Some features of the reaction of monochloramines of sulphoacids with unsaturated compound Текст научной статьи по специальности «Химические науки»

80

AZeRBAYCAN KIMYA JURNALI № 3 2018

ISSN 2522-1841 (Online) ISSN 0005-2531 (Print)

UDC 547.541.621/883

SOME FEATURES OF THE REACTION OF MONOCHLORAMINES OF SULPHOACIDS WITH UNSATURATED COMPOUNDS

S.A.Mammadov, L.F.Zeynalova, S.LMammadova, N.P.Ladokhina, A.A.Mahmudova,C.C.Babayev

A.Guliyev Institute of Chemistry of Additives, NAS of Azerbaijan

ninaJuad@rambler.ru

Received 31.03.2017

The reaction of monochloramide of benzene sulphonic acid with allyl chloride was studied. When using aprotic solvents chloro amidation reaction occurs, but with protic solvents ethylenechlorohydrin derivatives are formed. Atoms of chlorine in synthesized N-p-chlorosulphamides are very reactive and are easily substituted with nucleophiles even with 10 % of alkali water. When losing atom of chlorine they transform to aziridinesulphamides.

Keywords: chloramine-B and -T, hetarylsulphamides, aziridinesulphamides, anticorrosive activity, tribological properties.

Recently the research works on studying the reaction of N-mono- and N-dichloramides of sulphoacids with unsaturated compounds have been strengthened. These key reagents are commercially available, they are not toxic and sources of "halon", as well as "nitrogen anion" and contribute to molecular transformations. That's why they are used for amino hydroxyla-tion, epoxylation, aziridination of alkens, in the reaction of heterocyclization and so on.

Experimental part

l-Benzenesulphonylamido-N-2,3-dichlo-ropropan (I). 35 ml of concentrated (35.5%) solution of HC1 was added drop by drop into the mixture of 0.25 mol (28 g) of allylchloride, 0.3 mol (80.5 g) of chloroamine-B and 100 ml benzene after premixing for 25-30 min with sucha rate that temperature wouldn't increase higher than 40-45°C. The mixture was mixed for another 3 hours at 50°C temperature, cooled, 50 ml of hexane was added. The precipitated crystals were filtered off, washed with hexane and dried. Then they were crystallized from ethanol. 46.8 g (69.8 %) was obtained.

In PMR-spectrum of the compound I (Figurel) in the solution of DMSO-d we observed the signal in the form of multiplet in the region of 3.45 ppm (CH2CI), but in the region of 5.1 ppm we observed non-separated signal of protons CH2N. The signal of NH-proton is in the region of 6.8 ppm. Protons of monosubstituted benzene and CH-C1 are observed together in the region of 7.7 ppm.

N-2-Iodine-3-chloropropyl-l-benzene-sulphamide (II). The technique is similar to the method of obtaining the compound I. However, during the reaction 0.2 mol (33.2 g) of KJ was taken for 0.25 mol of chloramine-B, but the amount of hydrochloric acid was increased up to 56 ml. After the reaction obtained crystals were crystallized from ethanol.

N-2-Chloromethyl-N-(benzenesulpho-nyl)aziridin (III). 0.1 mol (26.2 g) of N-2,3-dichloropropyl-l-benzenesulphamide (I) was dissolved in 60 ml of benzene and 10% of NaOH solution was added at 10-20°C. The mixture was mixed at (25-3 5°C) temperature for an hour. Then 40 ml of hexane was added. The precipitate was filtered off, washed with water 2-3 times, dried and crystallized from ethanol. 17.7 g (76.8 %) was received.

Benzenesulphonylamido-N-2,3-propyl-dibenzamidothioacetic acid (IVa) and propyl-2,3-carboxypyridine (IV6). General technique. 0.03 mol of 1-benzenesulphonylamido-N-2,3-dichloropropan and 0.065 mol of ben-zamidothioacetic acid or nicotinic acid were mixed in the solution of benzene (25 ml) and 0.07 mol of triethylamine was added drop by drop. The mixture was boiled 5-6 hours, cooled and 20 ml of hexane was added. The precipitate was filtered off, washed with water, dried and crystallized from ethanol.

l-Benzenesulphonylamido-N-2,3-di-(N, N-diethyldithiocarbamate)propan (IVc). 0.03 mol (7.9 g) of compound I and 0.062 mol (9.3 g)

111

Fig. 1. PMR-spectrum of l-Benzenesulphonylamido-N-2,3-dicliloropropan (compound I).

