Patent GB-491323-A (GB)
Title: Manufacture of reaction products of alkylated aromatic hydroxy compounds and compositions containing the products
IPC: C07C37/18
Filed: 1937-03-11
Abstract: An aromatic hydroxy compound of the benzene, naphthalene or anthracene series is condensed with a chlorinated higher aliphatic hydrocarbon, and the product is acylated with an organic acid or a derivative thereof, e.g. an acid anhydride or chloride.  The final products are mainly esters, but may contain minor proportions of ketones and other bye-products.  The aromatic hydroxy compound used as starting material may be further substituted by one or more alkyl, aryl, aralkyl, aryloxy, or alkoxy groups.  Specified aromatic hydroxy compounds are phenol, benzylphenols, resorcinol, o-hydroxydiphenyl, b -naphthol, p-cresol, hydroquinone, catechol, xylenols, phenylethylphenols, methylhydroxydiphenyls, ethylhydroxydiphenyls, guaiacol, catechol monoethyl ether, dihydroxynaphthalenes, methylnaphthols, tolylnaphthols, xylylnaphthols, benzylnaphthols, methoxynaphthols, anthranols, and phenylmethylanthranols.  Suitable chlorinated aliphatic hydrocarbons are the chlorination products of heavy lubricating oil, petrolatum and paraffin wax.  Specified acylating agents are (a) saturated aliphatic monocarboxylic acids such as acetic, butyric, capric, palmitic, stearic or montanic acid, (b) unsaturated aliphatic monocarboxylic acids such as acrylic or oleic acid, (c) saturated or unsaturated aliphatic polycarboxylic acids such as succinic, oxalic, adipic, sebacic or fumaric acid, (d) aliphatic mono- or polycarboxylic acids substituted by halogen atoms or hydroxy, amino or keto groups, such as chloracetic, tartaric, glycollic, pyruvic, or acetoacetic acid, (e) aromatic monocarboxylic acids such as benzoic, xylic or naphthoic acid, (f) aromatic polycarboxylic acids such as phthalic acid, (g) alkylene-substituted aromatic monocarboxylic acids such as cinnamic acid, (h) aryl-substituted aliphatic mono- or polycarboxylic acids such as phenylstearic, naphthylstearic or naphthylpolystearic acid, (i) aromatic mono- or poly-carboxylic acids substituted by halogen atoms or hydroxy, amino, alkyl, aryl, aralkyl, keto, nitro or alkoxy groups, such as chlorobenzoic, salicylic, anthranilic, toluic, phenylbenzoic, benzylbenzoic, nitrobenzoic, anisic, and benzoylbenzoic acids, (j) non-benzenoid cyclic mono- or poly-carboxylic acids such as naphthenic, abietic and camphoric acids, and (k) heterocyclic carboxylic acids such as furoic acid; tricarboxylic acids are also mentioned, but none is specified.  The chlorides or anhydrides of these acids also may be used.  The proportion of acylating agent is preferably sufficient completely to esterify the alkylated aromatic hydroxy compound, but a lower proportion also may be used.  The products may be purified by washing them with water containing a small proportion of a lower alcohol, e.g. butanol.  An example is given in which chlorinated paraffin wax containing 14 per cent of chlorine is condensed with phenol in the presence of aluminium chloride and the product is treated with phthalyl chloride.  Reference is made also to the condensation of chlorinated paraffin wax with phenol, benzylphenol, resorcinol, o-hydroxydiphenyl, b -naphthol, and p-cresol, and to the treatment of the products with acetyl chloride, stearyl chloride, benzoyl chloride, phthalyl chloride, adipyl chloride, sebacyl chloride, cinnamyl chloride or montanyl chloride, examples of some of these processes being given.  The products are useful as pour-point depressants for lubricating oils, and in this connection numerous experimental results are given.  Specification 455,975, [Group IV], is referred to.  The Specification as open to inspection under Sect. 91 indicates that inorganic acids or their derivatives may be used as acylating agents, and includes examples in which a reaction product of chlorinated paraffin wax and phenol is treated with thionyl chloride and phosphorus oxychloride.  Reference is made also to the introduction of carbonic, sulphuric, phosphorous and pyrophosphoric acid radicles.  This subject-matter does not appear in the Specification as accepted.ALSO:An aromatic hydroxy compound of the benzene, naphthalene or anthracene series is condensed with a chlorinated higher aliphatic hydrocarbon, and the product is acylated with an organic acid or a derivative thereof, e.g. an acid anhydride or chloride.  