Arbeiten über Phosphorsäure- und Thiophosphorsäureester mit einem heterocyclischen Substituenten. 7. Mitteilung. Thio- und Dithiophosphorsäureester von der Art des GS 13005 mit einem analogen oder homologen heterocyclischen Ring

To complete results presented in this and in previous papers of this series as well as published in patents of other authors a review is given on known and new variations of the heterocyclic moiety in GS 13005 type thio- and dithiophosphoric acid esters ( 1, 2 ) by modification of the 1,3,4-thiadiazol-2(3H)-one ring 5 and by its replacement by analogue five- and homologue six-membered rings. Among new esters of this type some containing the pyrazolinone ring 3 or a 2-alkoxy-4H, 6H-1,3,4-thiadiazin-5-one ring 10 (homologue of the original 5-methoxy-1,3,4-thiadiazol-2(3H)-one ring in GS 13005) show no remarkable pesticidal activity, some others containing a pyrazolering 7 or a 3(2H)-pyridazinonc ring 8 are moderately to highly active but toxic to inauinials in the same proportion. Attempts to prepare seven-membered 2-alkoxy- and 2-alkylthio-6,7-dihydro-l, 3,4-thiadiazepin-S(4H)-ones 11 , Z-rnethoxy-l,3,4-thiadiazepin-S(4H)-one 12 (ring vinylogue of the original 5-methoxy-l,3,4-thiadIazol-2(3H)-one ring in GS 13005) and its 7-methyl-derivative have been unsuccessful due to unexpected side reactions, such as: five-ring closure of 3-(3-chloropropionyl)-thio- and -dithiocarbazic acid esters 22 to pyrazolidinone derivatives 23 , pyrazolinone ring closure of a 3-(acetoacety1)-thiocarbazic acid O-methyl ester derivative 26 , bromine attack on sulfur in 3-(2-alkenoyl)-thiocarbazic O-methyl esters 29 instead of bromine addition at the double bond, and halogen splitting off without ring closure in 3-(2,3-dihalogeno-alkanoyl) -thiocarbazic O-methyl esters 30 prepared by acylation of thiocarbazic acid O-methyl ester with dihalogeno-alkanoyl-chlorides.     

Arbeiten über Phosphorsäure- und Thiophosphorsäureester mit einem heterocyclischen Substituenten. 3. Mitteilung. Thiadiazol-Ringschluss und eine dabei auftretende Methylübertragung

Methods for the synthesis of 5-alkoxy- and 5-alkylthio-1,3,4-thiadiazol-2(3H)-ones and -thiones, known in principle, are extended and adapted for large scale preparations. In the particular case of 5-methoxy-1,3,4-thiadiazol-2(3H)-thione the cyclisation of thiocarbazic O-methyl ester using alcoholic alkali and carbon disulfide added in this order surprisingly yields by transmethylation 5-methylthio-1,3,4-thiadiazol-2(3H)-one, isomer of the expected 5-methoxy-1,3,4-thiadiazol-2(3H)-thione. This latter compound is obtained when the reactants are applied in the inverse sequence. A possible mechanism for this behaviour is presented.     

Arbeiten über Phosphorsäure- und Thiophosphorsäureester mit einem heterocyclischen Substituenten. 4. Mitteilung. 3-Isopropyliden-dithiocarbazinsäure-alkylester und deren Ringschluss zu 5-Alkylthio-1,3,4-thiadiazol-2(3H)-onen

Impurities in crude oily dithiocarbazic acid (2′-methoxy)-ethyl ester causing troubles in the ring closure to 5-(2′-methoxy-ethylthio)-1,3,4-thiadiazol-2(3H)-one and in succeeding reactions are eliminated by using the crystalline 3-isopropylidene-dithiocarbazic acid (2′-methoxy)-ethyl ester, which can be obtained directly by alkylation of potassium dithiocarbazate with 2-methoxy-ethyl bromide in presence of acetone. By the action of phosgene followed by that of water, the isopropylidene compound yields the oily 5-(2′-methoxy-ethylthio)-1,3,4-thiadiazol-2(3H)-one by splitting off the isopropylidene group and by ring closure in one single step.     

Arbeiten über Phosphorsäure und Thiophosphorsäureester mit einem heterocyclischen Substituenten 9. Mitteilung 1. Aza-Analogie I: Aza-Analoge von Phthalimid-, Benztriazol- und 1,2,3-Benztriazin-4(3H)-on-Derivaten

Aza-analogues of the known pesticidal dithiophosphates 2, 4 and 5 have been prepared by replacing the phthalimide, benzotriazole and 1,2,3-benzotriazin-4(3H)-one moieties resp. in 2 by those of quinolinic acid imide (6), cinchomeronic acid imide (7) and pyrazine-2,3-dicarboxylic acid imide (12), in 4 by 1H-v-triazolo[4,5-b]pyridine (15) and in 5 by pyrido[2,3-e]1,2,3-triazin-4(3H)-one (21). Compared to the known compounds the new esters are less or at best equally pesticidal with an equal or even higher mammalian toxicity.     

