Patent GB-781065-A (GB)
Title: Improvements in or relating to motor fuel lubricating oil and grease additives
IPC: C07F17/00
Filed: 1953-11-26
Abstract: Additives for internal combustion engine fuels, jet fuels, and rocket fuels comprise organo - metallic compounds of formula MAxByCz wherein M is a metal, A is a substituted or unsubstituted cyclopentadiene radical (as defined in the Specification) and each of B and C can be the same or different and is an electron donating group such that an+5x+py+qz=Sn wherein Sn is the atomic number of an inert gas of the nth period of the Periodic Table, x is an integer from 1 to 4 inclusive, y is an integer from 1 to 4 inclusive, z is an integer from 0 to 4 inclusive, n is a period of the Periodic Table and is greater than 1, p and q are the number of electrons donated by B and C respectively, and an is the atomic number of M and is defined such that an is within the inclusive parameters (Sn-1+1) and (Sn-6) where Sn-1 is the atomic number of an inert gas of the (n - 1) the period. Many additives are specified.  In examples XI and XII there are added to commercial fuels methylcyclopentadienyl manganese tricarbonyl and indenyl manganese tricarbonyl respectively.ALSO:The invention comprises compounds of formula MAxByCz, wherein M is a metal, A is a substituted or unsubstituted cyclopentadiene radical and each of B and C can be the same or different and is an electron donating group such that an+5x+py+Qz=Sn wherein Sn is the atomic number of an inert gas of the nth period of the Periodic Table, x is an integer from 1 to 4 inclusive, y is an integer from 1 to 4 inclusive, z is an integer from 0 to 4 inclusive, n is a period of the Periodic Table and is greater than 1, p and Q are the number of electrons donated by B and C respectively and an is the atomic number of M and is defined such (Sn-1+1) and Sn - 6) where Sn-1 is the atomic number of an inert gas of the (n - 1)th period.  Specified metals are lithium, sodium, potassium, rubidium, caesium, francium, copper, silver, gold, beryllium, magnesium, calcium, strontium, barium, radium, zinc, cadmium, mercury, scandium, yttrium, lanthanum, actinium, or the lanthanum and actinium rare earths, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.  The cyclopentadienyl radical A may be one of the four classes <FORM:0781065/IV (a)/1> <FORM:0781065/IV (a)/2> <FORM:0781065/IV (a)/3> or <FORM:0781065/IV (a)/4> where R1 ... R9 are hydrogen or univalent aliphatic, alicyclic, aromatic or aliphatic-aromatic hydrocarbon radicals (of which a long list is given), and either of a or b is 0 and the other an integer greater than 1 or a and b are the same or different and are integers greater than 1.  Electron donating groups specified include H, R, CN (donating one electron); CO, RR1CO, ROR1, ROH2, H2O, RHCO, H2S, RR1S, RR1S, RR1SO, RSH, NH3, NRR1R11, NXX1X11, RNOH, PXX1X11 (donating two electrons); NO (donating three electrons; and butadiene and methylbutadiene (donating four electrons).  The compounds of the invention may be prepared by reacting a substituted or unsubstituted cyclopentadiene hydrocarbon (as defined) or a reagent capable of liberating such a radical with the desired free metal M or a salt thereof and a reagent capable of providing the desired electron donating groups, or with a compound containing both the desired metal and the electron donating group in question.  This general process may be carried in the following three ways, viz. (1) a cyclopentadienyl magnesium halide, alkali metal compound or zinc halide with a compound of the desired metal and then introducing the desired electron donating groups; (2) introducing both the cyclopentadienyl group and the electron donating groups into the metal concurrently; and (3) a compound of the desired metal or the metal itself is reacted with a compound such that the desired electron donating groups are introduced into the starting material which is then reacted with a cyclopentadienyl alkali metal compound or Grignard reagent.  Examples and a list of typical compounds falling within the general formula are given.  These compounds may be employed as additives for internal combustion engine fuels, jet fuels, rocket fuels, lubricants and greases (see Group III).