Fig. 2. PMR-spectrum of l-Bcn/ciicsulphonyl-3-N-inctln lbcn/cncsulphoiiylaiiiidoiinidiizolc (compound VII).

of N,N-diethyldithiocarbamate of sodium were dissolved in 50 ml of ethanol. The mixture was boiled for 9 hours. Then ethanol was distilled and 50 ml of water was added into the reaction mass. The precipitated crystals were filtered off, dried and crystallized from ethanol. 12.9 g (63.6%) was obtained.

l-Benzenesulphonylamido-N-3-chloro-

2-benzamidosulphidopropan (V). 0.02 mol (7.2 g) of compound II and 0.22 mol (3.7 g) of benzamidomercaptoacetic acid were dissolved in 50 ml of isopropanol. 0.03 mol (3.1 g) of tri-ethylamine was added slowly into the mixture while mixing at (15-20)°C temperature drop by drop. Reaction mixture was mixed at 20°C temperature 10 hours. Then 50 ml of water was added. The obtained crystals were filtered off, dried and crystallized from ethanol. As a result 5.6 g (69.8%) was obtained.

N-3-Benzthioacetamido- (Via) and N-

3-(3-carboxypyridile)- (VIb) benzenesulpho-nylaziridines. General technique. 0.05 mol (11.6 g) of compound III and 0.052 mol (8.7 g) of benzamidomercaptoacetic acid or 0.052 mol (6.4 g) of nicotinic acid were dissolved in 40 ml of isopropanol and at 50-60°C temperature 0.055 mol (5.6 g) of triethylamine was dropped with stirring. Then the mixture was heated 5 hours while boiling, cooled and 30 ml of water was added. The obtained crystals were filtered off, washed with water, dried and crystallized from ethanol. 12.9 g (71.4%) of compound VI b was obtained.

l-Benzenesulphonyl-3-N-methylbenzene-sulphonylamidoimidazole (VII). 0.02 mol (5.4 g) of compound I and 0.02 mol (5.98 g) of ben-zenesulphonylguanidine were dissolved in 15 mol of ethanol. 0.04 mol (1.6 g) of NaOH was added into 10 ml of ethanol drop by drop at temperature of 50°C. The mixture was boiled 4 hours till full precipitation of crystals. 10 ml of water was added. Crystals were filtered off, washed with water, dried and crystallized from ethanol. 5.2 g (65.8%) was obtained.

In PMR-spectrum of the compound VII (Figure 2) protons of CH2N- and -CH2 (imidazole), related to each other as two doublets, appear in the region of 2.9-3.1 ppm. Protons of-CH and -NH of sulphamide group and proton of -CH

imidazole are in the region of 5.4-5.6 ppm. Proton of imidazole amine is in the region of 6.3 ppm. Protons of two monosubstituted aromatic fragments appear in the region of 7.2-7.9 ppm.

Physico-chemical characteristics of the compounds I-VII are given in the Table 1.

Table 1. Yields, melting point and elemental analysis of compounds i-vii_

№ comp. Yield, % tmelt.; °c Chemical formula Element analysis, %, found/calculated

n s

i 69.8 197-199 qfliinozsclz 5.68 5.24 12.30 11.95

ii 73.9 155-157 qfliinozscli 4.32 3.90 9.48 8.91

iii 77.8 225-227 c9h10no2sci 6.29 6.07 14.21 13.84

iva 59.8 206-207 C25H27N3O3S3 8.29 7.96 17.82 18.15

iv/) 65.3 170-173 C2aH17N306S 10.29 9.86 7.08 7.49

ivc 63.6 245-247 c19h30n3o2s5 8.91 8.56 32.05 32.52

V 69.8 185-187 c17h18n203s2ci 7.69 7.05 16.21 16.06

Via 71.4 250-251 c17h18n203s2 7.95 7.71 17.26 17.69

Ylb 62.2 200-203 c15h14n2o4s 8.96 8.83 9.73 10.07

vii 65.8 185-187 c10h18n4o4s2 14.69 14.26 15.93 16.25

Results and discussion

The products of sulphamidation reaction of unsaturated compounds with chloramine ply an important role in the synthesis of N-substituted sulphamide derivatives which are synthons for the synthesis of hetarylsulphamides. The method described for addition of chloramine to unsaturated compounds are different and depend on the structure of unsaturated compounds and use of N-mono- or N,N-dichloramines. Among literature data we often come across the reaction of unsaturated compounds with N,N-dichloramides of sul-phonic-acids. Study of the reaction n-CIC6H4SO2NCI2 with allylchloride showed that when using UV-irradiation or cyclohexyl-peroxydicarbonate chloramidation reaction goes better than without catalysts, but as a result of the rearrangement other compounds are formed along with basic products, which confirms ion-radical reaction [1]. Maybe that's why during the reac-

tion of acrylonitrile with N,N-dichloro-n-chlorobenzene sulphonamide telomerizarion of acrylonitrile takes place [2]. It was shown [3] that catalytic reaction of N,N-dichloro-//-tolu-enesulphamide with P-nitrostyrene leads to ami-do halogenation with high yield. In contrast the reaction of N,N-dichloro-«-tolylsulphamide with alkens in the presence of palladium leads to not only addition products, but also aziridination [4]. Stereoselective addition of monochloramide of sulpho acids to unsaturated compounds goes with promoter CO2 [5] or copper (1+) catalyst [6].

