EP0144934A2 - Smoking product containing nicotine-N'-oxide - Google Patents
Smoking product containing nicotine-N'-oxide Download PDFInfo
- Publication number
- EP0144934A2 EP0144934A2 EP84114573A EP84114573A EP0144934A2 EP 0144934 A2 EP0144934 A2 EP 0144934A2 EP 84114573 A EP84114573 A EP 84114573A EP 84114573 A EP84114573 A EP 84114573A EP 0144934 A2 EP0144934 A2 EP 0144934A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- nicotine
- oxide
- trans
- cis
- tobacco
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/18—Treatment of tobacco products or tobacco substitutes
- A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
- A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
- A24B15/36—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring
- A24B15/38—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring having only nitrogen as hetero atom
Definitions
- the invention relates to a smoking product, in particular tobacco with or without wrapping material, containing nicotine N'-oxide.
- the invention is based on the knowledge that the cis isomer of nicotine N'-oxide leads to a considerable deterioration in the taste of smoke. Accordingly, the invention is primarily directed to a smoke product whose smoke has an increased nicotine content due to the addition of nicotine N'-oxide, the above-mentioned taste impairment of the smoke by the cis isomer being able to be avoided.
- smoking product used here includes cut tobacco, pipe tobacco, cigarettes, cigarillos or cigars To understand tobacco with or without added non-tobacco materials and / or reconstituted tobacco.
- the smoking product of the invention can be produced with or without wrapping material, wherein the wrapping material used can be cigarette paper, cigar or cigarillo wrappers made of tobacco or non-tobacco materials.
- the smoking product of the invention contains trans-nicotine-N'-oxide which is free or essentially free of cis-nicotine-N'-oxide or has a content of at most 10% by weight of the cis isomer, namely in an amount up to 5% by weight, based on the dry weight of the smoke product.
- the trans-nicotine N'-oxide to be used according to the invention which is free or essentially free of cis-nicotine N'-oxide or has a content of at most 10% by weight of the cis isomer, can be used in tobacco or non-tobacco materials contained therein and / or the wrapping materials which may be present, for example be added to the cigarette paper or the cigar or cigarillo wrappings made of tobacco and / or non-tobacco materials.
- the addition is advantageously carried out on the finished tobacco material, e.g. in the form of an aqueous solution, or on the finished wrapping material, e.g. in an alcoholic or aqueous-alcoholic solution.
- the invention is further directed to a process for the production of trans-nicotine N'-oxide that is free or substantially free of cis-nicotine-N'-oxide is particularly directed for use as an additive to smoking products of the invention.
- the invention is therefore further directed to a process for the production of trans-nicotine N'-oxide, which is free or essentially free of cis-nicotine N'-oxide, requires short reaction times, and in which only auxiliaries which are unobjectionable under food law come into use.
- the process of the invention is characterized in that the oxidation is carried out in the presence of catalytic amounts of non-oxidizing inorganic and / or organic acids with a pK value of less than 5.
- the reaction temperature during the reaction should in any case be as low as possible higher reaction temperatures favor the formation of decomposition products and the cis isomer, albeit only to a small extent.
- the reaction temperature should never be above 90 ° C, otherwise explosive decomposition of the hydrogen peroxide can occur.
- Monocarboxylic, dicarboxylic or polycarboxylic acids and their hydroxy, keto or unsaturated derivatives are particularly suitable as catalytically active acids with a pK value of less than 5.
- the reaction of nicotine with hydrogen peroxide is preferably carried out in essentially equimolar amounts, hydrogen peroxide being initially introduced and nicotine being added dropwise; the reverse procedure is also possible.
- an oxidizing agent it is expedient to add commercially available hydrogen peroxide in the form of a 30-50% aqueous solution.
- the acids used as catalysts are preferably used in an amount of 10-150, in particular 20-100 mmol per mole of nicotine.
- the oxidation mixture obtained during the oxidation is dewatered.
- the dewatering can preferably be carried out by azeotropic distillation using n-propanol as the azeotropic dewatering agent. Remaining traces of water can be removed from the reaction mixture dried in this way using a molecular sieve (pore size 4A).
- the trans-nicotine N'-oxide crystallizes out of the dry oxidation mixture in pure form. It can be added to the tobacco and / or the wrapping material in the manner described above, but with up to for cost reasons Can stretch 10 wt .-% of the cis isomer.
- the cis isomer remaining after working up the oxidation mixture is advantageously reduced to nicotine; the nicotine thus obtained can be oxidized again.
- the colorless solution thus obtained which is free of nicotine and hydrogen peroxide, can be processed directly.
- Example 1 The solution obtained in Example 1 is dewatered with n-propanol by azeotropic distillation. The dewatered solution is then dried with molecular sieve (4A). On cooling, pure trans-nicotine N'-oxide crystallizes out of the mixture thus obtained and can be filtered off with suction. The remaining mother liquor contains predominantly cis-nicotine-N'-oxide.
- the mixture obtained has a cis / trans ratio of the nicotine N'-oxides of 1: 1.67.
- the crude product thus obtained is mixed with 25 kg of n-propanol and distilled.
- the reaction residue thus dewatered is then dried with 5 kg of molecular sieve (4A) in 5 kg of methylene chloride.
- the reaction mixture is subjected to azeotropic dewatering.
- azeotropic dewatering For this purpose, 10.6 kg of n-propanol are added and a water-containing distillate (75% by mass n-propanol / 25% water) is separated off under a slight vacuum.
- the low-water residue has a residual water content of 7.7% by mass.
- Nicotinization of a cigarette strand Nicotinization of a cigarette strand.
- the tobacco nicotine content is increased with the help of a 10% alcoholic trans-nicotine N'-oxide solution by 1.13% to 2.62%; the addition is made by spraying on the tobacco material.
- the cigarettes made from the tobacco material obtained in this way have a smoke nicotine yield which is 0.3 mg higher when smoking under DIN conditions.
- the condensate content remains unchanged compared to untreated cigarettes.
- Cigarette strand nicotinization Cigarette strand nicotinization.
- a tobacco mixture with a nicotine content of 1.66% is raised to 6.1% with a 20% aqueous trans-nicotine N'-oxide solution in the leaf cut nicotine content.
- the cigarettes then made from this tobacco material result in a smoke nicotine yield increased by 0.5 mg when smoking under DIN conditions.
- the condensate content did not change compared to untreated cigarettes.
- Ci arettenpapierbahn be reverse with the aid of rollers with a 10% trans-nicotine-N'-oxide solution in water / ethanol (1: 1) moistened and dried in a hot air stream. After drying, the cigarette paper obtained is similar in color and mechanical stability to the untreated pattern and contributes to an increase in nicotine smoke.
- the amount of the trans-nicotine N'-oxide applied in accordance with the process is 5%, based on the weight of the cigarette paper.
