PL237731B1 - New iodonium salts, method of their preparation and use, new intermediates for preparing new iodonium salts, methods of preparing new intermediates and use of intermediates - Google Patents

Abstract

The present invention relates to new iodonium salts of general formula (1) wherein R1 is -H, -CN, -COOC2H5; R2 is -CN, -COOC2H5; R3 is -H, -OCH3, -CH3, -Ph; R4 - R8 are each independently -H, -CN, -CH3, -CH(CH3)2; E- is an anion selected from the group consisting of PF6-, SbF6-, BF4-, CF3SO3-, B(C6F5)4-, [Al(OC(CF3)3)4]-. The invention also relates to a process for the preparation and use of new iodonium salts, new intermediates for the preparation of new iodonium salts, methods for preparing new intermediates and the use of intermediates.

Description

Description of the invention

TECHNICAL FIELD

The invention relates to new iodonium salts, their preparation and use, as well as new intermediates for the preparation of new iodonium salts, processes for the preparation of new intermediates and the use of the intermediates. The iodonium salts of the invention can be used as photoinitiators for cationic polymerization.

STATE OF THE ART

Today, the most modern technologies for the production of polymeric materials are based on photochemically initiated processes. It uses electromagnetic radiation ranging from ultraviolet (UV) to visible light (Vis). The synthesis of polymeric materials carried out by these processes is one of the most efficient methods, therefore it is currently a very widespread and rapidly developing technique. Light polymerization was initially used primarily in the coating industry, mainly in varnishing, in the production of solvent-free paints and varnishes for the printing, furniture and automotive industries [(1) S.P. Pappas, Radiation Curing, Science and Technology, Plenum Press, New York, 1992], Photopolymerization also plays an increasingly important role in the design and formation of models using stereolithography, in medicine for the preparation of hydrogel polymeric materials [(2) JP Fisher, D. Dean , PS Engel, AG Mikos, Annual Review of Materials Science 2001, 31, 171-81] and in dentistry for photocurable fillings [(3) KD Jandt, BW Sigusch, Dental Materials 2009, 2, 1001-1006], Cationic photopolymerization is an area of science that is developing very dynamically and revolutionizing many areas of modern technology. There is not only an astonishingly rapid growth in applications, but also the development of new materials determining the pace of this development.

Currently, however, the greatest hopes are associated with the development of new chemical compounds as photoinitiators of cationic polymerization. The result of the conducted research is the development of an extensive spectrum of chemical compounds intended as initiators of cationic polymerization. Despite such extensive scientific work, the number of systems commonly used in industrial practice for the role of cationic photoinitiators is negligible and is mainly limited to diaryliodonium salts of the general formula (1), in which E "stands for a counterion, usually PFe, SbFe, AsFe" , BF ₄ ”, FSO ₃ ”, CF3SO3 ·, CIOzT, (Ο ₆ Η ₅ ) 4Β ”, (C6F ₅ ) 4B”.

E ^{Ar kAr} [XX] and triarylsulfonium salts.

The onium salts, which include the diaryliodonium salts, are widely regarded as materials of the future due to the numerous advantages that are brought by the industrial application of these systems. This is because they turn out to be the most promising solutions that will revolutionize the photochemical industry when they are improved by eliminating the existing basic disadvantages of not matching the absorption characteristics to the emission characteristics of industrial ultraviolet (UV) and visible (Vis) light sources. From the application point of view, the most important properties of iodonium salts used as polymerization photoinitiators (apart from solubility in monomers) are their optical properties, i.e. the scope and amount of light absorption.

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Table I.

Known and commercially available iodonium photoinitiators commonly used in industrial practice, all the mentioned salts absorb radiation in the range of 200-300 nm.

Currently, almost all iodonium salts used in industry as photoinitiators show similar UV absorption characteristics in the wavelength range 7max = 220-280 nm [(4) J.V. Crivello, Advances in Polymer Science 1984, 62, 1-48] [(5) JV Crivello, Journal of Polymer Science: Part A: Polymer Chemistry 1999, 37, 4241-4254] (Table I), i.e. the light sensitivity of commercial iodonium photoinitiators is in the short wavelength range of UV light, which is a significant technological problem in their mass applications [(6) WA Green, Industrial Photoinitiators A Technical Guide, Taylor & Francis Group, 2010],

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Chart I. Comparison of the emission characteristics of the medium pressure mercury lamp (MPM) with the absorption characteristics of commercial iodonium photoinitiators.

This is due to the fact that in this wavelength range, there are no highly efficient light sources that would emit light of sufficiently high power. Below 300 nm, they only emit low-pressure mercury lamps and deuterium lamps, which are low-power light sources and are not used for industrial applications [(7) M. Montalti, S.L. Murov, Handbook of Photochemistry, Taylor & Francis Group, LLC, 2006], In industry, the basic high-power UV light sources used to induce photochemical reactions, including photopo-humerization reactions, are medium pressure mercury lamps (MPM lamp · medium pressure mercury lamp) which emit the most UV energy at approx. 365 nm (Graph I and Table II).

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Table II

Relative spectral distribution of mercury lamp radiation [(8) J Pączkowski, Photochemistry of polymers theory and application, Nicolaus Copernicus University Publishing House, Toruń 2003],

Low pressure mercury lamp (Hanovia SC2537 type) High pressure mercury lamp (type Hanovia A673, 550 W) Wavelength Intensity [nm] [j. relative] Wavelength Intensity [nm] [j. relative] 253.7 100.00 248.2 8.6 296.7 0.20 253.7 16.6 312.9 0.60 265.3 15.3 365.4 0.54 280.4 9.3 404.7 0.39 289.4 6.0 435.8 1.00 296.7 16.6 546.1 0.88 302.3 23.9 312.9 9.9 334.2 9.3 365.4 100.0 404.7 42.2 435.8 77.5 546.1 93.0

A similar technological problem occurs in the case of using lamps equipped with LED diodes (JJght Emitting Diodeś). LED lamps are becoming more and more popular on the market of photo-curable polymer coatings. Currently, there is a wide range of LED lamps on the market of various wavelengths - from visible to ultraviolet. Typically LED lamps emitting ultraviolet wavelengths of about 365, 385 or 395 nm, or the visible wavelength of 405 nm, are usually used for industrial scale photochemical processes.

From the industrial point of view, the main advantages of radiators equipped with LEDs are the fact that LEDs can be easily turned off and on in a fraction of a second. This saves electricity and time as the lamps do not have to heat up before starting work, as is the case with mercury lamps.

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II

III

Charts II and 111. Comparison of the emission characteristics of 365 nm and 395 nm UV-LED diodes with the absorption characteristics of commercial iodonium photoinitiators.

In addition to low power consumption, reduced heat emission and an almost unlimited service life, photochemical polymerization processes carried out with the use of LED lamps also result from a low drying temperature. Therefore, thanks to the use of photochemical curing technology with the use of LED light sources, currently in the printing industry it is possible to print substrates that were impossible to use in machines with mercury lamps due to their sensitivity to heat.

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This allows not only to expand the range of used media with new, interesting materials, but also to reduce costs thanks to the use of cheaper, more sensitive substrates. Nevertheless, the main technological problem that does not allow the use of LED light sources is the lack of matching the emission characteristics of LED lamps in the range from 365 nm to 405 nm with the absorption characteristics of commercially available photoinitiators, in particular cationic photoinitiators. For both medium pressure mercury lamps and lamps equipped with UV-LEDs (365 nm, 385 nm, 395 nm) or Vis-LEDs (e.g. 405 nm) only a small part of the energy is emitted in the absorption range of commercial iodonium photoinitiators. As a result, the previously used cationic photoinitiators based on diphenyliodonium salts have a bad adjustment of the absorption characteristics to the emission characteristics of industrial UV and Vis light sources, such as medium-pressure lamps and UV LEDs and Vis LEDs (Charts II and III).

In view of the above, the development of new cationic photoinitiators, which will show a light sensitivity in terms of medium-pressure mercury lamp emissions, is very important both from the cognitive and application point of view. So far, only a few iodonium salts dedicated to the role of photoinitiators of polymerization processes are known, showing the absorption of light above 300 nm. One of the first systems based on the skeleton of an iodonium salt coupled with a fluorenone chromophore is (9-oxy-9H-florin-2-yl) phenyl iodonium hexafluoroantimonate (V) [formula (II)] published by Hartwing's team in 2001 [(9 ) A. Hartwig, A. Harder, A. Luhring and H. Schroder, Eur. Polym. J., 2001, 37, 1449], The obtained photoinitiator is characterized by several absorption maxima (267 nm, 298 nm, 380 nm and 394 nm), however, the longest-wavelength band located at 394 nm is over 100 times less intense (molar coefficient extinction at this wavelength is only ε = 400 mol dm ³ mol ^-1 cm ^-1 ) from the shortest wave band located at 267 nm (the molar extinction coefficient at this wavelength is ε = 42,000 mol dm ³ mol ^-1 cnT ¹ ) . Therefore, (V) (9-oxy-9H-florin-2-yl) phenyl iodonium hexafluoroantimonate is not used in industrial applications.

^ max-i = 367 nm ε = 42,000 [lmor ¹ cm- ¹ ] = 298 nm ε = 8,500 [lmor ¹ cm ' ¹ ]

7 ^ -3 = 380 nm ε = 430 [lmol ' ¹ cm' ¹ ] ^ max-4 ⁼ 394 nm ε = 400 [lmol ' ¹ cm' ¹ ]

Another significant report on iodonium photoinitiators showing significantly improved absorption properties is the work of Ortyl [(10) J. Ortyl and R. Popielarz, Polimery, 2012, 57, 510], in which photoinitiators based on the coumarin skeleton were presented. The most effective derivative, presented below, shows the maximum absorption at the wavelength located at 345 nm, where the molar extinction coefficient is respectively ε = 16,300 mol dnr ³ mol ^-1 cm ^-1 . Such a high absorption coefficient allowed to achieve high speed and conversion even with the use of cationic monomers during the photopolymerization process of such light sources as UV LED diodes with a wavelength of 365 nm and a wavelength in the visible Vis-LED range [(11) H. Mokbel, J Toufaily, T. Hamieh, F. Dumur, D. Campolo, D. Gigmes, JP Fouassier, J. Ortyl and J. Laleve'e, J. Appl. Polym. Sci., 2015, 132, 42759],

X _max = 340 nm X _max = 308 nm ε = 18 430 [lmol ' ¹ cm' ¹ ] ε = 14 850 [Imol ^ cm ¹ ]

X _max = 350 nm 7 _max = 316 nm ε = 18,050 [ImorW] ε = 14,420 [ImorW ¹ ] gid

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Subsequently, in 2016, Lalevee et al. have been published by [(12) N. Zivic, M. Bouzrati-Zerrelli, S. Villotte, F. Morlet-Savary, C. Dietlin, F. Dumur, D. Gigmes, J. P. Fouassier and J. Lalevee, Polym. Chem., 2016, 7, 5873] detailed photochemical studies on an iodonium photoinitiator based on 1,8 naphthalimide (IV) skeleton. The product showed a maximum absorption at 340 nm, which allowed for efficient cationic photopolymerization of monomers using UV-LED diodes. However, this initiator is still not commercially available due to the cost-effectiveness of producing it. It is worth noting that in this case the chemical structure of the iodonium salt was complicated, and it was extended with the 1,8-naphthalimide chromophore. Accordingly, the molar mass of the photoinitiator also increased and, consequently, the molar yield of protic acid generation during the photopolymerization process decreased.

PFe

Due to the limited number of available iodonium photoinitiators, characterized by absorption in the long-wave UV spectrum (λ> 300 nm), the works aimed at designing and obtaining such iodonium salts are fully justified from the point of view of improving the kinetics of the photopolymerization process. On the other hand, adjusting the absorption characteristics of initiators to the emission characteristics of medium-pressure mercury lamps and light sources such as UV-LED and Vis-LED diodes will enable better use of energy by increasing the photolysis rate of iodonium salts, and thus increase the initiation rate.

2 - [(3,5-dimethoxyphenyl) methylene] propanedinitrile is known from Chinese patent application (13) CN 104497007. It was used, in addition to the thioindolone derivative, to produce chiral compounds - indenothiopyran derivatives, which were intermediates for the production of drugs and pesticides.

From the publication [(14) "Photoinduced Nitric Oxide Release from Nitrobenzene Derivatives"; Takayoshi Suzuki, Osamu Nagae, Yuka Kato, Hidehiko Nakagawa, Kiyoshi Fukuhara, Naoki Miyata; J. AM. CHEM. SOC. 2005, 127, 11720-11726], (E) -3- (3,5-dimethoxyphenyl) prop-2-enenitrile is known. This compound was an intermediate for the preparation of 3- (3,5-dimethoxyphenyl) propenal.

From the publication [(15) "Synthesis and anti-tumor activity of novel ethyl 3-aryl-4-oxo-3,3a, 4,6-tetrahydro-1H-furo [3,4-c] pyran-3a-carboxylates" ; Tiantian Wang, Jia Liu, Hanyu Zhong, Huan Chen, Zhiliang Lv, Yikai Zhang, Mingfeng Zhang, Dongping Geng, Chunjuan Niu, Yongmei Li, Ke Li; Bioorganic & Medicinal Chemistry Letters 21 (2011) 3381-3383] diethyl 2 - [(3,5-dimethoxyphenyl) methylene] malonate is known. This compound was prepared from 3,5-dimethoxy-benzaldehyde and diethyl malonate and it was used to prepare the title compounds of which reference is made in (15).

The use of 2 - [(3,5-dimethoxyphenyl) methylene] propanedinitrile, (E) -3- (3,5-dimethoxyphenyl) prop-2-enenitrile, or 2 - [(3.5-dimethoxyphenyl) methylene] diethyl-dimethoxyphenyl) methylene] malonate for the preparation of iodonium salts used as photoinitiators in cationic photoinitiated polymerization processes.

