April, 1947
PREPARATION OF ETHERS OF TRIFLUOROMETHYL-SUBSTITUTED PHENOLS 947
Muskat apparatus a t a reaction temperature of 84-88'. Rates of flow were adjusted so that the ratio of CFaCHClCH:I to chlorine was always greater than 3 : l . The product contained 72% CFaCClzCHa and 28% CFICHCICHJCI.
2. Both photochemical and thermal chlorination of C C I F ~ C H Z C H have ~ yielded several new chlorofluoropropanes. 3. Several new fluorine-containing, propanes have been prepared by the fluorination of certain chloro- and chlorofluoropropenes with mercury(I1) oxide and hydrogen fluoride. Some bromofluoropropanes also were synthesized by fluorination of the corresponding bromides.
Acknowledgment.-The authors wish t o acknowledge the financial assistance of Mallinckrodt Chemical works which made this research possible.
Summary
LAFAYETTE, INDIANA
1. The preparation of C F ~ C H Z C and H ~ CClF2CH2CH3has been accomplished in excellent yields.
[ CO~TRIBTJTION FROM THE DEPARTMENT O F CHEMIsTRr AND
RECEIVED1' JANUARY 2, 1947
(17) Original manuscript received February 2.5, IO-ICI.
THE PURDUE
RESEARCH FOUNDATION, PURDUE UNIVERSIT\r]
The Preparation of Certain Ethers of Trifluoromethyl-substituted Phenols1.2 By EARLT. MCBEE,ROBERT 0. BOLT,3 PETER J. GRAHAXAND ROBERT F. T E B B E ~ Certain alkoxy-(trifluoromethy1)-benzenes and alkoxy- and aryloxy-his-(trifluoromethy1)-benzenes have been synthesized. The preparation of these compounds involves the action of a sodium or potassium alkoxide on a trifluoromethyl-substituted chloro- or bromobenzene. Such ethers are of interest as possible heat-transfer fluids since they exhibit a tendency toward non-flammability, a wide liquid range, and an enhanced stability to heat and the action of metals. Further, it would seem desirable for a heat transfer agent to possess an electron donor center, such as an oxygen atom, in the molecular structure. Dative bond formation between this electron donor and the metallic atoms of a heat transfer wall should effect more efficient transfer of heat. Other interesting possibilities for these ethers might include use as dielectric media, and as materials to improve the lubricating properties of oils. The new compounds prepared, together with their physical properties, are listed in Table I. Of the compounds synthesized, only 3-methoxy(trifluoromethy1)-benzene has been mentioned previously in the 1iteraturc.j However, the method of preparation of this compound was not disclosed. During the present study it was observed that, in the preparation of methyl ethers from trifluoromethyl-siibstituted chlorobenzenes, the temperature required for a particular synthesis was de(1) Presented as a part of the Meeting-in-Miniature, Purdue University, November 17, 1945. Abstracted in part from a thesis suhmitted (October, 1945) by R. F. Tebbe and a thesis t o be submitted (1947) by P. J. Graham to the faculty of Purdue University in partial fulfilmeut of the requirements for the degree of doctor of philosophy. (2) Acknowledgment is gratefully made to the Ethyl Corporation for sponsoring the research fellowship on which this work was accomplisheci. (3) Present address: California Research Corporation, a subsidiary of the Standard Oil Company for California, Richmond, California. (4) Present address: University of Maine, Orono, Maine. ( 5 ) Zitscher and Xehlen (to General Aniline), U. S. Patent 2,141,893. Dec. 27, 1938.
pendent upon the relative reactivity of the chlorine atom in the benzene derivative. Analogous to the behavior of the nitro-substituted chlorobenzenes, this reactivity appears to be a function of the position of the chlorine atom relative to the meta-directing group or groups. For the compounds investigated the order of reactivity was found to be c1 c1 c1
,
~ ~ ' - 0 - c ~Q-cF~ ~ CFs 1
,~ ~ c - 0 - >c ~ ~
CFs
2
3
c1
c1
c1
4
CFI 5
6
c1 &FJ
7
c1
= F3c--~-cF, 8
Experimental Preparation of Starting Materials 2- and 4-Chloro-(trifluoromethyl)-benzenes.-These compounds were prepared by the fluorination of commercially available 2- and 4-chloro-(trichloromethyl)-benzenes. The fluorination was carried out a t room temperature in iron equipment using anhydrous hydrogen fluoride in the presence of a small quantity of antimony(V) chloride as the fluorinating agent. 2-Chloro-(trifluoromethyl)-benzene (b. p. 148-150" (745)) was obtained in 85y0 yield; 4-chloro-(trifluoromethyl) -benzene (b. p. 135-136' (745)) was obtained in 91% yield. 3-Chloro-(trifluoromethyl)-benzene .-This compound (b. p . 135-136' (745)) was prepared according to the method of Holt and Daudta by the chlorination, in glass (6) Holt and Daudt (to du Pout). U. S. Patent 2,174,513, Oct. 3,
1939.