- Nicotine compensation by adding trans-nicotine N'-oxide before an expansion process is a factor
- a filler grade with a nicotine content of 1.8% by weight and a moisture content of 11% by weight are made using a trans-nicotine-N'-oxide solution consisting of 4.3 l of water and 200 g of trans-nicotine N'-oxide, brought to an expansion moisture of approx. 18% by weight.
- trans-nicotine-N'-oxide compensates for the 25% loss of nicotine which is always to be expected in tobacco expansion processes, so that the expanded tobacco with its original nicotine content can contribute to the mixture build-up.
Abstract
Rauchprodukte, z.B. Cigaretten, Schnittabak, Pfeifentabak, Zigarillos und dergleichen, ergeben eine erhöhte Nicotinausbeute im Tabakrauch ohne Beeinträchtigung des Rauchgeschmacks, wenn ihnen trans-Nicotin-N'-oxid, das frei oder im wesentlichen frei von cis-Nicotin-N'-oxid ist oder höchstens 10 Gew.-%, des cis-Isomeren enthält, in einer Menge bis zu 5 Gew.-% bezogen auf Tabaktrockengewicht, zugesetzt werden.Smoking products, e.g. Cigarettes, cut tobacco, pipe tobacco, cigarillos and the like result in an increased nicotine yield in tobacco smoke without impairing the taste of smoke if they contain trans-nicotine-N'-oxide which is free or essentially free of cis-nicotine-N'-oxide or at most 10% by weight of the cis isomer is added in an amount of up to 5% by weight based on the tobacco dry weight.
Description
Die Erfindung betrifft ein Rauchprodukt, insbesondere Tabak mit oder ohne Umhüllungsmaterial, enthaltend Nicotin-N'-oxid.The invention relates to a smoking product, in particular tobacco with or without wrapping material, containing nicotine N'-oxide.
Aus "Die Nahrung",4. Jahrgang 1960, Heft 4, Seite 310 - 323, insbesondere Seite 322, Zusammenfassung bzw. Summary, ist bekannt, daß Nicotin-N'-oxid, enthalten in Rauchtabak, beim Abrauchen Nicotin bildet und zu einer Steigerung des Nicotingehaltes im Haupt- und Nebenstromrauch führt.From "The Food", 4. Year 1960, Issue 4, pages 310 - 323, in particular page 322, summary, is known that nicotine-N'-oxide, contained in smoking tobacco, forms nicotine when smoking and to an increase in the nicotine content in main and sidestream smoke leads.
Die Erfindung beruht auf der Erkenntnis, daß das cis-Isomere des Nicotin-N'-oxids zu einer erheblichen Verschlechterung des Rauchgeschmacks führt. Demgemäß ist die Erfindung in erster Linie auf ein Rauchprodukt gerichtet, dessen Rauch durch Nicotin-N'-oxidzusatz einen erhöhten Nicotingehalt aufweist,wobei die oben genannte Geschmacksbeeinträchtigung des Rauches durch den cis-Isomeren vermieden werden kann.The invention is based on the knowledge that the cis isomer of nicotine N'-oxide leads to a considerable deterioration in the taste of smoke. Accordingly, the invention is primarily directed to a smoke product whose smoke has an increased nicotine content due to the addition of nicotine N'-oxide, the above-mentioned taste impairment of the smoke by the cis isomer being able to be avoided.
Unter dem hier verwendeten Begriff "Rauchprodukt" sind Schnitttabak, Pfeifentabak, Cigaretten, Zigarillos oder Zigarren aus Tabak mit oder ohne zugesetzten Nicht-Tabak-Materialien und/ oder rekonstituiertem Tabak zu verstehen. Das Rauchprodukt der Erfindung kann mit oder ohne Umhüllungsmaterial hergestellt sein, wobei als Umhüllungsmaterial Cigarettenpapier, Zigarren-oder Zigarilloumhüllungen aus Tabak oder Nicht-Tabak-Materialien verwendet werden können.The term "smoking product" used here includes cut tobacco, pipe tobacco, cigarettes, cigarillos or cigars To understand tobacco with or without added non-tobacco materials and / or reconstituted tobacco. The smoking product of the invention can be produced with or without wrapping material, wherein the wrapping material used can be cigarette paper, cigar or cigarillo wrappers made of tobacco or non-tobacco materials.
Das Rauchprodukt der Erfindung enthält erfindungsgemäß trans-Nicotin-N'-oxid, das frei oder im wesentlichen frei von cis-Nicotin-N'-oxid ist oder einen Gehalt von höchstens 10 Gew.-% des cis-Isomeren aufweist, und zwar in einer Menge bis zu 5 Gew.-%, bezogen auf das Rauchprodukttrockengewicht.According to the invention, the smoking product of the invention contains trans-nicotine-N'-oxide which is free or essentially free of cis-nicotine-N'-oxide or has a content of at most 10% by weight of the cis isomer, namely in an amount up to 5% by weight, based on the dry weight of the smoke product.
Es wurde gefunden, daß ein Gehalt von höchstens 10 Gew.-% des cis-Isomeren in dem trans-Isomeren ohne Geschmacksbeeinträchtigungen bleibt. Höhere Anteile an den cis-Isomeren in der Größenordnung von 10 bis 30 Gew.-% können hingenommen werden, erfordern dann jedoch bestimmte geschmacksverbessernde Zusätze (Flavours), die den nachteiligen Geschmack des cis-Isomeren, wenn auch nicht vollständig, überdecken können.It has been found that a content of at most 10% by weight of the cis isomer remains in the trans isomer without any taste impairments. Higher proportions of the cis isomer in the order of 10 to 30% by weight can be accepted, but then require certain flavor-enhancing additives (flavors) which can, if not completely, mask the disadvantageous taste of the cis isomer.
Das erfindungsgemäß einzusetzende trans-Nicotin-N'-oxid, das frei oder im wesentlichen frei von cis-Nicotin-N'-oxid ist oder einen Gehalt von höchstens 10 Gew.-% des cis-Isomeren aufweist, kann dem Tabak bzw. den darin enthaltenen Nicht-Tabak-Materialien und/oder den gegebenenfalls vorhandenen Umhüllungsmaterialien, z.B. dem Cigarettenpapier oder den Zigarren- oder Zigarilloumhüllungen aus Tabak und/oder Nicht-Tabak-Materialien,zugesetzt sein. Die Zugabe erfolgt zweckmäßigerweise auf das fertige Tabakmaterial, z.B. in Form einer wässrigen Lösung, oder auf das fertige Umhüllungsmaterial, z.B. in einer alkoholischen oder wässrig-alkoholischen Lösung.The trans-nicotine N'-oxide to be used according to the invention, which is free or essentially free of cis-nicotine N'-oxide or has a content of at most 10% by weight of the cis isomer, can be used in tobacco or non-tobacco materials contained therein and / or the wrapping materials which may be present, for example be added to the cigarette paper or the cigar or cigarillo wrappings made of tobacco and / or non-tobacco materials. The addition is advantageously carried out on the finished tobacco material, e.g. in the form of an aqueous solution, or on the finished wrapping material, e.g. in an alcoholic or aqueous-alcoholic solution.
