generally , the process of the invention involves treatment of the saturated starting lactam , lactone or azasteroid with a silyating agent in the presence of a quinone . a number of silylating agents capable of sily lactams , lactones and azasteroids can be used . for example , bistrimethylsilylacetamide , bistrimethylsilyltrihaloacetamide , hexamethyldisilazane or bistrimethylsilylurea are silyating agents that can be used in the processes of the present invention . the bistrimethylsilyltrihaloacetamide silyating agent can have any halo group as a moiety thereof , such as chloro , fluoro , bromo or iodo . the preferred silyating agent is bistrimethylsilyltrifluoroacetamide ( bstfa ). primarily , the readily available 2 , 3 dichloro - 5 , 6 - dicyano 1 , 4 - benzoquinone ( ddq ) and 3 , 4 , 5 , 6 - tetrachloro - 1 , 2 - benzoquinone are preferred for use in the process of the present invention , but any other quinone of sufficient reaction potential can also be used . for example , ortho - or para - benzoquinones of the following formula : ## str10 ## where r 14 is hydrogen , c 1 - 6 alkyl , c 1 - 6 alkoxy , halo such as cl , f , i , br , nitro or cyano , can be used in the present invention . this would include quinones such as 2 , 3 , 5 - trimethyl - 1 , 4 benzoquinone , 2 , 6 - dimethyl - 1 , 4 - benzoquinone , 2 , 6 - di - t - butyl - 1 , 4 - benzoquinone , 3 , 5 - di - t - butyl - 1 , 2 - benzoquinone and 2 , 3 di - alkoxy - 1 , 4 benzo quinone . other quinones of sufficient reaction potential can be substituted for ddq and still be within the scope of the present invention . as a general procedure , a lactam , lactone or 3 - keto - 4 - azasteroid is treated with a quinone and a silyating agent in aliphatic or cyclic ethers , or chlorinated or aromatic hydrocarbon solvents with or without strong acid actalysis and with or without preliminary low temperature aging and then , first at a lower temperature , and then at elevated temperatures under nitrogen for 5 to 25 hours to cleanly produce the corresponding dehydrogenated lactam , or lactone in high yield . these conditions were also used to convert a 3 - keto - 4 - azasteroid to the corresponding δ 1 - azasteroid with consistently high yields . when x is nr 1 , o or ch 2 , the compound of a is reacted with ddq and bstfa to form a diastereomeric intermediate b of the following partial structure : ## str12 ## heating the diastereomeric mixture b results in formation of the corresponding δ 1 compound . cyclohexane - 1 , 3 - dione is used to decompose the residual ddq prior to thermolysis . when x is n or ch 2 , the compound a is reacted with ddq and bstfa to form an intermediate according to the following partial structure : ## str13 ## for example , the 17β - carboxy - 4 - aza - androstan -- 3 - one ( a ) is reacted with dichlorodicyano - p - benzoquinone ( ddq ) and bistrimethyl - silyltrifluoro - acetamide ( bstfa ) to form a diastereomeric intermediate ( b ). the intermediate ( b ) is subjected to dioxane reflux under heat to form the 17β - carboxy - 3 - oxo - 4 - substituted - 4 - aza - androst - 1 - ene - 3 - one ( c ) corresponding to formula i . the novel chemical intermediates formed in the process disclosed herein is also a significant part of the present invention . these novel chemical intermediates ( b ) are formed as diastereomeric mixtures , however , each diastereomer is included within the scope of the invention . the intermediates are compounds of the formula : ## str14 ## wherein : q is absent or is ## str15 ## where r 4 is methyl , c 1 - 8 straight or branched chain alkyl , c 3 - 6 cycloalkyl , phenyl , or combinations thereof ; and r 14 is hydrogen , c 1 - 6 straight or branched alkyl , c 1 - 6 alkoxy , halo , nitro or cyano ; ( a ) when q is present , ## str16 ## where x is nr 1 , o or ch 2 ; and r 1 is absent or is hydrogen , methyl or ethyl ; ( b ) ## str17 ## where x &# 39 ; is n or ch ; ( c ) ## str18 ## where x &# 34 ; is o or ch 2 ; z is ( a ) ## str19 ## where alk is present or absent and is a straight or branched hydrocarbon chain of 1 to 12 carbon atoms ; and r 8 is , ( iv ) nr 9 r 10 , where r 9 and r 10 are each independently selected from hydrogen ; c 1 - 12 straight or branched chain alkyl ; c 1 - 12 straight or branched chain alkyl having a hydroqen substituted with a hydroxy , carboxylic acid or c 1 - 4 alkyl ester ; c 3 - 6 cycloalkyl ; phenyl ; or r 9 and r 10 taken together with the nitrogen to which they are attached represent a 5 - 6 membered saturated ring comprising up to one other heteroatom selected from oxygen and nitrogen ; or ( v ) or 11 , where is m , where m is hydrogen or alkali metal , or c 1 - 18 straight or branched chain alkyl ; benzyl ; or ( b ) --( alk )-- or 12 , where alk is always present and has the same meaning as above ; and ( vi ) hydrogen , provided that alk is a branched c 3 - 8 chain ; ( 3 ) ## str20 ## or ═ ch -- alk -- or 12 , where alk is present or absent and has the same meaning as above , and r 8 and r 12 have the same meaning as above , and r 12 is also hydroqen or c 1 - 20 alkylcarbonyl ; ( 5 ) α - hydrogen and ## str22 ## where r 13 is , ( a ) c 1 - 12 alkyl ; or the following examples should be considered as not limiting the invention and will serve to illustrate the manner in which the present invention is accomplished . a 1 l three neck round bottom flask equipped with a nitrogen inlet , reflux condenser , addition funnel , mechanical stirrer and an immersion thermometer was charged with 180 ml dioxane followed by 18 g of 3 oxo - 4 - aza 5α - androstan - 17β - carboxylic acid portionwise with stirring . to the stirred suspension was added portionwise 13 . 86 g of ddq . the flask was evacuated ( 22 &# 34 ; hg ) and flushed with nitrogen three times . to this stirred suspension was added bstfa via the addition funnel at the rate of 50 ml / minute . the temperature slowly went up form 22 ° to 25 ° in a period of thirty minutes as most of the solids dissolved within this period to afford a clear solution . the solution was stirred for 18 hours at 22 ° after which time formation of the two diastereomeric adducts were observed . to the solution was added 0 . 54 g cyclohexane - 1 , 3 - dione and the reaction mixture was stirred at 22 ° for an additional three hours to decompose any residual ddq . the solution was then heated in an oil bath so that a very gentle reflux was maintained . ( bath temperature 120 °, internal temperature 108 °) after refluxing for 20 hours complete disappearance of the adducts and formation of δ 1 acid were observed . the reaction mixture was cooled to 22 ° and poured slowly over a period of 2 minutes into a stirred mixture of 300 ml ch 2 cl 2 and 60 ml 1 % aqueous sodium bisulfite solution . the flask was rinsed with 50 ml ch 2 cl 2 . after the mixture was stirred for thirty minutes , 18 ml 6n hcl was added to this mixture and stirred for an additional thirty minutes . the heterogeneous mixture was filtered and the residue was washed with 60 ml in hcl followed by 250 ml ch 2 cl 2 . the filtrated was transferred into a seperatory funnel and allowed to settle . the bottom ch 2 cl 2 layer containing the product was separated from the top aqueous layer and the top layer was washed with 60 ml ch 2 cl 2 . the combined ch 2 cl 2 layer was washed with 200 ml 2n hcl . the aqueous layer was washed with 60 ml ch 2 cl 2 . the two ch 2 cl 2 solutions were combined . the liquid chromatography yield at this stage was 16 . 