ISSN 0965�5441, Petroleum Chemistry, 2012, Vol. 52, No. 4, pp. 261–266. © Pleiades Publishing, Ltd., 2012.Original Russian Text © R.I. Khusnutdinov, A.R. Bayguzina, L.I. Gallyamova, U.M. Dzhemilev, 2012, published in Neftekhimiya, 2012, Vol. 52, No. 4, pp. 292–298.

261

Benzyl alkyl ethers find wide application in per�fumery and food industry as fragrances and food addi�tives. Typically they are prepared by the Williamsonreaction between alkali metal alkoxides and benzylbromide [1] or Ag2O [2]. The synthesis of ethers fromsubstrates that are unstable in an alkaline medium isperformed with benzyl trifluoroacetimidate, whichallows the reaction to be carried out in an acidicmedium [3].

When 2�benzyloxy�1�methylpyridinium triflate isused as a benzylating agent, the successful synthesis ofbenzyl alkyl ethers can be accomplished in a neutralmedium [4]; they can be also prepared from silylethers and aromatic aldehydes in the presence of tri�ethylsilane and catalytic amounts of FeCl3 [5]. Sirke�cioglu et al. [6] reported the synthesis of benzyl alkylethers by the Cu(acac)2�catalyzed reaction of benzylchloride with structurally different alcohols.

The goal of the present work was to develop a novelefficient synthetic method for benzyl alkyl ethers bythe reaction of toluene with alcohols in a CCl4medium under the action of metal complex catalysts.

EXPERIMENTAL

NMR spectra were recorded on a Bruker Avance�400 (400.13 and 100.62 MHz, respectively) spectrom�eter in CDCl3; the chemical shifts (δ) are given in ppmrelative to TMS. Mass spectra were recorded on a Shi�madzu GCMS�QP2010Plus gas chromatograph/massspectrometer (SPB�5 capillary column, 30 m ×

0.25 mm; carrier gas, helium; temperature program�ming from 40°C to 300oC at a rate of 8oC min–1; evap�orator temperature, 280°C; ion source temperature.200°C; ionization energy—70 eV). The chromato�graphic analysis was performed on a Shimadzu GC�9A instrument (column dimensions of 2 m × 3 mm;stationary phase, silicone SE�30 (5%) supported onChromaton N�AW�HMDS, temperature program�

ming mode, from 50 to 270°C at a rate of 8оC/min;carrier gas, helium (47 mL/min)).

The reactants were commercially available metha�nol, ethanol, propanol�1, propanol�2, butanol�1,pentanol�1, hexanol�1, heptanol�1, octanol�1, unde�canol�1, cyclopentanol, cyclohexanol, benzyl alcohol,toluene, ССl4, CHCl3, СHBr3, CBrCl3, formamide,pyridine, and acetonitrile, which were distilled prior touse. The catalysts V2O5, VO2, V2O3, VO(acac)2, VCl3,and VCl4 were dried in a vacuum desiccator; СBr4,2,2'�bipyridyl, 4,4'�bipyridyl, and triphenylphosphine(Acros) were recrystallized from benzene and ethanolprior to use.

The reactions were carried out in a glass ampoule(V = 10 mL) placed in a stainless steel microautoclave(V = 17 mL) with continuous stirring and controlledheating.

General Procedure for Synthesis of Benzyl Alkyl Ethers (1, 6–18)

An ampoule was charged under argon with 0.0058 g(0.022 mmol) of VO(acac)2, 0.01 mL (0.077 mmol) ofEt3N, 0.2 mL (2.08 mmol) of CCl4, and 8.7 mmol(0.28 g of СН3OH, 0.4 g of С2Н5OH, 0.52 g of n�С3Н7OH, 0.52 g of iso�С3Н7OH, 0.64 g of n�С4Н9OH,0.77 g of n�С5Н11OH, 0.89 g of n�С6Н13OH, 1.01 g of n�С7Н15OH, 1.13 g of n�С8Н17OH, 1.5 g of n�С11Н23OH,0.94 g of PhCH2OH, 0.75 g of cyclo�C5H9OH, or 0.87 gof cyclo�C6H11OH) (or 34.7 mmol (2.6 g) in the case ofn�С4Н9OH).

