McConnell, N.’s team published research in Green Chemistry Letters and Reviews in 11 | CAS: 350-30-1

Green Chemistry Letters and Reviews published new progress about 350-30-1. 350-30-1 belongs to chlorides-buliding-blocks, auxiliary class Fluoride,Chloride,Nitro Compound,Benzene, name is 3-Chloro-4-fluoronitrobenzene, and the molecular formula is C6H3ClFNO2, Category: chlorides-buliding-blocks.

McConnell, N. published the artcileMicrowave-assisted green synthesis of anilines, phenols, and benzenediamines without transition metals, ligands, or organic solvents, Category: chlorides-buliding-blocks, the publication is Green Chemistry Letters and Reviews (2018), 11(3), 286-295, database is CAplus and MEDLINE.

A novel, microwave-assisted method producing anilines I (R = H, 2-F, 2-Cl, etc.; EWG = 2-NO2, 4-NO2, 3-NO2, etc.) and phenols II (R = H, 4-Br, 2-CF3, etc.; EWG = 4-NO2, 2-NO2) from activated aryl halides is reported. This high-yielding method reduces current reaction requirements and removes organic solvents and catalysts making a more efficient and eco-friendly alternative for the synthesis of important pharmaceutical building blocks.

Green Chemistry Letters and Reviews published new progress about 350-30-1. 350-30-1 belongs to chlorides-buliding-blocks, auxiliary class Fluoride,Chloride,Nitro Compound,Benzene, name is 3-Chloro-4-fluoronitrobenzene, and the molecular formula is C6H3ClFNO2, Category: chlorides-buliding-blocks.

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

Nesmeyanov, A. N.’s team published research in Doklady Akademii Nauk SSSR in 112 | CAS: 14799-94-1

Doklady Akademii Nauk SSSR published new progress about 14799-94-1. 14799-94-1 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Dichloro(hexyl)(methyl)silane, and the molecular formula is C7H16Cl2Si, Recommanded Product: Dichloro(hexyl)(methyl)silane.

Nesmeyanov, A. N. published the artcileThermal telomerization of methyldichlorosilane with olefins, Recommanded Product: Dichloro(hexyl)(methyl)silane, the publication is Doklady Akademii Nauk SSSR (1957), 271-2, database is CAplus.

Heating 123 g. MeSiHCl2 2 hrs. in a steel autoclave with C2H4 to 260° and a final pressure of 560 atm. gave 80% conversion to telomerization products MeSiCl2(CH2CH2)nH, with n = 1-6, as follows (n, % yield, b.p., nD20, and d20 shown): 1, 23.6, b. 100°, -, -; 2, 25.6, b. 147-8°, 1.4312, 1.0427; 3, 17.7, b32 91°, 1.4390, 0.9931; 4, 13.4, b6 94° 1.4440, 0.9761; 5, 4.7, b3 111-14°, 1.4490, 0.9600; 6, 3.8, b3 124-7°, 1.4532, 0.9552. About 8.5% undescribed higher telomers were also formed. A similar reaction of MeSiHCl2 and C3H6 was run 3 hrs. at 260-75° and 100 atm. maximum pressure yielded from 151 g. MeSiHCl2, 216 g. products giving MeSiCl2(C3H6)nH (n shown) as follows: 1, 49, b. 123-4°, 1.4240, -; 2, 26.2, b32 82°, 1.4400, -; 3, 3.9, b2 80-2°, 1.4540, -; 10% undescribed higher telomers.

Doklady Akademii Nauk SSSR published new progress about 14799-94-1. 14799-94-1 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Dichloro(hexyl)(methyl)silane, and the molecular formula is C7H16Cl2Si, Recommanded Product: Dichloro(hexyl)(methyl)silane.

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

Nesmeyanov, A. N.’s team published research in Tetrahedron in 1 | CAS: 14799-94-1

Tetrahedron published new progress about 14799-94-1. 14799-94-1 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Dichloro(hexyl)(methyl)silane, and the molecular formula is C7H16Cl2Si, Product Details of C7H16Cl2Si.

Nesmeyanov, A. N. published the artcileThermal telomerization of silanes with olefins, Product Details of C7H16Cl2Si, the publication is Tetrahedron (1957), 248-52, database is CAplus.