948
E. T. MCBEE,R. 0. BOLT,P.J. GRAHAM AND R. F. TEBBE
Vol. 69
apparatus, of trifluoromethylbenzene in the presence of other alkanol derivatives were made either by treating a n iron(II1) chloride. excess of alkanol with sodium (U.S. P.), sodium hydroxide 3-Bromo-(trifluoromethyl)'-benzene.-Trifluoroniethyl( C . P.) or potassium hydroxide ( C . P . ) . The resulting benzene was brominated &h the aid of an iron(II1) chlo- solutions were then used directly in the appropriate prothe bromo derivative7 cedures. Sodium phenoxide was prepared b y treating ride catalvst at 80" t o DreDare . I ( b . p. 15$L1540 (745)). a n excess of phenol (U. S. P.) with sodium in anhydrous 4-Chloro-l,3-bis-(trifluoromethyl) -benzene .-Technicai ether solution. The solid phenoxide which precipitated 1,8-dimethylLenzene was purified according t o the method was filtered from the solution for the syntheses. The alkaof Clarke anid Tavlor? and the purified 1.3-dimethvlben- nols were of commercial grade and the 3,6,9-trioxahenzene \vas chloriiiafed a t 10 t o Zj" in the presence of iron- decane was diethyl carbitol solvent. (111) chloride catalyst .!' The 4-chloro-1,3-dimethplberizene ( b . p . 119-OOo ( 2 4 ) ) thus ohtnincd was chlorinated Syntheses of Ethers of Trifluoromethyl-subsiituted photochemically a t temperatures ranging from 3U a t Phenols The the beginning of the reaction, t o 1 X o , a t the end. The several procedures which were used are described fraction of this product boiling a t 170 to 180' a t 8 nini. generally in the following paragraphs. Table I lists the was 4..chloro-l,S-liis-(trichloromethyl) -benzene. compounds and the methods used in their syntheses toAnai. Ca'Lcd. for C&jCl(CC1,)I: Cl, 71.6. Found: gether with results. C1, 72.0. Procedure A-1 .-A mixture of one mole of a trifluoroThe 4-chloro-1 ,j-bis- (trichloromethyl) -benzene was methyl-substituted chlorobenzene, 2 : 5 moles of a sodium converted t o 1-chloro-1,3-bis-(trifluoromethyl)-benzene alkoxide and 300 ml. of the corresponding alkanol was reby treatment with hydrogen fluoride in the presence of a fluxed a t atmospheric pressure for a period of twelve hours. small quantity of antimony(V) chloride. The reaction At the end of this time the volatile reaction product was was carried out in a nickel vessel at 70 t o 80". The yield steam-distilled. The lever layer of the distillate was -benzene (b. p . 148 ") scparated and dried over calcium sulfate. The aqueous of 4-chloro-1,3-bis-(trifluoromethyl) was 41 .S%. layer of the distillate was extracted three times with 100A m ! . Calcd. for C&Cl(CF,)t: C1, 11.3; F, 45.8; ml. portions of chloroform and the extracts mixed with the mol. n t . , 218.5. Found: C1, 1 4 . / ; F , 46.1; mol. wt., original organic layer and drying agent. This mixture was then rectified. 251 .o. Procedure A-2.-This is identical with 'Procedure A-1 5-Chloro-l,3-bis-(tr~fluoromethyl) -benzene.-This niaterial ( b . p . 135--13(3 (743)) was furnished by M . R. except t h a t 3,0,0-trioxahendecane was usetl in place of the Frederick of I'urdue University. The method of prepara- alkanol. The reaction temperature realized with this method depends on the boiling point of the halohydrotion will be published a t a later date. carbon used and/or on the boiling points of the products Ami'. Calcd. for CsH3C1JCFP)2: C1, 14.3; F, 45.8; obtained. mol. wt., 24S.j. Found: C1, 14.1; F, 45.6; mol. wt., Procedure A-3 .