CA1237145A - Acetylenic compounds containing urea moieties useful as environmental indicating materials - Google Patents
Acetylenic compounds containing urea moieties useful as environmental indicating materialsInfo
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- CA1237145A CA1237145A CA000457436A CA457436A CA1237145A CA 1237145 A CA1237145 A CA 1237145A CA 000457436 A CA000457436 A CA 000457436A CA 457436 A CA457436 A CA 457436A CA 1237145 A CA1237145 A CA 1237145A
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Abstract
ABSTRACT OF THE DISCLOSURE
ACETYLENIC COMPOUNDS CONTAINING
UREA MOIETIES USEFUL AS
ENVIRONMENTAL INDICATING MATERIALS
A novel class of acetylenic compounds is dis-closed. The acetylenic compounds include at least one -C?C-C?C-moiety and two urea moieties with at least one methylene moiety being between each -C?C-C?C- moiety and one of said urea moieties. The compounds are especially useful as environmental indicating materials.
ACETYLENIC COMPOUNDS CONTAINING
UREA MOIETIES USEFUL AS
ENVIRONMENTAL INDICATING MATERIALS
A novel class of acetylenic compounds is dis-closed. The acetylenic compounds include at least one -C?C-C?C-moiety and two urea moieties with at least one methylene moiety being between each -C?C-C?C- moiety and one of said urea moieties. The compounds are especially useful as environmental indicating materials.
Description
~3~
DESCRIPTION
ACETYLENIC COMPOUNDS CONTAINING
UREA MOIETIES USEFUL AS
ENVIRONMENTAL INDICATING MATERIALS
BACKGROUND OF THE INVENTION
This invention relates to a novel class of acety-lenic compounds that are useful as environmental indi-cating materials. The acetylenic compounds include at least one -C_C-C-C- moiety and two urea moieties, said compounds having at least one methylene moiety between each -C-C-C-C- etylene moiety and one of said urea moities. The usefulness of the compounds resides in the fact that they undergo incremental or progressive color changes upon exposure to environmental stimuli such as temperature, cumulative time-temperature and radiation. The reactivity of the compounds of this invention may be increased or decreased in some cases by co-crystallizing two or more compounds from a common solvent. The compounds of this invention, like other acetylenic compounds, change color due to polymerization via 1,4- addi~ion reactions upon exposure to environmental stimuli.
Acetylenic compounds that undergo the described color changes are known to the art. For example, acety-lenic compounds having at least one -C_C-C-C-, have been disclosed as time-temperature history indicators in U.S.
Patent No. 3,999,946 (Patel et al.). Patel et al. dis-closes monomeric acetylenic compounds of the formula, R-C-C-C--C-R, where R includes an alkyl, aryl, benzoate, sulfonate, urethane, acid or alcohol moiety. The compounds disclosed by Patel et al. are colorless and are polymerizable in the solid state, either thermally or by actinic radiation. As the polymerization pro-ceeds, these compounds undergo a contrasting colorchange to blue or red and in some instances the color intensifies with time until the compounds finally develop into metallic-looking polymers. Thus, the compounds can be used as time-temperature history indicators and as radiation-dosage indicators. The .
. .
~;~3~ 5 reference also describes polymers oE the type [c c_(cH2)mOCONM(CH2)6NHOco(cEl2)-c-c]n where m is 2~ 3 or 4 and n is large, wherein a polymer containing polymeric repeating units of the same empirical formula, undergoes color changes upon thermal annealing.
Other exemplary U.S. patents relating to acetylenic compounds and their use as environmental indicating materials include U.S. Patent No. 4,215,208 (thermo-chromic materials), 4,125,534 (carbazolyl diacetylenes), and 4,189,399 (co-crystallized compositions).
G. Wegner in an article entitled "Topochemical Polymerization of Monomers with Conjugated Triple Bonds"
in Die Makromolekulare Chemie 154, pp. 35-48 (1972) discloses acetylenic compounds having at least one -C C-C-C- moiety and two urea moieties, the urea moieties being separated from the diaetylene by a phenylene moiety. EIowever, the compounds disclosed by Wegner were not very reactive and did not exhibit color changes that would be useful in monitoring environmental exposure.
The compounds of the present invention are generally more highly reactive and are extremely useful environmental indicating materials.
BRIEF DESCRIPTION OF THE INVENTION
This invention relates to an organic, compound comprising an acetylenic compound having at least one -C_C-C_C- moiety and two urea moieties, said composition being capable o~ undergoing incremental reflectivity changes upon exposure to environmental stimuli; wherein said compounds include at least one methylene moiety between each -C-C-C-C- moiety and one o~ said urea moieties.
DETAILED D_SCRIPTION OF THE INVENTION
This invention relates to novel acetylenic com-pounds that are useful for monitoring the environmentalexposure of various products that undergo progressive quality changes upon environmental exposure. Environ-~' ~3';~1S
mental exposure refers to temperature, cumulative time-temperature, and radiation exposure.
The novel organic compounds of this invention con tain at least one -C_C-C_C- moiety and two urea moie-5 ties, said compounds having at least one methylenemoiety between each -C-C-C_C- moiety and one of said urea moieties. The acetylenic ureas of this invention undergo incremental or progressive color changes upon exposure to environmental stimuli. Thus, there is a corresponding change in reflectance or reflectivity due to exposure to environmental stimuli. Reflectance or reflectivity is defined as the amount of light at selected wavelengths that is reflected by an indicating material after said light has impinged upon the indicat-ing material. A perfectly reflective material has a - reflectance or reflectivity equal to one. Percent reflectance or reflectivity is equal to one hundred times the reflectivity. Since the acetylenic ureas undergo reflectivity changes upon exposure to environ-mental stimuli, said compounds will undergo contrasting color changes upon exposure to given amounts of actinic radiation or thermal annealing. The term "thermal annealing" refers to heating at sufficient temperatures, as by infrared radiation, flame, heat gun, laser-beam, and the like which is sufficiently high to cause poly-meri~ation by 1,4-addition of the acetylenic compounds.
It is known to the art that many acetylenic com-pounds will undergo the described reflectance or reflec-tivity contrasting color changes upon exposure to environmental stimuli actinic radiation, or thermal annealing. It is also known to use acetylenic compounds that undergo ~he described color changes as environ-mental indicating materials in view of the fact that the compounds will undergo measurable incremental color changes in response to environmental exposure. The coIor changes may be correlated with product quality by color matching procedures when a certain color corre-sponds to a given amount of product degradation or pro-.
7~5 cessing. PreEerably, however, product quality is deter-mined by the more precise incremental reflectance measurement technique descrlbed in copending Can. Appl.
Ser. No. 446,711 filed Feb. 3, 1934. The novel com-pounds of this invention exhibit highly desirableproperties which render them an especially preferred class of acetylenic compounds for use as environmental indicating materials. These properties are discussed in more detail herein below following the description of preferred urea acetylenic compounds and methods for their syntheses.
The preferred acetylenic compounds of this inven-tion are of the general structures I, II, and III as depicted hereinbelow. Structure I represents the most preferred family of compounds and is as follows:
o (I) [R-NH-C-NH-(CH2)n-C-C~2 wherein n is an integer of 1-10; wherein R is an organic moiety comprising one or more moieties selected from the group comprising a cycloalkyl moiety of 3-7 carbon atoms, an alkenyl moiety of 3-18 carbon atoms, a cyclo-alkenyl moiety of 3-7 carbon atoms, an alkoxy moiety of
DESCRIPTION
ACETYLENIC COMPOUNDS CONTAINING
UREA MOIETIES USEFUL AS
ENVIRONMENTAL INDICATING MATERIALS
BACKGROUND OF THE INVENTION
This invention relates to a novel class of acety-lenic compounds that are useful as environmental indi-cating materials. The acetylenic compounds include at least one -C_C-C-C- moiety and two urea moieties, said compounds having at least one methylene moiety between each -C-C-C-C- etylene moiety and one of said urea moities. The usefulness of the compounds resides in the fact that they undergo incremental or progressive color changes upon exposure to environmental stimuli such as temperature, cumulative time-temperature and radiation. The reactivity of the compounds of this invention may be increased or decreased in some cases by co-crystallizing two or more compounds from a common solvent. The compounds of this invention, like other acetylenic compounds, change color due to polymerization via 1,4- addi~ion reactions upon exposure to environmental stimuli.
Acetylenic compounds that undergo the described color changes are known to the art. For example, acety-lenic compounds having at least one -C_C-C-C-, have been disclosed as time-temperature history indicators in U.S.
Patent No. 3,999,946 (Patel et al.). Patel et al. dis-closes monomeric acetylenic compounds of the formula, R-C-C-C--C-R, where R includes an alkyl, aryl, benzoate, sulfonate, urethane, acid or alcohol moiety. The compounds disclosed by Patel et al. are colorless and are polymerizable in the solid state, either thermally or by actinic radiation. As the polymerization pro-ceeds, these compounds undergo a contrasting colorchange to blue or red and in some instances the color intensifies with time until the compounds finally develop into metallic-looking polymers. Thus, the compounds can be used as time-temperature history indicators and as radiation-dosage indicators. The .
. .
~;~3~ 5 reference also describes polymers oE the type [c c_(cH2)mOCONM(CH2)6NHOco(cEl2)-c-c]n where m is 2~ 3 or 4 and n is large, wherein a polymer containing polymeric repeating units of the same empirical formula, undergoes color changes upon thermal annealing.
Other exemplary U.S. patents relating to acetylenic compounds and their use as environmental indicating materials include U.S. Patent No. 4,215,208 (thermo-chromic materials), 4,125,534 (carbazolyl diacetylenes), and 4,189,399 (co-crystallized compositions).
G. Wegner in an article entitled "Topochemical Polymerization of Monomers with Conjugated Triple Bonds"
in Die Makromolekulare Chemie 154, pp. 35-48 (1972) discloses acetylenic compounds having at least one -C C-C-C- moiety and two urea moieties, the urea moieties being separated from the diaetylene by a phenylene moiety. EIowever, the compounds disclosed by Wegner were not very reactive and did not exhibit color changes that would be useful in monitoring environmental exposure.
The compounds of the present invention are generally more highly reactive and are extremely useful environmental indicating materials.
BRIEF DESCRIPTION OF THE INVENTION
This invention relates to an organic, compound comprising an acetylenic compound having at least one -C_C-C_C- moiety and two urea moieties, said composition being capable o~ undergoing incremental reflectivity changes upon exposure to environmental stimuli; wherein said compounds include at least one methylene moiety between each -C-C-C-C- moiety and one o~ said urea moieties.
DETAILED D_SCRIPTION OF THE INVENTION
This invention relates to novel acetylenic com-pounds that are useful for monitoring the environmentalexposure of various products that undergo progressive quality changes upon environmental exposure. Environ-~' ~3';~1S
mental exposure refers to temperature, cumulative time-temperature, and radiation exposure.
The novel organic compounds of this invention con tain at least one -C_C-C_C- moiety and two urea moie-5 ties, said compounds having at least one methylenemoiety between each -C-C-C_C- moiety and one of said urea moieties. The acetylenic ureas of this invention undergo incremental or progressive color changes upon exposure to environmental stimuli. Thus, there is a corresponding change in reflectance or reflectivity due to exposure to environmental stimuli. Reflectance or reflectivity is defined as the amount of light at selected wavelengths that is reflected by an indicating material after said light has impinged upon the indicat-ing material. A perfectly reflective material has a - reflectance or reflectivity equal to one. Percent reflectance or reflectivity is equal to one hundred times the reflectivity. Since the acetylenic ureas undergo reflectivity changes upon exposure to environ-mental stimuli, said compounds will undergo contrasting color changes upon exposure to given amounts of actinic radiation or thermal annealing. The term "thermal annealing" refers to heating at sufficient temperatures, as by infrared radiation, flame, heat gun, laser-beam, and the like which is sufficiently high to cause poly-meri~ation by 1,4-addition of the acetylenic compounds.
It is known to the art that many acetylenic com-pounds will undergo the described reflectance or reflec-tivity contrasting color changes upon exposure to environmental stimuli actinic radiation, or thermal annealing. It is also known to use acetylenic compounds that undergo ~he described color changes as environ-mental indicating materials in view of the fact that the compounds will undergo measurable incremental color changes in response to environmental exposure. The coIor changes may be correlated with product quality by color matching procedures when a certain color corre-sponds to a given amount of product degradation or pro-.
7~5 cessing. PreEerably, however, product quality is deter-mined by the more precise incremental reflectance measurement technique descrlbed in copending Can. Appl.
Ser. No. 446,711 filed Feb. 3, 1934. The novel com-pounds of this invention exhibit highly desirableproperties which render them an especially preferred class of acetylenic compounds for use as environmental indicating materials. These properties are discussed in more detail herein below following the description of preferred urea acetylenic compounds and methods for their syntheses.
