Synthesis of diazaheterocycles with a bridgehead nitrogen by photocyclisation ofN-substituted alicyclic imides

摘要

J. CHEM. SOC. PEKKIN TRANS. I 1983 Synthesis of Diazaheterocycles with a Bridgehead Nitrogen by Photocycl i sat i on of N-Substituted A1 i cycl ic I mides John D. Coyle * and Laurence R. B. Bryant Chemistry Department, The Open University, Milton Keynes MK7 6AA N-(Dialkylaminomethyl) -succinimides or -glutarimides give 1,3-diazabicyclo3.3.Ooctanes or -r4.3.01-nonanes on irradiation in acetonitrile, accompanied by variable amounts of the parent imide. Two di- astereoisomers of the products can be obtained, and the relative stereochemistry assigned on the basis of n.m.r. data. With unsymmetrical substrates mixtures of products are formed that demonstrate orientational preferences. Analogous N-substituted pyrrolidin-2-ones do not give photocyclised products (an unusual cleavage product is isolated in low yield), and similar dihydrouracils are relatively photostable.N-(Di-alkylaminoethyl) aliphatic imides give azepine- or azocine-diones on irradiation, whereas N-(dialkyl-aminopropyl) compounds undergo photocyclisation to products with a new perhydro-I ,4-diazepine ring (as do a corresponding 3,4,5,6-tetrahydrophthalimide and phthalimide, although photoreduction is a major process for the latter system). An N-(dialkylaminobuty1)succinimide does not give products with a new perhydrodiazocine ring. An N-(dialkylaminoethyl)maleimide and the analogous 3,4,5,6-tetrahydro- phthalimide give compounds that contain a new piperazine ring, which is in contrast to the saturated imide analogues but similar to the corresponding phthalimide; this process competes effectively with the more usual photoreactions of maleimides involving the carbon-carbon double bond.The intramolecular photochemical hydrogen abstraction and cyclisation reactions of ketones have been extensively studied and applied in a number of synthetic sequences, but amides do not undergo analogous reactions. However, imides do resemble ketones in this respect, and photocyclisations of imides have been reported over the past decade,' especially those of phthalimides,* with particular interest in the formation of macrocyclic products (ring sizes up to 38 atoms) from phthalimides substituted on nitrogen with a long chain ter- minating in a dialkylamino or methylthio group.3 There are far fewer reports of photocyclisation reactions for aliphatic imides: N-alkyl-succinimides and -glutarimides (1) give azepine- or azocine-diones on irradiation ; N-(alkoxymethy1)-succinimides (2) lead to pyrroloI ,2-coxazoles in good yield,' and low yields of photocyclised products are obtained from N-(alkoxyethyl), N-(methylthioethyl) and related derivatives of succinimide.We now report on our study of alicyclic imides substituted on nitrogen with a dialkylaminoalkyl group, which explores the scope of the reaction, and the relationship between systems based on saturated, unsaturated, and aromatic cyclic imides. A 0 hv+CNT00 -iR'R2 (2) the appropriate secondary amine.' On irradiation in aceto-nitrile with light from a medium-pressure mercury arc (quartz filter) they give two diastereoisomers of 1,3-diazabi- cyclo3.3.0octanes in reasonable yield (based on unrecovered substrate), except for (4) which gave more than 90 of succinimide.The reason for this anomalous behaviour is not known, and only from (5) amongst the other succinimides was an appreciable amount (1 8) of succinimide itself isolated after irradiation. hJ_,3-R2 'R2R' (3) R' =H; R~=M~ 52 "I0 (4) R'=Me; R2=Et 5 + 2OIo ( 5) R' = CH = CH2 ;R2= CH 2CH = CH2 26 + 20deg;/0 (6) R' ,R2=(CH2)L 33 13 ( 7) R' ,R2= CH = CHCH2CH2 56 + 6O/o (8) R' , R2= CH20CH2CH2 59 + 18'10 (9) R' ,R2= o -C6HL CHzCH2 44 + 7'10 The assignment of structures for the photoproducts is made on the basis of elemental analysis and spectroscopic data.In particular there is evidence for a five-membered cyclic amide carbonyl (vmax.1 700 cm-'; 6, 175-180 p.p.m.), a quaternary carbon atom adjacent to nitrogen and bearing a hydroxy group (6, singlet at 95-100 p.p.m.; vnlax.3 350 cm-I), a methine group in place of the CH2(R1)group of the sub- strate (6, doublet at 65-75 p.p.m.), and an NCH2N group constrained in a ring system (6, AB pattern in the range 3-5 p.p. rn.). The yields given above are those for the two diastereo- Results and Discussion isomers of the cyclised product; for all the imides except (3),S~~ccinimides.-N-(Dialkylaminomethyl)succinimides (3)-for which only one isomer of the product is possible, the (9) are readily prepared from succinirnide, formaldehyde, and diastereoisomers can be separated by silica-gel column chromatography.The assignment of stereochemistry is based on interpretation of the n.m.r. spectra; to summarise our results and hypotheses, the isomers with OH and R' trans with respect to each other (a)exhibit a smaller difference in 6H values for the two hydrogens of the cyclic NCH2N group because of greater flexibility in the ring system; (b) show a smaller geminal coupling constant between these two hydro- gens because of steric compression of the rings leading to a reduced dihedral angle; (c) have a lower Fc value for the quaternary (C-OH) carbon due to bond lengthening that results from steric compression; and (d) have a lower 6c value for the amide carbonyl because the amide nitrogen is more planar.The difference (0.1-1.2 p.p.m.) in 6, for the hydrogen atoms of the NCH2N group arises basically because the signal for one of the hydrogens is shifted upfield to around 3.6 p.p.m. from the position (typically 4.5 p.p.m.) of the signal for the NCH2N protons in the imides (3)-(9). This effect is most probably caused by the lone pairs of the nitrogen atoms (an effect of the hydroxy group is ruled out because this should be very different for the two diastereoisomers, which is not the case). It has been shown that there is a large 6, difference (0.92 p.p.m.) between the geminal hydrogens adjacent to nitrogen in the spectrum of quinolizidine (lo), and this is ascribed to the shielding effect of the axial lone pair on the axial hydrogens of the adjacent methylenes.The difference m (101 between the diastereoisomers arises because the cyclised product e.g. from the imide (8) with OH and R1groups cis has a more rigid structure, whereas that with OH and R1 groups trans is more flexible and