Surprisingly, it has been found that the new iodonium salts according to the present invention can play the role of photoinitiators for the photoinitiated cationic polymerization processes.

SUMMARY OF THE INVENTION

The invention relates to new iodonium salts of general formula (1)

Fb

(1)

PL 237 731 B1 in which

Ri is -H, -CN, -COOC2H5;

R2 is -CN, -COOC2H5;

R3 is -H, -OCH3, -CH3, -Ph;

R4-R8 are each independently -H, -CN, -CH3, -CH (CH3) 2;

E ^- is an anion selected from the group consisting of PFe ^- , SbFe ^- , BF4 ^- , CF3SO3 ^- , B (C6Fs) 4 ^- , [Al (OC (CF3) 3) 4] ^- .

Preferred iodonium salts according to the present invention are selected from the group consisting of:

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium triflate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium alkoxyaluminate ([Al (OC (CF3) 3) 4] ^- );

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium triflate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium alkoxyquinate ([Al (OC (CF3) 3) 4] ^- );

(2-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate;

(3-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate;

(4-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (3-methylphenyl) iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate;

2 [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate;

[2- (2,2-dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2- (2,2-dicyano-1-phenylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2- (2,2-dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2- (3-ethoxy-2-ethoxycarbonyl-3-oxoprop-1-enyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2 - [(E) -2-cyano-1-methylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate.

The preferred novel iodonium salts are listed in Table No. 1 below with the chemical names, structural formulas, and acronyms given.

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Table number 1

Preferred iodonium salts according to the invention.

Preferred iodonium salts are the anterior the subject of the invention - basic structures Z 'i? o ° Ol pf ₈ CN L Jl CN OX 24-180 basic structure 1 24-181 basic structure 2 [2-j (E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyl iodonium hexafluorophosphate [2- (2,2-dicyanovinite) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate Co-operative iodonium salts with the cation [2 - [(E) -2-cyanovinyl-4,6 <phymethoxyphenyl} thenyiodonium coordinated with different anions pp Ol SbF ₆ 'kJ With 0 L ł m \ Κ-Τ / Λ O ° s 24-180 basic structure 1 24-175 24-176 | 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate [2 [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate ⁺ CF3SO3 O 1-CN TT Cl B (CeF ₅ ), TT AI (OC (CF ^) 3) 4 ^ 0 24-177 24-178 24-179 [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyl iodonium triflate [2-KE) -2-cyanovinyl] -4,6 · dimethoxyphenyl | phenyliodonium tetrapentafl uorophenylborate (2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium alkoxyaluminate (fAI (OC (CF3) 3) 4 |) Preferred iodonium salts with the cation [2- (2,2 <flcyanovinio} -4,6-dimethoxyphenylphenyl] iodonium coordinated with different anions f Λ O ° And after \ ^ω 0— <® ¹ z Cc ^bf "LT CN" 0 24-181 basic structure 2 24-182 24-183 [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyl iodonium tetrafluoroborate

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Ok, * CFiSaT CN \ ⁰⁵ o · / $ o zl Al (OC (CF3) ₃ ) ^CN ^ O 24-184 24-185 24-186 [2- (2,2-Dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium triflate [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate [2- (2,2-dicyanovinyio) -4,6-dimethoxyphenyl] phenyliodonium alkoxyaluminate ([Al (OC (C Fihh] ^- ) Preferred iodonium salts are cation derivatives [2 - [(E) -2-cyanovinyl] -4 , 6-dimethoxyphenyl] phenyl iodonium > Q \ _ / ⁺ z) uo z CN ^PF ^ .o Ύ] ^p Fg ^- 30-105 30-025 30-024 (2-cyanophenyl) - [2 - ((E) -2cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate (3-cyanophenyl) - [2 - [(E) -2cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate (4-cyanophenyl) - [2 - [(E) -2cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate ΓΥΡ PFe Yj 3 ° O ~ o z WITH AT 1 \ £ // CL < p ° ·. 30-023 30-022 30-094 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2-methylphenyl] iodonium hexafluorophosphate 24 (E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (3-methylphenyl) iodonium hexafluorophosphate 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate \ I about z pf ₆ 1 ' With o ° x O ° x 29-026 29-025 24-180 basic structure 1 2 [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate 2 - ((E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl) phenyl iodonium hexafluorophosphate Preferred iodonium salts derived from the cation [2- (2,2-dicyanovinylp l ₁ 6-dimethoxyphenyl] phenyliodoniumflo ^:

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_{PFg from} O. 1 / sCfi ^CN O _O _Q-C // Λ ¹ o— <1 ^of 0 o with ® + / \ οΓ 24-181 basic structure 2 27-124 30-083 [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexatluorophostorane [2- (2,2-dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate [2- (2,2-dicyano-1-phenylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate Z z £ ⁰ O 27-117 [2- (2,2-dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenylpyodonium hexafluorophosphate The preferred iodonium salts of the invention (IL / Ł \ ⁰ 0 of 30-041 31-032 | 2- (3-ethoxy-2-ethoxycarbonyl-3oxoprop-1-enyl) -4,6-dimethoxyphenyl] phenyl iodonium hexafluorophosphate [2 - [(E) -2-cyano-1-methylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

The present invention also relates to a process for the preparation of new iodonium salts. Method for the preparation of new iodonium salts of general formula (1)

wherein

Ri is -H, -CN, -COOC2H5;

R2 is -CN, -COOC2H5;

R3 is -H, -OCH3, -CH3, -Ph;

R4-R8 are each independently -H, -CN, -CH3, -CH (CH3) 2;

E ~ is an anion selected from the group consisting of PFe ", SbFe", BF4 ~, CFsSOs ", B (C6F5) 4 ~, [Al (OC (CF ₃ ) 3) 4]", characterized by dissolving in acetic acid is the compound of general formula (2)

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(2), wherein the meaning of the substituents Ri to R3 is as in general formula (1), and diacetoxyiodo-benzene or a derivative thereof encompassed by general formula (3) with

(3), in which the meaning of substituents from R4 to Re is as in the compound of general formula (1), and then an inorganic acid selected from the group consisting of sulfuric acid (VI), nitric acid and phosphoric acid (VI) is added, and the reaction is carried out by mixing the reagents in the temperature range from room temperature 20 ° C to 80 ° C for a period of 5 minutes to 240 minutes, monitoring the progress of the reaction, and then, after reacting the reactants, an inorganic or organic-inorganic salt selected from the group consisting of KPFe, NaSbFe, NaBF4, CF3SO3K, (CeFs ^ BNa, NaPFe, KSbFe, KBF4, CFsSOsNa, (CeFs ^ BLi, [Al (OC (CF3) 3) 4] Li and acetic anhydride, and stirring is continued at a temperature from room temperature of 20 ° C to 80 ° C for a period of 1 minute to 60 minutes, then added water and the product precipitated out, washed with water and dried.

Preferred compounds of general formula (2) are compounds selected from the group consisting of: (E) -3- (3,5-dimethoxyphenyl) prop-2-enenitrile, 2 - [(3,5-dimethoxyphenyl) methylene] propanedinitrile, 2- [1- (3,5-dimethoxyphenyl) ethylidene] propanedinitrile, 2- [1- (3,5-dimethoxyphenyl) phenylmethylene] propanedinitrile, 2 - [(3,5-dimethoxyphenyl) methoxymethylene] propanedinitrile, 2 - [( Diethyl 3,5-dimethoxyphenyl) methylene] malonate, (E) -3- (3,5-dimethoxyphenyl) but-2-enenitrile.

Preference is given to using compounds of the general formula (3) selected from the group consisting of: diacetoxy iodobenzene, 2'-cyano-diacetoxy iodobenzene, 3'-cyano-diacetoxyiodine benzene, 4'-cyano-diacetoxy iodobenzene, 2'-methyl-diacetoxy iodobenzene, 3'-methylenediacetene , 4'-methyl-diacetoxy iodobenzene, 4'-isopropyl-diacetoxy iodobenzene, 2 ', 4', 6'-trimethyl-diacetoxy iodobenzene.

Preferably, the reaction of the compounds of general formulas (2) and (3) is carried out in a molar ratio of the compound (2) to the compound (3) ranging from 1: 1 to 1: 2.

Preferably, the reaction of the compounds of general formulas (2) and (3) is carried out in a molar ratio of the compound (2) to the compound (3) of 1: 1.1.

According to a preferred version of the process according to the invention, the compound of general formula (2) and the compound of general formula (3) are reacted by stirring the reagents at 50 ° C for a period of 2 h, monitoring the progress of the reaction using thin layer chromatography (TLC) and then after reacting the reactants, an inorganic or organo-inorganic salt, preferably potassium hexafluorophosphate, and acetic anhydride are added to the mixture and stirring is continued at a temperature of up to 70 ° C for at least 5 minutes, then water is added, and then the filtered and washed product is dried outdoors.

According to a preferred version of the process of the invention, new iodonium salts are prepared selected from the group consisting of: [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyl iodonium hexafluorophosphate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

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[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium triflate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium alkoxyaluminate ([Al (OC (CF3) 3) 4]);

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium triflate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium alkoxyaluminate ([Al (OC (CF3) 3) 4]);

(2-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate;

(3-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate;

(4-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (3-methylphenyl) iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate;

2 [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate;

[2- (2,2-dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2- (2,2-dicyano-1-phenylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2- (2,2-dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2- (3-ethoxy-2-ethoxycarbonyl-3-oxoprop-1-enyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2 [(E) -2-cyano-1-methylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate.

The present invention also relates to the use of the new iodonium salts of general formula (1)

wherein

Ri is -H, -CN, -COOC2H5;

R2 is -CN, -COOC2H5;

R3 is -H, -OCH3, -CH3, -Ph;

R4-R8 are each independently -H, -CN, -CH3, -CH (CH3) 2;

E ~ is an anion selected from the group consisting of PFe ", SbFe", BF4 ~, CFsSOs ", B (C6F5) 4 ~, [Al (OC (CF ₃ ) 3) 4]", as photoinitiators for the photoinitiated cationic polymerization of monomers that can be polymerize in cationic polymerization processes.

According to a preferred version of the application, the cationic polymerization is carried out as a ring-opening polymerization or as a chain polymerization.

According to a preferred version of the use, the ring-opening polymerization monomers are at least one monomer selected from the group consisting of cycloaliphatic epoxy monomers, preferably 3,4-epoxycyclohexanecarboxylate-3,4-epoxycyclohexylmethyl (CADE - CAS number 2386 87-0), cyclohexene oxide (CAS number 286-20-4) or glycidyl monomers selected from tris (4-hydroxyphenyl) methane triglycidyl ether (CAS number 66072-38-6), 1,4-butanediol diglycidyl ether (CAS number 2425 79-8), bis [4- (glycidyloxy) phenyl] methane (CAS number 2095-03 6), bisphenol A diglycidyl ether (CAS number 1675-54-3), bisphenol F diglycidyl ether (CAS number 2095 03-6).

According to a preferred version of the use, at least one monomer selected from the group consisting of vinyl ethers, preferably triethylene glycol divinyl ether (TEGDVE - CAS number 765-12-8), divinyl glycol divinyl ether is used as monomers for the chain polymerization.

PL237 731 Β1 (DEGDVE - CAS number 764-99-8), 1,4-cyclohexanedimethanol divinyl ether (CAS number 17351-75-6), 1,4-butanediol divinyl ether (CAS number 3891-33-6), ether polyethylene glycol divinyl (CAS number 50856-26-3).

According to a preferred version of the application, the mixture to be polymerized contains additional initiators, additional monomers and moreover sensitizers, stabilizers, modifiers, regulators, solvents, fillers, dyes, pigments and mixtures thereof.

According to a preferred embodiment of the application, the iodonium salts are selected from the group consisting of: [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium triflate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium alkoxyaluminate ([Al (OC (CF3) 3) 4]);

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium triflate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium alkoxyaluminate ([Al (OC (CF3) 3) 4]);

(2-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate;

(3-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate;

(4-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (3-methylphenyl) iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate;

[2- (2,2-dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2- (2,2-dicyano-1-phenylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2- (2,2-dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2- (3-ethoxy-2-ethoxycarbonyl-3-oxoprop-1-enyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2 [(E) -2-cyano-1-methylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate.

During the work on new iodonium salts, it was surprisingly found that new intermediates for the synthesis of new iodonium salts had been developed.

The invention therefore also relates to novel intermediates for the synthesis of new iodonium salts.

New 2- [1- (3,5-dimethoxyphenyl) ethylidene] propanedinitrile of formula (4)

New 2- [1- (3,5-dimethoxyphenyl) phenylmethylene] propanedinitrile of formula (5)

New 2 - [(3,5-dimethoxyphenyl) methoxymethylene] propanedinitrile of formula (6)

PL 237 731 Β1 θ ''

LY CN (6).

New (E) -3- (3,5-dimethoxyphenyl) but-2-enenitrile of formula (7)

Yj (7).

The invention also relates to methods for the preparation of new compounds of the formulas (4), (5), (6) and (7).

A method for producing the new 2- [1- (3,5-dimethoxyphenyl) ethylidene] propanedinitrile of formula (4)

LJI CN (4) is characterized by the fact that 3 ', 5'-dimethoxyacetophenone of formula (8) is introduced into the reactor

and malonodinitrile, which are dissolved in an organic solvent selected from the group consisting of chloroform, acetone, dichloromethane and ethyl acetate, then titanium (IV) chloride and a basic agent selected from the group consisting of pyridine, piperidine, morpholine and triethylamine are added dropwise to the resulting mixture, and then the contents of the reactor are stirred for a period from 1 h to 6 h at room temperature, monitoring the progress of the reaction, after which the dilute acid is dosed into the reactor in the form of 10% aqueous hydrochloric acid or 10% aqueous sulfuric acid (VI ) and extraction of the reactor contents with an organic solvent selected from the group consisting of ethyl acetate, diethyl ether, toluene and tetraphydrofuran, and then the combined organic layers are washed with water and brine, dried over a drying agent selected from anhydrous sodium sulfate and anhydrous sulfate of magnesium (VI), the drying agent is filtered off, the filtrate is concentrated by rotary evaporation the crude product residue is purified.

