前苏联专利SU1277890A3 Method of producing beta-(benzthiazolylthio) or beta-(benzimidazolylthio)-carboxylic acids

专利PDF首页>>前苏联专利

专利附录

专利说明

权利要求

类似技术

同族专利

引用文献

法律状态

优先权

专利摘要:
Die Reaktion von 2-Mercapto-benzthiazol oder -benzimidazol mit a,ß-ungesättigten Carbonsäuren in stark saurem Reaktionsmedium liefert Verbindungen der Formel worin X Schwefel oder NH ist, jedes R unabhängig voneinander H, Alkyl, Halogenalkyl, alkoxy, Alkylthio, Alkylsulfonyl, Phenyl, Alkylphenyl, Phenylalkyl, Cycloalkyl, Halogen, NO2, CN, COOH, COOAlkyl, OH oder eine Amino- oder Carbamoylgruppe bedeutet und R', R2 und R3 unabhängig voneinander H, Alkyl, Halogenalkyl, Hydroxyalkyl, Alkoxyalkyl, Carboxyalkyl, Carboxyl, unsubstituiertes oder substituiertes Aryl oder Aralkyl bedeuten oder R' und R2 zusammen unverzweigtes oder verzweigtes Alkylen bedeuten, das durch 1 oder 2 Carboxylgruppen substituiert sein kann.
公开号:SU1277890A3
申请号:SU843741050
申请日:1984-05-11
公开日:1986-12-15
发明作者:Боссхард Ханс；Гройтер Ханс
申请人:Циба-Гейги А.Г. (Фирма)；
IPC主号:

专利说明:

The invention relates to a process for the preparation of new p- (benzthiazole cltib) or 6- (benzimidazolylthio) -carboxylic acids, which can be used as corrosion inhibitors in aqueous systems or in metal coatings. The purpose of the invention is a new method of obtaining new compounds with valuable properties. Example. In 40 ml of 70% sulfuric acid, 16.8 g of finely divided powdered 2-mercaptobenzthiazole are suspended and to the resulting suspension is added with stirring for one hour at 48-51 C 10.2 of powdered maleic anhydride. After stirring for 1 h more, the reaction mixture is cooled to room temperature and diluted with 250 ml of water added dropwise at 25-35 ° C. After 1 h, the precipitated product is filtered off and dissolved in a dilute solution of sodium hydroxide. The solution is filtered and acidified with hydrochloric acid. The precipitated precipitate is filtered off and dried in vacuo at. As a result, 24.7 g (87% of the theoretical yield) of benzthiazol-2-ylthio-succinic acid are obtained, melting with decomposition at 75-176 ° C. Calculated,%: C, 46.64; H 3.18; N 4.94; S 22.61. C..H N0. S, If9 th 2 Found: C 46.6; H 3.4; N 5.0; S 22.5. I If 12.1 g of maleic acid is used as the starting material instead of the anhydride, then 22.6 g (807, from the theoretical yield) of benzothiazolothiotartic acid are obtained. If 12.1 g of fumaric acid is used as the starting material and the reaction is carried out 12 h at, then the result is 21.1 g (75% of the theoretical yield) of benzthiazolylthiartaric acid. Example 2. A finely divided powdered mixture of 16.8 g of 2-Mercaptobenzthiazole and 10.3 g of maleic anhydride is added with stirring to a mixture of 60 ml of 36% hydrochloric acid and 60 ml of 99% acetic acid. The reaction mixture is heated at 70-75 ° C for 4 hours and the resulting solution is poured into 500 ml of water. The precipitated precipitate is filtered off, washed cold with water and dried. The result is 2D g (85% of theoretical yield) benzthiazol-2-ylthio-succinic acid. Example 3. 3.4 g of 2-mercaptobenzthiazole and 2.0 g of maleic anhydride are heated in 40 ml of trifluoroacetic acid for 12 hours while stirring at 50 ° C. The reaction mixture is diluted with ice water and the precipitated product is dissolved in ethyl acetate. The solution is washed three times with water and evaporated to dryness. The result is 4.5 g (79% of theoretical yield) benzthiazol-2-ylthio-succinic acid. Example 4. 16.8 g of powdered 2-mercaptobenzthiazole are suspended in 50 ml of 70% sulfuric acid, and 13.7 g of itaconic acid are added to the resulting suspension for 30 minutes at 40-44 ° C. After holding the reaction mixture for another 1.5 hours at 40-44 ° C, it is cooled to room temperature and diluted with water, the temperature being kept lower. The precipitate of 3- (benzthiazol-2-ylthio) propane-1,2-dicarboxylic acid is filtered off, washed with cold water and dried in vacuo at. The yield is 27.5 g (92% of theory), m.p. 160-166C. C 48.48; H 3.93; Calculated,%: N 4.71; S 21.57. C ,, H ,,, Found,%: C 48.2; H 3.7; N 4,6; 821.3. When the addition reaction of itaconic acid to 2-mercapto benzazazole in trifluoroacetic acid is carried out, by analogy with Example 3, 3- (benzthiazol-2-ylthio) -propan1, 2-dicarboxylic acid is obtained with a yield of 96%. Example 5. In 100 ml of cistil ether are dissolved at 0-5C J, 3 g of AlClg and then 3.4 g of 2-mercaptobenzthiazole and 2.6 g of itaconic acid are added to the resulting solution. After 24 hours of stirring at 2025 ° C, the ether solution is poured, and the residue is mixed with 100 ml of water and 100 ml of ethyl acetate. The organic phase is separated, dried and evaporated. The result is 3 g of 3- (benzthiazole31 -2-ylthio) propane-, 2-dicarboxylic acid. Example 6. Into 50 ml of 70% suspension, 16.8 g of 2-mercapto benzthiazole are suspended and 13.7 g of glutamic acid are added to the suspension while stirring and 4550 ° C over 30 minutes. The reaction mixture is stirred for another 1.5 h at 45-50 ° C and the resulting product is isolated by analogy with example 5. As a result, 26 g (88% of theoretical distilled) of 3- (benzisol-2-ylthio) -glutaric acid are obtained. acids with t. pl. 153-154C. Calculated,%: C, 48.48; H 3.71; N 4, S 21., 57. C ,,, Found,%: C 48.5; H 3.8; N 4,6; S 21, 2. Example 7. 16.8 g of finely powdered 2-mercaptobenzthiazole is suspended in 50 ml of a 70% aqueous solution of sulfuric acid, and to the suspension obtained, 30.0 ml of 9.0 g of methacrylic acid are added dropwise with vigorous stirring at 45-50 ° C. The mixture is kept for 1 hour at and then diluted with 20 ml of water added dropwise at 20-30 ° C. The precipitated product is dissolved in water with the addition of sodium hydroxide and the insoluble residue is separated by filtration. From the filtrate, the product is sown by adding hydrochloric acid thereto. After separating the precipitate and drying it in vacuum at 60 ° C, 22.3 g (88% of the theoretical yield) of 3- (benzthiazol-2-ylthio-propane-2-carboxylic acid) are obtained, which, after recrystallization from a mixture of cyclohexane and reKcaiia, in the ratio of 1: 1, melts at 9799 ° C. Calculated,%: C 52.15; H 4.38; N 5.53; S 25.31, C, D, KO S, Found:%: C 52.3; H 4.4; N 5.7; S 25.7.
In a similar way, using instead of methacrylic cretonic acid, 2- (benzthiazol-2-Sh1thio) -propan-1-carboxylic acid is obtained, which, after recrystallization from a mixture of cyclohexane and hexane, taken in the ratio of 1: 1, melts at 61 ° C.
Calculated,%: C 54.04; H 4.54; N 12.6; S 14.43,
S
Found,%: C 54.3; H 4.5; N 12.5; 514.1.
When using instead of acrylic acid, 10.8 g of methacrylic acid and carrying out the reaction with semi-904 EXAMPLE 8. A mixture of 47.4 g of 2-mercapto-6enzthiazole and 40.7 g of itaconic acid in finely powdered form is added 1 hour to 50 ml 70% aqueous solution of sulfuric acid. The temperature of the mixture while stirring is maintained at 4043 ° C. The mixture is then left for 1, 5 hours at this temperature, after which it is diluted with water and ice to 2 liters, the pH of the solution by adding a 30% aqueous solution of caustic soda is set equal to 4. The precipitate is filtered off. After washing with water and drying in vacuum at 30 ° C, 92.5 g of 3- (benzimidazol-2-ylthio) propane-1,2-dicarboxylic acid (97% of the theoretical yield) are obtained in the form of a dihydrate. - mp, (with decomposition), Anhydrous product is obtained by recrystallization from acetone, m, 165-168s. Calculated,%: C, 51.42; H 4.32; N 10.00; S 11.44, S Found,%: C 51.6; H 4.4; N 9.8; S 11,2, In a similar manner, using maleic anhydride instead of itaconic acid, benzimidazole-2-ylthio-succinic acid, melting, is obtained (with decomposition) at. Example 9. 15, O g of 2-mercaptobenzimidazole was dissolved in 50 ml of a 70% aqueous solution of sulfuric acid, and to the resulting solution was added 1 dropwise for 1 hour at 20-25 ° C, 9.0 g of acrylic acid. The mixture is kept at a temperature of 20-25 ° for 2 hours, after which it is diluted with ice water to 250 ml. After adding caustic soda to the mixture, its pH is set to 5. The precipitated product is filtered off, washed with water and dried. As a result, 22.0 g (99% of the theoretical yield) of 2- (benzimidazol2-ylthio) -propionic acid, which, after recrystallization from glacial acetic acid, melts G to decomposition) at 188 ° C,

