Synthesis of new azetidinonyl/thiazolidinonyl quinazolinone derivatives as antiparkinsonian agents

Several 3-amantadinyl-2-[(2-substituted benzylidenehydrazinyl)methyl]-quinazolin-4(3H)-ones (5a–5l) were prepared by the reaction of 3-amantadinyl-2-hydrazinylmethyl substituted quinazolin-4(3H)-ones (4a–4b) with various substituted aromatic aldehydes. Cycloaddition of compounds (5a–5l) with thioglycolic acid in the presence of anhydrous zinc chloride yielded 3-amantadinyl-2-[((substitutedphenyl)-4-oxo-thiazolidin-3-yl)methylamino]-quinazolin-4(3H)-ones (6a–6l). Compounds 5a–5l on further reaction with chloro acetyl chloride in the presence of triethylamine gave 3-amantadinyl-2-[((substitutedphenyl)-3-chloro-2-oxo-azetidin-1-yl)methylamino]-quinazolin-4(3H)-ones (7a–7l). The compounds 5a–5l, 6a–6l and 7a–7l were screened for their antiparkinsonian activity. The most active compound was 6g i.e. 3-amantadinyl-6-bromo-2-[((3,4-dimethoxyphenyl)-4-oxo-thiazolidin-3-yl)methylamino]-quinazolin-4(3H)-ones. Structures of the newly synthesized compounds were established on the basis of elemental and spectral (IR, ¹H NMR and mass) analysis.     

In vitro antioxidant properties of new thiazole derivatives

A series of novel N2-[2-chloro-4(3,4,5-trimethoxy phenyl azetidin-1-yl]-N4-(substituted aryl)-1,3-thiazole-2,4-diamine (4a–g) were synthesized starting from 3,4,5-trimethoxy benzaldehyde thiosemicarbazone (1). The compound (1) was obtained by condensing 3,4,5-trimethoxy benzaldehyde with thiosemicarbazide in methanol. 3,4,5-Trimethoxy benzaldehyde thiosemicarbazone (1) on treatment with chloracetyl chloride afforded 4-chloro-[2-(3,4,5-trimethoxy benzylidine) hydrazinyl]-1,3-thiazole (2). Compound (2) was reacted with chloracetyl chloride and triethylamine to obtain the corresponding 4-chloro-N-[2-chloro-4(3,4,5-trimethoxy phenyl) azetidin-1-yl]-1,3-thiazole-2-amine (3). Various substitutions on compound 3 with secondary amines yielded series of compounds (4a–g). The newly synthesized compounds were characterized by IR, ¹H NMR, elemental analysis and mass spectral studies. All the compounds were screened for their in vitro antioxidant properties. The IC₅₀ values of compounds 3 and 4a–g revealed that some of the synthesized compounds were showing potent antioxidant activity.     

Reactions in microemulsion media. Borohydride reduction of mono- and dicarbonyl compounds

Microemulsions were prepared at 26° from mixtures of hexanes (O), a 50: 1 (w/w) solution (W) of 0.1 M KOH-NaBH₄, and a 1.23:1 (w/w) mixture (S) of hexadecyltrimethylammonium bromide (HTABr) and 1-butanol. A pseudoternary phase map contained a significant microemulsion (μE) region, and μE's A and B (60:35:5 and 20:10:70 S:W:O, respectively) were used for reduction of several monocarbonyl compounds [benzophenone (1a), benzaldehyde (2a), acetophenone (3a), and 1-phenyl-1-octadecanone (4a)], an α,β-unsaturated ketone [trans-4-phenyl-3-buten-2-one (6a)], and a diketone [4-(4'-benzoylphenyl)-2-butanone (7a)]at 26°. For comparison purposes, reductions were also performed in aqueous 2-propanol (2-PrOH A and 2-PrOH B) prepared by the substitution of 2-propanol for the S and O components of μE's A and B. Generally, the reductions were slightly faster in the microemulsion media than in the corresponding aqueous 2-propanol media. The significantly slower reduction of 4a relative to that of 3a in μE B indicated that the interphase is the reactive site. With enone 6a, the influence of microemulsions on the competition between 1,2- and 1,4-reduction was determined. In μE's A and B there was 8% and ll% 1,4-reduction, respectively, whereas in 2-PrOH A and B there was only a trace. With diketone 7a, the reactivity of the aromatic carbonyl group relative to that of the aliphatic carbonyl group increased on going from 2-PrOH A and B to μE's A and B, respectively. For the sodium borohydride reduction of ketones, microemulsion catalysis is more effective than phase transfer catalysis or the use of a tetraalkylammonium borohydride in a hydrocarbon solvent.     

