JPH07258198A - Urea-moity-containing acetylenic compound useful as environment indicating substance - Google Patents

Abstract

PURPOSE: To provide novel urea moiety-containing acetylenic substances useful as environmental indicator substances which incrementally and progressively change colors on exposure to environmental stimuli such as temperature, cumulative time-temperature and radiation.

CONSTITUTION: Acetylenic organic compounds capable of incrementally varying reflectance on exposure to environmental stimuli are represented by the formula (wherein R is at least one group of a 3-7C cycloalkyl moiety, 3-18C alkenyl, 3-7C cycloalkenyl, 2-18C alkoxy, 1-8C alkyl, etc.; (y) is an integer of 1-8; and (x) is an integer of 1-6) and include, e.g. 2,4-hexadyne-1,6-bis(ethylurea). In the compounds of the formula it is preferred that R is 1-18C alkyl, 3-14C alkoxycarbonylmethyl or phenyl. The compounds of the formula can be obtained via the two-step reaction of, e.g. reacting monopropargylamine with a suitable isocyanate and subsequently subjecting the resulting alkyne intermediate to oxidation coupling.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel acetylenic compound useful as an environmental indicator material. The acetylenic compound has at least one —C≡C—C≡C— moiety and 2
Urea moieties and at least one methylene moiety between each —C≡C—C≡C-acetylene moiety and one of the urea moieties. The utility of the compounds is that when they are exposed to environmental stimuli such as temperature, cumulative time-temperature and radiation.
The fact is that the color changes incrementally or progressively. The reactivity of the compound of the present invention may be increased or decreased depending on the case by co-crystallizing two or more compounds from a common solvent. The compounds of the present invention, like other acetylenic compounds, change color based on polymerization by 1,4 addition reaction upon exposure to environmental stimuli.

[0002]

The color-changing acetylenic compounds described above are known in the art. For example, acetylenic compounds having at least one -C [identical to] C-C [identical to] C- are disclosed in U.S. Pat. No. 3,999,946 (Patee et al.) As a time-temperature history indicator. There is. Peter et al. Disclose an acetylenic compound monomer of the formula R-C≡C-C≡C-R (wherein
R includes alkyl, aryl, benzoate, sulfonate, urethane, acid or alcohol moieties. ). The compounds disclosed by Peter et al. Are colorless and can be polymerized thermally or in the solid state by actinic radiation. As the polymerization progresses, these compounds change color in contrast to blue or red, optionally changing color with time until the compound eventually becomes a metallic polymer. Thus, this compound can be used as a time-temperature history indicator and a radiation administration indicator. In the cited patent

[Chemical 2] (Where m is 2, 3 or 4 and n is a large number), polymers containing repeating units of the same empirical formula change color upon thermal annealing. Other examples of U.S. Patents relating to acetylenic compounds and environmental indicators include U.S. Pat. Nos. 4,215,208 (thermochromic materials), 4,125,534 (carbazolyl diacetylenes) and 4,4. No. 189,399 (eutectic composition)
I have a statement. Alkoxycarbonyl urethane acetylenic compositions are disclosed in US Patent Application No. 364,590.

G. Wegner
Is Die Makromolekulare Che
Mie 154, pp. 35-48 (1972), "To
pochemical Polymerization
of Monomers With Conjuga
Ted Triple Bonds ”, at least 1
Having -C≡C-C≡C- moieties and two urea moieties,
Also disclosed are acetylenic compounds in which the urea moiety is separated from the diacetylene by a phenylene moiety. However, the compounds disclosed by Wegner were not very reactive and did not exhibit color changes that would be useful in monitoring environmental exposure.

[0004]

The object of the present invention is therefore to provide highly reactive compounds which are very useful as environmental indicators.

[0005]

The present invention contains at least one --C.ident.C--C.ident.C-- moiety and two urea moieties,
When exposed to environmental stimuli, the reflectance changes incrementally and each -C
It relates to an acetylenic organic compound containing at least one methylene moiety between a .tbd.C--C.tbd.C-- moiety and one of the above urea moieties.

[0006] The present invention relates to a novel acetylenic compound which is progressively changed in quality due to environmental exposure and is useful for monitoring environmental exposure of various products. Environmental exposure is exposure to temperature, cumulative time temperature and radiation.

The novel organic compounds of the present invention contain at least one --C.ident.C--C.ident.C-- moiety and two urea moieties,
There is at least one methylene moiety between each -C≡C-C≡C- moiety and one of the urea moieties. The acetylenic ureas of the present invention undergo an incremental or progressive color change upon exposure to environmental stimuli. That is, the reflectance changes according to the exposure to the environmental stimulus. The reflectance is defined as the amount of light of a specific wavelength reflected by the indicator substance after the light is made to act on the indicator substance. The reflectance of the perfectly reflective material is 1. The reflectance percentage is equal to 100 times the reflectance. The exposure of acetylenic ureas to their reflectance changes upon exposure to environmental stimuli, resulting in a contrasting color change when exposed to a given amount of actinic radiation or thermal annealing. The term "thermal annealing" means heating to a sufficient temperature with infrared radiation, a flame, a heat gun laser beam, and the like, which causes the polymerization by 1,4-addition of an acetylenic compound to a sufficiently high degree. To do. It is known in the art that many acetylenic compounds undergo contrasting color changes in the aforementioned reflectance upon exposure to environmental stimuli such as actinic radiation or thermal annealing. It is also known to use acetylenic compounds that change color as described above as environmental indicators, due to the fact that acetylenic compounds undergo a measurable incremental color change in response to environmental exposure. If a certain color corresponds to a given amount of product degradation or treatment, the color matching method can correlate the color change with product quality. However, product quality is preferably measured by the more accurate incremental reflectance measurement method described in U.S. Patent Application Serial No. 469,880. The novel compound of the present invention is
It gives acetylenic compounds which exhibit highly desirable properties and are particularly suitable as environmental indicators. These properties will be discussed in more detail below after a description of suitable urea acetylenic compounds and methods for their synthesis.

