SU1336494A1 - Method of producing nъ,nъ-dialkyl-n2-arenesulfonylformamidines - Google Patents

Abstract

The invention relates to the formamidine / in particular the method of producing N, N-dialkyl-N-arynesulfonyl-amidines of the general formula (R) jN-CH-H5 (0) g-Ar, where Ar is C Iupri RC, SLD; Ar - 4-CH5SbN priK-S, -C haps; Ar - 4-C1C4H4 with R - CHj, used as reactive intermediates and biologically active compounds. To increase the yield of the target products, simplify the process, dichloroarenesulfonates are first reacted with trichl ethylene at 85–90 s, then dialkylamine at 20–30 ° C at a molar ratio of: (4–12) :( 2-3) . The introduction of the process according to this scheme allows to increase the yield of target products up to 69-92% against 30-50% in a known method, to simplify the process. through the use of available reagents, and also to obtain a number of new Substances. W with with CR

Description

1336494

This invention relates to an improved process for the preparation of N, N -lalkyl-N -arensulfonyl forms-amides of the general formula

(R) jN-CH NSO, Ar,

where Ar -, R - OjHj (l), CjH, (ll), of kiln groups, integral integersC Hg (III),., (IV),

. CH, (V); Ar - 4-СНзС Н, К - CjHj (VI) ,.

CHj (VII); Ar - A-ClCgH, R - CjHj (VIII),

CHj (IX), which can be used in op- | g

which properties correspond to structure-fQ frames of formamidines (l-IX).

And: the invention is illustrated by the following examples.

Example. N, to -Diethyl-and-phenylsulfonylformamidine (I).

Mixture. A, 52 g (0.02 mol) I, H-dichlorobenzenesulfamide (dichloramine-B) and 7.2 ml (0.08 mol) of trichlorethylene are heated under nitrogen atmosphere for 8 hours until chlorine evolution ceases.

synthetic synthesis as reactive intermediates and biologically active compounds.

The purpose of the invention is to increase the yield of target products, simplify the process, increase its versatility due to the fact that the derivatives of N, H-dichlorarenesulfonamides are subjected to interaction with trichlorostilen and dialkylamines under certain conditions.

The process is carried out as follows:

RSOjN (Cl) (C1, j) CHCl + 2NH (Alkyl) RSOjN CHN (Alkyl) 2, (Alkyl) j j SG

where R has the indicated meanings.

The process is carried out as follows: dichloramides of sulphonic acids are dissolved in trichlorostilen and heated at 85-90 ° C in an inert atmosphere for 6-9 hours, controlling the course of the reaction by the release of chlorine (iodkrahmalny indicator), then to the reaction mixture

It is obtained similarly from 4.52 g (0.02 mol) of dichloramine-B, 7.2 ml (0.08 mol) of trichlorethylene and 4.05 g

, ° (0.04 mol) of dipropylamine at ki from 20-30 o 1 h. The yield of the target products is 60-90%.

The compounds obtained are slightly colored substances.

crystalline nature, odorless, 45 radiate s, 3b g (69%) of product (S) with persistence during storage, pacTBopHNaie in a melting point of 60-65 ° C alcohol acetone, chloroform, trichloride ethylene, dimethyl sulfoxide, dimethylformamide.

The structure of the compounds was confirmed by g0 and proved by the methods of IR and PMR spectroscopy and counter synthesis. Purity confirmed by elemental analysis.

In the IR spectra of the synthesized soy; E11nie (l-IX), marked absorption band, cm: 3090-3060 (CH aryl): 2990-2960; 2950-2930; 2880 with trichlorethylene with dichloramine-B, under an inert atmosphere for 8 hours. When adding dipropylamine, the mixture is heated to 70 seconds. Found,%: C 57.64; H 7.38} S 11.91; and 10.43 C jH oOiKiS

Calculated,%: C 58.21; H 7.46; S 11.94; N 10.45.

Example 3. N, n -Di5utsh1-N - phenylsulfonylformamidine (ill), gg Prepared similarly from 4.52 g

2820 (alkyl); 1630-1610: (); 1330-1290, 1160-1140 (SOj).

(0.02 mol) of dichloramine-B, 7.2 NP (0.08 mol) of trichlorostilen and 5.15 g (0.04 mp) of dibutylamine p | boiling trichlorethylene with dichlorams om-B

The PMR spectra of compounds (l-IX) show signals of protons of the azemethine group in region 8, ppm. (s), the protons of the aromatic ring are 7.89-7.71 and 7.57-7.30 and ID (m.), and also signals of protons al | g

which properties correspond to structure-fQ frames of formamidines (l-IX).

