Patented Nov. 26, 1946 2,411,516 s PATENT OFFICE UNITED STATE 2,411,516 ETHERS OF ENDOETHYLENE-SUBSTITUTED CYCLOPENTANOLS Herman A Bruson, Philadelphia, Pa., assignor to The Resinous Products & Chemical Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application May 24, 1944, Serial No. 537,183 8 Claims. (C. 260-61) 2 This invention relates to addition-rearrange acetate, allyl oleate, vinyl methyl ketone, vinyl ment products from organic compounds having acetate, vinyl benzoate, and the like. There may alcoholic hydroxyl groups and adducts of cyclo also be used other adducts of cyclopentadiene pentadiene with mono-olefinic compounds hav with olefinic compounds, such as courmarOne, ing at least three carbon atoms, said products safrole, eugenol, and with allyl ethers, Such as being ethers of an endoethylene-substituted cy benzyl allyl ether, phenyl allyl ether, Octyl allyl clopentanol. ether,In practicing and the like. this invention, it has been found In my copending application, Serial No. 476,- that a wide variety of organic compounds con 640, filed February 20, 1943, it is shown that non taining one or more alcoholic hydroxyl groups resinous polycyclopentadienes having two double 0 may be employed. The hydroxyl group is pref bonds per molecule, such as dicyclopentadiene, erably primary or secondary. Compounds con tricyclopentadiene, and tetracyclopentadiene add taining a tertiary hydroxyl group may also be alcohols in the presence of acidic condensing used, provided, however, that they are not readily agents to form addition-rearrangement products dehydrated. . f which are ethers of a new ring System termed 5 The useful alcoholic hydroxyl-containing com the 'nordicyclopentadiene' ring system. pounds may be aliphatic, arylaliphatic, cycloali In accordance with the present invention, phatic, hydroaromatic, or heterocyclic and may which is a continuation-in-part of copending ap be saturated or unsaturated, straight- or plication Serial No. 529,195, filed April 1, 1944, branched-chained, or cyclic. It has also been adducts of cyclopentadiene with mono-olefinic 20 established that the non-hydroxyl portion of the compounds having at least three carbon atoms in reacting hydroxyl-containing compound may the molecule are reacted with alcohols in the contain a wide variety of groups or substituents, presence of acidic condensing agents to form ad for example, halogen, cyano, thiocyano, nitro, dition products which are rearranged ethers keto or acyl, mercapto, ether, acyloxy, alkoxy, from endo-ethylene-substituted cyclopentanols. 25 aryloxy, carbalkoxy, or carboxy groups, etc. A typical illustration is that, for example, in It should be noted at this point that, in the volving the action of an alcohol, ROH, upon the case of alcoholic hydroxyl-containing compounds cyclopentadiene-styrene adduct, having free carboxyl groups, excess cyclopenta 30 diene-olefine adduct is necessary since esterifica cf CB off? R CH, tion of the carboxyl group by addition and simul ROH . taneous rearrangement occurs in addition to CE seamed CH etherification with the alcoholic hydroxyl group. C CE-CBIs R-O-CH----C-CI From the above discussion, it will be evident N f that under the influence of acidic condensing C CE 35 agents cyclopentadiene-olefine adducts of the The product formed by the molecular addition rearrangement is very probably that represented type set forth form rearranged ethers with a wide by formula (A). In any event, the product is not variety of alcoholic hydroxyl-containing com a simple addition of (R-O-) to one side of the pounds and that the reaction is one of wide ap double bond and of H to the other. The reaction 440 plicability. Hydroxyl-containing reactants of involves both addition and rearrangement and perhaps greatest interest belong to the general leads to a new class of substituted cyclic Com class of unsubstituted alcohols, whether mono pounds which