Smoking compositions containing a flavorant-release saccharide additive

This invention provides smoking compositions which contain a novel flavorant-release additive. Under cigarette smoking conditions, a combustible filler and/or paper wrapper additive such as 4'-formyl-2'-methoxyphenyl 4,6-O-cinnamylidene-.beta.-D-glucopyranoside pyrolyzes into cinnamaldehyde and vanillin flavorants as volatile components of the cigarette smoke.

BACKGROUND OF THE INVENTION 
A variety of flavorants have been developed and proposed for incorporation 
into tobacco products. Illustrative of such tobacco flavorants are those 
described in U.S. Pat. Nos. 3,580,259; 3,625,224; 3,722,516; 3,750,674; 
3,879,425; 3,881,025; 3,884,247; 3,890,981; 3,903,900; 3,914,451; 
3,915,175; 3,920,027; 3,924,644; 3,937,228; 3,943,943; 3,568,387; 
3,379,754; and the like. 
J. C. Leffingwell et al "Tobacco Flavoring For Smoking Products (R. J. 
Reynolds publication, 1972) recites a listing of desirable flavorants for 
smoking compositions, which include phenols, terpenols and lactones such 
as guaiacol, 1-undecanol and 5-dodecalactone. 
The high degree of volatility and ease of sublimation of flavorant 
additives in tobacco products have presented problems in the manufacturing 
operations, and have resulted in a decreased shelf-life of the products 
due to losses of flavorant by evaporation on storage. 
Recent developments have involved incorporating a low volatility organic 
additive to a smoking composition, which under smoking conditions is 
pyrolyzed into one or more fragments that function to improve the taste 
and character of mainstream tobacco smoke, and in some cases a 
consequential improvement of sidestream smoke aroma. 
U.S. Pat. No. 3,312,226 describes smoking tobacco compositions which 
contain an ester additive such as 1-menthyl linalool carbonate. Under 
smoking conditions pyrolysis of the carbonate ester releases menthol which 
flavors the mainstream smoke. 
U.S. Pat. No. 3,332,428 and U.S. Pat. No. 3,419,543 describe smoking 
tobacco compositions which contain a menthyl carbonate ester of a glycol 
or saccharide, which under smoking conditions decomposes to release free 
menthol into the mainstream smoke. U.S. Pat. No. 3,499,452 discloses 
similar smoking tobacco compositions in which a carbonate ester additive 
releases flavorant volatiles other than menthol. 
U.S. Pat. Nos. 4,119,106; 4,171,702; 4,177,339; and 4,212,310 describe 
other oligomeric and polymeric carbonate ester derivatives which as 
constituents of smoking compositions are stable and non-volatile under 
storage conditions, and are adapted to release pyrolysis products under 
smoking conditions that improve the taste and aroma of smoke. 
U.S. Pat. Nos. 4,036,237; 4,141,906; and 4,178,458 describe 
.beta.-hydroxyesters which as additives in smoking compositions pyrolyze 
into volatile aldehyde and ester flavorants under smoking conditions. 
Of specific interest with respect to the present invention is the proposed 
utilization of an organic additive to a cigarette paper wrapper to enhance 
sidestream smoke aroma under smoking conditions. U.S. Pat. No. 4,804,002 
describes a tobacco product wrapper containing a flavorant additive 
comprising a glycoside of a carbohydrate and phenolic compound. Under 
cigarette smoking conditions a flavorant additive such as ethyl 
vanillyl-D-glucoside yields ethyl vanillin and levoglucosan as pyrolysis 
products. 
There is continuing research effort to develop low delivery smoking 
compositions which generate mainstream smoke with enhanced taste and 
sidestream smoke with a pleasant aroma under smoking conditions. 
Accordingly, it is an object of this invention to provide smoking 
compositions having incorporated therein a flavorant-release component 
which is characterized by lack of mobility and/or volatility at ambient 
temperature. 
It is another object of this invention to provide cigarette smoking 
products having a paper wrapper which has incorporated therein a 
flavorant-release additive which under normal smoking conditions imparts 
improved aroma to sidestream smoke. 
It is a further object of this invention to provide novel glucopyranose and 
qlucopyranoside acetals and ketals which are adapted to be incorporated 
into cigarette filler and/or paper wrapper components, and which under 
normal smoking conditions release a volatile carbonyl flavorant into 
cigarette smoke. 
