A process for producing a cyclopropane derivative comprising contacting a diazo compound and an olefinically unsaturated compound in the presence of a catalytic amount of copper cation-exchanged perfluorinated ion exchange polymer is disclosed.

FIELD OF THE INVENTION 
This invention relates to catalytic processes for producing cyclopropane 
derivatives. 
BACKGROUND OF THE INVENTION 
Many transition metals and their complexes have been used as catalysts for 
the formation of cyclopropanes from olefins and diazo compounds. For many 
years, copper compounds were favored for their combination of ready 
availability, low cost and acceptable reactivity with a wide range of 
olefins and diazo compounds. Recently, homogeneous rhodium 
cyclopropanation catalysts have been developed which are more active than 
analogous copper catalysts. Although both heterogeneous and homogeneous 
copper cyclopropanation catalysts are known, all of the well-known rhodium 
cyclopropanation catalysts are homogeneous. Improved cyclopropanation 
catalysts are of considerable interest to the chemical industry. 
The earliest reported copper cyclopropanation catalysts were heterogeneous 
systems. References which are representative of this technology include: 
Loose, J. Prakt. Chim., 79 (2):505 (1909) which discloses copper bronze; 
Ebel et al., Helv. Chim. Acta, 12:19 (1926) which discloses copper powder; 
and Skell and Etter, Chem. Ind.(London), 6 (1958) which discloses copper 
sulfate. The following patents disclose heterogeneous copper compounds as 
cyclopropanation catalysts: U.S. Pat. No. 4,198,527 discloses Cu or 
CuSO.sub.4 ; U.S.S.R. Patent No. 652,172 discloses CuO; U.S.S.R. Patent 
No. 576,313 discloses CuO on pumice or alumina; U.S.S.R. Patent No. 4299 
discloses CuSO.sub.4 on pumice, alumina, activated carbon or Cu chips; 
Japanese Patent No. 50,116,465 discloses Cu; DE No. 3,244,641 discloses Cu 
or Cu salts; and European Patent No. 22,608 discloses Cu or Cu salts. 
Kirmse, Carbene Chemistry, 2nd Ed., (Academic Press, New York, N.Y., 1971) 
in Chapter 3, reviews both homogeneous and heterogeneous metal catalyzed 
decompositions of diazo-alkanes, -esters and -ketones. The use of 
transition metal compounds, including copper and copper salts, as 
cyclopropanation catalysts is described. 
In a more recent review of transition metal catalyzed cyclopropanations, 
Catalysis of Organic Reactions, Ed. by R. L. Augustine,(M. Dekker, New 
York, N.Y., 1985) in Chapter 4, the author concludes that Rh(II)acetate is 
generally the most suitable catalyst for intermolecular cyclopropanation 
reactions. However, Cu(II)triflate (i.e., Cu(II)trifluoromethanesulfonate) 
in nitromethane is a better catalyst for intramolecular cyclopropanations. 
Anciaux et al., J. Org. Chem., 45:695 (1980) disclose a comparison of 
several rhodium, copper and palladium cyclopropanation catalysts. With few 
exceptions, the relative efficiencies of three common cyclopropanation 
catalysts, Rh(II)acetate, Cu(II)triflate and Pd(II)acetate, were found to 
be Rh&gt;Cu&gt;Pd. The order of selectivity in competitive cyclopropanations is 
generally Rh&lt;Cu&lt;Pd. 
Salomon and Kochi, J. Amer. Chem. Soc., 95:3300 (1973), show that Cu(I), 
not Cu(II), is probably the active catalyst species in copper-catalyzed 
cyclopropanations, even when the copper reagent used is nominally Cu(II), 
e.g. CuSO.sub.4, CuCl.sub.2, or Cu(OTf).sub.2. This disclosure is 
consistent with earlier observations reported by others including 
Komendantov et al., J. Org. Chem. U.S.S.R., 2:561 (1966), and Wittig and 
Schwarzenbach, Justus Lieb. Ann. Chem., 650:1 (1961). 
Campbell and Harper, J. Chem. Soc., 283 (1945), disclose the synthesis of 
ethyl chrysanthemumates (i.e., 
2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropanecarboxylic acid ethyl 
esters) from the copper bronze catalyzed reaction of ethyl diazoacetate 
with 2,5-dimethyl-2,4-hexadiene. The use of copper catalysts in the 
synthesis of chrysanthemic acid esters is disclosed in the following 
references: Japanese Patent No. 49066660, Japanese Patent No. 54073758 and 
European Patent No. 128012. 
