CN1349128A - Timely released development inhibiting primary yellow former and its prepn - Google Patents

Timely released development inhibiting primary yellow former and its prepn Download PDF

Info

Publication number
CN1349128A
CN1349128A CN 00123092 CN00123092A CN1349128A CN 1349128 A CN1349128 A CN 1349128A CN 00123092 CN00123092 CN 00123092 CN 00123092 A CN00123092 A CN 00123092A CN 1349128 A CN1349128 A CN 1349128A
Authority
CN
China
Prior art keywords
yellow coupler
inhibiting
timed release
formula
release development
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 00123092
Other languages
Chinese (zh)
Other versions
CN1167980C (en
Inventor
修煜
欧阳贵平
李善柱
代秀全
陈学慧
范天奕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
INST OF PHOTOSENSITIVE CHEMICAL ENGINEERING CHINA LEUKAI FILM GROUP
Institute of Photographic Chemistry of CAS
Original Assignee
INST OF PHOTOSENSITIVE CHEMICAL ENGINEERING CHINA LEUKAI FILM GROUP
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by INST OF PHOTOSENSITIVE CHEMICAL ENGINEERING CHINA LEUKAI FILM GROUP filed Critical INST OF PHOTOSENSITIVE CHEMICAL ENGINEERING CHINA LEUKAI FILM GROUP
Priority to CNB001230921A priority Critical patent/CN1167980C/en
Publication of CN1349128A publication Critical patent/CN1349128A/en
Application granted granted Critical
Publication of CN1167980C publication Critical patent/CN1167980C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Landscapes

  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

The invention relates to a coupling agent of restraining developed base yellow with timing released. Its molecular structural formula is: A-COC(-)HCONHB(-)(Timing)n-PUG Here A is as an alkyl, aromatic group or rsidue of heterocyclic compound containing N,S,O,C etc; B is as linear chain saturation alkyl, branched chain saturation alkyl and aromatic ring base group; Timing represents timing base; PUG is sulfhydryl commpound. Under certain condition Timing-PUG radical is cracked from 'Timing', generating PUG radical so as to improve performance of film. The invention provides features of reasonable synthesized technique, high purity of the product, high yield and easy to be refined.

