Int.J.Curr.Microbiol.App.Sci (2014) 3(9) 211-223

ISSN: 2319-7706 Volume 3 Number 9 (2014) pp. 211-223 http://www.ijcmas.com

Original Research Article The dichlorocyclopropanation of 3-methyl-1-cyclohexene and 4-vinyl-1- cyclohexene using water soluble multi-site phase transfer catalyst-A kinetic study

K.Shanmugam* and E.Kannadasan

Deptartment of Chemistry, Government Arts College, Chidambaram, TamilNadu, India *Corresponding author

A B S T R A C T

The present study focuses the attention towards the utility of multi-site phase K e y w o r d s transfer catalyst (MPTC), is demonstrated by studying -ion initiated reaction like dichlorocarbene addition to olefins. The formation of the product was Multi-site phase monitored by GLC.Dichlorocyclopropanation of 3-methyl-1-cyclohexene and 4- transfer catalysts, vinyl-1-cyclohexene catalysed by multi-site phase transfer catalyst carried out in Dichlorocyclopro biphasic medium under pseudo-first-order conditions by keeping aqueous panation, hydroxide and in excess. The effect of various experimental parameters 3-methyl-1- on the rate of the reaction has been studied. Also thermodynamic parameters such cyclohexene;4- as S#, G# and H# were evaluated; based on the experimental results, a suitable vinyl-1- mechanism is proposed.It also deals in greater detail on the kinetic aspects of cyclohexene, Kinetics chosen reactions. An attempt has been made to compare the ability of MPTC-1 with MPTC-II and single-site PTC for dichlorocarbeneaddition to olefins like 3- methyl-l-cyclohexene and 4-vinyl-l-cyclohexene.

Introduction

The reaction of chloroform with strong to be generated in, or transferred to the bases to generate synthetically useful organic phase, where its reaction with 3- dichlorocarbene normally requires methyl-l-cyclohexene is much greater than anhydrous conditions to avoid its rapid with water addition of dichlorocarbene to 3- hydrolysis (Reeves et al., 1976). Thus methyl-l-cyclohexene gave only normal addition of chloroform to a mixture of 3- dichlorocyclopropane product. Makosza and methyl-l-cyclohexene and aqueous 25% Bialecka (1977) formulated the mechanism solution gives 60-70% of the olefin (cyclohexene) yield in the presence of a phase transfer dichlorocyclopropanation under phase catalyst such as tridecyl methyl transfer conditions as reaction of CHCl3 chloride or benzyl triethyl ammonium with OH- at the aqueous organic phase chloride. The remarkable increase in yield of boundary, from where it is then taken in to the dechlorocarbene adduct reflects the the organic phase by the quaternary cation. ability of the quaternary salt to cause :CCl2 Soluble phase transfer catalysts for 211

Int.J.Curr.Microbiol.App.Sci (2014) 3(9) 211-223 dichlorocarbene addition to cyclohexene bicyclo[4.1.0]-heptane derivatives by the with concentrated aqueous sodium addition of dichlorocarbene to 3-methyl-l- hydroxide as the base were first reported by cyclohexene; the method involves the von Doering et al., 1980 and were reaction of 3-methyl-l-cyclohexene with investigated in detail by Makosza, 1978. The chloroform in the presence of concentrated phase transfer catalyzed dichlorocarbene aqueous solution of sodium hydroxide addition reaction of 3-methyl-l-cyclohexene (15%w/w) and catalytic amount of MPTC-I. was thought to proceed by rate-limiting The reaction proceeds exothermically when generation of the dichlorocarbene and the reagents are mixed at 500C and the hydroxide ion at the aqueous / organic yields of the product obtained by this interface. method are very high usually about 100%, within one hour with no excess of the 3- The reaction of chloroform with 4-vinyl-l- methyl-l-cyclohexene required. The ratio of cyclohexene (Starks and Napier, 1976) in 3-methyl-l-cyclohexene to chloroform the presence of sodium hydroxide gives an applied is 1: 10 in volume, depending on the excellent yield of a product C9H12Cl2which availability of the olefin. In a similar way, contains the bicyclo [4.1.0] heptane the addition of dichlorocarbene with 4- (norcarane) skeleton. In the early work, we vinyl-1-cyclohexene yielded 100% product have observed that dichlorocarbene addition within one hour under PTC conditions. reaction was carried out with excess of 3- methyl-l-cyclohexene; dichloronorcarane The dichlorocarbene addition with 3-methyl- product was obtained in a yield of about l-cyclohexene and with 4-vinyl-l- 63% under single-site PTC conditions. The cyclohexene were chosen to investigate the present detailed investigation of this reaction kinetic aspects using the new, water-soluble permitted us to develop a new method for multi-site phase transfer catalyst (MPTC- the preparation of 7,7 dichloro-3-methyl- I).