0 g ( 88 %). the combined ch 2 cl 2 solution was then distilled and concentrated to about 120 ml volume . the distillation was continued and acetonitrile was added to the flask at such a rate so that the total volume was maintained at approximately 120 ml . after addition of about 400 ml acetonitrile the distillation head showed a temperature of about 82 °. gas chromatography analysis performed on the mother liquor showed the presence of about 2 % dioxane . the distillation was discontinued at this point . the suspension was cooled to 20 ° and aged at 20 ° for 20 hours with stirring . the crystals were filtered and washed with acetonitrile until the filtrate was colorless . approximately 100 ml acetonitrile was used for the wash . the wet cake was dried at 60 ° c . under vacuum ( about 1 mm μg ) overnight to produce 15 . 3 g of the δ 1 acid . a 50 ml three neck round bottom flask equipped with a nitrogen inlet , reflux condenser , addition funnel , magnetic stirrer and an immersion thermometer was charged with 10 ml dioxane followed by 1 g of 17β - n ( t - butylcarbamoyl )- 4 - aza - 5α - androstan - 3 - one portionwise with stirring . to the stirred suspension was added portionwise 0 . 656 g ddq . the flask was evacuated ( 20 &# 34 ; hg ) and flushed with nitrogen three times . to this stirred suspension was added bstfa via a syringe at the rate of about 2 ml / min . most of the solids dissolved during a period of half of an hour to afford a clear red solution . the solution was stirred for 18 hours at 22 ° after which time complete disappearance of standing material and formation of the two diastereometric adducts were observed by liquid chromatography . to this solution was added cyclohexane 1 , 3 - dione and the reaction mixture was stirred at 22 ° for an additional three hours to decompose any residual ddq . the solution was then heated in an oil bath so that a very gentle reflux was maintained . after refluxing for 20 hours complete disappearance of the adducts and formation of the title compound were observed by liquid chromatography . the reaction mixture was cooled to 22 ° and poured slowly into a stirred mixture of 30 ml ch and 6 ml 1 % aqueous sodium bisulfite solution . the flask was rinsed with 10 ml ch 2 cl 2 . after the mixture was stirred for 15 minutes 4 ml 6n hcl was added to this mixture and stirred for an additional 15 minutes . the heterogeneous mixture was filtered and the residue was washed with 20 ml ch 2 cl 2 . the filtrate was transferred to a seperatory funnel and allowed to settle . the bottom ch 2 cl 2 layer containing the product was separated from the top aqueous layer and the top layer was washed with 20 ml ch 2 cl 2 . the combined ch 2 cl 2 layer was washed with 20 ml 2 % sodium hydroxide solution . the ch 2 cl 2 solution was then distilled and concentrated to about 6 ml volume . the distillation was continued and isopropyl acetate was added to the flask at such a rate so that the total volume was maintained at approximately 6 ml . the distillation was discontinued when the distillation head showed a temperature of about 85 °. the suspension was cooled at 0 ° for 6 hours . the crytals were filtered and washed with 2 ml isopropyl acetate . the crystals were dried at 60 ° under vacuum ( 1 mr hg ) overnight to produce 0 . 