are not available by any previously hydric or polyhydric, which are not dehydrated proposed method of synthesis. at 60° C. by sulfuric acid. There are, however, Warious adducts of cyclopentadiene with mono 45 importantple alcohols. types Other of reactants important other groups than includehy the sim olefinic compounds having three or more carbon droxy-acid esters, hydroxy-acids, hydroxy-ke atoms in the molecule may be used for the pur tones, hvdroxy-lactones, hydroxy-aldehydes, pose of this invention. These comprise not only the so-called "Diels-Alder' type of adducts of ether alcohols, cyano alcohols, thiocyano alco cyclopentadiene with unsaturated hydrocarbons 50 hols, halohydrins, nitro alcohols, and polymeric as, for example, propylene, cyclopentene, styrene, hydroxyl-containing compounds, including poly indene, allylbenzene, and the like, but also the vinyl alcohol, polysaccharides, starches, sugars, adducts of cyclopentadiene with unsaturated al cellulose, cellulose ethers, cellulose esters, and the cohols, esters, halides, or ketones, as, for example, like. . . . . allyl alcohol, allyl chloride, allyl benzoate, allyl 55 Typical wseful hydroxyl-containing com

2,411,516 - 3 . 4 pounds for the purpose of this invention are the toluene sulfonic acid, or aliphatic sulfonic acids, following: methanol, ethanol, propanol, iso as butylsulfonic acid and the like. propanol, n-butanol, isobutanol, butanol-2, the Sulfuric acid is of particular value in promot primary and various isomeric amyl alcohols, n ing reactions involving the lower primary hexanol, 2-ethylbutanol, n-heptanol, n-Octanol, aliphatic alcohols. It is generally of use in the capryl alcohol, 2-ethyl hexanol, decanol, 5 case of other alcohols also, which are not readily ethyl-nonanol-2, dodecyl alcohol, tetradecanol, 7 polymerized) or dehydrated by the presence of ethyl-2-methyl-undecanol-4, cetyl alcohol, 39 concentrated sulfuric acid. diethyl-tridecanol-6, oley alcohol, n-octadecanol, The boron trifluoride group of catalysts is one allyl alcohol, crotonyl alcohol, cinnamyl alcohol, 0. of considerable value. Of these, the complexes geraniol, phenylethyl alcohol, methoxyethanol, with ethers are of particular utility since they ethoxyethanol, butoxyethanol, phenoxyethanol, are soluble in the reaction mixtures and pro ethylene glycol, propylene glycol, butylene gly duce no troublesome by-products. Typical of col-1,3, diethylene glycol, triethylene glycol, these complexes are BF.C2H-O-Cahs and polyethylene glycols, di-isopropylene glycol, di 5 BF.C4H-O-C4Ho, with diethyl ether and di ethylene glycol monoethyl ether, diethylene n-butyl ether, respectively. glycol monobutylether, diethylene glycol mono The quantity of active catalyst employed may phenylether, glycerol, glycerol monochlorohy be varied over a wide range. Good results have drin, glycerol dichlorohydrin, glyceryl-a-phenyl been obtained with as little as two per cent of ether, 2-ethyl -hexandiol - 1,3, glyceryl - ox,y- 20 catalyst, based on the Weight of the cyclopenta dimethyl ether, trimethylene glycol, tetramethyl diene adduct, up to and exceeding a molar equiv ene glycol, decamethylene glycol-1,10, pentaery alent of the catalyst permol of adduct used. The thritol, ethylene? chlorohydrin, propylene chloro catalysts need not be used under anhydrous con hydrin, ethylene bromohydrin, propargyl alcohol, ditions. In fact, the presence of water in small ethylene cyanohydrin, p - thiocyanophenoxy 25 amounts often increases the rate of reaction. ethanol, 2-nitro-2-methyl-1-propanol, 3 - thio The addition-rearrangement reaction involv cyanoethoxyethanol, p - tertiary-butylphenoxy ing an alcoholic hydroxyl-containing compound ethanol, o - cyclohexylphenoxyethanol, 2,4-di and the adduct of cyclopentadiene and a mono-, chlorophenoxyethanol, p - ter - octylphenoxy olefinic compound is readily carried out in the ethanol, plphenylphenoxyethanol, 