CH3 H3C

MPTC-I (0.1 mol%) Cl

CHCl3, 15% NaOH, 500rpm, 500C Cl

7,7'-dichloro-3-methyl-bicyclo[4.1.0]-heptane (Scheme-1)

MPTC(0.1 mol%) Cl

CHCl , 15% NaOH, 3 Cl 500rpm, 500C 7,7'-dichloro-4-vinyl-bicyclo[4.1.0]-heptane (Scheme-2) Dichlorocarbine addition to 3-methyl-l-cyclohexene and 4-vinyl-l-cyclohexene under PTC conditions

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The kinetic experiments for the 89%. This reaction was also carried out by dichlorocarbene addition to 3-methyl-l- Winberg et al, 2007, using 50% aqueous cyclohexene and 4-vinyl-l-cyclohexene sodium hydroxide and catalytic amount of (schemes 1, 2) were conducted under bi- TEBA (PTC) and obtained 72% yield of the phase conditions with excess of aqueous norcarane product, 7, 7 dichlorobicylo sodium hydroxide and chloroform under [4.1.0]-heptane.In the present study, the rate pseudo first order conditions. The reaction constant is dependent on the stirring speed was studied at a stirring speed of 500rpm in up to 500rpm and maintains constancy the temperature range 40-600C. Before the beyond the limit. The reaction is carried out kinetic run was started, the catalyst was in aqueous medium; the anion exchange conditioned with aqueous sodium hydroxide equilibrium between the anions in the and chloroform for 10 minutes. The aqueous phase and those associated with substrate, 3-methyl-l-cyclohexene/4-vinyl-l- quaternary salt in the organic phase was cyclohexene preheated at the appropriate very relative to the organic phase temperature, was added to the reaction transformation reaction. The mass transfer mixture. The samples were collected from across the interface is regarded as evident the organic layer at regular intervals of time. from Fig. 1 at low stirring speed. At The kinetics of dichlorocarbene was agitation level 500rpm, anion exchange followed by estimating the formation of two equilibrium is very fast relative to the different norcarane products namely 7,7 - reaction and the substrate consumption rate dichloro-3-methyl-bicyclo[4.1.0]-heptane becomes independent of the stirring rate as and 7,7 dichloro-4-vinyl-bicyclo[4.1.0]- observed by Makoszaet al, 1975,, in the heptane using gas chromatographic study of dichlorocarbene addition to technique. The effect of various cyclohexene catalyzed by triethyl benzyl experimental parameters such as stirring ammonium chloride (TEBA) under PTC speed, substrate concentration, sodium conditions. Doering, Wawrzyniewicz and hydroxide concentration and temperature on Jawdosiak, 1985 reported independently a the reaction rate constants were studied. The similar observation that reflected kinetic kinetics was measured up to 30% of the control by chemical reaction in which [Q+X] formation of the product. is at a steady-state concentration. Below 500rpm the requirement for sufficiently Effect of Stirring Speed rapid mass transfer of the reacting anion is not met and diffusion controlled kinetics is The effect of varying stirring speed on the observed. rate of dichlorocarbene to 3-methyl-l- cyclohexene and 4-vinyl-l-cyclohexene was Hence the independence of the reaction rate studied in the range 100-800 rpm. From the constants on the stirring speed above plots of log(a-x) versus time, the pseudo- 500rpm in the present study is indicative of first order rate constants were evaluated. A extrication mechanism. The behavior is in plot of kobs against stirring speed is shown in short contrast to reactions operative through Fig. 1 (Table1). Balakrishnan et al,2005, had interfacial mechanism, where the reaction documented the kinetic studies of rate is directly proportional to the stirring dichlorocarbene addition to cyclohexene speed. using aqueous sodium hydroxide and chloroform catalyzed by polymer supported Parham, 1983, reported the continuous phase transfer catalyst, obtained an yield of increase in the rate of dichlorocarbene