Matlin et al., J. Chem. Soc., Chem. Commun., 1038 (1984), disclose a method 
of attaching a chiral ligand to silica, coordinating Cu(II) or Ni(II) to 
the immobilized chiral ligand and using this modified silica as a 
cyclopropanation catalyst. When the substrate olefin is styrene, the 
catalyst tends to become coated with polystyrene, reducing the activity of 
the catalyst substantially and limiting the recycle value of the catalyst. 
Waller, Catal. Rev. Sci. Eng., 28(1):1 (1986), reviews catalysis with 
metal cation-exchanged resins. U.S. Pat. No. 4,446,329 discloses the 
preparation of several metal salts of perfluorosulfonic acid polymers, 
including a Cu(II) salt obtained from the reaction of 
Cu(NO.sub.3).sub.2.xH.sub.2 O with the acid form of a perfluorosulfonic 
acid polymer. This (perfluorosulfonic acid polymer)-supported copper salt 
was shown to be only a slightly active catalyst for the ethylation of 
benzene, perhaps due to resin fusion at the reaction temperature, 
240.degree. C. 
Pittman, Polymer-supported Reactions in Organic Synthesis, Ed. by P. Hodge 
and D. C. Sherrington, (Wiley and Sons, 1980) in Chapter 5, reviews 
catalysis by polymer-supported transition metal complexes. The problem of 
metal loss due to leaching or chemical changes is disclosed. 
SUMMARY OF THE INVENTION 
The present invention provides a process for producing a cyclopropane 
derivative comprising contacting a diazo compound and an olefinically 
unsaturated compound in the presence of a catalytic amount of copper 
cation-exchanged perfluorinated ion exchange polymer. 
DETAILED DESCRIPTION OF THE INVENTION 
The invention resides in a process for catalyzing the reaction of a diazo 
compound with an olefinically unsaturated compound to form one or more 
cyclopropane derivatives, wherein the catalyst comprises copper 
cation-exchanged perfluorinated ion exchange polymer (PFIEP). As used 
herein, the expression "cyclopropane derivative" refers to a compound 
containing a substituted three-membered carbocyclic ring. Suitable 
substituents are compatible with the cyclopropanation process of the 
present invention. A partial list of suitable substituents includes 
saturated and unsaturated hydrocarbons, optionally containing heteroatoms, 
such as, halogens, nitrogen, oxygen, sulphur, or phosphorus. The 
advantages of using copper cation-exchanged perfluorinated ion exchange 
polymers as catalysts in this invention include increased catalytic 
activity over most known cyclopropanation catalysts for a wide range of 
unsaturated substrates, increased thermal stability of the catalyst due to 
the high degree of fluorination of the polymer backbone, ease of catalyst 
preparation and separation from the reaction mixture, and decreased 
leaching of the catalytic metal from the support compared to analogous 
rhodium catalysts. 
A wide variety of olefinically unsaturated compounds can be employed in the 
process of the present invention, including compounds with more than one 
ethylenic group and substituted compounds. It has been found that 
substituents with Hammett sigma-values less than 0.2, e.g., alkyl, aryl, 
alkoxy and aryloxy, do not interfere with the cyclopropanation reaction. 
The Hammett sigma-value is a numerical constant for a specified 
substituent. This value represents the effect of a selected substituent on 
the ionization of benzoic acid under standard conditions (water at 
25.degree. C.). Sigma-values provide a measure of the electron-withdrawing 
(.sigma.&gt;0) or electron-releasing (.sigma.&lt;0) properties of a substituent 
relative to hydrogen (.sigma.=0). A list of representative sigma-values 
for a variety of common substituents can be found in "Fundamentals of 
Organic Chemistry", page 571, by C. D. Gutsche and D. J. Pasto, published 
by Prentice-Hall, 1975. Some electron-withdrawing substituents with 
Hammett sigma-values greater than 0.2 can also be suitable, but only if 
the olefin contains no more than two such electron-withdrawing groups. 
Such substituents include, e.g., halo, acyl, aroyl, and alkoxycarbonyl. 
The ethylenic unit can be an isolated double bond, or part of a conjugated 
system. 