During the reaction of monochloramines -TsNClNa, BuNClNa with allyl derivatives [7] stereoselective addition occurs and cis- and trans-isomers of hydroxyaziridines are formed.

Our researches [8] showed that N-so-dium-monochloramines are easily attached to unsaturated compounds in acidic medium. On Chattaway's opinion perhaps during interaction of chloramines with acid unstable monochloramines are formed. Like very active substances they are easily attached to double bonds. The reaction of N-sodium-N-chlorsulphonamides with allylchlorides, acrylonitriles, and styrene leads to N-P-chlorsulphamides with high yield:

C1CH2-CH=CH2 + C6H5S02NNaCl

H

c6h5so2nh

I

CI

CI

One chlorine atom is substituted with iodine during the reaction of chloramine-B with allylchlorides in the presence of KI:

HC1

C1CH?-CH=CH? + C,H,SO,NNaCl + KI-»

2 2 6 5 2 _kq

-NaCl

c6h5 s02nh-ch2-ch-ch2c1

OH

CI

ch„

;CH-CH2C1

S02C6H5

in

During interaction of N-2,3-dichlor-ethanebenzenesulphamide with benzamidomer-captoacetic acid and N,N-diethylthiocarbamate and nicotinic acid sulphide derivatives are formed with an excess mercapto compounds and longer period of heating:

c6h5s02nh

CI

CI

+ hxr

xr xr

r=ch2conhc6h,, x=s (\\a) ;

c6h5so2nh

R=

, X=OOC

N

C1CH2-CH-CH2I

R=C-N(C2H5)2, x=S(IVc) s

Under mild conditions and low temperatures only one atom of iodine is substituted by compound II with benzamidomercaptoacetic acid, which is in position 2 and confirms their high reactivity:

C1CTL-CH-CTLI H SCT^ CONHC6Hs

2 2 -».

nh-so2c6h5

II

Under the effect of 10-15% alkali solution synthesized N-2,3-dichlorpropylbenzene-sulphamide transforms to azirdinesulphamide which confirms high reactivity of chlorine atom:

nh-so2c6h5

c6h5so2nh

y

Cl

sch2conhc6h5

During the reaction of sulphonylaziridine (III) with nucleophile opening of aziridine cycle was not observed:

CI

N

xr

+ HXR

so2c6h5

N

so2c6h5

r=ch conhc6h x=s (Via); r=

x=coo -(vi6);

N

Compounds I—III can be synthons for the synthesis of hetarylsulphamides. Imidazoledi-sulphamides are formed during the reaction of compound I with benzenesulphonylguanidine in alcohol alkali solution:

c6h5s02nh^ 7c1

hn

L

+

CI

^-nhso2c6h5

NFL

c6h5so2nhch2

-<

N'

n^/ ch7nhs02c6h5

H vii

Synthesized sulphamides were studied as additives to lubricating oils and lubricants. The data are presented in Table 2.

As follows from Table, all synthesized S-and N-derivatives of products of allylchloride reaction with chloramine-B have high anticor-rosive properties. With high content of chlorine atom in sulphamides (compound I and III) anti-corrosive properties get worse, but when they are substituted with sulphur and nitrogen in compounds (IV b,c) they sharply increase. With high content of functional groups in aziridinesulphamides (Yla-b) and in heterocyclic derivative (VII) anticorrosive properties are higher than in compounds (IV a-c).

Sulphamides (IV6, IVc, VI b, VII) have a high anticorrosive activity not only in oil M-8, but also in jointing pastes.

Table 2. Impact of synthesized sulphamides on exploitation properties of lubricating oils and lubricants in 3% concentration

Й .2 c о 5 Tribological properties

Name Critical Welding Wear scar

Ь bb load, load, diameter,

О 4H dm mm

Oil M-8 160-180 - - -

Oil AK-15 - 441 1558 0.58

Compound I 23.8 710 2750 0.50

Compound III 46.5 600 2350 0.55

Compound IVc/ 12.1 850 3200 0.49

Compound IV/) 10.2 800 3400 0.48

Compound IVc 8.1 1050 3900 0.41

Compound Via 5.5 1100 4000 0.40

Compound VI/) 4.3 1050 3950 0.41

Compound VII 3.2 1150 4050 0.39

DF-11 5.1 750 2830 0.45

Lubricant 141/ji 58.9 760 2850 0.49

+ Compound IVa 16.5 1100 3850 0.45

+ Compound IVc 10.1 1200 3950 0.40

+ Compound Via 6.5 1250 4000 0.39

+ Compound VII 1.8 1250 4050 0.38

Study of anti-wear and antiscuffing properties of synthesized compounds showed that they have high tribological properties. This can be explained by the presence of sulphide, ether and sulphamide groups in their composition. The highest anticorrosive and tribological effectiveness are observed in sulphamides which contain an ether group (compound VI b) and heterocyclic fragments (compound VII).