Bromination of 3-phenylindoles

Brominations of 3-phenylindole (1a) and its 1-methyl-(1b) and 1-acetyl-(1c) derivatives with NBS in AcOH and CCl₄ have been carried out. In AcOH 1 gave 2-bromo derivatives (2) in high yields and the relative reactivity was found to be NH > NMe ? NAc by competitive reactions. In boiling CCl₄1a and 1b gave 2 but bromination of 1c did not proceed. Bromination of 1a with 2 moles of NBS in AcOH gave 2,6-(major) and 2,5-dibromides (8 and 9). Reaction of 2a with thiourea gave 19. Selective reduction of the bromine atom at the 2-position in 2,6-dibromide (10) was achieved by Zn3CuNaOH, and irradiation of 8 in EtOH-alkali reduced 2,6-dibromide to 1a.     

Synthesis of some new 4-oxo-thiazolidines,tetrazole and triazole derived from 2-SH-benzothiazole and antimicrobial screening of some synthesized

A new heterocyclic derivative of 2-mercaptobenzothiazole (MBT) comprising 4-oxothiazolidines, tetrazole and triazole, through the reaction of (MBT) with hydrazine hydrate obtained 2-hydrazobenothiazol (1), which was condensed with various aromatic aldehydes. Azomethine derivatives (2a–c) are converted into a number of 4-oxothiazolidines (3a–c) and tetrazole derivatives (4a–c), through the reaction of azomethine derivatives (2a–c) with mercaptoacetic acid and sodium azide, respectively. Also the reaction of compound (1) with triethylorthoformate and nitrous acid to produce the corresponding (triazole and tetrazole) benzothiazole (5,6) was reported.Triazole moieties reported condensation (MBT) with ethylbromo acetate and potassium hydroxide by the fusion method and resulted in ester-2-mercaptobenzothiazole (7), which was treated with hydrazine hydrate to give a hydrazine derivative (8), then converting these compounds (8) to phenyl semicarbazide (9) and phenyl thiosemicarbazide (10) derivatives. Cyclization compounds (9,10) in alkaline media (4 N·NaOH) gave triazoles compounds (11,12). Furthermore the compound (8) was converted to the dithiocarbazate salt (13) which was then cyclized with hydrazine hydrate to give substituted triazole (14). The prepared compounds were identified by spectral methods (FTIR, ¹H NMR, ¹³C NMR) and some of its physical properties were measured and furthermore the effects of the preparing compounds on some strains of bacteria were studied.     

Nucleophilic subsitution at silicon: Synthesis of sterically-hindered bis(2,6-di-t-butylaryloxy)silanes

The reaction of the monomethylsilane (8a) with two equivalents of the 4-(carboalkoxy)-2,6-di-t-butyl-substituted phenol (7b) in toulene using triethylamine as an acid acceptor gave the bis(aryloxy) adduct (9a). The analogus reaction of the dimethylsilane (8b) with sodium 2,6-di-t-butyl-4-(methoxycarboxyl)-phenolate (7a) gave only the monosubstitution product (10a). The reaction of the corresponding phenolate (7e) with 8b gave a mixture of 7a, 10a, and bis-adduct (9b), whereas, in the presence of 15-crown-5, the bis-adduct 9b was obtained. The bis-adducts 9c–e were prepared in an analogous manner. The reaction of n-hexyl 3,5-di-t-butyl-4-hydoxylbenzoate (7h) with the diphenylsilane (8c) gave only the monosubstitution product 12, while forcing conditions gave, unexpectedly, the methyl ether 13. The reaction of 4-(carboalkoxyethyl)-2,6-di-t-butylphenol (16a) with 8a gave the bis adduct. The reaction of 16a with 8b in THF, without a crown ether, gave a low yield of the monosubstitution product. The bis-adducts 17b–c were obtained by the reaction of 8b with the corresponding phenolates (16a–b) in tetraglyme. Compound 17b was also obtained by the reaction of 8b with 16a in THF with a crown ether. These results are discussed in terms of charge dispersal in the phenolate ion and the corresponding effect upon both ion-pairing and aggregation in solution.     