The sealed ampoule was heated in the autoclave at175оС for 14 h in the case of СН3OH, С2Н5OH,n�С3Н7OH, iso�С3Н7OH, n�С4Н9OH, n�С5Н11OH,n�С6Н13OH, n�С7Н15OH, n�С8Н17OH, or n�С11Н23OH; 20 h in the case of PhCH2OH; and 10 h inthe case of cyclo�C5H9OH or cyclo�C6H11OH withvigorous stirring. After the reaction completion, theautoclave was cooled to 20оС, the reaction mixturewas neutralized with a 10% Na2CO3 aqueous solution

A Novel Method for Synthesis of Benzyl Alkyl Ethers Using Vanadium�Based Metal Complex Catalysts

R. I. Khusnutdinov, A. R. Bayguzina, L. I. Gallyamova, and U. M. DzhemilevInstitute of Petroleum Chemistry and Catalysis, Russian Academy of Sciences, pr. Oktyabrya 141, Ufa, 450075 Russia

e�mail: ink@anrb.ruReceived January 16, 2012

Abstract—A novel method has been developed for the synthesis of benzyl alkyl ethers in 25–85% yields viathe reaction of toluene with alcohols in a CCl4 medium catalyzed by Et3N�activated VO(acac)2.

DOI: 10.1134/S0965544112040044

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(stirring for 1h), the organic layer was extracted withchloroform, and the extract was filtered through a padof silica gel (2 g). The unreacted toluene, light ethers,and chloroform were removed on a rotor evaporator.The residue was analyzed by GLC using decane as aninternal standard.

To obtain chromatographically pure samples, todetermine the yield, and to identify the resulting ben�zyl alkyl ethers, the experiments were performed witha tenfold greater charge.

An ampoule (50 mL) was charged under argon with0.058 g (0.022 mmol) of VO(acac)2, 0.1 mL (0.077 mmol)of Et3N, 2 mL (2.08 mmol) of CCl4, 8.7 mmol (2.8 gof СН3OH, 4 g of С2Н5OH, 5.2 g of n�С3Н7OH, 5.2 gof iso�С3Н7OH, 6.4 g of n�С4Н9OH, 7.7 g of n�С5Н11OH, 8.9 g of n�С6Н13OH, 10.1 g of n�С7Н15OH,11.3 g of n�С8Н17OH, 15 g of n�С11Н23OH, 9.4 g ofPhCH2OH, 7.5 g of cyclo�C5H9OH, or 8.7 g of cyclo�C6H11OH) (or 34.7 mmol (26 g) in the case of n�С4Н9OH). The sealed ampoule was placed in theautoclave (V = 100 mL), the autoclave was tightlysealed and heated at 175оС for 14 h in the case ofСН3OH, С2Н5OH, n�С3Н7OH, iso�С3Н7OH, n�С4Н9OH, n�С5Н11OH, n�С6Н13OH, n�С7Н15OH, n�С8Н17OH, or n�С11Н23OH; 20 h in the case ofPhCH2OH; and 10 h in the case of cyclo�C5H9OH orcyclo�C6H11OH, respectively) under continuous stir�ring. After completion of the reaction, the autoclavewas cooled to 20оС, the ampoule was unsealed, thereaction mixture was neutralized with 10% Na2CO3aqueous solution (stirring with a magnetic stirrer for 1h), the organic layer was extracted with chloroform,and the extract was filtered through a pad of silica gel(20 g). The unreacted toluene, light ethers, and chlo�roform were preliminary evaporated on a rotor evapo�rator. Benzyl chloride, higher dialkyl ethers, and ben�zyl alkyl ethers were isolated by vacuum distillation.

