hexa-2,4-diyne-1,6-diol

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500-ml tree-neck flask equipped with a stirrer, a dropping funnel and an inlet for feeding argon was charged with anhydrous (additionally dried over 4A molecular sieves) dimethylsulfoxide (DMSO) (200 ml) and 11.0 g (0.1 mol) of 2,4-hexadiyn-1,6-diol. To the vigorously stirred mixture, a solution of p-toluenesulfonyl isocyanate (Aldrich) (40 ml, 0.22 mol) in 50 ml of dry DMSO was added drop-wise for 0.5 h. After stirring for additional 2 hrs at room temperature, the mixture was discharged into 1000 ml of chilled water. The water layer was decanted off the yellow heavy oil, and the oil was triturated with diethyl ether, giving a cake of fine crystals which rapidly attained blue color under effect of UV light. Recrystallization from hot ethanol/ethyl acetate 2:1 mixture gave 45.2 g (yield 90%) of 2,4-hexadiyn-1,6-diol p-toluenesulfonyl urethane as fine white crystals with m.p. 128-130° C. The crystals were readily polymerizable under effect of both UV-irradiation and temperature. Analysis: I.R. (KBr pellet, cm−1: 3080 (Ar—H stretching), 2980+2920 (CH stretching), 1596 (phenyl C═C stretching), 1368 (S—O), 1184 (S—O), 742 (Ar—H). NIR-FT Raman: 2270 cm−1 (diacetylenic monomer —C═C— stretch), 2105 cm−1 (polymer backbone —C≡C— stretch), 1540 cm−1 (polymer backbone —C═C— stretch). Having been held in an oven at 85° C. for 2 hrs and then analyzed as described in Example 1, the compound gave an intense NIR Raman spectrum identical to that shown in FIG. 1(J, top). The simultaneous presence of the two Raman bands in 2300-1900 cm−1 spectral region, one (weak) belonging to ν(—C≡C—) vibrations of the monomer and the other (strong) belonging to ν(—C≡C—) vibrations of corresponding polymer, evidenced for partial polymerization of the compound. A 500-ml tree-neck flask equipped with a stirrer, a dropping funnel and an inlet was charged with anhydrous ( The water layer was decanted off the yellow heavy oil the oil was triturated with diethyl ether giving a cake of fine crystals which rapidly attained blue color under effect of UV light Recrystallization from hot ethanol/ethyl acetate 2:1 mixture

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a glass reaction vessel, 400 milligrams (3.75 mmol) HOCH2C≡C—C≡CCH2OH prepared in Step 1, was dissolved in a mixture of 25 milliliters THF and 1 milliliters pyridine. To this stirred solution was added 1.0 gram (4.1 mmol) N3(CH2)10C(O)Cl prepared in Step 2, and 950 μL (4.1 mmol) CH3(CH2)10C(O)Cl. The resulting mixture was stirred for 3 h, concentrated, dissolved into hexanes and filtered to remove the salts. The filtrate was concentrated and purified using column chromatography eluting with 10% by volume of ethyl acetate in hexanes to yield 750 milligrams CH3(CH2)10C(O)OCH2C≡C—C≡CCH2OC(O)(CH2)10N3. In a glass reaction vessel, 280 milligrams (0.56 mmol) CH3(CH2)10C(O)OCH2C≡C—C≡CCH2OC(O)(CH2)10N3 was dissolved in 1 milliliters water and 8 milliliters THF. To this solution, 350 milligrams (1.3 mmol) triphenylphosphine was added. After 20 h of stirring, hydrogen chloride gas was bubbled through the mixture for 30 seconds. The resulting solid was filtered and washed with diethyl ether to yield 150 milligrams CH3(CH2)10C(O)OCH2C≡C—C≡CCH2OC(O)(CH2)10NH3Cl. concentrated dissolved into hexanes filtered to remove the salts The filtrate was concentrated purified eluting with 10% by volume of ethyl acetate in hexanes