Thermal telomerization of MeSiHCl2 (I) with C2H4 at 260-75°/560 atm. was effected in a 500 cc. stainless steel autoclave. I (123 g.) in an N atm. was mixed with C2H4, the autoclave heated to 260°/500 atm., and the mixture maintained 2 hrs. at 260-70° with the pressure falling to 50 atm. The collected products (499 g.) from 3 runs (381 g. I) were fractionated to give 51 g. I and the tabulated pure MeSiCl2(C2H4)nH products (n, % yield, n20D, d20, MR, b.p., given): 1, 23.6, -, -, -, 100°; 2, 25.6, 1.4312, 1.0427, 43.48, 147-8°; 3, 17.7, 1.4390, 0.9931, 52.75, 91°/32 mm.; 4, 13.4, 1.4440, 0.9761, 61.83, 94°/6 mm.; 5, 4.7, 1.4490, 0.9600, 71.32, 111-14°/3 mm.; 6, 3.8, 1.4532, 0.9552, 80.20, 124-7/3 mm.; above 6, 8.5, -, -, -, -. The reaction with SiCl3H (II) was carried out 2 hrs. at 270-85° at maximum pressure 200 atm. in 4 runs (261 g. II) and yielded 353 g. product, distilled over a 15 plate column to give 10 g. II and pure alkyltrichlorosilanes, SiCl3(C2H4)nH (n, % yield, n20D, d20, MR, and b.p. recorded): 1, 20.1, -, -, -, 98°; 2, 25.3, 1.4352, 1.1577, 43.19, 146-7°; 3, 15.4, 1.4440, 1.1094, 52.51, 87-9°/30; 4, 13.1, 1.4490, 1.0744, 61.76, 96.5°/10; 5, 4.0, 1.4547, 1.0501, 71.17, 76°/2; above 5, 12.2,-,-,- -. The structures of the methylalkyldichloro- and alkyltrichlorosilanes were substantiated by the MR determinations and by formation by the Grignard reaction of the corresponding trimethyl derivatives (compound, b.p., n20D, d20, and MR given): BuSiMe3, 114°, 1.4030, 0.7203, 44.12; C6H13SiMe3, 163°, 1.4160, 0.7412, 53.58; C8H17SiMe3, 75°/10 mm., 1.4242, 0.7646, 62.58. The reaction of I with C3H6 was carried out in 2 runs at 260-75° 3 hrs. at 100 atm. maximum pressure to give 216 g. product from 151 g. I. Distillation gave 21 g. I and MeSiCl2(C3H6)nH (n, n20D, and b.p./mm. given): 1, 1.4240, 123-4°; 2, 1.4400, 82°/32; 3, 1.4540, 80-2°/2. The telomerization reactions resulted from the cleavage of the Si-H bond, as evidenced by its absence in the compounds obtained as shown by the neg. test with KOH in H2O. It is evident that the thermal reaction is of a chain character.

Tetrahedron published new progress about 14799-94-1. 14799-94-1 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Dichloro(hexyl)(methyl)silane, and the molecular formula is C7H16Cl2Si, Product Details of C7H16Cl2Si.

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

Nesmeyanov, A. N.’s team published research in Nesmeyanov, A. N., Izbrannye Trudy in 2 | CAS: 14799-94-1

Nesmeyanov, A. N., Izbrannye Trudy published new progress about 14799-94-1. 14799-94-1 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Dichloro(hexyl)(methyl)silane, and the molecular formula is C7H16Cl2Si, Quality Control of 14799-94-1.

Nesmeyanov, A. N. published the artcileThermal telomerization of olefins with silanes, Quality Control of 14799-94-1, the publication is Nesmeyanov, A. N., Izbrannye Trudy (1959), 688-95, database is CAplus.