The structure of the resulting benzyl alkyl etherswas confirmed by the spectral data and by comparingwith the known samples and reference data:

benzyl methyl ether, 1 (yield 85%) [7], benzyl ethylether, 6 (yield 26%), benzyl propyl ether, 7 (yield 27%)[8], benzyl 2�propyl ether, 8 (yield 32%) [9], benzylbutyl ether, 9 (yield 34%) [7], benzyl amyl ether, 10(yield 24%) [10], dibenzyl ether, 15 (yield 62%) [11–12], benzyl cyclohexyl ether, 18 (yield 64%) [13].

Benzyl hexyl ether, 11. Yield 52%, bp 106–107°C/6 torr. 13C NMR (CDCl3, δ, ppm): 138.74(C�1), 128.34 (C�3, C�5), 127.59 (C�2, C�6), 127.45(C�4); 72.90 (C�7), 70.54 (C�8), 29.91 (C�9), 28.78(C�10), 25.87 (C�11), 22.78 (C�12), 14.14 (C�13). 1HNMR (CDCl3, δ, ppm): 1.04 (3H, t, 3JHH = 7.2 Hz,СН3), 1.35⎯1.80 m (8H, СH2(СH2)4СH3), 3.57 t(2H, 3JHH = 6.4 Hz, OСН2CH2), 4.54s (2Н, СH2O),7.30–7.50 m (5H, Ar, CH). Found (%): C, 81.41; H,10.37; O, 8.22. Calculated for C13H20O (%): C, 81.20;H, 10.48; O, 8.32.

Benzyl heptyl ether, 12. Yield 25%, bp 99–100°C/2torr. 13C NMR (CDCl3, δ, ppm): 138.78 (C�1), 128.34(C�3, C�5), 127.60 (C�2, C�6), 127.45 (C�4); 72.88(C�7), 70.55 (C�8), 31.88 (C�9), 29.84 (C�10), 29.21(C�11), 26.22 (C�12), 22.66 (C�13), 14.11 (C�14). 1HNMR (CDCl3, δ, ppm): 0.94 t (3H, 3JHH = 6.8 Hz,СН3), 1.25–1.80 m (10H, СH2(СH2)5СH3), 3.52 t(2H, 3JHH = 6.8 Hz, OСН2CH2), 4.55 s (2Н, СH2O),7.20–7.45 (5H, Ar, CH). Found (%): C, 81.63; H,10.86; O, 7.53. Calculated for C14H22O (%): C, 81.50;H, 10.75; O, 7.76.

Benzyl octyl ether, 13. Yield 69%, bp 88–90°C/0.5torr. 13C NMR (CDCl3, δ, ppm): 138.79 (C�1), 128.40(C�3, C�5), 127.7 (C�2, C�6), 127.59 (C�4); 72.88 (C�7), 70.54 (C�8), 31.91 (C�9), 30.00 (C�10), 29.86 (C�11), 29.52 (C�12), 28.73 (C�13), 25.08 (C�14), 14.00(C�15). 1H NMR (CDCl3, δ, ppm): 0.94 t (3H, 3JHH =6.8 Hz, СН3), 1.35–1.80 m (12H, СH2(СH2)6СH3),3.52 t (2H, 3JHH = 6.4 Hz, OСН2CH2), 4.55 s (2Н,СH2O), 7.20–7.50 m (5H, Ar, CH). Found (%): C,81.52; H, 10.88; O, 7.60. Calculated for C15H24O (%):C, 81.76; H, 10.98; O, 7.26.

