Month: November 2022

Simonetta, Massimo; Carra’, Sergio published an article in 1957, the title of the article was Reaction velocity of some ο- and p-chloronitrotoluenes with sodium methylate.Application of 38939-88-7 And the article contains the following content:

The reaction velocity at 70, 80, and 90° of 6 isomeric chloronitrotoluenes and 6 isomeric chloronitroanisoles was measured in MeOH with MeONa [position of Cl, NO2, and Me (and MeO) and 105K (l. mole-1. sec.-1) given]: 1, 4, 2, 4.86, 3.82; 1, 4, 3, 5.08, 10.69; 1, 2, 6, 0.77, 1.19; 1, 2, 5, 4.19, 14.56; 1, 2, 4, 1.37, 0.69; 1, 2, 3, 0.68, 0.61. The results were compared with those of Miller and Williams (C.A. 48, 5815h) for the reaction of the same compounds with piperidine in C6H6 and with those of Brieux and Deulofen (C.A. 49, 8158a). 19 references. The experimental process involved the reaction of 2-Chloro-4-methyl-1-nitrobenzene(cas: 38939-88-7).Application of 38939-88-7

2-Chloro-4-methyl-1-nitrobenzene(cas:38939-88-7) belongs to chlorides. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst. Application of 38939-88-7

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Wibaut, J. P. published an article in 1914, the title of the article was Quantitative researches on the nitration of chlorotoluenes.HPLC of Formula: 38939-88-7 And the article contains the following content:

The o-ClC6H4Me used was obtained by converting com. o-H2NC4H4Me into the oxalate (van der Laan, Idem, 26, 1 (1908)) and the NH2 replaced by Cl by Erdmann’s method (Ann., 272, 145). It b759 159-5° (corrected), n59.4° 1.4977. o-H2NC6H4Me nitrated with HNO3 + H2SO4 gave 4,2-O2N(H2N)C6H3Me, m. 107°, which, treated with 25% HCl, diazotized and treated With CuCl2, gave 2,4-Cl(O2N)C6H3Me. m. 62.3° (not 65° nor 68°), n69.4° 1.5470. 2,4-Cl(H2N)C4H3Me was prepared from 15 g. of the preceding in 1 l. H2O + 30 g. powdered Fe + H2SO4. With Ac2O it gave 4-acetylamino-2-chlorotoluene, m. 105°; similarly Bz3O gave 4-benzoylamino-2-chlorotoluene, m. 122°. 2,6-(O2N)2C6H2Me reduced with H2S in EtOH in the presence of NH3 gave 6,2-O2N(H2N)C4H3Me, m. 9t°, which, diazotized, etc., gave 6-nitro-2 chlorotoluene, m. 35-3°, n69.6° 1.5377; reduced, the latter gave 2,6-Cl(H2N)C6H3Me, m. 2.8°, which with Ac2O gave 2,6.Cl(AcNH)C6H3Me, m. 156°, and with Bz2O gave 2,6-Cl(BzNH)C6H3Me, m. 170°. 5,2-O2N(H2N)C6H3Me was prepared by the method of Goldschmidt and Hönig (Ber., 20, 200) from o-AcNHC6H4Me, and when diazotized, etc., gave 2,5-Cl(O2N)C6H3Me, m. 42.9°, n69.4° 1.5511. The latter on reduction gave 2,5-Cl(H2N)C6H2Me, m. 83°, which with Ac2O gave 2,5-Cl(AcNH)C6H3Me, m. 92°, and with Bz2O gave 2,5-Cl(BzNH)C6H2Me. m. 119.5°. 3,2-O2N(H2N)C6H3Me (obtained along with the 5-NO3 derivative), diazotized, etc., gave 2,3-Cl(O2N)C6H3Me, m. 22.1°, n69.4° 1.5327, which on reduction gave 2,3-Cl(H2N)C6H3Me, m. 6.6°; this, with Ac2O, gave 2,3-Cl(AcNH)C6H3Me, m. 133°, or with Bz2O gave 3-benzoylamino-2-chlorotoluene, m. 125°. The o-ClC6H4Me (n69.4° 1.4977) was nitrated with 4 times as much HNO3 (d. 1.52) at 0° ƛ 1°; after standing some time at 0° the mixture was poured on crushed ice, extracted with C6H6, etc., the C6H6 distilled off under reduced pressure and the nitration product (60 g. from so g. o-ClC6H4Me) distilled fractionally under 30 mm.; fraction (1) 120-30°, n69.4 1.5428; (2) 130-7°, n69.4 1.5438; (3) 137-40°, n69.4 1.5447; (4) above 140°, n69.4 1.5462. The values for n show that there is no unchanged o-ClC6H4Me nor was 3,4,6-Cl(O2N)2C6H2Me (n69.4 1.5723) formed. No attempts at direct isolation or identification of the complex mixtures of mono-NO2 derivatives were successful. The mixture was reduced with Fe + H2SO4, distilled with steam, etc. (crystals of 2,5-Cl(H2N)C6H2Me separated at this point, m. 81-2°), finally dissolved in C6H6 and treated with the calculate amount of Ac2O. This solution deposited white crystals which proved to be 2,6-Cl(AcNH)C6H3Me, m. 156°. The mother liquor was concentrate and gave 2,3-Cl(AcNH)C6H3Me, m. 133-4°. Attempts to isolate the 4th isomer in this way failed. A number of ways were tried but finally 120 g. of the nitration product were reduced and subjected to an elaborate fractional crystallization (for details see original) by which the presence of the 4th isomer was established, although it was not isolated. For a quant. study of the nitration products the fusion curve method used by Valeton (C. A., 5, 1283) was applied. When one has to do with a mix. of 4 compounds, A, B, C and D, the branch A of the crystallization curve of A-B is easily confused with branch A of A-C or A-D. The effect of a quantity of B on the f. p. of A is the same if a mixture of B, C and D is substituted for the same amount of either pure B, C or D. So that in order to determine the amount of A in any mixture add to a known amount of the mixture a known amount of A, such that A seps. first from the fused mass, and from the f. p. thus observed deduce the amount of A present on the basis of a binary solidification curve and from this calculate the amount of A present in the original mixture The 6 binary curves of solidification of the 4 isomeric Cl(O2N)C6H3Me were worked out and afterwards it was attempted to determine the comp. of complex mixtures of known comp. It was found that 3 of the isomers (all but 2,3-Cl(O2N)C6H3Me) could be accurately determined in this way. 10.3 g. o-ClC3H4Me nitrated for 1.5 hrs. with 41.3 g. HNO3 (d. 1.52) at 0° gave 10.3 g. nitration products (74%), m. 2-3°, which on analysis by the above method gave: 43.6% 2,5-, 16.9% 2,4-, 20.6% 2,6-, and 18.9% 2,3-Cl(O2N)C6H3Me. Another portion nitrated for 3 hrs. gave 43.2, 17.2, 20.9 and 18.7%, resp. Nitration of m-chlorotoluene. The m-ClC6H4Me used b. 229.5-30°, m. 15.2°. 45 g. m-AcNHC6H4Me were dissolved a little at a time in 300 cc. concentrate H2SO4 with cooling in ice + NaCl and 21 g. HNO3 (d. 1.52) + 50 cc. concentrate H2SO4 added slowly at 5° to -3°. This finally gave an 80% yield of 6,2-O2N(AcNH)C6H3Me. The Ac was removed by b. until dissolved in 100 cc. H2O + 100 cc. concentrate H2SO4. The NH2 was replaced with Cl by diazotizing, etc., which gave 6-nitro-3-chlorotoluene, m. 24.9° (and a metastable form, m. 24-2°). n65.6 1.5495. 2,6-(O2N)2C6H3Me was reduced electrolytically to 2,6-O3N(HONH)C6H3Me (Brand, Zoller, Ber., 40, 3332) which with HCl gives 3,2,6-Cl(O2N)(H2N)C6H2Me; this, diazotized, etc., gives 3,2-Cl(O2N)C4H3Me, dimorphous, m. 23.4° (the m. p. of the metastable form was not accurately determined), n68.5 1.5204. o-AcNHC6H4Me was chlorinated with Ca(OCl)2, the Ac eliminated with KOH in aqueous EtOH, the Cl(H3N)C6H3Me converted into the nitrate and this into 3,4,6-Cl(O2N)(H2N)C3H2Me according to Claus and Stapelburg (Ann., 274, 285), of which 20 g. were dissolved by b. in 160 cc. 50% H2SO4, diazotized and the 300 cc. of solution obtained added drop by drop to 600 cc. b. EtOH, which finally gave 4-nitro-3-chlorotoluene, m. 24.2°, n68.5° 1.5428. 3,5-Cl(O2N)C6H3Me, prepared by Hönig’s method (Ber., 20, 2419), m. 58.4°, n68.5° 1.5404. m-ClC6H4Me was nitrated like the o-derivative The nitration product was distilled fractionally at 8 cm.: (1) up to 173°, n68.5° 1.5447; (2) 173-8°, n68.5° 1.5453; (3) 178-80°, n68.5° 1.5448; (4) 180-5°, n68.5° 1.5448; (5) n68.5° 1.5452. The values of n show that m-ClC6H4Me and 3,4,6-Cl(O2N)2C6H2Me (n69.6 1.5723) are not present. The 6 binary curves of solidification of the 4 isomers of Cl(O2N)C6H3Me were worked out as for the o-derivatives and the nitration mixtures analyzed as above. The result shows 58.9% 3,6-, 32.3%, 3,4-, and 8.8% 3,2-Cl(O2N)C6H3Me; the presence of 3,5-Cl(O2N)C6H3Me could not be established experimentally but cannot exceed a few %. The latter part of the paper is devoted to a theoretical discussion in which it is shown that the quant. results obtained in the nitration of m- and o-ClC6H4Me are in perfect agreement with the theoretical predictions of Holleman and a formula is proposed which permits a satisfactory calculate of the proportions of the isomers formed. (For details see the original.) The experimental process involved the reaction of 2-Chloro-4-methyl-1-nitrobenzene(cas: 38939-88-7).HPLC of Formula: 38939-88-7