According to a preferred version of the process according to the invention, 3 ', 5'-dimethoxyacetophenone and malonodinitrile are dissolved in dichloromethane, titanium (IV) chloride and pyridine are added dropwise to the resulting mixture, and the reactor contents are stirred for 4 h at room temperature, monitoring the progress of the reaction using thin layer chromatography (TLC), then 10% aqueous hydrochloric acid is added and the reactor contents are extracted with ethyl acetate, the combined organic layers are washed with water and brine, dried over anhydrous sodium sulfate and then the drying agent is filtered off and concentration of the filtrate, the crude product is purified by column chromatography.

PL237 731 Β1

The method of producing the new 2- [1- (3,5-dimethoxyphenyl) phenylmethylene] propanedinitrile of formula (5)

characterized in that (3,5-dimethoxyphenyl) phenylmethanone of formula (9) is introduced into the reactor

and malonodinitrile, which are dissolved in an organic solvent selected from the group consisting of chloroform, acetone, dichloromethane and ethyl acetate, then titanium (IV) chloride and a basic agent selected from the group consisting of pyridine, piperidine, morpholine and triethylamine are added dropwise to the resulting mixture, and then the contents of the reactor are stirred for a period from 1 h to 6 h at room temperature, monitoring the progress of the reaction, after which the dilute acid is dosed into the reactor in the form of 10% aqueous hydrochloric acid or 10% aqueous sulfuric acid (VI ) and extraction of the reactor contents with an organic solvent selected from the group consisting of ethyl acetate, diethyl ether, toluene and tetrahydrofuran, and then the combined organic layers are washed with water and brine, dried over a drying agent selected from anhydrous sodium sulfate and anhydrous sulfate of magnesium (VI), the drying agent is filtered off, the filtrate is concentrated by rotary evaporation the crude product residue is purified.

According to a preferred version of the process according to the invention, 2- [1- (3,5-dimethoxyphenyl) phenylmethylene] propanedinitrile and malonodinitrile are dissolved in dichloromethane, titanium (IV) chloride and pyridine are added dropwise to the resulting mixture, and the reactor contents are stirred for 4 hours in room temperature while monitoring the progress of the reaction by thin layer chromatography, after the reaction is completed, 10% aqueous hydrochloric acid is added and the contents of the reactor are extracted with ethyl acetate, the combined organic layers are washed with water and brine, dried over anhydrous sulfate (VI) sodium, and after filtering off the drying agent and concentrating the filtrate, the crude product is purified by column chromatography.

A method for producing a new 2 - [(3,5-dimethoxyphenyl) methoxymethylene] propanedinitrile of formula (6)

(6) is characterized by the following steps:

- step A), in which a 60% (m / m) suspension of sodium hydride in tetrahydrofuran is introduced into the reactor, a solution of malonodinitrile in tetrahydrofuran is added to the reactor, and after 15 min. While stirring, a solution of 3,5-dimethoxybenzoyl chloride in tetrahydrofuran is added, and the reagents are stirred for a period of 10 minutes to 120 minutes at 0 ° C, after which the reactor contents are further stirred for up to 6 h to 18 h at room temperature, monitoring the progress of the reaction, and after its completion, water and hydrochloric acid are added to the reactor until the reaction mixture is pH = 3, then the mixture is extracted with an organic solvent selected from the group consisting of ethyl acetate, diethyl ether, toluene and tetrahydrofuran,

The combined organic layers are washed with water and brine, dried over a drying agent selected from anhydrous sodium sulfate and anhydrous magnesium sulfate, then the drying agent is filtered off, the filtrate is concentrated and the residue is purified to give 2- (3,5-dimethoxybenzoyl) propanedinitrile which is used as starting material in step B);

- step B) in which a mixture of 1,4'dioxane and water is introduced into the reactor, to which 2- (3,5-dimethoxybenzoyl) propanedinitrile has been added, then sodium bicarbonate and methyl sulfate are added and the reactor contents are heated to boiling for a period from 1 h to 5 h, monitoring the progress of the reaction, and after its completion and cooling the reaction mixture to room temperature, water is added and extraction is carried out with an organic solvent selected from the group consisting of ethyl acetate, diethyl ether, toluene and tetrahydrofuran, the combined organic layers are washed brine, dried over a drying agent selected from anhydrous sodium sulfate and anhydrous magnesium sulfate, then the drying agent was filtered off, the filtrate was concentrated on a rotary evaporator and the residue, the crude end product, was purified.

According to a preferred version of the process according to the invention, in step A), after adding a solution of 3,5-dimethoxybenzoyl chloride in tetrahydrofuran to the contents of the reactor, the reactants are stirred for 1 h at 0 ° C and 12 h at room temperature, monitoring the progress of the reaction by means of thin layer chromatography (TLC). ), and after adding water and hydrochloric acid and adjusting the reaction mixture to pH = 3, this mixture is extracted with ethyl acetate, and after washing the combined organic layers, they are dried over anhydrous sodium sulphate, and then the drying agent is filtered off and concentrated of the filtrate, the residue is purified by column chromatography;

In step B), the reagents are boiled for 2 h, monitoring the progress of the reaction by thin layer chromatography (TLC), after completion of the reaction and cooling of the reaction mixture, water is added and the reaction mixture is extracted with ethyl acetate, the combined organic layers after washing with brine are dried over with anhydrous sodium sulfate, and after the drying agent has been filtered off and the filtrate is concentrated, the residue is purified by column chromatography.

Method for the preparation of the new (E) -3- (3,5-dimethoxyphenyl) but-2-enenitrile of formula (7)

characterized in that a 60% (m / m) suspension of sodium hydride in tetrahydrofuran is introduced into the reactor, a solution of diethyl cyanomethylphosphate in tetrahydrofuran is added to the reactor and the contents of the reactor are stirred for a period from 5 minutes to 60 minutes, then a solution of 3 ', 5'-dimethoxyacetophenone in tetrahydrofuran is added and stirring is continued at room temperature for 1 h to 6 h while monitoring the progress of the reaction, and upon completion of the reaction, an aqueous saturated ammonium chloride solution is added and the contents of the reactor are extracted With ethyl acetate, the combined organic layers are washed with brine, dried over a drying agent selected from anhydrous sodium sulfate and anhydrous magnesium sulfate, the drying agent is filtered off, the filtrate is concentrated on a rotary evaporator, and the crude residue is cleans up.

According to a preferred version of the process according to the invention, a 60% (m / m) suspension of sodium hydride in tetrahydrofuran is introduced into the reactor at 0 ° C, a solution of diethyl cyanomethylphosphate in tetrahydrofuran is added to the reactor, and the reactor contents are stirred for 15 minutes, and then added solution of 3 ', 5'-dimethoxyacetophenone in tetrahydrofuran and continued stirring at room temperature for 3 h, monitoring the progress of the reaction using thin layer chromatography (TLC), followed by extraction, washing the combined organic layers with brine, drying them over anhydrous sodium sulfate, and after filtering off the drying agent and concentrating the filtrate, the residue is purified by column chromatography.

PL237 731 Β1

The invention also relates to the use of compounds of general formula (2)

wherein

Ri is -H, -CN, -COOC2H5;

R2 is -CN, -COOC2H5;

R3 is -H, -OCH3, -CH3, -Ph;

for the preparation of iodonium salts of general formula (1)

wherein

R1 is -H, -CN, -COOC2H5;

R2 is -CN, -COOC2H5;

R3 is -H, -OCH3, -CH3, -Ph;

R4-R8 are each independently -H, -CN, -CH3, -CH (CH3) 2;

E is an anion selected from the group consisting of PFe, SbFe, BF4, CF3SO3, B (CeF5) 4, [Al (OC (CF ₃ ) 3) 4] ".

Preferred is the use of compounds of general formula (2) for the preparation of iodonium salts selected from the group consisting of: [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyl iodonium hexafluorophosphate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium triflate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate;

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium alkoxyaluminate ([Al (OC (CF3) 3) 4]);

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium triflate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate;

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium alkoxyquinate ([Al (OC (CF3) 3) 4]);

(2-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate;

(3-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate;

(4-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (3-methylphenyl) iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate;

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate;

2 [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate;

[2- (2,2-dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2- (2,2-dicyano-1-phenylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2- (2,2-dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2- (3-ethoxy-2-ethoxycarbonyl-3-oxoprop-1-enyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate;

[2 - [(E) -2-cyano-1-methylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate.

PL 237 731 Β1

The invention has been illustrated in more detail and explained in non-limiting examples.

EXAMPLES

Example 1 Preparation of iodonium salts of the invention coordinated with the [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyl iodonium cation and various anions.

STEP 1 - (E) -3- (3,5-dimethoxyphenyl) prop-2-enenitrile (24-150)

3,5-dimethoxybromobenzene (0.1 mol), acrylonitrile (0.4 mol), Pd (dppf) Cl2CH2Cl2 (0.005 mol), K2CO3 (0.15 mol) and NBu4Br (0.01 mol) were dissolved in N -methylpyrrolidone (200 ml). The resulting solution was stirred at 120 ° C under an inert gas atmosphere for 8 h. The reaction was monitored by thin layer chromatography (TLC). Water (1000 ml) was added and the resulting mixture was extracted with ethyl acetate, the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, the drying agent was filtered off, the filtrate was concentrated on a rotary evaporator and the residue was recrystallized from methanol to give white crystals.

Spectral data:

(E) -3A3,5-dimethoxyphenyl) prop'2-enenitrile (24-150) T J Ή NMR (400 MHz, de- DMSO) δ 7.55 (cl, J - 16.7 Hz, 1H), 6.85 (d, J - ^ 0 2.2 Hz, 2H), 6.59 (t, J = 2.2 Hz, 1H), 6.51 (d, J - 16.7 Hz, 1H), 3.77 (a, 6H)

STEP 2 - Synthesis of the iodonium salts of the invention coordinated with the [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium cation and various anions.

(E) -3- (3,5-dimethoxyphenyl) prop-2-enenitrile (0.01 mol) and diacetoxy-iodobenzene (0.011 mol) were dissolved in acetic acid (20 ml), then sulfuric acid (VI) (0.011 mol) was added and the resulting mixture was stirred for 2 h at 50 ° C. The progress of the reaction was monitored by thin layer chromatography (TLC). Then ion exchange was performed by adding KPFe (0.011 mol) and acetic anhydride (20 ml). Stirring was continued at 50 ° C for 5 min. Water (200 ml) was added and the resulting precipitate was filtered off, washed with water and air dried.

The salts used for this reaction step depending on the obtained derivative of the iodonium salt with the cationic center in the form of [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium were KPF ₆ , NaSbF ₆ , NaBF ₄ , CF3SO3K, (C ₆ F ₅ ) 4BLi, [Al (OC (CF ₃ ) ₃ ) 4] Li.

Spectral data:

> p) Ό 0 z 2 [(E) -2cyπvinylol · 4,6-dimethoxyphenylphenylphenyliodonium hexafluorophosphate 24 * 180 Ή NMR (400 MHz, de- DMSO) δ 8.10 (d, J = 7.6 Hz, 2H), 8.09 (d, J = 16.3 Hz, 1H), 7.64 (t, J = 7.4 Hz, 1H), 7.50 (t , J = 7.6 Hz, 2H), 7.15 (d, J = 2.3 Hz, 1H), 6.91 (d, J = 2.3 Hz, 1H), 6.69 (d, J = 16.3 Hz, 1H), 3.97 (s, 3H ). 3.89 (s, 3H) Ol SbF ₆ Yj f2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate 24-175 Ή NMR (400 MHz, de- DMSO) δ 8.11 (d, J = 7.6 Hz, 2H), 8 09 (d, J = 16.5 Hz, 1H), 7.64 (t, J = 7.4 Hz, 1H), 7.50 ( t, J = 7.6 Hz, 2H), 7.15 (d, J = 2.2 Hz, 1H), 6.91 (d, J - 2.2 Hz, 1H), 6.69 (d, J = 16.4 Hz, 1H), 3.97 (s, 3H), 3.89 (s, 3H)

PL237 731 Β1

WITH ABOUT '? □ 7 \ m \ j-yh O ° x f2-KE) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyl iodonium tet rafluoroborate 24-176 Ή NMR (400 MHz, de- DMSO) δ 8.10 (d, J = 7.6 Hz, 2H), 8.09 (d, J = 16.2 Hz, 1H), 7.64 (t, J - 7.4 Hz, 1H), 7.50 (t , J = 7.6 Hz, 2H), 7.15 (d, J = 2.3 Hz, 1H), 6.91 (d, J = 2.3 Hz, 1H), 6.69 (d, J = 16.3 Hz, 1H), 3.97 (s, 3H ). 3.89 (s, 3H) S. | * CF3SO3 ^ 0 [2 - [(E) -2-cyanovinylol · 4,6-dimethoxyphenyl] phenyliodonium triflate 24-177. NMR (400 MHz, d _e - DMSO) 8 8.10 (d, J = 7.6 Hz, 2H), 8.09 (d , J - 16.3 Hz, 1H), 7.64 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.6 Hz, 2H), 7.15 (d, J = 2.3 Hz, 1H), 6.91 (d, J = 2.3 Hz, 1H), 6.69 (d, J = 16.3 Hz, 1H), 3.97 (s, 3H), 3.89 (s, 3H) Λ 9 \ w of l 12 - [(E) -2 cyanovinyl] '4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate 24-178 Ή NMR (400 MHz, d ₆ - DMSO) 8 8.12 (d, J = 7.4 Hz, 2H), 8.10 (d, J - 16.3 Hz, 1H), 7.64 (t, J = 7.4 Hz, III), 7.51 (t, J - 7.4 Hz, 2H), 7.15 (d, J = 2.3 Hz, 1H), 6.93 (d, J = 2.3 Hz, 1H), 6.70 (d, J = 16.3 Hz, IH), 3.97 (s, 3H), 3.90 (s, 3H) rj ^ Al (OC (CF3) 3) 4 ^ .O | 24 (E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium alkoxyaluminate ([AliOCiCFsWJ ^- ) 24-179 'H NMR (400 MHz, de-DMSO) δ 8.13 (d, J = 7.4 Hz, 2H) , 8.10 (d, J = 16.3 Hz, 1H), 7.64 (t, J = 7.4 Hz, 1H), 7.52 (t, J = 7.4 Hz, 2H), 7.15 (d, J = 2.3 Hz, 1H), 6.93 (d, J = 2.3 Hz, 1H), 6.73 (d, J = 16.3 Hz, 1H), 3.97 (s, 3H), 3.90 (s, 3H)

Example 2 Preparation of iodonium salts of the invention coordinated with the [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium cation and various anions.