Other objects and advantages of the present invention shall become apparent 
from the following description and examples. 
DESCRIPTION OF THE INVENTION 
One or more objects of the present invention are accomplished by the 
provision of a smoking composition comprising an admixture of (1) 
combustible filler selected from natural tobacco, reconstituted tobacco 
and tobacco substitutes, and (2) between about 0.0001-5 weight percent, 
based on the total weight of filler, of a flavorant-release additive 
corresponding to the formula: 
##STR1## 
where R--C.dbd. is a C.sub.7 -C.sub.12 benzylidene or C.sub.9 -C.sub.15 
cinnamylidene structure, R.sup.1 is hydrogen or a C.sub.6 -C.sub.10 
aromatic substituent, and R.sup.2 is hydrogen or a C.sub.1 -C.sub.6 alkyl 
substituent. 
In another embodiment this invention provides a cigarette smoking product 
comprising (1) a combustible filler selected from natural tobacco, 
reconstituted tobacco and tobacco substitutes, and (2) a paper wrapper 
which has incorporated therein a flavorant-release additive corresponding 
to the formula: 
##STR2## 
where R--C.dbd. is a C.sub.7 -C.sub.12 benzylidene or C.sub.9 -C.sub.15 
cinnamylidene structure, R.sup.1 is hydrogen or a C.sub.6 -C.sub.10 
aromatic substituent, and R.sup.2 is hydrogen or a C.sub.1 -C.sub.6 alkyl 
substituent. 
Illustrative of the R--C.dbd. divalent radical in the above represented 
flavorant-release additive formula are structures which are derived from 
benzaldehyde having one or more substituents which include hydroxy, 
C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.1 -C.sub.6 
alkanoyl, and the like; or derived from cinnamaldehyde having similar ring 
substituents as the benzaldehyde structure, or having substituents such as 
C.sub.1 -C.sub.6 alkyl on the ethylenic sidechain. 
Illustrative of the R.sup.1 substituent in the additive formula are 
structures which are derived from phenols such as vanillin, ethyl 
vanillin, thymol, guaiacol, methyl salicylate, eugenol, and the like. 
The R.sup.1 substituent in the additive formula also can be a saccharide 
structure, which taken together with the pyranose elements can represent a 
disaccharide such as cellobiose or lactose. 
Illustrative of the R.sup.2 substituent are hydrogen, methyl, ethyl, 
propyl, isopropyl, butyl, isobutyl, 2-butyl, pentyl, hexyl, and the like. 
The pyranose or pyranoside structure in the additive formula is derived 
from an aldohexose such as glucose, mannose, galactose, and the like. 
A cigarette smoking product with treated paper wrapper in accordance with 
the present invention typically contains between about 0.01-5 weight 
percent of flavorant-release additive in the paper wrapper. 
In a further embodiment an invention cigarette product contains between 
about 0.01-5 weight percent of flavorant-release additive in the paper 
wrapper, and contains between about 0.0001-5 weight percent of 
flavorant-release additive in the combustible filler, based on the weight 
of filler. 
A present invention flavorant-release additive which is incorporated in 
smoking compositions as described above is a low volatility compound which 
under normal smoking conditions in the case of a preferred species 
pyrolyzes into two volatile constituents, both of which enhance the flavor 
and aroma of low delivery cigarette smoke: 
##STR3## 
An important feature of the above illustrated invention smoking composition 
is the release of two aromatic flavorants under smoking conditions, one of 
which is a cinnamaldehyde type structure. 
Both the cinnamaldehyde and vanillin volatiles which are released have 
exceptional organoleptic properties. Each of the compounds contributes a 
pleasant flavor and aroma to cigarette smoke. 
Preparation Of Flavorant-release Compounds 
One method of preparing the invention flavorant-release compounds is by the 
condensation of a benzaldehyde or cinnamaldehyde type reactant with a 
hexoaldose derivative: 
##STR4## 
The ethyl vanillin reactant in the above illustrated flow diagram is 
obtained by a synthesis procedure similar to that described in U.S. Pat. 
No. 4,804,002. 