The preferred acetylenic compounds of this inven-tion are of the general structures I, II, and III as depicted hereinbelow. Structure I represents the most preferred family of compounds and is as follows:
o (I) [R-NH-C-NH-(CH2)n-C-C~2 wherein n is an integer of 1-10; wherein R is an organic moiety comprising one or more moieties selected from the group comprising a cycloalkyl moiety of 3-7 carbon atoms, an alkenyl moiety of 3-18 carbon atoms, a cyclo-alkenyl moiety of 3-7 carbon atoms, an alkoxy moiety of
2-18 carbon atoms, a linear or branched alkyl moiety of 1 to 18 carbon atoms, an alkoxycarbonylmethylene moiety of 3-14 carbon atoms, or a phenyl moiety. In many pre-ferred embodiments of the invention, R is a linear or branched alkyl moiety of 1-18 carbon atoms, an allcoxy-carbonylmethylene moeity of 3-13 carbon atoms i.e.
CH3(CH2)0 1o~O~C(o)CH2 or a phenyl moiety. The linear or branched alkyl moieties are espeically preferred.
Especially preferred alkyl moieties include ethyl, n-propyl, n-butyl, n-octyl, n-dodecyl and n-octadecyl.
Especially preferred alkoxycarbonylmethylene moeties include ethoxycarbonylmethylene and butoxycarbony-lmethylene. With respect to all compounds of structure I, n is preferably 1-4 and more preferably I.
other preEerred acetylenic compounds of this inven-tion include tetraynes and hexaynes. The tetraynes and ~i ~L~3~
hexaynes are illustrated by genera:L structures II and III as follows:
n [R-NH-C-NH- (CH2)y~C_C~C~C~2 (CH2) z II
[ R-NH-C-NH- (CH2 ) y~C~C~C~C~ (CH2tx-C ~C~ 2 III
wherein R is as described for structure I; wherein y is an integer from 1 to 18, with z being an integer of l to 6 and with x being an integer of l to 6.
Syntheses of the novel compounds of this invention may be easily accomplished by employing procedures which are well known by those having skill is the art of organic chemistry. For example, compounds of general structure I wherein n=l, the most preferred group of compounds, may be synthesized by the following two step reaction scheme: -o H2NCH2-C_CH + R-N=C=O THF ~ RNHCNHCH2-C_CH
CuCl/N~N~N ~N ~ tetramethylethylenediamine~lRNHCNHCH2-C-C~
wherein R is as described hereinabove. In the above synthetic route, monopropargylamine is reacted with a suitable isocyanate (i.e., having the desired R group conforming to the R groups as described for compounds of general structure I) in the presence of tetrahydrofuran or other similar solvent such as 2-methoxyethyl ether to form an alkyne intermediate having a urea moiety and the desired R group. The first reaction shown above will occur at temperatures between about 25C and about 50C
and requires a reaction time between about 1 and about 2 ~3~ 5 hours. ~ catalyst is not required for the reaction.
Thereafter, without isolation of the intermediate, the intermediate is oxiclatively coupled via conventional procedures to produce the final product. The oxidative 5 coupling reaction may be conducted at temperatures between about 25C and about 50C and will generally require only about 2 to about 4 hours to complete. Iso-lation of the product from the reaction mixture may be aecomplished by eonventional preeipitation, filtration, and recrystallization procedures ete. However, re-erystallization for some eompounds from eertain solvents results in indieator materials of varying reactivity.
Syntheses of compounds of structure I wherein n=2-10 is somewhat more complex, but conventional procedures are also available for produetion of compo~nds of this nature. These compounds may be formed by a five step reaction scheme that initially involves oxidatively coupling an acetylenic compounds having a terminal hydroxyl moiety sueh as 3-butyn-1-ol, 4-pentyn-l-ol, 5-hexyn-1-ol or the like to the eorresponding diyn-diol. The diyn-diol is then reaeted with p-toluene sulfonyl ehloride to form a bis(p-toluensulfonate) eompound. This reaetion employs tetrahydrofuran or another similar solvent as a reaetion medium and pyridine is employed as a promoter. The diyn-bis(p-toluenesulfonate) compounds are then converted to diphthalimido-diyn eompounds using a Gabriel type synthesis as described in an article entitled "The Gabriel Synthesis of Primary Amines", Angew. Chem.
In~ernat. Edit., 7,919 (1968) by M.S. Gibson and R.W.
Bradshaw. Thereafter, the dipthalimido-diyn compounds are hydrolyzed via a two stage hydrolysis to produce a diyn-diamine salt~ the two-stage hydrolysis that should preferably be employed is also described in the Gibson and Bradshaw article. Finally, the diyn-diamine may be reaeted with a suitable isoeyanate, R-N_C_O in aeeordanee with the proeedures described herein where n=~ to produee the di-urea having . ,. ~ .
~3~
the desired R groups and n=2-10.
Syntheses of the tetraynes of general structure II
and the hexaynes of general structure III is preferably accomplished by the following reaction scheme:
(l)HC-C-(CH2)x-C-CH H 0 ~ BrC_C-(CH2)x-C_CBr Oa) (2)H2N(CH2)y~C_CH + R-N=C=O THF + RNHCNH(CH2) -C-CH
O (b)
CH3(CH2)0 1o~O~C(o)CH2 or a phenyl moiety. The linear or branched alkyl moieties are espeically preferred.
Especially preferred alkyl moieties include ethyl, n-propyl, n-butyl, n-octyl, n-dodecyl and n-octadecyl.
Especially preferred alkoxycarbonylmethylene moeties include ethoxycarbonylmethylene and butoxycarbony-lmethylene. With respect to all compounds of structure I, n is preferably 1-4 and more preferably I.
other preEerred acetylenic compounds of this inven-tion include tetraynes and hexaynes. The tetraynes and ~i ~L~3~
hexaynes are illustrated by genera:L structures II and III as follows:
n [R-NH-C-NH- (CH2)y~C_C~C~C~2 (CH2) z II
[ R-NH-C-NH- (CH2 ) y~C~C~C~C~ (CH2tx-C ~C~ 2 III
wherein R is as described for structure I; wherein y is an integer from 1 to 18, with z being an integer of l to 6 and with x being an integer of l to 6.
Syntheses of the novel compounds of this invention may be easily accomplished by employing procedures which are well known by those having skill is the art of organic chemistry. For example, compounds of general structure I wherein n=l, the most preferred group of compounds, may be synthesized by the following two step reaction scheme: -o H2NCH2-C_CH + R-N=C=O THF ~ RNHCNHCH2-C_CH
CuCl/N~N~N ~N ~ tetramethylethylenediamine~lRNHCNHCH2-C-C~
wherein R is as described hereinabove. In the above synthetic route, monopropargylamine is reacted with a suitable isocyanate (i.e., having the desired R group conforming to the R groups as described for compounds of general structure I) in the presence of tetrahydrofuran or other similar solvent such as 2-methoxyethyl ether to form an alkyne intermediate having a urea moiety and the desired R group. The first reaction shown above will occur at temperatures between about 25C and about 50C
and requires a reaction time between about 1 and about 2 ~3~ 5 hours. ~ catalyst is not required for the reaction.
Thereafter, without isolation of the intermediate, the intermediate is oxiclatively coupled via conventional procedures to produce the final product. The oxidative 5 coupling reaction may be conducted at temperatures between about 25C and about 50C and will generally require only about 2 to about 4 hours to complete. Iso-lation of the product from the reaction mixture may be aecomplished by eonventional preeipitation, filtration, and recrystallization procedures ete. However, re-erystallization for some eompounds from eertain solvents results in indieator materials of varying reactivity.
Syntheses of compounds of structure I wherein n=2-10 is somewhat more complex, but conventional procedures are also available for produetion of compo~nds of this nature. These compounds may be formed by a five step reaction scheme that initially involves oxidatively coupling an acetylenic compounds having a terminal hydroxyl moiety sueh as 3-butyn-1-ol, 4-pentyn-l-ol, 5-hexyn-1-ol or the like to the eorresponding diyn-diol. The diyn-diol is then reaeted with p-toluene sulfonyl ehloride to form a bis(p-toluensulfonate) eompound. This reaetion employs tetrahydrofuran or another similar solvent as a reaetion medium and pyridine is employed as a promoter. The diyn-bis(p-toluenesulfonate) compounds are then converted to diphthalimido-diyn eompounds using a Gabriel type synthesis as described in an article entitled "The Gabriel Synthesis of Primary Amines", Angew. Chem.
In~ernat. Edit., 7,919 (1968) by M.S. Gibson and R.W.
Bradshaw. Thereafter, the dipthalimido-diyn compounds are hydrolyzed via a two stage hydrolysis to produce a diyn-diamine salt~ the two-stage hydrolysis that should preferably be employed is also described in the Gibson and Bradshaw article. Finally, the diyn-diamine may be reaeted with a suitable isoeyanate, R-N_C_O in aeeordanee with the proeedures described herein where n=~ to produee the di-urea having . ,. ~ .
~3~
the desired R groups and n=2-10.
Syntheses of the tetraynes of general structure II
and the hexaynes of general structure III is preferably accomplished by the following reaction scheme:
(l)HC-C-(CH2)x-C-CH H 0 ~ BrC_C-(CH2)x-C_CBr Oa) (2)H2N(CH2)y~C_CH + R-N=C=O THF + RNHCNH(CH2) -C-CH
O (b)
(3)2RNHCNH(CH2)y~C_CH ~ BrC_C-(cH2) O
HCl, [RNHCNH(CH2)y~C_C~C C~2(CH2)X
II
o RNHcNH~cH2)y-c-c-c-c-(cH2)x-c-CH
HCl, [RNHCNH(CH2)y~C_C~C C~2(CH2)X
II
o RNHcNH~cH2)y-c-c-c-c-(cH2)x-c-CH
(4)RNHCNH(cH2)y-c--c-c-c-(cH2)x-c-cH CuCléTMEDA
(c) 2 [RNHCNH(cH2)y-c-c-c-c-(cH2)x-c-c]2 III
In reaction (1) above a diyne having x=1-6 is reacted with a suitable hypobromite such as sodium hypo-bromite to produce a dibromo diyne compound (a). Reac~
tion (2) involves reacting an alkyne having a terminal primary amine wherein y=l-10 with an isocyanate having a ~3~7~ ~S
suitable R group as described hereinabove to produce urea (b) having a terminal acetylene moiety and desired R group. Thereafter, compounds (a) and (b) are coupled by reaction in the presence of a solution comprising
(c) 2 [RNHCNH(cH2)y-c-c-c-c-(cH2)x-c-c]2 III
In reaction (1) above a diyne having x=1-6 is reacted with a suitable hypobromite such as sodium hypo-bromite to produce a dibromo diyne compound (a). Reac~
tion (2) involves reacting an alkyne having a terminal primary amine wherein y=l-10 with an isocyanate having a ~3~7~ ~S
suitable R group as described hereinabove to produce urea (b) having a terminal acetylene moiety and desired R group. Thereafter, compounds (a) and (b) are coupled by reaction in the presence of a solution comprising
5 CuCl, n-ethylamine and hydroxylamine hydrochloride to produce tetraynes of general structure II. This coupl-ing reaction is more particularly illustrated in Example 12. The triyne (c) in the above reaction scheme may be extracted from the reaction medium by addition of a non--10 polar solvent such as petroleum ether, heptane, orhexane or the like. Thereafter, triyne (c) may be oxi-~atively coupled to hexaynes of general structure III by well known procedures in accordance with reaction 4 above.
Following preparation of the compounds of this invention, the compounds should be recrystallized from an appropriate solvent in order to provide an active or inactive phase depending upon the desired phase for a particular application. A compound in the active phase will begin to polymerize, and thus undergo color changes, upon exposure to environmental stimuli. A com-pound in the inactive phase will not begin polymeriza-tion until some action, such as the application of heat or mechanical pressure or exposure to appropriate sol-vents or solutions, is undertaken to convert the inac-tive phase to the active phase.
The polymerization reactivity of many of the acety-lenic ureas may be increased or decreased by dissolvin~
two or more of the compounds to produce a co-crystal-lized composition. The co-crystallized compositions may be distinguished from simple mixtures of the individual compounds in that the co-crystallized composition exhi-bits a substantially different polymerization reactivity and subsequent rate of color change upon exposure to actinic radiation or thermal annealing; whereas the sim-ple mixture will exhibit properties which are merely an additive combination of the individual compounds depend-ing upon the properties of each compound present.
7~S
Many of the acetylenic urea compounds of this invention undergo a color change from white, pink, or light gray to various shades of blue upon exposure to environmental stimuli and will thus absorb light in a 5 spectral region ranging from about 250 nm to about 700 nm. Thus, environmental indicator labels prepared from the compounds of this invention may be read by optical scanners consisting of a light source capable of illu-minating a surface; a detector to sense the amount of 10 reflected light; and a means to output the signal from the optical detector that operate in this spectral region. The alkyl ureas of general structure I, the most preferred class of compounds, wherein R is linear or branched alkyl of 1-18 carbon atoms are especially 15 useful in this respect as most ureas of this nature gradually polymerize to a blue color upon being exposed to environmental stimuli, with speed of polymerization and degree of color response being directly related to the amount of environmental exposure. The alkyl ureas are also especially useful because they characteristic-ally either melt at high temperatures, generally above about 170C, or they do not melt at all but simply decompose at temperatures above about 200C. This is a highly desirable feature in addition to the optimal 25 spectroscopic properties of these compounds. Many of the acetylenic compositions described in the prior art melt at modest temperatures. Melting of a partially polymerized acetylenic composition usually causes a color change which could yield false information regard-ing cumulative temperature exposures. It will be appre-ciated that many of the compounds of this in~vention other than the alkyl ureas also have high melting points or no melting points. This appears to be true with respect to the tetraynes and hexaynes of general struc-tures II and III.