so the shielding effect of the lone pairs will be less pronounced. This hypothesis requires that inversion at the amine nitrogen in the photoproducts be unimportant (i.e. that the amine lone pair be essentially uni- directional), and support for this idea comes from the spec- trum of the single isomeric photoproduct from imide (3). There is much less hindrance to nitrogen inversion in this compound, and at room temperature the signal for both hydrogens of the cyclic NCH2N group appears as a singlet.Only as the temperature is lowered does the difference become apparent (the difference in ZiH is just over 0.1 p.p.m. at 220 K). The diastereoisomer with OH and R1groups trans is more sterically strained than the other isomer, and this leads to a number of effects in the n.m.r. spectra. Steric compression leads to a small increase in the internal bond angle of the imidazolidine ring, and hence to a decrease in the angle between the geminal hydrogen atoms of the NCH2N group; this would be expected to lead to a reduction in the geminal coupling constant, as is observed. The steric compression is also taken up in two other ways. First the C-C bond between the bulky groups (HO-C-C-R') lengthens slightly, and this produces lo a decrease in SC for one or both of the carbon atoms; in our systems a decrease is seen most clearly for the quaternary carbon (the signal for the other carbon shows a much smaller variation between the diastereoisomers). Secondly the steric strain is relieved in part by the amide nitrogen becoming more nearly planar; this results in a lower for the amide carbonyl (ca.175 p.p.m., as compared with ca. 180 p.p.m. for the other isomer). The hypotheses are plausible and consistent with the spectroscopic results obtained, and they are in keeping with spectral data for related photoproducts from phthalimide J. CHEM. SOC. PERKIN TRANS. I 1983 substrates," where definite structural assignment has been made for compound (1 1) by X-ray crystallographic analysis.Ph (11) The ratio of isolated amounts of the two diastereoisomers ranges from 1.3: 1 for imide (5) to 9: 1 for imide (7). Changing the solvent from acetonitrile to water for imide (8) does not affect the ratio of products, nor the isolated yield; however, in toluene the proportion of the major isomer in- creases (from 3.3 : 1 to ca. 8 : l), although the isolated yield is lower. In toluene as solvent the reaction may be photo- sensitised, since the solvent absorbs much more strongly than the imide. With imides (7) and (9) derived from an unsymmetrical amine, the major products arise by reaction at the allylic or benzylic methylene group, rather than at the less activated position.However, a small amount (ca. 6) of a product (12) arising from the alternative mode of cyclisation was also isolated after irradiation of (7). The product (12) is dis-tinguished from the major products in that the alkene gives rise to n.m.r. signals that are much closer together (6, 5.75-5.8; 6c 124.5 p.p.m.; cf. 6, 5.85-6.2; 128.2 and 122.2 p.p.m. for the major photoproduct). We were interested to see if there is also an orientational preference with regard to an unsymmetrical imide ring, and so the 2-phenylsuccini- mide derivatives (1 3) and (1 8) were prepared and irradiated. From (1 3), all four diastereoisomeric products (14)-( 17) were formed; three were isolated in a pure state in the ratio 7 : 3 : 1, and were assigned structures (14), (15), and (16), respectively, and a smaller amount of the fourth (17) was obtained contaminated with one of the others.The main arguments in the assignment of orientation and stereo-chemistry are as follows. The 6H value for one of the protons of the CH2(N) group adjacent to the quaternary C(0H) atom, and the aC value for the carbon atom of this group, are much lower for the major photoproduct than for the others (1.87 and 62.4 p.p.m., cf. 2.8-3.0 and ca. 66.3 p.p.m. for the other isomers). This is attributed to the shielding effect of the phenyl ring, and a study using molecular models indicates that this operates effectively only in isomer (14), which has the hydroxy and phenyl groups trans with respect to each other.The other product with the same orientation of cyclisation (15) is taken to be the one that shows a similar pattern of signals (doublets of doublets at 3.70, 3.44, and 2.62 p.p.m.) for the CH2CH- (Ph) protons as for (14) (dd at 3.66, 3.30, and 2.63 p.p.m.),whereas (16) shows a different pattern (dd at 3.80, 2.71, and 2.39 p.p.m.) and (17) also shows more signals (not completely resolved) in the 2.3-2.8 p.p.m. region. The assignment for (16) is based largely on the pattern of coupling constants for the CH2CH(Ph) protons J 14, 10, and 2.5 Hz, compared with 17, 8.5, and 2.5 Hz for (14), and 16, 12.5, and 8.5 Hz for (15), which is taken to be characteristic of the relative stereo- chemistry of the OH and Ph groups.From the reaction of (18) six products were identified by t.l.c., and the major one was isolated by silica-gel chromato- graphy. Although the stereochemistry cannot be assigned, the orientation of cyclisation corresponds to structure (1 9) rather than (20), as judged by the ZiC value for the carbonyl group. We conclude that cyclisation can occur at either carbonyl J. CHEM. SOC. PERKIN TRANS. I 1983 HO + + (17) (16) + group in a 2-phenylsuccinimide system, but that there is a preference for reaction at the C-1 carbonyl (adjacent to CHPh). This could be due to an interaction of the partially positive amine nitrogen (arising from an initial charge transfer process) with the electrons of the phenyl ring, which promotes transfer of a hydrogen (or proton) to the C-1 carbonyl because it brings the reacting N-Me group closer to C-1 than to C-4.The major diastereoisomer (14) is the most hindered sterically, and it is possible for the cis relationship between the phenyl group and the ring methylene NCH2C(OH) to be preserved if ring-closure follows very rapidly after the hydro- gen or proton has been transferred, PyrroZidin-2-ones.