Month: December 2022

Fuson, Reynold C. published the artcileLevinstein mustard gas. IV. The bis(2-chloroethyl)polysulfides, Recommanded Product: 1,2-Bis(2-chloroethyl)disulfane, the publication is Journal of Organic Chemistry (1946), 487-98, database is CAplus and MEDLINE.

In the preparation of II according to the L. process, a considerable amount of products with a high S content is formed. These products are considered to consist of bis(2-chloroethyl) polysulfides (XXVII) (cf. Conant, et al., loc. cit.). XXVII are identified and synthesized. H₂O₂ (503 g., 30%) is slowly added over a period of 2 hrs. to 624 g. XX with stirring and cooling to maintain a temperature of 50-60°. The mixture is kept 2 hrs. and the H₂O distilled off in vacuo. Heating the crude (HOCH₂CH₂)₂S₂ (XXVIII) with 2800 cc. concentrated HCl on a steam bath for 0.5 hr. gives 94% III, b_0.4 97-8°, n_D²⁰ 1.5656. An apparatus for a continuous process for the preparation of III is described. When to Na₂S₃, prepared by dissolving 256 g. S and 960 g. Na₂S.9II₂O in 1300 cc. H₂O, 644 g. HOCH₂CH₂Cl (XXIX) is added over a period of 0.5 hr. with cooling with ice-H₂O, the mixture stirred an addnl. 4 hrs., the oily layer separated, and the H₂O and excess XXIX are distilled off in vacuo, 80% (HOCH₂CH₂)₂S₃ is obtained and is converted with SOCl₂ into crude IV which is purified by distillation at 0.01 mm. The fractions with n_D 1.59-1.62 are crystallized from absolute EtOH, giving pure IV, m. 30.5-1.5°, n_D²⁰ 1.6110. When 120 g. II from the Levinstein process is stirred with H₂O for 11 days and the H₂O frequently changed until the H ion concentration becomes negligible, 29.1% unhydrolyzed XXVII is obtained and dissolved in Cellosolve (XXX). S (77.5 g.) and a small amount of viscous oil are filtered off and the XXX is washed out with H₂O, leaving crude (ClCH₂CH₂)₂S₅ (XXXI), n_D²⁰ 1.6763. Calculated on the S recovered, the original XXVII has the composition (ClCH₂ CH₂)₂S_7.5. XXXI is further purified by steam distillation to remove any III and IV. The residual XXXI is treated again with XXX, washed with H₂O, taken up in ether, and the ether solution dried and evaporated, giving 70% pure XXXI, n_D²⁰ 1.6853, d_D²⁰ 1.5013. When IV is treated 6-36 hrs. at temps, ranging from 115-40° with various mol. amounts of S, homogeneous products are obtained. These compounds, when kept in the refrigerator for several days, deposit S in amounts equal to the amount used in excess of that required to form XXXI. Treatment of the products with XXX gives XXXI. III and S at 145-50° for 20-30 hrs. also give XXXI. On treatment of the hydrolysis products of II with XXX, a small amount of alc.-insoluble oil (the analysis of which agrees with C₄H₈Cl₂S₁₁), which slowly deposits S on standing, is obtained. Me₂S₄, b_1.5 68-70°, n_D²⁰ 1.6621, d₄²⁰ 1.3008, is prepared according to the method of Levi and Baroni (C.A. 23, 4927) in 25% yield. An attempt to sulfurize III with Me₂S₄ failed. When 0.14 mol. Me₂S₄ and 0.06 mol. IV are heated at 35-40° and 3-4 mm., Me₂S₃, n_D²⁰ 1.5999, slowly distills, and, on raising the temperature to 120° for 2 hrs., 50% XXXI, n_D²⁰ 1.6850, is obtained. Sulfurization of XXXI with Me₂S₄ 4 hrs. at 75° in a N atm. and finally at 130° several hrs., gives 97% (ClCH₂CH₂)₂S₇ (XXXII), n_D²⁰ > 1.74, which deposits S upon standing. When treated with NH₃, XXXII is reconverted into XXXI. When the sulfurization is carried out by using a large amount of Me₂S₄, higher polysulfides are formed which lose S rapidly upon standing. When XXXI is subjected to a steam distillation and the residue is allowed to stand for 1 week, no S is deposited. The residue, n_D²⁰ 1.702, has the composition (ClCH₂CH₂)₂S_5.5. When 10 g. XXXI is heated with 9 g. S at 110° for 3 days, (ClCH₂CH₂)₂S₁₂, red viscous oil, is obtained. IV, when shaken with finely divided S, dissolves 4.4% S, while XXXI dissolves 7.4%. In lieu of XXX, moist NH₃ can be used for the stripping of XXVII, resulting in the formation of XXXI. When the stripping is carried out with NH₃ in the presence of XXX or ether, IV is obtained. When XXXI is refluxed with Me₂CO for 2 days, a XXVII is obtained, corresponding approx. to a tetrasulfide, n_D²⁰ 1.6545. Steam distillation of XXXI gives an impure IV, m. 13°, n_D²⁰ 1.611. On heating of IV at 145-60° and 0.5 mm., III, n_D²⁰ 1.5690, distills, leaving a mixture of S and XXVII from which no IV can be isolated. III and IV are quite stable to hydrolysis with H₂O. By exhaustive hydrolysis of II from the L. process and stripping the residue with XXX, a mixture of III and XXXI, n_D²⁰ 1.6740, is obtained. From this n_D and on the basis of n_D²⁰ 1.6835 for XXXI and 1.5656 for III, a content of 1.8% III is calculated for the original II. When 3.1 g. III is slowly added to 5.5 g. com. 90% thiosalicylic acid and 2.6 g. NaOH in 150 cc. 95% EtOH, the mixture refluxed h 1 hr., and poured into 400 cc. H₂O, acidification of the solution with dilute HCl precipitates 5.1 g. of a compound, C₁₈H₁₈O₄S₄, crystals from EtOH, m. 185-6°. Heating 7 g. III in 50 cc. MeOH with 165 g. XXII in 125 cc. MeOH and 15 cc. H₂O 2 hrs. on a steam bath gives 92% of a compound, C₁₄H₂₄N₂O₂S₆, fine needles from 95% EtOH, m. 109-10°. III and piperidine give 53% bis[2-(1-piperidyl)ethyl] disulfide, oil, n_D²⁰ 1.5478 (di-HCl salt, crystals, m. 236°). The structure of XXVII is discussed and it is concluded that III and IV possess a linear structure rather than an angular one. Structure XXXIa is proposed for XXXI.