权利要求:
Claims (2)
[1]
Formula of inventions
one . The method of obtaining j) - (benzthiazolylthio) or / - (benzimidazolylthio) - carboxylic acids of the general formula
Cun
each of the substituents R independently of one another is a lower alkyl atom, a halogen atom or a COOH-group;
five
each of the substituents R independently of one another is a lower alkyl atom, a halogen atom or a COOH group;
- independently of one another - a hydrogen atom, lower alkyl, carbsyalkyl, carboxyl group; 30 R-R 2 - together straight or branched alkylene, which may be substituted by one or two carboxyl groups,
characterized in that 35 compound of formula
and diluted with another 200 ml of water. After 1 hour of stirring, the precipitated precipitate is filtered off and dried. The resulting 4- (benzthiazol-2-yl-thio) -butane-1,2,3-tricarboxylic acid, after recrystallization from a mixture of methanol and water, melts at 188-190 ° C.
Calculated,%: C 47.32; H 3.69; N 3.94.
C ,, NO, S,
Found,%: C, 47.40; H, 3.86; N, 3.89. Example 11. The reaction was carried out under the conditions of example between 8.6 g of 6-chloro-2-mercapto-4-methylbenzthiazole.
and 4.4 g of maleic anhydride in 70% 40 sulfuric acid at 47-50 0. The crude product is purified by reprecipitation from the solution of MANSO. In p-R it has the indicated values - as a result, 6-chloro-4-methyl-benzene is reacted with an unsaturated thiazol-2-lthi-succinic acid, which is promoted to the thromboylum (decomposed) at 168 ni c .
Calculated,%: C 43.44; H 3.04; N 4.22.
P-SH
.g
1 s with s-soon
Calculated. %: C 44.04; H 2 4.28.
NOg s.
Found,%: C 43.9; H 2.78; 4.39.
Calculated. %: C 44.04; H 2.78; 4.28.
Formula of inventions
one . The method of obtaining j) - (benzthiazolylthio) or / - (benzimidazolylthio) - carboxylic acids of the general formula
Cun
each of the substituents R independently of one another is a hydrogen atom, a lower alkyl, a halogen atom or a COOH-group;
- independently of one another - a hydrogen atom, lower alkyl, carbsyalkyl, carboxyl group; R-R 2 is together a straight or branched alkylene, which may be substituted by one or two carboxyl groups,
characterized in that the compound of formula
P-SH
The indicated values of the interaction with non-access to
.g
1 s with s-soon
Found,%: C 53.48; H 3.20 :; K 4.17.
Similarly, using 20 g of carboxy-2-mercaptobenzthiazole and 10.26 g of maleic anhydride as a starting material, semi-HBG IIBI Order 6766/60 Circulation 379
Subscription
Random polygons pr-tie, Uzhgorod, st. Project, 4
50 where R, -R have the indicated meanings, or with its anhydride in a strongly acidic medium at 20-75 ° C.
[2]
2. Method 1, characterized by the fact that 70% sulfuric acid or 36% hydrochloric acid is used as a strongly acidic medium.
Subscription