cf. CA 51, 14541i; 52, 6165d. MeSiCl2H (11.5 g.) was autoclaved with 4.3 g. ethylene in a glass ampul at 320-40° for 3 hrs. A 46% conversion was realized, with MeEtSiCl2 and EtBuSiCl2 comprising 80% and 17% of the product, resp. This was repeated in a steel 2.7-1. bomb with 1 mole MeSiCl2H and 2.7 moles ethylene at 340° for 40 min. A 46% conversion was also realized with 42% MeEtSiCl2 and 28% MeBuSiCl2 (CA 51, 11988b). Ph3SiH (32 g.), 30 ml. n-hexane, and 25 g. ethylene autoclaved 12 hrs. at 290-300° gave EtSiPh3, m. 68-70°, BuSiPh3, m. 81-2°, and (Ph3Si)2O, m. 221°. In a 0.5-1. steel autoclave was placed 65 g. MeSiCl2H, 50 ml. propylene, and 0.1 ml. of a solution containing 0.00865 g. H2PtCl6.6H2O in iso-PrOH. The mixture was warmed to room temperature, the reaction proceeding exothermally. After an hr., the mixture was removed and distilled to give 77 g. BuSiMeCl2, b. 123-4°, n20D 1.4230, d20 1.0432, Raman spectra given. Propylene and MeSiCl2H treated (CA 51, 11988b) and the MePrSiCl2 isolated and methylated by the Grignard method gave Me3SiPr, n20D 1.3925, d20 0.7020, Raman spectra given. Lines corresponding to Me3SiPr-iso were not observed. C6H13SiMeCl2 (from propylene and MeSiCl2H) was also methylated with a Grignard to give C6H13SiMe3, b60 82-3°, n20D 1.4171, d20 0.7493. A study was done with MeSiCl2H and ethylene to determine optimum conditions for preparation of MeSiCl2(C2H4)nH, where n = 1, 2, 3, >3. A temperature of 300 ± 10° and 150 ± 5 atm. in an autoclave were best. Maximum yield, n = 1, when by moles C2H4/MeSiCl2H = 0.75; n = 2, when C2H4/MeSi- Cl2H = 1.5; n = 3, when C2H4/MeSiCl2H = 2.8 and 3.4; n > 3 when C2H4/MeSiCl2H = 9. The ratio C2H4/MeSiCl2H was 2 and the pressure held at 100 atm. to give the maximum yield, n = 1, when temperature was raised to 400° and the mixture allowed to cool; n = 2, when the temperature = 320° for 10 min.; n = 3, when the temperature = 305° for 50 min.; n > 3, when the temperature = 285° for 120 min.

Nesmeyanov, A. N., Izbrannye Trudy published new progress about 14799-94-1. 14799-94-1 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Dichloro(hexyl)(methyl)silane, and the molecular formula is C7H16Cl2Si, Quality Control of 14799-94-1.

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

Nesmeyanov, A. N.’s team published research in Doklady Akademii Nauk SSSR in 112 | CAS: 14799-93-0

Doklady Akademii Nauk SSSR published new progress about 14799-93-0. 14799-93-0 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Dichloro(methyl)(octyl)silane, and the molecular formula is C9H20Cl2Si, Recommanded Product: Dichloro(methyl)(octyl)silane.

Nesmeyanov, A. N. published the artcileThermal telomerization of methyldichlorosilane with olefins, Recommanded Product: Dichloro(methyl)(octyl)silane, the publication is Doklady Akademii Nauk SSSR (1957), 271-2, database is CAplus.

Heating 123 g. MeSiHCl2 2 hrs. in a steel autoclave with C2H4 to 260° and a final pressure of 560 atm. gave 80% conversion to telomerization products MeSiCl2(CH2CH2)nH, with n = 1-6, as follows (n, % yield, b.p., nD20, and d20 shown): 1, 23.6, b. 100°, -, -; 2, 25.6, b. 147-8°, 1.4312, 1.0427; 3, 17.7, b32 91°, 1.4390, 0.9931; 4, 13.4, b6 94° 1.4440, 0.9761; 5, 4.7, b3 111-14°, 1.4490, 0.9600; 6, 3.8, b3 124-7°, 1.4532, 0.9552. About 8.5% undescribed higher telomers were also formed. A similar reaction of MeSiHCl2 and C3H6 was run 3 hrs. at 260-75° and 100 atm. maximum pressure yielded from 151 g. MeSiHCl2, 216 g. products giving MeSiCl2(C3H6)nH (n shown) as follows: 1, 49, b. 123-4°, 1.4240, -; 2, 26.2, b32 82°, 1.4400, -; 3, 3.9, b2 80-2°, 1.4540, -; 10% undescribed higher telomers.

Doklady Akademii Nauk SSSR published new progress about 14799-93-0. 14799-93-0 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Dichloro(methyl)(octyl)silane, and the molecular formula is C9H20Cl2Si, Recommanded Product: Dichloro(methyl)(octyl)silane.

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

Nesmeyanov, A. N.’s team published research in Tetrahedron in 1 | CAS: 14799-93-0

Tetrahedron published new progress about 14799-93-0. 14799-93-0 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Dichloro(methyl)(octyl)silane, and the molecular formula is C9H20Cl2Si, Related Products of chlorides-buliding-blocks.

Nesmeyanov, A. N. published the artcileThermal telomerization of silanes with olefins, Related Products of chlorides-buliding-blocks, the publication is Tetrahedron (1957), 248-52, database is CAplus.