3-naphthoxy 30 presence of one or more acidic condensing agents. ethanol, 2 - nitrophenoxyethanol, p - acetyl The reaction may be initiated by mixing the phenoxyethanol, p-benzoylphenoxyethanol, cyclo components and catalyst at room temperature, hexanol, o-, m-, or p-methylcyclohexanol, cyclo at temperatures even around 0° C. in some cases, pentanol, o- or p-cyclohexyl-cyclohexanol, p-tert or at elevated temperatures. While it is genera amylcyclohexanol, hydroxydihydronordicyclo ally desirable to control the temperature at the rentadiene, borneo, fenchol, cholesterol, ethyl start, the reaction may be carried to completion glycolate, ethyl lactate, dimethyl tartrate, ethyl either by continuing the reaction for a long time citrate, benzyl alcohol, 2-nitro-2-methyl-1,3- or by raising the temperature to accelerate the propanediol, ethyl-10-hydroxy-stearate, tetrahy reactions involved. Temperatures as high as 100° drofurfuryl alcohol, phenyl thioethanol, ceryl 40 C. to about 200° C. may thus be used. The re alcohol, 2-nitro-2-ethyl-1,3-propanediol, castor action range of about 50 to 125° C. is, however, oil, hydrogenated castor oil, ethyl ricinoleate, generally the most useful and is to be preferred. ethyl maleate, sorbitol, dibutyl tartrate, glyceryl In Some cases the reactions are sufficiently or, y-diphenyl ether, mannitol, ethylene glycol exothermic that it is desirable to cool the react monobenzylether, and many others. The hy ing mixture in order to control the reaction. droxyl-containing compound need not be pure. This may also be controlled by the rate of mix There may be used, for instance, technical al ing the reactants and by the use of a solvent or cohol mixtures such as are obtained as by-prod diluent such as ethylene dichloride or dioxane. lucts from the Synthetic production of methanol After the reaction has been carried to a de-' by the reaction of hydrogen and carbon monoxide 50 sired point, the acidic condensing agent is re and known as "higher alcohols from the moved, as by washing with water or by neutral methanol synthesis.' These comprise branched ization. The reaction product may then be dis chained primary and secondary... alcohols having tilled in many cases, or otherwise purifled, as by from about 7 to about 18 carbon atoms and in treatment with decolorizing clay or carbon, strip some cases even more. Mixtures of higher ali ping, extraction, etc. - phatic alcohols obtained by the catalytic hy The following examples illustrate this inven drogenolysis of fatty glycerides or of higher fatty tion, it being understood that the proportions, acid esters may likewise be used. temperatures and time can be varied to a con Among the acidic condensing agents or cat siderable extent without departing from the alysts which serve to promote the addition-rear 60 spirit of the invention. - rangement of alcoholic hydroxyl-containing For the purpose of this invention it is desir compounds with cyclopentadiene mono-olefines able, although not necessary, to employ not more of the type set forth are boron trifluoride and than one mol equivalent of the alcohol per Eno its coordination complexes with oxygenated of the adduct. compounds, such as ethers, as, for example, Eacample 1 BF.C3HOC3Ha; carboxylic acids, as ethyleneA mixture chlorohydrin of 4 g. of and B.F.O(CHo) 134 g. of athe .08 cyclog. of 33.2CH3COOH pentadiene-allyl phenyl ether adduct carboxylic esters, as BF3.CH3COOCas; ketones, 70 such as BF3.CH3COCH3; alcohols, such as BF3.2C4HigOH; and water, such as BF3. CH2O) where ac is one or two. There may also be used as a catalyst Sulfuric acid, its esters, such as ethyl acid sulfate, aromatic sulfonic acids, such as 5