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Int.J.Curr.Microbiol.App.Sci (2014) 3(9) 211-223 addition even up to stirring speeds of Effect of catalyst amount 1200rpm. It has also been reported that the rate of an interfacial reaction is proportional The amount of catalyst was varied from to the stirring speed in the range of 600 to 0.05-0.25 mol% for the dichlorocarbene 1400rpm.The interfacial area per unit addition to 3-methyl-l-cyclohexene and 4- volume of dispersion increased linearly with vinyl-l-cyclohexene (based on the substrate increasing speed till a stage is reached where amount) and the experiments were there is no significant increase in the conducted using 15% w/w aqueous NaOH interfacial area per unit volume of dispersion solution. The pseudo first order rate with the corresponding increase in the constants are calculated from the plots of log speed. Thus increasing the stirring speed [a-x] versus time. The rate constants are changes the particle size of the dispersed dependent on the amount of catalyst used in phase.Above certain stirring speed each reaction.The increase in rate constants (500rpm), the particle size does not change. is attributed to the increase in the number of The constancy of the rate constants is active sites. Control experiments were observed not because the process is performed and no product was detected even necessarily reaction rate limited but because after 2 hours of the reaction. Only a catalytic the mass transfer rate has reached constant amount (0.1 mol% based on the substrate) is value. Therefore Fig. 1(Table 1) is required in order to obtain good yields of the indicative of an extraction mechanism and product emphasizing the indispensability of not of a real phase Transfer . the catalyst. Sasson et al, 1987, evaluated first order rate constants for the Effect of Substrate Amount dichlorocarbene addition to cyclohexene using N, N-di-n-butyl piperidinium iodide as Kinetic experiments were performed by the catalyst. varying the amount of 3-methyl-l- cyclohexene from 6.34-25.36mmol and 4- Abilogrithmic plot of reaction rate constants vinyl-l-cylohexene from 3.87-23.24 mmol versus the concentrations of catalyst gave a and keeping other reagents such as straight line having a slope of 4.6 for l- chloroform and NaOH in excess. Pseudo- methyl-l-cyclohexene and 1.35 for 4-vinyl-l- first order rate constants are evaluated from cyclohexene (Table 1, Fig.2). In the study the linear plots of log (a-x) versus time. The of dehydrobromination of ethylbromide, observed reaction rate constants decrease as zero order kinetics with respect to the the amount of substrate increases Fig. 3 catalyst was observed. (Table 1). Effect of sodium hydroxide concentration The decrease in rate may be attributed to the proportionate decrease in the number of The rate of dichlorocarbene addition to 3- catalytic active sites available. The results methyl-l-cyclohexene and 4-vinyl-l- suggest that the concentration of the cyclohexene strongly depends on the substrate in the organic phase is not strength of sodium hydroxide; kinetic important and the concentration of the experiments were carried out employing substrate at the inter-phase may be vital. 3.41-7.89MaqueousNaOH for both the Similar observation was earlier reported by olefins. Pseudo-first order rate constants are Balakrishnanet al,2004, in the study of evaluated from the plots of log (a-x) versus dichlorocarbene to cyclohexene with NaOH time. The reaction rate constants and PS-PTC under tri-phase conditions. 214

Int.J.Curr.Microbiol.App.Sci (2014) 3(9) 211-223 tremendously increased with increase in Kcal mol-1 for 4-vinyl-l-cyclohexene (Table basicity of hydroxide ion. Bilogrithmic 1, Fig.5). The other thermodynamic plots of the reaction rate against sodium parameters, H#, S#and G# are Evaluated hydroxide concentrations give a straight line and presented in Table2. having a slope of 1.3 for 3-methyl-l- cyclohexene and 1.8 for 4-vinyl-l- The very low activation energy indicates cyclohexene (Table 1, Fig.4). that the step (2) (ie., chemical reaction) is not the rate-determining step; on the other In the case of the isomerization of allyl hand, these results are characteristic of benzene, the effective kinetic order with diffusion control. At a given temperature, respect to aqueous NaOH concentration was stirring speed and shape of the reaction reported to be 4-8, where extraction vessel, there exists a definite rate of mass mechanism is operative. Makosza reported transfer between two phases on contact (the the successful, application of two phase aqueous-organic phase boundary), which is catalytic and ion-pair extractive methods in also dependent on the catalyst concentration the reaction of carbanions and halocarbenes. upon a certain value. It can be seen from the The instability of some C-H acids in the Table.1 andFig.5 that the dependence of the presence of aqueous alkali (such as reaction rate constants on the concentration hydrolysis of of other functional of the catalyst is stronger at the lower groups) was pointed out.The remedy concentration (in the present case, between suggested was the use of less concentrated 0.05-0.2 mol%) and is weakly dependent at solution of the base. This requirement is higher catalyst concentrations (0.25mol%). met by employing MPTC-I as the optimum In the concentration range examined, the NaOH concentration is 15% as against 25% dependence ofkobs on the [catalyst] does used in the case of TEABr. Generally not attain linearity. Therefore it may be quaternary salts are stable up to ~1500 C but 0 concluded that a process involving less stable at temperature 78 C, when strong maximum rate of diffusion occurs in the alkalis were used. While employing MPTC- present reaction and that the maximum rate I, the need to use low concentration of of diffusion is being approached at the alkali in spite of the fact that the reaction is higher catalyst concentration (0.25mol %). in a great measure dependent on it reveals At still higher concentration, the capacity of the higher activity and applicability of the the system to accommodate diffusion of MPTC-I. additional catalyst is smaller or negligible.

