Antiradical activity of morpholine- and piperazine-functionalized triphenylantimony(V) catecholates

The antiradical activity of the functionalized triphenylantimony(V) catecholates Ph₃Sb[4-O(CH₂CH₂)₂N-3,6-DBCat] (I), Ph₃Sb[4,5-Piperaz-3,6-DBCat] (II), and Ph₃Sb[4-PhN(CH₂CH₂)₂N-3,6-DBCat] (III) (where [4-O(CH₂CH₂)₂N-3,6-DBCat]^2?, [4,5-Piperaz-3,6-DBCat]^2?, and [4-PhN(CH₂CH₂)₂N-3,6-DBCat]^2? are the dianionic ligands 3,6-di-tert-butyl-4-(morpholin-1-yl)-, 3,6-di-tert-butyl-4,5-(piperazine-1,4-diyl)-, and 3,6-di-tert-butyl-4-(4-phenylpiperazin-1-yl)catecholates, respectively) was studied in reactions with the diphenylpicrylhydrazyl radical during autooxidation of unsaturated fatty (oleic and linoleic) acids with lipid peroxidation of Russian sturgeon (Acipenser gueldenstaedti B.) sperm and human blood erythrocytes in vitro as examples. The EC₅₀ and n _DPPH values obtained indicate the high antiradical activity of complexes II and III in the reactions with the stable radical. On the whole, complexes I–III inhibit the lipid peroxidation in both model (oxidation of unsaturated fatty acids) and in vitro experiments. The inhibiting effects of the complexes are comparable with and even, in some cases, higher than those of the known antioxidant ionol.     

Amino(tert-butyl-NNO-azoxy)furoxans: synthesis, isomerization, and rearrangement of N-acetyl derivatives

3-Amino-4-(tert-butyl-NNO-azoxy)furoxan (1a) and 4-amino-3-(tert-butyl-NNO-azoxy)-furoxan (1b) and their acetyl derivatives 6a,b were obtained. The equilibria 1a ai 1b and 6a ? 6b were studied. Furoxan 6b can undergo thermal rearrangement into 3-[(tert-butyl-NNO-azoxy)(nitro)methyl]-5-methyl-1,2,4-oxadiazole (7), prolonged heating of which gives N-(2-tert-butyl-5-nitro-1-oxido-2H-1,2,3-triazol-4-yl)acetamide (8). With the transformation 7 → 8 as an example, the possibility of participation of the azoxy group in the Boulton-Katritzky rearrangements was demonstrated for the first time.     

Tin(IV) complexes based on 2-hydroxy-3,6-di-tert-butyl-para-benzoquinone: Syntheses,structures, and electrochemical behavior in solution

A series of new tin(IV) complexes based on 2-hydroxy-3,6-di-tert-butyl-para-benzoquinone (LH) of the general formula L₂SnR₂ (R = Me (I), Et (II), Bu ⁿ (III), Ph (IV)) and LSnMe₃ (V) were synthesized. The obtained compounds were characterized by IR and ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy and elemental analysis. The X-ray diffraction analysis was carried out for complexes L₂Sn(Bu ⁿ )₂ (III) and LSnMe₃ (V). The low-frequency region of the IR spectra, which has not earlier been studied in detail, was interpreted for compounds I–V and previously described complex LSnPh₃ (VI). The electrochemical properties of LH and related tin complexes I–VI were studied. The nature of the hydrocarbon groups at the metal atom affects the stability of the intermediates formed in the electrochemical reactions.     

Further studies on the properties and effect of high energetic ionizing radiation on copper(II) complexes: 1H NMR,electronic absorption,ESR spectra and solid electrical conductivity