Die Erfindung ist weiterhin auf ein Verfahren zur Herstellung von trans-Nicotin-N'-oxid, das frei oder im wesentlichen frei von cis-Nicotin-N'-oxid ist, insbesondere zur Verwendung als Additiv zu Rauchprodukten der Erfindung, gerichtet.The invention is further directed to a process for the production of trans-nicotine N'-oxide that is free or substantially free of cis-nicotine-N'-oxide is particularly directed for use as an additive to smoking products of the invention.
Isomerengemische des Nicotin-N'-oxids wurden erstmals durch Oxidation von Nicotin mit wässrigem Wasserstoffperoxid erhalten, vgl. Chem. Ber. 24, 61 - 67 (1891) . Eine Verbesserung dieses Verfahrens unter Verwendung eines Molverhältnisses von Nicotin zu Wasserstoffperoxid von 1 : 3 ist in J. org.Chem. 24, 275 - 277 (1970) beschrieben. Nachteilig an diesem Verfahren ist insbesondere die lange Reaktionszeit von 2 - 3 Tagen und der große Uberschuß an Oxidationsmitteln, der eine wirtschaftliche Nutzung dieses Verfahrens verbietet. Zudem ließ sich das erhaltene Isomerengemisch des Nicotin-N'-oxids nicht isolieren; die Endprodukte mußten als Pikrate isoliert und charakterisiert werden.Mixtures of isomers of nicotine N'-oxide were obtained for the first time by oxidation of nicotine with aqueous hydrogen peroxide, cf. Chem. Ber. 24, 61-67 (1891). An improvement of this method using a molar ratio of nicotine to hydrogen peroxide of 1: 3 is in J. org.Chem. 24, 275-277 (1970). A disadvantage of this process is in particular the long reaction time of 2-3 days and the large excess of oxidizing agents, which prohibits the economical use of this process. In addition, the resulting mixture of isomers of nicotine N'-oxide could not be isolated; the end products had to be isolated and characterized as picrates.
Wesentlich kürzere Oxidationszeiten lassen sich bei der Herstellung der Isomerengemische des Nicotin-N'-oxids erzielen, wenn man gemäß J. org. Chem. 35, 1721 - 1722 (1970) Nicotin mit organischen Persäuren oxidiert. Die gewünschten Reaktionsprodukte erfordern jedoch einen erhöhten Reinigungsaufwand; zudem ist ein solches Verfahren zur Herstellung von Nicotin-N'-oxiden wegen des hohen Preises organischer Persäuren unwirtschaftlich.Much shorter oxidation times can be achieved in the preparation of the isomer mixtures of nicotine-N'-oxide if, according to J. org. Chem. 35, 1721-1722 (1970) nicotine oxidized with organic peracids. However, the desired reaction products require an increased cleaning effort; In addition, such a process for the production of nicotine N'-oxides is uneconomical because of the high price of organic peracids.
Die Erfindung ist somit weiterhin auf ein Verfahren zur Herstellung von trans-Nicotin-N'-oxid gerichtet, das frei oder im wesentlichen frei von cis-Nicotin-N'-oxid ist, kurze Reaktionszeiten benötigt, und bei dem zusätzlich nur lebensmittelrechtlich unbedenkliche Hilfsstoffe zur Anwendung kommen.The invention is therefore further directed to a process for the production of trans-nicotine N'-oxide, which is free or essentially free of cis-nicotine N'-oxide, requires short reaction times, and in which only auxiliaries which are unobjectionable under food law come into use.
Das Verfahren der Erfindung ist dadurch gekennzeichnet, daß man die Oxidation in Gegenwart katalytischer Mengen an nicht-oxidierenden anorganischen und/oder organischen Säuren mit einem pK-Wert von weniger als 5 durchführt. Die Reaktionstemperatur bei der Umsetzung soll in jedem Falle möglichst niedrig sein, da höhere Raktionstemperaturen die Bildung von Zersetzungsprodukten sowie des cis-Isomeren, wenn auch letzteresnur in geringem Umfang, begünstigen. Die Reaktionstemperatur sollte keinesfalls über 90°C liegen, da es sonst zu explosionsartigen Zersetzungen des Wasserstoffperoxids kommen kann. Als katalytisch wirksame Säuren mit einem pK-Wert von weniger als 5 sind insbesondere Monocarbon-, Dicarbon- oder Polycarbonsäuren sowie deren Hydroxy-, Keto- oder ungesättigte Derivate geeignet. Bevorzugt ist die Verwendung von im Tabak vorkommenden natürlichen Carbon-, Dicarbon- oder Polycarbonsäuren, wie sie beispielsweise aus Chem. Rev. 68, 169 - 171 (1968) bekannt sind, insbesondere Malon-, Bernstein- und Apfelsäure . Die Verwendung von Citronensäure ist besonders bevorzugt.The process of the invention is characterized in that the oxidation is carried out in the presence of catalytic amounts of non-oxidizing inorganic and / or organic acids with a pK value of less than 5. The reaction temperature during the reaction should in any case be as low as possible higher reaction temperatures favor the formation of decomposition products and the cis isomer, albeit only to a small extent. The reaction temperature should never be above 90 ° C, otherwise explosive decomposition of the hydrogen peroxide can occur. Monocarboxylic, dicarboxylic or polycarboxylic acids and their hydroxy, keto or unsaturated derivatives are particularly suitable as catalytically active acids with a pK value of less than 5. Preference is given to using natural carboxylic, dicarboxylic or polycarboxylic acids occurring in tobacco, as are known, for example, from Chem. Rev. 68, 169-171 (1968), in particular malonic, succinic and malic acid. The use of citric acid is particularly preferred.
Die Umsetzung von Nicotin mit Wasserstoffperoxid erfolgt vorzugsweise in im wesentlichen äquimolaren Mengen, wobei Wasserstoffperoxid vorgelegt und Nicotin zugetropft wird; auch das umgekehrte Verfahren ist möglich. Als Oxidationsmittel setzt man zweckmäßigerweise handlesübliches Wasserstoffperoxid in Form einer 30-50%-igen wässrigen Lösung zu.The reaction of nicotine with hydrogen peroxide is preferably carried out in essentially equimolar amounts, hydrogen peroxide being initially introduced and nicotine being added dropwise; the reverse procedure is also possible. As an oxidizing agent, it is expedient to add commercially available hydrogen peroxide in the form of a 30-50% aqueous solution.
Die als Katalysatoren verwendeten Säuren werden vorzugsweise in einer Menge von 10-150, insbesondere 20-100 mMol pro Mol Nicotin verwendet.The acids used as catalysts are preferably used in an amount of 10-150, in particular 20-100 mmol per mole of nicotine.