Journal of Organic Chemistry published new progress about 1002-41-1. 1002-41-1 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is 1,2-Bis(2-chloroethyl)disulfane, and the molecular formula is C4H8Cl2S2, Recommanded Product: 1,2-Bis(2-chloroethyl)disulfane.

Referemce:
https://en.wikipedia.org/wiki/Chloride,
Chlorides – an overview | ScienceDirect Topics

Mal, Sanjib published the artcileFacile one pot synthesis of 8-chloro-[1,2,4]triazolo[4,3-a]pyrazines via oxidative cyclisation using chloramine T, Category: chlorides-buliding-blocks, the publication is Tetrahedron Letters (2015), 56(22), 2896-2901, database is CAplus.

A facile and expedient one pot synthesis of 8-chloro-[1,2,4]triazolo[4,3-a]pyrazine derivatives I [R¹ = H, Cl; R = Ph, 3-MeO-C₆H₄, 4-Br-C₆H₄, etc.] from 2-chloro-3-hydrazinylpyrazine and aldehydes is described using chloramine T trihydrate as a safe and convenient electrocyclisation (oxidising) agent. The presence of the chloro group on pyrazine enabled us to access versatile new synthetic scaffolds II [R¹ = Ph, 2-thiophenyl, 2,4-diCl-C₆H₃] by easy diversification using palladium catalyzed Suzuki-Miyaura and Sonogashira cross coupling reactions. The products are obtained in high yields in short reaction time under mild conditions without the need for chromatog. purification

Tetrahedron Letters published new progress about 7080-50-4. 7080-50-4 belongs to chlorides-buliding-blocks, auxiliary class Halogenation Reagent,Inhibitor, name is Sodium chloro(tosyl)amide trihydrate, and the molecular formula is C7H13ClNNaO5S, Category: chlorides-buliding-blocks.