2-Chloro-4-methyl-1-nitrobenzene(cas:38939-88-7) belongs to chlorides. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst. HPLC of Formula: 38939-88-7

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Elson, Leslie A.; Gibson, Charles S.; Johnson, John D. A. published an article in 1929, the title of the article was Monohalomononitrotoluenes. Arsenical compounds derived from 3-bromo-4-nitrotoluene.Computed Properties of 38939-88-7 And the article contains the following content:

The 2 remaining bromonitrotoluenes are described. Reduction of the 5-NO2 derivative with Fe and dilute AcOH gives 5-amino-2-acetamidotoluene, m. 143°; partial deamination of the 2,5-di-NH2 derivative was not very successful. 4,3-O2N(H2N)C6H3Me (I) was prepared by heating 3,4-(O2N)2C6H3Me with concentrated NH4OH at 150° for 6 h. Through the diazo reaction there resulted from 15 g. I 9.9g. of the 3-Cl derivative, b19 146°, m. 22°; 30 g. I gives 23 g. of the 3-Br derivative, yellow, b19 156-8°, m. 37°; the 3-I derivative, orange-yellow, m. 103-5°. 3,5-Br(AcNH)C6H3Me with HNO3 of d. 1.5 gives the di-NO2 derivative but is unchanged with HNO3 of d. 1.45 at 0° for 10 min. Treating a mixture of 4,2,3-H2N(O2N)2C6H2Me in HCl-EtOH with NaNO2 below 0° and gradually warming to 70° gives a moderate yield of 3-chloro-2-nitrotoluene, m. 21-2°; 3-Br derivative, pale yellow, b10 129-30°, m. 27°; the residue consists of a pale yellow compound, C12H9O4N2Br2, m. 95-6°. 4,2,6-H2N(O2N)2C6H2Me, through the diazo reaction, gives the 4-Br derivative, orange-yellow, m. 89-90°. 3,2-Br(O2N)C6H3Me did not yield a satisfactory condensation product with o-H2NC6H4AsO2H2 but 3,4-Br(O2N)-C6H3Me gives 2-nitro-5-methyldiphenylamine-6′-arsonic acid, golden yellow, m. 228 30°; reduction with SO2 in EtOH-HCl gives the 6′-dichloroarsine, orange-red, m. 137° (decomposition), which, heated with AcOH for 2 h., yields 10-chloro-4-nitro-1-methyl-5,10-dihydrophenarsazine, deep red, m. 198-200° (decomposition). The experimental process involved the reaction of 2-Chloro-4-methyl-1-nitrobenzene(cas: 38939-88-7).Computed Properties of 38939-88-7

2-Chloro-4-methyl-1-nitrobenzene(cas:38939-88-7) belongs to chlorides. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst. Computed Properties of 38939-88-7

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Kohlrausch, K. W. F. published an article in 1947, the title of the article was Studies of Raman effect. CLXXIII. Benzene derivatives. 30. Interpolated Raman spectra.Computed Properties of 452-75-5 And the article contains the following content:

Since a stepwise substitution of X = NH2, OH, Me, Cl, Br, I produces a regular frequency transition from one derivative to another, the spectra of members of the series not yet determined or undeterminable for any reason can be determined by interpolation. This is done for m- and o-C6H4(NH2)2, NH2C6H4OH, NH2C6H4F, FC6H4OH, BrC6H4OH, FC6H4Br, IC6H4NH2, IC6H4OH, IC6H4F, IC6H4Br, C6H4I2 1,3,5-F3C6H3, 1,3,5-Me2FC6H3, 1,3,2-Me2FC6H3, 1,2 3-Me2FC6H3, 1,3,4-Me2FC6H3, 1,2,4-Me2FC6H3, 1,4,2-Me2FC6H3, 1,4,2-MeClFC6H3, 1,4,2-Cl2FC6H3, 1,3,4-Cl2FC6H3. The experimental process involved the reaction of 4-Chloro-2-fluorotoluene(cas: 452-75-5).Computed Properties of 452-75-5

4-Chloro-2-fluorotoluene(cas:452-75-5) belongs to chlorides. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst. Computed Properties of 452-75-5