Es hat sich als günstig für die Abtrennung des erfindungsgemäß herzustellenden trans-Isomeren erwiesen, wenn man das bei der Oxidation erhaltene Oxidationsgemisch entwässert. Dabei kann die Entwässerung vorzugsweise durch azeotrope Destillation unter Verwendung von n-Propanol als azeotropes Entwässerungsmittel erfolgen. Verbleibende Wasserspuren können aus dem so getrockneten 0 Reaktionsgemisch mittels Molekularsieb (Porengröße 4A) entfernt werden. Aus dem trocknen Oxidationsgemisch kristallisiert das trans-Nicotin-N'-oxid in reiner Form aus. Es kann dem Tabak und/oder dem Umhüllungsmaterial in der oben beschriebenen Weise zugesetzt werden, wobei man es aus Kostengründen mit bis zu 10 Gew.-% des cis-Isomeren strecken kann.It has proven to be advantageous for the removal of the trans isomer to be prepared according to the invention if the oxidation mixture obtained during the oxidation is dewatered. The dewatering can preferably be carried out by azeotropic distillation using n-propanol as the azeotropic dewatering agent. Remaining traces of water can be removed from the reaction mixture dried in this way using a molecular sieve (pore size 4A). The trans-nicotine N'-oxide crystallizes out of the dry oxidation mixture in pure form. It can be added to the tobacco and / or the wrapping material in the manner described above, but with up to for cost reasons Can stretch 10 wt .-% of the cis isomer.
Das nach der Aufarbeitung des Oxidationsgemisches zurückbleibende cis-Isomere wird zweckmäßigerweise zu Nikotin reduziert; das so erhaltene Nicotin kann erneut oxidiert werden.The cis isomer remaining after working up the oxidation mixture is advantageously reduced to nicotine; the nicotine thus obtained can be oxidized again.
Die Oxidation von Nicotin mit Wasserstoffperoxid verläuft exotherm und wirft daher Sicherheitsprobleme auf. Zweckmäßigerweise erfolgt daher die Durchführung des Verfahrens der Erfindung im industriellen Maßstab im Teilfließbetrieb, wobei Wasserstoffperoxid vorgelegt und Nicotin chargenweise zur Regulierung der Reaktionsgeschwindigkeit und damit der Wärmetönung zugegeben wird. Als besonderer Vorteil des Verfahrens der Erfindung ist hervorzuheben, daß überraschenderweise bei der Verwendung der erfindungsgemäß einzusetzenden Katalysatoren ein farbloses Oxidationsgemisch erhalten wird.The oxidation of nicotine with hydrogen peroxide is exothermic and therefore poses safety problems. It is therefore expedient to carry out the process of the invention on an industrial scale in partial flow mode, with hydrogen peroxide initially being added and nicotine being added in batches to regulate the reaction rate and thus the heat. It should be emphasized as a particular advantage of the process of the invention that, surprisingly, a colorless oxidation mixture is obtained when using the catalysts to be used according to the invention.
Das Verfahren der Erfindung wird im folgenden anhand von bevorzugten Ausführungsbeispielen näher erläutert.The method of the invention is explained in more detail below on the basis of preferred exemplary embodiments.
Herstellung eines cis/trans-Gemisches von Nicotin-N'-oxid.Preparation of a cis / trans mixture of nicotine N'-oxide.
500 g Nicotin (3,08 Mol) werden langsam in eine äquimolare 30 %-ige Wasserstoffperoxidlösung, enthaltend 5,9 g Citronensäure (30,8 mMol) eingetropft, wobei die Temperatur unter 90°C gehalten wird. Nach Beendigung der Zugabe erhitzt man 5 Stunden bei 80°C.500 g of nicotine (3.08 mol) are slowly added dropwise to an equimolar 30% hydrogen peroxide solution containing 5.9 g of citric acid (30.8 mmol), the temperature being kept below 90 ° C. After the addition has ended, the mixture is heated at 80 ° C. for 5 hours.
Die so erhaltene farblose Lösung, die frei von Nicotin und Wasserstoffperoxid ist, kann direkt weiterverarbeitet werden.The colorless solution thus obtained, which is free of nicotine and hydrogen peroxide, can be processed directly.
Herstellung eines reinen trans-Nicotin-N'-oxids.Production of a pure trans-nicotine N'-oxide.
Die in Beispiel 1 erhaltene Lösung wird mit n-Propanol durch azeotrope Destillation entwässert. Die entwässerte Lösung wird 0 mit Molekuarsieb (4A) nachgetrocknet. Aus dem so erhaltenen Gemisch kristallisiert beim Abkühlen reines trans-Nicotin-N'-oxid aus, das abgesaugt werden kann. Die zurückgebliebene Mutterlauge enhält überwiegend cis-Nicotin-N'-oxid.The solution obtained in Example 1 is dewatered with n-propanol by azeotropic distillation. The dewatered solution is then dried with molecular sieve (4A). On cooling, pure trans-nicotine N'-oxide crystallizes out of the mixture thus obtained and can be filtered off with suction. The remaining mother liquor contains predominantly cis-nicotine-N'-oxide.
Die hier beschriebene Methode zur Trennung des trans- von dem cis-Iscmeren ist erheblich einfacher als die in Phytochemistry, 14, 2683-2690 (1975), Pergamon Press, bzw. in Biochemical Pharmacology 19, 733-742 (1970), nur für analytische Mengen beschriebenen Verfahren.The method described here for separating the trans from the cis ismer is considerably simpler than that in Phytochemistry, 14, 2683-2690 (1975), Pergamon Press, or in Biochemical Pharmacology 19, 733-742 (1970), only for procedures described in analytical quantities.
Herstellung von trans-Nicotin-N'-oxid im halbtechnischen Maßstab im Teilfließbetrieb.Production of trans-nicotine-N'-oxide on a semi-industrial scale in a partial flow operation.
In einem Reaktor mit Rühwerk werden 7,75 kg 30 %-ige Wasserstoffperoxidlösung (68 Mol) und 125 g Citronensäure (0,65 Mol) vorgelegt und auf 40°C erwärmt; die Vorwärmung ist wichtig für die schnelle Einstellung des Betriebspunktes während der Nicotinzufuhr und muß daher sorgfältig durchgeführt werden. Anschließend werden 10 kg Nicotin (61,8 Mol) dem Reaktor zugeführt (VNi = 5 1/h) wobei durch die freiwerdende Reaktionswärme der Betriebspunkt von ca. 80°C eingestellt wird. Nach zweistündigem Nicotineintrag wird die Reaktion im Batchbetrieb unter Wärmezufuhr bei 80°C zuendegeführt. Dabei kann der Umsatz-Zeit-Verlauf spektroskopisch, jodometrisch oder elektrochemisch verfolgt werden.7.75 kg of 30% hydrogen peroxide solution (68 mol) and 125 g of citric acid (0.65 mol) are placed in a reactor with an agitator and heated to 40.degree. Preheating is important for the quick adjustment of the operating point during the nicotine supply and must therefore be carried out carefully. 10 kg of nicotine (61.8 mol) are then fed to the reactor (V Ni = 5 l / h), the operating point being set at approximately 80 ° C. by the heat of reaction liberated. After two hours of nicotine entry, the reaction is carried out in batch mode with the addition of heat at 80 ° C. The turnover-time course can be monitored spectroscopically, iodometrically or electrochemically.