2,411,516 6 was stirred at 95° C. for5 six hours. The product at 95-97° C. for seven hours. The product was was washed with dilute sodium hydroxide solu washed with sodium hydroxide solution and with tion, then with water, dried, and distilled in water, then dried, and distilled in vacuo. The vacuo to yield 138 g. of the B-chloroethoxy endo 6-hydroxyethyl ether of phenyl endoethylene ethylene phenoxymethyl cyclopentarie as a color 5 cyclopentanol having the probable formula less oil boiling at 166-169°C/1 mm, having the C probable formula R . f".BH f OE O O-CECE-O- " 2 distilled over at 160-163° C./2 mm. as a color less oil a yield of ig. Upon redistillation. co-le-CCH The cyclopentadiene-allyl phenyl ether adduct 15 the pure compound boiled at 153°-163° C/1 mm. used is a colorless oil boiling at 134 C./6 mm. Ecample 5 obtainable by heating cyclopentadiene Or dicy A mixture of 11.6 g. of allyl alcohol, 1 g, of clopentadiene with allyl phenyl ether at BF.O(CH5)2, and 17 g. of 2,5-endomethylene 170°-180° C. as described in Copending applica 1,2,5,6-tetrahydro-diphenyl was heated at 90° C. tion Serial No. 529,196, fled April 1, 1944. 20 for four hours. The product was worked up as Ecample 2 in Example 3. The allyloxy phenyl endothylene A mixture of 9.6 g. Of methanol, 2 g, of 95% cyclopentane having the probable formula sulfuric acid, and 17 g. of the cyclopentadiene styrene adduct 25 C - CH C B d. gf ". cro-likD 30 distilled over at 155-170° C./10 mm. as a color less oil. Upon redistillation the pure compound known as 2,5-endomethylene-1,2,5,6-tetrahydro boiled at 164-168° C./10 mm. diphenyl was boiled under reflux for seven hours Eacample 6 at 72-81° C. The product was washed with 35 A mixture of 3 g. of BF3.O (C4H9)2, 64 g. of dilute sodium hydroxide solution, then with ethylene ochlorohydrin and 90 g. of cyclopenta- . Water, dried, and distilled in vacuo. diene-allylbenzoate adduct was stirred at 97° C. The rearranged methyl ether of phenyl endo for eight hours. The product was washed with ethylene cyclopentanol having the probable dilute soda solution, then with water, dried, and formula 40 distilled in vacuo to yield 96 g. of the B-chloro CH ethoxy derivative as a viscous oil boiling at f 195-200° C./1-2 mm. having the probable f". . . formula ur CH-O- E-2 -C CB CH C " distilled over at 135-148° C./10 mm. as a color less oil. Upon redistillation the pure compound CICECB-O-roll H-e -OH,-o-cog> boiled at 140-145 C/10 mm. bí? Eacample 3 Eacample 7 A mixture of 16 g. of ethylene chlorohydrin, A mixture of 11.9 g, of 2-nitro-2-methyl-1- 1 g. of BF3.O(C4H9)2, and 17 g. of 2,5-endo propanol, 0.5 g. of BF3.O(Cas)a, and 17 g. of methylene - 1,2,5,6 - tetrahydrodipheny Was 2,5-endomethylene - 1,2,5,6- tetrahydrodiphenyl stirred at 95-97° C. for four hours. The prod was stirred at 90° C. for three hours. The prod duct was washed with sodium carbonate solu tion and water, dried, and distilled in vacuo. uct was washed with water, dried, and distilled The 3-chloroethyl ether of phenyl endo in vacuo. ethylene cyclopentanol having the probable The nitro-isobutyloxy-phenyl endoethylene 60 Cyclopentane having the probable formula formula CB C f NCH, of". CH \ ClCHCH-0- H-e g X 65 CE--OH-0--like "it bf boiled at 180°-183° C./11 mm. It was a pale distilled over at 160-170° C./1 mm. as a color yellow oil. . . less oil. Upon redistillation the pure compound Eacample 8 boiled at 148-152 C./0.5-1 mm. 70 A mixture of 17 g. of 2,5-endomethylene Eacample 4 s 1,2,5,6-tetrahydrodiphenyl, 14.7 g. of B-thiocy A mixture of 31 g, of ethylene glycol (0.5 mol), anoethoxyethanol, and 3 g. of BF3.O(CH3)2 was . 2 g. of BFs.O (C4H9)2, and 31 g. of 2,5-endo stirred at 95 C. for seven hours. The product methylene-1,2,5,6-tetrahydrodiphenyl was stirred 75 was washed with dilute soda solution and water,

'' s41,52G then distied in Waco. The thiocyanoethoxy . 8 ethoxy-phenyi endoethylene cyclopentane hav and 2 g of BO(Ce) was stirred at 95 C. ing the probable formalia, for six hours. The product was Washed with was 5. tilledter and in withvacuo. dilute soda solution and then dis the ether ester having the probabie formula fi, (8.

