US3814752A - 6,6'-methylenebis(2-styryl benzopyrylium salt)as sensitizers for use in electrophotographic light-sensitive materials - Google Patents
6,6'-methylenebis(2-styryl benzopyrylium salt)as sensitizers for use in electrophotographic light-sensitive materials Download PDFInfo
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- 239000000463 material Substances 0.000 title abstract description 15
- -1 2-styryl benzopyrylium salt Chemical class 0.000 title description 8
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 36
- 150000001875 compounds Chemical class 0.000 description 33
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 24
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 4
- OWPBOKWFRAIKTD-UHFFFAOYSA-N 5-[(3-formyl-4-hydroxyphenyl)methyl]-2-hydroxybenzaldehyde Chemical compound C1=C(C=O)C(O)=CC=C1CC1=CC=C(O)C(C=O)=C1 OWPBOKWFRAIKTD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- JPBGLQJDCUZXEF-UHFFFAOYSA-N chromenylium Chemical class [O+]1=CC=CC2=CC=CC=C21 JPBGLQJDCUZXEF-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- LWRSYTXEQUUTKW-UHFFFAOYSA-N 2,4-dimethoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C(OC)=C1 LWRSYTXEQUUTKW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- UCTUXUGXIFRVGX-UHFFFAOYSA-N 2,3,4-trimethoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C(OC)=C1OC UCTUXUGXIFRVGX-UHFFFAOYSA-N 0.000 description 1
- VDVOJNBNSUJCSZ-UHFFFAOYSA-M 3-phenylchromenylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC=CC=C1C1=C[O+]=C(C=CC=C2)C2=C1 VDVOJNBNSUJCSZ-UHFFFAOYSA-M 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 239000006001 Methyl nonyl ketone Substances 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- KMPQYAYAQWNLME-UHFFFAOYSA-N Undecanal Natural products CCCCCCCCCCC=O KMPQYAYAQWNLME-UHFFFAOYSA-N 0.000 description 1
- CHZWRIFDYXSVOD-UHFFFAOYSA-M chromenylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.[O+]1=CC=CC2=CC=CC=C21 CHZWRIFDYXSVOD-UHFFFAOYSA-M 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 229960000443 hydrochloric acid Drugs 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- BGEHHAVMRVXCGR-UHFFFAOYSA-N methylundecylketone Natural products CCCCCCCCCCCCC=O BGEHHAVMRVXCGR-UHFFFAOYSA-N 0.000 description 1
- NTQLADLBRQMNQJ-UHFFFAOYSA-M pyrylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC=[O+]C=C1 NTQLADLBRQMNQJ-UHFFFAOYSA-M 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- CYIFVRUOHKNECG-UHFFFAOYSA-N tridecan-2-one Chemical compound CCCCCCCCCCCC(C)=O CYIFVRUOHKNECG-UHFFFAOYSA-N 0.000 description 1
- KYWIYKKSMDLRDC-UHFFFAOYSA-N undecan-2-one Chemical compound CCCCCCCCCC(C)=O KYWIYKKSMDLRDC-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0664—Dyes
- G03G5/0666—Dyes containing a methine or polymethine group
- G03G5/0672—Dyes containing a methine or polymethine group containing two or more methine or polymethine groups
- G03G5/0674—Dyes containing a methine or polymethine group containing two or more methine or polymethine groups containing hetero rings
Definitions
- FIG. 6 o zra 3 4 0 7 s 9 :0 2025 z 9 R LUV) mm 0 l l l l l l l I l l V l l l l l l l A l Q 4000 3200 2400 I800 I600
- sensitizers for use in an electrophotographic light-sensitive material containing an organic photoconductor.
- the sensitizers comprise derivatives of 6,6-methylenebisbenzopyrylium salts.
- the present invention relates to sensitizers for use in electrophotographic light-sensitive materials which contain organic photoconductors such as polyvinylcarbazole.