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Kuhn, Richard; Trischmann, Heinrich published an article in 1958, the title of the article was Trimethylsulfoxonium ion.Synthetic Route of 5034-06-0 And the article contains the following content:

Me2SO (I) (16 g.) and 30 ml. MeI refluxed 3 days gave 25 g. octagonal plates of trimethylsulfoxonium iodide, Me3S+OI- (II), m. 200° (H2O), insoluble in C6H6, Et2O, CHCl3, petr. ether, sparingly soluble in MeOH, soluble in H2O (1.5 g. in 100 ml. at 20°). II shaken with an aqueous suspension of AgCl gave the H2O-soluble chloride, long needles, (MeOH-C6H6); picrate, decompose 210° (H2O); tetraphenylborate, m. 195° (aqueous EtOH). The reineckate, phosphomolybdate, and phosphotungstate are very little soluble Thermal decomposition of II gave I. II shaken with aqueous CO2-free Ag2O gave the oily hydroxide, which in the presence of air crystallized to the bicarbonate or carbonate. Reduction of II with HI gave blue-black crystals of the periodide, Me3S+I3-, which on boiling with H2O yielded iodine and Me3S+I-, identical with an authentic specimen. II (1 g.) and 5 ml. pyridine (III), refluxed 15 min., or the chloride and III refluxed 240 min. at 115°, gave quant. yields of III.MeI and III.MeCl, resp. Similarly II and quinoline gave the corresponding MeI derivative, m. 70-2° (monohydrate) (EtOH). II (2.2 g.), 0.7 g. p-O2NC6H4OH, and 10 g. Ag2O in Me2NCHO shaken 2 days at 20°, CHCl3 added, the mixture filtered, washed with 2N NaOH and H2O, dried, and concentrated gave 78% p-O2NC6H4OMe, m. 55°, b0.1 100-5°. The experimental process involved the reaction of trimethyloxosulphonium chloride(cas: 5034-06-0).Synthetic Route of 5034-06-0

trimethyloxosulphonium chloride(cas:5034-06-0) belongs to chlorides. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst. Synthetic Route of 5034-06-0

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Brown, J. P.; McCall, E. B. published an article in 1955, the title of the article was Some chlorinated hydroxyphenoxyacetic acids.Synthetic Route of 74672-01-8 And the article contains the following content:

Efforts to determine the fate of 2,4-Cl2C6H3OCH2CO2H in plants and in soil substrates led to the present syntheses of various chlorinated (hydroxyphenoxy)acetic acids. A metabolite isolated from cultures of bacteria grown in a medium containing 4-ClC6H4OCH2CO2H [Evans and Smith, Biochem. J. 57, Number 4, xxx(1954)] was believed to be 4,2-Cl(HO)C6H3OCH2CO2H (I), so its synthesis was first undertaken. 4-ClC6H4OCH2CO2H (10 g.) heated 2 h. at 90° with 100 mL. concentrated HNO3 gave 7.0 g. 4,2-Cl(O2N) C6H3OCH2CO2H (II), m. 173-5° (from aqueous MeOH); II (1.0 g.) reduced with Na Na2S2O4 at 90° and acidified to pH 4 gave 0.15 g. white needles, m. 215-18°, and the filtrate boiled with 32% HCl yielded 0.52 g. of the same material. This was the lactam of 4,2-Cl(H2N)C6H3OCH2CO2H, 6-chloro-3,4-dihydro-3-oxobenzoxazine, m. 217-18° (from EtOH). II (5.0 g.)was also boiled in 50 mL. C6H6, with 8.0 mL. SOCl2, 8 h., the C6H6 and excess SOCl2 evaporated, 4.0 g. 20% solution of NHMe2 in C6H6 added to the residue, and the mixture allowed to stand overnight, then concentrated, and filtered, giving 4.7 g. crude 4,2-Cl(O2N)C6H3OCH2CONMe2, m. 84° (100-1° on recrystallization from MeOH), reduced by Fe and HOAc in aqueous EtOH to the 2-H2N analog, m. 121° (from EtOH). Attempts to replace the NH2 group by OH in both the NH2 acid and its dimethylamide failed. 5,2-Cl(HO)C6H3Ac (2.8 g.) boiled 4 h. with 3.2 g. NaOH and 4.7 g. ClCH2CO2H in 30 mL. H2O, cooled, and acidified gave 2.4 g. 4,2-ClAcC6H3COCH2CO2H, m. 177-8° (from aqueous MeOH). Efforts to oxidize this to I were unsuccessful. 4,1,2-ClC6H3(OH)2 (14.8 g.) added to a solution of 2.8 g. Na in 60 mL. dry EtOH and the boiling mixture treated with 3.7 g. ClCH2CO2Et, gave 6.4 g. impure 5,2-Cl(HO)C6H3OCH2CO2H, m. 157° (from H2O), forming with Me2SO4 and hot 20% aqueous NaOH with a Me ether (III), m. 143-5° (from aqueous MeOH). The identity of III was established by first reducing 4-nitroguaiacol with H at room temperature and atm. pressure over Pd-C to the amino compound, converting it to the HCl salt, diazotizing, and adding CuCl to give 4-chloroguaiacol, m. 36-7°, which, allowed to react with ClCH2CO2H in NaOH and H2O 2 h. at 95°, then acidified, gave 5,2-Cl(MeO)C6H3OCH2CO2H, m. 141-3° (from C6H6), identical with III. 4-Nitroguaiacol and ClCH2CO2H condensed in the presence of NaOH to either 2,5-HO(O2N)C6H3OCH2CO2H (IV), m. 191° (from aqueous MeOH), or the 2-MeO analog (V), m. 180-2° (from aqueous MeOH), depending on the concentration of NaOH used. IV reduced, diazotized, and treated with CuCl as above gave 5,2-Cl(HO)C6H3OCH2CO2H, m. 157° (from H2O and aqueous MeOH), and V gave first 5,2-H2N(MeO) C6H3OCH2CO2H, m. 232° (from H2O), and finally 5,2-Cl(MeO)C6H3OCH2CO2H, m. 140-2° (from aqueous MeOH). 5-Nitroguaiacol converted to 5-chloroguaiacol, m. 16-17°, as described above for the 4-Cl compound, then treated with ClCH2CO2H, yielded 4,2-Cl(MeO)C6H3OCH2CO2H, m. 135-6° (from C6H6 or aqueous MeOH), which (0.2 g.), boiled 1 h. with 2.0 mL. 48% aqueous HBr, gave on cooling 0.15 g. I; after recrystallization from H20, slowly I, m. 110° on slow, 124-30° on rapid heating. 5-Nitroguaiacol (2.0 g.) with 1.5 g. ClCH2CO2Et in the presence of NaOMe gave 0.5 g. 2,4-MeO(O2N)C6H3OCH2CO2Et, m. 88-91° (from MeOH). 3,5,1,2-Cl2C6H2,(OH)2 and ClCH2CO2Et gave 2,4,6-Cl2(HO)C6H2OCH2CO2H (VI), m. (depending on the rate of heating) 130-55° (after recrystallization from H2O), identical with the substance prepared by Cavill and Ford (C.A. 49, 3072h). Its Me ether, m. 174-6°. 2,4-Cl2C6H3OH nitrated with concentrated HNO3 at 30-40° to 2,4,6-Cl2(O2N)C6H2OH, m. 122-4°, then reduced in alk. Na2S2O4, neutralized with HOAc, and the resulting aminophenol acetylated with Ac2O yielded 4,6,2-Cl2(AcNH)C6H2OH, m. 138-40° (from aqueous EtOH), which, boiled 6 h. in acetone with MeI and K2CO3, formed 4,6,2-Cl2(AcNH)C6H2OMe, m. 112-14° (from light petroleum, b. 60-80°), hydrolyzed by boiling 1 h. in 20% HCl to 4,6,2-Cl2(H2N)C6H2OMe.HCl, m. 196° (from dilute HCl), converted with NaOH to the amine, f.p. 16°. The amine diazotized and the diazonium solution added to CuSO4 in H2O with simultaneous passage of steam yielded from the steam distillate 4,6-dichloroguaiacol, m. 63-4° (from light petroleum, b. 60-80°), converted in the usual way into 3,5,2-Cl2(MeO)C6H2OCH2CO2H, m. 106-7° (from PhMe). The MeO acid, boiled 1 h. with 48% HBr gave 3,5,2-Cl2(HO)C6H2OCH2CO2H, m. 154° (from H2O). 2,4-Cl2C6H3NH2 (12 g.) in 450 mL. acetone and 700 mL. H2O containing 11 g. KOH treated during 5 h. at 25° with 20 g. K2S2O8 in 450 mL. H2O gave only 1.5 g. product which, boiled with 20% HCl, basified with NaHCO3, and Ac2O added yielded 0.4 g. 3,5,2-Cl2(AcNH)C6H2OH, m. 190-3° (from aqueous MeOH), methylated with MeI to 3,5,2-Cl2(AcNMe)C6H2OMe (VII), m. 107-9° (from light petroleum, b. 60-80°). This route to 3,5-dichloroguaiacol was abandoned, though, because of the poor yields in these 2 steps. When 9.0 g. 5-chlorovanillic acid in 90 mL. glycerol containing 0.2 g. Cu bronze was heated 10 min. at 250-60°, and steam was passed through the mixture, 1.7 g. 3-chloroguaiacol, m. 54° (from light petroleum, b. 60-80°) was recovered from the distillate; a C6H6 solution of this compound did not react with SO2Cl2 at room temperature, and boiling with a large excess of SO2Cl2 gave a mixture from which 5% of a trichloroguaiacol, m. 102-4° (from light petroleum, b. 60-80°) was isolated. 5-Chlorovanillic acid (5.0 g.) was dissolved in 30 mL., warm concentrated H2SO4, 50 mL. CHCl3 added, and the mixture stirred at 45° while 2.5 g. NaN3 was added during 30 min., then poured onto ice, and filtered. If the filtrate was basified at this point, it gave a rapidly discoloring precipitate of 5-amino-3-chloroguaiacol which could be converted by the addition of Ac2O into 5-acetamido-3-chloroguaiacol, m. 165° (from H2O). To obtain 3,5-dichloroguaiacol, the filtrate was treated with BaCl2 solution to remove the sulfate, and the remaining amine hydrochloride solution diazotized and treated with urea and a solution of CuCl2; steam distillation, extraction with Et2O, and vacuum-distillation gave 0.3 g. material, b15 170° (bath temperature), which, recrystallized 3 times from light petroleum (b. 60-80°), gave 3,5-dichloroguaiacol (VIII), m. 64-5°, also obtained from 2,4,6-Cl3C6H2NO2 by condensation with NaOMe to 3,5,6-Cl2(O2N)C6H2OMe, m. 70-2° (from EtOH) and reduction with H (Raney Ni) to 3,5,2-Cl2(H2N)C6H2OMe (IX). Acetylation of IX gave the N-Ac derivative, m. 169.5-71.5° (from PhMe), and methylation gave VII. IX in concentrated H2SO4 converted into VIII as described in the diazotization of the 4,6-Cl2 isomer. VIII (0.6 g.) yielded in the usual way 0.7 g. VI, identical with the acid from 3,5,1,2-Cl2C6H2(OH)2. 2-ClC6H3OCH2CO2H boiled with concentrated HNO3 5 min. gave the 4-O2N derivative, m. 179-81° (from aqueous EtOH), esterified with MeOH and. concentrated H2SO4 to the Me ester, m. 124°. Hydrogenation of the ester in MeOH over Pd gave 2,4-Cl(H2N)C6H3OCH2CO2Me, m. 69° (from petr. ether, b. 60-80°), which was diazotized, added to CuSO4 in boiling H2O, the product extracted with Et2O, dissolved in NaOH, precipitated with acid, dried, treated with boiling C6H6, and the fraction insoluble in C6H6 recrystallized twice from H2O to give 2,4-Cl(HO)C6H3O CH2 CO2H acid (X), m. 146-7° [Me ether, m. 136-8° (from PhMe)]. Another synthesis of X involved chlorinating p-MeOC6H4OH with SO2Cl2 to 2,4-Cl(MeO)C6H3OH, b15 108°, m. 46-7° (from petr. ether, b. 60-80°), and converting this in the usual way to a phenoxyacetic acid, which was identical with the above 2,4-Cl(MeO)C6H3OCH2CO2H and on boiling with 48% HBr gave X. A bacterial metabolite of 2,4-Cl2C6H3OCH2CO2H has been isolated by Evans which is not identical with any of the hydroxyphenoxyacetic acids described above. The experimental process involved the reaction of 1,5-Dichloro-3-methoxy-2-nitrobenzene(cas: 74672-01-8).Synthetic Route of 74672-01-8

