I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
September 1954
(39) Danner, J. JI., and Zerweck, W., Brit. Patent 688,651 (March 11, 1953). (40) Eley, D. D., and King, P. J., J . Chem. Soc., 1952, p. 2517. (41) Eley, D. D., and King, P. J., Trans. Faraday SOC.,47, 1287 (1951). (42) Englert, R. D., and associates, J . Am. Oil Chemists' SOC.,30, 337-9 (1953). (43) Ettel, V., and associates, Chem. Listy, 46, 232-7 (1952). (44) Ferguson, L. N., Chem. Eews., 50, 47 (1952). (46) Fierens. P. J. C.. Industrie ehim. belae. 17. 3-8 (1953). (46j Fuson, R. C., and Cooke, H. G., jr., J . Am.'Chem. Soc., 73, * 3515-16 (1951). (47) Fuson, R. C., and Rouse, H. O., J . Org. Chem., 18, 496-500 (1953). (48) Goebbel, C. G. (to Emery Industries, Inc.), U. S: Patent 2,573,433 (Oct. 30, 1951). (49) Granger, R., and associates, Compt. Rend., 234, 1058-60 (1982). (50) Haddock, N. H., Slinger. F. H., Wood, C. and Imperial Chemical Industries, Ltd., Brit. Patent 686,391 (Jan. 21, 1953). (51) Hennion, G. F., and associates, J . Org. Chem., 17, 1102 (1952). (52) Inatome, M.,and associates, J . Am. Chem. Soc., 74, 292-5 (1952). (53) Ingram, J. (to Monsanto), U. S. Patent 2,626,253 (Jan. 20, 1953). 154) Kimoto, S.,and Asaki, K., J . P h a r m . SOC.J a p a n , 72, 300-3 (1952). (55) Kosolapoff, G. VI.,J . Am. Chem. Soc., 74, 4119-20 (1952). (56) Kosolapoff. G. M. (to Monsanto Chemical Co.), U. S. Patent 2,594,454 (April 29, 1952). (57) Krauss, W., and Grund, H., ~ ~ a t u r w i s s e n s c h u f t e n40, , 18-19 (1953). (58) Lien, A. P., and McCaulay, D. A., J . Am. Chem. Soc., 75, 2407 (1953). (59) Ibid., p. 2411. (60) ;\IcCaulay, D. A., and Lien, A. P., Ibid., 73, 2013 (1951). (61) Ibid., 74, 6246 (1952). (62) AlcCormack, 1%'. H., and Stilmar, F. B. (to Du Pont), U. S. Patent 2,613,129 (Oct. 7, 1952).
1835
(63) Alan, E. H., and Hauser, C. R., J . Org. Chem., 17, 397-403 (1952). (64) Mason, C. T., and Gist, L. A., Jr., J . Am. Chem. Soc., 73,4644-7 (1951). (65) Illessina, N., and Brown, E. V., Ibid., 74, 920-3 (1952). (66) Xlosby, W. L., Ibid., 74, 2564 (1952). (67) Alosby, W. L., J . Org. Chem., 18, 964 (1953). (68) Nukherji, S. M.,and Bhattacharyya, N. K., Ibzd., 17, 1202-9 (1952). (69) Karston, H. E., and Peters, A. T., J . Chem. Soc., 1950, p. 729. (70) Parkinson, A., and Wardleworth, J., Brit. Patent 675,863 (July 16, 1952). (71) Reinheimer, J. D., and Smith, J. C., J . Org. Chem., 17, 1505-7 (1952). (72) Richter, C., and Frey, W. (to Cilag Ltd.), Swiss Patent 278,939 (Feb. 16, 1952). (73) Scalera, M., and associates (to American Cyanamid Co.), U. S. Patent 2,628,964 (Feb. 17, 1953). (74) Schoental, R., J . Chem. Soc., 1952, pp. 4403-6. (75) Shaver, F. W. (to B. F. Goodrich Co.), U. S. Patent 2,587,540 (Feb. 26, 1952). (76) Shorygina, N. V., Zhur. Obshchet Khim., 21, 1273-6 (1951). (77) Somerville, W. T., and Spoerri, P. E., J . Am. Chem. SOC.,74, 3803-7 (1952). (78) Takegami, Y., and Shingu, H., Bull. Inst. Chem. Research, Kgoto Univ., 24, 8 4 (1951). (79) Taylor, W. J., Wagman, D. D., and associates, J . Research YutZ. Bur. Standards, 37, 95 (1946). (80) Taylor, E. P. and Watts, G. E., J . Chem. SOC.,1952, pp. 1123, 5054. (81) Truce, W. E., and Milionis, J. P., J . Ant. Chem. Soe., 74, 974-7 (1952). (82) Truce, W. E., and Olsen, C. E., Ibid., 74, 4721 (1952). (83) Wood, C. (to Imperial Chemical Industries Ltd.), Brit. Patent 681,917 (Oct. 29, 1952). (84) Young, D. W. (to Standard Oil Development Co.), U. S. Patent 2,603,665 (July 15, 1952).
