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United States Patent O?iice l 3,146,314 1-ARYL-2,2ETHALOCYCLOPRGPANEEi Ellis K. Fields and .loseph M. Sandri, Chicago, ilh, as signors to Standard Oil Company, Chicago, iii, a cor poration of Indiana No Drawing. Filed 0st. 30, 1959, Ser. No. 849,751 5 Claims. (Cl. 260-650) 3,045,314 Patented July 24, 1962 2 The novel compounds of this invention having the for mula hereinbeiore set forth include compounds whose Ar-groups are not appreciably more acidic than are the aryl hydrocarbon groups such as phenyl, tolyl, ethyl phenyl, cumyl, the monobutylphenyls, xylyl, diethyl phenyl, diisopropylphenyl, cymyl, naphthyl, methyl naphthyls, ethylnaphthyls, biphenyl, .alkylated biphenyls, vinylphenyl, a-methylvinylphenyl, and the like. The Ar This invention relates to a novel class of substituted group may contain a single aromatic ring as in the phenyl, aromatic compounds, the 1-a~ryl-2,2-dihalocyclopropanes and l-aryl-1-methyl-2,Z-dihalocyclopropanes and especial ly pertains to l-aryl and l-aryl-1-methyl-2,2~dichloro-V 10 alkylated phenyls, phenylene, etc. groups, two or more and 2,2-dibromo-cyclopropanes and a process for prepar ing them. independent six-membered rings such as in biphenyl, ter phenyls, quaterphenyls and alkylated derivatives thereof, or two or more fused aromatic rings as in naphthyl, anthracene, phenanthrene, chrysene, pentacene, and the The novel class of substituted aromatics to which this invention relates has the following general formula: like. Those containing only one aromatic ring are, of course, derivatives of styrene, oc-methylstyrene, divinyl benzene and di-(a-methylvinyl) benzene and their nuclear alkylated derivatives. Those containing two or more aromatic rings, independent or fused, ‘are the vinyl and a-vinyl derivatives of the corresponding aromatic hydro carbons and their nuclear alkylated derivatives. The lat~ ter, the vinyl and u-methylvinyl derivatives of the poly ring aromatics, can be prepared according to the process wherein Ar is a mono or divalent aryl radical, R is hy drogen or methyl, X is chlorine or bromine and n is 1 or 2. These compounds are derived from the reaction of a vinyl or alpha-methyl vinyl substituted aromatic com— pound with a dichlorocarbene or dibromocarbene formed in situ by the alkaline hydrolysis of chloroform or bromo form. These dihalo carbenes are su?iciently stable and/ or p-vinyl acetophenone, p-vinyl benzophenone, alkoxy —(|)=CH2 J.A.C.S., 80, S275 (1958). By opening the ring of the of US. Patent 2,404,235 or according to the process de scribed in the articles in J.A.C.S., 68, 1105—11l2. In ad dition to the ar-nuclear substituted alkyl hydrocarbon groups, there may also be present keto groups as in form suf?ciently readily to react with the vinyl group: iii) groups as in methoxy styrenes, and the like. The compounds of this invention are exceptionally use ful because of the presence of the 2,2-dichloro- or 2,2-di —-G=CH2 brornocyclopropyl groups. These groups may be reacted as the same groups attached to an aliphatic chain. The or a-methyl vinyl group: preparation of such compounds from ole?ns and dichloro CH3 carbene is described in J.A.C.S., 76, 6162 (1954), and to form the 2,2-dichloro- or 2,2-dibromo-cyclopropyl or 2,2-dichloro- or dibromocyclopropyl group with a strong l-methylcyclopropyl group. The reaction is accomplished by combining the aromatic vinyl or u-methylvinyl com acid such as H2804, hydrobromic, glacial acetic, and the resulting mixture is heated to its boiling point and there maintainedwith external heating until the reaction begins. There is a short initiation period of about 10 to 30 min utes during which the addition of heat to maintain re?ux conditions is necessary. After the reaction begins, as may be noted by the formation of sodium or potassium without destroying the cyclopropane groups. like, in a manner known to the art, there is ‘formed a pound with an alkali metal alkoxide of a lower aliphatic 40 three-carbon aliphatic group which may be unsaturated or which may contain the elements of the acid used to alcohol; i.e., sodium or potassium methoxide, ethoxide, open the ring. Also, the ar-alkyl 1-aryl-2,2-dichloro- or t-butoxide, and the like, and an inert reaction solvent dibromo-cyclopropanes can be oxidized to the correspond such as a paraf?nic hydrocarbon. A small quantity of ing aromatic mono, di and higher polycarboxylic acids