The acetylenic urea compounds of this invention maybe fabricated into environmental indicator devices in accordance with well known procedures. An environmental 3L~3'7~
indicating device is a device that may be attached in some form to a product that undergoes progressive quality changes in response to environmental exposure, said device being eapable of reeording the amount of environmental exposure of said product. The acetylenic compounds of this invention record the amount of environmental exposure by color changes that may be determined by visual observation or by an optieal seanning method as deseribed in eopending Application Serial No. 469,880. Optical scanning of environmental indieators that employ aeetylenie ureas of this invention is illustrated in Example 17.
Substrates that may be employed for eonstruetion of deviees that employ the acetylenic ureas of this invention include paper, paperboard, fiberboard, cardboard, Kimdura, Mylar~ polyethylene, polypropylene t polyacrylate polymers and copolymers, cellulose ethers, cellulose esters, mixed esters or other similar materials. Other exemplary of materials that may be employed as substrates for environmental indieator labels that employ acetylenie ureas include synthetic resins and plasties and deseribed in U.S. Patent 3,501,302, eol. 19, lines 14-15. Additionally, it should be appreeiated that eontainers for various produets may also serve as substrate upon which the environmental indieator labels are constructed.
The acetylenic ureas may be applied to the substrate in various fashions. For example, an ink solution comprising an acetylenic urea compound and solvent may be sprayed onto the substrate in order to deposit the aeetylenie urea eompound onto the desired area of the substrate. The solution should include the acetylenic urea compound in an amount comprising about 1% to about 5% and preferably about 2% by weight. This method in effect, employs an acetylenie urea monomer as a dye (i.e., monomer soluble in the ink vehiele). This method is more partieularly described in U.S. Patent No.
4,189,399 where aeetone, with laequer added as a binder, . .
", ~3~ S
is employed to dissolve an acetylneic compound more soluble in acetone than the present compounds. Upon spray coating of a subs-trate, Eollowed by evaporation of the acetone, an ac-tive indicator is printed. Of course, this ink system could be printed by more conventional methods such as flexography, screen, gravure, letter-press, ink-jet printing, or the like.
Solvents that may be employed for forming the above-described ink solutions include acetic acid, propanoic acid, heptanoic acid, nonanoic acid, hydroxy acetone, 1,1,3,3-tetramethylurea, triethanolamine, n-decylamine, sec-phenethyl alcohol, dimethyl sulfoxide, 2,6-lutidine, and the like.
Another, and more preferred, method for applying the acetylenic urea compound to the indicator device substrates involves initially grinding the acetylenic compound into fine particles and forming a suspension of the particles in a suitable binder-solvent system.
Suitable binders for forming these suspensions include natural and synthetic plastics, resins, waxes, colloids, gels, and the like including gelatin and other similar binders described in U.S~ Patent No. 3,501,302 at col.
20, lines 13-43. The suspension comprising the binder and the acetylenic compound may then be applied to the desired area of the label by spraying, screen printing, gravure, flexography letterpress, or other conventional printing means. This method of applying the acetylenic compound to the substrate employs the active acetylenic material as a pigment in a conventional ink. This method is more particularly described by U.S. Patent No.
3,501,297.
General Procedure A three neck flask fitted with a stirrer, thermometer, N2 flow tube which was exchanged with an 2 dip tube for oxidative coupling reactions, and a dropping funnel was employed for producing the compounds of Exam-~3~145 ples 1 15. An excess o~ an isocyanate compound dis-solved in tetrahydrofuran ~hereinafter referred to as THF) was added to the reaction flask to which a solution comprising mono-propargylamine and THF had been previ-5 ously added. Since the reactions were rapid, a catalystwas not employed. To moderate the temperature of the reaction, a water bath (typically 18C) was used during the addition of the isocyanate. After 1 to 2 hours, the reaction media was charged with CuCl and complexation 10 agent, N,N,N',N'-tetramethylethylenediamine (hereina~ter referred to as TMEDA), followed by a continuous moderate bubbling of 2 to effect the oxidative coupling reac-tion. A water bath was used to moderate the intitial temperature excursion. Typically, after 2~2hours, the 15 media was dea~tivated with HCl. Purification was effected by filtration, washings, and recrystallization.
In cases where ultraviolet radiation was employed to cause polymerization and corresponding color changes of the acetylenic ureas, the ultraviolet source employed 20 was a model U~S-llE ultraviolet lamp ~Ultra Violet Products Inc., Pasadena, Calif.) EXAMPL _l 2,4-hexadiyn-1,6-bis(ethylurea) A 1 liter flask was charged with 50 9 (0.9 mol) 25 mono-propargylamine and 300 mL T~F. 89 9 (1.25 mol) ethylisocyanate diluted with 50 mL THF was added drop-wise over a 30 minute time period. During the addition, the reaction flask was placed in a water bath (18C) to moderate the exotherm during the ethylisocyanate addi-tion. The temperature did not exceed 40C. 2.5 9 CuCland 6 mL TMEDA were added to the reaction media after 11/2 hours. Oxygen was bubbled into the reaction medium at a moderate rate while stirring. Initially~ a water bath was used to keep the temperature between 25 to 35C.
The water bath was removed after 15 minutes and the tem~
perature slowly rose to 55C and then decreased. After 2~2 hours, the medium ~as deactivated by adding 200 mL
10% HCl solution. The product was filtered, washed with ~3~7~9~5 additional HCl solution, followed by washing with H2O.
The product was stirred in a solution of 200 mL methanol and 200 mL 10~ HCl solution, filtered, washed with El2O, methanol, and finally acetone. The product was recry-5 stallized by dissolving it in 500 mL hot acetic acid (90C), filtering, and cooling to 15-20C. The preci pitate was filtered, washed with petroleum ether (50 110C) and then vacuum dried. Yield: 88 g (78~ of theoretical) fine powder product which turned blue at a 10 moderate rate under ambient conditions, about 25C, in ~he dark. The product did not melt when heated to 300C
on a Mettler hot stage. Upon heating, rapid polymeriza-tion to dark blue and then black occurred.
ELEMENTAL ANALYSIS
15 C12~118N4O2(MW = 250.277) Calcd. C 57~59 H 7.25 - N 22.38 O12.78 Found. C 57.47 H 7.34 N 22.45 O12.73 2,4-hexadiyn-1,6-bis(but~lurea) Same as Example 1 except 25.8 g ~0 25 mol) butyl-isocyanate diluted with 25 mL THF and 10.0 g (0.18 mol) mono-propargylamine in 100 mL THF was used to synthesiæe the mono-urea derivative. The complexing agent was 2S derived ~rom 1 9 CuCl and 3 mL TMEDA to form the di-urea. The reaction media was deactivated with 125 mL
HCl (10~). T~e methanol, acetone, and water used in the work-up were reduced proportionally to Example 1.
Yield: 26.6 g (97~) of a greenish product which moder-ately changed to blue at ambient conditions (about 25C)in the dark indicating an active phase.
A 1 g sample was recrystallized from 100 mL
ethanol. Initially, the color of the recrystallized product was light pink, but the color slowly changed to orange at ambient conditions (about 25C). Upon irra-diation for 5-10 seconds with the UV source, the color of the product changed to blue. When recrystallized from acetic acid an orange or blue phase was obtained `:`
~3~7~'~S
that intensified upon irradiation with the UV source.
ELEMENTAL ANALYSIS
C16H26N4O2(MW = 306.385) Calcd. C62.72 H 8.55 N 18.28 O 1~.44 Found. C 62.53 H 8.81 N 18.08 O 10.01 2,4-hexadiyn-1,6-bis(octylurea) Same as Example 1 and 2 except 21.5 g (0.14 mol) 10 octylisocyanante, 6.6 g (0.12 mol) mono-propargylamine, and 200 mL THF were used to synthesize the mono-urea. A
proportionally larger amount of THF was necessary to keep the mono-urea solubilized. Synthesis of the mono-urea required 1 hour at 25C. 1 g CuCl, 3 mL TMEDA, and 15 50 mL THF were added to the reaction media for the coupling reaction to obtain the di-urea. The tempera-ture was maintained between 45-50C throughout the reac-tion. The coupling reaction was complete in 2 hours.
Yield: 25.2 g (99%) of light blue product which melted 20 and decomposed at about 195C upon heating. The peoduct was recrystallized from ethanol (1 g/40 mL). The recry-stallized product was thermochromic and underwent a light blue to red-purple reversible transition at 80C.
ELEMENTAL ANALYSIS
. . . ~ _ .
25 C24H24N4O2(MW = 418.626) Calcd. C68.86 H 10.11 N 13.38 O 7.64 Found. C 68.83 H 10~34 N 13.23 O 7.60 2,4-hexad~yn-1,6-bis(dodecylurea) Same as Example 1 and 2 except 25 g (0.45 mole) monopropargylamine, 100 g (0.47 mole) dodecylisocyanate, 3S0 mL THF were used to form the mono-urea. After the addition of the isocyanate, the temperature was increased to 45-50C to keep the product solubilized.
The reaction was continued for 1 hour at which time 2.5 g CuCl and 6 mL TMEDA were added to the reaction media. The temperature was maintained between 45-50C
~3~4~
for 242 hours; the product precipitated as it formed tthe temperature during this reaction should not exceed S0C
because above 50C appreciable polymer Eormation occurs). The product was deactivated with a l:l mixture 5 of 20% HCl solution/MeOH (500 mL), filtered and washed twice with methanol and acetone. The resulting product was yello~. The yellow color intensified upon exposure to ultraviolet light. Upon placing a sample of the product on filter paper and applying mechanical pressure 10 ~ith a spatula to the product, subsequent UV irradiation or thermal annealing changed the yellow color to blue.
It was also ~ound that rapidly heating the ~ellow phase above about 150C results in an abrupt color change from yellow to blue-purple. In order to recrystallize the 15 product, it was added to 2.5 L dimethylsul~oxide, heated to 80-85C on a hot plate, and rapidly brought up to 95C before it was removed and filtered. The product was precipitated with 1.3 L ethanol, filtered, and washed with additional ethanol followed by petroleum ether (50-110C). Yield: 112 g (93%) pale to light blue product which melted and decomposed at 215C upon heating.
ELEMENTAL ANALYSIS
C32H58N4O2(MW = 530.842) Calcd. C 72.40 H 11.01 25 N 10.5S O 6.03 Found. C 72 25 H 11.13 N 10~65 O 6010 2,4-hexadiyn-1,6-bis(octadecylurea);
Same as Examples 1 and 2 except ~0.6 g (0.036 mol) n-octadecylisocyanate, 2.0 g ~0.036 mol) mono-propargyl-amine, and 75 mL THF were used to snythesize the mono-urea. The reaction proceeded for 1 hour at a tempera-ture between 50C-60C. The coupling reaction was con-3 ducted using 0.25 g CuCl and 3mL TMEDA, allowing the reaction to continue for 2~2hours at 45-50C. Yield:
1~.8 g ~94%) light yellow product which changed to a dark yellow upon exposure to 5-10 seconds o~ ultraviolet . .
radiation. A sample (about 0.5 g) was placed on filter paper. Mechanical pressure (i.e., shearing with spatula) was applied to the product. Fol]owing the application of pressure, the product was irradiated with 5 ultraviolet radiation and the color of the product changed from ~ellow to blue.
2-4-hexadiyn-1,6-bis(n-propylurea);
Same as Examples 1 and 2 except 2.0 g (0.03 mol) lO mono-propargylamine, 3.1 9 (0.036 mol) n-propyliso-cyanate, 50 mL THF were employed to synthesize the mono-urea. The synthesis of the mono-urea required l hour at -25C. 0.25 9 CuCl and 2 mL TMEDA were added for the coupling reaction which was complete in 2~2 hours at 15 40C. Yield: 1.7 g (33%) of a yellowish white product which changed to a bright yellow upon exposure UV radia-tion. Recrystallization from acetic acid or ethanol (l g/lO0 mL) resulted in an active phase in each case which changed from pink to blue upon exposure to UV radia-tion. Upon heating to 300C, the product decomposed. A
melting point was not observed.
ELEMENTAL ANALYS IS
Cl4H22N4O2(MW = 27~.356) Calcd. C 60.~1 H 7.97 N 20.13 O 11.50 25Found. C 60.81 H ~.ll N 19.78 o 12.22 2,4-hexadiyn-1!6-bis(iso-propylurea) Same as Examples 1 and 2 except 2.0 9 (0.036 mol) 30 mono-propargylamine, 50 mL THF were used to synthesize the mono-urea and 0.25 9 CuCl and 2 mL TMEDA were added for the coupling reaction. Yield: 2.0 g (39%) of a white product which changed to a bright yellow upon expos~re to ultraviolét radiation. Recrystallization from various solvents such as acetic acid or ethanol (1 9/170 mL) did not result in an active blue phase when treated with UV light. The product melted and decom-posed at 270C.
:
.