The effect of energetic γ-radiation on ¹H NMR, electronic absorption, ESR spectra, differential thermal analysis (DTA) and solid state dc electrical conductivity of the ligand N-phenyl-2-(2-(phenylamino)acetyl)hydrazine carbothioamide (H₂L) and its copper(II) complexes; Cu(HL)(OAc)H₂O, Cu(HL)BrH₂O and Cu(H₂L)₂(NO₃)₂?3H₂O before and after γ-irradiation (hereafter referred to as (B), (B ₁ ), (B ₂ ), (B ₃ ) and (A), (A ₁ ), (A ₂ ), (A ₃ ), respectively) has been studied. Electronic spectral bands of the complexes after irradiation exhibited some better resolved shapes with a remarkably higher absorbance, ESR spectrum of complex Cu(HL)BrH₂O (B ₂ ) before irradiation showed isotropic spectrum with g _iso = 2.075 however, after irradiation (A ₂ ) displayed axial ESR spectrum with g _∥ > g _⊥ > 2.0023 and d _(x2?y2) ground state. DTA of the compounds reveals that γ-irradiation induced generation of new peaks as well as changes in the peak intensities. Solid state dc electrical conductivity for complexes was investigated before and after γ-irradiation. Complexes were found to be semiconductors, the activation energies (E _a) were calculated for the complexes by using the Arrhenius plot.     

7,15-Diazadispiro[5.1.5.3]hexadecan und Derivate, 1. Mitt.: Darstellung der Grundkörper

As starting materials for theoretical and pharmacological studies 7,15-diazadispiro[5.1.5.3]hexadecane (1), its 14-imino-(2) and 14-oxo-derivative (3) were prepared. Reduction of bis-(1-cyanocyclohexyl)-amine (4) withLAH leads to a mixture of1 and2. For the exclusive preparation of1, 4 is treated with conc. H₂SO₄ to yield the corresponding 14,16-dioxohexadecane, which is reduced to1 withLAH. The preparation of3 is effected by acid hydrolysis of acetylated2.     

Trialkylantimony(V) o-amidophenolates: Electrochemical transformations and antiradical activity

The electrochemical transformations and antiradical activity of trialkylantimony(V) o-amidophenolate derivatives, (AP)SbR₃ (AP = 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-amidophenolate); R = CH₃ (I), C₂H₅ (II), and C₆H₁₁ (III), are studied. The electrochemical oxidation of compounds I–III proceeds successively to form mono- and dicationic forms of the complexes. The presence of the donor hydrocarbon groups at the antimony(V) atom shifts the oxidation potentials to the cathodic range and decreases the stability of the monocationic complexes formed in electrochemical oxidation. The second anodic process is irreversible and accompanied by o-iminoquinone decoordination. The antiradical activity of compounds I–III is studied in the reaction with the diphenylpicrylhydrazyl radical and oleic acid autooxidation. The values obtained for indices EC₅₀ and IC₅₀ indicate the antiradical activity of the studied compounds. Complexes I–III were found to be the efficient inhibitors of oleic acid oxidation and act as efficient destructors of hydroperoxides.     

Über die Bromierung von substituierten 3,4-Dihydro- und 6-Hydroxy- bzw. 6-Äthoxy-3,4,5,6-tetrahydro-2(1H)-pyrimidinonen

Bromination of 1-benzyl-4-methyl-3.4-dihydro-2(1H)-pyrimidinone (9 a) with 1 mole Br₂ in CHCl₃ yields 1-benzyl-5-bromo-6-hydroxy-4-methyltetrahydro-2(1H)-pyrimidinone,12 a, or the 6-ethoxypyrimidinone13 a, according to whether H₂O orEtOH is used in working up. With 2 moles Br₂,9 a analogously affords the 5.5-dibromopyrimidinnes14 a or15 a. Bromination of the 6-hydroxypyrimidinone10 a yields the same products,12 a and13 a, or14 a and15 a respectively, while the 4-phenyl-pyrimidinones9 b and11 b yield the corresponding 5-bromo-and 5.5-dibromopyrimidinones13 b and15 b. The structures of the compounds12 a-15 b are confirmed by their NMR data and chemical properties: the oxopyrimidinylmethylureas16 a and17 a are formed by the action of methylurea on12 a and13 a, or on14 a and15 a respectively; with hexamethylenetetramine,12 a reacts to give the 5.6-dihydroxypyrimidinone18 a, while13 b is transformed to the 4-phenylpyrimidinone19 b. 13 b was also synthesized from α-bromocinnamaldehyde. The mechanism of bromination is discussed.     