Thermal telomerization of MeSiHCl2 (I) with C2H4 at 260-75°/560 atm. was effected in a 500 cc. stainless steel autoclave. I (123 g.) in an N atm. was mixed with C2H4, the autoclave heated to 260°/500 atm., and the mixture maintained 2 hrs. at 260-70° with the pressure falling to 50 atm. The collected products (499 g.) from 3 runs (381 g. I) were fractionated to give 51 g. I and the tabulated pure MeSiCl2(C2H4)nH products (n, % yield, n20D, d20, MR, b.p., given): 1, 23.6, -, -, -, 100°; 2, 25.6, 1.4312, 1.0427, 43.48, 147-8°; 3, 17.7, 1.4390, 0.9931, 52.75, 91°/32 mm.; 4, 13.4, 1.4440, 0.9761, 61.83, 94°/6 mm.; 5, 4.7, 1.4490, 0.9600, 71.32, 111-14°/3 mm.; 6, 3.8, 1.4532, 0.9552, 80.20, 124-7/3 mm.; above 6, 8.5, -, -, -, -. The reaction with SiCl3H (II) was carried out 2 hrs. at 270-85° at maximum pressure 200 atm. in 4 runs (261 g. II) and yielded 353 g. product, distilled over a 15 plate column to give 10 g. II and pure alkyltrichlorosilanes, SiCl3(C2H4)nH (n, % yield, n20D, d20, MR, and b.p. recorded): 1, 20.1, -, -, -, 98°; 2, 25.3, 1.4352, 1.1577, 43.19, 146-7°; 3, 15.4, 1.4440, 1.1094, 52.51, 87-9°/30; 4, 13.1, 1.4490, 1.0744, 61.76, 96.5°/10; 5, 4.0, 1.4547, 1.0501, 71.17, 76°/2; above 5, 12.2,-,-,- -. The structures of the methylalkyldichloro- and alkyltrichlorosilanes were substantiated by the MR determinations and by formation by the Grignard reaction of the corresponding trimethyl derivatives (compound, b.p., n20D, d20, and MR given): BuSiMe3, 114°, 1.4030, 0.7203, 44.12; C6H13SiMe3, 163°, 1.4160, 0.7412, 53.58; C8H17SiMe3, 75°/10 mm., 1.4242, 0.7646, 62.58. The reaction of I with C3H6 was carried out in 2 runs at 260-75° 3 hrs. at 100 atm. maximum pressure to give 216 g. product from 151 g. I. Distillation gave 21 g. I and MeSiCl2(C3H6)nH (n, n20D, and b.p./mm. given): 1, 1.4240, 123-4°; 2, 1.4400, 82°/32; 3, 1.4540, 80-2°/2. The telomerization reactions resulted from the cleavage of the Si-H bond, as evidenced by its absence in the compounds obtained as shown by the neg. test with KOH in H2O. It is evident that the thermal reaction is of a chain character.

Tetrahedron published new progress about 14799-93-0. 14799-93-0 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Dichloro(methyl)(octyl)silane, and the molecular formula is C9H20Cl2Si, Related Products of chlorides-buliding-blocks.

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

Larsson, Malin’s team published research in Environmental Science and Pollution Research in 25 | CAS: 42074-68-0

Environmental Science and Pollution Research 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, Application In Synthesis of 42074-68-0.

Larsson, Malin published the artcileIdentification of potential aryl hydrocarbon receptor ligands by virtual screening of industrial chemicals, Application In Synthesis of 42074-68-0, the publication is Environmental Science and Pollution Research (2018), 25(3), 2436-2449, database is CAplus and MEDLINE.

We have developed a virtual screening procedure to identify potential ligands to the aryl hydrocarbon receptor (AhR) among a set of industrial chems. AhR is a key target for dioxin-like compounds, which is related to these compounds’ potential to induce cancer and a wide range of endocrine and immune system-related effects. The virtual screening procedure included an initial filtration aiming at identifying chems. with structural similarities to 66 known AhR binders, followed by 3 enrichment methods run in parallel. These include two ligand-based methods (structural fingerprints and nearest neighbor anal.) and one structure-based method using an AhR homol. model. A set of 6445 commonly used industrial chems. was processed, and each step identified unique potential ligands. Seven compounds were identified by all three enrichment methods, and these compounds included known activators and suppressors of AhR. Only approx. 0.7% (41 compounds) of the studied industrial compounds was identified as potential AhR ligands and among these, 28 compounds have to our knowledge not been tested for AhR-mediated effects or have been screened with low purity. We suggest assessment of AhR-related activities of these compounds and in particular 2-chlorotrityl chloride, 3-p-hydroxyanilino-carbazole, and 3-(2-chloro-4-nitrophenyl)-5-(1,1-dimethylethyl)-1,3,4-oxadiazol-2(3H)-one.