~3~ 5 ELEMENTAL ANALYSIS
C14H22N4O2(MW = 278.356~ Calcd. C 60.41 H 7.97 N 20.13O 11.50 Found. C 60.84 H 8.09 N 19.75O 11.93 2,4-hexadi~n-1,6-bis(methylurea);
Same as Examples 1 and 2 except 2.0 9 ~0.036 mol) mono-propargylamine, 2.1 g (0.036 mol) methylisocyanate, 10 and 50 mL THF were used to synthesize the mono-urea and O.25 g CuCl and 2 mL TMEDA were added for the coupling reaction. Synthesis of the mono-urea required 1 hour at ~
25C. The coupling reaction required ~2 hours at 40C. Yield: 1~7 g (41~) light pinkish white product 15 which changed to bright yellow upon exposure to 5-10 seconds of ultraviolet radiation. Recrystallization from dimethylsulfoxide, ethanol (1 9/250 mL~, or acetic acid did not result in an active blue phase~ Upon heat-ing, the product melted and decomposed at 255C.
ELEMENTAL ANALYSIS
CloH14N402(MW = 222.248) Calcd. C~4.04 ~ 6.35 N 25.21 O 14.40 Found. C 53.96 H 6.60 N 24.48 O 13.32 2,4-hexadiyn-1,6 bis(ethox~carbonylmethylene urea) Same as Examples 1 and 2 except 2.0 9 (0.036 mol) mono-propargylamine, 4.6 g (0.036 mol) ethylisocyanato-acetate, and 50 mL THF were used for the synthesis of the mono-urea and 0.25 g CuCl and 2 mL TMEDA were added for the coupling reaction. Synthesis of the mono-urea required 1 hour at 25C~ The coupling reaction required ~2hours at 45C. Yield: 5.0 9 (76%) of a pinkish product which changed to blue upon exposure to 5-10 seconds ultraviolet radiation. Upon heating, the product melted between 190 and 195C.
3~ 5 ELEMENTAL ANALYSIS
C16H22N4O6(MW = 366.374) Calcd. C 52.45 ~l6.05 N 15.29 O26.20 Found. C 52.13 H6O05 N 15.36 O25.68 2,4-hexa iyn-1,6-bis(butoxycarbonylmethylene urea), Same as Examples 1 and 2 except 2.0 9 (0.036 mol) mono-propargylamine, 5.6 9 (0.036 mol) butylisocyanato-10 acetate, and 50 mL THF were used for the synthesis ofthe mono-urea and 0.25 9 CuCl and 2 mL TMEDA were used for the coupling reaction. Synthesis of the mono-urea required 1 hour at 25C. The coupling reaction required 1~2 hours at 45C. Yield: 3.9 9 (51~) of a white prod-15 uct was obtained by recrystallization of the productfrom ethanol ~1 9/75 mL). A sample of the product turned blue upon exposure to 5-10 seconds of ultraviolet radiation. Upon heating, a sample of the product melted at 168-169C and turned 20 red upon cooling and solidification. The cooled and solidified product turned blue upon e~posure to 5-10 seconds of ultraviolet radiation.
ELEMENTAL ANALYSIS
C20H30N4O6(MW = 422.482) Calcd. C 56.86 H 7.16 N 13.26 O 22.72 Found. C 57.07 H 7.67 N 13.01 O ~1.61 2,4-hexadiyn-1,6-bis(phenylurea), Same as Examples 1 and 2 except 5.5 9 (0.1 mole,
Following preparation of the compounds of this invention, the compounds should be recrystallized from an appropriate solvent in order to provide an active or inactive phase depending upon the desired phase for a particular application. A compound in the active phase will begin to polymerize, and thus undergo color changes, upon exposure to environmental stimuli. A com-pound in the inactive phase will not begin polymeriza-tion until some action, such as the application of heat or mechanical pressure or exposure to appropriate sol-vents or solutions, is undertaken to convert the inac-tive phase to the active phase.
The polymerization reactivity of many of the acety-lenic ureas may be increased or decreased by dissolvin~
two or more of the compounds to produce a co-crystal-lized composition. The co-crystallized compositions may be distinguished from simple mixtures of the individual compounds in that the co-crystallized composition exhi-bits a substantially different polymerization reactivity and subsequent rate of color change upon exposure to actinic radiation or thermal annealing; whereas the sim-ple mixture will exhibit properties which are merely an additive combination of the individual compounds depend-ing upon the properties of each compound present.
7~S
Many of the acetylenic urea compounds of this invention undergo a color change from white, pink, or light gray to various shades of blue upon exposure to environmental stimuli and will thus absorb light in a 5 spectral region ranging from about 250 nm to about 700 nm. Thus, environmental indicator labels prepared from the compounds of this invention may be read by optical scanners consisting of a light source capable of illu-minating a surface; a detector to sense the amount of 10 reflected light; and a means to output the signal from the optical detector that operate in this spectral region. The alkyl ureas of general structure I, the most preferred class of compounds, wherein R is linear or branched alkyl of 1-18 carbon atoms are especially 15 useful in this respect as most ureas of this nature gradually polymerize to a blue color upon being exposed to environmental stimuli, with speed of polymerization and degree of color response being directly related to the amount of environmental exposure. The alkyl ureas are also especially useful because they characteristic-ally either melt at high temperatures, generally above about 170C, or they do not melt at all but simply decompose at temperatures above about 200C. This is a highly desirable feature in addition to the optimal 25 spectroscopic properties of these compounds. Many of the acetylenic compositions described in the prior art melt at modest temperatures. Melting of a partially polymerized acetylenic composition usually causes a color change which could yield false information regard-ing cumulative temperature exposures. It will be appre-ciated that many of the compounds of this in~vention other than the alkyl ureas also have high melting points or no melting points. This appears to be true with respect to the tetraynes and hexaynes of general struc-tures II and III.
The acetylenic urea compounds of this invention maybe fabricated into environmental indicator devices in accordance with well known procedures. An environmental 3L~3'7~
indicating device is a device that may be attached in some form to a product that undergoes progressive quality changes in response to environmental exposure, said device being eapable of reeording the amount of environmental exposure of said product. The acetylenic compounds of this invention record the amount of environmental exposure by color changes that may be determined by visual observation or by an optieal seanning method as deseribed in eopending Application Serial No. 469,880. Optical scanning of environmental indieators that employ aeetylenie ureas of this invention is illustrated in Example 17.
Substrates that may be employed for eonstruetion of deviees that employ the acetylenic ureas of this invention include paper, paperboard, fiberboard, cardboard, Kimdura, Mylar~ polyethylene, polypropylene t polyacrylate polymers and copolymers, cellulose ethers, cellulose esters, mixed esters or other similar materials. Other exemplary of materials that may be employed as substrates for environmental indieator labels that employ acetylenie ureas include synthetic resins and plasties and deseribed in U.S. Patent 3,501,302, eol. 19, lines 14-15. Additionally, it should be appreeiated that eontainers for various produets may also serve as substrate upon which the environmental indieator labels are constructed.
The acetylenic ureas may be applied to the substrate in various fashions. For example, an ink solution comprising an acetylenic urea compound and solvent may be sprayed onto the substrate in order to deposit the aeetylenie urea eompound onto the desired area of the substrate. The solution should include the acetylenic urea compound in an amount comprising about 1% to about 5% and preferably about 2% by weight. This method in effect, employs an acetylenie urea monomer as a dye (i.e., monomer soluble in the ink vehiele). This method is more partieularly described in U.S. Patent No.
4,189,399 where aeetone, with laequer added as a binder, . .
", ~3~ S
is employed to dissolve an acetylneic compound more soluble in acetone than the present compounds. Upon spray coating of a subs-trate, Eollowed by evaporation of the acetone, an ac-tive indicator is printed. Of course, this ink system could be printed by more conventional methods such as flexography, screen, gravure, letter-press, ink-jet printing, or the like.
Solvents that may be employed for forming the above-described ink solutions include acetic acid, propanoic acid, heptanoic acid, nonanoic acid, hydroxy acetone, 1,1,3,3-tetramethylurea, triethanolamine, n-decylamine, sec-phenethyl alcohol, dimethyl sulfoxide, 2,6-lutidine, and the like.
Another, and more preferred, method for applying the acetylenic urea compound to the indicator device substrates involves initially grinding the acetylenic compound into fine particles and forming a suspension of the particles in a suitable binder-solvent system.
Suitable binders for forming these suspensions include natural and synthetic plastics, resins, waxes, colloids, gels, and the like including gelatin and other similar binders described in U.S~ Patent No. 3,501,302 at col.
20, lines 13-43. The suspension comprising the binder and the acetylenic compound may then be applied to the desired area of the label by spraying, screen printing, gravure, flexography letterpress, or other conventional printing means. This method of applying the acetylenic compound to the substrate employs the active acetylenic material as a pigment in a conventional ink. This method is more particularly described by U.S. Patent No.
3,501,297.
General Procedure A three neck flask fitted with a stirrer, thermometer, N2 flow tube which was exchanged with an 2 dip tube for oxidative coupling reactions, and a dropping funnel was employed for producing the compounds of Exam-~3~145 ples 1 15. An excess o~ an isocyanate compound dis-solved in tetrahydrofuran ~hereinafter referred to as THF) was added to the reaction flask to which a solution comprising mono-propargylamine and THF had been previ-5 ously added. Since the reactions were rapid, a catalystwas not employed. To moderate the temperature of the reaction, a water bath (typically 18C) was used during the addition of the isocyanate. After 1 to 2 hours, the reaction media was charged with CuCl and complexation 10 agent, N,N,N',N'-tetramethylethylenediamine (hereina~ter referred to as TMEDA), followed by a continuous moderate bubbling of 2 to effect the oxidative coupling reac-tion. A water bath was used to moderate the intitial temperature excursion. Typically, after 2~2hours, the 15 media was dea~tivated with HCl. Purification was effected by filtration, washings, and recrystallization.
In cases where ultraviolet radiation was employed to cause polymerization and corresponding color changes of the acetylenic ureas, the ultraviolet source employed 20 was a model U~S-llE ultraviolet lamp ~Ultra Violet Products Inc., Pasadena, Calif.) EXAMPL _l 2,4-hexadiyn-1,6-bis(ethylurea) A 1 liter flask was charged with 50 9 (0.9 mol) 25 mono-propargylamine and 300 mL T~F. 89 9 (1.25 mol) ethylisocyanate diluted with 50 mL THF was added drop-wise over a 30 minute time period. During the addition, the reaction flask was placed in a water bath (18C) to moderate the exotherm during the ethylisocyanate addi-tion. The temperature did not exceed 40C. 2.5 9 CuCland 6 mL TMEDA were added to the reaction media after 11/2 hours. Oxygen was bubbled into the reaction medium at a moderate rate while stirring. Initially~ a water bath was used to keep the temperature between 25 to 35C.
The water bath was removed after 15 minutes and the tem~
perature slowly rose to 55C and then decreased. After 2~2 hours, the medium ~as deactivated by adding 200 mL
10% HCl solution. The product was filtered, washed with ~3~7~9~5 additional HCl solution, followed by washing with H2O.
The product was stirred in a solution of 200 mL methanol and 200 mL 10~ HCl solution, filtered, washed with El2O, methanol, and finally acetone. The product was recry-5 stallized by dissolving it in 500 mL hot acetic acid (90C), filtering, and cooling to 15-20C. The preci pitate was filtered, washed with petroleum ether (50 110C) and then vacuum dried. Yield: 88 g (78~ of theoretical) fine powder product which turned blue at a 10 moderate rate under ambient conditions, about 25C, in ~he dark. The product did not melt when heated to 300C
on a Mettler hot stage. Upon heating, rapid polymeriza-tion to dark blue and then black occurred.
ELEMENTAL ANALYSIS
15 C12~118N4O2(MW = 250.277) Calcd. C 57~59 H 7.25 - N 22.38 O12.78 Found. C 57.47 H 7.34 N 22.45 O12.73 2,4-hexadiyn-1,6-bis(but~lurea) Same as Example 1 except 25.8 g ~0 25 mol) butyl-isocyanate diluted with 25 mL THF and 10.0 g (0.18 mol) mono-propargylamine in 100 mL THF was used to synthesiæe the mono-urea derivative. The complexing agent was 2S derived ~rom 1 9 CuCl and 3 mL TMEDA to form the di-urea. The reaction media was deactivated with 125 mL
HCl (10~). T~e methanol, acetone, and water used in the work-up were reduced proportionally to Example 1.
Yield: 26.6 g (97~) of a greenish product which moder-ately changed to blue at ambient conditions (about 25C)in the dark indicating an active phase.
A 1 g sample was recrystallized from 100 mL
ethanol. Initially, the color of the recrystallized product was light pink, but the color slowly changed to orange at ambient conditions (about 25C). Upon irra-diation for 5-10 seconds with the UV source, the color of the product changed to blue. When recrystallized from acetic acid an orange or blue phase was obtained `:`
~3~7~'~S
that intensified upon irradiation with the UV source.