8 g of the title compound ( 80 %). to 250 mg of 17 - β -( t butylcarbamoyl )- 4 - aza - 5α - androstan - 3 - one in a glass nmr tube were added approximately 2 ml of methylene chloride ( as a ch 2 cl 2 cd 2 cl 2 mixture suitable for nmr studies ), 0 . 7 ml bstfa and 60 mcl cf 3 so 3 h . the tube was cooled in methanol - ice and 168 mg tetrachloro - 1 , 2 - benzoquinone added accompanied by injection of a stream of dry n 2 . the tube was then closed with a snugly fitting polyethylene stopper , sealed with stretched parafilm ®, agitated briefly with only momentary warming , and placed in a cooled nmr probe which had been previously adjusted for 13 c observations of reaction intermediates at approximately - 5 ° c . spectra were obtained from time to time over a period of two days during which the sample temperature was maintained between zero and - 10 ° c . the solution was then allowed to age five days at ambient temperature while additional spectra were recorded from time to time . at the end of this aging the entire solution was quantitatively transferred , quenched with 1 ml acetic acid and volumetrically diluted for replicate hplc analyses which gave 80 - 84 % yield , based on assay vs pure 17β -( t - butylcarbamoyl )- 4 - aza - 5α - androst - 1 - ene - 3 - one , from the saturated lactam precursor . a 100 ml three - neck round bottom flask equipped with a nitrogen inlet , reflux condenser , magnetic stirrer and a septum inlet was charged with 17 - β -( t - butylcarbamoyl )- 4 - aza - 5α - androstan - 3 - one ( 4 . 0 g ), ddq ( 4 . 0 g ) and dioxane ( 26 ml ). to this suspension was added bstfa ( 10 . 5 g ) with stirring via a syringe over a period of 1 min . heating the mixture at reflux for 10 minutes afforded a clear solution . the solution was refluxed for 18 hours at the end of which complete disappearance of starting material was observed by lc . the solution was cooled to room temperature and added to a mixture of 100 ml each 5 % nahso 3 and ch 2 cl 2 , precipitating the hydroquinone which was separated by filtration . the ch 2 cl 2 layer of the filtrate was separated , extracted twice with 100 ml of 5 % nahso 3 , concentrated to a thick oil and triturated with 200 ml diethyl ether . first and second crop solids were isolated and dried 4 hours at 50 ° under vacuum yielding a total of 3 . 28 g of 88 % pure 17 - β -( t - butylcarbamoyl )- 4 - aza - 5α - androst - 1ene - 3 - one . a 1 l 3 - neck round bottom flask equipped with a nitrogen inlet , reflux condenser , additional funnel , mechanical stirrer and an immersion thermometer was charged with 320 ml of toluene , 20 g of 3 - oxo - 4 - aza - 5α - androstan - 17β - carboxylic acid , 5 . 7 g of ddq , 70 ml of bstfa and 0 . 32 ml of triflic acid . the flask was evacuated and flushed with n 2 three times . the reaction mixture was stirred for 18 h at 38 °- 40 ° after which time complete disappearance of starting material and formation of two diastereomeric adducts was observed by lc . cyclohexane 1 , 3 - dione ( 0 . 8 g ) was added and the reaction mixture was stirred at 38 °- 40 ° for 3 hours to quench any residual ddq . the solution was then heated to gentle reflux for 20 h after which time complete disappearance of the adducts and formation of the δ 1 - acid ( 95 % assay yield ) was observed by lc . the reaction was cooled to 20 ° c . aqueous naoh ( 430 ml , 1 % by wt ) and 20 ml of isopropanol were added . the mixture was stirred for 30 min , allowed to settle and the bottom aqueous layer was re extracted with a mixture of 430 ml toluene and 120 ml i - propanol . the combined toluene layers were