- the sensitizers of the present invention are derivatives of 6,6-methylenebisbenzopyrylium salts having the following general formula:
- Such derivatives of 6,6 methylenebisbenzopyrylium salts are used as sensitizers for an organic photoconductors such as polyvinylcarbazole or derivatives thereof. They are preferably used in an amount of 0.1 to 2.0% by weight based on the solid content, in a light-sensitive solution.
- each light-sensitive product was allowed to stand in a dark place for several days, it was negatively charged by means of conventional corona discharge of 6 kv. and exposed to white light in contact with an image Original while illuminating the surface of the light-sensitive layer at 20 lux.
- the wave length of absorption maximum was measured by reflection method for each of Compounds No. 1 to No. 15.
- Electrophotographic light-sensitive materials were obtained following the same procedures as that of Examples 1-15 except that chlorinated polyvinylcarbazole was employed as a substitute for brominated polyvinylcarbazole.
- the electrophotographic light-sensitive materials yielded an exact reproduction of original images in the same manner as that of Examples 1-15 except that the lightsensitive materials were exposed to light for 2 seconds while illuminating the surface of the light-sensitive layer at 20 lux.
- the reaction temperature of the condensation and the cyclic condensation is preferably between 0 C. and 5 C.
- reaction solution is poured into ether to crystallize.
- reaction solution is poured into a cooled solution (concentration: 5-20%) containing acid or salt having a desired anion to crystallize.
- This compound showed wave length of absorption maximum (A at 576 111,11. and molecular extinction coefficient (e) of 1016x10 in dichloroethane.
- This compound showed wave length of absorption maximum (A at 559 my and molecular extinction coefiicient (e) of 8.79X10 in dichloroethane.
- benzopyrylium salts having C10 as an anion have been shown.
- Benzopyrylium salts having BF;- or AuCl; as an anion can be obtained by using an aqueous solution of sodium tetrafluoroborate (NaBF or chloroauric acid (HAuCl instead of an aqueous solution of perchloric acid (H010).
- a sensitizer for use in an electrophotographic lightsensitive material having the formula (I):
- a rivative isj- 6;6' methvlenebisn (4Gmethoxynaphthyii '4.
- a sensitize: afbording'tofclaim'lfwheiiein rivativ'e" is 6,6 "'methy1enebis'[2 (p"-methoxystyryl)-3'- decylbenzopyryliumperchlorate a 5.
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- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
Abstract
THERE ARE PROVIDED SENSITIVIZERS FOR USE IN AN ELECTROPHOTOGRAPHC LIGHT-SENSITIVE MATERIAL CONTAINING AN ORGANIC PHOTOCONDUCTOR. THE SENSITIZERS COMPRISES DERIVATIVES OF 6,6''-METHYLENEBISZOPYRYLIUM SALTS.
Description
June 4, 1974 SHOJI MARUYAMA ETAL 3,814,752
6,6"METHYLENEBIS[ZSTYRYL BENZOPYRYLIUM SALTS] AS SENSITIZERS FOR USE IN ELECTROPHOTOGRAPHIC LIG-HTSENSITIVE MATERIALS Filed June 5, 1972 2 Sheets-Sheet 1 FIG. I'
WAVE LENGTH (my) |00 Z lv z w 0 m 800 700 600 500 400 WAVE LENGTH (m 100 I I: Z L'. (D z m 0 800 700 600 500 400 WAVE LENGTH (mg) WAVE LENGTH(m,u) 4 2.53 45 6 75010 1152025 5100 I Z 9. 3 E5 LLIU) 8?: 1 i'E 4800 3200 2400 I800 |600|4OO I200 |OOO8006OO 400 WAVE NUMBER (cm") June 4, 1974 SHOJI MARUYAMA ETAL 3,814,752
{3,(1' -METHYLENEBISCZ-STYRYL BENZOPYRYLIUM SALTS AS SENSITIZERS FOR USE IN ELECTROPHOTOGRAPHIC LIGHT-SENSITIVE MATERIALS Filed June 5, 1972 2 Sheets-Sheet 2 WAVE LENGTH(m;L) 5
o zra 3 4 0 7 s 9 :0 2025 z 9 R LUV) mm 0 l l l l l l l l I l l V l l l l l l A l Q 4000 3200 2400 I800 I600 |400|200 |000 800 600 400 WAVE NUMBER (cm") FIG. 6
PERCENT TRANSMISSION I 500 I I I 600 I I I I 700 WAVE LENGTH (m FIG? PERCENT TRANSMISSION ("/o) 500 I I 600 700 WAVE LENGTH (mp) United States Patent Oflice- 3, 14,752 Patented June 4, 1974 US. Cl. 260-240 D 6 Claims ABSTRACT OF THE DISCLOSURE There are provided sensitizers for use in an electrophotographic light-sensitive material containing an organic photoconductor. The sensitizers comprise derivatives of 6,6-methylenebisbenzopyrylium salts.