The preferred acetylenic compounds of the present invention are the compounds of the following general structural formulas I, II and III. Structure I
Is the most preferred family of compounds and is as follows:

[0009]

[Chemical 3] Wherein n is an integer of 1-10; R is a cycloalkyl moiety of 3-7 carbon atoms, an alkenyl moiety of 3-18 carbon atoms,
Group consisting of cycloalkenyl moieties of 3-7 carbon atoms, alkoxy moieties of 2-18 carbon atoms, linear or branched alkyl moieties of 1-18 carbon atoms, alkoxycarbonylmethylene moieties of 3-14 carbon atoms or phenyl moieties. Is one or more organic moieties selected from In many preferred embodiments of the invention R is a linear or branched alkyl moiety of 1-18 carbon atoms, an alkoxycarbonylmethylene moiety of 3-13 carbon atoms, ie CH ₃ (CH ₂ ).
_0-10 —O—C (O) CH ₂ — or a phenyl moiety.
Linear or branched alkyl moieties are especially preferred. Particularly suitable alkyl moieties include ethyl, n-propyl, n-butyl, n-octyl, n-dodecyl and n-octadecyl. Particularly preferred alkoxycarbonylmethylene moieties are ethoxycarbonylmethylene and butoxycarbonylmethylene. For all compounds of structure I, n
1-4 are preferable and 1 is more preferable.

Other preferred acetylenic compounds of the present invention include tetrayne and hexayne. Tetrayne and hexayne are represented by the following general formulas II and III.

[0011]

[Chemical 4] In the above formula, R is as described in the structure I, y is an integer of 1 to 18, z is an integer of 1 to 6, and x is an integer of 1 to 6.

The synthesis of the novel compounds of the present invention is easily accomplished by using methods well known to those skilled in the field of organic chemistry. For example, the compound having n = 1 in the general structure I is the most preferable compound group, but is synthesized by the following two-step reaction.

[0013]

[Chemical 5] In the above formula, R is as described above. In the upper reaction path,
Reacting the monopropargylamine with a suitable isocyanate (ie, having the desired R group corresponding to the R group described in compounds of general structure I) in tetrahydrofuran or other similar solvent such as 2-methoxyethyl ether, Form the alkyne intermediate with the urea moiety and the desired R group. The first reaction described above will occur at a temperature of about 25 ° C to about 50 ° C and will require a reaction time of about 1 to about 2 hours. No catalyst is needed. Then, without isolation of the intermediate, it is oxidatively coupled to the final product by a conventional method. The oxidative coupling reaction is from about 25 ° C to about 50 ° C.
It is carried out at a temperature of ° C and will generally require only about 2 to about 4 hours to complete the reaction. Isolation of the product from the reaction mixture is performed by conventional precipitation, filtration and recrystallization methods. However, some compounds give indicators with different reactivities depending on the recrystallization solvent.

The synthesis of compounds of structure I, where n = 2-10, is somewhat complicated, but conventional methods can be used. These compounds are formed by a five-step reaction mechanism, and in the first-step reaction, 3-butyn-1-ol and 4-pentyne-1 are formed.
Oxidative coupling of acetylenic compounds having a hydroxyl moiety at the end, such as -ol, 5-hexyn-1-ol or the like, to the corresponding diyne-diols. The diyne-diol is then reacted with p-toluene sulfonyl chloride to form a bis (p-toluene sulfonate) compound. In this reaction, tetrahydrofuran or other similar solvent is used as the reaction medium and pyridine is used as the promoter. Next, this diyne-bis (p-toluenesulfonate) compound was treated with "Angew. Chem. Int.
tern. Edit. , 7, 919 (1968)
Under the heading "Gabriel Synthesis of Primary Amines" by MS Gibson and RW Broadshaw.
Conversion to the diphthalimido-diyne compound using a Gabriel type synthetic method as described in w). The paper is cited. Then, the diphthalimide-diyne compound is hydrolyzed by two-step hydrolysis to produce a diyne-diamine salt. This two-step hydrolysis is also described in the Gibson and Broadjoe article and the use of this method is preferred.
Finally, the diyne-diamine is reacted with the appropriate RN = C = O according to the method described herein (n = 4),
A di-urea with the desired R group and n = 2-10 is prepared.

Tetraynes of general structure II and general structure I
The synthesis of hexain of II is conveniently accomplished by the following reaction scheme.

[0016]

[Chemical 6] In the above reaction (1), the diyne of x = 1-6 is reacted with a suitable hypobromite such as sodium hypobromite to produce the dibromodiyne compound (a). In reaction (2), a primary amine-terminated alkyne (y = 1-10) is reacted with the aforementioned isocyanate having an appropriate R group to produce urea (b) having an acetylene moiety and a desired R group at the terminal. To do. Then, the compounds (a) and (b) are subjected to a coupling reaction in the presence of a solution containing CuCl, n-ethylamine and hydroxylamine hydrochloride to produce a tetrayne of the general structural formula II. This coupling reaction is described in more detail in Example 12. The triyne (c) in the above reaction scheme is extracted from the reaction medium by the addition of a non-polar solvent such as petroleum ether, heptane, hexane or the like. Then, triyne (c) is oxidatively coupled by a well-known method according to the above reaction (4) to give a compound of general structural formula
Make the hexain of II.

Following the preparation of the compounds of the present invention, the compounds must be recrystallized from a suitable solvent in order to impart an active or inactive phase depending on the desired phase for the particular application. The compounds in the active phase will begin to polymerize upon exposure to environmental stimuli and will therefore change color. The compound in the inert phase will not initiate polymerization until it undergoes any action such as heating or application of mechanical pressure or exposure to a suitable solvent or solution to convert the inert phase to the active phase. .