Über cyclische Guanidin—Mesityloxid- und Guanidin—Phoron-Kondensate

The basic product synthesized byTraube andSchwarz from mesityl oxide and guanidine has not been 4.4.6-trimethyl-4.5-dihydro-2-pyrimidinamine (1), but a mixture containing the 4.4.6-trimethyl-3.4-dihydro-2(1H)-pyrimidinimine (resp. an isomeric pyrimidinamine)2 a (resp.2 b, 2 c) and the dimeric 4.4′-methylenedi[2(1H)-pyrimidinimine] (resp. an isomeric methylenedipyrimidinamine)3 a (resp.3 b, 2 c) and the dimerisation reaction were studied in a series of experiments. The product of the reaction of guanidine and phorone is not the guanidinopropylpyrimidine8 ⁴, but the 4.4′-spirobi[2(1H)-pyrimidinimine] (resp. a spirobipyrimidinamine)11 a (resp.11 b, 11 c). No determination was possible on the basis of NMR whether the condensation products of guanidine—in solutions ofDMSO-d₆—are pyrimidinimines (2 a, 3 a, 11 a) or pyrimidinamines (2 b resp.2 c, 3 b resp.3 c, 11 b resp.11 c) or mixtures of the isomeric compounds. The NMR-and mass spectra of2 a (resp.2 b, 2 c),3 a (resp.3 b, 3 c),11 a (resp.11 b, 11 c) and their derivates are discussed.     

Autoassembly of cage structures

Thed,l-(1a) andmeso-forms (1b) of α,α'-dihydroxy-α,α'-dimethyladipic acid, dilactone (3), diiminodilactone (4), and lactonolactam (5) were obtained by the reaction of acetonylacetone with KCN and HCl. The transformations of1 to the esters2, dilactone3 to la, and diiminodilactone4 to dilactone3 were studied. It was shown that3 can be readily obtained from la by thermolysis, acid catalysis, and DCC action as well as by acid catalyzed cyclization of2a, while dilactone3 can be obtained from1b and2b in negligible yield only under drastic conditions, obviously, due to the partial epimirization of themeso-forms. The mild thermolysis of1b leads totrans-lactonoacid (6), from which the ester7 has been obtained. The effective acid catalyzed cyclization of amides8 and9 to3, lactamoamide12 to5, and amide14 to model lactone13 was found. The NMR spectra of the products were studied, and a¹H NMR test was suggested for identification ofd,l- andmeso-forms1 and2. The stereochemistry of monolactones6, 7, 9, 10a, 10b, 11, and dilactone3 was established. The differences in the chemical behavior of α,α'-dihydroxyglutaric and adipic acids were explained by the significant reduction of the non-bonded interactions of the substituents in the corresponding monolactones during the transfer from 1,3- to 1,4-substituted systems.     

New copper(II) 2-(alkylamino)troponates

The copper aminotropones Cu[ON(R′)C₇H₄R-4]₂ [R = H, R′ = Me (13), Et (14), n-Pr (15), n-Bu (16), Bz (17), MenOCH₂CH₂ (20); R = i-Pr, R′ = Me (18), n-Pr (19), MenOCH₂CH₂ (21)] have been prepared from the corresponding aminotropones HN(R′)OC₇H₄R-4 (1–7) by reacting with copper(II) acetate in aqueous ethanol. 20, 21 contain the flavourant, menthol, as part of the ligand. The structures of 5 (R = H, R′ = Bz), a hydrogen-bonded dimer, 14 and 20, both incorporating square-planar, four-coordinate copper centres, have been determined by X-ray crystallography. The antibacterial activities of complexes 13, 17, 20 and 21 have been assayed against Staphylococcus waneri, an in vitro model of plaque inhibition effects, and found to be more active than a commercial toothpaste formulation, but less active than the O,O-chelated copper(II) complex of ethylmaltol.     

Über die Reaktionen von 2-Cyclohexenonen mit Ammoniumthiocyanat bzw. Thioharnstoff Über Heterocyclen, 59. Mitteilung

The 2-cyclohexenones1 a, b andc react with NH₄SCN to give 3,5,5-trimethyl-, 3-methyl-5-phenyl- and 3-methyl-2-cyclohexeniminiumthiocyanates8 a, b andc resp. (i.e. salts of α,β-unsaturated imines) and not the expected diazabicyclononane-thiones5 a, b andc. Alternative formulae for the1—NH₄SCN-condensates are discussed and rejected on the basis of IR- and NMR-spectra and the chemical properties of5 a-c. By action of thiourea inMeOH/NaOMe the 2-cyclohexenones1a, d ande are transformed into 1-hydroxy-5,7,7-trimethyl-, 1-hydroxy-5-methyl- and 1-hydroxy-2,4-diazabicyclo[3.3.1]nonane-3-thiones5 a, d ande resp. The structure of the diazabicyclononane-thiones5 a, d ande is established by means of NMR-, IR- and MS-spectra. 8 a-c and5 e showed no significant herbicidal and only small fungicidal (8 b, c) and insecticidal (8 a-c) activities in screening tests.     

