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Polielektrolity otrzymywane w wyniku reakcji Rittera oraz funkcjonalizowania merów winyloaminowych

Bortel E., Kochanowski A., Witek E.

Prace Naukowe Instytutu Technologii Organicznej i Tworzyw Sztucznych Politechniki Wrocławskiej. Konferencje

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2003

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Vol. 52, nr 25

194-201

PL

Istnieje możliwość regulowania stosunku ładunków +/- w polielektrolitach amfoterycznych dzięki usadowieniu jonogennych grup funkcyjnych w N-pochodnych akryloamidu syntezowanych za pomocą reakcji Rittera. Bardzo zbliżone współczynniki reaktywności do niejonowego akryloamidu pozwalają także kontrolować gęstość ładunku w kopolimerach. Nowe możliwości formowania poliamfolitów oraz polimerów amfifilowych powstały dzięki uruchomieniu produkcji N-winyloformamidu, który jako mer wbudowany w łańcuch łatwo hydrolizuje do merów winyloaminowych. Funkcjonalizowanie grup NH2 toruje drogę do polielektrolitów dotąd nieosiągalnych.

EN

Ionogenic monomers obtainable via Ritter reaction show similar reactivity coefficients causing that the control of +/- charge ratios in amphoteric copolymers appears to be feasible. By introducing acrylamide into the polyreaction charge densities can also be regulated. A novel route toward polyampholites and amphiphilic polyelectrolytes has been made facile due to the commercialization of N-vinylformamide, which can be easily hydrolyzed to vinylamide units after incorporation into polymer chain. Functionalization of NH2 groups enables to prepare polyelectrolytes hitherto not obtainable.

2

Amidation-Sulfonation of Selected Unasaturated Monoterpenes

Wełniak M.

Polish Journal of Chemistry

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2003

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Vol. 77 / nr 2

203-210

EN

Amidation-sulfonation of (+)-camphene (1), (-)-_- and (-)-_-pinene (3,4), (+)-limonene (5), (+)-2-carene (16), and (+)-carvone (21) with a mixture of 25% oleum and aceto- or propionitrile is described. Camphene (1) gave racemic exo-2-amidobornanesulfonic acids (8,9), whereas 3 and 4 produced optically active p-mentheneamidosulfonic acids (10-15). Under the same reaction conditions 1,4-addition to (+)-2-carene (16) leading to (1R,4R)-(-)-4-(1-acetylamino-1-methylethyl)-1-methyl-cyclohex-2-enesulfonic acid (17) was observed. Mixtures of diastereomeric structural terpene analogues of N-acetyltaurine were obtained from 5 and 21. Mechanisms of the investigated reactions are proposed.

3

The Reactions of Selected Terpene Alcohols with Acetonitrile in the Presence of Boron Trifluoride Etherate

Wełniak M.

Polish Journal of Chemistry

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2002

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Vol. 76 / nr 10

1405-1411

EN

Aseries of thirteen terpene alcohols 1-13 of bornane, fenchane and isotricyclene systems was subjected to the reaction with acetonitrile in the presence of BF3_Et2O as a catalyst to give respective acetamides and/or alkenes. The use of boron trifluoride etherate instead of the usually applied protonic donors let us establish beyond any doubt the carbonium ion stage participation. The assumed reaction course was corroborated by cationic Wagner-Meerwein, Namietkin and homoallylic rearrangements observed during studies under investigation. Simultaneously no evidence for the imidate formation was found. Such a mode of the reaction mechanism was alternatively suggested earlier by Sjöberg [9] for the reaction of sec- and tert-butanol with acetonitrile in the presence of boron trifluoride etherate.

4

Novel Rearrangement of Tertiary Fenchyl Alcohols with Sulfuric Acid in Acetonitrile

Wełniak M.

Polish Journal of Chemistry

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2002

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Vol. 76 / nr 1

37-44

EN

The influence of steric hindrance on rearrangements of tertiary 2-fenchyl cations under the Ritter reaction conditions (CH3CN/H2SO4) has been described. Depending on the branching of alkyl substituents at the C-2 position, the reaction time and temperature, different reaction courses have been observed. After 10 minutes at -20 to -15°C alcohol 2 (R = iso-Am) gave alkenes 7, whereas a pair of amides 8 and 9 for 24 hours at ambient temperature as a result of successive exo-3,2-methyl shift,Wagner-Meerwein rearrangement and endo-6,2-hydride shift. Alkene 10 was obtained as a primary product from alcohol 3 (R = iso-Bu) after 10 minutes at -20 to -15°C. When the same reaction was continued for 24 hours at room temperature, amide 12 has been obtained as the only product. It was explained by the operation of endo-6,2-hydride shift after protonation of alkene 10 and further reaction with acetonitrile. In the case of alcohols 4-6 with bulky isopropyl, sec-butyl and 2-sec-amyl substituents, a novel rearrangement to tetrasubstituted alkenes containing the bicyclo[3.1.1]heptane skeleton have been notified. The mechanistic proposals for the investigated reaction are presented.

5

The Ritter Reaction of Terpenes. Part 3. Investigation of Carvone Related Compounds

Wełniak M.

Polish Journal of Chemistry

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2001

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Vol. 75, nr 1

55-62

EN

The Ritter reaction of (R)-carvone (1), cis-carveol (2) and carvyl ethers 3 and 4 was investigated.For ketone 1 formation of 8-amido-6-p-menthen-2-ones (7-12) in moderate yields was observed. Alcohol 2 gave, depending on the reaction conditions, 2-amido- 6,8(9)-p-menthadienes, 2-amido-4(8),6-p-menthadienes and/or 2,8-diamido-6-p-menthenes. Ethers 3 and 4 underwent cleavage to almost the same amides as it was observed for cis-carveol (2). Additionally, tertiary phenylcarveol (5) under similar conditions furnished 6-acetamido-2-phenyl-1,8(9)-p-menthadiene (28) as a result of dehydration, followed by migration of a double bond. The proposed mechanisms of the reactions are presented.

6

The Ritter reaction of terpenes. Part 2. The fenchyl system

Wełniak M.

Polish Journal of Chemistry

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1998

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Vol. 72, nr 6

1021-1027

EN

The Ritter reaction of fenchyl alcohols 2a-f was examined. Surprisingly, in the case of alcohols 2a-d, formation of the corresponding alkenes 3 was observed. These compounds underwent, in turn, Namietkin and Wagner-Meerwein rearrangements, followed by endo-6,2-hydrogen shift to give acetamides 8 and 9, The alcohol 2e gave a mixture of hydrocarbons 11 and 12 as well as an anti acetamide 9e. For secondary ando-2-fenchol (2f) exo-isofenchyl acetamide (15) was the only product as a result of endo-6,2-hydrogen shift and subsequent reaction with acetonitrile.