Many of the acetylenic ureas have their polymerization reactivity increased or decreased by dissolving two or more compounds into a eutectic composition. Eutectic compositions differ in that they differ substantially in polymerization reactivity from mere mixtures of each compound, and thus in their rate of color change upon exposure to actinic radiation or thermal annealing. On the other hand, a mere mixture shows only the properties obtained by combining and adding the properties of the components corresponding to the properties of the existing components.

Many of the acetylenic urea compounds of the present invention change color from white, pink or light gray to a blue of various tones upon exposure to environmental stimuli and, therefore, emit light in the spectral range from about 250 nm to about 700 nm. Will absorb. Therefore, environmental indicator labels prepared from the compounds of the invention are optical comprising a light source illuminating the surface; a detector sensitive to the amount of reflected light; and means for outputting a signal from an optical detector operating in this spectral range. Read by a dynamic scanner. Alkyl ureas of the general structural formula I in which R is a linear or branched alkyl of 1-18 carbon atoms are the most preferred compounds, but most ureas of this nature are gradually exposed to environmental stimuli. It is particularly useful in that it polymerizes to a blue color, and the rate of polymerization and color responsiveness are directly related to environmental exposure. Alkyl ureas are also particularly useful in that they have the property of melting at elevated temperatures, generally above about 170 ° C., or simply decomposing at temperatures above about 200 ° C. without any melting. This property is a highly desirable property in addition to the optical spectral properties of such compounds. Many of the acetylenic compounds described in the prior art melt at moderate temperatures. Melting of partially polymerized acetylenic compositions usually changes color and can give false information about cumulative temperature exposure. Many compounds of the invention other than alkylureas also have high melting points or no melting points. This has the general structural formula II
And III appear to be true for tetraynes and hexaynes.

The acetylenic urea compound of the present invention is manufactured into an environmental indicator according to a known method. The environment indicating device is a device attached in some form to a product whose quality gradually changes in response to environmental exposure, and is a device capable of recording the environmental exposure amount of the product. The acetylenic compound of the present invention records the amount of environmental exposure as a color change, and the color change is observed visually or in US patent application Serial No. 469,8.
It is measured by an optical scanning method as described in No. 80.
Optical scanning of an environmental indicator using the acetylenic urea of the present invention is described in Example 17.

Substrates used to fabricate the apparatus using the acetylenic urea of the present invention include paper, paperboard, fiberboard, cardboard, Kimdura, Mylar, polyethylene, polypropylene, polyacrylic acid ester. Polymers and copolymers, cellulose ethers, cellulose esters, mixed esters and similar materials. Other examples of materials that can be used as substrates for environmentally friendly labels that use acetylenic urea include:
U.S. Pat. No. 3,501,302, column 19, lines 14-15
There are synthetic rubbers and plastics such as those mentioned in the line, which patent is cited. Further, various product containers can also be used as the base material constituting the environmental instruction label.

The application of acetylenic urea to the substrate can be done in various ways. For example, in order to deposit the acetylenic urea compound on a desired area of the substrate, an ink solution containing the acetylenic urea compound and a solvent is sprayed on the substrate. The solution should contain from about 1% to about 5% acetylenic urea, with about 2% by weight being preferred. This method
In fact, it uses acetylenic urea monomers as dyes (ie, monomers that are soluble in the ink vehicle). This method is described in more detail in U.S. Pat. No. 4,189,399, in which acetone is used with a lacquer added as a binder to produce an acetylenic compound which is more soluble in acetone than the present compound. Dissolve. Spray coating the substrate followed by evaporation of the acetone will print the active indicator. Of course, the ink system can be printed by more conventional methods such as flexographic printing, screen printing, gravure printing, type printing, ink-jet printing or similar methods.

Solvents used for forming the ink solution include acetic acid, propanoic acid, heptanoic acid, nonanoic acid, hydroxyacetone, 1,1,3,3-tetramethylurea,
Included are triethanolamine, n-decylamine, secondary-phenethyl alcohol, dimethyl sulfoxide, 2,6-lutidine and the like.

Another more preferred method of applying the acetylenic urea compound to the indicator substrate is to first mill the acetylenic compound into fine particles and prepare a suspension of the particles in a suitable binder-solvent. Regarding forming. Suitable binders for forming such suspensions include natural and synthetic plastics, resins, waxes, colloids, gels and those described in US Pat. No. 3,501,302, column 20, lines 13-43. There are analogs, including gelatin and other similar binders, which are incorporated by reference. The suspension of binder and acetylenic compound is then applied to the desired areas of the label by spraying, screen printing, gravure printing, type printing or other conventional printing means. This method of applying an acetylenic compound to a substrate typically uses an active acetylenic material as a pigment in the ink. This method is described in US Pat.
No. 1,297, the description of which is incorporated herein by reference.

Example 1-15 General Procedure After stirring, a three-necked flask equipped with a thermometer, a N ₂ flow tube (replaced with an O ₂ immersion tube in the case of oxidative coupling reaction) and a dropping funnel was used in Example 1. Used for preparation of compound -15. An excess amount of an isocyanate compound dissolved in tetrahydrofuran (hereinafter referred to as THF) was added to a reaction flask to which a solution containing pre-cured mono-propargylamine and THF was added. No catalyst was used because the reaction is rapid. A water bath (typically 18 ° C.) was used during the isocyanate addition to moderate the reaction temperature. After 1 to 2 hours, CuCl and a complexing agent N, N, N ', N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) were added to the reaction medium, and then O ₂ was bubbled continuously in an appropriate amount. An oxidative coupling reaction was performed. A water bath was used to mitigate the initial temperature excursion.
Typically, the medium was quenched with HCl after 21/2 hours. It was purified by filtration, washing with water and recrystallization.

