, 0.535 mmol) and imidazole (0.076 g, 1.123 mmol, 2.1 mol/mol of

4c) in Et₂O (5 mL). Then petroleum ether (30 mL) was added, and

the reaction mixture was ﬁltered through a short layer (1.5−2 cm) of

silica gel (5−40 μm) using a water-jet vacuum pump. Then the solvent

was evaporated using a water-jet vacuum pump. A mixture of peroxides

10, 10′, and 11 was obtained in a total amount of 0.195 g. The yields

of peroxides 10, 10′, and 11 were approximately 30, 5, and 50%,

wt % silica fume, 32 °C, BPP-LED pulse sequence, Δ = 100 ms, T_e= 5

ms. The components in the spectrum are represented by horizontal

dashed lines of diﬀerent colors: 8, blue; 8′, gray (minor); dibenzo-18-

crown-6, green; pyridine, light blue. The peak enclosed by a blue

dashed oval is not observed upon the ﬁtting due to overlap with more

intense signals.

Reaction of 1,2-Bis(dimethylchlorosilyl)ethene (6) with gem-

Bis(hydroperoxide) 2d in the Presence of Dibenzo-18-crown-6

and Peroxide (3d) as Calibrants. Analysis of the Products on

the Basis of 2D DOSY ¹H NMR Data (Figure 4). The reaction was

carried out as described above. After 1 h, dibenzo-18-crown-6 (0.0250

g, 0.0694 mmol) and tetraoxadisilonate 3d (0.0241 g, 0.0694 mmol)

were added as the calibrants. Then silica fume (1 wt %) was added to

the NMR tube, and the mixture was shaken. The 2D DOSY ¹H NMR

spectrum was processed with the SCORE algorithm for peroxide using

dibenzo-18-crown-6 and 3d as the calibrants. Conditions: see Figure 3.

The components in the spectra are represented by horizontal dashed

lines of diﬀerent colors: 8, blue; 3d, red; dibenzo-18-crown-6, green;

pyridine, light blue.

3,18-Di-tert-butyl-9,9,12,12,23,23,26,26-octamethyl-

7,8,13,14,21,22,27,28-octaoxa-9,12,23,26-tetrasiladispiro[5.8.5.8]-

octacosa-10,24-diene (8, Major) and 3-tert-Butyl-9,9,12,12-tetra-

methyl-7,8,13,14-tetraoxa-9,12-disiladispiro[5.8]tetradec-10-ene

1

respectively (2D DOSY H NMR spectroscopic data).

Reaction of 1,2-Bis(dimethylchlorosilyl)ethyne (7) with 1,1′-

Bis(hydroperoxy)bis(cycloheptyl)peroxide (4c). Analysis of the

Products on the Basis of ¹H, ¹³C, ²⁹Si, COSY, HSQC, and HMBC

NMR Data. 1,1′-Bis(hydroperoxy)bis(cycloheptyl)peroxide (4c; 0.05

g, 0.1724 mmol) and pyridine (0.0286 g, 0.362 mmol) taken in a

molar ratio of 1:2.1 were dissolved in CDCl₃(0.6 mL) in an NMR

tube. The tube was purged with argon, and then bis-

(chlorodimethylsilyl)ethyne (7; 0.0364 g, 0.1724 mmol) was added.

1

(8′, Minor). R_f= 0.88 (TLC, hexane−ethyl acetate, 10:1). H NMR

(400.1 MHz, CDCl₃): δ 0.2−0.45 (m, 24H, 12H), 0.8−2.4 (m, 36H,

18H), 6.65−6.95 (m, 4H, 2H). ¹³C NMR (100.6 MHz, CDCl₃): δ

−2.6 (br), 22.7, 23.7, 27.7, 30.6, 32.3, 47.6, 109.3, 149.1. ²⁹Si NMR

(59.6 MHz, CDCl₃): δ 12.7, 13.5. Anal. Calcd for C₃₂H₆₄O₈Si₄: C,

55.77; H, 9.36; Si, 16.30. Found: C, 54.32; H, 9.78; Si, 15.79.

