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Chroman Compounds and Their Use

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Chroman Compounds and Their Use fcrop^chesPa.en.am. II 1 1 II II ill i|l I II I II I 1 1 1 III II I II European Patent Office fllQOQCQQI © Publication number: U I OO OD3 D I Jffice europeen des brevets S) EUROPEAN PATENT SPECIFICATION 4s) Date of publication of patent specification: 17.04.91 © Int. CI.5: C07D 31 1/72, C07D 31 1/92, C09K 15/08, A61K 31/355 zj) Application number: 84114879.4 §) Date of filing: 06.12.84 5«) Chroman compounds and their use. Date of publication of application: (73) Proprietor: KURARAY CO., LTD. 11.06.86 Bulletin 86/24 1621 Sakazu Kurashiki-City Okayama Prefecture 710(JP) Publication of the grant of the patent: 17.04.91 Bulletin 91/16 @ Inventor: Shiono, Manzo 2-2-34, Showa Designated Contracting States: Kurashiki City Okayama Pref.(JP) CH DE FR GB IT LI NL Inventor: Fujita, Yoshiji 2- 2-30, Showa References cited: Kurashiki City Okayama Pref.(JP) JP-A-55 943 82 Inventor: Nishida, Takashi US-A- 4 321 270 3- 9, Kurashikihaitsu Kurashiki City Okayama Pref.(JP) PATENTS ABSTRACTS OF JAPAN, vol. 6, no. 250 (C-139)[1128], 9th December 1982; & JP - A - 57 145 871 © Representative: Vossius & Partner Siebertstrasse 4 P.O. Box 86 07 67 E. SCHROEDER et al, (Eds) Pharmazeutische W-8000 Miinchen 86(DE) Chemie, G. Thieme, 1982; p. 639 CQ 03 CO 00 CO 00 O Note: Within nine months from the publication of the mention ot tne grant ot tne turopean paiem, any pei&un Office of to the European patent granted. Notice of opposition ^ may give notice to the European Patent opposition 2j shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid (Art. 99(1) European patent convention). Rank xerox (UK) business services EP 0 183 869 B1 Description This invention relates to novel chroman compounds, and to the use of these compounds as analgesics or precursors for the compounds having analgesic activity. 5 It is known that compounds having a chroman skeleton such as 2-(N,N-dimethylamino)ethyl 2-(2,2,5,7,8- pentamethyl-6-chromanyloxy)isobutyrate, 2-(2,2,5,7,8-pentamethyl-6-chromanyloxy)isobutyl nicotinate, etc. have cholesterol lowering activity [Japanese Laid-Open Patent Publication No. 94382/1980] JP-A-57 145 871 describes a chromanolcarboxylic acid derivative of formula w CH2CH2COOR ca, 15 wherein R is a hydrogen atom or a lower alkyl group and an antioxidant containing said derivative as an active ingredient. In E.Schroder, C.Rufer, R.Schmiechen (Hrsg.), Pharmazeutische Chemie, Verlag G.Thieme, 1982, page 639, it is described that a-tocopherol (vitamine E) has an antioxidant and an antithrombic activity. US-A-4321270 describes chroman derivatives of formula 25 R2 alkyl-(^) Cp wherein is -lower , -lower alkyl- , H , , lower alkyl ,- lower a^yi-N^iowIr or lower a Iky 1-N- lower alkyl, 30 alkyl H and salts and hydrates thereof which are useful as anti-inflammatory agents, for inhibition of blood platelet aggregation, as antiallergy and as antihypertensive agents. 35 It is an object of the invention to provide novel chroman compounds which are either analgesics or useful as precursors for such analgesic compounds. It is a further object of the invention to provide pharmaceutical compositions which contain the chroman compounds as active ingredients for use as analgesics. In accordance with this invention, there are provided compounds of general formula (I) 40 R4YlTVCH> iHl 45 wherein R is a hydrogen atom or a hydroxymethyl or carboxyl group, R1 is a hydrogen atom or a C1-C4. alkyl group, R2 and R3 are the same or different and each is a hydrogen atom or a C1-C4 alkyl or alkoxy so group or R2 and R3 combinedly represent a -CH = CH-CH = CH- group, R+ is a hydrogen atom or a protective group and n is an integer of 0-2, inclusive of the ester and/or salt forms thereof [hereinafter collectively referred to as "chroman compounds (I)"]. Further in accordance with this invention, there are provided pharmaceutical compositions with analge- sic activity said compositions being composed of (1) an analgetically effective amount of a compound of 55 general formula (I-2) 2 :P 0 183 869 Bl :h3 ?H2 (1-2) CH2)nCH-R therein R, R1, R2, R3 and n are as defined above relative to general tormuia (i), inclusive ot me pharmaceutical^ acceptable ester and/or salt forms thereof [hereinafter collectively referred to as "chroman and acceptable diluent or carrier. '00 compounds (I-2)"], (2) a pharmaceutical^ Referring to the above general formula (I), R is a hydrogen atom or a hydroxymethyl or carboxyl group. R1 is a hydrogen atom or a lower alkyl group such as methyl, ethyl, propyl or butyl, R2 and R3 are