chloroform or bromoform is added to this mixture. The chloride or bromide, the external source of heating can be stopped since the reaction is exothermic and the re mainder of the chloroform or brornoform added, pref~ erably slowly, to maintain a gentle re?ux. To insure good contact between the reactants, the reaction mixture may be stirred. The resulting reaction mixture is permitted to reach ambient or room temperature. Water may be added to dissolve the sodium or potassium chloride or bromide by-product and to permit a separation of the l-aryl dihalocyclopropane formed which is dissolved in the reaction solvent. The resulting mixture is separated into an organic phase and an aqueous phase as, for ex ample, by settling and decantation. The two liquid phases are separated. The aqueous phase may be extracted with solvent such as the paraf?nic hydrocarbon employed as the reaction solvent. The extracts and the organic phase are combined, dried, if desired, and the l-aryl dihalo cyclopropane is recovered, for example, by distillation These unique acids and their preparation are more ‘fully de scribed in our copending application Serial No. 849,752, ?led October 30, 1959, and now abandon-ed. In order to facilitate a clear understanding of the in vention, the process ‘for preparing the novel substituted aromatic compounds is illustrated by the following de tailed description. Example 1 l-(p-tolyl)-2,2-dichlorocyclopropane is prepared in the following manner. A three liter, 3-neck ?ask equipped with a stirrer, condenser and dropping funnel is charged with 3 moles (162 grams) sodium methoxide, 500 milli liters pentane as the reaction solvent, and 2.77 moles (354 grams) p-methylstyrene. Three moles (360 grams) of chloroform are added to the dropping funnel and 30 mil liliters of chloroform are added to the ?ask. The mixture in the ?ask is heated to its boiling point and maintained under re?ux conditions until the reaction is initiated. The heat source s removed and chloroform is added dropwise at a rate to maintain a gentle re?ux, about three hours. After the addition of chloroform is complete, the resulting mixture is stirred at room temperature overnight. To the resulting mixture there are added 800 milliliters of water. or by evaporation of the solvent associated therewith. The l-aryl dihalocyclopropane can be further purified by 70 The mixture is permitted to separate into two phases. The fractionation when feasible or by extraction or recrystal lization when applicable. Water phase is extracted with pentane. The pentane ex tracts and the organic layer are combined and dried over 3,046,314. 223 4 anhydrous magnesium sulfate. The dried material is dis and found to be in close agreement with the correspond tilled to recover p-methyl-1-(2,2-dichlorocyclopropyl) benzene with boiling point 122° C. at 12 mm. Hg and re cates : ing calculated values for Cwl-lmClz as the following indi- v fractive index nDZ" 1.5460. By analysis of this compound the carbon, hydrogen and chlorine content was deter— mined and found to be in close agreement with the corre_ COMPOSITION sponding values calculated for CmI-I10Cl2 as the following .13 y analy- Calculated, indicates: sis, percent 10 COMPOSITION Carbon _____ __ 58. 7 Hydregen__ __ 5. 26 Chlorine. _ _ __ 35.3 percent 59. 7 4. 98 35. 3 By an aly- Calculated, sis, percent Carbon ______________________________________ __ Hydrogen __ 60. 3 5. 28 Chlorine ____________________________________ __ 35. 2 percent Example 5 By repeating the process of Example 1 employing 480 grams of p-isopropyl-a-methylstyrene in place of 354 grams p-methylstyrene, there was obtained l-methyl-l-p 59. 7 4. 98 35. 3 cumyl-2,2-dichlorocyclopropane with boiling point 133° Example 2 20 C. at 9 mm. Hg and refractive index nD2° 1.5291. By By repeating the process of Example 1 employing 284 analysis of this compound the carbon, hydrogen and chlo grams styrene in place of 354 grams p-methylstyrene, there was obtained by the distillation of the dried pentane rine content was determined and found to be in close agreement With the corresponding calculated values for C13H16Cl2 as the following indicates: solution 1-phenyl-2,2-dichlorocyclopropane with boiling point 103° C. at 10 mm. Hg and refractive index nDZ" 25 1.5508. By analysis of this compound the chlorine con C 0MP OSI’I‘ION tent was determined and found to be in close agreement with the corresponding values calculated for C9H8Cl2 as the following indicates: By analy- Calculated, sis, percent percent 30 Carbon COMPOSITION _ ___ Hydrogen ___________________________________ __ Chlorine ____________________________________ ._ 63. 