Two polymorphs of N‐(2,6‐difluorophenyl)formamide

The structures of two distinct polymorphic forms of N‐(2,6‐difluorophenyl)formamide, C₇H₅F₂NO, have been studied using single crystals obtained under different crystallizing conditions. The two forms crystallize in different space groups, viz. form (Ia) in the orthorhombic Pbca and form (Ib) in the monoclinic P2₁ space group. Each polymorph crystallizes with one complete molecule in the asymmetric unit and they have a similar molecular geometry, showing a trans conformation with the formamide group being out of the plane of the aromatic ring. The packing arrangements of the two polymorphs are quite different, with form (Ia) having molecules that are stacked in an alternating arrangement, linked into chains of N—H...O hydrogen bonds along the crystallographic a direction, while form (Ib) has its N—H...O hydrogen‐bonded molecules stacked in a linear fashion. A theoretical study of the two structures allows information to be gained regarding other contributing interactions, such as π–π and weak C—H...F, in their crystal structures.     

O‐Ethyl and O‐methyl N‐(2,3,4,6‐tetra‐O‐acetyl‐β‐d‐glucopyranosyl)thiocarbamate

In both the title structures, O‐ethyl N‐(2,3,4,6‐tetra‐O‐acetyl‐β‐d ‐gluco­pyran­osyl)­thio­carbam­ate, C₁₇H₂₅NO₁₀S, and O‐methyl N‐(2,3,4,6‐tetra‐O‐acetyl‐β‐d ‐gluco­pyran­osyl)­thiocar­bam­ate, C₁₆H₂₃NO₁₀S, the hexo­pyran­osyl ring adopts the ⁴C₁ conformation. All the ring substituents are in equatorial positions. The acetoxy­methyl group is in a gauche–gauche conformation. The S atom is in a synperi­planar conformation, while the C—N—C—O linkage is antiperiplanar. N—H?O intermolecular hydrogen bonds link the mol­ecules into infinite chains and these are connected by C—H?O interactions.     

The Synthesis of N‐(Glycosylthioureylene)‐aminothiophosphonic and ‐diaminothiophosphinic O‐aryl Esters

Reactions of O‐aryl dihydrazinothiophosphinates ( 4, 5 ) or O,O′‐diarylhydrazinothio‐phosphonates ( 2 ) with glycosyl isocyanates ( 6 ) gave corresponding N‐(glycosylthioureylene)‐aminothiophosphonic and ‐diaminothiophosphinic O‐aryl esters. Their structures were confirmed by IR, ¹H NMR, ³¹P NMR, MS and elemental analyses.     

N‐(Ferrocenecarbonyl)‐N′‐(quinolin‐8‐yl)thio­urea

In the title compound, [Fe(C₅H₅)(C₁₆H₁₂N₃OS)], the 8‐am­inoquinoline and acyl­thio­urea moieties are almost planar. There are two perpendicular arrangements of the mol­ecules in the crystal with slightly different conformations. The two cyclo­penta­dienyl rings in each mol­ecule are parallel and eclipsed.     

(E)‐4‐Methoxy­benzaldehyde O‐(N‐phenyl­carbamo­yl)oxime

There are two mol­ecules, C₁₅H₁₄N₂O₃, in the asymmetric unit of the title compound, the first structurally characterized carbamoyl benzaldehyde oxime derivative; these mol­ecules do not differ significantly. Inter­molecular N—H⋯O hydrogen bonds connect mol­ecules into infinite …ABAB… ribbons along the [100] direction.     

N‐(4‐Methyl­phenyl)‐N‐(5‐nitro­furfuryl)‐N‐prop‐2‐ynyl­amine

The title compound, C₁₅H₁₄N₂O₃, is the first example of a structurally determined tertiary amine with both N‐5‐nitro­furfuryl and N‐prop‐2‐ynyl moieties. The mol­ecule is not planar, i.e. the furan ring is inclined at an angle of 84.35 (4)° to the phenyl ring. The crystal structure is dominated by van der Waals forces. The terminal alkynyl group as the strongest C—H hydrogen‐bond donor is not involved in hydrogen‐bond formation.     

N‐(4‐Methoxy­benzyl­idene)‐N′‐(2‐pyridyl)­hydrazine

Molecules of the title compound (alternative name p‐methoxybenzaldehyde 2‐pyridyl­hydrazone), C₁₃H₁₃N₃O, adopt an E configuration about the azomethine C=N double bond. Molecules are almost planar, the dihedral angle between the pyridine and methoxy­phenyl rings being only 6.19 (12)°. Pairwise N—H⃛N hydrogen bonds [R(8) in graph‐set notation] link centrosymmetrically related mol­ecules into discrete pairs.     