Description

Timed-release development-inhibiting yellow-based color former and preparation thereof
The present invention relates to a functional yellow colour-forming agent in the field of photographic chemistry, in particular, it is a timing-release development-inhibiting yellow colour-forming agent in negative silver halide photographic emulsion.
When the color former reacts with an oxidation product of the developer, a development inhibitor is released and has an improvement effect on the photosensitive property. For example: USP 3,227,554; 3,148,064, respectively; 3,933,500, respectively; 4,477,563 demonstrates that in negative-working photographic photosensitive materials, the DIR color former used to improve image definition and color reduction, when reacted with the oxidation product of the developer, the developer binds to the parent of the color former at the coupling site to form a dye, and the released development inhibitor can improve the silver halide granularity of the photosensitive material, creating intra-layer and edge effects. Further, Japanese patent Nos. JPK 03-189645, JPK 03-215869, JPK 03-127057 also describe release development inhibiting yellow couplers with a timed release base, and in particular, such couplers have the effect of reducing the graininess, improving the in-layer and interlayer effects of the film.
Although various researchers in various countries issue numerous patents, many of them have the defects of complicated process route, unsuitability for practical production and the like in the synthesis process. In the published type of time release development inhibiting yellow couplers, a sequential process is generally used, in which the coupler precursor is first bonded to the timing base and then bonded to the inhibiting base. The method has the defects of difficult industrialization in production, high impurity content of products, low yield, difficult product purification, high production cost and the like. For example: JPK 56-114946.
The invention aims to provide a yellow color former with a timed-release development inhibition function and a preparation method thereof, and the yellow color former has the advantages of reasonable synthesis process, high product purity, high yield and easiness in refining.
The invention provides a timed-release development inhibition yellow-based color former, which has the characteristic molecular structure as follows:
Figure A0012309200111
wherein n is 0 or 1;
a is the residue of a color former, which is alkyl or aryl with 1-20 carbon atoms and halogen atom substituent, or the residue of a heterocyclic compound consisting of N, S, O, C;
b is an oil-soluble group of the color former, which is a straight-chain saturated alkyl group or a branched-chain saturated alkyl group consisting of N, S, O and 1-30 carbon atoms, or an aromatic group with a saturated alkane substituent;
TIMING is a TIMING group which, under certain chemical reaction conditions, is detached from the molecule of the color former together with a development-inhibiting group PUG to generate a TIMING-PUG group;
the developing inhibition group PUG is a diazole sulfhydryl compound substituted by oxadiazole five-membered ring sulfhydryl compounds and aryl, substituted aryl, heteroatomsubstituted aryl and the like, and has a structural general formula as follows:
Figure A0012309200112
wherein R is one of the following groups.
Figure A0012309200113
In the invention, A can be one of the following groups:
Figure A0012309200114
(CH3)3C-* (CH3)2CH-* CH3CH2-* CH3(CH2)3CH2-*
in the invention, B can be one of the following groups:
Figure A0012309200121
wherein: n-1-6
Wherein: n-4-18
Wherein: n is 1-5.
The Timing in the invention can be one of the following groups:
Figure A0012309200124
based on the aboveThe invention also provides a preparation method of the timed-release development inhibition yellow color former, which is characterized in that the synthesis route is as follows:
Figure A0012309200126
Figure A0012309200131
specifically, U.S. patent No. USP 4618571; USP No. 4770982; the synthesis methods described in Japanese patent laid-open Nos. 63-284159, 60-203943, and 63-23152. The invention overcomes the defects of the prior art and adopts a process route of a reverse grafting method to synthesize the compound, namely, a fixed time base (Timing) is firstly connected with an inhibiting base (PUG), and then the compound is connected with a parent color former. The method can ensure that the process is smoothly carried out, and has the advantages of high product purity, high yield, easy refining and the like. The present invention is described in detail below by way of examples.
FIG. 1 is a CP-T-ZB nuclear magnetic spectrum;
FIG. 2 shows a CP-ZB nuclear magnetic spectrum.
FIG. 3 is a CP-T-ZC nuclear magnetic spectrum;
example 1
Synthesis of N- [5- [ [4- [2, 4-bis (1, 1-dimethylpropyl) phenoxy]-1-oxobutyl]amino]-2-chlorophenyl]-4, 4-dimethyl-3-oxo-2- [ 4-nitro-2- [5- [ [ [ (4-methylphenoxy) methyl]-1, 3, 4-oxadiazol-2-yl]mercapto]methyl]phenoxy]-N-pentanamide (abbreviated to CP-T-ZB)
And (3) synthesis of an intermediate:
2- [5- [ (4-Methylphenoxy) methyl group]-1, 3, 4-oxadiazole-2-mercaptomethyl]-4-nitrophenol (T-Z13 for short) is synthesized by the following reaction formula:
Figure A0012309200132
the operation method comprises the following steps:
in a 125 ml three-necked flask equipped with a thermometer, a condenser, a dropping funnel and a stirring device, 2.6 g of ZBTA and 50 ml of acetone were added, and dissolved by stirring, and 20 ml of acetone solution containing 2.1 g of benzal chloride was slowly dropped. After the dropwise addition, the mixture was stirred for half an hour, heated to reflux, then thermally filtered to remove insoluble substances, cooled to precipitate a solid, filtered and dried to obtain 3.4 g of a white solid. Yield 91.2%, melting point mp: 159-160 ℃.
Synthesis of DIAR yellow coupler CP-T-ZB, reaction formula:
the operation method comprises the following steps:
adding 1.56 g of parent color former chloride, 0.94 g of T-ZB and 30 ml of acetonitrile into a 50 ml three-necked bottle provided with a thermometer, a condenser and a stirring device, stirring and dissolving, heating to 40 ℃, adding 0.4 ml of triethylamine, controlling the temperature to be about 40-50 ℃, cooling after 3.5 hours, and filtering. Putting the wet filter cake into a 50 ml three-necked bottle, adding 30 ml of methanol, carrying out hot melting, freezing, separating out, filtering and drying to obtain 1.5 g of a product. Yield 63.8%, melting point mp: 177 to 178 ℃. The actual values (%) of the elemental analysis of C, H, N were: 63.35; 6.57; 7.31. (theoretical values: 63.72; 6.37; 7.43, respectively)
Example 2
Synthesis of N- [5- [ [4- [2, 4-bis (1, 1-dimethylpropyl) phenoxy]-1-oxobutyl]amino]-2-chlorophenyl]-4, 4-dimethyl-3-oxo-2- [ [5- [ (4-methylphenoxy) methyl]-1, 3, 4-oxadiazol-2-yl]mercapto]-N-pentanamide (abbreviated to CP-ZB)
The reaction formula is as follows:
Figure A0012309200151
the operation method comprises the following steps:
adding 3.12 g of parent color former chloride, 1.12 g of ZB and 50 ml of acetonitrile into a 100 ml three-mouth bottle provided with a thermometer, a condenser and a stirring device, stirring and dissolving, heating to 40 ℃, adding 0.8 ml of triethylamine, controlling the temperature to be about 40-50 ℃, cooling after8 hours, pouring into water, filtering and drying to obtain brown solid. After dissolving the solid in ethyl acetate, the solution was washed with water to neutrality using a separatory funnel, and a little anhydrous magnesium sulfate was added thereto and allowed to stand overnight. The next day, the mixture is filtered, 30 ml of petroleum ether (bp: 60-90 ℃) is added, solid is gradually separated out the next day, and the product 1.5 g is obtained after filtration and drying. Melting point mp: 78-80 ℃. The actual values (%) of the elemental analysis of C, H, N were: 65.10; 6.87; 7.12. (theoretical values: 65.28; 6.96; 7.09 respectively)
Example 3
Synthesis of N- [5- [ [4- [2, 4-bis (1, 1-dimethylpropyl) phenoxy]-1-oxobutyl]amino]-2-chlorophenyl]-4, 4-dimethyl-3-oxo-2- [ 4-nitro-2- [5- [ [ [ (4-chlorophenoxy) methyl]-1, 3, 4-oxadiazol-2-yl]mercapto]methyl]phenoxy]-N-pentanamide (abbreviated to CP-T-ZC)
And (3) synthesis of an intermediate:
synthesis of 2- [5- [ (4-chlorophenoxy) methyl]-1, 3, 4-oxadiazole-2-mercaptomethyl]-4-nitrophenol (abbreviated as T-ZC):
the reaction formula is as follows:
Figure A0012309200161
the operation method comprises the following steps:
adding ZCNa 2.64 g and 50 ml of acetone into a 125 ml three-neck flask provided with a thermometer, a condenser, a dropping funnel and a stirring device, stirring and dissolving, slowly dropping 20 ml of acetone liquid containing 2.1 g of benzyl chloride, stirring for half an hour after dropping, heating to reflux, then carrying out hot filtration, removing insoluble substances, cooling to separate out solid, filtering, and drying to obtain 3.0 g of white solid. Yield 88%, melting point mp: 179-181 ℃.
Synthesis of DIAR yellow coupler CP-T-ZC:
the reaction formula is as follows:
the operation method comprises the following steps:
in a 50 ml three-necked flask equipped with a thermometer, condenser and stirring device, 1.56 g of the parent coupler chloride, 0.97 g of T-ZC and 30 ml of acetonitrile were added. The operation method refers to the synthetic method of CP-T-ZB. 1.48 g of product is obtained, yield 60.0%, melting point mp: 187-189 ℃. The actual values (%) of the elemental analysis of C, H, N were: 61.09; 5.89; 7.27. (theoretical values: 61.11; 5.92; 7.28, respectively)
The present invention also synthesizes the following compounds by a method similar to the above examples, but the present invention is not limited thereto.
Example 4
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 5
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
Figure A0012309200181
example 6
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 7
Following the procedure of example 3, using the corresponding intermediate, the following compound was prepared:
Figure A0012309200183
example 8
Following the procedure of example 3, using the corresponding intermediate, the following compound was prepared:
example 9
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 10
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 11
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
Figure A0012309200193
example 12
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 13
Following the procedure of example 3, using the corresponding intermediate, the following compound was prepared:
example 14
Following the procedure of example 3, using the corresponding intermediate, the following compound was prepared:
Figure A0012309200202
example 15
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 16
Following the procedure of example 3, using the corresponding intermediate, the following compound was prepared:
Figure A0012309200204
example 17
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 18
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
Figure A0012309200212
example 19
Following the procedure of example 3, using the corresponding intermediate, the following compound was prepared:
Figure A0012309200213
example 20
Preparation method according to example 3Using the corresponding intermediate, the following compounds were prepared:
example 21
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
Figure A0012309200221
example 22
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
comparative example 1: synthesis of CP-T-ZB
The reaction equation is as follows:
Figure A0012309200231
the operation method comprises the following steps:
adding 7 g of 2-nitro-5-hydroxybenzyl alcohol, 12.16 g of compound (A) and 100 ml of acetone into a 250 ml three-neck flask provided with a thermometer, a condenser, a dropping funnel and a stirring device, stirring to fully dissolve, adding 3 ml of triethylamine, heating to 50 ℃, preserving heat for reacting for 8 hours, cooling to 10 ℃ after the reaction is finished, dropwise adding hydrochloric acid for neutralizing, adding 400 ml of water, stirring for separating out, standing for solidification, and filtering the mixture the next day to obtain a light yellow solid substance. And naturally drying, and leaching and drying the obtained solid in a funnel by using 30 ml of petroleum ether for three times to obtain 9.40 g of solid with a light yellow solid appearance. Liquid chromatography analysis, content 81%, melting point mp: 78-84 ℃.
Adding 9.40 g of the light yellow solid into a 250 ml three-mouth bottle provided with a thermometer, a condenser and a stirring device, adding 70 ml of dry chloroform, stirring and dissolving, keeping the internal temperature at 20 ℃, adding phosphorus pentachloride in small parts, reacting for 5 hours after half an hour until no hydrogen chloride gas is emitted. After stirring for 10 minutes with addition of 50 ml of water, the reaction solution was poured into a separatory funnel and washed with water until the pH of the solution became 7, and then 50 ml of chloroform was added thereto, and dried overnight with addition of anhydrous calcium chloride. The next day, the drying agent calcium chloride is removed, the chloroform is evaporated by pumping water under reduced pressure until the internal temperature does not exceed 50 ℃, the chloroform is evaporated until the temperature is all the time, 20 ml of acetone is added for dissolution, 10% hydrochloric acid and 200 ml of ice water are added, the pH value is adjusted to 2-3, and after solid is separated out, the filtration is carried out to obtain 2 g of light yellow solid. The yield is 12.5 percent, and the content is 94 percent by liquid chromatography detection.
Adding the prepared large parent benzyl chloride into a 150 ml three-neck flask provided with a stirrer, a condenser and a heating device, adding 40 ml of acetonitrile, 1.0 g of compound (B) and 0.4 ml of triethylamine, heating and stirring, refluxing for 4 hours, cooling the reaction solution, pouring into a beaker filled with 100 ml of ice water, and filtering after the solid is completely separated out to obtain a yellow solid. Silica gel column chromatography gave 0.3 g of a yellow oily product.