STEP 1 - 2 - [(3,5-dimethoxyphenyl) methylene] propanedinitrile (26 057)

3,5-dimethoxybenzaldehyde (1 mol) and malononitrile (1 mol) were dissolved in methanol (500 ml), piperidine (0.1 mol) was added and the mixture was stirred at 25 ° C for 4 hours. The progress of the reaction was monitored by thin layer chromatography (TLC). The volatiles were evaporated and the residue was recrystallized from methanol.

Spectral data:

2 - [(3,5-dimethoxyphenyl) methylene] propanedinitrile (26Ό57) ^ .O CN > H NMR (400 MHz, de-DMSO) 8.42 (s, 1H). 7.11 (d, J = 2.2 Hz, 2H), 6.83 (t, J = 2.2 Hz, 1H), 3.80 (s, 6H)

PL 237 731 Β1

STEP 2 - Synthesis of the diaryliodonium salt of the invention coordinated with the [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium cation and various anions.

2 - [(3,5-dimethoxyphenyl) methylene] propanedinitrile (26-057) (0.01 mol) and diacetoxyiodinitrile (0.011 mol) were dissolved in acetic acid (20 ml), then sulfuric acid (VI) (0.011 mol) was added and the resulting mixture was stirred for 2 h at 50 ° C. The progress of the reaction was monitored by thin layer chromatography (TLC). Then, ion exchange was performed by adding KPFe, (0.011 mol) and acetic anhydride (20 ml). Stirring was continued at 50 ° C for 5 min. Water (200 ml) was added and the resulting precipitate was filtered off, washed with water and air dried.

The salts used for this reaction step depending on the obtained derivative of the iodonium salt with the center in the form of the [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium cation were KPF ₆ , NaSbF ₆ , NaBF ₄ , CF3SO3K, (C ₆ F ₅ ) ₄ BLi, [Al (OC (CF ₃ ) ₃ ) 4] Li.

Spectral data:

Ol p _F6 LJJ CN O [2- (2,2-Dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate (24-181) NMR (400 MHz, de * DMSO) δ 9.05 (s, 1H). 8.20-8.16 (m, 211), 7.67 (tt, J = 7.5, 1.1 Hz, 1H), 7.52 (tt, J = 7.8, 1.9 Hz, 2H), 7.27 (d, J = 2.5 Hz, 1H), 7.01 (d, J = 2.5 Hz, 1H), 3.99 (s, 3H), 3.89 (s, 3H) WITH And k * u? ώ / 7 w \ O [2- (2,2-Dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate (24-182) Ή NMR (400 MHz, de-DMSO) δ 9.05 (s, 1H), 8.20-8.16 (m, 2H), 7.67 (tt, J = 7.7, 1.1 Hz, 1H), 7.52 (tt, J = 7.9, 1.9 Hz, 2H), 7.27 (d, J = 2.5 Hz, 1H), 7.00 (d, J = 2.5 Hz, 1H), 3.99 (s, 3H), 3.89 (s, 3H) ^ O ^ k ^^ CN kJJ CN [2- (2,2-Dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate (24-183) > H NMR (400 MHz, de- DMSO) 6 9.03 (s, 1H), 8.20 8.16 (m, 2H), 7.67 (tt, J = 7.5, 1.1 Hz, 1H), 7.52 (tt, J = 7.8, 1.6 Hz, 2H), 7.27 (d, J = 2.4 Hz, 1H), 7.01 (d, J = 2.4 Hz, 1H), 4.00 (s, 3H). 3.89 (s, 3H) CFjSCh ^- kPI CN O [2- (2,2-Dicyanovinic)) - 4,6-dimethoxyphenyl] phenyl iodonium triflate. (24184) • H NMR (400 MHz, de-DMSO) δ 9.05 (s, 1H), 8.21-8.16 (m, 2H), 7.67 (tt, J = 7.5, 1.1 Hz, 1H), 7.52 (tt, J = 7.8, 1.9 Hz, 2H), 7.27 (d, J = 2.5 Hz, 1H), 7.01 (d, J = 2.5 Hz, 1H), 3.99 (s, 3H), 3.90 (s, 3H) > p ' _O -Q— <\ OJ UA, Tl ^z 0 gz I [2- (2,2-Dicyanovinyl) -4,6-dimethoxyphenylphenyl] iodonium tetrapentafluorophenylborate (24-185) • H NMR (400 MHz, dr DMSO) δ 9.08 (s, 1H), 8.208.16 (m, 2H), 7.65 (tt, J = 7.5, 1.1 Hz, 1H), 7.52 (tt, J = 7.8, 2.2 Hz, 2H), 7.27 (d, J = 2.5 Hz, 1H), 7.01 (d, J = 2.5 Hz, 1H), 4.01 (s, 3H), 3.91 (s, 3H) Ipk AI (OC (CF)) ₃ ) * ^, O ^^ k_x¾_, CN kjl CN _x o [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium alkoxyaluminate ([AKOCKCFaiahO (24-186) • H NMR (400 MHz, d ₆ - DMSO) 6 9.09 (s, 1H), 8.20-8.16 (m , 211), 7.65 (tt, J = 7.5, 1.1 Hz, 1H), 7.55 (tt, J = 7.8, 2.2 Hz, 2H), 7.27 (d, J = 2.5 Hz, 1H), 7.01 (d, J = 2.5 Hz, 1H), 4.01 (s, 3H), 3.93 (s, 3H)

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Example 3 Preparation of [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] aryliodonium salts formed by reaction with various diacetoxyiodonium derivatives.

^ cn

STEP 1 - (E) -3- (3,5-dimethoxyphenyl) prop-2-enenitrile (24-150)

This step repeats step number 1 of example number 1.

STEP 2 - Synthesis of [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] aryliodonium salts formed by reaction with various diacetoxyiodonium derivatives.

2 - [(3,5-dimethoxyphenyl) methylene] propanedinitrile (26-057) (0.01 mol) and diacetoxyiodoarene (0.011 mol) were dissolved in acetic acid (20 ml), then sulfuric acid (VI) (0.011 mol) was added and the resulting mixture was stirred for 2 h at 50 ° C. The progress of the reaction was monitored by thin layer chromatography (TLC). Then, ion exchange was performed by adding KPFe (0.011 mol) and acetic anhydride (20 ml). Stirring was continued at 50 ° C for 5 min. Water (200 ml) was added and the resulting precipitate was filtered off, washed with water and air dried.

Derivatives of diacetoxyiodiodobenzene in this synthesis stage were respectively: 2'-cyanodiacetoxyiodiodobenzene, 3'-cyanodiacetoxyiodo-benzene, 4'-cyanodiacetoxyiodo-benzene, 2'-methyldiacetoxyiodo-benzene, 3'-methyldiacetoxy-iodobenzene, 4'-methyldiacetoxy-iodobenzene, 4'-methyenzo-iodiacy-ethyldiacet. 6'-trimethyl diacetoxy iodobenzene.

Spectral data:

x o z about z (2-cyanophenyl) - (2-I (E) -2-cyanovinyl] -4,6-dimethoxyphenyl] o} iodonium hexafluorophosphate (30 '105) 1 H NMR (400 MHz, de-DMSO) δ 8.29 (dd, J = 7.9, 1.2 Hz, 1H), 8.10 (d, J - 16.3 Hz, 1H), 8.07 (dd, J = 7.5, 1.7 Hz, 1H ), 7.76 (td, J - 7.5, 1.4 Hz, 1H), 7.71 (dd, J = 7.7, 2.0 Hz, 1H), 7.14 (d, J = 2.4 Hz, 1H), 6.83 (d, J = 2.4 Hz , 1H), 6.71 (d, J = 16.3 Hz, 1H), 3.91 (s, 3H), 3.87 (s, 3H) CN ίίι ^PF ® ~ (3-cyanophenyl) - [2-l (E) -2-cyanovinyl] -4,6-dimethoxyphenyl-iodonium hexafluorophosphate (30-025) Ή NMR (400 MHz, de-DMSO) δ 8.74 (t, J = 1.7 Hz, 1H), 8.40 (dt, J = 8.2, 1.4 Hz, 1H), 8.10 (d, J = 16.1 Hz, 1H), 8.10 (t, J = 1.1 Hz, 1H), 7.68 (t, J = 8.1 Hz, 1H), 7.16 (d, J = 2.6 Hz, 1H), 6.90 (d, J - 2.6 Hz, 1H), 6.69 (d , J = 16.1 Hz, 1H), 3.96 (s, 3H), 3.89 (s, 3H) \ "O ( ^Z ° l 0 z (4-cyanophenyl) - [2 - [(E) -2 * cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate (30,024) NMR (400 MHz, d _G - DMSO) δ 8.27 (d, J = 8.2 Hz, 2H) , 8.10 (d, J = 16.0 Hz, 1H), 7.96 (d, J = 8.2 Hz, 1H), 7.17 (d. J = 2.3 Hz, 1H), 6.92 (d, J = 2.3 Hz, 1H), 6.71 (d, J = 16.0 Hz, 1H), 3.95 (s, 3H), 3.90 (s, 3H) j ° q \ i about z 2 - [(E) -2-cyanovinyio] * 4,6-dimethoxyphenyl] '(2-methylphenyl) iodonium hexafluorophosphate 30Ό23 > H NMR (400 MHz, de-DMSO) δ 8.12-8.06 (m, 2H), 7.56-7.51 (m, 2H), 7.27-7.22 (m, 114), 7.14 (d, J = 2.2 Hz, 1H) , 6.88 (d, J = 2.2 Hz, 1H), 6.70 (d, J = 16.1 Hz, 1H), 3.92 (s, 3H), 3.88 (s, 3H). 2.58 (s, 3H)

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\ 1 about z 2 - [(E) '2-cyanovinyl]' 4,6'-methoxyphenyl] '(3'-methylphenyl) iodonium hexafluorophosphate 30 022 Ή NMR (400 MHz, dc DMSO) δ 8.09 (d, J = 16.1 Hz, 1H), 7.98.7.97 (m, 1H), 7.89 (d, J = 8.2 Hz. 1H), 7.45 (d, J = 7.7 Hz. 1H), 7.37 (t, J = 7.7 Hz, 1H), 7.13 (d, J = 2.5 Hz, 1H), 6.90 (d, J = 2.5 Hz, 1H). 6.68 (d, J = 16.0 Hz, 1H), 3.98 (s, 3H), 3.89 (s, 3H), 2.34 (s, 3H) \ 1 about with 2 - [(E) -2-cyanovinyl] 4,6-dimethoxyphenylH4-methylphenyl) iodonium hexafluorophosphate 30Ό94 > H NMR (400 MHz, dc DMSO) δ 8.08 (d, J = 16.1 Hz. 1H), 7.98 (dt, J = 8.5, 2.3 Hz, 2H), 7.29 (dt, J = 8.5, 2.3 Hz, 2H) , 7.13 (cl, J = 2.6 Hz, 1H), 6.89 (d, J - 2.6 Hz, 1H), 6.68 (d, J = 16.1 Hz, 1H), 3.97 (s, 3H), 3.89 (s, 3H) , 2.33 (s. 3H) \ / ^ χ, ° W> Ό // ę "। about Z 2l (E) -2 cyanvinylol 4,6-dimethoxyphenylol (4 isopropylphonyl) iodonium hexafluorophosphate 29Ό26 Ή NMR (400 MHz, de * DMSO) δ 8.10 (d, J = 16.1 Hz, 1H), 8.01 (dt, J = 8.6, 2.1 Hz, 2H), 7.37 (dt, J = 8.6, 2.1 Hz, 2H) , 7.14 (d, J = 2.6 Hz, 111), 6.91 (d, J = 2.6 Hz, 1H), 6.69 (d, J = 16.1 Hz, 1H), 3.99 (s, 311), 3.89 (s, 3H) , 2.92 fouin, J - 6.8 Hz, 1H), 1.17 (d, J = 6.8 Hz, 6H) XX pf ₆ - 1 * JOj 2i (E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate 29 * 025 Ή NMR (400 MHz, dc DMSO) 6 7.97 (d, J = 16.2 Hz, 1H), 7.17 (d, J = 2.5 Hz, 1H), 7.14 (s, 2H), 6.86 (d, J = 2.5 Hz, 11D, 6.75 (d, J = 16 2 Hz, 1H). 3.89 (s, 3H), 3.81 (s, 3H), 2.51 (s, 9H)

Example 4 Synthesis of [2- (2,2-dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate (27-124)

STEP 1 - 2- [1- (3,5-Dimethoxyphenyl) ethylidene] propanedinitrile 27-121

3 ', 5'-dimethoxyacetophenone (0.05 mol) and malononitrile (0.12 mol) were dissolved in dichloromethane (300 ml). Titanium (IV) chloride (0.25 mol) and pyridine (90 ml) were added dropwise to the resulting mixture. The mixture was stirred for 4 hours at room temperature. The progress of the reaction was monitored by thin layer chromatography (TLC). Then 10% hydrochloric acid (500 ml) was added and the whole was extracted with ethyl acetate, the combined organic layers were washed with water and brine, dried over anhydrous sodium sulfate, the drying agent was filtered off, the filtrate was concentrated by rotary evaporation, and the residue was purified by column chromatography. .