Influence of temperature variation Similar observation was earlier reported by Rabinovitzetal, 1981, in the study of The effect of varying temperature on the rate dehydrobromination of (2-bromoethyl) of dichlorocarbene addition to 3-methyl-l- benzene where Ea is reported to be 12.4 K cyclohexene and 4-vinyl-l-cyclohexene was -1 0 cal mol . In general, Ea is equal to 0-10 studied in the range of 40-60 C. The kinetic Kcal mol-1 for diffusion-controlled processes profile of the reaction is obtained by plotting and usually over15Kcal mol-1 for chemical log (a-x) versus time. The rate constants reaction controlled processes. A higher Ea increase with the increase in value has been reported for the polystyrene temperature.The energy of activation is bound trimethyl ammonium ion catalyzed calculated from Arrhenius plot, Ea=9.2 Kcal -1 reaction, which was controlled by strict mol for 3-methyl-l-cyclohexene and 11.5 intrinsic reactivity under tri-phase reactions.

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______Table 1- Effect of MPTC-1 on the rates of dichlorocarbene addition to 3-methyl-1- cyclohexene and 4-vinyl-1-cyclohexene reactions 4 -1 Type of variable Rates of the reaction (kobs x 10 , S ) Variation parameters ______3-methyl-1- 4-vinyl-1- Cyclohexene cyclohexene Stirring 100 0.72 0.19 Speed (rpm) 200 0.81 2.75 300 0.82 3.80 400 1.25 5.21 500 1.83 6.03 600 1.86 6.05 700 1.88 6.07 800 1.88 6.07

Catalyst 0.05 1.04 1.98 Amount0.10 1.65 2.22 (mmols) 0.15 1.98 3.87 0.20 2.69 4.69 0.25 3.29 5.02

Substrate 6.34 7.90 16.59 Amount8.45 5.74 12.46 (mmols) 12.68 3.77 9.17 16.91 3.15 5.28 21.13 2.23 2.85 25.36 1.33 2.21

[NaOH] (M) 3.41 1.01 1.30 4.41 1.26 2.43 5.49 2.02 3.68 6.65 2.60 4.30 7.89 3.42 4.93

Temperature 313 0.75 1.30 (K)318 1.30 1.82 323 1.98 3.26 228 2.71 3.63 333 3.27 4.32 ______

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Table.2 Thermodynamicparameters. -1 # -1 # -1 # -1 Substrate E a Kcalmol H Kcalmol - S CalK G Kcalmol mol-1 3-methyl-1- 9.2 8.5 181.0 56.9 cyclohexene 4 vinyl-1- 11.5 10.8 175.6 55.2 cyclohexene Table.3 Comparison of reaction rate constants with different catalysts.

-4 -1 Entry Catalyst Amount k obs /10 ,S (mol %) 3-methyl-1-cyclohexene 4-vinyl-1-cyclohexene A None None Nil* Nil* B MPTC-I 0.1 3.08 5.35 C MPTC-II 0.1 2.01 3.16 D SPTC 0.1 0.45 2.00 *No Conversion after 3 hours

MULTI-SITE PHASE TRANSFER CATALYST-I SACTIVITY INHYDROXIDE-ION INITIATED REACTIONS. The results shown in Table.4 establish the synthetic utility of the new MPTC-I under PTC / OH-conditions.