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Fifty grams of p-methoxybenzenesulfonyl chloride was reacted, at 15° to 18° C., with 11 grams of 2,4-hexadiyn-1,6-diol in 100 ml tetrahydrofuran, while a solution of 20 grams potassium hydroxide in 180 ml water was added dropwise over a 10 minute period. The resulting exothermic reaction was cooled at 15° to 18° C. with the aid of an ice-water bath. After the addition of the potassium hydroxide solution, the solution was allowed to stir overnight at room temperature. The mixture was then poured into 500 ml cold aqueous sodium chloride solution which resulted in a yellow precipitate. The precipitate was collected by filtration, washed with water and dried. Obtained was 41.6 grams (93% yield of theory) of a yellow brown solid, melting point 120° to 122° C. was added dropwise over a 10 minute period The resulting exothermic reaction was cooled at 15° to 18° C. with the aid of an ice-water bath resulted in a yellow precipitate The precipitate was collected by filtration washed with water dried Obtained

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Fifty grams of p-methoxybenzenesulfonyl chloride was reacted, at 15° to 18° C., with 11 grams of 2,4-hexadiyn-1,6-diol in 100 ml tetrahydrofuran, while a solution of 20 grams potassium hydroxide in 180 ml water was added dropwise over a 10 minute period. The resulting exothermic reaction was cooled at 15° to 18° C. with the aid of an ice-water bath. After the addition of the potassium hydroxide solution, the solution was allowed to stir overnight at room temperature. The mixture was then poured into 500 ml cold aqueous sodium chloride solution which resulted in a yellow precipitate. The precipitate was collected by filtration, washed with water and dried. Obtained was 41.6 grams (93% yield of theory) of a yellow brown solid, melting point 120° to 122° C. was added dropwise over a 10 minute period The resulting exothermic reaction was cooled at 15° to 18° C. with the aid of an ice-water bath resulted in a yellow precipitate The precipitate was collected by filtration washed with water dried Obtained

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a glass reaction vessel, 400 milligrams (3.75 mmol) HOCH2C≡C—C≡CCH2OH prepared in Step 1, was dissolved in a mixture of 25 milliliters THF and 1 milliliters pyridine. To this stirred solution was added 1.0 gram (4.1 mmol) N3(CH2)10C(O)Cl prepared in Step 2, and 950 μL (4.1 mmol) CH3(CH2)10C(O)Cl. The resulting mixture was stirred for 3 h, concentrated, dissolved into hexanes and filtered to remove the salts. The filtrate was concentrated and purified using column chromatography eluting with 10% by volume of ethyl acetate in hexanes to yield 750 milligrams CH3(CH2)10C(O)OCH2C≡C—C≡CCH2OC(O)(CH2)10N3. In a glass reaction vessel, 280 milligrams (0.56 mmol) CH3(CH2)10C(O)OCH2C≡C—C≡CCH2OC(O)(CH2)10N3 was dissolved in 1 milliliters water and 8 milliliters THF. To this solution, 350 milligrams (1.3 mmol) triphenylphosphine was added. After 20 h of stirring, hydrogen chloride gas was bubbled through the mixture for 30 seconds. The resulting solid was filtered and washed with diethyl ether to yield 150 milligrams CH3(CH2)10C(O)OCH2C≡C—C≡CCH2OC(O)(CH2)10NH3Cl. concentrated dissolved into hexanes filtered to remove the salts The filtrate was concentrated purified eluting with 10% by volume of ethyl acetate in hexanes