extracted with 320 ml of 1 % naoh . the bottom aqueous layer containing the product was extracted and the organic layer was washed with another 160 ml of 1 % naoh . the aqueous layers were combined and isopropanol removed by vacuum distillation and replaced with 100 ml of acetonitrile . the mixture was warmed to 60 °- 65 ° c . and acidified with 12 ml of 6n hcl to ph 1 , aged at 60 °- 65 ° c . for 2 hours , cooled to 20 ° c . and aged for 18 hours and filtered . the filter cake was washed with 100 ml of h 2 o / ch 3 cn ( 4 / 1 ). the product was dried at 50 °- 60 ° c . under vacuum to yield 17 . 6 g ( 88 %) of the desired δ 1 - aza acid . a 1 l three - neck round bottom flask equipped with a nitrogen inlet , reflux condenser , additional funnel , mechanical stirrer and an immersion thermometer was charged with 320 ml of toluene , 20 g of methyl - 3 oxo 4 - aza 5α - androstan 17β - carboxylate , 14 . 73 g of ddq , 67 ml of bstfa and 0 . 32 ml triflic acid . the flask was evacuated and flushed with n 2 three times . the reaction mixture was stirred for 18 h at 22 ° after which time complete disappearance of starting material and formation of the two diastereomeric adducts was observed by lc . cyclohexane 1 , 3 - dione was added and the reaction mixture was stirred at 22 ° for 3 hours to quench any residual ddq . the solution was then heated to gentle reflux for 20 h after which time complete disappearance of the adducts and formation of the methyl 3 - oxo - 4 - aza - 5 - androst - 1 - ene - 17 - carboxylate was observed by lc . the toluene solution was cooled to 22 ° c . and 42 ml ch 2 cl 2 and 390 ml saturated sodium bicarbonate solution added with stirring . the bottom layer was separated from the top organic layer containing the product . the top layer was washed once more with 390 ml saturated sodium bicarbonate solution . the toluene solution was distilled to 100 ml volume . toluene was displaced by n butylacetate via distillation maintaining 100 ml volume . the slurry was aged at 22 ° for 18 hours and filtered to produce the product steroid in 91 % yield . by following the procedure of the preceding example a 90 % yield of 17β -( t - butylcarbamoyl )- 4 - aza - 5α - androst - 1 - ene - 3 - one was obtained from the corresponding 17β -( t - butylcarbamoyl )- 4 - aza - 5 - α - androstan - 3 - one . by following the procedure of the preceeding example a 90 % yield of 22 ( r , s )- methyl - 4 - aza - 21 - nor - 5α - cholen - 3 , 20 dione was obtained from the corresponding 22 ( r , s )- methyl - 4 - aza - 21 - nor - 5α - cholan - 3 , 20 - dione . a 100 ml three neck round bottom flask equipped for magnetic stirring and a nitrogen inlet was charged with 2 g of 17β -( t - butylcarbamoyl )- 4 - aza - 5α - androstan - 3 - one , 20 ml ch 2 cl 2 , and 1 . 344 g of ortho chloranil . the solution was cooled to - 8 ° by means of methanol / ice cooling and 6 ml bstfa was added via syringe ( ca . 1 min ) followed by 0 . 48 ml triflic acid . the solution was stirred at - 10 ° for 2 days followed by 22 ° for 6 days , after which time complete disappearance of starting material was observed by lc . at the end of this age hplc analyses showed 1 . 6 g of 17β -( t - butylcarbamoyl )- 4 - aza - 5α - androst - 1 - ene - 3 - one ( based on assay vs pure 17β -( t - butylcarbamoyl )- 4 - aza - 5α - androst - 1 - ene - 3 - one ; yield 80 %. isolation of the diastereomeric adduct formed between 3 - oxo - 4 - aza - 5α - androstan - 17β - carboxylic acid and ddq a 100 ml 3 neck round bottom flask equipped with a nitrogen inlet and magnetic stirring was charged with 20 ml tetrahydropyran , 2 g of 3 - oxo - 4 - aza - 5α - androstan - 17β - carboxylic acid , 6 . 