Benzyl undecyl ether, 14. Yield 61%, bp 105–107°C/0.2 torr. 13C NMR (CDCl3, δ, ppm): 138.72(C�1), 128.31 (C�3, C�5), 127.60 (C�2, C�6), 127.44(C�4); 72.84 (C�7), 70.54 (C�8), 31.93 (C�9), 29.78(C�10), 29.60 (C�11), 29.50 (C�12), 29.48 (C�13),29.35 (C�14), 28.91 (C�15), 28.61 (C�16), 22.69 (C�17), 14.10 (C�18). 1H NMR (CDCl3, δ, ppm): 0.94(3H, t, 3JHH = 7.2 Hz, СН3), 1.35–1.80 m (18H,СH2(СH2)6СH3), 3.64 t (2H, 3JHH = 6.8 Hz,OСН2CH2), 4.52 s (2Н, СH2O), 7.20–7.50 m (5H,Ar, CH). Found (%): C, 82.54; H, 11.45; O, 6.01. Cal�culated for C18H30O (%): C, 82.38; H, 11.52; O, 6.10.

Benzyl cyclopentyl ether, 17. Yield 69%, bp 116–117°C/10 torr. 13C NMR (CDCl3, δ, ppm): 138.29(C�1), 128.42 (C�3, C�5), 127.80 (C�2, C�6), 127.35(C�4); 80.90 (C�8), 70.71 (C�7), 32.32 (C�9, C�12),23.61 (C�10, C�11). 1H NMR (CDCl3, δ, ppm): 1.2–1.8 m (8H, CH2), 3.95–4.08 m (1H, CH), 4.59 s (2H,CH2), 7.10–7.60 m (5H, Ar, CH). Found (%): C,81.79; H, 9.23; O, 8.98. Calculated for C12H16O (%):C, 81.77; H, 9.15; O, 9.08.

RESULTS AND DISCUSSION

Preliminary experiments showed that benzylmethyl ether 1, a valuable fragrance with a fruit smellof ilang�ilang and green hyacinth flowers, can be syn�thesized by reacting toluene with methanol in a ССl4medium in the presence of the following vanadiumcompounds: V2O5, VO2, V2O3, VCl3, VCl4, or VO(acac)2,of which VO(acac)2 is the best (the reaction is too sen�sitive to the moisture content). As ligands, the follow�ing compounds were also tested: formamide, pyridine,2,2'�bipyridyl, 4,4'�bipyridyl, acetonitrile, and triphe�nylphosphine, which are inferior in activity to triethy�lamine (see table).

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A NOVEL METHOD FOR SYNTHESIS OF BENZYL ALKYL ETHERS 263

Among the tested halogenated methanes: ССl4,CHCl3, СHBr3, CBr4, and CBrCl3, the reaction pro�ceeds best of all with carbon tetrachloride. Chloro�form and bromoform appeared to be inactive in thisreaction, and the use of CBr4 or CBrCl3 made the pro�cess nonselective despite a high conversion of the reac�tant toluene (47% and 59% for 4 h at 175оС, respec�tively). Thus, the reaction of toluene with CBr4 andMeOH in the presence of the VO(acac)2–Et3N cata�lytic system affords benzyl methyl ether (4%), benzylbromide (3%), methyl benzoate (20%), benzyl alcohol

(8%), benzaldehyde (8%), and diarylmethanes in theratio of 2�methyldiphenylmethane : 3�methyldiphe�nylmethane : 4�methyldiphenylmethane = 5 : 1 : 5(4%) [14, 15], as well as CHBr3, MeOMe, HCO2Me,and MeBr. The analogous reaction with CBrCl3 led tothe formation of a more complex product mixtureconsisting of benzyl methyl ether (12%), benzyl bro�mide (3%), benzyl chloride (2%), benzaldehyde(11%), methyl benzoate (20%), benzyl alcohol (6%),and diarylmethanes in the 2�methyldiphenylmethane :3�methyldiphenylmethane : 4�methyldiphenyl�

Effect of the catalyst nature, ligand nature, and reaction time on the toluene conversion and product yields in the reactionof toluene with CCl4 and MeOH (175°C)

