Reaction of the Acid Chlorides of Aromatic Acids

with Bromine and Silver Oxide'


Received June 4, 1956 I t has been found that the acid chlorides of several aromatic acids on treatment with silver oxide and bromine in carbon tetrachloride solution loose carbon dioxide. The acid chloride is substituted by the halide.

It has been reported3 that when the acid chlorides of acetylated hexonic acids are dissolved in carbon tetrachloride and heated at reflux temperature with silver oxide and bromine, the acid chloride loses carbon dioxide and forms the aldehpdo-l-bromo-penta0-acetyl-pentose. Either acetic anhydride or acetyl chloride3react with mixtures of silver oxide and bromine and after respectively losing 2 moles and 1 mole of carbon dioxide, form methyl bromide. Although the product formed by the reaction of acid chlorides with silver oxide and bromine is essentially the same as that obtained by the decarboxylation of the silver salts of organic acids by reaction with bromine,4 the acid chlorides, in contrast

like the sugar acid chlorides, would react to form carbon dioxide and the corresponding halide. Benzoyl chloride was found to react, with silver oxide and bromine to yield bromobenzene. The mand p-nitrobenzoyl chlorides formed the corresponding rn- and p-bromonitrobenzenes. Kaphthoyl chloride also reacted, although slowly, under the same conditions to form bromonaphthalene. The reaction as measured by the evolution of carbon dioxide was essentially quantitative (Table I). A possible mechanism for the above reaction is that the acid chloride reacts with silver oxide to form the silver salt of the acid and silver chloride. The silver salt would then react with bromine to

TABLE I DECARBOXYLATION OF AROMATIC ACID CHLORIDES WITH BROMINEN D SILVER A OXIDE COZevolved. Equivalent in ml. 0.1 N HCl Calc'd Obsv'd 143 228 216 196 140 211 210 116

Weight, Compound
~~ ~ ~


Compound" Isolated Bromobenzene p-Nitrobromobenzene m-Nitrobromobenzene Bromonaphthalene

w p . , OC. Observed Literature

Benzoyl chloride p-Xitrotwnzovl chloride7 (m.p. 72-73) m-Sitrobrnzoyl chloride7eT1 (m.p. 32-33) Yaphthoyl chloride12 (m.p. 52-53)

1.0 1 95

155-1 57 (b.p.) 125-127 56 59

155O 126-1278t9 5610,ll 59'3



Thr compounds gave the cor] rct elemental analyses.

to the silver salts are easily prepared in an anhydrous condition and hence are more convenient to use than the silver salts. We were not able to find that the decarboxylation of aromatic or aliphatic acids via their acid chlorides had been studied and hence it was considered of interest to investigate several aromatic acid chlorides to find out if they,
(1) Published with permission of the Bureau of Ordnance, Navy Department. The opinions and conclusions are those of the authors. (2) Graduate Student at the Ohio State University, Columbus, Ohio. Appointee for the summer of 1955 under the summer Research program of the Research and Development Department, U. s. Naval Powder Factory. (3) F. A. H. Rice, Abstracts 0.f the 198th Meeling of the American Chemical Soczely, Minneapolis, Minn., 21D (1955); F. .4. H. Rice, J . Am. Chem. Soc., 78, 3171 (1956). 14) J. Kleinberg, C h e m Revs , 40, 381 (1947).

(5) I,. Birckenback, J. Goubeau, and E. Berninger, Rer.,
65, 1339 (1932); W. Bockemuller and F. W. Hoffman, iinn., 519, 165 (1935); C. C. Price, Reactions at Carbon-Carbon

' Double Bonds, Interscience Publisheis, New York, h . Y., p. 55 (1946). (6) J. H. Gladstone, J . Chem. SOC.,45, 241 (1884): W. Ramsav and S. Young, J. Chem. Soc., 47, 640 (1885). (7) H. &lever, Monatsrh, 22, 425 (1901), Org. Syntheses, Coll. Vol. 1, 2nd ed., 394 (1941). (8) J. H. CoRte and E. J. Parry, Be?., 29, 788 (1896). (9) o-Bromonitrobenzene has m.p. 43", F. Ullman, Ber., 29, 1878 (1896). (10) I. Hrilbron and H. RI. Bunbury, Dictionary of Orgnnic Compounds, revised Ed., Vol. I, Oxford University Press, New York, S . Y., p. 350 (1953). (11) L. Claison and C. M. Thompson, Ber., 12, 1942 (1879 ). (12) P. T'ieth, Ann., 180, 305 (1876). (13) A. Michaelis, Ann., 321, 141 (1902), footnote p. 246.