Acyclic and cyclic double bonds can be cyclopropanated by the present 
process. A partial list of olefinically unsaturated compounds which can be 
cyclopropanated by the process include , e.g., propene, butenes, pentenes, 
hexenes, octenes, decenes, tetradecenes, octadecenes, dococenes, 
cyclopentene, cyclohexene, cycloheptene, cyclooctene, butadiene, 
pentadienes, hexadienes, cyclohexadiene, cyclooctadiene, isoprene, 
styrene, norbornene, vinyl acetate, indene, dihydropyran, 
1,1-dichloro-4-methyl-3-pentadiene, 2,5-dimethyl-2,4-hexadiene and 
norbornadiene. Preferred olefinically unsaturated compounds contain from 
about 3 to about 20 carbon atoms, and most preferably from about 4 to 
about 10 carbon atoms. Most preferred olefinically unsaturated compound 
are selected from the group consisting of 2,5-dimethyl-2,4-hexadiene, 
styrene, cyclohexene, and 1,1-dichloro-4-methyl-1,3-pentadiene. 
Preferred diazo compounds which can be employed in the process of the 
present invention contain at least one electron-withdrawing substituent 
which is compatible with the diazo functionality and also has a Hammett 
sigma-value greater than zero. Most preferred diazo compounds are selected 
from the group consisting of diazo esters and diazo diesters, e.g., ethyl 
diazoacetate and diethyl diazodiacetate. 
The present process is conducted in the presence of a catalytic amount of a 
copper cation-exchanged perfluorinated ion exchange polymer. Preferably, 
the perfluorinated ion-exchange polymer PFIEP) is a perfluorinated 
sulfonic acid polymer (PFIEP[SO.sub.3 H]) or a blend of perfluorinated 
sulfonic acid and perfluorinated carboxylic acid polymers (PFIEP[SO.sub.3 
H]/PFIEP[CO.sub.2 H]). Most preferred perfluorinated sulfonic acid 
polymers have a number average molecular weight of at least about 5000. 
Preferably, the PFIEP contains a sufficient number of sulfonic acid groups 
to give an equivalent weight of from about 500 to about 20,000, and most 
preferably from about 900 to about 2000. Although the polymer backbone 
comprises, for the most part, fluorinated carbon atoms, it is not 
necessary that all other atoms be excluded. For example, ether oxygen 
atoms may be present in the backbone, as well as in the side chains of the 
polymer. Such other atoms and or groups as hydrogen (H), chlorine (Cl) and 
carboxy (COOH) may be present in limited amounts without significantly 
affecting the stability or operability of the polymer under the process 
conditions. It is preferred that the polymer contain no greater than about 
5 weight percent total of hydrogen and chlorine groups. Representative of 
suitable perfluorinated ion exchange polymers are the Nafion.RTM. 
perfluorinated ion exchange polymers, commercially available from E. I. du 
Pont de Nemours and Company. 
Perfluorosulfonic acid polymers may be employed in in a variety of known 
forms including beads, powders and films. The preparation of blends of 
perfluorinated sulfonic acid and perfluorinated carboxylic acid polymers 
is disclosed in U.S. Pat. No. 4,176,215, the disclosure of which is 
incorporated herein by reference. Preferred blends of perfluorinated 
sulfonic acid and perfluorinated carboxylic acid polymers include blends 
of tetrafluoroethylene copolymers with 
methylperfluoro-5-methyl-4,7-dioxanon-8-eneoate and tetrafluoroethylene 
copolymers with perfluoro(3,6-dioxa-4-methyl-7-octene) sulfonic acid. Most 
preferred blends have an ion exchange capacity of at least 0.7 meq/g. 
Preferably, the ratio of sulfonic acid to carboxylic acid groups in the 
blend is from about 1:1 to about 10:1, and most preferably from about 2:1 
to about 10:1. 
Although perfluorinated ion exchange polymers are generally available in 
the acid (or hydrogen ion) form, it may be desirable to exchange a portion 
of the acidic hydrogens of the polymer with alkali metal cations, e.g. 
K.sup.+, prior to the formation of the copper cation-exchanged 
perfluorinated ion exchange polymer. Methods for exchanging cations on 
perfluorinated ion exchange polymer are well known in the art. Two 
preferred methods for exchanging H.sup.+ by K.sup.+ are described in 
Examples 1 and 5. 