ELEMENTAL ANALYSIS
C16H26N4O2(MW = 306.385) Calcd. C62.72 H 8.55 N 18.28 O 1~.44 Found. C 62.53 H 8.81 N 18.08 O 10.01 2,4-hexadiyn-1,6-bis(octylurea) Same as Example 1 and 2 except 21.5 g (0.14 mol) 10 octylisocyanante, 6.6 g (0.12 mol) mono-propargylamine, and 200 mL THF were used to synthesize the mono-urea. A
proportionally larger amount of THF was necessary to keep the mono-urea solubilized. Synthesis of the mono-urea required 1 hour at 25C. 1 g CuCl, 3 mL TMEDA, and 15 50 mL THF were added to the reaction media for the coupling reaction to obtain the di-urea. The tempera-ture was maintained between 45-50C throughout the reac-tion. The coupling reaction was complete in 2 hours.
Yield: 25.2 g (99%) of light blue product which melted 20 and decomposed at about 195C upon heating. The peoduct was recrystallized from ethanol (1 g/40 mL). The recry-stallized product was thermochromic and underwent a light blue to red-purple reversible transition at 80C.
ELEMENTAL ANALYSIS
. . . ~ _ .
25 C24H24N4O2(MW = 418.626) Calcd. C68.86 H 10.11 N 13.38 O 7.64 Found. C 68.83 H 10~34 N 13.23 O 7.60 2,4-hexad~yn-1,6-bis(dodecylurea) Same as Example 1 and 2 except 25 g (0.45 mole) monopropargylamine, 100 g (0.47 mole) dodecylisocyanate, 3S0 mL THF were used to form the mono-urea. After the addition of the isocyanate, the temperature was increased to 45-50C to keep the product solubilized.
The reaction was continued for 1 hour at which time 2.5 g CuCl and 6 mL TMEDA were added to the reaction media. The temperature was maintained between 45-50C
~3~4~
for 242 hours; the product precipitated as it formed tthe temperature during this reaction should not exceed S0C
because above 50C appreciable polymer Eormation occurs). The product was deactivated with a l:l mixture 5 of 20% HCl solution/MeOH (500 mL), filtered and washed twice with methanol and acetone. The resulting product was yello~. The yellow color intensified upon exposure to ultraviolet light. Upon placing a sample of the product on filter paper and applying mechanical pressure 10 ~ith a spatula to the product, subsequent UV irradiation or thermal annealing changed the yellow color to blue.
It was also ~ound that rapidly heating the ~ellow phase above about 150C results in an abrupt color change from yellow to blue-purple. In order to recrystallize the 15 product, it was added to 2.5 L dimethylsul~oxide, heated to 80-85C on a hot plate, and rapidly brought up to 95C before it was removed and filtered. The product was precipitated with 1.3 L ethanol, filtered, and washed with additional ethanol followed by petroleum ether (50-110C). Yield: 112 g (93%) pale to light blue product which melted and decomposed at 215C upon heating.
ELEMENTAL ANALYSIS
C32H58N4O2(MW = 530.842) Calcd. C 72.40 H 11.01 25 N 10.5S O 6.03 Found. C 72 25 H 11.13 N 10~65 O 6010 2,4-hexadiyn-1,6-bis(octadecylurea);
Same as Examples 1 and 2 except ~0.6 g (0.036 mol) n-octadecylisocyanate, 2.0 g ~0.036 mol) mono-propargyl-amine, and 75 mL THF were used to snythesize the mono-urea. The reaction proceeded for 1 hour at a tempera-ture between 50C-60C. The coupling reaction was con-3 ducted using 0.25 g CuCl and 3mL TMEDA, allowing the reaction to continue for 2~2hours at 45-50C. Yield:
1~.8 g ~94%) light yellow product which changed to a dark yellow upon exposure to 5-10 seconds o~ ultraviolet . .
radiation. A sample (about 0.5 g) was placed on filter paper. Mechanical pressure (i.e., shearing with spatula) was applied to the product. Fol]owing the application of pressure, the product was irradiated with 5 ultraviolet radiation and the color of the product changed from ~ellow to blue.
2-4-hexadiyn-1,6-bis(n-propylurea);
Same as Examples 1 and 2 except 2.0 g (0.03 mol) lO mono-propargylamine, 3.1 9 (0.036 mol) n-propyliso-cyanate, 50 mL THF were employed to synthesize the mono-urea. The synthesis of the mono-urea required l hour at -25C. 0.25 9 CuCl and 2 mL TMEDA were added for the coupling reaction which was complete in 2~2 hours at 15 40C. Yield: 1.7 g (33%) of a yellowish white product which changed to a bright yellow upon exposure UV radia-tion. Recrystallization from acetic acid or ethanol (l g/lO0 mL) resulted in an active phase in each case which changed from pink to blue upon exposure to UV radia-tion. Upon heating to 300C, the product decomposed. A
melting point was not observed.
ELEMENTAL ANALYS IS
Cl4H22N4O2(MW = 27~.356) Calcd. C 60.~1 H 7.97 N 20.13 O 11.50 25Found. C 60.81 H ~.ll N 19.78 o 12.22 2,4-hexadiyn-1!6-bis(iso-propylurea) Same as Examples 1 and 2 except 2.0 9 (0.036 mol) 30 mono-propargylamine, 50 mL THF were used to synthesize the mono-urea and 0.25 9 CuCl and 2 mL TMEDA were added for the coupling reaction. Yield: 2.0 g (39%) of a white product which changed to a bright yellow upon expos~re to ultraviolét radiation. Recrystallization from various solvents such as acetic acid or ethanol (1 9/170 mL) did not result in an active blue phase when treated with UV light. The product melted and decom-posed at 270C.
:
.
~3~ 5 ELEMENTAL ANALYSIS
C14H22N4O2(MW = 278.356~ Calcd. C 60.41 H 7.97 N 20.13O 11.50 Found. C 60.84 H 8.09 N 19.75O 11.93 2,4-hexadi~n-1,6-bis(methylurea);
Same as Examples 1 and 2 except 2.0 9 ~0.036 mol) mono-propargylamine, 2.1 g (0.036 mol) methylisocyanate, 10 and 50 mL THF were used to synthesize the mono-urea and O.25 g CuCl and 2 mL TMEDA were added for the coupling reaction. Synthesis of the mono-urea required 1 hour at ~
25C. The coupling reaction required ~2 hours at 40C. Yield: 1~7 g (41~) light pinkish white product 15 which changed to bright yellow upon exposure to 5-10 seconds of ultraviolet radiation. Recrystallization from dimethylsulfoxide, ethanol (1 9/250 mL~, or acetic acid did not result in an active blue phase~ Upon heat-ing, the product melted and decomposed at 255C.
ELEMENTAL ANALYSIS
CloH14N402(MW = 222.248) Calcd. C~4.04 ~ 6.35 N 25.21 O 14.40 Found. C 53.96 H 6.60 N 24.48 O 13.32 2,4-hexadiyn-1,6 bis(ethox~carbonylmethylene urea) Same as Examples 1 and 2 except 2.0 9 (0.036 mol) mono-propargylamine, 4.6 g (0.036 mol) ethylisocyanato-acetate, and 50 mL THF were used for the synthesis of the mono-urea and 0.25 g CuCl and 2 mL TMEDA were added for the coupling reaction. Synthesis of the mono-urea required 1 hour at 25C~ The coupling reaction required ~2hours at 45C. Yield: 5.0 9 (76%) of a pinkish product which changed to blue upon exposure to 5-10 seconds ultraviolet radiation. Upon heating, the product melted between 190 and 195C.
3~ 5 ELEMENTAL ANALYSIS
C16H22N4O6(MW = 366.374) Calcd. C 52.45 ~l6.05 N 15.29 O26.20 Found. C 52.13 H6O05 N 15.36 O25.68 2,4-hexa iyn-1,6-bis(butoxycarbonylmethylene urea), Same as Examples 1 and 2 except 2.0 9 (0.036 mol) mono-propargylamine, 5.6 9 (0.036 mol) butylisocyanato-10 acetate, and 50 mL THF were used for the synthesis ofthe mono-urea and 0.25 9 CuCl and 2 mL TMEDA were used for the coupling reaction. Synthesis of the mono-urea required 1 hour at 25C. The coupling reaction required 1~2 hours at 45C. Yield: 3.9 9 (51~) of a white prod-15 uct was obtained by recrystallization of the productfrom ethanol ~1 9/75 mL). A sample of the product turned blue upon exposure to 5-10 seconds of ultraviolet radiation. Upon heating, a sample of the product melted at 168-169C and turned 20 red upon cooling and solidification. The cooled and solidified product turned blue upon e~posure to 5-10 seconds of ultraviolet radiation.
ELEMENTAL ANALYSIS
C20H30N4O6(MW = 422.482) Calcd. C 56.86 H 7.16 N 13.26 O 22.72 Found. C 57.07 H 7.67 N 13.01 O ~1.61 2,4-hexadiyn-1,6-bis(phenylurea), Same as Examples 1 and 2 except 5.5 9 (0.1 mole,
6.2 mL) monopropargylamine, 14.9 9 (0.125 mole) phenyl isocyanate, and 100 mL THF were used to synthesize the mono-urea and 0.25 g CuCl and 2.5 9 TMEDA were used for the coupling reaction. Synthesis of the mono-urea required 1~2 hours at 25C. The coupling reaction was complete in ~2hours at 35C. Yield: 10.5 9 (61%~ of a white product. Upon exposure to ultraviolet radiation for 1-2 minutes the product underwent a color change ~L~3~
from white to light blue. Upon heating to 275C the product melted and decomposed.
_XAMPLE 12 Synthesis_of 2,4,8,10~dodecyltetrayn-1,12- -5 bis(ethy-lurea) This compound was produced by a 3 step synthesis that involved preparing two reactants, 1,6-dibromo-1,5 hexadiyne and l-propyn-3-ethylurea, and then oxidatively coupling the two reactants.
1,6-dibromo-1,5-hexadiyne was prepared in the fol-lowing manner:
Sodium hypobromite, NaOBr, was prepared by incre-mentally adding 120 9 (0.732 mole, 39.0 mL) bromine to a 6.35N NaOH solution composed of 76.2 9 (1.95 mole) NaOH
in 300 mL aqueous cooled to 0C. The solution was stirred for approximately ~2 hours. The solution was added dropwise over a 30 minute period to 1,5-hexadiyne 23.4 g (0.30 mole) and 100 mL H20 contained in a 1 liter 3-necked flask which was fitted with a mechanical 20 stirrer, thermometer, N2 flow tube to blanket the react-ants, and an ice-bath. The temperatu~e was kept below 18C throughout the additions. After 3 hours, the solid product was extracted with 100 mL diethylether, washed with H20 and then kept over 25 g ammonium chloride until 25 needed.
l-propyn-3-ethylurea was prepared in the following manner: To a 500 mL flask fitted with a stirrer, ther-mometer, N2 flow tube, and a dropping funnel, 75 mL THF
and 5.5 g (0.1 mole, 6~9 mL) monopropargylamine was 30 added followed by the dropwise addition of 7.1 9 (0.1 mole) ethylisocyanate in 10 mL THF; the temperature was initially moderated with a water bath and continued for 1 hour at room temperature.
In order to oxidatively couple 1,6-dibromo-1,5-hexadiyne and 1-propyn-3-ethylurea to thereby produce 2,4,8, 10-dodecyltetrayn-1, 12-bis(ethylurea), 0.2 g CuCl, lS mL n-ethylamine (70%) followed by 1.5 g NH2OH.HCl was added to the reaction media containing the ~3~7~5 urea. 13.5 9 (0.058 mole) 1,6-dibromo-1,5-hexadiyne in 25 mL THF was then added dropwise t:o the reaction media over a 20 minute period. Initially, the reaction media was cooled with a cold water bath so that the tempera-5 ture did not exceed 40C during the addition. There-after, the bath was removed and the reaction was con-tinued with stirring for 2 ~2hours at a temperature of 25C. Product precipitation occurred during the addi-tion of the dibromohexadiyne. The product was filtered 10 and washed with several small portions of T~F (50 mL
total). The filtrate was saved, then washed twice with a 10% HCl solution, followed by H2O washings and finally -washing with methanol and dried Yield: 12.1 9 (74.2~) pale blue product which changed to dark blue upon e~pos-15 ure to 5-10 seconds ultraviolet radiation. Upon con tinued irradiation (i.e. 4 minutes), the product changed to a metallic gold color at a moderate rate. The prod-uct did not melt when heated to 300C. When heated beyond 300C, it changed to red, then black, then decom-20 posed.
Synthesis of 1,5,7-nonatriy~-9-ethylurea This compound, a triyne, was recovered from ~he filtrate o~ the oxidative coupling reaction of Example 25 12. Addition of petroleum ether (50-110C) to the fil-trate caused precipitation of a brown product which was washed with 10~ HCl followed by H2O. The product was recrystallized from acetone/petroleum ether (50-110C). Yield: 3.~ 9 (34.5%) of a white product which changed to red upon exposure to 5-10 seconds of ultra violet radiation.
EL~ENTAL ~æLYSIS
C12H14N2O(202.257) Calcd C 71.~6 H 6.98 N 13.85 O 7.91 Fo~nd C 69.70 H 7.08 N 13.84 O 7.67 Br 1.7 Elemental analysis indicates that 6~ of the total theoretically possible bromide remained unhydrolysed.