Reaction conditions for mild acid-catalyzed transacetalation of aldehyde 
acetals with saccharides are described in technical publications which 
include Carbohyd. Res., 21, 473(1972); Tetrahedron Lett., 29 (No. 9), 
991(1988); and Aust. J. Chem., 41, 91(1988). 
Preparation Of Tobacco Compositions 
In a further embodiment the present invention provides a method of 
preparing a smoking composition which is adapted to impart flavor and 
aroma to mainstream and sidestream smoke under conditions, which method 
comprises incorporating into natural tobacco, reconstituted tobacco or 
tobacco substitute between about 0.0001-5 weight percent, based on 
composition weight, of a flavorant-release additive corresponding to the 
formula: 
##STR5## 
where R--C.dbd. is a C.sub.7 -C.sub.12 benzylidene or C.sub.9 -C.sub.15 
cinnamylidene structure, R.sup.1 is hydrogen or a C.sub.6 -C.sub.10 
aromatic substituent, and R.sup.2 is hydrogen or a C.sub.1 -C.sub.6 alkyl 
substituent. 
The invention flavorant-release additive can be incorporated into the 
tobacco or tobacco substitute in accordance with methods known and used in 
the art. Preferably the flavorant-release additive is dissolved in a 
solvent such as alcohol or aqueous alcohol and then sprayed or injected 
into the tobacco and/or tobacco substitute matrix. Such method ensures an 
even distribution of the flavorant additive throughout the filler, and 
thereby facilitates the production of a more uniform smoking composition. 
Alternatively, the flavorant may be incorporated as part of a concentrated 
tobacco extract which is applied to a fibrous tobacco web as in the 
manufacture of reconstituted tobacco. Another suitable procedure is to 
incorporate the flavorant in tobacco or tobacco substitute filler in a 
concentration between about 0.5-5 weight percent, based on the weight cf 
filler, and then subsequently to blend the treated filler with filler 
which does not contain flavorant additive. 
The term "tobacco substitute" is meant to include non-tobacco smoking 
filler materials such as are disclosed in U.S. Pat. Nos. 3,703,177; 
3,796,222; 4,019,521; 4,079,742; and references cited therein, 
incorporated herein by reference. 
U.S. Pat. No. 3,703,177 describes a process for preparing a non-tobacco 
smoking product from sugar beet pulp, which process involves the acid 
hydrolysis of the beet pulp to release beet pectins, and at least an 
alkaline earth treatment thereafter to cause crosslinking of the pectins 
and the formation of a binding agent for the exhausted beet matrix. 
U.S. Pat. No. 3,796,222 describes a smoking product derived from coffee 
bean hulls. The hulls are treated with reagents that attack the alkaline 
earth metal crosslinks causing the release of the coffee pectins. The 
pectins act as a binding agent and together with the treated hulls may be 
handled and used similarly to a tobacco product. 
U.S. Pat. No. 4,019,521 discloses a process for forming a smoking material 
which involves heating a cellulosic or carbohydrate material at a 
temperature of 150.degree.-750.degree. C. in an inert atmosphere for a 
period of time sufficient to effect a weight loss of at least 60 percent 
but not more than 90 percent. 
U.S. Pat. No. 4,079,742 discloses a process for the manufacture of a 
synthetic smoking product from a cellulosic material, which process 
involves a pyrolysis step and a basic extraction step to yield a resultant 
matrix which has a tobacco-like brown color and has improved smoking 
characteristics. 
As previously described hereinabove, an invention flavorant-release 
additive also can be incorporated in the paper wrapper of cigarette 
products, for the purpose of enhancing the aroma of cigarette sidestream 
smoke under smoking conditions.

The following Examples are further illustrative of the present invention. 
The specific ingredients and processing parameters are presented as being 
typical, and various modifications can be derived in view of the foregoing 
disclosure within the scope of the invention. 
EXAMPLE I 
4'-Formyl-2,'-methoxyphenyl 
4,6-O-(.alpha.-hexylcinnamylidene)-.beta.-D-glucopyranoside 
##STR6## 
A 3.14 g (10 mmole) quantity of glucovanillin and 0.5 g of Amberlite.RTM. 