Copper salts useful for cation-exchanging into perfluorinated ion exchange 
polymer to form the catalyst system of the present invention include, but 
are not limited to, CuCl.sub.2, Cu(NO.sub.3).sub.2, CuSO.sub.4, CuCO.sub.3 
Cu(OH).sub.2, Cu(OTf).sub.2, Cu(OAc).sub.2, CuBr.sub.2 and 
Cu(ClO.sub.4).sub.2 and the hydrated salts thereof. Typically, copper is 
incorporated into perfluorinated ion exchange polymer in the cupric, i.e. 
Cu(II), form. Although not wishing to be bound by theory, there is 
evidence that the catalytically reactive form of the metal is Cu(I). It is 
believed that the diazo compound acts as a reducing agent to convert 
Cu(II) to Cu(I). Typically, between about 50% and about 98% of the cations 
or acidic hydrogen atoms of the polymeric support are replaced with copper 
to form the catalyst system of the present invention. Preferably, between 
about 50% and about 90% of the cation(s) or acidic hydrogen is replaced 
with copper. It is believed that maximum cyclopropanation activity is 
obtained from catalysts with the minimum number of acidic hydrogens. 
Preferably, the present process is conducted with a molar ratio of 
olefinically unsaturated compound to copper of from about 100:1 to about 
5000:1, and most preferably from about 400:1 to about 2000:1. Larger 
ratios may provide too little catalyst to achieve rate enhancement, and 
smaller ratios are uneconomical with regard to the perfluorinated ion 
exchange polymer. In addition, the ratio of olefinically unsaturated 
compound to diazo compound is, preferably, from about 5:1 to about 500:1, 
and most preferably from about 10:1 to about 100:1. Smaller ratios tend to 
result in the formation of diazines and diesters due to diazo coupling 
reactions, and larger ratios are uneconomical with regard to the olefin. 
Although a solvent is not required in the present process, it may be 
advantageous to employ one, particularly when higher molecular weight 
olefinically unsaturated compounds are used as substrates. Suitable 
solvents include aromatic hydrocarbons such as benzene or toluene, and 
chlorinated hydrocarbons such as methylene chloride, and fluorochlorinated 
solvents such as 1,1,2-trichlorotrifluoroethane. 
In a preferred embodiment, the process of the invention is effected by 
adding a solution of the diazo compound, the olefinically unsaturated 
compound and an optional solvent slowly, dropwise to a stirred suspension 
of the catalyst and olefinic substrate. It is desirable to maintain an 
excess of olefinic substrate relative to diazo compound to minimize the 
formation of diazines, diesters and other diazo coupling products. In some 
cases, it may be necessary to heat the reaction mixture during the 
addition of the diazo compound or after the addition is complete. 
Suitable reaction temperatures will depend on the reactivity of the olefin, 
the stability of the diazo compound and the volatility of the reactants. 
Preferred reaction temperatures are from about 0.degree. to about 
120.degree. C., and most preferably from about 20.degree. to about 
80.degree. C. It is not necessary to conduct the process in an inert 
atmosphere. The reaction time is not critical. The process can be run for 
periods as long as about 48 hours, but typically the reaction time is from 
about 0.25 hours to about 24 hours. 
As the reaction proceeds, N.sub.2 is evolved and the cessation of gas 
formation can be used to indicate completion of the reaction. When the 
reaction is complete, the reaction mixture can be filtered to remove the 
catalyst and the products isolated by standard techniques such as 
distillation or chromatography. 
The catalyst may be reused in further cyclopropanation reactions. The 
cyclopropanation process of this invention is useful in the preparation of 
functionalized cyclopropanes, some of which are key intermediates in the 
manufacture of synthetic pyrethroid insecticides.

The invention is further defined in the following examples wherein all 
parts, percentages, and equivalents are by weight, mesh sizes are U.S. 
Standard Sieve units, and all degrees are Celsius unless otherwise noted. 
Comparative examples are also included to point out the particular 
advantages of this invention. In the Examples and Comparative Experiments, 
gas chromatographic analysis was performed on either a 1/8" (3 mm) 
diameter, 10' (3.05 m) column packed with SE-30ABS or a 50' (15.3 m) 
cross-linked methyl silicone fused silica capillary column programmed from 
60.degree. to 200.degree. at 8.degree. min.sup.-1. 