~3~7~45 Synthesis of 2,4,8,10,14,16-Octahexayn-1,18-bis(ethylurea) This compound was obtained by oxidatively coupling 5 the triyne of Example 13. Using the method described in Example 1, 1.0 g (0.005 mol) 1,5,7-ethylurea was coupled in a complex composed of 0.25 g CuCl, 2.5 mL TMEDA, and 75 mL methanol, with oxygen being bubbled into reaction media at a moderate rate. The temperature of the reac-10 tion media was raised to 6~C during the initial 5-10 minutes of the reaction time and then heating was dis-continued. After 1 hour, 75 mL water was then added.
Thereafter, the reaction media was filtered to recover the product. The product was washed with water, ~Cl/H2O
15 and then water. The product was recrystallized from 125 mL acetic acid. Yield: 0.5 g (50%) of a light pink product which changed to a blue color upon being irradi-ated with UV light for 5-10 seconds. After 30 seconds of irradiation, the product changed to a blue-black 20 color.
ELEMENTAL ANALYSIS
C24H26N42(MW 402.5) Calcd. C 71.62 H 6.51 N 13.92 O 7.95 Found. C 71.13 H 6.75 N 13.57 O 8.55 Synthesis of 5,7-dodecadiyn-1,12-bis(ethylurea) This compound was synthesized via the following 5 step reaction sequence:
a) oxidatively coupling 5-hexyn-1-ol to produce 5,7-dodecadiyn-1,12-diol;
b) reacting the product of (a) with p-toluene-sulfonylchloride to produce 5-7-dodecadiyn-1,12-bis(p-toluenesulfonate);
c) reacting the product of (b) with potassium phthalimide to produce 1,12-diphthalimido-5,7-dodecadiyne;
d) subjecting the product of (c) to a two stage .~ .
~L~37~
hydrolysis (i.e., base hydrolysis followed by acid hydrolysis) followed by treatment with a base to produce 5-7-dodecadiyn-1,12-diamine;
e) reacting the product of (d) with ethylisocyanate to produce 5,7-dodecadiyn-1,12-bis(ethylurea).
Reaction steps a-e were conducted as follows:
a) A 1 liter 3-necked flask was charged with 150 mL methanol, 15 mL TMEDA, and 9 9 CuCl D 150 mL 5-hexyn-l-ol was oxidatively coupled using the Hay method by 10 adding it dropwise to the reaction media over a 45 minute time period while oxygen was being bubbled into the reaction media. During the addition, the tempera-ture of the media rose to approximately 60C, then sub-sided. Oxygen was bubbled into the reaction media for 15 an additional 15 hours before isolation of the prod-uct. Isolation: 800 mL chilled water was added to pre-cipitate the product. The product was filtered and washed with additional water. Recrystallization: The product was dissolved in 100 mL methanol and 5 to 10 mL
20 TMEDA. Precipitation was effected by adding chilled water (8-11C). After filtration and,washing with water, the product was recrystallized, again. After removal of most of the water, the product was washed with heptane three times and dried under vacuum.
25 Yield: 120 9 of a fluffy whi~e product.
b) 150 mL pyridine was added dropwise to a solu-tion composed of 58.2 9 (0.3 mole) 5,7-dodecadiyn-1,12-diol, (produced from reaction step ~a)), 150 9 (0.78 mole) p-toluenesulfonylchloride, and 150 mL THF over a 0.5 hour period at a temperature of 20 to 25C. The reaction was continued with stirring for 6.5 hours at a temperature of 25-30C. Isolation: The product was obtained by pouring the reaction media into 1 liter chilled water followed by filtration and several water washings~ Recrystallization: The particulate was dis-soIved in 1.5 liters methanol and refrigerated at -8C. Thereafter, it was filtered, washed with petroleum ether (50-110C), and vacuum dried. Yield:
.
~L~3~ S
110 g (73%) of a light tan product which changed to red upon exposure to 5-10 seconds of ultraviolet radia-tion. The product had a melting range of 58.5-59.8C.
c) 32.0 9 (0.064 mole) 5,7-dodecadiyn-1,12~bis(p-5 toluenesulfonate) from reaction step (b) and 32.0 g (0.17 mole~ potassium phthalimide were reacted in dimethylsulfoxide at 123-128C for 0.5 hours. The reac-tion media was cooled to 75C and 250 mL water was added to precipitate the product. The product was filtered, 10 washed several times with boiling water, acetone, and then heptane. Yield: 24.6 g (85~) of a light tan ~ine powdered product.
d) 10 g (0.022 mole) 1,12-diphthalimido-5,7-dodecadiyne, from reaction step (c), 50 mL H2O, 3.1 g (0-055 mole) ROH, 5 mL pyridine and 80 mL ethanol were refluxed for 1 hour then cooled to 50C.
e) 30 mL 10N HCl (0.3 mole) was added increment-ally to the reaction media followed by 1 g ZnC12 and refluxed for 3 hours. During the refluxing a product 20 began precipitating (probably the phthalic acid).
Isolation: Thereafter, the solvent was reduced by 75%. 100 mL H2O was added to the reaction media, boiled, filtered, and washed with 50 mL additional boiling H2O. (The filtrant contained 2.5 g (33% o~
25 theoretical) phthalic acid; the filtrate contained the diamine-acid salt, (ClH3NCH2-C-Ct2, and was observed as two phase separated layers both of which contain the diamine-acid. If the solvent is evaporated from the dark brown layer, a solid forms which changes to blue slowly. The addition of water transforms the blue solid to red). 50 mL 5N NaOM (10 g, 0.25 mole) was added incrementally to the filtrate to neutralize the diamine-acid and generate the diamine. Af ter cooling to 30C, the diamine was extracted with diethylether (150 mL) by shaking. The ether was distilled leaving 2.5 g yellow semi-viscous crude product.
f ) To the crude product of step (e), 50 mL THF and 3 g of MgS04 (anhydrous) were added. The solution was :., ~;~3'~4L5 filtered and 3.2 g (0.045 mole) ethylisocyanate was added in one-shot at room temperature (25C). A solid precipitated immediately. After 1/2hour, 200 mL heptane was added to fully precipitate the product. It was 5 filtered and washed with heptane. Yield: l.B g (25~ of theoretical) white product which changes to blue slowly in daylight. When exposed to UV light, it changes to dark blue within 15 seconds time. The product was con-firmed by IR and elemental analyses. Additional product 10 was obtained by adding 200 mL xylene to the dark viscous layer of the filtrate after pouring off the top layer, boiling, then filtering through MgSO4. After cooling to -50C, 3.2 g (0.045 mole) ethylisocyanate was added. The product tcontaining both symmetrical and unsymmetrical 15 compounds) was precipitated with heptane after ~2hour, filtered, and washed vith additional heptane. Yield:
2~1 g crude white product which changes to blue slowly in daylight and dark blue within 30 seconds under a UV
lamp.
COLOR RESPONSE BROADENING FROM CO-CRYSTALLIZATION
A solution composed of 1.2 g 2,4-hexadiyn-1,6-bis(ethylurea) (hereinafter referred to as l-KE) in 60 mL acetic acid was prepared; likewise a solution com-5 posed of 1.2 g 2,4-hexadiyn-1,6-bis(butylurea) (herein-after referred to as l-KB) was also prepared. The solu-tions were mixed in the proportions shown in Table I and precipitated with an equal volume (about 10 mL) of petroleum ether ~50-110C), filtered, and dried. The 30 color responses of the co-crystalized composition were visually monitored. After 3 days at ambient conditions (about 25C) in the dark the co-crystallized composi-tions were assigned a relative reactivity value from 1 to 4.
TARLE I
Visual Color Response and Relative Reactivity for Co-Crystallized 1-KE and 1-~
Visual Soln (mls) Soln (~) Color Response Relative IKE lK~ lK~ lKB After 3 days Reactivity n.n o.o loo n light gray blue 3 .5 0.5 95 5 light to med. blue 1 (most reactive) 9.0 1.0 90 10 light to light - med. blue 2 10 5,0 5.0 50 50 off-white l.o s.n lo 90 off-white 0.5 9.5 5 95 pale blue 4 0.0 ln.0 0 100 yellow-orange Characterization of Incremental Reflectivity Changes An ink was formed by mixing 12.5 grams of 2,4-hexadiyn-1, h-bis(ethylurea) (l-KE) with 36 ml of n-butanol and grinding this mixture in a ball mill for 16 hours. ln grams of this suspension was mixed wth 22.5 grams of a 12% (w/w) solution of Ethocell (trademark) 45 dissolved in n-butanol. A portion of the ink was diluted so that the diluted ink had an acetylenic concentration that was only one half of the acetylenic concentration of the non-diluted ink.
A number of indicator labels were prepared by printing a rectangular image (0.3 cm X 2.1 cm) on pres-sure sensitive white labels with the ink. A solid black bar (0.2 cm x 2.1 cm) was printed on each side of the acteylenic urea bar at distance of 0.2 cm from the outer edge of the acetylenic urea bar. Thus, a white space n . 2 cm wide was between the acetylenic urea bar and the black barsO Thereafter, the labels were placed in controlled temperature baths (i.e. 60C, 40C, and 30C), and removed periodically in order to determine the reflectance of the indicator after exposure to a given temperature for a given period of time. Upon removal of the indicators from the temperature con-~ s
from white to light blue. Upon heating to 275C the product melted and decomposed.
_XAMPLE 12 Synthesis_of 2,4,8,10~dodecyltetrayn-1,12- -5 bis(ethy-lurea) This compound was produced by a 3 step synthesis that involved preparing two reactants, 1,6-dibromo-1,5 hexadiyne and l-propyn-3-ethylurea, and then oxidatively coupling the two reactants.
1,6-dibromo-1,5-hexadiyne was prepared in the fol-lowing manner:
Sodium hypobromite, NaOBr, was prepared by incre-mentally adding 120 9 (0.732 mole, 39.0 mL) bromine to a 6.35N NaOH solution composed of 76.2 9 (1.95 mole) NaOH
in 300 mL aqueous cooled to 0C. The solution was stirred for approximately ~2 hours. The solution was added dropwise over a 30 minute period to 1,5-hexadiyne 23.4 g (0.30 mole) and 100 mL H20 contained in a 1 liter 3-necked flask which was fitted with a mechanical 20 stirrer, thermometer, N2 flow tube to blanket the react-ants, and an ice-bath. The temperatu~e was kept below 18C throughout the additions. After 3 hours, the solid product was extracted with 100 mL diethylether, washed with H20 and then kept over 25 g ammonium chloride until 25 needed.
l-propyn-3-ethylurea was prepared in the following manner: To a 500 mL flask fitted with a stirrer, ther-mometer, N2 flow tube, and a dropping funnel, 75 mL THF
and 5.5 g (0.1 mole, 6~9 mL) monopropargylamine was 30 added followed by the dropwise addition of 7.1 9 (0.1 mole) ethylisocyanate in 10 mL THF; the temperature was initially moderated with a water bath and continued for 1 hour at room temperature.
In order to oxidatively couple 1,6-dibromo-1,5-hexadiyne and 1-propyn-3-ethylurea to thereby produce 2,4,8, 10-dodecyltetrayn-1, 12-bis(ethylurea), 0.2 g CuCl, lS mL n-ethylamine (70%) followed by 1.5 g NH2OH.HCl was added to the reaction media containing the ~3~7~5 urea. 13.5 9 (0.058 mole) 1,6-dibromo-1,5-hexadiyne in 25 mL THF was then added dropwise t:o the reaction media over a 20 minute period. Initially, the reaction media was cooled with a cold water bath so that the tempera-5 ture did not exceed 40C during the addition. There-after, the bath was removed and the reaction was con-tinued with stirring for 2 ~2hours at a temperature of 25C. Product precipitation occurred during the addi-tion of the dibromohexadiyne. The product was filtered 10 and washed with several small portions of T~F (50 mL
total). The filtrate was saved, then washed twice with a 10% HCl solution, followed by H2O washings and finally -washing with methanol and dried Yield: 12.1 9 (74.2~) pale blue product which changed to dark blue upon e~pos-15 ure to 5-10 seconds ultraviolet radiation. Upon con tinued irradiation (i.e. 4 minutes), the product changed to a metallic gold color at a moderate rate. The prod-uct did not melt when heated to 300C. When heated beyond 300C, it changed to red, then black, then decom-20 posed.
Synthesis of 1,5,7-nonatriy~-9-ethylurea This compound, a triyne, was recovered from ~he filtrate o~ the oxidative coupling reaction of Example 25 12. Addition of petroleum ether (50-110C) to the fil-trate caused precipitation of a brown product which was washed with 10~ HCl followed by H2O. The product was recrystallized from acetone/petroleum ether (50-110C). Yield: 3.~ 9 (34.5%) of a white product which changed to red upon exposure to 5-10 seconds of ultra violet radiation.
EL~ENTAL ~æLYSIS
C12H14N2O(202.257) Calcd C 71.~6 H 6.98 N 13.85 O 7.91 Fo~nd C 69.70 H 7.08 N 13.84 O 7.67 Br 1.7 Elemental analysis indicates that 6~ of the total theoretically possible bromide remained unhydrolysed.