Herstellung und Solvolyse von 3-substituierten p-Toluolsulfonsäure-(1-adamantyl)estern

The Preparation and Solvolysis of 3-substituted 1-Adamantyl Toluenesulfonates Methods for the preparation of some hitherto unknown 3-iubstitutetl 1-adamantyl toluenesulfonates are evaluated. Their solvolysis products in dioxane/water 70:30 are reported.     

Ringerweiterung von 1,2-Thiazol-3(2H)-on-1,1-dioxiden und 3-Amino-2H-azirinen zu 4H-1,2,5-Thiadiazocin-6-on-1,1-dioxiden

Ring Enlargement of 1,2-Thiazol-3(2H)-one-1,1-dioxides and 3-Amino-2H-azirines to 4H-1,2,5-Thiadiazocin-6-one-1,1-dioxides Reaction of 3-amino-2H-azirines 2 with the 1,1-dioxides 4 and 7 of 1,2-thiazol-3(2H)-ones and 1,2-thiazoli-din-3-ones, respectively, in i-PrOH at room temperature leads to 4H-1,2,5-thiadiazocin-6(5H)-one-1,1-dioxides 5 (Scheme 2, Table) and the corresponding 7,8-dihydro derivatives 8 (Scheme 4), respectively. The structure of some of the new 8-membered heterocycles as well as the structure of the minor by-product 6 (Scheme 3) have been established by X-ray crystallography (Chapt. 4). The proposed reaction mechanism for the ring expansion to 5 and 8 (Scheme 2) is in accordance with previously published results of reactions of 2 and NH-acidic heterocycles and is further supported by the results of the reaction of 4a and the (1-¹⁵N)-labelled aminoazirine 2a *.     

Carotinoid-Glycosylester 4. Mitteilung. Synthese von 8′-Apo-β-carotin-8′-säure-(β-D-glucosyl)ester und Vitamin-A-säure-(β-D-glucosyl)ester

Carotenoid Glycosyl Esters Synthesis of β-D -Glucosyl 8′-Apo-β-carotene-8′-oate and β-D -Glucosyl Vitamin-A-oate (β-D -Glucosyl Retionate) β-D -glucosyl 8′-apo-β-carotene-8′-oate (III) and β-D -glucosyl vitamin-A-oate (VI) were regio- and stereoselectively synthesized in high yields from the N-acylimidazoles I and IV, respectively, or from the N-acyltriazoles II and V, respectively, and unprotected β-D -glucose, according to the method described for the synthesis of di(β-D -glucosyl) 8,8′-diapo-carotene-8,8′-dioate [1]. It seems that this method can generally be applied for the synthesis of β-D -glucosyl esters of polyene carboxylic acids.     

Kristallstruktur von Trimethylisocyanursäure, (CH3NCO)3, und von Trichlorisocyanursäure-1/2-Ethylenchlorid, (ClNCO)3·1/2C2H4Cl2

X-ray crystal structure analyses of (CH₃NCO)₃ (M) and (ClNCO)₃·1/2C₂H₄Cl₂ (C) were carried out at room temperature (MoK, graphite monochromator, =0.71069 Å): 1.M=171.16, monochlinic, P2₁/c,a=14.848 (1) Å,b=13.400 (2) Å,c=8.149 (1) Å, =100.87 (1)°,V=1 592.3 ų,Z=8,F(000)=720,d _x =1.428 Mgm^–3, =76m^–1,R=6.51%,R _w =7.01% (964 reflections, 218 parameters). 2.M=281.89, monochlinic, P 2₁/c,a=9.416 (3) Å,b=5.728 (1) Å,c=18.199 (8) Å, =98.64 (2)°,V=970.4 Å₃,Z=4,F(000)=556,d _x =1.929 Mgm^–3, =1.11 mm^–1,R=3.96%,R _w =3.44% (605 reflections, 132 parameters). The ring systems together with the C atoms of the methyl groups in (M) and with the Cl atoms in (C) are planar and have D_3h-symmetry. Bond lengths and bond angles are discussed with regard to¹⁴N-NQR,³⁵Cl-NQR and vibrational spectroscopic data.