flask. Reagent grade benzoyl chloride was used.1 il' hydrochloric acid and subtracting the hlank which had been run without the addition of the acid chloride. The acid chlorides were prepared by heating the corresponding acid with thionyl chloride a t reflux temperature and.2 N aqueous barium hydroxide. of redistilled bromine in 20 ml. but otherwise under the same conditions.MARYLAND . after four hours heating only traces of silver salt can be found. INDIAN HEAD. Acknowledgment.5 g. is suggested by the observation that when either the acid chloride of Dgluconic acid penta-O-acetate3 or an aromatic acid chloride is added slowly to a boiling mixture of bromine and silver oxide in carbon tetrachloride. A stream of nitrogen from which traces of carbon dioxide had been removed by bubbling the gas through saturated aqueous sodium hydroxide and from which moisture had been removed by bubbling the gas through conc'd sulfuric acid was used to sweep out the carbon dioxide as it was formed. P. after concentrating the solution t o dryness under reduced pressure a t room temperature. The carbon tetrachloride had been previously dried over phosphorus pentoxide and then redistilled.4. On the contrary.6That the above mechawould give R X nism may not be the true one. On the other hand. The decarboxylated product was isolated by filtering the carbon tetrachloride solution. the carbon dioxide was absorbed in 0. Approximately one gram of the acid chloride was dissolved in approximately 50 ml. refluxing the acid chloride with silver oxide does not lead to the immediate formation of the silver salt of the acid. to remove any trace of bromine. We wish to thank Mrs. was added and the mixture was stirred and heated under reflux. concentrating it to dryness and distilling or crystallizing the product from ethanol. Table I shows the amount of carbon dioxide evolved from a number of acid chlorides. Reaction of acid chloride with bromine and silver oxide. carbon dioxide is immediately and continuously evolved. of dry carbon tetrachloride. Wheeler for performing the microanalyses.~ C02. were dried under high vacuum at room temperature. After the gases had passed through two traps immersed in Dry Ice-Acetone. of carbon tetrachloride in a threeneck 250-ml. dried over phosphorus pentoxide in a high vacuum a t 100' for 24 hours) and 2 g.p.DECEMBER 1956 BROMINE A N D SILVER OXIDE ON AROMATIC ACID CHLORIDES 1389 give the p r o d ~ c t RCOOBr which when heated ~. The amount of carbon dioxide evolved was determined by titrating the barium hydroxide solution with 0. 3-0) Before use the acid chlorides 06'. P. + EXPERIMENTAL Preparation of the acid chlorides f r o m the free acid. crystallizing the resulting product from petroleum ether (b. An excess amount of silver oxide (2.

Osuga.280 COMMUNICATIONS VOL.the carboxylic acid to give the acyl hypohalite.8a-octahydro-exo-endo 1.p. of carbon tetrachloride for salts. and reaction in light gives polybromination.6 No 7-butyrolactone was found in the latter case.19 mole of red dures involving preparation of silver or mercury mercuric oxide in 150 ml. E. Org. the preexcellent yields of the corresponding alkyl bromide. unpublished work. I11 IV Br I Acknmledgment.6 and in poor yield to give 1.J. D. unpublished work. Nelson. Meek and P. W. Chem. It seems most likely that the mercuric oxide fashion. Cow). C. UNIVEESITT OF COLORADO WILLIAM FIRTH.4Silver oxide may not be substituted for (1) For leading references see: (a) H.25 mole of bromine and 0.5.anorg. JR. S.' Of these reactions.' This intermediate RCOOX. (c) C. the reaction has been found to go in fair to excellent yields with cyclopropanecarboxylic acid and bromine14 with 9. 226..2 of the silver salt (generally termed the Hunsdiecker This suggests that both procedures lead to the same reaction) appears to be the most useful.. W. as reagents and opera.7. 370 (1936). R.with the reaction as it apparently does in the Hunsboxylic acid in carbon tetrachloride with approxi.' I n any case. P. m. 32" for pure material).3.2. J. . 1960 (7) W. unpublished work. The reaction gave poor yields with benzoic acid and bromine.(b) R. parative value of this procedure lies in its convenFor example. Nelson for permission to mention their work previous to publication.9. Suc.4a15. (4) J. 2 physikal. When either exo. W.V. J . S. 1928 (1960). that from the silver salt of either acid with bromine. T. W. K. This is halogenative decarboxylation reaction RCOOM precisely the same mixt. J.-CChem. Ber . F. Brenshede and H. we do not underTreatment of a slurry of excess red mercuric stand why the water formed does not interfere oxide in a refluxing solution of an aliphatic car.3dibromopropane from glutaric acid. 26 mercuric oxide. 9. H. (2) S.and R. S.8Sir: dimethano-2-naphthoic acid (11)2was treated under The salts of R variety of metals and carboxylic these conditions. Douglass. 356 (1935).8.. ( 6 ) S. In the course of our studies2 on the mecha. one hour gave a 93% yield of crude heptadecyl bromide. and (b) glutaric nism of the decomposition o the acyl hypobromite acid does not. C Firth. W. Reactions.25 mole of stearic acid ience and simplicity in comparison to those procewith 0. 56.4. Wilson. Jennings.G Johnson and R.10-ethano-9-anthroic with broacid mine in carbon tetrachloride and with iodine in cyclohexane. is further indebted to the Shell Development Company and the University of Colorado for research fellowships.8.+ RX MX CO. Ingham.(I) or endo-5. Received October 21.5 with lauric acid and bromine.normal Hunsdiecker reaction. The authors are indebted to Professor John S. 291 (1942). C.'Oldham. 100 (1950). Chem. Cristol and J.9-hexach10ro-1.diecker procedure where glassware and chemicals mately one equivalent of bromine in the dark led to need to be scrupulously dry. Krall. Jenningsand n/IissJ. 22" ( l k 3m.7J. tions are much more convenient than the silver If this is the case. Revs. Tetrachloroethane may also be used as solvent.e with stearic acid and iodine. The reaction may involve reaction has the practical disadvantage that the the existence of the mercuric salt although (a) it has silver salt must be relatively pure and must be been reportedla that mercury salts of acids such as scrupulously dry in order to obtain satisfactory stearic acid do not give good yields following the yields. Soc.ure of bromides obtained X.219 (1956). 29B. (3) For comparable results with the silver salt see: J. a mixture of 71% em-(111) and acids upon treatment with halogens lead to the 29% endo-bromides (IV)z was formed. The presumable stoichiometric equation is as follows: A Convenient Synthesis of Alkyl Halides from Carboxylic Acids - + + + "3 2 RCOOH + HgO + 2 Brp+ 2 RBr + HgBrt + H20 + 2 Cot c 1 (1) COzH c 1 / Cl I Since our original observation. we a b silver (and presumably the mercury) salt gives the tempted to prepare this intermediate in another lactone. Cristol. BOULDER. Meek. J. This has led to what appears to us to be a gives a positive halogen species: which reacts with useful preparative method. Am..10-dihydro-9. treatment of 0. Hunsdiecker. Chem.332 (1957). and if equation (1) represents the salt-bromine reaction.4. stoichiometry of the reaction. whereas the f intermediate' in the Hunsdiecker reaction. DEPARTMENT OF CREM~STFU STANLEY CRISTOL J.6.. Chem.Schumacher. Z. (5) J.. 82. S. Jr . Osuga. . J.p. Hunsdiecker and C. Meek and D T. give ybutyrolactone.