1,5-Dichloro-3-methoxy-2-nitrobenzene(cas:74672-01-8) belongs to chlorides. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst. Synthetic Route of 74672-01-8

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Brieux, Jorge A.; Deulofeu, Venancio published an article in 1954, the title of the article was The reaction velocity of some substituted o- and p-chloro-nitrobenzenes with piperidine.Application In Synthesis of 2-Chloro-4-methyl-1-nitrobenzene And the article contains the following content:

cf. C.A. 46, 2382i. The velocity constants for the reaction of some R-monosubstituted (R = Me, OMe, and OEt) o-and p-chloronitrobenzenes with piperidine (I) in C6H6 at 100° have been determined Possible reasons for the order of reactivity are given. Rates were measured at 100° by halide determination The rate constants were calculated for the over-all reaction O2NC6H3RCl + 2C5H10NH → O2NC6H3RNC5H10 + C5H10-NH.ClH. The mean deviation of the mean for the reaction of the rates was 2-3%. Average mean values of at least 2 independent runs expressed as 107k (1. mole-1sec.-1, are as follows for ClRC6H3NO2, where R = H, Me, MeO, and EtO, resp.: 4-ClC6H4NO2, 16.8, -, -, -; 4,3-ClRC6H3NO2, -, 0, 7.0, 4.16; 4,2-ClRC6H3NO2, -, 3.6, 14.1, 4.45; 2-ClC6H4NO2, 779, -, -, -; 2,3-ClRC6H3NO2, -, 5.55, 152, 123; 2,4-ClRC6H3NO2, -, 772, 2630, 1820; 2,5-Cl RC6H3NO2, -, 152, 35.9, 30.2; 2,6-ClRC6H3NO2, -, 12.1, 23.3, 9.73. The experimental process involved the reaction of 2-Chloro-4-methyl-1-nitrobenzene(cas: 38939-88-7).Application In Synthesis of 2-Chloro-4-methyl-1-nitrobenzene

