SU496260A1 - The method of obtaining cyclohexyl chloride - Google Patents

Description

{54} The method of producing cyclohexylchloride is not more than 1.5 wt.%, Ha-J. at 50 ° C in the presence of fipHMep. 2.5 mol) king of 1 6 g. -, -, Ye.; C1 1 .4 (SI,) :, so in the dark 6 - 32 out of 39 g (50 no. „0.465 mol) of cyclohexane for 4 hours and in total: 25 g of cyclohexyl chloride with a content of cyclohexane dichloro derivatives not higher than 1.5 weight. % gfy conversion w-1clohexane, equal to 46D%. | • The dipolar aprotic solvent can be used not only as a ligand in the catalyst, but also as carbon tetrachloride (in a mixture or separately) as a medium in which cyclohexane is chlorinated. At the same time, the speed of the process increases, and IS: B1I move and target products are separated. Reacton1; th mass either directly - 1O {due to its separation), or after the reaction mass is processed by water or refining. ; Catalyst solution - iron complex -. after separation of cyclohexyl chloride. The subject can be reused for the chlorination of a new portion of cyclohexane. The catalyst is synthesized in a glass flask equipped with a reflux condenser and a magnetic stirrer. The chlorination of the xan xpog is carried out in the dark in a thermostatically controlled glass reactor, equipped with a reflux condenser. A cytotoxane with a catalyst before the start of the experiment saturates gum chlorine (at room temperature and roacpy is carried out at 50 ° C. The reaction medium is stirred at rc.Kow of chlorine,. In Example -7 for the reaction {39 g 0.465 mol) B1Clob 50 ml of the remaining experiments - 5 ml of Lksa: 1a, and in (3.9 1-, 0.0465 mol). In Example 7, the reaction products of cyclohexane chlorites were isolated by preparative gas-liquid chromatography (GLC) on a glass column, and in other experiments they were determined analytically on the same instrument., Synthesis of a catalyst ..

Pr them im p 1. Hexacis - (acetonitrile) iron (I) -bis- (tetrachloroferrate)

Re (ANG ReС141 (ResSvbDN).

1.233 g of 1 ”elm, 25 ml of acetonitrile and 5O CC 1 are heated for 4 hours at.

 R. D),.

 C in the atmosphere with CO until complete solution, rhenium iron. In three days from rast-. a thief of a reddish-brown color shed shakl-; sleek shiny crystals in the form

m.p. 207-2О8 С.

cuome.

50

Found,%; C 19.98; H 3.77; N 7.54; C 39.51; fe 20.49.

3%

6

Calculated

about: C 19.85; And 3.86; -N 7; 75; C1 39.20; Fe 20.5. sublimates at, 1 mm

Claims (1)