HALOGENATION OGDEN R. PIERCE, DOW CORNING CORP., MIDLAND, MICH. Commercial production OF halogens and halogen acids is still at a high level and shows an increase over the previous year. Production OF chlorinated organic compounds is slightly lower than previously. In the field of chlorination research, process improvements have received much attention with emphasis on preparation of olefins and polymers. Fluorination research has been devoted primarily to synthesis of olefins and a study of polymerization techniques. Considerable work has been done in the area OF oxygen-containing compounds, especially esters. The field of bromination has not been extensively studied and is concerned with aliphatic and aromatic hydrocarbons. Iodination still remains the least explored area of halogenation and only a few investigations are reported.
T
HE production of chlorine, hydrogen chloride, and hydrogen fluoride has increased during the past gear as shown in the comparative total tonnages for the years 1952 and 1953
Clz
HC1 HF
1952 (Short Tons) 2,608,690 683,742 41,512
1953 (Short Tons) 2,796,070 771,241 51,048
The production of chlorinated organic compounds has shown a slight decline over the previous year. The total production figures are given below (47A). CCla CaHsCl c2c14 CzHC13
1953 (Lb.) 239 206 384 356:417 :276 151,666,704 324,751,572
CsHeCls
DDT 2,4-D 2,4,5-T
1953 (Lb.) 59,793,110 83,981,474 25,214,630 5,112,129
CHLORINATION PARAFFIN HYDROCARBONS
Chlorination of methane (bA) a t 1500 to 4500 c. in the presence of ultraviolet light at a tirne of 5 minutes produced tetrachloroethvlene (35% conversion) as well as a high yield of carbon tetrachloride. A commercial process for the chlorination of methane (3'5A) yields an 85 to 90% conversion of methane to chlorinated products a t 650" to 700' F. By varying the reaction conditions a desirable product distribution may be obtained. Reaction of methane with chlorine ( 9 A ) a t 315' C. in a tube packed with fuller's earth formed 46% CzCl.,, 45% CCl,, and 9% CsCl6 and C2C16. The conversion based on chlorine was 67%. A novel chlorination apparatus ( 1 A )has been described in which both light and heat are obtained for reaction purposes from an external reaction of hydrogen and chlorine that is conducted in a concentric tube inside the reaction tube. I n this manner, methane gave both CCla and CHC13 together with the bpproduct hydrogen chloride. Chlorination of ethane ( I l A ) at 400" C. and a contact time of 0.19 second gave the following results: C2HsC1, 4%; C2H6C1, 60.2%; CHClzCHI, 29.2%; CHzClCH2C1, 6.401,; and CHCll-
INDUSTRIAL AND ENGINEERING CHEMISTRY
1836
CHr('1, 0.2%. An over-rill ~ ~ o i i v r i ~of ~ i81.2% on based on et,hane was obtained. Chlorination of hexaiie (3f.1 ) :it 97" C. arid a contact tinw of 0.2 to 0.3 second yielded :i 6 i % mixturc of the primary and secondary chlorides. Heptnne \vas cliloririatcd at 157" C. to produce 3%secondary m d 1 4 % primary chloridcs; octane required a temperature of 177' (', to yield 66% secondary ant1 32Yeprimary chlorides; noiiaiie a t 187" C. gave 65'3, secondar>and 3370 primary chloriilcs. ant1 decane react'ed at 197' C. to give 61% secondary and :37% primary chlorodecanes. .4 sunimary (SZA) of the chloiination of hydroc2trbons states that increased molecular n-cighi of the liytli~ocarbonleads to lesser rea(:tiori selectivity and greater amounts of dichlorides. h high ratio of hydrocarbon to chlorinc is said l o be beneficial for t>heformation of primary chlorides. S-chlorosuccinimide ( 7 Aj is suititbk for the chlorination of saturated compounds. It a t t a c h mcthylene groups more reatlily than methyl groups.
