Патент USA US3092675код для вставки
3,092,665 United States Patent 0 Mlce Patented June 4, 1963 1 Z In similar tests, compounds of the type R3P:BCl3 were _ 3,092,665 ?HGS?HINE BORENES AND THEiR P'EEEPARATi-QN Ross 3. Wagner, Whittier, Cali?, assignor to American Potash & Chemical Corporation, a corporation of Dela ware - No Drawing. Fiied h'iar. 14-, 1969, Ser. No. 14,553 8 (Ilairns. (Cl. 266-6065) This invention relates in general to phosphine borines and more particularly to phosphine borine compounds which are derived from various tertiary phosphines and boron tribromide; these phosphine borines may be added to gasoline which may contain tetraethyl lead (TEL) and which will probably contain ethylene dichloride and di bromide (in the case of automotive fuels) and ethylene dibromide alone (in the case of aviations fuels), the phosphine borines serving to reduce preignition of gaso line used as a motor fuel. found to be even less satisfactory. On standing, precipi tates formed containing boron and nitrogen (from the gasoline). Bromo analogs showed no formation of a precipitate or other deleterious affects of the type encoun tered with the tri?uorides and trichlorides. A further desirable feature of most of the phosphine bromoborines of this invention is that they are liquids or low-melting solids and all are amply soluble in hydro carbons. The latter property is especially important in a gasoline additive since additives which have low solu bilities have a strong tendency to precipitate and form solid deposits when the fuel mixture is vaporized in the carburetor. It is desirable, but not essential, that the phosphine bromoborines be low-melting materials, since this property also reduces the tendency of the additives to precipitate and form the aforementioned solid deposits. Such deposits cause malfunctioning of the engine in addi tion to defeating the purpose of feeding the additive into It is the object of this invention to provide for prepara 20 the combustion chamber. Liquids are also desirable from a material-handling standpoint since they may be blended tion of certain phosphine borines which are particularly conveniently with liquid fuels. useful as preignition additives for gasoline. Also, it is self—evident that if the compounds are to Ancillarly objects and advantages of this invention, if be used as gasoline additives, they must be su?iciently not speci?cally set forth, will become apparent in the source of the description which follows. 25 soluble in the hydrocarbon fuel material to provide the desired results. For example, for a standard leaded Broadly, this invention concerns phosphine borines of the general formula R3PzBBr3, where each R is hydro gasoline containing 3 ml. per gallon of tetraethyl lead, it is necessary that the phosphorus-containing additive be carbon and where the number of carbon atoms in the present at 0.3 theory, which represents 3.07 org-atoms three R groups totals 4 to 30, inclusive. These materials may be added to unleaded gasoline or 30 of P per gallon or 0.81 ‘mg-atoms of P per liter. In gasoline which contains TEL or a similar metal-containing anti-detonant such as methylcyclopentadienyl manganese tricarbonyl, and serve as excellent preignition additives therein, as set forth in greater detail in our co-pending the table below, the solubility of certain of the com pounds of this invention in petroleum ether is con trasted with the solubility of various other closely related compounds: ‘ application Serial No. 796,223, ?led March 2, 1959. When the phosphine borines of this invention are added to' motor fuel, the resulting motor fuel is found to have a low preignition index and a high resistance to detonation knocking. Another effect of the use of these phosphine borines is to decrease the tendency of the 40 presence of TEL in the gasoline to raise the octane re Sol. in Unleaded Gaso line-Type Hydrocar Compound ,M.P., ‘‘ C. quirement of the engine in which the gasoline is used. A further ‘advantage of these phosphine borines as gasoline additives is that such phosphine borines are highly re sistant to hydrolysis, as a result of which they have 45 little tendency to be “leached” from the fuel by the action of such free Water as may be present. In this respect, the phosphine borines as a class are decidedly advan bon) B.R, 65—100° C.) g./1. (CHahCzHrPZBBl'a CH3(C2H5)2P:BBr3 (OH3).1P:BBr3._.__ (O2H5)3P:BBr;-___ (n-O3H7)3PZBB1'3__ 155. 5-157. 5 120-121 267-268 118-119 mmoles/l. 1. 5 3. 2 0. 175 5.1 4. 4 9.1 0. 54 13.8 ___ 159-161 3. 65 8. 8 (11-04119) 3P : BBra _____________ __ 200-201 2. 8 6. 