Synthesis of Isooctenyl Alcohols from Diisobutylene Via Chlorination*

161

Synthesis of Isooctenyl Alcohols from Diisobutylene via Chlorination*

by YasuhiroFurukawa**, Koichi Asano** and YoujiKomatsu**

Summary: Isooctenylalcohols were prepared from hydrolysisof diisobutylene monochlorides which were obtained by chlorinationof diisobutylene. Analysis and identificationof diisobuylene monochlorideand isooctenylalcohol and hydrolysisof the diisobutylenemonochloride to isooctenyl alcohol in the presenceof alkalis and solventswere studied. Thefollowing results were obtained. (1) Structuresof the products were determinedby the comparisonof their IR and NMR spectra with those of authentic compounds. The diisobutylenemonochloride contained 1-chloro-2-neopentyl-2-propene, cis-1-chloro-2,4, 4-trimethyl-2-pentene,trans-1-chloro-2, 4, 4-trimethyl-2-pentene and 3-chloro-2,4, 4-trimethyl-1-pentene,and the isooctenylalcohol contained2-neopentyl-2-propene- 1-ol, cis-2,4, 4-trimethyl-2-pentene-1-ol, trans-2,4, 4-trimethyl-2-pentene-1-oland 2, 4, 4-trimethyl-1-pentene-3-ol. (2) Reactionconditions in the presenceof alkalis were studied. Among the alkalis used, sodium carbonate, sodium bicarbonateand calcium hydroxidegave favorable results, and the optimum

pH value was in the range of 8～11. When a strong alkali such as sodium hydroxide was used, favorable results were obtained by keeping pH at 8～10. (3) DMSO was found to be one of most effectivesolvents in that the rate of hydrolysiswas high and primary isooctenylalcohols were obtained in high selectivity. (4) The kinetic studies showed that hydrolysisof monochloridewas of the SN2 type. (5) Examination of the product compositionduring hydrolysisin DMSO showed that secondary monochloridechanged to primary isooctenylalcohols by isomerization. The reactionpath of four isooctenylchlorides, which were contained in the monochloride,was discussed.

monochloride and isooctenyl alcohol, and de- 1 Introduction tails of the reactions have not been clarified. Many processes are known for the preparation In the present work, the components contained of octyl alcohols, for example, n-octyl alcohol in the diisobutylene monochloride and isooctenyl by Ziegler process or high pressure reduction of alcohol were separated by fractional distillation the esters of fatty acids and 2-ethylhexyl alcohol or by preparative gas chromatography. The and isooctyl alcohols by oxo process or acetal- isolated chlorides and alcohols were identified dehyde process. On the other hand, the syn- by the comparison of their IR and NMR spectra thesis of alcohols by hydrolysis of the halogenated with those of authentic compounds which were hydrocarbons has been widely studied, particu- synthesized by unambiguous methods. The larly, hydrocarbons of lower molecular weights. hydrolysis of diisobutylene monochloride in the For higher hydrocarbons, the yields of the al- presence of alkalis and solvents were carried out, cohols are low because of the occurrence of such and the effects of reaction conditions and the side reaction as the formation of olefinic hydro- reaction path were discussed. carbons by the elimination of halogen and its hydride1). 2 Experimental The preparative method of isooctenyl alcohols 2.1 Materials through hydrolysis of diisobutylene monochloride, 2.1.1 Diisobutylene (DIB) and Chlorine which was obtained by chlorination of diiso- DIB used was a product of isobutene poly- butylene, has been described in patents2)～4). merization by sulfuric acid catalyst (Maruzen However, no studies have been made on the Oil Co.) and was purified by fractional distil- compositions and structures of the diisobutylene lation. Purity was above 99.9%. Purified DIB contained 68.4% of 2, 4, 4-trimethyl-1-pentene * Received June 11, 1973. ** Research & Development ** Center, Maruzen Oil and 31.6% of 2, 4, 4-trimethyl-2-pentene. Chlo- Co., Ltd. (Gongendo, Satte-Machi, Saitama, 340-01). rine was commercially obtained and purified by