类似技术:

公开号 | 公开日 | 专利标题

SU1277890A3|1986-12-15|Method of producing beta-| or beta-|-carboxylic acids

US2553771A|1951-05-22|Method of preparing n-trichloromethylthioimides

DD247216A5|1987-07-01|PROCESS FOR PREPARING 4- | -2-CHLORO-3-HYDROXYBENZOENAEUREE

US2734904A|1956-02-14|Xcxnhxc-nh

DK118403C|1983-03-07|Alpha-aminopenicillin derivatives and salts thereof for use as intermediates in the preparation of alpha-aminopenicillins.

IL31082A|1969-05-28|Derivatives of heptenoic acid

DE1176660B|1964-08-27|Process for the preparation of triaryl-substituted imidazolinones-4 |

JP2864475B2|1999-03-03|Method for producing 2-phenylbenzotriazoles

US6239277B1|2001-05-29|Process for preparing piperazine-substituted aliphatic carboxylates

US4139555A|1979-02-13|Recovery of |-2-oxo-bornane-10-sulphonate

SU1052158A3|1983-10-30|Process for preparing derivatives of pyrimidylquinazolines or their salts |

US3890364A|1975-06-17|{60 -Aryl-b-|acrylonitriles with an O-dialkyl sulphamidoxy or sulfuric acid semi-ester group

SU415869A3|1974-02-15|

US4233440A|1980-11-11|Triazolyl-stilbenes

US4495351A|1985-01-22|Method for the production of 1-alkyl-6,7-methylene-dioxy-4|-oxo-cinnolin-3-carboxylic acids

US3947464A|1976-03-30|Salts of phenylpropanolamine with thiazolidine carboxylic acids

US3210348A|1965-10-05|6h-6-trichloromethylmercapto-dibenzo[c, e][1, 2]thiazine 5, 5-dioxide compounds

US2748120A|1956-05-29|2-amino-6-aryl-5, 6-dihydro-4-hydroxy-pyrimidines

US3128273A|1964-04-07|4-amino-pteridine-7-carboxamides and method of preparation

US2202212A|1940-05-28|Preparation of guanyl-urea-nu-sulphonic acid

WO1986002069A1|1986-04-10|Biotin intermediates and process therefor

Ghosh et al.1933|EXTENSION OF MICHAEL'S REACTION PART III

RU374272C|1993-11-30|Method of producing 3,5,3',5'-tetrabrom-2,4,2',4'-tetraoxidiphenyl

SU727145A3|1980-04-05|Method of preparing n-substituted oxazolidines

US2723978A|1955-11-15|2-amino-5-alkenyl-6-phenyl-4-pyrimidols

同族专利:

公开号 | 公开日

BR8402250A|1984-12-18|

JPH053464B2|1993-01-14|

US4612378A|1986-09-16|

ES532470A0|1985-12-16|

EP0126030A2|1984-11-21|

GB8313321D0|1983-06-22|

JPS59212477A|1984-12-01|

ES8602692A1|1985-12-16|

EP0126030A3|1987-04-15|

引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

RU2673338C1|2017-11-29|2018-11-26|Федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский государственный химико-фармацевтический университет" Министерства здравоохранения Российской Федерации |Antihypoxic and act-protective agent based on 2--1h-benzimidazol-3-y -3-carboxyprop-2-enoate|US2725364A|1952-12-31|1955-11-29|Monsanto Chemicals|Vinyl halide polymers plasticized with diesters of acid derivatives of 2-benzothiazolyl mercaptan|