Mechanism of the von Braun amide degradations with carbonyl bromide or phosphorus pentabromide

The isolation of the α-bromobenziminium hexafluoroantimonate 6, the first intermediate in the amide degradation with carbonyl bromide, was previously announced. Present studies reveal that using either COBr₂ or PBr₅, the very first intermediate is the iminium tribromide (7). Reaction of the crystalline tribromide with cyclohexane gave the monobromide 8 nearly quantitatively and in crystalline form. Heating of the cyclic iminium monobromide 8 to 120° generates in high yield the α,ω-dihalogenoalkane (type 13) and benzonitrile, while heating to 100° in bromobenzene allows isolation of the ω-bromoalkyl benzimidoyl bromide (9 or 10). An independent synthesis of this and other imidoyl bromides is elaborated. the equilibrium of imidoyl bromides with N-alkyl nitrilium (11) can be shifted toward the nitrilium salt by dissolving in liquid sulfur dioxide or reacting with methyl fluorosulfate. All these steps have been monitored by NMR. The ω-bromoalkyl imidoyl bromide at 120° undergoes fragmentation via the nitrilium ion to an α,ω-dibromoalkane and benzonitrile. In addition to gaining mechanistic information (1) we achieved isolation of crystalline n-alkylene-α-bromoiminium bromides, and their smooth thermal decomposition, which makes the von Pechmann-von Braun type of degradation competitive to the Hofmann methylation; (2) new procedure was found for preparing ammonium tribromides and iododibromides using carbonyl bromide; (3) a number of the heterofore unknown imidoyl bromides have been prepared and characterized, and their thermolysis and mass spectra studied.     

Diphenyl N-halosulfilimines : Preparation,decomposition, and reactions with nucleophiles

Diphenyl N chloro (l)-N bromo (2) and N-iodo-sulfilimines (3) were prepared by halogenation of diphenyl free sulfilimine. Compound 1 decomposed in benzene at room temperature. The decomposition of 1 is a chain reaction since the reaction was induced by chlorine or t-butyl hypochlorite affording diphenyl(diphenylsulfilimino) sulfonium chloride(4a) while it was inhibited by styrene or stilbene. Compound 4a was also obtained by the reaction of 1 with diphenyl sulfide in benzene. Decomposition of 1 in acetic acid proceeded smoothly affording various products. Compound 1 reacted with sulfides sulfoxides triarylphosphines and triethylamine affording the N-substituted iminosulfonium salts. Compounds 1 and 2 were hydrolyzed with sodium hydroxide affording diphenyl sulfoximine. The reaction of 1 with sodium cyanide gave diphenyl N cyanosulfilimine(17). The reaction of 1 with Grignard reagent gave diphenyl free sulfilimine. Compounds 2 and 3 are more stable than 1. Decomposition of 2 in benzene or acetic acid gave diphenyl(diphenylsulfilimino)sulfonium perbromide(4c)     

Studies on the syntheses of heterocyclic compounds—DLIX : A synthesis of benzocarbazole derivatives by thermolysis

A thermal reaction of indolylmagnesium bromide (5) with 1-cyano-4,5-dimethoxybenzocyclobutene (6) gave a mixture of 6-cyano-5a, 6,11,11a-tetrahydro-8,9-dimethoxy-5H-benzo [b] carbazole (8a) and 6-cyano-5a, 6, 11, 11a-tetrahydro-9-hydroxy-8-methoxy-5H-benzo [b] carbazole (10). Compound 8a was easily converted to 6-cyano-8, 9-dimethoxy-5H-benzo [b] carbazole (12) by dehydrogenation on 30% Pd-C.     