6 63. 9 7. 12 29. 1 6. 97 29. 1 By analy- Calculated, sis, percent percent Example 6 35 Chlorine ____________________________________ __ 37. 9 38. 0 By repeating the process of Example 1 employing 480 grams m-isopropyl-a-methylstyrene instead of 354 grams p-methylstyrene, there was obtained l-methyl-l-m-cumyl Example 3 The process of Example 1 is repeated except that354 40 2,2-dichlorocyclopropane with boiling point 135° C. at 11 mm. Hg and refractive index 111320 1.5249. grams (2.77 moles) mixed meta and para vinyl toluenes, 60% meta and 40% para, are employed in place of p Example 7 methylstyrene. The dried combined pentane extracts and The compound p-bis (2,2-dichlorocyclopropyl) benzene organic layer are distilled to remove the pentane. The residue is distilled at 10 mm. Hg. There are collected 45 having the formula: 86.6 grams of a fraction boiling in the range of 114-1 17° C. This material is fractionated through an Oldershaw column and a center cut boiling at 115°~116° C. at 10 mm. Hg is taken. This center cut has a refractive index Cl nD2° 1.5458. By analysis of this center cut the carbon, hy drogen and chlorine content was determined and found to may be prepared by stirring and heating a mixture of 130 be in close agreement with the corresponding calculated grams (1.0 mole) divinyl benzene, 230 grams (2.05 values for CmHmclz as the following indicates: moles) potassium tert. butoxide, 50 grams chloroform and 800 grams heptane to its boiling point and maintained 55 under re?ux conditions until the reaction is initiated. COMPOSITION Thereafter, external heating is stopped and 265 grams (2.1 moles) of chloroform are slowly added to maintain a By analy- Calculated, sis, percent percent Carbon Hydrogen 60. 1 5. 29 59. 7 4. 98 Chlorine ____________________________________ __ 35. 3 35. 3 gentle re?ux. After completion of the chloroform addi tion, the reaction mixture is stirred until its temperature 60 cools to 25° C. Water is added to the mixture to dis solve the solids formed. The aqueous layer and organic layer are separated. The aqueous layer is extracted with heptane. The extracts and organic layer are combined, By oxidation of the center cut it is found that the prod 65 dried and distilled to remove heptane. The residue may be puri?ed by fractionation. uct of this process contains l-(m-tolyl)-2,2-dichlorocyclo propane (60%) and l-(p-tolyl)-2,2-dicl1lorocyclopropane Example 8 (40% ). By the procedure of Example 1 or 7, there may be pre Example 4 pared 4-(2,2-dichlorocyclopropyl) biphenyl: By repeating the process of Example 1 employing 354 70 grams of a-methylstyrene in place of p-methylstyrene, there was obtained l-methyl-1-phenyl-2,Z-dichlorocyclo propane with boiling point 92° C. at 6 mm. Hg and refrac tive index nD2° 1.5400. By analysis of this compound the carbon, hydrogen and chlorine content was determined 75 3,046,314 Reactan'ts Ex. Product structural formula and name No. 18_____ Dihalo- Vinyl Aromatic Carbene Precursor l-vinylnaphthalene _____________ __ CHBra ‘ It —C——CH¢ \ / (VI-Br I Br 1-(2,2-dibromocyclopropyl)naphthalene We claim: 15 3. A 1-tolyl_2,2-dichlorocyclopropane having the for mula: 1. An aromatic dihalocyclopropane having the formula: R I’! Ar—-C——C / H L \ G / \H X/ \X 11 wherein Ar is an aromatic hydrocarbon radical Whose valence corresponds to the value of 11 selected from the 4. A l-xy1yl-2,Z-dichlorocyclopropane having the for class consisting of alkyl substituted phenyl radicals, the 25 mula: (CH3): H H divalent phenylene radical, aromatic hydrocarbon radi _<';__'O_H \CZCI cals containing more than one independent joined 6 membered aromatic ring, aromatic hydrocarbons contain ing fused rings, and alkyl hydrocarbon derivatives of these multi-ring aromatics, R is a member selected from the class consisting of hydrogen and an alkyl hydrocar 30 5. p-Di-(2,2-dichlorocyclopropyl) benzene having the bon radical, X is a halogen selected from the class con sisting of chlorine and bromine and n is an integer from formula: 1 to 2. 2. l-(p-Biphenyl)-2,2-dich1orocyclopropane having the formula: ‘ ('11 H 35 H H H_é__é_Oé__é_H \C—/-C1 \CZCI Cl 40 H J31 References Cited in the ?le of this patent Skell et aL: J. Am. Chem. Soc. 78, 5430-3, 1956.