Referemce:
https://en.wikipedia.org/wiki/Chloride,
Chlorides – an overview | ScienceDirect Topics

Kalola, Anirudhdha G. published the artcileReduction of aliphatic, aromatic and heteroaromatic carboxylic acid derivatives to alcohol promoted by trityl resin under presence of copper sulphate and sodium borohydride catalytic system, COA of Formula: C19H14Cl2, the publication is Heterocyclic Letters (2022), 12(1), 87-99, database is CAplus.

An efficient, eco-friendly, mild protocol for the acid-alc. transformation is developed. Varied aliphatic, aromatic and heteroaromatic carboxylic acid derivatives RC(O)OH [R = n-heptadecan-1-yl, 1-naphthyl, furan-2-yl, etc.] loaded on to the 2-chloro trityl chloride resin under perseverance of DIPEA base followed by subsequent reduction into corresponding alcs. ROH using CuSO₄-NaBH₄ catalytic system have been achieved in excellent yield with easy product isolation technique. Facile recycling of the recovered resin is also associated to this methodol.

Heterocyclic Letters published new progress about 42074-68-0. 42074-68-0 belongs to chlorides-buliding-blocks, auxiliary class Chloride,Benzyl chloride,Benzene, name is 2-Chlorotrityl chloride, and the molecular formula is C19H14Cl2, COA of Formula: C19H14Cl2.

Referemce:
https://en.wikipedia.org/wiki/Chloride,
Chlorides – an overview | ScienceDirect Topics

Nagarajaiah, H. published the artcileSequential One-Pot Synthesis of 2-Aminothiazoles Using Corresponding Ketones: Insights into Their Structural Features, Safety of 1-(4-Chlorophenyl)thiourea, the publication is Polycyclic Aromatic Compounds (2022), 42(4), 1909-1919, database is CAplus.

2-Aminothiazoles have been synthesized by a one-pot, two-step sequential procedure in solution state which does not involve the isolation of intermediates. It involves α-halogenation of corresponding precursor ketones followed by condensation with substituted thiourea derivatives All the products were analyzed by IR, NMR, mass spectral techniques and four of them were evaluated crystallog. One of them crystallizes in the triclinic crystal system with space group P, while, all the other compounds crystallize in the monoclinic crystal system in two different space groups viz. P2₁/c and P2₁/n. The modified 2-aminothiazole core did not show any change in the intermol. interaction. The N-H… N interaction predominates over other interactions forming centrosym. head to head dimer with the neighboring atoms. This feature is observed in all the mols. except N-(4-(4-bromophenyl)-3-(2,5-dimethylphenyl)thiazol-2(3H)-ylidene)-2,5-dimethylaniline.

Polycyclic Aromatic Compounds published new progress about 3696-23-9. 3696-23-9 belongs to chlorides-buliding-blocks, auxiliary class Chloride,Thiourea,Amine,Benzene,Amide, name is 1-(4-Chlorophenyl)thiourea, and the molecular formula is C7H7ClN2S, Safety of 1-(4-Chlorophenyl)thiourea.

Referemce:
https://en.wikipedia.org/wiki/Chloride,
Chlorides – an overview | ScienceDirect Topics

Ramacharyulu, P. V. R. K. published the artcilePhotocatalytic decontamination of sulfur mustard using titania nanomaterials, Application of 1,2-Bis(2-chloroethyl)disulfane, the publication is Journal of Molecular Catalysis A: Chemical (2012), 132-137, database is CAplus.