Fluorinated molecules relevant to conducting polymer research

The synthesis of versatile fluorine compounds for conducting polymer research on fluorinated materials is presented. 1,2,4,5-Tetrafluorobenzene was converted to 1,2,4,5-tetrafluorobenzaldehyde (1) and protected as an acetal. This gave the acetals 1,2,4,5-tetrafluoro-3-(1,3-dioxol-2-yl)benzene (2a) and 1,2,4,5-tetrafluoro-3-(5,5-dimethyl-1,3-dioxan-2-yl)benzene (2b). Compounds 2a and 2b were converted into the semiprotected 2,3,5,6-tetrafluoroterephthaldehydes: 1,2,4,5-tetrafluoro-3-(1,3-dioxol-2-yl)-6-formylbenzene (3a) and 1,2,4,5-tetrafluoro-3-(5,5-dimethyl-1,3-dioxan-2-yl)-6-formylbenzene (3b). While 3a was easily deprotected to give 2,3,5,6-tetrafluoroterephthaldehyde (4) compound 3b proved very resilient to hydrolysis and gave a 1:1 mixture of 4 and 1,2,4,5-tetrafluoro-3,6-bis(5,5-dimethyl-1,3-dioxan-2-yl)benzene (5). Compound 4 was reduced to 1,2,4,5-tetrafluoro-3,6-dihydroxymethylbenzene (6) and converted into 1,2,4,5-tetrafluoro-3,6-dibromomethylbenzene (7). Compound 7 was finally converted into 1,2,4,5-tetrafluoro-3,6-bis(diethylphosponylmethyl)benzene (8). Compounds 4 and 8 are versatile fluorinated molecules that can be used to replace their hydrogen counterparts in many molecules and materials. To illustrate this compounds 4 and 8 were oligomerised to give partially fluorinated polyphenylenevinylene (9).     

Base-catalyzed oxygenation of 2,6-di-t-butylanilines: X-ray analysis of 2,4,6-tri-t-butyl-4,5-epoxy-6-hydroxy-2-cyclohexen-1-imine

Oxygenation of 2,4,6-tri-t-butylaniline (1a) catalyzed by t-BuOK in hexamethylphosphoric triamide (HMPA) at 75° leads to the incorporation of molecular oxygen into the aromatic ring giving rise to 2,4,6-tri-t-butyl-4,5-epoxy-6-hydroxy-2-cyclohcxen (12a). A similar result is obtained in the oxygenation of 2,6-di-t-butyl-4-phenylaniline (11b). The oxygenation of 11a in toluene containing n-BuLi gave exclusively 2,4,6-tri-t-butyl-nitrosobenzeoe. The oxygénation of 2,6-di-t-butyl-4-methoxyaniline (1d) in tetrahydrofuran with n-BuLi gave dimeric products in fairiy good yields. The structure of 12a has been confirmed by X-ray analysis. The crystals are monoclinic ($\text{P2}{}_1\text{a}$) with a = 9.99, b = 23.16, c = 8.70 Å, β = 116.19°; Z = 4. The structure was determined by direct methods and refined to R = 0.089.     

Palladium-catalyzed syntheses of naturally-occurring acetylenic thiophens and related compounds

5-(3-Buten-l-ynyl)-2,2'-bithienyl (1a), a natural product first isolated from Tagetes roots which shows nematicidal and photo-induced fungicidal activity, and 2-phenyl-5-(3-buten-l-ynyl) thiophen (1b) have been synthesized using two different methods. The first one (Method A) involves the palladium-catalyzed cross-coupling of vinyl bromide with the Grignard reagents derived from 5-ethynyl-2,2'-bithienyl (6a) and 2-ethynyl-5-phenylthiophen (6b). The second method (Method B) utilizes the coupling reaction of vinyl bromide with 6a and 6b, respectively, in the presence of a catalytic amount of (PPh₃)₄Pd and CuI. Such reaction, which was carried out under phase-transfer conditions employing BnEt₃N⁺Cl^- as phase transfer agent and 2.5NaqNaOH as base, has been also employed to prepare a large number of heterocyclic acetylene derivatives including some naturally-occurring compounds. The experimetal conditions of Method B allow also the direct production of heterocyclic acetylene derivatives (1) starting from 1-alkynyltrimethylsilanes (5) and organic halides (2).     

Thio-acids—V : Some reactions of 3-oxo-1,2-dithioles

Diphenyldiazomethane with compound (1) gave dibenzoyl, while 2 and 3 gave the corresponding 3-oxo(2H)thiophenes 5. With copper-bronze 1 gave 2,2′-di-(thiobenzoate) (4), while 2 gave 2,7-diphenylthiepin (6a) and 2,5-diphenylthiophene (7a), but 3 gave only 2,5-di-(p-methoxyphenyl)thiophene (7b). With Grignard reagents 1 gave the corresponding methanol derivative 14, while 2 gave the thiobenzoylethylenes 13a and b, but 3 gave 2,7-di-(p - methoxyphenyl) - 4,4,5,5- tetraphenyl(4H)thiepin (15). The reaction mechanisms are discussed.     