     

Aminomethylierung von Thiophosphorsäuredialkylester-, Phosphon- bzw. Thiophosphonsäurealkylesteramiden,Phosphon- bzw. Thiophosphonsäurediamiden und Diphenylthiophosphinsäureamid

Aminomethylation of Phosphoro-, Phosphono-, Phosphinoamidoates and -amidothioates Dialkylphosphoroamidates, alkyl-phosphonoamidates and phosphonoamidothioates react with C₂H₅O? CH₂? NR₂ and HCOH/HNR₂, respectively, as like as a N-aminomethylation forming the corresponding derivatives of the general formula R₂P(X)? NR′? CH₂? NR″₂? R = alkoxy, alkyl, aryl; R′ = H, alkyl; X = O, S; R″ = alkyl, cycloalkyl —. Under the same conditions phosphonodiamidoates and phosphonodiamidothioates yield RP(X)-[NR′? CH₂? NR″₂]₂ or RP(X)? NHR′? (NR′? CH₂? NR″₂) only. These compounds are not formed by interactions of RP(X)(NR′? CH₂OH)₂ with sec. amines. The aminomethylation of (C₆H₅)₂P(S)NH₂ gives unexceptional [(C₆H₅)₂P(S)]₂N? CH₂? NR′₂. The i.r. and ¹H-n.m.r. data of the prepared compounds, which can't be distilled mostly, are discussed.     

Über Chalkogenolate. 133. Untersuchungen über Ester von Halogenoameisensäuren 1. Chloroameisensäure-, Chloromonothioameisensäure- und Chlorodithioameisensäurealkylester

On Chalcogenolates. 133. Studies on Esters of Haloformic Acids. 1. Alkyl Esters of Chloroformic, Chloromonothioformic, and Chlorodithioformic Acids The prepared esters RO? CO? Cl, RS? CO? Cl, RO? CS? Cl, and RS? CS? Cl with R = alkyl have been characterized by means of electron absorption, infrared, nuclear magnetic resonance, and mass spectra.     

Chloracylierung und Bromacylierung von Carbonylverbindungen. IV. Bildungsmechanismus von Carbonsäure-(1-halogenalkyl)estern

Chloroacylation and bromoacylation of carbonyl compounds IV. Investigations of the reaction mechanism The kinetics of the Lewis acid catalyzed reaction between acyl chlorides and carbonyl compounds (especially aldehydes) is investigated by ¹H-NMR.-spectroscopy. With acetyl chloride as starting material a second order reaction is observed; the rate of the reaction increases in polar solvents as well as with increasing electron-donating capacity of the aldehyde. - With benzoyl chloride as starting material the reaction is first order with respect to benzoyl chloride, but zero order with respect to the aldehyde. The reaction rate is strongly influenced by the substituents of the benzoyl chloride. - Two polar reaction mechanisms which are in accord with these results are outlined and discussed.     

Triorganoantimon- und Triorganobismutderivate von 2-Pyridincarbonsäure und 2-Pyridylessigsäure Kristall- und Molekülstrukturen von (C6H5)3Sb(O2C-2-C5H4N)2 und (CH3)3Sb(O2CCH2-2-C5H4N)2

Triorganoantimony and Triorganobismuth Derivatives of 2-Pyridinecarboxylic Acid and 2-Pyridylacetic Acid. Crystal and Molecular Structures of (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂ and (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ Triorganoantimony and triorganobismuth dicarboxylates R₃M(O₂C-2-C₅H₄N)₂ (M = Sb, R = CH₃, C₆H₅, 4-CH₃OC₆H₄; M = Bi, R = C₆H₅, 4-CH₃C₆H₄) and (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ have been prepared from (CH₃)₃Sb(OH)₂, R₃SbO (R = C₆H₅, 4-CH₃OC₆H₄), or R₃BiCO₃ (R = C₆H₅, 4-CH₃C₆H₄) and the appropriate heterocyclic carboxylic acid. Vibrational spectroscopic data indicate a trigonal bipyramidal environment of M the O(? C)-atoms of the carboxylate ligands being in the apical and three C atoms (of R) in the equatorial positions; in addition coordinative interaction occurs in the 2-pyridinecarboxylates between M and O(?C) of one and N of the other carboxylate ligand and in (CH₃)₃)Sb(O₂CCH₂-2-C₅H₄N)₂ between Sb and O(?C) of both carboxylate ligands. (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂/(CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ crystallize monoclinic [space group P2₁/c/P2₁/n; a = 892.6(9)/1043.4(6), b = 1326.9(6)/3166.2(18), c = 2233.1(9)/1147.5(7) pm, β = 99.74(8)°/97.67(5)° Z = 4/8; d(calc.) = 1.522/1.553 × Mg m^?3; V_cell = 2606.7 × 10⁶/3757.0 × 10⁶pm³, structure determination from 3798/4965 independent reflexions (F ≥ 4.0 σ(F))/(I ≥ 1.96 σ(I), R(unweighted) = 0.024/0.036]. Sb is bonding to three C₆H₅/CH₃ groups in the equatorial plane [mean distances Sb? C: 212.2(3)/208.7(6) pm] and two carboxylate ligands via O in the apical positions [Sb? O distances: 218.5(2), 209.9(2)/212.1(3), 213.2(3) pm]. In (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂ there is a short Sb? O(?C) and a short Sb? N contact [Sb? O: 272.1(2), Sb? N: 260.2(2) pm] and distoritions of the equatorial angles [C? Sb? C: 99.2(1)°, 158.2(1)°, 102.0(1).] and of the axial angle [O? Sb? O: 169.9(1)°], and in (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂, which contains two different molecules in the asym-metric unit, there are two Sb? O(?C) contacts [Sb? O, mean: 302.2(4), and 310.7(4)pm, respectively] and distortions of the equatorial angles [C? Sb? C: 114.5(2)°, 132.4(3)° 113.1(2)°, and 123.9(3)° 115.5(2)°, 120.6(3)°, respectively] and of the axial angles [O? Sb? O: 174,9(1)°, 177.9(1)°, respectively].     