Spectral data:

o ^ 7 o — x z 2'll- (3,5 dimethoxyphenyl) ethylideneJpropanedinitrile 27-121 Ή NMR (400 MHz, dc DMSO) δ 6.82 (d, J = 2.2 Hz, 2H), 6.72 (t, J = _x o 2.2 Hz, 1H), 3.80 (s, 6H), 2.61 (s, 3H)

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STEP 2 - [2 (2,2-Dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate (27-124)

2- [1- (3,5-dimethoxyphenyl) ethylidene] propanedinitrile (0.01 mol) and diacetoxyiodinitrile (0.011 mol) were dissolved in acetic acid (20 ml), then sulfuric (VI) acid (0.011 mol) was added and the resulting mixture it was stirred for 2 h at 50 ° C. The progress of the reaction was monitored by thin layer chromatography (TLC). Then, ion exchange was performed by adding KPFe (0.011 mol) and acetic anhydride (20 ml). Stirring was continued at 50 ° C for 5 min. Water (200 ml) was added and the resulting precipitate was filtered off, washed with water and air dried.

Spectral data:

Z ° _x z ¹ 11? . o. \ O £ [2- (2,2-Dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate (27-124) Ή NMR (400 MHz, de- DMSO) δ 8.05-8.02 (m, 2H), 7.65 (tt, J = 7.3, 1.1 Hz, 1H), 7.51 (tt, J = 7.7, 1.8 Hz, 2H), 6.98 ( d, J = 2.6 Hz, 1H). 6.87 (d, J - 2.6 Hz, 1H), 4.11 fe, 3H), 3.88 (s, 3H), 2.66 (s, 3H)

Example 5 Synthesis of [2- (2,2-dicyano-1-phenylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate (30-083)

STEP 1- 2- [1- (3,5-Dimethoxyphenyl) phenylmethylene] propanedinitrile 30 077 (3,5-dimethoxyphenyl) phenylmethanone (0.05 mol) and malononitrile (0.12 mol) were dissolved in dichloromethane (300 ml). Titanium (IV) chloride (0.25 mol) and pyridine (90 ml) were added dropwise to the resulting mixture. The mixture was stirred for 4 hours at room temperature. The progress of the reaction was monitored by thin layer chromatography (TLC). Then 10% hydrochloric acid (500 ml) was added and the whole was extracted with ethyl acetate, the combined organic layers were washed with water and brine, dried over anhydrous sodium sulfate, the drying agent was filtered off, the filtrate was concentrated by rotary evaporation, and the residue was purified by column chromatography. .

Spectral data:

2- [1- (3,5-dimethoxyphonyl) -phenylmethylene] propanedinitrile

Ή NMR (400 MHz, de- DMSO) δ 7.66 (tt, J = 7.2, 1.4 Hz, 1H), 7.57 (tt, J = 7.5, 1.6 Hz, 2H), 7.53-7.50 (m, 2H), 6.78 ( t, J = 2.3, HI), 6.62 (d, J = 2.2 Hz, 2H), 3.76 (s, 6H)

STEP 2 - [2- (2,2-Dicyano-1-phenylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate (30,083)

2- [1- (3,5-dimethoxyphenyl) -phenylmethylene] propanedinitrile (0.01 mol) and diacetoxyiodinitrile (0.011 mol) were dissolved in acetic acid (20 ml), then sulfuric acid (VI) (0.011 mol) was added and the resulting the mixture was stirred for 2 h at 50 ° C. The progress of the reaction was monitored by thin layer chromatography (TLC). Then, ion exchange was performed by adding KPFe (0.011 mol) and acetic anhydride (20 ml). Stirring was continued at 50 ° C for 5 min. Water (200 ml) was added and the resulting precipitate was filtered off, washed with water and air dried.

PL 237 731 Β1

Spectral data:

pf ₆ ' [2 (2,2-dicyano-1-phenylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate (30-083) Λ o Ή NMR (400 MHz, de- DMSO) δ 7.70 (tt, J = 7.2,1.4 Hz, 1H), 7.63 (d, J = _z ° llcN 7.2 Hz, 2H), 7.58 (d, J = 7.5 Hz, 2H), 7.54 (d, J = 7.7 Hz, 1H), 7.38 (d, J = 2.6 Lj! CN Hz, 1H), 7.33 (t, J = 7.4 Hz, 2H), 7.28-7.24 (m, 2H), 7.07 (d, J = 2.6 Hz, 1H), 4.06 (s, 3H), 3.96 (s, 3H)

Example 6 Synthesis of [2- (2,2-dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate (27-117)

STEP 1-2 (3,5-dimethoxybenzoyl) propanedinitrile 27-115

To a suspension of sodium hydride (60%, 0.02 mol) in tetrahydrofuran (4 ml) was added a solution of malononitrile (0.01 mol) in tetrahydrofuran (4 ml) at 0 ° C. After 15 min. With stirring, a solution of 3,5-dimethoxybenzoyl chloride (0.01 mol) in tetrahydrofuran (4 ml) was added, then stirring was continued for 1 h at 0 ° C and 12 h at room temperature. The progress of the reaction was monitored by thin layer chromatography (TLC). Water (20 ml) and hydrochloric acid were added to give Ph = 3. The resulting mixture was extracted with ethyl acetate, the combined organic layers were washed with water and brine, dried over anhydrous sodium sulfate, the drying agent was filtered off, the filtrate was concentrated, and the residue was used directly in the next stage.

STEP 2 - 2 - [(3,5-dimethoxyphenyl) methoxymethylene] propanedinitrile 27-116

2- (3,5-dimethoxybenzoyl) propanedinitrile (0.005 mol) and sodium bicarbonate (0.040 mol) and methyl sulfate (0.035 mol) were added to a mixture of 1,4-dioxane (10 ml) and water (2 ml). It was then heated to reflux for 2 h. The progress of the reaction was monitored by thin layer chromatography (TLC). After cooling the reaction mixture to room temperature, water (30 ml) was added and the whole was extracted with ethyl acetate, the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, the drying agent was filtered off, the filtrate was concentrated by rotary evaporation, and the residue was purified by chromatography. columnar.

Spectral data:

CN 2 - [(3,5-dimethoxyphenyl) methoxymethylenolpropanedinitrile 27-116 Ή NMR (400 MHz, de- DMSO) δ 6.83 (d, J = 2.2 Hz, 2H), 6.79 (t, J = 2.2 Hz, 1H), 3.90 (s, 3H), 3.81 (s, 6H)

STEP 3 - [2- (2,2-Dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate (27-117)

2 - [(3,5-dimethoxyphenyl) methoxymethylene] propanedinitrile (0.01 mol) and diacetoxyiodinitrile (0.011 mol) were dissolved in acetic acid (20 ml), then sulfuric (VI) acid (0.011 mol) was added and the resulting mixture was stirred for 2 h at 50 ° C. The progress of the reaction was monitored by thin layer chromatography (TLC). Then, ion exchange was performed by adding KPFe, (0.011 mol) and acetic anhydride (20 ml). Stirring was continued at 50 ° C for 5 min. Water (200 ml) was added and the resulting precipitate was filtered off, washed with water and air dried.

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Spectral data:

Ol ^pf ® ~ ^cn ^ .0 [2 (2,2-dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenyldonium hexafluorophosphate (27-117) Ή NMR (400 MHz, de-DMSO) δ 7.99-7.96 (m, 2H), 7.67 (mp, J - 7.4, 1.0 Hz, 1H), 7.53 (tt, J = 7.6, 1.7 Hz, 2H), 7.16- 7.15 (m, 2H), 4.16 (s, 3H), 3.93 (s, 3H), 3.88 (s, 3H)

Example 7 Synthesis of [2- (3-ethoxy-2-ethoxycarbonyl-3-oxoprop-1-enyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate 30-041

STEP 1 -2 - [(3,5 dimethoxyphenyl) methylene] diethyl malonate 27-178

3,5-dimethoxybenzaldehyde (1 mol) and diethyl malonate (1 mol) were dissolved in methanol (500 ml), piperidine (0.1 mol) was added and the mixture was stirred at 25 ° C for 4 hours. The progress of the reaction was monitored by thin layer chromatography (TLC). The volatiles were evaporated and the residue was recrystallized from methanol.

Spectral data:

Diethyl 2 - ((3,5-dimethoxyphenyl) methylene] malonate 27-178

Ή NMR (400 MHz, de-DMSO) δ 7.67 (s, 1H), 6.69 (d, 1 = 2.2 Hz, 2H), 6.63 (t, J = 2.2 Hz, 1H), 4.31-4.22 (m, 4H) , 3.75 (s, 6H), 1.26 (t, J = 7.0 Hz, 3H), 1.23 (t, J = 7.1 Hz, 3H)

STEP 2 - [2- (3-ethoxy-2-ethoxycarbonyl-3-oxoprop-1-enyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate 30-041

Diethyl 2 - [(3,5-dimethoxyphenyl) methylene] malonate (0.01 mol) and diacetoxyodobenzene (0.011 mol) were dissolved in acetic acid (20 ml), then sulfuric (VI) acid (0.011 mol) was added and the resulting mixture was stirred 2 h at 50 ° C. The progress of the reaction was monitored by thin layer chromatography (TLC). Then, ion exchange was performed by adding KPFe, (0.011 mol) and acetic anhydride (20 ml). Stirring was continued at 50 ° C for 5 min. Water (200 ml) was added and the resulting precipitate was filtered off, washed with water and air dried.

Spectral data:

'-o) = oo / = \ / O ^-0 o Diethyl 2 - ((3,5-dimethoxyphenyl) methylene] malonate 27-178 Ή NMR (400 MHz, de-DMSO) δ 7.67 (s, 1H), 6.69 (d, 1 = 2.2 Hz, 2H), 6.63 (t, J = 2.2 Hz, 1H), 4.31-4.22 (m, 4H) , 3.75 (s, 6H), 1.26 (t, J = 7.0 Hz, 3H), 1.23 (t, J = 7.1 Hz, 3H)

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Example 8 Synthesis of [2 - [(E) -2-cyano-1-methylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate 31-032

STEP 1 - (E) -3- (3,5-dimethoxyphenyl) but-2-enenitrile 31-057

A solution of diethyl cyanomethylphosphate (0.05 mol) in tetrahydrofuran (10 ml) was added to a suspension of sodium hydride (60%, 0.05 mol) in tetrahydrofuran (20 ml) at 0 ° C, followed by stirring for 15 minutes. A solution of 3 ', 5'-dimethoxyacetophenone (0.04 mol) in tetrahydrofuran (10 ml) was added and stirring was continued at room temperature for 3 h. The progress of the reaction was monitored by thin layer chromatography (TLC). Aqueous saturated ammonium chloride solution was added and the whole was extracted with ethyl acetate, the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, the drying agent was filtered off, the filtrate was concentrated by rotary evaporation, and the residue was purified by column chromatography.

Spectral data:

With u 9 o \ (E) -3 '(3,5-dimethoxyphenyl) but-2-enenitrile ΡΗΤ31Ό57 NMR (400 MHz, de-DMSO) δ 6.76 (d, J = 2.2 Hz, 2H), 6.60 (t, J = 2.2 Hz, 1H). 6.14 (d, J = 1.0 Hz, 1H), 3.78 (s. 6H), 2.39 (d, J = 1.0 Hz, 3H)

STEP 2 - [2 - [(E) -2 cyano-1-methylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate 31-032 (E) -3- (3,5-dimethoxyphenyl) but-2-enenitrile (0 0.1 mol) and diacetoxy-iodobenzene (0.011 mol) was dissolved in acetic acid (20 ml), then sulfuric (VI) acid (0.011 mol) was added and the resulting mixture was stirred for 2 h at 50 ° C. Then, ion exchange was performed by adding KPFe (0.011 mol) and acetic anhydride (20 ml). Stirring was continued at 50 ° C for 5 min. Water (200 ml) was added and the resulting precipitate was filtered off, washed with water and air dried. The progress of the reaction was monitored by thin layer chromatography (TLC).

Spectral data:

li and ^PFe ~ _z o A z ° [2-1 (E) -2-cyano-1-methylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate 31-032 Ή NMR (400 MHz, de- DMSO) δ 7.95-7.92 (m, 2H), 7.66 (tt, J = 7.4, 1.0 Hz, 1H), 7.52 (tt, J = 7.7, 1.9 Hz, 2H), 6.87 ( d, J = 2.6 Hz, 1H), 6.78 (d, J = 2.6 Hz, 1H), 5.66 (d, J - 1.2 Hz, 1H), 4.02 (s, 3H), 3.87 (s, 3H), 2.37 ( d, J = 1.2 Hz, 3H)

Example 9 Investigation of the absorption characteristics of the obtained iodonium salts in order to determine their suitability as photoinitiators of polymerization processes.

Absorption studies

The Silver Nova spectrometer by StellarNet Inc. was used to measure the absorption of the tested derivatives of iodonium salts. (USA), which has a spectral range of 190-1100 nm. Measurements were made in spectroscopically pure acetonitrile (Sigma Aldrich), using a quartz cuvette with an optical path length of 1 cm. The light source was a deuterium-halogen lamp by StellarNet Inc. (USA). All measurements were made at room temperature. In order to test the effectiveness of the compounds of the invention as photoinitiators, measurements of their molar absorption coefficients as a function of wavelength were carried out. Table 2 compares the obtained values of the molar absorption coefficients in the maximum of the absorption band and at the wavelengths characteristic for the maximum emission of medium-pressure mercury lamps, i.e. 365 nm and diodes

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UV-LED 365 nm and Vis-LED 405 nm. Values of the same parameter are also shown for commercial photoinitiators with the same or a different anion.