EXAMPLE 1 
Synthesis of Ethyl Chrysanthemumate Using Cu,K-PFIEP[SO.sub.3 H] 
Catalyst Preparation 
A slurry of powder PFIEP[SO.sub.3 H](200-325 mesh) in the acid form (3.0 g, 
2.73 mequiv) was stirred with an aqueous (100 mL) exchanging solution of 
KCl (1.0 g, 13.4 mmol) for approximately 2 hours at 60.degree.-70.degree.. 
The exchanging solution was decanted and a fresh exchanging solution was 
slurried with the partially exchanged powder PFIEP for approximately 4 
hours. The resulting K-exchanged resin was filtered, washed with 50 mL 
distilled water, and dried in a vacuum oven under a stream of N.sub.2 at 
approximately 110.degree. for 2 hours. The resulting dried K-exchanged 
resin weighed 2.75 g. 
The K-exchanged resin was stirred with an aqueous (100 mL) solution of 
Cu(NO.sub.3).sub.2.2H.sub.2 O (0.6 g, 2.68 mmol) at 60.degree.-70.degree. 
for 5 hours. The resulting resin was filtered, washed with 50 mL of water, 
and dried in a vacuum oven under a stream of N.sub.2 at about 110.degree. 
for 3 hours. The resulting dried resin catalyst (Cu,K-PFIEP[SO.sub.3 H]) 
weighed 2.5 g. Elemental analysis gave 2.18% Cu and 0.60% K. 
Synthesis of Ethyl Chrysanthemumate 
A flask was charged with CH.sub.2 Cl.sub.2 (25 mL), 
2,5-dimethyl-2,4-hexadiene (25 mL) and 0.45 g of the Cu,K-PFIEP[SO.sub.3 
H] catalyst, prepared as described above. A solution of ethyl diazoacetate 
(2.5 g) in CH.sub.2 Cl.sub.2 (25 mL) was added slowly dropwise and the 
resulting reaction mixture was stirred for 24 hours at ambient 
temperature. Gas chromatography analysis showed that the resulting product 
contained cis- and trans-ethyl chrysanthemumates in a 1:1.66 isomer ratio 
and a combined yield of 89.6%. 
Comparison Experiment A 
Synthesis of Ethyl Chrysanthemumate using Copper Bronze 
The reaction described in Example 1 was substantially repeated except that 
a copper bronze catalyst (90% Cu, 10% Sn), available commercially from 
B.D.H. Chemicals Ltd., Poole, England (Product #27814), was used in place 
of the Cu,K-PFIEP[SO.sub.3 H] catalyst. To induce the reaction, it was 
necessary to eliminate the CH.sub.2 Cl.sub.2 and heat the reaction mixture 
to 100.degree.. Only traces of ethyl chrysanthemumate could be detected by 
gas chromatography analysis. 
EXAMPLE 2 
Synthesis of Ethyl Chrysanthemumate Using Cu,K-PFIEP[SO.sub.3 H] 
Catalyst Preparation 
A slurry of powder PFIEP[SO.sub.3 H] in the potassium form (11.0 g, 1100 
equiv) was stirred with an aqueous (100 mL) exchange solution of 
Cu(NO.sub.3).2H.sub.2 O (2.4 g, 10.7 mmol) at about 70.degree. for 8.5 
hours. The resulting resin was filtered, washed with 100 mL of water and 
dried in a vacuum oven under a stream of N.sub.2 at 110.degree. for 4 h. 
The dried resin catalyst (Cu,K-PFIEP[SO.sub.3 H]) weighed 10.8 g. 
Elemental analysis gave 1.98% Cu, 0.8% K and 0.018% N. 
Synthesis of Ethyl Chrysanthemumate 
Ethyl diazoacetate (5.0 g) in methylene chloride (50 mL) was added dropwise 
to a slurry of the Cu,K-PFIEP[SO.sub.3 H] catalyst described above (2.0 g) 
in methylene chloride (100 mL) and 2,5-dimethyl-2,4-hexadiene (8.33 g). 
After stirring for about 18 h at ambient temperature, the reaction product 
was isolated by filtering off the catalyst, evaporating the solvent and 
chromatographing the resulting residue on silica with 10% ethyl acetate 
and 90% hexane as eluant. The isolated chrysanthemumate had an identical 
.sup.1 H nmr spectrum to a commercial sample. Anal. Calcd. for C.sub.12 
H.sub.20 O.sub.2 : C, 73.43; H, 10.27; Found: C, 74.08; H, 10.58. 