Complex I Hg. Art. needles The complex is filtered and washed with SS 1 and pentane, so pl. 125-127 C. Found,%: C 20.56; And 2.55; N, 12.07; C1 40.13; p 23.44. 18 8Calculated,%: C 20.70; H 2.60; N12.00; C1 40.70; Fe 24.00. Example 2, Tetrakis- (dimethyl-. Formamide) dichloro iron (1P) tetrachlorofermateSHMPHFREC 0.1 g of iron is dissolved in an atmosphere of sulfur CC4: (1: 1) CO; in a mixture of 10 ml of DMF and -o at 70 ° C. After 0.5 hour, the excess ... solvent is distilled off in vacuum. The oily residue is repeatedly washed with pentane. The yellow crystalline substance is reprecipitated by carbon tetrachloride from tetrahydrofuran (THF), washed with pentane and dried in vacuo at room temperature. Found,%; C 22.87; H 4.53; N 8.74; C1 33.88; f- e 18.46. P 2 2 284 ° 4 6 Calculated,%: C 23.30f H 4.55; , 05; C I 34.50; D 18O. PRI and measures 3. Tris- (d methylformamide) dichloro iron (P1) tetrachloroferrate C Fe (aMP) cC1a GReCi (, -DMDM}, iron dissolve ts atmosphere, 56 g re, CO in a mixture of 2 O ml of CC 1 and DMF About 1/1 (1: 1) at 70 ° C. After 1 hour, the solvent is distilled off in vacuum at 20 ° C / 0.1 mm Hg, station. The oily substance is rinsed several times with pentane and dried under vacuum. The substance is a solution 30 ml of oxyhydric pentane are recovered and 10 ml of absolute THF are replanted, and the oil is separated and dried under vacuum at 20 ° C / 0.1 mm Hg. The resulting solid is washed with pentane and dried in vacuo. g Note 4 , Tetrakis - (dimethyl sulfoxide) dichloro iron (L /) -Fe chloride (L s1.Hsid5G 0.1 g of iron is heated in a mixture of 5 DMSS and 5 ml of CC1 at 00-70 C 4,: in an argon atmosphere. After 20 A yellow solution was obtained on which; during the cooling of the vigil the yellow crystals fell, the crystalline powder was washed with foam and dried in vacuum, t, mp 59-60%, C 20.51; H 5, OO; .. G 21.40; 26.37; G e 12, O4. 3 Calculated,%: C 20.23; H 5, O5: C1 22.44; $ 26.97; Fe 11.80. PRI me R 5. Tetrakis- (dkmetilsul foksid) dichloro iron. (111) .- PSI tetrachlorofer. ffЕГЛМCQ) a LFeClJ- (Fe, Ci, 0.2 g of iron is heated in a mixture - 1 O ml of DMSO and 10 ml of its Id in a stream of CO; at 5 O s. After 0, 5 hours during cooling, they precipitate yellow-green crystals. The precipitate was washed with CC1, o with ether and pentane, mp P. 176 C. Found:% C 14.87; C I D30, 74; H 3.64; 519.30; re 17, 64. 5 tg Calculated,% :. From 15.07; il.3.88;: C from 33.5O; $ 2O, 10; Fe 17.50, Approx. Air Bis-Tetrakis-Sdime (| xxid a) dichloro iron (S) - tetra 1 E 0, 1 g of iron in 1 O ml see, if DMSO + + CG1, (1: 1) is heated and at 100-120 ° C for 30 minutes. When the Solution is cooled, the green drops out Crystals. Crystals of effluvium JV Qt Pea) {dione mass, they are washed with GC I and pentane and are nourished, so pl. 94-95 C. Found,%: C 17.98; And 4.58; ; C1 24.65; : S 22.71; fel6,30. S8 8- 8Calculated,% :. G 17.85; H 4.45; Cl 26.50; S.23.80; Fe 15.60. Chlorination of dicloxane in the presence of a VII catalyst. 3 P er im er.7. To 1.6 g (2.5. Mol) of a catalyst (p e, C i., 4 UMGO | 50: ml (39 g / O, 465: up) of cyclohexane is poured, ng. Is saturated with chlorine -; The mixture is heated in the dark for 5 minutes, then the reaction mixture is heated and heated for 4 hours. After cooling, the reaction mixture is filtered to separate the catalyst and separated by the preparative method. The weight of the isolated product is cyclohexyl chloride ::. - 25 g (98.5 wt.%) I lih.IQ 1.4625, dichloroproductive and cyclohexaigus, 0.38 g. Conversion of cyclohexane 46.1% / Example B. K OD6 g (2.5.1 mol) catalyst (G e c1.) 