BACKGROUND OF THE INVENTION It is well to use organic photoconductive materials such as polyvinylcarbazole instead of inorganic photoconductors such as photoconductive zinc oxide or selenium in electrophotographic light-sensitive materials. However, with organic photoconductors the sensitivity is low compared with inorganic photoconductors. Accordingly, in order to improve the sensitivity of organic photoconductors, it has been proposed to add certain coloring materials for sensitization. In this manner, the sensitivity of the organic photoconductive matter may be improved to a degree that it can be used in a practical manner. There is however still need for improvement.
It is an object of the present invention to provide sensitizers which will impart high sensitivity to organic photoconductors.
SUMMARY OF THE INVENTION The present invention relates to sensitizers for use in electrophotographic light-sensitive materials which contain organic photoconductors such as polyvinylcarbazole.
The sensitizers of the present invention are derivatives of 6,6-methylenebisbenzopyrylium salts having the following general formula:
6,6-methylenebis[2-(2',3',4'-trimethoxystyryl)-3 -phenylbenzopyrylium perchlorate] Compound No. 2
6, 6'-methylenebis [2- 4'-methoxynaphthylvinylene 3-phenylbenzopyrylium perchlorate] used as Compound No. 3
6,6-methylenebis[2-(3',4'-dimethoxystyryl)-3-phenylbenzopyrylium perchlorate] Compound No. 4
6, 6'-methylenebis[2-(p-methylstyry1) -3-phenylbenzopyrylium perchlorate] Compound No. 5
6,6-methylenebis [2- (2',4'-dimethoxystyryl) -3-phenylbenzopyrylium perchlorate] Compound No. 6
6,6'-methylenebis[2- (p-methoXystyryl)-3 -phenylbenzopyrylium perchlorate] Compound No. 7
6, 6-methylenebis [2- (p-ethoxystyryl) -3 -phenylbenzopyrylium perchlorate] Compound No. 8
6,6-methylenebis[2- (p-butoxystyryl)-3 -phenylbenzopyrylium perchlorate] Compound No. 9
6,6-methylenebis [2- (p-methoxystyryl) -3 -butylb enzopyrylium perchlorate] Compound No. 11
6,6-methylenebis[2-(p-ethoxystyryl)-3-octylbenzopyrylium perchlorate] Compound No. 12
6,6-methylenebis[2-(2',4'-dimethoxystyryl) -3-octylbenzopyrylium perchlorate] Compound No. 13
6,6-methylenebis[2-(p-methoxystyryl)-3-decylbenzopyrylium perchlorate] Compound No. 14
6,6-methylenebis [2-naphthylvinylene-3 -phenylbenzopyrylium perchlorate] Compound No. 15
6,6-methylenebis [2- (3 ',4'-diethoxystyryl) -3 -phenylb enzopyrylium perchlorate) Such derivatives of 6,6 methylenebisbenzopyrylium salts are used as sensitizers for an organic photoconductors such as polyvinylcarbazole or derivatives thereof. They are preferably used in an amount of 0.1 to 2.0% by weight based on the solid content, in a light-sensitive solution. Y
The elfects of the sensitizers of the present invention are illustrated in the following examples.