-Saturated aliphatic amides are quite different from ketones or imides in their photochemical behaviour; they do not react with alkenes to form oxetanes, nor do they take part in intramolecular hydrogen abstraction reactions. For example, N-alkylpyrrolidin-2-onesundergo only cleavage reactions,'2 and there is no evidence for hydrogen abstraction from the alkyl group.As model amides related to succinimides(3)-(9), Mannich bases (21)-(22), of pyrrolidin- 2-one were prepared and irradiated, but the photolysis pro- duced complex mixtures of products. From (21) only one product was isolated pure, and this was identified on the basis of spectroscopic data as N-(but-3-enylamino)methylpyr-rolidin-2-one (23). The identity was confirmed by reaction with formaldehyde and pyrrolidin-Zone to give (24), which was synthesised independently from pyrrolidin-2-one, form- aldehyde, and but-3-enylamine. Despite many attempts, (23) could not itself be made by a Mannich-type procedure. ( H N Mbsol; (21) R', R2= CH2CH =CHCH2CH2 ( 23) (22) R', R2= CH2CH20CH2CH2 0 The formation of (23) from (21) is very unusual, involving the loss of a carbon atom from the tetrahydropyridine ring, and at this stage any mechanistic suggestions are purely speculative.The photolysis of (21) and (22) suggests that, even with N-dialkylaminomethyl substituents, saturated amides are not useful substrates for photochemical hydrogen abstraction and cyclisation. GZuturirnides.-Only two previous examples of glutarimide Mannich bases have been de~cribed,'~ based on the specific, pharmacologically active compounds bernegride and thalido- mide. We needed to modify normal Mannich reaction proce- dures in order to prepare N-dialkylaminomethyl derivatives (24)-(27) of glutarimide ; the corresponding derivatives of 3,3-dimethylglutarimide were also prepared but not irradiated. Irradiation of the glutarimides gave photoproducts with the 1,8-diazabicyclo4.3.Ononane ring system, and as with the succinimide analogues, two diastereoisomers were formed.In the case of imides (24), (25), and (26), glutarimide was also isolated in high yield (85, 50, and 53). (24) R',R~=(cH,), 0.6 + 0 .Lo/o (25) R',R2= CH =CHCH2CH2 30 + 8"/0 (26) R',R2= CH20CH2CH2 8 + Lo/, (27) R',R*= o -CGHLCH2CH2 19 + 17'/0 The glutarimides (24)-(27) react as readily as the cor- responding succinimides, but this is not true of derivatives of another six-membered cyclic imide analogue, dihydrouracils. It has been reported l4 that dihydrouracil does not form Man- nich bases, but we were able to prepare the derivatives (28)- (31).However, these compounds are photochemically stable, unlike the analogous five-membered ring hydant~ins,'~ and only small amounts of product mixtures appear, even after 50 times the extent of irradiation that is required for the imide derivatives to give products in greater than 50 conversion. Formation of Larger Rings.-It has been reported pre-viously that N-alkylphthalimides,16 -glutarimides, or -succin- imides 4~17give ring-expanded products e.g.(32) by way of an initial fused azetidinol. We irradiated N-(dialkylaminoethyl) derivatives of succinimide, (33) and (34), glutarimide, (33, and 1,2,3,6-tetrahydrophthalimide,(36), to see if the presence of a nitrogen atom in the side-chain might lead instead to products with a new piperazine ring. In the event all of these systems gave perhydroazepine- or perhydroazocine-diones, as shown by the presence of ketone and amide carbonyl groups and the presence of an unchanged symmetrical amine sub- stituent.(33) R' = R2=Me 17'/o (34) R',R2= CH,CH,OCH,CH, 46O/o 0 The reactions of the glutarimide (35) and the tetrahydro- phthalimide (36) give good isolated yields of photoproduct. The value of this type of photochemical reaction for preparing azepinediones from N-alkylsuccinimides has been ques-tioned,I8 and compounds with sulphur in the side-chain give only very low yields of product, but evidently some nitrogen- substituted derivatives can lead to much better yields.The formation of a photocyclised product from (36) is in direct contrast to the production of a cyclobutane dimer from the N-ethyl derivative of the same imide.'* In principle this opens J. CHEM. SOC. PERKIN TRANS. I 1983 up a route to benzazepinediones which are not available from N-(dialkylaminoethy1)phthalimides l9 because of a com-peting reaction to give photocyclised products such as (37). However, our attempts to dehydrogenate the photoproduct from (36) using dichlorodicyanobenzoquinonewere not suc- cessful, perhaps because of the a-aminoketone group in the molecule. N-3-(Dialkylaminopropyl)-succinimides, (38) and (39), and -3,4,5,6-tetrahydrophthalimide,(40), were found to give cyclic products on irradiation that contain a new perhydro- 1,4-diazepine ring.The main evidence for these product structures is that the compounds are isomeric with the sub- strates, contain an aromatic lactam carbonyl group and a quaternary (N)C(OH), do not have pairs of equivalent carbon atoms in an ' intact ' morpholine ring (as would be expected if a new five-membered ring were formed), but do have four protons on carbons adjacent to oxygen. Such reactions have been reported previously for the corresponding phthalimides,20 but not for aliphatic imides. However, the isolated yields of these aliphatic products are not high, and it is possible that other isomeric photoproducts are present in the reaction mixtures. The diastereoisomers of the product from (40) exhibit unusual differences in the carbon-13 n.m.r.signals for the carbon atoms of the morpholine ring. These signals are at 68.5, 66.7, 66.5, and 52.7 p.p.m. for the major isomer, but at higher field (63.5, 61.1, 60.1, and 50.6 p.p.m.) for the other isomer. The effect probably arises because the more cage-like structure of the minor stereoisomer can hold some of the carbon atoms in the shielding zone of the C=C double bond. hJ (37) Ph '-Ph hV HO R' I R2 (38) R' =H; R2=Me 31 O/o (39) R',R2= CH20CH2CH2 12"/0 0 0 11 + 6OlO A second product (8) from the reaction of (39) could not be identified, although it is certainly not a photocyclised pro- duct with a new 5-membered or 7-membered ring, nor an azepinedione. For comparison, we irradiated the analogous phthalimide (41), which has not been included in other reports of phthalimide photochemistry.The formation of the photoreduced imide as the major J. CHEM. SOC. PERKIN TRANS. I 1983 .o .O + + HO Ca. 30deg;/o ca. 20deg;/0 product even in a normally non-reducing solvent such as acetonitrile, suggests that intramolecular reaction for this particular phthalimide is quite slow. The presence of both pyrrolidine and diazepine products indicates that there are some limitations on the application of this photoreaction