The final products are mainly esters, but may contain minor proportions of ketones and other bye-products.  The aromatic hydroxy compound used as starting material may be further substituted by one or more alkyl, aryl, aralkyl, aryloxy, or alkoxy groups. Specified aromatic hydroxy compounds are phenol, benzylphenols, resorcinol, o-hydroxydiphenyl, b -naphthol, p-cresol, hydroquinone, catechol, xylenols, phenylethylphenols, methylhydroxydiphenyls, ethylhydroxydiphenyls, guaiacol, catechol monoethyl ether, dihydroxynaphthalenes, methylnaphthols, tolylnaphthols, xylylnaphthols, benzylnaphthols, methoxynaphthols, anthranols, and phenylmethylanthranols.  Suitable chlorinated aliphatic hydrocarbons are the chlorination products of heavy lubricating oil, petrolatum and paraffin wax.  The condensation of the aromatic hydroxy compound with the chlorinated aliphatic hydrocarbon is preferably effected at a temperature rising to 350 DEG  F. in the presence of aluminium chloride or like condensing agent. Specified acylating agents are (a) saturated aliphatic monocarboxylic acids such as acetic, butyric, capric, palmitic, stearic or montanic acid; (b) unsaturated aliphatic monocarboxylic acids such as acrylic or oleic acid; (c) saturated or unsaturated aliphatic polycarboxylic acids such as succinic, oxalic, adipic, sebacic or fumaric acid; (d) aliphatic mono- or poly-carboxylic acids substituted by halogen atoms or hydroxy, amino or keto groups, such as chloracetic, tartaric, glycollic, pyruvic, or acetoacetic acid; (e) aromatic monocarboxylic acids such as benzoic, xylic or naphthoic acid; (f) aromatic polycarboxylic acids such as phthalic acid; (g) alkylene-substituted aromatic monocarboxylic acids such as cinnamic acid; (h) aryl-substituted aliphatic mono- or poly-carboxylic acids such as phenylstearic, naphthylstearic or naphthylpolystearic acid; (i) aromatic mono- or poly-carboxylic acids substituted by halogen atoms or hydroxy, amino, alkyl, aryl, aralkyl, keto, nitro or alkoxy groups, such as chlorobenzoic, salicylic, anthranilic, toluic, phenylbenzoic, benzylbenzoic, nitrobenzoic, anisic, and benzoylbenzoic acids; (j) non-benzenoid cyclic mono- or poly-carboxylic acids such as naphthenic, abietic and camphoric acids, and (k) heterocyclic carboxylic acids such as furoic acid; tricarboxylic acids are also mentioned, but none is specified.  The chlorides or anhydrides of these acids may also be used, and when chlorides of hydroxy- or amino-carboxylic acids are taken, the hydroxy or amino group is preferably acylated before the chloride is prepared.  The proportion of acylating agent is preferably sufficient completely to esterify the alkylated aromatic hydroxy compound, but a lower proportion may also be used.  The acylation step is preferably effected with an organic acid chloride at about 100 DEG  F. in the presence or absence of a diluent, e.g. ethylene dichloride.  The products may be purified by washing them with water containing a small proportion of a lower alcohol, e.g. butanol.  An example is given in which chlorinated paraffin wax containing 14 per cent of chlorine is condensed with phenol in the presence of aluminium chloride, and the product is treated with phthalyl chloride. Reference is made also to the condensation of chlorinated paraffin wax with phenol, benzylphenol, resorcinol, o-hydroxydiphenyl, b -naphthol, and p-cresol, and to the treatment of the products with acetyl chloride, stearyl chloride, benzoyl chloride, phthalyl chloride, adipyl chloride, sebacyl chloride, cinnamyl chloride or montanyl chloride, examples of some of these processes being given. The products are useful as pour-point depressants for lubricating oils, and in this connection numerous experimental results are given. The products may be used also in the manufacture of synthetic resins and coating compositions.  Specification 455,975 is referred to. Naphthylpolystearic acid is prepared by condensing naphthalene with several mols. of chlorostearic or oleic acid in the presence of aluminium chloride.  The Specification as open to inspection under Sect. 91 indicates that inorganic acids or their derivatives may be used as acylating agents, and includes examples in which a reaction product of chlorinated paraffin wax and phenol is treated with thionyl chloride and phosphorus oxychloride.  Reference is made also to the introduction of carbonic, sulphuric, phosphorous and pyrophosphoric acid radicles.  This subject-matter does not appear in the Specification as accepted.