Patent GB-1481671-A (GB)
Title: Multiheterocycles their preparation and use
IPC: C07D493/08
Filed: 1975-08-20
Abstract: 1481671 Macrocyclic crown compounds UNIVERSITY OF CALIFORNIA REGENTS OF 20 Aug 1975 [12 Sept 1974] 34582/75 Heading C2C [Also in Division C3] The invention comprises compound (I) wherein (1) S in a group (A<SP>1</SP>), (B<SP>1</SP>) or (C<SP>1</SP>) s is 2, 3 or 4 and t, u and v are 0; (2) S is as defined in (1) above or is a group (D<SP>1</SP>) T is -CH 2 CH 2 -, s is 1, t is an integer of 2-7 and u and v are 0; (3) S and U have the meanings given to S in (1) above, T and V are s and u are 1, t is an integer of 1-6 and v is 0 or an integer of 1-6; (4) S is a p-phenylene group, T is -CH 2 CH 2 - s is 1, t is an integer of 3-9 and u and v are 0; (5) S and U are pphenylene groups, T and V are -CH 2 CH 2 -, s and u are 1 and t and v are integers of 3-9; (6) S is -(CH 2 ) 5 -, T is -CH 2 CH 2 -, s is 1, t is 4 and u and v are 0 ; (7) S and U are groups (A<SP>1</SP>), T and V are o-phenylene or groups (H<SP>1</SP>) and s, t, u and v are 1; (8) S is a group (A<SP>1</SP>), T and V are groups (H<SP>1</SP>) and U is a group (E<SP>1</SP>) and s, t, u and v are 1; (9) S is a group (A<SP>1</SP>), T and V are groups (H<SP>1</SP>), U is -(CH 2 ) 5 - and s, t, u and v are 1; (10) S is a group (A), (H<SP>1</SP>) or -(CH 2 ) 5 -, T and V are groups (H<SP>1</SP>), U is -CH 2 CH 2 -, s, t and v are 1 and u is 2; (11) S is a group (F<SP>1</SP>) (where R is H, Cl, Br, CO 2 CH 3 , CO 2 H, CN, CONH 2 , NH 2 , OH or OCH3), T is -CH 2 CH 2 -, s is 1, t is an integer of 3-8 and u and v are 0; (12) S is a group (G<SP>1</SP>) (where R<SP>1</SP> is CO 2 CH 3 , or CO 2 H (except when R<SP>11</SP> is CO 2 CH 3 ) and R<SP>11</SP> is CO 2 CH3, CO 2 H, CH 2 OH, CH 2 OCH 2 CO 2 CH 3  or CH 2 OCH 2 CO 2 H), T is -CH 2 CH 2 -, s is 1, t is an integer of 3-8 and u and v are 0; or (13) S is a group (L<SP>1</SP>) where R<SP>2</SP> is H or C 1-3  alkyl, T and V are groups (H<SP>1</SP>), U is -CH 2 CH 2 -, s, t and v are 1 and u is 2 and their preparation by conventional processes which form the cyclic ether groups and by formation of or conversion of substituents, where present, one into another. The compounds of the invention form complexes with other organic compounds. 2,6 - Bis - (bromomethyl)pyridine and 2. bromomethyl - 6 - hydroxymethylpyridine are made by reacting 2,6-bis-(hydroxymethyl)pyridine with HBr. Di - (2 - hydroxymethylpyridyl - 6 - methyl)- ether is made by reacting 2-methyl-6-hydroxypyridine with NaH and then with 2-methyl-6- chloromethylpyridine, reacting the resulting di - (2 - methylpyridyl - 6 - methyl)ether with H 2 O 2  to give the bis-N-oxide, reacting this with acetic anhydride to give di-(2-acetoxymethylpyridyl-6-methyl)ether and hydrolysing the latter. The polyether CH 3 (OCH 2 CH 2 ) 5 OCH 3  is made by reacting T 5 (OCH 2 CH 2 ) 5 OT 5  (where T 5  is tosyl) with CH 3 0Na. 1,3 - Di - (hydroxymethyl) - 2 - bromobenzene is made by hydrolysing the corresponding diacetate, which is made by reacting 1,3-di-(bromomethyl)-2-bromobenzene with potassium acetate. 1,3 - Di - (bromomethyl) - 2 - cyanobenzene, 1,3 - di - (bromomethyl) - 2 - bromobenzene, 1,3- di - (bromomethyl) - 2 - methoxycarbonylbenzene and 1,3 - di - (bromomethyl) - 2,5 - di - (methoxycarbonyl)benzene are made by reacting the corresponding 1,3-dimethyl-compounds with N- bromosuccinimide. 2 - (Vinyloxymethyl) - 5 - hydroxymethylfuran is obtained as a by-product of a process of the invention by reacting, with NaH, 2-(2-chloroethoxymethyl)-5-hydroxymethylfuran. The latter is made by reacting 5-chloromethylfurfural with 2-chloroethanol and BaCO 3  and reducing the resulting 2-(2-chloroethoxymethyl)furfuraldehyde. Di - (2 - hydroxymethylfuryl - 5 - methyl)ether is made by condensing 5-hydroxymethylfurfuraldehyde by azeotropic distillation in the presence of p-toluenesulphonic acid and reducing the resulting di-aldehyde.