for making compounds with a perhydro-l,4-diazepine ring," although the use of N-acylated derivatives 2o may overcome this. As with some of our other photoproducts, the diastereo- isomers of the perhydrodiazepine product from (41)show quite large differences in the carbon-13 chemical shift values for certain of the atoms of the ring system.Irradiation of the N-4-(morpholin-4-yl)butylsuccinimide (42) gives a perhydroazepinedione and a photocyclised product with a new pyrrolidine ring, with no products isolated in which reaction takes place at either of the positions adjacent to the amine nitrogen. This indicates that in the aliphatic systems there is no strong preference for reaction at a remote but activated position, at least not for compounds with a chain of four methylenes between the two nitrogen atoms. In turn this could mean that the aromatic ring of phthalimides enhances the electron-acceptor properties of the imide ring to such an extent that charge-transfer interactions in the excited state 0 0 CNbsol;So0 N, / w bsol; (42) + 26'/" 0 lead to conformations in which the terminal heteroatom and the imide are in close proximity, whereas such interactions are less important for aliphatic imides.MaZeimides.-In order to test this hypothesis we prepared and irradiated two compounds (43)and (44)with a maleimide ring system. The double bond in conjugation with the imide carbonyl groups provides a chromophore more like that of an aromatic imide than of a succinimide, and in confirmation of this the major products of irradiation are compounds with a new fused piperazine ring, analogous to products from similar phthalimides l9 rather than those from succinimides.It follows that a range of medium- and large-ring photoproducts may be accessible by photocyclisation of maleimide derivatives, as it is for phthalimides but not for succinimides. These are the first examples of maleimides that undergo photochemical hydrogen abstraction and cyclisation to a position in the N-substituent, and it contrasts with the reac- tions at the C=C double bond that dominate so much of maleimide photochemistry. Irradiation of the analogous phthalimide system (45)has not been reported previously, and for completeness we prepared it and isolated the two di- astereoisomers of the expected photoproduct. (45) 31+ 12 bsol;J0 A maleimide Mannich base (46) was prepared and ir- radiated, but this proved, unexpectedly, to be photochemically unreactive.Experimental N-(Dialkylaminomethyl) substituted imides and amides were made by Mannich reaction procedures.2' The glutarimide derivatives were prepared by warming glutarimide with an equimolar mixture of aqueous formaldehyde (40) and secondary amine without extra solvent. Compounds (6),7 (8),7 (18),22 (22),14and (46) 23 have been reported previously. N-(Dialkylaminoethy1)imides and higher homologues were prepared by standard methods.24 2-Phenylsuccinimide 25 and but-3-enylamine26 were prepared according to published pro- cedures. Light petroleum refers to the fraction with b.p. in the range 40-60 "C; ether refers to diethyl ether. N-(Diulky1uminomethyl)succinimide(3)was obtained in 74 yield; m.p.45-47 "C (ether-light petroleum) (Found: C, 53.9; H, 8.1; N, 17.9. C7H12N202requires C, 53.8;H, 7.8; N, 17.9); vmx. 1 775 and 1 720cm-'; 6" (90MHz, CDCl,) 2.30 (6H, s), 2.75 (4 H, s), and 4.34 (2 H, s); (90MHz, CDCl,) 28.1, 43.1, 60.8, and 178.0 p.p.m. N-(Diethylaminomethy1)succinimide (4) was obtained in 58 yield; m.p. of HCl salt 142-144 "C (Pr'OH) (Found: C, 58.6;H, 8.9;N, 15.3.C9Hl6N2o2requires C, 58.7;H, 8.75;N,15.2); vmx. 1 775 and 1710 cm-'; 6H (60MHz, CDCl,) 1.08 (6H, t, J 7 Hz), 2.63 (4H, q, J 7 Hz), 2.73 (4 H, s), and 4.45 (2H, s). N-(Diullyluminomethy1)succinimide(5) was obtained in 72 yield (Found: C, 63.8;H, 7.65;N, 13.3.CllH16N202requires C, 63.4;H, 7.7;N, 13.45); vmx. 3090, 1710, and 1645sh cm-'; 6~ (60MHz, CDCl,) 2.71 (4 H, s), 3.32 (4H, d, J6 Hz),4.41 (2 H, s), 4.95-5.3 (4 H, m), and 5.55-6.2 (2 H, m).N-(1,2,5,6-Tetruhydropyridin-1-ylmethyl)succinimide (7) was obtained in 47 yield; m.p. 73-75 "C (EtOH) (Found: C, 61.7;H, 7.0;N, 14.2.Cl0Hl4N2O2requires C, 61.8;H, 7.3; N, 14.4); vmax.3 080,1 770,and 1 700 cm-'; 6H (60MHz, CDCl,) 1.9-2.3 (2H, m), 2.55-2.85 (6 H, m), 2.95-3.25 (2H, m), 4.45 (2H, s), and 5.63 (2H, s); 6c (90MHz, CDCI,) 26.1, 28.2, 48.0, 49.7, 60.0, 124.9, 125.1, and 178.1p.p.m. N-(1,2,3,4-Tetrahydroisoquinolin-2-ylmethyl)succinimide(9) was obtained in 71 yield; m.p. 122-124 "C (EtOH) (Found: C, 69.0;H, 6.4;N, 11.3. C14H16N202 requires C, 68.85;H, 6.6;N, 11.45); vmax.1775 and 1710 cm-'; ZiH (60 MHz, CDCl3) 2.72 (4 H, s), 2.91 (4H, s), 3.80 (2 H, s), 4.62 (2 H, s), and 7.10 (4 H, s); (90MHz, CDCI,) 28.2,29.3, 49.0, 52.9, 60.0, 125.7, 126.2,126.7,128.8, 134.2, 134.5, and 178.1 p.p.m.N-(Dimethylaminomethyl)-2-phenylsuccinimide(1 3) was ob- tained in 68 yield; m.p. 96-98 "C (EtOH) (Found: C, 67.0; H, 7.0;N, 12.1. Cl3HI6N202 requires C, 67.2;H, 6.9;N, 12.1); vmax.1 770and 1 695 cm-'; amp;H (60MHz, CDCl,) 2.33 (6 H, s), 2.84 (1 H, dd, J 18.5 and 5 Hz), 3.25 (1 H, dd, J 18.5 and 9 Hz), 4.05(1 H, dd, J9 and 5 Hz), 4.45 (2 H, s), and 7.2-7.35 (5 H, m); Sc (90MHz, CDCI,) 37.1 (t), 43.1 (q),46.0 (d), 61.2, 127.2, 128.0, 129.2, 137.3, 177.0, and 178.6 p.p.m. N-(1,2,5,6-Tetrahydropyridin-1 -ylnzethyl)pyrrolidin-2-one (21)was obtained in 63 yield; m.p.of HCl salt 163-165 "C (EtOH) (Found: C, 66.4;H, 9.1;N, 15.5. C1oH16N20 requires C, 66.6;H, 8.95;N,15.5); v,,,,. 3 033 and 1 680 cm-'; 6H (60MHz, CDC13) 1.7-2.8 (8 H, m), 3.03 (2 H, s), 3.51 (2 H, t, J 6 Hz), 4.05 (2 H, s), and 5.71 (2 H, s); 6c (90MHz, CDCM 18.1, 26.0, 31.2, 47.6, 47.7, 49.9, 64.3, 125.0, 125.1, and 175.6 p.p.m.N-(Piperidin-1-ylmethyl)glutarimide (24) was obtained in 49 yield; m.p. 83-85 "C (ether-light petroleum) (Found: C, 62.6; H, 8.5; N, 13.2. CllH18N202 requires C, 62.8; H, 8.6; N, 13.3); vmns, 1 726 and 1 667 cm-'; 6" (60 MHz, CDC13)1.2-2.2 (8H, m), 2.3-2.9 (8H, m), and 4.73 (2 H, s).Tetrahydrupyridin-1-ylnzethyl)glutarimicle (25)N-( 1 ,2,5,6-was obtained in 61 yield; m.p. 71-74 "C (ether) (Found: C, 63.4;H, 7.85;N, 13.4.Cl1H16N202 requires C, 63.4;H, 7.75; N, 13.45);v,,,:~~.3 029,I 720,and 1 684 crn-'; amp;H (60MHz, CDCI,) 1.85-2.4 (4 H, m), 2.55-2.9 (6 H, m), 3.05-3.3 (2H, ni), 4.86 (2 H, s), and 5.70 (2 H, s).N-(Morphulin-4-ylmethyl)glutarinzide(26)was obtained in 42 yield; m.p.103.5-106.5 "C (ethanol-ether) (Found: C, 56.2; H, 7.4;N,13.1. C10H16NZ03requires C, 56.6;H, 7.6; N, 13.204); v,,,:,,. 