Run no. Catalyst Ligand Time, h Toluene

conversion,%

Yields of products, %

PhC

HO

BnO

Me

BnC

l

BnO

H

PhC

O2M

e

diar

ylm

etha

nes*

1 V2O3 – 4 15 0.4 2.8 0.3 0.5 3 8

2 VO2 – '' 16 1 12 2 1 0 0

3 V2O5 – '' 4 0.3 0.4 2.4 0.3 0.5 0.1

4 VCl3 – '' 27 0 19 4 1 1 2

5 VCl4 – '' 20 0 10 6.5 1.5 2 0

6 VO(acac)2 – '' 40 4 32 3 1 0 0

7 '' HCONH2 '' 0 0 0 0 0 0 0

8 '' 2,2'�bipyridyl

'' 9 1 4 3 0 0 1

9 '' 4,4'�bipyridyl

'' 10 0.5 6 1 0.5 1 1

10 '' CH3CN '' 47 6 31 3 1 3 3

11 '' PPh3 '' 100 26 39 12 2 11 10

12 '' pyridine '' 12 2 4 4 3 0

13 '' Et3N '' 47 2 42 2 1 0 0

14 VO(acac)2 '' 1.5 32 0.6 29 2 0.4 0 0

15 '' '' 2 39 1 35 2.5 0.5 0 0

16 '' '' 4 47 2 42 2 1 0 0

17 '' '' 6 55 5 48 1 1 0 0

18 '' '' 7 57 6.5 49 1 0.5 0 0

19 '' '' 9 65 10 52 2 1 0 0

20 '' '' 10 74 10 61 2 1 0 0

21 '' '' 12 95 10 80 3 2 0 0

22 '' '' 14 100 10 85 3 2 0 0

* 2�methyldiphenylmethane, 3�methyldiphenylmethane, 4�methyldiphenylmethane (5 : 1 : 5).

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KHUSNUTDINOV et al.

methane ratio of 3 : 1 : 3 (5%), as well as CHBrCl2,CHBr2Cl, CHBr3, C2Cl4, C2Cl6, MeOMe, HCO2Me,MeBr, and MeCl.

The greatest yield of benzyl methyl ether 1 (85%over 14 h) is achieved using triethylamine�activatedVO(acac)2 as a catalyst.

Along with compounds 1–4, the reaction mix�ture also contained the following byproducts:chloroform, HCl, water, dimethyl ether, formalde�

hyde dimethyl acetal, methyl formate, which areformed by the following scheme according to pub�lished data [16, 17]:

A key byproduct affecting the reaction course ismethyl hypochlorite, which was also detected in ourexperiments (iodometric titration, concentration of0.03–0.05 mg/mL). Taking into account the forma�tion of methyl hypochlorite, we first assumed the reac�tion scheme suggesting toluene oxidation with MeOClto the final product.

However, since benzyl chloride 2 and chloroformhave been found in reaction mixture, the most likelyscheme of the formation of ether 1 seems to involvetwo steps, toluene is initially chlorinated with carbon

tetrachloride by the action of VO(acac)2 to give benzylchloride, which undergoes methanolysis at the finalstage.

This assumption is supported by the results ofexperiments with an authentic sample of benzyl chlo�ride 2, which transforms into benzyl methyl ether 1with a quantitative yield under the reaction condi�tions; when the reaction is run with an admixture ofcarbon tetrachloride ([VO(acac)2] : [BnCl] :[MeOH] : [CCl4] = 1 : 100 : 400 : 100), the yield ofbenzyl methyl ether makes 91%.

Benzaldehyde 3 detected in a small amount (10%)in the reaction mixture (Table 1, run 22) is likely to

result from the benzyl alcohol oxidation mediated byCCl4 according to the following scheme:

PhMe + MeOH + CCl4 BnOMe + BnCl + PhCHO + BnOHVO(acac)2⎯Et3N

–Me2O175°C, 14 h

1 2 3 485% 3% 10% 2%

VO(acac)2 : Et3N : toluene : MeOH : CCl4 = 1 : 5 : 100 : 400 : 100.

Scheme 1.

MeOH + CCl4 CH2OVO(acac)2

–CHCl3MeOH

–HCl

H+, MeOH

MeOCl

CH2(OMe)2

HCO2Me.

Scheme 2.