When UV light is used to cause the polymerization of acetylenic urea and the corresponding color change, the UV light source is U.
VS-11E type UV lamp (UltraViolet
Products Inc. , Pasadena, California, USA).

Example 1. 2,4-hexadiyne-1,
6-bis (ethylurea) 50 ml of mono-propargylamine in a 1 liter flask.
g (0.9 mol) and 300 ml of THF were charged. Fifty
89 g of ethyl isocyanate diluted with ml of THF
(1.25 mol) was added dropwise over 30 minutes. During the addition, the reaction flask was placed in a water bath (18 ° C.) to moderate the exotherm upon addition of ethylisocyanate. The temperature did not exceed 40 ° C. After 11/2 hours, 2.5 g of CuCl and T
6 ml of MEDA was added to the reaction medium. Oxygen bubbles were introduced into the reaction medium with stirring at a moderate rate. Initially, a water bath was used to keep the temperature at 25-35 ° C. After 15 minutes, the water bath was removed and the temperature was gradually raised to 55 ° C, followed by a decrease. After 21/2 hours, 10% HCl
The medium was inactivated by adding 200 ml of solution. The product was filtered and washed with additional HCl solution followed by water. The product was stirred in a solution of 200 ml of methanol and 200 ml of 10% HCl solution, filtered and washed with water, methanol and finally acetone. The product was dissolved in 500 ml of hot acetic acid (90 ° C) to recrystallize, filtered and
Cooled to -20 ° C. The precipitate was filtered, washed with petroleum ether (50-110 ° C) and subsequently dried under vacuum. Yield: 88 g (78% of theory), a finely divided product,
It turned blue at a moderate speed in the dark under room temperature conditions of about 25 ° C. The product did not melt upon heating to 300 ° C on a Mettler heating table. Upon heating, it polymerized rapidly to a dark blue color, then black.

Elemental analysis C ₁₂ H ₁₈ N ₄ O ₂ (molecular weight = 2
50.227) Calculated: C, 57.59; H, 7.25; N, 22.3
8; O, 12.78 Found: C, 57.47; H, 7.34; N, 22.4.
5; O, 12.73 Example 2.2,4-hexadiyne-1,6-bis (bu
Cylurea ) mono-urea derivative was synthesized by adding 25.8 g (0.25 mol) of butyl isocyanate diluted with 25 ml of THF and T
HF 100 ml mono-propargylamine 10.0 g
Example 1 was repeated except that (0.18 mol) was used. A complexing agent was derived from 1 g CuCl and 3 ml TMEDA to form diurea. HCl as the reaction medium
Inactivated with 125 ml (10%). Methanol, acetone and water used for washing were reduced proportionally with respect to Example 1. Yield: 26.6 g (97%) of a greenish product, moderately bluish in the dark at room temperature (about 25 ° C.) 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 slowly changed to orange at room temperature (about 25 ° C). Upon irradiation of the UV source for 5-10 seconds, the product color changed to blue. When recrystallized from acetic acid,
An orange or blue phase was obtained, which deepened upon irradiation with a UV source.

Elemental analysis C ₁₆ H ₂₆ N ₄ O ₂ (MW = 30
6.385) Calculated: C, 62.72; H, 8.55; N, 18.2.
8; O, 10.44 Found: C, 62.53; H, 8.81; N, 18, 0.
8; O, 10.01 Example 3.2, 4-hexadiyne-1,6-bis (o
Octyl urea) octyl isocyanate 21.5 g (0.14 mol),
The procedure of Example 1 was repeated, except that 6.6 g (0.12 mol) of mono-propargylamine and 200 ml of THF were used to synthesize mono-urea. A proportionally large amount of THF was required to keep the mono-urea soluble. The synthesis of mono-urea took 1 hour at 25 ° C.
In order to obtain di-urea in the coupling reaction, CuCl · 1 g, TMEDA 3 ml and THF 50 ml are added to the reaction medium.
Was added. The temperature was maintained at 45-50 ° C during the reaction. The coupling reaction was completed in 2 hours. Yield: 25.2 g (99%) of light blue product, ca. 195 on heating.
Melted and decomposed at ℃. The product was recrystallized from ethanol (1 g / 40 ml). The recrystallized product is thermochromic,
It reversibly changed from light blue to magenta at 80 ° C.

Elemental analysis C ₂₄ H ₂₄ N ₄ O ₂ (molecular weight = 4
18.626) Calcd: C, 68.86; H, 10.11; N, 13.
38; O, 7.64 Found: C, 68.83; H, 10.34; N, 13.
23; O, 7.60 Example 4.2, 4-hexadiyne-1,6-bis (do)
Decyl urea) monopropargyl amine 25 g (0.45 mol), dodecyl isocyanate 100 g (0.47 mol), THF
The same procedure as in Examples 1 and 2 was repeated except that 350 ml was used to produce mono-urea. After the isocyanate was added, the temperature was raised to 45-50 ° C to keep the product soluble. The reaction was continued for 1 hour at which time 2.5 g CuCl and 6 ml TMEDA were added to the reaction medium. Two
The temperature was maintained at 45-50 ° C for 1/2 hour.
The product precipitated immediately after formation (temperature was 5 during this reaction).
Do not exceed 0 ° C. This is because when the temperature exceeds 50 ° C., a polymer is considerably formed. ). 20% HCl solution / M
The product was quenched with a 1: 1 mixture of eOH (500 ml), filtered and washed twice with methanol and acetone. The product was yellow. This yellow color deepened due to exposure to ultraviolet light. When the product sample was placed on filter paper, mechanical pressure was applied with a spatula, followed by UV irradiation or thermal annealing, the yellow color changed to blue. It was also found that when this yellow phase was rapidly heated above about 150 ° C., the color suddenly changed from yellow to bluish purple. To recrystallize the product, 2.5 liters of dimethyl sulfoxide were added to it, heated on a hot plate to 80-85 ° C. and brought to 95 ° C. rapidly before its removal and filtration. The product was precipitated with 1.3 L of ethanol, filtered and washed with more ethanol followed by petroleum ethanol (50-110 ° C). Yield: 112 g (93%) of pale blue to light blue product. When heated, it melted and decomposed at 215 ° C.