2 tageous as compared with most other boron-containing gasoline additives which are highly vulnerable to hydroly 50 sis. The phosphine borines of this invention are also superior to the closely related compounds R3P:BCl3 and R3P:BF3 (e.g., (CH3)3P:BCI3; (CH3)3P:BF3) with re spect to hydrolytic stability. For example, in a series of As noted in the table above, the hydrocarbon used was unleaded, but it has been found that the solubility of the tests wherein 0.81 mg] atoms P/l concentration in leaded 55 phosphine borines in the 65-110° C. B.'P. hydrocarbon gasoline is stored in the presence of water in an iron corresponds closely to the solubility of the same phos container for several months (which conditions simulate phine borines in leaded gasoline. Hence, the table above the environment commonly found in re?neries, shipping gives an accurate picture of the solubility of the various and storage facilities and in automobile gasoline tanks), phosphine borines in leaded gasoline. it was found that the ?uoro derivatives apparently con 60 The phosphine borines of the present invention, while vert to the water soluble dimeric form sufficiently soluble in hydrocarbons, are relatively insolu ble in water and this also tends to maintain quantitative 3,092,605 3 4. temperature, after which the solvent and excess boron tribromide were removed by distillation at reduced pres sure. The remaining white powder was slurried with 100 ml. of hexane, ?ltered, washed with hexane, dried. and re requirements at low levels since there is essentially no loss by extraction. ‘Finally, the fact that bromine may here be introduced in the form of the phosphine borine compound permits crystallized from isopropyl alcohol. The yield was 34.6 g. (0.094 mole) 74% of white needles melting at 118 a reduction in the amount of ethylene dihalide normally required in leaded gasoline; this enables a reduction in costs by providing means for simultaneously controlling ignition and scavenging lead with a single additive. 119° C. Analysis.—Calcd. for C6H15BBr3P: P, 8.40; Br, 65.02; B, 2.93. Found: P, 8.45; Br, 64.60; B, 2.92. Such a phosphine bromoborine, when used as a pre ignition additive for gasoline, combines the known bene 10 ?cial effects of both boron and phosphorus in a single molecule of relatively small size and lower molecular Example IV In a similar manner, 6 g. (0.0375 mole) of tri-n-pro pylphosphine and 12 g. (0.047 mole) of boron tribromide in 100 ml. of hexane yielded 13 g. (0.032 mole, 84.4%) of white crystals from isopropyl alcohol melting at 159— 161° C. weight; but, unexpectedly, small amounts of phosphine bromoborines are found to be superior to mixtures of in dividual commercially~available preignition additives con taining phosphorus on the one hand and boron on the other. Further, the phosphine borines are relatively non Analysis.—-Calcd. for C9I-I21BBr3P: P, 7.54; Br, 58.36; reactive and resist decomposition, even at relatively high B, 2.63. Found: P, 7.60; Br, 58.58; B, 2.63. temperatures. The range of effective concentrations for these ma 20 terials and details of their effects on gasoline will not be further described here as this information is set out in the aforementioned co-pending application. Example V A nitrogen-swept 250 ml. round-bottom flask was charged with 100.73 g. (0.402 mole) of boron tribromide A general preparative method for these new compounds is as follows: To a weighed quantity of the boron tri 25 while the flask was held in an ice bath. To the flask was slowly added 81.33 g. tributylphosphine at such a bromide contained in a suitable reaction vessel in added rate that the reaction mixture was maintained in a fluid an equimolar quantity of the tertiary phosphine at such state without excessive re?ux of the BBr3. A good yield a rate that the evolved heat can be dissipated by external of the addition product, (C4H9)3P:BBr3, M.P. 200—201° means and the reaction mixture may be maintained as a liquid. C., was obtained after recrystallization from either n The reverse addition may be used if more con venient. A large number of tertiary phosphines are known; see, for example, pages 31—37 of Organophos propyl alcohol, ethyl acetate, or a methanol-ethyl acetate mixture. phorus Compounds, Kosolapotf, John Wiley & Sons, New York, 1950. Example VI are for illustrative purposes only and are not to be in terpreted as imposing limitations on the scope of the phosphine and boron tribromide were reacted both with and without a solvent. The yield was 94%; the compound obtained has a M.P. range of 119-121“ C. Speci?c examples are set forth below showing the 35 preparation of the materials of this invention, but these invention other than as set forth in the appended claims. 