Volume 15, No. 2, November 1973 162 Furukawa, Asano and Komatsu: Synthesis of

70～75℃/12mmHg) by preparative gas chro- passing it through concentrated sulfuric acid and calcium oxide. matography (Chromosorb P/Reoplex 400=80/20 2.1.2 Diisobutylene Monochloride [I] by wt., 5mmφ×7.5mm, 175℃). B. p. 173.6 DIB was chlorinated at 90℃ by introducing ℃ (Lit.9) 72.5～73.5℃/12mmHg); d204 0.8550; gaseous chlorine in a mole ratio of 0.9 to DIB n20D1.4440 (Lit.9) 1.4441); 3, 5-dinitrobenzoate m.p. into a glass flask. The reaction product was 57,3℃ (Lit.9) 56℃). washed with water and distilled in Widmer co- 2.3.3 cis- and trans-2, 4, 4-Trimethyl-2-pente- lumn, and monochloride fraction [I] (b. p. 156～ ne-1-ol [V] and [VI] 158℃, yield 85%) was obtained. Crude ethyl-2, 4, 4-trimethyl-2-pentenoate [IX] 2.1.3 Isooctenyl Alcohol [II] obtained by Wadswarth's reaction10) involving Monochloride fraction [I] was hydrolyzed at trimethyl acetaldehyde and ethyl-α-phosphono- 150℃ for 6 hours in a 500ml autoclave with a propionate was separated into cis- and trans-iso- calcium hydroxide-water mixture with a mole mers ([VII] and [VIII], respectively) by fractional ratio of Ca(OH)2/[I] of 0.55 and the ratio of distillation. Alcohol [V] and [VI] were obtained water/[I] of 5 by weight. by the reduction of the corresponding esters

Isooctenyl alcohol fraction [II] (b. p. 98～ [VII] and [VIII] with LiAlH4. 100℃/50mmHg, yield 70%) was obtained from cis-and trans-Ethyl-2,4, 4-trimethyl-2-pentenoate[VII], the reaction mixture by adding isooctane and [VIII] distilling resulting mixture. 170ml of dimethylformamide and 4.1g of 2.2 Analysis sodium hydride were introduced into a glass Conditions of gas chromatography used for flask, and while stirring the mixture, 20g of determinations of chlorides, alcohols and hy- ethyl-α-phosphonopropionate prepared from ethyl- drolysis products were as follows: α-bromopropionate and α-triethyl phosphite was 1) Determination of chlorides added. During the addition, the reaction tem-

Column: PPG 0.25mmφ ×90m. Column perature was kept at 20℃ and then the reaction temp.: 90℃. Detector: FID. Carrier was continued for 1hr at room temperature. gas: He 3.0kg/cm2. To the reaction mixture, 7.2g of trimethyl- 2) Determination of alcohols and hydrolysis acetaldehyde freshly prepared from tert-butyl products chloride and methyl formate by Grignard re- Column: Reoplex 400 0.25mmφ×90m. action was added at 30℃. After continuing

Column temp.: 125℃ (for alcohols), 142℃ the reaction for 1hr at room temperature and (for hydrolysis products). Detector: FID. 3hr at 80℃, the reaction mixture was hydro- Carrier gas: He 3.0kg/cm2. lyzed with 300ml of water, extracted with ethyl NMR spectra were obtained with a Nihon ether, and finally dehydrated with anhydrous Denshi Model JNM-C-60 (60MHz) spectro- sodium sulfate. The product [IX] was separated meter using tetramethylsilane as the internal into two fractions of b. p. 71～73℃/15mmHg standard in carbon tetrachloride at 25℃. (1.7g, yield 13.1%) and b. p. 83～85℃/15mmHg IR spectra were recorded by a Shimadzu (1.8g, yield 14.3%) by fractional distillation Model AR-275 infrared spectrophotometer using (4mmφ×60cm column packed with helipack, NaCl prism at 27℃. reflux ratio 1/120).