Synthesis of aromatic tetracyclic tin compounds by template and transmetallation reactions: Alkyl vs aryl migration from tin to nitrogen

The syntheses of [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)amine]diphenyltin (1) and [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)amine]dichloro-phenyl-stannate (2) by template reactions using 3,5-di-tert-butylcatechol, aqueous ammonia and SnPh₂Cl₂ are reported. We also report the syntheses of compounds 2, [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)amine]trichloro-stannate (4), [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)methylamine]chloro-methyltin (5), and [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)-n-butylamine]n-butyl-chlorotin (6) and [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)amine]n-butyl-dichloro-stannate (7), performed by transmetallation reactions of the octahedral zinc coordination compound Zn[3,5-di-tert-butyl-1,2-quinone-(3,5-di-tert-butyl-2-hydroxy-1-phenyl)imine]₂ (3) with SnPhCl₃ or SnPh₂Cl₂, SnCl₄, SnMe₂Cl₂, Sn(nBu)₂Cl₂ and Sn(nBu)Cl₃, respectively. The X-ray diffraction structures of compounds 1, 2, 4 and 6 are reported. The transmetallation reactions with Sn(alkyl)₂Cl₂ afforded pentacoordinated tin compounds, where an alkyl group migrated from tin to nitrogen, while similar reactions with Sn-Ph compounds did not present any phenyl group migration.     

Microwave Promoted Oxidative Addition Reactions of Os3(CO)12: Efficient Syntheses of Triosmium Clusters of the Type Os3(μ-X)2(CO)10 and Os3(μ-H)(μ-OR)(CO)10

Microwave heating allows for the high-yield, one-step synthesis of the known triosmium complexes Os₃(μ-Br)₂(CO)₁₀ (1), Os₃(μ-I)₂(CO)₁₀ (2), and Os₃(μ-H)(μ-OR)(CO)₁₀ with R = methyl (3), ethyl (4), isopropyl (5), n-butyl (6), and phenyl (7). In addition, the new clusters Os₃(μ-H)(μ-OR)(CO)₁₀ with R = n-propyl (8), sec-butyl (9), isobutyl (10), and tert-butyl (11) are synthesized in a microwave reactor. The preparation of these complexes is easily accomplished without the need to first prepare an activated derivative of Os₃(CO)₁₂, and without the need to exclude air from the reaction vessel. The syntheses of complexes 1 and 2 are carried out in less than 15 min by heating stoichiometric mixtures of Os₃(CO)₁₂ and the appropriate halogen in cyclohexane. Clusters 3–6 and 8–10 are prepared by the microwave irradiation of Os₃(CO)₁₂ in neat alcohols, while clusters 7 and 11 are prepared from mixtures of Os₃(CO)₁₂, alcohol and 1,2-dichlorobenzene. Structural characterization of clusters 2, 4, and 5 was carried out by X-ray crystallographic analysis. High resolution X-ray crystal structures of two other oxidative addition products, Os₃(CO)₁₂I₂ (12) and Os₃(μ-H)(μ-O₂CC₆H₅)(CO)₁₀ (13), are also presented.     

Synthesis and characterization of palladium(II) complexes [PdX2(p-diben)] (X = Cl,Br, I,N3, or NCO; p-diben = N,N′-bis(4-dimethylaminobenzylidene)ethane-1,2-diamine): crystal structure of [Pd(N3)2(p-diben)]

Five new complexes of general formula [PdX₂(p-diben)], where p-diben = N,N′-bis(4-dimethylaminobenzylidene)ethane-1,2-diamine) (1) and X = Cl (2), Br (3), I (4), N₃ (5), or CNO (6), were synthesized and characterized by physicochemical and spectroscopic methods. The crystal structure of compound (5) was determined by single-crystal X-ray diffraction. Complexes 2–6 were characterized as N,N-chelated products. The crystal structure confirmed this formulation for [Pd(N₃)₂(p-diben)], besides showing the isomerism inversion of one of the C=N bonds, caused by Pd(II) coordination.     