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500-ml tree-neck flask equipped with a stirrer, a dropping funnel and an inlet for feeding argon was charged with anhydrous (additionally dried over 4A molecular sieves) dimethylsulfoxide (DMSO) (200 ml) and 11.0 g (0.1 mol) of 2,4-hexadiyn-1,6-diol. To the vigorously stirred mixture, a solution of p-toluenesulfonyl isocyanate (Aldrich) (40 ml, 0.22 mol) in 50 ml of dry DMSO was added drop-wise for 0.5 h. After stirring for additional 2 hrs at room temperature, the mixture was discharged into 1000 ml of chilled water. The water layer was decanted off the yellow heavy oil, and the oil was triturated with diethyl ether, giving a cake of fine crystals which rapidly attained blue color under effect of UV light. Recrystallization from hot ethanol/ethyl acetate 2:1 mixture gave 45.2 g (yield 90%) of 2,4-hexadiyn-1,6-diol p-toluenesulfonyl urethane as fine white crystals with m.p. 128-130° C. The crystals were readily polymerizable under effect of both UV-irradiation and temperature. Analysis: I.R. (KBr pellet, cm−1: 3080 (Ar—H stretching), 2980+2920 (CH stretching), 1596 (phenyl C═C stretching), 1368 (S—O), 1184 (S—O), 742 (Ar—H). NIR-FT Raman: 2270 cm−1 (diacetylenic monomer —C═C— stretch), 2105 cm−1 (polymer backbone —C≡C— stretch), 1540 cm−1 (polymer backbone —C═C— stretch). Having been held in an oven at 85° C. for 2 hrs and then analyzed as described in Example 1, the compound gave an intense NIR Raman spectrum identical to that shown in FIG. 1(J, top). The simultaneous presence of the two Raman bands in 2300-1900 cm−1 spectral region, one (weak) belonging to ν(—C≡C—) vibrations of the monomer and the other (strong) belonging to ν(—C≡C—) vibrations of corresponding polymer, evidenced for partial polymerization of the compound. A 500-ml tree-neck flask equipped with a stirrer, a dropping funnel and an inlet was charged with anhydrous ( The water layer was decanted off the yellow heavy oil the oil was triturated with diethyl ether giving a cake of fine crystals which rapidly attained blue color under effect of UV light Recrystallization from hot ethanol/ethyl acetate 2:1 mixture

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500-ml tree-neck flask equipped with a stirrer, a dropping funnel and an inlet for feeding argon was charged with anhydrous (additionally dried over 4A molecular sieves) dimethylsulfoxide (DMSO) (200 ml) and 11.0 g (0.1 mol) of 2,4-hexadiyn-1,6-diol. To the vigorously stirred mixture, a solution of p-toluenesulfonyl isocyanate (Aldrich) (40 ml, 0.22 mol) in 50 ml of dry DMSO was added drop-wise for 0.5 h. After stirring for additional 2 hrs at room temperature, the mixture was discharged into 1000 ml of chilled water. The water layer was decanted off the yellow heavy oil, and the oil was triturated with diethyl ether, giving a cake of fine crystals which rapidly attained blue color under effect of UV light. Recrystallization from hot ethanol/ethyl acetate 2:1 mixture gave 45.2 g (yield 90%) of 2,4-hexadiyn-1,6-diol p-toluenesulfonyl urethane as fine white crystals with m.p. 128-130° C. The crystals were readily polymerizable under effect of both UV-irradiation and temperature. Analysis: I.R. (KBr pellet, cm−1: 3080 (Ar—H stretching), 2980+2920 (CH stretching), 1596 (phenyl C═C stretching), 1368 (S—O), 1184 (S—O), 742 (Ar—H). NIR-FT Raman: 2270 cm−1 (diacetylenic monomer —C═C— stretch), 2105 cm−1 (polymer backbone —C≡C— stretch), 1540 cm−1 (polymer backbone —C═C— stretch). Having been held in an oven at 85° C. for 2 hrs and then analyzed as described in Example 1, the compound gave an intense NIR Raman spectrum identical to that shown in FIG. 1(J, top). The simultaneous presence of the two Raman bands in 2300-1900 cm−1 spectral region, one (weak) belonging to ν(—C≡C—) vibrations of the monomer and the other (strong) belonging to ν(—C≡C—) vibrations of corresponding polymer, evidenced for partial polymerization of the compound. A 500-ml tree-neck flask equipped with a stirrer, a dropping funnel and an inlet was charged with anhydrous ( The water layer was decanted off the yellow heavy oil the oil was triturated with diethyl ether giving a cake of fine crystals which rapidly attained blue color under effect of UV light Recrystallization from hot ethanol/ethyl acetate 2:1 mixture