Derivatizable novel β-tetra 7-oxycoumarin-3-carboxylate substituted metallophthalocyanines: Synthesis and characterization

In this study, a novel phthalonitrile, ethyl 7-(3,4-dicyanophenoxy)coumarin-3-carboxylate (1), was prepared and characterized. The metallophthalocyanines (3–6) were prepared by cyclotetramerization of 1 with the corresponding metal salts {Zn(OAc)₂·2H₂O, Co(OAc)₂·4H₂O, Cu(OAc)₂, Ni(OAc)₂·4H₂O} in 2-chloronaphthalene. Reaction of 3 with aqueous hydrochloric acid gave the coumarino-zincphthalocyanine (3a) carrying carboxyl groups at the 3-position of all the coumarin moieties. Treatment of compound 3a with aqueous NaOH_./AgNO₃ or aqueous NaOH in N,N-dimethylformamide (DMF) gave the expected silver (3c) or sodium (3d) salts, respectively. The four carboxylic groups in coumarino-zincphthalocyanine (3a) and the four carboxylate groups in 3d make the compounds have good solubility in water. Heating of the acyl chloride derivative of 3 with morpholine in DMF yielded the corresponding 3-carboxymorpholinamide (3b). The newly prepared compounds, phthalonitrile and metallophthalocyanines, have been characterized by FT-IR, UV–Vis, MALDI-TOF and ¹H NMR spectroscopies.     

2'-Desoxytubercidin: synthese des o-3'-phosphoramidites und kondensation zu 2'-desoxytubercidylyl(3' → 5')-2'-desoxytubercidin

The phosphoramidite of 2'-deoxytubercidin (2) has been prepared by phosphitylation of compound 3b with chlorodiisopropylaminomethoxyphosphane. The intermediate 3b was obtained from 2'-deoxytubercidin (1) by N⁴-benzoylation and subsequent O-5'-dimethoxytritylation. Condensation of compound 2 with O-3'-silylated 3e gave the fully protected dimer 4b, which was converted into 2'-deoxytubercidylyl (3' → 5')-2'-deoxytubercidin(4a). Compound 4a isoster with 2'-deoxyadenosylyl(3' → 5')-2'-deoxyadenosine (d(ApA)) exhibits a hypochromicity of 11% (270 nm) due to strong stacking interactions. Cleavage of the dinucleoside monophosphate 4a with nuclease S₁ occurs five times faster than that of d(ApA). This shows that the single strand specific enzyme recognises the geometry of the stacked nucleobases.     

Surprising 1,7-cyclization of vinyl carbonyl ylides generated from reaction of indanetrione with vinyl diazo compounds

Reactions of tricarbonyl compounds with vinyl diazo compounds 2 were carried out. Reaction of 1,2,3-indanetrione with 2a,b,c gave the spiroindan-1,3-dione-2,2′-benzodihydrooxepin 7a,b,c, but not normal products oxirane and dihydrofuran derivatives expected from intermediate vinyl carbonyl ylides 4. Formation of 7 requires isomerization of vinyl carbonyl ylides 4 bearing a (Z)-cyanostyryl group to unstable (E)-form 5 and subsequent cyclization to oxepin 6 followed by a 1,5-hydrogen shift. However, reaction of 2 with six-membered cyclic tricarbonyl compounds 1,2,3-trioxo-2,3-dihydrophenalene 11 and dimethylalloxane 13 gave the dioxole 12 and the dihydrofuran 14, respectively, typical products expected from vinyl carbonyl ylides.     

Preparations and reactions of 1,2,3-trialkyl-1,2-dihydroquinolines and its related compounds

Several 1,2,3-trialkyl-1,2-dihydroquinolines (4 and 5) were prepared from the reactions of N-alkylanilinomagnesium bromide (1 and 2) with aliphatic aldehydes (3). Solutions of these dihydroquinolines in carbon tetrachloride or chloroform gave the corresponding 1,2,3- trialkylquinolinium chlorides (10 and 11) in high yields. Alkali treatment of 1,3-dimethyl-2- ethylquinolinium chloride (10b) led to 1,3 - dimethyl - 2 - acetyl - 1,2 - dihydroquinoline (13), which was unstable and readily converted to 1,3-dimethyl-2-quinolone (6) in the air.     