Nach einer Gesamtreaktionszeit von 5 Stunden erhält man einen Nicotin-Umsatz von 98%; der Restgehalt an Wasserstoffperoxid beträgt 1,5%. Die erhaltene ölige Lösung der Oxidationsprodukte ist gelblich gefärbt und weist keinen Nicotingeruch auf.After a total reaction time of 5 hours, a nicotine conversion of 98% is obtained; the residual hydrogen peroxide content is 1.5%. The oily solution of the oxidation products obtained is colored yellow and has no nicotine smell.
Das erhaltene Gemisch weist ein cis/trans-Verhältnis der Nicotin-N'-oxide von 1 : 1,67 auf.The mixture obtained has a cis / trans ratio of the nicotine N'-oxides of 1: 1.67.
Das so erhaltene Rohprodukt wird mit 25 kg n-Propanol versetzt und destilliert. Dabei destilliert n-Propanol/Wasser im Verhältnis von 75 : 25 als Azeotrop ab. Der so entwässerte Reaktions-0 rückstand wird anschließend mit 5 kg Molekularsieb ( 4A) in 5 kg Methylenchlorid nachgetrocknet.The crude product thus obtained is mixed with 25 kg of n-propanol and distilled. Here, n-propanol / water distilled off in the ratio of 75:25 as an azeotrope. The reaction residue thus dewatered is then dried with 5 kg of molecular sieve (4A) in 5 kg of methylene chloride.
Aus dem trockenen Reaktionsgemisch kristallisiert reines trans-Nicotin-N'-oxid (4 kg; Fp. 171-173°C) aus. Es wird unter Zugabe von 5 kg Acetor, abgesaugt und bei 60°C im Trockenschrank getrocknet.Crystallized from the dry reaction mixture, pure trans-nicotine-N'-oxide (4 kg; F p 171-173 ° C.) From. It is suctioned off with the addition of 5 kg of Acetor and dried at 60 ° C. in a drying cabinet.
Ausbeute: 36,4 %,bezogen auf eingesetztes Nicotin, 58,7 %, bezogen auf gebildetes trans-Nicotin-N'-oxid.Yield: 36.4%, based on the nicotine used, 58.7%, based on the trans-nicotine N'-oxide formed.
In einem Reaktor mit Rührwerk werden 10 kg Nicotin (61,8 Mol) vorgelegt und auf ca. 40°C vorgewärmt. Anschließend werden 4,62 kg (68 Mol) 50 % H202, das mit 125 g Citronensäure (0,65 Mol) versehen wurde, sehr langsam dem Reaktor mit Hilfe einer Dosierpumpe zugeführt. Die Zugabegeschwindigkeit wird so eingestellt, daß eine Reaktionstemperatur von ca. 80°C erhalten wird. Der eingespeiste Volumenstrom ist abhängig von der Reaktionsführung, wobei eine eingebaute Kühlung für schnellere Wärmeabfuhr sorgt und deshalb das Zugabevolumen pro Zeiteinheit schneller sein kann.10 kg of nicotine (61.8 mol) are placed in a reactor with a stirrer and preheated to about 40.degree. Then 4.62 kg (68 mol) of 50% H 2 O 2 , which was provided with 125 g of citric acid (0.65 mol), are fed very slowly to the reactor using a metering pump. The rate of addition is adjusted so that a reaction temperature of about 80 ° C is obtained. The volume flow fed in depends on the reaction procedure, with built-in cooling ensuring faster heat dissipation and therefore the addition volume per unit of time may be faster.
Nach dem Eintrag des Wasserstoffperoxids (ca. 2 h) wird unter Wärmezufuhr die Reaktion bei 80°C zuendegeführt. Bei einer Gesamtreaktionszeit von ca. 5 h erhält man einen Nicotinumsatz von 98 %; der Restgehalt an Wasserstoffperoxid beträgt 1,5 Mas- sen-%. Der erhaltene Rückstand ist schwach gelb und weist keinen Nicotingeruch auf. Das cis/trans Verhältnis der beiden diastereomeren Nicotin-N'-oxide beträgt 1:1,67.After the hydrogen peroxide has been introduced (approx. 2 h), the reaction is completed at 80 ° C. with the addition of heat. With a total reaction time of approx. 5 h, a nicotine conversion of 98% is obtained; the residual hydrogen peroxide content is 1.5% sen - % . The residue obtained is pale yellow and has no N in icotingeruch. The cis / trans ratio of the two diastereomeric nicotine N'-oxides is 1: 1.67.
Das Reaktionsgemisch wird einer azeotropen Entwässerung unterworfen. Zu diesem Zweck werden 10,6 kg n-Propanol hinzugegeben und unter leichtem Vakuum ein wasserhaltiges Destillat (75 Massen-% n-Propanol/25 % Wasser) abgetrennt.The reaction mixture is subjected to azeotropic dewatering. For this purpose, 10.6 kg of n-propanol are added and a water-containing distillate (75% by mass n-propanol / 25% water) is separated off under a slight vacuum.
Der wasserarme Rückstand weist einen Restwassergehalt von 7,7 Massen-% auf.The low-water residue has a residual water content of 7.7% by mass.
Nicotinisierung eines Cigarettenstranges.Nicotinization of a cigarette strand.
Der Tabaknicotingehalt wird mit Hilfe einer 10 %-igen alkoholischen trans-Nicotin-N'-oxid-Lösung um 1,13 % auf 2,62 % angehoben; die Zugabe erfolgt durch Aufsprühen auf das Tabakmaterial.The tobacco nicotine content is increased with the help of a 10% alcoholic trans-nicotine N'-oxide solution by 1.13% to 2.62%; the addition is made by spraying on the tobacco material.
Die aus dem so erhaltenen Tabakmaterial gefertigten Cigaretten weisen beim Abrauchen unter DIN-Bedingungen eine um 0,3 mg erhöhte Rauchnicotinausbeute auf. Der Kondensatgehalt bleibt gegenüber unbehandelten Cigaretten unverändert.The cigarettes made from the tobacco material obtained in this way have a smoke nicotine yield which is 0.3 mg higher when smoking under DIN conditions. The condensate content remains unchanged compared to untreated cigarettes.
Cigarettenstrangnicotinisierung.Cigarette strand nicotinization.
Eine Tabakmischung mit einem Nicotingehalt von 1,66% wird mit einer 20 %-igen wässrigen trans-Nicotin-N'-oxid-Lösung im Blattschnittnicotingehalt auf 6,1 % angehoben. Die anschließend aus diesem Tabakmaterial gefertigten Cigaretten ergeben beim Abrauchen unter DIN-Bedingungen eine um 0,5 mg erhöhte Rauchnicotinausbeute.A tobacco mixture with a nicotine content of 1.66% is raised to 6.1% with a 20% aqueous trans-nicotine N'-oxide solution in the leaf cut nicotine content. The cigarettes then made from this tobacco material result in a smoke nicotine yield increased by 0.5 mg when smoking under DIN conditions.