2 b poured 5 ml (3.9. g, O, 0465 mol) cyclic hexane gas, were sprinkled with chlorine at a coherent temperature for 2-3 minutes, and then the mixture was reacted and heated for 4 hours. After cooling, the reaction mass was filtered} 1l of the catalytic separation. Ator and analytical method GLC op- ", and .so.the holding of the products of the reaction. Conversion of pi.clohexa1 and 39.2%. Output and cyclohexyl chloride 98.7%, When the mor 9. The reaction is carried out as in Example 8, Take Oh, 16 g (2.5 l Omol) of the catalyst (Pe G 4 / lMGO). Conversion of cyclohexane 42.3%. Yield: piclohexyl chloro. A. 97.5%. P v; and m c-p 10, Reakshpo conducted as B primore ;. 8. Take O, 12 g (2.5 10 Moj-b) - catalysis mountain (f eC, .4ZIMGO). Koier.S.S. Logex 45.2%. The output of cyclohexyl chloro and 97%. Example ... 11, Reakhshuyu conducted, as in the example.9 8. Take 0.18 g (2.5 10-mol) of catalyst {. 6AN), Conversion of cyclohexane 33%. The yield of cycleexyl chloride is .99.5%, PRI me R 12, the reaction is carried out as in Example 8, O is taken, 20 g (2.5. 1C mol) of catalyst (Pe Ci. 8 DMOO), -. .. . . . onversi di 1: l6hexane. The yield of cyclo-J eksiphlorkda 98.3%, Chlorination of cyclohexane on the preparation of catalizer during che; ICL and, P p., Er 13,; For the reaction ber / t (0b g (10-O 3 mol) of metallic iron, 5 mp (5.5 g, 7 g) MSO 5 ml of CC: and 5 ml of cyclohexop. -I certain mix of g-assychak / t hporo- and then I go at .З-С In Hecheshte 4 hours, as a result, the stretch layer formed two layers. The lower maslos -... the base layer was separated. When standing for two weeks, yellow-green cristealls crystallized from the crystalline layers. The crystals were washed with ether, CC and pentane, T. Ill. 127-130 ° C. Found,%; C 14.16} H 2.91; C G 39, Q2; 526.72; fe 15.66. DeC H 5zSL4Viichioleno,%: C 13.66; H 2.57; C 1 40.43 G 527.38; fe 15.96. Conversion of cyclohexyl chloride 97%. Example 4. The reaction is carried out, as in example 8. Take 0.18 g (5. ICT mol) of catalyst (S feCl.). O4 Conversion of cyclohexane 46%. Output of picloxy chloride 98% P. p Imer / 15. ,, For the reaction they take 0; 015 g (2.5 f.lOr4 mol) of metallic iron, 5, g / dF (4.75 g, 6.5.102. M € ffi.i) iti 5..il, C1 | klogeksaia. Reaction pr, k, ak, E; example 8, As a result, reaction,; 1; and w; lasr dissolves and a / tfia layer forms. The top layer / separated. Conversion: cyclohexane 40 / b. The yield of cyclohexyl / ju 96,5%. The bottom layer — the catalyst solution — is used to chlorinate a new batch of cyclohexa. . .. Example 16. For the reaction, the catalyst solution of example 15 is taken. The action is carried out as in example 8. After the reaction, the lower layer of the catalyst solution is separated. Conversion of cyclohexane 42%, yield. Hexyl chloride 97%. Example 17. The reaction is carried out as in Example 15. The reaction is taken. O., 015 metallic iron (2.5 mol), 5 ml (.3.95 g, 9.6; 10-2 mol) of acetonitri 60 V8 la 5 ml of cyclohexane. The reaction is carried out as in example 8. Conversion of piclohexane is 38%, the yield of cyclohexyl chloride is 98.5%. P; Measure 18. The reaction is carried out as in Example 8. O, 05 g (2.5 U mol) Fed 4H O and 1.3 ml xd, -3 1.4 g, 1.6 are taken. , 10 mol) DMSO. Conversion, .cyclohexane 43%. Bvvsod cyclohexyl chloride 97.8%. P19 and measures 19. The reaction is carried out as in Example 8. O, Ob7 g (2.5 mol), resC 1 3 2,1 |, 2.4. mole) DMSO. Liklokoekoan conversion 45.2%. The yield of cyclohexyl chloride is 97.9%. The invention The method of obtaining cyclohexyl chloride by chlorination of cyclohexane with chlorine at elevated temperatures in the dark in the presence of. catalyst with a continuous release of the target product by known methods, distinguished by the fact that, in order to increase the selectivity of the process, the complex compound of the iron compound of the general formula g in J) IfimAn p, where X is used, is used as a catalyst. chlorine; 5f is a dipolar apotoin solvent, for example, dimethylformamide, dimethyl sulfoxide, adetonitrile; t 1-a; . P 1-8; p - 3-8,