-A solution of 69. 96. S6. Anal.c. b. b.3mole) of water was added intermittently over a period of 1.29. Naval Ordnance Laboratory. Soc.). H. Since mercuric oxide is relatively expensive and mercury compounds are tokic. E. O w . Distillation after work-up yielded 4. A part of the 1.I. a t 50". H. 46" (0. (217.).'^ JIMB U N D SAND~DOUGLAS SON^^ H .~ JOHN Department of Chemistry.m. A study has been made of the possible use of oxides other than mercuric oxide and of the effectiveness of various solvents. of carbon tetrachloride a t 76". H. Rice. (0. G. Chem. Unfortunately. Silver Spring.5-trihydroperfluoropentanoland 5.). 7 8 .p. Found: C. fractionation of the product yielded 24. Fund. b. (5) F. The reaction also was reported to give poor yields with benzoic acid arid glutaric acids. Chem. l. furnishing aldehydo-1-bromo-D-arabinose penta-0-acetate in an excellent yield. ~ .15mm... A. p-nitrobenzoyl chloride.1.lO-ethane-9-ant hronic acid. H.25 hr.p. 198 g. 1. Kansas Received August 18. 1. JAMESE R Y N KSAMCAR ROLL.5 ml. 332 (1957). A.). and lauric acid. Topeka. Chem. phthal(1) (a) This work was made possible b y Grant R897-B from the Petroleum Research Fund. Large amounts of phosgene and hydrogen chloride were evolved over a period of 5 hr.).~ generally quite good (usually better than 60%). tlle presence of which leads to the recovery of unchanged acid. K .p.7g. Ingham. (3) C. bromine. (0.) of the bis carbonate. Acknowledgment.1. and fair to excellent yields with cyclopropanecarboxylic acid. and acid chlorides were redistilled before use. 0 Methyl chlorocarbonate (10. Johnson are gratefully acknowledged. b. and 295 g. DAVIS. 3173 (1956). J. 62ycyield based on unrecovered alcohol. Johnson and R .1mole) of 1. of ferric chloride in 60 ml.44. The many stimulating discussions with Dr. H. b.) at the U. bromides were obtained by fractional distillation of the reaction mixtures. Jr. i b i d .1 mole) of 1. especially bromine.. As soon as we learned of the Cristol-Firth modification. Chem. Rice and W. b.05. and p-chlorobenzoyl chloride. Morganroth.. Reactions.5trihydroperfluoropentyl carbonate. W. H .1 mm. 2230 (1954). 0. J .l. oyl chloride.5mm.FEBRUARY 1965 MODIFICATIONSTHE HUNSDIECKER OF REACTION 415 the crude product produced recovered alcohol.7-trihydroperfluoroheptyl orthebenzoate. 31.1 mm. J .p.1. Org.p.6 g. 155"(0.1. 40 g. or iodine in an inert solvent is commonly Yields are known as the Hunsdiecker r e a c t i ~ n . The silver oxide was carefully dried as was all the glassware and the carbon tetrachloride. dried. analyses and determination of the same retention times by g. Although numerous variations of the reaction conditions were tried. . to a mixture of 26. Wilson. the preparation of dry silver salts of carboxylic acids is frequently very difficult and. The fractionation gave recovered alcohol. n-butyryl chloride.0 g. by treatment of the anhydrous silver salt of the acid with bromine. Shoppee and R .7-trihydroperfluoroheptyl benzoate.. for C28H14F3803: 31. Calcd.02 mole) was added to excess methanol in ether a t 50". Rev. (70y0of methyl 1. H.3mole) of 1. and 15 g. After the addition of 2. 1.1 g. . S.7-Trihydroperfluoroheptyl chlorocarbonate was prepared in a similar manner except the alcohol and water were added portionwise simultaneously. Sickman and Dr. Less than 10% of chlorocarbonate was obtained. 0. but the reaction is extremely sensitive to trace amounts of water. C. Maryland. of 1. A second report6 described the reactions of benzoyl chloride and three other aromatic acid chlorides with bromine and silver oxide in carbon tetrachloride. Replacement of the carboxyl group in organic acids by a halogen atom.5-trihydroperfluoropentanoland 8. Several years ago there appeared a report5 that the acid chloride of penta-0-acetyl-D-gluconic acid undergoes smooth decarboxylation when heated with bromine and silver oxide in carbon tetrachloride. more of water.2 g. The two methyl fluoro alcohol carbonates from these experiments were found to be identical by infrared and n.02 mole of titanium tetrachloride for 5 hr.11 mole) was stirred with 23. washed very quickly with cold water. 27. Anal.4 g. Cristol and William C.3 g.2 g. (6) F. Phosgene was bubbled through a mixture of 22. its apparent convenience and simplicity in comparison to those procedures involving preparation of silver salts or acid chlorides immediately suggested a broad study of this modified procedure using different classes of carboxylic acids and the use of solvents other than carbon tetrachloride. they are &n quite hard to dry thoroughly. 219 (1956). 53" (13 mm.4 g.S-TrihydroperfluoropentylCh1orocarbonate.r. 5 ' (0. (0. V. 73" (14mm. 0. for C8H3ClF1202: C.36. 11.05 mole) of ferric chloride for 6 hr. (2) R. (4) C. the reaction was allowed to continue an additional 8 hr. Cristol. Firth. A m . a study also was made of the possibility of using other oxides for this reaction. Stephenson.5-trihydroperfluoropentanolin chloro- form containing 0. and distilled. administered by the American Chemical Society: (b) American Chemical Society Petroleum Research Fund Scholar. D.)of the chlorocarbonate. However. chlorine.21. because such salts are usually quite sensitive to heat also.lO-dihydro-9.p.4 g. 9. 27.1. The chlorocarbonate was obtained in 40% yield. Modifications of the Hunsdiecker Reaction'" JOHN A.54.81. fair yields of bromobenzene were obtained from silver benzoate by the original Hunsdiecker reaction. Soc.1.~~ . 9 ..1.1. Washburn University of Topeka.-This paper is related to an observation by one of us (M. (0. After cooling. 187" (0.5-trihydroperfluoropentyl chlorocarbonate (6.p.1. 1. 196'4 Bromodecarboxylation of organic acids by the Cristol-Firth modification of the Hundsiecker reaction using the free acid and red mercuric oxide was found to be much more effective than the modification using the acid chloride and silver oxide.. only trace amounts of the desire(. (6097. 280 (1961) . the entire reaction mixture was dissolved in ether. (80%) of the methyl fluoro alcohol carbonate. and Firth have reported' that treatment of a slurry of excess red mercuric oxide in a refluxing solution of stearic acid in carbon tetrachloride with approximately an equivalent amount of bromine in the dark gave a 93% yield of crude heptadecyl bromide. (7) Stanley J. V. 1388 (1956). a t 50'. After work-up similar to above experiments. Found: C. of 1.). 1. Calcd. H. An investigation of this modification of the Hunsdiecker reaction was started using the following acid chlorides: benzoyl chloride.70. (0.