1 726 and 1 668 cm-'; 6H(60 MHz, CDC13)1.75-2.15 (2 H, m), 2.4-2.85 (8 H, m), 3.55-3.9 (4 H, m), and 4.75 (2 H, s); (90 MHz, CDCI3)17.1, 33.0, 51.4, 60.0, 67.0,and 173.4p.p.m. J. CHEM. SOC. PERKIN TRANS. I 1983 N-(1,2,3,4-Tetrahydroisoquinolin-2-ylmethy1)glutarimide(27) was obtained in 67 yield; m.p. 93-95 "C (ethanol-ether) requires C,(Found: C, 70.1;H, 7.15;N, 10.85.Cl5Hl8N2O2 69.75;H, 7.0;N, 10.85); vmx.1735 and 1686 cm-'; ti,, (60MHz, CDCl,) 1.85-2.2 (2H, m), 2.5-3.0 (8 H, m), 3.84 (2H, s), 4.96 (2 H, s), and 7.08 (4 H, s); aC (90MHz, CDCI,)17.0,29.1, 32.9, 49.1, 53.2, 59.8, 125.5, 126.0, 126.6, 128.6, 133.9, 134.8, and 173.4p.p.m. 3-(Piperidin-l-y2methyl)dihydrouracil(28)was obtained in 62 yield; m.p. 109-111 "C (EtOH) (Found: C, 56.75;H, 8.0;N, 20.1. C10H17N302requires C, 56.85; H, 8.1; N, 19.9); vmx. 3 225, 1 725,and 1 680 cm-l; 6, (60 MHz, CDCl,) 1.3-1.5 (6 H, m), 2.45-2.5 (4 H, m), 2.65 (2 H, t, J7 Hz), 3.55 (2 H, t, J7 Hz), 4.11 (2 H, s), and 8.75 (1 H, br); 6c (90MHz, CDCI,) 24.5, 26.0, 31.4, 41.8, 51.9, 69.0, 153.6, and 170.4p.p.m.Tetruh ydropyr idin- 1-y lmethy1)dihy drouracil (29)3 -(1 ,2,5,6-was obtained in 69 yield; m.p.107-109 "C (EtOH) (Found: C, 57.3;H, 7.5; N, 20.0. C10H15N302 requires C, 57.4;H, 7.2;N, 20.1); vmax.3 200, 3 080,1 730,and 1 675 cm-'; 6, (60MHz, CDCI,) 2.0-2.35 (2 H, m), 2.5-2.8 (4H, m), 2.95-3.25 (2 H, m), 3.55 (2 H, t, J7 Hz), 4.22 (2 H, s), 5.70 (2 H, s), and 8.8 (1 H, br); 6c (90 MHz, CDC1,) 26.2, 31.5, 41.9, 47.7, 50.1, 68.2, 125.4, 125.5, 153.8, and 170.6 p.p.m. 3-(Morpholin-4-ylmethyl)dihydrouracil(30)was obtained in 68 yield; m.p. 152.5-154.5 "C (EtOH) (Found: C, 50.6; H, 7.15;N, 19.8. C9H15N303requires C, 50.7;H, 7.1; N, 19.7);vmX. 3 203,3 090,l 730, and 1 680cm-'; 6H(60MHz, CDC1,) 2.35-2.8 (6 H, m), 3.53 (2H, t, J 7 Hz), 3.65-3.75 (4H, m),4.15 (2 H, s), and 8.55 (1 H, br); (90 MHz, CDC13)31.1, 41.6, 50.9, 66.8,68.5,153.4,and 170.0 p.p.m.3-( 1,2,3,4- Tetrahydroisoquinolin-2-y2methyl)dihydrourucil (31)was obtained in 64 yield; m.p.124-126 "C (EtOH) (Found: C, 64.8;H, 6.45;N, 16.0.C14H17N302requires C, 64.85;H, 6.6;N,16.2); vmx. 3 200,3 080, 1728, and 1680 cm-'; 6H (60MHz, CDCl3) 2.61 (2 H, t, J 7Hz),2.88 (4 H, s),3.55 (2H,t, J 7 Hz), 3.75 (2H, s), 4.30 (2 euro;3, s), 7.11 (4 H, s), and 8.85 (1 H, br); tic (90 MHz, CDCI,) 29.0,31.1, 41.2, 48.3, 53.1, 67.9, 125.7, 126.3, 126.6, 128.7, 134.0, 134.1, 153.4,and 170.2 p.p.m. N-2-(Dirnethylarnino)ethylsuccinimide(33)was obtained in 51 yield; m.p. of HCl salt 196-198 "C (EtOH) (Found: C, 56.3; H, 8.5; N, 16.5.C8HI4N2O2requires C, 56.45;H, 8.3; N, 16.5); vmx.1770 and 1700 cm-I; (60 MHz, CDCI,) 2.25 (6 H, s), 2.51 (2 H, t, J 7 Hz),2.72 (s, 4 H), and 3.64(2H, t, J 7 Hz); for hydrochloride salt SC(90 MHz, D20)30.8 (t), 36.2 (t), 45.6 (q), 57.2,and 183.5 p.p.m. N-2-(Morpholin-4-yl)ethylsuccinimide(34)was obtained in 58 yield; m.p. 79-81 "C(Found: C, 56.5; H, 7.7;N, 13.1. CloH16N20, requires C, 56.6;H, 7.6;N, 13.2); vmau,1 770 and 1700 cm-'; SH(60 MHz, CDCI,) 2.35-2.85 (10H, m, including singlet at 2.72)and 3.5-3.85 (6 H, m). N-2-(Morpholin-4-yl)ethylglutarimide(35)was obtained in 72 yield; m.p. 80-82 "C (Found: C, 58.2; H, 7.9;N, 12.2. Cl1HlaN2O3requires C, 58.4;H, 8.0;N,12.4);v,,,~~. 1 721and 1 667 cm-'; 6H(60MHz, CDCI,) 1.93 (2 euro;3, quintet,J 6 Hz), 2.4-2.75 (10 H, m),3.6-3.7 (4 H, m), and 3.92 (2H, t, J 7 Hz); 6c (90MHz, CDCI,) 17.2,32.8, 36.3, 53.7,55.9, 67.0,and 172.4 p.p.m.N-2-( 1,2,3,6-terrahydrophthalimideMorpholin-4-yl)ethyl-(36)was obtained in 63 yield (Found: C, 63.6;H, 7.7;N, 10.5.C14H20NZ03requires C, 63.6;H, 7.6;N, 10.6); v,,,~~. 3042,I 772,1 709,and 1645sh cm-'; 6H (60MHz, CDCl3)2.25-2.65 (10 H, m), 3.0-3.2 (2 H, m), 3.45-3.85 (6 H, m),and 5.8-6.0 (2 H, m); (90MHz, CDCI,) 23.5, 35.7, 39.0, 53.4,55.1, 67.0, 127.6, and 180.0p.p.m. N-3-( Dimethyfumino)propylsuccinimide (38)was obtained J. CHEM. SOC. PERKIN TRANS. I 1983 in 72 yield; m.p. of HCl salt 193-195"C (EtOH) (Found: C, 58.6;H, 8.8;N,15.3.CgH16N202 requires C, 58.7;H, 8.75; N, 15.2); vmax.1 770and 1 700cm-'; SH (60MHz, CDCl3)1.5-2.45 (10H, m, including singlet at 2.19), 2.69 (4H, s), and 3.57(2H, t, J7Hz); 6c (90MHz, CDC13) 25.7, 28.1, 37.2 (t),45.4(q), 57.0,and 177.2p.p.m.photoproducts from (4),(6), (7), @), (91,and (34)were described in our preliminary report.6 Irradiation of (3) gave 5-hydroxy-3-methyl-1,3-diazabicyclu-3.3.0octan-8-one (52); v,,,. 3 350and 1690cm-'; 6, (90 MHz, CDC13) 2.1-2.5 (7 H, m, incl. 2.41,s), 2.65(1 H, d, J9Hz), 2.96(1 H, d, J9Hz), 3.9(1 H, v.br), and 3.97(3 H, N-3-(Morpholin-4-yl)propylsuccinimide(39) was obtained in 78 yield; m.p. 65.5-67.5 "C (Found: C, 58.5;H, 7.9;N, 12.4.CllH18N203 requires C, 58.4;H, 8.0;N, 12.4); v,, 1 760and 1 690cm-'; SH(60MHz, CDC13) 1.74 (2 H, quintet,J 8 Hz), 2.25-2.55 (6 H, m), 2.73 (4H, s), and 3.5-3.85 (6H, m); Sc (90 MHz, CDC13) 24.3, 28.2, 37.2, 53.6, 56.3, 67.0,and 177.2p.p.m.N-3-(Morpholin-4-yl)propyl-3,4,5,6-tetrahydrophthalimide(40)was obtained in 55 yield; m.p. of HC1 salt 211-214 "C (EtOH) (Found: C, 64.9;H, 8.0; N, 10.0. C15HzzN203 requires C, 64.7;H, 8.0;N, 10.1); vmx. 1763, 1705, and 1675sh cm-'; 6H (60 MHz, CDC13) 1.65-1.80 (6 H, m),2.0-2.4 (10H, m), and 3.45-3.7 (6H, m); 6c (90 MHz, CDC13) 20.0, 21.4, 25.4, 36.0, 53.7, 56.4, 67.0, 141.5, and 171.2p.p.m. N-3-(Morpholin-4-yl)propylphthalimide (41) was obtained in 62 yield; m.p. of HCl salt 238-240 "C (EtOH) (Found: C, 65.7;H, 6.8;N, 10.3.C15H18N203requires C, 65.7;H, 6.6; N, 10.2); vmx. 1 770and 1 710cm-'; 6, (60MHz, CDC13)1.86(2H, quintet, J 7Hz), 2.3-2.5 (6 H, m), 3.45-3.55 (4H, m), 3.78 (2 H, t, J7Hz), and 7.65-7.9 (4H, m); 6, (90MHz, CDC13) 24.8, 36.6, 53.6, 56.5, 66.8, 123.1, 132.4, 133.9, and 168.4p.p.m.N-4-(Morpholin-4-yl)butylsuccinimide(42) was obtained in 56 yield (Found: C, 59.9;H, 8.3;N, 11.6.ClzH20Nz03 requires C, 60.0;H, 8.4;N,11.65); vmx. 1 772and 1 700 cm-'; 6, (60 MHz, CDC13) 1.5-1.6 (4H, m), 2.25-2.45 (6H, m), 2.7(4H, s), 3.53 (2H, t, J 7Hz), and 3.65-3.75 (4 H, m); 6, (90 MHz, CDC13) 23.8, 25.6, 28.1, 38.6, 53.7, 58.3, 66.9, and 177.2p.p.m. N-2-(Morpholin-4-yl)ethylmaleimide(43)was obtained in 31 yield (Found: C, 56.9;H, 6.6;N, 13.2. C10H14N203 requires C, 57.1; H, 6.7;N, 13.3); vmax.3095,1 768,1 710, and 1 678shcm-'; tjH (60MHz, CDCl,) 2.35-2.7 (6 H, m),3.45-3.65 (6 H, m), and 6.71 (2 H, s); 8, (90MHz, CDC13) 34.8,53.4,55.9, 66.9, 134.1, and 170.7p.p.m.N-2-(Morpholin-4-yl)ethyl-3,4,5,6-tetrahydrophthalimide(44)was obtained in 61 yield; m.p. of HC1 salt 226.5-228.5 "C (EtOH) (Found: C, 63.4;H, 7.8;N,10.7.C14HZONZ03 requires C, 63.6;H, 7.6;N,10.6); vmax.1765, 1710, and s, becomes an AB pattern at low temperature, e.g. 220 K); SC (90 MHz, CDC13) 33.0, 33.1, 39.6, 66.0, 66.3, 95.8, and 176.8 p.p.m. (M+, m/z 156.0900. C7Hl2N2O2 requires M, 156.0894). Irradiation of (5) gave 3-allyl-5-hydroxy-4-vinyl-1,3-di-azabicyclo3.3.0octan-8-one.First isomer (26); vmax. 3 350, 3085, 1 710,and 1 645 cm-'; SH (90MHz, CDC13)2.05-3.7 (8H, m), 3.83 (1 H, d, J 6 Hz), 4.28(1 H, d, J 6Hz), and 5.1-6.0 (6 H, m); 6, (90MHz, CDC13)30.7, 32.9, 54.2, 63.4, 74.9, 96.0, 118.8, 121.7, 132.5, 133.2, and 175.6 p.p.m.Second isomer (20); vmax. 3380,3080, 1 705,and 1 645 crn-l; 6" (90MHz, CDCI,) 1.85-3.3 (7 H, m), 3.45(1 H, d, J 7.5 Hz), 4.45(1 H, d, J 7.5 Hz), and 4.9-6.15 (7 H, m); 6, (90MHz, CDCI,) 31.2, 31.9, 53.7, 63.2, 75.1, 97.8, 117.9, 120.9, 132.8, 134.4, and 178.1p.p.m. Irradiation of (13) gave 5-hydroxy-3-methyl-6-phenyl-1,3-diazabicyclo3.3.0octan-8-one(14)and (15) and 5-hydroxy-3-methyZ-7-phenyZ-l,3-diazahicyclo3.3.Ooctan-8-one(1 6) and (17). Compound (14)was isolated as a colourless oil (34); v,,,. 3330and 1 700cm-'; 6H (400MHz, CDC13) 1.87(1 H, d, J9.5Hz), 2.44(3 H, s), 2.55(1 H, d, J, 9.5Hz), 2.62(1 H, dd, J 17 and 2.5 Hz), 3.44(1 H, dd, J 17 and 8.5 Hz), 3.70 (1 H, dd, J 8.5 and 2.5Hz), 3.73(1 H, d, J 6Hz), 4.15,(1 H, d, J6Hz), 4.65(1 H, br), and 7.1-7.4 (5H, m); 6, (90MHz, CDC13) 39.4(t), 39.8(q), 48.8(d), 62.4(t), 66.2(t), 99.0(s),127.4, 127.5, 128.9, 139.7, and 175.3p.p.m.A mixture (51) of the other three isomers was separated by repeated column chromatography. Compound (1 5) was a colourless oil ; vmL 3335 and 1 700cm-'; SH (400MHz, CDCI,) 2.42,(3 H, s), 2.63(1H,dd,J16and7.5Hz),2.83(1 H,d,J9Hz),3.01(1H, d, J9Hz), 3.30(1 H, dd, J 16 and 12.5Hz), 3.66(1 H, dd, J 12.5and 7.5Hz), 3.89(1 H, d, J 6.5Hz), 4.16(1 H, d, J 6.5 Hz), and 7.3-7.4 (5 H, m); 6, (90 MHz, CDCl,) 37.8(t),39.5 (q), 51.1 (d), 66.1 (t), 66.3 (t), 95.9(s), 126.3, 127.8, 128.4, 128.6, 128.9, 136.0, and 175.1 p.p.m.(M+, in/z 232.1 197. cl3Hl6N2o2requires M, 232.1206).Compound (16) was a colourless oil; vmax.3 335and 1 698cm-'; SH(400MHz CDC13) 2.40(3 H, s), 2.39(1 H, dd, J 14and 2.5Hz), 2.53 (1 H, d, J9.5Hz), 2.71(1 H, dd, J 14and 10.5Hz), 3.01 (1 H, 1 675shcm-'; tiH (60MHz, CDC13)1.6-1.95 (4H, m), 2.25-2.75(10 H, m), and 3.45-3.85 (6 H, m); 6, (90MHz, CDCI3)19.9, 21.4, 34.5, 53.5, 56.4, 66.9, 141.4,and 171.0p.p.m. N-2-(Morpholin-4-yl)ethylphthaliriiide(45)was obtained in 77 yield; m.p. 129-131 "C (EtOH) (Found: C, 64.8;H, 6.3;N,10.8.Cl4HI6N2O3requires C, 64.6;H, 6.2;N,10.8); vmax.1765 and 1710cm-'; 8" (60 MHz, CDCI,) 2.45-2.7 (6H, m, including 2.63,t, J 7Hz), 3.6-3.9 (6 H, m, including 3.83,t, J 7 Hz), and 7.65-7.85 (4H, m); 6, (90MHz, CDC13)35.0,53.5, 56.1, 67.0, 123.2, 132.2, 133.9, and 168.3.N-(Morpholin-4-ylmethyl)maleimide(46)was prepared by way of W(hydroxymethy1)maleimide 23 in 46 overall yield; m.p. 142.5-144.5 "C (lit.,23 143-145 "C); vmas. 3 140,1 770, and 1 710cm-'; tiH (90 MHz, CDC13)2.6(4H, m), 3.7(4H, m), 4.43 (2 H, s), and 6.79 (2 H, s); 6, (90 MHz, CDC13)50.7, 59.3, 66.8, 134.3,and 171.6p.p.m. Irradiations were carried out with a 400-Wmedium-pressure mercury arc with quartz filter (Pyrex for phthali- mides), using ca. 0.01mol of the imide in acetonitrile solvent. After removal of the solvent, the product mixture was separated by silica-gel chromatography with chloroform, chloroform-acetone, or chloroform-methanol as eluant.The d, J 9.5Hz), 3.80(1 H, dd, J 10.5and 2.5Hz), 3.95(1 H, d, J 6.5Hz), 4.06(1 H, d, J 6.5Hz), and 7.25-7.5 (5 H, m);6, (90 MHz, CDCl3) 38.8 (t), 39.7(q), 51.5 (d), 66.3(t), 66.4 (t), 94.8 (s), 127.2, 127.6, 128.4, 128.8, 130.9, 139.2, and 176.1 p.p.m. Compound (17)was not obtained pure, but its carbon-13 n.m.r. spectrum was identified from that of a mix-ture containing it: 6, (90 MHz, CDCl,) 37.8, 39.5, 49.8, 66.3, 66.7, 92.9, 127.3, 128.4, 128.7, 130.7, 130.9, 137.4, and 174.8p.p.m. Irradiation of (18) gave a stereoisomer of 2-hydroxy-3-phenyl-11-oxa-6,9-diazatricyclo6.4.0.0z~6dodecan-5-one(19)as the major product (20); vmnx.3 345 and 1 700cm-'; aH (220MHz, CDCIj) 2.19(1 H, t, J 11 Hz), 2.59(1 H, t, J4Hz),2.51 and 2.65(1 H, two d, J3 Hz), 2.75-2.85 (2 H, m), 3.15 (1 H, td, J 12 and 2.5Hz), 3.29(1 H, dd, J 11 and 3 Hz), 3.40 (1 H, t, J9 Hz), 3.55(1 H, dd, J 12 and 4Hz), 3.68(1 H, d, J7Hz), 3.79(1 H, dd, J9and 3 Hz), 4.65(1 H, br), 4.78(I H, d, J 7 Hz), and 7.25-7.45 (5 H, m); tjC (90 MHz, CDC13) 39.0, 48.1, 48.5, 62.1, 62.9, 63.9, 69.5, 99.0, 127.7, 127.9, 128.6, 138.3, and 176.7p.p.m.; m/z 274 (M+),256,and 99 (base) (M+, m/z 274.1318. C15H18N103 requires M, 274.1317).Irradiation of (2I ) gave N-(hut-3-eny/amirzomethy/)pyrro/i- din-2-one (23) as the only product (5) that could be isolated, vnlax.3225, 3 110,and 1 683 cm-'; 88 (90 MHz, CDCl,)1.8-2.95 (9 H, m), 3.44(2H, t, J6Hz), 4.24 (2 H, s), 4.8-5.3 (2H, m), and 5.5-6.15 (1 H, m); 6, (90MHz, CDCI,)18.0(t), 31.3 (t), 34.1(t), 45.6(t), 46.6(t), 57.3 (t), 116.5(t),136.2(d), and 175.7(s); m/z 127, 113,98(base), 84,and 70. Compound (23)could not be synthesised from pyrrolidin-2- one, formaldehyde, and but-3-enylamine, despite many attempts which included amine exchange. Instead it was converted by reaction with formaldehyde and pyrrolidin-2- one into N,N-bis(2-oxop~rrolidin-l-ylmethyl)but-3-eny/amine J.CHEM. SOC. PERKIN TRANS. I 1983 33.5,45.1,67.1, 73.0, 89.5, 126.0, 127.1, 127.7, 128.6, 131.0, 133.8,and 170.4p.p.m. Irradiation of (33) gave 6-dimethylaminoperhydroazepine-2,5-dione (17); vmax.3220,1 701,and 1 660cm-'; FH (220 MHz, CDCI,) 2.25-3.1 (11 H, m,including singlet at 2.29),3.36(1 H, dd, J 15.5 and 5 Hz), 3.53 (1 H, td, J 15.5 and 6 Hz), and 7.56(1 H, br); FC (90 MHz, CDCl,) 31.7, 36.3, 41.6, 42.9, 75.7, 176.6, and 210.5; m/z 170 (M+),126, and 71 (base) (M+, m/z 170.1047.CsHl4N2O2 requires M, 170. 