Ringtransformation von 3,1-Benzothiazin-2,4-dithionen mit Carbonsäurehydraziden zu substituierten 1,3,4-Thiadiazolen oder (in Gegenwart von Hydroxidionen) zu 3-Acylaminochinazolin-2,4-dithionen

The substituted 1,3,4-thiadiazoles4–14 were prepared in one step by reaction of 3,1-benzothiazin-2,4-dithiones1 and3 withRCONHNH₂ (R=Me, Ph, substitutedPh, 4-Pyridyl, CONHNH₂). Reaction of1 with RCONHNH₂ in the presence of HO^? leads to substituted quinazolin-2,4-dithiones18–20. Under the action of CS₂ the yield of19 and20 increases. Possible reaction mechanisms are discussed.     

The use of Pearlman's catalyst for the oxidation of Si–H bonds. Synthesis, structures and acid-catalysed condensation of novel α, ω-oligosiloxanediols HOSiMe2O(SiPh2O)nSiMe2OH (n = 1−4)

The preparation of α , ω-oligosiloxanediolsHOSiMe₂O(SiPh₂O)_nSiMe₂OH(5–8; n=1–4) by the mild oxidation of thecorresponding organo-H-siloxaneHSiMe₂O(SiPh₂O)_nSiMe₂H(1–4; n = 1–4) using Pearlman's catalyst,Pd(OH₂)/C, is reported. Compounds 5–7 possessnew hydrogen bonding modes, whose influences on the Si–O chainconformation are discussed and compared with the published analoguesHOSiPh₂OSiPh₂OSiPh₂OH (9),HOSit-Bu₂OSiMe₂OSit-Bu₂OH (10) andHOSiPh₂OSiPh₂OSiPh₂OSiPh₂OH(11), whereas compound 8 appears to be polycrystalline.Preliminary results of the HCl-catalysed condensation of5–8 are also reported, which provided complex mixtures ofoligomeric products in the case of 5 and 8, and (almost)exclusivelycyclo-(Me₂SiO)₂(Ph₂SiO)₂(12) andcyclo-(Me₂SiO)₂(Ph₂SiO)₃(13) in the case of 6 and 7, respectively. Compounds5–7 and 13 were investigated by X-raycrystallography.     

Redox behavior of trinuclear M3(μ-H)(μ3-μ1:μ2:μ2-C2Fe)(Co)9 and tetranuclear RuM3 3(μ-H)(μ4-μ1:μ1:μ1:μ2-C2Fe)(Co)12 (M=Ru or Os; and Fc=ferrocenyl) clusters. Electronic interaction between the ferrocenylacetylide ligand and the metal core of the cluster

The redox properties of the clusters Ru₃(CO)₁₂(1), Ru₃(μ-H)(μ₃-μ¹:μ²:μ²-C₂Fe)(CO)₉ (2), OS₃(μ-H)(μ₃-μ¹:μ²:μ²-C₂Fe)(CO)₉ (3), Ru₄(μ-H)(μ₄-μ¹:μ¹:μ¹:μ²-C₂Fe)(CO)₁₂ (4), and RuOS₃(μ-H)(μ₄-μ¹:μ¹:μ¹:μ²-C₂Fe)(CO)₁₂ (5) in THF have been studied by cyclic voltammetry in the temperature range from ?60 to +20°C. It was demonstrated that reversible one-electron oxidation of the ferrocenyl fragment in clusters 2–5 occurs at more positive potentials (δE ⁰=0.15–0.26 V) than that of free ferrocene. This is indicative of the electron-withdrawing character of the cluster core with respect to the ferrocenylacetylide ligand. The electron-withdrawing effect of the metal core is more pronounced in tetranuclear clusters4 and 5 than in trinuclear clusters2 and3. Unlike complexes1–3, which undergo irreversible reduction, complexes4 and5 undergo reversible one-electron reduction to form the corresponding radical anions4 ^? and5 ^?.     