AROMATIC HYDROCARBONS
The preparation of benzeiic hesoohloride (29A) was accomplished in a 95% conversion by rcact,ion of chlorine and benzenc cwntinuously a t 20' to 80" C. in the presence of actinic light at :L pressure of 5 pounds per square inch. An alternative iiicthod (&?A, 91A) involves the m e of :queous sodium hypochlorite a t -10" C. The reaction is reported l o be rapid and the conversion of benzene to CsIlsCls amounts t o 80 to 90%. Five isomers of benzene tetrachloride (S3Aj have been isolated from the iodine-catalyzed photocheniical chlorination of benzene. The steric st,ructures of these isomers have been established by chlorination to benzene hexachloride, and the structural relationships have made possible a chemical confirmation of the configurations of the benzene hexachlorides. A similar chlorination of inonochloro- and p-dichlorobenxenc ( 1 9 A ) resulted in the formation of I 3,4,5,6-pentachloro-1-cyclohexene and 1.2,3,.+,5,6-hesachloro-l-cyclohexene, respectively. A% st,udy of side-chain and nuclrar chlorination (1SA) of alkylaromatic compounds in light, indicates that, although side-chain substitut,ion predominates, sonic nuclear substit'ution occurs in cert,ain cases. The use of chlorinci acetate (8-4)as a chlorination agent demonstrated its grwter. reactivity over ehloririe when used as an electrophilic r e a c b n t . 4 review (14A) of the chlorination of hydrocarbons for thc: purpose of producing pctrochcmicals is recommended i o t h c reader. ~
OXYGEN-CONTAINING COMPOUNDS
Rcxaction of methanol (41-4) with coiiceiit,rat,ed hydrocliloric acid a t 100" C. yields 97% in(>tliylcliloritie. The use of phosphorus trichloride (1211j as a mciins of replacing the hydroxyl group in alcohols has been described, anti the reaction is postulated as the stepwise alkoxylation of phosphorus followed '05dealkylation of t,he trialkyl phosphite. Phenol (@A) was chlorinated in the temperature range of 130' t o 180' C. in the presence of ferric chloride t o give octachlorocyclohexenone in good yield. The selective chlorination (g2A) of 2,5-dichlorophenol to 2,4.5-tricblorophenol in the presence of 2,4-dichlorophenol can be accomplished by treating the mixed phenols Tyith one molar equivalent of chlorine at 40' to 60" C. The reaction of o-cresol ( 4 a A ) with chlorine a t 55' oduced 6-chloro-o-cresol as the predominant isomer in high The chlorination of isobornyl acetate (45~4) at, 70" C. in carbon tetrachloride solution resulted in a, product coiit,aining 44 to 47% chlorine that was an effective insecticide. A similar chlorination ( 4 A ) of camphor produced a polgchloro derivative containing €18.77~chlorine that also was an excellent insecticide. An (Xicient method ( 2 7 A ) of chlorinating copper phthalocyanine
Vol. 46, No. 9
comprises treating it with clilorine a t 90" C. in a chlorosulfonic acid solvent containing sulfur monochloridc and iodine chloride. OLEFINS AND POLYMERS
-4description (3UA) of the comimrcial hydrochlorination of d i y l e n e at 40' to 50" C. in the presence of aluminum chloride rccommeiidcd to the reader. The reaction of ethylene (%"A) th chlorine at 50" C. and 20 pounds per square inch yielded ethylene dichloride. A similar chlorination (24A j of dilut'e mistures of ethylene in incrt gases under pressure permits the conversion of such mixtures to olefin dihalides. a% stud!. vaiiahles in the formatmion of ethylene chlorohydrin s!io\r-e:l the rccyclo-ty pe react'or to be superior to t,h(? &le-pass column. A revien- (2621) of the preparation of vinyl chloride from dilrltc, acetylene ia suggested reading. Thc reaction (36Aj of acetylenc~ with hydrogen chloride in the presence of activated carbon impregnaied n.ith mcicxric chloride yielded 85% vinyl chloride. Chlorination (48.1) of acetylene at' 400" to 600" C. and a eontact time of 0.5 second prodcccd tetrachloroethylene in high yield. The reaction of propene (16'il) with hydrogen chloride :ii 20" C. in a silent electrical discharge effected a 3% conversion pt:r pass to 2- chloropropanc. Chlorination of propene (%?A)a t 300" to GOO" C. a t a contact timc of 0.2 second produced a mixturc? of polychlorinated materials containing principally 1,2-dichloropropene. Propyne ( 8 5 8 ) was chloriiiatcd at 70' C. to form 1,1,2,2-tetrac!iloropropanein 65'34 yield. Reaction of polychloropciitanes (28A) with chlorine a t 100" (>, and a cont,act time of 6 seconds in the presence of floridin yieldwl 90% hexachlorocyclopentadiene. Chlorination (288j of cyclopentadiene with sodium hypochlorite a t 25' C. in the presericc: of sodium sulfaniate produced hexac1ilorocycloDentaeiiene in 55% yield. Cyclohexene ( 1 6 9 ) \vas chlorinated a t 25" to 40" C, in the presence of benzoyl pcroxide to yield a product coiitainiily 74% chlorine having insecticidal properties. The photochemic:al chlorination ( 5 4 ) of dicyclohexadiene in carbon tetrachlorid(, solution a t 50' to 80' C . gave a product containing 5 t o 12 chlorine atoms per molecule that showed high insecticidal a('tivity. A similar chlorination (614) of 2-methylbicyclo[2.2.i~-.i-heptene produced useful insecticides. MISCELLANEOUS