Synthesis of formazans from Mannich base of 5-(4-chlorophenyl amino)-2-mercapto-1,3,4-thiadiazole as antimicrobial agents

5-(4-Chlorophenyl amino)-2-mercapto-1,3,4-thiadiazole (I) was refluxed with formaldehyde and ammonium chloride in ethanol yielding the Mannich base 5-(4-chloro phenyl amino)-3-aminomethyl-2-mercapto-1,3,4-thiadiazole (II). Esterification with 4-chloro-(2,6-dinitro phenoxy)-ethyl acetate (III) under anhydrous conditions gave the intermediate (IV). Subsequent hydrazinolysis with hydrazine hydrate gave the corresponding hydrazide 3-amino methyl-5-(4-chloro phenyl amino)-2-mercapto-4′-(2′,6′-dinitro phenoxy)-acetyl hydrazide (V). The hydrazide was converted into the Schiff bases (VI_a–b) by reacting with 2-chlorobenzaldehyde and 3-methoxy-4-hydroxy benzaldehyde in presence of methanol containing 2–3 drops of acetic acid. Diazotisation with aromatic amines, sulphanilic acid and sulphur drugs gave the formazans (VII_a–g) respectively. Chemical structures have been established by elemental analysis and the spectral techniques of FTIR, ¹H NMR and mass. Antimicrobial activity (in vitro) was evaluated against the two pathogenic bacterial strains. Escherichia coli and Salmonella typhi, three fungal strains Aspergillus niger, Penicillium species and Candida albicans. The compounds have shown moderate activity.     

The synthesis of octavalene (tricyclo[5.1.0.02,8]octa-3,5-diene) and several substituted octavalenes

The first synthesis of octavalene (1a) is reported. The starting material is homobenzvalene (5), to which monobromocarbene is added. The resulting compound 3a takes up bromine across the central bicyclo[1.1.0]butane bond to form the tribromide 7a which undergoes a cyclopropyl bromide-allyl bromide rearrangement on heating. From the product (1Oa) HBr is eliminated to give a 1,3-dibromocyclobutane with a 1,3-butadiene bridge across its 2- and 4-position (11a). Finally, t-butyllithium removes the two Br atoms from 11a and converts it into a 4:1 mixture of 1a and cyclooctatetraene. This reaction sequence represents the first application of protective group strategy in bicyclo[1.1.0]butane chemistry. Octavalene (1a) is shown to rearrange to cyclooctatetraene at 50°. Deuterium-labeled 1a ([1,8-D₂] 1a) is used to prove that a [1,5]-sigmatropic shift does not occur in 1a. Utilizing the above methodology 4-bromooctavalene (1b) and 3-phenyl-5-bromooctavalene (1c) are synthesized from the dibromocarbene adducts 3b and c of homobenzvalene (5) and 5-phenylhomobenzvalene (6), respectively. Surprisingly, 1c was accompanied by a small quantity of 3-bromo-1-phenyloctavalene (1d). Possible mechanisms for the addition of bomine to the bicyclo[1.1.0]butane system of compounds 3 and for the formation of the octavalenes 1 are discussed. In the ¹³C-NMR spectra of 1 and 11 chemical shifts at unexpectedly high field are observed for C-6 of the 1,3-cycloheptadiene moieties.     

Hydantoins,thiohydantoins, glycocyamidines—36: 1,5,5- and 3,5,5-triphenyl derivatives

In contrast to the α-chloroamides 1a-c which, when reacted with potassium N-cyanoanilide, furnish anomalous substitution products (2a-c), the related nitrile and ester yields normal substitution products (3a and b) under the same conditions. 1,5,5-Triphenylhydantoin (4a) and a series (5a-8a, 13 and 14) of its derivatives have been prepared starting with 3a and b. Acid hydrolysis of 3a yields, in addition to the normal products (4a and 5a) considerable quantities of the rearranged product 4b. An authentic sample of the latter, as well as a series of its derivatives (5b-8b and 11) have been prepared starting with α,α-diphenylglycinonitrile and 2-methylthio-1,4,4-triphenyl-2-imidazolin-5-one (9). When reacted with ammonia and ammonium iodide, 9 gave, in addition to the normal ammonolysis product 7b, the Dimroth rearrangement product 16, as well as 5,5-diphenylglycocyamidine, by apparent dephenylation of 16. The mass spectra of the imidazole derivatives 4–8, a and b, 9, 11, 13 and 14 are discussed.