re-el-el-liki> ogI. disties (oves at 326-335 (C/2 ram, as a viscos CE-CB-0- * pale ye low oi2. Ogof redistiation the are booca, g egEaggad Boied at 222-23 C/.3 Ran. distilled over at 60°-270 (C/1.5-2 mya. as a co gagingle 9 Oess oil. A Exture of 3 S. of 3F.O(CHs)2, 100 g. of 3 35328382 32 eaylene efioronycia and 180 g. of the cyclo A Enixture of 6 g. of E.O.(CEs) 2, 130 g. of gagakadegheap-establyphenyi ally ether ad ethylene chlorohydria, and 168 g. of the cycica diage, gentadene-alyoxyetano. 3dduct ar of" Nos* -KD-allN-1 N61 I l C -Ciao-CSCO was stirred at 95° C. of six hours. The product was stirred at 95 C. for eight hours. The prod was washed with dilute sodium hydroxide solu uct was washed with dilute sodium hydroxide so tion, then with water, dried, and distilled in lution, then with water, dried, and distilled in vacuo to yield 160 g. of the B-chloroethoxy de vacuo to yield 89 g, of the B-chloroethoxy deriv rivative as a colorless ol boiling at 185-195 80 ative as a colorless oil boiling at 162-165 C/0.5-1 mm. having the probable formula C/0.5-1 mm. having the probable formula C CB C ap.H. of ". on- X-0-0E-cN. B-O-CECEO C1CC-0-!". " -CH-O-OHCHOE, The cyclopentadiene-p-tertiary butylphenyl allyl ether adduct used above is a low melting. acample 13 solid boiling at 140 C/1 mm. obtained by heat A mixture of 24.9 g, of 8-chloroethoxyethanol, ing cyclopentadiene or dicyclopentadiene with p 17 g. of 2,5-endomethylene-1,2,5,6-tetrahydro diphenyl, and 1 g. of B.F.O(CHs)a was stirred at tertiary butylphenyl allyl ether at 170-175° C. 95 C. for four hours and worked up by washing Example 10 . 45 with soda solution and with water, followed by To a mixture of 80.5 g. of ethylene chlorohy vacuum distillation. . . The product having the probable formula drinproponitrile and 88.5 adduct g. of cyclopentadiene-p-allyloxy O ofC So, . f".2Es I !---a on-al- {X 55 there was added 4 g. of BF.O(C.E.), and the distilledless viscous over ol. at 180°-185 - C/1.5 mm. as a color mixture stirred at 95-97° C. for seven hours. carpe 14 The product was washed with dilute sodium hy A mixture of 22 g. of glyceryl-a-monochloro distilleddroxide insolution, vacuo. then with water, dried, and hydrin, 17 g. of 2,5-endomethylene-1,2,5,6-tetra The p-chloroethoxy derivative obtained boiled 60 hydro-diphenyl, and 1 g of B.O.(CBs) a was at 164-189 C/1 mm. It was a colorless thick stirred at 90°-95 C. for four and one-half hours, oil, having the probable formula then cooled, washed with dilute sodium hydrox ide solution and water, and distilled in vacuo. C the product having the probable formula c6. 65 B OCC-O-CE -CH-O-CECHON The yield amounted to 74 grams. 70 Sacamaple a boiled at 190-195 C/2 mm. It is a thick oil. A mixture of 24 g. of ethyl lactate, 17 g. of - cample 15 2,5uendomethylene-1,2,5,6-tetrahydro - dipheny 76 A mixture of 35.4 g. of n-butoxyethanol ("bu 2,411,516 ty Celilosolve'), 17 g. of 2,5-endomethylene- a colorless oil boiling at 130°-135° C./1 mm. ob 1,2,5,6-tetrahydro-diphenyl, and 3 g of tained by heating cyclopentadiene or dicyclopen BF.O(CHo)2 tadiene with safrole at 170°-180° C. * was stirred at 95°-97° C. for seven hours. The is Eacample 18 product was washed with dilute Sodium hydrox- A mixture of 6 g. of BF.O (C4Hg), 160 g. of ide solution, then with water, and distilled in ethylene chlorohydrin, and 148 g. of cyclopen vacuo. The n-butoxyethoxy endoethylene phenyl tadiene-vinyl acetate adduct cyclopentane having the probable formula C O of".