And: the invention is illustrated by the following examples.

Example. N, to -Diethyl-and-phenylsulfonylformamidine (I).

Mixture. A, 52 g (0.02 mol) I, H-dichlorobenzenesulfamide (dichloramine-B) and 7.2 ml (0.08 mol) of trichlorethylene are heated under nitrogen atmosphere for 8 hours until chlorine evolution ceases.

2Q Chlorine emission control is carried out by breaking with iodine paper. At the end of the chlorine evolution, the reaction mixture is cooled to 20 and 2.96 g (0.04 mol) are added.

25 N, N-dietsh1amina. See self-heating up. The reaction mixture is stirred for 1 hour, then the excess trichlorethylene is distilled off in vacuo. 4.18 g (87.1% of the theory) of duct (I) with t, pl. 73-75 C.

Found,%: C 54.63; H 6.51; S 13.66; N 11.65 C ,, H ,, 0,

Calculated,%: C And 6.67; S 13.33; N P, 67.

35 Approx 2. N, K-Dipropyl-N-phenylsulfonylformamidine (I).

It is obtained similarly from 4.52 g (0.02 mol) of dichloramine-B, 7.2 ml (0.08 mol) of trichlorethylene and 4.05 g

 ° (0.04 mol) of dipropylamine with a killer h, 3b g (69%) of the product (S) with a melting point of 60-65 ° C

cooking trichlorethylene with dichloramine-B under an inert atmosphere for 8 hours. Adding dipropylamine warms the mixture to 70 seconds. 45 g C, 3b g (69%) of product (S) with a melting point of 60-65 C

g0

Found,%: C 57.64; H 7.38} S 11.91; and 10.43 C jH oOiKiS

Calculated,%: C 58.21; H 7.46; S 11.94; N 10.45.

Example 3. N, n -Di5utsh1-N - phenylsulfonylformamidine (ill), gg Prepared similarly from 4.52 g

(0.02 mol) of dichloramine-B, 7.2 NP (0.08 mol) of trichlorostilen and 5.15 g (0.04 mp) of dibutylamine p | boiling trichlorethylene with dichlorams om-B

in an inert atmosphere for 8 hours. When dibutylamine is added, the mixture is heated to SO C. 4.26 g (70%) of product (III) is obtained with m.p. 40-45 C.

Found,%: C 56, A5; And 7.30; S 11.49; N 10.30 .C ,, H ,, 0, N, H

Calculated,%: C 60.81; H 8.11; S 10.49; N 9.46.

Prime

15

 l

p 4. N N -Digexyl-N - phenylsulfonylformamidine (IV).

Similarly, from 4.52 g (0.02 mol) of dichloramine-B, 7.2 ml (0.08 mol) of trichlorethylene and 7.42 g (0.04 mol) of dihexylamine are obtained at boiling trichlorethylene with dichloramin-B at 90 ° C in an inert atmosphere for 8 hours. Adding dihexylamine, the mixture is heated to 7 () ° C. Obtain 4.1 g (56.3%) of the product (IV) with so pl. 38-40 ° C.

Found,%: C 62.84; H-9.09; S 9.63; N 9.00

ten

WITH.

Calculated,%: C 64.77, H 11.00; S 11.00; N 7.96.

PRI me R 5. N, K -Diethyl-K-D-tolylsulfonylformamidine (Vl).

It is obtained similarly from 4.8 g (0.02 mol) of N, N-dichloro-tollosulfonamide (dichloramine-T), 7.2 ml (0.08 mol) of trichlorethylene and 2.96 g (o, 04 mol) of diethylamine boiling trichlorethylene with dichloramin-T at 90 ° C in an inert atmosphere for 8 hours. Adding diethylamine warms the mixture to 60 ° C. 4.01 g (SOf) of product (Vl) is obtained with m.p. 60-63 ° C.

Found,%: C 56.66; H 7.17; S 12.14; N 10.71

C, j H, g02ri - S

Calculated,%: C 56.69; H 7.09; S 12.60; N 11.02

PRI me R 6. N, to -Distil-K

It is obtained analogously from 4.8 g (0.02 mol) of dichloramine-T, 7.2 ml (0.08 mol) of trichlorethylene, 15 g (o, 18 mol) of dimethyl-amine hydrochloride and 7, -5 g (0, 18 mol) sodium hydroxide at boiling trichlorethylene with dichloramin-T at 90 ° C in an inert atmosphere for 8 hours, then a stream of dimethylamine obtained from (CH,) ,, NH-HC1 and IOH, is passed, 1 hour is obtained. 82%) of the product (VIl) with a melting point of 35 125-130 s.