~3~7~45 Synthesis of 2,4,8,10,14,16-Octahexayn-1,18-bis(ethylurea) This compound was obtained by oxidatively coupling 5 the triyne of Example 13. Using the method described in Example 1, 1.0 g (0.005 mol) 1,5,7-ethylurea was coupled in a complex composed of 0.25 g CuCl, 2.5 mL TMEDA, and 75 mL methanol, with oxygen being bubbled into reaction media at a moderate rate. The temperature of the reac-10 tion media was raised to 6~C during the initial 5-10 minutes of the reaction time and then heating was dis-continued. After 1 hour, 75 mL water was then added.
Thereafter, the reaction media was filtered to recover the product. The product was washed with water, ~Cl/H2O
15 and then water. The product was recrystallized from 125 mL acetic acid. Yield: 0.5 g (50%) of a light pink product which changed to a blue color upon being irradi-ated with UV light for 5-10 seconds. After 30 seconds of irradiation, the product changed to a blue-black 20 color.
ELEMENTAL ANALYSIS
C24H26N42(MW 402.5) Calcd. C 71.62 H 6.51 N 13.92 O 7.95 Found. C 71.13 H 6.75 N 13.57 O 8.55 Synthesis of 5,7-dodecadiyn-1,12-bis(ethylurea) This compound was synthesized via the following 5 step reaction sequence:
a) oxidatively coupling 5-hexyn-1-ol to produce 5,7-dodecadiyn-1,12-diol;
b) reacting the product of (a) with p-toluene-sulfonylchloride to produce 5-7-dodecadiyn-1,12-bis(p-toluenesulfonate);
c) reacting the product of (b) with potassium phthalimide to produce 1,12-diphthalimido-5,7-dodecadiyne;
d) subjecting the product of (c) to a two stage .~ .
~L~37~
hydrolysis (i.e., base hydrolysis followed by acid hydrolysis) followed by treatment with a base to produce 5-7-dodecadiyn-1,12-diamine;
e) reacting the product of (d) with ethylisocyanate to produce 5,7-dodecadiyn-1,12-bis(ethylurea).
Reaction steps a-e were conducted as follows:
a) A 1 liter 3-necked flask was charged with 150 mL methanol, 15 mL TMEDA, and 9 9 CuCl D 150 mL 5-hexyn-l-ol was oxidatively coupled using the Hay method by 10 adding it dropwise to the reaction media over a 45 minute time period while oxygen was being bubbled into the reaction media. During the addition, the tempera-ture of the media rose to approximately 60C, then sub-sided. Oxygen was bubbled into the reaction media for 15 an additional 15 hours before isolation of the prod-uct. Isolation: 800 mL chilled water was added to pre-cipitate the product. The product was filtered and washed with additional water. Recrystallization: The product was dissolved in 100 mL methanol and 5 to 10 mL
20 TMEDA. Precipitation was effected by adding chilled water (8-11C). After filtration and,washing with water, the product was recrystallized, again. After removal of most of the water, the product was washed with heptane three times and dried under vacuum.
25 Yield: 120 9 of a fluffy whi~e product.
b) 150 mL pyridine was added dropwise to a solu-tion composed of 58.2 9 (0.3 mole) 5,7-dodecadiyn-1,12-diol, (produced from reaction step ~a)), 150 9 (0.78 mole) p-toluenesulfonylchloride, and 150 mL THF over a 0.5 hour period at a temperature of 20 to 25C. The reaction was continued with stirring for 6.5 hours at a temperature of 25-30C. Isolation: The product was obtained by pouring the reaction media into 1 liter chilled water followed by filtration and several water washings~ Recrystallization: The particulate was dis-soIved in 1.5 liters methanol and refrigerated at -8C. Thereafter, it was filtered, washed with petroleum ether (50-110C), and vacuum dried. Yield:
.
~L~3~ S
110 g (73%) of a light tan product which changed to red upon exposure to 5-10 seconds of ultraviolet radia-tion. The product had a melting range of 58.5-59.8C.
c) 32.0 9 (0.064 mole) 5,7-dodecadiyn-1,12~bis(p-5 toluenesulfonate) from reaction step (b) and 32.0 g (0.17 mole~ potassium phthalimide were reacted in dimethylsulfoxide at 123-128C for 0.5 hours. The reac-tion media was cooled to 75C and 250 mL water was added to precipitate the product. The product was filtered, 10 washed several times with boiling water, acetone, and then heptane. Yield: 24.6 g (85~) of a light tan ~ine powdered product.
d) 10 g (0.022 mole) 1,12-diphthalimido-5,7-dodecadiyne, from reaction step (c), 50 mL H2O, 3.1 g (0-055 mole) ROH, 5 mL pyridine and 80 mL ethanol were refluxed for 1 hour then cooled to 50C.
e) 30 mL 10N HCl (0.3 mole) was added increment-ally to the reaction media followed by 1 g ZnC12 and refluxed for 3 hours. During the refluxing a product 20 began precipitating (probably the phthalic acid).
Isolation: Thereafter, the solvent was reduced by 75%. 100 mL H2O was added to the reaction media, boiled, filtered, and washed with 50 mL additional boiling H2O. (The filtrant contained 2.5 g (33% o~
25 theoretical) phthalic acid; the filtrate contained the diamine-acid salt, (ClH3NCH2-C-Ct2, and was observed as two phase separated layers both of which contain the diamine-acid. If the solvent is evaporated from the dark brown layer, a solid forms which changes to blue slowly. The addition of water transforms the blue solid to red). 50 mL 5N NaOM (10 g, 0.25 mole) was added incrementally to the filtrate to neutralize the diamine-acid and generate the diamine. Af ter cooling to 30C, the diamine was extracted with diethylether (150 mL) by shaking. The ether was distilled leaving 2.5 g yellow semi-viscous crude product.
f ) To the crude product of step (e), 50 mL THF and 3 g of MgS04 (anhydrous) were added. The solution was :., ~;~3'~4L5 filtered and 3.2 g (0.045 mole) ethylisocyanate was added in one-shot at room temperature (25C). A solid precipitated immediately. After 1/2hour, 200 mL heptane was added to fully precipitate the product. It was 5 filtered and washed with heptane. Yield: l.B g (25~ of theoretical) white product which changes to blue slowly in daylight. When exposed to UV light, it changes to dark blue within 15 seconds time. The product was con-firmed by IR and elemental analyses. Additional product 10 was obtained by adding 200 mL xylene to the dark viscous layer of the filtrate after pouring off the top layer, boiling, then filtering through MgSO4. After cooling to -50C, 3.2 g (0.045 mole) ethylisocyanate was added. The product tcontaining both symmetrical and unsymmetrical 15 compounds) was precipitated with heptane after ~2hour, filtered, and washed vith additional heptane. Yield:
2~1 g crude white product which changes to blue slowly in daylight and dark blue within 30 seconds under a UV
lamp.
COLOR RESPONSE BROADENING FROM CO-CRYSTALLIZATION
A solution composed of 1.2 g 2,4-hexadiyn-1,6-bis(ethylurea) (hereinafter referred to as l-KE) in 60 mL acetic acid was prepared; likewise a solution com-5 posed of 1.2 g 2,4-hexadiyn-1,6-bis(butylurea) (herein-after referred to as l-KB) was also prepared. The solu-tions were mixed in the proportions shown in Table I and precipitated with an equal volume (about 10 mL) of petroleum ether ~50-110C), filtered, and dried. The 30 color responses of the co-crystalized composition were visually monitored. After 3 days at ambient conditions (about 25C) in the dark the co-crystallized composi-tions were assigned a relative reactivity value from 1 to 4.
TARLE I
Visual Color Response and Relative Reactivity for Co-Crystallized 1-KE and 1-~
Visual Soln (mls) Soln (~) Color Response Relative IKE lK~ lK~ lKB After 3 days Reactivity n.n o.o loo n light gray blue 3 .5 0.5 95 5 light to med. blue 1 (most reactive) 9.0 1.0 90 10 light to light - med. blue 2 10 5,0 5.0 50 50 off-white l.o s.n lo 90 off-white 0.5 9.5 5 95 pale blue 4 0.0 ln.0 0 100 yellow-orange Characterization of Incremental Reflectivity Changes An ink was formed by mixing 12.5 grams of 2,4-hexadiyn-1, h-bis(ethylurea) (l-KE) with 36 ml of n-butanol and grinding this mixture in a ball mill for 16 hours. ln grams of this suspension was mixed wth 22.5 grams of a 12% (w/w) solution of Ethocell (trademark) 45 dissolved in n-butanol. A portion of the ink was diluted so that the diluted ink had an acetylenic concentration that was only one half of the acetylenic concentration of the non-diluted ink.
A number of indicator labels were prepared by printing a rectangular image (0.3 cm X 2.1 cm) on pres-sure sensitive white labels with the ink. A solid black bar (0.2 cm x 2.1 cm) was printed on each side of the acteylenic urea bar at distance of 0.2 cm from the outer edge of the acetylenic urea bar. Thus, a white space n . 2 cm wide was between the acetylenic urea bar and the black barsO Thereafter, the labels were placed in controlled temperature baths (i.e. 60C, 40C, and 30C), and removed periodically in order to determine the reflectance of the indicator after exposure to a given temperature for a given period of time. Upon removal of the indicators from the temperature con-~ s
7~5 trolled compartments, each indicator was scanned with an Intermec (trademark) 1401 scanning wand. The signal generated was forwarded through an amplifier (Signal Control Module T 22050, Skan-a-matic Corp~) and into a TECH LAB I computer. The signal was processed by averaging the reflectance values of the white (W) sections and black (~) bars and the reflectance values of the acetylenic urea bars (AC) as R= WACBB . This value was used to determine the reflectance of the acetylenic urea compound relative to the white and black reference colors. These data are presented in Tables I, II, and III.
TABLE I_ Temperature 60C
Indicator 1 Indicator 2*
Time (Days) ~ Reflectance ~ Reflectance ~ 99 98 n.ll 94 ~~
0.25 gn --0.37 83 92 20n. 59 77 ~7 1.08 64 78 1.97 39 59 2.91 25 44 3.68 17 33 254.41 12 27 4.71 25 *Indicator 2 had an acetylenic urea concentration equal to one half that of Indicator l.
,. . t 1~3~
TABLE II
Temperature 40C
Indicator 3* Indicator 4*
Time (Days) ~ Reflectance Time tDays) _~ Reflectance .0 98 .0 98 O. 11 99 0 . 11 1.01 95 1.01 1.81 94 1.81 96 102.03 93 4.84 93 2.52 93 5.33 90 9.35 76 12.16 81 20.43 53 18.37 71 24O64 46 23.24 61 a 15 27~45 57 b 26 , *Indicator 4 had an acetylenic urea concentration equal to that of Indicator 2, Indicator 3 had an acetylenic urea concentration equal to that of Indicator 1.
20 a - stored for 49 additional hours at 60C.
b - stored for 49 additional hours at 60C.
TAB E III
Temperature 30C
Indicator 5* Indicator 6*
25 Time tDaYS) % Refl ctance % Reflectance .0 99 98 3.8 95 98 24.0 86 93 _ *Indicator 6 had a acetylenic urea concentration equal to that of Indicator 2, Indicator 5 had an acetylenic urea concentration equal to that of Indicator 1.
The data in Tables, I r II, and III illustrate that percent re1ectance is a function of time, temperature and concentration of indicating material, with higher temperatures, longer exposures and higher concentrations of indicating materials resulting in a more rapid decrease in reflectance. Using the data in Tables I and ~,-,,, - - - - - - .:, ~L~3~ S
II, an activation energy of 29 kcal/mol was determined for l-KE. The activation energy was calculated from these data by determining the time necessary to reach a given reflectance value at two temperatures usin.g a form 5 of the Arrhenius equation.
-Color Characterization l-KE and 2,4-hexadiyn-1,6 bis(butylurea) (l-KB) inks haYing a concentration equal to the non-diluted 1-KE ink of Example 17 were produced as in Example 17.cm diameter dots of these inks were screen printed on Kimdura substrate Thereafter, the dot indicators were placed on a Mettler bot stage for varying lengths of time at 110C and 90C. The colors of the dot indica-tors exposed to these temperatures for varying lengthsof time were correlated with the Munsell Color Code.
The results appear in Tables IV and VO
TABLE IV
Temperature 110C
l-KE l-KB
Time (min.) Munsell Color Code Munsell Color Code 0 lOPB 8/2 2.5P 9/2 6 lOPB 6/4 lOPB 4/8 11 lOPB 4/67.5PB 4/8 2524 2.5P 3/45PB 3/8 31 2.5P 2.5/4 5PB 3/8 42 2.5P 2.5/2 5PB 3/6 53 5P 2. 5/2 5PB3/6 64 lOPB 3/15PB 3/6 30100 5R 2. 5/1 5PB3/6 118 54R 2.5/1 5PB3/4 _ .. . .