636 (1943). CARROLL. Chem.446231(1. only the five listed in Table I11 showed any reaction. In these determinations 0. then filtered and washed with 5y0sodium hydroxide solution.2-tetrachloroethane solvent. J. It was then filtered and the bromide was separated by fractional distillation and identified by its boiling point and refractive index (see Table I). zinc. If a reaction did not occur spontaneously.. of bromine was slowly added. antimony. cobaltic.05 mm.425026( 1. Am.. The literature values for 1-bromopropane and for all the compounds below it in the table are taken from A. AND JOHNSON VOL. Traynelis. The carbon dioxide was swept out of the apparatus with nitrogen and absorbed in a standard barium hydroxide solution.444031(1. BUNDS. C. Mukherjee. Literature values of refractive index are given for 20". Stevens. heating was continued until the reaction started.447028(1.4254) CzH zC14 2-Bromopropane Isobutyric 2-Bromobutane C2HzClr 61 90-94 (91) 1 . aa Numbers in parentheses are per cent yields baaed upon the amount of organic bromide recovered by fractional distillation. nickelic. J. Discussion In this investigation it was found that the CristolFirth method using red mercuric oxide and the free acid gave much more decarboxylation than did the method .2.2.456826 (1.2-tetrachloroethanewere used as solvents. See Table I1 for yields obtained when carbon tetrachloride and 1. bismuth. cuprous.4795%(1.1.4366) 2-Methylbutyric CCl4 1-Bromopentane 31 125-130 (128) 1. The barium carbonate precipitate was removed by filtration and the excess barium hydroxide was titrated with standard acid. L.30 TABLE I PERCENTYIELDS BASED N WEIQHT BROMIDE O OF RECOVERED Acid Solvent Product Yield. Vogel.2-tetrachloroethane solvent and oxides other aa than red mercuric oxide. it was found that best yields were obtained when the acid.a CzHzCli Bromochloromethane 38 68-73 (68-69)b 1. barium.. OC. K. of solvent. Chem. ferric. Soe. stannic. (an excess) of red mercuric oxide (or an equivalent amount of other oxide) and 50 ml. The mixture was warmed and 2 ml. T. calcium. and the solvent were mixed and stirred with a magnetic stirrer. Of the oxides that were tested as replacements for red mercuric oxide. a large number of determinations was made in which the extent of reaction was determined by measuring the amount of carbon dioxide evolved. I.4348y n-Butyric 21 59-62 (59) 1.01 mole of acid was mixed with 5 g. and dried over anhydrous magnesium sulfate. The mixture was then heated and a small fraction of the bromine was added. Value given for 0. 1-Bromopropane 53 70-74 (72 )" 1. HERYNK.4569) Dodecanoic a Numbers in parentheses refer to literature values. %- HgO b-1Acid low) AgnO PbO Pbso4 CdO Propionic Palmitic Acid chlorides 87 76 78 12 42 45 5 (CClr) 8 After trying a number of variations of the method. 78. the red mercuric oxide. SOC.4478) Heptanoic 1-Bromoheptane 31 175-180 (177. 2264 (1956). liturature value given for 5 mm. 4832)b Chloroacetic C2HzC1. cupric.416 DAVIS. TABLE I11 PERCENTYIELDS BASED N AMOUNT CARBON O OF DIOXIDE PRODUCEDO -Yield. then the remainder of the bromine was slowly added. Benzoyl chloride 7 (CCla) Palmitoyl chloride 8 (cc4) Butyryl chloride 45 a Using 1.. The mixture was kept warm for 1 hr.1. 7 '0 B.p. and V.430126(1.. TABLE I1 PERCENTYIELDS BASED AMOUNT CARBON ON OF DIOXIDE PRODUCED~ Acid8 CChb CiHnClrb Chloroacetic 71 (38) Trichloroacetic 82 (13) Propionic 94 n-Butyric 99 (53) Isobutyric 90 (21) 77 (61) 2-Methylbutyric 2-Ethylbutyric 80 87 (17) Trimethylacetic 85 (13) Hexanoic 88 (31) Cyclohexanecarboxylic 88 90 (37) Heptanoic 59 (31) Octanoic 2-Ethylhexanoic 76 92 69 Decanoic 67 (46) Lauric 91 Myristic 90 81 Palmitic 95 Stearic 41 71 Phenylacetic Diphenylacetic 51 48 83 Benzoic 40 76 p-Toluic 54 Anisic p-Nitrobenzoic 0 70 85 Phthalic 20 Terephthalic 19 33 Malonic 85 Glutaric 53 Hexanedioic 29 75 Octanedioic 66 79 Decanedioic Using red mercuric oxide and either carbon tetrachloride or lll. magnesium. and sodium and titanium dioxides.4505) cc4 Octanoic 1-Bromoundecane c1 c4 46 55-60 (114)d 1. As the isolation by fractional distillation of a small amount of liquid product from a relatively large volume of solvent is a time-consuming operation and normally is not quantitative.43512' (1.2.4450) Hexanoic cc4 1-Bromohexane 37 150-158 (159) 1. Propionic acid dissolved in tetrachloroethane and treated with bromine in the presence of an oxide of each of the following gave no reaction: aluminum.5) 1. then with water." nDOC. J. For the effectiveness of solvents other than carbon tetrachloride and tetrachloroethane see Table IV.