1055). Irradiation of (34)gave 6- (morpho lin-4-yl)perhydroazep ine-2,5-dione (46) (Found: C, 56.7;H, 7.5;N,13.3.C10H16N2O3(24),which was synthesised independently (46) ; vmax,3070, 1 690,and 1 650sh cm-'; FH (90MHz, CDCl,) 1.7-2.9 (12 H, m), 3.47(4H, t, J 6.5 Hz), 4.20(4H, s), 4.85-5.25 (2 H, m), and 5.5-6.15 (1 H, m); 6, (90MHz, CDC1,) 18.0,31.3,32.2, 47.0, 49.7, 60.4, 115.9, 136.6, and 175.8 p.p.m. (M+,m/z 265.1785.Cl4HZ3N3O2requires M+, 265.1789). Irradiation of (24)gave glutarimide (85) and very small amounts (0.6and 0.4) of compounds believed to be 2-hydroxy-7,9-diazatricyclo7.4.O.O2~7tridecan-6-one.First isomer: FH (400 MHz, CDC13) 1.15-1.7 (5 H, m), 1.75-1.9 (2H, m), 1.95-2.0 (1 H, m), 2.0-2.05 (2 H, m), 2.05-2.3 (2H, m), 2.5-2.6 (2 H, m), 3.10(1 H, td, J 10.5 Hz), 3.2(1 H, br), 3.63(1 H, d, J 6Hz), and 4.49(1 H, d, J6Hz); FC (400 MHz, CDCl,) 16.7, 22.6, 24.1, 24.7, 29.6, 31.0,49.8, 66.6, 71.4, 87.6, and 168.8.Second isomer: FH (400MHz, CDC13) 1.2-1.65 (3 H, m), 1.75-2.05 (3 H, m), 2.15-2.4 (3 H, m), 2.5-2.6 (2 H, m), 2.74(1 H, dt, J 13 and 3.5Hz), 2.90(1 H, dd, J 12and 3 Hz), 3.0-3.05 (1 H, m), 4.10(1 H, dd, J 16.5 and6Hz), 4.12(1 H, d, J6.5Hz), and4.49 (1 H, d, J6.5Hz); 6c (400MHz, CDCl3) 16.3, 20.0, 22.0, 23.1, 27.7, 30.6, 46.3, 62.1, 69.9, 90.0, and 169.3p.p.m. Irradiation of (25)gave glutarimide (50) and 2-hydroxy-7,9-diazatricyc/o7.4.0.0z~7~ridec-12-en-6-one.First isomer (30); m.p.99-101 "C (Found: C, 63.6;H, 7.9;N,13.45. CllH16N202requires C, 63.45;H, 7.75;N,13.45); v,,,. 3340,3045,and 1 635cm-'; FH (90MHz, CDCl3) 1.3-3.1 (10H, m), 3.81(1 H, s), 4.32(1 H, d, J8Hz), 4.58(1 H, d, J 8Hz), 5.2(1 H, br), and 5.5-6.1 (2 H, m); FC (90 MHz, CDC13) 16.8, 21.4, 30.3,31.2, 43.1, 63.9, 69.2, 88.5, 122.5, 128.1,and 169.5 p.p.m. (M+, m/z 208.1203. CllH16N202 requires M, 208.1211). Second isomer (8); v,~,,. 3 350, 3045,and 1640cm-' (Found: C, 63.65;H, 7.9;N, 13.45. CllHl6N2O2 requires C, 63.45;H, 7.5;N,13.45); 6, (90MHz, CDCI,) 1.7-2.9 (10H, m), 3.0-3.3 (2H, m), 3.97(1 H, d, J 7 Hz), 4.52(1 H, d, J 7 Hz), and 5.5-6.2 (2 H, m); 6c (90MHz, CDCl,) 16.6,26.0, 30.3, 31.1,45.3,66.1,68.9, 87.3, 121.2, 129.9, and 169.2.Irradiation of (26)gave glutarimide (53) and small am- ounts (8 and 4) of compounds believed to be l-hydroxy- 4-oxa-7,9-diazatricyclo7.4.O.O2~7tridecan-lO-one;vn,',bsol;. 3200 and 1 620;3 325 and 1 615crn-'; 6H (90 MHz, CDCl,) in-cludes 4.54(d, J 6 Hz), and 4.22(d, J 8 Hz) and 4.70(d, J 8Hz). lrradiation of (27) gave I 7-hydroxy-l0,12-diazatetracyclo-8.7.0.02~7.0'2~17hepfade~a-2,4,6-trie~z-l3-one. First isomer (17); m.p. 138.5-140 "C (Found: C, 69.7;H, 6.95;N,10.7.Cl5HI8N2O2requires C, 69.75;H, 7.0;N, 10.85); v,~,,. 3 170 and I 605 cm-'; FH (90 MHz, CDC13) 1.7-3.5 (11 H, m), 3.57(I H, s), 4.16(1 H, d, J7.5 Hz), 4.56(1 H, d, J 7.5Hz), and 7.21 (4 H, s); Fc (90MHz, CDCI3),16.7, 29.3, 30.7, 32.9, 46.4, 66.7, 70.8, 88.7, 125.6, 126.0, 127.4, 129.3, 131.2, 136.0, and 169.6.Second isomer (1976); m.p.150-152"C (Found: C, 69.7;H, 7.1;N, 10.8.C15HlsN,0, requires C, 69.75;H, 7.0;H, 10.85); v,,,..~.3340and 1 620dm"; FH (90MHz, CDC13) 1.25-3.0 (10H, m), 4.38(1 H, d, J 10.5 Hz), 4.50(1 H, s), 4.99(1 H, d, J 10.5Hz), 5.4(1 H, br), and 7.1-7.25 (4 H, m); amp; (90 MHz, CDCI,) 16.6, 28.6, 29.6, requires C,56.6;H, 7.6;N,13.2); vmax.3 320,3 200,1 710, and 1680cm-'; FH (220MHz, CDC1,) 2.25-2.75 (7 H, m),2.85-3.1 (2 H, m), 3.36(1 H, dd, J 16 and 5Hz), 3.59(I H, td, J 16 and 6Hz), 3.75(4H, t, J5 Hz), and 7.6(1 H, br); FC (90 MHz, CDC13) 31.6, 36.3, 40.7, 50.9, 66.7, 74.9, 176.3, and 220.5p.p.m.Irradiation of (35) gave 7-(morpholin-4-yl)perhydroazocine-2,5-dione (77); vnlaX.3 120,3090,1 710,and 1 665cm-'; FH (90MHz, CDCl,), 1.7-2.75 (10H, m), 2.85-3.4 (2 H, m),3.45-3.8 (5 H, m), and 6.77(1 H, br); FC (90MHz, C5D5N) 23.6,32.9,36.4,41.2,52.0,66.9, 79.3, 175.3, and 213.0p.p.m; m/z 198, 170, 141,127,and 113 (base). Irradiation of (36) gave 5-(morpholin-4-yl)-3-azabicyc/o-5.4.0undec-9-ene-2,6-dione(74); vmax.3295,3220,3030, 1 710,1 664,and 1 645shcm-'; 6H (220MHz, CDC13)2.2-2.45(6H, m), 2.65-2.75 (2 H, m), 3.05-3.2 (2 H, m), 3.35-3.65(3 H, m), 3.76(4H, t, J4.5Hz), 5.77 (2 H, s), 6.9(1 H, br); 6, (90 MHz, CDCl,) 25.0(t), 25.5(t), 40.4(t), 41.4(d),50.8(t), 66.8 (t), 74.0(d), 124.8 (d), 125.2(d), 175.7,and 210.0p.p.m.; m/z 264 (M+),236 (base), and 178 (M+,m/z 264.1475.C14H20N203requires M, 264.1473).Irradiation of (38) gave 7-hydruxy-5-methyl-1,5-diaza-bicyclo5.3.Odecan-lO-one(31); vmau.3 340and 1 675cm-'; 8H (220MHz, CDC13) 1.7-2.15 (4 H, m), 2.3-2.4 (2 H, ni),2.45-2.6 (4H, m,including singlet at 2.51), 2.65-2.8 (3 H, m), 2.9-3.0 (1 H, m), and 3.50(2H, t, J5.5Hz); 6c (90MHz, CDCI,) 27.1(t), 29.5(t), 31.5 (t), 39.0(t), 47.6(q), 58.7(t),65.0(t), 89.3(s), and 174.4p.p.m.; m/z 184 (M+),166,and 58 (base) (M+,m/z 184.1233. C9Hl6N2O2requires M, 184.1211). Irradiation of (39) gave 2-hydroxy-l2-oxa-6,9-diazatri-~yclo7.4.0.0~~~trideca~-5-one(12); vmau.3335 and 1 685 cm-'; FH (90 MHz, C5D5N) 1.8-3.4 (12 H, m) and 3.4-4.45(6 H, m); (90MHz, C5D5N),25.8, 29.2, 30.3, 36.0, 51.8, 57.2, 65.5, 66.3, 66.7, 92.4, and 174.4.p.p.m. Irradiation of (40) gave 1-hydroxy-4-oxa-7,11-diazatetra-cyclo9.7.0.02~7.0'3~'8octadec-13( 18)-en-12-one.First isomer (11); vmax.3 310,1 700,and 1 665sh cm-'; FH (90 MHz, CDC13) 1.2-2.8 (16 H, m), 2.85-3.2 (2 H, m), and 3.4-4.05 (4 H, m); 6c (90MHz, CDCl,) 20.5, 21.6, 22.7, 24.3, 25.3, 39.4, 52.7, 58.8, 66.5, 66.7, 68.5, 92.5, 134.3,153.8,and 170.0 p.p.m.; m/z 278 (M+),260,and 100(base) (M+,m/z 278.1627. C15H22NZ03requires M, 278.1 629). Second isomer (6); v,,,:~~.3 315, 1 700,and 1 665sh cm-'; FH (90 MHz, CDCI,)1.2-2.35 (14H, m), and 2.8-3.9 (8 H, m); FC (90 MHz, CDCI,) 20.0, 21.2, 21.7, 22.2, 25.4, 41.3, 50.6, 54.5, 60.1, 61.1, 63.5,90.4, 133.0, 153.8, and 170.9p.p.m.; m/z278(M+).260,and 100 (base) (M+,m/z 278.1631. Cl5HZ2NZ03requires M, 278.1629).Irradiation of (41)gave two pure products. 3-Hydroxy-2-3-(morpholin-4-yl)propylisoitzdo/in-1-one (32); v,,,;,,. 3330 and 1 690cm '; ?jH(90MHz, CDCI,) 2.15-2.65 (8 H, m), 4.1-4.7 (7 H, m, reduced to 6 H with DzO), 5.76(1 H, s), and 7.4-7.85 (4H, m); 6c (90 MHz, CDQ) 23.5, 39.5, 52.9, 56.6, 66.0, 83.2, 122.8, 123.1, 129.3, 131.5,132.1, 145.3, and 167.5 p.p.m.; m/z 276 (M+)and 100 (base) (M+,m/z276.1473.C,5HzoNz03requires M, 276.1473). 