1

After storage for 1 h, H, ¹³C, and ²⁹Si NMR spectra were recorded

Synthesis and Analysis of 24-Membered Peroxide

1 9 , 1 9 , 2 2 , 2 2 , 4 3 , 4 3 , 4 6 , 4 6 - O c t a m e t h y l -

8,9,17,18,23,24,32,33,41,42,47,48-dodecaoxa-19,22,43,46-

tetrasilatetraspiro[6.2.6¹⁰.8.6²⁵.2.6³⁴.8⁷]octatetraconta-20,44-

diene (9) from 1,2-Bis(dimethylchlorosilyl)ethene (6) and 1,1′-

Bis(hydroperoxy)bis(cycloheptyl)peroxide (4c). A solution of

bis(chlorodimethylsilyl)ethylene (6; 0.114 g, 0.535 mmol) in Et₂O (2

mL) was added with vigorous stirring under argon at 20−25 °C for 2−

3 min to a solution of 1,1′-bis(hydroperoxy)bis(cycloheptyl)peroxide

(4c; 0.155 g, 0.535 mmol) and imidazole (0.076 g, 1.123 mmol, 2.1

mol/mol of 4c) in Et₂O (5 mL). The mixture was stirred for 1.5 h.

Then petroleum ether (30 mL) was added, and the reaction mixture

using 2D correlation techniques COSY, HSQC, and HMBC.

Reaction of 1,2-Bis(dimethylchlorosilyl)ethyne (7) with 1,1′-

Bis(hydroperoxy)bis(cycloheptyl)peroxide (4c) in the Presence

of Dibenzo-18-crown-6 as the calibrant. Analysis of the

1

Products on the Basis of 2D DOSY H NMR Data (Figure 5).

The reaction was performed as described above. After 1 h, dibenzo-18-

crown-6 (0.025 g, 0.0694 mmol) was added as the calibrant. Then

silica fume (1 wt %) was added to the NMR tube, and the mixture was

shaken. The 2D DOSY ¹H NMR spectrum was processed by the

monoexponential ﬁtting for peroxides 10 and 11 using dibenzo-18-

crown-6 as the calibrant. Conditions: CDCl₃, see Figure 3. The major

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Organometallics

Article

compounds in the spectrum are indicated by a solid triangle; possible

and minor compounds are represented by dashed triangles of diﬀerent

colors: 10, blue; 11, red; dibenzo-18-crown-6, yellow; 10′ (minor; its

peaks are observed upon strong enhancement of the signal intensity in

the spectrum), green; oligomeric peroxides (not observed), brown;

pyridine, light blue.

was purged with argon, and then bis(chlorodimethylsilyl)ethyne (7;

1

0.0364 g, 0.1724 mmol) was added. After 1 h, H, ¹³C, and ²⁹Si NMR

spectra were recorded using 2D correlation techniques COSY, HSQC,

and HMBC.

Reaction of 1,2-Bis(dimethylchlorosilyl)ethyne (7) with gem-

Bis(hydroperoxide) 2d in the Presence of Dibenzo-18-crown-6

as the Calibrant. Analysis of the Products on the Basis of 2D

DOSY ¹H NMR Data. The reaction was performed as described

above. Then silica fume (1 wt %) was added to the NMR tube, and the

mixture was shaken. The 2D DOSY ¹H NMR spectrum was recorded.

Reaction of 1,2-Bis(dimethylchlorosilyl)ethyne (7) with gem-

Bis(hydroperoxide) 2d. Analysis of the Products on the Basis

of 3D ¹H−²⁹Si-HMBC-DOSY Data. 1,1-Bis(hydroperoxy)-4-tert-

butylcyclohexane (2d; 0.0352 g, 0.1724 mmol) and pyridine (0.0286

g, 0.362 mmol) taken in a molar ratio of 1:2.1 were dissolved in CDCl₃

(0.6 mL) in an NMR tube. The tube was purged with argon, and then

bis(chlorodimethylsilyl)ethyne (7; 0.0364 g, 0.1724 mmol) was added.

After 1 h, silica fume (1 wt %) was added to the tube, and the mixture

Reaction of 1,2-Bis(dimethylchlorosilyl)ethyne (7) with 1,1′-

Bis(hydroperoxy)bis(cycloheptyl)peroxide (4c). Analysis of the

1

Products on the Basis of 3D H−²⁹Si-HMBC-DOSY NMR Data

(Figure 6). The reaction was performed as described above. After 1 h,

silica fume (1 wt %) was added to the NMR tube, and the mixture was

shaken. The 3D ¹H−²⁹Si-HMBC-DOSY NMR spectrum was

processed by the monoexponential ﬁtting of cross-peak volumes for

peroxides 10 and 11. Conditions: CDCl₃, 0.3 mol/L, 1 wt % silica

fume, 32 °C. Pulse sequence: Δ = 100 ms, T_e= 5 ms, J_Si,H= 6 Hz. The

top of Figure 6 gives a 3D view of the HMBC-DOSY data; the methyl

region of the products is shown. The components in the spectra are

represented by horizontal dashed planes of diﬀerent colors: 10, blue;