EXAMPLES 1-15 r so that the dried light-sensitivellayer, (coated layer) had a thickness of Sp. to 6p.
After each light-sensitive product was allowed to stand in a dark place for several days, it was negatively charged by means of conventional corona discharge of 6 kv. and exposed to white light in contact with an image Original while illuminating the surface of the light-sensitive layer at 20 lux.
In this manner, the optimum amount of exposure [lux-sec] required to obtain an exact reproduction of an original image on the light-sensitive layer was measured for each of Compounds No. 1 to No. 15.
Furthermore, by using the electrophotographic lightsensitive materials obtained above, the wave length of absorption maximum was measured by reflection method for each of Compounds No. 1 to No. 15.
The measured values are shown in the Table 1 below, and the curves of spectral sensitivity of the electrophotographic light-sensitive material sensitized with Compounds No. 1, No. 2 and No. 13 are shown in FIG. 1, FIG. 2 and FIG. 3 of the accompanying drawings, respectively.
EXAMPLES 16-30 Electrophotographic light-sensitive materials were obtained following the same procedures as that of Examples 1-15 except that chlorinated polyvinylcarbazole was employed as a substitute for brominated polyvinylcarbazole.
The electrophotographic light-sensitive materials yielded an exact reproduction of original images in the same manner as that of Examples 1-15 except that the lightsensitive materials were exposed to light for 2 seconds while illuminating the surface of the light-sensitive layer at 20 lux.
Derivatives of 6,6-methylenebisbenzopyrylium salts having general formula (I) are synthesized as follows:
Condensation of 5,5'-methylenebissalicylaldehyde of formula (II) with a ketone of general formula ('III) is carried out and to this reaction solution is added an aldehyde of general formula (IV) to carry out cyclic condensation.
C H O 2R2CHO OH; OH ZRICHBCOCHQ! As a condensingage'nt for the condensation "andth'e cyclic condensation, hydrochloricacid or hydrogen chlo ride may be used.
The reaction temperature of the condensation and the cyclic condensation is preferably between 0 C. and 5 C.
Introduction of an anion is effected as follows:
(1) After the cyclic condensation with aldehyde has'been' carried out in the presence of acid or salt having the desired anion, the reaction solution is poured into ether to crystallize.
(2) After cyclic condensation has been carried out, the reaction solution is poured into a cooled solution (concentration: 5-20%) containing acid or salt having a desired anion to crystallize.
Methods of producing derivatives of 6,6'-methylenebisbenzopyrylium salt are illustrated by the following Preparations No. 1 to No. 5.
Preparation No. 1
6,6-methylenebis[Z-(p-methoxystyryl) 3 phenylbenzopyrylium perchlorate] (Compound N0. 6 having the following formula) 2.5 g. of 5,5'-methylenebissalicylaldehyde was dissolved in 40 ml. of tetrahydrofuran and to this solution was added a solution containing 3 g. of benzyl methyl ketone in 20 ml. of formic acid. After having been well mixed, the solution was saturated with hydrogen chloride while cooling. The solution was allowed to stand in an ice box for 2 hours and then to this solution was added a solution containing 3 g. of p-methoxybenzaldehyde in 20 ml. of 90% formic acid. After this solution was saturated with hydrogen chloride while cooling and allowed to stand in an ice box for 2 days, the solution was poured into a 15% cooled aqueous solution of perchloric acid (HCI'O Crude crystals separated from the solution by allowing to stand for 30 minutes were filtered and recrystallized from 300 ml. of 90% acetic acid. 9.3 g. of crystals of the captioned compound (M.P. C- 187 C.) was thus obtained.
Percent of- Analysis (for ClOHasClzOlz) C H 01 Calculated 66. 21 4. 27 7. 88 Found- 66. 12 4. 18 8. 05
This compound showed wave length of absorption maximum (A at 576 111,11. and molecular extinction coefficient (e) of 1016x10 in dichloroethane.