2.3 Syntheses of Standard Isooctenyl Al- NMR spectra (δ, ppm) of the former were cohols and Chlorides 5.42 (-CH=C-), 3.97～4.33 (-O-CH2-C-), 1.84

2.3.1 2,4, 4-Trimethyl-1-pentene-3-ol [III] (-C=C-CH3), 1.17～1.41 (-O-C-CH3), 1.08 (tert- Alcohol [III] was obtained by reacting me- Bu); and those of the latter were 6.68 (-CH=C-), thacrolein5),6) with tert-butyl-lithium7) followed 3.95～4.30 (-O-CH2-C), 1.90 (C=C-CH3), 1.29～ by hydrolysis. B. p. 154.7℃ (Lit.8) 154.8～155 .0 1.38 (-O-C-CH3), 1.19 (tert-Bu). NMR spectra ℃); d204 0.8556; n20D 1.4428; 3, 5-dinitrobenzoate at 5.42 showed the cis-conformation hydrogen m. p. 123.3℃ (Lit.8) 123℃). with respect to carbonyl and at 6.68 showed that 2.3.2 2-Neopentyl-2-propene-1-ol [IV] of the trans. Therefore, the former fraction is 1,2-Epoxy-2, 4, 4-trimethylpentane was isomeriz- [VII] and the latter is [VIII]. ed in the presence of ethanol9). [IV] was ob- cis-2,4, 4-Trimethyl-2-pentene-1-ol[V] tained by purification of the crude alcohol (b. p. Ester [VII] was reduced with LiAlH4 followed Bulletinof The Japan Petroleum Institute Isooctenyl Alcohols from Diisobutylene via Chlorination 163 by hydrolysis. The crude product (yield 66.3%) 2.3.7 3-Chloro-2, 4,4-trimethyl-1-pentene was purified by fractional distillation. B.p. [XIII] 172.5℃; d204 0.8539; n20D 1.4518; 3, 5-dinitroben- Chloride [XIII] was obtained from alcohol [III] zoate m. p. 182.1℃. in the same manner used in the preparation of trans-2,4, 4-Trimethyl-2-pentene-1-ol [VI] chloride [X]. In this reaction, chloride [XII] Alcohol [VI] was synthesized from ester [VIII] was formed as a by-product by allyl rearrange- in a similar manner as alcohol [V] (yield 49.2%). ment11),12). Chloride [XIII] was separated from B. p. 178.1℃; d204 0.8529; n20D 1.4505; 3, 5- [XII] by preparative gas chromatography. dinitrobenzoate m. p. 203.1℃. 2.4 Procedure for Hydrolysis of Monochlo- 2.3.4 1-Chloro-2-neopentyl-2-propene [X] ride To the mixture of 9.64g (0.075mol) of al- Prescribed amounts of alkali, solvent and water cohol [IV] and 14.19g (0.077mol) of tri-n- were placed in a reaction vessel and heated to a butylamine in 110ml of ethyl ether, 9.55g (0.08 given temperature while stirring; then mono- mol) of thionyl chloride was added slowly under chloride which was kept at this temperature was vigorous stirring at -10～0℃. The reaction charged to the vessel, and the reaction was started. was continued for 1hr at room temperature. The reaction mixture was filtered to remove the The product was washed with water, dried solid material. The upper layer of the filtrate over anhydrous sodium sulfate and purified by and the isooctane extracted of the lower (water) distillation and preparative gas chromatography. layer were combined and distilled. An example 2.3.5 cis-1-Chloro-2, 4, 4-trimethyl-2-pentene of gas chromatogram of the hydrolysis product is [XI] shown in Fig. 1. Chloride [XI] was obtained from alcohol [V] by the same method used in the preparation of 3 Results and Discussion chloride [X]. 3.1 Analysis of Diisobutylene Monochlo- 2.3.6 trans-1-Chloro-2, 4, 4-trimethyl-2-pen- ride [I] tene [XII] Analytical data of synthesized authentic iso- Chloride [XIII] was obtained from alcohol octenyl chlorides are shown in Table 1, 2 and 3. [III] by the same method used in the preparation Monochloride [I] consisted mainly of five of chloride [X]. components, and these components were separated