Synthesis,spectroscopic characterization,X-ray crystal structure,biological screening and catalytic studies of organotin(IV) carboxylates of 3-(4-cyanophenyl) acrylic acid

A series of six organotin(IV) carboxylates [Me₂SnL₂] (1), [n-Bu₂SnL₂] (2), [n-Oct₂SnL₂] (3), [Me₃SnL] (4), n-Bu₃SnL (5) and [Ph₃SnL] (6), where L = 3-(4-cyanophenyl) acrylic acid have been synthesized and characterized by elemental analysis, FT-IR and NMR (¹H, ¹³C). The complex (4) was also analyzed by single crystal X-ray analysis which showed distorted trigonal bipyramidal geometry with polymeric bridging behavior. The complexes 1–6 were screened for antimicrobial activities and cytotoxicity. The results showed significant activity with few exceptions. The catalytic activity of complexes was assessed in transesterification reaction of Brassica campestris oil (triglycerides) to produce biodiesel (fatty acid methyl esters). The results showed that triorganotin(IV) complexes exhibited good catalytic activity than their di-analogues.     

New N-nicotinyl and N-isonicotinyl, N′,N″-diaryl phosphorictriamides with new Er(III) complex: synthesis, spectroscopic study and crystal structures

Ten new N-nicotinyl and N-isonicotinyl phosphoramidates with formula XP(O)R₂, X?=?Nicotinamide(nia), R?=?NHCH₂Ph (1), N(CH₃)CH₂Ph (2), NHCH(CH₃)Ph (3), NH-CH₂C₄H₃O (4), NHCH₂(C₅H₄N) (5), 3-NH-C₅H₄N (6), and YP(O)R₂, Y?=?isonicotinamide(iso), R?=?NHCH₂Ph (7), N(CH₃)CH₂Ph (8), NHCH(CH₃)Ph (9), NH-CH₂C₄H₃O (10) plus one new Er(III) complex with formula Er(L)₂(NO₃)₃ (11), L?=?(iso)PO(NHCH₂C₄H₃O)₂ (10), were synthesized and characterized by elemental analysis and ¹H, ¹³C, ³¹P NMR, IR, UV?Cvis spectroscopy. Crystal structures of compounds 10 and 11 were also determined by X-ray crystallography. Interestingly, the ¹H NMR spectra of compounds 1, 2, 6, 7, 9 indicated long-range ⁿ J _P,H (n?=?5,6,7) coupling constants, in the range of 1.4?C1.9?Hz, for the splitting of pyridine ring protons with phosphorus atom. IR results showed that the ??(C=O) values of compounds 7?C10 are greater than those of compounds 1?C5 which means that isonicotinyl moiety is more electron withdrawing than nicotinyl group. X-ray outcomes revealed that in complex 11 three phosphoric triamide ligands have been connected to each Er(III); one from N_pyridine and two from P=O donor sites. One of the P=O donor ligands is mono dentate while the other one acts as a bidentate ligand and coordinates to another Er atom via its N_pyridine site. By forming complex 11 the P=O and C?CN_amide bond lengths of ligand is increased in both, mono and bi dentate, ligands while the C=O bond length is decreased to lower values. These variations are in good agreement with IR results. All H-bonds and electrostatic interactions lead to form a three-dimensional polymeric cluster in the crystal lattice of 10 and 11.     

1,2,4,5-Tetrahydro-3,2,4-benzothiadiazepin-3,3-dioxide und 1,2,3,5,6,7-Hexahydro-4,3,5-benzothiadiazonin-4,4-dioxide

1.2.4.5-Tetrahydro-3.2.4-benzothiadiazepine-3.3-dioxide (3a) (1 a) was prepared both by treating o-xylylene dibromide with sulfamide and by reaction of o-xylylene diamine (1 c) with SO₂Cl₂ or sulfamide. 4-Chloro-o-xylylene-diamine (2 c) and 1.2-bis(β-aminoethyl)benzene (8), resp., yield 7-chloro-1.2.4.5-tetrahydro-3.2.4-benzothiadiazepine-3.3-dioxide (4 a) and 1.2.3.5.6.7-hexahydro-4.3.5-benzothiadiazonine-4.4-dioxide (9), resp., on treatment with sulfamide. 3 a, 4 a, and9 yield the corresponding N,N′-dialkyl derivatives on treatment of their Na-salts with alkyl halides. Several dialkyl derivatives of3 a were prepared also by reaction of1 a with N,N′-dialkyl sulfamides.