Table number 2

Quantitative parameters describing the absorption properties of the iodonium salts of the present invention and of the commercially available photoinitiators.

Relationship no Structure Amax [nm] Cniax | dm ^a mole ¹ cm Ί C365 [dm ³ mol · ¹ cm * 1 C405 Idm 'mole ¹ cm' 1 --.- I P 'Ύ- ^: 'ίΑ ; · Ώ7’Τ i? T :: TJiii · Fotoinicj commercial attributes HłP σ'Ό 228 14600 0 0 Speedcure 938 annuities ρτ'τρ 242 16503 0 0 Omnicat 440 Refe 241 13830 0 0 Irgacure 250 242.1 14522 0 0

Cationic photoinitiators according to the invention with different cationic centers.

PL 237 731 Β1

(2-f (E) -2-cyanovinyl J4,6-dimethoxyphenyl) phenyl or odonium hexafluorophosphate 24-180 * ^pF s ^- _x o 240 24500 920 0 [2- (2,2-dicyanovinyl) 4,6-dimethoxyphenyl | phenylpyranium hexafluorophosphate 24-181 Ol LJi CN 303 10,000 2200 385 [2- (3-ethoxy-2-ethoxycarbonyl-3-oxoprop-1-phenyl) -4,6-dimethoxyphenyl] phenyl] odonium hexafluorophosphate 30-041 about L J Y O ^ O 204 31650 440 0 ii. (2-cyanophenylH2 - ((E) 2-cyanovinyl] -4,6-dimethoxyphenyl | iodonium hexafluorophosphate 30-105 ii Ψ 204 29800 675 0 (3-cyanophenyl) - [2 - [(E) 2-cyanovine (o] -4,6d-methoxyphenyl] iodonium hexafluorophosphate 30-025 CN Π ^PF · 'Ψ 206 29700 790 0 (4-cyanophenyl) - [2 - [(E) 2-cyanovinyl] -4,6-dimethoxyphenyl-iodonium hexafluorophosphate 30-024 at 2 235 24300 855 0 2 - [(E) -2-cyanovinyl J-4,6-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate 30-023 and 241 21,000 625 0 2 - [(E) -2-cyanovinyl] 4,6-idethoxyphenyl] - (3-methylphenyl) iodonium hexafluorophosphate 30-022 δ 'at? 0. ( -O o \ = / \ 240.5 21550 665 0 2 - [(E) -2-cyanovinyl) 4,6-dimethoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate 30-094 Bi ^pf » 242 24250 795 0

PL237 731 Β1

2 - [(E) -2-cyanovinyl] 4,6-dimethoxyphenyl] - (4-isopropylphenyl] iodonium hexafluorophosphate 29-026 about z 233 21750 690 0 2 - [(E) -2-cyanovinyl | 4,6-dimethoxyphenyl] (2,4,6-trimethylphenyl] iodonate hexafluorophosphate 29-025 A 1 * 243 27800 885 0 - [2- (2,2-dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyl] odonium hexafluorophosphate 27-124 z \ z ¹ JP Zr O 204 27350 515 0 [2- (2,2-dicyano-1-phenylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate 30-083 a, .o 309.5 15700 1310 0 [2- (2,2-dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenyl] odonium hexafluorophosphate 27-117 \ = s / TJ Ο-Ϋ ^{x 2} Λ z 303 7530 365 0

PL 237 731 Β1

Wavelength [nm]

24-180 basic structure 1 [2 - [(E) -2-cyanovinyl] -4,6di methoxyphenyloylenyl iodonium hexafluorophosphate

24-181 basic structure 2 [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenylenic hexafluorophosphate

[2- (3-ethoxy-2-ethoxica ± ionyl-3-oxoprop-1-phenyl) -4,6-dimethoxyphenyl] phenylqiodonium hexafluorophosphate

Graph 1. Graph of the dependence of extinction on the wavelength for the iodonium salts of the invention coordinated with different cationic centers

PL237 731 Β1

Wavelength [nm]

30-105

30-025

(2-cyanophenyl) - [2 - [(E) -2 cyanovinyl] -4 ₍ 6-dimethoxyphenyl] iodonium hexafluorophosphate (3-cyanophenyl) - [2-I (E) -2 cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate (4-cyanophenyl) [2-cyanophenyl] iodonium hexafluorophosphate [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate

24-180 basic structure 1 [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyl iodonium hexafluorophosphate

Graph 2. Extinction versus wavelength plot for the inventive iodonium salts coordinated with different cationic centers.

PL 237 731 Β1

Wavelength [nm]

30-023

2 - ((E) -2-cyanovinyl | -4,6-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate

2 - [(E) -2-cyanovinyl] 4,6-dimethoxyphenyl] (3-methylphenyl) iodonium hexafluorophosphate

30-094

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-methylphenyl] iodonium hexafluorophosphate

basic structure 1

[2-NE) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

Graph of the extinction versus wavelength for the inventive iodonium salts coordinated with different cationic centers.

PL237 731 Β1

30-094

2 - [(E) -2-cyanovinyl J-4,6-dimethoxyphenyl] (4-methylphenyl] iodonium hexafluorophosphate

24-180 basic structure 1 [2 - [(E) -2cyanovinyl] -4,6-dimethoxyphenyl] phenyl oodonium hexafluorophosphate

30-024

29-026

29-025 (4-cyanophenyl) - [2 - [(E) 2-cyanovinyl] -4,6-dimethoxyphenyl | iodonium hexafluorophosphate

2 - [(E) -2-cyanovinyl] 4,6-dimethoxyphenyl J- (4-isopropylphenyl) iodonium hexafluorophosphate

2 - [(E) -2-cyanovinyl] 4,6-dimethoxyphenyl] (2.4,6-trimethylphenyl) iodonium hexafluorophosphate

Graph 4. Extinction-wavelength plot for the inventive iodonium salts coordinated with different cationic centers.

PL 237 731 Β1

basic structure 2 [2- (2,2-di cyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

[2- (2,2-dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

[2- (2,2-dicyano-1fenylowinylo) -4 6dimetoksyfenylo _l] fenylojodoni head hexafluorophosphate (2- (2,2-dicyano-1metoksywinylo) -4,6dimetoksyfenylo] fenylojodoni head hexafluorophosphate

Graph 5. Extinction-wavelength plot for the inventive iodonium salts coordinated with different cationic centers.

Example 10 Investigation of the kinetics of cationic photopolymerization by the FT-IR method in order to determine the suitability of the developed iodonium salts as photoinitiators of photopolymerization processes.

The FTIR - Jasco FT / IR-4700 spectrophotometer equipped with a horizontal adapter was used to study the photopolymerization processes with the real time FT-IR method. A 365 nm UV-LED diode of 190 mW nominal power emitting light perpendicular to the sample surface with a wavelength of Xmax = 365 nm was used as the light source. Measurements were carried out for up to 900 seconds, and the obtained data were saved in the SPECTRA MENAGER program, dedicated to the processing of FT-IR spectra. Data were recorded in a darkened room with only red light lamps used as lighting.

PL237 731 Β1

Preparation of samples for monitoring the photopolymerization process using the real time FT-IR method

Compositions for real time FT-IR tests were prepared in dark amber glass vials in a darkened room. Each composition contained 2 wt. of the iodonium initiator in relation to the total composition, which was an epoxy monomer in the form of a cycloaliphatic epoxy resin with the acronym CADE produced by Lambson. A drop of the prepared measuring composition was placed on a barium fluoride pellet with a diameter of φ = 25 ± 0.2 mm x 5 ± 0.1 mm using a glass pipette in the case of monitoring the cationic photopolymerization processes. After that, the pellet was put on a metal holder and placed in the horizontal adapter of the spectrometer. Measurements were made while maintaining the same thickness of the applied layer of the composition, amounting to 25 μητ, respectively. 10 seconds after starting the MENAGER SPECTRA software recording the IR spectrum, the UV-LED diode emitting light with a wavelength of Xmax = 365 nm was turned on. All compositions were tested in a room with limited daylight. Thanks to the combination of registration of the infrared spectrum of individual compositions in time, with simultaneous exposure of the sample to a given light source, it is possible to observe the photopolymerization reaction in real time. Peak intensity change with appropriate wavenumbers:

• For cationic photopolymerization of CADE epoxy monomer (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl-methyl carboxylate produced by Lambson) at 790 cm ' ¹ and 1080 cm ^-1 • For cationic photopolymerization of the vinyl monomer TEGDVE (Triethylene glycol divinyl ether) in the production of a band with a length of 1630 cm ^-1 indicates the effective course of the photopolymerization process. The functional group conversion can be calculated from the following formula:

K = (l- (A / Ao »* 100% where:

K - conversion

A - value of the area of the band monitored during the photopolymerization process as a function of time

Ao - initial band area value at the monitored wavenumber • Cationic photopolymerization of CADE epoxy monomer (3,4-epoxycyclohexanecarboxylate 3,4-epoxycyclohexylmethyl at 365 nm wavelength).

Table number 3

Data collected during measurements of the photopolymerization process of the epoxy monomer with the ring opening at a wavelength of 365 nm and the setting of 700 mA as well as data for photopolymerization at a wavelength of 405 nm (visible range) and 1000 mA using the FT-IR technique in compositions containing iodonium salts subject of the present invention or commercial photoinitiators.

Relationship no Structure Conversion (K) [% 1 _: UV-LED 365 nm CADE epoxy monomer Conversion (K) [%] Vis * LED 405 nm CADE epoxy monomer Commercial derivatives of diaryliodonium salts - HJP X PFx no polymerization no polymerization Speedcure 938 PF. _: no polymerization no polymerization

PL 237 731 Β1

Omnical 440 no polymerization no polymerization Irgacure 250 xr'A no polymerization no polymerization Cationic photoinitiators according to the invention with different cationic centers. [2 - [(E) -2-cyanovinyl] -4,6-dt-methoxyphenyl] phenyliodonium hexafluorophosphate 24-180 L O o z 68 15 [2- (2,2-Dicyanovinyl) -4,6-dimethoxyphenyl] phenyldonium hexafluorophosphate 24-181 Cl ppf LII cn 75 64 [2- (3-ethoxy-2-ethoxycarbonyl-3-oxoprop-1-phenyl) -4,6-dimethoxyphenyl] phenyldonium hexafluorophosphate 30-041 W Ί / -o> o 'o ⁾ I 38 no polymerization (2-cyanophenyl) - (2 - [(E) -2cyanovinyl | -4,6-dimethoxyphenyl] iodonium hexafluorophosphate 30-105 with ¹ o 'i? 46 no polymerization (3-cyanophenyl) - [24 (E) -2-cyanovinyl | -4,6-dimethoxyphenyl] iodonium hexafluorophosphate 30-025 1 1 ¹ ) '1 C 7 1 ¹ 45 no polymerization (4-cyanophenyl) - [2 - [(E) -2cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate 30-024 di ' About z 42 no polymerization 2 - [(E) -2-cyanovinyl | -4,6-dimethoxyphenyl] - (2-methylphenyl] iodonium hexafluorophosphate 30-023 OC ^{PF $} 46 no polymerization 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (3-methylphenyl] iodonium hexafluorophosphate 30-022 ck- ^PF '- 51 no polymerization 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-methylphenyl] iodonium hexafluorophosphate 30-094 about z 36 no polymerization

PL237 731 Β1

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4- (zopropylphenyl) iodonium hexafluorophosphate 29-026 ^PFg Ψ _x o 45 no polymerization 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl ]- (2,4,6-trimethylphenyl) iodonium hexafluorophosphate 29-025 pi '^ r' ^p fr l ^ł φ no polymerization no polymerization j: N ”·; . :; .... [2- (2,2-dicyano-1-methylvinyl) 4,6- dimethoksyphenyljphenyliodonium hexafluorophosphate 27-124 p '„/ AC o- # ii ² 2 28 no polymerization [2- (2,2-dicyan o-1-phenylvinyl) 4,6-dimethoxyphenyl] phenyl iodonium hexafluorophosphate 30-083 , PP o- # \ ~ / ^z oz 33 no polymerization [2- (2,2-Dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate 27-117 with Until O ~ 4 i £,) = \ i O ° x 22 no polymerization

PL 237 731 B1

Conversion [%] • 10

100 200 300 400 500 600 700 800 900

Time [s]

24-180

24-181

30-041

24-180 basic structure 1 | 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyl iodonium hexafluorophosphate

24-181 basic structure 2

[2- (2,2-dicyanovinyio) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

[2- (3-ethoxy-2-ethoxycarbonyl-3-oxoprop-1-phenyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

Graph G. Comparison of the kinetics of the cationic photopolymerization process of CADE epoxy monomer during irradiation with light with a wavelength of 365 nm and settings of 700 mA for iodonium salts coordinated with different cationic centers.

PL237 731 Β1

ΡΗΤ24-181

-10 I I ’I ι ι’ and -r-r

100 200 300 400 500 600 700 800 900

Time [s]

24-181 basic structure 2 | 2- (2,2-dicyanovine! O) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

27-124

[2- (2,2-dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

[2- (2,2-dicyano-1-phenylvinyl) -4,6-dimethoxyphenyl | phenyl iodone hexafluorophosphate

^ .o

27-117 (2- (2,2-dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

Graph 7. Comparison of the kinetics of the cationic photopolymerization process of CADE epoxy monomer during irradiation with light with a wavelength of 365 nm and settings of 700 mA for iodonium salts coordinated with different cationic centers.

PL 237 731 Β1

30-105

30-025

24-180 (2-cyanophenyl) -12 - [(E) -2 cyanovinyl) -4,6-dimethoxyphenyliodonium hexafluorophosphate (3-cyanophenyl) - [2 - [(E) -2 cyanovinyl] -4,6 dimethoxyphenyl] iodonium hexafluorophosphate phenyl (4) ) - [2 - [(E) -2cyanovinyl | -4,6-dimethoxyphenyl] iodonium hexafluorophosphate basic structure 1

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

Graph 8. Comparison of the kinetics of the cationic photopolymerization process of CADE epoxy monomer during irradiation with light with a wavelength of 365 nm and settings of 700 mA for iodonium salts coordinated with different cationic centers.