Fig. 1 Gas Chromatogram of Hydrolysis Product of Diisobutylene Monochloride

Volume 15, No. 2, November 1973 164 Furukawa, Asano and Komatsu: Synthesis of

Table 1 Characterization of the Synthesized Compounds

by preparative gas chromatography. The results was shown that separation efficiency of the pre- of elemental analysis and molecular weight de- parative gas chromatography was not adequate terminations of peaks No. 2～No. 5 (Table 4) so the two components were collected in one showed that the molecular formulas of these fraction, and the ratio of the two components compounds were C8H15Cl. IR and NMR spectra was about 68:32. The elemental analysis of and retention times of gas chromatogram of peaks this fraction showed C, 73.68; H, 11.40; Cl, No. 2, No. 3, No. 4 and No. 5 were consistent 14.92%, which corresponded to the calculated with those (Table 1, 2 and 3) of authentic com- values for 64 parts of C8H15Cl and 36 parts of pounds [XIII], [XI], [X] and [XII], respec- C12H24. Referring to the analytical conditions, tively. Therefore, peaks No. 2, No. 3, No. 4 retention times of pure C8H15Cl and C12H24 and No. 5 were identified as 3-chloro-2, 4, 4- were very close to each other. IR spectra (cm-1): trimethyl-1-pentene [XIII], cis-1-chloro-2,4, 4-tri- 800(s), 894(s), 1,640(s), 3,040(s), (olefin); 1,203 methyl-2-pentene [XI], 1-chloro-2-neopentyl-2- (m), 1,240(s) (tert-Bu); 486(s), 593(s), 732(s) propene [X] and trans-1-chloro-2, 4,4-trimethyl-2- (C-Cl). NMR spectra (6, ppm): 5.74 (-CH= pentene [XII], repectively. C-), 2.00 (-CH2-), 2.87 (C=C-CH3), 0.96 (tert-Bu). The isolated sample of peak No. 1 showed two It was considered from these results that this peaks in the analytical gas chromatogram (re- peak was a mixture of C8H15Cl and C12H24,but tention times were 30.9 and 31.2 minutes) . It the structures of these compounds could not be Bulletinof The Japan PetroleumInstitute Isooctenyl Alcohols from Diisobutylene via Chlorination 165

Table 2 IR Spectra of the Synthesized Chlorides and Alcohols

confirmed. cular weight determination (Table 4) and re- 3.2 Analysis of Isooctenyl Alcohol [II] tention time of gas chromatography showed that In alcohol [II], which was obtained by hy- peaks No. 6, No. 8, No. 9 and No. 10 corresponded drolysis of diisobutylene monochloride [I], five to 2,4, 4-trimethyl-1-pentene-3-ol [III], cis-2,4, 4- components, peaks No. 6, 7, 8, 9 and 10, were trimethyl-2-pentene-1-ol [V], trans-2,4, 4-trime- found. As alcohol [II] could not be separated thyl-2-pentene-1-ol [VI] and 2-neopentyl-2-pro- from them by painstaking fractional distillation, pene-1-ol [IV], respectively. the separation of each component was carried As the content of peak No. 7 was very small in out by preparative gas chromatography, and alcohol [II], it could not be isolated by preparative these components, except peak No. 7, were col- gas chromatography. A comparison of the re- lected. Retention times of gas chromatogram of tention time of this peak (14.8 minutes) with peaks No. 6, 8, 9 and 10 agreed with those (Table authentic samples (Table 1) was made, but no 1) of alcohol [III], [V], [VI], and [IV], respecti- concurrence was observed. The structure of the vely. component of this peak could not be clarified IR and NMR spectra of peaks No. 6, No. 8, in this work. No. 9 and No. 10 were consistent with those 3.3 Hydrolysis with Aqueous Alkali So- (Table 2 and 3) of authentic alcohols [III], lution [V], [VI] and [IV], respectively. This result 3.3.1 Hydrolysis with NaOH Solution and the results of the elemental analysis, mole- The effect of temperature is shown in Fig. 2.