Preparation No. 2
6,6 methylenebis[2 (4' methoxynaphthylvinylene)- 3-phenylbenzopyrylium perchlorate] (Compound No. 2 having the following formula) OCH solution conta i I Percent of Analysis roi- (261111015012) 1 o" 2 n '01 Calculated-.'..'.. 69.23 e25 7.08 Found;-;-. "--'Y69.18' e14 ass This compound showed wave length of absorption maximama... at 660 mpzand molecular extinction coefiicient (e) of 8.7) (10 in dichloroethane." Infrared absorption spectrum and transmission absorption spectrum of this compound are respectively shown'in FIG. 4 and FIG. 6 of the accompanying drawings.
Preparation No. 3
6,6-methylenebis [2 (p methoxystyryl) 3 decylbenzopyrylium-perchlorate] (Compound No. 13 having the following formula) v DoCI-Ia 7 2 g. of 5,5-'-methylenebissalicylaldehyde was dissolved in 50 ml. of ethyl alcohol and to'this solution was added a solution containing 7.6 g. of methyl undecyl ketone in 40 ml. of 90%% acetic acid. After having been well mixed, the solution was saturated with hydrogen chloride while cooling. The solution was allowed to stand in an ice box for 4 days and then to this solution was added a solution containing 5.2 g. of p-methoxybenzaldehyde in 20 ml. of 90% formic acid. This solution was saturated with hydrogen chloride, and thereafter the same procedure as that of Preparation No. 1 was repeated. 13.5 g. of crystals of the captioned compound (M.P. 173 C.- 174 %C.) was thus obtained.
Percent of- Analysis (for C5'IH70C11012) C H 01 Calculated 62. 40 6. 38 6. 38 Found 62. 38 6. 42 6. 35
This compound showed wave length of absorption maximum (A at 559 my and molecular extinction coefiicient (e) of 8.79X10 in dichloroethane.
Preparation No. 4
6,6 methylenebis[2 (2',3',4' trimethoxystyryl)-3- phenylbenzopyrylium perchlorate] (Compound No. 1 having the following formula) H 00 OCH;
2.5 g. of 5,5-methylenebissalicylaldehyde was dissolved in 40 ml. of tetrahydrofuran and to this solution was added a solution containing 3 g. of benzyl methyl ketone in 20 ml. of 90% acetic acid. After having been well mixed, the solution was saturated with hydrogen chloride while cooling. The solution was allowed to stand in an ice box for 2 hours and then to this solution was added a solution containing 4 g. of 2,3,4-trimethoxybenzaldehyde in 30 ml. of 90% acetic acid. This solution was saturated with hydrogen chloride while cooling and thereafter the same procedure as that of Preparation No. l was repeated 8.0g. of crystals ofithe captioned compound (M.P. 223 C.'225- C.) was'thus obtained.
Percent ofmaximum x at 607 my and molecular extinction coefiicient (e) of 7.4x 10 in dichloroethane.
Preparation No. 5
6,6'-methylenebis[2 (2',4' dimethoxystyry1)-3-octylbenzopyrylium perchlorate] (Compound No. 12 having the following formula) zlzC a 2 2.6 g. of 5,5'-methylenebissalicylaldehyde was dissolved in 50 ml. of tetrahydrofuran and to this solution Was added a solution containing 3.4 g. of methyl nonyl ketone in 20 ml. of formic acid. After having been well mixed, the solution was saturated with hydrogen chloride while cooling. The solution was allowed to stand in an ice box for 3 days and then to this solution was added a solution containing 3.2 g. of 2,4-dimethoxybenzaldehyde in 10 ml. of 90% formic acid. This solution was saturated with hydrogen chloride while cooling and thereafter the same procedure as that of Preparation No. 1 was repeated. 7.5 g. of crystals of the captioned compound (M.P. 200 C.;202 C.) was thus obtained.