PL237 731 Β1.

ΡΗΤ24-180

-i 0 'ί -'- Ί -5 — τη — I — ΓΤ “! * and —I —— Γ “Γ — ΤΤ” · Γ ’-» - ΓΤ

100 200 300 400 500 600 700 800 900

Time [s]

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate

2 - [(E) -2-cyanovin1o | 4,6-dimethoxyphenyl] (3-methylphenyl) iodonium hexafluorophosphate

30-094

2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl) - (4-methylphenyl) iodonium hexafluorophosphate

24-180 basic structure 1 [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyl iodonium hexafluorophosphate

Graph 9. Comparison of the kinetics of the cationic photopolymerization process of CADE epoxy monomer during irradiation with light with a wavelength of 365 nm and settings of 700 mA for iodonium salts coordinated with different cationic centers.

PL 237 731 Β1 <ρ ·

ΈΓ g 40 ο

0

’1’

100 200 300 400 500 600 700 800 90C

Time [s]

2 - [(Ε) -2-cy novany) o | 4,6-dimethoxyphenyl] (4-methylphenyl) iodonium hexafluorophosphate

24-180 basic structure 1 (2 - [(E) -2cyanovinyl] -4,6-dimethoxyphenyl] phenyl) oodonium hexafluorophosphate

(4-cyanophenyl) - [2 - [(E) - 2 - ((E) -2-cyanovinyl] - 2 - [(E) -2-cyanovine! O] 2-cyanovinyl] -4.6- 4, 6-dimethoxyphenyl] - (4- 4,6-dimethoxyphenyl] dimethoxyphenyl] iodonio isopropylphenyl) iodonium (trimethylphenyl 2,4,6w hexafluorophosphate) iodonium hexafluorophosphate hexafluorophosphate

Graph 10. Comparison of the kinetics of the cationic photopolymerization process of CADE epoxy monomer during irradiation with light with a wavelength of 365 nm and settings of 700 mA for iodonium salts coordinated with different cationic centers.

PL237 731 Β1

Ο 100 200 300 400 500 600 700 800 900

Time [s]

24-180 basic structure 1 [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl | phenyl iodonium hexafluorophosphate

24-181 basic structure 2 (2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

Graph 11. Comparison of the kinetics of the cationic photopolymerization process of CADE epoxy monomer during irradiation with light with a wavelength of 405 nm 1 A for iodonium salts coordinated with different cationic centers.

• Cationic photopolymerization of TEGDVE vinyl monomer (triethylene glycol divinyl ether) at 365 nm and in the visible range at 405 nm.

PL 237 731 Β1

Table number 4

Data collected during measurements of the course of the photopolymerization process of TEGDVE vinyl monomer at a wavelength of 405 nm (with a power of 1000 mA) as well as for tests at a wavelength of 365 nm (with a power of 700 mA) using the FT-IR technique in compositions containing iodonium salts that are subject of the present invention

Relationship no Structure Conversion (K) 1%] UV-LED 365 nm TEGDVE vinyl monomer Conversion (K) 1%] Vis-LED 405 nm TEGDVE vinyl monomer Commercial derivatives of diaryliodonium salts HIP . PF.- no polymerization no polymerization Speedcure 938 no polymerization no polymerization Omnicat 440 no polymerization no polymerization lrgacure 250 ^pf «A no polymerization no polymerization Cationic photoinellators wec Hug of the invention with 2 different cationic centers. [2 - [(E) -2-cyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate 24-180 '° o 0 Z i 93 71 [2- (2,2-dicyanovinite) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate 24-181 Ol _PFe - LJl CN 89 90 [2- (3-ethoxy-2-ethoxycabonyl-3-oxoprop-1-phenyl) -4,6-dimethoxyphenyl] phenyl iodonium hexafluorophosphate 30-041 Ol ^pFe '0 ^ 0 38 no polymerization (2-cyanophenyl) - [2 - [(E) -2cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate 30-105 3 ° 0 ° -ó-- § 0 Z 84 no polymerization (3-cyanophenyl) - [2 - [(E) -2cyanovinyl] -4,6-dimethoxyphenyliodonium hexafluorophosphate 30-025 zu ^S -O < 92 no polymerization

PL237 731 Β1

(4-cyanophenyl) - [2 - [(E) -2cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate 30-024 ¹ o of ^z 94 no polymerization 2- | (E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate 30-023 iZE ^PFe 93 no polymerization 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (3-methylphenyl] iodonium hexafluorophosphate 30-022 Ck ,. Ie O Χ ' 92 no polymerization 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-methylphenyl] iodonium hexafluorophosphate 30-094 With □ L- / > - 0-0. P ° x 92 no polymerization 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate 29-026 about z 92 no polymerization 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2,4,6-tri-methylphenyl] iodonium hexafluorophosphate 29-025 A - 1 * Ie 92 no polymerization [2- (2,2-dicyano-1-methylvinyl) 4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate 27-124 O — Y 1 ^of oz 92 52 (2- (2,2-dicyano-1-phenylvinyl) 4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate 30-083 PF _e Οι (ΓΊ] ^cn 93 91 [2- (2,2-dicyano-1-methoxyvinyl) 4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate 27-117 with V with u? θ ”\. A O ° x 89 5

PL 237 731 B1

Conversion [%]

basic structure 1

[2 - [(E) -2-cyanovin) o] -4,6-dimethoxyphenyl] phenyl iodonium hexafluorophosphate

24-181 basic structure 2

[2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

[2- (3-ethoxy-2-ethoxycfoonyl-3-oxoprop-1-phenyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

Diagram 12. Comparison of the kinetics of the cationic photopolymerization of TEGDYE vinyl monomer during irradiation with light with a wavelength of 365 nm (at 0.7 A) for iodonium salts coordinated with different cationic centers.

PL237 731 Β1

basic structure 2 [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

[2- (2,2-dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

[2- (2,2-dicyano-1-phenylvinyl) -4,6-dimethoxyphenyl} phenyliodonium hexafluorophosphate

[2- (2,2-dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

Diagram 13. Comparison of the kinetics of the cationic photopolymerization of TEGDVE vinyl monomer during irradiation with light with a wavelength of 365 nm (at 0.7 A) for iodonium salts coordinated with different cationic centers.

PL 237 731 Β1

100 200 300 400

Time [S]

30-105

30-025

(2-cyanophenyl) - [2 - ((E) -2 cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate (3-cyanophenyl) - (2 - [(E) -2 cyanovinyl] -4,6 dimethoxyphenyl iodonium hexafluorophosphate

30-024 (4-cyanophenyl) - [2 - [(E) -2cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate

24-180 basic structure 1

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodium hexafluorophosphate

Figure 14. Comparison of the kinetics of the cationic photopolymerization of TEGDVE vinyl monomer during irradiation with light with a wavelength of 365 nm (at 0.7 A) for iodonium salts coordinated with different cationic centers.

PL237 731 Β1

2 - [(E) -2-cyanavinyl | -4,6-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate

2 - [(E) -2-cyanovinyl J-4,6-dimethoxyphenyl] (3-methylphenyl! O) iodonium hexafluorophosphate

2 - [(E) -2-cyanovinyl) -4,6-dimethoxyphenyl] - (4-methylphenyl] iodonium hexafluorophosphate basic structure 1

[2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

Figure 15. Comparison of the kinetics of the cationic photopolymerization of TEGDVE vinyl monomer during irradiation with light with a wavelength of 365 nm (at 0.7 A) for iodonium salts coordinated with different cationic centers.

PL 237 731 Β1

30-094

2 - [(E) -2-cyanovinyl) 4,6-dimethoxyphenyl] (4-methylphenyl) odonium hexafluorophosphate

24-180 basic structure 1 | 2 - [(E) -2cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate

30-024 29-026 29-025 (4-cyanophenyio) - [2 - [(E) 2-cyanovinyl-I-4,6-dimeloxyphenyl] iodonium hexafluorophosphate

2- | (E) -2-cyanovinyl | 4,6-di methoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate

2 - [(E) -2cyanovinyl] -4,6-dimethoxyphenyl] (2,4,6-trimethytophenyl] iodonium hexafluorophosphate

Figure 16. Comparison of the kinetics of the cathionic photopolymerization of TEGDVE vinyl monomer during irradiation with light with a wavelength of 365 nm (at 0.7 A) for iodonium salts coordinated with different cationic centers.

PL237 731 Β1

Time [s]

Chart 17. Comparison of the kinetics of the cationic photopolymerization of TEGDVE vinyl monomer during irradiation with light with a wavelength of 405 nm (at 1 A) for iodonium salts coordinated with different cationic centers

Claims (2)