Volume 15, No. 2, November 1973 166 Furukawa, Asano and Komatsu: Synthesis of

Table 3 NMR Spectra of the Synthesized Chlorides and Alcohols

The optimum temperature range was 130～150℃. At higher temperatures, the selectivity of prim- C8H15OH decreased and lighter hydrocarbon compounds were formed as by-products by the elimination reaction. As shown in Fig. 3, the reaction rate increased with the increase in the amount of water. On the other hand, the amount of alkali did not affect the reaction rate above the alkali/monochloride mole ratio of 1.0. These results were consistent with those of the hydrolysis of allyl chloride1),13),14)and benzyl chlori- de15),16). 3.3.2 Effects of Alkali Compounds The results of hydrolysis with some alkali compounds are compared in Table 5. High selectivity for the formation of primary isooctenyl alcohol was obtained in cases of Na2CO3, NaHCO3 and Ca(OH)2, but in the case of NaOH, the Fig. 2 Effects of Temperature (NaOH) selectivity decreased after a long reaction time Bulletinof The Japan PetroleumInstitute Isooctenyl Alcohols from Diisobutylene via Chlorination 167

Table 4 Characterization of the Isolated Samples of the Monochloride and the Isooctenyl Alcohol

Table 5 Hydrolysis with Alkali Solution

Fig. 3 Effectsof H2O/MonochlorideRatio (NaOH) due to the formation of lighter by-products. In the presence of NH4OH, the rate of hydrolysis was low, and the formation of sec-isooctenyl alcohol was preferred. It was supposed that and pyridine resulted in high conversion of mono- the reason of the good results obtained in the chloride and high selectivity of prim-isooctenyl cases of Na2CO3, NaHCO3 and Ca(OH)2 would alcohol (prim-C8OH). However, triethanolamine be due to the effects of pH values of the reaction and pyridine were decomposed during the re- mixtures14); therefore, in the case of NaOH, good action, and the products were changed to dark results were expected when the hydrolysis was brown in color. With morphorin, methanol and carried out at the same pH value as that of ethylene glycol, high conversion of monochloride Na2CO3, NaHCO3 and Ca(OH)2 aqueous so- was obtained, but selectivity of prim-C8OH was lutions. Effects of pH on hydrolysis with NaOH low. Probably the monochloride reacted with are shown in Table 5. As expected, the same methanol or ethylene glycol to form ethers. It results were obtained in the optimum pH range is known in the hydrolysis of allyl chloride that of 8～10. diallyl ether is formed by the reaction of allyl 3.4 Hydrolysis in the Presence of Alkali chloride with the allyl alcohol1),14) produced. and Solvent 3.4.2 Hydrolysis by Using DMSO and DMF 3.4.1 Effects of Solvents a) Hydrolysis with NaOH and Ca(OH)2 in Results of hydrolysis by using some solvents DMSO are shown in Fig. 4. Dimethylsulfoxide (DM- Results of hydrolysis in DMSO are shown in SO), dimethylformamide (DMF), triethanolamine Fig. 5 for NaOH and Fig. 6 for Ca(OH)2, re-

Volume 15, No. 2, November 1973 Furukawa, Asano and Komatsu: Syntchesis of 168

Fig. 6 Effectsof Amount of H2O and DMSO [DMSO-Ca(OH)2]

Further, it was interesting to note that, at a lower level of water content, a higher conversion

of monochloride was obtained in contrast with the case in which DMSO was absent. As an Fig. 4 Effects of Solvents (NaOH) alkali catalyst, Ca(OH)2 was preferable to NaOH because of its higher selectivity for prim-C8OH formation and of its lesser decrease in selectivity at low levels of water content. b) Hydrolysis with Ca(OH)2 in DMF Results are shown in Table 6 and compared with those in the absence of DMF. From these results it was observed that DMF increased the conversion of monochloride but did not increase the selectivity for prim-C8OH formation because of the increase in the lighter by-products formed by the elimination reaction. Therefore, DMF was found to be undesirable as a hydrolysis solvent. 3.4.3 Reaction Rate and Activation Energy The kinetics shown in Fig. 7 indicated that hydrolysis of monochloride with Ca(OH)2 in DMSO was SN2 reaction, and the activation energy was calculated as 19kcal/mol. On the other hand, the activation energy of hydrolysis Fig. 5 Effectsof Amount of H2O and DMSO with Ca(OH)2 in the absence of DMSO was (DMSO-NaOH) found to be 25kcal/mol (the temperature de- spectively. It was found from these results that, pendence of this reaction was determined under in the presence of DMSO, the rate of hydrolysis the same reaction conditions as those in Table 5). of monochloride was high, prim-C8OH was form- These results suggested that accelerating effect ed selectively and the formation of sec-C8OH of DMSO might be attributed to the stabilization was supressed (product ratio was below 2%). of the transition state by solvation17)～19).

