Patent GB-1347201-A (GB)
Title: Benzodioxan derivatives
IPC: C07C45/69
Filed: 1972-03-22
Abstract: 1347201 Benzodioxan-2-ylmethoxy compounds F HOFFMANN-LA ROCHE & CO AG 22 March 1972 [23 March 1971] 13412/72 Heading C2C [Also in Division A5] The invention comprises benzodioxan derivatives having juvenile hormone properties of the general Formula (I) wherein R 8  represents a hydrogen atom or a lower alkyl group and Z represents the grouping (A), in which R 6  and R 7  each represent a hydrogen atom or a lower alkyl group, or the grouping (B), in which R 2  and R 4  each represent a lower alkyl group, R 3  represents a hydrogen atom or a lower alkyl group, C and D each represent a hydrogen atom or C represents a hydrogen arom and D represents a lower alkyl, hydroxy, lower alkoxy, lower alkenyloxy, lower alkynyloxy or lower alkanoyloxy group or a benzyloxy group which may be substituted in the phenyl ring by lower alkyl, lower alkoxy, methylenedioxy or halogen, or C and D together represent an additional bond or an oxygen bridge and m stands for 1 or 2, or the grouping (C), in which R 1  represents a hydrogen atom or a lower alkyl group, or the grouping (D) in which A represents a hydrogen atom and B represents a hydrogen atom or a lower alkoxy group or A and B together represent an additional bond or an oxygen bridge, E and F each represent a hydrogen atom or E and F together represent an additional bond when A and B together represent an additional bond, or the grouping (E), in which R represents a hydrogen atom or a lower alkyl group, R 5  represents a lower alkyl group, M, T and Q each represent a hydrogen atom and G represents a hydrogen atom or a lower alkoxy group or Q and T together and M and G together each represent an additional bond, or the grouping (F) in which R represents a hydrogen atom or a lower alkyl group, R 5  represents a lower alkyl group, A, B 1 , E, F and M each represent a hydrogen atom and G represents a hydrogen atom or a lower alkoxy group or A and B 1  together and M and G together each represent an additional bond and E and F together represent an additional bond when A and B 1  together represent an additional bond, and their preparation by (a) reacting a compound of the general Formula (II) with a compound of the general formula Z-X(III), where in Formulµ II and III, one of the symbols V and X represents a chlorine, bromine or iodine atom or the tosyloxy group and the other symbol represents the group -OM in which M represents an alkali metal or an alkaline earth metal, or (b) catalytically hydrogenating a benzodioxan derivative of Formula I in which at least one of the pairs of symbols A and B, A and B 1 , E and F, M and G, Q and T and C and D represent an additional bond, or (c) epoxidizing a benzodioxan derivative of Formula I in which A and B 1  and/or C and D together represent an additional bond, or (d) etherifying a benzodioxan derivative of Formula I in which D represents a hydroxy group, or (e) esterifying a benzodioxan derivative of Formula I in which D represents a hydroxy group. The term lower defines the groups to which it applies as having up to 6 carbon atoms. 2 - Tosyloxymethyl - 1,4 - benzodioxan and tosyloxy - 3,7 - dimethyl - 7 - hydroxy octane are made by treating the corresponding alcohols with tosyl chloride. 3,7 - Dimethyl - 2,4 - octadien - 1 - ol is made by reducing ethyl 3,7-dimethyl-2,4-octadienoate with sodium dihydro-bis-(2-methoxy-ethoxy)- aluminate. 3,7,7 - Trimethyl - octa - 2,4 - dien - 1 - ol; 3,7,11 - trimethyl - 2 - cis/trans, 4 cis/transdodecadien - 1 - ol; and 3,7,11 - trimethyl- 2,4,1 -0 dodecatrien - 1 - ol and 3,7 - dimethyl - 7- methoxyoctan-1-ol are made similarly. 1 - Bromo - 3,7,7 - trimethyl - 2 - octene is made by reacting the corresponding alcohol with PBr 3 . 1 - Bromo - 3,7,7 - trimethylocta - 2,4 - dien and 1 - bromo - 3,7,11 - trimethyl - 2 - cis/trans, 4-cis/trans-dodecadiene are made similarly. 3,7,7-Trimethyl-1-octen-3-ol is made by reacting neopentyllithium with methyl vinyl kerone and reacting the resulting 6,6-dimethyl-2-heptanone with vinyl lithium. Ethyl 3,7,7-trimethylocta-2,4-dienoate is made by reacting the triphenylphosphonium salt of cis,trans-ethyl 4-bromo-3-methyl-2-butenoate with 3,3-dimethylbutyraldehyde. Ethyl 3,7,11 - trimethyl - 2 - cis / trans, 4 - cis/ trans - dodecadienoate and ethyl 3,7,11 - trimethyl - 2 - cis / trans, 4 - cis / trans, 10 - dodecatrienoate are made by reacting tetrahydrocitral and citronellal respectively with 1-carbethoxy- 2-methyl - 1-propenyl diethylphosphonate.