5

MeOH + CCl4VO(acac)2 MeOCl + CHCl3

PhMe + MeOCl BnOMe.VO(acac)2

–HCl175°C, 6 h

1Scheme 3.

PhMe + CCl4[V]

–CHCl3BnCl –HCl

Scheme 4.

+CH3OH, [V]BnOMe.

12

BnCl + MeOH

BnOMe 100%VO(acac)2–Et3N

175°C, 6 h

CCl4

conv. 91%

175°C, 6 h conv. 100%

BnOMe 91%.

1

1Scheme 5.

2

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A NOVEL METHOD FOR SYNTHESIS OF BENZYL ALKYL ETHERS 265

We performed a kinetic study of the reaction of tol�uene with CCl4 and methanol in the presence of theVO(acac)2–Et3N catalytic system. As can be seen fromthe data presented, the amount of benzyl chloride inthe reaction products does not exceed 3% for a reac�tion time of 1.5–14 h (see table).

The reaction is common in character for the alco�hol series: ethanol, propanol�1, propanol�2, butanol�1, pentanol�1, hexanol�1, heptanol�1, octanol�1, and

undecanol�1 enter this reaction. The yields of the cor�responding ethers 6–14 are 25–69%. It is noteworthythat as the length of the alkyl radical in the alcoholmolecule increases, the yield of benzyl alkyl etherincreases, a fact that can be explained by the ease offormation of homoethers from lower alcohols andtheir active oxidation with CCl4 into the correspond�ing aldehydes and esters, which are detected indeed insmall amounts in the reaction mixture.

Benzyl butyl ether 9, which has a fruit smell is themost valuable in the series of benzyl alkyl ethers. It isallowed for use in many countries as a flavor for foodproducts: drinks, desserts, baked goods, ice cream,and ice. Therefore, we carried out an additional studyto find the conditions that would facilitate increasingthe yield of benzyl butyl ether. In particular, the reac�tion selectivity for benzyl butyl ether can be enhancedby increasing the concentration of n�С4Н9OH, withthe reaction time being reduced to 10 h.

Under the optimal conditions: 175оС, 10 h, and acatalyst to reactants ratio of [VO(acac)2] : [Et3N] : [tol�uene] : [СCl4] : [n�С4Н9OH] = 1 : 5 : 100 : 100 : 1600,

toluene transforms into benzyl butyl ether 9 with ayield of 67% at a toluene conversion of 69%.

When benzyl chloride is used instead of toluene asa reactant (at the catalyst to reactants ratioof [VO(acac)2] : [Et3N] : [benzyl chloride] : [n�С4Н9OH] = 1 : 5 : 100 : 400) at 175°С, the reactiontime reduces to 5 h, but the yield of benzyl butyl ether9 makes ~100% despite this fact.

The above reaction with toluene is characteristic ofbenzyl alcohol. The main product of the reaction isdibenzyl ether 15 (53%). At the same time, a markedamount of the alcohol is oxidized to benzaldehyde 3(11%) and undergoes substitution chlorination toconvert into benzyl chloride 2 (30%).

2MeOH H2O + (Me)2OHCl

Scheme 6.

PhMe H2OCCl4 BnCl BnClCCl4 BnOCl [V]

–HClPhCHO.

2 4 5 3

PhMe + ROH + CCl4 VO(acac)2–Et3N

–ROR175°C, 14 h BnOR.

1–14

Scheme 7.

R = C2H5 (6) 26%

n�C3H7 (7) 27%

i�C3H7 (8) 32%

n�C4H9 (9) 34%

n�C5H11 (10) 24%

n�C6H13 (11) 52%

n�C7H15 (12) 25%

n�C8H17 (13) 69%

n�C11H23 (14) 61%

BhOH + PhOH + CCl4 Bn2O + BnCl + PhCHO VO(acac)2–Et3N

toluene 175°C, 20 h

15 2 3

VO(acac)2 : Et3N : toluene : BnOH : CCl4 = 1 : 5 : 100 : 400 : 100 [4.2 : 2.5 : 1]

Scheme 8.

conversion 100%

VO(acac)2 : Et3N : toluene : BnOH : CCl4 = 1 : 5 : 100 : 800 : 100 [20 : 10 : 1]

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KHUSNUTDINOV et al.