Photocatalytic decontamination of sulfur mustard (HD) was studied on titania nanomaterials, and data obtained with irradiation of sunlight and UV-A light were compared with that obtained without irradiation Role of particle size on photocatalytic decontamination of HD was also studied. Decontamination efficiency decreased when particle size was increased from 11 to 1000 nm. TiO₂ nanoparticles of ∼11 nm size of anatase phase exhibited superior decontamination properties relative to larger ones. 100% of HD was decontaminated on their surface within 6 h with irradiation of light. Without irradiation, only 24.7% of HD was removed. GC-MS data indicated decontamination of HD to acetaldehyde, CO₂, sulfur mustard sulfoxide, thiodiglycol, acetic acid, etc. due to photocatalysis. Without irradiation only hydrolysis products of HD like thiodiglycol were observed to be formed.

Journal of Molecular Catalysis A: Chemical published new progress about 1002-41-1. 1002-41-1 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is 1,2-Bis(2-chloroethyl)disulfane, and the molecular formula is C4H8Cl2S2, Application of 1,2-Bis(2-chloroethyl)disulfane.

Referemce:
https://en.wikipedia.org/wiki/Chloride,
Chlorides – an overview | ScienceDirect Topics

Kapoor, Jitander K. published the artcileSelective Synthesis of 3-(α,α-Dibromoacetyl)-4-hydroxy-6-methyl-2H-pyran-2-one as an Excellent Precursor for the Synthesis of 2-Substituted 4-(4-Hydroxy-6-methyl-2H-2-oxopyran-3-yl)thiazoles as Antimicrobial and Antifungal Agents, Recommanded Product: 1-(4-Chlorophenyl)thiourea, the publication is Journal of Heterocyclic Chemistry (2018), 55(4), 899-906, database is CAplus.

A selective synthesis of 3-(α,α-dibromoacetyl)-4-hydroxy-6-methyl-2H-pyran-2-one has been achieved by bromination of DHA using CuBr₂/CHCl₃-EtOAc. The reaction of the above compound with different thioureas/thiomides/thiosemicarbazide offers a convenient and efficient method for the syntheses of 2-substituted 4-(4-hydroxy-6-methyl-2H-2-oxopyran-3-yl)thiazoles I (R = C₆H₅NH, 4-MeC₆H₄NH, 4-ClC₆H₄NH, etc.). These thiazoles were evaluated for their antimicrobial and antifungal activity.

Journal of Heterocyclic Chemistry published new progress about 3696-23-9. 3696-23-9 belongs to chlorides-buliding-blocks, auxiliary class Chloride,Thiourea,Amine,Benzene,Amide, name is 1-(4-Chlorophenyl)thiourea, and the molecular formula is C7H7ClN2S, Recommanded Product: 1-(4-Chlorophenyl)thiourea.

Referemce:
https://en.wikipedia.org/wiki/Chloride,
Chlorides – an overview | ScienceDirect Topics

Alagiri, Kaliyamoorthy published the artcileCatalyst-Free Regio- and Stereospecific Synthesis of β-Sulfonamido Dithiocarbamates: Efficient Ring-Opening Reactions of N-Tosyl Aziridines by Dialkyldithiocarbamates, COA of Formula: C7H13ClNNaO5S, the publication is Chemistry – A European Journal (2011), 17(25), 6922-6925, S6922/1-S6922/62, database is CAplus and MEDLINE.

We have developed an efficient protocol for the synthesis of β-sulfonamido dithiocarbamates by using a ring-opening strategy of aziridines by thiocarbamates. These methods avoid toxic catalysts and, in most cases, give nearly quant. yields without any byproducts. This strategy provides an elegant method for synthesizing a wide range of β-sulfonamido dithiocarbamates by using inexpensive and readily available starting materials. In addition, a one-pot method has been developed for a facile ring-opening of aziridines by using in situ generated dialkyldithiocarbamate. This methodol. could potentially prove useful for the synthesis of medicinally active and other com. dithiocarbamate derivatives

Chemistry – A European Journal published new progress about 7080-50-4. 7080-50-4 belongs to chlorides-buliding-blocks, auxiliary class Halogenation Reagent,Inhibitor, name is Sodium chloro(tosyl)amide trihydrate, and the molecular formula is C7H13ClNNaO5S, COA of Formula: C7H13ClNNaO5S.