1. New iodonium salts of general formula (1) wherein Ri is -H, -CN, -COOC2H5; R2 is -CN, -COOC2H5; R3 is -H, -OCH3, -CH3, -Ph; R4-R8 are each independently -H, -CN, -CH3, -CH (CH3) 2; PL 237 731 Β1 E is an anion selected from the group consisting of PFe, SbFe, BF4, CF3SO3, B (CeF5) 4, [Al (OC (CF ₃ ) 3) 4] ". 2. The iodonium salt according to claim 1 1 selected from the group consisting of: [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium triflate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium alkoxyaluminate ([Al (OC (CF3) 3) 4]); [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium triflate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium alkoxyquinate ([Al (OC (CF3) 3) 4]); (2-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate; (3-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate; (4-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate; 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate; 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (3-methylphenyl) iodonium hexafluorophosphate; 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate; 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; 2 [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate; [2- (2,2-dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2- (2,2-dicyano-1-phenylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2- (2,2-dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2- (3-ethoxy-2-ethoxycarbonyl-3-oxoprop-1-enyl) -4,6-dimethoxyphenyl] phenyliodonium h e xaf I u o rophosphate; [2 - [(E) -2-cyano-1-methylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate. 3. The method of producing new iodonium salts of general formula (1) R? wherein R1 is -H, -CN, -COOC2H5; R2 is -CN, -COOC2H5; R3 is -H, -OCH3, -CH3, -Ph; R4-R8 are each independently -H, -CN, -CH3, -CH (CH3) 2; E ~ is an anion selected from the group consisting of PFe ", SbFe", BF4 ~, CFsSOs ", B (C6F5) 4 ~, [Al (OC (CF ₃ ) 3) 4]", characterized by dissolving in acetic acid compound of general formula (2) (2), PL237 731 Β1 wherein the meaning of Ri to R3 is as in general formula (1), and diacetoxyiodo-benzene or a derivative thereof encompassed by general formula (3) with (3), in which the meaning of the substituents R4 to R8 is as in the compound of general formula (1), and then an inorganic acid selected from the group consisting of sulfuric acid), nitric acid (V) and phosphoric acid (VI) are added, and the reaction is carried out by mixing the reagents in the temperature range from 20 ° C to 80 ° C for a period of 5 minutes to 240 minutes, monitoring the progress of the reaction, and then, after reacting the reactants, an inorganic or organic-inorganic salt selected from the group consisting of KPFe, NaSbFe, NaBF ₄ , CF3SO3K, (C ₆ F ₅ ) 4BNa, NaPF ₆ , KSbF ₆ , KBF ₄ , CF ₃ SO ₃ Na, (C ₆ F ₅ ) 4BLi, [AI (OC (CF3) 3) 4 ] Li and acetic anhydride, and stirring is continued at 20 ° C to 80 ° C for 1 minute to 60 minutes, then water is added and the precipitate product is filtered off, washed with water and dried. 4. The method according to p. A process according to claim 3, characterized in that the compounds of general formula (2) are compounds selected from the group consisting of: (E) -3- (3,5-dimethoxyphenyl) prop-2-enenitrile, 2 - [(3,5-dimethoxyphenyl) methylene] propanedinitrile, 2- [1- (3,5-dimethoxyphenyl) ethylidene] propanedinitrile, 2 - [1- (3,5-dimethoxyphenyl) phenylmethylene] propanedinitrile, 2 - [(3,5-dimethoxyphenyl) methoxymethylene] propanedinitrile, 2 - [(3,5-dimethoxyphenyl) methylene] diethyl malonate, (E) -3- (3,5-dimethoxyphenyl) but-2-enenitrile. 5. The method according to p. A process according to claim 3, characterized in that the compounds of general formula (3) are compounds selected from the group consisting of: diacetoxyiodo-benzene, 2'-cyano-diacetoxy-iodobenzene, 3'-cyano-diacetoxy-iodobenzene, 4'-cyano-diacetoxy-iodobenzene, 2'-methyl-diacetoxy-iodobenzene, 3'-methyl-diacetoxy-iodobenzene, 4'-methoxy-isodobenropenylacetyl , 2 ', 4', 6'-trimethyl diacetoxy iodobenzene. 6. The method according to p. 3. The process of claim 3, wherein the reaction of the compounds of general formulas (2) and (3) is carried out with a molar ratio of the compound (2) to the compound (3) ranging from 1: 1 to 1: 2. 7. The method according to p. 6. The process according to claim 6, characterized in that the reaction of the compounds of general formulas (2) and (3) is carried out with a molar ratio of the compound (2) to the compound (3) of 1: 1.1. 8. The method according to p. 3. The process according to claim 3, characterized in that the compound of general formula (2) and the compound of general formula (3) are reacted by stirring the reagents at 50 ° C for a period of 2 h, monitoring the progress of the reaction using thin-layer chromatography, and then reacting the reactants. an inorganic or an organic-inorganic salt, preferably potassium hexafluorophosphate, and acetic anhydride are added to the mixture and stirring is continued at 70 ° C for at least 5 minutes, then water is added, and the filtered and washed product is then dried on the air. 9. The method according to p. A process as claimed in claim 3, characterized in that new iodonium salts are prepared selected from the group consisting of: [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium triflate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium alkoxyaluminate ([Al (OC (CF3) 3) 4]); PL 237 731 -1 [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium triflate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium alkoxyquinate ([Al (OC (CF3) 3) 4]); (2-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate; (3-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate; (4-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate; 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate; 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (3-methylphenyl) iodonium hexafluorophosphate; 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate; 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; 2 [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate; [2- (2,2-dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2- (2,2-dicyano-1-phenylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2- (2,2-dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2- (3-ethoxy-2-ethoxycarbonyl-3-oxoprop-1-enyl) -4,6-dimethoxyphenyl] phenyliodonium h e xaf I u o rophosphate; [2 - [(E) -2-cyano-1-methylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate. 10. The use of new iodonium salts of general formula (1) wherein Ri is -H, -CN, -COOC2H5; R2 is -CN, -COOC2H5; R3 is -H, -OCH3, -CH3, -Ph; R4-R8 are each independently -H, -CN, -CH3, -CH (CH3) 2; E ~ is an anion selected from the group consisting of PFe ", SbFe", BF4 ~, CFsSOs ", B (C6F5) 4 ~, [Al (OC (CF ₃ ) 3) 4]", as photoinitiators for the photoinitiated cationic polymerization of monomers that can be polymerize in cationic polymerization processes. 11. The use according to claim 1 The process of claim 10, wherein the cationic polymerization is performed as a ring-opening polymerization or as a chain polymerization. 12. The use according to claim 1 14. The process of claim 11, wherein the ring-opening monomers used are at least one monomer selected from the group consisting of cycloaliphatic epoxy monomers, preferably 3,4-epoxycyclohexanecarboxylate-3,4-epoxycyclohexylmethyl, cyclohexene oxide or glycidyl monomers selected from tris (4 -hydroxyphenyl) methane, 1,4-butanediol diglycidyl ether, bis [4- (glycidyloxy) phenyl] methane, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether. 13. Use according to claim 1 The process of claim 11, wherein at least one monomer selected from the group consisting of vinyl ethers, preferably triethylene glycol divinyl ether, divinyl glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,4-butanediol divinyl ether, polyethylene glycol divinyl. 14. Use according to claim 1 The process of claim 10, wherein the mixture to be polymerized contains additional initiators, additional monomers, and further sensitizers, stabilizers, modifiers, regulators, solvents, fillers, dyes, pigments, and mixtures thereof. PL237 731 Β1 15. Use according to any one of claims 1 to 15 from 10 to 14, wherein the iodonium salts are selected from the group consisting of: [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium triflate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium alkoxyaluminate ([Al (OC (CF3) 3) 4]); [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium triflate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium alkoxyquinate ([Al (OC (CF3) 3) 4]); (2-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate; (3-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate; (4-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate; 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate; 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (3-methylphenyl) iodonium hexafluorophosphate; 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate; 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; 2 [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate; [2- (2,2-dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2- (2,2-dicyano-1-phenylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2- (2,2-dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2- (3-ethoxy-2-ethoxycarbonyl-3-oxoprop-1-enyl) -4,6-dimethoxyphenyl] phenyliodonium h e xaf I u o rophosphate; [2 - [(E) -2-cyano-1-methylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate. 16. A new 2- [1- (3,5-dimethoxyphenyl) ethylidene] propanedinitrile of formula (4) cn (4). 17. A new 2- [1- (3,5-dimethoxyphenyl) phenylmethylene] propanedinitrile of formula (5) 18. A new 2 - [(3,5-dimethoxyphenyl) methoxymethylene] propanedinitrile of formula (6) (6). 19. New (E) -3- (3,5-dimethoxyphenyl) but-2-enenitrile of formula (7) PL 237 731 Β1 20. A method for producing a new 2- [1- (3,5-dimethoxyphenyl) ethylidene] propanedinitrile of formula (4) (4), characterized in that 3 ', 5'-dimethoxyacetophenone of formula (8) is introduced into the reactor and malonodinitrile, which are dissolved in an organic solvent selected from the group consisting of chloroform, acetone, dichloromethane and ethyl acetate, then titanium (IV) chloride and a basic agent selected from the group consisting of pyridine, piperidine, morpholine and triethylamine are added dropwise to the resulting mixture, and then the contents of the reactor are stirred for a period from 1 h to 6 h at room temperature, monitoring the progress of the reaction, after which the dilute acid is dosed into the reactor in the form of 10% aqueous hydrochloric acid or 10% aqueous sulfuric acid (VI ) and extraction of the reactor contents with an organic solvent selected from the group consisting of ethyl acetate, diethyl ether, toluene and tetrahydrofuran, and then the combined organic layers are washed with water and brine, dried over a drying agent selected from anhydrous sodium sulfate and anhydrous sulfate of magnesium (VI), the drying agent is filtered off, the filtrate is concentrated by rotary evaporation the crude product residue is purified. 21. The method according to p. 20, characterized in that 3 ', 5'-dimethoxyacetophenone and malonodinitrile are dissolved in dichloromethane, titanium (IV) chloride and pyridine are added dropwise to the resulting mixture, and the reactor contents are stirred for 4 hours at room temperature, monitoring the progress of the reaction using thin layer chromatography, and after completion of the reaction, 10% aqueous hydrochloric acid solution is added and the reactor contents are extracted with ethyl acetate, the combined organic layers are washed with water and brine, dried over anhydrous sodium sulfate, and after filtering the drying agent and After concentration of the filtrate, the crude product is purified by column chromatography. 22. A method for producing a new 2- [1- (3,5-dimethoxyphenyl) phenylmethylene] propanedinitrile of formula (5) characterized in that it introduces dimethoxyphenyljphenylmethanone of formula (9) into the reactor PL237 731 Β1 _χ Ο and malonodinitrile, which are dissolved in an organic solvent selected from the group consisting of chloroform, acetone, dichloromethane and ethyl acetate, and then titanium (IV) chloride and a basic agent selected from the group consisting of pyridine, piperidine, morpholine and tri are added dropwise to the resulting mixture. ethylamine, and then the contents of the reactor are stirred for a period from 1 h to 6 h at room temperature, monitoring the progress of the reaction, after which the dilute acid is dosed into the reactor in the form of a 10% aqueous hydrochloric acid solution or a 10% aqueous acid solution sulfuric acid (VI) and extraction of the reactor contents with an organic solvent selected from the group consisting of ethyl acetate, diethyl ether, toluene and tetrahydrofuran, then the combined organic layers are washed with water and brine, dried over a drying agent selected from anhydrous sodium sulfate and anhydrous magnesium sulfate (VI), the drying agent is filtered off, the filtrate is concentrated on an evaporator at the crude product residue is purified. 23. The method according to p. 22, characterized in that 2- [1- (3,5-dimethoxyphenyl) phenylmethylene] propanedinitrile and malonodinitrile are dissolved in dichloromethane, titanium (IV) chloride and pyridine are added dropwise to the resulting mixture, and the reactor contents are stirred for 4 hw room temperature while monitoring the progress of the reaction by thin layer chromatography, after the reaction is completed, 10% aqueous hydrochloric acid is added and the contents of the reactor are extracted with ethyl acetate, the combined organic layers are washed with water and brine, dried over anhydrous sulfate (VI) sodium, and after filtering off the drying agent and concentrating the filtrate, the crude product is purified by column chromatography. 24. A method for the preparation of a new 2 - [(3,5-dimethoxyphenyl) methoxymethylene] propanedinitrile of formula (6) with J ^ CN CN (6) o characterized by the following stages: - step A), in which a 60% (m / m) suspension of sodium hydride in tetrahydrofuran is introduced into the reactor, a solution of malonodinitrile in tetrahydrofuran is added to the reactor, and after 15 min. While stirring, a solution of 3,5-dimethoxybenzoyl chloride in tetrahydrofuran is added, and the reagents are stirred for a period of 10 minutes to 120 minutes at 0 ° C, after which the reactor contents are further stirred for up to 6 h to 18 h at room temperature, monitoring the progress of the reaction, and after its completion, water and hydrochloric acid are added to the reactor until the reaction mixture is pH = 3, then the mixture is extracted with an organic solvent selected from the group consisting of ethyl acetate, diethyl ether, toluene and tetrahydrofuran, the combined organic layers are washed with water and brine, dried over a drying agent selected from anhydrous sodium sulfate and anhydrous magnesium sulfate, then the drying agent was filtered off, the filtrate was concentrated and the residue was purified to give 2- (3,5-dimethoxybenzoyl) propanedinitrile, which is used as a substrate in step B); - step B) in which a mixture of 1,4-dioxane and water is charged to the reactor, to which 2- (3,5-dimethoxybenzoyl) propanedinitrile has been added, then water is added PL 237 731 Β1 sodium carbonate and methyl sulphate and the contents of the reactor are boiled for a period of 1 h to 5 h, monitoring the progress of the reaction, and after completion of the reaction and cooling the reaction mixture to room temperature, water is added and extraction is carried out with an organic solvent of the selected from the group consisting of ethyl acetate, diethyl ether, toluene and tetrahydrofuran, the combined organic layers are washed with brine, dried over a drying agent selected from anhydrous sodium sulfate and anhydrous magnesium sulfate, then the drying agent is filtered off, the filtrate is concentrated on rotary evaporator and the crude end product residue is purified. 25. The method according to p. 24, characterized in that in step A), after adding a solution of 3,5-dimethoxybenzoyl chloride in tetrahydrofuran to the contents of the reactor, the reagents are stirred for 1 h at 0 ° C and 12 h at room temperature, monitoring the progress of the reaction using thin-layer chromatography, and after adding water and hydrochloric acid and adjusting the reaction mixture to pH = 3, this mixture is extracted with ethyl acetate, and after washing the combined organic layers, they are dried over anhydrous sodium sulphate, then the drying agent is filtered off and the filtrate is concentrated, the residue is purified using column chromatography; in step B) the reagents are boiled for 2 h, monitoring the progress of the reaction by thin-layer chromatography, after the reaction is complete and the reaction mixture cooled, water is added and the reaction mixture is extracted with ethyl acetate, the combined organic layers are dried over anhydrous sulfate after washing with brine (VI) of sodium, and after filtering off the drying agent and concentrating the filtrate, the residue is purified by column chromatography. 26. The method of producing the new (E) -3- (3,5-dimethoxyphenyl) but-2-enenitrile of formula (7) characterized in that a 60% (m / m) suspension of sodium hydride in tetrahydrofuran is introduced into the reactor, a solution of diethyl cyanomethylphosphate in tetrahydrofuran is added to the reactor and the contents of the reactor are stirred for a period from 5 minutes to 60 minutes, then a solution of 3 ', 5'-dimethoxyacetophenone in tetrahydrofuran is added and stirring is continued at room temperature for 1 h to 6 h while monitoring the progress of the reaction, and upon completion of the reaction, an aqueous saturated ammonium chloride solution is added and the contents of the reactor are extracted With ethyl acetate, the combined organic layers are washed with brine, dried over a drying agent selected from anhydrous sodium sulfate and anhydrous magnesium sulfate, the drying agent is filtered off, the filtrate is concentrated on a rotary evaporator, and the crude residue is cleans up. 27. The method according to p. 26, characterized in that a 60% (m / m) slurry of sodium hydride in tetrahydrofuran is introduced into the reactor, a solution of diethyl cyanomethylphosphate in tetrahydrofuran is added to the reactor and the reactor contents are stirred for 15 minutes, and then added solution of 3 ', 5'-dimethoxyacetophenone in tetrahydrofuran is continued and stirring is continued at room temperature for a period of 3 h, monitoring the progress of the reaction using thin layer chromatography, and after extraction, washing the combined organic layers with brine, drying them over anhydrous sodium sulfate, and after filtering off the drying agent and concentrating the filtrate, the residue is purified by column chromatography. 28. The use of compounds of general formula (2) PL237 731 Β1 (2) in which Ri is -H, -CN, -COOC2H5; R2 is -CN, -COOC2H5; R3 is -H, -OCH3, -CH3, -Ph; for the preparation of iodonium salts of general formula (1) wherein R1 is -H, -CN, -COOC2H5; R2 is -CN, -COOC2H5; R3 is -H, -OCH3, -CH3, -Ph; R4-R8 are each independently -H, -CN, -CH3, -CH (CH3) 2; E "is an anion selected from the group consisting of PFe", SbFe ", BF4", CF3SO3 ", B (C6F5) 4 ^- , [Al (OC (CF ₃ ) 3) 4] ·. 29. Use according to claim 1 The process of claim 28, wherein compounds of general formula (2) are used to prepare iodonium salts selected from the group consisting of: [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyl iodonium hexafluorophosphate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium triflate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate; [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] phenyliodonium alkoxyaluminate ([Al (OC (CF3) 3) 4]); [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluoroantimonate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrafluoroborate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium triflate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium tetrapentafluorophenylborate; [2- (2,2-dicyanovinyl) -4,6-dimethoxyphenyl] phenyliodonium alkoxyquinate ([Al (OC (CF3) 3) 4]); (2-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate; (3-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate; (4-cyanophenyl) - [2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] iodonium hexafluorophosphate; 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2-methylphenyl) iodonium hexafluorophosphate; 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-methylphenyl) iodonium hexafluorophosphate; 2 - [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (4-isopropylphenyl) iodonium hexafluorophosphate; 2 [(E) -2-cyanovinyl] -4,6-dimethoxyphenyl] - (2,4,6-trimethylphenyl) iodonium hexafluorophosphate; [2- (2,2-dicyano-1-methylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2- (2,2-dicyano-1-phenylvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2- (2,2-dicyano-1-methoxyvinyl) -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate; [2- (3-ethoxy-2-ethoxycarbonyl-3-oxoprop-1-enyl) -4,6-dimethoxyphenyl] phenyliodonium h e xaf I u o rophosphate; [2 - [(E) -2-cyano-1-methylvinyl] -4,6-dimethoxyphenyl] phenyliodonium hexafluorophosphate.