Der Kondensatgehalt veränderte sich gegenüber unbehandelten Cigaretten nicht.The condensate content did not change compared to untreated cigarettes.
Nicotinisierung von Cigarettenpapier.Nicotinization of cigarette paper.
200 m einer Cigarettenpapierbahn werden rückseitig mit Hilfe von Walzen mit einer 10 %-igen trans-Nicotin-N'-oxid-Lösung in Wasser/Ethanol (1 : 1) befeuchtet und im Heißluftstrom getrocknet. Das erhaltene Cigarettenpapier gleicht nach der Trocknung in Farbe und mechanischer Stabilität dem unbehandelten Muster und trägt zur Rauchnicotinerhöhung bei. Die verfahrensgemäß aufgebrachte Menge an dem trans-Nicotin-N'-oxid beträgt 5 %, bezogen auf das Cigarettenpapiergewicht.200 m g of a Ci arettenpapierbahn be reverse with the aid of rollers with a 10% trans-nicotine-N'-oxide solution in water / ethanol (1: 1) moistened and dried in a hot air stream. After drying, the cigarette paper obtained is similar in color and mechanical stability to the untreated pattern and contributes to an increase in nicotine smoke. The amount of the trans-nicotine N'-oxide applied in accordance with the process is 5%, based on the weight of the cigarette paper.
Nicotinkompensation durch Zugabe von trans-Nicotin-N'-oxid vor einem Expansionsprozess.Nicotine compensation by adding trans-nicotine N'-oxide before an expansion process.
50 kg eines Filler-Grades mit einem Nicotingehalt von 1,8 Gew.-% und einer Feuchte von 11 Gew.-% werden mit Hilfe einer trans-Nicotin-N'-oxid-Lösung, bestehend aus 4,3 1 Wasser und 200 g trans-Nicotin-N'-oxid, auf eine Expansionsfeuchte von ca. 18 Gew. gebracht.50 kg of a filler grade with a nicotine content of 1.8% by weight and a moisture content of 11% by weight are made using a trans-nicotine-N'-oxide solution consisting of 4.3 l of water and 200 g of trans-nicotine N'-oxide, brought to an expansion moisture of approx. 18% by weight.
Die aufgebrachte trans-Nicotin-N'-oxid-Menge kompensiert den bei Tabakexpansionsverfahren stets zu erwartenden 25 %-igen Nicotinverlust, so daß der expandierte Tabak mit seinem ursprünglichen Nicotingehalt zum Mischungsaufbau beitragen kann.The applied amount of trans-nicotine-N'-oxide compensates for the 25% loss of nicotine which is always to be expected in tobacco expansion processes, so that the expanded tobacco with its original nicotine content can contribute to the mixture build-up.
Dieses Beipiel zeigt deutlich den mit einem Zusatz von trans-Nicotin-N'-oxid erreichbaren Vorteil bei Tabakmaterial, dessen Volumen in einem üblichen Expansionsschritt vergrößert werden soll; diese Expansion ist stets mit einem Nicotinverlust verbunden.This example clearly shows the advantage that can be achieved with the addition of trans-nicotine-N'-oxide in tobacco material, the volume of which is to be increased in a conventional expansion step; this expansion is always associated with a loss of nicotine.
Claims (15)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3344554 | 1983-12-09 | ||
DE19833344554 DE3344554A1 (en) | 1983-12-09 | 1983-12-09 | SMOKING PRODUCT CONTAINING NICOTIN-N 'OXIDE |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0144934A2 true EP0144934A2 (en) | 1985-06-19 |
EP0144934A3 EP0144934A3 (en) | 1986-03-19 |
EP0144934B1 EP0144934B1 (en) | 1988-05-04 |
Family
ID=6216485
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84114573A Expired EP0144934B1 (en) | 1983-12-09 | 1984-11-30 | Smoking product containing nicotine-n'-oxide |
Country Status (5)
Country | Link |
---|---|
US (1) | US4641667A (en) |
EP (1) | EP0144934B1 (en) |
AU (1) | AU3642084A (en) |
CA (1) | CA1249831A (en) |
DE (2) | DE3344554A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023213392A1 (en) * | 2022-05-04 | 2023-11-09 | Martin Schwarz | Combustion-free cigarette |
Families Citing this family (73)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6479558B1 (en) * | 2000-04-04 | 2002-11-12 | Westinghouse Savannah River Company | Microbial processing of used rubber |
US7810507B2 (en) * | 2006-02-10 | 2010-10-12 | R. J. Reynolds Tobacco Company | Smokeless tobacco composition |
US7946295B2 (en) * | 2007-07-23 | 2011-05-24 | R. J. Reynolds Tobacco Company | Smokeless tobacco composition |
US8061362B2 (en) | 2007-07-23 | 2011-11-22 | R. J. Reynolds Tobacco Company | Smokeless tobacco composition |
DK2377413T3 (en) | 2007-07-23 | 2017-05-01 | Reynolds Tobacco Co R | Smokeless tobacco compositions and methods of treating tobacco for use therein |
US8506936B2 (en) * | 2008-11-25 | 2013-08-13 | Watson Laboratories, Inc. | Stabilized nicotine chewing gum |
US8434496B2 (en) | 2009-06-02 | 2013-05-07 | R. J. Reynolds Tobacco Company | Thermal treatment process for tobacco materials |
US8944072B2 (en) * | 2009-06-02 | 2015-02-03 | R.J. Reynolds Tobacco Company | Thermal treatment process for tobacco materials |
US8991403B2 (en) | 2009-06-02 | 2015-03-31 | R.J. Reynolds Tobacco Company | Thermal treatment process for tobacco materials |
US9420825B2 (en) | 2012-02-13 | 2016-08-23 | R.J. Reynolds Tobacco Company | Whitened tobacco composition |
US9339058B2 (en) | 2012-04-19 | 2016-05-17 | R. J. Reynolds Tobacco Company | Method for producing microcrystalline cellulose from tobacco and related tobacco product |
US20160073686A1 (en) | 2014-09-12 | 2016-03-17 | R.J. Reynolds Tobacco Company | Tobacco-derived filter element |
US11154087B2 (en) | 2016-02-02 | 2021-10-26 | R.J. Reynolds Tobacco Company | Method for preparing flavorful compounds isolated from black liquor and products incorporating the flavorful compounds |
US10196778B2 (en) | 2017-03-20 | 2019-02-05 | R.J. Reynolds Tobacco Company | Tobacco-derived nanocellulose material |
US10757964B2 (en) | 2017-07-20 | 2020-09-01 | R.J. Reynolds Tobacco Company | Purification of tobacco-derived protein compositions |
US20200196658A1 (en) | 2018-12-20 | 2020-06-25 | R.J. Reynolds Tobacco Company | Method for whitening tobacco |
EP3911167A1 (en) | 2019-01-18 | 2021-11-24 | R. J. Reynolds Tobacco Company | Plant-derived rubisco protein purification |