Elemental analysis C ₃₂ H ₅₈ N ₄ O ₄ (molecular weight = 5
30.842) Calculated: C, 72.40; H, 11.01; N, 10.
55; O, 6.03 Found: C, 72.25; H, 11.13; N, 10.
65; O, 6.10 Example 5.2,4-hexadiyne-1,6-bis (o
Kutadecyl urea) 10.6 g (0.03 g ) of n-octadecyl isocyanate
6 mol), 2.0 g of mono-propargylamine (0.0
36 mol) and 75 ml of THF were used to synthesize mono-urea, and the same procedure as in Examples 1 and 2 was repeated. The reaction was continued for 1 hour at a temperature of 50 ° C-60 ° C. Coupling reaction is 0.25g CuCl and TMEDA3
The reaction was continued for 21/2 hours at 45-50 ° C. Yield: light yellow product, 11.8 g (94
%). Exposure to UV for 5-10 seconds turned a dark yellow color. A sample (about 0.5 g) was placed on filter paper and mechanical pressure (ie shearing with a spatula) was applied to the product. After applying pressure, the product was irradiated with UV light and turned from yellow to blue.

Example 6.2,4-hexadiyne-1,
2.0 g (0.036 mol) of 6-bis (n-propylurea) mono-propargylamine, 3.1 g (0.03) of n-propyl isocyanate.
6 mol), and the same procedure as in Examples 1 and 2 except that mono-urea was synthesized using 50 ml of THF. The synthesis of mono-urea took 1 hour at 25 ° C. CuCl 0.25g and TMEDA for coupling reaction
When 2 ml was added, the coupling reaction was 21
/ Completed within 2 hours. Yield: pale yellow product, 1.7
g (33%). The product turned bright yellow upon exposure to UV radiation. Recrystallization with acetic acid or ethanol (1 g / 100 ml) produced an active phase, which in each case turned from pink to blue upon exposure to UV light. The product decomposed when heated to 300 ° C. No melting point was observed.

Elemental analysis C ₁₄ H ₂₂ N ₄ O ₄ (molecular weight = 2
78.356) Calculated: C, 60.41; H, 7.97; N, 20.1
3; O, 11.50 Found: C, 60.81; H, 8.11; N, 19.7.
8; O, 12.22 Example 7.2,4-Hexadiyne-1,6-bis (ii)
So-propylurea) mono-propargylamine 2.0 g (0.036 mol) and THF 50 ml were used to synthesize mono-urea,
In addition, 0.25 g of CuCl and TM for coupling reaction
It carried out like Example 1 and 2 except having added 2 ml of EDA. Yield: white product, 2.0 g (39
%). When exposed to UV light, it turned bright yellow. Those recrystallized with various solvents such as acetic acid or ethanol (1 g / 170 ml) did not show an active blue phase upon UV treatment. The product melted and decomposed at 270 ° C.

Elemental analysis C ₁₄ H ₂₂ N ₄ O ₄ (molecular weight = 2
78.356) Calculated: C, 60.41; H, 7.97; N, 20.1
3; O, 11.50 Found: C, 60.84; H, 8.09; N, 19.7.
5; O, 11.93 Example 8.2,4-Hexadiyne-1,6-bis (meth)
Cylurea) mono-propargylamine 2.0 g (0.036 mol), methylisocyanate 2.1 g (0.036 mol) and THF 50 ml were used to synthesize mono-urea,
And for coupling reaction, CuCl 0.25g and TME
The procedure was as in Examples 1 and 2, except that 2 ml of DA was added. The synthesis of mono-urea took 1 hour at 25 ° C. The coupling reaction took 21/2 hours at 40 ° C. Yield: bright pinkish white product 1.7.
g (41%). When exposed to UV light for 5-10 seconds, it turned bright yellow. Dimethyl sulfoxide, ethanol (1g
/ 250 ml) or recrystallization with acetic acid did not produce an active blue phase. When heated, it melted and decomposed at 225 ° C.

Elemental analysis C ₁₀ H ₁₄ N ₄ O ₂ (molecular weight = 22
2.248) Calcd: C, 54.04; H, 6.35; N, 25.2
1; O, 14.40 Found: C, 53.96; H, 6.60 N, 24.4.
8; O, 13.32 Example 9 . 2,4-hexadiyne-1,6-bis (d
Toxycarbonylmethylene urea) mono-propargylamine 2.0 g (0.036 mol), ethyl isocyanatoacetate 4.6 g (0.0
36 mol) and 50 ml of THF to synthesize mono-urea, and CuCl 0.25 g for coupling reaction.
The same procedure as in Examples 1 and 2 was performed except that 2 ml of TMEDA was added. The synthesis of mono-urea requires 1 hour at 25 ° C and the coupling reaction takes 21/2 at 45 ° C.
It took time. Yield: 5.0 g of pinkish product (76
%). When exposed to ultraviolet light for 5-10 seconds, it turned blue. Upon heating, the product melted at 190-195 ° C.

Elemental analysis C ₁₆ H ₂₂ N ₄ O ₆ (molecular weight = 3
66.374) Calculated: C, 52.45; H, 6.05; N, 15.2
9; O, 26.20 Found: C, 52.13; H, 6.05; N, 15.3
6; O, 25.68 Example 10.2,4-hexadiyne-1,6-bis
(Butoxycarbonylmethylurea) mono-propargylamine 2.0 g (0.036 mol), butyl isocyanatoacetate 5.6 g (0.0
36 mol) and 50 ml THF and used for the synthesis of mono-urea and using 0.25 g CuCl and 2 ml TMEDA for the coupling reaction.
It carried out similarly to. 1 at 25 ° C for the synthesis of mono-urea
It took time and the coupling reaction took 11/2 hours at 45 ° C. Yield: recrystallization with ethanol (1 g / 7
5 ml) gave 3.9 g (51%) of white product.