The reaction (4411) of the silver salts of carboxylic: acidr with halogens has been reviewed and is recommended rcading. Thrb chlorination ( 4 O A ) of methylchlorosilanes in the presence of ultraviolet light results in a series of chlorosubstihted products The reaction ( S A ) of alkoxytrichlorosilanes with chlorine produces a series of polychloro products among n-hich vxre trichloromet,liosy- and pentachloroetlioxytrichlorosilaiie. Chlorination (384)of tiifluoroniethane a t 350" C. and a coiitact t h e of 18 secoutls produced both CF& and CIIF2C1 in a total conversion of 77 %. Similarily, bromodifluoromethanc was chlorinated at 230" C. to iorm CF2BrCl. The reaction of CF:CI-I,CR, ( 2 7 A ) n-ith chlorine a t 365' to 450" C. g a m both thc 2- and 3-chloro derivatives. The chlorination (.CaA) of fluorine-containingcompounds of the general formula Cn1FCI m d ('Cl=CClCF&FClCF2 i._
-----_I
Reaction ( 4 f B )of CCl=CClCF&FzCF2 L---_
-i
Dow Corning Carp. Unit Process for Preparation of M e t h y l Chloride The rat,e of polymerization (27'B) of chlorotrifluoroethSleiie by a persulfate system was relat'ed to the ionic strength rather than the p H of the aqueous phase. A kinetic study (85B) of t'hri peroxide-catalyzed bulk polymerization of chlorotrifluoroethylene shows that the reaction is zero order for 60 to SO% conversion, the rate varies as the 0.7 to 0.8 power of the peroxide concentration, and the over-all activation energy is 17 kcal. per mole. A suspension polymerization system ( I 4 B ) for chlorotrifluoroethylene comprised Rater, sodium bisulfite, ferric phosphate and tert-butyl perbenzonte. The system yielded a 90% conversion to high polymer in 9 hours a t 250' C. Copolymerization (58B) of chlorolrifluoroethylene with tetrafluoroethylene a t -20" to 0' C. using trichloroacetyl peroxide gave a plastic material of good chemical and solvent resistance. Pyrolysis (59B)of a solid polymer of chlorotrifluoroethylene at 370" C, yielded a l p e r oil fraction than t,hnt, obtained by honiopolymerieation of the monomeric ethylene. Copolymerization (RSR) oE 1,l-tiichlorodifluoroethylenen-ith vinylidene cyanide at 40" C. in the, presence of a peroxide gave a resinous product capable of forming films and filaments. Terpolymers (RIB) prepared from 1,l-dichlorodifluoroethylene, butadiene, and vinylidenc chloride in an emulsion system using a persulfate initiator resembled highly plasticized polyvinylidene chloride in their stress-strain characteristics. The polymerization (1.8) of a series of perfluoro-olefins indicated that while homopolpmerization vas difficult, copolymerization was ieasihb
1838
INDUSTRIAL AND ENGINEERING CHEMISTRY
with compounds such as ethylene, vinyl chloride, vinyl esters, and vinyl ethers. The longer-chain fluoro-olefins react less readily than the lower members of the series. Homopolymerization (636') of C3Fs, C4F8,and CFZ=CFCN was achieved by exposure of t,he monomer to irradiation of a nuclear reactor. -% polymer (74B), prepared by reaction of phenyltrifluoroethylene wit,h benzoyl peroxide a t 75' C . had a relatively high soft'ening point and reduced flammability. OXYGEN-CONTAINING COMPOUNDS
A study (18B) of the surface tension characteristics of fluorinated diest,ers indicates that the surface bension decreases with increasing fluorine content. Also, the boiling points and refractive indices are lower, the densities higher, and the viscosity index lower than in the nonfluorinated diesters (2OB). A detailed study (29B, 7 5 B ) of the effect of fluorine substitution on the infrared absorption in the region of the carbonyl frequency was presented. A series ( 5 2 B ) of fluorine-containing acetoacetic esters mas prepared by reaction of a fluorinated acetate ester with sodium in ethanol, B y using sodium in an inert solvent (51B), ethyl trifluoracetate formed ethyl-r,-i,r-trifluoroacetoacetate in 30% yield. Secondary alcohols ( 7 3 3 ) can be prepared from fluorine-containing esters by using a mixed Grignard reagent composed of isopropyl and another Grignard reagent chosen from methyl, ethyl, or phenyl. The rates of hydrolysis (2@) of ethyl fluoroacetates were determined, and et'hyl trifluoroacetate was the most rapidly hydrolyzed of the three fluoroacetates. Several aromatic esters ( S 7 B ) of perfluoro acids were prepared, and the most useful preparative method was the reaction of the perfluoro acid anhydride Tyith phenol. Fluorinecontaining esters ( 2 B ) of acrylic acid were prepared by reaction of acrylyl chloride with the fluorine-containing alcohol. Polymers of these est'ers were solvent resistant elastomers. The preparation of fluoromethanol (66B) in good yield ha,s been reported by the reduction of ethyl fluoroformate with lithium aluminum hydride. Similarly, 2-fluoroethanol ( 6 6 B ) was prepared by reduction of methyl fluoroacetate. An alternative procedure comprised the reaction of ethylene chlorohydrin with potassium fluoride a t reflux temperature to give fluoroethanol in 50% yield (26B). The production of 1,l-dihydroperfluoro alcoby hydrogenation of the corresponding perfluoro acid hols (48s) esters using a copper chromite catalyst was accomplished in high yield. 4 new aynthesis (?OB) of perfluoro aldehydes was achieved by reduction of the corresponding perfluoro acid esters n-ith lithium aluminum hydride a t -70" C. Yields of TO to 80% were obtained, Perfluoroalkyl aryl ketones ( 7 8 B ) were prepared in good yield by t,he reaction of a perfluoro acid halide with an aromatic hydrocarbon, such as benzene, in the presence of aluminum chloride or aluminum bromide. Thenoyltrifluoroacetone (1SB) was produced by the reaction of ethyl trifluoroacetate wit,h sodium methoxide a t 40" 6. followed by addit'ion of acetothienone t,o t8hemixture and by hydrolysis with hydrochloric acid to give the desired fluorinated diketone. The acetylides (8SB) of sodium or potassium react viith trifluoroacetone in the presence of aqueous caustic t o give 3-trifluoromet,hyl-l-butyne-3-01 in 15% yield. The glycol, 23-bis( trifluoromethyl)-3-hexyne-2,5-diolwas obtained in 37% yield. 