Found,%: C 51.72; C 6.70; S 14.42; N 11.95

Xu N..I

Calculated,%: C 53.10; H 6.19; S 14.16; N 12.39.

Example9. K, N -Dimethyl-K-4-chlorophenylsulfonylformamidine (IX).

Prepared similarly from 5.13 g

(0.02 mol) dichloramine-CB, 7.2 ml of 4-chlorophenylsulfonylformamidine (VIIl). l5 (0.08 mol) of trichlorethylene, 15 g

It is obtained analogously from 5.13 g (0.18 mol) of dimethylami- (0.02 mol) H, H-dichloro-chlorobenzene hydrochloride, 7.5 g (0.18 mol) of sodium sulfonamide hydroxide (dichloramine-CB ), 7.2 ml of boiling trichlorethylene with (0.08 mol) of trichlorethylene and 2.96 g of dichloramine-CB in inert (0.04 mol) diethylamine at boiling temperature of 50 h for 8 h, then the current of the scientific research institute is passed trichlorethylene with dichloramin-CB at 90 ° C in an inert atmosphere of 8 h. Adding diethylamine warms the mixture to 55 ° C. 4.22 g (77.0%) of product (VIIl) are obtained with a mp. 75-78 ° C.

Found,%: C 47.67; H 5.65; S 11.57; N 9.69

C, H

dimethylamine, obtained from (CH,), KN HC1 and NaOH, 1 hour. Obtain 4.5 g (92%) of the product (ix) with so pl. I08-lll c.

55% found: C) 16.90; S 12.93; N 11.54

Calculated, ° L: C1 14.40; S 12.93; N 11.35.

15

B C.

36D94

Calculated,%: C 48.07; H 5.46; S 11.65; N 10.20.

PRI me R 7. N, N-Dimethyl-N - phenylsulfonylformamidine (V).

4.52 g (0.02 mol) of dichloramine-B, 7.2 ml (0.08 mol) of trichlorethylene, 15 g of dimethylamine hydrochloride and 7.5 g (0.18 mol) of sodium hydroxide are obtained. while boiling trichlorethylene with dichloramin-B at 90 ° C in an inert atmosphere for 8 hours, then a current of dimethylamine obtained from (CH3) HC HCl and NaOH is passed through, 1 hour. Trichlorethylene is distilled off in vacuum. Obtain 2.92 g (66.0%) of the product (v) with so pl. 127-130 C.

Found,%: C 50.60; H 5.80;

ten

S 15.27; N 12.73

Cg N, O, K ,; S

Calculated,%: C 50.92; H 5.66; S 15.09; N 13.20.

PRI me R 8. N, 1H-dimethyl-K - 4-tolylsulfonylformamidine (VIl).

It is obtained analogously from 4.8 g (0.02 mol) of dichloramine-T, 7.2 ml (0.08 mol) of trichlorethylene, 15 g (o, 18 mol) of dimethyl-amine hydrochloride and 7, -5 g (0, 18 mol) sodium hydroxide at boiling trichlorethylene with dichloramin-T at 90 ° C in an inert atmosphere for 8 hours, then a stream of dimethylamine obtained from (CH,) ,, NH-HC1 and IOH, is passed, 1 hour is obtained. 82%) of the product (VIl) with a melting point of 5 125-130 s.

Found,%: C 51.72; C 6.70; S 14.42; N 11.95

Xu N..I

Calculated,%: C 53.10; H 6.19; E S 14,16; N 12.39.

Example9. K, N -Dimethyl-K-4-chlorophenylsulfonylformamidine (IX).

Prepared similarly from 5.13 g

(0.18 mol) of dimethylamine hydrochloride, 7.5 g (0.18 mol) of sodium hydroxide at boiling of trichlorethylene with dichloramine-CB in an inert atmosphere for 8 hours, then a current is passed

dimethylamine, obtained from (CH,), KN HC1 and NaOH, 1 hour. Obtain 4.5 g (92%) of the product (ix) with so pl. I08-lll c.

Found,%: C) 16.90; S 12.93; N 11.54

Calculated, ° L: C1 14.40; S 12.93; N 11.35.

Example 10. N, N —flHMeTW-N Phenyl phonylformamidine (I).

It is obtained from 4.52 g (0.02 mop) of dichporomy-B, 5.4 ml (0.06 mol) of trichlorethylene and 2.96 g (0.04 mol) of diethylamine by boiling trichloro ethylene with dichloramine-B at 90 C in an inert atmosphere for 18 hours

When diethylamine is added, the mixture is heated up to. Obtain 2.74 g (57, it) of product (l) with so pl. 73-75 C.