-This method is similar t o Procedure 250. A-1 except t h a t a n equimolar mixture of potassium hyZ-Chloro-l,3-bis-(trifluoromethyl) -benzene .-The di- droxide and the alkanol was used in place of the anhydrous rections of Kalischer and Frister'" were followed for the sodium alkoxide. preparation of 2-chloro-l,3-dimethylbenzene. This inaProcedure B-1 .-One mole of a trifluoromethyl-subterial was chlorinated and fluorinated in the usual manner, stituted chlorobenzene, 2.5 moles of a sodium alkoxide or A 27.87; yield and conversion t o 2-chloro-1,3-bis-(tri- aryloxidc, and 300 ml. of the corresponding alkanol were fluoromethyl)-benzene ( b . p . 154-158" (745)) was ob- placed in a n iron autoclave (constructed to withstand 40 tained. 4 sizable fraction boiling a t about 147' x m s also atm. a t L ' O l l O ) of one-liter capacity fitted into a n elecisolated which is presumably 4-chloro-l,3-bis- (trifluoro- tric heater mounted on a mechanical rocker. The methyl) -benzene, a possible isomcr in the synthesis. vessel was heated to 100" in four hours, after which it was 2 -Chloro-l,4 -bis- (trifluoromethyl)-benzene .-This coni - alloneti to cool t o 85" in four and one-half hours. The repound n-as syiithesized from 1,4-tlimethylbenzene in a action product was removed from the autoclave a t about mannet' simi1a.r to t h a t outlined for the preparation of 1- room temperature and treated as in Procedure A-1 prior chloro- I ,3-bis-i trifluoromethyl) -benzene. The yield of to rectification. 2-chlor~~-l,4-bis-~trifluoromethy1) -benzene f b . p . 147 ') Procedure B-2 .-This method is similar to Procedure B-1 exccpt that an equimolar mixture of sodium hywas 60';. A n d . Calcd. for CJI3Cl(CF3)2: C1, 14.3; F, 45.8; droxide and the alkanol or phenol was used in place of the mol. w t . , 248.5. Found: C1, 14.1; F , 46.1; mol. w t . , anhydrous sodium alkoxide or aryloxide. Procedure C-1 .-One mole of a trifluoromethyl-sub247.0. stituted phenol was dissolved in one mole of sodium hyThough 4-chloro- and 5-chloro-l,3-bis-( trifluorodroxide in 415 ml. of water. The solution was cooled with - agitation methyl) -benzene and 2-chloro-l,4-bis-(trifluoromethyl) t o 0 " and one mole of a dialkyl sulfate added benzene have been anticipated in the patent literature," the physical properties of these compounds (see Table I ) dropwise. After one hour, the mixture was heated a t reflux temperature for about three hours. The resulthave not been reported. ether was recovered by the method described i n 3-Trifluoromethylphenol.-This material (b. p. 68-69" ing Procedure 8-1. \12)) was synthesized in small quantities by the method of bwartsI2 which involves the hydrolysis of 3-trifluoroDiscussion methylbenzenediazonium sulfate. T h e latter compound was derived from trifluoromethylbenzene b y nitration,13 In the general procedures described for the reduction13 and diazotization.12 preparation of the ethers, the only basic differences Metallic Alkoxides and Ary1oxides.-The sodium methI n general, are those in temperature, exposure time, and the purity. oxide was commercial material of 95y0 .. . O,
(7) Sirnons and Ramler, THISJOURNAL, 65, 389-392 (1913). ( 8 ) Clnrke and Taylor, i b i d . , 45, 830-833 (1923). (9) P. Jacobson, Be?., 18, 1760-1762 (1885). (10) Ralischer and Frister (to General Aniline), U. S. Patent 1,796,105, March 10, 1931. (11) Holt and Mattison (to Kinetic Chemicals, Inc.), U. S. Patent 1,967,244, July 24, 1934. (12) Swarts, Bull. acad. roy. Belg., 241-278 (1913). (13) Swnrts. ibid.. [3] 35, 37.5-420 ( l X 9 X ) .