EXAMPLES 3 and 4 
Synthesis of Ethyl 2-Phenylcyclopropanecarboxylate Using 
Cu,K-PFIEP[SO.sub.3 H] 
Synthesis of Ethyl 2-Phenylcyclopropanecarboxylate 
In Example 3, a flask was charged with 0.5 g of the catalyst described in 
Example 1, CH.sub.2 Cl.sub.2 (2.5 mL) and styrene (2.5 mL). A solution of 
ethyl diazoacetate (0.23 g), styrene (10 mL), and CH.sub.2 Cl.sub.2 (10 
mL) was added slowly dropwise and the resulting mixture was stirred for 24 
hours. Gas chromatographic analysis of the reaction product showed that 
cis- and trans-ethyl-2-phenylcyclopropanecarboxylates had been produced in 
a combined yield of 91%. 
In Example 4, a flask was charged with 1.0 g of the catalyst described in 
Example 1, CH.sub.2 Cl.sub.2 (2.5 mL), and styrene (2.5 mL). A solution of 
ethyl diazoacetate (0.23 g), CH.sub.2 Cl.sub.2 (12.5 mL), and styrene 
(12.5 mL) was added slowly dropwise and the resulting mixture was stirred 
for 24 hours. The reaction product was analyzed by gas chromatography and 
the catalyst recovered by filtration. This process was repeated for a 
total of ten cycles during which yields of ethyl 
2-phenylcyclopropane-carboxylate remained essentially constant at about 
91%. The recovered catalyst was dried in vacuo. Duplicate elemental 
analyses gave copper contents of the recovered catalyst of 1.83 and 1.88%. 
Comparison Experiment B 
Synthesis of Ethyl 2-Phenylcyclopropanecarboxylate using Rh-PFIEP[SO.sub.3 
H] Catalysts 
Catalyst Preparation 
A sample of Rh.sup.+2 -exchanged PFIEP was prepared by refluxing a slurry 
of powder PFIEP[SO.sub.3 H] (100-400 mesh, 1.4 g, 1.27 mequiv) and 
Rh.sub.2 (OAc).sub.4 (0.14 g, 0.317 mmol) in CH.sub.2 Cl.sub.2 (30 mL) 
for 1.5 hours. The resulting slurry was cooled to ambient temperature and 
filtered. The resulting resin was washed with CH.sub.2 Cl.sub.2 (10 mL) 
and air dried to give 1.65 g of light green Rh-PFIEP[SO.sub.3 H]. 
Elemental analysis: 3.99% Rh. This represents 0.639 mmol Rh, suggesting 
that all of the sulfonic acid sites were exchanged. 
Synthesis of Ethyl 2-Phenylcyclopropanecarboxylate 
A solution of CH.sub.2 Cl.sub.2 (12.5 mL), styrene (12 5 mL) and ethyl 
diazoacetate (0.25 g, 2.19 mmol) was added slowly dropwise at ambient 
temperature to a stirred slurry of Rh-PFIEP[SO.sub.3 H] (1.0 g, 0.387 
mmol, prepared as described above), styrene (2.5 mL) and CH.sub.2 Cl.sub.2 
(2.5 mL). Gas evolution ceased about 1 hour after the addition of the 
ethyl diazoacetate solution was complete. The resulting slurry was stirred 
for 24 hours and then allowed to settle. The solution was removed, the 
resulting resin was washed with 3.0 mL of CH.sub.2 Cl.sub.2. The solution 
and the wash were combined and analyzed for cyclopropane products. Yield 
(based on ethyl diazoacetate): 73.9%. 
This procedure was substantially repeated using the washed resin for a 
total of nine cycles during which yields of ethyl 
2-phenylcyclopropanecarboxylate decreased to 32.5%. The color of the 
exchanged resin changed from green to orange during the third cycle. The 
color of the decanted solution changed from light green to light yellow on 
the fourth cycle. The color changes and decreases in yield are presumed to 
be due to metal leaching. 
Comparison Experiment C 
Synthesis of Ethyl 2-Phenylcyclopropanecarboxylate Using Cu-Amberlyst.RTM. 