~l~3~7~L~S
TABLE V
Temperature 90C
l-KE l-KB
Time (min.) Munsell Color Code Munsell Color Code . . _ . . . _ _ 5 0 5PB 8/1 2.5P 9/2 6 5P 7/4 2.5PB 5/6 18 2.5P 6/6 7.5PB 4/6 38 5P 5/6 7.SPB 4/6 104 2.5P 3/8 7/5PB 3/6 10 133 2.5PB 3/8 7.5PB 3/4 170 2.5PB 3/4 7.5PB 3/4 192 2.5 205/4 7.5PB 3/9 230 7.5PB 2.5/4 7.5PB 3/4 The results of Examples 17 and 18 illustrate tha-t 15 l-KE and l-KB can be employed to monitor a wide variety of perishable products, or processes. For example, the data of Example 17 demonstrate that l-KE can be employed to monitor a product with a shelf-life of about 1.5-3 years at 25C. The results also demonstrate that by increasing the acetylenic urea concentration one can monitor periods of time of one year or shorter at room temperature. The results of Example 18 demonstrate that the color changes associated with the compounds tested could be used to verify that foodstuff cans have been 25 properly sterilized by thermal treatment, as some cans for this purpose are sub]ected to temperatures in the 90C - 100C range for 10-30 minutes for sterilization purposes.
TABLE I_ Temperature 60C
Indicator 1 Indicator 2*
Time (Days) ~ Reflectance ~ Reflectance ~ 99 98 n.ll 94 ~~
0.25 gn --0.37 83 92 20n. 59 77 ~7 1.08 64 78 1.97 39 59 2.91 25 44 3.68 17 33 254.41 12 27 4.71 25 *Indicator 2 had an acetylenic urea concentration equal to one half that of Indicator l.
,. . t 1~3~
TABLE II
Temperature 40C
Indicator 3* Indicator 4*
Time (Days) ~ Reflectance Time tDays) _~ Reflectance .0 98 .0 98 O. 11 99 0 . 11 1.01 95 1.01 1.81 94 1.81 96 102.03 93 4.84 93 2.52 93 5.33 90 9.35 76 12.16 81 20.43 53 18.37 71 24O64 46 23.24 61 a 15 27~45 57 b 26 , *Indicator 4 had an acetylenic urea concentration equal to that of Indicator 2, Indicator 3 had an acetylenic urea concentration equal to that of Indicator 1.
20 a - stored for 49 additional hours at 60C.
b - stored for 49 additional hours at 60C.
TAB E III
Temperature 30C
Indicator 5* Indicator 6*
25 Time tDaYS) % Refl ctance % Reflectance .0 99 98 3.8 95 98 24.0 86 93 _ *Indicator 6 had a acetylenic urea concentration equal to that of Indicator 2, Indicator 5 had an acetylenic urea concentration equal to that of Indicator 1.
The data in Tables, I r II, and III illustrate that percent re1ectance is a function of time, temperature and concentration of indicating material, with higher temperatures, longer exposures and higher concentrations of indicating materials resulting in a more rapid decrease in reflectance. Using the data in Tables I and ~,-,,, - - - - - - .:, ~L~3~ S
II, an activation energy of 29 kcal/mol was determined for l-KE. The activation energy was calculated from these data by determining the time necessary to reach a given reflectance value at two temperatures usin.g a form 5 of the Arrhenius equation.
-Color Characterization l-KE and 2,4-hexadiyn-1,6 bis(butylurea) (l-KB) inks haYing a concentration equal to the non-diluted 1-KE ink of Example 17 were produced as in Example 17.cm diameter dots of these inks were screen printed on Kimdura substrate Thereafter, the dot indicators were placed on a Mettler bot stage for varying lengths of time at 110C and 90C. The colors of the dot indica-tors exposed to these temperatures for varying lengthsof time were correlated with the Munsell Color Code.
The results appear in Tables IV and VO
TABLE IV
Temperature 110C
l-KE l-KB
Time (min.) Munsell Color Code Munsell Color Code 0 lOPB 8/2 2.5P 9/2 6 lOPB 6/4 lOPB 4/8 11 lOPB 4/67.5PB 4/8 2524 2.5P 3/45PB 3/8 31 2.5P 2.5/4 5PB 3/8 42 2.5P 2.5/2 5PB 3/6 53 5P 2. 5/2 5PB3/6 64 lOPB 3/15PB 3/6 30100 5R 2. 5/1 5PB3/6 118 54R 2.5/1 5PB3/4 _ .. . .
~l~3~7~L~S
TABLE V
Temperature 90C
l-KE l-KB
Time (min.) Munsell Color Code Munsell Color Code . . _ . . . _ _ 5 0 5PB 8/1 2.5P 9/2 6 5P 7/4 2.5PB 5/6 18 2.5P 6/6 7.5PB 4/6 38 5P 5/6 7.SPB 4/6 104 2.5P 3/8 7/5PB 3/6 10 133 2.5PB 3/8 7.5PB 3/4 170 2.5PB 3/4 7.5PB 3/4 192 2.5 205/4 7.5PB 3/9 230 7.5PB 2.5/4 7.5PB 3/4 The results of Examples 17 and 18 illustrate tha-t 15 l-KE and l-KB can be employed to monitor a wide variety of perishable products, or processes. For example, the data of Example 17 demonstrate that l-KE can be employed to monitor a product with a shelf-life of about 1.5-3 years at 25C. The results also demonstrate that by increasing the acetylenic urea concentration one can monitor periods of time of one year or shorter at room temperature. The results of Example 18 demonstrate that the color changes associated with the compounds tested could be used to verify that foodstuff cans have been 25 properly sterilized by thermal treatment, as some cans for this purpose are sub]ected to temperatures in the 90C - 100C range for 10-30 minutes for sterilization purposes.
Claims (12)
1. An organic compound comprising an acetylenic compound having at least one -C?C-C?C- moiety and two urea moieties, said compound being capable of undergoing incremental reflectivity changes upon exposure to environmental stimuli; wherein said compound includes at least one methylene moiety between each -C?C-C?C- moiety and one of said urea moieties.
2. A compound in accordance with claim 1 of the structure wherein R is an organic moiety comprising one or more moieties selected from the group comprising a cycloalkyl moiety of 3-7 carbon atoms, an alkenyl moiety of 3-18 carbon atoms, a cycloalkenyl moiety of 3-7 carbon atoms, an alkoxy moiety of 2-18 carbon atoms, a linear or branched alkyl moiety of 1 to 18 carbon atoms, an alkoxycarbonylmethylene moiety of 3-14 carbon atoms, or a phenyl moiety; wherein n is an integer of 1 to 10.
3. A compound in accordance with claim 2 wherein R
is a linear or branched alkyl moiety of 1-18 carbon atoms, an alkoxycarbonymethylene moiety of 3-14 carbon atoms, or a phenyl moiety.
is a linear or branched alkyl moiety of 1-18 carbon atoms, an alkoxycarbonymethylene moiety of 3-14 carbon atoms, or a phenyl moiety.
4. A compound in accordance with claim 3 wherein R
is a linear or branched alkyl moiety of 1 to 18 carbon atoms and n is 1.
is a linear or branched alkyl moiety of 1 to 18 carbon atoms and n is 1.
5. A compound in accordance with claim 4 wherein R
is ethyl.
is ethyl.
6. A compound in accordance with claim 4 wherein R
is n-propyl.
is n-propyl.
7. A compound in accordance with claim 1 of the structure wherein R is an organic moiety comprising one or more moieties selected from the group comprising a cycloalkyl moiety of 3-7 carbon atoms, an alkenyl moiety of 3-18 carbon atoms, a cycloalkenyl moiety of 3-7 carbon atoms, an alkoxy moiety of 2-18 carbon atoms, a linear or branched alkyl moiety of 1 to 18 carbon atoms, an alkoxycarbonylmethylene moiety of 3-14 carbon atoms, or a phenyl moiety; wherein y is an integer of 1 to 18 and wherein x is an integer of 1 to 6.
8. A compound in accordance with claim 7 wherein R
is a linear or branched alkyl moiety of 1-18 carbon atoms, an alkoxycarbonylmethylene moiety of 3-14 carbon atoms, or a phenyl moiety.
is a linear or branched alkyl moiety of 1-18 carbon atoms, an alkoxycarbonylmethylene moiety of 3-14 carbon atoms, or a phenyl moiety.
9. A compound in accordance with claim 1 wherein said composition is of the structure wherein R is an organic moiety comprising one or more moieties selected from the group comprising a cycloalkyl moiety of 3-7 carbon atoms, an alkenyl moiety of 3-18 carbon atoms, a cycloalkenyl moiety of 3-7 carbon atoms, an alkoxy moiety of 2-18 carbon atoms, a linear or branched alkyl moiety of 1 to 18 carbon atoms, an alkoxycarbonylmethylene moiety of 3-14 carbon atoms, or a phenyl moiety; wherein y is an integer of 1 to 8 and wherein x is an integer of 1 to 6.
10. A compound in accordance with claim 9 wherein R
is a linear or branched alkyl moiety of 1-18 carbon atoms, an alkoxycarbonylmethylene moiety of 3-14 carbon atoms, or a phenyl moiety.
is a linear or branched alkyl moiety of 1-18 carbon atoms, an alkoxycarbonylmethylene moiety of 3-14 carbon atoms, or a phenyl moiety.
11. A composition comprising at least two cocrystallized acetylenic compounds, at least one of said acetylenic compounds being a compound in accordance with claims 1 or 9.
12. A composition comprising two co-crystallized acetylenic compounds, each acetylenic compound being a compound in accordance with any of claims 1 or 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US51439983A | 1983-07-18 | 1983-07-18 | |
| US514,399 | 1983-07-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1237145A true CA1237145A (en) | 1988-05-24 |
Family
ID=24046965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000457436A Expired CA1237145A (en) | 1983-07-18 | 1984-06-26 | Acetylenic compounds containing urea moieties useful as environmental indicating materials |
Country Status (3)
| Country | Link |
|---|---|
| JP (3) | JPH0742266B2 (en) |
| CA (1) | CA1237145A (en) |
| DK (1) | DK348884A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0633145A1 (en) * | 1993-07-08 | 1995-01-11 | Nippon Paper Industries Co., Ltd. | Thermal recording sheet |
| US6504161B1 (en) | 1999-09-10 | 2003-01-07 | Sunspots, Inc. | Radiation indicator device |
| US8269042B2 (en) * | 2007-10-30 | 2012-09-18 | Temptime Corporation | Crystallized diacetylenic indicator compounds and methods of preparing the compounds |
| CN111269128A (en) * | 2020-04-02 | 2020-06-12 | 苏州爱玛特生物科技有限公司 | Synthesis method of 1, 1' - (hexa-2, 4-diyne-1, 6-diyl) bis (3-alkyl urea) compound |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5248748A (en) * | 1986-05-16 | 1993-09-28 | Dir. General Of Agency Of Industrial Science And Technology | Diacetylene compound having double bond and shaped article thereof |
| US4987257A (en) * | 1986-05-16 | 1991-01-22 | Director-General Of Agency Of Industrial Science And Technology | Diacetylene compound having double bond and shaped article thereof |
| US5175307A (en) * | 1986-05-16 | 1992-12-29 | Agency Of Industrial Science & Technology | Diacetylene compound having double bond and shaped article thereof |
| US6046455A (en) * | 1998-01-30 | 2000-04-04 | Segan Industries | Integrating ultraviolet exposure detection devices |
| CN103038271B (en) * | 2009-03-31 | 2016-03-16 | 坦普泰姆公司 | Can the diine monomer composition of cocrystallization, crystalline phase and mixture and methods involving |
-
1984
- 1984-06-26 CA CA000457436A patent/CA1237145A/en not_active Expired
- 1984-07-16 JP JP59147432A patent/JPH0742266B2/en not_active Expired - Lifetime
- 1984-07-17 DK DK348884A patent/DK348884A/en unknown
-
1994
- 1994-10-19 JP JP6253956A patent/JP2545703B2/en not_active Expired - Lifetime
- 1994-10-19 JP JP6253884A patent/JP2545702B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0633145A1 (en) * | 1993-07-08 | 1995-01-11 | Nippon Paper Industries Co., Ltd. | Thermal recording sheet |
| US6504161B1 (en) | 1999-09-10 | 2003-01-07 | Sunspots, Inc. | Radiation indicator device |
| US8269042B2 (en) * | 2007-10-30 | 2012-09-18 | Temptime Corporation | Crystallized diacetylenic indicator compounds and methods of preparing the compounds |
| US8642807B2 (en) | 2007-10-30 | 2014-02-04 | Temptime Corporation | Crystallized diacetylenic indicator compounds and methods of preparing the compounds |
| US8813675B2 (en) * | 2007-10-30 | 2014-08-26 | Temptime Corporation | Time-temperature indicators comprising crystallized diacetylenic indicator compounds |
| CN111269128A (en) * | 2020-04-02 | 2020-06-12 | 苏州爱玛特生物科技有限公司 | Synthesis method of 1, 1' - (hexa-2, 4-diyne-1, 6-diyl) bis (3-alkyl urea) compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2545702B2 (en) | 1996-10-23 |
| JPH0742266B2 (en) | 1995-05-10 |
| DK348884A (en) | 1985-01-19 |
| JPH07267916A (en) | 1995-10-17 |
| DK348884D0 (en) | 1984-07-17 |
| JP2545703B2 (en) | 1996-10-23 |
| JPH07258198A (en) | 1995-10-09 |
| JPS6038352A (en) | 1985-02-27 |
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