Bulletin of The Japan Petroleum Institute Isooctenyl Alcohols from Diisobutylene via Chlorination 169

Table 6 Hydrolysis with Ca(OH)2 in the Presence of DMF

Fig. 7 Plotsof x/a(a-x) vs.Time for Hydrolysisin the Presenceof DMSO-Ca(OH)2

3.4.4 Change of Product Composition by Hydrolysis Fig. 8 Change of the Product Compositionin Hy- As shown in Fig. 1, four isomers contained in drolysis[DMSO-Ca(OH)2] the monochloride were changed to alcohols by hydrolysis. Behavior of each isomer was studied chlorides reacted during hydrolysis are shown by analysis of the reaction mixture samples taken in Table 7. A control experiment revealed during the course of the reaction. The optimum that the four C8 alcohols did not interconvert to conditions of hydrolysis with Ca(OH)2 in DMSO each other. As the ratios of prim-C8 alcohols were taken up in this study, and the results ob- formed/prim-C8 chlorides reacted (Table 7) were tained are shown in Fig. 8. These results showed approximately constant (0.9～1.0) throughout the that primary chlorides were hydrolyzed more reaction, it was considered that most of the prim- easily than the secondary chloride, and these C8 chlorides changed to prim-C8 alcohols without results were opposite to those described in the rearrangement. On the other hand, the ratios patents3), in which the secondary chloride reacted of sec-C8 alcohol formed/sec-C8 chloride reacted rapidly. In SN2 reaction OH- ions attacked the were extremely small in the latter half of the

C atom with δ+ combined with chlorine and it reaction (after 3hr) where sec-C8 chloride had was considered that primary chlorides which had reacted, and most of the reacted sec-C8 chloride

C with stronger δ+ showed higher reactivity (above 90%) changed into other compounds than the secondary chloride. than to sec-C8 alcohol. It was assumed that The ratios of the amounts of alcohols formed/ the reacted sec-C8 chloride changed to cis and

Volume 15, No. 2, November 1973 170 Furukawa, Asano and Komatsu: Synthesis of

Table 7 Formed Alcohol/Reacted Chloride Ratios in the Hydrolysis [DMSO-Ca(OH)2]

Table 8 Ratios of cis-/traps-isomer in Formed Alcohol [DMSO-Ca(OH)2]

trans-C8 alcohols because the ratio of cis and CH=CH2) and HCl aqueous solution, contained trans-C8 alcohols formed/cis and trans-C8 chlorides mainly trans-isomer. reacted was over 1.0 in the latter half of the The reaction path for the formation of iso- reaction. In addition, the ratio of cis, traps octenyl alcohols from chlorides discussed above and sec-C8 alcohols formed/cis, trans and sec-C8 was summarized as follows: chlorides reacted was less than 1.0 (0.7～0.8) even in the latter half of the reaction. This result did not conflict with the prediction that sec-C8 chloride changed to cis and trans-C8 alcohols. Moreover, the isomerization of secondary isomers to primary isomers (cis and trans) was supported by the results of the ratios of trans- isomer/cis-isomer in alcohol given hereinafter. Ratios of trans-isomer/cis-isomer (t/c ratio) of cis and trans-C8 alcohols are shown in Table 8. The t/c ratio was close to that of cis and trans- The allyl rearrangement in the hydrolysis of C8 chloride in the first half of the reaction halogenated hydrocarbons has not been reported, (within 2hr), while the t/c ratio was high in the but it is known in the chlorination of alcohol. latter half of the reaction where sec-C8 chloride Young et al.20),21)showed that primary allylic type was considered to form primary cis and trans-C8 chlorides were formed by allyl rearrangement in alcohols by isomerization. It was considered that the chlorination of allylic type alcohols by thionyl high t/c ratio was due to the lesser steric hind- chloride and they explained these results by rance for the trans-isomer. Hatch et al.12) have ion pair mechanism. In this work, the reaction confirmed that crotyl chloride (CH3-CH=CH- rate was acceralated by use of DMSO solvent, CH2-Cl), which was obtained by isomerization and nearly complete isomerization of secondary in the reaction of 3-butene-2-ol (CH3-CHOH- to paimary isomer took place (Fig. 8), while Bulletinof The Japan PetroleumInstitute Isooctenyl Alcohols from Diisobutylene via Chlorination 171