. Dehydrobromination of these phosphonium bromides with sodamide in liquid ammonia led to the corresponding triphenylphosphazines. 1964 Some 8-N-alkylidene. Singh. of solvent. and the organic bromide was separated by fractional distillation. The remainder of the bromine solution was added slowly and the reaction mixture was refluxed for 1 hr.2 N barium hydroxide solution. and dried with anhydrous magnesium sulfate.) was added slowly to a warm. Chem. spectroscopic studies. The barium carbonate precipitate was filtered off and the excess barium hydroxide titrated with standard hydrochloric acid. 40 40 0 using silver oxide and the acid chloride. The latter method proved to be of . This probably was due to the higher boiling point of the tetrachloroethane which permitted a higher reaction temperature. Experimental For the preparation and isolation of the organic bromides. 0.. In many cases higher yields were obtained with tetrachloroethane as solvent than with carbon tetrachloride. Chem. 46. Singh. Intern. represent a convenient tool for the synthesis of certain. The following is typical of the method used. three-neck flask.FEBRUARY 1965 p31-Hl COUPLING STRUCTURE FOR DETERMINATION 417 TABLE IV BASED AMOUNT CARBON ON OF DIOXIDE PERCENTYIELDS PRODUCED' Benzene Yield.-Acknowledgment is made to the donors of The Petroleum Research Fund. such as triphenylphosphinalkylimines2 and triphenylphosphin. University of Cincinnati. of dry carbon tetrachloride. Phys. in excellent yields. of carbon tetrachloride. yielding 0. containing a phosphorus-nitrogen double bond. 1. Bromodecarboxylation of Palmitic Acid. Kaplan. Singh.01 mole of acid. 574 (1983): Angew. of I-bromohexane. The flask was fitted with a dry nitrogen inlet. these compounds.Btrisubstituted hydrazines. Careful fractional distillation of the solution gave 6 g. Ziminer and G. $ '& Nitro. for support of this research and to the E.Bromo. J . chemical behavior.and -arylidenehydrazinotriphenylphosphoniumbromides have been synthetized by reacting triphenylphosphine dibromide with appropriate hydrazones. stirred mixture of 13. spectroscopy. '2.1 mole) of heptanoic acid and 22 g. 2509 (1963). (0. were proved by elemental analyses. washed. of . Ziinmerand G . and 5 g. 12% 1. and H. 11. Anoew. J . The carbon dioxide produced was swept out of the flask by nitrogen and passed through three Dry Ice traps to remove all bromine vapor and then absorbed in standard barium hydroxide solution. 2. washed with 5y0 sodium hydroxide solution and then with water. G .Chlorobenbenben. The reaction mixture was then refluxed for a t least 1 hr. Hy(1) Author to whom inquiries should be addressed. (2) H. J . stirred mixture containing 50 ml. O w .and a-S-alkyl-P-N-disubstituted hydrazinotriphenylphosphonium iodides14 respectively. Acknowledgment.. and ultraviolet and n. The ultraviolet and visible absorption data of triphenylphosphazines are compared with those of the corresponding hydrazones. Chem. b. 2 ml. stirred mixture of 0.01 mole) of palmitic acid.-Bromine (2 ml. (4) H. Ed. respectively. drolysis of dialkylaminotriphenylphosphonium iodides and a-N-alkyl-p-N-disubstituted hydrazinotriphenylphosphonium iodides furnished the corresponding secondary amines and 1.-A few drops of a solution containing 16 g.r. of red mercuric oxide in a 500-ml. 1579 (1964). separatory funnel for addition of the bromine.1 mole) of bromine in 50 ml.solvent. The carbon dioxide produced was swept out of the flask by nitrogen and absorbed in 125. Bromobenzene and tetrachlorodifluoroethane seem to offer soine promise as other solvents for this reaction.m.C&lanene zene nene F z F3 Hexane Acid Palmitic 69 82 76 67 71 58 0 0 32 Phthalic 26 Terephthalic Propionic 79 61 2 Benzoic 6 48 41 Stearic 81 60 43 2-Ethylbutyric a Using red mercuric oxide and different solvents. of dry carbon tetrachloride produced an immediate reaction when added to a warm. and dried. of standard 0. of red mercurir oxide in 150 ml.Ztrisubstituted hydrazines. The barium carbonate precipitate was filtered off and the excess barium hydroxide was titrated with standard acid. The Use of Long-Range P3I-H1 Coupling for Structure Determination GURDIAL SINGH AND HANS ZIMMER~ Department of Chemistry. To determine the per cent yield based on the amount of carbon dioxide produced. 61. (3) F. Cincinnati d l . Eng. Yellow mercuric oxide was found to be almost as effective as red mercuric oxide. Ohio Received July 17. then filtered. stirred mixture containing 50 ml. 28. 0 7 0 . The structures of all organophosphorus compounds. The CristolFirth method is simpler than the original Hunsdiecker method in that it does not require the preparation of the dry silver salt. 150-159". Recently we became interested in the synthesis and reactions of organophosphorus compounds containing a -N=P 6 linkage. mentioned above. administered by the American Chemical Society.564 g...1 mole of bromine was slowly added to a warm.p. 3 . du Pant de Nelllours and Company for furnishing samples of tetrachlorodifluoroethane and trichlorotrifluoroethane. Zimrner. of bromine was slowly added to a warm. Preparation of I-Bromohexane from Heptanoic Acid.and -arylidenehydrazinotriphenylphosphoniumiodides.4470. The preparation of 1-bromohexane is typical of the method used. Synthesis and Reactions of Some Triphenylphosphazines. These triphenylphosphazines are nucleophiles as is shown by their reactions with methyl and ethyl iodides t o yield a-N-alkyl-8-N-alkylidene. (0. and a reflux condenser.I ..1 mole of red mercuric oxide in 150 to 200 ml.1 mole of acid and 0. Chem..m. secondary amines and 1. and 5 g.0 g.0090 (goyo) mole of carbon dioxide.CzClr. (0. As a general rule aromatic and dicarboxylic acids underwent less bromodecarboxylation than did aliphatic monocarboxylic acids. 395 (1963). especially sterically hindered.l. The mixture was then filtered.0 ml.. Thus. Thes tructures of these phosphonium iodides have been verified through n. 4 These compounds reacted readily with methyl and ethyl iodides to give dialkylaminotriphenylphosphonium iodides2 and a-N-alkylhydrazino. of red mercuric oxide.and disubstituted aminoimines. Chem.483 (1963).r. 0.