Claims (27)

1. A timed release development-inhibiting yellow coupler characterized by the molecular structure:
Figure A0012309200021
wherein n is 0 or 1;
a is the residue of a color former, which is alkyl or aryl with 1-20 carbon atoms and halogen atom substituent, or the residue of a heterocyclic compound consisting of N, S, O, C;
b is an oil-soluble group of the color former, which is a straight-chain saturated alkyl group or a branched-chain saturated alkyl group consisting of N, S, O and 1-30 carbon atoms, or an aromatic group with a saturated alkane substituent;
TIMING is a TIMING group which, under certain chemical reaction conditions, is detached from the molecule of the color former together with a development-inhibiting group PUG to generate a TIMING-PUG group;
the method is characterized in that: the development inhibiting group PUG is a diazole sulfhydryl compound substituted by oxadiazole five-membered ring sulfhydryl compounds and aryl, substituted aryl, heteroatom substituted aryl and the like, and has a structural general formula as follows:
Figure A0012309200022
wherein R is one of the following groups.
Figure A0012309200023
Figure A0012309200031
2. The timed release development-inhibiting yellow coupler according to claim 1 wherein a is one of the following groups:
(CH3)3C-* (CH3)2CH-* CH3CH2-* CH3(CH2)3CH2-*
3. the timed release development-inhibiting yellow-based color former according to claim 1, characterized in that B is one of the following groups:
wherein: n-1-6
Wherein: n-4-18
Wherein: n is 1-5.
4. The timed release development-inhibiting yellow coupler according to claim 1, wherein Timing is one of the following groups:
Figure A0012309200041
5. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
Figure A0012309200042
6. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
Figure A0012309200043
7. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
Figure A0012309200044
8. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
Figure A0012309200051
9. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
Figure A0012309200052
10. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
Figure A0012309200053
11. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
Figure A0012309200054
12. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
Figure A0012309200061
13. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
14. the timed release development inhibiting base according to claim 1A yellow coupler characterized in that the yellow coupler has the structural formula:
Figure A0012309200063
15. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
16. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
17. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
18. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
Figure A0012309200073
19. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
Figure A0012309200074
20. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
Figure A0012309200081
21. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
Figure A0012309200082
22. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
23. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
Figure A0012309200084
24. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
25. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
Figure A0012309200092
26. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
Figure A0012309200093
27. a process for preparing a timed release development-inhibiting yellow coupler according to claim 1, characterized by the following synthetic route:
CNB001230921A 2000-10-18 2000-10-18 Timely released development inhibiting primary yellow former and its prepn Expired - Fee Related CN1167980C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB001230921A CN1167980C (en) 2000-10-18 2000-10-18 Timely released development inhibiting primary yellow former and its prepn