Hexanuclear Wheel‐Shaped Lithium N‐(2,6‐Diisopropylphenyl)‐N′‐(2‐pyridylethyl)benzamidinate

Lithiation of N‐(2,6‐diisopropylphenyl)‐N′‐(2‐pyridylethyl)benzamidine ( 1 ) with LiN(SiMe₃)₂ in a solvent mixture of toluene and TMEDA yields hexameric lithium N‐(2,6‐diisopropylphenyl)‐N′‐(2‐pyridylethyl)benzamidinate ( 2 ), which can be purified by recrystallization from a solvent mixture of toluene and THF. The three‐coordinate lithium ions have T‐shaped coordination spheres. The negative charge is delocalized within the 1,3‐diazaallylic system, which adopts a (syn‐Z)‐arrangement.     

Five Aromatics Bearing a 4‐O‐Methylglucose Unit from Cordyceps cicadae

Five new aromatics bearing a 4‐O‐methylglucose unit, namely 3‐methoxy‐1,4‐hydroquinone 1‐(4′‐O‐methyl‐β‐glucopyranoside) (=4‐hydroxy‐3‐methoxyphenyl 4‐O‐methyl‐β‐glucopyranoside; 1 ), 3‐methoxy‐1,4‐hydroquinone 4‐(4′‐O‐methyl‐β‐glucopyranoside) (=4‐hydroxy‐2‐methoxyphenyl 4‐O‐methyl‐β‐glucopyranoside; 2 ), vanillic acid 4‐(4′‐O‐methyl‐β‐glucopyranoside) (=3‐methoxy‐4‐[(O‐methyl‐β‐glucopyranosyl)oxy]benzoic acid; 3 ), 5‐methoxycinnamic acid 3‐O‐(4′‐O‐methyl‐β‐glucopyranoside) (=(2E)‐3‐{3‐methoxy‐5‐[(4‐O‐methyl‐β‐glucopyranosyl)oxy]phenyl}prop‐2‐enoic acid; 4 ), and naphthalene‐1,8‐diol 1,8‐bis(4′‐O‐methyl‐β‐glucopyranoside) (=naphthalene‐1,8‐diyl bis(4‐O‐methyl‐β‐glucopyranoside; 5 ), were isolated from the cultivated Cordyceps cicadae mycelia, together with thirteen known compounds. Their structures were determined by spectroscopic methods. The absolute configurations of the sugar units were not determined.     

N‐(2,6‐Dibromophenyl)formamide

In the crystal structure of the title compound, C₇H₅Br₂NO, molecules related by translation are linked through N—H...O hydrogen bonds to form chains in the crystallographic a direction, with the aryl rings stacked parallel to each other along the chain. Besides the N—H...O hydrogen bonds, Br...O and Br...Br intermolecular interactions complete the packing of molecules in the crystal structure.     

Synthesis and insecticidal evaluation of N‐tert‐butyl‐N′‐thio[O‐(1‐methylthioethylimino)‐N″‐methylcarbamate]‐N,N′‐diacylhydrazines

A series of novel N‐tert‐butyl‐N′‐thio[O‐(1‐methylthioethylimino)‐N″‐methylcarbamate]‐N,N′‐diacylhydrazines were synthesized by the reaction of chlorosulfenyl[O‐(1‐methylthioethylimino)‐N‐methylcarbamate] with N‐tert‐butyl‐N,N′‐diacylhydrazine in the presence of sodium hydride. The reaction of sulfur dichloride with O‐(1‐methylthioethylimino)‐N‐methylcarbamate (Methomyl) in the presence of pyridine to yield chlorosulfenyl[O‐(1‐methylthioethylimino)‐N‐methylcarbamate] was reported for the first time. X‐ray single crystal diffraction of N‐tert‐butyl‐N′‐thio[O‐(1‐methylthioethylimino)‐N″‐methylcarbamate]‐N,N′‐dibenzoylhydrazine demonstrated that the parent compounds N‐tert‐butyl‐N,N′‐dibenzoylhydrazine and O‐(1‐methylthioethylimino)‐N‐methylcarbamate were combined by N S N band to give the product. Their larvicidal activities against Oriental armyworm and Aphis laburni were evaluated. All of them exhibited excellent larvicidal activities against Oriental armyworm, with some of them showing higher larvicidal activities than the parent diacylhydrazines. Toxicity assays indicated that the products show knockdown activity for O‐(1‐methylthioethylimino)‐N‐methylcarbamate at higher concentration and insect growth regulators' activities of diacylhydrazines at lower concentrations. At the same time, the products possess insecticidal activities against the aphids. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:631–636, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20360     