24e 1. the solution was then titrated by a 1 M solution of sec-butyl alcohol in xylene or a 1 M solution of benzoic acid in tetrahydrofuran. 664. benzene. 780-25-6.18 1.: Firth. Meyers* and Michael P. 415. 6 M for n-BuLi. 591-51-5. J. The lithium compound RLi is quantitatively transformed into 2 and 3 (method A) or 4 and 3 (method B). 110. 1. In method A. these methods can be used to control the quality of the solvents. J .50e 1 .8 Experimental Section Solvents were drit?d on molecular sieves. K.30. sec-butyl alcohol/xylene as acid solution.25 1. A 5-mL aliquot of the solution to be analyzed was added a t room temperature under nitrogen to a solution of 2 g (6) (a) T.. Hernyk. Gracheva. the organolithium is converted to lithium diisopropylamide (4). sample 2 sec-BuLi in cyclohexane sample 1 sample 2 t-BuLi in pentane sample 1 sample 2 PhLi in benzene-diethyl ether solvent Et. 280 (4) Davis. 1. (3) Cristol. J . A 5-mL aliquot of the solution to be analyzed was added at room temperature under nitrogen t. Habersaat. Org. Colorado 80523 Received March 28..61e 1. A. Vol. Photoassisted Cristol-Firth-Hunsdiecker Reaction A.O THF THF Et.6sesf 1. 341. Imine 1 (2-3 drops) was added to this mixture. 44. benzylidenebenzylamine (1) are known to produce a red purple color? and this coloration remains intense as long as carbanion is present in the solution.Notes J. In method B. the added acid is equal to the initial quantity of RLi.. The solution was then titrated as in method A.49 1.26e 1. t-BuLi.67 M for PhLi. easily prepared from benzylamine and b e n ~ a l d e h y d e . Bunds. C.15e8f 1. Layer.O THF THF Et.00/0 0 1979 American Chemical Society . Org. the organolithium reacts with a solution of an excess of the Schiff base 1 by addition and metalation. Kauffmanr.76 l. Table I. titrations (method A) by an identical acid solution 0022-326317911944-3405$01.59. J. which produces anion 3 from a few drops of Schiff base 1.. Johnson. Chem.. J . Registry No. benzene or hexane as solvent. 489 (1963). 1. These methods have the advantage of using organolithium compounds in the common conditions of use of these reagents in various solvents such as diethyl ether. concentrations indicated by Aldrich were 1 . 37. W.o a solution of 2 mL of diisopropylamine (in excess) in 10 mL of solvent (see Table I). 50e 1.62e 1. Recent studies on the scope and mechanism4* of the Cristol-Firth modification indicate that the carboxylic (1) National Service Award (NIH) Postdoctoral Fellow. At the end point.PhLi.46 1.. The a Each value is an average of two or more titrations. The colored anion 3 is obtained by metalation of the Schiff base by means of RLi or the lithium amide 2 formed by addition. Chem. Method A. and hexane. I. S. Org. Khin. 1961. Method B. Walba. N. Chem. the end point was reached when the color of the solution became a persistent yellow. Results are summarized in Table I.O THF benzene hexane method A method B 1.96 The organolithium solutions were purchased from Aldrich. Reu. Zh. Fleming‘ Department of Chemistry. Sivova. S. These are single titrations. 1972. React. e sec-Butyl alcohol/xylene as acid solution.64 1. C. Titration of Organolithium Reagents Using N-Benzylidenebenzylamine ( 1 ) as Indicatora titration conditions organolithiumb n-BuLi in hexane sample 3. 669. tetrahydrofuran. after hydrolysis of a 5-mL aliquot of the organolithium solution by 10 mL of distilled water. A strong crimson color appeared immediately with the addition of organolithium.. Sivov.Ole 0. I. We used this property for the analysis of organolithium reagents by two methods (see Scheme I). Colorado State University.9ge 1. D.14 1. according t o ref 2. D. simple and rapid to realize in the laboratory. R. Ore. J... (b) L. (7) For a review see for example: R. Jr. 1957. J.lOPhenanthroline as indicator. J. of an identical solution of n-BuLilhexane in THF freshly distilled from LAM4and THF distilled some months prior to the experimentationyielded N = 1. and present a sharp and easy to observe end point. The Schiff base 1. (6) Cason.3 The latter workers found that mercuric salts of carboxylic acids could replace the more tediously prepared and sensitive silver salts in the key bromodecarboxylation step upon treatment with bromine. liquid at room temperature and can be stored as a solid at -30 OC.6 M for t-BuLi. M. 1. ~ a~ is . then distilled from LiAIHl prior to use. A. 1979 A well-known route to aryl and alkyl bromides is the Hunsdiecker reaction2 or its more recent modification by Cristol and Firth. ~ V O19. and the crimson color appeared immediately.Ooe 1. 37. N . f Benzoic acid/THF as acid solution.00 1...sec-BuLi.0oe l. (2) Wilson. Ber. J. W. Titration is made by addition of an acid solution which reacts both with the lithium amide 2 or 4. 594-19-4. 1 . Koppelmann.638 (1977). and V. Chem. and E. ( 5 ) Bunce. 26.n-BuLi.46e. of imine 1 (in excess) in 10 mL of solvent (see Table I).60 1. Fort Collins. Potapov.O THF THF Et.69 1. IF32CA 05946-02. 1979 3405 . Chem. and with the colored anion 3. Chem. 109-72-8. Obtained by titration by a standard acid using phenolphthalein as indicator. 14.Carroll. In the two methods. Org. 63. J. (8) For example. Org. A. Chem. 791 (1978). 4 M for sec-BuLi. 1965. respectively. Finally.f Watson and EasthamC method total alkalid 1. 598-30-1. 9. V. 1972.69 and N = 1. The difference between these two values is attributed to impurities contained in “old” THF. Org.