A sample of the product turned blue when exposed to UV light for 5-10 seconds, melted at 168-169 ° C. when heated and turned red when cooled and solidified. The cooled and solidified product turned blue when exposed to ultraviolet rays for 5 to 10 seconds.

Elemental analysis C ₂₀ H ₃₀ N ₄ O ₆ (molecular weight = 4
22.482) calculated: C, 56.86; H, 7.16; N, 13.2
6; O, 22.72 found: C, 57.67; H, 7.67; N, 13.0.
1; O, 21.61 Example 11.2,4-hexadiyne-1,6-bis
(Phenylurea) monopropargylamine 5.5 g (0.1 mol, 6.2
ml), phenylisocyanate 14.9 g (0.12
5 mol) and 100 ml of THF to synthesize mono-urea, and 0.25 g of CuCl and 2.5 of TMEDA.
The procedure was as in Examples 1 and 2, except that g was used in the coupling reaction. The synthesis of mono-urea requires 11/2 hours at 25 ° C, and the coupling reaction is 21 ° C at 35 ° C.
It was completed in 2 hours. Yield: white product, 10.5 g
(61%), when irradiated with UV light for 1-2 minutes, the product turned from white to pale blue. Upon heating to 275 ° C, the product melted and decomposed.

Example 12.2,4,8,10-dodecyl
Synthesis of Lutetrain-1,12-bis (ethylurea) This compound is prepared by preparing two reactants of 1,6-dibromo-1,5-hexadiyne and 1-propyne-3-ethylurea and subsequent reaction of these two kinds. Produced by three synthetic steps for oxidative coupling of products.

1,6-Dibromo-1,5-hexadiyne was prepared as follows.

Sodium hypobromite NaOBr is
Bromine was added to a solution of 76.2 g (1.95 mol) of NaOH in 00 ml cooled to 0 ° C. in a 6.35 N NaOH solution.
It was prepared by adding 0 g (0.732 mol, 39.0 ml) little by little. The solution is stirred for about 1/2 hour,
A 1 liter three-necked flask equipped with a stirrer, a thermometer, a N ₂ flow tube for covering the reaction product, and an ice bath was used to
23.4 g (0.30 mol) of 5-hexadiyne and H ₂ O
The solution was added dropwise to 100 ml over 30 minutes. The temperature was maintained below 180 ° C throughout the addition. After 3 hours, the solid product was extracted with 100 ml of diethyl ether, washed with water and kept on 25 g of ammonium chloride for the required time.

1-Propine-3-ethylurea was prepared as follows. In a 500 ml flask equipped with a stirrer, a thermometer, a N ₂ flow tube and a dropping funnel, 75 ml of THF and 5.5 g of monopropargylamine (0.1 mol, 6.
9 ml) was added, followed by dropwise addition of 7.1 g (0.1 mol) of ethyl isocyanate in 10 ml of THF. The initial temperature was tempered with a water bath and continued at room temperature for 1 hour.

Oxidative coupling of 1,6-dibromo-1,5-hexanediyne and 1-propyne-3-ethylurea, whereby 2,4,8,10-dodecyltetrayne-1,12-bis ( To produce ethylurea), Cu
Cl 0.2 g, n-ethylamine (70%) 15 m
1, followed by 1-5 g of NH ₂ OH.HCl was added to the reaction medium containing the urea compound. Next, THF2
1,6-dibromo-1,5-hexadiyne 1 in 5 ml
3.5 g (0.058 mol) was added dropwise to the reaction medium over 20 minutes. The reaction medium was initially cooled with a cold water bath so that the temperature did not exceed 40 ° C. during the addition. Then, the bath was removed, and the reaction was continued while stirring at a temperature of 25 ° C. for 21/2 hours. The product precipitated during the addition of dibromohexadiyne. The product is filtered and a small amount of T
Washed several times with HF (50 ml total). 10 excluding filtrate
% HCl solution twice, then several times with water, and finally with methanol and dried. Yield: light blue product, 1
2.1 g (74.2%). When exposed to UV light for 5-10 seconds, it turned dark blue. If irradiation is continued (4 minutes),
The product turned a metallic golden color at medium speed. The product did not melt upon heating to 300 ° C. When heated to 300 ° C. or higher, the color changed from red to black and decomposed.

Example 13.1,5,7-Nonatriin
Synthesis of -9- ethylurea The triyne of this compound was recovered from the filtrate of the oxidative coupling reaction of Example 12. Petroleum ether (50-
(110 ° C.) a brown product precipitated which was washed with 10% HCl followed by H ₂ O. The product was recrystallized with acetone / petroleum ether (50-110 ° C). Yield: 3.5 g (34.5%) of white product. When exposed to UV light for 5-10 seconds, it turned red.

Elemental analysis C ₁₂ H ₁₄ N ₂ O (molecular weight = 20
2.257) Calculated: C, 71.26; H, 6.98; N, 13.8.
5; O; 0.791 Found: C, 69.70; H, 7.08; N, 13.8.
4; O; 0.767; Br; 1.7 Elemental analysis shows that 6% of the theoretically possible total bromide remained unhydrolyzed.