References

1. Freidlina R.KH., Rybakova N.A., Semin G.K., Kravchenko E.A. Vliianie okislitelei i sredyna reaktciiu N,N-dikhlor-n-khlorbenzolsulphamida s al-lilkhloridom // Docl. AN SSSR. 1967. T. 176. № 2. S. 352-353.

2. Rybakova N.A., Freidmina R.KH. Telomerizatciia akrilonitrila pri reaktcii ego s N,N-dikhloramid-n-khlorbenzolsulphamidom // Izv. AN SSSR, OKHN. 1969. №5. S. 1194-1196.

3. Thu Sanjun, Hon Jianlin, Lin Chen, An Guanghin, Pan Yi, Li Guigen. Catalytic reaction of aminohal-ogenation of P-nitrostyrenes with N,N-dichlor-n-tolylsulphonamide leading to dichlorinated haloid-amide with regiochemistry, opposite to preceding systems // Synthesis. 2006. No 10. P. 1570-1574.

4. Han Jiantin, Li Yufeng, Thi Sanjun, Pan Yi, Tim-mans Gody, Li Guigen. Aziridination of alkens catalyzed by palladium as a source of nitrogen using N,N-dichlor-n-tolylsulphonamide // Tetrahedron. 2006. No 40. P. 7226-7228.

5. Minokata S., Yeneda J., Oderaotosh Y., Komatsu M. Unprecedented promoting C02 aminochlorination of olefins with chloramine // Org. Lett. 2006. V. 8. No 5. P. 967-969.

6. Hauger G., Kolsow S., Göttlich D. Copper (1+) catalysts of stereoselective addition of N-chloramides to double bonds: diastereotselective

radical cyclization // J. Org. Chem. 2003. No 11. P. 1848-1854.

7. Susannah C., O'Brien P., Whitwood A.C. Stereoselective aziridination of cyclic alcohols using chloramine-T // Org. and Biomol. Chem. 2006. V.6. No 23. P. 4299-4314.

8. Mamedov S.A., Levshina A.M., Kerimov K.O., Gasanova T.Sh., Adigezalova F. A. Sintez N-(3-khloralkilarilsuFfamidov i issledovanie ikh v kachestve prisadok k smazochnym maslam // Neftehimiia. 1988. T. 28. № 3. S. 396-401.

SULPHOTURSULARIN MONOXLORAMiNLORlNiN DOYMAMI§ BiRLO^MOLORLO REAKSiYASININ

BOZi XUSUSiYYOTLORl

S.A.Mamm3dov, L.F.Zeynalova, S.LMammadova, N.P.Ladoxina, 0.0.Mahmudova, S.S.Babayev

В с и/о 1 s u 1 p 1 ю t u rs u пи n monoxloramidinin allilxloridb reaksiyasi ovronilmisdir. Aproton molilullar istirakinda xloramidlosmo reaksiyasi gedir, proton molilullarla iso ctilcnxlorliidrinlorin toromolori этэ1э golir. Sintez olunmus N-P-xlorsulphamidbrda xlor atomlari дох reaksiyaqabiliyyatlidir vo liotta 10%-li sulu qolovi molilulunda дох asanliqla nukleofilbrb 9V9z olunurlar. Xlor atomunu itirdikdo a/iridinsulpliamidloro cc\ rilirlor.

Agar si'n.br: xloramin-B V3 -T, hetarilsulphamid, aziridinsulphamid, antikorrozion aktivlik, triboloji xassshr.

НЕКОТОРЫЕ ОСОБЕННОСТИ РЕАКЦИИ МОНОХЛОРАМИНОВ СУЛЬФОКИСЛОТ С

НЕПРЕДЕЛЬНЫМИ СОЕДИНЕНИЯМИ

С.А.Мамедов, Л.Ф.Зейналова, С.И.Мамедова, Н.П.Ладохина, А.А.Махмудова, С.С.Бабаев

Изучена реакция монохлорамида бензолсульфокислоты с аллилхлоридом. При использовании аиротонных растворителей происходит реакция хлорамидирования, а с протонными растворителями образуются производные этиленхлоргидринов. Атомы хлора в синтезированных N-p-хлорсульфамидах очень реакционноспособны и легко замещаются нуклеофилами в присутствии даже 10%-го водного раствора щелочи. Теряя атом хлора, они превращаются в азиридинсульфамиды.

Ключевые слова: хлорамин-Б и -Т, гетарилсулъфамиды, азиридинсульфамиды, антикоррозионная активность, трибологические свойства.