2-Chloro-4-methyl-1-nitrobenzene(cas:38939-88-7) belongs to chlorides. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst. Application In Synthesis of 2-Chloro-4-methyl-1-nitrobenzene

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Brieux, J. A.; Deulofeu, V. published an article in 1956, the title of the article was Reaction velocity of 2- and 4-chloronitrotoluenes, -anisoles and -phenetoles with piperidine in benzene.Application In Synthesis of 2-Chloro-4-methyl-1-nitrobenzene And the article contains the following content:

cf. C.A. 46, 11126a. The velocity constant for the reaction of piperidine with the title compounds was determined at 100° by titrating potentiometrically the liberated Cl-. The equation k = t(b – 2a) ln [a(b – 2x)/b(a – x)] (a and b = initial concentrations of chloro compounds and piperidine, x = concentration of Cl- at time t) was used. Thus were determined the following (compound, k × 107 mole-1 sec.-1): 4-ClC6H4NO2, 16.8; 3,4-MeClC6H3NO2, 0;4,3-Cl(MeO)C6H3NO2, 7.0; 4,3-Cl(EtO)C6H3NO2, 4.16; 2,4-MeClC6H3NO2, 3.6; 4,2-Cl(MeO)ClC6H3NO2, 14.1; 4,2-Cl(EtO)C6H3NO2, 4.45; 2-ClC6H4NO2, 779; 2,3-ClMeC6H3-NO2, 5.55; 2,3-Cl(MeO)C6H3NO2, 152; 2,3-Cl(EtO)C6H3-NO2, 123; 2,4-ClMeC6H3NO2, 772; 2,4-Cl(MeO)C6H3NO2, 2630; 2,4-Cl(EtO)C6H3NO2, 1820; 2,5-ClMeC6H3NO2, 152; 2,5-Cl(MeO)C6H3NO2, 35.9; 2,5-Cl(EtO)C6H3NO2, 30.2, 2,6-ClMeC6H3NO2, 12.1; 2,6-Cl(MeO)C6H3NO2, 23.3; 2,6-Cl(EtO)C6H3NO2, 9.73. The experimental process involved the reaction of 2-Chloro-4-methyl-1-nitrobenzene(cas: 38939-88-7).Application In Synthesis of 2-Chloro-4-methyl-1-nitrobenzene

2-Chloro-4-methyl-1-nitrobenzene(cas:38939-88-7) belongs to chlorides. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst. Application In Synthesis of 2-Chloro-4-methyl-1-nitrobenzene

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Chardonnens, Louis; Wurmli, Albert published an article in 1946, the title of the article was Derivatives of fluorenone. II. 3,6-Dimethylfluorenone.Application In Synthesis of 5,5′-Dimethyl-[1,1′-biphenyl]-2,2′-dicarboxylic acid And the article contains the following content:

cf. C.A. 40, 1479.2. Diazotization of 4,2-Me(H2N)C6H3CO2H (I) and treatment of the solution with NH3-Cu2O gives 84% 5,5′-dimethyl-2,2′-dicarboxybiphenyl, m. 269° (all m.ps. corrected). When this is mixed with CaO and heated 2 hrs. at 350° it gives 23% 3,6-dimethylfluorenone (II), m. 118° (oxime m. 189-91°), but the product is always contaminated with a red oil which can be separated only by chromatography. It is therefore better to treat I with NaOH and MeC6H4SO2Cl to get 77% 4-methyl-2-tosylaminobenzoic acid, m. 208-9°. With PCl5 this gives the acid chloride which reacts with MePh and AlCl3. The product is saponified to give 65% 4,4′-dimethyl-2-aminobenzophenone (III), m. 119°. 4,4′-Dimethyldiphenyl sulfone is a by-product. Diazotization of III in H2SO4 gives 70% II and a little 4,4′-dimethyl-2-hydroxybenzophenone, m. 73-4°. When II is heated 6 hrs. at 175° in a sealed tube with N2H4.H2O and Na in EtOH, it gives 85% 3,6-dimethylfluorene, m. 130-1°. Direct nitration of II with H2SO4 and KNO3 gives only 3,6-dimethyl-2,7-dinitrofluorenone (IV), m. 281° (decomposition). The mononitro compound cannot be prepared in this way. 4-Methyl-5-nitro-2-chlorobenzoic acid is converted to the acid chloride which, with MePh and AlCl3, gives 69% 4,4′-dimethyl-5-nitro-2-chlorobenzophenone, m. 108.5°. This heated 8 hrs. in a sealed tube at 160-70° with alc. NH3 gives 82% 4,4′-dimethyl-2-amino-5-nitrobenzophenone, m. 162.5°. This is diazotized in H2SO4 to give 59% 3,6-dimethyl-2-nitrofluorenone (V), m. 222-4°, and some 4,4′-dimethyl-5-nitro-2-hydroxybenzophenone, m. 144°. Nitration of V gives IV. The experimental process involved the reaction of 5,5′-Dimethyl-[1,1′-biphenyl]-2,2′-dicarboxylic acid(cas: 93012-36-3).Application In Synthesis of 5,5′-Dimethyl-[1,1′-biphenyl]-2,2′-dicarboxylic acid