IR-120 (Rohm & Haas Co.) were mixed with 40 ml of acetonitrile, and the 
admixture was heated to reflux. A total of three 2.6 g (10 mmole) 
quantities of a .alpha.-hexylcinnamylaldehyde dimethyl acetal were added 
in one hour intervals. After the additions were completed, the heating at 
reflux was continued for an additional hour. The reaction medium then was 
cooled to room temperature, and the ion exchange resin catalyst was 
removed by filtration. After removal of solvent by rotary evaporation 
under vacuum, the residual syrup was distilled by Kugelrohr at a pot 
temperature of &lt;115.degree. C. and a vacuum of &lt;0.3 mm Hg. The residue 
after distillation was recrystallized from 95% ethanol to yield 4 g of 
product. NMR and IR spectra confirmed the title compound structure. 
EXAMPLE II 
4'-Formyl-2'-methoxyphenyl 
4,6-O-(.alpha.-amylcinnamylidene)-.beta.-D-glucopyranoside 
##STR7## 
The title compound was prepared following the procedures of Example I, 
using 3.14 g (10 mmole) of glucovanillin and 3.times.2.5 g (30 mmole) of 
.alpha.-amylcinnamylaldehyde dimethyl acetal. After recrystallization from 
95% ethanol, 4.5 g of product was obtained. NMR and IR spectra confirmed 
the title compound structure. 
EXAMPLE III 
4'-Formyl-2'-methoxyphenyl 4,6-O-cinnamylidene-.beta.-D-glucopyranoside 
##STR8## 
The title compound was prepared following the procedures of Example I, 
using 3.14 g of glucovanillin (10 mmole) and 3.times.1.8 g of 
cinnamylaldehyde dimethyl acetal (30 mmole). After recrystallization from 
95% ethanol, 3 g of product was obtained. NMR and IR spectra confirmed the 
title compound structure. 
EXAMPLE IV 
2'-Methoxy-4'-methylphenyl 
4,6-O-(.alpha.-hexylcinnamylidene)-.alpha.-D-glucopyranoside 
##STR9## 
The title compound was prepared following the procedures of Example I, 
using 3 g (10 mmole) of 2'-methoxy-4'-methylphenyl 
.alpha.-D-glucopyranoside and 3.times.2.6 g (30 mmole) of 
.alpha.-hexylcinnamylaldehyde dimethyl acetal. After recrystallization 
from acetone, 3.8 g of product was obtained. NMR and IR spectra confirmed 
the title compound structure. 
EXAMPLE V 
4-6-O-Cinnamylidene-D-glucopyranose 
##STR10## 
A 1.8 g quantity of glucose was dissolved in 40 ml of dimethylformamide, 
and 1 g amount of Amberlite.RTM. IR-120 was added. The mixture was heated 
to 80.degree. C., and a total of three 1.78 g quantities of 
cinnamylaldehyde dimethyl acetal were added in one hour intervals. After 
the additions were completed, the mixture was heated for an additional 
hour. The ion exchange resin catalyst was removed by filtration, and the 
solvent and excess cinnamylaldehyde dimethyl acetal were removed by vacuum 
distillation. The residual material was recrystallized from 95% ethanol to 
give 1.5 g of product. NMR and IR spectra confirmed the title compound 
structure. 
EXAMPLE VI 
4,6-O-(.alpha.-Amylcinnamylidene)-D-glucopyranose 
##STR11## 
The title compound was prepared following the procedures of Example V, 
using 3.6 g (20 mmole) of glucose and 3.times.4.96 g (60 mmole) of 
.alpha.-amylcinnamylaldehyde dimethyl acetal in 80 ml of 
dimethylformamide. After recrystallization from 95% ethanol (containing a 
few drops of concentrated ammonium hydroxide), 5.5 g of product was 
obtained. NMR and IR spectra confirmed the title compound structure. 
EXAMPLE VII 
4,6-O-(.alpha.-Hexylcinnamylidene)-D-glucopyranose 
##STR12## 
The title compound was prepared following the procedures of Example V, 
using 3.6 g of glucose (20 mmole) and 3.times.5.14 g of 
.alpha.-hexylcinnamylaldehyde dimethyl acetal (60 mmole) in 80 ml of 
dimethylformamide. After recrystallization from 80% ethanol, 5.2 g of 
product was obtained. NMR and IR spectra confirmed the title compound 
structure. 