11, red. The bottom of Figure 6gives the 3D HMBC-DOSY pulse

sequence. This pulse sequence is constructed of BPP-LED and HMBC

sequences. The narrow and wide ﬁlled rectangles represent 90 and

180° pulses (dark blue for the ¹H channel, dark red for the ²⁹Si

channel), and gray solid half-ellipses are z-gradient pulses. Vertical

arrows indicate diﬀusion-encoding gradient pulses, which are

incremented in sympathy, and half-ellipses without arrows are

homospoil-type gradients. Delays: Δ is the diﬀusion time, T_eis the

eddy current delay, δ is the gradient recovery delay. Gradient ratios: G₁

= 0−100%, diﬀusion-encoding gradient pulses; G₂= −17.13%; G₃=

−13.17%; G₄= 50−70%; G₅= 20−30%; G₆= (G₄+ G₅)/(γ_H/γ_X) +

(G₄− G₅). Phases: ϕ₁= 0; ϕ₂= 0; ϕ₃= 0; ϕ₄= 0; ϕ₅= 0; ϕ₆= 0022;

ϕ₇= 02; ϕ₈= 00002222; ϕ_R= 02022020.

1

was shaken. The 3D H−²⁹Si-HMBC-DOSY spectrum was recorded.

3,18-Di-tert-butyl-9,9,12,12,23,23,26,26-octamethyl-

7,8,13,14,21,22,27,28-octaoxa-9,12,23,26-tetrasiladispiro[5.8.5.8]-

octacosa-10,24-diyne (12. Major), 3,18,32-Tri-tert-butyl-

9 , 9 , 1 2 , 1 2 , 2 3 , 2 3 , 2 6 , 2 6 , 3 7 , 3 7 , 4 0 , 4 0 - d o d e c a m e t h y l -

7,8,13,14,21,22,27,28,35,36,41,42-dodecaoxa-9,12,23,26,37,40-

hexasilatrispiro[5.8.5¹⁵.8.5²⁹.8⁶]dotetraconta-10,24,38-triyne (13,

Major), and 3-tert-Butyl-9,9,12,12-tetramethyl-7,8,13,14-tetraoxa-

9,12-disilaspiro[5.8]tetradec-10-yne (12′, Minor). R_f= 0.76 (TLC,

hexane−ethyl acetate, 10:1). ¹H NMR (400.1 MHz, CDCl₃): δ 0.25−

0.45 (m, 24H, 36H, 12H), 0.8−2.45 (m, 36H, 54H, 18H). ¹³C NMR

(100.6 MHz, CDCl₃): δ −1.38 (br), 23.6, 27.7, 30.6, 32.5, 47.7, 109.6,

139.4. ²⁹Si NMR (59.6 MHz, CDCl₃): δ −2.5, −2.0. Anal. Calcd for

C₃₂H₆₀O₈Si₄, C₄₈H₉₀O₁₂Si₆: C, 56.10; H, 8.83; Si, 16.40. Found: C,

55.95; H, 9.02; Si, 15.67.

1 9 , 1 9 , 2 2 , 2 2 , 4 3 , 4 3 , 4 6 , 4 6 - O c t a m e t h y l -

8,9,17,18,23,24,32,33,41,42,47,48-dodecaoxa-19,22,43,46-

tetrasilatetraspiro[6.2.6¹⁰.8.6²⁵.2.6³⁴.8⁷]octatetraconta-20,44-diyne

(10, Major), 19,19,22,22,43,43,46,46,67,67,70,70-Dodecamethyl-

8,9,17,18,23,24,32,33,41,42,47,48,56,57,65,66,71,72-octadecaoxa-

1 9 , 2 2 , 4 3 , 4 6 , 6 7 , 7 0 - h e x a s i l a h e x a s p i r o -

[6.2.6¹⁰.8.6²⁵.2.6³⁴.8.6⁴⁹.2.6⁵⁸.8⁷]doheptaconta-20,44,68-triyne (11,

Major), and 19,19,22,22-Tetramethyl-8,9,17,18,23,24-hexaoxa-

19,22-disiladispiro[6.2.6.8]tetracos-20-yne (10′, minor). R_f= 0.61

(TLC, hexane−ethyl acetate, 10:1). ¹H NMR (400.1 MHz, CDCl₃): δ

0.2−0.45 (m, 24H, 36H, 12H), 1.35−2.2 (m, 48H, 72H, 24H). ¹³C

NMR (100.6 MHz, CDCl₃): δ −1.5 (br), 22.65 (br), 30.5(br),

33.1(br), 114.8, 138.6. ²⁹Si NMR (59.6 MHz, CDCl₃): δ −2.7 Anal.