US20210068447A1 (en) | 2019-09-11 | 2021-03-11 | R. J. Reynolds Tobacco Company | Pouched products with enhanced flavor stability |
EP4027817A1 (en) | 2019-09-11 | 2022-07-20 | Nicoventures Trading Limited | Alternative methods for whitening tobacco |
US20210068448A1 (en) | 2019-09-11 | 2021-03-11 | Nicoventures Trading Limited | Method for whitening tobacco |
US20210068446A1 (en) | 2019-09-11 | 2021-03-11 | R. J. Reynolds Tobacco Company | Oral product with cellulosic flavor stabilizer |
US11369131B2 (en) | 2019-09-13 | 2022-06-28 | Nicoventures Trading Limited | Method for whitening tobacco |
US11903406B2 (en) | 2019-09-18 | 2024-02-20 | American Snuff Company, Llc | Method for fermenting tobacco |
MX2022005285A (en) | 2019-10-31 | 2022-05-24 | Nicoventures Trading Ltd | Oral product and method of manufacture. |
WO2021116856A2 (en) | 2019-12-09 | 2021-06-17 | Nicoventures Trading Limited | Oral products |
US20210169129A1 (en) | 2019-12-09 | 2021-06-10 | Nicoventures Trading Limited | Lipid-containing oral composition |
WO2021116916A1 (en) | 2019-12-09 | 2021-06-17 | Nicoventures Trading Limited | Oral product with multiple flavors having different release profiles |
US20210169868A1 (en) | 2019-12-09 | 2021-06-10 | Nicoventures Trading Limited | Oral compositions with reduced water content |
US20210169784A1 (en) | 2019-12-09 | 2021-06-10 | Nicoventures Trading Limited | Buffered oral compositions |
US11617744B2 (en) | 2019-12-09 | 2023-04-04 | Nico Ventures Trading Limited | Moist oral compositions |
US20210169785A1 (en) | 2019-12-09 | 2021-06-10 | Nicoventures Trading Limited | Oral compositions with reduced water activity |
MX2022006901A (en) | 2019-12-09 | 2022-09-21 | Nicoventures Trading Ltd | Oral product with dissolvable component. |
US20210169123A1 (en) | 2019-12-09 | 2021-06-10 | Nicoventures Trading Limited | Pouched products with enhanced flavor stability |
US20210169783A1 (en) | 2019-12-09 | 2021-06-10 | Nicoventures Trading Limited | Oral products with controlled release |
US20210169126A1 (en) | 2019-12-09 | 2021-06-10 | Nicoventures Trading Limited | Oral composition with salt inclusion |
US20210169138A1 (en) | 2019-12-09 | 2021-06-10 | Nicoventures Trading Limited | Fibrous fleece material |
US11672862B2 (en) | 2019-12-09 | 2023-06-13 | Nicoventures Trading Limited | Oral products with reduced irritation |
US11793230B2 (en) | 2019-12-09 | 2023-10-24 | Nicoventures Trading Limited | Oral products with improved binding of active ingredients |
US20210169890A1 (en) | 2019-12-09 | 2021-06-10 | Nicoventures Trading Limited | Oral composition with polymeric component |
US20210169121A1 (en) | 2019-12-09 | 2021-06-10 | Nicoventures Trading Limited | Liquid oral composition |
MX2022006980A (en) | 2019-12-09 | 2022-08-25 | Nicoventures Trading Ltd | Pouched products with heat sealable binder. |
US11889856B2 (en) | 2019-12-09 | 2024-02-06 | Nicoventures Trading Limited | Oral foam composition |
WO2021116881A1 (en) | 2019-12-09 | 2021-06-17 | Nicoventures Trading Limited | Oral product in a pourous pouch comprising a fleece material |
US20210169132A1 (en) | 2019-12-09 | 2021-06-10 | Nicoventures Trading Limited | Oral composition including gels |
US20210169788A1 (en) | 2019-12-09 | 2021-06-10 | Nicoventures Trading Limited | Oral product and method of manufacture |
US20210169786A1 (en) | 2019-12-09 | 2021-06-10 | Nicoventures Trading Limited | Oral composition with beet material |
WO2021116842A1 (en) | 2019-12-09 | 2021-06-17 | Nicoventures Trading Limited | Oral products with controlled release |
WO2021116865A1 (en) | 2019-12-09 | 2021-06-17 | Nicoventures Trading Limited | Agents for oral composition |
US20210169137A1 (en) | 2019-12-09 | 2021-06-10 | Nicoventures Trading Limited | Pouched products |
WO2021116919A1 (en) | 2019-12-09 | 2021-06-17 | Nicoventures Trading Limited | Fleece for oral product with releasable component |
US11712059B2 (en) | 2020-02-24 | 2023-08-01 | Nicoventures Trading Limited | Beaded tobacco material and related method of manufacture |
US11937626B2 (en) | 2020-09-04 | 2024-03-26 | Nicoventures Trading Limited | Method for whitening tobacco |
US20240008522A1 (en) | 2020-11-18 | 2024-01-11 | Nicoventures Trading Limited | Oral products |
US20220232881A1 (en) | 2021-01-28 | 2022-07-28 | Nicoventures Trading Limited | Method for sealing pouches |
WO2022195562A1 (en) | 2021-03-19 | 2022-09-22 | Nicoventures Trading Limited | Extruded substrates for aerosol delivery devices |
EP4307927A1 (en) | 2021-03-19 | 2024-01-24 | Nicoventures Trading Limited | Beaded substrates for aerosol delivery devices |
EP4326095A1 (en) | 2021-04-22 | 2024-02-28 | Nicoventures Trading Limited | Orally dissolving films |
WO2022229929A1 (en) | 2021-04-30 | 2022-11-03 | Nicoventures Trading Limited | Oral products with high-density load |
US20220354155A1 (en) | 2021-04-30 | 2022-11-10 | Nicoventures Trading Limited | Multi-compartment oral pouched product |
BR112023023129A2 (en) | 2021-05-06 | 2024-02-06 | Nicoventures Trading Ltd | ORAL COMPOSITIONS AND RELATED METHODS TO REDUCE THROAT IRRITATION |
CA3222813A1 (en) | 2021-06-16 | 2022-12-22 | Anthony Richard Gerardi | Pouched product comprising dissolvable composition |
WO2022269475A1 (en) | 2021-06-21 | 2022-12-29 | Nicoventures Trading Limited | Oral product tablet and method of manufacture |
CA3223902A1 (en) | 2021-06-25 | 2022-12-29 | Richard Svensson | Oral products and method of manufacture |
WO2023007440A1 (en) | 2021-07-30 | 2023-02-02 | Nicoventures Trading Limited | Aerosol generating substrate comprising microcrystalline cellulose |
CA3233389A1 (en) | 2021-09-30 | 2023-04-06 | Nicolas H. VON COSMOS | Oral gum composition |
CA3233375A1 (en) | 2021-09-30 | 2023-04-06 | Michael Zawadzki | Oral product with a basic amine and an ion pairing agent |
WO2023084498A1 (en) | 2021-11-15 | 2023-05-19 | Nicoventures Trading Limited | Oral products with nicotine-polymer complex |