7 ml of bstfa , 1 . 47 g of ddq and 2 mcl of triflic acid . the solution was stirrd under n 2 for 20 hours at 22 ° after which time complete disappearance of starting material and formation of the two diastereomeric adducts was observed by lc . the solution was cooled to 4 ° ( ice cooling ) and 0 . 2 ml water was added to it . the mixture was stirred at 4 ° for 3 hours . the solvent was removed at 20 ° in the rotovapor to afford a yellow oil which was tritiated with 60 ml ch 2 cl 2 . the two diastereomeric adduct crystallized . the crystals were aged for 1 hour at 22 ° filtered , washed with 20 ml ch 2 cl 2 and dried in vacuum at 22 ° to afford 90 % yield of the two diastereomeric adducts . 100 mg of the two diasteromeric adducts ( obtained in example 10 ) were heated in 2 ml dioxane under n 2 atmosphere for 18 hours to produce 36 mg ( by lc analysis , 60 %) of the desired 3 - oxo - 4 - aza - 5α - androst - 1 - ene - 17β - carboxylic acid . by following the procedures of example 1 or 2 but substituting the corresponding 1 , 2 - saturated steroid as a starting material , the following compounds could be obtained . ______________________________________ compoundexample name______________________________________12 17β - hydroxy - 4 - aza - 5α - androst - 1 - en - 3 - one13 3 - oxo - 4 - aza - 5α - preg - 1 - ene - 20α - carboxylic acid14 methyl - 3 - oxo - 4 - aza - 5α - pregn - 1 - ene - 20α - car - boxylate15 2 &# 39 ;, 3 &# 39 ; α - tetrahydro - furan - 2 &# 39 ;- spiro - 17 -( 4 - aza - 5α - androst - 1 - en - 3 - one ) 16 23 - methyl - 4 - aza - 21 - nor - 5α - chol - 1 - ene - 3 , 20 - dione17 17β -( 2 - pyrrylcarbonyl )- 4 - aza - 5α - androst - 1 - en - 3 - one18 17β -( t - butyldimethyl - silyloxy )- 4 - aza - 5α - androst - 1 - en - 3 - one19 3 - oxo - 4 - aza - 5α - androst - 1 - ene - 17β - carboxamide20 n - ethyl - 3 - oxo - 4 - aza 5α - androst - 1 - ene - 17β - carboxamide21 n -( 2 , 4 , 4 ,- trimethyl - 2 - pentyl ) 3 - oxo - 4 - aza - 5α - androst - 1 - ene - 17β - carboxamide22 n , n - bis ( 2 - propyl ) 3 - oxo - 4 - aza - 5α - androst - 1 - ene - 17β - carboxamide23 17β - hydroxy - 4 - methyl - 4 - aza - 5α - androst - 1 - en - 3 - one24 4 - methyl - 3 - oxo - 4 - aza - 5α - pregn - 1 - ene - 20α - carboxylic acid25 methyl - 4 - methyl - 3 - oxo - 4 - aza - 5α - pregn - 1 - 20α - carboxylate26 2 &# 39 ;, 3 &# 39 ; α - tetrahydro - furan - 2 &# 39 ;- spiro - 17 -( 4 - methyl - 4 - aza - 5α - androst - 1 - en - 3 - one ) 27 4 , 23 - dimethyl - 4 - aza - 21 - nor - 5α - chol - 1 - ene - 3 , 20 - dione28 4 , 22 - dimethyl - 4 - aza - 21 - nor - 5α - chol - 1 - ene - 3 , 20 - dione29 4 - methyl - 17β -( 2 - pyrryl - carbonyl )- 4 - aza - 5α - androst - 1 - en - 3 - one30 17β -( t - butyldimethyl - silyloxy )- 4 - methyl - 4 - aza - 5α - androst - 1 - en - 3 - one31 methyl 4 - methyl - 3 - oxo - 4 - aza - 5α - androst - 1 - ene - 17β - carboxylate32 4 - methyl - 3 - oxo - 4 - aza - 5α - androst - 1 - ene - 17β - carboxamide33 n - ethyl 4 - methyl - 3 - oxo - 4 - aza - 5α - androst - 1 - ene - 17β - carboxamide34 n -( t - butyl ) 4 - methyl - 3 - oxo - 4 - aza - 5α - androst - 1 - ene - 17β - carboxamide35 n - octyl 4 - methyl - 3 - oxo - 4 - aza - 5α - androst - 1 - ene - 17β - carboxamide36 n -( 2 , 4 , 4 - trimethyl - 2 - pentyl ) 4 - methyl - 3 - oxo - 4 - aza - 5α - androst - l - ene - 17β - carboxamide37 n , n - bis ( 2 - propyl ) 4 - methyl - 3 - oxo - 4 - aza - 5a - androst - 1 - ene - 17β - carboxamide______________________________________