00/0 (1) (a) Centre d'Etudes et de Recherches de Chimie Organique Appliquge.. Perkin Trans. 1979 RBr % yield % yield (without light) Notes 579-75-9.CO2H. 6933 (1977). A.74-11-3. Sharts and W. 18242-39-2. 86-55-5. Registry No. 877 (1977). J . LC. H. Malissard. M.. ~~(8) C. are 1. 118-91-2.CO. Welvart. 586-76-5.(2-chloro-1.0 mmol). Chem.-4%l-~-MeOd6H.CO. Chem.0 mmol) was cautiously added via syringe.6 Phenyltetrafluorophosphorane7 (3). (3) H.lb and Claude Wakselman'"* C.H 81 75 m-ClC. however.H.CHFCH2CH3+ octenes + FSi(CH3)3+C6HSPOF2 (2) CGH13CHOHCH3 + (C2Hh)ZNCF2CHFCl-+ 1 + octenes - + (C. C6H. I. three-neck.H. 0022-326317911944-3406$01. 5'74 (1975). 108-37-2..p-C1C6H. 12.H 99 9lf n-C. carbon tetrachloride (reagent grade. Mazaleyrat.I 0 1979 American Chemical Society . n-C15HB1Br.106-39-8. n-C13H2.o-ClC6H4Br.5-(N02)2C6H3C02H. m-BrC6H4Br. and red mercuric oxide (B & A. 29. o-Me0C&I4CO2H.). Flatau.. and (diethy1amino)sulfur trifluorideg ( 5 ) (DAST) were used according to slightly modified procedures. Mazaleyrat. Robert. Tetrahedron Lett. ( 7 ) D.R.p-N02C6H4Br.CO.n-C&1C02H. 40. (b) Groupe de Recherche No. 1-naphthoic acid. nitrogen-purged.2' (neat). O-CIC&~CO~H. G.H.1. . 629-72-1.. Chem.CO. By the maximum optical rotation of 2-fluorooctane remains unknown. 125 (1974).-liahtP (with light)b 80 Oe p-CIC. H ~ ) ~ P ( O T ~ ) C H ~ + (1) + 1 Experimental Section General Procedure for Light-Assisted Bromodecarboxlyation. R. In this fashion excellent and reproducible yields of aryl and alkyl bromides were obtained (Table I). we had occasion to investigate the CFH reaction with aromatic acids. J..H - 70f Maximum Optical Rotation of 2-Fluorooctane? Survey of Fluorinating Reagents Jacques Leroy. (6) G.. 544-63-8. We now describe a further modification of the CFH reaction which simply involves irradiating the reaction mixture with a 100-W bulb. Wakselman.. Gave only Based on carpolybrominated products. as no chemical correlation has been established.H.. 15.NSOF + HF (4) Acknowledgment. 21.3CH[OSi(CH3)3JCH3 C6HbPF. acids form a diacyloxy mercury salt 1. 71001-78-0. 2-bromo-.anisic acid) the reaction gave only polybrominated products. in 60% yield from the mesylate of by (-)-(R)-2-octanol anion exchange resins. nC13HnC02H. 57-10-3. SOC.~ Recent results obtained with methyltri-n-butylfluorophosphorane5 (2) leading to 2-fluorooctane of higher optical rotation than that of San Filippo and Romano4 (stated as about 100% optical purity) have prompted us to check other fluorinating reagents. Cambon. 1979 a Reactions run in carbon tetrachloride a t reflux.. and C. G. J.CH(OTs)CH3 + (n-C4Hg)3PFCH.o-BrC6H4Br. J . p-BrC6H.H t o RBr (HaO-Br. H o-MeOC.586-78-7.CO. "purified". 2 C6H13CHFCH3 octenes + ( ~ Z . J .. Thus. Bensoam.n-C17H&02H. Rim. E.0 mmol). J. Commun.H&HOHCH3 + (CzHS)zNSF3 5 1 + octenes + (CzH. Middleton.U. 3-N02-4-C1-5-MeOC6H2c02H. Financial assistance for this study came from the National Institutes of Health (CA-16051). 