Referemce:
https://en.wikipedia.org/wiki/Chloride,
Chlorides – an overview | ScienceDirect Topics

Olmstead, Marilyn M. published the artcileCrystal and molecular structure of chloramine-T trihydrate. Absence of a sodium-nitrogen interaction in the oxidant. N-chloro-N-sodiotoluene-p-sulfonamide, Product Details of C7H13ClNNaO5S, the publication is Inorganic Chemistry (1986), 25(22), 4057-8, database is CAplus.

The title compound is triclinic, space group PT, with a 6.393(1), b 7.510(1)8 c 13.767(2) Å, α 85.33(1), β 83.92(1), and γ 74.11(1)°; Z = 2. Final R = 0.039 for 2366 data. At. coordinates are given. The main feature of the structure involves the lack of the commonly represented interaction between Na and N. Instead, the Na ion is coordinated to one of the sulfonamide oxygens. The rest of the Na coordination sphere involves oxygens (from water of crystallization) and a Cl from a neighboring mol. The structure is the first for an [RSO₂NCl]^– moiety.

Inorganic Chemistry published new progress about 7080-50-4. 7080-50-4 belongs to chlorides-buliding-blocks, auxiliary class Halogenation Reagent,Inhibitor, name is Sodium chloro(tosyl)amide trihydrate, and the molecular formula is C7H13ClNNaO5S, Product Details of C7H13ClNNaO5S.

Referemce:
https://en.wikipedia.org/wiki/Chloride,
Chlorides – an overview | ScienceDirect Topics

Gaglione, Maria published the artcileTuning RNA Interference by Enhancing siRNA/PAZ Recognition, Quality Control of 33697-81-3, the publication is ACS Medicinal Chemistry Letters (2013), 4(1), 75-78, database is CAplus and MEDLINE.

Chem. modified siRNAs were synthesized to enhance the corresponding silencing activities. The introduced modifications endowed siRNAs with high silencing effect, long RNAi persistence, and better serum resistance. Theor. data allowed us to correlate the observed siRNAs interfering performance with the peculiar interactions with PAZ.

ACS Medicinal Chemistry Letters published new progress about 33697-81-3. 33697-81-3 belongs to chlorides-buliding-blocks, auxiliary class Chloride,Carboxylic acid,Benzene,Phenol, name is 3-Chloro-4-hydroxyphenylacetic acid, and the molecular formula is C8H7ClO3, Quality Control of 33697-81-3.

Referemce:
https://en.wikipedia.org/wiki/Chloride,
Chlorides – an overview | ScienceDirect Topics

Davies, W. published the artcilePolymerization of thiophene derivatives. V. The self-condensation of 4,5- and 6,7-benzothianaphthene 1,1-dioxides. A new route to 1-(1-naphthyl)- and 4-(2-naphthyl)phenanthrene, Related Products of chlorides-buliding-blocks, the publication is Journal of the Chemical Society (1956), 2609-14, database is CAplus.