Examples 14.2, 4, 8, 10, 14,
16-octadecahexain-1,18-bis (ethyl
Synthesis The compounds of urea) was obtained by the oxidative coupling of avian Example 13. Using the method described in Example 1,
1.0 g of 5,7-nonatriin-9-ethylurea (0.
005 g) CuCl 0.25 g, TMEDA2.
Oxygen was coupled into the reaction medium in a complex consisting of 5 ml and 75 ml of methanol with moderate bubbling. During the first 5-10 minutes of the reaction time, the temperature of the reaction medium was raised to 60 ° C., followed by discontinuing the heating. After 1 hour, 75 ml of water was added. The reaction medium is then filtered to recover the product. The product was washed with water, HCl / H ₂ O followed by water. The product was recrystallized with 125 ml of acetic acid. Yield: 0.5 g (50%) of pale pink product. When it was irradiated with ultraviolet rays for 5-10 seconds, it turned blue. After 30 seconds of irradiation, the product turned bluish black.

Elemental analysis C ₂₄ H ₂₆ N ₄ O ₂ (molecular weight = 4
02.5) 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 Example 15.5, 7-dodecadinein-1,12-bis
Synthesis of (Ethylurea) This compound was synthesized through the following continuous 5-step reaction.

A) Oxidative coupling of 5-hexyn-1-ol to produce 5,7-dodecadiyne-1,12-diol; b) The product of (a) is reacted with p-toluene sulfonyl chloride. 5,7-dodecadiyne-1,12-bis (p-
Toluene sulfonate); c) reacting the product of (b) with potassium phthalimide to produce 1,12-diphthalimido-5,7-dodecadiyne; d) two-stage hydrolysis of the product of (c) Decomposition (base hydrolysis as well as subsequent acid hydrolysis) followed by base treatment to produce 5,7-dodecadiyne-1,12-diamine; e) reacting the product of (d) with ethylisocyanate 5,7-Dodecadiyne-1,12-bis (ethylurea) is produced.

The steps of reactions a to e were carried out as follows.

A) 150 ml of methanol, 150 ml of TMEDA and CuCl in a 1 liter three-necked flask.
9g was charged. Using the Hay method, 150 ml of 5-hexyn-1-ol was added dropwise to the reaction medium over 45 minutes, during which oxygen was bubbled in the reaction medium for oxidative coupling. At the time of addition, the temperature of the medium is approx.
Rose and then declined. Oxygen was bubbled through the reaction medium for a further 15 hours before the product was isolated. single
Release : 800 ml of cold water was added to precipitate the product.
The product was filtered and washed with additional water. Recrystallization : 100 ml of the product and 5 to 10 ml of TMEDA
Dissolved in. Cold water (8-11 ° C) was added to cause precipitation. After filtration and washing with water, the product was recrystallized again.
After removing most of the water, the product was washed 3 times with heptane and dried under vacuum.

Yield: fluffy white product, 120
g.

B) 5,7-dodecadiyne-1,12-diol (prepared in reaction (a)) 58.2 g (0.
3 mol), 150 g of p-toluene sulfonyl chloride (0.
(78 mol) and 150 ml of THF, 150 ml of pyridine were added dropwise at a temperature of 20 to 25 ° C over 0.5 hour. The reaction continued under stirring at 25-30 ° C. for 6.5 hours. Isolation : The reaction medium is poured into 1 liter of cold water, subsequently filtered and washed several times with water to obtain the product. Recrystallization : The fine particles were dissolved in 1.5 liter of methanol and frozen at -8 ° C. Then, it was filtered, washed with petroleum ether (50-110 ° C.), and dried under vacuum. Yield: light tan product, 110 g (73%). It turned red when exposed to UV light for 5-10 seconds. The melting point range of the product was 58.5-59.8 ° C.

C) 5,7-Dodecadiyne-1,12-bis (p-toluenesulfonate) 3 from reaction (b)
2.0 g (0.064 mol) and potassium phthalimide 3
2.0 g (0.17 mol) of 1 in dimethyl sulfoxide
The reaction was carried out at 23-128 ° C for 0.5 hours. 7 reaction media
It was cooled to 5 ° C. and 250 ml of water was added to precipitate the product. The product was filtered and washed with boiling water several times with acetone and then with heptane. Yield: light tan fine powder product 2
4.6 g (85%).

D) 1,12-Diphthalimido-5,7-dodecadiyne 10 g (0.022 mol) from reaction (c), H ₂ O 50 ml, KOH 3.1 g (0.055 mol), pyridine 5 ml and ethanol 80 ml. Was refluxed for 1 hour and then cooled to 50 ° C.

E) 30 ml (0.3 mol) of 10N HCl was added to the reaction medium in small portions, followed by ZnCl ₂ 1
g and refluxed for 3 hours. During reflux, the product (probably phthalic acid) started to precipitate. Isolation : The solvent was then reduced to 75%. H ₂ O 100 ml Add to reaction medium, boil and filter to 50 ml additional boiling water H
Washed with ₂ O. The filtrate contains 2.5 g of phthalic acid (theoretical value of 3
3%), the diamine salt (ClH ₃ NCH ₂ -C≡C) -
_It contained ₂ and _two separated phases were observed, both phases containing diamic acid. When the solvent was evaporated from the dark brown layer,
A solid formed and gradually turned blue. The blue solid turned red upon addition of water. 5N NaOH 50ml
(NaOH 10 g, 0.25 mol) was added little by little to the filtrate to neutralize the diamine acid and generate diamine. Three
After cooling to 0 ° C., the diamine was extracted with diethyl ether (150 ml) with shaking. Distillation of the ether left 2.5 g of a yellow semi-viscous crude product.