EXAMPLE VIII 
4,6-O-(4'-Hydroxy-3'-methoxybenzylidene)-D-glucopyranose 
##STR13## 
The title compound was prepared following the procedures of Example V, 
using 3.6 g (20 mmole) of glucose and 3.times.4.0 g (60 mmole) of vanillin 
dimethyl acetal. After removal of solvent and unreacted starting acetal by 
vacuum distillation, the residual material was recrystallized from 80/20 
ethanol/10% ammonium hydroxide to give 5.1 g of product. NMR and IR 
spectra confirmed the title compound structure. 
EXAMPLE IX 
4,6-O-(3'-Ethoxy-4'-hydroxybenzylidene)-D-glucopyranose 
##STR14## 
The title compound was prepared following the procedures of Example V, 
using 1.8 g of glucose and 3.times.2.12 g of ethyl vanillin dimethyl 
acetal. Isolation of the product (2.5 g ) was achieved by preparative 
HPLC. NMR and IR spectra confirmed the title compound structure. 
EXAMPLE X 
4,6-O-(3',4'-Dimethoxybenzylidene)-D-glucopyranose 
##STR15## 
The title compound was prepared following the of Example V, using 3.6 g (20 
mmole) of glucose and 3.times.4.24 g (60 mmole) of dimethoxybenzaldehyde 
dimethyl acetal. After recrystallization from 95% ethanol, 4.8 g of 
product was obtained. NMR and IR spectra confirmed the title compound 
structure. 
EXAMPLE XI 
4,6-O-(4'-Acetoxy-3'-methoxybenzylidene)-D-glucopyranose 
##STR16## 
The title compound was prepared following the procedures of Example V, 
using 3.6 g (20 mmole) of glucose and 3.times.4.8 g (60 mmole) of vanillin 
acetate dimethyl acetal. Recrystallization from acetone yielded 5.1 g of 
product. NMR and IR spectra confirmed the title compound structure. 
EXAMPLE XII 
4,6-O-[.alpha.-(4'-Hydroxy-3'-methoxyphenyl)ethylidene]-D-glucopyranose 
##STR17## 
The title compound was prepared following the procedures of Example V, 
using 3.6 g (20 mmole) of glucose and 3.times.4.2 (60 mmole) of 
acetovanillone dimethyl ketal. After removal of solvent and unreacted 
starting ketal by vacuum distillation, the residual material was 
recrystallized from 80/20 ethanol/10% ammonium hydroxide to yield 4.1 g of 
product. NMR and IR spectra confirmed the title compound structure. 
EXAMPLE XIII 
This Example illustrates the relative flavorant-release efficiencies of 
4,6-O-pyranose and 4,6-O-pyranoside derivatives under pyrolysis conditions 
in comparison with a methyl glucoside derivative. 
The samples were analyzed by Curie Point Pyrolysis/GC/MS at 315.degree. C. 
and 590.degree. C. temperatures. The instruments utilized included Japan 
Analytical Industry JHP3S Pyroprobe, Varian 3400 Gas Chromatograph and a 
Finnigan 700 Ion Trap Mass Spec Detector (ITD). Samples of a 
flavorant-release compound (.about.30-45 .mu.g) were pyrolyzed at each 
temperature for 5 seconds and the volatile products swept onto the head of 
a DB5-30M fused silica capillary column which was held at 0.degree. C. 
After 4 minutes, the column oven was heated to 280.degree. C. at 
10.degree. /minute. Detection was accomplished using the ITD, in the 
Electron Ionization mode. The relative amount of released flavorant 
material is calculated from the reconstructed chromatogram as area counts 
per microgram pyrolyzed. 
______________________________________ 
Area Count Per Microgram Pyrolyzed 
Compound 315.degree. C. 
590.degree. C. 
______________________________________ 
Aromatek A-245.sup.(1) 
2.4 .times. 10.sup.5 
7.2 .times. 10.sup.5 
Example III compound 
1.4 .times. 10.sup.5 
14.9 .times. 10.sup.5 
Example V compound 
25.0 .times. 10.sup.5 
21.0 .times. 10.sup.5 
______________________________________ 
.sup.(1) Fritzsche, Dodge & Olcott. Methyl 
4,6O-(hexylcinnamylidene)-D-glucopyranoside. 
The data demonstrated that invention pyranose and pyranoside derivatives 
exhibited a higher flavorant-release efficiency than a known methyl 
glucoside under pyrolysis conditions.