1,3,3,3-Tetrafluoropropyleneoxide (60B) was prepared by a sequence of reactions involving, first, preparation of tet'rafluoroacetoacetic ester followed by bromination and hydrolysis to form bromotetrafluoroacetone which u'aa treated with lit,hium aluminum hydride to give t,he corresponding alcohol. This alcohol was converted to the desired epoxide in 96% yield Tvith aqueous sodium hydroxide. Cyclic perfluoro ethers (44B)lyere obtained by electrolysis of a solution of an organic acid in hydrogen fluoride a t 20" C. using a potent,ial of 5 to 6 volts. The ethers were extremely &able mat,erials. A st'udy ( 8 B ) of the effect of structure on viscosity of a perfluoro ether indicated t'hat the
Vol. 46, No. 9
ebher has a lower viscosity than a fluorocarbon of similar chain length. The ionization constants (38B, 39B) of several unsaturated fluorine-containing acids were measured and were somewhat smaller than expected from consideration of inductive pffects. The influence of resonance effects was definitely established. Several trifluoromethyl derivatives of hydroxybenzoic acids (35B)m-ere prepared in 88% yield by reaction of trifluoroinethyl phenolates with carbon dioxide. Pentafluoropropionyl hypofluorite (54B) was obtained by direct fluorination of perfluoropropionic acid. The reaction x a s also extended to trifluoro4 solut,ion ( 1 7 B ) ol liyacetic and heptafluorobutyric acids. ' drogen peroxide in trifluoroacetic acid has proved to be tin cxcellent oxidizing agent for aniline derivatives. Its activity is attributed to the in situ formation of trifluoroperacetic acitl. ORGANOMETALLIC AND METALLOIDAL DERIVATIVES
The preparation of n-perfluoroprop-llithium ( 7 2 B ) by reaction of ?i-C3F~ILvith NeLi in ether is described. Perfluoropropyllithium gives addition reactions characteiistic of an allcyllithium. n-Perfluoropropylzinc iodide (34B) Tvas prepared by react'iori of n-C3FiI with zinc in a variety of solvents. Yields of 50 to 60% are reported. Reaction of CFJ ( 1 6 B )wit,h arsenic has produced t'hrcc products, (CF3)3As, (CF,),AsI, and CF3AsI2. A number of derivatives was prepared including various halide, cyanides, and thiocyanates. Trifluoromethyl iodide ( 7 B )reacts with phosphorus a t 200" to 220" C. to yield all three expected products, (CFB)BP, (CFB)sPI, and (CF,)PI,. These were quantitat'ively hydrolyzed to form CHF3. Fluorination ( 3 l B ) of carbon disulfide with IFS gave SFd and bis(trifluoromethy1)disulfide. The sulfur chain in the latter compound iyas unbranched. Electrochemical fluorination ( I l l ? ) of (CH3)nS in anhydrous hydrogen fluoride gave CFZSF, and (CF3)*SF4. A similar reaction of C S n produced CF3SF6! CF2(SFS)Q, and CFn(SF3)2. Reaction of carbon disulfide with fluorine (86B) in a packed tubular reactor yielded C F Q ( S F ~ ) ~ , SF8CF2SF6,CF3SF,, and S 2 F l ~ .Direct fluorination of thiophene, (63B)a t 90" C. produced no fluorot,hiophenesbut instead dcgradation products including CF4, C3F8, C ~ F ISFs, O ~ and ( C F ~ ) I . Fluorine-containing silanes ( 7 l B ) of the formulas (C,F;CkL-CH2),SiXa- sl were prepared by reaction of the correspontlingGrignard reagent with SiCl, or Si(0Et)i. A series of silnncs. (79B) of the structure (C,,F2a+l)mSiXd-m where m is 1-3 WE obtained by reaction of fluorine, silicon tetrafluoride, and calcium carbide a t 300" C. or by reaction of a perfluoroalkyl bromide with silicon-copper alloy a t 295' C. Reaction (8713) of' vinylidene fluoride and trichlorosilane a t 150" C. in the prescnce of a platinum cat'alyst produced /3&difluoroethyltrichlorosilanc in an 8 to 10% yield. Trifluoromethylphenyl silanols (46R: were prepared by hydrolysis of the corresponding chlorosilanes. These were obtained by reaction of a trifluoromethylphen).1 Grignard reagent with silicon tet,rachloride. NITROGEN-CONTAINING COMPOUNDS
A series of fluorine-cont,aining nitro compounds ( 1 2 B ) w a ~ prepared by reaction of a perfluoro aldehyde n-ith nitroalkancs and by further reactions of the resulting nitro alcohols. Perfluoro allqrl isocyanat'es ( 6 2 B ) were obtained by reaction of an amine of the general formula CnF2,-1CH2NII, wit,h phosgene a t 5' to 55' C. Perfluoro nitroso and nitro compounds (6B, 30B)' were produced eit,her by reaction of the silver salt of a perfluoro acid with nit,rosyl chloride or by irradiation of a mixture of a perfluoro alkyl iodide and nit,ric oxide in the presence of mercury. Reaction of trifluoronitrosomethane (43B) iyith aqueous sodium hydroxide yielded hexafluoroazoxymethane and trifluoronitromethane. Pyrolysis ( 6 9 B ) of a perfluoro amine gave rise to a series of products containing azomet,hines. The perfluoro amine, (C2Fj)3r a t 745' C. yielded CF,CF2N=CF, as weU. as CaFa and;
INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY
September 1954
C2F4. Fluorine-containing amines (1OB)were prepared by reduction of the corresponding amines by lithium aluminum hydride in 52% yield. 1,3-Bis(2,2,2-trifluoroethyl)urea(49B) was prepared in 84% yield by reaction of trifluoroethylamine with phosgene a t 18' C. in the presence of alkali. Reaction of pentafluoroallyl chloride (61B)with sodium cyanide a t reflux temperature gave pentafluoroallyl cyanide in good yield.