Percent of- Analysis (for CaaHzsClzOu) C H 01 Calculated 64. 57 6. 45 6. 84 Found 64. 38 6. 51 6. 90
6,6'-methylenebis[Z-naphthylvinylene-3-phenylbenzopyrylium perchlorate] (Compound No. 14)
o\ oH=oH (M.P. 218 C.-220 C.)
6,6'-methylenebis[2-(p-methoxystyryl)-3-butylbenzopyrylium perchlorate] (Compound No. 10)
OCHa
on, 421 j (M.P.249 C.250 C.) I H I 6,6-methyle'nebis[2-( g-ethoxystyryl.)r3 phenylbenzq 1; pyrylium perchlorate] (Compound No.7)
0+ l cn=ono 02115 CH: 'CIOF (M.P. 250 C'251 C.)
In the above-mentioned Examples and Preparations, benzopyrylium salts having C10 as an anion have been shown. Benzopyrylium salts having BF;- or AuCl; as an anion can be obtained by using an aqueous solution of sodium tetrafluoroborate (NaBF or chloroauric acid (HAuCl instead of an aqueous solution of perchloric acid (H010 We claim:
1. A sensitizer for use in an electrophotographic lightsensitive material having the formula (I):
\ CH=CHRg CH1 A rivative isj- 6;6' methvlenebisn (4Gmethoxynaphthyii '4. A sensitize: afbording'tofclaim'lfwheiiein rivativ'e" is 6,6 "'methy1enebis'[2 (p"-methoxystyryl)-3'- decylbenzopyryliumperchlorate a 5. A sensitizer according? to; claim .IWherein thevderi-var tive is 6,6 methylenebis[2-(2Z3i,4f-trimethoxystyryl)& 3-phenylbenzopyrylium perchlorate,
6. A sensitizer according to elaim l yvherein the deriva-v tive is 6,6 methy1enebis[2 =.(,2,, -,dimethoxystyryl)-3- octylbenzopyryliumperchlorate Y
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP46044739A JPS4926634B1 (en) | 1971-06-21 | 1971-06-21 | |
| JP46050171A JPS515786B1 (en) | 1971-07-07 | 1971-07-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3814752A true US3814752A (en) | 1974-06-04 |
Family
ID=26384702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00259392A Expired - Lifetime US3814752A (en) | 1971-06-21 | 1972-06-05 | 6,6'-methylenebis(2-styryl benzopyrylium salt)as sensitizers for use in electrophotographic light-sensitive materials |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3814752A (en) |
| DE (1) | DE2230302C3 (en) |
| FR (1) | FR2143195B1 (en) |
| GB (1) | GB1390429A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9663477B1 (en) | 2014-09-19 | 2017-05-30 | The United States Of America As Represented By The Secretary Of The Navy | Synthesis and structure of 3,5-diamino-2,6-di-(tert-butyl-NNO-azoxy) pyrazine as a critical intermediate in the synthesis of a novel energetic compound |
-
1972
- 1972-06-05 US US00259392A patent/US3814752A/en not_active Expired - Lifetime
- 1972-06-08 GB GB2691072A patent/GB1390429A/en not_active Expired
- 1972-06-21 DE DE2230302A patent/DE2230302C3/en not_active Expired
- 1972-06-21 FR FR727222367A patent/FR2143195B1/fr not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9663477B1 (en) | 2014-09-19 | 2017-05-30 | The United States Of America As Represented By The Secretary Of The Navy | Synthesis and structure of 3,5-diamino-2,6-di-(tert-butyl-NNO-azoxy) pyrazine as a critical intermediate in the synthesis of a novel energetic compound |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2230302C3 (en) | 1975-05-15 |
| FR2143195A1 (en) | 1973-02-02 |
| GB1390429A (en) | 1975-04-09 |
| DE2230302A1 (en) | 1972-12-28 |
| FR2143195B1 (en) | 1973-07-13 |
| DE2230302B2 (en) | 1974-09-05 |
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