5,5′-Dimethyl-[1,1′-biphenyl]-2,2′-dicarboxylic acid(cas:93012-36-3) belongs to chlorides. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst. Application In Synthesis of 5,5′-Dimethyl-[1,1′-biphenyl]-2,2′-dicarboxylic acid

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

On November 17, 1954, there was a patent about dyes.Computed Properties of 452-75-5 The title of the patent was Anthraquinone vat dyes. And the patent contained the following:

A series of anthraquinone vat dyes of the general formula I, where R is p-ClC6H4CONH, or 2,4-F(Cl)C6H3CONH, or 2,5-F(Cl)C6H3CONH and A represents a dicarboxylic acid residue, was prepared Thus, 1-amino-5-(4-chloro-2-fluorobenzamido)anthraquinone (II) 5.9 and p-ClC6H4COCl 4 parts heated 0.5 hr. with stirring in C6H3Cl3 150 at 200-5°, the mixture cooled and filtered, and the residue washed with EtOH and dried gave a dye which could be purified further with hypochlorite solution, red in concentrated H2SO4, dyed cotton from a Bordeaux-colored Na2S2O4 vat fast pure-yellow tints. The 5-Cl isomer of II gave similarly a dye yielding somewhat more reddish yellow dyeings. II, m. 279°, was prepared by the acylation of 1,5-diaminoanthraquinone with 2,4-F(Cl)C6H3COCl (III) or from 1-chloro-5-(4-chloro-2-fluorobenzamido)anthraquinone by replacing the 1-Cl atom by a p-MeC6H4SO2NH residue followed by cleavage. The 5-Cl isomer of II, m. 269°, was prepared in the same manner. 2,4-F(Cl)C6H3Me, b743 158°, obtained from 2,4-NH2(Cl)C6H3NH2 through the diazonium fluoborate, gave by KMnO4 oxidation 2,4-F(Cl)C6H3CO2H (IV), m. 205°. IV treated with SOCl2 yielded III, b14 105-6°. 2,5-H2N(Cl)C6H3Me was converted through the diazonium fluoborate to 2,5-F(Cl)C6H3Me, b741 156°, and further to 2,5-F(Cl)C6H3CO2H, m. 149-50°, which yielded 2,5-F(Cl)C6H3COCl, b15 103-4°. II 7.9, (COCl)2 1.27, and C6H3Cl3 150 parts heated with stirring during 2 hrs. to 150°, the mixture heated further to 190°, kept 1 hr. at 190-200°, cooled to 100°, and filtered, and the residue washed with EtOH and dried (it may be purified by boiling the neutral aqueous suspension with hypochlorite) gave I, where A = O:CC:O and R = 2,4-F(Cl)C6H3CONH, Bordeaux in concentrated H2SO4, which dyed cotton fast greenish yellow tints from a Bordeaux vat. II 4,p-C6H4(COCl)2 1, and C6H3Cl3 150 parts refluxed 2 hrs. with stirring gave I, where A = p-O:CC6H4C:O and R = 2,4-F(Cl)C6H3CONH, which dyed cotton fast pure yellow tints. Thianthrene dicarboxylic acid 1.12, SOCl2 6, pyridine 0.05, and C6H3Cl3 90 stirred 0.5 hr. at 80° and then 0.5 hr. at 120°, the excess SOCl2 and some of the solvent distilled off. the residual solution cooled to 100° and treated with II 3 parts, and the mixture heated 2 hrs. at 200-10°, cooled to 120°, and filtered gave I, where R = 2,4-F(Cl)C6H3CONH and A = thianthrenedicarbonyl, red in concentrated H2SO4, dyed cotton fast yellow tints. The experimental process involved the reaction of 4-Chloro-2-fluorotoluene(cas: 452-75-5).Computed Properties of 452-75-5

4-Chloro-2-fluorotoluene(cas:452-75-5) belongs to chlorides. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst. Computed Properties of 452-75-5

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics