Patent GB-1439542-A (GB)
Title: Derivatives of norbornene
IPC: C07C309/63
Filed: 1973-08-28
Abstract: 1439542 Derivatives of norbornene compounds F HOFFMAN-LA ROCHE & CO AG 28 Aug 1973 [28 Aug 1972] 40529/73 Heading C2C The invention comprises a racemic or optically active compound of formula where R<SP>1</SP> represent a hydrogen atom or the acid residue of an aromatic or aliphatic dicarboxylic acid, an optically active aliphatic or araliphatic monocarboxylic acid, an optically active sulphonic acid or an optically active carbamic acid. The invention also comprises the tetrahydropyranyl ethers of above compound which are represented by formula The invention also comprises a compound of formula  where R<SP>4</SP> represents a sulphonyloxy group derived from an organic sulphonic acid, or a Cl, Br, or I 2  atom and R 2  is an acid residue of an aliphatic dicarboxylic acid, and optically active aliphatic or araliphatic monocarboxylic acid, an optically active sulphonic acid or an optically active carbamic acid. This compound may be obtained by reductively opening the anhydride group of 5,6-dimethyl-bicyclo[2,2,1] hept-5-en-2-endo-3-endo-dicarboxylic acid anhydride and, if desired, esterifying a hydroxy group of the thus obtained 5,6-dimethylbicyclo [2,2,1]hept - 5 - en - 2 - endo - 3 - endo - dimethanol with a compound yielding an acid residue R<SP>1</SP> and, also if desired, separating a diastereomer pair thereby obtained or resolving a recemate thereby obtained. The invention also comprises two further processes in which starting with the compound according to the invention there are obtained, through a long series of reactions, compounds of formulae In the preparation of compounds XV and XVa and the compounds according to the invention the following intermediates are prepared: (IR) 5.6 - dimethyl - 3 - exo - [(tetrahydro - 2H- pyran - 2 - yl) - oxy]methyl - [5 - norbomen - 2- endomethanol] by the treatment of [(IR) 5,6- dimethyl - 3 - exo] - [(tetrahydro - 2H - pyran- 2 -yl) - oxy]methyl - (5 - norbornen - 2 - endoyl) - methyl (IR) - 2 - exo - bornane carbamate with KOH/CH 3 OH in Example 12 (see also Examples 31 and 44); (IR)-5,6-dimethyl-3-exo- [(tetrahydro - 2H - pyran - 2 - yl)oxy]methyl - 5- norbornen - 2 - endo - yl - methyl - methane sulphonate is prepared by treating the corresponding hydroxy compound with CH 3 SO 2 Cl in Example 13 (see also Example 32); (IR)-5,6- dimethyl - 3 - endo - [(methylsulphonyl) - oxy] methyl - 5 - norbornen - 2 - endo - yl - methyl (IR) 2 - oxo - bornene - carbamate is prepared by treating [(IR)-3-endo-hydroxymethyl-5,6-dimethyl - 5 - norbornen - 2 - endo - yl]methyl (IR) - 2 - exobornane carbamate with CH 3  SO 2 Cl, in Example 14; (3-exo-formyl-5,6- dimethyl - 5 - norbornene - 2 - endo - yl) - methyl methyl phthalate is prepared by treating (3- acetoxymethylene - 5,6 - dimethyl - 5 - norbornen - 2 - endo - yl) - methyl methyl phthalate with H 2 S0 4  in Example 27 (see also Examples 25, 28, 40 and 41); (3aR,4S,5R,6aS)-4- benzyloxymethyl - hexahydro - 5 - hydroxy - 2H- cyclopenta[b]furan is obtained by treating (1S,3R,5S,5R) - 4 - benzyloxymethyl - 5 - [(1- pyrrolidinyl - carbonyl) -methyl] - 1,3 - cyclopentylene - diacetate with alcoholic KOH, in Examples 24; 5,6-dimethyl-3-exo-tetrahydropyran - 2 - yl) - oxymethyl - 5 - norbornen - 2- endo-acetonitrile is prepared by treating 5,6- dimethyl - 3 - exo - (tetrahydro - 2H 8 pyran - 2- yl) - oxymethyl - 5 - norbornen - 2 - endo - ylmethyl with NaCN in Example 33; 3- exo - (hydroxymethyl) - 5,6 - dimethyl - 5 - norbornen - 2 - endo - acetonitrile is obtained by the reaction of the product of Example 33 with CH 3 OH/HCl in Example 34; 3-exo-(benzyloxy)- methyl - 5.6 - dimethyl - 5 - norbornen - 2 - endoacetonitrile is obtained by treating the product of Example 34 with monoglyme in Example 35; 3α,5α - diacetyl - 2# - benzyloxymethyl - lα - cyclopentane acetonitrile is prepared by ozonizing the product of Example 35 at -70‹ C. in Example 36; 4,4-benzyloxymethyl-5α-cyanomethyl - 1α,3α - cyclopentylene diacetate is prepared by the oxidation of the product of Example 36 with trifluoro-peracetic acid in Example 37. The intermediates described in Examples 14-23 are described in the Specifications 1,439,543 and 1,439,544.