secondary alcohol was formed in an appreciable 7) Bartlett, P. D., Lefferts, E. L., ibid., 77, 2804 (1955). amount in the absence of DMSO (Table 5). 8) Byers, A., Hickinbottom, W. J., J. Chem. Soc., 1948, 248. Therefore, it might be supposed that hydrolysis 9) Gasson, E. J., Graham, A. R., Millidge, A. F., was accelerated by the activation22),23) of free Robson, I. K. M., Webster, W., Wild, A. M., Young, D. P., ibid., 1954, 2170. OH- ion due to the action of DMSO, and, si- 10) Wadswarth, Jr., W. S., J. Am. Chem. Soc., 83, 1733 multaneously, this reaction proceeded through (1961). the stabilized transition state by solvation17)～19) 11) Young, W. G., Caserio, F. F., Jr., Brandon, D. D., Jr., ibid., 82, 6163 (1960). where isomerization took place. 12) Hatch, L. F., Nesbitt, S. S., ibid., 72, 727 (1950). 13) Ando, S., Ono, I., Tada, H., Uchida, Y., Anual Acknowledgement Report of the Engineering Research Inst., Faculty of Eng., Univ. Tokyo, 18, (2), 18 (1959). The authors wish to thank Dr. Hiroshi Hase- 14) William, E. C., Trans. Am. Inst. Chem. Eng., 37, gawa for his helpful discussions and suggestions. 157 (1941). The authors also wish to express their gratitude 15) Yamashita, Y., Shimamura, T., Kogyo Kagaku Zasshi (J. Chem. Soc. Japan, Ind. Chem. Sect.), 61, to Dr. Tozo Amemiya, Executive Vice President, 1185 (1958). Maruzen Oil Co., Ltd. for permission to publish 16) Yamamura, J., Scientific Papers of Faculty of Eng., Tokushima Univ., 3, 14 (1951). this paper. 17) Miller, J., Parker, A. J., J. Am. Chem. Soc., 83, 117 (1961). References 18) Parker, J., J. Chem. Soc., 1961, 1328; 4398. 1) Shih, T. W., Kamiya, Y., Ono, I., Ando, S., J. 19) Parker, J., Quart. Rev., 16, 163 (1962). Japan Petrol. Inst., 3, (10), 809 (1960). 20) Young, W. G., Gaserio, F. F. Jr., Brandon, D. D. 2) U. S. 2,783,285 (1957). Jr., J. Am. Chem. Soc., 82, 6163 (1960). 3) U. S. 2,885,445 (1959). 21) Sharman, S. H., Caserio, F. F., Nystron, R. F., 4) Brit. 950,476 (1964). Leak J. C., Young, W. G., ibid., 80, 5965 (1958). 5) Blicke, F. F., "Organic Reactions", Vol. I, 303 22) Leary, J. A., Kahn, M., ibid., 81, 4173 (1959). (1954) John Wiley & Sons, New York. 23) Cavell, E. A. S., J. Chem. Soc., 1958, 4217; 1960, 6) Marvel, C. S., Myers, R. L., Saunders, J. H., J. 1453; 1961, 226. Am. Chem. Soc., 70, 1694 (1948).

Volume 15, No. 2, November 1973