F) THF 50 in the crude product of step (e)
ml and 3 g of MgSO ₄ (anhydrous) were added. The solution is filtered, and 3.2 g of ethyl isocyanate at room temperature (25 ° C)
(0.045 mol) was added at once. Immediately a solid precipitated. After 1/2 hour, 200 ml of heptane was added and the product was totally precipitated. It was filtered and washed with heptane. Yield : 1.8 g (25% of theory) of white product. It gradually turned blue in sunlight. Upon exposure to ultraviolet light, it turned dark blue within 15 seconds. Confirmation of product is I
R and elemental analysis. A further addition of 200 ml of xylene to the dark viscous filtrate layer after pouring off the top layer, boiling and filtering through MgSO ₄ yielded further product. After cooling to 50 ° C., 3.2 g (0.045 mol) of ethyl isocyanate was added. The product (containing symmetrical and asymmetrical compounds) was precipitated with heptane after 1/2 hour, filtered and washed with additional heptane. Yield :
2.1 g of crude white product. It gradually turned blue in sunlight and turned dark blue within 30 seconds under a UV lamp.

Example 16 Wide range of color response due to eutectic
Of 2,4-hexadiyn-1,6-bis (ethyl urea)
A solution was prepared by dissolving 1.2 g (hereinafter referred to as 1-KE) in 60 ml of acetic acid. Similarly, a solution containing 1.2 g of 2,4-hexadiyne-1,6-bis (butylurea) (hereinafter referred to as 1-KB) was prepared. These solutions were mixed at the ratios shown in Table 1, precipitated with an equal volume (about 10 ml) of petroleum ether (50-110 ° C.), filtered and dried. The color response of the eutectic composition was monitored visually. Room temperature (about 2
After 3 days in the dark (5 ° C.), the relative reactivity of the eutectic composition was expressed as a value of 1 to 4.

[0059]

[Table 1] Example 17 Incremental change characteristic of reflectance 2,4-hexadiyne-1,6-bis (ethylurea)
(1-KE) 12.5 g to n-ptanol 36 ml
And the mixture was milled in a ball mill for 16 hours to form an ink. Ten grams of this suspension was mixed with a 12% (w / w) solution of Ethocell 45 in n-butanol. A part of this ink was diluted so that the concentration of the acetylenic compound in the diluted ink was 1/2 of the concentration of the acetylenic compound in the non-diluted ink.

A number of indicator labels were prepared by printing a rectangular image (0.3 cm x 2.1 cm) with this ink on a pressure sensitive white label. From the outer end of the acetylene urea bar to 0.
A dark black bar (0.2 cm x 2.1 cm) was printed on each side of the acetylene urea bar at a distance of 2 cm. That is, between the acetylene urea bar and the black bar, 0.
There was a 2 cm wide white space. The label was then placed in a temperature controlled bath (60 ° C., 40 ° C. and 30 ° C.) and withdrawn periodically to measure indicator reflectance after exposure to a given temperature for a given time. Pull out the indicators from the conditioning room and insert each indicator into Intermec 1
Scanning was performed with a 401 scanning Wand. The generated signal is amplified by an amplifier (Skan-a-ma
tic Corp. ) Made by Signal Contro
l Module T 22050) and TEC
Connected to HLABI computer. The reflectance value of the white (W) section and the reflectance value of the black (B) bar of this signal were averaged, and the reflectance value (AC) of the acetylene urea bar was calculated as R = AC-B / WB. This value was used to determine the reflectance of the acetylene urea compound for white and black reference colors. These data are shown in Tables 2, 3 and 4.

[0061]

[Table 2]

[Table 3] * The acetylene urea concentration of the indicator 4 is equal to that of the indicator 2, and the acetylene urea concentration of the indicator 3 is equal to that of the indicator 1.

Stored at a-60 ° C for a further 49 hours.

B Stored at 60 ° C. for a further 49 hours.

[0064]

[Table 4] * The acetylene urea concentration of the indicator 6 is equal to that of the indicator 2, and the acetylene urea concentration of the indicator 5 is equal to that of the indicator 1.

The data in Tables 2, 3 and 4 are reflectance percentages as a function of time, temperature and indicator substance concentration, with higher temperatures, longer exposure times and higher indicator substance concentrations. It shows that the decline is more rapid.
Using the data in Tables 2 and 3, the activation energy of 1-KE was 29 KCal / mol. The activation energy is calculated from these data using the Arlenius equation to determine the time it takes to reach a given reflectance value at two temperatures.

Example 18 Determination of Color Properties A concentration of 2,4-hexadiyne-1,6-bis (butylurea) (1-KB) ink equal to 1-KE and the undiluted 1-KE ink of Example 17 was performed. Prepared as in Example 17. 1 cm diameter dots of these inks were screen printed on a Kimudura substrate. The dot-type indicator was then placed on a Mettler heating table at 110 ° C. and 90 ° C. for each hour. The color of the dots exposed each time to these temperatures was correlated with the Munsell color code. The results are shown in Tables 5 and 6.

[0067]

[Table 5]

[Table 6] The results of Examples 17 and 18 show that 1-KE and 1-KB can be used to monitor a wide range of perishable products or processes. For example, the data of Example 17 is 1-K.
It shows that E can be used to monitor products with a shelf life of about 1.5-3 years (25 ° C). These results indicate that increasing the acetylene urea also allows monitoring at room temperature for less than a year. The results of Example 18 show that the color change associated with the test compound was properly sterilized by heat treatment of canned food, ie the canned was treated for this sterilization purpose at temperatures in the range 90-100 ° C for 10-30 minutes. It also shows that it can be used for proof.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G01K 11/12 Q G03F 7/004 511 7/025

Claims (2)

[Claims] 1. The structural formula is: An organic compound whose reflectance can change incrementally when exposed to environmental stimuli, wherein R is a cycloalkyl moiety of 3-7 carbon atoms, 3- An alkenyl moiety of 18 carbon atoms, 3-7
Selected from the group consisting of cycloalkenyl moieties of carbon atoms, alkoxy moieties of 2-18 carbon atoms, linear or branched alkyl moieties of 1-18 carbon atoms, alkoxycarbonylmethylene moieties of 3-14 carbon atoms, or phenyl moieties. And y is an integer from 1 to 8 and x is an integer from 1 to 6. 2. A compound according to claim 1, 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.