cf. C.A. 50, 1752d. 2-(1-Naphthyl)ethanol, b_0.2 130-2°, with PBr₃ gave 2-(1-naphthylethyl) bromide (I). I (98 g.) was refluxed and stirred 15 hrs. with 170 g. of Na₂SO₃.7H₂O to give 81 g. of Na 2-(1-naphthyl)ethanesulfonate (II). II stirred 30 min. with 66 g. PCl₅ at room temperature, the mixture warmed 30 min. on a steam bath and extracted with Et₂O, and the extract cooled precipitated gave 48 g. 2-(1-naphthyl)ethanesulfonyl chloride (III), m. 48-8.5°; anilide, m. 133.5-34°; amide, m. 172.5-73°. III (40 g.) in 75 ml. PhNO₂ was added to 24 g. powd. AlCl₃ in 200 ml. PhNO₂, the mixture kept 1 hr. at room temperature and 2 hrs. at 70°, the complex decomposed with dilute HCl, the solvent steam distilled, and the residue extracted with C₆H₆ gave 14.8 g. 2,3-dihydro-4,5-benzothianaphthene 1,1-dioxide (IV), m. 178-8.5°. IV (6.0 g.) refluxed 8 hrs. with 4.8 g. N-bromosuccinimide and 0.1 g. Bz₂O₂ in 150 ml. CCl₄, the solvent removed, and the residue dissolved in hot C₆H₆, filtered, and chromatographed on Al₂O₃ gave 2.7 g. 4,5-benzothianaphthene 1,1-dioxide (V), m. 136-7° or 141-2° with evolution of SO₂. V was reduced with LiAlH₄ to give 2,3-dihydrothianaphthene (VI), m. 86.5-87°. VI refluxed with chloranil in xylene 6 hrs. and the mixture cooled, filtered, diluted with C₆H₆, and chromatographed gave 4,5-benzothianaphthene. V (2.5 g.) in 50 ml. xylene was refluxed until evolution of SO₂ ceased. Evaporation gave 1.6 g. 10,11-dihydro-9-thia-5,6-benzonaphtho(1′,2′,3,4)fluorene 9,9-dioxide (VII), m. 226°. VII refluxed 10 min. in 50% aqueous KOH in (HOCH₂CH₂)₂O and the mixture diluted with H₂O and extracted with Et₂O gave 1-(1-naphthyl)phenanthrene, m. and mixed m.p. 115-16°. By the same sequence of reactions, the following compounds were prepared from 2-(2-naphthyl)ethanol, m. 66°: Na 2-(2-naphthyl)ethanesulfonate; 2,2′-naphthylethanesulfonyl chloride, m. 66-6.5° (amide, m. 200-200.5°); 2,3-dihydro-6,7-benzothianaphthene 1,1-dioxide, m. 187.5-88°; 6,7-benzothianaphthene 1,1-dioxide, m. 181-2°or 194-5° (decomposition); 10,11-dihydro-9-thia-7,8-benzonaphtho(2′,1′-3,4)fluorene 9,9-dioxide, m. 166-7°; and 4-(2-naphthyl)phenanthrene, m. 105-6°. 6-Tetralinsulfonyl chloride, m. 57-8°, was reduced with Zn and H₂SO₄ to 6-mercaptotetralin (VIII), b₃₅ 161-2°. VIII added to still-reacting Na in EtOH, followed by chloroacetal and NaBr, the mixture refluxed 6 hrs., the solution extracted with 2% aqueous NaOH, then Et₂O, the Et₂O extract distilled gave (6-tetralylthio)acetaldehyde di-Et acetal (IX), b_0.5 160-1°. Slow addition of IX to mixed P₂O₅ and H₃PO₄ gave a yellow oil which was distilled to give a mixture of tetrahydrobenzothianaphthenes, b_0.3 119-21°. Tetralin (50 g.) stirred 1 hr. into ClSO₃H at -5° warmed to room temperature, the mixture precipitated with ice and extraction with CCl₄, and the extract evaporated gave a mixture of 68 g. of 5- and 6-tetralinsulfonyl chlorides; this product (20 g.) added to 14.5 g. ClCH₂CO₂H on 12 g. NaOH in 250 ml. H₂O and the mixture heated 1 hr. on a water bath, cooled, and acidified precipitated 25 g. of an acid mixture (X). X (20 g.) in 80 ml. 5% KOH was added to 40 ml. 40% KOH. The acidified precipitate gave 9.2 g. (6-tetralylthio)acetic acid, m. 78.5-79. Acidification of the filtrate gave 9.0 g. of (5-tetralylthio)acetic acid, m. 133-4°.

Journal of the Chemical Society published new progress about 61551-49-3. 61551-49-3 belongs to chlorides-buliding-blocks, auxiliary class Liquid Crystal &OLED Materials, name is 5,6,7,8-Tetrahydronaphthalene-2-sulfonyl chloride, and the molecular formula is C10H11ClO2S, Related Products of chlorides-buliding-blocks.

Referemce:
https://en.wikipedia.org/wiki/Chloride,
Chlorides – an overview | ScienceDirect Topics