amount of water present. The position of the halogen atom to be replaced in the benzene nucleus and the complexity of the carbon chain of the alkoxide or aryloxide determine the procedure necessary. These factors fix the threshold temperature required for a finite reaction rate and determine the amount of hydrolysis product. Once t h e threshold
has
heen
siirpassd, the,
April, 1947
PREPARATION OF ETHERS OF TRIFLUOROMETHYL-SUBSTITUTED PHENOLS 949
TABLE I ETHERS OF TRIFLUOROMETHYL-SUBSTITUTED PHENOLS AND CHLOROBIS(TRIFLUOROMETHYL) -BENZENES Procedure," Ether used B-le 2-CFaCeH,OCH3 B-2f B-20 ~-CF~C~HIOCZHS B-Zh 2-CFaCeH OCH(CHrl2 B-I, 3-CFaCeHzOCHq A-2% B-li B-lK C-1 C-1 3-CFaCsHrOCzHi A-Z2 4-CFsCsH4OCHs B-1"' B-2" B-2 ~-CP~C~HIOCIH~ ~ - C F ~ C ~ H I O C H ( C H ~ ) ~ B-Zo A-3 1,3-(CF:)zCsHa-4-C)CH: B-1 A-3 1,3-(CFa)zCsHa-4-C)CzHs 1, ~ - ( C F ~ ) Z C ~ H ~ - ~ - O C ~B-1 HT B-2* B-1 1,3-( CFa)zCsHa-4-OCH (CHa)a 1,3-(CFa)zCeHa-4-OCH~csH4 A-1 B-1 1,3-(CF3)zCsH3-4-C)-octyl 1,3-( C F ~ ) ~ C B H ~ - ~ - C ) C ~ B-19 H~ B-l 1,4-(CFa)zCsHs-2-C)CHs B-lr 1,3-(CF3)2CbH3-5-ClCHa A-3 1,3-(CFa)zCsHs-2-OCHs 1,4-(CFa)1CsH3-2-C)CHa 1,3-(CFs)zCsHa-4-C1 1,3-(CFa)zCaHa-5-CI 1,4-(CFa)zCsHs-2-C1
Conver-
sion,b Yield,b
%
%
36 4 29.6 40.0 20.4 28.4 7.9 23.3 8.0 55.5 37.6 8.5 56.8 52.4 49.8 77.5 43.8 52.5 41.6 41.2 34.8 35.3 48.5 48.8 27.1 22.9 48.0 31.2
57.5 27.2 62.0 43.2 54.5 20.5 31.2 31.0 55.5 37.6 29.3 75.2 66.0 67.8 77.5 56.2 64.0 64.5 48.5 50.0 43.6 58.5 48.8 27.1 22.9 76.0 44.5
B. p . , c j d o c . (754)
M. p.,d
173.7
-14.1 to
184.5 202.9 159.5
-
OC.
-
n%
14.3 1.4524
2 4 to - 2 . 8 1,4470 -29 7 to -30 3 1.1488 1.4435 -6.5 0
Fluorine, yo d% Calcd. Obs. 1.2616 32.4 32.9
Mol. wt. Calcd. Obs. 176 174
1.1970 1,1624 1.2426
30 0 27 9 32.4
30 3 28 1 32 7
190 204 176
190 204 181
173.0 168.6
-16.0 - 9.1
1.4418 1.4455
I . 1903 1.2445
30.0 32.4
3U.2
33.0
190 176
192 175
182.6 200.0 176.0
9.3 3.0 f 1 7 . 5 to 18.0
1.4451 1.4458 1.4149
1,1912 1.1524 1.4330
30.0 27.9 46.7
30.6 28.4 47.2
190 204 244
190 203 249
185.0 200.0
26.0 t o 26..5 -15.0 t o -16.0
1.4130 1.4162
1.3559 1.3101
44.2 42.0
44.6 41.8
258 272
257 270
192.0 275.0-277.0 278.0 244.0 163.0 160.5 173.0 163.5 148.0 137.5 147
Sets t o a glass Sets t o a glass 8.5to 9.5 Sets to a glass 26.5 to 27.5 2.0 t o 3 . 0 4 . 0 to 5 . 0 26.5 t o 27.5 -58.0 to -59.0 -29.5 to -30.0 - 1 2 . 0 t o -13.0
1.4128 1.4887 1.4304 1.4756 1.4221 1.4084 1.4170 1.4150 1.4150 1.3611 1.4135
1.2958 1.3454 1.1705 1.3777 1.4110 1.4192 1.4507 1.4110 1,5201 1.4942 1.5112
42.0 35.6 33.3 37.3 46.7 46.7 46.7 46.7 45.8 45.8 45.8
41.9 34.6 33.5 37.8 46.9 46.6 46.6 46.9 45.9'
272
270
-
-
...