O‐Iso­propyl N‐(2‐furoyl)­thio­car­bam­ate

The title compound, C₉H₁₁NO₃S, has crystallographic mirror symmetry, occurs in the thio­carbamate form and is stabilized in an s‐cisoid,s‐transoid conformation with respect to the C—N—C group. There are two intramolecular hydrogen bonds, one between the H atom of the N—H group and the O atom of the furan ring, and the other between the H atom of the secondary carbon of the iso­propyl group and the S atom. The packing of the mol­ecules is assumed to be dictated by van der Waals interactions.     

Enzymatic Synthesis of Nucleoside‐5′‐O‐(1‐thiophosphates) and (SP)‐Adenosine‐5′‐O‐(1‐thiotriphosphate)

Treatment of adenosine with PSCl₃ in trimethyl phosphate gave, after ion‐exchange chromatography, adenosine‐5′‐O‐monophosphate (AMP; 28%) and adenosine‐5′‐O‐monothiophosphate (AMPS; 48%). AMPS was studied as a thiophosphate residue donor in an enzymatic transphosphorylation with nucleoside phosphotransferase (NPase) of the whole cells of Erwinia herbicola. As exemplified by a number of natural and sugar‐ and base‐modified nucleosides, it was demonstrated that NPase of the whole cells of Erwinia herbicola catalyzes the transfer of both thiophosphate and phosphate residues with a similar efficiency. An incubation of AMPS in a phosphorylating extract of Saccharomyces cerevisiae (K‐phosphate buffer (0.3 M , pH 7.0); 3% glucose; 15 mM MgCl₂; 28°, 8 h), followed by ion‐exchange column chromatography afforded AMP (8%), AMPS (recovered, 23%), ATP (11%), and (S_P)‐adenosine‐5′‐O‐(1‐thiotriphosphate) ((S_P)‐ATPαS); (total yield 37%; 48% based on the consumed AMPS). For comparison of physicochemical properties, adenosine was chemically transformed into ATPαS as a mixture of the (S_P) (53%) and (R_P) (44%) diastereoisomers.     

(E)‐N′‐(4‐Chlorobenzylidene)‐, (E)‐N′‐(4‐bromobenzylidene)‐ and (E)‐N′‐[4‐(diethylamino)benzylidene]‐ derivatives of 4‐hydroxybenzohydrazide

The 4‐chloro‐ [C₁₄H₁₁ClN₂O₂, (I)], 4‐bromo‐ [C₁₄H₁₀BrN₂O₂, (II)] and 4‐diethylamino‐ [C₁₈H₂₁N₃O₂, (III)] derivatives of benzylidene‐4‐hydroxybenzohydrazide, all crystallize in the same space group (P2₁/c), (I) and (II) also being isomorphous. In all three compounds, the conformation about the C=N bond is E. The molecules of (I) and (II) are relatively planar, with dihedral angles between the two benzene rings of 5.75 (12) and 9.81 (17)°, respectively. In (III), however, the same angle is 77.27 (9)°. In the crystal structures of (I) and (II), two‐dimensional slab‐like networks extending in the a and c directions are formed via N—H...O and O—H...O hydrogen bonds. The molecules stack head‐to‐tail viaπ–π interactions involving the aromatic rings [centroid–centroid distance = 3.7622 (14) Å in (I) and 3.8021 (19) Å in (II)]. In (III), undulating two‐dimensional networks extending in the b and c directions are formed via N—H...O and O—H...O hydrogen bonds. The molecules stack head‐to‐head viaπ–π interactions involving inversion‐related benzene rings [centroid–centroid distances = 3.6977 (12) and 3.8368 (11) Å].     

An interesting cyclization of N‐methyl‐3‐phenyl‐N‐(2‐(Z)‐phenylethenyl)‐cis‐oxiranecarboxamide

Under Lewis acid condition, N‐methyl‐3‐phenyl‐N‐(2‐(Z)‐phenylethenyl)‐cis‐oxiranecarboxamide undergoes elegant double cyclizations to give interesting products.     