Substrate with Products (S) %Conv. Spectral eference S.No experimental awith Reaction datab conditions time

1 3-methyl-1- Product 100.00; 1H-NMR cyclohexene (1.49 min) One hour (CDCl3/TMS O Donnel (0.60min) CH3 ) l, CH3 =2.33 Etal,2007 (s,3H) Cl 1.71- 1.29(m,10H) Cl

1. Subs. amount: 2.0 ml 2. Cat.amount: 0.1mol% 3. Solvent: CHCl3; 20 ml 4. [NaOH]: 15%w/w, 25ml(4.41m) 5. Temp: 50oC

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2 4-vinyl-1- Product 100.00; 1H-NMR cyclohexene (1.49 min.) One hour (CDCl3/TMS (0.60 min.) ) Fedoryns =1.98- ki, C 0.949 Etal,1993 C (m,8H) 1.91 1.78 1. Subs. amount: 2.0 (dd,2H) ml 2. Cat. amount: 0.1 mol% 3. Solvent: CHCl3; 20 ml 4. [NaOH]: 15%w/w, 25ml (4.41M) 5. Temp. 50oC a: Conv.by Gaschromatography, b: for known compounds only selected spectral data given. Table: 4. Hydroxide-ion initiated reactions under the PTC conditions using the new MPTC-I.

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The activation energy for the conducted at identical reaction conditions dichlorocarbene addition to cis 1, 4-poly taking 2.0ml substrate, 20ml chloroform, butadienewas reported to be 21 K cal mol-1 0.1mol% catalyst (MPTC-1, MPTC-II and and for this an interfacial mechanism was SPTC) and 15% w/w NaOH. The reactions proposed (Selvaraj, Rajendran, 2011). The were run at 500C with a stirring speed of activation energy of intra particle diffusion 500rpm.The observed rate constants of anion exchange resins in aqueous -4 -1 -1 (kobs/10 , S )for 3-methyl-l-cyclohexene solutions is of the order of 5-10 K cal mol . and 4-vinyl-l-cyclohexene are found to be The observed energy of activation for the 2.65 and 7.03 respectively (Table.3). These dichlorocarbene addition to 3-methyl-l- values are in an approximate ratio 3: 1 (4- cyclohexene and 4-vinyl-l-cyclohexene are -1 vinyl-l-cyclohexene: 3-methyl-l- 9.2 and 11.5 Kcal mol and hence a cyclohexene). hydroxide ion extraction mechanism is proposed for the reaction under study which The reaction rate of 4-vinyl-l-cyclohexene is is governed by diffusion control. three times faster than 3-methyl-l- Comparison of reaction rate constants cyclohexene which can be attributed to the electron-rich nature due to the possibility of A comparison of reaction rate constants of secondary orbital interaction of the vinyl the two dichlorocarbene additions can be group in 4-vinyl-1-cyclohexene which attempted since all the reactions were readily attached to the electron-deficient 219 Int.J.Curr.Microbiol.App.Sci (2014) 3(9) 211-223 dichlorocarbene. Also the transitions state systems), has been the subject of much of 4-vinyl-l-cyclohexene is far less hindered discussion. The anion (: CCl2) which is than 3-methyl-l-cyclohexene which makes derived from chloroform is sensitive 4-vinyl-l-cyclohexene more reactive than 3- towards the aqueous NaOH concentration methyl-l-cyclohexene. may be explained by a combination of several major factors, the mass law, the MPTC-I : , 1, 11 tris(triethyl ammonium salting out effect and the basicity of the methylene bromide) hydroxyl hydroxide ion. Past studies have also ethylbenzene (Shanmugan, Balakrishnan, revealed that the nature (singlet or triplet) 2007), MPTC -II : 2-Benzylidine- and reactivity of dichlorocarbenes depend N,N,N,N1,N1, N1-hexa ethyl propane- 1,3-di significantly on the mode and medium of ammonium dichloride (Balakrishnan, Paul generation as well as whether the Jayachandran,1995), SPTC : Single site substituents are directly bound or conjugated phase transfer catalyst (TEBAB) with .The rate-determining step of the reaction involves the attack of InTable3, the results reflect a comparative dichlorocarbene on the olefins such as 3- trend among the different catalysts used. mrthyl-l-cyclohexene and 4-vinyl-l- Based on the observed rate constants, it is cyclohexene. The kinetically controlled step evident that the MPTC-I is 60% and 75% is greatly influenced by the orientation of all more active than the MPTC-II and single- the relevant factors around the site TEBAB respectively. Control dichlorocarbene anion during the attack. experiments of dichlorocarbene additions to From GC studies, it is clear that there is no olefins in the absence of the catalyst resulted norcarane product, at all hydroxide ion in <1% conversion in three hours. As is concentration and this may be due to the evident from Table 4, the new MPTC association of the active site and site the catalyst-I is found to perform extremely well electrophilic nature of: CCl2. for hydroxide-ion initiated reaction systems resulting in excellent yields of the products. Two major mechanisms have been proposed All the dichlorocarbene additions reactions for PTC reactions, the Stark s extraction were conducted at identical reaction mechanism(Starks, 1971) and the Masoksza conditions taking 20ml chloroform, 0.1 interfacial mechanism (Makosza, 1972). mol% catalyst (MPTC-I) and 15% w/w Reactions proceed through the extraction NaOH. The reactions were run at 500C with mechanisms are characterized by a stirring speed of 500rpm. The reaction, 1.increased reaction rate with increased viz., dichlorocarbene addition to olefins organophilicity or with larger symmetrical such as 3-methyl-l-cyclohexene and 4-vinyl- tetra alkyl ammonium ions, 2.independence l-cyclohexene in the presence of MPTC-I of reaction rate on stirring speed above a resulted in 100% conversion within one certain valueand 3.linear dependence of hour. reaction rate on catalyst concentration.Incontrast, reaction believed Mechanism to proceed through the Makosza s interfacial mechanism are characterized by The mechanism of hydroxide-ion initiated 1. Maximum reactivity with relatively reactions, like dichlorocarbeneaddition hydrophilic quats (Yang etal, 2010), usually reactions which were performed under phase 2. Increased reaction rate with stirring speed - transfer catalyzed conditions (PTC/OH even up to 1950rpm (Wang etal, 2006) and