Found,%: C 54.63} H 6.51; S 13.66; N 11.65

Ci, H ,, 0, N, S

Calculated,%: C 55.03; H 6.67; S 13.33; N 11.67.

PRI me R 11. N, N -DIETHYL-N - fennsulfonylformamidine (I).

Prepared from 4.52 g (0.02 mol) Dshshoramin-B, 7.2 ml (0.08 mol) of trichlorethylene and 1.48 g (0.02 mol) of diethylamine at boiling trichlorethylene with dichloramin-B at 90 ° C in an inert atmosphere for 8 hours. This gives 2.36 g (49.18 /) of product (l) with mp 73-75 C.

Found,%: C 54,635; H 6.51; S 13.66; N 11.65

.OjNjS

Calculated,%: C 55.03; H 6.67; S 13,335 N 11,67 2

Example 12. N, N-Diethyl-N - phenylsulfonylformamidine (I).

Prepared from 4.52 g (0.02 mol) of dichloramine-B, 7.2 ml (0.08 mol) of trichlorethylene and 4.44 g (0.06 mol) of diethylamine by boiling trichlorethylene with dichloramin-B at 90 ° C in an inert atmosphere. Into 4 hours; 4; 22 g (87.9%) of the product (l) with m.p. 73-75 C.

Found, / j; C, 54.63; .H 6.51; S 13.66; N P, 65

CfVHie iNrS

Calculated,%: C 55.03; H 6.67; S 13.33; N 11.67

 Example 13. N, s-Diethyl-H - phenylsulfonylformamidine (I).

Prepared from 4.52 g (0.02 mol) of dichloramine-B, 14.4 ml (0.16 mol) of trichlorethylene and 2.96 g (0.04 mol) of diethylamine at reflux of trichlorethylene with dichloramin-B at 90 ° C in an inert atmosphere for 8 hours, followed by the addition of dialkylamine. After evaporation of trichlorethylene and washing the residue with cold water (100 ml) to the floor .16494. .

Chnno 4.17 g (87.7%) of the product (l) with a melting point of 73-75 C.

Found,%: C 54.62; H 6.51; S 13.67; N II, 64 C, H,

Calculated,%: C 55.03; H 6.67; S 13.33; N 11.67

Example 14. N, N -fln3Tfui-N - Q Phenylsulfonylformamidine (l).

Prepared from 4.52 g (0.02 mol) of dichloramine-B, 21.6 ml (0.24 mol) of trichlorethylene and 2.96 g (0.04 Mojib) of diethylamine by boiling trichloro-g of ethylene with dichloramine at 90 with in an inert atmosphere of 8 hours. 4.19 g (87.8%) of the product (l) with m.p. 73-75 C.

Found,%: C 54.67; H 6.53; Q S 13.59; N I 1.69

C ,, K, 0, N, S

Calculated,%: C 55.03; H 66.67; S 13.33; N II, 67.

The proposed method allows 5 to increase the yield of target products up to 69-92% against 30-50% in the known method, to simplify the process by using available reagents, ease of implementation of the stage of completion, while in the known method hard-to-reach and unstable reagents and multistage purification of target products. In addition, the proposed method, along with obtaining the known compounds

five

The scientific research institute allows to synthesize new compounds with high output.

Claims (1)

Invention Formula .,one The method of obtaining N, N-dialkyl-N-ar nsulfonylform-midin common o opMyjibi (R) J Ar, where priAg-C Hj, R- C, jHj, CjH,,, C (., CH j; with Ar-4-CH} C4H4, R-CjHj, Ar-4-Cl-C H4, R-CjHj, CH3, using sulfamides, which is due to the fact that the expansion of the target products is increased. the assortment of final products, simplifying the process, increasing its versatility, use K, K-dichlorarensulfamnda of the general formula as sulphonamide derivatives ),   1336494 8 where R has the indicated values, then with dialkylamines at 20, which are reacted at 30 ° C at a molar ratio of 1: (4, first with trichlorethylene at 85-12) :( 2-3), respectively. Compiled by N.Kulikova Editor B.Horin Tehred L.Serdyukova Proofreader M.Pojo Order 156 / Circulation 252Subscription VNIIPI USSR State Committee on affairs of inventions and discoveries P3035, Ioskva, Zh-35, Raushsk nab., 4/5 Proizvodstviiii-polygraphic enterprise, Uzhgorod, st. Design, - 4