Calcd for C₄₀H₇₂O₁₂Si₄, C₆₀H₁₀₈O₂₄Si₆: C, 56.04; H, 8.46; Si, 13.10.

Found: C, 55.97; H, 8.83; Si, 13.16.

ASSOCIATED CONTENT

■

S

* Supporting Information

Text, tables, ﬁgures, and CIF ﬁles giving H, ¹³C, 2D, and 3D

1

NMR spectra, mass spectra, and details of X-ray data. This

material is available free of charge via the Internet at http://

pubs.acs.org.

AUTHOR INFORMATION

Corresponding Author

*A.O.T.: e-mail, alterex@yandex.ru; tel, +7 (499) 1356428; fax,

+7 (499) 1355328.

■

Synthesis and Analysis of 18- and 27-Membered Peroxides

3,18-Di-tert-butyl-9,9,12,12,23,23,26,26-octamethyl-

7,8,13,14,21,22,27,28-octaoxa-9,12,23,26-tetrasiladispiro-

[5.8.5.8]octacosa-10,24-diyne (12) and 3,18,32-Tri-tert-butyl-

9,9,12,12,23,23,26,26,37,37,40,40-dodecamethyl-

7 , 8 , 1 3 , 1 4 , 2 1 , 2 2 , 2 7 , 2 8 , 3 5 , 3 6 , 4 1 , 4 2 - d o d e c a o x a -

9,12,23,26,37,40-hexasilatrispiro[5.8.5¹⁵.8.5²⁹.8⁶]dotetraconta-

10,24,38-triyne (13) from 1,2-Bis(dimethylchlorosilyl)ethyne

(7) and gem-Bis(hydroperoxide) 2d. A solution of dichlorodisilane

7 (0.113 g, 0.535 mmol) in Et₂O (2 mL) was added with vigorous

stirring under argon at 20−25 °C for 2−3 min to a solution of 1,1-

bis(hydroperoxy)-4-tert-butylcyclohexane (2d; 0.109 g, 0.535 mmol)

and imidazole (0.076 g, 1.123 mmol, 2.1 mol/mol of 2d) in Et₂O (5

mL). Petroleum ether (30 mL) was added, and the reaction mixture

was ﬁltered through a short layer (1.5−2 cm) of silica gel (5−40 μm)

using a water-jet vacuum pump. Then the solvent was evaporated

using a water-jet vacuum pump. A mixture of peroxides 12, 12′, and 13

was obtained in a total amount of 0.145 g. The yields of peroxides 12,

12′, and 13 were approximately 32, 7, and 40%, respectively (2D

Author Contributions

The manuscript was written through contributions of all

authors. All authors have given approval to the ﬁnal version of

the manuscript.

Notes

The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENTS

■

This work is supported by the Russian Foundation for Basic

Research (Grant 14-03-00237-a), the Program for Basic

Research of the Presidium of the Russian Academy of Sciences,

and the Ministry of Education and Science of the Russian

Federation. We are grateful to the ESRF for providing access to

the ID31 beamline (Experiment CH-3696). High-resolution

mass spectra were recorded in the Department of Structural

Studies of Zelinsky Institute of Organic Chemistry, Moscow.

We thankfully acknowledge Doctor Levon L. Khemchyan for

implementation of HRMS experiments.

1

DOSY H NMR spectroscopic data).

Reaction of 1,2-Bis(dimethylchlorosilyl)ethyne (7) with gem-

Bis(hydroperoxide) 2d. Analysis of the products on the Basis

of ¹H, ¹³C, ²⁹Si, COSY, HSQC, and HMBC NMR Data. 1,1-

Bis(hydroperoxy)-4-tert-butylcyclohexane (2d; 0.0352 g, 0.1724

mmol) and pyridine (0.0286 g, 0.362 mmol) taken in a molar ratio

of 1:2.1 were dissolved in CDCl₃(0.6 mL) in an NMR tube. The tube

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