BROMINATION HYDROCARBONS AND OLEFINS
The kinetics of the gas phase photochemical bromination of isobutane (3C) to yield tert-butyl bromide was investigated in t h e temperature range of 40" to 95' C.; the reaction proceeds through an atom-radical chain mechanism. The thermal reaction in the range 112" to 130" C. has a similar mechanism. Bromination of difluoromethane ( 1 3 3 a t 500" C. and a contact time of 15 seconds gave a 61% conversion to dibromodifluoromethane By the use of chlorine ( f 4 C ) together with bromine, similar brominations could be conducted a t 300" C. resulting in less decomposition of the organic reactant. Reaction of ethylene (QC)with hydrogen bromide a t 20" C. in a silent electric discharge formed ethyl bromide in 80% conversion. Diallyl ( 6 C ) was treated with hydrogen bromide a t 0' C. to form 5-bromo-lhexene in 26% yield and 6-bromo-1-hexene in 21% yield. 1Riomo-1-propyne, 1,3-dibromopropyne, and 1-bromo-3-chloropropyne ( 8 C ) were prepared by reaction of the corresponding acetylenic derivative with alkaline potassium hypobromite. T h e use of AT-bromosuccinimide ( 7 C ) in the bromination of 2heptene was described employing carbon tetrachloride solvent with benzoyl peroxide as initiator. A yield of 99% was obtained. A kinetic study ( 1 8 C ) of the iodine-catalyzed bromination of toluene indicates t h a t the rate determining step is the loss of hydrogen bromide from a 1 : l toluene-bromine complex. A probable rate expression is
V = K[C8H5Me-Brz][BrI]
1839
of methylchlorosilanes was accomplished by passing chlorine through a mixture of the silane and bromine a t temperatures of 25" to 50' c.
IODINATION During the past year little activity has been reported in this area of halogenation. The photochemical reaction of heptene ( S D ) with iodine has been investigated in the liquid phase. The yield was nearly independent of the iodine concentration and of reaction temperature. The reaction was inhibited by dissolved oxygen. The reagent, iodine-potassium iodide-ethylenediamine ( 4 D ) , was found to be very satisfactory for the iodination of phenols, amines, and hydroxybenzoic acids. The reaction of iodine ( d D ) with triaryl or alkyl phosphites showed that a n important step in the over-all reaction is the formation of phosphite polyiodides. These can form aryl or alkyl iodides in excellent yields. The use of N-iodosuccinimide ( I D ) as an iodination agent for enol acetates gave rise to a-iodoketones or aldehydes in good yielda.
ACKNOWLEDGMENT The authors wish to express their appreciation to Mrs. Thomas Riethof for her assistance in the preparation of this article.
LITERATURE CITED CHLORINATION
Badische Anilin- & Sodafabrik (I. G. Farbenindustrie Akt .Ges. "In Auflosung") Brit. Patent 688,004(Feb. 25, 1953). Badische Anilin- & Sodafabrik (I. G. Farbenindustrie Akt.Ges. "In Auflosung"), (Otto Rommel, inventor), Ger. Patent 857,955 (Dee. 4, 1952). Breederveld, H., and Waterman, H. I., Research (London), 7, 512-514 (1954).
Buntin, G. A. (to Hercules Powder Co.),U. S. Patent 2,657,164 (Oct. 27, 1953). Ibid., 2,657,165. Ibid., 2,657,168. Buu-Hoi, Xg. Ph., and Dernerseman, P., J . Org. Chem., 18, 649-52 (1953).
De la Mare, P. B. D., and associates, Research (London), 6 , 12s-13s (1953).
Bromination (12C) of a series of alkylbenzenes was studied and the ortho-para ratios of the monobromides evaluated as follows: bromopropylbenzene-23 :77; bromobutylbenzene-37 :63; bromoisobutylbenzene-25 :75; and bromo-seobutylbenzene-21: 79. Reaction of halobenzenee ( 4 C ) with bromine in the presence of aluminum bromide was studied; bromination does not take place by a homolytic mechanism. Toluene (5C), saturated with ferric chloride and hydrogen bromide, was treated with bromine a t 25' C. to form mono-, di-, and tribromotoluenes in high yield.