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The limitation in this process is that the total number of diols and isocyanates or diols and organic sulfonic acid agents is at least three, thereby resulting in a co-crystallized composition directly recoverable from the reaction mixture. For example, methylisocyanate can be reacted with a mixture of 2,4-hexadiyn-1,6-diol and 3,6-octadiyne-1,8-diol to yield a co-crystallized composition of (1) 2,4-hexadiyn-1,6-diol bis(methylurethane) and (2) 3,5-octadiyn-1,8-diol bis(methylurethane). Similarly, methylisocyanate and ethylisocyanate can be reacted with 2,4-hexadiyn-1,6-diol to yield a co-crystallized composition of (1) 2,4-hexadiyn-1,6-diol bis(methylurethane), (2) 2,4-hexadiyn-1,6-diol bis(ethylurethane) and (3) 2,4-hexadiyn-1-ol-methylurethane-6-ol-ethylurethane. resulting in a co-crystallized composition directly recoverable from the reaction mixture

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The monomer 2,4-hexadiyn-1,6-diol-bisethylurethane is synthesized in 95% yield by the reaction of 11.0 gm (0.10 mole) 2,4-hexadiyn-1,6-diol with 26.5 gm (0.37 mole) ethylisocyanate in the presence of 1,2-dimethoxyethane (50 ml), dibutyltin bis(2-ethylhexanoate (0.1 gm), and triethylamine (2 ml). The monomer is recrystallized as approximately 3 cm long needles by the slow cooling of a 10:90 acetone/petroleum either solution (75 ml) containing 0.2 sample, as described in Example 4. These crystals rapidly turn pink upon exposure to light. Polymerization proceeded quantitatively by 60Co γ-ray irradiation at a dose rate of 1 Mrad/hr and a total dosage of 60 Mrad. The resulting polymer fibers are copper-like in appearance and strongly dichroic, with dichroic axis in the fiber axis direction. The polymer fibers are monoclinic monocrystals in which the polymer chain axis, with repeat length 4.9 A is in a non-unique axis direction. The polymer fibers are annealed as described in Examples 4 and 5, in order to obtain reversible thermal-dimensional behavior. The annealed polymer fiber has a negative thermal expansion coefficient over the entire temperature range from -50° to 100° C. The average thermal expansion coefficient is -1.46×10-5 ° C.-1 between -50° and +100° C. and -1.31×10-5 ° C.-1 between -50° and +40° C. The monomer is recrystallized as approximately 3 cm long needles by the slow cooling of a 10:90 acetone/petroleum either solution (75 ml) containing 0.2 sample Polymerization proceeded quantitatively by 60Co γ-ray irradiation at a dose rate of 1 Mrad/hr to obtain reversible thermal-dimensional behavior from -50° to 100° C is -1.46×10-5 ° C. 1 between -50° and +100° C. and -1.31×10-5 ° C. 1 between -50° and +40° C.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The limitation in this process is that the total number of diols and isocyanates or diols and organic sulfonic acid agents is at least three, thereby resulting in a co-crystallized composition directly recoverable from the reaction mixture. For example, methylisocyanate can be reacted with a mixture of 2,4-hexadiyn-1,6-diol and 3,6-octadiyne-1,8-diol to yield a co-crystallized composition of (1) 2,4-hexadiyn-1,6-diol bis(methylurethane) and (2) 3,5-octadiyn-1,8-diol bis(methylurethane). Similarly, methylisocyanate and ethylisocyanate can be reacted with 2,4-hexadiyn-1,6-diol to yield a co-crystallized composition of (1) 2,4-hexadiyn-1,6-diol bis(methylurethane), (2) 2,4-hexadiyn-1,6-diol bis(ethylurethane) and (3) 2,4-hexadiyn-1-ol-methylurethane-6-ol-ethylurethane. resulting in a co-crystallized composition directly recoverable from the reaction mixture