Environmental Science and Pollution Research 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, Application In Synthesis of 42074-68-0.

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

Robertson, Jeremy’s team published research in Organic & Biomolecular Chemistry in 4 | CAS: 866-23-9

Organic & Biomolecular Chemistry published new progress about 866-23-9. 866-23-9 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Diethyltrichloromethylphosphonate, and the molecular formula is C5H10Cl3O3P, Name: Diethyltrichloromethylphosphonate.

Robertson, Jeremy published the artcileSynthesis and Claisen rearrangement of bridged bicyclic enol ethers of relevance to the course of ketene s-cis-diene cycloaddition, Name: Diethyltrichloromethylphosphonate, the publication is Organic & Biomolecular Chemistry (2006), 4(23), 4307-4318, database is CAplus and MEDLINE.

The synthesis is described of a range of 3-alkylidene-2-oxabicyclo[2.2.1]hept-5-ene and 3-alkylidene-2-oxabicyclo[2.2.2]oct-5-ene derivatives; Claisen rearrangement of these substrates either thermally or in the presence of an added Lewis acid results in the formation of bicyclic cyclobutanones with generally good conversions. These reactions may be performed in hydroxylic solvents, supporting a largely non-dissociative pathway for the rearrangement.

Organic & Biomolecular Chemistry published new progress about 866-23-9. 866-23-9 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Diethyltrichloromethylphosphonate, and the molecular formula is C5H10Cl3O3P, Name: Diethyltrichloromethylphosphonate.

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

Kapp, Tobias G.’s team published research in Journal of Visualized Experiments in | CAS: 42074-68-0

Journal of Visualized Experiments 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, Application In Synthesis of 42074-68-0.

Kapp, Tobias G. published the artcileModification and functionalization of the guanidine group by tailor-made precursors, Application In Synthesis of 42074-68-0, the publication is Journal of Visualized Experiments (2017), e54873/1-e54873/7, database is CAplus and MEDLINE.

The guanidine group is one of the most important pharmacophoric groups in medicinal chem. The only amino acid carrying a guanidine group is arginine. In this article, an easy method for the modification of the guanidine group in peptidic ligands is provided, with an example of RGD-binding integrin ligands. It was recently demonstrated that the distinct modification of the guanidine group in these ligands allows for the selective modulation of the subtype (e.g., between the subtypes αv and α5). Moreover, a formerly unknown strategy for the functionalization via the guanidine group was demonstrated, and the synthetic approach is reviewed in this document. The modifications described here involve terminally (Nω) alkylated and acetylated guanidine groups. For the synthesis, tailor-made precursor mols. are synthesized, which are then subjected to a reaction with an orthogonally deprotected amine to transfer the pre-modified guanidine group. For the synthesis of alkylated guanidines, precursors based on N,N′-Di-Boc-1H-pyrazole-1-carboxamidine are used to synthesize acylated compounds, the precursor of choice being a correspondingly acylated derivative of N-Boc-S-methylisothiourea, which can be obtained in one- and two-step reactions.

Journal of Visualized Experiments 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, Application In Synthesis of 42074-68-0.

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

Cadogan, J. I. G.’s team published research in Journal of the Chemical Society in | CAS: 866-23-9

Journal of the Chemical Society published new progress about 866-23-9. 866-23-9 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Diethyltrichloromethylphosphonate, and the molecular formula is C5H10Cl3O3P, COA of Formula: C5H10Cl3O3P.

Cadogan, J. I. G. published the artcileReactivity of organophosphorus compounds. V. Reaction of trichloromethyl radicals with trialkyl phosphites, COA of Formula: C5H10Cl3O3P, the publication is Journal of the Chemical Society (1961), 3071-6, database is CAplus.