Furr, J. B., and Neher, C. RI. (to Ethyl Corp.), U. S. Patent 2,644,016(June 30, 1953). Gerrard, W., and associates, J . Chem. Soc., 1953, pp. 1920-6. Harvey, P. G., and associates, Chemastry & Industrg, 1954,pp.
MISCELLANEOUS
Hertog, H. J. den, and Bruin, P. (to Shell Development G o ) , U. S.Patent 2,672,438 (March 16, 1954). Holtsman, H., and Simon, E., (to Ansbacher-Riegle Corp ) , Ibid., 2,662,085 (Dee. 8, 1953). Kleiman, M. (to Arvey Corp.), Ibid., 2,658,085 (Kov. 3,
Bromination (11C) of aromatic amines by use of a 1: 1 complex of bromine and dioxane in the presence of aqueous alkali gave the following products: p-bromoaniline, 68%; p-bromodimethylaniline, 85%; 2-bromo-4-nitroaniline, 45%; and 2bromo-4-methylaniline, 53 %. Reaction of n-butyronitrile ( I 7 C ) with bromine and phosphorus tribromide was found to form abromobutyronitrile in 60% yield. The reaction was also applicable to carboxylic acids. Thiophene (1OC) was brominated in the vapor phase a t temperatures to 750' C., and the monosubstitution product changed from the 2-bromo to the 3-bromo derivative a t the higher temperatures. Reaction of phenol ( 1 5 C ) with iodine bromide a t 25' C. was rapid, forming p-bromophenol in 80% yield. Cyclohexanone (2C) was treated with two molecular equivalents of bromine to form dibromocyclohexanone in 20% yield. The identity of the three dibromocyclohexanones was established. The reaction of silver caprylate (IC) with bromine in carbon tetrachloride solution gave n-heptyl bromide in 79% yield. Bromination (16C)
Diamond Alkali Co., Brit. Patent 701,244 (Dee. 23, 1953). Domask, W. G., and Kobe, K. A,, IND.ENG. CHEM.,46, 680-9 (1954).
300-1.
Hatch, L. E., Petroleum Refiner, 32, No. 9, 207-9 (1953). Henkel and Cie, G.m.b.H., Ger. Patent 863,942 (Jan. 22, 1953).
1953).
Kolka, A. J., and associates, J . Am. Chem. Soc., 76, 1244-9 (1954).
Koninkligjke Industrieele Maatschappij voorheen Noury, and van der Lande N. V.. Brit. Patent 685,294 (Deo. 31, 1952). Koninklijke Industrieele Maatschappij voorheen Noury, van der Lande, N. V., and Joseph Diekmann, Ibid., 685,833 (Jan. 14, 1953). Krantz, K. W. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2.665.314 (Jan. 5. 1954). Lacomble, A. L., and associates '(to Shell Development Co.), Ibid., 2,643,272 (June 23, 1953). Landau, R., and Egbert, R. B. (to Chempatents Inc.), Ibid., 2,658,088 (Nov. 3, 1953). Leitch, L. C., Can. J . Chem., 31, 385-6 (1953). Lynn, R. E., Jr., and Kobe, K. A., IND. ENG.CHEni., 46, 63343 (1954). McBee, E. T. (to Purdue Research Foundation), U. S. Patent 2,644,845(July 7,1953). Maude, -4. H., and Rosenberg, D. S. (to Hooker Electrochemical Co.), Ibid., 2,650,942(Sept. 1, 1953).
INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY
1840
(29A) AIiller, L. A , , Dunn, J. H , and Neher, C. 11. (to Ethyl Corp.), Ibzd., 2,656,313 (Oct 20 1953). (30A) Naugatuclr Chemical Co , Ptirolswn Refiner, 32, No 11, 134 (19.53). (31A) Sebrasova, 1'. d..D o i ~ l a d :A~k a d . .\'uuI: S,S..5'3,, 88, 73-6
(32d)
(33A)
(1053). Ibid., pp. 475-8. Orloff. 11. D., Rolka, A. .J.. and associates, J . ,47?1.C h e m . SOC., 75, 4243--9 (1953). Park, J. D., and associates, I h i d . , 75, 1387-8 (19%). Petroleum R e ~ h e r 32, . S o . 11, I24 (1953).
(34.1) (35A) (36.4) I b i d . , p. 134. (37A) Ibid., p. 136. (38-4)Ruh, R.P., and Davis, H . A . ( t o The Dov: Chci U. S.Patent 2,639,300 (May 19, 1953).
(39X) Ibitl., 2,639,302. (40A) Iiunge, F.. and Zimmerman, Ti., Chon. H e r . , 87, 282-7 (1954). (41A) Seko, AI. (to Edogan-a Clleinicitl Industries Co.), ,Japan. Patent 1670 ('53) (April 20, 1953j. (42-i) Simons, 3. H., and asiociates (to Minnesota llininp and hlancfacturing Co.), U. S. Patent 2,658,928 (Kov. 10,
(43A) (44-4)
(45A) (46.k) (47.4) (484 (49A)
1953). Spauldirig, D. C. (t,o B. I:. Goodrich Co.). Ibid.,2,662,918 (Dee. 15, 1953). Stanek, J., C h e m . List!), 47, 1244-9 (1953). Stonecipher, IT.D. (to IIercules Poivder Co.), U. S. Patent 2,657,166 (Oct. 27, 1953). E. S. Dept. of Commerce, Bur. of Census, SPA'+, "Pacts for industry." Scr. M19A-14 (April 8, 1954). U. S. T a d Commission, "Facts for Industry," Synthetic Organic C,heinicalsSeries 6-2-125 (1954). Wacker, A . (to Cornpang. for E1ectrochc:nioal Induitiy), Swiss Patent 292.407 iNov. 24. 19531, Zemba, J. W. (to The Dow Chemical Co.), U S.Patent 2,659,759 (Kov. 17, 1953).