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB001230921A CN1167980C (en) 2000-10-18 2000-10-18 Timely released development inhibiting primary yellow former and its prepn

Publications (2)

Publication Number Publication Date
CN1349128A true CN1349128A (en) 2002-05-15
CN1167980C CN1167980C (en) 2004-09-22

Family

ID=4589571

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB001230921A Expired - Fee Related CN1167980C (en) 2000-10-18 2000-10-18 Timely released development inhibiting primary yellow former and its prepn

Country Status (1)

Country Link
CN (1) CN1167980C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1320403C (en) * 2003-08-14 2007-06-06 中国乐凯胶片集团公司 Yellow colour coupler

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1320403C (en) * 2003-08-14 2007-06-06 中国乐凯胶片集团公司 Yellow colour coupler

Also Published As

Publication number Publication date
CN1167980C (en) 2004-09-22

Similar Documents

Publication Publication Date Title
CN1495157A (en) Preparation method of cyanophthaofluoroaniline
FR2962731A1 (en) PROCESS FOR THE PREPARATION OF AMINO-BENZOYL-BENZOFURAN DERIVATIVES
CN1106666A (en) Pharmaceutical use of 24-homo-vitamin-D-derivative
CN86101277A (en) Trisubstituted phenylformic acid intermediates preparation
CN1325400A (en) Chemiluminescent 1,2-dioxietanes
CN1173928C (en) Process for preparing (1R,2S,4R)-(-)-2-[(2'-{N,N-dimethylamino}-ethoxy)]-2-[phenyl]-1,7,7-tri-[methyl]-bicyclo[2.2.1] heptane and pharmaceutically acceptable acid addition salts thereof
EP0331556A2 (en) Process for the preparation of ethylene diamine N,N'-bis(ortho-hydroxyphenylacetic) acid and derivatives thereof
CN1349128A (en) Timely released development inhibiting primary yellow former and its prepn
EP0002978A2 (en) Thiazolidinedione-2,4 derivatives, their preparation and pharmaceutical applications
CN1308289C (en) Synthesis method for water-soluble bisamide oxide
CN1205204C (en) 3-hydroxymethylbenzo [b] thiphene derivatives and process for their preparation
CN1261420C (en) Process for the manufacture of thiazole derivativs with pesticide activity
CN1196665C (en) Process for the preparation of 5-[4-chlorophenyl)-methyl]-2, 2-dimethylcyclopentanone
CN1121383C (en) Process for recycle of waste product of diltiazem synthesis
KR100407720B1 (en) Preparing Method for N-[3-{3-(1-Piperidinylmethyl)phenoxy}propyl]acetoxyacetamide
CN1274783C (en) Hexahydrogen bonded self-assembled supermolecular yellow-green luminescent material and its synthesizing method
CN1075055C (en) Process for reducing amino acids and derivatives thereof
RU2007129433A (en) SELENORGANIC COMPOUNDS AND THEIR APPLICATION
JP2007246517A (en) Process for producing optically active 5-hydroxy-3-keto ester compound
EP1095937B1 (en) Process for the preparation of trisubstituted oxazoles
CN1220674C (en) Levodopa methyl ester hydrochloride purifying method
WO2005051897A1 (en) Process for the preparation of tamsulosin
CN1489577A (en) Cyanothioacetamide derivatives and process for preparing same
CN1070647A (en) Preparation has the method for optically active false bufotoxin amidoalcohol
CN1622935A (en) Process for producing 4,4'-bisphenol sulfone

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20040922

Termination date: 20131018