BE578934A|1958-05-23|

US3136689A|1959-12-28|1964-06-09|Monsanto Co|Heterocyclic esters effective against micro-organisms|

SU149785A1|1961-12-11|1962-11-30|В.Г. Песин|The method of obtaining 2, 1, 3-thiodiazol-4, 5-dicarboxylic acid|

DE1542886A1|1966-10-04|1970-05-14|Bayer Ag|Fungicides|

EP0006347B1|1978-06-15|1984-01-25|Monsanto Company|Compositions and method for regulating soybean plant growth utilizing substituted benzazolylthioalkanoic acids|

US4289886A|1979-07-05|1981-09-15|Monsanto Company|Imides derived from 2-thioxo-3-benzoxazoline acetic, and propionic acids|

JPH0128108B2|1982-05-22|1989-06-01|Sanshin Kagaku Kogyo Co|GB8313322D0|1983-05-14|1983-06-22|Ciba Geigy Ag|Heterocyclic-aliphatic carboxylic acids|

DE3341633C2|1983-11-17|1991-09-19|Sanshin Kagaku Kogyo Co., Ltd., Yanai, Yamaguchi, Jp|

GB8412065D0|1984-05-11|1984-06-20|Ciba Geigy Ag|Preparation of carboxylic acid derivatives|

GB8412063D0|1984-05-11|1984-06-20|Ciba Geigy Ag|Compositions containing heterocyclic corrosion inhibitors|

IT1185511B|1985-02-19|1987-11-12|Hoechst Italia|AQUEOUS ANTI-CORROSIVE AGENTS CONTAINING AN AMMONIC SALT OF 2-BENZOTHIAZOLYLTHIOCARBOXYLIC ACID|

HU193951B|1985-03-11|1987-12-28|Richter Gedeon Vegyeszet|Process for producing new sulfur-containing 5-substituted benzimidazol derivatives and pharmaceutical compositions containing them|

US5243047A|1988-02-15|1993-09-07|Imperial Chemical Industries Plc|Triazole/thiazole amino-s-triazine bonding agents|

GB2290789B|1994-07-01|1998-09-16|Ciba Geigy Ag|Titanium and zirconium complexes of carboxylic acids as corrosion inhibitors|

US6083416A|1996-07-18|2000-07-04|Fmc Corporation|Corrosion inhibiting processes for refrigeration systems|

FR2765595B1|1997-07-01|1999-10-01|Lorraine Laminage|COMPOSITION FOR TEMPORARY PROTECTION AGAINST CORROSION OF METAL PARTS, PREPARATION AND APPLICATION METHODS THEREOF AND METAL PARTS OBTAINED FROM THIS COMPOSITION|

US6004476A|1997-07-26|1999-12-21|Fmc Corporation|Corrosion inhibiting solutions and processes for refrigeration systems comprising heteropoly complex anions of transition metal elements additional additives|

US6024892A|1997-10-06|2000-02-15|Fmc Corporation|Anticorrosion and pH stable alkali metal halide solutions for air dehumidification|

US6326384B1|1999-08-26|2001-12-04|Robert R. Whittle|Dry blend pharmaceutical unit dosage form|

US6316020B1|1999-08-26|2001-11-13|Robert R. Whittle|Pharmaceutical formulations|

US6369087B1|1999-08-26|2002-04-09|Robert R. Whittle|Alkoxy substituted benzimidazole compounds, pharmaceutical preparations containing the same, and methods of using the same|

US6312723B1|1999-08-26|2001-11-06|Robert R. Whittle|Pharmaceutical unit dosage form|

US6262085B1|1999-08-26|2001-07-17|Robert R. Whittle|Alkoxy substituted Benzimidazole compounds, pharmaceutical preparations containing the same, and methods of using the same|

