Patent GB-858134-A (GB)
Title: Improvements in and relating to fulveno-iron compounds
IPC: C07F17/02
Filed: 1957-12-09
Abstract: Fulveno-iron compounds of formula: <FORM:0858134/IV(a)/1> wherein B and B1 are monovalent or divalent hydrocarbon radicals, n and n1 being 0 to 4 when the appropriate B or B1 is monovalent and 0 to 1 when the appropriate B or B1 is divalent and R is a monovalent hydrocarbon radical or hydrogen may be used as curing agents for epoxy resins, as cross linking agents for silicone oils or may themselves be polymerized. The cure of an epoxy polymer of mol. wt. 390 containing two epoxy groups per molecule by heating with a fulveno-iron compound containg two m-aminophenyl groups is specifically referred to.  1, 1-(2, 3-dimethyl-butylidene -2,3) ferrocene of formula: <FORM:0858134/IV(a)/2> may be polymerized by an aluminium chlorideacetyl chloride complex.  The product, which is a mixture of polymers, comprises an ether-soluble portion containing acetyl groups and an etherinsoluble portion free from acetyl groups. Fulveno-iron compounds containing olefinic unsaturation in the hydrocarbon chains may be used to incorporate iron into vinyl polymers resulting in magnetically responsive products.  Fulveno-iron compounds of formula (I) above may be used as accelerators for cross-linking silicone oil by ionizing radiation. The crosslinking of a dimethyl silicon oil (100 cs) by 1, 11-(5, 8-diethyldodecylidene-6, 7) ferrocene: <FORM:0858134/IV(a)/3> is specifically referred to. The new compounds may be used also for putting iron into silicone oils for additive effects.ALSO:The invention comprises fulveno-iron compounds of formula:  <FORM:0858134/IV(b)/1> wherein B-B1 are mono or di-valent hydrocarbon radicals n and n1 being 0 to 4 when the appropriate B or B1 is monovalent and 0 or 1 when the appropriate B or B1 is divalent and R is a monovalent hydrocarbon radical or hydrogen. They may be prepared by reacting a fulvene of formula: <FORM:0858134/IV(b)/2> with an alkali-metal and reacting the derivative thus formed with an iron halide at a temperature not above 50 DEG  C., as follows:  <FORM:0858134/IV(b)/3> The fulvene used may be substituted by radicals such as methyl, ethyl, butyl, heptyl, allyl, vinyl, phenyl, aminophenyl, benzyl and tolyl, and preferably contains a reactive hydrogen on the methylene carbon (6).  Specified fulvenes are 6, 6-dimethyl fulvene, 6-(1-ethyl-pentyl)-fulvene, 6 (butenyl-3) fulvene, 6-methyl-6-phenyl-fulvene, 6-methyl-6-isopropyl-fulvene, 6-methyl-6-(1-ethyl-pentyl) fulvene, 6, 6-di-n-propyl fulvene and 6-methyl-6-(3-aminophenyl) fulvene. Ferrous halides are preferred : using ferric halides substantial amounts of fulvene and alkali metal are used up in reducing the ferric iron to ferrous. Solvents such as ethers, acetals, methyl morpholine, benzene, triethylamine and especially glycol dialkyl ethers may be used. The reaction is preferably carried out in an inert atmosphere such as nitrogen or argon.  The fulvene starting materials may be prepared by condensing cyclopentadiene with a ketone or aldehyde in the presence of a small amount of a base, or by reacting an alkali-metal cuclopentadiene or substituted cyclopentadiene with the carbonyl group of an aldehyde.  The examples describe the preparation of : (1) 6-(1-ethylpentyl) fulvene : (2) dimethylfulvone : (7) methyl-6-(1-ethyl-pentyl) fulvene and also disclose (5) methyl isobutyl fulvene : (6) methyl isopropyl fulvene : and (8) 6-methyl-6-(3-aminophenyl) fulvene.  Alkali metal derivatives are disclosed : (1) 6-(1-ethyl-pentyl) fulveno sodium : (2) dimethyl fulveno sodium : (5) methyl isobutyl fulveno sodium : (6) methyl isopropyl fulveno sodium and (8) 6-methyl-6-(3-aminophenyl) fulveno sodium.  The compounds of the invention may be used to cure epoxy polymers, may be polymerised or used to cross-link silicone oils (see Group IV(a) for all three) or used to form decocrative stains on ceramic surfaces.ALSO:Solutions of fulveno-iron compounds of formula: p   <FORM:0858134/II/1> wherein B and B1 are monovalent or divalent hydrocarbon radicals, n and n1 being 0 to 4 when the appropriate B or B1 is monovalent and 0 to 1 when the appropriate B or B1 is divalent and R is a monovalent hydrocarbon radical or hydrogen, or of polymers of such compounds may be used for decorative staining of ceramic surfaces.  The solutions applied may be: (1) an ether solution of a polymeric fulveno-iron compound containing acetyl groups; (2) a methylene chloride solution of a polymeric fulveno-iron compound free from acetyl groups, or (3) an ether solution of a fulveno-iron compound such as 1, 11 - (5, 8 - diethyldodecylidene - 6, 7)-ferrocene:  <FORM:0858134/II/2> After painting the surface and evaporating the solvent, the ceramic is heated to 350 DEG C to produce a light brown stain.