2-Hydroxy-3- J. CHEM. SOC. PERKIN TRANS. I 1983 morpholin-4-yl-6-azatricy~Io6.4.O.O~~~dodeca-8,10,12-trien-7-one (10); m.p.194-196 "C (EtOH) (Found: C, 65.85; H, 6.6; N, 10.1. Ct5HI8N2O3requires C, 65.7; H, 6.6; N, 10.2); v,~,~~.3 260 and 1 680 cm-'; SH (90 MHz, CDC13) 2.2-3.0 (7 H, m), 3.25-3.7 (3 H, m), 3.80 (4 H, t, J4.5 Hz), and 7.35-7.75 (4 H, m); SC (90 MHz, CDC1,) 29.8 (t), 39.4 (t), 52.6 (t), 67.1 (t), 69.2 (d), 94.6, 123.7, 129.7, 132.5, 146.9, and 170.0; m/z 274 (M+),188, and 126(base) (M+,mlz274.1318. C15Ht8-N203 requires M, 274.1317). Mixtures (18 and 21) were ob- tained of what was believed to be a diastereoisomer of this compound with two diastereoisomers of 1-hydroxy-7,11-diaza-4-oxatetracyclo9.7.0.02~7.013~18octadeca-l3,15,17-trien-12-one, on the basis of characteristic SC values for quaternary C(0H) (90.4, 91.7, and 99.3 p.p.m.) and other features of the carbon-1 3 n.m.r.spectrum. Irradiation of (42) gave two products. 6-2-(Morpholin-4-yl)ethylperhydroazepine-2,5-dione(26); v,,,. 3 210, 3 080, 1 700, and 1 670 cm-'; SH (90 MHz, CDCl,) 1.4-2.05 (2 H, m), 2.25-2.7 (11 H, m), 3.2-3.45 (2 H, m), 3.3-3.75 (4 H, m), and 7.35 (1 H, br); SC (90 MHz, CDC1,) 25.4 (t), 30.9 (t), 38.0 (t), 43.0 (t), 52.2 (d), 53.6 (t), 56.0 (t), 66.8 (t), 176.3, and 209.6. p.p.m. (M+,m/z 240.1470. ClzHzoNzO3requires M, 240.1467). 5-Hydroxr-4-(morpholin-4-ylmethyl)-1-azabicyclo3.3.O-octan-8-one (13); vnlax 3 345 and 1 695 cm-'; SH (90 MHz, CDCl,) 1.95-2.25 (4 H, m), 2.35-2.75 (8 H, m), 2.8-3.4 (4 H, m), and 3.6-3.8 (4 H, m); (90 MHz, CDC13) 30.5 (t), 33.5 (t), 39.8 (t), 44.6 (d), 54.3 (t), 58.0 (t), 66.9 (t), 97.7 (s), and 174.5 p.p.m.Irradiation of (43) gave 2-hvdroxy-l2-oxa-6,9-diazatri-~yclo7.4.0.0~*~tridec-3-en-5-one.First isomer (2173, vnlay. 3 360 and 1 690 cm-'; SH (90 MHz, CDC1,) 2.45-2.7 (5 H, m), 3.65-3.9 (7 H, m), 6.22 (1 H, d, J 6 Hz), and 6.90 (1 H, d, J6 Hz); 6c(90 MHz, CDCl,) 35.4, 53.9, 54.5, 66.5, 66.9, 67.0, 86.5, 129.7, 145.2, and 166.4 p.p.m.; m/z 310 (M+)and 100 (base) (M+,m/z 210.1003. Cl0HI4N2O3requires M+,210.1004). Second isomer (1 3), vIoa,. 3 440 and 1 700 cm-' ;SH(90 MHz, CDCI,) 2.45-2.85 (2 H, m), 2.95-3.4 (6 H, m), 3.54.1 (4 H, m), 6.14 (1 H, d, J 6 Hz),and 6.85 (1 H, d, J 6 Hz); SC (90 MHz, CDC13) 34.6, 44.3, 53.3. 60.8, 62.6, 66.9, 87.1, 128.6, 145.9, and 167.4; m/z 210 (M+),192, and 98 (base) (M+,m/z 210.1005.CI0Hl4N2O3requires M, 210.1004). Irradiation of (44)gave 1-hydroxy-4-oxa-7,1 O-diazatetra- cy~lo8.7.0.O~*~.O'~*~~heptadec-l2(17)-en-ll-one. First isomer (23), vnlL,, 3 320, 1690, and I 660sh cm-'; SH (90 MHz, CDC13) 1.25-2.5 (11 H, m), 2.6-2.9 (2 H, m), and 3.0-4.2 (7 H, m); amp; (90 MHz, CDCI,) 20.2, 21.5, 22.3, 23.2, 35.5, 54.2,54.3,66.5,66.7,66.8,85.9,133.9, 153.3, and 167.6p.p.m.; m/z 264 (M+),246, and 100 (base) (M+, m/z 264.1475. C14H20N203requires M, 264.1473). Second isomer (1573, v,,,,,. 3 320, 1 695, and 1 665sh cm-'; ZiH (90 MHz, CDC1,) 1.4-1.85 (4 H, m), 1.95-3.5 (13 H, m), and 3.6-4.55 (3 H, m); 6c (90 MHz, CDCI,) 20.0, 21.2, 21.6, 21.7, 34.4, 43.3, 53.3, 58.8, 60.0, 61.2, 85.5, 134.1, 151.8, and 167.4 p.p.m.; m/z 264 (M+),246, and 100 (base) (M+,m/z 264.1471.CI4HZON2O3requires M, 264-1473). Irradiation of (45)gave 1-hydroxy-4-oxu-7,1 O-diuzatetra- cyclo8.7.0.02~7.0'2~17.heptadec~-l2,l4,l6-trien-ll-one.First isomer (3 l), v,),amp;,3 320 and 1 700 cm-' ;6" (90 MHz, CDC1,) 1.85-2.8 (5 H, m), 3.1-4.2 (6 H, m), 4.9 (1 H, br), and 7.3-7.5 (4 H, m); Zc (90 MHz, CDCI3) 35.5, 54.1, 54.4, 66.2, 66.5, 67.2, 85.4, 123.2, 123.7, 129.8, 131.5, 131.9, 144.6, and 164.8; m/z 260 (M+),242, and 100(base) (M+,m/z260.1 158. C14Ht6-N203 requires M, 260.1 160). Second isomer (1273, vIllrty, 3 300 and 1 700 cm-'; SH(90 MHz, CDC13) 2.35-3.35 (8 H, m), 3.4-4.15 (4 H, m), and 7.35-7.75 (4 H, m); Sc (90 MHz, CDCl,) 34.8, 43.1, 53.1, 59.2, 59.3, 62.2, 85.3, 122.5, 123.7, 130.1, 131.5, 132.3, 143.7, and 164.9; m/z (deuteriated) 261 (M+)and 100 (base) (M+, m/z 261.1232.CI4Hl5DN2O3 requires M, 261.1222). Acknowledgements We thank the S.E.R.C. and Reckitt and Colman (Pharma- ceutical Division) for support through a CASE studentship (to L. R. B. B.). References 1 For a review, see P. H. Mazzocchi, in A. Padwa (ed.), ' Organic Photochemistry,' Marcel Dekker, New York, 1981, vol. 5, p. 42 I. 2 Y. Kanaoka, Acc. Chem. Res., 1978, 11, 407; J. D. Coyle, in W. H. Horspool (ed.), ' Synthetic Organic Photochemistry,' Plenum Press, London, 1983, ch. 7. 3 M. Wada, H. Nakai, Y.Sato, and Y. Kanaoka, Tetrahedron Lett., 1982, 23, 3077, and references therein.4 Y. Kanaoka and Y.Hatanaka, J. Org. Chem., 1976, 41, 400; Y. Kanaoka, H. Okajima, Y. Hatanaka, and M. Terashima, Heterocycles, 1978, 11, 455. 5 H. Nakai, Y. Sato, T. Mizoguchi, M. Yamazaki, and Y. Kanaoka, Heterocycles, 1977, 8, 345. 6 For a preliminary report of some of the succinimide systems, see L. R. B. Bryant and J. D. Coyle, J. Chem. Res. (S), 1982, 164. 7 H. Hellmann and I. Loschmann, Ber., 1954, 87, 1684. 8 H. P. Hamlow, S. Okuda, and N. Nabagawa, Tetrahedron Lett., 1964, 2553; F. Bohlmann, D. Schumann, and H. Schulz, ibid., 1965, 173. 9 R. J. Abraham and P. Loftus, ' Proton and Carbon-13 NMR Spectroscopy,' Heyden, London, 1978, p. 46. 10 J. B. Stothers, ' Carbon-I3 Nuclear Magnetic Resonance Spectroscopy,' Academic Press, London and New York, 1972, p. 166. 11 J. F. Challiner, J. D. Coyle, and E. J. Haws, unpublished results. 12 P. H. Mazzocchi, J. Thomas, and F. Danisi, J. Org. Chew., 1979, 44, 50. 13 W. Werner and H. Fritzsche, Arch. Pharm. (Weinheim), 1969, 302, 188. 14 C. C. Bombardieri and A. Taurins, Car;.J. Chem., 1955,33, 923. 15 J. D. Coyle and L. R. B. Bryant, J. Chem. SOC.,Perkin Trans. I, 1983, 531. 16 Y. Kanaoka, Y. Migita, K. Koyama, Y. Sato, H. Nakai, and T. Mizoguchi, Tetrahedron Lett., 1973, 1193. 17 K. Maruyama and Y. Kubo, Chem. Lett., 1978, 769; G. T. Hutchinson, R. H. Prager, and A. D. Ward, Aust. J. Chem., 1980, 33, 2477. 18 B. A. Mooney, R. H. Prager, and A. H. Ward, Ausr. J. Chem., 1981, 34, 2695. 19 J. D. Coyle and G. L. Newport, Synthesis, 1979, 381; M. Machida, H. Takechi, and Y. Kanaoka, Heterocycles, 1980, 14, 1255. 20 M. Machida, H. Takechi, Y. Shishido, and Y. Kanaoka, Synthesis, 1 982, 1078. 21 B. Reichert, ' Die Mannich-Reaktion,' Springer-Verlag, Berlin, 1959. 22 M. Eckstein, A. Zejc, and A. Klusek, Diss. Pharm. Pharmacol., 1967, 19, 263. 23 P. 0. Tawney, R. H. Snyder, R. P. Conger, K. A. Leibbrand, C. H. Stiteler, and A. R. Williams, J. Org. Chem., 1961, 46, 15. 24 S. R. Sandler and W. Karo, 'Organic Functional Group Preparations,' Academic Press, London and New York, 1972, vol. 3. 25 R. bsol;Vegscheider and J. Hecht, Monatsh., 1903, 24, 422. 26 N. M. Yoon and H. C. Brown, J. Am. Chenr. Soc., 1968, 90, 2928. Received 29th March 1983; Puper 3/504