US20230148660A1 (en) | 2021-11-15 | 2023-05-18 | Nicoventures Trading Limited | Products with enhanced sensory characteristics |
US20230309603A1 (en) | 2022-03-31 | 2023-10-05 | R.J. Reynolds Tobacco Company | Agglomerated botanical material for oral products |
WO2023194959A1 (en) | 2022-04-06 | 2023-10-12 | Nicoventures Trading Limited | Pouched products with heat sealable binder |
WO2023242822A1 (en) | 2022-06-17 | 2023-12-21 | Nicoventures Trading Limited | Tobacco-coated sheet and consumable made therefrom |
WO2024069544A1 (en) | 2022-09-30 | 2024-04-04 | Nicoventures Trading Limited | Reconstituted tobacco substrate for aerosol delivery device |
WO2024069542A1 (en) | 2022-09-30 | 2024-04-04 | R. J. Reynolds Tobacco Company | Method for forming reconstituted tobacco |
-
1983
- 1983-12-09 DE DE19833344554 patent/DE3344554A1/en not_active Withdrawn
-
1984
- 1984-11-30 EP EP84114573A patent/EP0144934B1/en not_active Expired
- 1984-11-30 DE DE8484114573T patent/DE3470830D1/en not_active Expired
- 1984-12-07 US US06/679,573 patent/US4641667A/en not_active Expired - Fee Related
- 1984-12-07 CA CA000469624A patent/CA1249831A/en not_active Expired
- 1984-12-07 AU AU36420/84A patent/AU3642084A/en not_active Abandoned
Non-Patent Citations (5)
Title |
---|
CHEMICAL ABSTRACTS, Band 59, Nr. 13, 23. Dezember 1963, Spalte 15616d,e, Columbus, Ohio, US; N. IVANOV: "Study of alkaloids in Bulgarian cigarets and smoke by means of paper chromatography", & COMPT. REND. ADAD. BULGARE SCI. 12(4), 317-20(1959) * |
JOURNAL OF ORGANIC CHEMISTRY, Band 24, Februar 1959, Seiten 275-277, US; E.C. TAYLOR et al.: "Pyridine-1-oxides. IV. Nicotine-1-oxide, nicotine-1'-oxide, and nicotine-1,1'-dioxide" * |
JOURNAL OF ORGANIC CHEMISTRY, Band 35, Nr. 5, Mai 1970, Seiten 1721-1722, US; J. CYMERMAN CRAIG et al.: "An improved preparation of tertiary amine N-oxides" * |
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Band 77, 5. November 1955, Seiten 5728-5730, US; W.G. FRANKENBURG et al.: "The chemistry of tobacco fermentation. I. Conversion of the alkaloids. B. The formation of oxynicotine" * |
JOURNAL OF THE CHEMICAL SOCIETY, 1958, Seiten 3230-3231, US; A.W. JOHNSON et al.: "New transformation products of nicotine" * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023213392A1 (en) * | 2022-05-04 | 2023-11-09 | Martin Schwarz | Combustion-free cigarette |
Also Published As
Publication number | Publication date |
---|---|
DE3470830D1 (en) | 1988-06-09 |
EP0144934A3 (en) | 1986-03-19 |
AU3642084A (en) | 1985-06-13 |
EP0144934B1 (en) | 1988-05-04 |
CA1249831A (en) | 1989-02-07 |
DE3344554A1 (en) | 1985-06-20 |
US4641667A (en) | 1987-02-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0144934B1 (en) | Smoking product containing nicotine-n'-oxide | |
EP0035683B1 (en) | Process for the production of aromatic substances | |
DD233126A5 (en) | PROCESS FOR THE PREPARATION OF PYRIDINE N-OXIDES | |
DE1692759B2 (en) | Flavored tobacco | |
DE2639010C2 (en) | Process for the preparation of concentrated hydrazine hydrate solutions | |
EP0346648B1 (en) | Process for impregnating the fibres of a tobacco smoke filter with di- or polycarboxylic acids or their anhydrides | |
EP0083799B1 (en) | Process to improve the filling capacity of tobacco, in particular cut tobacco leaves | |
CH650128A5 (en) | AN UNSATURATED CARBOXYL FATTY ACID CONTAINING A FRAGRANCE MIXTURE. | |
DE2142653C3 (en) | 1,1-bis (subst-phenyl) -2-nitroalkanes, processes for their preparation and insecticides containing these compounds | |
DE2458639C3 (en) | Tobacco products with an additive that changes taste or aroma | |
DE1517018A1 (en) | Process for the preparation of beta, gamma-unsaturated aliphatic aldehydes | |
DE1692940A1 (en) | Process for the manufacture of a tobacco product | |
DE828104C (en) | Process for the preparation of N, N -substituted piperazines | |
DE1008277B (en) | Process for the production of ªÏ, ªÏ'-dicarboxylic acids | |
DE1470256A1 (en) | Process for the preparation of new heterocyclic compounds | |
DE1517331B1 (en) | Process for improving a tobacco product | |
DE1620479C3 (en) | Xylitol pentanicotinate and its acid addition salts | |
DE1517325C (en) | Process for improving tobacco | |
DE1517331C (en) | Process for improving a tobacco product | |
EP0007582B1 (en) | Compositions and process for reinforcing, modifying or improving the organoleptic properties of tobacco products and compounds useful therefor | |
DE2712901A1 (en) | METHOD OF MANUFACTURING FURFURAL | |
DE2221123C2 (en) | Reserpic acid derivatives, processes for their preparation and pharmaceuticals | |
DE3132687A1 (en) | "METHOD FOR PRODUCING KETOAIDS FROM (ALPHA), SS-UNSATURATED CYCLIC KETONES" | |
CH476661A (en) | Process for the preparation of 4,4a, 5,6-tetrahydro-4,4,7-trimethyl-2 (3H) -naphthalenone | |
DE2219116C3 (en) | Process for the preparation of 5-hydroxy-1-tetralone |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): BE CH DE GB LI NL |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE CH DE GB LI NL |
|
17P | Request for examination filed |
Effective date: 19860409 |
|
17Q | First examination report despatched |
Effective date: 19870721 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE CH DE GB LI NL |
|
REF | Corresponds to: |
Ref document number: 3470830 Country of ref document: DE Date of ref document: 19880609 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19890103 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19890207 Year of fee payment: 5 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19891130 Ref country code: GB Effective date: 19891130 Ref country code: CH Effective date: 19891130 Ref country code: BE Effective date: 19891130 |
|
BERE | Be: lapsed |
Owner name: B.A.T. CIGARETTEN-FABRIKEN G.M.B.H. Effective date: 19891130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19900601 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19931203 Year of fee payment: 10 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19950801 |