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The monomer 2,4-hexadiyn-1,6-diol-bisethylurethane is synthesized in 95% yield by the reaction of 11.0 gm (0.10 mole) 2,4-hexadiyn-1,6-diol with 26.5 gm (0.37 mole) ethylisocyanate in the presence of 1,2-dimethoxyethane (50 ml), dibutyltin bis(2-ethylhexanoate (0.1 gm), and triethylamine (2 ml). The monomer is recrystallized as approximately 3 cm long needles by the slow cooling of a 10:90 acetone/petroleum either solution (75 ml) containing 0.2 sample, as described in Example 4. These crystals rapidly turn pink upon exposure to light. Polymerization proceeded quantitatively by 60Co γ-ray irradiation at a dose rate of 1 Mrad/hr and a total dosage of 60 Mrad. The resulting polymer fibers are copper-like in appearance and strongly dichroic, with dichroic axis in the fiber axis direction. The polymer fibers are monoclinic monocrystals in which the polymer chain axis, with repeat length 4.9 A is in a non-unique axis direction. The polymer fibers are annealed as described in Examples 4 and 5, in order to obtain reversible thermal-dimensional behavior. The annealed polymer fiber has a negative thermal expansion coefficient over the entire temperature range from -50° to 100° C. The average thermal expansion coefficient is -1.46×10-5 ° C.-1 between -50° and +100° C. and -1.31×10-5 ° C.-1 between -50° and +40° C. The monomer is recrystallized as approximately 3 cm long needles by the slow cooling of a 10:90 acetone/petroleum either solution (75 ml) containing 0.2 sample Polymerization proceeded quantitatively by 60Co γ-ray irradiation at a dose rate of 1 Mrad/hr to obtain reversible thermal-dimensional behavior from -50° to 100° C is -1.46×10-5 ° C. 1 between -50° and +100° C. and -1.31×10-5 ° C. 1 between -50° and +40° C.

Conditions: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,4-Hexadiyn-1,6-diol (66.1 g, 0.6 mole), triethylamine (70 g) and (THF) (400 ml) were charged into a 1-liter flask which was equipped with a mechanical stirrer, thermometer, gas inlet, and a dry ice condenser. The solution was brought to 50° C. under a blanket of nitrogen. A solution of cinnamoyl chloride (110 g, 0.6 moles) and THF (200 ml) was added through a dropping funnel to the above solution which was vigorously stirred over a period of one hour at 45°. The resulting solution was held for 5 hours at this temperature and then heated to 55° C. and held at this temperature for an additional 20 hours to complete the reaction, after which the THF was stripped off and the remaining solid was redissolved in 500 ml of toluene. The toluene solution was washed three times with water, dried over magnesium sulfate and filtered. After the toluene was removed from the filtrate, 134 g. of the colorless, crystalline 2,4-hexadiyn-1,6-diyl dicinnamate product having a m.p. of 102°-104° was identified by NMR and IR analyses. One gram of the dicinnamate was spread on a filter paper and subjected to UV irradiation at 254 nm. After 30 seconds, no color change was observed; indicating that this product is unsuitable for photoimaging. was equipped with a mechanical stirrer was brought to 50° C. under a blanket of nitrogen The resulting solution was held for 5 hours at this temperature held at this temperature for an additional 20 hours the reaction The toluene solution was washed three times with water dried over magnesium sulfate filtered After the toluene was removed from the filtrate, 134 g subjected to UV irradiation at 254 nm After 30 seconds