As the benzyl alcohol concentration increased rel�ative to that of toluene ([VO(acac)2] : [Et3N] : [tolu�ene] : [СCl4] : [BnOH] = 1 : 5 : 100 : 100 : 800) theyield of dibenzyl ether 15 reached 62%, and the tolu�ene conversion was complete.

The analogous reaction of toluene with cyclopen�tanol and cyclohexanol led to the production of benzylcyclopentyl 17 and benzyl cyclohexyl 18 ethers in 64and 69 % yields, respectively.

Thus, the reaction under study offers a simple routefor the synthesis of benzyl alkyl ethers from availablereagents: toluene, CCl4, and alcohols.

ACKNOWLEDGMENTS

This work was supported by the Russian Founda�tion for Basic Research and the Government ofRepublic of Bashkortostan, RFBR project Povolzh’e12�03�97019.

REFERENCES1. S. Czernecki, C. Georgoulis, C. Provelenghiou, and

G. Fusey Tetrahedron Lett. 17, 3535 (1976).2. A. Bouzide and G. Sauve, Tetrahedron Lett. 38, 5945

(1997).3. P. R. Skaanderup, C. S. Poulsen, L. Hyldtoft, et al.,

Synthesis, No. 12, 1721.4. K. W. C. Poon and G. B. Dudley, J. Org. Chem. 71,

3923 (2006).5. K. Iwanami, K. Yano, and T. Oriyama, Synthesis,

No. 16, 2669 (2005).6. O. Sirkecioglu, B. Karliga, and N. Talinli, Tetrahedron

Lett. 44, 8483 (2003).

7. S. A. Voitkevich, 865 Fragrances for Perfumery andHousehold Chemistry (Pishchevaya promyshlennost’,Moscow, 1994) [in Russian].

8. W. J. Monacelli and G. F. Hennion, J. Am. Chem. Soc.63, 1722 (1941).

9. W. T. Olson, H. F. Hipsher, C. M. Buess, I. A. Good�man, I. Hart, J. H. Lamneck, L. C. Gibbons, J. Am.Chem. Soc. 69, 2451 (1947).

10. F. C. Whitmore and D. P. Langlois, J. Am. Chem. Soc.55, 1518 (1933).

11. S. Kim, K. Chung, and S. Yang, J. Org. Chem. 52, 3917(1987).

12. The Aldrich Catalog/Handbook of Fine Chemicals; (Ald�rich, Milwaukee, 2007⎯2008).

13. M. B. Sassaman, K. D. Kotian, G. K. S. Prakash, andG. A. Olah, J. Org. Chem. 52, 4314 (1987).

14. R. I. Khusnutdinov, N. A. Shchadneva, A. R. Baiguz�ina, Yu. Yu. Lavrent’eva, R. Yu. Burangulova,U. M. Dzhemilev, Pet. Chem. 44, 265 (2004).

15. S. Meyerson, H. Drews, and E. K. Fields, J. Am.Chem. Soc. 86, 4964 (1964).

16. R. I. Khusnutdinov, N. A. Shchadneva, A. R. Bayguz�ina, et al., ARKIVOC XI, 53 (2004).

17. R. I. Khusnutdinov, N. A. Shchadneva, R. Yu. Buran�gulova, et al., Russ. J. Org. Chem. 42, 1615 (2006)

CCl4, VO(acac)2, Et3N

175°C, 10 h

VO(acac)2 : Et3N : toluene : ROH : CCl4 = 1 : 5 : 100 : 400–1600 : 100

Scheme 9.

n = 2 (17) 69%

n = 2 (17) 64%

(CH2)n OH (CH2)nOBnPhMe +

n = 2, 3