N‐(2‐Amino­benz­yl)‐N,N‐bis­(quinolin‐2‐ylmeth­yl)amine

The title new diquinaldine derivative, C₂₇H₂₄N₄, forms mol­ecular assemblies organized by inter­molecular quinoline π–π stacking [3.356 (3) and 3.440 (3) Å] and both inter‐ and intra­molecular N—H⋯N hydrogen bonds [3.039 (3)–3.104 (3) Å and 129 (2)–172 (2)°]. The combination of such inter­actions provides readily definable contacts that propagate along each crystallographic axis.     

Ene Reaction with Pummerer‐type Reaction Intermediate of α‐(Methylthio)‐N‐methoxy‐N‐methyl Acetamide: A New Synthesis of N‐methoxy‐N‐methyl‐(E,E)‐2,4‐dienamides

Pummerer‐type reaction intermediate 2 of α‐(methylthio)‐N‐methoxy‐N‐methyl acetamide (1) has been found to react with 1‐alkenes to afford ene adducts 3 . N‐Methoxy‐N‐methyl‐(E,E)‐2,4‐dienamides were synthesized from the adducts 3b‐f .     

N‐Germyl derivatives of sulfacetamide and ortho‐(sulfonamido)phenylamines: characterization of N‐[o‐(N′,N′‐dimethylsulfonamido)phenyl]‐N‐dimesitylgermaimine

Triethylgermylation of sulfacetamide occurs on the sulfonamido nitrogen in competition with the 1,2 addition of the starting triethylgermyl dimethylamine on the carbonyl group. Thermal decomposition in the presence of dimethylamine yields N‐triethylgermylsulfanilamide. Stable 1:1 sulfacetamide–DBU and 1:1 sulfacetamide–Et₃N complexes were isolated and fully characterized in the course of dehydrochlorination reactions. o‐Sulfonamidophenylamine yields N,N′‐bis‐triethylgermylated derivatives, whereas o‐(N,N‐dimethylsulfonamido)phenylamine leads to monogermylated compounds. The N‐dimethylaminodimesitylgermyl derivative is thermally stable. Dehydrohalogenation of the N‐dimesitylfluorogermyl compound leads to the thermally stable but water sensitive N‐[o‐(N′,N′‐dimethylsulfonamido)phenyl]‐N‐dimesitylgermaimine. Copyright © 2003 John Wiley & Sons, Ltd.     

Structural comparison of three N‐(4‐halogenophenyl)‐N′‐[1‐(2‐pyridyl)ethylidene]hydrazine hydrochlorides

2‐{1‐[(4‐Chloroanilino)methylidene]ethyl}pyridinium chloride methanol solvate, C₁₃H₁₃ClN₃⁺·Cl⁻·CH₃OH, (I), crystallizes as discrete cations and anions, with one molecule of methanol as solvent in the asymmetric unit. The N—C—C—N torsion angle in the cation indicates a cis conformation. The cations are located parallel to the (02) plane and are connected through hydrogen bonds by a methanol solvent molecule and a chloride anion, forming zigzag chains in the direction of the b axis. The crystal structure of 2‐{1‐[(4‐fluoroanilino)methylidene]ethyl}pyridinium chloride, C₁₃H₁₃FN₃⁺·Cl⁻, (II), contains just one anion and one cation in the asymmetric unit but no solvent. In contrast with (I), the N—C—C—N torsion angle in the cation corresponds with a trans conformation. The cations are located parallel to the (100) plane and are connected by hydrogen bonds to the chloride anions, forming zigzag chains in the direction of the b axis. In addition, the crystal packing is stabilized by weak π–π interactions between the pyridinium and benzene rings. The crystal of (II) is a nonmerohedral monoclinic twin which emulates an orthorhombic diffraction pattern. Twinning occurs via a twofold rotation about the c axis and the fractional contribution of the minor twin component refined to 0.324 (3). 2‐{1‐[(4‐Fluoroanilino)methylidene]ethyl}pyridinium chloride methanol disolvate, C₁₃H₁₃FN₃⁺·Cl⁻·2CH₃OH, (III), is a pseudopolymorph of (II). It crystallizes with two anions, two cations and four molecules of methanol in the asymmetric unit. Two symmetry‐equivalent cations are connected by hydrogen bonds to a chloride anion and a methanol solvent molecule, forming a centrosymmetric dimer. A further methanol molecule is hydrogen bonded to each chloride anion. These aggregates are connected by C—H...O contacts to form infinite chains. It is remarkable that the geometric structures of two compounds having two different formula units in their asymmetric units are essentially the same.