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3. Fractional kinetic order with respect to dichlorocarbene addition to 3-methyl-l- catalyst (when interfacial steps are at least cyclohexene /4-vinyl-l-cyclohexene on quat partially rate structure, stirring speed and concentration of limiting). the catalyst is consistent with that found for the extraction mechanism. The mechanism From the observed experimental results, it for the dichlorocarbene addition to 3- would be concluded that the dependency of methyl-l-lcyclohexene and 4-vinyl-l- the kinetic data on the stirring speed up to cyclohexenemay be written as. 500rpm, the dependency of the rate of

fast(1) 3 CCl - Na+ + H O 3 CHCl3 + 3 NaOH 3 2 (org) (aq) (interface)

MPTC , fast (2) ( org)

+ - Ph-CH(OH)-C [CH2N Et3 CCl3 ] 3 + 3 NaBr (org) (aq)

CH3 fast(3)

CH3

Cl 3 Cl 3 : CCl2 + MPTC (org) (org) Slow(4)

(A) (scheme - 3)

Cl 3 (A) slow(5) Cl

(Scheme- 4)

In summary, a multi-site phase transfer cyclohexene and 4-vinyl-1-cyclohexene catalyst was used, its catalytic efficiency from the experimental evidence; it is was investigated by following obvious that the reaction follows an dichlorocyclopropanation of 3-methyl-1- interfacial reaction mechanism. The tri-site cyclohexene and 4-vinyl-1-cyclohexene.the phase transfer catalyst MPTC-I, exhibits kinetic parameters such as stirring speed, higher reactivity than the conventional substrate amount, sodium hydroxide MPTC-II and single-site PTC (BTEAB). concentration and temperature were found to influence the rate constant (kobs) values Acknowledgments remarkably. The author would like to thank the Principal The energy of activation (Ea) and other and Head of the Department of Chemistry of thermodynamic parameters such as S#, G# Government Arts College C-Mutlur, and H# were evaluated for the Chidambaram-608102, TamilNadu for their dichlorocarbene addition to 3-methyl-1- grant of permission to do this research work.

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from electrophilic alkanes and Yang, H.M., and Peng, G.Y.2010, Ultra CHCl3under PTC conditions, J.Org. sound assisted third liquid phase Chem., 38 : 6120. transfer catalyzed esterification of Starks, C.M., 1971 phase transfer catalysis, sodium salicylate in a continuous two- Commercial usage of PTC techniques, phase flow reactor, Ultra son, Sono J.Am.Chem.Soc., 93:195. Chem.,17: 239-245. Makosza,M., Fedorynski,M.,Jonczyk,A., Wang. M.L., and Lee, Z.F. 2006, Kinetic 1972,Synthesis of 1-(1- cyano-1-phenyl) study of synthesizing Bisphenol - A alkyl-2-phenyl by phase diether in a phase transfer catalytic transfer catalysis, Tetrahedron Lett., reaction, Bull. Chem.Soc.Jpn.79:80-87. 2395.

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