the same or different and each is a hydrogen atom, a lower alkyl group such as methyl, ethyl, propyl or butyl, or a -CH = CH- lower alkoxy group such as methoxy, ethoxy, propoxy or butoxy, or R2 and R3 combinedly form a R* atom or a protective Said protective group may be any of 5 CH = CH-group. is a hydrogen group. conventional protective groups if only protection of hydroxyl group can be attained, and may be exemplified by acyl groups (e.g. acetyl, propionyl, butyryl or benzoyl), methyl, tert-butyl, triphenylmethyl, benzyl or trimethylsilyl, n is an integer of 0-2. The compounds of general formula (I) may be grouped, according to the substituent R, into the 0 following three classes: NHz 25 (I-a) J (CH2)nCHC02H 30 NH2 :h3 ~> (i-b) (CH2)nCHCH20H 35 R3 NHz 40 :hs i — (CH*)nCH* (i-c) 45 The esters and salts of the a-amino acids of general formula (l-a) include sucn ester rarms as an diKyi ester stearyl ester; ester, e.g. methyl ester, ethyl ester, propyl ester, butyl ester, octyl ester, tetradecyl or and such salt forms as an alkali metal salt, e.g. lithium salt, sodium salt or potassium salt, or a mineral acid or salt, e.g. hydrochloride, sulfate or nitrate, or an organic sulfonic acid salt, e.g. p-toluenesulfonate methanesulfonate. 50 The a-amino acids of general formula (l-a) can be produced by reacting an aldehyde of general formula R50 CH3 55 R2 ' (ii) (CH2)nCHO R* 3 EP 0 183 869 B1 wherein R1, R2, R3 and n each have the same meanings as in general formula (I), and R3 is the same as or different from R* in general formula (I) and represents a hydrogen atom or a protective group, with ammonium carbonate and an alkali metal cyanide and then hydrolyzing the thus-obtained hydantoin of general formula 0 it R1 C Rf 0 >v-\ hn" "to 10 3QcCH3 » / R2' J (III) y° (CH2)nCHC^0 15 wherein R1, R2, R3, R5 and n each have the same meanings as in general formula (II). Said alkali metal cyanide is, for example, sodium cyanide, potassium cyanide or lithium cyanide. The reaction of the aldehyde of general formula (II) with ammonium carbonate and the alkali metal cyanide can be carried out under conditions which are generally known to be adequate for hydantoin syntheses. Thus, for instance, the 20 aldehyde of general formula (II), about 1-10 moles, preferably about 1-3 moles, per mole of aldehyde, of ammonium carbonate and about 1-10 moles, preferably about 1-3 moles, per mole of aldehyde, of the alkali metal cyanide are reacted in a solvent such as water, methanol, ethanol or tetrahydrofuran, at a temperature ° between room temperature and 100° C, preferably in the range of 40-60 C. The reaction mixture is then concentrated, a small amount of concentrated hydrochloric acid is added to the concentrate, and the 25 mixture is heated at about 80-100° C for about 1-10 minutes, whereby the hydantoin of general formula (III) is obtained. Hydrolysis of the thus-obtained hydantoin by the conventional method gives the a-amino acid of general formula (l-a). The hydrolysis is carried out, for example, by reacting the hydantoin and about 1-5 moles, per mole of hydantoin, of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide in an aqueous medium at a temperature of 80-150° C, preferably 100-130° C, followed by 30 neutralization of the alkali being in the system with a mineral acid such as hydrochloric acid or sulfuric acid. When subjected to the generally known esterification and/or salt formation reaction, the a-amino acids of general formula (l-a) are converted to esters or salts of said a-amino acids or salts of said a-amino acid esters. Thus, for example, reacting the a-amino acids of general formula (l-a) with an alkyl alcohol such as. methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, octyl alcohol or stearyl alcohol, in the presence 35 of hydrogen chloride, sulfuric acid or thionyl chloride in an amount at least equivalent to said a-amino acid at about -20° C to +40° C, followed by neutralization of the reaction mixture, for example, with an aqueous sodium bicarbonate, gives the corresponding a-amino acid ester. The a-amino acid of general formula (l-a) or esters thereof are converted to the corresponding salts by dissolving said a-amino acids or esters thereof in water, methyl alcohol, ethyl alcohol, propyl alcohol, tetrahydrofuran or diethyl ether and then adding to 40 the solution an approximately equivalent amount, to the a-amino acid or ester thereof, of a mineral acid such as hydrogen chloride, sulfuric acid, nitric acid, or an organic sulfonic acid such as p-toluenesulfonic acid or methanesulfonic acid, or an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide.
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