Patent GB-666713-A (GB)
Title: Manufacture of new spirans
IPC: C07C49/683
Filed: 1949-02-14
Abstract: 1 : 11 - (Hydrodinaphthyl - 8 : 81) - spirans containing the nucleus of the formula <FORM:0666713/IV (b)/1> and containing a keto group in one or both of the 4- and 41-positions (with or without further substituents, e.g. a substituted amino group or a halogen atom in one or both of the 5- and 51- positions, or also alkyl or aryl groups, and with or without further fused-on rings), are manufactured by the action of an agent capable of bringing about ring closure on a fluorene derivative of the general formula <FORM:0666713/IV (b)/2> wherein the carbon atom C1 either forms with a vicinal benzene nucleus part of a partially hydrogenated naphthalene nucleus and carries a hydrocarbon residue substituted in the b -position by a - <FORM:0666713/IV (b)/3> group (R being a hydroxy group or a halogen atom), or carries two residues of the said kind.  Such starting materials may be hydrogenated fluoranthenes (e.g. 1 : 2-dihydro- or 1 : 2 : 3 : 4-tetrahydrofluoranthenes), fluorenes, benzofluorenes, naphthofluorenes or 4 : 5-methylenephenanthrenes (4 : 5-vinylenefluorenes) or their nuclear substitution products.  The reaction may be carried out in the presence or absence of a solvent (e.g. benzene, carbon disulphide, petroleum ether or ligroin), suitable ring-closing agents being substances of electrophilic character such as aluminium chloride, zinc chloride, stannic chloride, boron trifluoride or mixtures thereof, or concentrated inorganic acids or their anhydrides, e.g. sulphuric, phosphoric or hydrobromic acid, or phosphorus pentoxide, or mixtures thereof. Examples describe the preparation of: (1) and (4) 1 : 11 - (4 : 41 - diketo - 1 : 2 : 3 : 4 : 11 : 21 : 31 : 41 - octahydrodinaphthyl-8 : 81) - spiran from b  : b 1 - (fluorenylidene - 9 : 9)-bis-propionic acid chloride or from b -(4-keto - 1 : 2 : 3 : 4 - tetrahydrofluoranthenyl-1)-propionic acid chloride; (2) 1 : 11 - (4-keto - 1 : 2 : 3 : 4 : 11 : 21 : 31 : 41 - octahydrodinaphthyl - 8 : 81) - spiran from b  - (1 : 2 : 3 : 4 - tetrahydrofluoranthenyl - 1) - propionic acid chloride; (3) 1 : 11-(2 : 2 : 4-trimethyl-41-keto-1 : 2 : 11 : 21 : 31 : 41 - hexahydrodinaphthyl - 8 : 81)-spiran from b -(2 : 2 : 4-trimethyl-1 : 2-dihydrofluoranthenyl - 1) - propionic acid chloride; (5) 1 : 11-(4 : 41-diketo-7 : 71-vinylene-1 : 2 : 3 : 4 : 11 : 21 : 31 : 41 - octahydrodinaphthyl-8 : 81)-spiran from b  : b 1-(4 : 5-vinylenefluorenylidene-9 : 9)-bis-propionic acid chloride; (6) 1 : 11-(3-methyl-4-keto - 1 : 2 : 3 : 4 : 11 : 21 : 31 : 41-oxtahydrodinaphthyl - 8 : 81) - spiran from b  - (1 : 2 : 3 : 4 - tetrahydrofluoranthenyl - 1) - a  - methylpropionic acid chloride. Fluorene derivatives of the second general formula above are obtainable by converting into carboxylic acids or acid halides (e.g. chlorides) the corresponding nitriles obtained by reacting the appropriate fluorene or hydrogenated fluoranthene compound with an acrylic acid nitrile, e.g. 1 : 2 : 3 : 4-tetrahydrofluoranthene, 2 : 2 : 4 - trimethyl - 1 : 2 - dihydrofluoranthene or 4 : 5 - vinylenefluorene with acrylonitrile, or 1 : 2 : 3 : 4-tetrahydrofluoranthene with methacrylonitrile.  Alternatively an alkali compound of a fluorene or fluoranthene may be condensed with an organic halogen compound containing the desired b -substituent.  b - (4 - Keto - 1 : 2 : 3 : 4 - tetrahydrofluoranthenyl-1)-propionic acid chloride is prepared by the action of thionyl chloride on the corresponding acid obtained as a by-product in the saponification of 9 : 9-di-(b -cyanoethyl)-fluorene for the production of the bis-propionic acid.  A sample has been furnished under Sect. 2 (5) of 1 : 11 - (4 : 41 - diketo - 5 : 51 - dibromo - 1 : 2 : 3 : 4 : 11 : 21 : 31 : 41 - octahydrodinaphthyl-8 : 81)-spiran, prepared from b  : b 1-(2 : 7-dibromofluorenylidene - 9 : 9) - bis - propionic acid chloride, which is obtainable from the corresponding dinitrile produced by condensing 2 : 7-dibromofluorene with two molecular proportions of acrylonitrile.  The Specification as open to inspection under Sect. 91 comprises generally the manufacture of any compounds containing the spiran structure shown in the first general formula above from compounds of the second general formula above in which the carbon atom C1 carries any residue (or residues) capable of condensing with the vicinal benzene nucleus to form a partially hydrogenated naphthalene nucleus.  In particular, in the production of the ketonic compounds defined above, the starting materials defined above may be replaced by compounds (likewise obtainable from the corresponding nitriles) containing ester groups, or carbonyl (aldehyde or acyl) or functionally converted carbonyl groups in place of the carboxyl or acid halide groups.  This subject-matter does not appear in the Specification as accepted.