–From a knowledge of the reactions of benzyl and β,β-dimethylphenethyl radicals evidence was produced in favor of the radical-induced reaction of CCl4 with trialkyl phosphites to give dialkyl trichloromethylphosphonates proceeding by a radical chain reaction involving [(RO)3PCCl3]+ Cl rather than by decomposition of the phosphoranyl radical (RO)3(Cl3C)P. Evidence concerning the reactivity of phosphoranyl radicals was presented and discussed. Benzyl di-Et phosphite (I) b0.1 70°, n2D5 1.4900. PhCMe2CH2Cl (Ia), b12 101°, n2D1 1.5241, was converted into the alc. as follows: O passed during 3 h. through a solution in Et2O of the Grignard reagent from 250 g. Ia at 0°, and the mixture poured into 2 l. dilute H2SO4, washed, and distilled gave PhCMe2CH2OH (II), b12 110-12°, n24D 1.5248. II (25 g.) and 56.5 g. Et3PO3 kept 4.5 h. at 140°, the alc. formed removed, and the residue distilled gave 27 g. β,β-dimethylphenethyl di-Et phosphite (III), b0.1 98-102°. Attempts to prepare tris(β,β-dimethylphenethyl) phosphite gave oils which readily decomposed when heated. I (5.3 g.) and 0.3 g. Bz2O2 in 15 mL. CCl4 refluxed 18 h. gave 4 fractions: (a) 1.5 g. PhCH2Cl, b. 40-80°, n2D3.5 1.5240; (b) 0.8 g., b. 80-90°, n2D3.5 1.5070; (c) 0.95 g., b. 90-110°, n23.5D 1.4770; and (d) 4.2 g. di-Et trichloromethylphosphonate (IV), b. 120-30°; n2D305 1.4620. Fractions (b) and (c) were mixtures of PhCH2Cl and IV. Bz2O2 (0.44 g.) and 10 g. III in 24 g. CCl4 refluxed 18 h. and evaporated gave a residue, shown by gas chromatog. to contain no Ia. A portion (50%) of the residue distilled gave an unsaturated oil, b12 90-105°, n2D0 1.5208, a 53:47 mixture of 2-methyl-1-phenylpropene and 2-methyl-3-phenylpropene. Distillation of a further portion, attempted at 10-4 mm., gave an oil, b. 110°, n2D4 1.5080. Some decomposition occurred and the product was formulated as impure β,β-dimethylphenethyl Et trichloromethylphosphonate. Et3PO3 (5 g.) and 0.05 mol Bz2O2 in 15 g. CCl4 refluxed 18 h. gave 6.85 g. IV. In a similar experiment, in which CCl4 that had been passed through Al2O3 was used and the reaction carried out in the dark without Bz2O2, 6.94 g. IV was obtained. Ph3PO3 did not react with CCl4 or BrCCl3 under either of the above sets of conditions. The rate of disappearance of Et3PO3 on reaction with CCl4 at 80° was determined by following the reaction by gas-liquid chromatog. The first-order rate constant was 2.2 × 10-4 sec.-1. The experiment was repeated in the presence of Bz2O2 to give a rate constant of 3.5 × 10-4 sec.-1 Et3PO3 (5 g.) and 15 mL. CCl4 degassed and irradiated 1 h. at room temperature in a quartz flask with ultraviolet light gave 70% IV. Et3PO3 and CCl4 did not react in the dark at room temperature in 7 h. tert-Bu2O2 (3.7 g.) in 18.4 g. PhMe and 31.1 g. CCl4 was heated 48 h. at 130° in a sealed tube and the product separated into 2 fractions. Fraction (a) by gas-liquid chromatog. was shown to be largely PhCH2Cl and fraction (b) of 1.2 g., was PhCH2CH2Ph with an unidentified component, possibly PhCH2CCl3. Bis(9-benzyl-9-fluorenyl) peroxide (0.5 g.), m. 170.0-0.5°, was heated 48 h. at 130° in a sealed tube with 2.2 mL. CCl4 and 2 mL. C6H6; gas chromatog. showed the presence of (PhCH2)2 and PhCH2Cl. Et3PO3 (8.3 g.), 15.4 g. CCl4, 9 g. butane-1-thiol, and 0.61 g. Bz2O2 refluxed overnight, evaporated, and the 10.8-g. residue gas-chromatographed indicated tri-Et phosphorothionate, 18%; IV, 22%; and S-Bu di-Et phosphorothioate, 60%. Irradiation of 3.18 g. I in 15 mL. CCl4 under N at room temperature 4 h. followed by fractionation, gave 0.70 g. PhCH2Cl and 1.27 g. IV and left 1.8 g. of residue. Their nature was confirmed by IR spectra.

Journal of the Chemical Society published new progress about 866-23-9. 866-23-9 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Diethyltrichloromethylphosphonate, and the molecular formula is C5H10Cl3O3P, COA of Formula: C5H10Cl3O3P.

Referemce:
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