2 . 5 was stirred at 95° C. for five and one-half hours. class-lik) The product wasN le cooled, " ... washed. with dilute soda distilled at 175°-180° C./1.5 mm. as a colorless Solution, then with water, dried, and distilled in oil in a yield of 20 grams. vacuo to yield 85 g. of the rearranged ether as a Eacample 16 20 colorless oil boiling at 108°-115° C./1 mm, having A mixture of 10.6 g. of diethylene glycol, 34 g. the probable formula: of 2,5-endomethylene-1,2,5,6-tetrahydro-diphen- R yl, and 3 g. of BF3.O(C4H9)2 was stirred for seven off? C hours at 85°-90° C. and worked up as in Exam pleTwo 15. products were obtained. One product was 25 cichlich-0-bh-e -8-9s-ch,it? . . . . a colorless oil boiling at 200-210° C. at 12 mm. CE having the probable formula Eacample 19 CH A mixture of 5 g, of BF.O(CH), 36 g. of N 30 ethylene cyanohydrin, and 55 g. of cyclopenta f H, diene-indene adductCB CE HO-CHCH-O-CHCHO- "it2 {Ox ?t- Sch 35 The other product was a thick oil boiling at 285 290° C./1.5 mm. having the probable formula - Ng Yo?, Yo? cí?. CH . . gf R C - KDX S--CH-O-CH," CH-O-CHCH-O-a " "l{ X This examplesh. illustrates the fact that in the 45? was stirred at 95° C. for four hours. The product case of polyhydric alcohols one or more of the was washed with water, dried, and distilled in alcoholic hydroxyl groups may be reacted to vacuo to yield 50 g. of the rearranged cyanoethyl give one or more ether linkages to an endoethyl- ether as a colorless oil boiling at 1749-176° C./2 ene cyclopentane ring System, mm. having the probable formula Eacample 17 50 1 CHN. /C N . A mixture of 5 g. Of BF3.O (C4H9)2, 101 g, of f C-C C ethylenepentadiene-safrole chlorohydrin, adduct and 158 g. of the cyclo NC-C-C-O- " OH so 55 6 Yo?, Yo? H, o, ...... Eacample 20 . . . XE ch, A mixture of 10 g. of B.F.O (C4H9)2, 92 g of CE H-CH -O glycerol, and 55 g. of cyclopentadiene-indene ad N1 60 duct was stirred at 90-95° C. for eight hours. . The product was washed with dilute sodium hy was stirred at 95° C. for eight and One-halfN hours. droxide solution, then with water, dried, and dis hydroxideThe product solution, was wished then withWhite water, dried,possil. and glyceryliii," mono-ether as a colorlessg. of the oil rearranged boiling at distilled in vacuo to yield 110 g. of the B-chloro- d O ethoxy derivative as a pale yellow oil boiling at "' 200° C./0.5 mm. having the probableCH formulaCBI mula180-190° C./1-2 mm. having the probable for Cf1. C-C / N CB CE N.- . f B2 pH, -'npH, 70 Hoch-CHOH-CH-O-E.---6 NYo?, Yo?,CH elemen-o-on- CE -CH o A mixture of 60 Eacampleg. of ethylene 21 chlorohydrin, 5 The cyclopentadiene-Safrole adduct used above is 75 g, of BF.O(CHo), and 91 g of cyclopentadiene

a 2,411,516 indene adduct heated at 95 C. So, five hours - 12 yielded 102 g. of the p-chloroethyl ether of endor . . was stirred for six hours at 95 C. The produ was washed with dilute sodium hydroxide, the ethylene hydroxycyclopentanoindane as a color with water, dried, and distilled in vacuo to yiel probableless oil boiling Sorinus at 155-15 C/1 mm. having the mm.88 g. havingof a colorless the probable oil boiling formula at 210-213 C./0. (3 . C 9. f E-o? Sos C . 0 f".. . . . oloton-o-ba-tis Yo?, Yo?