...
306 244 244 244 244 248.5 218.5 415.1~ 248.5
...
... 302 239 240 243 239 254 250 237
Calculations based on the halohydrocarbons. e Determined by SiwoloSee text for explanation of procedyes. boff micromethod (Shriner and Fuson, Identification of Organic Compounds," 2nd ed., 1940, p. 93). Absolute values 7.2% conversion t o 2-HOc~Hac02H. 24% conversion to 2-HOCsH4COzH. 0 3% conversion accurate to *0.2". t o 2-HOCsH4C02H. Six hours to 200". a 3-CF3C6HaBr used; four hours a t 130". 3-CF3CaH4Br used; 21.2% Three hours to 140"; 5.4% conversion to CF&hHs. A.1 yields no ether; twenty-four hours conversion t o CF&!&,. at 110'. 6.5% conversion to ~ - H O C B H ~ C O Z H .17.7y0conversion to 4-HOCsH4COzH. Six hours to 200'. p PotasSeven and one-half hours to 225", 1 g. copper catalyst used. Five hours to 180'. sium hydroxide and 150' used. 14.3% C1 calcd., 14.1% obs. * 14.3% C1 calcd., 14.5% obs. 14.3% C1 calcd., 14.1% obs. Q
'
chosen proceclure is one involving a temperature which will produce a convenient reaction rate. The hydrolysis product occurs to an appreciable extent only in the preparation of the methoxy(trifluoromethy1)-benzenes, where hydroxybenzoic acids were isolated. Thus, in the case of the synthesis of 4-methoxy-(trifluoromethyl) -benzene, Procedure A-1 gives no ether, Procedure A-2 gives product after a long reaction period, Procedure B-2 gives an appreciable amount of hydrolysis, and Procedure B- 1 is satisfactory. Consideration of the data in Table I and the indicated relative reactivities of the halohydrocarbons and the alkoxides and aryloxides makes possible the selection of a suitable procedure for the synthesis of a particular ether. The optimum ratio of alkoxide to halohydrocarbon in the syntheses was determined to enable most complete utilization of the latter material. Conversions to the ethers increased with increasing mole ratios up to 2.5 to 3.0, with no significant improvement in efficiency being obtained a t higher ratios. A powdered copper catalyst when used in Procedure B-2 only increased the amount of hvdrolvsis product obtained and did not promote
formation of a methyl ether. However, the catalyst was found to improve conversion and yield of a phenyl ether in Procedure B-1. The difficulty of obtaining the trifluoromethylsubstituted bromobenzenes limits the utility of these compounds in the ether syntheses. Furthermore, experiments with 3-bromo-(trifluoromethy1)-benzene indicate that this material is inferior to the corresponding chloro compound. The low yields obtained testify to the multiplicity of reactions, including reduction and coupling, attendant upon the employment of 3-bromo-(trifluoromethy1)-benzene. In addition to the lirnited availability of the trifluoromethyl-substituted phenols, which a t present restricts the scope of Procedure C-1, the method also appears economically inferior to the others described.
Summary Various ethers of trifluoromethyl-substituted phenols have been synthesized and physical properties reported. These compounds were prepared by the action of a 'sodium or potassium alkoxide or aryloxide on a trifluoromethyl-substituted chlnro- or bromohenzene. The position on
950
AVERYA. A)~ORTON, EUGENE E. MAGATAND ROBERTI,. LETSINGER
the benzene ring of the halogen atom to be replaced and the complexity of the carbon chain of the alkoxide or aryloxide determined the procedure used in each synthesis. Variations in the
[CONTRIBUTION FROM
THE
Vol. 69
general procedure involved reaction temperature, exposure time and amount of water present. LAFAYETTE, INDIANA
RECEIVED'* JANUARY 2, 1917
(14) Original manuscript received July 15, 1946.
DEPARTMENT OF CHEMISTRY, MASSACHUSETTS INSTITUTE OF TECHKOLOGY 1
Polymerization. VI.