Kristallstrukturen von Säurehydraten und Oxoniumsalzen. XX. Die Oxoniumtetrafluoroborate H3OBF4, [H5O2]BF4 und [H(CH3OH)2]BF4

Crystal Structures of Acid Hydrates and Oxonium Salts. XX. Oxonium Tetrafluoroborates H₃OBF₄, [H₅O₂]BF₄, and [H(CH₃OH)₂]BF₄ The crystal structures of three oxonium tetrafluoroborates were determined. H₃OBF₄, oxonium tetrafluoroborate proper, is triclinic with space group P1 , Z = 2 and the unit cell dimensions a = 4.758, b = 6.047, c = 6.352 Å and α = 80.40, β = 79.48, γ = 88.25° at ?26°C. Cations H₃O⁺ and anions BF₄^? are linked by hydrogen bonds O? H…?F into ribbons of condensed rings. In [H₅O₂]BF₄ (diaquohydrogen tetrafluoroborate, monoclinic, P2₁/c, Z = 4, a = 6.584, b = 9.725, c = 7.084 Å, β = 95.15° at ?100°C) the hydrogen bond in the cation H₅O₂⁺ is 2.412 Å short, asymmetric and approximately centered and the linking of cations and anions three-dimensional. In [H(CH₃OH)₂]BF₄ (Bis(methanol)hydrogen tetrafluoroborate, monoclinic, P2₁/c, Z = 4, a = 5.197, b = 14.458, c = 9.318 Å, β = 94.61° at ?50°C) the cation [H(CH₃OH)₂]⁺ is characterized for the first time in a crystal structure with an again very short (2.394 Å), asymmetric and effectively centered hydrogen bond. By further hydrogen bonds cations and anions form only dimers of the formula unit of centrosymmetric cyclic structure.     

Herstellung der 1H-Indazole durch Photolyse von 2-Aminophenylketon-O-(äthoxycarbonyl)oximen und von 3,1,4-Benzoxadiazepin-2 (1H)-onen

1H-Indazoles Obtained by Photolysis of 2-Aminophenylketon-O-(ethoxycarbonyl)oximes and of 3, 1, 4-Benzoxadiazepine-2(1 H)-ones Irradiation of (E)- and (Z)-O-(ethoxycarbonyl)oximes 1 of 2-aminophenyl ketones in solution with UV, and/or visible light gives 1 H-indazole derivatives 2 in high yields (Scheme 1). For this reaction the amino group must be un- or mono substituted. With the N, N-disubstituted (E)- 1d (Scheme 2) no 1 H-indazole formation is observed, because the radicals formed by its photolysis react in an unspecific manner with each other and with the solvent. From the behaviour of (E)- 1d and from the lack of any E/Z-isomerization of 1 we conclude that the photoreaction starts with a splitting of the N, O-bond in two separate radicals, whereas the radical pair produced by the also studied photolysis of 3,1,4-benzoxadiazepine-2(1 H)-one derivatives 3 is fixed in the parent molecule, and therefore tends to recombine. This makes a prolonged irradiation necessary to convert the benzoxadiazepinones 3 into the 1 H-indazoles 2 . The different reaction rates of the (E) and (Z)-isomers of 1 (provided R⁴ = H) are understood by means of different intramolecular H-bridges.