Catalyst Preparation 
A commercial sample of a polystyrenesulfonic acid resin, commercially 
available from Rohm & Haas under the registered trademark Amberlyst.RTM. 
15 , (5.0 g, 23.5 mequiv) in the acid form was heated to approximately 
60.degree. for 2 hours with an exchanging solution of 
Cu(NO.sub.3).sub.2.3H.sub.2 O (9.9 mmol) dissolved in 100 mL distilled 
water. The resulting mixture was not stirred in order to prevent breakage 
of the beads. The exchanging solution was decanted and the procedure was 
repeated with another 9.9 mmol of Cu(NO.sub.3).sub.2.3H.sub.2 O in 100 mL 
distilled water. The resulting resin was filtered, washed with distilled 
water and dried in a vacuum oven under a stream of N.sub.2 at about 
110.degree. for 3 hours. The dried resin catalyst weighed 4.68 g. 
Elemental analysis of the Cu-Amberlys.RTM. catalyst gave 12.07% Cu. 
Synthesis of Ethyl 2-Phenylcyclopropanecarboxylate 
The reaction described in Example 3 was substantially repeated, except that 
0.5 g of the Cu-Amberlyst.RTM. catalyst described above was substituted 
for the Cu,K-PFIEP[SO.sub.3 H] catalyst. Gas chromatography analysis 
showed that the yield of ethyl 2-phenylcyclopropanecarboxylates was 60%. 
Comparison Experiment D 
Synthesis of Ethyl 2-Phenylcyclopropanecarboxylate Using Cu(II)-Triflate 
The reaction of Example 3 was substantially repeated except that a 0.05 g 
of a Cu(II)-triflate catalyst, commercially available from Alfa Products, 
(Cat.#17245), was employed as a homogeneous catalyst in place of the 
Cu,K-PFIEP[SO.sub.3 H] catalyst. The yield of ethyl 
2-phenylcyclopropanecarboxylate was 84%. The resulting solution was 
homogeneous, precluding catalyst recovery by filtration. 
EXAMPLE 5 
Synthesis of Ethyl 2-Phenylcyclopropanecarboxylate Using 
Cu,K-PFIEP[SO.sub.3 H]/PFIEP[CO.sub.2 H] 
Catalyst Preparation 
A Cu,K-PFIEP[SO.sub.3 H]/PFIEP[CO.sub.2 H] catalyst was prepared by 
stirring a slurry of powder PFIEP[SO.sub.3 H]/PFIEP[CO.sub.2 H] (35-60 
mesh, 15 g) in the acid form with aqueous KOH (21.4 mmol) at 80.degree. C. 
for 4 h. The resulting K-exchanged resin was filtered and washed with 
distilled water. This resin was stirred with Cu(NO.sub.3).sub.2.3H.sub.2 O 
(13.6 mmol) at 80.degree. for 4 hours, washed with distilled water and 
dried in a vacuum oven under a stream of nitrogen at approximately 
110.degree. for 2 hours. The dried Cu,K-exchanged resin catalyst weighed 
14 g. Elemental analysis: 1.33% K; 1.92% Cu; 8 ppm N. 
Synthesis of Ethyl 2-Phenylcyclopropanecarboxylate 
The reaction described in Example 3 was substantially repeated except that 
the Cu,K-PFIEP[SO.sub.3 H] catalyst was replaced by the 
Cu,K-PFIEP[SO.sub.3 H]/PFIEP[CO.sub.2 H] (0.58 g) catalyst described 
above. The reaction mixture was allowed to stir for 0.5 hour after the 
addition of the solution of ethyl diazoacetate, CH.sub.2 Cl.sub.2 and 
styrene. Analysis by gas chromatography showed that the combined yield of 
cis- and trans-ethyl-2-phenylcyclopropanecarboxylates was 95%. 
EXAMPLES 6-8 
Synthesis of Ethyl 7-Norcaranecarboxylate Using Cu,K-PFIEP[SO.sub.3 H] 
In Example 6, a flask was charged with cyclohexene (5 mL) and 1.0 g of the 
catalyst described in Example 1. A solution of ethyl diazoacetate (0.23 g) 
in cyclohexene (25 mL) was added slowly dropwise at 25.degree. and the 
resulting mixture was stirred for 2 hours at ambient temperature. The 
resulting reaction mixture was analyzed by gas chromatography and was 
shown to contain cis- and trans-ethyl-7-norcaranecarboxylate in a combined 
yield of 36%. 