40 Example I In the fashion of Example III above, phenyldimethyl Example VII In a similar manner, the compound Into an evacuated tube cooled to -l96° C. were con densed 2.3 g. (25.5 mmoles) dimethylethylphosphine. fol lowed by 6.5 g. (25.9 rnmoles) boron tribromide. The 45 tube was sealed and warmed to ~78° C., whereupon im m,p'C2H5C6I-I4(CH3 ) 2P : BB1}; was prepared in a 72% yield and found to have a melt ing point range of 68—90° C. The wide range was due to the fact that the compound was a mixture of the m mediate formation of the adduct dimethylethylphosphine tribromoborine, (CH3)2C2H5P:BBr3, occurred. The tube was opened at room temperature and the solid product p-isomers. was recrystallized from ethyl alcohol to give 7.9 g. (23.2 50 andAnalysis.—Calcd. for CmHlsBBrsP: P, 7.43; Br, 57.52; mmoles, ‘91% yield) of colorless solid melting at 155.5— B, 2.60. Found: P, 7.38; Br, 57.30; B, 2.60. 157.5 ‘‘ C. Analysis.--Calcd. for C.,HuBBraPz P, 9.09; Br, 70.37; B, 3.18. Found: P, 9.01; Br. 70.2; B, 3.15. Example VIII 55 In a similar manner, compound Example II 2,5-(CH3)2C6H3(CH3)2P:BBr3 In a similar manner, 1.3 g. (0.0125 mmole) of methyl diethylphosphine and 10.4 g. (41.5 mmoles) of boron was prepared in an 86% yield and found to have a melt tribromide in 30 ml. of hexane yielded 3.4g. (0.0096 60 ing point range of 161-163" C. mmole, 77.3% yield) of the adduct methyldiethylphos Analysis.—Calcd. for CmH15BBr3P: P, 7.43; Br, 57.52; phine tribromoborine, CH3(C2H5)2P:BBr3, from methyl B,2.60. Found: P, 6.88; Br, 56.86; B, 2.63. alcohol melting at 120-121° C. Analysis.-Calcd. for C5H13BBr3P: P, 8.73; Br, 67.59; B, 3.05. Found: P, 8.78; Br, 67.50; B, 3.11. Example 111 65 Example IX In a similar fashion, the compound 2,5-(CH3) 2C5H3(Il-C4H9)2P : BB1]; To a solution of 15 g. (0.127 mole) of triethylphos 70 phine in 150 m1. of hexane cooled to —-78° C. by means was prepared in 88% yield and found to have a melting of a Dry Ice bath was added slowly, with stirring, 37.7 point range of 107—109° C. Analysis.—Calcd. for C16H2qBBr3P: P, 6.18; Br, 47.86; g. (0.15 mole) of boron tribromide under an atmosphere B, 2.16. Found: P, 5.99; Br, 47.26; B, 2.21. of argon. The resulting white solid was stirred for 15 Following the method set forth above, various other minutes in the cooling bath and for one hour at room 75 8,092,665 5 materials may be prepared in like fashion; e.g., see the table below. Phosphine selected from the class consisting of alkyl and cycloalkyl together with an aryl radical; each of said alkyl radicals Phosphine Borinc Product CHz(CI-IQ) POH3 ___________________ ._ BB1‘; ___ (CH3)CH2(CH2)4PIBBI3 CH2(CH2)5P CH3 ___________________ __ BBra -__ (CH3) CH2(CH2)5P:BB1‘3 OH?CHmPCHa ___________________ __ BBra --_ (CH3) CH2(CH2)aP:BBra As aforementioned, a test for preignition has been de vised and the new compounds of this invention have been compared with other closely related compounds, as a result of which the superiority of these compounds has been made apparent. Brie?y, this test involves measur ing the number of instances per unit time of motor opera tion in which ?ames occur in the combustion chamber prior to the time at which the normal ?ames produced by the spark occur, in general following the procedure de scribed =by Hirschler, McCullough and Hall, SAE Trans. 62, 40, (1954). E?iciency of the preignition additive can be measured by the preignition index, which is a per centage of such abnormal ?ames occurring in the additive containing test gasoline as compared with the base fuel, i.e., the same TEL-containing gasoline which has not been treated with the preignition additive. Obviously, many modi?cations and variations of the invention may be made without departing from the spirit and scope thereof and only such limitations should be imposed as are indicated in the appended claims. This application is a continuation-in-part of applica tion Serial No. 796,294, ?led March 2, 1959, and now abandoned. I claim: having between one and twelve carbon atoms, the said R groups together containing from eight to thirty carbon atoms. 2. The compounds of claim 1 wherein ‘at least one R is phenyl. 3. The compounds of claim 1 wherein at least one R is Xylyl. 4. The compounds of claim 1 wherein at least one R is ethylphenyl. 5. The compound C6H5(CH3)2P:BBr3. 6. The compound C2H5C6H4(CH3)2P:BBr3. 7. The compounds 2,5-(CH3)2C6H3(CH3)2P:BBr2. 8. The compound 2,5-(CH3)2C6H3(n-C4H9)2P:BBr3. References Cited in the ?le of this patent UNITED STATES PATENTS 2,879,301 Stewart et al __________ __ Mar. 24, 1959 1,035,628 Germany _____________ .._ Aug. 7, 1958 FOREIGN PATENTS OTHER REFERENCES Hewitt et al.: J. Chem. Soc. (London), pp. 530-4 1. Compounds of the general formula RsPzBBr3 where 55 (1953). R3 is selected from the group consisting of two radicals Brown: J. Chem. Soc., page 1250 (1956) (London).