44. Org. J. Chem.CO.. Actual isolated yields were much lower in those instances where isolation was attempted (see ref 4). For those aromatic acids containing electron-rich substituents (e. I. Org. M. (2) M. which then leads to the acyl hypobromite 2 followed by thermal decomposition to the alkyl bromide.CO.NCOCHFCl + H F + 4 (3) Cp.C02H.H 9 6c -40 m-BrC. During the course of other 2RC02Br 2RBr 2 studies.CO.Hg ZBQ - Optically active 2-alkyl halides are of particular interest as they can serve as models in the study of numerous reactions of organic chemistry.2-trifluoroethy1)diethylamine8 (4) (FAR).. SOC. Gelbard and co-workers have recently prepared (+)-(S)-2fluorooctane. 1877 (1973). molar ratios of RC0. H. 40. The mixture was heated a t reflux and irradiated for 3 h. N ..765-09-3. [ a I m ~ 910. owing to the poor leaving-group character of fluorine. 535-80-8. Welwart. 100-mL flask containing a spin bar and fitted with a reflex condenser were placed the carboxylic acid (10.C.H.m-ClC6H4Br. .583-53-9.. (9) W. J . The observed trend@ is that aromatic acids form rather insoluble mercuric salts and give lower yields than aliphatic acids.106-37-6. 15. and J. 108-36-1. Conversion of RC0.CO. Removal of solvent and distillation gave the bromide.H. only an estimate of optical purity has been made for 2-fluorooctane (1) based on a correlation between molecular rotation and bond refra~tion. Vol. and L. (5) Preliminary communication: J. S.CO. Soc. Tetrahedron. 99. The organic phase of the filtrate was washed with saturated NaHC03 (30 mL) and brine (30 mL) and dried (MgS04).Br. Chem.H.g..m-ClC&C02H. Hoffman. Org. 1 + + 3 C5H. 3508-00-7. P. Org. 3. CGH. France Received March 28. m-BrC6H4Co2H. Am. The flask and an adjacent 100-W bulb were enclosed in aluminum foil. bon dioxide produced. 1 2RCOzH --HgO (RCOZ).la Eric Hebert. H.H d 42 8 5f o-phthalic acid 1-naphthoic acid d n-C. SOC. or 2-iodooctaneis commonly used2 and their optical purities are determined without ambig~ity. M. Tetrahedron Lett. Table I.).H 3~NO. A. Romano. 771 (1977). The mixture was heated to reflux in an oil bath while being irradiated. I ~~ . Leroy. Into a dry. Meyers. CO. 2-Chloro-. and Z. Kane and A.Br C. F.1249 (1964). p-C1CsH4Br. 353 (1979). e See ref 5. 94320 Thiais. P. and Z.585-76-2. Sheppard. Hebert. All yields are for pure (distilled o r crystallized) products and were identified by comparison with published IR and NMR data (Aldrich or Sadtler). and bromine (Baker. 57-11-4. Private communication on a further publication in J. o-phthalic acid. J.00:1. 62-23-7. J..N.H-HgO-Br. 0 : p-NO.. 694-80-4. and cooled to room temperature. 63603-16-7. 3-N02-4-C1-5-MeOC6H2Br. Chem.. 19. Saturated aqueous NaHC03 (30 mL) was added and the mixture was vigorously stirred for 15 min.5-(N02)2CBH3Br.C .. Filippo.H 85 95f RC0.p-NO2C6H4CO2H..50:1.p-BrC6H8r.H Oe 97 3.H. J. Chem.S. respectively. The two-phase mixture was vacuum filtered through a Celite pad and the pad was washed several times with chloroform.II 95 42.3406 J.H. Jr. No. Mathey. React. Chem.5-(NO.50.H 90 90f 11-C.N.CO.~ contrast. 99-34-3. 50 mL). n-C17H35Br.H 83 86 p . 3. (4) J. 88-99-3. 1 3 o-CIC. 1514 (1975).

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