In Example 7, the reaction described in Example 6 was substantially 
repeated except that half of the cyclohexene was replaced by CH.sub.2 
Cl.sub.2. A flask was charged with the catalyst described in Example 1, 
cyclohexene (2.5 mL) and CH.sub.2 Cl.sub.2 (2.5 mL). A solution of ethyl 
diazoacetate (0.23 g) in cyclohexene (12.5 mL) and CH.sub.2 Cl.sub.2 (12.5 
mL) was added slowly dropwise at 25.degree.. After stirring for 24 hours, 
the yield of ethyl 7-norcaranecarboxylate was 58%. 
In Example 8, the reaction described in Example 7 was substantially 
repeated except that the CH.sub.2 Cl.sub.2 was replaced with 
1,1,2-trichlorotrifluoroethane. After stirring for 24 hours, the yield of 
ethyl 7-norcaranecarboxylate was 36%. 
EXAMPLE 9 
Synthesis of Ethyl 
3-(2,2-Dichlorovinyl)-2,2-Dimethyl-1-Cyclopropanecarboxylate Using 
Cu,K-PFIEP[SO.sub.3 H] 
A flask was charged with the catalyst described in Example 1 (0.5 g) and 
1,1-dichloro-4-methyl-1,3-pentadiene (5 mL) and the resulting suspension 
heated to 75.degree.. A solution of ethyl diazoacetate (0.23 g) in the 
diene (20 mL) was added slowly dropwise while the temperature of the 
catalyst containing solution was maintained at 75.degree.. After stirring 
for 0.5 hour, the combined yield of cis- and 
trans-ethyl-3-(2,2-dichloro-vinyl)-2,2-dimethyl-1-cyclopropanecarboxylate 
was determined to be 17% by gas chromatography using a commercial sample 
as a calibration standard. 
EXAMPLE 10 
Synthesis of Ethyl 
3-(2,2-Dichlorovinyl)-2,2-Dimethyl-1-Cyclopropanecarboxylate Using 
Cu,K-PFIEP[SO.sub.3 H] 
Catalyst Preparation 
A slurry of powder PFIEP[SO.sub.3 H] in the potassium form (11.0 g, 1100 
equiv) was stirred with an aqueous (100 mL) solution of CuCl.sub.2. 
2H.sub.2 O (1.7 g, 9.94 mmol) at about 70.degree. C. for 6.75 hours. The 
resulting resin was filtered, washed with 100 mL of water and dried in a 
vacuum oven under a stream of N.sub.2 at 110.degree. for 4 hours. The 
dried resin catalyst weighed 10.6 g. Elemental analysis gave 1.75% Cu and 
1.26% K. 
Synthesis of 
Ethyl-3-(2,2-Dichlorovinyl)-2,2-Dimethyl-1-Cyclopropanecarboxylate 
The reaction described in Example 9 was substantially repeated except that 
the catalyst was prepared as described above using CuCl.sub.2.2H.sub.2 O 
as the Cu salt component. The yield of the cyclopropanated product was 
12%. 
EXAMPLE 11 
Synthesis of Ethyl 
3-(2,2-Dichlorovinyl)-2,2-Dimethyl-1-Cyclopropanecarboxylate Using 
Cu,K-PFIEP[SO.sub.3 H] 
Catalyst Preparation 
A slurry of powder PFIEP[SO.sub.3 H] in the potassium form (11.0 g, 1100 
equiv. wt.) was stirred with an aqueous (100 mL) solution of 
Cu(OAc).sub.2. H.sub.2 O (5.0 mmol) at about 70.degree. for 4.25 hours. 
The resulting resin was filtered, washed with 100 mL of water and dried in 
a vacuum oven under a stream of N.sub.2 at 110.degree. C. for 4 h. The 
dried resin catalyst weighed 10.6 g. Elemental analysis gave 1.52% Cu and 
1.72% K. 
Synthesis of 
Ethyl-3-(2,2-Dichlorovinyl)-2,2-Dimethyl-1-Cyclopropanecarboxylate 
The reaction described in Example 9 was substantially repeated except that 
the catalyst was prepared as described above using copper(II)acetate as 
the Cu salt component. The yield of cyclopropanated product was 13%.