FLUORINATION
(1B) Adams, R. AI., and Bovcy, F.d.,J . ~ ~ o l y n (,Sei., ~ - r 9, -181-92 (1952). (2B) Ahlbrecht. A. H., and associates (to l\Liniic.;ota 11iiiing and Manufacturing C o . ) , U. S.Patent 2,642,416 (June 16. 1953). (3B) Arend, A. G., Chem. Products, 15, 303-4 (1953). (4B) htkinson, B.,and Trenwith. A. B.,J . Ciiern. Soc.. 1953, pp. 2082--7. (5B) Badische Anilin- RS Sodsfahrilc (i. G. Farbenindudrie Akt.Ges. "In hufl6sung") (11. OTtO, €1. Tlieobald. and R.lIclan, inventors), German Parent 859,887 (Dcc. IS, 1952). (6B) Banus Chem. Soc.. 1553, p p 3755-61. (7B) Bennett, I'. IT., and iwociates, Ibid., 1953, pp. 1565-71. (8B) Brice, T. J., and Cooii, It. I.. J . A m . Chena. Soc., 75, 2921-5 (1953). (913) Bryce, H. G., Chemistry in C a n . , 5 , 202-5 (1953). (1OB) Carnahan,J . E.,aud Rampson, H. J . (to E. I. du Poiit de Nemours 6. Co.), U. S. Patent 2,646,449 (July 21, 1953). (11B) Clifford, -4. F.,El-Sliamy, FT. K.. and associates. .i.Chcm. SOC., 1953. a n . 2372--5. (12B) Cook, D. J., Pierce, 0. It.,and AIcBre, F:. T., J . A?n, Chrm. SOC., 76, 53-7 (19%). (13B) Davis, AI. W., J r . (to U. S. A , Atomic Energy Commisiion). U. S. Patent 2,670,353 (Fob. 23, 1954). (14B) Elliott, J . R., and assoriates, I s n . ESG. CHEM.,45, 1786-90 (1953). (15B) Emeleus, H. J., Bull. soc. chim. Prance. 1953, pp. 903-12. (16B) Emeleus, H. J.,and associates, J . C'hem. Soc., 1953, pp. 1552I
I .
64.
(17B) Emmons, W. D., and Ferris, -4.F., J . Am. Chenz. Soc., 75, 4623-4 (1953). (18B) Filler, R., Ibid., 75, 3016-17 (1953). (19B) Ihid., 76, 1376-7 (1954). (20B) Filler, R., O'Brien, 3. F., and associates, IND.EBG.CHEU.,46, 544-7 (1954). (21R) Folt, V. L., and Carlson, E. J . (to The R.F. Gooilrich Co.), U. S.Patent 2,657,199 (Oct. 27, 1953). (22Bj Fowler, R. D., and Burford, W. R.,I11 (to U. S. h.,Atoniic Energy Commission), Ibid., 2,651,613 (Sept. 8, 1953). (23B) Gilbert, H., and Miller, F. F. (to The B. F. Goodrich Co.), Ibid., 2,654,728 (Oot. 6, 1953). (24B) Gorin, G., Pierce, 0. R., and ZlcBee, E . T., J . Am. Cheni. SOC., 75, 5622-5 (1953). (25B) Gottlieh, 13.B., and Park, J. D. (to E. I. du Pont de Kernours 6. Co.), U. S.Patent 2,670,387 (Feb. 23, 1954). (26B) GrSszkiewicz-Trochiinon-ski, and Orysekie~ica-Trocliimonski. 0 . . Bull. soc. c i i i m . ance, 1953, pp. 123-4. (27B) Hamilton, J. AI.,.Jr., ISD. Esr:. CHEJI..45, 1347-50 (1953j. (28B) Hasaeldiiie, I{. N...J. C'hein. Soc.. 1953, pp, 3559-64.
Vol. 46, No. 9
(29B) I b i d . , pp. 3505-72. (30B) Hasaeldine, R.Ii.,and Jander. J . , Ihid., 1953, pp. 4172 :i. (31B) Haszeldine, R. K.,and Kidd. J. LI.,Ihid., 1953, pp. :,J . Am. C h s m . SOC.,75, 4W:i fi
(1953). Lindgren, V. V., and Cassaday, J. T. (to dmcrican Cyaii;rinirI Co.), U. 9. Patent 2,656,384 (Oct. 20, 1953). (5OB) 1lcRee. E. T.. Pierce, 0. R., and .Kilbourne, I-I. Chem. Soc., 75, 4091-2 (1953). (51B) AIcBee, E. T., Pierce, 0. R . , RiJbonrno. 1-1.T T , J . A , , Ib