US6268385B1|1999-08-26|2001-07-31|Robert R. Whittle|Dry blend pharmaceutical formulations|

US6312712B1|1999-08-26|2001-11-06|Robert R. Whittle|Method of improving bioavailability|

US6262086B1|1999-08-26|2001-07-17|Robert R. Whittle|Pharmaceutical unit dosage form|

US6780880B1|1999-08-26|2004-08-24|Robert R. Whittle|FT-Raman spectroscopic measurement|

US6758988B1|1999-09-07|2004-07-06|Fmc Corporation|Corrosion inhibiting solutions for absorption systems|

US6620341B1|1999-12-23|2003-09-16|Fmc Corporation|Corrosion inhibitors for use in oil and gas wells and similar applications|

US6790789B2|2000-10-25|2004-09-14|International Business Machines Corporation|Ultralow dielectric constant material as an intralevel or interlevel dielectric in a semiconductor device and electronic device made|

US8394969B2|2008-09-26|2013-03-12|Merck Sharp & Dohme Corp.|Cyclic benzimidazole derivatives useful as anti-diabetic agents|

EP2348857B1|2008-10-22|2016-02-24|Merck Sharp & Dohme Corp.|Novel cyclic benzimidazole derivatives useful anti-diabetic agents|

AU2009309007A1|2008-10-29|2010-05-06|Merck Sharp & Dohme Corp.|Novel cyclic benzimidazole derivatives useful anti-diabetic agents|

JP5557845B2|2008-10-31|2014-07-23|メルク・シャープ・アンド・ドーム・コーポレーション|Novel cyclic benzimidazole derivatives useful as antidiabetic agents|

WO2011106273A1|2010-02-25|2011-09-01|Merck Sharp & Dohme Corp.|Novel cyclic benzimidazole derivatives useful anti-diabetic agents|

AU2012220595B2|2011-02-25|2015-07-16|Merck Sharp & Dohme Corp.|Novel cyclic azabenzimidazole derivatives useful as anti-diabetic agents|

WO2014022528A1|2012-08-02|2014-02-06|Merck Sharp & Dohme Corp.|Antidiabetic tricyclic compounds|

WO2014031515A1|2012-08-22|2014-02-27|Merck Sharp & Dohme Corp.|Novel azabenzimidazole hexahydrofuro[3,2-b]furan derivatives|

EP2888007B1|2012-08-22|2019-09-18|Merck Sharp & Dohme Corp.|Benzimidazole tetrahydrofuran derivatives useful as amp-activated protein kinase activators|

US9556193B2|2012-08-22|2017-01-31|Merck Shapr & Dohme Corp.|Benzimidazole hexahydrofuro[3,2-b]furan derivatives|

EP2906040B1|2012-08-22|2021-02-17|Merck Sharp & Dohme Corp.|Novel benzimidazole tetrahydropyran derivatives|

US9382243B2|2012-08-22|2016-07-05|Merck Sharp & Dohme Corp.|Azabenzimidazole tetrahydropyran derivatives|

US9868733B2|2012-08-22|2018-01-16|Merck Sharp & Dohme Corp.|Azabenzimidazole tetrahydrofuran derivatives|

WO2014139388A1|2013-03-14|2014-09-18|Merck Sharp & Dohme Corp.|Novel indole derivatives useful as anti-diabetic agents|

WO2015051496A1|2013-10-08|2015-04-16|Merck Sharp & Dohme Corp.|Antidiabetic tricyclic compounds|

WO2015073342A1|2013-11-15|2015-05-21|Merck Sharp & Dohme Corp.|Antidiabetic tricyclic compounds|

WO2015089809A1|2013-12-19|2015-06-25|Merck Sharp & Dohme Corp.|Antidiabetic substituted heteroaryl compounds|

法律状态:

优先权:

申请号 | 申请日 | 专利标题

GB838313321A|GB8313321D0|1983-05-14|1983-05-14|Preparation of mercaptan substituted carboxylic acids|

[返回顶部]