í (CS CICHCH-0- " -O-O- -C: Eaggage 22 (1 A mixture of 3 g of Boccas), 54 g.of the products obtained according to this in benzyl alcohol, and S5 g. of cyclopentadiene-in. 5 vention are of potential value as intermediates dene adduct was stirred at 95 (C. or seven and for the preparation of resins, plasticizers, insecti one-quarter hours &nd Worked ap as above. Y cides, and pharmaceuticals, The benzyl ethes of endeehylene-hydroxycy claim: clopentanoimiane distilled over at 90-200 C./ 1. As a new compound, an acid-catalyzed ad an. as a colorless oil, 8th & Syield amounting to $20 dition-rearrangement product of an aliphatic 49 g, having the probable fossaula alcohol and an adduct of cyclopentadiene with styrene, said product being an ether of endo d e ethylene-substituted phenyl cyclopentanoi. 2. As a new compound, an acid-catalyzed ad of - ca dition-rearrangement product of an aliphatic 26 chloro alcohol and an adduct of cyclopentadiene sell with styrene, said product being a chloro alkyl ether ef, endoethylene-substituted phenyl cyclo Sacagmple 23 pentanol. 3. As a new compound, an acid-catalyzed ad A mixture of 5 g. of tetrahydro-furfuryl alco 30 dition-rearrangement product of ethylene chloro hol, 6 g. of B.F.O(CHs), and 55 g. of cyclopen hydrin and the cyclopentadiene-styrene adduct, tadiene-indene adduct was heated six and one said product being a chloroethyl ether of endo hydro-furfurylquarter hours at ether 90°-95 of C. endoethylene-hydroxy and yielded the tetra ethylene-substituted phenyl cyclopentanol. cyclopentanoindane as a colorless oil boiling at 35 4. As a new compound, an acid-catalyzed ad 169-173° C./0.5 mm. having the probable for dition-rearrangement product of p-chloroethoxy mula: r ethanol and cyclopentadiene-styrene adduct, said product being a 3-chloroethoxyethyl ether of . OE CB endoethylene-substituted phenyl cyclopentanol, Sna 5. A method for preparing a chloroalkyl ether H-B, of"- H 40 of endoethylene phenyl cyclopentanol, which comprises reacting in the presence of an acidic H. (B-CH-0- l".E-2 CB condensing agent an aliphatic chloro alcohol with N/O 6 Ye?, Yof the adduct of cyclopentadiene and styrene. Eacample 24 45 6. A method for preparing ethers which com prises reacting in the presence of an acidic con A mixture of 50 g. of cyclohexanol, g. of densing agent an aliphatic alcohol with the B.F.O(CHo)a, and 55 g. of cyclopentadiene. adduct of cyclopentadiene and styrene. indene adduct heated seven hours at 95 C. yielded 7. A method for preparing ethers which com the cyclohexyl ether of endoethylene-hydroxy 50 prises reacting in the presence of a boron tri cyclopentanoindane as a colorless oil boiling at fluoride catalyst an aliphatic alcohol with the 164-166° C./0.5 mm. adduct of cyclopentadiene and styrene. Eacample 25 8. As a new compound, an acid-catalyzed ad A mixture of 3 g. of B.F.O(CHs)a, 48.6 of dition-rearrangement product of glyceryl mono ethylene chlorohydrin, and 92 g. of cycloperata .55 chlorohydrin and cyclopentadiene-styrene ad diene adduct of 2,4,5-trichlorophenyl allyl ether duct, said product being a Y-choro-B-hydroxy CB . cyclopentanol.propyl ether of endoethylene-substituted phenyl of O BRMAN A. BRUSON. s B-CB-0 C