The Alfin Catalysts'"
BY AWRY .I. ~ I O R T O NEUGENE , E. MAG AT^^ The sodium salt of a methyl n-alkyl carbinol and the sodium salt of an olefin, for example propylene, form a complex that causes the catalytic polymerization of butadiene and isoprene. Agents of this type are called Alfin catalysts because an alcohol and an oleJin are involved in their preparation. This paper (1) gives a n account of the discovery of these catalysts, (2) lists the'types of compounds t h a t will form such agents, (3) describes the methods used for testing the catalysts (4) shows the unique features t h a t mark the polymerization, induced by these agents, to be distinctly different from that caused by other polymerizing agents, (5) lists the general characteristics of Xlfin polymerization, (6) shows some variations that are possible with different Alfin catalysts and (7) suggests a possible formula for the active catalyst complex. Discovery of the Catalyst The catalyst was discovered by accident in the course of our study2 of the addition of organosodium compounds t o dienes. The effect of diisopropyl ether was being tested in the same way as the effect of a tertiary amine on the addition of amylsodium to butadiene had previously been tested.2 The reaction took, however, an entirely different course and high polymers resulted in spite of the fact that the diene was added drop by drop t o a very large excess of the organoalkali metal reagent. A similar result was obtained with isoprene, although the polymer was stickier than that obtained from butadiene. The explanation for this unusual effect on the two dienes lay in the formation of two products, sodium isopropoxide and allylsodium, derived from the ether and amylsodium, according to the equations
,+ (C€I&CHOCEI(CH3)z -++ ,CH$)&HONa 4-CsHlz + CHz==CHC€Is C 3 H I ~ N+ a CHF=CHC&+ CHCHaNa + C&IIINa
c3H12
(1) (2)
This conclusion was drawn after a series of experiments, shown in Table I. A rubber-like polymer was obtained only when sodium isopropoxide (la) The authors are indebted to the Research Corporation and to the Rubber Reserve for financial support of this investigation. ( l b ) Present address: Experiment Station, E. I. du Pont de Nemours & Co., Wilmington, Del. (IC) Present address: Chemistry Department, Northwestern University, Evanston, Ill. (2) Morton, Brown and Magat. THISJOURNAL, 69, 161 (1947).
AND
ROBERT L.LETSINGER~C
and allylsodium were both present and no polymer was obtained if either one was absent (experiments 7 and 8). hmylsodium or the ether could be absent without destroying the catalytic effect (experiments 4 or 1 and 2, respectively). Only a trace of reaction with the ether was needed in order to furnish enough of the two pertinent salts (experiments 3 and 5), although the amount could fall too low, as it did in experiment 6. The catalytic action was not induced by any energy or free radical liberated from the reaction of amylsodium with the ether because in experiments 2 and 4 the catalytic activity was present long after ether cleavage was concluded. The preparation of the catalyst from other reagents besides the ether confirmed this point (experiment 9). This series of studies was concluded by a successful test with a catalyst made by mixing a preparation of the alkoxide with an independent preparation of allylsodium obtained from the reaction of amylsodium with propylene. The unusual effect on dienes is clearly a consequence of the simultaneous presence of two particular alkali metal salts. The Class of Compound -~llylsodiumand sodium isopropoxide f orm one of a class, the components of which, as shown in Table 11, are specific. Only alkoxides from methyl n-alkyl carbinols have so far proven effective. Only mono olefins that have a t least one alkyl group attached to a carbon atom of the vinyl group or two alkyl groups attached, one to each of the carbon atoms, have so far been suitable. The mercaptide (CH&CHSNa, and the amide (CH3)2CHNHNa, corresponding to the alkoxide, could not replace the isopropoxide in combination with 2-butene as the olefin. The metalation product of diallyl in the presence of isopropoxide proved unsuitable, although one of the products of such a reaction was a propenyl substituted allylsodium, CH2=CHCH (R) Na (where R=CHzCH=CHz). The addition product of amylsodium with butadiene likewise failed as a component of the catalyst, although the product2 of such addition is a hexylallylsodium, either Na(R)CHCH=CHt or RCH=CHCHzNa (R = CgH 1 3 ) depending on whether the addition occurs 1,2- or 1,4. Both failures are important because (3) Morton and Brown, Tats unpublished research.
JOURNAL,
69, 160 (1947), and
